CN101044269A - Pulse reverse electrolysis of acidic copper electroplating solutions - Google Patents
Pulse reverse electrolysis of acidic copper electroplating solutions Download PDFInfo
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- CN101044269A CN101044269A CNA2005800203503A CN200580020350A CN101044269A CN 101044269 A CN101044269 A CN 101044269A CN A2005800203503 A CNA2005800203503 A CN A2005800203503A CN 200580020350 A CN200580020350 A CN 200580020350A CN 101044269 A CN101044269 A CN 101044269A
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- copper
- electroplate liquid
- concentration
- pulse
- polyalkylene glycol
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention provides pulse reverse electrolysis of acid copper solutions is used for applying copper to printing cylinders, especially gravure printing cylinders. The plating composition generally comprising copper ions, counter ions, chloride ions, a polyalkylene glycol, and a bath-soluble divalent sulfur compound. The benefits include an improved thickness distribution of the copper electrodeposited on the plated article, reduced metal waste, reduced plating times and increased production capacity.
Description
Technical field
The present invention relates to a kind of method of making photogravure roller.
Background technology
Know by the acidic solution electro-coppering, have a lot of industrial application.In great majority were used, the object of electroplated was suspended in the electrolytic solution, and a kind of technology is commonly called rack plating.Rack plating is a kind of process of knowing, in people's such as Fueki U.S. Patent No. 3,939,056 and the U.S. Patent No. 4,176,039 of Wismer and the U.S. Patent No. 4 of Salman, can find the example of this process in 297,197, its theme separately is incorporated herein in the mode of all quoting.
Industrial, the application that another kind is known is to be used to print the copper steel plating of application examples such as intaglio printing and the cylinder of aluminium, wherein adopts steel or aluminium to provide cheap and firm base material for carving copper coating.Intaglio printing is a kind of method that adopts woodburytype, and pattern wherein to be printed comprises the recess of etching or engraving, usually its degree of depth difference.Be applied to the solvent inkjet ink of toughness slightly on the whole surface and the metal doctor blade sheet is removed excessive ink from non-print surface.Normally carve on the copper facing cylinder, chromium plating subsequently is so that wearing and tearing reduce to minimum.
The plating of printing cylinder and other associated treatment normally occur in the suitable groove that contains electrolytic solution, this drum segment or whole the immersion wherein.Cylinder is as negative electrode, and direct current is by this cylinder and have suitable anodic electrolytic solution, finishes the circuit that has power supply.Cylinder rotation during this process, groove is equipped with filtration and temperature-control device so that good process control to be provided usually.If desired, also can utilize solution stirring device for example air or solution mechanism.
Preparation be used for the galvanized printing cylinder of acid copper be by clean surface at first deoil to remove, dirt and grease and oxidation products, provide suitable surface to be used for electroplating thus.By copper (I) solion, normally cyanide-based electrolyte is coated with skim copper on the steel cylinder then.Guarantee the copper coating that obtains adhering to by avoiding on steel substrate carrying out replacement(metathesis)reaction with copper (II) electrolytic solution, this replacement(metathesis)reaction may cause adherence of coating poor.Process aluminum drum by the Chemical Pretreatment that can produce thin zinc layer on aluminium, it makes this base material be suitable for being applied near neutral solution by the pH value copper or the nickel of thin layer then.
To have the cylinder electricity plated with copper of thin copper or nickel coating to produce a thick-layer copper, about usually 100-500 micron by acid copper (II) electrolytic solution then.In subordinate phase, acidic copper electrolytes is better than copper (I) electrolytic solution, because acidic copper electrolytes is electroplated faster under employing high current density situation.Usually the current density that adopts is 20-25A/dm
2Described the example that is used for the copper-plated prior art process of photogravure roller in the United States Patent(USP) Nos. 5,417,841 and 4,781,801 of Frisby, their themes separately are incorporated herein in the mode of all quoting.
Owing to electroplate the character of distribution of current during processing, copper coating on the printing cylinder can be that the coating of very uneven and common cylinder end is central thick more a lot of than cylinder, though the degree of this variation since cylinder sizes with the plating condition and different, but the copper coating of printing cylinder is that the twice of cylinder central thickness is unrare in the cylinder end portion thickness, and it makes cylinder be unsuitable for printing process.For make cylinder be suitable for the printing, must handle copper-plated cylinder to provide the surface of a coating, for example the variation on this whole surface of cylinder be not more than the pact+/-2 microns.This obtains by the twice polishing operation usually: at first be machining operations, it removes a large amount of relatively copper, secondly is meticulous polishing operation.
Prepared then to be carved as mentioned above by the cylinder of plating, mechanical workout and polishing or etching on pattern to be printed.For obtaining accurately consistent engraving, the hardness that copper coating has suitable homogeneous is necessary, and this can control by the additive in the copper plating solution.Copper coating does not have plating defect, and for example space (pit) and coarse injustice also are necessary.In case printed patterns in engraving or the etching is just electroplated skim chromium so that it has wear resistance in printing operation at this cylinder.
The cylinder wearing and tearing take place during printing operation, and remove by further mechanical processing steps normally with old cylinder that the coating of pre-determined thickness repairs, so that whole printed patterns is removed from cylinder surface.The thickness of removing is about 100 microns usually.This cylinder can be manufactured then and be applicable to further electro-coppering, coating is got back to initial plated thickness.Subsequently, this cylinder passes through mechanical workout, polishing and the engraving process of standard and is made into can be used for further printing, and so independent cylinder can continue to use.
The shortcoming that is used to prepare the prior art of cylinder is: in order to reach the ideal thickness on the whole length of printing cylinder, the thickness of the copper coating of cylinder central authorities must be minimum.Remove excessive part from the edge by mechanical workout then, this is the expensive and operation consuming time of expense, and it produces a large amount of copper scrap metals.Therefore, needing a kind of improving one's methods of photogravure roller that prepare in the art, this method does not need just can reach by mechanical processing steps afterwards the copper coating of consistency of thickness on whole printing cylinder length.
Adopt the pulse reverse electroplating technology in electronic industry, to know, be used for copper being plated in printed circuit board (PCB) and other base material by acidic solution by acidic solution copper facing.People's such as Taylor U.S. Patent No. 6,319,384, its theme is incorporated herein in the mode of all quoting, disclose a kind of on the semiconductor-based end method of acid copper, wherein said acidic copper electroplating solutions does not have whitening agent and/or even paint substantially.
" the Effect of Pulsed Current On The Electrodeposition ofChromium and Copper " of T.Pearson, PhD thesis, Aston University, United Kingdom, 1989, illustrated the Essential Chemistry of the additive that is used for electronic application and they under the pulsed current plating condition with the direct current condition under performance relatively.This additive roughly is similar to those that are adopted in conventional rack plating is used, and roughly comprises sulfopropyl sulfide and polyalkylene glycol, and itself and chlorion act synergistically.These hole general diameters are that the 0.5mm and the degree of depth are 2-3mm.Usually the cathode current density that is adopted in the plating of printed circuit board (PCB) is 2.0A/dm
2But because geometry factor, the watt current density in the hole is very little and little more a lot of than the average current density that is applied on this plate generally.
People's such as Herdman U.S. Patent Application Publication No.2004/0074775, its theme is incorporated herein in the mode of all quoting, describe plating of use pulse reverse and acidic copper electrolytes and be used for the decorative copper application, for example be used for the plating on the plastics of automobile or hygiene applications, or on the alloy automobile wheel, electroplate.This method improvement the distribution of copper coating on whole base material.The current density range of describing in above application is 0.5-5.0A/dm
2, but the current density of using usually is 2.0-3.0A/dm
2Yet this current density range is lower than the copper-plated current density of printing cylinder and requires about order of magnitude.
The U.S. Patent Application Publication No.2002/0079228 of the Smith that another is nearest, its theme is incorporated herein in the mode of all quoting, described a kind of electroplanting device and method of photogravure roller, this method has adopted electroplates the plating bath that is applied to based on copper sulfate, sulfuric acid and chlorion with pulse reverse.
The inventor finds that surprisingly the pulse-reverse current electroplating technology that is used for printed circuit board (PCB) also can be converted into the application of electroplating electro-coppering under institute's employing condition at printing cylinder well.Surprisingly its current density range with during the electroplating printed circuit board or rack plating applied widely different during using, and be surprised at since routine electroplate use in the current density increase cause Metal Distribution poorer.When utilizing pulse reverse to electroplate to combine with the optimization additive system that is used for pulse reverse electrolysis when electroplating printing cylinder, the distribution of copper deposit on the whole length of this cylinder has significantly been improved.For the galvanizer, this has two tangible advantages: the excess copper that (1) is deposited on the cylinder end reduces, and (2) can reach desired thickness by the middle section of electro-plating roller in the less time or under the less current density.Above-described advantage can cause polishing to require reduction, metallic scrap product to reduce and throughput and energy-conservation increase.The coating of making is uniformly, does not have surface imperfection, and also can reach Hardness Control by specific solution additive.
Summary of the invention
The pulse reverse plating is used for copper-plated purposes and can be used for a kind of method of electroplating printing cylinder at acidic copper electroplating solutions, and this method may further comprise the steps:
(a) cylinder is suspended at contains cupric ion, gegenion, chlorion, polyalkylene glycol and dissolve in the electroplate liquid of divalent sulfur compound of plating bath; And
(b) at the copper of one section time enough of electro-plating roller under alternative negative electrode and the anodic current with formation desired thickness on described cylinder surface.
Embodiment
The present invention utilizes pulse-reverse current to electroplate photogravure roller so that form the copper of desired thickness on cylinder surface with copper in acidic copper electroplating solutions.The present invention is particularly conducive to power in whole printing cylinder length and plates the uniform copper of thickness.
Acidic copper electroplating solutions of the present invention generally includes cupric ion, source of counter, chlorion, polyalkylene glycol and dissolves in the divalent sulfur compound of plating bath.Also can with other additive for example wetting agent add in the plating bath to improve copper coating.
Copper ion concentration in electroplate liquid is about 30-70g/l.Salzburg vitriol is the example that can be used for the copper compound of plating bath of the present invention.Other copper compound well known by persons skilled in the art comprises as copper methanesulfonate, and the mixture of this compounds, also is fit to.Electroplate liquid generally includes Salzburg vitriol, and its concentration is about 120-280g/l, preferably is about 150-200g/l.
Source of counter in the electroplate liquid is that sulfate ion is the most general, but also can be methanesulfonate ions or this class ionic mixture.Preferred source of sulfate ions is a sulfuric acid.When sulfate radical was gegenion, the sulfuric acid concentration in electroplate liquid usually was about 50-250g/l, preferably is about 80-140g/l, and is most preferably 100-110g/l.
Chlorion also can be present in the electroplate liquid, and concentration is about 10-500mg/l, preferably is about 75-150mg/l.Chloride-ion source in the preferred electroplate liquid is a hydrochloric acid.
The concentration of the polyalkylene glycol in the electroplate liquid is about 50-10, and 000mg/l preferably is about 300-1,000mg/l.The molecular weight of this polyalkylene glycol is generally 500-100, and 000.Preferred polyalkylene glycol comprises polyoxyethylene glycol and ethylene oxide/propylene oxide multipolymer, also can adopt the mixture of the suitable polyalkylene glycol of this class.
Usually the concentration of the divalent sulfur compound that dissolves in electroplate liquid that is had in electroplate liquid is about 1-150mg/l, preferably is about 30-50mg/l.Preferred divalent sulfur compounds includes, but is not limited to: sulfydryl propanesulfonic acid or its an alkali metal salt, two-(propane-3-sulfonic acid) disulphide or its an alkali metal salt, with two-(ethane-2-sulfuric acid) disulphide or its an alkali metal salt, and above-mentioned one or more mixture.
Other commercially available additive for example wetting agent, whitening agent etc. also can add in the electroplating liquid composition of the present invention, can add these additives and reduce to minimum with the formation that will cave in, or change coating performance, for example hardness or visual appearance.For those skilled in the art, this class additive is normally known.
The pulse plating mode of electroplate liquid comprises alternative negative electrode and anodic pulse.The cathode pulse time is generally the 5-100 millisecond, and the anodic pulse time is generally the 0.1-10 millisecond.Optionally, plating mode can comprise the cathode deposition period of time expand in addition, for example reaches about 1 hour, or can comprise for example zero current of 0-10 millisecond of short period between anode and cathode pulse, is commonly referred to " dead time ".
Printing cylinder can completely or partially immerse in the copper electroplating liquid composition of the present invention.Preferred printing cylinder partly immerses in the copper electroplating liquid.In addition, printing cylinder can rotate in electroplating liquid composition.
The average current density that applies is about 10.0-35.0A/dm usually
2The current density during the anodic pulse normally the current density during the cathode pulse 1-5 doubly.
Optionally but in the preferred embodiment, can on the copper layer on the printing cylinder, apply one deck chromium subsequently.Generally be to apply this layer by electroplating.
Embodiment
Following non-limiting example has proved various feature of the present invention, in following examples, is that 210mm and length are that the typical print cylinder of 400mm is electroplated in acid copper solution with diameter.Before electroplating, this printing cylinder is coated with copper in advance and polishes.
The electrolyte temperature of experimental session is about 30 ℃.During the plating, will rotate in this cylinder 50% immersion solution and with 75rpm.What the current density that attention applies referred to only is the submergence part of this cylinder.
Embodiment 1-prior art
The electroplating liquid composition that adopts comprises following:
Salzburg vitriol 220g/l
Sulfuric acid 35g/l
Chlorion does not have
Specialist additive has
Plating mode: direct current 25A/dm
2
Electroplating time 1 hour
Copper coating has bright outward appearance, does not observe depression, irregular spherolite or other defective on the printing cylinder surface.
Embodiment 2
The electroplating liquid composition that adopts comprises following:
Salzburg vitriol 150g/l
Sulfuric acid 105g/l
Chlorion 85mg/l
Polyoxyethylene glycol (MW 12,000) 400mg/l
It is two-(propane-3-sulfonic acid) disulphide,
Disodium salt 35mg/l
Specialist additive does not have
Plating mode: average pulse 15A/dm
2
The 38ms forward
2ms reverse 2 times to forward current
Electroplating time 1 hour
Copper coating has bright outward appearance, does not observe depression, irregular spherolite or other defective on the printing cylinder surface.
Embodiment 3
The electroplating liquid composition that adopts comprises following:
Salzburg vitriol 150g/l
Sulfuric acid 105g/l
Chlorion 85mg/l
Ethylene oxide/propylene oxide
Multipolymer (MW 12,000) 400mg/l
The sulfydryl propane sulfonic acid,
Sodium salt 25mg/l
Specialist additive has
Plating mode: average pulse 15A/dm
2
The 20ms forward
1ms reverse 2 times to forward current
Electroplating time 1 hour
Copper coating has bright outward appearance, does not observe depression, irregular spherolite or other defective on the printing cylinder surface.
Embodiment 4
The electroplating liquid composition that adopts comprises following:
Salzburg vitriol 150g/l
Sulfuric acid 105g/l
Chlorion 85mg/l
Ethylene oxide/propylene oxide
Multipolymer (MW 33,000) 300mg/l
It is two-(ethane-2-sulfuric acid) disulphide,
Disodium salt 40mg/l
Specialist additive has
Plating mode: average pulse 15A/dm
2
The 10ms forward
0.5ms reverse 2 times to forward current
Electroplating time 1 hour
Copper coating has bright outward appearance, does not observe depression, irregular spherolite or other defective on the printing cylinder surface.
Be to determine the thickness of copper, before the plating stage and utilize accurate micrometer afterwards along five point measurement diameter of cylinder on the cylinder as shown in Figure 1.With the increase part of diameter after the plating stage divided by 2 thickness of coating of calculating in micron.Be shown in table 1 for the copper thickness measuring result that each embodiment carried out.
The thickness of coating of each point (μ m) on the whole width of table 1. printing cylinder
The commercially available hardness measuring device of utilization calibration (the CuH1 type, available from Graphische, Technikand Handel Heimann GmbH), measure coating hardness at identical point shown in Figure 1 place.The coating hardness measuring result of each point is shown in Table 2 on the whole width of printing cylinder.
Obviously, adopt process of the present invention, shown in embodiment 2-4, with the new electroplating composition of the present invention adopt pulse reverse electroplate the coating that forms on the whole surface of printing cylinder, change less than+/-2 microns.The coating that utilizes galvanic art methods to form on the other hand is widely different on the whole surface of printing cylinder.The prior art electro-plating roller in order to can be used as the purpose of printing cylinder, must carry out further polishing step as mentioned above, the time and the expense that need be spent more than the described novel method of the present inventor.
Utilize the commercially available hardness measuring device (CuH1 type, available from Graphische, Technikand Handel Heimann GmbH) of calibration to measure coating hardness, embodiment 1 and 4 measuring result are shown in table 2.Shown in the result be HV300 unit, i.e. Vickers' hardness scale, loading condiction are 300 grams.
The hardness (HV50) of each point on the whole width of table 2. printing cylinder
Described the present invention though just electroplate the context of photogravure roller, the invention is not restricted to this special application and can be applicable to other application that needs similar electroplating composition and plating condition and similar base material.
Claims (25)
1. method of in acidic copper electroplating solutions, making printing cylinder, this method comprises:
(a) described printing cylinder is suspended in the electroplate liquid of the divalent sulfur compound that contains cupric ion, gegenion, chlorion, polyalkylene glycol and dissolve in plating bath; And
(b) electroplating described printing cylinder for some time under alternative negative electrode and the anodic current on described printing cylinder surface, to form the copper of desired thickness.
2. method according to claim 1, wherein said gegenion is a sulfate radical.
3. method according to claim 2, wherein said gegenion comprises sulfuric acid, its concentration is about 50-250g/l.
4. method according to claim 3, wherein said sulfuric acid concentration is about 80-140g/l.
5. method according to claim 1, wherein said electroplate liquid contains cupric ion, and its concentration is about 30-70g/l.
6. method according to claim 1, wherein said copper ion source comprises Salzburg vitriol.
7. method according to claim 6, the Salzburg vitriol concentration in the wherein said electroplate liquid is about 120-180g/l.
8. method according to claim 1, the chlorine ion concentration in the wherein said electroplate liquid is about 10-500mg/l.
9. method according to claim 8, the chlorine ion concentration in the wherein said electroplate liquid is about 75-150mg/l.
10. method according to claim 1, the polyalkylene glycol concentration in the wherein said electroplate liquid is about 50-10,000mg/l.
9. method according to claim 8, the polyalkylene glycol concentration in the wherein said electroplate liquid is about 500mg/l.
10. method according to claim 1, the molecular weight of wherein said polyalkylene glycol is about 500-100, and 000.
11. method according to claim 10, wherein said polyalkylene glycol is a polyoxyethylene glycol.
12. method according to claim 10, wherein said polyalkylene glycol are a kind of ethylene oxide/propylene oxide multipolymers.
13. method according to claim 1, the divalent sulfur compound concentration that dissolves in plating bath in the wherein said electroplate liquid is about 1-150mg/l.
14. method according to claim 13, the divalent sulfur compound concentration that dissolves in plating bath in the wherein said electroplate liquid is about 30-50mg/l.
15. method according to claim 1, wherein said divalent sulfur compound are by sulfydryl propanesulfonic acid, two-(propane-3-sulfonic acid) disulphide, two-(ethane-2-sulfuric acid) disulphide, and select in the group of an alkali metal salt composition.
16. method according to claim 1, wherein said electroplate liquid also comprise the composition of selecting by in wetting agent, whitening agent and even paint, other known copper coating properties-correcting agent and above-mentioned one or more groups that form.
17. method according to claim 1, the wherein said cathode pulse time is about the 5-100 millisecond, and the anodic pulse time is about the 0.1-10 millisecond.
18. method according to claim 17, wherein said pulse plating mode also comprises the cathode deposition period of time expand.
19. method according to claim 18, wherein said final cathode pulse reaches about 1 hour.
20. method according to claim 1, the average impressed current density that wherein is applied to negative electrode and anodic pulse is about 10.0-35.0A/dm
2
21. method according to claim 1, the current density during the wherein said anodic pulse are 1-5 times of the current density during the described cathode pulse.
22. photogravure roller according to the described process manufacturing of claim 1.
23. wherein there is for some time that does not have electric current substantially in method according to claim 1 between the alternate cycle of described negative electrode and anodic current.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/876,795 US20050284766A1 (en) | 2004-06-25 | 2004-06-25 | Pulse reverse electrolysis of acidic copper electroplating solutions |
| US10/876,795 | 2004-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101044269A true CN101044269A (en) | 2007-09-26 |
Family
ID=35504436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800203503A Pending CN101044269A (en) | 2004-06-25 | 2005-03-15 | Pulse reverse electrolysis of acidic copper electroplating solutions |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20050284766A1 (en) |
| EP (1) | EP1766106A4 (en) |
| JP (1) | JP2008504435A (en) |
| CN (1) | CN101044269A (en) |
| WO (1) | WO2006011922A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768765B (en) * | 2008-12-29 | 2013-03-13 | 财团法人工业技术研究院 | Electrolyte and method for manufacturing copper foil by using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153408B1 (en) * | 2006-04-13 | 2006-12-26 | Herdman Roderick D | Copper electroplating of printing cylinders |
| WO2008126522A1 (en) * | 2007-03-15 | 2008-10-23 | Nippon Mining & Metals Co., Ltd. | Copper electrolyte solution and two-layer flexible substrate obtained by using the same |
| WO2019038666A1 (en) | 2017-08-22 | 2019-02-28 | Behboudikhiavi Sepideh | Synthesis of lithium manganese dioxide micro/nanostructures |
| CN112368424A (en) * | 2018-06-15 | 2021-02-12 | 阿尔贝托·托德斯卡 | Electrolytic treatment method for coating stainless steel objects |
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| US79228A (en) * | 1868-06-23 | Improvement in hoese eay-foees | ||
| US74775A (en) * | 1868-02-25 | Improvement in cultivatoes | ||
| US2558090A (en) * | 1947-12-11 | 1951-06-26 | Westinghouse Electric Corp | Periodic reverse current electroplating apparatus |
| US2700019A (en) * | 1951-07-05 | 1955-01-18 | Westinghouse Electric Corp | Acid copper plating |
| US4101386A (en) * | 1971-05-07 | 1978-07-18 | Siemens Aktiengesellschaft | Methods of coating and surface finishing articles made of metals and their alloys |
| US3703621A (en) * | 1971-07-21 | 1972-11-21 | Rapid Electric Co Inc | Reciprocating frusto-conical plug switch contact and assembly |
| US3939056A (en) * | 1973-10-19 | 1976-02-17 | Sony Corporation | Coated plating rack |
| US3923610A (en) * | 1974-08-27 | 1975-12-02 | Intaglio Service Corp | Method of copper plating gravure cylinders |
| US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
| US4301727A (en) * | 1977-10-27 | 1981-11-24 | Bardin Karl D | Metal plated plastic base intaglio printing cylinders & plates and method of manufacture |
| US4176039A (en) * | 1979-03-02 | 1979-11-27 | Wismer Joseph C | Electroplating rack |
| US4297197A (en) * | 1980-11-13 | 1981-10-27 | International Telephone And Telegraph Corp. | Electroplating rack |
| US4781801A (en) * | 1987-02-03 | 1988-11-01 | Mcgean-Rohco, Inc. | Method of copper plating gravure rolls |
| DD264030A1 (en) * | 1987-08-26 | 1989-01-18 | Leipzig Galvanotechnik | ELECTROLYTE FOR THE SEPARATION OF GLOSS-COPPER LAYERS WITH INCREASED MICROHAERTE |
| EP0469724B1 (en) * | 1990-08-03 | 1995-06-07 | Mcgean-Rohco, Inc. | Copper plating of gravure rolls |
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| DE4211881C2 (en) * | 1992-04-09 | 1994-07-28 | Wmv Ag | Process for the electrochemical application of a structured surface coating |
| DE19545231A1 (en) * | 1995-11-21 | 1997-05-22 | Atotech Deutschland Gmbh | Process for the electrolytic deposition of metal layers |
| US6319384B1 (en) * | 1998-10-14 | 2001-11-20 | Faraday Technology Marketing Group, Llc | Pulse reverse electrodeposition for metallization and planarization of semiconductor substrates |
| US6652727B2 (en) * | 1999-10-15 | 2003-11-25 | Faraday Technology Marketing Group, Llc | Sequential electrodeposition of metals using modulated electric fields for manufacture of circuit boards having features of different sizes |
| US20020079228A1 (en) * | 2000-12-27 | 2002-06-27 | Robert Smith | Electroplating of gravure cylinders |
| US6723219B2 (en) * | 2001-08-27 | 2004-04-20 | Micron Technology, Inc. | Method of direct electroplating on a low conductivity material, and electroplated metal deposited therewith |
| US20040074775A1 (en) * | 2002-10-21 | 2004-04-22 | Herdman Roderick Dennis | Pulse reverse electrolysis of acidic copper electroplating solutions |
| US6904658B2 (en) * | 2003-06-02 | 2005-06-14 | Electroformed Stents, Inc. | Process for forming a porous drug delivery layer |
-
2004
- 2004-06-25 US US10/876,795 patent/US20050284766A1/en not_active Abandoned
-
2005
- 2005-03-15 CN CNA2005800203503A patent/CN101044269A/en active Pending
- 2005-03-15 EP EP05725574A patent/EP1766106A4/en not_active Withdrawn
- 2005-03-15 JP JP2007518029A patent/JP2008504435A/en active Pending
- 2005-03-15 WO PCT/US2005/008502 patent/WO2006011922A2/en not_active Application Discontinuation
-
2009
- 2009-05-21 US US12/469,760 patent/US20090223827A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768765B (en) * | 2008-12-29 | 2013-03-13 | 财团法人工业技术研究院 | Electrolyte and method for manufacturing copper foil by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006011922A3 (en) | 2007-02-22 |
| WO2006011922A2 (en) | 2006-02-02 |
| EP1766106A2 (en) | 2007-03-28 |
| US20050284766A1 (en) | 2005-12-29 |
| EP1766106A4 (en) | 2007-09-05 |
| US20090223827A1 (en) | 2009-09-10 |
| JP2008504435A (en) | 2008-02-14 |
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Open date: 20070926 |