CN1764744A - Electrolytic copper foil with low roughness surface and process for producing the same - Google Patents
Electrolytic copper foil with low roughness surface and process for producing the same Download PDFInfo
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- CN1764744A CN1764744A CNA2004800078246A CN200480007824A CN1764744A CN 1764744 A CN1764744 A CN 1764744A CN A2004800078246 A CNA2004800078246 A CN A2004800078246A CN 200480007824 A CN200480007824 A CN 200480007824A CN 1764744 A CN1764744 A CN 1764744A
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- uneven surface
- copper foil
- electrolytic copper
- low
- electrolytic
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011889 copper foil Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 241000370738 Chlorion Species 0.000 claims description 17
- 239000002932 luster Substances 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 229920002873 Polyethylenimine Polymers 0.000 abstract description 5
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 2
- 125000006353 oxyethylene group Chemical group 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- -1 polyoxyethylene Polymers 0.000 description 14
- 238000000635 electron micrograph Methods 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XJJLDAFQFHBVBT-UHFFFAOYSA-N O1CC1.OC(CC)(C1=CC=CC=C1)O Chemical compound O1CC1.OC(CC)(C1=CC=CC=C1)O XJJLDAFQFHBVBT-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
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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)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
An electrolytic copper foil with low roughness surface whose surface roughness (Rz) is 2.0 mum or less, the surface uniformly provided with low roughness without uneven surge, which electrolytic copper foil exhibits a percent elongation of 10.0% or higher at 180 DEG C. This electrolytic copper foil with low roughness surface can be obtained by a process for producing an electrolytic copper foil, comprising passing a direct current between an insoluble anode consisting of a titanium plate coated with a Platinum Group element or oxide thereof and a titanium drum as a cathode counter to the anode in an electrolyte of an aqueous solution of sulfuric acid/copper sulfate, wherein the electrolyte contains an oxyethylene surfactant, a polyethyleneimine or derivative thereof, a sulfonate of active organosulfur compound and chloride ions.
Description
Technical field
The present invention relates to low uneven surface electrolytic copper foil and manufacture method thereof actual use, uneven surface no concave-convex uneven surface that rise and fall, that have uniform low roughness on printing distributing board and negative electrode for lithium secondary battery current collector.
Background technology
As everyone knows, electrolytic copper foil is to make electrolytic solution with sulfuric acid-copper sulfate solution, the insoluble anode that constitutes by the titanium plate of platinum element or its oxide elements lining and with respect to adopting titanium system roller on this anodic negative electrode, by logical direct current between these the two poles of the earth, electrolytic copper is separated out on titanium system roller, at this moment, titanium system roller rotates with certain speed, makes by the method that the electrolytic copper of will separate out is peeled off and batched continuously from roller surface.
In the present invention, the face with the roller surface contact side of electrolytic copper foil is called " glossy surface ", and its reverse side is called " uneven surface ".
Can make electrolytic copper foil as stated above, but these those skilled in the art are called this electrolytic copper foil " Copper Foil is untreated ", usually, this Copper Foil that is untreated can not directly use, as the used for printed circuit electrolytic copper foil time, process: be used to improve with resin bond be that the various surface treatment procedures that the roughened operation of purpose and being used to is given thermotolerance, resistance to chemical reagents and antirust power become goods.
Before this, in the manufacturing process of electrolytic copper foil of being untreated, there are the chlorion of 10～100mg/L and gelatine or the gelatin of 0.1～4.0mg/L by adopting in the electrolytic solution, make the method for (roughening) of the mountain valley shape sharpening of uneven surface side, and in recent years, the electrolytic copper foil that is used for printing distributing board and negative electrode for lithium secondary battery current collector, require the roughness of its uneven surface side low as far as possible, the roughness difference of glossy surface and uneven surface is little, and (because of glossy surface is the smooth-shaped of duplicating the cathode roller surface, so it is poor to certainly lead to roughness between glossy surface and uneven surface), and, require thin electrolytic copper foil.
This is because when being used for printing distributing board, being accompanied by graph thinning and thin patterning, need to improve the viewpoint of circuit precision desired, in addition, when being used for the lithium ion secondary battery cathode current collector, owing to consider that the roughness between glossy surface and the uneven surface is poor, in other words, consider the cause that the necessity based on the cell reaction difference of the difference of surface-area diminishes.
Yet, the roughness difference of glossy surface and uneven surface is diminished, and to satisfy practical various mechanical propertys to be difficult.
In the past, known in the manufacture method of electrolytic copper foil, by in electrolytic solution, suitably selecting to add various water-soluble high-molecular substances, various tensio-active agents, various organosulfur compounds, chlorion etc., the roughness difference of glossy surface and uneven surface is diminished, for example, Japanese Unexamined Patent Application Publication 2002-506484 communique discloses, in electrolytic solution, add the low-molecular weight water-soluble ether of cellulose, low-molecular weight water-soluble polyalkylene glycols ether, when low-molecular weight water-soluble polymine and water soluble sulfonated organosulfur compound, can obtain having on the uneven surface electrolytic copper foil (electrolytic copper foil is untreated) of the following trickle projection highly of about 3.8 μ m, for example, Japan's No. 3313277 communique of special permission discloses, when in electrolytic solution, adding ether of cellulose, lower molecular weight glue, when having the compound of sulfydryl and chloride ion, the roughness that can obtain the uneven surface side is low, the roughness difference of glossy surface and uneven surface is little, and shows the electrolytic copper foil (electrolytic copper foil is untreated) of high high temperature elongation.
Appropriate combination in the electrolytic solution that is made of sulfuric acid-copper sulfate solution such as the inventor is added the various water-soluble high-molecular substances of putting down in writing in above-mentioned each communique, various organosulfur compounds, chlorion etc., repeatedly carried out making the experiment of electrolytic copper foil, consequently, though the roughness of the uneven surface side of resulting electrolytic copper foil is low, on this uneven surface, produce concavo-convex fluctuating (Fig. 7 below the reference) slowly.
The concavo-convex fluctuating slowly that is produced on the uneven surface of electrolytic copper foil (electrolytic copper foil is untreated) becomes the major reason of separating out unusually of bringing out the copper crystalline particle in above-mentioned roughened operation, and the roughness (Rz) of the uneven surface of goods is risen.
In addition, in the time of on being used for flexible printing patch panel, with the bonding operation of insulating film in Copper Foil be heated because this being heated, when copper crystalline particle hour, this copper crystalline particle grow up become thick.
So, technical task of the present invention provides a kind of, can be useful on the uneven surface of printing distributing board and negative electrode for lithium secondary battery current collector and concavo-convex fluctuating not occur, low uneven surface electrolytic copper foil with uniformly low uneven surface, the concrete roughness Rz that provides a kind of uneven surface concavo-convex fluctuating do not occur on this uneven surface below 2.0 μ m, have the uneven surface of uniform low roughness, and, reach low uneven surface electrolytic copper foil more than 10.0% at 180 ℃ elongations.
The inventor etc., for solve above-mentioned problem concentrate one's attention on research found that, in the electrolytic solution of sulfuric acid-copper sulfate solution formation, add polyoxyethylene class tensio-active agent, the polymine or derivatives thereof, during 4 kinds of additives such as the sulfonate of active organosulfur compound and chlorion, the roughness Rz that can obtain uneven surface is below 2.0 μ m, concavo-convex fluctuating does not appear in fact on this uneven surface, uneven surface with uniform low roughness, and, reach low uneven surface electrolytic copper foil more than 10.0% at 180 ℃ elongations, finished this problem.
Summary of the invention
Low uneven surface electrolytic copper foil of the present invention is characterized in that the roughness Rz of the uneven surface of electrolytic copper foil is below 2.0 μ m, concavo-convex fluctuating does not appear on this uneven surface, uneven surface with uniform low roughness, and, reach more than 10.0% at 180 ℃ elongations.
Above-mentioned low uneven surface electrolytic copper foil of the present invention, according to JIS (JIS, below identical) Z8741, the mirror surface luster of the uneven surface of measuring with Gs (85 °) is more than 100.
In addition, the manufacture method of low uneven surface electrolytic copper foil of the present invention, with sulfuric acid-copper sulfate solution as electrolytic solution, the insoluble anode that employing is made of the titanium plate of platinum element or its oxide elements lining and with respect to using titanium system roller on this anodic negative electrode, logical direct current between these the two poles of the earth, it is characterized in that, by in described electrolytic solution, adding ethylene oxide class tensio-active agent, the polymine or derivatives thereof, the sulfonate and the chlorion of active organosulfur compound, the roughness Rz that can obtain uneven surface is below 2.0 μ m, concavo-convex fluctuating does not appear on this uneven surface, uneven surface with uniform low roughness, and, reach low uneven surface electrolytic copper foil more than 10.0% at 180 ℃ elongations.
In addition, the manufacture method of above-mentioned low uneven surface electrolytic copper foil of the present invention, the mirror surface luster that can obtain the uneven surface measured according to JIS Z8741, with Gs (85 °) is at the low uneven surface electrolytic copper foil more than 100.
In addition, the manufacture method of above-mentioned low uneven surface electrolytic copper foil of the present invention, the ethylene oxide class surfactant concentrations in its electrolytic solution is 10～200mg/L.
In addition, the manufacture method of above-mentioned low uneven surface electrolytic copper foil of the present invention, the concentration of the polymine or derivatives thereof in its electrolytic solution is 0.5～30.0mg/L.
In addition, the manufacture method of above-mentioned low uneven surface electrolytic copper foil of the present invention, the sulfonate concentration of the active organosulfur compound in its electrolytic solution are 5.5～450 μ mol/L.
In addition, the manufacture method of above-mentioned low uneven surface electrolytic copper foil of the present invention, the chlorine ion concentration in its electrolytic solution is 20～120mg/L.
Formation of the present invention is described in detail as follows.
In the present invention, the additive that adds in the electrolytic solution that is made of sulfuric acid-copper sulfate solution is 4 kinds of additives such as the sulfonate of ethylene oxide class tensio-active agent, polymine or derivatives thereof, active organosulfur and chlorion, but have only these additives to be in certain concentration range, and the water-soluble polymer group just can obtain the low uneven surface electrolytic copper foil of target when certain molecular weight region.
At first, as the ethylene oxide class tensio-active agent that uses among the present invention, can enumerate molecular-weight average and be 2000～35000 polyoxyethylene glycol; The molecular-weight average of propylene oxide part be 2000～4000 and in whole molecular weight the polyoxyethylene polyoxypropylene copolymer of weight ratio more than 80 weight % of ethylene oxide; Polyoxyethylene bay ether; Polyoxyethylene nonyl phenylate; Dihydroxyphenyl propane-ethylene oxide adduct etc.Also have, all the weight ratio of ethylene oxide is not dissolved in the electrolytic solution that is made of sulfuric acid-copper sulfate solution the following person of 80 weight % in the molecular weight.
The molecular-weight average of polyoxyethylene glycol causes the abnormal electrical precipitation 2000 when following on the surface of electrolytic copper foil.
In the present invention, with being made up more than a kind or 2 kinds in the above-claimed cpd, be added into make in the electrolytic solution its in electrolytic solution separately or the concentration that adds up to reach 10～200mg/L.The lower value of this concentration range is very important, even representing the sulfonate and the chlorion three of polymine and derivative thereof, active organosulfur are transferred to following each proper concentration, still can't obtain the threshold value of the low uneven surface electrolytic copper foil of target.In contrast to this, can higher limit be to distinguish the threshold value of the low uneven surface electrolytic copper foil that obtain target as lower value, considers that from the viewpoint of economy this concentration keeps high density not have any positive value but be illustrated under the industrial operational condition.Therefore, the set upper limit value has not been used to the value of the characteristic of stipulating resulting electrolytic copper foil here, even in fact surpassing on the zone of higher limit, can obtain the low uneven surface electrolytic copper foil of target yet, but unrealistic.
In addition, the lower value of molecular-weight average also is important, when molecular-weight average less than 2000 the time, can not get the low uneven surface electrolytic copper foil of target.On the other hand, higher limit can be described as identical implication with the higher limit of concentration range, can infer, and for example, even adopt molecular-weight average to surpass 35000 polyoxyethylene glycol, still can obtain low uneven surface electrolytic copper foil.
Secondly, by generating concavo-convex fluctuating slowly on the uneven surface that ethylene oxide class tensio-active agent, active organosulfur compound and chlorion is added into resulting electrolytic copper foil in the electrolytic solution, but, can suppress the generation of this fluctuating by adding polymine.
The polymine that the present invention uses, preferable weight-average molecular weight is the polymine more than 600, more preferably the polymine more than 10000.At the polymine more than 600, then can use linear pattern with following chemical formula (1) expression, any with the branched chain type of chemical formula (2) expression as weight-average molecular weight, also can use both mixtures:
Also have,, for example, can enumerate " ェ Port ミ Application: trade(brand)name numbering: P-1000 Japan catalyst is made weight-average molecular weight: 70000 " as the commodity of market sale.
As polyethylenimine derivates, propylene oxide adduct is arranged, its weight-average molecular weight is preferably more than 1000, and the molecular weight of the polymine of addition propylene oxide is preferably more than 600.
In addition, shown in following chemical formula (3), it is preferred that the hydrogen on primary and the secondary amine of polymine can be substituted basic substituent.
(chemical formula 3)
Also have,, can enumerate " ェ Port ミ Application: trade(brand)name numbering: PP-061 Japan catalyst is made weight-average molecular weight: 1200 " as the market sale product.
When the weight-average molecular weight of polymine is lower than 600 and the weight-average molecular weight of above-mentioned polyethylenimine derivates when being lower than 1000, no matter this concentration how, produce concavo-convex fluctuating slowly on the uneven surface of resulting electrolytic copper foil, do not produce gloss (low uniformly roughening).Also have, do not produce concavo-convex fluctuating slowly on uneven surface, when generating uniform low roughness, its outward appearance has gloss, but produces concavo-convex fluctuating slowly on uneven surface, and when not generating uniform low roughness, its outward appearance has semi-gloss and even tarnish.
As the concentration range of polymine and derivative thereof and the general trend of molecular weight relation, along with molecular weight raises, uneven surface begins to rise to chatoyant concentration threshold from semi-gloss, and beginning is to not forming electroplating film, separating out the concentration of " burning plating " regional change of powdery copper also to the greater concn side shifting.In addition, even in the gloss zone, when the concentration of polymine rose, then the elongation during high temperature descended.Be necessary to consider on the basis of the molecular weight of above-mentioned polymine and derivative thereof and the influence that concentration is brought, decide each scope of molecular weight and concentration, the molecular weight of polymine and derivative thereof is preferably 600～70000, concentration in its electrolytic solution is the scope of 0.5～30.0mg/L, is preferably the scope of 1.0～10.0mg/L.
When the concentration in electrolytic solution was lower than 0.5mg/L when polymine and derivative thereof, uneven surface presented lacklustre outward appearance, when surpassing 30mg/L, then moved to burning the plating zone, can not get electrolytic copper foil.
Secondly, the active organosulfur compound that uses among the present invention must be the compound of the alkyl sulfhydryl of solubilized slightly water-soluble, but when addition hydroxyl or carboxyl, then can not get the low uneven surface electrolytic copper foil of target for dissolving.Therefore, must dissolve with the form of sulfonate.The representative compounds of the sulfonate of the preferred active organosulfur compound of the present invention, available following chemical formula (4), chemical formula (5), chemical formula (6), chemical formula (7) expression:
Chemical formula (4)
The addition of these compounds is represented it is unsuitable with mass concentration.As notice these compounds be according to its structure memory thiol group determine the words of its effect, compound 2 molecular combinations shapes, that represent with chemical formula (5) as 3-sulfydryl-1-propanesulfonic acid of representing with chemical formula (4) then generates 2 thiol groups, even 1 molecule also can show 2 efficiency-timed fruits of 3-sulfydryl-1-propanesulfonic acid sodium, thus can according to molecular memory the mole number of thiol group stipulate.
Therefore, as represent the thiol group amount with volumetric molar concentration, then among the present invention active organosulfur compound to preferred electrolytic solution addition (volumetric molar concentration) be 5.5～450 μ mol/L scope, be preferably the scope of 55～180 μ mol/L.When the concentration in the electrolytic solution was lower than 5.5 μ mol/L, uneven surface generated concavo-convex fluctuating slowly, can not get uniform low roughness and presented gloomy outward appearance, did not produce gloss.And, also low at 180 ℃ elongations.Even addition surpasses 450 μ mol/L, the elongation that the uneven surface state is reached at 180 ℃ does not have influence yet, but the high density of the active organosulfur compound in the maintenance electrolytic solution, mean when using insoluble anode to make electrolytic copper foil, for obtaining high anode potential, decomposition and consumption falls the organosulfur compound of high price in vain, so unrealistic.
Secondly, in the present invention, existing of chlorion is extremely important, even the sulfonate three of ethylene oxide class tensio-active agent, polymine or derivatives thereof and active organosulfur compound is adjusted to above-mentioned each preferred concentration range for, also can not get the low uneven surface electrolytic copper foil of target.Have only when coexisting, just can reach purpose of the present invention with chlorion.
In addition, the relation of chlorine ion concentration and active organosulfur compound concentration also is important, uneven surface is the concentration range of glossy appearance (not producing concavo-convex fluctuating slowly, the state of uniform low roughness on the uneven surface), roughly by both decisions, this gloss range has the tendency that rises and dwindle with chlorine ion concentration, also for active organosulfur compound concentration being reduced and operating, it is preferred that chlorine ion concentration is suppressed to low value.Therefore, the chlorine ion concentration in the electrolytic solution is preferably the scope of 30～100mg/L in the scope of 20～120mg/L.When chlorine ion concentration was lower than 20mg/L, the roughness of uneven surface can not reach the following low roughness of 2.0 μ m.When chlorion surpassed 120mg/L, plating face produced rough.
The supply source of chlorion as long as can dissociate, emit the inorganic salts of chlorion in the aqueous solution, can be enumerated NaCl and HCl etc. as its representation example.
In the present invention, by with 4 kinds of additives such as the sulfonate of above-mentioned polyoxyethylene class tensio-active agent, above-mentioned polymine or derivatives thereof, above-mentioned active organosulfur compound and chlorions, sulfuric acid-the copper sulfate solution that is adjusted to above-mentioned each preferred concentration range respectively and is constituted is as electrolytic solution, use titanium plate on the anode with the platinum oxide lining, use titanium system roller on the negative electrode, at 35～50 ℃ of electrolytic solution temperature and electrolytic current density 30～50A/dm
2Condition under carry out electrolysis, can obtain the low uneven surface electrolytic copper foil of target.
Description of drawings
Fig. 1 is a electron micrograph (multiplying power * 1000) that adopt to implement the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that preferred plan of the present invention obtains.
Fig. 2 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains of comparative example 1.
Fig. 3 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains of comparative example 3.
Fig. 4 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains of comparative example 4.
Fig. 5 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains of comparative example 6.
Fig. 6 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains of comparative example 7.
Fig. 7 is the electron micrograph (multiplying power * 1000) that adopts the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that the electrolytic solution that do not add polymine obtains.
Embodiment
At first, will implement preferred plan of the present invention is described as follows.
Preparation is by sulfuric acid (H
2SO
4): 100g/L, copper sulfate pentahydrate (CuSO
45H
2O): the electrolytic solution that the sulfuric acid of 280g/L-copper sulfate solution constitutes (being " basic electrolytic solution ") to call this electrolytic solution in the following text.
70000), 3-sulfydryl-1-propanesulfonic acid sodium and hydrochloric acid is added in the basic electrolytic solution as additive (ェ Port ミ Application: trade(brand)name numbering: P-1000 Japan catalyst is made weight-average molecular weight:, being mixed with polyoxyethylene glycol is that 30mg/L, polymine are that 0.5mg/L, 3-sulfydryl-1-propanesulfonic acid sodium is 220 μ mol/L and chlorion 35mol/L with polyoxyethylene glycol (molecular-weight average 20000 Sanyos change into manufacturing), polymine.
Make the electrolytic solution that contains this additive, between as anodic platinum oxide lining titanium plate and titanium system roller, flow into, at electrolytic current density: 45A/dm as negative electrode
2, carry out electrolysis under 40 ℃ of the electrolytic solution temperature and separate out, obtaining thickness is the low uneven surface electrolytic copper foil of 18 μ m.Also have, confirm that by visual inspection the uneven surface of this low uneven surface electrolytic copper foil has gloss.
According to IPC-TM-650,2001 type tension testing machines with the manufacturing of ィ Application テ ス コ society, the above-mentioned low uneven surface electrolytic copper foil (electrolytic copper foil is untreated) that obtains is carried out the tension stress (MPa) under room temperature (about 25 ℃) and 180 ℃ and the mensuration of elongation (%), simultaneously, according to JIS B0601, with the サ one Off コ one グ one SE1700 α that little slope institute makes, carry out the mensuration of the surfaceness (Rz) of uneven surface.In addition, index as the concavo-convex fluctuating quantity of expression in the uneven surface of this low uneven surface electrolytic copper foil, according to JIS Z8741, glossmeter (trade(brand)name: マ Le チ グ ロ ス 268 types) with the manufacturing of ミ ノ Le Co., Ltd., with Gs (85 °), to the width of low uneven surface electrolytic copper foil and the both direction of length direction (flowing), carry out the mensuration of the mirror surface luster of uneven surface.Each measurement result is shown in table 1.
Also have, above-mentioned mirror surface luster Gs (85 °) represents the numerical value 100 or more when not generating concavo-convex the fluctuating on the uneven surface in fact, when concavo-convex fluctuating that generate on the uneven surface slowly, then represent 100 below numerical value (with reference under tabulate 2 and Fig. 1～Fig. 7).That is, can be with above-mentioned mirror surface luster Gs (85 °) value index as uneven surface concave projection volt degree, the little concavo-convex fluctuating of healing of this value is bigger, and the big concavo-convex fluctuating of healing of this value is then little.
Fig. 1 is the electron micrograph (multiplying power * 1000) of the uneven surface of the above-mentioned low uneven surface electrolytic copper foil (electrolytic copper foil is untreated) that obtains, and can confirm no concave-convex fluctuating in fact on the uneven surface from this figure, is the uneven surface state of uniform low roughness.
Below embodiments of the invention 1～7 and comparative example 1～9 are described as follows:
Except with the kind of additive and the concentration in electrolytic solution, and electrolytic current density and electrolytic solution temperature press changed shown in the table 1 outside, under the condition identical, make the electrolytic copper foil that thickness is 18 μ m with each condition in the preferred plan of enforcement the invention described above.Same measuring method in employing and the above-mentioned enforcement preferred plan of the present invention, resulting electrolytic copper foil (electrolytic copper foil is untreated) is carried out the mensuration of the above-mentioned mirror surface luster Gs (85 °) of the width of tension stress (MPa), elongation (%), surfaceness (Rz) (μ m) and uneven surface under room temperature (about 25 ℃) and 180 ℃ and length direction (flowing), show the result in table 2.
Table 1
| The additive concentration condition | Electrolytic condition | |||||
| Polyoxyethylene glycol (M.W.20,000) (mg/L) | Polyethylene imines (mg/L) | 3-sulfydryl-1-propanesulfonic acid sodium (μ mol/L) | Chlorine ion concentration (mg/L) | Current density (A/dm 2) | The liquid temperature (℃) | |
| Implement preferred plan of the present invention | 30 | 0.5 (1) | 220 | 35 | 45 | 40 |
| | 30 | 10.0 (1) | 220 | 35 | 45 | 40 |
| Embodiment 2 | 100 | 30.0 (2) | 140 | 35 | 50 | 45 |
| Embodiment 3 | 70 (6) | 1.0 (1) | 140 | 35 | 50 | 40 |
| Embodiment 4 | 200 | 1.0 (2) | 330 | 70 | 30 | 35 |
| Embodiment 5 | 10 | 6.0 (2) | 220 | 100 | 45 | 40 |
| Embodiment 6 | 25 | 10.0 (2) | 220 | 110 | 45 | 50 |
| Embodiment 7 | 20 | 20.0 (2) | 6.0 | 20 | 50 | 50 |
| Comparative example 1 | 70 (3) | 0.1 (1) | 140 | 35 | 45 | 40 |
| Comparative example 2 | 100 | 0.1 (1) | 140 | 35 | 45 | 40 |
| Comparative example 3 | 10 | 1.0 (4) | 170 | 35 | 45 | 40 |
| Comparative example 4 | 50 | 35.0 (5) | 170 | 35 | 45 | 40 |
| Comparative example 5 | 50 | 35.0 (1) | 140 | 35 | 45 | 40 |
| Comparative example 6 | 50 | 0.3 (1) | 140 | 35 | 45 | 40 |
| Comparative example 7 | 25 | 0.2 (1) | 3.0 | 35 | 45 | 40 |
| Comparative example 8 | 25 | 0.2 (1) | 140 | 150 | 45 | 40 |
| Comparative example 9 | 25 | 0.2 (1) | 140 | 2 | 45 | 40 |
(1) molecular-weight average 70000; (2) (ェ Port ミ Application: trade(brand)name numbering: PP-061 Japan catalyst is made weight-average molecular weight to polyethylenimine derivates: 1200); (3) molecular-weight average 1000; (4) molecular-weight average 300; (5) molecular-weight average 600.
Table 2
| Room temperature | 180℃ | Surfaceness (Rz) | The mirror surface luster Gs of uneven surface (85 °) | |||||
| Tension stress (MPa) | Extension rate (%) | Tension stress (MPa) | Extension rate (%) | Uneven surface (μ m) | Glossy surface (μ m) | Width | Length direction (flow direction) | |
| Implement preferred plan of the present invention | 350 | 16.0 | 230 | 14.0 | 1.8 | 2.2 | 121 | 128 |
| | 390 | 12.0 | 250 | 10.0 | 1.7 | 2.2 | 120 | 125 |
| Embodiment 2 | 500 | 15.0 | 280 | 12.0 | 1.7 | 2.1 | 122 | 125 |
| Embodiment 3 | 350 | 10.0 | 220 | 20.0 | 2.0 | 2.1 | 130 | 128 |
| Embodiment 4 | 340 | 18.0 | 180 | 15.0 | 1.2 | 2.2 | 125 | 126 |
| Embodiment 5 | 350 | 12.0 | 210 | 14.0 | 1.5 | 2.1 | 120 | 118 |
| Embodiment 6 | 360 | 11.0 | 210 | 10.0 | 1.5 | 2.2 | 131 | 135 |
| Embodiment 7 | 360 | 15.0 | 205 | 20.0 | 0.9 | 2.2 | 132 | 136 |
| Comparative example 1 | 350 | 5.0 | 200 | 6.0 | 2.5 | 2.2 | 78 | 73 |
| Comparative example 2 | 350 | 6.0 | 200 | 3.0 | 4.5 | 2.2 | 60 | 62 |
| Comparative example 3 | 360 | 20.0 | 250 | 24.0 | 3.0 | 2.2 | 74 | 74 |
| Comparative example 4 | 480 | 5.5 | 365 | 3.0 | 3.0 | 2.2 | 38 | 41 |
| Comparative example 5 | 430 | 4.5 | 305 | 2.8 | 1.8 | 2.1 | 40 | 42 |
| Comparative example 6 | 335 | 10.0 | 230 | 14.0 | 2.8 | 2.1 | 63 | 63 |
| Comparative example 7 | 350 | 10.0 | 220 | 3.0 | 4.0 | 2.1 | 21 | 18 |
| Comparative example 8 | 360 | 7.0 | 230 | 7.0 | 3.0 | 2.2 | 20 | 22 |
| Comparative example 9 | 350 | 6.0 | 210 | 5.0 | 3.2 | 2.2 | 26 | 25 |
Fig. 2～Fig. 6 is the electron micrograph (multiplying power * 1000) of the uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) that obtains in the comparative example, Fig. 2 is that (molecular-weight average of polyoxyethylene glycol is low for expression comparative example 1, when the concentration of polymine is hanged down) the uneven surface state, Fig. 3 is the uneven surface state of expression comparative example 3 (when the weight-average molecular weight of polymine is hanged down), Fig. 4 is that (molecular-weight average of polyoxyethylene glycol is low for expression comparative example 4, when the concentration of polymine is high) the uneven surface state, Fig. 5 is the uneven surface state of expression comparative example 6 (when the concentration of polymine is hanged down), and Fig. 7 is the uneven surface state of expression comparative example 7 (when the concentration of 3-sulfydryl-1-propanesulfonic acid sodium is hanged down).
Fig. 7 is except that not adding polymine, be the electron micrograph (multiplying power * 1000) of uneven surface of the electrolytic copper foil (electrolytic copper foil is untreated) of 18 μ m with the thickness that obtains with the same condition of the embodiment of foregoing invention, can confirm to produce on the uneven surface ups and downs state slowly.Also have, the Fig. 1 in Fig. 7 and the above-mentioned enforcement preferred plan of the present invention is contrasted, and can confirm not produce concavo-convex fluctuating slowly on the uneven surface by adding polymine, and surfaceness significantly reduces.
In addition, can confirm from table 1 and table 2, in each electrolytic solution in above-mentioned enforcement preferred plan of the present invention and the foregoing description 1～7, along with polymine concentration increases, tension stress under the room temperature increases, but the roughness of uneven surface (Rz) almost keeps certain value.
Also have, the inventor etc. pass through repeatedly experimental verification, and in basic electrolytic solution, when not having polyoxyethylene glycol, uneven surface does not present the glossy outward appearance; When not having polymine, uneven surface is coarse, presents gloomy outward appearance, and is low at 180 ℃ elongation; When not having 3-sulfydryl-1-propanesulfonic acid sodium, it is very coarse that uneven surface becomes, low at 180 ℃ elongation; When there not being Lv Li Time, galvanic deposit face (plating face) breaks, and is low at 180 ℃ elongation.
In addition, when the concentration of water-soluble polymer or molecular-weight average are increased, can confirm to be accompanied by increase in the scope of afore mentioned rules, above-mentioned mirror surface luster Gs (85 °) has the tendency of increase.Also have, in order to obtain above-mentioned mirror surface luster Gs (85 °) is low uneven surface electrolytic copper foil more than 100, it is preferred having polyoxyethylene glycol, 3-sulfydryl-1-propanesulfonic acid sodium, polymine and chlorion in basic electrolytic solution, but when any material that lacks in them, perhaps when concentration or molecular-weight average were in beyond the above-mentioned scope, above-mentioned mirror surface luster (85 °) was below 100.
The possibility of utilizing on the industry
According to the present invention, a kind of low matsurface electrolytic copper foil (electrolytic copper foil is untreated) can be provided, its have be suitable for use as most printing distributing board and secondary battery cathode collector body, matsurface roughness Rz is below the 2.0 μ m, do not produce in fact concavo-convex fluctuating on this matsurface, above-mentioned mirror surface luster Gs (85 °) is the matsurface of the uniform low roughness more than 100, and, 180 ℃ percentage elongation is more than 10.0%, and the roughness between glassy surface and the matsurface is poor as far as possible little.
Claims (8)
1. one kind low uneven surface electrolytic copper foil is characterized in that, the roughness Rz of the uneven surface of this electrolytic copper foil is below 2.0 μ m, and no concave-convex rises and falls on this uneven surface, has the uneven surface of uniform low roughness, and is more than 10.0% at 180 ℃ elongation.
2. according to the low uneven surface electrolytic copper foil of record in the claim 1, it is characterized in that according to JIS (JIS, below identical) Z8741, the mirror surface luster of the uneven surface of measuring with Gs (85 °) is more than 100.
3. the manufacture method of a low uneven surface electrolytic copper foil, this method is, with sulfuric acid-copper sulfate solution as electrolytic solution, the insoluble anode that employing is made of the titanium plate of platinum element or its oxide elements lining and with respect to using titanium system roller on this anodic negative electrode, logical direct current between these the two poles of the earth, it is characterized in that, by in above-mentioned electrolytic solution, adding ethylene oxide class tensio-active agent, the polymine or derivatives thereof, the sulfonate and the chlorion of active organosulfur compound, the roughness Rz that can obtain uneven surface is below 2.0 μ m, concavo-convex fluctuating does not appear on this uneven surface, uneven surface with uniform low roughness, and, reach low uneven surface electrolytic copper foil more than 10.0% at 180 ℃ elongations.
4. according to the manufacture method of low uneven surface electrolytic copper foil of record in the claim 3, it is characterized in that according to JIS Z8741, the mirror surface luster of the uneven surface of this uneven surface electrolytic copper foil being measured with Gs (85 °) is more than 100.
5. according to the manufacture method of the low uneven surface electrolytic copper foil of record in claim 3 or 4, it is characterized in that the ethylene oxide class surfactant concentrations in the electrolytic solution is 10～200mg/L.
6. according to the manufacture method of the low uneven surface electrolytic copper foil of record in claim 3 or 4, it is characterized in that the concentration of the polymine or derivatives thereof in the electrolytic solution is 0.5～30.0mg/L.
7. according to the manufacture method of the low uneven surface electrolytic copper foil of record in claim 3 or 4, it is characterized in that the sulfonate concentration of the active organosulfur compound in the electrolytic solution is 5.5～450 μ mol/L.
8. according to the manufacture method of the low uneven surface electrolytic copper foil of record in claim 3 or 4, it is characterized in that the chlorine ion concentration in the electrolytic solution is 20～120mg/L.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP100647/2003 | 2003-04-03 | ||
| JP2003100647A JP4120806B2 (en) | 2002-10-25 | 2003-04-03 | Low rough surface electrolytic copper foil and method for producing the same |
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| CN1764744A true CN1764744A (en) | 2006-04-26 |
| CN100554527C CN100554527C (en) | 2009-10-28 |
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| Country | Link |
|---|---|
| US (1) | US20060191798A1 (en) |
| KR (1) | KR100772946B1 (en) |
| CN (1) | CN100554527C (en) |
| WO (1) | WO2004090197A1 (en) |
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- 2004-04-05 WO PCT/JP2004/004927 patent/WO2004090197A1/en active Application Filing
- 2004-04-05 US US10/551,035 patent/US20060191798A1/en not_active Abandoned
- 2004-04-05 CN CNB2004800078246A patent/CN100554527C/en not_active Expired - Lifetime
- 2004-04-05 KR KR1020057018237A patent/KR100772946B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| US20060191798A1 (en) | 2006-08-31 |
| CN100554527C (en) | 2009-10-28 |
| KR20050114701A (en) | 2005-12-06 |
| WO2004090197A1 (en) | 2004-10-21 |
| KR100772946B1 (en) | 2007-11-02 |
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