JPWO2020149248A1 - Composite laminate, its manufacturing method, and metal resin joint - Google Patents

Abstract

Provided are a composite laminate capable of imparting excellent adhesiveness to a resin material to the surface of a metal base material such as aluminum, and a method for producing the same. A composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material, and the resin coating layer is surface-treated on the metal base material. At least one layer of the resin coating layer laminated on the surface comprises a resin composition containing a double-added linear polymer having a combination of double-added reactive compounds for producing a linear polymer as a constituent component. , The combination is at least one of the following (1) and (2), or at least one layer of the resin coating layer is a radical homopolymer or radical copolymer of a monofunctional monomer having an unsaturated group. It comprises a resin composition containing a certain linear polymer. (1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. At least one compound selected from and a bifunctional epoxy compound

Description

The present invention includes a composite laminate containing a metal base material and suitable for joining the metal base material and a resin material and a method for producing the same, and a metal resin bonded body and a method for producing the same using the composite laminate. Regarding.

In the fields of automobile parts and OA equipment, weight reduction of parts and products is required. In these fields, from the viewpoint of weight reduction of parts and products, composite materials in which a metal material such as aluminum and a resin material are firmly joined and integrated are often used. When aluminum is used as the metal material of these composite materials, the surface treatment of the aluminum material is performed in order to secure sufficient joint strength.

Conventionally, as a surface treatment of an aluminum material, a physical surface treatment method such as a shot blast treatment is generally used. However, these physical surface treatment methods are inferior in productivity and are not suitable for articles with thin or complicated shapes. Therefore, studies on chemical surface treatment methods for aluminum materials have been advanced. There is.

For example, a chemical surface treatment method (Patent Document 1) is known in which a metal surface coating is formed on the surface of an aluminum material and then brought into contact with an etching solution to form a porous etching layer on the surface of the material. Further, a method of forming an adhesive layer containing a modified polypropylene resin having a polar group introduced therein is also known on a base treatment film provided on the surface of a base material made of an aluminum alloy (Patent Document 2). Further, the aluminum material is immersed in an electrolytic bath of phosphoric acid or sodium hydroxide, and by direct current electrolysis, an anodic oxide film having holes having at least 85% of the holes opened on the surface having a diameter of 25 to 90 nm is formed. A method (Patent Document 3) is known in which a molten synthetic resin is injection-molded on the surface on which the anodized film is formed to improve the bonding strength by an anchor effect.

Further, a method of forming a concavo-convex thin layer of a metal oxide or a metal phosphor oxide on a fine concavo-convex surface formed by etching the surface of an aluminum material has also been proposed (Patent Document 4).

Further, a surface reaction formed by immersing a solid such as a metal material or a ceramic material in a solution containing a water-soluble alkoxysilane-containing triazinedithiol metal salt and adhering the water-soluble alkoxysilane-containing triazinedithiol metal salt to the surface of the solid. It has been proposed to use a sex solid (metal material or the like) (Patent Document 5).

Further, the polypropylene resin layer is bonded to the metal base material via a hydrophilic surface formed on the metal base material, and the thermoplastic resin molded product is compatible with the polypropylene resin layer and has an anchor effect. A metal-resin composite molded body bonded to a resin layer is known (see Patent Document 6).

Japanese Unexamined Patent Publication No. 2012-415579 Japanese Unexamined Patent Publication No. 2016-16584 Japanese Patent No. 4541153 Japanese Unexamined Patent Publication No. 2010-131888 Japanese Unexamined Patent Publication No. 2006-23677 JP-A-2017-1378

Although the surface-treated aluminum materials described in Patent Documents 1 to 3 can be satisfactorily bonded to objects to be bonded of various materials (metal materials, organic materials, etc.), it takes time to store the surface-treated aluminum materials. When joining with the object to be joined after a long period of time, there is a problem that it is difficult to obtain sufficient joining strength due to the change of the surface state with time. For example, when a surface-treated aluminum material is delivered to a molding maker and the molding maker joins the material to be joined, time often elapses for inspection, transportation, storage, etc. There is a problem that it is difficult to obtain sufficient bonding strength when the surface-treated aluminum material after a long period of time is bonded to the bonding target.

In the technique described in Patent Document 4, the surface treatment step of forming the uneven thin layer of the metal oxide or the metal phosphor oxide includes a chemical etching step of immersing the aluminum alloy in a strongly basic aqueous solution and an acidic aqueous solution of the aluminum alloy. A method including a neutralization step of immersing in an aqueous solution and a fine etching step of immersing an aluminum alloy in an aqueous solution containing one or more selected from hydrated hydrazine, ammonia, and a water-soluble amine compound (claim of Patent Document 4). 8) is adopted, so there is a problem that waste liquid treatment of hydrated hydrazine, ammonia, and water-soluble amine compound after use is required.

In the technique described in Patent Document 5, a water-soluble alkoxysilane-containing triazinedithiol metal salt can be attached to a solid surface to satisfactorily bond with a bonding target of a dissimilar material, but the water-soluble alkoxysilane-containing triazinedithiol can be bonded well. A surface-reactive solid (metal material, etc.) to which a metal salt is attached has a problem that it is difficult to obtain sufficient bonding strength when it is bonded to an object to be bonded after a long period of time has passed due to transportation, storage, or the like.

In the technique described in Patent Document 6, the viscosity is high even if the thermoplastic resin is melted, the thermoplastic resin cannot sufficiently enter into the fine holes (unevenness) on the surface of the metal base material, and sufficient bonding strength is obtained. It was difficult to obtain.

The present invention has been made in view of such a technical background, and is a composite laminate in which a metal base material and a resin coating layer are laminated, and has excellent bondability to a resin material on the surface of the composite laminate. It is an object of the present invention to provide a composite laminate to which the above is added and a method for producing the same. Another object of the present invention is to provide a metal-resin bonded body using the composite laminate and a method for producing the same.

In order to achieve the above object, the present invention provides the following means.

[1] A composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material, and the resin coating layer is the surface of the metal base material. A resin composition in which at least one layer of the resin coating layer laminated on the treated surface contains a double-addition linear polymer having a combination of double-addition-reactive compounds that produce a linear polymer as a constituent component. A composite laminate comprising a product and the combination of which is at least one of the following (1) and (2).
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. A composite laminate having at least one of the compounds selected from the above, a bifunctional epoxy compound [2] metal base material, and one or more resin coating layers laminated on the surface of the metal base material. The resin coating layer is laminated on the surface-treated surface of the metal substrate, and at least one layer of the resin coating layer is a radical homopolymer or a radical copolymer of a monofunctional monomer having an unsaturated group. A composite laminate comprising a resin composition containing a linear polymer which is a polymer.
[3] The resin coating layer is a plurality of layers, at least one of which is a cured product of a thermosetting resin, and the thermosetting resin is a urethane resin, an epoxy resin, a vinyl ester resin, and an unsaturated polyester resin. The composite laminate according to [1] or [2], which is at least one selected from the group consisting of.
[4] A functional group-adhering layer is provided between the surface of the metal base material and the resin coating layer, and the functional group-adhering layer is laminated in contact with the metal base material and the resin coating layer. The composite laminate according to any one of [1] to [3], wherein the functional group-adhering layer has a functional group introduced from at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound. body.
[5] The surface treatment is at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment, chemical conversion treatment, plasma treatment, corona discharge treatment and UV ozone treatment, according to [1] to [4]. The composite laminate according to any one.
[6] The composite laminate according to [1] to [5], wherein the metal base material is made of aluminum.
[7] The composite laminate according to [6], wherein the metal base material is made of aluminum, and the surface treatment includes at least one of an etching treatment and a boehmite treatment.
[8] The composite laminate according to [1] to [5], wherein the metal base material is made of a metal selected from the group consisting of iron, titanium, magnesium, stainless steel and copper.
[9] The composite laminate according to any one of [1] to [8], wherein the resin coating layer is a primer layer.

[10] A method for producing a composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material, wherein at least one layer of the resin coating layer is used. , A combination of polyaddition-reactive compounds for producing a linear polymer is formed by a polyaddition reaction on the surface-treated surface of the metal substrate, and the combination is described in (1) and (2) below. ), A method for producing a composite laminate.
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. A composite laminate having at least one compound selected from the above, a bifunctional epoxy compound [11] metal base material, and one or more resin coating layers laminated on the surface of the metal base material. In the production method, at least one layer of the resin coating layer is homopolymerized or copolymerized with a radical polymerizable compound which is a monofunctional monomer having an unsaturated group on the surface-treated surface of the metal substrate. A method for producing a composite laminate, which is formed by the above.
[12] Before forming the resin coating layer, at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment, chemical conversion treatment, plasma treatment, corona discharge treatment and UV ozone treatment on the metal substrate. The method for producing a composite laminate according to [10] or [11], which comprises subjecting the surface treatment of.
[13] Before forming the resin coating layer, the surface-treated surface of the metal substrate is treated with at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound to perform functionalization. The method for producing a composite laminate according to [10] to [12], which forms a base adhesion layer.

[14] A metal-resin bonded body in which a surface of the composite laminate according to [9] on the primer layer side and a resin material are bonded and integrated.

[15] The resin according to [14], which is at least one method selected from the group consisting of injection molding, press molding, filament winding molding, and hand lay-up molding. A method for producing a metal-resin bonded body, in which a surface of the composite laminate on the primer layer side and the resin material are joined and integrated when the material is molded.
[16] The method for producing the metal-resin bonded body according to [14], wherein the primer layer is subjected to an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, a hot press method, and the like. A method for producing a metal-resin bonded body, wherein the resin material is welded by at least one welding method selected from the group consisting of an injection welding method.

According to the present invention, it is possible to provide a composite laminate in which a metal base material and a resin coating layer are laminated, and the surface of the composite laminate is provided with excellent bondability to a resin material. it can.
Further, by using the composite laminate, it is possible to provide a metal resin bonded body bonded with high strength.

It is sectional drawing which shows typically one Embodiment of the composite laminated body of this invention. It is sectional drawing which shows typically one Embodiment of the metal resin bonded body of this invention. It is sectional drawing which shows typically the other embodiment of the metal resin bonded body of this invention.

The composite laminate of the present invention and a method for producing the same, and a metal resin bonded body using the composite laminate and a method for producing the same will be described in detail.

[Composite laminate]
The composite laminate of the present invention is a composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material.
At least one layer of the resin coating layer is composed of a resin composition containing a double-addition linear polymer containing a combination of double-addition reactive compounds that produce a linear polymer as a constituent component, and the combination is as follows. It is composed of a resin composition containing at least one of (1) and (2), a radical homopolymer of a monofunctional monomer having an unsaturated group, or a linear polymer which is a radical copolymer.
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. At least one of the compounds selected from the above and a bifunctional epoxy compound. In the present specification, the resin composition is a polymer, an additive, or the like obtained by polymerizing a polyadditive reactive composition or a radically polymerizable composition. Means a mixture of.

FIG. 1 shows an embodiment of the composite laminate. In the composite laminate 1 shown in FIG. 1, a functional group-adhering layer 3 is provided on the surface of the surface treatment portion 2a formed on the surface of the metal base material 2, and a resin coating layer is further provided on the surface of the functional group-adhering layer 3. It has a structure in which 4 is formed. The functional group adhesion layer 3 does not necessarily have to be formed between the metal base material 2 and the resin coating layer 4. That is, the resin coating layer 4 on the surface of the metal base material 2 may be directly laminated on the surface treatment portion 2a.

<Metal base material>
The metal type of the metal base material 2 is not particularly limited.
Examples of the metal type of the metal base material 2 include aluminum, iron, titanium, magnesium, stainless steel, and copper. 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 aluminum and its alloys. Similarly, iron, titanium, magnesium and copper shall also be used in the sense of including these simple substances and their alloys.

<Surface treatment part>
A surface treatment portion 2a is formed on the surface of the metal base material 2. The surface treatment portion 2a is regarded as a part of the metal base material 2.
Examples of the method for forming the surface treatment portion include cleaning with a solvent (hereinafter referred to as solvent cleaning), degreasing treatment, blasting treatment, polishing treatment, etching treatment, chemical conversion treatment, plasma treatment, corona discharge treatment, UV ozone treatment and the like. The surface treatment that generates a hydroxyl group on the surface of the metal substrate is preferable. These treatments may be performed by only one type or by two or more types. As a specific method of these surface treatments, known methods can be used.
In these surface treatments, contaminants on the surface of the metal base material are removed, and fine irregularities are formed on the surface of the metal base material 2 for the purpose of an anchor effect to roughen the surface. As a result, it is possible to exert an anchor effect that improves the adhesion between the surface of the metal base material 2 and the resin coating layer 4, and the bondability of various materials (metal materials, organic materials, etc.) to the bonding target. Can also contribute to the improvement of.

Therefore, when the composite laminate 1 is manufactured, the surface treatment of the metal base material 2 is performed before the resin coating layer 4 is formed.
When the surface properties of the metal base material 2 surface-treated by the above method are different from those immediately after the surface treatment due to the formation of a resin coating layer or the like on the surface-treated surface. There is also. Therefore, it is considered impossible or impractical to specify and express the surface properties of the surface-treated material layer. Therefore, in the present invention, the surface of the surface-treated material layer is specified by the surface treatment method.

When the metal base material 2 is aluminum, the surface treatment preferably includes an etching treatment and / or a boehmite treatment.
In order to effectively perform the surface treatment, it is also preferable to degreas the surface of the metal base material before the surface treatment with an organic solvent such as acetone in advance.
Various treatments of the surface treatment can be performed by a known method. As a specific processing method, for example, the method shown below can be used.

[Solvent cleaning, degreasing treatment]
Examples of the solvent cleaning and degreasing treatment include degreasing the surface of the metal substrate with an organic solvent such as acetone or toluene. The solvent cleaning and degreasing treatment are preferably performed before other surface treatments.

[Blasting]
Examples of the blasting process include shot blasting and sand blasting.

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

[Etching process]
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 chromium 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 base material 2 is aluminum, an alkaline method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable, and a 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 preferable to neutralize (de-smut) with a 5 to 20% by mass aqueous nitric acid solution, wash with water, and dry.

[Chemical conversion processing]
The chemical conversion treatment mainly forms a chemical conversion film on the surface of the metal base material 2 as a surface treatment portion 2a.
Examples of the chemical conversion treatment when the metal base material 2 is aluminum include boehmite treatment, zirconium treatment and the like, and boehmite treatment is particularly preferable.

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 immersed in a chemical agent for zirconium treatment (for example, "Palcoat 3762" manufactured by Nihon Parkerizing Co., Ltd., "Palcoat 3796", etc.) at 45 to 70 ° C. for 0.5 to 3 minutes. It is preferable to do this. The zirconium treatment is preferably performed after the etching treatment by the caustic soda method.

[Plasma processing]
The plasma treatment is to create a plasma beam with a high-voltage power supply and a rod and hit it against the surface of the material to excite molecules to make it in a functional state. Examples thereof include an atmospheric pressure plasma treatment method capable of imparting hydroxyl groups and polar groups to the surface of the material. Be done.

[Corona discharge treatment]
The corona discharge treatment includes a method applied to surface modification of a polymer film, and starts from a radical generated by cutting a polymer main chain or a side chain of a polymer surface layer by electrons emitted from an electrode. This is a method of generating a hydroxyl group or a polar group on the surface.

[UV ozone treatment]
The UV and ozone treatment, with a force of ozone (O ₃₎ generated energy and thereby having a short wavelength ultraviolet ray emitted from a low-pressure mercury lamp, a process for modifying or cleaning the surface. In the case of glass, it is one of the surface cleaning methods for removing organic impurities on the surface. Generally, a cleaning surface modifier using a low-pressure mercury lamp is called a "UV ozone cleaner", a "UV cleaning apparatus", an "ultraviolet surface modifier" or the like.

<Functional group attachment layer>
It is also preferable that the functional group adhering layer 3 is laminated in contact with the surface of the metal base material 2 and the resin coating layer 4. The functional group attachment layer 3 is a layer having a functional group introduced from at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound.
By forming a layer having the functional group between the surface of the metal base material 2 and the resin coating layer 4, the chemical bond formed by the reaction of the functional group causes the surface of the metal base material 2 and the surface of the metal base material 2 to be formed. The effect of improving the adhesiveness with the resin coating layer 4 can be obtained, and it can also contribute to the improvement of the bondability of various materials (metal materials, organic materials, etc.) with the bonding target.

Therefore, when the composite laminate 1 is produced, at least selected from the group consisting of a silane coupling agent, an isocyanate compound, and a thiol compound on the surface-treated surface of the metal base material 2 before forming the resin coating layer 4. It is preferable to form the functional group attachment layer 3 by treating with one kind.

Since the surface-treated portion 2a is formed on the metal base material 2, the chemistry formed by the reaction between the anchor effect due to the fine irregularities of the surface-treated portion 2a and the functional group of the functional group adhesion layer 3. Due to the synergistic effect with the bond, the adhesiveness between the surface of the metal base material 2 and the resin coating layer 4 and the bondability of various materials (metal material, organic material, etc.) to the bonding target can be improved. ..

The method for forming the functional group adhering layer 3 with the silane coupling agent, the isocyanate compound, or the thiol compound is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, the metal substrate is immersed in a solution such as 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 immersed at room temperature to 100 ° C. for 1 minute to 5 hours. It can be carried out by a method such as drying.

〔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 the silane coupling agent or the silanol group obtained by oligomerizing the silanol group reacts with the hydroxyl group existing on the surface of the metal substrate 2 and bonds to the resin coating layer 4 or the object to be bonded. A functional group based on the structure of the silane coupling agent that can be chemically bonded can be added (introduced) to the metal substrate 2.

The silane coupling agent is not particularly limited, but for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl. Methyldimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N -(Vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanuppropyltriethoxy Examples thereof include silane, dithioltriazinepurpyrtriethoxysilane and the like. These may be used alone or in combination of two or more.

[Isocyanate compound]
The isocyanate compound has a structure in which an isocyanate group in the isocyanate compound can be chemically bonded to the resin coating layer 4 or a bonding target by reacting with a hydroxyl group existing on the surface of the metal substrate 2 and bonding to the isocyanate compound. The functional group based on the above can be imparted (introduced) to the metal base material 2.

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 can be chemically bonded to the resin coating layer 4 or the object to be bonded by reacting and bonding the mercapto group (thiol group) in the thiol compound with the hydroxyl group existing on the surface of the metal base material 2. A functional group based on the structure of the thiol compound can be imparted (introduced) to the metal substrate 2.

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Corporation and "QE-340M" manufactured by Toray Fine Chemicals Co., Ltd. ”), Ether-based first-class thiols (for example,“ Cup Cure 3-800 ”manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example,“ Karenz MT ”manufactured by Showa Denko KK) (Registered Trademark) BD1 ”), Pentaerythritol tetrakis (3-mercaptobutylate) (for example,“ Karenz MT (registered trademark) PE1 ”manufactured by Showa Denko KK), 1,3,5-Tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Karensu MT (registered trademark) NR1" manufactured by Showa Denko KK) and the like can be mentioned.

<Resin coating layer>
The resin coating layer 4 is laminated on the surface-treated surface of the metal base material 2, that is, the surface of the surface-treated portion 2a of the metal base material 2. Alternatively, it may be laminated on the surface of the functional group attachment layer 3.
Further, the resin coating layer 4 may be composed of one layer or may be composed of a plurality of layers of two or more layers.
The resin coating layer 4 is formed on the surface-treated surface of the metal base material 2 with excellent adhesiveness, protects the surface of the metal base material 2, and adheres dirt to the surface of the metal base material 2. Deterioration such as oxidation can be suppressed.
Further, the resin coating layer 4 can impart excellent bondability to a bonding target of various materials (metal material, organic material, etc.), particularly to a resin material, on the surface of the metal base material 2. Further, it is also possible to obtain a composite laminate capable of maintaining a state in which excellent bondability can be obtained for a long period of several months while the surface of the metal base material 2 is protected as described above.

As described above, in the composite laminate 1, the resin coating layer 4 can impart excellent bondability to the metal substrate 2 to the bonding target of various materials (metal material, organic material, etc.), and thus the resin. It can be said that the coating layer 4 is a primer layer of the composite laminate 1.
The primer layer referred to here is, for example, like a metal resin bonded body described later, when the metal base material 2 is bonded and integrated with a bonding target such as a resin material, the metal base material 2 and the bonding target are joined together. It is meant to be a layer that is interposed between them and improves the bondability of the metal base material 2 to the bonding target.

<One Embodiment of the resin coating layer>
In one embodiment, at least one layer of the resin coating layer comprises a resin composition containing a polyaddition linear polymer containing a combination of polyaddition reactive compounds that produce a linear polymer as a constituent component. The combination of the polyaddition reactive compounds is at least one of the following (1) and (2).
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. At least one compound selected from the above and a bifunctional epoxy compound The combination may be a combination of three or more kinds as at least one of the following (3) and (4).
(3) At least two compounds selected from the group consisting of bifunctional glycol compounds, bifunctional amino compounds and bifunctional thiol compounds, bifunctional isocyanate compounds (4) Bifunctional carboxy compounds and bifunctional thiol compounds, and bifunctional Epoxy compound

A linear polymer forming a thermoplastic structure, that is, a linear polymer structure can be obtained by a multiple addition reaction in at least any combination of the above (1) and (2). Here, the linear polymer means a polymer that does not contain a crosslinked structure in the polymer molecule and is one-dimensional linear. That is, unlike the thermosetting resin that constitutes a three-dimensional network with a crosslinked structure, a resin coating layer made of a resin having thermoplasticity due to the multiple addition reaction in at least any combination of the above (1) and (2). 4 can be formed. Since the resin composition obtained by the above-mentioned heavy addition reaction has such characteristics, it is possible to form the resin coating layer 4 having excellent adhesion to the metal base material 2, and the resin composition is said to be capable of forming the resin coating layer 4. The resin coating layer 4 can be made to have excellent bondability with a bonding target.
Therefore, when the composite laminate 1 is produced, the resin coating layer 4 is subjected to a double addition reaction on the surface-treated surface of the metal base material 2 with at least one of the above combinations (1) and (2). It is preferable to form at least one layer of.
The heavy addition reaction is preferably carried out on the surface of the functional group attachment layer. The resin coating layer 4 formed in such an embodiment has excellent adhesion to the metal base material 2 and excellent bondability to the object to be bonded.
The coating method for forming the resin coating layer 4 from the resin composition is not particularly limited, and examples thereof include a spray coating method and a dipping method.
The method of the double addition reaction in at least one of the above combinations (1) and (2) differs depending on the functional group to be combined, such as the condition for the heavy addition reaction to proceed and the molecular weight distribution, and is specific based on the combination. It is also not possible to comprehensively express the aspect. Therefore, it can be said that it is impossible or impractical to directly specify the resin coating layer formed by the double addition reaction in at least any combination of the above (1) and (2) by the structure or characteristics.

The heavy addition reactive composition containing the combination of the heavy addition reactive compounds as a constituent component sufficiently proceeds with the heavy addition reaction to form a desired resin coating layer, so that a solvent or, if necessary, a solvent is used. It may contain an additive such as a colorant. In this case, it is preferable that the heavy addition reactive compound is the main component among the components other than the solvent of the resin composition. The main component means that the content of the polyaddition-reactive compound, which is the sum of the polyaddition-reactive compounds constituting the combination, is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.
As used herein, the polyaddition-reactive composition means a combination of a polyaddition-reactive compound and a mixture of a catalyst, a solvent, and the like.

The bifunctional glycol compound is a compound having two hydroxy groups, and examples thereof include aliphatic glycols such as ethylene glycol, propylene glycol, diethylene glycol, and 1,6 hexanediol. Of these, propylene glycol, diethylene glycol and the like are preferable from the viewpoint of primer toughness.

The bifunctional amino compound is a compound having two amino groups, and examples thereof include bifunctional aliphatic diamines and aromatic diamines. Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, and the like. Examples include 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, N- (2-aminoethyl) piperazine, and aromatics. Examples of the diamine include diaminodiphenylmethane and diaminodiphenylpropane. Of these, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine and the like are preferable from the viewpoint of primer toughness.

The bifunctional thiol compound is a compound having two mercapto groups in the molecule, and is, for example, a bifunctional secondary thiol compound 1,4-bis (3-mercaptobutylyloxy) butane (for example, manufactured by Showa Denko KK). "Karens MT (registered trademark) BD1") can be mentioned.

The bifunctional isocyanate compound is a compound having two isocyanato groups, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, dimerate diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof, p. -Diisocyanate compounds such as phenylenediocyanate, xylylene diisocyanate and diphenylmethane diisocyanate (MDI) can be mentioned. Among them, TDI, MDI and the like are preferable from the viewpoint of the strength of the primer.

The bifunctional carboxy compound may be a compound having two carboxy groups, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid. Be done. Of these, isophthalic acid, terephthalic acid, adipic acid and the like are preferable from the viewpoint of primer strength and toughness.

The bifunctional epoxy compound is a compound having two epoxy groups in one molecule. For example, aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, naphthalene type bifunctional epoxy resin, and aliphatic such as 1,6-hexanediol diglycidyl ether. Epoxy compounds can be mentioned.
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". In addition, an epoxy compound having a special structure can be used as long as it is bifunctional. Of these, one type may be used alone, or two or more types may be used in combination.

The compounding ratio of the combination of the bifunctional isocyanate compound and the bifunctional glycol compound (polyurethane) is preferably in the range of 0.7 to 1.5 in terms of −OH / −NCO equivalent ratio.
The urethanization catalyst used in the catalyst curing type as a two-component type is not particularly limited, and examples thereof include an amine-based catalyst and an organic tin-based catalyst. The amine-based catalyst is not particularly limited, but for example, triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyl etheramine, N, Examples thereof include N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and the like. The organic tin catalyst is not particularly limited, and examples thereof include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimalate. Generally, it is preferable to add 0.01 to 10 parts by weight of the urethanization catalyst with respect to 100 parts by mass of the bifunctional glycol component.

The compounding ratio of the combination of the bifunctional isocyanate compound and the bifunctional amino compound (polyurea) is preferably in the range of 0.7 to 1.5 in terms of _{-NH 2 / -NCO equivalent ratio.} No special reaction catalyst is required.

The compounding ratio of the combination of the bifunctional isocyanate compound and the bifunctional thiol compound is preferably in the range of 0.7 to 1.5 in terms of -SH / -NCO equivalent ratio.
A tertiary amine or phosphorus compound can be used as the reaction catalyst. Examples thereof include triethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, triphenylphosphine and the like. The above urethanization catalyst may be used.

The compounding ratio of the combination of the bifunctional epoxy compound and the bifunctional carboxy compound is preferably in the range of 0.7 to 1.5 in terms of −COOH / epoxy equivalent ratio.
A tertiary amine or phosphorus compound can be used as the reaction catalyst. Examples thereof include triethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, triphenylphosphine and the like. The above urethanization catalyst may be used.

The compounding ratio of the combination of the bifunctional epoxy compound and the bifunctional thiol compound is preferably in the range of 0.7 to 1.5 in the −SH / epoxy equivalent ratio.
A tertiary amine or phosphorus compound can be used as the reaction catalyst. Examples thereof include triethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, triphenylphosphine and the like. The above urethanization catalyst may be used.

The heavy addition reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 120 minutes, although it depends on the type of reaction compound and the like. Specifically, the polyaddition-reactive composition is coated on a metal substrate, the solvent is appropriately volatilized, and then the compound is heated to carry out the polyaddition reaction to generate heat of the polyaddition-reactive compound. A plastic resin layer can be formed.

<Another Embodiment of the resin coating layer>
In another embodiment, at least one layer of the resin coating layer 4 is formed from a resin composition containing a radical homopolymer of a monofunctional monomer having an unsaturated group or a linear polymer which is a radical copolymer. Become.

The radical (co) polymerization reaction of the monofunctional monomer forms a thermoplastic structure, that is, a linear polymer structure. That is, unlike the thermosetting resin that constitutes a three-dimensional network having a crosslinked structure, the resin coating layer 4 made of a resin having thermoplasticity can be formed. The radical polymerizable composition containing a radically polymerizable compound that produces a linear polymer by radical homopolymerization or radical copolymerization of the monofunctional monomer having an unsaturated group has such characteristics. The resin coating layer 4 having excellent adhesion to the metal base material 2 can be formed, and the resin coating layer 4 can be made to have excellent bondability to the bonding target.
Therefore, when the composite laminate 1 is produced, at least one layer of the resin coating layer 4 can be formed by subjecting the radically polymerizable compound to a radical polymerization reaction on the surface-treated surface of the metal base material 2. preferable.
The radical polymerization reaction is preferably carried out on the surface of the functional group attachment layer. The resin coating layer 4 formed in such an embodiment has excellent adhesion to the metal base material 2 and excellent bondability to the object to be bonded.
The method of applying the radically polymerizable composition to the surface of the metal substrate 2 is not particularly limited, and examples thereof include a spray coating method and a dipping method.
As used herein, the radically polymerizable composition means a mixture of a monofunctional monomer having an unsaturated group, a catalyst, a solvent, and the like.
The radical reaction of the monofunctional monomer is diverse depending on the type of polymerization initiator and the reaction conditions, and it is not possible to comprehensively express a specific mode based on the combination thereof. Therefore, it can be said that it is impossible or impractical to directly specify the resin coating layer formed by the radical reaction of the monofunctional monomer by the structure or characteristics.

The radically polymerizable composition may contain a solvent and, if necessary, an additive such as a colorant in order to sufficiently proceed the radical polymerization reaction and form a desired resin coating layer. In this case, it is preferable that the radically polymerizable compound is the main component among the components of the radically polymerizable composition other than the solvent. The main component means that the content of the radically polymerizable compound is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.

The monofunctional monomer having an unsaturated group is a monomer having one ethylenically unsaturated bond. For example, styrene monomers, styrene-based monomers such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, chlorostyrene, vinyltoluene, divinylbenzene, etc.; ethyl (meth) acrylate, Methyl (meth) acrylate, -n-propyl (meth) acrylate, -i-propyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and phenoxyethyl (meth) Examples thereof include (meth) acrylic acid esters such as meta) acrylate. Among them, a combination of styrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like is preferable from the viewpoint of primer strength and toughness.

As the polymerization initiator for the radical polymerization reaction of the radically polymerizable compound, for example, known organic peroxides, photoinitiators and the like are preferably used. A room temperature radical polymerization initiator in which an organic peroxide is combined with a cobalt metal salt or amines may be used. Examples of organic peroxides include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. As the photoinitiator, it is desirable to use one that can initiate polymerization with visible rays from ultraviolet rays.
The radical polymerization reaction is preferably carried out by heating at room temperature to 200 ° C. for 5 to 90 minutes, although it depends on the type of the reaction compound and the like. In the case of photocuring, the polymerization reaction is carried out by irradiating with ultraviolet rays or visible light. Specifically, the thermoplastic resin layer made of the radically polymerizable compound can be formed by coating the resin composition and then heating the resin composition to carry out a radical polymerization reaction.

(Thermosetting resin)
When the resin coating layer 4 is composed of a plurality of layers, at least one of them is a layer formed of a cured product of a resin composition containing a thermosetting resin (hereinafter, also referred to as a thermosetting resin layer). It is also preferable. Examples of the thermosetting resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
When the thermosetting resin layer is composed of a plurality of layers, each layer may be formed by one of these resins alone, or may be formed by mixing two or more of these resins. Alternatively, each of the two or more layers may be a different type of thermosetting tree layer.
Since the resin coating layer 4 has a laminated structure of a resin coating layer having a linear polymer structure having thermoplasticity and the thermosetting resin layer, various strengths and impact resistances based on the thermosetting resin can be obtained. The composite laminate 1 coated with the resin coating layer 4 having the characteristics can be formed.
The stacking order of the thermosetting resin layer and the resin coating layer having a linear polymer structure having thermoplasticity is not particularly limited, but the composite laminate 1 joins the metal base material 2 to the bonding target. In the case of the purpose of forming the resin, the resin coating layer having a linear polymer structure having thermoplasticity is laminated so as to be the outermost surface of the resin coating layer 4 from the viewpoint of obtaining excellent bondability with the bonding target. It is preferable to do so.

The coating method for forming at least one of the resin coating layers 4 with the resin composition containing the thermosetting resin is not particularly limited, and examples thereof include a spray coating method and a dipping method. ..
The resin composition may contain a solvent and, if necessary, additives such as a colorant, in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired resin coating layer. .. 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 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.

The thermosetting resin referred to in the present invention broadly means a resin that is crosslink-cured, and includes not only a heat-curable type but also a room temperature-curable type and a photocurable 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 with a hydroxyl group, and a urethane resin corresponding to what is defined in ASTM D16 as "a paint containing a polyisocyanate having a vehicle non-volatile component of 10 wt% or more" is used. preferable. The urethane resin may be a one-component type or a two-component type.

Examples of the one-component urethane resin include oil-modified type (cured by oxidative polymerization of unsaturated fatty acid groups), moisture-cured type (cured by reaction of isocyanato group with water in air), and block type (cured by reaction of isocyanato group with water in air). Examples thereof include a lacquer type (which cures when the solvent volatilizes and dries), a lacquer type (which cures when the isocyanato group dissociated by heating and regenerated and the hydroxyl group reacts with each other). 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 polyols, polyether polyols, and phenol resins.
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 diimmerate 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) and the like. Can be mentioned.
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, N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and other amine-based catalysts; dibutyltindi Examples thereof include organotin-based catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimalate.
In the polyol curing type, it is generally preferable that 0.01 to 10 parts by mass of the urethanization catalyst is blended with respect to 100 parts by mass of the polyol compound.

〔Epoxy resin〕
The prepolymer before curing of the epoxy resin is a compound having at least two epoxy groups in one molecule.
Examples thereof include ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, cyclic aliphatic epoxy resin, ether-ester-based epoxy resin, and the like. 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 the thiol compounds in the above-mentioned surface treatment. Among these, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Carens 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 (for example, styrene) in which a polycondensation 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. Etc.).
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.

[Metal resin joint]
In the metal-resin bonded body of the present invention, the resin coating layer 4 of the composite laminate 1 is a primer layer as described above, and the surface on the primer layer side and the resin material are bonded and integrated. ..
FIG. 2 shows an embodiment of the metal-resin bonded body of the present invention. The metal-resin bonded body shown in FIG. 2 is formed by joining and integrating the surface 14 of the composite laminate 1 on the resin coating layer (primer layer) side and the resin material to be joined 30A so as to be in direct contact with each other. is there.
As described above, since the surface of the primer layer is excellent in bonding targets of various materials (metal materials, organic materials, etc.), particularly the resin material, the metal base material 2 and the resin material can be bonded to each other. A metal-resin bonded body bonded with high strength can be preferably obtained.

The thickness (dry thickness) of the primer layer depends on the material to be bonded and the contact area of the bonded portion, but is 1 μm from the viewpoint of obtaining excellent bonding properties between the surface on the primer layer side and the resin material. It is preferably 10 mm, more preferably 2 μm to 8 mm, still more preferably 3 μm to 5 mm.
Depending on the heating temperature at the time of joining, the metal resin bonded body is likely to undergo thermal deformation due to the difference in the coefficient of thermal expansion between the metal base material 2 and the bonding target 30A in the process of cooling to room temperature after bonding. From the viewpoint of suppressing and alleviating such thermal deformation, it is desirable to provide a portion having a large elongation rate between the metal base material 2 and the bonding target 30A with a predetermined thickness. The thickness is determined in consideration of the temperature change at the time of joining (the temperature change from the heating temperature at the time of joining to the cooling at room temperature) and the physical properties such as the elongation rate of the primer layer.
For example, when an aluminum base material and a carbon fiber reinforced resin (CFRP) or the like are joined and integrated, the thickness of the primer layer is preferably 0.1 to 10 mm, more preferably 0.2 to 8 mm, and further. It is preferably 0.5 to 5 mm.

FIG. 3 shows another embodiment of the metal-resin bonded body of the present invention. The metal-resin bonded body shown in FIG. 3 is a composite laminate 1 in which the surface 14 on the resin coating layer (primer layer) side and the resin material to be bonded to the target 30B are bonded and integrated via an adhesive 31. Is.
As described above, depending on the type of the resin material of the bonding target 30B, by using the adhesive 31, it is possible to obtain a metal-resin bonded body in which the metal base material 2 and the resin material are bonded with higher adhesive strength.

The adhesive 31 is appropriately selected depending on the type of the resin material of the bonding target 30B, and for example, a known adhesive such as an epoxy resin type, a urethane resin type, or a vinyl ester resin type can be used.
Depending on the heating temperature at the time of bonding, the metal resin bonded body is likely to undergo thermal deformation due to the difference in the coefficient of thermal expansion between the metal base material 2 and the bonding target 30B in the process of cooling to room temperature after bonding. From the viewpoint of suppressing and alleviating such thermal deformation, the thickness of the adhesive layer 31 is set so that the total thickness of the primer layer and the adhesive layer 31 is 0.5 mm or more, and the metal substrate 2 is to be bonded. It is desirable to provide a portion having a characteristic of a large elongation rate between the 30B and the portion having a predetermined thickness. The total thickness is determined in consideration of the temperature change at the time of adhesion (temperature change from the heating temperature of the adhesive holding to room temperature cooling) and the physical properties such as the elongation rate of the primer layer and the adhesive.

The resin material in the metal-resin bonded body is not particularly limited, and may be a general synthetic resin. For example, resins such as polycarbonate resins (Example 1), polyester resins, polybutylene terephthalate resins (Examples 2, 3, 4, 6), polyetherimide resins (Example 5), and the like used for automobile parts and the like. Can also be mentioned. Further, for example, a carbon fiber reinforced resin (CFRP) such as a press-molded body such as a sheet molding compound (SMC) and a bulk molding compound (BMC) using carbon fibers, a glass fiber reinforced resin (GFRP) and the like can be mentioned.
The SMC is, for example, a mixture of unsaturated polyester resin and / or vinyl ester resin, polymerizable unsaturated monomer, curing agent, low shrinkage agent, filler, etc., and is a reinforcing fiber such as carbon fiber. It is a sheet-like molded product obtained by impregnating with.

As a method for producing the metal-resin bonded body, the composite laminate 1 and the molded body of the resin material can be separately produced, and they can be bonded and integrated. For example, at least one selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a hot pressing method on the primer layer of the composite laminate 1, and the molded body of the resin material. By welding, a metal-resin bonded body can be obtained. Of these welding methods, the ultrasonic welding method, the electromagnetic induction method, and the laser method are preferable.
Further, at the same time as molding the resin material, it can be joined and integrated with the composite laminate 1. Specifically, when the resin material is molded by, for example, injection molding, press molding, filament winding molding, hand lay-up molding, transfer molding, or the like, the surface of the composite laminate 1 on the primer layer side is used. A metal resin bonded body can be obtained by joining and integrating the resin material.
Of these molding methods, injection molding, press molding, filament winding molding, and hand lay-up molding are preferable.

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

<Example 1: "Bifunctional epoxy compound and bifunctional thiol compound">
(Surface treatment process)
An 18 mm × 45 mm rectangular aluminum plate (A6063) (aluminum article) having a thickness of 1.5 mm was immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by mass for 1.5 minutes, and then having a concentration of 5% by mass. Neutralization treatment with aqueous nitrate solution, washing with water, drying, chemical conversion treatment, and then boehmite treatment by boiling the aluminum plate after the chemical conversion treatment in pure water for 10 minutes and baking at 250 ° C. for 10 minutes. (Surface treatment) was performed. By this boehmite treatment, a surface-treated portion (boehmite film having surface irregularities) was formed on the surface of the aluminum plate.

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

(Resin coating layer forming process)
Next, 100 g of epoxy resin (“jER® 1001” manufactured by Mitsubishi Chemical Co., Ltd.), 1,4-bis (3-mercaptobutyryloxy) butane (“Karens MT® BD1” manufactured by Showa Denko Co., Ltd.) ”) 31.5 g, 5.3 g of 2,4,6-tris (dimethylaminomethyl) phenol (“DMP-30” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dissolved in 244 g of acetone. The polyaddition-reactive composition is applied to the functional group-adhering surface of the aluminum plate on which the functional group-adhering layer is formed by a spray method so that the dry thickness is 10 μm, and then left at room temperature in the air for 30 minutes. The solvent was volatilized by this, and then left in a furnace at 150 ° C. for 30 minutes to carry out an addition polymerization reaction and returned to room temperature to form a resin coating layer having a linear polymer structure with a thickness of 10 μm on the surface of the functional group adhesion layer. did. In this example, the resin coating layer is a primer layer, and in this way, an aluminum plate with a primer (aluminum article with a primer) was produced.

(Preparation of test piece)
Polycarbonate resin (PC resin) (SABIC's "LEXAN (registered trademark) 121R-111") (to be joined) is applied to the surface of the aluminum plate with a primer on the primer layer side, and an injection molding machine (Sumitomo Heavy Industries, Ltd.) "SE100V" manufactured by: Cylinder temperature 300 ° C, tool temperature 110 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]), by injection molding, tension conforming to ISO19095 (Part3) A test piece for testing (aluminum: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) was prepared.

<Example 2: "Bifunctional isocyanate compound and bifunctional glycol compound">
(Resin coating layer forming process)
A bisphenol A type epoxy resin (“jER828 (trade name)” manufactured by Mitsubishi Chemical Co., Ltd.) is used as a thermosetting resin on an aluminum plate obtained through the (surface treatment step) and (functional group adhesion layer forming step) of Example 1. ) 100 g, pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko Co., Ltd. "Karensu MT PE1 (trade name)"; epoxy resin curing agent) 70 g, 2,4,6-tris (dimethylaminomethyl) phenol ("DMP-30" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) A resin composition obtained by dissolving 10 g of a thermosetting resin in 344 g of acetone is sprayed so that the dry thickness is 10 μm. After coating, the solvent was volatilized and cured by leaving it in the air at room temperature for 30 minutes to form a first resin coating layer having a crosslinked structure.
Next, on the surface of this resin coating layer, further 4,4'-diphenylmethanediisocyanate: 100 g, propylene glycol: 76 g, 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) DMP-30 "): 0.6 g of acetone: 298 g of a polyaddition reactive composition was applied by a spray method so as to have a dry thickness of 10 μm, and then left in the air at room temperature for 30 minutes to obtain a solvent. Is volatilized, and then left in a furnace at 150 ° C. for 30 minutes for an addition polymerization reaction to return to room temperature, and a resin coating layer having a linear polymer structure with a thickness of 10 μm is formed on the outermost surface of the first resin coating layer. Formed. In this example, the resin coating layer is a primer layer, and in this way, an aluminum plate with a primer (aluminum article with a primer) was produced.

(Preparation of test piece)
Polybutylene terephthalate resin (PBT resin) (SABIC "VALOX® 507"; containing 30% by mass of glass fiber (GF)) (to be bonded) is applied to the surface of the aluminum plate with a primer on the primer layer side. Injection molding with an injection molding machine (“SE100V” manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature 240 ° C, tool temperature 80 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]). A test piece for tensile test (aluminum: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) conforming to ISO19095 was produced.

<Example 3: "Bifunctional epoxy compound and bifunctional carboxy compound">
(Surface treatment process)
An 18 mm × 45 mm rectangular iron plate having a thickness of 1.5 mm was degreased with acetone and the surface was roughened with # 100 sandpaper.

(Functional group adhesion layer forming step)
Next, 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was dissolved in 1000 g of industrial ethanol in a solution containing a silane coupling agent at 70 ° C. After immersing the surface-roughened iron plate for 20 minutes, the iron plate was taken out and dried to further form a functional group-adhering layer on the surface of the iron plate whose surface was roughened in the above (surface treatment step).

(Resin coating layer forming process)
Next, 100 g of epoxy resin (“jER® 1004” manufactured by Mitsubishi Chemical Industries, Ltd.), terephthalic acid: 9.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (Fuji Film Wako Pure Chemical Industries, Ltd.) The polyaddition-reactive composition obtained by dissolving 0.44 g of "DMP-30" manufactured by the company in 203 g of methyl ethyl ketone at 50 ° C. is put on the above-mentioned roughened iron plate to have a drying thickness of 10 μm. After applying by the spray method as described above, the solvent is volatilized by leaving it in the air at room temperature for 30 minutes, and then it is left in a furnace at 150 ° C. for 90 minutes to undergo an addition polymerization reaction and returned to room temperature to perform the surface treatment. A resin coating layer having a linear polymer structure with a thickness of 10 μm was formed on the surface of the later iron plate. In this example, the resin coating layer is a primer layer, and in this way, an iron plate with a primer (iron article with a primer) was produced.

(Preparation of test piece)
Polybutylene terephthalate resin (PBT resin) (SABIC "VALOX® 507"; containing 30% by mass of glass fiber (GF)) (to be bonded) is injected onto the surface of the iron plate with a primer on the primer layer side. By injection molding with a molding machine (“SE100V” manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature 245 ° C, tool temperature 80 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]) , ISO19095 compliant test piece for tensile test (iron: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) was prepared.

<Example 4: "Radical polymerizable compound">
(Surface treatment process)
A stainless steel (SUS304) plate having a thickness of 1.5 mm and having a rectangular shape in a plan view of 18 mm × 45 mm was degreased with acetone and the surface was roughened with # 100 sandpaper.

(Functional group adhesion layer forming step)
Next, 2 g of 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was dissolved in 1000 g of industrial ethanol in a solution containing a silane coupling agent at 70 ° C. After immersing the surface-roughened SUS304 plate for 20 minutes, the SUS304 plate was taken out and dried to form a functional group-adhering layer on the surface of the SUS304 plate whose surface was roughened in the above (surface treatment step).

(Resin coating layer forming process)
Next, 100 g of vinyl ester resin ("Lipoxy (registered trademark) R-802" manufactured by Showa Denko Co., Ltd., styrene monomer: 20 g, methyl methacrylate monomer: 20 g, organic peroxide catalyst ("Perbutyl" manufactured by Chemical Axo Co., Ltd.) (Registered Trademark) O ”) The thermosetting resin composition mixed with 1.4 g is applied to the functional group adhesion surface of the SUS304 plate after undergoing the functional group adhesion layer forming step, and the thickness after curing becomes 5 μm. After coating by the spray method as described above, the mixture was heated at 100 ° C. for 30 minutes and cured to form a first resin coating layer having a crosslinked structure.
Next, a radically polymerizable composition obtained by mixing 2 ethylhexyl acrylate: 70 g, lauryl methacrylate: 30 g, and perbutyl O: 1.0 g was applied to the outermost surface of the first resin coating layer to have a dry thickness. After applying by a spray method to a thickness of 10 μm, it is covered with a PET film and left in a furnace at 120 ° C. for 30 minutes to undergo a radical polymerization reaction and returned to room temperature to bring it back to room temperature, and the outermost surface of the first resin coating layer. As the second resin coating layer, a resin coating layer having a linear polymer structure having a thickness of 10 μm was formed. In this example, the resin coating layer is a primer layer, and in this way, a stainless steel plate with a primer (stainless steel article with a primer) was produced.

(Preparation of test piece)
Polybutylene terephthalate resin (PBT resin) (SABIC "VALOX® 507"; containing 30% by mass of glass fiber (GF)) (subject to bonding) is applied to the surface of the above stainless steel plate with a primer on the primer layer side. , Injection molding machine (“SE100V” manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature 245 ° C, tool temperature 80 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]) As a result, a test piece for tensile test (stainless steel: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) conforming to ISO19095 was produced.

<Example 5: "Bifunctional epoxy compound, bifunctional thiol compound and bifunctional carboxy compound">
(Surface treatment process)
A magnesium plate having a thickness of 1.5 mm and having a rectangular shape in a plan view of 18 mm × 45 mm was degreased with acetone and the surface was roughened with # 100 sandpaper.

(Functional group adhesion layer forming step)
Next, 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was dissolved in 1000 g of industrial ethanol in a solution containing a silane coupling agent at 70 ° C. After immersing the surface-roughened magnesium plate for 20 minutes, the magnesium plate was taken out and dried to form a functional group-adhering layer on the surface of the surface-roughened magnesium.

(Resin coating layer forming process)
Next, 200 g of epoxy resin (“jER® 1004” manufactured by Mitsubishi Chemical Industries, Ltd.), 9.2 g of terephthalic acid, 1,4-bis (3-mercaptobutyryloxy) butane (“jER®) butane (manufactured by Showa Denko Co., Ltd.” Karenz MT (registered trademark) BD1 ") 16.5 g, 2,4,6-tris (dimethylaminomethyl) phenol ("DMP-30 "manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.") 1.5 g in 406 g of acetone The polyaddition reactive composition obtained by dissolving in Wako Pure Chemical Industries, Ltd. was applied to the magnesium plate on which the functional group adhesion layer was formed by a spray method so as to have a dry thickness of 10 μm, and then at room temperature in the air for 30 minutes. The solvent is volatilized by leaving it to stand, and then it is left in a furnace at 150 ° C. for 60 minutes to carry out an addition polymerization reaction, and then returned to room temperature to coat the surface of the functional group adhesion layer with a resin coating having a linear polymer structure having a thickness of 10 μm. A layer was formed. In this example, the resin coating layer is a primer layer, and in this way, a magnesium plate with a primer (magnesium article with a primer) was produced.

(Preparation of test piece)
A polyetherimide resin (PEI resin) (SABIC's "Ultem (registered trademark)") (to be bonded) is applied to the surface of the above-mentioned magnesium plate with a primer on the primer layer side, and an injection molding machine (Sumitomo Heavy Industries, Ltd.) Made by "SE100V"; Cylinder temperature 350 ° C, tool temperature 150 ° C, injection speed 50 mm / sec, peak / holding pressure 160/140 [MPa / MPa]), by injection molding, tensile test test conforming to ISO19095 Pieces (magnesium: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) were prepared.

<Example 6: "Bifunctional isocyanate compound, bifunctional amino compound and bifunctional thiol compound">
(Resin coating layer forming process)
4,4'-Diphenylmethane diisocyanate: 100 g, hexamethylenediamine: 23 g, 1,4-bis (3) on the aluminum plate obtained through the (surface treatment step) and (functional group adhesion layer forming step) of Example 1. -Mercaptobutyryloxy) Butan ("Carens MT (registered trademark) BD1" manufactured by Showa Denko Co., Ltd.) 15 g ("DMP-30" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.): 0.6 g was dissolved in acetone: 338 g. After applying the polyadditive reactive composition by a spray method so that the drying thickness becomes 30 μm, the reaction between solvent volatilization and polyurea is promoted by leaving it in the air at room temperature for 30 minutes, and then in a furnace at 120 ° C. After leaving it for 20 minutes, the remaining addition polymerization reaction was carried out and the temperature was returned to room temperature to form a resin coating layer having a linear polymer structure having a thickness of 30 μm on the outermost surface. In this example, the resin coating layer is a primer layer, and in this way, an aluminum plate with a primer (aluminum article with a primer) was produced.

(Preparation of test piece)
Polybutylene terephthalate resin (PBT resin) (SABIC "VALOX® 507"; containing 30% by mass of glass fiber (GF)) (to be bonded) is applied to the surface of the aluminum plate with a primer on the primer layer side. Injection molding with an injection molding machine (“SE100V” manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature 240 ° C, tool temperature 80 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]). A test piece for tensile test (aluminum: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) conforming to ISO19095 was produced.

<Example 7: "Bifunctional epoxy compound and bifunctional thiol compound">
(Surface treatment process)
The same treatment as in Example 1 was performed.
(Functional group adhesion layer forming step)
The same treatment as in Example 1 was performed.
(Resin coating layer forming process)
Epoxy resin ("jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Co., Ltd.) 100 g, 1,4-bis (3-mercaptobutyryloxy) butane ("Carens MT (registered trademark) BD1" manufactured by Showa Denko Co., Ltd.) 31 Polymerization reaction obtained by dissolving 5.3 g of 5.5 g, 2,4,6-tris (dimethylaminomethyl) phenol (“DMP-30” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in 244 g of acetone. The sexual composition was applied onto a release film so that the dry thickness was 30 μm, left in a furnace at 150 ° C. for 30 minutes, subjected to an addition polymerization reaction, and returned to room temperature to have a linear polymer structure on the release film. A thermoplastic resin layer was formed.
The thermoplastic resin layer of the release film is placed on the surface of the functional group-adhering layer of the aluminum plate, melted at 160 ° C., stretched to a thickness of 80 μm, and then returned to room temperature to have a linear polymer structure having a thickness of 30 μm. Resin coating layer was formed. In this example, the resin coating layer is a primer layer, and in this way, an aluminum plate with a primer (aluminum article with a primer) was produced.

(Preparation of test piece)
Polycarbonate resin (PC resin) (SABIC's "LEXAN (registered trademark) 121R-111") (to be joined) is applied to the surface of the aluminum plate with a primer on the primer layer side, and an injection molding machine (Sumitomo Heavy Industries, Ltd.) "SE100V" manufactured by: Cylinder temperature 300 ° C, tool temperature 110 ° C, injection speed 10 mm / sec, peak / holding pressure 100/80 [MPa / MPa]), by injection molding, tension conforming to ISO19095 (Part3) A test piece for testing (aluminum: 18 mm × 45 mm × 1.5 mm, resin: 10 mm × 45 mm × 3 mm) (metal resin bonded body) was prepared.

<Comparative example 1>
An injection molding of a polycarbonate resin was attempted by the same method as in Example 1 without forming a resin coating layer on an aluminum plate obtained through the same surface treatment step and functional group adhesion layer forming step as in Example 1, but bonding was possible. There wasn't.

<Comparative example 2>
An injection molding of polybutylene terephthalate resin was attempted in the same manner as in Example 2 to an aluminum plate that had been subjected to the same treatment as in Example 2 except that the second resin coating layer was not formed, but it could be bonded. There wasn't.

<Comparative example 3>
A polymerized maleic anhydride-modified olefin-based adhesive paint "Hardlen TD-15B (registered trademark)" manufactured by Toyo Boseki Co., Ltd. was applied to an aluminum plate obtained through the same surface treatment step and functional group adhesion layer forming step as in Example 1. It was coated so that the dry thickness was 10 μm, and baked at 130 ° C. for 60 seconds to prepare an aluminum plate with an adhesive layer.
Polycarbonate was injected into the aluminum plate with an adhesive layer in the same manner as in Example 1, and insert molding was attempted, but the bonding was not possible.

<Comparative example 4>
(Surface treatment process)
The same treatment as in Example 1 was performed.
(Functional group adhesion layer forming step)
Next, 2 g of 4,4'-diphenylmethane diisocyanate (isocyanate compound) was immersed in a solution of 100 g of toluene (solvent) at 70 ° C. for 5 minutes, and then lifted and dried. In this way, an isocyanato group was imparted to the surface of the aluminum plate.
(Creation of test piece)
An attempt was made to insert molding by injecting a polycarbonate resin by the same operation as in Example 1 except that the resin coating layer was not formed on the aluminum plate, but the bonding was not possible.

<Comparative example 5>
(Surface treatment process)
The same treatment as in Example 1 was performed.
(Functional group adhesion layer forming step)
Next, pentaerythritol tetrakis (3-mercaptobutyrate) (thiol compound) (Carens MT PE1 (registered trademark) manufactured by Showa Denko Co., Ltd.): Immersed in a solution dissolved in 2 g and 100 g of toluene (solvent) at 70 ° C. for 5 minutes. After that, it was withdrawn and dried. In this way, a mercapto group was added to the surface of the aluminum plate.
(Creation of test piece)
An attempt was made to insert molding by injecting a polycarbonate resin by the same operation as in Example 1 except that the resin coating layer was not formed on the metal plate, but the bonding was not possible.

<Comparative Example 6>
(Surface treatment process)
The same treatment as in Example 1 was performed.
(Functional group adhesion layer forming step)
Next, the solution was immersed in a solution dissolved in 4,4'-diphenylmethane diisocyanate (isocyanate compound): 2 g and toluene (solvent) 100 g at 70 ° C. for 5 minutes, and then lifted and dried. In this way, an isocyanato group was added to the metal surface.
Further, pentaerythritol tetrakis (3-mercaptobutyrate) (thiol compound) (Carens MT PE1 (registered trademark) manufactured by Showa Denko Co., Ltd.): 2 g, immersed in a solution dissolved in 100 g of toluene (solvent) at 70 ° C. for 5 minutes. It was later lifted and dried. In this way, a mercapto group was extended over the isocyanato group.
(Creation of test piece)
An attempt was made to insert molding by injecting a polycarbonate resin by the same operation as in Example 1 except that the resin coating layer was not formed on the metal plate, but the bonding was not possible.

<Comparative Example 7>
(Surface treatment process)
The same treatment as in Example 1 was performed.
(Functional group adhesion layer forming step)
Next, 0.7 g of triethoxysilylpropylaminotriazine thiol monosodium: 0.7 g was immersed in 1 L of a 95 Vol% ethanol solution at 25 ° C. for 30 minutes, then withdrawn and dried at 160 ° C. for 10 minutes. Then, N, N'-m-phenylenedimaleimide: 1 g and dicumylperoxide: 2 g were immersed in a bonding aid dissolved in 1 L of acetone at 25 ° C. for 10 minutes, lifted and dried at 150 ° C. for 10 minutes. Then, a solution prepared by dissolving 2 g of dicumylperoxide in 1 L of ethanol was sprayed on the above aluminum plate at 25 ° C. and air-dried. In this way, a dehydrated silanol-containing triazine thiol derivative film was formed on the surface of the aluminum plate.
(Creation of test piece)
An attempt was made to insert molding by injecting a polycarbonate resin by the same operation as in Example 1 except that the resin coating layer was not formed on the aluminum plate, but the bonding was not possible.

[Adhesion evaluation]
The test pieces (metal resin bonded bodies) produced in each of the above examples were left at 20 to 25 ° C. for 24 to 48, and after being left at high temperature and high humidity (85 ° C., relative humidity 85%) for 200 hours. After being left in the high temperature and high humidity atmosphere for 600 hours and after being left in the high temperature and high humidity atmosphere for 1000 hours, the tensile tester (universal tester Autograph manufactured by Shimadzu Corporation) conforms to ISO19095 1-4. "AG-IS"; load cell 10 kN, tensile speed 10 mm / min, temperature 23 ° C., 50% RH), a tensile shear bond strength test was performed, and the bond strength was measured. The measurement results are shown in Tables 1 to 3 below.

As is clear from Tables 1 to 3, when at least one of the resin coating layers is the resin coating layer of the present invention (Examples 1 to 6), various metal substrates and various resin materials are used. It was confirmed that the object to be bonded can be bonded with high adhesive strength.

The composite laminate of the present invention is joined and integrated with other materials (parts, etc.) such as steel, aluminum, and CFRP, and is, for example, a door side panel, a bonnet, a roof, a tailgate, a steering hanger, and an A-pillar. , B-pillar, C-pillar, D-pillar, crash box, power control unit (PCU) housing, electric compressor member (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) Used as various automobile parts such as spacers, battery cases, and LED headlamps.
Further, the composite laminate is joined and integrated with, for example, a resin material such as a polycarbonate molded body, and is, for example, a smartphone housing, a notebook computer housing, a tablet personal computer housing, a smart watch housing, and a large liquid crystal television (LCD). -TV) Although it is used as a housing, an outdoor LED lighting housing, etc., it is not particularly limited to these exemplified applications.

1 Composite laminate 2 Metal substrate 2a Surface treatment part 3 Functional group adhesion layer 4 Resin coating layer 14 Surface on the resin coating layer (primer layer) side 30A, 30B Bonding target (resin material)
31 Adhesive

Claims (16)

A composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material.
The resin coating layer is laminated on the surface-treated surface of the metal substrate.
At least one layer of the resin coating layer comprises a resin composition containing a polyaddition linear polymer containing a combination of polyaddition reactive compounds that produce a linear polymer as a constituent component.
A composite laminate in which the combination is at least one of the following (1) and (2).
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. At least one compound selected from and a bifunctional epoxy compound A composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material.
The resin coating layer is laminated on the surface-treated surface of the metal substrate.
A composite laminate in which at least one of the resin coating layers is a resin composition containing a radical homopolymer of a monofunctional monomer having an unsaturated group or a linear polymer which is a radical copolymer. The resin coating layer is a plurality of layers, and at least one layer thereof is made of a cured product of a thermosetting resin.
The composite laminate according to claim 1 or 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-adhering layer is provided between the surface of the metal base material and the resin coating layer, and the functional group-adhering layer is laminated in contact with the metal base material and the resin coating layer.
The composite laminate according to any one of claims 1 to 3, wherein the functional group-adhering layer has a functional group introduced from at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound. body. The surface treatment is at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment, chemical conversion treatment, plasma treatment, corona discharge treatment and UV ozone treatment, according to any one of claims 1 to 4. The composite laminate described. The composite laminate according to any one of claims 1 to 5, wherein the metal base material is made of aluminum. The composite laminate according to claim 6, wherein the metal base material is made of aluminum, and the surface treatment includes at least one of an etching treatment and a boehmite treatment. The composite laminate according to any one of claims 1 to 5, wherein the metal base material is made of a metal selected from the group consisting of iron, titanium, magnesium, stainless steel and copper. The composite laminate according to any one of claims 1 to 8, wherein the resin coating layer is a primer layer. A method for producing a composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material.
At least one layer of the resin coating layer is formed by subjecting a combination of polyaddition-reactive compounds that produce a linear polymer to a polyaddition reaction on the surface-treated surface of the metal substrate.
A method for producing a composite laminate, wherein the combination is at least one of the following (1) and (2).
(1) At least one compound selected from the group consisting of a bifunctional glycol compound, a bifunctional amino compound and a bifunctional thiol compound, and a bifunctional isocyanate compound (2) A group consisting of a bifunctional carboxy compound and a bifunctional thiol compound. At least one compound selected from and a bifunctional epoxy compound A method for producing a composite laminate having a metal base material and one or a plurality of resin coating layers laminated on the surface of the metal base material.
A composite in which at least one layer of the resin coating layer is formed by homopolymerizing or copolymerizing a radically polymerizable compound which is a monofunctional monomer having an unsaturated group on the surface-treated surface of the metal substrate. Method for manufacturing a laminate. Before forming the resin coating layer, at least one surface treatment selected from the group consisting of blast treatment, polishing treatment, etching treatment, chemical conversion treatment, plasma treatment, corona discharge treatment and UV ozone treatment is performed on the metal substrate. The method for producing a composite laminate according to claim 10 or 11. Before forming the resin coating layer, the surface-treated surface of the metal substrate is treated with at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound to form a functional group-adhering layer. The method for producing a composite laminate according to any one of claims 10 to 12, wherein the composite laminate is formed. A metal-resin bonded body in which a surface of the composite laminate on the primer layer side according to claim 9 and a resin material are bonded and integrated. The method for producing a metal-resin bonded body according to claim 14.
When molding the resin material by at least one method selected from the group consisting of injection molding, press molding, filament winding molding, and hand lay-up molding, the surface of the composite laminate on the primer layer side and the resin material. A method of manufacturing a metal-resin bonded body that joins and integrates with. The method for producing a metal-resin bonded body according to claim 14.
The resin material is applied to the primer layer by at least one welding method selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, a hot pressing method, and an injection welding method. A method for manufacturing a metal resin bonded body to be welded.

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