US3542655A - Electrodeposition of copper - Google Patents

Electrodeposition of copper Download PDF

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Publication number
US3542655A
US3542655A US725209A US3542655DA US3542655A US 3542655 A US3542655 A US 3542655A US 725209 A US725209 A US 725209A US 3542655D A US3542655D A US 3542655DA US 3542655 A US3542655 A US 3542655A
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good
air
copper
group
carbon atoms
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Otto Kardos
Hugh B Durham
Arthur J Tomson
Donald A Arcilesi
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M&T Chemicals Inc
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M&T Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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

  • this invention relates to novel compositions and to a process for electrodepositing bright, strongly leveled, ductile copper from an aqueous acidic copper plating bath containing chloride ions and at least one member from each of the following groups:
  • each R is independently a divalent aliphatic or aromatic non-heterocyclic group of 1-10 carbon atoms;
  • R is hydrogen, a metal cation, a monovalent aliphatic or aromatic organo group of l-20 carbon atoms, or the groups R40 M or -R(S) -RSO M wherein q is an integer 2-5;
  • M is a cation;
  • R" is hydrogen or an alkyl, hydroxyalkyl or aminoalkyl group of 1-6 carbon atoms; Y is a divalent organo group of 1-10 carbon atoms which forms a '5-6-membered cyclic ring structure with the group and n is an integer 2-5 inclusive.
  • This invention relates to novel processes and compositions for the electrodeposition of copper from aqueous acidic baths. More particularly, this invention relates to certain bath compositions containing specified combinations of chemical ingredients and to the use of such compositions to obtain bright, ductile, strongly leveled copper electrodeposits.
  • a further object of the invention is to provide novel plating bath compositions from which bright copper electrodeposits may be obtained wherein said electrodeposits exhibit good leveling and ductility over wide current density ranges.
  • this invention relates to novel compositions and to a process for electrodepositing bright, strongly leveled, ductile copper from an aqueous acidic copper plating bath containing chloride ions and at least one member from each of the following groups:
  • each R is independently a divalent aliphatic or aromatic non-heterocyclic group of 1-10 carbon atoms;
  • R is hydrogen, a metal cation, a monovalent aliphatic or aromatic organo group of 1-20 carbon atoms, or the groups R-SO M or -R-(S) RSO M wherein q is an integer 2-5; M is a cation;
  • R is hydrogen or an alkyl, hydroxyalkyl or aminoalkyl group of 1-6 carbon atoms
  • Y is a divalent organo group of l-lO carbon atoms which forms a 5-6-membered cyclic ring structure with the group and n is an integer 2-5 inclusive.
  • the -R groups may or may not be identical.
  • leveled denotes a surface which is smoother than its substrate.
  • these additives When used alone these additives may be found to be deficient in that the copper deposits obtained may not be bright, smooth, and exhibit adequate leveling properties over a sufiicient current density range. Combinations utilizing two of the additives may give fairly bright copper deposits, but the current density range of brightness may be limited and/ or the rate of leveling (decrease of surface roughness) may be low. Other double combinations may give striated deposits and limited bright current density ranges.
  • novel compositions of the invention may be employed in combination with aqueous acidic copper plating baths.
  • Typical aqueous acidic copper plating baths which may be employed in combination with the novel compositions of the invention include the following:
  • Fluoborate bath (2) Cu(BF -600 g./l. (preferably about 224 g./l.)
  • HBF 1-60 g./l. (preferably about 3.5 g./l.)
  • the basis metals which may be electroplated in accordance with the process of this invention may include ferrous metals, such as steel, iron, etc. bearing a surface layer of nickel or cyanide copper; zinc and its alloys including zinc-base die-cast articles bearing a surface layer of cyanide copper or pyrophosphate copper; nickel, including nickel alloys with other metals such as cobalt-iron; aluminum, including its alloys, after suitable pretreatment, etc.
  • the bright leveled copper deposit of this invention After the deposition of the bright leveled copper deposit of this invention, generally a bright nickel deposit and a chromium deposit (which may be microporous or microcracked) may be applied.
  • the bright acid copper deposit of this invention contributes to the appearance and performance of the composite coating because of its very high rate of leveling, its excellent pore-filling capacity, its high luster, good ductility and low internal stress. It improves corrosion resistance and permits economy in nickel.
  • the bright acid copper electrodeposits of this invention may be used for industrial applications such as the plating of printing rolls, memory drums, etc., and for electroforming. It gives very good results also for the plating of non-conducting materials, such as plastics, after the usual pretreatment.
  • the plating conditions for electrodeposition from the aforementioned baths may, for example, include temperatures of C.-60 C. (preferably 20 C.-40 C.); pH (electrometric) of less than about 1.5; and a cathode current density of .1-30.0 amperes per square decimeter (a./s.d.).
  • 'Iypical average current densities may be 2-20 a./s.d. for the sulfate bath, and about 4-40 a./s.d. for the fluo borate bath.
  • Air agitation, volume agitation, or mechanical agitation may increase the effective current density ranges and enhance the uniformity of the copper deposit.
  • this invention relates to novel compositions and to a process for electrodepositing bright, strongly leveled, ductile copper from an aqueous acidic copper plating bath containing chloride ions and at least one member from each of the following groups:
  • R may be a divalent hydrocarbon group (including such hydrocarbon groups containing inert substituents such as hydroxyl, alkoxy, polyoxyalkylene, halogen, etc.) of 1-10 carbon atoms such as an alkylene group of 1-10 carbon atoms (i.e., CH -CH CH '(CH2)3 (CH2)4F 2)5' in general, (CH wherein p is an integer 1-10).
  • R may be a divalent non-heterocyclic group of 1-10 carbon atoms containing 1-3 oxygen, 1-3 sulfur, or 1-3 nitrogen atoms (such as --CH CH OCH CH CH CHOHCI-I CH CH CH NHCH CH -CH CH SCH CH etc.).
  • R may be a hydrocarbon radical preferably selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl, alkaryl, including such radicals when inertly substituted.
  • R When R is alkyl, it may typically be straight chain alkyl or branched alkyl, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl, heptyls, octyls, decyls, dodecyls, tetradecyl, octadecyl, etc.
  • Preferred alkyl includes lower alkyl, i.e., having less than about 8 carbon atoms, i.e., octyls and lower.
  • R alkenyl
  • it may typically be vinyl, allyl, methallyl, buten-lyl, buten-Z-yl, buten-S-yl, penten-l-yl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, tetra-decenyl, octadecenyl, etc.
  • R is alkynyl
  • it may typically be ethynyl, propargyl, butynyl, etc.
  • R When R is cycloalkyl, it may typically be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.
  • R is aralkyl it may typically be benzyl, [3- phenylethyl, u-phenylpropyl, B-phenylpropyl, etc.
  • R is aryl it may typically be phenyl, naphthyl, etc.
  • R When R is alkaryl, it may typically be tolyl, xylyl, pethylphenyl, p-nonylphenyl, etc.
  • K may be inertly substituted, e.g., may bear a non-reactive substituent such as alkyl, aryl, cycloalkyl, aralkyl, alkaryl, alkenyl, ether, etc.
  • Polysulfide compounds of the formula (1) may typically be prepared by the reaction of an alkali metal salt of a hydropolysulfide and a sultone according to the reaction:
  • R(S) Na compound may be prepared by the reaction of RSNa with sulfur if R is an aromatic group (compounds 8-1, 8-2, 8-3, S4, 8-5, -20).
  • a typical procedure is: To a methanol solution (150 ml.) containing sodium methoxide (0.1 m.) is added the RSH (0.1 m.) compound. The mixture is stirred at room temperature until the compound has dissolved. Sulfur powder (0.1 m.) compound. The mixture is stirred at room temuntil all the sulfur is dissolved. Propanesultone (0.12 m.) is added to the stirred solution. Stirring is continued for 30 minutes, during which time a solid precipitates from the solution. Acetone (250 ml.) is then added to give additional solid, which is then filtered, washed with acetone, and dried.
  • Aliphatic R'(S),,Na compounds are prepared by reaction of R'Q with Na S where Q is Cl, Br, I, OSOZCGH5, --OSO2C6H4'CH3, Compounds S-l7, 5-18, 5-19).
  • a typical procedure is: To a stirred methanol solution (150 ml.) containing sodium di sulfide (0.1 m.) is added dropwise a solution of RQ (0.1 m.) in methanol (50 ml.) at room temperature. The reaction is slightly exothermic. After the addition is completed the mixture is stirred for 30 minutes. Propane sultone (0.12 m.), which may be dissolved in methanol (50 ml.), is added to the stirred mixture. During the addition of propane sultone a white solid usually precipitates from the solution. The mixture may be heated and stirred at 65 C. for 30 minutes and then cooled. Acetone is added and the solid is filtered and dried.
  • haloalkane sulfonates including, e.g., ClCH CHOHCH SO Na (prepared by reaction of epichlorohydrin with sodium bisulfite), and in general compounds of the type QRSO M, may be used.
  • Some polysulfide compounds may also be prepared by the direct sulfonation of an organic polysulfide (e.g., S-7; or 8-21 by sulfonation of 8-20).
  • an organic polysulfide e.g., S-7; or 8-21 by sulfonation of 8-20.
  • Symmetrical disulfides may be prepared by careful oxidation of compounds of the type HSRSO Na.
  • the sulfide compounds of the invention may be present in the copper bath in eifective amount of about 0.001 g./l. 1.0 g./l., preferably 0.005 g./l.0.2 g./l.
  • heterocyclic cooperating additives of the invention may include heterocyclic compounds of the formulae:
  • Typical heterocyclic compounds which may be employed according to the invention may include compounds of Table 111 wherein the groups X and Y of formulae (1) and (2) are as shown.
  • the heterocyclic compounds may be employed in eifective amounts, typically 0.5l0.0 mg./l. and preferably 0.7-4.0 mg./l. of total aqueous bath composition.
  • heterocyclic cooperating additives of Table III may be obtained commercially or may be prepared as indicated herein.
  • compounds such as H-1 and H-4 may be prepared according to equation:
  • H- may be prepared from ethanolamine and carbon disulfide, which by oxidation with iodine gives bis-(2-hydr0xyethyl-)thiuram disulfide. Boiling of an aqueous suspension of this compound yields H-S.
  • Compounds such as H-l, H-2, H-4 may also be prepared by heating of the alkanolamine-carbon disulfide reaction product according to the equation:
  • Polyethers which may be used according to the process of the invention may have at least 5 ether oxygen atoms and include polyethers of the formulae:
  • Suitable polyethers which may be used according to the invention include polyethers set forth in Table IV.
  • the polyether additives may be employed in elfective amounts, typically 0.005-l0.0 g./l. and preferably 0.1- 1.0 g./l. of total aqueous bath composition.
  • aqueous copper plating bath Good results may be obtained using a chloride ion concentration of from about 4 mg./l. to 60 mg./1. of aqueous copper plating bath composition, and preferably a chloride ion concentration of from 20 mg./l. to 60 mg./l. of aqueous copper plating solution.
  • the aqueous copper plating bath contains:
  • the plating experiments were performed in a Hull Cell containing 250 ml. of this acid copper sulfate bath.
  • each of M1 and M is an alkali metal (preierably Na or K? or a hydrogen atom.
  • Hull Cell allows one to observe the appearance of the deposit over a wide current density range.
  • Type of Additives g./l. agitation Results udge the degree of leveling the polished brass panels 02 used for these plating tests were scratched with 4/0 11 ⁇ P-u 0.1 ⁇ Air Very good. emery polishing paper over a horizontal band of about r 51- 8; D 10 mm. width.
  • the plating temperature used in these 0 12 01 0 8-1 0.02 experiments was the ambient room temperature (24-30 13 1H3 0.20 Air Very good. 0.), unless otherwise stated.
  • the total current was 2 H-1 0.001 amperes and the plating time 10 minutes. Air agitation 14 @1 ⁇ Air Poor.
  • Each property in groups (1) and (2) is independently 1 measured as poor, fair, good, and very good as 21 1 0 3g Air 0 very good, follows: 11-7 0. 00075 Property (1) pe y Rating Width of lustrous current density range Rating Degree of leveling Poor Less than one half of length of test panel Poor No visual change in original roughness of scratched band Fair More than onehalf andless than two thirds of length oitestpanel Fair Ntg ig e a l i le decrease in roughness. but scratches still Good More than two thirds but less than entire length of test pane1 Good Rtiughlne ss decreased andportions of scratches completely 8V6 Very good... Entire length of test panel is lustrous Very good... Scratches on the portion of the panel having a current density greater than 2.5 a./s.d. are practically invisible.
  • H4 88 Good Good to very good leveling and good to very good semi- 7 .0 bright Olll'gllt ggnsity ratnge or good levehng and good to 00 very goo rig curren ensl yrange. I Poor Poor leveling and/or poor lustrous current density range. 25 H4 88 Very good- Fair All intermediate panels not otherwise classified. gg 0 2 26 8-7 0.05 Meclganicalu Poor. TABLE VI 28 0.20 ⁇ . 0 Do. A yp p 3 3: Additives g./l. agitation Result 29 Good H-1 0.001 Exam 10 No.2
  • R-SOaM in effective amount of 0.001 g./l.-1.0 g./l.
  • a polyether containing at least 5 ether oxygen atoms per molecule in effective amount of 0.005- 10.0 g./l.
  • each R is independently a divalent aliphatic or aromatic non-heterocyclic group of 1-10 carbon atoms;
  • R is hydrogen, a metal cation, a monovalent aliphatic or aromatic organo group of 1-20 carbon atoms, or the groups RSO M or R(S) RSO M wherein q is an integer 2-5;
  • M is a cation;
  • n is an integer 2-4.
  • n is an integer 2-4, R is an aromatic group, and R is a polymethylene group.
  • polysulfide compound is of the formula in which R is NaO S(CH n is 2; and R is (CH-Q 5.
  • the polysulfide compound is of the formula in which R is NaO S(CH S (CH n is 2; and R is 2)3- 6.
  • the polysulfide compound is of the formula in R, is n is 2; and R is (CH2)3.
  • polysulfide compound is of the formula in which R is NaO S(CH S (CH n is 2; and R is 2):;-
  • a process as claimed in claim 1 wherein the polysulfide compound is of the formula f R S in which R is NaO SCH CH(OH)CH n is 2; and R is CH CH(OH)CH 12.
  • a process as claimed in claim 1 wherein X is S-. 13.
  • polyether is RSOaNa RSOaNa RSOaNa Ill- ⁇ 41:30, and wherein the process is carried out in the presence of a dispersing agent of the formula 20.
  • a composition for electrodepositing bright, strongly leveled, ductile copper which comprises an aqueous acidic copper plating bath containing chloride ions and at least one member from each of the following groups:
  • a polyether containing at least 5 ether oxygen atoms per molecule in effective amount of 0.005- 10.0 g./l.
  • each R is independently a divalent aliphatic or aromatic non-heterocyclic group of 1-10 carbon atoms;
  • R is hydrogen, a metal cation, a monovalent aliphatic or aromatic organo group of 1-20 carbon atoms, or the groups RSO M or -R-(S),, --RSO wherein q is an integer 2-5;
  • M is a cation;
  • R" is hydrogen or an alkyl, hydroxyalkyl or aminoalkyl group of 1-6 carbon atoms; Y is a divalent organo group of 1-10 carbon atoms which forms a 5-6 membered cyclic ring structure with the group 24 28.
  • X is CH2CH2OH 29.
  • Y is CH CH 30.
  • the chloride ion concentration is at least 0.5 mg./l. of total aqueous bath composition.
  • a composition as claimed in claim 22 wherein the chloride ion concentration is 1-500 mg./l. of total aqueous bath composition.
  • a composition as claimed in claim 22 wherein the polyether is References Cited UNITED STATES PATENTS 2,663,684 12/1953 Pierce 20452 2,700,020 1/1955 Pierce 20452 2,840,518 6/1958 Condon 204-52 3,267,010 8/1966 Creutz et al. 20452 3,288,690 11/1966 Creutz et al. 20452 3,328,273 6/1967 CreutZ et al 20452 GERALD L, KAPLAN, Primary Examiner

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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JP (1) JPS4934887B1 (enrdf_load_stackoverflow)
BE (1) BE732051A (enrdf_load_stackoverflow)
BR (1) BR6908411D0 (enrdf_load_stackoverflow)
CA (1) CA924259A (enrdf_load_stackoverflow)
CH (1) CH537462A (enrdf_load_stackoverflow)
DE (1) DE1921845C3 (enrdf_load_stackoverflow)
ES (1) ES366560A1 (enrdf_load_stackoverflow)
FR (1) FR2007169A1 (enrdf_load_stackoverflow)
GB (1) GB1213097A (enrdf_load_stackoverflow)
NL (1) NL165513C (enrdf_load_stackoverflow)
SE (1) SE357771B (enrdf_load_stackoverflow)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715289A (en) * 1971-02-08 1973-02-06 Stauffer Chemical Co Brightener composition for acid copper electroplating baths
US3725220A (en) * 1972-04-27 1973-04-03 Lea Ronal Inc Electrodeposition of copper from acidic baths
US3770598A (en) * 1972-01-21 1973-11-06 Oxy Metal Finishing Corp Electrodeposition of copper from acid baths
US3940320A (en) * 1972-12-14 1976-02-24 M & T Chemicals Inc. Electrodeposition of copper
US3956079A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956078A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956084A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956120A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3966565A (en) * 1972-12-14 1976-06-29 M & T Chemicals Inc. Electrodeposition of copper
US4014760A (en) * 1974-11-21 1977-03-29 M & T Chemicals Inc. Electrodeposition of copper
US4036710A (en) * 1974-11-21 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4036711A (en) * 1975-12-18 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4781801A (en) * 1987-02-03 1988-11-01 Mcgean-Rohco, Inc. Method of copper plating gravure rolls
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US5417841A (en) * 1990-08-03 1995-05-23 Mcgean-Rohco, Inc. Copper plating of gravure rolls
US20040016502A1 (en) * 2002-07-26 2004-01-29 Jones Gregory K. Breathable materials comprising low-elongation fabrics, and methods
US20040217009A1 (en) * 2002-11-21 2004-11-04 Shipley Company, L.L.C. Electroplating bath
EP2537962A1 (en) * 2011-06-22 2012-12-26 Atotech Deutschland GmbH Method for copper plating
CN109778264A (zh) * 2017-11-10 2019-05-21 丹阳市金地生态园林发展有限公司 一种含环氧氯丙烷金属合金抗静电电镀液

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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US3804729A (en) * 1972-06-19 1974-04-16 M & T Chemicals Inc Electrolyte and process for electro-depositing copper
ZA739310B (en) * 1972-12-14 1974-11-27 M & T Chemicals Inc Electrode position of copper
US10060034B2 (en) * 2017-01-23 2018-08-28 Rohm And Haas Electronic Materials Llc Electroless copper plating compositions

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US2700020A (en) * 1952-06-02 1955-01-18 Houdaille Hershey Corp Plating copper
US2840518A (en) * 1954-07-19 1958-06-24 Westinghouse Electric Corp Acid copper addition agents and plating electrolytes embodying the same
US3267010A (en) * 1962-04-16 1966-08-16 Udylite Corp Electrodeposition of copper from acidic baths
US3288690A (en) * 1962-04-16 1966-11-29 Udylite Corp Electrodeposition of copper from acidic baths
US3328273A (en) * 1966-08-15 1967-06-27 Udylite Corp Electro-deposition of copper from acidic baths

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US2663684A (en) * 1952-06-02 1953-12-22 Houdaille Hershey Corp Method of and composition for plating copper
US2700020A (en) * 1952-06-02 1955-01-18 Houdaille Hershey Corp Plating copper
US2840518A (en) * 1954-07-19 1958-06-24 Westinghouse Electric Corp Acid copper addition agents and plating electrolytes embodying the same
US3267010A (en) * 1962-04-16 1966-08-16 Udylite Corp Electrodeposition of copper from acidic baths
US3288690A (en) * 1962-04-16 1966-11-29 Udylite Corp Electrodeposition of copper from acidic baths
US3328273A (en) * 1966-08-15 1967-06-27 Udylite Corp Electro-deposition of copper from acidic baths

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715289A (en) * 1971-02-08 1973-02-06 Stauffer Chemical Co Brightener composition for acid copper electroplating baths
US3770598A (en) * 1972-01-21 1973-11-06 Oxy Metal Finishing Corp Electrodeposition of copper from acid baths
US3725220A (en) * 1972-04-27 1973-04-03 Lea Ronal Inc Electrodeposition of copper from acidic baths
US3940320A (en) * 1972-12-14 1976-02-24 M & T Chemicals Inc. Electrodeposition of copper
US3956079A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956078A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956084A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956120A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3966565A (en) * 1972-12-14 1976-06-29 M & T Chemicals Inc. Electrodeposition of copper
US4014760A (en) * 1974-11-21 1977-03-29 M & T Chemicals Inc. Electrodeposition of copper
US4036710A (en) * 1974-11-21 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4036711A (en) * 1975-12-18 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4781801A (en) * 1987-02-03 1988-11-01 Mcgean-Rohco, Inc. Method of copper plating gravure rolls
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US5417841A (en) * 1990-08-03 1995-05-23 Mcgean-Rohco, Inc. Copper plating of gravure rolls
US20040016502A1 (en) * 2002-07-26 2004-01-29 Jones Gregory K. Breathable materials comprising low-elongation fabrics, and methods
US20040217009A1 (en) * 2002-11-21 2004-11-04 Shipley Company, L.L.C. Electroplating bath
EP2537962A1 (en) * 2011-06-22 2012-12-26 Atotech Deutschland GmbH Method for copper plating
CN103703167A (zh) * 2011-06-22 2014-04-02 安美特德国有限公司 镀铜方法
CN103703167B (zh) * 2011-06-22 2016-06-29 安美特德国有限公司 镀铜方法
US9506158B2 (en) 2011-06-22 2016-11-29 Atotech Deutschland Gmbh Method for copper plating
TWI560326B (en) * 2011-06-22 2016-12-01 Atotech Deutschland Gmbh Method for copper plating
CN109778264A (zh) * 2017-11-10 2019-05-21 丹阳市金地生态园林发展有限公司 一种含环氧氯丙烷金属合金抗静电电镀液

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GB1213097A (en) 1970-11-18
DE1921845A1 (de) 1969-11-06
CA924259A (en) 1973-04-10
CH537462A (de) 1973-05-31
BE732051A (enrdf_load_stackoverflow) 1969-10-01
FR2007169A1 (enrdf_load_stackoverflow) 1970-01-02
JPS4934887B1 (enrdf_load_stackoverflow) 1974-09-18
NL6906599A (enrdf_load_stackoverflow) 1969-10-31
BR6908411D0 (pt) 1973-01-09
SE357771B (enrdf_load_stackoverflow) 1973-07-09
NL165513B (nl) 1980-11-17
DE1921845C3 (de) 1980-07-31
NL165513C (nl) 1981-04-15
ES366560A1 (es) 1971-07-16
DE1921845B2 (de) 1979-11-15

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