JP2017036351A - Adhesive resin composition, method for producing adhesive, adhesive, adhesive laminate, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive resin composition having excellent adhesive strength and durability, a method for producing an adhesive, an adhesive, an adhesive laminate, and a laminate.SOLUTION: The adhesive resin composition contains: 80-99.9 pts.mass of an acid-modified polyolefin resin (A); and 0.1-20 pts.mass of an epoxy group-containing polyolefin resin (B) which has a main chain obtained by copolymerizing monomers including an olefin compound and an epoxy group-containing vinyl monomer, and a side chain bonded to the main chain and has a melting point of 80-120°C.SELECTED DRAWING: None

Description

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

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 situation, and is an adhesive resin composition and an adhesive having excellent adhesion and durability to various adherends such as metal, glass, and plastic. It aims at providing a manufacturing method, an adhesive agent, an adhesive laminated body, and a laminated body.

In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention is a main chain obtained by copolymerizing 80 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and a monomer containing an olefin compound and an epoxy group-containing vinyl monomer, And 0.1 to 20 parts by mass of an epoxy group-containing polyolefin resin (B) having a side chain bonded to the main chain and a melting point of 80 to 120 ° C. It is an adhesive resin composition.
It is preferable to contain 0.1 to 10 parts by mass of the epoxy group-containing polyolefin resin (B) with respect to 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A).
The side chain of the epoxy group-containing polyolefin resin (B) is preferably a polymer containing styrene.
The main chain of the epoxy group-containing polyolefin resin (B) is obtained by copolymerizing 10 to 30% by mass of the epoxy group-containing vinyl monomer with respect to all monomers constituting the main chain. Is preferred.
In the solid content of the adhesive resin composition, the ratio of the acid-modified polyolefin resin (A) is 95 to 99% by mass, and the ratio of the epoxy group-containing polyolefin resin (B) is 1 to 5% by mass. Is preferred.
The epoxy group-containing vinyl monomer is preferably glycidyl methacrylate.
The acid-modified polyolefin resin (A) is a maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C., and the melting point of the acid-modified polyolefin resin (A) is higher than the melting point of the epoxy group-containing polyolefin resin (B). Is preferably high.
A second aspect of the present invention is a method for producing an adhesive using the adhesive resin composition, comprising the acid-modified polyolefin resin (A) and the epoxy group-containing polyolefin resin (B). An adhesive manufacturing method characterized by melt-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 of the first aspect of the present invention is a main chain obtained by copolymerizing 80 to 99.9 parts by mass of an acid-modified polyolefin resin (A), an olefin compound and an epoxy group-containing vinyl monomer. And 0.1 to 20 parts by mass of an epoxy group-containing polyolefin resin (B) having a side chain bonded to the main chain and a melting point of 80 to 120 ° C.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “(A) component”, and the epoxy group-containing polyolefin 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 and 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. In addition, when the component (A) is reacted with the component (B) described later using melt kneading, it is preferable that the melting point of the component (B) is lower than that of the component (A). By using the component (A), the degree of freedom in selecting the component (B) can be increased.

  Further, as described above, the melting point of the component (A) is preferably higher than the melting point of the component (B) described later, but the melting point of the component (A) is higher by 10 ° C. than the melting point of the component (B). More preferably, it is more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. When the melting point of the component (A) is sufficiently higher than that of the component (B), the component (B) is melted first when the melt kneading is performed, and the component (A) in the state where the shape of the resin is maintained. As a result of penetrating and reacting uniformly, good durability can be obtained.

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

(Epoxy group-containing polyolefin resin (B))
In the present invention, the epoxy group-containing polyolefin resin (B) has a main chain obtained by copolymerizing a monomer containing an olefin compound and an epoxy group-containing vinyl monomer, and a side chain bonded to the main chain, And melting | fusing point is 80-120 degreeC.

-Main chain The main chain of the component (B) is obtained by copolymerizing an olefin compound, an epoxy group-containing vinyl monomer, and other optional monomers used as necessary.
Examples of the olefin compound include olefin monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin.
Examples of the epoxy group-containing vinyl monomer include glycidyl esters such as glycidyl methacrylate (GMA) and glycidyl acrylate, glycidyl ethers such as allyl glycidyl ether, and epoxy alkenes such as epoxy butene.
As an olefin compound and an epoxy group-containing vinyl monomer, one kind may be used alone, or two or more kinds may be used in combination.

The main chain of the component (B) may contain one or more other monomers in addition to the olefin compound and the epoxy group-containing vinyl monomer. Other monomers are not particularly limited as long as they are copolymerizable with olefin compounds and epoxy group-containing vinyl monomers. For example, (meth) acrylate monomers, (meth) acrylic ester monomers, (meth) acrylamide monomers And styrene monomer.
In the copolymer serving as the main chain of the component (B), the constituent ratio of each monomer (compound) is not particularly limited, but is 10 to 10% with respect to all monomers constituting the main chain of the component (B). A copolymer obtained by copolymerizing 30% by mass, more preferably 10 to 20% by mass of an epoxy group-containing vinyl monomer is preferred. By using an epoxy group-containing vinyl monomer within the above range, it is possible to suitably improve the adhesion to the adherend.

  Among these, as the main chain of the component (B), a copolymer obtained by copolymerizing an olefin compound and an epoxy group-containing vinyl monomer is preferable, and a copolymer of ethylene and glycidyl methacrylate is particularly preferable.

-Side chain (B) component can improve the characteristics, such as intensity | strength, adhesiveness, a synthesis | combination, of an olefin type copolymer, by having the side chain couple | bonded with the said principal chain. The side chain is not particularly limited. Styrenic resin (polymer containing styrene) such as polystyrene and styrene-acrylonitrile copolymer; (meth) methyl acrylate, (meth) ethyl acrylate, (meth) Examples thereof include (meth) acrylic resins obtained by polymerizing one or more alkyl (meth) acrylate monomers such as butyl acrylate and pentyl (meth) acrylate.
Especially, as a side chain of (B) component, the polymer containing styrene is preferable, for example, a polystyrene and a styrene-acrylonitrile copolymer are mentioned. Of these, polystyrene is particularly preferable.
When the component (B) is a polymer containing polystyrene as a side chain, fluidity in a molten state is improved. For this reason, it has an appropriate fluidity at the time of heat-bonding, and the epoxy group is likely to come into contact with the adherend, so that the adhesive strength and durability are improved.

The component (B) having the main chain and the side chain as described above includes, for example, a main chain copolymer obtained by a conventional method, a monomer constituting the side chain, an organic peroxide, an aliphatic azo compound, and the like. Can be obtained by graft polymerization using a radical polymerization initiator.
(B) Melting | fusing point of a component is 80-120 degreeC, and it is preferable that it is 90-110 degreeC. (B) component which has such melting | fusing point can be obtained by selecting suitably the monomer seed | species which comprises a principal chain and a side chain.
By using the component (B) having a melting point in the above range, the component (A) and the component (A) can be used at a temperature sufficiently higher than the melting point of the component (B) even when using a conventional method and a general apparatus. The component (B) can be melt-kneaded, and an adhesive or adhesive layer having excellent durability can be obtained. Moreover, when making said (A) component and (B) component react using melt-kneading, it is preferable that melting | fusing point of (B) component is low compared with (A) component, but it has melting | fusing point of the said range. By using the component (B), the degree of freedom in selecting the component (A) can be increased.

  As such component (B), commercially available products such as MODIPER A1100, A4100, and A4400 (all trade names) manufactured by NOF Corporation may be used.

In the adhesive resin composition of the present invention, both the acid functional group of the component (A) and the epoxy group of the component (B) are bonded to an adherend (particularly a functional group such as a hydroxyl group possessed by the adherend). By functioning as a functional functional group, it is considered that excellent adhesion to various adherends such as metal, glass, and plastic can be achieved.
In addition, a part of the acid functional group of the component (A) and a part of the epoxy group of the component (B) react to form a crosslinked structure of the component (A) and the component (B). It is considered that the strength of the resin is reinforced and good durability is obtained together with excellent adhesiveness.

  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 0.1-10 mass parts of (B) component is contained with respect to 90-99.9 mass parts of (A) component. More specifically, in the solid content of the adhesive resin composition of the present invention, the ratio of the component (A) is preferably 95 to 99% by mass, and the ratio of the component (B) is 1 to 5% by mass. Preferably there is.

  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 manufacturing method of the adhesive which is the 2nd aspect of this invention melt-kneads acid-modified polyolefin resin (A) and epoxy-group-containing polyolefin resin (B). The acid-modified polyolefin resin (A) and the epoxy group-containing polyolefin resin (B) are respectively the same as the component (A) and the component (B) in the first aspect described above. (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. In order to suppress the decomposition of the epoxy group of the component (B) during the reaction of the component (A) and the component (B), the volatile component that can react with the epoxy group such as moisture is previously removed from the apparatus, In addition, when a volatile component is generated during the reaction, it is desirable to discharge it from 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, the reactivity with the epoxy group of the component (B) is high, and the reaction can be performed under milder conditions. preferable.

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 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 layer is a cyclic olefin polymer (COP), the intermediate layer is selected from the group consisting of the first and second intermediate layers from acid-modified polypropylene, metallocene-based polyethylene, and metallocene-based polypropylene. It is preferable that it is at least one kind. 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. 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 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. Part, the blending amount of the polybutene 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, and more preferably 10 to 30 parts by weight. The part by mass is particularly preferred. 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 according to the sixth aspect of the present invention comprises the first metal layer, the adhesive laminate according to the fourth or 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 1-5]
(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 100 μm film 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 was produced according to the method described in JP-A-2002-201331.
(A) -1: Maleic anhydride-modified polypropylene (melting point: 140 ° C.)
(A) -2: Maleic anhydride-modified polyethylene-polypropylene copolymer (melting point 160 ° C., polyethylene: polypropylene = 50: 50 (mass ratio))
(A) -3: Maleic anhydride modified 1-butene-polypropylene copolymer (melting point 150 ° C., 1-butene: polypropylene = 50: 50 (mass ratio))
(B) -1: “Modiper A4100” (trade name, manufactured by NOF CORPORATION) (graft polymer of ethylene-glycidyl methacrylate copolymer and polystyrene; ratio of glycidyl methacrylate monomer to all monomers in the main chain = 30% by mass; melting point 97 ° C.)
(B) -2: Graft polymer of ethylene-glycidyl methacrylate copolymer and polystyrene (ratio of glycidyl methacrylate monomer to all monomers in main chain = 50 mass%; melting point 97 ° C.)
(B) -3: “Modiper A4400” (trade name, manufactured by NOF Corporation) (graft polymer of ethylene-glycidyl methacrylate copolymer and styrene-acrylonitrile copolymer; glycidyl for all monomers in the main chain) Ratio of methacrylate monomer = 30% by mass; melting point: 100 ° C.
(B) -4: “Modiper A4300” (trade name, manufactured by NOF Corporation) (graft polymer of ethylene-glycidyl methacrylate copolymer and butyl acrylate-methyl methacrylate copolymer; in the main chain Ratio of glycidyl methacrylate monomer to total monomer = 30% by mass; melting point 98 ° C.)
(B) -5: ethylene-glycidyl methacrylate copolymer (ratio of glycidyl methacrylate monomer to all monomers in the copolymer = 30% by mass; melting point 80 ° C.)
(B) -6: “Modiper A3400” (trade name, manufactured by NOF Corporation) (graft polymer of polypropylene polymer and styrene-acrylonitrile copolymer; melting point 165 ° C.)

(Durability 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 obtained laminated body of each example was immersed in hot water of 95 ° C. for 100 hours and subjected to a durability test. 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 1-5. It could be confirmed.

[Examples 2-1 to 2-4]
(Adhesive strength 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.
Next, an aluminum sheet having a thickness of 300 μm and a length of 10 mm × width of 30 mm, a thickness of 300 μm, a stainless steel foil of length 10 mm × width 30 mm, and an adhesive sheet piece obtained by cutting the adhesive sheet of each example obtained above to 10 mm × 10 mm Prepared.
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 2 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.

  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, The co-extrusion molding was performed together with a mixed polymer of “adhesive layer (thickness 20 μm) —intermediate layer (thickness 15 μm) —COP substrate (thickness 75 μm) —intermediate layer (thickness 15 μm) —adhesive layer (thickness 20 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)
300 μm thick, 30 mm long × 30 mm wide aluminum foil, 300 μm thick, 30 mm long × 30 mm wide stainless steel foil, and the above-obtained three-layer or five-layer adhesive laminate or adhesive film An adhesive sheet piece cut out 30 mm long × 30 mm wide was prepared.
After being stacked on the aluminum foil so that the end portions of the adhesive sheet pieces are aligned, the end portions of the stainless steel foil are aligned with the end portions of the adhesive sheet pieces, and the aluminum foil and the stainless steel foil are interposed via the adhesive sheet pieces. Were placed so as to overlap. A laminated body having an adhesion area of 900 m ³ was obtained by pasting together at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa.
This laminate was immersed in 95 ° C. hot water for 300 hours, and the state of the laminate after immersion was visually 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 (13)

80 to 99.9 parts by mass of the acid-modified polyolefin resin (A);
Epoxy group-containing polyolefin having a main chain obtained by copolymerizing a monomer containing an olefin compound and an epoxy group-containing vinyl monomer, and a side chain bonded to the main chain, and having a melting point of 80 to 120 ° C. An adhesive resin composition containing 0.1 to 20 parts by mass of the resin (B).   The adhesive resin according to claim 1, comprising 0.1 to 10 parts by mass of the epoxy group-containing polyolefin resin (B) with respect to 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A). Composition.   The adhesive resin composition of Claim 1 or 2 whose side chain which the said epoxy group containing polyolefin resin (B) has is a polymer containing styrene.   The main chain of the epoxy group-containing polyolefin resin (B) is obtained by copolymerizing 10 to 30% by mass of the epoxy group-containing vinyl monomer with respect to all monomers constituting the main chain. Item 4. The adhesive resin composition according to any one of Items 1 to 3.   In the solid content of the adhesive resin composition, the ratio of the acid-modified polyolefin resin (A) is 95 to 99% by mass, and the ratio of the epoxy group-containing polyolefin resin (B) is 1 to 5% by mass. Item 5. The adhesive resin composition according to any one of Items 1 to 4.   The adhesive resin composition according to any one of claims 1 to 5, wherein the epoxy group-containing vinyl monomer is glycidyl methacrylate. The acid-modified polyolefin resin (A) is a 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 6, wherein a melting point of the acid-modified polyolefin resin (A) is higher than a melting point of the epoxy group-containing polyolefin resin (B). A method for producing an adhesive using the adhesive resin composition according to any one of claims 1 to 7,
A method for producing an adhesive, comprising melt-kneading the acid-modified polyolefin resin (A) and the epoxy group-containing polyolefin resin (B).   The method for producing an adhesive according to claim 8, wherein the melt-kneading is performed under heating at 240 to 300 ° C.   An adhesive obtained by melt-kneading the adhesive resin composition according to any one of claims 1 to 7. 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 10, 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 10, The adhesive laminated body characterized by the above-mentioned.   A laminate comprising the first metal layer, the adhesive laminate according to claim 11 or 12, and the second metal layer in this order.