US3454416A - Aqueous bath and method for deposition of copper by chemical reduction - Google Patents
Aqueous bath and method for deposition of copper by chemical reduction Download PDFInfo
- Publication number
- US3454416A US3454416A US515753A US3454416DA US3454416A US 3454416 A US3454416 A US 3454416A US 515753 A US515753 A US 515753A US 3454416D A US3454416D A US 3454416DA US 3454416 A US3454416 A US 3454416A
- Authority
- US
- United States
- Prior art keywords
- copper
- deposition
- solutions
- chemical reduction
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 37
- 229910052802 copper Inorganic materials 0.000 title description 37
- 239000010949 copper Substances 0.000 title description 37
- 230000008021 deposition Effects 0.000 title description 27
- 239000003638 chemical reducing agent Substances 0.000 title description 11
- 238000000034 method Methods 0.000 title description 8
- 238000006722 reduction reaction Methods 0.000 title description 8
- 239000000243 solution Substances 0.000 description 35
- 238000000151 deposition Methods 0.000 description 29
- 239000003381 stabilizer Substances 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- -1 N-methylrhodanine N-phenylrhodanine Chemical compound 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000615 nonconductor Substances 0.000 description 4
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- JGRMXPSUZIYDRR-UHFFFAOYSA-N 2-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)acetic acid Chemical compound OC(=O)CN1C(=O)CSC1=S JGRMXPSUZIYDRR-UHFFFAOYSA-N 0.000 description 2
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 2
- ZBUUHLDYMKTVLT-UHFFFAOYSA-N 3-amino-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound NN1C(=O)CSC1=S ZBUUHLDYMKTVLT-UHFFFAOYSA-N 0.000 description 2
- JKLZCQWVERBDEZ-UHFFFAOYSA-N 3-methyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CN1C(=O)CSC1=S JKLZCQWVERBDEZ-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DVRWEKGUWZINTQ-UHFFFAOYSA-N 3-phenyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound O=C1CSC(=S)N1C1=CC=CC=C1 DVRWEKGUWZINTQ-UHFFFAOYSA-N 0.000 description 1
- ZDTDVFFZZQPGFM-UHFFFAOYSA-N 5-nitro-3-phenyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound C1(=CC=CC=C1)N1C(SC(C1=O)[N+](=O)[O-])=S ZDTDVFFZZQPGFM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NAASHBXYBMUAKZ-UHFFFAOYSA-J C(=O)([O-])C(O)C(O)C(=O)[O-].[Na+].[K+].[Na+].[Na+].C(=O)([O-])C(O)C(O)C(=O)[O-] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Na+].[K+].[Na+].[Na+].C(=O)([O-])C(O)C(O)C(=O)[O-] NAASHBXYBMUAKZ-UHFFFAOYSA-J 0.000 description 1
- KBNKENZGGCODIL-UHFFFAOYSA-O CC[S+]=C(N1)SCC1=O Chemical compound CC[S+]=C(N1)SCC1=O KBNKENZGGCODIL-UHFFFAOYSA-O 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Definitions
- This invention relates to the deposition of copper by chemical reduction. More particularly, this invention relates to metallizing, namely to the deposition of copper from aqueous solutions of its salts by chemical reduction.
- Copper is deposited by chemical reduction on such nonconductors as plastics or ceramics to provide a conductive primer coating on which heavier metallic deposits may then be formed by electrodeposition.
- the solutions employed generally contain an inorganic copper salt as a source of copper, a complexing agent, normally the salt of an organic acid or an organic base to form complex ions with copper, and a reducing agent.
- the known copper deposition solutions heretofore used are relatively unstable and decompose within one or two days. Their copper content is precipitated spontaneously, either as metallic copper or as a copper oxide.
- Stabilizers have been proposed heretofore, but have been found to be of limited value.
- the known stabilizers only moderately extend the useful life of the copper depositing solutions, and the relatively more effective known stabilizers tend to cause discoloration and other deterioration of the copper deposits formed. Yet, even the best known stabilizers do not permit uniform conditions to be maintained for continuous operation of the copper deposition process.
- X is S or NH; R is hydrogen, lower alkyl, phenyl, carboxy-lower alkyl, or amino; and R is hydrogen, lower alkyl, or nitro.
- the copper deposition solutions of the invention are stable not only at room temperature, but also even at elevated temperatures which are known to be deleterious to the conventional copper deposition solutions, thus permitting operation at temperatures at which the deposition rate is faster than at room temperature.
- the copper coatings formed from the solutions of the invention are bright red and consist of pure metal.
- the stabilizing agents of the invention are known chemical compounds, and are prepared by known methods, rhodanine, for example, is readily obtained by reacting salts of dithiocarbamic acid with a halocetic acid in aqueout solution and subsequent heating in the presence of hydrochloric acid.
- Thiohydantoin is formed at elevated temperature from glycine and isothiocyanates.
- Rhodanine N-methylrhodanine N-phenylrhodanine Rhodanine-N-acetic acid N-aminorhodanine 3-phenyl-5-nitrorhodanine S-ethylrhodanine Thiohydantoin Rhodanine and N-methylrhodanine have been found to stabilize copper deposition solutions over the longest periods, and are capable of preventing decomposition of such solutions over practically unlimited periods.
- the stabilizing agents of the invention may be employed in concentration between one milligram and 0.5 gram per liter, but they are so effective in small amounts that nothing is gained by using more than about 0.05 gram per liter.
- concentration of the conventional constituents of the solutions may be varied within the usual limits without affecting thestabilizing effect of the aforedefined compounds, and the specific nature and concentration of the copper salts, complexing agents, reducing agents, buffers, wetting and brightening agents employed is not critical.
- the presence of the stabilizing agents does not aifect the mode of operation of the deposition solution, and the deposits formed have the expected electrical conductivity so that heavier metal deposits can be formed thereon by electro-deposition.
- Metals as well as non-conductors may be metallized in copper deposition solutions of the invention.
- the coatings produced by chemical reduction in the presence of the aforedescribed stabilizing agents are distinguished by their clear, bright red, metallic appearance from the relatively dark and grainy deposits containing significant amounts of copper oxides which are characteristic of solutions containing the known 2-mercaptobenzthiazole as a stabilizing agent.
- Suitable tan-ks for storage are therefore such which consists of non-metallic vinyl chloride, polyethylene, polypropylene, or similar plastics which are nonconductors and are resistant to chemical attack by the copper solutions of the invention.
- the solutions of the invention When brought into contact with metals or non-metals suitably prepared in a known manner, the solutions of the invention promptly cause the deposition of copper coatings.
- the solutions are preferably used having a specific gravity of about 1.04, a pH value of 12.0 to 12.5, and at a temperature of 20 40 C.
- the containers employed are either plastic tanks or steel tanks coated with suitable plastics. Mechanical agitation is preferred to obtain or effect greater uniformity of the copper coatings. Furthermore, air agitation is not advisable so as to avoid oxidation.
- the usual time of immersion for steel objects is preferably about to 20 minutes, and a deposition time of more than 20 minutes is not usually needed.
- the deposition rate in the typical solutions of Examples I and II is 0.3 micron in 10 minutes at 20 C., and 0.6 micron in 20 minutes. At 40 C., the deposition rate rises to 0.8 micron in 10 minutes, and 1.3 microns in 20 minutes.
- the rate of deposition decreases with the use of the solution, and can be increased by raising the temperature if the time needed for adequate coverage becomes excessive.
- the solution composition is best controlled by determining the copper content by analysis, and making additions of a concentrated stock solution to restore the original copper content.
- the copper coatings produced by immersion in the solutions of the invention may be covered by electrolytically produced metal layers in a conventional manner.
- Plastics may be prepared for accepting 4 copper coatings by chemical etching and surface activation, and the following procedure, illustrate a typical process.
- Molded objects of acrylonitrile-butadiene-styrene copolymer were etched by immersion in concentrated sulfuric acid at 50-65 C. for about 15 to 30 minutes. The objects were then rinsed and immersed in a solution prepared by dissolving 2.5 to 5 kg. of stannous chloride in 5 liters of hydrochloric acid of density 1.19, and diluting to liters with water. The temperature of the stannous chloride solution was kept between 15 and 25 C., and the immersion time was about 1 to 3 minutes. The plastic objects were then transferred to a solution containing 0.1 to 0.3 kg. silver nitrate and 1.0 liter ammonium hydroxide, d. 0.9, in 100 liter water at 15 to 25 C. in which they were kept immersed for one to three minutes. They were then ready for copper deposition in any one of the copper deposition baths indicated in the invention hereinabove.
- An aqueous solution for the deposition of copper by chemical reduction containing a source of copper ions, a complexing agent for said ions, a reducing agent for reducing the complex copper ions and as a stabilizing agent 0.001 to 0.5 gram per liter of a compound of the formula wherein X is S or NH; R is hydrogen, lower alkyl, phenyl, carboxy-lower alkyl, or amino; and R is hydrogen, lower alkyl, or nitro.
- the stabilizing agent is selected from the group consisting of rhodanine, N-methylrhodanine, N-phenylrhodanine, rhodanine- N-acetic acid, N-aminorhodanine, 3-phenyl-5-nitrorhodanine, S-ethylrhodanine, thiohydantoin.
- a method of depositing copper on a receptive base from a solution set forth in claim 4 comprising etching such base, rinsing, and immersing said base in a solution as set forth in claim 4.
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)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH36568A DE1266099B (de) | 1965-02-20 | 1965-02-20 | Bad fuer die reduktive Kupferabscheidung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3454416A true US3454416A (en) | 1969-07-08 |
Family
ID=7433913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US515753A Expired - Lifetime US3454416A (en) | 1965-02-20 | 1965-12-22 | Aqueous bath and method for deposition of copper by chemical reduction |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3454416A (enrdf_load_stackoverflow) |
| BE (1) | BE676720A (enrdf_load_stackoverflow) |
| CH (1) | CH464643A (enrdf_load_stackoverflow) |
| DE (1) | DE1266099B (enrdf_load_stackoverflow) |
| GB (1) | GB1128306A (enrdf_load_stackoverflow) |
| NL (1) | NL149857B (enrdf_load_stackoverflow) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| US3793038A (en) * | 1973-01-02 | 1974-02-19 | Crown City Plating Co | Process for electroless plating |
| US4253875A (en) * | 1976-08-04 | 1981-03-03 | Schering Aktiengesellschaft | Catalytic lacquer for producing printing circuits |
| US4853320A (en) * | 1987-09-16 | 1989-08-01 | U.S. Philips Corporation | Method of locally providing metal on a surface of a substrate |
| US4908242A (en) * | 1986-10-31 | 1990-03-13 | Kollmorgen Corporation | Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures |
| CN110983309A (zh) * | 2019-12-26 | 2020-04-10 | 广东东硕科技有限公司 | 2-硫代海因类化合物或其盐的应用 |
| US20210009785A1 (en) * | 2018-02-19 | 2021-01-14 | Arkema Inc. | Accelerator solutions useful for resin curing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL164906C (nl) * | 1975-08-19 | 1981-02-16 | Philips Nv | Werkwijze voor de bereiding van een waterig alkalische verkoperbad. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2609339A (en) * | 1948-11-02 | 1952-09-02 | United Chromium Inc | Bright copper plating from cyanide baths |
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1243493B (de) * | 1961-02-04 | 1967-06-29 | Bayer Ag | Waessriges Bad zur chemischen Abscheidung von borhaltigen Metallueberzuegen |
-
1965
- 1965-02-20 DE DESCH36568A patent/DE1266099B/de active Pending
- 1965-12-22 US US515753A patent/US3454416A/en not_active Expired - Lifetime
-
1966
- 1966-02-10 CH CH189366A patent/CH464643A/de unknown
- 1966-02-15 GB GB6561/66A patent/GB1128306A/en not_active Expired
- 1966-02-18 NL NL666602102A patent/NL149857B/xx not_active IP Right Cessation
- 1966-02-18 BE BE676720D patent/BE676720A/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2609339A (en) * | 1948-11-02 | 1952-09-02 | United Chromium Inc | Bright copper plating from cyanide baths |
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| US3793038A (en) * | 1973-01-02 | 1974-02-19 | Crown City Plating Co | Process for electroless plating |
| US4253875A (en) * | 1976-08-04 | 1981-03-03 | Schering Aktiengesellschaft | Catalytic lacquer for producing printing circuits |
| US4908242A (en) * | 1986-10-31 | 1990-03-13 | Kollmorgen Corporation | Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures |
| US4853320A (en) * | 1987-09-16 | 1989-08-01 | U.S. Philips Corporation | Method of locally providing metal on a surface of a substrate |
| US20210009785A1 (en) * | 2018-02-19 | 2021-01-14 | Arkema Inc. | Accelerator solutions useful for resin curing |
| CN110983309A (zh) * | 2019-12-26 | 2020-04-10 | 广东东硕科技有限公司 | 2-硫代海因类化合物或其盐的应用 |
| CN110983309B (zh) * | 2019-12-26 | 2023-01-03 | 广东东硕科技有限公司 | 2-硫代海因类化合物或其盐的应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CH464643A (de) | 1968-10-31 |
| DE1266099B (de) | 1968-04-11 |
| NL149857B (nl) | 1976-06-15 |
| GB1128306A (en) | 1968-09-25 |
| NL6602102A (enrdf_load_stackoverflow) | 1966-08-22 |
| BE676720A (enrdf_load_stackoverflow) | 1966-08-18 |
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