WO2022130591A1

WO2022130591A1 - Vehicle side step and method for manufacturing same

Info

Publication number: WO2022130591A1
Application number: PCT/JP2020/047272
Authority: WO
Inventors: 信行高橋; 正広佐藤; 和男大谷
Original assignee: 昭和電工株式会社
Priority date: 2020-12-17
Filing date: 2020-12-17
Publication date: 2022-06-23
Also published as: JPWO2022130591A1; JP7480865B2

Abstract

Provided is a vehicle side step that is equipped with a metal member and a resin member and has high bonding strength between the two members. Also provided is a method for manufacturing the vehicle side step. This vehicle side step comprises: a metal member 1 with one or more resin coating layers 4 laminated on at least a portion of the surface of a metal base material 2; and a resin member 8 that is bonded to the resin coating layer 4-side surface 4s of the metal member 1. At least one of the resin coating layers 4 is a modified polyolefin layer formed from a resin composition containing a modified polyolefin, and the modified polyolefin layer is at least one selected from the group consisting of a layer containing a reaction product 1 of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenolic compound, a layer containing a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin.

Description

Vehicle side steps and their manufacturing methods

This disclosure relates to a vehicle side step provided on the side of the vehicle body and a method for manufacturing the same.

As typified by trucks and sport utility vehicles (SUVs), vehicles with high riding positions are provided with side steps under the door as a foothold for boarding.

For example, in Patent Document 1 (Japanese Unexamined Patent Publication No. 2019-151209), it is necessary to prevent the head of the screw from being exposed on the side step and to achieve both the ease of getting on and off the vehicle and the minimum ground clearance at a high level. The structure of the side step of the vehicle for the purpose of is disclosed. In Patent Document 1, in particular, the fastening portion on the outer side in the vehicle width direction projects downward from the lower surface of the step plate, and the fastening portion on the inner side in the vehicle width direction is inside in the vehicle width direction from the step surface on which the foot is placed when getting on and off the step plate. It is said that it is configured to protrude upward from the step surface.

Japanese Unexamined Patent Publication No. 2019-151209

In Patent Document 1, the side step is composed of a step plate made of a metal member and a cover made of a resin member attached to both ends of the step plate in the vehicle front-rear direction, but the joining method thereof is not particularly disclosed. ..

Further, in view of the recent tendency to increase the proportion of the resin member in the side step in order to reduce the weight of the vehicle, the metal member is required to satisfy the strength (eg, rigidity) required for the side step. It is desired that the resin member and the resin member are more firmly bonded to each other.

The present disclosure has been made in view of the above-mentioned technical background, and an object thereof is to provide a vehicle side step provided with a metal member and a resin member and having a high joint strength between the two members, and a method for manufacturing the same.

This disclosure includes the following aspects.

[1] A metal member in which one or a plurality of resin coating layers are laminated on at least a part of the surface of the metal base material is bonded to the surface of the metal member on the resin coating layer side of the metal base material. Equipped with a resin member,
At least one layer of the resin coating layer is a modified polyolefin layer formed from a resin composition containing a modified polyolefin, and the modified polyolefin layer is composed of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound. At least one selected from the group consisting of a layer containing a reactant 1, a layer containing a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin. Side step for vehicles.

[2] The vehicle side step according to item 1 above, wherein the reaction product 1 is subjected to a double addition reaction between a bifunctional epoxy resin and a bifunctional phenol compound in a solution containing maleic anhydride-modified polyolefin.

[3] The vehicle use according to item 1 above, wherein the reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. side step.

[4] The vehicle side step according to item 1 above, wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin.

[5] The resin coating layer is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer other than the modified polyolefin layer is a resin containing a thermoplastic epoxy resin. The vehicle according to any one of 1 to 4 above, which is at least one selected from a thermoplastic epoxy resin layer formed from a composition and a curable resin layer formed from a resin composition containing a curable resin. For side steps.

[6] The vehicle side step according to item 5 above, wherein the curable resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin.

[7] A functional group-containing layer laminated in contact with the metal base material and the resin coating layer is provided between the metal base material and the resin coating layer.
The vehicle side step according to any one of the above items 1 to 6, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from the silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2) An amino group derived from the silane coupling agent. A functional group generated by the reaction of at least one selected from a glycidyl compound and a thiol compound (3) A glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group are added to a mercapto group derived from a silane coupling agent. A functional group produced by the reaction of at least one selected from the group consisting of a compound having a (meth) acryloyl group and a compound having an amino group (4) A thiol compound to a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound

[8] The surface of the metal base material is subjected to at least one surface treatment selected from the group consisting of blast treatment, polishing treatment, etching treatment and chemical conversion treatment, and the resin coating layer is the metal base material. The vehicle side step according to any one of items 1 to 7 above, which is laminated on the surface-treated surface of the above item.

[9] The resin member includes a base resin member and a surface resin member.
The lower surface of the metal member in the vehicle height direction is joined to the upper surface of the base resin member in the vehicle height direction.
A part of the upper surface of the metal member in the vehicle height direction is joined to the lower surface of the surface resin member in the vehicle height direction, and the other part of the upper surface of the metal member in the vehicle height direction is exposed. The vehicle side step according to any one of 1 to 8.

[10] The vehicle side step according to any one of items 1 to 9 above, which includes a metal plate as the metal member.

[11] The metal base material is made of an extruded aluminum material of an A6000 alloy, and has the characteristics of a tensile strength of 180 MPa or more and a Young's modulus of 60 GPa or more. Side step for vehicles.

[12] The method for manufacturing a side step for a vehicle according to any one of the above items 1 to 11, wherein the resin is manufactured by an injection molding method, a transfer molding method, a press molding method, a filament winding molding method, or a hand lay-up molding method. A method for manufacturing a side step for a vehicle, in which a resin member is joined to a surface of a metal member on the resin coating layer side when the member is molded.

In the vehicle side step of the present disclosure, the resin member is bonded to the surface of the metal member on the resin coating layer side, and at least one layer of the resin coating layer is modified from a resin composition containing a modified polyolefin. It is a polyolefin layer, and the modified polyolefin layer contains a layer containing a reaction product 1 of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin and a bifunctional phenol compound, and a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin. Since it is at least one selected from the group consisting of a layer containing the layer and a layer containing a mixture of the polyolefin and the thermoplastic epoxy resin, the bonding strength between the metal member and the resin member is high.

FIG. 1 is a left side view showing a vehicle to which the vehicle side step according to the embodiment of the present disclosure is applied. FIG. 2 is a perspective view showing the relationship between the vehicle side step shown in FIG. 1 and each stay. FIG. 3 is a plan view of the vehicle side step shown in FIG. FIG. 4 is a cross-sectional view taken along the line AA'of FIG. FIG. 5A is a schematic cross-sectional view showing a state in which a resin coating layer is formed on a surface-treated surface of a metal base material in a metal member. FIG. 5B is a schematic cross-sectional view showing a state in which a functional group-containing layer is formed on a surface-treated surface of a metal base material and a resin coating layer is formed on the surface-treated surface of the metal member. FIG. 6 is a schematic cross-sectional view of a state in which a metal member and a resin member are joined. FIG. 7 is a schematic cross-sectional view of a state in which a metal member and a resin member are joined via an adhesive layer. FIG. 8 is an SEM photograph of the boehmite film.

Next, the embodiments of the present disclosure will be described below with reference to the drawings.

In the present disclosure, unless otherwise specified in the text, the term "metal" is meant to include both pure metals consisting of a single metal element and alloys of pure metals mixed with one or more other elements. Used. For example, the term "aluminum" includes pure metals of aluminum and alloys thereof.

In the present disclosure, bonding means connecting objects to each other, and adhesion is a subordinate concept thereof, and through organic materials such as tapes and adhesives (curable resin, thermoplastic resin, etc.), It means that two adherends (those to be bonded) are put into a bonded state.

FIG. 1 is a left side view showing a vehicle to which the vehicle side step according to the embodiment of the present disclosure is applied. As shown in the figure, the vehicle side step 10 according to the embodiment of the present disclosure is the lower side of the

doors

12 and 12 in a vehicle having a high riding position represented by a truck or a sports utility vehicle (SUV). It is installed in the vehicle and is used as a foothold for boarding.

FIG. 2 is a perspective view showing the relationship between the vehicle side step 10 shown in FIG. 1 and each stay 14 for attaching the vehicle side step 10 to the vehicle body. The vehicle side step 10 is fixed to the vehicle body via a stay 14 (for example, a substantially L-shaped member obtained by press-molding a steel plate) shown in FIG. The fixing method may be a method using bolts and nuts, or may be welding.

FIG. 3 is a plan view of the vehicle side step 10 shown in FIG. 2, and FIG. 4 is a cross-sectional view taken along the line AA'of FIG. As shown in these figures, the vehicle side step 10 has a flat plate-shaped base resin plate 10a and a metal plate having a plurality of protrusions in this order from the lower side in the vehicle height direction (lower side of the paper surface in FIG. 4). It is provided with 10b and a surface resin plate 10c having a plurality of holes for the convex portion to penetrate. On the premise that the vehicle side step 10 is composed of such components, the metal plate 10b is sandwiched between the two resin plates (base resin plate 10a and surface resin plate 10c), whereby these three plates 10a are sandwiched between the two resin plates (base resin plate 10a and surface resin plate 10c). It has a sandwich structure in which 10b and 10c are integrated.

The joining status of the plates in this sandwich structure is as follows. That is, as shown in FIG. 4, the upper surface of the base resin plate 10a in the vehicle height direction and the lower surface of the metal plate 10b in the vehicle height direction are joined. Further, a part of the upper surface of the metal plate 10b in the vehicle height direction (the upper surface of the non-convex portion) and the lower surface of the surface resin plate 10c in the vehicle height direction are joined. Further, a part of the side surface of the metal plate 10b and the surface for partitioning the hole portion of the surface resin plate 10c are joined. Due to such a joining state, the upper portion of the convex portion of the metal plate 10b protrudes from the hole portion of the surface resin plate 10c, so that the upper surface of the convex portion of the metal plate 10b is exposed.

As described above, the vehicle side step 10 shown in FIGS. 3 and 4 includes the resin plate 10a, the metal plate 10b, and the resin plate 10c in this order from the lower side in the vehicle height direction to the upper side. , The present embodiment is not limited to such an embodiment. That is, although not shown in the present embodiment, the metal plate, the resin plate, and the metal plate may be used as constituent elements in this order from the lower side in the vehicle height direction to the upper side. In this case, the metal plate and the resin plate in FIGS. 3 and 4 are interchanged, and the resin plate is sandwiched between the two metal plates to form a sandwich structure in which these three plates are integrated.

In this way, on the premise that members made of different materials (resin and metal) are used as a sandwich structure to reduce weight, one of them is projected upward in the vehicle height direction from the other to serve as a scaffold. It is possible to suppress slippage when getting on and off by adding unevenness to the side steps.

The vehicle side step 10 shown above is connected to the vehicle body via a stay on one side of the longitudinal edge portion thereof, and is used as a scaffold. At that time, if the bonding strength between the base resin plate 10a and the metal plate 10b and / or the bonding strength between the metal plate 10b and the surface resin plate 10c is not sufficient, at least one of the

resin plates

10a and 10c is an adjacent metal. It peels off from the plate 10b, and the vehicle side step 10 cannot guarantee the desired durability. However, in the vehicle side step 10 of the present embodiment, a specific resin coating layer is interposed between the base resin plate 10a and the metal plate 10b and / or between the metal plate 10b and the surface resin plate 10c. , The bonding strength between the base resin plate 10a and the metal plate 10b, and / or the bonding strength between the metal plate 10b and the surface resin plate 10c can be sufficiently ensured.

Next, the configuration of each member of the vehicle side step 10 shown in FIGS. 1 to 4 and the manufacturing method thereof will be described in detail. In the following, the metal plate 10b is also referred to as "metal member 1", and each resin plate (base resin plate 10a, surface resin plate 10c) is also referred to as "resin member 8".

[Metal member 1]
As shown in FIGS. 5A and 5B, the metal member 1 (metal plate 10b) has a metal base material 2 and a one-layer or a plurality of resin coating layers 4 laminated on the surface of the metal base material 2. is doing.

In FIGS. 5A and 5B, the resin coating layer 4 is laminated on the surface-treated surface of the metal substrate 2, and at least one layer of the resin coating layer 4 is formed from a resin composition containing a modified polyolefin. The modified polyolefin layer 4a.

The resin coating layer 4 is formed on the surface of the metal base material 2 with excellent bondability, and exhibits excellent bondability with polyolefin. As a result, the metal base material 2 is provided with excellent adhesiveness (bondability via the resin coating layer 4) to the resin member 8 containing polyolefin. Therefore, it can be said that the resin coating layer 4 is a primer layer arranged on the joint surface of the metal base material 2.

In the present disclosure, the primer layer is interposed between the metal base material 2 and the resin member 8 when the metal member 1 and the resin member 8 are joined, and the adhesiveness of the metal base material 2 to the resin member 8 ( It means that it is a layer that improves the bondability) via the resin coating layer 4.

Further, since the surface of the metal base material 2 is protected by the resin coating layer 4, deterioration such as adhesion of dirt to the surface of the metal base material 2 and oxidation can be suppressed. Therefore, it is possible to obtain the metal member 1 capable of maintaining excellent adhesiveness to the resin member even when stored for a long period of several months.

In one embodiment, as shown in FIG. 5A, in the metal member 1, the resin coating layer 4 may be directly laminated on the surface of the surface-treated portion 2a of the metal substrate 2. In another embodiment, as shown in FIG. 5B, in the metal member 1, the functional group-containing layer 3 is provided on the surface of the surface-treated portion 2a of the metal base material 2, and further, the resin is provided on the surface of the functional group-containing layer 3. The coating layer 4 may be formed. That is, the functional group-containing layer 3 may be arranged between the surface-treated portion 2a of the metal base material 2 and the resin coating layer 4.

As shown in FIG. 4, the surface-treated surface of the metal base material 2 is a surface to be joined with at least the resin member 8 on the surface of the metal member 1 (metal base material 2), that is, the metal member 1 (base material 2). 2) At least the contact portion with the resin member 8 on the surface, specifically, the entire lower surface of the metal plate 10b in the vehicle height direction and the vehicle of the metal plate 10b in the vehicle side step 10 shown in FIG. The upper surface of the upper surface in the high direction, which is not a convex portion, and the side surface of the side surface of the metal plate 10b, which does not protrude upward in the vehicle height direction from the hole portion of the surface resin plate 10c.

<Metal base material 2>
Examples of the metal type of the metal base material 2 include aluminum, iron, and stainless steel. Of these, aluminum is particularly preferably used from the viewpoint of light weight and ease of processing. In the following, the case where aluminum is applied will be described in detail.

When aluminum is applied to the metal base material 2, the type of the aluminum material of the metal base material 2 is not limited, and for example, the aluminum content is 50% by mass or more, and specifically, the aluminum material. Is preferably an A6000 series alloy (eg, A6061, A6N01, A6063, A6082, A6110), an A5000 series alloy, an A1000 series alloy, an A3000 series alloy, or the like, and the aluminum material has a high deformation energy absorption rate. A6N01 alloy, which is a highly ductile aluminum alloy, is more preferable.

It is preferable that the metal base material 2 is made of an extruded aluminum material of an A6000 alloy and has characteristics of a tensile strength of 180 MPa or more and a Young's modulus of 60 GPa or more. In this case, since the metal base material has high tensile strength (high strength) and high Young's modulus (high rigidity), it is possible to reduce the thickness of the metal plate 10b of the vehicle side step 10, and therefore, the vehicle. Contributes to weight reduction of the side step 10 for use. The upper limit of the tensile strength is not limited, and is, for example, 450 MPa. The upper limit of Young's modulus is not limited, and is, for example, 80 GPa. However, depending on the specifications, the metal base material 2 may be an aluminum die-cast material, a cast material, a forged material, or the like.

When the metal base material 2 is made of extruded aluminum, it is preferable that the metal base material 2 is manufactured by the following method.

In a preferable manufacturing method of the metal base material 2, a step of continuously casting a casting rod by supplying a molten metal of an aluminum material having predetermined characteristics to a continuous casting apparatus, a step of homogenizing the casting rod, and a step of homogenizing the casting rod are performed. A step of obtaining a billet as an extruded material by cutting to a predetermined length, a step of grinding the outer diameter of the billet, and a step of hot-extruding the billet to form an extruded material having a predetermined cross-sectional shape. The steps are performed in the order described in this description. Next, the extruded material is cut to a predetermined length, and the cut end surfaces are subjected to predetermined processing such as face cutting and deburring to obtain a metal base material 2 made of the extruded material.

[Surface treatment (part)]
When manufacturing the metal member 1, it is preferable to perform a surface treatment on the metal base material 2 before forming the resin coating layer 4. A surface-treated portion 2a is formed on at least the surface to be joined to the resin member 8 in the metal substrate 2 of FIGS. 5A and 5B. The surface treatment portion 2a is regarded as a part of the metal base material 2.

Examples of the surface treatment include cleaning / degreasing treatment with a solvent, blast treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, and chemical conversion treatment, and surface treatment for generating hydroxyl groups on the surface of the metal substrate 2. Is preferable. These surface treatments may be performed with only one type or two or more types. As a specific method for these surface treatments, known methods can be used.

The surface treatment removes contaminants on the surface of the metal base material 2 and / or forms fine irregularities on the surface of the metal base material 2 for the purpose of anchoring effect to roughen the surface. As a result, the bondability between the surface of the metal base material 2 and the resin coating layer 4 can be improved, and as a result, the adhesiveness between the metal member 1 and the resin member 8 to be bonded (resin coating layer 4) can be improved. It is also possible to improve the bondability through. From this point of view, as the surface treatment, at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment and chemical conversion treatment is preferable.

(Washing / degreasing treatment)
Examples of the cleaning / degreasing treatment with a solvent include degreasing the surface of the metal base material 2 with an organic solvent such as acetone or toluene. The cleaning / degreasing treatment is preferably performed before other surface treatments.

(Blast processing)
Examples of the blasting process include shot blasting and sand blasting.

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

(Plasma processing)
Plasma treatment uses a high-voltage power supply to inject a plasma beam emitted from a rod called an electrode onto the surface of a material to first clean the foreign matter or oil film on the surface and then put energy into the gas according to the material. This is a method of exciting surface molecules. Examples of the plasma treatment include atmospheric pressure plasma treatment capable of imparting a hydroxyl group or other polar groups to the surface.

(Laser processing)
Laser treatment is a technique for rapidly heating and cooling only the surface layer by laser irradiation to improve the surface properties of a material, and is an effective method for roughening the surface. As the laser treatment, a known laser treatment technique can be used.

(Etching process)
Examples of the etching treatment include 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. ..

When the metal base material 2 is aluminum, the etching treatment is preferably an alkaline method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide as an etching solution, and more preferably a caustic soda method using an aqueous solution of sodium hydroxide. The alkaline method can be carried out, for example, by immersing the metal substrate 2 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 an additive, a chelating agent, an oxidizing agent, a phosphate or the like may be added to the etching solution. After soaking, it is preferable to neutralize (de-smut) with a 5 to 20% by mass nitric acid aqueous 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 include boehmite treatment and zirconium treatment. When the metal base material 2 is aluminum, the chemical conversion treatment is preferably boehmite treatment.

In the boehmite treatment, a boehmite film is formed on the surface of the metal base material 2 by treating the metal base material 2 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 metal substrate 2 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 metal base material 2 by immersing the metal base material 2 in a zirconium salt-containing liquid such as zirconium phosphate. The metal substrate 2 is immersed in a chemical agent for zirconium treatment (for example, "Pearl Coat 3762" manufactured by Nihon Parkerizing Co., Ltd., "Pearl Coat 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.

When the metal base material 2 is aluminum, it is preferable that the metal base material 2 is subjected to at least one surface treatment selected from an etching treatment and a boehmite treatment.

<Functional group-containing layer 3>
As shown in FIG. 5B, a one-layer or a plurality of functional group-containing layers 3 laminated in contact with the metal base material 2 and the resin coating layer 4 may be provided between the metal base material 2 and the resin coating layer 4. can. When the functional group-containing layer 3 is provided, the functional group contained in the functional group-containing layer 3 reacts with the hydroxyl group on the surface of the metal base material 2 and the functional group contained in the resin constituting the resin coating layer 4, respectively, to form a chemical bond. By forming the metal base material 2, the adhesiveness between the surface of the metal base material 2 and the resin coating layer 4 can be improved, and as a result, the adhesiveness between the metal member 1 and the resin member 8 to be bonded (resin coating layer) can be improved. Bondability via 4) can also be improved.

〔process〕
The functional group-containing layer 3 may be formed by treating the surface of the metal base material 2 with at least one selected from the group consisting of the following (1') to (7'). preferable.
(1') Silane coupling agent containing at least one functional group selected from the group consisting of a glycidyl group, an amino group and a mercapto group (2') At least one selected from a glycidyl compound and a thiol compound, and an amino group. Combination of silane coupling agent having (3') Selected from the group consisting of a glycidyl compound, an amino compound, an isocyanate compound, a compound having a (meth) acryloyl group and a glycidyl group, and a compound having a (meth) acryloyl group and an amino group. Combination of at least one and a silane coupling agent having a mercapto group (4') A combination of a thiol compound and a silane coupling agent having a (meth) acryloyl group (5') having an amino group and a (meth) acryloyl group. A combination of at least one selected from the group consisting of compounds, amino compounds and thiol compounds and a silane coupling agent having a glycidyl group (6') isocyanate compound (7') thiol compound.

[Functional group]
The functional group-containing layer 3 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 the silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2) An amino group derived from the silane coupling agent. A functional group generated by the reaction of at least one selected from a glycidyl compound and a thiol compound (3) A glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group are added to a mercapto group derived from a silane coupling agent. A functional group produced by the reaction of at least one selected from the group consisting of a compound having a (meth) acryloyl group and a compound having an amino group (4) A thiol compound to a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound

Before forming the functional group-containing layer 3 on the metal base material 2, the above-mentioned surface treatment portion 2a can be provided on the surface of the metal base material 2. The anchor effect due to the fine irregularities of the surface treatment portion 2a and the functional group of the functional group-containing layer 3 react with each of the hydroxyl group on the surface of the metal substrate 2 and the functional group of the resin constituting the resin coating layer 4. Due to the synergistic effect with the formed chemical bond, the adhesiveness between the surface of the metal base material 2 and the resin coating layer 4 and the adhesiveness between the metal member 1 and the resin member 8 to be bonded (via the resin coating layer 4). Bondability) can be further improved.

The method for forming the functional group-containing layer 3 using a silane coupling agent, an isocyanate compound, a thiol compound, or the like is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, the metal base material 2 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 immersed at room temperature to 100 ° C. for 1 minute to 5 minutes. The functional group-containing layer 3 can be formed by drying for a time.

〔Silane coupling agent〕
As the silane coupling agent, for example, a known one used for surface treatment of glass fiber or the like can be used. A silanol group generated by hydrolyzing a silane coupling agent or a silanol group of an oligomer product formed by condensing a silanol group reacts with a hydroxyl group existing on the surface of the metal substrate 2 to bond to the resin. A functional group based on the structure of the silane coupling agent that can be chemically bonded to the coating layer 4 can be imparted (introduced) to the metal substrate 2.

The silane coupling agent is not particularly limited, and for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. , N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and other silane coupling agents with amino groups; 2- (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Silane coupling agent having an epoxy group such as silane; silane coupling agent having a mercapto group or isocianato group such as 3-mercaptopropylmethyldimethoxysilane, 3-isosyanatopropyltriethoxysilane, dithioltriazinepropyltriethoxysilane; vinyl Trimethoxysilane, Vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Silane coupling agent having a vinyl group such as ethoxysilane, 3-acryloxypropyltrimethoxysilane; 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl Examples thereof include trimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris (trimethoxysilylpropyl) isocyanurate, and 3-ureidopropyltrialkoxysilane. The silane coupling agent may be used alone or in combination of two or more.

[Isocyanate compound]
The isocyanate compound is a functional group based on the structure of an isocyanate compound that can be chemically bonded to the resin coating layer 4 by reacting and bonding an isocyanato group in the isocyanate compound with a hydroxyl group existing on the surface of the metal substrate 2. It can be applied (introduced) to the metal base material 2.

The isocyanate compound is not particularly limited, and is, for example, a polyfunctional isocyanate such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI); and 2-isosia. Natoethyl methacrylate (for example, "Karenzu MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (for example, "Karenzu AOI (registered trademark)" manufactured by Showa Denko Co., Ltd. "," AOI-VM (registered). Examples thereof include isocyanate compounds having a radically reactive group such as ")") and 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example, "Karenzu BEI (registered trademark)" manufactured by Showa Denko Co., Ltd.).

[Thiol compound]
The thiol compound is a functional group based on the structure of the thiol compound that can be chemically bonded to the resin coating layer 4 by reacting and bonding the mercapto group in the thiol compound with the hydroxyl group existing on the surface of the metal substrate 2. It can be applied (introduced) to the metal base material 2.

The thiol compound is not particularly limited, and is, for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Co., Ltd., "QE-340M" manufactured by Toray Fine Chemical Co., Ltd.). , Ether-based first-class thiol (for example, "Cup Cure 3-800" manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example, "Karensu MT (registered) manufactured by Showa Denko KK). BD1 "), pentaerythritol tetrakis (3-mercaptobutyrate) (for example," Karens MT (registered trademark) PE1 "manufactured by Showa Denko KK), and 1,3,5-tris (3-mercaptobutyloxyethyl). )-1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -Torion (for example, "Karensu MT (registered trademark) NR1" manufactured by Showa Denko KK).

<Resin coating layer 4>
A resin coating layer 4 is laminated on the metal base material 2. The resin coating layer 4 may be one layer or may be composed of a plurality of layers.

[Modified polyolefin layer 4a]
At least one layer of the resin coating layer 4 is a modified polyolefin layer 4a formed from a resin composition containing a modified polyolefin. Since the resin coating layer 4 contains the modified polyolefin layer 4a, the metal member 1 can exhibit excellent adhesiveness to the resin member 8 (bondability via the resin coating layer 4).

The resin coating layer 4 was composed of a plurality of layers including a modified polyolefin layer 4a and a layer other than the modified polyolefin layer 4a, and the layer other than the modified polyolefin layer 4a was formed from a resin composition containing a thermoplastic epoxy resin. It may be at least one selected from the curable resin layer 4c formed from the thermoplastic epoxy resin layer 4b and the resin composition containing the curable resin.

When the resin coating layer 4 is composed of a plurality of layers, it is preferable that the essential modified polyolefin layer 4a is laminated so as to be the outermost surface on the opposite side to the metal base material 2.

The modified polyolefin layer 4a is obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a maleic anhydride-modified polyolefin, and at the same time, reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton. A reaction product obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a layer containing the reaction product 1 and maleic anhydride in a maleic anhydride-modified polyolefin skeleton. It is preferably at least one selected from the group consisting of a layer containing 2 and a layer containing a mixture of a thermoplastic epoxy resin and a polyolefin.

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

(Maleic anhydride-modified polyolefin)
The maleic anhydride-modified polyolefin is obtained by grafting maleic anhydride on the polyolefin, and examples thereof include maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene. Specific examples of the maleic anhydride-modified polyolefin include Kayaku Akzo Corporation's Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW, and Mitsubishi Chemical Corporation's Modic series. SCONA TPPP2112GA, TPPP8112GA, or TPPP9212GA manufactured by BYK may be used in combination with maleic anhydride-modified polyolefin as a polypropylene additive functionalized with maleic anhydride.

(Bifunctional epoxy resin)
Examples of the bifunctional epoxy resin include a bisphenol type epoxy resin and a biphenyl type epoxy resin. The bifunctional epoxy resin may be used alone or in combination of two or more. Specific examples of the bifunctional epoxy resin include "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", and "jER (registered trademark)" manufactured by Mitsubishi Chemical Corporation. 1004 ”,“ jER® 1007 ”, and“ jER® YX-4000 ”.

(Bifunctional phenol compound)
Examples of the bifunctional phenol compound include bisphenol and biphenol. The bifunctional phenol compound may be used alone or in combination of two or more. Examples of the combination of the bifunctional phenol compound 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 "WPE190" manufactured by Nagase ChemteX Corporation. "And" EX-991L ".

As the catalyst for the double addition reaction of the thermoplastic epoxy resin, for example, a tertiary amine such as triethylamine, 2,4,6-tris (dimethylaminomethyl) phenol; and a phosphorus-based compound such as triphenylphosphine are preferable.

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

(Thermoplastic epoxy resin)
The thermoplastic epoxy resin used for producing the reaction product 2 is a resin also called a field-polymerized phenoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound are catalysts. By the double addition reaction in the presence, a thermoplastic structure, that is, a linear polymer structure is formed. Here, the linear polymer means a polymer that does not contain a crosslinked structure in the polymer molecule and is one-dimensional linear. The thermoplastic epoxy resin has thermoplasticity unlike the curable resin that constitutes a three-dimensional network with a crosslinked structure.

The total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in producing the reactant 1 or the reactant 2 is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified polyolefin. It is more preferably 5 to 60 parts by mass, further preferably 10 to 30 parts by mass.

The reaction that occurs when the reactant 1 and the reactant 2 are obtained is the reaction between the maleic anhydride-modified polyolefin and the bifunctional epoxy resin, the reaction between the maleic anhydride-modified polyolefin and the bifunctional phenol compound, and the maleic anhydride. Specifics based on a wide variety of reactions such as the reaction of connecting epoxies, the reaction of the epoxy group at the end of the thermoplastic epoxy resin with maleic anhydride, and the reaction of the secondary hydroxyl group in the skeleton of the thermoplastic epoxy resin with maleic anhydride. 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 modified polyolefin obtained as the reactant 1 or the reactant 2 by the structure or the property.

The mixture of the thermoplastic epoxy resin and the polyolefin can be obtained by mixing the same thermoplastic epoxy resin as that used for producing the above-mentioned reaction product 2 and the polyolefin by a conventional method.

(Polyolefin)
As the polyolefin used for forming the mixture, the polyolefin used for the resin member 8 can be used. The polyolefin is not particularly limited and may be a general synthetic resin. Examples of the polyolefin include polyethylene and polypropylene.

The resin coating layer 4 is laminated on the surface of the metal base material 2. As described above, the resin coating layer 4 may be laminated on the surface of the metal base material 2 which has not been surface-treated, or may be laminated on the surface of the metal base material 2 which has been surface-treated. .. The resin coating layer 4 may be laminated on the surface of the functional group-containing layer 3.

[Thermoplastic epoxy resin layer 4b]
A resin composition in which the resin coating layer 4 is composed of a plurality of layers including a modified polyolefin layer 4a and a layer other than the modified polyolefin layer 4a, and at least one layer of the layers other than the modified polyolefin layer 4a is a resin composition containing a thermoplastic epoxy resin. It can be composed of a thermoplastic epoxy resin layer 4b formed from.

The resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably 70% by mass or more.

(Thermoplastic epoxy resin)
Similar to the thermoplastic epoxy resin used for producing the reactant 2, the thermoplastic epoxy resin has a thermoplastic structure, that is, a thermoplastic structure, that is, a double-addition reaction between the bifunctional epoxy resin and the bifunctional phenol compound in the presence of a catalyst. It is a resin that forms a linear polymer structure, and has thermoplasticity unlike curable resins that form a three-dimensional network with a crosslinked structure. Due to these characteristics, the thermoplastic epoxy resin has excellent bondability with the metal substrate 2 and with excellent bondability with the modified polyolefin layer 4a by in-situ polymerization. Layer 4b can be formed. Therefore, when the metal member 1 is manufactured, it is preferable to form the thermoplastic epoxy resin layer 4b by subjecting a composition containing a monomer of the thermoplastic epoxy resin to a double addition reaction on the surface of the lower layer.

It is preferable that the heavy addition reaction of the composition containing the monomer of the thermoplastic epoxy resin is carried out on the surface of the functional group-containing layer 3 as the lower layer. The resin coating layer 4 including the thermoplastic epoxy resin layer 4b formed in such an embodiment is excellent in bondability with the metal base material 2 and also with excellent bondability with the resin member 8 described later.

The method for forming the thermoplastic epoxy resin layer 4b using the composition containing the monomer of the thermoplastic epoxy resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.

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

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

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

[Curable resin layer 4c]
The resin coating layer 4 is composed of a plurality of layers including a modified polyolefin layer 4a and a layer other than the modified polyolefin layer 4a, and the layer other than the modified polyolefin layer 4a is cured by forming from a resin composition containing a curable resin. It can also be composed of the sex resin layer 4c.

The resin composition containing the curable resin may contain a solvent and, if necessary, an additive such as a colorant in order to sufficiently proceed the curing reaction of the curable resin and form a desired resin coating layer. You may go out. In this case, it is preferable that the curable 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 curable resin is 40 to 100% by mass. The content of the curable resin is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more.

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

The curable resin layer 4c may be formed of one of these resins, or may be formed by mixing two or more of them. The curable resin layer 4c may be composed of a plurality of layers, and each layer may be formed of a resin composition containing different types of curable resin.

The method for forming the curable resin layer 4c using the composition containing the monomer of the curable resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.

In the present disclosure, the curable resin means a resin that is cross-linked and cured, and is not limited to the thermosetting type, but also includes a room temperature curing type and a photocuring type. The photo-curing type can be cured in a short time by irradiation with visible light or ultraviolet rays. The photo-curing type may be used in combination with the heat-curing type and / or the 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)
Urethane resin is a resin usually obtained by the reaction of the isocyanato group of an isocyanate compound with the hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a paint containing 10% by weight or more of a vehicle non-volatile component polyisocyanate". The urethane resin corresponding to the above is 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 group), moisture-curable type (cured by reaction between isocyanato group and water in air), and block type (cured by reaction between isocyanato group and water in air). Examples thereof include a lacquer type (a type in which a solvent is volatilized and cured by drying) and a lacquer type (a type in which a blocking agent is dissociated by heating and regenerated by reacting with an isocyanato group and a hydroxyl group to be cured). Among these, a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling. Specific examples of the moisture-curable one-component urethane resin include "UM-50P" manufactured by Showa Denko KK.

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

Examples of the polyol compound in the polyol curing type include polyester polyols and polyether polyol-phenol resins.

Examples of the isocyanate compound having an isocyanato group in the polyol-cured 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, aromatic isocyanates such as p-phenylenediisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or a polynuclear mixture thereof, Polymeric MDI; and alicyclic isocyanates such as isophorone diisocyanate (IPDI).

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, amine-based catalysts such as triethylamine; and dibutyltindi Examples thereof include organic tin-based catalysts such as acetate, dibutyltin dilaurate, dibutyltinthiocarboxylate, and dibutyltin zimarate.

In the polyol curing type, it is generally preferable to add 0.01 to 10 parts by mass of the urethanization catalyst with respect 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, novolak-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. And ether ester type epoxy resin. Among these, bisphenol A type epoxy resin is preferably used. The epoxy resin may be used alone or in combination of two or more.

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 aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts. By using the curing agent in combination with long-chain aliphatic amines and / and thiols, a resin coating layer 4 having a large elongation rate and excellent impact resistance can be formed.

Specific examples of the thiols include the same compounds as those exemplified as the thiol compounds for forming the functional group-containing layer 3. Among these, pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Karensu MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation rate and impact resistance of the resin coating layer 4.

(Vinyl ester resin)
The vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene). The vinyl ester resin is also generally referred to as an epoxy (meth) acrylate resin, but in the present disclosure, 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. can be used. can. Specific examples of the vinyl ester resin include "Lipoxy (registered trademark) R-802", "Lipoxy (registered trademark) R-804", and "Lipoxy (registered trademark) R-806" manufactured by Showa Denko KK. Can be mentioned.

The urethane (meth) acrylate resin is, for example, radical polymerization obtained by 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 include sex-unsaturated radical-containing oligomers. Specific examples of the urethane (meth) acrylate resin include "Lipoxy (registered trademark) R-6545" manufactured by Showa Denko KK.

Vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.

Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. By combining these organic peroxides with a cobalt metal salt or the like, curing at room temperature is also possible.

Examples of the cobalt metal salt include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Among these, cobalt naphthenate and cobalt octylate are preferable.

(Unsaturated polyester resin)
The unsaturated polyester resin dissolves a condensation product (unsaturated polyester) of an esterification reaction between a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) in a polymerizable monomer (for example, styrene). It was done.

As the unsaturated polyester 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 be used. Can be done. Specific examples of the unsaturated polyester resin include "Rigolac (registered trademark)" manufactured by Showa Denko KK.

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

[Vehicle side step 10 (metal member-resin member joint)]
FIG. 6 is a schematic cross-sectional view of a state in which a metal member and a resin member are joined, and is a diagram showing, for example, regions B and C in FIG. In the area B and FIG. 6 of FIG. 4, the metal member 1 and the resin member 8 have the same positional relationship in the vertical direction of the paper surface, but in the area C and FIG. 6 of FIG. 4, the metal member 1 And the resin member 8 have an opposite positional relationship in the vertical direction of the paper surface. As shown in FIG. 6, in the vehicle side step 10, the surface 4s of the metal base material 2 of the metal member 1 (that is, the metal plate 10b) on the resin coating layer 4 side and the resin member 8 (that is, the

resin plates

10a and 10c) Are joined. The resin coating layer 4 is a primer layer of the metal base material 2 as described above. Specifically, the surface 4s on the resin coating layer 4 side arranged on the contact surface of the metal base material 2 included in the metal member 1 and the resin member 8 are joined so as to be in direct contact with each other.

As described above, since the surface 4s on the resin coating layer 4 side has excellent bondability with the resin member 8, the vehicle side step 10 in which the metal member 1 and the resin member 8 are bonded with high bonding strength is used. Can be manufactured.

The thickness (dry thickness) of the resin coating layer 4 depends on the type of resin of the resin member 8 and the bonding area, but is a viewpoint of obtaining excellent bonding property with the resin member 8 on the surface 4s on the resin coating layer 4 side. Therefore, it is preferably 1 μm to 10 mm, more preferably 2 μm to 8 mm, and further preferably 3 μm to 5 mm. When the resin coating layer 4 is a plurality of layers, the thickness of the resin coating layer 4 (thickness after drying) is the total thickness of each layer.

Specifically, when the metal member 1 and the carbon fiber reinforced resin member (CFRP member) as the resin member 8 are joined and integrated, the metal member 1 and the glass fiber reinforced resin member (GFRP member) as the resin member 8 are joined and integrated. The thickness of the resin coating layer 4 is preferably 0.1 to 10 mm, more preferably 0.2 to 8 mm, and even more preferably 0.5 to 5 mm in the case of joining and integrating the resins.

[Resin member 8]
The resin member 8 contains polyolefin. The polyolefin is not particularly limited, and examples thereof include polyethylene and polypropylene.

Polypropylene is generally a highly rigid homopolymer obtained by polymerizing only propylene, a highly transparent and flexible random polymer copolymerized with a small amount of ethylene, and a rubber component (EPR) uniformly and finely dispersed in the homopolymer or random polymer. It is classified as a block copolymer with high impact resistance. Polypropylene may contain homopolymers, random polymers, or block copolymers, or mixtures thereof. Polypropylene may be a high-strength type containing talc, glass fiber, or carbon fiber. Examples of the talc-containing polypropylene include TRC104N, which is a trade name manufactured by SunAllomer Ltd. Examples of the glass fiber-containing polypropylene include product name PP-GF40-01 F02 manufactured by Daicel FineChem Co., Ltd. Examples of the carbon fiber-containing polypropylene include product name PP-CF40-11 F008 manufactured by Daicel FineChem Co., Ltd.

Glass fiber-containing polypropylene is a type of glass fiber reinforced resin (GFRP), and carbon fiber-containing polypropylene is a type of carbon fiber reinforced resin (CFRP). The resin containing reinforcing fibers such as glass fiber and carbon fiber may be in the form of a molded body such as a sheet molding compound (SMC) or a bulk molding compound (BMC). SMC is a sheet-shaped molded body obtained by impregnating reinforcing fibers such as glass fiber and carbon fiber with a resin composition in which polypropylene, a low shrinkage agent, a filler and the like are mixed.

Examples of the method for manufacturing the side step 10 for a vehicle include a method in which a metal member 1 and a resin member 8 are separately manufactured and joined (adhered) to be integrated. The bonding (adhesion) between the metal member 1 and the resin member 8 is performed by at least one 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, and a hot pressing method. It can be carried out.

As a method for manufacturing the side step 10 for a vehicle, a method of forming the resin member 8 and at the same time joining the metal member 1 and the resin member 8 to integrate them is preferable. Specifically, when the resin member 8 is molded by a method such as an injection molding method (including an insert molding method), a transfer molding method, a press molding method, a filament winding molding method, or a hand lay-up molding method, the metal member 1 By joining the resin member 8 to the surface 4s on the resin coating layer 4 side of the above, the metal member 1 and the resin member 8 can be integrated to obtain the vehicle side step 10. In this case, the number of manufacturing steps of the vehicle side step 10 can be reduced.

Specifically, although not shown, when the resin member 8 is molded by, for example, an injection molding method, the metal member 1 is arranged in an injection molding mold, and the resin is molded by an injection device (not shown). By injecting into the cavity, the resin member 8 is molded, and at the same time, the metal member 1 and the resin member 8 are joined.

Next, another embodiment will be described below.

As shown in FIG. 7, in the vehicle side step 10, the surface 4s on the resin coating layer 4 side of the metal member 1 and the resin member 8 may be joined and integrated via the adhesive layer 7.

As described above, depending on the type of resin of the resin member 8, by using an adhesive, it is possible to obtain a side step in which the metal member 1 and the resin member 8 are joined with a higher joining strength.

The adhesive of the adhesive layer 7 is appropriately selected depending on the type of resin of the resin member 8, and for example, known adhesives such as epoxy resin-based, urethane resin-based, and vinyl ester resin-based adhesives may be used. can.

Depending on the heating temperature at the time of joining (bonding), the vehicle side step 10 is thermally deformed due to the difference in the coefficient of thermal expansion between the metal base material 2 and the resin member 8 in the process of cooling to room temperature after joining (bonding). May be done. From the viewpoint of suppressing and alleviating such thermal deformation, the thickness of the adhesive layer 7 is such that the resin coating layer 4 and the adhesive are formed as a portion having a large elongation rate between the metal base material 2 and the resin member 8. It is desirable that the total thickness with the layer 7 is 4 μm or more. The above-mentioned total thickness can be determined in consideration of physical properties such as the elongation rate of the resin coating layer 4 and the adhesive layer 7 in the temperature change at the time of joining (the temperature change from the heating temperature at the time of joining to room temperature cooling). preferable. The preferable upper limit of the total thickness of the resin coating layer 4 and the adhesive layer 7 is 10 mm.

In the present disclosure, the layer involved in the joining between the metal member 1 and the resin member 8 is referred to as a joining layer, and the thickness thereof is referred to as the thickness of the joining layer. When the adhesive layer 7 is formed on the surface 4s on the resin coating layer 4 side of the metal member 1, both the resin coating layer 4 and the adhesive layer 7 are bonding layers, and the resin coating layer 4 and the adhesive layer are formed. The total thickness of 7 is the thickness of the bonding layer. When the adhesive layer 7 is not formed on the surface 4s on the resin coating layer 4 side of the metal member 1, the resin coating layer 4 is the bonding layer, and the thickness of the resin coating layer 4 is the thickness of the bonding layer. ..

In another embodiment, at least one layer of the resin coating layer 4 is a layer derived from a film formed on a base material different from the metal base material 2. At least one layer of the film is the modified polyolefin layer 4a described above.

The film may have one layer or may be composed of a plurality of layers. The film is composed of a plurality of layers including the above-mentioned modified polyolefin layer 4a and the layer other than the above-mentioned modified polyolefin layer 4a, and the layers other than the above-mentioned modified polyolefin layer 4a are formed of the above-mentioned thermoplastic epoxy resin layer 4b and the above-mentioned curing. It may be at least one selected from the sex resin layer 4c. In this case, the modified polyolefin layer 4a of the film is bonded to the resin member 8, and the layers other than the modified polyolefin layer 4a of the film are bonded to the metal base material 2 or the functional group-containing layer 3 having or not having a surface treatment. ..

The film can be produced, for example, by the following procedure. (1) A reaction product obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a maleic anhydride-modified polyolefin and at the same time reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton. 1, (2) Reactant 2 obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with maleic anhydride in a maleic anhydride-modified polyolefin skeleton, or (3) A film precursor composition 1 containing a mixture of a thermoplastic epoxy resin and a polyolefin and, if necessary, a solvent is prepared. The reactant 1, the reactant 2, and the mixture of the thermoplastic epoxy resin and the polyolefin are the same as those described for the modified polyolefin layer 4a. The film precursor composition 1 is applied, sprayed, or extruded and laminated on a release film or release paper having a release coating such as a silicone type so as to form a film having a thickness of 1 μm to 10 mm after drying. .. The coating can be performed using a bar coater, a roll coater, or the like. The spraying can be performed using a spray coater or the like. Extrusion stacking can be performed using a single-screw or twin-screw extruder. Then, the film can be formed on the release film or the release paper by leaving it in an environment of room temperature to 40 ° C. to volatilize the solvent. After forming the film, the release film or the release paper may be used for handling the film as a carrier (support) of the film, or the film may be peeled off from the release film or the release paper to obtain a self-standing film.

The modified polyolefin layer 4a of the film contains a reactant (for example, a bifunctional epoxy resin, a bifunctional phenol compound, a maleic anhydride-modified polyolefin, etc.) as a constituent unit of the reactant 1, the reactant 2, or the thermoplastic epoxy resin. It may be contained in a completely reacted state, or some of them may be contained in an unreacted state. In the latter case, when the metal base material 2 or the resin member 8 and the film (resin coating layer 4) are bonded, the unreacted components may be further reacted. With the reaction of the unreacted components, the bonding strength between the film (resin coating layer 4) and the metal base material 2 or the resin member 8 may be increased.

A film composed of a plurality of layers including a modified polyolefin layer 4a and a layer other than the modified polyolefin layer 4a can be produced, for example, by the following procedure. A film containing (1a) a resin composition containing a thermoplastic epoxy resin, (1b) a composition containing a monomer of a thermoplastic epoxy resin, or (2) a resin composition containing a curable resin and, if necessary, a solvent. The precursor composition 2 is prepared. The resin composition containing the thermoplastic epoxy resin and the composition containing the monomer of the thermoplastic epoxy resin are the same as those described for the thermoplastic epoxy resin layer 4b. The resin composition containing the curable resin is the same as that described for the curable resin layer 4c. The film precursor composition 2 is applied, sprayed, or extruded and laminated on a release film or release paper having a release coating such as a silicone type so as to form a film having a thickness of 1 μm to 10 mm after drying. .. Then, the thermoplastic epoxy is left to stand in an environment of room temperature to 40 ° C. to volatilize the solvent, heat it to proceed with the double addition reaction or the curing reaction, or irradiate it with visible light or ultraviolet rays to proceed with the curing reaction. The resin layer 4b or the curable resin layer 4c is formed on the release film or the release paper. By forming the modified polyolefin layer 4a on these layers by the above procedure, a film composed of a plurality of layers including the modified polyolefin layer 4a and layers other than the modified polyolefin layer 4a can be obtained. ..

A component (for example, a bifunctional epoxy resin, a bifunctional phenol compound, a polyol, an isocyanate compound, etc.), which is a constituent unit of these resins, completely reacts with the thermoplastic epoxy resin layer 4b or the curable resin layer 4c of the film. It may be contained in an unreacted state, or a part thereof may be contained in an unreacted state. In the latter case, when the metal base material 2 and the film are bonded, the unreacted components may be further reacted. With the reaction of the unreacted components, the bonding strength between the film and the metal substrate 2 may be increased.

By arranging the film on the metal base material 2, pressurizing and heating it, the metal member 1 in which the resin coating layer 4 is laminated on the metal base material 2 can be produced. The metal base material 2 may have the above-mentioned surface treatment and / or the functional group-containing layer 3 as needed, and a resin coating layer is formed by arranging a film on these and applying pressure and heating. 4 may be laminated. In a film composed of a plurality of layers including a modified polyolefin layer 4a and a layer other than the modified polyolefin layer 4a, the layer other than the modified polyolefin layer 4a has or does not have a surface treatment as a metal substrate 2 or a functional group. It is laminated so as to be in contact with the content layer 3.

By joining (adhering) and integrating the metal member 1 and the resin member 8 thus obtained, the vehicle side step 10 can be manufactured. The bonding (adhesion) between the metal member 1 and the resin member 8 is performed by at least one 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, and a hot pressing method. It can be carried out.

On the resin coating layer 4 (derived from the film) of the metal member 1, by an injection molding method (including an insert molding method), a transfer molding method, a press molding method, a filament winding molding method, a hand lay-up molding method, or the like. By molding the resin member 8, the metal member 1 and the resin member 8 may be joined (bonded) and integrated to form the vehicle side step 10.

A film is sandwiched between the metal base material 2 and the resin member 8, and at least one 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, and a hot pressing method. The side step 10 for a vehicle can also be manufactured by joining (adhering) the metal base material 2 and the resin member 8 via the resin coating layer 4 (derived from the film) and integrating them. In this case, the metal member 1 and the vehicle side step 10 are manufactured at the same time. When the metal substrate 2 has a surface treatment and / or a functional group-containing layer 3, the film is arranged so as to be in contact with the surface-treated surface of the metal substrate 2 or the functional group-containing layer 3.

Although some embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments and can be variously modified without departing from the gist of the present invention.

The implementation test examples and comparative test examples related to the present invention are shown below. However, the present invention is not limited to the following implementation test examples.

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

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

<Manufacturing example 3>
The flask was charged with xylene: 95 g, bifunctional epoxy resin (jER1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.20 g, bisphenol A: 0.066 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.003 g. The mixture was stirred at 125 ° C. for 30 minutes and reacted to obtain a thermoplastic epoxy resin solution. Next, 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation): 5 g was put into a flask and dissolved, and the maleic anhydride-modified polypropylene modified with a thermoplastic epoxy resin (20% by mass): Modified PP-3 was obtained.

<Implementation test example 1>
The aluminum plate was formed by hot extrusion, the extruded aluminum plate was cut into a length of 45 mm, a width of 18 mm, and a thickness of 1.5 mm, and the surface thereof was smoothed by mechanical cutting.

The material of the aluminum plate is A6063 aluminum alloy, specifically, Si: 0.45% by mass, Fe: 0.21% by mass, Cu: 0.05% by mass, Mg: 0.75% by mass, Cr: It had a chemical component of 0.05% by mass and the balance was Al and unavoidable impurities. The tensile strength of the aluminum plate was 240 MPa, and its Young's modulus was 68 GPa.

(surface treatment)
The aluminum plate was immersed in a sodium hydroxide aqueous solution having a concentration of 5% by mass for 1.5 minutes, neutralized with a nitric acid aqueous solution having a concentration of 5% by mass, washed with water, and dried to perform an etching treatment. Next, the etched aluminum plate was boiled in pure water for 10 minutes and then baked at 250 ° C. for 10 minutes to perform boehmite treatment to form a boehmite film on the surface of the aluminum plate.

When the surface of the aluminum plate after the boehmite treatment was observed by SEM photography (scanning electron micrograph, 45 ° tilt observation), as shown in FIG. 8, a boehmite film having whisker-like irregularities on the surface was formed. It was confirmed that.

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

(Resin coating layer 4)
Next, the modified PP-1 obtained in Production Example 1 was applied to the surface of the functional group-containing layer 3, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer 3. A metal member 1 on which the resin coating layer 4 of the modified PP-1 having a thickness of 30 μm was formed was produced.

Polypropylene resin (PP resin) containing talc (TRC104N manufactured by Sun Aroma Co., Ltd.) (to be joined) is applied to the surface 4s on the resin coating layer 4 side of the metal member 1 by an injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature). The resin member 8 was bonded to the metal member 1 by injection molding at 200 ° C., a tool temperature of 30 ° C., an injection speed of 50 mm / sec, and a peak / holding pressure of 195/175 [MPa / MPa]). As a result, a test piece for tensile test (PP resin, 10 mm × 45 mm × 3 mm, joint length 5 mm) (metal member 1-resin member 8 joint body) conforming to ISO19095 was produced.

[Adhesion evaluation]
After leaving the prepared test piece (metal member 1-resin member 8 bonded body) at room temperature for 1 day, a tensile tester (Universal Testing Machine Autograph "AG-" manufactured by Shimadzu Corporation) is compliant with ISO19095 1-4. IS ”; load cell 10 kN, tensile speed 10 mm / min, temperature 23 ° C., 50% RH), a tensile shear joint strength test was performed, and the joint strength was measured. The measurement results are shown in Table 1.

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

(Functional group-containing layer 3)
Next, the same operation as in Example 1 was carried out to form the functional group-containing layer 3 on the surface of the boehmite film.

(Resin coating layer 4: 1st layer)
Obtained by dissolving 100 g of a bifunctional epoxy resin (jER® 1001 manufactured by Mitsubishi Chemical Corporation), 24 g of bisphenol A, and 0.4 g of triethylamine on the surface of the functional group-containing layer 3 in 250 g of acetone. The obtained thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, and then allowed to cool to room temperature to allow the first resin coating layer (1st layer). A thermoplastic epoxy resin layer 4b) was formed.

(Resin coating layer 4: 2nd layer)
Next, the modified PP-2 obtained in Production Example 2 was applied to the surface of the thermoplastic epoxy resin layer 4b to volatilize xylene and held at 150 ° C. for 30 minutes to apply the modified PP-2 to the surface of the thermoplastic epoxy resin layer 4b. A metal member 1 on which a resin-coated layer (modified polyolefin layer 4a) of modified PP-2 having a thickness of 30 μm was formed was produced.

The same operation as in Example 1 was performed on the surface 4s on the resin coating layer 4 side of the second layer (modified polyolefin layer 4a) of the metal member 1 to perform a tensile test test piece (metal member 1-resin member 8 bonded body). ) Was produced. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 1.

<Implementation test example 3>
(surface treatment)
As the metal base material 2, an iron plate having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was sanded using # 100 sandpaper to form fine irregularities on the surface of the iron plate.

(Resin coating layer 4: 1st layer)
The same operation as in Example 2 was performed on the uneven surface of the iron plate to form the first resin coating layer (thermoplastic epoxy resin layer 4b).

(Resin coating layer 4: 2nd layer)
Next, the same operation as in Example 2 was performed to form the metal member 1 on which the resin coating layer (modified polyolefin layer 4a) of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer 4b. Made.

A tensile test test piece (metal member 1-resin member 8 bonded body) was prepared by performing the same operation as in Example 1 on the surface 4s on the resin coating layer 4 side of the metal member 1. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 1.

<Implementation test example 4>
(surface treatment)
The aluminum plate used in Example 1 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, washed with water, and dried. Etching treatment was performed.

(Functional group-containing layer 3)
Next, the same operation as in Example 1 was carried out to form the functional group-containing layer 3 on the surface of the aluminum plate after the etching treatment.

(Resin coating layer 4)
The same operation as in Example 1 was carried out to form the resin coating layer 4 on the surface of the functional group-containing layer 3 to prepare the metal member 1.

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

The same injection molding operation as in Example 1 was performed without providing the functional group-containing layer 3 and the resin coating layer 4 on the surface of the boehmite film of the aluminum plate. However, the PP resin did not bond to the surface of the boehmite film, and it was not possible to produce a metal member-resin member bonded body.

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

(Resin coating layer)
Next, a solution prepared by dissolving 5 g of maleic anhydride-modified polypropylene (Modic® ER321P manufactured by Mitsubishi Chemical Corporation) in 95 g of xylene was applied to the surface of the functional group-containing layer 3 to volatilize xylene, and 150 It was held at ° C. for 30 minutes to prepare a metal member having a maleic anhydride-modified polypropylene layer having a thickness of 30 μm formed on the surface of the functional group-containing layer.

The same operation as in Example 1 was performed on the surface of the metal member on the resin coating layer side to prepare a test piece for tensile test (metal member-resin member joint). The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 1.

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

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

(Resin coating layer 4)
Next, the modified PP-3 obtained in Production Example 3 was applied to the surface of the functional group-containing layer 3, xylene was volatilized, and the mixture was held at 150 ° C. for 30 minutes to thicken the surface of the functional group-containing layer 3. A metal member 1 on which the resin coating layer 4 of the modified PP-3 having a thickness of 30 μm was formed was produced.

Polypropylene resin (PP resin) containing glass fibers (pp-GF40-01 F02 manufactured by Daicel FineChem Co., Ltd.) (to be bonded) was applied to the surface 4s on the resin coating layer 4 side of the metal member 1 under the same conditions as in Test Example 1. A test piece for tensile test (metal member 1-resin member 8 bonded body) was produced by injection molding. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 2.

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

(Functional group-containing layer 3)
Next, the same operation as in Example 5 was carried out to form the functional group-containing layer 3 on the surface of the boehmite film.

(Resin coating layer 4: 1st layer)
The same operation as in Example 2 was performed except that the epoxy resin was changed to jER® 1004 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer 3, and the first resin coating layer (thermoplastic epoxy) was performed. A resin layer 4b) was formed.

(Resin coating layer 4: 2nd layer)
Next, the same operation as in Example 2 was carried out to form the metal member 1 having the modified PP-2 resin coating layer (modified polyolefin layer 4a) having a thickness of 30 μm formed on the surface of the thermoplastic epoxy resin layer 4b. Made.

The same operation as in Example 5 was performed on the surface 4s on the resin coating layer 4 side of the second layer (modified polyolefin layer 4a) of the metal member 1 to perform a tensile test test piece (metal member 1-resin member 8 bonded body). ) Was produced. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 2.

<Implementation Test Example 7>
(surface treatment)
As the metal base material 2, an aluminum plate (A6063) having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was subjected to the same sanding treatment as in Example 3 to form fine irregularities on the surface of the aluminum plate.

(Functional group-containing layer 3)
Next, the same operation as in Example 1 was carried out to form the functional group-containing layer 3 on the surface of the aluminum plate after the sanding treatment.

(Resin coating layer 4: 1st layer)
The same operation as in Example 6 was performed to form the first resin coating layer (thermoplastic epoxy resin layer 4b).

(Resin coating layer 4: 2nd layer)
Next, the same operation as in Example 2 was carried out to form the metal member 1 on which the resin coating layer (modified polyolefin layer 4a) of modified PP-2 having a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer 4b. Made.

The same operation as in Example 5 was performed on the surface 4s on the resin coating layer 4 side of the metal member 1 to prepare a test piece for a tensile test (metal member 1-resin member 8 bonded body). The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 2.

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

The same injection molding operation as in Example 5 was performed without providing the functional group-containing layer 3 and the resin coating layer 4 on the surface of the boehmite film of the aluminum plate. However, the PP resin did not bond to the surface of the boehmite film, and it was not possible to produce a metal member-resin member bonded body.

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

(Resin coating layer)
Next, the same operation as in Comparative Test Example 2 was carried out to prepare a metal member having a maleic anhydride-modified polypropylene layer having a thickness of 30 μm formed on the surface of the functional group-containing layer 3.

The same operation as in Example 5 was performed on the surface of the metal member on the resin coating layer side to prepare a test piece for tensile test (metal member-resin member joint). The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 2.

<Implementation Test Example 8>
(surface treatment)
The same operation as in Example 1 was carried out to form a boehmite film having whisker-like irregularities on the surface of an aluminum plate (18 mm × 45 mm, thickness 1.5 mm A6063).

(Resin coating layer 4)
Next, the same operation as in Example 5 was carried out to prepare a metal member 1 having a resin coating layer 4 of modified PP-3 having a thickness of 30 μm formed on the surface of the functional group-containing layer 3.

A polypropylene resin (PP resin) containing carbon fibers (pp-GF40-01 F008 manufactured by Daicel FineChem Co., Ltd.) (to be bonded) was applied to the surface 4s on the resin coating layer 4 side of the metal member 1 under the same conditions as in Test Example 1. A test piece for tensile test (metal member 1-resin member 8 bonded body) was prepared by injection molding. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 3.

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

(Resin coating layer 4: 1st layer)
The same operation as in Example 2 was performed except that the epoxy resin was changed to jER® 1007 manufactured by Mitsubishi Chemical Co., Ltd. on the surface of the functional group-containing layer 3, and the first resin coating layer (thermoplastic epoxy) was performed. The resin layer 4b) was formed.

The same operation as in Example 8 was performed on the surface 4s on the resin coating layer 4 side of the second layer (modified polyolefin layer 4a) of the metal member 1 to perform a tensile test test piece (metal member 1-resin member 8 bonded body). ) Was produced. The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 3.

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

(Functional group-containing layer 3)
Next, the same operation as in Example 1 was carried out to introduce a functional group derived from a silane coupling agent onto the surface of the boehmite film. Further, 2-isocyanatoethyl methacrylate (Carens MOI (registered trademark) manufactured by Showa Denko KK): 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g in toluene It was immersed in a solution dissolved in 150 g at 70 ° C. for 5 minutes, then withdrawn and dried. In this way, the functional group-containing layer 3 in which the chemically bondable functional group was extended in the three-dimensional direction was formed.

(Resin coating layer 4)
Next, the same operation as in Example 1 was carried out to prepare a metal member 1 having a resin coating layer 4 of modified PP-1 having a thickness of 30 μm formed on the surface of the functional group-containing layer 3.

The same operation as in Example 8 was performed on the surface 4s on the resin coating layer 4 side of the metal member 1 to prepare a test piece for a tensile test (metal member 1-resin member 8 bonded body). The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 3.

<Implementation Test Example 11>
(surface treatment)
As the metal base material 2, a martensitic stainless steel (SUS403) steel sheet having a thickness of 18 mm × 45 mm and a thickness of 1.5 mm was sanded by the same operation as in Test Example 3 to form fine irregularities on the surface of the stainless steel sheet. ..

(Functional group-containing layer 3)
Next, the same operation as in Example 1 was carried out to form the functional group-containing layer 3 on the surface of the stainless steel sheet after the sanding treatment.

(Resin coating layer 4: 1st layer)
Epoxy resin (jER® 1007 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 5.6 g, and triethylamine: 0.4 g were dissolved in 196 g of acetone on the surface of the functional group-containing layer 4. The obtained thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 μm. After volatilizing the solvent by leaving it in the air at room temperature for 30 minutes, it is left in a furnace at 150 ° C. for 30 minutes for a heavy addition reaction, and then allowed to cool to room temperature to allow the first resin coating layer (1st layer). A thermoplastic epoxy resin layer 4b) was formed.

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

The same injection molding operation as in Example 8 was performed without providing the functional group-containing layer 3 and the resin coating layer 4 on the surface of the boehmite film of the aluminum plate. However, the PP resin did not bond to the surface of the boehmite film, and it was not possible to produce a metal member-resin member bonded body.

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

The same operation as in Example 8 was performed on the surface of the metal member on the resin coating layer side to prepare a test piece for a tensile test (metal member-resin member joint). The joint strength of the test piece was measured by the same method as in Test Example 1. The measurement results are shown in Table 3.

As can be seen from the evaluation results in Tables 1 to 3, the metal member-resin member joints of Example 1 to 11 all had high joint strength.

Therefore, according to the present disclosure, it is possible to manufacture a vehicle side step in which a metal member and a resin member are firmly joined.

The present disclosure can be used for a vehicle side step provided under the door of a vehicle having a high boarding position and used as a footrest when boarding, and a method for manufacturing the same.

1: Metal member 2: Metal base material 2a: Surface treatment part 3: Functional group-containing layer 4: Resin coating layer (primer layer)
4a: Modified polyolefin layer 4b: Thermoplastic epoxy resin layer 4c: Curable resin layer 4s: Resin coating layer surface 7: Adhesive layer 8: Resin member 10: Vehicle side step (metal member-resin member joint)
10a: Base resin plate 10b: Metal plate 10c: Surface resin plate 12: Door 14: Stay

Claims

A metal member in which one or more resin coating layers are laminated on at least a part of the surface of the metal substrate, and a resin member bonded to the surface of the metal member on the resin coating layer side of the metal substrate. Equipped with
At least one layer of the resin coating layer is a modified polyolefin layer formed from a resin composition containing a modified polyolefin, and the modified polyolefin layer is composed of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound. At least one selected from the group consisting of a layer containing a reactant 1, a layer containing a reaction product 2 of a maleic anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin. Side step for vehicles.
The vehicle side step according to claim 1, wherein the reaction product 1 is formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing maleic anhydride-modified polyolefin.
The vehicle side step according to claim 1, wherein the reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin. ..
The vehicle side step according to claim 1, wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin.
The resin coating layer is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer of the layer other than the modified polyolefin layer is made of a resin composition containing a thermoplastic epoxy resin. The vehicle side according to any one of claims 1 to 4, which is at least one selected from the formed thermoplastic epoxy resin layer and the curable resin layer formed from the resin composition containing the curable resin. Step.
The vehicle side step according to claim 5, wherein the curable 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 base material and the resin coating layer is provided between the metal base material and the resin coating layer.
The vehicle side step according to any one of claims 1 to 6, wherein the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
(1) At least one functional group derived from the silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2) An amino group derived from the silane coupling agent. A functional group generated by the reaction of at least one selected from a glycidyl compound and a thiol compound (3) A glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group are added to a mercapto group derived from a silane coupling agent. A functional group produced by the reaction of at least one selected from the group consisting of a compound having a (meth) acryloyl group and a compound having a (meth) acryloyl group and a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound. (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound
The surface of the metal substrate is subjected to at least one surface treatment selected from the group consisting of blast treatment, polishing treatment, etching treatment and chemical conversion treatment, and the resin coating layer is the surface of the metal substrate. The vehicle side step according to any one of claims 1 to 7, which is laminated on the treated surface.
The resin member includes a base resin member and a surface resin member.
The lower surface of the metal member in the vehicle height direction is joined to the upper surface of the base resin member in the vehicle height direction.
A claim that the lower surface of the surface resin member in the vehicle height is joined to a part of the upper surface of the metal member in the vehicle height direction, and the other part of the upper surface of the metal member in the vehicle height direction is exposed. The vehicle side step according to any one of Items 1 to 8.
The vehicle side step according to any one of claims 1 to 9, which includes a metal plate as the metal member.
The vehicle according to any one of claims 1 to 10, wherein the metal base material is made of an extruded aluminum material of an A6000 series alloy and has characteristics of a tensile strength of 180 MPa or more and a Young's modulus of 60 GPa or more. For side steps.
The method for manufacturing a side step for a vehicle according to any one of claims 1 to 11, wherein the resin member is formed by an injection molding method, a transfer molding method, a press molding method, a filament winding molding method, or a hand lay-up molding method. A method for manufacturing a side step for a vehicle, in which a resin member is joined to a surface of a metal member on the resin coating layer side during molding.