JPH11279493A - Adhesive sheet, metallic foil with adhesive, multilayer board covered with metallic foil, and layered board and printed circuit board covered with metallic foil - Google Patents
Adhesive sheet, metallic foil with adhesive, multilayer board covered with metallic foil, and layered board and printed circuit board covered with metallic foilInfo
- Publication number
- JPH11279493A JPH11279493A JP10087627A JP8762798A JPH11279493A JP H11279493 A JPH11279493 A JP H11279493A JP 10087627 A JP10087627 A JP 10087627A JP 8762798 A JP8762798 A JP 8762798A JP H11279493 A JPH11279493 A JP H11279493A
- Authority
- JP
- Japan
- Prior art keywords
- clad
- adhesive
- copper
- adhesive sheet
- laminate
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 95
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 95
- 239000011888 foil Substances 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000000155 melt Substances 0.000 claims abstract description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 abstract description 31
- 229920000647 polyepoxide Polymers 0.000 abstract description 31
- 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 abstract description 24
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 70
- 229910052802 copper Inorganic materials 0.000 description 38
- 239000010949 copper Substances 0.000 description 38
- 239000011889 copper foil Substances 0.000 description 33
- 238000009413 insulation Methods 0.000 description 16
- 229920003986 novolac Polymers 0.000 description 16
- 239000002966 varnish Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- -1 glycidyl ester Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、接着剤シート、接
着剤付き金属はく、金属はく張多層積層板、金属はく張
積層板及びプリント配線板に関する。The present invention relates to an adhesive sheet, a metal foil with an adhesive, a metal-clad multilayer laminate, a metal-clad laminate, and a printed wiring board.
【０００２】[0002]
【従来の技術】電子機器に広く用いられているプリント
配線板は、金属はく張積層板に回路加工を施して得られ
る。この金属はく張積層板としては、織布基材に熱硬化
性樹脂組成物のワニスを含浸乾燥して得られるプリプレ
グを金属はくとともに積層成形したものが広く用いられ
ていた。すなわち、絶縁基材層が熱硬化性樹脂組成物の
硬化物と織布基材とからなりこれに金属はくが接着され
た構造となっていた。なお、単にプリント配線板という
ときは、両面プリント配線板のほか多層プリント配線板
を含む。また、従来汎用の多層プリント配線板は、両面
プリント配線板と金属はくとをプリプレグを介して加熱
加圧して接着一体化し得た内層回路入り金属はく張多層
積層板に回路加工を施して得られたものであった。４層
金属はく張積層板は、両面プリント配線板１枚の両面に
金属はくを接着一体化したものであり、６層金属はく張
積層板は、両面プリント配線板２枚の間にプリプレグを
介し、さらに、その両面に金属はくを接着一体化したも
のであった。2. Description of the Related Art A printed wiring board widely used in electronic equipment is obtained by performing circuit processing on a metal-clad laminate. As the metal-clad laminate, a prepreg obtained by impregnating a woven fabric base material with a varnish of a thermosetting resin composition and drying and laminating the prepreg together with a metal foil has been widely used. That is, the insulating base material layer has a structure in which the cured product of the thermosetting resin composition and the woven fabric base material are bonded to the metal foil. In addition, when simply called a printed wiring board, it includes a multilayer printed wiring board in addition to a double-sided printed wiring board. In addition, conventional multi-layer printed wiring boards are made by applying circuit processing to a metal-laminated multilayer laminated board containing an inner layer circuit, which is obtained by bonding and bonding a double-sided printed wiring board and a metal foil through a prepreg by applying heat and pressure. It was obtained. The four-layer metal-clad laminate is made by bonding and integrating metal foils on both sides of one double-sided printed wiring board. The six-layer metal-clad laminate is placed between two double-sided printed wiring boards. A metal foil was bonded and integrated on both sides of the prepreg via a prepreg.
【０００３】最近、電子機器が小型化するのにともな
い、プリント配線板も薄型化し、さらに、配線を高密度
化する必要がでてきている。材料として織布基材を用い
ると、薄型化には限度があることから、金属はく張多層
積層板の製造において、熱硬化性樹脂に電気絶縁性ウィ
スカーを分散させてシート状にした接着剤シートを用い
ることが提案された。In recent years, as electronic devices have become smaller, the thickness of printed wiring boards has been reduced, and furthermore, it has become necessary to increase the density of wiring. When a woven base material is used, there is a limit to the reduction in thickness.Therefore, in the production of metal-clad multilayer laminates, an adhesive in which electrically insulating whiskers are dispersed in a thermosetting resin to form a sheet is used. It has been proposed to use sheets.
【０００４】近年、電子機器の小型軽量化、高性能化、
低コスト化が進行し、プリント配線板には高密度化、薄
型化、高信頼性化、低コスト化が要求されている。高密
度化のためには、微細配線が必要であり、そのためには
表面の平坦性が良好でかつ、寸法安定性が良好でなくて
はならない。さらに微細なスルーホールやインターステ
ーシャルバイアホール（ＩＶＨ）が必要であり、ドリル
加工性、レーザ穴加工性が良好であることが要求されて
いる。表面の平坦性を良好にするためには、多層化積層
成形時に適正な流動性を有する必要がある。In recent years, electronic equipment has been reduced in size and weight and improved in performance.
Cost reduction is progressing, and printed wiring boards are required to have higher density, thinner, higher reliability, and lower cost. For high density, fine wiring is required, and for that purpose, the surface must have good flatness and good dimensional stability. Further, fine through holes and interstitial via holes (IVH) are required, and good drill workability and laser hole workability are required. In order to improve the flatness of the surface, it is necessary to have proper fluidity during multilayer lamination molding.
【０００５】前記接着剤シートは、薄くでき、小径ドリ
ル加工性、レーザ穴加工性及び表面平坦性に優れる。ま
た、剛性も良好であって部品実装工程においてたわみを
生じることがなく、ワイヤーボンディング性も極めて良
好である。また織布基材を用いていないにもかかわら
ず、熱膨張係数が小さく、実装部品との接続信頼性が良
好である。[0005] The adhesive sheet can be made thin and has excellent small-diameter drill workability, laser hole workability, and surface flatness. In addition, the rigidity is good, no bending occurs in the component mounting process, and the wire bonding property is extremely good. Moreover, despite the use of no woven fabric base material, the thermal expansion coefficient is small, and the connection reliability with the mounted components is good.
【０００６】[0006]
【発明が解決しようとする課題】金属はく張多層積層板
の製造において、金属はくの接着に用いられる接着剤シ
ートは、内層の両面プリント配線板に形成された内層回
路間の凹みを埋める必要がある。配線の高密度化に伴い
回路幅及び回路間隔が小さくなり、例えば、回路幅４０
μｍ、回路間隔４０μｍというような狭い回路間隔とな
ってきている。また、接着剤シートにより構成される絶
縁層の厚さも薄くすることが要求されるようになってき
ている。このような状況のもとで、接着剤中に電気絶縁
性ウィスカーを分散させた接着剤シートを用いて製造し
た金属はく張多層積層板は、ある時間経過後に、特に、
高温高湿条件下において、絶縁性が劣化することがあっ
た。請求項１、２又は３に記載の発明は、熱硬化性樹脂
及び電気絶縁性ウィスカーを必須成分とし、時間経過後
の絶縁性劣化の少ない接着剤シートを提供することを目
的とする。金属はく張多層積層板の製造に用いられる接
着剤シートは、金属はくの片面に接着剤シートが形成さ
れていると製造作業に便利である。請求項４に記載の発
明は、請求項１、２又は３に記載の発明の目的に加え
て、金属はく張多層積層板の製造に便利な接着剤付き金
属はくを提供することを目的とする。また、請求項５に
記載の発明は、時間経過後の絶縁性劣化の少ない金属は
く張多層積層板を提供することを目的とする。本発明に
なる接着剤シートは、時間経過後の絶縁性劣化が少ない
ことから、金属はく張積層板の製造においても有用であ
る。請求項６に記載の発明は、時間経過後の絶縁性劣化
の少ない金属はく張積層板を提供することを目的とす
る。また、請求項７に記載の発明は、時間経過後の絶縁
性劣化の少ないプリント配線板を提供することを目的と
する。In the production of a metal-clad multilayer laminate, an adhesive sheet used for bonding the metal foil fills in a recess between inner-layer circuits formed on an inner double-sided printed wiring board. There is a need. As the wiring density increases, the circuit width and the circuit interval become smaller.
The circuit interval is as narrow as μm and the circuit interval is 40 μm. Also, it has been required to reduce the thickness of the insulating layer formed of the adhesive sheet. Under such circumstances, a metal-clad multilayer laminate manufactured using an adhesive sheet in which an electrically insulating whisker is dispersed in an adhesive, after a certain period of time,
Under the conditions of high temperature and high humidity, the insulating property sometimes deteriorated. An object of the present invention is to provide an adhesive sheet containing a thermosetting resin and an electrically insulating whisker as essential components, and having less insulation deterioration after a lapse of time. The adhesive sheet used for manufacturing the metal-clad multilayer laminate is convenient for the manufacturing operation if the adhesive sheet is formed on one side of the metal foil. The object of the invention described in claim 4 is to provide a metal foil with an adhesive which is convenient for manufacturing a metal-clad multilayer laminate in addition to the object of the invention described in claim 1, 2 or 3. And Another object of the present invention is to provide a metal-clad multilayer laminate with little deterioration in insulation after a lapse of time. The adhesive sheet according to the present invention is useful in the production of a metal-clad laminate, since the insulation property after the lapse of time is small. It is an object of the present invention to provide a metal-clad laminate with little deterioration in insulation after a lapse of time. Another object of the present invention is to provide a printed wiring board with less deterioration in insulation after a lapse of time.
【０００７】[0007]
【課題を解決するための手段】請求項１に記載の発明
は、熱硬化性樹脂及び電気絶縁性ウィスカーを必須成分
とする接着剤をシート状に形成してなり、溶融粘度が１
００〜１，０００Ｐａ・ｓの範囲にある接着剤シートで
ある。According to the first aspect of the present invention, an adhesive having a thermosetting resin and an electrically insulating whisker as essential components is formed in a sheet shape, and has a melt viscosity of 1%.
It is an adhesive sheet in the range of 00 to 1,000 Pa · s.
【０００８】溶融粘度が１００Ｐａ・ｓ未満であると、
時間経過後の絶縁性劣化が大きくなる。また、１，００
０Ｐａ・ｓを超えると、内層回路間の凹みを埋めること
ができなくなる。このことから、溶融粘度が２００〜８
００Ｐａ・ｓの範囲にあるのが好ましい。なお、溶融粘
度とは、フローテスターにより測定され、１３０℃にお
いて示される一番低い粘度の値（ηｍｉｎ）をいう。フ
ローテスターとしては、市販品を使用でき、例えば、株
式会社島津製作所製のフローテスターＣＦＴ−２０型
（商品名）などを挙げることができる。When the melt viscosity is less than 100 Pa · s,
Deterioration of insulation after the passage of time increases. Also, 1,00
If it exceeds 0 Pa · s, it becomes impossible to fill the dent between the inner layer circuits. From this, the melt viscosity is 200 to 8
It is preferably in the range of 00 Pa · s. The melt viscosity means the lowest viscosity value (ηmin) measured at 130 ° C. by a flow tester. As the flow tester, a commercially available product can be used, and examples thereof include a flow tester CFT-20 (trade name) manufactured by Shimadzu Corporation.
【０００９】電気絶縁性ウィスカーは、平均直径０．３
〜３．０μｍの範囲であり、平均長さが３〜２０μｍの
範囲であるのが好ましい。すなわち、請求項２に記載の
発明は、電気絶縁性ウィスカーが、平均直径０．３〜
３．０μｍの範囲であり、平均長さが３〜２０μｍの範
囲である請求項１に記載の接着剤シートである。The electrically insulating whisker has an average diameter of 0.3.
The average length is preferably in the range of 3 to 20 μm. That is, in the invention according to claim 2, the electrically insulating whisker has an average diameter of 0.3 to 0.3.
The adhesive sheet according to claim 1, wherein the adhesive sheet has a range of 3.0 µm and an average length of 3 to 20 µm.
【００１０】平均直径が０．３μｍ未満であると、熱硬
化性樹脂に均一に分散させることが困難となる傾向にあ
り、平均直径が３．０μｍを超えると表面平滑性が悪く
なる傾向にあり、また、平均長さが３．０μｍ未満であ
ると、補強効果が不充分となる傾向にあり、２０μｍを
超えると均一に分散させることが困難となるほか、回路
間又は異なる導体層間にまたがって接触する可能が高く
なり、繊維に沿って生じやすいとされる金属マイグレー
ションを生じやすくなり、時間経過後の絶縁性劣化を生
じやすくなる傾向にある。このことから、平均直径が
０．５〜１μｍで、平均長さが４〜１５μｍの範囲であ
るのがより好ましい。When the average diameter is less than 0.3 μm, it tends to be difficult to uniformly disperse in the thermosetting resin, and when the average diameter exceeds 3.0 μm, the surface smoothness tends to deteriorate. When the average length is less than 3.0 μm, the reinforcing effect tends to be insufficient, and when the average length is more than 20 μm, it is difficult to uniformly disperse the reinforcement, and it also extends between circuits or between different conductor layers. The possibility of contact increases, metal migration, which is likely to occur along the fiber, tends to occur, and the insulation property tends to deteriorate over time. From this, it is more preferable that the average diameter is 0.5 to 1 μm and the average length is 4 to 15 μm.
【００１１】また、電気絶縁性ウィスカーは、最大長さ
が５０μｍであるようにするのが好ましい。すなわち、
請求項３に記載の発明は、電気絶縁性ウィスカーの最大
長さが５０μｍである請求項２に記載の接着剤シートで
ある。Preferably, the electrically insulating whisker has a maximum length of 50 μm. That is,
The invention according to claim 3 is the adhesive sheet according to claim 2, wherein the maximum length of the electrically insulating whisker is 50 μm.
【００１２】電気絶縁性ウィスカーの最大長さが５０μ
ｍを超えると、金属マイグレーションを生じやすくな
り、時間経過後の絶縁性劣化を生じやすくなる傾向にあ
る。また、回路間隔が小さくなっていることから、最大
長さが４０μｍであるのがより好ましい。The maximum length of the electrically insulating whisker is 50 μm.
If it exceeds m, metal migration tends to occur, and the insulation property tends to deteriorate after a lapse of time. Further, since the circuit interval is small, it is more preferable that the maximum length is 40 μm.
【００１３】本発明の接着剤シートは、必要な成分を溶
剤に溶解・分散させてワニスとし、このワニスをキャリ
ヤーフィルムに塗工して製造される。キャリヤーフィル
ムとして金属はくを用いれば、金属はく張多層積層板を
製造するときに、接着剤シートと金属はくとを別々に重
ねる手間が省けて省力化できる。すなわち、請求項４に
記載の発明は、金属はくの片面に請求項１、２又は３に
記載の接着剤シートが形成されてなる接着剤付き金属は
くである。また、請求項５に記載の発明は、請求項１、
２又は３に記載の接着剤シートにより外層金属はくが接
着されてなる金属はく張多層積層板である。また、請求
項６に記載の発明は、請求項１、２又は３に記載の接着
剤シートにより金属はくが接着されてなる金属はく張積
層板である。また、請求項７に記載の発明は、請求項５
に記載の金属はく張多層積層板又は請求項６に記載の金
属はく張積層板に回路加工を施してなるプリント配線板
である。The adhesive sheet of the present invention is produced by dissolving and dispersing necessary components in a solvent to form a varnish, and applying the varnish to a carrier film. If a metal foil is used as the carrier film, the labor for laminating the adhesive sheet and the metal foil separately can be eliminated when manufacturing the metal-clad multilayer laminate, thereby saving labor. That is, the invention according to claim 4 is a metal foil with an adhesive, wherein the adhesive sheet according to claim 1, 2 or 3 is formed on one side of the metal foil. Further, the invention described in claim 5 is based on claim 1,
4. A metal-clad multilayer laminate in which an outer-layer metal foil is adhered by the adhesive sheet according to 2 or 3. According to a sixth aspect of the invention, there is provided a metal-clad laminate obtained by bonding a metal foil with the adhesive sheet according to the first, second, or third aspect. Further, the invention described in claim 7 is the same as claim 5.
Or a printed wiring board obtained by subjecting the metal-clad laminate according to claim 6 to circuit processing.
【００１４】[0014]
【発明の実施の形態】本発明で使用する熱硬化性樹脂と
しては、従来積層板用として公知の熱硬化性樹脂を使用
することができる。このような熱硬化性樹脂としては、
エポキシ樹脂、ビスマレイミド−トリアジン樹脂、ポリ
イミド樹脂、フェノール樹脂、メラミン樹脂、けい素樹
脂、不飽和ポリエステル樹脂、シアン酸エステル樹脂、
イソシアネート樹脂又はこれらの種々の変性樹脂類が挙
げられる。これらのうち、耐熱性及び電気的な特性が良
好であることからビスマレイミド−トリアジン樹脂又は
エポキシ樹脂が好ましい。エポキシ樹脂としては、ビス
フェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポ
キシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェ
ノールＡノボラック型エポキシ樹脂、フェノールノボラ
ック型エポキシ樹脂、クレゾールノボラック型エポキシ
樹脂、サリチルアルデヒドノボラック型エポキシ樹脂、
ビスフェノールＦノボラック型エポキシ樹脂、脂肪族環
状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、
グリシジルアミン型エポキシ樹脂、ヒダントイン型エポ
キシ樹脂、イソシアヌレート型エポキシ樹脂、これらの
ハロゲン化物、これらの水素添加物を挙げることができ
る。これらは、単独で使用してもよく、２種以上を併用
してもよい。これらのうち、耐熱性が良好であることか
らビスフェノールＡノボラック型エポキシ樹脂又はサリ
チルアルデヒドノボラック型エポキシ樹脂が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the thermosetting resin used in the present invention, a thermosetting resin conventionally known for a laminated board can be used. As such a thermosetting resin,
Epoxy resin, bismaleimide-triazine resin, polyimide resin, phenol resin, melamine resin, silicon resin, unsaturated polyester resin, cyanate ester resin,
Examples include isocyanate resins or various modified resins thereof. Among these, a bismaleimide-triazine resin or an epoxy resin is preferable because of its good heat resistance and electrical characteristics. As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, salicylaldehyde novolak type epoxy resin,
Bisphenol F novolak type epoxy resin, aliphatic cyclic epoxy resin, glycidyl ester type epoxy resin,
Glycidylamine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, halides thereof, and hydrogenated products thereof can be exemplified. These may be used alone or in combination of two or more. Of these, bisphenol A novolak type epoxy resin or salicylaldehyde novolak type epoxy resin is preferable because of its good heat resistance.
【００１５】このほか、熱硬化性樹脂の硬化剤が配合さ
れる。硬化剤としては、熱硬化性樹脂がエポキシ樹脂の
場合、ジシアンジアミド、フェノール系硬化剤などが挙
げられる。フェノール系硬化剤としては、ビスフェノー
ルＡ、ビスフェノールＦ、ポリビニルフェノール、フェ
ノールノボラック樹脂（ハロゲン化物又は水素化物を含
む）、ビスフェノールＡノボラック樹脂（ハロゲン化物
又は水素化物を含む）などが挙げられる。中でも、硬化
物の耐熱性が優れることから、ビスフェノールＡノボラ
ック樹脂が好ましい。この硬化剤の配合割合は熱硬化性
樹脂よって異なるが、例えば、エポキシ樹脂の場合、エ
ポキシ樹脂１００重量部に対して、ジシアンジアミドで
は２〜５重量部、フェノール系硬化剤では３０〜８０重
量部の範囲で適宜選択される。[0015] In addition, a curing agent for a thermosetting resin is blended. When the thermosetting resin is an epoxy resin, examples of the curing agent include dicyandiamide and phenol-based curing agents. Examples of phenolic curing agents include bisphenol A, bisphenol F, polyvinyl phenol, phenol novolak resins (including halides or hydrides), and bisphenol A novolak resins (including halides or hydrides). Among them, bisphenol A novolak resin is preferred because the cured product has excellent heat resistance. The mixing ratio of this curing agent varies depending on the thermosetting resin. For example, in the case of an epoxy resin, 2 to 5 parts by weight of dicyandiamide and 30 to 80 parts by weight of a phenolic curing agent, relative to 100 parts by weight of epoxy resin. It is appropriately selected within the range.
【００１６】硬化剤のほか、必要により硬化促進剤を使
用する。硬化促進剤としては、熱硬化性樹脂がエポキシ
樹脂の場合、イミダゾール化合物、有機リン化合物、第
３級アミン、第４級アンモニウム塩などが挙げられる。
この硬化促進剤の配合割合は、エポキシ樹脂１００重量
部に対して、０．０１〜２０重量部の範囲で適宜選択さ
れる。In addition to the curing agent, a curing accelerator is used if necessary. When the thermosetting resin is an epoxy resin, examples of the curing accelerator include an imidazole compound, an organic phosphorus compound, a tertiary amine, and a quaternary ammonium salt.
The compounding ratio of this curing accelerator is appropriately selected within the range of 0.01 to 20 parts by weight based on 100 parts by weight of the epoxy resin.
【００１７】本発明で用いられる電気絶縁性ウィスカー
としては、ほう酸アルミニウムウィスカー、ウォラスト
ナイトウィスカー、チタン酸カリウムウィスカー、塩基
性硫酸マグネシウムウィスカー、窒化けい素ウィスカ
ー、二酸化けい素ウィスカー、α−アルミナウィスカー
など、セラミックウィスカーの範疇に含まれるウィスカ
ーを使用することができる。これらは単独で使用しても
よく、２種以上併用してもよい。なかでも、低熱膨張係
数及び高電気絶縁性であることからホウ酸アルミニウム
ウィスカーが好ましい。ホウ酸アルミニウムウィスカー
を用いると、常温及び高温下における剛性が高く、ワイ
ヤーボンディング性に優れ、電気信号の伝達特性に優
れ、熱膨張係数が小さく、寸法安定性に優れた金属はく
張多層積層板を製造できる。これらの電気絶縁性ウィス
カーは、市販品を使用することができ、所定の直径のウ
ィスカーをボールミル、ビーズミル、ナノメーカー、ナ
ノマイザーなどのせん断力がかかる公知の装置により粉
砕することにより所望の長さにして使用される。The electrically insulating whiskers used in the present invention include aluminum borate whiskers, wollastonite whiskers, potassium titanate whiskers, basic magnesium sulfate whiskers, silicon nitride whiskers, silicon dioxide whiskers, α-alumina whiskers and the like. And whiskers included in the category of ceramic whiskers can be used. These may be used alone or in combination of two or more. Among them, aluminum borate whiskers are preferable because of their low coefficient of thermal expansion and high electrical insulation. Using aluminum borate whiskers, metal-clad multilayer laminates with high rigidity at normal and high temperatures, excellent wire bonding properties, excellent electrical signal transmission characteristics, low thermal expansion coefficient, and excellent dimensional stability Can be manufactured. Commercially available products can be used for these electrically insulating whiskers, and whiskers having a predetermined diameter are crushed by a known device such as a ball mill, a bead mill, a nano maker, or a nanomizer, to which a whisker having a predetermined shearing force is applied. Used.
【００１８】電気絶縁性ウィスカーをカップリング剤で
表面処理しておくのが好ましい。これにより、樹脂成分
との流れ性及び結合性を向上でき、金属はく張多層積層
板の強度及び耐熱性が向上する。カップリング剤として
は、シリコン系、チタン系、アルミニウム系、ジルコニ
ウム系、ジルコアルミニウム系、クロム系、ボロン系、
リン系、アミノ酸系など、従来公知のカップリング剤を
使用できる。It is preferable that the surface of the electrically insulating whisker is treated with a coupling agent. Thereby, the flowability and bonding property with the resin component can be improved, and the strength and heat resistance of the metal-clad multilayer laminate are improved. As coupling agents, silicon-based, titanium-based, aluminum-based, zirconium-based, zirconaluminum-based, chromium-based, boron-based,
Conventionally known coupling agents such as phosphorus-based and amino-acid-based can be used.
【００１９】電気絶縁性ウィスカーは、熱硬化性樹脂、
硬化剤及び必要に応じて配合される硬化促進剤からなる
樹脂固形分１００重量部に対して、５〜３５０重量部配
合されるのが好ましく、３０〜２３０重量部配合される
のがより好ましい。電気絶縁性ウィスカーの配合量が５
重量部未満であると、接着剤シートを切断するときに、
樹脂が細かく砕けて飛散しやすくなるなどの取扱性が悪
くなるとともに金属はく張多層積層板としたときに十分
な剛性が得られなくなる傾向にある。また、電気絶縁性
ウィスカーの配合量が３５０重量部を超えると、成形時
の回路間の凹みを埋められなくなる可能性が大きくな
り、ボイドやかすれが発生しやすくなり、プリント配線
板に加工したとき、配線板特性を損なう恐れがある。The electrically insulating whisker is made of a thermosetting resin,
The amount is preferably from 5 to 350 parts by weight, more preferably from 30 to 230 parts by weight, based on 100 parts by weight of the resin solid content of the curing agent and the curing accelerator optionally added. The amount of the electrically insulating whisker is 5
If it is less than the weight part, when cutting the adhesive sheet,
There is a tendency for the resin to be crushed finely and to be easily scattered, for example, to be poor in handleability, and for the metal-clad multilayer laminate to have insufficient rigidity. Further, when the amount of the electrically insulating whisker exceeds 350 parts by weight, the possibility that the dent between the circuits at the time of molding cannot be filled becomes large, and voids and blurs are likely to be generated. Therefore, there is a possibility that the characteristics of the wiring board may be impaired.
【００２０】さらに本発明においては、接着剤成分とし
て、前記した各成分の他に、必要に応じて従来より公知
のカップリング剤、充填材等を適宜配合してもよい。Further, in the present invention, conventionally known coupling agents, fillers, and the like may be appropriately compounded as necessary in addition to the above-mentioned components as adhesive components.
【００２１】本発明において、接着剤成分はワニスとし
て以後の工程に供される。必要に応じてカップリング剤
を配合してもよい。ワニスの溶剤としては、アセトン、
メチルエチルケトン、トルエン、キシレン、メチルイソ
ブチルケトン、酢酸エチル、エチレングリコールモノエ
チルエーテル、エチレングリコールモノメチルエーテ
ル、メタノール、エタノール、Ｎ，Ｎ−ジメチルホルム
アミド、Ｎ，Ｎ−ジメチルアセトアミドなどを使用する
ことができる。これらは単独で使用してもよく、２種以
上を併用してもよい。溶剤の配合割合は、熱硬化性樹脂
組成物の固形分１００重量部に対して１〜２００重量部
の範囲が好ましく、３０〜１００重量部の範囲がより好
ましい。１重量部未満であると塗工性が悪くなる傾向に
あり、２００重量部を超えると成形後の耐熱性が悪くな
る傾向にある。In the present invention, the adhesive component is provided to the subsequent steps as a varnish. A coupling agent may be added as needed. Acetone, varnish solvent
Methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. These may be used alone or in combination of two or more. The mixing ratio of the solvent is preferably in the range of 1 to 200 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the solid content of the thermosetting resin composition. If the amount is less than 1 part by weight, the coatability tends to deteriorate, and if it exceeds 200 parts by weight, the heat resistance after molding tends to deteriorate.
【００２２】本発明の接着剤シートは、上記のようにし
て調製した接着剤ワニスをキャリヤーフィルムの片面に
塗工し、加熱して溶剤を除くと共に、熱硬化性樹脂を半
硬化状態にすることにより調製される。塗工方法として
は、例えばナイフコーター法、流延法など公知の方法に
よることができ、特に制限はない。シートの厚さは、３
０〜１５０μｍの範囲で用途に応じて適宜選択される。
シートの厚さが３０μｍ未満であると、内層回路と外層
回路との絶縁性を確保できない恐れがある。また、また
１５０μｍを超えるとシートを平滑に形成するのが困難
となる傾向にある。The adhesive sheet of the present invention is obtained by applying the adhesive varnish prepared as described above to one side of a carrier film, heating to remove the solvent, and bringing the thermosetting resin into a semi-cured state. Prepared by The coating method can be a known method such as a knife coater method and a casting method, and is not particularly limited. The thickness of the sheet is 3
It is appropriately selected in the range of 0 to 150 μm according to the use.
If the thickness of the sheet is less than 30 μm, insulation between the inner layer circuit and the outer layer circuit may not be ensured. On the other hand, if it exceeds 150 μm, it tends to be difficult to form the sheet smoothly.
【００２３】電気絶縁性ウィスカーは、２次元配向に近
い状態（軸方向が接着剤シートの面と平行に近い状態）
にさせることが好ましい。このような配向とすることに
より、本発明の接着剤シートしとて良好な取扱性が得ら
れると同時に金属はく張多層積層板及び金属はく張積層
板としたときに高い剛性が得られる。The electrically insulating whisker is in a state close to two-dimensional orientation (state in which the axial direction is close to parallel to the surface of the adhesive sheet).
It is preferable to make With such an orientation, good handling properties can be obtained for the adhesive sheet of the present invention, and at the same time, high rigidity can be obtained when the metal-clad multilayer laminate and the metal-clad laminate are used. .
【００２４】電気絶縁性ウィスカーを２次元配向に近い
状態にするためには、前述した好ましい範囲の電気絶縁
性ウィスカーを使用すると同時に、キャリヤーフィルム
に接着剤ワニスを塗工する際に、ブレードコータ、ロッ
ドコータ、ナイフコータ、スクイズコータ、リバースロ
ールコータ、トランスファロールコータ等のキャリヤー
フィルムの面と平行な面方向にせん断力を負荷できるか
又はキャリヤーフィルムの面に垂直な方向に圧縮力を負
荷できる塗工方式を採用すればよい。In order to bring the electrically insulating whisker into a state close to two-dimensional orientation, the electrically insulating whisker in the preferred range described above is used, and at the same time, when the adhesive varnish is applied to the carrier film, a blade coater, Coating that can apply a shearing force in the direction parallel to the surface of the carrier film, such as a rod coater, knife coater, squeeze coater, reverse roll coater, transfer roll coater, or can apply a compressive force in the direction perpendicular to the surface of the carrier film A method may be adopted.
【００２５】キャリヤーフィルムとしては、銅はく、ア
ルミはくなどの金属はく、ポリエステルフィルム、ポリ
イミドフィルム、ポリエチレンテレフタレートフィルム
などを使用することができる。キャリヤーフィルムは通
常取り除かれることから、表面を離型剤により処理した
ものを使用することができる。また、銅はくをキャリヤ
ーフィルムとしたときには、キャリヤーフィルムを通常
取り除かずにそのまま金属はく張多層積層板の製造に供
することもできる。As the carrier film, metal foil such as copper foil and aluminum foil, polyester film, polyimide film, polyethylene terephthalate film and the like can be used. Since the carrier film is usually removed, a carrier film whose surface has been treated with a release agent can be used. Further, when the copper foil is used as the carrier film, the carrier film can be used for the production of the metal-clad multilayer laminate without removing the carrier film.
【００２６】接着剤シートの溶融粘度は、硬化促進剤の
配合量により調整することができる。硬化促進剤の配合
量を多くすると溶融粘度が高くなり、少なくすると溶融
粘度が低くなる。また、キャリヤーフィルムに接着剤ワ
ニスを塗工した後の乾燥条件により調整することもでき
る。乾燥温度を高くすると溶融粘度が高くなり、低くす
ると溶融粘度が低くなる。また、乾燥時間を長くすると
溶融粘度が高くなり、短くすると溶融粘度が低くなる。
これらの条件を適宜選択することにより所望の溶融粘度
に調整することができる。The melt viscosity of the adhesive sheet can be adjusted by adjusting the amount of the curing accelerator. When the amount of the curing accelerator is increased, the melt viscosity increases, and when the amount is decreased, the melt viscosity decreases. It can also be adjusted by the drying conditions after applying the adhesive varnish to the carrier film. Increasing the drying temperature increases the melt viscosity, and decreasing the drying temperature decreases the melt viscosity. The longer the drying time, the higher the melt viscosity, and the shorter the drying time, the lower the melt viscosity.
By appropriately selecting these conditions, a desired melt viscosity can be adjusted.
【００２７】このようにして得られた接着剤シートを介
して金属はくを内層のプリント配線板に重ね、又は、接
着剤付金属はくを内層のプリント配線板に重ね、加熱加
圧して成形することにより金属はく張多層積層板が得ら
れる。また、接着剤シートと金属はくとを重ねて加熱加
圧して成形することにより金属はく張積層板が得られ
る。このときの方法及び条件については、公知の方法及
び条件によることができ、特に制限はない。また、金属
はく張多層積層板又は金属はく張積層板に回路加工を施
してプリント配線板が得られる。このときの方法及び条
件についても、公知の方法及び条件によることができ、
特に制限はない。The metal foil is laminated on the printed wiring board of the inner layer via the adhesive sheet thus obtained, or the metal foil with the adhesive is laminated on the printed wiring board of the inner layer, and molded by heating and pressing. By doing so, a metal-clad multilayer laminate is obtained. In addition, a metal-clad laminate is obtained by laminating an adhesive sheet and a metal foil and molding them by heating and pressing. The method and conditions at this time can be based on known methods and conditions, and are not particularly limited. In addition, a printed wiring board can be obtained by performing circuit processing on the metal-clad multilayer laminate or the metal-clad laminate. The method and conditions at this time can also be based on known methods and conditions,
There is no particular limitation.
【００２８】[0028]
【実施例】実施例１ ビスフェノールＡノボラック型エポキシ樹脂（エポキシ
当量２１０、大日本インキ化学工業株式会社製、エピク
ロンＮ８６５（商品名）を使用）１００部（重量部、以
下同じ）、ビスフェノールＡノボラック樹脂（水酸基当
量１２３、大日本インキ化学工業株式会社製、プライオ
ーフェンＶＨ−４１７０（商品名）を使用）１００部及
びジシアンジアミド１部をメチルエチルケトン８０部に
溶解した。さらに、平均直径０．８μｍ、平均長さ２０
μｍ、最大長さ３０μｍの硼酸アルミニウムウィスカー
（四国化成工業株式会社製、アルボレックス（商品名）
を使用）を樹脂固形分１００部に対して９０部配合し、
ワニス中に均一に分散するまで撹拌して接着剤ワニスを
調製した。Example 1 100 parts (parts by weight, hereinafter the same) of bisphenol A novolak resin (epoxy equivalent: 210, using Epicron N865 (trade name) manufactured by Dainippon Ink and Chemicals, Inc.), bisphenol A novolak resin 100 parts of (hydroxyl equivalent 123, Plyofen VH-4170 (trade name) manufactured by Dainippon Ink and Chemicals, Inc.) and 1 part of dicyandiamide were dissolved in 80 parts of methyl ethyl ketone. Furthermore, the average diameter is 0.8 μm and the average length is 20
μm, aluminum borate whisker with a maximum length of 30 μm (Alvolex (trade name) manufactured by Shikoku Chemicals Co., Ltd.)
90 parts per 100 parts of resin solids,
Stir until uniformly dispersed in the varnish to prepare an adhesive varnish.
【００２９】この接着剤ワニスを、厚さ５０μｍのポリ
エチレンテレフタレートフィルムをキャリヤーフィルム
として用い、加熱乾燥後の厚さが５０μｍ及び１００μ
ｍとなるようにナイフコータにより塗工し、温度１５０
℃で１０分間加熱乾燥し、加熱乾燥後にキャリヤーフィ
ルムを剥がして接着剤シートを作製した。The adhesive varnish was prepared by using a polyethylene terephthalate film having a thickness of 50 μm as a carrier film, and having a thickness of 50 μm or 100 μm after heating and drying.
m with a knife coater and a temperature of 150
After heating and drying at 10 ° C. for 10 minutes, the carrier film was peeled off after heating and drying to prepare an adhesive sheet.
【００３０】この接着剤シートの溶融粘度は５８０Ｐａ
・ｓであった。なお、溶融粘度は、フローテスター（株
式会社島津製作所製、フローテスターＣＦＴ−２０型
（商品名）を使用）により、キャリヤーシートから剥が
した接着剤を適宜の大きさに切断して、先端に直径１ｍ
ｍのノズルを有する直径１０ｍｍで１３０℃に加熱され
たシリンダーに挿入し、荷重５ｋｇ／ｍｍ2 で押出すこ
とにより測定した。The melt viscosity of the adhesive sheet is 580 Pa
-It was s. The melt viscosity was measured using a flow tester (made by Shimadzu Corporation, flow tester CFT-20 (trade name)) to cut the adhesive peeled from the carrier sheet into an appropriate size, 1m
It was measured by inserting it into a cylinder heated to 130 ° C. having a diameter of 10 mm and having a nozzle of m and extruding under a load of 5 kg / mm 2 .
【００３１】厚さ０．８ｍｍのガラス布基材エポキシ樹
脂両面銅張積層板（日立化成工業株式会社製、ＭＣＬ−
Ｅ−６７（商品名）を使用）に回路加工を施し、その上
下に前記で作製した厚さ５０μｍの接着剤シートを重
ね、さらにその両外側に厚さ１８μｍの片面粗化銅はく
を該粗化面が接着剤シートに向き合うように重ね、１７
５℃、３ＭＰａで６０分間加熱加圧して銅はく張４層積
層板Ａを作製した。銅はく張４層積層板Ａの表面銅はく
をエッチングして、前記ガラス布基材エポキシ樹脂両面
銅張積層板に形成した回路に位置を合わせて同一の回路
を形成した。そして、内層の回路と表面の回路間に、８
５℃、８５％ＲＨの雰囲気下で直流５０Ｖの電圧を連続
して印加し、絶縁抵抗値の経時変化を測定した。その結
果、１０００時間経過後においても１０9 Ω以上であっ
た。A 0.8 mm thick glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., MCL-
E-67 (trade name) was subjected to circuit processing, and the adhesive sheet having a thickness of 50 μm prepared above was laminated on the upper and lower sides of the circuit sheet. Lay so that the roughened surface faces the adhesive sheet.
Heat and pressure were applied at 5 ° C. and 3 MPa for 60 minutes to produce a copper clad four-layer laminate A. The same circuit was formed by etching the surface copper foil of the copper clad four-layer laminate A and aligning it with the circuit formed on the glass cloth base epoxy resin double-sided copper clad laminate. And between the circuit of the inner layer and the circuit of the surface, 8
A voltage of 50 V DC was continuously applied in an atmosphere of 5 ° C. and 85% RH, and the change over time in the insulation resistance was measured. As a result, the value was 10 9 Ω or more even after 1000 hours.
【００３２】前記で作製した厚さ１００μｍの接着剤シ
ートの上下に厚さ１８μｍの片面粗化銅はくを該粗化面
が接着剤シートに向き合うように重ね、温度１７５℃、
圧力３ＭＰａで６０分間加熱加圧して両面銅はく張積層
板（以下銅張積層板という）Ａを作製した。この銅張積
層板Ａについて、銅はくを除去して、三点曲げ法により
曲げ弾性率を測定した。その結果、たて方向及びよこ方
向の平均で２０ＧＰａであった。また、この銅張積層板
Ａを１０枚重ね、直径０．３ｍｍのドリルにて穴あけし
たときの最上板と最下板の穴位置のずれ量を測定したと
ころ、２０μｍ以下であった。The above-prepared adhesive sheet having a thickness of 100 μm is laid on the upper and lower sides of the adhesive sheet having a thickness of 18 μm so that the roughened surface faces the adhesive sheet at a temperature of 175 ° C.
A double-sided copper-clad laminate (hereinafter referred to as a copper-clad laminate) A was produced by heating and pressing at a pressure of 3 MPa for 60 minutes. For this copper-clad laminate A, the copper foil was removed, and the flexural modulus was measured by a three-point bending method. As a result, the average in the vertical direction and the horizontal direction was 20 GPa. Further, when ten copper-clad laminates A were stacked and drilled with a drill having a diameter of 0.3 mm, the amount of displacement between the uppermost plate and the lowermost plate was measured and found to be 20 μm or less.
【００３３】銅張積層板Ａに回路加工を施し、その両面
に先に作製した厚さ５０μｍの接着剤シートを重ね、そ
のさらに外側に厚さ１８μｍの片面粗化銅はくを粗化面
が接着剤シートに向き合うように重ね、温度１７５℃、
圧力３ＭＰａで６０分間加熱加圧して銅はく張４層積層
板Ｂを作製した。この銅はく張４層積層板Ｂの表面粗さ
を、触針式表面粗さ計にて測定した。測定箇所は直下に
内層回路が存在する部分から存在しない部分にかけて長
さ２５ｍｍの一直線上とした。その結果、直下に内層回
路が存在する部分から存在しない部分の段差の１０点平
均粗さは３μｍ以下であり、回路加工に支障のない良好
な平面平坦性であった。Circuit processing is performed on the copper-clad laminate A, and the adhesive sheet having a thickness of 50 μm previously prepared is superimposed on both surfaces thereof. Lay to face the adhesive sheet, temperature 175 ℃,
Heat and pressure were applied at a pressure of 3 MPa for 60 minutes to produce a copper clad four-layer laminate B. The surface roughness of the copper clad four-layer laminate B was measured with a stylus type surface roughness meter. The measurement location was a straight line having a length of 25 mm from a portion where the inner layer circuit was present to a portion where it was not present. As a result, the 10-point average roughness of the step from the portion where the inner layer circuit was present immediately below to the portion where the inner layer circuit was not present was 3 μm or less, and the flatness was good and did not hinder circuit processing.
【００３４】前記で得られた銅はく張４層積層板Ｂの所
定位置にエッチングにより直径７５μｍの穴をあけ、そ
の穴に、インパクトレーザ（住友重機械工業株式会社製
を使用）によりレーザ光を照射して内層の回路導体を露
出させ、以下、過マンガン酸処理によるデスミア、無電
解めっき、パターン焼付け、エッチングの工程を順次行
う回路加工を施して４層プリント配線板Ａを作製した。
この４層プリント配線板Ａを用いて、以下前記銅はく張
４層積層板Ｂの製造と同様の工程を繰り返すことによ
り、銅はく張１０層積層板Ａを作製した。この銅はく張
１０層積層板Ａについて、たて方向及びよこ方向の熱膨
張係数をＴＭＡにより常温で測定した。その結果、たて
方向及びよこ方向の平均で１０ｐｐｍ／℃であった。ま
た、常温及び２００℃において、たて方向及びよこ方向
の曲げ弾性率をＤＭＡの曲げモードにより測定した。そ
の結果、たて方向及びよこ方向の平均で、常温において
４０ＧＰａ、２００℃において２５ＧＰａであった。さ
らに、常温及び２００℃において、表面硬度をバーコル
硬度計により測定した。その結果、常温における表面硬
度は６５、２００℃における表面硬度は５０であった。A hole having a diameter of 75 μm is formed by etching at a predetermined position of the copper clad four-layer laminate B obtained above, and a laser beam is formed in the hole by an impact laser (manufactured by Sumitomo Heavy Industries, Ltd.). To expose the inner layer circuit conductors, and then perform circuit processing in which the steps of desmearing, electroless plating, pattern baking, and etching by permanganate treatment are sequentially performed to produce a four-layer printed wiring board A.
Using this four-layer printed wiring board A, the same steps as in the production of the copper-clad four-layer laminate B were repeated to produce a copper-clad ten-layer laminate A. With respect to this copper clad ten-layer laminate A, the coefficients of thermal expansion in the vertical and horizontal directions were measured at room temperature by TMA. As a result, the average in the vertical and horizontal directions was 10 ppm / ° C. Further, at room temperature and 200 ° C., the bending elastic modulus in the vertical direction and the horizontal direction was measured by a bending mode of DMA. As a result, the average in the vertical and horizontal directions was 40 GPa at room temperature and 25 GPa at 200 ° C. Further, at room temperature and 200 ° C., the surface hardness was measured with a Barcol hardness meter. As a result, the surface hardness at room temperature was 65, and the surface hardness at 200 ° C. was 50.
【００３５】銅はく張１０層積層板Ａの表面に常法によ
り回路加工を施して表面回路を形成して１０層プリント
配線板Ａを作製した。この１０層プリント配線板Ａにベ
アチップを実装し、ワイヤボンディングにより、表面回
路と接続した。ワイヤボンディング条件は、超音波出力
を１Ｗ、超音波出力時間を５０μｓ、ボンド荷重を１０
０ｇ、ワイヤボンディング温度を１８０℃としたとこ
ろ、良好にワイヤボンディングできた。また、この１０
層プリント配線板Ａに、８×２０ｍｍのＴＳＯＰをはん
だにより表面回路と接続した。そして、−６５℃３０分
間保持−１５０℃３０分間保持の冷熱サイクル試験に供
したところ、２，０００サイクル後もはんだ接続部に断
線等の不良は発生しなかった。またこの１０層プリント
配線板Ａ内部のインターステーシャルバイアホールを含
む回路の導通試験を行ったが断線等のトラブルの発生は
なかった。A circuit was formed on the surface of the copper-clad 10-layer laminated board A by a conventional method to form a surface circuit, thereby producing a 10-layer printed wiring board A. A bare chip was mounted on this 10-layer printed wiring board A and connected to a surface circuit by wire bonding. The wire bonding conditions were as follows: ultrasonic output 1 W, ultrasonic output time 50 μs, bond load 10
When the wire bonding temperature was 0 ° C. and the wire bonding temperature was 180 ° C., the wire bonding was successfully performed. Also, this 10
8 × 20 mm TSOP was connected to the surface printed circuit board A by soldering. Then, when subjected to a cooling / heating cycle test of holding at −65 ° C. for 30 minutes and holding at −150 ° C. for 30 minutes, no failure such as disconnection occurred in the solder connection even after 2,000 cycles. Further, a continuity test was performed on a circuit including the interstitial via hole inside the 10-layer printed wiring board A, but no trouble such as disconnection occurred.
【００３６】実施例２ キャリヤーフィルムを厚さ１８μｍの銅はくに変更し、
以下、実施例１と同様にして、加熱乾燥し、銅はくを剥
がさないことにより接着剤の厚さが５０μｍの接着剤付
銅はくＡ及び１００μｍの接着剤付銅はくＢを作製し
た。そして、銅はくを剥がし、実施例１と同様にして溶
融粘度を測定したところ、５８０Ｐａ・ｓであった。Example 2 The carrier film was changed to a copper foil having a thickness of 18 μm,
Thereafter, by heating and drying in the same manner as in Example 1, a copper foil A with an adhesive having a thickness of 50 μm and a copper foil B with an adhesive having a thickness of 100 μm were prepared by not peeling the copper foil. . Then, when the copper foil was peeled off and the melt viscosity was measured in the same manner as in Example 1, it was 580 Pa · s.
【００３７】接着剤付銅はくＡを用い、ガラス布基材エ
ポキシ樹脂両面銅張積層板の回路加工面と接着剤付銅は
くＡの接着剤面とが向き合うようにして重ね、以下実施
例１における銅はく張４層積層板Ａの作製と同様にして
銅はく張４層積層板Ｃを作製した。そして、銅はく張４
層積層板Ａと同様にして絶縁抵抗値の経時変化を測定し
た。その結果、１０００時間経過後においても１０9 Ω
以上であった。Using copper foil A with an adhesive, the circuit processing surface of the glass cloth base epoxy resin double-sided copper-clad laminate and the adhesive face of the copper foil A with the adhesive are superimposed on each other. A copper clad four-layer laminate C was produced in the same manner as in the production of the copper clad four-layer laminate A in Example 1. And copper foil 4
The time-dependent change of the insulation resistance value was measured in the same manner as in the layer laminate A. As a result, even after 1000 hours, 10 9 Ω
That was all.
【００３８】接着剤付銅はくＢの接着剤面に厚さ１８μ
ｍの片面粗化銅はくを該粗化面が接着剤面に向き合うよ
うに重ね、温度１７５℃、圧力３ＭＰａで６０分間加熱
加圧して銅張積層板Ｂを作製した。この銅張積層板Ｂに
ついて、実施例１と同様にして銅はくを除去して、銅張
積層板Ａと同様にして曲げ弾性率を測定した。その結果
たて方向及びよこ方向の平均で２０ＧＰａであった。ま
た、この銅張積層板Ｂを１０枚重ね、直径０．３ｍｍの
ドリルにて穴あけしたときの最上板と最下板の穴位置の
ずれ量を測定したところ、２０μｍ以下であった。接着
剤付銅はくＡを用いるようにしたほかは、実施例１の銅
はく張４層積層板Ｂと同様にして銅はく張４層積層板Ｄ
を作製した。この銅はく張４層積層板Ｄの表面粗さを実
施例１と同様にして測定したところ、実施例１と同様の
結果が得られた。また、接着剤付銅はくＡを用いるよう
にしたほかは、銅はく張１０層積層板Ａと同様にして４
層プリント配線板Ｂ、銅はく張１０層積層板Ｂ、さらに
１０層プリント配線板Ｂを作製した。銅はく張１０層積
層板Ｂ及び１０層プリント配線板Ｂについて、銅はく張
１０層積層板Ａ及び１０層プリント配線板Ａと同様の特
性が得られた。The copper foil with adhesive has a thickness of 18 μm on the adhesive surface of B.
The copper-clad laminate B was prepared by heating and pressurizing a single-sided roughened copper foil having a thickness of m over the adhesive surface with the roughened surface facing the adhesive surface at 175 ° C. and a pressure of 3 MPa for 60 minutes. With respect to the copper-clad laminate B, the copper foil was removed in the same manner as in Example 1, and the flexural modulus was measured in the same manner as the copper-clad laminate A. As a result, the average in the vertical direction and the horizontal direction was 20 GPa. Further, when the ten copper-clad laminates B were stacked and drilled with a drill having a diameter of 0.3 mm, the amount of displacement between the uppermost plate and the lowermost plate was measured and found to be 20 μm or less. A copper clad four-layer laminate D was prepared in the same manner as the copper clad four-layer laminate B of Example 1 except that the copper foil A with an adhesive was used.
Was prepared. When the surface roughness of the copper clad four-layer laminate D was measured in the same manner as in Example 1, the same results as in Example 1 were obtained. In addition, except that copper foil A with an adhesive was used, the same as copper foil clad 10-layer laminate A was used.
A layer printed wiring board B, a copper-clad 10-layer laminated board B, and further a 10-layer printed wiring board B were produced. For the copper clad ten-layer laminate B and the ten-layer printed wiring board B, the same characteristics as those of the copper clad ten-layer laminate A and the ten-layer printed wiring board A were obtained.
【００３９】実施例３ 実施例１におけるビスフェノールＡノボラック型エポキ
シ樹脂をサリチルアルデドノボラック型エポキシ樹脂
（エポキシ当量２５０、住友化学工業株式会社製、スミ
エポキシＴＭＨ５７４（商品名）を使用）に変更した。
また、電気絶縁性ウィスカーとして、平均直径０．８μ
ｍ、平均長さ３０μｍの硼酸アルミニウムウィスカー
（四国化成工業株式会社製、アルボレックス（商品名）
を使用）をボールミルで粉砕し、平均長さを１８μｍ、
最大長さ２８μｍにしたものを用いた。そして、硼酸ア
ルミニウムウィスカーを配合し、ワニス中に均一に分散
するまで撹拌し、２００メッシュのナイロンフィルタを
通過させて５０μｍ以上のサイズのウィスカーの凝集体
を分別して接着剤ワニスを調製した。Example 3 The bisphenol A novolak type epoxy resin in Example 1 was changed to a salicyl alded novolak type epoxy resin (epoxy equivalent 250, Sumiepoxy TMH574 (trade name) manufactured by Sumitomo Chemical Co., Ltd.).
In addition, as an electrically insulating whisker, an average diameter of 0.8 μm
m, aluminum borate whisker with an average length of 30 μm (Alvolex (trade name) manufactured by Shikoku Chemicals Co., Ltd.)
Is milled with a ball mill, the average length is 18 μm,
One having a maximum length of 28 μm was used. Then, aluminum borate whiskers were blended, stirred until uniformly dispersed in the varnish, passed through a 200-mesh nylon filter, and whisker aggregates having a size of 50 μm or more were separated to prepare an adhesive varnish.
【００４０】以下実施例１と同様にして接着剤シートを
作製した。得られた接着剤シートについて、実施例１と
同様にして溶融粘度を測定したところ、７２０Ｐａ・ｓ
であった。Thereafter, an adhesive sheet was produced in the same manner as in Example 1. When the melt viscosity of the obtained adhesive sheet was measured in the same manner as in Example 1, 720 Pa · s
Met.
【００４１】以下実施例１における銅はく張４層積層板
Ａの作製と同様にして銅はく張４層積層板Ｅを作製し
た。得られた銅はく張４層積層板Ｅについて銅はく張４
層積層板Ａと同様にして絶縁抵抗値の経時変化を測定し
た。その結果、１０００時間経過後においても１０9 Ω
以上であった。Hereinafter, a copper clad four-layer laminate E was prepared in the same manner as in the preparation of the copper clad four-layer laminate A in Example 1. About the obtained copper clad four-layer laminate E, copper clad 4
The time-dependent change of the insulation resistance value was measured in the same manner as in the layer laminate A. As a result, even after 1000 hours, 10 9 Ω
That was all.
【００４２】ここで作製した厚さ１００μｍの接着剤シ
ートを用いるようにしたほかは、銅張積層板Ａと同様に
して銅張積層板Ｃを作製した。この銅張積層板Ｃについ
て、実施例１と同様にして銅はくを除去して、銅張積層
板Ａと同様にして曲げ弾性率を測定した。その結果たて
方向及びよこ方向の平均で２０ＧＰａであった。また、
この銅張積層板Ｃを１０枚重ね、直径０．３ｍｍのドリ
ルにて穴あけしたときの最上板と最下板の穴位置のずれ
量を測定したところ、２０μｍ以下であった。また、こ
こで作製した厚さ５０μｍの接着剤シートを用いるよう
にしたほかは、銅はく張４層積層板Ｂと同様にして銅は
く張４層積層板Ｆを作製した。この銅はく張４層積層板
Ｆの表面粗さを実施例１と同様にして測定したところ、
実施例１と同様の結果が得られた。また、ここで作製し
た厚さ５０μｍの接着剤シートを用いるようにしたほか
は、銅はく張１０層積層板Ａと同様にして４層プリント
配線板Ｃ、銅はく張１０層積層板Ｃ、さらに１０層プリ
ント配線板Ｃを作製した。銅はく張１０層積層板Ｃ及び
１０層プリント配線板Ｃについて、ＤＭＡの曲げモード
により測定した２００℃における曲げ弾性率が２８ＧＰ
ａとなり、２００℃におおける表面硬度が５５となった
ほかは、銅はく張１０層積層板Ａ及び１０層プリント配
線板Ａと同様の特性が得られた。A copper-clad laminate C was prepared in the same manner as the copper-clad laminate A, except that the prepared adhesive sheet having a thickness of 100 μm was used. With respect to this copper-clad laminate C, the copper foil was removed in the same manner as in Example 1, and the flexural modulus was measured as in the case of the copper-clad laminate A. As a result, the average in the vertical direction and the horizontal direction was 20 GPa. Also,
When ten copper-clad laminates C were piled up and a hole with a drill having a diameter of 0.3 mm was drilled, the amount of displacement between the uppermost plate and the lowermost plate was 20 μm or less. Further, a copper clad four-layer laminate F was produced in the same manner as the copper clad four-layer laminate B, except that the adhesive sheet having a thickness of 50 μm produced here was used. When the surface roughness of the copper clad four-layer laminate F was measured in the same manner as in Example 1,
The same results as in Example 1 were obtained. A four-layer printed wiring board C and a ten-layer copper clad laminate C were used in the same manner as the copper clad ten-layer laminate A except that the adhesive sheet having a thickness of 50 μm prepared here was used. Then, a 10-layer printed wiring board C was produced. The bending elastic modulus at 200 ° C. of the copper-clad 10-layer laminated board C and the 10-layer printed wiring board C measured at a bending mode of DMA was 28 GP.
a, and the same properties as those of the copper-clad 10-layer laminate A and the 10-layer printed wiring board A were obtained except that the surface hardness at 200 ° C. was 55.
【００４３】実施例４ キャリヤーフィルムを厚さ１８μｍの銅はくに変更し、
以下、実施例３と同様にして、加熱乾燥し、銅はくを剥
がさないことにより接着剤の厚さが５０μｍの接着剤付
銅はくＣ及び１００μｍの接着剤付銅はくＤを作製し
た。そして、銅はくを剥がし、実施例１と同様にして溶
融粘度を測定したところ、７２０Ｐａ・ｓであった。Example 4 The carrier film was changed to a copper foil having a thickness of 18 μm,
Thereafter, by heating and drying in the same manner as in Example 3, a copper foil C with an adhesive having a thickness of 50 μm and a copper foil D with an adhesive having a thickness of 100 μm were produced by not peeling the copper foil. . Then, when the copper foil was peeled off and the melt viscosity was measured in the same manner as in Example 1, it was 720 Pa · s.
【００４４】接着剤付銅はくＣを用い、ガラス布基材エ
ポキシ樹脂両面銅張積層板（日立化成工業株式会社製、
ＭＣＬ−Ｅ−６７９（商品名）を使用）に回路加工を施
し、その回路加工面と接着剤付銅はくＣの接着剤面とが
向き合うようにして重ね、以下実施例１における銅はく
張４層積層板Ａの作製と同様にして銅はく張４層積層板
Ｇを作製した。そして、銅はく張４層積層板Ａと同様に
して絶縁抵抗値の経時変化を測定した。その結果、１０
００時間経過後においても１０9 Ω以上であった。Using copper foil C with an adhesive, a glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd.
MCL-E-679 (trade name)) was subjected to circuit processing, and the circuit processing surface was overlapped so that the adhesive surface of the copper foil with adhesive C faced. A copper clad four-layer laminate G was produced in the same manner as the production of the four-layer laminate A. Then, the change with time of the insulation resistance value was measured in the same manner as in the case of the copper clad four-layer laminate A. As a result, 10
Even after the lapse of 00 hours, the value was 10 9 Ω or more.
【００４５】接着剤付銅はくＤの接着剤面に厚さ１８μ
ｍの片面粗化銅はくを該粗化面が接着剤面に向き合うよ
うに重ね、温度１７５℃、圧力３ＭＰａで６０分間加熱
加圧して銅張積層板Ｄを作製した。この銅張積層板Ｄに
ついて、実施例１と同様にして銅はくを除去して、銅張
積層板Ａと同様にして曲げ弾性率を測定した。その結果
たて方向及びよこ方向の平均で２０ＧＰａであった。ま
た、この銅張積層板Ｄを１０枚重ね、直径０．３ｍｍの
ドリルにて穴あけしたときの最上板と最下板の穴位置の
ずれ量を測定したところ、２０μｍ以下であった。接着
剤付銅はくＣを用いるようにしたほかは、実施例１の銅
はく張４層積層板Ｂと同様にして銅はく張４層積層板Ｈ
を作製した。この銅はく張４層積層板Ｈの表面粗さを実
施例１と同様にして測定したところ、実施例１と同様の
結果が得られた。また、接着剤付銅はくＣを用いるよう
にしたほかは、銅はく張１０層積層板Ａと同様にして４
層プリント配線板Ｄ、銅はく張１０層積層板Ｄ、さらに
１０層プリント配線板Ｄを作製した。銅はく張１０層積
層板Ｄ及び１０層プリント配線板Ｄについて、ＤＭＡの
曲げモードにより測定した２００℃における曲げ弾性率
が２８ＧＰａとなり、２００℃における表面硬度が５５
となったほかは、銅はく張１０層積層板Ａ及び１０層プ
リント配線板Ａと同様の特性が得られた。18 μm thick copper foil D with adhesive
The copper-clad laminate D was produced by laminating a single-sided roughened copper foil having a surface roughness of m over the adhesive surface and heating and pressing at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes. With respect to the copper-clad laminate D, the copper foil was removed in the same manner as in Example 1, and the flexural modulus was measured in the same manner as the copper-clad laminate A. As a result, the average in the vertical direction and the horizontal direction was 20 GPa. Further, when ten copper-clad laminates D were stacked and a hole was drilled with a drill having a diameter of 0.3 mm, the amount of deviation between the hole positions of the uppermost plate and the lowermost plate was measured and found to be 20 μm or less. A copper clad four-layer laminate H was made in the same manner as the copper clad four-layer laminate B of Example 1 except that the copper foil C with an adhesive was used.
Was prepared. When the surface roughness of the copper clad four-layer laminate H was measured in the same manner as in Example 1, the same results as in Example 1 were obtained. Also, except that copper foil C with adhesive was used, the same procedure as for copper foil 10-layer laminate A was used.
A layer printed wiring board D, a copper-clad 10-layer laminated board D, and further a 10-layer printed wiring board D were produced. For the copper-clad 10-layer laminated board D and the 10-layer printed wiring board D, the flexural modulus at 200 ° C. measured by the bending mode of DMA was 28 GPa, and the surface hardness at 200 ° C. was 55.
Other than the above, the same characteristics as those of the copper-clad 10-layer laminate A and the 10-layer printed wiring board A were obtained.
【００４６】比較例 ビスフェノールＡノボラック型エポキシ樹脂（エポキシ
当量２１０、大日本インキ化学工業株式会社製、エピク
ロンＮ８６５（商品名）を使用）１００部ビスフェノー
ルＡノボラック樹脂（水酸基当量１１８、大日本インキ
化学工業株式会社製、プライオーフェンＶＨ−４１７０
（商品名）を使用）６０部及びジシアンジアミド２部を
メチルエチルケトン１２０部に溶解した。さらに、平均
直径０．８μｍ、平均長さ２０μｍ、最大長さ３０μｍ
の硼酸アルミニウムウィスカー（四国化成工業株式会社
製、アルボレックス（商品名）を使用）を樹脂固形分１
００部に対して９０部配合し、ワニス中に均一に分散す
るまで撹拌して接着剤ワニスを調製した。Comparative Example Bisphenol A novolak type epoxy resin (epoxy equivalent: 210, using Epicron N865 (trade name), manufactured by Dainippon Ink and Chemicals, Inc.) 100 parts Bisphenol A novolak resin (hydroxyl equivalent: 118, Dainippon Ink and Chemicals, Inc.) Manufactured by Plyofen VH-4170
(Using trade name) 60 parts and dicyandiamide 2 parts were dissolved in methyl ethyl ketone 120 parts. Furthermore, average diameter 0.8 μm, average length 20 μm, maximum length 30 μm
Of aluminum borate whisker (Alvolex (trade name) manufactured by Shikoku Chemicals Co., Ltd.)
90 parts were mixed with 00 parts, and the mixture was stirred until uniformly dispersed in the varnish to prepare an adhesive varnish.
【００４７】この接着剤ワニスを、厚さ５０μｍのポリ
エチレンテレフタレートフィルム（東レ株式会社製、ル
ミラー（商品名）を使用）をキャリヤーフィルムとして
用い、加熱乾燥後の厚さが５０μｍ及び１００μｍとな
るようにナイフコータにより塗工し、温度１５０℃で１
０分間加熱乾燥し、加熱乾燥後にキャリヤーフィルムを
剥がして接着剤シートを作製した。得られた接着剤シー
トについて、実施例１と同様にして溶融粘度を測定した
ところ、７０Ｐａ・ｓであった。The adhesive varnish was prepared by using a 50 μm-thick polyethylene terephthalate film (Lumirror (trade name) manufactured by Toray Industries, Inc.) as a carrier film so that the thickness after heating and drying was 50 μm and 100 μm. Coated with knife coater, 1 at 150 ° C
After heating and drying for 0 minutes, the carrier film was peeled off after heating and drying to prepare an adhesive sheet. When the melt viscosity of the obtained adhesive sheet was measured in the same manner as in Example 1, it was 70 Pa · s.
【００４８】以下実施例１における銅はく張４層積層板
Ａの作製と同様にして銅はく張４層積層板Ｉを作製し
た。得られた銅はく張４層積層板Ｉについて銅はく張４
層積層板Ａと同様にして絶縁抵抗値の経時変化を測定し
た。その結果、２５０時間経過後において絶縁抵抗値が
１０9 Ω以下に低下した。A copper clad four-layer laminate I was prepared in the same manner as in the preparation of the copper clad four-layer laminate A in Example 1. About the obtained copper clad four-layer laminate I, copper clad 4
The time-dependent change of the insulation resistance value was measured in the same manner as in the layer laminate A. As a result, the insulation resistance decreased to 10 9 Ω or less after 250 hours.
【００４９】ここで作製した厚さ１００μｍの接着剤シ
ートを用いるようにしたほかは、銅張積層板Ａと同様に
して銅張積層板Ｅを作製した。この銅張積層板Ｅについ
て、実施例１と同様にして銅はくを除去して、銅張積層
板Ａと同様にして曲げ弾性率を測定した。その結果たて
方向及びよこ方向の平均で２０ＧＰａであった。また、
この銅張積層板Ｅを１０枚重ね、直径０．３ｍｍのドリ
ルにて穴あけしたときの最上板と最下板の穴位置のずれ
量を測定したところ、２０μｍ以下であった。また、こ
こで作製した厚さ５０μｍの接着剤シートを用いるよう
にしたほかは、銅はく張４層積層板Ｂと同様にして銅は
く張４層積層板Ｊを作製した。この銅はく張４層積層板
Ｊの表面粗さを実施例１と同様にして測定したところ、
３μｍ以下であった。また、ここで作製した厚さ５０μ
ｍの接着剤シートを用いるようにしたほかは、銅はく張
１０層積層板Ａと同様にして４層プリント配線板Ｅ、銅
はく張１０層積層板Ｅ、さらに１０層プリント配線板Ｅ
を作製した。銅はく張１０層積層板Ｅ及び１０層プリン
ト配線板Ｅについて、ＤＭＡの曲げモードにより測定し
た常温における曲げ弾性率が６０ＧＰａとなり、２００
℃における曲げ弾性率が４０ＧＰａとなったほかは、銅
はく張１０層積層板Ａ及び１０層プリント配線板Ａと同
様の特性が得られた。A copper-clad laminate E was produced in the same manner as the copper-clad laminate A, except that the adhesive sheet having a thickness of 100 μm produced here was used. With respect to this copper-clad laminate E, the copper foil was removed in the same manner as in Example 1, and the flexural modulus was measured as in the case of the copper-clad laminate A. As a result, the average in the vertical direction and the horizontal direction was 20 GPa. Also,
When the ten copper-clad laminates E were stacked and drilled with a drill having a diameter of 0.3 mm, the amount of displacement between the uppermost plate and the lowermost plate was measured and found to be 20 μm or less. Further, a copper clad four-layer laminate J was produced in the same manner as the copper clad four-layer laminate B, except that the adhesive sheet having a thickness of 50 μm produced here was used. The surface roughness of the copper clad four-layer laminate J was measured in the same manner as in Example 1.
It was 3 μm or less. In addition, the thickness of 50μ
m, except that an adhesive sheet of m is used, in the same manner as the copper clad ten-layer laminate A, the four-layer printed wiring board E, the copper clad ten-layer laminate E, and the ten-layer printed wiring board E
Was prepared. The bending elastic modulus at room temperature of the copper-clad 10-layer laminate E and the 10-layer printed wiring board E measured by the DMA bending mode was 60 GPa,
The same properties as those of the copper clad 10-layer laminate A and the 10-layer printed wiring board A were obtained except that the flexural modulus at 40 ° C. was 40 GPa.
【００５０】[0050]
【発明の効果】本発明になる接着剤シート又は接着剤付
金属はくを使用して製造されたプリント配線板は、高温
高湿条件下においても時間経過後の絶縁性劣化が少な
く、信頼性が良好である。The printed wiring board manufactured by using the adhesive sheet or the metal foil with the adhesive according to the present invention has little insulation deterioration even after a lapse of time even under high temperature and high humidity conditions, and has a high reliability. Is good.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 神代 恭 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 (72)発明者 森田 高示 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasushi Yashiro 1500 Oji Ogawa, Shimodate City, Ibaraki Pref.Hitachi Kasei Kogyo Co., Ltd. Inside the Shimodate Research Laboratory
Claims (7)
を必須成分とする接着剤をシート状に形成してなり、溶
融粘度が１００〜１，０００Ｐａ・ｓの範囲にある接着
剤シート。1. An adhesive sheet comprising an adhesive containing a thermosetting resin and an electrically insulating whisker as essential components and having a melt viscosity in the range of 100 to 1,000 Pa · s.
３〜３．０μｍの範囲であり、平均長さが３〜２０μｍ
の範囲である請求項１に記載の接着剤シート。2. An electrically insulating whisker having an average diameter of 0.
It is in the range of 3 to 3.0 μm and the average length is 3 to 20 μm
The adhesive sheet according to claim 1, wherein
μｍである請求項２に記載の接着剤シート。3. The maximum length of the electrically insulating whisker is 50.
3. The adhesive sheet according to claim 2, which has a thickness of μm.
記載の接着剤シートが形成されてなる接着剤付き金属は
く。4. A metal foil with an adhesive, wherein the adhesive sheet according to claim 1, 2 or 3 is formed on one side of the metal foil.
トにより外層金属はくが接着されてなる金属はく張多層
積層板。5. A metal-clad multilayer laminate in which an outer metal foil is adhered by the adhesive sheet according to claim 1, 2 or 3.
トにより金属はくが接着されてなる金属はく張積層板。6. A metal-clad laminate obtained by bonding metal foils with the adhesive sheet according to claim 1, 2, or 3.
又は請求項６に記載の金属はく張積層板に回路加工を施
してなるプリント配線板。7. A printed wiring board obtained by performing circuit processing on the metal-clad multilayer laminate according to claim 5 or the metal-clad laminate according to claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10087627A JPH11279493A (en) | 1998-03-31 | 1998-03-31 | Adhesive sheet, metallic foil with adhesive, multilayer board covered with metallic foil, and layered board and printed circuit board covered with metallic foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10087627A JPH11279493A (en) | 1998-03-31 | 1998-03-31 | Adhesive sheet, metallic foil with adhesive, multilayer board covered with metallic foil, and layered board and printed circuit board covered with metallic foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11279493A true JPH11279493A (en) | 1999-10-12 |
Family
ID=13920226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10087627A Pending JPH11279493A (en) | 1998-03-31 | 1998-03-31 | Adhesive sheet, metallic foil with adhesive, multilayer board covered with metallic foil, and layered board and printed circuit board covered with metallic foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11279493A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214526A (en) * | 2011-03-28 | 2012-11-08 | Hitachi Chemical Co Ltd | Film adhesive, adhesive sheet and semiconductor apparatus |
| WO2022009937A1 (en) * | 2020-07-08 | 2022-01-13 | パナソニックＩｐマネジメント株式会社 | Resin sheet, prepreg, insulating resin material, and printed wiring board |
-
1998
- 1998-03-31 JP JP10087627A patent/JPH11279493A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214526A (en) * | 2011-03-28 | 2012-11-08 | Hitachi Chemical Co Ltd | Film adhesive, adhesive sheet and semiconductor apparatus |
| WO2022009937A1 (en) * | 2020-07-08 | 2022-01-13 | パナソニックＩｐマネジメント株式会社 | Resin sheet, prepreg, insulating resin material, and printed wiring board |
| AT525487A5 (en) * | 2020-07-08 | 2024-07-15 | Panasonic Ip Man Co Ltd | Resin layer, prepreg, insulating resin element and circuit board |
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