TW202342584A - Liquid crystalline resin composition for planar connectors, and planar connector using same - Google Patents
Liquid crystalline resin composition for planar connectors, and planar connector using same Download PDFInfo
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- TW202342584A TW202342584A TW112102251A TW112102251A TW202342584A TW 202342584 A TW202342584 A TW 202342584A TW 112102251 A TW112102251 A TW 112102251A TW 112102251 A TW112102251 A TW 112102251A TW 202342584 A TW202342584 A TW 202342584A
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- Prior art keywords
- resin composition
- liquid crystalline
- crystalline resin
- content
- mol
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- 239000011342 resin composition Substances 0.000 title claims abstract description 80
- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 229920006038 crystalline resin Polymers 0.000 title claims abstract description 75
- 239000011256 inorganic filler Substances 0.000 claims abstract description 48
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 125000003118 aryl group Chemical group 0.000 claims abstract description 39
- 229920000728 polyester Polymers 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims description 9
- 239000004973 liquid crystal related substance Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 239000005337 ground glass Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 125000000732 arylene group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 239000000945 filler Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 16
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000005452 bending Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 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 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- -1 1,2-phenylene, 1,3-phenylene, 1,4-phenylene Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- RHCQEPWEBDOALW-MUCWUPSWSA-K cobalt(3+);(e)-4-oxopent-2-en-2-olate Chemical compound [Co+3].C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O RHCQEPWEBDOALW-MUCWUPSWSA-K 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003703 image analysis method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明是關於平面狀連接器用液晶性樹脂組合物及使用其之平面狀連接器。The present invention relates to a liquid crystal resin composition for planar connectors and a planar connector using the same.
以液晶性聚酯樹脂為代表的液晶性樹脂在優異的機械強度、耐熱性、耐藥品性、電氣性質等之間具有良好的平衡，也具有優異的尺寸穩定性，因此作為高機能工程塑料被廣泛利用。另外，由於液晶性樹脂的流動性等亦優異，因此歷來被作為各種電子部件的材料而採用。特別是，隨著近年電子設備的高性能化，具有對含有微細結構等的成形品(平面狀連接器等)的需求。為了滿足這樣的需求，例如在專利文獻1中提案了一種平面狀連接器，由特定的液晶性聚合物、無機填充劑及玻璃纖構成的複合樹脂組合物而成形，其成形性、平面度、翹曲變形、耐熱性等的性能優異，在格子部等難以發生破裂(也稱為裂痕)。 [先前技術文獻] [專利文獻] Liquid crystalline resins represented by liquid crystalline polyester resins have a good balance between excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and also have excellent dimensional stability, so they are used as high-performance engineering plastics. widely used. In addition, since liquid crystalline resins are also excellent in fluidity and the like, they have been conventionally used as materials for various electronic components. In particular, as electronic equipment becomes more advanced in performance in recent years, there is a demand for molded products (planar connectors, etc.) containing fine structures and the like. In order to meet such needs, for example, Patent Document 1 proposes a planar connector formed from a composite resin composition composed of a specific liquid crystalline polymer, an inorganic filler, and glass fiber. Its formability, flatness, It has excellent properties such as warpage deformation and heat resistance, and is unlikely to cause cracks (also called cracks) in the lattice portion, etc. [Prior technical literature] [Patent Document]
[專利文獻1]日本特開2012-214652號公報[Patent Document 1] Japanese Patent Application Publication No. 2012-214652
[發明所欲解決的問題][Problem to be solved by the invention]
近年來，隨著從LTE向5G的轉移，通信終端的計算處理能力有提升的需求。為此，必須提高CPU的性能，實現高速演算處理。高速演算處理例如可以通過對CPU賦予高速演算功能來達成。作為具體例，可以舉出數位信號處理裝置(Digital Signal Processor，以下也稱為「DSP」)。DSP是用於進行數位信號處理的演算處理裝置，是CPU的一種。以往，為了對信號處理中使用非常多的乘積累加演算進行高速處理，由其他硬體構成乘法功能及加法功能來實現高速化，但隨著CPU模組的高速化，在開發動向向CPU自身執行乘積累加演算的方向變化中，DSP開始被製造。In recent years, with the shift from LTE to 5G, there is a need to improve the computing processing capabilities of communication terminals. For this reason, it is necessary to improve the performance of the CPU and realize high-speed calculation processing. High-speed calculation processing can be achieved, for example, by providing a high-speed calculation function to a CPU. As a specific example, a digital signal processing device (Digital Signal Processor, also referred to as "DSP" below) can be cited. DSP is an arithmetic processing device used for digital signal processing and is a type of CPU. In the past, in order to perform high-speed processing of a large number of multiplication and accumulation calculations used in signal processing, the multiplication function and the addition function were constructed by other hardware to achieve high speed. However, as the speed of CPU modules has become faster, the development trend is towards the CPU itself. In the change of direction of multiply-accumulate calculation, DSP began to be manufactured.
在CPU的安裝中，通常使用對應的CPU插座。根據CPU的形狀，安裝CPU的CPU插座的形狀也有複雜化的傾向。另外，在達成高速演算處理的基礎上，因應CPU的引脚數增加及集積密度增加，CPU插座的多引脚化及窄節距化持續發展。同時，為了降低由CPU插座材料引起的訊號傳輸損耗，所述材料本身需要具有低介電常數和低介電損耗正切。作為CPU插座材料的候補，可以舉出液晶性樹脂組合物。在使用液晶性樹脂組合物製造安裝CPU的CPU插座的情况下，根據CPU插座的複雜形狀，液晶性樹脂組合物的流動性有可能降低，或者在成形後產生機械強度降低或裂紋。另外，如上所述，期望所述CPU插座材料具有適當的介電特性。In the installation of the CPU, the corresponding CPU socket is usually used. Depending on the shape of the CPU, the shape of the CPU socket for mounting the CPU tends to become complicated. In addition, on the basis of achieving high-speed computing processing, in response to the increase in the number of CPU pins and the increase in packaging density, the multi-pin and narrow-pitch CPU sockets continue to develop. At the same time, in order to reduce the signal transmission loss caused by the CPU socket material, the material itself needs to have a low dielectric constant and a low dielectric loss tangent. As a candidate for the CPU socket material, a liquid crystal resin composition can be cited. When a CPU socket for mounting a CPU is manufactured using a liquid crystalline resin composition, depending on the complex shape of the CPU socket, the fluidity of the liquid crystalline resin composition may decrease, or mechanical strength may decrease or cracks may occur after molding. Additionally, as mentioned above, it is desirable that the CPU socket material has appropriate dielectric properties.
但是，根據本發明人的研究，以往的液晶性樹脂組合物熔融黏度非常高、流動性不良，或者，即使使用以往的液晶性樹脂組合物製造以CPU插座為代表的平面狀連接器，也無法充分抑制裂紋產生、機械強度降低、或是介電特性降低。本發明是為了解决上述問題而完成的，其目的在於提供一種流動性良好的液晶性樹脂組合物，以及包含所述液晶性樹脂組合物的平面狀連接器，所述液晶性樹脂組合物能夠實現耐裂紋性、機械強度、及介電特性優異的平面狀連接器的製造。 [解決問題的方法] However, according to research by the present inventors, conventional liquid crystalline resin compositions have very high melt viscosity and poor fluidity, or cannot produce planar connectors such as CPU sockets even if conventional liquid crystalline resin compositions are used. Fully suppresses the occurrence of cracks, reduction in mechanical strength, or reduction in dielectric properties. The present invention has been made to solve the above problems, and its object is to provide a liquid crystalline resin composition with good fluidity and a planar connector containing the liquid crystalline resin composition that can achieve Manufacturing of planar connectors with excellent crack resistance, mechanical strength, and dielectric properties. [Methods to solve the problem]
本發明人為了解决上述課題反復進行了深入的研究。結果發明，藉由以規定量含有：大量含有來自6-羥基-2-萘甲酸的構成單元的規定的全芳香族聚酯、重量平均平均纖維長為150~500 μm的纖維狀無機填充劑、無機球狀中空體的平面狀連接器用液晶性樹脂組合物，能够解决上述課題，從而完成了本發明。更具體地說，本發明提供以下發明。The present inventors have conducted intensive research to solve the above-mentioned problems. As a result, the invention was invented by containing in a prescribed amount: a prescribed fully aromatic polyester containing a large amount of structural units derived from 6-hydroxy-2-naphthoic acid, a fibrous inorganic filler with a weight average fiber length of 150 to 500 μm, A liquid crystalline resin composition for a planar connector of an inorganic spherical hollow body can solve the above problems, and the present invention has been completed. More specifically, the present invention provides the following inventions.
(1) 一種液晶性樹脂組合物，含有：(A)全芳香族聚酯；(B)纖維狀無機填充劑；以及(C)無機球狀中空體的平面狀連接器用液晶性樹脂組合物， 其中，相對於整個構成單元，前述(A)全芳香族聚酯含有下述構成單元(I)~(IV)， 構成單元(I)的含有量為40~75莫耳%；構成單元(II)的含有量為0.5~7.5莫耳%；構成單元(III)的含有量為8.5~30莫耳%；構成單元(IV)的含有量為8.5~30莫耳%， 前述(B)纖維狀無機填充劑的重量平均纖維長為150~500μm， 相對於前述液晶性樹脂組合物整體，前述(A)全芳香族聚酯的含有量為57~85質量%；前述(B)纖維狀無機填充劑的含有量為5~14質量%；前述(C)無機球狀中空體的含有量為7.5~29質量%；前述(B)纖維狀無機填充劑及前述(C)無機球狀中空體的合計含有量為15~43質量%。 (1) A liquid crystalline resin composition containing: (A) a fully aromatic polyester; (B) a fibrous inorganic filler; and (C) a liquid crystalline resin composition for a planar connector of an inorganic spherical hollow body, Among them, the aforementioned (A) fully aromatic polyester contains the following structural units (I) to (IV) with respect to the entire structural units, The content of the structural unit (I) is 40 to 75 mol%; the content of the structural unit (II) is 0.5 to 7.5 mol%; the content of the structural unit (III) is 8.5 to 30 mol%; the structural unit The content of (IV) is 8.5~30 mol%, The weight average fiber length of the aforementioned (B) fibrous inorganic filler is 150 to 500 μm, The content of the aforementioned (A) fully aromatic polyester is 57 to 85% by mass relative to the entire liquid crystalline resin composition; the content of the aforementioned (B) fibrous inorganic filler is 5 to 14% by mass; the content of the aforementioned (B) is 5 to 14% by mass; The content of C) inorganic spherical hollow bodies is 7.5 to 29 mass %; the total content of the aforementioned (B) fibrous inorganic filler and the aforementioned (C) inorganic spherical hollow bodies is 15 to 43 mass %.
[化1] (式中Ar 1及Ar 2各自獨立表示伸芳基) [Chemical 1] (Ar 1 and Ar 2 each independently represent an aryl group in the formula)
(2) 如(1)所記載的液晶性樹脂組合物，其中前述(B)纖維狀無機填充劑為選自由玻璃纖維及磨碎玻璃纖維所組成之群組中的1種以上。(2) The liquid crystal resin composition according to (1), wherein the fibrous inorganic filler (B) is at least one selected from the group consisting of glass fiber and ground glass fiber.
(3) 如(1)或(2)所記載的液晶性樹脂組合物，其中前述(C)無機球狀中空體為玻璃球。(3) The liquid crystal resin composition according to (1) or (2), wherein the inorganic spherical hollow body (C) is a glass sphere.
(4) 如(1)~(3)中任一項所記載的液晶性樹脂組合物，於測定頻率5GHz的相對介電係數為3.4以下。(4) The liquid crystalline resin composition according to any one of (1) to (3), having a relative dielectric coefficient of 3.4 or less at a measurement frequency of 5 GHz.
(5) 一種平面狀連接器，包含如(1)~(4)中任一項所記載之液晶性樹脂組合物，具有外框部及在外框部的內側形成的格子構造，前述格子構造的格子部的節距間隔為1.5mm以下。 [發明效果] (5) A planar connector, including the liquid crystalline resin composition as described in any one of (1) to (4), having an outer frame part and a lattice structure formed inside the outer frame part, the lattice structure The pitch interval of the grid portion is 1.5 mm or less. [Effects of the invention]
根據本發明，能够提供一種流動性良好的液晶性樹脂組合物，以及包含所述液晶性樹脂組合物的平面狀連接器，所述液晶性樹脂組合物能夠實現耐裂紋性、機械強度、及介電特性優異的平面狀連接器的製造。According to the present invention, it is possible to provide a liquid crystalline resin composition with good fluidity that can achieve crack resistance, mechanical strength, and media, and a planar connector including the liquid crystalline resin composition. Manufacturing of planar connectors with excellent electrical characteristics.
以下，針對本發明的實施形態進行說明。此外，本發明不限定於以下的實施形態。Hereinafter, embodiments of the present invention will be described. In addition, the present invention is not limited to the following embodiments.
＜平面狀連接器用液晶性樹脂組合物＞ 本發明的平面狀連接器用液晶性樹脂組合物含有：(A)全芳香族聚酯、(B)纖維狀無機填充劑、及(C)無機球狀中空體，所述(B)纖維狀無機填充劑的重量平均纖維長為150~500 μm。 <Liquid crystalline resin composition for planar connectors> The liquid crystal resin composition for planar connectors of the present invention contains: (A) fully aromatic polyester, (B) fibrous inorganic filler, and (C) inorganic spherical hollow body, said (B) fibrous inorganic filler The weight average fiber length of the filler is 150~500 μm.
[(A)全芳香族聚酯] 本發明的液晶性樹脂組合物含有(A)全芳香族聚酯。(A)全芳香族聚酯可以單獨使用1種或組合使用2種以上。(A)全芳香族聚酯含有下述構成單元(I)~(IV)， 相對於全部構成單元， 構成單元(I)的含有量為40~75莫耳%， 構成單元(II)的含有量為0.5~7.5莫耳%， 構成單元(III)的含有量為8.5~30莫耳%， 構成單元(IV)的含有量為8.5~30莫耳%。 [(A) Fully aromatic polyester] The liquid crystalline resin composition of the present invention contains (A) wholly aromatic polyester. (A) Fully aromatic polyester can be used individually by 1 type or in combination of 2 or more types. (A) Fully aromatic polyester contains the following structural units (I) to (IV), Relative to all constituent units, The content of structural unit (I) is 40~75 mol%, The content of structural unit (II) is 0.5~7.5 mol%, The content of structural unit (III) is 8.5~30 mol%, The content of the structural unit (IV) is 8.5 to 30 mol%.
[化2] (式中Ar 1及Ar 2各自獨立地表示伸芳基) [Chemicalization 2] (In the formula, Ar 1 and Ar 2 each independently represent an aryl group)
構成單元(I)衍生自6-羥基-2-萘甲酸(以下也稱為「HNA」(6-hydroxy-2-naphthoic acid))。(A)成分相對於全部構成單元含有40~75莫耳%的構成單元(I)。如果構成單元(I)的含有量在所述範圍內，則介電特性、耐熱性及製造性容易變得良好。從介電特性、耐熱性及製造性的觀點出發，構成單元(I)的含有量相對於全部構成單元較佳為40~60莫耳%，更佳為45~60莫耳%。The structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as "HNA" (6-hydroxy-2-naphthoic acid)). The component (A) contains 40 to 75 mol% of the structural unit (I) based on all the structural units. If the content of the structural unit (I) is within the above range, the dielectric properties, heat resistance and manufacturability are likely to be improved. From the viewpoint of dielectric properties, heat resistance and manufacturability, the content of the structural unit (I) is preferably 40 to 60 mol%, more preferably 45 to 60 mol% based on the total structural units.
構成單元(II)衍生自4-羥基苯甲酸(以下也稱為「HBA」(4-hydroxybenzoic acid))。(A)成分相對於全部構成單元含有0.5~7.5莫耳%的構成單元(II)。如果構成單元(II)的含有量在所述範圍內，則耐熱性及製造性容易變得良好。從耐熱性和製造性的觀點出發，構成單元(II)的含有量相對於全部構成單元較佳為1~6莫耳%。The structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as "HBA" (4-hydroxybenzoic acid)). The component (A) contains 0.5 to 7.5 mol% of the structural unit (II) based on all the structural units. When the content of the structural unit (II) is within the above range, heat resistance and manufacturability are likely to be improved. From the viewpoint of heat resistance and manufacturability, the content of the structural unit (II) is preferably 1 to 6 mol% based on the total structural units.
構成單元(III)是衍生自二羧酸的構成單元。作為Ar 1，可以舉出1,2-伸苯基(1,2-phenylene)、1,3-伸苯基、1,4-伸苯基等。從耐熱性的觀點出發，構成單元(III)較佳衍生自1,4-伸苯基二羧酸(1,4-phenylenedicarboxylic acid)(以下也稱為「TA」)。構成單元(III)的含有量相對於全部構成單元為8.5~30莫耳%，較佳為17.5~30莫耳%。 The structural unit (III) is a structural unit derived from a dicarboxylic acid. Examples of Ar 1 include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and the like. From the viewpoint of heat resistance, the structural unit (III) is preferably derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as "TA"). The content of the structural unit (III) is 8.5 to 30 mol%, preferably 17.5 to 30 mol%, based on all the structural units.
構成單元(IV)是衍生自二醇的構成單元。作為二醇，可以使用對苯二酚、二羥基聯苯等，從耐熱性的觀點出發，二羥基聯苯，特別是4,4’-二羥基聯苯(以下也稱為「BP」)較佳。構成單元(IV)的含有量相對於全部構成單元為8.5~30莫耳%，較佳為17.5~30莫耳%。The structural unit (IV) is a structural unit derived from diol. As the diol, hydroquinone, dihydroxybiphenyl, etc. can be used. From the viewpoint of heat resistance, dihydroxybiphenyl, especially 4,4'-dihydroxybiphenyl (hereinafter also referred to as "BP") is relatively good. The content of the structural unit (IV) is 8.5 to 30 mol%, preferably 17.5 to 30 mol%, based on all the structural units.
由於(A)成分相對於全部構成單元含有特定量的特定的構成單元的(I)~(IV)，因此介電特性、耐熱性和製造性皆優異。另外，相對於全部構成單元，(A)成分較佳含有合計100莫耳%的構成單元(I)~(IV)。Since component (A) contains a specific amount of specific structural units (I) to (IV) with respect to all structural units, it is excellent in dielectric properties, heat resistance, and manufacturability. In addition, the component (A) preferably contains a total of 100 mol% of the structural units (I) to (IV) with respect to all the structural units.
接著，對本發明的全芳香族聚酯的製造方法進行說明。本發明中的全芳香族聚酯使用直接聚合法、酯交換法等進行聚合。聚合時，可以使用熔融聚合法、溶液聚合法、漿料聚合(slurry polymerization)法、固相聚合法等、或其2種以上的組合，較佳可使用熔融聚合法、或熔融聚合法與固相聚合法的組合。Next, the method for producing the wholly aromatic polyester of the present invention will be described. The fully aromatic polyester in the present invention is polymerized using a direct polymerization method, a transesterification method, or the like. During polymerization, melt polymerization, solution polymerization, slurry polymerization, solid phase polymerization, etc., or a combination of two or more thereof can be used. It is preferable to use melt polymerization, or melt polymerization and solid phase polymerization. A combination of phase polymerization methods.
在本發明中，聚合時，可以對聚合單體使用醯化劑、作為醯氯化合物衍生物的末端活性化的單體等。作為醯化劑，可以舉出乙酸酐等的脂肪酸酐等。In the present invention, during polymerization, a chelating agent, a terminally activated monomer that is a chloride compound derivative, or the like may be used for the polymerized monomer. Examples of the chelating agent include fatty acid anhydrides such as acetic anhydride and the like.
這些的聚合時可以使用各種觸媒，作為代表性的觸媒，可舉出醋酸鉀、醋酸鎂、醋酸亞錫、鈦酸四丁酯、醋酸鉛、醋酸鈉、三氧化銻(antimony trioxide)、參(2,4-戊二酮)鈷(III)(tris(2,4-pentanedionato)cobalt(III))等的金屬鹽系觸媒、1-甲基咪唑、4-二甲基氨基吡啶等的有機化合物系觸媒。Various catalysts can be used for the polymerization of these. Typical catalysts include potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and antimony trioxide. Metal salt catalysts such as (2,4-pentanedionato)cobalt(III) (tris(2,4-pentanedionato)cobalt(III)), 1-methylimidazole, 4-dimethylaminopyridine, etc. Organic compounds are catalysts.
作為反應條件，例如為反應溫度200~380℃、最終到達壓力0.1~760 Torr(即13~101,080 Pa)。特別在熔融反應中，例如反應溫度為260~380℃，較佳為300~360℃，最終到達壓力為1~100 Torr(即133~13,300 Pa)，較佳為1~50 Torr(即133~6,670Pa)。Reaction conditions include, for example, a reaction temperature of 200 to 380°C and a final pressure of 0.1 to 760 Torr (ie, 13 to 101,080 Pa). Especially in melting reactions, for example, the reaction temperature is 260~380℃, preferably 300~360℃, and the final pressure is 1~100 Torr (i.e. 133~13,300 Pa), preferably 1~50 Torr (i.e. 133~ 6,670Pa).
反應可以將全部原料單體(HNA、HBA、TA、及BP)、醯化劑及觸媒裝入同一反應容器中而開始反應(一段方式)，也可以使原料單體HNA、HBA及BP的羥基藉由醯化劑醯化後，與TA的羧基反應(二段方式)。The reaction can be carried out by putting all the raw material monomers (HNA, HBA, TA, and BP), chelating agent, and catalyst into the same reaction vessel to start the reaction (one-step method), or the raw material monomers HNA, HBA, and BP can be After the hydroxyl group is chelated by a chelating agent, it reacts with the carboxyl group of TA (two-stage method).
熔融聚合在反應系內達到規定溫度後，開始減壓以成為規定的減壓度而進行。在攪拌機的扭力(torque)達到規定值後，導入惰性氣體，從減壓狀態經常壓至規定的加壓狀態，從反應系排出全芳香族聚酯。After the melt polymerization reaches a predetermined temperature in the reaction system, the pressure is reduced to a predetermined degree of pressure reduction. After the torque of the mixer reaches a predetermined value, an inert gas is introduced, the pressure is increased from a reduced pressure state to a predetermined pressurized state, and the fully aromatic polyester is discharged from the reaction system.
藉由上述聚合方法而製造的全芳香族聚酯可以進一步藉由在常壓或減壓，惰性氣體中加熱的固相聚合來謀求分子量的增加。固相聚合反應的較佳條件為反應溫度230~350℃，較佳為260~330℃，最終到達壓力10~760 Torr(即，1,330~101,080 Pa)。The molecular weight of the fully aromatic polyester produced by the above-mentioned polymerization method can be further increased by solid-state polymerization by heating under normal pressure or reduced pressure in an inert gas. The preferred conditions for the solid-state polymerization reaction are a reaction temperature of 230~350°C, preferably 260~330°C, and a final pressure of 10~760 Torr (ie, 1,330~101,080 Pa).
接著，對全芳香族聚酯的性質進行說明。本發明中的全芳香族聚酯在熔融時顯示出光學異向性。一樹脂在熔融時顯示光學異向性意味著所述樹脂為液晶性樹脂。本發明中的全芳香族聚酯兼具熱安定性和易加工性。Next, the properties of wholly aromatic polyester will be described. The wholly aromatic polyester in the present invention exhibits optical anisotropy when melted. A resin showing optical anisotropy when melted means that the resin is a liquid crystalline resin. The fully aromatic polyester in the present invention has both thermal stability and ease of processing.
熔融異向性的性質可以藉由使用正交偏光件的慣用的偏光檢查方法來確認。更具體而言，熔融異向性的確認可以藉由使用OLYMPUS公司製的偏光顯微鏡，將放置在LINKAM公司製的熱載台上的試料熔融，在氮氣氣氛下以150倍的倍率進行觀察而實施。全芳香族聚酯在光學上是異向性的，在插入正交偏光件間時使光透過。如果試料在光學上為異向性，則即使在例如熔融靜止液狀態下，偏光也會透過。The nature of the melt anisotropy can be confirmed by conventional polarization inspection methods using crossed polarizers. More specifically, the confirmation of melting anisotropy can be carried out by melting a sample placed on a hot stage made by LINKAM using a polarizing microscope made by OLYMPUS, and observing it at a magnification of 150 times in a nitrogen atmosphere. . Fully aromatic polyester is optically anisotropic, allowing light to pass through when inserted between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted even in a molten and still liquid state, for example.
由於向列型(nematic)全芳族聚酯在熔點以上會產生明顯的黏度降低，因此一般以於熔點或其以上的溫度顯示出液晶性作為加工性的指標。從耐熱性的觀點出發，熔點越高越好，但考慮到全芳香族聚酯的熔融加工時的熱劣化、擠出機的加熱能力等，熔點以360°C以下為較佳的標準。另外，更佳為300~360℃，又更佳為320~358℃。Since nematic fully aromatic polyester will have a significant decrease in viscosity above the melting point, liquid crystallinity at or above the melting point is generally used as an indicator of processability. From the viewpoint of heat resistance, the higher the melting point, the better. However, considering thermal degradation during melt processing of fully aromatic polyester, the heating capacity of the extruder, etc., the melting point is preferably 360°C or lower. In addition, 300~360°C is more preferred, and 320~358°C is still more preferred.
於本發明的製膜溫度且剪切速度1000/秒，上述全芳香族聚酯的熔融黏度較佳為500Pa·s以下，更佳為50~400Pa·s，又更佳為100~300Pa·s。當上述熔融黏度在上述範圍內時，上述全芳香族聚酯本身或含有上述全芳香族聚酯的組合物在其擠出時容易確保製膜性。另外，在本說明書中，採用根據ISO11443測定所得到的值作為上述熔融黏度。At the film forming temperature of the present invention and the shearing speed of 1000/second, the melt viscosity of the above-mentioned fully aromatic polyester is preferably 500 Pa·s or less, more preferably 50 to 400 Pa·s, and still more preferably 100 to 300 Pa·s. . When the melt viscosity is within the above range, the wholly aromatic polyester itself or the composition containing the wholly aromatic polyester can easily ensure film forming properties during extrusion. In addition, in this specification, the value measured based on ISO11443 is used as the said melt viscosity.
(A)成分的含有量相對於液晶性樹脂組合物整體為57~85質量%，較佳為59~83質量%，更佳為62.5~77.5質量%。如果(A)成分的含有量在上述範圍內，則容易得到介電特性優異的液晶性樹脂組合物。The content of component (A) is 57 to 85 mass %, preferably 59 to 83 mass %, more preferably 62.5 to 77.5 mass %, based on the entire liquid crystalline resin composition. If the content of component (A) is within the above range, a liquid crystalline resin composition excellent in dielectric properties can be easily obtained.
[(B)纖維狀無機填充劑] 若本發明的液晶性樹脂組合物含有纖維狀無機填充劑，則由所述液晶性樹脂組合物構成的成形體的耐裂紋性容易提高，另外，彎曲彈性模數等的機械強度容易提高。纖維狀無機填充劑可以單獨使用1種或組合使用2種以上。 [(B) Fibrous inorganic filler] When the liquid crystalline resin composition of the present invention contains a fibrous inorganic filler, the crack resistance of a molded article composed of the liquid crystalline resin composition is easily improved, and the mechanical strength such as bending elastic modulus is easily improved. The fibrous inorganic filler can be used individually by 1 type or in combination of 2 or more types.
纖維狀無機填充劑的平均纖維長為150~500μm，較佳為200~450μm，更佳為250~400μm。如果上述平均纖維長為150μm以上，則由本發明的液晶性樹脂組合物構成的成形體的耐裂紋性容易提高。如果上述平均纖維長為500μm以下，則容易提高由液晶性樹脂組合物構成的成形體的介電特性。另外，在本說明書中，採用以下作為纖維狀無機填充劑的平均纖維長：將10張纖維狀無機填充劑的立體顯微影像從CCD相機導入到PC中，並藉由影像測定機的影像處理手法，對每1張立體顯微影像100根的纖維狀無機填充劑，即合計1000根的纖維狀無機填充劑測定纖維長的值的平均。藉由將上述方法應用於藉由將液晶性樹脂組合物於600℃加熱2小時而灰化所殘存的纖維狀無機填充劑，以測定液晶性樹脂組合物中的纖維狀無機填充劑的平均纖維長。另外，在本說明書中，除非另有說明，否則平均纖維長是指重量平均纖維長。The average fiber length of the fibrous inorganic filler is 150~500 μm, preferably 200~450 μm, more preferably 250~400 μm. If the average fiber length is 150 μm or more, the crack resistance of the molded article composed of the liquid crystalline resin composition of the present invention is likely to be improved. If the average fiber length is 500 μm or less, the dielectric properties of a molded article made of the liquid crystalline resin composition can be easily improved. In addition, in this specification, the following is used as the average fiber length of the fibrous inorganic filler: 10 three-dimensional microscopic images of the fibrous inorganic filler are imported from a CCD camera to a PC, and image processing is performed by an image measuring machine. The method is to measure the average value of the fiber length for 100 fibrous inorganic fillers per one stereoscopic microscopic image, that is, 1000 fibrous inorganic fillers in total. The average fiber of the fibrous inorganic filler in the liquid crystalline resin composition was measured by applying the above method to the fibrous inorganic filler remaining in ashes by heating the liquid crystalline resin composition at 600° C. for 2 hours. long. In addition, in this specification, unless otherwise stated, the average fiber length means the weight average fiber length.
纖維狀無機填充材料的纖維徑沒有特別限制，例如可以為20μm以下，也可為5~15μm。另外，在本說明書中，採用以下作為纖維狀無機填充劑的纖維徑：以掃描型電子顯微鏡觀察纖維狀無機填充劑，並對30根的纖維狀無機填充劑測定纖維徑的值的平均。藉由將上述方法應用於藉由將液晶性樹脂組合物於600℃加熱2小時而灰化所殘留的纖維狀無機填充劑，以測定液晶性樹脂組合物中的纖維狀無機填充劑的纖維徑。The fiber diameter of the fibrous inorganic filler material is not particularly limited, and may be, for example, 20 μm or less, or 5 to 15 μm. In addition, in this specification, as the fiber diameter of a fibrous inorganic filler, the following is used: the fibrous inorganic filler was observed with a scanning electron microscope, and the average value of the fiber diameter of 30 fibrous inorganic fillers was measured. The fiber diameter of the fibrous inorganic filler in the liquid crystalline resin composition was measured by applying the above method to the fibrous inorganic filler remaining in ashes by heating the liquid crystalline resin composition at 600° C. for 2 hours. .
可以使用任何纖維，只要其為滿足上述形狀的纖維狀無機填充劑。作為纖維狀無機填充劑，例如可舉出玻璃纖維、磨碎玻璃纖維、碳纖維、石棉纖維(asbestos fiber)、二氧化矽纖維、二氧化矽・氧化鋁纖維、二氧化鋯纖維、氮化硼纖維、氮化矽纖維、硼纖維、鈦酸鉀纖維、矽酸鈣纖維(矽灰石(wollastonite))、另外還有不銹鋼、鋁、鈦、銅、黃銅等的金屬的纖維狀物等的無機質纖維狀物質。在本發明中，從耐裂紋性的觀點來看，作為纖維狀無機填充劑，較佳使用選自由玻璃纖維和磨碎玻璃纖維所組成的群組中的至少1種。Any fiber can be used as long as it is a fibrous inorganic filler that satisfies the above-mentioned shape. Examples of the fibrous inorganic filler include glass fiber, ground glass fiber, carbon fiber, asbestos fiber, silica fiber, silica/alumina fiber, zirconium dioxide fiber, and boron nitride fiber. , silicon nitride fiber, boron fiber, potassium titanate fiber, calcium silicate fiber (wollastonite), and inorganic substances such as fibrous materials of stainless steel, aluminum, titanium, copper, brass, etc. Fibrous material. In the present invention, from the viewpoint of crack resistance, it is preferred to use at least one selected from the group consisting of glass fibers and ground glass fibers as the fibrous inorganic filler.
(B)成分的含有量相對於液晶性樹脂組合物整體為5~14質量%，較佳為6~12.5質量%，更佳為7~10質量%。如果(B)成分的含有量在上述範圍內，則在充分確保液晶性樹脂組合物的流動性的同時，容易提高由液晶性樹脂組合物構成的成形體的耐裂紋性及機械強度。The content of component (B) is 5 to 14 mass %, preferably 6 to 12.5 mass %, more preferably 7 to 10 mass %, based on the entire liquid crystalline resin composition. When the content of component (B) is within the above range, the crack resistance and mechanical strength of a molded article composed of the liquid crystalline resin composition can be easily improved while ensuring sufficient fluidity of the liquid crystalline resin composition.
[(C)無機球狀中空體] (C)無機球狀中空體通常被稱為中空球(balloon)，作為無機球狀中空體的材料，例如可以舉出氧化鋁、二氧化矽、玻璃等的無機材料。其中，從耐熱性、强度等的觀點出發，較佳為玻璃。即，作為無機球狀中空體，較佳使用玻璃球。(C)成分可以單獨使用，也可以並用2種以上。 [(C) Inorganic spherical hollow body] (C) Inorganic spherical hollow bodies are generally called balloons. Examples of materials for the inorganic spherical hollow bodies include inorganic materials such as alumina, silica, and glass. Among them, glass is preferred from the viewpoint of heat resistance, strength, etc. That is, as the inorganic spherical hollow body, glass spheres are preferably used. (C) Component may be used individually or in combination of 2 or more types.
從抑制熔融黏度上升及流動性惡化及成形性等觀點出發，(C)無機球狀中空體的長寬比(aspect ratio)較佳為1.15以上，更佳為1.20以上2.00以下，又更佳為1.22以上1.50以下，又進一步更佳為1.25以上小於1.30。在本說明書中，採用下述作為長寬比：使用動態圖像解析法/粒子狀態分析儀，對3000個粒子測定粒子投影面中最長部分的長度即最大長度L、和粒子投影面中與最大長度L垂直的方向上最長部分的長度即最大垂直長度S，重複此測定數次，對各粒子計算出的L/S的平均的值。From the viewpoint of suppressing an increase in melt viscosity, deterioration of fluidity, and formability, the aspect ratio of (C) the inorganic spherical hollow body is preferably 1.15 or more, more preferably 1.20 or more and 2.00 or less, and still more preferably 1.22 or more and 1.50 or less, and further preferably 1.25 or more and less than 1.30. In this specification, the following is used as the aspect ratio: using a dynamic image analysis method/particle state analyzer, 3000 particles are measured, which is the length of the longest part of the particle projection plane, that is, the maximum length L, and the length of the particle projection plane and the maximum length L. The length of the longest part in the vertical direction of length L is the maximum vertical length S. This measurement is repeated several times, and the average value of L/S is calculated for each particle.
從成形性的觀點出發，(C)成分的中位直俓(median diameter)較佳為5μm以上，更佳為10μm以上，從破壞抑制、成形性等的觀點出發，(C)成分的較佳為200μm以下，更佳為100μm以下，又更佳為50μm以下。另外，在本說明中，中位直俓為使用雷射折射/散射式粒度分佈測定法而測定的體積基準的中央值。From the viewpoint of formability, the median diameter of component (C) is preferably 5 μm or more, more preferably 10 μm or more. From the viewpoint of damage suppression, formability, etc., component (C) is preferably 5 μm or more, and more preferably 10 μm or more. It is 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less. In addition, in this description, the median value is a volume-based central value measured using the laser refraction/scattering particle size distribution measuring method.
(C)成分的含有量相對於液晶性樹脂組合物整體為7.5~29質量%，較佳為9~28.5質量%，更佳為15~28質量%。若(C)成分的含有量在7.5質量%以上，則容易得到介電特性優異的液晶性樹脂組合物。若(C)成分的含有量為29質量%以下，則容易得到流動性良好的液晶性樹脂組合物，容易提高液晶性樹脂組合物所構成的成形體的機械強度及介電特性。The content of component (C) is 7.5 to 29 mass%, preferably 9 to 28.5 mass%, more preferably 15 to 28 mass%, based on the entire liquid crystalline resin composition. If the content of component (C) is 7.5% by mass or more, a liquid crystalline resin composition excellent in dielectric properties can be easily obtained. If the content of component (C) is 29% by mass or less, a liquid crystalline resin composition with good fluidity can be easily obtained, and the mechanical strength and dielectric properties of a molded article composed of the liquid crystalline resin composition can be easily improved.
(B)纖維狀無機填充劑及(C)無機球狀中空體的合計含有量相對於液晶性樹脂組合物整體為15~43質量%，較佳為17~41質量%，更佳為22.5~37.5質量%。若上述合計含有量在上述範圍內，則容易得到介電特性優異的液晶性樹脂組合物。The total content of (B) the fibrous inorganic filler and (C) the inorganic spherical hollow body is 15 to 43 mass %, preferably 17 to 41 mass %, more preferably 22.5 to 22.5 mass % with respect to the entire liquid crystal resin composition. 37.5% by mass. If the total content is within the above range, a liquid crystalline resin composition excellent in dielectric properties can be easily obtained.
[(D)除(B)纖維狀無機填充劑及(C)無機球狀中空體之外的無機填充劑] 本發明的液晶性樹脂組合物也可以任意地含有(D)除(B)纖維狀無機填充劑及(C)無機球狀中空體之外的無機填充劑。若所述液晶性樹脂組合物含有(D)成分，則所述液晶性樹脂組合物的成形體容易提高彎曲彈性模量等的機械強度。(D)成分可以單獨使用，也可以並用2種以上。作為(D)成分，例如可以舉出板狀填充劑、粒狀填充劑等。 [(D) Inorganic fillers other than (B) fibrous inorganic filler and (C) inorganic spherical hollow body] The liquid crystalline resin composition of the present invention may optionally contain (D) an inorganic filler other than the (B) fibrous inorganic filler and (C) the inorganic spherical hollow body. When the liquid crystalline resin composition contains the component (D), the mechanical strength such as bending elastic modulus of the molded article of the liquid crystalline resin composition can be easily improved. (D) Component may be used individually or in combination of 2 or more types. Examples of the component (D) include plate-shaped fillers, granular fillers, and the like.
(板狀填充劑) 當本發明的液晶性樹脂組合物含有板狀填充劑時，由所述液晶性樹脂組合物構成的成形體容易提高彎曲彈性模數等的機械強度，容易抑制翹曲。板狀填充劑可以單獨使用，也可以並用2種以上。 (plate filler) When the liquid crystalline resin composition of the present invention contains a plate-shaped filler, the molded article composed of the liquid crystalline resin composition can easily increase mechanical strength such as bending elastic modulus, and can easily suppress warpage. The plate-shaped filler may be used alone, or two or more types may be used in combination.
板狀填充劑的中位直徑較佳為15~50 μm。若上述中位直徑為15 μm以上，容易確保必要的機械強度，成形體的翹曲抑制效果容易變高。若上述中位直徑為50 μm以下，容易提高組合物熔融時的流動性。較佳上述中位直徑為20~30 μm。The preferred median diameter of the plate-shaped filler is 15~50 μm. If the above-mentioned median diameter is 15 μm or more, the necessary mechanical strength can be easily ensured, and the warpage suppressing effect of the molded article can be easily increased. If the above-mentioned median diameter is 50 μm or less, the fluidity of the composition when melted is easily improved. The preferred above-mentioned median diameter is 20~30 μm.
作為板狀填充劑，沒有特別限定，例如可以舉出雲母、滑石、玻璃片(glass flake)、石墨、各種的金屬箔(例如鋁箔、鐵箔、銅箔)等。The plate-shaped filler is not particularly limited, and examples thereof include mica, talc, glass flake, graphite, and various metal foils (for example, aluminum foil, iron foil, copper foil), and the like.
(粒狀填充劑) 當本發明的液晶性樹脂組合物含有粒狀填充劑時，由所述液晶性樹脂組合物構成的成形體容易提高彎曲彈性模數等的機械強度，容易抑制表面白化。粒狀填充劑可以單獨使用1種或組合使用2種以上。 (granular filler) When the liquid crystalline resin composition of the present invention contains a granular filler, the molded article composed of the liquid crystalline resin composition can easily increase mechanical strength such as bending elastic modulus, and can easily suppress surface whitening. A granular filler can be used individually by 1 type or in combination of 2 or more types.
粒狀填充劑中位直徑較佳為0.3~5.0 μm。上述中位直徑為0.3 μm以上時，容易維持成形體的耐衝擊性。上述中位直徑為5.0 μm以下時，成形體的表面白化抑制效果容易變高。上述中位直徑更佳為0.5~5.0 μm，又更佳為0.5~4.0 μm。The preferred median diameter of the granular filler is 0.3~5.0 μm. When the above-mentioned median diameter is 0.3 μm or more, the impact resistance of the molded body can be easily maintained. When the above-mentioned median diameter is 5.0 μm or less, the surface whitening inhibitory effect of the molded article is likely to be high. The above-mentioned median diameter is more preferably 0.5~5.0 μm, and more preferably 0.5~4.0 μm.
作為粒狀填充劑，例如可舉出二氧化矽、石英粉末、玻璃珠、玻璃粉、矽酸鉀鋁、矽藻土、氧化鐵、氧化鈦、氧化鋅、氧化鋁等的金屬氧化物；碳酸鈣、碳酸鎂等的金屬碳酸鹽；硫酸鈣、硫酸鋇等的金屬硫酸鹽；焦磷酸鈣、無水磷酸二鈣等的磷酸鹽；碳化矽；氮化矽；氮化硼等。在本發明中，從成形體的表面白化抑制及成形體的低發塵性的觀點出發，較佳使用選自由二氧化矽及硫酸鋇所組成之群組中的1種以上作為粒狀填充劑，更佳使用二氧化矽作為粒狀填充劑。Examples of the granular filler include metal oxides such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, aluminum oxide; and carbonic acid. Metal carbonates such as calcium and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and dicalcium phosphate anhydrous; silicon carbide; silicon nitride; boron nitride, etc. In the present invention, from the viewpoint of suppressing surface whitening of the molded article and reducing dust generation of the molded article, it is preferred to use at least one selected from the group consisting of silica and barium sulfate as the granular filler. , it is better to use silica as a granular filler.
(D)成分的含有量相對於液晶性樹脂組合物整體較佳為0.1~5質量%，更佳為0.2~2質量%，又更佳為0.5~1質量%。(D)成分的含有量在上述範圍內時，能够充分確保液晶性樹脂組合物的流動性，同時容易提高由液晶性樹脂組合物構成的成形體的機械強度。The content of component (D) is preferably 0.1 to 5 mass%, more preferably 0.2 to 2 mass%, and still more preferably 0.5 to 1 mass%, based on the entire liquid crystalline resin composition. When the content of component (D) is within the above range, the fluidity of the liquid crystalline resin composition can be sufficiently ensured, and the mechanical strength of the molded article composed of the liquid crystalline resin composition can be easily improved.
[其他成分] 在不損害本發明的效果的範圍內，本發明的液晶性樹脂組合物中也可以根據所需性能適當添加其他聚合物、其他填充劑、一般添加在合成樹脂中的公知物質，即抗氧化劑、紫外線吸收劑等的穩定劑、抗靜電劑、阻燃劑、染料、顏料等的著色劑、潤滑劑、脫模劑、結晶化促進劑、結晶成核劑等。 [Other ingredients] In the range that does not impair the effects of the present invention, other polymers, other fillers, and known substances generally added to synthetic resins, that is, antioxidants, can also be appropriately added to the liquid crystalline resin composition of the present invention according to the required performance. Stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, release agents, crystallization accelerators, crystal nucleating agents, etc.
其他聚合物是指(A)全芳香族聚酯以外的聚合物，例如可以舉出含有環氧基的共聚物。其它填充劑是指除(B)纖維狀無機填充劑、(C)無機球狀中空體及(D)無機填充劑以外的填充劑，例如可以舉出有機填充劑、炭黑。Other polymers refer to polymers other than (A) wholly aromatic polyester, and examples include epoxy group-containing copolymers. Other fillers refer to fillers other than (B) fibrous inorganic filler, (C) inorganic spherical hollow body, and (D) inorganic filler, and examples thereof include organic fillers and carbon black.
[液晶性樹脂組合物的製備] 本發明的液晶性樹脂組合物的製備沒有特別限定。例如，配合(A)成分、(B)成分、(C)成分、任意地配合(D)成分及任意地配合其他成分，使用1軸或2軸擠出機對其進行熔融混煉處理，以進行液晶性樹脂組合物的製備。 [Preparation of liquid crystalline resin composition] The preparation of the liquid crystalline resin composition of the present invention is not particularly limited. For example, component (A), component (B), component (C), component (D) optionally, and other components are optionally blended, and the mixture is melt-kneaded using a 1-screw or 2-screw extruder to obtain A liquid crystalline resin composition is prepared.
[液晶性樹脂組合物] 從熔融時的流動性的觀點、成形加工性的觀點出發，如上所述得到的本發明的液晶性樹脂組合物的熔融黏度較佳為80Pa·sec以下，更佳為75Pa·sec以下，又更佳為73Pa·sec以下。在本說明書中，作為熔融黏度，採用在比液晶性樹脂的熔點高10~30℃的料管(cylinder)溫度、剪切速度1000sec -1的條件下，以基於ISO 11443的測定方法而得到的值。 [Liquid crystalline resin composition] From the viewpoint of fluidity during melting and molding processability, the melt viscosity of the liquid crystalline resin composition of the present invention obtained as described above is preferably 80 Pa·sec or less, more preferably 75 Pa·sec or less, more preferably 73 Pa·sec or less. In this specification, the melt viscosity is obtained by the measurement method based on ISO 11443 under the conditions of a cylinder temperature 10 to 30°C higher than the melting point of the liquid crystal resin and a shear speed of 1000 sec -1 value.
本發明的液晶性樹脂組合物於測定頻率5GHz的相對介電係數較佳為3.4以下，更佳為3.2以下，又更佳為3.0以下。本發明的液晶性樹脂組合物於測定頻率5GHz的介電損耗正切較佳為0.0045以下，更佳為0.0042以下，又更佳為0.0040以下。The relative dielectric coefficient of the liquid crystalline resin composition of the present invention at a measurement frequency of 5 GHz is preferably 3.4 or less, more preferably 3.2 or less, and still more preferably 3.0 or less. The dielectric loss tangent of the liquid crystalline resin composition of the present invention at a measurement frequency of 5 GHz is preferably 0.0045 or less, more preferably 0.0042 or less, and still more preferably 0.0040 or less.
＜平面狀連接器＞ 藉由將本發明的液晶性樹脂組合物成形，可以得到本發明的平面狀連接器。平面狀連接器的形狀沒有特別限定。平面狀連接器具有外框部和形成在外框部內側的格子構造，上述格子構造中的格子部的節距間隔可以為1.5mm以下。平面連接器可以在前述格子構造的內部具有開口部。平面狀連接器的上述外框部和前述格子部的厚度比率可以為1.0以下。另外，平面狀連接器也可以是非常薄壁的平面狀連接器，其保持平面狀連接器的端子的格子部的樹脂部分的寬度為0.5mm以下，製品整體的高度為5.0mm以下。 ＜Planar Connector＞ By molding the liquid crystalline resin composition of the present invention, the planar connector of the present invention can be obtained. The shape of the planar connector is not particularly limited. The planar connector has an outer frame part and a lattice structure formed inside the outer frame part, and the pitch interval of the lattice parts in the lattice structure may be 1.5 mm or less. The planar connector may have an opening inside the lattice structure. The thickness ratio of the outer frame part and the grid part of the planar connector may be 1.0 or less. In addition, the planar connector may be a very thin-walled planar connector in which the width of the resin portion of the grid portion holding the terminals of the planar connector is 0.5 mm or less, and the height of the entire product is 5.0 mm or less.
作為本發明的平面狀連結器的形狀，例如可舉出如第1圖所示的形狀。所述平面狀連結器的整體的大小為43.88mm×43.88mm×3mmt，具有厚度為3mm以下的外框部、厚度為1.5mm以下的格子部、中央部13.88mm×13.88mm的開口部。另外，所述平面狀連結器的引腳插入孔為了防止插入平面狀連結器的引腳的脫落，引腳插入孔的寬度也可以部分變窄。As a shape of the planar connector of this invention, the shape shown in FIG. 1 is mentioned, for example. The overall size of the planar connector is 43.88 mm × 43.88 mm × 3 mmt, and has an outer frame part with a thickness of 3 mm or less, a grid part with a thickness of 1.5 mm or less, and an opening part of 13.88 mm x 13.88 mm in the center. In addition, in order to prevent the pins inserted into the planar connector from falling off, the width of the pin insertion holes of the planar connector may be partially narrowed.
本發明的平面狀連接器的格子部的引腳插入孔的形狀沒有特別限定，可以為方形、圓形等。The shape of the pin insertion holes in the grid portion of the planar connector of the present invention is not particularly limited, and may be square, circular, or the like.
作為得到本發明的平面狀連接器的成形方法沒有特別限定，但為了防止得到的平面狀連接器的變形，得到具有良好平面度的平面狀連接器，較佳選擇不會殘留內部應力的成形條件。為了降低填充壓力、降低所得平面狀連接器的殘留內部應力，成形機的料管溫度較佳為液晶性聚合物的熔點以上的溫度。There is no particular limitation on the molding method for obtaining the planar connector of the present invention. However, in order to prevent deformation of the obtained planar connector and obtain a planar connector with good flatness, it is preferable to select molding conditions in which internal stress does not remain. . In order to reduce the filling pressure and reduce the residual internal stress of the resulting planar connector, the temperature of the tube of the molding machine is preferably higher than the melting point of the liquid crystal polymer.
另外，金屬模具溫度較佳為70~100℃。如果金屬模具溫度低，則填充在金屬模具中的複合樹脂組合物有可能引發流動不良，因此不較佳。如果金屬模具溫度高，則有可能產生毛刺(burr)等的問題，因此不較佳。關於射出速度，較佳以150mm/秒以上成形。如果射出速度低，則有可能只得到未填充成形品，即使得到完全填充的成形品，也有可能成為填充壓力高、殘留內部應力大的成形品，只得到平面度差的連接器。In addition, the metal mold temperature is preferably 70~100℃. If the temperature of the metal mold is low, it is not preferable because the composite resin composition filled in the metal mold may suffer from flow failure. If the temperature of the metal mold is high, problems such as burrs may occur, which is not preferable. Regarding the injection speed, it is preferably 150 mm/second or more for molding. If the injection speed is low, an unfilled molded product may be obtained. Even if a fully filled molded product is obtained, the molded product may have high filling pressure and high residual internal stress, resulting in a connector with poor flatness.
本發明的平面狀連接器的耐裂紋性、機械強度、及介電特性優異。 [實施例] The planar connector of the present invention has excellent crack resistance, mechanical strength, and dielectric properties. [Example]
以下舉出實施例，更詳細地說明本發明，但本發明並不僅限定於這些實施例。 ＜全芳香族聚酯＞ The present invention will be explained in more detail below using examples, but the present invention is not limited only to these examples. ＜Fully aromatic polyester＞
・全芳香族聚酯1 將下述原料裝入聚合容器之後，將反應系的溫度提升至140℃，於140℃反應1小時。之後，再用5.5小時升溫至360℃，之後用30分鐘減壓至5 Torr(即667 Pa)，一邊蒸餾出醋酸、過剩的乙酸酐、其他低沸成分一邊進行熔融聚合。在攪拌扭力達到規定值後，導入氮氣，從減壓狀態經常壓至加壓狀態，從聚合容器的下部排出聚合物，將股(strand)造粒而粒化。在氮氣流下，對得到的顆粒(pellet)以300℃進行3小時的熱處理，得到全芳香族聚酯1的顆粒。顆粒的熔點為348℃，熔融黏度為9Pa·s。另外，按照後述的熔點的測定方法測定全芳香族聚酯1的熔點，與後述的熔融黏度的測定方法同樣地測定全芳香族聚酯1的熔融黏度。 6-羥基-2-萘甲酸(HNA)：1218g(48莫耳%) 4-羥基苯甲酸(HBA)：37g(2莫耳%) 1,4-伸苯基二羧酸：560g(TA)：(25莫耳%) 4,4’-二羥基聯苯(BP)：628g(25莫耳%) 金屬觸媒(醋酸鉀觸媒)：165mg 醯化劑(乙酸酐)：1432g ・Fully aromatic polyester 1 After the following raw materials were put into the polymerization vessel, the temperature of the reaction system was raised to 140°C, and the reaction was carried out at 140°C for 1 hour. Thereafter, the temperature was raised to 360°C over another 5.5 hours, and then the pressure was reduced to 5 Torr (ie, 667 Pa) over 30 minutes, and melt polymerization was performed while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reaches a predetermined value, nitrogen gas is introduced and the pressure is constantly increased from a reduced pressure state to a pressurized state. The polymer is discharged from the lower part of the polymerization vessel, and the strands are granulated and granulated. The obtained pellets were heat-treated at 300° C. for 3 hours under a nitrogen flow to obtain pellets of wholly aromatic polyester 1. The melting point of the particles is 348°C and the melt viscosity is 9 Pa·s. In addition, the melting point of the wholly aromatic polyester 1 was measured according to the method for measuring the melting point described below, and the melt viscosity of the wholly aromatic polyester 1 was measured in the same manner as the method for measuring the melt viscosity described below. 6-Hydroxy-2-naphthoic acid (HNA): 1218g (48 mol%) 4-Hydroxybenzoic acid (HBA): 37g (2 mol%) 1,4-phenylenedicarboxylic acid: 560g (TA): (25 mol%) 4,4’-dihydroxybiphenyl (BP): 628g (25 mol%) Metal catalyst (potassium acetate catalyst): 165mg Chelating agent (acetic anhydride): 1432g
[熔點的測定方法] 在TA Instruments公司製造DSC中，在將全芳香族聚酯從室溫以20℃/分鐘的升溫條件加熱時觀測到的吸熱峰溫度(Tm1)的測定後，在(Tm1+40)℃的溫度下保持2分鐘後，以20℃/分鐘的降溫條件暫時冷卻到室溫後，再次測定以20℃/分鐘的升溫條件加熱時觀測到的吸熱峰的溫度，作為聚合物的熔點。 [Measurement method of melting point] In the DSC manufactured by TA Instruments, after measuring the endothermic peak temperature (Tm1) observed when the fully aromatic polyester was heated from room temperature at a temperature rise condition of 20°C/min, the temperature at (Tm1+40)°C After holding at 20°C/min for 2 minutes, the polymer was temporarily cooled to room temperature with a temperature drop of 20°C/min, and then the temperature of the endothermic peak observed during heating with a temperature increase of 20°C/min was measured again as the melting point of the polymer.
＜全芳香族聚酯以外的材料＞ ・玻璃纖維：ECS03T-786H(日本電氣硝子股份有限公司製造，短切絲(chopped strands)，纖維徑10μm，長度3mm，真比重2.6) ・磨碎玻璃纖維：PF70E001(日東紡股份有限公司製造，纖維徑10 μm，平均纖維長70 μm(製造商公稱值)) ・玻璃球：Y12000(SEISHIN ENTERPRISE股份有限公司，長寬比（平均）1.264，中位直徑35μm，真比重0.6) ・滑石：ROWN TALC PP(松村產業股份有限公司製造，滑石，中位直徑14.6μm) ＜Materials other than fully aromatic polyester＞ ・Glass fiber: ECS03T-786H (manufactured by Nippon Electric Glass Co., Ltd., chopped strands, fiber diameter 10μm, length 3mm, true specific gravity 2.6) ・Ground glass fiber: PF70E001 (manufactured by Nittobo Co., Ltd., fiber diameter 10 μm, average fiber length 70 μm (manufacturer’s nominal value)) ・Glass sphere: Y12000 (SEISHIN ENTERPRISE Co., Ltd., aspect ratio (average) 1.264, median diameter 35 μm, true specific gravity 0.6) ・Talc: ROWN TALC PP (manufactured by Matsumura Industrial Co., Ltd., talc, median diameter 14.6 μm)
＜液晶性樹脂組合物的製造＞ 利用二軸擠出機(日本製鋼所股份有限公司製TEX30α型)將上述成分以表1所示的比率，於370°C料管溫度熔融混煉，得到液晶性樹脂組合物顆粒。 <Manufacture of liquid crystalline resin composition> The above ingredients were melt-kneaded at a tube temperature of 370°C using a twin-screw extruder (TEX30α type manufactured by Nippon Steel Works Co., Ltd.) at the ratio shown in Table 1 to obtain liquid crystalline resin composition particles.
＜熔融黏度＞ 使用東洋精機製作所股份有限公司製造的Capilograph 1B型，於高於液晶性樹脂熔點10~30°C的溫度，使用內徑為1 mm、長度為20 mm的孔口(orifice)，在1000/秒的剪切速率下，根據ISO 11443測定液晶性樹脂組合物的熔體黏度。其中，具體的測定溫度為370℃。結果如表1所示。 ＜Melt viscosity＞ Capilograph 1B type manufactured by Toyo Seiki Seisakusho Co., Ltd. is used. At a temperature of 10 to 30°C higher than the melting point of liquid crystal resin, an orifice with an inner diameter of 1 mm and a length of 20 mm is used at 1000/second. The melt viscosity of the liquid crystalline resin composition is measured according to ISO 11443 at a shear rate of . Among them, the specific measurement temperature is 370°C. The results are shown in Table 1.
＜重量平均纖維長＞ 液晶性樹脂組合物中的纖維狀無機填充劑的重量平均纖維長藉由下述的方法測定。 將液晶性樹脂組合物顆粒5g於600℃加熱2小時灰化。將灰化殘渣充分分散於5質量%聚乙二醇水溶液中後，用滴管移至培養皿中，用立體顯微鏡觀察纖維狀無機填充劑。採用以下作為纖維狀無機填充劑的重量平均纖維長：將纖維狀無機填充劑的10張立體顯微鏡影像從CCD相機導入到PC中，藉由影像測定機(NIRECO股份有限公司製LUZEXFS)的影像處理方法，對每1張立體顯微鏡影像100根的纖維狀無機填充劑，即合計1000根的纖維狀無機填充劑測量纖維長的值的平均。結果如表1所示。 ＜Weight average fiber length＞ The weight average fiber length of the fibrous inorganic filler in the liquid crystalline resin composition is measured by the following method. 5 g of liquid crystalline resin composition particles were heated at 600° C. for 2 hours to ashes. After the ashed residue was fully dispersed in a 5% by mass polyethylene glycol aqueous solution, it was moved to a petri dish with a dropper, and the fibrous inorganic filler was observed with a stereomicroscope. The following weight average fiber length of the fibrous inorganic filler was used: 10 stereoscopic microscope images of the fibrous inorganic filler were imported from a CCD camera to a PC, and image processing was performed with an image measuring machine (LUZEXFS manufactured by NIRECO Co., Ltd.) In this method, the average value of the fiber length is measured for 100 fibrous inorganic fillers per one stereoscopic microscope image, that is, a total of 1,000 fibrous inorganic fillers. The results are shown in Table 1.
＜荷重撓曲溫度＞ 在下述成形條件下，將液晶性樹脂組合物射出成形，得到ISO試驗片A形。將所述試驗片切成80mm×10mm×4mm以製作試驗片。使用所述試驗片，按照ISO75-1和2測定荷重撓曲溫度。使用荷重撓曲溫度作為表示成形體的耐熱性的指標。結果如表1所示。 [成形條件] 成形機：住友重機械工業股份有限公司，SE100DU 料管溫度：370℃ 金屬模具溫度：90℃ 射出速度：33mm/sec ＜Load deflection temperature＞ The liquid crystalline resin composition was injection molded under the following molding conditions to obtain ISO test piece A-shaped. The test piece was cut into 80 mm×10 mm×4 mm to prepare a test piece. Using the test piece, the load deflection temperature was measured in accordance with ISO75-1 and 2. The deflection temperature under load is used as an index indicating the heat resistance of the molded article. The results are shown in Table 1. [Forming conditions] Forming machine: Sumitomo Heavy Industries, Ltd., SE100DU Material tube temperature: 370℃ Metal mold temperature: 90℃ Injection speed: 33mm/sec
＜彎曲試驗＞ 在下述成形條件下，將液晶性樹脂組合物射出成形，得到ISO試驗片A形。將所述試驗片切成80mm×10mm×4mm以製作彎曲試驗片。使用所述試驗片，按照ISO178測定彎曲強度、彎曲彈性模數及彎曲應變。結果如表1所示。 [成形條件] 成形機：住友重機械工業股份有限公司 SE100DU 料管溫度：370℃ 金屬模具溫度：90℃ 射出速度：33mm/sec ＜Bending test＞ The liquid crystalline resin composition was injection molded under the following molding conditions to obtain ISO test piece A-shaped. The test piece was cut into 80 mm×10 mm×4 mm to prepare a bending test piece. Using the test piece, the bending strength, bending elastic modulus, and bending strain were measured in accordance with ISO178. The results are shown in Table 1. [Forming conditions] Forming machine: Sumitomo Heavy Industries, Ltd. SE100DU Material tube temperature: 370℃ Metal mold temperature: 90℃ Injection speed: 33mm/sec
＜介電特性＞ 使用成形機（住友重機械工業股份有限公司製「SE-100DU」），於以下成形條件成形實施例及比較例的顆粒，製作80mm×80mm×1mm的平板狀試驗片。如第3圖所示，從沿著平板狀試驗片反澆口側的流動直角方向的一邊至內側10mm處，以流動直角方向為長度方向切出80mm×1mm×1mm的試驗片，將其作為流動直角方向的介電特性評估用試驗片。另外，如第4圖所示，從沿著平板狀試驗片的流動方向的一邊至內側10mm處，以流動方向為長度方向切出80mm×1mm×1mm的試驗片，將其作為流動方向的介電特性評估用試驗片。對於這些試驗片，使用關東電子應用開發股份有限公司製的以下結構的空腔共振器微擾法(cavity resonator perturbation method)複介電常數(complex dielectric constant)評估裝置，於5GHz測定相對介電係數和介電損耗正切。對於相對介電係數及介電損耗正切，分別計算出流動直角方向的值與流動方向的值的平均值，作為上述平板狀試驗片的相對介電係數及介電損耗正切。結果如表1所示。 純量網絡分析儀(scalar network analyzer)：Agilent Technologies 8757D 頻率合成器：Agilent Technologies 83650L Swept CW Generator 固定衰减器：Agilent Technologies 85025D Detector 空腔共振器：關東電子應用開發CP431 測定程式：關東電子應用開發CPMA-S2/V2 [成形條件] 料管溫度：370℃ 金屬模具溫度：80℃ 射出速度：33mm/sec 保壓：60Mpa ＜Dielectric properties＞ Using a molding machine ("SE-100DU" manufactured by Sumitomo Heavy Industries, Ltd.), the pellets of the examples and comparative examples were molded under the following molding conditions to produce flat test pieces of 80 mm×80 mm×1 mm. As shown in Figure 3, cut out a test piece of 80 mm × 1 mm × 1 mm from one side along the flow direction perpendicular to the back gate side of the flat test piece to 10 mm inside, with the flow perpendicular direction as the length direction, and use it as Test piece for evaluating dielectric properties in the direction perpendicular to the flow. In addition, as shown in Figure 4, cut out a test piece of 80 mm × 1 mm × 1 mm from one side along the flow direction of the flat test piece to 10 mm inside, with the flow direction as the length direction, and use this as an intermediary in the flow direction. Test piece for electrical characteristics evaluation. For these test pieces, the relative dielectric coefficient was measured at 5 GHz using a cavity resonator perturbation method complex dielectric constant evaluation device manufactured by Kanto Electronics Application Development Co., Ltd. with the following structure and dielectric loss tangent. Regarding the relative dielectric coefficient and the dielectric loss tangent, the average value of the value in the flow direction perpendicular to the flow direction and the value in the flow direction were respectively calculated and used as the relative dielectric coefficient and the dielectric loss tangent of the above-mentioned flat test piece. The results are shown in Table 1. Scalar network analyzer: Agilent Technologies 8757D Frequency synthesizer: Agilent Technologies 83650L Swept CW Generator Fixed attenuator: Agilent Technologies 85025D Detector Cavity Resonator: Kanto Electronics Application Development CP431 Measurement program: Kanto Electronics Application Development CPMA-S2/V2 [Forming conditions] Material tube temperature: 370℃ Metal mold temperature: 80℃ Injection speed: 33mm/sec Keeping pressure: 60Mpa
＜耐裂紋性＞ 將液晶性樹脂組合物射出成形為如第1圖所示的平面狀連接器(引腳孔數1248引腳)，其整體大小為43.88mm×43.88mm×3mmt，中央部具有13.88mm×13.88mm的開口部，格子部節距間隔為1.0mm。另外，澆口(gate)使用了第2圖所示的特殊的澆口(溢流(overflow))。對於得到的平面狀連接器，在下述條件下進行IR回流，用光學顯微鏡觀察格子部，量測裂紋數。裂紋數越少，表示耐裂紋性越高。具體而言，計數在1個平面狀連接器中產生的裂紋的數量，按照以下的基準評價耐裂紋性。 ○(良好)：裂紋的數量小於8個。 ×(不良)：裂紋數為8個以上。 [IR回流條件] 測定機：日本脈衝技術研究所製造的大型臺式回流焊接裝置RF-300(使用遠紅外線加熱器) 試料輸送速度：140mm/sec 回流爐通過時間：5min 溫度條件： 預熱區：150℃ 回流區：240℃ 峰值溫度：260℃ [成形條件] 成形機：住友重機械工業SE100DU 料管溫度(表示由噴嘴側的溫度)： 370℃-370℃-370℃-370℃-370℃-380℃ 金屬模具溫度：80℃ 射出速度：2m/min 保壓力：50MPa 保壓時間：2sec 冷卻時間：10sec 螺桿轉速：120rpm 螺桿背壓：1.2Mpa ＜Crack resistance＞ The liquid crystalline resin composition is injection molded into a planar connector (number of pin holes: 1248 pins) as shown in Figure 1. The overall size is 43.88mm×43.88mm×3mmt, and the central part has a diameter of 13.88mm×13.88mm. The opening part and the grid part pitch interval are 1.0mm. In addition, a special gate (overflow) as shown in Figure 2 is used as the gate. The obtained planar connector was subjected to IR reflow under the following conditions, the grid portion was observed with an optical microscope, and the number of cracks was measured. The smaller the number of cracks, the higher the crack resistance. Specifically, the number of cracks generated in one planar connector was counted, and the crack resistance was evaluated based on the following criteria. ○ (Good): The number of cracks is less than 8. × (Defect): The number of cracks is 8 or more. [IR reflow conditions] Measuring machine: Large desktop reflow soldering device RF-300 manufactured by Japan Pulse Technology Research Institute (using far infrared heater) Sample conveying speed: 140mm/sec Reflow oven passing time: 5min Temperature conditions: Preheating zone: 150℃ Reflow zone: 240℃ Peak temperature: 260℃ [Forming conditions] Forming machine: Sumitomo Heavy Industries SE100DU Material pipe temperature (indicated by the temperature from the nozzle side): 370℃-370℃-370℃-370℃-370℃-380℃ Metal mold temperature: 80℃ Injection speed: 2m/min Maintaining pressure: 50MPa Holding time: 2sec Cooling time: 10sec Screw speed: 120rpm Screw back pressure: 1.2Mpa
[表1]
如表1所記載的結果所表明，實施例的液晶性樹脂組合物可實現耐裂紋性、機械強度、及介電特性優異的平面狀連接器的製造，且流動性良好。As shown by the results shown in Table 1, the liquid crystalline resin compositions of the Examples enable the production of planar connectors excellent in crack resistance, mechanical strength, and dielectric properties, and have good fluidity.
無without
第1圖係表示以實施例成形的平面狀連結器的圖，(a)為平面圖，(b)為右側面圖。另外，圖中的數值的單位為mm。 第2圖係表示以實施例成形的平面狀連結器的澆口(gate)位置的圖，(a)為平面圖，(b)為右側面圖。另外，圖中的數值的單位為mm。 第3圖係表示在實施例及比較例中使用的流動直角方向的介電特性評價用試驗片的切出位置的上視圖。 第4圖係表示在實施例及比較例中使用的流動方向的介電特性評價用試驗片的切出位置的上視圖。 Figure 1 is a diagram showing a planar connector molded according to the embodiment, (a) is a plan view, and (b) is a right side view. In addition, the unit of the numerical value in the figure is mm. Figure 2 is a diagram showing the gate position of the planar connector molded according to the embodiment, (a) is a plan view, and (b) is a right side view. In addition, the unit of the numerical value in the figure is mm. Figure 3 is a top view showing the cut-out position of the test piece for dielectric property evaluation in the direction perpendicular to the flow used in the Examples and Comparative Examples. FIG. 4 is a top view showing the cutting position of the test piece for dielectric property evaluation in the flow direction used in the Examples and Comparative Examples.
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| JP2007154169A (en) * | 2005-11-08 | 2007-06-21 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition and molded product for electronic part |
| JP5165492B2 (en) * | 2008-05-23 | 2013-03-21 | ポリプラスチックス株式会社 | Planar connector |
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