JP6918894B2 - Composite laminate and metal-polyamide resin joint - Google Patents

Description

The present invention relates to a composite laminate capable of bonding a metal and a polyamide resin with high strength and a method for producing the same, and a metal-polyamide resin conjugate using the composite laminate and a method for producing the same.

In the fields of automobile parts, OA equipment, etc., where weight reduction of products is required, there is an increasing demand for metal-resin joints in which a metal material such as aluminum and a resin are joined and integrated.

As a resin member for a metal-resin joint, various resin members according to the application are being studied. For example, polyamide is excellent in heat resistance, chemical resistance, mechanical properties, stress cracking resistance, creep properties, etc., and is useful as a resin member for a metal-resin joint in which these properties are required.
Regarding a metal resin bonded body using polyamide as a metal bonding target, a metal member obtained by injection molding a polyamide resin on a metal member having a specific surface roughness (Patent Document 1), or a specific glass transition temperature and a specific A polyamide-based resin member satisfying a crystallization temperature is bonded to a metal member (Patent Document 2).

Japanese Unexamined Patent Publication No. 2007-182071 JP-A-2019-77154

However, in the prior art, there is a problem that sufficient bonding strength cannot be realized for applications such as automobile parts and OA equipment.
Further, the technique of Patent Document 1 is premised on the use of a metal member having a specific surface roughness, and the technique of Patent Document 2 is premised on the use of a specific polyamide-based resin member. There is also a problem that they lack versatility.

The present invention has been made in view of such a technical background, and provides a composite laminate suitable for an application of joining an arbitrary metal and an arbitrary polyamide resin with high strength, and related techniques thereof. Make it an issue. The related technology means a method for producing the composite laminate, a metal-polyamide resin bonded body using the composite laminate, and a method for producing the same.

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

<Composite laminate>
[1] A composite laminate having a metal material and a resin coating layer composed of one or a plurality of resin layers laminated on the metal material, and at least one layer of the resin layer is the metal material. A composite laminate which is a nylon 6-based resin layer containing nylon 6 obtained by ring-opening polymerization of ε-caprolactam above.
[2] The resin coating layer is further formed from a thermosetting resin layer formed of a resin composition containing a thermosetting resin and a polymer of a field-polymerized resin composition containing a field-polymerized resin. The composite laminate according to [1], which comprises at least one resin layer selected from the in-situ polymerization type resin layers.
[3] The composite laminate according to [2], wherein the field-polymerized resin layer is a field-polymerized thermoplastic phenoxy resin layer formed of a polymer of a resin composition containing a field-polymerized phenoxy resin.
[4] The composite laminate according to [2] or [3], 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.
[5] A functional group-containing layer laminated in contact with the metal material and the resin coating layer is provided between the metal material and the resin coating layer, and the functional group-containing layer is described in (1) to (1) to the following. The composite laminate according to any one of [1] to [4], which contains at least one functional group selected from the group consisting of (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) A mercapto group derived from a silane coupling agent, and an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group. A functional group obtained by reacting at least one selected from the group consisting of a compound having (meth) acryloyl group and a compound having an amino group (4) a thiol compound with a (meth) acryloyl group derived from a silane coupling agent. (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound [6] The surface of the metal material is subjected to plasma treatment, corona discharge treatment, blast treatment, polishing treatment, laser treatment, etc. The composite laminate according to any one of [1] to [5], which is subjected to at least one pretreatment selected from the group consisting of an etching treatment and a chemical conversion treatment.
[7] The composite laminate according to any one of [1] to [6], wherein the metal material is aluminum.
[8] The composite laminate according to [7], wherein the pretreatment is at least one selected from plasma treatment, corona discharge treatment, and etching treatment.
[9] The composite laminate according to any one of [1] to [6], wherein the metal material comprises at least one selected from the group consisting of iron, titanium, magnesium, stainless steel and copper.

<Manufacturing method of composite laminate>
[10] The method for producing a composite laminate according to any one of [1] to [9], wherein ε-caprolactam is ring-opened and polymerized on the metal material to form the nylon 6-based resin layer. , A method for manufacturing a composite laminate.
[11] The method for producing a composite laminate according to any one of [2] to [9], at least selected from the thermosetting resin layer and the field polymerization type resin layer on the metal material. A method for producing a composite laminate, in which one type of resin layer is laminated and ε-caprolactam is ring-opened polymerized on the resin layer to form the nylon 6 resin layer.
[12] The composite laminate according to [11], wherein the field-polymerized resin layer is a field-polymerized thermoplastic phenoxy resin layer formed of a polymer of a resin composition containing a field-polymerized phenoxy resin. Production method.
[13] The metal material is subjected to at least one pretreatment selected from the group consisting of plasma treatment, corona discharge treatment, blast treatment, polishing treatment, laser treatment, etching treatment and chemical conversion treatment [10] to [12]. ]. The method for producing a composite laminate according to any one of.
[14] The surface of the metal material is subjected to at least one treatment selected from the group consisting of the following (1') to (7') to form the functional group-containing layer, and the functional group-containing layer is formed on the functional group-containing layer. The method for producing a composite laminate according to any one of [10] to [13], wherein the nylon 6 resin layer is formed by ring-opening polymerization of ε-caprolactam.
(1') Treatment with a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group (2') A silane coupling agent having an amino group Treatment to add at least one selected from epoxy compounds and thiol compounds after treatment with (3') After treatment with a silane coupling agent having a mercapto group, epoxy compounds, amino compounds, isocyanate compounds, (meth) acryloyl Treatment to add at least one selected from the group consisting of compounds having a group and an epoxy group, and a compound having a (meth) acryloyl group and an amino group (4') In a silane coupling agent having a (meth) acryloyl group. Treatment to add a thiol compound after treatment (5') After treatment with a silane coupling agent having an epoxy group, it is selected from the group consisting of compounds having amino groups and (meth) acryloyl groups, amino compounds, and thiol compounds. Treatment to add at least one (6') Treatment with isocyanate compound (7') Treatment with thiol compound

<Metal-polyamide resin joint>
[15] A metal-polyamide resin bonded body in which a surface of the composite laminate according to any one of [1] to [9] on the resin coating layer side and a polyamide resin are bonded and integrated.

<Manufacturing method of metal-polyamide resin joint>
[16] The method for producing a metal-polyamide resin bonded body according to [15], wherein the polyamide resin is injection-molded or press-molded on the surface on the resin coating layer side to form the polyamide resin. A method for producing a metal-polyamide resin bonded body, which is bonded to the surface on the resin coating layer side.
[17] The metal-polyamide resin joint according to [15], wherein the polyamide resin is welded to the surface on the resin coating layer side. Manufacturing method.

According to the present invention, it is possible to provide a composite laminate suitable for an application of joining an arbitrary metal and an arbitrary polyamide resin with high strength, and related techniques thereof.

It is explanatory drawing which shows the structure of the composite laminated body in one Embodiment. It is explanatory drawing which shows the structure of the composite laminated body in another embodiment. It is explanatory drawing which shows the structure of the composite laminated body in still another embodiment. It is explanatory drawing which shows the structure of the metal-polyamide resin bonded body in one Embodiment.

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

[Composite laminate]
As shown in FIG. 1, the composite laminate 1 of the present embodiment has a metal material 2 and a resin coating layer 3 composed of one or a plurality of resin layers laminated on the metal material 2. At least one layer of the resin coating layer 3 is a nylon 6-based resin layer 31 containing nylon 6 obtained by ring-opening polymerization of ε-caprolactam on the metal material 2.

<Metal material 2>
The metal type of the metal material 2 is not particularly limited. Examples of the metal type include aluminum, iron, titanium, magnesium, stainless steel, copper and the like. Of these, aluminum is particularly preferably used from the viewpoint of light weight and ease of processing.

Before laminating the resin coating layer 3 on the metal material 2, it is preferable to remove contaminants on the surface of the metal material and / or perform a pretreatment for the purpose of anchoring effect.

By the pretreatment, as shown in FIG. 1, fine irregularities 21 can be formed on the surface of the metal material 2 to roughen the surface.
By the pretreatment, the adhesiveness between the surface of the metal material 2 and the resin coating layer 3 can be improved. In addition, these pretreatments can also contribute to improving the bondability with the polyamide resin to be bonded.

Examples of the pretreatment include plasma treatment, corona discharge treatment, blast treatment, polishing treatment, laser treatment, etching treatment, chemical conversion treatment and the like. Of these, surface treatment that generates hydroxyl groups on the surface of the metal material 2 is preferable, and specifically, plasma treatment, blast treatment, polishing treatment, laser treatment, etching treatment, chemical conversion treatment, and the like are preferable. These surface 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.

Normally, the surface of the metal material 2 in the air is covered with an oxide film, and it is considered that hydroxyl groups are present there. However, new hydroxyl groups are generated by the above pretreatment to increase the number of hydroxyl groups on the surface of the metal material 2. Can be done.

Plasma treatment is a method of creating a plasma beam with a high-voltage power supply and a rod and hitting it against the surface of the material to excite molecules to create 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. ..

Corona discharge treatment includes a method applied to surface modification of a polymer film, starting from radicals generated by electrons emitted from electrodes cutting the polymer main chain and side chains of the polymer surface layer. This is a method of generating a hydroxyl group or a polar group on the surface.

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

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

The laser treatment rapidly heats only the surface layer by laser irradiation and then cools the surface layer to improve the surface characteristics, which is an effective method for roughening the surface. Known laser processing techniques can be used.

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

The chemical conversion treatment mainly forms a chemical conversion film on the surface of a metal material.
Examples of the chemical conversion treatment include boehmite treatment and zirconium treatment.
In the boehmite treatment, a boehmite film is formed on the surface of the base material by treating aluminum, which is a metal 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 aluminum, which is a metal material, in hot water containing triethanolamine at a concentration of 0.1 to 5.0% by mass at 90 to 100 ° C. for 3 seconds to 5 minutes.
In the zirconium treatment, a film of a zirconium compound is formed on the surface of the metal material by immersing aluminum, which is a metal material, in a zirconium salt-containing liquid such as zirconium phosphate. For example, aluminum, which is a metal material, is placed in a chemical agent for zirconium treatment (for example, "Parcolate 3762" manufactured by Nippon Polarizing Co., Ltd., "Parcolate 3796", etc.) at 45 to 70 ° C. It is preferable to immerse the metal in 0.5 to 3 minutes. The zirconium treatment is preferably performed after the etching treatment by the caustic soda method.

When the metal material 2 is aluminum, it is particularly preferable to include at least one pretreatment selected from plasma treatment, corona discharge treatment, etching treatment and boehmite treatment, but plasma treatment and corona discharge which are dry treatments are included. The treatment is more preferred.

<Resin coating layer 3>
The resin coating layer 3 is laminated on the metal material 2.
The resin coating layer may be laminated on the surface of the metal material 2 which has not been subjected to the pretreatment, or may be laminated on the surface of the metal material 2 which has been subjected to the pretreatment. Alternatively, it may be laminated on the surface of the functional group-containing layer 4 described later.

[Nylon 6 resin layer 31]
At least one of the resin layers constituting the resin coating layer 3 is nylon 6 containing nylon 6 (hereinafter, may be abbreviated as "PA6") formed by ring-opening polymerization of ε-caprolactam on the metal material 2. The based resin layer 31.
Here, above the metal material 2 is not limited to the surface of the metal material 2, but is the surface of the functional group-containing layer 4 described later, the surface of the field-polymerized resin layer 32, and the thermosetting resin layer 33. It means to include any case of the surface.

The resin coating layer 3 may be composed of a plurality of layers including a nylon 6 resin layer 31 and a layer other than the nylon 6 resin layer.

When the resin coating layer is composed of a plurality of layers, it is preferable that the essential nylon 6-based resin layer 31 is laminated so as to be the outermost surface on the opposite side to the metal material 2.

Specifically, when the composite laminate 1 has a functional group-containing layer 4 and the resin coating layer 3 is composed of a single layer, ring-opening polymerization of ε-caprolactam is carried out on the surface of the functional group-containing layer 4, which will be described later. It is preferable to carry out with. When the resin coating layer 3 is composed of a plurality of layers, it is preferable that the ring-opening polymerization of ε-caprolactam is performed on the surface of the resin coating layer 3 other than the nylon 6-based resin layer 31.
The resin coating layer 3 formed in such an embodiment has excellent adhesiveness to any polyamide-based resin to be bonded.

The nylon 6-based resin layer 31 preferably contains nylon 6 in an amount of 50 to 95% by mass, more preferably 70 to 90% by mass.
In addition to nylon 6, the nylon 6-based resin layer 31 may contain nylon 11 and nylon 12, which are n-nylons synthesized by a polycondensation reaction of ω amino acids.

[In-situ polymerization type resin layer 32]
As shown in FIG. 2, the resin coating layer 3 is composed of a plurality of resin layers of the nylon 6 resin layer 31 and other layers, and at least one of the resin layers other than the nylon 6 resin layer 31. The layer can be composed of a layer formed of a polymer of a field-polymerized resin composition containing a field-polymerized resin (hereinafter referred to as a field-polymerized resin layer 32).
The field-polymerized resin composition preferably contains the field-polymerized resin in an amount of 40% by mass to 100% by mass, more preferably 70% by mass to 100% by mass.

In the present specification, the in-situ polymerization type resin composition is heated by subjecting a combination of specific bifunctional compounds to a polyaddition reaction in the presence of a catalyst, or by a radical polymerization reaction of a specific monofunctional monomer. It means a resin composition that forms a plastic structure, that is, a linear polymer structure. Unlike the thermosetting resin that forms a three-dimensional network with a crosslinked structure, the in-situ polymerization type resin composition does not form a three-dimensional network with a crosslinked structure and has thermoplasticity.
The field-polymerized resin layer 32 is formed by field-polymerization, that is, the field-polymerized resin composition dissolved in a solvent is applied onto the metal material 2 or the functional group-containing layer 4, and then the solvent is volatilized. It can be obtained by polymerizing the in-situ polymerization type resin composition. The field-polymerized resin layer 32 is preferably a field-polymerized thermoplastic phenoxy resin layer formed of a polymer of a resin composition containing a field-polymerized phenoxy resin. The field-polymerized phenoxy resin is a resin also called a thermoplastic epoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound undergo a double addition reaction in the presence of a catalyst. By doing so, a thermoplastic structure, that is, a linear polymer structure is formed. The in-situ polymerization type phenoxy resin can form a resin coating layer having thermoplasticity, unlike a thermosetting resin that constitutes a three-dimensional network having a crosslinked structure. Since the field-polymerized phenoxy resin has such characteristics, it is possible to form a field-polymerized thermoplastic phenoxy resin layer which is a field-polymerized resin layer 32 having excellent adhesiveness by field polymerization. ..

The method for forming the in-situ polymerization type resin layer 32 is not particularly limited, and examples thereof include a spray coating method and a dipping method.

The resin composition containing the field-polymerized resin may contain a solvent and, if necessary, an additive such as a colorant in order to sufficiently proceed the heavy addition reaction of the field-polymerized resin. In this case, it is preferable that the in-situ polymerization type resin is the main component among the components other than the solvent. The main component means that the content of the in-situ polymerization type resin is 50 to 100% by mass. The content is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass.

As the polyaddition reactive compound for obtaining the in-situ polymerization type resin, a combination of a bifunctional epoxy resin and a bifunctional phenolic compound is preferable.
Examples of the bifunctional epoxy resin include bisphenol type epoxy resin and biphenyl type epoxy resin. Of these, one type may be used alone, or two or more types may be used in combination. Specifically, "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", "jER (registered trademark) 1004", and the same, manufactured by Mitsubishi Chemical Corporation. Examples thereof include "jER (registered trademark) YX-4000".
Examples of the bifunctional phenol compound include bisphenol and biphenol. Of these, one type may be used alone, or two or more types may be used in combination.
Examples of these combinations include bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, biphenyl type epoxy resin and 4,4'-biphenol and the like. Further, for example, a combination of "WPE190" and "EX-991L" manufactured by Nagase ChemteX Corporation can be mentioned.

As the catalyst for the polyaddition reaction of the in-situ polymerization type resin, for example, tertiary amines such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; phosphorus compounds such as triphenylphosphine are suitable. Used for.
The heavy addition reaction is preferably carried out by heating at 120 to 200 ° C. for 5 to 90 minutes, although it depends on the type of reaction compound and the like. Specifically, the on-site polymerization type resin layer can be formed by coating the resin composition, volatilizing a solvent as appropriate, and then heating to carry out a double addition reaction.

[Thermosetting resin layer 33]
As shown in FIG. 2, the resin coating layer 3 is composed of a plurality of resin layers of the nylon 6 resin layer 31 and other layers, and at least of the resin layers other than the nylon 6 resin layer 31. One layer may also be composed of a thermosetting resin layer 33 formed of a cured product of a resin composition containing a thermosetting resin.

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

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

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

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

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

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

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

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

Examples of the polyol compound in the polyol curing type include polyester polyols, polyether polyols, phenol resins and the like.
Further, examples of the isocyanate compound having an isocyanato group in the polyol-curable type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate. (TDI) or a mixture thereof, p-phenylenediocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) 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, Amine-based catalysts such as N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine; dibutyltindi Examples thereof include organotin catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate and dibutyltin dimalate.
In the polyol curing type, it is generally preferable to add 0.01 to 10 parts by mass of the urethanization catalyst to 100 parts by mass of the polyol compound.

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

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

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

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

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

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

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

[Action of resin coating layer]
The resin coating layer 3 is formed on the metal material 2 with excellent adhesiveness. The surface of the metal material 2 is protected by the resin coating layer 3, and deterioration such as dirt adhesion to the surface of the metal material 2 and oxidation of the surface of the metal material 2 can be suppressed.

The resin coating layer 3 imparts excellent bondability to the polyamide resin 6 to be bonded to the metal material 2.
The resin coating layer 3 makes it possible to obtain a composite laminate 1 capable of maintaining a state in which excellent adhesiveness can be obtained for a long period of several months.

The resin coating layer 3 can be a primer layer of the composite laminate.
The primer layer referred to here is interposed between the metal material and the bonding target when the metal material 2 is bonded and integrated with the bonding target, for example, as in the metal-polyamide resin bonding body 5 described later. However, it shall mean a layer that improves the adhesiveness of the metal material to the object to be joined.

<Functional group-containing layer 4>
As shown in FIG. 3, between the metal material 2 and the resin coating layer 3, there is a one-layer or a plurality of functional group-containing layers 4 laminated in contact with the metal material 2 and the resin coating layer 3. You can also do it.
When the functional group-containing layer 4 is provided, the functional group formed by the functional group-containing layer reacts with the hydroxyl group on the surface of the metal material and the functional group of the resin constituting the resin coating layer, respectively. As a result, the effect of improving the adhesiveness between the surface of the metal material and the resin coating layer can be obtained. In addition, the effect of improving the bondability with the bonding target can also be obtained.

"process"
The functional group-containing layer 4 is preferably formed by subjecting the surface of the metal material 2 to at least one treatment selected from the group consisting of the following (1') to (7').
(1') Treatment with a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group (2') A silane coupling agent having an amino group Treatment to add at least one selected from epoxy compounds and thiol compounds after treatment with (3') After treatment with a silane coupling agent having a mercapto group, epoxy compounds, amino compounds, isocyanate compounds, (meth) acryloyl Treatment to add at least one selected from the group consisting of compounds having a group and an epoxy group, and a compound having a (meth) acryloyl group and an amino group (4') In a silane coupling agent having a (meth) acryloyl group. Treatment to add a thiol compound after treatment (5') After treatment with a silane coupling agent having an epoxy group, it is selected from the group consisting of compounds having amino groups and (meth) acryloyl groups, amino compounds, and thiol compounds. Treatment to add at least one (6') Treatment with isocyanate compound (7') Treatment with thiol compound << Functional group >>
The functional group-containing layer 4 preferably contains the functional group introduced by the above treatment, and specifically, preferably contains at least one functional group selected from the group consisting of the following (1) to (7). ..
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group (meth) acryloyl group, and a mercapto group. (2) An amino group derived from a silane coupling agent , A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) An epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group are added to a mercapto group derived from a silane coupling agent. A functional group formed by reacting at least one selected from the group consisting of a compound having a compound and a compound having a (meth) acryloyl group and an amino group. (4) A thiol compound is added to a (meth) acryloyl group derived from a silane coupling agent. Reacting functional group (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound In the present specification, the term "(meth) acryloyl group" means an acryloyl group and / or a methacryloyl group. .. Similarly, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate.

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

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

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

The silane coupling agent is not particularly limited, but examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxy. Examples thereof include propylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be mentioned. Examples of the silane coupling agent having a mercapto group include 3-thiolpropylmethyldimethoxysilane and dithioltriazinepurpyrtriethoxysilane. Examples of the silane coupling agent having a (meth) acryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like. In addition, as other effective silane coupling agents, silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, 3-tri. Ethethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris-( Trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, and the like. These may be used alone or in combination of two or more.

[Epoxy compound]
As the epoxy compound, a known epoxy compound or the like can be used. A polyvalent epoxy compound or a compound having an alkenyl group other than the epoxy group is preferable. The epoxy compound is not particularly limited, but for example, glycidyl (meth) acrylate, allyl glycidyl ether, which can have a (meth) acryloyl group or an allyl group whose terminal group is a radical reactive group, and allyl glycidyl ether, and the like. Examples thereof include 1,6-hexanediol diglycidyl ether having an epoxy group as a terminal group, and an epoxy resin having two or more epoxy groups in the molecule. It may also be an alicyclic epoxy compound, such as 3,4-epoxycyclohexylmethylmethacrylate (Cyclomer M100 manufactured by Daicel Co., Ltd.), 1,2-epoxy-4-vinylcyclohexane (Ceroxide 2000 manufactured by Daicel Co., Ltd.), 3', Examples thereof include 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (celloxide 2021P manufactured by Daicel Co., Ltd.).

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

The thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-thiol propionate) having a mercapto group as a terminal group (for example, "QX40" manufactured by Mitsubishi Chemical Corporation). Toray Fine Chemicals Co., Ltd. "QE-340M"), ether-based first-class thiols (for example, "Cup Cure 3-800" manufactured by Cognis), 1,4-bis (3-thiolbutyryloxy) butane ( For example, "Karen's MT (registered trademark) BD1" manufactured by Showa Denko Co., Ltd.), pentaerythritol tetrakis (3-thiol butylate) (for example, "Karen's MT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.), 1 , 3,5-Tris (3-thiolbutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Karens MT (registered)" manufactured by Showa Denko Co., Ltd. Trademark) NR1 ”) and the like.

[Amino compound]
As the amino compound, a known amino compound or the like can be used. Polyfunctional amino compounds and compounds having an alkenyl group in addition to the amino group (including amide) are preferable. The amino compound is not particularly limited, but for example, ethylenediamine having an amino group at the terminal, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, and the like. 2,5-dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3 '-Iminobis (propylamine), 3,3'-methylimiminobis (propylamine), bis (3-aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine , Bisaminomethylnorbornan, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, 3,9-bis (3-aminopropyl) -2,4 , 8,10-Tetraoxaspiro [5,5] undecane, aminoethylpiperazine, (meth) acrylamide, which can be a (meth) acryloyl group whose terminal group is a radically reactive group, and the like.

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

The isocyanate compound is not particularly limited, but is, for example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate, which are polyfunctional isocyanates having an isocyanato terminal group. 2-Isocyanatoethyl methacrylate (for example, "Karens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd., which is an isocyanate compound whose terminal group can be a (meth) acryloyl group which is a radical reactive group in addition to (IPDI) and the like. ) ”), 2-Isocyanate ethyl acrylate (for example,“ Karens AOI (registered trademark) ”manufactured by Showa Denko Co., Ltd.,“ AOI-VM (registered trademark) ”), 1,1- (bisacryloyloxyethyl) ethyl isocyanate (For example, "Karens BEI (registered trademark)" manufactured by Showa Denko Co., Ltd.) and the like.

[Metal-Polyamide Resin Bonded Body 5]
As shown in FIG. 4, in the metal-polyamide resin bonding body 5 of the present embodiment, the resin coating layer 3 of the composite laminate 1 is a primer layer as described above, and the surface on the primer layer side and the surface on the primer layer side. The polyamide resin 6 is joined and integrated.

The thickness of the primer layer (thickness after drying) depends on the material to be bonded and the contact area of the bonded portion, but from the viewpoint of obtaining excellent adhesiveness between the surface on the primer layer side and the polyamide resin. From the viewpoint of suppressing thermal deformation of the bonded body due to the difference in thermal expansion coefficient between different materials, it is preferably 1 μm to 10 mm, more preferably 20 μm to 3 mm, and further preferably 30 μm to 1 mm. .. When the primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) is the total thickness of each layer.

The polyamide resin in the metal-polyamide resin conjugate is preferably an aliphatic polyamide, and is preferably polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyundecaneamide (nylon 11), or polydodecaneamide. (Nylon 12) is more preferable, and polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 66) are most preferable.
However, the polyamide resin is not limited to the above, and any polyamide resin can be used as a copolymer / mixture depending on the required properties such as moldability and compatibility.

Examples of the method for producing the metal-polyamide resin bonded body include a method of molding the molded body of the polyamide resin 6 and at the same time joining and integrating the molded body with the composite laminate 1. Specifically, the polyamide-based resin 6 is molded on the surface of the composite laminate 1 on the resin coating layer side by, for example, injection molding, press molding, transfer molding, or the like, and the polyamide-based resin 6 is molded into the resin coating layer. A method of obtaining a metal-polyamide resin bonded body by bonding to the side surface can be mentioned.
A metal-polyamide resin bonded body can also be obtained by welding a molded body of the polyamide resin 6 to the surface of the composite laminate 1 on the resin coating layer side.
Examples of the welding method include various welding methods such as hot air welding, hot plate welding, high frequency welding, induction heating welding, ultrasonic welding, vibration welding, and spin welding.

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

Composite laminates 1 to 4 were prepared by the methods described in Example 1-1, Example 2-1 and Example 3-1 below, and Comparative Example 3-1 below. Laminates 1 and 2 were produced by the methods described in Comparative Example 1-1 and Comparative Example 2-1 below.
The metal-resin bonded bodies 1 to 3 for the tensile shear adhesive strength test were prepared by the methods described in Examples 1-2, 2-2, and 3-2 below.
[Evaluation of bondability]
After leaving the metal resin bonded bodies 1 to 3 at room temperature for 1 day, a tensile tester (universal tester Autograph "AG-IS" manufactured by Shimadzu Corporation; load cell 10 kN, tensile speed) conforms to ISO19095 1-4. A tensile shear adhesive strength test was performed at 10 mm / min, a temperature of 23 ° C., and 50% RH), and the adhesive strength was measured. The measurement results are shown in Table 1 below.

<Example 1-1>
(Preprocessing)
An 18 mm × 45 mm, 1.5 mm thick aluminum plate (A6063) was immersed in a 5% by mass sodium hydroxide aqueous solution for 1.5 minutes, neutralized with a 5% by mass nitric acid aqueous solution, and washed with water. Etching treatment was performed by drying.
Then, atmospheric pressure plasma treatment was performed using an atmospheric pressure plasma apparatus manufactured by Plasmatreat (Germany).

(Formation of functional group-containing layer)
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. The aluminum plate after the atmospheric pressure plasma treatment was immersed for 20 minutes. The aluminum plate was taken out and dried to form a functional group-containing layer on the surface (surface-treated portion) of the aluminum plate after the atmospheric pressure plasma treatment.

(Formation of resin coating layer)
A solution in which 10 g of ε-caprolactam was dissolved in 10 g of acetone; a solution in which 2.3 g of 6-aminohexanoic acid was mixed with 8 g of acetone: solution B was prepared.
Next, an equal mass mixture of solution A and solution B was applied to the surface of the functional group-containing layer of the aluminum plate. Then, after holding in a vacuum dryer under reduced pressure for 30 minutes at room temperature, the operation of removing the resin from the vacuum dryer and putting it in the machine again is repeated three times to volatilize acetone, and further, holding under reduced pressure at 190 ° C. for 1 hour. A composite laminate 1 having a 40 μm-thick PA6 coating layer (a resin coating layer composed of a resin layer containing PA6 ring-opened and polymerized on a metal material) formed on the surface of the functional group-containing layer. Made.

<Example 1-2>
(Metal resin joint 1)
On the surface of the composite laminate 1 on the resin coating layer side, a 30% glass-reinforced PA6 (DSM trade name: Novamid 1013G30 (bonding target)) is applied to an injection molding machine ("SE100V" manufactured by Sumitomo Heavy Industries, Ltd .; cylinder. Metal resin bonding, which is a test piece for tensile test conforming to ISO19095, by injection molding at a temperature of 270 ° C, a tool temperature of 80 ° C, an injection speed of 50 mm / sec, and a peak / holding pressure of 100/100 [MPa / MPa]). Body 1 (PA6, 10 mm × 45 mm × 3 mm, joint length 5 mm) was produced.

<Example 2-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out, and the surface of an aluminum plate (A6063 having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm) was subjected to atmospheric pressure plasma treatment.

(Formation of functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to form a functional group-containing layer on the surface (surface-treated portion) of the aluminum plate after the atmospheric pressure plasma treatment.

(Formation of resin coating layer_1 layer)
In-situ polymerization type in which 100 g of epoxy resin (“jER® 1001” manufactured by Mitsubishi Chemical Corporation), 24 g of bisphenol A, and 0.4 g of triethylamine are dissolved in 250 g of acetone on the surface of the functional group-containing layer. The phenoxy resin composition was applied to the surface of the functional group-containing layer of the aluminum plate by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it was left in a furnace at 150 ° C. for 30 minutes to carry out a polymerization reaction, and then allowed to cool to room temperature to allow the first resin coating layer (1st layer). In-situ polymerization type thermoplastic phenoxy resin layer) was formed.

(Formation of resin coating layer_2nd layer)
Next, a solution in which 10 g of ε-caprolactam was dissolved in 10 g of acetone; a solution in which 0.6 g of 6-aminohexanoic acid was mixed with 5 g of acetone: solution B was prepared.
Next, an equal mass mixture of solution A and solution B is applied to the surface of the resin coating layer of the first layer of the aluminum plate, and then held in a vacuum dryer under reduced pressure and at room temperature for 30 minutes, and then vacuumed. The operation of taking it out of the dryer and putting it in the machine again was repeated three times to volatilize the acetone, and then the mixture was kept under reduced pressure at 190 ° C. for 1 hour, and the surface of the first resin coating layer had a thickness of 30 μm. A composite laminate 2 in which a PA6 coating layer (a resin coating layer composed of a resin layer containing PA6 formed by ring-opening polymerization on a metal material) was formed was produced.

<Example 2-2>
(Metal resin joint 2)
30% glass-reinforced PA66 (DSM "Novamid 3021GH30" (bonding target)) is applied to the surface of the composite laminate 2 on the resin coating layer side, and an injection molding machine ("SE100V" manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature. A metal resin joint that is a test piece for tensile test conforming to ISO19095 by injection molding at 270 ° C., tool temperature 80 ° C., injection speed 50 mm / sec, peak / holding pressure 100/100 [MPa / MPa]). 2 (PA66, 10 mm × 45 mm × 3 mm, joint length 5 mm) was produced.

<Example 3-1>
(Preprocessing)
The surface of an aluminum plate (A6063) having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was polished with # 100 sandpaper, and then washed and degreased with acetone.

(Formation of functional group-containing layer)
Next, a silane coupling agent solution prepared by dissolving 0.5 g of 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) in 100 g of industrial ethanol is applied by spraying. After drying at room temperature, the mixture was kept at 120 ° C. for 20 minutes.
Further, a bifunctional thiol compound 1,4 bis (3-mercaptobutyryloxy) butane (“Karens MT (registered trademark) BD1” manufactured by Showa Denko Co., Ltd.): 0.6 g, 2,4,6-tris (dimethylamino) A solution prepared by dissolving 0.05 g of methyl) phenol (DMP-30) in 150 g of toluene is applied by spraying, dried at room temperature, and held at 120 ° C. for 20 minutes to form chemically bondable functional groups in a three-dimensional direction. I extended it.

(Formation of resin coating layer)
Next, as a field-polymerized PA6, "GAP-1R / GAP-1DA" manufactured by Nagase Chemtex Co., Ltd. was applied to the surface of the functional group-containing layer of the aluminum plate. Then, in a vacuum dryer, the mixture is kept under reduced pressure at 190 ° C. for 1 hour, and the surface of the functional group-containing layer contains a PA6 coating layer having a thickness of 40 μm (PA6 formed by ring-opening polymerization on a metal material). A composite laminate 3 in which a resin coating layer composed of a resin layer) was formed was produced.

<Example 3-2>
(Metal resin joint 3)
Using the composite laminate 3, the same operation as in Example 1-2 was carried out to prepare a metal resin joint 3 (PA6, 10 mm × 45 mm × 3 mm, joint length 5 mm) as a test piece for a tensile test.

<Example 4-1>
The composite laminated body 4 was produced in the same manner as in Example 1-1.
<Example 4-2>
(Metal resin joint 4)
Long fiber CF reinforced 6 nylon: CFRTP1 of 10 mm × 45 mm × 3 mm was obtained by injection molding using “TLP1040” (20% carbon fiber) manufactured by Toray Industries, Inc.
The primer surface of the composite laminate 4 and the CFRTP1 are overlapped so as to have a bonding area of 10 mm × 5 mm, held in a dryer at 180 ° C. for 5 minutes while being held by a clip, and welded. A metal-resin bonded body 4 (CFRTP, 10 mm × 45 mm × 3 mm, joint length 5 mm), which is a test piece for use, was prepared.

<Comparative Example 1-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out, and the surface of an aluminum plate (A6063 having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm) was subjected to atmospheric pressure plasma treatment.

(Formation of functional group-containing layer)
Next, the same operation as in Example 1-1 was carried out to prepare a laminate 1 in which a functional group-containing layer was formed on the surface (surface-treated portion) of the aluminum plate after the atmospheric pressure plasma treatment.

<Comparative Example 1-2>
Similar to Example 1-2, 30% glass tempered PA6 was injection-molded on the surface of the laminate 1 on the functional group-containing layer side to try to prepare a test piece for a tensile test, but the molding could not be performed.

<Comparative Example 2-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out, and the surface of an aluminum plate (A6063 having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm) was subjected to atmospheric pressure plasma treatment.

(Formation of functional group-containing layer)
Next, the same operation as in Example 3-1 was carried out to prepare a laminate 2 in which a functional group-containing layer was formed on the surface (surface-treated portion) of the aluminum plate after the atmospheric pressure plasma treatment.

<Comparative Example 2-2>
Similar to Example 2-2, 30% glass tempered PA66 was injection-molded on the surface of the laminate 2 on the functional group-containing layer side to attempt to prepare a test piece for a tensile test, but the molding could not be performed.

<Comparative Example 3-1>
(Preprocessing)
The same operation as in Example 1-1 was carried out, and the surface of an aluminum plate (A6063 having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm) was subjected to atmospheric pressure plasma treatment.

(Formation of functional group-containing layer)
Next, the same operation as in Example 3-1 was carried out to form a functional group-containing layer on the surface (surface-treated portion) of the aluminum plate after the atmospheric pressure plasma treatment.

(Formation of resin coating layer)
Nylon 6 manufactured by DSM (trade name: Akulon (registered trademark) polyamide 6) is placed on the surface of the functional group-containing layer of the aluminum plate, melted at 250 ° C., stretched to a thickness of 80 μm, and then returned to room temperature. , A composite laminate 4 on which a PA6 coating layer having a thickness of 80 μm was formed was produced.

<Comparative Example 3-2>
Similar to Example 2-2, 30% glass tempered PA66 was injection-molded on the surface of the composite laminate 4 on the PA6 coating layer side to prepare a test piece for a tensile test. It peeled off and a test piece for tensile test could not be prepared.

As shown in the examples of Table 1, by using a composite laminate having a resin coating layer including a nylon 6-based resin layer formed by ring-opening polymerization on a metal material, the metal and the polyamide-based resin can be obtained with high strength. Can be joined.

The composite laminate according to the present invention includes, for example, a door side panel, a bonnet, a roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, a power control unit (PCU) housing, and an electric compressor. Parts (inner wall part, suction port part, exhaust control valve (ECV) insertion part, mount boss part, etc.), lithium-ion battery (LIB) spacer, battery case, automobile parts such as LED headlamps, smartphones, laptop computers, etc. It is used as a tablet personal computer, a smart watch, a large liquid crystal television (LCD-TV), a structure for outdoor LED lighting, and the like, but is not particularly limited to these exemplified applications.

1 Composite laminate 2 Metal material 21 Fine irregularities 3 Resin coating layer (primer layer)
31 Nylon 6-based resin layer 32 In-situ polymerization type resin layer 33 Thermosetting resin layer 4 Functional group-containing layer
5 Metal-polyamide resin joint 6 Polyamide resin

Claims (17)

A composite laminate having a metal material and a primer layer composed of one or a plurality of resin layers laminated on the metal material.
Wherein at least one layer of the resin layer, on the metal material, directly or via another layer, Ri nylon 6 resin layer der containing nylon 6 obtained by ring-opening polymerization of ε- caprolactam,
The thickness of the primer layer is 1 μm to 10 mm.
A composite laminate in which the nylon 6-based resin layer is laminated on the outermost surface opposite to the material layer in the primer layer. The primer layer is a field-polymerized type formed of a thermosetting resin layer formed of a resin composition containing a thermosetting resin and a polymer of a field-polymerized resin composition containing a field-polymerized resin. The composite laminate according to claim 1, which comprises at least one resin layer selected from the resin layers. The composite laminate according to claim 2, wherein the field-polymerized resin layer is a field-polymerized thermoplastic phenoxy resin layer formed of a polymer of a resin composition containing a field-polymerized phenoxy resin. The composite laminate according to claim 2 or 3, wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin. A functional group-containing layer laminated in contact with the metal material and the primer layer is provided between the metal material and the primer layer.
The composite laminate according to any one of claims 1 to 4, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group, and a mercapto group. (2) An amino group derived from a silane coupling agent. A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3) A mercapto group derived from a silane coupling agent, and an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group. A functional group obtained by reacting at least one selected from the group consisting of a compound having (meth) acryloyl group and a compound having an amino group (4) a thiol compound with a (meth) acryloyl group derived from a silane coupling agent. (5) An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound The surface of the metal material is subjected to at least one pretreatment selected from the group consisting of plasma treatment, corona discharge treatment, blast treatment, polishing treatment, laser treatment, etching treatment and chemical conversion treatment. The composite laminate according to any one of 5 to 5. The composite laminate according to any one of claims 1 to 6, wherein the metal material is aluminum. The composite laminate according to claim 7, wherein the pretreatment is at least one selected from a plasma treatment, a corona discharge treatment, and an etching treatment. The composite laminate according to any one of claims 1 to 6, wherein the metal material comprises at least one selected from the group consisting of iron, titanium, magnesium, stainless steel and copper. The method for producing a composite laminate according to any one of claims 1 to 9.
A method for producing a composite laminate, wherein ε-caprolactam is ring-opened and polymerized on the metal material directly or via another layer to form the nylon 6-based resin layer. The method for producing a composite laminate according to any one of claims 2 to 9.
At least one resin layer selected from the thermosetting resin layer and the in-situ polymerization type resin layer is laminated on the metal material, and ε-caprolactam is directly ring-opened polymerized on the resin layer. A method for producing a composite laminate, which forms the nylon 6-based resin layer. The method for producing a composite laminate according to claim 11, wherein the field-polymerized resin layer is a field-polymerized thermoplastic phenoxy resin layer formed of a polymer of a resin composition containing a field-polymerized phenoxy resin. Any one of claims 10 to 12, wherein the metal material is subjected to at least one pretreatment selected from the group consisting of plasma treatment, corona discharge treatment, blast treatment, polishing treatment, laser treatment, etching treatment and chemical conversion treatment. The method for producing a composite laminate according to the item. The surface of the metal material is subjected to at least one treatment selected from the group consisting of the following (1') to (7') to form the functional group-containing layer, and directly or directly on the functional group-containing layer. The method for producing a composite laminate according to any one of claims 10 to 13, wherein the nylon 6 resin layer is formed by ring-opening polymerization of ε-caprolactam via another layer.
(1') Treatment with a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group (2') A silane coupling agent having an amino group Treatment to add at least one selected from epoxy compounds and thiol compounds after treatment with (3') After treatment with a silane coupling agent having a mercapto group, epoxy compounds, amino compounds, isocyanate compounds, (meth) acryloyl Treatment to add at least one selected from the group consisting of compounds having a group and an epoxy group, and a compound having a (meth) acryloyl group and an amino group (4') In a silane coupling agent having a (meth) acryloyl group. Treatment to add a thiol compound after treatment (5') After treatment with a silane coupling agent having an epoxy group, it is selected from the group consisting of compounds having amino groups and (meth) acryloyl groups, amino compounds, and thiol compounds. Treatment to add at least one (6') Treatment with isocyanate compound (7') Treatment with thiol compound A metal-polyamide resin bonded body in which a surface of the composite laminate according to any one of claims 1 to 9 on the primer layer side and a polyamide resin are bonded and integrated. The method for producing a metal-polyamide resin bonded body according to claim 15, wherein the polyamide resin is injection-molded or press-molded on the surface on the primer layer side, and the polyamide resin is formed into the primer layer. A method for manufacturing a metal-polyamide resin bonded body to be bonded to the side surface. The method for producing a metal-polyamide resin bonded body according to claim 15, wherein the polyamide resin is bonded to the surface on the primer layer side by welding.

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