JP2013104121A - Method for producing copper foil for environmentally friendly printed circuit board composed of fine granular surface with high peeling strength - Google Patents
Method for producing copper foil for environmentally friendly printed circuit board composed of fine granular surface with high peeling strength Download PDFInfo
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- JP2013104121A JP2013104121A JP2011250445A JP2011250445A JP2013104121A JP 2013104121 A JP2013104121 A JP 2013104121A JP 2011250445 A JP2011250445 A JP 2011250445A JP 2011250445 A JP2011250445 A JP 2011250445A JP 2013104121 A JP2013104121 A JP 2013104121A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011889 copper foil Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 238000007747 plating Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000007788 roughening Methods 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000003746 surface roughness Effects 0.000 claims description 6
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 abstract description 16
- 230000002378 acidificating effect Effects 0.000 abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000008151 electrolyte solution Substances 0.000 abstract description 4
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 abstract description 3
- 239000000057 synthetic resin Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 7
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl silicate Chemical compound 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 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 2
- 238000007429 general method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 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
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017868 Cu—Ni—Co Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Abstract
Description
本発明はプリント回路基板用銅箔に関する。更に詳しくは，基板用の銅箔表面の剥離強度が高く，環境にやさしい微細な粒状表面からなるプリント回路基板であって、多層のプリント配線基板等の基材として広く適用されているものに関する。 The present invention relates to a copper foil for printed circuit boards. More specifically, the present invention relates to a printed circuit board having a fine granular surface that has high peel strength on the surface of a copper foil for a board and is widely applied as a base material such as a multilayer printed wiring board.
昨今、電子産業分野に使われている銅箔は，一般的に硫酸銅の電解液にて銅を原箔の表面に電気めっきし，おのおのの処理過程を経て，最終的に表面粗化処理された銅箔となる。この表面粗化処理銅箔は，銅或いはニッケルを熱プレス又は圧延し、出来た金属片をプリント回路基板の基礎材料として、高ガラス転移温度(Tg)であるエポキシ樹脂基材，フエノールアルレヒド樹脂基材及びポリイミド樹脂基材等とマット（mat）してプリント電気回路基板又は積層板となる。 In recent years, copper foil used in the electronics industry is generally subjected to surface roughening treatment after electroplating copper on the surface of the original foil with copper sulfate electrolyte and through each treatment process. Copper foil. This surface-roughened copper foil is made by hot-pressing or rolling copper or nickel, and using the resulting metal piece as a basic material for a printed circuit board, an epoxy resin base material having a high glass transition temperature (Tg), phenol aldehyde resin A printed electric circuit board or a laminate is formed by matting with a base material and a polyimide resin base material.
銅箔の表面が粗化処理されているプリント電気回路基板に必要とされる主な基本特性としては，銅箔と各種のエポキシ樹脂，フエノル樹脂，ポリイミド樹脂基材の基板等との間に優位且つ充分な剥離強度があり，熱圧又は後で行なう各種の処理過程においても剥離強度が標準以上に維持されていなければならないことである。このため，この銅箔は酸，アルカリに対し必ず優位な耐化学品，耐熱、耐酸等の特性を有するだけでなく，又電気回路配線図案作成のときのエッチング（etching）作業においても残留物質によるぎざぎざのヘリ〈deckle edge〉現象のない優位なエッチング特性があることになる。これら上記の特性を達成するため，通常は先に銅箔表面粗化処理(roughening)，その後に耐熱層，防錆層(Antirust)，又はアルキルシリケート(alkylsilicate) の処理、塗装を行なってきた。 The main basic characteristics required for printed circuit boards with a roughened copper foil surface are superiority between the copper foil and various epoxy resin, phenolic resin, and polyimide resin-based substrates. In addition, it has a sufficient peel strength, and the peel strength must be maintained above the standard even in the hot press or in various treatment processes performed later. For this reason, this copper foil not only has the characteristics of chemical resistance, heat resistance, acid resistance, etc., which are always superior to acids and alkalis, but also due to residual substances in the etching work when creating electrical circuit wiring designs. It has superior etching characteristics without the jagged helicopter phenomenon. In order to achieve these characteristics, the copper foil surface is usually roughened first, followed by heat-resistant layer, antirust layer, or alkylsilicate treatment and coating.
ここ数年、携帯電話(mobile phone)，ノートブック(Note Book)等の普及に伴い、高ガラス転移温度(Tg)基材としてエポキシ樹脂プリント電気回路基板使用の増加が激しい。しかしながら、銅箔と高Tg基材との剥離強度は、伝統的なFR-4基材に比べ低くなっている。このために，強度を高くすべく業者は銅箔表面の粗化度を高く調整することで克服してきた。だがこの方法では容易に粉末剥落とエッチングの銅残渣現象（銅エッチング残渣）を発生させやすいという欠点がある。 In recent years, with the popularization of mobile phones, notebooks, etc., the use of epoxy resin printed circuit boards as a high glass transition temperature (Tg) substrate has increased dramatically. However, the peel strength between the copper foil and the high Tg substrate is lower than the traditional FR-4 substrate. For this reason, in order to increase the strength, the traders have overcome it by adjusting the roughness of the copper foil surface to a high level. However, this method has a drawback that it easily causes powder peeling and etching copper residue phenomenon (copper etching residue).
又，電子部分品の高密度化，高性能化と小型化傾向により、プリント回路基板の配線も高密度化してきており，配線の線と線との間の幅も又微細化に向け発展している。このため，プリント回路基板用の銅箔も又これら高密度化，微細化に対応可能な低い粗化特性表面を特徴としている。しかし、これら1μm以下の低い表面粗化特性である銅箔では、樹脂回路基板とマットしたときの剥離強度が悪くなってしまい，上記銅箔の基本特性を達成することが出来ないという矛盾がある。 In addition, due to the trend toward higher density, higher performance, and miniaturization of electronic components, printed circuit board wiring has also been increased in density, and the width between wiring lines has also been developed toward miniaturization. ing. For this reason, copper foils for printed circuit boards are also characterized by a low roughening characteristic surface that can cope with these higher density and miniaturization. However, these copper foils with low surface roughness characteristics of 1 μm or less have a contradiction that the peel strength when matted with a resin circuit board is deteriorated and the basic characteristics of the copper foil cannot be achieved. .
そこで、銅箔表面の粗さが低く，又銅箔が必要とする特性を維持している先行技術としては、以下のようなものが知られている。特開昭５２−１４５７６９及び特開昭５５−０５８５０２に記載の二元合金Cu-Ni系では，耐熱性剥離強度及び耐塩酸性に優ぐれている反面，アルカリエッチング液でエッチングすることが出来ないという欠陥がある。 Therefore, the following are known as prior arts in which the roughness of the copper foil surface is low and the characteristics required by the copper foil are maintained. The binary alloy Cu-Ni system described in JP-A-52-145769 and JP-A-55-0585502 is superior in heat-resistant peel strength and hydrochloric acid resistance, but cannot be etched with an alkaline etching solution. There is a defect.
Cu-Co系を使用する特開昭５８−０２８８９３及び特開平２−２９２８９５は、Cucl2を含んでおり、アルカリエッチング液でエッチングすることが出来るが，その耐熱性剥離強度及び耐塩酸性はCu-Ni系処理に比べ悪いという問題点がある。 JP-A-58-028883 and JP-A-2-292895 using a Cu—Co system contain Cucl 2 and can be etched with an alkaline etchant, but its heat-resistant peel strength and hydrochloric acid resistance are Cu— There is a problem that it is worse than Ni processing.
特開平２−２９２８９４，特開平８−２３６９３０に記載のCu-Ni-Co系では、クロム又はタングステン（Tungsten）の金属イオンとバナジウム（Vanadium）、ニッケル、鉄、コバルト、亜鉛、モリブデンから選ばれた一種又は二種以上の金属イオンとからなる酸性銅めっき液で処理することが記載され，特開平１１−２５６３８９ではモリブデン、鉄,ニッケル、タングステン等の金属イオン酸性めっき液にて,粗化処理をする方法等が記載され，尚又実際上熱に耐えられる耐熱剥離強度を得ることが出来る比較的有効な銅箔の粗化処理として、毒性のあるヒ素，アンチモン，ビスマス又はセレニウム等を添加してある酸性銅電解溶液(特公昭５４−３８０５３，特公昭５３−３９３２７)を用いた方法も記載されているが、その廃液は環境保全問題をもたらす。これら技術は部分的な問題は処理解決出来るが，表面粗さの極めて低い銅箔が要求する、剥離強度、耐熱、耐酸、耐吸湿、及びエッチング粉落等，おのおのの各特性を充分且完全に維持し，まかなうことの出来る銅箔が未だに存在しない。 In the Cu-Ni-Co system described in JP-A-2-292894 and JP-A-8-236930, it was selected from chromium or tungsten metal ions and vanadium, nickel, iron, cobalt, zinc, and molybdenum. The treatment with an acidic copper plating solution composed of one or more metal ions is described. In JP-A-11-256389, a roughening treatment is carried out with a metal ion acidic plating solution of molybdenum, iron, nickel, tungsten or the like. In addition, toxic arsenic, antimony, bismuth, or selenium is added as a relatively effective roughening treatment of copper foil that can obtain heat-resistant peel strength that can actually withstand heat. Although a method using a certain acidic copper electrolytic solution (Japanese Patent Publication No. 54-38053, Japanese Patent Publication No. 53-39327) is also described, the waste liquid has an environmental conservation problem. Russ. These technologies can solve the partial problems, but each of the properties such as peel strength, heat resistance, acid resistance, moisture absorption resistance, and etching dust removal required by copper foils with extremely low surface roughness are fully and completely achieved. There is still no copper foil that can be maintained and covered.
そこで，本発明の目的は、銅箔が極めて低い微細な粗化処理表面でも，合成樹脂基板との間が充分な接着力(強度)を有し，エッチング処理において粉末剥落（粉落）がなく、粗化処理用の電解溶液及び電解後の廃水処理等も良く、環境にやさしいプリント電気回路基板用銅箔を提供することにある。 Therefore, the object of the present invention is to have a sufficient adhesion (strength) between the copper foil and the synthetic resin substrate even on a very rough surface with a very low roughness, and there will be no powder peeling off during the etching process. In addition, an electrolytic solution for roughening treatment, waste water treatment after electrolysis and the like are good, and an object is to provide a copper foil for a printed electric circuit board that is environmentally friendly.
上記銅箔の課題を解決するため，本願発明者は多年の経験，調査，研究と試験の結果，微細な粒状の突起群からなる銅原箔の接着面を、先に硫酸銅五水和物と硫酸からなる硫酸銅酸性溶液で表面上の汚れ又は付着物を洗浄し，その後微量のリンタングステン酸ナトリウムからなる金属イオン化合物を添加し硫酸銅電解液浴槽に投入して電気めっきしたとき，電着した（electrodeposited）銅の瘤(Tumor)が、微細な粒状の突起群からなる銅箔接着面上の微細な粒状の峰の上ばかりだけではなく，深いその谷底迄にも数多く蓄積することを見出した。さらに，銅箔接着面の粗化処理の善し悪しは合成樹脂基板とのマット(mat)に莫大な影響を与えることがわかり，これらに基づいて本発明を完成したものである。 In order to solve the above-mentioned problems of copper foil, the inventor of the present application, as a result of many years of experience, investigation, research and test, previously described the adhesive surface of copper raw foil consisting of a group of fine granular protrusions, copper sulfate pentahydrate When the surface is cleaned of dirt or deposits with an acidic solution of copper sulfate consisting of sulfuric acid and sulfuric acid, a small amount of metal ion compound consisting of sodium phosphotungstate is added to the copper sulfate electrolyte bath and electroplating is performed. It can be seen that electrodeposited copper tumors accumulate not only on the fine grained peaks on the copper foil bonding surface consisting of a group of fine grained protrusions, but also on the deep valley bottom. I found it. Further, it has been found that the roughening treatment of the copper foil bonding surface has an enormous influence on the mat with the synthetic resin substrate, and the present invention has been completed based on these.
上記発明の目的を達成するため、本発明は硫酸銅からなる酸性洗浄溶液で先に銅箔表面を洗浄し，その後に微量のリンタングステン酸ナトリウムからなる金属イオン化合物を含む酸性硫酸銅電解浴に投入して銅箔表面をめっきし粗化処理層となし，更にこの粗化処理層の上に公知技術の耐熱Zn合金層と防錆層を施し，最後に防錆層上にアルキルシリケート（Alkylsilicate）を塗装してなるものである。 In order to achieve the above object, the present invention provides an acidic copper sulfate electrolytic bath containing a metal ion compound consisting of a small amount of sodium phosphotungstate after first cleaning the surface of the copper foil with an acidic cleaning solution consisting of copper sulfate. The copper foil surface is plated and a roughened layer is formed, and a heat-resistant Zn alloy layer and a rust-proof layer are applied on the roughened layer. Finally, an alkyl silicate (Alkylsilicate) is formed on the rust-proof layer. ) Is painted.
上記本発明の酸性洗浄溶液は、硫酸銅五水和物 245〜265 g/l，硫酸90〜100 g/lを含有する。この酸性洗浄溶液の硫酸銅五水和物の濃度が245 g/l以下で硫酸濃度が90g/l以下である場合は、洗浄効果が悪い。硫酸銅五水和物の濃度が265 g/lと硫酸濃度100g/lとが以上の場合、結晶状の酸化斑点現象がある。 The acidic cleaning solution of the present invention contains copper sulfate pentahydrate 245 to 265 g / l and sulfuric acid 90 to 100 g / l. When the concentration of copper sulfate pentahydrate in this acidic cleaning solution is 245 g / l or less and the sulfuric acid concentration is 90 g / l or less, the cleaning effect is poor. When the copper sulfate pentahydrate concentration is 265 g / l and the sulfuric acid concentration is 100 g / l, there is a crystalline oxidation spot phenomenon.
特殊な電解液として、本発明の電解浴は、硫酸銅五水和物80〜90 g/l，硫酸90〜100 g/lと、微量のリンタングステン酸ナトリウム18水和物15〜55ppmは二元合金Cu-W系からなる。その微量のリンタングステン酸ナトリウムからなる金属イオン化合物は分子式が2Na2O,P2O5,12WO3,18H2Oであり、水に溶ける白い粒状粉末で，カリウム，尿酸の分析試剤として使用されている。通常は温度20〜750C,電流密度30〜45 A/dm2，めっき時間は３〜５秒にてめっきする。 As a special electrolytic solution, the electrolytic bath of the present invention contains copper sulfate pentahydrate 80 to 90 g / l, sulfuric acid 90 to 100 g / l, and a trace amount of sodium phosphotungstate 18 hydrate 15 to 55 ppm. It consists of the original alloy Cu-W. The metal ion compound consisting of a small amount of sodium phosphotungstate has a molecular formula of 2Na 2 O, P 2 O 5 , 12WO 3 , 18H 2 O, and is a white granular powder that dissolves in water. It is used as an analytical reagent for potassium and uric acid. ing. Normally the temperature 20 to 75 0 C, a current density of 30~45 A / dm 2, plating time is plated at 3-5 seconds.
ここで特に強調することは、酸性硫酸銅電解浴の硫酸銅五水和物の濃度が80 g/l 以下であれば銅粉を発生（粉末剥落）し，90 g/l 以上のときは剥離強度が劣り不足となり；硫酸濃度が90 g/l 以下のときはめっきの質が悪く，100 g/l 以上であればエッチング不良；リンタングステン酸ナトリウム18水和物が15ppm以下では深く谷底迄にめっきすることが出来ず；55ppm以上では粉落の現象がある。 What is particularly emphasized here is that copper powder is generated (powder stripping) if the concentration of copper sulfate pentahydrate in the acidic copper sulfate electrolytic bath is 80 g / l or less, and peeling if it is 90 g / l or more. The strength is inferior and insufficient; when the sulfuric acid concentration is 90 g / l or less, the plating quality is poor, and when it is 100 g / l or more, the etching is poor; when the sodium phosphotungstate 18 hydrate is 15 ppm or less, Can not be plated; at 55ppm or more, there is a phenomenon of powder falling.
又，温度が200C以下，電流密度も30 A/dm2以下，及びめっき時間とが3秒以下のときは剥離強度が不足で，温度が750C以上，電流密度が45 A/dm2以上と，めっき時間が5秒以上であるときは粉落をきたす。 When the temperature is 20 0 C or less, the current density is 30 A / dm 2 or less, and the plating time is 3 seconds or less, the peel strength is insufficient, the temperature is 75 0 C or more, and the current density is 45 A / dm. If it is 2 or more and the plating time is 5 seconds or more, powdering will occur.
熱変色を避けるため，本発明は公知の一般的方法とおなじく粗化処理層の上に，例えば，Zn-Ni，Zn-Co，Zn-Mo，或いはZn-Ni-Co系等の合金液でめっきして耐熱層を形成する。これら耐熱層の電解浴は，Zn化合物1〜10 g/l，その他の金属は0.5〜15 g/l，PH=4〜10からなり，温度を35〜600C，電流密度0.1〜4 A/dm2，めっき時間は3〜5秒にしてめっきする。 In order to avoid thermal discoloration, the present invention is applied to a roughened layer similar to a known general method, for example, with an alloy liquid such as Zn-Ni, Zn-Co, Zn-Mo, or Zn-Ni-Co. Plating to form a heat resistant layer. Electrolytic baths for these heat-resistant layers consist of Zn compounds 1-10 g / l, other metals 0.5-15 g / l, PH = 4-10, temperature 35-50 0 C, current density 0.1-4 A. / dm 2 , plating for 3-5 seconds.
上記Zn合金耐熱層が形成された後，更にこの耐熱層の上に防錆のクロム層をめっき，又はアルキルシリケートを塗装しても良い。その防錆層電解浴はクロム酸濃度が1〜12 g/l，アルカリ液の濃度が20〜50 g/l，温度が35〜750C，電流密度が0.1〜3 A/dm2にて3〜5秒めっきすれば良い効果が得られる。アルキルシリケート 剤の塗装処理は0.1〜1.0%重量のアルキルシリケートを純水で希釈したのち防錆層の上に塗装し乾燥すれば良い。 After the Zn alloy heat-resistant layer is formed, a rust-proof chromium layer may be further plated on the heat-resistant layer or an alkyl silicate may be applied. Its anticorrosive layer electrolytic bath is chromic acid concentration 1 to 12 g / l, the concentration of the alkali solution is 20 to 50 g / l, temperature 35 to 75 0 C, the current density at 0.1 to 3 A / dm 2 A good effect can be obtained by plating for 3 to 5 seconds. The coating treatment of the alkyl silicate agent may be performed by diluting 0.1 to 1.0% by weight of alkyl silicate with pure water, coating it on the anticorrosive layer and drying it.
以下本発明を実施例に基づいて詳しく説明する。但し，本発明はこれらに限定されるものでない。 Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to these.
実施例１
厚さ30〜40μm，表面粗さが0.82μm以下の表面粗度からなるプリント回路基板用原箔(銅又はニッケル)を；
(1) 硫酸銅五水和物255 g/lと硫酸95 g/lからなる酸性溶液で5秒間、先に原箔表面上の汚れ又は附着物を洗い流し；
(2) 水洗後，硫酸銅五水和物86 g/lと硫酸95 g/lとの溶液に微量のリンタングステン酸ナトリウム18水和物(Sodium-phophotungstate octadecylhydrate)26ppmを添加してなる、温度が250Cであるめっき浴中に投入し，電気密度42 A/dm2 にて微細な粒状の突起群からなる銅箔被接着面を3秒通電めっきして粗化処理し；
(3) 水洗後，硫酸銅五水和物300 g/lと硫酸100 g/lの浴温が600Cであるめっき浴槽にて電流密度を32.5 A/dm2で３秒通電して、銅からなる粗化層を生成し；
(4) 銅からなる銅箔の粗化層を更に水洗した後(２)と同様のめっき液で，電流密度40 A/dm2で３秒通電めっきしてなる複合金属層を形成し；
(5) 最後に複合金属層を水洗し(３)と同様のめっき液を用い電流密度を36A/dm2で3秒通電めっきして完壁な銅箔粗化処理層を得る。
(6) 上記(5)で得られた銅箔は、更に公知の一般方法で剥離層或いは複合金属層の上に亜鉛或いはニッケル，例えば硫酸亜鉛7H2O或いは硫酸ニッケル6H2O，又はクロム酸塩等をめっきして耐熱防錆処理，又は3-グリシリルトリメチルシラン (３−glycidyl trimethy Silane) を塗布して剥離強度を向上することが出来る。上記ステップにより得られるおのおのの物理特性は後記の試験方法に従って測試した。その結果は表２に示す。
Example 1
A raw foil for printed circuit boards (copper or nickel) having a surface roughness of 30 to 40 μm in thickness and a surface roughness of 0.82 μm or less;
(1) First wash away dirt or attachments on the surface of the raw foil with an acidic solution consisting of 255 g / l of copper sulfate pentahydrate and 95 g / l of sulfuric acid;
(2) After washing with water, a temperature obtained by adding a small amount of sodium phosphotungstate octadecylhydrate 26ppm to a solution of 86 g / l copper sulfate pentahydrate and 95 g / l sulfuric acid Put in a plating bath with a temperature of 25 0 C, and roughen the copper foil adherend surface consisting of fine granular projections at an electric density of 42 A / dm 2 for 3 seconds.
(3) After washing with water, energize at a current density of 32.5 A / dm 2 for 3 seconds in a plating bath with a bath temperature of 300 g / l copper sulfate pentahydrate and 100 g / l sulfuric acid at a temperature of 60 0 C. Producing a roughened layer of copper;
(4) After further washing the roughened layer of copper foil made of copper, a composite metal layer is formed by conducting current plating at a current density of 40 A / dm 2 for 3 seconds with the same plating solution as in (2);
(5) Finally, the composite metal layer is washed with water and electroplated for 3 seconds at a current density of 36 A / dm 2 using the same plating solution as in (3) to obtain a complete copper foil roughening layer.
(6) The copper foil obtained in the above (5) is further prepared by a known general method on the release layer or the composite metal layer with zinc or nickel, such as zinc sulfate 7H 2 O or nickel sulfate 6H 2 O, or chromic acid. Peeling strength can be improved by plating with salt or the like and applying heat-resistant rust-proofing treatment or 3-glycidyl trimethy Silane. Each physical property obtained by the above steps was measured according to the test method described later. The results are shown in Table 2.
実施例２
実施例１の（２）の微量26ppmのリンタングステン酸ナトリウム18水和物を微量17ppmのリンタングステン酸ナトリム18水和物に代えたことを徐き，実施例１と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Example 2
In the same manner as in Example 1, a roughening treatment and a sodium phosphotungstate 18 hydrate in Example 2 (2) were gradually replaced with a 17 ppm sodium phosphotungstate 18 hydrate. Each surface-treated copper foil was fabricated and the physical characteristics of each were evaluated. The results are shown in Table 2.
実施例３
実施例１の（２）の微量26ppmのリンタングステン酸ナトリウム18水和物を微量５２ppmのリンタングステン酸ナトリウム１８水和物に代えたことを徐き、実施例１と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Example 3
In the same manner as in Example 1, the roughening treatment and the phosphotungstate sodium hydrate 18 hydrate of Example 1 (2) were gradually replaced with the phosphotungstate 18 hydrate of 52 ppm. Each surface-treated copper foil was fabricated and the physical characteristics of each were evaluated. The results are shown in Table 2.
実施例４
実施例１の（２）の硫酸95 g/lを100 g/lに代えたことを徐き、実施例１と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Example 4
Gradually, the sulfuric acid 95 g / l in Example 1 (2) was replaced with 100 g / l, and a roughening treatment and a surface-treated copper foil were prepared in the same manner as in Example 1, and the physical properties of each were obtained. Evaluation was performed. The results are shown in Table 2.
実施例５
実施例１の（２）の硫酸95 g/lを90 g/lに，リンタングステン酸ナトリウム18水和物26ppmを17ppmに代えたことを徐き、実施例１と同様にして粗化処理及び表面粗化処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Example 5
In the same manner as in Example 1, a roughening treatment was carried out in the same manner as in Example 1, except that 95 g / l of sulfuric acid in Example 2 (2) was changed to 90 g / l and 26 ppm of sodium phosphotungstate 18 hydrate was replaced with 17 ppm. Each surface-roughened copper foil was fabricated and the physical characteristics of each were evaluated. The results are shown in Table 2.
比較例1
1) 上記実施例1の（２）の「硫酸銅五水和物86g/lと硫酸95 g/lとの溶液に微量のリンタングステン酸ナトリウム18水和物26ppmを添加してなる、温度が250Cであるめっき浴中に投入し，電気密度42 A/dm2 にて微細な粒状の突起群からなる銅箔被接着面を3秒通電めっきして粗化処理し」における、硫酸95 g/lを90 g/lに，リンタングステン酸ナトリウム18水和物26ppmは毒性のあるアルセニックトリオキサイド(AS2O3)528ppmに代えたことを除き，実施例1と同じ方法で粗化処理を行い；
2) 前記 １）の銅箔被接着面上に、硫酸銅五水和物86 g/l，硫酸90 g/lとAS2O3528ppmのめっき液温度が250Cからなるめっき浴を電流密度42 A/dm2 にて3秒通電めっきして銅イオンからなる粗化層を生成し；
3) 水洗後，銅イオンからなる粗化層の上に１)と同様なめっき液を用いて電流密度31.5 A/dm2 ，3秒通電めっきしてなる複合金属層となし，
4) 水洗後，更にこの複合金属層の上に前記 ２）と同じのめっき液で電流密度を40.6 A/dm2，3秒通電めっきして完全に粗化処理された銅箔を得る。
上記のステップにより得られたおのおのの物理特性評価の結果を表２に示す。
Comparative Example 1
1) In the above Example 1 (2), “a solution of copper sulfate pentahydrate 86 g / l and sulfuric acid 95 g / l with a small amount of sodium phosphotungstate 18 hydrate 26 ppm added, In a plating bath at 25 0 C, the copper foil adherend surface consisting of fine granular protrusions was plated for 3 seconds at an electric density of 42 A / dm 2 and roughened, and the sulfuric acid 95 Roughing in the same way as Example 1 except that g / l was changed to 90 g / l and 26 ppm of sodium phosphotungstate 18 hydrate was replaced with 528 ppm of toxic arsenic trioxide (AS 2 O 3 ) Do the processing;
2) the on the copper foil to be bonded surface of 1), current plating bath Copper sulfate pentahydrate 86 g / l, the plating solution temperature of the sulfuric acid 90 g / l and AS 2 O 3 528ppm consists 25 0 C Generate a roughened layer made of copper ions by electroplating for 3 seconds at a density of 42 A / dm 2 ;
3) After washing with water, on the roughened layer made of copper ions, using a plating solution similar to 1), a current density of 31.5 A / dm 2 and a composite metal layer formed by conducting current plating for 3 seconds,
4) After washing with water, a copper foil that has been completely roughened is obtained by applying a current density of 40.6 A / dm 2 for 3 seconds on the composite metal layer with the same plating solution as in 2) above.
Table 2 shows the results of the physical property evaluation obtained by the above steps.
比較例２
比較例1の１）のアルセニックトリオキサイド528ppmをアルセニックトリオキサイド396ppmに代えたことを徐き，比較例1と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Comparative Example 2
Slowly replacing arsenic trioxide 528ppm in Comparative Example 1 1) with arsenic trioxide 396ppm, and preparing roughened and surface-treated copper foils in the same manner as Comparative Example 1, respectively, physical properties Evaluation was performed. The results are shown in Table 2.
比較例３
比較例1の１）のアルセニックトリオキサイド５２８ppmをアルセニックトリオキサイド１３２ppmに代えたことを徐き，比較例1と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Comparative Example 3
Slowly replacing 528 ppm of Arsenic Trioxide in 1) of Comparative Example 1 with 132 ppm of Arsenic Trioxide, and preparing a roughening treatment and a surface-treated copper foil in the same manner as in Comparative Example 1, respectively, and physical properties of each Evaluation was performed. The results are shown in Table 2.
比較例４
比較例1の１）のアルセニックトリオキサイド５２８ppmをアルセニックトリオキサイド66ppmに代えたことを除き、比較例1と同様にして粗化処理及び表面処理銅箔をそれぞれ作製し，おのおのの物理特性評価を行った。結果を表２に示す。
Comparative Example 4
Roughening treatment and surface-treated copper foil were prepared in the same manner as in Comparative Example 1 except that 528 ppm of Arsenic Trioxide in Comparative Example 1) was replaced with 66 ppm of Arsenic Trioxide, and physical properties were evaluated for each. Went. The results are shown in Table 2.
本発明の実施例及び比較例に用いた物理特性試験は下述の項目で行なった。 The physical property tests used in the examples and comparative examples of the present invention were conducted in the following items.
1)剥離強度：
NP-180 (南亜會社（出願人）製ハロゲン樹脂)基材を銅箔の接着面にマットして幅32milの積層板試験片となし，剥離強度を引っぱり試験機にて測定した。
1) Peel strength:
NP-180 (Nanya Co., Ltd. (Applicant) Halogen Resin) base material was mated on the adhesive surface of copper foil to form a 32 mil wide laminate test piece, and the peel strength was measured with a tester.
2)耐熱剥離強度：
試験片を1770Cのオーブンに置き，２４０時間後剥離強度を測定した。
2) Heat-resistant peel strength:
The test piece placed in an oven at 177 0 C, the peel strength was measured after 240 hours.
3)耐HCl性：
試験片を18 %HCl溶液の中に一時間漬けた後，剥離強度の悪化率を測定した。
3) HCl resistance:
After the specimen was immersed in an 18% HCl solution for 1 hour, the rate of deterioration of peel strength was measured.
4) 耐吸湿性：
試験片を圧力が１atm，温度が1210Cの圧力鍋内に2時間置いた後，剥離強度の悪化率を測定した。
4) Hygroscopic resistance:
The test piece is pressure 1 atm, After 2 hours at the temperature of 121 0 in C pressure cooker of was measured deterioration rate of the peel strength.
5) 粉落：
濾紙の粗い濾紙面を、左位置で銅箔の平滑でない面に指先で抑えつけ，左から右へ約30cm濾紙を滑らし、終了後サンプルカードと比較して等級を判定する。
粉落の等級評価基準は，
○； 1〜1級
△； ≦1〜2級
Ｘ； ≦2級
5) Powder fall:
Hold the rough filter paper surface of the filter paper to the non-smooth surface of the copper foil at the left position with your fingertips, slide the filter paper about 30 cm from left to right, and compare the sample card with the grade after completion.
The grade evaluation criteria for dust fall are:
○; 1st to 1st class △; ≤ 1st to 2nd class X; ≤ 2nd class
6) 蝕刻性：
試験片(線幅/線間；75/75μmの基材)を，塩化銅(CuCl2) 265.9 g/l，過酸化水素(H2O2)150ml/l 及びHCl 224 ml/lを含む酸性のエッチング液中に入れ，温度550Cの条件下で五分間漬けた後，温度が480Cの3％NaOH溶液に漬け、膜型を取る。水洗後アルカリめっき層を切片し，光学顕微鏡(OM)及び走査式電子顕微鏡(SEM)にてぎざぎざのヘリ現象を観察判定する。
エッチング性等級(Class)の評価基準は：
○； エッチング後，基材上には残留のぎざぎざのヘリ現象がない。
△； エッチング後，基材上には若干の残留ぎざぎざのヘリ現象がある。
Ｘ；エッチング後，基材上には多くの残留ぎざぎざのヘリ現象がある。
6) Etchability:
Specimens (line width / line spacing; 75/75 μm substrate) were acidified with copper chloride (CuCl 2 ) 265.9 g / l, hydrogen peroxide (H 2 O 2 ) 150 ml / l and HCl 224 ml / l of placed in an etching solution, after soaking five minutes under the conditions of temperature 55 0 C, the temperature is immersed in 3% NaOH solution 48 0 C, take the membrane. After washing with water, cut the alkali plating layer and observe and judge the jagged helicopter phenomenon with an optical microscope (OM) and scanning electron microscope (SEM).
The evaluation criteria for etching grade (Class) are:
○: There is no residual jagged helicopter on the substrate after etching.
Δ: After etching, there is some residual jagged helicopter phenomenon on the substrate.
X: After etching, there are many residual jagged helicopters on the substrate.
発明の効果：本発明実施例1〜5の剥離強度，耐熱剥離強度，耐HCl性，耐湿性の等の品質特性は表２から明らかに優秀である。 Advantages of the Invention: From Table 2, the quality characteristics such as peel strength, heat-resistant peel strength, HCl resistance, and moisture resistance of the inventive examples 1 to 5 are clearly excellent.
本発明実施例1〜5の銅箔接着面の粗さが比較例1〜4に比べ低いにもかかわらず、エッチング等の品質特性は非常に優れている。又これら以外の品質に対しても本発明実施例1〜5の各特性は比較例1〜4の品質特性に比べ良いことがわかる。 Although the roughness of the copper foil bonding surface of Examples 1 to 5 of the present invention is lower than that of Comparative Examples 1 to 4, the quality characteristics such as etching are very excellent. It can also be seen that the characteristics of Examples 1 to 5 of the present invention are better than those of Comparative Examples 1 to 4 for quality other than these.
例として本発明実施例1〜5の剥離強度，耐熱剥離強度，耐HCl性及び耐吸湿性等の各品質特性を比較例1〜4 の品質特性と比較した場合、本発明実施例の各品質特性は比較例の各品質特性より約11.7％、52.4％、26.3％、11.6％以上良い。 As an example, when each quality characteristic such as peel strength, heat-resistant peel strength, HCl resistance, and moisture absorption resistance of Examples 1 to 5 of the present invention was compared with the quality characteristics of Comparative Examples 1 to 4, each quality of Examples of the present invention The characteristics are about 11.7%, 52.4%, 26.3%, 11.6% better than each quality characteristic of the comparative example.
上記の如く, 本発明実施例の粗化処理にて製造された微細な粒状表面からなるプリント回路基板用銅箔は,その接着面の粗さが比較例の粗さよりも低く,かつ高剥離強度,高耐熱剥離強度,高耐HCl性及び高耐吸湿性とエッチング等の優良な品質特性を有し,粗化処理のめっき時間が短く、毒性のある例えばヒ素等の化合物を使わない,高い効率で生産の出来る優点を有する環境にやさしいプリント回路基板用銅箔であり,各種のプリント回路基板に適用されるものである。 As described above, the copper foil for a printed circuit board having a fine granular surface manufactured by the roughening treatment of the embodiment of the present invention has a lower adhesive surface roughness than that of the comparative example and a high peel strength. Excellent quality characteristics such as high heat-resistant peel strength, high HCl resistance, high moisture absorption resistance and etching, short plating time for roughening treatment, no use of toxic compounds such as arsenic, high efficiency It is an environmentally friendly copper foil for printed circuit boards that has the advantages that it can be produced in, and is applied to various printed circuit boards.
Claims (2)
(1)表面粗さが1μm以下の原箔を硫酸銅五水和物245〜265g/l，硫酸90〜100g/lからなる酸性溶液で原箔表面上の汚れ附着物を洗浄し；
(2)水洗後，硫酸銅五水和物80〜90 g/lと硫酸90〜100 g/lとの溶液に微量のリンタングステン酸ナトリウム18水和物15〜55ppmを添加してなる、温度が20〜750Cであるめっき浴中に投入し，電流密度を30〜45 A/dm2 、めっき時間3〜5秒にて銅箔被接着面をめっき粗化処理し；
(3)水洗後，硫酸銅五水和物と硫酸とを含有するめっき浴槽にて電流密度を30〜45 A/dm2，3〜5秒通電めっきして銅粗化層を生成し；
(4)上記銅からなる銅箔の粗化層を水洗した後(2)と同様のめっき液で電流密度を30〜45A/dm23〜5秒通電めっきして複合金属層となし；
(5)複合金属層を水洗し(3) と同様のめっき液を用い電流密度を30〜45 A/dm2で3〜5秒通電めっきしてなる粗化処理層とからなることを特徴とする高剥離強度と環境にやさしい微細な粒状表面からなるプリント回路基板用銅箔の製造方法。 It is a copper foil for a printed wiring circuit board, the surface of which is composed of a group of fine granular projections,
(1) Washing dirt deposits on the surface of the original foil with an acidic solution consisting of 245 to 265 g / l of copper sulfate pentahydrate and 90 to 100 g / l of sulfuric acid on the original foil having a surface roughness of 1 μm or less;
(2) A temperature obtained by adding a trace amount of sodium phosphotungstate 18-hydrate 15-55 ppm to a solution of copper sulfate pentahydrate 80-90 g / l and sulfuric acid 90-100 g / l after washing with water There was placed in the plating bath is 20 to 75 0 C, and a plating roughened copper foil adherend surface current density 30~45 a / dm 2, at plating time 3-5 seconds;
(3) After washing with water, a copper roughening layer is formed by conducting current plating at a current density of 30 to 45 A / dm 2 for 3 to 5 seconds in a plating bath containing copper sulfate pentahydrate and sulfuric acid;
(4) After washing the roughened copper foil layer made of copper, a current density of 30 to 45 A / dm 2 for 3 to 5 seconds with a plating solution similar to (2) is used to form a composite metal layer;
(5) The composite metal layer is washed with water, and a roughening treatment layer is formed by conducting plating for 3 to 5 seconds with a current density of 30 to 45 A / dm 2 using the same plating solution as in (3). The manufacturing method of the copper foil for printed circuit boards which consists of a fine granular surface which is high peeling strength and environmentally friendly.
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| JP2017066528A (en) * | 2015-09-30 | 2017-04-06 | イルジン マテリアルズ カンパニー リミテッドＩｌｊｉｎ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． | Surface treated copper foil for fine circuit board and manufacturing method therefor |
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