WO2016147709A1 - 治具用電解剥離剤 - Google Patents
治具用電解剥離剤 Download PDFInfo
- Publication number
- WO2016147709A1 WO2016147709A1 PCT/JP2016/052588 JP2016052588W WO2016147709A1 WO 2016147709 A1 WO2016147709 A1 WO 2016147709A1 JP 2016052588 W JP2016052588 W JP 2016052588W WO 2016147709 A1 WO2016147709 A1 WO 2016147709A1
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- WO
- WIPO (PCT)
- Prior art keywords
- palladium
- electrolytic
- jig
- jigs
- stripper
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
- C23C18/163—Supporting devices for articles to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/06—Suspending or supporting devices for articles to be coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
Definitions
- the present invention relates to an electrolytic stripper for jigs.
- a plating jig is generally used to fix an object to be plated.
- the plating jig is made of a metal such as stainless steel for energization, and is coated with an insulating material such as vinyl chloride, polyolefin, or fluorine resin except for the energized portion.
- Examples of the method for peeling the metal film deposited on the energized portion of the plating jig include a method of immersing in a nitric acid aqueous solution, a method of immersing in an aqueous solution containing an electrolytic remover, and electrolysis.
- an acidic etching solution containing manganese as an active ingredient may be used instead of the chromic acid mixed solution.
- the chromic acid mixed solution described above it adheres to the plating jig. There is a problem that the palladium is dissolved and accumulated in the etching solution and the etching performance is lowered.
- the palladium adhering to the insulating material coating part can also be removed, and the metal erosion of the current-carrying part of the plating jig is suppressed. Development of an electrolytic stripper for jigs is desired.
- the present invention can sufficiently remove palladium adhering to the energized portion of the plating jig, can also remove palladium adhering to the insulating material coating portion, and the metal of the energized portion of the plating jig It is an object of the present invention to provide an electrolytic stripper for a jig in which erosion of the steel is suppressed.
- the present inventor has (A) at least one selected from nitric acid and its salt, and (B) ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound and amino acid.
- the electrolytic stripping agent for jigs containing at least one selected from the group and (C) bromide the inventors have found that the above object can be achieved, and have completed the present invention.
- Electrolytic release agent for jigs containing the following components (A) to (C): (A) at least one selected from nitric acid and salts thereof; (B) at least one selected from the group consisting of ammonia, ammonium salts, ethyleneamine compounds, alkyldiamine compounds and amino acids, (C) Bromide. 2. (D) The electrolytic stripping agent for jig
- a method for removing palladium comprising bringing the electrolytic stripper for jigs according to any one of Items 1 to 3 into contact with a workpiece to which palladium is attached. 5.
- Item 5. The method for removing palladium according to Item 4, wherein electrolytic stripping is performed by bringing the cathode and the anode to be processed into contact with an electrolytic stripper for jig. 6).
- Item 6. The palladium removal method according to Item 5, wherein the cathode is isolated by a diaphragm. 7).
- Item 7. The method for removing palladium according to any one of Items 4 to 6, wherein the electrolytic stripper for jig is stirred with air. 8).
- Item 8 A method for suppressing the concentration of palladium accumulated in an acidic etching solution containing manganese by performing the method for removing palladium according to any one of Items 4 to 7.
- the electrolytic stripping agent for jigs of the present invention (A) at least one selected from nitric acid and its salt, (B) selected from the group consisting of ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound and amino acid. Since at least one kind of (C) bromide is contained, palladium adhering to the current-carrying portion of the plating jig can be sufficiently removed, palladium adhering to the insulating material coating portion can also be removed, and It is possible to suppress metal erosion of the energized portion of the plating jig.
- the electrolytic stripper for jigs of the present invention is (A) at least one selected from nitric acid and its salt, (B) at least selected from the group consisting of ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound and amino acid. 1 type and (C) containing bromide.
- the electrolytic stripping agent for jigs of the present invention is not particularly limited as long as it contains the above components (A) to (C), but normally the above components (A) to (C) are dissolved. Used as an aqueous solution.
- a component is at least 1 sort (s) selected from nitric acid and its salt. Although it does not specifically limit as nitric acid and its salt, A water-soluble thing is preferable.
- the nitrate include sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, iron nitrate, silver nitrate, lead nitrate, zinc nitrate, and barium nitrate.
- sodium nitrate, potassium nitrate, ammonium nitrate, and calcium nitrate because stainless steel, which is a current-carrying part of the plating jig, is unlikely to corrode and can be used stably because generation of precipitation is suppressed.
- nitric acid or nitrate may be used alone or in combination of two or more.
- the content of the component (A) in the electrolytic release agent for jigs is preferably 1 to 500 g / L, more preferably 5 to 200 g / L, and still more preferably 10 to 100 g / L. If the content of the component (A) in the electrolytic stripper for jigs is too small, there is a risk of corrosion of the stainless steel as the current-carrying part of the plating jig, and if it is too much, mist is generated and the working environment is lowered. There is a risk of accelerating the corrosion of the equipment.
- component Component (B) is at least one selected from the group consisting of ammonia, ammonium salts, ethyleneamine compounds, alkyldiamine compounds, and amino acids.
- ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound, and amino acids are not particularly limited, but are preferably compounds capable of forming a water-soluble complex with palladium.
- ammonium salt examples include ammonium sulfate, ammonium carbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium nitrate, and ammonium acetate.
- ethyleneamine compound examples include ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
- alkyl diamine compound examples include 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,6-hexamethylene diamine and the like.
- amino acids include glycine, alanine, cysteine and the like.
- ammonia and / or an ammonium salt are preferable in that palladium adhering to the insulating material coating portion of the plating jig can be sufficiently removed.
- ammonium sulfate, ammonium bromide, ammonium nitrate, and ammonium acetate are preferable. More preferred.
- the content of the component (B) in the electrolytic stripping agent for jigs is preferably 1 to 500 g / L, more preferably 10 to 400 g / L, and still more preferably 30 to 300 g / L. If the content of the component (B) in the electrolytic stripping agent for jigs is too small, the removal of palladium may not be sufficient, and if it is too much, the odor may become strong and the working environment may be deteriorated.
- ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound or amino acid may be used alone or in combination of two or more.
- Component (C) is bromide. Although it does not specifically limit as a bromide, A water-soluble thing is preferable. Specific examples of the bromide include hydrogen bromide, sodium bromide, potassium bromide, calcium bromide, ammonium bromide, silver bromide, lead bromide, zinc bromide, aluminum bromide and the like. Above all, palladium adhering to the insulating material coating part of the plating jig can be removed sufficiently, and the occurrence of precipitation is suppressed and can be used stably. Hydrogen bromide, sodium bromide, potassium bromide, bromide It is preferable to use calcium or ammonium bromide.
- the above bromides may be used alone or in a combination of two or more.
- the content of the component (C) in the electrolytic release agent for jigs is preferably 1 to 300 g / L, more preferably 5 to 200 g / L, and still more preferably 10 to 100 g / L. If the content of the component (C) in the electrolytic stripper for jigs is too small, there is a possibility that the palladium adhering to the insulating material coating portion of the plating jig cannot be removed sufficiently. There is a possibility that the deposited nickel film cannot be sufficiently peeled off. If the amount is too large, there is a risk that the stainless steel, which is the current-carrying portion of the plating jig, will corrode.
- the electrolytic stripping agent for jigs of the present invention may contain components other than the components (A) to (C).
- examples of other components include (D) copper ions, (E) oxidizing agents, and (F) complexing agents.
- the electrolytic stripping agent for jigs of the present invention may contain (D) copper ions in order to further improve palladium removability. It does not specifically limit as a copper ion, For example, the copper ion formed by melt
- the copper compound is not particularly limited as long as it can be dissolved in the electrolytic stripper of the present invention to give copper ions, but a water-soluble one is preferable. Examples of such copper compounds include copper sulfate, copper chloride, copper bromide, copper iodide, copper acetate, copper nitrate, and copper oxide.
- copper sulfate, copper bromide, copper acetate, copper nitrate are excellent in that the palladium adhering to the insulating material coating part of the plating jig is excellent and the stainless steel that is the current-carrying part of the plating jig is not easily corroded. It is preferable to use copper oxide.
- the (D) copper ion a copper ion obtained by electrolytic oxidation of metallic copper may be used.
- metallic copper may be immersed in the electrolytic stripper for jigs of the present invention, and the metallic copper may be electrolytically oxidized.
- the content of the component (D) in the electrolytic release agent for jigs is preferably 0.01 to 100 g / L, more preferably 0.1 to 50 g / L, and still more preferably 1 to 30 g / L. If the content of the component (D) in the electrolytic stripping agent for jigs is too small, the removability of palladium may not be sufficiently improved, and if it is too large, sludge of copper compounds may be easily generated.
- the electrolytic stripping agent for jigs of the present invention may contain (E) an oxidizing agent in order to further improve palladium removability.
- the oxidizing agent is not particularly limited, and examples thereof include persulfate, halogen oxoacid, halogen oxoacid salt, chromium trioxide, chromate, permanganate, hydrogen peroxide, and the like.
- persulfate, halogen oxoacid, halogen oxoacid salt are excellent in removing palladium adhering to the insulating material coating part of the plating jig and stainless steel, which is the current-carrying part of the plating jig, is difficult to corrode.
- persulfate, bromate, and bromate are more preferred.
- persulfate sodium persulfate, potassium persulfate, ammonium persulfate and the like can be used.
- bromate sodium bromate, potassium bromate, ammonium bromate, etc. can be used.
- the above oxidizing agents may be used alone or in combination of two or more.
- the content of the component (E) in the electrolytic release agent for jigs is preferably 0.01 to 100 g / L, more preferably 0.05 to 50 g / L, and still more preferably 0.1 to 20 g / L. . If the content of the component (E) in the electrolytic stripper for jigs is too small, the removability of palladium may not be improved sufficiently, and if it is too much, stainless steel, which is the current-carrying part of the plating jig, is likely to corrode. There is a risk.
- the electrolytic stripping agent for jigs of the present invention may contain (F) a complexing agent.
- production of precipitation of a metal hydroxide can be suppressed because the electrolytic release agent for jig
- the complexing agent is not particularly limited, and examples thereof include acetic acid, citric acid, maleic acid, succinic acid, lactic acid, malic acid, tartaric acid, and ethylenediaminetetraacetic acid. Among these, acetic acid, maleic acid, succinic acid, and malic acid are preferable in that metal ions can be easily removed by a metal flocculant when wastewater treatment is performed.
- the above complexing agents may be used alone or in a combination of two or more.
- the content of the component (F) in the electrolytic release agent for jigs is preferably 0.1 to 200 g / L, more preferably 1 to 100 g / L, and still more preferably 5 to 50 g / L. If the content of the component (F) in the electrolytic stripper for jigs is too small, there is a risk that the suppression effect on the precipitation of metal hydroxide may not be sufficient. There is a possibility that the removability of the deposited palladium may be lowered.
- the electrolytic stripping agent for jigs of the present invention may contain a solvent.
- the components (A) to (C) are usually dissolved in a solvent, and the components (D) to (F) and other additives are added as necessary. Is dissolved.
- water etc. can be used and it is more preferable to use water. That is, in the electrolytic stripper for jig of the present invention, the above components (A) to (C) are dissolved in water, and the above components (D) to (F) and other additives are added as necessary. It is preferable that the aqueous solution is dissolved.
- the pH of the electrolytic stripping agent for jigs of the present invention is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more. If the pH is too low, sludge of the metal compound may be easily generated, and the metal material in the current-carrying portion of the jig may be easily eroded. Further, the pH of the electrolytic stripper for jig is preferably 12 or less, and more preferably 10 or less. If the pH is too high, the odor becomes strong and the working environment may be deteriorated.
- the present invention is also a palladium removal method in which the electrolytic stripping agent for jigs is brought into contact with a workpiece to which palladium is attached.
- the object to be treated is a plating jig for fixing the object to be plated when electroless plating or electroplating is performed on the object to be plated.
- the plating jig includes an energization portion for performing plating, and has an insulating material coating portion coated with an insulating material in order to suppress erosion at locations other than the energization portion.
- the metal material forming the energized portion is coated with the insulating material to form the insulating material coating portion, and a portion of the metal material is exposed without being covered with the insulating material, so that the energized portion Is formed.
- palladium adheres to the current-carrying portion, and further palladium adheres to the surface of the insulating material.
- the metal material is not particularly limited as long as it can be energized.
- stainless steel, titanium, or the like is used. Of these, stainless steel is preferably used.
- the insulating material is not particularly limited as long as it can exhibit insulating properties, but resins such as vinyl chloride, polyolefin, and fluorine resin can be used. Of these, vinyl chloride is preferably used.
- the method for bringing the electrolytic stripping agent for jigs into contact with the workpiece to which palladium is attached is not particularly limited.
- the workpiece may be immersed in the electrolytic stripping agent for jigs by a conventionally known method.
- the pH of the electrolytic stripping agent for jigs is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more. If the pH is too low, sludge of the metal compound may be easily generated, and the metal material in the current-carrying portion of the jig may be easily eroded. Further, the pH of the electrolytic stripper for jig is preferably 12 or less, and more preferably 10 or less. If the pH is too high, the odor becomes strong and the working environment may be deteriorated.
- the temperature of the electrolytic stripper for jig is preferably 20 ° C. or higher, more preferably 30 ° C. or higher. If the temperature of the electrolytic stripping agent for jigs is too low, the palladium removability may be reduced. Moreover, although the upper limit of the liquid temperature of the electrolytic stripping agent for jig
- the object to be treated is immersed in the electrolytic stripping agent for jigs, so that the palladium adhering to the surface of the metal material forming the energized portion and the insulating material coating portion are Palladium adhering to the surface of the insulating material to be formed can be removed, but palladium removal is performed by performing electrolytic stripping by using the object to be treated as an anode and bringing the anode and cathode into contact with an electrolytic stripper for jigs. A method is preferred. By adopting such a palladium removal method, the palladium adhering to the surface of the metal material and the insulating material can be peeled off more efficiently.
- the cathode used for electrolytic stripping is not particularly limited, and a conventionally known cathode used for electrolytic stripping can be used.
- a conventionally known cathode used for electrolytic stripping can be used.
- examples of such a cathode include stainless steel, copper, nickel, lead, tin, iron, zinc, brass, aluminum, and carbon.
- the anode current density at the time of electrolytic stripping is not particularly limited, but can usually be in a wide range of about 0.3 to 15 A / dm 2, but if the current density is too low, the time required for electrolytic stripping becomes long. If the current density is too high, the metal material may be etched.
- the cathode is isolated by a diaphragm. That is, the cathode is preferably immersed in the electrolytic stripper for jigs of the present invention, and the cathode is preferably separated by a diaphragm together with the peripheral electrolytic stripper for jigs in contact with the cathode.
- the cathode is preferably immersed in the electrolytic stripper for jigs of the present invention, and the cathode is preferably separated by a diaphragm together with the peripheral electrolytic stripper for jigs in contact with the cathode.
- the material of the diaphragm is not particularly limited as long as it is a stable material in the electrolytic stripper for jigs.
- Examples of such a diaphragm include a cation exchange membrane, an anion exchange membrane, a membrane membrane, and an unglazed membrane.
- a perfluorinated sulfonic acid resin cation exchange membrane is used in terms of maintaining palladium removal performance. Is preferred.
- the electrolytic stripping agent for jigs is stirred with air.
- the electrolytic stripping agent for jigs is stirred with air, palladium can be removed more efficiently.
- the method of air agitation is not particularly limited, and examples thereof include a method of feeding air into the electrolytic stripper for jigs using a commercially available air pump and piping such as vinyl chloride and stainless steel.
- the air flow rate during the air agitation is preferably 0.1 to 5.0 L / min, more preferably 0.3 to 3.0 L / min per liter of bath volume. If the air flow rate during air agitation is too small, the removal efficiency of palladium may not be sufficiently improved, and if it is too much, the liquid may easily volatilize.
- the palladium removal method of the present invention By performing the palladium removal method of the present invention described above, it is possible to remove palladium adhering to the jig that is the object to be processed. For this reason, by repeatedly using the jig, even if the object to be plated is fixed to the jig and immersed in an acidic etching solution containing chromium trioxide or manganese, the palladium adhered to the jig It is possible to suppress an increase in the concentration of palladium due to dissolution and accumulation in the acidic etching solution.
- Such a method for suppressing the concentration of palladium accumulated in an acidic etching solution containing chromium trioxide and a method for suppressing the concentration of palladium accumulated in an acidic etching solution containing manganese are also disclosed in the present invention.
- a commercially available soft vinyl chloride coating sol polymer is applied to a flat plate (5 cm ⁇ 5 cm, thickness 0.3 mm, surface area 0.5 dm 2 ) of a vinyl chloride resin coated plate SUS304, dried, and then soft vinyl chloride coating It is immersed in sol (trade name: PG2401 (registered trademark), manufactured by Alpha Kasei Co., Ltd.) for 5 seconds and baked at 180 ° C. for 30 minutes to give a vinyl chloride resin-coated plate (hereinafter also referred to as “vinyl chloride plate”). Produced.
- a SUS304 flat plate (5 cm ⁇ 5 cm, thickness 0.3 mm, surface area 0.5 dm 2 ) heated to a polyethylene coated plate 180 ° C. is immersed in powdered polyethylene having an average particle diameter of 1000 ⁇ m for 1 minute, and 5 ° C. at 180 ° C. The surface was melted and smoothed by heating for a minute. Subsequently, it was immersed in water and cooled to prepare a polyethylene-coated plate (hereinafter also referred to as “polyethylene plate”).
- the vinyl chloride plate or polyethylene plate to which palladium was attached was immersed in the electrolytic stripper for jigs of Examples 1 to 15 and Comparative Examples 1 to 5 for 5 minutes.
- the temperature of the electrolytic stripping agent for jigs at this time was 40 ° C., and when air stirring was performed, the air flow rate was 0.5 L / min.
- the palladium adhering to the vinyl chloride plate or the polyethylene plate is peeled and dissolved with 10 ml of hot aqua regia, and the solution is adjusted with ion-exchanged water so that the volume becomes 100 ml, and the palladium concentration is measured by ICP emission spectrometry. did. From the measured concentration, the amount of palladium per unit area attached to the vinyl chloride plate or the polyethylene plate was calculated, and the palladium removal rate was calculated according to the following formula 1.
- the mass of the test material before and after electrolysis was measured, and the peeling rate of copper or nickel was calculated according to the following formula 3.
- the metal density was calculated as 8.94 g / cm 3 for copper and 8.91 g / cm 3 for nickel.
- the electrolytic stripping agent for jigs (Examples 14 and 15) that was not subjected to air stirring had lower palladium removability than the electrolytic stripping agent for jigs that was subjected to air stirring. It was found that the palladium removability was improved by stirring.
- the electrolytic stripping agent for jigs of the present invention has very little erosion of the stainless steel wire, and therefore there is little erosion of the energized contact points of the plating jig.
- the copper and nickel peeling rates were about 5 ⁇ m / min and 4 ⁇ m / min, respectively, indicating that the copper and nickel peeling performance was high.
- the electrolytic stripping agent for jigs (Comparative Example 1) containing no ammonia, ammonium salt, ethyleneamine compound, alkyldiamine compound and amino acid has a low palladium removal rate and a low palladium removal property. It was. Similarly, it was found that the electrolytic stripping agent for jigs not containing bromide (Comparative Example 2) also had low palladium removability and low nickel stripping ability.
- Example 16 The perfluorinated sulfonic acid resin cation exchange membrane used in Example 16 and the neutral membrane diaphragm used in Example 17 were fixed using an acrylic fixture to produce a cathode chamber, and the anode The cathode was isolated from the electrolytic stripping agent for jigs in contact. At this time, the cathode chamber was filled with the electrolytic stripping agent for jigs having the same composition as the object to be treated. In Examples 19 to 21, 1 g / L of the oxidizing agent was included in the electrolytic stripper for jig before electrolysis, and 1 g / L was supplied every time electrolysis was performed.
- the amount of palladium adhering to the vinyl chloride plate was measured, and the palladium removal rate was calculated according to the above formula 1.
- the amount of palladium before immersion in the electrolytic stripper was 0.250 mg / dm 2 .
- the above operation was repeated 10 times. At this time, the same vinyl chloride plate was repeatedly used. In addition, the liquid volume of the process liquid used for each process was all 1L, and it washed with water between each process. After the above operation was repeated 10 times, the palladium concentration in the etching solution was analyzed by ICP emission spectroscopy, and the palladium accumulation concentration was measured.
- Electrolytic release agents for jigs of Examples 24 to 30 were prepared according to the formulation shown in Table 20.
- the pH of the jig electrolytic stripper was adjusted using sulfuric acid or a sodium hydroxide aqueous solution.
- a copper sulfate plating film (Top Lucina 2000 bath, Okuno Pharmaceutical Co., Ltd.) applied to a SUS304 flat plate (3 cm ⁇ 3.3 cm, thickness 0.3 mm, surface area 20 cm 2 ), Electrolysis was performed under the conditions shown in FIG. Next, the amount of sludge derived from the insoluble copper compound was visually observed and evaluated.
Abstract
Description
1.下記(A)~(C)成分を含有する治具用電解剥離剤;
(A)硝酸及びその塩から選択される少なくとも一種、
(B)アンモニア、アンモニウム塩、エチレンアミン化合物、アルキルジアミン化合物及びアミノ酸からなる群より選択される少なくとも一種、
(C)臭化物。
2.(D)銅イオンを含有する、項1に記載の治具用電解剥離剤。
3.(E)酸化剤を含有する、項1又は2に記載の治具用電解剥離剤。
4.項1~3のいずれかに記載の治具用電解剥離剤をパラジウムが付着した被処理物と接触させることを特徴とする、パラジウム除去方法。
5.陰極、及び、被処理物である陽極を、治具用電解剥離剤に接触させて電解剥離を行う、項4に記載のパラジウム除去方法。
6.陰極が隔膜によって隔離されている、項5に記載のパラジウム除去方法。
7.治具用電解剥離剤が空気攪拌される、項4~6のいずれかに記載のパラジウム除去方法。
8.項4~7のいずれかに記載のパラジウム除去方法を行うことにより、三酸化クロムを含有する酸性エッチング液中に蓄積するパラジウムの濃度を抑制する方法。
9.項4~7のいずれかに記載のパラジウム除去方法を行うことにより、マンガンを含有する酸性エッチング液中に蓄積するパラジウムの濃度を抑制する方法。
本発明の治具用電解剥離剤は、(A)硝酸及びその塩から選択される少なくとも一種、(B)アンモニア、アンモニウム塩、エチレンアミン化合物、アルキルジアミン化合物及びアミノ酸からなる群より選択される少なくとも一種、及び(C)臭化物を含有する。本発明の治具用電解剥離剤は、上記(A)~(C)成分を含有していれば他の組成については特に限定されないが、通常は、上記(A)~(C)成分が溶解した水溶液として用いられる。
(A)成分は、硝酸及びその塩から選択される少なくとも1種である。硝酸及びその塩としては特に限定されないが、水溶性のものが好ましい。硝酸塩としては、具体的には、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウム、硝酸カルシウム、硝酸鉄、硝酸銀、硝酸鉛、硝酸亜鉛、硝酸バリウム等が挙げられる。中でも、めっき用治具の通電部分であるステンレスが腐食し難く、沈殿の発生が抑制されて安定して使用できる点で、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウム、硝酸カルシウムを用いることが好ましい。
(B)成分は、アンモニア、アンモニウム塩、エチレンアミン化合物、アルキルジアミン化合物及びアミノ酸からなる群より選択される少なくとも一種である。
(C)成分は、臭化物である。臭化物としては特に限定されないが、水溶性のものが好ましい。臭化物としては、具体的には、臭化水素、臭化ナトリウム、臭化カリウム、臭化カルシウム、臭化アンモニウム、臭化銀、臭化鉛、臭化亜鉛、臭化アルミニウム等が挙げられる。中でも、めっき用治具の絶縁材料コーティング部分に付着したパラジウムを十分に除去でき、沈殿の発生が抑制されて安定して使用できる点で、臭化水素、臭化ナトリウム、臭化カリウム、臭化カルシウム、臭化アンモニウムを用いることが好ましい。
本発明の治具用電解剥離剤は、上記(A)~(C)成分以外の他の成分を含有していてもよい。他の成分としては、例えば、(D)銅イオン、(E)酸化剤、(F)錯化剤等が挙げられる。
本発明の治具用電解剥離剤は、パラジウム除去性をさらに向上させるために、(D)銅イオンを含んでいてもよい。銅イオンとしては、特に限定されず、例えば、銅化合物が本発明の電解剥離剤に溶解して形成された銅イオンが挙げられる。銅化合物としては、本発明の電解剥離剤に溶解して銅イオンを付与することができれば特に限定されないが、水溶性のものが好ましい。このような銅化合物としては、例えば、硫酸銅、塩化銅、臭化銅、ヨウ化銅、酢酸銅、硝酸銅、酸化銅等が挙げられる。中でも、めっき用治具の絶縁材料コーティング部分に付着したパラジウムの除去性に優れ、めっき用治具の通電部分であるステンレスが腐食し難い点で、硫酸銅、臭化銅、酢酸銅、硝酸銅、酸化銅を用いることが好ましい。
本発明の治具用電解剥離剤は、パラジウム除去性をさらに向上させるために、(E)酸化剤を含んでいてもよい。酸化剤としては、特に限定されず、例えば、過硫酸塩、ハロゲンオキソ酸、ハロゲンオキソ酸塩、三酸化クロム、クロム酸塩、過マンガン酸塩、過酸化水素等が挙げられる。中でも、めっき用治具の絶縁材料コーティング部分に付着したパラジウムの除去性に優れ、めっき用治具の通電部分であるステンレスが腐食し難い点で、過硫酸塩、ハロゲンオキソ酸、ハロゲンオキソ酸塩が好ましく、過硫酸塩、臭素酸、臭素酸塩がより好ましい。
本発明の治具用電解剥離剤は、(F)錯化剤を含んでいてもよい。治具用電解剥離剤が錯化剤を含有することで、金属水酸化物の沈殿の発生を抑制することができる。錯化剤としては、特に限定されず、例えば、酢酸、クエン酸、マレイン酸、コハク酸、乳酸、リンゴ酸、酒石酸、エチレンジアミン四酢酸等が挙げられる。中でも、排水処理を実施する際に金属凝集剤により金属イオンを容易に除去できる点で、酢酸、マレイン酸、コハク酸、リンゴ酸が好ましい。
本発明の治具用電解剥離剤は、溶媒を含んでいてもよい。本発明の治具用電解剥離剤は、通常溶媒に上記(A)~(C)成分が溶解しており、必要に応じて上記(D)~(F)成分及び他の添加剤が添加されて溶解している。上記溶媒としては、水等を用いることができ、水を用いることがより好ましい。すなわち、本発明の治具用電解剥離剤は、水に上記(A)~(C)成分が溶解しており、必要に応じて上記(D)~(F)成分及び他の添加剤が添加されて溶解している水溶液であることが好ましい。
本発明は、また、上記治具用電解剥離剤をパラジウムが付着した被処理物と接触させるパラジウム除去方法でもある。
表9~11に示す配合により、各成分を混合し、実施例1~15及び比較例1~8の治具用電解剥離剤を調製した。なお、これらの実施例及び比較例では、硫酸又は水酸化ナトリウムを用いてpHを8.0に調整した。
絶縁材料が被覆した治具に相当する試料として、以下の樹脂が被覆したプレートを作製した。
SUS304の平板(5cm×5cm、厚さ 0.3mm、表面積0.5dm2)に市販の軟塩化ビニル系コーティングゾル用ポリマーを塗布し、乾燥させた後、軟塩化ビニル系コーティングゾル(商品名:PG2401(登録商標)、アルファ化成株式会社製)に5秒間浸漬し、180℃で30分間焼き付けることにより、塩化ビニル樹脂被覆プレート(以下、「塩化ビニルプレート」とも示す。)を作製した。
180℃に加熱したSUS304の平板(5cm×5cm、厚さ0.3mm、表面積 0.5dm2)を、平均粒子径1000μmの粉末状ポリエチレン中に1分間浸漬して、180℃で5分間加熱して表面を溶融させて平滑にした。次いで、水中に浸漬して冷却して、ポリエチレン被覆プレート(以下、「ポリエチレンプレート」とも示す。)を作製した。
めっき用治具の絶縁材料コーティング部分に付着したパラジウムの除去性を評価するために、以下の試験を行った。具体的には、塩化ビニルプレートまたはポリエチレンプレートを表1~6に記載した処理工程に従って浸漬法により処理を行い、パラジウムを付着させた。なお、各工程間には、水洗を行った。
めっき用治具の通電部分である、めっき用治具と樹脂成形体との通電接点箇所の侵食性を評価するために、以下の試験を行った。具体的には、SUS304線(φ2mm、長さ5cm)を試験片として用い、表7に記載の条件に従って、実施例1~8及び比較例1~8の治具用電解剥離剤を用いて電解処理を行った。試験片の電解処理前後の質量を測定し、下記式2に従って侵食量を算出した。
めっき用治具の通電箇所に析出した金属皮膜の剥離性能を評価するために、以下の試験を行った。具体的には、SUS304の平板(3cm×3.3cm、厚さ0.3mm、表面積20cm2)に、硫酸銅めっき(トップルチナ2000浴、奥野製薬工業(株)製)、又は光沢ニッケルめっき(改良アクナB浴、奥野製薬工業(株)製)を施して、試験片とした。次いで、表8に記載した条件に従って、実施例1~8及び比較例1~8の治具用電解剥離剤を用いて10分間電解を行った。電解前及び電解後の試験材の質量を測定し、下記式3に従って、銅またはニッケルの剥離速度を算出した。なお、下記式3において、金属密度は、銅については8.94g/cm3、ニッケルについては8.91g/cm3として算出した。
表14に示す配合により、各成分を混合し、治具用電解剥離剤を調製した。当該治具用電解剥離剤のpHは、水酸化ナトリウム水溶液で8.0に調整した。得られた治具用電解剥離剤を用いて、表15に示す条件により、表16に示す隔膜、又は酸化剤を用いて電解を行った。実施例16~18においては、表16に記載した隔膜により、陰極を陽極から隔離した。実施例16で用いた過フッ化スルホン酸樹脂カチオン交換膜、及び、実施例17で用いた中性メンブレン隔膜については、アクリル製の取り付け具を用いて固定して陰極室を作製し、陽極に接する治具用電解剥離剤から、陰極を隔離した。この際、陰極室内は処理対象と同組成の治具用電解剥離剤で満たした。実施例19~21において、酸化剤は電解前に治具用電解剥離剤に1g/L含有させ、電解を1時間行う毎に1g/L補給した。
塩化ビニルプレート10枚を用いて、表18に示すように、表1又は表4の工程で処理を行った。次いで、表14に示す治具用電解剥離剤に、当該塩化ビニルプレートを40℃の温度条件下で、空気攪拌を0.5L/分の流量で行いながら5分間浸漬させた。
表20に示す配合により、実施例24~30の治具用電解剥離剤を調製した。なお、治具用電解剥離剤のpHは、硫酸又は水酸化ナトリウム水様液を用いて調整した。当該電解剥離剤を用いて、SUS304の平板(3cm×3.3cm、厚さ0.3mm、表面積20cm2)に施した硫酸銅めっき皮膜(トップルチナ2000浴、奥野製薬工業(株))を、表19に示す条件で電解し、剥離溶解させた。次いで、不溶性の銅化合物由来のスラッジ量を目視により観察し、評価した。
Claims (9)
- 下記(A)~(C)成分を含有する治具用電解剥離剤;
(A)硝酸及びその塩から選択される少なくとも一種、
(B)アンモニア、アンモニウム塩、エチレンアミン化合物、アルキルジアミン化合物及びアミノ酸からなる群より選択される少なくとも一種、
(C)臭化物。 - (D)銅イオンを含有する、請求項1に記載の治具用電解剥離剤。
- (E)酸化剤を含有する、請求項1又は2に記載の治具用電解剥離剤。
- 請求項1~3のいずれかに記載の治具用電解剥離剤をパラジウムが付着した被処理物と接触させることを特徴とする、パラジウム除去方法。
- 陰極、及び、被処理物である陽極を、治具用電解剥離剤に接触させて電解剥離を行う、請求項4に記載のパラジウム除去方法。
- 陰極が隔膜によって隔離されている、請求項5に記載のパラジウム除去方法。
- 治具用電解剥離剤が空気攪拌される、請求項4~6のいずれかに記載のパラジウム除去方法。
- 請求項4~7のいずれかに記載のパラジウム除去方法を行うことにより、三酸化クロムを含有する酸性エッチング液中に蓄積するパラジウムの濃度を抑制する方法。
- 請求項4~7のいずれかに記載のパラジウム除去方法を行うことにより、マンガンを含有する酸性エッチング液中に蓄積するパラジウムの濃度を抑制する方法。
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EP3168332B2 (en) | 2023-07-26 |
CN106715763A (zh) | 2017-05-24 |
JPWO2016147709A1 (ja) | 2017-04-27 |
US11649558B2 (en) | 2023-05-16 |
JP6142408B2 (ja) | 2017-06-07 |
EP3168332A1 (en) | 2017-05-17 |
EP3168332A4 (en) | 2017-12-27 |
US20170283979A1 (en) | 2017-10-05 |
CN106715763B (zh) | 2019-06-07 |
EP3168332B1 (en) | 2019-03-13 |
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