JP3926835B1 - Formation method of plating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive electroless plating film having high adhesion strength on the surface of various kinds of polymer members.
SOLUTION: A polymer member impregnated with metal fine particles is prepared inside the surface, high-pressure carbon dioxide is brought into contact with the polymer member to swell the vicinity of the surface of the polymer member, and the vicinity of the surface of the polymer member is swollen. A method for forming a plating film comprising: contacting a polymer member with an electroless plating solution containing high-pressure carbon dioxide and causing a plating reaction in a state; and forming a plating film on the polymer member. Solve the above problems.
[Selection] FIG.

Description

  The present invention relates to a method for forming a plating film on a polymer member, and more particularly to a method for forming a plating film on a polymer member by an electroless plating method.

  Conventionally, an electroless plating method is known as a method for forming a metal film on the surface of a polymer member (polymer molded product) at low cost. However, in the electroless plating method, in order to ensure the adhesion of the plating film, the surface of the polymer member is etched using an oxidizing agent having a large environmental load such as hexavalent chromic acid or permanganic acid as a pretreatment of the electroless plating. It is necessary to roughen the surface of the polymer member. In addition, polymers immersed in such an etching solution, that is, polymers to which electroless plating can be applied are limited to polymers such as ABS. This is because ABS contains a butadiene rubber component, which is selectively immersed in an etching solution to form irregularities on the surface, whereas other polymers are selective for such an etching solution. This is because there are few components that are oxidized to the surface and it is difficult to form irregularities on the surface. Therefore, for a polycarbonate or the like which is a polymer other than ABS, a plating grade in which ABS or an elastomer is mixed to enable electroless plating is commercially available. However, with such plating grade polymers, deterioration of physical properties such as a decrease in heat resistance of the main material is inevitable, and it has been difficult to apply to molded products that require heat resistance.

  Conventionally, a technique for applying a surface modification method using high-pressure carbon dioxide such as supercritical carbon dioxide to plating pretreatment has been proposed. In the surface modification method using high-pressure carbon dioxide, the functional material is dissolved in high-pressure carbon dioxide, and the functional material is dissolved on the surface of the polymer member by bringing the high-pressure carbon dioxide dissolved in the functional material into contact with the polymer member. The polymer member surface is highly functionalized (modified) by penetrating the inside. For example, the present inventors have disclosed a method of performing a surface modification treatment using high-pressure carbon dioxide at the same time as injection molding to make the surface of a polymer molded product highly functional (for example, see Patent Document 1).

  Patent Document 1 discloses the following surface modification method. First, after plasticizing and weighing the resin in a heating (plasticizing) cylinder of an injection molding machine, the screw in the heating cylinder is sucked back and moved backward. Next, a functional organic material such as high pressure carbon dioxide in a supercritical state and a metal complex dissolved therein is applied to the front part (flow front part) of the molten resin that has become negative pressure (reduced pressure) due to the suck back of the screw. Introduce. By this operation, the high pressure carbon dioxide and the functional material can be infiltrated into the molten resin in the front portion of the screw. Next, the molten resin is injection-filled into a mold. At this time, the molten resin in the front portion of the screw infiltrated with the functional material is first injected into the mold, and then the molten resin in which the functional material is hardly infiltrated is injected and filled. When the molten resin in the front part of the screw infiltrated with the functional material is injected, the molten resin in the front part of the screw is pulled by the mold surface due to the fountain flow phenomenon (fountain effect) of the flowing resin in the mold. A surface layer (skin layer) is formed in contact with the mold. Therefore, in the surface modification method described in Patent Document 1, a polymer molded article in which a functional material is impregnated (surface-modified by the functional material) is produced inside the surface of the polymer molded article. When a metal complex containing metal fine particles as a plating catalyst is used as a functional material, a polymer molded product impregnated with the plating catalyst on the surface can be obtained, so that the surface is roughened with an etching solution as in the conventional plating pretreatment method. An injection-molded article that can be electrolessly plated can be obtained without the need to make it.

  Furthermore, conventionally, a method of performing electroless plating using an electroless plating solution containing supercritical carbon dioxide has been disclosed (for example, Patent Document 2 and Non-Patent Document 1). In these documents, an electroless plating solution and supercritical carbon dioxide are dissolved using a surfactant, and an emulsion (emulsion state) is formed by stirring to cause a plating reaction in the emulsion. A method is disclosed. Usually, in electroplating or electroless plating, hydrogen gas generated during the plating reaction stays on the surface of the object to be plated, causing pinholes in the plating film. However, when an electroless plating solution containing supercritical carbon dioxide is used as in the electroless plating method disclosed in the above-mentioned document, supercritical carbon dioxide dissolves hydrogen, so it is generated during the plating reaction. It is said that the hydrogen that is removed is removed, so that a pinhole is hardly generated and an electroless plating film having high hardness is obtained.

Japanese Patent No. 3696878 Japanese Patent No. 3571627 Surface technology Vol. 56, NO. 2, P83 (2005)

  As described above, in the conventional resin plating method, it is necessary to perform a pretreatment with a large environmental load, and the selectivity of the polymer material is also narrow.

  In addition, when the metal fine particles serving as the plating catalyst are infiltrated into the surface of the polymer member using the surface modification method of the polymer member using high-pressure carbon dioxide such as supercritical fluid described in Patent Document 1, As described above, a polymer member having metal fine particles serving as a plating catalyst on the surface and inside the surface is obtained. However, when electroless plating is applied to such a polymer member, only the fine metal particles present on the outermost surface of the polymer member contribute to the catalyst core of the electroless plating, and the inside of the polymer member (inside the surface) The existing metal fine particles become excessive catalyst nuclei and are uneconomical. In addition, when a plating film is formed on a polymer member obtained using the technique described in Patent Document 1, the surface of the polymer member is not roughened, so that it is difficult to obtain a physical anchor effect of the plating film. There was a problem that it was difficult to obtain strong adhesion of the molded product.

  The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for forming an electroless plating film having a low adhesion and high adhesion strength on the surface of a polymer member. is there.

  According to the first aspect of the present invention, there is provided a method for forming a plating film on a polymer member, comprising preparing a polymer member impregnated with metal fine particles inside the surface, and contacting the polymer member with high-pressure carbon dioxide. The surface of the polymer member is swollen, and the surface of the polymer member is swollen, and an electroless plating solution containing high-pressure carbon dioxide is brought into contact with the polymer member to form a plating film on the polymer member. Forming a plating film.

  The term “high-pressure carbon dioxide” as used herein means not only supercritical carbon dioxide but also high-pressure liquid carbon dioxide and high-pressure carbon dioxide gas. The “electroless plating method” as used herein refers to a method of depositing a metal film using a reducing agent on the surface of a substrate having catalytic activity without using an external power source.

  When the present inventors diligently examined the electroless plating method using the electroless plating solution containing supercritical carbon dioxide disclosed in Patent Document 2 and Non-Patent Document 1, etc., metal fine particles are formed inside the surface. Simply contacting the impregnated polymer member (polymer member containing fine metal particles in the vicinity of the surface) with an electroless plating solution containing high-pressure carbon dioxide (an electroless plating solution in a state in which a plating reaction occurs) Although an electroless plating film is formed on the surface, it has been found that it is difficult to form a plating film having sufficient adhesion. According to the inventors' verification experiment, in this case, the plating film grows mainly using metal fine particles present on the outermost surface of the polymer member as a catalyst nucleus, and the physical anchor effect of the plating film is obtained. I found it difficult. Therefore, it is considered that the strong adhesion between the plating film and the molded product cannot be obtained simply by bringing the electroless plating film in a state where the plating reaction occurs into contact with the polymer member together with the high-pressure carbon dioxide.

  In contrast, in the method for forming a plating film of the present invention, first, high pressure carbon dioxide is brought into contact with a polymer member impregnated with metal fine particles such as Pd, Ni, Pt, and Cu that serve as plating catalyst nuclei. At this time, when the polymer member is formed of an amorphous material, the glass transition temperature is lowered and the vicinity of the surface is softened and swells. On the other hand, when the polymer member is formed of a crystalline material, the intermolecular distance increases in the vicinity of the surface and swells even if it is not softened.

  Next, the polymer member in such a surface state is brought into contact with an electroless plating solution containing high-pressure carbon dioxide (an electroless plating solution in a state where a plating reaction occurs (for example, a high temperature state)). At this time, since the electroless plating solution is brought into contact with the vicinity of the surface of the polymer member being swollen, the electroless plating solution can penetrate into the inside of the polymer member together with the high-pressure carbon dioxide. At this time, since the electroless plating solution mixed with high-pressure carbon dioxide in a supercritical state has a low surface tension, the electroless plating solution is more easily penetrated into the polymer member. As a result, the electroless plating solution reaches the metal fine particles present inside the polymer member, and the plating film grows using the metal fine particles present inside the polymer member as catalyst nuclei. That is, in the method for forming a plating film of the present invention, the plating film grows not only on the surface of the polymer member but also with the metal fine particles present inside as a catalyst nucleus, so that the plating film bites into the inside of the polymer member. Formed on the member. Therefore, in the plating film forming method of the present invention, it is not necessary to roughen the surface of the polymer member by etching unlike the conventional electroless plating method, and it can easily adhere to various types of polymer members. An excellent plating film can be formed. Further, in the method for forming a plating film of the present invention, the surface of the polymer member is not roughened as in the conventional electroless plating method, so that a plating film having a very small surface roughness (nano order) can be formed. .

  In the method for forming a plating film of the present invention, when high pressure carbon dioxide is brought into contact with the polymer member, an electroless plating solution having a temperature at which a plating reaction does not occur together with the high pressure carbon dioxide is brought into contact with the polymer member. It is preferable to increase the temperature of the electroless plating solution to a temperature at which a plating reaction occurs when the plating solution is infiltrated into the polymer member to form a plating film on the polymer member. In this method, before the plating reaction occurs, the polymer member is swollen by contacting the polymer member with an electroless plating solution that is not in a plating reaction state together with high-pressure carbon dioxide, and at the same time, the electroless plating solution is allowed to flow inside the polymer member. Can penetrate. Therefore, in this method, the electroless plating solution can be surely penetrated into a deeper position, and a strong metal film having high adhesion can be stably formed on the surface of the polymer member.

  In the method for forming a plating film of the present invention, when the high-pressure carbon dioxide is brought into contact with the polymer member, the first electroless plating solution having a plating solution concentration that does not cause a plating reaction together with the high-pressure carbon dioxide is added to the polymer member. When forming a plating film on the polymer member, it is preferable to contact the polymer member with a second electroless plating solution containing high-pressure carbon dioxide and having a plating solution concentration that causes a plating reaction. As used herein, “plating solution concentration” refers to the concentration of a reducing agent such as sodium hypophosphite that is a factor that determines the plating reaction in the plating solution.

  In the plating film forming method of the present invention, the electroless plating solution preferably contains alcohol.

  According to the study of the present inventor, in the electroless plating method using the electroless plating solution containing supercritical carbon dioxide disclosed in Patent Document 2 and Non-Patent Document 1, etc., the carbon dioxide and the aqueous solution are in a high pressure state. It has been found that the electroless plating solution is difficult to be compatible even if a surfactant is used, and it is necessary to increase the stirring effect. Specifically, it has been found that it is necessary to use a stirrer with high stirring torque or a high-pressure vessel with a shallow bottom. That is, in order to obtain a stable emulsion by uniformly mixing the electroless plating solution and high-pressure carbon dioxide, it has been found that there are large restrictions on the shape of the high-pressure vessel and the stirrer and the rotation speed of the stirrer.

  Therefore, as a result of repeated studies to solve this problem, the present inventors have found that the electroless plating solution is mainly composed of water, but further, by mixing alcohol with the electroless plating solution, It has been found that even if the plating solution and high-pressure carbon dioxide are not stirred, the high-pressure carbon dioxide and the plating solution can be mixed stably and easily. This is considered to be because alcohol is easily compatible with high-pressure carbon dioxide. Therefore, normally, when preparing an electroless plating solution, the stock solution containing metal ions, a reducing agent, etc. is diluted with water according to, for example, the component ratio recommended by the manufacturer, and the plating solution is bathed. In this method of forming a plating film, a stable electroless plating solution in which an electroless plating solution and high-pressure carbon dioxide are uniformly mixed can be prepared by further mixing alcohol with water at an arbitrary ratio. The volume ratio of water and alcohol is arbitrary, but is preferably in the range of 10 to 80%. When there is little alcohol, it will become difficult to obtain a stable liquid mixture. Moreover, when there are too many alcohol components, since organic solvents, such as ethanol, are insoluble in nickel sulfate used for nickel-phosphorus plating, for example, the bath may not be stable.

  In addition, the kind of alcohol which can be used for this invention is arbitrary, Methanol, ethanol, n-propanol, isopropanol, butanol, heptanol, ethylene glycol, etc. can be used.

  Further, in the method for forming a plating film of the present invention, when alcohol is added to the electroless plating solution, the surface tension of the electroless plating solution to which alcohol is added is remarkably low because the alcohol has a lower surface tension than water. descend. Therefore, the electroless plating solution is more likely to penetrate into the free volume (inside) of the polymer member.

  In the plating film forming method of the present invention, the electroless plating solution preferably contains a surfactant. Thereby, the compatibility (affinity) of the high pressure carbon dioxide such as supercritical carbon dioxide and the electroless plating solution that is an aqueous solution can be further improved, and the formation of the emulsion can be promoted. In addition, the affinity of the plating solution for the polymer member can be improved.

  As the surfactant, it is desirable to select and use at least one of known nonionic, anionic, cationic and zwitterionic surfactants. In particular, it is desirable to use various surfactants that have been confirmed to be effective for forming an emulsion of supercritical carbon dioxide and water. For example, polyethylene oxide (PEO) -polypropylene oxide (PPO) block copolymer, ammonium carboxylate perfluoropolyether (PFPE), PEO-polybutylene oxide (PBO) block copolymer, octaethylene glycol monododecyl ether, etc. Can do.

  In the plating film forming method of the present invention, the high-pressure carbon dioxide is preferably supercritical carbon dioxide having a pressure of 7.38 MPa to 20 MPa. The critical pressure of carbon dioxide is 7.38 MPa, but a supercritical state higher than that is preferable because the density becomes high and it is easy to be compatible with the plating solution. On the other hand, when the pressure is increased to 30 MPa or more, problems such as excessive use of carbon dioxide and difficulty in sealing a high-pressure vessel are undesirable.

  The plating film forming method of the present invention preferably further includes performing at least one of electroless plating and electrolytic plating at normal pressure after the plating film is formed on the polymer member.

  In the method for forming a plating film of the present invention, it is preferable that a minimum thin metal film is formed on the surface of the polymer member in a short time to ensure adhesion between the metal film and the polymer member. Thereby, it is possible to suppress the electroless plating solution from excessively penetrating into the polymer member, and it is possible to suppress deformation and alteration of the polymer member due to the electroless plating solution. When it is necessary to increase the thickness of the plating film, after forming the electroless plating film on the polymer member by the above method of the present invention, the conventional plating method (electroless plating method and / or Alternatively, a metal film having a desired film thickness can be laminated on the polymer member by applying an electrolytic plating method). According to this method, a plating film having both the reliability (adhesiveness) of the metal film and securing of physical properties such as conductivity can be obtained.

  The plating film forming method of the present invention preferably further includes performing black electroless plating after the plating film is formed on the polymer member. In this case, since a black electroless plating film is formed on the polymer member, for example, by applying to an inner wall of a camera module or the like, an electromagnetic wave shielding effect can be obtained while suppressing ghost flare due to light reflection. .

  In the plating film forming method of the present invention, preparing a polymer member impregnated with metal fine particles inside the surface may include bringing a high-pressure fluid in which the metal complex containing the metal fine particles is dissolved into contact with the polymer member. preferable. The term “high pressure fluid” as used in the present specification means not only supercritical fluid but also high pressure liquid fluid (liquid) and high pressure gas such as high pressure inert gas. As the high-pressure fluid, high-pressure carbon dioxide is preferable, and supercritical carbon dioxide is particularly preferable.

  In the plating film forming method of the present invention, preparing a polymer member impregnated with metal fine particles inside the surface includes forming the polymer member impregnated with metal fine particles inside the surface in a mold of an injection molding machine. It is preferable.

  As a method for infiltrating the metal fine particles derived from the metal complex into the polymer member using an injection molding machine, for example, a method of infiltrating the metal fine particles into the flow front portion of the molten resin as described in Patent Document 1 is used. Also good. This method is suitable because it allows metal fine particles to penetrate only in the vicinity of the surface of the molded product during injection molding, while reducing material loss and modifying various materials simultaneously with molding. In addition, when a plating film is grown on the surface of the molded article by electroless plating in the same mold after molding, a metal film with high adhesion can be formed simultaneously with injection molding, so a polymer molded article can be produced at low cost. Can be manufactured. A sandwich molding method may be used as a method for infiltrating the metal fine particles into the polymer using an injection molding machine.

  In the method for forming a plating film of the present invention, a method for allowing metal fine particles to penetrate into the polymer member is arbitrary. For example, a material obtained by blending metal fine particles and a resin is mixed by extrusion molding to produce a pellet. Also good. A resin dissolved in a solvent and metal fine particles may be mixed by a casting method. Alternatively, metal fine particles may be dispersed in a varnish such as polyimide and applied to a substrate such as a polyimide sheet and cured.

  In the method for forming a plating film of the present invention, when forming a plating film on the polymer member, a metal high-pressure vessel having a film formed of a material that does not grow the plating film on the inner wall surface is used. The polymer member is preferably brought into contact with the electroless plating solution containing the high-pressure carbon dioxide in a high-pressure vessel.

  In a conventional electroless plating method, a resin container is generally used as a plating solution container. For example, high-pressure carbon dioxide as described in Patent Document 2 and Non-Patent Document 1 is included in the plating solution. In the method of plating, it is necessary to carry out the plating reaction in a high-pressure vessel, that is, a metal vessel that requires pressure resistance. However, according to the verification experiment of the present inventors, when a metal material such as SUS is used for the high-pressure vessel, the plating film grows on the surface of the high-pressure vessel that is not the object to be plated (polymer member), and the plating bath is not used. As a result, it has been found that it is difficult to grow a uniform metal film on the plating object. Further, since the adhesion of the plating film grown on the surface of the container is poor, the plating film grown on the surface of the container is peeled off during the plating, and there is a problem that the plating object (polymer member) is mixed as a foreign object. I understood it. That is, in the method of plating by including high-pressure carbon dioxide in an electroless plating solution, when a metal high-pressure vessel is used as a container for the electroless plating solution, industrialization is difficult due to the problems described above. It has been found.

  In contrast, in the plating film forming method of the present invention, the plating reaction is performed in a metal high-pressure vessel having a film (hereinafter also referred to as a non-plated growth film) formed of a material on which the plating film does not grow. In such a case, the above-described problem can be solved, so that an emulsion of an electroless plating solution and high-pressure carbon dioxide can be easily formed to stabilize the plating reaction. In addition, since the electroless plating solution is stabilized in the high-pressure vessel and the plating film is stably grown on the material to be plated such as a polymer member, industrialization becomes possible.

  In the plating film forming method of the present invention, the film is preferably formed of diamond-like carbon.

  The material for forming the non-plated growth film formed on the inner wall of the above-described high-pressure vessel is arbitrary as long as the plating film does not grow on the surface. For example, a dense carbon film such as diamond-like carbon (hard carbon film) or a thin film of an organic substance such as PTFE (polytetrafluoroethylene) or PEEK (polyetheretherketone) that is not easily affected by supercritical carbon dioxide is used. it can. These thin films can be formed using high-frequency plasma CVD, sputtering, thermal spraying, painting, or the like. Alternatively, a stable metal film such as gold (Au) or titanium may be coated by plating or sputtering. The material of the metal high-pressure vessel that can be used in the present invention is arbitrary, but a material that is not easily attacked by the acid of the plating solution is preferable. For example, SUS316, SUS316L, Hastelloy, titanium, Inconel, or the like can be used.

  In the method for forming a plating film of the present invention, when forming the plating film on the polymer member, a metal high-pressure vessel, and an inner container formed of a material that does not grow the plating film disposed inside the high-pressure vessel; It is preferable that the polymer member is brought into contact with the electroless plating solution containing the high-pressure carbon dioxide in the inner container.

  In the case of using an internal container formed of a material in which a plating film does not grow in a metal high-pressure container, for example, a plating apparatus provided with a resin container, the emulsion of high-pressure carbon dioxide and plating solution has a stirring effect. It is formed only inside the resin container. Therefore, the plating solution is less likely to come into direct contact with the inner wall of the high-pressure container that accommodates the inner container, and the plating reaction occurs only in the inner container, so that stable plating can be performed. In this case, since it is not necessary to coat the inner wall of the high-pressure vessel, the device is inexpensive. In addition, since the diffusibility of the electroless plating solution in which high-pressure carbon dioxide is dispersed is low, the electroless plating solution hardly leaks out of the inner container.

  In the plating film forming method of the present invention, it is preferable that the material for forming the inner container is polytetrafluoroethylene. Moreover, as a forming material of the inner container, other than polytetrafluoroethylene (PTFE), a resin material such as polyether ether ketone (PEEK) and polyimide, and a material obtained by mixing an inorganic substance such as glass fiber in the resin material, In addition, as the metal material, a metal material such as titanium, hastelloy, or Inconel can be used.

  Further, according to the study of the present inventor, in the method of plating by adding high-pressure carbon dioxide as described in Patent Document 2 and Non-Patent Document 1 to the plating solution, when high-pressure carbon dioxide is mixed, It has been found that problems such as a decrease in the deposition rate of electroless plating occur depending on the mixing conditions. This is because the acidic high-pressure carbon dioxide is mixed with the electroless plating solution at a high density, so that the pH of the electroless plating solution is lowered, and the plating bath mixed with the high-pressure carbon dioxide is lower than the lower limit of the optimum pH range. It is thought that it is to become. Therefore, in the method for forming a plating film of the present invention, the pH of the electroless plating solution may be adjusted to be high in advance. In this case, when an electroless plating solution containing high-density carbon dioxide is prepared, the pH of the electroless plating solution is lowered by mixing high-density carbon dioxide, and the plating bath can be brought to an optimum pH range. . Therefore, when this method is used, problems such as a decrease in the deposition rate of the plating film described above can be suppressed.

  In the plating method of the present invention, Ni, Co, Pd, Cu, Ag, Au, Pt, Sn, etc. can be used as the metal to be the plating film, and these are nickel sulfate and palladium chloride in the electroless plating solution. Supplied from a metal salt such as copper sulfate. As the reducing agent, dimethylamine borane, sodium hypophosphite (sodium phosphinate), hydrazine, formalin, sodium borohydride, potassium borohydride, titanium trichloride, or the like can be used.

  Various known additives may be added to the electroless plating solution. For example, a complexing agent such as citric acid, acetic acid, succinic acid, or lactic acid that forms a stable soluble complex with metal ions in the electroless plating solution may be added. Moreover, you may add sulfur compounds, such as thiourea, lead ion, a brightener, and a wetting agent (surfactant) as a stabilizer of an electroless plating solution.

  The material for forming the polymer member that can be used in the plating film forming method of the present invention is arbitrary, and a thermoplastic resin, a thermosetting resin, and an ultraviolet curable resin can be used. In particular, it is desirable to use a polymer member formed of a thermoplastic resin. The type of thermoplastic resin is arbitrary, and can be applied to either amorphous or crystalline. For example, synthetic fibers such as polyester, polypropylene, polyamide resin, polymethyl methacrylate, polycarbonate, amorphous polyolefin, polyetherimide, polyethylene terephthalate, liquid crystal polymer, ABS resin, polyamideimide, polyphthalamide, polyphenylene sulfide, polylactic acid Biodegradable plastics such as nylon resin, nylon resin and the like and composite materials thereof can be used. Further, a resin material in which various inorganic fillers such as glass fiber, carbon fiber, nanocarbon, and mineral are kneaded can also be used.

  Further, in the method for forming a plating film of the present invention, the form and production method of the polymer member are arbitrary. For example, a sheet or pipe produced by extrusion molding, or a polymer molded article produced by ultraviolet curing or injection molding is used. be able to. In consideration of industrial properties, it is preferable to use a polymer molded product obtained by injection molding with high continuous productivity.

  According to the second aspect of the present invention, in the method for forming a plating film according to the first aspect, a high-pressure container used for bringing an electroless plating solution into contact with a polymer member, a metal high-pressure container main body, There is provided a high-pressure vessel including a film formed on the inner wall surface of the high-pressure vessel main body and formed of a material on which the plating film does not grow. In the high-pressure vessel of the present invention, the film is preferably formed of diamond-like carbon.

  According to a third aspect of the present invention, there is provided a plating apparatus for use in the method for forming a plating film according to the first aspect, comprising: a metal high-pressure vessel; and an electroless polymer member disposed inside the high-pressure vessel. There is provided a plating apparatus comprising an inner container used for contacting a plating solution, wherein the inner container is formed of a material that does not allow the plating film to grow. Moreover, in the plating apparatus of this invention, it is preferable that the formation material of the said inner container is a polytetrafluoroethylene.

  According to the plating film forming method of the present invention, a plating film grown not only from the surface of the polymer member but also from the inside thereof can be formed on the polymer member, so that a plating film having better adhesion can be formed. Can do.

  Further, according to the method for forming a plating film of the present invention, since the electroless plating solution penetrates into the inside of the polymer member to cause a plating reaction, it is not necessary to roughen the surface of the polymer member as in the past, A plating film having excellent adhesion can be formed on all types of polymer members.

  Further, in the method for forming a plating film of the present invention, when alcohol is further mixed with the electroless plating solution, the compatibility (affinity) between the electroless plating solution and carbon dioxide can be improved.

  Furthermore, in the method for forming a plating film of the present invention, when using a metal high-pressure vessel equipped with a non-plated growth film on the inner wall surface, or a resin-made inner vessel, the plating film is formed in the vessel. It is possible to suppress the plating film from growing other than the substrate to be plated (polymer member), and the plating reaction can be stabilized in the container. Therefore, the repeated stability of plating film formation is improved and industrialization is possible.

  Hereinafter, embodiments of the method for forming a plating film of the present invention will be specifically described with reference to the drawings. However, the embodiments described below are preferred specific examples of the present invention, and the present invention is not limited thereto.

  In Example 1, a method of forming an electroless plating film on the surface of a polymer member by batch processing will be described.

  In this embodiment, the mount of a camera lens module used in a mobile phone, a digital camera, or the like is used as the polymer member. A schematic cross-sectional view of the polymer member of this example is shown in FIG. As shown in FIG. 2, the camera lens module 101 includes a mount 102 having an inner hole 108, a lens 104, and a lens holder 103 that fixes the lens 104. 2A is a diagram when the mount 102 and the lens holder 103 are disassembled, and FIG. 2B is a diagram when the mount 102 and the lens holder 103 are combined. As shown in FIG. 2A, the lens holder 103 is provided with an inner hole 107, and the lens 104 is fixed to the inner hole 107. An imaging element such as a C-MOS sensor (not shown) is fixed to the lower part of the camera module 101.

  As shown in FIG. 2A, a screw groove 105 is formed on the outer wall of the lens holder 103, and the upper end portion of the inner wall 108 of the mount 102 is fitted with the screw groove 105 of the lens holder 103. A thread groove 106 is formed. By fitting the screw groove 105 of the lens holder 103 with the screw groove 106 of the mount 102, the mount 102 and the lens holder 103 are combined as shown in FIG.

  In the camera lens module 101 used in a mobile phone, a digital camera, or the like, a subject image is formed on a sensor such as an image sensor such as a CCD or C-MOS by the lens 104, but due to electric signal noise from the mobile phone body. As a method for suppressing the adverse effect on the module, it is desirable to shield the mount 102 adjacent to the image sensor with an electromagnetic wave. However, when a plating film is formed on the entire mount 102, if the inner wall surface of the mount 102 is a metallic gloss film, light is reflected inside the mount 102, which causes ghost flare. Therefore, in the final step of the plating film of this example, the surface of the mount 102 was subjected to black electroless plating.

  Further, in this example, reinforced polyphthalamide containing 65% glass fiber and mineral (Amodel AS-1566HS made by Solvay Advanced Polymer) was used as a material for forming the polymer member 102 (mount).

[Plating equipment]
A schematic configuration diagram of the plating apparatus used in Example 1 is shown in FIG. As shown in FIG. 1, the plating apparatus 100 mainly includes a carbon dioxide cylinder 21, a filter 26, a high-pressure syringe pump 20, and a high-pressure container 1, and these components are connected by a pipe 27. As shown in FIG. 1, manual valves 22 to 24 for controlling the flow of high-pressure carbon dioxide are provided at predetermined positions on the piping 27 that connects the components.

  As shown in FIG. 1, the high-pressure container 1 (high-pressure container main body) includes a container main body 2 in which an electroless plating solution 8 and a polymer member 102 (polymer) are accommodated, and a lid 3. The lid 3 is provided with a polyimide seal 4 containing a known spring, and the high pressure gas is sealed inside the high pressure vessel 1 by the polyimide seal 4. A holding member 5 that can suspend and hold a plurality of polymer members 102 in the electroless plating solution 8 is provided on the surface (lower surface) of the lid 3 on the plating solution 8 side. On the other hand, a magnetic stirrer 6 for stirring the electroless plating solution 8 is provided at the bottom of the container body 2. Further, the container body 2 has a temperature control flow path 7, and the temperature control water whose temperature is controlled by a temperature controller (not shown) is caused to flow into the temperature control flow path 7. The temperature is adjusted. In this example, the temperature can be adjusted at any temperature from 30 ° C. to 145 ° C. Further, as shown in FIG. 1, a high-pressure carbon dioxide inlet 25 is provided in the side wall of the container body 2.

  In this example, SUS316L was used as a material for forming the high-pressure vessel 1. In addition, as a forming material of the high-pressure vessel 1, it is desirable to use a material that is not easily corroded, and SUS316, SUS316L, Inconel, Hastelloy, titanium, or the like can be used. Further, in this embodiment, when the inner wall surface of the high-pressure vessel 1 comes into contact with the electroless plating solution, a plating film does not grow on the inner wall of the vessel, so that the inner wall surface of the high-pressure vessel 1 has a CVD (Chemical Vapor Deposition). A non-plated growth film made of DLC (diamond-like carbon) was formed by a chemical vapor deposition method. As the non-plated growth film, PTFE (polytetrafluoroethylene), PEEK (polyethyl ether ketone), or the like can also be used.

  In this example, nickel-phosphorus was used as the electroless plating solution 8. Note that nickel-boron, palladium, copper, silver, cobalt, or the like may be used as the electroless plating solution. Further, as the electroless plating solution 8, a solution that can be plated with a neutral or weakly alkaline to acidic bath is suitable. In the case of nickel-phosphorus, it can be used in a pH range of 4 to 6, and is desirable. Depending on the conditions of the electroless plating solution 8 before introducing high-pressure carbon dioxide, the pH of the electroless plating solution 8 is lowered by infiltrating (introducing) the high-pressure carbon dioxide into the electroless plating solution. Since the concentration may increase and the adverse effect such as a decrease in the deposition rate of the plating film may occur, the pH of the electroless plating solution 8 may be increased in advance.

  In this example, Nicolon DK manufactured by Okuno Pharmaceutical Co., Ltd. containing a metal salt of nickel sulfate, a reducing agent, and a complexing agent was used as a stock solution of the electroless plating solution 8. Further, alcohol was mixed with the electroless plating solution 8. The type of alcohol that can be used in this example is arbitrary, and methanol, ethanol, n-propanol, isopropanol, butanol, heptanol, ethylene glycol, and the like can be used. In this example, ethanol was used. More specifically, the ratio of each component in 1 l of the electroless plating solution is as follows: 150 ml of stock solution (Nicolon DK manufactured by Okuno Seiyaku Co., Ltd.) containing a metal salt of nickel sulfate and a reducing agent or complexing agent, 350 ml of water, And alcohol (ethanol) was made into 500 ml. That is, the proportion of alcohol in the electroless plating solution 8 was 50%. In addition, since nickel sulfate was insoluble in alcohol, it was found that when the amount of alcohol added exceeds 80%, a large amount of nickel sulfate precipitates, which makes it impossible to apply.

  According to the study by the present inventors, the electroless plating solution 8 is mainly composed of water, but it is understood that the high pressure carbon dioxide and the electroless plating solution are easily mixed stably by mixing alcohol. It was. This is considered due to the fact that alcohol and supercritical carbon dioxide are easily compatible. Therefore, when alcohol is mixed with the electroless plating solution as in this embodiment, it is not necessary to add a surfactant to the electroless plating solution or to stir the electroless plating solution. Furthermore, in order to allow the plating solution to penetrate into the polymer together with high-pressure carbon dioxide to grow the plating reaction inside the polymer, it is more preferable to add alcohol to the plating solution because the surface tension is lower than water alone. It is. However, in the present invention, a surfactant may be added or the electroless plating solution may be stirred in order to further improve the compatibility (affinity) between the high pressure carbon dioxide and the electroless plating solution. In this example, as described later, a surfactant was added to the electroless plating solution, and the electroless plating solution was also stirred.

  In this example, 3 wt% of octaethylene glycol monododecyl ether as a surfactant was further added to the electroless plating solution 8.

  In the syringe pump 20 of the plating apparatus 100 used in this embodiment, when the pressure inside the high-pressure vessel 1 and the density of high-pressure carbon dioxide are changed by controlling the pressure constant with the manual valves 22 and 23 opened. In addition, the pressure fluctuation can be absorbed, whereby the pressure inside the high-pressure vessel 1 can be stably maintained.

[Method of forming plating film]
First, a polymer member 102 (mount) in which metal fine particles penetrated into the surface was prepared (prepared) as follows. The polymer member 102 having a predetermined shape shown in FIG. 2 was formed by injection molding. Next, the molded polymer member 102 and the metal complex were mounted in a high-pressure container (not shown) of a surface modification device (not shown). At this time, the polymer member 10 was held in the high-pressure vessel so that the entire surface of the polymer member 102 was in contact with supercritical carbon dioxide (hereinafter referred to as supercritical carbon dioxide) to be introduced into the high-pressure vessel later. In this example, hexafluoroacetylacetonato palladium (II) was used as the metal complex.

  Next, 15 MPa of supercritical carbon dioxide was introduced into the high-pressure vessel. At this time, the metal complex charged in the high-pressure vessel is dissolved in supercritical carbon dioxide and penetrates into the entire surface of the polymer member 102 together with the supercritical carbon dioxide. Next, by holding the pressure in the high-pressure vessel at 120 ° C. for 30 minutes, a part of the metal complex that has permeated the entire surface of the polymer member 102 is reduced. In this example, the polymer member 102 in which the metal fine particles penetrated into the inside of the surface was produced in this way (step S11 in FIG. 12). FIG. 3 shows this state, and the black circles in FIG. 3 are the metal fine particles penetrating the inside of the surface of the polymer member 102.

  Next, after attaching the polymer member 102 produced as described above to the holding member 5 of the lid 5 of the high-pressure vessel 1 shown in FIG. 1, the polymer member 102 is inserted into the vessel body 2 and the lid 3 is inserted. Was closed and the high-pressure vessel 1 was sealed. The container main body 2 is filled with 70% of the inner volume of the container main body 2 in advance, and the container main body 2 is sealed with the lid 3 so as to contain the surfactant and alcohol. 8 is a state in which a plurality of polymer members 102 are suspended (state in FIG. 1, step S12 in FIG. 12). However, at this time, the temperature of the high-pressure vessel 1 and the electroless plating solution 8 is 50 or less than the plating reaction temperature (70 ° C. to 85 ° C.) due to the temperature adjustment water flowing through the temperature adjustment flow path 7 of the high-pressure vessel 1. Adjusted to ° C. Therefore, at this time, the polymer member 102 is in contact with the electroless plating solution at a temperature lower than the plating reaction temperature (the temperature at which the plating reaction does not occur), and the plating film does not grow on the surface of the polymer member 102.

  Next, high-pressure carbon dioxide was introduced into the high-pressure vessel 1 that was temperature-controlled at a low temperature where no plating reaction occurred as follows. In this example, supercritical carbon dioxide was used as high-pressure carbon dioxide. First, liquid carbon dioxide taken out from the liquid carbon dioxide cylinder 21 was sucked up by the high-pressure syringe pump 20 through the filter 26, and then the pressure was increased to 15 MPa in the pump (supercritical carbon dioxide was generated). Next, the manual valves 22 and 23 were opened, 15 MPa of supercritical carbon dioxide was introduced into the high-pressure vessel 1 through the inlet 25, and contacted with the polymer member 102 (step S13 in FIG. 12). At this time, the surface of the polymer member 102 is swollen by the introduced supercritical carbon dioxide, and the surface tension of the plating solution mixed with the supercritical carbon dioxide is low. Therefore, the electroless plating solution 8 is supercritical. Penetrates inside the polymer with carbon dioxide. As a result, the electroless plating solution 8 reaches the metal fine particles existing inside the polymer member 102. In this example, since the electroless plating solution 8 contains alcohol, the surface tension of the electroless plating solution 8 is further reduced, so that the electroless plating solution 8 is more easily penetrated into the polymer member 102.

  In this example, after the introduction of supercritical carbon dioxide, the electroless plating solution 8 was agitated by rotating the magical stirrer 6 at a high speed. As described above, in this example, since the electroless plating solution contains alcohol, the phase between the supercritical carbon dioxide and the plating solution can be obtained without diffusing the electroless plating solution 8 by using the magical stirrer 6. Although sufficient solubility can be ensured, in this example, the electroless plating solution 8 was agitated with a magical stirrer 6 in order to increase the compatibility between the supercritical carbon dioxide and the plating solution.

  Next, the temperature of the high-pressure vessel 1 is raised to 85 ° C., a plating reaction is caused in the high-pressure vessel 1 (electroless plating is performed), and a plating film is formed on the surface of the polymer member 102 (in FIG. 12). Step S14). At this time, in the plating film forming method of this example, since the electroless plating solution penetrates to the metal fine particles existing inside the polymer member 102 as described above, not only the surface of the polymer member 102, A plating film grows using the metal fine particles existing inside as catalyst nuclei. That is, in the plating film forming method of this example, the plating film grows also in the free volume inside the polymer member 102, and the plating film is formed on the polymer member 102 in a state of biting into the polymer member 102. The

  After the end of plating, the magnetic stirrer 6 was stopped and allowed to stand for a while to separate the carbon dioxide and the plating solution into two phases in the high-pressure vessel 1. Thereafter, the manual valve 22 was closed, the manual valve 24 was opened, and the carbon dioxide in the high-pressure vessel 1 was exhausted. Next, the high-pressure vessel 1 was opened, and the polymer member 102 was taken out from the high-pressure vessel 1. When the taken-out polymer member 102 was visually confirmed, metallic luster was observed on the entire surface of the polymer member 102.

  Next, the polymer member 102 was annealed at 150 ° C. for 1 hour in order to degas the carbon dioxide and the electroless plating solution from the inside of the polymer member 102 taken out from the high-pressure vessel 1. Next, the oxidized plating film surface was activated with hydrochloric acid. After that, electroless plating is performed at atmospheric pressure using a conventional electroless nickel-phosphorus solution in the atmosphere, a 500 nm plating film is laminated, and further, 1 μm of electroless copper plating is laminated thereon, and an electromagnetic wave shield. A membrane was applied. Next, black electroless plating was performed, and a black electroless nickel-phosphorous plating film was laminated on the electroless copper plating film. The blackening was performed by plating using a dedicated electroless nickel-phosphorous plating solution and then roughening the surface by etching. This is because the inner wall of the polymer member 102 (mount) is blackened to suppress ghost flare due to light reflection. In this example, as described above, a polymer member was obtained in which the entire surface of the polymer member 102 as shown in FIG. 4 was covered with a metal film (reference number 300 in FIG. 4).

[Evaluation of plating film]
For the polymer member 102 produced as described above, a high temperature and high humidity test (conditions: temperature 80 ° C., humidity 90% Rh, standing time 500 hours) and heat cycle test (between the temperatures between 80 ° C. and 150 ° C.) After performing a peel test after 15 cycles, no film peeling occurred. Further, when the above process of this example was repeated, no growth of the plating film or corrosion of the inner wall of the container was observed inside the high pressure container 1.

  Moreover, the cross section of the surface vicinity of the polymer member 102 produced in this example was observed with SEM (scanning electron microscope). The results are shown in FIG. A region 102 a in FIG. 5 is a region of the polymer member 102 where no plating film is formed, and a region 102 b is a layer in which a metal film is grown inside the polymer member 102. A region 102c in FIG. 5 is a region of a metal film formed when electroless plating is performed at normal pressure using a conventional electroless nickel-phosphorus solution in the atmosphere. The region 102d is a region of the electroless copper plating film. Therefore, the vicinity of the boundary between the region 102 b and the region 102 c is the outermost surface of the polymer member 102. As is clear from the observation image of FIG. 5, it was confirmed that a layer in which a metal film was grown was formed inside the polymer member 102 (region 102b in FIG. 5).

  In this example, when the metal present in the polymer member 102 was further subjected to component analysis by XRD (X-ray diffractometer), Ni, P and Pd were detected. From this result, it was confirmed that Pd derived from the metal complex that penetrated into the polymer member 102 worked as a catalyst, and a Ni—P plating film was grown inside the polymer.

  In Example 2, as in Example 1, a method for forming an electroless plating film on the polymer surface by batch processing will be described. In this example, a high pressure vessel having a structure different from that of Example 1 was used as the high pressure vessel in the plating apparatus. The electroless plating solution used in this example was the same as in Example 1. In this example, similarly to Example 1, a metal film was formed on the surface of the camera lens module mount (mount 102 having the structure shown in FIG. 2). Further, supercritical carbon dioxide was used as high-pressure carbon dioxide introduced into the electroless plating solution.

[Plating equipment]
A schematic configuration diagram of the plating apparatus used in Example 2 is shown in FIG. As shown in FIG. 6, the plating apparatus 200 mainly includes a carbon dioxide cylinder 21, a filter 26, a high-pressure syringe pump 20, and a high-pressure vessel 1 ′, and these components are connected by a pipe 27. ing. In addition, as shown in FIG. 6, manual valves 22 to 24 for controlling the flow of supercritical carbon dioxide are provided at predetermined positions on the piping 27 that connects the components.

  As shown in FIG. 6, the high-pressure container 1 ′ includes a container main body 2, a lid 3, and an internal container 9 accommodated in the container main body 2. The lid 3 has the same structure as that of the first embodiment except that it does not include a holding member that holds the polymer member 102 as in the first embodiment. The container body 2 of this example has the same structure as that of Example 1 except that the non-plated growth film is not provided on the inner wall surface. In the plating apparatus 200 of this example, an inner container 9 made of PTFE (polytetrafluoroethylene) that can be accommodated in the metal container body 2 is used, and the polymer member 102 is electrolessly plated in the inner container 9. Was given.

  As shown in FIG. 6, the inner container 9 includes a container main body portion 9 a in which the electroless plating solution 8 and the polymer member 102 are accommodated, and a lid portion 9 b. A holding member 5 capable of suspending and holding a plurality of polymer members 102 in the electroless plating solution 8 is provided on the surface (lower surface) of the lid portion 9b on the electroless plating solution 8 side. The holding member 5 has the same structure as the holding member of the first embodiment. On the other hand, a magnetic stirrer 6 for stirring the electroless plating solution 8 is provided at the bottom of the container body 9a. In addition, a screw groove is formed on the outer wall near the upper end of the container main body 9a, and a screw groove that fits into a screw groove provided on the outer wall of the upper end of the container main body 9a is formed on the inner wall of the lid 9b. Yes. Then, the inner container 9 is closed by fitting the screw groove of the container main body portion 9a and the screw groove of the lid portion 9b.

[Method of forming plating film]
First, in this example, in the same manner as in Example 1, a polymer member 102 (mount 102 having the shape shown in FIG. 2) in which metal fine particles penetrated into the surface was prepared (prepared). In this example, hexafluoroacetylacetonato palladium (II) was used as the metal complex.

  Next, after the molded polymer member 102 was attached to the holding member 5 of the lid portion 9b of the inner container 9 shown in FIG. 6, the polymer member 102 was inserted into the container body portion 9a to close the lid portion 9b. . At this time, as shown in FIG. 6, a plurality of polymer members 102 are suspended in the electroless plating solution 8 containing a surfactant and alcohol. And this state was kept at room temperature. Therefore, at this time, since the temperature of the electroless plating solution 8 is equal to or lower than the plating reaction temperature (70 ° C. to 85 ° C.), the plating film does not grow on the surface of the polymer member 102.

  Next, the inner vessel 9 is inserted into the high-pressure vessel 1 ′ that has been temperature-controlled in advance at 90 ° C., the lid 3 is closed, and immediately after the supercritical carbon dioxide is introduced into the inlet 25 in the same manner as in Example 1. And introduced into the high-pressure vessel 1 ′. Thereafter, the electroless plating solution 8 was stirred with a magnetic stirrer 6. At this time, the container body portion 9a and the lid portion 9b of the inner container 9 are fitted with screws as described above. Even in this state, supercritical carbon dioxide has a low viscosity and a high diffusivity. The container 9 is sufficiently introduced into the inner container 9 through a slight gap in the portion engaged with the screw. Further, at this time, since the resin having low thermal conductivity is used for the inner container 9, the temperature in the inner container 9 does not increase rapidly, so that the temperature becomes lower than the temperature at which the plating reaction occurs. In addition, the plating film does not grow on the surface of the polymer member 102. Therefore, when the internal container 9 is inserted into the high-pressure container 1 ′ and the supercritical carbon dioxide is immediately introduced, the surface of the polymer member 102 swells and the supercritical carbon dioxide is mixed as in the first embodiment. Since the plating solution has a low surface tension, the electroless plating solution penetrates into the inside of the polymer member 102 together with the supercritical carbon dioxide, and the electroless plating solution reaches the metal fine particles existing inside the polymer member 102. .

  Thereafter, with the passage of time, the temperature in the inner container 9 rises, and finally the temperature of the electroless plating solution 8 etc. rises to the plating reaction temperature. At that time, a plating reaction occurs in the inner container 9, and a plating film grows on the surface of the polymer member 102. At this time, in the plating film forming method of this example, since the electroless plating solution penetrates to the metal fine particles existing inside the polymer member 102 as described above, not only the surface of the polymer member 102, A plating film grows using the metal fine particles existing inside as catalyst nuclei. In other words, in the plating film forming method of this example, the plating film is formed on the polymer in a state of being bitten into the polymer member 102.

  Next, after the plating process described above (about 30 minutes after the insertion of the inner container 9), supercritical carbon dioxide was exhausted from the high-pressure container 1 ′, and the inner container 9 was kept at 90 ° C. as it was. By this process, a plating film was further grown at normal pressure on the plating film grown from the inside of the polymer member 102. Thereafter, the inner container 9 was taken out from the high-pressure vessel 1 ′, and then the polymer member 102 was taken out from the inner container 9. Subsequently, the polymer member 102 taken out from the inner container 9 was subjected to electroless copper plating and black electroless nickel-phosphorous plating in the same manner as in Example 1. In this example, as described above, the polymer member 102 having the entire surface as shown in FIG. 4 covered with the metal film (reference numeral 300 in FIG. 4) was obtained.

[Evaluation of plating film]
When the environmental test (high temperature and high humidity test, heat cycle test) and the adhesion evaluation (peel test) were performed on the polymer member 102 produced as described above in the same manner as in Example 1, Example 1 and Similarly, it was found that a plating film with high adhesion was formed on the polymer member 102.

  Further, no plating solution was confirmed inside the high-pressure vessel 1 ′ of this example. Therefore, when a resin-made inner container is used as in the present embodiment, the plating does not grow on the inner wall of the high-pressure container 1 ′ without coating the inside of the high-pressure container 1 ′. Plating can be performed. Moreover, since the corrosion of the surface of the high-pressure vessel 1 ′ can be suppressed, the plating apparatus is suitable as a plating film forming method using supercritical carbon dioxide.

  In Example 3, the same plating apparatus as in Example 2 was used except that the surfactant was not added to the electroless plating solution and that the electroless plating solution was not stirred by a magnetic stirrer. Then, the electroless plating treatment was performed on the polymer member by the same method.

  Moreover, when the environmental test (high temperature and humidity test, heat cycle test) and adhesion evaluation (peel test) were performed on the polymer member produced in this example in the same manner as in Example 2, Example 2 and Similarly, it was found that a highly adhesive plating film was formed on the polymer member. That is, according to the method for forming a plating film of the present invention, using a surfactant or a magnetic stirrer, even if the affinity (compatibility) between the supercritical carbon dioxide and the electroless plating solution is not improved, It was found that a plating film having good adhesion can be formed on the polymer.

  In Example 4, the same plating apparatus as in Example 2 except that no alcohol was mixed with the electroless plating solution and that the pressure of supercritical carbon dioxide introduced into the electroless plating solution was increased to 20 MPa. The polymer member was subjected to electroless plating by the same method.

  Moreover, when the environmental test (high temperature and humidity test, heat cycle test) and adhesion evaluation (peel test) were performed on the polymer member produced in this example in the same manner as in Example 2, Example 2 and Similarly, it was found that a highly adhesive plating film was formed on the polymer member. That is, in the method for forming a plating film of the present invention, the affinity between the aqueous solvent (electroless plating solution) and supercritical carbon dioxide can be increased by using a surfactant and mechanical stirring without using alcohol. I understood that I could do it.

  In Example 5, the polymer member was coated on the polymer member in the same manner as in Example 1 except that the non-plated growth film was not coated on the inner wall of the high-pressure vessel of the plating apparatus. Electrolytic plating was performed.

  Further, for the polymer member produced in this example, an environmental test (high temperature and humidity test, heat cycle test) and adhesion evaluation (peel test) were conducted in the same manner as in Example 1. Similarly, it was found that a plating film with good adhesion was formed on the polymer member. However, in this example, since the non-plated growth film was not formed on the inner wall of the high-pressure vessel of the plating apparatus, the growth and corrosion of the plating film was confirmed on the inner wall of the high-pressure vessel.

[Comparative Example 1]
In Comparative Example 1, the polymer member was electrolessly plated in the same manner as in Example 4 (when alcohol was not mixed in the electroless plating solution) except that stirring was not performed in the inner container of the plating apparatus.

  Also, for the polymer member produced in this example, environmental tests (high temperature and humidity test, heat cycle test) and adhesion evaluation (peel test) were conducted in the same manner as in Example 1. The polymer member peeled off the electroless plating film. From this result, it was found that when the alcohol is not mixed with the electroless plating solution, the electroless plating solution needs to be stirred even if the surfactant is added to the electroless plating solution.

[Comparative Example 2]
In Comparative Example 2, the polymer member in which the electroless plating solution and metal fine particles had permeated into the surface was inserted into the inner container of the plating apparatus, and then heated to 80 ° C. Next, in the same manner as in Example 3, the inner vessel was inserted into the high-pressure vessel, and supercritical carbon dioxide was introduced to perform electroless plating. That is, in Comparative Example 2, the temperature of the electroless plating solution brought into contact with the polymer member was made substantially constant before and after the introduction of supercritical carbon dioxide.

  Also, for the polymer member produced in this example, environmental tests (high temperature and humidity test, heat cycle test) and adhesion evaluation (peel test) were conducted in the same manner as in Example 1. The polymer member peeled off the electroless plating film. This is because the electroless plating solution was adjusted to the plating reaction temperature before the introduction of supercritical carbon dioxide (before the supercritical carbon dioxide was brought into contact with the polymer member) in the plating film forming method of Comparative Example 2. Before the plating solution penetrates into the inside of the polymer member, the plating reaction and the plating film are deposited on the surface of the polymer member. The electroless plating solution does not penetrate into the inside of the polymer member, and the plating film grows inside the polymer member. This is thought to be due to inhibition.

Table 1 summarizes the form of the high-pressure vessel, the conditions of the electroless plating solution, and the evaluation results in Examples 1 to 5 and Comparative Examples 1 and 2. In addition, the evaluation criteria of the adhesion of the plating film and the corrosivity of the high-pressure inner wall in Table 1 are as follows.
Plating film adhesion:
◎ When there is no problem in the peel test after the environmental test (high temperature and humidity, heat cycle test) (when there is no peeling of the plating film, film swelling, etc.)
○ When there is no problem in the peel test before the environmental test × When peeled off during the peel test before the environmental test Corrosion of the inner wall of the container and growth of the plating film:
○ When there is no rust or plating film growth on the container inner wall × When rust or plating film growth occurs on the container inner wall

  In Example 6, a method of performing electroless plating in the same injection molding machine after injection molding of a polymer molded product using the injection molding machine will be described. In this example, an automobile headlight reflector was produced as a polymer molded product.

[Production equipment for polymer molded products]
FIG. 7 shows a schematic configuration of the apparatus for producing a polymer molded product used in this example. As shown in FIG. 7, the manufacturing apparatus 500 of the present embodiment mainly supplies and discharges a vertical injection molding apparatus section 503 including a mold and an electroless plating solution including high-pressure carbon dioxide to the mold. The electroless plating apparatus section 501 for controlling the pressure and the surface modification apparatus section 502 for infiltrating the high-pressure carbon dioxide in which the metal complex is dissolved in the molten resin in the plasticizing cylinder of the injection molding apparatus section 503.

  As shown in FIG. 7, the vertical injection molding apparatus unit 503 mainly includes a plasticizing and melting apparatus 110 that plasticizes and melts a resin for forming a polymer molded product, and a mold clamping apparatus 111 that opens and closes a mold. .

  The plasticizing and melting apparatus 110 mainly includes a plasticizing cylinder 52 with a built-in screw 51, a hopper 50, and a high-pressure carbon dioxide introduction valve 65 provided in the vicinity of a tip portion (flow front portion) in the plasticizing cylinder 52. It consists of. Further, a pressure sensor 40 for measuring the resin internal pressure was provided at a position facing the introduction valve 65 of the plasticizing cylinder 52. Poniphenylene sulfide (FZ-8600 Black manufactured by Dainippon Ink & Chemicals, Inc.) was used as a material for resin pellets (not shown) supplied from the hopper 50 into the plasticizing cylinder 52.

  The mold clamping device 111 is mainly composed of a fixed mold 53 and a movable mold 54. The movable mold 54 is connected to a movable platen 56 and a hydraulic mold clamping mechanism (not shown) connected to the movable mold 54 in conjunction with the drive. It is structured to open and close between the tie bars 55 of the book. In addition, a plating solution introduction path 61 for supplying and discharging high-pressure carbon dioxide and electroless plating solution to and from a cavity 504 defined between the movable die 54 and the fixed die 53 is provided in the movable die 54. , 62 are formed. The plating solution introduction paths 61 and 62 are connected to a pipe 15 of an electroless plating apparatus unit 501 described later as shown in FIG. 7, and the high pressure carbon dioxide and the electroless plating solution are cavities 504 through the pipe 15. It is a structure that is introduced into. The cavity 504 is sealed by fitting the spring-incorporated seal 17 provided on the outer diameter portion of the fixed mold 53 and the movable mold 54.

  As shown in FIG. 7, the surface reformer unit 502 mainly dissolves the liquid carbon dioxide cylinder 21, the syringe pumps 20, 34, the filter 57, the back pressure valve 48, and the metal complex in high pressure carbon dioxide. It is comprised from the dissolution tank 35 and the piping 80 which connects these components. Further, as shown in FIG. 7, the pipe 80 of the surface reformer unit 502 is connected to the introduction valve 65 of the plasticizing cylinder 52, and the pressure sensor 47 is provided in the pipe 80 near the introduction valve 65. Yes. In this example, a metal complex (hexafluoroacetylacetona palladium (II)) was used as a raw material for the metal fine particles charged in the dissolution tank 35.

  As shown in FIG. 7, the electroless plating apparatus unit 501 mainly includes a liquid carbon dioxide cylinder 21, a pump 19, a buffer tank 36, and a high pressure container 10 that mixes an electroless plating solution and high pressure carbon dioxide, Circulation pump 90, plating tank 11 for replenishing electroless plating solution, syringe pump 33, recovery container 63 for recovering electroless plating solution, recovery tank 12, and piping 15 connecting these components Consists of Further, automatic valves 43 to 46 and 38 for controlling the flow of the high-pressure carbon dioxide and the electroless plating solution are provided at predetermined positions of the pipe 15. Further, as shown in FIG. 7, the pipe 15 is connected to plating solution introduction paths 61 and 62 of the movable mold 54. In this example, as the electroless plating solution, an electroless plating solution obtained by mixing the same alcohol and surfactant as in Example 1 was used, and the composition was the same as in Example 1.

[Molding method of polymer molded product]
Next, a method for forming a polymer molded article in which metal fine particles are infiltrated into the surface will be described. In the present invention, the method for infiltrating the metal fine particles into the resin is arbitrary, but in this embodiment, the metal fine particles were dissolved in the tip portion (flow front portion) of the molten resin plasticized and measured in the plasticizing cylinder 52. High pressure carbon dioxide was introduced.

  First, the metal complex was dissolved in ethanol in the dissolution tank 35, and the ethanol in which the metal complex was dissolved was increased to 15 MPa in the syringe pump 34. On the other hand, the liquid carbon dioxide cylinder 21 was supplied to the syringe pump 20 via the filter 53, and the liquid carbon dioxide pressure was increased to 15 MPa in the syringe pump 20. Then, the pressurized carbon dioxide and ethanol in which the metal complex was dissolved were mixed in the pipe 80 (a high-pressure mixed fluid was generated). Note that when the high-pressure mixed fluid was supplied to the plasticizing and melting apparatus 110, the supply pressure of the high-pressure mixed fluid was controlled by the back pressure valve 48 so that the display of the pressure gauge 49 became 15 MPa. Further, the feeding of the high-pressure mixed fluid of ethanol solution and high-pressure carbon dioxide from both syringe pumps 20 and 34 was performed by switching the control of each syringe pump 20 and 34 from pressure control to flow rate control. Furthermore, when supplying the high-pressure mixed fluid to the plasticizing and melting apparatus 110, the high-pressure mixed fluid was supplied to the plasticizing and melting apparatus 110 while controlling the temperature in the pipe 80 to 50 ° C. with a heater (not shown).

  Next, a procedure for introducing the high-pressure mixed fluid into the plasticizing and melting apparatus 110 will be described with reference to FIGS. 8A and 8B are enlarged cross-sectional views of the vicinity of the introduction valve 65 of the plasticizing and melting apparatus 110. FIG. First, while supplying resin pellets from the hopper 50, the screw 51 in the plasticizing cylinder 52 was rotated to measure plasticization of the resin. FIG. 8A shows a state in the vicinity of the introduction valve 65 when the plasticizing measurement is completed. At this time, as shown in FIG. 8A, the introduction pin 651 of the introduction valve 62 moves backward (moves to the left in FIG. 8A), so that the high-pressure mixed fluid 67 is introduced into the molten resin 66. Is being blocked.

  Next, the screw 51 is sucked back (retracted) to reduce the internal pressure of the molten resin 66, and at the same time, both syringe pumps 20, 34 are switched from pressure control to flow rate control, and ethanol and carbon dioxide in which the metal complex is dissolved. The high-pressure mixed fluid 67 was introduced into the molten resin 66 at the flow front portion in the plasticizing cylinder 52 through the introduction valve 65 (the state shown in FIG. 8B). ). A region 68 in FIG. 8B is a portion of the molten resin into which the high pressure mixed fluid 67 has penetrated.

  In the introduction valve 65 of the plasticizing cylinder 52 of this embodiment, when the pressure difference between the molten resin 66 and the high pressure mixed fluid 67 becomes 5 MPa or more, the high pressure mixed fluid 67 is melted in the plasticizing cylinder 52. The introduction principle of the high-pressure mixed fluid 67 by the introduction valve 65 is as follows. When the screw 51 is sucked back after the plasticization measurement is completed, the molten resin 66 is decompressed and the density is lowered. When the pressure difference between the molten resin 66 and the high pressure mixed fluid 67 becomes 5 MPa or more, the pressure of the high pressure mixed fluid 67 overcomes the return force (elastic force) of the spring 652 in the introduction valve 65, and the introduction pin 651 It advances to the molten resin 66 side, and the high-pressure mixed fluid 67 is introduced into the molten resin 66. The high-pressure mixed fluid 67 was introduced while monitoring the resin pressure and the pressure of the high-pressure mixed fluid 67 with the pressure sensors 40 and 47, respectively.

  Subsequently, both syringe pumps 20 and 34 were stopped, and liquid feeding of the high pressure mixed fluid 67 was stopped. At the same time, the screw 51 is advanced to increase the resin pressure again, and the introduction pin 64 is retracted (moved to the left in FIG. 8B). Thereby, the introduction of the high-pressure mixed fluid 67 was stopped, and the high-pressure mixed fluid 67 and the molten resin 66 were made compatible.

  Next, both syringe pumps 20 and 34 are closed with an automatic valve (not shown) in the pipe 80, and then the flow rate of the ethanol solution in which the high-pressure carbon dioxide and the metal complex are supplied to the plasticizing and melting apparatus 110 is changed to the syringe pump 20 and 34 was refilled. After that, the pressure control was switched to 15 MPa, and the system was kept waiting until the next shot was fed.

  Next, after introducing the high-pressure mixed fluid 67 into the molten resin 66 at the flow front portion in the plasticizing cylinder 52, the mold is clamped by a hydraulic clamping mechanism (not shown) of the clamping device 111, and a temperature control circuit (not shown). The molten resin was injected and filled into the cavity 504 defined in the mold whose temperature was controlled by the above method. Next, the molded product was cooled and solidified (state shown in FIG. 9). When the molten resin is injection-molded into the mold, the molten resin 68 in the flow front portion that is injected first forms the skin of the injection-molded product by the fountain effect (fountain flow). That is, in this example, metal fine particles derived from the metal complex are dispersed in the vicinity of the flow front portion, and therefore, as shown in FIG. 9, the skin 505 (inside the surface) of the polymer molded product 507 is impregnated with the metal fine particles. A molded product 507 is obtained (step S61 in FIG. 13). In this example, in this way, the metal fine particles were dispersed in the skin layer 505 as the epidermis, and the polymer molded product 507 having almost no metal fine particles in the core layer 506 as the endothelium was obtained.

[Method of forming plating film]
The polymer molded product 507 in which metal fine particles were dispersed inside the surface produced as described above was subjected to electroless plating in a mold as follows. During the electroless plating process, the temperature inside the mold was adjusted to 80 ° C.

  First, as shown in FIG. 10, the movable platen 56 and the movable mold 54 are moved backward by retreating the hydraulic mold clamping mechanism (not shown) of the mold clamping device 111 (downward in FIG. 10), so that the fixed mold is fixed. A gap 508 (cavity 508) was provided between the mold 53 and the polymer molded product 507.

  Next, the carbon dioxide supplied from the carbon dioxide cylinder 21 of the electroless plating apparatus unit 501 was pressurized by the pump 19 and stored in the buffer tank 36. Next, the automatic valve 43 is opened, and the high-pressure carbon dioxide stored in the buffer tank 36 is introduced into the cavity 508 through the plating solution introduction path 61 to bring the high-pressure carbon dioxide into contact with the surface of the polymer molded product 507. (Step S62 in FIG. 13). At this time, since the cavity 508 is sealed by fitting the spring built-in seal 17 provided on the outer diameter portion of the fixed mold 13 and the movable mold 54, the introduced high-pressure carbon dioxide is introduced to the outside of the mold. There is no leakage. At this time, the pressure of the high-pressure carbon dioxide in the cavity 508 was set to 15 MPa. Since the surface of the polymer molded product 507 swells when the high pressure carbon dioxide is brought into contact with the surface of the polymer molded product 507 in this way, the polymer molding of the mixed fluid of the high pressure carbon dioxide and the electroless plating solution to be introduced next is performed. The effect that the penetration into the inside of the product 507 is performed more smoothly is obtained.

  Next, an electroless plating solution containing high-pressure carbon dioxide was introduced into the cavity 508 and brought into contact with the polymer molded product 507 as follows. First, an alcohol and surfactant-mixed electroless plating solution supplied from the plating tank 11 of the electroless plating apparatus unit 501 and a 15 MPa high-pressure carbon dioxide supplied from the buffer tank 36 in advance are stored in the high-pressure vessel 10. And mixed. The electroless plating solution of this example was prepared so that the ratio of each component contained therein was the same as in Example 1. At this time, the high-pressure carbon dioxide and the electroless plating solution were dissolved in the high-pressure vessel 10 by driving the stirrer 16 and rotating the magnetic stirrer 17 at high speed. Subsequently, the automatic valve 43 was closed and the automatic valves 44 and 45 were opened.

  Next, the circulation pump 9 is operated, and an electroless plating solution containing high-pressure carbon dioxide is circulated through a circulation flow path including the high-pressure vessel 10, the pipe 15, and the cavity 508, so Was contacted to form a plating film (nickel phosphorous film) (step S63 in FIG. 13). At this time, since the surface of the polymer molded product 507 is swollen, the electroless plating solution permeates into the polymer molded product 507 from the surface of the polymer molded product 507 and the metal fine particles dispersed inside the polymer molded product 507 are dispersed. A plating film grows as a catalyst nucleus. That is, since the plating film formed on the polymer molded product 507 grows in a state of being bitten into the polymer molded product 507, a plating film having excellent adhesion is formed. When the electroless plating solution containing high-pressure carbon dioxide is circulating, the pressures in the cavity 508 and the circulation line 15 are the same by the pressure sensors 58 and 59. Further, replenishment of the electroless plating solution was performed at any time by increasing the pressure of the plating solution supplied from the plating tank 11 with the syringe pump 33 and feeding it simultaneously with the opening of the automatic valve 46.

  Next, after forming a plating film on the polymer molded product 507 as described above, the electroless plating solution containing high-pressure carbon dioxide is recovered through the recovery container 63 from the circulation path of the electroless plating solution containing high-pressure carbon dioxide. The tank 12 was evacuated. Specifically, the automatic valves 44 and 45 were closed, and then the automatic valve 38 was opened, whereby the electroless plating solution containing high-pressure carbon dioxide was discharged into the collection container 16. In the collection container 63, the electroless plating solution containing the collected high-pressure carbon dioxide is separated into an aqueous solution (plating solution) and a high-pressure gas (carbon dioxide) by the principle of centrifugation. The plating solution can be recovered in the recovery tank 12 and reused. The gasified carbon dioxide is discharged from the upper part of the recovery container 63 and recovered in an exhaust duct (not shown).

  Next, the automatic valve 43 is opened for a certain period of time, high-pressure carbon dioxide is introduced into the gap 508 (cavity 508) between the fixed mold 53 and the polymer molded product 507, and the plating solution residue remaining in the cavity 508 is high-pressured. It was discharged out of the mold together with carbon dioxide. Next, when the internal pressure of the cavity 508 became zero as monitored by the pressure sensor 59, the mold was opened and the polymer molded product 507 was taken out.

  Next, the extracted polymer molded product 507 was subjected to normal substitutional gold plating, and a gold plating film was laminated on the surface of the polymer molded product 507. In this example, a polymer molded product 507 having a plating film formed on the surface was obtained as described above.

  FIG. 11 shows a schematic cross-sectional view of a part of the polymer molded product 507 produced in this example. It was confirmed that metal fine particles 600 (black circles in FIG. 11) are dispersed inside the skin layer 505 of the polymer molded product 507 produced in this example. Further, a nickel-phosphorus metal film 509 grown in a mold is formed on one side of the polymer molded article 507, and the nickel-phosphorus metal film 509 grew from the inside of the polymer molded article 507 (metal The permeation layer of the membrane 509 was formed). Also, a gold highly reflective film 510 was formed on the nickel-phosphorus metal film 509.

  In addition, the adhesion evaluation of the metal film was also performed on the polymer molded product 507 manufactured in this example by the same high temperature and high humidity environment test as in Example 1. A high temperature test was also conducted under conditions of a temperature of 150 ° C. and a notification time of 500 hours. As a result, the same results as in Example 1 were obtained, and no decrease in the adhesion of the metal film was observed. Furthermore, when the surface roughness Ra of the polymer molded product 507 produced in this example was measured, Ra = 100 nm, which is equivalent to the surface roughness of the mold. That is, according to the plating film forming method of this example, the plating process can be performed simultaneously with the injection molding, and not only can the process be simplified, but also a metal film having high adhesion and smoothness can be made heat resistant. It was found that it can be formed into a high resin material.

  In the electroless plating treatment of Example 6 above, first, only the high pressure carbon dioxide was brought into contact with the polymer molded product to swell the surface of the polymer molded product, and then the electroless plating solution was brought into contact with the polymer molded product. However, the present invention is not limited to this. For example, a first electroless plating solution containing high-pressure carbon dioxide in a polymer molded article and having a plating solution concentration that does not cause a plating reaction is contacted with the polymer molded article, and then plating containing a high-pressure carbon dioxide and causing a plating reaction occurs. A plating film may be formed by bringing a second electroless plating solution having a solution concentration into contact with the polymer molded product. Here, the plating solution concentration is the concentration of a reducing agent such as sodium hypophosphite that is a factor that determines the plating reaction in the plating solution. That is, the above method will be described more specifically. An electroless plating solution (first electroless plating solution) and a high-pressure carbon dioxide having a sufficiently small amount of reducing agent so as not to cause a plating reaction are brought into contact with a polymer molded product. Then, the plating solution is infiltrated into the polymer, and then the first electroless plating solution is converted into an electroless plating solution (second electroless plating solution) containing a reducing agent to such an extent that a plating reaction occurs sufficiently. It may be replaced. Alternatively, a second electroless plating solution is formed by adding a solvent containing water or alcohol containing a reducing agent as a main component and high-pressure carbon dioxide to the first electroless plating solution having a small reducing agent. May be.

  In Examples 1 to 6 described above, the example in which the crystal material is used as the forming material of the polymer member (polymer molded product) has been described. However, the present invention is not limited to this, and as the forming material of the polymer member (polymer molded product). The same effect can be obtained even when an amorphous material is used.

  In the method for forming a plating film of the present invention, a plating film grown from the inside of the polymer surface can be formed without roughening the surface of the polymer, so that it has excellent adhesion to various types of polymers. It is optimal as a method for forming a plating film.

  Further, in the method for forming a plating film of the present invention, when an electroless plating process is performed in an injection molding machine, a smooth metal film with high adhesion can be formed on a resin material with high heat resistance. It is suitable as a method for producing a reflector for an automotive headlight that requires heat resistance.

FIG. 1 is a schematic configuration diagram of a plating apparatus used in the first embodiment. FIG. 2 is a schematic cross-sectional view of the polymer member produced in Example 1, FIG. 2 (a) is a view when the mount and the lens holder are disassembled, and FIG. 2 (b) is a combination of the mount and the lens holder. FIG. FIG. 3 is a schematic cross-sectional view of the polymer member after surface modification of the polymer member in the plating film forming method of Example 1. FIG. 4 is a schematic cross-sectional view of the polymer member after the plating film is formed on the surface of the polymer member in the plating film forming method of the first embodiment. FIG. 5 is an SEM image of the vicinity of the surface of the polymer member produced in Example 1. FIG. 6 is a schematic configuration diagram of the plating apparatus used in the second embodiment. FIG. 7 is a schematic configuration diagram of the manufacturing apparatus used in the sixth embodiment. FIG. 8 is a view showing a state when high-pressure carbon dioxide in which a metal complex is dissolved in a molten resin in a plasticizing cylinder is introduced, and FIG. 8 (a) shows a state when the plasticizing and lightening of the molten resin is completed. FIG. 8B is a diagram showing a state when high-pressure carbon dioxide is introduced. FIG. 9 is a view showing a state when the injection molding of the polymer molded product is completed in the method of manufacturing a polymer molded product of Example 6. FIG. 10 is a diagram illustrating a state where the polymer molded product is subjected to electroless plating in the method of manufacturing a polymer molded product of Example 6. FIG. 11 is a diagram schematically showing a cross-sectional structure of a polymer molded product produced in Example 6. FIG. 12 is a flowchart for explaining the procedure of the plating film forming method according to the first embodiment. FIG. 13 is a flowchart for explaining the procedure of the plating film forming method according to the sixth embodiment.

Explanation of symbols

1, 1 ', 10 High-pressure vessel 8 Electroless plating solution 9 Inner vessel 21 Liquid carbon dioxide cylinder 20, 33, 34 Syringe pump 100, 200 Plating device 102 Polymer member (mount)
109,600 Metal fine particles 300 Electroless plating film 500 Manufacturing apparatus 501 Electroless plating apparatus section 502 Surface modification apparatus section 503 Injection molding apparatus section 504 Cavity 505 Skin layer (skin)
506 Core layer 507 Polymer molded product 509 Electroless nickel-phosphorus film 510 Gold plating film

Claims (17)

A method of forming a plating film on a polymer member,
Preparing a polymer member impregnated with fine metal particles inside the surface;
Contacting the polymer member with high-pressure carbon dioxide to swell the vicinity of the surface of the polymer member;
A method for forming a plating film, comprising: bringing a non-electrolytic plating solution containing high-pressure carbon dioxide into contact with the polymer member in a state where the vicinity of the surface of the polymer member is swollen to form a plating film on the polymer member. When the high pressure carbon dioxide is brought into contact with the polymer member, an electroless plating solution having a temperature at which a plating reaction does not occur together with the high pressure carbon dioxide is brought into contact with the polymer member to allow the electroless plating solution to permeate the polymer member. 2. The method of forming a plating film according to claim 1, wherein when forming the plating film on the polymer member, the temperature of the electroless plating solution is raised to a temperature at which a plating reaction occurs. The electroless plating solution, the method of forming the plating film according to claim 1 or 2, characterized in that it comprises an alcohol. The method of forming a plating film according to claim 1, wherein the electroless plating solution contains a surfactant . The method for forming a plating film according to any one of claims 1 to 4 , wherein the high-pressure carbon dioxide is supercritical carbon dioxide having a pressure of 7.38 MPa to 20 MPa . Furthermore, after forming a plating film in the said polymer member, the formation method of the plating film as described in any one of Claims 1-5 including performing at least one of electroless plating and electrolytic plating at a normal pressure . Furthermore, after forming a plating film in the said polymer member, the formation method of the plating film as described in any one of Claims 1-6 including performing black electroless plating . 8. The preparation of a polymer member impregnated with metal fine particles inside the surface includes bringing a high-pressure fluid in which the metal complex containing the metal fine particles is dissolved into contact with the polymer member. The method for forming a plating film according to claim 1. 9. The preparation of a polymer member impregnated with metal fine particles inside the surface includes molding the polymer member impregnated with metal fine particles inside the surface within a mold of an injection molding machine. The method for forming a plating film according to any one of the above. When forming a plating film on the polymer member, the inside of the metal high-pressure vessel provided with a film formed of a material that does not grow the plating film on the inner wall surface, the polymer member in the high-pressure vessel, The method for forming a plating film according to claim 1, wherein the plating film is brought into contact with an electroless plating solution containing high-pressure carbon dioxide . The method for forming a plating film according to claim 10 , wherein the film is made of diamond-like carbon . When forming a plating film on the polymer member, using a plating apparatus comprising a metal high-pressure vessel and an inner vessel formed of a material that does not grow a plating film disposed inside the high-pressure vessel, the inner vessel the polymer member in the inner, the method of forming the plating film according to any one of claims 1 to 9, wherein the contacting in an electroless plating solution containing the pressurized carbon dioxide. The method for forming a plating film according to claim 12 , wherein a material for forming the inner container is polytetrafluoroethylene . A method for forming a plating film according to any one of claims 1 to 9, wherein the high-pressure vessel is used for bringing an electroless plating solution into contact with a polymer member,
A metal high-pressure vessel body;
A high-pressure vessel provided with a film formed on the inner wall surface of the high-pressure vessel main body and formed of a material that does not allow the plating film to grow. The high-pressure vessel according to claim 14, wherein the film is formed of diamond-like carbon . It is a plating apparatus used for the formation method of the plating film as described in any one of Claims 1-9,
A metal high pressure vessel;
An inner vessel disposed inside the high-pressure vessel and used to bring the electroless plating solution into contact with the polymer member;
The plating apparatus, wherein the inner container is formed of a material that does not allow the plating film to grow. The plating apparatus according to claim 16, wherein a material for forming the inner container is polytetrafluoroethylene .

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