JP2015063730A - Carrier-fitted hole-opened metal foil and method for producing the same - Google Patents
Carrier-fitted hole-opened metal foil and method for producing the same Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000011888 foil Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000007747 plating Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 24
- 238000007740 vapor deposition Methods 0.000 claims description 19
- 238000007639 printing Methods 0.000 claims description 8
- 238000007646 gravure printing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 38
- -1 polyethylene terephthalate Polymers 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AZUHEGMJQWJCFQ-UHFFFAOYSA-N 1,1-bis(2h-benzotriazol-4-ylmethyl)urea Chemical compound C1=CC2=NNN=C2C(CN(CC=2C3=NNN=C3C=CC=2)C(=O)N)=C1 AZUHEGMJQWJCFQ-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- WYOHYGGHYATVOZ-UHFFFAOYSA-L nickel(2+);sulfate;pentahydrate Chemical compound O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O WYOHYGGHYATVOZ-UHFFFAOYSA-L 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Electroplating Methods And Accessories (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
本発明は、二次電池用の負極集電体などに用いられるパターン状の穴開き金属箔であって、キャリア上に積層されて形成された穴開き金属箔に関する。また、その製造方法に関する。 The present invention relates to a perforated metal foil in a pattern shape used for a negative electrode current collector or the like for a secondary battery, and is formed by being laminated on a carrier. Moreover, it is related with the manufacturing method.
リチウムイオン二次電池に代表される二次電池は、ノート型パーソナルコンピュータ、携帯電話、スマートフォンなど携帯型情報端末機の普及に伴い、より小型化、軽量化が求められている。また電池容量増大の観点からも、二次電池に用いられる集電体はより薄いものが要求されるようになってきている。 Secondary batteries typified by lithium ion secondary batteries are required to be smaller and lighter with the spread of portable information terminals such as notebook personal computers, mobile phones, and smartphones. Further, from the viewpoint of increasing the battery capacity, a thinner current collector used for a secondary battery has been required.
二次電池用や電気二重層キャパシタ用の集電体として、金属箔にパターン状の貫通孔が形成されたものが用いられている。このような穴開き金属箔を製造する方法として、機械的に打ち抜きをするパンチング方式が公知である。また、特許文献１や２には、エッチング方式による穴開き集電体の製造方法が開示されている。 As a current collector for a secondary battery or an electric double layer capacitor, a metal foil having a patterned through hole is used. As a method for manufacturing such a perforated metal foil, a punching method in which punching is mechanically performed is known. Patent Documents 1 and 2 disclose a method of manufacturing a perforated current collector by an etching method.
しかしながら、パンチング方式による穴開き金属箔の製造方法においては、貫通孔の周辺に発生するバリが問題となる。集電体とセパレータを多数積層するような二次電池、キャパシタにおいては、わずかなバリによってその厚みが増大してしまう。また、バリのような突起部が存在すると電流集中によるショートを引き起こすという問題があった。更に、微細なパターンの穴を打ち抜くためには、精度の高い金型を作成する必要がある。 However, in the method of manufacturing a perforated metal foil by the punching method, burrs generated around the through hole are a problem. In a secondary battery and capacitor in which a large number of current collectors and separators are stacked, the thickness increases due to slight burrs. In addition, there is a problem that a short-circuit due to current concentration is caused when a protrusion such as a burr exists. Furthermore, in order to punch out holes with a fine pattern, it is necessary to create a highly accurate mold.
一方、エッチング方式においては、レジスト層の形成においてパターンサイズに制限があり、連続したシームレスなパターンを形成するには限界があった。また、製造工程も多く、設備も大掛かりになってしまう。更に、これら従来の方式においては、打ち抜いた部分、エッチングによって除去した部分の金属を無駄にしてしまうという欠点もあった。 On the other hand, in the etching method, the pattern size is limited in forming the resist layer, and there is a limit in forming a continuous seamless pattern. In addition, there are many manufacturing processes and the equipment becomes large. Further, these conventional methods have a disadvantage that the metal in the punched portion and the portion removed by etching is wasted.
そこで本発明は、これら従来の方式における上記欠点を解決し、バリや金属のロスなく、シームレスで微細なパターンの貫通孔が形成された穴開き金属箔を提供することを目的とする。また、そのような穴開き金属箔の製造方法を提供する。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a perforated metal foil in which through holes having a seamless and fine pattern are formed without the loss of burrs and metals. Moreover, the manufacturing method of such a perforated metal foil is provided.
本発明のキャリア付き穴開き金属箔は、支持体の一方の面に形成されたパターン状銅蒸着層と、このパターン状銅蒸着層上に積層された剥離層と、から成るキャリア、このキャリアの剥離層上のみに形成された電解金属めっき処理による穴開き金属箔とから成る。 The perforated metal foil with a carrier of the present invention is a carrier comprising a patterned copper vapor-deposited layer formed on one surface of a support, and a release layer laminated on the patterned copper vapor-deposited layer. It consists of a perforated metal foil formed by electrolytic metal plating formed only on the release layer.
また、本発明のキャリア付き穴開き金属箔の製造方法は、支持体の一方の面に水溶性インク、または溶剤可溶性インクを印刷法によってパターン状にインクを付与する工程と、次いでこの支持体を銅蒸着処理後、インクを水洗することでパターン状銅蒸着層を形成する工程と、前記パターン状銅蒸着層上に剥離層を形成する工程と、次いで電解金属めっき処理をして穴開き金属箔を前期剥離層に重ねて形成する工程とを含むものである。ここで前記印刷法がグラビア印刷法であることが好ましい。 The method for producing a perforated metal foil with a carrier according to the present invention comprises a step of applying a water-soluble ink or a solvent-soluble ink to one side of a support in a pattern by a printing method, and then applying the support to the surface. After the copper vapor deposition treatment, the step of forming a patterned copper vapor deposition layer by washing the ink with water, the step of forming a release layer on the patterned copper vapor deposition layer, and then performing electrolytic metal plating treatment to form a perforated metal foil And a step of superposing the film on the release layer. Here, the printing method is preferably a gravure printing method.
本発明によれば、非常に薄く均一な厚さを有するパターン状の貫通孔を有する穴開き金属箔を得ることができる。この穴開き金属箔は、キャリア上に形成されているので取り扱いが容易である。また、バリの発生もなく、表面が平滑であり、継ぎ目のないシームレスなパターンの貫通孔が金属のロスを最小限に抑えて形成されている。更に穴開き金属箔を剥離した後のキャリアを再利用して、新たな穴開き金属箔を繰り返し製造することができる。 According to the present invention, it is possible to obtain a perforated metal foil having a patterned through-hole having a very thin and uniform thickness. The perforated metal foil is easy to handle because it is formed on the carrier. Further, there are no burrs, the surface is smooth, and seamless seamless pattern through holes are formed with minimal metal loss. Furthermore, a new perforated metal foil can be repeatedly produced by reusing the carrier after peeling the perforated metal foil.
本発明のキャリア付き穴開き金属箔とその製造方法について、図１に示す手順を参照しながら説明する。本発明における支持体は、合成樹脂からなる可撓性のフィルムが好適に用いられる（図１のＡ）。合成樹脂としては特に限定されないが、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリプロピレン、ポリイミドなどが挙げられ、なかでも強度があり汎用性が高いという理由でポリエチレンテレフタレートが好ましい。 The perforated metal foil with a carrier of the present invention and the manufacturing method thereof will be described with reference to the procedure shown in FIG. As the support in the present invention, a flexible film made of a synthetic resin is preferably used (A in FIG. 1). Although it does not specifically limit as a synthetic resin, For example, a polyethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate, polyethylene, a polypropylene, a polyimide etc. are mentioned, A polyethylene terephthalate is preferable because it is especially strong and versatile.
支持体上に銅蒸着層を形成するのに先立ち、水溶性インク、もしくは溶剤可溶性インクをパターン状に付与する（図１のＢ）。具体的な付与方法としては、水溶性インク、もしくは溶剤可溶性インクを用いて所望のパターンに印刷する方法が挙げられる。印刷の方法は特に限定されないが、シームレスなパターンを形成することが可能であり、微細なパターンの印刷に適している点で、グラビア印刷が好ましい。 Prior to forming the copper vapor deposition layer on the support, water-soluble ink or solvent-soluble ink is applied in a pattern (B in FIG. 1). A specific application method includes a method of printing in a desired pattern using water-soluble ink or solvent-soluble ink. The printing method is not particularly limited, but gravure printing is preferable because a seamless pattern can be formed and it is suitable for printing a fine pattern.
支持体上に印刷する水溶性インク、もしくは溶剤可溶性インクをパターン状に形成する方法は特に限定されず、リフトオフ方式として公知の処理方法を採用することができる。 The method for forming the water-soluble ink or solvent-soluble ink to be printed on the support in a pattern is not particularly limited, and a known processing method can be adopted as a lift-off method.
支持体上に、水溶性インク、もしくは溶剤可溶性インクをパターン状に付与した後、これを銅蒸着処理に供し、さらにインク及びインク上の銅蒸着層を除去することにより、パターン銅蒸着層を形成する（図１のＣ）。銅蒸着処理の方法は特に限定されず、公知の処理方法を採用することができる。ここで、表面状態を調整する目的で、銅蒸着層の上に重ねて、電解銅めっき層を形成してもよい。これによれば、本発明の穴開き金属箔の表面粗さを調整することが可能となる。 After applying water-soluble ink or solvent-soluble ink in a pattern on the support, it is subjected to copper vapor deposition treatment, and the copper vapor deposition layer on the ink and ink is further removed to form a patterned copper vapor deposition layer. (C in FIG. 1). The method for the copper vapor deposition treatment is not particularly limited, and a known treatment method can be employed. Here, for the purpose of adjusting the surface state, an electrolytic copper plating layer may be formed on the copper vapor deposition layer. According to this, it becomes possible to adjust the surface roughness of the perforated metal foil of the present invention.
剥離層を構成する化合物は、窒素含有有機化合物、硫黄含有有機化合物およびカルボン酸などが挙げられ、これらのなかから１種または２種以上を混合して用いられる。具体的には、窒素含有有機化合物としては、置換基を有するトリアゾール化合物である１，２，３−ベンゾトリアゾール、カルボキシベンゾトリアゾール、Ｎ’，Ｎ’−ビス（ベンゾトリアゾリルメチル）ユリア、１Ｈ−１，２，４−トリアゾールおよび３−アミノ−１Ｈ−１，２，４−トリアゾール等である。硫黄含有有機化合物には、メルカプトベンゾチアゾール、チオシアヌル酸および２−ベンズイミダゾールチオール等である。カルボン酸は、特にモノカルボン酸を用いることが好ましく、なかでもオレイン酸、リノール酸及びリノレイン酸等を用いることが好ましい。 Examples of the compound constituting the release layer include a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. Among these, one or a mixture of two or more is used. Specifically, examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which are triazole compounds having a substituent, and 1H. -1,2,4-triazole and 3-amino-1H-1,2,4-triazole. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, and 2-benzimidazolethiol. As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
上記化合物のなかでもベンゾトリアゾールが好適に用いられる。これら化合物は溶媒に溶解して用いられる。前記支持体をこの溶液に浸漬することで、銅蒸着層にのみ、前記化合物が選択的に吸着し、剥離層が形成される（図１のＤ）。溶媒としては水、エタノールなどが挙げられる。 Of these compounds, benzotriazole is preferably used. These compounds are used by dissolving in a solvent. By immersing the support in this solution, the compound is selectively adsorbed only on the copper deposition layer, and a release layer is formed (D in FIG. 1). Examples of the solvent include water and ethanol.
支持体上に形成されたパターン状銅蒸着層、更にこのパターン状銅蒸着層上に積層された剥離層を合わせて、本発明ではキャリアと呼ぶ。このキャリアに対して電解金属めっき処理を施して、目的のキャリア付き穴開き金属箔が得られる（図１のＥ）。電解金属めっき処理は公知の処理方法を採用することができる。穴開き金属箔の金属材料は特に限定されないが、例えば、銅やニッケルが挙げられる。また、二種類以上の金属による合金であってもよい。 The patterned copper vapor deposition layer formed on the support and the release layer laminated on the patterned copper vapor deposition layer are collectively referred to as a carrier in the present invention. By subjecting this carrier to electrolytic metal plating, the desired perforated metal foil with carrier is obtained (E in FIG. 1). For the electrolytic metal plating treatment, a known treatment method can be adopted. The metal material of the perforated metal foil is not particularly limited, and examples thereof include copper and nickel. Moreover, the alloy by two or more types of metals may be sufficient.
また、穴開き金属箔は単層の電解金属めっき層であってもよいし、電解金属めっき層に重ねて、無電解金属めっき層および／または電解金属めっき層を積層した多層構造としてもよい。これによれば、例えば銅層の両面をニッケル−亜鉛合金層でサンドイッチした穴開き金属箔を得ることもできる。 Further, the perforated metal foil may be a single-layer electrolytic metal plating layer or a multilayer structure in which an electroless metal plating layer and / or an electrolytic metal plating layer is laminated on the electrolytic metal plating layer. According to this, for example, a perforated metal foil in which both surfaces of a copper layer are sandwiched by nickel-zinc alloy layers can be obtained.
本発明のキャリア付き穴開き銅箔から穴開き金属箔の部分のみが剥離され、例えば二次電池の負極用集電体として利用される。残ったキャリア部分は再利用することが可能である。剥離層に損傷が無い場合はそのまま電解金属めっき処理を施して、新たに穴開き金属箔を製造するこができる。必要であれば、剥離層の形成工程を経て再利用してもよい。 Only the portion of the perforated metal foil is peeled off from the perforated copper foil with a carrier of the present invention, and is used, for example, as a current collector for a negative electrode of a secondary battery. The remaining carrier portion can be reused. When the release layer is not damaged, electrolytic metal plating can be performed as it is, and a new perforated metal foil can be produced. If necessary, it may be reused through a release layer forming step.
［実施例１］
ＰＥＴ（ポリエチレンテレフタレート）フィルムに、水溶性インクとして酸化珪素を添加したポリビニルアルコール樹脂を使用して、多孔パターンでグラビア印刷した。多孔パターンは、穴径１００μｍ、穴ピッチ２００μｍ、開口率２０％である。印刷後、銅蒸着処理を実施し、その後水洗処理することで、不要な蒸着銅層を除去し、膜厚１００ｎｍのパターン状銅蒸着層を形成した（図２）。更に、ベンゾトリアゾール５ｇ／ｌの水溶液を用いて、４０℃で３０秒間浸漬処理することで、剥離層としてベンゾトリアゾールのキレート被膜を形成してキャリアとした。このキャリアを、硫酸銅五水和物２５０ｇ／ｌ、硫酸５０ｇ／ｌを含む電解銅めっき液を用いて、液温２５℃、電流密度５Ａ／ｄｍ２で９分間電解銅めっき処理を実施した。その後、剥離層形成時と同様の処理を行うことで電解銅めっき層の表面に防錆皮膜を形成し、キャリア付き穴開き銅箔を得た。
[Example 1]
A PET (polyethylene terephthalate) film was subjected to gravure printing with a porous pattern using a polyvinyl alcohol resin to which silicon oxide was added as a water-soluble ink. The porous pattern has a hole diameter of 100 μm, a hole pitch of 200 μm, and an aperture ratio of 20%. After printing, a copper vapor deposition treatment was performed, and then a water washing treatment was performed to remove an unnecessary vapor deposition copper layer, thereby forming a patterned copper vapor deposition layer having a thickness of 100 nm (FIG. 2). Further, the carrier was formed by immersing at 40 ° C. for 30 seconds using an aqueous solution of benzotriazole 5 g / l to form a benzotriazole chelate film as a release layer. This carrier was subjected to an electrolytic copper plating treatment for 9 minutes at a liquid temperature of 25 ° C. and a current density of 5 A / dm 2 using an electrolytic copper plating solution containing 250 g / l of copper sulfate pentahydrate and 50 g / l of sulfuric acid. Then, the process similar to the time of peeling layer formation was performed, the rust prevention film was formed in the surface of an electrolytic copper plating layer, and the perforated copper foil with a carrier was obtained.
［実施例２］
ＰＥＴフィルムをＰＩ（ポリイミド）フィルムに変更した以外は、実施例１と同様にしてキャリア付き穴開き銅箔を得た。
[Example 2]
A perforated copper foil with a carrier was obtained in the same manner as in Example 1 except that the PET film was changed to a PI (polyimide) film.
［実施例3］
剥離層を形成する化合物を、ベンゾトリアゾールに替えてメルカプトベンゾチアゾールとした以外は、実施例１と同様にしてキャリア付き穴開き銅箔を得た。
[Example 3]
A perforated copper foil with a carrier was obtained in the same manner as in Example 1 except that the compound forming the release layer was changed to benzotriazole and replaced with mercaptobenzothiazole.
［実施例4］
電解銅めっき処理に替えて、硫酸ニッケル５水和物２５０ｇ／ｌ、ホウ酸３０ｇ／ｌを含む電解ニッケルめっき液を用いて、液温２５℃、電流密度５Ａ／ｄｍ２で電解ニッケルめっき処理をおこなった以外は実施例１と同様にしてキャリア付き穴開きニッケル箔を得た。
[Example 4]
In place of electrolytic copper plating treatment, electrolytic nickel plating treatment is performed at a liquid temperature of 25 ° C. and a current density of 5 A / dm 2 using an electrolytic nickel plating solution containing nickel sulfate pentahydrate 250 g / l and boric acid 30 g / l. A holed nickel foil with a carrier was obtained in the same manner as in Example 1 except for the above.
実施例１で得られたキャリア付き穴開き銅箔から穴開き銅箔を剥離して取り除き、キャリア部分のみとした。このキャリアを酸洗い処理した後、実施例１と同様にして再度剥離層を形成し、電解銅めっき処理をおこなった。得られたキャリア付き穴開き銅箔は亀裂や形状の乱れもなく、十分実用に耐えるものであり、キャリアの繰り返し利用が可能であることを示すものであった。 The perforated copper foil was peeled off from the perforated copper foil with a carrier obtained in Example 1 to remove only the carrier portion. After this carrier was pickled, a release layer was formed again in the same manner as in Example 1, and an electrolytic copper plating process was performed. The obtained perforated copper foil with a carrier was not practically cracked or disturbed in shape and sufficiently withstands practical use, indicating that the carrier can be used repeatedly.
１ 支持体
２ 水溶性インク、もしくは溶剤可溶性インク
３ 銅蒸着層
４ 剥離層
５ 穴開き金属箔
６ キャリア
DESCRIPTION OF SYMBOLS 1 Support body 2 Water-soluble ink or solvent soluble ink 3 Copper vapor deposition layer 4 Release layer 5 Perforated metal foil 6 Carrier
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10820457B1 (en) | 2019-05-30 | 2020-10-27 | Toyo Ink Sc Holdings Co., Ltd. | Electromagnetic wave shielding sheet and printed wiring board |
| JP2021068636A (en) * | 2019-10-25 | 2021-04-30 | 株式会社豊田自動織機 | Electrode foil manufacturing method |
| JP2021068884A (en) * | 2019-10-23 | 2021-04-30 | 東洋インキＳｃホールディングス株式会社 | Production method of electromagnetic wave shield film |
| US11271199B2 (en) | 2017-08-17 | 2022-03-08 | Lg Energy Solution, Ltd. | Method for patterning lithium metal surface and electrode for lithium secondary battery using the same |
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2013
- 2013-09-25 JP JP2013198245A patent/JP2015063730A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11271199B2 (en) | 2017-08-17 | 2022-03-08 | Lg Energy Solution, Ltd. | Method for patterning lithium metal surface and electrode for lithium secondary battery using the same |
| US10820457B1 (en) | 2019-05-30 | 2020-10-27 | Toyo Ink Sc Holdings Co., Ltd. | Electromagnetic wave shielding sheet and printed wiring board |
| US11533833B2 (en) | 2019-05-30 | 2022-12-20 | Toyo Ink Sc Holdings Co., Ltd. | Electromagnetic wave shielding sheet and printed wiring board |
| JP2021068884A (en) * | 2019-10-23 | 2021-04-30 | 東洋インキＳｃホールディングス株式会社 | Production method of electromagnetic wave shield film |
| JP2021068636A (en) * | 2019-10-25 | 2021-04-30 | 株式会社豊田自動織機 | Electrode foil manufacturing method |
| JP7283349B2 (en) | 2019-10-25 | 2023-05-30 | 株式会社豊田自動織機 | Manufacturing method of electrode foil |
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