JP2000280401A - Resin-clad copper foil - Google Patents
Resin-clad copper foilInfo
- Publication number
- JP2000280401A JP2000280401A JP11089395A JP8939599A JP2000280401A JP 2000280401 A JP2000280401 A JP 2000280401A JP 11089395 A JP11089395 A JP 11089395A JP 8939599 A JP8939599 A JP 8939599A JP 2000280401 A JP2000280401 A JP 2000280401A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- resin
- layer
- thickness
- zinc
- 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 85
- 239000011889 copper foil Substances 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- -1 cyanic acid ester Chemical class 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 239000011701 zinc Substances 0.000 claims description 31
- 229910052725 zinc Inorganic materials 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 26
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 61
- 238000007747 plating Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 238000001035 drying Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 238000009432 framing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011156 evaluation Methods 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
- 238000005246 galvanizing Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 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
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は印刷回路基板の製造
時に用いる樹脂付き銅箔に関し、更に詳しくは、高密度
超微細配線の形成が可能であり、また基材との接合強度
も高く難燃性を備え、とくに多層印刷回路基板の製造に
用いて好適な難燃性樹脂付き銅箔に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated copper foil used in the manufacture of a printed circuit board, and more particularly, it is capable of forming high-density ultrafine wiring and has high bonding strength with a base material and flame retardancy. The present invention relates to a copper foil with a flame-retardant resin, which is particularly suitable for use in the production of multilayer printed circuit boards.
【０００２】[0002]
【従来の技術】印刷回路基板は、概ね次のようにして製
造されている。まず、エポキシ樹脂やポリイミド樹脂な
どから成る電気絶縁性の基板の表面に、熱硬化性の接着
剤を用いて表面回路形成用の薄い銅箔を貼着したのち、
加熱・加圧して銅張り積層板を製造する。2. Description of the Related Art A printed circuit board is generally manufactured as follows. First, a thin copper foil for surface circuit formation is attached to the surface of an electrically insulating substrate made of epoxy resin or polyimide resin using a thermosetting adhesive,
Heat and press to produce copper clad laminates.
【０００３】ついで、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線幅と所望す
る線間ピッチを備えた配線パターンを形成し、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。このとき、用いる銅箔に対しては、基材に熱圧着さ
れる表面を粗化面とし、この粗化面で基材に対するアン
カー効果を発揮させ、もって基材と銅箔との接合強度を
高めて印刷回路基板としての信頼性を確保することがな
されている。[0003] Then, after drilling through holes and plating through holes in the copper-clad laminate in order, the copper foil on the surface is subjected to an etching treatment to provide a desired line width and a desired line pitch. Form a wiring pattern, and finally,
A solder resist is formed and other finishing processes are performed. At this time, for the copper foil to be used, the surface to be thermocompression-bonded to the substrate is a roughened surface, and the roughened surface exerts an anchoring effect on the substrate, thereby increasing the bonding strength between the substrate and the copper foil. The reliability of the printed circuit board has been increased to enhance the reliability.
【０００４】また、最近では、銅箔の上記粗化面を予め
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（Ｂステージ）の絶縁樹脂層にした樹
脂付き銅箔を表面回路形成用の銅箔として用い、その絶
縁樹脂層側を基材に熱圧着して印刷回路基板、とりわけ
多層印刷回路基板を製造することが行われている。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
基板における配線パターンも高密度化が要求され、微細
な線幅や線間ピッチの配線から成る配線パターンが形成
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り、更には集積化に伴う発熱量の
増加に対応するために優れた耐熱性や難燃性と誘電特性
も要求されるようになっている。Recently, a resin-coated copper foil in which the above-described roughened surface of a copper foil is coated in advance with an adhesive resin such as an epoxy resin, and the adhesive resin is an insulating resin layer in a semi-cured state (B stage). 2. Description of the Related Art A foil is used as a copper foil for forming a surface circuit, and the insulating resin layer side is thermocompression-bonded to a substrate to produce a printed circuit board, especially a multilayer printed circuit board. By the way, recent various electronic components are highly integrated, and small ICs and LSIs having a high-density printed circuit are used. Corresponding to this, the wiring pattern on the printed circuit board is also required to have a high density, and a so-called fine-pattern printed circuit board on which a wiring pattern composed of wiring having a fine line width and a line pitch is formed. Are required, and further, in order to cope with an increase in the amount of heat generated by integration, excellent heat resistance, flame retardancy and dielectric properties are also required.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、最近、樹脂
付き銅箔に要求されている上記した問題に対応すべく開
発された樹脂付き銅箔であって、ファインパターンの配
線を形成できることは勿論のこと、耐熱性や難燃性が優
れ、また良好な誘電特性も備えている樹脂付き銅箔の提
供を目的とする。SUMMARY OF THE INVENTION The present invention relates to a resin-coated copper foil which has been recently developed to address the above-mentioned problems required for a resin-coated copper foil. Needless to say, an object of the present invention is to provide a resin-coated copper foil having excellent heat resistance and flame retardancy and also having good dielectric properties.
【０００６】[0006]
【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、銅箔の表面が半硬化状態の
絶縁樹脂層で被覆されている樹脂付き銅箔において、前
記絶縁樹脂層が、多官能性シアン酸エステル化合物を５
０〜７０重量％含有し、かつ、臭素化エポキシ化合物を
臭素換算量で１２重量％以上２０重量％未満含有する樹
脂組成物から成ることを特徴とする樹脂付き銅箔が提供
される。According to the present invention, there is provided a resin-coated copper foil having a semi-cured insulating resin layer coated on the surface of the copper foil. Is a polyfunctional cyanate compound
The present invention provides a resin-coated copper foil comprising a resin composition containing 0 to 70% by weight and containing a brominated epoxy compound in an amount of 12% by weight or more and less than 20% by weight in terms of bromine.
【０００７】とくに、前記銅箔の表面粗度（Rz）が２.
０〜４.０μｍであり、かつ、前記銅箔の表面には、更
に、厚み０.０１〜０.０５mg／dm2のニッケル層と厚み
０.１５〜０.５mg／dm2の亜鉛層がこの順序で形成され
ている樹脂付き銅箔が提供される。[0007] In particular, the surface roughness (Rz) of the copper foil is 2.
A 0～4.0Myuemu, and, on the surface of the copper foil is further nickel layer having a thickness of 0.01-0.05 mg / dm 2 and zinc thickness 0.15~0.5mg / dm 2 layer A copper foil with resin formed in this order is provided.
【０００８】[0008]
【発明の実施の形態】まず、本発明の樹脂付き銅箔の１
例Ａを図１に示す。この樹脂付き銅箔Ａは、銅箔１と、
その片面１ａを被覆して形成された半硬化状態の絶縁樹
脂層２で構成されている。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、その絶縁樹脂層２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。BEST MODE FOR CARRYING OUT THE INVENTION First, the copper foil with resin of the present invention 1
Example A is shown in FIG. This copper foil A with resin is a copper foil 1
It is composed of a semi-cured insulating resin layer 2 formed by covering one surface 1a. The semi-cured state here means
It is a so-called B-stage state, in which there is no stickiness even when the surface is touched with a finger, the insulating resin layer 2 can be stored in an overlapping state, and a curing reaction occurs when further subjected to a heat treatment. .
【０００９】この絶縁樹脂層２は、少なくとも多官能性
シアン酸エステル化合物と臭素化エポキシ化合物を含有
している熱硬化性樹脂組成物から成る。ここで、多官能
性シアン酸エステル化合物としては、特開平１０−１４
６９１５号公報に開示されているものを用いることがで
きる。その場合、多官能性シアン酸エステル化合物の含
有量が５０重量％より少ないと、絶縁樹脂層の耐熱性や
誘電特性が低下するようになり、また含有量が７０重量
％より多くなると、製造した樹脂付き銅箔を基材に例え
ば温度１７０℃で６０分間という標準プレス条件で熱圧
着したときの接着性が低下するようになるので、樹脂組
成物における当該多官能性シアン酸エステル化合物の含
有量は５０〜７０重量％に設定される。The insulating resin layer 2 is made of a thermosetting resin composition containing at least a polyfunctional cyanate compound and a brominated epoxy compound. Here, as the polyfunctional cyanate compound, JP-A-10-14
No. 6,915, can be used. In this case, when the content of the polyfunctional cyanate compound is less than 50% by weight, the heat resistance and the dielectric properties of the insulating resin layer are reduced, and when the content is more than 70% by weight, the product is produced. Since the adhesiveness when the resin-coated copper foil is thermocompression-bonded to the substrate under a standard press condition of, for example, a temperature of 170 ° C. for 60 minutes is reduced, the content of the polyfunctional cyanate compound in the resin composition Is set to 50 to 70% by weight.
【００１０】臭素化エポキシ化合物は、絶縁樹脂層２を
難燃化し、その耐熱性を高めるために配合される。この
ような働きをする臭素化エポキシ化合物としては、例え
ば、油化シエルエポキシ（株）製のエピコート５０５０
（臭素含有量４７〜５１重量％）、旭チバ（株）製のア
ラルダイト８０１８などをあげることができる。The brominated epoxy compound is blended to make the insulating resin layer 2 flame-retardant and to improve its heat resistance. Examples of the brominated epoxy compound having such a function include, for example, Epicoat 5050 manufactured by Yuka Shell Epoxy Co., Ltd.
(Bromine content: 47 to 51% by weight), and Araldite 8018 manufactured by Asahi Ciba Co., Ltd.
【００１１】この臭素化エポキシ化合物の配合量は、臭
素換算量にして１２重量％以上２０重量％未満に設定さ
れる。配合量が１２重量％未満の場合には、難燃規格で
あるＵＬ−９４Ｖ０を満たすことができず、また２０重
量％以上にすると、製造した樹脂付き銅箔を基材に熱圧
着したときの柔軟性が悪くなり、更には製造した積層板
の切断加工時に粉吹きが多くなるからである。The compounding amount of the brominated epoxy compound is set to be 12% by weight or more and less than 20% by weight in terms of bromine. When the compounding amount is less than 12% by weight, UL-94V0, which is a flame retardant standard, cannot be satisfied. This is because flexibility is deteriorated, and moreover, powder blowing increases during cutting processing of the manufactured laminated board.
【００１２】なお、上記臭素化エポキシ化合物と一緒に
酸化アンチモンを配合すると、臭素化エポキシ化合物の
配合量を少なくすることができる。例えば酸化アンチモ
ンを２重量％程度配合すると、臭素化エポキシ化合物の
配合量が１０重量％程度であっても、ＵＬ規格を満たす
ことができる。この樹脂付き銅箔Ａは次のようにして製
造することができる。When antimony oxide is blended together with the above-mentioned brominated epoxy compound, the amount of the brominated epoxy compound can be reduced. For example, when about 2% by weight of antimony oxide is added, even if the amount of the brominated epoxy compound is about 10% by weight, the UL standard can be satisfied. This copper foil A with resin can be manufactured as follows.
【００１３】すなわち、上記した各成分を例えばメチル
エチルケトン（ＭＥＫ），トルエンなどの溶剤に溶解し
て樹脂液とし、これを銅箔の片面１ａに例えばロールコ
ータ法などによって塗布し、必要に応じて加熱乾燥して
溶剤を除去してＢステージ状態にする。乾燥には例えば
熱風乾燥炉を用いればよく、乾燥温度は１００〜２５０
℃、好ましくは１３０〜１７０℃であればよい。That is, each of the above components is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to form a resin solution, which is applied to one surface 1a of the copper foil by, for example, a roll coater method and, if necessary, heated. After drying, the solvent is removed to obtain a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature is 100 to 250.
C, preferably 130 to 170C.
【００１４】このとき、用いる銅箔１の片面１ａは、Ｊ
ＩＳ Ｂ０６０１で規定する１０点平均粗さの値（Rz）
が２.０〜４.０μｍになっている粗化面であることが好
ましい。このRz値が２.０μｍより小さい場合は前記し
た基材に熱圧着したときに充分な接合強度が得られず、
またRz値が４.０μｍより大きい場合には、熱圧着時に
おける基材への突起部の喰い込み量が大きくなり、エッ
チング時にその突起部の完全除去に要するエッチング時
間が長くなってエッチングファクタ値は小さくなり、結
局、信頼性の高いファインな配線パターンの形成が困難
になるからである。At this time, one side 1a of the copper foil 1 used is J
10-point average roughness value (Rz) specified in IS B0601
Is preferably a roughened surface having a thickness of 2.0 to 4.0 μm. If the Rz value is smaller than 2.0 μm, sufficient bonding strength cannot be obtained when thermocompression-bonded to the above-described substrate,
If the Rz value is greater than 4.0 μm, the amount of protrusion of the protrusion into the substrate at the time of thermocompression bonding increases, and the etching time required for complete removal of the protrusion during etching increases. Is small, and eventually it becomes difficult to form a highly reliable fine wiring pattern.
【００１５】また、銅箔の片面１ａに更にクロメート処
理を行うと、そこに酸化防止膜が形成されるので好適で
ある。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、銅箔には優れた防
食能を付与することができる。Further, it is preferable to further perform a chromate treatment on one surface 1a of the copper foil, since an antioxidant film is formed thereon. The chromate treatment to be applied may be a known method, for example, a method disclosed in JP-A-60-86894. By adhering about 0.01 to 0.2 mg / dm 2 of chromium oxide and its hydrate in terms of the amount of chromium, the copper foil can be provided with an excellent anticorrosive ability.
【００１６】また、前記したクロメート処理面に対し更
にシランカップリング材を用いた表面処理を行うと、銅
箔表面には接着剤との親和力の強い官能基が付与される
ので、銅箔と基材との接合強度は一層向上し、銅箔の防
錆性，耐熱性も更に向上するので好適である。用いるシ
ランカップリング材としては、例えばビニルトリス（２
−メトキシエトキシ）シラン，３−クリシドキシプロピ
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。こ
れらのシランカップリング剤は通常０.００１〜５％の
水溶液にし、これを銅箔の表面に塗布したのちそのまま
加熱乾燥して用いればよい。なお、シランカップリング
剤に代えて、チタン系，ジルコン系などのカップリング
剤を用いても同様の効果を得ることができる。Further, when a surface treatment using a silane coupling material is further performed on the above-mentioned chromate-treated surface, a functional group having a strong affinity for an adhesive is provided on the surface of the copper foil. It is preferable because the bonding strength with the material is further improved, and the rust resistance and heat resistance of the copper foil are further improved. As the silane coupling material to be used, for example, vinyl tris (2
-Methoxyethoxy) silane, 3-crysidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like. These silane coupling agents are usually prepared as a 0.001 to 5% aqueous solution, applied to the surface of a copper foil, and dried by heating as it is. The same effect can be obtained by using a titanium-based or zircon-based coupling agent instead of the silane coupling agent.
【００１７】図２に本発明の樹脂付き銅箔の別の例Ｂを
示す。この樹脂付き銅箔Ｂは、銅箔１の表面１ａにニッ
ケル層３，亜鉛層４をこの順序で形成し、亜鉛層４の表
面が前記した絶縁樹脂層２で被覆された構造になってい
る。この亜鉛層４は、樹脂付き銅箔Ｂと基材とを接着剤
を用いて例えば熱圧着したときに、銅箔１と接着剤との
反応による接着剤の劣化や銅箔１の表面酸化を防止して
基材との接合強度を高める働きをし、更には、銅箔１の
粗化面の突起部が基材に喰い込んでいる場合、突起部と
基材との界面に存在している亜鉛の働きで突起部の銅が
エッチングされやすくなり、もってエッチングファクタ
値を向上させる。またニッケル層３は、熱圧着時に亜鉛
層４の亜鉛が銅箔１側へ熱拡散することを防止し、もっ
て亜鉛層４の上記機能を有効に発揮させる働きをする。FIG. 2 shows another example B of the copper foil with resin of the present invention. The copper foil with resin B has a structure in which a nickel layer 3 and a zinc layer 4 are formed in this order on the surface 1a of the copper foil 1 and the surface of the zinc layer 4 is covered with the insulating resin layer 2 described above. . This zinc layer 4 is used to prevent the deterioration of the adhesive due to the reaction between the copper foil 1 and the adhesive and the surface oxidation of the copper foil 1 when the copper foil with resin B and the base material are thermocompression-bonded using the adhesive, for example. It acts to prevent and increase the bonding strength with the base material, and furthermore, when the protrusions on the roughened surface of the copper foil 1 bite into the base material, they are present at the interface between the protrusions and the base material. The function of the zinc makes it easier to etch the copper on the protrusions, thereby improving the etching factor value. Further, the nickel layer 3 functions to prevent the zinc of the zinc layer 4 from thermally diffusing to the copper foil 1 side during thermocompression bonding, thereby effectively exerting the above function of the zinc layer 4.
【００１８】ここで、亜鉛は銅へ拡散しやすいので、亜
鉛層４の厚みが薄すぎると、拡散の結果、銅箔１の表面
に存在する亜鉛の量は極度に減少してしまい、結局、亜
鉛層４を形成した意味が消失してしまう。亜鉛層４の厚
みが厚くなれば上記した問題は起こらなくなるが、しか
し他方ではエッチング時に溶出する亜鉛量も多くなって
銅箔１の粗化面と基材との間にクリアランスが生じてこ
の場合も接合強度の低下が引き起こされる。このような
ことから、亜鉛層４の厚みは、０.１５〜０.５mg／dm2
の範囲に設定されることが好ましい。Here, since zinc is easily diffused into copper, if the thickness of the zinc layer 4 is too thin, the amount of zinc present on the surface of the copper foil 1 is extremely reduced as a result of the diffusion. The meaning of forming the zinc layer 4 disappears. When the thickness of the zinc layer 4 is increased, the above-mentioned problem does not occur. However, on the other hand, the amount of zinc eluted at the time of etching also increases, and a clearance is generated between the roughened surface of the copper foil 1 and the base material. This also causes a decrease in bonding strength. Thus, the thickness of the zinc layer 4 is 0.15 to 0.5 mg / dm 2.
Is preferably set in the range.
【００１９】一方、亜鉛の拡散防止層として機能するニ
ッケル層３の厚みは、上記した亜鉛層４の厚みと相関関
係をもっている。例えば、ニッケル層３の厚みが薄い場
合には、亜鉛の拡散防止層としての機能は充分に発揮さ
れないので、樹脂付き銅箔Ｂと基材との接合強度を高め
るときには、銅箔１側への亜鉛の拡散量を見込んで比較
的多量の亜鉛をニッケル層３の上に存在させることが必
要になる。そして、ニッケル層３の厚みを０.０１mg／d
m2よりも薄くすると、亜鉛の拡散防止層としての機能は
ほとんど発現せず、また０.０４〜０.０５mg／dm2の厚
みのときには、この上に形成する亜鉛層の厚みは、０.
１５〜０.５mg／dm2の範囲における下限前後の厚みであ
っても亜鉛の拡散が有効に防止できる。On the other hand, the thickness of the nickel layer 3 functioning as a zinc diffusion preventing layer has a correlation with the thickness of the zinc layer 4 described above. For example, when the thickness of the nickel layer 3 is small, the function as a zinc diffusion preventing layer is not sufficiently exhibited. It is necessary to allow a relatively large amount of zinc to exist on the nickel layer 3 in consideration of the diffusion amount of zinc. Then, the thickness of the nickel layer 3 is set to 0.01 mg / d.
When the thickness is smaller than m 2 , the function of the zinc as a diffusion preventing layer is hardly exhibited, and when the thickness is 0.04 to 0.05 mg / dm 2 , the thickness of the zinc layer formed thereon is 0.1 mm.
Even when the thickness is around the lower limit in the range of 15 to 0.5 mg / dm 2 , diffusion of zinc can be effectively prevented.
【００２０】しかし、ニッケル層３の厚みを０.０５mg
／dm2より厚くすると、亜鉛の拡散防止層としての機能
向上は達成されるものの、他方では、ニッケル層３はエ
ッチングを阻害するので、銅箔１のエッチング時にエッ
チングファクタ値は小さくなり、ファインな配線パター
ンの形成ができなくなる。このようなことから、例えば
線間ピッチや線幅を３０μｍ程度にするためには、ニッ
ケル層３の厚みを、０.０１〜０.０５mg／dm2の範囲に
設定することが好ましい。However, the thickness of the nickel layer 3 is 0.05 mg.
When the thickness is greater than / dm 2 , the function as a zinc diffusion preventing layer can be improved, but on the other hand, the nickel layer 3 hinders the etching. Wiring patterns cannot be formed. For this reason, it is preferable to set the thickness of the nickel layer 3 in the range of 0.01 to 0.05 mg / dm 2 in order to set the line pitch and line width to about 30 μm, for example.
【００２１】なお、これらのニッケル層や亜鉛層は、公
知の電解めっき法や無電解めっき法を適用して形成する
ことが好ましい。また、上記したニッケル層は、純ニッ
ケルで形成してもよく、６重量％以下のリンを含有する
含リンニッケルで形成してもよい。なお、この樹脂付き
銅箔Ｂの場合、絶縁樹脂層２の形成に先立ち、前記した
クロメート処理，シランカップリング剤処理などを行っ
てもよい。The nickel layer and the zinc layer are preferably formed by applying a known electrolytic plating method or electroless plating method. Further, the above-mentioned nickel layer may be formed of pure nickel, or may be formed of phosphorus-containing nickel containing 6% by weight or less of phosphorus. In the case of the resin-coated copper foil B, the above-described chromate treatment, silane coupling agent treatment, or the like may be performed before the formation of the insulating resin layer 2.
【００２２】本発明の樹脂付き銅箔は、その絶縁樹脂層
２を図示しない基材に重ね合わせたのち全体を熱圧着し
て絶縁樹脂層を熱硬化し、銅箔１に所定の配線パターン
を形成するという態様で使用される。この樹脂付き銅箔
を使用すると、多層印刷回路基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、絶
縁樹脂層２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ていなくても銅張り
積層板を製造することができる。またこのとき、基材の
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 copper foil with resin of the present invention, the insulating resin layer 2 is overlaid on a base material (not shown), and the whole is thermocompressed to thermally cure the insulating resin layer. Used in the form of forming. The use of this resin-coated copper foil can also reduce the number of prepreg materials used in manufacturing a multilayer printed circuit board. In addition, a copper-clad laminate can be manufactured even if the thickness of the insulating resin layer 2 is set to a value that ensures interlayer insulation, or no prepreg material is used. At this time, the surface of the base material may be undercoated with an insulating resin to further improve the smoothness of the surface.
【００２３】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は薄くなり、１層の厚みが１００μ
ｍ以下である極薄の多層印刷回路基板を製造することが
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, which is economically advantageous. The thickness of the multilayer printed circuit board is reduced, and the thickness of one layer is 100 μm.
The advantage is that an ultra-thin multilayer printed circuit board having a thickness of not more than m can be manufactured.
【００２４】この絶縁樹脂層２の厚みは２０〜８０μｍ
であることが好ましい。絶縁樹脂層２の厚みが２０μｍ
より薄くなると、基材との接着力は低下し、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を備
えた基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。The thickness of the insulating resin layer 2 is 20 to 80 μm
It is preferred that The thickness of the insulating resin layer 2 is 20 μm
When it becomes thinner, the adhesive strength with the base material decreases, and when this resin-coated copper foil is laminated on the base material with the inner layer material without interposing the prepreg material, the interlayer insulation between the circuit of the inner layer material and Is difficult to secure.
【００２５】また、絶縁樹脂層２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。If the thickness of the insulating resin layer 2 is more than 80 μm, it becomes difficult to form an insulating resin layer having a desired thickness in a single coating step, which requires extra material costs and man-hours, which is economically disadvantageous. Becomes 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.
【００２６】[0026]
【実施例】実施例１ （１）銅箔の製造 下記の条件で長さ３００ｍ，幅５００mm，厚み１０μｍ
の電解銅箔を製造した。EXAMPLES Example 1 (1) Production of copper foil Under the following conditions, length 300m, width 500mm, thickness 10μm
Was produced.
【００２７】浴組成：金属銅５５ｇ／Ｌ，硫酸５５ｇ／
Ｌ，塩化物イオン３０ppm（ＮａＣｌとして），３−メ
ルカプト１−プロパンスルホン酸ナトリウム１.５ppm，
ヒドロキシエチルセルロース１０ppm。 浴温：５８℃、対極：含リン銅板、電流密度：５０Ａ／
dm2。 得られた電解銅箔の表面粗度をＪＩＳＢ０６０１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１.２μｍであった。Bath composition: metallic copper 55 g / L, sulfuric acid 55 g / L
L, 30 ppm of chloride ion (as NaCl), 1.5 ppm of sodium 3-mercapto 1-propanesulfonate,
Hydroxyethyl cellulose 10 ppm. Bath temperature: 58 ° C, counter electrode: phosphorus-containing copper plate, current density: 50A /
dm 2 . The surface roughness of the obtained electrolytic copper foil was measured by the method specified in JIS B0601. 10-point average surface roughness (Rz)
Was 1.2 μm.
【００２８】この電解銅箔の表面に更に次のような銅め
っきを行って粗化面を形成した。まず、金属銅：２０ｇ
／Ｌ，硫酸：１００ｇ／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、金属銅：６０ｇ／
Ｌ，硫酸：１００ｇ／Ｌから成る電析浴を建浴した。こ
れを浴(2)とする。前記した電解銅箔に対し、浴(1)を用
い、浴温２５℃，電流密度３０Ａ／dm2の条件下で時間
を変えためっき処理を行い、その表面に銅粒子を析出さ
せた。ついで、浴(2)を用い、浴温６０℃，電流密度１
５Ａ／dm2の条件下で時間を変えてめっき処理を行い、
前記銅粒子を被覆する緻密な銅のカプセルめっき層を形
成した。The surface of the electrolytic copper foil was further subjected to the following copper plating to form a roughened surface. First, metal copper: 20g
/ L, sulfuric acid: an electrodeposition bath having a composition of 100 g / L was prepared. This is called bath (1). Metallic copper: 60 g /
L, sulfuric acid: An electrodeposition bath consisting of 100 g / L was prepared. This is called bath (2). The above-mentioned electrolytic copper foil was subjected to a plating treatment using a bath (1) under the conditions of a bath temperature of 25 ° C. and a current density of 30 A / dm 2 for various times to deposit copper particles on the surface. Then, using bath (2), bath temperature 60 ° C, current density 1
Performs a plating process by changing the time under the conditions of 5A / dm 2,
A dense copper encapsulation plating layer covering the copper particles was formed.
【００２９】この時点で電解銅箔の表面を顕微鏡観察し
たところ、全面に微粒子状の突起物が形成されている粗
化面になっていた。この粗化面のRz値は表１，２で示し
たとおりである。ついで、この粗化面の上に次のように
してニッケル層，亜鉛めっき層を形成した。At this point, when the surface of the electrolytic copper foil was observed with a microscope, it was found to be a roughened surface in which fine projections were formed on the entire surface. The Rz value of the roughened surface is as shown in Tables 1 and 2. Next, a nickel layer and a zinc plating layer were formed on the roughened surface as follows.
【００３０】まず、下記組成のニッケルめっき浴を建浴
した。硫酸ニッケル六水塩２４０ｇ／Ｌ，塩化ニッケル
六水塩４５ｇ／Ｌ，ホウ酸３０ｇ／Ｌ，次亜リン酸ナト
リウム５ｇ／Ｌ。また、下記組成の亜鉛めっき浴を建浴
した。硫酸亜鉛七水塩２４ｇ／Ｌ，水酸化ナトリウム８
５ｇ／Ｌ。First, a nickel plating bath having the following composition was prepared. Nickel sulfate hexahydrate 240 g / L, nickel chloride hexahydrate 45 g / L, boric acid 30 g / L, sodium hypophosphite 5 g / L. In addition, a galvanizing bath having the following composition was constructed. Zinc sulfate heptahydrate 24 g / L, sodium hydroxide 8
5 g / L.
【００３１】前記した電解銅箔の粗化面に、ニッケルめ
っき浴の浴温を５０℃とし、対極にステンレス鋼板を用
い、電流密度０.５Ａ／dm2でめっき時間を変化させてニ
ッケルめっきを行い、粗化面に表１，２で示した厚みの
含リンニッケルめっき層を形成し、更にその上に、亜鉛
めっき浴の浴温を２５℃とし、対極にステンレス鋼板を
用い、電流密度０.４Ａ／dm2でめっき時間を変化させて
亜鉛めっきを行い、表１，２で示した厚みの亜鉛めっき
層を形成した。On the roughened surface of the above-mentioned electrolytic copper foil, a nickel plating bath was set at a bath temperature of 50 ° C., a stainless steel plate was used as a counter electrode, and the plating time was changed at a current density of 0.5 A / dm 2 to perform nickel plating. Then, a phosphorous-containing nickel plating layer having the thickness shown in Tables 1 and 2 was formed on the roughened surface, and the bath temperature of the zinc plating bath was set at 25 ° C., and a stainless steel plate was used as a counter electrode. Galvanization was performed by changing the plating time at 0.4 A / dm 2 to form a galvanized layer having a thickness shown in Tables 1 and 2.
【００３２】ついで、この銅箔を水洗したのち、三酸化
クロム３ｇ／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、銅箔を、ビニルトリス（２
−メトキシエトキシ）シラン２ｇ／Ｌの水溶液に５秒間
浸漬したのち取り出し、温度１００℃の温風で乾燥して
シランカップリング剤処理を行った。Then, after the copper foil was washed with water, it was immersed in a 3 g / L of 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, the copper foil is replaced with vinyl tris (2
-Methoxyethoxy) silane was immersed in an aqueous solution of 2 g / L for 5 seconds, taken out, dried with hot air at a temperature of 100 ° C., and treated with a silane coupling agent.
【００３３】（２）樹脂付き銅箔の製造 まず、多官能性シアン酸エステル化合物として旭チバ
（株）製のアロシーを選び、また臭素含量が５２重量％
である臭素化エポキシ化合物として旭チバ（株）製の臭
素化エポキシアラルダイト８０１８を選んだ。そして、
両者を表１，２で示した割合（重量％）で混合し、更に
両者の合計量１００重量部に対し、液状エポキシ樹脂１
１.１重量部，ニッカオクチニックス亜鉛（商品名、亜
鉛含有量１８重量％）０.０６重量部を配合して各種の
ワニスを調製した。ついで、このワニスを前記した銅箔
のシランカップリング剤処理面にロールコータで塗布し
たのち、温度１６０℃で３分間の熱処理を行い、厚み６
０μｍのＢステージの絶縁樹脂層を形成した。(2) Production of Copper Foil with Resin First, Allothy manufactured by Asahi Chiba Co., Ltd. was selected as a polyfunctional cyanate ester compound, and bromine content was 52% by weight.
As a brominated epoxy compound, brominated epoxy araldite 8018 manufactured by Asahi Ciba Co., Ltd. was selected. And
Both were mixed at the ratio (% by weight) shown in Tables 1 and 2, and 100 parts by weight of the total amount of both were mixed with the liquid epoxy resin 1
Various varnishes were prepared by mixing 1.1 parts by weight and 0.06 parts by weight of Nikka Octinix zinc (trade name, zinc content: 18% by weight). Then, the varnish was applied to the surface of the copper foil treated with the silane coupling agent using a roll coater, and then heat-treated at a temperature of 160 ° C. for 3 minutes to obtain a thickness of 6 mm.
A 0-μm B-stage insulating resin layer was formed.
【００３４】（３）特性の評価 各樹脂付き銅箔を縦３００mm，横３００mmに切断したの
ちその絶縁樹脂層側の面を、厚み１mmのガラス繊維エポ
キシプレプリグシート（ＦＲ−４）の上に配置し、全体
を２枚の平滑なステンレス鋼板で挟み、温度１７０℃，
圧力５０kg／cm 2で６０分間熱圧着して片面銅張り積層
板を製造した。(3) Evaluation of characteristics Each resin-coated copper foil was cut into a length of 300 mm and a width of 300 mm.
The surface on the insulating resin layer side is coated with a 1 mm thick glass fiber
Placed on xy-prepreg sheet (FR-4)
Sandwiched between two smooth stainless steel plates at a temperature of 170 ° C.
Pressure 50kg / cm TwoThermocompression bonding for 60 minutes on one side and copper-laminated
Boards were manufactured.
【００３５】この片面銅張り積層板の銅箔表面に対し、
下記の仕様によるエッチング特性と、プレプリグ材との
接合強度と耐塩酸性、および耐熱性と難燃性と誘電特性
を測定した。 エッチング特性：片面銅張り積層板から縦１００mm，横
１００mmの試料を切り出した。試料の銅箔の上に、厚み
２.５μｍのレジスト膜を形成したのち線幅３５μｍ，
線間ピッチ２５μｍの直線平行パターンを描画現像し
た。ついで、塩化第二鉄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してエッチング処
理を行い配線パターンを形成した。With respect to the copper foil surface of this single-sided copper-clad laminate,
The etching characteristics according to the following specifications, the bonding strength with the prepreg material and hydrochloric acid resistance, and the heat resistance, flame retardancy and dielectric characteristics were measured. Etching characteristics: A sample having a length of 100 mm and a width of 100 mm was cut out from a single-sided copper-clad laminate. A resist film having a thickness of 2.5 μm was formed on the copper foil of the sample, and then a line width of 35 μm was formed.
A line parallel pattern with a line pitch of 25 μm was drawn and developed. Then, an etching treatment was performed by spraying an etchant composed of 2.0 mol / L of ferric chloride and 0.4 mol / L of hydrochloric acid to form a wiring pattern.
【００３６】なお、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、配線パターンの基部に
残銅が認められなくなるまでの最適時間を調べ、当該時
間を採用した。得られた配線パターンにつき、ショート
部と切断部の有無を顕微鏡観察した。いずれも存在しな
いものを良好とした。The etching time for the laminated board was determined by conducting a preliminary test using the same laminated board, examining the optimum time until no residual copper was found at the base of the wiring pattern, and employing the time. The resulting wiring pattern was observed under a microscope for the presence or absence of shorts and cuts. Those which did not exist were evaluated as good.
【００３７】接合強度：片面銅張り積層板から試料を切
りだし、その試料につき、ＪＩＳＣ６５１１で規定する
方法に準拠して引き剥がし強度を測定した。なお、この
値が０.８kg／cm以上であるものは良品と判定される。 耐塩酸性：線幅１mmのテストパターン描画試料を濃度１
２％の塩酸（温度２５℃）に３０分間浸漬したのち取り
出して前記した引き剥がし強度を測定し、塩酸浸漬前後
における引き剥がし強度の低下率（％）を算出した。こ
の値が小さいものほど耐塩酸性が優れていることを表
す。Bonding strength: A sample was cut out from a single-sided copper-clad laminate, and the peeling strength of the sample was measured according to the method specified in JIS C6511. If the value is 0.8 kg / cm or more, it is determined to be good. Hydrochloric acid resistance: Test pattern drawing sample with 1mm line width, density 1
After being immersed in 2% hydrochloric acid (temperature: 25 ° C.) for 30 minutes, it was taken out and the above-mentioned peel strength was measured, and the reduction rate (%) of the peel strength before and after immersion in hydrochloric acid was calculated. The smaller the value, the better the hydrochloric acid resistance.
【００３８】耐熱性：ＪＩＳ Ｃ６４８１で規定するＤ
ＳＣ法により樹脂のガラス転移温度（Ｔｇ）を測定し
た。この値が１８０℃以上であることが好ましい。 難燃性：ＪＩＳ Ｃ６４８１で規定する耐熱性測定法に
より、試料着火後のフレーミング時間（１回目の着火
後、消えるまでの時間）とグローイング時間（２回目の
着火後、消えるまでの時間）を測定する。Heat resistance: D specified in JIS C6481
The glass transition temperature (Tg) of the resin was measured by the SC method. This value is preferably 180 ° C. or higher. Flame retardancy: Measure the framing time after ignition of the sample (the time from the first ignition until it goes out) and the glowing time (the time from the second ignition until it goes out) by the heat resistance measurement method specified in JIS C6481. I do.
【００３９】試料５個、各２回、計１０回のフレーミン
グ時間が、平均５秒以下でかつ最大１０秒以下であり、
グローイング時間が３０秒を超えない場合、ＵＬ−９４
Ｖ０に合格する。 誘電特性：ＪＩＳ Ｃ６４８１の自動平衡ブリッジ法で
比誘電率を測定する。測定値が３.２以下であることが
好ましい。以上の結果を一括して表１，２に示した。The framing time of 5 samples, 2 times each, a total of 10 times, is an average of 5 seconds or less and a maximum of 10 seconds or less,
If the glowing time does not exceed 30 seconds, UL-94
Pass V0. Dielectric property: The relative dielectric constant is measured by the automatic equilibrium bridge method of JIS C6481. It is preferable that the measured value is 3.2 or less. The above results are collectively shown in Tables 1 and 2.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【発明の効果】以上の説明で明らかなように、本発明の
樹脂付き銅箔は、基材であるプリプレグとの接合強度が
高く、しかもエッチング特性は良好で耐熱性，難燃性も
優れ、更には誘電特性も良好で、線間ピッチや線幅が３
０μｍ前後の高密度超微細配線を有する印刷回路基板用
の銅箔として好適である。As is apparent from the above description, the resin-coated copper foil of the present invention has a high bonding strength with the prepreg as the base material, has good etching characteristics, and has excellent heat resistance and flame retardancy. Furthermore, the dielectric properties are good, and the line pitch and line width are 3
It is suitable as a copper foil for a printed circuit board having a high-density ultrafine wiring of about 0 μm.
【図１】本発明の樹脂付き銅箔Ａの断面構造を示す断面
図である。FIG. 1 is a cross-sectional view showing a cross-sectional structure of a copper foil with resin A of the present invention.
【図２】本発明の他の樹脂付き銅箔Ｂの断面構造を示す
断面図である。FIG. 2 is a sectional view showing a sectional structure of another copper foil with resin B of the present invention.
１ 銅箔 １ａ 銅箔１の表面 ２ 絶縁樹脂層 ３ ニッケル層 ４ 亜鉛層 Reference Signs List 1 copper foil 1a surface of copper foil 1 2 insulating resin layer 3 nickel layer 4 zinc layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ３２Ｂ 27/18 Ｂ３２Ｂ 27/18 Ｂ 27/38 27/38 Ｃ２５Ｄ 7/00 Ｃ２５Ｄ 7/00 Ｊ Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｈ ６１０Ｌ 1/09 1/09 Ｃ 3/46 3/46 Ｔ Ｓ (72)発明者 加藤 人士 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 Ｆターム(参考） 4E351 AA03 AA04 BB01 BB30 BB33 BB35 BB38 CC06 CC21 DD04 DD08 DD19 GG02 GG04 GG13 4F100 AB16C AB17A AB18D AB33A AH05B AK01B AK51B AK53 BA02 BA04 BA07 BA10A BA10B DD07A EH71 EJ69 GB43 JA20C JA20D JB12B JB13B JG04B JG05 JJ03 JJ07 JK06 YY00A YY00C YY00D 4K024 AA05 AA09 AB02 BA09 BB11 BC02 DB04 DB06 GA16 5E346 AA05 AA12 AA15 BB01 CC08 CC09 CC31 CC32 CC37 DD03 DD12 EE02 EE06 EE19 GG02 GG27 HH11 HH16 HH18 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) B32B 27/18 B32B 27/18 B 27/38 27/38 C25D 7/00 C25D 7/00 J H05K 1 / 03 610 H05K 1/03 610H 610L 1/09 1/09 C 3/46 3/46 TS (72) Inventor Hitoshi Kato 2-6-1 Marunouchi, Chiyoda-ku, Tokyo F-term in Furukawa Electric Co., Ltd. (Reference) 4E351 AA03 AA04 BB01 BB30 BB33 BB35 BB38 CC06 CC21 DD04 DD08 DD19 GG02 GG04 GG13 4F100 AB16C AB17A AB18D AB33A AH05B AK01B AK51B AK53 BA02 BA04 BA07 BA10A BA10B DD07A EJ71J04 J03 GB AA05 AA09 AB02 BA09 BB11 BC02 DB04 DB06 GA16 5E346 AA05 AA12 AA15 BB01 CC08 CC09 CC31 CC32 CC37 DD03 DD12 EE02 EE06 EE19 GG02 GG27 HH11 HH16 HH18
Claims (2)
被覆されている樹脂付き銅箔において、 前記絶縁樹脂層が、多官能性シアン酸エステル化合物を
５０〜７０重量％含有し、かつ、臭素化エポキシ化合物
を臭素換算量で１２重量％以上２０重量％未満含有する
樹脂組成物から成ることを特徴とする樹脂付き銅箔。1. A resin-coated copper foil in which the surface of the copper foil is covered with a semi-cured insulating resin layer, wherein the insulating resin layer contains 50 to 70% by weight of a polyfunctional cyanate compound, A resin-coated copper foil comprising a resin composition containing a brominated epoxy compound in an amount of 12% by weight or more and less than 20% by weight in terms of bromine.
０μｍであり、かつ、前記銅箔の表面には、更に、厚み
０.０１〜０.０５mg／dm2のニッケル層と厚み０.１５〜
０.５mg／dm2の亜鉛層がこの順序で形成されている請求
項１の樹脂付き銅箔。2. The copper foil has a surface roughness (Rz) of 2.0 to 4.0.
0 μm, and a nickel layer having a thickness of 0.01 to 0.05 mg / dm 2 and a thickness of 0.15 to 0.05 mg / dm 2 on the surface of the copper foil.
Resin-coated copper foil according to claim 1, the zinc layer of 0.5 mg / dm 2 are formed in this order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11089395A JP2000280401A (en) | 1999-03-30 | 1999-03-30 | Resin-clad copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11089395A JP2000280401A (en) | 1999-03-30 | 1999-03-30 | Resin-clad copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000280401A true JP2000280401A (en) | 2000-10-10 |
Family
ID=13969474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11089395A Pending JP2000280401A (en) | 1999-03-30 | 1999-03-30 | Resin-clad copper foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000280401A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003015483A1 (en) * | 2001-08-06 | 2003-02-20 | Mitsui Mining & Smelting Co., Ltd. | Printed wiring board-use copper foil and copper clad laminated sheet using the printed wiring board-use copper foil |
| JP2003136626A (en) * | 2001-11-02 | 2003-05-14 | Toyo Kohan Co Ltd | Conductive layer-laminated material and part using the material |
| JP2004079523A (en) * | 2002-08-01 | 2004-03-11 | Furukawa Techno Research Kk | Electrolytic copper foil and electrolytic copper foil for current collector of secondary battery |
| WO2012173178A1 (en) * | 2011-06-14 | 2012-12-20 | 大日本印刷株式会社 | Conductive base for forming wiring pattern of collector sheet for solar cells, and method for producing collector sheet for solar cells |
| JP2013004236A (en) * | 2011-06-14 | 2013-01-07 | Dainippon Printing Co Ltd | Conductive base material for forming wring pattern of current collection sheet for solar cell |
-
1999
- 1999-03-30 JP JP11089395A patent/JP2000280401A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003015483A1 (en) * | 2001-08-06 | 2003-02-20 | Mitsui Mining & Smelting Co., Ltd. | Printed wiring board-use copper foil and copper clad laminated sheet using the printed wiring board-use copper foil |
| US6989199B2 (en) * | 2001-08-06 | 2006-01-24 | Mitsui Mining & Smelting Co., Ltd. | Copper foil for printed-wiring board and copper-clad laminate using copper foil for printed-wiring board |
| JP2003136626A (en) * | 2001-11-02 | 2003-05-14 | Toyo Kohan Co Ltd | Conductive layer-laminated material and part using the material |
| JP2004079523A (en) * | 2002-08-01 | 2004-03-11 | Furukawa Techno Research Kk | Electrolytic copper foil and electrolytic copper foil for current collector of secondary battery |
| WO2012173178A1 (en) * | 2011-06-14 | 2012-12-20 | 大日本印刷株式会社 | Conductive base for forming wiring pattern of collector sheet for solar cells, and method for producing collector sheet for solar cells |
| JP2013004236A (en) * | 2011-06-14 | 2013-01-07 | Dainippon Printing Co Ltd | Conductive base material for forming wring pattern of current collection sheet for solar cell |
| CN103732798A (en) * | 2011-06-14 | 2014-04-16 | 大日本印刷株式会社 | Conductive base for forming wiring pattern of collector sheet for solar cells, and method for producing collector sheet for solar cells |
| US9666746B2 (en) | 2011-06-14 | 2017-05-30 | Dai Nippon Printing Co., Ltd. | Conductive base for forming wiring pattern of collector sheet for solar cells, and method for producing collector sheet for solar cells |
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