TW202413724A - Surface treated copper foil, copper clad laminates and printed wiring boards - Google Patents
Surface treated copper foil, copper clad laminates and printed wiring boards Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 239000011889 copper foil Substances 0.000 title claims abstract description 182
- 239000010949 copper Substances 0.000 title claims description 32
- 229910052802 copper Inorganic materials 0.000 title claims description 21
- 239000010410 layer Substances 0.000 claims description 168
- 239000002335 surface treatment layer Substances 0.000 claims description 89
- 239000000758 substrate Substances 0.000 claims description 72
- 239000011347 resin Substances 0.000 claims description 71
- 229920005989 resin Polymers 0.000 claims description 71
- 238000007788 roughening Methods 0.000 claims description 64
- 239000007787 solid Substances 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 description 60
- 238000009713 electroplating Methods 0.000 description 53
- 239000000243 solution Substances 0.000 description 41
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 35
- 238000007747 plating Methods 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 31
- 239000000126 substance Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000005259 measurement Methods 0.000 description 20
- 229910020630 Co Ni Inorganic materials 0.000 description 15
- 229910002440 Co–Ni Inorganic materials 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 239000006087 Silane Coupling Agent Substances 0.000 description 14
- 230000008878 coupling Effects 0.000 description 14
- 238000010168 coupling process Methods 0.000 description 14
- 238000005859 coupling reaction Methods 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 14
- 229910000679 solder Inorganic materials 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000004873 anchoring Methods 0.000 description 12
- 229910018605 Ni—Zn Inorganic materials 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 239000003989 dielectric material Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 150000003658 tungsten compounds Chemical class 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 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
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- -1 methacryloyl Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
本發明係一種表面處理銅箔，其具有銅箔及形成於上述銅箔之至少一面之表面處理層。表面處理層之山部之實體部體積Vmp為0.022～0.060 μm 3/μm 2。 The present invention is a surface treated copper foil, which comprises a copper foil and a surface treated layer formed on at least one side of the copper foil. The volume Vmp of the mountain portion of the surface treated layer is 0.022-0.060 μm 3 /μm 2 .
Description
本發明係關於一種表面處理銅箔、覆銅積層板及印刷配線板。The present invention relates to a surface treated copper foil, a copper clad laminate and a printed wiring board.
覆銅積層板於可撓性印刷配線板等各種用途中被廣泛使用。可撓性印刷配線板係藉由對覆銅積層板之銅箔進行蝕刻形成導體圖案（亦稱為「配線圖案」），於導體圖案上利用焊料連接並構裝電子零件而製造。Copper clad laminates are widely used in various applications such as flexible printed wiring boards. Flexible printed wiring boards are manufactured by etching the copper foil of copper clad laminates to form conductor patterns (also called "wiring patterns"), and then connecting and mounting electronic components on the conductor patterns using solder.
近年來，於個人電腦、行動終端等電子機器，電信號之高頻化隨著通訊之高速化及大容量化而不斷發展，要求能夠因應此情況之可撓性印刷配線板。尤其是電信號之頻率越高，信號功率之損耗（衰減）越大，資料越難讀取。因此，要求降低信號功率之損耗。In recent years, the high frequency of electrical signals in electronic devices such as personal computers and mobile terminals has been continuously developing along with the high speed and large capacity of communications, and flexible printed wiring boards that can cope with this situation are required. In particular, the higher the frequency of the electrical signal, the greater the loss (attenuation) of the signal power, and the more difficult it is to read the data. Therefore, it is required to reduce the loss of signal power.
電子電路中之信號功率損耗（傳輸損耗）發生之原因可大致分為兩個。其一係導體損耗，即因銅箔引起之損耗。其二係介電損耗，即因樹脂基材引起之損耗。 於高頻區域中，電流具有於導體表面流動之特性（即，集膚效應）。因此，若銅箔表面粗糙，則電流會沿著複雜之路徑流動。因此，為了減少高頻信號之導體損耗，較理想的是減小銅箔之表面粗糙度。 以下，於本說明書中，於僅記載為「傳輸損耗」及「導體損耗」之情形時，主要係指「高頻信號之傳輸損耗」及「高頻信號之導體損耗」。 The causes of signal power loss (transmission loss) in electronic circuits can be roughly divided into two. One is conductor loss, which is the loss caused by copper foil. The other is dielectric loss, which is the loss caused by the resin substrate. In the high-frequency region, the current has the characteristic of flowing on the surface of the conductor (i.e., the skinning effect). Therefore, if the surface of the copper foil is rough, the current will flow along a complex path. Therefore, in order to reduce the conductor loss of high-frequency signals, it is more ideal to reduce the surface roughness of the copper foil. In the following, in this manual, when only "transmission loss" and "conductor loss" are recorded, they mainly refer to "transmission loss of high-frequency signals" and "conductor loss of high-frequency signals".
介電損耗取決於樹脂基材之種類。因此，於高頻信號流動之電路基板中，較理想的是使用由低介電材料（例如，液晶聚合物、低介電聚醯亞胺）形成之樹脂基材。又，介電損耗亦因將銅箔與樹脂基材之間接著之接著劑而受到影響。因此，較理想的是銅箔與樹脂基材之間不使用接著劑進行接著。 因此，提出有為了將銅箔與樹脂基材之間不利用接著劑進行接著，而於銅箔之至少一面形成表面處理層。例如，於專利文獻1中提出有以下方法：於銅箔上設置由粗化粒子形成之粗化處理層，且於最表層形成矽烷偶合處理層。 [先前技術文獻] [專利文獻] Dielectric loss depends on the type of resin substrate. Therefore, in a circuit substrate where high-frequency signals flow, it is more ideal to use a resin substrate formed of a low dielectric material (e.g., liquid crystal polymer, low dielectric polyimide). In addition, dielectric loss is also affected by the adhesive between the copper foil and the resin substrate. Therefore, it is more ideal to bond the copper foil to the resin substrate without using an adhesive. Therefore, it is proposed to form a surface treatment layer on at least one side of the copper foil in order to bond the copper foil to the resin substrate without using an adhesive. For example, the following method is proposed in Patent Document 1: a roughening treatment layer formed by roughening particles is provided on the copper foil, and a silane coupling treatment layer is formed on the outermost layer. [Prior art literature] [Patent literature]
[專利文獻1]日本特開2012-112009號公報[Patent Document 1] Japanese Patent Application Publication No. 2012-112009
[發明所欲解決之課題][The problem that the invention wants to solve]
若銅箔表面經粗化處理，則藉由因粗化粒子帶來之定錨效應，可提高銅箔與樹脂基材之間之接著性，但是有時會因集膚效應而使導體損耗增大。因此，較理想的是減少電沉積於銅箔表面之粗化粒子。 另一方面，若減少電沉積於銅箔表面之粗化粒子，則由粗化粒子帶來之定錨效應降低。其結果，無法充分地獲得銅箔與樹脂基材之接著性。尤其，由液晶聚合物、低介電聚醯亞胺等低介電材料形成之樹脂基材較以往之樹脂基材難以與銅箔接著，故而期望開發提高銅箔與樹脂基材之間之接著性的方法。 又，矽烷偶合處理層雖然具有提高銅箔與樹脂基材之間之接著性的效果，但是亦存在根據其種類而使得接著性之提高效果不足之情況。 If the surface of the copper foil is roughened, the anchoring effect brought about by the roughened particles can improve the adhesion between the copper foil and the resin substrate, but sometimes the conductor loss is increased due to the skinning effect. Therefore, it is more ideal to reduce the roughened particles deposited on the surface of the copper foil. On the other hand, if the roughened particles deposited on the surface of the copper foil are reduced, the anchoring effect brought about by the roughened particles is reduced. As a result, the adhesion between the copper foil and the resin substrate cannot be fully obtained. In particular, the resin substrate formed by low dielectric materials such as liquid crystal polymers and low dielectric polyimide is more difficult to bond to the copper foil than the previous resin substrates, so it is expected to develop a method to improve the adhesion between the copper foil and the resin substrate. In addition, although the silane coupling treatment layer has the effect of improving the adhesion between the copper foil and the resin substrate, there are cases where the adhesion improvement effect is insufficient depending on its type.
本發明之實施形態係為了解決如上述之問題而完成者。本發明之實施形態於一個態樣中，目的在於提供一種表面處理銅箔，其能夠提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性。 又，本發明之實施形態於另一態樣中，目的在於提供一種覆銅積層板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與表面處理銅箔之間之接著性優異。 進而，本發明之實施形態於另一態樣中，目的在於提供一種印刷配線板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與電路圖案之間之接著性優異。 [解決課題之技術手段] The embodiment of the present invention is completed to solve the above-mentioned problems. In one embodiment of the present invention, the purpose is to provide a surface-treated copper foil that can improve the adhesion with a resin substrate, especially a resin substrate suitable for high-frequency use. In another embodiment of the present invention, the purpose is to provide a copper-clad laminate, wherein the adhesion between the resin substrate, especially a resin substrate suitable for high-frequency use, and the surface-treated copper foil is excellent. Furthermore, in another embodiment of the present invention, the purpose is to provide a printed wiring board, wherein the adhesion between the resin substrate, especially a resin substrate suitable for high-frequency use, and a circuit pattern is excellent. [Technical means for solving the problem]
本發明人等為了解決上述問題而對表面處理銅箔進行潛心研究後，結果發現基於表面處理層之山部之實體部體積Vmp與表面處理層（尤其是粗化處理層中之粗化粒子）之形狀之複雜性有關係的見解，藉由將表面處理層之山部之實體部體積Vmp控制為規定之範圍，可提高由表面處理層帶來之定錨效應，使表面處理銅箔與樹脂基材之接著性提高。In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive research on surface-treated copper foil, and found that based on the understanding that the volume Vmp of the solid part of the mountain part of the surface treatment layer is related to the complexity of the shape of the surface treatment layer (especially the roughened particles in the roughened layer), by controlling the volume Vmp of the solid part of the mountain part of the surface treatment layer within a specified range, the anchoring effect brought by the surface treatment layer can be enhanced, thereby improving the adhesion between the surface-treated copper foil and the resin substrate.
即，本發明之實施形態於一個態樣中，係關於一種表面處理銅箔，其具有銅箔及形成於上述銅箔之至少一面之表面處理層，上述表面處理層之山部之實體部體積Vmp為0.022～0.060 μm 3/μm 2。 That is, one embodiment of the present invention relates to a surface treated copper foil having a copper foil and a surface treated layer formed on at least one surface of the copper foil, wherein the volume Vmp of the peaks of the surface treated layer is 0.022 to 0.060 μm 3 /μm 2 .
又，本發明之實施形態於另一態樣中，係關於一種覆銅積層板，其具備上述表面處理銅箔及接著於上述表面處理銅箔之上述表面處理層之樹脂基材。 進而，本發明之實施形態於另一態樣中，係關於一種印刷配線板，其具備對上述覆銅積層板之上述表面處理銅箔進行蝕刻而形成之電路圖案。 [發明之效果] In another embodiment of the present invention, a copper-clad laminate is provided, which has the surface-treated copper foil and a resin substrate of the surface-treated layer connected to the surface-treated copper foil. Furthermore, in another embodiment of the present invention, a printed wiring board is provided, which has a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate. [Effect of the invention]
若根據本發明之實施形態，於一個態樣中，可提供一種表面處理銅箔，其能夠提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性。 又，若根據本發明之實施形態，於另一態樣中，可提供一種覆銅積層板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與表面處理銅箔之間之接著性優異。 進而，若根據本發明之實施形態，於另一態樣中，可提供一種印刷配線板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與電路圖案之間之接著性優異。 According to an embodiment of the present invention, in one embodiment, a surface-treated copper foil can be provided, which can improve the adhesion with a resin substrate, especially a resin substrate suitable for high-frequency use. Furthermore, according to an embodiment of the present invention, in another embodiment, a copper-clad laminate can be provided, wherein the adhesion between the resin substrate, especially a resin substrate suitable for high-frequency use, and the surface-treated copper foil is excellent. Furthermore, according to an embodiment of the present invention, in another embodiment, a printed wiring board can be provided, wherein the adhesion between the resin substrate, especially a resin substrate suitable for high-frequency use, and a circuit pattern is excellent.
以下，對本發明之較佳實施形態具體地進行說明，但是本發明不應限定於該等實施形態來解釋，只要不脫離本發明之主旨，則可基於該行業者之知識進行各種變更、改良等。以下之實施形態所揭示之多個構成要素可藉由適當之組合而形成各種發明。例如，既可自以下之實施形態所示之所有構成要素刪除幾個構成要素，亦可將不同之實施形態之構成要素適當組合。The preferred embodiments of the present invention are described in detail below, but the present invention should not be limited to the embodiments. Various changes and improvements can be made based on the knowledge of the industry as long as they do not deviate from the main purpose of the present invention. The multiple components disclosed in the following embodiments can form various inventions by appropriate combination. For example, some components can be deleted from all the components shown in the following embodiments, and the components of different embodiments can be appropriately combined.
本發明之實施形態之表面處理銅箔具有銅箔及形成於銅箔之至少一面之表面處理層，該表面處理層之山部之實體部體積Vmp為0.022～0.060 μm 3/μm 2。 若根據以上之構成，可實現一種能夠提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性的表面處理銅箔。 The surface treated copper foil of the embodiment of the present invention comprises a copper foil and a surface treated layer formed on at least one side of the copper foil, wherein the volume Vmp of the mountain portion of the surface treated layer is 0.022-0.060 μm 3 /μm 2 . According to the above structure, a surface treated copper foil capable of improving adhesion with a resin substrate, especially a resin substrate suitable for high frequency applications, can be realized.
表面處理層既可僅形成於銅箔之一面，亦可形成於銅箔之兩面。當在銅箔之兩面形成表面處理層之情形時，表面處理層之種類既可相同亦可不同。當形成在銅箔之兩面之表面處理層的種類不同之情形時，例如，包含粗化處理層之表面處理層形成於銅箔之一面，不包含粗化處理層之表面處理層形成於銅箔之另一面。The surface treatment layer may be formed on only one side of the copper foil or on both sides of the copper foil. When the surface treatment layer is formed on both sides of the copper foil, the types of the surface treatment layer may be the same or different. When the types of the surface treatment layers formed on both sides of the copper foil are different, for example, a surface treatment layer including a roughening treatment layer is formed on one side of the copper foil, and a surface treatment layer not including a roughening treatment layer is formed on the other side of the copper foil.
表面處理層之表面形狀可使用表面性狀參數來特定。表面性狀參數可藉由依據ISO 25178-2：2012，測定表面形狀，對根據測定資料算出之負載曲線進行解析而獲得。 於說明負載曲線時，首先，對負載面積率進行說明。 所謂負載面積率，係指將立體的測定對象物於某高度之面切斷時，相當於該測定對象物之剖面之區域除以測定視野之面積而求出之比率。再者，於本發明中，作為測定對象物，假定銅箔或表面處理銅箔之表面處理層等。 負載曲線係表示各高度處的負載面積率之曲線。負載面積率0%附近之高度表示測定對象物之最高部分之高度。負載面積率100%附近之高度表示測定對象物之最低部分之高度。 The surface shape of the surface treatment layer can be specified using surface property parameters. The surface property parameters can be obtained by measuring the surface shape according to ISO 25178-2:2012 and analyzing the load curve calculated based on the measurement data. When explaining the load curve, first, the load area ratio is explained. The so-called load area ratio refers to the ratio obtained by dividing the area equivalent to the cross section of the three-dimensional measurement object when the surface of the measurement object is cut at a certain height by the area of the measurement field. Furthermore, in the present invention, copper foil or the surface treatment layer of the surface-treated copper foil is assumed as the measurement object. The load curve is a curve that represents the load area ratio at each height. The height near the load area ratio of 0% indicates the height of the highest part of the object being measured. The height near the load area ratio of 100% indicates the height of the lowest part of the object being measured.
圖1係表示表面處理層之典型的負載曲線之曲線圖。 可靈活應用負載曲線來表現表面處理層之實體部體積及空間部體積。所謂實體部體積，相當於在測定視野下測定對象物之實體所占之部分的體積。而所謂空間部體積，則相當於測定視野下之實體部分之間之空間所占的體積。 於本發明所記載之負載曲線中，將負載面積率為10%及80%之位置設為邊界，而分為谷部、核心部及山部。 參照圖1，且同時對應於本發明之實施形態之表面處理層，對各參數進行說明。Vvv意指表面處理層之谷部之空間部體積，Vvc意指表面處理層之核心部之空間部體積，Vmp意指表面處理層之山部之實體部體積，Vmc意指表面處理層之核心部之實體部體積。Sk意指表面處理層之核心部之水平差（核心部之上限水平與下限水平之差），Spk意指表面處理層之山部之平均高度，Svk意指表面處理層之谷部之平均深度。 再者，所謂山部，係指測定對象物中高度高之部分。所謂谷部，係指測定對象物中高度低之部分。而所謂核心部，則意指測定對象物中，山部與谷部以外之部分，即接近平均之高度之部分。 FIG. 1 is a graph showing a typical load curve of a surface treatment layer. The load curve can be flexibly applied to express the solid volume and space volume of the surface treatment layer. The so-called solid volume is equivalent to the volume of the solid part of the measured object under the measurement field of view. The so-called space volume is equivalent to the volume occupied by the space between the solid parts under the measurement field of view. In the load curve recorded in the present invention, the positions where the load area ratio is 10% and 80% are set as boundaries, and divided into valleys, cores and mountains. Referring to FIG. 1, each parameter is explained for the surface treatment layer corresponding to the implementation form of the present invention. Vvv means the volume of the space of the valley of the surface treatment layer, Vvc means the volume of the space of the core of the surface treatment layer, Vmp means the volume of the solid part of the mountain of the surface treatment layer, and Vmc means the volume of the solid part of the core of the surface treatment layer. Sk means the level difference of the core of the surface treatment layer (the difference between the upper limit level and the lower limit level of the core), Spk means the average height of the mountain of the surface treatment layer, and Svk means the average depth of the valley of the surface treatment layer. Furthermore, the so-called mountain refers to the high part of the measured object. The so-called valley refers to the low part of the measured object. And the so-called core refers to the part of the measured object other than the mountain and the valley, that is, the part close to the average height.
表面處理層之山部之實體部體積Vmp（以下，有時簡略為「Vmp」）與表面處理層之形狀之複雜性有關係。尤其當表面處理層包含粗化處理層之情形時，與構成粗化處理層之粗化粒子之形狀的複雜性有關係。 如上述，於本發明之實施形態之表面處理銅箔中，表面處理層之Vmp被規定為0.022～0.060 μm 3/μm 2。若為該範圍之Vmp，則可提高表面處理層之定錨效應，故而表面處理銅箔與樹脂基材之接著性提高。若表面處理層之Vmp為0.022 μm 3/μm 2以上，則表面處理層之複雜性提高，可獲得所期望之定錨效應。若表面處理層之Vmp為0.060 μm 3/μm 2以下，則可減少傳輸損耗。 自穩定地提高表面處理層之定錨效應之觀點，表面處理層之Vmp較佳為0.030～0.055 μm 3/μm 2，更佳為0.035～0.046 μm 3/μm 2。 The volume Vmp of the solid part of the mountain part of the surface treatment layer (hereinafter, sometimes simply referred to as "Vmp") is related to the complexity of the shape of the surface treatment layer. In particular, when the surface treatment layer includes a roughening treatment layer, it is related to the complexity of the shape of the roughening particles constituting the roughening treatment layer. As mentioned above, in the surface-treated copper foil of the embodiment of the present invention, the Vmp of the surface treatment layer is specified to be 0.022 to 0.060 μm 3 /μm 2. If the Vmp is within this range, the anchoring effect of the surface treatment layer can be improved, thereby improving the adhesion between the surface-treated copper foil and the resin substrate. If the Vmp of the surface treatment layer is 0.022 μm 3 /μm 2 or more, the complexity of the surface treatment layer is improved, and the desired anchoring effect can be obtained. If the Vmp of the surface treatment layer is 0.060 μm 3 /μm 2 or less, the transmission loss can be reduced. From the perspective of steadily improving the anchoring effect of the surface treatment layer, the Vmp of the surface treatment layer is preferably 0.030 to 0.055 μm 3 /μm 2 , and more preferably 0.035 to 0.046 μm 3 /μm 2 .
表面處理層之山部之平均高度Spk（以下，有時簡略為「Spk」），與使表面處理層與樹脂基材接著時表面處理層之山部（較平均高之部分）向樹脂基材之嵌入容易度有關係。尤其當表面處理層包含粗化處理層之情形時，與構成粗化處理層之粗化粒子之較平均高之部分向樹脂基材之嵌入容易度有關係。 當表面處理層之Vmp處於上述範圍之情形時，自確保表面處理層之山部向樹脂基材之嵌入的觀點，表面處理層之Spk亦可為0.42～1.00 μm。若為該範圍之Spk，則可提高表面處理層之山部向樹脂基材之嵌入所帶來的定錨效應，使得表面處理銅箔與樹脂基材之接著性提高。若表面處理層之Spk為0.42 μm以上，則表面處理層之山部容易向樹脂基材嵌入，可獲得所期望之定錨效應。若表面處理層之Spk為1.00 μm以下，則例如粗化粒子不易折斷，可獲得所期望之定錨效應。 自穩定地確保表面處理層之山部向樹脂基材之嵌入的觀點，表面處理層之Spk更佳為0.60～0.95 μm，進而佳為0.71～0.90 μm。 The average height Spk of the peaks of the surface treatment layer (hereinafter, sometimes simply referred to as "Spk") is related to the ease with which the peaks of the surface treatment layer (higher than average portion) are embedded in the resin substrate when the surface treatment layer is bonded to the resin substrate. In particular, when the surface treatment layer includes a roughening treatment layer, it is related to the ease with which the higher than average portion of the roughening particles constituting the roughening treatment layer is embedded in the resin substrate. When the Vmp of the surface treatment layer is within the above range, the Spk of the surface treatment layer may be 0.42 to 1.00 μm from the perspective of ensuring that the peaks of the surface treatment layer are embedded in the resin substrate. If the Spk is within this range, the anchoring effect brought about by the embedding of the mountain portion of the surface treatment layer into the resin substrate can be improved, so that the adhesion between the surface-treated copper foil and the resin substrate is improved. If the Spk of the surface treatment layer is 0.42 μm or more, the mountain portion of the surface treatment layer is easily embedded in the resin substrate, and the desired anchoring effect can be obtained. If the Spk of the surface treatment layer is 1.00 μm or less, for example, the roughened particles are not easily broken, and the desired anchoring effect can be obtained. From the perspective of stably ensuring the embedding of the mountain portion of the surface treatment layer into the resin substrate, the Spk of the surface treatment layer is preferably 0.60 to 0.95 μm, and further preferably 0.71 to 0.90 μm.
表面處理層之展開界面面積率Sdr（以下，有時簡略為「Sdr」）亦可為40～130%。 Sdr係ISO 25178-2：2012中規定之複合參數，表示表面處理層之表面積大小。因此，發明人認為若表面處理層之Sdr過大，則表面處理層之表面緻密且起伏變得激烈，故而於將表面處理銅箔接著於樹脂基材之情形時，容易發揮定錨效應，另一方面，傳輸損耗因集膚效應而變大。因此，藉由將表面處理層之Sdr設為上述範圍，可確保保證定錨效應與抑制傳輸損耗之平衡。 自穩定地確保該效果之觀點，表面處理層之Sdr更佳為53～120%，進而佳為62～110%。 The open interface area ratio Sdr (hereinafter, sometimes simply referred to as "Sdr") of the surface treatment layer can also be 40 to 130%. Sdr is a composite parameter specified in ISO 25178-2:2012, which indicates the surface area of the surface treatment layer. Therefore, the inventors believe that if the Sdr of the surface treatment layer is too large, the surface of the surface treatment layer becomes dense and the undulations become violent, so when the surface-treated copper foil is attached to the resin substrate, the anchoring effect is easily exerted, and on the other hand, the transmission loss becomes larger due to the skinning effect. Therefore, by setting the Sdr of the surface treatment layer to the above range, a balance between ensuring the anchoring effect and suppressing the transmission loss can be ensured. From the perspective of stably ensuring this effect, the Sdr of the surface treatment layer is preferably 53 to 120%, and further preferably 62 to 110%.
於形成表面處理層之銅箔之表面，一般而言存在微小之凹凸部。例如，於軋製銅箔之情形時，於軋製時由軋製油形成之油坑會以微小凹部之形式形成於表面。又，於電解銅箔之情形時，在研磨時形成之轉筒之研磨條紋會造成析出形成於轉筒上之電解銅箔之轉筒側表面的微小凹凸部。若於銅箔存在微小凹凸部，則例如於形成粗化處理層時，於凸部周邊，電流集中而粗化粒子過生長，另一方面，於凹部周邊，電流無法充分地被供給，粗化粒子難以生長。其結果，成為於銅箔之凸部周邊形成粗大之粗化粒子，另一方面，於銅箔之凹部周邊粗化粒子變得過小或未形成粗化粒子之狀態，即，銅箔表面之粗化粒子未均勻地形成之狀態。於粗大之粗化粒子多之表面處理銅箔中，若於與樹脂基材接合後，賦予使表面處理銅箔剝離之力，則應力集中於粗大之粗化粒子而容易折斷，結果，存在相對於樹脂基材之接著力降低之情況。又，於粗化粒子之大小不足之表面處理銅箔中，存在由粗化粒子帶來之定錨效應降低，無法充分獲得銅箔與樹脂基材之接著性之情況。 發明人認為若表面處理層之Sdr為上述範圍，則有可能於銅箔之微小凹部之周邊亦充分形成有粗化粒子，有助於與樹脂基材之接著力之粗化粒子的形成區域（面積）增加，結果表面處理銅箔與樹脂基材之接著性提高。 Generally speaking, there are tiny uneven parts on the surface of the copper foil that forms the surface treatment layer. For example, in the case of rolled copper foil, oil pits formed by rolling oil during rolling will form on the surface in the form of tiny recesses. Also, in the case of electrolytic copper foil, the grinding lines of the drum formed during grinding will cause tiny uneven parts to precipitate on the drum side surface of the electrolytic copper foil formed on the drum. If there are tiny uneven parts on the copper foil, for example, when forming the roughening treatment layer, the current will concentrate around the protrusions and the roughening particles will overgrow. On the other hand, the current cannot be fully supplied around the recesses, and the roughening particles will have difficulty growing. As a result, coarse roughening particles are formed around the convex part of the copper foil, while on the other hand, the roughening particles become too small or no roughening particles are formed around the concave part of the copper foil, that is, the roughening particles on the surface of the copper foil are not formed uniformly. In the surface-treated copper foil with many coarse roughening particles, if a force is applied to peel the surface-treated copper foil after bonding with the resin substrate, the stress is concentrated on the coarse roughening particles and it is easy to break. As a result, there is a situation where the bonding force relative to the resin substrate is reduced. In addition, in the surface-treated copper foil with insufficient size of roughening particles, there is a situation where the anchoring effect brought by the roughening particles is reduced, and the bonding between the copper foil and the resin substrate cannot be fully obtained. The inventor believes that if the Sdr of the surface treatment layer is within the above range, it is possible to form sufficient roughened particles around the micro-concave portion of the copper foil, which helps increase the formation area (area) of the roughened particles that improve the adhesion with the resin substrate, resulting in improved adhesion between the surface treated copper foil and the resin substrate.
表面處理層中之Zn附著量並無特別限定，較佳為6～200 μm/dm 2。藉由將Zn附著量控制為該範圍，可提高由表面處理銅箔形成之電路圖案之焊料耐熱性。自穩定地提高該效果之觀點，表面處理層中之Zn附著量更佳為82～200 μm/dm 2。 表面處理層中之Zn附著量，可藉由將表面處理層溶解於20質量%之硝酸，使用原子吸光分光光度計（VARIAN公司製造，AA240FS）以原子吸光法進行定量分析而測定。當在銅箔之兩面設置有表面處理層之情形時，於保護非測定對象之表面處理層之表面後，使測定對象之表面處理層溶解而進行定量分析。 The amount of Zn deposited in the surface treatment layer is not particularly limited, but is preferably 6 to 200 μm/dm 2 . By controlling the amount of Zn deposited within this range, the solder heat resistance of the circuit pattern formed by the surface-treated copper foil can be improved. From the viewpoint of stably improving this effect, the amount of Zn deposited in the surface treatment layer is more preferably 82 to 200 μm/dm 2 . The amount of Zn deposited in the surface treatment layer can be measured by dissolving the surface treatment layer in 20 mass % nitric acid and performing quantitative analysis using an atomic absorption spectrophotometer (manufactured by VARIAN, AA240FS) by an atomic absorption method. When a surface treatment layer is provided on both sides of the copper foil, after protecting the surface of the surface treatment layer not being measured, the surface treatment layer of the measured object is dissolved for quantitative analysis.
表面處理層之種類，若具有上述表面形狀，則並無特別限定，可使用在該技術領域中公知之各種表面處理層。 作為表面處理層之例，可舉粗化處理層、耐化學品處理層、耐熱處理層、鉻酸鹽處理層、矽烷偶合處理層等。該等之層可單一地使用或將2種以上組合使用。其中，自與樹脂基材之接著性之觀點，表面處理層較佳含有粗化處理層。 當表面處理層含有選自由耐化學品處理層、耐熱處理層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中之1種以上之層的情形時，該等之層較佳設置於粗化處理層上。 The type of surface treatment layer is not particularly limited as long as it has the above-mentioned surface shape, and various surface treatment layers known in the technical field can be used. Examples of surface treatment layers include roughening treatment layers, chemical resistance treatment layers, heat resistance treatment layers, chromate treatment layers, silane coupling treatment layers, etc. These layers can be used alone or in combination of two or more. Among them, from the perspective of adhesion to the resin substrate, the surface treatment layer preferably contains a roughening treatment layer. When the surface treatment layer contains one or more layers selected from the group consisting of a chemical-resistant treatment layer, a heat-resistant treatment layer, a chromate treatment layer, and a silane coupling treatment layer, such layers are preferably disposed on the roughening treatment layer.
粗化處理層含有粗化粒子。粗化粒子亦可含有1次粗化粒子及2次粗化粒子。2次粗化粒子亦可具有與1次粗化粒子不同之化學組成。又，較佳於1次粗化粒子之表面之至少一部分形成有覆蓋鍍覆層。 圖2係示意性地表示於銅箔之一面具有粗化處理層之表面處理銅箔的剖視圖。 如圖2所示，本發明實施形態之一例包含形成於銅箔（10）之一面之粗化處理層。粗化處理層含有1次粗化粒子（20）、被覆1次粗化粒子（20）之覆蓋鍍覆層（30）及形成於覆蓋鍍覆層（30）上之2次粗化粒子（40）。較佳為由覆蓋鍍覆層（30）被覆之1次粗化粒子（20）為大致球狀，2次粗化粒子（40）以擴展成樹枝狀之方式形成。認為Vmp、Spk及Sdr被控制為上述範圍之表面處理層具有此種剖面構造。 The roughening layer contains roughening particles. The roughening particles may also contain primary roughening particles and secondary roughening particles. The secondary roughening particles may also have a chemical composition different from that of the primary roughening particles. In addition, it is preferred that a coating layer is formed on at least a portion of the surface of the primary roughening particles. FIG. 2 is a schematic cross-sectional view of a surface-treated copper foil having a roughening layer on one side of the copper foil. As shown in FIG. 2 , an example of an embodiment of the present invention includes a roughening layer formed on one side of a copper foil (10). The roughening layer contains primary roughening particles (20), a coating layer (30) covering the primary roughening particles (20), and secondary roughening particles (40) formed on the coating layer (30). It is preferred that the primary roughened particles (20) covered by the coating layer (30) are roughly spherical, and the secondary roughened particles (40) are formed in a manner that expands into a tree-like shape. It is believed that the surface treatment layer in which Vmp, Spk and Sdr are controlled within the above range has such a cross-sectional structure.
粗化粒子並無特別限定，可由選自由銅、鎳、鈷、磷、鎢、砷、鉬、鉻及鋅所組成之群中之單一元素或含有該等元素之2種以上的合金形成。 1次粗化粒子較佳由銅或銅合金形成，尤其由銅形成。 2次粗化粒子較佳由含有銅、鈷及鎳之合金形成。 覆蓋鍍覆層並無特別限定，可由銅、銀、金、鎳、鈷、鋅等形成。其中，覆蓋鍍覆層較佳由銅形成。 The roughening particles are not particularly limited and can be formed of a single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing two or more of these elements. The primary roughening particles are preferably formed of copper or a copper alloy, especially copper. The secondary roughening particles are preferably formed of an alloy containing copper, cobalt and nickel. The overlay coating is not particularly limited and can be formed of copper, silver, gold, nickel, cobalt, zinc, etc. Among them, the overlay coating is preferably formed of copper.
粗化處理層例如可藉由在進行用以形成1次粗化粒子之1次粗化處理後，進行用以形成覆蓋鍍覆層之覆蓋鍍覆，繼而進行用以形成2次粗化粒子之2次粗化處理而形成。藉由利用此種方法進行粗化處理，而容易形成具有如上述之表面形狀之表面處理層。 各粒子及層之形成可藉由電鍍而進行。具體而言，1次粗化粒子可藉由使用添加有微量鎢化合物之鍍覆液之電鍍而形成。覆蓋鍍覆層及2次粗化粒子可藉由使用含有規定成分之鍍覆液之電鍍而形成。 The roughening treatment layer can be formed, for example, by performing a primary roughening treatment for forming primary roughening particles, performing a covering plating for forming a covering plating layer, and then performing a secondary roughening treatment for forming secondary roughening particles. By performing the roughening treatment using this method, a surface treatment layer having a surface shape as described above can be easily formed. The formation of each particle and layer can be performed by electroplating. Specifically, the primary roughening particles can be formed by electroplating using a plating solution to which a trace amount of tungsten compound is added. The covering plating layer and the secondary roughening particles can be formed by electroplating using a plating solution containing a predetermined component.
作為鎢化合物，並無特別限定，例如，可使用鎢酸鈉（Na 2WO 4）等。 作為鍍覆液中之鎢化合物之含量，較佳設為1 ppm以上。有時於形成粗化處理層之銅箔之表面，存在油坑等微小之凹部，於凹部周邊粗化粒子變得過小或未形成粗化粒子，但是若為此種含量，則抑制形成於銅箔之相對較平滑之部分的1次粗化粒子之過生長，且容易於凹部周邊形成1次粗化粒子。再者，鎢化合物之含量上限值並無特別限定，自抑制電阻增大之觀點，較佳為20 ppm。 There is no particular limitation on the tungsten compound, and for example, sodium tungstate (Na 2 WO 4 ) can be used. The content of the tungsten compound in the plating solution is preferably set to 1 ppm or more. Sometimes, there are tiny recesses such as oil pits on the surface of the copper foil forming the roughening layer, and the roughened particles around the recesses become too small or no roughened particles are formed. However, if this content is used, the overgrowth of the primary roughened particles formed in the relatively smoother part of the copper foil is suppressed, and the primary roughened particles are easily formed around the recesses. Furthermore, the upper limit of the content of the tungsten compound is not particularly limited, and from the viewpoint of suppressing the increase in resistance, it is preferably 20 ppm.
形成粗化處理層時之電鍍條件，根據所使用之電鍍裝置等來調整即可，並無特別限定，典型條件如下。再者，各電鍍既可為1次，亦可進行多次。 （1次粗化粒子之形成條件） 鍍覆液組成：5～15 g/L之Cu，40～100 g/L之硫酸，1～6 ppm之鎢酸鈉 鍍覆液溫度：20～50℃ 電鍍條件：電流密度30～90 A/dm 2，時間0.1～8秒 The electroplating conditions for forming the roughening layer can be adjusted according to the electroplating equipment used, etc., and there is no particular limitation. Typical conditions are as follows. In addition, each electroplating can be performed once or multiple times. (Conditions for forming roughening particles once) Coating solution composition: 5-15 g/L Cu, 40-100 g/L sulfuric acid, 1-6 ppm sodium tungstate Coating solution temperature: 20-50°C Electroplating conditions: current density 30-90 A/dm 2 , time 0.1-8 seconds
（覆蓋鍍覆層之形成條件） 鍍覆液組成：10～30 g/L之Cu，70～130 g/L之硫酸 鍍覆液溫度：30～60℃ 電鍍條件：電流密度4.8～15 A/dm 2，時間0.1～8秒 (Conditions for forming the coating) Coating liquid composition: 10-30 g/L Cu, 70-130 g/L sulfuric acid coating liquid temperature: 30-60°C Electroplating conditions: current density 4.8-15 A/dm 2 , time 0.1-8 seconds
（2次粗化粒子之形成條件） 鍍覆液組成：10～20 g/L之Cu，5～15 g/L之Co，5～15 g/L之Ni 鍍覆液溫度：30～50℃ 電鍍條件：電流密度24～50 A/dm 2，時間0.3～0.8秒 (Forming conditions of secondary coarsening particles) Plating solution composition: 10-20 g/L Cu, 5-15 g/L Co, 5-15 g/L Ni Plating solution temperature: 30-50°C Electroplating conditions: current density 24-50 A/dm 2 , time 0.3-0.8 seconds
作為耐化學品處理層及耐熱處理層，並無特別限定，可由在該技術領域中公知之材料形成。再者，耐化學品處理層由於有時亦作為耐熱處理層而發揮功能，故亦可形成具有耐化學品處理層及耐熱處理層兩者之功能的1個層作為耐化學品處理層及耐熱處理層。 作為耐化學品處理層及/或耐熱處理層，可形成為含有選自由鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵及鉭所組成之群中之1種以上之元素（亦可為金屬、合金、氧化物、氮化物、硫化物等任意之形態）之層。其中，耐化學品處理層較佳為Co-Ni層。耐熱處理層較佳為Ni-Zn層。 The chemical-resistant layer and the heat-resistant layer are not particularly limited and can be formed of materials known in the art. Furthermore, since the chemical-resistant layer sometimes also functions as a heat-resistant layer, a single layer having the functions of both a chemical-resistant layer and a heat-resistant layer can be formed as the chemical-resistant layer and the heat-resistant layer. As a chemical treatment resistant layer and/or heat treatment resistant layer, a layer containing one or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron and tantalum (can also be in any form such as metal, alloy, oxide, nitride, sulfide, etc.) can be formed. Among them, the chemical treatment resistant layer is preferably a Co-Ni layer. The heat treatment resistant layer is preferably a Ni-Zn layer.
耐化學品處理層及耐熱處理層可藉由電鍍而形成。其條件根據所使用之電鍍裝置來調整即可，並無特別限定，使用通常之電鍍裝置形成耐化學品處理層（Co-Ni層）及耐熱處理層（Ni-Zn層）時之條件如下。再者，電鍍既可為1次，亦可進行多次。The chemical treatment resistant layer and the heat treatment resistant layer can be formed by electroplating. The conditions can be adjusted according to the electroplating device used and are not particularly limited. The conditions for forming the chemical treatment resistant layer (Co-Ni layer) and the heat treatment resistant layer (Ni-Zn layer) using a common electroplating device are as follows. In addition, electroplating can be performed once or multiple times.
（耐化學品處理層：Co-Ni層之形成條件） 鍍覆液組成：1～8 g/L之Co，5～20 g/L之Ni 鍍覆液pH：2～3 鍍覆液溫度：40～60℃ 電鍍條件：電流密度1～20 A/dm 2，時間0.3～0.6秒 (Chemical resistant layer: Co-Ni layer formation conditions) Plating solution composition: 1-8 g/L Co, 5-20 g/L Ni Plating solution pH: 2-3 Plating solution temperature: 40-60°C Electroplating conditions: current density 1-20 A/dm 2 , time 0.3-0.6 seconds
（耐熱處理層：Ni-Zn層之形成條件） 鍍覆液組成：1～30 g/L之Ni，1～30 g/L之Zn 鍍覆液pH：2～5 鍍覆液溫度：30～50℃ 電鍍條件：電流密度0.1～10 A/dm 2，時間0.1～5秒 (Heat-resistant treatment layer: Ni-Zn layer formation conditions) Plating solution composition: 1-30 g/L Ni, 1-30 g/L Zn Plating solution pH: 2-5 Plating solution temperature: 30-50°C Electroplating conditions: current density 0.1-10 A/dm 2 , time 0.1-5 seconds
作為鉻酸鹽處理層，並無特別限定，可由在該技術領域中公知之材料形成。 此處，於本說明書中所謂「鉻酸鹽處理層」，意指由含有鉻酸酐、鉻酸、二鉻酸、鉻酸鹽或二鉻酸鹽之液體形成之層。 鉻酸鹽處理層可形成為含有選自由鈷、鐵、鎳、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦所組成之群中之1種以上之元素（亦可為金屬、合金、氧化物、氮化物、硫化物等任意之形態）之層。作為鉻酸鹽處理層之例，可舉經利用鉻酸酐或二鉻酸鉀水溶液處理之鉻酸鹽處理層、經利用含有鉻酸酐或二鉻酸鉀及鋅之處理液處理之鉻酸鹽處理層等。 The chromate treatment layer is not particularly limited and can be formed from materials known in the art. Here, the "chromate treatment layer" in this specification means a layer formed from a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer can be formed as a layer containing one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (it can also be in any form of metal, alloy, oxide, nitride, sulfide, etc.). Examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc, and the like.
鉻酸鹽處理層可藉由浸漬鉻酸鹽處理、電解鉻酸鹽處理等公知方法而形成。其等之條件並無特別限定，例如，形成通常之鉻酸鹽處理層時之條件如下。再者，鉻酸鹽處理既可為1次，亦可進行多次。 鉻酸鹽液組成：1～10 g/L之K 2Cr 2O 7，0.01～10 g/L之Zn 鉻酸鹽液pH：2～5 鉻酸鹽液溫度：30～55℃ 電解條件：電流密度0.1～10 A/dm 2，時間0.1～5秒（電解鉻酸鹽處理之情形時） The chromate treatment layer can be formed by known methods such as immersion chromate treatment and electrolytic chromate treatment. The conditions are not particularly limited. For example, the conditions for forming a normal chromate treatment layer are as follows. Furthermore, the chromate treatment can be performed once or multiple times. Chromate solution composition: 1-10 g/L K 2 Cr 2 O 7 , 0.01-10 g/L Zn Chromate solution pH: 2-5 Chromate solution temperature: 30-55°C Electrolysis conditions: current density 0.1-10 A/dm 2 , time 0.1-5 seconds (in the case of electrolytic chromate treatment)
作為矽烷偶合處理層，並無特別限定，可由在該技術領域中公知之材料形成。 此處，於本說明書中所謂「矽烷偶合處理層」，意指由矽烷偶合劑形成之層。 作為矽烷偶合劑，並無特別限定，可使用在該技術領域中公知者。作為矽烷偶合劑之例，可舉胺基系矽烷偶合劑、環氧系矽烷偶合劑、巰基系矽烷偶合劑、甲基丙烯醯氧基系矽烷偶合劑、乙烯基系矽烷偶合劑、咪唑系矽烷偶合劑、三𠯤系矽烷偶合劑等。該等之中，較佳為胺基系矽烷偶合劑、環氧系矽烷偶合劑。上述矽烷偶合劑可單獨使用或將2種以上組合使用。 作為代表性的矽烷偶合處理層之形成方法，可舉藉由塗佈上述矽烷偶合劑之1～3體積%水溶液，使之乾燥而形成矽烷偶合處理層之方法。 The silane coupling treatment layer is not particularly limited, and can be formed of materials known in the art. Here, the "silane coupling treatment layer" in this specification means a layer formed by a silane coupling agent. The silane coupling agent is not particularly limited, and those known in the art can be used. Examples of silane coupling agents include amino-based silane coupling agents, epoxy-based silane coupling agents, butyl-based silane coupling agents, methacryloyl-based silane coupling agents, vinyl-based silane coupling agents, imidazole-based silane coupling agents, tris-based silane coupling agents, and the like. Among them, amino-based silane coupling agents and epoxy-based silane coupling agents are preferred. The above-mentioned silane coupling agents can be used alone or in combination of two or more. As a representative method for forming a silane coupling treatment layer, there can be cited a method of forming a silane coupling treatment layer by applying a 1 to 3 volume % aqueous solution of the above-mentioned silane coupling agent and drying it.
作為銅箔，並無特別限定，可為電解銅箔或軋製銅箔之任一者。 電解銅箔通常藉由自硫酸銅鍍覆浴使銅電解析出於鈦或不鏽鋼之滾筒上而製造，具有形成於轉筒側之平坦之S面（光澤面）及形成於S面之相反側之M面（消光面）。電解銅箔之M面通常具有微小之凹凸部。又，電解銅箔之S面由於轉印有於研磨時形成之轉筒之研磨條紋，故而具有微小之凹凸部。 軋製銅箔由於在軋製時藉由軋製油而形成油坑，故而於表面具有微小之凹凸部。 The copper foil is not particularly limited and may be either an electrolytic copper foil or a rolled copper foil. Electrolytic copper foil is usually produced by electrolytically depositing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and has a flat S surface (glossy surface) formed on the drum side and an M surface (matte surface) formed on the opposite side of the S surface. The M surface of the electrolytic copper foil usually has minute uneven portions. In addition, the S surface of the electrolytic copper foil has minute uneven portions due to the transfer of grinding stripes of the drum formed during grinding. Rolled copper foil has minute uneven portions on the surface due to the formation of oil pits by rolling oil during rolling.
作為銅箔之材料，並無特別限定，於銅箔為軋製銅箔之情形時，可使用通常被用作印刷配線板之電路圖案之精銅（JIS H3100 合金編號C1100）、無氧銅（JIS H3100 合金編號C1020或JIS H3510 合金編號C1011）等高純度之銅。又，例如，亦可使用摻Sn銅、摻Ag銅、添加有Cr、Zr或Mg等之銅合金、添加有Ni及Si等之卡遜系銅合金之類的銅合金。再者，於本說明書中，「銅箔」之概念亦包含銅合金箔。The material of the copper foil is not particularly limited. When the copper foil is a rolled copper foil, high-purity copper such as refined copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) which are usually used for circuit patterns of printed wiring boards can be used. In addition, for example, copper alloys such as Sn-doped copper, Ag-doped copper, copper alloys with Cr, Zr or Mg added, and Carsonite copper alloys with Ni and Si added can also be used. Furthermore, in this specification, the concept of "copper foil" also includes copper alloy foil.
於銅箔為軋製銅箔之情形時，軋製銅箔亦可具有如下組成：含有99.0質量%以上之Cu及0.003～0.825質量%之選自由P、Ti、Sn、Ni、Be、Zn、In及Mg所組成之群中之1種以上之元素，且其餘部分由不可避免之雜質所組成。又，軋製銅箔亦可具有如下組成：含有99.9質量%以上之Cu及0.0005質量%～0.0220質量%之P，且其餘部分由不可避免之雜質所組成。進而，軋製銅箔亦可具有如下組成：含有99.0質量%以上之Cu，且其餘部分由不可避免之雜質所組成。 又，於銅箔為軋製銅箔之情形時，平均結晶粒徑為0.5～4.0 μm，且於軋製方向之拉伸強度亦可為235～290 MPa。 進而，軋製銅箔亦可具有75%IACS以上之導電率。銅箔之導電率可依據JIS H0505（1975），藉由4端子法，於室溫（25℃）測定。 In the case where the copper foil is a rolled copper foil, the rolled copper foil may also have the following composition: containing 99.0% by mass or more of Cu and 0.003-0.825% by mass of one or more elements selected from the group consisting of P, Ti, Sn, Ni, Be, Zn, In and Mg, and the remainder is composed of inevitable impurities. In addition, the rolled copper foil may also have the following composition: containing 99.9% by mass or more of Cu and 0.0005% by mass or 0.0220% by mass of P, and the remainder is composed of inevitable impurities. Furthermore, the rolled copper foil may also have the following composition: containing 99.0% by mass or more of Cu, and the remainder is composed of inevitable impurities. In addition, when the copper foil is a rolled copper foil, the average crystal grain size is 0.5 to 4.0 μm, and the tensile strength in the rolling direction can also be 235 to 290 MPa. Furthermore, the rolled copper foil can also have a conductivity of 75% IACS or more. The conductivity of the copper foil can be measured at room temperature (25°C) by a 4-terminal method in accordance with JIS H0505 (1975).
銅箔之厚度並無特別限定，例如可設為1～1000 μm、1～500 μm、1～300 μm、3～100 μm、5～70 μm、6～35 μm或9～18 μm。The thickness of the copper foil is not particularly limited, and may be, for example, 1 to 1000 μm, 1 to 500 μm, 1 to 300 μm, 3 to 100 μm, 5 to 70 μm, 6 to 35 μm, or 9 to 18 μm.
具有如上述之構成之表面處理銅箔可依據於該技術領域中公知之方法來製造。此處，表面處理層之Vmp等表面性狀參數可藉由調整表面處理層之形成條件，尤其是上述粗化處理層之形成條件等來控制。The surface treated copper foil having the above-mentioned structure can be manufactured according to the method known in the art. Here, the surface property parameters such as Vmp of the surface treatment layer can be controlled by adjusting the formation conditions of the surface treatment layer, especially the formation conditions of the above-mentioned roughening treatment layer.
本發明之實施形態之表面處理銅箔由於將表面處理層之Vmp控制為0.022～0.060 μm 3/μm 2，故而可提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性。 The surface treated copper foil of the embodiment of the present invention can improve the adhesion with the resin substrate, especially the resin substrate suitable for high frequency application, because the Vmp of the surface treated layer is controlled to 0.022-0.060 μm 3 /μm 2 .
本發明之實施形態之覆銅積層板具備上述表面處理銅箔及接著於該表面處理銅箔之表面處理層之樹脂基材。 該覆銅積層板可藉由在上述表面處理銅箔之表面處理層接著樹脂基材而製造。 作為樹脂基材，並無特別限定，可使用在該技術領域中公知者。作為樹脂基材之例，可舉紙基材酚樹脂、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃布/紙複合基材環氧樹脂、玻璃布/玻璃不織布複合基材環氧樹脂、玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺樹脂、液晶聚合物、氟樹脂等。該等之中，樹脂基材較佳為聚醯亞胺樹脂。 又，作為特別適合於高頻用途之樹脂基材，可舉由低介電材料形成之樹脂基材。作為低介電材料之例，可舉液晶聚合物、低介電聚醯亞胺、氟樹脂等。低介電材料例如亦可為於1 MHz具有3.5以下之介電常數之材料。作為適合於高頻用途之低介電材料，亦可為於30 GHz具有3.4以下之介電常數之材料。 The copper-clad laminate of the embodiment of the present invention has the surface-treated copper foil and a resin substrate connected to the surface-treated layer of the surface-treated copper foil. The copper-clad laminate can be manufactured by connecting the resin substrate to the surface-treated layer of the surface-treated copper foil. The resin substrate is not particularly limited, and those known in the technical field can be used. Examples of the resin substrate include paper-based phenolic resin, paper-based epoxy resin, synthetic fiber cloth-based epoxy resin, glass cloth/paper composite-based epoxy resin, glass cloth/glass non-woven cloth composite-based epoxy resin, glass cloth-based epoxy resin, polyester film, polyimide resin, liquid crystal polymer, fluororesin, etc. Among them, the resin substrate is preferably a polyimide resin. In addition, as a resin substrate particularly suitable for high-frequency use, a resin substrate formed of a low-dielectric material can be cited. Examples of low-dielectric materials include liquid crystal polymers, low-dielectric polyimides, fluororesins, etc. The low-dielectric material can also be a material having a dielectric constant of 3.5 or less at 1 MHz. As a low-dielectric material suitable for high-frequency use, a material having a dielectric constant of 3.4 or less at 30 GHz can also be cited.
作為表面處理銅箔與樹脂基材之接著方法，並無特別限定，可依據在該技術領域中公知之方法來進行。例如，使表面處理銅箔與樹脂基材積層且進行熱壓接即可。 以上述方式製造之覆銅積層板可用於製造印刷配線板。 There is no particular limitation on the method for bonding the surface-treated copper foil and the resin substrate, and the method can be performed according to a method known in the art. For example, the surface-treated copper foil and the resin substrate can be laminated and heat-pressed. The copper-clad laminate manufactured in the above manner can be used to manufacture printed wiring boards.
本發明之實施形態之覆銅積層板由於使用上述表面處理銅箔，故而可提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性。The copper-clad laminate of the embodiment of the present invention uses the surface-treated copper foil, so the adhesion with the resin substrate, especially the resin substrate suitable for high-frequency use, can be improved.
本發明之實施形態之印刷配線板，具備對上述覆銅積層板之表面處理銅箔進行蝕刻而形成之電路圖案。 該印刷配線板可藉由對上述覆銅積層板之表面處理銅箔進行蝕刻形成電路圖案而製造。 作為電路圖案之形成方法，並無特別限定，可使用減成法、半加成法等公知方法。其中，電路圖案之形成方法較佳為減成法。 The printed wiring board of the embodiment of the present invention has a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate. The printed wiring board can be manufactured by etching the surface-treated copper foil of the copper-clad laminate to form a circuit pattern. There is no particular limitation on the method for forming the circuit pattern, and known methods such as a subtractive method and a semi-additive method can be used. Among them, the method for forming the circuit pattern is preferably a subtractive method.
於藉由減成法而製造印刷配線板之情形時，較佳以如下方式進行。首先，藉由在覆銅積層板之表面處理銅箔之表面塗佈阻劑，進行曝光及顯影，而形成規定之阻劑圖案。其次，藉由蝕刻去除未形成阻劑圖案之部分（即，多餘部分）之表面處理銅箔而形成電路圖案。最後，去除表面處理銅箔上之阻劑圖案。 再者，該減成法中之各種條件並無特別限定，可依據在該技術領域中公知之條件來進行。 When a printed wiring board is manufactured by a subtractive method, it is preferably carried out as follows. First, a resist is applied to the surface of the surface-treated copper foil of the copper-clad laminate, and then exposed and developed to form a prescribed resist pattern. Secondly, a circuit pattern is formed by etching away the portion of the surface-treated copper foil where the resist pattern is not formed (i.e., the excess portion). Finally, the resist pattern on the surface-treated copper foil is removed. Furthermore, the various conditions in the subtractive method are not particularly limited and can be carried out according to conditions known in the technical field.
本發明之實施形態之印刷配線板由於使用上述覆銅積層板，故而樹脂基材尤其是適合於高頻用途之樹脂基材與電路圖案之間之接著性優異。 [實施例] Since the printed wiring board of the embodiment of the present invention uses the above-mentioned copper-clad laminate, the adhesion between the resin substrate, especially the resin substrate suitable for high-frequency use, and the circuit pattern is excellent. [Example]
以下，藉由實施例對本發明之實施形態更具體地進行說明，但是本發明並不受該等實施例任何限定。Hereinafter, the embodiments of the present invention will be described in more detail, but the present invention is not limited to these embodiments.
（實施例1） 準備厚度12 μm之軋製銅箔（JX金屬股份有限公司製造之HG箔）。於將該銅箔之兩面脫脂及酸洗後，藉由在一面（以下，稱為「第1面」）依次形成粗化處理層、耐化學品處理層（Co-Ni層）、耐熱處理層（Ni-Zn層）、鉻酸鹽處理層及矽烷偶合處理層作為表面處理層，而獲得表面處理銅箔。 各處理層之形成條件如下。 （1）粗化處理層/第1面 ＜1次粗化粒子之形成條件＞ 鍍覆液組成：12 g/L之Cu，50 g/L之硫酸，5 ppm之鎢（來自鎢酸鈉二水合物） 鍍覆液溫度：27℃ 電鍍條件：電流密度39.5 A/dm 2，時間1.2秒 電鍍處理次數：2次 (Example 1) A rolled copper foil (HG foil manufactured by JX Metal Co., Ltd.) with a thickness of 12 μm was prepared. After both sides of the copper foil were degreased and pickled, a roughening treatment layer, a chemical resistance treatment layer (Co-Ni layer), a heat resistance treatment layer (Ni-Zn layer), a chromate treatment layer, and a silane coupling treatment layer were sequentially formed on one side (hereinafter referred to as the "first side") as surface treatment layers to obtain a surface-treated copper foil. The formation conditions of each treatment layer are as follows. (1) Roughening layer/1st surface <1st roughening particle formation conditions> Plating solution composition: 12 g/L Cu, 50 g/L sulfuric acid, 5 ppm tungsten (from sodium tungstate dihydrate) Plating solution temperature: 27°C Electroplating conditions: current density 39.5 A/dm 2 , time 1.2 seconds Electroplating treatment times: 2 times
＜覆蓋鍍覆層之形成條件＞ 鍍覆液組成：20 g/L之Cu，100 g/L之硫酸 鍍覆液溫度：50℃ 電鍍條件：電流密度9.6 A/dm 2，時間1.8秒 電鍍處理次數：2次 <Conditions for forming the coating> Coating liquid composition: 20 g/L Cu, 100 g/L sulfuric acid Coating liquid temperature: 50°C Electroplating conditions: Current density 9.6 A/dm 2 , time 1.8 seconds Electroplating treatment times: 2 times
＜2次粗化粒子之形成條件＞ 鍍覆液組成：15.5 g/L之Cu，7.5 g/L之Co，9.5 g/L之Ni 鍍覆液溫度：50℃ 電鍍條件：電流密度33.3 A/dm 2，時間0.55秒 電鍍處理次數：2次 <Conditions for forming the second roughened particles> Plating solution composition: 15.5 g/L Cu, 7.5 g/L Co, 9.5 g/L Ni Plating solution temperature: 50°C Electroplating conditions: current density 33.3 A/dm 2 , time 0.55 seconds Electroplating treatment times: 2 times
（2）耐化學品處理層/第1面 ＜Co-Ni層之形成條件＞ 鍍覆液組成：3 g/L之Co，13 g/L之Ni 鍍覆液pH：2.0 鍍覆液溫度：50℃ 電鍍條件：電流密度4.5 A/dm 2，時間0.48秒 電鍍處理次數：1次 (2) Chemical resistance layer/1st surface <Co-Ni layer formation conditions> Plating solution composition: 3 g/L Co, 13 g/L Ni Plating solution pH: 2.0 Plating solution temperature: 50°C Electroplating conditions: current density 4.5 A/dm 2 , time 0.48 seconds Electroplating treatment times: 1 time
（3）耐熱處理層/第1面 ＜Ni-Zn層之形成條件＞ 鍍覆液組成：23.5 g/L之Ni，4.5 g/L之Zn 鍍覆液pH：3.6 鍍覆液溫度：40℃ 電鍍條件：電流密度0.7 A/dm 2，時間0.90秒 電鍍處理次數：1次 (3) Heat-resistant treatment layer/1st surface <Conditions for forming the Ni-Zn layer> Plating solution composition: 23.5 g/L Ni, 4.5 g/L Zn Plating solution pH: 3.6 Plating solution temperature: 40°C Electroplating conditions: Current density 0.7 A/dm 2 , time 0.90 seconds Electroplating treatment times: 1 time
（4）鉻酸鹽處理層/第1面 ＜電解鉻酸鹽處理層之形成條件＞ 鉻酸鹽液組成：3 g/L之K 2Cr 2O 7，0.33 g/L之Zn 鉻酸鹽液pH：3.7 鉻酸鹽液溫度：55℃ 電解條件：電流密度1.2 A/dm 2，時間0.90秒 鉻酸鹽處理次數：2次 (4) Chromate treatment layer/1st surface <Conditions for forming the electrolytic chromate treatment layer> Chromate solution composition: 3 g/L K 2 Cr 2 O 7 , 0.33 g/L Zn Chromate solution pH: 3.7 Chromate solution temperature: 55°C Electrolysis conditions: Current density 1.2 A/dm 2 , time 0.90 seconds Chromate treatment times: 2 times
（5）矽烷偶合處理層/第1面 藉由塗佈N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷之1.2體積%水溶液，使之乾燥而形成矽烷偶合處理層。 (5) Silane coupling treatment layer/first surface A silane coupling treatment layer is formed by applying a 1.2 volume % aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and drying it.
（實施例2） 於1次粗化粒子之形成條件中，將電鍍條件變更為電流密度43.7 A/dm 2，及於覆蓋鍍覆層之形成條件中，將電鍍條件變更為電流密度12.3 A/dm 2、時間1.8秒，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 2) A surface treated copper foil was obtained under the same conditions as in Example 1 except that the electroplating conditions for forming the primary roughened particles were changed to a current density of 43.7 A/dm 2 and the electroplating conditions for forming the covering coating were changed to a current density of 12.3 A/dm 2 and a time of 1.8 seconds.
（實施例3） 於第1面之耐熱處理層（Ni-Zn層）之形成條件中，將電鍍條件變更為電流密度0.5 A/dm 2、時間0.90秒，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 3) A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the electroplating conditions were changed to a current density of 0.5 A/dm 2 and a time of 0.90 seconds in forming the heat-resistant treatment layer (Ni—Zn layer) on the first surface.
（實施例4） 於第1面中不形成耐熱處理層，並且於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 4) A surface-treated copper foil was obtained under the same conditions as in Example 1 except that no heat-resistant layer was formed on the first surface and the electroplating conditions for forming the chemical-resistant layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例5） 於第1面中不形成耐熱處理層，且於1次粗化粒子之形成條件中，將電鍍條件變更為電流密度31.4 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 5) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of the primary roughened particles were changed to a current density of 31.4 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例6） 於第1面中不形成耐熱處理層，且於1次粗化粒子之形成條件中，將電鍍條件變更為電流密度35.2 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 6) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of the primary roughened particles were changed to a current density of 35.2 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例7） 於第1面中不形成耐熱處理層，且於1次粗化粒子之形成條件中，將電鍍條件變更為電流密度42.9 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 7) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of the primary roughened particles were changed to a current density of 42.9 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例8） 於第1面中不形成耐熱處理層，且於1次粗化粒子之形成條件中，將電鍍條件變更為電流密度46.7 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 8) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of the primary roughened particles were changed to a current density of 46.7 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例9） 於第1面中不形成耐熱處理層，且於2次粗化粒子之形成條件中，將電鍍條件變更為電流密度28.9 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 9) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of secondary roughened particles were changed to a current density of 28.9 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例10） 於第1面中不形成耐熱處理層，且於2次粗化粒子之形成條件中，將電鍍條件變更為電流密度37.7 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 10) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of secondary roughened particles were changed to a current density of 37.7 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（實施例11） 於第1面中不形成耐熱處理層，且於2次粗化粒子之形成條件中，將電鍍條件變更為電流密度42.1 A/dm 2，及於耐化學品處理層（Co-Ni層）之形成條件中，將電鍍條件變更為電流密度3.0 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 11) A surface treated copper foil was obtained under the same conditions as in Example 1 except that no heat resistant treatment layer was formed on the first surface, the electroplating conditions in the formation of secondary roughened particles were changed to a current density of 42.1 A/dm 2 , and the electroplating conditions in the formation of the chemical resistant treatment layer (Co-Ni layer) were changed to a current density of 3.0 A/dm 2 .
（比較例1） 準備厚度12 μm之軋製銅箔（JX金屬股份有限公司製造之HG箔）。於將該銅箔之兩面脫脂及酸洗後，於一面（第1面）依次形成粗化處理層、耐化學品處理層（Co-Ni層）、耐熱處理層（Ni-Zn層）、鉻酸鹽處理層及矽烷偶合處理層作為表面處理層，由此獲得表面處理銅箔。 各處理層之形成條件如下。 （1）粗化處理層/第1面 ＜1次粗化粒子之形成條件＞ 鍍覆液組成：12 g/L之Cu，50 g/L之硫酸，5 ppm之鎢（來自鎢酸鈉二水合物） 鍍覆液溫度：27℃ 電鍍條件：電流密度46 A/dm 2，時間1.2秒 電鍍處理次數：2次 (Comparative Example 1) A rolled copper foil (HG foil manufactured by JX Metal Co., Ltd.) with a thickness of 12 μm was prepared. After both sides of the copper foil were degreased and pickled, a roughening treatment layer, a chemical resistance treatment layer (Co-Ni layer), a heat resistance treatment layer (Ni-Zn layer), a chromate treatment layer, and a silane coupling treatment layer were sequentially formed on one side (the first side) as surface treatment layers, thereby obtaining a surface-treated copper foil. The formation conditions of each treatment layer are as follows. (1) Roughening layer/1st surface <1st roughening particle formation conditions> Plating solution composition: 12 g/L Cu, 50 g/L sulfuric acid, 5 ppm tungsten (from sodium tungstate dihydrate) Plating solution temperature: 27°C Electroplating conditions: current density 46 A/dm 2 , time 1.2 seconds Electroplating treatment times: 2 times
＜覆蓋鍍覆層之形成條件＞ 鍍覆液組成：20 g/L之Cu，100 g/L之硫酸 鍍覆液溫度：50℃ 電鍍條件：電流密度9.6 A/dm 2，時間1.8秒 電鍍處理次數：2次 <Conditions for forming the coating> Coating liquid composition: 20 g/L Cu, 100 g/L sulfuric acid Coating liquid temperature: 50°C Electroplating conditions: Current density 9.6 A/dm 2 , time 1.8 seconds Electroplating treatment times: 2 times
（2）耐化學品處理層/第1面 ＜Co-Ni層之形成條件＞ 鍍覆液組成：3 g/L之Co，13 g/L之Ni 鍍覆液pH：2.0 鍍覆液溫度：50℃ 電鍍條件：電流密度4.5 A/dm 2，時間0.48秒 電鍍處理次數：1次 (2) Chemical resistance layer/1st surface <Co-Ni layer formation conditions> Plating solution composition: 3 g/L Co, 13 g/L Ni Plating solution pH: 2.0 Plating solution temperature: 50°C Electroplating conditions: Current density 4.5 A/dm 2 , time 0.48 seconds Electroplating treatment times: 1 time
（3）耐熱處理層/第1面 ＜Ni-Zn層之形成條件＞ 鍍覆液組成：23.5 g/L之Ni，4.5 g/L之Zn 鍍覆液pH：3.6 鍍覆液溫度：40℃ 電鍍條件：電流密度0.9 A/dm 2，時間0.90秒 電鍍處理次數：1次 (3) Heat-resistant treatment layer/1st surface <Conditions for forming the Ni-Zn layer> Plating solution composition: 23.5 g/L Ni, 4.5 g/L Zn Plating solution pH: 3.6 Plating solution temperature: 40°C Electroplating conditions: Current density 0.9 A/dm 2 , time 0.90 seconds Electroplating treatment times: 1 time
（4）鉻酸鹽處理層/第1面 ＜電解鉻酸鹽處理層之形成條件＞ 鉻酸鹽液組成：3 g/L之K 2Cr 2O 7，0.33 g/L之Zn 鉻酸鹽液pH：3.7 鉻酸鹽液溫度：55℃ 電解條件：電流密度1.2 A/dm 2，時間0.90秒 鉻酸鹽處理次數：2次 (4) Chromate treatment layer/1st surface <Conditions for forming the electrolytic chromate treatment layer> Chromate solution composition: 3 g/L K 2 Cr 2 O 7 , 0.33 g/L Zn Chromate solution pH: 3.7 Chromate solution temperature: 55°C Electrolysis conditions: Current density 1.2 A/dm 2 , time 0.90 seconds Chromate treatment times: 2 times
（5）矽烷偶合處理層/第1面 藉由塗佈N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷之1.2體積%水溶液，使之乾燥而形成矽烷偶合處理層。 (5) Silane coupling treatment layer/first surface A silane coupling treatment layer is formed by applying a 1.2 volume % aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and drying it.
對在上述實施例及比較例中所得之表面處理銅箔，進行下述特性評價。 ＜表面處理層（第1面）之Vmp、Spk及Sdr＞ 使用奧林巴斯股份有限公司製造之雷射顯微鏡（LEXT OLS4000）進行圖像拍攝。所拍攝之圖像之解析係使用奧林巴斯股份有限公司製造之雷射顯微鏡（LEXT OLS4100）之解析軟體來進行。表面處理層之Vmp、Spk及Sdr之測定，則依據ISO 25178-2：2012來進行。又，該等之測定結果係將於任意10處所測定之值之平均值作為測定結果。測定時之溫度設為23～25℃。 雷射顯微鏡及解析軟體中之主要的設定條件如下述。 物鏡：MPLAPON50XLEXT（倍率：50倍，數值孔徑：0.95，液浸類型：空氣，機械性鏡筒長度：∞，覆蓋玻璃厚度：0，視野數：FN18） 光學變焦倍率：1倍 掃描模式：XYZ高精度（高度解析度：60 nm，輸入資料之像素數：1024×1024） 輸入圖像尺寸[像素數]：橫257 μm×縱258 μm[1024×1024] （由於在橫向進行測定，故而評價長度相當於257 μm） DIC：關閉 Multilayer：關閉 雷射強度：100 偏移：0 共焦水平：0 光束直徑光圈：關閉 圖像平均：1次 雜訊降低：打開 亮度不均修正：打開 光學性噪音濾波器：打開 截止：λc＝200 μm，無λs及λf 濾波器：高斯濾波器 雜訊去除：測定前處理 表面(傾斜)修正：實施 亮度：以成為30～50之範圍之方式進行調整 亮度係應根據測定對象之色調而適當設定之值。上述設定係適合於測定L＊為-69～-10、a＊為2～32、b＊為2～21之表面處理銅箔的表面時之值。 The following characteristics were evaluated for the surface treated copper foil obtained in the above-mentioned embodiment and comparative example. <Vmp, Spk and Sdr of the surface treated layer (first surface)> Images were taken using a laser microscope (LEXT OLS4000) manufactured by Olympus Corporation. The images taken were analyzed using the analysis software of a laser microscope (LEXT OLS4100) manufactured by Olympus Corporation. The Vmp, Spk and Sdr of the surface treated layer were measured in accordance with ISO 25178-2:2012. In addition, the measurement results were the average values of the values measured at any 10 locations. The temperature during the measurement was set to 23-25°C. The main setting conditions in the laser microscope and analysis software are as follows. Objective lens: MPLAPON50XLEXT (magnification: 50x, numerical aperture: 0.95, immersion type: air, mechanical barrel length: ∞, cover glass thickness: 0, field number: FN18) Optical zoom ratio: 1x Scanning mode: XYZ high precision (height resolution: 60 nm, number of pixels of input data: 1024×1024) Input image size [number of pixels]: horizontal 257 μm × vertical 258 μm [1024×1024] (Since the measurement is performed in the horizontal direction, the evaluation length is equivalent to 257 μm) DIC: Off Multilayer: Off Laser intensity: 100 Offset: 0 Confocal level: 0 Beam diameter aperture: Off Image averaging: 1 time Noise reduction: On Brightness unevenness correction: On Optical noise filter: On Cutoff: λc=200 μm, no λs and λf Filter: Gaussian filter Noise removal: Pre-measurement processing Surface (tilt) correction: Implemented Brightness: Adjusted to a range of 30 to 50 Brightness is a value that should be appropriately set according to the color tone of the object being measured. The above settings are suitable for measuring the surface of surface-treated copper foil with L* of -69 to -10, a* of 2 to 32, and b* of 2 to 21.
＜測定對象之色調之測定＞ 使用HunterLab公司製造之MiniScan（註冊商標）EZ Model 4000L作為測定器，依據JIS Z8730：2009來進行CIE L＊a＊b＊表色系統之L＊、a＊及b＊之測定。具體而言，將在上述實施例及比較例所得之表面處理銅箔之測定對象面壓抵於測定器之感光部，以使光不自外部進入之方式進行測定。又，L＊、a＊及b＊之測定係基於JIS Z8722：2009之幾何條件C來進行。再者，測定器之主要條件如下述。 光學系統：d/8°，積分球尺寸：63.5 mm，觀察光源：D65 測定方式：反射 照明直徑：25.4 mm 測定直徑：20.0 mm 測定波長/間隔：400～700 nm/10nm 光源：脈衝氙氣燈/1發光/測定 追蹤能力標準：基於CIE 44及ASTM E259，依據美國標準技術研究所（NIST）校正 標準觀察者：10° 又，成為測定基準之白色瓷磚，係使用下述物體顏色者。 於經以D65/10°測定之情形時，CIE XYZ表色系統中之值為X：81.90，Y：87.02，Z：93.76 <Measurement of the color tone of the measurement object> MiniScan (registered trademark) EZ Model 4000L manufactured by HunterLab was used as a measuring instrument to measure L*, a* and b* of the CIE L*a*b* colorimetric system in accordance with JIS Z8730:2009. Specifically, the surface-treated copper foil obtained in the above-mentioned embodiment and comparative example was pressed against the photosensitive part of the measuring instrument to prevent light from entering from the outside. In addition, the measurement of L*, a* and b* was performed based on the geometric condition C of JIS Z8722:2009. In addition, the main conditions of the measuring instrument are as follows. Optical system: d/8°, integrating sphere size: 63.5 mm, observation light source: D65 Measurement method: reflection Illumination diameter: 25.4 mm Measurement diameter: 20.0 mm Measurement wavelength/interval: 400-700 nm/10nm Light source: pulsed xenon lamp/1 emission/measurement Tracking capability standard: Based on CIE 44 and ASTM E259, calibrated according to the National Institute of Standards and Technology (NIST) Standard observer: 10° In addition, the white tile used as the measurement standard is the one using the following object color. When measured at D65/10°, the values in the CIE XYZ colorimetric system are X: 81.90, Y: 87.02, Z: 93.76
＜剝離強度＞ 於將表面處理銅箔（第1面側）與由低介電材料形成之樹脂基材貼合之後，於MD方向（軋製銅箔之長邊方向）形成寬度3 mm之電路。電路之形成按照通常之方法來實施。其次，依據JIS C6471：1995來測定將電路（表面處理銅箔）相對於樹脂基材之表面以50 mm/分鐘之速度於180°方向，即MD方向剝離時之強度（MD180° 剝離強度）。測定進行5次，將其平均值作為剝離強度之結果。若剝離強度為0.60 kgf/cm以上，則可謂電路（表面處理銅箔）與樹脂基材之接著性良好。 <Peel strength> After bonding the surface treated copper foil (first side) to a resin substrate formed of a low dielectric material, a circuit with a width of 3 mm is formed in the MD direction (long side direction of the rolled copper foil). The circuit formation is carried out according to the usual method. Next, the strength (MD180° peel strength) when the circuit (surface treated copper foil) is peeled off from the surface of the resin substrate at a speed of 50 mm/min in the 180° direction, i.e., the MD direction, is measured in accordance with JIS C6471:1995. The measurement is performed 5 times, and the average value is taken as the peel strength result. If the peel strength is 0.60 kgf/cm or more, it can be said that the adhesion between the circuit (surface treated copper foil) and the resin substrate is good.
將上述特性評價之結果示於表1中。The results of the above-mentioned characteristic evaluation are shown in Table 1.
[表1]
如表1所示，表面處理層之Vmp處於0.022～0.060 μm 3/μm 2之範圍內的實施例1～11之表面處理銅箔，相較於表面處理層之Vmp處於規定之範圍外的比較例1，剝離強度高。 As shown in Table 1, the surface treated copper foils of Examples 1 to 11, in which the Vmp of the surface treated layer is in the range of 0.022 to 0.060 μm 3 /μm 2 , have higher peeling strength than Comparative Example 1, in which the Vmp of the surface treated layer is outside the prescribed range.
其次，調查表面處理層中之Zn附著量對焊料耐熱性之影響。Secondly, the effect of the amount of Zn deposited in the surface treatment layer on the heat resistance of the solder was investigated.
（實施例12） 於第1面中不形成耐熱處理層，且於鉻酸鹽處理層之形成條件中，在不施加電流的情況下進行浸漬，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 12) A surface-treated copper foil was obtained under the same conditions as in Example 1 except that no heat-resistant treatment layer was formed on the first surface and the immersion was performed without applying a current in the formation conditions of the chromate treatment layer.
（實施例13） 於第1面中不形成耐熱處理層，且於鉻酸鹽處理層之形成條件中，將電鍍條件變更為電流密度0.64 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 13) A surface-treated copper foil was obtained under the same conditions as in Example 1 except that no heat-resistant treatment layer was formed on the first surface and the electroplating conditions were changed to a current density of 0.64 A/dm 2 in the formation conditions of the chromate treatment layer.
（實施例14） 於第1面中不形成耐熱處理層，且於鉻酸鹽處理層之形成條件中，將電鍍條件變更為電流密度1.4 A/dm 2，除此以外利用與實施例1相同之條件而獲得表面處理銅箔。 (Example 14) A surface-treated copper foil was obtained under the same conditions as in Example 1 except that no heat-resistant treatment layer was formed on the first surface and the electroplating conditions for forming the chromate treatment layer were changed to a current density of 1.4 A/dm 2 .
對在上述實施例中所得之表面處理銅箔，與上述相同地進行Vmp、Spk、Sdr及剝離強度之測定，且進行下述評價。For the surface treated copper foil obtained in the above embodiment, Vmp, Spk, Sdr and peeling strength were measured in the same manner as above, and the following evaluation was performed.
＜表面處理層（第1面）中之Zn附著量之測定＞ 表面處理層（第1面）中之Zn附著量，係藉由將表面處理層（第1面）溶解於20質量%之硝酸，使用原子吸光分光光度計（VARIAN公司製造，AA240FS），以原子吸光法進行定量分析而測定。 <Measurement of the amount of Zn attached to the surface treatment layer (first surface)> The amount of Zn attached to the surface treatment layer (first surface) was measured by dissolving the surface treatment layer (first surface) in 20 mass % nitric acid and using an atomic absorption spectrophotometer (manufactured by VARIAN, AA240FS) to perform quantitative analysis by atomic absorption method.
＜焊料耐熱性＞ 於將表面處理銅箔與由低介電材料形成之樹脂基材貼合後，以該表面處理銅箔之表面成為25 mm×25 mm之方式進行蝕刻。電路之形成按照通常之方法實施。其次，將樣品放入恆溫恆濕機內，以溫度85℃，相對濕度85%保持48小時。然後，使樣品浮於收容有規定溫度之焊料之焊料槽30秒後取出，以目視確認於樣品之電路是否產生氣泡。當在樣品之電路未產生氣泡之情形時，準備其他樣品，提高焊料槽之焊料之溫度，再次確認於樣品之電路是否產生氣泡。重複該操作直至在樣品之電路產生氣泡。由在樣品之電路未產生氣泡之焊料的最高溫度來表示此評價之結果。若在樣品之電路未產生氣泡之焊料的最高溫度為290℃以上，則可謂焊料耐熱性良好。 <Solder Heat Resistance> After bonding the surface treated copper foil to a resin substrate formed of a low dielectric material, the surface of the surface treated copper foil is etched in a manner such that it becomes 25 mm × 25 mm. The circuit formation is carried out according to the usual method. Next, the sample is placed in a constant temperature and humidity machine and maintained at a temperature of 85°C and a relative humidity of 85% for 48 hours. Then, the sample is floated in a solder tank containing solder at a specified temperature for 30 seconds and then taken out to visually confirm whether bubbles are generated in the circuit of the sample. When bubbles are not generated in the circuit of the sample, prepare other samples, increase the temperature of the solder in the solder tank, and confirm again whether bubbles are generated in the circuit of the sample. Repeat this operation until bubbles are generated in the circuit of the sample. The result of this evaluation is expressed by the highest temperature of the solder without bubbles in the sample circuit. If the highest temperature of the solder without bubbles in the sample circuit is above 290℃, the solder heat resistance is considered good.
[表2]
如表2所示，實施例12～14之表面處理銅箔與實施例1～11之表面處理銅箔相同地，由於表面處理層之Vmp處於0.022～0.060 μm 3/μm 2之範圍內，故而與比較例1之表面處理銅箔相比，剝離強度高。又，實施例12～14之表面處理銅箔由於表面處理層中之Zn附著量為6～200 μm/dm 2，故而焊料耐熱性亦良好。尤其是Zn附著量為82～200 μm/dm 2之實施例13及14，焊料耐熱性特別優異。 As shown in Table 2, the surface treated copper foils of Examples 12 to 14 have a Vmp of the surface treated layer in the range of 0.022 to 0.060 μm 3 /μm 2 , similar to the surface treated copper foils of Examples 1 to 11, and therefore have higher peel strength than the surface treated copper foil of Comparative Example 1. In addition, the surface treated copper foils of Examples 12 to 14 have good solder heat resistance because the Zn adhesion amount in the surface treated layer is 6 to 200 μm/dm 2. In particular, Examples 13 and 14, in which the Zn adhesion amount is 82 to 200 μm/dm 2 , have particularly excellent solder heat resistance.
根據以上之結果可知，若根據本發明之實施形態，可提供一種表面處理銅箔，其能夠提高與樹脂基材，尤其是適合於高頻用途之樹脂基材之接著性。又，若根據本發明之實施形態，可提供一種覆銅積層板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與表面處理銅箔之間之接著性優異。進而，若根據本發明之實施形態，可提供一種印刷配線板，其中，樹脂基材尤其是適合於高頻用途之樹脂基材與電路圖案之間之接著性優異。According to the above results, it can be seen that according to the implementation form of the present invention, a surface-treated copper foil can be provided, which can improve the adhesion with a resin substrate, especially a resin substrate suitable for high-frequency use. In addition, according to the implementation form of the present invention, a copper-clad laminate can be provided, wherein the adhesion between the resin substrate, especially the resin substrate suitable for high-frequency use and the surface-treated copper foil is excellent. Furthermore, according to the implementation form of the present invention, a printed wiring board can be provided, wherein the adhesion between the resin substrate, especially the resin substrate suitable for high-frequency use and the circuit pattern is excellent.
因此，本發明之實施形態可設為以下之態樣。 [1] 一種表面處理銅箔，其具有銅箔及形成於該銅箔之至少一面之表面處理層， 該表面處理層之山部之實體部體積Vmp為0.022～0.060 μm 3/μm 2。 [2] 如[1]記載之表面處理銅箔，其中，該山部之實體部體積Vmp為0.030～0.055 μm 3/μm 2。 [3] 如[1]記載之表面處理銅箔，其中，該山部之實體部體積Vmp為0.035～0.046 μm 3/μm 2。 [4] 如[1]至[3]中任一項記載之表面處理銅箔，其中，該山部之平均高度Spk為0.42～1.00 μm。 [5] 如[1]至[3]中任一項記載之表面處理銅箔，其中，該山部之平均高度Spk為0.60～0.95 μm。 [6] 如[1]至[3]中任一項記載之表面處理銅箔，其中，該山部之平均高度Spk為0.71～0.90 μm。 [7] 如[1]至[6]中任一項記載之表面處理銅箔，其中，該表面處理層之展開界面面積率Sdr為40～130%。 [8] 如[1]至[6]中任一項記載之表面處理銅箔，其中，該表面處理層之展開界面面積率Sdr為53～120%。 [9] 如[1]至[6]中任一項記載之表面處理銅箔，其中，該表面處理層之展開界面面積率Sdr為62～110%。 [10] 如[1]至[9]中任一項記載之表面處理銅箔，其中，該表面處理層中之Zn附著量為6～200 μm/dm 2。 [11] 如[10]記載之表面處理銅箔，其中，該表面處理層中之Zn附著量為82～200 μm/dm 2。 [12] 如[1]至[11]中任一項記載之表面處理銅箔，其中，該表面處理層含有粗化處理層。 [13] 一種覆銅積層板，其具備如[1]至[12]中任一項記載之表面處理銅箔及接著於該表面處理銅箔之該表面處理層之樹脂基材。 [14] 一種印刷配線板，其具備對如[13]記載之覆銅積層板之該表面處理銅箔進行蝕刻而形成之電路圖案。 Therefore, the embodiment of the present invention can be set as follows. [1] A surface-treated copper foil, comprising a copper foil and a surface-treated layer formed on at least one side of the copper foil, wherein the volume Vmp of the mountain portion of the surface-treated layer is 0.022 to 0.060 μm 3 /μm 2 . [2] The surface-treated copper foil as described in [1], wherein the volume Vmp of the mountain portion is 0.030 to 0.055 μm 3 /μm 2 . [3] The surface-treated copper foil as described in [1], wherein the volume Vmp of the mountain portion is 0.035 to 0.046 μm 3 /μm 2 . [4] A surface-treated copper foil as described in any one of [1] to [3], wherein the average height Spk of the peaks is 0.42 to 1.00 μm. [5] A surface-treated copper foil as described in any one of [1] to [3], wherein the average height Spk of the peaks is 0.60 to 0.95 μm. [6] A surface-treated copper foil as described in any one of [1] to [3], wherein the average height Spk of the peaks is 0.71 to 0.90 μm. [7] A surface-treated copper foil as described in any one of [1] to [6], wherein the surface treatment layer has an open interface area ratio Sdr of 40 to 130%. [8] The surface treated copper foil as described in any one of [1] to [6], wherein the surface treatment layer has an open interface area ratio Sdr of 53 to 120%. [9] The surface treated copper foil as described in any one of [1] to [6], wherein the surface treatment layer has an open interface area ratio Sdr of 62 to 110%. [10] The surface treated copper foil as described in any one of [1] to [9], wherein the Zn adhesion amount in the surface treatment layer is 6 to 200 μm/dm 2. [11] The surface treated copper foil as described in [10], wherein the Zn adhesion amount in the surface treatment layer is 82 to 200 μm/dm 2 . [12] A surface treated copper foil as described in any one of [1] to [11], wherein the surface treated layer includes a roughening treatment layer. [13] A copper clad laminate comprising a surface treated copper foil as described in any one of [1] to [12] and a resin substrate of the surface treated copper foil connected to the surface treated copper foil. [14] A printed wiring board having a circuit pattern formed by etching the surface treated copper foil of the copper clad laminate as described in [13].
10:銅箔 20:1次粗化粒子 30:覆蓋鍍覆層 40:2次粗化粒子 10: Copper foil 20: 1st roughening particles 30: Covering coating 40: 2nd roughening particles
[圖1]係表示表面處理層之典型的負載曲線之曲線圖。 [圖2]係示意性地表示本發明實施形態之一例，即於銅箔之一面具有粗化處理層之表面處理銅箔的剖視圖。 [Figure 1] is a graph showing a typical load curve of a surface treatment layer. [Figure 2] is a schematic diagram showing an example of an embodiment of the present invention, i.e., a cross-sectional view of a surface treated copper foil having a roughening treatment layer on one side of the copper foil.
Claims (17)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022-155419 | 2022-09-28 |
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| TW202413724A true TW202413724A (en) | 2024-04-01 |
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