CN110278654A - 层叠板 - Google Patents
层叠板 Download PDFInfo
- Publication number
- CN110278654A CN110278654A CN201910192433.4A CN201910192433A CN110278654A CN 110278654 A CN110278654 A CN 110278654A CN 201910192433 A CN201910192433 A CN 201910192433A CN 110278654 A CN110278654 A CN 110278654A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- insulating substrate
- plywood
- fluororesin
- alkoxy silane
- 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.)
- Granted
Links
- 239000011120 plywood Substances 0.000 title claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 80
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 68
- 229910000077 silane Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims description 32
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 32
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000000034 method Methods 0.000 description 35
- 238000001069 Raman spectroscopy Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- SQYDLDODGFFDLT-UHFFFAOYSA-N [Ru].CO[SiH](OC)OC Chemical compound [Ru].CO[SiH](OC)OC SQYDLDODGFFDLT-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052839 forsterite Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QOTGGUKPKRQHKS-UHFFFAOYSA-N C(C)O[SiH](OCC)OCC.[Ru] Chemical compound C(C)O[SiH](OCC)OCC.[Ru] QOTGGUKPKRQHKS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- VLWUKSRKUMIQAX-UHFFFAOYSA-N diethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[SiH](OCC)CCCOCC1CO1 VLWUKSRKUMIQAX-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- PGVSPORIGRCPMG-UHFFFAOYSA-N triethoxy(1-triethoxysilylhexyl)silane Chemical class CCCCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC PGVSPORIGRCPMG-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-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
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- VDUCVVHTKMKFTL-UHFFFAOYSA-N CCCCCCCCC(CCCCC)([Si](OC)(OC)OC)[Si](OC)(OC)OC Chemical class CCCCCCCCC(CCCCC)([Si](OC)(OC)OC)[Si](OC)(OC)OC VDUCVVHTKMKFTL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NFCHYERDRQUCGJ-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[SiH](OC)CCCOCC1CO1 NFCHYERDRQUCGJ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- XCMFHUYZTPVWAY-UHFFFAOYSA-N methyl-tris(methylperoxy)silane Chemical compound C[Si](OOC)(OOC)OOC XCMFHUYZTPVWAY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
-
- 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
- B32B15/046—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 foam
-
- 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
- B32B15/04—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
- B32B15/085—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 comprising polyolefins
-
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Abstract
提供一种即使在高湿环境下长时间使用时介电损耗角正切也难以发生变化、且高频特性也优异的层叠板。该层叠板为在绝缘基板的一个面或两个面上层叠有金属制导体层的层叠板，特征在于：该绝缘基板含有烷氧基硅烷的聚合物以及氟树脂，且该氟树脂分散在该烷氧基硅烷的聚合物中。
Description
技术领域
本发明涉及用于高频基板等的层叠板。
背景技术
作为高频用的电子部件材料，由于介电损耗角正切低、低相对介电常数等原因，广泛地使用了氟树脂。
例如，作为高频基板，广泛已知有在包含氟树脂的预浸料(绝缘基板)上层叠有金属箔的印刷线路板(例如参照专利文献1)。
[现有技术文献]
[专利文献]
[专利文献1]国际公开第2001/003478号
[专利文献2]日本特开平10-226009号公报
发明内容
[发明所要解决的课题]
另一方面，氟树脂的成形体在内部具有许多微细的空隙。因此，在具备包含诸如专利文献1所示的那种氟树脂的绝缘基板的高频基板中，水分有时会进入到绝缘基板的空隙中。若水分侵入上述绝缘基板中，则该水分的侵入会使介电损耗角正切发生变化，可能会使上述高频基板的线路损失增加。
另外，专利文献2提出：作为将耐湿性赋予至印刷线路板、并防止压力蒸煮试验后的剥离强度劣化的技术，使用了在铜箔的被粘接面上具有由硅烷偶联剂及聚硅氧烷构成的混合物被覆层的印刷线路板用铜箔。然而，在专利文献2的技术中，无法充分地防止水分侵入至包含氟树脂的绝缘基板的内部，作为具备包含氟树脂的绝缘基板的高频基板，需要更难以吸水、介电损耗角正切难以发生变化的高频基板。
本发明人基于这样的需要而进行深入研究并完成了本发明。
[用于解决课题的手段]
本发明的层叠板是在绝缘基板的一个面或两个面上层叠有金属制的导体层的层叠板，其特征在于：上述绝缘基板含有烷氧基硅烷的聚合物以及氟树脂、且上述氟树脂分散在上述烷氧基硅烷的聚合物中。
由于构成上述层叠板的绝缘基板含有烷氧基硅烷的聚合物以及氟树脂、且上述氟树脂分散在上述烷氧基硅烷的聚合物中，因而微细的空隙极少(或者不存在微细的空隙)，难以发生水分侵入到空隙内的吸水。因此，难以发生由上述吸水所引起的介电损耗角正切的变化，即使在高湿环境下使用时也能够长时间地保持优异的高频特性。
在上述层叠板中，上述烷氧基硅烷为烷基三烷氧基硅烷，上述烷基三烷氧基硅烷所具有的烷基的碳原子数优选为3至9。
在这种情况下，具有碳原子数为3至9的烷基的烷基三烷氧基硅烷的聚合物的疏水性特别优异，上述层叠板成为更难以吸水的层叠板。
在上述层叠板中，上述氟树脂优选为聚四氟乙烯(PTFE)。
由于在氟树脂当中，聚四氟乙烯是在成形体的内部容易产生微小空隙的氟树脂，因而在本发明的绝缘基板中，特别适合用作与上述烷氧基硅烷的聚合物组合使用的氟树脂。
在上述层叠板中，上述绝缘基板优选进一步含有无机填料。
通过将无机填料混合到上述绝缘基板中，从而能够调整相对介电常数。
此外，通过混合上述无机填料，从而能够减小绝缘基板的线膨胀系数。
另外，上述层叠板通过含有烷氧基硅烷的聚合物，从而也能够抑制由上述无机填料所引起的吸水。
在上述层叠板中，上述绝缘基板的空隙率优选为5％以下。
若上述绝缘基板的空隙率为5％以下，则能够显著地抑制在高湿环境下长时间使用上述层叠板的情况下的介电损耗角正切的增加。
[发明的效果]
本发明的层叠板由于具备上述构成，因而即使在高湿环境下长时间使用时，介电损耗角正切也难以发生变化，且高频特性也优异。
附图简要说明
[图1]为示意性示出了根据本发明实施方式的层叠板的一个例子的截面图。
[图2]为实施例1中所测定的拉曼曲线图。
[图3](a)和(b)为实施例1中所拍摄的电子显微镜照片，(b)为将(a)放大显示的图。
[图4]为实施例1中所拍摄的扫描电子显微镜的反射电子图像。
[图5]为比较例1中所拍摄的扫描电子显微镜的反射电子图像。
符号说明
10：层叠板、11：绝缘基板、12：导体层
具体实施方式
以下，对于本发明的实施方式，参照附图来进行说明。
(第1实施方式)
图1为示意性示出了根据本发明实施方式的层叠板的一个例子的截面图。
如图1所示，根据本实施方式的层叠板10由绝缘基板11以及设置在其两个面上的导体层12(12A、12B)构成。如后所述，绝缘基板11是通过将凝胶层彼此热压接而形成的层，凝胶层固化而得的层11A、11B成为一体。
绝缘基板11含有烷氧基硅烷的聚合物、氟树脂以及无机填料。
作为上述氟树脂，例如可列举出：聚四氟乙烯(PTFE)、全氟烷氧基烷烃(PFA)、全氟乙烯-丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物(ETFE)、四氟乙烯-全氟二氧杂环戊烯共聚物(TFE/PDD)、聚偏二氟乙烯(PVDF)、聚三氟氯乙烯(PCTFE)、乙烯-三氟氯乙烯共聚物(ECTFE)、聚氟乙烯(PVF)等。它们可以单独使用，也可以两种以上组合使用。
上述氟树脂可以是直链状的，也可以具有支链，从与烷氧基硅烷的聚合物的相容性优异的观点考虑，优选为直链状的。
作为上述氟树脂，更优选为聚四氟乙烯(PTFE)。
作为烷氧基硅烷，使用了具有在硅原子上直接键结有3个烷氧基而成的三烷氧基甲硅烷基的化合物。作为上述烷氧基硅烷，除了具有三烷氧基甲硅烷基的化合物以外，也可以组合使用具有在硅原子上直接键结有2个烷氧基而成的二烷氧基甲硅烷基的化合物。
作为上述具有三烷氧基甲硅烷基的化合物的具体例子，例如可列举出：甲基三甲氧基硅烷、乙基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、苯基三乙氧基硅烷、正丙基三甲氧基硅烷、正丙基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、辛基三乙氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、1,6-双(三甲氧基甲硅烷基)己烷、1,6-双(三乙氧基甲硅烷基)己烷、三氟丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷、对-苯乙烯基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基-亚丁基)丙胺、N-苯基-3-氨基丙基三甲氧基硅烷、N-(乙烯基苄基)-2-氨基乙基-3-氨基丙基三甲氧基硅烷的盐酸盐、三-(三甲氧基甲硅烷基丙基)异氰脲酸酯、(十三氟-1,1,2,2-四氢辛基)三乙氧基硅烷、(十七氟-1,1,2,2-四氢癸基)三乙氧基硅烷等。它们可以单独使用，也可以两种以上组合使用。
作为上述具有二烷氧基甲硅烷基的化合物，例如可列举出：3-缩水甘油氧基丙基甲基二甲氧基硅烷、3-缩水甘油氧基丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷等。它们可以单独使用，也可以两种以上组合使用。
作为上述烷氧基硅烷，优选为烷基三烷氧基硅烷。
关于上述烷基三烷氧基硅烷所具有的烷基，碳原子数为3以上的烷基是优选的，碳原子数为5至9的烷基是更优选的。
在这种情况下，特别适合于对绝缘基板赋予疏水性并抑制绝缘基板的吸水性。
相对于100重量份的上述氟树脂，上述烷氧基硅烷的聚合物的含量优选为0.3至4.0重量份。在这种情况下，适合于构成以上述烷氧基硅烷的聚合物为海、并以上述氟树脂为岛的海岛结构。
另外，以上述烷氧基硅烷的聚合物为海并且以上述氟树脂为岛的海岛结构适合于作为使上述绝缘基板的空隙率减少的结构。
作为上述无机填料的材质，例如可列举出：由BaTi14O9、BaTi5O11、Ba2Ti9O20表示的钛酸钡；由TiO2表示的二氧化钛；Mg2SiO4(镁橄榄石)；由非晶态二氧化硅、晶态二氧化硅、石英、合成二氧化硅等SiO2表示的无机物等。它们可以单独使用，也可以两种以上组合使用。
通过混合这些无机填料，从而能够减小上述绝缘基板的线膨胀系数的绝对值。因此，能够抑制由上述绝缘基板的温度变化所引起的变形。
对于构成本发明实施方式所涉及的层叠板的绝缘基板而言，重要的是对应于用途及尺寸来调整相对介电常数。另一方面，对于烷氧基硅烷的聚合物及氟树脂的各自的相对介电常数而言，即使结构不同也变化不大。
因此，上述绝缘基板的相对介电常数的调整优选通过选择上述无机填料来进行。
例如，在上述绝缘基板含有上述无机填料的情况下，考虑到由钛酸钡、二氧化钛、镁橄榄石构成的无机填料当中的任一者均为相对介电常数超过8的无机填料，以及由非晶态二氧化硅、晶态二氧化硅、石英、合成二氧化硅构成的无机填料当中的任一者均为相对介电常数小于4的无机填料，可以根据绝缘基板的相对介电常数的设计值来适宜地选择无机填料。具体而言，例如，在想要提高绝缘基板的相对介电常数的情况下可以选择相对介电常数超过8的无机填料，另一方面，在想要将绝缘基板的相对介电常数抑制为较低的情况下可以选择相对介电常数小于4的无机填料。当然，也可以组合地选择相对介电常数超过8的无机填料和相对介电常数小于4的无机填料。
上述无机填料的形状没有特别的限定，例如可列举出：球状、椭圆状、碎片状、块状等。
上述无机填料可以进行表面处理。
作为上述表面处理的方法，例如可列举出使用下述烷氧基硅烷并采用公知的整体掺混法对上述无机填料进行处理的方法等，该烷氧基硅烷为：甲基三甲氧基硅烷、乙基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、苯基三乙氧基硅烷、正丙基三甲氧基硅烷、正丙基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、辛基三乙氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、1,6-双(三甲氧基甲硅烷基)己烷、1,6-双(三乙氧基甲硅烷基)己烷、三氟丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-缩水甘油氧基丙基甲基二甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基甲基二乙氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷、对-苯乙烯基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基-亚丁基)丙胺、N-苯基-3-氨基丙基三甲氧基硅烷、N-(乙烯基苄基)-2-氨基乙基-3-氨基丙基三甲氧基硅烷的盐酸盐、三-(三甲氧基甲硅烷基丙基)异氰脲酸酯、(十三氟-1,1,2,2-四氢辛基)三乙氧基硅烷、(十七氟-1,1,2,2-四氢癸基)三乙氧基硅烷等。
通过进行这样的表面处理，从而能够提高上述烷氧基硅烷的聚合物与无机填料的粘接性。
相对于上述绝缘基板，上述无机填料的含量优选为30重量％至70重量％。
若上述无机填料的含量小于30重量％，则上述绝缘基板的线膨胀系数的绝对值有时会变得过大。另一方面，若上述无机填料的含量超过70重量％，则氟树脂变得过少，有时绝缘基板的成形会变得困难。
在上述层叠板中，上述绝缘基板的空隙率优选为5％以下。
通过使上述空隙率为5％以下，从而能够显著地抑制在高湿环境下长时间使用上述层叠板的情况下的介电损耗角正切的增加。
在本发明的实施方式中，上述空隙率通过以下方法确定。
采用扫描电子显微镜(SEM)对上述绝缘基板的沿厚度方向的截面进行观察，将所得的观察图像内的一部分区域作为分析范围，计算出该分析范围的面积S2以及该分析范围内的空隙所占的面积S1，通过下述方程式(1)计算出空隙率。
空隙率(％)＝(S1/S2)×100 (1)
在此，作为分析对象的观察图像，采用选自10个视野的观察图像当中的1个代表性视野的观察图像。
另外，作为上述空隙所占的面积S1的计算方法，可以采用以下方法。
可将SEM(扫描型电子显微镜)的反射电子图像的信号强度划分为256级，将黑设为强度0级，将白设为强度255级，将信号强度为100以下的部分识别为空隙，并将上述信号强度为100以下的区域的总和算作空隙所占的面积S1。
此时，信号强度可根据每个像素(pixel)＝0.0278μm×0.0278μm来判定。另外，分析范围可设为纵向1208pixel(33.5824μm)以及横向2048pixel(56.9344μm)，分析范围的面积S2可设为2473984pixel2(1912.0μm2)。
接下来，对于制造上述层叠板的方法进行说明。
上述层叠板(例如)可通过下述(1)至(4)的步骤来进行制造。
(1)首先，制备了含有氟树脂、烷氧基硅烷、无机填料及溶剂等的涂布液(溶胶液)以用于制作绝缘基板。
在此，可使氟树脂以粒料、氟树脂的水分散液、氟树脂的有机溶剂分散液、或者氟树脂在水和有机溶剂的混合溶剂中的分散液的形式进行供给。另外，在以分散液的形式来供给上述氟树脂的情况下，可利用该分散液中所含的水及/或有机溶剂作为用于溶胶液的溶剂。
在本步骤中，为了各个成分的混合，可以添加表面活性剂(优选为非离子型的表面活性剂)来制备上述涂布液。
在上述涂布液的制备中，将氟树脂、烷氧基硅烷、无机填料、溶剂及表面活性剂等原料成分混合，制备包含由烷氧基硅烷水解而得的甲硅烷醇的溶胶液。在此，作为将烷氧基硅烷水解以形成甲硅烷醇的方法，可采用公知的方法，例如可采用将原料成分的混合物搅拌的方法等。
(2)接下来，将步骤(1)所制备的涂布液进行涂布以形成由溶胶层构成的涂膜。
作为形成上述涂膜的被涂布材料，例如可使用树脂制的支持体或金属薄带等。
在此，当采用金属薄带作为上述被涂布材料时，可设为已经完成了上述金属薄带的层叠板的导体层。因此，采用金属薄带的方法在经济上是优异的。作为上述金属薄带，从适合作为高频基板的导体层的观点考虑，优选为铝箔或铜箔。
作为上述树脂制的支持体，例如可列举出由聚对苯二甲酸乙二醇酯、聚酰胺酰亚胺、聚酰亚胺等构成的塑料膜。
可以对上述被涂布材料的上述溶胶液涂布面进行表面处理。
当上述被涂布材料为金属薄带时，作为上述表面处理，例如可列举出利用含有硅烷偶联剂的处理液的前处理等。通过进行这些表面处理，从而在完成了的层叠板中，能够提高绝缘基板与导体层(金属薄带)的密合性。
当上述被涂布材料为树脂制的支持体时，作为上述表面处理，例如可列举出公知的脱模处理等。
作为将上述涂布液涂布于上述被涂布材料的方法，例如可以采用浸渍法、凹版印刷法、刮刀法等公知的方法，这些当中，从容易确保涂布厚度的均匀性、容易增加厚度的观点考虑，优选为刮刀法。
(3)接下来，在涂布于上述被涂布材料的溶胶液中，进行甲硅烷醇缩合以形成聚硅氧烷的凝胶化。在此，进行加热处理(干燥处理)以促进甲硅烷醇的缩合反应。在本步骤中，可在被涂布材料的一个面上形成凝胶层。
在上述加热处理中，可以使溶胶及表面活性剂挥发。
上述加热处理的温度通常可设为80℃至320℃左右。
(4)最后，通过下述步骤(4-1)或步骤(4-2)来完成层叠板。
(4-1)当在上述步骤(2)中采用金属薄带作为被涂布材料时，使用2片形成有经由上述步骤(3)制作的凝胶层的金属薄带，将两者配置为使得上述凝胶层彼此面对，并进行热压接。由此，能够得到凝胶层彼此热压接、且在凝胶层固化而形成的绝缘基板的两个面上设置有由金属薄带构成的导体层的层叠板。
(4-2)当在上述步骤(2)中采用树脂制的支持体作为被涂布材料时，从形成有经由上述步骤(3)而制作的凝胶层的支持体中剥离出该支持体并且只留下凝胶层，将金属薄带配置于该凝胶层的两个面上并进行热压接。在这种情况下也能够得到在绝缘基板的两个面上设置有由金属薄带构成的导体层的层叠板。
关于在上述步骤(4-1)及上述步骤(4-2)中进行的热压接处理，为了不使金属薄带氧化，优选在真空下、减压下、或惰性气体氛围下进行。在上述热压接处理中，例如可以在超过氟树脂软化点的温度下加压30分钟至数小时左右，然后冷却至121℃以下，再放开压力。
上述热压接处理的方式可以是间歇式的，也可以是连续式的。
通过采用这样的制造方法，从而能够适宜地制造本发明实施方式所涉及的层叠板。在上述制造方法中，经由烷氧基硅烷的凝胶化步骤而得的聚硅氧烷(烷氧基硅烷的聚合物)将无机填料彼此或无机填料与金属薄带结合，并且进一步将表面能低、粘接力弱的氟树脂的周边包围起来(形成了以上述聚硅氧烷为海、以上述氟树脂为岛的海岛结构)。因此，上述制造方法适合于制造由于空隙少因而吸水性低的层叠板。
(第2实施方式)
在图1所示的层叠板10中，在绝缘基材11的两个面上层叠有导体层12，但是根据本发明的实施方式的层叠板并非一定需要在绝缘基板的两个面上形成导体层，也可以仅在绝缘基板的一个面上形成导体层。
当制作仅在绝缘基板的一个面上形成有导体层的层叠板时，例如，在第1实施方式的层叠板制造方法的步骤(4)中，可准备1片在一个面上形成有凝胶层的金属薄带，对该凝胶层进行加热处理以形成绝缘基板。另外，可从形成有凝胶层的树脂制的支持体中剥离出该支持体并且只留下凝胶层，将金属薄带配置于该凝胶层的一个面上并进行热压接。
(其他实施方式)
在上述的实施方式中，利用溶胶-凝胶法制造了构成层叠板的绝缘基板，但是制造上述绝缘基板的方法并不限于利用溶胶-凝胶法的方法，也可以是利用诸如挤出成型或压延成形等方法的其他公知方法的方法。
[实施例]
以下，通过实施例来更具体地说明本发明的实施方式，但是本发明并不限于以下的实施例。
(实施例1)
在本实施例中，使用了以下物质作为原料(试剂)。
作为烷氧基硅烷，使用了癸基三甲氧基硅烷。
作为氟树脂的试剂，使用了聚四氟乙烯的水分散液(58重量％)。
作为无机填料，使用了预先对以非晶态二氧化硅为主成分的无机粉末(相对介电常数小于4)进行了表面处理而得的材料。在此，表面处理通过以下方法进行：使用癸基三甲氧基硅烷(1重量份)并采用已知的整体掺混法对100重量份的上述无机粉末进行处理。
作为表面活性剂，使用了聚氧乙烯烷基醚(非离子型表面活性剂)。
(1)将作为上述氟树脂的试剂的聚四氟乙烯的水分散液100重量份以及作为上述烷氧基硅烷的癸基三甲氧基硅烷0.6重量份混合，并稀释至168倍。
随后，向所得的稀释液中加入上述无机填料以将稀释液的重量增加至1.7倍，进一步混合上述表面活性剂3.5重量份。
将它们置于密封容器中，并使每个容器旋转，制备了用于形成绝缘基板的涂布液(溶胶液)。
需要说明的是，在本实施例中，相对于100重量份的聚四氟乙烯，以烷氧基硅烷成为1重量份(但是不包括对无机粉末进行表面处理的癸基三甲氧基硅烷)的方式进行制备。
在此，使用激光拉曼光谱仪(“TechnoSpex Pte Ltd公司”制，“uRaman-M”)，向上述溶胶液照射波长532nm的激光，测定拉曼位移。结果示出于图2中。图2中，拉曼曲线(1)为在本步骤中所测得的拉曼曲线。
如图2所示，在本步骤的测定中，在298cm-1附近及389cm-1附近(图2中，参照(b))确认到了对应于甲硅烷醇基团或甲硅烷醇基基团缩合过程的缺陷对结构的拉曼位移，在737cm-1附近(图2中，参照(c))确认到了对应于聚四氟乙烯的末端基团-CF3的拉曼位移，但是没有确认到对应于硅氧烷键的拉曼位移。
进一步，将上述溶胶液氮冷冻后，进行破碎，采用扫描电子显微镜在冷冻下观察冷冻溶胶液的破损横截面。观察图像示出于图3中。
图3(a)为实施例1中所拍摄的电子显微镜照片(倍率：1500倍)，(b)为将(a)放大显示的照片。
如图3所示，在冷冻后的上述溶胶液中，确认到了以下述方式存在的海岛结构：在以非晶态二氧化硅为主成分并经过表面处理后的无机填料(C)的间隙充满含有甲硅烷醇的海(A)，且聚四氟乙烯的粒子(B)被包围在含有甲硅烷醇的海(A)中。
(2)接下来，使用具备刮刀及加热炉的涂布装置，将上述(1)中所准备的溶胶液注入至刮刀的前侧，配置铜箔，将溶胶涂布时的传送铜箔的速度设为0.2m/分钟，将溶胶液涂布于铜箔的一个面上。然后，将涂布有溶胶液的铜箔输送到加热炉，使炉内温度从80℃上升至320℃，在使癸基三甲氧基硅烷的水解产物发生缩聚反应的同时将溶胶液凝胶化，在上述铜箔上形成了凝胶层。在此，将加热炉内设为氮气气氛以防止铜箔的氧化。
在此，使用上述激光拉曼光谱仪，向上述凝胶照射波长532nm的激光，并测定了拉曼位移。结果示出于图2中。图2中，拉曼曲线(2)是本步骤中所测定的拉曼曲线。
如图2所示，在本步骤的测定中，在485cm-1附近(图2中，参照(a))也确认到了表示硅氧烷键的显著的拉曼位移。
(3)接下来，准备具备模具的热压机，以凝胶层彼此面对的方式，将2片形成有凝胶层的铜箔配置于上述模具内，并进行加热和加压，从而经由凝胶层而将2片铜箔热压接。
在此，热压接的条件采用了依照已知的聚四氟乙烯的成形条件的温度和压力。另外，在加热和加压后，将温度降至121℃后取出经过了热压接的铜箔。
在本步骤中，通过加热和加压处理，凝胶层完全固化，该凝胶层成为了绝缘基板。也就是说，在本步骤中，得到了在绝缘基板的两个面上层叠有铜箔的层叠板。
对于本步骤中所得的层叠板，通过蚀刻除去铜箔，仅获得了绝缘基板。
随后，使用上述激光拉曼光谱仪，向上述绝缘基板照射波长532nm的激光，并测定了拉曼位移。结果示出于图2中。图2中，拉曼曲线(3)是本步骤中所测定的拉曼曲线。
如图2所示，在本步骤的测定中，在485cm-1附近(图2中，参照(a))确认到了表示硅氧烷键的显著的拉曼位移。
另外，为了对构成层叠板的绝缘基板内的空隙的存在比例进行观察，使用离子束得到上述绝缘基板的截面，采用扫描电子显微镜观察该截面，获得了反射电子图像(参照图4)。图4为在本实施例中所拍摄的扫描电子显微镜的反射电子图像，是从10个视野中所拍摄的反射电子图像当中选择的1个代表性视野的反射电子图像。
在此，如图4所示，在观察图像中设定了由黑框包围的分析范围(图4中的分析范围的面积S2：1912.0μm2)。随后，将分析范围内的反射电子图像的信号强度划分为256级，其中将黑设为强度0，将白设为强度255，提取出信号强度为100以下的部分(看起来为黑色的部分)，并计算出其面积。结果是，信号强度100以下的部分的面积S1为70.9μm2。基于所得的S1及S2算得的空隙率为3.7％。
此外，对构成层叠板的绝缘基板在高湿环境下的介电损耗角正切随时间的变化进行观察。介电损耗角正切的测定通过平衡圆板谐振器法来进行。上述平衡圆板谐振器法是根据日本电子电路协会的JPCA-FCL01(2006)标准的已知方法。
在此，对铜箔进行蚀刻，并在绝缘基板上绘制由平衡圆板谐振器法进行测定的谐振器，然后使所需数量的、仅包括没有铜箔的纯粹绝缘基板的片材进行绝缘基板重合，随后，向谐振器施加10GHz左右的频率，并测定上述绝缘基板的初始介电损耗角正切。
进一步地，在测定了初始介电损耗角正切以后，在将绝缘基板重叠的状态下，将绝缘基板在85℃×85％RH的环境中放置2000小时。每经过预定时间时，就取出绝缘基板并测定介电损耗角正切，重复上述操作直到2000小时。结果示出于表1中。
[表1]
| 时间(小时) | 介电损耗角正切 |
| 0 | 0.000844 |
| 200 | 0.000868 |
| 500 | 0.000885 |
| 1000 | 0.000896 |
| 1500 | 0.000905 |
| 2000 | 0.000909 |
结果是，如表1所示，初始介电损耗角正切为约0.0008，相对于此，经过2000小时后的介电损耗角正切为约0.0009。
如此地，构成本实施例的层叠板的绝缘基板即使在高湿环境下经过了2000小时后，也保持了小于0.001的介电损耗角正切，可知根据本发明实施方式的层叠板为高频特性优异的层叠板。
(实施例2至11)
除了如下述表2所示地改变癸基三甲氧基硅烷的混合量以外，与实施例1同样地制作了层叠板。
与实施例1同样地，表2所示的烷氧基硅烷的混合量是相对于100重量份聚四氟乙烯而混合的烷氧基硅烷的量(但是不包括对无机粉末进行表面处理的癸基三甲氧基硅烷)。
对于所制作的层叠板，与实施例1同样地，进行空隙率的计算、以及对高湿环境下的介电损耗角正切随时间的变化进行观察。结果示出于表2中。需要说明的是，在表2中，介电损耗角正切随时间而变化的观察结果表示为经过2000小时后的介电损耗角正切的增加率(％)。另外，表2中也列出了实施例1的结果以供参考。
[表2]
从表2的结果可明确得知，在根据本发明实施方式的层叠板中，通过将绝缘基板的空隙率抑制为5％以下，从而在高温环境中的既定条件下进行评价时，能够显著地抑制介电损耗角正切随时间的增加。
另外，当通过利用上述的溶胶-凝胶法的方法来制造层叠板时，可知：相对于100重量份聚四氟乙烯，将烷氧基硅烷的混合量设为0.3重量份至4重量份，这适合于使上述空隙率成为5％以下。其原因推测如下：若烷氧基硅烷的量少，则填充氟树脂及无机填料的间隙的烷氧基硅烷或其聚合物的量不足，另一方面，若烷氧基硅烷的量过多，则含有烷氧基硅烷的液体的溶胶凝胶反应变得剧烈，剧烈的凝胶化会使得液体难以进入到氟树脂及无机填料的间隙中。
(比较例1)
除了不混合癸基三甲氧基硅烷以外，与实施例1同样地制作了层叠板。
对于所得到的层叠板，与实施例1同样地，使用离子束得到绝缘基板的截面，采用扫描电子显微镜观察该截面，获得了反射电子图像(参照图5)。图5为在本比较例中所拍摄的扫描电子显微镜的反射电子图像，是从10个视野中所拍摄的反射电子图像当中选择的1个代表性视野的反射电子图像。
随后，通过与实施例1相同的方法，设定分析范围(图5中，由黑框包围的部分(面积S2：1912.0μm2))，并获得了与上述分析范围内的空隙相对应的部分的面积S1(图5中为110.4μm2)。基于所得的S1及S2算得的空隙率为5.8％。
进一步地，对于所得的层叠板，在测定了初始介电损耗角正切后，在将绝缘基板叠加的状态下，将绝缘基板在85℃×85％RH的环境中放置2000小时。每经过预定时间时，就取出绝缘基板并测定介电损耗角正切，重复上述操作直到2000小时。结果示出于表3中。
需要说明的是，介电损耗角正切的测定采用与实施例1相同的方法来进行。
[表3]
| 时间(小时) | 介电损耗角正切 |
| 0 | 0.000933 |
| 200 | 0.001114 |
| 500 | 0.001218 |
| 1000 | 0.001249 |
| 1500 | 0.001257 |
| 2000 | 0.001263 |
Claims (5)
1.一种层叠板，其为在绝缘基板的一个面或两个面上层叠有金属制导体层的层叠板，特征在于：
所述绝缘基板含有烷氧基硅烷的聚合物以及氟树脂，且所述氟树脂分散在所述烷氧基硅烷的聚合物中。
2.根据权利要求1所述的层叠板，其中，
所述烷氧基硅烷为烷基三烷氧基硅烷，
所述烷基三烷氧基硅烷所具有的烷基的碳原子数为3至9。
3.根据权利要求1或2所述的层叠板，其中，
所述氟树脂为聚四氟乙烯(PTFE)。
4.根据权利要求1至3中任一项所述的层叠板，其中，
所述绝缘基板进一步含有无机填料。
5.根据权利要求1至4中任一项所述的层叠板，其中，
所述绝缘基板的空隙率为5％以下。
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