TWI726132B - Polyolefin adhesive composition - Google Patents

Abstract

The invention provides an adhesive composition, which contains modified polyolefin and epoxy resin, has good pot life performance, and has good adhesion to metal substrates and polyolefin resin substrates. The present invention is an adhesive composition containing: crystalline acid-modified polyolefin (A) with an acid value of 5-50 mgKOH/g-resin, glycidyl amine epoxy resin (B1), and chelate modified ring Oxygen resin (B2) and organic solvent (C).

Description

Polyolefin adhesive composition

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

In the past, metal substrates such as exterior panels of home appliances, furniture materials, and building interior components have been laminated with vinyl chloride resin (hereinafter also referred to as "polyvinyl chloride") coated on the surface. , But nowadays environmental issues have received much attention, and some people have proposed polyolefin resin as a substitute for polyvinyl chloride. Polyolefin resins are non-toxic, exhibit strong durability against acids, alkalis, organic solvents, etc., have excellent mechanical strength, abrasion resistance, and are inexpensive, so they are widely used in various fields.

However, polyolefin resins are difficult to adhere to metal substrates due to their non-polarity. In the past, in order to adhere the polyolefin resin to the metal substrate, various adhesives have been proposed. As a typical example, there is a base adhesive obtained by dissolving thermosetting resins such as phenol resin, melamine resin, and epoxy resin, or thermoplastic resin in an organic solvent, and mixing a solvent-dispersed modified polyolefin resin. However, it is difficult to say that these adhesives have sufficient adhesiveness. In addition, it has also been proposed to blend an adhesive composition such as catechol with crystalline acid-modified polyolefin and epoxy resin (Patent Document 1), blend maleic acid-modified chlorinated polypropylene, and chelate epoxy resin. Adhesive composition of resin and solvent (Patent Document 2). [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2003-261847 [Patent Document 2] Japanese Patent Application Publication No. 2009-292853

[Problem to be solved by the invention] However, the above method may have poor pot life performance after blending with the acid-modified polyolefin solution, and even if pot life performance is not a big problem, it is important to compare with the metal substrate. Adhesion and chemical resistance are still unsatisfactory. In other words, it is not the one that meets the pot life performance, adhesiveness, 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 of 80°C or less where the influence of heat shrinkage or the like is small. Here, the pot life performance refers to the stability of the solution when the modified polyolefin is blended with a crosslinking agent or a hardener, and immediately after blending or after a certain period of time.

The present invention was made in view of the above-mentioned problems in the past. The inventors of the present case conducted diligent research on the adhesive between polyolefin resin substrate and metal substrate, and found that it contains crystalline acid-modified polyolefin, epoxy resin, and organic solvent. The adhesive composition can take into account the pot life performance and the bonding under 80°C, the adhesiveness during maturation, and the chemical resistance, thus completing the present invention.

That is, the present invention aims to provide an adhesive composition, which has good pot life performance after blending crystalline acid-modified polyolefin and hardener, and is effective for polyolefin resin base during low-temperature bonding and maturation. Both the material and the metal substrate have good adhesion and chemical resistance. [Means to solve the problem]

In order to achieve the above-mentioned problems, the inventors of the present application have made diligent studies, and have proposed the following inventions.

An adhesive composition containing: crystalline acid-modified polyolefin (A) with an acid value of 5-50 mgKOH/g-resin, glycidyl amine type epoxy resin (B1), and chelate-modified epoxy resin ( B2) and organic solvents (C).

The aforementioned glycidamine type epoxy resin (B1) is preferably an epoxy resin having two or more glycidyl groups in one molecule.

通式(1) 通式(1)中，R為也可以有取代基之芳基，X1及X2各自獨立地為也可以有取代基之碳數1～5之伸烷基，m為1或2，n為1或2。The aforementioned glycidamine type epoxy resin (B1) is preferably a compound represented by the general formula (1). 【化1】

General formula (1) In general formula (1), R is an optionally substituted aryl group, X1 and X2 are each independently an optionally substituted alkylene group with 1 to 5 carbon atoms, and m is 1 or 2, n is 1 or 2.

The aforementioned chelate-modified epoxy resin (B2) is preferably an epoxy having two or more glycidyl groups in one molecule, and one or more functional groups that do not contain nitrogen atoms but have a chelating effect The resin is better.

It is preferable to contain 0.01-20 parts by mass of glycidyl amine epoxy resin (B1) and 1-20 parts by mass of chelate-modified epoxy resin (B2) relative to 100 parts by mass of crystalline acid-modified polyolefin (A) , The organic solvent (C) is preferably 80-1000 parts by mass.

The organic solvent (C) is preferably a mixture of solvent (C1) and solvent (C2), and solvent (C1) is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons One or more solvents, the solvent (C2) is one or more solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents and glycol ether solvents, solvent (C1)/ Solvent (C2)=50～97/50～3 (mass ratio) is preferable.

The adhesive composition of any one of the foregoing is used for the adhesion of polyolefin resin substrate and metal substrate.

A laminate of a polyolefin resin substrate and a metal substrate is adhered by the adhesive composition as described above. [Effects of Invention]

The adhesive composition of the present invention contains a crystalline acid-modified polyolefin, two types of epoxy resins and an organic solvent, and does not increase viscosity or gelation even if stored for a long period of time, and can maintain good pot life performance. And even if the thermal shrinkage of the polyolefin substrate is small, such as the low temperature below 80°C, the bonding and curing can also take into account the good adhesion and chemical resistance of the polyolefin resin substrate and the metal substrate.

Hereinafter, the 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 limited, and it is preferable to use at least one of α, β-unsaturated carboxylic acid and its anhydride It is preferably obtained by grafting at least one of polyethylene, polypropylene, and propylene-α-olefin copolymer.

The propylene-α-olefin copolymer is obtained by copolymerizing α-olefin with propylene as the main body. As the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, and the like can be used. Among these α-olefins, ethylene and 1-butene are preferred. 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.

At least one of α,β-unsaturated carboxylic acids and anhydrides thereof includes, for example, maleic acid, itaconic acid, citraconic acid, and their anhydrides. Among them, acid anhydride is preferred, and maleic anhydride is more preferred. Specifically, examples include: maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer For the substance and the like, one kind of these crystalline acid-modified polyolefins or a combination of two or more kinds can be used. Among them, maleic anhydride modified propylene-butene copolymer is preferred. The propylene component/1-butene component (mole ratio) of the maleic anhydride modified propylene-butene copolymer is preferably 90-50/10-50, more preferably 85-60/15-40, and 80 ~55/20~45 is particularly preferred, and 75~60/25~40 is particularly preferred. By being within the above range, particularly excellent pot life performance, adhesiveness, and chemical resistance can be exhibited.

Regarding the acid value of the crystalline acid-modified polyolefin (A), considering the pot life performance and the adhesion to the polyolefin resin substrate and the metal substrate, the lower limit must be 5 mgKOH/g-resin or more, preferably It is 10mgKOH/g-resin or more, more preferably 14mgKOH/g-resin or more, particularly preferably 16mgKOH/g-resin or more, particularly preferably 18mgKOH/g-resin or more, most preferably 20mgKOH/g-resin or more. If the above-mentioned value is not reached, the compatibility with epoxy resin may be low, and the adhesive strength may not be exhibited. In addition, the cross-linking density may be low and chemical resistance may be insufficient. The upper limit must be 50mgKOH/g-resin or less, preferably 48mgKOH/g-resin or less, more preferably 46mgKOH/g-resin or less, particularly preferably 44mgKOH/g-resin or less, particularly preferably 42mgKOH/g-resin or less, The best is below 40mgKOH/g-resin. If the value exceeds the foregoing value, the viscosity and stability of the solution may decrease, and the pot life performance may decrease. And the manufacturing efficiency will be reduced, so it is not good. 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. More preferably, it is in the range of 50,000 to 160,000, particularly preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably in the range of 80,000 to 130,000. If the above value is not reached, the cohesion will be weakened and the adhesion will be poor. On the other hand, if the above-mentioned value is exceeded, fluidity may be low, and workability may be problematic during adhesion. If it is within the aforementioned range, the hardening reaction with the epoxy resin can be exerted, which is preferable.

The crystallinity of the crystalline acid-modified polyolefin (A) refers to the temperature rise from -100°C to 250°C at a temperature of 20°C/min using a differential scanning calorimeter (DSC), and it becomes clear during the heating process The melting peak.

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

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

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. It is more preferably in the range of 10J/g to 50J/g, and most preferably in the range of 20J/g to 40J/g. If it does not reach the aforementioned value, the cohesive force derived from the crystal may be weak, and the adhesiveness and chemical resistance may be poor. On the other hand, if the above-mentioned value is exceeded, solution stability and fluidity may be low, and workability may be problematic during adhesion.

The method for producing the crystalline acid-modified polyolefin (A) is not particularly limited. For example, a radical grafting reaction (that is, a radical substance is generated for the polymer that becomes the main chain, and the radical substance is used as the polymerization starter). Point, and graft polymerization of unsaturated carboxylic acid and acid anhydride) and so on.

The radical generator is not particularly limited, and organic peroxides are preferably used. Organic peroxides are not particularly limited, and examples include: di-tert-butyl peroxyphthalate, tertiary butyl hydroperoxide, dicumyl peroxide, benzyl peroxide, and benzoyl peroxide. Peroxides such as tributyl ester, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide trimethyl acetate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauryl peroxide, etc. ; Azo nitriles such as azobisisobutyronitrile and azobisisopropionitrile.

<Glycidylamine-type epoxy resin (B1)> The glycidylamine-type epoxy resin (B1) used in the present invention may be an epoxy resin having at least one glycidyl group in one molecule. Specially limited. It is better to have 2 or more glycidyl groups per molecule of epoxy resin, more preferably 3 or more glycidyl groups per molecule of epoxy resin, and more than 4 glycidyl groups per molecule of epoxy resin. Kyuja.

通式(1) 通式(1)中，R為也可以有取代基之芳基，較佳為也可以有取代基之苯基。前述芳基之取代基並無特別限定，可列舉：碳數1以上5以下之烷基、碳數1以上5以下之烷氧基、羥基、胺基、環氧丙基、環氧丙胺基、或環氧丙醚基。X1及X2各自獨立地為碳數1以上5以下之也可以有取代基之直鏈伸烷基，較佳碳數為4以下，更佳為3以下，尤佳為2以下。前述伸烷基之取代基並無特別限定，可列舉：碳數1以上5以下之烷基、碳數1以上5以下之烷氧基、或胺基。m為1或2，n為1或2。較佳為m或n中之任一者為2，更佳為m、n皆為2。In addition, it is preferable that the glycidyl amine type epoxy resin (B1) uses a compound represented by the following general formula (1) to improve chemical resistance. 【化1】

General formula (1) In general formula (1), R is an aryl group which may also have a substituent, preferably a phenyl group which may also have a substituent. The substituent of the aforementioned aryl group is not particularly limited, and examples include: alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups, amino groups, glycidyl groups, glycidylamino groups, Or glycidyl ether group. X1 and X2 are each independently a linear alkylene group having a carbon number of 1 or more and 5 or less that may also have a substituent. Preferably, the carbon number is 4 or less, more preferably 3 or less, and particularly preferably 2 or less. The substituent of the aforementioned 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 amino group. m is 1 or 2, and n is 1 or 2. It is preferable that either m or n is 2, and it is more preferable that both m and n are 2.

The specific examples of the glycidamine type epoxy resin (B1) are not particularly limited, and examples include: tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, tetraglycidyl bis Aminomethylcyclohexanone, N,N,N',N'-tetraglycidyl-m-xylenediamine and other glycidyl amines, etc. Among them, N,N,N',N'-tetraepoxypropyl-m-xylenediamine is preferred. These glycidamine type epoxy resins (B1) may be used alone, or two or more types may be used.

The blending amount of the glycidamine type epoxy resin (B1) is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more relative to 100 parts by mass of the crystalline acid-modified polyolefin (A) Particularly preferred, 1 part by mass or more is particularly preferred, and 2 parts by mass or more is most preferred. If it does not reach the aforementioned range, it may not exhibit the catalytic effect, and the adhesiveness and chemical resistance during bonding and curing at 80°C or lower may be low. Furthermore, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, particularly 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 aforementioned range, the cross-linking reaction will proceed excessively, resulting in increased rigidity and decreased adhesiveness. In addition, the adhesive composition tends to undergo a cross-linking reaction when stored in a solution, and the pot life tends to be shortened.

<Chelate-modified epoxy resin (B2)> The chelate-modified epoxy resin (B2) used in the present invention may be an epoxy resin having a functional group with a chelating effect in the molecule, and There is no particular limitation. It is preferably an epoxy resin that has 2 or more glycidyl groups and 1 or more functional groups with chelating effect in one molecule of epoxy resin, and does not contain nitrogen atoms, considering reactivity, adhesiveness, and chemical resistance The viewpoint of improved sexuality is preferable. That is, by blending the chelate-modified epoxy resin (B2), the rust resistance of metal substrates such as aluminum is improved, and at the same time, the chemical resistance is improved. Thereby, even if the surface treatment (for example, chromate treatment) of the metal substrate is not applied, the excellent adhesiveness of the adhesive composition and the chemical resistance of the metal substrate can be exhibited.

Chelation refers to the bonding (coordination) of a ligand (multidentate ligand) with multiple coordination sites to a metal ion, with chelation The functional groups for the effect are not particularly limited, and examples include acid groups such as carboxyl, phosphonic acid, sulfonic acid, phosphoric acid, sulfuric acid, nitric acid, and boric acid groups; alcoholic hydroxyl groups, phenolic hydroxyl groups, nitrile groups, and thiols. Those that are not acid groups such as amino groups and amino groups. Preferably, it is a phosphate group.

The blending amount of the chelate-modified epoxy resin (B2) is 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass relative to 100 parts by mass of the crystalline acid-modified polyolefin (A) The above is particularly preferable, 4 parts by mass or more is particularly preferable, and 5 parts by mass or more is most preferable. Furthermore, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, particularly preferably 16 parts by mass or less, particularly preferably 14 parts by mass or less, and most preferably 12 parts by mass or less. By being within the aforementioned range, excellent adhesiveness and chemical resistance can be exhibited.

The chelate-modified epoxy resin (B2) used in the present invention may be used singly or multiple types. Specifically, marketed products such as the EP-49-10 series manufactured by ADEKA can be used.

The present invention is characterized in that two types of epoxy resins of the aforementioned glycidylamine type epoxy resin (B1) and the aforementioned chelate-modified epoxy resin (B2) are used as essential components. By using epoxy propylene amine type epoxy resin (B1) and chelate-modified epoxy resin (B2), it can exhibit excellent adhesion and chemical resistance. That is, the glycidamide type epoxy resin (B1) has a hardening effect when the crystalline acid-modified polyolefin (A) reacts with the chelate-modified epoxy resin (B2). Furthermore, the glycidamine type epoxy resin (B1) chelates the crystalline acid-modified polyolefin (A), the glycidamide type epoxy resin (B1), and the glycidamide type epoxy resin (B1). It has a hardening catalyst effect when reacting with the modified epoxy resin (B2), the glycidyl amine epoxy resin (B1) and the chelate modified epoxy resin (B2), so it can be improved to 80% by blending. Adhesion to metal substrates and chemical resistance during bonding and curing below ℃.

The total blending amount of glycidamine type epoxy resin (B1) and chelate-modified epoxy resin (B2) is 2-40 parts by mass relative to 100 parts by mass of crystalline acid-modified polyolefin (A) Preferably, it is 5-20 parts by mass, more preferably 10-16 parts by mass. If the above range is not reached, sufficient curing effects may not be obtained, and the adhesiveness and chemical resistance may be low. If the above range is exceeded, the pot life performance and adhesion to the olefin substrate will decrease. Considering the cost perspective, Is not good.

The blending amount of the glycidamine type epoxy resin (B1) is preferably 1-50% by mass of the total epoxy resin, more preferably 2-30% by mass, and most preferably 3-10% by mass. If the blending amount is less than the aforementioned range, the catalytic effect may not be exhibited, and the adhesiveness and chemical resistance during low-temperature bonding and curing may be low. If the blending amount exceeds the aforementioned range, the cross-linking reaction may proceed excessively. The rigidity becomes higher and the adhesiveness tends to decrease. In addition, the adhesive composition tends to undergo a cross-linking reaction when stored in a solution, and the pot life tends to be shortened.

As for the epoxy resin used in the present invention, other epoxy resins can also be used. Examples include: glycidyl ether type epoxy resins, glycidyl hexahydrophthalate, glycidyl dimer acid, etc.; triglycidyl isocyanurate, or 3,4-epoxycyclohexyl methyl carboxylate (3,4-epoxycyclohexyl methyl carboxylate), epoxidized polybutadiene, epoxidized soybean oil and other alicyclic or aliphatic epoxides, etc., epoxy propylene The specific example of the ether type epoxy resin is not specifically limited, A phenol novolak type epoxy resin, a cresol novolak type epoxy resin are mentioned, These may be used individually by 1 type, and may use 2 or more types together.

<Organic solvent (C)> The organic solvent (C) used in the present invention, as long as it is a crystalline acid-modified polyolefin (A), a glycidyl amine type epoxy resin (B1), and a chelate-modified epoxy The resin (B2) only needs to be dissolved, and it is not particularly limited. Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, methylcyclohexane, Alicyclic hydrocarbons such as ethyl cyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, phenol, etc. Solvents; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, etc.; methyl serosol, ethyl serosol and other serosols ; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc.; ethylene glycol mono n-butyl ether, ethylene glycol mono isobutyl ether, ethylene glycol mono tertiary butyl ether , Diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether and other glycol ether solvents, etc., one of them can be used Two or more species or more.

The organic solvent (C) is preferably 80 parts by mass or more relative to 100 parts by mass of the crystalline acid-modified polyolefin (A), more preferably 90 parts by mass or more, particularly preferably 100 parts by mass or more, and 110 parts by mass or more. good. If it does not reach the aforementioned range, the solution state and pot life performance may decrease. In addition, it is preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, particularly preferably 800 parts by mass or less, and particularly preferably 700 parts by mass or less. If it exceeds the aforementioned range, there will be disadvantages in terms of manufacturing costs and shipping costs.

As for the organic solvent (C), considering the solution state and pot life performance of the adhesive composition, it is preferably selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons A mixture of one or more solvents (C1) and one or more solvents (C2) selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and glycol ether solvents is preferred . The mixing ratio is solvent (C1)/solvent (C2)=50～97/50～3 (mass ratio), preferably 55～95/45～5 (mass ratio), 60～90/40～10 The (quality ratio) is particularly good, and 70～80/30-20 (the quality ratio) is particularly good. If it falls outside the above range, the solution state and pot life performance of the adhesive composition may decrease. In addition, the solvent (C1) is an aromatic hydrocarbon or an alicyclic hydrocarbon, and the solvent (C2) is particularly preferably a ketone solvent.

<Adhesive composition> The adhesive composition of the present invention is the aforementioned crystalline acid-modified polyolefin (A), glycidamine type epoxy resin (B1), chelate-modified epoxy resin (B2), and organic Mixture of solvents (C). Crystalline acid-modified polyolefin (A), glycidyl amine type epoxy resin (B1) and chelate-modified epoxy resin (B2) can be dissolved in organic solvent (C) or dispersed in organic solvent (C) ). From the viewpoint of pot life performance, it is better to dissolve in an organic solvent (C).

The adhesive composition of the present invention, within the range that does not impair the performance of the present invention, in addition to blending the aforementioned crystalline acid-modified polyolefin (A), glycidamine-type epoxy resin (B1), and chelate modification In addition to the curable epoxy resin (B2) and the organic solvent (C), various hardening accelerators can be blended and used. The hardening accelerator is not particularly limited, and examples include metal carboxylic acid salts, tertiary amines, quaternary ammonium salts, organic peroxides, hydrazine compounds, metal chelate compounds, thioureas, phosphorus-containing compounds, and alkaline vulcanization. Agents, etc. Examples of the aforementioned carboxylic acid metal salt include metal salts of carboxylic acids having 1 to 30 carbon atoms. Examples of carboxylic acids constituting the metal salt of carboxylic acid include acetic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and octenoic acid. , Erucic acid, elaidic acid, adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, diglycolic acid and other aliphatic carboxylic acids; benzoic acid, chlorobenzoic acid, anisic acid , Aminobenzoic acid, phthalic acid, terephthalic acid, naphthoic acid (naphthoic acid), naphthalene dicarboxylic acid, trimellitic acid and other aromatic carboxylic acids; naphthenic acid; pyruvic acid, etc. In addition, examples of the metals constituting the carboxylic acid metal salt include Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti, and the like. The carboxylic acid metal salt specifically includes: 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, terephthalate Magnesium formate, calcium naphthalate, dibutyltin laurate, tributyltin laurate, dioctyltin laurate, tributyltin acetate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin 2-ethylhexanoate , Tetrabutyl titanate, tetraisobutyl titanate, tetra 2-ethylhexyl titanate, cobalt naphthenate, copper naphthenate, magnesium naphthenate, cobalt acetyl acetate, etc. Among these, preferably, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, palmitic acid Magnesium, sodium stearate, potassium stearate, calcium stearate, zinc stearate, sodium oleate. Moreover, the metal salt of a carboxylic acid can also use the polymer which has a metal salt structure of a carboxylic acid. Examples of such polymers include metal salts of Group IA, Group IIA, Group IIB, Group IIIB (such as Li, Na, K, Mg, Ca, Zn, Al, etc.) of ethylene and radical polymerizable carboxylic acid. Those having a structure obtained by copolymerization; those having a structure obtained by multi-polymerizing ethylene and a metal salt of a radically polymerizable carboxylic acid and other radically polymerizable carboxylic acids and/or derivatives thereof Moreover, the said tertiary amines, for example, dimethylaniline, triethanolamine, dimethyl-p-toluidine, etc. are mentioned. In addition, examples of the aforementioned hydrazine compound include 1-acetyl-2-phenylhydrazine. In addition, as the aforementioned metal chelate compound, for example, vanadium acetoacetone can be exemplified. In addition, examples of the aforementioned phosphorus-containing compounds include dimethylphosphine and triphenylphosphine. In addition, examples of the aforementioned alkaline vulcanizing agents include hexamethylenetetramine, n-butylaldehyde-aniline condensate, and the like.

The adhesive composition of the present invention, within the range that does not impair the performance of the present invention, in addition to blending the aforementioned crystalline acid-modified polyolefin (A), glycidamine-type epoxy resin (B1), and chelate modification In addition to the epoxy resin (B2) and the organic solvent (C), various additives can be blended and used. The additives are not particularly limited, and flame retardants, pigments, anti-blocking agents, etc. are preferably used.

<Laminate> The laminate of the present invention is obtained by laminating a polyolefin resin base material and a metal base material using the adhesive composition of the present invention.

The lamination method can utilize conventionally known lamination manufacturing techniques. For example, the adhesive composition can be applied and dried on the surface of the metal substrate using a suitable coating tool such as a roll coater or a coating bar. 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 laminated structure, which is not particularly limited. The thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5-10 μm, more preferably 0.8-9.5 μm, and particularly preferably 1-9 μm.

<Polyolefin resin substrate> The polyolefin resin substrate may be appropriately selected from conventionally known polyolefin resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, etc. can be used, and it is not particularly limited. Among them, it is preferable to use a non-stretched polypropylene film (hereinafter, also referred to as CPP). The thickness is not particularly limited, but is preferably 20-100 μm, more preferably 25-95 μm, and particularly preferably 30-90 μm. In addition, pigments and various additives may be blended with the polyolefin resin base material as needed.

<Metal base material> The metal base material is not particularly limited. For example, various metals such as aluminum, copper, iron steel, zinc, duralumin, and die cast, and alloys thereof can be used. In addition, the shape can be any shape such as metal foil, rolled steel plate, flat plate, tube, can, lid, etc. Generally speaking, from the viewpoint of workability and the like, aluminum foil is more preferable. In addition, it varies depending on the purpose of use, but it is generally used in the form of a sheet with a thickness of 0.01-10 mm, preferably 0.02-5 mm. In addition, the surfaces of the metal substrates may be surface-treated in advance, or may be untreated. In either case, the same effect can be exerted. [Example]

Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited to the examples. In the examples and comparative examples, simply describing "parts" means parts by mass.

<Production example of crystalline acid-modified polyolefin (A)> [Production example 1] A propylene-butene copolymer (manufactured by Mitsui Chemicals Corporation "Tafmer (registered trademark) XM7080") was added to a 1L autoclave After 100 parts by mass, 150 parts by mass of toluene, 25 parts by mass of maleic anhydride, and 6 parts by mass of di-tert-butyl peroxide were raised to 140° C., they were further stirred for 3 hours. After that, the obtained reaction liquid was cooled, and then poured into a container containing a large amount of methyl ethyl ketone to precipitate the resin. Afterwards, the liquid containing the resin is centrifuged to separate and purify the acid-modified propylene-butene copolymer of graft-polymerized maleic anhydride, (poly)maleic anhydride and low molecular weight products. After that, it was dried at 70°C for 5 hours under reduced pressure to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, acid value 48mgKOH/g-resin, weight average molecular weight 50,000, Tm75°C, △H25J /g).

[Production Example 2] Except that the feed amount of maleic anhydride was changed to 20 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a maleic anhydride-modified propylene-butene copolymer (PO-2, acid value 25 mgKOH /g-resin, weight average molecular weight 80,000, Tm75°C, △H30J/g).

[Production Example 3] Except that the feed amount of maleic anhydride was changed to 3 parts by mass and the di-tert-butyl peroxide was changed to 0.5 parts by mass, the same procedure as in Production Example 1 was carried out to obtain maleic anhydride modification Propylene-butene copolymer (PO-3, acid value 5mgKOH/g-resin, weight average molecular weight 180,000, Tm80°C, △H25J/g).

[Production Example 4] Except that the feed amount of maleic anhydride was changed to 30 parts by mass, the same procedure as in Production Example 1 was performed to obtain a maleic anhydride-modified propylene-butene copolymer (PO-4, acid value 55 mgKOH /g-resin, weight average molecular weight 40,000, Tm70°C, △H25J/g).

[Production Example 5] Except that the feed amount of maleic anhydride was changed to 2 parts by mass and the di-tert-butyl peroxide was changed to 0.5 parts by mass, the same procedure as in Production Example 1 was carried out to obtain maleic anhydride modification Propylene-butene copolymer (PO-5, acid value 3mgKOH/g-resin, weight average molecular weight 200,000, Tm80°C, △H25J/g).

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

(Preparation of main ingredients 2 to 12) The crystalline acid-modified polyolefin and organic solvent were changed as shown in Table 1, and the main ingredients 2 to 12 were produced in the same manner as in the main ingredient 1. The blending amount and solution state are shown in Table 1.

【Table 1】

[Example 1] ADEKA RESIN (registered trademark) EP-49-10P (registered trademark) EP-49-10P, 0.2 parts by mass of ADEKA RESIN (registered trademark) EP-49-10P of the main agent 1, 2 parts by mass as the hardener It is blended with TETRAD (registered trademark)-X of epoxy propylene amine type epoxy resin (B1) to obtain an adhesive composition. The evaluation results of pot life performance, adhesiveness and chemical resistance are shown in Table 2.

[Examples 2 to 21, Comparative Examples 1 to 7] The main agents 1 to 12 and each curing agent were changed as shown in Tables 2 and 3, and the examples 2 to 21 and comparison were performed in the same manner as in Example 1. Examples 1-7. The blending amount, pot life performance, adhesiveness and chemical resistance are shown in Tables 2 and 3.

1) N,N,N’,N’-四環氧丙基-間二甲苯二胺 2) 苯酚酚醛清漆型環氧樹脂【Table 2】

1) N,N,N',N'-tetraepoxypropyl-m-xylenediamine 2) Phenolic novolac type epoxy resin

*因凝膠化而無法測定25℃溶液黏度。 **浸漬時CPP與鋁箔發生剝離而無法進行T型剝離試驗。【table 3】

*The solution viscosity at 25°C cannot be measured due to gelation. **During immersion, the CPP and aluminum foil peeled off and the T-type peel test could not be performed.

The hardeners used in Tables 2 and 3 are as follows. <Glycidamine type epoxy resin (B1)> N,N,N',N'-tetraepoxypropyl-m-xylenediamine: TETRAD (registered trademark)-X (manufactured by Mitsubishi Gas Chemical Corporation) <chelate Compound 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 (DSM Coating) Resins Co., Ltd.) <Glycidyl ether type epoxy resin> Phenolic novolac type epoxy resin: jER (registered trademark) 152 (Mitsubishi Chemical Corporation) <Other hardeners> Polyisocyanate: DURANATE (registered trademark) TPA-100 (Manufactured by Asahi Kasei Co., Ltd.) Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)

According to the following methods, the crystalline acid-modified polyolefin, the main agent and the adhesive composition obtained in the above manner were analyzed, measured and evaluated. [Measurement of acid value] 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) , Measured in accordance with the test method of JIS K0070 (1992). Specifically, 1 g of acid-modified polyolefin was dissolved in 100 g of xylene whose temperature was adjusted to 100°C, and then, at the same temperature, using phenol peptide as an indicator, a 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.] for titration. At this time, the amount of potassium hydroxide required for titration is 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 uses a gel permeation chromatograph Alliance e2695 manufactured by Japan Waters Corporation (hereinafter referred to as 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: value measured by photodiode array detector (wavelength 254nm = ultraviolet).

[Measurement of melting point and heat of fusion] The melting point and heat of fusion in the present invention are melted by using a differential scanning calorimeter (hereinafter referred to as DSC, manufactured by TA Instrument Japan, Q-2000) at a rate of 20°C/min. The value measured at the top temperature and area of the melting peak when the resin is cooled and heated again to melt.

[Evaluation of the solution state of the main agent] For the solution state of the main agent 1 to 12, the Brookfield viscometer TVB-10M (hereinafter, also referred to as type B viscometer) manufactured by Toki Sangyo Co., Ltd. was used to measure the viscosity of the solution at 25°C. For evaluation. <Evaluation criteria> ○ (excellent for practical use): less than 500mPa･s △(practical): 500mPa･s or more and less than 1000mPa･s × (not practical): 1000mPa･s or more or the viscosity cannot be measured due to gelation

[Evaluation of pot life performance] Pot life performance refers to the stability of the solution when the crystalline acid-modified polyolefin is blended with a crosslinking agent or hardener immediately after blending or after a certain period of time after blending. When the pot life performance is good, it means that the viscosity of the solution rises little and can be stored for a long time; when the pot life performance is poor, it means that the viscosity of the solution rises (viscosity). In severe cases, gelation occurs and it is difficult to apply to the substrate. Cannot be saved for a long period of time. The pot life performance of the adhesive composition obtained in Examples 1-21 and Comparative Examples 1-7 was evaluated by measuring the viscosity of the solution at 25°C using a B-type viscometer after storage at 25°C and 40°C for 24 hours . The evaluation results are shown in Tables 2 and 3. <Evaluation criteria> ○ (excellent for practical use): less than 500mPa･s △(practical): 500mPa･s or more and less than 1000mPa･s × (not practical): 1000mPa･s or more or the viscosity cannot be measured due to gelation

[Production of a laminate of a metal substrate and a polyolefin resin substrate] The metal substrate uses aluminum foil (manufactured by Sumiki Aluminum Foil Co., Ltd., 8079-0, thickness 40μm), and the polyolefin resin substrate uses a non-stretched polypropylene film (Toyobo Pylen (registered trademark) film CT manufactured by the company, thickness 40 μm) (hereinafter, also referred to as CPP). The adhesive compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 7 were coated on a metal substrate using a coating bar, and adjusted so that the film thickness of the adhesive layer after drying became 3 μm. Use a warm air dryer to dry the coated surface at 100°C for 1 minute to obtain an adhesive layer with a thickness of 3 μm. The polyolefin resin substrate was superimposed on the surface of the aforementioned adhesive layer, and a small desktop test laminator (Test Laminator, SA-1010-S) manufactured by TESTER SANGYO was used to paste at 80°C, 0.3MPa, and 1m/min. Together, they were aged at 40°C and 50% RH for 120 hours to obtain a laminate.

The laminate obtained in the above manner was evaluated by the following method.

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

<T-type peel test> According to the test method of ASTM-D1876-61, Tensilon RTM-100 manufactured by Orientic Coporation was used, and the peel strength at a tensile speed of 50 mm/min was measured in an environment of 25°C. The peel strength (N/cm) between the metal substrate and the polyolefin resin substrate is the average value of 5 test values.

<Evaluation Criteria> ☆ (Extremely excellent for practical use): 8.0 N/cm or more or material failure of CPP occurs (hereinafter, also referred to as "material failure"). Material failure means that no peeling occurs at the metal substrate/CPP interface , But the metal substrate or CPP damage. ◎(Especially excellent for practical use): 7.5N/cm or more and less than 8.0N/cm ○(excellent for practical use): less than 7.5N/cm or more than 7.0N/cm △(practicable): less than 6.0N/cm or more 7.0N/cm × (not practical): less than 6.0N/cm

[Evaluation of chemical resistance] In order to investigate the usability of a packaging material for lithium-ion batteries, which is one of the use forms of a laminate of aluminum foil and CPP, chemical resistance was performed by an electrolyte test (hereinafter, also referred to as electrolyte resistance) Sex) evaluation. Cut the aforementioned laminate into a size of 100mm×15mm, and add lithium hexafluoride phosphate to the electrolyte [ethylene carbonate/diethyl carbonate/dimethyl carbonate=1/1/1 (volume ratio)] Soak in 85°C for 1 day. After that, the laminate was taken out and washed with ion-exchanged water. The water was wiped off with a paper wiper to fully dry the water and cut into a size of 100mm×15mm. The T-type peel test was used to evaluate the chemical resistance .

<Evaluation criteria> ☆ (extremely excellent in practical use): 8.0N/cm or more or material broken ◎ (especially excellent in practical use): 7.5N/cm or more and less than 8.0N/cm ○ (excellent in practical use): 7.0N/cm The above is less than 7.5N/cm △(practical): 6.0N/cm and above, less than 7.0N/cm × (not practical): less than 6.0N/cm [Industrial applicability]

The adhesive composition of the present invention contains crystalline acid-modified polyolefin, epoxy resin and organic solvent, and will not increase viscosity or gelation even if stored for a long time, can maintain good pot life performance, and can be compatible with metal Good adhesion between substrate and polyolefin resin substrate. Therefore, the laminated structure of the polyolefin resin base material and the metal base material formed by the adhesive composition of the present invention can be used not only in the fields of home appliance outer panels, furniture materials, building interior components, etc., but also widely used Used as packaging material (pouch form) for lithium batteries used in personal computers, mobile phones, video cameras, etc.

no

Claims (7)

An adhesive composition containing: crystalline acid-modified polyolefin (A) with an acid value of 5-50 mgKOH/g-resin, glycidyl amine type epoxy resin (B1), and chelate-modified epoxy resin ( B2) and an organic solvent (C), the glycidyl amine type epoxy resin (B1) is a compound represented by the following general formula (1), and the blending amount of the glycidyl amine type epoxy resin (B1) is relative to the 100 parts by mass of the crystalline acid-modified polyolefin (A) is 0.01 parts by mass or more and 20 parts by mass or less, and the blending amount of the chelate-modified epoxy resin (B2) is relative to the crystalline acid-modified polyolefin 100 parts by mass of the olefin (A) is 1 part by mass or more and 20 parts by mass or less, the organic solvent (C) is 80 parts by mass or more with respect to 100 parts by mass of the crystalline acid-modified polyolefin (A),

In the general formula (1), R is an aryl group that may also have substituents, X1 and X2 are each independently an alkylene group with 1 to 5 carbon atoms that may also have substituents, m is 1 or 2, and n is 1. Or 2. For example, the adhesive composition of item 1 in the scope of patent application, wherein the glycidyl amine type epoxy resin (B1) is an epoxy resin having two or more glycidyl groups in one molecule. For example, the adhesive composition of item 1 or 2 of the scope of patent application, wherein the chelate modified epoxy resin (B2), It is an epoxy resin having two or more glycidyl groups in one molecule, and one or more functional groups that do not contain nitrogen atoms but have a chelating effect. Such as the adhesive composition of item 1 or 2 of the scope of patent application, which contains 1000 parts by mass or less of the organic solvent (C) relative to 100 parts by mass of the crystalline acid-modified polyolefin (A). For example, the adhesive composition of item 1 or 2 of the scope of patent application, wherein the organic solvent (C) is a mixture of solvent (C1) and solvent (C2), and solvent (C1) is selected from aromatic hydrocarbons, One or more solvents in the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons. The solvent (C2) is selected from the group consisting of alcohol-based solvents, ketone-based solvents, ester-based solvents, and glycol ether-based solvents One or more solvents in the group, solvent (C1)/solvent (C2)=50~97/50~3 (mass ratio). For example, the adhesive composition of item 1 or 2 of the scope of patent application is used for the adhesion of polyolefin resin substrate and metal substrate. A laminate of a polyolefin resin substrate and a metal substrate is adhered by the adhesive composition of any one of items 1 to 6 in the scope of the patent application.