JP6430863B2 - Zygote - Google Patents

Description

  The present invention relates to a joined body of a metal material and a resin, and a joining method.

  A joined body of a metal material and a resin is used in a wide range of industrial fields mainly in the electric and automobile fields. Examples of such a joined body of a metal material and a resin include a lead frame of a semiconductor package used for an electronic component and a power card used for an automobile. Power cards for automobile parts have a structure in which a metal heat sink or metal element is wrapped with a mold resin such as epoxy resin, and currently treated with an expensive primer to bond the metal material and the resin together. ing.

  As a joined body of a metal material and a resin, for example, Patent Document 1 discloses a resin composite molded product in which a metal part is inserted, and the metal part and the phenol resin are bonded with a silane coupling agent. A metal insert resin composite molded product characterized by the above is described.

  Patent Document 2 includes an intermediate layer and a silane coupling agent layer formed on the metal member at the interface between the metal member and the resin, and the silane coupling agent layer and the resin are in contact with each other. The intermediate layer is any one of the metal oxide layer, the chelating agent layer, the composite layer of the oxide layer and the chelating agent layer, and the mixed layer of the oxide chelating agent, and the intermediate layer is electrically coated. A bonded body of a metal member and a resin characterized by being insulative is described.

  Since the joined body of the metal material and the resin is sometimes used under severe conditions, it is necessary that the joined body has high joint strength. However, the joints of Patent Document 1 and Patent Document 2 have room for improvement in joint strength.

  In addition, a metal material having gold plating on the outermost surface may be used for a joined body with a resin. However, since the gold plating surface has no functional group and is stable, a metal material having a gold plating layer on the outermost surface and a resin are used. In order to join, it is necessary to introduce a functional group such as an amino group or a carboxy group on the gold plating surface. As a method for introducing a functional group into the gold plating surface, a method using an alkanethiol derivative having a thiol group that easily binds to gold is known (Patent Document 3).

  However, the method of introducing functional groups onto the gold plating surface using an alkanethiol derivative is expensive because the alkanethiol derivative used is expensive and the alkanethiol derivative needs to be assembled in a self-assembled manner on the gold plating surface. Takes time. Furthermore, the joint strength of the obtained joined body is insufficient.

  Moreover, it is known that a joined body of a metal material having a gold plating on the outermost surface and a resin can be obtained by using a silane coupling agent having a mercapto group. In the epoxy resin composition containing (A) an epoxy resin, (B) a phenol resin-based curing agent, (C) an inorganic filler, (D) a curing accelerator, and (E) a coupling agent, the curing accelerator (D) Includes a curing accelerator (d1) having a cation part that can promote the curing reaction of the epoxy resin and a silicate anion part that suppresses the catalytic activity of the cation part that promotes the curing reaction, and the coupling agent (E) Includes a silane coupling agent (e1) having a mercapto group, and an epoxy resin composition for encapsulating a semiconductor, and a semiconductor element is encapsulated using the composition Conductor device is described. In the example of Patent Document 4, a NiPd alloy frame plated with gold is used as a metal material. However, in the method of Patent Document 4, since the bond between the gold plating surface and the thiol group of the silane coupling agent is weak, there is room for improvement in the bonding strength of the obtained bonded body.

JP 2009-126126 A JP 2013-131595 A JP 2001-152363 A JP 2007-321012 A

  As described above, the metal material having a metal plating layer that does not have a functional group, such as a noble metal such as gold, on the outermost surface of the metal material, and the joined body of the resin increase the manufacturing cost, Since the reaction time becomes long, it is disadvantageous in terms of efficiency, and there is room for improvement in the bonding strength of the obtained bonded body. Therefore, the present invention efficiently provides a bonded body of a metal material having a noble metal plating layer having no functional group on the outermost surface of the metal material and a resin with high bonding strength and low cost. For the purpose.

  As a result of various studies on means for solving the above problems, the present inventors have provided a metal plating layer having a specific metal under the noble metal plating layer, and the metal of the metal plating layer is subjected to noble metal plating by heat treatment. It was found that the bonding strength of the bonded body of the metal material and the resin was increased by precipitation on the surface of the layer, and the present invention was completed.

That is, the gist of the present invention is as follows.
(1) A joined body of a metal base material, a metal material having a first plating layer formed on the metal base material, and a second plating layer formed on the first plating layer, and a resin. The first plating layer includes at least one metal selected from nickel, iron, copper, zinc, cobalt, and alloys thereof, and the second plating layer includes at least one metal selected from precious metals, A bonded body in which the metal of the layer is deposited on the surface of the second plating layer, and the metal material and the resin are bonded via the silane coupling agent layer formed on the second plating layer.
(2) The joined body according to (1), wherein the metal of the first plating layer deposited on the surface of the second plating layer is oxidized or hydroxylated.
(3) The joined body according to (1) or (2), wherein the metal contained in the second plating layer is gold.
(4) The joined body according to any one of (1) to (3), wherein the metal contained in the first plating layer is nickel or an alloy thereof.
(5) The joined body according to any one of (1) to (4), wherein the silane coupling agent has at least one functional group selected from an amino group, an epoxy group, a mercapto group, and a vinyl group.

  According to the present invention, it is possible to efficiently provide a bonded body of a metal material having a noble metal plating layer having no functional group on the outermost surface of the metal material and a resin with high bonding strength and at low cost. It becomes.

FIG. 1 is a cross-sectional view of the joined body of the present invention. FIG. 2A is a diagram showing the results of FE-AES analysis before heat treatment for nickel (Ni) atoms on the gold plating layer surface in Example 3. FIG. FIG. 2B is a diagram showing the results of FE-AES analysis after heat treatment for nickel (Ni) atoms on the surface of the gold plating layer in Example 3. FIG. 3A is a diagram showing the result of FE-AES analysis before heat treatment for gold (Au) atoms on the surface of the gold plating layer in Example 3. FIG. FIG. 3B is a diagram showing the results of FE-AES analysis after heat treatment for gold (Au) atoms on the surface of the gold plating layer in Example 3. 4A is a diagram showing the results of FE-AES analysis before heat treatment for phosphorus (P) atoms on the surface of the gold plating layer in Example 3. FIG. FIG. 4B is a diagram showing the results of FE-AES analysis after heat treatment for phosphorus (P) atoms on the surface of the gold plating layer in Example 3. FIG. 5A is a diagram showing a result of FE-AES analysis before heat treatment for oxygen (O) atoms on the surface of the gold plating layer in Example 3. FIG. FIG. 5B is a diagram showing the results of FE-AES analysis after heat treatment for oxygen (O) atoms on the surface of the gold plating layer in Example 3. FIG. 6 is a diagram showing the bonding strength of the bonded bodies of Examples 1-4 and Comparative Example 1.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The present invention relates to a joined body of a metal material and a resin.

  FIG. 1 is a schematic diagram illustrating the structure of the joined body of the present invention. As shown in FIG. 1, the joined body 1 of the present invention includes a metal base material 2, a first plating layer 3 formed on the metal base material 2, and a second plating formed on the first plating layer 3. The metal material 5 having the layer 4 and the resin 7 are joined together, and the metal material 5 and the resin 7 are joined via the silane coupling agent layer 6 formed on the second plating layer 4. . In the joined body of the present invention, the metal 8 of the first plating layer is deposited on the surface of the second plating layer 4.

I. Conjugate 1. Metal Material The metal material includes a metal base material, a first plating layer formed on the metal base material, and a second plating layer formed on the first plating layer.

  The metal of the metal base material is not particularly limited, and examples thereof include nickel, iron, copper, zinc, cobalt, tin, chromium, and alloys thereof, and copper is preferable from the viewpoint of high thermal diffusibility. The thickness of the metal base material is not particularly limited.

  The metal contained in the first plating layer is at least one metal selected from nickel, iron, copper, zinc, cobalt, and alloys thereof, and nickel and alloys thereof are preferable from the viewpoint of corrosion resistance. The thickness of the first plating layer is not particularly limited, and is usually 1 nm to 100 μm.

  The metal contained in the second plating layer is at least one metal selected from precious metals, such as gold, silver, platinum, palladium, rhodium, ruthenium and iridium. From the viewpoint of solderability, gold is more preferable. The thickness of the second plating layer is not particularly limited, and is usually 1 nm to 100 μm.

  In the metal material, the metal of the first plating layer is deposited on the surface of the second plating layer. In the present invention, the surface of the second plating layer usually means from the outermost surface of the second plating layer to a depth of several nanometers. The metal of the first plating layer deposited on the surface of the second plating layer is preferably oxidized or hydroxylated. That is, the surface of the second plating layer preferably has an oxygen atom or a hydroxyl group. When the metal of the first plating layer deposited on the surface of the second plating layer is oxidized or hydroxylated, the metal of the first plating layer deposited on the surface of the second plating layer and oxidized, and the second Since the silanol group of the silane coupling agent of the silane coupling agent layer formed on the plating layer is covalently bonded, the second plating layer and the resin are firmly bonded via the silane coupling agent layer, The joint strength of the resulting joined body is increased. The metal of the first plating layer deposited on the surface of the second plating layer and the metal that has been oxidized or hydroxylated can be obtained by a conventional surface analysis method such as field emission Auger Electron Spectroscopy (FE). -AES).

  In the metal material, the second plating layer only needs to have the metal of the first plating layer deposited on at least its surface. That is, the metal of the first plating layer may not be contained in the second plating layer. The ratio of the metal of the first plating layer deposited on the surface of the second plating layer is not particularly limited, and is, for example, 10% or more with respect to the surface area of the second plating layer. From the viewpoint of high bonding strength, it is preferably 50% or more.

  Preferably, the metal of the first plating layer can be deposited on the surface of the second plating layer by heat-treating the metal material. The heat treatment temperature is not particularly limited, and is, for example, 150 to 500 ° C., and preferably 200 to 400 ° C., more preferably 250 to 400 ° C. from the viewpoint of the bonding strength of the obtained bonded body. Especially preferably, it is 275-350 degreeC.

  The heat treatment time varies depending on the heat treatment temperature, but is, for example, 10 seconds to 24 hours, preferably 10 seconds to 3 hours from the viewpoint of productivity, and more preferably 5 minutes from the viewpoint of quality. ~ 3 hours. The heat treatment time is, for example, 5 minutes to 1 hour if the heat treatment temperature is 300 ° C., and 30 minutes to 3 hours if the heat treatment temperature is 200 ° C.

  In the present invention, it is preferable to use a metal material that is heat-treated at a temperature of 150 to 500 ° C., preferably 200 to 400 ° C., more preferably 250 to 400 ° C., and particularly preferably 275 to 350 ° C. When a metal material heat-treated at a temperature in the above range is used, the bonding strength of the obtained bonded body is increased.

2. Silane coupling agent layer The silane coupling agent layer is formed on the second plating layer of the metal material, and the metal material and the resin are bonded via the silane coupling agent layer. More specifically, in the silane coupling agent layer, the silanol group of the silane coupling agent is bonded to the metal of the first plating layer deposited on the surface of the second plating layer, and the terminal functional group of the silane coupling agent is a resin. The second plating layer and the resin are bonded together by bonding with the. In the present invention, the silane coupling agent layer and the resin are preferably present as separate layers, but may have a structure in which the silane coupling agent layer is contained in the resin.

  Although a silane coupling agent is not specifically limited, It is preferable that it is the alkoxysilane which has a functional group according to the kind of resin, and an alkoxy group. In the present invention, silanol groups generated by hydrolysis of alkoxy groups can be combined with the metal of the first plating layer deposited on the surface of the second plating layer. The functional group of the silane coupling agent is preferably an amino group, an epoxy group, a mercapto group, or a vinyl group. The thickness of the silane coupling agent layer is not particularly limited, and is usually several nm to several μm.

3. Resin The resin can be selected according to the functional group of the silane coupling agent, and is not particularly limited, and any of a thermoplastic resin and a thermosetting resin can be used. The thermoplastic resin includes polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, polyvinyl chloride resin, polycarbonate resin, nylon resin, urethane resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, acrylonitrile-butadiene. -Styrene copolymer (ABS) resin etc. are mentioned. Examples of the thermosetting resin include melamine resin, phenol resin, epoxy resin, urethane resin, polyimide resin, diallyl phthalate resin, unsaturated polyester resin, furan resin and the like. As resin used for the joined body of the present invention, polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, polyvinyl chloride resin, nylon resin, phenol resin and epoxy resin are preferable. The thickness of the resin layer is not particularly limited.
In the present invention, the combination of the functional group of the silane coupling agent and the resin is not particularly limited, and various combinations are possible.

II. The manufacturing method of a conjugate | zygote This invention also includes the manufacturing method of said conjugate | zygote.
The manufacturing method of the joined body of this invention includes heat-processing said metal material at the temperature of 150-500 degreeC. By the heat treatment of the metal material, the metal of the first plating layer is deposited on the surface of the second plating layer. The metal of the first plating layer deposited on the surface of the second plating layer is preferably oxidized or hydroxylated.

  The heat treatment temperature of the metal material is preferably 200 to 400 ° C, more preferably 250 to 400 ° C, and particularly preferably 275 to 350 ° C. When the metal material is heat-treated at a temperature in the above range, the joint strength of the obtained joined body is increased.

  The heat treatment time is as described above and varies depending on the heat treatment temperature, but is, for example, 10 seconds to 24 hours, from the viewpoint of productivity, preferably 10 seconds to 3 hours, and from the viewpoint of quality, More preferably, it is 5 minutes to 3 hours. The heat treatment time is, for example, 5 minutes to 1 hour if the heat treatment temperature is 300 ° C., and 30 minutes to 3 hours if the heat treatment temperature is 200 ° C.

  In addition to the above heat treatment of the metal material, the method for producing a joined body according to the present invention includes forming a silane coupling agent layer on the heat-treated metal material, and passing the metal material through the silane coupling agent layer. And bonding the resin.

  The silane coupling agent layer is formed, for example, by immersing the heat-treated metal material in a silane coupling agent solution and forming the silane coupling agent layer as a thin film on the second plating layer of the metal material.

  As a solvent for the silane coupling agent solution, water is preferable, but in order to increase the solubility of the silane coupling agent, a water-soluble organic solvent such as ethanol, methanol, and acetone may be used in combination with water. When using an organic solvent with water, the ratio of the organic solvent in a solvent is 1 to 70 weight%, for example, Preferably, it is 5 to 30 weight%. The concentration of the silane coupling agent solution is usually 0.1% by weight to 20% by weight.

  The immersion time of the metal material in the silane coupling agent solution is not particularly limited, and is usually 5 seconds to 16 hours, and preferably 1 minute from the viewpoint of reliable formation of the silane coupling agent layer and cost. ~ 1 hour. The thinning of the silane coupling agent layer is not particularly limited as long as it is a means capable of removing the liquid, and can be performed by an ordinary method, for example, a spin coater, a bar coater, or the like. The metal material formed with the silane coupling agent layer can be fixed to the metal material usually by heat treatment. The heat treatment conditions are not particularly limited, and are usually 80 to 140 ° C. and 5 minutes to 1 hour.

  The joining of the metal material and the resin is not particularly limited, and can be performed by an ordinary method such as an injection molding method, a transfer molding method, or a compression molding method. For example, in the injection molding method, a metal material is placed in an injection mold and a molten resin is injected into the injection mold to join the metal material and the resin. The molding conditions are not particularly limited, and preferable conditions can be appropriately set according to the physical properties of the resin used. Alternatively, the resin is manufactured in advance by a general molding method such as an injection molding method, the metal material and the resin are brought into contact with each other, heat is applied to the contact surface, and the vicinity of the resin contact surface is melted. You may join material and resin.

In the method for producing a joined body of the present invention, the formation of the silane coupling agent layer and the joining of the metal material and the resin may be performed simultaneously in order to shorten the production process. In this case, a silane coupling agent and a resin are mixed in advance and used. In the manufacturing method of the present invention, since the efficiency of bonding between the metal of the first plating layer deposited on the surface of the second plating layer and the silane coupling agent is increased, the formation of the silane coupling agent layer, the metal material, The bonding with the resin is preferably performed separately.
The present invention also includes a joined body manufactured by the above manufacturing method.

  In a preferred embodiment of the present invention, the joined body includes a metal base material, a metal material having a first plating layer formed on the metal base material, and a second plating layer formed on the first plating layer. , A joined body with a resin, wherein the first plating layer includes at least one metal selected from nickel, iron, copper, zinc, cobalt and alloys thereof, and the second plating layer is at least one selected from noble metals. The metal of the first plating layer is formed by heat treatment at 150 to 500 ° C. (preferably 200 to 400 ° C., more preferably 250 to 400 ° C., particularly preferably 275 to 350 ° C.). It is deposited on the surface of the second plating layer, and the metal material and the resin are joined via the silane coupling agent layer formed on the second plating layer.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the technical scope of the present invention is not limited to these examples.

(Example 1)
The aqueous solution was prepared using N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-603) as the silane coupling agent.

  As the metal material, a metal material having a copper base material, a nickel-phosphorous plating layer formed on the copper base material, and a gold plating layer formed on the nickel-phosphorous plating layer was used. The metal material was heat-treated at 200 ° C. for 1 hour in the air.

  The heat-treated metal material was immersed in an aqueous solution of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. Excess liquid was removed using a spin coater, and a thin film of a silane coupling agent was formed on the gold plating layer of the metal material. The metal material was heat-treated at 100 ° C. for 15 minutes to immobilize the silane coupling agent on the gold plating layer.

  An epoxy resin was transfer molded at 175 ° C. and 7 MPa and bonded to the obtained metal material having a silane coupling agent layer immobilized on a gold plating layer. After the obtained bonded body was post-cured at 180 ° C. for 2 hours, the bonding strength of the bonded body was measured with a compression tester. The joint strength of the joined body was determined as an average of three measurements. The joint strength of the obtained joined body was 16.0 MPa.

(Example 2)
A joined body was obtained in the same manner as in Example 1 except that the heat treatment temperature of the metal material was changed from 200 ° C to 250 ° C. The joint strength of the obtained joined body was 23.6 MPa.

Example 3
A joined body was obtained in the same manner as in Example 1 except that the heat treatment temperature of the metal material was changed from 200 ° C to 300 ° C. The joint strength of the obtained joined body was 28.0 MPa. In Example 3, the gold plating layer surface (570 μm × 570 μm) of the metal material before and after the heat treatment was examined for the following atoms by FE-AES analysis (manufactured by JEOL: JAMP-7830F). In the FE-AES analysis, analysis can be performed from the outermost surface of the gold plating layer to a depth of about several nm. FIG. 2 shows the surface analysis results of nickel (Ni) atoms before heat treatment (FIG. 2 (a)) and after heat treatment (FIG. 2 (b)). From FIG. 2 (a) and FIG. 2 (b), nickel atoms did not exist on the gold plating layer surface before heat treatment, but nickel appeared on the gold plating layer surface by heat treatment of the metal material. Was confirmed. FIG. 3 shows the surface analysis results of gold (Au) atoms before heat treatment (FIG. 3A) and after heat treatment (FIG. 3B). From FIG. 3 (a) and FIG. 3 (b), gold atoms existed on the surface of the gold plating layer before the heat treatment, but the gold atoms decreased from the surface of the gold plating layer by heat treatment of the metal material. Was confirmed. FIG. 4 shows the surface analysis results of phosphorus (P) atoms before the heat treatment (FIG. 4 (a)) and after the heat treatment (FIG. 4 (b)). 4 (a) and 4 (b), it was confirmed that phosphorus atoms were not present on the surface of the gold plating layer in both cases before and after the heat treatment of the metal material. FIG. 5 shows the surface analysis results of oxygen (O) atoms before the heat treatment (FIG. 5 (a)) and after the heat treatment (FIG. 5 (b)). From FIG. 5 (a) and FIG. 5 (b), oxygen atoms were not present on the surface of the gold plating layer before the heat treatment, but when the metal material was heat treated, oxygen atoms appeared on the surface of the gold plating layer. It was confirmed that nickel atoms on the surface of the gold plating layer were oxidized or hydroxylated.

(Example 4)
A joined body was obtained in the same manner as in Example 1 except that the heat treatment temperature of the metal material was changed from 200 ° C to 400 ° C. The joint strength of the obtained joined body was 24.0 MPa.

(Comparative example)
A joined body was obtained in the same manner as in Example 1 except that the metal material was not heat-treated. The joint strength of the obtained joined body was 4.5 MPa.

  FIG. 6 shows the bonding strengths of the bonded bodies of Examples 1-4 and Comparative Examples. FIG. 6 shows that the bonded body of Example 1-4 in which the metal material was heat-treated had higher bonding strength than the bonded body of the comparative example in which the metal material was not heat-treated. Among Examples 1-4, the joint strength of the joined body of Example 2-4 was higher.

  The joined body of the present invention can be used for electronic parts and automobile parts.

1: Bonded body 2: Metal base material 3: First plating layer 4: Second plating layer 5: Metal material 6: Silane coupling agent layer 7: Resin 8: Metal of first plating layer

Claims (5)

A bonded body of a metal base material, a metal material having a first plating layer formed on the metal base material, and a second plating layer formed on the first plating layer, and a resin, The plating layer includes at least one metal selected from nickel, iron, copper, zinc, cobalt and alloys thereof, the second plating layer includes at least one metal selected from noble metals, and the metal of the first plating layer Is deposited on the surface of the second plating layer, and the metal material and the resin are joined via the silane coupling agent layer (excluding the mercapto-based silane coupling agent) formed on the second plating layer. Body (excluding joined bodies having a polyester adhesive layer) . The joined body according to claim 1 , wherein the metal of the first plating layer deposited on the surface of the second plating layer is oxidized or hydroxylated. The joined body according to claim 1 or 2 , wherein the metal contained in the second plating layer is gold. The joined body according to any one of claims 1 to 3, wherein the metal contained in the first plating layer is nickel or an alloy thereof. Silane coupling agent, an amino group, having at least one functional group selected from epoxy Moto及 beauty vinyl group, the conjugate according to any one of claims 1 to 4.

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