US3373113A - Process for etching copper printed circuits - Google Patents
Process for etching copper printed circuits Download PDFInfo
- Publication number
- US3373113A US3373113A US480750A US48075065A US3373113A US 3373113 A US3373113 A US 3373113A US 480750 A US480750 A US 480750A US 48075065 A US48075065 A US 48075065A US 3373113 A US3373113 A US 3373113A
- Authority
- US
- United States
- Prior art keywords
- etching
- printed circuits
- copper
- printed
- solution
- 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
Links
- 238000005530 etching Methods 0.000 title description 31
- 239000010949 copper Substances 0.000 title description 18
- 238000000034 method Methods 0.000 title description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 15
- 229910052802 copper Inorganic materials 0.000 title description 15
- 239000000243 solution Substances 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229940108928 copper Drugs 0.000 description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 235000010755 mineral Nutrition 0.000 description 11
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- -1 H 80 Chemical class 0.000 description 3
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Definitions
- the present invention concerns a process for etching the portions of the copper printed circuits which are not protected by printing ink.
- an insulating backing is first provided with a copper coating 35 or 70 m. thick which is then printed with an etch resistant printing ink on the portions which should be retained as conductor lines after the etching.
- the etching is effected by spraying the printed plates with an etching liquid or by dipping such printed plates in an etching bath in order to dissolve the copper which is not protected by the printed resist.
- Usual etching liquids are strong mineral acids such as H 80, and HNO;,, as well as chromic acid, iron chloride or ammonium persulfate solutions.
- H 80, and HNO mineral acids
- chromic acid iron chloride or ammonium persulfate solutions.
- the use of such solutions entail certain disadvantages.
- ammonium persulfate While several disadvantages could be avoided by the use of ammonium persulfate, its use still has several drawbacks. As ammonium persulfate only attacks the copper slowly, it is necessary to add activators or the solution is activated with heat. In spite of this the etching periods necessary, even though not very great, are still longer than those required for iron chloride. Ammonium persulfate solutions can only effectively be used in a concentration range of 150 to 250 g./liter of water.
- H O activated mineral acid baths
- the essence of the process according to the invention resides in the use of aqueous H O, containing mineral acid solutions which in addition contain phosphoric acid, as stabilizer, for the etching of printed circuits.
- a process for etching printed copper circuits which comprises contacting the printed copper circuit with an aqueous etching solution of a mineral acid selected from the group consisting of sulfuric acid and nitric acid containing H O, as an activator for the mineral acid, the step of incorporating an effective stabilizing amount of H PO, as a stabilizer for the H 0 in said aqueous etching solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED45263A DE1253008B (de) | 1964-08-22 | 1964-08-22 | Verfahren zum AEtzen von Kupferfolien fuer die Herstellung von gedruckten Schaltungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3373113A true US3373113A (en) | 1968-03-12 |
Family
ID=7048878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US480750A Expired - Lifetime US3373113A (en) | 1964-08-22 | 1965-08-18 | Process for etching copper printed circuits |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3373113A (OSRAM) |
| BE (1) | BE668423A (OSRAM) |
| DE (1) | DE1253008B (OSRAM) |
| FR (1) | FR1442848A (OSRAM) |
| GB (1) | GB1063007A (OSRAM) |
| NL (1) | NL6510928A (OSRAM) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3864271A (en) * | 1972-12-04 | 1975-02-04 | Du Pont | Stabilized acidic hydrogen peroxide solutions |
| US3869401A (en) * | 1972-12-04 | 1975-03-04 | Du Pont | Stabilized acidic hydrogen peroxide solutions |
| US3892833A (en) * | 1972-11-10 | 1975-07-01 | Matsushita Electric Industrial Co Ltd | Method of making an ion-selective electrode |
| US3905907A (en) * | 1972-12-22 | 1975-09-16 | Furukawa Electric Co Ltd | Solutions for chemical dissolution treatment of metal materials |
| US3953263A (en) * | 1973-11-26 | 1976-04-27 | Hitachi, Ltd. | Process for preventing the formation of nitrogen monoxide in treatment of metals with nitric acid or mixed acid |
| US4051001A (en) * | 1974-08-26 | 1977-09-27 | Hitachi, Ltd. | Process for regenerating etching solution |
| US4356069A (en) * | 1981-03-09 | 1982-10-26 | Ross Cunningham | Stripping composition and method for preparing and using same |
| US4401509A (en) * | 1982-09-07 | 1983-08-30 | Fmc Corporation | Composition and process for printed circuit etching using a sulfuric acid solution containing hydrogen peroxide |
| US4491500A (en) * | 1984-02-17 | 1985-01-01 | Rem Chemicals, Inc. | Method for refinement of metal surfaces |
| US4497687A (en) * | 1983-07-28 | 1985-02-05 | Psi Star, Inc. | Aqueous process for etching cooper and other metals |
| EP0079505B1 (en) * | 1981-10-29 | 1987-02-04 | LeaRonal, Inc. | A method of recovering copper from spent etch solutions |
| EP0387057A1 (en) * | 1989-03-08 | 1990-09-12 | Tokai Denka Kogyo Kabushiki Kaisha | Surface-treating agents for copper and copper alloy |
| US5362712A (en) * | 1990-08-17 | 1994-11-08 | Hoechst Aktiengesellschaft | Process for removing a copper mold from a molded body |
| US5364549A (en) * | 1989-10-05 | 1994-11-15 | Interox Chemicals Limited | Hydrogen peroxide solutions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2923608A (en) * | 1956-04-13 | 1960-02-02 | Fmc Corp | Method of improving the bonding properties of steel surfaces |
| US2978301A (en) * | 1957-01-11 | 1961-04-04 | Fmc Corp | Process and composition for the dissolution of copper |
| US2982625A (en) * | 1957-03-22 | 1961-05-02 | Sylvania Electric Prod | Etchant and method |
| GB955000A (en) * | 1961-04-13 | 1964-04-08 | Marconi Co Ltd | Improvements in or relating to copper etching solutions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2211400A (en) * | 1938-08-10 | 1940-08-13 | Chase Brass & Copper Co | Pickling solution for copper-base alloys |
| US2428804A (en) * | 1945-09-07 | 1947-10-14 | Esther M Terry | Copper cleaning composition |
-
1964
- 1964-08-22 DE DED45263A patent/DE1253008B/de active Pending
-
1965
- 1965-07-31 FR FR26820A patent/FR1442848A/fr not_active Expired
- 1965-08-04 GB GB33405/65A patent/GB1063007A/en not_active Expired
- 1965-08-17 BE BE668423D patent/BE668423A/xx unknown
- 1965-08-18 US US480750A patent/US3373113A/en not_active Expired - Lifetime
- 1965-08-20 NL NL6510928A patent/NL6510928A/xx unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2923608A (en) * | 1956-04-13 | 1960-02-02 | Fmc Corp | Method of improving the bonding properties of steel surfaces |
| US2978301A (en) * | 1957-01-11 | 1961-04-04 | Fmc Corp | Process and composition for the dissolution of copper |
| US2982625A (en) * | 1957-03-22 | 1961-05-02 | Sylvania Electric Prod | Etchant and method |
| GB955000A (en) * | 1961-04-13 | 1964-04-08 | Marconi Co Ltd | Improvements in or relating to copper etching solutions |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3892833A (en) * | 1972-11-10 | 1975-07-01 | Matsushita Electric Industrial Co Ltd | Method of making an ion-selective electrode |
| US3864271A (en) * | 1972-12-04 | 1975-02-04 | Du Pont | Stabilized acidic hydrogen peroxide solutions |
| US3869401A (en) * | 1972-12-04 | 1975-03-04 | Du Pont | Stabilized acidic hydrogen peroxide solutions |
| US3905907A (en) * | 1972-12-22 | 1975-09-16 | Furukawa Electric Co Ltd | Solutions for chemical dissolution treatment of metal materials |
| US3953263A (en) * | 1973-11-26 | 1976-04-27 | Hitachi, Ltd. | Process for preventing the formation of nitrogen monoxide in treatment of metals with nitric acid or mixed acid |
| US4051001A (en) * | 1974-08-26 | 1977-09-27 | Hitachi, Ltd. | Process for regenerating etching solution |
| US4356069A (en) * | 1981-03-09 | 1982-10-26 | Ross Cunningham | Stripping composition and method for preparing and using same |
| EP0079505B1 (en) * | 1981-10-29 | 1987-02-04 | LeaRonal, Inc. | A method of recovering copper from spent etch solutions |
| US4401509A (en) * | 1982-09-07 | 1983-08-30 | Fmc Corporation | Composition and process for printed circuit etching using a sulfuric acid solution containing hydrogen peroxide |
| US4497687A (en) * | 1983-07-28 | 1985-02-05 | Psi Star, Inc. | Aqueous process for etching cooper and other metals |
| US4491500A (en) * | 1984-02-17 | 1985-01-01 | Rem Chemicals, Inc. | Method for refinement of metal surfaces |
| EP0387057A1 (en) * | 1989-03-08 | 1990-09-12 | Tokai Denka Kogyo Kabushiki Kaisha | Surface-treating agents for copper and copper alloy |
| US5364549A (en) * | 1989-10-05 | 1994-11-15 | Interox Chemicals Limited | Hydrogen peroxide solutions |
| US5362712A (en) * | 1990-08-17 | 1994-11-08 | Hoechst Aktiengesellschaft | Process for removing a copper mold from a molded body |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1442848A (fr) | 1966-06-17 |
| GB1063007A (en) | 1967-03-22 |
| BE668423A (OSRAM) | 1965-12-16 |
| NL6510928A (OSRAM) | 1966-02-23 |
| DE1253008B (de) | 1967-10-26 |
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