JPS63274795A - Composite foil and production thereof - Google Patents
Composite foil and production thereofInfo
- Publication number
- JPS63274795A JPS63274795A JP10753687A JP10753687A JPS63274795A JP S63274795 A JPS63274795 A JP S63274795A JP 10753687 A JP10753687 A JP 10753687A JP 10753687 A JP10753687 A JP 10753687A JP S63274795 A JPS63274795 A JP S63274795A
- Authority
- JP
- Japan
- Prior art keywords
- foil
- layer
- copper
- alloy
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011888 foil Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011889 copper foil Substances 0.000 claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 18
- 229910017932 Cu—Sb Inorganic materials 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009713 electroplating Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 3
- 239000010951 brass Substances 0.000 claims abstract description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000011135 tin Substances 0.000 claims abstract 3
- 229910000906 Bronze Inorganic materials 0.000 claims abstract 2
- 239000010974 bronze Substances 0.000 claims abstract 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000007788 roughening Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 73
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- KGHMFMDJVUVBRY-UHFFFAOYSA-N antimony copper Chemical compound [Cu].[Sb] KGHMFMDJVUVBRY-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 101000760703 Cupiennius salei Cupiennin-3b Proteins 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001462 antimony Chemical class 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- -1 copper salt Chemical class 0.000 description 2
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ICBPURKUPVLVCM-UHFFFAOYSA-N 1,5-dimethyl-2-phenylpyrazol-3-one;2-hydroxy-2-phenylacetic acid Chemical class OC(=O)C(O)C1=CC=CC=C1.CN1C(C)=CC(=O)N1C1=CC=CC=C1 ICBPURKUPVLVCM-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910017784 Sb In Inorganic materials 0.000 description 1
- 229910017847 Sb—Cu Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XRZJYOVMWCUNER-UHFFFAOYSA-L copper;sulfate;trihydrate Chemical compound O.O.O.[Cu+2].[O-]S([O-])(=O)=O XRZJYOVMWCUNER-UHFFFAOYSA-L 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001880 stiboryl group Chemical group *[Sb](*)(*)=O 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は印刷回路用極薄銅箔を提供する複合箔、さらに
詳しくは支持体金属箔層と極薄銅箔眉間に適度な接着力
をもつ中間薄層を有する複合箔およびその製造方法に関
するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a composite foil that provides an ultra-thin copper foil for printed circuits, and more specifically, a composite foil that provides an ultra-thin copper foil for printed circuits, and more specifically, a composite foil that provides an appropriate adhesive force between the support metal foil layer and the ultra-thin copper foil eyebrows. The present invention relates to a composite foil having an intermediate thin layer and a method for manufacturing the same.
印刷回路板は電子機器の発展とともに、急速に高密度化
、高精度化している。回路中、回路間隔は年々、極細化
してきており、従来より使用されている、３５μｍ１１
８μ鋼クラスの銅箔では、印刷回路製造工程に於けるエ
ツチング段階での導体端部のへこみ量、いわゆるアンダ
ーカットが大きく、回路の一層のファインパターン化に
は難点がある。Printed circuit boards are rapidly becoming denser and more precise with the development of electronic devices. The circuit spacing in the circuit is becoming finer year by year, and the conventionally used 35μm11
In the case of 8μ steel class copper foil, there is a large amount of indentation, or so-called undercut, at the end of the conductor during the etching stage in the printed circuit manufacturing process, making it difficult to create finer patterns for the circuit.
それを解決するために銅箔の厚みをさらに薄クシた極薄
銅箔で対応しようという試みがなされているが、１２μ
ｍ以下の極薄銅箔はその取り扱い上、自重でシワや傷を
生じるため、支持体が必要である。In order to solve this problem, attempts have been made to use ultra-thin copper foil, which is made even thinner.
An ultra-thin copper foil with a thickness of less than 100 m is required to have a support because it wrinkles and scratches due to its own weight when handled.
そのため、従来よりアルミニウム支持体（キャリアー）
などに支持された極薄銅箔が公知である。Therefore, conventionally aluminum supports (carriers)
Ultra-thin copper foils supported by, for example, are known.
例えば特公昭５４−１４２９８号にはアルミニウム箔の
表面を機械的あるいは化学的に梨地化し、脱脂、酸洗、
亜鉛置換処理などで活性化した後、銅層を設ける方法が
、また特公昭５６−３５０３８号には銅とアルミニウム
を重ねて圧延した複合圧延箔を使用することが、また、
特開昭５８−１０８７８５号には銅支持層と１〜１２μ
重厚の銅の薄層間にニッケル及びその合金などの中間層
を設けることなどが提案されているが、これらはキャリ
アーとしてアルミニウムや銅をエツチング除去せねばな
らず、その工程が煩雑となり、エツチング廃液の処理に
費用が掛かる等の問題もあり、極薄ｗ４箔を使用する上
で充分満足される特性を有するものではなかった。For example, in Japanese Patent Publication No. 54-14298, the surface of aluminum foil is mechanically or chemically polished, degreased, pickled,
There is a method of providing a copper layer after activation by zinc substitution treatment, and Japanese Patent Publication No. 56-35038 describes the use of a composite rolled foil made by laminating and rolling copper and aluminum.
JP-A No. 58-108785 has a copper support layer and a 1 to 12μ
It has been proposed to provide an intermediate layer of nickel or nickel alloys between thin layers of thick copper, but these require the use of aluminum or copper as a carrier to be removed by etching, making the process complicated and requiring a waste of etching liquid. There are also problems such as high processing costs, and the properties are not fully satisfactory when using ultra-thin W4 foil.
また特公昭５７−１６７５８号にはアルミニウム箔を特
殊なアルカリ水溶液中で活性化した後、ピロリン酸銅め
っきにより極薄銅箔を製造する方法や、その他、特公昭
６０−３０７５１号など剥離方式（ピーラブルタイプ）
の極薄銅箔の製造方法が多々提案されているが、これら
の複合箔を基材と積層成型したとき、その支持体と極薄
銅箔との接着が強固でありすぎたり、不十分で支持体と
極薄銅箔の間でふくれや剥れを生じたりして充分満足で
きる特性を有するものではなかった。In addition, Japanese Patent Publication No. 57-16758 describes a method of manufacturing ultra-thin copper foil by pyrophosphate copper plating after activating aluminum foil in a special alkaline aqueous solution, and other peeling methods such as Japanese Patent Publication No. 60-30751 Peelable type)
Many methods for producing ultra-thin copper foil have been proposed, but when these composite foils are laminated with a base material, the adhesion between the support and the ultra-thin copper foil is either too strong or insufficient. Blistering and peeling occurred between the support and the ultra-thin copper foil, and the properties were not completely satisfactory.
さらに、特公昭５３−１８３２９号には銅を支持体とし
て、離型層がクロム、鉛、ニッケル、銀、あるいはクロ
ム酸塩、硫化物である極薄銅箔が記載されているが、ニ
ッケルは離型層となりえず、引き剥し困難であるし、他
の離型層についてもその処理法が厳密を要するものであ
り、また接着力が強く引き剥しが困難となったり、また
、基材と積層させる際などにおいて、支持体から極薄銅
箔が自然剥離するほどに接着力が弱い場合などがあり、
必ずしも満足のいくものではなかった。Furthermore, Japanese Patent Publication No. 53-18329 describes an ultra-thin copper foil using copper as a support and having a release layer of chromium, lead, nickel, silver, chromate, or sulfide, but nickel is It cannot be used as a mold release layer and is difficult to peel off, and other mold release layers also require strict treatment methods, and the adhesive strength is strong and it is difficult to peel off, and it is difficult to peel off from the base material. When laminating, there are cases where the adhesive strength is so weak that the ultra-thin copper foil naturally peels off from the support.
It wasn't always satisfying.
そこで従来技術の欠点を解決するため、すなわち、極薄
銅箔を提供することに関し、金属支持体をエツチング除
去する工程を必要としない剥離方式の複合箔を提供し、
かつその金属支持体と極薄銅層間に均一で適度な接着性
（引き剥し強さ）をもつ中間層を有する新規な複合箔お
よびその製造を種々検討した結果、本発明を完成したも
のである。Therefore, in order to solve the drawbacks of the prior art, namely, to provide an ultra-thin copper foil, we provide a peel-off composite foil that does not require a step of etching away the metal support.
The present invention was completed as a result of various studies on a novel composite foil having an intermediate layer having uniform and appropriate adhesion (peel strength) between the metal support and the ultra-thin copper layer, and the production thereof. .
即ち、本発明は、支持体金属箔層と１２μｍ以下の厚さ
の極薄銅箔層との間にＳｂ又はＣｕｆｆＳｂ合金の中間
層を有することを特徴とする複合箔、であり、必要に応
じて、極薄銅箔層が粗面化処理層及び／又は不働態化処
理層をもつもので、またその製造方法は支持体金属箔上
にＳｂ又はＣｕ−Ｓｂ合金層を電気めっきし、その上に
１２μｍ以下の銅層を電解析出させ、さらにその表面に
粗面化処理及び／又は不働態化処理を行うことを特徴と
する複合箔の製造方法である。That is, the present invention is a composite foil characterized in that it has an intermediate layer of Sb or CuffSb alloy between a support metal foil layer and an ultra-thin copper foil layer with a thickness of 12 μm or less. The ultra-thin copper foil layer has a roughening treatment layer and/or a passivation treatment layer, and its manufacturing method involves electroplating an Sb or Cu-Sb alloy layer on a support metal foil. This method of manufacturing a composite foil is characterized in that a copper layer of 12 μm or less is electrolytically deposited thereon, and the surface thereof is further roughened and/or passivated.
本発明は、Ｓｂ又はＣｕ−Ｓｂ合金の中間層を設けたこ
とに特徴があり、このＳｂ又はＣｕ−Ｓｂ合金層の厚さ
は０．００５〜１ μＩ、好ましくは０．０３〜０．３
μｍである。０．００５μｍ以下では支持体金属箔−極
薄銅箔間の接着力が強固になり、引き剥し困難となる。The present invention is characterized by providing an intermediate layer of Sb or Cu-Sb alloy, and the thickness of this Sb or Cu-Sb alloy layer is 0.005 to 1 μI, preferably 0.03 to 0.3
It is μm. If the thickness is less than 0.005 μm, the adhesive force between the support metal foil and the ultrathin copper foil becomes strong, making it difficult to peel off.
ここで適度な接着力とは、基材との積層成型後、支持体
の引き剥し強さが０．１〜０．４ ｋｇ／ｃｍである。Appropriate adhesive strength here means that the peel strength of the support after lamination molding with the base material is 0.1 to 0.4 kg/cm.
これが０．６〜０．７ｋｇ／ｃｍ以上では引き剥しか困
難となってくる。一方、Ｓｂ又はＣｕ−Ｓｂ合金の中間
層の厚さが１μｍ以上とした場合には、経済的でないた
め好ましくない。If the weight exceeds 0.6 to 0.7 kg/cm, it becomes difficult to remove the film. On the other hand, if the thickness of the intermediate layer of Sb or Cu-Sb alloy is 1 μm or more, it is not economical and therefore not preferable.
また、Ｃｕ−Ｓｂ合金層を形成させる場合、その合金中
Ｓｂは好ましくは３％以上、さらに好ましくは８％以上
であり、これ以下では引き剥しか困難となる。Further, when forming a Cu-Sb alloy layer, the Sb content in the alloy is preferably 3% or more, more preferably 8% or more, and if it is less than this, it will be difficult to peel it off.
本発明のＳｂ又はＣｕ−Ｓｂ合金層を支持体金属箔表面
上に形成させる方法は、公知の電気めっき法、化学めっ
き法、真空蒸着法、スパッタリング法など各種の方法に
よって可能であるが、工業土臭うインに最適と思われる
ものは、水溶液電気めっき法である。その電解浴として
は例えば、酒石酸または、クエン酸浴を使用する。Ｓｂ
単独層形成の場合は、水酸化ナトリウム、水酸化カリウ
ムを使用したアルカリ浴も良い。The Sb or Cu-Sb alloy layer of the present invention can be formed on the surface of the metal foil of the support by various known methods such as electroplating, chemical plating, vacuum evaporation, and sputtering. Aqueous electroplating seems to be the most suitable method for insulating environments with earthy smells. As the electrolytic bath, for example, a tartaric acid or citric acid bath is used. Sb
In the case of forming a single layer, an alkaline bath using sodium hydroxide or potassium hydroxide is also suitable.
酒石酸浴を例にとると、酒石酸濃度は３０〜２００ｇ／
βの範囲が適当である。アンチモンイオン源としては酒
石酸アンチモニルカリウム、酒石酸アンチモニルナトリ
ウム、二酸化アンチモンなどを使用し、その量はＳｂ単
独層の場合塩として、２０〜１００ｇ／ｌが適当であり
、Ｃｕ−３ｂ合金層の場合は、アンチモン塩は、銅塩量
にもよるが、１〜１００ｇ＃！が適当である。銅イオン
源は硫酸銅、酒石酸銅などを使用し、塩としてＯからア
ンチモン塩と同量かそれ以上の量も加えることができる
。また、酒石酸銅の場合、あるいはその沈澱生成の場合
、適量の硫酸を加えると良い。また浴電圧を下げるため
、硫酸ナトリウムあるいは硫酸カリウムを添加しても良
い。浴温は室温から５０℃が良い、陽極は白金など不溶
性陽極を使用するが、Ｃｕ−Ｓｂ合金層の場合はｗ４陽
極でも良い。電流密度は０．５〜５ Ａ／ｄｍ”が適当
である。Taking a tartaric acid bath as an example, the tartaric acid concentration is 30-200g/
The range of β is appropriate. Potassium antimonyl tartrate, sodium antimonyl tartrate, antimony dioxide, etc. are used as the antimony ion source, and the appropriate amount is 20 to 100 g/l as a salt in the case of an Sb single layer, and in the case of a Cu-3b alloy layer. The amount of antimony salt is 1 to 100g, depending on the amount of copper salt! is appropriate. Copper sulfate, copper tartrate, or the like is used as the copper ion source, and O to antimony salt can be added in an amount equal to or larger than that of the salt. Furthermore, in the case of copper tartrate or its precipitation, it is advisable to add an appropriate amount of sulfuric acid. Furthermore, sodium sulfate or potassium sulfate may be added to lower the bath voltage. The bath temperature is preferably room temperature to 50°C. An insoluble anode such as platinum is used as the anode, but in the case of a Cu-Sb alloy layer, a W4 anode may be used. A suitable current density is 0.5 to 5 A/dm''.
支持体金属箔は、銅、ニッケル、アルミニウム、スズ、
真鍮より選ばれた箔を使用するのが好ましい。支持体金
属箔の厚さは１０〜１００μｍが適当である。上記のう
ちアルミニウムについては、直接アンチモン、あるいは
銅−アンチモンめっきができないため、アルミニウム表
面を脱脂水洗後、必要に応じて、硝酸などで酸洗し、水
洗し、ジンケート浴で亜鉛置換処理を行い、水洗後この
支持体金属箔を陰極としてアンチモンまたは銅−アンチ
モンめっきを施す。Support metal foils include copper, nickel, aluminum, tin,
Preferably, a foil chosen over brass is used. The appropriate thickness of the support metal foil is 10 to 100 μm. Of the above, aluminum cannot be directly plated with antimony or copper-antimony, so after degreasing and washing the aluminum surface with water, if necessary, pickling with nitric acid etc., washing with water, and performing zinc replacement treatment in a zincate bath. After washing with water, antimony or copper-antimony plating is applied using the support metal foil as a cathode.
これらのＳｂ又はＣｕ−Ｓｂ合金層を設けた支持体金属
箔上に、やはり電気めっきにより厚さ１２μｍ以下Φ銅
層をつける。本発明のＳｂ又はＣｕ−Ｓｂ合金層は、そ
の表面に析出させる極薄銅箔層に悪影響を全く与えない
ので析出異常のない均一できわめて薄い銅箔層を形成す
ることができる。その銅めっき浴としてはビロリン酸浴
、硫酸浴などいかなる浴でも適用可能であるが、浴管理
の容易さやコスト的な面から、硫酸浴が好ましい。On the support metal foil provided with these Sb or Cu-Sb alloy layers, a Φ copper layer with a thickness of 12 μm or less is applied by electroplating. The Sb or Cu-Sb alloy layer of the present invention has no adverse effect on the ultra-thin copper foil layer deposited on its surface, so it is possible to form a uniform and extremely thin copper foil layer with no precipitation abnormalities. Any bath such as a birophosphoric acid bath or a sulfuric acid bath can be used as the copper plating bath, but a sulfuric acid bath is preferable from the viewpoint of ease of bath management and cost.
この銅層をめっきした後、基材とのより高い接着性を得
るためにはその表面に粗面化処理を施す。After plating this copper layer, its surface is roughened in order to obtain higher adhesion to the substrate.
これは例えば特公昭４５−３４２４５号に記載された方
法や、その他、硫酸銅−硫酸浴中で限界電流密度以上で
陰極電解するなどの方法がある。This can be done, for example, by the method described in Japanese Patent Publication No. 45-34245, or by cathodic electrolysis in a copper sulfate-sulfuric acid bath at a current density higher than the critical current density.
また必要に応じ、この粗面化処理された複合箔表面に不
働態化処理を行う０例えば、異種金属でコーティングす
る方法や重クロム酸イオンを含む水溶液に浸漬するクロ
メート処理法などがあり、また、ＢＴＡ （ベンゾトリ
アゾール）やその誘導体の水溶液中に浸漬するなどの有
機防錆皮膜を施してもよい。以上で本発明の複合箔が得
られる。If necessary, the surface of the roughened composite foil may be subjected to passivation treatment.For example, there is a method of coating with a different metal, a chromate treatment method of immersing it in an aqueous solution containing dichromate ions, etc. , an organic rust-preventive coating may be applied by immersion in an aqueous solution of BTA (benzotriazole) or its derivatives. The composite foil of the present invention is thus obtained.
次に、本発明の複合箔を樹脂含浸基材と積層し成型する
場合、その中間層であるＳｂ又はＣｕ−Ｓｂ合金層はそ
の熱と圧力で支持体金属箔及び極薄銅箔層へある程度拡
散すると考えられ、支持体金属箔を引き剥すと、極薄銅
箔表面にこの中間層（接着Ｎ）が多少残る。しかし、前
記中間層が残ったとしても研磨により、除去する必要は
なく、一般によく使用されている塩化第二鉄や塩化第二
銅などのエツチング液に対し、銅と同程度の速度で溶解
するため、エツチングによる回路の形成に障害とならず
、また、回路上にスティンを残さない。Next, when the composite foil of the present invention is laminated with a resin-impregnated base material and molded, the intermediate layer, Sb or Cu-Sb alloy layer, is partially bonded to the support metal foil and the ultra-thin copper foil layer by the heat and pressure. It is thought that it diffuses, and when the support metal foil is peeled off, some of this intermediate layer (adhesion N) remains on the surface of the ultra-thin copper foil. However, even if the intermediate layer remains, it does not need to be removed by polishing, and it dissolves at the same rate as copper in commonly used etching solutions such as ferric chloride and cupric chloride. Therefore, it does not interfere with the formation of a circuit by etching, and does not leave stains on the circuit.
また、アルミニウム箔を支持体金属箔としたとき、従来
技術では、積層成型時にアルミニウムと極ｆ３１ ｍ
Ｆｆｉ間にふくれや剥れを生じやすいという欠点があっ
たが、本発明の、特にＳｂ層を中間層として適用すると
、そのふくれや剥れの現象が全く生じず、きわめて良好
な成型体を得ることができる。In addition, when aluminum foil is used as a support metal foil, in the conventional technology, aluminum and pole f31 m are formed during lamination molding.
However, when the present invention, especially the Sb layer, is applied as an intermediate layer, the phenomenon of blistering and peeling does not occur at all, and an extremely good molded product can be obtained. be able to.
しかしながらＣｕ−Ｓｂ合金層を中間層として用いた場
合、その合金層の銅量を約２０％以上に増加させるとそ
のふくれ現象が生じやすくなる。However, when a Cu--Sb alloy layer is used as an intermediate layer, if the amount of copper in the alloy layer is increased to about 20% or more, the blistering phenomenon tends to occur.
以下、本発明の具体的な実施例を示す。Hereinafter, specific examples of the present invention will be shown.
実施例（１）
３５μｍ厚さの電解＃ｒ４箔を用意し、その光沢面に、
（Ａ−１）酒石酸アンチモニルカリウム ３０ｇ／ １
酒石酸 ５０ｇ／ １硫酸ナトリ
ウム ５０ｇ／ １浴温
３５℃
の浴で、電流密度２Ａ／ｄｍ” 、１０秒間陰極電解し
、０．１２μｍ厚さのアンチモン層を析出させた。これ
を水洗し、その表面に
（Ｂ） 硫酸銅（三木塩） ２００ｇ／
１硫酸 １００ｇ／ １塩酸
４０ｐｐｍ浴温
５０℃
の浴で、電流密度３Ａ／ｄＩＩ＋２．８分間陰極電解し
、約５μｍ厚さの極薄銅箔層を析出させた。これを水洗
し、
（Ｃ） 硫酸銅（三水塩） １５０ｇ／
１硫酸 ５０ｇ／ １硝酸ナ
トリウム ３０ｇ／ １浴温
４０℃
の浴で、電流密度１５Ａ／ｄｍ”、１１分間陰極電解し
、粗面化処理を施した。これを水洗し、さらにその表面
を重クロム酸ナトリウム１０ｇ／ １２水溶液中に室温
で１０秒間浸漬し、水洗後乾燥させ、複合箔を得た。Example (1) A 35 μm thick electrolytic #r4 foil was prepared, and its glossy surface was coated with
(A-1) Potassium antimonyl tartrate 30g/1
Tartaric acid 50g/1 Sodium sulfate 50g/1 Bath temperature
In a bath at 35°C, cathodic electrolysis was carried out for 10 seconds at a current density of 2 A/dm'' to deposit an antimony layer with a thickness of 0.12 μm. This was washed with water, and 200 g of (B) copper sulfate (Miki salt) was deposited on the surface. /
1 sulfuric acid 100g/1 hydrochloric acid
40ppm bath temperature
Cathodic electrolysis was carried out in a bath at 50° C. at a current density of 3 A/dII for 2.8 minutes to deposit an ultra-thin copper foil layer with a thickness of about 5 μm. Wash this with water, (C) Copper sulfate (trihydrate) 150g/
1 Sulfuric acid 50g/ 1 Sodium nitrate 30g/ 1 Bath temperature
The surface was roughened by cathodic electrolysis for 11 minutes at a current density of 15 A/dm in a bath at 40°C. This was washed with water, and the surface was soaked in a 10 g/12 aqueous solution of sodium dichromate for 10 seconds at room temperature. The composite foil was obtained by immersion, washing with water, and drying.
この複合箔をＰＲ−４基材に積層し、１６８℃、４０ｋ
ｇ／ｃｄの条件で６０分間加熱圧着させ成型した。この
成型体から支持体であったＳｒ４ ｆ＆を引き剥す時の
引き剥し強度（ＪＩＳ−Ｃ−６４８１に準拠、以下の実
施例についても同じ）を測定したところ、０．２０ｋｇ
／ｃｍであった。このため、成型体から支持体の銅箔は
容易に引き剥すことができ、かつ適度な接着力であった
。支持体銅箔を引き剥した成型体の極薄銅箔をフォトレ
ジスト法（塩化第二銅エツチング）により回路中０．１
ｍｍのファインパターンを作成したが、この回路はアン
ダーカットが非常に小さく、また断線やブリッジのない
良好な高密度回路であった。This composite foil was laminated on a PR-4 base material and heated to 40k at 168°C.
Molding was carried out by heat-pressing for 60 minutes under the conditions of g/cd. The peel strength (based on JIS-C-6481, the same applies to the following examples) when peeling off the support Sr4 f& from this molded body was 0.20 kg.
/cm. Therefore, the copper foil of the support could be easily peeled off from the molded body, and the adhesive strength was moderate. The ultra-thin copper foil of the molded body after peeling off the supporting copper foil is coated with a photoresist method (cupric chloride etching) to form a circuit with a thickness of 0.1
A fine pattern of mm in diameter was created, and this circuit had very small undercuts and was a good high-density circuit with no disconnections or bridges.
実施例（２）
３５μｍ厚さの電解銅箔を用意し、その光沢面に、（＾
−２）酒石酸アンチモニルカリウム ３０ｇ／ １硫酸
ｔＲ（三水塩） １０ｇ／ １２酒石酸
５０ｇ／β硫酸ナトリウム
５０ｇ／ １浴温
３５℃
の浴で、電流密度２Ａ／ｄｍ” 、１０秒間陰極電解し
、銅−アンチモン合金層を析出させた。この層は別に電
解ニッケル箔上に同じ条件で析出させ、その分析をした
ところ、Ｓｂ７１χ、 Ｃｕ２９χの合金層で、厚さは
０．１０μｍであった。このＳｂ−Ｃｕ合金層を持つ支
持体銅箔上に種菌銅箔層、粗面化処理層、クロメート処
理層を実施例（１）と同じ条件で析出又は処理し複合箔
を得た。これを実施例（１）と同じ条件でＰＲ−４基材
に積層成型し、その成型体から支持体で、あった銅箔を
引き剥すときの引き剥し強度を測定したところ、０．３
０ｋｇ／ｃｍであった。Example (2) Prepare an electrolytic copper foil with a thickness of 35 μm, and put (^
-2) Potassium antimonyl tartrate 30g/1sulfuric acid tR (trihydrate) 10g/12tartrate 50g/sodium β sulfate
50g/1 bath temperature
A copper-antimony alloy layer was deposited by cathodic electrolysis in a 35°C bath at a current density of 2 A/dm for 10 seconds. This layer was separately deposited on an electrolytic nickel foil under the same conditions and analyzed. It was an alloy layer of Sb71χ and Cu29χ, and the thickness was 0.10 μm.A seed copper foil layer, a roughening treatment layer, and a chromate treatment layer were placed on the support copper foil having this Sb-Cu alloy layer in the example ( A composite foil was obtained by depositing or treating under the same conditions as in Example (1).This was laminated and molded on a PR-4 base material under the same conditions as in Example (1), and the copper foil was removed from the molded body using a support. When peeling strength was measured, it was 0.3
It was 0 kg/cm.
実施例（３）
３５μｍ厚さの電解銅箔を用意し、その光沢面に、（Ａ
−３）酒石酸アンチモニルカリウム ３０ｇ／ ｊ！硫
酸銅（三木塩） ２０ｇ／ １酒石酸
５０ｇ／ Ｉｌ硫酸ナトリウム
５０ｇ／ Ｉｔ浴温
３５℃
の浴で、電流密度２Ａ／ｄｍ” 、１０秒間陰極電解し
、銅−アンチモン合金層を析出させた。この層は別に電
解ニッケル箔上に同じ条件で析出させ、その分析をした
ところ、Ｃｕ５８χ、 Ｓｂ４２χの合金層で、厚さは
０．０９μｍであった。このＣｕ−３ｂ合金層を持つ支
持体銅箔上に極薄銅箔層、粗面化処理層、クロメート処
理層を実施例（１）と同じ条件で析出又は処理して複合
箔を得た。これを実施例（１）と同じ条件でＰＲ−４基
材に積層成型し、その成型体から支持体であった銅箔を
引き剥すときの引き剥し強度を測定したところ、０．３
０ｋｇ／ｃｍであった。Example (3) Electrolytic copper foil with a thickness of 35 μm was prepared, and (A
-3) Potassium antimonyl tartrate 30g/j! Copper sulfate (Miki salt) 20g/1 tartaric acid
50g/ Sodium Il sulfate
50g/It bath temperature
A copper-antimony alloy layer was deposited by cathodic electrolysis in a 35°C bath at a current density of 2 A/dm for 10 seconds. This layer was separately deposited on an electrolytic nickel foil under the same conditions and analyzed. It was an alloy layer of Cu58χ and Sb42χ, and the thickness was 0.09 μm.A very thin copper foil layer, a roughening treatment layer, and a chromate treatment layer were formed on the supporting copper foil having this Cu-3b alloy layer. A composite foil was obtained by precipitation or treatment under the same conditions as in Example (1).This was laminated and molded on a PR-4 base material under the same conditions as in Example (1), and the molded body was separated from the copper foil that was the support. When we measured the peel strength when peeling off, it was 0.3
It was 0 kg/cm.
実施例（４）
２５μｍの厚さの電解ニッケル箔を用意し、その光沢面
に、実施例（２）と同じ条件でＣｕ−３ｂ合金層を形成
し、そして実施例（１）と同じ条件で極薄銅箔層、粗面
化処理層およびクロメート処理層を析出又は処理して複
合箔を得た。このようにして得られた複合箔を実施例（
１）と同じ条件でＰＲ−４基材に積層成型し、その成型
体から支持体であったニッケル箔を引き剥し、そのとき
の引き剥し強度を測定したところ、０．２５ｋｇ／ｃｍ
であった。Example (4) An electrolytic nickel foil with a thickness of 25 μm was prepared, and a Cu-3b alloy layer was formed on its shiny surface under the same conditions as Example (2), and then under the same conditions as Example (1). A composite foil was obtained by depositing or treating an ultrathin copper foil layer, a roughened layer, and a chromate layer. The composite foil thus obtained was used in Example (
Laminate molding was performed on a PR-4 base material under the same conditions as in 1), the nickel foil that was the support was peeled off from the molded body, and the peel strength at that time was measured, and it was 0.25 kg/cm
Met.
実施例（５）
３５μｍ厚さの圧延銅箔を用意し、８０ｇ／ １水酸化
ナトリウム水溶液中で５０℃、電流密度１０Ａ／ｄｍ２
で３分間陰極電解し、脱脂した。これを水洗し、次いで
３χ硫酸水溶液中に室温で１分間浸漬し、水洗し、
（Ａ−４）酒石酸アンチモニルカリウム ３０ｇ／ Ｉ
ｔ酒石酸 １００ｇ／ Ｉ！浴温
３５℃
の浴で、電流密度２Ａ／ｄｎ＋２．５秒間陰極電解し、
厚さ０．０６μ題のアンチモン層を析出させた。その後
、この表面上に極薄銅箔層、粗面化処理層、クロメート
処理層を実施例（１）と同じ条件で析出又は処理して複
合箔を得た。この複合箔を実施例（１）と同じ条件でＰ
Ｒ−４基材に積層成型し、その成型体から支持体である
圧延銅箔を引き剥し、そのときの引き剥し強度を測定し
たところ、Ｏ；２０ｋｇ／ｃｍであった。Example (5) A rolled copper foil with a thickness of 35 μm was prepared and heated at 50° C. with a current density of 10 A/dm2 in an 80 g/1 sodium hydroxide aqueous solution.
It was degreased by cathodic electrolysis for 3 minutes. This was washed with water, then immersed in a 3χ sulfuric acid aqueous solution at room temperature for 1 minute, and washed with water. (A-4) Potassium antimonyl tartrate 30 g/I
ttartaric acid 100g/I! bath temperature
Cathodic electrolysis was carried out for 2.5 seconds at a current density of 2 A/dn in a bath at 35°C.
An antimony layer with a thickness of 0.06 μm was deposited. Thereafter, an ultrathin copper foil layer, a roughened layer, and a chromate layer were deposited or treated on the surface under the same conditions as in Example (1) to obtain a composite foil. This composite foil was heated under the same conditions as in Example (1).
It was laminated and molded on an R-4 base material, the rolled copper foil serving as a support was peeled off from the molded body, and the peel strength at that time was measured, and it was found to be O: 20 kg/cm.
実施例（６）
３５μｍ厚さのアルミニウム箔を用意し、これを、（Ａ
−４） リン酸三ナトリウム ２５ｇ／ １炭
酸ナトリウム ２５ｇ／ １浴温
５０℃
の脱脂浴中に１分間浸漬し、水洗し、次に１８χ硝酸水
溶液に室温で１分間浸漬し、水洗し、（Ｅ） 水酸化
ナトリウム １２０ｇ／ １０ツセル塩
５０ｇ／ １亜鉛イオン
１８ｇ／ １２硝酸ナトリウム Ｉ
ｇ＃！塩化第二鉄 ２ｇ／ （１の浴
中に室温で１分間浸漬し、水洗した後、この支持体アル
ミニウム箔を陰極として実施例（１）で用いた（Ａ−１
）浴で、電流密度２Ａ／ｄｎ＋” 、 ５秒間電解し
、アンチモン層を析出させた。この表面上に極薄銅箔層
、粗面化処理層、クロメート処理層を実施例（１）と同
じ条件で析出又は処理し、複合箔を得た。これを実施例
（１）と同じ条件でＰＲ−４基材に積層し、加熱圧着成
型したが、ふ（れなどかまった（無（、良好な成型体を
得た。この成型体から支持体であったアルミニム箔を引
き剥し、そのときの引き剥し強度は０．４０ｋｇ／ｃ＋
＋＋であった。Example (6) An aluminum foil with a thickness of 35 μm was prepared, and this was
-4) Trisodium phosphate 25g/1 sodium carbonate 25g/1bath temperature
(E) Sodium hydroxide 120g/10 Tussel salt
50g/1 zinc ion
18g/12 Sodium Nitrate I
g#! Ferric chloride 2g/(A-1) was immersed in the bath for 1 minute at room temperature and washed with water, and the support aluminum foil was used as a cathode in Example (1) (A-1).
) bath at a current density of 2 A/dn+" for 5 seconds to deposit an antimony layer. On this surface, an ultra-thin copper foil layer, a roughened layer, and a chromate layer were applied in the same manner as in Example (1). A composite foil was obtained by depositing or treating under the same conditions as in Example (1).This was laminated on a PR-4 base material under the same conditions as in Example (1) and molded under heat and pressure. A molded body was obtained.The aluminum foil that was the support was peeled off from this molded body, and the peel strength at that time was 0.40 kg/c+
It was ++.
〔発明の効果〕
本発明のＳｂまたはＣｕ−Ｓｂ合金層を中間層として有
する支持体金属箔−極薄銅箔からなる複合箔はその実用
化が容易であり、大量生産が可能である。[Effects of the Invention] The composite foil comprising a support metal foil and an ultrathin copper foil having an Sb or Cu-Sb alloy layer as an intermediate layer of the present invention is easy to put into practical use and can be mass-produced.
支持体金属箔は剥離型であり、印刷回路板製造時、エツ
チング除去型のような排液処理の問題はなく、またその
剥離時の接着力は適度でかつ均一であり、剥離不能、あ
るいは自然剥離による脱落などの問題もない。またＳｂ
ＳＣｕ−３ｂは塩化第二鉄、塩化第二銅など代表的なエ
ツチング液に可溶で、障害とならない。The support metal foil is a removable type, and there is no problem with drainage treatment unlike the etching removal type during the production of printed circuit boards, and the adhesive strength when peeled off is moderate and uniform, making it impossible to peel off or naturally. There are no problems such as falling off due to peeling. Also Sb
SCu-3b is soluble in typical etching solutions such as ferric chloride and cupric chloride, and does not pose a problem.
以上、本発明の複合箔は例えばガラス系樹脂含浸基材と
積層成型することで良好な成型体を得ることができ、そ
の支持体金属箔を剥離して、印刷回路の高密度化に対応
できる極薄銅箔層を提供することで実用上きわめて有益
なものである。As described above, the composite foil of the present invention can be laminated and molded with, for example, a glass-based resin-impregnated base material to obtain a good molded product, and by peeling off the supporting metal foil, it can be used for high-density printed circuits. It is extremely useful in practice by providing an ultra-thin copper foil layer.
Claims (6)
層との間にＳｂ又はＣｕ−Ｓｂ合金の中間層を有するこ
とを特徴とする複合箔。(1) A composite foil characterized by having an intermediate layer of Sb or Cu-Sb alloy between a support metal foil layer and an ultra-thin copper foil layer having a thickness of 12 μm or less.
ズ、真鍮、青銅より選ばれた箔であることを特徴とする
特許請求の範囲第１項に記載の複合箔。(2) The composite foil according to claim 1, wherein the support metal foil is a foil selected from copper, nickel, aluminum, tin, brass, and bronze.
層と接する面に亜鉛置換層を有するアルミニウム箔であ
ることを特徴とする特許請求の範囲第１項に記載の複合
箔。(3) The composite foil according to claim 1, wherein the support metal foil is an aluminum foil having a zinc substitution layer on the surface in contact with the intermediate layer of Sb or Cu-Sb alloy.
層を有することを特徴とする特許請求の範囲第１項〜３
項のいずれかに記載の複合箔。(4) Claims 1 to 3, characterized in that the ultra-thin copper foil has a roughening treatment layer and/or a passivation treatment layer.
Composite foil according to any of paragraphs.
気めっきし、その上に１２μｍ以下の銅層を電解析出さ
せ、さらにその表面に粗面化処理及び／又は不働態化処
理を行うことを特徴とする複合箔の製造方法。(5) Electroplating an Sb or Cu-Sb alloy layer on the support metal foil, electrolytically depositing a copper layer of 12 μm or less on it, and further roughening and/or passivating the surface. A method for manufacturing a composite foil, characterized by performing the following steps.
亜鉛置換層を形成した支持体金属箔を用いることを特徴
とする特許請求の範囲第５項に記載された複合箔の製造
方法。(6) The method for producing a composite foil according to claim 5, characterized in that a support metal foil is used in which aluminum foil is treated with a zincate bath to form a zinc substitution layer on the surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10753687A JPH0235040B2 (en) | 1987-04-30 | 1987-04-30 | FUKUGOHAKUOYOBISONOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10753687A JPH0235040B2 (en) | 1987-04-30 | 1987-04-30 | FUKUGOHAKUOYOBISONOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63274795A true JPS63274795A (en) | 1988-11-11 |
| JPH0235040B2 JPH0235040B2 (en) | 1990-08-08 |
Family
ID=14461677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10753687A Expired - Lifetime JPH0235040B2 (en) | 1987-04-30 | 1987-04-30 | FUKUGOHAKUOYOBISONOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0235040B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016402A1 (en) * | 1999-08-31 | 2001-03-08 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001021859A1 (en) * | 1999-09-21 | 2001-03-29 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001034879A1 (en) * | 1999-11-11 | 2001-05-17 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001034880A1 (en) * | 1999-11-11 | 2001-05-17 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same |
-
1987
- 1987-04-30 JP JP10753687A patent/JPH0235040B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016402A1 (en) * | 1999-08-31 | 2001-03-08 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001021859A1 (en) * | 1999-09-21 | 2001-03-29 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil |
| US6777108B1 (en) | 1999-09-21 | 2004-08-17 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001034879A1 (en) * | 1999-11-11 | 2001-05-17 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and copper-clad laminate using the electrolytic copper foil with carrier foil |
| WO2001034880A1 (en) * | 1999-11-11 | 2001-05-17 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil with carrier foil and method for manufacturing the same |
| CN1293236C (en) * | 1999-11-11 | 2007-01-03 | 三井金属鉱业株式会社 | Electrolytic copper foil with carrier foil and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0235040B2 (en) | 1990-08-08 |
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