JP6919075B2 - Composite laminates and metal-polyolefin conjugates - Google Patents

Description

The present invention relates to a composite laminate of a metal material that can be bonded to polyolefin with high strength and a method for producing the same, and a metal-polyolefin conjugate using the composite laminate and a method for producing the same.

In the fields of automobile parts and OA equipment where weight reduction of products is required, there is an increasing demand for a metal-resin joint in which a metal material such as aluminum and a resin are joined and integrated. When aluminum is used as the metal material in these metal-resin joints, surface treatment is performed on the aluminum in order to secure sufficient joint strength between the metal and the resin.

As the surface treatment, studies are underway to perform physical methods such as blast treatment, chemical conversion treatment, and anodizing treatment, and chemical surface treatment.

When a polyolefin such as polypropylene is used as the resin in the metal-resin bonded body, since the polyolefin has no polarity, studies are underway to use an acid-modified polyolefin in order to improve the bondability with the metal.
For example, a method in which an adhesive layer containing a modified polypropylene resin having a polar group introduced is formed on a base treatment film provided on the surface of a base material made of an aluminum alloy, and bonded to polypropylene by compatibilization and anchor effect (patented). Documents 1 and 2), a method of forming an acid-modified polypropylene layer having a defined melt viscosity, melting point, crystallinity, etc. on an aluminum alloy (Patent Document 3), chromate phosphate, chromium for surface treatment of an aluminum alloy. A method of providing a modified polypropylene layer having a polar group using acid chromate, zirconium oxide, titanium zirconium, etc. (Patent Document 4), with an epoxy resin of 15 to 40 μm as the first layer on the surface of a metal chemical conversion treatment film. A method of forming a layer made of blocked isocyanate and providing an acid-modified polyolefin layer of 4 to 30 μm in the second layer is disclosed (Patent Document 5).

Japanese Unexamined Patent Publication No. 2016-16584 WO2016 / 199339 WO2016 / 152118 Japanese Patent No. 063766867 JP-A-2018-154834

However, in the above-mentioned conventional technique, there is a problem that the bonding strength of the metal-polyolefin bonded body remains at a predetermined level, and it is difficult to meet the demand for further improvement of the bonding strength and durability.
The present invention has been made in view of such a technical background, and an object of the present invention is to provide a composite laminate suitable for an application in which a metal and a polyolefin are firmly bonded, and a related technique thereof. The related technology means a method for producing the composite laminate, a metal-polyolefin conjugate using the composite laminate, and a method for producing the same.

The present invention provides the following means for achieving the above object.
In this specification, joining means connecting objects to each other, and adhesion is a subordinate concept thereof, and organic materials such as tapes and adhesives (thermosetting resins and thermoplastics). It means that the two adherends (those to be bonded) are put into a bonded state via a resin or the like.

[1] A composite laminate having a metal material and one or a plurality of resin coating layers laminated on the metal material, and at least one layer of the resin coating layer is a resin composition containing a modified polyolefin. It is a modified polyolefin layer formed of, and the modified polyolefin layer is a layer containing a reaction product 1 of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound, a maleic anhydride-modified polyolefin and a thermoplastic epoxy. A composite laminate that is at least one selected from the group consisting of a layer containing a reactant 2 with a resin and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin.
[2] The composite laminate according to [1], wherein the reaction product 1 is formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing maleic anhydride-modified polyolefin.
[3] The composite according to [1], wherein the reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. Laminated body.
[4] The composite laminate according to [1], wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin.
[5] The resin coating layer is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer other than the modified polyolefin layer is a resin containing a thermoplastic epoxy resin. Any of [1] to [4], which is at least one selected from a thermoplastic epoxy resin layer formed of a composition and a thermocurable resin layer formed of a resin composition containing a thermosetting resin. The composite laminate described in Crab.
[6] The composite laminate according to [5], wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin.
[7] A functional group-containing layer laminated in contact with the metal material and the resin coating layer is provided between the metal material and the resin coating layer.
The composite laminate according to any one of [1] to [6], wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from a glycidyl compound and a thiol compound (3) A mercapto group derived from a silane coupling agent has a glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group. A functional group obtained by reacting at least one selected from the group consisting of a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, and an amino compound and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound
[8] Any one of [1] to [7], wherein the surface of the metal material is subjected to at least one pretreatment selected from the group consisting of blasting treatment, polishing treatment, etching treatment and chemical conversion treatment. The composite laminate according to.
[9] The composite laminate according to any one of [1] to [8], wherein the metal material is aluminum.
[10] The composite laminate according to [9], wherein the pretreatment is at least one selected from an etching treatment and a boehmite treatment.
[11] The composite laminate according to any one of [1] to [8], wherein the metal material comprises at least one selected from the group consisting of iron, titanium, magnesium, stainless steel and copper.

[12] The method for producing a composite laminate according to any one of [1] to [11], wherein the composite laminate has the metal material and the resin coating layer between the metal material and the resin coating layer. It has a functional group-containing layer laminated in contact with a resin coating layer, and the functional group-containing layer is at least one selected from the group consisting of the following (1') to (7') on the surface of the metal material. A method for producing a composite laminate, which is prepared by using.
(1') At least one functional group silane coupling agent selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2') At least one selected from a glycidyl compound and a thiol compound, and Combination of silane coupling agents having an amino group (3') A group consisting of a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one selected from the above and a silane coupling agent having a mercapto group (4') Combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Amino group and (meth) acryloyl A combination of at least one selected from the group consisting of a compound having a group, an amino compound and a thiol compound, and a silane coupling agent having a glycidyl group (6'), an isocyanate compound (7'), and a thiol compound.
[13] The method for producing a composite laminate according to [12], wherein the treatment is at least one selected from the group consisting of the following (2 ″) to (5 ″).
(2'') Treatment to add at least one selected from a glycidyl compound and a thiol compound after treatment with a silane coupling agent having an amino group (3'') After treatment with a silane coupling agent having a mercapto group , A treatment to add at least one selected from the group consisting of a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group (4'). ') Treatment to add a thiol compound after treatment with a silane coupling agent having a (meth) acryloyl group (5'') After treatment with a silane coupling agent having a glycidyl group, amino groups and (meth) acryloyl groups Treatment to add at least one selected from the group consisting of compounds having
[14] When the functional group-containing layer is provided before the resin coating layer is formed, the metal material is subjected to a blasting treatment, a polishing treatment, an etching treatment and a chemical conversion treatment before the functional group-containing layer is formed. The method for producing a composite laminate according to [12] or [13], wherein at least one pretreatment selected from the above is applied.

[15] A metal-polyolefin conjugate in which a surface of the composite laminate according to any one of [1] to [11] on the resin coating layer side and a polyolefin are bonded and integrated.
[16] The method for producing a metal-polyolefin conjugate according to [15], wherein when the polyolefin is molded by injection molding or press molding, the surface on the resin coating layer side and the polyolefin are joined and integrated. Method for manufacturing metal-polyolefin conjugate

[17] A modified polyolefin resin composition obtained by reacting a maleic anhydride-modified polyolefin with a bifunctional epoxy resin and a bifunctional phenol resin.
[18] A modified polyolefin resin composition obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol resin with a maleic anhydride-modified polyolefin.
[19] The modified polyolefin resin according to [17] or [18], wherein the total amount of the bifunctional epoxy resin and the bifunctional phenol resin is 5 to 100 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified polyolefin. Composition.

According to the present invention, it is possible to provide a composite laminate suitable for an application in which a metal material and a polyolefin are firmly bonded, and a related technique thereof.

It is explanatory drawing which shows the structure of the composite laminated body in one Embodiment. It is explanatory drawing which shows the structure of the composite laminated body in another embodiment. It is explanatory drawing which shows the structure of the metal-polyolefin conjugate in one Embodiment. It is an SEM photograph of a boehmite film.

The composite laminate of the embodiment of the present invention and related techniques thereof will be described in detail.

[Composite laminate]
As shown in FIG. 1, the composite laminate 1 of the present embodiment is a composite laminate having a metal material 2 and a one-layer or a plurality of layers of a resin coating layer 3 laminated on the metal material. At least one layer of the resin coating layer 3 is a modified polyolefin layer 31 formed of a resin composition containing a modified polyolefin.

<Metal material 2>
The metal type of the metal material 2 is not particularly limited. Examples of the metal type include aluminum, iron, titanium, magnesium, stainless steel, copper and the like. Of these, aluminum is particularly preferably used from the viewpoint of light weight and ease of processing.
In the present invention, the term "aluminum" is used to include a simple substance of aluminum and an alloy thereof. Similarly, iron, titanium, magnesium and copper shall also be used in the sense of including these simple substances and their alloys.

Before laminating the resin coating layer 3 on the metal material 2, it is preferable to perform a pretreatment on the surface of the metal material.

Examples of the pretreatment include cleaning with a solvent, degreasing treatment, blasting treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical conversion treatment and the like, and pretreatment for generating hydroxyl groups on the surface of a metal material is preferable. These pretreatments may be performed with only one type or two or more types. As a specific method of these pretreatments, a known method can be used.
These pretreatments remove contaminants on the surface of the metal material 2 and / or form fine irregularities 21 on the surface of the metal material 2 for the purpose of anchoring effect to roughen the surface. As a result, the adhesiveness between the surface of the metal material and the resin coating layer can be improved, and it can also contribute to the improvement of the adhesiveness of various materials (metal materials, organic materials, etc.) to the bonding target.

Therefore, when the composite laminate is manufactured, the metal material removes contaminants on the surface of the metal material 2 before forming the resin coating layer, and the surface of the metal material 2 has fine irregularities for the purpose of an anchor effect. It is preferable to perform a treatment for forming 21 to roughen the surface, specifically, at least one pretreatment selected from the group consisting of a blast treatment, a polishing treatment, an etching treatment and a chemical conversion treatment.

Examples of the cleaning and degreasing treatment with the solvent and the like include degreasing the surface of the metal material with an organic solvent such as acetone and toluene. This washing and degreasing treatment is preferably performed before other pretreatments.

Examples of the blasting process include shot blasting and sand blasting.

Examples of the polishing treatment include buffing polishing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing, and the like.

Plasma treatment uses a high-pressure power supply for plasma treatment, hits the surface of the material with a plasma beam emitted from a rod called an electrode, first cleans the foreign matter oil film existing on the surface, and then inputs gas energy according to the material to the surface. Examples of the method of exciting a molecule include an atmospheric pressure plasma treatment method capable of imparting a hydroxyl group or a polar group to the surface.

Laser treatment is a technique that improves the surface characteristics by rapidly heating and cooling only the surface layer by laser irradiation, and is an effective method for roughening the surface. Known laser processing techniques can be used.

The etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method. Can be mentioned.
When the metal material is aluminum, the alkali method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable, and the caustic soda method using an aqueous solution of sodium hydroxide is particularly preferable. The alkali method can be carried out, for example, by immersing an aluminum base material in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70 ° C. for 1 to 15 minutes. As the additive, a chelating agent, an oxidizing agent, a phosphate or the like may be added. After the immersion, it is preferably neutralized (de-smuted) with a 5 to 20% by mass aqueous nitric acid solution, washed with water, and dried.

The chemical conversion treatment mainly forms a chemical conversion film on the surface of a metal material.

Examples of the chemical conversion treatment include boehmite treatment and zirconium treatment.
In the boehmite treatment, a boehmite film is formed on the surface of the base material by treating the aluminum base material with hot water. Ammonia, triethanolamine, or the like may be added to water as a reaction accelerator. For example, it is preferable to immerse the aluminum base material in hot water at 90 to 100 ° C. containing triethanolamine at a concentration of 0.1 to 5.0% by mass for 3 seconds to 5 minutes.
In the zirconium treatment, a film of a zirconium compound is formed on the surface of the base material by immersing the aluminum base material in a zirconium salt-containing liquid such as zirconium phosphate. For example, the aluminum base material is placed in a chemical agent for zirconium treatment (for example, "Pearl Court 3762" manufactured by Nihon Parkerizing Co., Ltd., "Pearl Court 3796", etc.) at 45 to 70 ° C. for 0.5 to 3 minutes. It is preferable to immerse. The zirconium treatment is preferably performed after the etching treatment by the caustic soda method.

When the metal material is aluminum, it is particularly preferable to include at least one pretreatment selected from an etching treatment and a boehmite treatment.

<Resin coating layer 3>
[Modified polyolefin layer 31]
At least one layer of the resin coating layer is a modified polyolefin layer 31 formed of a resin composition containing a modified polyolefin.

By laminating such a predetermined resin coating layer on the metal material, the composite laminate of the present embodiment can exhibit excellent adhesiveness to polyolefin.

The resin coating layer is composed of a plurality of layers including the modified polyolefin layer 31 and a layer other than the modified polyolefin layer, and the layer other than the modified polyolefin layer is formed from a resin composition containing a thermoplastic epoxy resin. It may be at least one selected from the thermoplastic epoxy resin layer 32 and the thermosetting resin layer 33 formed from the resin composition containing the thermosetting resin.

When the resin coating layer is composed of a plurality of layers, it is preferable that the essential modified polyolefin layer 31 is laminated so as to be the outermost surface on the opposite side to the metal material.

The modified polyolefin layer 31 is obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a maleic anhydride-modified polyolefin and at the same time reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton. A reaction product obtained by reacting a layer containing the reaction product 1 with a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with maleic anhydride in a maleic anhydride-modified polyolefin skeleton. It is preferably at least one selected from the group consisting of a layer containing 2 and a layer containing a mixture of a thermoplastic epoxy resin and a polyolefin.

(Reactant 1)
The reaction product 1 can be obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a catalyst in a solution of maleic anhydride-modified polyolefin. At this time, the maleic anhydride-modified polyolefin also reacts with the bifunctional epoxy resin, the bifunctional phenol compound, and the thermoplastic epoxy resin produced from the bifunctional epoxy resin and the bifunctional phenol compound described later in the section of the reactant 2. Conceivable.

(Maleic anhydride-modified polyolefin)
Examples of the maleic anhydride-modified polyolefin include maleic anhydride-modified polyolefin obtained by grafting maleic anhydride on the polyolefin, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and the like. There are Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW manufactured by Kayaku Akzo, and the Modic series manufactured by Mitsubishi Chemical Corporation.
Further, as a polypropylene additive functionalized with maleic anhydride, SCONA TPPP2112GA, TPPP8112GA, and TPPP9212GA manufactured by BYK Co., Ltd. may be used in combination.

(Bifunctional epoxy resin)
Examples of the bifunctional epoxy resin include bisphenol type epoxy resin and biphenyl type epoxy resin. Of these, one type may be used alone, or two or more types may be used in combination. Specifically, "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", "jER (registered trademark) 1004", and the same, manufactured by Mitsubishi Chemical Corporation. Examples thereof include "jER (registered trademark) YX-4000".

(Bifunctional phenol compound)
Examples of the bifunctional phenol compound include bisphenol and biphenol. Of these, one type may be used alone, or two or more types may be used in combination.
Examples of these combinations include bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, biphenyl type epoxy resin and 4,4'-biphenol and the like. Further, for example, a combination of "WPE190" and "EX-991L" manufactured by Nagase ChemteX Corporation can be mentioned.

As the catalyst for the polyaddition reaction of the thermoplastic epoxy resin, for example, tertiary amines such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; phosphorus compounds such as triphenylphosphine are preferably used. Used.

(Reactant 2)
Reactant 2 can be obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. As the maleic anhydride-modified polyolefin bifunctional epoxy resin and the bifunctional phenol compound used in this reaction, the same compounds as those used for producing the reaction product 1 can be used.

(Thermoplastic epoxy resin)
The thermoplastic epoxy resin used for producing the reaction product 2 is a resin also called a field-polymerized phenoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and is composed of a bifunctional epoxy resin and a bifunctional phenol compound. A thermoplastic structure, that is, a linear polymer structure, is formed by a double addition reaction in the presence of a catalyst. Here, the linear polymer means a polymer that does not contain a crosslinked structure in the polymer molecule and is one-dimensional linear. Thermoplastic epoxy resins have thermoplasticity, unlike thermosetting resins that form a three-dimensional network with a crosslinked structure.

The total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in producing the reaction product 1 and the reaction product 2 shall be 5 to 100 parts by mass when the maleic anhydride-modified polyolefin is 100 parts by mass. Is more preferable, 5 to 60 parts by mass is more preferable, and 10 to 30 parts by mass is further preferable.

The reaction method that occurs when the reaction product 1 and the reaction product 2 are obtained is a reaction between a maleic anhydride-modified polyolefin and a bifunctional epoxy resin, a reaction between a maleic anhydride-modified polyolefin and a bifunctional phenol compound, and maleic anhydride. A wide variety of reactions such as the reaction of epoxy connecting acids, the reaction of the epoxy group at the end of the thermoplastic epoxy resin with maleic anhydride, and the reaction of the secondary hydroxyl group in the frame of the thermoplastic epoxy resin with maleic anhydride. It is also not possible to comprehensively express the specific aspect based on this. Therefore, it can be said that it is impossible or impractical to directly specify the modified polyolefin obtained as the reactant 1 and the reactant 2 by the structure or property.

The mixture of the thermoplastic epoxy resin and the polyolefin can be obtained by mixing the same thermoplastic epoxy resin as that used in the production of the above-mentioned Reactant 2 and the polyolefin by a conventional method.

(Polyolefin)
As the polyolefin used for forming the mixture, the polyolefin used as the object to be bonded can be used as it is. The polyolefin is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene and the like.

The resin coating layer is laminated on the surface of the metal material. As described above, the resin coating layer may be laminated on the surface of the metal material that has not been pretreated, or may be laminated on the surface of the metal material that has been pretreated. Alternatively, it may be laminated on the surface of the functional group-containing layer described later.

[Thermoplastic epoxy resin layer 32]
The resin coating layer 3 is composed of a plurality of layers of the modified polyolefin layer and other layers, and at least one layer other than the modified polyolefin layer is formed of a resin composition containing a thermoplastic epoxy resin. It can be composed of the thermoplastic epoxy resin layer 32.
The resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably 70% by mass or more.

(Thermoplastic epoxy resin)
Similar to the thermoplastic epoxy resin used for producing the reactant 2, the thermoplastic epoxy resin has a thermoplastic structure by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to undergo a crosslink reaction in the presence of a catalyst. That is, it is a resin that forms a linear polymer structure, and has thermoplasticity unlike a thermosetting resin that forms a three-dimensional network with a crosslinked structure.
Since the thermoplastic epoxy resin has such characteristics, the thermoplastic epoxy resin layer 32 has excellent adhesiveness to the metal material and also has excellent adhesiveness to the modified polyolefin layer 31 by in-situ polymerization. Can be formed.

Therefore, when producing the composite laminate, it is preferable to form the thermoplastic epoxy resin layer 32 by subjecting the composition containing the monomer of the thermoplastic epoxy resin to a double addition reaction on the surface of the lower layer.
The polyaddition reaction of the composition containing the monomer of the thermoplastic epoxy resin is preferably carried out as a lower layer on the surface of the functional group-containing layer described later. The resin coating layer 3 including the thermoplastic epoxy resin layer formed in such an embodiment is excellent in adhesiveness to a metal material and also excellent in bondability to a bonding object described later.

The coating method for forming the thermoplastic epoxy resin layer 32 with the composition containing the monomer of the thermoplastic epoxy resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.

In addition, in the composition containing the monomer of the thermoplastic epoxy resin, in order to sufficiently proceed the polyaddition reaction of the thermoplastic epoxy resin and form a desired resin coating layer, an additive such as a solvent and, if necessary, a colorant, etc. May include. In this case, it is preferable that the monomer of the thermoplastic epoxy resin is the main component among the components other than the solvent of the composition. The main component means that the content of the thermoplastic epoxy resin is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.

The monomer for obtaining the thermoplastic epoxy resin is preferably a combination of a bifunctional epoxy resin and a bifunctional phenolic compound.

The heavy addition reaction is preferably carried out by heating at 120 to 200 ° C. for 5 to 90 minutes, although it depends on the type of reaction compound and the like. Specifically, the thermoplastic epoxy resin layer can be formed by coating the resin composition, volatilizing a solvent as appropriate, and then heating to carry out a polyaddition reaction.

[Thermosetting resin layer 33]
The resin coating layer 3 is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and the layer other than the modified polyolefin layer is formed from a resin composition containing a thermosetting resin. It can also be composed of a thermosetting resin layer 33.

In addition, in the resin composition containing the thermosetting resin, in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired resin coating layer, an additive such as a solvent and, if necessary, a colorant, etc. May include. In this case, it is preferable that the thermosetting resin is the main component among the components other than the solvent of the resin composition. The main component means that the content of the thermosetting resin is 40 to 100% by mass. The content is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more.

Examples of the thermosetting resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.

The thermosetting resin layer 33 may be formed by one of these resins alone, or may be formed by mixing two or more of these resins. Alternatively, the thermosetting resin layer 33 may be composed of a plurality of layers, and each layer may be formed of a resin composition containing a different type of thermosetting resin.

The coating method for forming the thermosetting resin layer 33 with the composition containing the monomer of the thermosetting resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.

The thermosetting resin referred to in the present embodiment broadly means a resin that is cross-linked and cured, and is not limited to the heat-curing type, but also includes a room temperature curing type and a photocuring type. The photocurable type can be cured in a short time by irradiating with visible light or ultraviolet rays. The photo-curing type may be used in combination with a heat-curing type and / or a room temperature curing type. Examples of the photocurable type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and "Lipoxy (registered trademark) LC-720" manufactured by Showa Denko KK.

(Urethane resin)
The urethane resin is usually a resin obtained by reacting an isocyanato group of an isocyanate compound with a hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a coating material containing a polyisocyanate having a vehicle non-volatile component of 10 wt% or more". The urethane resin corresponding to is preferable. The urethane resin may be a one-component type or a two-component type.

Examples of the one-component urethane resin include an oil-modified type (which cures by oxidative polymerization of unsaturated fatty acid groups), a moisture-curing type (which cures by the reaction of isocyanato groups with water in the air), and a block type (which cures by the reaction of isocyanato groups with water in the air). Examples thereof include a lacquer type (which cures when the solvent volatilizes and dries), a lacquer type (which cures when the isocyanato group which is dissociated by heating and regenerated and the hydroxyl group reacts with each other and cures). Among these, a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling and the like. Specific examples thereof include "UM-50P" manufactured by Showa Denko KK.

Examples of the two-component urethane resin include a catalyst-curable type (a catalyst-curable type in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst) and a polyol-curable type (a reaction between an isocyanato group and a hydroxyl group of a polyol compound). (Those that are cured by) and the like.

Examples of the polyol compound in the polyol curing type include polyester polyol, polyether polyol-phenol resin and the like.
Further, examples of the isocyanate compound having an isocyanato group in the polyol-curable type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate. (TDI) or a mixture thereof, p-phenylenediocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) Examples thereof include isocyanate.
The compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in the molar equivalent ratio of the hydroxyl group / isocyanato group.

Examples of the urethanization catalyst used in the two-component urethane resin include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, Amine-based catalysts such as N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholine, bis (2-dimethylaminoethyl) ether, dimethylaminoatexiethanol, triethylamine; Examples thereof include organotin catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimalate.
In the polyol curing type, it is generally preferable to add 0.01 to 10 parts by mass of the urethanization catalyst to 100 parts by mass of the polyol compound.

(Epoxy resin)
The epoxy resin is a resin having at least two epoxy groups in one molecule.
Examples of the prepolymer before curing of the epoxy resin include ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. , Ether-ester type epoxy resin and the like, and among these, bisphenol A type epoxy resin is preferably used. Of these, one type may be used alone, or two or more types may be used in combination.
Specific examples of the bisphenol A type epoxy resin include "jER (registered trademark) 828" and "jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
Specific examples of the novolak type epoxy resin include "DEN (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.

Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts. When the curing agent is used in combination with a long-chain aliphatic amine and / or a thiol, the effect of having a large elongation rate and excellent impact resistance can be obtained.
Specific examples of the thiols include the same compounds as those exemplified as thiol compounds for forming a functional group-containing layer described later. Among these, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Karens MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation and impact resistance.

(Vinyl ester resin)
The vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene). Although it is also called an epoxy (meth) acrylate resin, the vinyl ester resin also includes a urethane (meth) acrylate resin.
As the vinyl ester resin, for example, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary" (Japan Society of Color Material, published in 1993), etc. shall also be used. In addition, specifically, "Lipoxy (registered trademark) R-802", "Lipoxy (registered trademark) R-804", "Lipoxy (registered trademark) R-806", etc. manufactured by Showa Denko KK, etc. Can be mentioned.

The urethane (meth) acrylate resin is obtained by, for example, reacting an isocyanate compound with a polyol compound and then reacting with a hydroxyl group-containing (meth) acrylic monomer (and, if necessary, a hydroxyl group-containing allyl ether monomer). Examples thereof include radically polymerizable unsaturated group-containing oligomers. Specific examples thereof include "Lipoxy (registered trademark) R-6545" manufactured by Showa Denko KK.

The vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
The organic peroxide is not particularly limited, but for example, ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxides. Oxide carbonates and the like can be mentioned. By combining these with a cobalt metal salt or the like, curing at room temperature is also possible.
The cobalt metal salt is not particularly limited, and examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Of these, cobalt naphthenate and / and cobalt octylate are preferred.

(Unsaturated polyester resin)
The unsaturated polyester resin is a monomer (eg, styrene, etc.) in which a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is polymerized. ) Is dissolved.
As the unsaturated polyester resin, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary" (Japan Society of Color Material, published in 1993), etc. can also be used. Yes, and more specifically, "Rigolac (registered trademark)" manufactured by Showa Denko KK can be mentioned.

The unsaturated polyester resin can be cured by radical polymerization by heating in the presence of a catalyst similar to that of the vinyl ester resin.

The resin coating layer is formed on the surface of a metal material with excellent adhesiveness, and exhibits excellent adhesiveness with polyolefin. Further, the surface of the metal material is protected, and deterioration such as dirt adhesion and oxidation on the surface of the metal material can be suppressed.

Therefore, the resin coating layer can impart excellent bondability between the metal material and the polyolefin to be bonded. Further, it is possible to obtain a composite laminate capable of maintaining a state in which excellent adhesiveness can be obtained for a long period of several months while the surface of the metal material is protected as described above.

As described above, the resin coating layer exerts an action of imparting excellent bondability to the polyolefin to be bonded to the metal material. It can be said that the resin coating layer is a primer layer of the composite laminate.
The primer layer referred to here is interposed between the metal material and the bonding target when the metal material is bonded and integrated with the bonding target such as a resin material, for example, as in the metal-polyolefin bond described later. However, it shall mean a layer that improves the adhesiveness of the metal material to the object to be joined.

<Functional group-containing layer 4>
As shown in FIG. 2, between the metal material 2 and the resin coating layer 3, there is a one-layer or a plurality of functional group-containing layers 4 laminated in contact with the metal material 2 and the resin coating layer 3. You can also do it.
When it has a functional group-containing layer, the functional group formed by reacting the functional group of the functional group-containing layer with the hydroxyl group on the surface of the metal material and the functional group of the resin constituting the resin coating layer is formed by a chemical bond. , The effect of improving the adhesiveness between the surface of the metal material and the resin coating layer can be obtained, and it can also contribute to the improvement of the bondability with the bonding target.

"process"
The functional group-containing layer 4 is preferably formed by treating the surface of the metal material 2 with at least one selected from the group consisting of the following (1') to (7').
(1') Silane coupling agent containing at least one functional group selected from the group consisting of a glycidyl group, an amino group and a mercapto group (2') At least one selected from a glycidyl compound and a thiol compound, and an amino group. Combination of silane coupling agent having (3') Selected from the group consisting of a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one silane coupling agent having a mercapto group (4') Combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Having an amino group and a (meth) acryloyl group Combination of at least one selected from the group consisting of compounds, amino compounds and thiol compounds and a silane coupling agent having a glycidyl group (6') isocyanate compound (7') thiol compound << functional group >>
The functional group-containing layer 4 preferably contains the functional group introduced by the above treatment, and specifically, preferably contains at least one functional group selected from the group consisting of the following (1) to (7). ..
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of a glycidyl group, an amino group and a mercapto group (2) An amino group derived from a silane coupling agent, from a glycidyl compound and a thiol compound Functional group obtained by reacting at least one selected type (3) A glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group in a mercapto group derived from a silane coupling agent, and (meth). A functional group obtained by reacting at least one selected from the group consisting of compounds having an acryloyl group and an amino group (4) A functional group obtained by reacting a (meth) acryloyl group derived from a silane coupling agent with a thiol compound (4) 5) A functional group (6) isocyanate compound obtained by reacting a glycidyl group derived from a silane coupling agent with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound and a thiol compound. Derived isocyanato group (7) Mercapto group derived from thiol compound

Before forming the functional group-containing layer 4 on the metal material, the surface of the metal material can be pretreated.
By applying the pretreatment, the anchor effect due to the fine irregularities and the functional groups of the functional group-containing layer react with the hydroxyl groups on the surface of the metal material and the functional groups of the resin constituting the resin coating layer 3. By the synergistic effect with the chemical bond formed in the above, it is possible to improve the adhesiveness between the surface of the metal material and the resin coating layer and the bondability with the object to be bonded.

The method for forming the functional group-containing layer with the silane coupling agent, the isocyanate compound, the thiol compound, or the like is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, the metal material is immersed in a solution of a silane coupling agent having a concentration of 5 to 50% by mass at room temperature to 100 ° C. for 1 minute to 5 days, and then dried at room temperature to 100 ° C. for 1 minute to 5 hours. It can be done by a method such as making it.

〔Silane coupling agent〕
As the silane coupling agent, for example, known ones used for surface treatment of glass fibers and the like can be used. The silanol group generated by hydrolyzing a silane coupling agent or the silanol group obtained by oligomerizing the silanol group reacts with a hydroxyl group existing on the surface of the metal material and bonds to the resin coating layer 3 so that the silanol group can be chemically bonded. A functional group based on the structure of the silane coupling agent can be imparted (introduced) to the metal material 2.

The silane coupling agent is not particularly limited, but for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyl. A silane coupling agent having an amino group such as dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriatexisilane, 2- (3) , 4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiatexisilane, 3-glycidoxypropylmethyldiatexisilane, 3-glycidoxypropyl A silane coupling agent having an epoxy group such as triatexisilane, a silane coupling agent having a mercapto group or an isocyanate group such as 3-mercaptopropylmethyldimethoxysilane, 3-isocyanuppropyltriatexisilane, and dithioltriazinepurpyrtriatexisilane. , Vinyltrimethoxysilane, Vinyltriatexylsilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiatexisilane, 3-methacryloxy A silane coupling agent having a vinyl group such as propyltriatexisilane and 3-acryloxypropyltrimethoxysilane, 3-triatexisilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3- Examples thereof include aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, and 3-ureidopropyltrialkoxysilane. These may be used alone or in combination of two or more.

[Isocyanate compound]
The isocyanate compound is a functional group based on the structure of the isocyanate compound, which can be chemically bonded to the resin coating layer 3 by reacting and bonding an isocyanato group in the isocyanate compound with a hydroxyl group existing on the surface of the metal material 2. Can be imparted (introduced) to the metal material.

The isocyanate compound is not particularly limited, but for example, other polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI). , 2-Isocyanate ethyl methacrylate (for example, "Karens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), 2-isocyanate ethyl acrylate (for example, "Karens AOI" manufactured by Showa Denko Co., Ltd.), which is an isocyanate compound having a radically reactive group. (Registered trademark) ”,“ AOI-VM (registered trademark) ”), 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example,“ Karens BEI (registered trademark) ”manufactured by Showa Denko Co., Ltd.), etc. Be done.

[Thiol compound]
The thiol compound is based on the structure of the thiol compound which can be chemically bonded to a resin coating layer or a bonding target by reacting and bonding a mercapto group in the thiol compound with a hydroxyl group existing on the surface of the metal material 2. A functional group can be imparted (introduced) to a metal material.

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Corporation and "QE-" manufactured by Toray Fine Chemicals Co., Ltd. 340M "), ether-based first-class thiol (for example," Cup Cure 3-800 "manufactured by Cognis), 1,4-bis (3-mercaptobutylyloxy) butane (for example," Karenz "manufactured by Showa Denko KK. MT (registered trademark) BD1 "), pentaerythritol tetrakis (3-mercaptobutyrate) (for example," Karenz MT (registered trademark) PE1 "manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyl) Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Karens MT (registered trademark) NR1" manufactured by Showa Denko KK) and the like can be mentioned.

[Metal-polyolefin conjugate 5]
As shown in FIG. 3, in the metal-polyolefin conjugate 5 of the present embodiment, the resin coating layer 3 of the composite laminate 1 has, as described above, the surface on the primer layer side and the polyolefin 6 as a primer layer. Is joined and integrated.

The thickness of the primer layer (thickness after drying) depends on the material to be bonded and the contact area of the bonded portion, but from the viewpoint of obtaining excellent adhesion between the surface on the primer layer side and the polyolefin, from the viewpoint of obtaining excellent adhesion between the surface on the primer layer side and the polyolefin. It is preferably 1 μm to 500 μm, more preferably 3 μm to 100 μm, and even more preferably 5 μm to 70 μm. When the primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) is the total thickness of each layer.

The polyolefin in the metal-polyolefin conjugate is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene and the like.
Polypropylene is generally a highly rigid homopolymer in which only propylene is polymerized, a highly transparent and flexible random polymer in which a small amount of ethylene is copolymerized, and a resistance to which the rubber component (EPR) is uniformly and finely dispersed in the homo-random polymer. It is classified as a block copolymer having high impact resistance, but any one of them may be used. Further, a type containing talc, glass fiber and carbon fiber may be used to increase the strength. The product containing talc is manufactured by Sun Aromar, and the product name is TRC104N. The product containing glass fiber is manufactured by Daicel Polymer Co., Ltd. There is a product name PP-CF40-11 F008 and the like.

As a method for producing the metal-polyolefin bonded body, a composite laminate and a molded body of the resin material separately produced can be bonded and integrated.
Further, at the same time as molding the resin material, it can be joined and integrated with the composite laminate. Specifically, when the resin material is molded by, for example, injection molding, press molding, transfer molding, or the like, the surface of the composite laminate on the primer layer side and the resin material are joined and integrated. Thereby, a metal-polyolefin conjugate can be obtained.

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to those of these examples.

<Manufacturing example 1>
Maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g and xylene: 95 g were placed in a flask and dissolved by heating to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1001: polycondensate of bisphenol A and epichlorohydrin manufactured by Mitsubishi Chemical Co., Ltd.): 1.01 g, bisphenol A: 0.24 g, 2,4,6- Tris (dimethylaminomethyl) phenol: 0.006 g was put into a flask, stirred at 125 ° C. for 30 minutes, and modified with a thermoplastic epoxy resin, a bifunctional epoxy resin, and a bifunctional phenol compound. Maleic anhydride-modified polypropylene: Modified. PP-1 was obtained.

<Manufacturing example 2>
Maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g and xylene: 95 g were placed in a flask and dissolved by heating to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1004: 0.49 g manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A: 0.06 g, 2,4,6-tris (dimethylaminomethyl) phenol): 0.003 g. It was put into a flask and stirred at 125 ° C. for 30 minutes to obtain a maleic anhydride-modified polypropylene modified with a thermoplastic epoxy resin, a bifunctional epoxy resin, and a bifunctional phenol compound: modified PP-2.

<Manufacturing example 3>
Talc-containing polypropylene (TRC104N manufactured by SunAllomer Ltd.): 5 g and xylene: 95 g were placed in a flask and dissolved by raising the temperature to 125 ° C. with stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.): 1.01 g, bisphenol A: 0.24 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.006 g. It was put into a flask and stirred at 125 ° C. for 30 minutes to obtain a mixture of thermoplastic epoxy resin (20% by mass) and polypropylene: modified PP-3.

<Manufacturing example 4>
A flask was charged with 95 g of xylene, a bifunctional epoxy resin (jER1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.20 g, bisphenol A: 0.066 g, and 2,4,6-tris (dimethylaminomethyl) phenol: 0.003 g. The mixture was stirred at 125 ° C. for 30 minutes and reacted to obtain a thermoplastic epoxy resin solution. Next, 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g was added to the flask to dissolve it, and the maleic anhydride-modified polypropylene modified with a thermoplastic epoxy resin (20% by mass): Modified PP-4 was obtained.

<Example 1-1>
(Preprocessing)
An 18 mm × 45 mm, 1.5 mm thick aluminum plate (A6063) was immersed in a 5% by mass sodium hydroxide aqueous solution for 1.5 minutes, neutralized with a 5% by mass nitric acid aqueous solution, and washed with water. Etching treatment was performed by drying.
Next, the etched aluminum plate was boiled in pure water for 10 minutes and then baked at 250 ° C. for 10 minutes to perform boehmite treatment to form a boehmite film on the surface of the aluminum plate.
When the surface of the aluminum plate after the boehmite treatment was observed by a SEM photograph (scanning electron micrograph, 45 ° tilt observation), as shown in FIG. 4, a boehmite film having whisker-like irregularities on the surface was formed. It was confirmed that there was.

(Functional group-containing layer)
Next, the aluminum plate after the boehmite treatment was prepared by dissolving 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicon Co., Ltd .; a silane coupling agent) in 1000 g of industrial ethanol at 70 ° C. After immersing in the silane coupling agent-containing solution of silane for 20 minutes, the aluminum plate was taken out and dried to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, the modified PP-1 obtained in Production Example 1 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer. A composite laminate having a resin coating layer of modified PP-1 having a thickness of 30 μm was prepared.

<Example 1-2>
A polypropylene resin (PP resin) containing talc (TRC104N manufactured by Sun Aroma Co., Ltd.) (to be joined) was applied to the surface of the composite laminate produced in Example 1-1 on the resin coating layer side, and an injection molding machine (Sumitomo Heavy Industries, Ltd.) SE100V manufactured by the company; by injection molding at cylinder temperature 200 ° C., tool temperature 30 ° C., injection speed 50 mm / sec, peak / holding pressure 195/175 [MPa / MPa]). A test piece for tensile test (PP resin, 10 mm × 45 mm × 3 mm, joint length 5 mm) (metal-polyolefin joint) conforming to ISO19095 was prepared.

[Adhesion evaluation]
The test piece (metal-polyolefin conjugate) produced in Example 1-2 was left at room temperature for 1 day, and then subjected to a tensile tester (Shimadzu Corporation universal testing machine autograph) in accordance with ISO19095 1-4. "AG-IS"; load cell 10 kN, tensile speed 10 mm / min, temperature 23 ° C., 50% RH), a tensile shear joint strength test was performed, and the joint strength was measured. The measurement results are shown in Table 1 below.

<Example 2-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer: 1st layer)
A bifunctional epoxy resin (jER® 1001 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 24 g, and triethylamine: 0.4 g are dissolved in 250 g of acetone on the surface of the functional group-containing layer. The thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes to perform a heavy addition reaction, and then allowed to cool to room temperature to allow the first resin coating layer (1st layer). A thermoplastic epoxy resin layer 32) was formed.

(Resin coating layer: 2nd layer)
Next, the modified PP-2 obtained in Production Example 2 was applied to the surface of the thermoplastic epoxy resin layer to volatilize xylene and held at 150 ° C. for 30 minutes to apply the modified PP-2 to the surface of the thermoplastic epoxy resin layer. A composite laminate in which a resin coating layer (modified poreolefin layer 31) of modified PP-2 having a thickness of 30 μm was formed was produced.

<Example 2-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 2-1 on the resin coating layer side of the second layer.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 3-1>
(Preprocessing)
A copper plate of 18 mm × 45 mm and a thickness of 1.5 mm was degreased with acetone.

(Functional group-containing layer)
Next, the degreased copper plate is prepared by dissolving 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicon Co., Ltd .; a silane coupling agent) in 100 g of industrial ethanol. After immersing in a silane coupling agent solution at ° C. for 5 minutes, the copper plate was taken out and dried, and a functional group derived from the silane coupling agent was introduced into the surface of the copper plate after the degreasing treatment.
Further, a bifunctional thiol compound 1,4 bis (3-mercaptobutyryloxy) butane (Carens MT BD1 manufactured by Showa Denko KK): 0.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-) 30): After immersing 0.05 g in a solution of 0.05 g in 150 g of toluene at 70 ° C. for 10 minutes, the mixture was lifted and dried. In this way, two functional group-containing layers were formed.

(Resin coating layer)
Next, the modified PP-3 obtained in Production Example 3 was applied to the surface of the functional group-containing layer of the copper plate to volatilize xylene and held at 150 ° C. for 30 minutes to obtain a thickness on the surface of the functional group-containing layer. A composite laminate on which a resin coating layer of modified PP-3 having a thickness of 30 μm was formed was prepared.

<Example 3-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 3-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 4-1>
(Preprocessing)
An iron plate of 18 mm × 45 mm and a thickness of 1.5 mm was sanded using # 100 sandpaper to form fine irregularities on the surface of the iron plate.

(Resin coating layer: 1st layer)
The same operation as in Example 2-1 was carried out on the surface of the uneven surface to form a first resin coating layer (thermoplastic epoxy resin layer).

(Resin coating layer: 2nd layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 4-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 4-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Comparative Example 1-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

<Comparative Example 1-2>
The same injection molding operation as in Example 1-2 was carried out without providing the functional group-containing layer and the resin coating layer on the surface of the polyolefin film of the aluminum plate produced in Comparative Example 1-1, but the PP resin was used. , It was not possible to prepare a metal-polyolefin conjugate without adhering to the surface of the boehmite film.

<Comparative Example 2-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, a solution prepared by dissolving 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation) in 95 g of xylene was applied to the surface of the functional group-containing layer to volatilize xylene, and 150 The mixture was held at ° C. for 30 minutes to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 2-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Comparative Example 2-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 5-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, 2 g of 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shinetsu Silicon Co., Ltd .; a silane coupling agent) was dissolved in 1000 g of industrial ethanol in the aluminum plate after the boehmite treatment. After immersing in a silane coupling agent-containing solution at 70 ° C. for 20 minutes, the aluminum plate was taken out and dried to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, the modified PP-4 obtained in Production Example 4 was applied to the surface of the functional group-containing layer, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer. A composite laminate having a resin coating layer of modified PP-4 having a thickness of 30 μm was prepared.

<Example 5-2>
A polypropylene resin (PP resin) containing glass fibers (pp-GF40-01 F02 manufactured by Daicel Polymer Co., Ltd.) (to be bonded) was applied to the surface of the composite laminate produced in Example 5-1 on the resin coating layer side. A test piece for a tensile test was prepared by injection molding under the same conditions as in 1-2.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 6-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 5-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer: 1st layer)
The same operation as in Example 2-1 was performed except that the epoxy resin was changed to jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer, and the first resin coating layer (thermoplastic) was performed. Epoxy resin layer) was formed.

(Resin coating layer: 2nd layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 6-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 5-2 on the surface of the composite laminate prepared in Example 6-1 on the resin coating layer side of the second layer.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 7-1>
(Preprocessing)
A magnesium plate having a size of 18 mm × 45 mm and a thickness of 1.5 mm was sanded in the same manner as in Example 4-1 to form fine irregularities on the surface of the magnesium plate.

(Functional group-containing layer)
Next, the same operation as in Example 3-1 was carried out on the magnesium plate to form a functional group-containing layer.

(Resin coating layer)
Next, the same operation as in Example 1-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-1 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 7-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 5-2 on the surface of the composite laminate prepared in Example 7-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 8-1>
(Preprocessing)
An aluminum plate (A6063) having a size of 18 mm × 45 mm and a thickness of 1.5 mm was subjected to the same sanding treatment as in Example 4-1 to form fine irregularities on the surface of the aluminum plate.

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the aluminum plate after the sanding treatment.

(Resin coating layer: 1st layer)
The same operation as in Example 6-1 was carried out to form the first resin coating layer (thermoplastic epoxy resin layer).

(Resin coating layer: 2nd layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 8-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 5-2 on the surface of the composite laminate prepared in Example 8-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Comparative Example 3-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

<Comparative Example 3-2>
The same injection molding operation as in Example 5-2 was performed without providing the functional group-containing layer and the resin coating layer on the surface of the polyolefin film of the aluminum plate produced in Comparative Example 3-1. , It was not possible to prepare a metal-polyolefin conjugate without adhering to the surface of the boehmite film.

<Comparative Example 4-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, the same operation as in Comparative Example 2-1 was carried out to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 4-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 5-2 on the surface of the composite laminate prepared in Comparative Example 4-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 9-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, the same operation as in Example 5-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-4 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 9-2>
A polypropylene resin (PP resin) containing carbon fibers (pp-GF40-01 F008 manufactured by Daicel Polymer Co., Ltd.) (to be bonded) was applied to the surface of the composite laminate produced in Example 9-1 on the resin coating layer side. A test piece for a tensile test was prepared by injection molding under the same conditions as in 1-2.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 10-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer: 1st layer)
The same operation as in Example 2-1 was performed except that the epoxy resin was changed to jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer, and the first resin coating layer (thermoplastic) was performed. Epoxy resin layer) was formed.

(Resin coating layer: 2nd layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 10-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 9-2 on the surface of the composite laminate prepared in Example 10-1 on the side of the resin coating layer of the second layer.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 11-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to introduce a functional group derived from a silane coupling agent onto the surface of the boehmite film.
Further, 2-isocyanate ethyl methacrylate (Showa Denko KK Karens MOI (registered trademark)): 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g and toluene 150 g After immersing in the solution dissolved in it at 70 ° C. for 5 minutes, it was withdrawn and dried. In this way, a functional group-containing layer in which chemically bondable functional groups were extended in the three-dimensional direction was formed.

(Resin coating layer)
Next, the same operation as in Example 1-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-1 having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 11-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 9-2 on the surface of the composite laminate prepared in Example 11-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 12-1>
(Preprocessing)
A martensitic stainless steel (SUS403) steel sheet having a size of 18 mm × 45 mm and a thickness of 1.5 mm was sanded in the same manner as in Example 4-1 to form fine irregularities on the surface of the stainless steel sheet.

(Functional group attachment layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the stainless steel sheet after the sanding treatment.

(Resin coating layer: 1st layer)
Epoxy resin (jER® 1007 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 5.6 g, and triethylamine: 0.4 g are dissolved in 196 g of acetone on the surface of the functional group-containing layer. The thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes to perform a heavy addition reaction, and then allowed to cool to room temperature to allow the first resin coating layer (1st layer). Thermoplastic epoxy resin layer) was formed.

(Resin coating layer: 2nd layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a resin coating layer of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 12-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 9-2 on the surface of the composite laminate prepared in Example 12-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

<Comparative Example 5-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

<Comparative Example 5-2>
The same injection molding operation as in Example 9-2 was performed without providing the functional group-containing layer and the resin coating layer on the surface of the polyolefin film of the aluminum plate produced in Comparative Example 5-1. , It was not possible to prepare a metal-polyolefin conjugate without adhering to the surface of the boehmite film.

<Comparative Example 6-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface of the boehmite film.

(Resin coating layer)
Next, the same operation as in Example 2-1 was carried out to prepare a composite laminate in which a maleic anhydride-modified polypropylene layer having a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Comparative Example 6-2>
A test piece for a tensile test was prepared by performing the same operation as in Example 9-2 on the surface of the composite laminate prepared in Comparative Example 6-1 on the resin coating layer side.
The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

The composite laminate according to the present invention is bonded and integrated with a polyolefin, for example, a door side panel, a bonnet, a roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, and a power control. Vehicles such as unit (PCU) housings, electric compressor members (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacers, battery cases, LED headlamps, etc. It is used as a component for parts, a smartphone, a notebook computer, a tablet computer, a smart watch, a large LCD TV (LCD-TV), a structure for outdoor LED lighting, and the like, but is not particularly limited to these exemplified applications.

1 Composite laminate 2 Metal material 21 Fine irregularities 3 Resin coating layer (primer layer)
31 Modified polyolefin layer 32 Thermoplastic epoxy resin layer 33 Thermosetting resin layer 4 Functional group-containing layer 5 Metal-polyolefin conjugate 6 Polyolefin

Claims (15)

A composite laminate having a metal material and one or a plurality of resin coating layers laminated on the metal material.
At least one layer of the resin coating layer is a modified polyolefin layer formed of a resin composition containing a modified polyolefin.
The modified polyolefin layer is laminated so as to be the outermost surface on the opposite side to the metal material.
The modified polyolefin layer is a reaction formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of maleic anhydride-modified polyolefin and at the same time reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton. A composite laminate that is a layer containing the substance 1. The resin coating layer comprises a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer.
At least one layer other than the modified polyolefin layer is a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a thermosetting resin composition formed of a resin composition containing a thermosetting resin. The composite laminate according to claim 1 , which is at least one selected from the resin layer. The composite laminate according to claim 2 , wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin. A functional group-containing layer laminated in contact with the metal material and the resin coating layer is provided between the metal material and the resin coating layer.
The composite laminate according to any one of claims 1 to 3 , wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from a glycidyl compound and a thiol compound (3) A mercapto group derived from a silane coupling agent has a glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group. A functional group obtained by reacting at least one selected from the group consisting of a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, and an amino compound and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound The metal material according to any one of claims 1 to 4 , wherein the surface of the metal material is subjected to at least one pretreatment selected from the group consisting of blasting treatment, polishing treatment, etching treatment and chemical conversion treatment. Composite laminate. The composite laminate according to any one of claims 1 to 5 , wherein the metal material is aluminum. The composite laminate according to claim 5 , wherein the metal material is aluminum, and the pretreatment is at least one selected from an etching treatment and a boehmite treatment. The composite laminate according to any one of claims 1 to 5 , wherein the metal material comprises at least one selected from the group consisting of iron, titanium, magnesium, stainless steel and copper. The method for producing a composite laminate according to any one of claims 1 to 8.
The composite laminate has a functional group-containing layer laminated between the metal material and the resin coating layer in contact with the metal material and the resin coating layer.
A method for producing a composite laminate, wherein the functional group-containing layer treats the surface of the metal material with at least one selected from the group consisting of the following (1') to (7').
(1') Silane coupling agent having at least one functional group selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2') At least one selected from a glycidyl compound and a thiol compound. And a combination of a silane coupling agent having an amino group (3') from a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one selected from the above group and a silane coupling agent having a mercapto group (4') Combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') Amino group and (meth) ) A combination of at least one selected from the group consisting of a compound having an acryloyl group, an amino compound and a thiol compound, and a silane coupling agent having a glycidyl group (6') isocyanate compound (7') thiol compound. The method for producing a composite laminate according to claim 9 , wherein the treatment is at least one selected from the group consisting of the following (2 ″) to (5 ″).
(2'') Treatment to add at least one selected from a glycidyl compound and a thiol compound after treatment with a silane coupling agent having an amino group (3'') After treatment with a silane coupling agent having a mercapto group , A treatment to add at least one selected from the group consisting of a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group (4'). ') Treatment to add a thiol compound after treatment with a silane coupling agent having a (meth) acryloyl group (5'') After treatment with a silane coupling agent having a glycidyl group, amino groups and (meth) acryloyl groups Treatment to add at least one selected from the group consisting of compounds having When the functional group-containing layer is provided before the resin coating layer is formed, the metal material is selected from the group consisting of blasting treatment, polishing treatment, etching treatment and chemical conversion treatment before forming the functional group-containing layer. The method for producing a composite laminate according to claim 9 or 10 , wherein at least one kind of pretreatment is applied. A metal-polyolefin conjugate in which a surface of the composite laminate according to any one of claims 1 to 8 on the resin coating layer side and a polyolefin are bonded and integrated. The method for producing a metal-polyolefin conjugate according to claim 12.
A method for producing a metal-polyolefin conjugate in which a surface on the resin coating layer side and the polyolefin are joined and integrated when the polyolefin is molded by injection molding or press molding. A modified polyolefin obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a maleic anhydride-modified polyolefin and at the same time reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton . The modified polyolefin according to claim 14, wherein the total amount of the bifunctional epoxy resin and the bifunctional phenol compound is 5 to 100 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified polyolefin.

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