US3902908A - Catalyst system for activating surfaces prior to electroless deposition - Google Patents

Catalyst system for activating surfaces prior to electroless deposition Download PDF

Info

Publication number
US3902908A
US3902908A US403502A US40350273A US3902908A US 3902908 A US3902908 A US 3902908A US 403502 A US403502 A US 403502A US 40350273 A US40350273 A US 40350273A US 3902908 A US3902908 A US 3902908A
Authority
US
United States
Prior art keywords
catalyst
solution
accelerator
booster compound
preparing
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
US403502A
Inventor
Alan Rantell
Abraham Holtzman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MacDermid Inc
Original Assignee
MacDermid Inc
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 Inc filed Critical MacDermid Inc
Application granted granted Critical
Publication of US3902908A publication Critical patent/US3902908A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C18/20—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 the preparation and use of a catalyst composition for activating nonconductive surfaces prior to electroless deposition of metals.
  • activator or catalyst For the purpose of electroless or chemical plating of non-conductive substrates, small quantities of activator or catalyst must first be placed on the surface of the substrate.
  • Palladium is found to be the most satisfactory catalyst but any metal selected from palladium, gold, silver or the platinum group of metals is suitable.
  • the activating or catalyzing process is often carried out by consecutive immersion of the substrate in solutions containing PdCl and SnCl respectively. More recently the use of single step activators comprising colloidal mixtures of PdCl and SnCl has been proposed.
  • Typical working strength catalyst solutions contain:
  • Accelerators are generally solutions of strong acids or strong alkalis and are employed between the catalyst treatment and electroless deposition.
  • the principle of the invention involves the formation of a highly active compound by reaction at high temperature between a stannous salt, usually the chloride, and low concentrations of palladous or other similar catalytic ions; e.g. Au(l), Au( III), Pt(II), Pt(IV), Rh(IIl), Ru(IlI), Ru(IV), Os(III), Os(IV), Ir(III), Ir- (IV) or Ag(l).
  • the choice of booster compound is determined by the nature of the accelerator solution employed in the processing cycle. It is essential that the 5 booster compound should form a sparingly soluble compound when contacted with the accelerator; i.e.
  • the booster com pound should be an acid salt of metal ion-forming insoluble hydroxides at alkaline pH values; e.g. compounds containing Mg, Fe, Fe, Mn, Cu, Ni, Co or Cr.
  • the catalyst is formed by heating the component supplying the catalytic ion and the booster compound in strong acid solution at temperatures in excess of 75C, and then adding an excess of stannous ion. The temperature of the mixture is maintained above 75C until the reaction is completed. During the reaction, the color of the mixture changes from light amber to dark brown, returning to light amber. Finally the completion of the reaction is indicated when the color of the mixture becomes dark brown for the second time.
  • the stannous ion may be added in two stages. Sufficient stannous salt to carry out the reaction is first added to the mixture of catalytic ion and booster compound at temperatures in excess of C. The quantity required may be between 2 and 50 g/l as SnCl depending on temperature and concentration of catalytic ion. When the reaction is complete after 1-20 minutes, a vast excess of an acid stannous salt is added. Small quantities of sodium stannate are found useful for stabilizing the compound formed between Sn(II) and the catalytic ion, e.g. (Pd(II)).
  • the preheating of the reactants to temperatures in excess of 75C prior to admixing them in the preparation step is an important part of the invention.
  • the catalytic activity of the reaction product formed between Sn(II) and the catalytic ion, e.g. Pd(II) increases with increase of reaction temperature during manufacture, allowing relatively low concentrations of catalytic ion to be used. At temperatures below 75C much greater concentrations of catalytic ion are required in order to maintain catalytic activity; viz. greater than 150 mg/l of PdCl
  • the reaction between Sn(II) and Pd(II), i.e. the catalytic ion may take two routes.
  • the preferred reac tion yields a Sn(II)/Pd(ll) addition compound whereas a secondary reaction causes formation of metallic palladium. The latter reaction is generally undesirable.
  • the use of high manufacturing temperatures and excess stannous salt encourages the preferred reaction and inhibits the secondary reaction.
  • the invention is illustrated by the following examples for the preparation and use of the catalyst.
  • the temperature is maintained at C for 15 minutes and then allowed to cool prior to use.
  • the catalyst may be used to activate plastic surfaces or copper clad printed circuit boards prior to electroless deposition.
  • the following processing cycle is preferred:
  • ABS plastic is etched in a mixture containing 200-400 g/l CrO and 300600 g/l H 50 at 4070C for 2l0 minutes. After thorough rinsing, the plastic is immersed in the catalyst solution for l-5 minutes at 5 room temperature. For increased activation it is perg/l NaOH for lminutes at 20-60C. The preferred temperature of the accelerator is 40C. The activated plastic is then immersed in any electroless nickel or copper plating solution.
  • a preferred composition is:
  • the electroless nickel solution is employed at 20-30C for 5-l0 minutes.
  • the time allowed for the reaction of the first addition is not critical and may be for any period greater than 1 minute, but 15 minutes is preferred.
  • the reaction temperature again is important, as it must be greater than 75C, 90-95C being preferred.
  • the catalyst solution may be used to activate plastic surfaces in the manner described in Example 1.
  • the temperature of the mixture is maintained at 90C for IS minutes and then cooled to room temperature for use.
  • the electroless plating procedure then proceeds in a similar manner to that described in Example I, except that in this instance the accelerator solution should be l0500 ml/] of ammonia solution (28% w/v).
  • AICL acts as a booster compound when used in conjunction with an ammonium hydrox- LII idc accelerator since Al(OH) is not soluble in ammonia solution.
  • the temperature of the mixture is maintained at 90C for 15 minutes and then the catalyst is cooled at room temperature for use.
  • the catalyst solution may be used to activate plastic Surfaces in a similar manner to that described in Example 1, except that in this instance the accelerator solution should be 10-200 g/l H 50
  • the activated catalysts referred to in the invention are not colloidal in nature. Tyndall effect measurements taken on the undiluted catalyst solutions and electron microscopy of the adsorbed catalyst fail to show any colloidal particles.
  • the active component of the snCl /Pdcl catalyst is an acid soluble complex formed between Sn(ll) and Pd(ll). On contact with the accelerator solution, a slow redox reaction occurs:
  • the elemental palladium formed can then initiate electroless deposition.
  • the presence of the booster enables a concentration of catalytic metal ion in solution equivalent to about 10 mg/l of Pd as PdCl to be effective. For economic reasons a concentration equivalent to about 500 mg/] of PdCl represents a practical maximum.
  • Booster compounds such as MnCl and FeCl; produce a voluminous surface precipitate when the adsorbed catalyst contacts the sodium hydroxide accelerator.
  • the precipitated metal hydroxides help to retain the Pd(ll) on the plastic surface until the redox reaction has occurred. If no booster compound is used the Pd(ll) may leach into the accelerator before any reaction has occurred.
  • An aqueous acid catalyst solution comprising a Pd(ll) catalytic ion wherein said catalytic ion is present in amount sufficient to provide in the working strength catalyst solution a concentration equivalent to about l()5()0 mg/l of Pd as PdCl a stochiometric excess of stannous salt, and a booster compound consisting of a soluble metal salt of which the cation is capable of forming a precipitate when contacted with the accelerator solution used in an electroless plating process employing a substrate which has been catalyzed in said catalyst solution, said booster compound being present in amount of about 0.1 mol/l up to 5 mol/l in the working strength solution.
  • aqueous catalytic solution composition as defined in claim 7, wherein the booster compound is selected from the group consisting of Ca Ba, Fr, 2+ 2+ 2+ m -1+ :i+ 2+ 2+ C 3+ 2+ 2+ 2+ a+

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)

Abstract

An electroless metal plating catalyst and a particular method of preparing it at elevated temperature by reaction of a stannous salt and palladous or other similar catalytic metal ion augmented by incorporating a booster compound are disclosed. The resultant catalyst is useable at much lower catalytic metal concentration in plating operations than conventional prior catalysts. The booster compounds employed are acid or alkali soluble metal salts forming a sparingly soluble compound when contacted with conventional alkali or acid accelerators in the plating process.

Description

United States Patent [191 Rantell et al.
[4 1 Sept. 2, 1975 CATALYST SYSTEM FOR ACTIVATING SURFACES PRIOR TO ELECTROLESS DEPOSITION [75] Inventors: Alan Rantell, London, England; Abraham Holtzman, Bat-Yam,
Israel [73] Assignee: MacDermid Incorporated,
Waterbury, Conn.
22 Filed: Oct. 4, 1973 21 Appl.No.:403,502
[30] Foreign Application Priority Data Mar. 21, 1973 United Kingdom 13545/73 [52] US. Cl. 106/1; 1 17/47 A; 204/30 [51] Int. Cl. C23C 3/00 [58] Field of Search 106/1; 204/30; 117/47 A;
[56] References Cited UNITED STATES PATENTS 3,532,518 lO/l97O DOttavio 204/30 X 3,650,913 3/1972 DOttavio 204/30 3,698,919 10/1972 Kuzmik ..204/3OX Primary ExaminerLewis T. Jacobs Attorney, Agent, or FirmSteward & Steward 57 ABSTRACT compound when contacted with conventional alkali or acid accelerators in the plating process.
8 Claims, No Drawings CATALYST SYSTEM FOR ACTIVATING SURFACES PRIOR TO ELECTROLESS DEPOSITION CROSS REFERENCE TO PRIOR RELATED APPLICATIONS This application corresponds to British Provisional Specification No. 13545/73, filed Mar. 21, 1973.
FIELD OF THE INVENTION The present invention relates to the preparation and use of a catalyst composition for activating nonconductive surfaces prior to electroless deposition of metals.
For the purpose of electroless or chemical plating of non-conductive substrates, small quantities of activator or catalyst must first be placed on the surface of the substrate. Palladium is found to be the most satisfactory catalyst but any metal selected from palladium, gold, silver or the platinum group of metals is suitable.
The activating or catalyzing process is often carried out by consecutive immersion of the substrate in solutions containing PdCl and SnCl respectively. More recently the use of single step activators comprising colloidal mixtures of PdCl and SnCl has been proposed. Typical working strength catalyst solutions contain:
PdCI. 300- lUUOmg/I SnCL |s SOg/l wt sno smo 1 7 g/l HCl 250- 3(J0ml/l However, these PdCl- /sncl mixtures are more effective when used in conjunction with an additional treatment solution known as an accelerator. Accelerators are generally solutions of strong acids or strong alkalis and are employed between the catalyst treatment and electroless deposition.
The method and conditions of preparation of PdCIg/SIICI- mixtures is critical. Further, the high con ccntration of PdCIg employed makes the catalyst solutions very expensive. Less critical yet cheaper solutions would be an advantage.
SUMMARY OF THE INVENTION The principle of the invention involves the formation of a highly active compound by reaction at high temperature between a stannous salt, usually the chloride, and low concentrations of palladous or other similar catalytic ions; e.g. Au(l), Au( III), Pt(II), Pt(IV), Rh(IIl), Ru(IlI), Ru(IV), Os(III), Os(IV), Ir(III), Ir- (IV) or Ag(l). The choice of booster compound is determined by the nature of the accelerator solution employed in the processing cycle. It is essential that the 5 booster compound should form a sparingly soluble compound when contacted with the accelerator; i.e. if a NaOH accelerator is employed, the booster com pound should be an acid salt of metal ion-forming insoluble hydroxides at alkaline pH values; e.g. compounds containing Mg, Fe, Fe, Mn, Cu, Ni, Co or Cr.
In one method of implementing the present invention, the catalyst is formed by heating the component supplying the catalytic ion and the booster compound in strong acid solution at temperatures in excess of 75C, and then adding an excess of stannous ion. The temperature of the mixture is maintained above 75C until the reaction is completed. During the reaction, the color of the mixture changes from light amber to dark brown, returning to light amber. Finally the completion of the reaction is indicated when the color of the mixture becomes dark brown for the second time.
This may take from 1 to 20 minutes.
Alternatively the stannous ion may be added in two stages. Sufficient stannous salt to carry out the reaction is first added to the mixture of catalytic ion and booster compound at temperatures in excess of C. The quantity required may be between 2 and 50 g/l as SnCl depending on temperature and concentration of catalytic ion. When the reaction is complete after 1-20 minutes, a vast excess of an acid stannous salt is added. Small quantities of sodium stannate are found useful for stabilizing the compound formed between Sn(II) and the catalytic ion, e.g. (Pd(II)).
The preheating of the reactants to temperatures in excess of 75C prior to admixing them in the preparation step is an important part of the invention. The catalytic activity of the reaction product formed between Sn(II) and the catalytic ion, e.g. Pd(II), increases with increase of reaction temperature during manufacture, allowing relatively low concentrations of catalytic ion to be used. At temperatures below 75C much greater concentrations of catalytic ion are required in order to maintain catalytic activity; viz. greater than 150 mg/l of PdCl The reaction between Sn(II) and Pd(II), i.e. the catalytic ion, may take two routes. The preferred reac tion yields a Sn(II)/Pd(ll) addition compound whereas a secondary reaction causes formation of metallic palladium. The latter reaction is generally undesirable. The use of high manufacturing temperatures and excess stannous salt encourages the preferred reaction and inhibits the secondary reaction. V
The invention is illustrated by the following examples for the preparation and use of the catalyst.
EXAMPLE I For 1 liter of working strength catalyst a mixture containing:
PdCl 45 mg. MnCl. 15 g.
HCl (37% w/v) 200 ml. H. ,O 400 ml.
is heated to.90C and reacted with a solution containing:
SnCI 2H O 150 g. Na- SnO 3H- 4 g. HCl (3771 w/v) 300 ml.
The temperature is maintained at C for 15 minutes and then allowed to cool prior to use.
The catalyst may be used to activate plastic surfaces or copper clad printed circuit boards prior to electroless deposition. For the plating of ABS plastics the following processing cycle is preferred:
ABS plastic is etched in a mixture containing 200-400 g/l CrO and 300600 g/l H 50 at 4070C for 2l0 minutes. After thorough rinsing, the plastic is immersed in the catalyst solution for l-5 minutes at 5 room temperature. For increased activation it is perg/l NaOH for lminutes at 20-60C. The preferred temperature of the accelerator is 40C. The activated plastic is then immersed in any electroless nickel or copper plating solution. A preferred composition is:
pH adjusted to 8.0 8.5 with NH.
The electroless nickel solution is employed at 20-30C for 5-l0 minutes.
EXAMPLE 2 For 1 liter of working strength catalyst a mixture containing:
Pd(l 45 mg. FeCl 40 g.
HCl (37% w/v) 200 ml. H. 400 ml.
is heated to 90C and then reacted with 20g SnCl .2H-,O. After the reaction has continued for a period of minutes, a mixture containing:
The time allowed for the reaction of the first addition is not critical and may be for any period greater than 1 minute, but 15 minutes is preferred. The reaction temperature again is important, as it must be greater than 75C, 90-95C being preferred.
The catalyst solution may be used to activate plastic surfaces in the manner described in Example 1.
EXAMPLE 3 The catalyst is prepared and used-as in Example 1 except that in this instance the PdCl is replaced by 75 mg of HAu Cl EXAMPLE 4 For 1 liter of working strength catalyst a mixture containing:
Pdcl 40 mg. AICL, g.
HCI (37% w/ 200 ml. up 400 ml.
is heated to 90C and reacted with a solution containing:
The temperature of the mixture is maintained at 90C for IS minutes and then cooled to room temperature for use. The electroless plating procedure then proceeds in a similar manner to that described in Example I, except that in this instance the accelerator solution should be l0500 ml/] of ammonia solution (28% w/v).
In this example AICL, acts as a booster compound when used in conjunction with an ammonium hydrox- LII idc accelerator since Al(OH) is not soluble in ammonia solution.
EXAMPLE 5 For 1 liter of working strength catalyst a mixture containing:
PdCl- 45 mg. BaCl 40 g.
HCl (37% w/v) 200 ml. H 0 400 ml.
is heated to 90C and reacted with a solution containing:
The temperature of the mixture is maintained at 90C for 15 minutes and then the catalyst is cooled at room temperature for use.
The catalyst solution may be used to activate plastic Surfaces in a similar manner to that described in Example 1, except that in this instance the accelerator solution should be 10-200 g/l H 50 The activated catalysts referred to in the invention are not colloidal in nature. Tyndall effect measurements taken on the undiluted catalyst solutions and electron microscopy of the adsorbed catalyst fail to show any colloidal particles. The active component of the snCl /Pdcl catalyst is an acid soluble complex formed between Sn(ll) and Pd(ll). On contact with the accelerator solution, a slow redox reaction occurs:
Sn(-ll) Pd(lll) Sn(lV) Pd(O).
The elemental palladium formed can then initiate electroless deposition. The presence of the booster enables a concentration of catalytic metal ion in solution equivalent to about 10 mg/l of Pd as PdCl to be effective. For economic reasons a concentration equivalent to about 500 mg/] of PdCl represents a practical maximum.
Booster compounds such as MnCl and FeCl;, produce a voluminous surface precipitate when the adsorbed catalyst contacts the sodium hydroxide accelerator. The precipitated metal hydroxides help to retain the Pd(ll) on the plastic surface until the redox reaction has occurred. If no booster compound is used the Pd(ll) may leach into the accelerator before any reaction has occurred.
What is claimed is:
l. A method for preparing a catalyst solution by heating an acid solution of a Pd(ll) catalytic ion wherein said catalytic ion is present in amount sufficient to provide in the working strength catalyst solution a concentration equivalent to about 10500 mg/l of Pd as PdCI- with a solution containing a stochiometric excess of stannous salt wherein at least one of said catalytic ion and stannous salt solutions is first heated to a temperature in excess of C before the other is added to it, and wherein a booster compound consisting of a soluble metal salt, of which the cation is capable of forming a precipitate when contacted with the accelerator solution used in an electroless plating process, is added to the catalyst mixture during preparation, said booster compound being present in amount of about 0.] mol/l up to 5 mol/l in the working strength solution.
2. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a strong alkali, wherein the booster compound is a salt containing a cation selected from the group consisting of Mg, Fe, Fe. Mn, Mn, Cu, Ni, Co, Cr.
3. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator an alkaline ammonia solution, wherein the booster compound is a salt containing a cation selected from the group consisting of Mg, Fe. Mn'. Mn, zu: Pb2+ AliH 4. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator sulphuric acid or a soluble acid sulphate, wherein the booster compound is a salt containing a cation selected from the group consisting of Ca Ba, Sr, Pb.
5. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a soluble carbonate or phosphate, wherein the booster compound is a salt containing a cation selected from the group consisting of Ca Ba, Sr, Pb'l't', Mgl-i" F ll+q 11 3+g M 2+, M 3+ C 2+, bJiZ-i-q CO2+, c 3+q Cd2+s 2 2+g l)b.l-l-s Alli-F 6. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a soluble fluoride, wherein the booster compound is salt containing a cation selected from the group consisting of Mg, Ca, Ba, Sr, Zn, Cd, Al3+ Pb2+ M l-F, M 3+ 7. An aqueous acid catalyst solution comprising a Pd(ll) catalytic ion wherein said catalytic ion is present in amount sufficient to provide in the working strength catalyst solution a concentration equivalent to about l()5()0 mg/l of Pd as PdCl a stochiometric excess of stannous salt, and a booster compound consisting of a soluble metal salt of which the cation is capable of forming a precipitate when contacted with the accelerator solution used in an electroless plating process employing a substrate which has been catalyzed in said catalyst solution, said booster compound being present in amount of about 0.1 mol/l up to 5 mol/l in the working strength solution.
8. An aqueous catalytic solution composition as defined in claim 7, wherein the booster compound is selected from the group consisting of Ca Ba, Fr, 2+ 2+ 2+ m -1+ :i+ 2+ 2+ C 3+ 2+ 2+ 2+ a+

Claims (8)

1. A METHOD FOR PREPARING A CATALYST SOLUTION BY HEATING AN ACID SOLUTION OF A PD(11) CATALYTIC ION WHEREIN SAID CATALYTIC ION IS PRESENT IN AMOUNT SUFFICIENT TO PROVIDE IN THE WORKING STRENGTH CATALYST SOLUTION A CONCENTRATION EQUIVALENT TO ABOUT 10-500 MG/1 OF PD2+ AS PDCL2, WITH A SOLUTION CONTAINING A STOCHIOMETRIC EXCESS OF STANNOUS SALT WHEREIN AT LEAST ONE OF SAID CATALYTIC ION AND STANNOUS SALT SOLUTIONS IS FIRST HEATED TO A TEMPERATURE IN EXCESS OF 75*C BEFORE THE OTHR IS ADDED TO IT, SND WHEREIN A BOOSTER COMPOUND CONSISTING OF A SOLUBLE METAL SALT, OF WHICH THE CATION IS CAPABLE OF FORMING A PRECIPITATE WHEN CONTACTED WITH THE ACCELERATOR SOLUTION USED IN AN ELECTROLESS PROCESS, IS ADDED TO THE CATALYST MIXTURE DURING PREPARATION, SAID BOOSTER COMPOUND BEING PRESENT IN AMOUNT OF ABOUT 0.1 MOL/1 UP TO 5 MOL/1 IN THE WORKING STRENGTH SOLUTION.
2. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a strong alkali, wherein the booster compound is a salt containing a cation selected from the group consisting of Mg2 , Fe2 , Fe3 , Mn2 , Mn3 , Cu2 , Ni2 , Co2 , Cr3 .
3. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator an alkaline ammonia solution, wherein the booster compound is a salt containing a cation selected from the group consisting of Mg2 , Fe3 , Mn2 , Mn3 , Cr3 , Pb2 , Al3 .
4. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator sulphuric acid or a soluble acid sulphate, wherein the booster compound is a salt containing a cation selected from the group consisting of Ca2 , Ba2 , Sr2 , Pb2 .
5. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a soluble carbonate or phosphate, wherein the booster compound is a salt containing a cation selected from the group consisting of Ca2 , Ba2 , Sr2 , Pb2 , Mg2 , Fe2 , Fe3 , Mn2 , Mn3 , Cu2 , Ni2 , Co2 , Cr3 , Cd2 , Zn2 , Pb2 , Al3 .
6. A method for preparing a catalyst as in claim 1, for use in an electroless plating process employing as the accelerator a soluble fluoride, wherein the booster compound is salt containing a cation selected from the group consisting of Mg2 , Ca2 , Ba2 , Sr2 , Zn2 , Cd2 , Al3 , Pb2 , Mn2 , Mn3 .
7. An aqueous acid catalyst solution comprising a Pd(II) catalytic ion wherein said catalytic ion is present in amount sufficient to provide in the working strength catalyst solution a concentration equivalent to about 10-500 mg/l of Pd2 as PdCl2, a stochiometric excess of stannous salt, and a booster compound consisting of a soluble metal salt of which the cation is capable of formIng a precipitate when contacted with the accelerator solution used in an electroless plating process employing a substrate which has been catalyzed in said catalyst solution, said booster compound being present in amount of about 0.1 mol/l up to 5 mol/l in the working strength solution.
8. An aqueous catalytic solution composition as defined in claim 7, wherein the booster compound is selected from the group consisting of Ca2 , Ba2 , Fr2 , Pb2 , Mg2 , Fe2 , Fe3 , Mn2 , Mn3 , Cu2 , Ni2 , Co2 , Cr3 , Cd2 , Zn2 , Pb2 , Al3 .
US403502A 1973-03-21 1973-10-04 Catalyst system for activating surfaces prior to electroless deposition Expired - Lifetime US3902908A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1354573 1973-03-21

Publications (1)

Publication Number Publication Date
US3902908A true US3902908A (en) 1975-09-02

Family

ID=10024901

Family Applications (2)

Application Number Title Priority Date Filing Date
US403503A Expired - Lifetime US3884704A (en) 1973-03-21 1973-10-04 Catalyst system for activating surfaces prior to electroless deposition
US403502A Expired - Lifetime US3902908A (en) 1973-03-21 1973-10-04 Catalyst system for activating surfaces prior to electroless deposition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US403503A Expired - Lifetime US3884704A (en) 1973-03-21 1973-10-04 Catalyst system for activating surfaces prior to electroless deposition

Country Status (1)

Country Link
US (2) US3884704A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181759A (en) * 1976-08-05 1980-01-01 Nathan Feldstein Process for metal deposition of a non-conductor substrate
US4212768A (en) * 1975-05-05 1980-07-15 Jameson Melvin N Electroless plating of nonconductive substrates
US4239538A (en) * 1976-03-30 1980-12-16 Surface Technology, Inc. Catalytic primer
DE3443471A1 (en) * 1983-12-02 1985-06-13 Omi International Corp., Warren, Mich. METHOD FOR REACTIVATING AN AQUEOUS INITIATOR SOLUTION CONTAINING PRECIOUS METALS, AND THE INITIATOR SOLUTION ITSELF
US5242713A (en) * 1988-12-23 1993-09-07 International Business Machines Corporation Method for conditioning an organic polymeric material
US6586047B2 (en) 2001-09-05 2003-07-01 Brad Durkin Process for plating particulate matter
US6645557B2 (en) 2001-10-17 2003-11-11 Atotech Deutschland Gmbh Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions
US20050202583A1 (en) * 2004-03-15 2005-09-15 Canon Kabushiki Kaisha Antistatic film forming composition, and producing method for conductive film pattern, electron source and image display apparatus

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA764709B (en) * 1976-01-26 1978-02-22 Borg Warner Catalytically active composition for electroless plating
US4233344A (en) * 1978-07-20 1980-11-11 Learonal, Inc. Method of improving the adhesion of electroless metal deposits employing colloidal copper activator
US4908259A (en) * 1986-11-18 1990-03-13 Sankyo Kasei Kabushiki Kaisha Molded article with partial metal plating and a process for producing such article
JPH0660416B2 (en) * 1986-11-18 1994-08-10 三共化成株式会社 Manufacturing method of plastic molded products
US4812353A (en) * 1986-12-27 1989-03-14 Sankyo Kasei Kabushiki Kaisha Process for the production of circuit board and the like
US5079600A (en) * 1987-03-06 1992-01-07 Schnur Joel M High resolution patterning on solid substrates
US5077085A (en) * 1987-03-06 1991-12-31 Schnur Joel M High resolution metal patterning of ultra-thin films on solid substrates
CN100419120C (en) * 2005-12-30 2008-09-17 东北大学 Process for silver caating on surface of magnesium and magnesium alloy
GB0915251D0 (en) * 2009-09-02 2009-10-07 Univ Bangor Low temperature platinisation for dye-sensitised solar cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532518A (en) * 1967-06-28 1970-10-06 Macdermid Inc Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US3650913A (en) * 1969-09-08 1972-03-21 Macdermid Inc An electroless plating process employing a specially prepared palladium-tin activator solution
US3698919A (en) * 1969-08-14 1972-10-17 Macdermid Inc Preparation of plastic substrates for electroless plating and solutions therefor

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632388A (en) * 1969-04-14 1972-01-04 Macdermid Inc Preactivation conditioner for electroless metal plating system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532518A (en) * 1967-06-28 1970-10-06 Macdermid Inc Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US3698919A (en) * 1969-08-14 1972-10-17 Macdermid Inc Preparation of plastic substrates for electroless plating and solutions therefor
US3650913A (en) * 1969-09-08 1972-03-21 Macdermid Inc An electroless plating process employing a specially prepared palladium-tin activator solution

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212768A (en) * 1975-05-05 1980-07-15 Jameson Melvin N Electroless plating of nonconductive substrates
US4239538A (en) * 1976-03-30 1980-12-16 Surface Technology, Inc. Catalytic primer
US4181759A (en) * 1976-08-05 1980-01-01 Nathan Feldstein Process for metal deposition of a non-conductor substrate
DE3443471A1 (en) * 1983-12-02 1985-06-13 Omi International Corp., Warren, Mich. METHOD FOR REACTIVATING AN AQUEOUS INITIATOR SOLUTION CONTAINING PRECIOUS METALS, AND THE INITIATOR SOLUTION ITSELF
US5242713A (en) * 1988-12-23 1993-09-07 International Business Machines Corporation Method for conditioning an organic polymeric material
US6586047B2 (en) 2001-09-05 2003-07-01 Brad Durkin Process for plating particulate matter
US6645557B2 (en) 2001-10-17 2003-11-11 Atotech Deutschland Gmbh Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions
US20050202583A1 (en) * 2004-03-15 2005-09-15 Canon Kabushiki Kaisha Antistatic film forming composition, and producing method for conductive film pattern, electron source and image display apparatus

Also Published As

Publication number Publication date
US3884704A (en) 1975-05-20

Similar Documents

Publication Publication Date Title
US3902908A (en) Catalyst system for activating surfaces prior to electroless deposition
US3993799A (en) Electroless plating process employing non-noble metal hydrous oxide catalyst
US4004051A (en) Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating
US4048354A (en) Method of preparation and use of novel electroless plating catalysts
US4136216A (en) Non-precious metal colloidal dispersions for electroless metal deposition
US4087586A (en) Electroless metal deposition and article
US3597266A (en) Electroless nickel plating
US4301190A (en) Pretreatment with complexing agent in process for electroless plating
US20150129540A1 (en) Process for metallizing nonconductive plastic surfaces
US4339476A (en) Dispersions for activating non-conductors for electroless plating
US4220678A (en) Dispersions for activating non-conductors for electroless plating
US4035227A (en) Method for treating plastic substrates prior to plating
US3547830A (en) High area catalyst preparation
US4321285A (en) Electroless plating
US2976181A (en) Method of gold plating by chemical reduction
US4282271A (en) Dispersions for activating non-conductors for electroless plating
US4151311A (en) Post colloid addition of catalytic promoters to non noble metal principal catalytic compounds in electroless plating catalysts
JPH0613753B2 (en) Method for producing solution containing fine metal body used for electroless plating
US20150307992A1 (en) Process for metallizing nonconductive plastic surfaces
US4082557A (en) Silver base activating solutions for electroless copper deposition
US4261747A (en) Dispersions for activating non-conductors for electroless plating
US4265942A (en) Non-noble metal colloidal compositions comprising reaction products for electroless deposition
US4132832A (en) Method of applying dispersions for activating non-conductors for electroless plating and article
US3976816A (en) Activation of surfaces intended for electroless plating
CA1084895A (en) Catalytically active composition for electroless plating