CN1806067A - Copper electrolytic solution containing polymer having dialkylamino group of specified structure and organic sulfur compound as additive and electrolytic copper foil produced therewith - Google Patents
Copper electrolytic solution containing polymer having dialkylamino group of specified structure and organic sulfur compound as additive and electrolytic copper foil produced therewith Download PDFInfo
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- CN1806067A CN1806067A CN200480016822.3A CN200480016822A CN1806067A CN 1806067 A CN1806067 A CN 1806067A CN 200480016822 A CN200480016822 A CN 200480016822A CN 1806067 A CN1806067 A CN 1806067A
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- copper foil
- compound
- electrolytic
- additive
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011889 copper foil Substances 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 239000000654 additive Substances 0.000 title claims abstract description 22
- 150000002898 organic sulfur compounds Chemical class 0.000 title claims abstract description 16
- 230000000996 additive effect Effects 0.000 title claims description 20
- 239000008151 electrolyte solution Substances 0.000 title abstract description 18
- 125000004663 dialkyl amino group Chemical group 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- -1 acrylic compound Chemical class 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 125000003368 amide group Chemical group 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000007261 regionalization Effects 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000059 patterning Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 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 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 210000001364 upper extremity Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/18—Electrolytes
Landscapes
- 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)
- Electrolytic Production Of Metals (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
An electrolytic copper foil of low profile whose surface roughness on the rough surface side (side opposite to shiny surface) in the electrolytic copper foil production using a cathode drum is low, which electrolytic copper foil can especially realize fine pattern formation and excels in extensibility and tensile strength at ordinary and high temperatures. In particular, there are provided a copper electrolytic solution comprising as additives a polymer having dialkylamino group, this polymer obtained by carrying out homopolymerization of an acrylic compound having dialkylamino group or copolymerization thereof with another compound having unsaturated bond, and an organic sulfur compound; and an electrolytic copper foil produced with the electrolytic solution.
Description
Technical field
The present invention relates to the copper electrolyte that in the manufacturing of electrolytic copper foil, uses, particularly be used to make the copper electrolyte of the electrolytic copper foil that can realize fine patterning, the elongation when normal temperature and high temperature and tensile strength excellence.
Background technology
Generally when making electrolytic copper foil, be to use the metal system negative electrode rotating cylinder of the rotation of glazed surface, with the insoluble petal anode (anode) around this negative electrode rotating cylinder of encirclement of cardinal principle lower part position configuration of this negative electrode rotating cylinder, copper electrolyte is flowed between above-mentioned negative electrode rotating cylinder and anode, simultaneously between them, apply potential difference, make copper galvanic deposit on the negative electrode rotating cylinder, when reaching specific thickness, peel off the copper of galvanic deposit, manufacturing copper foil continuously from this negative electrode rotating cylinder.
The Copper Foil that obtains although it is so is commonly referred to as living paper tinsel, but implements surface treatment several times thereafter, can be used for printed circuit board etc.
The summary of existing Copper Foil manufacturing installation as shown in Figure 1.This electrolytic copper foil device in accommodating the electrolyzer of electrolytic solution, is provided with negative electrode rotating cylinder 1.This negative electrode rotating cylinder 1 is with the state rotation of part in electrolytic solution (lower part substantially) dipping.
Mode with the periphery lower part of surrounding this negative electrode rotating cylinder 1 is provided with insoluble anode (anode) 2.Between this negative electrode rotating cylinder 1 and the anode 2 certain clearance 3 is arranged, electrolytic solution betwixt flows.Dispose 2 positive plates in the device of Fig. 1.
Constitute in the device of this Fig. 1, supply with electrolytic solution from the below, this electrolytic solution flows through the gap 3 of negative electrode rotating cylinder 1 and anode 2, overflow from the upper limb of anode 2, and then this circulation of elecrolyte.Between negative electrode rotating cylinder 1 and anode 2, insert rectifier, can between keep the voltage of regulation.
Along with the rotation of negative electrode rotating cylinder 1, the copper thickness of galvanic deposit increases from electrolytic solution, when reaching more than or equal to certain thickness, peels off this life paper tinsel 4, and batches continuously.The livings paper tinsel that manufactures of operation like this, the flow velocity of the electrolytic solution by the distance between adjustment negative electrode rotating cylinder 1 and the anode 2, supply or the electric weight of supply can be adjusted thickness.
With the Copper Foil that such electrolytic copper foil manufacturing installation produces, the face that contacts with the negative electrode rotating cylinder becomes minute surface, and the face of opposition side becomes irregular uneven surface.In common electrolysis, exist the concavo-convex fluctuating of this uneven surface very big, the problem of undercut, fine patterning difficulty takes place during etching easily.
In addition, follow the densification of printed circuit board recently, people require to follow narrow and smallization of circuit width, the Copper Foil that multiple stratification can realize fine patterning gradually.In order to realize this fine patterning, need have the deliquescent Copper Foil of etching speed and homogeneous, i.e. the Copper Foil of etching characteristic excellence.
On the other hand, printed circuit board is with Copper Foil desired performance, the elongation when being not only normal temperature, and the high temperature elongation characteristics of the crackle that also requires to be used to prevent that thermal stresses from causing, and then require to be used to obtain the high-tensile of the dimensional stability of printed circuit board.But as mentioned above, there is the problem that is not suitable for above-mentioned fine patterning fully in the big Copper Foil of concavo-convex fluctuating of above-mentioned uneven surface.The low sectionization of uneven surface thus begins one's study.
Known generally in order to realize this low sectionization, can realize by in electrolytic solution, adding a large amount of glue, thiocarbamides.
But the problem that the elongation when such additive existence can cause normal temperature and high temperature sharply descends, reduce greatly with the performance of Copper Foil as printed circuit board.
Summary of the invention
Problem of the present invention is, in the electrolytic copper foil that has used the negative electrode rotating cylinder is made, obtain the little low section electrolytic copper foil of surfaceness of uneven surface side (opposition side of light face), particularly obtain to realize the electrolytic copper foil of fine patterning and then elongation when normal temperature and high temperature and tensile strength excellence.
Present inventors find, by add the only additive that can realize low sectionization in electrolytic solution, can obtain to realize the electrolytic copper foil of fine patterning, the elongation when normal temperature and high temperature and tensile strength excellence.
Present inventors are based on this knowledge, copper electrolyte circulates between negative electrode rotating cylinder and anode, make copper electrodeposition on the negative electrode rotating cylinder, the Copper Foil of galvanic deposit is peeled off from this negative electrode rotating cylinder, continuously in the electrolytic copper foil manufacture method of manufacturing copper foil, contain the polymkeric substance that contains dialkyl amido and the copper electrolyte of organosulfur compound carries out electrolysis by use with specific skeleton, can obtain to realize the electrolytic copper foil of fine patterning, the elongation when normal temperature and high temperature and tensile strength excellence, thereby finish the present invention.
That is, the present invention is made of following.
[1] a kind of copper electrolyte, it contains: contain the polymkeric substance of dialkyl amido and organosulfur compound as additive, described polymkeric substance is by making the acrylic compounds with dialkyl amido carry out homopolymerization or obtain with other compound copolymerization with unsaturated link(age).
As [1] described copper electrolyte, it is characterized in that [2] above-mentioned acrylic compounds with dialkyl amido is with following general formula (1), (2) or (3) expression,
(in general formula (1)～(3), R
1The alkyl of expression hydrogen or carbonatoms 1～5, R
2And R
3The alkyl of representing carbonatoms 1～5 respectively, n are represented 1～5 integer).
As [1] described copper electrolyte, it is characterized in that [3] above-mentioned organosulfur compound is the compound shown in following general formula (4) or (5),
X-R
1-(S)
n-R
2-Y (4)
R
4-S-R
3-SO
3Z (5)
(in general formula (4) and (5), R
1, R
2And R
3Be the alkylidene group of carbonatoms 1～8, R
4Be selected from hydrogen,
, X is selected from hydrogen, sulfonic group, phosphonate group, sulfonic acid or phosphonic basic metal alkali or ammonium salt base, and Y is selected from sulfonic group, phosphonate group, sulfonic acid or phosphonic basic metal alkali, and Z is hydrogen or basic metal, n is 2 or 3).
[4] a kind of electrolytic copper foil is to use the described copper electrolyte of each of above-mentioned [1]～[3] to make.
[5] a kind of copper plate pressing plate is to use above-mentioned [4] described electrolytic copper foil to make.
Description of drawings
As described, Fig. 1 is the diagrammatic illustration figure of existing Copper Foil manufacturing installation.This electrolytic copper foil device is provided with negative electrode rotating cylinder 1 in accommodating the electrolyzer of electrolytic solution.This negative electrode rotating cylinder 1 is with the state rotation of part in electrolytic solution (lower part substantially) dipping.
Mode with the periphery lower part of surrounding this negative electrode rotating cylinder 1 is provided with insoluble anode (anode) 2.Between this negative electrode rotating cylinder 1 and the anode 2 certain clearance 3 is arranged, electrolytic solution betwixt flows.Dispose 2 positive plates in the device of Fig. 1.
Embodiment
In the present invention importantly, contain in electrolytic solution: contain the polymkeric substance and the organosulfur compound of dialkyl amido, described polymkeric substance is by making the acrylic compounds with dialkyl amido carry out homopolymerization or obtain with other compound copolymerization that contain unsaturated link(age).Only add anyly, all can not realize purpose of the present invention.
As the acrylic compounds among the present invention with dialkyl amido, can list, have dialkyl amido acrylic compound, have the methacrylic compound of dialkyl amido etc., be included in the compound that is combined with alkyl on the carbon of the vinyl inside in the compound.As acrylic compounds with dialkyl amido, the compound shown in preferred following general formula (1)～(3).
(in general formula (1)～(3), R
1The alkyl of expression hydrogen or carbonatoms 1～5, R
2And R
3The alkyl of expression carbonatoms 1～5, n represents 1～5 integer.)
As R
1, preferred hydrogen or methyl are as R
2, R
3Alkyl, preferable methyl or the ethyl of carbonatoms 1～5.
As the compound shown in above-mentioned general formula (1)～(3), for example can use, vinylformic acid dimethylamino ethyl ester, diethyl aminoethyl methacrylate, dimethylaminoethyl methacrylate, N, N-diethyl acrylamide, N, N-DMAA, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl Methacrylamide etc.
The polymkeric substance that contains dialkyl amido with specific skeleton is by making these acrylic compounds that contain dialkyl amido carry out homopolymerization or obtain with other the compound copolymerization that contains unsaturated link(age).
When carrying out homopolymerization, preferably with water as solvent, use potassium peroxydisulfate, the such radical initiator of peroxo disulfate acid ammonium as polymerization starter.
In addition, when carrying out copolymerization with other compounds that contain unsaturated link(age) other have the compound of unsaturated link(age), it is the unsaturated compound of copolymerization, as preferred compound, can list vinylformic acid 2-hydroxyethyl ester, vinylformic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxyethyl ester etc.
The weight-average molecular weight that contains the alkylamino polymkeric substance as obtaining by homopolymerization or copolymerization is preferably 1000～500000.
Fully do not finish though respond, the situation of monomer residue, if the residual monomer mol ratio smaller or equal to 40%, so promptly use and monomeric mixture, also no problem on characteristic.
In addition, organosulfur compound is preferably the compound of the structural formula with above-mentioned general formula (4) or (5).
As the organosulfur compound shown in the above-mentioned general formula (4), can enumerate and preferably use for example following compound.
H
2O
3P-(CH
2)
3-S-S-(CH
2)
3-PO
3H
2
HO
3S-(CH
2)
4-S-S-(CH
2)
4-SO
3H
NaO
3S-(CH
2)
3-S-S-(CH
2)
3-SO
3Na
HO
3S-(CH
2)
2-S-S-(CH
2)
2-SO
3H
CH
3-S-S-CH
2-SO
3H
NaO
3S-(CH
2)
3-S-S-S-(CH
2)
3-SO
3Na
(CH
3)
2CH-S-S-(CH
2)
2-SO
3H
In addition, as the organosulfur compound shown in the above-mentioned general formula (5), can enumerate and preferably use for example following compound.
HS-CH
2CH
2CH
2-SO
3Na
HS-CH
2CH
2-SO
3Na
The polymkeric substance that contains dialkyl amido in the copper electrolyte and the ratio of organosulfur compound in weight ratio, are preferably 1: 5～5: 1, more preferably 1: 2～2: 1.The concentration of polymkeric substance in copper electrolyte that contains dialkyl amido is preferably 1～200ppm.
In copper electrolyte, except the above-mentioned polymkeric substance and organosulfur compound that contains dialkyl amido, can also add the known additive such as polyether compound, polymine, phenazine dyes, glue, Mierocrystalline cellulose of polyoxyethylene glycol, polypropylene glycol etc.
In addition, lamination the electrolytic copper foil of the present invention and copper plate pressing plate that obtains becomes the copper plate pressing plate that can realize fine patterning and elongation when normal temperature and high temperature and tensile strength excellence.
Embodiment
Enumerate embodiment below, the present invention is described in more detail.
The synthesis example 1 that contains the dialkyl amino based polyalcohol
With the N of 50g, N-dimethylaminopropyl acrylamide is dissolved in the 50g ion exchanged water, to wherein adding the 0.5g potassium peroxydisulfate, under nitrogen atmosphere, 60 ℃ of polyreactions 3 hours.The compound that obtains is the mixture that contains dialkyl amino based polyalcohol (I) (weight-average molecular weight 8500) and monomer whose shown in the following chemical formula, and the monomer containing ratio is 20～30%.
The synthesis example 2 that contains the dialkyl amino based polyalcohol
Except the N with above-mentioned synthesis example 1, N-dimethylaminopropyl acrylamide becomes beyond the dimethylaminoethyl methacrylate, uses with the same method of synthesis example 1 and carries out polymerization.The compound that obtains is the mixture that contains dialkyl amino based polyalcohol (II) (weight-average molecular weight 4500) and monomer whose shown in the following chemical formula, and the monomer containing ratio is about 6%.
The synthesis example 3 that contains the dialkyl amino based polyalcohol
Except the N with above-mentioned synthesis example 1, N-dimethylaminopropyl acrylamide becomes beyond the N,N-DMAA, uses with the same method of synthesis example 1 and carries out polymerization.The compound that obtains is the mixture that contains dialkyl amino based polyalcohol (III) (weight-average molecular weight 9200) and monomer whose shown in the following chemical formula, and the monomer containing ratio is about 10%.
Embodiment 1～6 and comparative example 1～5
Use electrolytic copper foil manufacturing installation as shown in Figure 1, produce the electrolytic copper foil of thickness 35 μ m.Electrolytic solution composed as follows.
Cu： 90g/L
H
2SO
4： 80g/L
Cl： 60ppm
Polyoxyethylene glycol (PEG): 20mg/L or 0mg/L
Fluid temperature: 55～57 ℃
Additive A: two (3-sulfo group propyl group) sodium disulfide
(the system SPS of RASCHIG society)
Additive B 1: the dialkyl group that contains that above-mentioned synthesis example 1 obtains with ad hoc structure
Amino polymeric blends
Additive B 2: the dialkyl group that contains that above-mentioned synthesis example 2 obtains with ad hoc structure
Amino polymeric blends
Additive B 3: the dialkyl group that contains that above-mentioned synthesis example 3 obtains with ad hoc structure
Amino polymeric blends
The surfaceness Rz of the electrolytic copper foil that obtains (μ m) is a standard with JIS B 0601, normal temperature elongation (%), room temperature tensile strength (kgf/mm
2), high temperature elongation (%), high temperature tensile strength (kgf/mm
2) be standard with IPC-TM650, measure.The result is shown in table 1～table 3.
Table 1
| PEG (mg/L) | Additive A (mg/L) | Additive B 1 (mg/L) | Rz (μm) | Normal temperature elongation (%) | Room temperature tensile strength (kgf/mm 2) | High temperature elongation (%) | High temperature tensile strength (kgf/mm 2) | |
| Embodiment 1 | 20 | 50 | 100 | 0.98 | 11.0 | 34.8 | 15.0 | 20.9 |
| Embodiment 2 | 0 | 50 | 100 | 0.75 | 9.7 | 37.0 | 16.2 | 20.8 |
| Comparative example 1 | 20 | 0 | 0 | 5.5 | 9.85 | 35.2 | 12.3 | 19.8 |
| Comparative example 2 | 20 | 0 | 100 | 5.8 | 0.8 | 13.2 | 1.5 | 14.3 |
| Comparative example 3 | 20 | 50 | 0 | 5.1 | 0.2 | 10.6 | 2.9 | 12.6 |
Table 2
| PEG (mg/L) | Additive A (mg/L) | Additive B 2 (mg/L) | Rz (μm) | Normal temperature elongation (%) | Room temperature tensile strength (kgf/mm 2) | High temperature elongation (%) | High temperature tensile strength (kgf/mm 2) | |
| Embodiment 3 | 20 | 50 | 100 | 0.88 | 10.5 | 36.2 | 15.8 | 20.5 |
| Embodiment 4 | 0 | 50 | 100 | 0.91 | 9.5 | 35.5 | 15.7 | 20.7 |
| Comparative example 4 | 20 | 0 | 100 | 5.4 | 0.5 | 9.9 | 3.2 | 13.2 |
Table 3
| PEG (mg/L) | Additive A (mg/L) | Additive B 3 (mg/L) | Rz (μm) | Normal temperature elongation (%) | Room temperature tensile strength (kgf/mm 2) | High temperature elongation (%) | High temperature tensile strength (kgf/mm 2) | |
| Embodiment 5 | 20 | 50 | 100 | 0.82 | 10.0 | 35.2 | 16.0 | 20.8 |
| Embodiment 6 | 0 | 50 | 100 | 0.82 | 10.8 | 35.4 | 15.8 | 20.6 |
| Comparative example 5 | 20 | 0 | 100 | 5.3 | 0.6 | 11.4 | 2.6 | 12.8 |
Shown in above-mentioned table 1～3, in the embodiment 1～6 that has added additive of the present invention (polymkeric substance that contains dialkyl amido and organosulfur compound with ad hoc structure), surfaceness Rz is that 0.75～0.98 μ m, normal temperature elongation are 9.5～11.0%, room temperature tensile strength is 34.8～37.0kgf/mm
2, the high temperature elongation is 15.0～16.2%, high temperature tensile strength is 20.5～20.9kgf/mm
2Though can realize significant so low sectionization, normal temperature elongation, room temperature tensile strength, high temperature elongation, high temperature tensile strength and the comparative example 1 that does not add any additives are compared, and show equal excellent specific property.Relative therewith, do not having the comparative example 1 that adds and only adding in a kind of comparative example 2～5 of additive, can not realize low sectionization.In addition, when only adding a kind of additive, normal temperature elongation, room temperature tensile strength, high temperature elongation, high temperature tensile strength are bad on the contrary.
The industry utilizability
As known from the above, the copper electrolyte that contains dialkyl amino based polyalcohol and organosulfur compound with ad hoc structure that added of the present invention, has following excellent specific property, namely, low sectionization to the matsurface of resulting electrolytic copper foil is very effective, percentage elongation in the time of not only can effectively keeping normal temperature in addition also can effectively be kept high temperature percentage elongation characteristic, further also can obtain equally high-tensile. In addition, above-mentioned common interpolation is important, just can obtain above-mentioned characteristic thus.
In addition, utilize electrolytic copper foil of the present invention, can obtain being suitable for the copper-clad laminate of low section by conventional method.
Claims (5)
1. copper electrolyte, it contains: contain the polymkeric substance of dialkyl amido and organosulfur compound as additive, this polymkeric substance is by making the acrylic compounds with dialkyl amido carry out homopolymerization or obtain with other the compound copolymerization that contains unsaturated link(age).
2. copper electrolyte as claimed in claim 1 is characterized in that, above-mentioned acrylic compounds with dialkyl amido is with following general formula (1), (2) or (3) expression,
(in general formula (1)～(3), R
1The alkyl of expression hydrogen or carbonatoms 1～5, R
2And R
3The alkyl of representing carbonatoms 1～5 respectively, n are represented 1～5 integer).
3. copper electrolyte as claimed in claim 1 is characterized in that, above-mentioned organosulfur compound is the compound with following general formula (4) or (5) expression,
X-R
1-(S)
x-R
2-Y (4)
R
4-S-R
3-SO
3Z (5)
(in general formula (4) and (5), R
1, R
2And R
3Be the alkylidene group of carbonatoms 1～8, R
4Be selected from hydrogen,
, X is selected from hydrogen, sulfonic group, phosphonate group, sulfonic acid or phosphonic basic metal alkali or ammonium salt base, and Y is selected from sulfonic group, phosphonate group, sulfonic acid or phosphonic basic metal alkali, and Z is hydrogen or basic metal, n is 2 or 3).
4. electrolytic copper foil is to use each described copper electrolyte of claim 1～3 to make.
5. a copper plate pressing plate is to use the described electrolytic copper foil of claim 4 to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003202920 | 2003-07-29 | ||
| JP202920/2003 | 2003-07-29 | ||
| PCT/JP2004/008791 WO2005010239A1 (en) | 2003-07-29 | 2004-06-16 | Copper electrolytic solution containing polymer having dialkylamino group of specified structure and organic sulfur compound as additive and electrolytic copper foil produced therewith |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1806067A true CN1806067A (en) | 2006-07-19 |
| CN1806067B CN1806067B (en) | 2010-06-16 |
Family
ID=34100616
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480016822.3A Expired - Lifetime CN1806067B (en) | 2003-07-29 | 2004-06-16 | Copper electrolytic solution containing polymer having dialkylamino group of specified structure and organic sulfur compound as additive and electrolytic copper foil produced therewith |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4255130B2 (en) |
| KR (1) | KR100729061B1 (en) |
| CN (1) | CN1806067B (en) |
| TW (1) | TWI250226B (en) |
| WO (1) | WO2005010239A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104854265A (en) * | 2012-11-26 | 2015-08-19 | 德国艾托特克公司 | Copper plating bath composition |
| TWI649455B (en) * | 2013-09-11 | 2019-02-01 | 古河電氣工業股份有限公司 | Electrolytic copper foil, flexible circuit board and battery |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5329715B2 (en) | 2010-11-15 | 2013-10-30 | Ｊｘ日鉱日石金属株式会社 | Electrolytic copper foil |
| KR102377286B1 (en) | 2017-03-23 | 2022-03-21 | 에스케이넥실리스 주식회사 | Electrodeposited copper foil, current collectors for negative electrode of lithium-ion secondary batteries and lithium-ion secondary batteries |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57114685A (en) * | 1981-01-07 | 1982-07-16 | Kuraray Co Ltd | Brightener for plating bath |
| JP3313277B2 (en) * | 1995-09-22 | 2002-08-12 | 古河サーキットフォイル株式会社 | Electrodeposited copper foil for fine pattern and its manufacturing method |
| US5863410A (en) * | 1997-06-23 | 1999-01-26 | Circuit Foil Usa, Inc. | Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby |
| JP3506411B2 (en) * | 1997-12-29 | 2004-03-15 | 日本表面化学株式会社 | Zinc plating method |
| LU90532B1 (en) * | 2000-02-24 | 2001-08-27 | Circuit Foil Luxembourg Trading Sarl | Comosite copper foil and manufacturing method thereof |
| KR100389061B1 (en) * | 2002-11-14 | 2003-06-25 | 일진소재산업주식회사 | Electrolytic copper foil and process producing the same |
| JP4083171B2 (en) * | 2002-12-25 | 2008-04-30 | 日鉱金属株式会社 | Copper electrolyte containing quaternary amine compound polymer having specific skeleton and organic sulfur compound as additive, and electrolytic copper foil produced thereby |
-
2004
- 2004-06-16 JP JP2005511980A patent/JP4255130B2/en not_active Expired - Lifetime
- 2004-06-16 CN CN200480016822.3A patent/CN1806067B/en not_active Expired - Lifetime
- 2004-06-16 KR KR1020067000706A patent/KR100729061B1/en active IP Right Grant
- 2004-06-16 WO PCT/JP2004/008791 patent/WO2005010239A1/en active Application Filing
- 2004-06-21 TW TW93117890A patent/TWI250226B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104854265A (en) * | 2012-11-26 | 2015-08-19 | 德国艾托特克公司 | Copper plating bath composition |
| US9551080B2 (en) | 2012-11-26 | 2017-01-24 | Atotech Deutschland Gmbh | Copper plating bath composition |
| CN104854265B (en) * | 2012-11-26 | 2017-08-08 | 德国艾托特克公司 | Electroless copper bath composition |
| TWI649455B (en) * | 2013-09-11 | 2019-02-01 | 古河電氣工業股份有限公司 | Electrolytic copper foil, flexible circuit board and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060026963A (en) | 2006-03-24 |
| WO2005010239A1 (en) | 2005-02-03 |
| TWI250226B (en) | 2006-03-01 |
| JP4255130B2 (en) | 2009-04-15 |
| KR100729061B1 (en) | 2007-06-14 |
| CN1806067B (en) | 2010-06-16 |
| TW200506097A (en) | 2005-02-16 |
| JPWO2005010239A1 (en) | 2006-09-07 |
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