JP6757832B2 - Adhesive resin composition and adhesive - Google Patents

Description

The present invention comprises an adhesive and a method for producing an adhesive having excellent adhesiveness to various adherends, particularly metals, an adhesive resin composition that can be used as the adhesive material, and the adhesive. The present invention relates to an adhesive laminate having an adhesive layer and an adhesive laminate.

Conventionally, a hot melt adhesive having an acid-modified polyolefin resin has been known as a material for adhering to an adherend such as a metal.
For example, Patent Document 1 describes an adhesive resin composition for a polyolefin multilayer film, which contains a dibasic carboxylic acid anhydride-modified polyolefin resin having a weight average molecular weight of 1500 to 150,000 and a solid acid value of 100 to 300. Is disclosed.

Japanese Unexamined Patent Publication No. 2012-1661

Patent Document 1 states that good adhesiveness to organic / inorganic materials such as resins and metals can be obtained by using the composition. Certainly, when an adhesive resin composition that requires only an acid-modified polyolefin resin as described in Patent Document 1 is used, the adhesion between the adhesive layer made of the adhesive resin composition and the adherend is good. That is possible depending on the conditions. However, when the metal adherends are laminated via the adhesive layer, there is a problem that the durability is inferior.
Therefore, in the prior art, an adhesive resin composition having excellent adhesiveness and durability to various adherends such as metal, glass, and plastic has not been known.

The present invention has been made in view of the above situation, and is an adhesive resin composition and an adhesive having excellent adhesive strength and durability with respect to various adherends such as metal, glass and plastic. It is an object of the present invention to provide a manufacturing method, an adhesive, an adhesive laminate, and a laminate.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is 0 to 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0 to 0. It is an adhesive resin composition characterized by containing 1 to 20 parts by mass.
It is preferable to contain 90 to 99 parts by mass of the acid-modified polyolefin resin (A) and 1 to 10 parts by mass of the oxazoline group-containing styrene resin (B).
The oxazoline group-containing styrene resin (B) preferably has a melt flow rate of 5 to 10 g / 10 minutes as measured according to ASTM D1238 under the conditions of a temperature of 200 ° C. and a load of 5 kg.
The acid-modified polyolefin resin (A) is preferably maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C.
The adhesive resin composition according to any one of claims 1 to 4, wherein the adhesive resin composition is thermosetting by heating at 100 to 200 ° C.
A second aspect of the present invention is a method for producing an adhesive using an adhesive resin composition, in which the acid-modified polyolefin resin (A) and the oxazoline group-containing styrene resin (B) are melted. It is a method for producing an adhesive, which is characterized by kneading.
It is preferable that the melt-kneading is performed under heating at 240 to 300 ° C.
A third aspect of the present invention is an adhesive obtained by melt-kneading an adhesive resin composition.
A fourth aspect of the present invention is an adhesive laminate comprising a first adhesive layer, a base material layer, and a second adhesive layer in this order, wherein the first adhesive layer or the second adhesive layer is bonded. An adhesive laminate characterized in that either or both of the layers comprises the adhesive according to the third aspect of the present invention.
A fifth aspect of the present invention is an adhesive laminate comprising a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and a second adhesive layer in this order. , One or both of the first adhesive layer and the second adhesive layer is an adhesive laminate according to the third aspect of the present invention.
A sixth aspect of the present invention is a laminate comprising a first metal layer, the adhesive laminate, and a second metal layer in this order.

According to the present invention, an adhesive resin composition having excellent adhesiveness and durability to various adherends such as metal, glass, and plastic, a method for producing an adhesive, an adhesive, and an adhesive laminate. , And a laminate can be obtained.

Hereinafter, the present invention will be described based on preferred embodiments.

[Adhesive resin composition]
The adhesive resin composition according to the first aspect of the present invention comprises 80 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and an oxazoline group-containing styrene resin (B) having a number average molecular weight of 30,000 to 250,000. ) To 0.1 to 20 parts by mass.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “component (A)”, and the oxazoline group-containing styrene resin (B) may be referred to as “component (B)”.

(Acid-modified polyolefin resin (A))
In the present invention, the acid-modified polyolefin resin (A) is a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof, and an acid-functional group such as a carboxy group or an anhydrous carboxylic acid group is contained in the polyolefin-based resin. It has.
The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, copolymerizing an acid functional group-containing monomer with olefins, or the like. Among them, the component (A) is preferably obtained by acid-modifying a polyolefin resin.
Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.

Examples of the polyolefin-based resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or α-olefin, and a block copolymer of propylene and ethylene or α-olefin. Be done. Among them, homopolypropylene (propylene homopolymer; hereinafter, sometimes referred to as “homo PP”), propylene-ethylene block copolymer (hereinafter, sometimes referred to as “block PP”), propylene-ethylene. Polypropylene-based resins such as Random Copolymer (hereinafter, may be referred to as "Random PP") are preferable, and Random PP is particularly preferable.
Examples of the olefins in the case of copolymerization include olefin-based monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene and α-olefin.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxy group or a carboxylic acid anhydride group in the same molecule, and is an acid of various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acids. An anhydride is mentioned.
Examples of the acid functional group-containing monomer having a carboxy group (carboxy group-containing monomer) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, and endo. Examples thereof include α, β-unsaturated carboxylic acid monomers such as −bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of the acid functional group-containing monomer having a carboxylic acid anhydride group (carboxylic acid anhydride group-containing monomer) include unsaturated dicarboxylic acids such as maleic anhydride, nadicic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride. Anhydride monomer can be mentioned.
As these acid functional group-containing monomers, one type may be used alone in the component (A), or two or more types may be used in combination.

Among them, as the acid functional group-containing monomer, an acid functional group-containing monomer having an acid anhydride group is preferable, and a carboxylic acid anhydride group-containing monomer is more preferable, and anhydrous because of its high reactivity with the component (B) described later. Maleic anhydride is particularly preferred.
When a part of the acid functional group-containing monomer used for acid modification was unreacted, the unreacted acid functional group-containing monomer was removed in advance in order to prevent the adhesive strength from being lowered by the unreacted acid functional group-containing monomer. It is preferable to use the one as the component (A).

In the component (A), the component derived from the polyolefin resin or the olefins is preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A).

The melting point of the component (A) is preferably 100 ° C. to 180 ° C. in consideration of the temperature at which the component (A) and the component (B) described later are melt-kneaded. By using the component (A) having a melting point in the above range, the component (A) and the component (B) described later can be separated from the melting point of the component (A) even when a conventional method and a general device are used. Can be melt-kneaded at a sufficiently high temperature.

Among them, maleic anhydride-modified polypropylene is preferable as the component (A) from the viewpoint of adhesiveness and an appropriate melting point.

(Oxazoline group-containing styrene resin (B))
The component (B) is an oxazoline group-containing styrene resin having a number average molecular weight of 30,000 to 250,000. When the component (B) has an oxazoline group, the oxazoline group of the component (B) reacts with the acid functional group of the component (A) (for example, a carboxy group, a carboxylic acid group, etc.) to form a crosslinked structure. To. For example, when the acid functional group of the component (A) is a carboxy group, the following cross-linking reaction occurs to form an amide ester bond. As a result, it is considered that the strength of the resin is reinforced by this crosslinked structure, and good durability as well as excellent adhesiveness can be obtained.

Among them, as the component (B), a resin obtained by copolymerizing a styrene-based monomer and an oxazoline group-containing monomer is preferable.
As the styrene-based monomer, styrene and its derivatives can be used. Specifically, alkyl styrenes such as styrene, α-methyl styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; chloro. Examples thereof include halogenated styrene such as styrene, fluorostyrene, bromostyrene, dibromostyrene and iodostyrene. Of these, styrene is preferable.

The skeleton of the oxazoline group-containing monomer is not particularly limited as long as it is a monomer containing an oxazoline group and capable of copolymerizing with a styrene-based monomer, but a monomer having an oxazoline group and a vinyl group is preferable. Can be used.
Examples of the oxazoline group-containing vinyl monomer include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 4,4-Dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyloxymethyl-2,4-dimethyl-2-oxazoline, 4 − Methacryloyloxymethyl-2-phenyl-4-methyl-2-oxazoline, 2- (4-vinylphenyl) -4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxymethyl-2-isopropenyl- Examples thereof include 2-oxazoline and 4-ethyl-4-carboethoxymethyl-2-isopropenyl-2-oxazoline. Of these, 2-isopropenyl-2-oxazoline is preferable.

As the styrene-based monomer and the oxazoline group-containing monomer, one type may be used alone, or two or more types may be used in combination.
Further, the component (B) may contain one or more of other monomers in addition to the styrene-based monomer and the oxazoline group-containing monomer. The other monomers are not particularly limited as long as they can be copolymerized with these monomers, and examples thereof include (meth) acrylate monomers, (meth) acrylic ester monomers, and (meth) acrylamide monomers.
In the component (B), the composition ratio of each monomer is not particularly limited, but 5 to 50% by mass, more preferably 10 to 30% by mass of oxazoline with respect to all the monomers constituting the component (B). A resin obtained by copolymerizing a group-containing monomer is preferable. By using the oxazoline group-containing monomer within the above range, the component (A) and the component (B) can be sufficiently crosslinked to obtain good durability.

The number average molecular weight of the component (B) is 30,000 to 250,000, preferably 50,000 to 200,000, more preferably 60,000 to 100,000, and most preferably 60,000 to 80,000. By using the component (B) having a number average molecular weight within the above range, the compatibility between the component (A) and the component (B) is improved, and the component (A) and the component (B) are sufficiently crosslinked. Is possible.

As such the component (B), a commercially available product such as Epocross RPS-1005 (trade name) manufactured by Nippon Shokubai Co., Ltd. can be used.

In the adhesive resin composition of the present invention, the component (B) is contained in an amount of 0.1 to 20 parts by mass with respect to 80 to 99.9 parts by mass of the component (A). Among them, it is preferable that the component (B) is contained in an amount of 1 to 10 parts by mass with respect to 90 to 99 parts by mass of the component (A). The amount of the component (B) is preferably 1 to 5 parts by mass with respect to 95 to 99 parts by mass of the component (A).
The adhesive composition of the present invention can appropriately contain miscible additives, additional resins, plasticizers, stabilizers, colorants and the like, if desired.

[Adhesive manufacturing method]
The method for producing an adhesive according to the second aspect of the present invention is to melt-knead an acid-modified polyolefin resin (A) and an oxazoline group-containing styrene resin (B). The acid-modified polyolefin resin (A) and the oxazoline group-containing styrene resin (B) are the same as the components (A) and (B) of the first aspect described above, respectively. The adhesive resin composition containing the component (A) and the component (B) is melt-kneaded using a known device to react the component (A) and the component (B). Can be done.
As the melt-kneading device, a uniaxial extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heating roll kneader, or the like can be used. It is desirable to remove volatile components such as water to the outside of the device in advance, and if volatile components are generated during the reaction, discharge them to the outside of the device at any time by degassing or the like.
When the acid-modified polyolefin resin (A) has an acid anhydride group as an acid functional group, it is preferable because the reactivity with the oxazoline group of the component (B) is high and the reaction can be carried out under more mild conditions. ..

The heating temperature during melt-kneading is preferably selected from the range of 240 to 300 ° C. in that the components (A) and (B) are sufficiently melted and do not undergo thermal decomposition.
The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the adhesive resin composition in a molten state immediately after being extruded from the melt-kneading apparatus.

[adhesive]
The adhesive according to the third aspect of the present invention is obtained by melt-kneading the adhesive resin composition of the first aspect, and the method of melt-kneading is the same as that of the second aspect described above. is there. Since the adhesive of the present invention comprises the adhesive resin composition containing the component (A) and the component (B), various adherends such as metal, glass, and plastic are deteriorated over time. It can be adhered well in a state where environmental deterioration is suppressed.

[Adhesive laminate]
The adhesive laminate according to the fourth aspect of the present invention comprises a first adhesive layer, a base material layer, and a second adhesive layer in this order, and is a first adhesive layer or a second adhesive layer. Either one or both consist of the adhesive of the third aspect.
Further, the adhesive laminate according to the fifth aspect of the present invention includes a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and a second adhesive layer in this order. In the adhesive laminate, either or both of the first adhesive layer and the second adhesive layer comprises the adhesive of the third aspect.
The fourth and fifth adhesive laminates are laminates formed from the adhesive resin composition of the present invention and having a shape such as a film or a sheet, such as an adhesive resin film or an adhesive resin sheet. Can be used for many purposes.

At least one of the first and second adhesive layers in the fourth and fifth aspects is made of the adhesive of the third aspect, but both are made of the adhesive of the third aspect. Is preferable.

The base material layer in the fourth and fifth aspects is not particularly limited as long as it has sufficient mechanical strength, and is, for example, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or the like. Polyolefin resin; synthetic resin film made of polyolefin polymer such as cyclic olefin polymer (COP) and methylpentene polymer (TPX); metal layer; glass plate and the like can be used.
Among them, PEN, COP or TPX is preferable, and COP or TPX is particularly preferable because the coefficient of linear expansion is low and delamination is unlikely to occur even when an adherend such as metal is adhered using the adhesive laminate. preferable.
By using a resin having a low coefficient of linear expansion, the shrinkage of the laminate becomes small when the laminate is heated or cooled, and the strain of the laminate containing metal becomes small.
Further, a particulate or fibrous filler can be added to the base material layer as an additive. The filler may be any filler having high heat resistance, and examples thereof include organic fillers and inorganic fillers. By adding a filler, the shrinkage force of the hot-melt adhesive laminate can be further suppressed, and the strength of the hot-melt adhesive resin laminate itself can be increased. In the present invention, it is preferable to add an inorganic filler from the viewpoint of heat resistance and shrinkage of the base material layer. Inorganic fillers include carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, sulfates such as calcium sulfate, magnesium sulfate and barium sulfate, chlorides such as sodium chloride, calcium chloride and magnesium chloride, aluminum oxide and calcium oxide. Examples thereof include oxides such as magnesium oxide, zinc oxide, titanium oxide and silica, minerals such as talc, smectite, mica and kaolinite, carbon compounds such as carbon fibers and carbon particles, and fine particles made of glass. The shape may be spherical, rod-shaped, plate-shaped or the like, but a plate-shaped compound is preferable.

The first intermediate layer in the fifth aspect is a layer having adhesiveness to the base material layer and the first adhesive layer. The second intermediate layer is a layer having adhesiveness to the base material layer and the second adhesive layer.
The adhesiveness required for the first and second intermediate layers refers to the strength for maintaining the strength of the base material layer and the adhesive layer as a laminate, and if the adhesiveness is high, delamination is unlikely to occur. Become.
The material for forming the first and second intermediate layers is not particularly limited as long as the first and second intermediate layers have the above-mentioned adhesiveness, but is appropriately selected depending on the material for forming the base material layer. ..

When the material for forming the base material layer is a cyclic olefin polymer (COP), the material for forming the first and second intermediate layers is at least one selected from the group consisting of acid-modified polypropylene, metallocene-based polyethylene and metallocene-based polypropylene. It is preferably a seed. That is, as the material for forming the first and second intermediate layers, one selected from the group consisting of polypropylene, metallocene-based polyethylene, and metallocene-based polypropylene may be used alone, or two or more thereof may be used in combination. May be good.
For example, when the material for forming the first and second intermediate layers is composed of three components of acid-modified polypropylene, metallocene-based polyethylene, and metallocene-based polypropylene, when the total of these three components is 100 parts by mass, the metallocene-based polyethylene The compounding amount is preferably 30 parts by mass to 50 parts by mass, the compounding amount of metallocene polypropylene is preferably 30 parts by mass to 40 parts by mass, the compounding amount of acid-modified polypropylene is 20 parts by mass, and the compounding amount of metallocene polyethylene is 50 parts by mass. It is particularly preferable that the amount of the metallocene polypropylene compounded is 30 parts by mass. When the fifth aspect of the present invention, that is, the five-layer structure of the adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer is formed by using the intermediate layer, a film is formed at the same time by melt extrusion flow. It is preferable to form.

When the material for forming the base material layer is methylpentene polymer (TPX), the material for forming the first and second intermediate layers is at least one selected from the group consisting of methylpentene polymer, polybutene-based elastomer and polypropylene. It is preferable to have. That is, as the material for forming the first and second intermediate layers, one selected from the group consisting of methylpentene polymer, polybutene elastomer and polypropylene may be used alone, or two or more thereof may be used in combination. Good. As the methylpentene polymer, an acid-modified methylpentene polymer may be used.
For example, when the material for forming the first and second intermediate layers is composed of four components of a methylpentene polymer, an acid-modified methylpentene polymer, a polybutene-based elastomer, and polypropylene, when the total of these four components is 100 parts by mass. The amount of the methylpentene polymer compounded is 10 parts by mass to 70 parts by mass, more preferably 20 parts by mass to 50 parts by mass, and the amount of the acid-modified methylpentene polymer compounded is 0 parts to 50 parts by mass, more preferably 0 to 30 parts by mass. The amount of the polybutene-based elastomer compounded is 5 parts by mass to 40 parts by mass, more preferably 10 to 30 parts by mass, and the compounding amount of polypropylene is preferably 5 parts by mass to 40 parts by mass. When the fifth aspect of the present invention, that is, the five-layer structure of the adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer is formed by using the intermediate layer, a film is formed at the same time by melt extrusion flow. It is preferable to form.

The adhesive laminate may be, for example, a first adhesive layer, a base material layer and a second adhesive layer, or a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer and a second adhesive layer. The adhesive layer may be produced by coextruding using an extrusion molding machine; the first adhesive layer and the second adhesive layer, which are separately melt-deposited, are thermally laminated on both sides of the base material layer. May be (fourth aspect); the first and second intermediate layer materials are solution-coated on both sides of the substrate layer and then dried to form the first and second intermediate layers, which are then separately melted. It may be produced by thermally laminating the formed first adhesive layer and the second adhesive layer on the formed first and second intermediate layers (fifth embodiment).

When the intermediate layer is provided by coating in the fifth aspect, it is preferable that the intermediate layer is provided by using an olefin polymer. The olefin polymer is preferably polyethylene, polypropylene or polybutene, and is preferably acid-modified with a carboxylic acid such as maleic acid.

The thickness of each layer in the adhesive laminate is preferably 5 to 80 μm, more preferably 10 to 50 μm for the first and second adhesive layers. The base material layer is preferably 50 to 300 μm, more preferably 60 to 200 μm. The first and second intermediate layers are preferably 5 to 20 μm when manufactured by coextrusion, and preferably 0.5 to 5 μm when manufactured by solution coating.

[Laminate]
The laminate of the sixth aspect of the present invention comprises the first metal layer, the adhesive laminate of the fifth aspect, and the second metal layer in this order. Since the adhesive layer in the adhesive laminate is formed from the adhesive resin composition of the present invention, it is possible to obtain good adhesiveness and durability even when metals are adhered to each other. Since both sides of the adhesive laminate used for the sixth laminate are in contact with the metal layer, both the first and second adhesive layers are made of the adhesive resin composition (adhesive) of the present invention. Is preferable.
A generally known metal plate, metal flat plate, or metal foil can be used as the first metal layer and the second metal layer, which are adherends to be adhered using the laminate of the present invention. The metal used for these may be, for example, iron, copper, aluminum, lead, zinc, titanium, chromium, stainless steel which is an alloy, or the like. Further, a metal or non-metal surface-processed by plating with a metal or coating with a paint containing a metal may be used as the first or second metal layer. Particularly preferred is a metal flat plate or metal foil made of iron, aluminum, titanium, stainless steel, or a surface-treated metal, which can be used as the first metal layer and / or the second metal layer. , The adhesive layer of the present invention exhibits particularly strong adhesive force.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

[Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-6]
(Adhesive resin film)
The components (A) and (B) shown in Table 1 were melt-kneaded at 280 ° C. for 2 minutes and then molded into a film having a predetermined thickness by extrusion molding to obtain an adhesive sheet.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass). The following (B) -2 to (B) -5 were manufactured in accordance with the method described in Patent Publication No. 2980673.
(A) -1: Maleic anhydride-modified polypropylene (melting point 140 ° C.)
(A) -2: Polypropylene polymer (melting point 140 ° C)
(A) -3: Maleic anhydride-modified 1-butene-polypropylene copolymer (melting point 140 ° C., 1-butene: polypropylene = 50: 50 (mass ratio))
(B) -1: "Epocross RPS-1005" (trade name, manufactured by Nippon Catalyst Co., Ltd.) (resin obtained by copolymerizing styrene and 2-isopropenyl-2-oxazoline; number average molecular weight = 70,000)
(B) -2: Resin obtained by copolymerizing styrene and 2-isopropenyl-2-oxazoline (number average molecular weight = 50,000)
(B) -3: Resin obtained by copolymerizing styrene and 2-isopropenyl-2-oxazoline (number average molecular weight = 200,000)
(B) -4: Resin obtained by copolymerizing styrene and 2-isopropenyl-2-oxazoline (number average molecular weight = 20,000)
(B) -5: Resin obtained by copolymerizing styrene and 2-isopropenyl-2-oxazoline (number average molecular weight = 300,000)

(Adhesion evaluation)
Prepare an aluminum foil with a thickness of 300 μm and a length of 10 mm and a width of 30 mm, a stainless foil with a thickness of 300 μm and a length of 10 mm and a width of 30 mm, and an adhesive sheet piece obtained by cutting out the adhesive sheet of each example obtained above to a size of 10 mm × 10 mm. did.
After stacking the short side ends of the aluminum foil so that one end of the adhesive sheet piece is aligned, the short side ends of the stainless steel foil are further aligned with the other end of the adhesive sheet piece, and aluminum is interposed through the adhesive sheet piece. The foil and the stainless steel foil were placed so as to overlap each other. By laminating at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa, a laminated body having an adhesive area of 100 m ³ and a size of 10 mm in length × 50 mm in width in a plan view was obtained.
The aluminum foil and the end of the stainless steel foil of each of the obtained laminates are sandwiched between jigs, and a tensile shear test is performed using a tensile shear tester under the conditions of speed = 10 mm / min and distance between chucks = 20 mm. went.
Evaluation was performed based on the following evaluation criteria. The results are also shown in Table 1 as "adhesiveness".
A: The shearing force was 320 N or more.
B: The shearing force was 250 N or more and less than 320 N.
C: The shear force was 200 N or more and less than 250 N.
D: The shear force was less than 200 N.

(Durability evaluation)
The laminates of each example obtained in the same manner as in the above adhesiveness evaluation were immersed in hot water at 95 ° C. for 100 hours to perform a durability test. Tension shear using a tensile shear tester under the conditions of speed = 10 mm / min and distance between chucks = 20 mm by sandwiching the ends of the aluminum foil and stainless steel foil of the laminated body, which are the test samples after the durability test, with jigs. The test was conducted.
Evaluation was performed based on the following evaluation criteria. The results are also shown in Table 1 as "durability".
A: The shearing force was 250 N or more.
B: The shearing force was 200 N or more and less than 250 N.
C: The shearing force was 100 N or more and less than 200 N.
D: The shear force was less than 100 N.

From the results shown in Table 1, it can be seen that Examples 1-1 to 1-8 using the adhesive resin composition of the present invention have excellent durability as compared with Comparative Examples 1-1 to 1-6. It could be confirmed.

[Examples 2-1 to 2-4]
(Adhesion evaluation)
98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 are melt-kneaded at the temperatures shown in Table 2 for 2 minutes, and then molded into a film having a predetermined thickness by extrusion molding. Obtained an adhesive sheet.
Using the obtained adhesive sheet, a laminate was prepared in the same manner as in the above adhesiveness evaluation, and a tensile shear test was performed in the same manner as described above.
The results of the evaluation similar to the above evaluation criteria are also shown in Table 2.

From the results shown in Table 2, it was confirmed that the adhesive resin composition of the present invention had particularly excellent adhesiveness when melt-kneading was performed at 240 to 300 ° C.

[Examples 3-1 to 3-5]
In Examples 3-1 to 3-5, an adhesive resin composition having 98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 was used.

(Example 3-1)
The adhesive composition containing the components (A) and (B) is melt-kneaded at 280 ° C. for 2 minutes and then coextruded together with PEN to obtain "adhesive layer (thickness 42 μm) -PEN substrate (thickness 75 μm). An adhesive laminate having a three-layer structure of "-adhesive layer (thickness 42 μm)" was obtained.

(Example 3-2)
A dispersion solution of a maleic acid-modified propylene-butene copolymer was applied as a solution on both sides of a PEN substrate having a thickness of 75 μm so as to form an intermediate layer having a thickness of 2.0 μm, and dried.
Further, an adhesive composition having the components (A) and (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce two adhesive films (thickness 40 μm).
Next, the separately obtained adhesive film was placed on the intermediate layers provided on both sides of the PEN base material and heat-laminated at 170 ° C. to obtain "adhesive layer-intermediate layer-PEN base material-intermediate layer-adhesive". An adhesive laminate having a five-layer structure of "layers" was obtained.

(Example 3-3)
After melt-kneading the adhesive composition having the component (A) and the component (B) at 280 ° C. for 2 minutes, the COP as the base material and the metallocene-based polyethylene, the metallocene-based polypropylene, and the styrene-based thermoplastic elastomer as the intermediate layer are used. Coextruded together with the mixed polymer of the above, "Adhesive layer (thickness 27 μm) -Intermediate layer (thickness 15 μm) -COP base material (thickness 75 μm) -Intermediate layer (thickness 15 μm) -Adhesive layer (thickness 27 μm) ) ”” Was obtained.

(Example 3-4)
The adhesive composition containing the components (A) and (B) is melt-kneaded at 280 ° C. for 2 minutes, and then coextruded together with TPX as a base material and a mixed polymer of methylpentene polymer, polybutene and polypropylene as an intermediate layer. After molding, a five-layer structure of "adhesive layer (thickness 27 μm) -intermediate layer (thickness 15 μm) -TPX base material (thickness 75 μm) -intermediate layer (thickness 15 μm) -adhesive layer (thickness 27 μm)" An adhesive laminate made of was obtained.

(Example 3-5)
An adhesive composition containing the components (A) and (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce an adhesive film (thickness 159 μm).

(Evaluation of durability strength of laminated body)
An aluminum foil having a thickness of 300 μm and a length of 30 mm × a width of 30 mm is laminated with a three-layer or five-layer adhesive laminate or an adhesive film cut out to a size of 30 mm × 30 mm, and the thickness is 300 μm and the length is 30 mm. × The end of the stainless foil cut out to a width of 30 mm was placed, and the laminated body was formed by laminating at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa.
This laminate was immersed in hot water at 95 ° C. for 300 hours, and the state of the laminate after immersion was observed and evaluated. The results are shown in Table 3 as "laminate strength".
A: There was no visible peeling and no distortion of the laminate.
B: No visibly noticeable peeling was seen, and no major distortion was seen.
C: Some peeling or slight distortion of the laminated body was observed, but it was within the allowable range.
D: Peeling was seen on the entire surface, and the laminate was distorted.

From the results shown in Table 3, it can be confirmed that when the adhesive resin composition of the present invention is used and an intermediate layer is provided between the adhesive layer and the base sheet, the laminate has particularly excellent strength. It was.
In addition, the adhesiveness and durability of the bonded laminate were both good.

Claims (4)

90 to 99 parts by mass of the acid-modified polyolefin resin (A) and
It contains 1 to 10 parts by mass of an oxazoline group-containing styrene resin (B) having a number average molecular weight of 30,000 to 250,000.
The acid-modified polyolefin resin (A) is an adhesive resin composition characterized by being maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C. The oxazoline group-containing styrene resin (B) has a melt flow rate of 5 to 10 g / 10 minutes measured according to ASTM D1238 under the conditions of a temperature of 200 ° C. and a load of 5 kg, according to claim 1. Adhesive resin composition. The adhesive resin composition according to claim 1 or 2, wherein the adhesive resin composition is thermosetting by heating at 100 to 200 ° C. An adhesive obtained by melt-kneading the adhesive resin composition according to any one of claims 1 to 3.