JP2022120813A - Ultrathin copper foil, and method of producing the same - Google Patents
Ultrathin copper foil, and method of producing the same Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011889 copper foil Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010410 layer Substances 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000012044 organic layer Substances 0.000 claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- RGMPVOQKBHKFLS-UHFFFAOYSA-N P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.C1(CCCCC1)O Chemical compound P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.C1(CCCCC1)O RGMPVOQKBHKFLS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 10
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000008151 electrolyte solution Substances 0.000 claims abstract 3
- 239000003792 electrolyte Substances 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000007654 immersion Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 10
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 238000007747 plating Methods 0.000 abstract 3
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 5
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000000080 wetting agent Substances 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or 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
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、超薄型銅箔の作製の技術分野に関し、特に超薄型銅箔とその作製方法に関するものである。 TECHNICAL FIELD The present invention relates to the technical field of making ultra-thin copper foils, and more particularly to ultra-thin copper foils and methods of making them.
超薄型銅箔の生産技術は微細化、専門化の程度が高く、各環節の制御基準が高い製造技術である。電子製品の高集積化、小型化の進展に伴う、プリント基板は多層化、高集積化の方向に発展し、プリント配線パターンの線幅とピッチもますます微細化の方向に発展する。そのため、配線基板の信頼性性能に対してより高い要求が出されている。例えば、微細配線に要求される薄型化銅箔は、より高い剥離性を有し、配線をエッチングする際に発生する「サイドエッチ」現象を効果的に低減または回避することができる。したがって、剥離可能な超薄型銅箔は、高品位、多層、薄型、高密度のプリント基板に広く使用され、特に近年では、リチウムイオン電池の普及により、この超薄型銅箔の開発に広い市場空間が提供されることになる。 The production technology of ultra-thin copper foil is a manufacturing technology with a high degree of miniaturization and specialization, and a high control standard for each link. Along with the development of high integration and miniaturization of electronic products, the printed circuit board develops toward multi-layering and high integration, and the line width and pitch of the printed wiring pattern also develops toward finer. Therefore, higher demands are being made for the reliability performance of wiring boards. For example, a thin copper foil required for fine wiring has higher releasability and can effectively reduce or avoid the "side etch" phenomenon that occurs when wiring is etched. Therefore, the peelable ultra-thin copper foil is widely used in high-grade, multilayer, thin, and high-density printed circuit boards. Market space will be provided.
超薄型銅箔はリチウム電池で負極活物質の担体と負極電子流の収集と輸送体の両方として機能し、銅箔の厚さが薄いほど電池のエネルギー向上作用が大きい。エネルギー密度が２６０ｗｈ／ｋｇのリチウム電池を例にとると、１ｋｗｈの電気量に対するセルの総質量は約３．８５ｋｇである、主流の８μｍ銅箔の１５％重量占有率で計算すると、銅箔の重量は約０．５８ｋｇであり、銅箔の厚さを６μｍまで下げると、総面積を変えずに銅箔の重量は２５％減少し、５０％気孔率銅箔技術を重ねると、換算したエネルギー密度は２８７ｗｈ／ｋｇに上昇し、８μｍ銅箔よりも携帯電力が多くなる。しかし、６μｍ以下の銅箔は加工が難しいため、国内メーカーの超薄型銅箔製品は、引張強度が３００～４５０ＭＰａ、伸び率が３％以上、表面粗さＲｚが２μｍ以下であることを実現できる６～９μｍが主流となっている。 The ultra-thin copper foil functions as both a carrier of the negative electrode active material and a collector and transporter of the negative electrode electron current in the lithium battery. Taking a lithium battery with an energy density of 260 wh/kg as an example, the total mass of the cell for 1 kwh of electricity is about 3.85 kg. The weight is about 0.58 kg, and when the thickness of the copper foil is reduced to 6 μm, the weight of the copper foil is reduced by 25% without changing the total area. Density increases to 287 wh/kg, more portable power than 8 μm copper foil. However, since it is difficult to process copper foil with a thickness of 6 μm or less, domestic manufacturers' ultra-thin copper foil products have a tensile strength of 300 to 450 MPa, an elongation of 3% or more, and a surface roughness Rz of 2 μm or less. 6 to 9 μm, which is possible, is the mainstream.
既存の超薄型銅箔の厚さは要求を満たすことができず、引張強度と伸び率は悪いが、現在、研究開発チームは６μｍ未満、最低４μｍの超薄型銅箔製品を試作したが、銅箔の表面粗さＲａは０．３５μｍ未満、引張性能は最大４０８ＭＰａ、伸び率は最大９．５％に達し、超薄型銅箔の各性能面での突破を実現した。しかし、薄型化、軽量化、コストダウン、効率化の要求のうち、銅箔のさらなる軽量化は、現在、銅箔業界の発展のための重要な方向性となっている。超薄型銅箔の厚さをいかに薄くし、かつ多様な生産ニーズに対応できるような大きな性能ブレークスルーを実現するか、これが超薄型銅箔の開発を達成するための重要かつ難しい問題なのである。 The thickness of the existing ultra-thin copper foil cannot meet the requirements, and the tensile strength and elongation are poor. , the surface roughness Ra of the copper foil is less than 0.35 μm, the tensile strength is up to 408 MPa, and the elongation is up to 9.5%, realizing a breakthrough in various performance aspects of ultra-thin copper foil. However, among the demands for thinness, weight reduction, cost reduction, and efficiency improvement, further weight reduction of copper foil is currently an important direction for the development of the copper foil industry. How to reduce the thickness of ultra-thin copper foil and achieve a large performance breakthrough that can meet various production needs is an important and difficult problem to achieve the development of ultra-thin copper foil. be.
本発明の目的は、先行技術の上記問題点を解決し、超薄型銅箔の多様化、高性能化に対応するため、超薄型銅箔の厚みが薄く、性能が良い超薄型銅箔及びその作製方法を提供することである。 The object of the present invention is to solve the above-mentioned problems of the prior art, and to respond to the diversification and high performance of ultra-thin copper foils. It is to provide a foil and a method of making the same.
上記目的を達成するために、本発明は以下の解決策を提供する。 In order to achieve the above objects, the present invention provides the following solutions.
本発明は、以下のステップを含む超薄型銅箔の作製方法を提供する。
（１）金属箔担体の表面に有機層を吸着させる（ステップ（１））：
シクロヘキサノール六リン酸と２－チオウラシルの混合水溶液に金属箔担体を浸漬して吸着させ、有機層吸着用担体を得る。
（２）吸着した有機層の表面に合金層を成膜する（ステップ（２））：
電流密度が２５～３０Ａ／ｄｍ２、電解液温度が４８～５０℃、ｐＨが４．５～５．０で、有機層の表面に合金層を成膜させ、
前記電解液は、希土類元素のＰｒとＮｄを含むタングステン－ニッケル電解液である。
（３）合金層の表面に超薄型銅箔層を成膜する（ステップ（３））：
成膜電解液は、リグニンスルホン酸ナトリウムとキトサンオリゴ糖を含む硫酸銅電解液である。
さらに、前記シクロヘキサノール六リン酸の濃度が１～１５ｇ／Ｌであり、前記２－チオウラシルの濃度が１～８ｇ／Ｌである。
The present invention provides a method of fabricating an ultra-thin copper foil, including the following steps.
(1) Adsorbing an organic layer on the surface of a metal foil carrier (step (1)):
A metal foil carrier is immersed in a mixed aqueous solution of cyclohexanol hexaphosphate and 2-thiouracil for adsorption to obtain a carrier for adsorbing an organic layer.
(2) forming an alloy layer on the surface of the adsorbed organic layer (step (2)):
forming an alloy layer on the surface of the organic layer at a current density of 25 to 30 A/dm 2 , an electrolyte temperature of 48 to 50° C., and a pH of 4.5 to 5.0;
The electrolyte is a tungsten-nickel electrolyte containing the rare earth elements Pr and Nd.
(3) Forming an ultra-thin copper foil layer on the surface of the alloy layer (step (3)):
The film-forming electrolyte is a copper sulfate electrolyte containing sodium ligninsulfonate and chitosan oligosaccharide.
Furthermore, the concentration of cyclohexanol hexaphosphate is 1 to 15 g/L, and the concentration of 2-thiouracil is 1 to 8 g/L.
さらに、ステップ（１）の浸漬吸着を室温で７０～７５秒間行うことである。 Further, the immersion adsorption of step (1) is performed at room temperature for 70-75 seconds.
さらに、前記金属箔が銅箔である。
Furthermore, the metal foil is copper foil.
さらに、前記希土類元素のＰｒとＮｄを含むタングステン－ニッケル電解液には、硫酸ニッケルの濃度が２０～３５ｇ／Ｌで、タングステン酸ナトリウムの濃度が２０～３５ｇ／Ｌで、希土類元素Ｐｒの濃度が０．０５～０．０６ｇ／Ｌで、Ｎｄの濃度は０．０３－０．０４ｇ／Ｌである。 Further, the tungsten-nickel electrolyte containing rare earth elements Pr and Nd has a nickel sulfate concentration of 20 to 35 g/L, a sodium tungstate concentration of 20 to 35 g/L, and a rare earth element Pr concentration of 0.05-0.06 g/L and the concentration of Nd is 0.03-0.04 g/L.
さらに、ステップ（３）の成膜電解液中のリグノスルホン酸ナトリウムの濃度は０．１～０．２ｇ／Ｌ、キトサンオリゴ糖の濃度は１０～２５ｇ／Ｌである。 Furthermore, the concentration of sodium lignosulfonate in the film forming electrolyte in step (3) is 0.1 to 0.2 g/L, and the concentration of chitosan oligosaccharide is 10 to 25 g/L.
さらに、前記ステップ（３）には、超薄型銅箔層は３回成膜で、第１回成膜電解液のＣｕ２＋濃度が６５～６８ｇ／Ｌで、硫酸濃度が１４５～１５０ｇ／Ｌで、第２回成膜電解液のＣｕ２＋濃度が２０～３０ｇ／Ｌで、硫酸濃度が１１０～１２０ｇ／Ｌで、第３回成膜電解液のＣｕ２＋濃度が６０～６５ｇ／Ｌで、硫酸濃度が１２０～１３０ｇ／Ｌで行うことである。 Further, in the step (3), the ultra-thin copper foil layer is formed three times, the Cu 2+ concentration of the first film-forming electrolyte is 65-68 g/L, and the sulfuric acid concentration is 145-150 g/L. The Cu 2+ concentration of the second deposition electrolyte is 20 to 30 g/L, the sulfuric acid concentration is 110 to 120 g/L, the Cu 2+ concentration of the third deposition electrolyte is 60 to 65 g/L, The concentration of sulfuric acid should be 120-130 g/L.
また、本発明は、上記の作製方法により作製された超薄型銅箔を提供するものである。 Moreover, the present invention provides an ultra-thin copper foil produced by the above production method.
本発明は、以下の技術的効果を開示している。 The present invention discloses the following technical effects.
本発明は、まず清浄な３５μｍの銅箔担体の上にシクロヘキサノール六リン酸及び２－チオウラシルを原料とする有機層を吸着させてから、その有機層の上に希土類元素ＰｒとＮｄを含むタングステン－ニッケル合金を成膜する。希土類元素ＰｒとＮｄの導入により銅箔の剥離強度が向上し、超薄型銅箔表面の結晶粒を微細化することができる。同時にシクロヘキサノール六リン酸はチオフェンと一緒に有機層として機能するため、有機層自体が良好な剥離ポテンシャルを有し、合金層と複合した場合、わずかな希土類元素ＰｒとＮｄの添加量で優れる剥離効果を実現できる。これにより、剥離剤の吸着が少ないと剥離しにくく、吸着が多いと導電性が悪くなり、その後の電着ステップに影響を及ぼすという問題を効果的に解決することができる。 The present invention first adsorbs an organic layer made of cyclohexanol hexaphosphate and 2-thiouracil on a clean 35 μm copper foil carrier, and then deposits tungsten containing rare earth elements Pr and Nd on the organic layer. - depositing a nickel alloy; The introduction of the rare earth elements Pr and Nd improves the peel strength of the copper foil and makes it possible to refine the crystal grains on the surface of the ultra-thin copper foil. At the same time, cyclohexanol hexaphosphate functions as an organic layer together with thiophene, so the organic layer itself has a good peeling potential, and when combined with an alloy layer, excellent peeling can be achieved with a small amount of rare earth elements Pr and Nd added. effect can be achieved. As a result, it is possible to effectively solve the problem that if the release agent is less adsorbed, it is difficult to release, and if the release agent is more adsorbed, the conductivity deteriorates, which affects the subsequent electrodeposition step.
現在、リグニンスルホン酸ナトリウムは工業的に分散剤や湿潤剤として広く使用されているが、本発明には、リグニンスルホン酸ナトリウムとキトサンオリゴ糖を複合添加剤として硫酸銅電解液に添加することを創造的に行い、合金層中の極めて少量の希土類元素Ｐｒ、Ｎｄによって超薄型銅箔の軽量化の均一成膜を実現し、超薄型銅箔が４μｍの限界を突破して３．５μｍの超軽量化を実現し、かつ引張性能が５１０ＭＰａと高く、伸び率が最高１０％に達し、軽量化超薄型銅箔に優れた性能を与えている。 At present, sodium lignosulfonate is widely used industrially as a dispersing agent and a wetting agent. Creatively, the extremely small amount of rare earth elements Pr and Nd in the alloy layer realizes uniform deposition of light weight ultra-thin copper foil. It has a high tensile performance of 510 MPa and a maximum elongation of 10%, giving the lightweight, ultra-thin copper foil excellent performance.
本発明の調製方法は安定的かつ制御可能であり、複合銅箔は優れた剥離強度を有し、調製された超薄型銅箔は、主流の超薄型銅箔８μｍ、６μｍ、４μｍの限界を突破し、引張特性、伸度等の面で優れた性能を反映しながら、３．５μｍの超薄効果を達成でき、超薄型銅箔の開発、超薄型銅箔の開発を依存する多くの産業に大きな意義を持っている。 The preparation method of the present invention is stable and controllable, the composite copper foil has excellent peel strength, and the prepared ultra-thin copper foil is the limit of the mainstream ultra-thin copper foil 8 μm, 6 μm, 4 μm , and can achieve an ultra-thin effect of 3.5 μm while reflecting excellent performance in terms of tensile properties, elongation, etc., and depends on the development of ultra-thin copper foil. It has great significance for many industries.
次に、本発明の様々な例示的な実施形態を詳細に説明するが、この詳細な説明は、本発明の限定とみなされるべきではなく、本発明の特定の局面、特徴および実施形態のより詳細な説明として理解されるべきである。 Various exemplary embodiments of the invention will now be described in detail; however, this detailed description should not be construed as a limitation of the invention, but rather of specific aspects, features and embodiments of the invention. It should be understood as a detailed description.
本発明に記載された用語は、特定の実施形態を説明することのみを意図しており、本発明を限定することを意図していないことを理解することができる。さらに、本発明における数値の範囲に関しては、その範囲の上限と下限の間の各中間値も具体的に開示されていると理解される。また、記載された範囲内の任意の記載値または中間値と、記載された範囲内の他の記載値または中間値との間の各小範囲も、本発明に含まれる。これらの小さい範囲の上限と下限は、独立して範囲に含めたり除外したりすることができる。 It is to be understood that the terminology used herein is intended to describe particular embodiments only and is not intended to be limiting of the invention. Moreover, with respect to any numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Also included within the invention is each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range. The upper and lower limits of these smaller ranges can independently be included or excluded from the range.
特に断らない限り、本明細書で使用されるすべての技術用語および科学用語は、本発明で説明する分野の通常の技術者によって一般的に理解されるのと同じ意味を有する。本発明では、好ましい方法および材料のみを説明するが、本明細書に記載したものと類似または同等の任意の方法および材料も、本発明の実施または試験に使用することができる。本明細書で言及するすべての文献は、当該文献に関連する方法および／または材料を開示し、説明する目的で参照により組み込まれるものである。本仕様書と組み込まれた文献が矛盾する場合、本仕様書の内容が優先されるものとする。 Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art described in this invention. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All publications mentioned herein are incorporated by reference for the purpose of disclosing and describing the methods and/or materials in connection with which they are associated. In the event of any conflict between this specification and an incorporated document, the contents of this specification shall control.
本発明の明細書の具体的な実施の形態には、本発明の範囲または精神から逸脱することなく、多くの改良や変更を加えることができることは当業者にとって明らかである。本発明の明細書から得られる他の実施形態は、当業者にとって明らかである。本発明の明細書および実施形態は、あくまで例示に過ぎない。 It will be apparent to those skilled in the art that many modifications and variations may be made to the specific embodiments of the specification of the invention without departing from the scope or spirit of the invention. Other embodiments derived from the specification of the invention will be apparent to those skilled in the art. The specification and embodiments of the invention are merely exemplary.
本明細書で使用される用語「含む」、「有する」、「ある」等などについては、いずれも開放的な用語であり、含むがこれに限定されないことを意味する。本発明で使用する「部」は、特に断らない限り、質量部で表す。 As used herein, the terms “including,” “having,” “a,” etc. are all open terms and mean including but not limited to. Unless otherwise specified, the "parts" used in the present invention are parts by mass.
（１）銅箔担体の表面に有機層を吸着させる：
厚さが３５μｍの銅箔を成膜担体とし、担体を酸洗処理を行い、担体表面の酸化物及び不純物を除去した後、洗浄処理後の担体銅箔をシクロヘキサノール六リン酸及び２－チオウラシルの混合水溶液〔シクロヘキサノール六リン酸の濃度が１ｇ／Ｌで、２－チオウラシル濃度が１ｇ／Ｌである〕に浸漬し、室温で７０ｓ浸漬処理し、取り出した後、脱イオン水で洗い、有機層を吸着する担体を得る。
(1) Absorption of an organic layer on the surface of a copper foil carrier:
A copper foil with a thickness of 35 μm is used as a film-forming carrier, and the carrier is subjected to pickling treatment to remove oxides and impurities on the surface of the carrier. [The concentration of cyclohexanol hexaphosphate is 1 g / L and the concentration of 2-thiouracil is 1 g / L], immersed at room temperature for 70 s, removed, washed with deionized water, organic A carrier is obtained which adsorbs the layer.
（２）担体に吸着した有機層の上に合金層を成膜させる：
タングステン－ニッケル合金電解液の調製；電解液中の硫酸ニッケルの濃度が２０ｇ／Ｌで、タングステン酸ナトリウム濃度が３５ｇ／Ｌで、希土類元素Ｐｒの添加量が０．０５ｇ／Ｌ、Ｎｄの添加量は０．０３ｇ／Ｌで、電解液のｐｈが４．５である。
成膜プロセスパラメータ；電流密度が２５Ａ／ｄｍ２で、電解液温度が４８℃で、成膜時間は５ｓである。
(2) Depositing an alloy layer on the organic layer adsorbed on the carrier:
Preparation of a tungsten-nickel alloy electrolyte; the concentration of nickel sulfate in the electrolyte is 20 g/L, the concentration of sodium tungstate is 35 g/L, the amount of rare earth element Pr added is 0.05 g/L, and the amount of Nd added. is 0.03 g/L and the pH of the electrolyte is 4.5.
Deposition process parameters; current density is 25 A/dm 2 , electrolyte temperature is 48° C., deposition time is 5 s.
（３）合金層の表面に超薄型銅箔層は３回で成膜する：
初回浸漬銅プロセスパラメータ；電解液中のＣｕ２＋の濃度が６５ｇ／Ｌで、硫酸の濃度が１４５ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が１０ｇ／Ｌで、電解液の温度が４５℃である。電流密度が１０Ａ／ｄｍ２で、成膜時間８ｓである。
第二回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が２０ｇ／Ｌで、硫酸の濃度が１１０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が１０ｇ／Ｌで、電解液温度が４８℃である。電流密度が２０Ａ／ｄｍ２で、成膜時間が８ｓである。
第三回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が６０ｇ／Ｌで、硫酸の濃度が１２５ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が１０ｇ／Ｌで、電解液温度が４５℃である。電流密度が１０Ａ／ｄｍ２で、成膜時間が１０ｓである。
(3) Forming an ultra-thin copper foil layer on the surface of the alloy layer in three steps:
Initial immersion copper process parameters: the concentration of Cu 2+ in the electrolyte is 65 g/L, the concentration of sulfuric acid is 145 g/L, the concentration of sodium lignosulfonate is 0.1 g/L, and the concentration of chitosan oligosaccharide is 10 g. /L and the temperature of the electrolyte is 45°C. The current density is 10 A/dm 2 and the film formation time is 8 s.
Second immersion copper process parameters; The concentration is 10 g/L and the electrolyte temperature is 48°C. The current density is 20 A/dm 2 and the film formation time is 8 s.
Third immersion copper process parameters; The concentration is 10 g/L and the electrolyte temperature is 45°C. The current density is 10 A/dm 2 and the film formation time is 10 s.
（１）銅箔担体の表面に有機層を吸着させる：
厚さが３５μｍの銅箔を成膜担体とし、担体を酸洗処理を行い、担体表面の酸化物及び不純物を除去した後、洗浄処理後の担体銅箔をシクロヘキサノール六リン酸及び２－チオウラシルの混合水溶液〔シクロヘキサノール六リン酸の濃度が５ｇ／Ｌで、２－チオウラシル濃度が５ｇ／Ｌである〕に浸漬し、室温で７５ｓ浸漬処理し、取り出した後、脱イオン水で洗い、有機層を吸着する担体を得る。
(1) Absorption of an organic layer on the surface of a copper foil carrier:
A copper foil with a thickness of 35 μm is used as a film-forming carrier, and the carrier is subjected to pickling treatment to remove oxides and impurities on the surface of the carrier. [The concentration of cyclohexanol hexaphosphate is 5 g / L and the concentration of 2-thiouracil is 5 g / L], immersed at room temperature for 75 s, removed, washed with deionized water, organic A carrier is obtained which adsorbs the layer.
（２）担体に吸着した有機層の上に合金層を成膜させる：
タングステン－ニッケル合金電解液の調製；電解液中の硫酸ニッケルの濃度が２２ｇ／Ｌで、タングステン酸ナトリウム濃度が３０ｇ／Ｌで、希土類元素Ｐｒの添加量が０．０６ｇ／Ｌ、Ｎｄの添加量は０．０４ｇ／Ｌで、電解液のｐｈが５．０である。
成膜プロセスパラメータ；電流密度が２８Ａ／ｄｍ２で、電解液温度が４９℃で、成膜時間は５ｓである。
(2) Depositing an alloy layer on the organic layer adsorbed on the carrier:
Preparation of a tungsten-nickel alloy electrolyte; the concentration of nickel sulfate in the electrolyte is 22 g/L, the concentration of sodium tungstate is 30 g/L, the amount of rare earth element Pr added is 0.06 g/L, and the amount of Nd added. is 0.04 g/L and the pH of the electrolyte is 5.0.
Deposition process parameters: current density is 28 A/dm 2 , electrolyte temperature is 49° C., deposition time is 5 s.
（３）合金層の表面に超薄型銅箔層は３回で成膜する：
初回浸漬銅プロセスパラメータ；電解液中のＣｕ２＋の濃度が６８ｇ／Ｌで、硫酸の濃度が１５０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．２ｇ／Ｌで、キトサンオリゴ糖の濃度が２５ｇ／Ｌで、電解液の温度が４８℃である。電流密度が２０Ａ／ｄｍ２で、成膜時間９ｓである。
第二回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が３０ｇ／Ｌで、硫酸の濃度が１２０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．２ｇ／Ｌで、キトサンオリゴ糖の濃度が２５ｇ／Ｌで、電解液温度が４５℃である。電流密度が３５Ａ／ｄｍ２で、成膜時間が１０ｓである。
(3) Forming an ultra-thin copper foil layer on the surface of the alloy layer in three steps:
Initial immersion copper process parameters: the concentration of Cu2 + in the electrolyte is 68g/L, the concentration of sulfuric acid is 150g/L, the concentration of sodium lignosulfonate is 0.2g/L, and the concentration of chitosan oligosaccharide is 25g. /L and the temperature of the electrolyte is 48°C. The current density is 20 A/dm 2 and the film formation time is 9 s.
Second immersion copper process parameters; The concentration is 25 g/L and the electrolyte temperature is 45°C. The current density is 35 A/dm 2 and the film formation time is 10 s.
第三回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が６５ｇ／Ｌで、硫酸の濃度が１２０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．２ｇ／Ｌで、キトサンオリゴ糖の濃度が１５ｇ／Ｌで、電解液温度が４８℃である。電流密度が３５Ａ／ｄｍ２で、成膜時間が８ｓである。 Third immersion copper process parameters; The concentration is 15 g/L and the electrolyte temperature is 48°C. The current density is 35 A/dm 2 and the film formation time is 8 s.
（１）銅箔担体の表面に有機層を吸着させる：
厚さが３５μｍの銅箔を成膜担体とし、担体を酸洗処理を行い、担体表面の酸化物及び不純物を除去した後、洗浄処理後の担体銅箔をシクロヘキサノール六リン酸及び２－チオウラシルの混合水溶液〔シクロヘキサノール六リン酸の濃度が１０ｇ／Ｌで、２－チオウラシル濃度が６ｇ／Ｌである〕に浸漬し、室温で７３ｓ浸漬処理し、取り出した後、脱イオン水で洗い、有機層を吸着する担体を得る。
(1) Absorption of an organic layer on the surface of a copper foil carrier:
A copper foil with a thickness of 35 μm is used as a film-forming carrier, and the carrier is subjected to pickling treatment to remove oxides and impurities on the surface of the carrier. [cyclohexanol hexaphosphate concentration is 10 g / L, 2-thiouracil concentration is 6 g / L], immersed at room temperature for 73 s, taken out, washed with deionized water, organic A carrier is obtained which adsorbs the layer.
（２）担体に吸着した有機層の上に合金層を成膜させる：
タングステン－ニッケル合金電解液の調製；電解液中の硫酸ニッケルの濃度が２３ｇ／Ｌで、タングステン酸ナトリウム濃度が２５ｇ／Ｌで、希土類元素Ｐｒの添加量が０．０６ｇ／Ｌ、Ｎｄの添加量は０．０４ｇ／Ｌで、電解液のｐｈが５．０である。
成膜プロセスパラメータ；電流密度が３０Ａ／ｄｍ２で、電解液温度が５０℃で、成膜時間は６ｓである。
(2) Depositing an alloy layer on the organic layer adsorbed on the carrier:
Preparation of a tungsten-nickel alloy electrolyte; the concentration of nickel sulfate in the electrolyte is 23 g/L, the concentration of sodium tungstate is 25 g/L, the amount of rare earth element Pr added is 0.06 g/L, and the amount of Nd added. is 0.04 g/L and the pH of the electrolyte is 5.0.
Deposition process parameters; current density is 30 A/dm 2 , electrolyte temperature is 50° C., deposition time is 6 s.
（３）合金層の表面に超薄型銅箔層は３回で成膜する：
初回浸漬銅プロセスパラメータ；電解液中のＣｕ２＋の濃度が６５ｇ／Ｌで、硫酸の濃度が１４５ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．２ｇ／Ｌで、キトサンオリゴ糖の濃度が１５ｇ／Ｌで、電解液の温度が４５℃である。電流密度が３５Ａ／ｄｍ２で、成膜時間１０ｓである。
第二回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が２５ｇ／Ｌで、硫酸の濃度が１１０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が２０ｇ／Ｌで、電解液温度が４８℃である。電流密度が２５Ａ／ｄｍ２で、成膜時間が９ｓである。
第三回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が６３ｇ／Ｌで、硫酸の濃度が１３０ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が２０ｇ／Ｌで、電解液温度が４６℃である。電流密度が２０／ｄｍ２で、成膜時間が９ｓである。
(3) Forming an ultra-thin copper foil layer on the surface of the alloy layer in three steps:
Initial immersion copper process parameters: the concentration of Cu 2+ in the electrolyte is 65g/L, the concentration of sulfuric acid is 145g/L, the concentration of sodium lignosulfonate is 0.2g/L, and the concentration of chitosan oligosaccharide is 15g. /L and the temperature of the electrolyte is 45°C. The current density is 35 A/dm 2 and the film formation time is 10 s.
Second immersion copper process parameters; The concentration is 20 g/L and the electrolyte temperature is 48°C. The current density is 25 A/dm 2 and the film formation time is 9 s.
Third immersion copper process parameters; The concentration is 20 g/L and the electrolyte temperature is 46°C. The current density is 20/dm 2 and the film formation time is 9 s.
（１）銅箔担体の表面に有機層を吸着させる：
厚さが３５μｍの銅箔を成膜担体とし、担体を酸洗処理を行い、担体表面の酸化物及び不純物を除去した後、洗浄処理後の担体銅箔をシクロヘキサノール六リン酸及び２－チオウラシルの混合水溶液〔シクロヘキサノール六リン酸の濃度が１２ｇ／Ｌで、２－チオウラシル濃度が８ｇ／Ｌである〕に浸漬し、室温で７２ｓ浸漬処理し、取り出した後、脱イオン水で洗い、有機層を吸着する担体を得る。
(1) Absorption of an organic layer on the surface of a copper foil carrier:
A copper foil with a thickness of 35 μm is used as a film-forming carrier, and the carrier is subjected to pickling treatment to remove oxides and impurities on the surface of the carrier. [The concentration of cyclohexanol hexaphosphate is 12 g / L and the concentration of 2-thiouracil is 8 g / L], immersed at room temperature for 72 s, removed, washed with deionized water, organic A carrier is obtained which adsorbs the layer.
（２）担体に吸着した有機層の上に合金層を成膜させる：
タングステン－ニッケル合金電解液の調製；電解液中の硫酸ニッケルの濃度が２５ｇ／Ｌで、タングステン酸ナトリウム濃度が２０ｇ／Ｌで、希土類元素Ｐｒの添加量が０．０５ｇ／Ｌ、Ｎｄの添加量は０．０４ｇ／Ｌで、電解液のｐｈが５．０である。
成膜プロセスパラメータ；電流密度が３０Ａ／ｄｍ２で、電解液温度が４８℃で、成膜時間は６ｓである。
(2) Depositing an alloy layer on the organic layer adsorbed on the carrier:
Preparation of a tungsten-nickel alloy electrolyte; the concentration of nickel sulfate in the electrolyte is 25 g/L, the concentration of sodium tungstate is 20 g/L, the amount of rare earth element Pr added is 0.05 g/L, and the amount of Nd added. is 0.04 g/L and the pH of the electrolyte is 5.0.
Deposition process parameters; current density is 30 A/dm 2 , electrolyte temperature is 48° C., deposition time is 6 s.
（３）合金層の表面に超薄型銅箔層は３回で成膜する：
初回浸漬銅プロセスパラメータ；電解液中のＣｕ２＋の濃度が６６ｇ／Ｌで、硫酸の濃度が１４８ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が２０ｇ／Ｌで、電解液の温度が４６℃である。電流密度が３０Ａ／ｄｍ２で、成膜時間１０ｓである。
第二回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が３０ｇ／Ｌで、硫酸の濃度が１１５ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．１ｇ／Ｌで、キトサンオリゴ糖の濃度が２５ｇ／Ｌで、電解液温度が４６℃である。電流密度が３０Ａ／ｄｍ２で、成膜時間が８ｓである。
第三回浸漬銅プロセスパラメータ；電解液には、Ｃｕ２＋の濃度が６２ｇ／Ｌで、硫酸の濃度が１２５ｇ／Ｌで、リグニンスルホン酸ナトリウムの濃度が０．２ｇ／Ｌで、キトサンオリゴ糖の濃度が２５ｇ／Ｌで、電解液温度が４７℃である。電流密度が２５／ｄｍ２で、成膜時間が１０ｓである。
＜比較例１＞
(3) Forming an ultra-thin copper foil layer on the surface of the alloy layer in three steps:
Initial immersion copper process parameters: the concentration of Cu 2+ in the electrolyte is 66 g/L, the concentration of sulfuric acid is 148 g/L, the concentration of sodium lignosulfonate is 0.1 g/L, and the concentration of chitosan oligosaccharide is 20 g. /L and the temperature of the electrolyte is 46°C. The current density is 30 A/dm 2 and the film formation time is 10 s.
Second immersion copper process parameters; The concentration is 25 g/L and the electrolyte temperature is 46°C. The current density is 30 A/dm 2 and the film formation time is 8 s.
Third immersion copper process parameters; The concentration is 25 g/L and the electrolyte temperature is 47°C. The current density is 25/dm 2 and the film formation time is 10 s.
<Comparative Example 1>
実施例１と異なる点は、有機層の原料にベンゾトリアゾールを用いることである。
＜比較例２＞
The difference from Example 1 is that benzotriazole is used as the raw material for the organic layer.
<Comparative Example 2>
実施例１と異なる点は、合金層に希土類元素を添加しないことである。
＜比較例３＞
The difference from Example 1 is that no rare earth element is added to the alloy layer.
<Comparative Example 3>
実施例１と異なる点は、合金層中の希土類元素ＮｄをＬａに置き換えることである。
＜比較例４＞
The difference from Example 1 is that the rare earth element Nd in the alloy layer is replaced with La.
<Comparative Example 4>
実施例１と異なる点は、浸漬銅電解液にリグニンスルホン酸ナトリウムを添加しないことである。 The difference from Example 1 is that sodium ligninsulfonate is not added to the immersion copper electrolyte.
実施例１－４及び比較例１－４で作制する複合箔をプリプレグに６０ＫＮの圧力、１７５℃の条件で圧着して複合積層板を作制する、万能試験機に載せて剥離強度試験を行う。テスト結果を表１に示す。
テストの結果として、本発明の実施例１～４の担体と超薄型銅箔との間の剥離効果は優れて、剥離強度は０．１４ｋｇ／ｃｍに達することができ、剥離後の超薄型銅箔の表面は光沢がきれいである。比較例１－４の担体と超薄型銅箔との間の剥離強度は低く、その中で比較例１－２は超薄型銅箔が担体に残留する現象がある。 The test results show that the peeling effect between the carrier of Examples 1-4 of the present invention and the ultra-thin copper foil is excellent, the peel strength can reach 0.14 kg/cm, and the ultra-thin The surface of the mold copper foil has a beautiful luster. The peel strength between the carrier of Comparative Example 1-4 and the ultra-thin copper foil is low, and in Comparative Example 1-2 there is a phenomenon that the ultra-thin copper foil remains on the carrier.
実施例１－４及び比較例３－４で剥離した超薄型銅箔について性能試験を行った（比較例１－２では超薄型銅箔が担体に残留する現象があり、完全な超薄型銅箔が得られなかったため性能試験を行わなかった）結果を表２に示す。
以上述べた実施例は、本発明の好ましい態様を説明しただけであり、本発明の範囲を限定するものではなく、本発明の設計精神を逸脱することなく、当業者が本発明の請求項に対して行った様々な変形や改良は、本発明の特許請求の範囲によって定められる保護範囲内に収まるべきである。 The above-described embodiments merely illustrate preferred embodiments of the invention, and are not intended to limit the scope of the invention, and those skilled in the art may make modifications to the claims of the invention without departing from the design spirit of the invention. Various modifications and improvements made to it should fall within the protection scope defined by the claims of the present invention.
Claims (5)
シクロヘキサノール六リン酸と２－チオウラシルの混合水溶液に前記金属箔担体を浸漬して吸着させ、有機層吸着用担体を得て、
（２）吸着した前記有機層の表面に合金層を成膜するステップ（２）であって、
電流密度が２５～３０Ａ／ｄｍ２、電解液の温度が４８～５０℃、ｐＨが４．５～５．０で、前記有機層の表面に前記合金層を成膜させ、
前記電解液は、希土類元素のＰｒとＮｄを含むタングステン－ニッケル電解液であり、
（３）前記合金層の表面に超薄型銅箔層を成膜するステップ（３）であって、
成膜電解液は、リグニンスルホン酸ナトリウムとキトサンオリゴ糖を含む硫酸銅電解液であり、
前記シクロヘキサノール六リン酸の濃度が１～１５ｇ／Ｌであり、前記２－チオウラシルの濃度が１～８ｇ／Ｌであり、
前記希土類元素のＰｒとＮｄを含む前記タングステン－ニッケル電解液には、硫酸ニッケルの濃度が２０～３５ｇ／Ｌで、タングステン酸ナトリウムの濃度が２０～３５ｇ／Ｌで、前記希土類元素Ｐｒの濃度が０．０５～０．０６ｇ／Ｌで、Ｎｄの濃度は０．０３－０．０４ｇ／Ｌであり、
前記ステップ（３）の前記成膜電解液中の前記リグノスルホン酸ナトリウムの濃度は０．１～０．２ｇ／Ｌ、前記キトサンオリゴ糖の濃度は１０～２５ｇ／Ｌである、
というステップを含むこと、を特徴とする超薄型銅箔の作製方法。 (1) A step (1) of adsorbing an organic layer on the surface of a metal foil carrier,
The metal foil carrier is immersed in a mixed aqueous solution of cyclohexanol hexaphosphate and 2-thiouracil for adsorption to obtain a carrier for adsorbing an organic layer,
(2) forming an alloy layer on the surface of the adsorbed organic layer (2),
forming the alloy layer on the surface of the organic layer at a current density of 25 to 30 A/dm 2 , an electrolyte temperature of 48 to 50° C., and a pH of 4.5 to 5.0;
The electrolytic solution is a tungsten-nickel electrolytic solution containing rare earth elements Pr and Nd,
(3) forming an ultra-thin copper foil layer on the surface of the alloy layer (3),
The film-forming electrolyte is a copper sulfate electrolyte containing sodium ligninsulfonate and chitosan oligosaccharide,
The concentration of cyclohexanol hexaphosphate is 1 to 15 g/L, the concentration of 2-thiouracil is 1 to 8 g/L,
The tungsten-nickel electrolyte containing the rare earth elements Pr and Nd has a nickel sulfate concentration of 20 to 35 g/L, a sodium tungstate concentration of 20 to 35 g/L, and a rare earth element Pr concentration of 0.05-0.06 g/L, the concentration of Nd is 0.03-0.04 g/L;
The sodium lignosulfonate concentration in the film-forming electrolyte in step (3) is 0.1 to 0.2 g/L, and the chitosan oligosaccharide concentration is 10 to 25 g/L.
A method for fabricating an ultra-thin copper foil, comprising:
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