CN116601230A - Conductive liquid crystalline resin composition - Google Patents
Conductive liquid crystalline resin composition Download PDFInfo
- Publication number
- CN116601230A CN116601230A CN202180081329.3A CN202180081329A CN116601230A CN 116601230 A CN116601230 A CN 116601230A CN 202180081329 A CN202180081329 A CN 202180081329A CN 116601230 A CN116601230 A CN 116601230A
- Authority
- CN
- China
- Prior art keywords
- liquid crystalline
- crystalline resin
- conductive filler
- filler
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 229920006038 crystalline resin Polymers 0.000 title claims abstract description 69
- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 239000011231 conductive filler Substances 0.000 claims abstract description 67
- 239000000945 filler Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003365 glass fiber Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052618 mica group Inorganic materials 0.000 claims description 11
- 239000000454 talc Substances 0.000 claims description 11
- 229910052623 talc Inorganic materials 0.000 claims description 11
- 239000010445 mica Substances 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 6
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 6
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 10
- 239000000835 fiber Substances 0.000 description 34
- 125000003118 aryl group Chemical group 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 12
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 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
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 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 1
- 238000009835 boiling Methods 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- CCPVLWRYBOQDFU-UHFFFAOYSA-N cobalt(3+);pentane-2,4-dione Chemical compound [Co+3].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O CCPVLWRYBOQDFU-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 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
- 150000002148 esters Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011133 lead Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 150000004760 silicates Chemical class 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
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- 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
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a conductive liquid crystalline resin composition which gives a molded article having excellent molding processability and low volume resistivity and which has little fluctuation in volume resistivity regardless of thickness. The electroconductive liquid crystalline resin composition of the present invention contains: a liquid crystalline resin (A), a fibrous conductive filler (B), a particulate conductive filler (C), and a non-conductive filler (D), wherein the total content of the fibrous conductive filler (B) and the particulate conductive filler (C) is 25 to 50 mass%, the mass ratio of the fibrous conductive filler (B) to the particulate conductive filler (C) is 0.50 to 3.00, and the non-conductive filler (D) is 2 to 8 mass%.
Description
Technical Field
The present invention relates to a conductive liquid crystalline resin composition.
Background
Liquid crystalline resins, typified by liquid crystalline polyester resins, have excellent mechanical strength, heat resistance, chemical resistance, electric properties, and the like in good balance, and also have excellent dimensional stability, and therefore are widely used as high-functional engineering plastics. In addition, the excellent fluidity of the liquid crystalline resin is effectively utilized, and the liquid crystalline resin is blended with a conductive filler to impart conductivity (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2005-187696
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the shift from LTE to 5G, it has been required to greatly improve signal transmission speed and signal accuracy in many products such as connectors, transmission substrates, antennas, and the like. In the development of conductive materials such as connector materials for high-speed communication, importance of thermoplastic conductive materials capable of imparting a complex shape is increasing as a countermeasure against noise caused by an electromagnetic wave shield or a ground point. Such a conductive material is required to have not only a low volume resistivity as an index of conductivity but also excellent formability in order to be easily formed into a complicated shape, and further, to have a small fluctuation in volume resistivity regardless of the thickness of a molded article after being formed into a complicated shape.
As a candidate of the above-mentioned conductive material, a liquid crystalline resin composition is given. However, according to the studies by the present inventors, the conventional liquid crystalline resin composition is insufficient in molding processability because the volume resistivity is inherently high and the melt viscosity is high. The present invention has been made to solve the above-described problems, and an object thereof is to provide a conductive liquid crystalline resin composition capable of providing a molded article having excellent moldability and low volume resistivity and having small fluctuation in volume resistivity regardless of thickness.
Solution for solving the problem
The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, it has been found that the above-described problems can be solved and the present invention has been completed by using a conductive liquid crystalline resin composition containing: the liquid crystalline resin, the fibrous conductive filler, the particulate conductive filler, and the non-conductive filler, wherein the total content of the fibrous conductive filler and the particulate conductive filler is within a predetermined range, the mass ratio of the content of the fibrous conductive filler to the content of the particulate conductive filler is within a predetermined range, and the content of the non-conductive filler is within a predetermined range. More specifically, the present invention provides the following compositions.
(1) An electroconductive liquid crystalline resin composition comprising:
a liquid crystalline resin (A), a fibrous conductive filler (B), a particulate conductive filler (C), and a non-conductive filler (D), wherein the total content of the fibrous conductive filler (B) and the particulate conductive filler (C) is 25 to 50 mass%, the mass ratio of the fibrous conductive filler (B) to the particulate conductive filler (C) is 0.50 to 3.00, and the non-conductive filler (D) is 2 to 8 mass%.
(2) The electroconductive liquid crystalline resin composition according to (1), wherein the fibrous electroconductive filler (B) is carbon fiber, and the granular electroconductive filler (C) is carbon black.
(3) The electroconductive liquid crystalline resin composition according to (1) or (2), wherein the non-electroconductive filler (D) is 1 or more selected from the group consisting of talc, mica, glass flakes, silica, glass beads, glass hollow microspheres, potassium titanate whiskers, calcium silicate whiskers, milled glass fibers, and glass fibers.
(4) The electroconductive liquid crystalline resin composition according to any one of (1) to (3), wherein the non-electroconductive filler (D) is 1 or more selected from the group consisting of talc, mica, silica, and glass fiber.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a conductive liquid crystalline resin composition which gives a molded article having excellent moldability and low volume resistivity and having small fluctuation in volume resistivity regardless of thickness.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.
< electroconductive liquid crystalline resin composition >
The electroconductive liquid crystalline resin composition of the present invention contains (A) a liquid crystalline resin, (B) a fibrous electroconductive filler, (C) a granular electroconductive filler, and (D) a non-electroconductive filler.
[ (A) liquid crystalline resin ]
The liquid crystalline resin (a) used in the present invention is a melt processable polymer having a property of forming an optically anisotropic melt phase. The nature of the anisotropic melt phase can be confirmed by a conventional polarization detection method using orthogonal polarizers. More specifically, the confirmation of the anisotropic melt phase may be performed as follows: the molten sample placed on the Leitz hot stage was observed under a nitrogen atmosphere at a magnification of 40 times using a Leitz polarization microscope. When the liquid crystalline polymer which can be applied to the present invention is detected between orthogonal polarizers, polarized light is generally transmitted even in a molten state of rest, and optical anisotropy is exhibited.
The type of the liquid crystalline resin (a) is not particularly limited, but aromatic polyesters and/or aromatic polyester amides are preferable. In addition, polyesters comprising partially aromatic polyesters and/or aromatic polyester amides in the same molecular chain are also within this range. As the liquid crystalline resin (A), it is preferable to use: when dissolved in pentafluorophenol at a concentration of 0.1 mass% at 60 ℃, it preferably has a logarithmic viscosity (i.v.) of at least about 2.0dl/g, more preferably 2.0 to 10.0 dl/g.
The aromatic polyester or aromatic polyester amide of the (a) liquid crystalline resin which can be used in the present invention is particularly preferably an aromatic polyester or aromatic polyester amide having 1 or more than 2 kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof as a constituent component.
More specifically, there may be mentioned:
(1) Polyesters mainly comprising 1 or more than 2 kinds of repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof;
(2) A polyester mainly comprising (a) 1 or more than 2 kinds of repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, and (b) 1 or more than 2 kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof;
(3) A polyester mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, (b) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, and (c) at least 1 or 2 or more repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof;
(4) A polyester amide mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and its derivative, (b) 1 or 2 or more repeating units derived from an aromatic hydroxylamine, an aromatic diamine, and its derivative, and (c) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and its derivative;
(5) Mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, (b) 1 or 2 or more repeating units derived from an aromatic hydroxylamine, an aromatic diamine, and a derivative thereof, (c) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, and (d) a polyesteramide derived from at least 1 or 2 or more repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof, and the like. Further, a molecular weight regulator may be used in combination with the above components as required.
Preferable examples of the specific compound constituting the (a) liquid crystalline resin which can be used in the present invention include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and a compound represented by the following general formula (II); aromatic dicarboxylic acids such as 1, 4-phenylene dicarboxylic acid, 1, 3-phenylene dicarboxylic acid, 4' -diphenyl dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, and a compound represented by the following general formula (III); aromatic amines such as p-aminophenol, p-phenylenediamine, and N-acetyl-p-aminophenol.
(X is selected from alkylene (C1-C4), alkylidene, -O-, -SO 2 -S-, and-CO-. )
(Y is selected from- (CH) 2 ) n - (n=1 to 4) and-O (CH) 2 ) n O- (n=1 to 4). )
The liquid crystalline resin (a) used in the present invention can be produced from the above-mentioned monomer compound (or mixture of monomers) by a known method using a direct polymerization method or an ester exchange method, and generally by a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of these, preferably by a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method. The above-mentioned compounds having an ester-forming ability may be used directly for polymerization, or may be modified from a precursor to a derivative having an ester-forming ability at a stage before polymerization. In the polymerization, various catalysts can be used, and typical catalysts include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and cobalt (III) tris (2, 4-pentanedione), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of the catalyst to be used is usually preferably about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, relative to the total mass of the monomers. If further desired, the polymer produced by these polymerization methods may be increased in molecular weight by a solid-phase polymerization method in which heating is performed under reduced pressure or in an inert gas.
The melt viscosity of the liquid crystalline resin (a) obtained by the above method is not particularly limited. Melt viscosity at shear rate of 1000sec at forming temperature can be generally used -1 The lower range is 3 Pa.s to 500 Pa.s. However, when the viscosity is too high, fluidity is extremely deteriorated, which is not preferable. The liquid crystal resin (a) may be a mixture of 2 or more liquid crystal resins.
In the electroconductive liquid crystalline resin composition of the present invention, the content of the liquid crystalline resin (a) is preferably 42 to 73 mass%, more preferably 47.3 to 67.7 mass%, still more preferably 52.5 to 64.5 mass%. (A) When the content of the component is within the above range, fluidity, heat resistance and the like are preferable.
[ (B) fibrous conductive filler ]
The conductive liquid crystalline resin composition of the present invention contains a fibrous conductive filler. The fibrous conductive filler may be used singly or in combination of 1 or more than 2.
(B) The average fiber length of the fibrous conductive filler is not particularly limited, and may be, for example, 50 μm or more and 10mm or less, 80 μm or more and 8mm or less, or 100 μm or more and 7mm or less from the viewpoint of conductivity. In the present specification, the following values are used as the average fiber length of the fibrous conductive filler (B): a solid microscopic image of 10 fibrous conductive fillers was taken in a PC from a CCD camera, and the average value of the values obtained by measuring the fiber length of 100 fibrous conductive fillers, that is, 1000 fibrous conductive fillers in total, in each 1 solid microscopic image was measured by an image processing method using an image measuring machine. The average fiber length of the fibrous conductive filler (B) in the conductive liquid crystalline resin composition was measured by applying the above method to the fibrous conductive filler remaining by ashing after heating the conductive liquid crystalline resin composition at 500 ℃ for 4 hours.
(B) The fiber diameter of the fibrous electroconductive filler is not particularly limited, and may be, for example, 0.2 to 15 μm, 0.25 to 13 μm, or 0.3 to 11 μm from the viewpoint of electroconductivity. In the present specification, the following values are used as the fiber diameter of the fibrous electroconductive filler (B): the fibrous conductive filler was observed by a scanning electron microscope, and the average value of the values obtained by measuring the fiber diameters of 30 fibrous conductive fillers was measured. The fiber diameter of the fibrous conductive filler (B) in the conductive liquid crystalline resin composition was measured by applying the above method to the fibrous conductive filler remaining after heating the conductive liquid crystalline resin composition at 500 ℃ for 4 hours and ashing.
Examples of the fibrous conductive filler (B) include carbon fibers; conductive fibers such as metal fibers; the fiber to which a metal such as nickel or copper is applied to an inorganic fibrous material or the like to impart conductivity is preferably a carbon fiber from the viewpoint of conductivity.
Examples of the carbon fibers include PAN-based carbon fibers made of polyacrylonitrile and pitch-based carbon fibers made of pitch.
Examples of the metal fibers include fibers containing mild steel, stainless steel, steel and its alloys, copper, brass, aluminum and its alloys, titanium, lead, and the like. These metal fibers may be coated with other metals for imparting further conductivity, if necessary, depending on the conductivity.
Examples of the inorganic fibrous material include glass fibers, milled glass fibers, asbestos fibers, silica/alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate whiskers, calcium silicate whiskers (fibrous wollastonite), and the like.
[ (C) granular conductive filler ]
The electroconductive liquid crystalline resin composition of the present invention contains a granular electroconductive filler. The particulate conductive filler may be used singly or in combination of 1 or more than 2.
(C) The median particle diameter of the particulate conductive filler is not particularly limited, and may be, for example, 10nm to 50 μm, 15nm to 20 μm, or 18nm to 10 μm from the viewpoint of conductivity. In the present specification, the median particle diameter refers to a volume-based median value measured by a laser diffraction/scattering particle size distribution measurement method.
The particulate conductive filler (C) includes carbon black, particulate metal powder (for example, aluminum, iron, copper), particulate conductive ceramics (for example, zinc oxide, tin oxide, indium tin oxide), and the like, and carbon black is preferable from the viewpoint of conductivity. Carbon black is not particularly limited as long as it is available for general use in resin coloration. Generally, carbon black contains a lump of primary particles, but it is difficult to generate many pimples (fine pimple-like projections (fine irregularities) of carbon black aggregation) on the surface of a molded article obtained by molding the resin composition of the present invention unless a significant amount of lump of 50 μm or more is contained. When the content of the particles having a particle diameter of 50 μm or more is 20ppm or less, the smoothness of the surface of the molded article tends to be high. The preferable content is 5ppm or less.
In the electroconductive liquid crystalline resin composition of the present invention, the total content of the fibrous electroconductive filler (B) and the granular electroconductive filler (C) is 25 to 50 mass%, preferably 29 to 45 mass%, more preferably 33 to 40 mass%. When the total content is 25 mass% or more, the volume resistivity of the molded article tends to be low, and a molded article having improved conductivity tends to be obtained. When the total content is 50 mass% or less, the fluidity of the conductive liquid crystalline resin composition is easily improved, and a conductive liquid crystalline resin composition excellent in molding processability is easily obtained.
The mass ratio of the content of the fibrous conductive filler (B) to the content of the granular conductive filler (C) is 0.50 to 3.00, preferably 0.60 to 2.50, and more preferably 0.70 to 2.00. When the mass ratio is 0.50 or more, the fluidity of the conductive liquid crystalline resin composition is easily improved, a conductive liquid crystalline resin composition excellent in molding processability is easily obtained, the thickness dependence of the conductivity of the molded article is easily reduced, and a molded article having small fluctuation in volume resistivity irrespective of thickness is easily obtained. When the mass ratio is 3.00 or less, the thickness dependence of the electrical conductivity of the molded article tends to be reduced, and a molded article having small variations in volume resistivity regardless of thickness tends to be obtained.
[ (D) non-conductive filler ]
The electroconductive liquid crystalline resin composition of the present invention contains a non-electroconductive filler. The non-conductive filler may be used alone or in combination of 1 or more than 2. Examples of the non-conductive filler (D) include a plate-like non-conductive filler, a granular non-conductive filler, and a fibrous non-conductive filler.
The median particle diameter of the plate-like nonconductive filler is not particularly limited, and may be, for example, 10to 100. Mu.m, 12 to 50. Mu.m, or 14 to 30. Mu.m. When the median particle diameter of the plate-like nonconductive filler is 10to 100 μm, the thickness dependence of the electrical conductivity of the molded article tends to be reduced, and a molded article having small variations in volume resistivity regardless of thickness is easily obtained. Examples of the plate-like nonconductive filler include talc, mica, and glass flakes.
The median particle diameter of the particulate nonconductive filler is not particularly limited, and may be, for example, 0.3 to 50. Mu.m, 0.4 to 25. Mu.m, or 0.5 to 5.0. Mu.m. When the median particle diameter of the particulate nonconductive filler is 0.3 to 50. Mu.m, the thickness dependence of the electrical conductivity of the molded article tends to be reduced, and a molded article having small variations in volume resistivity irrespective of the thickness is easily obtained. Examples of the particulate nonconductive filler include silicates such as silica, quartz powder, glass beads, glass hollow microspheres, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide, and aluminum oxide; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide; silicon nitride; boron nitride, and the like.
The average fiber length of the fibrous nonconductive filler is not particularly limited, and may be, for example, 50 μm or more and 10mm or less, 80 μm or more and 7mm or less, or 100 μm or more and 4mm or less. When the average fiber length of the fibrous nonconductive filler is 50 μm or more and 10mm or less, the thickness dependence of the electrical conductivity of the molded article is easily reduced, and a molded article having a small variation in volume resistivity regardless of the thickness is easily obtained. The fibrous nonconductive filler has a fiber diameter of, for example, 0.2 to 15. Mu.m, 0.25 to 13. Mu.m, or 0.3 to 11. Mu.m. When the fiber diameter of the fibrous nonconductive filler is 0.2 to 15. Mu.m, the thickness dependence of the electrical conductivity of the molded article is easily reduced, and a molded article having a small variation in volume resistivity regardless of the thickness is easily obtained. As the average fiber length of the fibrous nonconductive filler and the fiber diameter of the fibrous nonconductive filler, average values of values measured in the same manner as described above in the (B) fibrous conductive filler are used, respectively. Examples of the fibrous nonconductive filler include inorganic fibrous materials such as glass fibers, milled glass fibers, asbestos fibers, silica/alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate whiskers, and calcium silicate whiskers (fibrous wollastonite).
The non-conductive filler (D) is preferably 1 or more selected from the group consisting of talc, mica, glass flake, silica, glass beads, glass hollow microspheres, potassium titanate whiskers, calcium silicate whiskers, milled glass fibers, and glass fibers, more preferably 1 or more selected from the group consisting of talc, mica, silica, and glass fibers, and even more preferably 1 or more selected from the group consisting of talc, mica, and silica, since the thickness dependence of the electrical conductivity of the molded article is more easily reduced, and it is easier to obtain a molded article having small variations in thickness and volume resistivity.
In the electroconductive liquid crystalline resin composition of the present invention, the content of the (D) non-electroconductive filler is 2 to 8 mass%, preferably 2.3 to 7.7 mass%, more preferably 2.5 to 7.5 mass%. When the content is 2 to 8 mass%, the fluidity of the conductive liquid crystalline resin composition is easily improved, and a conductive liquid crystalline resin composition excellent in molding processability is easily obtained.
[ other Components ]
The liquid crystalline resin composition of the present invention may contain other polymers, other fillers, and known substances usually added to synthetic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, crystallization nucleating agents, and other components such as mold release agents, as appropriate in the range where the effects of the present invention are not impaired. The other components may be used alone or in combination of 1 or more than 2.
Examples of the other polymer include an epoxy group-containing copolymer. Other polymers may be used alone or in combination of 2 or more.
The other filler is a fibrous conductive filler (B), a granular conductive filler (C), or a filler other than a non-conductive filler (D), and examples thereof include a conductive filler other than the component (B) and the component (C). The other fillers may be used alone or in combination of 2 or more. Examples of the conductive filler other than the component (B) and the component (C) include plate-like conductive fillers.
[ method for producing conductive liquid crystalline resin composition ]
The method for producing the electroconductive liquid crystalline resin composition of the present invention is not particularly limited. For example, the conductive liquid crystalline resin composition is prepared by compounding at least 1 of the above components (a) to (D) and any other components, and melt-kneading them using a single screw or twin screw extruder.
[ conductive liquid crystalline resin composition ]
The conductive liquid crystalline resin composition of the present invention obtained as described aboveFrom the viewpoint of fluidity at the time of melting and from the viewpoint of molding processability, the melt viscosity is preferably 150pa·sec or less, more preferably 145pa·sec or less, and even more preferably 140pa·sec or less. In the present specification, as the melt viscosity, the following values are used: at a barrel temperature of 10to 20 ℃ higher than the melting point of the liquid crystalline resin, a shear rate of 1000sec -1 Under the conditions of ISO 11443.
< conductive Material >
The conductive liquid crystalline resin composition of the present invention can be used to produce a conductive material. The conductive material of the present invention is made of a molded body of the conductive liquid crystalline resin composition of the present invention. The conductive material of the present invention has low volume resistivity and small variation in volume resistivity regardless of thickness. Accordingly, the conductive material of the present invention can be suitably used for products having complex shapes of various thicknesses, and specifically, can be used for, for example, connectors, transmission substrates, antennas, and the like.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
< liquid Crystal resin >
Liquid crystalline polyester amide resin
After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140℃and reacted at 140℃for 1 hour. Thereafter, the temperature was further raised to 340℃over 4.5 hours, and then reduced to 10Torr (i.e., 1330 Pa) over 15 minutes, and melt polymerization was carried out while distilling off acetic acid, excessive acetic anhydride, and other low boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced and the pressure was increased from a reduced pressure state to a pressurized state, and the polymer was discharged from the lower part of the polymerization vessel and the strand was pelletized to obtain pellets. The obtained pellets were subjected to heat treatment at 300℃for 2 hours under a nitrogen gas stream to obtain a target polymer. The melting point of the obtained polymer was 336℃and the melt viscosity at 350℃was 19.0 Pa.s. The melting point of the polymer was measured by the method for measuring the melting point described later, and the melt viscosity of the polymer was measured in the same manner as the method for measuring the melt viscosity described later.
(I) 4-hydroxybenzoic acid (HBA); 1380g (60 mol%)
(II) 2-hydroxy-6-naphthoic acid (HNA); 157g (5 mol%)
(III) 1, 4-phenylene dicarboxylic acid (TA); 484g (17.5 mol%)
(IV) 4,4' -dihydroxybiphenyl (BP); 388g (12.5 mole%)
(V) N-acetyl-para-aminophenol (APAP); 126g (5 mol%)
Metal catalysts (potassium acetate catalysts); 110mg
Acylating agents (acetic anhydride); 1659g
< materials other than liquid Crystal resin >
Fibrous conductive filler: HTC432 (PAN carbon fiber, chopped strands, fiber diameter 7 μm, length 6 mm) manufactured by Diren Co., ltd.)
Carbon black: VULCAN XC305 (Cabot Japan Co., ltd., median particle diameter of 20nm, proportion of particles having particle diameter of 50 μm or more of 20ppm or less)
Talc: CROWN TALC PP (Talc, median particle diameter 14.6 μm, manufactured by Songcun industries Co., ltd.)
Mica: AB-25S (YAMAGUCHI MICA CO., LTD, MICA, median particle size 25.0 μm)
Silica: denka fused silica FB-5SDC (manufactured by Denka Corporation Co., ltd., silica, median particle diameter 4.0 μm)
Glass fiber: ECS03T-786H (chopped strands, fiber diameter 10 μm, length 3mm, manufactured by Nitro Kagaku Co., ltd.)
[ method of measuring melting Point ]
After measuring the endothermic peak temperature (Tm 1) observed when the liquid crystalline resin was heated from room temperature at a temperature rise condition of 20 ℃/min using a DSC manufactured by TA Instruments, the liquid crystalline resin was kept at a temperature of (Tm1+40) DEG C for 2 minutes, and then cooled to room temperature at a temperature drop condition of 20 ℃/min, and then the temperature of the endothermic peak observed when the liquid crystalline resin was heated again at a temperature rise condition of 20 ℃/min was measured.
< production of conductive liquid crystalline resin composition >
The above components were melt-kneaded at a barrel temperature of 350℃using a twin-screw extruder (TEX 30. Alpha. Type manufactured by Nippon Steel Co., ltd.) at the proportions shown in Table 1 or Table 2 (unit: mass%) to obtain pellets of the conductive liquid crystalline resin composition.
< melt viscosity >
The melt viscosity of the conductive liquid crystalline resin composition was measured according to ISO11443 using a Capilograph type 1B manufactured by Toyo Seiki Seisakusho Co., ltd at a temperature of 10to 20℃higher than the melting point of the liquid crystalline resin and using an orifice having an inner diameter of 1mm and a length of 20mm at a shearing rate of 1000/sec. The measurement temperature was 350 ℃. The results are shown in tables 1 and 2.
< volume resistivity >
The pellets of examples and comparative examples were molded under the following molding conditions using a molding machine (SE 100DU manufactured by Sumitomo heavy machinery Co., ltd.) to obtain a flat plate test piece 1 of 80 mm. Times.80 mm. Times.1 mmt or a flat plate test piece 2 of 80 mm. Times.80 mm. Times.2 mmt. The volume resistivity (hereinafter also referred to as "1mmt volume resistivity") was measured in accordance with JIS K7194 using a resistivity meter (Nittoseiko Analytech co., ltd "Loresta-GP"). Further, using a flat plate test piece 2, the volume resistivity (hereinafter also referred to as "2mmt volume resistivity") was measured in accordance with JIS K7194 using a resistivity meter (Nittoseiko Analytech co., ltd "Loresta-GP"). Further, the difference between the volume resistivity of 1mmt and the volume resistivity of 2mmt was calculated. The results are shown in tables 1 and 2. When the absolute value of the difference is 0.10Ω·cm or less, it is evaluated that the variation in volume resistivity is small regardless of the thickness.
[ Forming conditions ]
Barrel temperature: 350 DEG C
Mold temperature: 80 DEG C
Injection rate: 33mm/sec
TABLE 1
TABLE 2
The results shown in tables 1 and 2 demonstrate that the compositions of examples are excellent in molding processability because of low melt viscosity and high flowability, and that the molded articles imparted with the compositions of examples are low in volume resistivity and small in variation in volume resistivity regardless of thickness.
Claims (4)
1. An electroconductive liquid crystalline resin composition comprising:
(A) a liquid crystalline resin, (B) a fibrous electroconductive filler, (C) a granular electroconductive filler, and (D) a non-electroconductive filler,
the total content of the fibrous conductive filler (B) and the granular conductive filler (C) is 25 to 50 mass%,
the mass ratio of the content of the fibrous conductive filler (B) to the content of the granular conductive filler (C) is 0.50 to 3.00,
the content of the non-conductive filler (D) is 2 to 8 mass%.
2. The electroconductive liquid crystalline resin composition according to claim 1, wherein the (B) fibrous electroconductive filler is carbon fiber,
the granular conductive filler (C) is carbon black.
3. The electroconductive liquid crystalline resin composition according to claim 1 or 2, wherein the (D) non-electroconductive filler is 1 or more selected from the group consisting of talc, mica, glass flakes, silica, glass beads, glass hollow microspheres, potassium titanate whiskers, calcium silicate whiskers, milled glass fibers, and glass fibers.
4. The electroconductive liquid crystalline resin composition according to any one of claims 1 to 3, wherein the (D) non-electroconductive filler is 1 or more selected from the group consisting of talc, mica, silica, and glass fiber.
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| PCT/JP2021/044205 WO2022124180A1 (en) | 2020-12-07 | 2021-12-02 | Conductive liquid-crystalline resin composition |
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| KR (1) | KR20230116010A (en) |
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| CN109476922A (en) * | 2016-07-11 | 2019-03-15 | 宝理塑料株式会社 | Liquid crystalline resin composition |
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| JPH0739533B2 (en) * | 1986-12-10 | 1995-05-01 | ポリプラスチックス株式会社 | Liquid crystalline polyester resin composition |
| JP4161494B2 (en) * | 1998-12-11 | 2008-10-08 | 東レ株式会社 | Flame retardant resin composition, its long fiber pellets and its molded product |
| JP4724900B2 (en) * | 1999-07-13 | 2011-07-13 | 東レ株式会社 | Flame retardant polyamide resin composition and molded article thereof |
| JP2001067933A (en) * | 1999-08-24 | 2001-03-16 | Toray Ind Inc | Conductive resin composition and mold thereof |
| JP2002194194A (en) | 2000-12-25 | 2002-07-10 | Polyplastics Co | Semiconductive resin composition and molded product |
| US20040113129A1 (en) | 2002-07-25 | 2004-06-17 | Waggoner Marion G. | Static dissipative thermoplastic polymer composition |
| JP4302508B2 (en) | 2003-12-26 | 2009-07-29 | ポリプラスチックス株式会社 | Conductive resin composition |
| JP6231243B1 (en) | 2016-09-14 | 2017-11-15 | 住友化学株式会社 | Liquid crystalline resin composition |
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| JPH04311758A (en) * | 1991-04-10 | 1992-11-04 | Toray Ind Inc | Liquid crystal polymer resin composition |
| CN104822775A (en) * | 2012-12-03 | 2015-08-05 | 宝理塑料株式会社 | Liquid crystal resin composition for camera module and camera module using same |
| CN109476922A (en) * | 2016-07-11 | 2019-03-15 | 宝理塑料株式会社 | Liquid crystalline resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202231763A (en) | 2022-08-16 |
| JPWO2022124180A1 (en) | 2022-06-16 |
| KR20230116010A (en) | 2023-08-03 |
| WO2022124180A1 (en) | 2022-06-16 |
| JP7373080B2 (en) | 2023-11-01 |
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