US3704213A - Acid coppering bath - Google Patents
Acid coppering bath Download PDFInfo
- Publication number
- US3704213A US3704213A US108141A US3704213DA US3704213A US 3704213 A US3704213 A US 3704213A US 108141 A US108141 A US 108141A US 3704213D A US3704213D A US 3704213DA US 3704213 A US3704213 A US 3704213A
- Authority
- US
- United States
- Prior art keywords
- acid
- urea
- bath
- lit
- agent
- 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
- 239000002253 acid Substances 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229960004279 formaldehyde Drugs 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 235000019256 formaldehyde Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- -1 cyclic alcohols Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DSKJXGYAJJHDOE-UHFFFAOYSA-N methylideneurea Chemical compound NC(=O)N=C DSKJXGYAJJHDOE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the present invention relates in general to the electrolytic deposit of bright copper from an acid aqueous bath, and more particularly to the use of products added to baths of this character with a view to improve the deposit obtained therefrom.
- These metal elements must further receive a complementary nickel or chromium deposit.
- thiourea addition or substitution compounds mercuric salts of triarylmethanes, certain dyestuffs of the methylene blue group, etc.
- the present invention aims at avoiding the above-disclosed inconveniences by providing a method of depositing copper by electrolysis, which consists in electrolyzing an aqueous solution containing on the one hand one or a plurality of copper salts such as copper sulfate or copper nitrate and on the other hand additives having levelling properties, which are stable and economical since their cost is only one fraction of that of other additives utilized heretofore.
- the present invention provides an aqueous bright acid electrolytic coppering bath containing a copper salt, a brightener, a surface tension agent and a levelling agent resulting from the combination of two formaldehyde molecules on one urea molecule, the resultant product being firstly modified by using a heavy alcohol or one of its derivatives, then polymerized and possibly sulfonated.
- butanol is the most frequently used due on the one hand to the satisfactory results obtained therewith and on the other hand to its low cost.
- glycol esters o phthalic acid, malonic acid and maleic acid.
- the initial pH value is about 8.
- the temperature is gradually raised to 95 C.
- the temperature is maintained at 95 C. Then the water in the formol solution distils slowly by azeotropy and the condensation is continued during one hour.
- the pH value of the reaction medium is then about 3.
- the resulting resin has the following formula:
- n has a value within the range of 500 to 1,000.
- this resin i.e. when it is introduced as a levelling agent into an aqueous bright acid electrolytic coppering bath, a sulfonation is carried out according to the known method by reason of 100 g. of resin per liter of 30% (volume) H 50 solution, with the consequence that the solubility of said resin is increased considerably in the electrolyte bath.
- EXAMPLE 1 The following substances are mixed in succession in the electrolytic coppering vat, with the proportions given hereinafter:
- Example 1 The coppered pieces obtained from the above Examples 1 and 2 are compared with coppered pieces obtained with conventional baths without the levelling agent; the procedure used for comparing the surface condition of the pieces coppered according to these various methods is the profile test. It proved that in Example 1 the improvement in levelling of the copper deposit obtained in the treated parts is of the order of 30%, and in the case of Example 2 the improvement is of the order of 50% These examples clearly show the advantages deriving from the use of these additives in methods designed for covering oxidizable metal parts with protective deposits, notably preliminary to nickel-plating or chromium-plating processes as currently applied-to automotive parts.
- the satisfactory surface condition of the copper deposit thus obtained permits reducing the thickness of the noble metals subsequently deposited thereon while preserving an eventually identical exterior appearance. Under these conditions, this invention is characterized by the economy resulting from the process set forth hereinabove, with the additional advantage resulting from the difference between the cost of the levelling agent of this invention and the additives previously utilized for the same purpose.
- this invention should not be construed as being limited by the composition of electrolytic baths containing such levelling agents but should also be considered as comprising all articles provided with a deposit obtained from such baths.
- An aqueous acid electrolytic coppering bath containing a copper salt, a brightener, and a surface tension agent, further comprising a leveling agent having the genwherein n is an integer in the range of about 500 to about 1000 and the -OR linkage is a derivative of a compound selected from the group consisting of: aliphatic alcohols having 4-8 carbon atoms, benzyl alcohol, and esters resulting from the reactions of a glycol with an acid selected from the group consisting of phthalic acid, malonic acid and maleie acid.
- modified urea-formaldehyde resin is a sulfonated modified ureaformaldehyde resin, for facilitating its solution in the aqueous acid bath.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7002242A FR2076646A5 (enExample) | 1970-01-22 | 1970-01-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3704213A true US3704213A (en) | 1972-11-28 |
Family
ID=9049444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US108141A Expired - Lifetime US3704213A (en) | 1970-01-22 | 1971-01-20 | Acid coppering bath |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3704213A (enExample) |
| BE (1) | BE761663A (enExample) |
| CA (1) | CA978891A (enExample) |
| FR (1) | FR2076646A5 (enExample) |
| GB (1) | GB1337841A (enExample) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923613A (en) * | 1972-02-22 | 1975-12-02 | Kampschulte & Cie Dr W | Acidic galvanic copper bath |
| US5232575A (en) * | 1990-07-26 | 1993-08-03 | Mcgean-Rohco, Inc. | Polymeric leveling additive for acid electroplating baths |
| CN111501072A (zh) * | 2020-05-09 | 2020-08-07 | 广东哈福科技有限公司 | 一种电镀铜镀液去钝化剂及电镀铜镀液 |
-
1970
- 1970-01-22 FR FR7002242A patent/FR2076646A5/fr not_active Expired
-
1971
- 1971-01-15 BE BE761663A patent/BE761663A/xx unknown
- 1971-01-20 US US108141A patent/US3704213A/en not_active Expired - Lifetime
- 1971-01-21 CA CA103,476A patent/CA978891A/en not_active Expired
- 1971-04-19 GB GB2013171A patent/GB1337841A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923613A (en) * | 1972-02-22 | 1975-12-02 | Kampschulte & Cie Dr W | Acidic galvanic copper bath |
| US5232575A (en) * | 1990-07-26 | 1993-08-03 | Mcgean-Rohco, Inc. | Polymeric leveling additive for acid electroplating baths |
| CN111501072A (zh) * | 2020-05-09 | 2020-08-07 | 广东哈福科技有限公司 | 一种电镀铜镀液去钝化剂及电镀铜镀液 |
| CN111501072B (zh) * | 2020-05-09 | 2021-01-05 | 广东哈福科技有限公司 | 一种电镀铜镀液去钝化剂及电镀铜镀液 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1337841A (en) | 1973-11-21 |
| DE2102779B2 (de) | 1972-11-30 |
| FR2076646A5 (enExample) | 1971-10-15 |
| BE761663A (fr) | 1971-06-16 |
| DE2102779A1 (de) | 1971-07-29 |
| CA978891A (en) | 1975-12-02 |
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