JP2005344133A - Plating treatment method and treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To securely obtain a plating film formed sufficiently on the object to be treated by a simple constitution by stably feeding a bubbled gas to the object to be treated. <P>SOLUTION: The plating treatment method where a plating film is formed on the surface of the object to be treated by arranging the object to be treated in a surface treatment solution is characterized in that a gas is injected into the surface treatment solution, the bubbles of the gas are formed in the surface treatment solution and are fed to the object to be treated as the surface treatment solution and the bubbles are made to flow, and the plating film is formed on the object to be treated. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a plating method and a plating apparatus which are dense and homogeneous and have a good turn around a workpiece.

  2. Description of the Related Art Conventionally, in order to form a high-quality plating film, a gas is supplied into a plating solution in which an object to be processed is immersed, and the gas is bubbled (see, for example, Patent Documents 1 to 3). Since the gas bubbled in the plating solution at the time of the plating process removes bubbles adhering to the object to be processed, a high-quality plating film can be obtained.

  In addition, in order to form a good plating film, there is a method of performing plating under a supercritical pressure of carbon dioxide (see, for example, Patent Document 4).

JP2003-247077 JP-A-10-287981 JP-A-6-330398 JP 2003-147591

  However, when bubbling gas in the plating solution and supplying the gas bubbles to the plated product, the gas was supplied from the lower side of the plated product exclusively by the buoyancy of the bubbles. For this reason, it is conceivable that the bubbling effect cannot be obtained with certainty.

  In addition, in order to form a good plating film, increasing the pressure of gas such as carbon dioxide until it reaches the supercritical pressure requires taking various safety measures and making the overall configuration of the plating apparatus large. It can be considered that.

  Further, when electroplating is performed, there is a problem that the film thickness at the end of the object to be processed increases due to local concentration of concentration depending on the potential gradient generated on the plating surface. For this reason, the proposal of the new method of preparation of plating film with high uniform electrodeposition property, ie, a uniform film thickness, is required.

  The present invention solves the above-mentioned problems, and an object of the present invention is to provide an easy-to-use structure formed on the object to be processed with a simple structure by stably supplying the bubbling gas to the object to be processed. It is to obtain a plating film reliably.

  The first invention according to the present invention for achieving the above object is a plating method for forming a plating film on the surface of an object to be processed by disposing the object to be processed in a surface treatment solution, A gas is injected into the surface treatment solution, bubbles of the gas are generated in the surface treatment solution, and the surface treatment solution and the bubbles are supplied to the treatment object while flowing, and a plating film is formed on the treatment object Is a plating method characterized in that

  2nd invention is a plating processing method as described in 1st invention, Comprising: The said surface treatment solution is a plating processing method characterized by having surfactant.

  A third invention is the plating method according to the first or second invention, wherein the surface treatment solution flows at a rate of 50 cm / sec or more.

  According to a fourth aspect of the present invention, there is provided a circulation path for circulating the surface treatment solution, a pressure feeding means for pumping the surface treatment solution to circulate in the circulation path, and a reaction for injecting a gas into the surface treatment solution. A gas injection means disposed on the upstream side of the tank, a bubble generation means for generating bubbles of the gas in the surface treatment solution, and inserted into a circulation path downstream of the bubble generation means. It is a plating processing apparatus characterized by having a reaction tank which stores processed material.

  5th invention is a plating processing method as described in 4th invention, Comprising: The said surface treatment solution is a plating processing apparatus characterized by having surfactant.

  A sixth invention is the plating apparatus according to the fourth or fifth invention, wherein the pumping means circulates the surface treatment solution in the circulation path at a speed of 50 cm / sec or more. It is a plating processing apparatus.

  A seventh invention is the plating apparatus according to any one of the fourth to sixth inventions, wherein the bubble generating means arranges a plurality of fixing members in the circulation path, and the fixing members The plating apparatus is characterized in that bubbles are generated in the surface treatment solution by passing the surface treatment solution and stirring.

  An eighth invention is the plating apparatus according to any one of the fourth to sixth inventions, wherein the bubble generating means agitates the surface treatment solution by rotating a blade-shaped member in the circulation path. This is a plating apparatus characterized by generating bubbles.

  According to a ninth aspect of the present invention, there is provided a circulation path for circulating the surface treatment solution, a reaction tank that is inserted in the circulation path and stores an object to be treated, and a gas injection means for injecting a gas into the surface treatment solution And a pressurized bubble generating means for generating bubbles of the gas in the surface treatment solution by stirring the surface treatment solution and the gas while pumping. is there.

  A tenth invention is the plating apparatus according to any one of the fourth to ninth inventions, wherein the circulation path seals the surface treatment solution and the gas in the circulation path. It is a processing device.

  An eleventh aspect of the invention is the plating apparatus according to any one of the fourth to ninth aspects of the invention, wherein the circulation path releases the gas on the downstream side of the reaction tank in the circulation path. It is a plating processing apparatus.

  According to the first invention, bubbles are uniformly generated in the surface treatment solution by stirring the surface treatment solution and the gas. In a state where the bubbles are dispersed in the surface treatment solution, the surface treatment solution is flowed and supplied to the object to be treated. Then, bubbles dispersed in the surface treatment solution are removed by dissolving by-products such as hydrogen and oxygen by electrolysis of water that occurs as a by-product during the plating process. The by-product adheres to the plating of the object to be processed and causes a hole formed without performing a plating process called pinhole, but the by-product dissolves in the bubbles. Since it is removed, the formation of the pinhole is effectively prevented. For this reason, the plating film without a pinhole can be formed. Thus, since the produced | generated bubble is contained uniformly in the said surface treatment solution which flows together, the plating film with a sufficient circumference | surroundings can be stably formed with respect to the said to-be-processed object.

  According to the second invention, since the surface treatment solution has the surfactant, the surface treatment solution can be easily made uniform, and the plating film can be stably formed on the object to be treated. .

  According to the third invention, since the surface treatment solution is caused to flow at a high speed of 50 cm / sec or more, new bubbles uniformly distributed in the surface treatment solution are continuously supplied to the object to be treated. The bubbles remove the bubbles already attached to the workpiece. Moreover, by causing the bubbles dispersed in the surface treatment solution to collide with the surface of the plating film at high speed, it is possible to more effectively dissolve the gas derived from the electrolysis of water, and hence uniform and pinhole-free plating. A film can be formed. In addition, by flowing the surface treatment solution at high speed, the concentration of local concentration depending on the potential gradient generated on the plating surface is dispersed, and the concentration on the plating surface is made uniform, resulting in high uniform electrodeposition and film thickness. A uniform plating film can be formed.

  According to the fourth invention, gas is injected from the gas injection means into the surface treatment solution in the circulation path, and bubbles of the gas are generated by the bubble generation means. By supplying the surface treatment solution together with the bubbles to the reaction vessel, it is possible to stably form a plating film having a good turn around the object to be treated in the reaction vessel.

  According to the fifth invention, since the surface treatment solution has the surfactant, the surface treatment solution can be easily made uniform, and the plating film can be stably formed on the object to be treated. .

  According to the sixth invention, by flowing the surface treatment solution at a high speed of 50 cm / sec or more, the new bubbles uniformly distributed in the surface treatment solution are constantly supplied to the object to be treated. The air bubbles can remove the air bubbles already attached to the object to be processed and can stably form a plating film having a good surroundings.

  According to the seventh invention, the bubble generating means is agitated by disposing a plurality of static stirring members in the circulation path and allowing the surface treatment solution to pass through the static stirring member. By generating bubbles in the solution, the stirring operation is performed using the kinetic energy of the surface treatment solution, and thus the stirring operation can be performed efficiently.

  According to the eighth invention, the bubble generating means generates the bubbles by rotating the blade-shaped member in the circulation path and stirring the surface treatment solution, thereby further sufficiently stirring the surface treatment solution. can do.

  According to the ninth aspect, by using the pressure-feeding stirring means for simultaneously feeding and stirring the surface treatment solution, the surface-treatment solution can be stirred while being pumped, and the two means are combined into one device. Can be miniaturized.

  According to the tenth invention, since the circulation path is sealed so that the gas does not leak from the circulation path, the sound is quiet and the outside air is not sucked in. It can handle liquids that change quality when touched.

  According to the eleventh aspect of the present invention, the circulation path does not need to be sealed for sealing by opening the gas on the downstream side of the reaction tank in the circulation path. Can be configured.

  Embodiments of the present invention will be described with reference to the drawings. In addition, this invention is not limited to a following example.

FIG. 1 is a schematic configuration diagram of a plating apparatus when a bubble generating means is used in a closed system, FIG. 2 is an explanatory view of a variation of the bubble generating means, and FIG. 3 uses a pressure agitating means in a closed system. FIG. 4 is a schematic explanatory view of the plating apparatus when the bubble generating means is used in an open system, and FIG. 5 is an explanatory view of the plating apparatus of another embodiment. It is.

  First, the surface treatment solution, the surfactant, and the gas that are circulated in the circulation path of each embodiment will be described in detail.

(Surface treatment solution)
As the surface treatment solution used for the plating treatment, a solution obtained by dissolving one or two or more kinds of metal salts, organic electrolytes, acids such as phosphoric acid, and various electrolytes such as alkaline substances in a solvent is used. The solvent is not particularly limited as long as it is a polar solvent. Specific examples include water, alcohols such as ethanol and methanol, cyclic carbonates such as ethylene carbonate and propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl. Examples thereof include linear carbonates such as carbonate, or a mixed solvent thereof.

 The metal salt may be appropriately selected in consideration of the type of metal, alloy, oxide, etc. to be deposited. The metals that can be electrochemically deposited include Cu, Zn, Ga, As, Cr, Se, Mn, Fe, Co, Ni, Ag, Cd, In, Sn, Sb, Te, Ru, Rh, Pd. Au, Hg, Tl, Pb, Bi, W, Po, Re, Os, Ir, Pt, and the like. Examples of the organic electrolyte include an anionic electrolyte such as polyacrylic acid and a cationic electrolyte such as polyethyleneimine, but are not limited thereto.

  In addition to the above substances, the surface treatment solution may contain one or more substances for the purpose of stabilizing the solution. Specifically, substances that form complex salts with metal ions to be deposited, irrelevant salts to improve the conductivity of the surface treatment solution, stabilizers for the surface treatment solution, buffer materials for the surface treatment solution, and change the physical properties of the deposited metal Examples thereof include substances, substances that help dissolve the cathode, substances that change the properties of the surface treatment solution or the deposited metal, and stabilizers for mixed solutions containing two or more metals.

  More specifically, the main components of the surface treatment solution in the main electrochemical reaction method are as follows, but are not limited thereto.

a. When depositing copper: crystalline copper sulfate and sulfuric acid, copper borofluoride and borofluoric acid, copper cyanide and sodium cyanide, copper pyrophosphate, potassium pyrophosphate, and aqueous ammonia b. When depositing nickel: nickel sulfate, ammonium chloride, and boric acid, nickel sulfate, nickel chloride, and boric acid, nickel sulfamate, nickel chloride, and boric acid c. When depositing chromium: chromic acid and sulfuric acid, chromic acid, barium acetate, and zinc acetate d. When precipitating zinc: zinc sulfate, ammonium chloride, ammonium sulfate, boric acid and dextrin, zinc oxide, sodium cyanide and caustic soda, (3) zinc oxide and caustic soda e. When precipitating cadmium: cadmium oxide, sodium cyanide, gelatin, and dextrin f. When precipitating tin: stannous sulfate, sulfuric acid, cresolsulfonic acid, β-naphthol, and gelatin, potassium stannate and free caustic potash g. When silver is precipitated: silver cyanide and potassium cyanide h. When depositing gold: gold, potassium cyanide, potassium carbonate, and potassium hydrogen phosphate i. When precipitating platinum: chloroplatinic acid, dibasic ammonium phosphate, and dibasic sodium phosphate, chloroplatinic acid and acetate j. When precipitating rhodium: concentrated sulfuric acid and rhodium, phosphoric acid and rhodium phosphate k. When depositing ruthenium: ruthenium complex l. When depositing brass: cuprous cyanide, zinc cyanide, sodium cyanide, and sodium carbonate m. When depositing tin-lead alloys: tin, lead, free borofluoric acid, and peptone, tin, lead, free borohydrofluoric acid, and peptone n. When precipitating iron-nickel alloy: nickel sulfamate, ferrous sulfamate, and sodium acetate o. In the case of depositing cobalt phosphorus: cobalt chloride, phosphorous acid, and phosphoric acid The charging ratio of the substance and the surface treatment solution in the reaction vessel (described later) is not particularly limited, It can be set as appropriate in consideration of the concentration of the surface treatment solution, reaction conditions, and the like.

(Surfactant)
Here, if the amount of the surface treatment solution is too small, the reaction is difficult to proceed. Therefore, it is preferable to include at least 0.01 wt% or more of the surface treatment solution with respect to the substance. Further, the reaction tank and the circulation path to be reacted can contain a surfactant in addition to the substance and the surface treatment solution in the above-described state. For example, when carbon dioxide is selected as the substance, since carbon dioxide is nonpolar, it is incompatible with the surface treatment solution, so that phase separation may usually occur. Therefore, by adding a surfactant, the system is agitated to be uniform, and the reaction efficiency is improved.

  As the surfactant, at least one or more of conventionally known anionic, nonionic, cationic, and zwitterionic surfactants can be appropriately selected and used.

  Examples of the anionic surfactant include soap, alpha olefin sulfonate, alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, phenyl ether sulfate ester salt, methyl taurate, sulfosuccinate, ether Sulfonate, sulfated oil, phosphate ester, perfluoroolefin sulfonate, perfluoroalkylbenzene sulfonate, perfluoroalkyl sulfate, perfluoroalkyl ether sulfate, perfluorophenyl ether sulfate, perfluoro Examples thereof include, but are not limited to, fluoromethyl taurate, sulfoperfluorosuccinate, perfluoroethersulfonate, and the like.

  Examples of the cation of the salt of the anionic anionic surfactant include sodium, potassium, calcium, tetraethylammonium, triethylmethylammonium, diethyldimethylammonium, tetramethylammonium and the like, but are not limited thereto. Any cations that can be electrolyzed can be used.

  Examples of the nonionic surfactant include C1-25 alkylphenols, C1-20 alkanols, polyalkylene glycols, alkylolamides, C1-22 fatty acid esters, C1-22 aliphatic amines, alkylamine ethylene oxide adducts. , Arylalkylphenol, C1-25 alkylnaphthol, C1-25 alkoxylated phosphoric acid (salt), sorbitan ester, styrenated phenol, alkylamine ethylene oxide / propylene oxide adduct, alkylamine oxide, C1-25 alkoxylated phosphoric acid (salt) ), Perfluorononylphenol, perfluoro higher alcohol, perfluoropolyalkylene glycol, perfluoroalkylolamide, perfluoro fatty acid ester, perfluoroa Kill amine oxide adduct, perfluoroalkyl amine oxide / perfluoro propylene oxide adduct, there may be mentioned perfluoro alkylamine oxides, not limited thereto.

  Examples of the cationic surfactant include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, trimethyl benzyl ammonium salt, Hexadecylpyridinium salt, laurylpyridinium salt, dodecylpicolinium salt, stearylamine acetate, laurylamine acetate, octadecylamine acetate, monoalkylammonium chloride, dialkylammonium chloride, ethylene oxide addition-type ammonium chloride, alkylbenzylammonium chloride, tetramethylammonium chloride , Trimethylpheny Ammonium chloride, tetrabutylammonium chloride, monoalkylammonium acetate, imidazolinium betaine, alanine, alkylbetaine, monoperfluoroalkylammonium chloride, diperfluoroalkylammonium chloride, perfluoroethylene oxide adduct ammonium chloride, perfluoro Examples include alkylbenzylammonium chloride, tetraperfluoromethylammonium chloride, triperfluoromethylphenylammonium chloride, tetraperfluorobutylammonium chloride, monoperfluoroalkylammonium acetate, perfluoroalkylbetaine, and the like. There is nothing to be done.

  Examples of the zwitterionic surfactant include betaine, sulfobetaine, aminocarboxylic acid, and the like, and sulfated or sulfonated adducts of condensation products of ethylene oxide and / or propylene oxide with alkylamine or diamine. However, it is not limited to these. Although the usage-amount of the said surfactant is not specifically limited, It is preferable to set it as about 0.0001-20 wt% with respect to a surface treatment solution, Most preferably, it is 0.001-10 wt%.

(gas)
As the gas used for the plating treatment, inert gas such as neon (Ne) and argon (Ar) is preferable in addition to nitrogen (N ₂ ) and carbon dioxide (CO ₂ ), but normal air is also possible. This gas is enclosed in a gas cylinder 40 described later.

[Example 1]
The outline | summary of the plating processing apparatus A of Example 1 is demonstrated using FIG. As shown in FIG. 1, the plating apparatus A of Example 1 includes a reaction tank 10 containing an object 11, a circulation path 20 in which a surface treatment solution or the like circulates, and a surface treatment in the circulation path 20. A circulation pump 30 (pressure feeding means) that gives power to circulate the solution, a gas cylinder 40 (gas injection means) that contains the gas and injects the gas into the circulation path 20, and a surface treatment solution and gas in the circulation path 20 And bubble generating means 50 for generating bubbles by stirring. Incidentally, 60 is a tank for storing the surface treatment solution, 70 is a tank for storing the surfactant, and 80 is a tank for storing the stored fluid. Hereinafter, the configuration of each unit will be described in detail.

(Configuration of plating equipment)
The reaction vessel 10 accommodates an object 11 to be processed such as a separator of a fuel cell and an anode plate 12 inside, and these are connected to the negative electrode side and the anode side of the power supply 14 via lead wires 13. The reaction tank 10 is inserted into the circulation path 20, and is disposed in a surface treatment solution supplied from the upstream side of the circulation path 20 to the object to be processed 11, and plating is performed with the surface treatment solution.

  The circulation path 20 is configured by connecting conduits in an annular shape. The circulation path 20 of the present embodiment is a closed system that is sealed so that once the surface treatment solution is sealed, the solution is not leaked to the outside until the plating process is completed. Since the circuit 20 is a closed system, the sound inside the circuit 20 is not leaked to the outside, so the sound is quiet, the outside air is not sucked in, and the system can be operated in a vacuum system. Can be handled. As shown in FIG. 1, in addition to the reaction tank 10 described above, a bubble generating means 50 is inserted in the circulation path 20 upstream of the reaction tank 10 in the flow direction of the surface treatment solution. A circulation pump 30 for pumping the surface treatment solution is inserted.

  The circulation pump 30 circulates the surface treatment solution in the circulation path 20 by pumping the surface treatment solution. The flow rate of the surface treatment solution in the circulation path 20 is determined according to the power of the circulation pump 30.

  The gas cylinder 40 is filled with the above-described inert gas such as nitrogen or carbon dioxide, and is connected to the circulation path 20 downstream of the circulation pump 30 in the flow direction of the surface treatment solution by a gas conduit.

  The bubble generating means 50 agitate the surface treatment solution circulating in the circulation path 20 and the gas to make the gas in the solution a bubble. Further, by uniformly stirring the surface treatment solution, it is possible to improve the performance of the surface treatment solution with respect to the object to be treated.

  As the bubble generating means 50, a static stirring device can be used. The static agitation device does not include dynamic parts, and is configured by a tube having a partition plate disposed inside. The surface treatment solution and the gas are mixed by dividing the flow into a number of stages in a static stirrer tube. For example, as shown in FIG. 2 (a), a spiral-shaped member (static stirring member) 51a that divides the fluid into two and rotates it 180 ° in the pipe 51 of the bubble generating means 50 is 90 °. Stirring is performed by alternately shifting and fixing to the piping of the circulation path 20 and passing the surface treatment solution and gas through the spiral member. Alternatively, as shown in FIG. 2 (b), a plurality of square columnar members (static stirring members) 52 a are fixed to the piping of the circulation path 20 in the pipe 52 of the bubble generating means 50, and the surface treatment solution And it stirs by letting gas pass, dividing | segmenting. In this way, the gas is turned into bubbles in the static stirring device, and the bubbles in the liquid are made finer, so that the contact interface becomes larger. Thereby, the dissolution efficiency of a surface treatment solution and gas increases.

  As the bubble generating means 50, a dynamic stirring device can be used. The dynamic stirring device has a rotating member having a rotating shaft, and the rotating member is powered by a motor (not shown) and rotated to stir the surface treatment solution and the gas. For example, as shown in FIG. 2 (c), a blade member 53 a having a rotation axis may be installed in the conduit 53 of the bubble generating means 50. Thereby, the surface treatment solution and the gas are agitated, and bubbles of the gas are generated.

(Plating treatment method)
The plating method will be described with reference to FIG. First, as a pretreatment of the plating process for the object to be processed, a degreasing process and a pickling process for the object to be processed are completed.

  When entering a plating process for forming a plating film on the workpiece 11, first, the surfactant in the tank 70 is mixed into the surface treatment solution in the tank 60, and the surface treatment solution is injected into the circulation path 20. Then, the valve 41 between the tank 60 and the circulation path 20 is closed. Next, an inert gas sealed in the gas cylinder 40 is injected into the circulation path 20, and the valve 61 between the gas cylinder 40 and the circulation path 20 is closed.

  The surface treatment solution is caused to flow by driving the circulation pump 30. The surface treatment solution circulates while passing through the bubble generating means 50 and the reaction vessel 10 inserted in the circulation path 20. At this time, it is desirable to flow at a high speed of 50 cm / sec or higher. Moreover, it is preferable to make it flow in a turbulent flow region in order to improve stirring efficiency.

  The surface treatment solution of the circulation path 20 is stirred by the bubble generating means 50. By stirring, the surfactant in the surface treatment solution is uniformly mixed. Further, when the gas sealed in the circulation path 20 from the gas cylinder 40 passes through the bubble generating means 50, the gas becomes bubbles and diffuses uniformly in the surface treatment solution. Then, in a state where ions in the surface treatment solution are uniformly distributed by the action of the surfactant, the surface treatment solution is supplied to the object to be treated 11 in the reaction tank 10, so that the ions are applied to the surface of the object to be treated. It can be made to adhere uniformly.

  The surface treatment solution flows in a certain direction at a high speed in the reaction vessel 10 in a state where the surfactant is uniformly mixed and the bubbles are uniformly diffused. Here, the surface treatment solution that flows at high speed preferably passes through the reaction vessel 10 in 2 seconds or less.

  By causing the bubbles dispersed in the surface treatment solution to collide with the surface of the plating film at a high speed, by-products such as hydrogen, oxygen and nitrogen resulting from water electrolysis are more effectively dissolved in the bubbles. Can be made. Therefore, a uniform plating film can be formed. Further, by flowing the surface treatment solution at a high speed, the concentration of local concentration depending on the potential gradient generated on the plating surface is dispersed, and the concentration on the plating surface is made uniform, that is, the film has a high uniform electrodeposition property, that is, a film. A film having a uniform thickness can be formed.

  In the plating process, there is a phenomenon in which byproducts such as hydrogen, nitrogen, and oxygen adhere to the object to be processed due to the electrolysis of water that occurs as a by-product. If the plating process is continued in a state where the by-product is attached, a hole formed without performing a plating process called a pinhole is formed on the object to be processed. However, according to the present embodiment, the by-product is dissolved and removed in the bubbles, thereby effectively preventing the formation of the pinhole. For this reason, the plating film without a pinhole can be formed.

  Further, the configuration of the plating apparatus can be achieved even at room temperature and normal pressure, and it is not necessary to increase the pressure until a gas such as carbon dioxide reaches a supercritical pressure in order to form a high-quality plating film. For this reason, it is not necessary to take various safety measures that must be taken under high pressure, and a high-quality film can be reliably obtained with a simple structure.

  According to this example, the plating film on the object to be processed obtained has a film thickness distribution on one side of the plating film with respect to the object to be processed having a side length of 3 cm or more. % Can be suppressed. Moreover, the plated product obtained can make the metal particle size of a plating film 8 nm or more and 50 nm or less.

  After the plating film is formed, the surface treatment solution can be taken out from the circulation path 20 to the tank 80 and reused by operating the switching valve 81.

[Example 2]
The structure of the plating apparatus B of Example 2 will be described with reference to FIG. The present embodiment is characterized in that it does not have the bubble generating means 50 of the first embodiment, and the pressure agitating means 130 having both functions of the circulation pump 30 and the bubble generating means 50 is inserted in the circulation path 20. To do. The same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted. Further, the plating method is substantially the same as that of the above-described embodiment, and therefore will be omitted.

(Configuration of plating equipment)
As the pressure-feed stirring means 130, for example, a device that stirs the solution while pumping the surface treatment solution, such as a canned motor pump, can be used. By using the pressure-feeding stirring means for simultaneously feeding and stirring the surface treatment solution, stirring can be performed while pressure-feeding the surface treatment solution, and the apparatus can be downsized by combining two means.

  Further, in order to perform the stirring operation of the surface treatment solution by the pressure feed stirring means 130, the gas inlet from the gas cylinder 40 is arranged on the upstream side of the pressure feed stirring means 130.

Example 3
The structure of the plating apparatus C of Example 3 will be described with reference to FIG. In this embodiment, unlike the previous embodiment, the circulation path is an open system. That is, the circulation path is opened to the atmosphere on the way. The plating method is substantially the same as in the above-described embodiment.

(Configuration of plating equipment)
In the present embodiment, the circulation path 20 is provided with a circulation pump 30, a bubble generation means 50, a reaction tank 10, and a gas-liquid separation means 200. By adopting a configuration in which the circulation path 20 opens the gas on the downstream side of the reaction tank 10, it is not necessary to perform sealing so as to seal, and a plating apparatus can be configured with a simple configuration.

  The gas-liquid separation means 200 separates the surface treatment solution and the gas after performing the plating process in the reaction vessel 10. Here, the gas portion is discharged from the exhaust port 200a. On the other hand, the liquid portion is sucked by the suction force of the circulation pump 30 and circulates in the circulation path 20 again. The gas discharged from the exhaust port 200a is preferably returned to the gas cylinder 40 or its downstream side by being reused.

(Plating treatment method)
This embodiment is also substantially the same as the embodiment described above, but it is necessary to continuously supply gas from the gas cylinder 40 during the plating process in order to extract the gas from the exhaust port 200a. For this reason, the valve 41 is kept open during the plating process.

[Other Examples]
In the second embodiment described above, the pressure-feed agitating means 130 is used in the closed circuit, but the present invention is not limited to this, and it is possible to use the pressure-feed agitating means 130 in the open circuit.

  In the embodiment described above, the static stirring device and the dynamic stirring device are used as the bubble generating means, but the present invention is not limited to this. For example, the surface treatment solution can be vibrated by attaching an ultrasonic oscillator to a part of the upstream side of the reaction tank 10 in the circulation path, whereby the gas in the circulation path can be made into fine bubbles.

  In the embodiment described above, the workpiece 11 is assumed to be conductive and the anode plate 12, the lead wire 13 and the like are attached to the reaction vessel 10, but this is not restrictive. For example, by appropriately selecting a surface treatment solution, it is possible to perform a plating process even on a non-conductive material such as an ABS resin.

  In the embodiment described above, the reaction vessel 10 is used to flow the surface treatment solution in the reaction vessel 10, but the present invention is not limited to this. For example, as shown in FIG. 5A, the surface treatment solution may be jetted from the orifice 300 attached to the circulation path 20 toward the workpiece 11. In this case, the gas can be recovered by means not shown, and the surface treatment solution can be recovered by the recovery means 310 and used again in the circulation path 20. Note that 320 is a conveying means such as a belt conveyor for conveying the object 11 to be processed. In addition, as shown in FIG. 5B, the object to be processed 11 does not necessarily have to be transported by the transport means 320, and a method of supplying the surface treatment solution from the orifice 300 after being fixed upright may be used. Also in this case, the surface treatment solution after the plating treatment is collected by the collecting means 310 and reused in the circulation path 20.

  INDUSTRIAL APPLICABILITY The present invention can be used for a plating method and a plating apparatus that are dense and homogeneous and have good circulation around a workpiece.

The schematic block diagram of the plating apparatus in the case of using a bubble generation means by a closed system. Explanatory drawing of the variation of a bubble generation means. The schematic explanatory drawing of the plating processing apparatus in the case of using a pressure-feed stirring means by a closed system. The schematic explanatory drawing of the plating processing apparatus in the case of using a bubble generation means by an open system. Explanatory drawing of the plating processing apparatus of another Example.

Explanation of symbols

A: Plating apparatus, B: Plating apparatus,
C: plating apparatus, D: plating apparatus,
10 ... Reaction tank, 11 ... Workpiece, 12 ... Anode plate, 13 ... Lead wire, 14 ... Power supply,
20… circulation path, 30… circulation pump, 40… gas cylinder, 41… valve,
50 ... bubble generating means, 51 ... pipe, 51a ... spiral member,
52 ... Pipe line, 52a ... Square columnar member, 53 ... Pipe line, 53a ... Blade member,
60 ... Tank, 61 ... Valve, 70 ... Tank, 80 ... Tank, 81 ... Switching valve,
130 ... pressure feed stirring means, 200 ... gas-liquid separation means, 200a ... exhaust port,
300 ... Orifice, 310 ... Recovery means, 320 ... Conveyance means

Claims (11)

A plating treatment method for forming a plating film on the surface of an object to be treated by disposing the object to be treated in a surface treatment solution,
A gas is injected into the surface treatment solution, bubbles of the gas are generated in the surface treatment solution, and the surface treatment solution and the bubbles are supplied to the treatment object while flowing, and a plating film is formed on the treatment object The plating method characterized by forming. The plating method according to claim 1,
The plating treatment method, wherein the surface treatment solution contains a surfactant. The plating method according to claim 1 or 2,
The plating treatment method, wherein the surface treatment solution flows at a rate of 50 cm / sec or more. A circulation path for circulating the surface treatment solution;
Pumping means for pumping the surface treatment solution to circulate in the circulation path;
A gas injection means disposed on the upstream side of the reaction tank for injecting a gas into the surface treatment solution;
Bubble generating means for generating bubbles of the gas in the surface treatment solution;
A reaction vessel that is inserted into a circulation path downstream of the bubble generating means and stores an object to be processed;
A plating apparatus characterized by comprising: It is a plating processing method of Claim 4, Comprising:
The plating apparatus according to claim 1, wherein the surface treatment solution includes a surfactant. The plating apparatus according to claim 4 or 5, wherein
The plating apparatus is characterized in that the pressure feeding means circulates the surface treatment solution in the circulation path at a speed of 50 cm / sec or more. The plating apparatus according to any one of claims 4 to 6,
The bubble generating means arranges a plurality of stirring members in the circulation path, and generates bubbles in the surface treatment solution by passing the surface treatment solution through the stirring member and stirring. Plating processing equipment. The plating apparatus according to any one of claims 4 to 6,
The said bubble generation means produces | generates a bubble by rotating a blade-shaped member in the said circulation path, and stirring the said surface treatment solution, The metal-plating processing apparatus characterized by the above-mentioned. A circulation path for circulating the surface treatment solution;
A reaction vessel that is inserted in the circulation path and stores an object to be processed;
A gas injection means for injecting a gas into the surface treatment solution;
A pressure agitating means for generating bubbles of the gas in the surface treatment solution by agitating while feeding the surface treatment solution and the gas;
A plating apparatus characterized by comprising: The plating apparatus according to any one of claims 4 to 9,
The plating apparatus is characterized in that the circulation path seals the surface treatment solution and the gas in the circulation path. The plating apparatus according to any one of claims 4 to 9,
The plating apparatus characterized in that the circulation path releases the gas on the downstream side of the reaction tank in the circulation path.

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