WO2004059040A1 - 特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 - Google Patents
特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 Download PDFInfo
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- WO2004059040A1 WO2004059040A1 PCT/JP2003/011858 JP0311858W WO2004059040A1 WO 2004059040 A1 WO2004059040 A1 WO 2004059040A1 JP 0311858 W JP0311858 W JP 0311858W WO 2004059040 A1 WO2004059040 A1 WO 2004059040A1
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- WIPO (PCT)
- Prior art keywords
- compound
- copper foil
- copper
- group
- electrolytic
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- -1 amine compound Chemical class 0.000 title claims abstract description 44
- 239000011889 copper foil Substances 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 19
- 150000002898 organic sulfur compounds Chemical class 0.000 title claims abstract description 15
- 239000000654 additive Substances 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 title abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 150000001879 copper Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229940050176 methyl chloride Drugs 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
Definitions
- the present invention relates to a copper electrolytic solution used for producing an electrolytic copper foil, and particularly to a copper electrolytic solution which can be formed into a fine pattern and which is excellent in elongation and tensile strength at ordinary and high temperatures.
- a rotating metal cathode drum having a polished surface and an insoluble metal anode (anode) surrounding the cathode drum arranged at a position substantially lower half of the cathode drum are used.
- anode insoluble metal anode
- a copper electrolyte is caused to flow between the cathode drum and the anode, and a potential difference is applied between them to cause electrodeposition of copper on the cathode drum.
- the adhered copper is peeled off to produce copper foil continuously.
- the copper foil obtained in this way is generally called raw foil, but after some surface treatment, it is used for printed wiring boards.
- Fig. 3 shows an outline of a conventional copper foil production system.
- a cathode drum 1 is installed in an electrolytic cell containing an electrolytic solution.
- the cathode drum 1 rotates so as to be partially (substantially lower half) immersed in the electrolytic solution.
- An insoluble anode (anode) 2 is provided so as to surround the lower half of the outer periphery of the cathode drum 1.
- the device shown in Fig. 3 has two anode plates.
- the electrolytic solution is supplied from below, passes through the gap 3 between the cathode drum 1 and the anode 2, overflows from the upper edge of the anode 2, and further flows into the electrolytic solution. Is configured to circulate.
- a predetermined voltage can be maintained between the cathode drum 1 and the anode 2 via a rectifier.
- the thickness of the copper electrodeposited from the electrolytic solution increases, and when the thickness exceeds a certain value, the raw foil 4 is peeled off and continuously wound up.
- the thickness of the raw foil thus manufactured can be adjusted by the distance between the cathode drum 1 and the anode 2, the flow rate of the supplied electrolyte, or the amount of electricity supplied.
- the copper foil manufactured by such an electrolytic copper foil manufacturing apparatus has a mirror surface on the surface in contact with the cathode drum, but has a rough surface on the opposite side. In ordinary electrolysis, this rough surface has severe irregularities, which tends to cause an undercut during etching and has difficulty in fine patterning.
- the performance required of copper foil for printed wiring boards is not only elongation at room temperature, but also high temperature elongation characteristics to prevent cracks due to thermal stress, and high tensile strength due to dimensional stability of printed wiring boards. Is required.
- this rope mouth filing can be achieved by adding a large amount of thiourea to an electrolytic solution.
- the present invention provides a rope-opened file electrolytic copper foil having a small surface roughness on the rough side (opposite to the glossy side) in the production of electrolytic copper foil using a cathode drum, It is another object of the present invention to obtain an electrolytic copper foil that can be formed into a copper foil and has excellent elongation and tensile strength at normal and high temperatures.
- the present inventors obtain an electrolytic copper foil which is capable of forming a fine pattern and which is excellent in elongation and tensile strength at room temperature and high temperature by adding an optimum additive capable of forming a rope mouth file to the electrolytic solution. I got the knowledge that I can do it.
- the present inventors flow a copper electrolyte between the cathode drum and the anode to electrodeposit copper on the cathode drum, and peel off the electrodeposited copper foil from the cathode drum to continuously
- a copper electrolytic solution containing a quaternary amine compound polymer having a specific skeleton and an organic sulfur compound was used.
- the present inventors have found that by performing electrolysis, a fine pattern can be formed, and an electrolytic copper foil excellent in elongation and tensile strength at ordinary and high temperatures can be obtained.
- the present invention has the following configurations.
- a quaternary amine compound polymer obtained by homopolymerizing a quaternized nitrogen compound of an acrylic compound having a dialkylamino group or copolymerizing it with another compound having an unsaturated bond; A copper electrolyte containing a sulfur compound as an additive.
- R 2 represents an alkyl group having 1 to 5 carbon atoms
- R 3 represents an alkyl group having 1 to 5 carbon atoms.
- X one is CI-, B r-, or CH 3 S0 4 - represents, n is an integer of 1 to 5).
- RR 2 and R 3 are an alkylene group having 1 to 8 carbon atoms, and R 4 is hydrogen,
- X is hydrogen, a sulfonic acid group, a phosphonic acid group , Sulfonic acid or phosphonic acid; selected from the group consisting of lithium metal bases and ammonium bases; and Y is selected from alkali metal bases of sulfonic acid groups, phosphonic acid groups, sulfonic acid or phosphonic acid.
- Z is hydrogen or an alkali metal, and n is 2 or 3.
- a quaternary amine compound obtained by homopolymerizing a compound obtained by quaternizing nitrogen of an acrylic compound having a dialkylamino group and copolymerizing the compound with another compound having an unsaturated bond is used in the electrolytic solution. It is important to include the compound polymer and the organic sulfur compound. The object of the present invention cannot be achieved by adding only one of them.
- the acrylic compound having a dialkylamino group in the present invention include an acrylic compound having a dialkylamino group and a methacryl compound having a dialkylamino group. And those in which an alkyl group is bonded to the carbon inside the bull group in the compound.
- a quaternizing agent is added to the acrylic compound having a dialkylamino group, and the mixture is heated and reacted to quaternize nitrogen. It can be manufactured by
- R represents hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 represents an alkyl group having 1 to 5 carbon atoms
- R 3 represents an alkyl group having 1 to 5 carbon atoms.
- X - is CI-, B r-, or CH 3 S0 4 - represents, n is an integer of 1 to 5).
- alkyl group having 1 to 5 carbon atoms for R 2 and R 3 a methyl group or an ethyl group is preferable.
- Examples of the quaternizing agent used for quaternizing nitrogen include alkyl halides, benzyl chloride, and dimethyl sulfate.
- R 3 and X— It is determined by the quaternizing agent.
- Examples of the compounds represented by the above general formulas (1) to (3) include, for example, a compound obtained by quaternizing N, N-dimethylaminopropyl acrylamide with methyl chloride (DMAPAA manufactured by Kojin Co., Ltd.). — Q) and a compound obtained by quaternizing N, N-dimethylaminoethyl atalylate with methyl chloride (DMAEA-Q) manufactured by Kojin Co., Ltd. can be used.
- DMAPAA N-dimethylaminopropyl acrylamide with methyl chloride
- DMAEA-Q N-dimethylaminoethyl atalylate with methyl chloride
- the quaternary amine compound polymer having a specific skeleton can be obtained by homopolymerizing these quaternary amine compounds or copolymerizing them with another compound having an unsaturated bond.
- the homopolymerization is preferably carried out using water as a solvent and a radical initiator such as potassium peroxodisulfate and ammonium peroxodisulfate as a polymerization initiator.
- the compound having another unsaturated bond when copolymerized with a compound having another unsaturated bond is an unsaturated compound having copolymerizability, and a preferable compound is 2-hydroxyl compound.
- a preferable compound is 2-hydroxyl compound. Examples thereof include tyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyshethyl methacrylate, and dimethylaminoethyl methacrylate.
- the weight average molecular weight of the quaternary amine compound polymer obtained by homopolymerization or copolymerization is preferably from 2,000 to 500,000.
- the reaction may not be completed sufficiently and the monomer may remain, if the residual monomer is 40% or less in terms of mole ratio, the characteristics can be obtained even when using a mixture with the monomer when using a quaternary amine compound polymer. There is no problem. '
- organic sulfur compound is preferably a compound having the structural formula of the above general formula (4) or (5).
- the alkali metal salts of sulfonic acid or phosphonic acid in X and Y are preferably sodium salts and potassium salts, and the alkali metals in Z are also sodium and potassium. preferable.
- Examples of the organic sulfur compound represented by the above general formula (4) include, for example, the following, which are preferably used.
- examples of the organic sulfur compound represented by the general formula (5) include the following, and are preferably used.
- the weight ratio of the quaternary amine compound polymer to the organic sulfur compound in the copper electrolyte is preferably 1: 5 to 5: 1. The ratio is more preferably 1: 2 to 2: 1.
- the concentration of the quaternary amine polymer in the copper electrolyte is preferably 1 to 50 ppm.
- polyether compounds such as poly (ethylene glycol) and polypropylene glycol, poly (ethylene imine), phenazine dye, glue, and cellulose are used. Additives may be added.
- the copper-clad laminate obtained by laminating the electrolytic copper foil of the present invention is a copper-clad laminate excellent in elongation and tensile strength at ordinary temperature and high temperature.
- FIG. 1 is an FT-IR spectrum of a quaternary amine compound polymer obtained in a synthesis example.
- FIG. 2 is a 13 C-NMR spectrum of a quaternary amine compound polymer obtained in a synthesis example.
- FIG. 3 is a diagram illustrating an example of an electrolytic copper foil device. Explanation of reference numerals
- the obtained quaternary amine compound polymer was subjected to molecular weight distribution measurement using hydrogen SEC column under the following conditions, and as a result, the weight average molecular weight was about 80,000 (the residual monomer was subject to control). Outside).
- a polymer was obtained in the same manner as in Synthesis Example 1 by the method shown below.
- a compound obtained by quaternizing N, N-dimethylacrylamide (DMAA manufactured by Kojin Co., Ltd.) with methyl chloride is dissolved in 50 g of ion-exchanged water, and 0.5 g of peroxodisulfuric acid rim is added thereto.
- the polymerization reaction was carried out at 60 ° C. for 3 hours under a nitrogen atmosphere.
- the obtained compound was a mixture of a quaternary amine compound polymer represented by the following chemical formula and its monomer, and the monomer content was 20 to 30%.
- the molecular weight was measured in the same manner as in Synthesis Example 1. As a result, the weight average molecular weight was about 90,000.
- a polymer was obtained in the same manner as in Synthesis Example 1 by the method shown below.
- the molecular weight was measured in the same manner as in Synthesis Example 1, and as a result, the weight average molecular weight was about 70,000.
- An electrolytic copper foil with a film thickness of 35 m was manufactured using an electrolytic copper foil manufacturing device as shown in Fig. 3.
- the composition of the electrolytic solution is as shown below and in Table 1.
- Polyethylene glycol 2 OmgZL or Omg / L
- Additive A1 Disodium bis (3-sulfopropyl) disulphide
- Additive B 1 quaternary amine compound having a specific structure obtained in Synthesis Example 1 above
- Polymer B 2 quaternary amine compound having a specific structure obtained in Synthesis Example 2 above
- the surface roughness R Z was 0.73 to: L 4 ⁇ , room temperature elongation of 9.2 ⁇ ; L 1.96%, room temperature tensile strength of 33.2 ⁇ 35. Lkgi / mm High temperature elongation of 10.2-14.8%, high temperature tensile strength of 20 . it became 1 ⁇ 21. 1 kgf / mm 2.
- the copper electrolytic solution to which the quaternary amine compound polymer having a specific structure and the organic sulfur compound of the present invention are added is extremely effective for low profile formation of the rough surface of the obtained electrolytic copper foil.
- the above co-addition is important, and it is only by this that the above characteristics can be obtained.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004562861A JP4083171B2 (ja) | 2002-12-25 | 2003-09-17 | 特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
US10/486,861 US20060011488A1 (en) | 2002-12-25 | 2003-09-17 | Copper electrolytic solution containing quaternary amine compound polymer with specific skeleton and organo-sulfur compound as additives, and electrolytic copper foil manufactured using the same |
KR1020047003348A KR100598994B1 (ko) | 2002-12-25 | 2003-09-17 | 특정골격을 갖는 4급아민화합물 중합체 및 유기유황화합물을 첨가제로서 포함하는 동전해액 및 그것에 의하여 제조되는 전해동박 |
EP03788704A EP1607495A4 (en) | 2002-12-25 | 2003-09-17 | COPPER ELECTROLYTE SOLUTION CONTAINS A QUINTERNATIVE AMINO-BONDED POLYMER COMPRISING A PARTICULAR SCAFFOLD AND ORGANIC SULFUR COMPOUND AS ADDITIONS AND ELECTROLYTIC COPPER FOIL MANUFACTURED THEREWITH |
HK05101029A HK1068654A1 (en) | 2002-12-25 | 2005-02-07 | Copper electrolytic solution containing quaternaryamine compound polymer of specified skeleton and organic sulfur compound as additives and electrolytic copper foil produced therewith |
US11/974,462 US7678257B2 (en) | 2002-12-25 | 2007-10-12 | Copper electrolytic solution containing quaternary amine compound polymer with specific skeleton and organo-sulfur compound as additives, and electrolytic copper foil manufactured using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-373719 | 2002-12-25 | ||
JP2002373719 | 2002-12-25 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10486861 A-371-Of-International | 2003-09-17 | ||
US11/974,462 Division US7678257B2 (en) | 2002-12-25 | 2007-10-12 | Copper electrolytic solution containing quaternary amine compound polymer with specific skeleton and organo-sulfur compound as additives, and electrolytic copper foil manufactured using the same |
Publications (1)
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WO2004059040A1 true WO2004059040A1 (ja) | 2004-07-15 |
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Family Applications (1)
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PCT/JP2003/011858 WO2004059040A1 (ja) | 2002-12-25 | 2003-09-17 | 特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20060011488A1 (ja) |
EP (1) | EP1607495A4 (ja) |
JP (1) | JP4083171B2 (ja) |
KR (1) | KR100598994B1 (ja) |
CN (1) | CN1312323C (ja) |
HK (1) | HK1068654A1 (ja) |
TW (1) | TWI285683B (ja) |
WO (1) | WO2004059040A1 (ja) |
Cited By (12)
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JP2004162172A (ja) * | 2002-11-14 | 2004-06-10 | Iljin Copper Foil Co Ltd | 電解銅箔製造用の電解液及びそれを用いた電解銅箔の製造方法 |
JP2007016265A (ja) * | 2005-07-06 | 2007-01-25 | Adeka Corp | 電解銅メッキ用添加剤、該添加剤を含有する電解銅メッキ浴及び該メッキ浴を使用する電解銅メッキ方法 |
JP2007131946A (ja) * | 2005-10-14 | 2007-05-31 | Mitsui Mining & Smelting Co Ltd | フレキシブル銅張積層板、そのフレキシブル銅張積層板を用いて得られるフレキシブルプリント配線板、そのフレキシブル銅張積層板を用いて得られるフィルムキャリアテープ、そのフレキシブル銅張積層板を用いて得られる半導体装置、フレキシブル銅張積層板の製造方法及びフィルムキャリアテープの製造方法 |
JP2008513503A (ja) * | 2004-09-21 | 2008-05-01 | バイオニューメリック・ファーマスーティカルズ・インコーポレイテッド | 医薬用ジスルフィド塩 |
WO2009116432A1 (ja) * | 2008-03-17 | 2009-09-24 | 日鉱金属株式会社 | 電解銅箔製造用の電解液 |
WO2009145207A1 (ja) * | 2008-05-28 | 2009-12-03 | 三井金属鉱業株式会社 | 銅箔の粗化処理方法及びその粗化処理方法で得られるプリント配線板用銅箔 |
WO2009151124A1 (ja) * | 2008-06-12 | 2009-12-17 | 古河電気工業株式会社 | 電解銅皮膜、その製造方法及び銅電解皮膜製造用の銅電解液 |
WO2010004988A1 (ja) * | 2008-07-07 | 2010-01-14 | 古河電気工業株式会社 | 電解銅箔および銅張積層板 |
WO2012066991A1 (ja) | 2010-11-15 | 2012-05-24 | Jx日鉱日石金属株式会社 | 電解銅箔 |
KR20180107990A (ko) | 2017-03-23 | 2018-10-04 | 케이씨에프테크놀로지스 주식회사 | 리튬 이온 2차전지, 이 2차전지의 음극 전극을 구성하는 집전체 및 이 음극 집전체를 구성하는 전해동박 |
KR20180110552A (ko) | 2017-03-29 | 2018-10-10 | 케이씨에프테크놀로지스 주식회사 | 리튬 이온 2차전지, 이 2차전지의 음극 전극을 구성하는 집전체 및 이 음극 집전체를 구성하는 전해동박 |
JP2020057581A (ja) * | 2018-10-01 | 2020-04-09 | 長春石油化學股▲分▼有限公司 | リチウム二次電池の集電体用銅箔及びそれを含む負極 |
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WO2005010239A1 (ja) * | 2003-07-29 | 2005-02-03 | Nikko Materials Co., Ltd. | 特定骨格を有するジアルキルアミノ基含有重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
JP4992308B2 (ja) * | 2006-06-14 | 2012-08-08 | 日本電気株式会社 | 通信システム、動作制御方法、位置管理サーバ及びプログラム |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4555315A (en) * | 1984-05-29 | 1985-11-26 | Omi International Corporation | High speed copper electroplating process and bath therefor |
JPS6364519B2 (ja) * | 1981-01-07 | 1988-12-12 | ||
EP1069211A2 (en) * | 1999-07-15 | 2001-01-17 | The Boc Group, Inc. | Electroplating solutions |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
US4667049A (en) * | 1984-11-02 | 1987-05-19 | Etd Technology Inc. | Method of making dialkylamino-thioxomethyl-thioalkanesulfonic acid compounds |
US5232575A (en) * | 1990-07-26 | 1993-08-03 | Mcgean-Rohco, Inc. | Polymeric leveling additive for acid electroplating baths |
JPH0853789A (ja) * | 1994-08-09 | 1996-02-27 | Furukawa Circuit Foil Kk | 電解銅箔の製造方法 |
JP4394234B2 (ja) * | 2000-01-20 | 2010-01-06 | 日鉱金属株式会社 | 銅電気めっき液及び銅電気めっき方法 |
US6800188B2 (en) * | 2001-05-09 | 2004-10-05 | Ebara-Udylite Co., Ltd. | Copper plating bath and plating method for substrate using the copper plating bath |
-
2003
- 2003-09-17 EP EP03788704A patent/EP1607495A4/en not_active Withdrawn
- 2003-09-17 CN CNB038009188A patent/CN1312323C/zh not_active Expired - Lifetime
- 2003-09-17 JP JP2004562861A patent/JP4083171B2/ja not_active Expired - Lifetime
- 2003-09-17 KR KR1020047003348A patent/KR100598994B1/ko active IP Right Grant
- 2003-09-17 WO PCT/JP2003/011858 patent/WO2004059040A1/ja active Application Filing
- 2003-09-17 US US10/486,861 patent/US20060011488A1/en not_active Abandoned
- 2003-09-22 TW TW092126053A patent/TWI285683B/zh not_active IP Right Cessation
-
2005
- 2005-02-07 HK HK05101029A patent/HK1068654A1/xx not_active IP Right Cessation
-
2007
- 2007-10-12 US US11/974,462 patent/US7678257B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6364519B2 (ja) * | 1981-01-07 | 1988-12-12 | ||
US4555315A (en) * | 1984-05-29 | 1985-11-26 | Omi International Corporation | High speed copper electroplating process and bath therefor |
EP1069211A2 (en) * | 1999-07-15 | 2001-01-17 | The Boc Group, Inc. | Electroplating solutions |
Non-Patent Citations (1)
Title |
---|
See also references of EP1607495A4 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004162172A (ja) * | 2002-11-14 | 2004-06-10 | Iljin Copper Foil Co Ltd | 電解銅箔製造用の電解液及びそれを用いた電解銅箔の製造方法 |
JP2008513503A (ja) * | 2004-09-21 | 2008-05-01 | バイオニューメリック・ファーマスーティカルズ・インコーポレイテッド | 医薬用ジスルフィド塩 |
JP4750486B2 (ja) * | 2005-07-06 | 2011-08-17 | 株式会社Adeka | 電解銅メッキ用添加剤、該添加剤を含有する電解銅メッキ浴及び該メッキ浴を使用する電解銅メッキ方法 |
JP2007016265A (ja) * | 2005-07-06 | 2007-01-25 | Adeka Corp | 電解銅メッキ用添加剤、該添加剤を含有する電解銅メッキ浴及び該メッキ浴を使用する電解銅メッキ方法 |
JP2007131946A (ja) * | 2005-10-14 | 2007-05-31 | Mitsui Mining & Smelting Co Ltd | フレキシブル銅張積層板、そのフレキシブル銅張積層板を用いて得られるフレキシブルプリント配線板、そのフレキシブル銅張積層板を用いて得られるフィルムキャリアテープ、そのフレキシブル銅張積層板を用いて得られる半導体装置、フレキシブル銅張積層板の製造方法及びフィルムキャリアテープの製造方法 |
KR101247475B1 (ko) * | 2008-03-17 | 2013-03-29 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 전해 동박 제조용 전해액 |
WO2009116432A1 (ja) * | 2008-03-17 | 2009-09-24 | 日鉱金属株式会社 | 電解銅箔製造用の電解液 |
JP5524833B2 (ja) * | 2008-05-28 | 2014-06-18 | 三井金属鉱業株式会社 | 銅箔の粗化処理方法及びその粗化処理方法で得られるプリント配線板用銅箔 |
WO2009145207A1 (ja) * | 2008-05-28 | 2009-12-03 | 三井金属鉱業株式会社 | 銅箔の粗化処理方法及びその粗化処理方法で得られるプリント配線板用銅箔 |
JP2010018885A (ja) * | 2008-06-12 | 2010-01-28 | Furukawa Electric Co Ltd:The | 電解銅皮膜、その製造方法及び銅電解皮膜製造用の銅電解液 |
WO2009151124A1 (ja) * | 2008-06-12 | 2009-12-17 | 古河電気工業株式会社 | 電解銅皮膜、その製造方法及び銅電解皮膜製造用の銅電解液 |
JP2010037654A (ja) * | 2008-07-07 | 2010-02-18 | Furukawa Electric Co Ltd:The | 電解銅箔および銅張積層板 |
WO2010004988A1 (ja) * | 2008-07-07 | 2010-01-14 | 古河電気工業株式会社 | 電解銅箔および銅張積層板 |
WO2012066991A1 (ja) | 2010-11-15 | 2012-05-24 | Jx日鉱日石金属株式会社 | 電解銅箔 |
KR20150091192A (ko) | 2010-11-15 | 2015-08-07 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 전해 구리박 |
KR20180107990A (ko) | 2017-03-23 | 2018-10-04 | 케이씨에프테크놀로지스 주식회사 | 리튬 이온 2차전지, 이 2차전지의 음극 전극을 구성하는 집전체 및 이 음극 집전체를 구성하는 전해동박 |
KR20180110552A (ko) | 2017-03-29 | 2018-10-10 | 케이씨에프테크놀로지스 주식회사 | 리튬 이온 2차전지, 이 2차전지의 음극 전극을 구성하는 집전체 및 이 음극 집전체를 구성하는 전해동박 |
JP2020057581A (ja) * | 2018-10-01 | 2020-04-09 | 長春石油化學股▲分▼有限公司 | リチウム二次電池の集電体用銅箔及びそれを含む負極 |
US10665865B2 (en) | 2018-10-01 | 2020-05-26 | Chang Chun Petrochemical Co., Ltd. | Copper foil for current collector of lithium secondary battery and negative electrode including the same |
Also Published As
Publication number | Publication date |
---|---|
US20080075972A1 (en) | 2008-03-27 |
CN1312323C (zh) | 2007-04-25 |
US7678257B2 (en) | 2010-03-16 |
TWI285683B (en) | 2007-08-21 |
HK1068654A1 (en) | 2005-04-29 |
EP1607495A1 (en) | 2005-12-21 |
JP4083171B2 (ja) | 2008-04-30 |
JPWO2004059040A1 (ja) | 2006-04-27 |
US20060011488A1 (en) | 2006-01-19 |
KR100598994B1 (ko) | 2006-07-07 |
TW200411082A (en) | 2004-07-01 |
CN1564881A (zh) | 2005-01-12 |
KR20040076847A (ko) | 2004-09-03 |
EP1607495A4 (en) | 2006-07-12 |
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