Engine ECU and its manufacturing method

Abstract

To provide an engine ECU which enables reduction in weight and size.SOLUTION: A metal member (2) is a first part, a resin member (5) is a second part, and the metal member and the resin member are joined to each other through a resin coating layer (3). At least one layer of the resin coating layer is formed of a cured product of a composition containing a difunctional epoxy resin and a divalent phenol compound, and an epoxy resin composition containing a specific composition.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present disclosure relates to an engine ECU and a manufacturing method thereof. [Background technology]

[0002] An engine ECU (Electronic Control Unit) is installed near the engine in the engine room to electronically control fuel injection and other functions of an automobile engine. As electronic control becomes faster and more complex, engine ECUs generate a lot of heat from elements on their electronic boards, and many of them are equipped with a metal housing that also serves as a heat sink for dissipating heat and a resin lid that also serves as a connector. Since the engine room is a place that is subject to the inflow of moisture from outside the vehicle and the effects of heat and vibration from the engine, the engine ECU needs to reliably protect the internal electronic boards even under harsh operating conditions. Therefore, the engine ECU has been required to have a joint between the housing and the lid that has high reliability and long-term stability under the above operating conditions.

[0003] Patent Document 1 (JP 2021-5620 A) discloses an engine ECU consisting of an electronic board on which semiconductor elements such as a microcomputer and a transistor are mounted, a connector, a case, and a lid. The case and the lid of Patent Document 1 each have a hole for attaching a fastening member for fastening them to each other. A sealant is provided between the case and the lid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-5620 Summary of the Invention [Problem to be solved by the invention]

[0005] The engine ECU in Patent Document 1 is joined by screwing a screw as a fastening member into a hole provided in each of the case and the lid. Therefore, the engine ECU in Patent Document 1 requires a screw for joining the case and the lid and a sealant for achieving a waterproof seal between the case and the lid, which not only increases the number of manufacturing steps but also makes it difficult to achieve weight reduction and cost reduction.

[0006] An object of the present disclosure is to provide an engine ECU that can be made lighter and smaller. [Means for solving the problem]

[0007] The present invention is based on the discovery that by providing a resin coating layer (primer layer) made of a specific material on the surface of a metal component, the bonding strength between the metal component and the resin component can be increased even when exposed to high temperatures exceeding 100°C.

[0008] The present disclosure includes the following aspects.

[0009] [1] A metal member, a resin member, and one or more resin coating layers laminated on at least one of the metal member and the resin member. An engine ECU comprising: the metal member is a first part, the resin member is a second part, the metal member and the resin member are joined via the resin coating layer, at least one of the resin coating layers is formed from a cured product of an epoxy resin composition containing a composition (A) including a difunctional epoxy resin and a dihydric phenol compound, and a composition (B); The composition (B) for an engine ECU includes at least one combination selected from the following (B1) to (B3): (B1) A combination of an epoxy resin having a fluorene skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B2) A combination of an epoxy resin having a biphenyl skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B3) Combination of an allylphenol compound and a bismaleimide compound [2] The engine ECU according to the above [1], wherein a content of the composition (B) in the epoxy resin composition is 10 to 80 parts by mass per 100 parts by mass of a total content of the compositions (A) and (B). [3] The engine ECU according to either [1] or [2] above, wherein the surface of the metal member has been subjected to one or more surface treatments selected from the group consisting of blasting, polishing, etching and chemical conversion treatment. [4] A functional group-containing layer is provided between the metal member and the resin coating layer and is laminated in contact with the metal member and the resin coating layer, The engine ECU according to any one of the above [1] to [3], wherein the functional group-containing layer has a structure derived from one or more functional groups selected from the following (C1) to (C7): (C1) One or more functional groups selected from an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, and an isocyanato group derived from a silane coupling agent (C2) A functional group generated by the reaction of an amino group derived from a silane coupling agent with an epoxy compound (C3) A functional group formed by the reaction of a mercapto group derived from a silane coupling agent with one or more compounds selected from an epoxy compound, an isocyanate compound, an epoxy-modified (meth)acrylate compound, and an amino group-containing (meth)acrylate compound. (C4) A functional group formed by the reaction of a (meth)acryloyl group derived from a silane coupling agent with a thiol compound. (C5) A functional group formed by the reaction of an epoxy group derived from a silane coupling agent with one or more compounds selected from an amino compound, a thiol compound, and an amino group-containing (meth)acrylate compound. (C6) Isocyanato group derived from isocyanate compounds (C7) Mercapto group derived from thiol compound [5] The resin coating layer is a plurality of layers, and further includes a resin coating layer formed from a cured product of a curable resin; The engine ECU according to any one of the above [1] to [4], wherein the curable resin is at least one selected from an allyl-modified maleimide resin, a urethane resin, an epoxy resin, a vinyl ester resin, and an unsaturated polyester resin. [6] The engine ECU according to any one of the above [1] to [5], wherein the metal member contains an aluminum material, and the aluminum material has a thermal conductivity of 150 W / (m·K) or more. [7] The engine ECU according to any one of the above [1] to [6], wherein the metal member includes an aluminum extrusion material, and the aluminum extrusion material has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more. [8] The engine ECU according to any one of the above [1] to [6], wherein the metal member includes an aluminum forging, and the aluminum forging has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more. [9] A method for manufacturing an engine ECU described in any one of [1] to [8], comprising heating the resin coating layer and pressing the metal member and the resin member together so that the heated resin coating layer is interposed between the metal member and the resin member, thereby joining the metal member and the resin member. Effect of the Invention

[0010] According to the present disclosure, it is possible to provide an engine ECU that can be made lighter and smaller. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a perspective view of an engine ECU according to an embodiment of the present disclosure. [Diagram 2] FIG. 2 is a cross-sectional view taken along line AA' in FIG. [Diagram 3]FIG. 3 is a schematic cross-sectional view of a resin coating layer laminate according to one embodiment. [Figure 4] FIG. 4 is a schematic cross-sectional view of a resin coating layer laminate according to another embodiment. [Diagram 5] FIG. 5 is a schematic cross-sectional view of a state in which a metal member and a resin member are joined via a resin coating layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Next, embodiments of the present disclosure will be described below with reference to the drawings.

[0013] In this disclosure, unless otherwise specified, the term "metal" is used to include both pure metals consisting of a single metal element and alloys in which a pure metal is mixed with one or more other elements. For example, the term "aluminum" includes pure aluminum metal and its alloys.

[0014] In this disclosure, bonding means connecting two objects together, and adhesion and welding are subordinate concepts. Adhesion means joining two adherends (objects to be bonded) together using an organic material such as tape or adhesive (curable resin, thermoplastic resin, etc.). Welding means melting the surface of the adherend, such as thermoplastic resin, by heat, and joining the two by entanglement and crystallization caused by molecular diffusion through contact pressure and cooling.

[0015] In this disclosure, "(meth)acryloyl" means acryloyl or methacryloyl. Similarly, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0016] In this disclosure, "normal temperature" means general room temperature within the range of 25±5°C.

[0017] [Engine ECU] An engine ECU 10 according to an embodiment of the present disclosure will be described with reference to Fig. 1. The engine ECU 10 shown in Fig. 1 includes a first part 12 made of metal and a second part 14 made of resin. Hereinafter, the description will be given using an orthogonal coordinate system having an X-axis, a Y-axis, and a Z-axis that are orthogonal to each other. The direction parallel to the X-axis is the X-direction, the direction parallel to the Y-axis is the Y-direction, and the direction parallel to the Z-axis is the Z-direction.

[0018] The first part 12 is a cover and has a plate-shaped base 16 and a heat dissipation fin 17. The base 16 has one side surface 13 parallel to the X direction and the Y direction, and the other side surface 15 opposite to the one side surface 13. The other side surface 15 of the base 16 is flat. The heat dissipation fin 17 is made of a plurality of plate-shaped protrusions 18 provided on the one side surface 13 of the base 16. The plurality of plate-shaped protrusions 18 protrude in the Z direction from the one side surface 13 of the base 16 and are arranged parallel to each other at a predetermined interval. The plurality of plate-shaped protrusions 18 shown in FIG. 1 are rectangular and arranged at a predetermined interval in the X direction with their longitudinal directions parallel to the Y direction. The heat dissipation fin 17 is not limited to the case where the plurality of plate-shaped protrusions 18 are provided, but may be a plurality of columnar protrusions. The base 16 and the plurality of plate-shaped protrusions 18 may be integral with each other.

[0019] The second part 14 is a case, and as shown in FIG. 2, has a bottom 22, side parts 24 formed integrally with the outer edge of the bottom 22, and a space 26 surrounded by the bottom 22 and the side parts 24. The bottom 22 has a rectangular shape in a plan view. The base ends of the side parts 24 are connected to the four sides of the bottom 22, respectively, and the sides of the side parts 24 are continuous with each other. The second part 14 has a joint surface 27 at the tip of the side part 24 in the Z direction. The joint surface 27 is flat. A connector 20 is provided on one of the four side parts 24. The second part 14 accommodates a circuit board 32 on which a semiconductor element 30 is mounted in the space 26 surrounded by the bottom 22 and the side parts 24. The circuit board 32 is electrically connected to the connector 20.

[0020] The first part 12 is disposed so as to close the opening of the second part 14. The first part 12 is joined to the second part 14 with the other surface 15 of the first part 12 in contact with the joining surface 27 of the second part 14. The semiconductor element 30 on the circuit board 32 is in contact with the other surface 15 of the first part 12 via the thermally conductive sheet 28 on the surface opposite to the surface in contact with the circuit board 32. The thermally conductive sheet 28 is not particularly limited as long as it is used for heat dissipation of semiconductors, and examples of the thermally conductive sheet 28 include a thermoplastic resin sheet, an elastomer sheet, a cured resin sheet, and an adhesive sheet in which a thermally conductive filler such as silica, alumina, boron nitride, aluminum nitride, silicon carbide, boron carbide, boron carbon nitride, graphite, carbon fiber, carbon nanotube, and alumina is dispersed in a binder such as silicone, acrylic resin, and epoxy resin.

[0021] In the present disclosure, engine ECU 10 includes first part 12 as a metal member and second part 14 as a resin member. First part 12 and second part 14 are joined at other side surface 15 of first part 12 and joining surface 27 of second part 14. Although a case has been described in which first part 12 is a lid and second part is a case, the present invention is not limited thereto, and as long as an airtight container for accommodating circuit board 32 can be formed, first part 12 may be a case and second part may be a lid.

[0022] The first part 12 and the second part 14 are joined via a resin coating layer described below. The resin coating layer may be laminated on the first part 12, may be laminated on the second part 14, or may be laminated on both the first part 12 and the second part 14. Hereinafter, the first part 12 will also be referred to as the "metal member 2," and the second part 14 will also be referred to as the "resin member 5."

[0023] [Resin coating layer laminate 1] In one embodiment, one or more resin coating layers are laminated on a metal member 2 to form a resin coating layer laminate 1. FIG. 3 shows a schematic cross-sectional view of the resin coating layer laminate 1 of one embodiment. The resin coating layer laminate 1 shown in FIG. 3 includes a metal member 2 and one or more resin coating layers 3 laminated on the metal member 2. At least one layer of the resin coating layer 3 is formed from a cured product of an epoxy resin composition containing a composition (A) containing a bifunctional epoxy resin and a dihydric phenol compound, and a composition (B). The composition (B) is characterized by including at least one combination selected from the following (B1) to (B3). (B1) A combination of an epoxy resin having a fluorene skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B2) A combination of an epoxy resin having a biphenyl skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B3) Combination of an allylphenol compound and a bismaleimide compound

[0024] When the resin coating layer 3 of the resin coating layer laminate 1 is bonded to the resin member 5, it is possible to maintain high bonding strength between the metal member 2 and the resin member 5 even when exposed to high temperatures exceeding 100°C.

[0025] <Metal material 2> The metal type of the metal member 2 is not particularly limited. Examples of metal types include aluminum, iron, titanium, magnesium, stainless steel, and copper. These metal types may be pure metals or alloys. Among these, aluminum is preferably used from the viewpoints of heat dissipation characteristics, light weight, and ease of processing. The following describes in detail the case where aluminum is used.

[0026] When aluminum is used for the metal member 2, the type of aluminum material for the metal member 2 is not limited, and may be, for example, an aluminum content of 50 mass% or more. The aluminum material is preferably an A1000 series alloy, an A6000 series alloy (e.g., A6061, A6063, A6082, A6110), an A4000 series alloy, etc. The aluminum material is more preferably an A6063 aluminum alloy having high thermal conductivity and high strength.

[0027] The thermal conductivity of the aluminum material is preferably 150 W / (m·K) or more, and more preferably 180 W / (m·K) or more.

[0028] The metal member 2 preferably includes an aluminum extrusion or an aluminum forging. The aluminum extrusion preferably has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more. The aluminum forging preferably has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more. In these cases, since the metal member 2 has a high thermal conductivity (high thermal conductivity) and a high tensile strength (high strength), the strength of the metal member 2 can be increased, and the heat dissipation characteristics of the metal member 2 can be improved. The upper limit of the tensile strength is not limited, and is, for example, 450 MPa. The upper limit of the thermal conductivity is not limited, and is, for example, 250 W / (m·K). In the present disclosure, the thermal conductivity and tensile strength are values ​​at room temperature.

[0029] When the metal member 2 includes an aluminum extrusion material, the metal member 2 is preferably manufactured by the following method. Specifically, the steps of continuously casting a cast rod by supplying a molten aluminum material having predetermined properties to a continuous casting device, homogenizing the cast rod, cutting the cast rod to a predetermined length to obtain a billet as an extrusion material, grinding the outer diameter of the billet, and hot extruding the billet to form an extrusion material having a predetermined cross-sectional shape are performed in this order. Next, the extrusion material is cut to a predetermined length, and predetermined processes such as grinding and deburring are performed on both cut end faces to obtain the metal member 2 including the aluminum extrusion material. When a high-strength alloy such as an A6000 series alloy or an A4000 series alloy is used as the metal member 2, it is preferable to apply high strength by T6 heat treatment (a combination of water-cooled quenching from a solution treatment and age hardening (tempering)) before processing the extrusion material.

[0030] When the metal member 2 includes an aluminum forging, the metal member 2 is preferably manufactured by the following method. Specifically, the steps of continuously casting a cast rod by supplying a molten aluminum material having a predetermined characteristic to a continuous casting device, obtaining a billet (raw material) by cutting the cast rod to a predetermined length, homogenizing the billet, surface-cutting the outer diameter of the billet, and hot die forging the billet to form a base material having a shape roughly equivalent to a base plate with heat dissipation fins as a forging material are performed in this order. When a high-strength alloy such as an A6000 series alloy or an A4000 series alloy is used as the metal member 2, a T6 heat treatment (a combination of water-cooled quenching from a solution treatment and age hardening treatment (tempering)) is subsequently performed. Next, a predetermined portion of the base material (such as a surface to be joined with the resin member 5) is finished by machining (e.g., cutting). As a result, the metal member 2 including the aluminum forging is obtained. A plurality of such preforms may be produced and joined by MIG welding, friction stir welding, or the like.

[0031] <Resin coating layer 3> In one embodiment, the resin coating layer 3 is laminated on the metal member 2. The resin coating layer 3 may be composed of one layer, or may be composed of multiple layers.

[0032] The resin coating layer 3 formed on the surface of the metal member 2 allows the metal member 2 to be bonded with high bonding strength to the resin member 5. The resin coating layer 3 is also firmly adhered to the surface of the metal member 2, and can protect the surface of the metal member 2 from contamination and deterioration such as oxidation.

[0033] At least one of the resin coating layers 3 is a layer (hereinafter also referred to as "epoxy resin layer") formed from a cured product of an epoxy resin composition containing a composition (A) including a bifunctional epoxy resin and a dihydric phenol compound, and a composition (B) described below.

[0034] By curing the epoxy resin composition by in-situ polymerization, it is possible to form a resin coating layer 3 that has excellent adhesion to the metal member 2 and can provide high bonding strength with the resin member 5 even when exposed to high temperatures exceeding 100°C.

[0035] Composition (A) is a resin composition that forms a so-called in-situ polymerized thermoplastic epoxy resin. The epoxy resin layer is formed by the reaction of an epoxy resin composition containing composition (A) and composition (B), and has a linear polymer structure, or a linear polymer structure in which a crosslinked structure is partially formed to the extent that the molecular miscibility with the thermoplastic resin is not impaired. Therefore, unlike a curable resin that is entirely composed of a three-dimensional network due to a crosslinked structure, the epoxy resin layer can form a resin coating layer 3 that has excellent molecular miscibility with the thermoplastic resin.

[0036] The epoxy resin layer may be formed in one layer or in two or more layers. When the epoxy resin layer has two or more layers, each layer may be formed from a cured product of the same epoxy resin composition or from a cured product of a different epoxy resin composition.

[0037] It is common knowledge for those skilled in the art that the epoxy resin composition forming the epoxy resin layer contains a plurality of compounds as compositional components, and that various complex reactions may occur with the participation of a plurality of functional groups depending on the compounding ratio of these compounds, reaction conditions, etc. For this reason, it is considered impossible or impractical to directly specify and comprehensively express the specific chemical structure or properties of the epoxy resin layer. Therefore, in the present disclosure, the epoxy resin layer is specified by the composition raw material forming the epoxy resin layer, i.e., the composition of the epoxy resin composition.

[0038] In the present disclosure, an epoxy resin composition "contains" composition (A) and composition (B) means that composition (A) and composition (B) are blended as composition raw materials of the epoxy resin composition. A composition that can be either composition (A) or composition (B) is considered to be composition (B).

[0039] (Composition (A)) The composition (A) contains a difunctional epoxy resin and a dihydric phenol compound.

[0040] Examples of bifunctional epoxy resins include bisphenol type epoxy resins "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", "jER (registered trademark) 1004", and "jER (registered trademark) 1007" and biphenyl type epoxy resin "jER (registered trademark) YX4000" (all manufactured by Mitsubishi Chemical Corporation). These bifunctional epoxy resins may be used alone or in combination of two or more kinds.

[0041] Examples of the dihydric phenol compound include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S, and biphenol compounds such as 4,4'-biphenol. These dihydric phenol compounds may be used alone or in combination of two or more kinds.

[0042] Combinations of bifunctional epoxy resins and dihydric phenol compounds in the composition (A) include, for example, bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, bisphenol A type epoxy resin and bisphenol S, and biphenyl type epoxy resin and 4,4'-biphenol. In addition, for example, "EX-991L" and "WPE190" manufactured by Nagase ChemteX Corporation may be used in combination.

[0043] The blend ratio of the bifunctional epoxy resin and the bivalent phenol compound in the composition (A) is preferably set so that the molar equivalent ratio of the epoxy group to the hydroxyl group is 0.7 to 1.5, taking into consideration the reactivity of both, etc. The molar equivalent ratio of the epoxy group to the hydroxyl group is more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.3.

[0044] (Composition (B)) The composition (B) includes at least one combination selected from the following (B1) to (B3). (B1) A combination of an epoxy resin having a fluorene skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B2) A combination of an epoxy resin having a biphenyl skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B3) Combination of an allylphenol compound and a bismaleimide compound

[0045] (B1) and (B2) are a combination that constitutes an epoxy resin composition different from the composition (A), and (B3) is a combination that forms an allyl-modified maleimide resin.

[0046] By using at least one of (B1) to (B3) in combination with composition (A) to form an epoxy resin composition, it is possible to form a resin coating layer 3 that exhibits high bonding strength with a resin member 5 even when exposed to high temperatures exceeding 100° C. In other words, (B1) to (B3) are components that improve the heat resistance of the epoxy resin.

[0047] The blending ratio of the epoxy resin and the phenol compound in (B1) is preferably set so that the molar equivalent ratio of the epoxy group to the hydroxyl group is 0.7 to 1.5, taking into consideration the reactivity of the two, etc. The molar equivalent ratio of the epoxy group to the hydroxyl group is more preferably 0.8 to 1.4, and further preferably 0.9 to 1.3.

[0048] The mixing ratio of the epoxy resin to the phenol compound in (B2) is the same as that in (B1) above.

[0049] The blending ratio of the allylphenol compound to the bismaleimide compound in (B3) is preferably set so that the molar equivalent ratio of maleimide groups to allyl groups is 0.7 to 1.5, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.3.

[0050] The content of composition (B) in the epoxy resin composition is preferably 10 to 80 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 65 parts by mass, relative to 100 parts by mass of the total content of compositions (A) and (B).

[0051] By containing composition (B) in the epoxy resin composition in an amount within the above range, it is possible to form a resin coating layer 3 having good heat resistance while maintaining molecular compatibility with the thermoplastic resin.

[0052] In the present disclosure, the content of composition (A) and / or composition (B) refers to the blended amount of composition (A) and / or composition (B), and does not include the amount of the solvent described below.

[0053] From the viewpoint of forming an epoxy resin layer having molecular compatibility with thermoplastic resins and heat resistance, the total content of composition (A) and composition (B) in 100% by mass of the epoxy resin composition (excluding the solvent) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0054] The epoxy resin having a fluorene structure in (B1) is preferably a bifunctional epoxy resin. Examples of the epoxy resin having a fluorene structure include "OGSOL (registered trademark) PG-100", "OGSOL (registered trademark) CG-500", "OGSOL (registered trademark) EG-200", and "OGSOL (registered trademark) EG-280" (all manufactured by Osaka Gas Chemicals Co., Ltd.). These epoxy resins having a fluorene structure may be used alone or in combination of two or more kinds.

[0055] The phenolic compound having a fluorene structure in (B1) and (B2) is preferably a divalent phenolic compound. Examples of the phenolic compound having a fluorene structure include "BPF" (bisphenol fluorene; 9,9-bis(4-hydroxyphenyl)fluorene), "BPEF" (bisphenoxyethanol fluorene; 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene), and "BCF" (biscresol fluorene; 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (all manufactured by Osaka Gas Chemicals Co., Ltd.). These phenolic compounds having a fluorene structure may be used alone or in combination of two or more kinds.

[0056] An example of the phenolic compound having an imidazolidinone skeleton in (B1) and (B2) is "TAM-005" (manufactured by Aica Kogyo Co., Ltd.) derived from a novolac-type phenolic resin. These phenolic compounds having an imidazolidinone skeleton may be used alone or in combination of two or more kinds.

[0057] Examples of the phenolic compounds having an aminotriazine skeleton in (B1) and (B2) include novolak-type phenolic resins modified with melamine, benzoguanamine, etc., such as "Phenolite (registered trademark) LA-7052", "Phenolite (registered trademark) LA-7054", "Phenolite (registered trademark) LA-7751", "Phenolite (registered trademark) LA-1356", and "Phenolite (registered trademark) LA-3018-50P" (all manufactured by DIC Corporation). These phenolic compounds having an aminotriazine skeleton may be used alone or in combination of two or more kinds.

[0058] Examples of the epoxy resin having a biphenyl skeleton in (B2) include "jER (registered trademark) YX-4000", "jER (registered trademark) YX-4000H", "jER (registered trademark) YL6121HA", and "jER (registered trademark) YL6677" (all manufactured by Mitsubishi Chemical Corporation), as well as "NC-3000", "NC-3000-L", "NC-3000-H", "NC-3000-FH-75M", "NC-3100", and "CER-3000-L" (all manufactured by Nippon Kayaku Co., Ltd.). These epoxy resins having a biphenyl skeleton may be used alone or in combination of two or more kinds.

[0059] Examples of the allylphenol compound in (B3) include "APG low viscosity allylphenol resin", "LVA low volatility allylphenol resin", "FTC-AE low polarity allyl ether phenol resin", and "FATC low polarity polyfunctional allylphenol resin" (all manufactured by Gun-ei Chemical Industry Co., Ltd.). These allylphenol compounds may be used alone or in combination of two or more kinds.

[0060] Examples of the bismaleimide compound in (B3) include 4,4'-diphenylmethane bismaleimide "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", m-phenylene bismaleimide "BMI-3000", "BMI-3000H", bisphenol A diphenyl ether bismaleimide "BMI-4000", 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide "BMI-5000", and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane "BMI-TMH" (all manufactured by Daiwa Chemical Industry Co., Ltd.). These bismaleimide compounds may be used alone or in combination of two or more.

[0061] A catalyst for accelerating the polyaddition reaction may be added to the epoxy resin composition. Suitable catalysts include, for example, tertiary amines such as triethylamine and 2,4,6-tris(dimethylaminomethyl)phenol, and phosphorus compounds such as triphenylphosphine.

[0062] The catalyst may be contained in either composition (A) or composition (B), or in both composition (A) and composition (B).

[0063] When a catalyst is added, the amount of the catalyst used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of the raw material compounds forming the epoxy resin, from the viewpoint of appropriately promoting the polyaddition reaction.

[0064] Composition (A) and / or composition (B) may contain a solvent from the viewpoints of ease of mixing these compositions, ease of coating of the epoxy resin composition, etc. As the solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, cyclohexane, n-hexane, ethanol, and methanol are preferably used from the viewpoints of solubility of composition (A) and / or composition (B) and suppression of residues after the polyaddition reaction of the epoxy resin composition.

[0065] Composition (A) and / or composition (B) may contain additives such as colorants as necessary in order to form a desired resin coating layer 3. In this case, the total amount of raw material compounds forming the epoxy resin in 100% by mass of the epoxy resin composition (excluding the solvent) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.

[0066] The resin coating layer laminate 1 is preferably produced through a process of reacting an epoxy resin composition containing composition (A) and composition (B) on the surface of a metal member 2 to form one or more layers of the resin coating layer 3.

[0067] By forming an epoxy resin layer by reacting an epoxy resin composition on the surface of a metal component 2, a resin coating layer laminate 1 can be obtained in which a resin coating layer 3 is firmly adhered to the surface of the metal component 2.

[0068] The method for coating the epoxy resin composition on the surface of the metal member 2 is not particularly limited, but examples thereof include a spray coating method and a dipping method.

[0069] The heating temperature when reacting the coated epoxy resin composition to form an epoxy resin layer depends on the types of compounds to be reacted, but is preferably 120 to 200° C., more preferably 120 to 180° C., and even more preferably 130 to 170° C. from the viewpoints of ease of operation in on-site polymerization and production efficiency of the resin coating layer laminate 1. From the same viewpoint, the heating time is preferably 5 to 90 minutes, more preferably 10 to 80 minutes, and even more preferably 15 to 60 minutes.

[0070] When the epoxy resin composition contains a solvent, it is preferable that after coating the epoxy resin composition, it is appropriately dried to volatilize the solvent, and then heated to cause the reaction.

[0071] (curable resin layer) When the resin coating layer 3 is made up of multiple layers, it may further include, in addition to the epoxy resin layer, a resin coating layer formed from a cured product of a resin composition containing a curable resin (hereinafter, also referred to as a "curable resin layer"). Examples of the curable resin include allyl-modified maleimide resin, urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.

[0072] The curable resin layer may be formed of one of these resins, or may be formed by mixing two or more of them. The curable resin layer may be composed of two or more layers, and each layer may be formed of a resin composition containing a different type of curable resin.

[0073] Since the resin coating layer 3 has a laminated structure of an epoxy resin layer and a curable resin layer, various properties such as strength and impact resistance based on the curable resin can be imparted to the resin coating layer 3.

[0074] The order in which the curable resin layer and the epoxy resin layer are stacked is not particularly limited, but from the viewpoint of bonding the metal member 2 and the resin member 5 with high bonding strength, it is preferable to stack them so that the outermost surface of the resin coating layer 3 is the epoxy resin layer.

[0075] The method for coating the resin composition containing the curable resin is not particularly limited, but examples thereof include a spray coating method and a dipping method.

[0076] The resin composition may contain a solvent from the viewpoint of ease of mixing and coating. The resin composition may contain additives such as a colorant as necessary in order to form a desired resin coating layer 3. In this case, the total amount of raw material compounds forming the curable resin in 100% by mass of the resin composition (excluding the solvent) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.

[0077] In the present disclosure, a curable resin means a resin that cures by crosslinking, and is not limited to a heat-curing type, but also includes a room temperature curing type and a light-curing type. The light-curing type can be cured in a short time by irradiation with visible light or ultraviolet light. The light-curing type may be used in combination with a heat-curing type and / or a room temperature curing type. Examples of the light-curing type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and "Lipoxy (registered trademark) LC-720" (both manufactured by Showa Denko K.K.).

[0078] [Allyl-modified maleimide resin] The allyl-modified maleimide resin is a reaction product obtained by combining an allyl compound with a bismaleimide compound. Allyl-modified maleimide resins are known as high heat-resistant resins, and some have a glass transition temperature of 250°C or higher. For this reason, the use of allyl-modified maleimide resins is effective in increasing the heat resistance of the resin coating layer 3.

[0079] The allyl compound may be, for example, the same as the allylphenol compound in (B3) above. The bismaleimide compound may be, for example, the same as the bismaleimide compound in (B3) above. The composition containing the combination of these allyl compounds and bismaleimide compounds may be cured, for example, using a peroxide catalyst, to form a curable resin layer.

[0080] [Urethane resin] The urethane resin is usually a resin obtained by the reaction of an isocyanato group with a hydroxyl group, and is preferably a urethane resin that corresponds to the definition of "a coating material containing 10% by weight or more of polyisocyanate as a non-volatile component of a vehicle" in ASTM D16. The urethane resin may be of one-component type or two-component type.

[0081] Examples of one-component urethane resins include oil-modified types (cured by oxidative polymerization of unsaturated fatty acid groups), moisture-cured types (cured by reaction of isocyanato groups with water in the air), block types (cured by reaction of hydroxyl groups with isocyanato groups regenerated by dissociation of a blocking agent by heating), and lacquer types (cured by evaporation of a solvent and drying). Among these, moisture-cured one-component urethane resins are preferably used from the viewpoint of ease of handling. Specific examples of moisture-cured one-component urethane resins include "UM-50P" (manufactured by Showa Denko K.K.).

[0082] Examples of two-component urethane resins include catalyst curing types (which cure when an isocyanato group reacts with water in the air in the presence of a catalyst) and polyol curing types (which cure when an isocyanato group reacts with a hydroxyl group of a polyol compound).

[0083] Examples of the polyol compound in the polyol curing type include polyester polyol, polyether polyol, and phenol resin.

[0084] Examples of isocyanate compounds having an isocyanato group in the polyol curing type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimer acid diisocyanate; aromatic isocyanates such as 2,4- or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, p-phenylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or polymeric MDI, which is a polynuclear mixture thereof; and alicyclic isocyanates such as isophorone diisocyanate (IPDI).

[0085] The blending ratio of the polyol compound to the isocyanate compound in the polyol-curing type two-component urethane resin is preferably set so that the molar equivalent ratio of hydroxyl groups to isocyanato groups is 0.7 to 1.5.

[0086] Examples of urethanization catalysts used in two-component urethane resins include amine-based catalysts such as triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N,N,N',N",N"-pentamethyldipropylene-triamine, N-methylmorpholine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethanol, and triethylamine; and organotin-based catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimaleate.

[0087] In the polyol curing type, it is generally preferable to mix 0.01 to 10 parts by mass of a urethane catalyst with respect to 100 parts by mass of a polyol compound.

[0088] [Epoxy resin] Epoxy resin is a resin having two or more epoxy groups in one molecule. Examples of prepolymers of epoxy resin before curing include ether-based bisphenol-type epoxy resins, novolac-type epoxy resins, polyphenol-type epoxy resins, aliphatic-type epoxy resins, ester-based aromatic epoxy resins, cyclic aliphatic epoxy resins, and ether-ester-based epoxy resins. Among these, bisphenol A-type epoxy resins are preferably used. These epoxy resins may be used alone or in combination of two or more.

[0089] Examples of bisphenol A type epoxy resins include "jER (registered trademark) 828" and "jER (registered trademark) 1001" (both manufactured by Mitsubishi Chemical Corporation).

[0090] An example of the novolac type epoxy resin is "DEN (registered trademark) 438 (registered trademark)" (manufactured by The Dow Chemical Company).

[0091] Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenolic resins, thiols, imidazoles, cationic catalysts, etc. By using the curing agent in combination with a long-chain aliphatic amine and / or thiols, a resin coating layer 3 having a large elongation rate and excellent impact resistance can be formed.

[0092] Examples of the thiols in the curing agent include the same compounds as those exemplified as the thiol compounds used in forming the functional group-containing layer described below. Among these, pentaerythritol tetrakis(3-mercaptobutyrate) "Karenz MT (registered trademark) PE1" (manufactured by Showa Denko K.K.) is preferred from the viewpoints of the elongation rate and impact resistance of the resin coating layer 3.

[0093] [Vinyl ester resin] Vinyl ester resins are obtained by dissolving a vinyl ester compound in a polymerizable monomer such as styrene. Vinyl ester resins are also called epoxy (meth)acrylate resins, but in the present disclosure, vinyl ester resins also include urethane (meth)acrylate resins.

[0094] Examples of the vinyl ester resin that can be used include those described in "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988) and "Paint Terminology Dictionary" (published by Shikizai Kyokai, 1993). Specific examples of the vinyl ester resin include "Lipoxy (registered trademark) R-802", "Lipoxy (registered trademark) R-804", and "Lipoxy (registered trademark) R-806" (all manufactured by Showa Denko K.K.).

[0095] Examples of the urethane (meth)acrylate resin include a radical polymerizable unsaturated group-containing oligomer obtained by reacting an isocyanate compound with a polyol compound, followed by reacting a hydroxyl group-containing (meth)acrylic monomer with a hydroxyl group-containing allyl ether monomer, if necessary. A specific example of the urethane (meth)acrylate resin is "Lipoxy (registered trademark) R-6545" (manufactured by Showa Denko K.K.).

[0096] The vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide. The organic peroxide is not particularly limited, but examples thereof include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates. By combining these organic peroxides with a cobalt metal salt or the like, curing at room temperature is also possible.

[0097] The cobalt metal salt is not particularly limited, but examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Among these, cobalt naphthenate and cobalt octylate are preferred.

[0098] [Unsaturated polyester resin] The unsaturated polyester resin is prepared by dissolving an unsaturated polyester, which is a condensation product of an esterification reaction between a polyol compound, an unsaturated polybasic acid, and, if necessary, a saturated polybasic acid, in a polymerizable monomer such as styrene.

[0099] As the unsaturated polyester resin, for example, those described in "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988) and "Paint Terminology Dictionary" (published by Shikizai Kyokai, 1993) can be used. A specific example of the unsaturated polyester resin is "Rigolac (registered trademark)" (manufactured by Showa Denko K.K.).

[0100] Unsaturated polyester resins can be cured by radical polymerization through heating in the presence of a catalyst, similar to the case of vinyl ester resins.

[0101] <Surface treatment> The metal member 2 preferably has a surface that has been surface-treated.

[0102] The resin coating layer 3 is formed on the surface-treated surface of the metal member 2, and thus is easily adhered to the metal member 2 firmly.

[0103] Examples of the surface treatment include cleaning or degreasing with a solvent or the like, blasting, polishing, etching, and chemical conversion treatment. These surface treatments may be used alone or in combination of two or more. Among these, surface treatments by blasting, polishing, etching, or chemical conversion treatment are preferred.

[0104] The surface treatment is carried out for the purpose of improving the adhesion of the resin coating layer 3 to the surface of the metal component 2 by cleaning the surface of the metal component 2, generating hydroxyl groups on the surface, or by creating an anchor effect by forming fine irregularities (roughening) on ​​the surface.

[0105] The surface properties of the metal member 2 that has been surface-treated by the above-mentioned method may change from those immediately after the surface treatment due to the formation of the resin coating layer 3 on the surface-treated surface. For this reason, it is considered impossible or impractical to specify and express the surface properties of the surface-treated metal member 2 in the resin coating layer laminate 1. Therefore, in the present disclosure, the surface of the surface-treated metal member 2 is specified by the method of surface treatment.

[0106] The surface treatment can be carried out by a known method, and specific examples of the method include the following methods.

[0107] [Cleaning or degreasing treatment] Examples of the cleaning or degreasing treatment using a solvent or the like include cleaning the surface of the metal member 2 with an organic solvent such as acetone or toluene, or wiping to degrease the surface.

[0108] [Blast treatment] The blasting treatment includes, for example, shot blasting and sand blasting.

[0109] [Polishing process] Examples of the polishing treatment include buff polishing using an abrasive cloth, roll polishing using abrasive paper (sandpaper), and electrolytic polishing.

[0110] [Etching process] Examples of the etching treatment include chemical etching treatments such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and an iron salt method, and electrochemical etching treatments such as an electrolytic etching method.

[0111] When the metal member 2 contains aluminum, the etching treatment is preferably an alkali method using an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and more preferably a caustic soda method using an aqueous sodium hydroxide solution.

[0112] The alkali method can be carried out, for example, by immersing the aluminum material in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70° C. for 1 to 15 minutes. Additives such as chelating agents, oxidizing agents, and phosphates may be added. After immersion, it is preferable to neutralize (desmut) the material with an aqueous solution of nitric acid having a concentration of 5 to 20% by mass, wash with water, and dry it.

[0113] [Chemical conversion treatment] The chemical conversion treatment is mainly for forming a chemical conversion film on the surface of the metal member 2. When the metal member 2 contains aluminum, examples of the chemical conversion treatment include boehmite treatment and zirconium treatment, with boehmite treatment being preferred. The chemical conversion treatment is preferably carried out after the etching treatment.

[0114] The boehmite treatment is carried out, for example, by treating an aluminum material with hot water at about 90 to 100°C, and a boehmite (aluminum hydrated oxide) film is formed on the surface of the aluminum material. Ammonia, triethanolamine, or the like may be added to the water as a reaction accelerator. For example, the boehmite treatment can be carried out by immersing the aluminum material in hot water at 90 to 100°C containing triethanolamine at a concentration of 0.1 to 5.0 mass% for 3 seconds to 5 minutes. In the boehmite treatment, it is preferable to bake the material after the treatment with hot water in order to form a good boehmite film.

[0115] The zirconium treatment is carried out, for example, by immersing the aluminum material in a liquid containing a zirconium salt such as zirconium phosphate, and a coating of a zirconium compound is formed on the surface of the aluminum material. For example, the zirconium treatment can be carried out by immersing the aluminum material in a 45 to 70°C liquid of a zirconium treatment conversion agent such as "Palcoat 3762" or "Palcoat 3796" (both manufactured by Nihon Parkerizing Co., Ltd.) for 0.5 to 3 minutes.

[0116] When the metal member 2 containing aluminum is subjected to a surface treatment, the surface treatment is preferably one or more types selected from an etching treatment and a boehmite treatment.

[0117] <Functional group-containing layer 4> Fig. 4 shows a schematic cross-sectional view of a resin coating layer laminate 1 according to another embodiment. The resin coating layer laminate 1 shown in Fig. 4 has a functional group-containing layer 4 laminated between a metal member 2 and a resin coating layer 3 in contact with both of them. The functional group-containing layer 4 has a structure derived from one or more functional groups selected from the following (C1) to (C7). (C1) One or more functional groups selected from an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, and an isocyanato group derived from a silane coupling agent. (C2) A functional group generated by the reaction of an amino group derived from a silane coupling agent with an epoxy compound (C3) A functional group formed by the reaction of a mercapto group derived from a silane coupling agent with one or more compounds selected from an epoxy compound, an isocyanate compound, an epoxy-modified (meth)acrylate compound, and an amino group-containing (meth)acrylate compound. (C4) A functional group formed by the reaction of a (meth)acryloyl group derived from a silane coupling agent with a thiol compound. (C5) A functional group formed by the reaction of an epoxy group derived from a silane coupling agent with one or more compounds selected from an amino compound, a thiol compound, and an amino group-containing (meth)acrylate compound. (C6) Isocyanato group derived from isocyanate compounds (C7) Mercapto group derived from thiol compound

[0118] The structure derived from the functional group in the functional group-containing layer 4 chemically bonds with the metal member 2 and the resin coating layer 3, which are laminated in contact with the functional group-containing layer 4, and thereby the metal member 2 and the resin coating layer 3 can be firmly bonded together. It is considered that the functional group-containing layer 4 can also contribute to improving the bonding strength between the surface of the resin coating layer 3 side of the resin coating layer laminate 1 and the resin member 5.

[0119] The fact that the functional group-containing layer 4 has structures derived from the functional groups (C1) to (C7) may be confirmed by analysis immediately after the functional group-containing layer 4 is formed on the surface of the metal member 2. However, in the resin coating layer laminate 1, these structures derived from functional groups are changed by chemical bonding with the resin coating layer 3, and it is impossible or impractical to confirm the presence of the functional groups or structures in the functional group-containing layer 4. For this reason, in the present disclosure, the configuration of the functional group-containing layer 4 is specified based on the functional groups possessed by the silane coupling agent and / or other compounds capable of generating the structures derived from the functional groups (C1) to (C7).

[0120] The functional group-containing layer 4 is preferably laminated on the surface of the metal member 2 that has been subjected to the above-mentioned surface treatment. That is, the metal member 2 is preferably surface-treated before forming the functional group-containing layer 4. This makes it possible to firmly bond the metal member 2 and the resin coating layer 3 by a synergistic effect of the surface treatment and the chemical bond brought about by the functional group-containing layer 4. The above-mentioned synergistic effect may also improve the bonding strength between the resin coating layer 3 and the resin member 5.

[0121] The functional group-containing layer 4 can be formed by treating the surface of the metal member 2 with one or more compounds selected from the following (c1) to (c7) before forming the resin coating layer 3. (c1) a silane coupling agent having one or more functional groups selected from an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, and an isocyanato group; (c2) A combination of a silane coupling agent having an amino group and an epoxy compound (c3) A combination of a silane coupling agent having a mercapto group and one or more compounds selected from an epoxy compound, an isocyanate compound, an epoxy-modified (meth)acrylate compound, and an amino group-containing (meth)acrylate compound. (c4) A combination of a silane coupling agent having a (meth)acryloyl group and a thiol compound (c5) A combination of a silane coupling agent having an epoxy group and one or more compounds selected from an amino compound, a thiol compound, and an amino group-containing (meth)acrylate compound. (c6) Isocyanate compounds (c7) Thiol compounds

[0122] (c1) to (c7) correspond to the functional groups (C1) to (C7) formed therefrom, respectively. That is, the treatment with (c1) forms a functional group-containing layer 4 into which the functional group of (C1) is introduced, and the treatment with (c2) forms a functional group-containing layer 4 into which the functional group of (C2) is introduced. The same applies to the treatments with (c3) to (c7).

[0123] For example, in the treatment of (c2), when a bifunctional epoxy compound is reacted with an amino group, an epoxy group, which is a functional group of the bifunctional epoxy compound, is introduced to the terminal.Similarly, in the treatment of (c3), when a polyfunctional isocyanate compound is reacted with a mercapto group, an isocyanato group, which is a functional group of the polyfunctional isocyanate compound, is introduced to the terminal.

[0124] The method for forming the functional group-containing layer 4 is not particularly limited, but it can be formed by coating the surface of the metal member 2 with the silane coupling agents and / or other compounds shown in (c1) to (c7) by a known coating method such as spray coating, immersion, etc. For example, the metal member 2 can be immersed in a solution of a silane coupling agent or the like having a concentration of 5 to 50 mass % at room temperature to 100° C. for 1 minute to 5 days, and then dried at room temperature to 100° C. for 1 minute to 5 hours.

[0125] [Silane coupling agent] As the silane coupling agent in (c1) to (c5), for example, a known one used in the surface treatment of glass fiber can be used. A silanol group generated by hydrolysis of the silane coupling agent, or a silanol group of an oligomerized product generated by condensation of the silanol group, bonds with the surface of the metal member 2, particularly with a hydroxyl group generated by the surface treatment, thereby introducing a functional group derived from the silane coupling agent, such as an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, or an isocyanato group, onto the surface of the metal member 2. These functional groups contribute to the formation of a chemical bond with the compound forming the resin coating layer 3.

[0126] These functional groups can generate functional groups having chemical affinity with the compound forming the resin coating layer 3 by reacting with the functional groups of a compound other than the silane coupling agent used in forming the functional group-containing layer 4. For this reason, in each of the treatments (c2) to (c5), it is preferable to treat the surface of the metal member 2 with a silane coupling agent, and then with a compound that is to be combined with the silane coupling agent.

[0127] In this way, the silane coupling agent is suitably used as a compound for forming the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4 .

[0128] The silane coupling agent used has one or more functional groups selected from an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, and an isocyanato group. These silane coupling agents may be used alone or in combination of two or more.

[0129] Examples of silane coupling agents having an amino group include 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminopropyltrimethoxysilane hydrochloride.

[0130] Examples of silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0131] Examples of silane coupling agents having a (meth)acryloyl group include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane.

[0132] Examples of silane coupling agents having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0133] An example of a silane coupling agent having an isocyanato group is 3-isocyanatopropyltriethoxysilane.

[0134] [Thiol compounds] The thiol compound in (c4), (c5) or (c7) is a compound other than a silane coupling agent. The mercapto group of the thiol compound is likely to bond with the surface of the metal member 2, particularly with the hydroxyl group generated by the surface treatment. In addition, when used in combination with a silane coupling agent, the mercapto group of the thiol compound reacts with a functional group such as a (meth)acryloyl group or an epoxy group derived from the silane coupling agent, and can generate a functional group that has chemical affinity with the compound that forms the resin coating layer 3 on the surface of the metal member 2. For this reason, the thiol compound is preferably used as a compound that forms the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 through the functional group-containing layer 4.

[0135] The thiol compound is not particularly limited, but examples thereof include pentaerythritol tetrakis(3-mercaptopropionate) "jER Cure (registered trademark) QX40" (manufactured by Mitsubishi Chemical Corporation), "Polythiol (registered trademark) QE-340M" (manufactured by Toray Fine Chemicals Co., Ltd.); ether-based primary thiol compound "Cup Cure (registered trademark) 3-800" (manufactured by Cognis); 1,4-bis(3-mercaptobutyryloxy)butane "KarenzMT (registered trademark) BD1" (manufactured by Showa Denko K.K.); pentaerythritol tetrakis(3-mercaptobutyrate) "KarenzMT (registered trademark) PE1" (manufactured by Showa Denko K.K.); and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione "KarenzMT (registered trademark) NR1" (manufactured by Showa Denko K.K.). These thiol compounds may be used alone or in combination of two or more kinds.

[0136] [Isocyanate Compound] The isocyanate compound in (c3) or (c6) is a compound other than a silane coupling agent. The isocyanate group of the isocyanate compound is likely to bond with the surface of the metal member 2, particularly with hydroxyl groups generated by surface treatment. In addition, when used in combination with a silane coupling agent, it can react with functional groups such as mercapto groups derived from the silane coupling agent to generate functional groups that have chemical affinity with the compound that forms the resin coating layer 3 on the surface of the metal member 2. For this reason, the isocyanate compound is preferably used as a compound that forms the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4.

[0137] The isocyanate compound is not particularly limited, but examples thereof include polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI); and isocyanate compounds having a radical reactive group such as 2-isocyanatoethyl methacrylate "Karenz MOI (registered trademark)", 2-isocyanatoethyl acrylate "Karenz AOI (registered trademark)" and "AOI-VM (registered trademark)", and 1,1-(bisacryloyloxyethyl)ethyl isocyanate "Karenz BEI (registered trademark)" (all manufactured by Showa Denko KK). The isocyanate compound may be used alone or in combination of two or more kinds.

[0138] [Epoxy Compound] The epoxy compound in (c2) or (c3) is a compound other than a silane coupling agent. The epoxy group of the epoxy compound reacts with a functional group such as an amino group or a mercapto group derived from the silane coupling agent to generate a functional group having chemical affinity with a compound forming the resin coating layer 3 on the surface of the metal member 2. For this reason, the epoxy compound is suitably used as a compound forming the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4.

[0139] As the epoxy compound, a known epoxy compound can be used, and a polyfunctional epoxy compound and a compound having an alkenyl group in addition to an epoxy group are preferred. Examples of the epoxy compound include allyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and bifunctional epoxy resins. The epoxy compound may be an alicyclic epoxy compound. Examples of the alicyclic epoxy compound include 1,2-epoxy-4-vinylcyclohexane "Celloxide (registered trademark) 2000" and 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate "Celloxide (registered trademark) 2021P" (both manufactured by Daicel Corporation). These epoxy compounds may be used alone or in combination of two or more kinds.

[0140] [Amino Compounds] The amino compound in (c5) is a compound other than a silane coupling agent. The amino group of the amino compound reacts with a functional group such as an epoxy group derived from the silane coupling agent to generate a functional group having chemical affinity with a compound forming the resin coating layer 3 on the surface of the metal member 2. For this reason, the amino compound is suitably used as a compound forming the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4.

[0141] As the amino compound, known amino compounds can be used, and preferred are amino compounds having two or more amino groups in one molecule and compounds having an alkenyl group in addition to an amino group (including an amide group). Examples of the amino compound include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3'-iminobis(propylamine), 3,3'-methyl ... Examples of the amino compounds include bis(propylamine), bis(3-aminopropyl)ether, 1,2-bis(3-aminopropyloxy)ethane, menthene diamine, isophorone diamine, bisaminomethylnorbornane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and aminoethylpiperazine. These amino compounds may be used alone or in combination of two or more.

[0142] [Epoxy-modified (meth)acrylate compound] The epoxy-modified (meth)acrylate compound in (c3) is a compound other than a silane coupling agent, and has an epoxy group and a (meth)acryloyl group. Therefore, by reacting with a functional group such as a mercapto group derived from the silane coupling agent, a functional group having chemical affinity with a compound forming the resin coating layer 3 on the surface of the metal member 2 can be generated. Therefore, the epoxy-modified (meth)acrylate compound is suitably used as a compound forming the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4.

[0143] Examples of the epoxy-modified (meth)acrylate compound include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl methacrylate "Cyclomer (registered trademark) M100", and compounds in which a part of the multifunctional epoxy compound in (c2) and (c3) is (meth)acryloylated. These epoxy-modified (meth)acrylate compounds may be used alone or in combination of two or more kinds.

[0144] [Amino group-containing (meth)acrylate compound] The amino group-containing (meth)acrylate compound in (c3) or (c5) is a compound other than a silane coupling agent, and has an amino group and a (meth)acryloyl group. Therefore, by reacting with a functional group such as a mercapto group or an epoxy group derived from the silane coupling agent, a functional group having chemical affinity with a compound forming the resin coating layer 3 on the surface of the metal member 2 can be generated. Therefore, the amino group-containing (meth)acrylate compound is suitably used as a compound forming the functional group-containing layer 4 in order to firmly bond the metal member 2 and the resin coating layer 3 via the functional group-containing layer 4.

[0145] Examples of the amino group-containing (meth)acrylate compound include (meth)acrylamide and the above-mentioned (c5) amino compound having two or more amino groups in one molecule, which is partially (meth)acryloylated. These amino group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

[0146] [Engine ECU 10 (metal-resin bonded body)] Fig. 5 is a schematic cross-sectional view of a state in which a metal member 2 and a resin member 5 are joined via a resin coating layer 3, specifically, a schematic cross-sectional view of a state in which the other surface 15 of a first part 12 is joined to a joining surface 27 of a second part 14. In an engine ECU (metal-resin joined body) 10 shown in Fig. 5, a surface on the resin coating layer 3 side of a resin coating layer laminate 1 (a laminate of a resin coating layer 3 and a first part 12) is joined to a resin member 5 (second part 14).

[0147] Since the resin coating layer 3 exhibits high bonding strength with the resin member 5 even when exposed to high temperatures exceeding 100° C., the engine ECU 10 in which the metal member 2 and the resin member 5 are bonded via the resin coating layer 3 is firmly bonded, and thermal deterioration of the bonded portion is suppressed. In particular, when a resin member 5 with excellent heat resistance is bonded, an engine ECU 10 with excellent heat resistance can be obtained.

[0148] 5, in the engine ECU 10, a metal member 2 (i.e., the first part 12) and a resin member 5 (i.e., the second part 14) are joined via a resin coating layer 3 (contained in the resin coating layer laminate 1), and the resin coating layer 3 and the resin member 5 are welded together. The metal member 2 (i.e., the first part 12) and the resin member 5 (i.e., the second part 14) are joined by the resin coating layer 3 in an airtight manner.

[0149] The engine ECU 10 is installed in an engine room of an automobile (not shown) and is electrically connected to an external power source, various sensors such as a temperature sensor and an airflow sensor, and various control devices such as an ignition mechanism through a connector. The semiconductor element 30 on the circuit board 32 is supplied with power from an external power source through the connector 20, and receives detection signals from the various sensors. The semiconductor element 30 performs a predetermined arithmetic process based on the input detection signals and generates a control signal. The generated control signal is output to each control device through the connector 20. The semiconductor element 30 on the circuit board 32 generates heat in accordance with the above-mentioned series of arithmetic processes. The heat generated by the semiconductor element 30 is thermally conducted to the first part 12 through the thermally conductive sheet 28. The first part 12 exchanges heat with the outside air through the heat dissipation fin 17 provided on one side surface, thereby dissipating the thermally conducted heat.

[0150] As described above, the engine ECU 10 can omit screws and sealant because the first part 12 and the second part 14 are joined via the resin coating layer 3. Therefore, the engine ECU 10 can be lighter and the parts management and manufacturing man-hours can be simplified compared to when screws are used for fastening because the screws and sealant can be omitted. The engine ECU 10 can omit the mounting seat required for fastening the screws and the recess for loading the sealant, so that the engine ECU 10 can be made smaller and its shape can be simplified. As a result, the engine ECU 10 can be made lighter and smaller.

[0151] The first part 12 and the second part 14 are joined together in an airtight manner by the resin coating layer 3, which prevents foreign matter such as moisture and dust from entering from outside the vehicle. Therefore, the engine ECU 10 can more reliably prevent malfunctions caused by foreign matter.

[0152] The resin coating layer 3 eliminates the need for multiple treatments such as base treatment such as frame treatment or plasma treatment of the surface of the resin member 5, primer coating, adhesive application, and adhesive curing, and therefore simplifies the manufacturing process compared to the case of bonding with conventional adhesives.

[0153] <Resin material 5> The resin member 5 to be bonded to the metal member 2 is not particularly limited and may be a general synthetic resin. Since the resin coating layer 3 exhibits high bonding strength with the resin member 5 even when exposed to high temperatures exceeding 100° C. and suppresses thermal deterioration of the bonded portion between the metal member 2 and the resin member 5, a heat-resistant resin is preferably used in order to obtain an engine ECU 10 having excellent heat resistance and high bonding strength.

[0154] Examples of heat-resistant resins include resins used in automobile parts, such as polyetherimide resin, polybutylene terephthalate resin, polyphenylene sulfone resin, glass fiber reinforced polyphenylene terephthalate, and glass fiber reinforced nylon. For example, carbon fiber reinforced resin (CFRP) in the form of a molded body such as sheet molding compound (SMC) containing carbon fiber and bulk molding compound (BMC) and glass fiber reinforced resin (GFRP) can also be used. SMC is a sheet-like molded body obtained by impregnating a mixture of unsaturated polyester resin and / or vinyl ester resin, polymerizable unsaturated monomer, hardener, low shrinkage agent, filler, etc. into reinforcing fibers such as carbon fiber.

[0155] The thickness of the resin coating layer 3 in the engine ECU 10 depends on the material of the resin member 5 to be joined to the resin coating layer 3 and the contact area of ​​the joint, but from the viewpoint of sufficient joint strength and heat resistance, it is preferably 1 μm to 10 mm, more preferably 10 μm to 2 mm, and even more preferably 20 μm to 500 μm.

[0156] Even when exposed to high temperatures exceeding 100° C., the resin coating layer 3 exerts a stress relaxation effect that suppresses thermal deformation of the engine ECU 10 or separation between the metal member 2 and the resin member 5 caused by the difference in thermal expansion coefficient between the metal member 2 and the resin member 5. This suppresses thermal deterioration of the joints of the engine ECU 10.

[0157] [Manufacturing method of engine ECU 10] A method for manufacturing the engine ECU 10 (metal-resin bonded body) of one embodiment includes a method for bonding the resin member 5 to the resin coating layer 3 of the resin coating layer laminate 1 by at least one method selected from the group consisting of hot air welding, hot plate welding, ultrasonic welding, vibration welding, electromagnetic induction method, high frequency method, laser method, hot plate welding, and heat pressing. The resin member 5 can be produced separately from the resin coating layer laminate 1.

[0158] Another embodiment of the manufacturing method for the engine ECU 10 (metal-resin joint body) includes a method in which a resin member 5 is molded on the resin coating layer 3 of the resin coating layer laminate 1 by injection molding, press molding, filament winding molding, hand lay-up molding, transfer molding, or the like, and in the process, the surface of the resin coating layer laminate 1 facing the resin coating layer 3 is joined to the resin member 5.

[0159] From the viewpoints of reducing the requirements for the manufacturing device, simplifying the manufacturing process, and allowing freedom in designing the resin member, it is advantageous to manufacture the engine ECU 10 (metal-resin bonded body) by a heat press method. Specifically, the engine ECU 10 can be manufactured by heating the resin coating layer 3 and pressing the metal member 2 and the resin member 5 together so that the heated resin coating layer 3 is interposed between the metal member 2 and the resin member 5. The heating temperature of the resin coating layer 3 depends on the melting point or softening point of the resin to be bonded, and is preferably 100°C to 350°C. For example, when the resin is nylon 6, the heating temperature is preferably 230°C. The heating temperature of the resin coating layer 3 having a melting point is preferably set to the melting point ±5°C, and the heating temperature of the resin coating layer 3 having a softening point is preferably set to the softening point ±15°C. The pressure during pressing is preferably 0.005 MPa to 10 MPa.

[0160] In another embodiment, the resin coating layer laminate 1' may be formed by having one or more resin coating layers 3' laminated on the resin member 5 instead of the metal member 2. The resin coating layer 3' can be formed on the surface of the resin member 5 using the same material as the resin coating layer 3 described above. In this embodiment, the epoxy resin layer is preferably formed so as to be in direct contact with the resin member 5. Therefore, when the resin coating layer 3' is made of multiple layers, it is preferable to laminate other layers, such as a curable resin layer, on the epoxy resin layer after forming the epoxy resin layer on the resin member 5. In this embodiment, the bonding between the metal member 2 and the resin member 5 can be carried out by replacing the above-mentioned "metal member 2" with the "resin member 5" in this embodiment, the above-mentioned "resin member 5" with the "metal member 2" in this embodiment, and the above-mentioned "resin coating layer laminate 1" with the "resin coating layer laminate 1'".

[0161] In yet another embodiment, the resin coating layer laminates 1 and 1' are formed by laminating the above-mentioned resin coating layers 3 and 3' on the metal member 2 and the resin member 5, respectively, and the resin coating layer 3 of the resin coating layer laminate 1 and the resin coating layer 3' of the resin coating layer laminate 1' are welded. As a result, the metal member 2 and the resin member 5 are joined via the resin coating layers 3 and 3'. In this embodiment, the engine ECU 10 (metal-resin joined body) can be manufactured by welding the resin coating layer 3 of the resin coating layer laminate 1 and the resin coating layer 3' of the resin coating layer laminate 1' using at least one method selected from the group consisting of hot air welding, hot plate welding, ultrasonic welding, vibration welding, electromagnetic induction method, high frequency method, laser method, hot plate welding, and heat pressing, preferably heat pressing.

[0162] In the present embodiment, the engine ECU 10 has been described as being formed by joining the first part 12 as the metal member 2 and the second part 14 as the resin member 5, but the present invention is not limited to this. For example, the resin member 5 also includes resin members (positioning resin pins, and resin bracket members that hold connectors and various sensors) provided on the second part 12 as the metal member 2.

[0163] Although several embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments and can be modified in various ways without departing from the gist of the present invention. EXAMPLES

[0164] Experimental and comparative test examples related to the present invention are shown below, but the present invention is not limited to the experimental examples below.

[0165] Details of the main raw materials used in the following practical test examples and comparative test examples are shown below.

[0166] [Metal parts] Aluminum plate: Aluminum alloy; Al-Mg-Si A6063, 18mm x 45mm, thickness 1.5mm -Iron plate: 18mm x 45mm, thickness 1.5mm SUS304 plate: Stainless steel SUS304 (Cr-Ni type), 18mm x 45mm, thickness 1.5mm Copper plate: 18mm x 45mm, thickness 1.5mm

[0167] [Silane coupling agents] ·KBM-903: 3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM-903" ·KBM-503: 3-Methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM-503"

[0168] [Composition (A)] <Difunctional epoxy resin> jER1007: "jER (registered trademark) 1007" manufactured by Mitsubishi Chemical Corporation <Dihydric phenol compounds> ·BPS: Bisphenol S

[0169] [Composition (B)] PG-100: Epoxy resin with a fluorene structure, "OGSOL (registered trademark) PG-100" manufactured by Osaka Gas Chemicals Co., Ltd. TAM-005: Phenolic compound with an imidazolidinone skeleton, novolac-type phenolic resin "TAM-005" manufactured by AICA Corporation NC-3000: Epoxy resin with a biphenyl skeleton, "NC-3000" manufactured by Nippon Kayaku Co., Ltd. APG: Allylphenol compound, Gun-ei Chemical Industry Co., Ltd.'s "APG low viscosity allylphenol resin" BMI-1000: 4,4'-diphenylmethane bismaleimide, "BMI-1000" manufactured by Daiwa Chemical Industry Co., Ltd. BPEF: Bisphenoxyethanol fluorene, "BPEF" manufactured by Osaka Gas Chemicals Co., Ltd.

[0170] [Resin material] PEI: Polyetherimide resin, "Ultem (registered trademark) 1000" manufactured by SABIC Japan, LLC PBT: Polybutylene terephthalate resin, SABIC Japan "Valox (registered trademark) 507", containing 30% glass fiber by weight PPS: Polyphenylene ether resin, DIC Corporation's "FZ-2140", containing 40% glass fiber by weight

[0171] [Production of resin coating layer laminate] By carrying out each step shown in the following production example, a resin coating layer laminate in which a resin coating layer was laminated on the surface of a metal member was produced.

[0172] <Production Example 1> (Surface treatment process) An aluminum plate as a metal member was immersed in a 5% by mass aqueous sodium hydroxide solution for 1.5 minutes, neutralized with a 5% by mass aqueous nitric acid solution, washed with water, and dried for etching. The aluminum plate after etching was boiled in pure water for 10 minutes and then baked at 250°C for 10 minutes for boehmite treatment.

[0173] (Functional group-containing layer formation process) 2 g of the silane coupling agent KBM-903 was dissolved in 1000 g of industrial ethanol. The resulting silane coupling agent solution was heated to 70°C, and the aluminum plate after the boehmite treatment was immersed in the silane coupling agent solution for 20 minutes. The aluminum plate was then taken out and dried at room temperature for 1 hour to form a functional group-containing layer on the boehmite-treated surface.

[0174] (Resin coating layer formation process) 100 g of epoxy resin jER1007, 6.2 g of bisphenol S, and 0.4 g of triethylamine were dissolved in 197 g of acetone to obtain a composition (A).

[0175] 100 g of an epoxy resin PG-100 having a fluorene skeleton, 61.9 g of a phenol compound TAM-005 having an imidazolidinone skeleton, and 1.3 g of triethylamine were dissolved in 300 g of acetone to obtain a composition (B1-1).

[0176] A resin composition obtained by blending composition (A) and composition (B1-1) at a mass ratio of 40 / 60 (excluding acetone) was spray-coated on the surface of the functional group-containing layer of the aluminum plate so that the thickness after drying was 70 μm. The resin composition was left in air (relative humidity 50%) at room temperature for 30 minutes to volatilize the solvent, and then left in a 150°C oven for 30 minutes to react, and then cooled to room temperature to form a resin coating layer, thereby obtaining a resin coating layer laminate E1.

[0177] <Manufacturing example C1> A comparative resin coating layer laminate C1 was produced in the same manner as in Production Example 1, except that the resin composition used in the resin coating layer forming step was only the composition (A).

[0178] <Production Example 2> (Surface treatment process) As the metal member, an iron plate was polished with #100 sandpaper and then degreased with acetone.

[0179] (Resin coating layer formation process) 100 g of an epoxy resin NC-3000 having a biphenyl skeleton, 91.9 g of a phenolic compound TAM-005 having an imidazolidinone skeleton, and 1.54 g of triethylamine were dissolved in 356.5 g of acetone to obtain a composition (B2).

[0180] A resin composition prepared by blending the composition (A) and the composition (B2) prepared in Production Example 1 in a mass ratio of 50 / 50 (excluding acetone) was spray-coated on the polished surface of an iron plate so that the thickness after drying was 50 μm. The resin composition was left in air (relative humidity 50%) at room temperature for 30 minutes to volatilize the solvent, and then left in a 150°C oven for 30 minutes to react, and then cooled to room temperature to form a resin coating layer, thereby obtaining a resin coating layer laminate E2.

[0181] <Manufacturing example C2> A comparative resin coating layer laminate C2 was produced in the same manner as in Production Example 2, except that the resin composition used in the resin coating layer forming step was only the composition (A).

[0182] <Production Example 3> (Surface treatment process) As the metal member, a SUS304 plate was polished with #100 sandpaper and then degreased with acetone.

[0183] (Functional group-containing layer formation process) 2 g of the silane coupling agent KBM-503 was dissolved in 1000 g of industrial ethanol. The resulting silane coupling agent solution was heated to 70°C, and the polished SUS304 plate was immersed in the silane coupling agent solution for 20 minutes. The SUS304 plate was then taken out and dried at room temperature for 1 hour to form a functional group-containing layer on the surface of the SUS304 plate.

[0184] (Resin coating layer formation process) 100 g of an allylphenol compound APG and 100 g of a bismaleimide compound BMI-1000 were dissolved in 371 g of acetone to obtain a composition (B3).

[0185] A resin composition prepared by blending the composition (A) and the composition (B3) prepared in Production Example 1 in a mass ratio of 70 / 30 excluding acetone was spray-coated on the surface of the functional group-containing layer of the SUS304 plate so that the thickness after drying was 50 μm. The resin composition was left in air (relative humidity 50%) at room temperature for 30 minutes to volatilize the solvent, and then left in a 150°C oven for 30 minutes to react, and then cooled to room temperature to form a resin coating layer, thereby obtaining a resin coating layer laminate E3.

[0186] <Manufacturing example C3> A comparative resin coating layer laminate C3 was produced in the same manner as in Production Example 3, except that the resin composition used in the resin coating layer forming step was only the composition (A).

[0187] <Production Example 4> (Surface treatment process) As the metal member, a copper plate was polished with #1000 sandpaper and then degreased with acetone.

[0188] (Functional group-containing layer formation process) 2 g of the silane coupling agent KBM-903 was dissolved in 1000 g of industrial ethanol. The resulting silane coupling agent solution was heated to 70°C, and the copper plate after polishing was immersed in the silane coupling agent solution for 20 minutes. The copper plate was then taken out and dried, forming a functional group-containing layer on the surface of the copper plate.

[0189] (Resin coating layer formation process) 100 g of an epoxy resin PG-100 having a fluorene skeleton, 84.3 g of a phenol compound BPEF having a fluorene skeleton, and 1.4 g of triethylamine were dissolved in 342 g of acetone to obtain a composition (B1-2).

[0190] The resin composition prepared by blending the composition (A) and the composition (B1-2) prepared in Production Example 1 in a mass ratio of 60 / 40 excluding acetone was spray-coated on the surface of the functional group-containing layer of the copper plate so that the thickness after drying was 50 μm. The resin composition was left in air (relative humidity 50%) at room temperature for 30 minutes to volatilize the solvent, and then left in a 150°C oven for 30 minutes to react, and then cooled to room temperature to form a resin coating layer, thereby obtaining a resin coating layer laminate E4.

[0191] [Manufacturing of metal-resin joints] The produced resin coating layer laminate or comparative resin coating layer laminate was bonded to various resin members by the methods shown in the following practical test examples and comparative test examples, thereby producing metal-resin joints in which the surface of the resin coating layer laminate on the resin coating layer side was bonded to a resin member.

[0192] The metal-resin joints were produced as test pieces conforming to ISO19095 (resin member width 10 mm × length 45 mm × thickness 3 mm, joint length between resin member and metal member 5 mm, width 10 mm) for use in the joint strength evaluation test described below.

[0193] <Test Example 1> The PEI resin component (width 10 mm × length 45 mm × thickness 3 mm) was produced by injection molding using an injection molding machine (Sumitomo Heavy Industries, Ltd. "SE100V", cylinder temperature 370°C, tool temperature 150°C, injection speed 14 mm / sec, peak / holding pressure 160 / 140 [MPa / MPa]).

[0194] The resin coating layer of the resin coating layer laminate E1 obtained in Production Example 1 was heated to 225°C, and the surface of the resin coating layer side of the resin coating layer laminate E1 and the resin member PEI were overlapped with each other so that the joints had an overlapping length of 5 mm and a width of 10 mm, and then pressed together by applying a pressure of 0.1 MPa to produce a metal-resin joint.

[0195] <Comparative Test Example 1> Using the comparative resin coating layer laminate C1 obtained in Production Example C1, the same operation as in Experimental Test Example 1 was carried out to produce a metal-resin bonded body.

[0196] <Test Example 2> The resin component PBT (width 10 mm x length 45 mm x thickness 3 mm) was produced by injection molding PBT using an injection molding machine (Sumitomo Heavy Industries, Ltd. "SE100V", cylinder temperature 245°C, tool temperature 80°C, injection speed 10 mm / sec, peak / holding pressure 100 / 80 [MPa / MPa]).

[0197] The resin coating layer of the resin coating layer laminate E2 obtained in Production Example 2 was heated to 225°C, and the surface of the resin coating layer side of the resin coating layer laminate E2 and the resin member PBT were overlapped with each other so that the joints had an overlapping length of 5 mm and a width of 10 mm, and then pressed together by applying a pressure of 0.1 MPa to produce a metal-resin joint.

[0198] <Comparative Test Example 2> Using the comparative resin coating layer laminate C2 obtained in Production Example C2, the same operation as in Experimental Test Example 2 was carried out to produce a metal-resin joint body.

[0199] <Test Example 3> The resin part PPS (width 10 mm × length 45 mm × thickness 3 mm) was produced by injection molding PPS using an injection molding machine (Sumitomo Heavy Industries, Ltd. "SE100V", cylinder temperature 310°C, tool temperature 150°C, injection speed 14 mm / sec, peak / holding pressure 160 / 140 [MPa / MPa]).

[0200] The resin coating layer of the resin coating layer laminate E3 obtained in Production Example 3 was heated to 290°C, and the surface of the resin coating layer side of the resin coating layer laminate E3 and the resin member PPS were overlapped so that the joints had an overlap length of 5 mm and a width of 10 mm, and then pressed together under a pressure of 0.1 MPa to produce a metal-resin joint.

[0201] <Comparative Test Example 3> Using the comparative resin coating layer laminate C3 produced in Production Example C3, the same operation as in Experimental Test Example 3 was carried out to produce a metal-resin joint body.

[0202] <Test Example 4> A resin member PEI was pressure-bonded to the surface of the resin coating layer side of the resin coating layer laminate E4 obtained in Production Example 4 in the same manner as in Experimental Test Example 1 to produce a metal-resin bonded body.

[0203] [Bonding strength evaluation] The test pieces of the metal-resin bonded bodies produced in the above-mentioned Working Test Examples and Comparative Test Examples were left to stand for one day at each temperature shown in Table 1 below within the range of 23 to 160°C, and then the tensile shear strength (bonding strength) was measured using a tensile testing machine (Shimadzu Corporation's universal testing machine autograph "AG-IS", load cell 10 kN, tensile speed 10 mm / min, measurement temperature 23°C, 50% RH) in accordance with a method conforming to ISO 19095-1 to 4.

[0204] The results of these measurements are shown in Table 1. In cases where the joint of the test piece peeled off during exposure to high temperatures exceeding 130°C, making measurement impossible, the column for tensile shear strength in Table 1 is marked with a "-".

[0205] [Table 1]

[0206] As is clear from Table 1, it was confirmed that the resin coating layer formed from the epoxy resin composition containing composition (A) and composition (B) maintained high tensile shear strength (bonding strength) even after the metal-resin bonded body was exposed to a high temperature exceeding 100°C, and thermal deterioration of the bonded portion between the metal member and the resin member was suppressed. In particular, in the practical test examples 1 and 4, it was confirmed that the tensile shear strength was high, at 15 MPa or more, even at 150°C.

[0207] These results demonstrate that the resin coating layer of the present disclosure can suppress thermal deterioration of the joint of a metal-resin joint body and improve heat resistance. [Industrial Applicability]

[0208] The present invention can be used in an engine ECU and a manufacturing method thereof. [Explanation of symbols]

[0209] 1 Resin coating layer laminate 2 Metallic parts 3 Resin coating layer 4 Functional group-containing layer 5 Resin parts 10 Engine ECU (metal-resin joint) 12 First Part 13 One side surface of the base 14 Second Part 15 Other surface of base 16 Base 17 Heat dissipation fin 18 protrusions 20 Connectors 22 Bottom 24 Side 26 Space 27 Joint surface 28 Thermal Conductive Sheet 30 Semiconductor elements 32 Circuit Board

Claims

1. A metal member, a resin member, and one or more resin coating layers laminated on at least one of the metal member and the resin member. An engine ECU comprising: the metal member is a first part, the resin member is a second part, the metal member and the resin member are joined via the resin coating layer, at least one of the resin coating layers is formed from a cured product of an epoxy resin composition containing a composition (A) including a difunctional epoxy resin and a dihydric phenol compound, and a composition (B); The composition (B) includes at least one combination selected from the following (B1) to (B3): (B1) A combination of an epoxy resin having a fluorene skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B2) A combination of an epoxy resin having a biphenyl skeleton and a phenol compound having one or more skeletons selected from a fluorene skeleton, an imidazolidinone skeleton, and an aminotriazine skeleton. (B3) Combination of an allylphenol compound and a bismaleimide compound

2. 2. The engine ECU according to claim 1, wherein a content of the composition (B) in the epoxy resin composition is 10 to 80 parts by mass with respect to 100 parts by mass of a total content of the composition (A) and the composition (B).

3. 3. The engine ECU according to claim 1, wherein a surface of the metal member has been subjected to at least one surface treatment selected from the group consisting of blast treatment, polishing treatment, etching treatment and chemical conversion treatment.

4. a functional group-containing layer is provided between the metal member and the resin coating layer and is laminated in contact with the metal member and the resin coating layer, The engine ECU according to any one of claims 1 to 3, wherein the functional group-containing layer has a structure derived from one or more functional groups selected from the following (C1) to (C7): (C1) One or more functional groups selected from an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group, and an isocyanato group, which are derived from a silane coupling agent (C2) A functional group formed by reacting an amino group derived from a silane coupling agent with an epoxy compound. (C3) A functional group produced by the reaction of a mercapto group derived from a silane coupling agent with one or more compounds selected from an epoxy compound, an isocyanate compound, an epoxy-modified (meth)acrylate compound, and an amino group-containing (meth)acrylate compound. (C4) A functional group formed by reacting a (meth)acryloyl group derived from a silane coupling agent with a thiol compound. (C5) A functional group produced by the reaction of an epoxy group derived from a silane coupling agent with one or more compounds selected from an amino compound, a thiol compound, and an amino group-containing (meth)acrylate compound. (C6) Isocyanato group derived from an isocyanate compound (C7) Mercapto group derived from a thiol compound

5. The resin coating layer is a plurality of layers, and further includes a resin coating layer formed from a cured product of a curable resin, 5. The engine ECU according to claim 1, wherein the curable resin is at least one selected from the group consisting of an allyl-modified maleimide resin, a urethane resin, an epoxy resin, a vinyl ester resin, and an unsaturated polyester resin.

6. 6. The engine ECU according to claim 1, wherein the metal member includes an aluminum material, and the aluminum material has a thermal conductivity of 150 W / (m·K) or more.

7. 7. The engine ECU according to claim 1, wherein the metal member includes an aluminum extrusion material, and the aluminum extrusion material has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more.

8. 7. The engine ECU according to claim 1, wherein the metal member includes an aluminum forging, and the aluminum forging has a thermal conductivity of 180 W / (m·K) or more and a tensile strength of 150 MPa or more.

9. A manufacturing method for an engine ECU according to any one of claims 1 to 8, comprising heating the resin coating layer and pressing the metal member and the resin member together so that the heated resin coating layer is interposed between the metal member and the resin member, thereby joining the metal member and the resin member.

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