Process for bonding metals to electrophoretically deposited resin coatings

• US 4,601,916 A
• Filed: 07/18/1984
• Issued: 07/22/1986
• Est. Priority Date: 07/18/1984
• Status: Expired due to Fees

• Current Assignee: Amp-Akzo Corporation
• Original Assignee: Kollmorgen Technologies Corporation
• Inventors: Arachtingi, James J.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US06/632,041
• Time in Patent Office: 734 Days
• Field of Search: 427/97, 427/98, 427/435, 204/181 R, 204/181 C, 428/131, 428/209, 428/901
• US Class Current: 204/479
• CPC Class Codes: C25D 13/00 Electrophoretic coating characterised by the process C25D15/00 takes precedence; compositions for electrophoretic coating C09D5/44
• CPC Class Codes: H05K 1/056 the metal substrate being covered by an organic insulating layer
• CPC Class Codes: H05K 2201/0209 Inorganic, non-metallic particles
• CPC Class Codes: H05K 2201/09581 Applying an insulating coating on the walls of holes
• CPC Class Codes: H05K 2203/0315 Oxidising metal
• CPC Class Codes: H05K 2203/0323 Working metal substrate or core, e.g. by etching, deforming
• CPC Class Codes: H05K 2203/1184 Underetching, e.g. etching of substrate under conductors or etching of conductor under dielectrics; Means for allowing or controlling underetching
• CPC Class Codes: H05K 2203/135 Electrophoretic deposition of insulating material
• CPC Class Codes: H05K 2203/1438 Treating holes after another process, e.g. coating holes after coating the substrate
• CPC Class Codes: H05K 3/385 by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
• CPC Class Codes: H05K 3/422 characterised by electroless plating method; pretreatment therefor
• CPC Class Codes: H05K 3/427 initial plating of through-holes in metal-clad substrates
• CPC Class Codes: H05K 3/44 Manufacturing insulated metal core circuits or other insulated electrically conductive core circuits H05K3/0058, H05K3/4608, and H05K3/4641 take precedence
• CPC Class Codes: H05K 3/445 having insulated holes or insulated via connections through the metal core
• CPC Class Codes: Y10S 428/901 Printed circuit
• CPC Class Codes: Y10T 428/24273 including aperture
• CPC Class Codes: Y10T 428/24917 including metal layer

Abstract

An economical process for producing metal plated through holes in metal core circuit boards which permits the formation of small holes and fine conductor lines is disclosed. A metal sheet, which will become the core of a metal core circuit board, is provided with insulation layers on both sides, and through holes are provided through the insulation layers. The process involves incorporating fillers in a resinous coating solution which is electrophoretically applied to the hole walls to form an insulating layer of uniform thickness thereon. An increased diameter in the metal wall portion of each hole acts to restrict flow of the filled resinous coating solution during cure resulting in a straight hole wall. The coating is adhesion promoted and a metal layer is deposited thereon.

Claims

1. In a process for producing a printed circuit on an insulated metal substrate, which process includes providing one or more insulating layers on surfaces of a metal sheet to form the insulated metal substrate;

providing one or more holes through the insulated substrate for through connections;

etching the hole walls defined by the metal sheet to enlarge by a predetermined amount only the portion of the holes extending through the metal sheet, electrophoretically depositing a resinous coating comprising a cathodic or anodic electrophoretic thermosetting resin from a solution thereof on the etched portion of the hole walls;

curing the resinous coating; and

forming the printed circuit on the surface of the insulating layers and on the walls of the holes;

the improvement comprising;

incorporating in the resin solution a solid filler in finely divided form and having an average particle size of about 1 micron or less, the filler being non-resinous, inorganic, non-reactive with the solution and uniformly dispersed therethrough, the filler being capable of improving the adhesion of a metal layer to the electrophoretically deposited resinous coating after the coating is adhesion promoted, the resinous coating containing the filler having a volume resistivity greater than 10⁴ megohm-cm between the printed circuit conductor and the metal sheet;

electrophoretically depositing the resinous coating and the filler from the solution onto the metal wall portions of the holes, the deposited coating having fillers dispersed therethrough;

curing the resinous coating, the thickness of the cured resinous coating being between about 0.025 mm and about 0.055 mm, the cured resinous coating being comprised of (a) 1% to 25% by weight of said filler, and (b) the balance being said thermosetting resin;

adhesion promoting the surface of the resinous coating containing the filler to create a hydrophilic, microetched surface on the coating;

depositing a metal layer on the surface of the resinous coating on the hole walls, and on the insulating layers, the metal layer deposited on the microetched surface of the resinous coating being continuous and free of blisters, and

forming said printed circuit on the insulated metal substrate.

2. A process as defined in claim 1, wherein the solid filler is selected from the group consisting of clays, silicas, aluminas, silicates, earths, barium sulfide, zinc oxide and titanium dioxide.

3. A process as defined in claim 1, wherein the adhesion promotion is accomplished by oxidation.

4. A process as defined in claim 3, wherein the oxidation is accomplished by an aqueous oxidizing solution.

5. A process as defined in claim 1, wherein the adhesion promotion is accomplished with a hexavalent chromium solution.

6. A process as defined in claim 1, wherein the adhesion promotion is accomplished with a first acid solution and a second oxidizing solution, said second oxidizing solution comprising hexavalent chromium.

7. A process as defined in claim 1 wherein the metal layer deposited on the microetched surface of the resinous coating passes a tape test.

8. A process as defined in claim 1, wherein the metal layer deposited on the microetched surface of the resinous coating adheres to the coating with a peel strength of at least about 0.1 N/mm.

13. A process as defined in claim 2 wherein said filler is a clay.

14. A process as defined in claim 13 wherein said clay is a hydrous aluminum silicate clay with an average particle size of 0.5 micrometers.

9. In a process for producing a printed circuit on an insulated metal substrate comprised of a metal sheet with insulating surface layers in which the substrate is provided with holes for through connections, the portions of hole walls extending through the metal sheet are enlarged by a predetermined amount and metal wall portions of the holes are insulated with a resinous coating electrophoretically deposited from a solution thereof, the solution comprising an anodic or cathodic electrophoretic epoxy resin, the improvement comprising:

incorporating in the resin solution a solid filler in particulate form, the average particle size of which is finer than about 1 micron in diameter, said filler being non-resinous, inorganic, non-reactive with the solution and uniformly dispersed therethrough, the filler being capable of improving the adhesion of a metal layer to the electrophoretically deposited resinous coating after the coating is adhesion promoted, the filler being selected from the group consisting of clays, aluminas, silicates, earths, barium sulfate, zinc oxide and titanium dioxide, the resinous coating containing the filler having a volume restivity greater than 10⁴ megohm-cm between the printed circuit conductor and the metal sheet;

electrophoretically depositing the resinous coating and filler from the solution onto the metal wall portions of the holes, the deposited coating having filler uniformly dispersed therethrough;

curing the resinous coating, the thickness of the coating after curing being between about 0.025 mm and about 0.055 mm, the cured resinous coating being comprised of 1 to 25% by weight of said filler, the balance being said epoxy resin;

adhesion promoting the surface of the resinous coating with an aqueous oxidizing solution to create a hydrophilic, microetched surface on the coating;

depositing a metal layer on the surface of the resinous coating on the hole walls, and on the insulating surface layers, the metal layer deposited on the microetched surface of the resinous coating being continuous and free of blisters, and

forming said printed circuit on the insulated metal substrate.

10. A process for depositing an adherent metallic film on at least part of a surface of a metal substrate coated with an electrophoretically deposited resinous coating, the resinous coating including a anodic or cathodic electrophoretic thermosetting resin, the process comprising:

(a) incorporating in the resinous coating a filler in finely divided form selected from the group consisting of clays, alumina, silica, silicates, earths, barium sulfate, zinc oxide and titanium dioxide;

(b) electrophoretically depositing the resinous coating onto the surface of a metal substrate;

(c) curing said resinous coating, the cured resinous coating being comprised of 1% to 25% by weight of said filler, the balance being said thermosetting resin;

(d) adhesion promoting the surface of said resinous coating to expose some of the filler and to create a microporous, hydrophilic surface on at least part of the coating, wherein the adhesion promotion is accomplished with a first acid solution followed by a second oxidizing solution, said second oxidizing solution comprising hexavalent chromium; and

(e) electrolessly depositing an adherent metallic film on the part of the surface which has been adhesion promoted, the metal film deposited being continuous, free of blisters and adhering to the resinous coating when tested with a pressure-sensitive tape.

11. A process as defined in claim 10, wherein the hexavalent chromium compound is chromium trioxide.

12. A process as defined in claim 11, wherein the aqueous solution of chromium trioxide comprises 400-900 g/l.

15. A process as defined in claim 10, wherein said filler is a clay.

16. A process as defined in claim 15, wherein said clay is a hydrous aluminum silicate clay with an average particle size of 0.5 micrometers.