WO2013061773A1 - 還元型無電解銀めっき液及び還元型無電解銀めっき方法 - Google Patents

還元型無電解銀めっき液及び還元型無電解銀めっき方法 Download PDF

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WO2013061773A1
WO2013061773A1 PCT/JP2012/076141 JP2012076141W WO2013061773A1 WO 2013061773 A1 WO2013061773 A1 WO 2013061773A1 JP 2012076141 W JP2012076141 W JP 2012076141W WO 2013061773 A1 WO2013061773 A1 WO 2013061773A1
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silver
plating solution
plating
silver plating
electroless silver
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PCT/JP2012/076141
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English (en)
French (fr)
Japanese (ja)
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大督 橋本
晃太 北島
享 岡田
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上村工業株式会社
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Priority to EP12843616.9A priority Critical patent/EP2772566B1/en
Priority to US14/352,145 priority patent/US20140242288A1/en
Publication of WO2013061773A1 publication Critical patent/WO2013061773A1/ja

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    • 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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • 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

Definitions

  • the present invention relates to a reduced electroless silver plating solution and a reduced electroless silver plating method. More specifically, the solution is stable and a good plating film can be formed without excessively roughening a base metal or the like.
  • the present invention relates to a reduced electroless silver plating solution and a reduced electroless silver plating method using the silver plated solution.
  • Silver plating has been used for decorative purposes in the past, and in recent years it has been widely used in the fields of electrical industry, optical industry, other electromagnetic shielding, sterilization coating, etc., taking advantage of its electrical properties and high reflectance. ing. Among them, electroless silver plating is widely used in that the film thickness can be controlled and a plating film having a required film thickness can be easily formed.
  • Electroless silver plating is roughly divided into substitution type and reduction type.
  • Substitutional electroless silver plating is relatively excellent as a plating solution and is widely used in the market (see, for example, Patent Documents 1 and 2).
  • substitutional electroless silver plating has a problem that the base substrate is limited because silver plating is deposited by a substitution reaction with the base metal.
  • reduction type electroless silver plating is a method in which a reducing agent is contained in a plating solution, and a water-soluble silver compound is reduced to metallic silver to deposit silver plating on the underlying metal.
  • a good silver plating film can be formed without roughening the surface and without limiting the type of the base material.
  • the reduced electroless silver plating solution contains a silver cyanide compound such as potassium silver cyanide as a water-soluble silver salt, particularly from the viewpoint of the stability of the solution.
  • a silver cyanide compound such as potassium silver cyanide as a water-soluble silver salt
  • this silver cyanide compound is used as a water-soluble silver salt, generally, cyan of a molar ratio of 2 times or more with respect to silver is contained in the plating solution.
  • Patent Document 3 a method of improving the stability of the solution by adding a cyanide compound such as potassium cyanide has been proposed, and a large amount of free cyanide is present in the plating solution.
  • Patent Document 3 a method of improving the stability of the solution by adding a cyanide compound such as potassium cyanide has been proposed, and a large amount of free cyanide is present in the plating solution.
  • the present invention has been made in view of the above-described conventional situation, and prevents the decomposition of silver in the plating solution to maintain stability, and the metal or the like of the plating base is excessively roughened.
  • a reduced electroless silver plating solution capable of forming a plating film having good film characteristics and good appearance, and a reduced electroless silver plating method using the silver plating solution The purpose is to do.
  • the present inventors maintain the stability of the plating solution by controlling the cyan concentration in the plating solution, and excessively roughen the base metal and the like.
  • the inventors have found that a plating film having good film characteristics and excellent appearance can be formed, and the present invention has been completed.
  • the reduced electroless silver plating solution according to the present invention is a reduced electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and is 0.006 ⁇ 10 ⁇ 3 mol / L to 12 Contains 5 ⁇ 10 ⁇ 3 mol / L of cyanide ion.
  • the water-soluble silver salt is preferably a silver salt other than a cyanide compound, and the cyanide ion is preferably contained as an alkali metal cyanide.
  • the reducing agent is preferably at least one selected from hydroxylammonium sulfate and hydroxylammonium acetate.
  • the pH of the reduced electroless silver plating solution according to the present invention is preferably 8-11.
  • the reducing electroless silver plating method according to the present invention is a reducing electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and is 0.006 ⁇ 10 ⁇ 3 mol / L to 12 Electroless silver plating is applied to the object to be plated using a reduced electroless silver plating solution containing cyanide ions at 5 ⁇ 10 ⁇ 3 mol / L.
  • the decomposition of silver in the plating solution is prevented to improve the stability of the solution, and the plating base and It is possible to prevent an excessively roughened object to be plated such as a metal, and to form a plating film having good film characteristics and excellent appearance.
  • FIG. 1 is a graph showing the relationship between the plating film thickness and the plating time when the reducing agent is changed.
  • this embodiment specific embodiments of the reduced electroless silver plating solution according to the present invention (hereinafter referred to as “this embodiment”) will be described in detail.
  • the reduced electroless silver plating solution according to the present embodiment is a reduced electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and the water-soluble silver salt is reduced to metallic silver by the reducing agent. Then, a silver plating film is formed by depositing silver plating on an object to be plated such as a base metal.
  • the plating solution containing a water-soluble silver salt and a reducing agent contains cyanide ions prepared in a predetermined concentration range. It is said. Specifically, it contains 0.006 ⁇ 10 ⁇ 3 mol / L to 12.5 ⁇ 10 ⁇ 3 mol / L of cyanide ions.
  • cyan-free plating solutions have also been developed in order to avoid excessive dissolution of the base metal, etc., but silver plating solutions with particularly low solution stability can be made free of cyan by using cyan-free plating solutions. The silver was rapidly decomposed and the stability of the plating solution was significantly impaired. Further, with such a cyan-free plating solution, a yellowish plating film is formed, and a plating film having a good appearance cannot be formed. Such a silver plating film having a poor appearance has also caused a decrease in reflectance when used for an LED device, for example.
  • cyanide ions in the plating solution are 0.006 ⁇ 10 ⁇ 3 mol / L to 12.5 ⁇ 10 ⁇ 3 mol / L. It is made to contain.
  • the cyanide ion source is not particularly limited, and for example, alkali metal cyanides such as potassium cyanide and sodium cyanide can be used. Further, a silver cyanide compound such as potassium silver cyanide may be used as a water-soluble silver salt, and this may be contained as part or all of the cyanide ion source so as to have the above-described content.
  • alkali metal cyanide it is particularly preferable to use alkali metal cyanide.
  • the cyanide ion concentration can be appropriately and easily adjusted within the above-mentioned concentration range, and more efficiently and effectively maintaining the stability of the liquid and improving the film properties.
  • a good plating film can be formed.
  • the water-soluble silver salt is not particularly limited as long as it is soluble in the plating solution.
  • silver nitrate, silver oxide, silver sulfate, silver chloride, sulfite Silver, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver sulfonate, silver sulfamate, silver oxalate and the like can be used.
  • a silver cyanide compound such as silver potassium cyanide may be used as the water-soluble silver salt.
  • These water-soluble silver salts can be used alone or in combination of two or more.
  • the content of the water-soluble silver salt is preferably 0.1 g / L to 10 g / L (0.9 ⁇ 10 ⁇ 3 mol / L to 90 ⁇ 10 ⁇ 3 mol / L) as the silver concentration. More preferably, it is set to 1 g / L to 3.0 g / L (0.9 ⁇ 10 ⁇ 3 mol / L to 30 ⁇ 10 ⁇ 3 mol / L).
  • the content of the water-soluble silver salt in the range of 0.1 g / L to 10 g / L as the silver concentration, the deposition rate of silver plating can be improved and a more stable plating solution can be obtained. .
  • the content of the cyanide compound to be added, or the cyanide compound to be added as the silver cyanide compound and the additive is the above-mentioned cyanide ion concentration. It is contained in a range, that is, 0.006 ⁇ 10 ⁇ 3 mol / L to 12.5 ⁇ 10 ⁇ 3 mol / L.
  • the reducing agent is not particularly limited as long as it is capable of reducing a water-soluble silver salt in a plating solution to metallic silver and is a water-soluble compound.
  • hydrazine and its derivatives formaldehyde compounds, hydroxylammonium salts Saccharide, Rossell salt, borohydride compound, hypophosphite, DMAB (dimethylamine borane), ascorbic acid and the like can be used.
  • reducing agents can be used alone or in combination of two or more.
  • hydroxylammonium salts such as hydroxylammonium sulfate and hydroxylammonium acetate.
  • the plating film thickness can be easily changed by controlling the plating time. This is because a plating film having characteristics can be easily formed.
  • cyanide ions are controlled within a predetermined concentration range in order to prevent excessive dissolution of the base metal and the like. is doing. Therefore, when a reducing agent such as DMAB having a stronger reducing power is used, silver in the plating solution may be decomposed. In that respect, by using a hydroxylammonium salt such as hydroxylammonium sulfate or hydroxylammonium acetate, it is possible to prevent decomposition of silver in the plating solution and to cause a reduction reaction stably.
  • the base metal or the like can be coated with a silver plating having a desired film thickness, and a plating film having good film characteristics can be formed.
  • a plating film having a desired film thickness can be easily formed, and the stability of the liquid is further improved. In this way, it is possible to form a plating film with good film characteristics more effectively.
  • the content of the reducing agent is preferably 0.006 mol / L to 0.12 mol / L, and more preferably 0.006 mol / L to 0.03 mol / L.
  • the content of the reducing agent is less than 0.006 mol / L, there is a possibility that the water-soluble silver salt in the plating solution cannot be reduced to metallic silver and sufficient silver plating cannot be deposited.
  • it is more than 0.12 mol / L, it may adversely affect the stability of the plating solution and is not preferable economically.
  • the reduced electroless silver plating solution according to the present embodiment can be used in a temperature range of 0 to 80 ° C., and in particular, by using it at about 30 to 60 ° C., the stability of the plating solution is further improved. Can be improved. If the temperature of the plating solution is too low, the silver deposition rate is slow and a long time is required to obtain a predetermined amount of silver deposition. On the other hand, if the temperature of the plating solution is too high, loss of the reducing agent due to the autolysis reaction and deterioration of the plating solution stability are likely to occur.
  • the pH of the reduced electroless silver plating solution can be used in the range of 2 to 14, but since the cyanide ion at a predetermined concentration is contained as described above, the pH is particularly set to 8 to 11. It is preferable to set it as the range.
  • the pH of the plating solution By setting the pH of the plating solution to 8 or more, generation of cyan gas can be effectively suppressed, and the plating solution can be used safely without adversely affecting the environment.
  • the stability of the plating solution can be further improved. Further, by adjusting the pH to 11 or less, the stability of the plating solution and the film characteristics of the plating film can be further improved.
  • the pH of the plating solution is usually adjusted by lowering the pH by using an acid having an anion portion of the same kind as the water-soluble silver salt, for example, sulfuric acid or water-soluble silver when silver sulfate is used as the water-soluble silver salt.
  • an acid having an anion portion of the same kind as the water-soluble silver salt for example, sulfuric acid or water-soluble silver when silver sulfate is used as the water-soluble silver salt.
  • silver nitrate is used as the salt
  • nitric acid is used.
  • alkali metal hydroxide such as sodium hydroxide, ammonia or the like is used.
  • a complexing agent can be added as necessary.
  • a sulfite, a succinimide, a hydantoin derivative, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), etc. can be used. These complexing agents can be used alone or in combination of two or more.
  • the amount of complexing agent to be added varies depending on the type and is not particularly limited, but is preferably about 1 g / L to 100 g / L. By setting the concentration of the complexing agent in such a range, the deposition rate of silver plating can be improved, and a plating solution having further excellent stability can be obtained.
  • additives such as a known surfactant, pH adjuster, buffer, smoothing agent, stress relieving agent may be mixed as necessary.
  • the object to be plated is immersed in the reduced electroless silver plating solution adjusted to the above-described solution temperature and pH value. Apply silver plating.
  • a plating treatment may be performed by bringing the plating solution into contact with the object to be plated by spraying or applying a reduced electroless silver plating solution to the object to be plated.
  • this electroless silver plating method mainly reduces a water-soluble silver salt to metallic silver by a reducing agent contained in a plating solution, and then performs silver plating on a metal or other object to be plated.
  • a plating film is formed by precipitating.
  • the object to be plated for forming the electroless silver plating film is not particularly limited, and is applied to metal materials such as copper and nickel, various other conductive materials, and non-conductive materials. Can do.
  • metal materials such as copper and nickel, various other conductive materials, and non-conductive materials. Can do.
  • the plated object is directly immersed in a plating solution.
  • the object to be plated is activated and then immersed in a plating solution.
  • the activation treatment may be carried out in accordance with a conventional method, for example, using a palladium catalyst (catalyst-accelerator method, sensitizing-activator method, etc.), a silver catalyst, a copper catalyst, or the like according to known conditions. Do.
  • the reduced electroless silver plating solution according to the present embodiment is a reduced electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and is 0.006 ⁇ 10 ⁇ 3. Contains cyanide ions in mol / L to 12.5 ⁇ 10 ⁇ 3 mol / L. According to such a reduced electroless silver plating solution, it is possible to effectively prevent the decomposition of silver in the silver plating solution and to improve the stability of the solution, and to coat a metal such as a base metal. It is possible to prevent an object from being excessively roughened and to form a plating film having good film characteristics and excellent appearance.
  • Example 1 Silver nitrate is 9.0 ⁇ 10 ⁇ 3 mol / L (1.0 g / L) as the silver concentration, hydroxylammonium salt (hydroxylammonium sulfate) 1.24 ⁇ 10 ⁇ 3 mol / L as the reducing agent, and EDTA0 as the complexing agent.
  • the reduced electroless silver plating solution was adjusted to pH 9.0.
  • Example 2 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that 300 mg / L of potassium cyanide was added to adjust the cyanide ion concentration in the plating solution to 1.8 ⁇ 10 ⁇ 3 mol / L. .
  • Example 3 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that 500 mg / L of potassium cyanide was added to adjust the cyanide ion concentration in the plating solution to 3.0 ⁇ 10 ⁇ 3 mol / L. .
  • Example 4 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that 1000 mg / L of potassium cyanide was added to adjust the cyanide ion concentration in the plating solution to 6.5 ⁇ 10 ⁇ 3 mol / L. .
  • Example 5 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that 2000 mg / L of potassium cyanide was added to adjust the cyanide ion concentration in the plating solution to 12.5 ⁇ 10 ⁇ 3 mol / L. .
  • Example 3 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide was not added. That is, a cyan-free reduced electroless silver plating solution was prepared.
  • Example 4 A reduced electroless silver plating solution was prepared in the same manner as in Example 1 except that 2100 mg / L of potassium cyanide was added to adjust the cyanide ion concentration in the plating solution to 13.0 ⁇ 10 ⁇ 3 mol / L. did.
  • reduced electroless silver plating was performed using a BGA substrate (manufactured by Uemura Kogyo Co., Ltd.) as an object to be plated.
  • the steps shown in Table 1 below were sequentially performed as a pretreatment. That is, the BGA substrate, which is the object to be plated, was subjected to a cleaner treatment (degreasing) with ACL-738 (manufactured by Uemura Kogyo Co., Ltd.) and then subjected to a soft etching treatment with a 100 g / L sodium persulfate solution (SPS). .
  • a cleaner treatment degreasing
  • ACL-738 manufactured by Uemura Kogyo Co., Ltd.
  • SPS sodium persulfate solution
  • etching residue was removed with a 10% sulfuric acid (H 2 SO 4 ) solution (pickling), pre-dip treatment with a 3% sulfuric acid solution, and a Pd catalyst was applied with MNK-4 (manufactured by Uemura Kogyo Co., Ltd. (Catalist). Thereafter, a base metal film was formed using an electroless nickel solution NPR-4 (manufactured by Uemura Kogyo Co., Ltd.) and an electroless palladium solution TPD-30 (manufactured by Uemura Kogyo Co., Ltd.).
  • the electroless silver plating treatment was performed by immersing the object to be plated in the above-described reduced electroless silver plating solution at 60 ° C. for 20 minutes. Then, after the plating treatment, the temperature was allowed to stand for 100 hours at 60 ° C., and the stability of the plating solution, and the solder joint strength and appearance of the plating film were evaluated by the presence or absence of self-decomposition of the plating solution. The evaluation results are shown in Table 2 below.
  • the solder joint strength of the plating film is evaluated by reflow treatment at 240 ° C. once.
  • the joint strength is good (O), and when it is less than 16 Was evaluated as poor bonding strength (x). Further, the appearance of the plating film was visually confirmed when the film thickness of the silver plating film was 0.5 ⁇ m.
  • Examples 1 to 5 As shown in Table 2, reduction in Examples 1 to 5 in which the cyanide ion concentration in the plating solution was controlled in the range of 0.006 ⁇ 10 ⁇ 3 mol / L to 12.5 ⁇ 10 ⁇ 3 mol / L.
  • the type electroless silver plating solution showed good solution stability without decomposition of silver in the plating solution.
  • Example 6 Reduction with a cyanide ion concentration of 0.006 ⁇ 10 ⁇ 3 mol / L in the same manner as in Example 2 except that hydrazine (hydrazine sulfate) 1.24 ⁇ 10 ⁇ 3 mol / L was added as a reducing agent. A type electroless silver plating solution was prepared.
  • Example 7 Reduced electroless silver having a cyanide ion concentration of 0.006 ⁇ 10 ⁇ 3 mol / L in the same manner as in Example 2 except that 1.24 ⁇ 10 ⁇ 3 mol / L of formaldehyde was added as a reducing agent. A plating solution was prepared.
  • Example 2 Using the reduced electroless silver plating solution prepared in Example 2 and Examples 6 and 7, the relationship between the film thickness of the silver plating film and the plating time was examined.
  • FIG. 1 the graph about the measurement result of the film thickness with respect to the plating time when a reducing agent is changed is shown.
  • the film thickness of the silver plating film obtained by extending the plating time also increases substantially linearly. It can be seen that the film is formed by the silver deposition due to the reduction reaction.
  • Examples 6 and 7 using hydrazine or formaldehyde as a reducing agent it can be seen that after a predetermined time has elapsed, the film thickness is not so thick. This is presumably because hydrazine and formaldehyde cause silver to be precipitated by the reduction reaction, but the factors due to the substitution reaction also work greatly, so that the base metal is slightly dissolved.
  • hydroxylammonium sulfate is used as a reducing agent.
  • hydroxylammonium salts such as hydroxylammonium acetate, the reduction reaction can proceed more effectively, and a plating film with good film properties can be formed without causing dissolution of the underlying metal by the substitution reaction. I understood that I could do it.

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PCT/JP2012/076141 2011-10-27 2012-10-09 還元型無電解銀めっき液及び還元型無電解銀めっき方法 WO2013061773A1 (ja)

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EP12843616.9A EP2772566B1 (en) 2011-10-27 2012-10-09 Plating bath for the electroless deposition of silver and corresponding method
US14/352,145 US20140242288A1 (en) 2011-10-27 2012-10-09 Reducing electroless silver plating solution and reducing electroless silver plating method

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