JP2003094560A - Method for forming metallic film of resin substrate and metallic film forming resin substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a metallic film of a resin substrate, by which a surface layer of the resin substrate is removed by a short-time treatment without the necessity of disposing of a waste solution and the highly adhesive strength of a metallic film is ensured. SOLUTION: This surface layer 2 of the resin substrate 1 is removed by treating the surface layer 2 using at least one selected from among ozone, an oxygen ion and an oxygen radical. After that, the metallic film 3 is formed by metallizing the surface of the resin substrate 1. The metallic film 3 can be formed on the surface of the resin substrate 1 from which the fragile surface layer 2 is removed, and is no longer released from the resin substrate 1 on account of the breakage of the fragile surface layer 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a metal film on a resin substrate used as a resin molded circuit board, an illumination reflector, etc., and a metal film forming resin substrate.

[0002]

Liquid crystal polymer (LCP) is excellent in mechanical strength such as heat resistance, chemical resistance, low linear expansion coefficient, flame retardancy and high elastic modulus, and also excellent in electrical characteristics. ,
It is used in a wide range of fields such as electrical parts and mechanical parts. Since this liquid crystal polymer is thermoplastic, it is easy to mold by injection molding or the like, and the resin substrate obtained by molding the liquid crystal polymer is used as a resin molded circuit board such as MID or an illumination reflection plate. Is being carried out.

When a resin substrate made of a liquid crystal polymer is used as a resin molded circuit board or an illumination reflector, it is necessary to form a metal film on the surface of the resin substrate, but the liquid crystal polymer is chemically extremely inactive. Therefore, when the metal film is formed on the surface of the resin substrate by the PVD method such as the vacuum deposition method, the sputtering method and the ion plating method, the adhesion between the surface of the molded body and the metal film is extremely low. Therefore, the surface of the resin substrate is plasma-treated to modify the surface,
Attempts have been made to increase the adhesiveness with the metal film, but since the liquid crystal polymer is chemically extremely inactive, it is difficult to obtain a high surface modification effect and it is difficult to increase the adhesive strength. .

Therefore, the present applicant has filed Japanese Patent Application No. 2000-393.
No. 673, a method was proposed in which the surface of a resin substrate was subjected to a sulfonation treatment with sulfuric acid or the like, and a sulfo group was introduced into the surface of the resin substrate to enhance the adhesion of the metal film to the surface of the resin substrate. In this way, by introducing an ion-exchange group called sulfone group on the surface of the resin substrate,
The interface adhesion between the resin substrate and the metal film is certainly improved.As a result, the peeling of the resin substrate and the metal film is not the interface peeling between the resin substrate and the metal film, but the cohesive failure of the surface layer of the resin substrate. Is caused by. Therefore, the strength of the surface layer of the resin substrate is a factor that influences the adhesion of the metal film.

[0005]

When molding a resin substrate by performing injection molding and injecting resin into the mold, the resin injected into the mold is contacted with the wall surface of the mold. Due to the difference in viscosity, the flowing resin is less likely to flow than the resin flowing away from the wall surface. Therefore, the resin flowing in contact with the wall surface of the mold is pulled by the resin flowing away from the wall surface, and the molecules of the resin are oriented in the pulling direction. The surface layer formed of the resin near the wall surface is a layer in which the resin molecules are oriented in a direction parallel to the surface. In particular, in the case of liquid crystal polymers, the molecular chains are rigid and linear, so the molecules are much more easily aligned than other resins, and the degree of orientation of the resin molecules on the surface layer of the resin substrate is extremely high. ing. When the resin molecules on the surface layer of the resin substrate are oriented parallel to the surface in this way, the resin molecules on the surface layer of the resin substrate are oriented in a direction perpendicular to the orientation direction, that is, in the direction perpendicular to the surface of the resin substrate. Has a weak bonding force and the surface layer of the resin substrate is fragile. For this reason, the surface layer of the resin substrate has a very weak strength against cohesive failure.

Therefore, even if the sulfone group is introduced into the surface of the resin substrate to improve the interfacial adhesion between the resin substrate and the metal film as described above, as shown in FIG. Since the metal film 3 is peeled off from the resin substrate 1 by the destruction of the metal film 2, there is a problem that the adhesion strength of the metal film 3 cannot be increased.

Therefore, by treating such a resin substrate with an alkaline solution such as sodium hydroxide or potassium hydroxide, the fragile surface layer of the resin substrate is etched and removed, and a high-strength portion in the resin substrate is removed. Attempts have been made to secure high adhesion strength of the metal film to the resin substrate by allowing the metal film to appear on the surface and forming a metal film on the surface.

However, the treatment of the resin substrate with the alkaline solution is a wet process, and there is a problem that the treatment time becomes very long and a waste liquid treatment is required, which is not practical. In particular, since a liquid crystal polymer having high heat resistance has high chemical resistance and is hardly dissolved in an alkaline solution, it is difficult to apply such a treatment with an alkaline solution to the liquid crystal polymer.

The present invention has been made in view of the above points, and is a resin which can remove the surface layer of a resin substrate in a short time without the need for waste liquid treatment and can secure a high adhesion strength of a metal film. An object of the present invention is to provide a metal film forming method for a substrate and a metal film forming resin substrate.

[0010]

The method for forming a metal film on a resin substrate according to claim 1 of the present invention removes the surface layer of the resin substrate by treating it with at least one of ozone, oxygen ions and oxygen radicals. After that, metallization is performed on the surface of the resin substrate to form a metal film.

The invention of claim 2 is characterized in that, in claim 1, a resin substrate mixed with a filler is used, and the surface layer of the resin substrate is removed until the filler projects to the surface. .

The invention according to claim 3 is characterized in that, in claim 1, the resin substrate containing a filler is used, and the surface layer of the resin substrate is removed so that the filler does not protrude to the surface. is there.

The invention of claim 4 is characterized in that, in any one of claims 1 to 3, a resin substrate molded from a liquid crystal polymer is used.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the surface layer of the resin substrate is removed by ozone generated by atmospheric pressure plasma.

According to a sixth aspect of the present invention, in any one of the first to fourth aspects, the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by capacitively coupled plasma. It is characterized by.

According to a seventh aspect of the present invention, in the process of removing the surface layer of the resin substrate by capacitively coupled plasma using the parallel plate electrodes according to the sixth aspect, the resin plate is placed on the anode side of the parallel plate electrodes. Is arranged to perform processing.

According to an eighth aspect of the present invention, in the sixth or seventh aspect, when performing the process of removing the surface layer of the resin substrate by capacitively coupled plasma using parallel plate electrodes, a high frequency voltage is applied to both electrodes. It is characterized in that plasma is generated by applying it.

The invention according to claim 9 is the method according to any one of claims 1 to 4, wherein the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by the inductively coupled plasma. It is characterized by.

The invention of claim 10 relates to claims 1 to 4.
In any one of the above, it is characterized in that the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by surface wave plasma.

The invention of claim 11 relates to claims 5 to 1.
In any of No. 0, when performing the process of removing the surface layer of the resin substrate with plasma, an air flow is generated on the surface of the resin substrate.

The twelfth aspect of the present invention provides the fifth aspect.
In any of No. 0, when performing the process of removing the surface layer of the resin substrate with plasma, oxygen gas is caused to flow on the surface of the resin substrate.

The invention of claim 13 relates to claims 2 to 1.
In any one of 2), while performing the process of removing the surface layer of the resin substrate, the constituent element of the filler mixed in the resin substrate is detected, and the process of removing the surface layer of the resin substrate is performed based on the detection result. It is characterized by being stopped.

The invention of claim 14 relates to claims 2 to 1.
In any one of 2), the shape change of the treated surface of the resin substrate is observed while performing the treatment of removing the surface layer of the resin substrate, and the treatment of removing the surface layer of the resin substrate is stopped based on the observation result. It is characterized by doing so.

The invention of claim 15 is the same as claims 1 to 1.
In any one of 4 above, immediately after performing the treatment for removing the surface layer of the resin substrate, the treatment for imparting a functional group by polymerizing the functional group-providing molecule on the resin molecule on the surface of the resin substrate is performed. It is a thing.

According to the sixteenth aspect of the invention, in the fifteenth aspect of the invention, when the functional group-providing molecule is polymerized with the resin molecule on the surface of the resin substrate to give the functional group, a functional group previously radicalized is provided. It is characterized in that the polymerization is carried out using molecules.

Further, the invention of claim 17 is based on claims 1 to 1.
In any one of 4 above, immediately after performing the treatment of removing the surface layer of the resin substrate, the surface of the resin substrate is treated with sulfuric acid to impart a sulfo group to the surface of the resin substrate. is there.

In the metal film forming resin substrate according to claim 18 of the present invention, the surface layer of the resin substrate mixed with the filler is removed by a treatment with at least one of ozone, oxygen ions and oxygen radicals. Is removed to form a metal film on the surface of the resin substrate from which the filler is protruding.

The invention according to claim 19 is the invention according to claim 18, characterized in that the resin substrate is formed of a liquid crystal polymer.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

In the present invention, the resin substrate 1 is not particularly limited and any one can be used.
It is particularly preferable to use the resin substrate 1 obtained by molding a liquid crystal polymer (LCP) by injection molding or the like, because the effect of the invention can be further enhanced.

Further, it is preferable to use the resin substrate 1 in which the filler 4 is mixed. When molding is performed in a state where the filler 4 is mixed with a resin such as a liquid crystal polymer, the orientation of the resin molecules is disturbed by the presence of the filler 4, and the degree of orientation of the resin molecules in the surface layer 2 of the resin substrate 1 is reduced. Therefore, the fragility of the surface layer 2 of the resin substrate 1 can be reduced and the thickness of the fragile portion can be reduced. As the filler 4, those having a fibrous, plate-like, or spherical form can be used, and for example, glass or aluminum borate (both have a fibrous or spherical form).
Inorganic fillers such as can be used. Further, the content of the filler 4 in the resin substrate 1 is preferably about 30 to 35% by mass.

Then, prior to forming the metal film 3 on the surface of the resin substrate 1, a treatment for removing the brittle surface layer 2 of the resin substrate 1 is performed. In the present invention, ozone, oxygen ions,
By causing oxygen radicals to act on the surface of the resin substrate 1, the surface layer 2 can be removed by the ashing action of ozone, oxygen ions, and oxygen radicals. Ozone, oxygen ions, and oxygen radicals may be used alone or in combination of two or more.

In the present invention, as described above, the surface layer 2 of the resin substrate 1 is removed by the ashing treatment by the dry process using ozone, oxygen ions and oxygen radicals.
The surface layer 2 can be removed by a short-time treatment. Further, since it is a dry process, there is no problem such as waste liquid treatment.

In this way, as shown in FIGS. 1 (a) and 1 (b), after removing the surface layer 2 of the resin substrate 1, the surface layer 2 is removed and metallized on the exposed surface to obtain the surface shown in FIG. The metal film 3 is formed as in c). The metal film 3 can be formed by a PVD method such as a vacuum vapor deposition method, a sputtering method or an ion plating method. And
Surface layer 2 in which resin molecules of resin substrate 1 are oriented and weakened
Are removed by ashing treatment, and the metal film 3 is provided on the high-strength portion exposed on the surface of the resin substrate 1. Therefore, the fragile surface layer 2 is destroyed as shown in FIG. As a result, the metal film 3 is not peeled off from the resin substrate 1. By increasing the interface adhesion between the resin substrate 1 and the metal film 3, a high adhesion strength of the metal film 3 is ensured. Is something that can be done.

When the resin substrate 1 mixed with the filler 4 as described above is used, the surface layer 2 formed in contact with the mold is molded as a skin layer, and therefore the surface layer 2 is filled with the filler 4. Even if the filler 4 is an inorganic filler, the surface layer 2 can be easily removed by ashing with ozone, oxygen ions, and oxygen radicals. In removing the surface layer 2 by ashing, according to the second aspect of the invention, as shown in FIG.
As shown in FIG. 5, ashing is performed to remove the surface layer 2 until the filler 4 projects. Filler 4
Is an inorganic filler, the filler 4 is unlikely to be affected by ashing. Therefore, if ashing is performed so that the removal thickness when removing the surface layer 2 becomes thick, the filler 4 that is difficult to ash protrudes onto the surface of the resin substrate 1. Will be done. When the metal film 3 is metallized on the surface of the resin substrate 1 from which the filler 4 protrudes as shown in FIG. 2B, the anchor effect of the filler 4 further increases the adhesion strength of the metal film 3 to the resin substrate 1. Is.

When the filler 4 projects on the surface of the resin substrate 1 as described above, the surface of the resin substrate 1 becomes uneven. Therefore, for example, when a circuit for high frequency is formed by the metal film 3 provided on the surface of the resin substrate 1, a disadvantage such as an increase in skin resistance occurs. Therefore, in this case, ashing is performed so as to reduce the removal thickness when removing the surface layer 2, and the filler 4 is prevented from protruding onto the surface of the resin substrate 1 as shown in FIG. It is better to keep the surface smooth.

According to a fourth aspect of the present invention, the resin substrate 1 is formed of liquid crystal polymer (LCP). Since the liquid crystal polymer has high heat resistance and excellent high frequency characteristics, the resin substrate 1 formed of the liquid crystal polymer has a wide range of applications as a circuit board. On the other hand, however, the liquid crystal polymer has a rigid and linear molecular structure as described above, and the molecules are very easily aligned as compared with other resins, and the resin obtained by molding the liquid crystal polymer is a resin. The degree of orientation of the resin molecules of the surface layer 2 of the substrate 1 is very high, and the surface layer 2 is very fragile in the thickness range of several μm to 10 μm. Therefore, the fragile surface layer 2 of the resin substrate 1 formed of a liquid crystal polymer is removed by ashing as described above to ensure high adhesion strength of the metal film 3 while utilizing the excellent characteristics of the liquid crystal polymer. Is something that can be done.

Next, the ashing process for removing the surface layer 2 of the resin substrate 1 will be described. FIG. 4 shows an example of an embodiment of the invention according to claim 5, in which the surface layer 2 of the resin substrate 1 is formed by ozone generated by atmospheric pressure plasma.
The ashing process for removing the is performed.

That is, the pair of electrodes 6 and 7 arranged so as to face each other are arranged in an atmospheric pressure atmosphere, and the RF high frequency power source 8 is connected to one of the electrodes 6 and the other electrode. 7 is grounded. A dielectric material 9 is laminated on each facing surface of each of the electrodes 6 and 7. Glass or the like can be used as the dielectric 9. Then, the high-frequency power source 8 is turned on and a high-frequency voltage is applied between the electrodes 6 and 7, while a gas containing oxygen is passed between the electrodes 6 and 7 as indicated by the arrow, the gas causes dielectric breakdown between the electrodes 6 and 7. Then, the oxygen gas is excited, plasma is generated, and ozone is generated by the plasma. By causing the ozone thus generated to act on the surface of the resin substrate 1 as indicated by an arrow, the surface layer 2 of the resin substrate 1 is oxidized and decomposed by the action of ozone, and the surface layer 2 of the resin substrate 1 is ashed. It can be removed. For example, using an RF high frequency power supply 8 of 13.56 MHz, applying a high frequency voltage between the electrodes 6 and 7 with an input power of 200 W, an helium gas is supplied with an oxygen gas at 1
The surface layer 2 of the resin substrate 1 can be subjected to an ashing treatment by causing the mixed gas having a volume ratio of 0: 1 to flow at a flow rate of 11 mL / min. The resin substrate 1 is preferably heated to about 200 ° C. in order to accelerate the oxidative decomposition of the surface layer 2.

According to the fifth aspect of the invention, since the surface layer 2 of the resin substrate 1 is removed by the atmospheric pressure plasma treatment performed in the atmospheric pressure atmosphere as described above, equipment for depressurization and man-hours for depressurization are unnecessary. As a result, the device can be simplified and the processing can be easily performed. In addition, since the ashing process using ozone does not cause the ions to collide with the resin substrate 1 at high speed due to an electric attraction force as in the case of using oxygen ions, the ashing process does not damage the resin substrate 1. It can be processed. Further, since the dielectric 9 is provided on the facing surface of the electrodes 6 and 7, the discharge between the electrodes 6 and 7 becomes a dielectric barrier discharge.

FIG. 5 shows an example of an embodiment of the invention according to claim 6, which is an ashing treatment for removing the surface layer 2 of the resin substrate 1 by oxygen ions or oxygen radicals generated by capacitively coupled plasma. It was designed to do.

As shown in FIG. 5A, capacitively coupled plasma is generated between a pair of opposed electrodes 11 and 12 made of parallel plates under a reduced pressure condition.
1, 12 are arranged in the chamber 13. An RF high frequency power source 15 is connected to one of the electrodes 11 which are vertically opposed to each other through a matching circuit 14, and the other electrode 12 is grounded. Further, oxygen gas can be introduced into the chamber 13 through the gas introduction port 16.

When ashing the resin substrate 1, the resin substrate 1 is held by the electrode 11 connected to the high frequency power source 15, and the inside of the chamber 13 is evacuated to 1
After reducing the pressure to about 0 ⁻⁴ Pa, oxygen gas is introduced from the gas inlet 16 so that the oxygen gas pressure in the chamber 13 is 10 Pa.
Set to a degree. Next, from the high frequency power supply 15, for example, 13.
Electrode 1 with high power of 200W and high frequency voltage of 56MHz
When applied between 1 and 12, oxygen gas is excited and plasma P is generated by the gas discharge phenomenon due to the high frequency glow discharge between the electrodes 11 and 12. Oxygen ions and oxygen radicals are generated in this plasma P, as shown in FIG.
As shown in, the oxygen ions 17a and the oxygen radicals 17b in the plasma P collide with the surface of the resin substrate 1 to act,
The resin of the surface layer 2 of the resin substrate 1 is oxidatively decomposed by the action of the oxygen ions 17a and the oxygen radicals 17b, and the product 18 such as CO2 generated by the oxidative decomposition of the resin is removed from the surface of the resin substrate 1 to form a surface layer. 2 can be removed by ashing. The resin substrate 1 is preferably heated to about 200 ° C. in order to accelerate the oxidative decomposition of the surface layer 2, and the time required for ashing the resin substrate 1 is about 5 minutes.

As described above, the capacitively coupled plasma needs to be depressurized, but it has an advantage over the above atmospheric pressure plasma that it is possible to uniformly and ash a large area at once. Is. A pair of opposed electrodes 11 and 12 made of parallel plates that generate capacitively coupled plasma are connected to a high frequency power source 15 on one electrode 11 and the other electrode 12 is grounded. A negative DC voltage called self-bias appears on the electrode 11 on the side to be charged. Therefore, the electrode 11 to which a high frequency is applied serves as a cathode due to the negative bias, and the electrode 12 which is grounded serves as an anode. In the embodiment of FIG. 5, since the resin substrate 1 is held by the electrode 11 serving as a cathode, the positive oxygen ions generated in the plasma P are electrically attracted to the cathode electrode 11 and accelerated. Collide with the surface of the resin substrate 1. Therefore, the resin substrate 1
The surface layer 2 can be efficiently ashed, and the surface layer 2 can be removed in a short time.

However, when the oxygen ions are accelerated and collide with the surface of the resin substrate 1 as described above, the energy of collision is too large and the surface of the resin substrate 1 may be damaged. There is a possibility that the surface of the resin substrate 1 is weakened. Therefore, in the invention of claim 7, as shown in FIG. 6, the resin substrate 1 is held on the ground-side electrode 12 serving as an anode. Therefore, in this structure, the oxygen ions are not accelerated and collide with the surface of the resin substrate 1, and the surface of the resin substrate 1 can be prevented from being damaged. In this case, the processing time for removing the surface layer 2 is preferably set longer than in the case of FIG.

In the embodiment shown in FIG. 5, the high frequency power source 15 is connected to only one of the parallel plate electrodes 11 and 12 facing each other. In this structure, the density of the generated plasma P can be changed by changing the power of the high frequency voltage applied to the electrode 11 and the negative bias voltage applied to the electrode 11 can be changed. it can. Therefore, electrode 1
By changing the power or the like of the high frequency voltage applied to No. 1, it is possible to adjust the strength with which oxygen ions and the like act on the surface of the resin substrate 1, and it is possible to adjust the conditions of the ashing process. . However, the electrode 11
When the power of the high frequency voltage applied to the electrode 11 is changed, the density of the generated plasma P and the bias voltage applied to the electrode 11 are changed at the same time, and it is impossible to control them independently. There is a problem that the degree of freedom in setting conditions is low.

Therefore, in the eighth aspect of the invention, when performing the ashing treatment for removing the surface layer 2 of the resin substrate 1 by the capacitive coupling type plasma using the parallel plate electrodes 11 and 12 as described above, the electrodes 11 and 12 are performed. High frequency power sources 20 and 21 are individually connected to each other, and a high frequency voltage for bias application is applied to one electrode 11 and a high frequency voltage for plasma generation is applied to the other electrode 12 to generate plasma P. I am doing it. Thus, one electrode 11
A high frequency power source 20 for bias application is connected to
By connecting the high frequency power source 21 for plasma generation to the other electrode 12, the bias voltage applied to the electrode 11 can be controlled by controlling the power output from the high frequency power source 20, and the high frequency power source 21 also outputs the bias voltage. The density of the plasma P can be controlled by controlling the power, and the bias voltage and the plasma density can be controlled independently by individually controlling the high frequency power supplies 20 and 21. The degree of freedom in setting conditions is increased.

FIG. 7 (a) shows an example of the embodiment of the invention of claim 8, which is a high frequency power source 20 for bias application connected to the electrode 11 and a plasma generation connected to the electrode 12. The high frequency power supplies 21 are formed so as to apply high frequencies having different frequencies, the high frequency power supply 20 for bias application is set to a low frequency, and the high frequency power supply 21 for plasma generation is set to a high frequency. High frequency power supply 2
0 and 21 are grounded through the chamber 13, and the other configurations are the same as those in FIG. By using the high frequency power sources 20 and 21 having different frequencies in this way, it is possible to prevent the high frequencies of the high frequency power sources 20 and 21 from interfering with each other and canceling each other out, and to stably generate the plasma P. Is.

FIG. 7B shows another example of the embodiment of the invention of claim 8, which is connected to the electrode 12 and a high frequency power source 20 for bias application which is connected to the electrode 11. The high frequency power source 21 for plasma generation is, for example, 1
Although it is formed so as to apply a high frequency of the same frequency such as 3.56 MHz, a phase shifter 22 is connected to each of the high frequency power sources 20 and 21, and the high frequency power sources 20 and 21 are connected to the power source 1.
The phases of the high frequencies applied to 1 and 12 are controlled so as to be mutually shifted. High frequency power source 20, 21 is chamber 1
It is grounded through 3, and the other structure is the same as that of FIG. When the high frequency power supplies 20 and 21 having the same frequency are used in this way, the high frequency powers of the high frequency power supplies 20 and 21 are shifted by shifting the phase of the high frequency power applied from the high frequency power supplies 20 and 21 to the power supplies 11 and 12, for example, by an angle of π. It is possible to prevent plasma from interfering with each other and to generate plasma P stably.

FIG. 8 shows an example of an embodiment of the invention according to claim 9, which is an inductively coupled plasma (ICP).
The ashing process for removing the surface layer 2 of the resin substrate 1 is performed by the oxygen ions and oxygen radicals generated in step 2.

That is, as shown in FIG.
The dielectric coil 26 is formed on the outer periphery of the insulator 25 formed on a part of
Is wound, and an RF high frequency power source 66 is connected via a matching circuit 65. In FIG. 8, reference numeral 28 is a substrate holder to which an RF high frequency power source 30 is connected via a matching circuit 31. The resin substrate 1 is set in the substrate holder 28. Also the chamber 24
Is provided with an oxygen introducing port 27 so that oxygen is introduced into the chamber 24, and a vacuum pump is connected to the exhaust port 32.

Then, for example, the frequency 1 is applied to the induction coil 26.
When a high frequency current of 3.56 MHz and an output of 1 kW is passed, the induction magnetic field 33 is excited and formed in the dielectric coil 26. However, since the induction magnetic field 33 is a high frequency current, the induction magnetic field 33 is generated.
Fluctuates, and a fluctuating induction electric field 34 is generated around the induction magnetic field 33. The electric field generated by the electric field 34 accelerates electrons to collide with neutrons, causing ionization to generate plasma. The ashing process for removing the surface layer 2 of the resin substrate 1 can be performed by oxygen ions or oxygen radicals in the plasma thus generated. This inductively coupled plasma can generate a higher density plasma than the capacitively coupled plasma, and can efficiently ash the surface layer 2 of the resin substrate 1.

FIG. 9 shows an example of an embodiment of the invention according to claim 10, in which the surface layer 2 of the resin substrate 1 is removed by oxygen ions or oxygen radicals generated by surface wave plasma (SWP). The ashing process is performed.

That is, as shown in FIG. 9, the chamber 3
A waveguide 37 is arranged so as to face the inside of the waveguide 6, and a quartz plate 39 is arranged so as to face an opening 38 provided in the waveguide 37. A ground potential mesh electrode 40 is arranged in the chamber 36 at a position facing the quartz plate 39. At a position on the opposite side of the mesh electrode 40 from the quartz plate 39, a substrate holder 41 at a ground potential containing a heater. Is provided. Oxygen gas is supplied into the chamber 36, and the gas in the chamber 36 is exhausted from the exhaust port 42.

When the insulating substrate 1 is held in the substrate holder 41 and a microwave having a frequency of 2.45 GHz and a power of 3 kW is passed through the waveguide 37, the microwave leaking from the opening 38 propagates on the surface. As quartz plate 39
Plasma P is generated in the chamber 36. The ashing process for removing the surface layer 2 of the resin substrate 1 by the oxygen ions and oxygen radicals in the plasma P thus generated can be performed. This surface wave plasma can generate a plasma P having a higher density than that of the capacitively coupled plasma, and can generate the plasma P in a larger area than that of the inductively coupled plasma. The surface layer 2 of the resin substrate 1 can be highly ashed.

Next, the invention of claim 11 is based on FIG.
When performing the ashing process for removing the surface layer 2 of the resin substrate 1 with the plasma P as in each of the embodiments of FIG. 9, an air flow is generated on the surface of the resin substrate 1. 9, the vacuum pump 44 is connected to the exhaust port 42 in the configuration shown in FIG. When the vacuum pump 44 is operated and the gas in the chamber 36 is exhausted while performing the ashing process by the plasma P, an air flow can be generated on the surface of the resin substrate 1 as the gas is exhausted.

Here, when the surface layer 2 of the resin substrate 1 is ashed with the plasma P, the surface layer 2 can be removed by an oxidation reaction due to oxygen radicals generated in the plasma P. Since the reacted oxygen radicals have no ability to ash anymore, if the reacted oxygen radicals stay on the surface of the resin substrate 1,
The unreacted fresh oxygen radicals are prevented from acting on the surface layer 2 of the resin substrate 1. Further, when a product such as CO ₂ produced by the oxidation of the resin of the surface layer 2 stays on the surface of the resin substrate 1, oxygen radicals are similarly prevented from acting on the surface layer 2 of the resin substrate 1. To be In particular, since oxygen radicals and products such as CO ₂ are electrically neutral, their movement cannot be controlled by an electric field or the like, and they easily stay on the surface of the resin substrate 1.

In such a case, by reacting the oxygen radicals that have already reacted and substances generated by removing the surface layer of the resin substrate 1 by generating an air flow on the surface of the resin substrate 1 as described above, Since it can be quickly removed from the surface of the resin substrate 1 by the air flow, fresh unreacted oxygen radicals can efficiently act on the surface of the resin substrate 1, and the surface layer 2 of the resin substrate 1 can be efficiently formed. It can be ashed.

Further, in the twelfth aspect of the present invention, when the ashing treatment for removing the surface layer 2 of the resin substrate 1 by the plasma P is performed as described above, oxygen gas is caused to flow on the surface of the resin substrate 1. In the embodiment of FIG. 11, the oxygen gas introduction pipe 45 is connected to the chamber 36 in the embodiment of FIG. 10, and the oxygen gas is caused to flow to the surface of the resin substrate 1 while performing ashing with the plasma P. . By thus flowing the oxygen gas over the surface of the resin substrate 1, the reacted oxygen radicals and substances generated by removing the surface layer of the resin substrate 1 can be quickly removed from the surface of the resin substrate 1. In addition, fresh unreacted oxygen radicals can efficiently act on the surface of the resin substrate 1, and the resin substrate 1 can be efficiently used.
The surface layer 2 can be ashed.

According to the thirteenth aspect of the present invention, the constituent elements of the filler 4 mixed in the resin substrate 1 are detected while performing the ashing treatment for removing the surface layer 2 of the resin substrate 1, and the resin is detected based on the detection result. The ashing process for removing the surface layer of the substrate 1 is stopped.

FIG. 12A shows an example of the embodiment, and in the above-mentioned FIG. 5A, a mass analyzer 47 is provided in the chamber 13, and the inside of the chamber 13 is adjusted by the mass analyzer 47. The element is analyzed by mass spectrometry. Further, in the embodiment of FIG.
3 is provided with a spectrum analyzer 48, and the spectrum analyzer 4
8 detects the light emission in the plasma P, and the chamber 13
The elements inside are analyzed.

Here, when the resin substrate 1 with the filler 4 mixed therein is used, the surface layer 2 formed in contact with the mold is formed as a skin layer, so that the surface layer 2 has a filler 4 mixing ratio. small. Therefore, in the initial stage when only the surface portion of the surface layer 2 is removed in performing the ashing process, the element component generated by the oxidative decomposition of the resin is generated in the chamber 13, but constitutes the filler 4. Almost no elemental components were generated. When the ashing process proceeds and the surface layer 2 is removed, the filler 4 is also subjected to the ashing action.
Elemental components forming the filler 4 are generated in the material 3. Therefore, when the element in the chamber 13 is analyzed by the mass analyzer 47 and the spectrum analyzer 48 and the element of the filler 4 is detected, it means that the removal of the surface layer 2 has been completed, so that the generation of the plasma P is completed. The ashing process is stopped. In this way, the ashing process can be automatically stopped and the surface layer 2 of the resin substrate 1 can be removed without excess or deficiency.

According to a fourteenth aspect of the present invention, while performing the ashing treatment for removing the surface layer 2 of the resin substrate 1, the shape change of the treated surface of the resin substrate 1 is observed, and based on this observation result, the resin substrate 1 The processing for removing the surface layer 2 is stopped. FIG. 13 shows an example of the embodiment. In the structure shown in FIG. 6, the chamber 13 is provided with a laser light emitter 50 and a light receiver 51, and the laser light emitter 50 is provided on the surface of the insulating substrate 1. The light receiver 51 receives the laser light irradiated with light and reflected by the surface of the insulating substrate 1.

Here, when the resin substrate 1 with the filler 4 mixed therein is used, the surface layer 2 formed in contact with the mold is formed as a skin layer, so that the surface layer 2 has a mixed ratio of the filler 4 therein. small. Therefore, at the initial stage when only the surface portion of the surface layer 2 is removed in performing the ashing process, the filler 4 is hardly exposed on the surface,
When the ashing process proceeds and the surface layer 2 is removed, the filler 4 is exposed and protrudes from the surface. When the filler 4 protrudes and the shape of the treated surface of the resin substrate 1 changes as described above, the laser light emitted from the laser light emitter 50 to the surface of the insulating substrate 1 is scattered and the light receiver 5
The intensity of the laser light received at 1 becomes weak. Therefore,
By detecting the change in the intensity of the laser light received by the light receiver 51, the protruding state of the filler 4 on the surface of the resin substrate 1 can be observed, and it is observed that the filler 4 has protruded. If so, it means that the removal of the surface layer 2 is completed, so that the generation of the plasma P is stopped and the ashing process is stopped. In this way, the ashing process can be automatically stopped and the surface layer 2 of the resin substrate 1 can be removed without excess or deficiency. In the method shown in FIG. 12, it is necessary that the elements of the filler 4 react with each other to vaporize or be etched by ashing, and the amount thereof is so small that it is difficult to accurately analyze and detect. However, in the method of FIG. 13, since the state of the filler 4 existing in the resin substrate 1 is detected, there is no such problem.

As described above, the surface layer 2 of the resin substrate 1 is removed by ashing, and the surface of the resin substrate 1 from which the surface layer 2 has been removed is metallized to form the metal film 3. It is desirable to perform a treatment for enhancing the adhesion of the metal film 3 on the surface of the substrate 1 in advance.

Therefore, according to the fifteenth aspect of the invention, immediately after performing the ashing treatment for removing the surface layer 2 of the resin substrate 1,
The resin molecule on the surface of the resin substrate 1 is graft-polymerized to give a polar functional group.
Immediately after ashing with ozone, oxygen ions, and oxygen radicals to remove the surface layer 2, the resin molecules on the surface of the resin substrate 1 are in a state in which the molecular bonds are broken.
Very active. Therefore, when a functional group-imparting molecule is made to act on the surface of the resin substrate 1 immediately after the ashing process while the resin on the surface is still in an active state, the functional group-imposing molecule is added to the resin stem molecule 53 as shown in FIG. The branch molecule 54 can be easily graft-polymerized and can be provided with a highly polar functional group. By imparting a functional group to the surface of the resin substrate 1 in this manner, the metal film 3 to be metallized on the surface is bound to the functional group,
The adhesion strength of the metal film 3 to the resin substrate 1 can be increased.

FIG. 15 shows an example of a method for graft-polymerizing resin molecules on the surface of the resin substrate 1 to give a functional group. In FIG. 5 (a), the functional group is given to the chamber 13. A gas inlet 55 is provided. As the functional group-providing gas introduced through the functional group-providing gas introduction port 55, an inorganic gas such as NO _x , H ₂ S, SO _x , or NH ₃ or acrylic acid or imidazole (a monomer obtained by decomposing vinylimidazole) is used. be able to. Then, first, as shown in FIG. 15A, oxygen gas is introduced into the chamber 13 from the gas inlet 16 to generate the plasma P as described above, and the ashing treatment for removing the surface layer 2 of the resin substrate 1 is performed. Next, after the ashing process is completed, FIG.
As shown in (b), a gas of a functional group-providing molecule is introduced into the chamber 13 from the functional group-providing gas inlet 55, the surface layer 2 of the resin substrate 1 is removed, and functional groups are provided to the resin molecules on the surface exposed. A molecule can be graft-polymerized to give a functional group. Since the graft polymerization can be performed in the same chamber 13 in which the surface layer 2 of the resin substrate 1 is ashed, the functional group-providing molecule can be reacted with the resin of the resin substrate 1 which is still in an active state immediately after ashing. Therefore, it is possible to easily carry out the graft polymerization without having to perform a treatment for activating the surface of the resin substrate 1 again.

Here, in the case where the resin on the surface of the resin substrate 1 is graft-polymerized, the resin substrate 1 is immersed in a solution of a monomer for grafting and a radical polymerization initiator and heated to be grafted with radicals generated by decomposition of the initiator. There is a method of causing polymerization, but with this method of using a solution, since the polymerization of the grafting monomers also occurs, the loss is large,
As shown in FIG. 15, it is preferable to generate radicals by using radiation, ultraviolet rays, or plasma without using an initiator to cause graft polymerization in the gas phase. The radiation graft polymerization irradiates both the surface of the resin substrate 1 and the functional group-imparting molecule with radiation at the same time, and before the functional group-imparting molecule diffuses into the resin substrate 1, the resin trunk molecules on the surface of the resin substrate 1 Simultaneous irradiation method in which the functional group-imparting molecule is graft-polymerized as a branch molecule, and the resin substrate 1 is irradiated with radiation in the air to generate a peroxide-initiating species, and then the functional-group-imparting molecule is brought into contact to perform graft polymerization. There is an irradiation method, a pre-irradiation method in a vacuum that irradiates radiation under vacuum instead of in air,
Since radiation has a large penetrating power, it is difficult to perform graft polymerization only on the surface of the resin substrate 1. The UV graft polymerization is a method in which a resin substrate 1 is impregnated with a sensitizer to form radicals in the resin trunk molecules, a method in which a sensitizer is interposed in a solution to perform graft polymerization, and a sensitizer. There is a method in which the resin substrate 1 is impregnated with a solvent containing a functionalization molecule and the graft polymerization is started. Further, the plasma graft polymerization is a method in which low-temperature plasma treatment is performed for about several seconds to generate radicals in the resin, and then the functionalizing molecule is introduced as vapor or gas to directly react with the radicals. Is released into the air to convert the radicals into peroxide radicals, and then reacted with a functionalizing molecule. Although there are various methods as described above, only the surface of the resin substrate 1 needs to be modified. Therefore, the method in which the graft polymerization is performed only on the surface of the resin substrate 1 is preferable.

In the sixteenth aspect of the present invention, when the functional group-imparting molecule is polymerized with the resin molecule on the surface of the resin substrate 1 to impart the functional group as described above, plasma or electron beam is applied to the functional group-imparting molecule. Polymerization is carried out using a functional group-added molecule that has been radicalized in advance by acting with ultraviolet rays or the like. FIG. 16 shows an example of the embodiment, and in the above-mentioned FIG. 15, a plasma chamber 57 is connected to the chamber 13 via a functional group-providing gas introduction port 55. A pair of electrodes 58 and 59 are arranged in the plasma chamber 57, and a high frequency voltage is applied between the electrodes 58 and 59 by a high frequency power source 60.
Ar plasma P ₁ is generated in the plasma chamber 57. Then, when the gas of the functional group-providing molecule is introduced into the plasma chamber 57 from the supply port 61,
The functional group-added molecule is radicalized by the Ar plasma P ₁ . By introducing the functional group-provided molecules thus radicalized into the chamber 13 through the functional group-provided gas introduction port 55, resin molecules on the surface of the resin substrate 1 on which the surface layer 2 has been ashed in the same manner as described above are introduced. A functional group can be imparted to the surface of the resin substrate 1 by graft-polymerizing a functional group-imparting molecule. Since the functional group-imparting molecule is thus radicalized, it is capable of efficiently graft-polymerizing to the resin molecule on the surface of the resin substrate 1 and capable of efficiently imparting a functional group to the surface of the resin substrate 1. Is.

According to the seventeenth aspect of the invention, after the ashing treatment for removing the surface layer 2 of the resin substrate 1 is performed as described above, the resin on the surface exposed by the removal of the surface layer 2 is still active. While in the state, the surface of the resin substrate 1 is treated with sulfuric acid so that the surface of the resin substrate 1 is provided with a sulfone group. Sulfur (S) is the metal film 3,
Particularly, the bondability with copper is good, and by forming such a sulfone group (SO ₃ H) having S on the surface of the resin substrate 1, the metal film 3 which is metallized on the surface of the resin substrate 1 is formed. The adhesive strength can be increased.

For example, as shown in FIG. 17, the resin substrate 1 immediately after the ashing treatment is treated with a sulfuric acid solution 6 such as a sulfuric acid aqueous solution.
By immersing the resin substrate 3 in the resin 3, a sulfone group can be provided on the surface of the resin substrate 1. The sulfuric acid solution 63 preferably has a sulfuric acid concentration of 10 to 95% by mass, particularly 50 to 85% by mass, and the resin substrate 1 is immersed for 1 to 60 minutes under the condition of about 30 to 70 ° C. 1
Sulfone groups can be formed on the surface of. It is also possible to add a sulfo group dry using a gas such as H ₂ S or SO _x , but since H ₂ S or SO _x is highly corrosive, a sulfo group should be added using sulfuric acid. Is preferred.

[0072]

As described above, the method for forming a metal film on a resin substrate according to claim 1 of the present invention removes the surface layer of the resin substrate by treating it with at least one of ozone, oxygen ions and oxygen radicals. After that, since the metal film is formed on the surface of the resin substrate by metallization, the metal film can be formed on the surface of the resin substrate after removing the fragile surface layer, and the fragile surface layer is destroyed. As a result, the metal film is prevented from being peeled off from the resin substrate, and by increasing the interface adhesion between the resin substrate and the metal film, it is possible to secure high adhesion strength of the metal film. is there. Then, the surface layer of the resin substrate can be removed by a dry method by the oxidizing action of ozone, oxygen ions and oxygen radicals, and the surface layer can be removed in a short time without the need for waste liquid treatment.

According to the invention of claim 2, in the resin composition according to claim 1, the filler is mixed as the resin substrate, and the surface layer of the resin substrate is removed until the filler protrudes to the surface. By this, the brittleness of the surface layer can be reduced, and the adhesion effect of the metal film can be further enhanced by the anchor effect of the protruding filler.

According to a third aspect of the present invention, in the first aspect, the resin substrate mixed with the filler is used, and the surface layer of the resin substrate is removed so that the filler does not protrude to the surface. The inclusion can reduce the brittleness of the surface layer, and can prevent the surface of the resin substrate from becoming uneven due to the protrusion of the filler.

Further, according to the invention of claim 4, in any one of claims 1 to 3, the resin substrate molded with the liquid crystal polymer is used, so that the surface layer of the resin substrate molded with the liquid crystal polymer becomes fragile. However, the removal of the surface layer can ensure high adhesion strength of the metal film,
It is possible to obtain a metal film-forming resin substrate that takes advantage of the characteristics of the liquid crystal polymer.

Further, according to the invention of claim 5, in any one of claims 1 to 4, since the treatment for removing the surface layer of the resin substrate is carried out by ozone generated by the atmospheric pressure plasma, This eliminates the need for equipment and man-hours for decompression, simplifies the device, and makes it easy to perform processing, and furthermore, it is possible to perform processing without damaging the resin substrate with ozone. is there.

According to a sixth aspect of the present invention, in any one of the first to fourth aspects, the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by capacitively coupled plasma. Because I chose
The capacitively coupled plasma makes it possible to uniformly and simultaneously process a large area.

According to a seventh aspect of the present invention, in the process of removing the surface layer of the resin substrate by capacitively coupled plasma using the parallel plate electrodes according to the sixth aspect, the resin substrate is placed on the anode side of the parallel plate electrodes. Since the treatment is performed by disposing the oxygen ion, the resin substrate is placed on the anode side where oxygen ions are not electrically attracted, and it is possible to prevent the oxygen ions from colliding with the surface of the resin substrate at high speed. Therefore, it is possible to prevent the surface of the resin substrate from being damaged by the energy of this collision.

According to the eighth aspect of the present invention, in the sixth or seventh aspect, when the surface layer of the resin substrate is removed by capacitively coupled plasma using parallel plate electrodes, a high frequency voltage is applied to both electrodes. Since the applied voltage is used to generate the plasma, the bias voltage and the plasma density can be controlled independently by controlling the application of the high frequency voltage to each electrode. The degree of freedom in setting conditions is increased.

According to a ninth aspect of the present invention, in any one of the first to fourth aspects, the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by the inductively coupled plasma. Because I chose
The inductively coupled plasma system can generate high-density plasma, and can efficiently remove the surface layer of the resin substrate.

Further, the invention of claim 10 relates to claims 1 to 4.
In any of the above, the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated in the surface wave plasma. It is possible to generate plasma, and it is possible to efficiently perform the treatment for removing the surface layer of the resin substrate.

Further, the invention of claim 11 relates to claims 5 to 1.
In any of 0, when performing the process of removing the surface layer of the resin substrate with plasma, since the airflow is generated on the surface of the resin substrate, the reacted oxygen radicals and the surface layer of the resin substrate are removed. The substance generated by this can be quickly removed from the surface of the resin substrate by this air flow, and fresh unreacted oxygen radicals can be efficiently acted on the surface of the resin substrate. It is possible to perform a treatment for removing the surface layer.

The twelfth aspect of the present invention includes the fifth to first aspects.
In any of 0, when performing the process of removing the surface layer of the resin substrate by plasma, oxygen gas was made to flow to the surface of the resin substrate, so that the reacted oxygen radicals and the surface layer of the resin substrate are removed. The substance generated by this can be quickly removed from the surface of the resin substrate by this air flow, and fresh unreacted oxygen radicals can be efficiently acted on the surface of the resin substrate. It is possible to perform a treatment for removing the surface layer.

Further, the invention of claim 13 is based on claims 2 to 1.
In any one of 2), while performing the process of removing the surface layer of the resin substrate, the constituent element of the filler mixed in the resin substrate is detected, and the process of removing the surface layer of the resin substrate is performed based on the detection result. Since it is stopped, it is possible to detect the completion of the removal of the surface layer by detecting the element of the filler, it is possible to automatically stop the process, the surface layer of the resin substrate without excess or deficiency It can be removed.

Further, the invention of claim 14 is the invention of claims 2 to 1.
In any one of 2), the shape change of the treated surface of the resin substrate is observed while performing the treatment of removing the surface layer of the resin substrate, and the treatment of removing the surface layer of the resin substrate is stopped based on the observation result. Therefore, it is possible to detect the completion of removal of the surface layer by observing the state of the filler exposed on the surface, the process can be automatically stopped, and the surface layer of the resin substrate can be overheated. It can be removed without deficiency.

The invention of claim 15 relates to any one of claims 1 to 1.
In any one of 4 above, immediately after the treatment for removing the surface layer of the resin substrate, the treatment for polymerizing the functional group-providing molecule on the resin molecule on the surface of the resin substrate to give the functional group is performed. It is possible to increase the adhesion strength of the metal film to the resin substrate by bonding the metal film to the functional group, and the resin molecules on the surface of the resin substrate immediately after removing the surface layer are in an active state, It is possible to easily carry out a polymerization reaction for imparting a functional group.

According to a sixteenth aspect of the present invention, in the fifteenth aspect, the functional group imparted with a radical in advance is added in the process of polymerizing the functional group-imparting molecule with the resin molecule on the surface of the resin substrate to impart the functional group. Since the polymerization is carried out using molecules, it is possible to efficiently polymerize the functional group-imparting molecule with the resin molecule on the surface of the resin substrate, and to efficiently impart the functional group to the surface of the resin substrate. is there.

Further, the invention of claim 17 is based on claims 1 to 1.
In any one of 4 above, immediately after performing the treatment for removing the surface layer of the resin substrate, the surface of the resin substrate is treated with sulfuric acid so as to impart a sulfo group to the surface of the resin substrate. The sulfonic group having a high bondability with can enhance the adhesion strength of the metal film to the surface of the resin substrate.

In the metal film forming resin substrate according to claim 18 of the present invention, the surface layer of the resin substrate mixed with the filler is removed by a treatment with at least one of ozone, oxygen ions and oxygen radicals. It is characterized in that a metal film is formed on the surface of the resin substrate from which the filler is projected by removing the metal film, and the metal film is peeled from the resin substrate by breaking the fragile surface layer. The adhesion strength of the metal film can be ensured to be high, and the adhesion effect of the metal film can be further increased by the anchor effect of the protruding filler.

According to a nineteenth aspect of the present invention, in the eighteenth aspect, since the resin substrate is molded with a liquid crystal polymer, the surface layer of the resin substrate molded with the liquid crystal polymer tends to be fragile, but the surface layer By removing the metal film, a high adhesion strength of the metal film can be secured, and a metal film-forming resin substrate that takes advantage of the characteristics of the liquid crystal polymer can be obtained.

[Brief description of drawings]

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

FIG. 2 shows another example of the embodiment of the present invention, and (a) and (b) are partially enlarged schematic sectional views, respectively.

FIG. 3 is a partially enlarged schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 4 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 5 shows another example of the embodiment of the present invention, in which (a) and (b) are schematic sectional views, respectively.

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

FIG. 7 shows another example of the embodiment of the present invention, in which (a) and (b) are schematic sectional views, respectively.

FIG. 8 is a schematic cross-sectional view of another example of the embodiment of the present invention.

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

FIG. 10 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 11 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 12 shows another example of the embodiment of the present invention, in which (a) and (b) are schematic sectional views, respectively.

FIG. 13 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 14 is a schematic view of another example of the embodiment of the present invention.

FIG. 15 shows another example of the embodiment of the present invention, in which (a) and (b) are schematic sectional views, respectively.

FIG. 16 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 17 is a schematic cross-sectional view of another example of the embodiment of the present invention.

FIG. 18 is a schematic cross-sectional view showing a conventional example.

[Explanation of symbols]

1 resin substrate 2 surface layer 3 metal film 4 filler

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/38 H05K 3/38 AF term (reference) 4F100 AA02 AB01B AG00 AK01A AK80A BA02 BA07 CA23A CA23H EH66 EJ122 EJ132 EJ61A GB43 JL11 4K029 AA11 AA24 BA01 BC00 BD02 BD09 CA01 CA03 CA05 FA05 5E343 AA16 AA37 CC34 EE36 GG02 GG04

Claims (19)

[Claims] 1. A surface layer of a resin substrate is removed by treatment with at least one of ozone, oxygen ions, and oxygen radicals, and then metallized on the surface of the resin substrate to form a metal film. Method for forming a metal film on a resin substrate to be used. 2. The method for forming a metal film on a resin substrate according to claim 1, wherein a resin substrate mixed with a filler is used and the surface layer of the resin substrate is removed until the filler protrudes to the surface. 3. The method for forming a metal film on a resin substrate according to claim 1, wherein a resin substrate mixed with a filler is used, and the surface layer of the resin substrate is removed so that the filler does not protrude to the surface. . 4. The method for forming a metal film on a resin substrate according to claim 1, wherein a resin substrate molded from a liquid crystal polymer is used. 5. The method for forming a metal film on a resin substrate according to claim 1, wherein the surface layer of the resin substrate is removed by ozone generated by atmospheric pressure plasma. 6. The resin according to claim 1, wherein the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by capacitively coupled plasma. A method for forming a metal film on a substrate. 7. A process of removing a surface layer of a resin substrate by capacitively coupled plasma using a parallel plate electrode, wherein the resin substrate is arranged on the anode side of the parallel plate electrode and the process is performed. The method for forming a metal film on a resin substrate according to claim 6. 8. When performing a process of removing the surface layer of the resin substrate by capacitively coupled plasma using parallel plate electrodes, a high frequency voltage is applied to both electrodes to generate plasma. The method for forming a metal film on a resin substrate according to claim 6 or 7. 9. The resin according to claim 1, wherein the surface layer of the resin substrate is removed by at least one of oxygen ions and oxygen radicals generated by inductively coupled plasma. A method for forming a metal film on a substrate. 10. The resin substrate according to claim 1, wherein a treatment for removing the surface layer of the resin substrate is performed by at least one of oxygen ions and oxygen radicals generated by surface wave plasma. Method for forming metal film. 11. The resin substrate according to claim 5, wherein an airflow is generated on the surface of the resin substrate when the surface layer of the resin substrate is removed by plasma. Metal film forming method. 12. The resin substrate according to claim 5, wherein an oxygen gas is caused to flow on the surface of the resin substrate when the surface layer of the resin substrate is removed by plasma. Method for forming metal film. 13. A process for removing a surface layer of a resin substrate, a constituent element of a filler mixed in a resin substrate is detected, and a process for removing the surface layer of the resin substrate is stopped based on the detection result. 13. The method for forming a metal film on a resin substrate according to claim 2, wherein the method is performed. 14. The shape change of the treated surface of the resin substrate is observed while performing the treatment of removing the surface layer of the resin substrate,
13. The method for forming a metal film on a resin substrate according to claim 2, wherein the treatment for removing the surface layer of the resin substrate is stopped based on this observation result. 15. Immediately after performing the treatment for removing the surface layer of the resin substrate, the treatment for polymerizing the functional group-imparting molecule with the resin molecule on the surface of the resin substrate to impart the functional group is performed. Item 15. A method for forming a metal film on a resin substrate according to any one of Items 1 to 14. 16. A method of polymerizing a functional group-providing molecule on a resin molecule on the surface of a resin substrate to impart a functional group, wherein the radical-functionalized functional group-providing molecule is used for the polymerization. 16. The method for forming a metal film on a resin substrate according to claim 15. 17. The sulfo group is imparted to the surface of the resin substrate by treating the surface of the resin substrate with sulfuric acid immediately after the treatment for removing the surface layer of the resin substrate. 15. The method for forming a metal film on a resin substrate according to any one of 14 to 14. 18. A resin substrate in which a surface layer of a resin substrate mixed with a filler is removed by a treatment with at least one of ozone, oxygen ions and oxygen radicals, and the filler is projected by removing the surface layer. A metal film-formed resin substrate, wherein a metal film is formed on the surface of. 19. The metal film-forming resin substrate according to claim 18, wherein the resin substrate is formed of a liquid crystal polymer.