CN113677519A - Laminate - Google Patents
Laminate Download PDFInfo
- Publication number
- CN113677519A CN113677519A CN202080027107.9A CN202080027107A CN113677519A CN 113677519 A CN113677519 A CN 113677519A CN 202080027107 A CN202080027107 A CN 202080027107A CN 113677519 A CN113677519 A CN 113677519A
- Authority
- CN
- China
- Prior art keywords
- copper
- laminate
- laminate according
- base material
- resin base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000010949 copper Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 27
- 238000012360 testing method Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 239000005751 Copper oxide Substances 0.000 claims description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 8
- 229920001955 polyphenylene ether Polymers 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000011282 treatment Methods 0.000 description 37
- 239000011889 copper foil Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000007747 plating Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000010884 ion-beam technique Methods 0.000 description 5
- 150000004032 porphyrins Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002500 effect on skin Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZTVCAEHRNBOTLI-UHFFFAOYSA-L Glycine, N-(carboxymethyl)-N-(2-hydroxyethyl)-, disodium salt Chemical compound [Na+].[Na+].OCCN(CC([O-])=O)CC([O-])=O ZTVCAEHRNBOTLI-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- MLDWGLQSBBCMMO-UHFFFAOYSA-N [Na].[Na].[Na].CNCC(=O)O Chemical compound [Na].[Na].[Na].CNCC(=O)O MLDWGLQSBBCMMO-UHFFFAOYSA-N 0.000 description 1
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229950003476 aminothiazole Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DRKXDZADBRTYAT-DLCHEQPYSA-J tetrasodium (2S)-2-[bis(carboxymethyl)amino]pentanedioate Chemical compound C(=O)(O)CN([C@@H](CCC(=O)[O-])C(=O)[O-])CC(=O)O.[Na+].[Na+].[Na+].[Na+].C(=O)(O)CN([C@@H](CCC(=O)[O-])C(=O)[O-])CC(=O)O DRKXDZADBRTYAT-DLCHEQPYSA-J 0.000 description 1
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
- B32B2327/18—PTFE, i.e. polytetrafluoroethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
The invention aims to: provides a novel laminated body of a composite copper material and a resin base material. The present invention provides a laminate in which a resin base material having a dielectric constant of 3.8 or less is laminated on at least a part of the surface of a copper material having a plurality of fine protrusions on the surface thereof, wherein the fractal dimension of the laminated surface of the copper material and the resin base material is 1.25 or more.
Description
Technical Field
The present invention relates to a laminate.
Background
Copper foil used for printed wiring boards is required to have adhesion to resins. In order to improve the adhesion, a method of roughening the surface of the copper foil by etching or the like and improving the mechanical adhesion by so-called anchor effect is used. However, from the viewpoint of high density of printed wiring boards and transmission loss in high frequency bands, planarization of the surface of copper foil is required. In order to satisfy such a contrary requirement, a copper surface treatment method has been developed in which an oxidation step, a reduction step, and the like are performed (international publication No. 2014/126193). According to the description, the copper foil is pretreated, and after the copper foil surface is oxidized by being immersed in a chemical agent containing an oxidizing agent to form irregularities of copper oxide, the copper foil surface is immersed in a chemical agent containing a reducing agent to reduce the copper oxide, thereby adjusting the irregularities of the surface and modifying the roughness of the surface. In addition, as a method for improving adhesion in the treatment of a copper foil by oxidation and reduction, a method of adding a surface active molecule in an oxidation step (japanese patent application laid-open No. 2013-534054) or a method of forming a protective film on the surface of a copper foil using an aminothiazole compound or the like after a reduction step (japanese patent application laid-open No. 8-97559) have been developed. A method has also been developed in which the surface of a copper conductor pattern on an insulating substrate is roughened, and a plating film having metal particles distributed discretely is formed by electroless plating on the surface having a copper oxide layer formed thereon (japanese patent laid-open No. 2000-151096).
On the other hand, in addition to the mechanical adhesion, 1) physical bonding force due to intermolecular force between the resin and the metal and 2) chemical bonding force due to covalent bond between a functional group of the resin and the metal, etc. are involved in the adhesion between the resin and the metal. In order to achieve a low dielectric constant and a low dielectric loss tangent, the proportion of OH groups (hydroxyl groups) in an insulating resin for a high-frequency circuit is reduced, but since the OH groups of the resin participate in bonding with a metal, the chemical bonding force with a copper foil is weakened (international publication No. 2017/150043). Therefore, stronger mechanical adhesion is required for adhesion between an insulating resin for high-frequency circuits and a copper foil.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to: provides a novel laminated body of a composite copper material and a resin base material.
Technical solution for solving technical problem
The inventors of the present invention have made extensive studies and, as a result, succeeded in producing a novel laminate of a copper clad material and a resin base material, which is excellent in peel strength and heat resistance. The present invention includes the following embodiments:
[1] a laminate comprising a copper material having a plurality of fine protrusions on at least a part of the surface thereof and a resin base material having a dielectric constant of 3.8 or less laminated on the surface,
the fractal dimension of the laminated surface of the copper material and the resin base material is 1.25 or more.
[2] The laminate according to [1], wherein the fractal dimension of the lamination surface is more than 1.4.
[3] The laminate according to [1] or [2], wherein at least a part of the surface of the copper material contains a copper oxide layer.
[4] The laminate according to [1] or [2], wherein a metal layer other than copper is formed on at least a part of a surface of the copper material, and the metal other than copper is at least one metal selected from Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au and Pt.
[5] The laminate according to [4], wherein the metal layer other than copper has an average thickness of 10nm to 150nm in a vertical direction.
[6] The laminate according to any one of [1] to [5], wherein the height of the projection is 50nm or more and 500nm or less on average in a vertical cross section of the laminate.
[7] The laminate according to [6], wherein the laminate has 30 or more convex portions on average per 3.78 μm cross-sectional width in a vertical cross-section.
[8] The laminate according to any one of [1] to [7], wherein the resin substrate contains polyphenylene ether, polytetrafluoroethylene or a liquid crystal polymer containing p-hydroxybenzoic acid.
[9] The laminate according to [8], wherein,
when the resin base material and the composite copper material are peeled off, the peeling mode is cohesive failure.
[10] The laminate according to [9], wherein the deterioration rate in the heat resistance test is 50% or less.
[11] The laminate according to any one of [1] to [10], which is used for a high-frequency circuit of 1GHz or higher.
[12] An electronic component produced using the laminate according to any one of [1] to [11 ].
Cross reference to related documents
The present invention is based on the priority claim of japanese patent application No. 2019-089122, filed 5, 9, 2019, the contents of which are incorporated by reference in the present specification.
Drawings
Fig. 1 is a diagram showing an SEM cross-sectional analysis image (fractal dimension) of one embodiment of the present invention.
Fig. 2A is a schematic diagram for explaining the shape of the convex portion in the present invention.
Fig. 2B is a diagram showing the shape of the convex portion on the lamination surface in the SEM cross-sectional analysis image according to the embodiment of the present invention.
Fig. 3 is a view showing the appearance of a test piece after a peel test according to an embodiment of the present invention.
Fig. 4 is a diagram showing transmission loss measurement results according to an embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto. However, the objects, features, advantages and concepts of the present invention will be apparent to those skilled in the art from the description of the present specification, and the present invention can be easily reproduced by those skilled in the art from the description of the present specification. The embodiments of the invention and specific examples described below are preferred embodiments of the invention, and are intended to illustrate and explain the present invention, and do not limit the present invention to these embodiments. It is obvious to those skilled in the art that various changes and modifications can be made based on the description of the present specification within the intention and scope of the present invention disclosed in the present specification.
Laminate with two layers
One embodiment of the present invention is a laminate in which a resin base material having a dielectric constant of 3.8 or less is laminated on a copper material having a plurality of fine protrusions on the surface thereof.
The copper material and the resin base material are preferably bonded. For example, when a cross section of a laminate produced by Focused Ion Beam (FIB) is observed, it is preferable that no void is detected between the copper material and the layer of the resin base material in the obtained Scanning Electron Microscope (SEM) cross-sectional image (magnification 30000 times, resolution 1024 × 768).
The copper material includes, but is not limited to, copper foil such as electrolytic copper foil or rolled copper foil, copper wire, copper plate, and copper lead frame. The copper material is a material containing 50 mass% or more of Cu, that is, a material forming a part of the structure, and may include a material covered with a copper alloy (i.e., white copper, brass, aluminum bronze, etc.) or copper (e.g., copper-plated iron), preferably a material formed of pure copper having a Cu purity of 99.9 mass% or more, more preferably formed of tough pitch copper, acid-removed copper, oxygen-free copper, and further preferably formed of oxygen-free copper having an oxygen content of 0.001 mass% to 0.0005 mass%.
The resin substrate is not particularly limited, and may contain a thermoplastic resin or a thermosetting resin, and specific examples thereof include Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC), polyvinyl acetate (PVAc), Polyamide (PA), Polyacetal (POM), Polycarbonate (PC), modified polyphenylene ether (m-PPE), polyphenylene ether containing a polystyrene polymer, a polymer or copolymer of triallyl cyanurate, a phenol-added butadiene polymer, diallyl phthalate, divinylbenzene, polyfunctional methacryloyl, an unsaturated polyester, polybutadiene, styrene-butadiene, a crosslinked polymer of styrene-butadiene/styrene-butadiene, Bismaleimide Triazine (BT), polyethylene terephthalate (PET), glass fiber-reinforced polyethylene terephthalate (GF-PET), and the like, Polybutylene terephthalate (PBT), cyclic polyolefin (COP), polyphenylene sulfide (PPS), Polytetrafluoroethylene (PTFE), Polysulfone (PSF), Polyethersulfone (PES), amorphous Polyarylate (PAR), Liquid Crystal Polymer (LCP) (e.g., a polycondensate comprising p-hydroxybenzoic acid and ethylene terephthalate; a polycondensate of p-hydroxybenzoic acid, phenol, and phthalic acid; a polycondensate of p-hydroxybenzoic acid and 2, 6-hydroxynaphthoic acid, etc.), Polyetheretherketone (PEEK), thermoplastic Polyimide (PI), Polyamideimide (PAI), and mixtures thereof.
The resin substrate may further contain an inorganic filler and glass fibers.
The dielectric constant of such a resin substrate can be measured by a known Method, for example, according to The IPC (American society for Electronic Circuit interconnection and Packaging) Test Method) 6502.5.5.5 or IPC (International patent publication) TM-6502.5.5.9. An example of the resin substrate includes MEGTRON6 (manufactured by Panasonic corporation; dielectric constant 3.71(1GHz)) composed of20 to 70 wt% of polyphenylene ether (PPE), 0 to 20 wt% of silica, and 30 to 70 wt% of glass fiber.
The laminated surface of the resin base material and the metal layer preferably has a plurality of fine protrusions. The shape of the convex portion may be defined as a fractal dimension or an inscribed circle radius of a tip portion of the convex portion. The fractal dimension can be calculated as a fractal dimension of a curve appearing on the lamination surface in a cross-sectional image made by a Focused Ion Beam (FIB) using a Scanning Electron Microscope (SEM). For example, the fractal dimension may be calculated by a box counting method, but the calculation method is not limited thereto. The radius of the inscribed circle of the tip of the convex portion can be calculated by measuring the convex portion in a cross-sectional image created by a Focused Ion Beam (FIB) using a Scanning Electron Microscope (SEM).
The fractal dimension is an index indicating the complexity of a pattern, the degree of surface unevenness, and the like, and the larger the value of the fractal dimension, the more complicated the surface unevenness is. For example, the fractal dimension using the box counting method is defined as follows:
for a certain pattern F, when the number of boxes required to be covered with a square box having a side length δ is N δ (F), the fractal dimension is defined by the following equation.
In the present invention, the cross section of the laminate is divided by a lattice of equal intervals δ, and the number of boxes (i.e., squares that can be divided into lattices) including a curve appearing on the laminate surface is counted for a plurality of δ. Next, a log-log graph is drawn with the size of δ as the horizontal axis and the number of boxes counted for each δ as the vertical axis, and the fractal dimension can be determined from the slope of the graph.
More specifically, the obtained outline of the fine projection is pasted to a sheet having a resolution of 256, 128, 64, 32, 16, or 8 pixels from an SEM cross-sectional image (magnification of 30000 times, resolution of 1024 × 768), and the number of pixels including the outline is counted. Taking the logarithm value of the pixel size as a vertical axis, taking the logarithm of the pixel number as a horizontal axis, drawing the pixel number obtained by counting according to the pixel size to form an approximate straight line, and calculating the value of the fractal dimension according to the slope of the approximate straight line.
The value of the fractal dimension of the curve developed on the lamination surface is 1.250 or more or a value of more than 1.250, or preferably 1.300 or more or a value of more than 1.300, more preferably 1.350 or more than 1.350, and still more preferably 1.400 or more than 1.400.
In one embodiment of the present invention, the surface of the copper material may contain a copper oxide layer containing copper (I) oxide and/or copper (II) oxide. Such a copper oxide layer can be formed by oxidation treatment, oxidation dissolution treatment, oxidation reduction treatment, and oxidation dissolution reduction treatment.
The oxidation treatment includes a step of converting pure copper into copper (II) oxide by using an oxidizing agent.
The dissolution treatment includes a step of dissolving the copper (II) oxide oxidized by the oxidation treatment with a dissolution agent.
The reduction treatment includes a step of reducing the copper (II) oxide oxidized by the oxidation treatment to copper (I) oxide or pure copper by a reducing agent.
The oxidation treatment, the dissolution treatment, and the reduction treatment may include a step of forming fine protrusions (i.e., fine burrs) on the surface of the copper material and a step of adjusting the shape or number of the fine protrusions. The plurality of fine protrusions on the lamination surface of the resin substrate and the metal layer may be formed by fine protrusions formed by these processes.
A metal layer other than copper may be formed on at least a part of the surface of the copper material. In the case of forming the copper oxide layer, the metal layer is preferably formed on at least a part of the surface of the copper oxide layer, and a resin base material having a dielectric constant of 3.8 or less is laminated on at least a part of the surface of the metal layer. The kind of metal constituting the metal layer is not particularly limited, and is preferably at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, and Pt. In particular, in order to have heat resistance, metals having heat resistance higher than that of copper, such as Ni, Pd, Au, and Pt, are preferable.
The average thickness of the metal layer in the vertical direction is not particularly limited, but is preferably 6nm or more, and more preferably 10nm or more, 14nm or more, 18nm or more, or 20nm or more. However, when the thickness is too large, fine protrusions on the surface of the copper clad material are smoothed by leveling, and the fractal dimension becomes small, and the adhesion force is lowered, and therefore, it is preferably 150nm or less, and more preferably 100nm or less or 75nm or less.
As a method for measuring the thickness, for example, the thickness of the layered metal layer can be calculated by measuring the concentration of the metal component in the obtained solution using ICP emission analyzer 5100SVDV ICP-OES (manufactured by Agilent Technologies corporation) and taking into consideration the density of the metal and the surface area of the metal layer.
The metal layer can also be formed on the surface of the copper material by plating. The plating method is not particularly limited, and examples thereof include electroplating, electroless plating, vacuum evaporation, and chemical surface treatment, and electroplating is preferred.
In one embodiment of the present invention, in an SEM sectional image of the laminate, the height of the convex portion of the curve appearing on the laminate surface is preferably 10nm or more, more preferably 50nm or more, further preferably 100nm or more, further preferably 1000nm or less, more preferably 500nm or less, further preferably 200nm or less, on average. The height of the convex portion may be, for example, a distance between a midpoint of a line segment connecting minimum points of adjacent concave portions with the convex portion interposed therebetween and a maximum point of the convex portion located between the concave portions in the SEM cross-sectional image.
In one embodiment of the present invention, in the SEM sectional image of the laminate, the number of projections having a height of 50nm or more of a curve appearing on the laminate surface may be 25, 30, or 35 or more on average per 3.78 μm of the sectional width. Alternatively, the projections having a height of 100nm or more have an average of 6, 10, or 12 or more per 3.78 μm cross-sectional width. Alternatively, the number of projections having a height of 150nm or more is 2 or 3 or more per 3.78 μm of cross-sectional width.
The larger the height of the convex portion is, the larger the mechanical adhesion by the anchor effect is, and therefore, from the viewpoint of peel strength, the preferable effect is, but the influence of the skin effect phenomenon becomes large. The skin effect is a phenomenon in which a current flowing in a conductor concentrates on the surface of the conductor as the frequency increases, and the current density inside decreases. The thickness of the skin portion (skin depth) through which the current flows is inversely proportional to the square root of the frequency. When a high-frequency signal having a GHz band is transmitted through a conductor circuit by utilizing the skin effect phenomenon, the skin depth is about 2 μm or less, and a current flows only in the outermost layer of the conductor. Therefore, in a high-frequency circuit, when the convex portion on the surface of the copper material is large, the transmission path of the conductor formed of the copper material becomes long due to the influence of the skin effect phenomenon, and the transmission loss increases. Therefore, it is desirable that the surface of the copper material used for the high-frequency circuit has small projections, but when it is too small, sufficient peel strength cannot be obtained, and the projections are preferably of the above-mentioned degree.
In the present specification, the inscribed circle radius of the tip portion of the convex portion can be used as an index of the thickness of the convex portion. The inscribed circle radius of the tip portion of the fine convex portion here is defined as: in the SEM sectional image, 3 points, i.e., the maximum point a of the convex portion having the height of 10nm or more, and the intersection points b and c between the straight line parallel to the tangent of the maximum point a of the convex portion and the outer peripheral portion of the convex portion and having a distance of 10nm, are the radii of the outer periphery circle (fig. 2A). The larger the radius of the inscribed circle is, the thicker the front end part of the convex part is; the smaller the radius of the inscribed circle, the thinner the tip of the convex part.
In one embodiment of the present invention, when the resin base material and the copper clad material are peeled off, at least a part of the peel surface on the copper clad material side preferably has an aggregation failure mode. The cohesive failure is a state in which resin adheres to about half or more of the area of the copper side of the peeled surface.
In one embodiment of the present invention, the deterioration rate in the heat resistance test of the laminate may be 50% or less, preferably 40% or less, 30% or less, or 20% or less. The deterioration rate in the heat resistance test can be measured by a known method. This can be expressed, for example, as: the peel strength before and after the heat resistance test was measured, and the difference in peel strength was divided by the peel strength before the heat resistance test. The heat resistance test can be carried out, for example, according to the IPC TM-6502.4.8 standard.
Method for manufacturing laminate
One embodiment of the present invention is a method for manufacturing a laminate, including: a first step of forming a convex portion on the surface of a copper material; and a third step of heating and adhering the resin base material to the copper surface having the convex portion formed thereon or the surface after the plating treatment. The manufacturing method may include a second step of performing plating treatment on the copper surface on which the convex portion is formed, after the first step.
First, in the first step, the copper surface is oxidized with an oxidizing agent to form a copper oxide layer, and a convex portion is formed on the surface. The oxidation step may be performed without a roughening step such as etching. An alkali treatment for preventing mixing of an acid in the degreasing cleaning or the oxidation step can be performed. The method of alkali treatment is not particularly limited, and the treatment may be carried out at 30 to 50 ℃ for about 0.5 to 2 minutes by using an alkali aqueous solution, for example, an aqueous sodium hydroxide solution, preferably 0.1 to 10g/L, more preferably 1 to 2 g/L.
The oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, or the like can be used. Various additives (for example, phosphate such as trisodium phosphate dodecahydrate) and surface active molecules may be added to the oxidizing agent. Examples of the surface active molecule include porphyrin, porphyrin macrocycle, expanded porphyrin, cyclopropyrin, linear porphyrin polymer, porphyrin sandwich complex, porphyrin array, silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl) trimethoxysilane, 1- [ 3- (Trimethoxysilyl) propyl ] urea (l- [ 3- (Trimethoxysilyl) propyl ] urea, (3-aminopropyl) triethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, dimethyldichlorosilane, 3- (Trimethoxysilyl) propyl methacrylate, ethyltriacetoxysilane, triethoxy (isobutyl) silane, and the like, Triethoxy (octyl) silane, tris (2-methoxyethoxy) (vinyl) silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, vinyl-trimethoxysilane, amines, sugars, and the like.
The oxidation reaction conditions are not particularly limited, and the liquid temperature of the oxidizing agent is preferably 40 to 95 ℃, and more preferably 45 to 80 ℃. The reaction time is preferably 0.5 to 30 minutes, and more preferably 1 to 10 minutes.
In the first step, the surface of the oxidized copper material may be dissolved with a dissolving agent to adjust the irregularities on the surface of the oxidized copper material.
The dissolving agent used in the present step is not particularly limited, and is preferably a chelating agent, particularly a biodegradable chelating agent, and examples thereof include ethylenediaminetetraacetic acid, diethoglycine, tetrasodium L-glutamic diacetate, ethylenediamine-N, N '-disuccinic acid, sodium 3-hydroxy-2, 2' -iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N- (2-hydroxyethyl) iminodiacetate, and sodium gluconate.
The pH of the dissolving agent is not particularly limited, but is preferably alkaline, more preferably 8 to 10.5, still more preferably 9.0 to 10.5, and yet more preferably 9.8 to 10.2.
In the first step, the copper oxide layer formed on the copper material may be reduced using a chemical solution containing a reducing agent (a chemical solution for reduction), and the number and height of the projections may be adjusted.
As the reducing agent, DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine, or the like can be used. The chemical solution for reduction is a liquid containing a reducing agent, a basic compound (sodium hydroxide, potassium hydroxide, etc.) and a solvent (pure water, etc.).
In the second step, the copper oxide layer having the convex portion is subjected to plating treatment with a metal other than copper, thereby producing a copper clad material. The plating method may use a known technique, and for example, Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, Pt, or various alloys may be used as the metal other than copper. The plating step is also not particularly limited, and plating may be performed by electroplating, electroless plating, vacuum evaporation, chemical surface treatment, or the like.
In the electroless nickel plating, treatment using a catalyst is preferably performed. As the catalyst, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and salts thereof are preferably used. By performing the treatment using the catalyst, a metal layer which is uniform and in which particles do not exist in a dot shape can be obtained. This improves the heat resistance of the composite copper foil. In the electroless nickel plating, a reducing agent having no catalytic activity for copper and copper oxide is preferably used as the reducing agent. Examples of the reducing agent having no catalytic activity for copper and copper oxide include hypophosphite such as sodium hypophosphite.
The composite copper material produced in these steps may be subjected to coupling treatment with a silane coupling agent or the like, or to rust prevention treatment with a benzotriazole or the like, as desired.
As a third step, a resin base material is laminated on the copper oxide layer having the convex portion formed in the first step or the plated layer of the copper material plated in the second step, thereby producing a laminate. The method for producing the laminate is not particularly limited, and can be carried out by a known method such as vacuum thermocompression bonding using a vacuum press. The pressing pressure, temperature and pressing time are appropriately changed depending on the resin base material used. For example, recommend: when the resin base material comprises PPE resin MEGTRON6(Panasonic Co., Ltd.), the resin base material is thermally pressed at 0.49MPa to 110 ℃ while being heated, and then thermally pressed at 2.94MPa at 210 ℃ for 120 minutes; in the case of NX9255(Park Electrochemical corporation) containing a PTFE resin, thermocompression bonding is performed at 0.69MPa while heating to 260 ℃, followed by thermocompression bonding at 1.03MPa to 1.72MPa while heating to 385 ℃, and thermocompression bonding is performed at 385 ℃ for 10 minutes, but the present invention is not limited thereto.
A resin substrate for a high-frequency circuit having a dielectric constant of 3.8 or less tends to have a higher pressing temperature than a resin substrate for a circuit board having a dielectric constant of more than 3.8 (for example, FR-4), and thus the fine irregularities are more likely to be changed. Copper is affected by heat, and the effect is greater as the irregularities are finer. This is because, even when the change is caused by the same level of heat, the smaller the subject to be influenced is, the greater the degree of influence thereof is. For example, in the case of fine irregularities, the irregularities are damaged after pressing, and sufficient peel strength may not be exhibited. Therefore, the uneven portion is required to have an uneven shape which can withstand the temperature at the time of pressing and can exhibit sufficient peel strength even after lamination.
In this way, by performing steps 1 to 3 on the copper material, a novel laminate of the copper material and the resin base material can be produced. The copper material used for the laminate may be formed into a wiring pattern by a known method (e.g., etching).
The laminate according to the present invention can be used for the production of a printed wiring board, or can be used for the production of electronic components including a printed wiring board and electronic components.
The printed wiring board produced by using the laminate is particularly suitable as a substrate for a high frequency band having a signal frequency of 1GHz or higher.
In addition, since the laminate has irregularities on the lamination surface, the laminate has excellent adhesion and is also suitable for use in flexible substrates.
Examples
< 1. production of laminate
In examples 1 and 2 and comparative examples 1 and 2, DR-WS (manufactured by Kogaku corporation, thickness: 18 μm) was used as a copper foil.
(1) Pretreatment of
[ alkali degreasing treatment ]
The copper foil was immersed in a 40g/L aqueous solution of sodium hydroxide at a liquid temperature of 50 ℃ for 1 minute, and then washed with water.
[ acid cleaning treatment ]
The copper foil after the alkali degreasing treatment was immersed in a 10 wt% sulfuric acid aqueous solution at a liquid temperature of 25 ℃ for 2 minutes, and then washed with water.
[ Pre-impregnation treatment ]
The pretreatment was carried out in a 1.2g/L aqueous solution of sodium hydroxide at 40 ℃ for 1 minute. This is for degreasing and cleaning for the purpose of reducing the unevenness of the oxidation treatment.
(2) Oxidation treatment
Subjecting the copper foil subjected to alkali treatment to oxidation treatment with an aqueous solution (NaClO)2130 g/L; NaOH 12g/L) was subjected to oxidation treatment at 45 ℃ for 1 minute. After these treatments, the copper foil was washed with water. Comparative examples 1 and 2 were subjected to oxidation treatment, followed by reduction treatment by immersing in a reducing agent (dimethylamine borane 5 g/L; sodium hydroxide 5g/L) at room temperature for 1 minute.
(3) Plating treatment
In examples 1 and 2, the plain surface (glossy surface, flat surface when compared with the reverse surface) of the copper foil subjected to the oxidation treatment was plated with an electrolytic solution for nickel plating (nickel sulfamate 470 g/L-boric acid 40 g/L). The conditions were 50 degrees and the current density was 0.5A/dm2X 30 seconds (═ 15C/dm)2Unit copper foil area).
(4) Thermocompression bonding of resin base material
In example 1 and comparative example 1, a MEGTRON6 (prepreg R5670KJ, manufactured by Panasonic corporation, dielectric constant 3.71(1GHz), thickness 100 μm) was laminated on each copper foil, and thermocompression bonding was performed using a vacuum high-pressure press under conditions of a pressing pressure of 2.9MPa, a temperature of 210 ℃, and a pressing time of 120 minutes, thereby obtaining a laminate.
In example 2 and comparative example 2, a PTFE substrate (NX9255, manufactured by Park Electrochemical, dielectric constant 2.55(10GHz), thickness 0.762mm) was laminated on each copper foil, and thermocompression bonding was performed using a vacuum high-pressure press under conditions of a pressing pressure of 1.5MPa, a temperature of 385 ℃, and a pressing time of 10 minutes, thereby obtaining a laminate.
In the examples and comparative examples, a plurality of test pieces were prepared under the same conditions.
SEM Cross-sectional image analysis
1. Method of producing a composite material
The cross section of the obtained laminate (examples 1 and 2; comparative examples 1 and 2) was obtained by FIB (focused ion beam) processing under conditions of an acceleration voltage of 30kV and a probe current of 4 nA. The obtained cross section was observed with a focused ion beam scanning electron microscope (Auriga, manufactured by Carl Zeiss) at a magnification of 30000 times and a resolution of 1024 × 768 to obtain an SEM cross-sectional image. The obtained SEM sectional image is shown in fig. 1. Based on the image of the cross section, a value of fractal dimension, a measurement of height of the convex portion, and a measurement of inscribed circle radius of the tip of the convex portion were performed. The height of the convex portion and the radius of the inscribed circle at the tip of the convex portion were measured using image analysis software WinROOF2018 (mitsubishi ltd., ver4.5.5). Fig. 2B shows an example of measuring the radius of the inscribed circle of the tip of the projection.
2. Results
The results are shown in tables 1 to 3 below.
[ Table 1]
[ Table 2]
[ Table 3]
< 3. measurement of peeling Strength >
1. Method of producing a composite material
With respect to the laminates of examples 1 and 2 and comparative examples 1 and 2, the peel strength was measured based on a 90 ° peel test (japanese industrial standard (JIS) C5016).
2. Results
The results are shown in Table 4.
In the comparative examples, the peel strength was low and the failure mode was also interfacial or partial interfacial, as compared with the examples, which were resin aggregation failures. As described above, the laminate according to the present invention has a higher peel strength than the comparative example.
[ Table 4]
< 4. measurement of Heat resistance >
1. Method of producing a composite material
The laminates of example 1 and comparative example 1 were measured for peel strength before and after the heat resistance test. After baking at 125 ℃ for 4 hours, the steel sheet was floated in a solder bath at 288 ℃ for 10 seconds, whereby a heat resistance test (according to IPC. TM. -6502.4.8) was conducted. The difference in peel strength before and after the heat resistance test was divided by the peel strength before the heat resistance test to calculate the ratio.
2. Results
The results are shown in table 5 and fig. 3.
When the conventional state and the peel strength after the heat resistance test were compared, 53% deterioration occurred in comparative example 1, but only 19% deterioration occurred in example 1 (table 5). In addition, after the heat resistance test, it was confirmed that the copper material of the comparative example was discolored (highlighted by a red line in fig. 3). This is because the irregularities on the surface of the copper material are dissolved by the heat resistance test. As described above, the laminate according to the present invention is superior to the comparative examples in peel strength and heat resistance.
[ Table 5]
< 4. high frequency characteristics >
1. Method of producing a composite material
As example 1 and comparative example 3, MEGTRON6 (prepreg R5670KJ, manufactured by Panasonic corporation, 100 μm in thickness) as a resin base material was laminated on a copper foil FV-WS (manufactured by Kogawa electric Co., Ltd., 18 μm in thickness, Rz: 1.2 μm) by hot press molding, and then samples for transmission characteristic measurement were prepared, and transmission loss in a high frequency band was measured. The transmission characteristics were evaluated by a known stripline resonator method suitable for the measurement of the 0 to 50GHz band. Specifically, the S21 parameter was measured in a state without a coating film under the following conditions.
The measurement conditions were as follows: a microwave transmission band structure; substrate MEGTRON 6; the circuit length is 150 mm; the width of the conductor is 250 mu m; the thickness of the conductor is 18 μm; the thickness of the base material is 100 mu m; the characteristic impedance is 50 omega.
2. Results
The results are shown in FIG. 4.
The copper foil FV-WS used in comparative example 3 is a copper foil for a high-frequency substrate, which has low roughness and is required to have low transmission loss in the face of an antenna substrate for an information communication device or a communication base station, such as a high-end router or server, and the transmission loss in example 1 is smaller than that in comparative example 3. Thus, the laminate according to the present invention has excellent high-frequency characteristics.
Industrial applicability
The present invention can provide a novel laminate of a copper material and a resin base material.
Claims (12)
1. A laminate characterized by:
a resin base material having a dielectric constant of 3.8 or less is laminated on at least a part of the surface of a copper material having a plurality of fine protrusions on the surface,
the fractal dimension of the laminated surface of the copper material and the resin base material is more than 1.25.
2. The laminate according to claim 1, wherein:
the fractal dimension of the lamination surface is more than 1.4.
3. The laminate according to claim 1 or 2, wherein:
at least a portion of the surface of the copper material comprises a copper oxide layer.
4. The laminate according to claim 1 or 2, wherein:
at least a part of the surface of the copper material is formed of a metal layer other than copper, and the metal other than copper is at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, and Pt.
5. The laminate according to claim 4, wherein:
the average thickness of the metal layer other than copper in the vertical direction is 10nm to 150 nm.
6. The laminate according to any one of claims 1 to 5, wherein:
in a vertical cross section of the laminate, the height of the projection is 50nm or more and 500nm or less on average.
7. The laminate according to claim 6, wherein:
in the vertical cross section of the laminate, 30 or more of the projections are provided on average per 3.78 μm cross-sectional width.
8. The laminate according to any one of claims 1 to 7, wherein:
the resin substrate contains polyphenylene ether, polytetrafluoroethylene, or a liquid crystal polymer containing p-hydroxybenzoic acid.
9. The laminate of claim 8, wherein:
when the resin base material is peeled from the copper material, the peeling mode is cohesive failure.
10. The laminate of claim 9, wherein:
the deterioration rate in the heat resistance test is 50% or less.
11. The laminate according to any one of claims 1 to 10, wherein:
it is used for high frequency circuits above 1 GHz.
12. An electronic component produced by using the laminate according to any one of claims 1 to 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019089122A JP7328671B2 (en) | 2019-05-09 | 2019-05-09 | laminate |
| JP2019-089122 | 2019-05-09 | ||
| PCT/JP2020/018582 WO2020226162A1 (en) | 2019-05-09 | 2020-05-07 | Laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113677519A true CN113677519A (en) | 2021-11-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080027107.9A Pending CN113677519A (en) | 2019-05-09 | 2020-05-07 | Laminate |
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| Country | Link |
|---|---|
| JP (1) | JP7328671B2 (en) |
| KR (1) | KR20220007038A (en) |
| CN (1) | CN113677519A (en) |
| TW (1) | TW202043034A (en) |
| WO (1) | WO2020226162A1 (en) |
Citations (5)
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|---|---|---|---|---|
| CN101687390A (en) * | 2007-06-27 | 2010-03-31 | 富士胶片株式会社 | L layer laminate with metal surface roughened layer and process for producing the same |
| TW201352094A (en) * | 2012-05-10 | 2013-12-16 | Hitachi Chemical Co Ltd | Multilayer wiring board |
| US20140204546A1 (en) * | 2013-01-19 | 2014-07-24 | International Business Machines Corporation | PCB stackup having high- and low-frequency conductive layers and having insulating layers of different material types |
| CN104943270A (en) * | 2014-03-31 | 2015-09-30 | Jx日矿日石金属株式会社 | Copper foil with carrier, printed wiring board, laminate, electronic machine and method for manufacturing printed wiring board |
| CN107923047A (en) * | 2015-07-29 | 2018-04-17 | 三井金属矿业株式会社 | Roughening processing copper foil, copper-clad laminated board and printed circuit board (PCB) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10144944A (en) * | 1996-09-12 | 1998-05-29 | Canon Inc | Photovoltaic device |
| JP4528204B2 (en) * | 2005-05-31 | 2010-08-18 | 日立ビアメカニクス株式会社 | Method for manufacturing printed wiring board |
| JP2008173967A (en) * | 2006-12-18 | 2008-07-31 | Taisei Plas Co Ltd | Composite of metal and resin, and its manufacturing method |
| US20100159196A1 (en) * | 2007-04-06 | 2010-06-24 | Taisei Plas Co., Ltd. | Copper alloy composite and method for manufacturing same |
| EP3438166B1 (en) * | 2016-03-30 | 2021-12-15 | Asahi Kasei Kabushiki Kaisha | Resin composite film including cellulose microfiber layer |
-
2019
- 2019-05-09 JP JP2019089122A patent/JP7328671B2/en active Active
-
2020
- 2020-03-24 TW TW109109836A patent/TW202043034A/en unknown
- 2020-05-07 KR KR1020217026954A patent/KR20220007038A/en unknown
- 2020-05-07 WO PCT/JP2020/018582 patent/WO2020226162A1/en active Application Filing
- 2020-05-07 CN CN202080027107.9A patent/CN113677519A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687390A (en) * | 2007-06-27 | 2010-03-31 | 富士胶片株式会社 | L layer laminate with metal surface roughened layer and process for producing the same |
| TW201352094A (en) * | 2012-05-10 | 2013-12-16 | Hitachi Chemical Co Ltd | Multilayer wiring board |
| US20140204546A1 (en) * | 2013-01-19 | 2014-07-24 | International Business Machines Corporation | PCB stackup having high- and low-frequency conductive layers and having insulating layers of different material types |
| CN104943270A (en) * | 2014-03-31 | 2015-09-30 | Jx日矿日石金属株式会社 | Copper foil with carrier, printed wiring board, laminate, electronic machine and method for manufacturing printed wiring board |
| CN107923047A (en) * | 2015-07-29 | 2018-04-17 | 三井金属矿业株式会社 | Roughening processing copper foil, copper-clad laminated board and printed circuit board (PCB) |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202043034A (en) | 2020-12-01 |
| JP7328671B2 (en) | 2023-08-17 |
| WO2020226162A1 (en) | 2020-11-12 |
| KR20220007038A (en) | 2022-01-18 |
| JP2020183085A (en) | 2020-11-12 |
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