JP2009293103A - Ultrathin copper foil with support and method of manufacturing the same - Google Patents
Ultrathin copper foil with support and method of manufacturing the same Download PDFInfo
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- JP2009293103A JP2009293103A JP2008150118A JP2008150118A JP2009293103A JP 2009293103 A JP2009293103 A JP 2009293103A JP 2008150118 A JP2008150118 A JP 2008150118A JP 2008150118 A JP2008150118 A JP 2008150118A JP 2009293103 A JP2009293103 A JP 2009293103A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000011889 copper foil Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000011888 foil Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 238000007747 plating Methods 0.000 claims abstract description 9
- 230000003746 surface roughness Effects 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 150000003658 tungsten compounds Chemical class 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- -1 citric acid Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、微細配線の形成に適した支持体付極薄銅箔に関するものである。 The present invention relates to an ultrathin copper foil with a support suitable for forming fine wiring.
エッチング加工の対象となる銅箔層が薄いほど微細配線の形成が容易なことから、支持体付銅箔が超高密度微細配線板の形成に使用されている。支持体付銅箔は、支持体となる金属箔と剥離層と極薄銅箔層とからなり、基材に極薄銅箔層を積層接着した後、支持体の金属箔を剥離して使用される。厚さ１２μｍ未満の銅箔はシワになりやすく、単体で取り扱うことは困難であるが、支持体を用いることにより、厚さ５μｍ以下の極薄銅箔を容易に取り扱うことができる。支持体付銅箔は、支持体となる金属箔上に、めっきや蒸着などの方法により、剥離層と極薄銅箔層とを順次形成して製造される。支持体となる金属箔としては一般に電解銅箔が使用される。これは圧延銅箔に比べて幅広であり、また、銅の化学的特性が、剥離層と極薄銅箔層を形成するめっき工程に適しているからである。 The thinner the copper foil layer to be etched, the easier the fine wiring can be formed. Therefore, the support-attached copper foil is used for forming an ultra-high density fine wiring board. The copper foil with support consists of a metal foil that becomes the support, a release layer, and an ultrathin copper foil layer. After the ultrathin copper foil layer is laminated and bonded to the substrate, the support metal foil is peeled off and used. Is done. A copper foil having a thickness of less than 12 μm tends to be wrinkled and difficult to handle alone, but by using a support, an ultrathin copper foil having a thickness of 5 μm or less can be easily handled. The copper foil with a support is manufactured by sequentially forming a release layer and an ultrathin copper foil layer on a metal foil serving as a support by a method such as plating or vapor deposition. In general, an electrolytic copper foil is used as the metal foil serving as the support. This is because it is wider than the rolled copper foil and the chemical properties of copper are suitable for the plating process for forming the release layer and the ultrathin copper foil layer.
電解銅箔の表面は平滑なものではなく、いわゆる析出面に析出した銅粒子の結晶成長に基づく微小な凹凸が存在し、一方、電解銅箔の製造時に製箔ドラムに接していた面、すなわち光沢面には、製箔ドラムの研磨傷が転写された微細な凹凸が存在する。このため、形成された極薄銅箔層の露出面の表面粗さは支持体となる金属箔として用いた電解銅箔の形状を反映し、平滑性を欠くものとなる。 The surface of the electrolytic copper foil is not smooth, and there are minute irregularities based on the crystal growth of the copper particles deposited on the so-called precipitation surface, while the surface that was in contact with the foil-making drum at the time of manufacturing the electrolytic copper foil, On the glossy surface, there are fine irregularities to which polishing scratches of the foil-making drum are transferred. For this reason, the surface roughness of the exposed surface of the formed ultrathin copper foil layer reflects the shape of the electrolytic copper foil used as the metal foil to be the support, and lacks smoothness.
電子回路の製造工程において極薄銅箔層の露出面は基材と接着されることから、該表面の微細な突起は基材中に埋め込まれることとなり、エッチングの精度を低下させる原因となる。すなわち、基材に埋め込まれた微細突起を除去するために過剰なエッチングが必要となり、微細配線の形状を劣化させることとなる。
解決しようとする問題点は、露出面に微細突起がなく平滑性に優れた極薄銅箔層を形成することである。 The problem to be solved is to form an ultra-thin copper foil layer with no fine protrusions on the exposed surface and excellent in smoothness.
本発明は、支持体となる金属箔と剥離層と極薄銅箔層とからなり、極薄銅箔層の露出面に高さ０．５μｍ以上の突起が１０個/ｃｍ２以下であることを特徴とする支持体付銅箔であることを最も主要な特徴とする。 The present invention comprises a metal foil serving as a support, a release layer, and an ultrathin copper foil layer, and the number of protrusions having a height of 0.5 μm or more is 10 / cm 2 or less on the exposed surface of the ultrathin copper foil layer. The main feature is that the copper foil has a support.
本発明の支持体付銅箔は極薄銅箔層の露出面に微細突起がなく平滑性に優れていることから、微細配線の形成に特に適している。 The copper foil with a support of the present invention is particularly suitable for forming fine wiring because it has no fine protrusions on the exposed surface of the ultrathin copper foil layer and is excellent in smoothness.
本発明は、支持体となる金属箔と剥離層と極薄銅箔層とからなり、極薄銅箔層の露出面に高さ０．５μｍ以上の突起が１０個/ｃｍ２以下であることを特徴とする支持体付銅箔である。
また、本発明は、支持体となる金属箔と剥離層と極薄銅箔層とからなり、極薄銅箔層の露出面の表面粗さがＲｚで０．１〜１．０μｍ、光沢度が４００〜８００であることを特徴とする前記の支持体付銅箔であり、極薄銅箔層の厚さは０．１〜５μｍ、剥離層はモリブデンまたはタングステンを含有する。
The present invention comprises a metal foil serving as a support, a release layer, and an ultrathin copper foil layer, and the number of protrusions having a height of 0.5 μm or more is 10 / cm 2 or less on the exposed surface of the ultrathin copper foil layer. It is a copper foil with a support characterized by these.
Further, the present invention comprises a metal foil serving as a support, a release layer, and an ultrathin copper foil layer, and the surface roughness of the exposed surface of the ultrathin copper foil layer is 0.1 to 1.0 μm in Rz, glossiness The thickness of the ultra-thin copper foil layer is 0.1 to 5 μm, and the release layer contains molybdenum or tungsten.
本発明の支持体付銅箔は、支持体となる金属箔上に、モリブデンまたはタングステンを含有する金属酸化物からなる剥離層を形成し、剥離層上に極薄銅層を光沢銅めっきにより形成することにより製造することができる。 The copper foil with a support of the present invention is formed by forming a release layer made of a metal oxide containing molybdenum or tungsten on a metal foil as a support, and forming an ultrathin copper layer on the release layer by bright copper plating. Can be manufactured.
本発明で用いる支持体となる金属箔の材質、厚さは特に規定するものではないが、コストや製造工程、機械特性及び化学特性から、厚さ８μｍ〜３５μｍの銅箔が好ましい。剥離層及び極薄銅箔を形成する面は、電解銅箔の光沢面と析出面のいずれでもよいが、表面粗さがＲｚで２．０μｍ以下であり、かつ異常な突起がないことが好ましい。Ｒｚが大きいと形成された極薄銅箔の表面粗さが大きくなり好ましくない。また、異常な突起部があると同様な異常部が形成されることとなる。 Although the material and thickness of the metal foil used as the support used in the present invention are not particularly specified, a copper foil having a thickness of 8 μm to 35 μm is preferable from the viewpoint of cost, manufacturing process, mechanical characteristics, and chemical characteristics. The surface on which the release layer and the ultrathin copper foil are formed may be either a glossy surface or a deposited surface of the electrolytic copper foil, but preferably has a surface roughness of Rz of 2.0 μm or less and no abnormal protrusions. . When Rz is large, the surface roughness of the formed ultrathin copper foil becomes large, which is not preferable. In addition, if there is an abnormal protrusion, a similar abnormal portion is formed.
本発明の剥離層は、モリブデン化合物またはタングステン化合物を含有する電解液を用いて、支持体となる金属箔上に電気めっきを行うことにより形成することができる。電気めっきを行う前に、支持体金属層の表面を適切な前処理によって清浄化することが好ましい。通常の酸洗処理のほか、アルカリ脱脂や電解洗浄を行ってもよい。 The release layer of the present invention can be formed by performing electroplating on a metal foil serving as a support using an electrolytic solution containing a molybdenum compound or a tungsten compound. Prior to electroplating, it is preferable to clean the surface of the support metal layer by a suitable pretreatment. In addition to the usual pickling treatment, alkaline degreasing or electrolytic cleaning may be performed.
モリブデン化合物としては、モリブデン酸ナトリウムなどの金属塩、タングステン化合物としてはタングステン酸カリウムなどの金属塩を用いることができる。また、これらの金属塩に加えて、硫酸ニッケルや硫酸コバルトなどの鉄系金属を含有する化合物を加えてもよい。これらの化合物を添加することにより、極薄銅箔から支持体金属に銅が拡散して剥離が困難となることを防止できる。金属イオンの溶解性や析出状態を安定化させる目的で、電解液にはクエン酸などの多価カルボン酸など配位結合により錯体を形成する配位子となる化合物、また、抵抗値調整の目的で硫酸ナトリウムなどの無機塩を添加してもよい。モリブデン化合物の添加量は、各々金属換算で０.１〜１０ｇ／ｌ、好ましくは０.５〜２ｇ／ｌであり、タングステン化合物の添加量は、各々金属換算で０.１〜１０ｇ／ｌ、好ましくは０.５〜２ｇ／ｌである。また、鉄系金属を含有する化合物については、金属換算で６０ｇ／ｌ以下、好ましくは１２ｇ／ｌ以下であり、鉄系金属イオンが多いと鉄系金属が優先して析出して剥離層が形成されなくなる。クエン酸の濃度は、ナトリウムイオンを除く金属種に対してモル換算で、０.２〜５倍、より好ましくは０.５〜２倍である。電解液温度は５〜７０℃、好ましくは１０〜５０℃である。電流密度は０.２〜１０Ａ／ｄｍ２、好ましくは０.５〜５Ａ／ｄｍ２であり、主としてｐＨは２〜８、好ましくは４〜７の範囲である。
上記の条件で電気めっきを行うと、鉄系金属が共存する場合には、まず、主として鉄系金属とモリブデンまたはタングステンが金属として析出し、電気めっきの進行とともにモリブデンまたはタングステンの酸化物が主として析出する。これは、鉄系金属イオンが消費される一方で、その供給が拡散律則により制限されるために、鉄系金属イオンの濃度が低下することによる。鉄系金属濃度が十分に低下した段階で、低電流密度で電気分解を継続することにより、主としてモリブデンまたはタングステンと酸素からなる層が析出する。鉄系金属が共存しない場合には、モリブデンまたはタングステンの酸化物が主として析出する。
A metal salt such as sodium molybdate can be used as the molybdenum compound, and a metal salt such as potassium tungstate can be used as the tungsten compound. In addition to these metal salts, compounds containing iron-based metals such as nickel sulfate and cobalt sulfate may be added. By adding these compounds, it is possible to prevent copper from diffusing from the ultrathin copper foil to the support metal and becoming difficult to peel. For the purpose of stabilizing the solubility and precipitation state of metal ions, the electrolyte is a compound that forms a complex by coordination bonds such as polyvalent carboxylic acids such as citric acid, and the purpose of adjusting the resistance value Inorganic salts such as sodium sulfate may be added. The addition amount of the molybdenum compound is 0.1 to 10 g / l, preferably 0.5 to 2 g / l in terms of metal, and the addition amount of the tungsten compound is 0.1 to 10 g / l in terms of metal, Preferably it is 0.5-2 g / l. Moreover, about the compound containing an iron-type metal, it is 60 g / l or less in metal conversion, Preferably it is 12 g / l or less, and when there are many iron-type metal ions, an iron-type metal preferentially precipitates and a peeling layer forms. It will not be done. The concentration of citric acid is 0.2 to 5 times, more preferably 0.5 to 2 times in terms of moles relative to the metal species excluding sodium ions. The electrolyte temperature is 5 to 70 ° C, preferably 10 to 50 ° C. The current density is 0.2 to 10 A / dm 2 , preferably 0.5 to 5 A / dm 2 , and the pH is mainly in the range of 2 to 8, preferably 4 to 7.
When electroplating is performed under the above conditions, when iron-based metal coexists, first, iron-based metal and molybdenum or tungsten precipitate as metal, and molybdenum or tungsten oxide mainly precipitates as electroplating progresses. To do. This is because the iron-based metal ions are consumed, but the supply thereof is limited by the diffusion law, so that the concentration of the iron-based metal ions decreases. When the iron-based metal concentration is sufficiently lowered, the electrolysis is continued at a low current density, so that a layer mainly composed of molybdenum or tungsten and oxygen is deposited. When the iron-based metal does not coexist, molybdenum or tungsten oxide mainly precipitates.
本発明の薄銅層は特に限定するものではないが、ピロ燐酸銅を主体とする電解液を用いた場合には緻密な銅めっき層が形成されることから、ピンホールが減少する。また、硫酸銅を主体とする電解液を用いた場合は、高速めっきが可能となり、薄銅層を効率よく形成することができる。両方のめっき方法を組み合わせることにより、所望の厚さを有し、ピンホールの少ない薄銅層を効率よく形成することができる。薄銅層の厚さは、用途に応じて任意に設定してよい。いずれの電解液を用いた場合も、いわゆる光沢剤の添加が必須であり、光沢剤を添加することにより、本発明の、支持体となる金属箔と剥離層と極薄銅箔層とからなり、極薄銅箔層の露出面の表面粗さがＲｚで０．１〜１．０μｍ、光沢度が４００〜８００である支持体付銅箔が得られる。
光沢剤としては、一般的に用いられる市販の光沢剤が使用できるが、硫黄を含む光沢剤が好適に用いられ、特にメルカプト基を有する光沢剤がもっとも好適であり、このような光沢剤としては、たとえば、３−メルカプト−１−プロパンスルホン酸がある。また、複数の水酸基を有する有機化合物ないし線状重合体を添加することにより、光沢剤の作用を向上させることができ、さらに平滑で光沢に優れ、異常な突起部がない表面を形成することができる。このような化合物としては、たとえば平均分子量（重量平均)が５００〜５，０００，０００のポリエチレングリコールがある。
The thin copper layer of the present invention is not particularly limited, but when an electrolytic solution mainly composed of copper pyrophosphate is used, a dense copper plating layer is formed, so that pinholes are reduced. In addition, when an electrolytic solution mainly composed of copper sulfate is used, high-speed plating is possible, and a thin copper layer can be formed efficiently. By combining both plating methods, it is possible to efficiently form a thin copper layer having a desired thickness and few pinholes. The thickness of the thin copper layer may be arbitrarily set according to the application. When using any electrolytic solution, it is essential to add a so-called brightener. By adding a brightener, the present invention consists of a metal foil, a release layer, and an ultrathin copper foil layer as a support. A copper foil with a support having a surface roughness Rz of 0.1 to 1.0 μm and a glossiness of 400 to 800 is obtained.
As the brightener, commonly used commercially available brighteners can be used, but sulfur-containing brighteners are preferably used, and in particular, a brightener having a mercapto group is most preferred. For example, 3-mercapto-1-propanesulfonic acid. In addition, by adding an organic compound or linear polymer having a plurality of hydroxyl groups, the effect of the brightener can be improved, and a smooth, excellent glossy surface with no abnormal protrusions can be formed. it can. Examples of such a compound include polyethylene glycol having an average molecular weight (weight average) of 500 to 5,000,000.
薄銅層の表面には、公知の方法で、クロメート処理などの方法により防錆処理を行うことができる。また、必要に応じて、基材樹脂との接着性を向上させる目的で、シランカップリング剤等による接着強化処理を行ってもよい。 The surface of the thin copper layer can be subjected to rust prevention treatment by a known method such as chromate treatment. Moreover, you may perform the adhesion reinforcement | strengthening process by a silane coupling agent etc. for the purpose of improving adhesiveness with base-material resin as needed.
以下に実施例により、本発明を説明する。
（実施例１〜４）
厚さ１８μｍ、光沢面の表面粗さＲｚ０．８μｍ電解銅箔を支持体として用いた。光沢面の形状を倍率１０００倍の電子顕微鏡で観察し、表面に高さ１．０μｍ以上の突起がないことを確認した。この電解銅箔を１０％硫酸中、温度：３０℃、電流密度：５Ａ/ｄｍ２、処理時間：２０秒の条件で陰極処理により表面を清浄化した後、純水で２０秒洗浄した。ついで、表１に記載の組成で調製した電解液（剥離層用）で、表１記載の条件で電気分解することにより、光沢面に剥離層を形成した。ついで、この電解銅箔を流水で２０秒洗浄した後、ピロリン酸銅めっき浴により温度：３０℃、ｐＨ：６．０、電流密度：０．５Ａ/ｄｍ２、処理時間：２０秒、陰極処理を行った後、純水で２０秒洗浄した。さらに、表１記載の電解液（極薄銅箔層用）中、表１記載の条件で電気分解することにより、２μｍの極薄銅箔層を形成した。流水で２０秒洗浄した後、公知の方法で防錆処理とシランカップリング剤処理を行った。重量変換により求めた極薄銅箔層の厚さと表面粗さ、光沢度、高さ０．５μｍ以上の突起の発生状況を表１にあわせて示した。なお、高さ０．５μｍ以上の突起の発生状況は、キーエンス社製レーザ顕微鏡ＶＫ８５１０を用いて測定を行なった。また、光沢度は日本電色工業製の光沢計ＰＧ−１Ｍを用いて６０度で測定し、他の測定は通常の方法で行った。
（比較例１〜２）
比較例１はモリブデンまたはタングステンを含有しない剥離層用いたほかは、実施例１と同様にして支持体付銅箔を作成した。
比較例２は光沢剤を添加しないほかは、実施例１と同様にして支持体付銅箔を作成した。
The following examples illustrate the present invention.
(Examples 1-4)
An electrolytic copper foil having a thickness of 18 μm and a glossy surface roughness Rz of 0.8 μm was used as a support. The shape of the glossy surface was observed with an electron microscope having a magnification of 1000 times, and it was confirmed that there were no protrusions having a height of 1.0 μm or more on the surface. The surface of this electrolytic copper foil was cleaned by cathodic treatment in 10% sulfuric acid under conditions of temperature: 30 ° C., current density: 5 A / dm 2, treatment time: 20 seconds, and then washed with pure water for 20 seconds. Subsequently, a release layer was formed on the glossy surface by electrolysis with the electrolyte solution (for release layer) prepared with the composition shown in Table 1 under the conditions shown in Table 1. Next, this electrolytic copper foil was washed with running water for 20 seconds and then subjected to a temperature of 30 ° C., pH: 6.0, current density: 0.5 A / dm 2, treatment time: 20 seconds, and cathode treatment with a copper pyrophosphate plating bath. After performing, it was washed with pure water for 20 seconds. Furthermore, a 2 μm ultrathin copper foil layer was formed by electrolysis under the conditions described in Table 1 in the electrolytic solution (for ultrathin copper foil layer) described in Table 1. After washing with running water for 20 seconds, a rust prevention treatment and a silane coupling agent treatment were performed by a known method. Table 1 shows the thickness, surface roughness, glossiness, and the occurrence of protrusions having a height of 0.5 μm or more, as determined by weight conversion. The occurrence of protrusions having a height of 0.5 μm or more was measured using a laser microscope VK8510 manufactured by Keyence Corporation. Further, the glossiness was measured at 60 ° using a gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd., and other measurements were performed by ordinary methods.
(Comparative Examples 1-2)
In Comparative Example 1, a copper foil with a support was prepared in the same manner as in Example 1 except that a release layer containing no molybdenum or tungsten was used.
In Comparative Example 2, a copper foil with a support was prepared in the same manner as in Example 1 except that no brightener was added.
上表からあきらかなように本発明の支持体付銅箔は、極薄銅箔層の露出面に高さ０．５μｍ以上の突起が１０個/ｃｍ２以下であり、平滑性に優れている。 As clearly shown in the above table, the copper foil with a support of the present invention has 10 / cm 2 or less protrusions having a height of 0.5 μm or more on the exposed surface of the ultrathin copper foil layer, and is excellent in smoothness. .
露出面に微細凹凸がないことからエッチング性に優れ、微細配線の形成に適する。 Since there are no fine irregularities on the exposed surface, it has excellent etching properties and is suitable for forming fine wiring.
Claims (5)
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| WO2012121020A1 (en) * | 2011-03-04 | 2012-09-13 | Jx日鉱日石金属株式会社 | Electrolytic copper foil having high strength and less projections due to abnormal electrodeposition and method for manufacturing same |
| JP2012219368A (en) * | 2011-04-14 | 2012-11-12 | Nan Ya Plastics Corp | Ultra thin copper foil with very low profile copper foil as carrier and manufacturing method therefor |
| JP2013185163A (en) * | 2012-03-06 | 2013-09-19 | Toray Kp Films Inc | Metalized film and metal foil |
| WO2014033917A1 (en) * | 2012-08-31 | 2014-03-06 | Jx日鉱日石金属株式会社 | Electrolytic copper foil and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012121020A1 (en) * | 2011-03-04 | 2012-09-13 | Jx日鉱日石金属株式会社 | Electrolytic copper foil having high strength and less projections due to abnormal electrodeposition and method for manufacturing same |
| JP2012219368A (en) * | 2011-04-14 | 2012-11-12 | Nan Ya Plastics Corp | Ultra thin copper foil with very low profile copper foil as carrier and manufacturing method therefor |
| JP2013185163A (en) * | 2012-03-06 | 2013-09-19 | Toray Kp Films Inc | Metalized film and metal foil |
| JP2014148742A (en) * | 2012-05-11 | 2014-08-21 | Jx Nippon Mining & Metals Corp | Copper foil and laminate plate using the same, printed wiring board, electronic apparatus, and method for manufacturing printed wiring board |
| WO2014033917A1 (en) * | 2012-08-31 | 2014-03-06 | Jx日鉱日石金属株式会社 | Electrolytic copper foil and process for producing same |
| JPWO2016158775A1 (en) * | 2015-03-31 | 2017-07-27 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
| JP2017088943A (en) * | 2015-11-06 | 2017-05-25 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, manufacturing method of laminate, manufacturing method of printed wiring board and manufacturing method of electronic device |
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