WO2002036273A1 - Catalyst solutions useful in activating substrates for subsequent plating - Google Patents

Catalyst solutions useful in activating substrates for subsequent plating Download PDF

Info

Publication number
WO2002036273A1
WO2002036273A1 PCT/US2001/030655 US0130655W WO0236273A1 WO 2002036273 A1 WO2002036273 A1 WO 2002036273A1 US 0130655 W US0130655 W US 0130655W WO 0236273 A1 WO0236273 A1 WO 0236273A1
Authority
WO
WIPO (PCT)
Prior art keywords
gold
sulfonic acid
tin
organic sulfonic
composition according
Prior art date
Application number
PCT/US2001/030655
Other languages
French (fr)
Other versions
WO2002036273A8 (en
Inventor
Ronald Redline
Mark Wojtaszek
Original Assignee
Macdermid, Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Macdermid, Incorporated filed Critical Macdermid, Incorporated
Priority to AU2001294928A priority Critical patent/AU2001294928A1/en
Publication of WO2002036273A1 publication Critical patent/WO2002036273A1/en
Publication of WO2002036273A8 publication Critical patent/WO2002036273A8/en

Links

Classifications

    • B01J35/23—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating

Definitions

  • the present invention relates to improved catalyst solutions useful in preparing substrates for plating thereupon.
  • Metallization processes for non-conductive substrates using noble metal baths primarily baths containing palladium, as activators are well known. These processes are particularly useful in applying functional and decorative metal coatings to non-conductive substrates such as glass and various plastics, and are particularly useful in metallizing printed circuit boards.
  • Rhodenizer discloses a composition for activating a substrate for electroless metallization comprising: a noble metal that is catalytic to a chemical reduction plating process, salts capable of forming a protective metal sol, and at least one organic acid, which is substantially soluble in the plating bath, selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, amino acids and combinations of these.
  • a. source of gold a. source of gold
  • b. source of tin a. source of gold
  • tin a. source of tin
  • colloidal activator solutions of the foregoing ingredients prepared as noted herein, provide significant advantages in terms of colloidal stability, catalytic activity and other performance factors.
  • an improved colloidal activator solution comprising
  • a. source of gold a. source of gold
  • b. source of tin a. source of gold
  • c. an acid which is preferably an organic sulfonic acid a. source of gold
  • c. an acid which is preferably an organic sulfonic acid a. source of gold
  • c. an acid which is preferably an organic sulfonic acid a. source of gold
  • d. optionally, a colloid stabilizer a. source of gold
  • the source of gold may be any source that would supply gold containing ions to the activator solution.
  • Halogenated gold salts or acids are preferred. Examples of the most preferred gold sources are gold trichloride and tetrachloroauric acid. It is preferred for the concentration of gold (measured by gold content) in the activator colloid to range from about 0.01 to 15 g./l.
  • the source of tin is preferably a source of stannous tin.
  • stannous tin sources are stannous chloride, stannous sulfate, or stannous methanesulfonic acid (stannous methane sulfonate), with stannous methansulfonic acid being the most preferred.
  • concentration of tin (measured as tin content) in the activator colloid is preferred to range from about 45 to 200 g/1.
  • the activator colloid should contain an acid, which is preferably an organic sulfonic acid, most preferably methane sulfonic acid. Other acids such as hydrochloric acid, or sulfuric acid may be present as well.
  • the concentration of the acid in the activator colloid preferably ranges from about 1 to 5 moles per liter.
  • the inventors have found that the use of organic sulfonic acids in the activator colloid are greatly preferred and produce a colloid with improved stability and catalytic activity. It is most preferred to use the organic sulfonic acid corresponding to the anion provided by the source of tin (i.e. tin methane sulfonate and methane sulfonic acid).
  • the activator colloid may also contain colloid stabilizers.
  • Preferred colloid stabilizers include gum arabic, guar gum, xanthan gum and/or gelatin. If used, the concentration of the colloid stabilizer in the activator colloid may preferably range from 0.01% to 0.1% by weight.
  • the method of preparing the concentrated colloid is critical to the stability of the colloid formed and its catalytic activity.
  • a gold containing solution should be prepared by mixing the gold source with the chosen organic sulfonic acid.
  • a portion of the acid to be used in preparing the colloid should be mixed with the gold source in this first step.
  • a separate solution of the tin source, the other portion of the acid to be used in preparing the colloid, water and any other necessary ingredients is prepared.
  • the gold containing solution is then added to the tin containing solution, slowly, with stirring, over a period of from 10 to 60 seconds.
  • the reaction mixture is then stirred at room temperature for 2 hours.
  • reaction mixture may be rapidly heated, with stirring, to about 95° C and when that temperature is reached, allowed to cool naturally with stirring.
  • a third alternative is to heat the tin containing solution to about 95° and then add the gold containing solution to the tin containing solution over a period of from 10 to 60 seconds with stirring and allow the reaction mixture to cool naturally with stirring. Heating if used should be to between about 70° C and about 95° C but is preferably to about 95° C.
  • the activator working bath is prepared by mixing from about 1 to 25% by volume of the concentrated activator colloid with water or an aqueous solution of sodium chloride, potassium chloride, acids, or mixtures of the foregoing.
  • the working colloid should contain from about 0.05 to 2 g/1 of gold.
  • colloidal activator is useful in preparing substrates, particularly non- conductive substrates, for plating, usually by electroless or chemical reduction plating.
  • Typical electroless plating processes that may utilize this colloidal activator in plating upon plastics may include the following steps:
  • a plastic etchant which will etch the plastic surface such as chromic acid or potassium permanganate solutions.
  • a neutralizer to neutralize the plastic etchant residues such as hydroxylamine solutions.
  • a conditioner which cleans the surface of the plastic and conditions it to receive activator species.
  • the working bath activator colloid e. an acidic or alkaline accelerator used to enhance the catalytic activity of the activator species on the surface of the plastic.
  • an electroless plating bath usually an electroless nickel or an electroless copper plating bath
  • the working bath activator colloid is applied to the substrate by merely contacting the surface to be activated with the colloid, usually by immersion therein for from about 30 seconds to 5 minutes.
  • the temperature of the working activator colloid may range from room temperature to about 120° F, but is preferably from about 75° F to about 85° F.
  • a 600 mL beaker is charged with 125 mL methane sulfonic acid (70%) and 275 mL deionized water. With stirring and heating 150 grams (as tin) of stannous methane sulfonate is added. The volume is brought to 490 mL with deionized water. When the solution reaches 95°C, a mixture of 1.0 mL gold solution (31J grams gold per 100 mL) and 9 mL 6N hydrochloric acid is added over a 15 second period. The heat is then turned off and the reaction mixture allowed to cool. The product is a dark purple-brown liquid containing 0.55 grams of gold per liter.
  • a gold colloid manufactured as in the process described above is then used to activate a non-conductive substrate such as an ABS plastic coupon for electroless plating.
  • a non-conductive substrate such as an ABS plastic coupon for electroless plating.
  • the coupon surface is etched with a chromic acid/sulfuric acid mixture at 160°F for 8 minutes.
  • the coupon is rinsed with deionized water for 1 minute. 3.
  • the coupon is placed in a bath of Macuplex 9339 Neutralizer* at 85°F for 2 minutes.
  • the coupon is rinsed with deionized water for 1 minute. 5.
  • the coupon is placed in the activation bath consisting of a 10% solution of the colloid as prepared above in an aqueous solution of 75 g/1 sodium chloride and 1.5% by volume hydrochloric acid (37%).
  • the coupon is rinsed with deionized water for 1 minute.
  • the coupon is placed in MacDermid Ultracel 9369 Accelerator* at 120° F for 2 minutes.
  • Coupon is rinsed with deionized water for 1 minute.
  • the coupon is rinsed in deionized water for 2 minutes, then air-dried.
  • the activated coupon plated with a uniform gray nickel coating, 8 millionths inch thickness.
  • a gold colloid manufactured as described in example 1 was used to activate a double sided copper clad panel with through holes as follows:
  • the panel is placed in a bath of M-Treat BIO hole conditioner* at 110 F° for 5 minutes.
  • the panel is rinsed in deionized water for 2 minutes.
  • the panel is placed in a bath of M-Permanganate P* at 165° for 10 minutes. 4. The panel is rinsed in deionized water for 8 minutes.
  • the panel is placed in a bath of M-Neutralize* at 110° for 5 minutes.
  • the panel is rinsed in deionized water for 4 minutes.
  • the panel is placed in a bath of M-Condition Conditioner/Cleaner* at 125°F for 5 minutes.
  • the panel is rinsed in deionized water for 5 minutes.
  • the panel is placed in a bath of Macuprep Etch G4 Microetch* at 90° F for 1 minute.
  • the panel is rinsed in deionized water for 2 minutes.
  • the panel is placed in a bath of Metex 9008 PreDip* at ambient temperature for 1 minute.
  • the panel is placed in a bath consisting of 10% of a gold colloid prepared as in Example 1 in an aqueous solution of 75 g/1 sodium chloride and 1.5% by volume hydrochloric acid (37%) at 90°F for 5 minutes.
  • the panel is rinsed with deionized water for 1.5 minutes. 14.
  • the panel is placed in a bath of M- Accelerate* at 125°F for 2.5 minutes.
  • the panel is rinsed in deionized water for 1 minute.
  • the panel is plated in M-Copper 85 Electroless Copper* at 115°F for 30 minutes.
  • the panel was rinsed with deionized water for 6 minutes then air-dried * available from MacDermid, Incorporated, 245 Freight Water, Waterbury, CT 06702.
  • the panel had a uniform copper coating.
  • Backlight examination of the plated holes were done and given a rating of 10 from scale of 1 - 10 with a rating of 10 meaning complete coverage of the hole with no light visible showing through.

Landscapes

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

Abstract

An improved colloidal activator is disclosed which is useful in preparing substrates for plating. The activator comprises a source of gold, a source of tin and an organic sulfonic acid. The colloidal activator may also include colloid stabilizers. A method for preparing and a process for using the activator are also disclosed.

Description

CATALYST SOLUTIONS USEFUL IN ACTIVATING SUBSTRATES FOR
SUBSEQUENT PLATING
FIELD OF THE INVENTION
The present invention relates to improved catalyst solutions useful in preparing substrates for plating thereupon.
BACKGROUND ART
Metallization processes for non-conductive substrates using noble metal baths, primarily baths containing palladium, as activators are well known. These processes are particularly useful in applying functional and decorative metal coatings to non-conductive substrates such as glass and various plastics, and are particularly useful in metallizing printed circuit boards.
One of the earliest innovations in the area of activating substrates for subsequent plating employed a plurality of baths in which the substrate was subjected to a basic two- step activation process entailing immersion in a stannous chloride solution followed by immersion in an acidic palladium chloride solution. In some cases only immersion in the acidic palladium chloride solution was used, however, for many substrates and for many plating solutions this activation process was unacceptable.
Subsequent innovations combined the palladium and tin steps together into a single colloidal dispersion of palladium and tin. In this regard, please refer to U. S. Patent No. 3,011,920 to Shipley, Jr. the teachings of which are incorporated herein by reference in their entirety. These colloidal dispersions of palladium and tin were and are currently widely used in activating substrates, particularly non-conductive substrates, for subsequent plating. However, the stability of the colloidal dispersion and the catalytic ability of the activator towards plating require improvement.
U. S. Patent No. 3,672,938 to Zeblisky, the teachings of which are incorporated herein by reference in their entirety, discusses various improvements to these colloidal dispersions. Zeblisky proposes a metal complex consisting essentially of a precious metal selected from the group consisting of Group VIII and I-B of the Periodic Table of Elements, a Group IV metal which is capable of two valence states and an anion capable of forming a stable moiety with both valence states of the Group IV metal. U. S. Patent No. 4,863,758 to Rhodenizer, the teachings of which are incorporated herein by reference in their entirety, discloses further improvements to colloidal noble metal activation solutions. Rhodenizer discloses a composition for activating a substrate for electroless metallization comprising: a noble metal that is catalytic to a chemical reduction plating process, salts capable of forming a protective metal sol, and at least one organic acid, which is substantially soluble in the plating bath, selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, amino acids and combinations of these.
It is an object of this invention to provide a single step, colloidal, noble metal activator with improved stability and catalytic activity towards plating.
SUMMARY OF THE INVENTION
The inventors herein propose an activator solution comprising:
a. source of gold; b. source of tin; c. an acid which is preferably an organic sulfonic acid, most preferably methane sulfonic acid; and d. optionally, a colloid stabilizer
The inventors have discovered that colloidal activator solutions of the foregoing ingredients, prepared as noted herein, provide significant advantages in terms of colloidal stability, catalytic activity and other performance factors.
DETAILED DESCRIPTION OF THE INVENTION
As noted, an improved colloidal activator solution is prepared, comprising
a. source of gold; b. source of tin; c. an acid which is preferably an organic sulfonic acid; and d. optionally, a colloid stabilizer. The source of gold may be any source that would supply gold containing ions to the activator solution. Halogenated gold salts or acids are preferred. Examples of the most preferred gold sources are gold trichloride and tetrachloroauric acid. It is preferred for the concentration of gold (measured by gold content) in the activator colloid to range from about 0.01 to 15 g./l.
The source of tin is preferably a source of stannous tin. Examples of preferred tin sources are stannous chloride, stannous sulfate, or stannous methanesulfonic acid (stannous methane sulfonate), with stannous methansulfonic acid being the most preferred. It is preferred for the concentration of tin (measured as tin content) in the activator colloid to range from about 45 to 200 g/1.
The activator colloid should contain an acid, which is preferably an organic sulfonic acid, most preferably methane sulfonic acid. Other acids such as hydrochloric acid, or sulfuric acid may be present as well. The concentration of the acid in the activator colloid preferably ranges from about 1 to 5 moles per liter. As noted, the inventors have found that the use of organic sulfonic acids in the activator colloid are greatly preferred and produce a colloid with improved stability and catalytic activity. It is most preferred to use the organic sulfonic acid corresponding to the anion provided by the source of tin (i.e. tin methane sulfonate and methane sulfonic acid). Optionally the activator colloid may also contain colloid stabilizers. Preferred colloid stabilizers include gum arabic, guar gum, xanthan gum and/or gelatin. If used, the concentration of the colloid stabilizer in the activator colloid may preferably range from 0.01% to 0.1% by weight.
The method of preparing the concentrated colloid is critical to the stability of the colloid formed and its catalytic activity. Thus first a gold containing solution should be prepared by mixing the gold source with the chosen organic sulfonic acid. A portion of the acid to be used in preparing the colloid should be mixed with the gold source in this first step. Next, a separate solution of the tin source, the other portion of the acid to be used in preparing the colloid, water and any other necessary ingredients is prepared. The gold containing solution is then added to the tin containing solution, slowly, with stirring, over a period of from 10 to 60 seconds. The reaction mixture is then stirred at room temperature for 2 hours. Alternatively, the reaction mixture may be rapidly heated, with stirring, to about 95° C and when that temperature is reached, allowed to cool naturally with stirring. A third alternative is to heat the tin containing solution to about 95° and then add the gold containing solution to the tin containing solution over a period of from 10 to 60 seconds with stirring and allow the reaction mixture to cool naturally with stirring. Heating if used should be to between about 70° C and about 95° C but is preferably to about 95° C.
Once the concentrated activator colloid is prepared as above, the activator working bath is prepared by mixing from about 1 to 25% by volume of the concentrated activator colloid with water or an aqueous solution of sodium chloride, potassium chloride, acids, or mixtures of the foregoing. The working colloid should contain from about 0.05 to 2 g/1 of gold.
As noted this colloidal activator is useful in preparing substrates, particularly non- conductive substrates, for plating, usually by electroless or chemical reduction plating. Typical electroless plating processes that may utilize this colloidal activator in plating upon plastics may include the following steps:
a. a plastic etchant, which will etch the plastic surface such as chromic acid or potassium permanganate solutions. b. a neutralizer to neutralize the plastic etchant residues such as hydroxylamine solutions. c. a conditioner, which cleans the surface of the plastic and conditions it to receive activator species. d. the working bath activator colloid e. an acidic or alkaline accelerator used to enhance the catalytic activity of the activator species on the surface of the plastic. f. an electroless plating bath, usually an electroless nickel or an electroless copper plating bath
The working bath activator colloid is applied to the substrate by merely contacting the surface to be activated with the colloid, usually by immersion therein for from about 30 seconds to 5 minutes. The temperature of the working activator colloid may range from room temperature to about 120° F, but is preferably from about 75° F to about 85° F.
The foregoing invention is further described by the following examples, which should be considered illustrative but not limiting. EXAMPLE 1
A 600 mL beaker is charged with 125 mL methane sulfonic acid (70%) and 275 mL deionized water. With stirring and heating 150 grams (as tin) of stannous methane sulfonate is added. The volume is brought to 490 mL with deionized water. When the solution reaches 95°C, a mixture of 1.0 mL gold solution (31J grams gold per 100 mL) and 9 mL 6N hydrochloric acid is added over a 15 second period. The heat is then turned off and the reaction mixture allowed to cool. The product is a dark purple-brown liquid containing 0.55 grams of gold per liter.
A gold colloid manufactured as in the process described above is then used to activate a non-conductive substrate such as an ABS plastic coupon for electroless plating. To activate the non-conductive substrate, the following steps were done:
1. The coupon surface is etched with a chromic acid/sulfuric acid mixture at 160°F for 8 minutes.
2. The coupon is rinsed with deionized water for 1 minute. 3. The coupon is placed in a bath of Macuplex 9339 Neutralizer* at 85°F for 2 minutes.
4. The coupon is rinsed with deionized water for 1 minute. 5. The coupon is placed in the activation bath consisting of a 10% solution of the colloid as prepared above in an aqueous solution of 75 g/1 sodium chloride and 1.5% by volume hydrochloric acid (37%).
6. The coupon is rinsed with deionized water for 1 minute.
7. The coupon is placed in MacDermid Ultracel 9369 Accelerator* at 120° F for 2 minutes.
8. Coupon is rinsed with deionized water for 1 minute.
9. Activated coupon is placed in MacDermid Macuplex J-64 Electroless Nickel* at 90°F for 10 minutes.
10. The coupon is rinsed in deionized water for 2 minutes, then air-dried.
The activated coupon plated with a uniform gray nickel coating, 8 millionths inch thickness.
* - available from MacDermid, Incorporated, 245 Freight Street, Waterbury, CT 06702. EXAMPLE 2
To demonstrate the usefulness of the gold colloid for activating printed circuit boards for electroless copper plating, a gold colloid manufactured as described in example 1 was used to activate a double sided copper clad panel with through holes as follows:
The panel is placed in a bath of M-Treat BIO hole conditioner* at 110 F° for 5 minutes.
2. The panel is rinsed in deionized water for 2 minutes.
3. The panel is placed in a bath of M-Permanganate P* at 165° for 10 minutes. 4. The panel is rinsed in deionized water for 8 minutes.
5. The panel is placed in a bath of M-Neutralize* at 110° for 5 minutes.
6. The panel is rinsed in deionized water for 4 minutes.
7. The panel is placed in a bath of M-Condition Conditioner/Cleaner* at 125°F for 5 minutes.
8. The panel is rinsed in deionized water for 5 minutes.
9. The panel is placed in a bath of Macuprep Etch G4 Microetch* at 90° F for 1 minute.
10. The panel is rinsed in deionized water for 2 minutes.
11. The panel is placed in a bath of Metex 9008 PreDip* at ambient temperature for 1 minute.
12. The panel is placed in a bath consisting of 10% of a gold colloid prepared as in Example 1 in an aqueous solution of 75 g/1 sodium chloride and 1.5% by volume hydrochloric acid (37%) at 90°F for 5 minutes.
13. The panel is rinsed with deionized water for 1.5 minutes. 14. The panel is placed in a bath of M- Accelerate* at 125°F for 2.5 minutes.
15. The panel is rinsed in deionized water for 1 minute.
16. The panel is plated in M-Copper 85 Electroless Copper* at 115°F for 30 minutes.
17. The panel was rinsed with deionized water for 6 minutes then air-dried * available from MacDermid, Incorporated, 245 Freight Water, Waterbury, CT 06702.
The panel had a uniform copper coating. Backlight examination of the plated holes were done and given a rating of 10 from scale of 1 - 10 with a rating of 10 meaning complete coverage of the hole with no light visible showing through.

Claims

What is claimed is:
1. A composition useful in activating a substrate for metallization, said composition comprising: a. source of gold; b. source of tin; and c. organic sulfonic acid.
2. A composition according to claim 1 comprising a gold-tin colloidal dispersion.
3. A composition according to claim 1 wherein the source of gold is selected from the group consisting of goldtrichloride, tetrachloroauric acid, and mixtures thereof.
4. A composition according to claim 1 wherein the source of tin is selected from the group consisting of stannous chloride, stannous sulfate, stannous methane sulfonate, and mixtures thereof.
5. A composition according to claim 1 wherein the organic sulfonic acid is methane sulfonic acid.
6. A composition according to claim 1 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixtures of the foregoing.
7. A composition according to claim 1 comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
8. A composition according to claim 2 wherein the source of gold is selected from the group consisting of goldtrichloride, tetrachloroauric acid, and mixtures thereof.
9. A composition according to claim 2 wherein the source of tin is selected from the group consisting of stannous chloride, stannous sulfate, stannous methane sulfonate, and mixtures thereof.
10. A composition according to claim 2 wherein the organic sulfonic acid is methane sulfonic acid.
11. A composition according to claim 2 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixtures of the foregoing.
12. A composition according to claim 2 also comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
13. A composition according to claim 9 wherein the organic sulfonic acid is methane sulfonic acid.
14. A composition according to claim 13 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixtures of the foregoing.
15. A composition according to claim 14 comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
16. A process for plating a substrate, said process comprising: a. contacting the substrate with an activator comprising:
1. source of gold;
2. source of tin; and 3. organic sulfonic acid; and subsequently b. contacting the substrate substrate with a plating solution comprising ions of a metal which is less noble than gold.
17. A process according to claim 16 wherein the activator comprises a gold -tin colloidal dispersion.
18. A process according to claim 16 wherein the source of gold is selected from the group consisting of goldtrichloride, tetrachloroauric acid, and mixtures thereof.
19. A composition according to claim 16 wherein the source of tin is selected from the group consisting of stannous chloride, stannous sulfate, stannous methane sulfonate, and mixtures thereof.
20. A composition according to claim 16 wherein the organic sulfonic acid is methane sulfonic acid.
21. A composition according to claim 16 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixture of the forgoing.
22. A process according to claim 16 comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
23. A process according to claim 17 wherein the source of gold is selected from the group consisting of goldtrichloride, tetrachloroauric acid, and mixtures thereof.
24. A process according to claim 17 wherein the source of tin is selected from the group consisting of stannous chloride, stannous sulfate, stannous methane sulfonate, and mixtures thereof.
25. A process according to claim 17 wherein the organic sulfonic acid is methane sulfonic acid.
26. A process according to claim 17 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixtures of the forgoing.
27. A process according to claim 17 comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
28. A process according to claim 24 wherein the organic sulfonic acid is methane sulfonic acid.
29. A process according to claim 28 also comprising a colloid stabilizer selected from the group consisting of gum arabic, guar gum, xanthan gum, gelatin, and mixtures of the forgoing.
30. A process according to claim 29 comprising from 0.01 to 15 g/1 gold, from 45 to 200 g/1 tin, and from 1 to 5 moles per liter of organic sulfonic acid.
31. A method for forming a colloidal catalyst, said method comprising: a. preparing a gold containing solution comprising gold ions and an acid; b. preparing a tin containing solution comprising stannous tin ions and an acid; c. adding the gold containing solution to the tin containing solution with stirring to create an activator; d. continuing to stir the activator until a colloidal tin-gold dispersion is formed.
32. A method according to clam 31 wherein the activator is heated to from about 70°C to about 95°C and then cooled.
33. A method according to claim 31 wherein the tin containing solution is heated to between about 70°C to about 95°C prior to adding the gold containing solution.
34. A method according to claim 31 wherein the acid is an organic sulfonic acid.
35. A method according to claim 32 wherein the acid is an organic sulfonic acid.
36. A method according to claim 33 wherein the acid is an organic sulfonic acid.
PCT/US2001/030655 2000-11-06 2001-10-01 Catalyst solutions useful in activating substrates for subsequent plating WO2002036273A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001294928A AU2001294928A1 (en) 2000-11-06 2001-10-01 Catalyst solutions useful in activating substrates for subsequent plating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US70713400A 2000-11-06 2000-11-06
US09/707,134 2000-11-06

Publications (2)

Publication Number Publication Date
WO2002036273A1 true WO2002036273A1 (en) 2002-05-10
WO2002036273A8 WO2002036273A8 (en) 2002-06-06

Family

ID=24840486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/030655 WO2002036273A1 (en) 2000-11-06 2001-10-01 Catalyst solutions useful in activating substrates for subsequent plating

Country Status (2)

Country Link
AU (1) AU2001294928A1 (en)
WO (1) WO2002036273A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US3672938A (en) * 1969-02-20 1972-06-27 Kollmorgen Corp Novel precious metal sensitizing solutions
US4004051A (en) * 1974-02-15 1977-01-18 Crown City Plating Company Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating
US4244739A (en) * 1978-07-25 1981-01-13 Roberto Cagnassi Catalytic solution for the electroless deposition of metals
US4762560A (en) * 1982-09-27 1988-08-09 Learonal, Inc. Copper colloid and method of activating insulating surfaces for subsequent electroplating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US3672938A (en) * 1969-02-20 1972-06-27 Kollmorgen Corp Novel precious metal sensitizing solutions
US4004051A (en) * 1974-02-15 1977-01-18 Crown City Plating Company Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating
US4244739A (en) * 1978-07-25 1981-01-13 Roberto Cagnassi Catalytic solution for the electroless deposition of metals
US4762560A (en) * 1982-09-27 1988-08-09 Learonal, Inc. Copper colloid and method of activating insulating surfaces for subsequent electroplating

Also Published As

Publication number Publication date
WO2002036273A8 (en) 2002-06-06
AU2001294928A1 (en) 2002-05-15

Similar Documents

Publication Publication Date Title
EP1343921B1 (en) Method for electroless nickel plating
EP2009142B1 (en) Composition for etching treatment of resin molded article
EP0913498A1 (en) Electroless plating processes
EP0163831A2 (en) Catalytic metal of reduced particle size
EP2825690B1 (en) Process for metallizing nonconductive plastic surfaces
TWI226384B (en) Method of preparing a substrate material by sponsoring a catalytic reaction and plating a substrate with metal
EP0191433B1 (en) Process for manufacturing a concentrate of a palladium-tin colloidal catalyst
JP4189532B2 (en) Method for activating catalyst for electroless plating
JP4977885B2 (en) Electro copper plating method
US4581256A (en) Electroless plating composition and method of use
US20020062760A1 (en) Catalyst solutions useful in activating substrates for subsequent plating
JP4649666B2 (en) Electroless gold plating solution
JPH11241170A (en) Catalytic composition for electroless plating
WO2002036273A1 (en) Catalyst solutions useful in activating substrates for subsequent plating
JP2007126743A (en) Pretreatment method for electroless plating and method for forming electroless plating film
US4820547A (en) Activators for colloidal catalysts in electroless plating processes
CN103276375B (en) Plating coating catalyst and method
US20220154343A1 (en) A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization
EP0109402B1 (en) Catalyst solutions for activating non-conductive substrates and electroless plating process
JP2001323383A (en) Method for imparting catalyst for electroless plating
US5387332A (en) Cleaner/conditioner for the direct metallization of non-conductors and printed circuit boards
EP4204600A1 (en) A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization
JP2002309376A (en) Catalyst impartation method for electroless copper plating
JP2002309375A (en) Catalyst impartation method for electroless plating
JPH1030188A (en) Catalyst liquid for electroless plating

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: C1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

CFP Corrected version of a pamphlet front page
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP