JP6583997B2 - Adhesive manufacturing method, adhesive, adhesive laminate, and laminate - Google Patents

Description

The present invention, various adherends, in particular a method of manufacturing a glue and adhesives with excellent adhesion to metals, and to adhesive laminate and laminate with an adhesive layer made of the adhesive .

Conventionally, a hot melt adhesive having an acid-modified polyolefin resin is known as a material that adheres to an adherend such as metal.
For example, Patent Document 1 discloses an adhesive resin composition for polyolefin multilayer films containing a dibasic carboxylic acid anhydride-modified polyolefin resin having a weight average molecular weight of 15,000 to 150,000 and a solid content acid value of 100 to 300. Is disclosed.

JP 2012-1661 A

In patent document 1, it is supposed that favorable adhesiveness can be obtained with respect to organic and inorganic materials, such as resin and a metal, by using the said composition. When using an adhesive resin composition that requires only an acid-modified polyolefin resin as described in Patent Document 1, the adhesion between the adhesive layer composed of the adhesive resin composition and the adherend is improved. It is possible depending on conditions. However, when the metal adherend is laminated through the adhesive layer, there is a problem that the durability is poor.
Therefore, in the prior art, an adhesive resin composition having excellent adhesion 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-mentioned present situation, and for various adherends such as metal, glass, and plastic, a method for producing an adhesive having excellent adhesive strength and durability, an adhesive , An object is to provide an adhesive laminate and a laminate.

In order to solve the above problems, the present invention employs the following configuration.
That is, in the first aspect of the present invention, 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0. 0 of the oxazoline group-containing styrenic resin (B) having a number average molecular weight of 30,000 to 250,000. 1-20 mass parts, It is an adhesive resin composition characterized by the above-mentioned.
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 styrenic resin (B) preferably has a melt flow rate of 5 to 10 g / 10 minutes measured according to ASTM D1238 under 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 thermally cured 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, wherein the acid-modified polyolefin resin (A) and the oxazoline group-containing styrene resin (B) are melted. A method for producing an adhesive characterized by kneading.
The melt kneading is preferably 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 provided. Either or both of the layers are adhesive laminates comprising the adhesive described in 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 are made of the adhesive according to the third aspect of the present invention, and the adhesive laminate is characterized in that it is an adhesive laminate.
The sixth aspect of the present invention is a laminate comprising the first metal layer, the adhesive laminate, and the second metal layer in this order.

  ADVANTAGE OF THE INVENTION According to this invention, with respect to various adherends, such as a metal, glass, a plastic, the adhesive resin composition which has the outstanding adhesiveness and durability, the manufacturing method of an adhesive agent, an adhesive agent, and an adhesive laminated body And a laminated body 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 an 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. ) 0.1-20 parts by mass.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “(A) component”, and the oxazoline group-containing styrenic resin (B) may be referred to as “(B) component”.

(Acid-modified polyolefin resin (A))
In the present invention, the acid-modified polyolefin resin (A) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and an acid functional group such as a carboxy group or a carboxylic anhydride group in the polyolefin resin. It is what has.
The component (A) can be obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an acid functional group-containing monomer with an olefin. Especially, as (A) component, what was obtained by acid-modifying polyolefin resin is preferable.
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 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. It is done. Among these, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as “homo PP”), propylene-ethylene block copolymer (hereinafter sometimes referred to as “block PP”), propylene-ethylene. Polypropylene resins such as random copolymers (hereinafter sometimes referred to as “random PP”) are preferred, and random PP is particularly preferred.
Examples of the olefins for copolymerization include olefinic 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 anhydride group in the same molecule, and various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acid acids. Anhydrides are mentioned.
Acid functional group-containing monomers having carboxy groups (carboxy group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo -Α, β-unsaturated carboxylic acid monomers such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of acid functional group-containing monomers having carboxylic anhydride groups (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride An anhydride monomer is mentioned.
These acid functional group-containing monomers may be used alone or in combination of two or more in the component (A).

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

  (A) In a component, it is preferable that the component derived from polyolefin resin or olefins is 50 mass parts or more with respect to 100 mass parts of whole quantity of (A) component.

  The melting point of the component (A) is preferably 100 ° C. to 180 ° C. in consideration of the temperature when 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) to be described later can be obtained from the melting point of the component (A) even when a conventional method and a general apparatus are used. Can be melt-kneaded at a sufficiently high temperature.

  Among these, as the component (A), maleic anhydride-modified polypropylene is preferable from the viewpoints 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. The For example, when the acid functional group of the component (A) is a carboxy group, the following crosslinking reaction occurs and an amide ester bond is formed. As a result, it is considered that the strength of the resin is reinforced by this cross-linked structure, and excellent durability is obtained together with excellent adhesiveness.

Among these, the component (B) is preferably a resin obtained by copolymerizing a styrene monomer and an oxazoline group-containing monomer.
Styrene and its derivatives can be used as the styrene monomer. Specifically, alkyl styrene 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, octyl styrene; chloro; Examples thereof include halogenated styrene such as styrene, fluorostyrene, bromostyrene, dibromostyrene, and iodostyrene. Of these, styrene is preferable.

The oxazoline group-containing monomer is not particularly limited as long as it contains an oxazoline group and can be copolymerized with a styrenic monomer, but a monomer having an oxazoline group and a vinyl group is preferably used. 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- 2-oxazoline, 4-ethyl-4-carboethoxymethyl-2-isopropenyl-2- Kisazorin, and the like. Of these, 2-isopropenyl-2-oxazoline is preferable.

As the styrene monomer and the oxazoline group-containing monomer, one kind may be used alone, or two or more kinds may be used in combination.
In addition, the component (B) may contain one or more other monomers in addition to the styrene monomer and the oxazoline group-containing monomer. Other monomers are not particularly limited as long as they are copolymerizable with these monomers, and examples include (meth) acrylate monomers, (meth) acrylic ester monomers, (meth) acrylamide monomers, and the like.
In the component (B), the constituent ratio of each monomer is not particularly limited, but is 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total monomers constituting the component (B). A resin obtained by copolymerizing a group-containing monomer is preferred. By using the oxazoline group-containing monomer within the above range, the component (A) and the component (B) can be sufficiently cross-linked, and good durability can be obtained.

  The number average molecular weight of the component (B) is 3 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) can be sufficiently crosslinked. Is possible.

  As such component (B), commercially available products such as EPOCROS 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). Especially, it is preferable that (B) component is contained 1-10 mass parts with respect to (A) component 90-99 mass parts. Furthermore, Preferably (B) component is 1-5 mass parts with respect to (A) component 95-99 mass parts.
The adhesive composition of the present invention can appropriately contain miscible additives, additional resins, plasticizers, stabilizers, colorants and the like as desired.

[Method for producing adhesive]
The method for producing an adhesive according to the second aspect of the present invention involves melt-kneading 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 styrenic resin (B) are the same as the component (A) and the component (B) in the first aspect described above, respectively. (A) component and (B) component are made to react by melt-kneading the said adhesive resin composition containing the said (A) component and the said (B) component using a well-known apparatus. Can do.
As an apparatus for melt kneading, a single screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. It is desirable that volatile components such as moisture are removed from the apparatus in advance, and if volatile components are generated during the reaction, they are discharged out of the apparatus as needed 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 performed under milder conditions. .

The heating temperature at the time of melt kneading is preferably selected from the range of 240 to 300 ° C. in that the components (A) and (B) are sufficiently melted and are not thermally decomposed.
The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the molten adhesive resin composition immediately after being extruded from the melt kneader.

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

[Adhesive laminate]
The adhesive laminate according to the fourth aspect of the present invention includes a first adhesive layer, a base material layer, and a second adhesive layer in this order, and the first adhesive layer or the second adhesive layer. Either one or both are made of the adhesive of the third aspect.
Moreover, the adhesive laminated body of the 5th aspect of this invention is equipped with the 1st contact bonding layer, the 1st intermediate | middle layer, the base material layer, the 2nd intermediate | middle layer, and the 2nd contact bonding layer in this order. In the adhesive laminate, one or both of the first adhesive layer and the second adhesive layer are made of 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 have a shape such as a film or a sheet, and the adhesive resin film, the adhesive resin sheet, etc. 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 preferred.

The base material layer in the fourth and fifth embodiments is not particularly limited as long as it has sufficient mechanical strength. For example, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. Polyester resins of: synthetic resin films made of polyolefin polymers such as cyclic olefin polymers (COP) and methylpentene polymers (TPX); metal layers; glass plates and the like.
Among them, PEN, COP or TPX is preferable, and COP or TPX is particularly preferable because the linear expansion coefficient is low and it is difficult to cause delamination even when an adherend such as a metal is adhered using the adhesive laminate. preferable.
By using a resin having a low coefficient of linear expansion, when the laminated body is heated or cooled, the shrinkage of the laminated body is reduced, and the distortion of the laminated body containing metal is reduced.
In addition, a particulate or fibrous filler can be added to the base material layer as an additive. The filler should just be a filler with high heat resistance, and an organic filler and an inorganic filler are mentioned. By containing 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 shrinkability 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, 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 composed of glass. Further, examples of the shape include a spherical shape, a rod shape, and a plate shape, and a plate-like compound is preferable.

The 1st intermediate | middle layer in a 5th aspect is a layer which has adhesiveness with respect to a base material layer and a 1st contact bonding layer. The second intermediate layer is a layer having adhesion 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 as a laminate of the base material layer and the adhesive layer. When the adhesiveness is high, delamination hardly occurs. 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-described adhesiveness, but is appropriately selected according to 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 polyethylene, and metallocene polypropylene. Preferably it is a seed. That is, as a material for forming the first and second intermediate layers, one kind selected from the group consisting of polypropylene, metallocene polyethylene and metallocene polypropylene may be used alone, or two or more kinds may be used in combination. Also 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 blending amount is preferably 30 to 50 parts by weight, the blending amount of the metallocene polypropylene is preferably 30 to 40 parts by weight, the blending amount of the acid-modified polypropylene is 20 parts by weight, and the blending amount of the metallocene polyethylene is 50. It is particularly preferable that the blending amount of the mass part and the metallocene polypropylene is 30 parts by mass. When the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. Preferably formed.

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 elastomer and polypropylene. Preferably there is. That is, as a material for forming the first and second intermediate layers, one kind selected from the group consisting of methylpentene polymer, polybutene elastomer and polypropylene may be used alone, or two or more kinds may be used in combination. Good. An acid-modified methylpentene polymer may be used as the methylpentene polymer.
For example, when the material for forming the first and second intermediate layers is composed of four components of methylpentene polymer, acid-modified methylpentene polymer, polybutene elastomer and polypropylene, the total of these four components is 100 parts by mass. The amount of methyl pentene polymer is 10 to 70 parts by weight, more preferably 20 to 50 parts by weight, and the amount of acid-modified methyl pentene polymer is 0 to 50 parts by weight, more preferably 0 to 30 parts by weight. The blending amount of the part polybutene-based elastomer is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, and the blending amount of polypropylene is preferably 5 to 40 parts by weight. When the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. It is preferable to form.

  The adhesive laminate is, for example, the first adhesive layer, the base material layer, and the second adhesive layer, or the first adhesive layer, the first intermediate layer, the base material layer, the second intermediate layer, and the second adhesive layer. The adhesive layer may be manufactured by co-extrusion using an extrusion molding machine; manufactured by laminating the first adhesive layer and the second adhesive layer separately melt-formed on both sides of the base material layer (Fourth embodiment): First and second intermediate layer materials are applied on both sides of the substrate layer and then dried to form the first and second intermediate layers, and then separately melted. The first adhesive layer and the second adhesive layer thus formed may be manufactured by thermal lamination on the formed first and second intermediate layers (fifth aspect).

  In the fifth aspect, when the intermediate layer is provided by coating, the intermediate layer is preferably provided using an olefin-based 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 substrate 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, good adhesion and durability can be obtained even when metals are bonded together. Since the adhesive laminate used for the sixth laminate is 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 preferred.
As the first metal layer and the second metal layer, which are adherends to be bonded using the laminate of the present invention, a generally known metal plate, metal flat plate or metal foil can be used. Examples of the metal used for these include iron, copper, aluminum, lead, zinc, titanium, and chromium, and may also be stainless steel that is an alloy. Moreover, you may use the metal or nonmetal which carried out the surface processing process by the metal plating or the coating process by the coating material containing a metal as a 1st or 2nd metal layer. Particularly preferably, it is a metal flat plate or metal foil made of iron, aluminum, titanium, stainless steel, surface-treated metal, and these are used as the first metal layer and / or the second metal layer. The adhesive layer of the present invention exhibits a particularly strong adhesive force.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by 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 formed into a film having a predetermined thickness by extrusion to obtain an adhesive sheet.

In Table 1, each abbreviation has the following meaning. The numerical value in [] is a compounding amount (part by mass). The following (B) -2 to (B) -5 were produced according to the method described in Japanese 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 Shokubai 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 300 mm thick, 10 mm long x 30 mm wide aluminum foil, 300 μm thick, 10 mm long x 30 mm wide stainless steel foil, and 10 mm x 10 mm adhesive sheet pieces obtained by cutting each of the above obtained adhesive sheets. did.
After overlapping the short side edge part of the aluminum foil so that one end of the adhesive sheet piece is aligned, the short side edge part of the stainless steel foil is aligned to the other end of the adhesive sheet piece, and the aluminum is interposed via the adhesive sheet piece. It mounted so that foil and stainless steel foil might overlap. While applying a pressure of 0.5 MPa, the laminate was bonded at 150 ° C. for 5 seconds to obtain a laminate having an adhesive area of 100 m ³ and a size of 10 mm in length and 50 mm in width in plan view.
The ends of the aluminum foil and stainless steel foil of each of the obtained laminates were sandwiched with jigs, and a tensile shear test was 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: Shear force was 250N or more and less than 320N.
C: Shear force was 200N or more and less than 250N.
D: Shear force was less than 200N.

(Durability evaluation)
The laminated body of each example obtained similarly to the said adhesive evaluation was immersed in 95 degreeC hot water for 100 hours, and the durability test was done. The end of the aluminum foil and stainless steel foil of the laminate, which is a test sample after the durability test, was sandwiched between jigs, respectively, and tensile shear using a tensile shear tester under conditions of speed = 10 mm / min and chuck distance = 20 mm. A 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: Shear force was 200N or more and less than 250N.
C: Shear force was 100N or more and less than 200N.
D: Shear force was less than 100N.

  From the results shown in Table 1, Examples 1-1 to 1-8 using the adhesive resin composition of the present invention have superior durability compared to 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 were melt-kneaded for 2 minutes at the temperatures shown in Table 2, and then formed into a film having a predetermined thickness by extrusion. To obtain an adhesive sheet.
Using the obtained adhesive sheet, a laminate was produced in the same manner as in the above-described adhesion evaluation, and a tensile shear test was conducted in the same manner as described above.
The results of evaluation similar to the above evaluation criteria are also shown in Table 2.

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

[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 having the component (A) and the component (B) is melt-kneaded at 280 ° C. for 2 minutes, and then coextruded with PEN. “Adhesion 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 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.
Moreover, the adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce two adhesive films (thickness 40 μm).
Next, the adhesive film obtained separately was placed on the intermediate layer provided on both sides of the PEN base material and heat laminated at 170 ° C., and “adhesive layer-intermediate layer-PEN base material-intermediate layer-adhesion” was obtained. An adhesive laminate having a five-layer structure of “layer” 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, COP serving as a base material, metallocene polyethylene, metallocene polypropylene and styrene thermoplastic elastomer serving as an intermediate layer, And co-extrusion molding with a mixed polymer of “adhesive layer (thickness 27 μm) —intermediate layer (thickness 15 μm) —COP substrate (thickness 75 μm) —intermediate layer (thickness 15 μm) —adhesive layer (thickness 27 μm) ) ”Was obtained.

(Example 3-4)
After the adhesive composition having component (A) and component (B) is melt-kneaded at 280 ° C. for 2 minutes, it is coextruded 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 configuration of “adhesive layer (thickness 27 μm) —intermediate layer (thickness 15 μm) —TPX substrate (thickness 75 μm) —intermediate layer (thickness 15 μm) —adhesive layer (thickness 27 μm)” The adhesive laminated body which consists of was obtained.

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

(Evaluation of durability of laminates)
The aluminum foil having a thickness of 300 μm and a length of 30 mm × width of 30 mm is laminated with a three-layer or five-layer adhesive laminate or an adhesive film of each example cut into 30 mm × 30 mm, and the thickness is 300 μm and length is 30 mm. X The end of the stainless steel foil cut out to 30 mm in width was placed, and the laminate was laminated at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa.
The laminate was immersed in 95 ° C. hot water 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 was observed.
B: Visible and conspicuous, no peeling was seen, and no major distortion was seen.
C: Some peeling or some distortion of the laminate was observed, but it was within the allowable range.
D: Peeling was observed 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, it has particularly excellent laminate strength. It was.
Moreover, both the adhesiveness and durability of the laminated body adhered were good.

Claims (6)

80 to 99.9 parts by mass of the acid-modified polyolefin resin (A);
A method for producing an adhesive using an adhesive resin composition containing 0.1 to 20 parts by mass of an oxazoline group-containing styrene resin (B) having a number average molecular weight of 30,000 to 250,000 ,
A method for producing an adhesive, comprising melt-kneading the acid-modified polyolefin resin (A) and the oxazoline group-containing styrene resin (B). The method for producing an adhesive according to claim 1 , wherein the melt kneading is performed under heating at 240 to 300 ° C. 80 to 99.9 parts by mass of the acid-modified polyolefin resin (A);
Adhesion characterized by being obtained by melt-kneading an adhesive resin composition containing 0.1 to 20 parts by mass of an oxazoline group-containing styrene resin (B) having a number average molecular weight of 30,000 to 250,000 Agent. An adhesive laminate comprising a first adhesive layer, a base material layer, and a second adhesive layer in this order,
Either one or both of said 1st contact bonding layer or 2nd contact bonding layer consists of the adhesive agent of Claim 3 , The adhesive laminated body characterized by the above-mentioned. 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,
Either one or both of said 1st contact bonding layer or 2nd contact bonding layer consists of the adhesive agent of Claim 3 , The adhesive laminated body characterized by the above-mentioned. A laminate comprising the first metal layer, the adhesive laminate according to claim 4 or 5 , and the second metal layer in this order.