Classifications

• • 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
• • 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 palladium catalyst liquid.
• Electroless nickel plating is performed on copper circuits in electronics-related fields such as printed wiring boards, semiconductor packages, and electronic components.
• inorganic acids such as hydrochloric acid and sulfuric acid are used as palladium catalyst liquid.
• the palladium catalyst solution using the above-mentioned acid has the problem of corroding copper.
• composition disclosed in Patent Document 1 has a problem in that corrosion of copper is not sufficiently suppressed.
• composition disclosed in Patent Document 1 has the problem that the precipitation of nickel plating is not sufficient in the next step, and the nickel plating tends to spread, resulting in poor patternability.
• the present invention was made in view of the above-mentioned problems, and is capable of suppressing copper corrosion, imparting excellent nickel plating precipitation properties to the copper surface, and improving the nickel plating on copper.
• An object of the present invention is to provide a palladium catalyst liquid that can suppress spreading and provide excellent patterning properties.
• a palladium catalyst solution containing (A) an organic acid, (B) a chloride, and (C) a palladium salt has achieved the above object.
• the present inventors have discovered that the following can be achieved, and have completed the present invention.
• the present invention relates to the following palladium catalyst liquid.
• the palladium catalyst liquid according to Item 1 wherein the organic acid is at least one selected from the group consisting of organic sulfonic acids, organic carboxylic acids, and organic phosphonic acids.
• the palladium catalyst liquid according to Item 1 or 2 wherein the content of the organic acid is 10 to 250 g/L.
• the chloride is at least one selected from the group consisting of sodium chloride, potassium chloride, ammonium chloride, and calcium chloride. 5.
• the palladium salt is at least selected from the group consisting of palladium sulfate, palladium chloride, palladium oxide, palladium iodide, palladium bromide, palladium nitrate, palladium acetate, tetraamminepalladium chloride, dinitrodiammine palladium, and dichlorodiethylenediamine palladium.
• the palladium catalyst liquid of the present invention suppresses corrosion of copper, can provide excellent nickel plating deposition properties on the copper surface, and suppresses the spread of nickel plating on copper to form an excellent pattern. can be given gender.
• the palladium catalyst liquid of the present invention is characterized by containing (A) an organic acid, (B) a chloride, and (C) a palladium salt.
• component (A),""component(B)," and “component (C),” respectively.
• the palladium catalyst liquid of the present invention can suppress corrosion of the copper surface and provide excellent nickel plating deposition properties to the copper surface.
• the palladium catalyst liquid of the present invention can suppress corrosion of the copper surface, suppress the spread of nickel plating on copper, and provide excellent patternability. can.
• the palladium catalyst solution of the present invention improves selective precipitation of palladium on the copper surface by containing component (C). This is thought to be because local corrosion on the copper surface is suppressed. That is, according to the palladium catalyst liquid of the present invention, since it contains the above-mentioned components (A) to (C), corrosion of copper is suppressed and excellent precipitation of nickel plating is imparted to the copper surface. In addition, it is possible to suppress the spread of nickel plating on copper and provide excellent patternability.
• Component (A) is an organic acid.
• the palladium catalyst liquid of the present invention contains the component (A), it is possible to suppress corrosion of the copper surface and provide the copper surface with excellent nickel plating precipitation properties.
• the organic acid is not particularly limited, and includes organic sulfonic acids, organic carboxylic acids, organic phosphonic acids, and the like. Among these, organic sulfonic acids are preferred because they are more effective in suppressing corrosion on the copper surface and further improve the precipitation of nickel plating on the copper surface.
• organic sulfonic acids include aliphatic sulfonic acids having 1 to 5 carbon atoms such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and pentanesulfonic acid; aromatic sulfonic acids such as toluenesulfonic acid, pyridine sulfonic acid, and phenolsulfonic acid. Examples include acids. Among these, methanesulfonic acid is preferred because it is more effective in suppressing corrosion on the copper surface and further improves the precipitation of nickel plating on the copper surface.
• organic carboxylic acids examples include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, and fumaric acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.
• succinic acid is preferred because it is more effective in suppressing corrosion on the copper surface and further improves the precipitation of nickel plating on the copper surface.
• organic phosphonic acids examples include methyldiphosphonic acid, aminotri(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), nitrilotrismethylenephosphonic acid (NTMP), ethylenediaminetetra(methylenephosphonic acid), etc. can be mentioned.
• HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
• NTMP nitrilotrismethylenephosphonic acid
• HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
• HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
• the above organic acids may be used alone or in combination of two or more.
• the concentration of the organic acid in the palladium catalyst liquid is not particularly limited, and is preferably 10 to 250 g/L, more preferably 50 to 200 g/L, and even more preferably 80 to 150 g/L.
• the concentration of the organic acid is, for example, when using 70% methanesulfonic acid, the amount of methanesulfonic acid in the 70% methanesulfonic acid. When used in this case, the concentration of methanesulfonic acid is 105 g/L.
• Component (B) is a chloride.
• the palladium catalyst liquid of the present invention contains the component (B), it is possible to suppress corrosion of the copper surface, suppress spread of nickel plating on copper, and provide better patternability.
• the chloride is not particularly limited, and includes sodium chloride, potassium chloride, ammonium chloride, calcium chloride, and the like.
• sodium chloride is preferable since it can suppress the spread of nickel plating on copper while suppressing corrosion of the copper surface, thereby imparting better patternability.
• the chloride it is preferable to use a chloride other than hydrochloric acid, since corrosion of copper is further suppressed, and it is preferable that the palladium catalyst liquid of the present invention does not contain hydrochloric acid.
• the above chlorides may be used alone or in combination of two or more.
• the concentration of chloride in the palladium catalyst liquid is not particularly limited, and is preferably 3 to 50 g/L, more preferably 5 to 30 g/L, and even more preferably 7 to 20 g/L.
• Component (C) is a palladium salt.
• the palladium catalyst liquid of the present invention contains the component (C), it is possible to suppress corrosion of the copper surface and provide the copper surface with excellent nickel plating precipitation properties.
• Palladium salts are not particularly limited, and include palladium sulfate, palladium chloride, palladium oxide, palladium iodide, palladium bromide, palladium nitrate, palladium acetate, tetraamminepalladium chloride, dinitrodiammine palladium, dichlorodiethylenediamine palladium, and the like.
• palladium sulfate is preferred because it is more effective in suppressing corrosion on the copper surface and further improves the precipitation of nickel plating on the copper surface.
• the above palladium salts may be used alone or in combination of two or more.
• the concentration of the palladium salt in the palladium catalyst liquid is not particularly limited, and is preferably 1 to 100 mg/L, more preferably 20 to 80 mg/L, even more preferably 30 to 70 mg/L, and particularly preferably 40 to 60 mg/L.
• the palladium catalyst liquid of the present invention may contain other components in addition to the above-mentioned components (A), (B), and (C).
• Other components include stabilizers and the like.
• the above-mentioned components (A), (B), and (C), as well as other components included as necessary, are contained in the solvent in the above-mentioned contents. It is preferable. As such a solvent, water is preferable because it has less environmental impact and is excellent in safety.
• the content of the solvent in the palladium catalyst liquid is not particularly limited. It's good to be there.
• the pH of the palladium catalyst liquid of the present invention is not particularly limited, and is preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and particularly preferably 0.5 or less.
• the upper limit of the pH is within the above range, it is possible to impart better precipitation properties of nickel plating to the copper surface, and it is also possible to suppress the spread of nickel plating on copper to impart better patternability. can.
• Method for manufacturing palladium catalyst liquid The method for manufacturing the palladium catalyst liquid of the present invention is not particularly limited, and includes the above components (A), (B), and (C), and other components included as necessary. can be produced by a production method that includes a step of adding it to a solvent.
• the palladium catalyst liquid may be prepared by sequentially adding component (A), component (B), component (C), and other components included as necessary to the solvent.
• the order of addition is not particularly limited.
• the conditions for preparing the palladium catalyst liquid are not particularly limited, and may be stirred and mixed in a mixing tank or the like at 10 to 40°C for about 1 to 10 minutes.
• Palladium catalyst application method The method of applying palladium catalyst to the copper surface using the palladium catalyst liquid of the present invention is not particularly limited, and examples thereof include a palladium catalyst application method that includes a step of immersing a copper plate in the palladium catalyst liquid. .
• the temperature of the palladium catalyst liquid in the above step is not particularly limited, and is preferably 20 to 40°C, more preferably 25 to 35°C.
• the lower limit of the temperature of the palladium catalyst liquid is within the above range, the precipitation of nickel plating on the copper surface is further improved, and the spread of the nickel plating is suppressed, so that better patternability can be exhibited.
• the upper limit of the temperature of the palladium catalyst liquid is within the above range, corrosion of copper is further suppressed.
• the immersion time in the above step is not particularly limited, and is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes.
• the lower limit of the dipping time is within the above range, the precipitation of nickel plating on the copper surface is further improved, and the spread of the nickel plating is suppressed, so that more excellent patternability can be exhibited.
• the upper limit of the immersion time is within the above range, corrosion of copper is further suppressed.
• Example and comparative example The above-mentioned raw materials were added to water as a solvent in the amounts shown in Table 1, and stirred in a mixing tank to produce palladium catalyst liquids of Examples and Comparative Examples.
• Electroless nickel plating solution As an electroless nickel plating solution, ICP Nikolon FPF manufactured by Okuno Pharmaceutical Co., Ltd. was prepared.
• Plating precipitation As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having an over-resist type micro copper pad ( ⁇ 60 to 130 ⁇ m, number of pads 30) on a resin base material was used. Acidic degreasing and soft etching were performed on the material to be electroless plated. Next, catalyst application treatment was performed using the palladium catalyst liquids of Examples and Comparative Examples. Next, using the electroless nickel plating solution prepared as described above, electroless nickel plating was performed at 84° C. for 20 minutes, and evaluation was performed according to the following evaluation criteria. In addition, if it is rated ⁇ , it is evaluated that it can be used without any problems in actual use. ⁇ : No non-precipitation occurred ⁇ : Slight non-precipitation was observed ⁇ : Many non-precipitation occurred
• a BGA resin substrate having an over-resist type copper pad on a resin base material was prepared as a material to be electroless plated. Acidic degreasing and soft etching were performed on the material to be electroless plated. Next, catalyst application treatment was performed using the palladium catalyst liquids of Examples and Comparative Examples. Next, electroless nickel plating was performed using the electroless nickel plating solution prepared as described above at 84° C. for 20 minutes. Regarding the film after nickel plating, a cross-sectional observation of the Cu-Ni interface was performed using an FIB device (10,000 times magnification) to observe the presence or absence of local corrosion on the Cu layer, and the evaluation was performed according to the following evaluation criteria. In addition, if it is rated ⁇ , it is evaluated that it can be used without any problems in actual use. ⁇ : No local corrosion at all ⁇ : Slight local corrosion was observed ⁇ : Many local corrosions occurred

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemically Coating (AREA)
• Catalysts (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88729907

Family Applications (1)

Country Status (4)

Citations (3)

Family Cites Families (3)

• 2023
  • 2023-02-24 CN CN202380039015.6A patent/CN119173651A/zh active Pending
  • 2023-02-24 JP JP2024520264A patent/JPWO2023218728A1/ja active Pending
  • 2023-02-24 WO PCT/JP2023/006627 patent/WO2023218728A1/ja active Application Filing
  • 2023-03-10 TW TW112108981A patent/TW202344713A/zh unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events