CN113784838A - Resin film, high-frequency circuit board and method for producing same - Google Patents
Resin film, high-frequency circuit board and method for producing same Download PDFInfo
- Publication number
- CN113784838A CN113784838A CN202080029888.5A CN202080029888A CN113784838A CN 113784838 A CN113784838 A CN 113784838A CN 202080029888 A CN202080029888 A CN 202080029888A CN 113784838 A CN113784838 A CN 113784838A
- Authority
- CN
- China
- Prior art keywords
- resin film
- ether ketone
- resin
- circuit board
- frequency circuit
- 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
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- 239000011347 resin Substances 0.000 title claims abstract description 407
- 229920005989 resin Polymers 0.000 title claims abstract description 406
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- -1 ether ketone Chemical class 0.000 claims abstract description 104
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229920000412 polyarylene Polymers 0.000 claims abstract description 96
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- 239000012778 molding material Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims description 90
- 238000001125 extrusion Methods 0.000 claims description 52
- 239000010445 mica Substances 0.000 claims description 31
- 229910052618 mica group Inorganic materials 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 26
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 23
- 238000010438 heat treatment Methods 0.000 abstract description 22
- 230000008961 swelling Effects 0.000 abstract description 11
- 238000010030 laminating Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 64
- 239000004696 Poly ether ether ketone Substances 0.000 description 54
- 229920002530 polyetherether ketone Polymers 0.000 description 54
- 239000000155 melt Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 18
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 230000009477 glass transition Effects 0.000 description 16
- 238000000465 moulding Methods 0.000 description 15
- 238000004891 communication Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- KPXWHWLOLCWXRN-UHFFFAOYSA-N hexadecapotassium tetrasilicate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] KPXWHWLOLCWXRN-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000010295 mobile communication Methods 0.000 description 4
- 229920001643 poly(ether ketone) Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-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
- 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
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- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
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- 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
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- OIPQEPSMYUCOHY-UHFFFAOYSA-N methoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[SiH2]CCC(F)(F)F OIPQEPSMYUCOHY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- HMDRAGZZZBGZJC-UHFFFAOYSA-N n-[3-[3-aminopropoxy(dimethoxy)silyl]propyl]-1-phenylprop-2-en-1-amine Chemical compound NCCCO[Si](OC)(OC)CCCNC(C=C)C1=CC=CC=C1 HMDRAGZZZBGZJC-UHFFFAOYSA-N 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 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
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- ACMVLJBSYFHILY-UHFFFAOYSA-N oxo-di(tridecoxy)phosphanium Chemical compound CCCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCCC ACMVLJBSYFHILY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- B32B27/00—Layered products comprising a layer 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Waveguides (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention provides a resin film, a high-frequency circuit board and a manufacturing method thereof, wherein the resin film does not reduce the low dielectric property and heat resistance of a film for the high-frequency circuit board and the like made of polyarylene ether ketone resin, and can improve the heating dimensional stability. A resin film (1) which comprises 100 parts by mass of a polyarylene ether ketone resin and 10 to 80 parts by mass of a nonswelling synthetic mica. Since the resin film (1) is molded by using the molding material (4) containing non-swelling synthetic mica, the linear expansion coefficient can be reduced. Therefore, the heating dimensional stability of the resin film (1) can be improved, and the difference in heating dimensional characteristics from the metal layer made of metal foil (2) or the like can be suppressed, and the high-frequency circuit board can be prevented from curling or deforming when the high-frequency circuit board is manufactured by laminating the conductive layer (3).
Description
Technical Field
The present invention relates to a resin film used in a frequency band from MHz to GHz, a high-frequency circuit board, and a method for manufacturing the same, and more particularly, to a resin film used in a frequency band of 800MHz to 100GHz or less, a high-frequency circuit board, and a method for manufacturing the same.
Background
In recent years, there has been a demand for high-speed transmission and reception of data of a larger capacity for mobile information communication apparatuses such as multifunctional mobile phones (cellular phones) and tablet terminals, and electronic apparatuses such as next-generation televisions, which are rapidly increasing in demand. For example, in the field of mobile information communication, research on a fifth generation mobile communication system (5G) is progressing worldwide (see patent documents 1 and 2). The communication speed of the fifth generation mobile communication system is tens of times or more than that of the previous generation, and in order to achieve this, a high frequency band in which an electric signal is 10GHz or more is being studied. In the automotive field, it is also being studied to use signals in a high frequency band of 60GHz or more, which is called millimeter waves, as an on-vehicle radar system.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-502595;
patent document 2: japanese examined patent publication (Kokoku) No. 6-27002.
Disclosure of Invention
Problems to be solved by the invention
However, since the conventional circuit board is designed and developed mainly on the premise of effective use of communication in the low frequency band, and not on the premise of large capacity/high speed communication in the high frequency band, the relative dielectric constant is as high as about 4.3 of the ordinary type, and the dielectric loss tangent is not as low as about 0.018. On the other hand, circuit boards for large-capacity and high-speed communications are required to be materials having low dielectric properties such as relative permittivity and dielectric loss tangent and excellent properties such as heat resistance and mechanical strength.
To explain this point in detail, the relative permittivity is a parameter indicating the degree of polarization in the dielectric, and the higher the value is, the larger the transmission delay of the electric signal becomes. Therefore, in order to increase the transmission speed of the electrical signal and enable high-speed calculation, the relative dielectric constant is preferably low. The dielectric tangent (also referred to as tan δ) is a parameter indicating the amount of loss caused by the electric signal transmitted through the dielectric medium being converted into heat, and the lower the value, the less the loss of the signal, and the higher the transmission rate of the electric signal. Further, since the dielectric loss tangent increases with an increase in frequency in a high frequency band, it is necessary to use a material whose value can be reduced in order to suppress the loss as much as possible.
From the above, in order to realize large-capacity and high-speed communication, it is strongly desired that a circuit board used in a high frequency band from a MHz band to a GHz band is manufactured from a material having a relatively low dielectric constant and a relatively low dielectric loss tangent. In view of this, intensive studies have been made on materials having low relative dielectric constants and low dielectric loss tangents, and as a result, polyarylene ether ketone (also referred to as aromatic polyether ketone, PAEK) resins have been proposed and attracted attention.
Polyarylene ether ketone resins are thermoplastic crystalline resins having excellent electrical insulating properties, mechanical properties, heat resistance, chemical resistance, radiation resistance, hydrolysis resistance, low water absorption, recyclability, and the like. In view of such excellent properties, polyarylene ether ketone resins have been proposed and are being utilized in a wide range of fields such as the automotive field, the energy field, the semiconductor field, the medical field, and the aerospace field.
When a resin film is produced using the polyarylene ether ketone resin, the resin film has a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.007 or less at a frequency of 800MHz or more and 100GHz or less, and excellent low dielectric characteristics can be obtained. Further, according to the resin film, excellent heat resistance is obtained without deformation even if the resin film floats in a solder bath at 288 ℃ for 10 seconds.
However, a resin film made of a polyarylene ether ketone resin has poor dimensional stability under heating although excellent low dielectric characteristics and heat resistance are obtained, and therefore, when an electrically conductive layer is laminated, the dimensional characteristics under heating are greatly different from those of the electrically conductive layer, and thus a large problem of curling or deformation of the laminate newly arises.
As a method for improving the dimensional stability under heating of a resin film made of a polyarylene ether ketone resin, the following methods (1) and (2) have been proposed: a method (1) of molding a resin film from a molding material comprising a polyarylene ether ketone resin, hexagonal boron nitride and talc (see japanese patent No. 5896822); and a method (2) of subjecting a resin film containing 90 mass% or more of polyether ether ketone to biaxial stretching treatment (see japanese patent No. 5847522).
However, in the case of the method (1), since the hexagonal boron nitride is poor in uniform dispersibility, there newly arises a problem that the quality of the mechanical characteristics or the dielectric characteristics is not stable. In the case of the method (2), when the metal layer is formed on the resin film, the resin film and the metal foil may be bonded by an adhesive or the metal layer may be formed by laminating on the resin film via a seed layer, but the resin film and the metal foil are thermally fused to each other, and the resin film is removed from the biaxial stretching, and the laminate may be curled or deformed after lamination.
The present invention has been made in view of the above circumstances, and an object thereof is to: provided are a resin film, a high-frequency circuit board and a method for manufacturing the same, wherein the resin film can improve the dimensional stability under heating without reducing the low dielectric characteristics and heat resistance of a film for a high-frequency circuit board or the like made of polyarylene ether ketone resin.
Means for solving the problems
The present inventors have conducted extensive studies and as a result, have focused attention on polyarylene ether ketone resins having the highest heat resistance and excellent low dielectric characteristics among thermoplastic resin materials, and have completed the present invention by using the polyarylene ether ketone resins.
That is, in order to solve the above problems, the present invention is characterized in that: a resin film comprising 100 parts by mass of a polyarylene ether ketone resin and 10 to 80 parts by mass of non-swelling synthetic mica.
The relative crystallinity of the resin film is preferably 80% or more.
The resin film preferably has a linear expansion coefficient of 1 ppm/DEG C or more and 50 ppm/DEG C or less.
The nonswelling synthetic mica may be at least one of fluorophlogopite, tetrasilicic potassium mica, and potassium taeniolite.
Further, it is preferable that the synthetic mica has an average particle diameter of 0.5μm is more than or equal to 50μm is less than or equal to m.
Further, the aspect ratio of the synthetic mica is desirably 5 or more and 100 or less.
In order to solve the above problems, the present invention is characterized in that: a high-frequency circuit board comprising the resin film according to any one of claims 1 to 4.
The high-frequency circuit board may include a metal layer laminated by heat fusion with a resin film.
In order to solve the above problems, the present invention is characterized in that: a method for manufacturing a high-frequency circuit board according to claim 5 or 6,
the method comprises melt-kneading a molding material comprising at least 100 parts by mass of a polyarylene ether ketone resin and 10 to 80 parts by mass of a nonswelling synthetic mica, extruding the molding material through the die of an extrusion molding machine to form a resin film, and cooling the resin film by bringing the resin film into contact with a cooling roll to adjust the relative crystallinity of the resin film to 80% or more and to adjust the linear expansion coefficient of the resin film to 1 to 50 ppm/DEG C or more.
Here, the resin film in the claims includes a resin sheet in addition to the resin film. The resin film is not particularly limited to transparent, opaque, translucent, unstretched film, uniaxially stretched film, or biaxially stretched film. Further, examples of the non-swelling synthetic mica include: non-swelling synthetic mica heat-treated at 600 ℃ or higher. The metal layer is laminated on one surface or both surfaces of the resin film as necessary.
According to the present invention, since the resin film is molded by the molding material containing the nonswelling synthetic mica, the linear expansion coefficient of the resin film can be reduced, and the dimensional stability of the resin film under heating can be improved. Further, since the resin film is molded from a molding material containing a polyarylene ether ketone resin, the resin film has a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.006 or less in a frequency range of 800MHz or more and 100GHz or less, and the values of the relative dielectric constant and the dielectric loss tangent can be made lower than those of the conventional resin films.
Effects of the invention
According to the present invention, the polyarylene ether ketone resin has the following effects: the resin film for high-frequency circuit board can be improved in dimensional stability under heating without lowering the low dielectric characteristics and heat resistance of the resin film.
According to the invention of claim 2, since the relative crystallinity of the resin film is 80% or more, excellent soldering heat resistance can be obtained. Further, if the relative crystallinity of the resin film is 80% or more, it is expected to ensure dimensional stability in heating that can be used as a high-frequency circuit board.
According to the invention described in claim 3, since the linear expansion coefficient of the resin film is 1ppm/° c or more and 50ppm/° c or less, in the case of laminating the resin film and the conductive layer, it is possible to prevent curling or warping from easily occurring at the time of laminating these resin film and conductive layer. In addition, the fear of peeling of the resin film from the conductive layer can be eliminated.
According to the invention described in claim 4, since the synthetic mica is at least one of fluorophlogopite, tetrasilicic potassium mica and potassium taeniolite, excellent dimensional stability under heat, heat resistance and the like can be obtained.
According to the invention described in claim 5, the polyarylene ether ketone resin has the following effects: the resin film for a high-frequency circuit board can be improved in dimensional stability under heating without lowering the low dielectric characteristics and heat resistance of the resin film.
According to the invention of claim 6, since the resin film and the metal layer of the high-frequency circuit board do not need to be bonded with an adhesive, it is possible to prevent the adhesive from exerting an adverse effect on the high-frequency circuit board. Further, since the metal layer can be directly used as a conductive layer, the manufacturing cost can be reduced.
According to the invention described in claim 7, since the resin film of the high-frequency circuit board is molded by the melt extrusion molding method, the thickness accuracy, the yield, the workability of the resin film can be improved, or the manufacturing equipment can be simplified.
Drawings
FIG. 1 is a cross-sectional explanatory view schematically showing an embodiment of a resin film and a high-frequency circuit board according to the present invention.
Fig. 2 is an overall explanatory view schematically showing an embodiment of the resin film, the high-frequency circuit board, and the method for manufacturing the same according to the present invention.
FIG. 3 is a cross-sectional explanatory view schematically showing embodiment 2 of a resin film and a high-frequency circuit board according to the present invention.
Detailed Description
Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings, and as shown in fig. 1 or fig. 2, the high-frequency circuit board in the present embodiment is a circuit board for a fifth generation mobile communication system (5G) having a laminate structure including a resin film 1 and a conductive layer 3 laminated on the resin film 1, the resin film 1 is produced from a molding material 4 containing a polyarylene ether ketone resin as a thermoplastic resin and mica excellent in electrical insulation properties, and non-swelling synthetic mica contributing to dimensional stability is selected as the mica.
The resin film 1 is extrusion-molded 2 by a molding method using a molding material 4 containing a polyarylene ether ketone (PAEK) resinμm is more than 1000μA film having a thickness of m or less. The molding material 4 is prepared by adding 10 to 80 parts by mass of nonswelling synthetic mica to 100 parts by mass of a polyarylene ether ketone resin. In addition to the above-mentioned resins, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, an antistatic agent, a heat resistance improver, an inorganic compound, an organic compound, and the like may be optionally added to the molding material 4 within a range not to impair the characteristics of the present invention.
The polyarylene ether ketone resin of the molding material 4 is a crystalline resin composed of an arylene group, an ether group and a carbonyl group, and examples thereof include: japanese patent No. 5709878 or 5847522, or the document Asahi Research Center: resins described in super engineering plastics/PEEK (sho リサーチセンター, sho で long and rare するスーパーエンプラ, top) which have grown in advanced applications have excellent low dielectric characteristics, heat resistance, and the like.
Specific examples of the polyarylene ether ketone resin include: a polyether ether ketone (PEEK) resin having a chemical structure represented by chemical formula (1), a polyether ketone (PEK) resin having a chemical structure represented by chemical formula (2), a polyether ketone (PEKK) resin having a chemical structure represented by chemical formula (3), a polyether ether ketone (PEEKK) resin having a chemical structure represented by chemical formula (4), a polyether ketone ether ketone (PEKEKK) resin having a chemical structure represented by chemical formula (5), or the like.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
Among these polyarylene ether ketone resins, polyether ether ketone resins and polyether ketone resins are preferred from the viewpoints of availability, cost, and moldability of the resin film 1. Specific examples of the polyether ether ketone resin include: product name manufactured by Victrex corporation: product names manufactured by Victrex Powder series, Victrex Granules series, Daicel Evonik company: product names manufactured by Vestakeep series, Solvay Specialty Polymers, Inc.: the KetaSpire PEEK series. Further, as specific examples of the polyetherketoneketone resin, product names manufactured by Arkema corporation: the KEPSTAN series conforms.
The polyarylene ether ketone resin may be used alone in 1 kind, or may be used in combination with 2 or more kinds. The polyarylene ether ketone resin may be a copolymer having 2 or more chemical structures represented by chemical formulas (1) to (5). The polyarylene ether ketone resin is usually used in a form suitable for molding such as powder, pellet, or pellet form. The method for producing the polyarylene ether ketone resin is not particularly limited, and examples thereof include: literature [ Asahi Research Center: a preparation method described in super engineering plastics/PEEK (Asahi リサーチセンター, Hill application で long and rare するスーパーエンプラ, original PEEK) growing in advanced applications (supra).
The mica (also referred to as mica) of the molding material 4 is a plate-like crystal belonging to the family of layered silicate minerals mica, and is characterized by having a perfect cleavage at the bottom. The mica is divided into the following 2 types: natural mica (muscovite, biotite, phlogopite, etc.) produced in nature and synthetic mica produced artificially using talc as a main raw material are widely used industrially as excellent electrical insulating materials.
Since the natural mica has a composition or structure that varies depending on the place of production and contains many impurities, it is not suitable for producing the resin film 1 for a high-frequency circuit board having stable quality. Further, since natural mica has a hydroxyl group [ OH group ], it has a problem in heat resistance. On the other hand, since synthetic mica is artificially produced mica, has a constant composition and structure and contains few impurities, it is suitable for producing a high-quality resin film 1 for a high-frequency circuit board which is stable in dimensional stability under heating. Further, synthetic mica has all hydroxyl groups substituted by fluoro [ F ] groups, and therefore has excellent heat resistance as compared with natural mica. Thus, the mica used in the present invention is preferably synthetic mica as compared with natural mica.
Synthetic mica is classified into nonswelling mica and swelling mica according to the difference in behavior to water. The nonswelling mica is a type of synthetic mica which does not change dimensional stability or the like even when it is contacted with water. In contrast, the swellable mica is a synthetic mica having a property of swelling and splitting by absorbing moisture or the like in the air. When the swellable mica is used, the swellable mica contains moisture, and therefore the resin film 1 for a high-frequency circuit board may foam during molding. Therefore, the synthetic mica used in the present invention is preferably nonswelling mica having excellent dimensional stability under heating and water resistance, and more preferably synthetic mica heat-treated at 600 ℃ or higher.
The nonswelling synthetic mica is not particularly limited, and synthetic mica represented by the following general formula is suitably used.
A compound of the general formula: x1/3～1.0Y2～3(Z4O10)F1.5～2.0
Here, X is a cation occupying interlamination with a coordination number of 12, Y is a cation occupying an octahedral position with a coordination number of 6, and Z is a cation occupying a tetrahedron with a coordination number of 4, and these cations are substituted with the following 1 or 2 or more kinds of ions [ X: na (Na)+、K+、Li+、Rb+、Ca2+、Ba2+And Sr2+；Y：Mg2+、Fe2+、Ni2+、Mn2+、Co2+、Zn2+、Ti2+、Al3+、Cr3+、Fe3+、Li+；Z：Al3+、Fe3+、Si4+、Ge4+、B3+]。
Examples of the nonswelling synthetic mica include: fluorophlogopite (KMg)3(AlSi3O10)F2) Tetrasilicosylvite mica (KMg)2.5(Si4O10)F2) Potassium taeniolite (KMg)2Li(Si4O10)F2). Among these, nonswelling fluorophlogopite is most suitable. Specific examples of the synthetic mica include: high-purity and fine-powder tetrasilicic potassium mica manufactured by silo Co-op Agri corporation [ product name: micromica MK series]Fluorophlogopite [ PDM series ] manufactured by Topy industries Ltd]Tetrasilicosylpotassium mica manufactured by Topy industries Ltd [ PDM series ]]And the like.
Examples of the method for producing synthetic mica include: (1) a melting method, (2) a solid-phase reaction method, and (3) an Intercalation method. (1) The melting method of (1) is a production method comprising mixing raw materials such as silica, magnesia, alumina, fluoride, feldspar, olivine, and oxides or carbonates of various metals together, melting the mixture at a high temperature of 1300 ℃ or higher, and slowly cooling the mixture, (2) a production method comprising adding alkali fluoride, alkali silicofluoride, and oxides or carbonates of various metals including transition metals to talc as a main raw material, mixing the mixture, and reacting the mixture at about 1000 ℃; (3) the intercalation method of (2) is a production method in which talc is used as a main raw material and the production is carried out by the intercalation method.
The average particle diameter of the synthetic mica may be 0.5μm is more than or equal to 50μm is less than or equal to, preferably 1μm is less than and equal to 30μm is less than or equal to, more preferably 2μm is more than or equal to 20μm is less than or equal to, more preferably 3μm is more than or equal to 10μm is less than or equal to m. The reason for this is that: the average particle diameter of the synthetic mica was 0.5μWhen m is less than m, the synthetic mica particles tend to aggregate, and the uniform dispersibility in the polyarylene ether ketone resin is lowered.
In contrast, the reason is also that: the average particle diameter of the synthetic mica exceeds 50μIn the case of m, the toughness of the resin film 1 for a high-frequency circuit board obtained from a mixture of the polyarylene ether ketone resin and the synthetic mica is lowered. In addition, the reason is also that: the average particle diameter of the synthetic mica exceeds 50μIn the case of m, the synthetic mica protrudes from the surface of the resin film 1, and the surface of the resin film 1 is rough, which hinders the transmission characteristics.
The aspect ratio of the synthetic mica may be 5 or more and 100 or less. Here, in the case where the synthetic mica is flake powder, the aspect ratio is a value obtained by dividing the diameter of the particles by the thickness. The specific aspect ratio of the synthetic mica may be 5 or more and 100 or less, preferably 10 or more and 90 or less, more preferably 20 or more and 80 or less, and further preferably 30 or more and 50 or less.
The reason for this is that: when the aspect ratio is less than 5, the effect of improving the thermal dimensional stability is low, and the mechanical properties in the extrusion direction and the transverse direction of the resin film 1 and the anisotropy of the thermal dimensional stability are increased, which is not suitable. In contrast, the reason is also that: when the aspect ratio exceeds 100, the toughness of the resin film 1 obtained from the mixture of the polyarylene ether ketone resin and the synthetic mica is lowered.
The synthetic mica is added in a range of 10 parts by mass or more and 80 parts by mass or less, preferably 20 parts by mass or more and 70 parts by mass or less, and more preferably 30 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the polyarylene ether ketone resin. The reason for this is that: when the amount of the synthetic mica added is less than 10 parts by mass, the effect of controlling the dimensional stability under heating of the resin film 1 for a high-frequency circuit board is insufficient.
In contrast, the reason is also that: when the amount of the synthetic mica added exceeds 80 parts by mass, heat is generated significantly during the preparation of the molding material 4 composed of the polyarylene ether ketone resin and the synthetic mica, and the polyarylene ether ketone resin may be thermally decomposed. In addition, the reason is also that: the toughness of the resin film 1 obtained from the molding material 4 is lost, and the resin film 1 may be significantly brittle and damaged during molding. The following is also the reason: since the amount of the synthetic mica added is increased, the relative permittivity and the dielectric loss tangent are remarkably increased more than necessary.
The synthetic mica can be treated with various coupling agents, including, for example: silane coupling agents [ vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, glycidyloxy-substituted vinyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxy-methyldiethoxysilane, 3-glycidyloxy-substituted vinyltriethoxysilane, 3-substituted vinyltrimethoxysilane, 3-isopropyltriethoxysilane, 3-substituted vinyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-vinyltrimethoxysilane, 3-glycidyloxy-substituted vinyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, p-vinyltrimethoxysilane, and a, N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N-3-aminopropyltriethoxysilane, N-propyltrimethoxysilane, N-2-aminopropyltriethoxysilane, N-propyltriethoxysilane, N-2-aminopropyltriethoxysilane, N-isopropyltrimethoxysilane, N-2 (aminoethyl) -3-isopropylidenedimethoxysilane, N-3-isopropyltrimethoxysilane, N-3-isopropyltriethoxysilane, N-3-isopropyltriethoxysilane, N-3-isopropyltriethoxysilane, N-isopropyltriethoxysilane, N-3-N-isopropyltriethoxysilane, N-tert-one-, 3-mercaptopropyltrimethoxysilane, etc. ], silane agents [ methyltrimethoxysilane, dimethyldimethoxysilane, phenylsilane, dimethoxydiphenylsilane, N-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilylsilane) hexane, trifluoropropylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyltriethoxysilane, phenyltriethoxysilane, N-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, hexamethyldisilazane, imidazolesilane, etc. ], titanate-based coupling agents [ isopropyltriisostearoyltitanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (N-aminoethyl) titanate, tetraoctylbis (di (tridecyl) phosphite) titanate, methyltriethoxysilane, etc. ], titanium oxide, and titanium oxide, and titanium oxide, and titanium oxide, titanium oxide, Tetrakis (2, 2-diallyloxy-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, isopropyltrioctyl titanate, isopropyldimethacryloylstearyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoylpropyldiacryloyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate, etc. ], an aluminate ester coupling agent [ e.g., acetoacetoxyaluminum diisopropionate ], and the like.
The polyarylene ether ketone resin and the synthetic mica are melt-kneaded for a predetermined period of time to form a molding material 4 for the resin film 1, and examples of a method for preparing the molding material 4 include: method (1) in which a synthetic mica is added to molten polyarylene ether ketone without stirring and mixing the polyarylene ether ketone resin and the fine powder of the synthetic mica, and the mixture is melt-kneaded to prepare a molding material 4; in the method (2), the polyarylene ether ketone resin and the fine synthetic mica powder are stirred and mixed at room temperature (a temperature of about 0 ℃ to 50 ℃) and then melt-kneaded to prepare the molding material 4. Both of these methods (1) and (2) can be used, but the method (1) is preferred from the viewpoint of dispersibility and handling properties.
Specifically describing the method (1), in order to prepare the molding material 4, the polyarylene ether ketone resin is first melted by a melt-kneading machine such as a mixing roll, a pressure kneader, a banbury mixer, a single-screw extruder, or a multi-screw extruder (a twin-screw extruder, a three-screw extruder, or a four-screw extruder), and then the synthetic mica is added to the polyarylene ether ketone resin to be melt-kneaded and dispersed, thereby preparing the molding material 4.
The temperature of the melt kneader during preparation is not particularly limited as long as it is a temperature at which the polyarylene ether ketone resin can be melt kneaded and dispersed and does not decompose, and the temperature is in a range of not lower than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature. Specifically, the temperature may be 320 ℃ to 450 ℃, preferably 360 ℃ to 420 ℃, and more preferably 380 ℃ to 400 ℃.
This is based on the following reasons: if the temperature is lower than the melting point of the polyarylene ether ketone resin, the molding material 4 containing the polyarylene ether ketone resin cannot be melt-extrusion molded because the polyarylene ether ketone resin is not melted, and conversely, if the temperature exceeds the thermal decomposition temperature, the polyarylene ether ketone resin may be decomposed drastically. The molding material 4 thus prepared is usually extruded into a block, strand, sheet or rod shape, and then used in a form suitable for molding such as a block, pellet or pellet by a pulverizer or cutter.
Next, as a specific explanation of the method (2), a drum mixer, a henschel mixer, a V-type mixer, a nauta mixer, a ribbon mixer, a universal stirring mixer or the like is used in order to obtain a stirred mixture by stirring and mixing the polyarylene ether ketone resin and the synthetic mica. In this case, the polyarylene ether ketone resin is preferably in the form of a powder which can be dispersed more uniformly with the synthetic mica. Examples of the method of pulverizing into powder include: a shear pulverization method, an impact pulverization method, a collision pulverization method, a freeze pulverization method, a solution pulverization method, and the like.
The molding material 4 is prepared by melt-kneading and dispersing a stirred mixture of the polyarylene ether ketone resin and the synthetic mica by a melt-kneading machine such as a mixing roll, a pressure kneader, a banbury mixer, a single-screw extruder, or a multi-screw extruder (e.g., a twin-screw extruder, a three-screw extruder, or a four-screw extruder).
The temperature of the melt kneader in this preparation is not particularly limited as long as it is a temperature at which the polyarylene ether ketone resin can be melt kneaded and dispersed and does not decompose, and the temperature is in a range of not lower than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature. Specifically, for the same reason as in the case of the method (1), it may be in the range of 320 ℃ to 450 ℃, preferably 360 ℃ to 420 ℃, and more preferably 380 ℃ to 400 ℃. The molding material 4 thus prepared is usually extruded into a block, strand, sheet or rod shape, and then used in a form suitable for molding such as a block, pellet or pellet by a pulverizer or cutter.
The molding material 4 is molded into the resin film 1 by various molding methods such as a melt extrusion molding method, a calendar molding method, or a casting molding method. Among these molding methods, the melt extrusion molding method is most suitable from the viewpoint of improving the operability or simplifying the equipment. As shown in fig. 2, the melt extrusion molding method is a method of: the molding material 4 is melt-kneaded by a melt extrusion molding machine 10 such as a single-screw extrusion molding machine or a twin-screw extrusion molding machine, and is continuously extruded from a T-die 13 of the melt extrusion molding machine 10 in the direction of a plurality of cooling rolls 16 and a nip roll 17 to form a resin film 1 in a belt shape.
As shown in fig. 2, the melt extrusion molding machine 10 is constituted by, for example, a single-screw extrusion molding machine, a twin-screw extrusion molding machine, or the like, and functions to melt-knead the molding material 4 to be charged. A raw material inlet 11 for the polyarylene ether ketone resin of the molding material 4 is provided at the upper rear part on the upstream side of the melt extrusion molding machine 10, an inert gas supply pipe 12 is connected to the raw material inlet 11, and an inert gas such as helium, neon, argon, krypton, nitrogen, or carbon dioxide is supplied to the inert gas supply pipe 12 as needed, and the inert gas is flowed from the inert gas supply pipe 12, whereby the oxidative degradation or oxygen crosslinking of the polyarylene ether ketone resin of the molding material 4 is effectively prevented.
The temperature of the melt extrusion molding machine 10 is not particularly limited as long as it is a temperature at which the resin film 1 can be molded and the polyarylene ether ketone resin is not decomposed, and may be in a range of not lower than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature. Specifically, the temperature is adjusted to 320 ℃ or higher and 450 ℃ or lower, preferably 360 ℃ or higher and 420 ℃ or lower, and more preferably 380 ℃ or higher and 400 ℃ or lower. The reason for this is that: when the temperature of the melt extrusion molding machine 10 is lower than the melting point of the polyarylene ether ketone resin, the polyarylene ether ketone resin is not melted and molding of the resin film 1 becomes difficult, whereas when the temperature is not lower than the thermal decomposition temperature, the polyarylene ether ketone resin is decomposed drastically.
The T-die 13 is attached to the tip end of the melt extrusion molding machine 10 via a connecting pipe 14, and functions to continuously extrude the resin film 1 in a band shape downward. The temperature at the time of extrusion of the T-die 13 is in a range of not less than the melting point of the polyarylene ether ketone resin but less than the thermal decomposition temperature. Specifically, the temperature is adjusted to 320 ℃ or higher and 450 ℃ or lower, preferably 360 ℃ or higher and 420 ℃ or lower, and more preferably 380 ℃ or higher and 400 ℃ or lower. This is based on the following reasons: if the melting point of the polyarylene ether ketone resin is lower than the melting point of the polyarylene ether ketone resin, melt extrusion molding of the molding material 4 containing the polyarylene ether ketone resin is hindered, and if the temperature exceeds the thermal decomposition temperature, the polyarylene ether ketone resin may be decomposed drastically.
A gear pump 15 is preferably mounted on the connection pipe 14 upstream of the T-die 13. The gear pump 15 feeds the molding material 4 melt-kneaded by the melt extrusion molding machine 10 to the T-die 13 at a constant flow rate with high accuracy.
The plurality of cooling rollers 16 are, for example, rotatable metal rollers having a larger diameter than the nip rollers 17, are arranged in a row in the downstream direction from below the T-die 13 and are supported by a shaft, and hold the extruded resin film 1 between the adjacent nip rollers 17 and between the adjacent cooling rollers 16 and 16, and control the thickness of the resin film 1 within a predetermined range while cooling the resin film 1 together with the nip rollers 17.
Each cooling roller 16 is adjusted to a temperature range of [ glass transition temperature +20 ℃ ] of the polyarylene ether ketone resin to less than the melting point of the polyarylene ether ketone resin, preferably [ glass transition temperature +30 ℃ ] of the polyarylene ether ketone resin to less than [ glass transition temperature +160 ℃ ], more preferably [ glass transition temperature +50 ℃ ] of the polyarylene ether ketone resin to less than [ glass transition temperature +140 ℃ ] of the polyarylene ether ketone resin, and still more preferably [ glass transition temperature +60 ℃ ] of the polyarylene ether ketone resin to less than [ glass transition temperature +120 ℃ ] of the polyarylene ether ketone resin, and is brought into sliding contact with the resin film 1 for a high-frequency circuit board.
When the temperature of each cooling roll 16 is lower than [ glass transition temperature +20 ℃ C ] of the polyarylene ether ketone resin, the relative crystallinity of the resin film 1 is less than 80%, and the solder heat resistance cannot be obtained. On the other hand, when the temperature of each cooling roll 16 is equal to or higher than the melting point of the polyarylene ether ketone resin, the resin film 1 may be stuck to the cooling roll 16 and broken during the production of the resin film 1. The method of temperature adjustment or cooling of each cooling roll 16 includes: a method using a heat medium such as air, water, or oil, an electric heater, induction heating, or the like.
The plurality of nip rollers 17 are rotatably supported in a pair in a downstream direction from below the T-die 13 of the melt extrusion molding machine 10, and sandwich the plurality of cooling rollers 16 arranged in a row, thereby press-contacting the resin film 1 against the cooling rollers 16. The pair of nip rollers 17 is provided with a winder 18 for the resin film 1 downstream of the nip roller 17 on the downstream side, a slit blade 20 forming a slit on the side of the resin film 1 is arranged between the pair of nip rollers 17 and a winding tube 19 of the winder 18 so as to be at least movable up and down, and a necessary number of shaft-supported tension rollers 21 for applying tension to the resin film 1 to smoothly wind the resin film are rotatably supported between the slit blade 20 and the winder 18.
On the circumferential surface of each of the nip rollers 17, at least a rubber layer of natural rubber, isoprene rubber, butadiene rubber, norbornene rubber, acrylonitrile butadiene rubber, nitrile rubber, urethane rubber, silicone rubber, fluorine rubber or the like is formed so as to cover the circumference surface of the resin film 1 and the cooling roller 16 as necessary, and an inorganic compound such as silica or alumina is selectively added to the rubber layer. Among these, silicone rubber or fluororubber excellent in heat resistance is preferably used.
The nip roller 17 uses a metal elastic roller whose surface is metal as necessary, and when this metal elastic roller is used, it is possible to mold the polyarylene ether ketone resin film 1 whose surface has excellent smoothness. As specific examples of the metal elastic roller, a metal sleeve roller, an air roller (manufactured by Dymco: product name ], UF roller (manufactured by hitachi shipbuilding: product name ], and the like.
The nip roller 17 is adjusted to have a temperature range of [ glass transition temperature +20 ℃ C ] of the polyarylene ether ketone resin to less than the melting point of the polyarylene ether ketone resin, preferably [ glass transition temperature +30 ℃ C ] of the polyarylene ether ketone resin to less than [ glass transition temperature +160 ℃ C ] of the polyarylene ether ketone resin, more preferably [ glass transition temperature +50 ℃ C ] of the polyarylene ether ketone resin to less than [ glass transition temperature +140 ℃ C ] of the polyarylene ether ketone resin, and still more preferably [ glass transition temperature +60 ℃ C ] of the polyarylene ether ketone resin to less than [ glass transition temperature +120 ℃ C ] of the polyarylene ether ketone resin, and brought into sliding contact with the resin film 1, as in the same manner as the cooling roller 16.
The reason why the temperature of the stitching roller 17 is adjusted to the temperature range concerned is that: the relative crystallization of the resin film 1 is adjusted to 80% or more. That is, when the temperature of the nip roller 17 is lower than [ glass transition temperature +20 ℃ C ] of the polyarylene ether ketone resin film 1, the relative crystallinity of the polyarylene ether ketone resin film 1 is less than 80%, and there is a problem that the soldering heat resistance cannot be obtained. In addition, when the temperature of the nip roller 17 is not lower than the melting point of the polyarylene ether ketone resin, the resin film 1 may be stuck to the cooling roller 16 and broken during the production of the resin film 1.
The method of temperature adjustment or cooling of each nip roller 17 is not limited as in the cooling roller 16, and examples thereof include: a method using a heat medium such as air, water, or oil, an electric heater, induction heating, or the like.
In the above, in the case of producing the resin film 1 for a high-frequency circuit board, as shown in fig. 2, first, the molding material 4 is put into the melt extrusion molding machine 10 while supplying an inert gas indicated by an arrow in the drawing to the raw material inlet 11 of the melt extrusion molding machine 10, and the polyarylene ether ketone resin and the synthetic mica of the molding material 4 are melt-kneaded by the melt extrusion molding machine 10, thereby continuously extruding the resin film 1 in a strip form from the T-die 13.
In this case, the water content of the molding material 4 before melt extrusion is adjusted to 2000ppm or less, preferably 1000ppm or less, and more preferably 100ppm to 500 ppm. The reason for this is that: when the water content exceeds 2000ppm, the polyarylene ether ketone resin may foam immediately after extrusion from the T-die 13.
After the resin film 1 is extruded, the resin film 1 is wound around a pair of nip rollers 17, a plurality of cooling rollers 16, a tension roller 21, and a winding pipe 19 of a winder 18 in this order, the resin film 1 is cooled by the cooling rollers 16, and then both side portions of the resin film 1 are cut by a slit blade 20 and simultaneously wound around the winding pipe 19 of the winder 18 in this order, whereby the resin film 1 for a high-frequency circuit board can be manufactured. When the resin film 1 is produced, fine irregularities are formed on the surface of the resin film 1 within a range in which the effect of the present invention is not lost, and the friction coefficient of the surface of the resin film 1 can be reduced.
The thickness of the resin film 1 is 2μm is more than 1000μm is not more than m, and is not particularly limited, but is preferably 10 from the viewpoint of sufficient thickness, workability, and thinning of the high-frequency circuit substrateμm is more than or equal to 800μm is less than or equal to, more preferably 20μm is 500 or moreμm is not more than, more preferably 75μm is more than and equal to 250μm is less than or equal to m.
From the viewpoint of realizing high-speed communication that effectively utilizes a high-frequency band, the relative dielectric constant of the resin film 1 in the range of a frequency of 800MHz or more and 100GHz or less, preferably 1GHz or more and 90GHz or less, more preferably 10GHz or more and 85GHz or less, further preferably 25GHz or more and 80GHz or less may be 3.5 or less, preferably 3.3 or less, more preferably 3.1 or less, further preferably 3.0 or less. The lower limit of the relative permittivity is not particularly limited, and is practically 1.5 or more.
Specifically, the resin film 1 preferably has a relative permittivity of 3.4 or less at a frequency of 1GHz, a relative permittivity of 3.17 or less at a frequency of 10GHz, a relative permittivity of 3.29 or less at a frequency in the vicinity of 28GHz, and a relative permittivity of 3.42 or less at a frequency of 76.5 GHz. The reason for this is that: if the relative dielectric constant of the resin film 1 in the range of the frequency of 800MHz or more and 100GHz or less exceeds 3.5, the transmission speed of the electric signal is reduced, and therefore, there is a problem that it is not suitable for high-speed communication.
In order to realize high-speed communication that effectively utilizes a high frequency band, the dielectric loss tangent of the resin film 1 in the range of a frequency of 800MHz or more and 100GHz or less, preferably 1GHz or more and 90GHz or less, more preferably 10GHz or more and 85GHz or less, and further preferably 25GHz or more and 80GHz or less may be 0.007 or less, preferably 0.005 or less, more preferably 0.004 or less, and further preferably 0.003 or less. The lower limit of the dielectric loss tangent is not particularly limited, and is practically 0.0001 or more.
Specifically, the dielectric tangent of the resin film 1 is preferably 0.003 or less at a frequency of 1GHz and 0.003 or less at a frequency in the vicinity of 10 GHz. The dielectric loss tangent at a frequency around 28GHz may be 0.0037 or less, and the dielectric loss tangent at a frequency around 76.5GHz may be 0.0050 or less. These are based on the following reasons: when the dielectric loss tangent in the range of the frequency of 800MHz or more and 100GHz or less exceeds 0.007, the loss is large and the signal transmission rate is lowered, and therefore, the antenna is not suitable for large-capacity communication.
The method for measuring the relative permittivity and the dielectric loss tangent is not particularly limited, and examples thereof include: a reflection/transmission (S parameter) method such as a coaxial probe method, a coaxial S parameter method, a waveguide S parameter method, a free space S parameter method, a measurement method using a striped line (ring) resonator, a cavity resonator perturbation method, a measurement method using a split column dielectric resonator, a measurement method using a cylindrical (split cylindrical) cavity resonator, a measurement method using a multi-frequency balanced circular plate resonator, a measurement method using a block cylindrical waveguide cavity resonator, a resonator method such as an open resonator method using a Fabry-Perot resonator, and the like.
In addition, there may be enumerated: a method of obtaining a relative permittivity and a dielectric loss tangent of a high frequency by a cavity resonator perturbation method, a 3-terminal measurement method by a mutual induction bridge circuit, and the like. Among these, the Fabry-Perot method and the cavity resonator perturbation method, which are excellent in high resolution, are most suitably selected.
The relative crystallinity of the resin film 1 may be 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 100%. The reason for this is that: when the relative crystallinity of the resin film 1 is less than 80%, the soldering heat resistance of the resin film 1 may be problematic. In addition, the reason is that: if the relative crystallinity is 80% or more, it is expected to ensure dimensional stability in heating that can be used as a high-frequency circuit board.
The crystallinity of the resin film 1 can be expressed by a relative crystallinity. The relative crystallinity of the resin film 1 was calculated from the thermal analysis result measured at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter by the following formula.
Relative crystallinity (%) = { 1- (Δ Hc/Δ Hm) } × 100;
Δ Hc: heat of recrystallization peak (J/g);
Δ Hm: heat of fusion peak (J/g).
The dimensional stability under heat of the resin film 1 can be expressed by a linear expansion coefficient. The linear expansion coefficient is 1 ppm/DEG C or more and 50 ppm/DEG C or less, preferably 3 ppm/DEG C or more and 40 ppm/DEG C or less, more preferably 5 ppm/DEG C or more and 35 ppm/DEG C or less, and further preferably 10 ppm/DEG C or more and 30 ppm/DEG C or less in both the extrusion direction and the transverse direction (direction perpendicular to the extrusion direction) of the resin film 1. The reason for this is that: when the linear expansion coefficient is out of the range of 1 ppm/DEG C or more and 50 ppm/DEG C or less, curling or warping is likely to occur when the resin film 1 and the conductive layer 3 are laminated, and there is a possibility that the resin film 1 and the conductive layer 3 are peeled off.
The mechanical properties of the resin film 1 can be evaluated by the tensile elastic modulus at 23 ℃. The most suitable range of the tensile elastic modulus of the resin film 1 at 23 ℃ is 3500N/mm210000N/mm or more2Below, preferably 3800N/mm29000N/mm2Hereinafter, 3900N/mm is more preferable2Above 8880N/mm2The following. The reason for this is that: modulus of elasticity in tension of less than 3500N/mm2In the case of (3), since the resin film 1 has poor rigidity, there is a possibility that the resin film 1 is wrinkled or the resin film 1 is deformed during the production of the high-frequency circuit board. Conversely, for the following reasons: in excess of 10000N/mm2In the case of (3), the molding of the resin film 1 requires a long time, and cost reduction cannot be expected.
In view of the convenience of manufacturing a high-frequency circuit board, the heat resistance of the resin film 1 is preferably evaluated by solder heat resistance. Specifically, according to the test method of JIS standard C5016, the resin film 1 was allowed to float in the solder bath at 288 ℃ for 10 seconds, and when deformation or wrinkle of the resin film 1 was observed, it was evaluated that there was a problem in heat resistance, and when deformation or wrinkle of the resin film 1 was not observed, it was evaluated that there was no problem in heat resistance.
Next, in the case of manufacturing a high-frequency circuit board, if the conductive layer 3 is formed on the manufactured resin film 1, and then a wiring pattern of a conductive circuit is formed on the conductive layer 3, the high-frequency circuit board can be manufactured. The conductive layer 3 is formed on one of the front and back surfaces, the front surface, and the back surface of the resin film 1, and a wiring pattern of a conductive circuit is formed from the back surface. As the conductor used for the conductive layer 3, there can be generally mentioned: for example, metals such as copper, gold, silver, chromium, iron, aluminum, nickel, and tin, or alloys of these metals.
Examples of the method for forming the conductive layer 3 include the following methods: a method (1) in which a resin film 1 and a metal foil 2 are thermally fused to form a conductive layer 3; a method (2) in which the conductive layer 3 is formed by bonding the resin film 1 and the metal foil 2 with an adhesive; and a method (3) of forming a seed layer on the resin film 1 while forming a metal layer on the seed layer in a laminated manner, and forming the conductive layer 3 from the seed layer and the metal layer.
The method (1) comprises holding the resin film 1 and the metal foil 2 between a press molding machine or a roll, and heating/pressingThereby forming the conductive layer 3. In the case of this method, the thickness of the metal foil 2 may be 1μm is 100 or moreμm is less than or equal to, preferably 5μm is more than and equal to 80μm is less than or equal to, more preferably 10μm is more than and equal to 70μm is in the range of not more than m.
In order to improve the fusion strength at the time of hot fusion, fine irregularities may be formed on the surface of the resin film 1 or the metal foil 2. The surface of the resin film 1 or the metal foil 2 may be subjected to a surface treatment such as corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, flame irradiation treatment, ITRO irradiation treatment, oxidation treatment, hairline (hair line) processing, and sanding pad (sand mat) processing. The surface of the resin film 1 or the metal foil 2 may be treated with a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
The method (2) is a method of: an adhesive such as an epoxy resin adhesive, a phenol resin adhesive, or a siloxane-modified polyamideimide resin adhesive is placed between the resin film 1 and the metal foil 2, and the resin film 1 is heated and pressed by a pressing machine or a roll to form the metal foil 2 on the resin film 1. In the case of this method, the thickness of the metal foil 2 may be 1μm is 100 or moreμm is less than or equal to, preferably 5μm is more than and equal to 80μm is less than or equal to, more preferably 10μm is more than and equal to 70μm is in the range of not more than m.
From the viewpoint of improving the adhesive strength, the surface of the resin film 1 or the metal foil 2 can be formed with fine irregularities as described above. The surface of the resin film 1 or the metal foil 2 may be subjected to a surface treatment by corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, flame irradiation treatment, ITRO irradiation treatment, oxidation treatment, wire processing, sanding processing, or the like. Further, as described above, the surface of the resin film 1 or the metal foil 2 may be treated with a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
The method (3) is a method of: forming a seed layer for adhesion on the resin film 1 by sputtering, vapor deposition, plating or the like, and heatingA metal layer is formed on the seed layer by a fusion method, a vapor deposition method, or an electroplating method, and the seed layer and the metal layer are formed on the conductive layer 3. As the seed layer, for example, there can be used: metals such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, and zinc, or alloys of these metals. The thickness of the seed layer is typically 0.1μm is more than or equal to 2μm is in the range of not more than m.
When the seed layer is formed on the resin film 1, an anchor layer may be formed in order to improve their adhesive strength. Examples of the anchor layer include: metals such as nickel and chromium, but nickel which is excellent in environmental properties is preferable.
As the metal layer, for example: metals such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, and zinc, or alloys of these metals. The metal layer may be a single layer composed of 1 kind of metal, or may be a multiple layer or a multilayer composed of 2 or more kinds of metals. The thickness of the metal layer is not particularly limited, and may be 0.1μm is more than or equal to 50μm is less than or equal to, preferably 1μm is more than and equal to 30μm is less than or equal to m.
The conductive layer 3 consisting of the seed layer and the metal layer may be 0.2μm is more than or equal to 50μm is less than or equal to, preferably 1μm is more than and equal to 30μm is less than or equal to, more preferably 5μm is more than or equal to 20μm is less than or equal to, more preferably 5μm is more than or equal to 10μm is in the range of not more than m. The seed layer and the metal layer may be the same metal or different metals. Further, the surface of the metal layer may be covered with a metal protective layer of gold, nickel, or the like to prevent corrosion of the surface.
Among the methods for forming the conductive layer 3, the method (1) of thermally fusing the resin film 1 and the metal foil 2 is most suitable. The reason for this is that: in the case of the method (2), since the resin film 1 and the metal foil 2 need to be bonded by an adhesive, the relative permittivity or the dielectric loss tangent of the high-frequency circuit board may be increased by reflecting the dielectric characteristics of the adhesive. The following is also the reason: in the case of the method (3), the step of forming the conductive layer 3 becomes complicated, leading to an increase in cost.
The wiring pattern of the conductive circuit can be formed by a desired number by etching, plating, printing, or the like. In the method for forming a wiring pattern, an etchant of sulfuric acid-hydrogen peroxide system, ferric chloride, or the like can be used, and these etchants can minimize the occurrence of undercut or fine wiring and can form a good wiring. When such a wiring pattern having a predetermined shape is formed, a high-frequency circuit board having excellent low dielectric properties and reduced signal loss can be manufactured.
According to the above, since the resin film 1 is molded by the molding material 4 containing the nonswelling synthetic mica, the linear expansion coefficient can be reduced. Therefore, the heating dimensional stability of the resin film 1 can be improved, and the difference in the heating dimensional characteristics from the metal layer made of the metal foil 2 or the like can be suppressed, and the high-frequency circuit board can be prevented from curling or deforming when the high-frequency circuit board is manufactured by laminating the conductive layers 3.
Further, since the resin film 1 is molded by the molding material 4 containing the polyarylene ether ketone resin, the resin film 1 has a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.007 or less in a frequency range of 800MHz to 100GHz, and the values of the relative dielectric constant and the dielectric loss tangent can be made lower than those of the conventional resin film. Therefore, a high-frequency circuit board capable of transmitting and receiving a high-frequency signal having a large capacity at high speed can be obtained. In addition, by using the high-frequency circuit board, it is possible to contribute greatly to the realization of a fifth-generation mobile communication system.
Further, since the polyarylene ether ketone resin is used, the loss is reduced, and the resin film 1 for a high-frequency circuit board can be used for a long period of time, and high-speed communication utilizing a high-frequency band is very easily realized. Further, since the polyarylene ether ketone resin is used instead of the polyimide resin, the high-frequency circuit board can be easily multilayered. Further, since the resin film 1 having a relative crystallinity of 80% or more, which is excellent in heat resistance, is used as a substrate material, excellent soldering heat resistance can be obtained.
Next, fig. 3 is a view showing embodiment 2 of the present invention, in which metal foils 2 for wiring patterns are laminated on both front and back surfaces of a resin film 1 by a thermal fusion method, respectively, and a conductive layer 3 is formed by the pair of metal foils 2. Since the other portions are the same as those in the above embodiment, the description thereof is omitted.
In the present embodiment, the same operational effects as those of the above-described embodiment can be expected, and since the conductive layers 3 are formed on both surfaces of the resin film 1, it is possible to clearly understand that the density of the wiring of the high-frequency circuit board is increased and the number of layers of the high-frequency circuit board is increased.
In the above embodiment, 1 kind of synthetic mica is used alone, but 2 or more kinds may be used in combination. The conductive layer 3 is laminated on one resin film 1, but the conductive layer 3 may be further laminated on a plurality of resin films 1 having a laminated structure without any limitation. The metal foil 2 is laminated on the surface of the resin film 1 by a thermal fusion method, and the conductive layer 3 is formed by lamination, but the lamination may be performed by a vapor deposition method or a plating method without any limitation. Further, the high-frequency circuit board can be used for an anti-collision millimeter wave radar device, an Advanced Driving Assistance System (ADAS), an Artificial Intelligence (AI), and the like of an automobile.
Examples
Hereinafter, examples and comparative examples of the resin film, the high-frequency circuit board, and the method for manufacturing the same according to the present invention will be described together.
[ example 1]
First, in order to manufacture a resin film for a high-frequency circuit board, a commercially available polyetheretherketone resin [ product name: victrex Granules 450G (hereinafter, simply referred to as "450G") ] as the polyarylene ether ketone resin, the polyether ether ketone resin was dried for 12 hours or more by a hot-air dehumidifier heated to 160 ℃.
After drying the polyether ether ketone resin, the polyether ether ketone resin was charged into a twin-screw extruder [ 2] provided in the same direction of rotationϕ42mm, L/D =38, product name manufactured by Berstorff: k660]Is in the hopper as the first supply port near the root of the screw. Further, the non-swelling synthetic mica was the second from the side feeder of the co-rotating twin-screw extruder immediately adjacent to the vent opening to the atmospheric pressureThe two supply ports are forcibly pressed in. The synthetic mica used was commercially available potassium tetrasilicate mica (manufactured by Kangan Co-op Agri, product name: micromica MK-100, average particle diameter: 4.9μm]。
In this way, polyether ether ketone resin was charged, and non-swelling synthetic mica was pressed, and then they were melt-kneaded under conditions that the temperature of the cylinder of the co-rotating twin-screw extruder was 350 to 370 ℃, the rotation speed of the screw was 150rpm, and the discharge amount per unit time was 20 kg/hour, and extruded into a strand shape.
The molten state of the polyether ether ketone resin was observed visually from the vent of the co-rotating twin-screw extruder. The polyether ether ketone resin and the synthetic mica were added so that the synthetic mica was 25 parts by mass per 100 parts by mass of the polyether ether ketone resin. After a strip-shaped extruded product was extruded from a co-rotating twin-screw extruder, the extruded product was air-cooled and solidified, and then cut into pellets to prepare a molding material.
Then, the obtained molding material was fed into a single-screw extruder having a T-die with a width of 900mm and melt-kneaded, and the melt-kneaded molding material was continuously extruded from the T-die, and a resin film for a high-frequency circuit board was extrusion-molded into a belt shape. The single screw extrusion molding machine was L/D =32, compression ratio: 2.5, screw: types of full-flight screws. In addition, the temperature of the single-screw extrusion molding machine is adjusted to 380-400 ℃, the temperature of the T-shaped die is adjusted to 400 ℃, and the temperature of a connecting pipe and a gear pump which are used for connecting the single-screw extrusion molding machine and the T-shaped die is adjusted to 400 ℃. When the molding material was charged into the single-screw extrusion molding machine, nitrogen gas was supplied at 18L/min through an inert gas supply pipe.
After the resin film for the high-frequency circuit board was molded in this manner, the resin film was sequentially wound around a pair of nip rollers made of silicone rubber, a plurality of metal rollers as cooling rollers at 200 ℃, 230 ℃, 250 ℃, and a 6-inch winding pipe of a winder located downstream of the nip rollers as shown in fig. 2, and the resin film was sandwiched between the nip rollers and the metal rollers, and both side portions of the continuous resin film were cut by slit blades and sequentially wound around the winding pipe, thereby producing a resin film having a length of 100m and a width of 650 mm. A slit blade for cutting both side portions of the resin film is arranged between the nip roller and the take-up tube so as to be able to be raised and lowered, and a tension roller for applying tension to the resin film is rotatably supported between the take-up tube and the slit blade.
After the production of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties and heat resistance of the resin film were evaluated and are summarized in table 1. The mechanical properties were evaluated by tensile elastic modulus, the dimensional stability under heating by linear expansion coefficient, the dielectric properties by relative dielectric constant and dielectric loss tangent, and the heat resistance by solder heat resistance.
Film thickness of resin film for seed high-frequency circuit substrate
As for the film thickness of the resin film for the high-frequency circuit board, a micrometer (product name manufactured by sanfeng corporation: the anti-cooling liquid micrometer symbol MDC-25PJ ] is measured. In the measurement, arbitrary 10 sites in the transverse direction (the direction perpendicular to the extrusion direction) of the polyarylene ether ketone resin film were measured, and the average value thereof was used as the film thickness.
Relative crystallinity of resin film for seed high-frequency circuit substrate
Regarding the relative crystallinity of the resin film for a high-frequency circuit substrate, about 8mg of a measurement sample was weighed from the resin film, and the relative crystallinity was measured using a differential scanning calorimeter [ product name manufactured by SII Nano Technologies: EXSTAR 7000-series X-DSC7000], at a temperature rise rate of 10 ℃/min, in the measurement temperature range of 20 ℃ to 380 ℃. The heat quantity of the crystal melting peak (J/g) and the heat quantity of the recrystallization peak (J/g) obtained from the above calculation were calculated by the following formulas.
Relative crystallinity (%) = { 1- (Δ Hc/Δ Hm) } × 100
Here,. DELTA.Hc represents the heat quantity (J/g) of the recrystallization peak of the resin film at a temperature rise of 10 ℃ per minute, and. DELTA.Hm represents the heat quantity (J/g) of the crystal melting peak of the resin film at a temperature rise of 10 ℃ per minute.
Mechanical properties of resin film for seed high-frequency circuit substrate
The mechanical properties of the resin film for high-frequency circuit boards were evaluated from the tensile modulus at 23 ℃. The mechanical properties were measured for the extrusion direction and the transverse direction (direction perpendicular to the extrusion direction). The measurement was carried out at a drawing speed of 50 mm/min, a temperature of 23 ℃ C. + -. 2 ℃ C., and a relative humidity of 50 RH. + -. 5% RH in accordance with JIS K7127. The tensile modulus was measured 5 times, and the average value was defined as the tensile modulus.
Dielectric characteristics of resin film for seed high-frequency circuit substrate [ frequency: 1GHz, 10GHz ]
Resin film for high-frequency circuit board having: dielectric properties at 1GHz and 10GHz were measured by a cavity resonator perturbation method using a network analyzer (PNA-L network analyzer N5230A manufactured by Agilent technologies, Inc.). Dielectric properties at 1GHz were measured except that the cavity resonator was changed to 1GHz, a model manufactured by kanto electronic application development corporation; CP431], cavity resonator 10GHz [ manufactured by kanto electronics application development corporation model; CP531], according to ASTM D2520. The dielectric properties were measured at temperature: the preparation is carried out under the environment of 23 +/-1 ℃ and 50 +/-5% RH humidity.
Dielectric characteristics of resin film for seed high-frequency circuit substrate [ frequency: around 28GHz and around 76.5GHz ]
Resin film for high-frequency circuit board having: dielectric properties near 28GHz and near 76.5GHz were measured by the Fabry-Perot method, which is one of the open resonator methods, using a vector network analyzer. The resonator is an open resonator (manufactured by Keycom: Fabry-Perot resonator model: DPS03 ].
In the measurement, a resin film for a high-frequency circuit board was placed on a sample stage of an open resonator jig, and measurement was performed by a Fabry-Perot method, which is one of open resonator methods, using a vector network analyzer. Specifically, the relative permittivity and the dielectric loss tangent were measured by a resonance method using the difference in resonance frequency between the state where the resin film was not placed on the sample stage and the state where the resin film was placed. Specific frequencies for measuring the dielectric characteristics are shown in table 4.
Measurement of dielectric characteristics, specifically, dielectric characteristics in the vicinity of 28GHz and 76.5GHz were measured at temperatures: the measurement was carried out by a predetermined measuring apparatus under an environment of 24 ℃ and a humidity of 40%. As a predetermined measurement apparatus, a vector network analyzer E8361A (manufactured by agilent technologies: product name ]. A vector network analyzer N5227A (manufactured by agilent technologies) was used near 76.5 GHz: product name ].
Linear expansion coefficient of resin film for seed high-frequency circuit substrate
The linear expansion coefficient of the resin film for a high-frequency circuit board was measured in the extrusion direction and the transverse direction of the resin film (the direction perpendicular to the extrusion direction). Specifically, the linear expansion coefficient of the resin film in the extrusion direction was measured by cutting the resin film in a size of 20mm × 4mm in the transverse direction, and the linear expansion coefficient of the resin film in the transverse direction was measured by cutting the resin film in a size of 4mm × 20mm in the transverse direction. In the measurement of the linear expansion coefficient, the linear expansion coefficient was measured by using a thermomechanical analyzer [ product name manufactured by Hitachi High-Tech Science Co.: tensile mode of SII// SS7100] with load: 50mN, temperature rise rate: 5 ℃/min, at a rate of temperature rise: the temperature was raised from 25 ℃ to 250 ℃ at a rate of 5 ℃/min, the temperature change of the size was measured, and the linear expansion coefficient was determined from the slope in the range of 25 ℃ to 125 ℃.
Solder heat resistance of resin film for seed high-frequency circuit board
Solder Heat resistance of resin film for high frequency Circuit Board according to JIS C5016 test method, the resin film was floated in a solder bath at 288 ℃ for 10 seconds, cooled to room temperature, and then visually observed whether the resin film was deformed or wrinkled.
O: no deformation or wrinkle of the resin film was observed;
x: deformation or wrinkling of the resin film was observed.
[ example 2]
First, in order to manufacture a resin film for a high-frequency circuit board, a commercially available polyether ether ketone resin [ product name: ketaspira PEEK KT-851NL SP (hereinafter, abbreviated as "KT-851 NL SP")]The polyarylene ether ketone resin was dried for 12 hours by a hot air dehumidifier heated to 160 ℃The above. As the nonswelling synthetic mica, commercially available potassium tetrasilicate mica [ product name manufactured by silo Co-op Agri: micromica MK-100 DS, average particle diameter: 3.3μm]。
Then, a molding material of a resin film for a high-frequency circuit board was prepared by using a polyether ether ketone resin and synthetic mica in the same manner as in example 1. The polyether ether ketone resin and the synthetic mica were mixed so that the synthetic mica was 35 parts by mass per 100 parts by mass of the polyether ether ketone resin.
After preparing a molding material, a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After extrusion molding of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated in the same manner as in example 1, and are summarized in table 1.
[ example 3]
First, in order to manufacture a resin film for a high-frequency circuit board, a polyether ether ketone resin used in example 2 [ product name: ketasspire PEEK KT-851NL SP (hereinafter, abbreviated as "KT-851 NL SP") ] as a polyarylene ether ketone resin, the polyether ether ketone resin and the nonswelling synthetic mica were produced into a molding material for a resin film for a high-frequency circuit board in the same manner as in example 1. The polyether ether ketone resin and the synthetic mica were added such that the synthetic mica was 45 parts by mass with respect to 100 parts by mass of the polyether ether ketone resin. The synthetic mica was the potassium tetrasilicate mica of example 1.
After preparing a molding material, a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After extrusion molding of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated in the same manner as in example 1, and are summarized in table 1.
[ example 4]
For producing a resin film for a high-frequency circuit board, a commercially available polyetheretherketone resin [ product name: victrex Granules 381G (hereinafter, abbreviated as "381G") ] as the polyarylene ether ketone resin, the polyether ether ketone resin was dried for 12 hours or more by a dehumidifying hot air dryer heated to 160 ℃. The synthetic mica used the potassium tetrasilicate mica of example 1.
Then, non-swelling synthetic mica was added to the polyether ether ketone resin so that the amount of the synthetic mica was 45 parts by mass per 100 parts by mass of the polyether ether ketone resin, and the polyether ether ketone resin and the synthetic mica were produced as a molding material for a resin film for a high-frequency circuit board in the same manner as in example 1.
After preparing a molding material, a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After extrusion molding of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated by the same methods as in example 1, and are shown in table 2.
[ example 5]
For the production of the resin film for high-frequency circuit board, a polyetheretherketone resin used in example 4 was prepared [ product name: victrex Granules 381G (hereinafter, abbreviated as "381G") ] as the polyarylene ether ketone resin, the polyether ether ketone resin was dried for 12 hours or more by a dehumidifying hot air dryer heated to 160 ℃.
Then, a molding material of a resin film for a high-frequency circuit board was prepared from a polyetheretherketone resin and non-swelling synthetic mica in the same manner as in example 1. The nonswelling synthetic mica used was commercially available potassium tetrasilicate mica (product name: micromica MK-300, average particle diameter: 11.9μm]. The polyether ether ketone resin and the synthetic mica were added so that the synthetic mica was 65 parts by mass per 100 parts by mass of the polyether ether ketone resin.
After preparing a molding material, a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After extrusion molding of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated in the same manner as in example 1 and are shown in table 2.
[ Table 1]
[ Table 2]
Comparative example 1
The polyether ether ketone resin used in example 1 was prepared, and dried for 12 hours or more by a dehumidifying dryer heated to 160 ℃. Drying the polyether ether ketone resin, and placing the polyether ether ketone resin in a T-shaped die with the width of 900mmϕMelt-kneading the polyether ether ketone resin in an extrusion molding machine of 40mm, continuously extruding the melt-kneaded polyether ether ketone resin from a T die of a single-screw extrusion molding machine, and then cooling the melt-kneaded polyether ether ketone resin from the single-screw extrusion machine side by using a metal roll heated to 200 ℃, 230 ℃ and 250 ℃, thereby extrusion-molding a resin film for a high-frequency circuit board.ϕThe temperature of a 40mm single screw extrusion molding machine was 380 to 400 ℃ for confirmation, and the temperature of a T die was 400 ℃.
After the resin film for the high-frequency circuit board was extrusion-molded in this manner, the resin film was sequentially wound around a pair of nip rollers made of silicone rubber, a metal roller at 200 ℃, 230 ℃, 250 ℃ from the single-screw extruder side, and a 6-inch winding tube of a winder located downstream of the nip rollers and the metal roller, and the resin film was cut at both side portions of the continuous resin film by a slit blade and sequentially wound around the winding tube, thereby producing a resin film having a length of 100m and a width of 650mm, as shown in fig. 2. After obtaining a resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated in the same manner as in example 1, and are summarized in table 3.
Comparative example 2
The polyether ether ketone resin used in example 2 was prepared, and was dried by a dehumidifier heated to 160 ℃The polyether ether ketone resin is dried for 12 hours or more. After drying the polyether ether ketone resin for 12 hours or more in this manner, the polyether ether ketone resin and calcium carbonate [ manufactured by toyoyo Fine Chemical corporation, product name: whiton P-10, average particle diameter: 2.5μm]A molding material of a resin film for a high-frequency circuit board was prepared. The polyether ether ketone resin and calcium carbonate were mixed so that the amount of calcium carbonate was 43 parts by mass per 100 parts by mass of the polyether ether ketone resin.
Then, a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After extrusion molding of the resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated in the same manner as in example 1, and are summarized in table 3.
Comparative example 3
The polyether ether ketone resin used in example 4 was prepared, and dried for 12 hours or more by a dehumidifying dryer heated to 160 ℃. After drying the polyether ether ketone resin for 12 hours or more, the polyether ether ketone resin and amorphous silica (manufactured by Admatechs corporation, product name: SC5500-SQ, average particle diameter: 1.4μm]Amorphous silica was mixed so as to be 37 parts by mass with respect to 100 parts by mass of a polyether ether ketone resin.
Then, a molding material was prepared, and a resin film for a high-frequency circuit board was extrusion-molded using the molding material in the same manner as in example 1. After obtaining a resin film, the thickness, mechanical properties, thermal dimensional stability, dielectric properties, and heat resistance of the resin film were evaluated by the same methods as in examples, and are shown in table 3.
[ Table 3]
[ Table 4]
[ results ]
The resin film for a high-frequency circuit board of each example had a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.005 or less. In addition, in terms of mechanical properties, the tensile modulus of elasticity was 3500N/mm2As described above, since the high rigidity is provided, the workability is excellent when assembling the high-frequency circuit board. As for the dimensional stability under heating, the linear expansion coefficient was 50 ppm/DEG C or less, and the results were more excellent than ever. Further, as for the heat resistance, even if the solder was floated in a solder bath at 288 ℃ for 10 seconds, no deformation or wrinkle was observed at all, and the solder had a heat resistance usable as a high-frequency circuit board.
On the other hand, the resin film for a high-frequency circuit board of the comparative example had a linear expansion coefficient of 55 ppm/DEG C or more because no nonswelling synthetic mica was added, and thus insufficient results were obtained. These measurement results show that: the resin films of the examples have excellent dielectric properties and are most suitable for high-frequency circuit boards used in high frequency bands ranging from MHz to GHz.
Industrial applicability
The resin film, the high-frequency circuit board, and the method for manufacturing the same according to the present invention are used in the fields of information communication, automobile equipment, and the like.
Description of the symbols
1: a resin film;
2: a metal foil (metal layer);
3: a conductive layer;
4: molding a material;
10: a melt extrusion molding machine (extrusion molding machine);
11: a raw material input port;
13: t-die (die);
16: a cooling roll;
17: a press-fit roller;
18: a winding machine;
19: a winding tube;
20: a slit blade.
Claims (7)
1. A resin film characterized by: contains 100 parts by mass of a polyarylene ether ketone resin and 10 to 80 parts by mass of a nonswelling synthetic mica.
2. The resin film according to claim 1, wherein the relative crystallinity of the resin film is 80% or more.
3. The resin film according to claim 1 or 2, which has a linear expansion coefficient of 1ppm/° C or more and 50ppm/° C or less.
4. The resin film according to claim 1, 2 or 3, wherein the nonswelling synthetic mica is at least any one of fluorophlogopite, tetrapotassium silicate mica and potassium taeniolite.
5. A high-frequency circuit board, characterized in that: the resin film according to any one of claims 1 to 4.
6. A high-frequency circuit board according to claim 5, wherein the high-frequency circuit board comprises a metal layer laminated by heat-fusing with a resin film.
7. A method for manufacturing a high-frequency circuit board, comprising: a method for producing a high-frequency circuit board according to claim 5 or 6, wherein a molding material comprising at least 100 parts by mass of a polyarylene ether ketone resin and 10 to 80 parts by mass of a nonswelling synthetic mica is melt-kneaded, the molding material is extruded through a die of an extrusion molding machine to form a resin film, and the resin film is cooled by contacting with a cooling roll so that the relative crystallinity of the resin film is 80% or more and the linear expansion coefficient of the resin film is 1 to 50 ppm/DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-080405 | 2019-04-19 | ||
| JP2019080405 | 2019-04-19 | ||
| PCT/JP2020/016123 WO2020213527A1 (en) | 2019-04-19 | 2020-04-10 | Resin film, high-frequency circuit board, and production method for high-frequency circuit board |
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| Publication Number | Publication Date |
|---|---|
| CN113784838A true CN113784838A (en) | 2021-12-10 |
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| CN202080029888.5A Pending CN113784838A (en) | 2019-04-19 | 2020-04-10 | Resin film, high-frequency circuit board and method for producing same |
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| Country | Link |
|---|---|
| JP (1) | JPWO2020213527A1 (en) |
| KR (1) | KR20220005466A (en) |
| CN (1) | CN113784838A (en) |
| TW (1) | TWI809265B (en) |
| WO (1) | WO2020213527A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338823A (en) * | 2001-05-21 | 2002-11-27 | Mitsubishi Plastics Ind Ltd | Heat-resistant film for substrate and printed wiring board obtained using the same |
| CN1402760A (en) * | 1999-11-30 | 2003-03-12 | 大塚化学株式会社 | Resin composition and flexible printed circuit board |
| CN1486341A (en) * | 2001-01-22 | 2004-03-31 | 三菱树脂株式会社 | Polyaryl ketone resin film and laminates therof with metal |
| JP2018109090A (en) * | 2016-12-28 | 2018-07-12 | 株式会社クラレ | Thermoplastic liquid crystal polymer film and circuit board using the same |
| JP2019046980A (en) * | 2017-09-01 | 2019-03-22 | 信越ポリマー株式会社 | Electromagnetic wave shielding film and manufacturing method thereof and electromagnetic wave shielding film-equipped printed wiring board and manufacturing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1020708C (en) | 1988-01-21 | 1993-05-19 | 希欧欧匹化学株式会社 | Method for producing fluorine mica |
| CN104753627A (en) | 2013-12-26 | 2015-07-01 | 中兴通讯股份有限公司 | Multipath transmission method, multipath transmission system, data transmission device and data receiving device |
-
2020
- 2020-04-10 WO PCT/JP2020/016123 patent/WO2020213527A1/en active Application Filing
- 2020-04-10 CN CN202080029888.5A patent/CN113784838A/en active Pending
- 2020-04-10 KR KR1020217034273A patent/KR20220005466A/en unknown
- 2020-04-10 JP JP2021514923A patent/JPWO2020213527A1/ja active Pending
- 2020-04-17 TW TW109112942A patent/TWI809265B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402760A (en) * | 1999-11-30 | 2003-03-12 | 大塚化学株式会社 | Resin composition and flexible printed circuit board |
| CN1486341A (en) * | 2001-01-22 | 2004-03-31 | 三菱树脂株式会社 | Polyaryl ketone resin film and laminates therof with metal |
| JP2002338823A (en) * | 2001-05-21 | 2002-11-27 | Mitsubishi Plastics Ind Ltd | Heat-resistant film for substrate and printed wiring board obtained using the same |
| JP2018109090A (en) * | 2016-12-28 | 2018-07-12 | 株式会社クラレ | Thermoplastic liquid crystal polymer film and circuit board using the same |
| JP2019046980A (en) * | 2017-09-01 | 2019-03-22 | 信越ポリマー株式会社 | Electromagnetic wave shielding film and manufacturing method thereof and electromagnetic wave shielding film-equipped printed wiring board and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020213527A1 (en) | 2020-10-22 |
| KR20220005466A (en) | 2022-01-13 |
| TWI809265B (en) | 2023-07-21 |
| TW202104392A (en) | 2021-02-01 |
| WO2020213527A1 (en) | 2020-10-22 |
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