JPH11135952A - Copper foil with resin for printed circuit board and printed circuit board using the same - Google Patents
Copper foil with resin for printed circuit board and printed circuit board using the sameInfo
- Publication number
- JPH11135952A JPH11135952A JP9294429A JP29442997A JPH11135952A JP H11135952 A JPH11135952 A JP H11135952A JP 9294429 A JP9294429 A JP 9294429A JP 29442997 A JP29442997 A JP 29442997A JP H11135952 A JPH11135952 A JP H11135952A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- resin
- printed circuit
- resin layer
- circuit board
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000011889 copper foil Substances 0.000 title claims abstract description 145
- 229920005989 resin Polymers 0.000 title claims abstract description 109
- 239000011347 resin Substances 0.000 title claims abstract description 109
- 230000003746 surface roughness Effects 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims description 16
- 238000005530 etching Methods 0.000 abstract description 19
- 238000009413 insulation Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 81
- 239000000463 material Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 238000007788 roughening Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004840 adhesive resin Substances 0.000 description 6
- 229920006223 adhesive resin Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- -1 glycidoxy group Chemical group 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、印刷回路基板用樹
脂付き銅箔とそれを用いた印刷回路基板に関し、更に詳
しくは、エッチングファクタ（Ｅｆ）値が大きく、高密
度超微細配線が可能であり、多層印刷回路基板の製造に
用いて好適な印刷回路基板用樹脂付き銅箔と、それを用
いた印刷回路基板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated copper foil for a printed circuit board and a printed circuit board using the same, and more particularly to a printed circuit board having a large etching factor (Ef) value and capable of high-density ultrafine wiring. The present invention relates to a copper foil with a resin for a printed circuit board suitable for use in manufacturing a multilayer printed circuit board, and a printed circuit board using the same.
【０００２】[0002]
【従来の技術】多層印刷回路基板は、通常、次のように
して製造されている。すなわち、ガラス・エポキシ樹脂
やガラス・ポリイミド樹脂などから成る電気絶縁性の基
材と銅箔回路とを交互に複数層積層して形成した内層材
の表面に、熱硬化性の樹脂接着剤を介して表面回路形成
用の銅箔を積層して銅張り積層板とし、その銅張り積層
板に、スルーホールの穿設，スルーホールめっきを順次
行ったのち、表面の銅箔にエッチング処理を行って所望
する回路パターンを形成し、最後に、ソルダーレジスト
の形成やその他の仕上げ処理が行われる。2. Description of the Related Art A multilayer printed circuit board is usually manufactured as follows. That is, a thermosetting resin adhesive is applied to the surface of an inner layer material formed by alternately laminating a plurality of layers of an electrically insulating base material made of glass epoxy resin or glass polyimide resin and a copper foil circuit. The copper foil for surface circuit formation is laminated to form a copper-clad laminate, and through-holes are drilled and plated through the hole in the copper-clad laminate, and then the copper foil on the surface is etched. A desired circuit pattern is formed, and finally, formation of a solder resist and other finishing processes are performed.
【０００３】上記した工程における銅張り積層板の製造
時に用いる接着剤としては、通常、内層材を構成してい
る熱硬化性樹脂と同種の電気絶縁性樹脂のワニスをガラ
ス布などに含浸・嵌挿させて当該ワニスを半硬化状態に
し、それをマトリックス樹脂とするプリプレグ材が主流
になっている。すなわち、前記した内層材の上・下面に
所望枚数のプリプレグ材を配置し、更にプリプレグ材の
表面に表面回路形成用の銅箔を重ね合わせたのち、全体
を熱圧着して銅張り積層板が製造されている。[0003] As an adhesive used in the production of the copper-clad laminate in the above-mentioned process, a varnish of the same kind of electrically insulating resin as the thermosetting resin constituting the inner layer material is usually impregnated and fitted into a glass cloth or the like. The varnish is inserted into a semi-cured state, and a prepreg material using the varnish as a matrix resin is mainly used. That is, after arranging a desired number of prepreg materials on the upper and lower surfaces of the inner layer material described above, and further laminating a copper foil for forming a surface circuit on the surface of the prepreg material, the whole is thermocompressed to form a copper-clad laminate. Being manufactured.
【０００４】その場合、銅箔とプリプレグ材との接着強
度を高めるために、通常、当該銅箔の表面を粗化面にし
て、プリプレグ材のマトリックス樹脂との間でアンカー
効果を発揮させている。しかしながら、この方法にはガ
ラス布を強化材とするプリプレグ材の複数枚を重ねて使
用するため、次のような問題がある。In this case, in order to increase the adhesive strength between the copper foil and the prepreg material, the surface of the copper foil is usually roughened to exert an anchor effect with the matrix resin of the prepreg material. . However, this method has the following problems since a plurality of prepreg materials using a glass cloth as a reinforcing material are used in layers.
【０００５】まず、熱圧着後に得られた銅張り積層板の
銅箔面にガラス布の折り目が浮きでて銅箔面には数十μ
ｍオーダーの凹凸が生ずるため、そこに微細な回路パタ
ーンを形成しにくくなる。また、プリプレグ材それ自体
の厚みが、１枚１５０〜１８０μｍ程度の厚みであるた
め、製造する銅張り積層板の厚みを薄くすることができ
ない。更に、製造された銅張り積層板には、ガラス繊維
が包含されているため、微細なスルーホールやバイヤホ
ールの穿設時にレーザやプラズマなどを用いた加工が困
難になるということである。[0005] First, the folds of the glass cloth float on the copper foil surface of the copper-clad laminate obtained after thermocompression bonding, and several tens of μm are formed on the copper foil surface.
Since irregularities on the order of m are generated, it becomes difficult to form a fine circuit pattern there. Further, since the thickness of the prepreg material itself is about 150 to 180 μm, the thickness of the copper-clad laminate to be manufactured cannot be reduced. Furthermore, since the manufactured copper-clad laminate contains glass fiber, it is difficult to perform processing using a laser, plasma, or the like when drilling fine through holes or via holes.
【０００６】このようなことから、最近では、多層印刷
回路基板の製造に用いる表面回路形成用の銅箔として
は、内層材に接着させる側の銅箔表面を予めエポキシ樹
脂のような接着用樹脂で被覆し、当該接着用樹脂を半硬
化状態の絶縁樹脂層にして成る樹脂付き銅箔が登場して
いる。この樹脂付き銅箔は、接着用樹脂を最適条件で銅
箔に塗布することができ、また銅箔の下には必ず一定厚
みの接着用樹脂層が絶縁樹脂層として存在しているの
で、この接着用樹脂を介することにより前記したプリプ
レグ材のマトリックス樹脂と銅箔との接着強度は安定す
る。しかも熱圧着後の表面は非常に平滑になるので、高
密度な極微細配線の回路パターンの形成も容易である。For these reasons, recently, as a copper foil for forming a surface circuit used for manufacturing a multilayer printed circuit board, the surface of the copper foil to be bonded to the inner layer material has been previously coated with an adhesive resin such as an epoxy resin. A copper foil with a resin, which is made of a semi-cured insulating resin layer by coating with an adhesive resin, has appeared. This resin-coated copper foil allows the bonding resin to be applied to the copper foil under optimal conditions, and the bonding resin layer of a certain thickness always exists as an insulating resin layer under the copper foil. Through the bonding resin, the bonding strength between the matrix resin of the prepreg material and the copper foil is stabilized. Moreover, since the surface after thermocompression bonding is very smooth, it is easy to form a circuit pattern of high-density ultrafine wiring.
【０００７】また、この樹脂付き銅箔の場合、銅箔は接
着用樹脂（絶縁樹脂層）でバックアップされた状態にな
っているので、例えば、銅箔が非常に薄いときでも、印
刷回路基板の製造時に銅箔への皺などは発生しにくい。
すなわち、この樹脂付き銅箔は取り扱いやすい材料でも
ある。更に、この樹脂付き銅箔を使用すると、銅張り積
層板の製造時におけるプリプレグ材の使用枚数を減らす
こともできる。しかも、接着用樹脂層の厚みを層間絶縁
が確保できるような厚みにしたり、プリプレグ材を全く
使用しなくても銅張り積層板を製造することができる。
またこのとき、内層材の表面に絶縁樹脂をアンダーコー
トして表面の平滑性を更に改善することもできる。In the case of the copper foil with resin, since the copper foil is backed up by an adhesive resin (insulating resin layer), for example, even when the copper foil is extremely thin, Wrinkles and the like on the copper foil hardly occur during manufacturing.
That is, this resin-coated copper foil is also a material that is easy to handle. Furthermore, when this resin-coated copper foil is used, the number of prepreg materials used in the production of a copper-clad laminate can be reduced. In addition, a copper-clad laminate can be manufactured without making the thickness of the adhesive resin layer such that interlayer insulation can be ensured, or without using a prepreg material at all.
At this time, the surface of the inner layer material may be undercoated with an insulating resin to further improve the surface smoothness.
【０００８】なお、上記したようにプリプレグ材を使用
しない場合には、プリプレグ材の材料コストは節約さ
れ、また積層工程も簡略になるので経済的に有利とな
り、しかも、プリプレグ材の厚み分だけ製造される多層
印刷回路基板の厚みを薄くすることができるという利点
がある。When the prepreg material is not used as described above, the material cost of the prepreg material is saved, and the laminating process is simplified, so that it is economically advantageous. There is an advantage that the thickness of the multilayer printed circuit board can be reduced.
【０００９】[0009]
【発明が解決しようとする課題】ところで、最近の各種
電子部品は高度に集積化され、小型でかつ高密度の印刷
回路を内蔵するＩＣやＬＳＩなどが使用されている。そ
して、このことに対応して、印刷回路基板における回路
パターンも高密度化が要求され、微細な線幅の配線から
成る回路パターンが形成されている、いわゆるファイン
パターンの印刷回路基板が要求されるようになった。例
えば最近では、配線ピッチが５０〜１００μｍ程度で線
幅が３０μｍ前後という高密度極微細配線を有する印刷
回路基板が要求されている。By the way, recent various electronic components are highly integrated, and ICs and LSIs having a small and high-density printed circuit are used. Corresponding to this, a circuit pattern on a printed circuit board is also required to have a high density, and a so-called fine-pattern printed circuit board on which a circuit pattern composed of fine line width wiring is formed is required. It became so. For example, recently, there has been a demand for a printed circuit board having a high-density ultrafine wiring having a wiring pitch of about 50 to 100 μm and a line width of about 30 μm.
【００１０】このファインな回路パターンを形成しよう
とする場合には、エッチング時におけるエッチングファ
クタ（Ｅｆ）を考慮することが重要である。ここでエッ
チングファクタ（Ｅｆ）について説明する。いま、銅箔
へのエッチングにより、図３で示したような断面形状を
有する回路パターンが絶縁樹脂層２の上に形成されたも
のとする。図３において、Ｈは銅箔１の厚みであり、Ｔ
が回路パターンにおけるトップ幅、Ｂが回路パターンの
ボトム幅を示している。When trying to form this fine circuit pattern, it is important to consider the etching factor (Ef) at the time of etching. Here, the etching factor (Ef) will be described. Now, it is assumed that a circuit pattern having a cross-sectional shape as shown in FIG. 3 is formed on the insulating resin layer 2 by etching the copper foil. In FIG. 3, H is the thickness of the copper foil 1 and T is
Indicates the top width of the circuit pattern, and B indicates the bottom width of the circuit pattern.
【００１１】このような断面形状の回路パターンにおい
て、そのエッチングファクタ（Ｅｆ）は、次式： Ｅｆ＝２Ｈ／（Ｂ−Ｔ） に基づいて算出される値であり、この値が大きいほど、
形成された回路パターンの側壁は垂直に近い状態に成っ
ていることを表している。したがって、ファインな回路
パターンを形成しようとする場合には、できるだけＥｆ
値が大きくなるような条件の下で銅箔のエッチングを行
うことが必要になる。In the circuit pattern having such a cross-sectional shape, the etching factor (Ef) is a value calculated based on the following equation: Ef = 2H / (BT).
This indicates that the side wall of the formed circuit pattern is almost vertical. Therefore, when a fine circuit pattern is to be formed, Ef should be as small as possible.
It is necessary to perform etching of the copper foil under conditions that increase the value.
【００１２】ところで、Ｅｆ値は様々な条件でその大小
が決まってくるが、とりわけ、銅箔の表面粗度との間に
は密接な関係がある。前記した樹脂付き銅箔の場合、例
えば銅箔の表面粗度を大きくすると、接着用樹脂に喰い
込んでいる粗化面の突起部を完全にエッチング除去する
ためにはある時間が必要になる。したがって、粗化面の
突起部をエッチング除去する過程では、既に形成されて
いる回路パターンの側壁４は更に一層エッチングされる
ことになり、その形状は悪化してしまう。すなわち、Ｅ
ｆ値は小さくなる。By the way, the magnitude of the Ef value is determined under various conditions. In particular, the Ef value has a close relationship with the surface roughness of the copper foil. In the case of the above-described copper foil with resin, for example, when the surface roughness of the copper foil is increased, a certain time is required to completely remove the projections on the roughened surface that have been cut into the bonding resin. Therefore, in the process of removing the projections on the roughened surface by etching, the side walls 4 of the already formed circuit pattern are further etched, and the shape is deteriorated. That is, E
The f value decreases.
【００１３】このような問題は、形成する回路パターン
の線幅が大きい場合にはそれほど深刻な問題にはならな
いが、線幅が小さいファインな回路パターンの場合に
は、断線に結びつく深刻な問題になってしまう。一方、
前記した粗化面の突起部が完全に除去されないと、それ
は残銅となって、回路パターン間の間隔が狭い場合には
絶縁不良の原因を構成する。Such a problem does not become so serious when the line width of the circuit pattern to be formed is large, but becomes serious when it is a fine circuit pattern having a small line width. turn into. on the other hand,
If the above-described protrusions on the roughened surface are not completely removed, they will become residual copper, which will cause insulation failure if the space between the circuit patterns is small.
【００１４】また、最近の多層印刷回路基板では、基板
全体の厚みを薄くするために各回路層の厚みをできるだ
け薄くする傾向にある。その場合、接着用樹脂の厚みも
薄くするので、表面粗度の大きい銅箔を使用すると、そ
の粗化面の突起部がこれら薄い接着用樹脂に食い込ん
で、互いの層間における絶縁を不安定な状態にすること
もある。In recent multilayer printed circuit boards, the thickness of each circuit layer tends to be as small as possible in order to reduce the thickness of the entire board. In this case, since the thickness of the adhesive resin is also reduced, when a copper foil having a large surface roughness is used, the projections on the roughened surface bite into the thin adhesive resin, and the insulation between the layers becomes unstable. It may be in a state.
【００１５】しかしながら、銅箔の表面粗度をある程度
大きくしないと、銅箔と接着用樹脂とのアンカー効果は
小さくなるため、樹脂付き銅箔の巻取りや巻戻しなどの
ハンドリング時に、当該接着用樹脂にクラックが発生し
たり、剥離が生じたりする。また、最終製品として得ら
れた印刷回路基板において、表面の回路パターンと基材
との接合強度が不足して、当該回路パターンが剥離した
り、エッチング時に断線したりすることもある。However, if the surface roughness of the copper foil is not increased to some extent, the anchoring effect between the copper foil and the bonding resin is reduced. Cracks and peeling occur in the resin. Further, in the printed circuit board obtained as a final product, the bonding strength between the surface circuit pattern and the base material is insufficient, and the circuit pattern may be peeled off or may be disconnected during etching.
【００１６】本発明は、樹脂付き銅箔を用いてファイン
な回路パターンを形成するときにおける上記した問題を
解決し、ハンドリング時に絶縁樹脂層へのクラック発生
や銅箔からの剥離が起こりにくく、そして信頼性の高い
高密度極微細配線の回路パターンを形成することがで
き、多層印刷回路基板用の銅箔として有用な樹脂付き銅
箔とそれを用いた印刷回路基板の提供を目的とする。The present invention solves the above-mentioned problems when a fine circuit pattern is formed using a resin-coated copper foil, and it is difficult for cracks to occur in the insulating resin layer or peeling from the copper foil during handling. An object of the present invention is to provide a copper foil with a resin, which can form a highly reliable high-density ultrafine wiring circuit pattern and is useful as a copper foil for a multilayer printed circuit board, and a printed circuit board using the same.
【００１７】[0017]
【課題を解決するための手段】上記した目的を達成する
ために、本発明においては、表面粗度（Ｒｚ）２〜４μ
ｍの粗化面を有する電解銅箔の前記粗化面に、厚みが２
０〜８０μｍである半硬化状態の絶縁樹脂層が密着して
接合されていることを特徴とする印刷回路基板用樹脂付
き銅箔が提供され、またそれを用いた印刷回路基板が提
供される。According to the present invention, in order to achieve the above-mentioned object, the surface roughness (Rz) is 2 to 4 μm.
m on the roughened surface of the electrolytic copper foil having a roughened surface having a thickness of 2 m.
A resin-coated copper foil for a printed circuit board is provided, in which a semi-cured insulating resin layer having a thickness of 0 to 80 μm is adhered and bonded, and a printed circuit board using the same is provided.
【００１８】[0018]
【発明の実施の形態】本発明の樹脂付き銅箔の１例を図
１に示す。図１で示したように、本発明の樹脂付き銅箔
Ａは、電解銅箔１の片面が粗化面１ａになっていて、こ
の粗化面１ａに半硬化状態の絶縁樹脂層２が密着して接
合した構造になっている。本発明においては、この粗化
面１ａの表面粗度が、ＪＩＳ Ｂ０６０１が規定する値
（Ｒｚ）で２〜４μｍになっていることを特徴とする。FIG. 1 shows an example of a resin-coated copper foil of the present invention. As shown in FIG. 1, the copper foil with resin A of the present invention has a roughened surface 1a on one side of an electrolytic copper foil 1, and a semi-cured insulating resin layer 2 adheres to the roughened surface 1a. The structure is joined. The present invention is characterized in that the surface roughness of the roughened surface 1a is 2 to 4 μm as a value (Rz) specified by JIS B0601.
【００１９】Ｒｚ値が２μｍより小さい場合には、ここ
に形成される絶縁樹脂層２との間のアンカー効果が充分
に発揮されず、そのため、後述する内層材への積層工程
に先立つ過程における巻取りや巻戻しなどのハンドリン
グ時に、絶縁樹脂層２へのクラック発生，絶縁樹脂層２
が銅箔１から部分的に剥離するなどが起こりやすく、ま
た、内層材への積層後も表面の回路パターンと基材との
接合強度が不足して、当該回路パターンが剥離したり、
エッチング時に断線したりすることもあるなどの問題が
起こりやすく、良質の印刷回路基板の製造は困難にな
る。If the Rz value is smaller than 2 μm, the anchor effect between the insulating resin layer 2 and the insulating resin layer 2 formed thereon is not sufficiently exhibited. During handling such as removal and rewinding, cracks occur in the insulating resin layer 2 and the insulating resin layer 2
Is likely to be partially peeled off from the copper foil 1, and the bonding strength between the circuit pattern on the surface and the base material is insufficient even after lamination on the inner layer material, and the circuit pattern is peeled off,
Problems such as disconnection during etching are likely to occur, making it difficult to manufacture a high quality printed circuit board.
【００２０】また、Ｒｚ値が４μｍより大きい場合は、
粗化面１ａの突起部の絶縁樹脂層２への喰込み量が大き
くなり、エッチングによる回路パターンの形成時にこの
喰い込んだ突起部の完全除去に時間がかかるため、既に
形成されている回路パターンの側壁のエッチングが進行
し、その結果、前記したＥｆ値の低下を招き、ファイン
な回路パターンの形成は困難になる。更には、回路パタ
ーン間の絶縁や、層間絶縁の低下という問題も起こりや
すくなる。When the Rz value is larger than 4 μm,
The amount of protrusion of the roughened surface 1a into the insulating resin layer 2 becomes large, and it takes time to completely remove the bite protrusion when forming the circuit pattern by etching. Etching of the side wall proceeds, and as a result, the above-mentioned decrease in the Ef value is caused, and it becomes difficult to form a fine circuit pattern. Further, problems such as insulation between circuit patterns and deterioration of interlayer insulation are likely to occur.
【００２１】本発明において、銅箔として電解銅箔を用
いる理由は、電解銅箔の場合、圧延銅箔に比べてその厚
みが５〜１２μｍと極薄であっても、厚みは比較的均一
であり、しかも広幅な箔として比較的低コストで製造す
ることができるからである。本発明の樹脂付き銅箔の場
合、用いる電解銅箔としてその厚みが１５μｍ以下であ
るものに対して優れた効果を発揮する。In the present invention, the reason why the electrolytic copper foil is used as the copper foil is that, in the case of the electrolytic copper foil, the thickness is relatively uniform even though the thickness is as thin as 5 to 12 μm as compared with the rolled copper foil. This is because it can be manufactured as a wide foil at a relatively low cost. In the case of the resin-coated copper foil of the present invention, an excellent effect is exhibited for an electrolytic copper foil having a thickness of 15 μm or less.
【００２２】本願請求項３の発明で、電解銅箔の厚みを
１５μｍ以下としたものは、下記の理由による。すなわ
ち、一般に、銅箔の厚みは薄くなるほど前記したエッチ
ングファクタは大きくなってファインな回路パターンを
形成しやすくなるが、他方では、その厚みが１５μｍよ
り薄くなると銅箔の腰が急激に弱くなって取り扱いが困
難になるという問題がある。In the invention of claim 3 of the present application, the thickness of the electrolytic copper foil is set to 15 μm or less for the following reasons. That is, in general, as the thickness of the copper foil becomes thinner, the above-mentioned etching factor becomes larger and it becomes easier to form a fine circuit pattern. On the other hand, when the thickness becomes thinner than 15 μm, the stiffness of the copper foil rapidly becomes weak. There is a problem that handling becomes difficult.
【００２３】しかしながら、本発明の場合には、銅箔の
厚みが１５μｍより薄いときでも、その銅箔には後述す
る半硬化状態の絶縁樹脂層が接合されていて、この絶縁
樹脂が補強材の役割を果たしているので、銅箔の腰が弱
くなるという問題を生ずることなく高いエッチングファ
クタが得られることになるからである。電解銅箔は、表
面平滑な回転ドラムの当該表面に通常は硫酸銅浴を用い
て銅を電解析出させて成膜し、それを連続的に回転ドラ
ムから剥離して製造されている。したがって、得られた
電解銅箔の剥離面は比較的平滑であり、銅の析出面（マ
ット面）は比較的粗面になっており、銅張り積層板の製
造時には、このマット面が基材との接着面として機能す
る。However, in the case of the present invention, even when the thickness of the copper foil is thinner than 15 μm, a semi-cured insulating resin layer described later is joined to the copper foil, and this insulating resin serves as a reinforcing material. This is because, since it plays a role, a high etching factor can be obtained without causing the problem that the copper foil becomes weak. The electrolytic copper foil is produced by depositing copper on the surface of a rotating drum having a smooth surface, usually by electrolytic deposition of copper using a copper sulfate bath, and continuously peeling the film from the rotating drum. Therefore, the peeled surface of the obtained electrolytic copper foil is relatively smooth, and the copper deposition surface (mat surface) is relatively rough, and this mat surface is used as a base material during the production of a copper-clad laminate. Functions as an adhesive surface with
【００２４】そして、このマット面の表面粗度は基材と
の接合強度に影響を与えるため、適正な表面粗度の実現
を目的とした電解条件の選定が行われている。電解銅箔
は、その生産効率を高めるために、通常、２０〜１５０
Ａ／dm2という高電流密度で製造されている。このよう
な条件下では、例えば厚み１８μｍの電解銅箔を製造す
ると、その表面粗度はＲｚ５μｍ程度となり、比較的粗
いマット面が形成されている。しかしながら、例えば市
販の装飾用光沢銅めっき浴やチオ尿素，糖蜜などを添加
した電解浴を用いたり、また電流密度を２０Ａ／dm2以
下に下げるなど電解条件を変えることにより、マット面
をＲｚ１μｍ程度にまで平滑にすることもできる。更に
は、比較的粗いマット面に対して、例えば電解研磨法や
化学研磨法などを適用して当該マット面を平滑にするこ
ともできる。Since the surface roughness of the matte surface has an effect on the bonding strength with the base material, electrolytic conditions have been selected for the purpose of realizing an appropriate surface roughness. Electrodeposited copper foil is usually 20 to 150 to increase its production efficiency.
It is manufactured at a high current density of A / dm 2 . Under such conditions, for example, when an electrolytic copper foil having a thickness of 18 μm is manufactured, its surface roughness is about Rz 5 μm, and a relatively rough mat surface is formed. However, by using a commercially available bright copper plating bath for decoration, an electrolytic bath to which thiourea, molasses, etc. are added, or by changing the electrolytic conditions such as lowering the current density to 20 A / dm 2 or less, the mat surface can be made to have an Rz of about 1 μm. Can be smoothed. Further, for example, an electrolytic polishing method or a chemical polishing method may be applied to a relatively rough mat surface to smooth the mat surface.
【００２５】本発明で用いる電解銅箔は、上記した製造
方法において電解条件などを適切に選択することによ
り、そのマット面の表面粗度をＲｚ２〜４μｍにするこ
ともできる。その場合、本発明の電解銅箔の製造に際し
ては、次のような粗化処理を行うことが好ましい。The surface roughness of the matte surface of the electrolytic copper foil used in the present invention can be adjusted to Rz 2 to 4 μm by appropriately selecting electrolytic conditions and the like in the above-described production method. In that case, when manufacturing the electrolytic copper foil of the present invention, it is preferable to perform the following roughening treatment.
【００２６】例えば、電解銅箔製造における最終工程
で、既に成膜されている銅箔のマット面に更に粒子径が
０.１〜３μｍの突起物を形成するという処理である。
突起物の粒子径が０.１μｍより小さい場合は、銅張り
積層板の製造時における内層材への接合強度を高める効
果は不充分であり、逆に３μｍより大きい場合は、たし
かに上記接合強度は高くなるものの、他方では銅箔の表
面粗度が大きくなってエッチング時におけるファインな
回路パターンの形成に難点が生ずる。このようなことか
ら突起物の粒子径は０.１〜３μｍに制御することが好
ましい。For example, in a final step in the production of an electrolytic copper foil, there is a process in which a projection having a particle diameter of 0.1 to 3 μm is further formed on the mat surface of the already formed copper foil.
If the particle size of the protrusions is smaller than 0.1 μm, the effect of increasing the bonding strength to the inner layer material during the production of the copper-clad laminate is insufficient, and if the particle size is larger than 3 μm, the bonding strength is certainly higher. On the other hand, on the other hand, the surface roughness of the copper foil is increased, which causes difficulty in forming a fine circuit pattern during etching. For this reason, it is preferable to control the particle diameter of the protrusion to 0.1 to 3 μm.
【００２７】この突起物は通常銅粒子で形成される。し
かし、銅−亜鉛合金，銅−ニッケル合金，亜鉛−ニッケ
ル合金などで形成されてもよい。この突起物の形成方法
としては、通常、電着法が採用される。突起物を電着法
によって銅粒子で形成する場合、回転ドラムへの銅電着
に続けて行えばよい。そのとき、浴組成，浴温，処理時
間などを変化させることにより、銅粒子の粒子径や析出
量を所望の状態に制御することができるので、適切な条
件を選定して粒子径を上記範囲内に設定することができ
る。This projection is usually formed of copper particles. However, it may be formed of a copper-zinc alloy, a copper-nickel alloy, a zinc-nickel alloy, or the like. As a method for forming the projection, an electrodeposition method is usually employed. When the projections are formed of copper particles by an electrodeposition method, the projections may be performed following the copper electrodeposition on the rotating drum. At this time, by changing the bath composition, the bath temperature, the treatment time, and the like, the particle size and the amount of precipitation of the copper particles can be controlled to a desired state. Can be set within.
【００２８】なお、突起物の形成方法としては、無電解
めっき法，メタライジング法，スプレー法，蒸着法，ス
パッタ法など公知の他の方法であってもよい。その場
合、電解銅箔のマット面の全表面に均一な粒子径の突起
物が付着し、またマット面との間で充分な密着力が発現
するような条件を採用すべきである。上記した突起物の
形成に続けて、次のような突起物を更に形成して、いわ
ば２次粗化処理を行うと、銅箔の表面粗度を比較的小さ
く保ったままで内層材との接合強度を高めることができ
るので好適である。The projections may be formed by other known methods such as an electroless plating method, a metallizing method, a spray method, a vapor deposition method, and a sputtering method. In this case, conditions should be adopted such that projections having a uniform particle diameter adhere to the entire surface of the matte surface of the electrolytic copper foil, and that a sufficient adhesive force is exhibited between the matte surface. Following the formation of the above-described protrusions, the following protrusions are further formed, and so-called secondary roughening treatment is performed. When the surface roughness of the copper foil is kept relatively small, bonding with the inner layer material is performed. This is preferable because the strength can be increased.
【００２９】内層材との接合強度を高めることを目的と
して前記した突起物の形成量を多くすると、形成された
突起物は部分的に樹枝状に成長して表面粗度は非常に大
きくなってしまい、結局、ファインな回路パターンの形
成が困難になる。前記した２次粗化処理を行うことによ
り、上記した事態の発生が抑制されるのである。When the formation amount of the above-mentioned protrusions is increased for the purpose of increasing the bonding strength with the inner layer material, the formed protrusions partially grow into dendrites and the surface roughness becomes very large. Eventually, it becomes difficult to form a fine circuit pattern. The occurrence of the above-mentioned situation is suppressed by performing the above-mentioned secondary roughening processing.
【００３０】その場合、最初の粗化処理では、粒子径が
０.５〜３μｍの比較的粗い突起物をマット面に薄く均
一に形成し、ついでそこに、粒子径が０.０５〜１μｍ
のより微細な突起物を析出させて２次粗化処理を行うこ
とが好ましい。この２次粗化処理は電着法で行うことが
好ましく、例えば銅粒子を析出させる場合、浴組成や浴
温、電流密度や処理時間を適切に選定することにより、
望ましくは、既に形成されている粗い突起物の凸部だけ
ではなく凹部にも均一に析出させることが好ましい。そ
の場合、浴組成としては、硫酸銅浴に砒素やベンゾキノ
リン系添加剤などを加えたものを使用することができ
る。In this case, in the first roughening treatment, relatively coarse protrusions having a particle diameter of 0.5 to 3 μm are formed thinly and uniformly on the mat surface, and then a particle diameter of 0.05 to 1 μm is formed thereon.
It is preferable to perform a secondary roughening treatment by precipitating finer projections. This secondary roughening treatment is preferably performed by an electrodeposition method. For example, when copper particles are precipitated, by appropriately selecting a bath composition, a bath temperature, a current density, and a treatment time,
Desirably, it is preferable to uniformly deposit not only on the projections of the coarse projections already formed but also on the depressions. In this case, as the bath composition, a copper sulfate bath to which arsenic, a benzoquinoline-based additive, or the like is added can be used.
【００３１】このようにして、本発明の電解銅箔はその
マット面における表面粗度Ｒｚが２〜４μｍに調整され
る。前記した２次粗化処理後にあっても、その表面粗度
Ｒｚは上記範囲に設定されることが必要である。本発明
においては、電解銅箔の上記粗化面に半硬化状態の絶縁
樹脂層が形成される。Thus, the surface roughness Rz on the matte surface of the electrolytic copper foil of the present invention is adjusted to 2 to 4 μm. Even after the secondary roughening treatment, the surface roughness Rz needs to be set in the above range. In the present invention, a semi-cured insulating resin layer is formed on the roughened surface of the electrolytic copper foil.
【００３２】ここでいう半硬化状態とは、いわゆるＢス
テージ状態であって、表面を指で触れても粘着感はな
く、その樹脂層を重ね合わせて保管することができ、更
に加熱処理を受けると硬化反応が起こる状態のことをい
う。絶縁樹脂層を電解銅箔の上記粗化面に形成するに先
立ち、当該電解銅箔の粗化面に、銅，亜鉛，ニッケルま
たはそれらの合金から成る薄層を例えば電着法で形成す
ると、銅箔表面の酸化や前記した突起物の脱落が有効に
防止され、もって内層材との接合強度が低下することを
防止できるので好適である。The semi-cured state referred to herein is a so-called B-stage state in which the surface of the resin layer is not sticky even when touched with a finger, and the resin layers can be stored in an overlapped state, and further subjected to a heat treatment. And a state in which a curing reaction occurs. Prior to forming the insulating resin layer on the roughened surface of the electrolytic copper foil, a thin layer made of copper, zinc, nickel or an alloy thereof is formed on the roughened surface of the electrolytic copper foil by, for example, an electrodeposition method. It is preferable because oxidation of the copper foil surface and detachment of the above-mentioned protrusions can be effectively prevented, so that a decrease in bonding strength with the inner layer material can be prevented.
【００３３】また、上記電解銅箔に更にクロメート処理
を行うと、当該電解銅箔に酸化防止層が形成される。適
用するクロメート処理としては、公知の方法であってよ
く、例えば、特開昭６０−８６８９４号に開示されてい
る方法をあげることができる。クロム量に換算して０.
０１〜０.２mg／dm2程度のクロム酸化物とその水和物な
どを付着させることにより、電解銅箔には優れた防食能
を付与することができる。When the above-mentioned electrolytic copper foil is further subjected to a chromate treatment, an oxidation preventing layer is formed on the electrolytic copper foil. The chromate treatment to be applied may be a known method, for example, a method disclosed in JP-A-60-86894. Converted to the amount of chromium,
By attaching about 01 to 0.2 mg / dm 2 of chromium oxide and its hydrate, excellent corrosion protection can be imparted to the electrolytic copper foil.
【００３４】このような前処理の終了後、電解銅箔の表
面に対し更にシランカップリング剤を用いた表面処理を
行うことが好ましい。最終的に形成される絶縁樹脂層と
電解銅箔との接合強度を高くすることができるからであ
る。用いるシランカップリング剤としては、次式： ＹＲＳｉＸ3 …(1) （式中、Ｙは絶縁樹脂層のマトリックス樹脂と結合可能
な有機官能基，Ｒはアルキル基，Ｘは独立して加水分解
能を有する基を表す）で示されるものである。After the completion of the pretreatment, it is preferable that the surface of the electrolytic copper foil is further subjected to a surface treatment using a silane coupling agent. This is because the bonding strength between the finally formed insulating resin layer and the electrolytic copper foil can be increased. The silane coupling agent used is represented by the following formula: YRSix 3 (1) (where Y is an organic functional group capable of binding to the matrix resin of the insulating resin layer, R is an alkyl group, and X is independently a hydrolytic compound. Represents a group having).
【００３５】上記化合物は、空気中の水分や電解銅箔表
面の水和酸化物に付着する水分との間で、次式： ＹＲＳｉＸ3＋３Ｈ2Ｏ→ＹＲＳｉ（ＯＨ）3＋３ＨＸ …(2) に基づく反応を起こし、シラノール基を有する化合物に
なる。そして、上記化合物において、シラノール基は電
解銅箔の突起物の表面またはクロム水和酸化物層の表面
と結合し、基Ｙは後述する絶縁樹脂層のマトリックス樹
脂と結合するので、電解銅箔と絶縁樹脂層はこのシラン
カップリング剤を媒介にして強固に結合されることにな
る。The above compound has the following formula: YRSix 3 + 3H 2 O → YRSi (OH) 3 + 3HX (2) between water in the air and water adhering to the hydrated oxide on the surface of the electrolytic copper foil. And a compound having a silanol group is obtained. In the above compound, the silanol group is bonded to the surface of the projection of the electrolytic copper foil or the surface of the chromium hydrated oxide layer, and the group Y is bonded to the matrix resin of the insulating resin layer described later. The insulating resin layer is firmly bonded via the silane coupling agent.
【００３６】(1)式におけるＸとしては、例えば、クロ
ル基，アルコキシ基などをあげることができ、Ｙとして
は、ビニル基，エポキシ基，グリシドキシ基，メタクリ
ロキシ基，アミノ基，Ｎ−（２−アミノエチル）アミノ
基などをあげることができる。(1)式のシランカップリ
ング剤の具体例としては、ビニルトリス（２−メトキシ
エトキシ）シラン，３−グリシドキシプロピルトリメト
キシシラン，Ｎ−（２−アミノエチル）−３−アミノプ
ロピルトリメトキシシラン，３−アミノプロピルトリエ
トキシシランなどをあげることができる。In the formula (1), X can be, for example, a chloro group or an alkoxy group, and Y can be a vinyl group, an epoxy group, a glycidoxy group, a methacryloxy group, an amino group, an N- (2- Aminoethyl) amino group and the like. Specific examples of the silane coupling agent of the formula (1) include vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane and the like.
【００３７】シランカップリング処理は、上記したシラ
ンカップリング剤の濃度０.００１〜５％水溶液を調製
し、これを前記した電解銅箔の表面に塗布したのち、水
洗することなく、そのまま温度１００〜１３０℃程度で
乾燥すればよい。なお、本発明においては、上記シラン
カップリング剤に代えて、チタン系，ジルコン系のカッ
プリング剤を使用してもよい。In the silane coupling treatment, a 0.001 to 5% aqueous solution of the above-mentioned silane coupling agent is prepared, applied to the surface of the above-mentioned electrolytic copper foil, and then subjected to a temperature of 100 without washing with water. What is necessary is just to dry at about 130 degreeC. In the present invention, a titanium-based or zircon-based coupling agent may be used instead of the silane coupling agent.
【００３８】以上のような表面処理が施された電解銅箔
における内層材との接合面には熱硬化性樹脂が塗布さ
れ、それを加熱して半硬化状態にすることにより本発明
の樹脂付き銅箔が製造される。用いる熱硬化性樹脂とし
ては格別限定されるものではなく、例えば、エポキシ
系，ポリイミド系，ＢＴレジン系，フェノール系などを
あげることができるが、とくに、接合対象の内層材を構
成する熱硬化性のマトリックス樹脂と同系統のものであ
ることが好ましい。A thermosetting resin is applied to the surface of the electrodeposited copper foil which has been subjected to the surface treatment as described above and is bonded to the inner layer material. Copper foil is manufactured. The thermosetting resin to be used is not particularly limited, and examples thereof include an epoxy type, a polyimide type, a BT resin type, and a phenol type. Particularly, the thermosetting resin constituting the inner layer material to be joined is used. It is preferably of the same type as the matrix resin of the above.
【００３９】塗布は、上記した熱硬化性樹脂を、少量の
メチルエチルケトン，トルエン，メタノール，アセトン
などの溶剤で希釈したり、または、液状エポキシ樹脂や
フェニレングリシジルエーテルのような反応性希釈剤な
どで希釈して適当な粘度にし、それを、印刷法，浸漬
法，ロールコータ法，カーテンコータ法，グラビアコー
タ法などで塗布すればよい。The coating is performed by diluting the above-mentioned thermosetting resin with a small amount of a solvent such as methyl ethyl ketone, toluene, methanol or acetone, or diluting with a reactive diluent such as a liquid epoxy resin or phenylene glycidyl ether. The viscosity may be adjusted to a suitable value by a printing method, a dipping method, a roll coater method, a curtain coater method, a gravure coater method, or the like.
【００４０】塗布後、次に、塗膜を加熱乾燥して半硬化
状態の絶縁樹脂層にする。そのときの条件は、用いた熱
硬化性樹脂の種類や溶剤の希釈量や塗布量などによって
決まってくるが、通常は、温度１３０〜１８０℃で２〜
２０分程度の熱風乾燥を行えばよい。なお、このときの
塗布量は、加熱乾燥によって得られる絶縁樹脂層の厚み
が２０〜８０μｍになるように設定することが必要であ
る。After the application, the coating film is dried by heating to form a semi-cured insulating resin layer. The conditions at that time are determined by the type of the thermosetting resin used, the amount of dilution of the solvent, the amount of application, and the like.
Hot air drying may be performed for about 20 minutes. It is necessary to set the amount of application at this time so that the thickness of the insulating resin layer obtained by heating and drying becomes 20 to 80 μm.
【００４１】絶縁樹脂層の厚みが２０μｍより薄くなる
と、プリプレグ材を介在させることなくこの樹脂付き銅
箔を内層材に積層したときに、内層材の回路との間の層
間絶縁を確保することが困難になるからである。また、
絶縁樹脂層の厚みを８０μｍより厚くすると、１回の塗
布工程で目的厚みの絶縁樹脂層を形成することが困難と
なり、余分な材料費と工数がかかるため経済的に不利と
なる。更には、形成された絶縁樹脂層はその可撓性が劣
るので、ハンドリング時にクラックなどが発生しやすく
なり、また内層材との熱圧着時に過剰な樹脂流れが起こ
って円滑な積層が困難になるからである。When the thickness of the insulating resin layer is less than 20 μm, when the resin-coated copper foil is laminated on the inner layer material without the interposition of the prepreg material, it is necessary to ensure interlayer insulation between the inner layer material and the circuit. Because it becomes difficult. Also,
If the thickness of the insulating resin layer is more than 80 μm, it becomes difficult to form an insulating resin layer having a desired thickness in one coating step, and it is economically disadvantageous because extra material costs and man-hours are required. Furthermore, since the formed insulating resin layer is inferior in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. Because.
【００４２】本発明の印刷回路基板は、上記したように
して製造される樹脂付き銅箔を用いることにより次のよ
うにして製造される。まず、ロールに巻き取られている
樹脂付き銅箔を巻戻して所定の寸法形状に裁断する。回
路パターンが予め形成されている内層材の上・下面に樹
脂付き銅箔の絶縁樹脂層側の面を重ね合わせて全体を熱
圧着することにより銅張り積層板にする。この過程で従
来のように樹脂付き銅箔と内層材の間にプリプレグ材を
配置してもよい。しかし、プリプレグ材を配置しなくて
も充分に目的を達成することはできる。The printed circuit board of the present invention is manufactured as follows by using the resin-coated copper foil manufactured as described above. First, the resin-coated copper foil wound on the roll is rewound and cut into a predetermined size and shape. The surface of the resin-coated copper foil on the insulating resin layer side is overlapped on the upper and lower surfaces of the inner layer material on which the circuit pattern is formed in advance, and the whole is thermocompression-bonded to form a copper-clad laminate. In this process, a prepreg material may be arranged between the resin-coated copper foil and the inner layer material as in the related art. However, the purpose can be sufficiently achieved without disposing the prepreg material.
【００４３】ついで、この銅張り積層板に、スルーホー
ルやバイヤホールの穿設加工、更に最外表面をエッチン
グして所望の回路パターンを形成し、ソルダーレジスト
の塗布，半田コーティングやその他の加工工程を経て多
層印刷回路基板が製造される。Then, through holes and via holes are formed in the copper-clad laminate, and the outermost surface is etched to form a desired circuit pattern. Then, solder resist coating, solder coating and other processing steps are performed. After that, a multilayer printed circuit board is manufactured.
【００４４】[0044]
【実施例】 実施例１〜３，比較例１〜６ (1)電解銅箔の製造 下記の条件で、幅３００mm，厚み１２μｍの長尺電解銅
箔を連続的に製造した。EXAMPLES Examples 1 to 3 and Comparative Examples 1 to 6 (1) Production of Electrodeposited Copper Foil Under the following conditions, a long electrolytic copper foil having a width of 300 mm and a thickness of 12 μm was continuously produced.
【００４５】浴組成：銅５５ｇ／Ｌ，硫酸５５ｇ／Ｌ，
塩化物イオン９０ppm（ＮａＣｌとして）、ガパラシド
２１０（日本シェーリング社製の光沢用添加剤、メイキ
ャップ剤５mL／Ｌと光沢剤Ａ０.５mL／Ｌを含有）。 浴温：２７℃。 対極：含リン銅板。Bath composition: 55 g / L of copper, 55 g / L of sulfuric acid,
90 ppm of chloride ion (as NaCl), Gapalaside 210 (containing a glossing additive manufactured by Nippon Schering Co., Ltd., 5 mL / L of make-up agent and 0.5 mL / L of brightener A). Bath temperature: 27 ° C. Counter electrode: Phosphorous copper plate.
【００４６】電流密度：６Ａ／dm2。電解銅箔のマット
面の表面粗度をＪＩＳ Ｂ０６０１で規定する方法によ
って測定した。１０点平均表面粗度（Ｒｚ）は１.２μ
ｍであった。 (2)粗化処理 まず、銅：３０ｇ／Ｌ，硫酸：６０ｇ／Ｌ，砒素：０.
５ｇ／Ｌから成る組成の電析浴を建浴した。これを浴
(1)とする。また、銅：８０ｇ／Ｌ，硫酸：７０ｇ／Ｌ
から成る電析浴を建浴した。これを浴(2)とする。Current density: 6 A / dm 2 . The surface roughness of the matte surface of the electrolytic copper foil was measured by a method specified in JIS B0601. 10 point average surface roughness (Rz) is 1.2μ
m. (2) Roughening treatment First, copper: 30 g / L, sulfuric acid: 60 g / L, arsenic: 0.1 g / L
An electrodeposition bath having a composition of 5 g / L was prepared. Take this
(1) Copper: 80 g / L, sulfuric acid: 70 g / L
An electrodeposition bath consisting of This is called bath (2).
【００４７】前記した電解銅箔のマット面を、浴(1)を
用い、温度：２２℃，電流密度：３０Ａ／dm2の条件下
で表１，２に示した時間処理したのち、続けて、浴(2)
を用い、浴温：５５℃，電流密度：２０Ａ／dm2の条件
下で表１，２で示した時間処理して、マット面に銅粒子
を析出させる１次粗化処理を行った。これら１次処理銅
箔の粗化面を顕微鏡観察したところ、いずれも、全面に
微粒子状の突起が認められた。各１次処理銅箔の粗化面
のＲｚ値を測定し、それを表１，２に示した。The matte surface of the above-mentioned electrolytic copper foil was treated in a bath (1) under the conditions of a temperature of 22 ° C. and a current density of 30 A / dm 2 for the times shown in Tables 1 and 2, and subsequently. , Bath (2)
And a primary roughening treatment of depositing copper particles on the matte surface was performed under the conditions of bath temperature: 55 ° C. and current density: 20 A / dm 2 for the time shown in Tables 1 and 2. Microscopic observation of the roughened surfaces of these primary-treated copper foils revealed fine-particle projections on all surfaces. The Rz value of the roughened surface of each primary-treated copper foil was measured, and the results are shown in Tables 1 and 2.
【００４８】ついで、銅：１２ｇ／Ｌ，硫酸：６０ｇ／
Ｌの電析浴を建浴した。これを浴(3)とする。この浴(3)
を用い、前記した各１次処理銅箔を浴温：２７℃，電流
密度：１０Ａ／dm2の条件下で表１，２に示した時間処
理して２次粗化処理を行った。この２次処理銅箔の粗化
面を顕微鏡観察したところ、前記１次処理銅箔の突起の
表面には、更に細かい微粒子状の突起が認められた。Then, copper: 12 g / L, sulfuric acid: 60 g / L
The L electrodeposition bath was set up. This is called bath (3). This bath (3)
Each of the primary-treated copper foils was subjected to a secondary roughening treatment by treating the above-mentioned primary-treated copper foils at a bath temperature of 27 ° C. and a current density of 10 A / dm 2 for the times shown in Tables 1 and 2. Microscopic observation of the roughened surface of the secondary-treated copper foil revealed finer, fine-particle projections on the surface of the projections of the primary-treated copper foil.
【００４９】得られた各２次処理銅箔のＲｚ値を測定
し、それを表１，２に示した。なお、表１，２で示し
た、実施例１，２比較例１，２の銅箔については、上記
した２次粗化処理は行っていない。 (3)銅箔の化学処理 上記した粗化処理銅箔に硫酸亜鉛７水塩：２０ｇ／Ｌ，
水酸化ナトリウム：８０ｇ／Ｌの組成浴を用い、対極と
してステンレス鋼板を用い、浴温：２８℃，電流密度：
０.５Ａ／dm2の条件下で２秒間の処理を施して、各銅箔
の粗化面に亜鉛めっきを行った。The Rz value of each of the obtained secondary-treated copper foils was measured, and the results are shown in Tables 1 and 2. The copper foils of Examples 1 and 2 and Comparative Examples 1 and 2 shown in Tables 1 and 2 were not subjected to the above secondary roughening treatment. (3) Chemical treatment of copper foil Zinc sulfate heptahydrate: 20 g / L,
Sodium hydroxide: 80 g / L composition bath, stainless steel plate as counter electrode, bath temperature: 28 ° C., current density:
The treatment was performed for 2 seconds under the condition of 0.5 A / dm 2 , and the roughened surface of each copper foil was galvanized.
【００５０】ついで、各銅箔を水洗したのち、三酸化ク
ロム４ｇ／Ｌ，ｐＨ１１.５の水酸化ナトリウム水溶液
（液温：５５℃）に６秒間浸漬してクロメート処理を行
い、水洗乾燥した。更に、これらの各銅箔を、３−アミ
ノプロピルトリメトキシシラン２ｇ／Ｌの水溶液に浸漬
したのち取り出し、ついで銅箔の表面を軟質ゴム板でし
ごいて水切りを行ったのち温度１２０℃で乾燥してシラ
ンカップリング剤処理を行った。Then, after each copper foil was washed with water, it was immersed in a 4 g / L chromium trioxide aqueous solution of sodium hydroxide having a pH of 11.5 (liquid temperature: 55 ° C.) for 6 seconds, subjected to a chromate treatment, washed with water and dried. Further, each of these copper foils was immersed in an aqueous solution of 3-aminopropyltrimethoxysilane at 2 g / L and taken out. Then, the surface of the copper foil was wiped off with a soft rubber plate, and then dried at a temperature of 120 ° C. Then, a silane coupling agent treatment was performed.
【００５１】(4)樹脂付き銅箔の製造 エピクロン１１２１−７５Ｍ（商品名、大日本インキ化
学工業（株）製のビスフェノールＡ型エポキシ樹脂），
ジシアンジアミミド，２−エチル−４−メチルイミダゾ
ール，メチルセロソルブを、１３３：２.１：０.１：２
０の重量割合で充分に混合して、熱硬化性樹脂のワニス
を調製した。(4) Production of copper foil with resin Epicron 1121-75M (trade name, bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.),
Dicyandiamid, 2-ethyl-4-methylimidazole, methyl cellosolve 133: 2.1: 0.1: 2
The mixture was sufficiently mixed at a weight ratio of 0 to prepare a varnish of a thermosetting resin.
【００５２】ついで、前記した化学処理が終了した各銅
箔の粗化面に、前記ワニスを試験用ロールで乾燥後に表
１，２に示した厚みとなるように塗布したのち、塗布し
たワニスを温度１６０℃で５分間乾燥して半硬化状態の
絶縁樹脂層にし、それぞれを直径１００mmの巻取りロー
ルで巻き取った。各巻取りロールを２４時間室温下で放
置したのち、各樹脂付き銅箔を水平な面に巻き戻して絶
縁樹脂層の表面を精密観察し、絶縁樹脂層のクラック発
生の有無や銅箔からの部分剥離などを調べた。その結果
を表１，２に示した。Then, the varnish was applied to the roughened surface of each of the copper foils having been subjected to the above chemical treatment so as to have a thickness shown in Tables 1 and 2 after being dried with a test roll. The film was dried at a temperature of 160 ° C. for 5 minutes to form a semi-cured insulating resin layer, and each was wound up by a winding roll having a diameter of 100 mm. After leaving each take-up roll at room temperature for 24 hours, each resin-coated copper foil is rewound to a horizontal surface, and the surface of the insulating resin layer is closely observed to determine whether or not cracks have occurred in the insulating resin layer and the portion from the copper foil. Exfoliation was examined. The results are shown in Tables 1 and 2.
【００５３】(5)銅張り積層板の製造 上記した各樹脂付き銅箔の絶縁樹脂層側の表面を、別
途、最外層に厚み１８μｍの銅箔を用いて調製してあっ
た厚み１.２mmの多層印刷回路基板用の内層材の上・下
面に重ね合わせたのち、圧力３０kg／cm2，温度１７５
℃で１００分間熱圧着し、その後、４０℃で６０分間冷
却して銅張り積層板にした。(5) Production of copper-clad laminate The surface of the above-mentioned resin-coated copper foil on the insulating resin layer side was separately prepared using a 18-μm-thick copper foil as the outermost layer. Of the inner layer material for the multilayer printed circuit board of the above, the pressure is 30 kg / cm 2 , the temperature is 175
Thermocompression bonding was performed at 100 ° C. for 100 minutes, followed by cooling at 40 ° C. for 60 minutes to obtain a copper-clad laminate.
【００５４】各積層板からそれぞれ試料を切り出し、各
試料に付き、ＪＩＳ Ｃ６４８１で規定する方法に準拠
して、銅箔の引き剥がし強さを測定した。また、製造さ
れた銅張り積層板の場合、その積層断面を観察すると、
絶縁樹脂層２の厚みは図２で示したように、均一ではな
く、局部的に異なっている。そこで、全体を代表する製
造サンプルを採取し、積層板の長さ１cmの部分に亘って
積層断面を顕微鏡観察して、銅箔の粗化面１ａと内層材
の最外層の回路パターン３との間隔が最も狭くなる箇所
の間隔（図２におけるＬ）を測定し、その値を最小絶縁
層厚みとした。その結果を表１，２に示した。A sample was cut out from each laminated plate, and the peel strength of the copper foil was measured for each sample according to the method specified in JIS C6481. Also, in the case of the manufactured copper-clad laminate, when observing the laminated cross section,
As shown in FIG. 2, the thickness of the insulating resin layer 2 is not uniform, but differs locally. Therefore, a manufacturing sample representing the whole is taken, and the lamination cross section is observed under a microscope over a portion of 1 cm in length of the laminate, and the roughened surface 1a of the copper foil and the circuit pattern 3 of the outermost layer of the inner layer material are compared. The interval (L in FIG. 2) at the point where the interval became the narrowest was measured, and the value was defined as the minimum insulating layer thickness. The results are shown in Tables 1 and 2.
【００５５】(6)印刷回路基板の製造 各積層板の表面に、それぞれ、紫外線硬化レジストを塗
布し、ここに、紫外線露光・現像を行って、線幅６０μ
ｍ，線間ギャップ４０μｍ，配線ピッチ１００μｍのエ
ッチングレジストを形成したのち、塩化鉄２.０モル／
Ｌ，塩酸０.４モル／Ｌから成るエッチャントをスプレ
ー噴霧してエッチング処理を行って回路パターンを形成
した。(6) Production of Printed Circuit Board An ultraviolet-curing resist is applied to the surface of each laminated board, and is subjected to ultraviolet exposure and development, and has a line width of 60 μm.
m, an inter-line gap of 40 μm, and a wiring pitch of 100 μm.
An etchant consisting of 0.4 mol / L of L and hydrochloric acid was spray-sprayed to perform an etching treatment to form a circuit pattern.
【００５６】なお、各積層板へのエッチング時間は、同
一積層板を用いて予備試験を行い、回路パターンのボト
ム幅が５０μｍ、線間ギャップが５０μｍとなる最適時
間を調べ、当該時間を採用した。得られた印刷回路基板
における回路パターンの断面写真を撮影して回路パター
ンのトップ幅，ボトム幅を測定し、前記した(1)式に基
づいてＥｆ値を算出した。As for the etching time for each laminated board, a preliminary test was performed using the same laminated board, and the optimum time when the bottom width of the circuit pattern was 50 μm and the gap between lines was 50 μm was examined, and this time was adopted. . A cross-sectional photograph of the circuit pattern on the obtained printed circuit board was taken, the top width and the bottom width of the circuit pattern were measured, and the Ef value was calculated based on the above equation (1).
【００５７】以上の結果を一括して表１，２に示した。The above results are collectively shown in Tables 1 and 2.
【００５８】[0058]
【表１】 [Table 1]
【００５９】[0059]
【表２】 [Table 2]
【００６０】表１，２から次のことが明らかである。 (1)実施例１，２，３の樹脂付き銅箔は、そのハンドリ
ング時において、絶縁樹脂層へのクラック発生や銅箔か
らの部分剥離などの不都合を起こさない。そして、これ
らの樹脂付き銅箔を用いて製造した銅張り積層板におけ
る銅箔の引き剥がし強さも大きく、印刷回路基板製造時
のＥｆ値は充分大きく、形成された回路パターンは良好
な形状をしていた。The following is clear from Tables 1 and 2. (1) The copper foil with resin of Examples 1, 2, and 3 does not cause inconvenience such as generation of cracks in the insulating resin layer and partial peeling from the copper foil during handling. And the peeling strength of the copper foil in the copper-clad laminate manufactured using these resin-coated copper foils is large, the Ef value at the time of manufacturing a printed circuit board is sufficiently large, and the formed circuit pattern has a good shape. I was
【００６１】すなわち、本発明の樹脂付き銅箔はファイ
ンな回路パターンを形成することができ、高密度極微細
線回路パターンを有する多層印刷回路基板用の銅箔とし
て有用である。 (2)また、実施例１，２と実施例３は、いずれもＥｆ値
が良好な銅箔になっているが、２次粗化処理を行った実
施例３の方は、銅張り積層板における銅箔の引き剥がし
強さが大きく、より性能バランスの優れた銅箔であると
いうことができる。That is, the resin-coated copper foil of the present invention can form a fine circuit pattern and is useful as a copper foil for a multilayer printed circuit board having a high-density ultrafine circuit pattern. (2) In Examples 1 and 2 and Example 3, copper foils having good Ef values were obtained, but Example 3 in which secondary roughening treatment was performed was a copper-clad laminate. It can be said that the copper foil has a large peeling strength and a copper foil having a better performance balance.
【００６２】(3)実施例３と比較例４，５とを比較する
と、用いた銅箔のＲｚ値はいずれも同じであるが、比較
例４の場合はその絶縁樹脂層が薄すぎて、層それ自体は
良好な状態になっていても絶縁信頼性に欠ける。また比
較例５の場合はその絶縁樹脂層の厚みが厚すぎて、層間
および線間の絶縁耐圧はいずれも優れているが、ハンリ
ング時に絶縁樹脂層へのクラックが発生し、また銅箔か
らの剥離も起こっている。このため、内層材との積層は
行わなかった。(3) Comparing Example 3 with Comparative Examples 4 and 5, the Rz values of the copper foils used were all the same, but in the case of Comparative Example 4, the insulating resin layer was too thin. Even though the layers themselves are in good condition, they lack insulation reliability. In the case of Comparative Example 5, the thickness of the insulating resin layer was too large, and the insulation withstand voltage between the layers and between the lines was excellent. Peeling has also occurred. Therefore, lamination with the inner layer material was not performed.
【００６３】このようなことから、形成する絶縁樹脂層
の厚みは２０〜８０μｍに設定すべきことがわかる。 比較例６ 用いる電解銅箔の厚みが１８μｍであったことを除いて
は、実施例３の場合と同じ条件でその電解銅箔表面のＲ
ｚ値を３.７μｍにした。From the above, it is understood that the thickness of the insulating resin layer to be formed should be set to 20 to 80 μm. Comparative Example 6 Except that the thickness of the electrolytic copper foil used was 18 μm, the R of the surface of the electrolytic copper foil was measured under the same conditions as in Example 3.
The z value was 3.7 μm.
【００６４】この電解銅箔を用いて、実施例３と同様に
して銅張り積層板を製造した。この積層板のＥｆ値は
２.７であり、ファインな回路パターンの形成にやや難
点がある以外は、引き剥がし強さは実施例３と同様であ
った。なお、絶縁樹脂層のクラック発生や部分剥離は認
められなかった。Using this electrolytic copper foil, a copper-clad laminate was produced in the same manner as in Example 3. The Ef value of this laminate was 2.7, and the peel strength was the same as that of Example 3 except that there was some difficulty in forming a fine circuit pattern. No cracking or partial peeling of the insulating resin layer was observed.
【００６５】[0065]
【発明の効果】請求項１の樹脂付き銅箔は、銅箔の表面
粗度（Ｒｚ）が２〜４μｍであり、かつそこに形成され
ている絶縁樹脂層の厚みが２０〜８０μｍであるため、
内層材と積層して銅張り積層板を製造する際の前段のハ
ンドリング時においても、絶縁樹脂層へのクラック発生
や部分剥離などの不都合は起こらず、しかも、高密度で
極微細配線の回路パターン形成を可能とする。According to the copper foil with resin of claim 1, the surface roughness (Rz) of the copper foil is 2 to 4 μm and the thickness of the insulating resin layer formed thereon is 20 to 80 μm. ,
Even during the first stage of processing when manufacturing a copper-clad laminate by laminating it with the inner layer material, there are no inconveniences such as cracking or partial peeling of the insulating resin layer, and high-density circuit patterns of ultra-fine wiring Enables formation.
【００６６】請求項２の樹脂付き銅箔は、Ｅｆ値が大き
く、またハンドリング時における絶縁樹脂層へのクラッ
ク発生なども起こらず、ファインな回路パターン形成用
の銅箔として有用である。請求項３の樹脂付き銅箔の場
合、銅箔の厚みを１５μｍ以下としているので、Ｅｆ値
は大きくなり、ファインな回路パターンの形成が容易で
ある。また、絶縁樹脂層がこの薄い銅箔をバックアップ
しているので、全体としては適度の剛性を有し、ハンド
リング時に皺などが発生しづらい。The resin-coated copper foil according to the second aspect has a large Ef value, does not cause cracks in the insulating resin layer during handling, and is useful as a copper foil for forming a fine circuit pattern. In the case of the copper foil with resin according to the third aspect, since the thickness of the copper foil is 15 μm or less, the Ef value becomes large, and it is easy to form a fine circuit pattern. In addition, since the insulating resin layer backs up the thin copper foil, it has moderate rigidity as a whole, and is unlikely to have wrinkles during handling.
【００６７】請求項４の印刷回路基板は、上記した樹脂
付き銅箔を表面の回路パターン形成用にしているので、
ファインな回路パターンを備えたものになっている。In the printed circuit board according to the fourth aspect, the above-mentioned resin-coated copper foil is used for forming a circuit pattern on the surface.
It has a fine circuit pattern.
【図１】本発明の樹脂付き銅箔Ａの１例を示す断面図で
ある。FIG. 1 is a cross-sectional view showing an example of a resin-attached copper foil A of the present invention.
【図２】本発明の銅張り積層板における最小絶縁層厚み
を説明するための部分断面図である。FIG. 2 is a partial cross-sectional view for explaining a minimum insulating layer thickness in the copper-clad laminate of the present invention.
【図３】エッチングファクタを説明するための部分断面
図である。FIG. 3 is a partial cross-sectional view for explaining an etching factor.
１ 電解銅箔 １ａ 電解銅箔１の粗化面 ２ 絶縁樹脂層 ３ 内層材の最外層の回路パターン ４ 側壁 Reference Signs List 1 electrolytic copper foil 1a roughened surface of electrolytic copper foil 1 2 insulating resin layer 3 circuit pattern of outermost layer of inner layer material 4 side wall
───────────────────────────────────────────────────── フロントページの続き (72)発明者 戸嶋 秀勝 東京都千代田区丸の内２丁目６番１号 古 河電気工業株式会社内 (72)発明者 古谷 修一 東京都千代田区丸の内２丁目６番１号 古 河電気工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hidekatsu Tojima 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric Co., Ltd. (72) Shuichi Furuya 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric Co., Ltd.
Claims (4)
有する電解銅箔の前記粗化面に、厚みが２０〜８０μｍ
である半硬化状態の絶縁樹脂層が密着して接合されてい
ることを特徴とする印刷回路基板用樹脂付き銅箔。1. A roughened surface of an electrolytic copper foil having a roughened surface having a surface roughness (Rz) of 2 to 4 μm has a thickness of 20 to 80 μm.
The resin-coated copper foil for a printed circuit board, wherein the semi-cured insulating resin layer is tightly joined.
の粒子から成る２次粗化粒子層が形成されている請求項
１の印刷回路基板用樹脂付き銅箔。2. The roughened surface has a particle diameter of 0.05 to 1 μm.
The resin-coated copper foil for a printed circuit board according to claim 1, wherein a secondary roughened particle layer made of the particles is formed.
る請求項１または２の印刷回路基板用樹脂付き銅箔。3. The copper foil with resin for a printed circuit board according to claim 1, wherein the thickness of the electrolytic copper foil is 15 μm or less.
用樹脂付き銅箔を用いて製造されたことを特徴とする印
刷回路基板。4. A printed circuit board manufactured using the copper foil with resin for a printed circuit board according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9294429A JPH11135952A (en) | 1997-10-27 | 1997-10-27 | Copper foil with resin for printed circuit board and printed circuit board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9294429A JPH11135952A (en) | 1997-10-27 | 1997-10-27 | Copper foil with resin for printed circuit board and printed circuit board using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11135952A true JPH11135952A (en) | 1999-05-21 |
Family
ID=17807658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9294429A Pending JPH11135952A (en) | 1997-10-27 | 1997-10-27 | Copper foil with resin for printed circuit board and printed circuit board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11135952A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063990A1 (en) * | 2000-02-28 | 2001-08-30 | Zeon Corporation | Composite material and method of manufacturing multilayer circuit board |
| JP2003224367A (en) * | 2002-01-29 | 2003-08-08 | Hitachi Chem Co Ltd | High frequency printed wiring board and its manufacturing method |
| JP2006051687A (en) * | 2004-08-11 | 2006-02-23 | Hitachi Chem Co Ltd | Metal foil with adhesive layer and metal-clad laminate |
| JP2007048800A (en) * | 2005-08-08 | 2007-02-22 | Nippon Foil Mfg Co Ltd | Antenna coil for ic card and manufacturing method therefor |
| JP2011119611A (en) * | 2009-12-07 | 2011-06-16 | Furukawa Electric Co Ltd:The | Injection-molded substrate and injection-molded component |
| WO2011138876A1 (en) * | 2010-05-07 | 2011-11-10 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit |
| WO2012169249A1 (en) * | 2011-06-07 | 2012-12-13 | Jx日鉱日石金属株式会社 | Liquid crystal polymer-copper clad laminate and copper foil used for liquid crystal polymer-copper clad laminate |
| CN103958743A (en) * | 2011-11-04 | 2014-07-30 | Jx日矿日石金属株式会社 | Copper foil for printed circuit |
| CN104024488A (en) * | 2011-11-02 | 2014-09-03 | 吉坤日矿日石金属株式会社 | Copper foil for printing circuit |
| CN114828447A (en) * | 2021-01-28 | 2022-07-29 | 鹏鼎控股(深圳)股份有限公司 | Circuit board and manufacturing method thereof |
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|---|---|---|---|---|
| JPH05291741A (en) * | 1992-04-14 | 1993-11-05 | Mitsui Mining & Smelting Co Ltd | Manufacture of copper foil with adhesive |
| JPH07231152A (en) * | 1993-12-24 | 1995-08-29 | Mitsui Mining & Smelting Co Ltd | Copper foil for printed circuit inner layer and its manufacture |
| JPH0818171A (en) * | 1994-07-01 | 1996-01-19 | Shin Etsu Chem Co Ltd | Flexible printed circuit board |
| JPH08158100A (en) * | 1994-10-06 | 1996-06-18 | Furukawa Circuit Foil Kk | Roughening of copper foil surface |
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1997
- 1997-10-27 JP JP9294429A patent/JPH11135952A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05291741A (en) * | 1992-04-14 | 1993-11-05 | Mitsui Mining & Smelting Co Ltd | Manufacture of copper foil with adhesive |
| JPH07231152A (en) * | 1993-12-24 | 1995-08-29 | Mitsui Mining & Smelting Co Ltd | Copper foil for printed circuit inner layer and its manufacture |
| JPH0818171A (en) * | 1994-07-01 | 1996-01-19 | Shin Etsu Chem Co Ltd | Flexible printed circuit board |
| JPH08158100A (en) * | 1994-10-06 | 1996-06-18 | Furukawa Circuit Foil Kk | Roughening of copper foil surface |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063990A1 (en) * | 2000-02-28 | 2001-08-30 | Zeon Corporation | Composite material and method of manufacturing multilayer circuit board |
| JP2003224367A (en) * | 2002-01-29 | 2003-08-08 | Hitachi Chem Co Ltd | High frequency printed wiring board and its manufacturing method |
| JP2006051687A (en) * | 2004-08-11 | 2006-02-23 | Hitachi Chem Co Ltd | Metal foil with adhesive layer and metal-clad laminate |
| JP2007048800A (en) * | 2005-08-08 | 2007-02-22 | Nippon Foil Mfg Co Ltd | Antenna coil for ic card and manufacturing method therefor |
| JP2011119611A (en) * | 2009-12-07 | 2011-06-16 | Furukawa Electric Co Ltd:The | Injection-molded substrate and injection-molded component |
| JP5654581B2 (en) * | 2010-05-07 | 2015-01-14 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit, copper-clad laminate, printed circuit board, printed circuit and electronic equipment |
| WO2011138876A1 (en) * | 2010-05-07 | 2011-11-10 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit |
| US10472728B2 (en) | 2010-05-07 | 2019-11-12 | Jx Nippon Mining & Metals Corporation | Copper foil for printed circuit |
| US9580829B2 (en) | 2010-05-07 | 2017-02-28 | Jx Nippon Mining & Metals Corporation | Copper foil for printed circuit |
| WO2012169249A1 (en) * | 2011-06-07 | 2012-12-13 | Jx日鉱日石金属株式会社 | Liquid crystal polymer-copper clad laminate and copper foil used for liquid crystal polymer-copper clad laminate |
| US9060431B2 (en) | 2011-06-07 | 2015-06-16 | Jx Nippon Mining & Metals Corporation | Liquid crystal polymer copper-clad laminate and copper foil used for said laminate |
| JP2012255180A (en) * | 2011-06-07 | 2012-12-27 | Jx Nippon Mining & Metals Corp | Liquid crystal polymer-copper clad laminate and copper foil used in the laminate |
| CN104024488A (en) * | 2011-11-02 | 2014-09-03 | 吉坤日矿日石金属株式会社 | Copper foil for printing circuit |
| CN103958743A (en) * | 2011-11-04 | 2014-07-30 | Jx日矿日石金属株式会社 | Copper foil for printed circuit |
| CN114828447A (en) * | 2021-01-28 | 2022-07-29 | 鹏鼎控股(深圳)股份有限公司 | Circuit board and manufacturing method thereof |
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