US2950235A - Acid copper electroplating baths - Google Patents
Acid copper electroplating baths Download PDFInfo
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- US2950235A US2950235A US778075A US77807558A US2950235A US 2950235 A US2950235 A US 2950235A US 778075 A US778075 A US 778075A US 77807558 A US77807558 A US 77807558A US 2950235 A US2950235 A US 2950235A
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- acid
- copper
- azido
- bath
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052802 copper Inorganic materials 0.000 title claims description 36
- 239000010949 copper Substances 0.000 title claims description 36
- 239000002253 acid Substances 0.000 title claims description 28
- 238000009713 electroplating Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000010802 sludge Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000002659 electrodeposit Substances 0.000 claims description 7
- 239000011260 aqueous acid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- -1 aliphatic hydrocarbon radical Chemical class 0.000 description 9
- 238000005282 brightening Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000003254 radicals Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- ZKZNWRUUTQNYTH-UHFFFAOYSA-N 4-azidobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(N=[N+]=[N-])C=C1 ZKZNWRUUTQNYTH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000272534 Struthio camelus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 101150057833 THEG gene Proteins 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 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
- 230000006378 damage Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000008053 sultones Chemical class 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
- Acid copper electroplating baths which are usually operated with organic electroplating additives often have the disadvantage that they form a considerable amount of anode sludge.
- This sludge consists of finely dispersed, probably oxidized copper particles which also reach the objects to be copper plated by electrophoresis and thereby considerably reduce the quality of the copper electrodeposits.
- the typical blue color of the acid copper baths is discolored green through the presence of these fine particles.
- Another object is to provide an electroplating bath free from colloidal impurities.
- Yet another object is to provide a method and bath for acid copper plating wherein auxiliary measures to maintain purity of the bath such as filtering, oxidation, special anodes, etc. are unnecessary.
- Another object is to provide a method for obtaining a high quality copper deposit free from impurities in an acid copper plating bath such as anode sludge particles.
- Another object is to provide an additive compound for acid copper plating baths which maintains the bath in a highly pure state.
- the novel products also produce a certain brightening effect.
- the brightness can be .improved by further adding known brighteners to the baths.
- brighteners which may be used are: thiourea and its derivatives, N-monoand di-substituted dithiocarbamic acid alkyl esters-w-sulfonic acids or their salts,
- R is a lower saturated aliphatic hydrocarbon radical or an aromatic hydrocarbon radical
- -Z is an azido group
- n is a whole number of at least one.
- organic sulfonic acids having at least one azido group in the molecule are the following:
- the acids are customarily used in the form of their Water-soluble salts.
- Inorganic or organic bases such as the alkali metals, ammonia, dialkylamines or dialkanolamines, may be used as salt forming components.
- the compounds according to the present invention are added to the acid copper electroplating baths in amounts of 0.05-45 gm./liter, preferably of 0.2-0.8 gm./liter.
- the operating temperatures of such baths which are usually operated within a current density range of 0 to 12.5 amp./dm. may vary within wide limits up to about 60 C.
- the bath can-be operated within atemperature range of about 15 to about 50 C.
- the useable current densities at 15 C. lie between and 4.5 amp./ dmQ at 25 C. between 0 and 8'amp./dm. and at 50 '0.” between 1 and 12.5 amp./dm.
- the copper electro- "plating bath did not discolor and retained its blue color, even after prolonged periods of'operation. Sludge'for- "mation at the copper anodes did not occur; "Neither recycling pumps, filters, or anode bags were required. Alsludge free deposit of copper was obtained.
- An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge comprising an aqueous acid solution of a copper salt and a' compound selected from the group consisting of compounds having the following general structural formula:
- znrR-sonn group consisting of compounds having the following general structural formula:
- An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge comprising an aqueous acid solution of a copper salt; a brightening agent selected from the group consisting of N-monoand di-substituted dithiocarbamic .acid alkyl ester-w-sulfonic acids and their salts, and
- An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge comprising an aqueous acid solution of copper sulfate, at least 0.01 gm./liter of N,N diethyl dithiocarbarnic acid ethyl 'ester-w-sodium sulfonate and 0.05 to 4.5 gm./ liter w-azido-propane sodium sulfonate.
- a method for preventing anode sludge formation and for maintaining thepurity of an acid copper plating bath which comprises the step of adding to said bath a compound selected from the group consisting of compounds having the following general structural formula:
- R is a radical selected from theg roup consisting of lower saturated aliphatic hydrocarbon and aromatic hydrocarbon radicals, Z is an azido group and n is a'wh'ole number of at least one, said compound being added in an amount suflicient to prevent sludge formation.
- a method for preventing anode sludge formation and for maintaining the purity of an acid' copper pla t ing bath which comprises the step of adding to said bath a compound selected from the group consisting of compounds having the following general structural formula:
- R is a radical selected from the group consisting of lower saturated aliphatic hydrocarbon and aromatic hydrocarbon radicals,'Z is an azido group and n is a whole number of at least one, said compound being added in an amount sufiicient to prevent sludge formation.
- a method for preventing anode sludge formation and for maintaining the purity of an acid copper plating bath and the brightness of electrodeposits obtained therefrom which comprises the step of adding to said bath brightening agents selected from the group consisting of N-monoand di-substituted dithiocarbamic acid alkyl ester-w-sulfonic acids and their salts, and 1,3,5-triazine- '2,4,6-tris-(mercapto-alkane-sulfonic acids), the amount of said brightening agent being suflicient to effect said brightening; and a compound selected from the group consisting of compounds having the following general structural formula:
- Z ERSO H] V and water soluble salts thereof wherein R is a radical selected from the group consisting of lower saturated ahphatic hydrocarbon and aromatic hydrocarbon radicals, Z is an azido group and 'n is a whole number of fate and at least 0.01 gm./liter of N,N-diethyl-dithiocarbamic'acid ethyl ester-w-sodium sulfonate as a brightening agent, the step of adding to said bath from 0.05 to 4.5 gm./liter of w-azido-propane-sodium sulfonate.
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- 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)
- Electrolytic Production Of Metals (AREA)
Description
United States Patent 1 2,950,235 ACID COPPER ELECTROPLATING BATHS Wennemar Strauss and Wolf-Dieter Willmund, Dusseldorf-Holthausen, Germany, assignors to Dehydag, Dentsche Hydrierwerke G.m.b.H., Dusseldorf, Germany, a corporation of Germany No Drawing. Filed Dec. 4, 1958, Ser. No. 778,075 Claims priority, application Germany Dec. 17, 1957 8 Claims. (Cl. 204-52) This invention relates to acid copper plating baths containing organic compounds as brightening additives. It more specifically relates toan electroplating method and the baths therefore which eliminate anode sludge by the addition or" new additives to the acid copper plating bath.
Acid copper electroplating baths which are usually operated with organic electroplating additives often have the disadvantage that they form a considerable amount of anode sludge. This sludge consists of finely dispersed, probably oxidized copper particles which also reach the objects to be copper plated by electrophoresis and thereby considerably reduce the quality of the copper electrodeposits. The typical blue color of the acid copper baths is discolored green through the presence of these fine particles.
It has been attempted to avoid the formation of the anode sludge by using specially alloyed (phosphorus-containing) copper anodes. It has further been attempted to eliminate the presence of impurities by constantly filtering the baths through filter aggregates and/or surrounding the anodes with filter bags. Despite these measures it is unavoidable that small amounts of colloidal impurities remain in the copper bath.
It has also been proposed to eliminate the bath impurities by blowing air therethrough or by adding oxidizing agents, such as hydrogen peroxide. By blowing air through the bath the impurities are oxidized into copper- II-compounds which are again transformed into copper sulfate by the sulfuric acid in the bath, but this method is not recommended in most cases, especially if the copper baths are operated with wetting agents, because of the strong foam formation.
The addition of hydrogen peroxide leads to the destruction of the impurities within a short time, but this method has the disadvantage that it causes the copper electroplates to become brittle and that the usable current density range is greatly reduced. For this reason, if the copper electroplating bath is regenerated with hydrogen peroxide the bath must be taken out of operation for an extended period of time until all of the hydrogen peroxide has decomposed.
All of the measures described above make the operation of acid copper electroplating baths considerably more difficult and require additional work or additional apparatus. Moreover, in these methods, it was unavoidable that some sludge particles deposited with the electrodeposit.
It is an object of this invention to prevent anode sludge formation in acid copper plating baths.
Another object is to provide an electroplating bath free from colloidal impurities.
Yet another object is to provide a method and bath for acid copper plating wherein auxiliary measures to maintain purity of the bath such as filtering, oxidation, special anodes, etc. are unnecessary.
Another object is to provide a method for obtaining a high quality copper deposit free from impurities in an acid copper plating bath such as anode sludge particles.
Another object is to provide an additive compound for acid copper plating baths which maintains the bath in a highly pure state.
compounds.
Patented Aug. 23, 1960 We have now found that all of these disadvantageso'f the prior art methods can be avoided and the objects of our invention achieved by adding to the acid copperelec- ,troplating baths organic sulfonic acids containing at least one azido '(triazo) group in the molecule or salts of such The addition of these compounds has the effect that the baths remain deep blue in color and clear and-do not form asludge throughout their entire period of operativeness, even if they are operated at high loads, whereas baths which are operated without these additives turn green-after 2-4 a.h./liter acid and after some additional time begin to produce anode sludge.
At the same time, the novel products also produce a certain brightening effect. The brightness can be .improved by further adding known brighteners to the baths. Examples of brighteners which may be used are: thiourea and its derivatives, N-monoand di-substituted dithiocarbamic acid alkyl esters-w-sulfonic acids or their salts,
F 1 Zn R-SO H wherein R is a lower saturated aliphatic hydrocarbon radical or an aromatic hydrocarbon radical, -Z is an azido group and n is a whole number of at least one. I
Examples of organic sulfonic acids having at least one azido group in the molecule are the following:
.3-azido-propane-sulfonic acid-1 4-azido-butane-sulfonic acid-1 l-azido-l,1-dimethylpropane-sulfuric acid-3 3-azido-2-hydroxy-propane-sulfonic acid-1 2-azido-3-halo-propane-sulfonic acid-l 2,3-diazido-propane-sulfonic acid-1 2,3-d.iazido-butane-sulfonic acid-l 8-azido-naphthalene-sulfonic acid-1 4-azido-benzene-sulfonic acid Z-(azido-methyl)-benzene-sulfonic acid These compounds may be produced inaccordance with known processes, for example by reacting sultones, such as propane sultone, tolylsultone and 1,8-naphthylsultone, with hydrazoic acid or its salts (azides) or by reacting hydrazoic acid or its salts with halogen-substituted organic sulfonic acids.
The acids are customarily used in the form of their Water-soluble salts. Inorganic or organic bases, such as the alkali metals, ammonia, dialkylamines or dialkanolamines, may be used as salt forming components.
The compounds according to the present invention are added to the acid copper electroplating baths in amounts of 0.05-45 gm./liter, preferably of 0.2-0.8 gm./liter. The operating temperatures of such baths, which are usually operated within a current density range of 0 to 12.5 amp./dm. may vary within wide limits up to about 60 C.
The following examples are set forth to enable persons skilled in the art to better understand and practice the invention. It will be understood that there is no intention of limiting the invention to these examples.
Examples An acid copper electroplating bath containing 220 gm./ liter CuSO 5H O, 60 gm./ liter H 0.05 gin/liter N,N-diethyl-dithiocarbamic acid ethyl ester-w-sodium su1- 3 I fonate as a 'brightener, 0.25 gm./liter 1,3-bis-(dibutylamino)-propanol-2 as a ductility-improving agent, and 1 gm./ liter of the reaction product of dodecyl alcohol and .8 mols ethylene oxide as a wetting agent, was modified with: 0.5 gm./ liter w-azido-propane-sodium sulfonate. 'Fullbright copper ,electroplates were obtained upon elec troplating objects made of brass, bronze, iron or steel therein: The bath can-be operated within atemperature range of about 15 to about 50 C. The useable current densities at 15 C. lie between and 4.5 amp./ dmQ at 25 C. between 0 and 8'amp./dm. and at 50 '0." between 1 and 12.5 amp./dm. The copper electro- "plating bath did not discolor and retained its blue color, even after prolonged periods of'operation. Sludge'for- "mation at the copper anodes did not occur; "Neither recycling pumps, filters, or anode bags were required. Alsludge free deposit of copper was obtained.
' Without the addition of w-azido-propane-sodium sul- -fonate the bath must be continuously recycled and filtered. Despite filtration, a certain amount of reduction in the brightness may occur, which is undesirable;
In place of w-azido-propane-sodium sulfonate the following compounds were used according to the examples 'above in amounts of 0.2 to 0.8 gm./liter with comparable results:
3-azido-2-hydroxy-propane-sulfonie acid-1 .2-azido-3-halo-propane-sulfonic acid-1 2,3-diazido-propane-sulfonicV acid-1 '3-azido-butane-sulfonic acid-1 8-azido-naphthalene-sulfonic acid-1 4-azido-benzene-sulfonic acid or their water-soluble salts.
While we have disclosed certain specific embodiments of our invention, we wish it to be understood that these are not intended to be limitative, and that various changes and modifications may be made Without departing from the spirit of our invention or the scope of the appended claims.
We claim:
1. An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge, comprising an aqueous acid solution of a copper salt and a' compound selected from the group consisting of compounds having the following general structural formula:
znrR-sonn group consisting of compounds having the following general structural formula:
Z R--SO H] I and water soluble salts thereof, wherein R is a radical selected from the group consisting of lower aliphatic saturated hydrocarbon and aromatic hydrocarbon radi- -cals, Z is an azido group and n is a whole number of at least one, said compound being added in an amount suificient to prevent sludge formation.
3. An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge comprising an aqueous acid solution of a copper salt; a brightening agent selected from the group consisting of N-monoand di-substituted dithiocarbamic .acid alkyl ester-w-sulfonic acids and their salts, and
1,3,5 triazine 2,4,6 4 tris (mercapto alkane sulfonic acids), the amount of said brightening agent being sulficient to elfect said brightening; and a compound selected and water soluble salts thereof, wherein R is a radical selected from the group consisting of lower aliphatic saturated hydrocarbons and aromatic hydrocarbon radicals, Z is an'azido group and n is a whole number of at least one, said compound being added in an amount suflicient to prevent sludge formation.
4. An acid copper electroplating bath for producing copper electrodeposits of high quality free from anode sludge comprising an aqueous acid solution of copper sulfate, at least 0.01 gm./liter of N,N diethyl dithiocarbarnic acid ethyl 'ester-w-sodium sulfonate and 0.05 to 4.5 gm./ liter w-azido-propane sodium sulfonate.
5. A method for preventing anode sludge formation and for maintaining thepurity of an acid copper plating bath which comprises the step of adding to said bath a compound selected from the group consisting of compounds having the following general structural formula:
and water soluble salts thereof, wherein R is a radical selected from theg roup consisting of lower saturated aliphatic hydrocarbon and aromatic hydrocarbon radicals, Z is an azido group and n is a'wh'ole number of at least one, said compound being added in an amount suflicient to prevent sludge formation. 7
6. A method for preventing anode sludge formation and for maintaining the purity of an acid' copper pla t ing bath which comprises the step of adding to said bath a compound selected from the group consisting of compounds having the following general structural formula:
and water soluble salts thereof, wherein R is a radical selected from the group consisting of lower saturated aliphatic hydrocarbon and aromatic hydrocarbon radicals,'Z is an azido group and n is a whole number of at least one, said compound being added in an amount sufiicient to prevent sludge formation.
7. A method for preventing anode sludge formation and for maintaining the purity of an acid copper plating bath and the brightness of electrodeposits obtained therefrom, which comprises the step of adding to said bath brightening agents selected from the group consisting of N-monoand di-substituted dithiocarbamic acid alkyl ester-w-sulfonic acids and their salts, and 1,3,5-triazine- '2,4,6-tris-(mercapto-alkane-sulfonic acids), the amount of said brightening agent being suflicient to effect said brightening; and a compound selected from the group consisting of compounds having the following general structural formula:
Z ERSO H] V and water soluble salts thereof, wherein R is a radical selected from the group consisting of lower saturated ahphatic hydrocarbon and aromatic hydrocarbon radicals, Z is an azido group and 'n is a whole number of fate and at least 0.01 gm./liter of N,N-diethyl-dithiocarbamic'acid ethyl ester-w-sodium sulfonate as a brightening agent, the step of adding to said bath from 0.05 to 4.5 gm./liter of w-azido-propane-sodium sulfonate.
References Cited in the file of this patent UNITED STATES PATENTS 2,849,352 Kirstahler et a1 1 Aug. 26, 1958 UNITED STATES PATENT orricr CERTEFIATN 6F CORRECTION Patent No. 2,950,235 August 23, 1960 Wennemar Strauss et a1.
It is Hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, line 11 for -a.h.,/liter acid read amperehours per liter of acid bath column 4, line 26, for "theg roup read the group Signed and sealed this 8th day of August 1961.
(SEAL) Attest:
ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents
Claims (1)
1. AN ACID COPPER ELECTROPLATING BATH FOR PRODUCING COPPER ELECTRODEPOSITS OF HIGH QUALITY FREE FROM ANODE SLUDGE, COMPRISING AN AQUEOUS ACID SOLUTION OF A COOPER SALT AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FOLLOWING GENERAL STRUCTURAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED27038A DE1055912B (en) | 1957-12-17 | 1957-12-17 | Acid galvanic copper baths |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2950235A true US2950235A (en) | 1960-08-23 |
Family
ID=7039098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US778075A Expired - Lifetime US2950235A (en) | 1957-12-17 | 1958-12-04 | Acid copper electroplating baths |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US2950235A (en) |
| BE (1) | BE572186A (en) |
| CH (1) | CH369948A (en) |
| DE (1) | DE1055912B (en) |
| FR (1) | FR1208880A (en) |
| GB (1) | GB857409A (en) |
| NL (2) | NL110454C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075899A (en) * | 1958-04-26 | 1963-01-29 | Dehydag Gmbh | Baths for the production of metal electroplates |
| US3081240A (en) * | 1959-06-06 | 1963-03-12 | Debydag Deutsche Hydrierwerke | Acid copper electroplating baths |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| EP2669406A1 (en) * | 2012-05-31 | 2013-12-04 | Rohm and Haas Electronic Materials LLC | Electrolytic copper plating solution and method of electrolytic copper plating |
| CN114277413A (en) * | 2021-12-29 | 2022-04-05 | 广东利尔化学有限公司 | Copper plating solution for circuit board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184172B (en) * | 1961-08-31 | 1964-12-23 | Dehydag Gmbh | Process for the galvanic deposition of firmly adhering and high-gloss copper coatings |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
-
0
- BE BE572186D patent/BE572186A/xx unknown
- NL NL234197D patent/NL234197A/xx unknown
- NL NL110454D patent/NL110454C/xx active
-
1957
- 1957-12-17 DE DED27038A patent/DE1055912B/en active Pending
-
1958
- 1958-09-18 CH CH6407658A patent/CH369948A/en unknown
- 1958-10-29 GB GB34608/58A patent/GB857409A/en not_active Expired
- 1958-11-26 FR FR1208880D patent/FR1208880A/en not_active Expired
- 1958-12-04 US US778075A patent/US2950235A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075899A (en) * | 1958-04-26 | 1963-01-29 | Dehydag Gmbh | Baths for the production of metal electroplates |
| US3081240A (en) * | 1959-06-06 | 1963-03-12 | Debydag Deutsche Hydrierwerke | Acid copper electroplating baths |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| EP2669406A1 (en) * | 2012-05-31 | 2013-12-04 | Rohm and Haas Electronic Materials LLC | Electrolytic copper plating solution and method of electrolytic copper plating |
| CN114277413A (en) * | 2021-12-29 | 2022-04-05 | 广东利尔化学有限公司 | Copper plating solution for circuit board |
| CN114277413B (en) * | 2021-12-29 | 2024-05-17 | 广东利尔化学有限公司 | Copper plating solution for circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| GB857409A (en) | 1960-12-29 |
| CH369948A (en) | 1963-06-15 |
| FR1208880A (en) | 1960-02-26 |
| NL110454C (en) | |
| NL234197A (en) | |
| BE572186A (en) | |
| DE1055912B (en) | 1959-04-23 |
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