WO2022260087A1 - 多孔質液晶ポリマーシート、金属層付き多孔質液晶ポリマーシート、及び、電子回路基板 - Google Patents
多孔質液晶ポリマーシート、金属層付き多孔質液晶ポリマーシート、及び、電子回路基板 Download PDFInfo
- Publication number
- WO2022260087A1 WO2022260087A1 PCT/JP2022/023141 JP2022023141W WO2022260087A1 WO 2022260087 A1 WO2022260087 A1 WO 2022260087A1 JP 2022023141 W JP2022023141 W JP 2022023141W WO 2022260087 A1 WO2022260087 A1 WO 2022260087A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- crystal polymer
- polymer sheet
- porous liquid
- metal layer
- Prior art date
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 397
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 397
- 229910052751 metal Inorganic materials 0.000 title claims description 217
- 239000002184 metal Substances 0.000 title claims description 217
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000011347 resin Substances 0.000 claims abstract description 81
- 239000000155 melt Substances 0.000 claims abstract description 44
- 238000005259 measurement Methods 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 24
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 17
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 17
- 239000011889 copper foil Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000010008 shearing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 190
- 239000004020 conductor Substances 0.000 description 71
- 239000011229 interlayer Substances 0.000 description 71
- 238000000034 method Methods 0.000 description 33
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 20
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 238000002788 crimping Methods 0.000 description 9
- 238000010894 electron beam technology Methods 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- -1 aromatics Chemical class 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- MELXIJRBKWTTJH-ONEGZZNKSA-N (e)-2,3-dibromobut-2-ene-1,4-diol Chemical compound OC\C(Br)=C(/Br)CO MELXIJRBKWTTJH-ONEGZZNKSA-N 0.000 description 1
- DSESGJJGBBAHNW-UHFFFAOYSA-N (e)-[amino(anilino)methylidene]-phenylazanium;bromide Chemical compound Br.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 DSESGJJGBBAHNW-UHFFFAOYSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- OXYNQEOLHRWEPE-UHFFFAOYSA-N 2,3-dibromobutane-1,4-diol Chemical compound OCC(Br)C(Br)CO OXYNQEOLHRWEPE-UHFFFAOYSA-N 0.000 description 1
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IUGOPULVANEDRX-UHFFFAOYSA-N 2-ethylhexane-1,1-diol Chemical compound CCCCC(CC)C(O)O IUGOPULVANEDRX-UHFFFAOYSA-N 0.000 description 1
- IKJAVHKRVPYFOD-UHFFFAOYSA-N 2-hydroxyethylazanium;bromide Chemical compound Br.NCCO IKJAVHKRVPYFOD-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- LVFFZQQWIZURIO-UHFFFAOYSA-N 2-phenylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)C1=CC=CC=C1 LVFFZQQWIZURIO-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- IEDHGYYAGIASNQ-UHFFFAOYSA-N [amino(anilino)methylidene]-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[NH+]=C(N)NC1=CC=CC=C1 IEDHGYYAGIASNQ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QOHWJRRXQPGIQW-UHFFFAOYSA-N cyclohexanamine;hydron;bromide Chemical compound Br.NC1CCCCC1 QOHWJRRXQPGIQW-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- SPQWAFOMVNLPNC-UHFFFAOYSA-N n,n-diethylaniline;hydrobromide Chemical class Br.CCN(CC)C1=CC=CC=C1 SPQWAFOMVNLPNC-UHFFFAOYSA-N 0.000 description 1
- PQCWTNQXCXUEAO-UHFFFAOYSA-N n,n-diethylaniline;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=CC=C1 PQCWTNQXCXUEAO-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UKKLUBWWAGMMAG-UHFFFAOYSA-N tris(2-hydroxyethyl)azanium;bromide Chemical compound Br.OCCN(CCO)CCO UKKLUBWWAGMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0116—Porous, e.g. foam
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0141—Liquid crystal polymer [LCP]
Definitions
- the present invention relates to a porous liquid crystal polymer sheet, a porous liquid crystal polymer sheet with a metal layer, and an electronic circuit board.
- Patent Document 1 As a method for producing a porous liquid crystal polymer sheet, in Patent Document 1, a liquid crystal polymer substance having self-orientation and a non-liquid crystal polymer substance soluble in a solvent are mixed at a weight ratio of 70:30 to 40:60. and then extruded into a sheet, and then selectively solvent-extracting non-liquid crystal polymer substances from the molded body to remove the non-liquid crystal polymer material. A method is disclosed.
- liquid crystal polymer sheets are known as materials for improving the dielectric properties of electronic circuit boards used in various electronic devices in the high-frequency range.
- the inventors of the present invention have found that, in addition to the liquid crystal polymer, conventional porous liquid crystal polymer sheets such as the porous liquid crystal polymer sheet described in Patent Document 1, which have pores that can contribute to a further reduction in the dielectric constant, It was investigated to further improve the dielectric properties of electronic circuit boards in the high-frequency region by using a high-quality liquid crystal polymer sheet.
- the present invention was made to solve the above problems, and an object of the present invention is to provide a porous liquid crystal polymer sheet whose pores are less likely to collapse under high temperature and pressure. Another object of the present invention is to provide a porous liquid crystal polymer sheet with a metal layer having the above porous liquid crystal polymer sheet. A further object of the present invention is to provide an electronic circuit board having the porous liquid crystal polymer sheet with the metal layer.
- the porous liquid crystal polymer sheet of the present invention is a porous liquid crystal polymer sheet made of a resin sheet containing a liquid crystal polymer, and having pores in the resin sheet, wherein the melting point of the resin sheet is 20°C higher than the melting point of the resin sheet. It is characterized by having a melt viscosity of 20 Pa ⁇ s or more under conditions of a high temperature for measurement and a shear rate of 1000 s ⁇ 1 .
- a porous liquid crystal polymer sheet with a metal layer of the present invention comprises the porous liquid crystal polymer sheet of the present invention and a metal layer provided on at least one main surface of the porous liquid crystal polymer sheet. .
- the electronic circuit board of the present invention is characterized by comprising the porous liquid crystal polymer sheet with a metal layer of the present invention.
- the present invention it is possible to provide a porous liquid crystal polymer sheet whose pores are less likely to collapse under high temperature and pressure. Further, according to the present invention, it is possible to provide a porous liquid crystal polymer sheet with a metal layer having the above porous liquid crystal polymer sheet. Furthermore, according to the present invention, it is possible to provide an electronic circuit board having the porous liquid crystal polymer sheet with the metal layer.
- FIG. 1 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet of the present invention.
- FIG. 2 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet with a metal layer of the present invention.
- FIG. 3 is a schematic cross-sectional view showing an example of the electronic circuit board of the present invention.
- FIG. 4 is a schematic cross-sectional view showing a process for producing a porous liquid crystal polymer sheet with a metal layer in one example of the method for producing an electronic circuit board of the present invention.
- FIG. 5 is a schematic cross-sectional view showing a process for producing a porous liquid crystal polymer sheet with a metal layer in one example of the method for producing an electronic circuit board of the present invention.
- FIG. 1 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet of the present invention.
- FIG. 2 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet with a
- FIG. 6 is a schematic cross-sectional view showing a process for producing a porous liquid crystal polymer sheet with a metal layer in one example of the method for producing an electronic circuit board of the present invention.
- FIG. 7 is a schematic cross-sectional view showing a step of forming via holes in one example of the method for manufacturing an electronic circuit board according to the present invention.
- FIG. 8 is a schematic cross-sectional view showing a step of forming via holes in one example of the method for manufacturing an electronic circuit board according to the present invention.
- FIG. 9 is a schematic cross-sectional view showing a conductive paste filling step in one example of the method for manufacturing an electronic circuit board according to the present invention.
- FIG. 10 is a schematic cross-sectional view showing a conductive paste filling step in one example of the method for manufacturing an electronic circuit board according to the present invention.
- FIG. 11 is a schematic cross-sectional view showing a step of forming interlayer connection conductors in one example of the method of manufacturing an electronic circuit board according to the present invention.
- porous liquid crystal polymer sheet of the present invention the porous liquid crystal polymer sheet with a metal layer of the present invention, and the electronic circuit board of the present invention are described below. It should be noted that the present invention is not limited to the following configurations, and may be modified as appropriate without departing from the gist of the present invention.
- the present invention also includes a combination of a plurality of individual preferred configurations described below.
- the porous liquid crystal polymer sheet of the present invention is a porous liquid crystal polymer sheet made of a resin sheet containing a liquid crystal polymer and having pores provided in the resin sheet.
- sheet is synonymous with “film”, and the two are not distinguished by thickness.
- FIG. 1 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet of the present invention.
- the porous liquid crystal polymer sheet 1 shown in FIG. 1 has a first main surface 1a and a second main surface 1b facing each other in the thickness direction.
- the porous liquid crystal polymer sheet 1 consists of a resin sheet 1s containing a liquid crystal polymer.
- the pores 1h are provided in the resin sheet 1s. More specifically, in the porous liquid crystal polymer sheet 1, holes 1h are provided inside the resin sheet 1s.
- the porous liquid crystal polymer sheet of the present invention has a melt viscosity of 20 Pa ⁇ s or more under conditions of a measurement temperature of 20° C. higher than the melting point of the resin sheet and a shear rate of 1000 s ⁇ 1 .
- the porous liquid crystal polymer sheet 1 shown in FIG. 1 has a melt viscosity of 20 Pa ⁇ s or more under the conditions of a measurement temperature of 20° C. higher than the melting point of the resin sheet 1 s and a shear rate of 1000 s ⁇ 1 .
- the porous liquid crystal polymer sheet 1 has a melt viscosity of 20 Pa s or more under the above conditions.
- the pores 1h are less likely to collapse under high temperature and pressure during press-bonding. Therefore, in the electronic circuit board manufactured using the porous liquid crystal polymer sheet 1, the effect of reducing the dielectric constant by the porous liquid crystal polymer sheet 1 is easily exhibited, and the dielectric characteristics in the high frequency region are easily improved. Furthermore, since the liquid crystal polymer has a low hygroscopicity, the electronic circuit board manufactured using the porous liquid crystal polymer sheet 1 is less susceptible to changes in dielectric properties due to moisture absorption.
- melt viscosity of the porous liquid crystal polymer sheet 1 under the above conditions is lower than 20 Pa ⁇ s, the pores 1h are likely to collapse under high temperature and pressure.
- the melt viscosity of the porous liquid crystal polymer sheet 1 under the above conditions is preferably 500 Pa ⁇ s or less, more preferably 200 Pa ⁇ s or less.
- the melt viscosity is defined at a measurement temperature 20°C higher than the melting point of the resin sheet in order to accurately measure the melt viscosity while suppressing deterioration of the liquid crystal polymer.
- the melting point of the resin sheet is determined as follows. First, for example, using a differential scanning calorimeter such as a differential scanning calorimeter "DSC7000X" manufactured by Hitachi High-Tech Science Co., Ltd., the temperature of the resin sheet, that is, the porous liquid crystal polymer sheet is raised to completely melt it. In this temperature rising process, the temperature rising rate is, for example, 20° C./min. The resulting melt is then cooled and then heated again. At this time, the temperature is lowered to 175° C. at a temperature drop rate of 20° C./min in the temperature drop process, and the temperature is raised at a temperature rise rate of 20° C./min in the temperature rise process, for example.
- a differential scanning calorimeter such as a differential scanning calorimeter "DSC7000X” manufactured by Hitachi High-Tech Science Co., Ltd.
- the temperature corresponding to the endothermic peak observed during this heating process is defined as the melting point of the resin sheet, that is, the porous liquid crystal polymer sheet. If the endothermic peak is difficult to observe by the method described above, the melting point of the resin sheet, that is, the porous liquid crystal polymer sheet is determined by texture observation under crossed Nicols conditions with a polarizing microscope.
- the melt viscosity of the porous liquid crystal polymer sheet of the present invention under the above conditions is adjusted to 20 Pa ⁇ s or more by performing solid phase polymerization of the liquid crystal polymer during production of the porous liquid crystal polymer sheet, for example.
- the liquid crystal polymer is solid-phase polymerized, the molecular chain length of the liquid crystal polymer is elongated, and the liquid crystal polymers having the elongated molecular chain length are entangled with each other, and the melt viscosity of the porous liquid crystal polymer sheet tends to increase.
- the melt viscosity of the porous liquid crystal polymer sheet can also be increased by irradiating the liquid crystal polymer with electron beams, as described later, although the effect is slightly inferior to solid-phase polymerization of the liquid crystal polymer.
- melt viscosity of the porous liquid crystal polymer sheet can also be adjusted by the polymerization conditions such as the polymerization temperature and polymerization time of the liquid crystal polymer.
- the porous liquid crystal polymer sheet of the present invention preferably has a melt tension of 3 mN or more at the above measurement temperature.
- the porous liquid crystal polymer sheet 1 shown in FIG. 1 preferably has a melt tension of 3 mN or more at the above measurement temperature.
- the metal layer is formed from the porous liquid crystal polymer.
- the holes 1h are less likely to be crushed.
- the melt tension of the porous liquid crystal polymer sheet 1 at the above measurement temperature is preferably 20 mN or less, more preferably 10 mN or less, and even more preferably 7 mN or less.
- the reason why the melt tension is specified by the above measurement temperature is the same as the reason for specifying the melt viscosity by the above measurement temperature.
- the melt tension of the porous liquid crystal polymer sheet of the present invention at the above measurement temperature is adjusted to 3 mN or more by, for example, irradiating the liquid crystal polymer with an electron beam during the production of the porous liquid crystal polymer sheet.
- the liquid crystal polymer is irradiated with an electron beam, the cross-linking reaction of the liquid crystal polymer is accelerated, so that the number of cross-linking points increases, and the melt tension of the porous liquid crystal polymer sheet tends to increase.
- the melt tension of the porous liquid crystal polymer sheet can also be increased by performing solid phase polymerization of the liquid crystal polymer, although the effect is slightly inferior to the case of irradiating the liquid crystal polymer with an electron beam.
- melt tension of the porous liquid crystal polymer sheet can also be adjusted by the polymerization conditions such as the polymerization temperature and polymerization time of the liquid crystal polymer.
- the melting point of the resin sheet is preferably 275°C or higher and 330°C or lower.
- the melting point of the resin sheet 1s is preferably 275°C or higher and 330°C or lower.
- the melting point of the resin sheet 1s is lower than 275° C., for example, when an electronic circuit board manufactured using the porous liquid crystal polymer sheet 1 made of the resin sheet 1s is incorporated into an electronic device by reflow soldering, the resin sheet 1s is may lack heat resistance.
- the melting point of the resin sheet 1s is higher than 330°C, for example, a higher processing temperature is required during film formation of the resin sheet 1s, which may accelerate the deterioration of the liquid crystal polymer.
- the liquid crystal polymer preferably contains a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
- the liquid crystal polymer preferably contains a copolymer of p-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA).
- HBA p-hydroxybenzoic acid
- HNA 6-hydroxy-2-naphthoic acid
- a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid is generally called a type II wholly aromatic polyester (also called a 1.5 type wholly aromatic polyester).
- the type II wholly aromatic polyester is more resistant to hydrolysis than the type III partially aromatic polyester, and is therefore preferable as a constituent material for an electronic circuit board manufactured using the porous liquid crystal polymer sheet 1 .
- the type II wholly aromatic polyester has a small dielectric loss tangent due to the naphthalene ring, and therefore contributes to the reduction of electrical energy loss in the porous liquid crystal polymer sheet 1 in the electronic circuit board.
- the liquid crystal polymer may further contain type I wholly aromatic polyester in addition to type II wholly aromatic polyester, or may further contain type III partially aromatic polyester. or it may further contain a type I wholly aromatic polyester and a type III partially aromatic polyester.
- the structure (kind) of each monomer that constitutes the liquid crystal polymer can be analyzed by reactive pyrolysis gas chromatography mass spectrometry (reactive pyrolysis GC-MS method).
- the molar ratio of p-hydroxybenzoic acid to 6-hydroxy-2-naphthoic acid in the liquid crystal polymer is preferably 0.20 or more and 5 or less.
- the molar ratio of p-hydroxybenzoic acid to 6-hydroxy-2-naphthoic acid in the liquid crystal polymer is preferably 0.20 or more and 5 or less.
- the melting point of the resin sheet 1s will be higher than the preferred range described above. Sometimes.
- the liquid crystal polymer may contain p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in an amount of 10 mol% or more each when the total monomer amount is 100 mol%. preferable.
- the liquid crystal polymer contains 10 mol % or more of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, respectively, when the total monomer amount is 100 mol %. is preferred.
- the ratio and content of each monomer that constitutes the liquid crystal polymer can be analyzed by reactive pyrolysis gas chromatography mass spectrometry.
- the thickness of the porous liquid crystal polymer sheet of the present invention is preferably 10 ⁇ m or more and 200 ⁇ m or less.
- the thickness of the porous liquid crystal polymer sheet 1 shown in FIG. 1 is preferably 10 ⁇ m or more and 200 ⁇ m or less.
- the thickness of the porous liquid crystal polymer sheet 1 is less than 10 ⁇ m, the porosity of the pores 1h on at least one of the first main surface 1a and the second main surface 1b tends to increase, resulting in a decrease in smoothness. easier to do.
- the metal layer is etched to have a pattern shape such as a wiring. Pattern loss is likely to occur due to 1h.
- the thickness of the porous liquid crystal polymer sheet 1 is greater than 200 ⁇ m, when the porous liquid crystal polymer sheet 1 is used to manufacture an electronic circuit board having interlayer connection conductors, the via holes in which the interlayer connection conductors are formed are not porous. It may be difficult to form the liquid crystal polymer sheet 1 so as to penetrate it.
- the thickness of the porous liquid crystal polymer sheet is determined as follows. First, a 100 mm square sample is cut out from a porous liquid crystal polymer sheet. Then, the thickness is measured at 9 equally spaced points in a 25 mm square area that shares the center with the sample, and the average value of these measurements is determined as the thickness of the porous liquid crystal polymer sheet. If a 100 mm square sample cannot be cut from the porous liquid crystal polymer sheet, the thickness of the porous liquid crystal polymer sheet is determined in the same manner as described above, except that the porous liquid crystal polymer sheet itself is used as the sample.
- the thickness of the porous liquid crystal polymer sheet is measured at nine equally spaced locations, and the average value of these is taken as the porous liquid crystal polymer. Determine the thickness of the sheet.
- the porous liquid crystal polymer sheet 1, more specifically the resin sheet 1s, preferably has a closed cell structure as the arrangement structure of the pores 1h.
- a porous liquid crystal polymer sheet having a closed cell structure means that the porous liquid crystal polymer sheet has a structure in which all wall surfaces of pores (bubbles) are surrounded by resin. Observing the cross section along the thickness direction of the porous liquid crystal polymer sheet and the cross section along the in-plane direction perpendicular to the thickness direction of the porous liquid crystal polymer sheet, even if the wall surfaces of the pores are not connected to each other. For example, it is determined that the porous liquid crystal polymer sheet has a closed cell structure.
- the paths for the air in the pores 1h to escape to the outside are likely to be fewer than when the porous liquid crystal polymer sheet 1 has an open-cell structure.
- the porous liquid crystal polymer sheet 1 When pressed against the porous liquid crystal polymer sheet 1, the porous liquid crystal polymer sheet 1, more specifically, the pores 1h are less likely to collapse.
- the porous liquid crystal polymer sheet 1 is produced, for example, by the following method.
- a resin material is prepared by mixing a liquid crystal polymer and a foaming agent at a predetermined ratio.
- a so-called porous resin sheet that is, a resin sheet provided with pores is produced by an extrusion molding method.
- Extrusion molding methods include, for example, a T-die molding method and an inflation molding method.
- the porous resin sheet is subjected to solid-phase polymerization of the liquid crystal polymer, electron beam irradiation to the liquid crystal polymer, or both of these, so that the melt viscosity under the above conditions is 20 Pa s or more. increase to
- porous liquid crystal polymer sheet 1 made of the resin sheet 1s provided with the holes 1h is manufactured.
- the porous liquid crystal polymer sheet 1 has a melt viscosity of 20 Pa ⁇ s or more under the above conditions.
- the porous liquid crystal polymer sheet with a metal layer of the present invention comprises the porous liquid crystal polymer sheet of the present invention and a metal layer provided on at least one main surface of the porous liquid crystal polymer sheet.
- FIG. 2 is a schematic cross-sectional view showing an example of the porous liquid crystal polymer sheet with a metal layer of the present invention.
- a porous liquid crystal polymer sheet 10 with a metal layer shown in FIG. 2 has a porous liquid crystal polymer sheet 1 and a metal layer 2 in the stacking direction.
- the lamination direction corresponds to the direction along the thickness direction of the porous liquid crystal polymer sheet that constitutes the porous liquid crystal polymer sheet with the metal layer.
- the metal layer 2 is provided on at least one main surface of the porous liquid crystal polymer sheet 1, here, on the first main surface 1a. More specifically, the metal layer 2 is adjacent to the first major surface 1a side of the porous liquid crystal polymer sheet 1 .
- the metal layer 2 may have a pattern shape that is patterned into wiring or the like, or may have a planar shape that spreads all over.
- constituent materials of the metal layer 2 include copper, silver, aluminum, stainless steel, nickel, gold, and alloys containing at least one of these metals.
- the metal layer is preferably made of copper foil.
- the metal layer 2 is preferably made of copper foil.
- the surface of the copper foil may be plated with a metal other than copper.
- the thickness of the metal layer 2 is preferably 1 ⁇ m or more and 35 ⁇ m or less, more preferably 6 ⁇ m or more and 18 ⁇ m or less.
- the porous liquid crystal polymer sheet 10 with a metal layer may further have another metal layer provided on the second main surface 1 b of the porous liquid crystal polymer sheet 1 in addition to the metal layer 2 .
- the metal layer-attached porous liquid crystal polymer sheet 10 is manufactured, for example, by pressing the metal layer 2 onto the first main surface 1a of the porous liquid crystal polymer sheet 1 . After the metal layer 2 is pressure-bonded to the first main surface 1a of the porous liquid crystal polymer sheet 1, the metal layer 2 may be etched into a pattern shape.
- the metal layer-attached porous liquid crystal polymer sheet 10 may be produced by pressing the pre-patterned metal layer 2 onto the first main surface 1 a of the porous liquid crystal polymer sheet 1 .
- the electronic circuit board of the present invention comprises the metal layer-attached porous liquid crystal polymer sheet of the present invention.
- FIG. 3 is a schematic cross-sectional view showing an example of the electronic circuit board of the present invention.
- the electronic circuit board 50 shown in FIG. 3 has a porous liquid crystal polymer sheet 10A with a metal layer, a porous liquid crystal polymer sheet 10B with a metal layer, and a porous liquid crystal polymer sheet 10C with a metal layer in the stacking direction. ing. That is, in the electronic circuit board 50, the porous liquid crystal polymer sheet 10A with a metal layer, the porous liquid crystal polymer sheet 10B with a metal layer, and the porous liquid crystal polymer sheet 10C with a metal layer are laminated in order in the stacking direction. .
- a porous liquid crystal polymer sheet 10A with a metal layer has a porous liquid crystal polymer sheet 1A and a metal layer 2A.
- the porous liquid crystal polymer sheet 1A has a first main surface 1Aa and a second main surface 1Ab facing each other in the thickness direction.
- the porous liquid crystal polymer sheet 1A is made of a resin sheet 1As containing a liquid crystal polymer. In the porous liquid crystal polymer sheet 1A, holes 1Ah are provided in the resin sheet 1As.
- the metal layer 2A is provided on the first main surface 1Aa of the porous liquid crystal polymer sheet 1A. Also, the metal layer 2A is adjacent to the second main surface 1Bb side of the porous liquid crystal polymer sheet 1B, which will be described later.
- a porous liquid crystal polymer sheet 10B with a metal layer has a porous liquid crystal polymer sheet 1B, a metal layer 2B, a metal layer 2B', and a metal layer 2B''.
- the porous liquid crystal polymer sheet 1B has a first main surface 1Ba and a second main surface 1Bb facing each other in the thickness direction.
- the porous liquid crystal polymer sheet 1B consists of a resin sheet 1Bs containing a liquid crystal polymer. In the porous liquid crystal polymer sheet 1B, holes 1Bh are provided in the resin sheet 1Bs.
- the metal layer 2B, the metal layer 2B', and the metal layer 2B'' are provided on the first main surface 1Ba of the porous liquid crystal polymer sheet 1B. Moreover, the metal layer 2B, the metal layer 2B', and the metal layer 2B'' are adjacent to the second main surface 1Cb side of the porous liquid crystal polymer sheet 1C, which will be described later.
- a porous liquid crystal polymer sheet 10C with a metal layer has a porous liquid crystal polymer sheet 1C and a metal layer 2C.
- the porous liquid crystal polymer sheet 1C has a first main surface 1Ca and a second main surface 1Cb facing each other in the thickness direction.
- the porous liquid crystal polymer sheet 1C consists of a resin sheet 1Cs containing a liquid crystal polymer. In the porous liquid crystal polymer sheet 1C, holes 1Ch are provided in the resin sheet 1Cs.
- the metal layer 2C is provided on the first main surface 1Ca of the porous liquid crystal polymer sheet 1C.
- the metal layer 2B is preferably provided across the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C.
- the interface between the metal layer 2B and the porous liquid crystal polymer sheet 1B and the interface between the metal layer 2B and the porous liquid crystal polymer sheet 1C become the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C.
- the peeling at the interface between the metal layer 2B and the porous liquid crystal polymer sheet 1B and the peeling at the interface between the metal layer 2B and the porous liquid crystal polymer sheet 1C are suppressed.
- the metal layer 2B' and the metal layer 2B'' are also provided across the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C, similarly to the metal layer 2B.
- the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C is shown in FIG. 3, the interface does not have to appear clearly in practice.
- the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C does not clearly appear, in the cross section along the lamination direction as shown in FIG.
- the surface along the direction orthogonal to the stacking direction is regarded as the interface between the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C.
- porous liquid crystal polymer sheet 1A, the porous liquid crystal polymer sheet 1B, and the porous liquid crystal polymer sheet 1C, similarly to the porous liquid crystal polymer sheet 1 a temperature 20° C. higher than the melting point of the resin sheet constituting each was measured.
- the melt viscosity is 20 Pa ⁇ s or more under the conditions of temperature and shear rate of 1000 s ⁇ 1 . Therefore, in the porous liquid crystal polymer sheet 1A, the porous liquid crystal polymer sheet 1B, and the porous liquid crystal polymer sheet 1C, similarly to the porous liquid crystal polymer sheet 1, the pores are less likely to collapse under high temperature and pressure.
- the electronic circuit board 50 has the porous liquid crystal polymer sheet 1A, the porous liquid crystal polymer sheet 1B, and the porous liquid crystal polymer sheet 1C, the dielectric properties of the electronic circuit board 50 in the high frequency region are improved. easier. Also, in the electronic circuit board 50, the change in dielectric characteristics due to moisture absorption is less likely to occur.
- all the porous liquid crystal polymer sheets preferably have a melt viscosity of 20 Pa ⁇ s or more under the above conditions.
- the melt viscosity under the above conditions may be 20 Pa ⁇ s or more.
- porous liquid crystal polymer sheet 1A, the porous liquid crystal polymer sheet 1B, and the porous liquid crystal polymer sheet 1C are the same as the preferred features of the porous liquid crystal polymer sheet 1 described above.
- the thicknesses of the porous liquid crystal polymer sheet 1A, the porous liquid crystal polymer sheet 1B, and the porous liquid crystal polymer sheet 1C may be the same or different. It can be different in different departments.
- the constituent materials of the metal layer 2A, the metal layer 2B, the metal layer 2B', the metal layer 2B'', and the metal layer 2C similar to the constituent material of the metal layer 2, for example, copper, silver, aluminum, stainless steel, Examples include nickel, gold, and alloys containing at least one of these metals.
- the metal layer 2A, the metal layer 2B, the metal layer 2B', the metal layer 2B'', and the metal layer 2C are preferably made of copper foil, like the metal layer 2.
- the surface of the copper foil may be plated with a metal other than copper.
- the constituent materials of the metal layer 2A, the metal layer 2B, the metal layer 2B′, the metal layer 2B′′, and the metal layer 2C are preferably the same as each other, but may be different from each other, or partially different. may be
- the thicknesses of the metal layer 2A, the metal layer 2B, the metal layer 2B', the metal layer 2B'', and the metal layer 2C may be the same as shown in FIG. 3, or may be different. , may be different in part.
- the electronic circuit board 50 has three porous liquid crystal polymer sheets with metal layers in the stacking direction, but may have only one, two, or four or more. may have.
- the electronic circuit board 50 should have at least one porous liquid crystal polymer sheet having a melt viscosity of 20 Pa ⁇ s or more under the above conditions. As long as the electronic circuit board 50 has at least one porous liquid crystal polymer sheet with a melt viscosity of 20 Pa s or more under the above conditions, the electronic circuit board 50 has a porous liquid crystal polymer sheet with a melt viscosity of less than 20 Pa s under the above conditions. It may have a liquid crystal polymer sheet that is not porous.
- the electronic circuit board 50 is an interlayer connection conductor provided so as to be connected to the metal layer without penetrating the porous liquid crystal polymer sheet in the stacking direction but not the metal layer in the stacking direction. is preferably further provided.
- the electronic circuit board 50 further includes an interlayer connection conductor 20A, an interlayer connection conductor 20B, an interlayer connection conductor 20C, and an interlayer connection conductor 20D.
- the interlayer connection conductor 20A penetrates the porous liquid crystal polymer sheet 1B in the stacking direction, but does not penetrate the metal layer 2B' in the stacking direction, and is provided so as to be connected to the metal layer 2B'. More specifically, the interlayer connection conductor 20A penetrates the porous liquid crystal polymer sheet 1B in the stacking direction and is connected to the metal layer 2B' on the first main surface 1Ba side of the porous liquid crystal polymer sheet 1B. Further, the interlayer connection conductor 20A is connected to the metal layer 2A on the second main surface 1Bb side of the porous liquid crystal polymer sheet 1B. That is, the metal layer 2A and the metal layer 2B' are electrically connected via the interlayer connection conductor 20A.
- the interlayer connection conductor 20B penetrates the porous liquid crystal polymer sheet 1B in the stacking direction at a position separated from the interlayer connection conductor 20A, but does not penetrate the metal layer 2B'' in the stacking direction, and is connected to the metal layer 2B''. It is designed to be More specifically, the interlayer connection conductor 20B penetrates the porous liquid crystal polymer sheet 1B in the stacking direction at a position spaced apart from the interlayer connection conductor 20A, and is located on the first main surface 1Ba side of the porous liquid crystal polymer sheet 1B. It is connected to the metal layer 2B''.
- interlayer connection conductor 20B is connected to the metal layer 2A on the second main surface 1Bb side of the porous liquid crystal polymer sheet 1B at a position separated from the interlayer connection conductor 20A. That is, the metal layer 2A and the metal layer 2B'' are electrically connected via the interlayer connection conductor 20B.
- the interlayer connection conductor 20C penetrates the porous liquid crystal polymer sheet 1C in the stacking direction, but does not penetrate the metal layer 2C in the stacking direction, and is provided so as to be connected to the metal layer 2C. More specifically, the interlayer connection conductor 20C penetrates the porous liquid crystal polymer sheet 1C in the stacking direction and is connected to the metal layer 2C on the first main surface 1Ca side of the porous liquid crystal polymer sheet 1C. Further, the interlayer connection conductor 20C is connected to the metal layer 2B' on the second main surface 1Cb side of the porous liquid crystal polymer sheet 1C. That is, the metal layer 2B' and the metal layer 2C are electrically connected via the interlayer connection conductor 20C.
- the interlayer connection conductor 20D penetrates the porous liquid crystal polymer sheet 1C in the stacking direction but does not penetrate the metal layer 2C in the stacking direction at a position separated from the interlayer connection conductor 20C, and is connected to the metal layer 2C. is provided. More specifically, the interlayer connection conductor 20D penetrates the porous liquid crystal polymer sheet 1C in the stacking direction at a position separated from the interlayer connection conductor 20C, and is located on the first main surface 1Ca side of the porous liquid crystal polymer sheet 1C. It is connected to metal layer 2C.
- interlayer connection conductor 20D is connected to the metal layer 2B'' on the second main surface 1Cb side of the porous liquid crystal polymer sheet 1C at a position separated from the interlayer connection conductor 20C. That is, the metal layer 2B'' and the metal layer 2C are electrically connected via the interlayer connection conductor 20D.
- the metal layer 2A and the metal layer 2C are electrically connected via the interlayer connection conductor 20A, the metal layer 2B', and the interlayer connection conductor 20C.
- the metal layers 2A and 2C are also electrically connected via the interlayer connection conductors 20B, the metal layers 2B'', and the interlayer connection conductors 20D.
- the interlayer connection conductor 20A penetrates the porous liquid crystal polymer sheet 1B in the thickness direction, but does not penetrate the metal layer 2B′ in the thickness direction and reaches the metal layer 2B′. It is formed by performing a plating treatment on the inside or by performing a heat treatment after filling the conductive paste.
- the interlayer connection conductor 20B, the interlayer connection conductor 20C, and the interlayer connection conductor 20D are also formed in the same manner as the interlayer connection conductor 20A, except that the formation positions are different.
- interlayer connection conductor 20A, the interlayer connection conductor 20B, the interlayer connection conductor 20C, and the interlayer connection conductor 20D are formed by plating
- metals that constitute the interlayer connection conductors include copper, tin, and silver. Among them, copper is preferred.
- each interlayer connection conductor includes, for example, copper and tin. , silver and the like.
- each interlayer connection conductor preferably contains copper, more preferably copper and tin.
- the interlayer connection conductor 20A and the metal layer 2B' undergo an alloying reaction at low temperature, so that they are easily conductive. The same applies to other combinations of interlayer connection conductors and metal layers.
- the resin contained in each interlayer connection conductor is epoxy resin, phenol resin, At least one thermosetting resin selected from the group consisting of polyimide resin, silicone resin or modified resin thereof, and acrylic resin, or polyamide resin, polystyrene resin, polymethacrylic resin, polycarbonate resin, and cellulose resin It preferably contains at least one thermoplastic resin selected from the group consisting of
- the electronic circuit board 50 may have the metal layer 2B as a signal line for transmitting signals. In this case, the electronic circuit board 50 constitutes a transmission line.
- the electronic circuit board 50 may have the metal layer 2B as a signal line for transmitting signals, and the metal layers 2A and 2C as ground electrodes. In this case, the electronic circuit board 50 constitutes a stripline type transmission line.
- the metal layer 2B may be a signal line for transmitting high frequency signals.
- the porous liquid crystal polymer sheet 1B and the porous liquid crystal polymer sheet 1C having a small dielectric constant are in contact with the metal layer 2B, that is, the signal line. Transmission characteristics are easily improved.
- the electronic circuit board 50 is manufactured, for example, by the following method.
- FIG. 4 ⁇ Production process of porous liquid crystal polymer sheet with metal layer> 4, 5, and 6 are schematic cross-sectional views showing steps for producing a porous liquid crystal polymer sheet with a metal layer in one example of the method for producing an electronic circuit board of the present invention.
- a porous liquid crystal polymer sheet 10A with a metal layer is produced, in which a metal layer 2A is provided on the first main surface 1Aa of the porous liquid crystal polymer sheet 1A.
- the metal layer 2A is pressure-bonded to the first main surface 1Aa of the porous liquid crystal polymer sheet 1A.
- a porous liquid crystal polymer sheet 10B with a metal layer in which a metal layer 2B, a metal layer 2B′, and a metal layer 2B′′ are provided on the first main surface 1Ba of the porous liquid crystal polymer sheet 1B.
- the metal layer is etched to form a metal layer 2B, a metal layer 2B', and a metal layer 2B''. pattern to Alternatively, the metal layer 2B, the metal layer 2B', and the metal layer 2B'' are prepared in advance, and each metal layer is pressure-bonded to the first main surface 1Ba of the porous liquid crystal polymer sheet 1B.
- a porous liquid crystal polymer sheet 10C with a metal layer is produced, in which a metal layer 2C is provided on the first main surface 1Ca of the porous liquid crystal polymer sheet 1C.
- the metal layer 2C is pressure-bonded to the first main surface 1Ca of the porous liquid crystal polymer sheet 1C.
- ⁇ Formation process of via hole> 7 and 8 are schematic cross-sectional views showing the steps of forming via holes in one example of the method for manufacturing an electronic circuit board according to the present invention.
- the porous liquid crystal polymer sheet 1B is penetrated in the thickness direction, but the metal layer 2B' is not penetrated in the thickness direction, and the metal layer 2B' is formed.
- a via hole 21A is formed to reach.
- a portion of the metal layer 2B' is exposed from the via hole 21A.
- the porous liquid crystal polymer sheet 1B is penetrated in the thickness direction, but the metal layer 2B'' is penetrated in the thickness direction.
- a via hole 21B is formed so as to reach the metal layer 2B'' without penetrating through. As a result, a portion of the metal layer 2B'' is exposed from the via hole 21B.
- via holes 21A and 21B are formed in the metal layer-attached porous liquid crystal polymer sheet 10B.
- the via hole 21A and the via hole 21B may be formed at the same timing or may be formed at different timings.
- the porous liquid crystal polymer sheet 10C with a metal layer As shown in FIG. 8, for the porous liquid crystal polymer sheet 10C with a metal layer, the porous liquid crystal polymer sheet 1C is penetrated in the thickness direction, but the metal layer 2C is not penetrated in the thickness direction and the metal layer 2C is reached. , a via hole 21C is formed. Thereby, a portion of the metal layer 2C is exposed from the via hole 21C.
- the porous liquid crystal polymer sheet 1C is penetrated in the thickness direction and the metal layer 2C is penetrated in the thickness direction.
- a via hole 21D is formed so as to reach the metal layer 2C without cutting. As a result, part of the metal layer 2C is exposed from the via hole 21D.
- via holes 21C and 21D are formed in the metal layer-attached porous liquid crystal polymer sheet 10C.
- the via hole 21C and the via hole 21D may be formed at the same timing or may be formed at different timings.
- the via hole 21A, the via hole 21B, the via hole 21C, and the via hole 21D it is preferable to irradiate the porous liquid crystal polymer sheet with the metal layer with laser light from the porous liquid crystal polymer sheet side.
- ⁇ Filling process of conductive paste> 9 and 10 are schematic cross-sectional views showing the step of filling the conductive paste in one example of the method for manufacturing an electronic circuit board according to the present invention.
- the conductive paste 22A is filled into the via holes 21A of the metal layer-attached porous liquid crystal polymer sheet 10B.
- the conductive paste 22B is filled into the via holes 21B of the porous liquid crystal polymer sheet 10B with the metal layer.
- the conductive paste 22A and the conductive paste 22B may be filled at the same timing or at different timings.
- the conductive paste 22C is filled into the via holes 21C of the metal layer-attached porous liquid crystal polymer sheet 10C.
- the conductive paste 22D is filled into the via holes 21D of the metal layer-attached porous liquid crystal polymer sheet 10C.
- the conductive paste 22C and the conductive paste 22D may be filled at the same timing or may be filled at different timings.
- Examples of methods for filling the conductive paste 22A, the conductive paste 22B, the conductive paste 22C, and the conductive paste 22D include a screen printing method and a vacuum filling method.
- the conductive paste 22A, the conductive paste 22B, the conductive paste 22C, and the conductive paste 22D each contain metal and resin, for example.
- each conductive paste preferably contains copper, and more preferably contains copper and tin.
- the resin contained in each of the conductive pastes of the conductive paste 22A, the conductive paste 22B, the conductive paste 22C, and the conductive paste 22D includes epoxy resin, phenol resin, polyimide resin, silicon resin or modified resin thereof, and , At least one thermosetting resin selected from the group consisting of acrylic resins, or at least one selected from the group consisting of polyamide resins, polystyrene resins, polymethacrylic resins, polycarbonate resins, and cellulose resins It preferably contains a thermoplastic resin.
- Each conductive paste of the conductive paste 22A, the conductive paste 22B, the conductive paste 22C, and the conductive paste 22D may further contain a vehicle, a solvent, a thixotropic agent, an activator, and the like.
- Examples of the vehicle include rosin-based resins composed of rosin and its derivatives such as modified rosin, synthetic resins composed of rosin and its derivatives such as modified rosin, and mixtures of these resins. .
- rosin-based resins composed of rosin and derivatives thereof such as modified rosin include gum rosin, tall rosin, wood rosin, polymerized rosin, hydrogenated rosin, formylated rosin, rosin ester, rosin-modified maleic acid resin, and rosin-modified phenol.
- examples include resins, rosin-modified alkyd resins, and other various rosin derivatives.
- Examples of synthetic resins composed of rosin and derivatives such as modified rosin obtained by modifying rosin include polyester resins, polyamide resins, phenoxy resins, and terpene resins.
- solvents include alcohols, ketones, esters, ethers, aromatics, and hydrocarbons. Specific examples thereof include benzyl alcohol, ethanol, isopropyl alcohol, butanol, diethylene glycol, ethylene glycol, glycerin, ethyl cellosolve, butyl cellosolve, ethyl acetate, butyl acetate, butyl benzoate, diethyl adipate, dodecane, tetradecene, ⁇ -terpineol.
- terpineol 2-methyl-2,4-pentanediol, 2-ethylhexanediol, toluene, xylene, propylene glycol monophenyl ether, diethylene glycol monohexyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diisobutyl adipate, hexylene glycol, cyclohexanedimethanol, 2-terpinyloxyethanol, 2-dihydroterpinyloxyethanol, mixtures thereof, and the like.
- terpineol ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, or diethylene glycol monoethyl ether is preferable.
- thixotropic agents include hydrogenated castor oil, carnauba wax, amides, hydroxy fatty acids, dibenzylidene sorbitol, bis(p-methylbenzylidene) sorbitols, beeswax, stearic acid amide, hydroxystearic acid ethylene bisamide, and the like.
- thixotropic agents may optionally contain fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid, hydroxy fatty acids such as 1,2-hydroxystearic acid, and antioxidants. , surfactants, amines and the like may be added.
- activators include amine hydrohalides, organic halogen compounds, organic acids, organic amines, and polyhydric alcohols.
- Amine hydrohalides include, for example, diphenylguanidine hydrobromide, diphenylguanidine hydrochloride, cyclohexylamine hydrobromide, ethylamine hydrochloride, ethylamine hydrobromide, diethylaniline hydrobromide salts, diethylaniline hydrochloride, triethanolamine hydrobromide, monoethanolamine hydrobromide and the like.
- organic halogen compounds include paraffin chloride, tetrabromoethane, dibromopropanol, 2,3-dibromo-1,4-butanediol, 2,3-dibromo-2-butene-1,4-diol, tris(2 , 3-dibromopropyl) isocyanurate and the like.
- organic acids examples include malonic acid, fumaric acid, glycolic acid, citric acid, malic acid, succinic acid, phenylsuccinic acid, maleic acid, salicylic acid, anthranilic acid, glutaric acid, suberic acid, adipic acid, sebacic acid, stearic acid, abietic acid, benzoic acid, trimellitic acid, pyromellitic acid, dodecanoic acid and the like.
- organic amines examples include monoethanolamine, diethanolamine, triethanolamine, tributylamine, aniline, and diethylaniline.
- polyhydric alcohols examples include erythritol, pyrogallol, and ribitol.
- FIG. 11 is a schematic cross-sectional view showing a step of forming interlayer connection conductors in one example of the method of manufacturing an electronic circuit board according to the present invention.
- the porous liquid crystal polymer sheet 10C with a metal layer filled with 22D is sequentially laminated in the lamination direction. At this time, the surface (upper surface) of the metal layer-attached porous liquid crystal polymer sheet 10A on the metal layer 2A side and the surface (lower surface) of the metal layer-attached porous liquid crystal polymer sheet 10B on the porous liquid crystal polymer sheet 1B side are brought into contact.
- the metal layer-attached porous liquid crystal polymer sheets are shown separated from each other.
- a heat press is performed by applying pressure in the stacking direction while heating the obtained laminate.
- the porous liquid crystal polymer sheet 10A with the metal layer and the porous liquid crystal polymer sheet 10B with the metal layer are pressure-bonded
- the porous liquid crystal polymer sheet 10B with the metal layer and the porous liquid crystal polymer sheet 10C with the metal layer are pressure-bonded.
- the conductive paste 22A, the conductive paste 22B, the conductive paste 22C, and the conductive paste 22D are solidified during hot pressing, thereby forming the interlayer connection conductor 20A, the interlayer connection conductor 20B, the interlayer connection conductor 20C, and the interlayer connection conductor 20A, respectively. And it becomes the interlayer connection conductor 20D.
- interlayer connection conductors 20A, 20B, 20C, and 20D are formed in via holes 21A, 21B, 21C, and 21D, respectively.
- the interlayer connection conductor 20A When forming the interlayer connection conductor 20A, the interlayer connection conductor 20B, the interlayer connection conductor 20C, and the interlayer connection conductor 20D, instead of filling the via hole with a conductive paste, a metal such as copper, tin, or silver is used.
- a metal such as copper, tin, or silver is used.
- the inner wall of the via hole may be plated.
- the electronic circuit board 50 shown in FIG. 3 is manufactured.
- a porous resin sheet A and a porous resin sheet B were produced by the following method.
- ⁇ Porous resin sheet A> a liquid crystal which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and has a molar ratio of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid of 80:20.
- Polymer A was prepared.
- 99.6 parts by weight of the liquid crystal polymer A and 0.4 parts by weight of the blowing agent "Vinihole AC #6-K6" (main component: azodicarbonamide) manufactured by Eiwa Kasei Kogyo Co., Ltd. are mixed to obtain a resin material.
- A was prepared.
- a porous resin sheet A having the properties shown in Table 1 was produced by a T-die molding method.
- ⁇ Porous resin sheet B> a liquid crystal which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and has a molar ratio of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid of 73:27.
- Polymer B was prepared.
- resin material B was prepared by mixing 99.8 parts by weight of liquid crystal polymer B and 0.2 parts by weight of foaming agent "Vinihole AC#6-K6" manufactured by Eiwa Kasei Kogyo Co., Ltd. Then, using the resin material B, a porous resin sheet B having the properties shown in Table 1 was produced by a T-die molding method.
- Example 1 First, the porous resin sheet A was heated from 23° C. to 250° C. over 1 hour in a nitrogen atmosphere, then heated from 250° C. to 310° C. over 10 hours, and then heated to 310° C. Solid phase polymerization of the liquid crystal polymer was performed by holding for 6 hours. Then, the porous resin sheet A after solid phase polymerization is repeatedly irradiated with an electron beam at an acceleration voltage of 200 kV in a nitrogen atmosphere at 250 kGy increments until the total irradiation dose reaches 1000 kGy, whereby electrons are transferred to the liquid crystal polymer. radiation was performed. As described above, a porous liquid crystal polymer sheet of Example 1 was produced.
- Example 2 A porous liquid crystal polymer sheet of Example 2 was produced in the same manner as the porous liquid crystal polymer sheet of Example 1, except that the liquid crystal polymer was not irradiated with an electron beam.
- Example 3 A porous liquid crystal polymer sheet of Example 3 was produced in the same manner as the porous liquid crystal polymer sheet of Example 1, except that the liquid crystal polymer was not solid-phase polymerized.
- Example 4 First, the porous resin sheet B was heated from 23° C. to 250° C. over 1 hour in a nitrogen atmosphere, then heated from 250° C. to 270° C. over 10 hours, and then heated to 270° C. Solid phase polymerization of the liquid crystal polymer was performed by holding for 6 hours. Then, the porous resin sheet B after the solid phase polymerization is repeatedly irradiated with an electron beam at an acceleration voltage of 200 kV in a nitrogen atmosphere at 250 kGy intervals until the total irradiation dose reaches 1000 kGy, whereby electrons are transferred to the liquid crystal polymer. radiation was performed. As described above, a porous liquid crystal polymer sheet of Example 4 was produced.
- Example 5 A porous liquid crystal polymer sheet of Example 5 was produced in the same manner as the porous liquid crystal polymer sheet of Example 4, except that the liquid crystal polymer was not irradiated with an electron beam.
- Example 6 A porous liquid crystal polymer sheet of Example 6 was produced in the same manner as the porous liquid crystal polymer sheet of Example 4, except that the liquid crystal polymer was not solid-phase polymerized.
- ⁇ Melting point> First, using a differential scanning calorimeter "DSC7000X” manufactured by Hitachi High-Tech Science Co., Ltd., the temperature of the porous liquid crystal polymer sheet was raised at a temperature elevation rate of 20°C/min to completely melt it. Then, after the temperature of the obtained melt was lowered to 175°C at a temperature decrease rate of 20°C/min, it was again heated at a temperature increase rate of 20°C/min. The temperature was defined as the melting point of the porous liquid crystal polymer sheet. When the endothermic peak was difficult to observe by the method described above, the melting point of the porous liquid crystal polymer sheet was determined by texture observation under crossed Nicols conditions with a polarizing microscope.
- ⁇ Thickness reduction rate> First, a sample of 100 mm square was cut out from the porous liquid crystal polymer sheet, and the thickness of the sample was taken as the thickness A before crimping. Next, after laminating a copper foil with a thickness of 12 ⁇ m on one main surface of the sample, the obtained laminate is subjected to a hot press for 10 seconds at the above measurement temperature to apply a pressure of 0.5 MPa to remove copper. A foil was crimped onto the sample. After that, the copper foil was etched with ferric chloride, and the thickness of the remaining sample was defined as thickness B after crimping.
- the porous liquid crystal polymer sheets of Examples 1 to 6 which had a melt viscosity of 20 Pa ⁇ s or more, had a low thickness reduction rate of 5% or less.
- the thickness reduction rate was low, when the copper foil was crimped to the porous liquid crystal polymer sheet, the pores were crushed under high temperature and high pressure during crimping. I can say that it was difficult. Therefore, in the electronic circuit boards manufactured using the porous liquid crystal polymer sheets of Examples 1 to 6, the effect of reducing the dielectric constant due to the porous liquid crystal polymer sheet is easily exhibited, and the dielectric properties in the high frequency range are improved. presumably it will be easier.
- the porous liquid crystal polymer sheets of Examples 1 to 6 the porous liquid crystal polymer sheets of Examples 1, 3, 4, and 6 having a melt tension of 3 mN or more showed a decrease in thickness. rate was lower than 1%. Thus, in the porous liquid crystal polymer sheets of Examples 1, 3, 4, and 6, the thickness reduction rate was very low. In addition, it can be said that the pores were extremely resistant to crushing under high temperature and high pressure during crimping.
- the thickness reduction rate was higher than 5%.
- the thickness reduction rate was high, when the copper foil was crimped to the porous liquid crystal polymer sheet, the pores were formed under high temperature and high pressure during crimping. It can be said that it was easy to collapse.
- porous liquid crystal polymer sheets 1a, 1Aa, 1Ba, 1Ca first main surfaces of porous liquid crystal polymer sheets 1b, 1Ab, 1Bb, 1Cb second main surfaces 1h, 1Ah of porous liquid crystal polymer sheets, 1Bh, 1Ch holes 1s, 1As, 1Bs, 1Cs resin sheets 2, 2A, 2B, 2B', 2B'', 2C metal layers 10, 10A, 10B, 10C porous liquid crystal polymer sheets with metal layers 20A, 20B, 20C , 20D interlayer connection conductors 21A, 21B, 21C, 21D via holes 22A, 22B, 22C, 22D conductive paste 50 electronic circuit board
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
Abstract
Description
図4、図5、及び、図6は、本発明の電子回路基板の製造方法の一例について、金属層付き多孔質液晶ポリマーシートの作製工程を示す断面模式図である。
図7及び図8は、本発明の電子回路基板の製造方法の一例について、ビアホールの形成工程を示す断面模式図である。
図9及び図10は、本発明の電子回路基板の製造方法の一例について、導電性ペーストの充填工程を示す断面模式図である。
図11は、本発明の電子回路基板の製造方法の一例について、層間接続導体の形成工程を示す断面模式図である。
まず、p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸との共重合体であって、p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸とのモル比率が80:20である液晶ポリマーAを準備した。次に、液晶ポリマーAを99.6重量部、永和化成工業社製の発泡剤「ビニホールAC#6-K6」(主成分:アゾジカルボンアミド)を0.4重量部混合することにより、樹脂材料Aを調製した。そして、樹脂材料Aを用いて、Tダイ成形法により、表1に示す特性を有する多孔質樹脂シートAを作製した。
まず、p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸との共重合体であって、p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸とのモル比率が73:27である液晶ポリマーBを準備した。次に、液晶ポリマーBを99.8重量部、永和化成工業社製の発泡剤「ビニホールAC#6-K6」を0.2重量部混合することにより、樹脂材料Bを調製した。そして、樹脂材料Bを用いて、Tダイ成形法により、表1に示す特性を有する多孔質樹脂シートBを作製した。
まず、多孔質樹脂シートAを、窒素雰囲気下で、23℃から250℃まで1時間かけて昇温させ、続いて、250℃から310℃まで10時間かけて昇温させた後、310℃で6時間保持することにより、液晶ポリマーの固相重合を行った。そして、固相重合後の多孔質樹脂シートAに対して、窒素雰囲気下で、加速電圧200kVの電子線を、250kGyずつ総照射量が1000kGyとなるまで繰り返し照射することにより、液晶ポリマーへの電子線照射を行った。以上により、実施例1の多孔質液晶ポリマーシートを製造した。
液晶ポリマーへの電子線照射を行わなかったこと以外、実施例1の多孔質液晶ポリマーシートと同様にして、実施例2の多孔質液晶ポリマーシートを製造した。
液晶ポリマーの固相重合を行わなかったこと以外、実施例1の多孔質液晶ポリマーシートと同様にして、実施例3の多孔質液晶ポリマーシートを製造した。
まず、多孔質樹脂シートBを、窒素雰囲気下で、23℃から250℃まで1時間かけて昇温させ、続いて、250℃から270℃まで10時間かけて昇温させた後、270℃で6時間保持することにより、液晶ポリマーの固相重合を行った。そして、固相重合後の多孔質樹脂シートBに対して、窒素雰囲気下で、加速電圧200kVの電子線を、250kGyずつ総照射量が1000kGyとなるまで繰り返し照射することにより、液晶ポリマーへの電子線照射を行った。以上により、実施例4の多孔質液晶ポリマーシートを製造した。
液晶ポリマーへの電子線照射を行わなかったこと以外、実施例4の多孔質液晶ポリマーシートと同様にして、実施例5の多孔質液晶ポリマーシートを製造した。
液晶ポリマーの固相重合を行わなかったこと以外、実施例4の多孔質液晶ポリマーシートと同様にして、実施例6の多孔質液晶ポリマーシートを製造した。
多孔質樹脂シートAを、比較例1の多孔質液晶ポリマーシートとして用いた。
多孔質樹脂シートBを、比較例2の多孔質液晶ポリマーシートとして用いた。
実施例1~6、比較例1、及び、比較例2の多孔質液晶ポリマーシートについて、以下の測定を行った。結果を、表2に示す。
まず、日立ハイテクサイエンス社製の示差走査熱量計「DSC7000X」を用いて、多孔質液晶ポリマーシートを、20℃/分の昇温速度で昇温させて完全に溶融させた。そして、得られた溶融物を、20℃/分の降温速度で175℃まで降温させた後、再び、20℃/分の昇温速度で昇温させたときに観測される吸熱ピークに対応する温度を、多孔質液晶ポリマーシートの融点と定めた。なお、上述した方法で吸熱ピークが観測されにくい場合は、偏光顕微鏡のクロスニコル条件下でのテクスチャー観察により、多孔質液晶ポリマーシートの融点を定めた。
まず、多孔質液晶ポリマーシートから100mm角の試料を切り出し、試料の面積s、厚みt、重量mを測定した。また、多孔質液晶ポリマーシートの樹脂成分の比重σを、JIS Z 8807-2012に準拠して測定した。そして、多孔質液晶ポリマーシートの空孔率を、空孔率(体積%)=[1-(m/(s×t×σ))]×100、という式に基づいて算出した。
東洋精機製作所社製のキャピログラフ「F-1」を用いて、上述した方法で測定された多孔質液晶ポリマーシートの融点よりも20℃高い温度を測定温度とし、かつ、せん断速度を1000s-1とした条件において、多孔質液晶ポリマーシートの溶融粘度を測定した。この際、シリンダーのバレル径を9.55mm、キャピラリー径を1mmとした。
東洋精機製作所社製のキャピログラフ「F-1」を用いて、上記測定温度における多孔質液晶ポリマーシートの溶融張力を測定した。この際、シリンダーのバレル径を9.55mm、キャピラリー径を1mm、ストランド引取速度を150m/分とした。
まず、多孔質液晶ポリマーシートから100mm角の試料を切り出し、試料の厚みを圧着前厚みAとした。次に、試料の一方主面に厚み12μmの銅箔を積層した後、得られた積層体に対して、上記測定温度下で0.5MPaの圧力を加える加熱プレスを10秒間行うことにより、銅箔を試料に圧着した。その後、塩化第二鉄を用いて銅箔をエッチングし、残った試料の厚みを圧着後厚みBとした。ここで、圧着前厚みA及び圧着後厚みBについては、上述した多孔質液晶ポリマーシートの厚みの測定方法と同様にして測定した。そして、圧着前後での多孔質液晶ポリマーシートの厚み減少率を、厚み減少率(%)=(1-「圧着後厚みB」/「圧着前厚みA」)×100、という式に基づいて算出した。圧着前後での多孔質液晶ポリマーシートの厚み減少率の判定基準については、以下の通りとした。
◎(優):厚み減少率が1%よりも低かった。
○(良):厚み減少率が1%以上、5%以下であった。
×(不良):厚み減少率が5%よりも高かった。
1a、1Aa、1Ba、1Ca 多孔質液晶ポリマーシートの第1主面
1b、1Ab、1Bb、1Cb 多孔質液晶ポリマーシートの第2主面
1h、1Ah、1Bh、1Ch 空孔
1s、1As、1Bs、1Cs 樹脂シート
2、2A、2B、2B’、2B’’、2C 金属層
10、10A、10B、10C 金属層付き多孔質液晶ポリマーシート
20A、20B、20C、20D 層間接続導体
21A、21B、21C、21D ビアホール
22A、22B、22C、22D 導電性ペースト
50 電子回路基板
Claims (10)
- 液晶ポリマーを含む樹脂シートからなり、かつ、前記樹脂シートに空孔が設けられた、多孔質液晶ポリマーシートであって、
前記樹脂シートの融点よりも20℃高い温度を測定温度とし、かつ、せん断速度を1000s-1とした条件における溶融粘度が20Pa・s以上である、ことを特徴とする多孔質液晶ポリマーシート。 - 前記測定温度における溶融張力が3mN以上である、請求項1に記載の多孔質液晶ポリマーシート。
- 前記樹脂シートの融点は、275℃以上、330℃以下である、請求項1又は2に記載の多孔質液晶ポリマーシート。
- 前記液晶ポリマーは、p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸との共重合体を含む、請求項1~3のいずれかに記載の多孔質液晶ポリマーシート。
- 前記液晶ポリマーにおいて、前記6-ヒドロキシ-2-ナフトエ酸に対する前記p-ヒドロキシ安息香酸のモル比率は、0.20以上、5以下である、請求項4に記載の多孔質液晶ポリマーシート。
- 前記液晶ポリマーは、モノマー全量を100モル%としたとき、前記p-ヒドロキシ安息香酸と前記6-ヒドロキシ-2-ナフトエ酸とを、各々、10モル%以上含む、請求項4又は5に記載の多孔質液晶ポリマーシート。
- 厚みが10μm以上、200μm以下である、請求項1~6のいずれかに記載の多孔質液晶ポリマーシート。
- 請求項1~7のいずれかに記載の多孔質液晶ポリマーシートと、
前記多孔質液晶ポリマーシートの少なくとも一方主面に設けられた金属層と、を備える、ことを特徴とする金属層付き多孔質液晶ポリマーシート。 - 前記金属層は、銅箔からなる、請求項8に記載の金属層付き多孔質液晶ポリマーシート。
- 請求項8又は9に記載の金属層付き多孔質液晶ポリマーシートを備える、ことを特徴とする電子回路基板。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023527898A JPWO2022260087A1 (ja) | 2021-06-09 | 2022-06-08 | |
CN202280009537.7A CN116711468A (zh) | 2021-06-09 | 2022-06-08 | 多孔质液晶聚合物片材、带金属层的多孔质液晶聚合物片材以及电子电路基板 |
US18/322,764 US20230295506A1 (en) | 2021-06-09 | 2023-05-24 | Porous liquid crystal polymer sheet, metal layer-attached porous liquid crystal polymer sheet, and electronic circuit board |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-096552 | 2021-06-09 | ||
JP2021096552 | 2021-06-09 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/322,764 Continuation US20230295506A1 (en) | 2021-06-09 | 2023-05-24 | Porous liquid crystal polymer sheet, metal layer-attached porous liquid crystal polymer sheet, and electronic circuit board |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022260087A1 true WO2022260087A1 (ja) | 2022-12-15 |
Family
ID=84426071
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/023141 WO2022260087A1 (ja) | 2021-06-09 | 2022-06-08 | 多孔質液晶ポリマーシート、金属層付き多孔質液晶ポリマーシート、及び、電子回路基板 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20230295506A1 (ja) |
JP (1) | JPWO2022260087A1 (ja) |
CN (1) | CN116711468A (ja) |
WO (1) | WO2022260087A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009127024A (ja) * | 2007-11-28 | 2009-06-11 | Polyplastics Co | 全芳香族ポリエステル及びポリエステル樹脂組成物 |
JP2016051820A (ja) * | 2014-08-29 | 2016-04-11 | 住友電気工業株式会社 | プリント配線板、及びプリント配線板の製造方法 |
JP2018109090A (ja) * | 2016-12-28 | 2018-07-12 | 株式会社クラレ | 熱可塑性液晶ポリマーフィルムおよびそれを用いた回路基板 |
JP6434195B2 (ja) * | 2016-07-04 | 2018-12-05 | Jxtgエネルギー株式会社 | 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品 |
WO2020218140A1 (ja) * | 2019-04-23 | 2020-10-29 | 株式会社クラレ | 熱可塑性液晶ポリマーフィルム、積層体、および成形体、ならびにそれらの製造方法 |
-
2022
- 2022-06-08 WO PCT/JP2022/023141 patent/WO2022260087A1/ja active Application Filing
- 2022-06-08 CN CN202280009537.7A patent/CN116711468A/zh active Pending
- 2022-06-08 JP JP2023527898A patent/JPWO2022260087A1/ja active Pending
-
2023
- 2023-05-24 US US18/322,764 patent/US20230295506A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009127024A (ja) * | 2007-11-28 | 2009-06-11 | Polyplastics Co | 全芳香族ポリエステル及びポリエステル樹脂組成物 |
JP2016051820A (ja) * | 2014-08-29 | 2016-04-11 | 住友電気工業株式会社 | プリント配線板、及びプリント配線板の製造方法 |
JP6434195B2 (ja) * | 2016-07-04 | 2018-12-05 | Jxtgエネルギー株式会社 | 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品 |
JP2018109090A (ja) * | 2016-12-28 | 2018-07-12 | 株式会社クラレ | 熱可塑性液晶ポリマーフィルムおよびそれを用いた回路基板 |
WO2020218140A1 (ja) * | 2019-04-23 | 2020-10-29 | 株式会社クラレ | 熱可塑性液晶ポリマーフィルム、積層体、および成形体、ならびにそれらの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US20230295506A1 (en) | 2023-09-21 |
JPWO2022260087A1 (ja) | 2022-12-15 |
CN116711468A (zh) | 2023-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6766960B2 (ja) | 多層配線基板、電子機器、及び、多層配線基板の製造方法 | |
TWI413474B (zh) | 多層印刷配線板 | |
JP7196914B2 (ja) | 樹脂付金属箔、積層体の製造方法、積層体及びプリント基板 | |
TW201413750A (zh) | 導電膜的製造方法及導電膜形成用組成物 | |
JPWO2021025055A5 (ja) | ||
JP2007253366A (ja) | 両面銅張板 | |
WO2022260087A1 (ja) | 多孔質液晶ポリマーシート、金属層付き多孔質液晶ポリマーシート、及び、電子回路基板 | |
JP7230932B2 (ja) | 積層体及びその製造方法、複合積層体の製造方法、並びにポリマーフィルムの製造方法 | |
WO2022260092A1 (ja) | 液晶ポリマーフィルム、導体層付き液晶ポリマーフィルム、及び、積層基板 | |
JP2012182379A (ja) | 多層チップ部品およびその製造方法 | |
KR20230010621A (ko) | 열 용융성 테트라플루오로에틸렌계 폴리머를 포함하는 층을 갖는 적층체의 제조 방법 | |
JP7521702B2 (ja) | 多孔質液晶ポリマーシート、金属層付き多孔質液晶ポリマーシート、及び、電子回路基板 | |
CN211321678U (zh) | 多层布线基板 | |
WO2024004620A1 (ja) | 樹脂組成物、樹脂シート、導体層付き樹脂シート、積層基板、及び、樹脂シートの製造方法 | |
JP2015103720A (ja) | プリント配線板及びその製造方法 | |
WO2022239572A1 (ja) | 積層基板及びアンテナ基板 | |
WO2022118658A1 (ja) | 積層基板 | |
JP2013502704A (ja) | 基板に導電性ビアを製造する方法 | |
JP2001024328A (ja) | 多層配線板 | |
WO2022004504A1 (ja) | 積層基板 | |
Maekawa et al. | Influence of wavelength on laser sintering characteristics of Ag nanoparticles | |
JP2004179202A (ja) | 多層配線板製造用金属箔付き絶縁シート及び多層配線板 | |
JP7452534B2 (ja) | パウダー分散液、パウダー分散液の製造方法及び樹脂付基板の製造方法 | |
JP5526818B2 (ja) | プリント配線板 | |
KR102010658B1 (ko) | 미세회로용 다층 금속 클레이 소재의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22820266 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280009537.7 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023527898 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22820266 Country of ref document: EP Kind code of ref document: A1 |