JP2002192651A - Moldings with metal coating and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide moldings with a metal coating which are formed with the metal coating effectively adhering to the surface of resin moldings without impairing the characteristics of a resin as a constituent of the resin moldings. SOLUTION: The moldings with a metal coating are constituted of the resin moldings 1 and the metal film 2 applied to the surface of the former. An intermediate film 3 containing a resin showing higher adhesive properties to the metal film 2 than the adhesive properties between the resin of the resin moldings 1 and the metal film 2, is formed with a thickness of 5 μm or less between the resin moldings 1 and the metal film 2. In addition, the adhesive properties of the metal film 2 to the surface of the resin moldings 1 can be enhanced by the intermediate film 3 containing the resin showing higher adhesive properties to the metal film 2. The intermediate film 3 is set to be as thin as 5 μm or less, so that the characteristics of the resin moldings 1 are not impaired by the intermediate film 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-coated molded article used for a three-dimensional circuit board such as an MID and a method for producing the same.

[0002]

2. Description of the Related Art Three-dimensional circuit boards such as MIDs and sensor parts,
The reflection plate and the like are manufactured by producing a resin molded body by injection molding or the like of a resin composition, and forming a metal film serving as a circuit or a reflective film on the surface of the resin molded body. Liquid crystal polymer (LCP) and syndiotactic polystyrene (SPS) have excellent high-frequency characteristics and excellent heat resistance, and are therefore particularly suitable as a material for a resin molded body forming a three-dimensional circuit board, a sensor component, a reflector, and the like. . However, since the molecules of LCP and SPS do not have a polar group, even if a metal film is formed on the surface of a resin molded product made of LCP or SPS, the adhesion of the metal film to the resin molded product is extremely small.

[0003] In order to enhance the adhesion of the metal film to the resin molded body, plasma treatment is performed on the surface of the resin molded body. It is difficult to obtain a high effect of improving the adhesion. FIG. 16 shows polyphthalamide (PP
This shows the effect of improving the peel strength of the metal film by the nitrogen plasma treatment with respect to the non-treatment when A) and LCP were treated with nitrogen plasma, and the peel strength of PPA was greatly improved by the nitrogen plasma treatment. , LCP
Has a small improvement in peel strength by nitrogen plasma treatment,
The required peel strength of 0.6 N / mm has not been reached. This is because, as shown in Chemical Formula 1, PPA has many polar groups in the chemical structural formula, but LCP does not have a polar group in the chemical structural formula. It is considered that a polar group cannot be provided to the polymer.

[0004]

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On the other hand, for example, Japanese Patent Application Laid-Open No. 9-193293 discloses that a resin molded body is produced from a composite material of another resin and LCP, or a surface of the resin molded body is spray-coated with a primer paint. Attempts have been made to obtain adhesion of a metal film. However, the composite material obtained by mixing LCP with another resin may lose the properties of the LCP such as high-frequency characteristics and heat resistance by the other resin. The thickness is at least several tens of μm or more, and in this case also, the properties such as excellent high-frequency characteristics and heat resistance of the LCP may be damaged by the primer coating.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above points, and a metal film having high adhesion to the surface of a resin molded body without impairing the properties of the resin constituting the resin molded body. It is an object of the present invention to provide a metal-coated molded body that can be formed.

[0007]

A metal-coated molded product according to a first aspect of the present invention is a metal-coated molded product in which a metal film is coated on a surface of a resin molded product. An intermediate film containing a resin having higher adhesiveness to a metal film than adhesiveness to a film is placed at a distance of 5 μm between the resin molded body and the metal film.
It is characterized by being formed with the following thickness.

According to a second aspect of the present invention, in the first aspect, the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin.

A third aspect of the present invention is characterized in that, in the first or second aspect, the intermediate film is formed by a film in which a resin and a metal of a metal film are mixed.

According to a fourth aspect of the present invention, in the third aspect, the mixing ratio of the metal to the resin is gradually changed so as to be low in a portion near the resin molded body and high in a portion near the metal film. It is characterized by forming a film.

According to a fifth aspect of the present invention, in the first or second aspect, the intermediate film is formed of a film in which a resin and an inorganic material are mixed.

The invention of claim 6 is characterized in that, in claim 5, alumina is used as the inorganic substance.

According to a seventh aspect of the present invention, in the first or second aspect, the intermediate film is formed in a two-layer structure of a resin layer on the resin molded body side and a metal oxide layer on the metal film side. It is characterized by becoming.

According to an eighth aspect of the present invention, in the seventh aspect, the metal oxide layer is formed of a layer in which the metal of the metal film and the oxide of the metal film are mixed, and the mixing ratio of the metal oxide to the metal is resin. The metal oxide layer is formed by gradually changing the metal oxide layer so that the metal oxide layer is gradually increased so as to be higher near the layer and lower near the metal film.

According to a ninth aspect of the present invention, in the method for manufacturing a metal-coated molded article, a resin having higher adhesiveness to the metal film than adhesiveness between the resin of the resin molded article and the metal film is formed on the surface of the resin molded article. An intermediate film to be contained is formed with a thickness of 5 μm or less, and thereafter, a metal film is formed on the surface of the resin molded product from above the intermediate film.

A tenth aspect of the present invention is directed to the ninth aspect, wherein the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin.

The invention of claim 11 is the invention of claim 9 or 1
0, wherein an intermediate film is formed by gas-phase polymerization of the resin on the surface of the resin molded body.

The invention of claim 12 is the invention of claim 9 or 1
0, an intermediate film is formed by spraying a resin liquid on the surface of the resin molded body.

The thirteenth aspect of the present invention relates to the ninth to the first aspects.
2. The method according to any one of 2), wherein the surface of the resin molded body is roughened by plasma treatment, and then an intermediate film is formed on the surface of the resin molded body.

According to a fourteenth aspect of the present invention, in the thirteenth aspect, the plasma treatment for roughening the surface of the resin molded product is performed.
The method is characterized in that the plasma treatment is performed using oxygen or ozone as an atmospheric gas.

The invention of claim 15 is the invention of claims 9 to 1
4. The method according to any one of the items 4, wherein an intermediate film is formed on the surface of the resin molded article after performing a plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded article.

The invention of claim 16 is characterized in that, in claim 15, the plasma treatment for cleaving the bonding of the molecules of the resin on the surface of the resin molded body is performed by atmospheric pressure plasma.

The seventeenth aspect of the present invention relates to the ninth to the first aspects.
4. In any one of (4) and (4), after performing a plasma treatment for irradiating a laser to the surface of the resin molded body to cleave the bond of the molecules of the resin on the surface, forming an intermediate film on the surface of the resin molded body It is.

Further, the invention of claim 18 is the invention of claims 9 to 1
4. In any one of (4) and (4), an intermediate film is formed on the surface of the resin molded product after the surface of the resin molded product is subjected to plasma treatment by irradiating ultraviolet rays with an excimer lamp to cleave the bonding of the resin molecules on the surface. It is assumed that.

Further, the invention of claim 19 is the invention of claims 9 to 1
8. In any one of 8, the resin and the metal are mixed by forming a metal film on the intermediate film by physical vapor deposition of the metal while forming the intermediate film by vapor-phase polymerization of the resin on the surface of the resin molded body. Characterized in that a formed intermediate film is formed.

According to a twentieth aspect of the present invention, in the nineteenth aspect, a metal film is deposited on the intermediate film by physical vapor deposition of a metal while forming an intermediate film by gas phase polymerization of the resin on the surface of the resin molded product. By forming, in forming the intermediate film in which the resin and the metal are mixed, by increasing the physical vapor deposition of the metal while reducing the ratio of the gas phase polymerization of the resin, the mixing ratio of the metal to the resin is close to that of the resin molded body. Low in part,
The method is characterized in that an intermediate film that changes gradually is formed so as to increase in a portion near the metal film.

The invention of claim 21 is the invention of claims 9 to 1
8. The method according to any one of 8, wherein an intermediate is formed by vapor-phase polymerization of the resin on the surface of the resin molded body to form an intermediate film, and physical deposition of the inorganic material is performed to form an intermediate film in which the resin and the inorganic material are mixed. Things.

According to a twenty-second aspect of the present invention, the resin and the alumina are physically vapor-deposited as an inorganic substance while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded product. It is characterized in that a mixed intermediate film is formed.

Further, the invention of claim 23 is the invention of claims 9 to 2
2. In any one of (2), by forming a resin layer on the surface of the resin molded body and forming a metal oxide layer on the surface of the resin layer, an intermediate film having a two-layer structure of the resin layer and the metal oxide layer is formed. It is characterized by the following.

According to a twenty-fourth aspect of the present invention, in the twenty-third aspect, a metal oxide is formed by forming a resin layer on the surface of a resin molded body and depositing the metal on the resin layer while oxidizing the metal by reactive sputtering. By forming a layer,
Forming a metal film on the surface of the metal oxide layer of the intermediate film by forming a two-layered intermediate film of a resin layer and a metal oxide layer, and subsequently sputtering without oxidizing the metal; According to a twenty-fifth aspect of the present invention, in the twenty-fourth aspect, a metal oxide is formed by forming a resin layer on the surface of a resin molded body and depositing the metal on the resin layer while oxidizing the metal by reactive sputtering. In forming a two-layer intermediate film consisting of a resin layer and a metal oxide layer by forming a layer, the metal and its oxide are mixed by performing reactive sputtering while adjusting the oxidation reaction amount of the metal. And forming the metal oxide layer so that the mixture ratio of the metal oxide to the metal gradually changes so as to be high in the portion close to the resin layer and low in the portion far from the resin layer. It is an butterfly.

The invention of claim 26 is the invention of claims 9 to 2
In any one of 5, the intermediate film is formed on the surface of the resin molded body, and then the surface of the intermediate film is roughened by plasma treatment, and then the metal film is formed on the surface of the resin molded body from above the intermediate film. It is characterized by the following.

The invention of claim 27 is the invention of claims 9 and 2.
6. In any one of the above, after forming an intermediate film on the surface of the resin molded product and then performing a treatment of cleaving the bond of the resin molecules on the surface of the intermediate film, a metal film is formed on the surface of the resin molded product from above the intermediate film. Is formed.

The invention of claim 28 is the invention of claims 9 to 2
7. The method according to any one of items 7, wherein when forming a metal film by physically depositing a metal on the surface of the resin molded body from above the intermediate film, an ion beam of rare gas element ions is irradiated.

Further, the invention of claim 29 is the invention of claims 9 to 2
7. In any one of the above, in forming a metal film by physically depositing a metal on the surface of the resin molded body from above the intermediate film, irradiating an ion beam of a rare gas element ion after irradiating an ion beam of an oxygen ion It is characterized by doing.

[0035]

Embodiments of the present invention will be described below.

In the present invention, the resin molded body 1 is L
A resin composition mainly composed of CP or SPS can be used. An intermediate film 3 is formed on the surface of the resin molded body 1 as shown in FIG. By forming the metal film 2 on the surface of the resin molding 1 from above, a metal-coated molding as shown in FIG. 1B can be obtained.

The metal film 2 is formed by physical vapor deposition (PVD) such as sputtering, vacuum vapor deposition, or ion plating.
Method). FIG. 2 shows an apparatus for forming a metal film 2 by sputtering, in which a holder electrode 12 and a target metal 13 such as copper are arranged in a chamber 11, and the holder electrode 12 and the target metal 1 are placed.
3, a DC power supply 14 is connected. Then, the resin molded body 1 having the intermediate film 3 formed on the surface is placed on the holder electrode 1.
2, the inside of the chamber 11 is evacuated to a level of 10 ⁻⁴ Pa by a vacuum pump, and DC gas is passed through the target metal 13 while passing a rare gas such as argon gas through the chamber 11 at a gas pressure of about 0.5 Pa. By applying a DC voltage having a power of about 3 kW, the metal film 2 can be formed on the surface of the resin molding 1 from above the intermediate film 3 by the action of the plasma P generated. The thickness of the metal film 2 can be formed to about 0.5 μm, and when the obtained metal-coated molded body is used as a three-dimensional circuit board such as a MID, the metal film 2 is etched to form a desired pattern.
A circuit is formed by thickening a metal by electrolytic plating or the like.

The intermediate film 3 is formed of a resin having a higher adhesion to the metal film 2 than the adhesion between the resin of the resin molded body 1 and the metal film 2. It is desirable to have. When there are many polar groups, the adhesion of the metal film 2 can be increased by the reaction between the polar groups and the metal, and the polar groups are activated by plasma-treating the surface of the intermediate film 3 so that the metal film 2 can be activated. Can be obtained with higher adhesion.

As described above, by forming the metal film 2 on the surface of the resin molded body 1 from above the intermediate film 3 made of a resin having high adhesion to the metal film 2, the metal film 2 adheres to the surface of the resin molded body 1. High adhesion can be obtained by the intermediate film 3. The intermediate film 3 is formed with a thickness of 5 μm or less, more preferably 1 μm or less. If the thickness of the intermediate film 3 is large, the excellent properties of the resin molded article 1 formed by LCP or SPS will be impaired by the intermediate film 3, but by setting the thickness of the intermediate film 3 to 5 μm or less, This prevents the intermediate film 3 from impairing the properties of the resin molded body 1. Intermediate film 3
The lower limit of the film thickness is not particularly set, but in order to secure the effect of improving the adhesion of the metal film 2, the intermediate film 3 preferably has a thickness of 0.01 μm or more.

Here, the intermediate film 3 is formed of an active metal such as Ti, Cr, Ni or the like, and the adhesion of the metal film 2 formed of Cu or the like to the resin molded body 1 is enhanced by the active metal intermediate film 3. Has been performed conventionally. However, when the metal film 2 is etched to form a pattern such as a conductive circuit, if the intermediate film 3 below the metal film 2 is formed of metal, the intermediate film 3 also needs to be etched. However, there are problems such as an increase in the thickness and an increase in the etching thickness, which makes it difficult to form a fine circuit. However, in the case of the present invention in which the intermediate film 3 is formed of a resin, there is no such problem.

In the present invention, a polyimide resin or an epoxy resin can be used as the resin for forming the intermediate film 3 as described above. Since the polyimide resin or the epoxy resin has a polar group (functional group) and therefore has a high adhesiveness to a metal and a high heat resistance, it is also preferable to increase the heat resistance of the resin molded body 1.

In forming the intermediate film 3 on the surface of the resin molded product 1, the thickness of the intermediate film 3 is set to 5 μm as described above.
It is necessary to form the following very thin. For example, such a wet construction method in which the resin molded body 1 is immersed in the resin liquid, or the surface of the resin molded body 1 is spin-coated with the resin liquid to form the intermediate film 3 on the surface of the resin molded body 1. It is difficult to form the intermediate film 3 with a small thickness.
If the surface has a three-dimensional three-dimensional shape, it is difficult to form the intermediate film 3 with a uniform film thickness due to liquid pooling and liquid flow in such a wet method. Therefore, in the present invention, the intermediate film 3 is formed by gas-phase polymerization of the resin on the surface of the resin molded body 1.
It is possible to form the intermediate film 3 with a thin thickness of 5 μm or less on the surface of the resin molded body 1. Even if the surface of the resin molded body 1 has a three-dimensional three-dimensional shape, there is no problem such as a liquid pool or a liquid flow.
This makes it possible to form the intermediate film 3 with a uniform film thickness. As the gas phase polymerization method, a vapor deposition polymerization method, a plasma polymerization method, or the like can be employed.

FIG. 3 shows an example of an apparatus for forming an intermediate film 3 on the surface of the resin molded body 1 by vapor-depositing and polymerizing a polyimide resin. That is, a vacuum pump 18 such as a rotary pump is connected to a chamber 17 in which the holder 16 is provided, and the chamber 17 further contains pyromellitic anhydride (PMDA) and oxydianiline (O
Monomer tanks 19 and 20 for supplying DA) are connected. Then, the resin molded body 1 is set on the holder 16 and the inside of the chamber 17 is evacuated to about 10 Pa and heated to about 200 ° C. In this state, PMDA and ODA are vaporized from the monomer tanks 19 and 20 into the chamber 17 respectively. To form a film while reacting PMDA and ODA on the surface of the resin molded body 1, and then forming the film at 300 ° C.
The intermediate film 3 made of the polyimide resin can be formed on the surface of the resin molded body 1 by the reaction shown in Chemical Formula 2 by curing while maintaining the heating at about the temperature for about 60 minutes.

[0044]

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FIG. 4 shows an example of an apparatus for forming an intermediate film 3 on the surface of a resin molded body 1 by plasma-polymerizing a polyimide resin. That is, the holder electrode 2 is placed in the chamber 22.
3 and a counter electrode 24 are arranged, and a high frequency power supply 27 is connected to the holder electrode 23 and the counter electrode 24 via a matching box 25 and a blocking capacitor 26. The chamber 22 is further connected to monomer tanks 19 and 20 for supplying pyromellitic anhydride (PMDA) and oxydianiline (ODA) as raw material monomers. Then, the resin molded body 1 is set and held by the holder electrode 23, and the inside of the chamber 22 is evacuated to a level of 10 ⁻⁴ Pa by a vacuum pump, and then a rare gas such as argon gas is passed through the chamber 22 at a gas pressure of about 10 Pa. Between the holder electrode 23 and the counter electrode 24
Plasma P is generated by applying a high-frequency voltage of 300 W power, and P is generated from monomer tanks 19 and 20.
MDA and ODA are heated and evaporated, respectively, and introduced into the chamber 22. In this way, the vapors of PMDA and ODA are activated by the plasma P, and PMDA and ODA are deposited while reacting on the surface of the resin molded body 1, thereby forming an intermediate film 3 of polyimide resin on the surface of the resin molded body 1. Is what you can do. In order to prevent ions in the plasma P from colliding with the resin being deposited on the surface of the resin molded body 1, a holder electrode 2 holding the resin molded body 1 is used.
3 is preferably connected to the ground side.

In forming the resin intermediate film 3 on the surface of the resin molded body 1, it is possible to form the resin intermediate film 3 by a spray method in addition to the above-described gas phase polymerization method. . In the spray method, the resin is dissolved or dispersed in a solvent or the like, and the resin liquid is sprayed on the surface of the resin molded body 1 to form a film. The resin intermediate film 3 is formed on the surface. By adopting this method, even if the surface of the resin molded body 1 has a three-dimensional three-dimensional shape,
The intermediate film 3 can be formed with a uniform film thickness without problems such as a liquid pool and a liquid flow. Further, this spray method can be carried out with a simpler apparatus than a vapor phase polymerization method such as vapor deposition polymerization or plasma polymerization as described above.

Prior to forming the resin intermediate film 3 on the surface of the resin molded body 1 as described above, the surface of the resin molded body 1 is previously subjected to plasma treatment to roughen the surface of the resin molded body 1. You may keep it. By forming the intermediate film 3 after the surface of the resin molded body 1 is roughened by plasma treatment as described above, the adhesion of the intermediate film 3 to the resin molded body 1 is enhanced by the anchor effect due to the rough surface, and the intermediate film 3 is formed. 3, the adhesion between the resin molded body 1 and the metal film 2 can be further improved.

FIG. 5 shows an example of a plasma processing apparatus in which a holder electrode 30 is arranged in a chamber 29 and a high frequency power supply 27 is connected to the holder electrode 30 via a matching box 25 and a blocking capacitor 26. , Chamber 29 is grounded. In this apparatus, the resin molded body 1 is set on the holder electrode 30, and the inside of the chamber 29 is evacuated to a pressure of about 10 ⁻⁴ Pa by a vacuum pump. A plasma P is generated by applying a high-frequency voltage of 1 kW RF power to 30. As the atmosphere gas, a nitrogen gas or the like can be used. Then, a negative voltage is applied to the resin molded body 1 by applying a high frequency voltage to the holder electrode 30, and nitrogen ions in the plasma P using nitrogen gas as an atmospheric gas collide with the resin molded body 1, and the resin molding 1 Etching is performed in which carbon and hydrogen, which are elements constituting the resin of the resin body 1, react with nitrogen ions and are separated from the surface of the resin body 1, thereby forming fine irregularities on the surface of the resin body 1 and forming a rough surface. Some nitrogen functional groups can be simultaneously formed on the surface of the resin molded body 1 at this time.

When the surface of the resin molded article 1 is roughened by plasma treatment, the above-mentioned nitrogen gas can be used as an atmosphere gas for generating plasma, but oxygen or ozone is used as this atmosphere gas. By doing so, a large etching effect can be obtained, and the resin molding 1
The surface can be efficiently roughened. That is, oxygen and ozone are easily linked to the carbon element in the resin of the resin molded body 1, are separated from the surface of the resin molded body 1 as carbon monoxide and carbon dioxide, and the etching easily occurs. Ozone generation by atmospheric pressure plasma may be used.

Prior to forming the resin intermediate film 3 on the surface of the resin molded body 1 as described above, a plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded body 1 may be performed. Good. As described above, the surface of the resin molded body 1 is subjected to the plasma treatment to cleave the bonds of the molecules of the resin, so that the bonding between the resin on the surface of the resin molded body 1 and the resin of the intermediate film 3 is improved. The adhesiveness of the intermediate film 3 to the metal film 2 can be further improved through the intermediate film 3. In the case where the surface of the resin molded body 1 is roughened by plasma treatment as described above, it is preferable to perform this treatment for breaking molecular bonds after the roughening treatment.

[0051] This plasma treatment can be performed using the same device as FIG. 5, as an atmosphere gas for generating plasma, it is preferable to use an inert gas such as argon, ion resins such as Ar ⁺ It acts on the surface of the molded article 1 and can cleave molecular bonds of the resin on the surface. The time of the plasma treatment for cleaving the molecular bond of the resin on the surface of the resin molded body 1 is preferably about 20 to 50 seconds.

The plasma treatment for cleaving the molecular bonds of the resin on the surface of the resin molded body 1 may be performed under reduced pressure or may be performed using atmospheric pressure plasma. Since atmospheric pressure plasma can be performed at atmospheric pressure, there is no need to provide a vacuum pump or a vacuum chamber, and processing can be performed with a simple apparatus.

The treatment for cleaving the molecular bonds of the resin on the surface of the resin molding 1 can also be performed by irradiating the surface of the resin molding 1 with a laser. That is, a laser such as an excimer laser, an argon laser, or a He-Cd laser output from a laser oscillator is applied to the surface of the resin molded body 1 to cleave the bonds of the resin molecules on the surface of the resin molded body 1. Is what you can do. In the case of the treatment with a laser, treatment in the atmosphere is possible, so that the treatment for breaking molecular bonds is facilitated.

The treatment for cleaving the molecular bonds of the resin on the surface of the resin molded product 1 can also be performed by irradiating the surface of the resin molded product 1 with ultraviolet rays using an excimer lamp. Excimer lamps use a dielectric barrier discharge to form a rare gas or rare gas halide excimer and extract spontaneous emission light from the excimer, and emit light having a wavelength in the ultraviolet region. it can. Since the excimer lamp can be made simpler, smaller, and cheaper than a device that irradiates a laser, the process of breaking molecular bonds can be performed at low cost.

As the intermediate film 3 provided on the surface of the resin molded body 1, in addition to being formed of only the resin as in each of the above embodiments, as shown in FIG. 6, a resin 3a and a metal 3b are mixed. It is also possible to form the intermediate film 3 with a thin film. As the resin 3a, the above-described polyimide resin or epoxy resin can be used, and as the metal 3b, the metal constituting the metal film 2 provided on the intermediate film 3 can be used. The intermediate film 3 can be formed by dispersing particles of the metal 3b in a matrix of the resin 3a.

As described above, by mixing the metal 3b constituting the metal film 2 with the intermediate film 3, the metal 3b in the intermediate film 3 and the metal film 2 are integrated, so that the adhesion of the metal film 2 to the intermediate film 3 is achieved. Thus, the adhesiveness of the metal film 2 to the resin molded body 1 via the intermediate film 3 can be further improved.

When the intermediate film 3 is formed of a film in which the resin 3a and the metal 3b are mixed as described above, the mixing ratio of the metal 3b to the resin 3a is close to that of the resin molding 1 as shown in FIG. The distribution density of the particles of the metal 3b is gradually changed so that the distribution density of the metal 3b gradually increases from the resin molded body 1 side toward the metal film 2 side. Is also good. In this way, since the ratio of the resin is large in the portion where the intermediate film 3 comes into contact with the resin molded body 1, high adhesion between the intermediate film 3 and the resin molded body 1 can be secured, and at the same time, the intermediate film Since the ratio of the metal 3b is large in the portion where the metal film 3 contacts the metal film 2, the adhesion between the intermediate film 3 and the metal film 2 can be further improved. In this case, since the density of the metal 3b is high in the vicinity of the interface of the intermediate film 3 with the metal film 2, the electrical insulation is low, and it is not suitable for applications in which a circuit is formed using the metal film 2.

Here, metal 3b is added to resin 3a as shown in FIG.
A method for forming the intermediate film 3 in which is mixed will be described.
That is, as described above, while forming the intermediate film 3 on the surface of the resin molded body 1 by vapor phase polymerization such as vapor deposition polymerization or plasma polymerization, at the same time, metal deposition is performed by physical vapor deposition (PVD) such as vacuum vapor deposition or sputtering. When the process for forming the film 2 is performed,
The gas-phase polymerized resin 3a and the metal 3b physically deposited are mixed and deposited on the surface of the resin molded body 1 while being mixed.
The intermediate film 3 in which the metal 3b is mixed in a can be formed. Subsequently, the metal film 2 can be formed on the intermediate film 3 by stopping the gas phase polymerization of the resin 3a and continuing the physical vapor deposition of the metal 3b.

Further, while the resin 3a is vapor-phase polymerized on the surface of the resin molded body 1 and the metal 3b is simultaneously deposited by the physical vapor deposition method, the intermediate film 3 in which the resin 3a is mixed with the metal 3b is formed. In forming, the ratio between the vapor phase polymerization of the resin 3a and the vapor deposition of the metal 3b is changed so that the ratio of the vapor phase polymerization of the resin 3a is first increased, and then the ratio of the vapor deposition of the metal 3b is gradually increased. 7, the intermediate film 3 that changes gradually so that the mixing ratio of the metal 3b to the resin 3a is low in the portion near the resin molded body 1 and high in the portion near the metal film 2 Can be done.

FIG. 8 shows that the metal 3 is deposited while polymerizing the resin 3a.
3 shows an apparatus for vacuum-depositing b. Crucible 3 containing vapor deposition metal such as copper in chamber 32
3, and a holder 16 for holding the resin molded body 1 is disposed above the reference numeral 3. The chamber 32 further contains a raw material monomer, pyromellitic anhydride (PMD).
A) and monomer tanks 19 and 20 for supplying oxydianiline (ODA) and the like are connected. Then, the resin molded body 1 is set in the holder 16 and the inside of the chamber 32 is
While evacuating to about 0 Pa and heating to about 200 ° C., the PMDA
And ODA are vaporized and introduced into the chamber 32, respectively, to start vapor deposition polymerization, and at the same time, heat the crucible 33 to evaporate a metal such as copper to start vacuum vapor deposition. As described above, by performing the vapor deposition polymerization of the resin 3a and the vacuum deposition of the metal 3b simultaneously in the same chamber 32, the intermediate film 3 in which the metal 3b is mixed with the resin 3a as shown in FIG. Is what you can do. After the formation of the intermediate film 3, the raw material monomer PM
By stopping the introduction of DA and ODA into the chamber 32, the metal film 2 can be formed on the intermediate film 3. Of course, in addition to such a combination of vapor deposition polymerization and vacuum deposition, a combination of plasma polymerization and sputtering may be used.

At this time, the introduction amounts of the raw material monomers PMDA and ODA into the chamber 32 are initially increased and gradually decreased, or the heating temperature of the crucible 33 is initially lowered and gradually increased. In such a manner as shown in FIG. 7, the mixing ratio of the metal 3b to the resin 3a gradually changes so as to be low in the portion near the resin molded body 1 and to be high in the portion near the metal film 2. The film 3 can be formed, and also in this case, after the intermediate film 3 is formed, PMD which is a raw material monomer is formed.
By stopping the introduction of A and ODA into the chamber 32, the metal film 2 can be formed on the intermediate film 3.

As shown in FIG. 9, the intermediate film 3 provided on the surface of the resin molded body 1 includes a resin 3a and an inorganic material 3c.
Can be formed as a film in which is mixed. This resin 3
As a, the above-mentioned polyimide resin or epoxy resin can be used, and as the inorganic substance 3c, a metal oxide, carbide, nitride, or the like can be used, and the inorganic substance 3c is contained in the matrix of the resin 3a. The intermediate film 3 can be formed by dispersing the above particles. The inorganic material 3c is a metal film 2 provided on the intermediate film 3.
It is desirable that the metal is oxide, carbide, or nitride.

The adhesion between the inorganic substance 3c such as a metal oxide and the metal is higher than the adhesion between the resin and the metal.
Accordingly, the inorganic film 3 such as a metal oxide is
By mixing c, the adhesion of the metal film 2 to the intermediate film 3 can be increased, and the adhesion of the metal film 2 to the resin molded body 1 via the intermediate film 3 can be further enhanced. is there. Further, since the inorganic substance 3c has better compatibility with the resin than the metal, it is possible to form the intermediate film 3 having higher strength than the intermediate film 3 in which the resin 3a and the metal 3b are mixed. In addition, the inorganic substance 3c is electrically insulating, so that the electric insulation of the intermediate film 3 does not decrease, and the inorganic substance 3c can be used without any trouble in forming a circuit with the metal film 2 for use.

Alumina can be used as the inorganic substance 3c. Alumina has a very high wettability with copper, and when the metal film 2 is formed of copper, the intermediate film 3 and the metal film 2
And particularly high adhesion to the film. Moreover, since alumina has an excellent property that the dielectric loss is very small, the metal-coated molded article can be used as a circuit board having excellent properties.

In forming the intermediate film 3 in which the inorganic material 3c such as alumina is mixed in the resin 3a as shown in FIG.
As described above, while forming the intermediate film 3 on the surface of the resin molded body 1 by vapor phase polymerization such as vapor deposition polymerization or plasma polymerization, at the same time, a physical vapor deposition method (PV
D), and can be carried out by performing a process of depositing the inorganic substance 3c by the method of the present invention.
a and the inorganic substance 3c to be physically vapor-deposited are deposited on the surface of the resin molded body 1 while being mixed, so that the intermediate film 3 in which the inorganic substance 3c is mixed in the resin 3a can be formed. The apparatus shown in FIG. 8 can be used as the apparatus, and the crucible 33 is provided with an inorganic substance such as alumina.
c, vapor deposition polymerization and vacuum deposition are performed in the same chamber 32.
May be performed at the same time. Since the inorganic substance 3c has a high melting point, it is better to perform sputtering such as RF sputtering than vacuum evaporation.

Further, as shown in FIG. 10, the intermediate film 3 provided on the surface of the resin molded body 1 can be formed of a two-layer film composed of a resin layer 4 and a metal oxide layer 5. The resin layer 4 is formed on the resin molded body 1 side, and the metal oxide layer 5 is formed on the metal layer 2 side.
The resin layer 4 can be formed of the above-described polyimide resin, epoxy resin, or the like. The metal oxide layer 5 is not particularly limited, but can be formed of an oxide of a metal constituting the metal film 2. When the metal film 2 is formed of copper, copper oxide, When the metal film 2 is formed of aluminum, alumina can be used.

The adhesiveness between the metal oxide and the metal and the adhesiveness between the metal oxide and the resin are higher than the adhesiveness between the resin and the metal. The resin molded body 1 and the resin layer 4 are formed by forming a two-layer structure of the resin layer 4 on the side and the metal oxide layer 5 on the side of the metal film 2.
The metal film 2 and the metal oxide layer 5
, And the metal oxide layer 5 and the resin layer 4 can have high adhesion. As a result, the adhesion of the metal film 2 to the resin molded body 1 via the intermediate film 3 can be further improved. Is what you can do. In addition, since the metal oxide is electrically insulating, the electrical insulation of the intermediate film 3 does not decrease, and the metal oxide can be used without any trouble in forming a circuit using the metal film 2. .

In producing the intermediate film 3 having the two-layer structure of the resin layer 4 and the metal oxide layer 5 as described above, first, as shown in FIG. A resin layer 4 is formed by a gas phase polymerization method or the like, and then a metal oxide layer 5 is formed on the resin layer 4 by physical vapor deposition (PVD) as shown in FIG.
In this case, the intermediate film 3 having a two-layer structure including the resin layer 4 and the metal oxide layer 5 can be formed. After the surface of the metal oxide layer 5 of the intermediate film 3 is subjected to plasma treatment or the like as necessary, the metal film 2 is formed thereon by a physical vapor deposition method or the like.
A metal-coated molded article as shown in FIG. 1 (c) can be obtained.

FIG. 12 shows an apparatus for forming the metal oxide layer 5 by sputtering. A holder electrode 36 and a target oxide 37 such as copper oxide or alumina are arranged in a chamber 35, and the holder electrode 36 and the target A high frequency power supply 27 is connected between the oxide 37 via a matching box 25 and a blocking capacitor 26. Then, the resin molded body 1 having the resin layer 4 formed on the surface is set by holding it on the holder electrode 36, and the inside of the chamber 35 is evacuated to a pressure of 10 ⁻⁴ Pa by a vacuum pump. Through the target oxide 3 at a gas pressure of about 0.5 Pa.
7, a plasma P is generated by applying a high frequency voltage of about 1 kW of RF power to cause the metal oxide layer 5 to adhere to the surface of the resin layer 4, and the resin layer 4 and the metal oxide layer 5
Thus, the intermediate film 3 having a two-layer structure can be formed.

In producing the intermediate film 3 having a two-layer structure of the resin layer 4 and the metal oxide layer 5, the metal oxide layer 5
Can be formed by reactive sputtering. Reactive sputtering is to sputter a metal using a reactive gas as an atmosphere gas for generating a plasma P. For example, when oxygen is used as a reactive gas, the metal is deposited as a metal oxide while reacting the metal with oxygen. Is what you can do.

FIG. 13 shows an apparatus for reactive sputtering, in which a holder electrode 12 and a target metal 13 such as copper are arranged in a chamber 11, and a holder electrode 1 is provided.
A DC power supply 14 is connected to the target 2 and the target metal 13. Then, the resin molded body 1 having the resin layer 4 formed on the surface thereof is set and held by the holder electrode 12, and the inside of the chamber 11 is evacuated to a pressure of 10 ⁻⁴ Pa by a vacuum pump. A gas is introduced into the chamber 11 at, for example, a gas flow ratio of 1: 2, and while passing at a gas pressure of about 0.5 Pa, D
The plasma P is generated by applying a DC voltage of about 3 kW of C power. The metal struck out of the target metal 13 by the action of the plasma P is oxidized by the oxygen plasma and deposited as a metal oxide on the resin layer 4 to form the metal oxide layer 5. Thus, the intermediate film 3 having a two-layer structure of the resin layer 4 and the metal oxide layer 5 can be formed. After the intermediate film 3 is formed, the introduction of oxygen gas is stopped, and The metal film 2 can be formed on the metal oxide layer 5 by continuing the sputtering while continuously introducing an inert gas such as the above. In this way, the formation of the metal oxide layer 5 and the formation of the metal film 2 can be performed in the same sputtering step only by changing the atmosphere gas, and the number of steps can be reduced.

Here, as described above, the plasma P is generated using the mixed gas of the inert gas and the oxygen gas as the atmospheric gas, and the reactive gas is used to form the metal oxide layer 5 by the reactive sputtering. By adjusting the mixing ratio with the gas, the metal oxide layer 5 in which the metal 5a and the metal oxide 5b are mixed can be formed. At this time, the mixing ratio of the inert gas and the oxygen gas is initially set to a high ratio of the oxygen gas, and the reactive sputtering is performed while gradually decreasing the oxygen ratio and increasing the inert gas ratio. As a result, as shown in FIG. 14, the mixing ratio of the metal 5a in the metal oxide 5b is changed so that the mixing ratio is low near the resin layer 4 and gradually increases as the distance from the resin layer 4 increases. The oxide layer 5 can be formed. Thereafter, by stopping the introduction of the oxygen gas and continuing the sputtering while introducing only the inert gas, the metal film 2 can be formed on the metal oxide layer 5. Since the oxide layer 5 has a high ratio of the metal oxide 5b at the interface portion of the resin layer 4, the adhesion between the resin layer 4 and the metal oxide layer 5 can be ensured, and the oxide layer 5 Since the ratio of the metal 5a is high at the interface, the adhesion between the metal film 2 and the metal oxide layer 5 can be ensured, and the metal film 2 adheres to the resin molding 1 via the intermediate film 3. Can be obtained with even higher adhesion.

After forming the intermediate film 3 on the surface of the resin molded body 1 as in each of the above-described embodiments, when forming the metal film 2 on the intermediate film 3, prior to the formation of the metal film 2, The surface of the intermediate film 3 can be roughened by performing a plasma treatment on the surface of the intermediate film 3. The plasma treatment for roughening can be performed using oxygen or ozone as an atmospheric gas, as in the plasma treatment for roughening the surface of the resin molded body 1 described above. By roughening the surface of the intermediate film 3 in this manner, the adhesion of the metal film 2 to the intermediate film 3 can be further enhanced by an anchor effect, and the metal film on the resin molded body 1 via the intermediate film 3 can be improved. 2 can further improve the adhesion.

Further, after forming the intermediate film 3 on the surface of the resin molded body 1, before forming the metal film 2 on the intermediate film 3, the resin on the surface of the intermediate film 3 is formed prior to the formation of the metal film 2. It is preferable to carry out a treatment for cleaving the bond of the molecule.
The treatment for cleaving the molecular bond is performed after the plasma treatment for roughening the surface, and is similar to the treatment for cleaving the molecular bond of the resin of the resin molded body 1, as in the plasma treatment and the laser irradiation. Can be performed by ultraviolet irradiation. By cleaving the molecular bond of the resin on the surface of the intermediate film 3 in this way, the bonding between the intermediate film 3 and the metal film 2 can be enhanced, and the adhesion of the metal film 2 to the intermediate film 3 can be improved. And the resin molded body 1 with the intermediate film 3 interposed therebetween.
And the metal film 2 can be further improved in adhesion.

A metal is deposited on the intermediate film 3 by a physical vapor deposition method (PVD method) such as sputtering.
At the same time, the metal film 2 formed on the surface of the intermediate film 3 may be irradiated with an ion beam of a rare gas element such as argon. When the ion beam of the rare gas element is irradiated in this manner, the ion beam collides with the metal particles deposited on the surface of the intermediate film 3 from behind at high speed, and the metal particles are beaten into the resin of the intermediate film 3 and pushed. As a result, the surface layer of the resin of the intermediate film 3 is in a state where the resin and the metal are mixed. Therefore, the adhesion of the metal film 2 to the intermediate film 3 can be further enhanced, and the adhesion of the metal film 2 to the resin molded body 1 via the intermediate film 3 can be further enhanced. In addition, the kinetic energy of the high-speed ion beam can promote the bonding between the metal particles and the resin of the intermediate film 3, and from this point, the adhesion of the metal film 2 to the intermediate film 3 can be enhanced. .

FIG. 15 shows an apparatus for irradiating an ion beam as an assist when the metal film 2 is formed by sputtering. A holder electrode 12 and a target metal 13 such as copper are arranged in a chamber 11. A DC power supply 14 is connected to the holder electrode 12 and the target metal 13. Further, an ion gun 39 is provided in the chamber 11, and an ion beam of a rare gas element such as argon can be irradiated from the ion gun 39. As the ion gun 39 for irradiating the ion beam of the rare gas element, a filament type such as a Kauffman type can be used. Then, the resin molded body 1 having the intermediate film 3 formed on the surface is set while being held by the holder electrode 12, and the inside of the chamber 11 is
The plasma P is evacuated to the order of 0 ^-4 Pa, and a plasma P is applied by applying a DC voltage of about 3 kW to the target metal 13 while passing a rare gas such as argon gas through the chamber 11 at a gas pressure of about 0.5 Pa. Then, a metal can be vapor-deposited on the surface of the resin molded body 1 from above the intermediate film 3.
9 to, for example, an acceleration voltage of 500 eV and a beam current of 150 m
By irradiating an ion beam of a rare gas element such as argon under the condition A, it is possible to assist the driving of driving the particles of the deposited metal into the intermediate film 3.

Further, as described above, physical vapor deposition (PVD)
When assisting by irradiating an ion beam when forming the metal film 2 by the method (1), an ion beam of oxygen ions is irradiated from the ion gun 39.
The metal particles deposited on the surface of the metal film are beaten into the resin of the intermediate film 3 in a state where the metal particles have reacted with oxygen ions to form a metal oxide. Objects can be mixed. When the flow rate of oxygen to the ion gun 39 is reduced and a rare gas such as argon is gradually introduced, and the irradiation of the ion beam of rare gas element ions is increased, the metal oxide As the amount gradually decreases and the amount of metal increases, the metal oxide and the metal can be mixed in the surface layer of the intermediate film 3, and the adhesion of the metal film 2 to the intermediate film 3 can be further enhanced. It becomes.
When the ion beam is irradiated by using the active gas such as the oxygen gas, the ion gun 39 is made of E
It is necessary to use a non-filament type such as CR type.

[0078]

As described above, the metal-coated molded article according to the first aspect of the present invention is a metal-coated molded article in which the surface of a resin molded article is coated with a metal film, wherein the resin and the metal of the resin molded article are mixed. Since an intermediate film containing a resin having higher adhesion to a metal film than adhesion to a film is formed with a thickness of 5 μm or less between the resin molding and the metal film, The adhesion of the metal film can be increased by an intermediate film containing a resin having high adhesion to the metal film, and the thickness of the intermediate film is set to be as thin as 5 μm or less. It does not impair the characteristics of the body.

According to a second aspect of the present invention, in the first aspect, the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin, and these resins have a polar group and bind to a metal. It is easy to perform and has high heat resistance, so that the heat resistance of the resin molded article can be increased.

According to a third aspect of the present invention, in the first or second aspect, the intermediate film is formed of a film in which a resin and a metal film are mixed, so that the adhesion of the metal film to the intermediate film is improved. It is possible to further enhance the adhesion, and to obtain higher adhesion of the metal film to the resin molded body via the intermediate film.

According to a fourth aspect of the present invention, in the third aspect, the mixing ratio of the metal to the resin is gradually changed such that the mixing ratio of the metal to the resin molded body is low at a portion near the resin molded body and high at a portion near the metal film. Since the film is formed, the ratio of the resin is large at the interface in contact with the resin molded body of the intermediate film,
High adhesion between the intermediate film and the resin molded body can be ensured, and at the same time, the ratio of metal at the interface in contact with the metal film of the intermediate film is large, and the adhesion between the intermediate film and the metal film can be increased. Further, it is possible to obtain higher adhesion of the metal film to the resin molded body via the intermediate film.

According to a fifth aspect of the present invention, in the first or second aspect, the intermediate film is formed of a film in which a resin and an inorganic material are mixed. Adhesion of the metal film to the resin molded body through the intermediate film can be enhanced by mixing the inorganic substance into the intermediate film by mixing the inorganic substance into the intermediate film. Can be obtained even higher.

According to a sixth aspect of the present invention, since alumina is used as the inorganic material in the fifth aspect, alumina has a high wettability with copper, and when the metal film is formed of copper, the intermediate film and the metal film are used. And alumina can be obtained with particularly high adhesion, and alumina has a characteristic that dielectric loss is very small, and a metal-coated molded article can be used as a circuit board having excellent characteristics. .

According to a seventh aspect of the present invention, in the first or second aspect, the intermediate film is formed to have a two-layer structure of a resin layer on the resin molded body side and a metal oxide layer on the metal film side. Therefore, the adhesion between the metal oxide and the metal and the adhesion between the metal oxide and the resin are higher than the adhesion between the resin and the metal, and the adhesion between the resin molded article and the resin layer is higher. Of course, the adhesion between the metal film and the metal oxide layer and the adhesion between the metal oxide layer and the resin layer can be increased, and the adhesion of the metal film to the resin molded product via the intermediate film can be obtained. Can be obtained even higher.

The invention according to claim 8 is the invention according to claim 7, wherein the metal oxide layer is formed of a layer in which the metal of the metal film and its oxide are mixed, and the mixing ratio of the metal oxide is reduced to the resin layer. The metal oxide layer was formed by gradually changing the metal oxide layer so that it was higher near the metal film and lower near the metal film. Is high, the adhesion between the resin layer and the metal oxide layer can be secured, and the ratio of the metal at the interface with the metal film is high, and the adhesion between the metal film and the metal oxide layer can be improved. This ensures that the adhesion of the metal film to the resin molded body via the intermediate film can be further enhanced.

[0086] According to a ninth aspect of the present invention, in the method for manufacturing a metal-coated molded product, a resin having higher adhesiveness to the metal film than adhesiveness between the resin of the resin molded product and the metal film is formed on the surface of the resin molded product. The intermediate film to be contained was formed with a thickness of 5 μm or less, and thereafter, the metal film was formed on the surface of the resin molded product from above the intermediate film. An intermediate film containing a resin having high adhesion to the film can be obtained at a high level, and the thickness of the intermediate film is set to be as thin as 5 μm or less, and the characteristics of the resin molded article are impaired by the intermediate film. Is lost.

According to a tenth aspect of the present invention, in the ninth aspect, since the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin, these resins have a polar group and bind to a metal. It is easy to perform and has high heat resistance, so that the heat resistance of the resin molded article can be increased.

The invention of claim 11 is the invention of claim 9 or 1
0, the intermediate film is formed by gas-phase polymerization of the resin on the surface of the resin molded body, so that it is possible to form the intermediate film with a thin thickness of 5 μm or less on the surface of the resin molded body, In addition, even if the surface of the resin molded product has a three-dimensional three-dimensional shape, it is possible to form an intermediate film with a uniform film thickness without any problem such as liquid pool or liquid flow.

In the twelfth aspect of the present invention, the intermediate film is formed by spraying a resin liquid on the surface of the resin molded body. It is possible to form an intermediate film with a uniform film thickness without any problems such as liquid flow and the like.

Further, the invention of claim 13 is the invention of claims 9 to 1
2. In any one of the above, the surface of the resin molded body is roughened by plasma treatment, and then the intermediate film is formed on the surface of the resin molded body. And the adhesion between the resin molded body and the metal film via the intermediate film can be further improved.

According to a fourteenth aspect of the present invention, in the thirteenth aspect, the plasma treatment for roughening the surface of the resin molding is performed.
Since the etching is performed with plasma using oxygen or ozone as an atmospheric gas, a large etching effect can be obtained, and the surface of the resin molded body can be efficiently roughened.

Further, the invention of claim 15 is the invention of claims 9 to 1
In any one of (4) and (3), after performing a plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded body, an intermediate film is formed on the surface of the resin molded body. The adhesiveness of the intermediate film to the resin molded article can be improved by increasing the bonding property between the resin on the surface of the resin and the resin of the intermediate film, and the adhesion between the resin molded article and the metal film via the intermediate film can be improved. The property can be further enhanced.

According to a sixteenth aspect of the present invention, in the fifteenth aspect, the plasma treatment for cleaving the bonding of the resin molecules on the surface of the resin molded body is performed by atmospheric pressure plasma. It is possible to carry out the processing with a simple device without the need for providing equipment.

The seventeenth aspect of the present invention relates to the ninth to the first aspects.
4. In any one of the above, after performing a plasma treatment for irradiating a laser to the surface of the resin molded body to cleave the bonding of the resin molecules on the surface, an intermediate film is formed on the surface of the resin molded body. Can be performed at atmospheric pressure, and there is no need to provide a vacuum pump or a vacuum chamber, and the processing can be performed with a simple device.

The invention according to claim 18 is the invention according to claims 9 to 1
In any one of 4, the surface of the resin molded body is subjected to a plasma treatment for irradiating ultraviolet rays with an excimer lamp to cleave the bonding of the molecules of the resin on the surface, and then an intermediate film is formed on the surface of the resin molded body. Therefore, an excimer lamp can be made simpler, smaller, and cheaper than a device that irradiates a laser, and can be processed at low cost.

The nineteenth aspect of the present invention relates to the ninth to the first aspects.
8. In any of 8, the resin and the metal are mixed by forming the metal film on the intermediate film by physical vapor deposition of the metal while forming the intermediate film by vapor-phase polymerization of the resin on the surface of the resin molded body. Since an intermediate film is formed in this way, an intermediate film in which a resin and a metal are mixed can be easily produced by utilizing the characteristics of gas phase polymerization and physical vapor deposition.

[0097] According to a twentieth aspect of the present invention, in the nineteenth aspect, a metal film is formed by physical vapor deposition of a metal while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded product. By forming, in forming the intermediate film in which the resin and the metal are mixed, by increasing the physical vapor deposition of the metal while reducing the ratio of the gas phase polymerization of the resin, the mixing ratio of the metal to the resin is close to that of the resin molded body. Low in part,
An intermediate film that gradually changes is formed so that it becomes higher near the metal film, so the characteristics of gas-phase polymerization and physical vapor deposition are used to make the intermediate ratio of the resin and metal gradually change. A film can be easily produced.

The invention of claim 21 is the invention of claims 9 to 1
In any one of 8, while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded body, by performing physical vapor deposition of an inorganic material, an intermediate film in which the resin and the inorganic material are mixed is formed. By utilizing the characteristics of gas phase polymerization and physical vapor deposition, an intermediate film in which a resin and an inorganic substance are mixed can be easily produced.

The invention of claim 22 is the method of claim 21, wherein alumina is physically vapor-deposited as an inorganic substance while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded product, whereby the resin and the alumina are combined. Since the mixed intermediate film is formed, the intermediate film in which the resin and the alumina are mixed can be easily manufactured by utilizing the characteristics of the gas phase polymerization and the physical vapor deposition.

Also, the invention of claim 23 is the invention of claims 9 to 2
2. In any one of (2), by forming a resin layer on the surface of the resin molded body and forming a metal oxide layer on the surface of the resin layer, an intermediate film having a two-layer structure of the resin layer and the metal oxide layer is formed. Therefore, the adhesion between the metal oxide and the metal and the adhesion between the metal oxide and the resin are higher than the adhesion between the resin and the metal, and the adhesion between the resin molded body and the resin layer. Of course, the adhesion between the metal film and the metal oxide layer and the adhesion between the metal oxide layer and the resin layer can be increased, and the adhesion of the metal film to the resin molded body via the intermediate film can be obtained. It is possible to obtain higher properties.

According to a twenty-fourth aspect of the present invention, in the twenty-third aspect, a metal oxide is formed by forming a resin layer on the surface of a resin molded body and depositing the metal on the resin layer while oxidizing the metal by reactive sputtering. By forming a layer,
Since a two-layered intermediate film of a resin layer and a metal oxide layer was formed, and subsequently the metal film was sputtered without being oxidized, a metal film was formed on the surface of the metal oxide layer of the intermediate film. The formation of the metal oxide layer can be easily performed by utilizing the characteristics of the reactive sputtering, and further, by performing the sputtering while changing the atmosphere gas, the formation of the metal oxide layer and the formation of the metal film in the same sputtering process. The formation can be performed, and the number of steps can be reduced.

According to a twenty-fifth aspect of the present invention, in the twenty-fourth aspect, after forming a resin layer on the surface of the resin molded product, the metal oxide is deposited on the resin layer while oxidizing the metal by reactive sputtering. By forming a layer,
In forming a two-layer intermediate film of a resin layer and a metal oxide layer, reactive sputtering is performed while adjusting the amount of oxidation reaction of the metal, and the metal and its oxide are mixed, and the metal oxide is mixed. Since the metal oxide layer is formed so that the mixing ratio is gradually changed so as to be higher in a portion closer to the resin layer and lower in a portion farther from the resin layer, utilizing the characteristics of reactive sputtering, The metal oxide layer in which the mixing ratio of the metal oxide changes can be easily formed.

The invention according to claim 26 is the invention according to claims 9 and 2.
In any one of 5, the intermediate film is formed on the surface of the resin molded body, and then the surface of the intermediate film is roughened by plasma treatment, and then the metal film is formed on the surface of the resin molded body from above the intermediate film. As a result, the adhesion between the intermediate film and the metal film can be enhanced by the anchor effect of the rough surface, and the adhesion between the resin molded body and the metal film via the intermediate film can be further improved. is there.

The invention of claim 27 is the invention of claims 9 to 2
6. In any one of the above, after forming an intermediate film on the surface of the resin molded product and then performing a treatment of cleaving the bond of the resin molecules on the surface of the intermediate film, a metal film Is formed, so that the bond between the resin of the intermediate film and the metal film can be enhanced by the cleavage of molecular bonds, and the adhesion of the metal film to the intermediate film can be improved. It is possible to further enhance the adhesion between the formed resin molded body and the metal film.

The invention of claim 28 is the invention of claims 9 to 2
7. In any one of 7, when the metal film is formed by physical vapor deposition of the metal on the surface of the resin molded body from above the intermediate film, the ion beam of the rare gas element ion is irradiated.
The metal particles deposited on the surface of the intermediate film by physical vapor deposition are driven into the intermediate film by the ion beam, and the surface layer of the intermediate film is a state in which the metal is mixed, and the adhesion of the metal film to the intermediate film And the adhesion of the metal film to the resin molded body via the intermediate film can be further improved.

Further, the invention of claim 29 is the invention of claims 9 to 2
7. In any one of the above, in forming a metal film by physically depositing a metal on the surface of the resin molded body from above the intermediate film, irradiating an ion beam of a rare gas element ion after irradiating an ion beam of an oxygen ion Therefore, metal particles deposited on the surface of the intermediate film by physical vapor deposition are struck in a state where they are oxidized by an ion beam of oxygen ions, and then the metal particles struck into the intermediate film by an ion beam of rare gas element ions. The amount increases, and the metal oxide and the metal can be mixed in the surface layer of the intermediate film, so that the adhesion of the metal film to the intermediate film can be further enhanced.

[Brief description of the drawings]

FIG. 1 shows an example of an embodiment of the present invention,
(A), (b) is a sectional view, respectively.

FIG. 2 is a schematic view of a sputtering apparatus used in an example of the above embodiment.

FIG. 3 is a schematic diagram of a polyimide vapor deposition polymerization apparatus used in an example of the above embodiment.

FIG. 4 is a schematic view of a polyimide plasma polymerization apparatus used in an example of the above embodiment.

FIG. 5 is a schematic diagram of a plasma processing apparatus used in an example of the above embodiment.

FIG. 6 is a partially enlarged cross-sectional view showing another example of the embodiment of the present invention.

FIG. 7 is a partially enlarged cross-sectional view showing another example of the embodiment of the present invention.

FIG. 8 is a schematic diagram of an apparatus for performing vapor deposition polymerization and vacuum vapor deposition simultaneously, which is used in an example of the above embodiment.

FIG. 9 is a partially enlarged cross-sectional view showing another example of the embodiment of the present invention.

FIG. 10 is a sectional view showing another example of the embodiment of the present invention.

11 shows another example of the embodiment of the present invention, and (a), (b), and (c) are cross-sectional views, respectively.

FIG. 12 is a schematic view of a sputtering apparatus used in one example of the above embodiment.

FIG. 13 is a schematic diagram of a reactive sputtering apparatus used in an example of the above embodiment.

FIG. 14 is a partially enlarged cross-sectional view showing another example of the embodiment of the present invention.

FIG. 15 is a schematic view of an apparatus for performing sputtering and ion beam irradiation used in another example of the embodiment of the present invention.

FIG. 16 is a graph showing the peel strength of a metal film before and after treatment with plasma in the related art.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Resin molded object 2 Metal film 3 Intermediate film 4 Resin layer 5 Metal oxide layer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 3/38 H05K 3/38 EA // C08L 101: 00 C08L 101: 00 (72) Inventor Naoto Ikegawa Kadoma, Osaka 1048 Ichidai Kadoma Matsushita Electric Works Co., Ltd. (72) Inventor Takashi Shindo 1048 Oji Kadoma Osaka Kadoma City Matsushita Electric Works Co., Ltd.F term (reference) 4F006 AA15 AB34 AB38 AB73 BA01 CA08 DA01 DA04 EA03 4F100 AA01C AA17D AA19C AB01B AB01C AB01D AB33B AB33D AK01A AK01C AK12 AK49C AK53C BA03 BA04 BA10A BA10B BA25C CA23C CA23D EH462 EH662 EJ121 EJ541 EJ611 GB41 JK06 YY00C 4K029 AA11 BA01 CC04 FA02 ACO CC08 EE21 EE36 FF23 GG02 GG04

Claims (29)

[Claims] 1. A metal-coated molded article in which a surface of a resin molded article is coated with a metal film, wherein the resin contains a resin having higher adhesion to the metal film than adhesion between the resin of the resin molded article and the metal film. A metal-coated molded article formed by forming an intermediate film with a thickness of 5 μm or less between a resin molded article and a metal film. 2. The metal-coated body according to claim 1, wherein the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin. 3. The metal-coated molded product according to claim 1, wherein the intermediate film is formed of a film in which a resin and a metal of a metal film are mixed. 4. An intermediate film is formed by gradually changing a mixing ratio of a metal to a resin so as to be low in a portion near a resin molded body and to be high in a portion near a metal film. The metal-coated molded product according to claim 3. 5. The metal-coated molded product according to claim 1, wherein the intermediate film is formed by a film in which a resin and an inorganic substance are mixed. 6. The metal-coated molded article according to claim 5, wherein alumina is used as an inorganic substance. 7. An intermediate film, comprising: a resin layer on a resin molded body side;
The metal-coated molded product according to claim 1 or 2, wherein the metal-coated molded product is formed in a two-layer configuration with a metal oxide layer on a side of the metal film. 8. A metal oxide layer is formed of a layer of a metal film in which a metal and its oxide are mixed, and the mixing ratio of the metal oxide to the metal is high near the resin layer and high near the metal film. 8. The metal-coated molded body according to claim 7, wherein a metal oxide layer is formed by gradually changing the metal oxide layer so as to become lower. 9. An intermediate film containing a resin having higher adhesion to a metal film than adhesion between a resin and a metal film of the resin molding with a thickness of 5 μm or less is formed on the surface of the resin molding. A method for producing a metal-coated molded article, comprising forming a metal film on a surface of a resin molded article from above an intermediate film. 10. The method according to claim 9, wherein the resin contained in the intermediate film is at least one of a polyimide resin and an epoxy resin. 11. The method for producing a metal-coated molded article according to claim 9, wherein an intermediate film is formed by subjecting the resin to gas-phase polymerization on the surface of the resin molded article. 12. The method according to claim 9, wherein the intermediate film is formed by spraying a resin liquid on the surface of the resin molded body. 13. The metal coating according to claim 9, wherein an intermediate film is formed on the surface of the resin molded body after the surface of the resin molded body is roughened by plasma treatment. A method for producing a molded article. 14. The method according to claim 13, wherein the plasma treatment for roughening the surface of the resin molded body is performed with plasma using oxygen or ozone as an atmospheric gas. 15. The method according to claim 9, wherein an intermediate film is formed on the surface of the resin molded body after performing a plasma treatment for cleaving the bonding of the molecules of the resin on the surface of the resin molded body. A method for producing a metal-coated molded product according to the above. 16. The method according to claim 15, wherein the plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded body is performed by atmospheric pressure plasma. 17. The method according to claim 1, wherein the intermediate layer is formed on the surface of the resin molded body after the surface of the resin molded body is subjected to plasma treatment by irradiating a laser beam to cleave the bonds of the molecules of the resin on the surface. 15. The method for producing a metal-coated molded product according to any one of 9 to 14. 18. The method according to claim 1, wherein the surface of the resin molded body is subjected to a plasma treatment for irradiating ultraviolet rays with an excimer lamp to cleave the bonding of the molecules of the resin on the surface, and then forming an intermediate film on the surface of the resin molded body. The method for producing a metal-coated molded product according to any one of claims 9 to 14. 19. A method in which a resin and a metal are mixed by forming a metal film on the intermediate film by physical vapor deposition of a metal while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded body. 2. An intermediate film is formed.
9. The method for producing a metal-coated molded product according to any one of 8. 20. A method in which a resin and a metal are mixed by forming a metal film on the intermediate film by physical vapor deposition of a metal while forming an intermediate film by vapor-phase polymerization of the resin on the surface of the resin molded body. In forming the intermediate film, by increasing the physical vapor deposition of the metal while reducing the ratio of the gas phase polymerization of the resin, the mixing ratio of the metal to the resin is low in the portion close to the resin molded body and high in the portion close to the metal film. 2. The method according to claim 1, wherein the intermediate film is formed so as to change gradually.
10. The method for producing a metal-coated molded product according to item 9. 21. An intermediate film in which a resin and an inorganic material are mixed is formed by physical vapor deposition of an inorganic material while forming an intermediate film by gas-phase polymerization of the resin on the surface of the resin molded body. Item 19. The method for producing a metal-coated molded product according to any one of Items 9 to 18. 22. An intermediate film in which resin and alumina are mixed by physical vapor deposition of alumina as an inorganic substance while forming an intermediate film by vapor-phase polymerization of the resin on the surface of the resin molded body. The method for producing a metal-coated molded product according to claim 21. 23. A two-layer intermediate film composed of a resin layer and a metal oxide layer by forming a resin layer on the surface of a resin molded body and forming a metal oxide layer on the surface of the resin layer. The method for producing a metal-coated molded product according to any one of claims 9 to 22, characterized in that: 24. After forming a resin layer on the surface of the resin molded body, the metal is oxidized by reactive sputtering, and is vapor-deposited on the resin layer to form a metal oxide layer. 24. The method according to claim 23, wherein the metal film is formed on the surface of the metal oxide layer of the intermediate film by forming an intermediate film having a two-layer structure of the oxide layer and subsequently performing sputtering without oxidizing the metal. A method for producing a metal-coated molded product according to the above. 25. After forming a resin layer on the surface of a resin molded body, the metal is oxidized by reactive sputtering, and is vapor-deposited on the resin layer to form a metal oxide layer. In forming an intermediate film having a two-layer structure of an oxide layer, reactive sputtering is performed while adjusting the oxidation reaction amount of the metal, and the metal and its oxide are mixed, and the mixing ratio of the metal oxide is The method for producing a metal-coated molded product according to claim 24, wherein the metal oxide layer is formed so as to gradually change so as to be higher in a portion near the resin layer and to be lower in a portion far from the resin layer. 26. An intermediate film is formed on the surface of the resin molded body,
Then, after the surface of the intermediate film is roughened by plasma treatment,
The method for manufacturing a metal-coated molded product according to any one of claims 9 to 25, wherein a metal film is formed on the surface of the resin molded product from above the intermediate film. 27. An intermediate film is formed on a surface of the resin molded body,
27. A metal film is formed on the surface of the resin molded body from above the intermediate film after performing a process of cleaving the bond of the resin molecules on the surface of the intermediate film. The method for producing a metal-coated molded article according to the above. 28. An ion beam of rare gas element ions when a metal film is formed by physical vapor deposition of a metal on the surface of a resin molding from above the intermediate film. The method for producing a metal-coated molded product according to any one of the above. 29. When a metal film is formed by physical vapor deposition of a metal on the surface of a resin molded product from above an intermediate film, an ion beam of a rare gas element ion is irradiated after irradiation with an ion beam of oxygen ions. 28. A method according to claim 9, wherein:
The method for producing a metal-coated molded product according to any one of the above.