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
  • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
  • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
  • C23C18/1837—Multistep pretreatment
  • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • 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 is to prevent deposition of electroless metal plating on a resin surface that does not require plating when performing electroless metal plating on a copper circuit pattern on the printed wiring board during printed wiring board manufacture.
• the present invention relates to a bridging prevention liquid and a method for producing a printed wiring board using the same.
• a metal deposition catalyst such as a palladium catalyst is attached to the entire surface of the resin substrate, electroless copper plating is applied, and further, electrolytic copper plating is used for 10 to 10
• a method of forming a circuit by forming a 20 ⁇ m copper layer and then etching an unnecessary copper film using a resist is used.
• electroless nickel plating is usually applied as a base plating on a copper layer on a terminal portion or a component mounting portion, and gold plating is often performed thereon.
• Patent Documents 1 and 2 A method (Patent Documents 1 and 2) is known in which electroless nickel plating is performed after this.
• An object of the present invention is to provide a technique for preventing a bridge in which electroless metal plating performed after forming a circuit pattern is deposited on a resin of a wiring board.
• the present inventors have made an electroless metal plating after the circuit pattern is formed by allowing a bridge prevention liquid containing a polythiol compound to act on the resin of the wiring board. We found that bridging by can be prevented. In addition, by using a combination of the above bridging prevention solution and the metal deposition catalyst removal solution, it is possible to suppress copper wiring corrosiveness and remove the catalyst adhering to the resin between the wirings, and between higher density wirings. Even so, the present inventors have found that bridging can be prevented and completed the present invention.
• the present invention is the following (1) to (6).
• a method for preventing bridging of a printed wiring board comprising: applying an anti-bridging solution for metal plating and further performing electroless metal plating on the circuit.
• the above-described electroless metal plating bridging prevention liquid is allowed to act on the resin of the wiring board between the etching and the electroless metal plating step.
• a method for manufacturing a wiring board. (4) After providing a metal deposition catalyst on the resin of the wiring board, electroless copper plating is performed, then electrolytic copper plating is performed, and then an unnecessary copper film is etched to form a circuit pattern on the circuit. In the method for manufacturing a printed wiring board for performing electroless metal plating, after removing the metal deposition catalyst on the resin of the wiring board between the etching and the electroless metal plating step, the electroless metal plating is further performed.
• a method for producing a printed wiring board characterized in that an anti-bridging solution is applied.
• a metal deposition catalyst removing solution containing a thiourea compound (6) A method for removing a metal deposition catalyst attached to a resin, wherein the metal deposition catalyst removal solution is allowed to act on the resin to which the metal deposition catalyst is adhered.
• the bridge preventing liquid for electroless metal plating of the present invention can prevent deposition on the resin of the wiring board when electroless metal plating is performed after the circuit pattern is formed.
• the catalyst removal liquid in combination with the bridge prevention liquid of the electroless metal plating of the present invention, no bridging occurs and the copper wiring corrosiveness is suppressed, and The catalyst adhered on the resin between the wirings can be removed, and a printed wiring board having no catalyst residue and high insulation reliability can be manufactured.
• the bridge preventing solution for electroless metal plating of the present invention contains a polythiol compound.
• the polythiol compound used in the present invention prevention liquid is not particularly limited as long as it is a compound containing two or more thiol groups, and examples thereof include dithiol compounds, trithiol compounds, and tetrathiol compounds.
• dithiol compound 1,2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,8-octanedithiol 2,3-dimercapto-1-propanol, dithioerythritol, 3,6-dioxa-1,8-octanedithiol, bis (3-mercaptobutanoic acid) tetramethylene, ethylenebis (dithiocarbamic acid), and the like.
• Examples of the compound include trimethylolpropane tris (3-mercaptopropionate), and examples of the tetrathiol compound include pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and the like. Is mentioned.
• dithiol compounds are preferred, and 3,6-dioxa-1,8-octanedithiol, 1,8-octanedithiol, 2,3-butanedithiol, 1,4-butanedithiol, 1,2- Propanedithiol, 1,3-propanedithiol, and 1,2-ethanedithiol are preferred.
• These polythiol compounds can be used alone or in combination of two or more.
• the content of the polythiol compound in the prevention liquid of the present invention is not particularly limited, and is, for example, 0.1 to 100 g / L, preferably 0.2 to 50 g / L.
• the anti-inhibition liquid of the present invention has no particular problem whether it is aqueous or non-aqueous, but is preferably aqueous.
• the prevention liquid of the present invention is aqueous, it is preferable to add an organic solvent in order to improve the solubility of the polythiol compound in water.
• the organic solvent include alcohol, ether, ketone, ester and the like.
• examples of alcohol include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, and examples of ether include tetrahydrofuran, 1,4-dioxane, and the like.
• acetone and the like includes methyl acetate and ethyl acetate.
• examples of the ester include methyl acetate and ethyl acetate.
• alcohol is preferable, and ethanol and 2-propanol are more preferable.
• these organic solvents can use 1 type (s) or 2 or more types.
• the content of the organic solvent in the prevention liquid of the present invention is not particularly limited, but is, for example, 1 to 800 g / L, preferably 2 to 500 g / L.
• preventive liquid for example, an alkali such as sodium hydroxide or potassium hydroxide is used for further improving the solubility of the polythiol compound or for improving the precipitation preventing effect by improving the permeability.
• Nonionic surfactants such as salts, polyoxyethylene alkyl ethers, anionic surfactants such as alkylbenzene sulfonates, cationic surfactants such as quaternary ammonium salts, and amphoteric surfactants such as alkylbetaines You may add in the grade which does not impair the effect of a prevention liquid.
• Prevention liquid of the present invention (Composition 1) 1,2-ethanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L Ethanol: 1 to 800 g / L, preferably 2 to 500 g / L (Composition 2) 1,8-octanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L 2-propanol: 1 to 800 g / L, preferably 2 to 500 g / L (Composition 3) 3,6-dioxa-1,8-octanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L 2-propanol: 1 to 800 g / L, preferably 2 to 500 g / L (Composition 1) 1,2-ethanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L Ethanol: 1 to 800 g / L, preferably 2
• the removal liquid of a metal deposition catalyst in this invention prevention liquid it is preferable to contain the removal liquid of a metal deposition catalyst in this invention prevention liquid. As a result, it is possible to simultaneously perform bridge prevention and removal of a catalyst such as palladium used for electroless copper plating or the like on the wiring board.
• a conventionally known metal deposition catalyst removal solution can be used, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, borofluoric acid, hydrofluoric acid, sulfamic acid, Methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, isethionic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, glycolic acid, gluconic acid, malic acid, citric acid, tartaric acid and other organic acids, etc.
• an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, borofluoric acid, hydrofluoric acid,
• examples of the metal deposition catalyst removal liquid include those containing a thiourea compound newly found by the present inventors.
• examples of the thiourea compound include thiourea, N-methylthiourea, 1,3-dimethylthiourea, trimethylthiourea, tetramethylthiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, 1,1,3.
• thioacetamide 4-methylthiosemicarbazide, 1-allyl-2-thiourea, 1-acetyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, 1, 3-bis (dimethylaminopropyl) -2-thiourea, 1-phenyl-2-thiourea, 1,3-diphenylthiourea, 1-acetyl-2-thiourea, N-benzoylthiourea, guanylthiourea, 2 , 5-dithiobithiourea and the like.
• These thiourea compounds can be used alone or in combination of two or more. With this metal deposition catalyst removal solution containing a thiourea compound, the copper wiring corrosivity can be suppressed more than the conventional metal deposition catalyst removal solution, and the catalyst adhering to the resin between the wirings can be removed. .
• 1 to 140 g / L, preferably 10 to 100 g / L of the thiourea compound is contained in the removal solution of the metal deposition catalyst containing the thiourea compound.
• the removal liquid of the metal deposition catalyst containing the thiourea compound contains one or more selected from inorganic acids and organic acids, and the pH of the liquid is made acidic.
• the inorganic acid and organic acid used in the metal deposition catalyst removal solution are the same as those described above.
• the removal solution of the metal deposition catalyst containing a thiourea compound includes a nonionic surfactant such as polyoxyethylene alkyl ether, alkylbenzene sulfonic acid, etc. for improving the effect of removing the metal deposition catalyst by improving the permeability.
• a nonionic surfactant such as polyoxyethylene alkyl ether, alkylbenzene sulfonic acid, etc.
• An anionic surfactant such as a salt, a cationic surfactant such as a quaternary ammonium salt, an amphoteric surfactant such as an alkylbetaine, and the like can be contained.
• composition 1 Thiourea: 1 to 140 g / L, preferably 10 to 100 g / L Sulfuric acid: 5 to 700 g / L, preferably 10 to 600 g / L
• Composition 2 N-methylthiourea: 1 to 100 g / L, preferably 10 to 70 g / L Methanesulfonic acid: 5 to 700 g / L, preferably 10 to 600 g / L
• Composition 3 Thiourea: 1 to 140 g / L, preferably 10 to 100 g / L Sulfuric acid: 5 to 700 g / L, preferably 10 to 600 g / L
• Malic acid 5 to 400 g / L, preferably 10 to 300 g / L
• those containing one or more selected from thiourea compounds, inorganic acids and organic acids are preferred, and those containing thiourea compounds are particularly preferred.
• the content of the metal deposition catalyst removal liquid in the prevention liquid of the present invention is not particularly limited as long as the metal deposition catalyst removal liquid is at a concentration that exerts the metal deposition catalyst removal action.
• thiourea compounds, inorganic acids And organic acids respectively, 1 to 140 g / L, preferably 10 to 100 g / L, 5 to 700 g / L, preferably 10 to 600 g / L, 5 to 400 g / L, preferably 10 to 300 g / L. It is.
• composition 1 1,2-ethanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L Ethanol: 1 to 800 g / L, preferably 2 to 500 g / L Thiourea: 1 to 140 g / L, preferably 10 to 100 g / L Sulfuric acid: 5 to 700 g / L, preferably 10 to 600 g / L
• Composition 2 1,8-octanedithiol: 0.1 to 100 g / L, preferably 0.2 to 50 g / L 2-propanol: 1 to 800 g / L, preferably 2 to 500 g / L N-methylthiourea: 1 to 100 g / L, preferably 10 to 70 g / L Methanesulfonic acid
• this invention prevention liquid is obtained by adding at least a polythiol compound to an aqueous or non-aqueous solution, and stirring and mixing.
• a polythiol compound, an organic solvent or the like may be added to water, and the mixture may be stirred and mixed.
• these preventive liquids of the present invention can be used in a known printed wiring board manufacturing method. Specifically, after applying a metal deposition catalyst on the resin of the wiring board, electroless copper plating is performed, then electrolytic copper plating is performed, and then an unnecessary copper film is etched to form a circuit pattern.
• the present invention preventive liquid may be allowed to act on the resin of the wiring board between the etching and the electroless metal plating step. In addition, you may perform water washing, drying, etc. suitably between each process.
• the method of causing the present invention preventing liquid to act on the resin of the wiring board is not particularly limited, and the wiring board itself is immersed in the present preventing liquid or on the resin of the wiring board. What is necessary is just to inject this invention prevention liquid by a spray.
• the use conditions of the present prevention liquid are preferably 10 to 55 ° C., preferably 30 to 55 ° C., for 10 seconds to 5 minutes, preferably 1 to 5 minutes for both immersion and spraying. .
• the metal deposition catalyst removal liquid added to the present invention prevention liquid is not added to the present invention prevention liquid, but separately acts as a metal deposition catalyst removal liquid. Further, the preventive liquid of the present invention may be allowed to act. By doing so, it is possible to prevent bridging with respect to a wiring pattern having a higher density than when it is contained in the prevention liquid of the present invention.
• the method for allowing the metal deposition catalyst removal liquid to act on the wiring board resin is not particularly limited, and the wiring board itself is immersed in the metal deposition catalyst removal liquid, or the metal deposition catalyst removal is performed on the wiring board resin.
• the liquid may be sprayed or the like.
• the conditions for using the metal deposition catalyst removal solution are 10 to 55 ° C., preferably 30 to 55 ° C., for 10 seconds to 5 minutes, preferably 1 to 5 minutes for both immersion and spraying. Is preferred.
• Example 1 Preparation of anti-bridging solution: An aqueous solution containing 2 g / L of 1,2-ethanedithiol and 100 g / L of ethanol was prepared and used as an anti-bridging solution.
• Example 2 Preparation of anti-bridging solution: An aqueous solution containing 2 g / L of 1,8-octanedithiol and 100 g / L of ethanol was prepared and used as an anti-bridging solution.
• Example 3 Preparation of anti-bridging solution: An aqueous solution containing 2 g / L of 3,6-dioxa-1,8-octanedithiol and 100 g / L of ethanol was prepared and used as an anti-bridging solution.
• Example 4 Preparation of anti-bridging solution: An aqueous solution containing 2 g / L of trimethylolpropane tris (3-mercaptopropionate) and 100 g / L of ethanol was prepared and used as an anti-bridging solution.
• Test example 1 Bridge prevention test: Using the anti-bridging solutions prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the copper wiring corrosivity, catalyst removability, and anti-bridging properties were evaluated by the following methods. These results are shown in Table 1. In the following method, the bridging prevention liquid is heated to 50 ° C., and the treatment (immersion) time is 1 minute.
• ⁇ Catalyst removability> An electroless copper plating of about 0.3 ⁇ m is formed on a 5 ⁇ 10 cm epoxy resin substrate by the following steps, and then immersed in an aqueous solution of 7% sulfuric acid and 2% hydrogen peroxide. The plating film was peeled off to prepare a state in which the catalyst remained on the epoxy resin base material, and this was used as a test piece. After the test piece was treated with each bridging prevention solution, the residual palladium amount was measured, and the difference in the residual palladium amount from the untreated test piece was calculated and evaluated as a palladium removal rate.
• the palladium residual amount was measured by immersing the test piece in about 50 mL of aqua regia prepared by mixing 37% by mass hydrochloric acid and 68% by mass nitric acid at a volume ratio of 3: 1 for 5 minutes. Next, the test piece was washed with ion-exchanged water, and the washing water was also sampled into a 100 mL volumetric flask. Finally, the palladium concentration in the aqueous solution accurately measured up to 100 mL was measured by an atomic absorption spectrometer (AA240FS). Analysis by Varian).
• ⁇ Electroless nickel plating process > Acid degreasing (PB-242D), 45 ° C, 5 minutes ⁇ Washing with water ⁇ Soft etch (SC-300), 30 ° C, 1 minute ⁇ Washing with water ⁇ Catalyst application (PB-305), 30 ° C, 3 minutes ⁇ Washing with water ⁇ Electroless nickel plating (PB-606), 80 ° C, 20 minutes (All chemicals other than sulfuric acid are manufactured by JCU)
• Example 5 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding thiourea 60 g / L and methanesulfonic acid 200 g / L to the anti-bridging solution of Example 1.
• Example 6 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding 70 g / L of N-methylthiourea and 600 g / L of methanesulfonic acid to the anti-bridging solution of Example 2.
• Example 7 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding 70 g / L of N-methylthiourea and 600 g / L of methanesulfonic acid to the anti-bridging solution of Example 3.
• Example 8 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding 60 g / L of thiourea and 400 g / L of methanesulfonic acid to the anti-bridging solution of Example 4.
• Comparative Example 4 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding 60 g / L of thiourea and 200 g / L of methanesulfonic acid to the anti-bridging solution of Comparative Example 1.
• Comparative Example 5 Preparation of anti-bridging solution: An anti-bridging solution was prepared by further adding 60 g / L of thiourea and 200 g / L of methanesulfonic acid to the anti-bridging solution of Comparative Example 2.
• Test example 2 Bridge prevention test: Using the anti-bridging solutions prepared in Examples 5 to 8 and Comparative Examples 3 to 5, the copper wiring corrosivity, catalyst removability, and anti-bridging properties were evaluated in the same manner as in Test Example 1. These results are shown in Table 2.
• Example 9 Preparation of metal deposition catalyst removal solution: An aqueous solution containing 300 g / L hydrochloric acid and 30 g / L nitric acid was prepared, and this was used as a removal solution for the metal deposition catalyst.
• Example 10 Preparation of metal deposition catalyst removal solution: An aqueous solution containing thiourea 60 g / L and methanesulfonic acid 200 g / L was prepared, and this was used as a metal deposition catalyst removal solution.
• Example 11 Preparation of metal deposition catalyst removal solution: An aqueous solution containing 70 g / L of N-methylthiourea and 600 g / L of methanesulfonic acid was prepared, and this was used as a metal deposition catalyst removal solution.
• Test example 3 Bridge prevention test: In the same manner as in Test Example 1 using the anti-bridging solution prepared in Examples 1 to 3 and Comparative Example 6 and the metal deposition catalyst removing solution prepared in Examples 9 to 11, the copper wiring corrosiveness, catalyst removability and The bridge prevention property was evaluated. In addition, the process using the removal liquid of a metal deposition catalyst was performed before the process using a bridge
• the bridge preventing liquid for electroless metal plating of the present invention can be used for the production of printed wiring boards. more than

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Metallurgy (AREA)
• Inorganic Chemistry (AREA)
• Manufacturing Of Printed Wiring (AREA)
• Chemically Coating (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=52104391

Family Applications (1)

Country Status (5)

Cited By (4)

Citations (3)

Family Cites Families (7)

• 2014
  • 2014-05-12 WO PCT/JP2014/062551 patent/WO2014203649A1/ja active Application Filing
  • 2014-05-12 JP JP2015522655A patent/JP6290206B2/ja active Active
  • 2014-05-12 KR KR1020157034594A patent/KR20160021107A/ko not_active Application Discontinuation
  • 2014-05-12 CN CN201480032250.1A patent/CN105264114A/zh active Pending
  • 2014-05-29 TW TW103118810A patent/TWI586831B/zh active

Patent Citations (3)

Also Published As

Similar Documents

Legal Events