JP7588956B2 - Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board - Google Patents
Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board Download PDFInfo
- Publication number
- JP7588956B2 JP7588956B2 JP2020013319A JP2020013319A JP7588956B2 JP 7588956 B2 JP7588956 B2 JP 7588956B2 JP 2020013319 A JP2020013319 A JP 2020013319A JP 2020013319 A JP2020013319 A JP 2020013319A JP 7588956 B2 JP7588956 B2 JP 7588956B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- metal
- low dielectric
- dielectric film
- carrier layer
- 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.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 322
- 239000002184 metal Substances 0.000 title claims description 322
- 239000000758 substrate Substances 0.000 title claims description 129
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000010410 layer Substances 0.000 claims description 509
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 78
- 239000010949 copper Substances 0.000 claims description 65
- 229910052802 copper Inorganic materials 0.000 claims description 64
- 239000011888 foil Substances 0.000 claims description 35
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 28
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 28
- 229910045601 alloy Inorganic materials 0.000 claims description 20
- 239000000956 alloy Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 20
- 238000000992 sputter etching Methods 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 18
- -1 polyethylene fluoride Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 11
- 238000007788 roughening Methods 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- 239000011889 copper foil Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000005304 joining Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 2
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AZUHEGMJQWJCFQ-UHFFFAOYSA-N 1,1-bis(2h-benzotriazol-4-ylmethyl)urea Chemical compound C1=CC2=NNN=C2C(CN(CC=2C3=NNN=C3C=CC=2)C(=O)N)=C1 AZUHEGMJQWJCFQ-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Description
本発明は、キャリア層付き金属積層基材及びその製造方法、金属積層基材及びその製造方法、並びにプリント配線板に関する。 The present invention relates to a metal laminate substrate with a carrier layer and a manufacturing method thereof, a metal laminate substrate and a manufacturing method thereof, and a printed wiring board.
従来、微細配線（ファインピッチ）を形成するための部材としてキャリア層付き金属箔が知られている。このキャリア層付き金属箔は、剥離可能なキャリア層と極薄金属層との積層体であり、ガラスエポキシ樹脂等からなるリジッド基板と積層させてキャリア層付きの金属積層基材（金属張積層板）が得られる。また、上記リジッド基板に代えて、可撓性を有する高分子フィルムを積層させたものも知られており、フレキシブル回路基板を形成するための金属積層基材として用いられている。特に、高分子フィルムとして、低誘電率ポリイミド等の低誘電性ポリマーのフィルムを用いたものは、高周波回路用として、第５世代移動通信システム（５Ｇ）において有用である。 Conventionally, metal foil with a carrier layer has been known as a component for forming fine wiring (fine pitch). This metal foil with a carrier layer is a laminate of a peelable carrier layer and an extremely thin metal layer, and is laminated with a rigid substrate made of glass epoxy resin or the like to obtain a metal laminate substrate (metal-clad laminate) with a carrier layer. Also known is a substrate in which a flexible polymer film is laminated instead of the rigid substrate, and is used as a metal laminate substrate for forming a flexible circuit board. In particular, a substrate using a low dielectric constant polymer film such as low dielectric constant polyimide as the polymer film is useful for high frequency circuits in the fifth generation mobile communication system (5G).
（特許文献１）には、キャリアの一方の面、又は、両方の面に、中間層、極薄銅層をこの順に有するキャリア付銅箔であって、前記極薄銅層が、銅箔の表面に、銅を含む一次粒子層を形成した後、該一次粒子層の上に、銅、コバルト及びニッケルからなる３元系合金を含む二次粒子層を形成した銅箔であり、且つＪＩＳＺ８７３０に記載の色差系において粗化処理面の色差を測定した際の白色との色差Δａ＊値が４．０以下、色差Δｂ＊値が３．５以下の高周波回路用銅箔であるようなキャリア付銅箔が開示されている。また、（特許文献１）には、紙基材フェノール樹脂等のリジッド基板や、液晶ポリマー（ＬＣＰ）等の高分子フィルムを、上記キャリア付銅箔と積層させたキャリア付銅張積層板も記載されている。 (Patent Document 1) discloses a carrier-attached copper foil having an intermediate layer and an ultra-thin copper layer in this order on one or both sides of the carrier, the ultra-thin copper layer being a copper foil in which a primary particle layer containing copper is formed on the surface of the copper foil, and a secondary particle layer containing a ternary alloy of copper, cobalt, and nickel is formed on the primary particle layer, and the carrier-attached copper foil is a copper foil for high-frequency circuits in which the color difference Δa* value from white when the color difference of the roughened surface is measured using the color difference system described in JIS Z8730 is 4.0 or less, and the color difference Δb* value is 3.5 or less. (Patent Document 1) also discloses a carrier-attached copper-clad laminate in which a rigid substrate such as a paper-based phenolic resin or a polymer film such as a liquid crystal polymer (LCP) is laminated with the carrier-attached copper foil.
上記（特許文献１）では、キャリア付銅箔とリジッド基板とを貼り合わせる際に、ガラス布等の基材に樹脂を含浸させ、樹脂を半硬化状態まで硬化させたプリプレグを用意し、銅箔をプリプレグに重ねて加熱加圧させることにより行っている。また、リジッド基板に代えて高分子フィルムを用いる場合も、液晶ポリマー等の基材に対して、高温高圧下で銅箔を積層接着（熱圧着）することにより貼り合わせている。 In the above (Patent Document 1), when bonding the carrier-attached copper foil to the rigid substrate, a prepreg is prepared by impregnating a substrate such as glass cloth with resin and curing the resin until it is in a semi-cured state, and the copper foil is then placed on the prepreg and heated and pressurized. Also, when a polymer film is used instead of a rigid substrate, the copper foil is laminated and bonded (thermocompression bonded) to the substrate such as a liquid crystal polymer under high temperature and high pressure.
しかしながら、特に、高周波回路用途に適した液晶ポリマーやポリフッ化エチレン、低誘電率ポリイミド等の低誘電性フィルムに対してキャリア付金属箔を熱圧着する場合、低誘電性フィルムの融点等の諸特性を考慮すると熱圧着の温度を２８０℃以上、あるいは３００℃以上にする必要があり、このような温度範囲では、キャリア層と極薄金属層との間の剥離層が変質してしまい、キャリアの剥離性が損なわれるという問題があった。一方、剥離性を維持するため熱圧着の温度を低くすると、極薄金属層と低誘電性フィルムとの密着性が低下するという問題があった。したがって、キャリアと極薄金属層との剥離性（低密着性）の維持と、極薄金属層と低誘電性フィルムとの高い密着性の確保とを両立することは従来困難であった。 However, when a carrier-attached metal foil is thermocompressed onto a low dielectric film such as a liquid crystal polymer, polyethylene fluoride, or low dielectric constant polyimide, which is particularly suitable for high frequency circuit applications, the thermocompression temperature must be 280°C or higher, or 300°C or higher, taking into consideration the melting point and other characteristics of the low dielectric film. At such a temperature range, the peel layer between the carrier layer and the ultra-thin metal layer is altered, resulting in a problem of impaired peelability of the carrier. On the other hand, if the thermocompression temperature is lowered to maintain peelability, there is a problem of reduced adhesion between the ultra-thin metal layer and the low dielectric film. Therefore, it has been difficult to maintain the peelability (low adhesion) between the carrier and the ultra-thin metal layer while ensuring high adhesion between the ultra-thin metal layer and the low dielectric film at the same time.
そこで本発明は、キャリア層と極薄金属層との間の低密着性を維持しつつ、極薄金属層と低誘電性フィルムとの高い密着性が確保されたキャリア層付き金属積層基材及びその製造方法を提供することを目的とする。また、低誘電性フィルムと極薄金属層とが積層された金属積層基材及びその製造方法を提供することを目的とする。さらに、上記の金属積層基材から得られ、高周波回路用として好適に用いられるプリント配線板を提供することを目的とする。 The present invention therefore aims to provide a metal laminated substrate with a carrier layer that maintains low adhesion between the carrier layer and the ultra-thin metal layer while ensuring high adhesion between the ultra-thin metal layer and a low dielectric film, and a method for manufacturing the same. It also aims to provide a metal laminated substrate in which a low dielectric film and an ultra-thin metal layer are laminated, and a method for manufacturing the same. It also aims to provide a printed wiring board obtained from the above metal laminated substrate, which is suitable for use in high-frequency circuits.
本発明者らが鋭意検討を行った結果、低誘電性フィルムと、キャリア層、剥離層及び極薄金属層を含むキャリア層付き金属箔とを積層させる際に、特定の接合方法を採用し、極薄金属層と低誘電性フィルムの接合強度、並びにキャリア層と極薄金属層の剥離強度をそれぞれ制御することによって上記課題が解決できることを見い出し、発明を完成した。すなわち、本発明の要旨は次のとおりである。 As a result of intensive research, the inventors discovered that the above problems can be solved by adopting a specific bonding method when laminating a low dielectric film and a metal foil with a carrier layer, which includes a carrier layer, a peel layer, and an extremely thin metal layer, and by controlling the bonding strength between the extremely thin metal layer and the low dielectric film, and the peel strength between the carrier layer and the extremely thin metal layer, respectively, and thus completed the invention. In other words, the gist of the present invention is as follows.
（１）低誘電性フィルムの少なくとも一方の面に、キャリア層、剥離層及び極薄金属層を含む少なくとも３層以上からなるキャリア層付き金属箔が積層されたキャリア層付き金属積層基材であって、
前記極薄金属層と前記低誘電性フィルムの接合強度が、前記キャリア層と前記極薄金属層の剥離強度よりも大きい前記キャリア層付き金属積層基材。
（２）低誘電性フィルムと極薄金属層との間に、金属を含む中間層を１層以上有する上記（１）に記載のキャリア層付き金属積層基材。
（３）中間層が、銅、鉄、ニッケル、亜鉛、クロム、コバルト、チタン、スズ、白金、銀及び金からなる群より選択されるいずれか一種の金属又はその合金を含む上記（２）に記載の金属積層基材。
（４）低誘電性フィルムが、液晶ポリマー、ポリフッ化エチレン、ポリアミド及び低誘電率ポリイミドからなる群より選択される低誘電性ポリマーのフィルムである上記（１）～（３）のいずれか一つに記載のキャリア層付き金属積層基材。
（５）キャリア層と極薄金属層の剥離強度が、０．１５Ｎ／ｃｍ以上０．５Ｎ／ｃｍ以下である上記（１）～（４）のいずれか一つに記載のキャリア層付き金属積層基材。
（６）極薄金属層と低誘電性フィルムの接合強度が、２．０Ｎ／ｃｍ以上である上記（１）～（５）のいずれか一つに記載のキャリア層付き金属積層基材。
（７）剥離層が、有機系剥離層又は無機系剥離層である上記（１）～（６）のいずれか一つに記載のキャリア層付き金属積層基材。
（８）極薄金属層の厚みが、０．５μｍ以上１０μｍ以下である上記（１）～（７）のいずれか一つに記載のキャリア層付き金属積層基材。
（９）上記（２）に記載のキャリア層付き金属積層基材の製造方法であって、
低誘電性フィルムと、キャリア層、剥離層及び極薄金属層を含む少なくとも３層以上からなるキャリア層付き金属箔とを準備する工程と、
前記低誘電性フィルムの少なくとも一方の面をスパッタエッチングにより活性化した後、前記面上に金属を含む中間層をスパッタ成膜する工程と、
前記中間層の表面をスパッタエッチングにより活性化する工程と、
前記極薄金属層の表面をスパッタエッチングにより活性化する工程と、
前記活性化した表面同士を０～３０％の圧下率で圧延接合する工程と、
を含む前記キャリア層付き金属積層基材の製造方法。
（１０）低誘電性フィルムが、液晶ポリマー、ポリフッ化エチレン、ポリアミド及び低誘電率ポリイミドからなる群より選択される低誘電性ポリマーのフィルムである上記（９）に記載のキャリア層付き金属積層基材の製造方法。
（１１）圧延接合を行った後、１６０℃以上３００℃以下での熱処理を行う上記（９）又は（１０）に記載のキャリア層付き金属積層基材の製造方法。
（１２）低誘電性フィルムの少なくとも一方の面に、金属を含む中間層を介して極薄金属層が積層され、前記低誘電率フィルムと前記極薄金属層の接合強度が２．０Ｎ／ｃｍ以上である金属積層基材。
（１３）中間層が、銅、鉄、ニッケル、亜鉛、クロム、コバルト、チタン、スズ、白金、銀及び金からなる群より選択されるいずれか一種の金属又はその合金を含む上記（１２）に記載の金属積層基材。
（１４）極薄金属層の中間層側の表面に、Ｃｕ、Ｃｏ及びＮｉからなる群より選択されるいずれか一種の金属又はその合金を含む粗化粒子層、及び／又はＣｒ、Ｎｉ及びＺｎからなる群より選択されるいずれか一種の金属又はその合金を含む防錆層が積層された上記（１２）又は（１３）に記載の金属積層基材。
（１５）極薄金属層の厚みが、０．５μｍ以上１０μｍ以下である上記（１２）～（１４）のいずれか一つに記載の金属積層基材。
（１６）低誘電性フィルムの少なくとも一方の面に、金属を含む中間層を介して極薄金属層が積層された金属積層基材の製造方法であって、
上記（２）に記載のキャリア層付き金属積層基材における前記キャリア層を剥離する工程を含む前記金属積層基材の製造方法。
（１７）上記（１２）～（１５）のいずれか一つに記載の金属積層基材における中間層及び極薄金属層に、回路が形成されてなるプリント配線板。
(1) A metal laminated substrate with a carrier layer, in which a metal foil with a carrier layer, which comprises at least three layers including a carrier layer, a release layer, and an extremely thin metal layer, is laminated on at least one surface of a low dielectric film,
The metal laminate substrate with a carrier layer, wherein the bonding strength between the extremely thin metal layer and the low dielectric film is greater than the peel strength between the carrier layer and the extremely thin metal layer.
(2) The metal laminated substrate with a carrier layer according to the above (1), which has one or more intermediate layers containing a metal between the low dielectric film and the extremely thin metal layer.
(3) The metal laminate substrate according to (2) above, wherein the intermediate layer contains any one metal selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold, or an alloy thereof.
(4) The metal laminate substrate with a carrier layer according to any one of (1) to (3) above, wherein the low dielectric film is a film of a low dielectric polymer selected from the group consisting of liquid crystal polymers, polyethylene fluoride, polyamides, and low dielectric constant polyimides.
(5) The metal laminate substrate with a carrier layer according to any one of (1) to (4) above, wherein the peel strength between the carrier layer and the ultrathin metal layer is 0.15 N/cm or more and 0.5 N/cm or less.
(6) The metal laminated substrate with a carrier layer according to any one of (1) to (5) above, wherein the bonding strength between the ultrathin metal layer and the low dielectric film is 2.0 N/cm or more.
(7) The metal laminate substrate with a carrier layer according to any one of (1) to (6) above, wherein the release layer is an organic release layer or an inorganic release layer.
(8) The metal laminate substrate with a carrier layer according to any one of (1) to (7) above, wherein the thickness of the ultrathin metal layer is 0.5 μm or more and 10 μm or less.
(9) A method for producing a metal laminate substrate with a carrier layer according to the above (2), comprising the steps of:
A step of preparing a low dielectric film and a metal foil with a carrier layer, the metal foil having at least three layers including a carrier layer, a release layer, and an extremely thin metal layer;
a step of activating at least one surface of the low dielectric film by sputter etching, and then sputter-forming an intermediate layer containing a metal on the surface;
activating the surface of the intermediate layer by sputter etching;
activating the surface of the ultrathin metal layer by sputter etching;
Roll-bonding the activated surfaces together at a rolling reduction of 0 to 30%;
A method for producing the metal laminate substrate with a carrier layer comprising the steps of:
(10) The method for producing a metal laminated substrate with a carrier layer according to the above (9), wherein the low dielectric film is a film of a low dielectric polymer selected from the group consisting of liquid crystal polymers, polyethylene fluoride, polyamides and low dielectric constant polyimides.
(11) The method for producing a metal laminated substrate with a carrier layer according to the above (9) or (10), further comprising, after the roll-bonding, performing a heat treatment at 160° C. or more and 300° C. or less.
(12) A metal laminated substrate in which an extremely thin metal layer is laminated on at least one surface of a low dielectric film via an intermediate layer containing a metal, and the bonding strength between the low dielectric constant film and the extremely thin metal layer is 2.0 N/cm or more.
(13) The metal laminate substrate according to (12) above, wherein the intermediate layer contains any one metal selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold, or an alloy thereof.
(14) A metal laminated substrate according to (12) or (13) above, in which a roughening particle layer containing any one metal or alloy selected from the group consisting of Cu, Co, and Ni, and/or a rust-preventive layer containing any one metal or alloy selected from the group consisting of Cr, Ni, and Zn, is laminated on the surface of the intermediate layer side of the ultrathin metal layer.
(15) The metal laminated substrate according to any one of (12) to (14) above, wherein the thickness of the ultrathin metal layer is 0.5 μm or more and 10 μm or less.
(16) A method for producing a metal laminated substrate in which an extremely thin metal layer is laminated on at least one surface of a low dielectric film via an intermediate layer containing a metal, comprising:
A method for producing a metal laminated substrate, comprising the step of peeling off the carrier layer in the metal laminated substrate with a carrier layer described in (2) above.
(17) A printed wiring board comprising a circuit formed in the intermediate layer and the ultrathin metal layer of the metal laminated substrate according to any one of (12) to (15) above.
本発明によれば、キャリア層付き金属積層基材において、キャリア層及び極薄金属層の間の低密着性の維持と、極薄金属層及び低誘電性フィルムの間の高い密着性の確保との両立が可能となる。また、低誘電性フィルムと極薄金属層とが積層された金属積層基材を得ることができる。この金属積層基材は、高周波回路用として好適に用いられる。 According to the present invention, in a metal laminate substrate with a carrier layer, it is possible to maintain low adhesion between the carrier layer and the ultra-thin metal layer while ensuring high adhesion between the ultra-thin metal layer and the low dielectric film. It is also possible to obtain a metal laminate substrate in which a low dielectric film and an ultra-thin metal layer are laminated. This metal laminate substrate is suitable for use in high-frequency circuits.
以下、本発明を詳細に説明する。
図１に、本発明の第１実施形態に係るキャリア層付き金属積層基材の断面を示す。図１に示すキャリア層付き金属積層基材１Ａは、キャリア層１１、剥離層１２及び極薄金属層１３から構成されるキャリア層付き金属箔１０と、低誘電性フィルム２０とがこの順で積層して概略構成される。
The present invention will be described in detail below.
A cross section of a carrier layer-attached metal laminated substrate according to a first embodiment of the present invention is shown in Fig. 1. The carrier layer-attached metal laminated substrate 1A shown in Fig. 1 is roughly composed of a carrier layer-attached metal foil 10 composed of a carrier layer 11, a release layer 12, and an extremely thin metal layer 13, and a low dielectric film 20 laminated in this order.
なお、図１には記載していないが、極薄金属層１３の低誘電性フィルム２０側の表面には、粗化粒子層や防錆層、シランカップリング剤による処理層等が積層されていても良い。これらの層は、いずれか一種の層が積層されていても良いし、複数種の層が積層されていても良い。粗化粒子層は、例えば、Ｃｕ、Ｃｏ及びＮｉからなる群より選択されるいずれか一種の金属又はその合金を含むことができる。具体的には、コバルト－ニッケル合金めっき層、銅－コバルト－ニッケル合金めっき層等が挙げられる。また、防錆層は、例えば、Ｃｒ、Ｎｉ及びＺｎからなる群より選択されるいずれか一種の金属又はその合金を含むことができる。具体的には、クロム酸化物の皮膜処理、クロム酸化物と亜鉛／亜鉛酸化物との混合物皮膜処理、Ｎｉめっき層等を挙げることができる。さらに、シランカップリング剤としては、オレフィン系シラン、エポキシ系シラン、アクリル系シラン、アミノ系シラン、メルカプト系シランを挙げることができるが、これらに限定されるものではない。シランカップリング剤の塗布は、スプレーによる吹付け、コーターによる塗布、浸漬等の方法を適宜用いて行うことができる。 Although not shown in FIG. 1, the surface of the ultrathin metal layer 13 on the low dielectric film 20 side may be laminated with a roughened particle layer, an anti-rust layer, a layer treated with a silane coupling agent, etc. These layers may be laminated with any one of the layers, or with a plurality of layers. The roughened particle layer may contain, for example, any one of metals selected from the group consisting of Cu, Co, and Ni, or an alloy thereof. Specific examples include a cobalt-nickel alloy plating layer, a copper-cobalt-nickel alloy plating layer, etc. The anti-rust layer may contain, for example, any one of metals selected from the group consisting of Cr, Ni, and Zn, or an alloy thereof. Specific examples include a chromium oxide coating, a mixture coating of chromium oxide and zinc/zinc oxide, and a Ni plating layer. Furthermore, examples of the silane coupling agent include, but are not limited to, olefin-based silanes, epoxy-based silanes, acrylic-based silanes, amino-based silanes, and mercapto-based silanes. The silane coupling agent can be applied by any suitable method, such as spraying, applying with a coater, or immersion.
キャリア層１１は、シート形状を有するものであり、キャリア層付き金属積層基材１Ａへの皺や折れの発生、極薄金属層１３への傷を防止するための支持材料あるいは保護層として機能する。キャリア層１１としては、銅、アルミニウム、ニッケル、及びその合金類（ステンレス、真鍮等）、表面に金属をコーティングした樹脂等からなる箔もしくは板状のものが挙げられる。好ましくは、銅箔である。 The carrier layer 11 has a sheet shape and functions as a support material or protective layer to prevent wrinkles or folds in the metal laminate substrate 1A with the carrier layer, and to prevent scratches on the ultra-thin metal layer 13. Examples of the carrier layer 11 include foils or plates made of copper, aluminum, nickel, and alloys thereof (stainless steel, brass, etc.), resins with metal coatings on the surface, etc. Copper foil is preferred.
キャリア層１１の厚みは、特に限定されるものではなく、可撓性等の所望の特性に応じて適宜設定される。具体的には、１０μｍ以上１００μｍ以下程度とすることが好ましい。厚みが薄過ぎると、キャリア層付き金属箔１０の取り扱い性が損なわれる可能性があるため好ましくない。すなわち、取り扱い時に変形して、極薄金属層１３に皺や割れが生じる場合がある。また、キャリア層１１が厚過ぎると、支持材料として過剰な剛性を有し、極薄金属層１３と剥離し難くなる可能性があるため好ましくない。さらに、キャリア層付き金属箔１０を生産するコストも上昇してしまう。 The thickness of the carrier layer 11 is not particularly limited, and is appropriately set according to the desired characteristics such as flexibility. Specifically, it is preferably about 10 μm or more and 100 μm or less. If the thickness is too thin, the handleability of the metal foil 10 with the carrier layer may be impaired, which is not preferable. In other words, the carrier layer 11 may deform during handling, causing wrinkles or cracks in the ultra-thin metal layer 13. In addition, if the carrier layer 11 is too thick, it is not preferable because it has excessive rigidity as a support material and may be difficult to peel off from the ultra-thin metal layer 13. Furthermore, the cost of producing the metal foil 10 with the carrier layer also increases.
剥離層１２は、キャリア層１１の剥離強度を小さくし、さらに、キャリア層付き金属箔１０を低誘電性フィルム２０と接合するに際して加熱する場合には、キャリア層１１と極薄金属層１３の間で起こり得る相互拡散を抑制する機能をも有する。剥離層１２は、有機系剥離層及び無機系剥離層のいずれであっても良く、有機系剥離層に用いられる成分としては、例えば、窒素含有有機化合物、硫黄含有有機化合物、カルボン酸等が挙げられる。窒素含有有機化合物としては、トリアゾール化合物、イミダゾール化合物等が挙げられる。トリアゾール化合物の例としては、１，２，３－ベンゾトリアゾール、カルボキシベンゾトリアゾール、Ｎ’，Ｎ’－ビス（ベンゾトリアゾリルメチル）ユリア、１Ｈ－１，２，４－トリアゾール及び３－アミノ－１Ｈ－１，２，４－トリアゾール等が挙げられる。硫黄含有有機化合物の例としては、メルカプトベンゾチアゾール、チオシアヌル酸、２－ベンズイミダゾールチオール等が挙げられる。カルボン酸の例としては、モノカルボン酸、ジカルボン酸等が挙げられる。また、無機系剥離層に用いられる成分としては、例えば、Ｎｉ、Ｍｏ、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ｗ、Ｐ、Ｚｎ、クロメート処理膜等が挙げられる。なお、剥離層１２の形成は、キャリア層１１の表面に、剥離層１２の成分含有溶液を接触させ、剥離層成分をキャリア層１１の表面に固定すること等により行うことができる。キャリア層１１を剥離層１２の成分含有溶液に接触させる場合、この接触は、剥離層成分含有溶液への浸漬、剥離層成分含有溶液の噴霧、剥離層成分含有溶液の流下等により行えば良く、その後に乾燥等を行って固定することができる。その他、蒸着やスパッタリング等による気相法で剥離層１２の成分を被膜形成する方法も採用することができる。 The release layer 12 reduces the peel strength of the carrier layer 11, and also has the function of suppressing mutual diffusion that may occur between the carrier layer 11 and the ultrathin metal layer 13 when the carrier layer-attached metal foil 10 is heated when bonding to the low dielectric film 20. The release layer 12 may be either an organic release layer or an inorganic release layer, and examples of components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Examples of nitrogen-containing organic compounds include triazole compounds and imidazole compounds. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole, and 3-amino-1H-1,2,4-triazole. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, and 2-benzimidazolethiol. Examples of carboxylic acids include monocarboxylic acids and dicarboxylic acids. Examples of components used in the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and chromate-treated films. The release layer 12 can be formed by contacting the surface of the carrier layer 11 with a solution containing the components of the release layer 12 and fixing the release layer components to the surface of the carrier layer 11. When contacting the carrier layer 11 with the solution containing the components of the release layer 12, this contact can be performed by immersion in the solution containing the release layer components, spraying the solution containing the release layer components, or allowing the solution containing the release layer components to flow down, and then drying or the like can be performed to fix the components. In addition, a method of forming a film of the components of the release layer 12 by a gas phase method such as deposition or sputtering can also be used.
剥離層１２の厚みは、典型的には１ｎｍ以上１μｍ以下であり、好ましくは５ｎｍ以上５００ｎｍ以下であるがこれに限定されるものではない。剥離層１２の厚みが薄過ぎると、極薄金属層１３との分離が十分に行えず剥離不良になるという問題がある。また、厚みが大き過ぎると、剥離は可能であるが、製造コストが高くなるためこれらのバランスを考慮して適宜設定される。 The thickness of the peeling layer 12 is typically 1 nm to 1 μm, and preferably 5 nm to 500 nm, but is not limited to this. If the thickness of the peeling layer 12 is too thin, there is a problem that it cannot be sufficiently separated from the ultra-thin metal layer 13, resulting in poor peeling. Also, if the thickness is too large, peeling is possible, but the manufacturing costs will be high, so the thickness is set appropriately while taking these factors into consideration.
極薄金属層１３を構成する金属は、キャリア層付き金属積層基材１Ａの用途や目的とする特性に応じて適宜選択することができる。具体的には、銅、鉄、ニッケル、亜鉛、スズ、クロム、金、銀、白金、コバルト、チタン及びこれらのいずれかを基とする合金等が挙げられる。特に、銅又は銅合金の層であることが好ましい。これらの金属を低誘電性フィルム２０と圧延接合することで、例えば微細配線形成用のフレキシブル基板を得ることができる。 The metal constituting the ultra-thin metal layer 13 can be appropriately selected depending on the application and desired characteristics of the metal laminated substrate 1A with a carrier layer. Specific examples include copper, iron, nickel, zinc, tin, chromium, gold, silver, platinum, cobalt, titanium, and alloys based on any of these. In particular, a layer of copper or a copper alloy is preferable. By rolling-bonding these metals to the low dielectric film 20, a flexible substrate for forming fine wiring, for example, can be obtained.
極薄金属層１３の厚みは、０．５μｍ以上１０μｍ以下である。好ましくは、１μｍ以上７μｍ以下である。ここで、極薄金属層１３の厚みは、キャリア層付き金属積層基材１Ａの断面の光学顕微鏡写真を取得し、その光学顕微鏡写真において任意の１０点における極薄金属層１３の厚みを計測し、得られた値の平均値をいう。 The thickness of the ultra-thin metal layer 13 is 0.5 μm or more and 10 μm or less. Preferably, it is 1 μm or more and 7 μm or less. Here, the thickness of the ultra-thin metal layer 13 refers to the average value of the values obtained by taking an optical microscope photograph of the cross section of the metal laminate substrate 1A with a carrier layer, measuring the thickness of the ultra-thin metal layer 13 at any 10 points on the optical microscope photograph.
このような極薄金属層１３の製造方法は特に限定されないが、無電解めっき法、電解めっき法等の湿式成膜法、スパッタリング及び化学蒸着等の乾式成膜法、又はそれらの組み合わせにより剥離層１２上に形成することができる。 The method for producing such an ultra-thin metal layer 13 is not particularly limited, but it can be formed on the release layer 12 by wet film formation methods such as electroless plating and electrolytic plating, dry film formation methods such as sputtering and chemical vapor deposition, or a combination of these.
本実施形態において、極薄金属層１３と低誘電性フィルム２０の接合強度と、キャリア層１１と極薄金属層１３の剥離強度とを比較した場合、極薄金属層１３と低誘電性フィルム２０の接合強度の方が大きい。これにより、キャリア層１１を極薄金属層１３から剥離する際に、極薄金属層１３に皺や破れ等を生ずることなく剥離することができる。しかし、極薄金属層１３及び低誘電性フィルム２０の接合強度の値と、キャリア層１１と極薄金属層１３の剥離強度の値とが近過ぎると、実際上、極薄金属層１３と低誘電性フィルム２０との界面に影響を及ぼさずにキャリア層１１を剥離することが困難になる場合があるため、極薄金属層１３及び低誘電性フィルム２０の接合強度と、キャリア層１１と極薄金属層１３の剥離強度との差が、０．２５Ｎ／ｃｍ以上あることが好ましい。より好ましくは０．５Ｎ／ｃｍ以上、最も好ましくは１．５Ｎ／ｃｍ以上である。極薄金属層１３及び低誘電性フィルム２０の接合強度、及びキャリア層１１と極薄金属層１３の剥離強度の具体的な値としては、極薄金属層１３と低誘電性フィルム２０の接合強度が、２．０Ｎ／ｃｍ以上であることが好ましい。また、キャリア層１１と極薄金属層１３の剥離強度は、０より大きければ良く、０．５Ｎ／ｃｍ以下であることが好ましいが、約０．０５Ｎ／ｃｍを下回る領域では、引き剥がす材料（キャリア層１１、極薄金属層１３、低誘電性フィルム２０、その他防錆層等）自体の剛性の影響により、正確な剥離強度を測れない場合がある。キャリア層１１と極薄金属層１３の剥離強度は、好ましくは０．１５Ｎ／ｃｍ以上０．５Ｎ／ｃｍ以下の範囲である。なお、上記接合強度の値を測定するには、まずキャリア層付き金属積層基材１Ａから幅１ｃｍの試験片を作製する。その後、キャリア層１１を除去した後に極薄金属層１３表面に電解めっき（極薄金属層１３が銅である場合、例えば銅めっき）を施し、低誘電性フィルム２０表面に約１０～２０μｍ厚みの金属層（極薄金属層１３を含む）を形成する。そして、前記約１０～２０μｍ厚みの金属層と低誘電性フィルム２０を一部剥離後、低誘電性フィルム２０を支持体へ固定し、前記約１０～２０μｍ厚みの金属層を、低誘電性フィルム２０に対して９０°方向へ引っ張る。その際の引き剥がすのに要する力をもって接合強度とする（単位：Ｎ／ｃｍ）。また、上記剥離強度を測定するには、まずキャリア層付き金属積層基材１Ａから幅１ｃｍの試験片を作製する。キャリア層１１を一部剥離後、極薄金属層１３を含む低誘電性フィルム２０を支持体に固定し、キャリア層１１を極薄金属層１３を含む低誘電性フィルム２０に対して９０°方向へ引っ張る。その際の引き剥がすのに要する力をもって剥離強度とする（単位：Ｎ／ｃｍ）。 In this embodiment, when comparing the bonding strength between the ultra-thin metal layer 13 and the low dielectric film 20 and the peel strength between the carrier layer 11 and the ultra-thin metal layer 13, the bonding strength between the ultra-thin metal layer 13 and the low dielectric film 20 is greater. As a result, when the carrier layer 11 is peeled off from the ultra-thin metal layer 13, the ultra-thin metal layer 13 can be peeled off without wrinkles or tears. However, if the bonding strength value between the ultra-thin metal layer 13 and the low dielectric film 20 and the peel strength value between the carrier layer 11 and the ultra-thin metal layer 13 are too close, it may be difficult to peel off the carrier layer 11 without affecting the interface between the ultra-thin metal layer 13 and the low dielectric film 20, so it is preferable that the difference between the bonding strength between the ultra-thin metal layer 13 and the low dielectric film 20 and the peel strength between the carrier layer 11 and the ultra-thin metal layer 13 is 0.25 N/cm or more. More preferably, it is 0.5 N/cm or more, and most preferably, it is 1.5 N/cm or more. As specific values of the bonding strength between the ultrathin metal layer 13 and the low dielectric film 20, and the peel strength between the carrier layer 11 and the ultrathin metal layer 13, the bonding strength between the ultrathin metal layer 13 and the low dielectric film 20 is preferably 2.0 N/cm or more. In addition, the peel strength between the carrier layer 11 and the ultrathin metal layer 13 may be greater than 0, and is preferably 0.5 N/cm or less, but in the region below about 0.05 N/cm, the peel strength may not be accurately measured due to the influence of the rigidity of the material to be peeled off (the carrier layer 11, the ultrathin metal layer 13, the low dielectric film 20, other anti-rust layers, etc.). The peel strength between the carrier layer 11 and the ultrathin metal layer 13 is preferably in the range of 0.15 N/cm or more and 0.5 N/cm or less. In order to measure the value of the above bonding strength, first prepare a test piece having a width of 1 cm from the metal laminated base material 1A with the carrier layer. Thereafter, after removing the carrier layer 11, electrolytic plating (for example, copper plating when the very thin metal layer 13 is copper) is applied to the surface of the very thin metal layer 13, and a metal layer (including the very thin metal layer 13) having a thickness of about 10 to 20 μm is formed on the surface of the low dielectric film 20. Then, after the metal layer having a thickness of about 10 to 20 μm and the low dielectric film 20 are partially peeled off, the low dielectric film 20 is fixed to a support, and the metal layer having a thickness of about 10 to 20 μm is pulled in a 90° direction relative to the low dielectric film 20. The force required for peeling off at that time is taken as the bonding strength (unit: N/cm). In addition, to measure the peel strength, a test piece having a width of 1 cm is first prepared from the metal laminated base material 1A with a carrier layer. After partially peeling off the carrier layer 11, the low dielectric film 20 including the very thin metal layer 13 is fixed to a support, and the carrier layer 11 is pulled in a 90° direction relative to the low dielectric film 20 including the very thin metal layer 13. The force required to peel it off at that time is the peel strength (unit: N/cm).
本明細書において、「極薄金属層と低誘電性フィルムの接合強度」というときは、極薄金属層と低誘電性フィルムとの界面で剥離する場合の接合強度をいう他、極薄金属層の内部が破壊されることにより剥離する場合の接合強度、及び低誘電性フィルムの内部が破壊されることにより剥離する場合の接合強度をも意味し、さらに、上述のように極薄金属層における低誘電性フィルム側の表面に粗化粒子層や防錆層、シランカップリング剤による処理層等（総称して「処理層」という）が積層しているときは、極薄金属層と処理層との界面で剥離する場合の接合強度、処理層と低誘電性フィルムとの界面で剥離する場合の接合強度、及び、処理層の内部が破壊されることにより剥離する場合の接合強度をも意味する。また、後述の第２実施形態に係るキャリア層付き金属積層基材（図２）のように、低誘電性フィルム２０と極薄金属層１３との間に、金属を含む中間層３０を有する場合は、「極薄金属層と低誘電性フィルムの接合強度」は、極薄金属層の内部が破壊されることにより剥離する場合の接合強度、極薄金属層（処理層が存在する場合は処理層）と中間層との界面で剥離する場合の接合強度、中間層と低誘電性フィルムとの界面で剥離する場合の接合強度、中間層の内部が破壊されることにより剥離する場合の接合強度、及び低誘電性フィルムの内部が破壊されることにより剥離する場合の接合強度のいずれをも意味する。 In this specification, the term "bonding strength between an ultra-thin metal layer and a low dielectric film" refers not only to the bond strength when peeling occurs at the interface between the ultra-thin metal layer and the low dielectric film, but also to the bond strength when peeling occurs due to internal destruction of the ultra-thin metal layer, and the bond strength when peeling occurs due to internal destruction of the low dielectric film. Furthermore, when a roughening particle layer, anti-rust layer, or treatment layer using a silane coupling agent (collectively referred to as a "treatment layer") is laminated on the surface of the ultra-thin metal layer facing the low dielectric film as described above, it also refers to the bond strength when peeling occurs at the interface between the ultra-thin metal layer and the treatment layer, the bond strength when peeling occurs at the interface between the treatment layer and the low dielectric film, and the bond strength when peeling occurs due to internal destruction of the treatment layer. In addition, in the case of a metal laminated substrate with a carrier layer according to the second embodiment (FIG. 2) described later, in the case of a low dielectric film 20 and an extremely thin metal layer 13, which has an intermediate layer 30 containing metal between them, the "bonding strength between the extremely thin metal layer and the low dielectric film" refers to any of the following: bonding strength when peeling occurs due to internal destruction of the extremely thin metal layer, bonding strength when peeling occurs at the interface between the extremely thin metal layer (or the treatment layer, if present) and the intermediate layer, bonding strength when peeling occurs at the interface between the intermediate layer and the low dielectric film, bonding strength when peeling occurs due to internal destruction of the intermediate layer, and bonding strength when peeling occurs due to internal destruction of the low dielectric film.
低誘電性フィルム２０は、極薄金属層１３に積層されている。低誘電性フィルム２０の材質としては、フレキシブル基板として用い得る低誘電性のポリマー材料であれば適用可能であり、例えば、比誘電率εｒが３．３以下、誘電正接ｔａｎδの値が０．００６以下であるような材料であるが、これに限定されなくても良い。具体的には、液晶ポリマー、ポリフッ化エチレン（ポリテトラフルオロエチレン等のフッ素系樹脂）、ポリアミド、イソシアネート化合物、ポリアミドイミド、ポリイミド、低誘電率ポリイミド、ポリエチレンテレフタレート、ポリエーテルイミド等の材料から適宜選択して用いることができる。好ましくは、液晶ポリマー、ポリフッ化エチレン、ポリアミド又は低誘電率ポリイミドである。低誘電性フィルム２０は、単層のフィルムであるか、又は複数層からなる積層体であり、複数層である場合は、その複数層のうちのいずれか一層以上が上記の低誘電性のポリマー材料からなる層であれば良い。低誘電性のポリマー材料からなる層以外の層は、エポキシ樹脂等の従来知られた種々の材料から構成することができる。なお、液晶ポリマーとは、溶融状態で液晶の性質を示すような、パラヒドロキシ安息香酸等を基本構造とする芳香族ポリエステル系樹脂をいう。 The low dielectric film 20 is laminated on the very thin metal layer 13. The low dielectric film 20 may be made of any low dielectric polymer material that can be used as a flexible substrate, such as a material with a relative dielectric constant εr of 3.3 or less and a dielectric loss tangent tanδ of 0.006 or less, but is not limited thereto. Specifically, the low dielectric film 20 may be appropriately selected from materials such as liquid crystal polymer, polyethylene fluoride (fluorine resin such as polytetrafluoroethylene), polyamide, isocyanate compound, polyamideimide, polyimide, low dielectric constant polyimide, polyethylene terephthalate, polyetherimide, and the like. Preferably, the low dielectric film 20 is a liquid crystal polymer, polyethylene fluoride, polyamide, or low dielectric constant polyimide. The low dielectric film 20 is a single-layer film or a laminate made of multiple layers, and in the case of multiple layers, at least one of the multiple layers may be a layer made of the low dielectric polymer material. Layers other than the layer made of the low dielectric polymer material may be made of various conventionally known materials such as epoxy resin. The liquid crystal polymer refers to an aromatic polyester resin having a basic structure such as parahydroxybenzoic acid, which exhibits liquid crystal properties in a molten state.
低誘電性フィルム２０の厚みは、金属積層基材の用途等に応じて適宜設定することができる。例えば、フレキシブルなプリント配線板として用いる場合は、厚みは１０μｍ以上１５０μｍ以下であることが好ましく、より好ましくは１０μｍ以上１２０μｍ以下である。なお、接合前の低誘電性フィルム２０の厚みは、マイクロメータ等によって測定可能であり、対象とする低誘電性フィルムの表面上からランダムに選択した１０点において測定した厚みの平均値をいう。また、用いる低誘電性フィルムについては、１０点の測定値の平均値からの偏差が全ての測定値で１０％以内であることが好ましい。 The thickness of the low dielectric film 20 can be set appropriately depending on the application of the metal laminate substrate. For example, when used as a flexible printed wiring board, the thickness is preferably 10 μm or more and 150 μm or less, and more preferably 10 μm or more and 120 μm or less. The thickness of the low dielectric film 20 before bonding can be measured using a micrometer or the like, and refers to the average value of thicknesses measured at 10 points randomly selected from the surface of the target low dielectric film. In addition, for the low dielectric film used, it is preferable that the deviation from the average value of the measured values at 10 points is within 10% for all measured values.
次に、本発明の第２実施形態について説明する。図２に、本発明の第２実施形態に係るキャリア層付き金属積層基材の断面を示す。本実施形態では、図２に示すように、極薄金属層１３と低誘電性フィルム２０との間に、金属を含む中間層３０を備える。この中間層３０は、１層でも良いし、２層以上が積層していても良い。金属を含む中間層３０としては、低誘電性フィルム２０上に設けられた蒸着もしくは無電解めっき、スパッタ成膜による金属層が挙げられる。 Next, a second embodiment of the present invention will be described. FIG. 2 shows a cross section of a metal laminated substrate with a carrier layer according to the second embodiment of the present invention. In this embodiment, as shown in FIG. 2, an intermediate layer 30 containing metal is provided between the ultra-thin metal layer 13 and the low dielectric film 20. This intermediate layer 30 may be a single layer, or two or more layers may be laminated. Examples of the intermediate layer 30 containing metal include a metal layer formed by vapor deposition, electroless plating, or sputtering on the low dielectric film 20.
なお、図２には記載していないが、第１実施形態に係るキャリア層付き金属積層基材と同様に、極薄金属層１３の中間層３０側の表面には、粗化粒子層や防錆層、シランカップリング剤の層等が積層されていても良い。これらの層は、いずれか一種の層が積層されていても良いし、複数種の層が積層されていても良い。粗化粒子層は、例えば、Ｃｕ、Ｃｏ及びＮｉからなる群より選択されるいずれか一種の金属又はその合金を含むことができるが、これに限定されなくても良い。また、防錆層は、例えば、Ｃｒ、Ｎｉ及びＺｎからなる群より選択されるいずれか一種の金属又はその合金を含むことができるが、これに限定されなくても良い。 Although not shown in FIG. 2, similar to the carrier layer-attached metal laminate substrate according to the first embodiment, the surface of the ultrathin metal layer 13 on the intermediate layer 30 side may be laminated with a roughened particle layer, an anti-rust layer, a silane coupling agent layer, or the like. Any one of these layers may be laminated, or multiple types of layers may be laminated. The roughened particle layer may contain, for example, any one of metals selected from the group consisting of Cu, Co, and Ni, or an alloy thereof, but is not limited thereto. The anti-rust layer may contain, for example, any one of metals selected from the group consisting of Cr, Ni, and Zn, or an alloy thereof, but is not limited thereto.
中間層３０は、銅、鉄、ニッケル、亜鉛、クロム、コバルト、チタン、スズ、白金、銀及び金からなる群より選択されるいずれか一種の金属又はその合金を含むことが好ましい。特に、極薄金属層１３が銅又はその合金である場合には、中間層３０を構成する金属についても、銅、又は銅ニッケル合金等の銅を含む合金であることが好ましい。中間層３０が例えばＣｕ－Ｎｉ合金である場合は、Ｃｕに対するＮｉの比率がａｔ％で１０～９０％であることが好ましい。しかし、これに限定されるものではない。これらの中間層３０を設けることにより、極薄金属層１３又は低誘電性フィルム２０の表面を保護し、また極薄金属層１３と低誘電性フィルム２０との密着性を向上させることができるだけでなく、中間層３０特有の機能を付与することができる（例えば、エッチング加工時のエッチングストッパー層としての機能等）。中間層３０の厚みは、密着性向上等の機能を発揮し得る厚みであれば良く、特に限定されない。具体的には、５ｎｍ以上２００ｎｍ以下の厚みとすることが好ましく、より好ましくは１０ｎｍ以上１００ｎｍ以下である。 The intermediate layer 30 preferably contains any one of metals or alloys thereof selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold. In particular, when the ultra-thin metal layer 13 is copper or an alloy thereof, the metal constituting the intermediate layer 30 is preferably copper or an alloy containing copper, such as a copper-nickel alloy. When the intermediate layer 30 is, for example, a Cu-Ni alloy, the ratio of Ni to Cu is preferably 10 to 90% in at%. However, this is not limited thereto. By providing these intermediate layers 30, it is possible to protect the surface of the ultra-thin metal layer 13 or the low dielectric film 20, improve the adhesion between the ultra-thin metal layer 13 and the low dielectric film 20, and also to impart a function unique to the intermediate layer 30 (for example, a function as an etching stopper layer during etching). The thickness of the intermediate layer 30 may be any thickness that can exhibit a function such as improving adhesion, and is not particularly limited. Specifically, the thickness is preferably 5 nm or more and 200 nm or less, and more preferably 10 nm or more and 100 nm or less.
次に、本発明に係るキャリア層付き金属積層基材の製造方法について、特に図２に示すような、低誘電性フィルム２０と極薄金属層１３との間に金属を含む中間層３０を有するキャリア層付き金属積層基材１Ｂを製造する場合を例に説明する。図２に示すキャリア層付き金属積層基材１Ｂは、キャリア層１１、剥離層１２、極薄金属層１３からなるキャリア層付き金属箔１０と、低誘電性フィルム２０とを準備し、低誘電性フィルム２０の面上に金属を含む中間層３０を設け、次に、これらを冷間圧延接合、表面活性化接合等の各種の方法により互いに接合して、層間を密着させることにより得ることができる。なお、キャリア層付き金属積層基材１Ｂを製造する際の高圧下での接合及び／又は熱処理は、接合前後及び／又は熱処理前後でキャリア層付き金属積層基材１Ｂの各層における組織を著しく変化させ、キャリア層付き金属積層基材１Ｂの特性を損なう恐れがあるため、そのような組織変化を回避できる接合・熱処理条件を選択することが好ましい。 Next, the manufacturing method of the carrier layer-attached metal laminated substrate according to the present invention will be described by taking as an example the case of manufacturing a carrier layer-attached metal laminated substrate 1B having a metal-containing intermediate layer 30 between a low dielectric film 20 and an extremely thin metal layer 13 as shown in FIG. 2. The carrier layer-attached metal laminated substrate 1B shown in FIG. 2 can be obtained by preparing a carrier layer-attached metal foil 10 consisting of a carrier layer 11, a peeling layer 12, and an extremely thin metal layer 13, and a low dielectric film 20, providing a metal-containing intermediate layer 30 on the surface of the low dielectric film 20, and then bonding these to each other by various methods such as cold rolling bonding and surface activation bonding to bring the layers into close contact with each other. Note that bonding and/or heat treatment under high pressure when manufacturing the carrier layer-attached metal laminated substrate 1B may significantly change the structure of each layer of the carrier layer-attached metal laminated substrate 1B before and after bonding and/or heat treatment, which may impair the properties of the carrier layer-attached metal laminated substrate 1B, so it is preferable to select bonding and heat treatment conditions that can avoid such structure changes.
キャリア層付き金属積層基材１Ｂを製造する方法として好ましい態様を図３Ａ及び図３Ｂに基づき説明する。まず、図３Ａに示すように、低誘電性フィルム２０の面２０ａをスパッタエッチングにより活性化した後（図３Ａの（ａ））、低誘電性フィルム２０の面２０ａ上に金属を含む中間層３０をスパッタ成膜する。スパッタ成膜を行う際の条件は、中間層３０を構成する金属種や、中間層３０の厚みに応じて適宜設定することができる。 A preferred embodiment of the method for manufacturing the metal laminated substrate 1B with a carrier layer is described with reference to Figures 3A and 3B. First, as shown in Figure 3A, the surface 20a of the low dielectric film 20 is activated by sputter etching (Figure 3A (a)), and then the intermediate layer 30 containing a metal is sputter-deposited on the surface 20a of the low dielectric film 20. The conditions for sputter deposition can be set appropriately depending on the type of metal constituting the intermediate layer 30 and the thickness of the intermediate layer 30.
次に、図３Ｂに示すように、中間層３０の表面３０ａをスパッタエッチングにより活性化し、キャリア層付き金属箔１０における極薄金属層１３の表面１３ａをスパッタエッチングにより活性化し、それら活性化した表面同士を圧延接合することにより（図３Ｂの（ｃ））、キャリア層付き金属積層基材１Ｂを製造することができる（図３Ｂの（ｄ））。なお、極薄金属層１３の表面１３ａに粗化粒子層や防錆層が含まれている場合は、当該粗化粒子層や防錆層表面がスパッタエッチングにより活性化される。その際、スパッタエッチングによって、当該粗化粒子層や防錆層が完全に除去されても良いし、除去されずに残存しても良い。圧延接合する際の圧下率は、０～３０％とする。好ましくは０～１５％である。上記の表面活性化接合による方法は、圧下率を低くすることができるため、剥離層１２の機能（低密着性）を維持したまま接合することが可能であり、また、皺や割れ等を生ずることなく、厚み精度に優れた極薄金属層１３を形成することができる。さらに、極薄金属層１３と中間層３０及び低誘電性フィルム２０との界面のうねりを小さくすることができるため、極薄金属層１３及び中間層３０へパターンエッチングを施して回路を形成する場合に、厚み精度が優れるため精密な回路を得ることができる。 Next, as shown in FIG. 3B, the surface 30a of the intermediate layer 30 is activated by sputter etching, the surface 13a of the ultra-thin metal layer 13 in the metal foil 10 with the carrier layer is activated by sputter etching, and the activated surfaces are roll-bonded together ((c) of FIG. 3B), thereby manufacturing a metal laminated substrate 1B with a carrier layer ((d) of FIG. 3B). In addition, if the surface 13a of the ultra-thin metal layer 13 contains a roughened particle layer or an anti-rust layer, the surface of the roughened particle layer or the anti-rust layer is activated by sputter etching. At that time, the roughened particle layer or the anti-rust layer may be completely removed by sputter etching, or may remain without being removed. The reduction ratio during roll bonding is 0 to 30%. It is preferably 0 to 15%. The above-mentioned surface activation bonding method can reduce the reduction ratio, so that it is possible to bond while maintaining the function (low adhesion) of the peel layer 12, and it is also possible to form an ultra-thin metal layer 13 with excellent thickness accuracy without causing wrinkles or cracks. Furthermore, since the waviness of the interface between the ultra-thin metal layer 13 and the intermediate layer 30 and the low dielectric film 20 can be reduced, when a circuit is formed by pattern etching the ultra-thin metal layer 13 and the intermediate layer 30, a precise circuit can be obtained due to excellent thickness accuracy.
なお、スパッタエッチングにより活性化する前の中間層３０の表面３０ａ、又は極薄金属層１３の表面１３ａには、必要に応じて、酸化防止や密着性向上のため、Ｎｉめっき、クロメート処理、シランカップリング剤処理等が施されていても良い。また、極薄金属層１３の表面１３ａは、中間層３０との密着性を高めるため、必要に応じて粗化処理を施すことができる。 The surface 30a of the intermediate layer 30 or the surface 13a of the ultra-thin metal layer 13 before activation by sputter etching may be subjected to Ni plating, chromate treatment, silane coupling agent treatment, etc., as necessary, to prevent oxidation and improve adhesion. Furthermore, the surface 13a of the ultra-thin metal layer 13 may be subjected to a roughening treatment as necessary to improve adhesion with the intermediate layer 30.
スパッタエッチング処理は、例えば、接合するキャリア層付き金属箔１０あるいは中間層３０を設けた低誘電性フィルム２０を、幅１００ｍｍ～６００ｍｍの長尺コイルとして用意し、キャリア層付き金属箔１０又は低誘電性フィルム２０の接合面をアース接地した一方の電極とし、絶縁支持された他の電極との間に１ＭＨｚ～５０ＭＨｚの交流を印加してグロー放電を発生させ、且つグロー放電によって生じたプラズマ中に露出される電極の面積を前記の他の電極の面積の１／３以下として行うことができる。スパッタエッチング処理中は、アース接地した電極が冷却ロールの形をとっており、搬送材の温度上昇を防いでいる。 The sputter etching process can be carried out, for example, by preparing the metal foil 10 with carrier layer or the low dielectric film 20 with intermediate layer 30 to be joined as a long coil with a width of 100 mm to 600 mm, using the joining surface of the metal foil 10 with carrier layer or the low dielectric film 20 as one electrode grounded to earth, applying an alternating current of 1 MHz to 50 MHz between the other electrode supported insulated to generate a glow discharge, and setting the area of the electrode exposed to the plasma generated by the glow discharge to 1/3 or less of the area of the other electrode. During the sputter etching process, the earthed electrode takes the form of a cooling roll to prevent the temperature of the transported material from rising.
スパッタエッチング処理では、真空下でキャリア層付き金属箔１０又は低誘電性フィルム２０の接合する面を不活性ガスによりスパッタすることにより、表面の吸着物を完全に除去し、且つ表面の酸化物層の一部又は全部を除去する。銅の酸化物層は完全に除去することが好ましい。不活性ガスとしては、アルゴン、ネオン、キセノン、クリプトン等や、これらを少なくとも１種類含む混合気体を適用することができる。金属の種類にもよるが、極薄金属層１３又は中間層３０の表面の吸着物は、エッチング量約１ｎｍ程度で完全に除去することができ、特に銅の酸化物層は通常５ｎｍ～１２ｎｍ（ＳｉＯ２換算）程度で除去が可能である。 In the sputter etching process, the bonding surface of the carrier layer-attached metal foil 10 or the low dielectric film 20 is sputtered with an inert gas under vacuum to completely remove the adsorbed matter on the surface and to remove a part or all of the oxide layer on the surface. It is preferable to completely remove the copper oxide layer. As the inert gas, argon, neon, xenon, krypton, etc., or a mixed gas containing at least one of these can be applied. Depending on the type of metal, the adsorbed matter on the surface of the ultrathin metal layer 13 or the intermediate layer 30 can be completely removed with an etching amount of about 1 nm, and in particular, the copper oxide layer can be removed with an etching amount of about 5 nm to 12 nm ( SiO2 equivalent).
スパッタエッチングの処理条件は、極薄金属層１３又は中間層３０の種類等に応じて適宜設定することができる。例えば、真空下で、１００Ｗ～１０ｋＷのプラズマ出力、ライン速度０．５ｍ／分～３０ｍ／分で行うことができる。この時の真空度は、表面への再吸着物を防止するため高い方が好ましいが、例えば、１×１０－５Ｐａ～１０Ｐａであれば良い。 The processing conditions for sputter etching can be appropriately set depending on the type of ultrathin metal layer 13 or intermediate layer 30. For example, sputter etching can be performed under vacuum with a plasma output of 100 W to 10 kW and a line speed of 0.5 m/min to 30 m/min. The degree of vacuum at this time is preferably high in order to prevent re-adsorption onto the surface, but may be, for example, 1×10 −5 Pa to 10 Pa.
スパッタエッチングを経た極薄金属層１３及び中間層３０の表面同士の圧接は、ロール圧接により行うことができる。ロール圧接の圧延線荷重は、特に限定されずに、例えば、０．１ｔｆ／ｃｍ～１０ｔｆ／ｃｍの範囲に設定して行うことができる。ただし、キャリア層付き金属箔１０又は中間層３０を設けた低誘電性フィルム２０の接合前の厚みが大きい場合等には、接合時の圧力確保のために圧延線荷重を高くすることが必要になる場合があり、この数値範囲に限定されるものではない。一方で、圧延線荷重が高過ぎると、極薄金属層１３又は中間層３０の表層だけでなく、接合界面も変形しやすくなるため、キャリア層付き金属積層基材１Ｂにおけるそれぞれの層の厚み精度が低下する恐れがある。また、圧延線荷重が高いと接合時に加わる加工ひずみが大きくなる恐れがある。 The surfaces of the ultra-thin metal layer 13 and the intermediate layer 30 that have been subjected to sputter etching can be pressed together by roll pressing. The rolling line load of the roll pressing can be set to, for example, a range of 0.1 tf/cm to 10 tf/cm. However, when the thickness of the metal foil 10 with the carrier layer or the low dielectric film 20 with the intermediate layer 30 before bonding is large, it may be necessary to increase the rolling line load to ensure pressure during bonding, and the rolling line load is not limited to this numerical range. On the other hand, if the rolling line load is too high, not only the surface layer of the ultra-thin metal layer 13 or the intermediate layer 30 but also the bonding interface is easily deformed, so there is a risk that the thickness accuracy of each layer in the metal laminated base material 1B with the carrier layer will decrease. In addition, if the rolling line load is high, there is a risk that the processing strain applied during bonding will be large.
圧接する際の圧下率は、３０％以下であり、好ましくは８％以下、より好ましくは６％以下である。なお、圧接の前後で厚さは変わらなくても良いため、圧下率の下限値は０％である。 The reduction ratio during pressure welding is 30% or less, preferably 8% or less, and more preferably 6% or less. Since the thickness does not need to change before and after pressure welding, the lower limit of the reduction ratio is 0%.
ロール圧接による接合は、極薄金属層１３又は中間層３０表面への酸素の再吸着によって両者間の接合強度が低下するのを防止するため、非酸化雰囲気中、例えば真空中やＡｒ等の不活性ガス雰囲気中で行うことが好ましい。 The bonding by roll pressure is preferably performed in a non-oxidizing atmosphere, such as a vacuum or an inert gas atmosphere such as Ar, to prevent a decrease in the bonding strength between the two due to re-adsorption of oxygen onto the surface of the ultra-thin metal layer 13 or the intermediate layer 30.
また、圧接により得られたキャリア層付き金属積層基材１Ｂは、必要に応じて、さらに熱処理を行うことができる。熱処理によって、極薄金属層１３又は中間層３０のひずみが除かれ、層間の密着性を向上させることができる。この熱処理は、高温で長時間行うと、剥離層１２を起点にキャリア層１１にフクレが発生し、そのフクレを起点にキャリア層１１が剥離する恐れや、逆にキャリア層１１と極薄金属層１３との密着性が相互拡散等により高まり、キャリア層１１の剥離が困難となる恐れもある。また、極薄金属層１３と中間層３０の組合せ次第では界面に金属間化合物を生成し、密着性（接合強度）が低下する傾向がある。よって、上記の熱処理は１６０℃以上３００℃以下の温度で行う。より好ましくは１８０℃以上２９０℃以下である。あるいは、圧延接合した後に熱処理を行わないことが好ましい。なお、接合後のキャリア層付き金属積層基材１Ｂからキャリア層１１を剥離・除去した後であれば、極薄金属層１３及び中間層３０の界面において金属間化合物を生成しない温度範囲での熱処理を行っても良い。 In addition, the metal laminated substrate 1B with the carrier layer obtained by pressure welding can be further heat-treated as necessary. The heat treatment removes the distortion of the ultra-thin metal layer 13 or the intermediate layer 30, and improves the adhesion between the layers. If this heat treatment is performed at a high temperature for a long time, there is a risk that a blister will occur in the carrier layer 11 starting from the peeling layer 12, and the carrier layer 11 will peel off from the blister, or conversely, the adhesion between the carrier layer 11 and the ultra-thin metal layer 13 will increase due to mutual diffusion, etc., making it difficult to peel off the carrier layer 11. In addition, depending on the combination of the ultra-thin metal layer 13 and the intermediate layer 30, an intermetallic compound will be generated at the interface, and the adhesion (bonding strength) will tend to decrease. Therefore, the above heat treatment is performed at a temperature of 160 ° C or more and 300 ° C or less. More preferably, it is 180 ° C or more and 290 ° C or less. Alternatively, it is preferable not to perform heat treatment after rolling and bonding. In addition, after the carrier layer 11 is peeled off and removed from the metal laminate substrate 1B with the carrier layer after bonding, heat treatment may be performed in a temperature range that does not generate an intermetallic compound at the interface between the ultrathin metal layer 13 and the intermediate layer 30.
次に、本発明に係る金属積層基材及びその製造方法について説明する。図４は、本発明の一実施形態に係る金属積層基材の製造工程を示す図である。図４に示す金属積層基材２は、低誘電性フィルム２０の一方の面に、金属を含む中間層３０を介して極薄金属層１３が積層されて概略構成されている。金属積層基材２は、キャリア層１１及び剥離層１２を有しない以外は、図２に示すキャリア層付き金属積層基材１Ｂと同じであり、各層の構成は、キャリア層付き金属積層基材１Ｂにおける各層の構成と同様である。この金属積層基材２は、キャリア層付き金属積層基材１Ｂから得ることができる。すなわち、図４に示すように、キャリア層付き金属積層基材１Ｂを準備し（図４の（ａ））、このキャリア層付き金属積層基材１Ｂにおけるキャリア層１１を剥離層１２とともに剥離することにより（図４の（ｂ））、３層構造の金属積層基材２を得ることができる（図４の（ｃ））。 Next, the metal laminated substrate and its manufacturing method according to the present invention will be described. FIG. 4 is a diagram showing the manufacturing process of the metal laminated substrate according to one embodiment of the present invention. The metal laminated substrate 2 shown in FIG. 4 is roughly constructed by laminating an extremely thin metal layer 13 on one side of a low dielectric film 20 via an intermediate layer 30 containing a metal. The metal laminated substrate 2 is the same as the carrier layer-attached metal laminated substrate 1B shown in FIG. 2 except that it does not have the carrier layer 11 and the peeling layer 12, and the configuration of each layer is the same as the configuration of each layer in the carrier layer-attached metal laminated substrate 1B. This metal laminated substrate 2 can be obtained from the carrier layer-attached metal laminated substrate 1B. That is, as shown in FIG. 4, the carrier layer-attached metal laminated substrate 1B is prepared ((a) of FIG. 4), and the carrier layer 11 in the carrier layer-attached metal laminated substrate 1B is peeled off together with the peeling layer 12 ((b) of FIG. 4), thereby obtaining a three-layered metal laminated substrate 2 ((c) of FIG. 4).
製造された金属積層基材２は、例えば厚みが０．５μｍ以上１０μｍ以下であるような極薄金属層１３を有しており、フレキシブルな回路基板を作製するための金属積層基材（金属張積層板）として利用することができる。なお、本発明の金属積層基材には、極薄金属層１３における低誘電性フィルムと反対側の表面上に、無電解めっき、電解めっき（例えば銅めっき）等により追加の金属層を積層した形態を含むものである。 The manufactured metal laminated substrate 2 has an extremely thin metal layer 13, for example, having a thickness of 0.5 μm or more and 10 μm or less, and can be used as a metal laminated substrate (metal-clad laminate) for producing a flexible circuit board. The metal laminated substrate of the present invention also includes a form in which an additional metal layer is laminated by electroless plating, electrolytic plating (e.g., copper plating), etc. on the surface of the extremely thin metal layer 13 opposite the low dielectric film.
金属積層基材２を用いて微細な回路が形成されたプリント配線板を得ることができる。回路を形成する工程において、回路部分にのみ前記追加の金属層を形成することもできる。具体的には、モディファイドセミアディティブ法（ＭＳＡＰ法）やセミアディティブ法（ＳＡＰ法）等の従来知られた手法を適宜用いてプリント配線板を得ることができ、例えば、金属積層基材２における極薄金属層１３上の非回路部をマスクし、マスクされていない部分に銅めっきを施して追加の金属層を形成し、マスクを除去し、マスクにより隠れていた極薄金属層１３をエッチングにより除去することによってプリント配線板を製造することができる。なお、本発明における「プリント配線板」には、回路を形成した積層体のみならず、回路を形成した後にＩＣ等の電子部品類を搭載したものも含む。 A printed wiring board having a fine circuit formed thereon can be obtained using the metal laminated substrate 2. In the process of forming the circuit, the additional metal layer can be formed only on the circuit portion. Specifically, a printed wiring board can be obtained by appropriately using a conventionally known method such as the modified semi-additive method (MSAP method) or the semi-additive method (SAP method). For example, a printed wiring board can be manufactured by masking the non-circuit portion on the ultra-thin metal layer 13 in the metal laminated substrate 2, plating the unmasked portion with copper to form an additional metal layer, removing the mask, and removing the ultra-thin metal layer 13 hidden by the mask by etching. Note that the "printed wiring board" in the present invention includes not only a laminate on which a circuit is formed, but also a board on which electronic components such as ICs are mounted after the circuit is formed.
図１におけるキャリア層付き金属積層基材１Ａ、図２におけるキャリア層付き金属積層基材１Ｂ、及び図４における金属積層基材２の実施形態では、低誘電性フィルム２０の一方の面に、キャリア層付き金属箔１０ないし極薄金属層１３を積層させる場合について説明したが、これに限定されるものではない。すなわち、必要に応じて、低誘電性フィルム２０の両方の面に、中間層３０、極薄金属層１３、剥離層１２及びキャリア層１１を設けても良い。低誘電性フィルム２０の両面にこれらの各層を設けたキャリア層付き金属積層基材を利用することにより、低誘電性フィルム２０の両面に回路が形成されたフレキシブルなプリント配線板を得ることができる。 In the embodiments of the metal laminated substrate 1A with a carrier layer in FIG. 1, the metal laminated substrate 1B with a carrier layer in FIG. 2, and the metal laminated substrate 2 in FIG. 4, the case where the metal foil 10 with a carrier layer or the ultra-thin metal layer 13 is laminated on one side of the low dielectric film 20 has been described, but this is not limited to this. That is, if necessary, the intermediate layer 30, the ultra-thin metal layer 13, the peeling layer 12, and the carrier layer 11 may be provided on both sides of the low dielectric film 20. By using a metal laminated substrate with a carrier layer in which these layers are provided on both sides of the low dielectric film 20, a flexible printed wiring board in which circuits are formed on both sides of the low dielectric film 20 can be obtained.
以下、実施例及び比較例に基づき本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to these examples.
（実施例１）
まず、キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（有機系剥離層）を介して厚み１．５μｍの極薄銅層とその表面に粗化粒子層及び防錆層が設けられたキャリア層付き銅箔（三井金属鉱業（株）製ＭＴ１８ＦＬ）と、低誘電性フィルムとして厚み２５μｍの液晶ポリマー（ＬＣＰ）フィルムとを準備した。ＬＣＰフィルムの表面をスパッタエッチングにより活性化した後、銅からなる中間層（厚み４０ｎｍ）をスパッタ成膜により形成した。そして、極薄銅層及び中間層の表面同士を圧延接合して、目的のキャリア層付き金属積層基材を製造した。圧接する際の線荷重は１．５ｔ／ｃｍとし、表面活性化接合による圧下率は２．２％である。圧延接合後、２４０℃での熱処理を行った。
Example 1
First, as a metal foil with a carrier layer, a copper foil with a carrier layer (MITSUI MINING & SMELTING CO., LTD. MT18FL) in which an ultra-thin copper layer with a thickness of 1.5 μm and a roughening particle layer and an anti-rust layer are provided on the surface of the carrier layer with a release layer (organic release layer) on a carrier layer with a thickness of 18 μm made of copper, and a liquid crystal polymer (LCP) film with a thickness of 25 μm as a low dielectric film were prepared. After activating the surface of the LCP film by sputter etching, an intermediate layer (thickness 40 nm) made of copper was formed by sputter deposition. Then, the surfaces of the ultra-thin copper layer and the intermediate layer were roll-bonded to each other to produce the intended metal laminated base material with a carrier layer. The line load during pressure bonding was 1.5 t/cm, and the rolling reduction rate by surface activation bonding was 2.2%. After roll bonding, heat treatment was performed at 240 ° C.
（実施例２）
キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（有機系剥離層）を介して厚み１．５μｍの極薄銅層とその表面に粗化粒子層及び防錆層が設けられたキャリア層付き銅箔（三井金属鉱業（株）製ＭＴ１８ＦＬ）を用いた。また、低誘電性フィルムとして、厚み１００μｍのＬＣＰフィルムを用い、この表面をスパッタエッチングにより活性化した後、銅からなる中間層（厚み４０ｎｍ）をスパッタ成膜により形成した。そして、極薄銅層及び中間層の表面同士を圧延接合し、その後に熱処理を行ってキャリア層付き金属積層基材を製造した。接合条件は表１に示すとおりである。また、表面活性化接合による圧下率は２．５％である。
Example 2
As the metal foil with a carrier layer, a copper foil with a carrier layer (MITSUI MINING & SMELTING CO., LTD. MT18FL) was used, which was a 18 μm-thick carrier layer made of copper, with a 1.5 μm-thick ultra-thin copper layer and a roughened particle layer and an anti-rust layer provided on its surface via a release layer (organic release layer). In addition, a 100 μm-thick LCP film was used as the low dielectric film, and the surface was activated by sputter etching, and then an intermediate layer (thickness 40 nm) made of copper was formed by sputter deposition. Then, the surfaces of the ultra-thin copper layer and the intermediate layer were roll-bonded together, and then heat treatment was performed to produce a metal laminated base material with a carrier layer. The bonding conditions are as shown in Table 1. In addition, the rolling reduction rate by surface activation bonding was 2.5%.
（実施例３及び４）
接合条件を表１に示すとおりに変更した以外は、実施例２と同様にしてキャリア層付き金属積層基材を製造した。実施例３及び４における圧下率はそれぞれ２．５％及び３．５％である。
(Examples 3 and 4)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 2, except that the joining conditions were changed as shown in Table 1. The rolling reductions in Examples 3 and 4 were 2.5% and 3.5%, respectively.
（実施例５）
低誘電性フィルム及び中間層として、実施例１と同様に、厚み２５μｍのＬＣＰフィルムの表面に銅からなる中間層（厚み４０ｎｍ）をスパッタ成膜により形成したものを用い、さらに接合条件を表１に示すとおりに変更した以外は、実施例２と同様にしてキャリア層付き金属積層基材を製造した。圧下率は２．２％である。
Example 5
As the low dielectric film and intermediate layer, a copper intermediate layer (thickness 40 nm) formed by sputtering on the surface of a 25 μm-thick LCP film was used as in Example 1, and a metal laminated substrate with a carrier layer was produced in the same manner as in Example 2, except that the bonding conditions were changed as shown in Table 1. The rolling reduction was 2.2%.
（実施例６）
キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（無機系剥離層）を介して厚み３．０μｍの極薄銅層とその表面に粗化粒子層及び防錆層が設けられたキャリア層付き銅箔（ＪＸ金属（株）製ＪＸＵＴ－III）を用い、さらに接合条件を表１に示すとおりに変更した以外は、実施例５と同様にしてキャリア層付き金属積層基材を製造した。圧下率は４．３％である。
Example 6
A carrier layer-attached metal foil (JXUT-III manufactured by JX Nippon Mining & Metals Corporation) was used as the carrier layer-attached metal foil, which was a 18 μm-thick copper carrier layer, on which an ultrathin copper layer having a thickness of 3.0 μm and a roughened particle layer and an anti-rust layer were provided via a release layer (inorganic release layer), and the bonding conditions were changed as shown in Table 1. A carrier layer-attached metal laminated base material was produced in the same manner as in Example 5. The rolling reduction was 4.3%.
（実施例７）
低誘電性フィルム及び中間層として、厚み２５μｍの低誘電性ポリイミド（変性ポリイミド、ＭＰＩ）フィルムの表面に銅からなる中間層（厚み４０ｎｍ）をスパッタ成膜により形成したものを用いた以外は、実施例４と同様にしてキャリア層付き金属積層基材を製造した。圧下率は２．２％である。
(Example 7)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 4, except that a low dielectric film and intermediate layer were used in which an intermediate layer (thickness 40 nm) made of copper was formed on the surface of a low dielectric polyimide (modified polyimide, MPI) film having a thickness of 25 μm by sputtering deposition. The rolling reduction was 2.2%.
（実施例８）
キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（無機系剥離層）を介して厚み２．０μｍの極薄銅層とその表面に防錆層のみ（粗化粒子層なし）が設けられたキャリア層付き銅箔（試作材１）を用い、さらに接合条件を表１に示すとおりに変更した以外は、実施例６と同様にしてキャリア層付き金属積層基材を製造した。圧下率は２．２％である。
(Example 8)
A carrier layer-attached metal foil (prototype material 1) was used as the carrier layer-attached metal foil, which was a copper carrier layer having a thickness of 18 μm, on which an ultrathin copper layer having a thickness of 2.0 μm and only an anticorrosive layer (without a roughening particle layer) were provided on the surface of the carrier layer (prototype material 1) was used, and a carrier layer-attached metal laminated base material was produced in the same manner as in Example 6, except that the bonding conditions were changed as shown in Table 1. The rolling reduction was 2.2%.
（実施例９）
キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（有機系剥離層）を介して厚み５．０μｍの極薄銅層とその表面に防錆層のみ（粗化粒子層なし）が設けられたキャリア層付き銅箔（試作材２）を用い、さらに接合条件を表１に示すとおりに変更した以外は、実施例８と同様にしてキャリア層付き金属積層基材を製造した。圧下率は６．３％である。
(Example 9)
A carrier layer-attached copper foil (prototype material 2) was used as the carrier layer-attached metal foil, which was a 18 μm-thick copper carrier layer made of copper, on which a 5.0 μm-thick ultrathin copper layer and only a rust-proofing layer (without a roughening particle layer) were provided on the surface of the carrier layer (prototype material 2) was used, and a carrier layer-attached metal laminated base material was produced in the same manner as in Example 8, except that the bonding conditions were changed as shown in Table 1. The rolling reduction was 6.3%.
（比較例１）
接合条件を表１に示すとおりに変更した以外は、実施例５と同様にしてキャリア層付き金属積層基材を製造した。圧下率は２．２％である。
(Comparative Example 1)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 5, except that the joining conditions were changed as shown in Table 1. The rolling reduction was 2.2%.
（比較例２）
接合条件を表１に示すとおりに変更した以外は、実施例６と同様にしてキャリア層付き金属積層基材を製造した。圧下率は４．３％である。
(Comparative Example 2)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 6, except that the joining conditions were changed as shown in Table 1. The rolling reduction was 4.3%.
（比較例３）
接合条件を表１に示すとおりに変更した以外は、実施例５と同様にしてキャリア層付き金属積層基材を製造した。圧下率は２．２％である。
(Comparative Example 3)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 5, except that the joining conditions were changed as shown in Table 1. The rolling reduction was 2.2%.
（比較例４）
接合条件を表１に示すとおりに変更した以外は、実施例６と同様にしてキャリア層付き金属積層基材を製造した。圧下率は４．３％である。
(Comparative Example 4)
A metal laminated substrate with a carrier layer was produced in the same manner as in Example 6, except that the joining conditions were changed as shown in Table 1. The rolling reduction was 4.3%.
（比較例５）
まず、キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（有機系剥離層）を介して厚み２．０μｍの極薄銅層とその表面に粗化粒子層及び防錆層が設けられたキャリア層付き銅箔（三井金属鉱業（株）製ＭＴ１８ＦＬ）と、低誘電性フィルムとして厚み２５μｍの液晶ポリマー（ＬＣＰ）フィルムとを準備した。続いて、キャリア層付き銅箔とＬＣＰフィルムとを熱圧着により接合し、キャリア層付き金属積層基材を製造した。熱圧着の条件は表２に示すとおりである。
(Comparative Example 5)
First, as a metal foil with a carrier layer, a copper foil with a carrier layer (MITSUI MINING & SMELTING CO., LTD. MT18FL) was prepared, which was a 18 μm-thick copper carrier layer, a 2.0 μm-thick ultrathin copper layer, and a roughening particle layer and an anti-rust layer on its surface, via a release layer (organic release layer), and a 25 μm-thick liquid crystal polymer (LCP) film was prepared as a low dielectric film. Next, the copper foil with the carrier layer and the LCP film were bonded by thermocompression bonding to produce a metal laminated substrate with a carrier layer. The thermocompression bonding conditions are as shown in Table 2.
（比較例６及び７）
熱圧着の条件を表２に示すとおりに変更した以外は、比較例５と同様にしてキャリア層付き金属積層基材を製造した。
(Comparative Examples 6 and 7)
A metal laminated substrate with a carrier layer was produced in the same manner as in Comparative Example 5, except that the conditions for thermocompression bonding were changed as shown in Table 2.
（比較例８）
まず、キャリア層付き金属箔として、銅からなる厚み１８μｍのキャリア層に、剥離層（無機系剥離層）を介して厚み３．０μｍの極薄銅層とその表面に粗化粒子層及び防錆層が設けられたキャリア層付き銅箔（ＪＸ金属（株）製ＪＸＵＴ－III）と、低誘電性フィルムとして厚み２５μｍの液晶ポリマー（ＬＣＰ）フィルムとを準備した。続いて、キャリア層付き銅箔とＬＣＰフィルムとを熱圧着により接合し、キャリア層付き金属積層基材を製造した。熱圧着の条件は表２に示すとおりである。
(Comparative Example 8)
First, as the metal foil with a carrier layer, a copper foil with a carrier layer (JXUT-III manufactured by JX Metals Corporation) having a 18 μm-thick copper carrier layer, an ultra-thin copper layer with a thickness of 3.0 μm and a roughening particle layer and an anti-rust layer on its surface, were prepared via a release layer (inorganic release layer), and a liquid crystal polymer (LCP) film with a thickness of 25 μm was prepared as a low dielectric film. Next, the copper foil with the carrier layer and the LCP film were bonded by thermocompression bonding to produce a metal laminated substrate with a carrier layer. The thermocompression bonding conditions are as shown in Table 2.
（比較例９及び１０）
熱圧着の条件を表２に示すとおりに変更した以外は、比較例８と同様にしてキャリア層付き金属積層基材を製造した。
(Comparative Examples 9 and 10)
A metal laminated substrate with a carrier layer was produced in the same manner as in Comparative Example 8, except that the conditions for thermocompression bonding were changed as shown in Table 2.
実施例１～９及び比較例１～１０で得られたキャリア層付き金属積層基材について、極薄銅層と低誘電性フィルムの接合強度、キャリア層と極薄銅層の剥離強度、及び総厚みを測定した。測定結果を表３に示す。 The bonding strength between the ultra-thin copper layer and the low dielectric film, the peel strength between the carrier layer and the ultra-thin copper layer, and the total thickness were measured for the metal laminate substrates with carrier layers obtained in Examples 1 to 9 and Comparative Examples 1 to 10. The measurement results are shown in Table 3.
表１及び３に示すように、熱処理温度が高い場合（比較例１及び２）、及び熱処理温度が低い場合（比較例３及び４）には、キャリア層及び極薄銅層の間の低い密着性と、極薄銅層及び低誘電性フィルムの間の高い密着性との両立ができなかった。 As shown in Tables 1 and 3, when the heat treatment temperature was high (Comparative Examples 1 and 2) and when the heat treatment temperature was low (Comparative Examples 3 and 4), it was not possible to achieve both low adhesion between the carrier layer and the ultra-thin copper layer and high adhesion between the ultra-thin copper layer and the low dielectric film.
また、表２及び３に示すように、キャリア層付き銅箔と低誘電性フィルムとを熱圧着により接合した場合には、キャリア層及び極薄銅層の間の低い密着性と、極薄銅層及び低誘電性フィルムの間の高い密着性との両立ができなかった。特に、比較例６、７、９及び１０では、低誘電性フィルムが脆く変質し、回路を形成するための金属積層基材として不適であった。また、比較例１０では、キャリア層と極薄銅層とが剥離できなかった。 Furthermore, as shown in Tables 2 and 3, when the copper foil with a carrier layer and the low dielectric film were bonded by thermocompression bonding, it was not possible to achieve both low adhesion between the carrier layer and the ultra-thin copper layer and high adhesion between the ultra-thin copper layer and the low dielectric film. In particular, in Comparative Examples 6, 7, 9, and 10, the low dielectric film became brittle and deteriorated, making it unsuitable as a metal laminate substrate for forming a circuit. Furthermore, in Comparative Example 10, the carrier layer and the ultra-thin copper layer could not be peeled off.
さらに、実施例５において接合強度を測定した後の各々の剥離面について、走査型電子顕微鏡（ＳＥＭ）を用いて観察及びＥＤＸによる表面元素分析を実施した。走査型電子顕微鏡像を図５に示す。分析の結果、実施例５のＬＣＰ側の剥離面には銅が付着していないことが確認された。また、極薄銅層側（剥離表面は中間層）には凝集破壊したＬＣＰが一部付着していることから、剥離はＬＣＰの内部破壊及び中間層とＬＣＰの界面剥離の両方によって生じていることが明らかとなった。 Furthermore, after measuring the bonding strength in Example 5, each peeled surface was observed using a scanning electron microscope (SEM) and subjected to surface elemental analysis using EDX. Scanning electron microscope images are shown in Figure 5. As a result of the analysis, it was confirmed that no copper was attached to the peeled surface on the LCP side of Example 5. In addition, since some LCP that had undergone cohesive failure was attached to the ultra-thin copper layer side (the peeled surface was the intermediate layer), it became clear that the peeling was caused by both internal failure of the LCP and interfacial peeling between the intermediate layer and the LCP.
（実施例１０～１６）
実施例１～７で得られたキャリア層付き金属積層基材からキャリア層を除去することで、粗化粒子層及び防錆層を含む厚み１．５μｍ～３．０μｍの極薄銅層を備えた金属積層基材を製造した。
(Examples 10 to 16)
By removing the carrier layer from the metal laminated substrate with a carrier layer obtained in Examples 1 to 7, a metal laminated substrate having an extremely thin copper layer with a thickness of 1.5 μm to 3.0 μm including a roughening particle layer and an anticorrosive layer was produced.
（実施例１７、１８）
実施例８、９で得られたキャリア層付き金属積層基材からキャリア層を除去することで、防錆層のみ（粗化粒子層は含まない）を含む厚み２．０μｍ～５．０μｍの極薄銅層を備えた金属積層基材を製造した。
(Examples 17 and 18)
By removing the carrier layer from the metal laminated substrate with a carrier layer obtained in Examples 8 and 9, a metal laminated substrate having an ultrathin copper layer with a thickness of 2.0 μm to 5.0 μm including only an anticorrosive layer (not including a roughening particle layer) was produced.
得られた実施例１０～１８の金属積層基材について、極薄銅層と低誘電性フィルムの接合強度、総厚み、及び極薄銅層の厚みを測定した。測定結果を表４に示す。 The bonding strength between the ultra-thin copper layer and the low dielectric film, the total thickness, and the thickness of the ultra-thin copper layer were measured for the metal laminate substrates of Examples 10 to 18. The measurement results are shown in Table 4.
これら実施例１０～１６の金属積層基材は、極薄銅層、粗化粒子層、防錆層、中間層（銅）及びＬＣＰ又はＭＰＩフィルムからなる構成であり、また、実施例１７、１８の金属積層基材は、極薄銅層、防錆層、中間層（銅）及びＬＣＰからなる構成である。これらの金属積層基材については、グロー放電発光分光法（ＧＤＳ）、オージェ電子分光法（ＡＥＳ）による深さ方向の元素の分布状態（Ｄｅｐｔｈ Ｐｒｏｆｉｌｅ）測定や透過型電子顕微鏡（ＴＥＭ）による断面観察を用いて各層の積層状態を特定することが可能である。 The metal laminated substrates of Examples 10 to 16 are composed of an ultra-thin copper layer, a roughened particle layer, an anti-rust layer, an intermediate layer (copper), and an LCP or MPI film, and the metal laminated substrates of Examples 17 and 18 are composed of an ultra-thin copper layer, an anti-rust layer, an intermediate layer (copper), and an LCP. For these metal laminated substrates, it is possible to identify the layering state of each layer by measuring the distribution state of elements in the depth direction (depth profile) using glow discharge optical emission spectroscopy (GDS) or Auger electron spectroscopy (AES) or by observing the cross section using a transmission electron microscope (TEM).
また、金属積層基材における極薄銅層上に、レジスト等で回路パターンを形成し、モディファイドセミアディティブ法（ＭＳＡＰ法）やセミアディティブ法（ＳＡＰ法）等により低誘電性フィルム上に微細な回路を形成することが可能となる。 It is also possible to form a circuit pattern using a resist or the like on the ultra-thin copper layer of the metal laminate substrate, and then form fine circuits on the low dielectric film using the modified semi-additive method (MSAP method) or semi-additive method (SAP method), etc.
１Ａ キャリア層付き金属積層基材
１Ｂ キャリア層付き金属積層基材
２ 金属積層基材
１０ キャリア層付き金属箔
１１ キャリア層
１２ 剥離層
１３ 極薄金属層
１３ａ 極薄金属層の表面
２０ 低誘電性フィルム
２０ａ 低誘電性フィルムの面
３０ 中間層
３０ａ 中間層の表面
Reference Signs List 1A Metal laminated substrate with carrier layer 1B Metal laminated substrate with carrier layer 2 Metal laminated substrate 10 Metal foil with carrier layer 11 Carrier layer 12 Release layer 13 Ultra-thin metal layer 13a Surface of ultra-thin metal layer 20 Low dielectric film 20a Surface of low dielectric film 30 Intermediate layer 30a Surface of intermediate layer
Claims (11)
前記低誘電性フィルムと前記極薄金属層との間に、銅又はその合金を含むスパッタ成膜により得られた中間層を１層以上有し、
前記極薄金属層と前記低誘電性フィルムの接合強度が、前記キャリア層と前記極薄金属層の剥離強度よりも大きく、前記極薄金属層と前記低誘電性フィルムの接合強度が、２．０Ｎ／ｃｍ以上であり、
前記低誘電性フィルムにおいて、１０点の厚みの測定値の平均値からの偏差が全ての測定値で１０％以内であり、
前記剥離層が、有機系剥離層又は無機系剥離層からなる１層である前記キャリア層付き金属積層基材。 A metal laminated substrate with a carrier layer, comprising a metal foil with a carrier layer, the metal foil comprising at least three layers including a carrier layer, a release layer, and an extremely thin metal layer, laminated on at least one surface of a low dielectric film,
Between the low dielectric film and the ultrathin metal layer, there is one or more intermediate layers obtained by sputtering deposition containing copper or an alloy thereof;
The bonding strength between the ultra-thin metal layer and the low dielectric film is greater than the peel strength between the carrier layer and the ultra-thin metal layer, and the bonding strength between the ultra-thin metal layer and the low dielectric film is 2.0 N/cm or more;
In the low dielectric film, the deviation of all of the thickness measurements at 10 points from the average value is within 10%;
The above-mentioned metal laminate substrate with a carrier layer, wherein the release layer is a single layer consisting of an organic release layer or an inorganic release layer.
低誘電性フィルムと、キャリア層、剥離層及び極薄金属層を含む少なくとも３層以上からなるキャリア層付き金属箔とを準備する工程と、
前記低誘電性フィルムの少なくとも一方の面をスパッタエッチングにより活性化した後、前記面上に金属を含む中間層をスパッタ成膜する工程と、
前記中間層の表面をスパッタエッチングにより活性化する工程と、
前記極薄金属層の表面をスパッタエッチングにより活性化する工程と、
前記活性化した表面同士を０～３０％の圧下率で圧延接合する工程と、
前記圧延接合を行った後、１６０℃以上３００℃以下での熱処理を行う工程と、
を含む前記キャリア層付き金属積層基材の製造方法。 A method for producing a metal laminated substrate with a carrier layer, comprising: a metal foil with a carrier layer, the metal foil being composed of at least three layers including a carrier layer, a release layer, and an extremely thin metal layer, laminated on at least one surface of a low dielectric film; one or more intermediate layers containing a metal are provided between the low dielectric film and the extremely thin metal layer; and a bonding strength between the extremely thin metal layer and the low dielectric film is greater than a peel strength between the carrier layer and the extremely thin metal layer,
A step of preparing a low dielectric film and a metal foil with a carrier layer, the metal foil having at least three layers including a carrier layer, a release layer, and an extremely thin metal layer;
a step of activating at least one surface of the low dielectric film by sputter etching, and then sputter-forming an intermediate layer containing a metal on the surface;
activating the surface of the intermediate layer by sputter etching;
activating the surface of the ultrathin metal layer by sputter etching;
Roll-bonding the activated surfaces together at a rolling reduction of 0 to 30%;
a step of performing a heat treatment at 160° C. or more and 300° C. or less after the roll bonding;
A method for producing the metal laminate substrate with a carrier layer comprising the steps of:
請求項１に記載のキャリア層付き金属積層基材における前記キャリア層を剥離する工程を含む前記金属積層基材の製造方法。 A method for producing a metal laminated substrate in which an extremely thin metal layer is laminated on at least one surface of a low dielectric film via an intermediate layer containing copper or an alloy thereof, comprising:
A method for producing a metal laminated substrate comprising the step of peeling off the carrier layer of the metal laminated substrate with a carrier layer according to claim 1 .
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202080060045.1A CN114342571A (en) | 2019-08-26 | 2020-08-25 | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board |
| PCT/JP2020/031951 WO2021039759A1 (en) | 2019-08-26 | 2020-08-25 | Carrier-layer-included metal laminate base material and method for producing same, metal laminate base material and method for producing same, and printed wiring board |
| KR1020227008479A KR20220053602A (en) | 2019-08-26 | 2020-08-25 | Metal laminated substrate with carrier layer and manufacturing method thereof, metal laminated substrate and manufacturing method thereof, and printed wiring board |
| TW109129043A TWI868201B (en) | 2019-08-26 | 2020-08-26 | Carrier layer metal laminate substrate and manufacturing method thereof, metal laminate substrate and manufacturing method thereof, and printed circuit board |
| JP2024197866A JP2025015606A (en) | 2019-08-26 | 2024-11-13 | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019154167 | 2019-08-26 | ||
| JP2019154167 | 2019-08-26 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2024197866A Division JP2025015606A (en) | 2019-08-26 | 2024-11-13 | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021035755A JP2021035755A (en) | 2021-03-04 |
| JP7588956B2 true JP7588956B2 (en) | 2024-11-25 |
Family
ID=74716925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020013319A Active JP7588956B2 (en) | 2019-08-26 | 2020-01-30 | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7588956B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023074531A1 (en) * | 2021-10-26 | 2023-05-04 | 東洋鋼鈑株式会社 | Metal laminate, method for manufacturing same, and printed wiring board |
| WO2023102845A1 (en) * | 2021-12-09 | 2023-06-15 | 陆一平 | Cascaded material surface active catalytic structure |
| WO2023149007A1 (en) * | 2022-02-07 | 2023-08-10 | 尾池工業株式会社 | Electroconductive film for circuit substrate, and method for producing electroconductive film for circuit substrate |
| KR102511335B1 (en) * | 2022-05-09 | 2023-03-17 | 와이엠티 주식회사 | Composite release layer for metal foil with carrier and metal foil comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007007937A (en) | 2005-06-29 | 2007-01-18 | Furukawa Circuit Foil Kk | Very thin copper foil with carrier, flexible copper-clad polyimide laminate, and flexible printed wiring polyimide board |
| JP2008255462A (en) | 2006-05-19 | 2008-10-23 | Mitsui Mining & Smelting Co Ltd | Copper foil with carrier sheet, method for producing copper foil with carrier sheet, surface-treated copper foil with carrier sheet, and copper-clad laminate using the surface-treated copper foil with carrier sheet |
| JP2010006071A (en) | 2009-08-21 | 2010-01-14 | Furukawa Electric Co Ltd:The | Surface treatment copper foil, extremely thin copper foil with carrier, flexible copper clad laminate, and polyimide based flexible printed wiring board |
| JP2013107323A (en) | 2011-11-22 | 2013-06-06 | Sumitomo Chemical Co Ltd | Laminate |
| WO2016174998A1 (en) | 2015-04-28 | 2016-11-03 | 三井金属鉱業株式会社 | Roughened copper foil and printed wiring board |
-
2020
- 2020-01-30 JP JP2020013319A patent/JP7588956B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007007937A (en) | 2005-06-29 | 2007-01-18 | Furukawa Circuit Foil Kk | Very thin copper foil with carrier, flexible copper-clad polyimide laminate, and flexible printed wiring polyimide board |
| JP2008255462A (en) | 2006-05-19 | 2008-10-23 | Mitsui Mining & Smelting Co Ltd | Copper foil with carrier sheet, method for producing copper foil with carrier sheet, surface-treated copper foil with carrier sheet, and copper-clad laminate using the surface-treated copper foil with carrier sheet |
| JP2010006071A (en) | 2009-08-21 | 2010-01-14 | Furukawa Electric Co Ltd:The | Surface treatment copper foil, extremely thin copper foil with carrier, flexible copper clad laminate, and polyimide based flexible printed wiring board |
| JP2013107323A (en) | 2011-11-22 | 2013-06-06 | Sumitomo Chemical Co Ltd | Laminate |
| WO2016174998A1 (en) | 2015-04-28 | 2016-11-03 | 三井金属鉱業株式会社 | Roughened copper foil and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202116119A (en) | 2021-04-16 |
| JP2021035755A (en) | 2021-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7588956B2 (en) | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board | |
| JP6905157B2 (en) | Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board | |
| US8624125B2 (en) | Metal foil laminated polyimide resin substrate | |
| JP2025015606A (en) | Metal laminated substrate with carrier layer and method for producing same, metal laminated substrate and method for producing same, and printed wiring board | |
| CN102124823B (en) | Copper foil for printed wiring board | |
| US20090246554A1 (en) | Laminate having peelability and production method therefor | |
| CN106455341A (en) | Carrier-Attached Copper Foil, Laminate, Method For Producing Printed Wiring Board, And Method For Producing Electronic Device | |
| JP5346054B2 (en) | Copper foil for printed wiring board and laminated board using the same | |
| WO2021215353A1 (en) | Metal-laminated film and method for manufacturing same | |
| TWI783190B (en) | laminated body | |
| WO2002100136A1 (en) | Composite copper foil with copper or copper alloy support body, and printed circuit board using the composite copper foil | |
| JP5386652B1 (en) | Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board | |
| JP3664708B2 (en) | Polyimide metal laminate and manufacturing method thereof | |
| TWI868201B (en) | Carrier layer metal laminate substrate and manufacturing method thereof, metal laminate substrate and manufacturing method thereof, and printed circuit board | |
| WO2023074531A1 (en) | Metal laminate, method for manufacturing same, and printed wiring board | |
| JP2014193592A (en) | Carrier-fitted copper foil, method for manufacturing carrier-fitted copper foil, printed wiring board, printed circuit board, copper-clad laminate sheet, and method for manufacturing printed wiring board | |
| JP5650023B2 (en) | Copper foil for printed wiring board and laminated board using the same | |
| WO2020195748A1 (en) | Metal foil for printed wiring board, metal foil with carrier, and metal-clad laminate, and method for manufacturing printed wiring board using same | |
| WO2024219326A1 (en) | Metal laminate, method for manufacturing same, and printed wiring board | |
| JP5373453B2 (en) | Copper foil for printed wiring boards | |
| JP2006159632A (en) | Copper metallized laminated sheet and its manufacturing method | |
| JP2004103681A (en) | Composite copper foil equipped with copper or copper-alloy substrate and printed board using the foil | |
| WO2012066658A1 (en) | Copper foil for printed wiring board | |
| TW201212753A (en) | Copper foil for printed circuit board with excellent etching property and laminate using the same | |
| JP2017030350A (en) | Copper foil with release film and method for producing copper foil with release film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221025 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230425 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230626 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231010 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20231206 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240604 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240726 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20241015 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20241113 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7588956 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |