JP2002128927A - Method for forming metallic film on resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a metallic film on a resin molded article, which permits to efficiently incorporate a polar group in a high density into a resin molecule on the surface of a resin molded article and to form a metallic film having excellent adhesion properties on the resin molded article. SOLUTION: A plasma treatment is effected to split a bond of a molecule of a resin on the surface of a resin molded article 1. Then, plasma is introduced onto the surface of the resin molded article 1 by a downstream method thereby to allow free radicals in the plasma to reach mainly the surface of the resin molded article 1 and a polar group is incorporated into the molecule of the resin on the surface of the resin molded article 1 by the action of the free radicals. Subsequently, a metallic film is formed on the surface of the resin molded article 1. Thus, a polar group can be efficiently incorporated in a state where the molecule of the resin of the resin molded article 1 is cleaved. The treatment for incorporating the polar group is effected by means of free radicals to avoid etching of the surface of the resin molded article by ions having high energy thereby permitting highly dense formation of the polar groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a technique for forming a metal film on the surface of a resin molded product.

[0002]

2. Description of the Related Art For a three-dimensional circuit board, a sensor component, a reflector, and the like, a resin composition is formed by injection molding of a resin composition, and a metal film serving as a circuit and a reflection film is formed on the surface of the resin molded body. It is manufactured by: 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, LCP and SPS have no polar groups in their molecules,
Even if a metal film is formed on the surface of a resin molded product manufactured by LCP or SPS, the adhesion of the metal film to the resin molded product is extremely small.

Therefore, in order to enhance the adhesion of the metal film to the resin molded body, the surface of the resin molded body is subjected to a plasma treatment.

FIG. 12 shows an example of a plasma processing apparatus, in which a holding electrode 3 is provided in a chamber 15.
A counter electrode 4 is provided, the holding electrode 3 is connected to an RF high-frequency power source 8 and the counter electrode 4 is connected to a chamber 15 to be grounded. Atmosphere gas for generation can be introduced. And the holding electrode 3
By holding the resin molded body 1 in a state where the resin molded body 1 is brought into contact with the holding electrode 3 and setting it in the chamber 15, introducing an atmosphere gas such as a nitrogen gas into the chamber 15 and applying a high-frequency voltage to the holding electrode 3, A plasma P such as a nitrogen plasma is generated by a gas discharge phenomenon between the electrode 3 and the counter electrode 4. When the plasma P is generated in this manner, ions such as N ⁺ in the plasma P act on the surface of the resin molded body 1, perform cleaning to remove contaminants on the surface of the resin molded body 1, and perform nitrogen polar grouping. For example, a process of imparting a polar group such as to a molecule on the surface of the resin molded body 1 is performed. After the polar group is provided on the surface of the resin molded body 1 as described above, a metal film such as copper is formed on the surface of the resin molded body 1 by a PVD method such as vapor deposition or sputtering. It can improve the adhesion.

[0005]

However, it is not possible to obtain a high effect of improving the adhesion between a resin molded body made of LCP or SPS and a metal film only by such a treatment using plasma such as nitrogen plasma.

FIG. 13 shows polyphthalamide (PPA) and L
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 the CP is treated with the nitrogen plasma as described above, and the peel strength of PPA is greatly improved by the nitrogen plasma treatment. Is L
CP has a small improvement in peel strength by the nitrogen plasma treatment, and does not reach the required 0.6 N / mm peel strength. 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.

[0007]

Embedded image

When ions such as N.sup. ^{+ In} the plasma act on the surface of the resin molded body to impart a polar group such as a nitrogen polar group, simultaneously, ions having high energy cause the surface of the resin molded body to be exposed. Is etched, and a phenomenon occurs in which the polar group formed on the surface of the resin molded body is removed by this etching, which also prevents the effect of improving the adhesion between the resin molded body and the metal film from being high. Probable cause.

The present invention has been made in view of the above points, and it is possible to efficiently and efficiently provide a polar group to resin molecules on the surface of a resin molded product, and to adhere a metal film to the resin molded product. It is an object of the present invention to provide a method for forming a metal film on a resin molded body that can be formed at a high height.

[0010]

According to a first aspect of the present invention, there is provided a method for forming a metal film on a resin molded body, comprising the steps of: performing a plasma treatment for cleaving a bond of a resin molecule on a surface of the resin molded body; The plasma is led to the surface of the resin molded body 1 by the downstream method, so that radicals in the plasma mainly reach the surface of the resin molded body 1 and the action of the radicals causes polarities of the resin molecules on the surface of the resin molded body 1 to change. It is characterized by performing a treatment for providing a group, and thereafter, forming a metal film 2 on the surface of the resin molded body 1.

According to a second aspect of the present invention, there is provided a method for forming a metal film on a resin molded body, comprising: performing a plasma treatment for cleaving a bond of a resin molecule on the surface of the resin molded body; The radicals in the plasma mainly reach the surface of the resin molded body 1 by the action of the radicals, so that the radicals in the plasma do not reach the surface of the resin molded body 1 by the electric suction. A process for imparting a polar group to a resin molecule is performed, and thereafter, a resin molded body 1 is formed.
A metal film 2 is formed on the surface of the substrate.

According to a third aspect of the present invention, in the above-described second aspect, the resin molded body 1 is subjected to a process of imparting a polar group to a resin molecule on the surface of the resin molded body 1 by the action of radicals in plasma. Holding electrode 3 to be held and resin molded body 1
Plasma is generated between the opposing electrodes 4 facing each other and the resin molded body 1 is surrounded by the intermediate electrode 5 that electrically attracts ions in the plasma, so that the ions in the plasma reach the surface of the resin molded body 1. It is characterized in that it is not performed.

According to a fourth aspect of the present invention, in the above-mentioned second aspect, the resin molded body 1 is subjected to a process of imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 by the action of radicals in the plasma. Holding electrode 3 to be held and resin molded body 1
A plasma is generated between the opposing electrodes 4 facing each other, and a high-frequency voltage with a negative bias is applied to the opposing electrodes 4 so that ions in the plasma are electrically attracted to the opposing electrodes 4 so that the plasma is generated. Are prevented from reaching the surface of the resin molded body 1.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, plasma is generated between the holding electrode 3 holding the resin molded body 1 and the counter electrode 4 facing the resin molded body 1. In performing the plasma treatment for breaking the bond of the resin molecules on the surface of the resin molded body 1, a high frequency voltage with a negative bias is applied to the holding electrode 3, and the negative bias voltage is changed from −100 V to −700 V. Is controlled within the range.

According to a sixth aspect of the present invention, there is provided a method for forming a metal film on a resin molded body, wherein the surface of the resin molded body 1 is irradiated with a laser to cleave the bond of the resin molecules on the surface of the resin molded body 1. Is performed, the plasma is led to the surface of the resin molded body 1 by the downstream method so that radicals in the plasma mainly reach the surface of the resin molded body 1 and the action of the radicals causes the surface of the resin molded body 1 A process for imparting a polar group to a resin molecule is performed, and thereafter, a resin molded body 1 is formed.
A metal film 2 is formed on the surface of the substrate.

According to a seventh aspect of the present invention, there is provided a method of forming a metal film on a resin molded product, comprising: irradiating a laser on the surface of the resin molded product 1 to cleave the bonds of the resin molecules on the surface of the resin molded product 1. After performing the above, radicals in the plasma mainly reach the surface of the resin molded body 1 by electrically attracting ions in the plasma to the electrodes so as not to reach the surface of the resin molded body 1. It is characterized in that a process for imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 by the action of radicals is performed, and thereafter, the metal film 2 is formed on the surface of the resin molded body 1.

The invention according to claim 8 is the method according to any one of claims 1 to 7, wherein after the treatment in which a polar group in the surface of the resin molded body 1 is given a polar group to the resin molecules by the radicals in the plasma, the plasma treatment is performed. To crosslink the resin molecules on the surface of the resin molded body 1.

According to a ninth aspect of the present invention, in the eighth aspect, the resin molded body 1 is surrounded by a barrier 9 that allows ultraviolet rays emitted from the plasma to pass but does not allow ions in the plasma to pass. It is characterized by performing a plasma treatment for crosslinking the molecules of the resin on the surface.

According to a tenth aspect of the present invention, in any one of the first to seventh aspects, after performing a treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 with radicals in the plasma, the ultraviolet irradiation is performed. It is characterized in that a treatment is performed to crosslink the resin molecules on the surface of the resin molded body 1.

[0020] The invention of claim 11 provides the above-mentioned claim 10.
, Wherein the ultraviolet irradiation treatment is performed using an ultraviolet laser.

According to the twelfth aspect of the present invention,
Wherein the ultraviolet irradiation treatment is performed using an excimer lamp.

According to a thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the surface of the resin molded body 1 is subjected to a process of cleaving the bonding of the molecules of the resin on the surface of the resin molded body 1. The plasma treatment for roughening is performed.

The invention of claim 14 is the invention of claim 13
Wherein plasma treatment for roughening the surface of the resin molded body 1 with plasma using oxygen or ozone as an atmospheric gas is performed.

According to a fifteenth aspect of the present invention, in any one of the first to fourteenth aspects, the treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 by the action of radicals in the plasma is performed by resin molding. It is performed while heating the body 1.

The invention of claim 16 provides the above-mentioned claim 15.
Wherein the resin molded body 1 is heated at a temperature of the glass transition temperature of the resin of the resin molded body 1 ± 30 ° C.

The invention of claim 17 is characterized in that, in claim 15 or 16, only the surface layer of the resin molded article 1 is heated.

The invention of claim 18 is characterized in that, in claim 17, a surface of the resin molded body 1 is heated by irradiating the surface of the resin molded body 1 with a heat ray.

Further, the invention of claim 19 provides the invention according to claims 1 to 1
In any one of the above 8, the treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded article 1 by the action of radicals in the plasma may be performed by using a gas selected from NH ₃ , SO ₂ , NO ₂ , and CO as an atmosphere gas. It is characterized in that it is performed with the used plasma.

Further, the invention of claim 20 provides the invention as set forth in claims 1 to 1
9, the metal film 2 is formed on the surface of the resin molding 1.
Prior to forming the metal film 2, a metal having higher adhesiveness to the resin molded body 1 than the metal film 2 is pre-coated on the surface of the resin molded body 1.
Is formed.

[0030] The invention of claim 21 is the invention of claim 20.
, Wherein the resin molded body 1 is heated at a temperature of the glass transition temperature of the resin of the resin molded body ± 30 ° C. to perform the pre-coating of the metal.

Further, the invention of claim 22 provides the above-mentioned claim 20.
Or 21, wherein the precoat metal film 6 is formed of a metal oxide.

According to the twenty-third aspect of the present invention, in any one of the first to nineteenth aspects, prior to the formation of the metal film 2 on the surface of the resin molded body 1, the adhesion to the metal film 2 is reduced. A resin higher than the above resin is pre-coated on the surface of the resin molded body 1, and the metal film 2 is formed on the pre-coated resin film 7.

[0033]

Embodiments of the present invention will be described below.

In the present invention, the resin molded body 1 is LC
A resin composition containing P or SPS as a main component is used. First, a first-stage treatment for cleaving the bonding of the resin molecules on the surface of the resin molded product 1 is performed. The second step of imparting a polar group to the resin molecules on the surface of the molded body 1 is performed, and thereafter, the metal film 2 is formed on the surface of the molded resin body 1.

FIG. 1 (a) shows an example of a plasma processing apparatus used in the first and second aspects of the present invention for performing the first stage of processing for cleaving the bonding of the resin molecules on the surface of the resin molded article 1. The holding electrode 3 and the counter electrode 4 are provided in the chamber 15 so as to face each other.
The holding electrode 3 is formed as a tray and is connected to an RF high-frequency power source 8 via a blocking capacitor 18. The counter electrode 4 is connected to a chamber 15 to be grounded. Further, a gas inlet 16 is provided in the chamber 15 so that an atmospheric gas for plasma generation can be introduced into the chamber 15 from the gas inlet 16.

Then, the resin molded body 1 is held on the holding electrode 3 and set in the chamber 15.
Atmosphere gas such as argon is introduced into the chamber 15 from the high-frequency power source 8 and the high-frequency voltage (R
F: 13.56 MHz), plasma P is generated by a gas discharge phenomenon caused by a high-frequency glow discharge between the holding electrode 3 and the counter electrode 4. At this time, an inert gas such as an argon gas is used as the atmosphere gas, and the gas pressure is preferably set to about 1 to 15 Pa. By generating the Ar plasma P in this manner, ions such as Ar ⁺ in the plasma P act on the surface of the resin molded body 1 and the molecular bonds of the resin on the surface are cleaved. The time of the 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.

FIG. 1 (b) shows a second stage treatment for imparting a polar group to the resin molecules on the surface of the resin molding 1.
1 shows an example of a plasma processing apparatus used in the first embodiment of the present invention, which is formed by a plasma generation chamber 20 and a processing chamber 21. The plasma generation chamber 20 is formed of an ECR plasma generator that generates plasma by causing electron cyclotron resonance by a magnetic field and a microwave. The plasma generation chamber 20 has a gas introduction passage 22 for introducing an atmospheric gas.
And a plasma introduction path 23 that guides the plasma flow of the generated plasma P to the processing chamber 21. This plasma introduction path 23 is connected to the upper part of the processing chamber 21.

Then, as described above, the resin molded body 1 that has been subjected to the first-stage treatment for cleaving the bonds of the resin molecules on the surface is
It is set in the processing chamber 21 at a position below the tip of the plasma introduction path 23, and oxygen or nitrogen is supplied from the gas introduction path 22 as atmospheric gas to the plasma generation chamber 20.
To generate oxygen plasma or nitrogen plasma in the plasma generation chamber 20. In the plasma P generated in the plasma generation chamber 20 as described above, ions and electrons such as ionized O ⁺ or N ⁺ are present, and the plasma P further includes radicals such as oxygen radicals or nitrogen radicals. Exist as active molecules (atoms). The plasma P generated as described above in the plasma generation chamber 20 is introduced into the processing chamber 21 as a downstream through the gas introduction path 22 by the gas flow with the atmospheric gas serving as a carrier gas, and the resin P in the processing chamber 21 The compact 1 is processed by this downstream.

Here, the ion and the radical in the plasma P have different lifetimes, the ion has a short lifetime, and the radical has a long lifetime. Therefore, the plasma generation chamber 20 separated from the processing chamber 21 in which the resin molded body 1 is set
While the plasma P is generated and the plasma P is guided downstream to the resin molded body 1 in the processing chamber 21, the ions in the plasma P are combined with the electrons and neutralized, and the normal state of atoms and molecules is obtained. However, the radicals are carried downstream as they are and reach the surface of the resin molding 1. By introducing the plasma P to the surface of the resin molded body 1 by the downstream method in this manner, the plasma P
It is possible to make the radicals therein mainly reach the surface of the resin molded body 1 and prevent the ions from reaching them. The surface of the resin molded body 1 is mainly treated by the action of the radical, and the surface of the resin molded body 1 is treated. A polar group such as an oxygen polar group or a nitrogen polar group can be provided to the molecule of the resin. Since the molecules of the resin on the surface of the resin molded body 1 have been cleaved by the first-stage treatment as described above, the treatment for imparting a polar group can be performed efficiently. Also,
The treatment for imparting the polar group is mainly performed by radicals in the plasma P, and the ions hardly act on the surface of the resin molded body 1. Therefore, the surface of the resin molded body 1 is etched by ions having high energy. The polar group formed on the surface of the resin molded body 1 is not removed by this etching, and the polar group can be formed on the surface of the resin molded body 1 at a high density. is there. The processing time for imparting a polar group to the resin molecules on the surface of the resin molded body 1 is 5 to 4 times.
About 0 seconds is preferable. Incidentally, in the second-stage treatment for imparting a polar group by this radical, the radical generation amount E is large.
Although it is preferable to use CR plasma, plasma using high-frequency glow discharge as shown in FIG. 1A may be used.

After the first-stage and second-stage treatments are performed on the surface of the resin molded body 1 by the plasma as described above, the metal film 2 is formed on the surface of the resin molded body 1. FIG. 2 shows each step until the metal film 2 is formed on the resin molded body 1. The first and second steps of the process are performed on the surface of the resin molded body 1, and FIG. After the polar groups 10 are formed as described above, the metal film 2 is formed on the surface of the resin molded body 1 as shown in FIG. The formation of the metal film 2 can be performed by using any PVD method such as sputtering or vapor deposition.
Can be formed. Since the polar group 10 is formed on the surface of the resin molded body 1 with high efficiency and high density as described above, the resin molded body 1 is formed of a resin having no polar group in the molecule, such as LCP or SPS. However, the metal film 2 can be formed on the surface of the resin molded body 1 with high adhesion.

Here, regarding the invention of claim 1 described above,
The effect will be demonstrated with specific examples.

As the resin molded product 1, a product produced by injection molding LCP was used. Then, in the apparatus shown in FIG. 1A, argon gas was used as an atmosphere gas, and a gas pressure of 10 was used.
Plasma P was generated under the conditions of Pa and RF power of 500 W, and a treatment for cleaving molecules on the surface of the resin molded body 1 in the plasma P was performed for 30 seconds. Next, FIG.
In the apparatus described above, a nitrogen gas is used as an atmosphere gas, a plasma P is generated in the plasma generation chamber 20 under the conditions of a gas flow rate of 50 ml / min and an ECR power of 500 W, and the downstream of the plasma P is led to the processing chamber 21 for 30 seconds. Then, a treatment for giving a polar group to molecules on the surface of the resin molded body 1 was performed. Thereafter, DC magnetron sputtering was performed to form a 0.3 μm thick copper metal film 2 on the surface of the resin molded body 1. This metal film 2
Was measured to be 0.70 N / mm.

For comparison, in the apparatus shown in FIG. 1A, nitrogen gas was used
a, Plasma P was generated under the condition of RF power of 500 W, and a process of giving a polar group to molecules on the surface of the resin molded body 1 was performed in the plasma P for 30 seconds. Thereafter, sputtering was performed on the surface of the resin molded body 1 in the same manner as described above to form a copper metal film 2 having a thickness of 0.3 μm. When the peel strength of the metal film 2 was measured,
0.18 N / mm.

FIG. 3 shows the second and third embodiments of the present invention in which a polar group is added to a resin molecule on the surface of the resin molded article 1.
This shows an example of a plasma processing apparatus for performing a step process, in which a holding electrode 3 and a counter electrode 4 are provided in a chamber 25 so as to face each other. The holding electrode 3 is formed as a tray, and is connected to an RF high-frequency power source 8 via a matching box 26, and the counter electrode 4 is connected to a chamber 25 to be grounded. Further, a gas inlet 27 is provided in the chamber 25.
An atmosphere gas for plasma generation can be introduced into the inside. Further, a third intermediate electrode 5 is disposed between the holding electrode 3 and the counter electrode 4 so as to surround the resin molded body 1 held in contact with the holding electrode 3.
Are electrically connected to the holding electrode 3. This intermediate electrode 5
It is preferable to use one formed with a metal mesh or the like, and the holes have a pitch of 5 mm or less (preferably 1 mm
The following pitch is preferable. In this embodiment, a high-frequency voltage with a negative bias is applied to the holding electrode 3 from the high-frequency power supply 8.

After the first-stage treatment for cleaving the resin molecules on the surface of the resin molded body 1 as shown in FIG. 1A, the resin molded body 1 is moved to the holding electrode 3 in the chamber 25. , And surrounded by the intermediate electrode 5, an oxygen gas or a nitrogen gas is introduced as an atmospheric gas into the chamber 25 from the gas inlet 27, and a high-frequency voltage with a negative bias applied from the high-frequency power source 8 to the holding electrode 3. (RF: 1
3.56 MHz), the holding electrode 3
The plasma P is generated by a gas discharge phenomenon caused by a high-frequency glow discharge between the electrode P and the counter electrode 4. In the plasma P thus generated, as described above, the ionized O
⁺ Or N ⁺ ions and electrons are present and oxygen or nitrogen radicals are present.
Is applied with a negatively biased high-frequency voltage, so that the intermediate electrode 5 is in an electrically negative state. Therefore, O ⁺ or N ⁺ in the plasma P
Such ions are attracted to and sucked by the intermediate electrode 5, so that the ions in the plasma P cannot pass through the intermediate electrode 5. On the other hand, electrically neutral radicals in the plasma P are not attracted to the intermediate electrode 5 and can pass through the intermediate electrode 5.

As described above, the ions in the plasma P are attracted to the intermediate electrode 5, so that the radicals can mainly reach the surface of the resin molded body 1 and the ions can be prevented from reaching. The surface of the body 1 is treated mainly by the action of radicals, and polar groups such as an oxygen polar group and a nitrogen polar group can be provided to the resin molecules on the surface of the resin molded body 1. Since the resin molecules on the surface of the resin molded body 1 are cleaved by the first-stage treatment as described above, the treatment for imparting a polar group can be performed with high efficiency. The treatment to be applied is mainly performed by radicals in the plasma P, and the ions hardly act on the surface of the resin molded body 1, so that the surface of the resin molded body 1 is not etched by ions having high energy, and The polar group formed on the surface of the body 1 is not removed by this etching, and the polar group can be formed on the surface of the resin molded body 1 at a high density.
In the embodiment shown in FIG. 3, the ions in the plasma P can be removed by biasing the intermediate electrode 5 negatively.
However, it is also possible to cause the ions in the plasma P to be attracted to the intermediate electrode 5 by grounding the intermediate electrode 5.

After the first and second steps are performed on the surface of the resin molding 1 by the plasma as described above, the metal film 2 is formed on the surface of the resin molding 1 as described above. is there. Since the polar group is formed on the surface of the resin molded body 1 with high efficiency and high density as described above, the resin molded body 1 is formed of a resin having no polar group in the molecule, such as LCP or SPS. Even so, the metal film 2 can be formed on the surface of the resin molded body 1 with high adhesion. Further, according to the present invention, in performing the second stage processing,
As shown in FIG. 1 (b) of the invention, two chambers are not required, and the equipment can be miniaturized.

Here, the effects of the second and third aspects of the present invention will be demonstrated with specific examples.

The resin molded article 1 was prepared by injection molding LCP. Then, in the apparatus shown in FIG. 1A, a treatment for cleaving molecules on the surface of the resin molded body 1 was performed under the same conditions as described above. Next, in the apparatus of FIG. 3 provided with the mesh-shaped intermediate electrode 5 provided with holes at a pitch of 1 mm, a nitrogen gas was used as an atmosphere gas, and a gas pressure of 10 P
a, a plasma P was generated under the conditions of a bias voltage of -200 V and an RF power of 500 W, and a process of giving a polar group to molecules on the surface of the resin molding 1 was performed with the plasma P for 30 seconds. Thereafter, DC magnetron sputtering was performed to form a 0.3 μm thick copper metal film 2 on the surface of the resin molded body 1. When the peel strength of this metal film 2 was measured, it was 0.70 N / mm.

FIG. 4 is a cross-sectional view of the second and fourth embodiments of the present invention, in which a polar group is added to the molecules of the resin on the surface of the resin molded article 1
This shows an example of a plasma processing apparatus for performing a step process, in which a holding electrode 3 and a counter electrode 4 are provided in a chamber 29 so as to face each other. The holding electrode 3 is formed as a tray and is grounded, and the counter electrode 4 is connected to the R through a matching box 26.
F is connected to the high frequency power supply 8. Chamber 29
Is provided with a gas inlet 30 so that an atmospheric gas for plasma generation can be introduced into the chamber 29 from the gas inlet 30.

Then, after the first-stage treatment for cleaving the resin molecules on the surface of the resin molded body 1 as shown in FIG. 1 (a), the resin molded body 1 is moved to the holding electrode 3 in the chamber 29. And the gas inlet 30 and the chamber 29
An oxygen gas or a nitrogen gas is introduced as an atmospheric gas into the inside, and a high-frequency voltage (RF: 13.56 MHz) with a negative bias applied from a high-frequency power supply 8 is applied to the counter electrode 4 so that the holding electrode 3 and the counter electrode are The plasma P is generated by the gas discharge phenomenon caused by the high-frequency glow discharge during the period 4. In the plasma P thus generated,
As described above, ions and electrons such as ionized O ⁺ or N ⁺ are present and oxygen or nitrogen radicals are present, but a high frequency voltage with a negative bias is applied to the counter electrode 4. O ^{+ in} plasma P
Alternatively, ions such as N ⁺ are attracted to and attracted by the counter electrode 4, and ions in the plasma P are less likely to move toward the resin molded body 1 on the holding electrode 3. On the other hand, the electrically neutral radicals in the plasma P are not attracted to the counter electrode 4, so that the radicals can travel toward the resin molded body 1 on the holding electrode 3 without any trouble.

As described above, the ions in the plasma P are attracted to the counter electrode 4, so that electrically neutral radicals mainly reach the surface of the resin molding 1, and the ions hardly reach the resin molding 1. The surface of the resin molded article 1 is treated mainly by the action of radicals,
A polar group such as an oxygen polar group or a nitrogen polar group can be imparted to the molecules of the resin on the surface of the resin. Since the resin molecules on the surface of the resin molded body 1 are cleaved by the first-stage treatment as described above, the treatment for imparting a polar group can be performed with high efficiency. The treatment to be applied is mainly performed by radicals in the plasma P, and the ions hardly act on the surface of the resin molded body 1. Even if the ions act on the resin molded body 1, the collision energy is very small, so that the high energy is applied. The surface of the resin molded body 1 is not etched by the ions having the above, and the polar groups formed on the surface of the resin molded body 1 are not removed by this etching. It is possible to form a polar group at a high density on the surface. Note that a third intermediate electrode 5 formed of a metal mesh or the like may be disposed between the holding electrode 3 and the counter electrode 4 so that the intermediate electrode 5 may be negatively biased. The ions can be further prevented from acting on the resin molded article 1 by the ions being attracted.

After the first and second steps are performed on the surface of the resin molded body 1 by the plasma as described above, the metal film 2 is formed on the surface of the resin molded body 1 as described above. is there. Since the polar group is formed on the surface of the resin molded body 1 with high efficiency and high density as described above, the resin molded body 1 is formed of a resin having no polar group in the molecule, such as LCP or SPS. Even so, the metal film 2 can be formed on the surface of the resin molded body 1 with high adhesion. Further, according to the present invention, in performing the second stage processing,
As shown in FIG. 1 (b) of the invention, two chambers are not required, and the equipment can be miniaturized.

Here, the effects of the second and fourth aspects of the present invention will be demonstrated with specific examples.

As the resin molded product 1, a product produced by injection molding of LCP was used. Then, in the apparatus shown in FIG. 1A, a treatment for cleaving molecules on the surface of the resin molded body 1 was performed under the same conditions as described above. Next, in the apparatus shown in FIG. 4, a plasma P is generated under the conditions of a gas pressure of 10 Pa, a bias voltage of -200 V, and an RF power of 500 W using nitrogen gas as an atmosphere gas. A treatment for giving a polar group to molecules on the surface was performed. After that, DC magnetron sputtering is performed,
A 0.3 μm thick copper metal film 2 was formed on the surface of the resin molded body 1. When the peel strength of the metal film 2 was measured, it was 0.72 N / mm.

Next, the invention of claim 5 will be described.

In the embodiment shown in FIG. 1A, the high-frequency voltage (RF: 13.5) is applied to the holding electrode 3 from the high-frequency power source 8.
By applying 6 MHz), a plasma P such as Ar plasma is generated between the holding electrode 3 holding the resin molded body 1 and the counter electrode 4 to cleave the bonds of the resin molecules on the surface of the resin molded body 1. At this time, the plasma processing is performed. At this time, a high-frequency voltage with a negative bias is applied from the high-frequency power supply 8 to the holding electrode 3 holding the resin molded body 1 to generate plasma P, thereby forming the resin molded body 1. The holding electrode 3 for holding the electrode 1 is electrically negative, and ions such as Ar ⁺ in the plasma P are electrically attracted to easily collide with the surface of the resin molding 1 so that the resin molding 1 The treatment for cleaving the molecular bond of the resin on the surface of No. 1 is promoted. However, if the energy of ions such as Ar ⁺ colliding with the surface of the resin molding 1 is excessive, the resin surface layer of the resin molding 1 is damaged and deteriorated, and a fragile layer is formed on the resin surface layer. May be affected. The fragile layer is called a WBL (Weak Boundary Layer) as introduced in JP-A-8-3338 and the like. Even if a polar group is formed on the fragile layer, the strength of the fragile layer is weak. The peel strength of the metal film 2 cannot be improved.

Therefore, in the invention of claim 5, as shown in FIG.
As described above, the bias voltage control device 32 is connected to the high frequency power supply 8.
And a negative voltage applied to the holding electrode 3 from the high-frequency power source 8.
DC bias voltage value (V_DC) This bias voltage control
It is controlled by the device 32. And the holding electrode 3
V applied to_DCWithin the range of -100V to -700V
By controlling, Ar⁺Ions in plasma P
The collision energy when collides with the surface of the resin molding 1
It is something that can be optimized. V _DCIs -7
If the voltage is more negative than 00V, Ar⁺Ion opposition
The impact energy becomes excessive, and the resin
A fragile layer may be formed on the surface._DCIs -1
If the voltage is more positive than 00V, the surface of the resin molding 1
Ar to surface⁺Ion collision energy is too small
And the action of cleaving the resin molecules becomes insufficient.
There is it.

In each of the above-mentioned inventions, the first-stage treatment for cleaving the bond of the resin molecules on the surface of the resin molded body 1 is performed by plasma, but in the inventions of claim 6 and claim 7, The first-stage processing is performed by laser irradiation. That is, as shown in FIG. 6, a laser L such as an excimer laser, an argon laser, and a He-Cd laser output from the laser oscillator 34 is used.
By irradiating the surface of the resin molding 1 set on the posture control table 35 capable of changing the posture in the X, Y, and Z directions, the bond of the resin molecules on the surface of the resin molding 1 is cleaved. That can be done.

Here, when the surface of the resin molded body 1 has a three-dimensional three-dimensional shape, there are standing surfaces and slopes, but when performing the plasma treatment, the processing is performed between the flat surface and the standing surfaces or slopes. It is easy to make a difference in the effect. On the other hand, in the case of the processing by the laser, since the processing in the atmosphere is possible, the laser irradiation processing can be performed by using the attitude control table 35, and the flat surface or the rising surface of the resin molded body 1 can be obtained. It is easy to carry out the treatment in the state where each of them is at the same angle with respect to the laser, and it becomes easy to carry out a uniform treatment on the surface of the three-dimensionally shaped resin molded body 1.

The effect of the sixth aspect of the present invention will be demonstrated with reference to specific examples.

As the resin molded product 1, a product produced by injection molding LCP was used. In the apparatus shown in FIG. 6, the excimer laser L is irradiated with an energy density of 0.5 J / cm ² ,
Irradiation was performed under the condition of a number of shots of 100 shots, so that molecules on the surface of the resin molded body 1 were cleaved. Next, in the apparatus shown in FIG. 1 (b), a treatment for imparting a polar group to molecules on the surface of the resin molded body 1 was performed under the conditions described above. Thereafter, DC magnetron sputtering was performed to form a 0.3 μm thick copper metal film 2 on the surface of the resin molded body 1. When the peel strength of the metal film 2 was measured, it was 0.73 N / mm.

According to an eighth aspect of the present invention, as in each of the above-mentioned inventions, after performing the second step of providing a polar group to the resin molecules on the surface of the resin molded body 1 with radicals in the plasma, the resin molding is performed. The surface of the body 1 is further subjected to plasma treatment to obtain a resin molded body 1
The resin molecules on the surface, particularly the molecules of the fragile layer, are crosslinked. In this plasma processing, for example, an inert gas such as argon is used as an atmosphere gas, for example, a gas pressure of 15 Pa, an RF power of 100 W, and a processing time of 60 Pa.
It can be carried out under conditions of up to 120 seconds. By performing the plasma treatment in this manner, as shown in FIG. 7, ultraviolet rays UV generated from the plasma P are radiated to the surface of the resin molded body 1, and the molecules of the resin on the surface undergo a crosslinking reaction by the action of the ultraviolet rays, and Even if a fragile layer is formed on the surface by the first and second steps, the fragile layer can be reinforced by crosslinking the molecules on the resin surface. Therefore, the effect of improving the peel strength of the metal film 2 due to the weak strength of the fragile layer does not occur, and the effect of improving the peel strength of the metal film 2 can be effectively obtained.

According to the ninth aspect of the present invention, when the plasma treatment is performed to crosslink the resin molecules on the surface of the resin molded body 1, the resin molded body 1 emits light from the plasma P as shown in FIG. Ultraviolet UV is passed, but plasma P
The inside ions are surrounded by a barrier 9 that does not allow passage of ions. That is, the holding electrode 3 and the counter electrode 4 are provided so as to face each other in the chamber 37, and the third electrode is provided between the resin molded body 1 set on the holding electrode 3 and the counter electrode 4. The barrier 9 is arranged as a. The barrier 9 is formed of a metal mesh or the like, and is biased to a negative voltage. Then, an argon gas is introduced as an atmosphere gas into the chamber 37 and a high-frequency voltage is applied to the holding electrode 3 to generate a plasma P by a gas discharge phenomenon caused by a high-frequency glow discharge between the holding electrode 3 and the counter electrode 4. The surface of the resin molded body 1 is irradiated with ultraviolet rays emitted from P to crosslink the resin molecules on the surface of the resin molded body 1. At this time, since a negative bias is applied to the barrier 9 surrounding the resin molded body 1, ions such as Ar ^{+ in} the plasma P are attracted to and sucked by the barrier 9, and the ions in the plasma P are absorbed by the barrier 9. Can not pass through. Therefore, the ultraviolet rays UV emitted from the plasma P can be applied to the surface of the resin molded body 1 without the ions in the plasma P colliding with the surface of the resin molded body 1 and etching the surface. Things. In the above-described embodiment, an electrode biased to a negative voltage is used as the barrier 9, but any electrode may be used as long as it allows ultraviolet rays to pass but does not allow ions in the plasma P to pass.
For example, a quartz glass plate can be used as the barrier 9.

The tenth aspect of the present invention is the resin molded article 1 described above.
The process of cross-linking the resin molecules on the surface is performed by ultraviolet irradiation. When the resin molecules on the surface of the resin molded body 1 are crosslinked by the plasma treatment,
Molecules may be cleaved by the etching action of ions in the plasma, and the effect of surface strengthening by cross-linking may be reduced. The surface of the resin molded article 1 can be reinforced without any problem.

According to an eleventh aspect of the present invention, the ultraviolet irradiation is performed by using an ultraviolet laser. An excimer laser can be used as the ultraviolet laser. For example, using a KrF excimer laser having a wavelength of 248 nm, an energy density of 10 mj / cm ² ,
By irradiating under the condition of 10 shots, the resin molecules on the surface of the resin molded body 1 can be cross-linked by ultraviolet rays to enhance the surface.

According to a twelfth aspect of the present invention, the ultraviolet irradiation is performed 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. Excimer lamps can be made simpler, smaller, and cheaper than devices that irradiate ultraviolet laser.

Further, in the invention of claim 13, in the above-mentioned inventions, prior to performing the first step of cleaving the bonding of the molecules of the resin on the surface of the resin molded article 1, the pre-processing may be performed as a preliminary step. The plasma treatment for etching and roughening the surface of the molded body 1 is performed. This plasma treatment uses, for example, oxygen gas as an atmosphere gas, a gas pressure of 10 Pa, an RF power of 500 W, and a treatment time of 2 hours.
It can be performed under conditions of up to 5 minutes. By performing the plasma treatment in this manner, carbon and hydrogen as elements constituting the resin of the resin molded product 1 react with active species of oxygen to form carbon monoxide, carbon dioxide, water, and the like. It can be separated from the surface to form fine irregularities on the surface of the resin molded body 1 and roughen the surface. By roughening the surface of the resin molded body 1 in this manner, the adhesion of the metal film 2 formed on the surface of the resin molded body 1 can be improved by the anchor effect due to the roughening irregularities. is there.

According to a fourteenth aspect of the present invention, the preliminary plasma treatment for roughening the surface of the resin molded body 1 as described above is performed using an oxygen gas or an ozone gas as an atmosphere gas. When the treatment is performed with oxygen plasma or ozone plasma in this manner, oxygen or ozone is easily bonded to carbon of the molecules on the resin surface, so that the etching rate is increased and the processing time for surface roughening can be shortened.

[0070] Next, in the invention of claim 15, as in the above-mentioned inventions, in performing the second step of imparting a polar group to the molecules of the resin on the surface of the resin molded article 1 with radicals in the plasma, This process is performed while heating the resin molded body 1. By heating the resin molded body 1, the activity of the resin molecules of the resin molded body 1 increases,
The application of the polar group to the resin molecule is promoted, and the formation of the polar group can be performed with high efficiency and high density.

According to a sixteenth aspect of the present invention, when the resin molded body 1 is heated as described above, the heating temperature of the resin molded body 1 is set to the glass transition temperature (T
g) The temperature is set within a range of ± 30 ° C.
The resin molded body 1 is set to a temperature range of Tg ± 30 ° C.,
By performing a second-stage treatment of imparting a polar group to the resin molecules on the surface of the resin molded body 1 with radicals in the plasma while heating in the range of g ± 10 ° C., the polar groups are converted into the resin molecules. The application can be promoted, and the formation of the polar group can be performed with high efficiency and high density. When the heating temperature is lower than Tg-30 ° C., the effect of promoting the provision of the polar group becomes insufficient, and conversely, the heating temperature becomes Tg + 3.
When the temperature is higher than 0 ° C., the resin molded body 1 may be thermally deformed or thermally degraded.

According to a seventeenth aspect of the present invention, when heating the resin molded body 1 as described above, only the surface layer of the resin molded body 1 is heated. Resin molding 1 is T
g ± 30 ° C., when the entire resin molding 1 is heated to this temperature, the resin molding 1
May be deformed. Therefore, in the invention of claim 17, only the surface layer of the resin molded body 1 is heated so that only the surface layer of the resin molded body 1 is heated to a temperature of Tg ± 30 ° C. At this time, 10 to 50 μm from the surface of the resin molded body 1
The heating is preferably performed so that the range up to m is Tg ± 30 ° C.

According to the eighteenth aspect of the invention, when only the surface layer of the resin molded body 1 is heated as described above, heating is performed by irradiating the surface of the resin molded body 1 with heat rays. . Since the heat rays do not penetrate into the resin molded body 1, only the surface layer portion of the resin molded body 1 can be uniformly heated by scanning the heat rays along the surface of the resin molded body 1. As a heat ray, a CO ₂ laser, an infrared beam, or the like can be used, and a halogen lamp or the like can be used as a heat source of the heat ray. For example, when a CO ₂ laser is used as a heat ray, heating can be performed by irradiation with an energy density of 1 J / cm ² .

According to a nineteenth aspect of the present invention, as in each of the above-mentioned inventions, the radical in the plasma is subjected to the second step of imparting a polar group to the molecules of the resin on the surface of the resin molded body 1, and the radical is converted to the radical. NH ₃ ,
A gas selected from SO ₂ , NO ₂ , CO and the like is used. By using a plasma generated by using these gases as an atmosphere gas, a polar group having a higher electron affinity can be imparted to the molecules of the resin than by using plasma generated by using a nitrogen gas as an atmosphere gas. For example, the electron affinity of SO ₂ is 1.1
The electron affinity of eV and NO ₂ is 2.4 eV, and by using the above-mentioned gas such as NH ₃ , SO ₂ , NO ₂ , CO as an atmosphere gas, for example, an amino group (−N
H ₂ ), a sulfonyl group (—SO ₂ ), a carbonyl group (—C
A polar group having a high electron affinity such as O-) can be provided to a resin molecule. Here, in the bond between the resin and the metal, it is desirable to coordinate the bond from the viewpoint of the adhesion between the two. However, the higher the electron affinity of the resin and the lower the electronegativity of the metal, the easier the coordinate bond. Since the metal has a small electronegativity, NH ₃ , SO ₂ , N
By providing a polar group having a high electron affinity using plasma of a gas selected from O ₂ , CO, etc., the bonding force between the metal and the polar group is increased. Therefore, the resin molding 1
And a metal film 2 formed after providing a polar group on its surface
Thus, the adhesion between the resin molded body 1 and the metal film 2 can be increased.

According to a twentieth aspect of the present invention, as in each of the above-mentioned inventions, after the second stage treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 with radicals in the plasma, it is necessary After performing a process of crosslinking the resin molecules on the surface of the resin molded body 1 according to the above, prior to forming the metal film 2 on the surface of the resin molded body 1, the adhesion to the resin molded body 1 is higher than that of the metal film 2. A high metal is pre-coated on the surface of the resin molding 1.

That is, as shown in FIG. 9 (b), a polar group 10 is provided on the surface of the resin molded body 1, and the surface of the resin molded body 1 is coated with a metal by a PVD method such as sputtering to form a substrate. The pre-coated metal film 6 is formed as shown in FIG. The pre-coated metal film 6 is formed of a metal having higher adhesiveness to the resin molded body 1 than the metal film 2 as described above. For example, the resin molded body 1 made of LCP or SPS is used.
When a Cu metal film 2 is formed on the surface of Ti, Ti, C
The precoat metal film 6 is formed using a metal selected from r, Ni, and the like. After forming the pre-coated metal film 6, the metal film 2 such as Cu is formed on the pre-coated metal film 6 as shown in FIG. 9D. Since the adhesion between the metals is much higher than the adhesion between the metal and the resin, as described above, between the resin molded body 1 and the metal film 2,
The presence of the pre-coated metal film 6 having higher adhesion to the resin molded body 1 than the metal film 2 allows the resin molded body 1
High adhesion to the metal film 2 can be obtained. This pre-coated metal film 6 has a thickness of 0.01 to 0.1 μm.
It is preferable to form it with a thickness of m.

According to a twenty-first aspect of the present invention, in forming the pre-coated metal film 6 on the surface of the resin molded body 1 as described above, the resin molded body 1 is made to have a glass transition temperature (Tg) of the resin constituting the resin molded body 1. ) The metal coating is performed while heating in the range of ± 30 ° C. The resin molded body 1 is placed in a temperature range of Tg ± 30 ° C., particularly preferably Tg ± 30 ° C.
By coating a metal and forming a film while heating in the range of 10 ° C., high adhesion between the resin molded body 1 and the pre-coated metal film 6 can be obtained. If the heating temperature is lower than Tg−30 ° C., the effect of improving the adhesion of the pre-coated metal film 6 to the resin molded body 1 becomes insufficient, and if the heating temperature is higher than Tg + 30 ° C., 1 may be thermally deformed or thermally degraded. The heating of the resin molded body 1 is preferably performed only on the surface layer portion, as described above.

According to a twenty-second aspect of the present invention, in forming the pre-coated metal film 6 on the surface of the resin molded body 1 as described above, the pre-coated metal film 6 is formed of a metal oxide. As the metal oxide, an oxide of a metal having higher adhesion to the resin molded body 1 than the metal film 2 is used. For example, the surface of the resin molded body 1 made of LCP or SPS is made of Cu metal. When the film 2 is formed, an oxide of a metal selected from Ti, Cr, Ni and the like is used. In this case, copper oxide can be used as the metal oxide. By forming the pre-coated metal film 6 with the metal oxide in this manner, the adhesion of the metal film 2 to the resin molded body 1 can be further improved.

Here, the formation of the pre-coated metal film 6 of a metal oxide on the surface of the resin molded body 1 can be performed by a reactive sputtering method. FIG.
Reference numeral 0 denotes an example of a sputtering apparatus, and a holder 38 for holding the resin molded body 1 in a chamber 37.
And a metal target 39 selected from the above-mentioned Ti, Cr, Ni and the like are arranged, and sputtering is performed by generating plasma P of oxygen gas or plasma P of a mixed gas of an inert gas such as argon and oxygen. The metal of the target 39 is reacted with oxygen to form a metal oxide, and is deposited on the surface of the resin molded body 1.
Can form a pre-coated metal film 6 of a metal oxide on the surface thereof.

According to a twenty-third aspect of the present invention, after performing the second stage treatment of imparting a polar group to the molecules of the resin on the surface of the resin molded body 1 with radicals in the plasma,
Further, if necessary, after performing a process of crosslinking the resin molecules on the surface of the resin molded body 1, before forming the metal film 2 on the surface of the resin molded body 1, the adhesion to the metal film 2 is reduced. A resin higher than the resin No. 1 is pre-coated on the surface of the resin molded body 1.

That is, as shown in FIG. 11B, a polar group 10 is provided on the surface of the resin molded body 1, and the resin is vapor-phase polymerized on the surface of the resin molded body 1 by vapor deposition polymerization or plasma polymerization. A pre-coated resin film 7 is formed as shown in FIG.
The pre-coated resin film 7 is formed of a resin having higher adhesion to the metal film 2 than the resin of the resin molded body 1 as described above. For example, the surface of the resin molded body 1 made of LCP or SPS When the Cu metal film 2 is formed, the pre-coat resin film 7 is formed using polyimide, polyamide, or the like. After forming the pre-coat resin film 7, the metal film 2 of Cu or the like is formed on the pre-coat resin film 7 as shown in FIG. Since the adhesiveness between the resins is much higher than the adhesiveness between the resin and the metal, the adhesiveness between the resin molding 1 and the metal film 2 with the metal film 2 is higher than that of the resin of the resin molding 1. Of the resin molded product 1 due to the presence of the precoated resin film 7
High adhesion to the metal film 2 can be obtained. This pre-coated resin film 7 has a thickness of 0.05 to 0.1 μm.
It is preferable to form it with a thickness of m. For example, when forming a polyimide pre-coated resin film 7, vapor deposition polymerization is performed under the conditions of pyromellitic anhydride (PMDA) and diphenylamine (ODA) at a temperature of about 200 ° C., a chamber temperature of 300 ° C., and a temperature of the resin molded body 1 of 200 ° C. Thereby, the pre-coated resin film 7 having a thickness of 0.1 μm or less can be formed.

[0082]

As described above, in the method for forming a metal film on a resin molded product according to the first aspect of the present invention, after performing a plasma treatment for cleaving the bonding of the resin molecules on the surface of the resin molded product,
By directing the plasma to the surface of the resin molded article by the downstream method, radicals in the plasma mainly reach the surface of the resin molded article, and the action of these radicals imparts a polar group to the resin molecules on the surface of the resin molded article. After that, a metal film is formed on the surface of the resin molded body, so that a polar group can be provided in a state where the resin molecules on the surface of the resin molded body are cleaved, The treatment for imparting the polar group can be performed efficiently with radicals in the plasma,
The surface of the resin molded body is not etched by the ions having high energy, and the polar group can be formed at a high density, and the metal film can be formed on the resin molded body with high adhesion. Things.

According to the method for forming a metal film on a resin molded product according to the second aspect of the present invention, after performing a plasma treatment for cleaving the bonding of resin molecules on the surface of the resin molded product, ions in the plasma are applied to the electrode. By preventing it from reaching the surface of the resin molded body by being electrically sucked, the radicals in the plasma mainly reach the surface of the resin molded body, and the radicals act on the resin molecules on the surface of the resin molded body by the action of the radicals. Since a process for providing a polar group is performed, and thereafter, a metal film is formed on the surface of the resin molded body, the polar group can be provided in a state where the resin molecules on the surface of the resin molded body are cleaved. The polar group can be efficiently imparted, and the process of imparting the polar group is mainly performed by radicals in the plasma, and ions having high energy are applied to the surface of the resin molded body. Gone to be etched, which the polar group can be formed at a high density, it is capable of adhesion increases forming a metal film on the resin molding.

According to a third aspect of the present invention, in the above-mentioned second aspect, the resin molded body is held in the process of imparting a polar group to the resin molecules on the surface of the resin molded body by the action of radicals in the plasma. Plasma is generated between the holding electrode and a counter electrode facing the resin molded body, and the ions in the plasma are surrounded by an intermediate electrode that electrically attracts the ions in the plasma. Therefore, the ions in the plasma can be electrically attracted to the intermediate electrode so as not to reach the surface of the resin molded body.

According to a fourth aspect of the present invention, in the above-described second aspect, the resin molded body is held in the process of imparting a polar group to the resin molecules on the surface of the resin molded body by the action of radicals in the plasma. Plasma is generated between the holding electrode and the counter electrode facing the resin molded body, and a high frequency voltage with a negative bias is applied to the counter electrode, thereby electrically attracting ions in the plasma to the counter electrode. Since the ions in the plasma are prevented from reaching the surface of the resin molded body, the ions in the plasma are electrically attracted to the counter electrode side so as not to reliably reach the surface of the resin molded body. You can do it.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, a plasma is generated between a holding electrode for holding the resin molded body and a counter electrode opposed to the resin molded body, and the resin molding is performed. In performing the plasma treatment for breaking the bonds of the resin molecules on the body surface, a high frequency voltage having a negative bias applied to the holding electrode is applied, and the negative bias voltage is controlled in a range of -100V to -700V. , It is possible to optimize the collision energy of the ions in the plasma to the surface of the resin molded body,
The process for cleaving the resin molecules can be performed without forming a fragile layer on the surface of the resin of the resin molded body.

In the method for forming a metal film on a resin molded product according to a sixth aspect of the present invention, a treatment is performed to irradiate a laser to the surface of the resin molded product to cleave the bonds of the resin molecules on the surface of the resin molded product. After that, the plasma is led to the surface of the resin molded article by the downstream method, so that radicals in the plasma mainly reach the surface of the resin molded article, and the action of the radicals polarizes the resin molecules on the surface of the resin molded article. Since the treatment to add a group, after that, a metal film is formed on the surface of the resin molded body, it is possible to impart a polar group in a state where the resin molecules on the surface of the resin molded body are cleaved,
The addition of the polar group can be performed with high efficiency, and the process of providing the polar group is mainly performed by radicals in plasma, so that the surface of the resin molded body is not etched by ions having high energy,
A polar group can be formed at a high density, and a metal film can be formed on a resin molded body with high adhesion.

In the method for forming a metal film on a resin molded product according to the present invention, the surface of the resin molded product is irradiated with a laser to cleave the bonds of the resin molecules on the surface of the resin molded product. After that, the ions in the plasma are electrically attracted to the electrodes to prevent the ions from reaching the surface of the resin molded body, so that the radicals in the plasma mainly reach the surface of the resin molded body and the action of the radicals A process of adding a polar group to the resin molecules on the surface of the resin molded body,
After that, since the metal film is formed on the surface of the resin molded body, the polar group can be provided in a state where the resin molecules on the surface of the resin molded body are cleaved, and the polar group is efficiently provided. At the same time, the treatment for providing the polar group is performed mainly by radicals in the plasma, so that the surface of the resin molded body is not etched by ions having high energy, and the polar group is formed at a high density. The metal film can be formed on the resin molded body with high adhesion.

The invention according to claim 8 is the method according to any one of claims 1 to 7, wherein a treatment is carried out for imparting a polar group to the molecules of the resin on the surface of the resin molded body with radicals in the plasma, and then performing the plasma treatment. The resin molecules on the surface of the resin molded body are cross-linked to strengthen the surface of the resin molded body by the cross-linking of the molecules, thereby further improving the adhesion of the metal film to the surface of the resin molded body. Can be done.

Further, according to the invention of claim 9, the surface of the resin molded body is surrounded by a barrier which allows ultraviolet rays emitted from the plasma to pass but does not allow ions in the plasma to pass therethrough. Since the plasma treatment for cross-linking the resin molecules is performed, it is possible to prevent ions in the plasma from colliding with the surface of the resin molded body when cross-linking the resin molecules with ultraviolet light from the plasma, The crosslinking can be prevented from being cleaved by the action of ions.

The invention according to claim 10 is the method according to any one of claims 1 to 7, wherein the treatment in the plasma is carried out to give a polar group to the molecules of the resin on the surface of the resin molded article by radicals in the plasma, and then the ultraviolet irradiation treatment is performed. To crosslink the resin molecules on the surface of the resin molded body, so that the surface of the resin molded body can be strengthened by the crosslinking of the molecules, and the adhesion of the metal film to the surface of the resin molded body is further enhanced. Is what you can do.

The invention of claim 11 provides the above-mentioned claim 10.
In the above, the ultraviolet irradiation treatment is performed using an ultraviolet laser, so that the ultraviolet light is irradiated to crosslink the resin molecules on the surface of the resin molded body, and the surface of the resin molded body is reinforced by the crosslinking of the molecules. Can be done.

Further, the invention of claim 12 provides the above-mentioned claim 10
In, the ultraviolet irradiation treatment is performed using an excimer lamp, so that the resin molecules on the surface of the resin molded article are cross-linked by irradiating ultraviolet rays emitted from the excimer lamp, and the cross-linking of the molecules causes the resin molded article to be crosslinked. The surface can be strengthened.

According to a thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the surface of the resin molded body is roughened prior to the step of cleaving the bonding of the molecules of the resin on the surface of the resin molded body. Since the plasma treatment is performed, the adhesion of the metal film to the resin molded body can be increased by the anchor effect due to the roughening irregularities.

The invention of claim 14 is the invention of claim 13
In the above, the plasma treatment for roughening the surface of the resin molded body with plasma using oxygen or ozone as an atmospheric gas is performed, so that the oxygen or ozone plasma has a high etching rate and shortens the processing time for surface roughening. Is what you can do.

According to a fifteenth aspect of the present invention, in any one of the first to fourteenth aspects, the treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded product by the action of radicals in the plasma is performed by the resin molded product. Is performed while heating, the activity of the resin molecules of the resin molded body is increased, the provision of polar groups to the resin molecules is promoted, and the formation of the polar groups can be performed with high efficiency and high density. You can do it.

The invention of claim 16 is the invention of claim 15
In the method, the resin molded body is heated at a temperature of ± 30 ° C., which is the glass transition temperature of the resin of the resin molded body. It can promote the provision of a polar group.

The invention of claim 17 provides the above-mentioned claim 15.
Alternatively, in step 16, since only the surface layer of the resin molded body is heated, there is no risk of deformation of the resin molded body as in the case where the entire resin molded body is heated.

The invention according to claim 18 is based on claim 17.
In the method, since the surface of the resin molded body is irradiated with a heat ray to heat only the surface layer portion of the resin molded body, the heat ray hardly penetrates into the inside of the resin molded body, and only the surface layer portion is easily heated. Is what you can do.

The invention according to claim 19 is the invention according to any one of claims 1 to 18, wherein the treatment for imparting a polar group to the molecules of the resin on the surface of the resin molded article by the action of radicals in the plasma is performed as an atmosphere gas. NH ₃ , SO ₂ , NO ₂ , CO
Is performed by using a plasma selected from the group consisting of: a polar group having a high electron affinity can be imparted to the resin molecules of the resin molded body, and the adhesion of the metal film to the surface of the resin molded body is further enhanced. Is what you can do.

The invention according to claim 20 is the method according to any one of claims 1 to 19, wherein the metal having higher adhesion to the resin molded body than the metal film is formed before forming the metal film on the surface of the resin molded body. Since the surface of the resin molded body is pre-coated and the above-mentioned metal film is formed on the pre-coated metal film, the adhesion between the resin molded body and the metal film is higher than that of the metal film. The presence of the pre-coated metal film can further enhance the adhesion of the metal film to the resin molded product.

The invention according to claim 21 is based on the above-mentioned claim 20.
In the above, the resin molded body is heated at a temperature of ± 30 ° C. of the glass transition temperature of the resin of the resin molded body so that the metal is pre-coated, so that the resin molded body does not undergo thermal deformation or thermal deterioration. In addition, a pre-coated metal film can be formed by increasing the adhesion to a resin molded body.

According to a twenty-second aspect of the present invention, since the pre-coated metal film is formed of a metal oxide in the twentieth or twenty-first aspect, the adhesion of the metal film to the resin molding can be further improved. It is.

According to a twenty-third aspect of the present invention, prior to forming a metal film on the surface of the resin molded product, a resin having higher adhesion to the metal film than the resin of the resin molded product is precoated on the surface of the resin molded product. Since the above-mentioned metal film is formed on the pre-coated resin film, there is a pre-coated metal film between the resin molded product and the metal film, which has higher adhesion to the metal film than the resin of the resin molded product. Then, the adhesion of the metal film to the resin molded body can be further enhanced.

[Brief description of the drawings]

FIG. 1 shows an example of an embodiment of the present invention,
(A) is a schematic diagram showing a plasma treatment for cleaving a bond of a resin molecule of a resin molded product, and (b) is a schematic diagram showing a plasma treatment for giving a polar group to a resin molecule of the resin molded product.

FIG. 2 is a cross-sectional view showing a state of processing of the resin molded body according to the first embodiment, wherein (a), (b), and (c) are cross-sectional views.

FIG. 3, showing another example of the embodiment of the present invention, is a schematic view showing a plasma treatment for giving a polar group to a resin molecule of a resin molded product.

FIG. 4 shows another example of the embodiment of the present invention, and is a schematic view showing a plasma treatment for giving a polar group to a resin molecule of a resin molded product.

FIG. 5 shows another example of the embodiment of the present invention, and is a schematic view showing a plasma treatment for cleaving a bond between molecules of a resin of a resin molded product.

FIG. 6, showing another example of the embodiment of the present invention, is a schematic view showing a laser treatment for cleaving a bond of a resin molecule of a resin molded product.

FIG. 7 shows another example of the embodiment of the present invention, and is a schematic view showing a plasma treatment for cross-linking resin molecules of a resin molded product.

FIG. 8 shows another example of the embodiment of the present invention, and is a schematic view showing a plasma treatment for cross-linking resin molecules of a resin molded product.

FIG. 9 shows a state of processing of a resin molded body according to another example of the embodiment of the present invention, wherein (a), (b),
(C) and (d) are sectional views, respectively.

FIG. 10 illustrates another example of the embodiment of the present invention, and is a schematic view illustrating a process of forming a precoat resin film on a surface of a resin molded product.

FIG. 11 shows a state of processing of a resin molded body according to another example of the embodiment of the present invention, wherein (a),
(B), (c), and (d) are sectional views, respectively.

FIG. 12 is a schematic view showing a conventional plasma processing.

FIG. 13 is a graph showing the peel strength of a metal film before and after a conventional plasma process.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Resin molded object 2 Metal film 3 Holding electrode 4 Counter electrode 5 Intermediate electrode 6 Precoat metal film 7 Precoat resin film 8 High frequency power supply 9 Barrier 10 Polar group

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoto Ikegawa 1048 Kazumasa Kadoma, Osaka Prefecture Inside Matsushita Electric Works, Ltd. Term (reference) 4F006 AA38 AB73 CA05 CA08 DA01 EA03 4F073 AA01 BA29 BB01 CA01

Claims (23)

[Claims] After performing a plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded product, the plasma is guided to the surface of the resin molded product by a downstream method.
The radicals in the plasma mainly reach the surface of the resin molded body, and a process of imparting a polar group to the molecules of the resin on the surface of the resin molded body by the action of the radical is performed. Forming a metal film on a resin molding. 2. After performing a plasma treatment for cleaving the bond of the resin molecules on the surface of the resin molded body, ions in the plasma are electrically attracted to the electrodes so as not to reach the surface of the resin molded body. By doing so, the radicals in the plasma mainly reach the surface of the resin molded body, and a process of imparting a polar group to the molecules of the resin on the surface of the resin molded body by the action of the radical is performed. A method for forming a metal film on a resin molded product, comprising forming a metal film on a substrate. 3. A process for imparting a polar group to a resin molecule on the surface of a resin molded body by the action of radicals in plasma, wherein a holding electrode for holding the resin molded body and a counter electrode facing the resin molded body are provided. A plasma is generated between the electrodes, and by surrounding the resin molded body with an intermediate electrode that electrically attracts ions in the plasma, ions in the plasma are prevented from reaching the surface of the resin molded body. Item 3. A method for forming a metal film on a resin molded product according to Item 2. 4. A process for imparting a polar group to a resin molecule on the surface of a resin molded body by the action of radicals in plasma, wherein a holding electrode for holding the resin molded body and a counter electrode facing the resin molded body are provided. By generating a plasma between the electrodes and applying a negatively biased high-frequency voltage to the counter electrode, ions in the plasma are electrically attracted to the counter electrode, and the ions in the plasma are applied to the surface of the resin molding. The method for forming a metal film on a resin molded product according to claim 2, wherein the metal film is not allowed to reach. 5. A plasma is generated between a holding electrode holding the resin molded body and a counter electrode facing the resin molded body,
In performing the plasma treatment for cleaving the bonding of the resin molecules on the surface of the resin molded body, a high frequency voltage with a negative bias is applied to the holding electrode, and the negative bias voltage is controlled in a range of -100V to -700V. The method for forming a metal film on a resin molded product according to any one of claims 1 to 4, wherein: 6. A process for irradiating a laser to the surface of the resin molded body to cleave the bonds of the molecules of the resin on the surface of the resin molded body, and then guiding the plasma to the surface of the resin molded body by a downstream method. In this way, the radicals in the plasma mainly reach the surface of the resin molded body, and at the same time, a process of imparting a polar group to the molecules of the resin on the surface of the resin molded body by the action of the radicals is performed. A method for forming a metal film on a resin molding, comprising forming a metal film. 7. A process for irradiating a laser to the surface of the resin molded body to cleave the bonds of the molecules of the resin on the surface of the resin molded body, and then electrically attracting ions in the plasma to the electrode to cause a resin By preventing the radicals in the plasma from reaching the surface of the molded body, the process of causing the radicals in the plasma to mainly reach the surface of the molded resin body and imparting a polar group to the molecules of the resin on the surface of the molded resin body by the action of the radicals. Thereafter, a metal film is formed on the surface of the resin molded body, and a method of forming a metal film on the resin molded body. 8. A process for imparting a polar group to the resin molecules on the surface of the resin molded body by radicals in the plasma, followed by plasma treatment to crosslink the resin molecules on the surface of the resin molded body. A method for forming a metal film on a resin molded product according to any one of claims 1 to 7. 9. A plasma treatment for cross-linking resin molecules on the surface of the resin molded body in a state where the resin molded body is surrounded by a barrier that allows ultraviolet rays emitted from the plasma to pass but does not allow ions in the plasma to pass therethrough. The method for forming a metal film on a resin molded product according to claim 8. 10. A process for imparting a polar group to a resin molecule on the surface of a resin molded product by radicals in plasma, followed by an ultraviolet irradiation treatment to crosslink the resin molecule on the surface of the resin molded product. A method for forming a metal film on a resin molding according to any one of claims 1 to 7. 11. The method for forming a metal film on a resin molding according to claim 10, wherein the ultraviolet irradiation treatment is performed using an ultraviolet laser. 12. The method for forming a metal film on a resin molding according to claim 10, wherein the ultraviolet irradiation treatment is performed using an excimer lamp. 13. A plasma treatment for roughening the surface of the resin molded body prior to performing the treatment for cleaving the bond of the resin molecules on the surface of the resin molded body. A method for forming a metal film on a resin molded product according to any of the above items. 14. The method for forming a metal film on a resin molded product according to claim 13, wherein a plasma treatment for roughening the surface of the resin molded product is performed with plasma using oxygen or ozone as an atmospheric gas. 15. The resin molding according to claim 1, wherein the process of imparting a polar group to the resin molecules on the surface of the resin molding by the action of radicals in the plasma is performed while heating the resin molding. A method for forming a metal film on a resin molded product according to any of the above items. 16. The method for forming a metal film on a resin molded body according to claim 15, wherein the resin molded body is heated at a temperature of a glass transition temperature of the resin of the resin molded body ± 30 ° C. 17. The method for forming a metal film on a resin molded product according to claim 15, wherein only the surface layer portion of the resin molded product is heated. 18. Irradiating a surface of the resin molded body with a heat ray,
The method for forming a metal film on a resin molded product according to claim 17, wherein only the surface layer portion of the resin molded product is heated. 19. A process for imparting a polar group to a resin molecule on the surface of a resin molded body by the action of radicals in plasma using a gas selected from NH ₃ , SO ₂ , NO ₂ , and CO as an atmosphere gas. 19. The method for forming a metal film on a resin molded product according to claim 1, wherein the method is performed by plasma. 20. Prior to forming a metal film on the surface of the resin molded product, a metal having higher adhesiveness to the resin molded product than the metal film is pre-coated on the surface of the resin molded product, and The method for forming a metal film on a resin molded product according to any one of claims 1 to 19, wherein the metal film is formed. 21. The method according to claim 20, wherein the resin molded body is pre-coated with a metal by heating the resin molded body at a temperature of ± 30 ° C. of the glass transition temperature of the resin of the resin molded body. Film formation method. 22. The method for forming a metal film on a resin molding according to claim 20, wherein the pre-coated metal film is formed of a metal oxide. 23. Prior to forming a metal film on the surface of the resin molded body, a resin having higher adhesion to the metal film than the resin of the resin molded body is pre-coated on the surface of the resin molded body. The method for forming a metal film on a resin molding according to any one of claims 1 to 19, wherein the metal film is formed thereon.