TW202106506A - Composite multilayer body and metal-polyolefin bonded body - Google Patents

Abstract

A composite multilayer body which comprises a metal material and one or more resin coating layers that are superposed on the metal material, wherein: at least one of the resin coating layers is a modified polyolefin layer that is formed of a resin composition containing a modified polyolefin; and the modified polyolefin layer is one selected from the group consisting of a layer containing a reaction product 1 of a maleic acid anhydride-modified polyolefin, a bifunctional epoxy resin and a bifunctional phenol compound, a layer containing a reaction product 2 of a maleic acid anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin.

Description

Composite laminate and metal-polyolefin joint

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

In the fields of automobile parts and OA equipment where the weight reduction of products is required, the demand for metal-resin joints formed by joining and integrating metal materials such as aluminum and resin has increased. In these metal-resin joint bodies, when aluminum is used as the metal material, in order to sufficiently ensure the bonding strength between the metal and the resin, surface treatment of aluminum is performed.

As the aforementioned surface treatment, physical methods such as sandblasting treatment, chemical conversion treatment, and anodizing treatment or chemical surface treatments are being investigated.

When polyolefins such as polypropylene are used as resins in metal-resin joints, since polyolefins have no polarity, the use of acid-modified polyolefins is being studied in order to improve the adhesion to metals. For example, it is disclosed that an adhesive layer containing a modified polypropylene resin introduced with a polar group is formed on a substrate treatment film provided on the surface of a substrate made of aluminum alloy, and the adhesive layer is dissolved and anchored with polypropylene. Method of joining (Patent Documents 1 and 2); Method of forming an acid-modified polypropylene layer with predetermined melt viscosity, melting point, crystallinity, etc. on aluminum alloy (Patent Document 3); Using phosphoric acid for surface treatment of aluminum alloy Chromate, chromate chromate, zirconium oxide, titanium zirconium, etc. to provide a modified polypropylene layer with polar groups (Patent Document 4); on the surface of the metal chemical conversion treatment film, 15 is made on the first layer A method in which a ~40μm layer composed of epoxy resin and blocked isocyanate is provided with a 4-30μm acid-modified polyolefin layer on the second layer (Patent Document 5). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-16584 A [Patent Document 2] WO2016/199339 Publication [Patent Document 3] WO2016/152118 Publication [Patent Document 4] Patent No. 06376867 [Patent Document 5] Japanese Patent Application Publication No. 2018-154034

[The problem to be solved by the invention]

However, the problem in the above-mentioned past technology is that the bonding strength of the metal-polyolefin joint body stays at a predetermined level, and it is difficult to respond to the demand for further improvement of the bonding strength or improvement of durability. The present invention has been completed in view of such a technical background, and its subject is to provide a composite laminate suitable for the use of firmly joining metals and polyolefins and related technologies. The aforementioned related technology refers to the method of manufacturing the composite laminate, the metal-polyolefin junction using the composite laminate, and the method of manufacturing the composite laminate. [Means to solve the problem]

The present invention provides the following means in order to achieve the aforementioned object. In addition, in this specification, the term “bonding” refers to the connected object and the object, and then refers to the subordinate concept, which means that the two adhesive materials are interposed with organic materials (thermosetting resins or thermoplastic resins, etc.) like adhesive tapes or adhesives. (The person who wants to succeed) becomes the joined state.

[1] A composite laminate having a metal material and one or more resin coating layers laminated on the aforementioned metal material, At least one layer of the aforementioned resin coating layer is a modified polyolefin layer formed of a resin composition containing modified polyolefin, The aforementioned modified polyolefin layer is selected from a layer containing maleic anhydride modified polyolefin, a reactant 1 of a bifunctional epoxy resin and a bifunctional phenol compound, and a layer containing maleic anhydride modified polyolefin and a thermoplastic epoxy resin. At least one of the group of the layer of the reactant 2 and the layer containing the mixture of polyolefin and thermoplastic epoxy resin. [2] The composite laminate according to [1], wherein the reactant 1 is made by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to an addition polymerization reaction in a solution containing maleic anhydride modified polyolefin to make. [3] The composite laminate according to [1], wherein the above-mentioned reactant 2 is a thermoplastic epoxy resin produced by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound with Malay Polyolefin modified by acid anhydride and reacted. [4] The composite laminate according to [1], wherein the mixture is a mixture of polypropylene and thermoplastic epoxy resin. [5] The composite laminate according to any one of [1] to [4], wherein the resin coating layer is composed of a plurality of layers including the modified polyolefin layer and layers other than the modified polyolefin layer Layered, At least one layer other than the modified polyolefin layer is selected from a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a resin composition containing a thermosetting resin At least one of the formed thermosetting resin layers. [6] The composite laminate according to [5], wherein the thermosetting resin is at least selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin 1 kind. [7] The composite laminate according to any one of [1] to [6], which is between the metal material and the resin coating layer, and has a laminated layer in contact with the metal material and the resin coating layer With functional base layer, The aforementioned functional group-containing layer includes a functional group selected from at least one of the following groups (1) to (7); (1) A functional group derived from a silane coupling agent and selected from at least one of the group consisting of a glycidyl group, an amino group, a (meth)acryloyl group, and a mercapto group (2) A functional group formed by reacting at least one selected from a glycidyl compound and a thiol compound with an amine group derived from a silane coupling agent (3) Selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and glycidyl groups, and compounds having (meth)acrylic groups and amino groups At least one of them reacts with a sulfhydryl group derived from a silane coupling agent to form a functional group (4) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent (5) At least one selected from the group consisting of a compound having an amine group and a (meth)acryloyl group, and an amine group compound and a thiol compound is reacted with a glycidyl group derived from a silane coupling agent, and Functional group (6) Isocyanate groups derived from isocyanate compounds (7) Mercapto groups derived from thiol compounds. [8] The composite laminate according to any one of [1] to [7], wherein the surface of the metal material is selected from the group consisting of blast treatment, polishing treatment, etching treatment, and chemical conversion treatment. At least one pre-treatment in the group. [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 etching treatment and diaspore treatment. [11] The composite laminate according to any one of [1] to [8], wherein the metal material includes at least one selected from the group consisting of iron, titanium, magnesium, stainless steel, and copper.

[12] A method for manufacturing a composite laminate, which is the method for manufacturing a composite laminate as described in any one of [1] to [11], wherein: The composite laminate system 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, and The aforementioned functional group-containing layer is formed by treating the surface of the aforementioned metal material with at least one selected from the group consisting of (1') to (7') below; (1') Silane coupling agent having at least one functional group selected from the group consisting of glycidyl, amino, (meth)acrylic and mercapto groups (2') A combination of at least one selected from the group consisting of glycidyl compounds and thiol compounds and a silane coupling agent having an amino group (3') selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic acid groups and glycidyl groups, and compounds having (meth)acrylic acid groups and amino groups A combination of at least one of them and a silane coupling agent with a mercapto group (4') Combination of thiol compound and silane coupling agent with (meth)acryloyl group (5') A combination of at least one selected from the group consisting of a compound having an amino group and a (meth)acrylic acid group, and a group of an amino compound and a thiol compound, and a silane coupling agent having a glycidyl group (6’) Isocyanate compound (7') Thiol compound. [13] The method for manufacturing a composite laminate as described in [12], wherein the aforementioned treatment is selected from at least one of the following groups (2") to (5"); (2") After treatment with a silane coupling agent having an amine group, at least one selected from the group consisting of glycidol compounds and thiol compounds is added (3") After treatment with a silane coupling agent having a mercapto group, the addition is selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic acid groups and glycidyl groups, and compounds having (formaldehyde). (Base) treatment of at least one of the group consisting of acryloyl and amine compounds (4") After the treatment with the silane coupling agent with (meth)acrylic acid group, the treatment of adding thiol compound (5") After treatment with a glycidyl silane coupling agent, the addition is selected from the group consisting of compounds having amine groups and (meth)acrylic acid groups, and amine compounds and thiol compounds At least one treatment. [14] The method for producing a composite laminate as described in [12] or [13], wherein, in the case where there is a functional group-containing layer before forming the resin coating layer, the metal material is treated before the functional group-containing layer is formed. Apply at least one pretreatment selected from the group consisting of sandblasting treatment, polishing treatment, etching treatment, and chemical conversion treatment.

[15] A metal-polyolefin joined body formed by joining and integrating the resin coating layer side surface of the composite laminate as described in any one of [1] to [11] and polyolefin. [16] A method for producing a metal-polyolefin joint body, which is a method for producing the metal-polyolefin joint body as described in [15], wherein When molding the polyolefin by injection molding or press molding, the surface on the resin coating layer side is joined and integrated with the polyolefin.

[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 in which a thermoplastic epoxy resin produced by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol resin is combined with maleic anhydride modified polyolefin The reaction becomes. [19] The modified polyolefin resin composition according to [17] or [18], wherein the total amount of the bifunctional epoxy resin and the bifunctional phenol resin relative to 100 parts by mass of the maleic anhydride modified polyolefin is 5~100 parts by mass. [Effects of Invention]

According to the present invention, it is possible to provide a composite laminate suitable for the application of firmly joining a metal material and a polyolefin and its related technology.

A detailed description will be given of the composite laminate and related technologies of the embodiment of the present invention.

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

＜Metal material 2＞ The metal type of the metal material 2 is not particularly limited. Examples of metal types include aluminum, iron, titanium, magnesium, stainless steel, copper, and the like. Among these, aluminum is particularly suitable from the viewpoints of lightness and ease of processing. In addition, in the present invention, the term "aluminum" is used to mean the simple substance of aluminum and its alloys. Similarly, iron, titanium, magnesium, and copper are also used as meanings that include these simple substances and their alloys.

Before laminating the resin coating layer 3 on the metal material 2, it is better to apply pretreatment to the surface of the metal material.

As the pretreatment, for example, washing with a solvent or the like, degreasing treatment, sandblasting treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, chemical conversion treatment, etc. are mentioned, and treatment before hydroxyl groups are generated on the surface of the metal material is preferred. Only one kind of these pretreatments may be applied, or two or more kinds may be applied. As a specific method of these pretreatments, conventional methods can be used. The pre-treatment is to remove the surface contaminants of the metal material 2 and/or to form fine concavities and convexities 21 on the surface of the metal material 2 for the purpose of anchoring effect to roughen the surface. Thereby, the adhesion between the surface of the metal material and the resin coating layer can be improved, and it can also help to improve the adhesion with the bonding objects of various materials (metal materials, organic materials, etc.).

Therefore, when manufacturing a composite laminate, before forming the resin coating layer, it is preferable to apply to the metal material to remove the surface contaminants of the metal material 2 and to form fine irregularities 21 on the surface of the metal material 2 for the purpose of anchoring effect. The roughening treatment is, specifically, a pretreatment selected from at least one of the group consisting of sandblasting treatment, polishing treatment, etching treatment, and chemical conversion treatment.

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

As the aforementioned sandblasting treatment, for example, shot blast, sandblasting, and the like can be cited.

As the aforementioned polishing treatment, for example, buff polishing using a polishing cloth, roll polishing using abrasive paper (sand paper), electrolytic polishing, and the like can be cited.

The so-called plasma treatment includes the use of plasma to process a high-voltage power supply, which strikes the surface of the material with a plasma beam coming out of a rod called an electrode, firstly cleans the foreign matter and oil film on the surface, and then puts it in A method of exciting surface molecules in response to the gas energy of the material, and a surface-based atmospheric piezoelectric slurry treatment method that can give hydroxyl or polarity.

The so-called laser treatment refers to a technology that only rapidly heats and cools the surface layer by laser irradiation to improve the surface characteristics, and it is an effective method for roughening the surface. The conventional laser processing technology can be used.

Examples of the aforementioned etching treatment include chemical etching treatments such as alkaline method, phosphoric acid-sulfuric acid method, fluoride method, chromic acid-sulfuric acid method, and ferric chloride method, or electrochemical etching treatment such as electrolytic etching method. When the metal material is aluminum, the etching treatment is preferably an alkaline method using an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and particularly preferably a caustic soda method using an aqueous sodium hydroxide solution. As the aforementioned alkaline method, for example, the aluminum substrate can be immersed in an aqueous solution of sodium hydroxide or potassium hydroxide with a concentration of 3 to 20% by mass at 20 to 70° C. for 1 to 15 minutes. As additives, chelating agents, oxidizing agents, phosphates, etc. can be added. After the aforementioned immersion, it is preferably neutralized (desmuted) with a 5-20% by mass nitric acid aqueous solution, etc., washed with water and dried.

The aforementioned so-called chemical conversion treatment mainly refers to forming a chemical conversion film on the surface of a metal material.

As the chemical conversion treatment, for example, diaspore treatment, zirconium treatment, and the like can be cited. The diaspore treatment is to form a diaspore film on the surface of the aluminum substrate by subjecting the aluminum substrate to hot water treatment. As a reaction accelerator, ammonia, triethanolamine, etc. can be added to the water. For example, it is preferable to immerse the aluminum base material in hot water containing triethanolamine at a concentration of 0.1 to 5.0% by mass at 90 to 100° C. for 3 seconds to 5 minutes. The zirconium treatment involves immersing an aluminum substrate in a zirconium salt-containing solution such as zirconium phosphate to form a zirconium compound film on the surface of the substrate. For example, it is preferable to immerse the aluminum substrate in a chemical conversion agent for zirconium treatment (for example, "Palcoat 3762" made by Parker Nasei Co., Ltd., the same as "Palcoat 3796", etc.) at a temperature of 45 to 70°C for 0.5 to 3 minutes To proceed. The aforementioned zirconium treatment is preferably performed after the etching treatment by the aforementioned caustic soda method.

When the metal material is aluminum, it is particularly preferable to include at least one pretreatment selected from etching treatment and diaspore 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 modified polyolefin.

Since such a predetermined resin coating layer is laminated on the aforementioned metal material, the composite laminate of this embodiment can exhibit excellent adhesion to polyolefin.

A plurality of layers including the modified polyolefin layer 31 and layers other than the modified polyolefin layer may constitute the resin coating layer, and the layer other than the modified polyolefin layer may be selected from the group consisting of thermoplastic epoxy resins. At least one of the thermoplastic epoxy resin layer 32 formed of the resin composition of the above and the thermosetting resin layer 33 formed of the resin composition containing the thermosetting resin.

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

The aforementioned modified polyolefin layer 31 is preferably at least one selected from the group consisting of a layer containing reactant 1, a layer containing reactant 2, and a layer containing a mixture of thermoplastic epoxy resin and polyolefin; The reactant 1 is based on the presence of maleic anhydride-modified polyolefin, so that the bifunctional epoxy resin and the bifunctional phenol compound undergo addition polymerization reaction, and at the same time, it also modifies the maleic acid in the polyolefin skeleton with maleic anhydride. The reaction product 2 is obtained by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound, and maleic anhydride is used to modify the horse in the polyolefin skeleton. Derived from the reaction of acid anhydride.

(Reactant 1) Reactant 1 can be obtained by performing addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound in a solution of a polyolefin modified by maleic anhydride in the presence of a catalyst. At this time, the maleic anhydride-modified polyolefin is considered to be produced with a bifunctional epoxy resin, a bifunctional phenol compound, and a bifunctional epoxy resin and a bifunctional phenol compound described later in the item of reactant 2. The thermoplastic epoxy resin reacts.

(Maleic anhydride modified polyolefin) The maleic anhydride-modified polyolefin is a polyolefin grafted with maleic anhydride, and there are maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and the like. There are Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW manufactured by Kayaku Akzo, Modic series manufactured by Mitsubishi Chemical Corporation, etc. In addition, SCONA TPPP2112GA, TPPP8112GA, and TPPP9212GA manufactured by BYK can be used together as a polypropylene additive functionalized with maleic anhydride.

(2-functional epoxy resin) As said bifunctional epoxy resin, a bisphenol type epoxy resin and a biphenyl type epoxy resin are mentioned, for example. Among these, one type may be used alone, or two or more types may be used in combination. Specifically, "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Corporation, the same as "jER (registered trademark) 834", the same as "jER (registered trademark) 1001", and the same as "jER (registered trademark) 1004" , Same as "jER (registered trademark) YX-4000" etc.

(2-functional phenol compound) As said bifunctional phenol compound, bisphenol, biphenol, etc. are mentioned, for example. Among these, one type may be used alone, or two or more types may be used in combination. Moreover, as these combinations, for example, 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 can be cited. Also, for example, a combination of "WPE190" made by Nagase Chemical Co., Ltd. and "EX-991L" can also be cited.

As a catalyst for the addition polymerization of thermoplastic epoxy resins, for example, tertiary amines such as triethylamine, 2,4,6-gins(dimethylaminomethyl)phenol, etc.; triphenyl Phosphorus compounds such as phosphine, etc.

(Reactant 2) The reactant 2 is obtained by reacting the thermoplastic epoxy resin produced by the addition polymerization reaction of the bifunctional epoxy resin and the bifunctional phenol compound with the maleic anhydride modified polyolefin. As the maleic anhydride-modified polyolefin, the bifunctional epoxy resin, and the bifunctional phenol compound used in this reaction, the same ones as those used in the production of the reactant 1 can be used.

(Thermoplastic epoxy resin) The thermoplastic epoxy resin used in the production of the aforementioned reactant 2 is also called in situ polymerizable phenoxy resin, in situ hardening phenoxy resin, in situ hardening epoxy resin, etc. , By the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound in the presence of a catalyst to form a thermoplastic structure, that is, a linear polymer structure. Here, a linear polymer means a one-dimensional linear polymer without a cross-linked structure in the polymer molecule. Thermoplastic epoxy resin is different from the thermosetting resin constituting the three-dimensional network of the cross-linked structure, and has thermoplasticity.

When the total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in the production of the aforementioned reactant 1 and reactant 2, when the maleic anhydride-modified polyolefin is set to 100 parts by mass, it is preferably 5-100 Parts by mass, more preferably 5-60 parts by mass, still more preferably 10-30 parts by mass.

In addition, the reaction modes that occur when obtaining the aforementioned reactant 1 and the aforementioned reactant 2 are the reaction of maleic anhydride-modified polyolefin and bifunctional epoxy resin, the reaction of maleic anhydride-modified polyolefin and bifunctional phenol compound, The reaction between the epoxy group and maleic anhydride, the reaction between the epoxy group at the end of the thermoplastic epoxy resin and maleic anhydride, the reaction between the secondary hydroxyl group in the thermoplastic epoxy resin skeleton and the maleic anhydride, etc. involve various , And it is not possible to express the specific state based on its combination in a comprehensive manner. Therefore, it can be said that it is impossible or impractical to directly specify the modified polyolefin obtained as the aforementioned reactant 1 and the aforementioned reactant 2 by the structure or characteristics.

The aforementioned mixture of thermoplastic epoxy resin and polyolefin can be obtained by mixing the same thermoplastic epoxy resin used in the aforementioned production of reactant 2 with polyolefin by a common method.

(Polyolefin) As the polyolefin used to form the aforementioned mixture, the polyolefin used as the joined body can be used as it is. The polyolefin is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene, etc.

The resin coating layer is laminated on the surface of the metal material. As mentioned above, the resin coating layer can be laminated on the surface of the metal material that has not been pre-treated, or can be laminated on the surface of the metal material that has been pre-treated. 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 constituted by a plurality of layers of the modified polyolefin layer and other layers, and at least one of the layers other than the modified polyolefin layer may be formed of a resin composition containing a thermoplastic epoxy resin. It is composed of a thermoplastic epoxy resin layer 32. The aforementioned resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably contains 70% by mass or more.

(Thermoplastic epoxy resin) The thermoplastic epoxy resin is the same as the thermoplastic epoxy resin used in the production of the above-mentioned reactant 2. By the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound in the presence of a catalyst, a thermoplastic structure is formed , That is, the resin of the linear polymer structure, which is different from the thermosetting resin that constitutes the three-dimensional network of the cross-linked structure, has thermoplasticity. Due to the characteristics of the thermoplastic epoxy resin, by in-situ polymerization, it is possible to form a thermoplastic epoxy resin layer 32 with excellent adhesion to metal materials and excellent adhesion with the modified polyolefin layer 31.

Therefore, when manufacturing the composite laminate, it is preferable to form the thermoplastic epoxy resin layer 32 on the surface of the lower layer by the addition polymerization reaction of the composition containing the monomer of the thermoplastic epoxy resin. The addition polymerization reaction of the composition containing the monomer of the thermoplastic epoxy resin is preferably performed on the surface of the functional group-containing layer as the lower layer. The resin coating layer 3 including the thermoplastic epoxy resin layer formed in this manner has excellent adhesion to metal materials, and has excellent adhesion to the bonding object described later.

The coating method of forming the thermoplastic epoxy resin layer 32 from the composition containing the monomer of the thermoplastic epoxy resin is not particularly limited, but, for example, a spray coating method, a dipping method, etc. may be mentioned.

In addition, in order to make the addition polymerization reaction of the thermoplastic epoxy resin fully proceed to form the desired resin coating layer, the composition containing the monomer of the thermoplastic epoxy resin may contain additives such as a solvent or a coloring agent as needed . In this case, among the components other than the solvent of the aforementioned composition, the monomer of the thermoplastic epoxy resin is preferably the main component. The aforementioned main component means that the content of the thermoplastic epoxy resin is 50-100% by mass. The aforementioned 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.

Although the aforementioned addition polymerization reaction depends on the type of reaction compound, etc., it is preferably carried out by heating at 120 to 200°C for 5 to 90 minutes. Specifically, after coating the aforementioned resin composition, it is appropriate to volatilize the solvent, and then heat to perform an addition polymerization reaction, whereby a thermoplastic epoxy resin layer can be formed.

[Thermosetting resin layer 33] The resin coating layer 3 is constituted by a plurality of layers including the modified polyolefin layer and layers other than the modified polyolefin layer. The layers other than the modified polyolefin layer may also be composed of a resin containing a thermosetting resin It is composed of a thermosetting resin layer 33 formed by the object.

In addition, in order to fully advance the curing reaction of the thermosetting resin to form a desired resin coating layer, the resin composition containing the thermosetting resin may contain additives such as a solvent or a coloring agent as needed. In this case, among the components other than the solvent of the resin composition, the thermosetting resin is preferably the main component. The aforementioned main component means that the content of the aforementioned thermosetting resin is 40-100% by mass. The aforementioned 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 resins, epoxy resins, vinyl ester resins, and unsaturated polyester resins.

The thermosetting resin layer 33 may be formed by a single type of these resins, or may be formed by mixing two or more types. 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 different kinds of thermosetting resins.

The coating method for forming the thermosetting resin layer 33 from the composition containing the monomer of the thermosetting resin is not particularly limited, but, for example, a spray coating method, a dipping method, etc. may be mentioned.

In addition, the thermosetting resin in this embodiment is used to broadly mean a resin that undergoes cross-linking and curing, and is not limited to a heat-curing type, and includes a room-temperature curing type or a light-curing type. The aforementioned light-curing type can also be cured in a short time by irradiation of visible light or ultraviolet light. The aforementioned light-curing type, heat-curing type and/or room-temperature curing type can be used in combination. Examples of the photocurable type include vinyl ester resins such as "Ripoxy (registered trademark) LC-760" manufactured by Showa Denko Corporation and the same "Ripoxy (registered trademark) LC-720".

(Urethane resin) The aforementioned urethane resin is generally a resin obtained by the reaction of the isocyanate group of the isocyanate compound and the hydroxyl group of the polyol compound, preferably equivalent to ASTM D16, which is defined as "vehicle non-volatile Polyisocyanate-containing coatings with a composition of more than 10wt%" are urethane resins. The aforementioned urethane resin may be a one-component type or a two-component type.

As one-liquid type urethane resin, for example, oil modified type (hardened by oxidative polymerization of unsaturated fatty acid groups), moisture hardened type (by isocyanate groups and water in the air) It is hardened by reaction), blocked type (blocking agent is dissociated by heating, and the regenerated isocyanate group reacts with hydroxyl to harden), lacquer type (hardened by solvent volatilization and drying), etc. Among these, in terms of ease of handling, etc., a moisture-curable one-liquid urethane resin is suitably used. Specifically, "UM-50P" manufactured by Showa Denko Co., Ltd. can be cited.

The two-component urethane resin includes, for example, a catalyst hardening type (the isocyanate group reacts with water in the air to harden in the presence of a catalyst), and the polyol hardening type (by isocyanate The acid group reacts with the hydroxyl group of the polyol compound to harden), etc.

Examples of the polyol compound in the polyol curing type include polyester polyol, polyether polyol-phenol resin, and the like. In addition, examples of the isocyanate compound having an isocyanate group in the polyol curing type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimer acid diisocyanate; 2 ,4- or 2,6-Tylenylene diisocyanate (TDI) or its mixture, p-phenylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or its polynuclear mixture Aromatic isocyanates such as polymeric MDI; alicyclic isocyanates such as isophorone diisocyanate (IPDI), etc. The blending ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably a molar equivalent ratio of hydroxyl group/isocyanate group in the range of 0.7 to 1.5 .

As the urethane catalyst used in the aforementioned two-component urethane resin, for example, triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethyl Hexane-1,6-diamine, dimethyl ether amine, N,N,N',N”,N”-pentamethyldipropylene-triamine, N-methylmorpholine, bis( 2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and other amine catalysts; dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, Organotin catalysts such as dibutyl tin dimaleate. In the polyol curing type, it is generally preferable to blend 0.01 to 10 parts by mass of the urethane catalyst with respect to 100 parts by mass of the polyol compound.

(Epoxy resin) The aforementioned epoxy resin is a resin having at least two epoxy groups in one molecule. As the prepolymer before curing of the aforementioned epoxy resin, for example, ether type bisphenol type epoxy resin, novolak type epoxy resin, polyphenol type epoxy resin, aliphatic type epoxy resin, and ester type aromatic resin can be cited. Among these, bisphenol A type epoxy resins are suitable for use among group epoxy resins, cycloaliphatic epoxy resins, ether and ester epoxy resins, and the like. Among these, one type may be used alone, or two or more types may be used in combination. As the bisphenol A epoxy resin, specifically, "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Co., Ltd., the same "jER (registered trademark) 1001", and the like can be cited. Specific examples of novolac-type epoxy resins include "D.E.N. (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.

Examples of the curing agent used for the epoxy resin include conventional curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, mercaptans, imidazoles, and cationic catalysts. The aforementioned curing agent can be used in combination with long-chain aliphatic amines or/and mercaptans to obtain the effects of high elongation and excellent impact resistance. As specific examples of the aforementioned thiols, the same compounds as those exemplified as the thiol compound for forming the functional group-containing layer described later can be cited. Among them, from the viewpoint of elongation and impact resistance, pentaerythritol 4 (3-mercaptobutyrate) (for example, "KarenzMT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.) is preferred.

(Vinyl ester resin) The said vinyl ester resin is what melt|dissolved a vinyl ester compound in a polymerizable monomer (for example, styrene etc.). Although it may be called an epoxy (meth)acrylate resin, among the aforementioned vinyl ester resins, it is assumed that the urethane (meth)acrylate resin is also included. As the aforementioned vinyl ester resin, for example, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Paint Terms" (Colored Materials Association, published in 1993), etc. can also be used. For example, "Ripoxy (registered trademark) R-802" manufactured by Showa Denko Co., Ltd., the same "Ripoxy (registered trademark) R-804", and the same "Ripoxy (registered trademark) R-806".

As the aforementioned urethane (meth)acrylate resin, for example, after reacting an isocyanate compound with a polyol compound, a hydroxyl-containing (meth)acrylic monomer (and, if necessary, a hydroxyl-containing allyl Base ether monomer) to obtain an oligomer containing a radically polymerizable unsaturated group. Specifically, "Ripoxy (registered trademark) R-6545" manufactured by Showa Denko Co., Ltd. can be cited.

The aforementioned vinyl ester resin can be cured by radical polymerization caused by heating in the presence of a catalyst such as organic peroxide. The organic peroxide is not particularly limited, but for example, ketone peroxides, peroxide ketals, hydrogen peroxides, diallyl peroxides, diacyl peroxides, and peroxides can be cited. Oxyesters, peroxydicarbonates, etc. By combining these with cobalt metal salt, etc., it becomes possible to harden at room temperature. The cobalt metal salt is not particularly limited, but examples thereof include cobalt naphthenate, cobalt octoate, and cobalt hydroxide. Among these, cobalt naphthenate or/and cobalt octoate are preferred.

(Unsaturated polyester resin) In the aforementioned unsaturated polyester resin, the condensation product (unsaturated polyester) obtained by the esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is dissolved in a polymerizable monomer (for example, , Styrene, etc.). As the aforementioned unsaturated polyester resin, those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary" (Color Materials Association, published in 1993), etc. can also be used. For example, "Rigolac (registered trademark)" manufactured by Showa Denko Co., Ltd. can be cited.

The aforementioned unsaturated polyester resin can be cured by radical polymerization caused by heating in the presence of the same catalyst as in the aforementioned vinyl ester resin.

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

Therefore, the resin coating layer can impart excellent bonding properties between the metal material and the polyolefin to be bonded. Furthermore, as described above, even in the state where the surface of the metal material is protected, for a long period of several months, it is possible to obtain a composite laminate that can maintain a state of excellent adhesion.

As described above, the resin coating layer plays a role of imparting excellent bonding properties to the polyolefin to be bonded to the metal material. The resin coating layer can also be said to be the primer layer of the composite laminate. The term “undercoat layer” here means that, when a metal material and a resin material are joined and integrated, such as a metal-polyolefin joined body described later, it is interposed between the metal material and the joining object to increase the resistance of the metal material. The layer of adhesion of the bonding object.

＜Functional base layer 4＞ As shown in FIG. 2, between the metal material 2 and the resin coating layer 3, there may also be a functional group-containing layer 4 that is in contact with the metal material 2 and the resin coating layer 3 and laminated one or more layers. In the case of a functional group-containing layer, the chemical bond formed by the functional group of the functional group-containing layer reacts with the hydroxyl group on the surface of the metal material and the functional group of the resin constituting the resin coating layer to form a chemical bond, which can be improved The effect of the adhesion between the surface of the metal material and the resin coating layer can also help improve the adhesion with the bonding object.

"deal with" 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 (1') to (7') below. (1') Silane coupling agent containing at least one functional group selected from the group consisting of glycidyl group, amine group and sulfhydryl group (2') Combination of at least one selected from the group consisting of glycidyl compounds and thiol compounds and a silane coupling agent having an amino group (3') selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic acid groups and glycidyl groups, and compounds having (meth)acrylic acid groups and amino groups A combination of at least one of them and a silane coupling agent with a mercapto group (4') Combination of thiol compound and silane coupling agent with (meth)acryloyl group (5') A combination of at least one selected from the group consisting of a compound having an amine group and a (meth)acrylic acid group, an amine group compound, and a thiol compound, and a silane coupling agent having a glycidyl group (6’) Isocyanate compound (7’) Thiol compound "Functional Group" The functional group-containing layer 4 preferably includes a functional group introduced by the aforementioned treatment, and specifically, preferably includes at least one functional group selected from the group consisting of the following (1) to (7). (1) A functional group derived from a silane coupling agent and selected from at least one of the group consisting of a glycidyl group, an amine group, and a sulfhydryl group (2) A functional group formed by reacting at least one selected from a glycidyl compound and a thiol compound with an amine group derived from a silane coupling agent (3) Selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and glycidyl groups, and compounds having (meth)acrylic groups and amino groups At least one of them reacts with a sulfhydryl group derived from a silane coupling agent to form a functional group (4) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent (5) At least one selected from the group consisting of a compound having an amine group and a (meth)acryloyl group, an amine group compound, and a thiol compound is reacted with a glycidyl group derived from a silane coupling agent Functional group (6) Isocyanate groups derived from isocyanate compounds (7) Sulfhydryl groups derived from thiol compounds

It is also possible to apply pretreatment to the surface of the metal material before forming the functional group-containing layer 4 on the metal material. By applying pre-treatment, the anchoring effect caused by the fine unevenness 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, respectively. The additive effect of the formed chemical bond can also improve the adhesion between the surface of the metal material and the resin coating layer, and the adhesion with the bonding object.

The method for forming the functional group-containing layer by the silane coupling agent, the isocyanate compound, the thiol compound, and the like is not particularly limited, but, for example, a spray coating method, a dipping method, and the like can be mentioned. Specifically, the metal material can be immersed in a solution of a silane coupling agent with a concentration of 5-50% 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, etc. The way to proceed.

[Silane Coupling Agent] As the aforementioned silane coupling agent, for example, those conventionally used for the surface treatment of glass fiber can be used. The silanol group generated by the hydrolysis of the silane coupling agent, or its oligomerized silanol group, reacts with the hydroxyl groups present on the surface of the metal material to bond, and the metal material 2 can be given (introduced) energy and resin coating. The coating 3 chemically bonds the functional groups based on the structure of the silane coupling agent.

The silane coupling agent is not particularly limited, but for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amine Silane coupling agent with amino group such as propyl propyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl trimethoxy Silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy Silane and other epoxy-containing silane coupling agents, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, dithiol triazinepropyltriethoxysilane, etc. have mercapto groups Or isocyanate-based silane coupling agent, vinyl trimethoxy silane, vinyl triethoxy silane, p-styryl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Silane coupling agents with vinyl groups such as acryloxypropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-benzene 3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminopropyltrimethoxysilane hydrochloride, ginseng-(trimethoxysilylpropyl)isotris Polycyanate ester, 3-ureidopropyl trialkoxysilane. These may be used individually by 1 type, and may use 2 or more types together.

[Isocyanate compound] The aforementioned isocyanate compound is based on the reaction between the isocyanate group in the isocyanate compound and the hydroxyl group present on the surface of the metal material 2 to bond, whereby the metal material can be given (introduced) a basis that can chemically bond with the resin coating layer 3 The functional group of the structure of the isocyanate compound.

The isocyanate compound is not particularly limited, but for example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate, which are polyfunctional isocyanates In addition to (IPDI), etc., 2-isocyanatoethyl methacrylate (for example, "KarenzMOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl methacrylate, an isocyanate compound having a radical reactive group, and 2- Ethyl isocyanate (for example, "KarenzAOI (registered trademark)" manufactured by Showa Denko Co., Ltd., the same as "AOI-VM (registered trademark)"), 1,1-(bisacryloxyethyl) ethyl Isocyanate (for example, "KarenzBEI (registered trademark)" manufactured by Showa Denko Co., Ltd.) and the like.

[Thiol compound] The aforementioned thiol compound is that the mercapto group in the thiol compound reacts with the hydroxyl group present on the surface of the metal material 2 to bond, and thereby the metal material can be given (introduced) chemically bonded to the resin coating layer or the bonding object. A functional group based on the structure of the thiol compound.

The thiol compound is not particularly limited, but for example, pentaerythritol 4 (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Co., Ltd., and "QE-340M" manufactured by Toray Fine Chemical Co., Ltd.) ), ether-based first-class mercaptan (for example, "Capcure3-800" manufactured by Cognis), 1,4-bis(3-mercaptobutoxy)butane (for example, manufactured by Showa Denko Co., Ltd.) KarenzMT (registered trademark) BD1"), pentaerythritol 4 (3-mercaptobutyrate) (for example, "KarenzMT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.), 1,3,5-gin (3-mercaptobutyrate) Oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (for example, "KarenzMT (registered trademark) NR1" manufactured by Showa Denko Co., Ltd.), etc. .

[Metal-Polyolefin Joint 5] As shown in FIG. 3, the metal-polyolefin junction body 5 of this embodiment uses the resin coating layer 3 of the composite laminate 1 as the undercoat layer as described above, and the surface of the undercoat layer is connected to the polyolefin 6 Joined and integrated.

Although the thickness of the primer layer (thickness after drying) depends on the material of the bonding object or the contact area of the bonding portion, from the viewpoint of obtaining excellent adhesion between the surface of the primer layer and the polyolefin, It is preferably 1 μm to 500 μm, more preferably 3 μm to 100 μm, and still more preferably 5 μm to 70 μm. In addition, when the aforementioned primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) shall be the total thickness of each layer.

The polyolefin in the aforementioned metal-polyolefin junction is not particularly limited, as long as it is a general synthetic resin. For example, polyethylene, polypropylene, etc. Generally speaking, polypropylene can be classified into a homopolymer with high rigidity that polymerizes only propylene, a random polymer with high transparency and flexibility that copolymerizes a small amount of ethylene, and a rubber component (EPR) that is uniformly and finely dispersed in a uniform and random A block copolymer with high impact resistance of the polymer, but it may be any one. In addition, it may also be a type that contains talc, glass fiber, and carbon fiber to increase the strength. The product containing talc has the trade name TRC104N manufactured by SunAllomer Corporation, the product containing glass fiber has the product name PP-GF40-01 F02 manufactured by Daisil Polymer Co., and the one containing carbon fiber has the product name PP- made by Daisil Polymer Co. CF40-11 F008 and so on.

As a method of manufacturing the aforementioned metal-polyolefin joint body, the separately produced composite laminate and the aforementioned resin material molded body can be joined and integrated together. In addition, at the same time as molding the aforementioned resin material, it may be joined and integrated with the composite laminate. Specifically, for example, when the resin material is molded by injection molding, press molding, transfer molding, etc., the surface of the undercoat layer side of the composite laminate is joined and integrated with the resin material to obtain a metal-polymer Olefin conjugation. [Example]

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

＜Manufacturing example 1＞ The flask was charged with maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g, and xylene: 95 g, and the temperature was raised to 125°C for dissolution while stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.: polycondensate of bisphenol A and epichlorohydrin): 1.01 g, bisphenol A: 0.24 g, 2,4, 6-Ginseng (dimethylaminomethyl)phenol: 0.006g into the flask, stir at 125°C for 30 minutes to obtain a Malay modified with thermoplastic epoxy resin, bifunctional epoxy resin, and bifunctional phenol compound Polypropylene modified by acid anhydride: PP-1 modified.

＜Manufacturing example 2＞ The flask was charged with maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g, and xylene: 95 g, and the temperature was raised to 125°C for dissolution while stirring. Next, a bifunctional epoxy resin (jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation: 0.49 g, bisphenol A: 0.06 g, 2,4,6-ginseng (dimethylaminomethyl) phenol) was added. : 0.003g into the flask, stirring at 125°C for 30 minutes to obtain maleic anhydride modified polypropylene modified with thermoplastic epoxy resin, bifunctional epoxy resin, and bifunctional phenol compound: modified PP-2.

＜Manufacturing example 3＞ Into the flask, talc-containing polypropylene (TRC104N manufactured by SunAllomer Co., Ltd.): 5 g and xylene: 95 g were fed, and the temperature was raised to 125°C for dissolution while 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-ginseng (dimethylaminomethyl)phenol : 0.006g into the flask, stirring 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＞ Xylene: 95g, bifunctional epoxy resin (jER1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.20g, bisphenol A: 0.066g, 2,4,6-ginseng (dimethylaminomethyl) were fed into the flask. ) Phenol: 0.003 g, stirred at 125°C for 30 minutes to react to obtain a thermoplastic epoxy resin solution. Next, maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g was poured into the flask and dissolved to obtain maleic anhydride modified with thermoplastic epoxy resin (20% by mass) Modified polypropylene: Modified PP-4.

<Example 1-1> (Pre-treatment) An aluminum plate (A6063) with a thickness of 18mm×45mm and a thickness of 1.5mm is immersed in a 5 mass% sodium hydroxide aqueous solution for 1.5 minutes, then neutralized with a 5 mass% nitric acid aqueous solution, washed with water, and dried to perform etching treatment . Next, the aluminum plate after the etching treatment is boiled in pure water for 10 minutes, and then baked at 250° C. for 10 minutes to perform a diaspore treatment to form a diaspore film on the surface of the aluminum plate. The SEM photograph (scanning electron microscope photograph, 45° oblique observation) observed the surface of the aluminum plate after the diaspore treatment. As shown in Fig. 4, it was confirmed that a diaspore film with burr-like irregularities was formed on the surface. .

(Containing functional base layer) Next, the aluminum plate after the diaspore treatment was immersed in 2 g of 3-aminopropyltrimethoxysilane ("KBM-903" manufactured by Shin-Etsu Silicon Co., Ltd.; silane coupling agent) dissolved in 1000 g of industrial ethanol After 20 minutes of the resulting solution containing the silane coupling agent at 70°C, the aluminum plate was taken out and dried to form a functional group-containing layer on the surface of the diaspore film.

(Resin coating) Next, the modified PP-1 obtained in Production Example 1 was applied to the surface of the functional base-containing layer to volatilize xylene, and kept at 150°C for 30 minutes, and a modified PP-1 with a thickness of 30 μm was formed on the surface of the functional base-containing layer. A composite laminate of PP-1 resin coating layer.

<Example 1-2> On the surface of the resin coating layer side of the composite laminate produced in Example 1-1, a polypropylene resin (PP resin) (TRC104N manufactured by SunAllomer Co., Ltd.) (joint object) mixed with talc was used in an injection molding machine ( SE100V manufactured by Sumitomo Heavy Machinery Industry Co., Ltd.; barrel temperature 200°C, tool temperature 30°C, injection speed 50mm/sec, peak/hold pressure 195/175[MPa/MPa]) for injection molding to produce ISO19095 Test piece for tensile test (PP resin, 10 mm × 45 mm × 3 mm, joint length 5 mm) (metal-polyolefin joint body).

[Subsequent evaluation] The test piece (metal-polyolefin joint) produced in Example 1-2 was placed at room temperature for 1 day, and then used in accordance with ISO19095 1-4 with a tensile testing machine (Universal Testing Machine Autograph "AG" manufactured by Shimadzu Corporation -IS"; load element 10kN, tensile speed 10mm/min, temperature 23°C, 50%RH) conduct tensile shear bonding strength test to measure bonding strength. The measurement results are shown in Table 1 below.

<Example 2-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating layer: the first layer) Thermoplastic epoxy resin prepared by dissolving bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 24 g, and triethylamine: 0.4 g in 250 g of acetone The composition was sprayed on the surface of the functional base-containing layer so that the thickness after drying became 30 μm. After placing the solvent in the air at room temperature for 30 minutes to volatilize the solvent, place it in an oven at 150°C for 30 minutes for the addition polymerization reaction, and let it cool to room temperature to form the first resin coating layer (thermoplastic epoxy resin). Layer 32).

(Resin coating layer: 2nd layer) Next, the modified PP-2 obtained in Production Example 2 was coated on the surface of the aforementioned thermoplastic epoxy resin layer to volatilize xylene and kept at 150°C for 30 minutes to fabricate it on the surface of the aforementioned thermoplastic epoxy resin layer A composite laminate formed with a resin coating layer (modified polyolefin layer 31) of modified PP-2 with a thickness of 30 μm.

<Example 2-2> On the surface on the resin coating layer side of the second layer of the composite laminate produced in Example 2-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 3-1> (Pre-treatment) For copper plates of 18mm×45mm and thickness of 1.5mm, degreasing treatment with acetone.

(Containing functional base layer) Next, the copper plate after the aforementioned degreasing treatment was immersed in 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Silicon Co., Ltd.; silane coupling agent) dissolved in industrial ethanol After 5 minutes of 100 g of the silane coupling agent solution at 70°C, the copper plate was taken out and dried, and functional groups derived from the silane coupling agent were introduced on the surface of the copper plate after the degreasing treatment. Then, it was further immersed in the bifunctional thiol compound 1,4bis(3-mercaptobutanoyloxy)butane (KarenzMT BD1 manufactured by Showa Denko Co., Ltd.): 0.6g, 2,4,6-ginseng (dimethyl (Aminomethyl)phenol (DMP-30): 0.05g dissolved in 150g of toluene in a solution at 70°C for 10 minutes, then lifted up and dried. In this way, a two-layer functional base layer is formed.

(Resin coating) Next, the modified PP-3 obtained in Production Example 3 was coated on the surface of the functional group-containing layer of the aforementioned copper plate to volatilize xylene and kept at 150°C for 30 minutes to form a thickness of 30μm on the surface of the aforementioned functional group-containing layer It is a composite laminate of modified PP-3 resin coating layer.

<Example 3-2> On the surface of the resin coating layer side of the composite laminate produced in Example 3-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 4-1> (Pre-treatment) For the iron plate of 18mm×45mm and thickness of 1.5mm, use #100 sandpaper for sanding treatment to form fine irregularities on the surface of the iron plate.

(Resin coating layer: the first layer) The same operation as in Example 2-1 was performed on the aforementioned uneven surface 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 performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 4-2> On the surface of the resin coating layer side of the composite laminate produced in Example 4-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 1 below.

<Comparative Example 1-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

<Comparative Example 1-2> On the surface of the diaspore film of the aluminum plate produced in Comparative Example 1-1, the functional base layer and resin coating layer were not provided, and the same injection molding operation as in Example 1-2 was performed, but the aforementioned PP resin was not adhered to the aforementioned On the surface of the diaspore film, metal-polyolefin joints cannot be made.

<Comparative Example 2-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating) Then, on the surface of the functional base-containing layer, a solution of maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5g dissolved in 95g of xylene was applied to make two Toluene was volatilized and kept at 150°C for 30 minutes to produce a composite laminate in which a maleic anhydride modified polypropylene layer with a thickness of 30 μm was formed on the surface of the functional base-containing layer.

＜Comparative example 2-2＞ On the surface of the resin coating layer side of the composite laminate produced in Comparative Example 2-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 1 below.

<Example 5-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the aluminum plate after the diaspore treatment was immersed in 2 g of 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicon Co., Ltd.; silane coupling agent) to be dissolved in industrial After using 1000 g of ethanol in a 70°C silane-containing coupling agent solution for 20 minutes, the aluminum plate was taken out and dried to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating) Next, the modified PP-4 obtained in Production Example 4 was coated on the surface of the functional group-containing layer to volatilize xylene, and kept at 150°C for 30 minutes, and a modified PP-4 with a thickness of 30 μm was formed on the surface of the functional group-containing layer. A composite laminate of PP-4 resin coating layer.

<Example 5-2> On the surface of the resin coating layer side of the composite laminate produced in Example 5-1, glass fiber-infused polypropylene resin (PP resin) (pp-GF40-01 F02 manufactured by Dexieer Polymer Co., Ltd.) (Joint object) Injection molding was performed under the same conditions as in Example 1-2 to prepare a test piece for tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 6-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 5-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating layer: the first layer) Except that the epoxy resin was changed to jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation, the same operation as in Example 2-1 was performed to form the first resin coating layer (thermal Plastic epoxy layer).

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

<Example 6-2> On the surface on the resin coating layer side of the second layer of the composite laminate produced in Example 6-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 2 below.

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

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

(Resin coating) Next, the same operations as in Example 1-1 were performed to produce a composite laminate in which a resin coating layer of modified PP-1 with a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 7-2> On the surface of the resin coating layer side of the composite laminate produced in Example 7-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 8-1> (Pre-treatment) For an aluminum plate (A6063) of 18mm×45mm and a thickness of 1.5mm, the same sanding treatment as in Example 4-1 was performed to form fine irregularities on the surface of the aluminum plate.

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

(Resin coating layer: the first layer) The same operation as in Example 6-1 was performed 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 performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

<Example 8-2> On the surface of the resin coating layer side of the composite laminate produced in Example 8-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 2 below.

<Comparative Example 3-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

＜Comparative example 3-2＞ On the surface of the diaspore film of the aluminum plate produced in Comparative Example 3-1, the functional base layer and the resin coating layer were not provided, and the injection molding operation was performed as in Example 5-2, but the PP resin was not adhered to the aforementioned The surface of the diaspore film cannot be made into a metal-polyolefin joint.

<Comparative Example 4-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating) Next, the same operation as in Comparative Example 2-1 was performed to produce 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＞ On the surface of the resin coating layer side of the composite laminate produced in Comparative Example 4-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 2 below.

<Example 9-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

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

<Example 9-2> On the surface of the resin coating layer side of the composite laminate produced in Example 9-1, a carbon fiber-incorporated polypropylene resin (PP resin) (pp-GF40-01 F008 manufactured by Daixier Polymer Co., Ltd.) Joining object), injection molding was performed under the same conditions as in Example 1-2, and a test piece for tensile test was produced. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 10-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating layer: the first layer) Except that the epoxy resin was changed to jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Corporation, the same operation as in Example 2-1 was performed to form the first resin coating layer (thermal Plastic epoxy layer).

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

<Example 10-2> On the surface on the resin coating layer side of the second layer of the composite laminate produced in Example 10-1, the same operation as in Example 9-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 11-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to introduce a functional group derived from a silane coupling agent on the surface of the aforementioned diaspore film. Then, it was further immersed in 2-isocyanatoethyl methacrylate (Karenz MOI (registered trademark) manufactured by Showa Denko Co., Ltd.): 1.2 g, 2,4,6-ginseng (dimethylaminomethyl) Phenol (DMP-30): 0.05 g dissolved in 150 g of toluene in a solution at 70°C for 5 minutes, then lifted and dried. In this way, a functional group-containing layer is formed that extends chemically bondable functional groups in a three-dimensional direction.

(Resin coating) Next, the same operations as in Example 1-1 were performed to produce a composite laminate in which a resin coating layer of modified PP-1 with a thickness of 30 μm was formed on the surface of the functional group-containing layer.

<Example 11-2> On the surface of the resin coating layer side of the composite laminate produced in Example 11-1, the same operation as in Example 9-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 3 below.

<Example 12-1> (Pre-treatment) A 18mm×45mm, 1.5mm thick Asada bulk iron stainless steel (SUS403) steel plate was sanded in the same operation as in Example 4-1 to form fine irregularities on the surface of the aforementioned stainless steel plate.

(Functional group attachment layer) Then, the same operation as in Example 1-1 was performed to form a functional base layer on the surface of the stainless steel plate after the sanding treatment.

(Resin coating layer: the first layer) A thermoplastic epoxy resin composed of epoxy resin (jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 5.6 g, and triethylamine: 0.4 g dissolved in 196 g of acetone The substance is sprayed on the surface of the functional base-containing layer so that the thickness after drying becomes 30 μm. After placing the solvent in the air at room temperature for 30 minutes to volatilize the solvent, place it in an oven at 150°C for 30 minutes for the addition polymerization reaction, and let it cool to room temperature to form the first resin coating layer (thermoplastic epoxy resin). Floor).

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

<Example 12-2> On the surface of the resin coating layer side of the composite laminate produced in Example 12-1, the same operation as in Example 9-2 was performed to prepare a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 3 below.

<Comparative Example 5-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

<Comparative Example 5-2> On the surface of the diaspore film of the aluminum plate produced in Comparative Example 5-1, the functional base layer and resin coating layer were not provided, and the same injection molding operation as in Example 9-2 was performed, but the aforementioned PP resin was not adhered to the aforementioned The surface of the diaspore film cannot be made into a metal-polyolefin joint.

<Comparative Example 6-1> (Pre-treatment) The same operation as in Example 1-1 was performed to form a diaspore film with burr-like irregularities on the surface of an aluminum plate (A6063 of 18 mm × 45 mm, thickness 1.5 mm).

(Containing functional base layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned diaspore film.

(Resin coating) Next, the same operation as in Example 2-1 was performed to produce 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> On the surface on the resin coating layer side of the composite laminate produced in Comparative Example 6-1, the same operation as in Example 9-2 was performed to produce a test piece for a tensile test. With respect to this test piece, the bonding strength was measured in the same manner as in Example 1-2. The measurement results are shown in Table 3 below.

[產業上可利用性]

[Industrial availability]

The composite laminated system of the present invention is integrated with polyolefin, and can be used as, for example, door side panels, hoods, roofs, rear hoods, steering hooks, A-pillars, B-pillars, C-pillars, D-pillars, and extrusion boxes. , Power control unit (PCU) housing, electric compressor components (inner wall, intake port, exhaust control valve (ECV) insertion section, mounting boss, etc.), lithium ion battery (LIB) separator, battery Auto parts such as boxes, LED headlights, or smart phones, laptops, tablets, smart watches, large liquid crystal televisions (LCD-TV), outdoor LED lighting structures, etc., but not particularly limited to these examples The purpose.

1: Composite laminate 2: Metal material 21: Micro bumps 3: Resin coating layer (undercoating) 31: Modified polyolefin layer 32: Thermoplastic epoxy resin layer 33: Thermosetting resin layer 4: Functional base layer 5: Metal-polyolefin junction 6: Polyolefin

Fig. 1 is an explanatory diagram showing the structure of a composite laminate in an embodiment. [Fig. 2] is an explanatory diagram showing the structure of a composite laminate in another embodiment. Fig. 3 is an explanatory diagram showing the structure of a metal-polyolefin joint body in one embodiment. [Figure 4] is the SEM photograph of the diaspore film.

1: Composite laminate

2: Metal material

21: Micro bumps

3: Resin coating layer (undercoating)

31: Modified polyolefin layer

32: Thermoplastic epoxy resin layer

33: Thermosetting resin layer

Claims (19)

A composite laminate having a metal material and one or more resin coating layers laminated on the aforementioned metal material, At least one layer of the aforementioned resin coating layer is a modified polyolefin layer formed of a resin composition containing modified polyolefin, The aforementioned modified polyolefin layer is selected from a layer containing maleic anhydride modified polyolefin, a reactant 1 of a bifunctional epoxy resin and a bifunctional phenol compound, and a layer containing maleic anhydride modified polyolefin and a thermoplastic epoxy resin. At least one of the group of the layer of the reactant 2 and the layer containing the mixture of polyolefin and thermoplastic epoxy resin. The composite laminate of claim 1, wherein the reactant 1 is formed by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound in a solution containing maleic anhydride modified polyolefin. The composite laminate of claim 1, wherein the aforementioned reactant 2 is a thermoplastic epoxy resin produced by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol compound, and maleic anhydride is modified and polymerized. The olefin is formed by the reaction. The composite laminate of claim 1, wherein the aforementioned mixture is a mixture of polypropylene and thermoplastic epoxy resin. The composite laminate according to any one of claims 1 to 4, wherein the resin coating layer is composed of a plurality of layers including the modified polyolefin layer and layers other than the modified polyolefin layer, At least one layer other than the modified polyolefin layer is selected from a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a resin composition containing a thermosetting resin At least one of the formed thermosetting resin layers. The composite laminate of claim 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. The composite laminate of any one of claims 1 to 6, which is between the metal material and the resin coating layer, and has a functional base layer laminated in contact with the metal material and the resin coating layer, The aforementioned functional group-containing layer includes a functional group selected from at least one of the following groups (1) to (7); (1) A functional group derived from a silane coupling agent and selected from at least one of the group consisting of a glycidyl group, an amino group, a (meth)acryloyl group, and a mercapto group (2) A functional group formed by reacting at least one selected from a glycidyl compound and a thiol compound with an amine group derived from a silane coupling agent (3) Selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic groups and glycidyl groups, and compounds having (meth)acrylic groups and amino groups At least one of them reacts with a sulfhydryl group derived from a silane coupling agent to form a functional group (4) A functional group formed by reacting a thiol compound with a (meth)acryloyl group derived from a silane coupling agent (5) At least one selected from the group consisting of a compound having an amine group and a (meth)acryloyl group, and an amine group compound and a thiol compound is reacted with a glycidyl group derived from a silane coupling agent, and Functional group (6) Isocyanate groups derived from isocyanate compounds (7) Mercapto groups derived from thiol compounds. The composite laminate according to any one of claims 1 to 7, wherein the surface of the metal material is at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment, and chemical conversion treatment. Pre-processing. The composite laminate according to any one of claims 1 to 8, wherein the aforementioned metal material is aluminum. The composite laminate of claim 9, wherein the pretreatment is at least one selected from etching treatment and diaspore treatment. The composite laminate according to any one of claims 1 to 8, wherein the aforementioned metal material includes at least one selected from the group consisting of iron, titanium, magnesium, stainless steel, and copper. A method for manufacturing a composite laminate, which is the method for manufacturing a composite laminate according to any one of claims 1 to 11, wherein: The composite laminate system 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, and The aforementioned functional group-containing layer is formed by treating the surface of the aforementioned metal material with at least one selected from the group consisting of (1') to (7') below; (1') Silane coupling agent having at least one functional group selected from the group consisting of glycidyl, amino, (meth)acrylic and mercapto groups (2') A combination of at least one selected from the group consisting of glycidyl compounds and thiol compounds and a silane coupling agent having an amino group (3') selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic acid groups and glycidyl groups, and compounds having (meth)acrylic acid groups and amino groups A combination of at least one of them and a silane coupling agent with a mercapto group (4') Combination of thiol compound and silane coupling agent with (meth)acryloyl group (5') A combination of at least one selected from the group consisting of a compound having an amino group and a (meth)acrylic acid group, and a group of an amino compound and a thiol compound, and a silane coupling agent having a glycidyl group (6’) Isocyanate compound (7') Thiol compound. Such as the method for manufacturing a composite laminate of claim 12, wherein the aforementioned processing is selected from at least one of the following groups (2") to (5"); (2") After treatment with a silane coupling agent having an amine group, at least one selected from the group consisting of glycidol compounds and thiol compounds is added (3") After treatment with a silane coupling agent having a mercapto group, the addition is selected from the group consisting of glycidyl compounds, amino compounds, isocyanate compounds, compounds having (meth)acrylic acid groups and glycidyl groups, and compounds having (formaldehyde). (Base) treatment of at least one of the group consisting of acryloyl and amine compounds (4") After the treatment with the silane coupling agent with (meth)acrylic acid group, the treatment of adding thiol compound (5") After treatment with a glycidyl silane coupling agent, the addition is selected from the group consisting of compounds having amine groups and (meth)acrylic acid groups, and amine compounds and thiol compounds At least one treatment. The method for manufacturing a composite laminate of claim 12 or 13, wherein, in the case where there is a functional base-containing layer before forming the resin coating layer, before forming the functional base-containing layer, the metal material is selected from sandblasting, At least one pre-treatment in the group of polishing treatment, etching treatment and chemical conversion treatment. A metal-polyolefin joint body, which is formed by joining and integrating the surface on the resin coating layer side of the composite laminate according to any one of claims 1 to 11 and polyolefin. A method for manufacturing a metal-polyolefin joint body, which is a method for manufacturing a metal-polyolefin joint body as claimed in claim 15, wherein When molding the polyolefin by injection molding or press molding, the surface on the resin coating layer side is joined and integrated with the polyolefin. A modified polyolefin resin composition is formed by reacting maleic anhydride modified polyolefin with a bifunctional epoxy resin and a bifunctional phenol resin. A modified polyolefin resin composition, which is formed by reacting a thermoplastic epoxy resin produced by the addition polymerization reaction of a bifunctional epoxy resin and a bifunctional phenol resin with maleic anhydride modified polyolefin . The modified polyolefin resin composition of claim 17 or 18, wherein the total amount of the bifunctional epoxy resin and the bifunctional phenol resin is 5-100 parts by mass relative to 100 parts by mass of the maleic anhydride modified polyolefin.

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