Patent Publication Number: US-4321285-A

Title: Electroless plating

Description:
REFERENCE TO PRIOR APPLICATION 
     This is a division of application Ser. No. 060,969, filed July 26, 1979, abandoned, which is a division of Ser. No. 672,044, Mar. 30, 1976 abandoned, which is a continuation-in-part of U.S. application Ser. No.512,224, filed Oct. 4, 1974 abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     Electroless or autocatalytic coating of dielectric surfaces is a well-known process finding wide-spread utility in the preparation of such diverse articles as printed circuits, automotive trim, etc. 
     The normal commercial electroless coating process involves an initial etching of the dielectric substrate by physical or chemical means to improve adherence of the metallic coating. The etched surface is then sensitized by treatment with a solution of stannous ions, e.g., a stannous chloride solution, and then activated by treatment with a solution of palladium chloride. Generally, after etching, most substrates are hydrophilic. Activation is effected by reduction of the palladium ions to the zero valence state by the stannous ions to form palladium metal sites or by formation of a tin/palladium complex on the surface. 
     In the U.S. Pat. No. 3,011,920, issued Dec. 5, 1961, to Shipley, an alternative process for preparing the substrate prior to electroless coating is described in which the noble metal, e.g. palladium, is applied directly to the dielectric substrate in the form of a colloidal solution containing the metal in the zero valence state. Normally, the metal is formed in the colloidal solution by introducing both palladium chloride and stannous chloride into the solution, the palladium ions being reduced within the solution to the zero valence state by the stannous ions, or by formation of a tin/palladium complex on the surface. In processing an article with this type of catalyst (composed of SnCl 2  and PdCl 2 ), following a rinse step, an immersion into an accelerator solution is carried out. Typical accelerator solutions are composed of diluted acid such as fluoroboric acid. 
     Another procedure is described in U.S. Pat. No. 3,783,005, issued Jan. 1, 1974, to Kenney, wherein the sensitizing ions, e.g., stannous ions, are coated onto the substrate first treated by using hydrous oxide colloids of the type described in U.S. Pat. No. 3,657,003, issued Apr. 18, 1972, to Kenney. More specifically, the process described therein comprises forming a hydrous oxide colloid containing stannous ions, either as the hydrous oxide or in combination with the hydrous oxide of another metal, coating the dielectric substrate with the colloid, and thereafter activating the substrate with a solution of palladium or other noble metal ions, the palladium ions being converted to palladium metal by the stannous ions in the colloid. The hydrous oxide colloid used in promoting the stannous ion adsorption to the surface is unchanged in its oxidation state. As an alternative process, Kenney describes activating the surface with a one-step sensitizer-activator solution in which a noble metal ion colloid is applied to the untreated surface and then reduced to the zero valence state. 
     A similar disclosure of a one-step sensitizer-activator process using palladium is disclosed by F. Pearlstein in Metal Finishing, 53, (8), 59 (1955). 
     Processes of the above nature utilizing tin/palladium systems have inherent technical and economic disadvantages. Specifically, precious metals in such systems generally exhibit a low overvoltage for hydrogen gas evolution, often resulting in excess hydrogen gas evolution during the electroplating step yielding deposits of poor integrity and porosity which are thus susceptible to chemical attack and poor adhesion. Furthermore, precious metal ions in solution, when brought into contact with metallic surfaces, e.g., copper surfaces, tend to displace the metallic surface and be deposited by a chemical displacement reaction. Such effect is costly and often tends to produce poor adherent conditions. In some cases, too much palladium is deposited, leading to over-catalyzation. See D. Grabbe, &#34;Multilayer board plated-thru-hole Failure Mechanisms,&#34; 10th Ann. Proc. Reliability Physics, (IEEE), 1972. Furthermore, such systems cause contamination of the electroless plating baths with palladium, resulting in non-uniform coating and necessitating frequent replacing of the electroless plating baths, high operating costs because of the required use of noble metal ions, and increased costs resulting from the necessity of employing a stabilizer in such baths to inhibit oxidation and hydrolytic reactions of the stannous ions. 
     The aforesaid disadvantages attendant in the use of palladium or other noble metals are overcome by the process described in copending and commonly assigned U.S. application Ser. No. 521,901, which is incorporated by reference, filed Nov. 8, 1974 as a continuation-in-part of U.S. application Ser. No. 422,774, filed Dec. 7, 1973. In the process described therein, the dielectric substrate is treated with stannous and copper ions, either simultaneously or in sequence, the ions then being reduced to a lower oxidation state by treatment with a reducing agent. The substrate is then electrolessly coated by conventional procedures. 
     Another system utilizing non-precious metal ions is described in U.S. Pat. Nos. 3,772,055 and 3,772,078 to Polichette et al. In the systems described therein, the dielectric substrate to be plated is immersed in a solution of non-precious metal ions, and then dried to promote adherence of the ions to the dielectric surface. The ions may then be reduced to the metallic state by heat or chemical means. A system of this nature is a significant departure from the standard commercial process as a result of the required intermediate drying step to achieve the required adhesion. In standard commercial processes, the article to be plated is passed from one aqueous treating tank to another with intermediate rinsing steps to remove excessive material. Due to the automated nature of most plating operations any new process must be essentially the same procedure. Any significant deviation would require a major modification in standard equipment and procedures, thus rendering the process unattractive and costly. A process for electroless plating, to be commercially feasible must be adaptable to commercial processing techniques. 
     There is a need for electroless plating compositions and processes overcoming the aforesaid disadvantages while still being compatible with commercial procedures. The present invention provides such compositions and processes. 
     SUMMARY OF THE INVENTION 
     It is the principle object of the present invention to provide an effective and economical process for preparing dielectric substrates for electroless coating or plating of a metallic surface thereon, and to provide an electroless coating process including such preparation. 
     It is a particular object of the present invention to provide a process for preparing dielectric substrates for electroless plating which does not involve the use of stannous ions, thus avoiding the disadvantages attendant in such use. It is yet another object to provide a process of the nature in which the necessity of using noble metals is eliminated. 
     It is another object to the present invention to provide improved compositions for use in the electroless plating of dielectric substrates. 
     It is another object of the present invention to provide compositions and processes for the electroless plating of dielectric substrates which are compatible with commercial procedures. Other objects of the present invention, if not specifically set forth herein, will be apparent to the skilled artisan upon the reading of the detailed description of the invention which follows. 
     Surprisingly, it has been discovered that the aforesaid objectives may be achieved by a process comprising the coating of a dielectric substrate, which has preferably first been etched by conventional means to improve adherence, with a hydrous oxide colloid of non-precious metal ions preferably selected from the group consisting of copper, nickel and cobalt followed by reduction to a reduced or elemental state with a suitable reducing agent e.g., hydrazine sulfate, sodium borohydride, etc. to activate the surface for subsequent electroless coating. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The process of the present invention is applicable to the metallic plating of a wide variety of dielectric substrates, but will normally be employed commercially in the metallic plating of plastics such as ABS. Other dielectric substrates described in the prior art, including thermoplastic and thermosetting resins and glass, may also be suitably plated in accordance with the present invention. Normally, these substrates will be etched, e.g., by treatment with a solution of chromium oxide and sulfuric acid, prior to plating in order to improve adherence of the metallic coating. 
     The term &#34;hydrous oxide&#34; as used herein, is intended to encompass the insoluble oxides, insoluble hydroxides, insoluble oxides--hydroxides or insoluble mixtures of oxides and hydroxides of metals preferably selected from the group consisting of cobalt, nickel, copper, and mixtures thereof. 
     It is also recognized that metallic colloids (e.g., copper and nickel and alloys) due to their pyrophoric nature when in contact with air and water are really metallic nuclei with an outer surface which is oxidized. Due to the catalytic phenomenon on hand it is the surface properties which are of greatest interest. Hence, it should be recognized that in the use of pyrophoric metallic particles for the present catalytic solutions, they may be considered hydrous oxide colloids, and such use falls within the spirit of this invention. 
     The hydrous oxide colloids of the present invention are generally prepared by adding the selected element or a salt thereof e.g., the sulfate nitrate or acetate salt, to an aqueous medium to produce an aqueous solution. Next a hydrolysis and nucleation reaction is permitted or caused to take place at a controlled rate until the hydrous oxide is formed in situ, the hydrous oxide exceeding the solubility limits of the solution, thus forming a colloid. As is well known in the prior art, the pH of the aqueous medium, preferably formed using deionized water, is adjusted to prevent precipitation or flocculation. The formation of hydrous oxides is well known in the prior art as exemplified by Inorganic Colloid Chemistry by H. B. Weiser, Vol. II, John Wiley and Sons, Inc., New York (1935); Inorganic Chemistry, An Advanced Textbook, by T. Aloeller, John Willey and Sons, Inc., New York (1952); and U.S. Pat. No. 3,657,003. 
     One approach for the production of hydrous oxide colloid has been described in U.S. Pat. No. 2,438,230; however, such approach while it is simple to implement does not provide as a great freedom with respect to selectivity of colloid formed and their properties as those produced by the precipitation technique. U.S. Pat. No. 3,635,668 describes a process for the production of copper hydrate suitable for use as a fungicide. For instance U.S. Pat. No. 3,082,103 demonstrates a universal milling technique by which finely divided oxides may be formed. It should also be noted that while most of the examples in the above reference are directed to formation of the colloidal solutions via precipitation techniques, the present invention is not limited to this approach. Specifically, primer catalytic collodial solutions may also be prepared by the dissolution and stabilization of properly prepared oxides or hydroxide powders. Hence the manner by which the chemical components are used in preparing said colloidal primer catalytic solutions is a matter of convenience, e.g., shipping costs. The precipitation technique in producing the catalytic medium is believed however to possess certain advantages. Specifically, this technique is potentially capable of producing colloids of varied size, shape, and chemical make-up. This freedom in features is especially useful with respect to the subsequent catalytic properties desired. In the event that the colloids are prepared by a precipitation technique, it is further recommended that after centrifugation, washing and redispersion in pure water be undertaken thereby removing extraneous ionic species and insuring a medium with low ionic strength. In use, it is also recommended that mild agitation (mechanical, gas dispersion and thermal) be applied to the solution composed of the colloidal particles. 
     The stability of the above colloidal solutions may be enhanced by various techniques, e.g., dialysis, repetitive centrifugation and washings, as well as by the addition of various materials, referred to herein as stabilizers. The term stabilizer is used to generally describe substrates believed to be adsorbed onto the colloids thereby altering the charge characteristics of said colloids and thus preventing their coagulation. 
     Stabilizers contemplated by the present invention include secondary colloids, polyalcohols and sugars which, while themselves do not serve the catalyze the dielectric substrate in this process, are believed to stabilize the active hydrous oxide colloid by an encapsulation mechanism. 
     Typical secondary colloids are gum arabic, gelatin, agar agar, starch, albumim, hemoglobin, cellulose derivatives such as carboxymethyl cellulose and hydroxypropyl cellulose, N-alkylbeta-aminopropionic acid, carboxymethyl dextran, and the like. Typical sugars include mannitol, sorbitol, dulcitol maltose, and arbinose raffinose. 
     Surfactants may also be suitably employed as a stabilizer for the hydrous oxide colloids. The surfactant, or surface active agent, as used herein generally refers to substances which are capable of lowering the surface tension of a liquid or the interfacial tension between two liquids. All such substances possess the common feature of a water-soluble (hydrophilic) group attached to an organic (hydrophobic) chain. Surfactants as used herein are also intended to encompass detergents and emulsifing agents. 
     It is also contemplated that a mixture of surfactants or surfactants with other stabilizers may be used. Care should be exercised in the use of surfactants in the preparation of the present hydrous oxide colloids, as would be noted by anyone skilled in the art, whereas the use of excess surfactants may lead to a charge reversal. 
     Suitable reducing agents, i.e., developers, for use in the present invention are compositions or compounds which will reduce the non-precious metal, e.g., copper, nickel or cobalt, ions of the hydrous oxide to a lower valence or elemental state. Exemplary of such reducing agents, which are normally employed in the aqueous state, are dimethylamine borane (DMAB), diethylhydroxylamine, N-alkyl-borazones, borazenes, borazines and mixtures therof. Of particular utility are the alkali metal and alkaline earth metal borohydrides, such as the potassium and sodium borohydrides. 
     In general, the electroless coating process of the present invention comprises contacting, e.g., by immersion, the dielectric substrate, preferably previously etched with the hydrous oxide colloid, i.e., the colloidal catalytic solution, washing the substrate with deionized water and then contacting the hydrous oxide colloid adsorbed substrate with the reducing agent to form a discontinuous coating of the metal of the reduced oxidation state on the surface of the substrate, thus forming the catalytic nuclei active for the initiation of the electroless process upon subsequent immersion of the substrate in an appropriate electroless plating bath. 
     More specifically, the improved process of the present invention is comprised of the following sequence of steps followed by electroless plating. 
     (1) immersing a dielectric substrate in a solution comprised of a hydrous oxide colloid of a non-precious metal, preferably selected from the group consisting of copper, nickel, cobalt and mixtures thereof. 
     (2) Rinsing the substrate with water to remove excess colloid; 
     (3) Immersing the substrate after rinsing in a solution comprised of a reducing agent e.g., hydrazine sulfate, sodium borohydride, etc. capable of reducing the metallic ionic portion of the adsorbed colloid to a lower or zero oxidation state; and 
     (4) Optionally rinsing the substrate with water prior to electroless plating. 
     For the sake of convenience, certain of the examples set forth hereinafter will not refer to the intermediate rinsing step. A rinsing step (step 2) is, in all instances, involved however. In specific instances, it is possible to delete steps 3 and 4 as set forth above by directly immersing the substrate, after rinsing, in an electroless plating solution containing a suitable reducing agent capable of lowering the valence state of the metallic portion of the adsorbed colloid. 
     In addition to the water employed in steps (2) and (4) of the above process, the objects of the present invention are achieved using the following system of solutions: 
     (1) A hydrous oxide colloid of a non-precious metal preferably selected from the groups consisting of cobalt, nickel and copper and mixtures thereof; and 
     (2) An aqueous solution of a reducing agent which will reduce non-precious metal ions in said colloid following adsorption of said colloid onto the substrate to a lower valence or metallic state. 
    
    
     The following examples are illustrative of the present invention and are not to be take as in limitation thereof: 
     EXAMPLE 1 
     An ABS substrate was etched in a solution comprised of 400 g/l chromium oxide and 350 g/l concentrated sulfuric acid for approximately four minutes at a temperature of 70° C. Thereafter, the etched substrate was immersed in a primer solution for five minutes, the primer solution being prepared by dissolving one gram of NiCl 2 .6H 2  O in 100 milliliters of deionized water and raising the pH to 6.5 with the slow addition of one molar NaOH. The primed substrate was then rinsed and immersed in a developer solution comprised of one g/l of KBH 4  for two minutes. The substrate was then rinsed and immersed in an electroless copper bath at a temperature of 40° C. having the following composition to effect plating: 
     
         ______________________________________                                    
CaSO.sub.4 . 5H.sub.2 O                                                   
                     15 g/l                                               
EDTA (40)            68 cc/l                                              
NaOH                  9 g/l                                               
NaCN                  3 ppm                                               
Tergitol TMN         0.2 (wt. %)                                          
H.sub.2 CO (37%)     22 c/l                                               
______________________________________                                    
 
    
     EXAMPLE II 
     The electroless plating procedure of Example I was followed with the exception that the primer solution, i.e., the hydrous oxide colloid, was prepared by adding two grams of sucrose and 15 milliliters of one molar ammonium hydroxide to four millimeters of one molar cupric chloride. Good plating resulted at 25° C. 
     EXAMPLE III 
     A hydrous oxide colloid was prepared by adding five milliliter of 0.05 molar ammonium hydroxide to 20 milliliters of 0.25 molar copper acetate with good mixing. This colloid, when substituted for the colloid employed in Example I, produced good electroless plating. 
     EXAMPLE IV 
     An ABS substrate was prepared using the primer solution of Example II, developed with the developer solution of Example I. An electroless nickel plating was formed by immersion of the substrate at a temperature of 60° C. in an aqueous bath having the following composition: 
     
         ______________________________________                                    
NiSO.sub.4 . 6H.sub.2 O                                                   
                       25 g/l                                             
Na.sub.4 P.sub.2 O.sub.7 . 10H.sub.2 O                                    
                       50 g/l                                             
NH.sub.4 OH (conc.)    15 cc/l                                            
Dimethylamine                                                             
borane                  4 g/l                                             
______________________________________                                    
 
    
     EXAMPLE V 
     One gram of CoCl 2 .6H 2  O was dissolved in 100 ml of deionized water to which 0.5 ml of one molar NaOH was added. The suspension thus formed was heated for 24 hours at 65° C. and then additionally aged at room temperature for six days. Similar colloids were formed with 1.0 ml and 2.0 ml of NaOH being used. 
     EXAMPLE VI 
     The procedure of Example V was repeated substituting NiCl 2  6H 2  O for CoCl 2 .6H 2  O. 
     EXAMPLE VII 
     ABS substrates were immersed in the colloids of Example V and VI for five minutes at room temperature followed by rinsing and immersion in a developer solution containing 1 g/l KBH 4  at pH 8.5 for 2 to 5 minutes to reduce the cobalt and nickel to a lower oxidation state. Subsequent immersion of the plates into an electroless copper bath at 40° C. produced plating in all instances. 
     EXAMPLE VIII 
     An ABS substrate was immersed in a colloidal solution formed by adding to 1600 ml of 0.0125 molar copper acetate solution. 400 ml of 0.025 molar NH 4  OH dropwise with stirring of the solution. The substrate was thereafter developed and plated in the manner described in Example VII with good results. Successful results were also achieved using a developer solution containing only 0.1 g/l KBH 4 . 
     EXAMPLE IX 
     ABS substrates prepared in accordance with Example VIII were successfully plated utilizing the following electroless nickel bath at pH 6 and a temperature of 25° C. 
     
         ______________________________________                                    
Ni.sup.++ (from a sulfamate concentrate)                                  
                          8.0 g/l                                         
Dimethylamine borane      5.0 g/l                                         
______________________________________                                    
 
    
     EXAMPLE X 
     ABS substrates prepared in accordance with Example VIII were also successfully plated utilizing the following electroless cobalt bath at pH 7.6 and 50° C. 
     
         ______________________________________                                    
CoSO.sub.4 . 7H.sub.2 O 25 g/l                                            
Disodium succinate 6H.sub.2 O                                             
                        25 g/l                                            
Dimethylamine borane     4 g/l                                            
______________________________________                                    
 
    
     EXAMPLE XI 
     The ABS substrate of Example VIII was also successfully treated using the following developer solutions: 
     1. Borane-tertbutylamine complex (2 g/l) at 25° C. and 40° C. with immersion time of 5 minutes. 
     2. Borane morphine complex (2 g/l) at 25° C. and 40° C. with immersion time of 5 minutes. 
     3. Dimethylamine borane (2 g/l and pH 11 adjusted with NaOH) at 40° C. and immersion time of 5 minutes. 
     EXAMPLE XII 
     Four hundred ml of 0.025 molar NH 4  OH was added dropwise with stirring to 1600 ml of 0.0125 molar copper acetate to form a colloidal primer solution from which other solutions were prepared and evaluated. The nature of certain surfactants added is shown in parenthesis. The process of evaluation consisted of ABS treatment in colloidal primer, developer at room temperature with a 1 gram/liter solution of KBH 4  and coating with colloidal copper at 40° C. The following results were obtained: 
     
         ______________________________________                                    
                             Plating Evaluation                           
Sol-                         after 5 days from                            
ution                                                                     
     Additive        Conc.   Preparation of Control                       
______________________________________                                    
1    NaCl            .01M    positive                                     
2    NaCOOH          .01M    positive                                     
3    Tartaric Acid   .01M    positive                                     
4    Sucrose         .01M    positive                                     
5    Sodium Lauryl Sulfate                                                
                     .01M    negative                                     
     (anionic)                                                            
6    K . Na tartrate .01M    positive                                     
7    Na nitrate      .001M   negative                                     
8    Union Carbide Tergitol                                               
                     2ml/l   positive                                     
     15-S-3 (nonionic)                                                    
9    DuPont Zonyl FSC                                                     
                     2ml/l   negative                                     
     (cationic)                                                           
10   Union Carbide - TMN                                                  
                     2ml/l   positive                                     
     surfactant (nonionic)                                                
11   Zonyl FSA (anionic)                                                  
                     2ml/l   positive                                     
12   Zonyl FSB (amphoteric)                                               
                     2ml/l   negative                                     
13   Zonyl FSN (nonionic)                                                 
                     2ml/l   positive                                     
14   Zonyl FSP (anionic)                                                  
                     2ml/l   positive                                     
15   3M FC 170 (nonionic)                                                 
                     2ml/l   positive                                     
16   3M FC 176 (nonionic)                                                 
                     2ml/l   positive                                     
17   none (control)   --     positive                                     
18   control diluted (X10)                                                
                      --     positive                                     
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     It should be noted that the surfactants used in solutions 9. 11-16 are all composed of fluorocarbon chains rather than hydrocarbon chains. Such surfactants have shown good chemical stability in a wide variety of chemical environments. 
     EXAMPLE XIII 
     Kapton, a DuPont trademark for polyimide substrates:polyethylene and phenolic substrates, were also successfully plated with the control solution of Example XII. 
     EXAMPLE XIV 
     The control solution of Example XII was also employed in coating of ABS substrates with the exception that the developer solution was diluted from 1 gr/l to 0.1 gr/l. Successful initiation of electroless plating was noted. 
     EXAMPLE XV 
     The control solutions of Example XII were used in coating ABS substrates. The alkalinity of the electroless copper solution was varied, however, from 0.089 to 0.402 molar by the addition of sodium hydroxide. Improvement in the plating uniformity was noted as the alkalinity was increased, probably due to the increased reactivity of the electroless formulation. 
     EXAMPLE XVI 
     The procedure of Example XII was followed with the exception that the following electroless copper formulation was used at 50° C.: 
     
         ______________________________________                                    
CuSO.sub.4 . 5H.sub.2 O                                                   
                       10 gr/l                                            
NaOH                   10 gr/l                                            
Sodium potassium       50 gr/l                                            
tartrate . 4H.sub.2 O                                                     
HCHO (57%)             20 cc/l                                            
______________________________________                                    
 
    
     EXAMPLE XVII 
     Utilizing the control solutions of Example XII, ABS substrates were immersed in the developer solution for two minute and fifteen minute periods. No major difference in plating results was noted. Successful coating was also obtained using glass (soda lime) substrate instead of the ABS substrate. 
     EXAMPLE XVIII 
     Since surfactants are conventionally employed in electroless processes, the following surfactants were added to a 0.05% developer solution of potassium borohydride: Union-Carbide Tergitol TMN and 15-S-3; DuPont Zonyl FSA, FSC and FSN; 3M FC-98, FC-128, FC-170, FC-134 and FC-178 is a concentration range of few mg/liter of developer solution. No improvement in plating uniformity was noted. 
     EXAMPLE XIX 
     The following colloidal solutions were prepared by first dissolving 1 gram of NiCl 2 .6H 2  O in 100 ml DI water. In each case, a varied volume of 0.1 M NaOH was added slowly with agitation. 
     
         ______________________________________                                    
Case No.   Volume of NaOH added (ml)                                      
                              Final pH                                    
______________________________________                                    
1          0.4                6.6                                         
2          1.0                7.0                                         
3          2.0                7.2                                         
4          5.0                7.3                                         
5          10.0               7.4                                         
______________________________________                                    
 
    
     These solutions were sealed and immersed at 65° C. for 48 hours. Evaluation of the colloidal solutions was undertaken following 48 hours at 65° C. and 3 days of storage at room temperature. The procedure used to evaluate was using standard ABS substrate, immersion in colloidal solution (10 minutes), rinse, immersion in developer (KBH 4  1 gr/l for 5 minutes, rinse, and electroless plating. Using the electroless copper at 40° C., induction time was slow and coverage was incomplete. Using an electroless nickel of the following composition at 45° C., results showed improved coverage and a shorter induction time in comparison to the case of copper. 
     
         ______________________________________                                    
Ni.sup.++ (from a sulfamate Conc.)                                        
                        8 g/l                                             
DMAB                    5 g/l                                             
pH                      5.3                                               
______________________________________                                    
 
    
     The difference in the behavior between nickel and copper is probably due to the fact that in the case of copper the plating process is first dependent upon the successful galvanic reaction between the copper ions in solution and the reduced nickel on the surface. 
     EXAMPLE XX 
     The solutions and procedure of Example 13 were followed in testing of the control solution with the exception that sodium borohydride was substituted for potassium borohydride. The developer was adjusted to pH 10. 
     EXAMPLE XXI 
     In certain of the preceding examples, the deposition of Ni-B (from baths containing DMAB) onto surfaces treated with a nickel colloid were described. There are, however, economic advantages in depositing Ni-P (derived from solutions containing hypophosphite reducing agents) films. In this example, previously etched ABS substrates were immersed for several minutes in the colloidal nickel solution of Example XIX, case number four, rinsed, and then immersed in one of the following developer formulations for several minutes: 
     Case 1: 1 g/l KBH 4  pH 10 at 40° C. 
     Case 2: 1 g/l KBH 4  and 10 g/l NaH 2  PO 2 .H 2  O at pH 10 at 40° C. 
     Case 3: 25 g/l NaH 2  PO 2 .H 2  O at pH 9.1 at 40° C. 
     After immersion into the developer formulation, the substrates were rinsed and immersed into an electroless nickel bath of the following composition, 
     
         ______________________________________                                    
Ni.sup.++ (from a sulfamate concentrate)                                  
                           8 g/l                                          
NaH.sub.2 PO.sub.2 . H.sub.2 O                                            
                          10 g/l                                          
pH                        6.3                                             
Temperature               40° C.                                   
______________________________________                                    
 
    
     Plating of nickel occurred using the Case 1 and Case 2 developer formulations. No plating took place using the Case 3 developer formulation, however, for reasons which are not presently apparent. 
     EXAMPLE XXII 
     A copper colloid which initiated plating directly was prepared according to a procedure suggested by Weiser. &#34;Inorganic Colloid Chemistry&#34;. Vol. 1. p. 137. In this preparation, 40 ml of 0.01 M CuSO 4  was heated to 80° C. 10 ml of 0.5% H 3  PO 2  was added during stirring of solution at an approximate rate of 3 ml/min. Etched ABS substrates were immersed in the resulting colloid for 10 minutes, rinsed and directly immersed into the electroless copper solution of Example I at 45° C. Plating was noted to take place. 
     EXAMPLE XXIII 
     A colloidal nickel solution was prepared as follows: 25 ml of 0.005 M solution of potassium borohydride was added slowly to a solution composed of 30 ml of 0.0025 M nickel acetate and 0.1 ml of CF-54 surfactant (product of Rohm &amp; Haas). After immersion of the test substrate in the above printing solution, it was found necessary to activate the surface by further immersion in a reducing agent solution (e.g., 1 g/l KBH 4 ). Immersion in the electroless copper bath resulted in good initiation and coverage. 
     EXAMPLE XXIV 
     Colloidal cuprous oxide solutions were prepared according to MacFadyon, &#34;J. Colloid and Interface Science&#34; 44, 95 (1973), Run No. 13, Table I. Etched ABS substrates were immersed in the colloidal solutions at 40° C., rinsed developed by immersion in 1 g/l KBH 4 , and immersed in the electroless copper formulation of Example I. In all cases, good plating was noted. 
     EXAMPLE XXV 
     A positively charged colloid of copper was prepared by the thermal aging (18 hours at 75° C.) of a solution composed of 1×10 -3  M CuSO 4 , 2×10 -3  M NaOH and 4.0×10 -3  M, a cationic surfactant represented by the structure C 12  -C 14  NH(CH 2  CH 2  O) 15  H, with a final pH of 5.2. Using the above colloid with ABS at 40° C. with 1.5 g/l KBH 4  (5 minutes) and the electroless copper bath of Example I, good initiation and plating took place. 
     EXAMPLE XXVI 
     A negatively charged colloid of copper was prepared by the thermal aging (18 hours at 75° C.) of a solution composed of 1×10 -3  M CuSO 4 . 2×10 -3  M NaOH and 4.0×10 -3  M sodium lauryl sulfate with a final pH of 9.8. Using ABS with the above procedure and compositions, no plating took place. 
     EXAMPLE XXVII 
     A colloidal hydrous oxide solution of nickel was prepared in a similar fashion to Example XXV above with a final pH of 7.6. This colloidal solution was used at 40° C. followed by a developer solution (1.5 g/l KBH 4 ) with 5 minutes immersion time. The electroless nickel bath was similar to that of Example XXI except for the lowering of the nickel content to 5.5 g/l. Good plating was noted here as well as in the electroless copper of Example I. Preparing an hydrous oxide colloid of nickel similar to that of Example XXVI with a final pH of 11.3 did not yield effective plating with nickel under the conditions and procedure employed. It was also found that cobalt colloids were prepared in a similar fashion as the nickel ones. 
     EXAMPLE XXVIII 
     Colloidal catalytic hydrous oxides of copper and nickel were prepared by aging (18 hours at 75° C.) solutions composed of 9×10 -4  M NiSO 4 , 1×10 -4  M CuSO 4 , 2×10 -3  M NaOH and 4×10 -3  M of the cationic surfactant of Example XXV with a final pH of 4.4. Using the above binary colloidal solution at 40° C. and developer solution (1.5 g/l KBH 4 , 5 minutes) with a commercial electroless copper bath (Sel-Rex Oxytron Cu #990) at 31° C. gave good plating results; however, using the single colloids under the same conditions did not produce as good quality plating coverage. It was also found that due to the apparent greater activity of the catalytic surface, reduced concentrations of developer solutions may be used in conjunction with the electroless copper of Example I. It is recognized that cobalt may be substituted for nickel. 
     EXAMPLE XXIX 
     Ferric and chromium hydrous oxide colloids were prepared by aging at 75° C. for 18 hours the following compositions: 1×10 -3  M FeCl 3 , 2×10 -3  M NaOH and 4×10 -3  M of the cationic surfactant of Example XXV with a final pH=10.5; and 1×10 -3  M Cr(NO 3 ) 3 , 2×10 -3  M NaOH and 4×10 -3  M surfactant with a final pH=4.2. These primer solutions used at 40° C. with 1.5 g/l KBH 4  and electroless copper bath (of Example I) at 40° C. showed some evidence of plating on ABS substrate, and it should be recognized that increasing the developer concentration, or the colloid concentration, or both, could also bring the conditions for plating to an optimum. 
     In the primer solution and the ferric acid chromium ions are adsorbed onto the substrate and then reduced to the zero oxidation state when immersed in the developer solution. After the developer solution the substrate is then immersed in the electroless copper bath. It is believed in this solution a replacement mechanism occurs in which the copper replaces the iron (or chromium) on the substrate (e.g., Cu +2  +Fe°→Cu°) after which electroless initiation about the copper (Cu°) sites takes place. It is this replacement reaction which has been illustrated here in the previous example. It should be noted that this is only an example of the initiation mechanism and that any metal which will work for this mechanism falls within the contemplation of the present invention. Such metals are those having a more negative reduction potential than copper. Typical metals which fall into this category for use with electroless copper baths are iron, zinc and chromium. 
     Accordingly, any metallic nucleus which is more active with respect to copper ions or nickel ions contained within the electroless formulation could be a candidate with said metal nuclei derived from the adsorption of colloid of hydrous oxide and its reduction prior to the electroless plating strip. 
     EXAMPLE XXX 
     Several colloidal solutions of copper (5×10 -2  M) were prepared and aged with a final pH of 9. In this series of solutions the surfactant, sodium salt of Lauryl sulfate, was varied in the molar ratio to copper from 1/4 to 3 times. Using etched ABS and 0.5 g/l KBH 4  effective plating took place using the electroless copper of Example I. 
     EXAMPLE XXXI 
     Hydrous oxide copper colloids are prepared similarly to Example XXX with the addition singularly of the following additives: 
     
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Gum Arabic           4 mg/l                                               
Ethylene Glycol      25 ml/l                                              
Polyethylene Glycol  0.025 molar                                          
(M.W. average 1000)                                                       
Tannic Acid          5 × 10.sup.-3 molar                            
Glycerol             25 ml/l                                              
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     Effective colloids were formed. 
     As noted in Example XXIX, hydrous oxide colloids of metals other than copper, nickel and cobalt may be employed in the practice of the present invention. Substrates treated with such colloids, however, when immersed in an electroless plating bath, must first undergo a replacement reaction between a portion of the metal on the surface and the metal ions e.g., copper, in the electroless bath before the surface is catalytic. This initial replacement reaction not only renders the process slower, and thus less commercially desirable, but increases the number of interfaces between the dielectric substrate and the outer plating. 
     In this latter regard, it is recognized in the prior art that an increase in the number of interfaces may decrease the adherence of the overall coating i.e. the overall process reliability. In the present invention, when using the preferred hydrous oxide colloids of copper, nickel or cobalt, only one layer is present between the dielectric substrate and electroless coating. In conventional tin/palladium systems, however, two intermediate layers are present. 
     In the practice of the present invention, an increase in the reactivity of the collidal primers has been found to permit a decrease in the reactivity of the developer solutions. The latter may be modified by changes in the concentration of the reducing agent used and/or changing the nature of the agent used. Methods for increasing colloidal reactivity may include concentration, temperature, particle size and charge modifications. The ability to use developers of lower reactivity is a significant cost savings and means for the use of less expensive reducing agents. 
     The present invention is also effective in the formation of selective images on dielectric substrates, e.g., in the manufacture of printed circuits, utilizing cuprous oxide colloidal solutions by a process comprised of the following steps: 
     (1) Coating a dielectric substrate with a solution of a cuprous oxide colloid; 
     (2) Rinsing the substrate to remove excess colloid; 
     (3) Partially drying the substrate: 
     (4) Exposing selected portions of the substrate to actinic radiation; 
     (5) Contacting the exposed substrate with an electroless plating bath to form a real image and; 
     (6) Optionally, plating the substrate by electrolytic means. 
     It should also be recognized that while a specific colloidal medium may be effective on one substrate, this does not provide an assurance that the same would work on other substrate(s). A typical case encountered is the treatment of etched ABS and Noryl substrates. The difference in behavior is presumably due to the difference in the surface charge of these etched surfaces. It should also be recognized that this difference in behavior is not new and has been encountered in this art in using the colloidal catalytic solution based upon the admixture of acidic stannous chloride and palladium. 
     In the art of plating of plastics and printed circuits, not all surfaces (e.g. etched ABS vs. Noryl) have the same surface charge. It is thus obvious to those skilled in the art that the priming colloidal catalytic medium must be applicable to all surfaces and not be limited to a few. It should be obvious to those skilled in the art that a system containing aqueous solutions of metallic salts (e.g., CuSO 4 ) could not be effective on all surfaces which differ in the sign of their surface charge. It is thus the purpose of this invention to provide with primiing solutions which would be applicable to all substrates of commercial interest independent of their surface charge. It should thus be recognized that the application of the primer colloidal solutions and the ability to charge said colloid in a desired fashion thus permits effective adsorption on desired surfaces without limitation to specific subtrates. 
     It should also be obvious that various approaches may be taken in the charging of such colloids, e.g., controlled addition of compound with specific anions such as hydroxl ions and/or controlled addition of suitable surfactants and/or secondary colloids. It should also be recognized that depending upon the nature of surfactant being added, a reversal in charge may take place; this behavior depends upon the nature of the surfactant used (e.g., cationic vs. anionic, etc.) 
     It should be noted that the immersion times given in the examples are tailored for the etched standard ABS substrates used (Lustran PG 299 Grey Product of Monsanto Co.). Substitution of other dielectric substrates may require alteration in the immersion times based upon the absorption rate of the colloids. This optimum immersion time could be determined by simple experimental procedure. 
     It will be obvious to the skilled artisan that certain conditions normally observed in electroless coating technology should also be observed in the practice of the present invention. For example, the catalytic specie(s) present on the surface must interact with the reducing agent(s) present in the electroless plating bath. In this respect it is well known in the art that Ni-P type deposits (derived from hypophosphite containing baths) do not self initiate upon copper surfaces; however, Ni-B type deposits (derived from dimethylamine borane containing baths) do initiate on the same copper surface. The difference encountered is due to the choice of the reducing agent present. It is further possible that the initiation of the plating process takes place first via a galvanic replacement type reaction of the metallic ions in solution with the catalytic surface. A typical example is the immersion of a copper substrate into an electroless gold plating formulation. Furthermore, in choosing a specific electroless formulation , it is essential to know that none of the components present (complexing agents, pH adjuster, stabilizers, etc.) in the electroless formulation is capable of deactivating the catalytic surface either by dissolution or other mechanism and thus compatible electroless formulations should be selected. 
     While it is stated in this application the one should use compatible electroless plating formulations, this restriction is eliminated according to findings covered under a separate application. 
     It will be obvious upon a reading of the preceding description that the processes of the invention are especially useful in printed circuitry fabrication encompassing fully additive methods, semiadditive methods, and subtractive with through-hole metallization. 
     It will be further obvious to one skilled in the pertinent art that many modifications and variations may be made in the preceding description without departing from the spirit and scope of the present invention. For example, it will be apparent that mixtures of reducing agents may be used in a single developer solution or may be used in successive steps. Furthermore, it is within the scope of the present invention to delete the use of a separate developer solution by directly immersing the primed substrate in an electroless plating formulation containing one or more reducing agents capable of reducing the oxidation state of the primed surface.