JP4362863B2 - Plating method and pre-plating method - Google Patents

Description

The present invention relates to a plating method and a plating pretreatment method, and more particularly to a plating method for forming a metal film on the surface of a resin substrate and a pretreatment method therefor.

  As a plating method for forming a metal film on the surface of a substrate made of a carbon atom-containing material such as a resin, a so-called vapor deposition method, an electroless plating method, and the like are known. In general, a resin material has an adhesion property to a metal material. Therefore, there is a problem that the metal film cannot be formed on the surface of the base material unless the surface of the base material is previously modified (pretreatment for plating). For this reason, various plating pretreatment methods have been studied, and methods such as corona discharge treatment and plasma irradiation treatment have been carried out as plating pretreatment methods relating to plating methods by vapor deposition. In addition, as a plating pretreatment method related to a plating method by an electroless plating method, an etching method using an etchant, a laser irradiation treatment, a plasma irradiation treatment, an ozone irradiation treatment, an ultraviolet irradiation treatment, and the like are performed. Documents 1 to 4 describe an electroless plating method using an ultraviolet irradiation treatment as a plating pretreatment method.

However, there is a limit to improving the adhesion between various resin substrates and metal films using any of the above-described conventional plating pretreatment methods, and in corona discharge treatment, plasma irradiation treatment, and ultraviolet irradiation However, since the activated surface is deactivated relatively early, there is a problem that the process must be shifted to the plating process immediately after the pre-plating treatment, resulting in a great restriction on the process. Etching treatment, laser irradiation treatment, and ozone irradiation treatment are all methods for improving the adhesion between the metal film by roughening the surface of the resin substrate in principle to form an anchor (throwing) shape. However, the surface of the metal film is reflected to reflect the surface roughness of the resin base material, and there is a problem that the covering property, peristaltic property, shape accuracy, electrical property, mechanical strength, etc. are lowered. .
JP-A-8-253869 JP-A-6-87964 JP-A-10-310873 JP 2003-27250 A

The present invention has been made in view of the above-mentioned problems of the prior art, and is a metal having high adhesion and excellent surface smoothness without subjecting the surface of a resin base material to separate conventional plating pretreatment. A plating method capable of directly forming a film, and the active state of the substrate surface activated by the plating pretreatment is maintained for a long period of time, and adhesion can be achieved without roughening the substrate surface. It is an object of the present invention to provide a plating pretreatment method capable of forming a metal film having high surface smoothness and a plating method including the process.

As a result of intensive research to achieve the above object, the inventors of the present invention, as a plating method or a plating pretreatment method, scattered metal particles while irradiating the surface of the resin substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm. The inventors have found that the above-described object can be achieved by depositing, and have completed the present invention.

That is, in the first plating method of the present invention, metal scattering particles are deposited while irradiating the surface of the resin substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm to form a metal film on the substrate. This is a characteristic plating method.

In addition, the second plating method of the present invention includes:
A pre-plating treatment step of depositing metal scattering particles while irradiating vacuum ultraviolet light having a wavelength of 50 nm to 100 nm on the surface of the resin substrate to form a metal film on the substrate;
A plating step of forming a further metal film on the metal film formed on the surface of the substrate by an electroless plating method and / or an electroplating method;
The plating method characterized by including.

Furthermore, the plating pretreatment method of the present invention is characterized in that metal particles are formed on the substrate by depositing metal scattering particles while irradiating the surface of the resin substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm. This is a plating pretreatment method.

In the first plating method, the second plating method and the plating pretreatment method of the present invention, the vacuum ultraviolet light and the scattered particles have a pulse width of 10 picoseconds to 100 nanoseconds on a target made of metal, and It is preferable that the irradiation intensity is generated by irradiation with a pulse laser beam having an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ² .

Although the reason why a metal film having high adhesion strength and excellent surface smoothness is formed on the resin substrate by the method of the present invention is not necessarily clear, the present inventors have as follows. I guess. That is, when a pulse laser beam having a pulse width of 10 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ² is irradiated onto a target made of a metal material, the target surface is heated to a high temperature. Is generated, and vacuum ultraviolet light having a wavelength of 50 nm to 100 nm is generated from the plasma. Since such vacuum ultraviolet light has a high absorption rate with respect to the resin (carbon atom), when this vacuum ultraviolet light is irradiated onto the resin substrate, p electrons, which are outer electrons of carbon atoms, are excited on the substrate surface. By ionizing, the bond between the carbon atom and the atom bonded to the carbon atom is broken, and the surface of the resin substrate is activated without being roughened to form an active terminal. On the other hand, from the target surface irradiated with the laser light, atoms or clusters containing metal are scattered with high energy according to the material constituting the target, and the target is heated in the plasma or on the target surface heated by the plasma. Neutral atoms and ions formed by evaporation of the constituent materials and clusters formed by combining some of the neutral atoms and ions are scattered with high energy. And when such scattered particles reach the resin substrate activated by the vacuum ultraviolet light, the scattered particles have high energy, and thus adhere and deposit firmly on the substrate, and the active ends are scattered by the scattered particles. The metal film is formed on the substrate surface with sufficient adhesion strength while being fixed and maintained in an active state. Therefore, according to the first plating method of the present invention, a metal film having high adhesion strength and excellent surface smoothness is directly applied to the surface of the resin base material without performing separate plating pretreatment as in the prior art. The present inventors infer that it will be formed as follows. Further, according to the second plating method of the present invention and the plating pretreatment method of the present invention, the surface of the base material is maintained in an active state for a long time without being roughened, and in this way The metal film formed in close contact with the substrate surface that has been activated to act as a catalyst in the subsequent electroless plating method or an electrode in the electroplating method, so that the adhesion strength is high and the surface smoothness The present inventors presume that a thickened metal film is formed.

Here, the vacuum ultraviolet light having a wavelength of 50 nm to 100 nm means vacuum ultraviolet light having at least a part of wavelengths in the wavelength region of 50 nm to 100 nm, and satisfying at least one of the following conditions: Preferably it is.
(i) having at least one peak of light intensity in a wavelength region of 50 nm to 100 nm;
(ii) the total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 100 nm to 150 nm;
(iii) The total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 50 nm or less.
(iv) The energy density of light in the wavelength region of 50 nm to 100 nm is 0.1 μJ / cm ^{2 to} 10 mJ / cm ² (more preferably 1 μJ / cm ^{2 to} 100 μJ / cm ² ) on the substrate. In addition, when the energy density on the substrate is lower than 0.1 μJ / cm ² , the time required for the treatment tends to be excessively long. On the other hand, when the energy density is higher than 10 mJ / cm ^{2, the} substrate is decomposed. There is a tendency.

In the first plating method, the second plating method, and the plating pretreatment method of the present invention, a mask having an opening formed corresponding to a desired pattern is formed on the surface of the substrate. A masking step may be further included. In that case, the scattered particles are deposited while the vacuum ultraviolet light is irradiated on a portion of the surface of the base material corresponding to the opening to form a metal film. It will be. Therefore, if the substrate surface is previously masked in this way in the first plating method of the present invention, a metal film having a high adhesion and a desired pattern is directly formed on the surface of the resin substrate. Is done. Further, in the second plating method and the plating pretreatment method of the present invention, if the substrate surface is masked in advance as described above, the adhesion to the surface of the resin substrate is high and the desired pattern is formed in the plating pretreatment step. The formed metal film is formed. Then, since the metal film thus formed acts as a catalyst in the subsequent electroless plating method or an electrode in the electroplating method, a further metal film is formed only in a portion where the metal film exists, and adhesion And a thick metal film having a desired pattern is obtained.

Further, in the first plating method, the second plating method and the plating pretreatment method of the present invention, hydrogen gas under reduced pressure in the container and / or inside or outside the container, It is preferable to deposit the scattered particles on the surface of the base material in a shield gas atmosphere containing at least one gas selected from the group consisting of helium gas, neon gas, and argon gas. When using a container whose inside is in a reduced pressure state in this way, vacuum ultraviolet light is irradiated to the surface of the resin base material without being absorbed by a vacuum ultraviolet light absorbing material such as oxygen in the air, and the surface of the resin base material is It tends to be activated more efficiently. In addition, when the treatment is performed under a shielding gas atmosphere, the vacuum base light is irradiated to the surface of the resin base material without being absorbed by the vacuum ultraviolet light absorbing material without being in a reduced pressure state, and the resin base material surface is activated more efficiently. Tend to. Further, in the latter case, it is not necessary to use a vacuum pump or a pressure vessel as compared with the former case, and therefore, it tends to be more preferable in terms of simplicity of the apparatus and low cost.

According to the first plating method of the present invention, a metal film having high adhesion and excellent surface smoothness is directly applied to the surface of the resin base material without subjecting the conventional separate plating pretreatment. It becomes possible to form.

In addition, according to the plating pretreatment method of the present invention, the surface of the resin base material is activated without roughening, and the activated state can be maintained for a long time. A metal film formed in close contact with the substrate surface can be used as a catalyst in an electroless plating method or an electrode in an electroplating method. Therefore, according to the second plating method of the present invention, it becomes possible to form a thickened metal film having high adhesion and excellent surface smoothness on the surface of the resin base material, and further pre-plating treatment The process and the plating process can be performed separately and independently.

  Hereinafter, the first plating method, the second plating method, and the plating pretreatment method of the present invention will be described in detail according to preferred embodiments thereof. First, a preferred embodiment of the first plating method of the present invention and a preferred embodiment of the plating pretreatment method of the present invention suitable for the second plating method of the present invention will be described in detail.

FIG. 1 is a schematic diagram showing a basic configuration of an embodiment of a plating apparatus suitable for carrying out the first plating method of the present invention. The plating apparatus shown in FIG. 1 is also used as a plating pretreatment apparatus suitable for carrying out the plating pretreatment method of the present invention as it is, that is, FIG. 1 is suitable for carrying out the plating pretreatment method of the present invention. It is a schematic diagram which shows the basic composition of one Embodiment of a plating pre-processing apparatus. The apparatus shown in FIG. 1 is configured as a so-called laser ablation apparatus 1, and includes a laser light source 2 and a processing container 3 into which laser light L ₁ emitted from the laser light source 2 is introduced. a target 4 with the laser beam L ₁ is the interior is illuminated, the substrate 6 should metal film 5 is formed is disposed on the surface.

The laser light source 2 may be any laser light generator that can irradiate a pulse laser beam having a pulse width of 10 picoseconds to 100 nanoseconds (preferably 100 picoseconds to 100 nanoseconds), and is not particularly limited. For example, a YAG laser device or an excimer laser device is preferable, and a YAG laser device is particularly preferable. Then, the laser light source 2 is disposed at a position irradiated with laser light L ₁ towards the target 4 which is located inside the treatment container 3. Although not shown, the laser beam L ₁ is generated so that the metal scattering particles a and the vacuum ultraviolet light L ₂ are efficiently generated from the surface of the target 4 when the target 4 is irradiated with the laser beam L _1. The energy density and irradiation angle of the laser beam may be adjusted by appropriately arranging a lens, a mirror or the like in the middle of the optical path. In particular, a condenser lens (not shown) is disposed inside or outside the processing container 3 so that the irradiation intensity of the pulsed laser light L ₁ applied to the target 4 is 10 ⁶ W / cm ² to 10 ¹² W / cm. ² is preferable, and 10 ⁸ W / cm ² to 10 ¹¹ W / cm ² is particularly preferable.

The processing container 3 is a container (for example, a stainless steel container) for accommodating at least the target 4 and the base material 6 therein, and introduces the laser beam L ₁ into the surface of the target 4 disposed in the container 3. A window 7 (for example, a quartz window) is provided. Further, a vacuum pump (not shown) is connected to the processing container 3 so that the inside of the container 3 can be maintained in a reduced pressure state of a predetermined pressure. When the container 3 whose inside is in a reduced pressure state is used in this way, the vacuum ultraviolet light L ₂ is irradiated on the surface of the base material 6 without being absorbed by a vacuum ultraviolet light absorbing material such as oxygen in the air. Is activated more efficiently. In addition, as a pressure at the time of maintaining the inside of the container 3 in a pressure-reduced state, a pressure of 1 Torr or less is preferable, and a pressure of 1 × 10 ⁻³ Torr or less is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 1 Torr or less.

The target 4 only needs to be made of a material that generates scattered particles of metal by irradiation with the laser beam L ₁ described above, and those made of various metals are preferably used. As such a metal material, various transition element metals, typical element metals, metalloids, or alloys thereof can be used, for example, Cu, Al, Ti, Si, Cr, Pt, Au, Ag, Zr, Mg, Ni, Fe, Co, Zn, Sn, W, Be, Ge, Mn, Mo, Nb, Ta, Hf, Pd, Rh, alloys containing them as main components, etc. A combination of metal materials may also be used. And as the target 4 used for a 1st plating method, it can select from the said metal material suitably from a viewpoint of the intended purpose of using a plating film. Moreover, as the target 4 used in the plating pretreatment method, Pd, Au, Ag, Pt, Sn, Ni, Co, among the above metal materials from the viewpoint of more effectively acting as a catalyst in an electroless plating process described later. , Fe, Cu, and Rh can be suitably used, and Pd, Au, Pt, and Ag are particularly preferable. In the electroplating process, all metals used as electrodes can be used, and Al and Cu are particularly preferable from the viewpoint of cost. The shape of the target 4 is not particularly limited, and a bulk material made of the target material formed into a plate shape, a rod shape, or the like, a tape target formed by applying the target material on a tape, vapor deposition, or the like Can be used.

The substrate 6 is a substrate made of a resin on which the metal film 5 is to be formed, and is specifically determined as appropriate depending on the use of the product to be obtained. Such made of a resin base material, as long as it contains carbon atoms in the vicinity of at least a surface thereof, Ru can be used conventional resin substrate. Such resin base materials include olefin resins {polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, ethylene. -Propylene-diene copolymer, ethylene-butene-diene copolymer, polymethylpentene, etc.}, butyl rubber, polyester, polycarbonate, polyacetal, polyamide, polyamideimide, polyimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, Polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polybenzimidazole, polycarbodiimide, acrylic resin {polymethyl (meth) acrylate , Poly (meth) acrylamide, etc.}, acrylic rubber, fluororesin {poly-4-fluorinated ethylene, etc.}, fluororubber, liquid crystal polymer, epoxy resin, melamine resin, urea resin, diallyl phthalate resin, phenol resin, polysilane, silicone resin (Polysiloxane, etc.), silicone rubber, urethane resin, styrene resin {polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, etc.}, polyethylene terephthalate, polybutylene terephthalate , Polyethylene naphthalate, polyvinyl chloride, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate, etc. (homopolymer or copolymer), and products thereof Substrate comprising a body and the like. In addition, such resin base materials include dyes, pigments, fibrous reinforcements (glass fibers, etc.), particulate reinforcements (talc, carbon black, etc.), plasticizers, flame retardants, heat stabilizers, if necessary. An appropriate amount of additives such as an antioxidant, a weather resistance imparting agent, an antistatic agent, a transparency improver, and an ultraviolet absorber may be contained. In addition, the shape and thickness of the base material 6 made of such a resin are not particularly limited, and a film shape, a plate shape, various shaped molded bodies, and the like are appropriately selected depending on the use of the product to be obtained.

The positional relationship between the base material 6 and the target 4 is not particularly limited, and the surface of the base material 6 is reliably irradiated with the vacuum ultraviolet light L ₂ generated from the surface of the target 4 and the scattered particles a are efficiently deposited. Thus, the base material 6 is appropriately disposed with respect to the target 4, and in FIG. 1, the base material 6 is disposed at a position where the angle Θ with respect to the normal line of the target 4 is 45 °. Further, a target driving device (for example, a target turntable, not shown) can be connected to the target 4, and in this case, a fresh surface of the target (laser light non-irradiated surface) is at the irradiation position of the laser light L _1. It can be sent out sequentially. Further, a substrate driving device (for example, a substrate turntable, not shown) may be connected to the substrate 6 so that the surface of the substrate 6 is activated more uniformly.

As described above, the embodiment of the plating apparatus suitable for carrying out the first plating method of the present invention and the embodiment of the plating pretreatment apparatus suitable for carrying out the plating pretreatment method of the present invention have been described. The apparatus suitable for the present invention is not limited to the above embodiment. That is, for example, in the above embodiment, the processing container 3 is connected to a vacuum pump (not shown), but at least one kind of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas is introduced. In this case, the interior of the container 3 can be maintained in a predetermined shielding gas atmosphere. With such internal use container 3 which is a shielding gas atmosphere, the surface of the substrate 6 without without a container 3 and a vacuum is vacuum ultraviolet light L ₂ is absorbed in the vacuum ultraviolet light absorbing material Irradiated, the surface of the substrate 6 is activated more efficiently. Further, it is preferable to connect both a vacuum pump (not shown) and a gas cylinder (not shown) to the processing container 3 so that the inside of the container 3 has a predetermined shielding gas atmosphere and is maintained at a predetermined pressure condition. is there. As such conditions, for example, a pressure of atmospheric pressure or lower in a helium gas atmosphere is preferable, and a pressure of 500 Torr or lower is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 1 Torr or less.

In the above embodiment, the laser light source 2 is disposed outside the processing container 3. However, the laser light source 2 may be disposed inside the processing container 3, in which case the laser light L ₁ is introduced into the container 3. This window 7 becomes unnecessary.

Furthermore, in the said embodiment, although the base material 6 is arrange | positioned in the position where the angle (theta) with respect to the normal line of the target 4 is 45 degrees, it is not specifically limited to such a positional relationship, The normal line of the target 4 The substrate 6 may be disposed at a position where the angle Θ with respect to the angle is in the range of about 0 ° to 80 °. Further, for example, a base material 6 made of a resin that can transmit the laser light L ₁ is used. The base material 6 is disposed opposite to the target 4 between the laser light source 2 and the target 4, and the base material 6 is transmitted. laser beam L ₁ is may be irradiated to the target 4 which is.

In addition, a target 4 in which a thin metal film is attached on a transparent film that can transmit the laser beam L ₁ is used, and the target 4 is based on a metal film on the transparent film between the laser light source 2 and the substrate 6. It is arranged so as to face the material 6 side, and vacuum is applied from the metal film surface (target material side) of the target 4 by the laser light L ₁ transmitted from the back surface (transparent film side) of the target 4 to the metal film surface (target material side). Ultraviolet light L ₂ and scattered particles a may be generated and supplied to the surface of the substrate 6. With such a configuration, the plating process and pre-plating process for a relatively large base material tend to be easier. Moreover, as a target used for such a structure, the tape-shaped target which laminated | stacked the above-mentioned target material on the film (for example, PET film) transparent with respect to a laser beam by vapor deposition, sticking, etc. is preferable.

  Next, referring to FIG. 1, a preferred embodiment of the first plating method of the present invention and a preferred embodiment of the plating pretreatment method of the present invention suitable for the second plating method of the present invention will be described. I will explain.

In the first plating method of the present invention and the plating pretreatment method of the present invention, a pulse laser beam L ₁ having a pulse width of 10 picoseconds to 100 nanoseconds (preferably 100 picoseconds to 100 nanoseconds) is applied to the target 4 described above. Is irradiated from the laser light source 2. Then, a high-temperature plasma P is formed on the surface of the target 4, and vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is generated from the plasma P. At the same time, atoms or clusters containing metal scatter with high energy from the surface of the target 4 irradiated with the laser beam L ₁ depending on the material constituting the target, and are heated by the plasma P or inside the plasma P. From the surface of the target 4, there are high neutral atoms and ions formed by evaporation of the material constituting the target, and clusters formed by combining some of the neutral atoms and ions. Spatter with energy. The pulse width of the pulsed laser light L ₁ is as light having a wavelength less than 50nm for laser energy in a short time is less than 10 picoseconds is irradiated to the target in concentration occurs, while the 100 nanosecond If exceeded, the energy of the laser is not sufficiently concentrated in time, and the wavelength of the generated light exceeds 100 nm. Further, in both cases where the wavelength of the generated light L ₂ is less than 50 nm and more than 100 nm, the absorption rate of the light L ₂ with respect to the resin (carbon atom) is low, and the surface of the resin base 6 is sufficiently activated. In other words, the adhesion strength between the formed metal film 5 and the resin base 6 is insufficient. Further, it is preferred that the irradiation intensity of the pulsed laser light _{L 1} irradiated to the target 4 is ^{10 6 W / cm 2 ~10 12} W / cm 2. When the irradiation intensity of the pulse laser beam L ₁ is less than 10 ⁶ W / cm ^2, there is a tendency that the vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is not sufficiently generated, and when exceeding 10 ¹² W / cm ² , the target is irradiated. are for main wavelength region of electromagnetic wave generated is in a wavelength range 50nm when the tends to amount of vacuum ultraviolet light L ₂ having a wavelength 50nm~100nm decreases.

The various scattering particles (ablator) a generated from the surface of the target 4 by irradiation of such a pulse laser beam L ₁ is supplied to the surface of the resin base material 6 with a vacuum ultraviolet light L _2. This way, the vacuum ultraviolet light L ₂ irradiated to the surface of the substrate 6 has a high absorption rate with respect to the resin (carbon atom), the surface of the resin base material 6 vacuum ultraviolet light L ₂ is irradiated sufficiently active It becomes. Since the scattered particles a reach there with high energy, the scattered particles a firmly adhere to and accumulate on the base material 6 and the surface of the base material 6 is maintained in an active state for a long time. The metal film 5 is formed on the surface of the substrate 6 with sufficient adhesion strength.

Therefore, according to the first plating method of the present invention, the metal film (plating film) 5 having high adhesion is directly formed on the surface of the resin base 6 without performing separate plating pretreatment as in the prior art. It is formed. And according to the 1st plating method of this invention, since the base-material surface is not roughened by the separate separate plating pretreatment like the past, the metal film 5 formed in the surface of the resin base material 6 is surface smooth. Excellent in properties. In the first plating method of the present invention, the thickness of the metal film (plating film) 5 formed on the surface of the substrate 6 is not particularly limited, and is appropriately determined according to the use of the obtained plated product. However, generally about 0.1-100 micrometers is preferable and about 0.5-30 micrometers is more preferable. Further, the time required for forming the metal film (plating film) 5 on the surface of the substrate 6 in the first plating method of the present invention (laser light irradiation time) is not particularly limited, and the thickness of the metal film is desired. The thickness is appropriately determined so as to have a plating thickness of approximately 1 second to 1 hour, and more preferably approximately 30 seconds to 30 minutes.

Further, according to the plating pretreatment method of the present invention, the surface of the resin base 6 is maintained in an active state for a long time without being roughened, and is thus activated. The metal film (catalyst layer or electrode layer) 5 formed in close contact with the substrate surface acts as a catalyst in the subsequent electroless plating method or an electrode in the electroplating method. Therefore, on the metal film (catalyst layer or electrode layer) 5 formed on the surface of the resin substrate 6 by performing electroless plating and / or electroplating described later after the plating pretreatment of the present invention, A further metal film (plating film) is formed in close contact with the substrate 6 via the metal film 5. According to the plating pretreatment method of the present invention, since the substrate surface is not roughened as described above, the metal film (catalyst layer or electrode layer, and plating film) formed on the surface of the resin substrate 6 is Excellent surface smoothness. The thickness of the metal film (catalyst layer or electrode layer) 5 formed on the surface of the substrate 6 in the plating pretreatment method of the present invention is not particularly limited, and is sufficient for electroless plating and / or electroplating described later. However, the catalyst is preferably about 1 nm to 100 nm, and the electrode is preferably about 300 nm to 1 μm. Further, the time (laser light irradiation time) required for forming the metal film (catalyst layer or electrode layer) 5 on the surface of the substrate 6 in the plating pretreatment method of the present invention is not particularly limited, and the thickness of the metal film Is appropriately determined so as to have a desired thickness, but in general, about 1 second to 1 hour is preferable, and about 30 seconds to 30 minutes is more preferable.

  In the first plating method of the present invention and the plating pretreatment method of the present invention, it is not necessary to heat the substrate to a high temperature when activating the surface of the substrate 6, and the substrate temperature is particularly Although it does not restrict | limit, generally what is necessary is just about room temperature.

In the first plating method of the present invention and the plating pretreatment method of the present invention suitable for the second plating method of the present invention, a mask having an opening formed corresponding to a desired pattern ( (Not shown) may be formed in advance on the surface of the substrate 6 (masking step), and then the above-described first plating method of the present invention or the plating pretreatment method of the present invention may be performed. Such a masking method is not particularly limited, and a place on the surface of the substrate 6 that should prevent vacuum ultraviolet light irradiation and scattering particle deposition and a place where vacuum ultraviolet light irradiation and scattering particle deposition should be possible. For example, (i) a method of closely attaching a metal mask formed in a desired mask pattern on a base material, (ii) a photo-resist on a photoresist film formed in advance on the base material A method of forming a desired mask pattern by a lithography method, (iii ) a method in which a seal having a desired mask pattern formed on the surface is brought into close contact with the substrate, and the mask pattern is transferred onto the substrate. it can.

When the first plating method of the present invention described above or the plating pretreatment method of the present invention is applied to the base material that has been subjected to the masking treatment in this way, the portion corresponding to the opening portion on the surface of the base material is applied. The scattered particles are deposited while being irradiated with the vacuum ultraviolet light, and a metal film is formed. Therefore, if the substrate surface is previously masked in this way in the first plating method of the present invention, a metal film (plating film) having a high adhesion and a desired pattern is formed on the surface of the resin substrate. Formed directly. In addition, if the substrate surface is previously masked in this way in the plating pretreatment method of the present invention, a metal film having a high adhesion and a desired pattern on the surface of the resin substrate in the plating pretreatment step ( Catalyst layer or electrode layer) is formed. And since the metal film (catalyst layer or electrode layer) formed in this way acts as a catalyst in the electroless plating method in the second plating method of the present invention described later or an electrode in the electroplating method, such a metal film A further metal film is formed only on the portion where the film exists, and a thick metal film having a high adhesion and a desired pattern is obtained.

  In the first plating method of the present invention and the plating pretreatment method of the present invention suitable for the second plating method of the present invention, the surface of the substrate is formed before or after the metal film is formed on the substrate. It may be contacted with an acid solution, an alkali solution or an organic solvent. Specifically, a method of treating a substrate surface with an organic solvent before forming the metal film, a method of treating the metal film surface with an organic solvent, an acid solution or an alkali solution after forming the metal film, a metal, A method of treating the substrate surface with an organic solvent and an acid solution or an alkali solution before and after forming the film is preferably employed. If it does in this way, it will become possible to perform a degreasing process with respect to the base-material surface, and a surface oxide film removal process with respect to the metal film surface. As the organic solvent used here, alcohols such as methanol, ethanol, propanol and isopropyl alcohol, acetone, and the like are preferable for the purpose of degreasing the surface of the substrate. The acid solution is preferably an aqueous solution such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, and the alkaline solution is preferably an aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate or sodium phosphate. In addition, the concentration and temperature of the solution, the treatment time, the contact method, and the like in such treatment are not particularly limited, and are appropriately adjusted according to the solution to be used. Moreover, when processing with an acid solution or an alkali solution, you may add suitably the process of neutralizing those solutions.

Next, a preferred embodiment of the second plating method of the present invention will be described. The second plating method of the present invention includes the above-described plating pretreatment step, and an electroless plating method and / or on the metal film (catalyst layer or electrode layer) formed on the surface of the resin substrate in the step. And a plating step of forming a further metal film by electroplating.

  The specific method of the electroless plating method according to the present invention is not particularly limited, and a known electroless plating method can be appropriately employed. For example, a metal salt, a complexing agent, and a reducing agent are used as main components. A method of immersing the substrate in a plating bath such as an acidic plating solution, a neutral plating solution, an alkaline plating solution (for example, an alkali hydroxide bath, an ammonia bath, etc.), a spray method using such a plating solution, etc. For example, a method of supplying to the surface of the substrate is preferably employed. The metal salt used here is not particularly limited as long as it is a metal salt intended to form a metal film by electroless plating. Examples of such metal salts include various metal halides, acid salts, cyanides, etc. Among them, nickel sulfate, nickel chloride, nickel hypophosphite, cobalt sulfate, cobalt chloride, copper sulfate, gold cyanide Potassium and the like are preferable. Examples of the reducing agent include sodium hypophosphite, hydrazine, sodium borohydride, formaldehyde and the like. Furthermore, examples of the complexing agent include sodium citrate, sodium ethylenediaminetetraacetate, sodium tartrate and the like. In addition, the composition, temperature and pH, treatment time, contact method, etc. of the solution in such electroless plating treatment are not particularly limited and can be appropriately adjusted according to the method used, metal salt, etc. The conditions for performing electrolytic copper plating include a metal salt concentration of about 1.5 g / l to 4 g / l, a solution temperature of about 20 to 40 ° C., a solution pH of about 8 to 10 and a treatment time of about 3 to 30 minutes. Is used. Further, the thickness of the metal film (electroless plating film) formed by such electroless plating is not particularly limited, and is appropriately determined according to the use of the obtained plated product. About 1-5 micrometers is preferable.

  Further, the specific method of the electroplating method according to the present invention is not particularly limited, and a known electroplating method can be appropriately employed. For example, a metal film to be formed by electroplating can be used. Immerse the substrate in an electrolyte containing ions to give an appropriate potential difference between the substrate (usually the cathode) and the counter electrode (usually the anode, the metal or insoluble electrode on which the metal film is to be formed). The method to do is employ | adopted suitably. The metal used here can be appropriately selected depending on the application, and may be the same as or different from the target material. The composition, temperature and pH, treatment time, potential difference and the like of the electrolytic solution in such electroplating treatment are not particularly limited, and are appropriately adjusted according to the method used, the metal, and the like. In addition, the thickness of the metal film (electroplating film) formed by such electroplating is not particularly limited and is appropriately determined according to the use of the obtained plated product, and is, for example, about 2 μm to 30 μm depending on the use. Is preferred.

In the second plating method of the present invention, the metal film (catalyst layer or electrode layer) formed in close contact with the surface of the resin base material in the above-described plating pretreatment step is used as a catalyst in the electroless plating method. In order to act as an electrode in the electroplating method, a further metal film (plating film) is formed by the above-described electroless plating and / or electroplating, and between the metal film thus thickened and the substrate. High adhesion is achieved. In addition, since the surface of the base material is not roughened according to the above-described plating pretreatment method, the metal film (catalyst layer or electrode layer and plating film) formed by the second plating method of the present invention has a surface smoothness. It will be excellent. In the second plating method of the present invention, the thickness of the metal film (plating film) formed on the surface of the substrate 6 is not particularly limited, and is appropriately determined according to the use of the obtained plated product. In general, the thickness is preferably about 0.1 μm to 100 μm, more preferably about 0.5 μm to 30 μm.

  Further, the metal film (catalyst layer or electrode layer) formed in the above-mentioned plating pretreatment process and the metal film (plating film) formed by the electroless plating process and / or the electroplating process are made of the same metal material. However, they may be made of different metal materials, and the combination thereof is appropriately selected from the viewpoints of catalyst activity, environmental resistance, cost, and the like. Further, both the electroless plating process and the electroplating process may be performed after the above-described plating pretreatment process, and in the case where a thick metal film (plating film) is required, the electroless plating process is performed. The electroplating process may be performed a plurality of times and / or a plurality of times. In addition, since the substrate surface activated in the above-described pre-plating process is maintained in an active state for a long time, it is not always necessary to perform the plating process immediately after the above-mentioned pre-plating process. Even if the plating process is performed after about one month or more has elapsed since the execution of the treatment process, a high degree of adhesion strength is achieved.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-5)
[Plating step (first plating method)]
The laser light source 2 is a YAG laser device (manufactured by Continuum, product name: NY-81), the processing container 3 is a vacuum container with a quartz window (made of stainless steel, capacity 20 liters), and the target 4 is a copper plate (one side 45 mm square, thick 1 mm), and using a polyimide substrate (manufactured by Toray DuPont, Kapton 500V sheet, 40 mm × 40 mm × 0.125 mm) as the substrate 6, the plating apparatus shown in FIG. The incident angle of the laser beam on the target 4 is 45 °, the substrate 6 is arranged at a position where the angle Θ with respect to the normal line of the target 4 is 0 °, and the laser beam irradiation positions of the substrate 6 and the target 4 are The distance between them was 120 mm.

Next, using the manufactured apparatus, the inside of the container 3 is evacuated for 20 minutes or more with an oil rotary pump, and then the target 4 is rotated at about 120 rpm, and the wavelength of the laser light source 2 is 532 nm, the irradiation intensity is 2 × 10. ^The target 4 was irradiated with ⁹ W / cm ² ( ² GW / cm ² ), a pulse width of 8 nanoseconds, and a pulse laser beam L ₁ having a frequency of 10 Hz. The surface of the target 4 hot plasma P is formed, wavelength vacuum ultraviolet light L ₂ is generated in the range of 50 nm to 100 nm, at the same time, the neutral atoms of the copper from the surface of the target 4, ions, and among these Scattered particles (ablators) a such as clusters formed by combining some of the active atoms and ions were scattered. Then, the surface of the substrate 6 was irradiated with the vacuum ultraviolet light L ₂ generated from the plasma P and sufficiently activated, and the scattered particles a arrived there with high energy and adhered and deposited. The irradiation time was the time shown in Table 1, and the substrate temperature was about 25 ° C.

Then, after the substrate 6 after stopping the irradiation of the laser beam L ₁ and cooled over 20 minutes, by introducing air taken out substrate 6 in the container 3. A copper film 5 was formed on the surface of the substrate 6. When the film thickness was measured with a stylus type film thickness meter, the film thickness was as shown in Table 1. From the results shown in Table 1, it was confirmed that the film thickness increased as the irradiation time of the laser light increased.

[Crosscut tape peeling test]
Using the substrate having a metal film (plated film) formed on the surface in this manner, a cross-cut tape peeling test is performed in accordance with the test method described in JIS K5600, and the following evaluation criteria:
A: The number of cross cuts is 0/100
B: The number of cross-cuts is 1/100 to 10/100
C: The number of cross cuts is 11/100 to 100/100
Evaluated according to. The obtained results are shown in Table 1. From the results shown in Table 1, the adhesion of the copper film formed by the first plating method of the present invention to the substrate is high, and the adhesion is high on the substrate without a separate separate plating pretreatment as in the prior art. It was confirmed that the metal film can be directly formed.

（実施例６〜９）
基材６としてポリカーボネート基材（ＩＭＡＴＩＯＮ社製、ＣＤＲ８０Ｚ（ＣＤ−Ｒメディアのポリカーボネート基板部分）、３０ｍｍ×３０ｍｍ×１．２ｍｍ）を用い、基材６をターゲット４の法線に対する角度Θが２０°となる位置に配置し、基材６とターゲット４のレーザー光照射位置との間の距離を６０ｍｍとし、更にレーザー光Ｌ_１の照射強度及び照射時間を表２に示す値とした以外は実施例１と同様にしてメッキ工程（第１のメッキ方法）を実施した。基材６の表面には銅膜５が形成されており、表２に示す膜厚であった。また、実施例７において基材表面に形成された金属膜の表面を原子力間顕微鏡で観察したところ、表面の凹凸は１０ｎｍ以下であり、極めて表面平滑性に優れていることが確認された。さらに、このようにして表面に金属膜が形成された基材を用いて実施例１と同様にして碁盤目テープ剥離試験を行った結果を表２に示す。

(Examples 6 to 9)
A polycarbonate substrate (made by IMATION, CDR80Z (a polycarbonate substrate part of CD-R media), 30 mm × 30 mm × 1.2 mm) is used as the substrate 6, and the angle Θ with respect to the normal of the target 6 is 20 °. Example except that the distance between the substrate 6 and the laser beam irradiation position of the target 4 is set to 60 mm, and the irradiation intensity and irradiation time of the laser beam L ₁ are set to the values shown in Table 2. In the same manner as in No. 1, a plating step (first plating method) was performed. A copper film 5 was formed on the surface of the substrate 6, and the film thickness was as shown in Table 2. Moreover, when the surface of the metal film formed in the base-material surface in Example 7 was observed with the atomic force microscope, the surface unevenness | corrugation was 10 nm or less, and it was confirmed that it is extremely excellent in surface smoothness. Further, Table 2 shows the results of the cross-cut tape peeling test performed in the same manner as in Example 1 using the base material having the metal film formed on the surface in this manner.

From the above results, the copper film formed by the first plating method of the present invention has high adhesion to the substrate and excellent surface smoothness, and the irradiation intensity of the laser beam L ₁ is ² to 4 GW / cm ^2. In this case, it was confirmed that the adhesion was particularly high.

In Example 9 (irradiation intensity: 4 GW / cm ² ), the intensity of the vacuum ultraviolet light L ₂ emitted from the plasma P when the laser beam L ₁ is irradiated onto the target 4 is determined based on the oblique incidence diffraction grating spectrometer and the X-ray. The results obtained by measuring with a CCD camera are shown in FIG. Further, in the same manner as in Example 9 except that the irradiation intensity was set to 60 GW / cm ² , the intensity of the vacuum ultraviolet light L ₂ emitted from the plasma P was similarly measured, and the obtained result is shown in FIG. Show. From the results shown in FIG. 2, it was confirmed that vacuum ultraviolet light having a wavelength of 50 to 80 nm was efficiently generated under the condition where the irradiation intensity of the laser light was 4 to 60 GW / cm ² .

（実施例１０）
［メッキ前処理工程（第２のメッキ方法）］
ターゲット４としてＰｄ円板（直径４０ｍｍ、厚さ２ｍｍ）、基材６としてＡＢＳ樹脂基材（日本Ａ＆Ｌ社製、メッキ用ＡＢＳ樹脂ＡＰ−８Ａ、６０ｍｍ×３０ｍｍ×３ｍｍ）を用い、ターゲット４へのレーザー光の入射角を４５°とし、基材６をターゲット４の法線に対する角度Θが０°となる位置に配置し、基材６とターゲット４のレーザー光照射位置との間の距離を８０ｍｍとし、更にレーザー光Ｌ_１の照射強度を６ＧＷ／ｃｍ^２及び照射時間を１分間とした以外は実施例１と同様にしてメッキ前処理工程（第２のメッキ方法）を実施した。なお、本実施例においては図１に示す装置をメッキ前処理装置として使用し、実施例１におけるメッキ工程に対応する処理が本実施例においてはメッキ前処理工程に相当する。このようにしてメッキ前処理を施された基材６の表面にはＰｄ膜５が形成されており、膜厚は５ｎｍであった。

(Example 10)
[Plating pretreatment step (second plating method)]
A Pd disk (diameter 40 mm, thickness 2 mm) is used as the target 4, and an ABS resin base material (manufactured by Japan A & L, ABS resin AP-8A for plating, 60 mm × 30 mm × 3 mm) is used as the base 6. The incident angle of the laser beam is 45 °, the substrate 6 is arranged at a position where the angle Θ with respect to the normal of the target 4 is 0 °, and the distance between the substrate 6 and the laser beam irradiation position of the target 4 is 80 mm. and then, it was carried out further laser light L ₁ of the irradiation intensity 6GW / cm ² and except that the irradiation time was 1 minute in the same manner as in example 1 pre-plating process (second plating process). In this embodiment, the apparatus shown in FIG. 1 is used as a plating pretreatment apparatus, and the processing corresponding to the plating process in the first embodiment corresponds to the plating pretreatment process in this embodiment. A Pd film 5 was formed on the surface of the substrate 6 that had been subjected to the plating pretreatment in this way, and the film thickness was 5 nm.

[Plating process (second plating method)]
Next, when the base material subjected to the plating pretreatment was immersed in an electroless copper plating solution (MK-430 manufactured by Muromachi Chemical Co., Ltd.) at 25 ° C. for 30 minutes, an electroless copper plating treatment was performed. A copper film having a thickness of about 0.8 μm was formed on the Pd film.

Furthermore, the bath composition is CuSO ₄ .5H ₂ O concentration: 100 g / l, H ₂ SO ₄ concentration: 160 g / l, the temperature is 25 ° C., and the cathode current density is 2 A / dm with respect to the substrate on which the copper film is formed. ^{2. When} an electrolytic copper plating process was performed under the condition that the time was 60 minutes, a copper film having a film thickness of about 20 μm was formed on the Pd film on the surface of the substrate.

[Peeling test]
A peel test was carried out in accordance with the adhesion test method described in JIS H8630 using a substrate having a metal film (plating film) formed on the surface in this way, and the peel strength (peel strength) was measured. The result was 0.9 kg / cm. The test width was 10 mm.

  From the above results, according to the second plating method of the present invention, a metal film acting as a catalyst layer is formed on the substrate without any special surface treatment, and further, a base film is formed thereon by electroless plating and electroplating. It was confirmed that a metal film (plating film) having high adhesion to the material was formed.

Example 11
A plating pretreatment process (second plating method) was performed in the same manner as in Example 10 except that an Au disk (diameter 40 mm, thickness 2 mm) was used as the target 4. An Au film 5 was formed on the surface of the base material 6 that had been subjected to the plating pretreatment in this way, and the film thickness was 4 nm. Next, when only the electroless copper plating treatment in Example 10 was applied to the base material subjected to the plating pretreatment in the same manner as in the same example, the film thickness was about on the Au film on the surface of the base material. A 0.9 μm copper film was formed. From the above results, according to the second plating method of the present invention, a metal film acting as a catalyst layer is formed on the substrate without any special surface treatment, and further, a metal film (plating) is formed thereon by electroless plating. It was confirmed that a film) was formed.

Example 12
Pre-plating process as in Example 10 except that an Ag disk (diameter 40 mm, thickness 2 mm) is used as the target 4, the irradiation intensity of the laser beam L ₁ is 4 GW / cm ² and the irradiation time is 1 minute. (Second plating method) was performed. The Ag film 5 was formed on the surface of the base material 6 that had been subjected to the plating pretreatment in this way, and the film thickness was 1 nm. Next, an electroless copper plating treatment was performed by immersing the base material subjected to the pretreatment for plating for 15 minutes in an electroless copper plating solution (Okuno Pharmaceutical Co., Ltd., OPC Copper TG) at 30 ° C. However, a copper film having a film thickness of about 0.2 μm was formed on the Ag film on the substrate surface. From the above results, according to the second plating method of the present invention, a metal film acting as a catalyst layer is formed on the substrate without any special surface treatment, and further, a metal film (plating) is formed thereon by electroless plating. It was confirmed that a film) was formed.

(Example 13)
A copper plate (one side 45 mm square, 1 mm thick) is used as the target 4, and a glass epoxy base material (Risholite glass epoxy substrate, 40 mm × 40 mm × 0.2 mm) manufactured by Risho Kogyo Co., Ltd. is used as the base material 6. Is disposed at a position where the angle Θ with respect to the normal line is 0 °, the distance between the substrate 6 and the laser light irradiation position of the target 4 is 50 mm, and the irradiation intensity of the laser light L ₁ is ² GW / cm ² and A plating pretreatment step (second plating method) was performed in the same manner as in Example 10 except that the irradiation time was 120 minutes. The copper film 5 was formed on the surface of the base material 6 that had been subjected to the plating pretreatment in this way, and the film thickness was 0.8 μm. Next, when only the electrolytic copper plating process in Example 10 was applied to the base material subjected to the plating pretreatment in the same manner as in the same example, the film thickness was about 20 μm on the copper film on the base material surface. A copper film was formed.

  When the peel strength was measured in the same manner as in Example 10 on the substrate having the metal film (plated film) formed on the surface in this manner, the result was 0.7 kg / cm. From the above results, according to the second plating method of the present invention, a metal film acting as an electrode layer is formed on the base material without any special surface treatment, and the adhesion to the base material is further formed thereon by electroplating. It was confirmed that a high metal film (plating film) was formed.

(Example 14)
A polyimide base material (manufactured by Toray DuPont, Kapton 500V sheet, 20 mm × 20 mm × 0.125 mm) was used as the base material 6, and a stainless steel mask (10 mm × 10 mm × 20 μm) was adhered to the surface. The stainless mask has three L-shaped openings each having a side of 2 mm, and the line widths of the openings are three types of 200 μm, 100 μm, and 50 μm.

Next, using the base material 6 with the mask, the base material 6 is disposed at a position where the angle Θ with respect to the normal line of the target 4 is 0 °, and between the base material 6 and the laser light irradiation position of the target 4. The plating step (first plating method) was performed in the same manner as in Example 1 except that the distance was 40 mm, the irradiation intensity of the laser beam L ₁ was 1.3 GW / cm ² and the irradiation time was 30 minutes. An L-shaped copper film pattern (with a film thickness of about 100 nm) is formed on the surface of the substrate 6 thus plated, and the line width of the copper film pattern is the line width of the mask opening. And the error range.

  Thus, when the surface of the copper film pattern formed on the substrate surface was observed with an atomic force microscope, the surface unevenness was 10 nm or less, and it was confirmed that the surface smoothness was extremely excellent. Moreover, when the electroless copper plating treatment and / or the electrolytic copper plating treatment were performed on the base material having the copper film pattern formed on the base material in the same manner as in Examples 10 to 13, the base material was obtained. It was confirmed that a thicker copper film was formed on the copper film pattern on the surface.

As described above, according to the first plating method of the present invention, the surface of the resin base material is high in adhesion and excellent in surface smoothness without being subjected to a separate separate plating pretreatment as in the prior art. A metal film can be formed directly.

In addition, according to the plating pretreatment method of the present invention, the surface of the resin base material is activated without roughening, and the activated state can be maintained for a long time. A metal film formed in close contact with the substrate surface can be used as a catalyst in an electroless plating method or an electrode in an electroplating method. Therefore, according to the second plating method of the present invention, it becomes possible to form a thickened metal film having high adhesion and excellent surface smoothness on the surface of the resin base material, and further pre-plating treatment The process and the plating process can be performed separately and independently.

  Accordingly, the present invention provides a plating method for producing high-density electronic circuit boards, functional parts, structural parts, electromagnetic wave shielding materials, etc., which require high surface smoothness as well as high adhesion to a substrate. As well as a plating pretreatment method therefor.

It is a schematic diagram which shows the basic composition of suitable one Embodiment of the plating apparatus (or plating pretreatment apparatus) suitable for this invention. It is a graph which shows the relationship between the irradiation intensity | strength of a pulse laser beam, and the intensity | strength of vacuum ultraviolet light with a wavelength of 50-80 nm.

Explanation of symbols

1 ... plating apparatus (or plating pretreatment apparatus), 2 ... laser light source, 3 ... processing vessel 4 ... target, 5 ... metal film, 6 ... resin substrate 7 ... window, L 1 _... pulsed laser beam, L ₂ ... vacuum ultraviolet light, a ... scattered particles, P ... plasma.

Claims (9)

A plating method comprising depositing metal scattering particles while irradiating a surface of a resin substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm to form a metal film on the substrate. A pre-plating treatment step of depositing metal scattering particles while irradiating vacuum ultraviolet light having a wavelength of 50 nm to 100 nm on the surface of the resin substrate to form a metal film on the substrate;
A plating step of forming a further metal film on the metal film formed on the surface of the substrate by an electroless plating method and / or an electroplating method;
The plating method characterized by including. The vacuum ultraviolet light and the scattered particles irradiate a target made of metal with a pulse laser beam having a pulse width of 10 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. The plating method according to claim 1, wherein the plating method is generated.   The method further includes a masking step of forming a mask having openings formed corresponding to a desired pattern on the surface of the substrate, and the vacuum is applied to a portion of the surface of the substrate corresponding to the openings. The plating method according to any one of claims 1 to 3, wherein the metal particles are formed by depositing the scattered particles while irradiating with ultraviolet light.   Depositing the scattered particles on the surface of the substrate in a reduced pressure state and / or in a shield gas atmosphere containing at least one gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas The plating method according to any one of claims 1 to 4, wherein the plating method is characterized. A pretreatment method for plating, comprising depositing metal scattering particles while irradiating a surface of a resin substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm to form a metal film on the substrate. The vacuum ultraviolet light and the scattered particles irradiate a target made of metal with a pulse laser beam having a pulse width of 10 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. The plating pretreatment method according to claim 6, wherein the plating pretreatment method is generated.   The method further includes a masking step of forming a mask having openings formed corresponding to a desired pattern on the surface of the substrate, and the vacuum is applied to a portion of the surface of the substrate corresponding to the openings. The plating pretreatment method according to claim 6 or 7, wherein the metal particles are formed by depositing the scattered particles while irradiating with ultraviolet light.   Depositing the scattered particles on the surface of the substrate in a reduced pressure state and / or in a shield gas atmosphere containing at least one gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas The plating pretreatment method according to claim 6, wherein the plating pretreatment method is any one of claims 6 to 8.

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