CN114729171A - Dispersion, method for producing dispersion, and molded article - Google Patents
Dispersion, method for producing dispersion, and molded article Download PDFInfo
- Publication number
- CN114729171A CN114729171A CN202080078871.9A CN202080078871A CN114729171A CN 114729171 A CN114729171 A CN 114729171A CN 202080078871 A CN202080078871 A CN 202080078871A CN 114729171 A CN114729171 A CN 114729171A
- Authority
- CN
- China
- Prior art keywords
- dispersion
- anisotropic filler
- filler
- polymer
- molded article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 241
- 229920000642 polymer Polymers 0.000 claims abstract description 134
- 239000007788 liquid Substances 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 78
- 239000002245 particle Substances 0.000 claims abstract description 32
- -1 perfluoro Chemical group 0.000 claims abstract description 31
- 239000002612 dispersion medium Substances 0.000 claims abstract description 24
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 24
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims description 25
- 229910052582 BN Inorganic materials 0.000 claims description 19
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 229910052623 talc Inorganic materials 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000000454 talc Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 230000000704 physical effect Effects 0.000 abstract description 33
- 239000010410 layer Substances 0.000 description 49
- 239000004094 surface-active agent Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000005702 oxyalkylene group Chemical group 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 241000220304 Prunus dulcis Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011437 continuous method Methods 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
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/34—Silicon-containing 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing 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
-
- 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
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a dispersion liquid containing a predetermined tetrafluoroethylene polymer and a predetermined anisotropic filler, a method for producing the same, and a molded article having high physical properties of both. The dispersion liquid of the present invention comprises a powder of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit or a hexafluoropropylene-based unit, an anisotropic filler having a mohs hardness of 4 or less, and a liquid dispersion medium, the powder having an average particle diameter smaller than that of the anisotropic filler. The molded article of the present invention comprises a predetermined tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit and the anisotropic filler, and the anisotropic filler accounts for 10 mass% or more of the molded article.
Description
Technical Field
The present invention relates to a dispersion liquid containing a predetermined anisotropic filler, a method for producing the same, and a molded article.
Background
Hot-melt fluoropolymers such as tetrafluoroethylene Polymers (PFA) containing perfluoro (alkyl vinyl ether) units and tetrafluoroethylene polymers (FEP) containing hexafluoropropylene units are excellent in physical properties such as mold release properties, electrical insulation properties, water and oil repellency, chemical resistance, weather resistance, and heat resistance, and are used for processing into various molded articles.
Patent document 1 describes a conduit tube having excellent electrical insulation properties, which is obtained by extrusion molding a dry-blended mixture of PFA powder and a boron nitride filler.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-224228
Disclosure of Invention
Technical problem to be solved by the invention
However, the fluoropolymer has a high melt viscosity, and a strong stress is required for melt-kneading the fluoropolymer and the filler. In this case, the properties (particularly, physical properties such as shape and surface state) of the filler itself are impaired, and the physical properties of the filler in the molded article are liable to be deteriorated. The inventors have found that this tendency becomes more pronounced when brittle fillers of low hardness are used, and more pronounced when low-hardness and anisotropic fillers are used.
The present inventors have intensively studied to obtain a material suitable for molding the above molded article without melt kneading. As a result, the dispersion liquid containing the powder of the predetermined fluoropolymer and the predetermined anisotropic filler has excellent dispersion stability and good workability such as coatability. Further, the anisotropic filler of the molded article formed therefrom is not easily impaired in properties and has high physical properties of both.
The object of the present invention is to provide the dispersion and the molded article.
Technical means for solving the technical problems
The present invention has the following embodiments.
[1] A dispersion liquid comprising a powder of a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit or a hexafluoropropylene-based unit, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium, wherein the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler.
[2] The dispersion liquid according to [1], wherein the content of the tetrafluoroethylene polymer and the content of the anisotropic filler are both 5% by mass or more.
[3] The dispersion liquid according to [1] or [2], wherein the anisotropic filler has a scale-like or plate-like shape.
[4] The dispersion liquid according to any one of [1] to [3], wherein the aspect ratio of the anisotropic filler is 2 or more.
[5] The dispersion liquid according to any one of [1] to [4], wherein the anisotropic filler is an anisotropic filler containing boron nitride or talc
[6] The dispersion liquid according to any one of [1] to [5], further comprising polytetrafluoroethylene powder or an aromatic polymer.
[7] The dispersion liquid according to any one of [1] to [6], wherein the component dispersion layer ratio is 60% or more.
[8] A method for producing the dispersion according to any one of [1] to [7], which comprises mixing the powder, the anisotropic filler, an inorganic filler having an average particle diameter smaller than that of the anisotropic filler, and a liquid dispersion medium.
[9] The production method according to [8], wherein the mixing is carried out by stirring.
[10] A molded article comprising a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit and an anisotropic filler having a Mohs hardness of 4 or less,
the tetrafluoroethylene polymer is a polymer having a polar functional group or a polymer having no polar functional group, which contains 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit based on the whole units, and the anisotropic filler accounts for 10 mass% or more of the molded article.
[11] The molded article according to [10], wherein the aspect ratio of the anisotropic filler is 2 or more.
[12] The molded article according to [11], wherein the anisotropic filler is a scale-like anisotropic filler containing boron nitride or a plate-like anisotropic filler containing talc.
[13] The molded article according to any one of [10] to [12], wherein the anisotropic filler has an average particle diameter of 1 μm or more.
[14] The molded article according to any one of [10] to [13], which further comprises polytetrafluoroethylene or an aromatic polymer.
[15] The molded article according to any one of [10] to [14], wherein the molded article is a layered molded article having a thickness of 150 μm or less.
Effects of the invention
The present invention provides a dispersion liquid which is excellent in dispersibility and handling properties of a powder containing a predetermined fluoropolymer and a predetermined anisotropic filler. Further, a molded article having both of these properties and particularly excellent electrical characteristics is obtained.
Detailed Description
The "average particle diameter (D50)" is a cumulative 50% diameter on a volume basis of an object (powder or filler) determined by a laser diffraction/scattering method. That is, the particle size distribution of the object was measured by a laser diffraction scattering method, and a cumulative curve was obtained with the total volume of the particle group of the object as 100%, and the particle size at the point where the cumulative volume reached 50% on the cumulative curve.
"D90" is a cumulative 90% diameter on a volume basis of the object measured in the same manner.
The "particle size distribution" is a distribution represented by a curve obtained by plotting the particle amount (%) in each particle size range obtained in the same manner.
The "melting temperature" is a temperature corresponding to the maximum value of the melting peak of the polymer measured by Differential Scanning Calorimetry (DSC).
The "glass transition temperature" is a value measured by analyzing a polymer by a dynamic viscoelasticity measurement (DMA) method.
The "unit" in the polymer may be a radical formed directly from a monomer by polymerization, or a radical in which a part of the structure of a polymer obtained by polymerization is converted by treating the polymer in a predetermined method. The unit based on the monomer a contained in the polymer is also referred to simply as "monomer a unit".
The dispersion liquid of the present invention (hereinafter referred to as "present dispersion liquid") comprises a powder (hereinafter referred to as "F powder") of a tetrafluoroethylene-based polymer (hereinafter referred to as "F polymer") containing a perfluoro (alkyl vinyl ether) (PAVE unit) unit or a Hexafluoropropylene (HFP) unit (HFP unit), an anisotropic filler having a mohs hardness of 4 or less, and a liquid dispersion medium.
The average particle size of the F powder is smaller than the average particle size of the anisotropic filler. The dispersion liquid contains F powder and anisotropic filler dispersed therein.
The dispersion liquid is excellent in dispersion stability and workability, and can easily form a molded article having high physical properties of the F polymer and the anisotropic filler. The reason is not clear, but is considered to be the following.
The anisotropic filler of the present invention is amorphous and has various properties (crystal habit, etc.), and can be said to be a weak filler. In the present dispersion, the state of the anisotropic filler is unstable and aggregation or sedimentation is liable to occur. In addition, the shape or state of the anisotropic filler is easily destroyed by physical stress (shear stress or the like).
On the other hand, the F polymer is a polymer having plasticity represented by hot melt processability, and its powder (F powder) is less susceptible to physical stress and has excellent dispersibility.
The present dispersion is in a state where the average particle diameter of the F powder is smaller than the average particle diameter of the anisotropic filler, in other words, in a state where the dispersion is contained densely and the affinity between the anisotropic filler and the F powder tends to be relatively high. That is, in the present dispersion, since the F powder is contained densely in a finer particle state, it is considered that pseudo secondary particles are easily formed between the F powder and the anisotropic filler. As a result, the dispersion state of the anisotropic filler is stabilized, and therefore the dispersion liquid is considered to be excellent in dispersion stability and handling property.
When F powder is melt-fired while removing the liquid dispersion medium from the dispersion, it is easy to mold a molded article while suppressing deformation of the anisotropic filler. In addition, in the process of removing the liquid dispersion medium, a highly filled molded article can be easily obtained while the anisotropic filler is oriented. As a result, it is considered that a molded article having high physical properties of the F polymer and the anisotropic filler is obtained from the present dispersion.
For example, if a molded article is formed from the present dispersion liquid containing a scaly or plate-like anisotropic filler, the anisotropic filler is oriented parallel to the surface (planar direction) of the molded article, and the physical properties of the anisotropic filler in the molded article are likely to be highly exhibited. Therefore, if the dispersion is used, even a sheet-like molded article tends to exhibit high physical properties of the F polymer and anisotropic filler.
Further, when the anisotropic filler is in the form of a flake or a plate, the anisotropic filler forms a structure of a card house (structure カードハウス in Japanese), and not only the liquid properties (viscosity, dispersion stability, etc.) of the present dispersion are improved, but also the anisotropic filler is more easily highly dispersed in a molded product formed therefrom. As a result, the molded product can be easily made excellent in electrical characteristics. When the molded article is subjected to stress, the anisotropic filler easily disperses the stress, and the mechanical strength (e.g., bendability) is easily improved. Further, since channels for the anisotropic filler are formed in the molded article, the thermal conductivity of the molded article is easily improved.
The F powder in the present dispersion is preferably formed of an F polymer. The content of the F polymer in the powder is preferably 80% by mass or more, and more preferably 100% by mass.
Examples of the other component that may be contained in the F powder include a resin different from the F polymer and an inorganic substance. Examples of the different resin include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene ether.
Examples of the inorganic substance include silicon dioxide (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, and the like), boron nitride, and magnesium metasilicate (talc).
The F powder containing a resin or an inorganic substance different from the F polymer preferably has a core-shell structure in which the F polymer is a core and the resin or the inorganic substance is a shell, or a core-shell structure in which the resin or the inorganic substance is a core and the F polymer is a shell. The F powder can be obtained, for example, by bonding (collision, aggregation, or the like) a powder of the F polymer to a powder of the resin or inorganic substance.
D50 of the F powder is preferably 10 μm or less, more preferably 6 μm or less, and still more preferably 4 μm or less. D50 of the F powder is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more. The D90 content of the F powder is preferably 20 μm or less, more preferably 10 μm or less. If the D50 and D90 content in the F powder falls within this range, the affinity with the anisotropic filler is further improved, and the dispersion stability of the dispersion and the physical properties of the molded article are more easily improved.
The content of the F powder in the present dispersion is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 25 mass% or more. The content of the F powder is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less. When the content of the F powder is within this range, the F powder contained densely can improve the affinity between the F powder and the anisotropic filler, and the dispersion stability of the dispersion can be easily further improved. In addition, the physical properties of the polymer F in the molded article are likely to be remarkably exhibited.
The F polymer in the present dispersion is a polymer containing Tetrafluoroethylene (TFE) based units (TFE units). The F polymer may include both PAVE units and HFP units, or may include only either.
As PAVE, CF is mentioned2＝CFOCF3、CF2＝CFOCF2CF3Or CF2＝CFOCF2CF2CF3(PPVE), preferably PPVE.
The melting temperature of the F polymer is preferably 280-325 ℃, and more preferably 285-320 ℃.
The glass transition temperature of the F polymer is preferably 75 to 125 ℃, and more preferably 80 to 100 ℃.
The F polymer may have a polar functional group (polar functional group). Polar functional groups may be included in the units in the F polymer, as well as in the end groups of the polymer backbone. The latter form may, for example, be an F polymer having a polar functional group as an end group derived from a polymerization initiator, a chain transfer agent or the like, or an F polymer having a polar functional group obtained by subjecting an F polymer to plasma treatment or ionization treatment.
The polar functional group is preferably a hydroxyl-containing group and a carbonyl-containing group, and more preferably a carbonyl-containing group from the viewpoint of further improving the dispersion stability of the present dispersion.
The hydroxyl-containing group is preferably an alcoholic hydroxyl-containing group, more preferably-CF2CH2OH or-C (CF)3)2OH。
The carbonyl-containing group is preferably a carbonyl (& gt, C (O)) containing group, a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH)2) An anhydride residue (-CO (O) OC (O) -), an imide residue (-C (O) NHC (O) -, etc.) or a carbonate group (-OC (O) O-).
The number of carbonyl groups in the F polymer is 1X 10 relative to the number of carbon atoms in the main chain6Is described in10 to 5000, more preferably 100 to 3000, and still more preferably 800 to 1500. The number of carbonyl groups contained in the polymer F can be determined by the composition of the polymer or by the method described in International publication No. 2020/145133.
The F polymer is preferably a tetrafluoroethylene polymer containing PAVE units in an amount of 1.5 to 5.0 mol% relative to the total units, more preferably a polymer (1) having polar functional groups containing PAVE units and units derived from a monomer having polar functional groups, or a polymer (2) having no polar functional groups containing PAVE units in an amount of 2.0 to 5.0 mol% relative to the total units.
These F polymers are excellent in the dispersion stability of the powder, and are more easily densely and homogeneously distributed in a molded article (polymer layer or the like) formed from the dispersion. Further, fine spherulites are easily formed in the molded article, and adhesion to other components is easily improved. As a result, a molded product having high physical properties of each of the three components can be more easily formed.
The polymer (1) preferably contains units based on a monomer having a polar functional group in an amount of 90 to 99 mol% of TFE units, 1.5 to 9.97 mol% of PAVE units and 0.01 to 3 mol% relative to the total units.
The monomer having a polar functional group is preferably itaconic anhydride, citraconic anhydride or 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH").
Specific examples of the polymer (1) include the polymers described in International publication No. 2018/16644.
The polymer (2) preferably consists of TFE units and PAVE units alone, and contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units relative to the total units.
The content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, relative to the total units.
The polymer (2) having no polar functional group means that the number of carbon atoms constituting the main chain of the polymer is 1X 106And the number of the polar functional groups of the polymer is less than 500. As described aboveThe number of polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of the polar functional groups is usually 0.
The polymer (2) may be produced by using a polymerization initiator or a chain transfer agent which does not generate a polar functional group to be an end group of a polymer chain, or may be produced by subjecting an F polymer having a polar functional group (e.g., an F polymer having a polar functional group derived from a polymerization initiator at an end group of a polymer main chain) to a fluorination treatment. As a method of the fluorination treatment, a method using a fluorine gas can be mentioned (see Japanese patent laid-open publication No. 2019-194314).
The mohs hardness of the anisotropic filler in the present invention is 4 or less, preferably 3 or less. The mohs hardness of the anisotropic filler is preferably 1 or more, more preferably 2 or more. Even if the anisotropic filler is brittle and has a mohs hardness within this range, the affinity between the anisotropic filler and the F powder can provide the dispersion liquid with excellent dispersion stability, and the physical properties of the filler in the molded article can be easily improved.
The anisotropic filler may be used in 1 kind or 2 or more kinds having different average particle diameters or kinds.
The shape of the anisotropic filler of the present invention may be any of granular shape, needle shape (fibrous shape), and plate shape. Specific examples of the shape of the anisotropic filler include a spherical shape, a scaly shape, a lamellar shape, a leaf shape, an almond shape, a columnar shape, a chicken crown shape, an equiaxial shape, a leaf shape, a mica shape, a block shape, a flat plate shape, a wedge shape, a rosette shape, a mesh shape, and a square columnar shape.
The shape of the anisotropic filler is preferably scaly or plate-like. When the scale-like or plate-like anisotropic filler is used, the structure of the card house is formed, and not only the liquid properties (viscosity, dispersion stability, etc.) of the dispersion liquid are easily improved, but also the orientation of the filler in the molded product is easily improved, and the functions (mechanical strength, thermal conductivity, electrical characteristics, etc.) of the molded product are easily improved.
Examples of the anisotropic filler include a carbon filler, a nitride filler, a mica filler, a clay filler, and a talc filler, and preferably a filler containing boron nitride or talc, and more preferably a filler containing boron nitride. The crystal form of boron nitride may be any of hexagonal crystal, rhombohedral crystal, cubic crystal, and wurtzite. The anisotropic filler-containing dispersion liquid is excellent in dispersion stability and handling properties. Further, the electrical interference imparted to the F polymer by the filler in the molded article tends to increase, and as a result, the electrical characteristics (particularly, the dielectric loss tangent) of the molded article tends to be improved. Further, the molded article is easily improved in thermal conductivity.
The content of boron nitride in the boron nitride-containing filler is preferably 95% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more. The upper limit of the content is 100 mass%. In this case, the molded article is likely to have low linear expansibility and good electrical properties.
When the anisotropic filler is added to water, the pH of the water may be any of acidic, neutral, and basic, and is preferably basic.
The specific surface area of the anisotropic filler is preferably 1-20 m2(iv)/g, more preferably 3 to 8m2(ii) in terms of/g. In this case, the anisotropic filler in the dispersion is easily wetted and the affinity with the F polymer is easily improved. In addition, the anisotropic filler and the F polymer in the molded article are more easily uniformly dispersed (distributed), and the physical properties of both are more easily exhibited in a well-balanced manner.
The surface of the anisotropic filler may be surface-treated.
Examples of the surface treatment agent include polyhydric alcohols (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, amines (trimethylamine, triethylamine, etc.), paraffins, silane coupling agents, silicones, polysiloxanes, and inorganic substances (oxides, hydroxides, hydrated oxides, or phosphates of aluminum, silicon, zirconium, tin, titanium, antimony, etc.).
As the surface treatment agent, a silane coupling agent is preferable. In this case, the anisotropic filler is more compatible with the powder of the F polymer, and the dispersion stability of the dispersion is easily improved. The silane coupling agent preferably has an amino group, a mercapto group, a vinyl group, an acryloyloxy group or a methacryloyloxy group.
The anisotropic filler may be an anisotropic filler having a hydrophobic portion and a hydrophilic portion. The anisotropic filler may be an anisotropic filler having a hydrophobic layer on the surface and a hydrophilic layer inside. As a specific example thereof, a plate-like multilayer filler comprising a water-repellent layer, a hydrophilic layer (water-containing layer), and a water-repellent layer in this order may be mentioned. The water content of the hydrophilic layer is preferably 0.3 mass% or more. In this case, not only the dispersion state of the anisotropic filler in the dispersion liquid is easily stabilized, but also the orientation of the anisotropic filler when a molded article is formed from the dispersion liquid is further improved, and a molded article having high physical properties of the F polymer and the anisotropic filler is easily obtained.
The anisotropic filler preferably has a D50 value of 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. The D50 of the anisotropic filler is preferably 25 μm or less, more preferably 20 μm or less. The anisotropic filler preferably has a D90 value of 10 μm or more, more preferably 15 μm or more. The D90 of the anisotropic filler is preferably 30 μm or less, more preferably 20 μm or less. When D50 and D90 in the anisotropic filler are within the above range, the affinity with the F powder is improved, and the dispersion stability of the dispersion and the physical properties of the molded article are more improved. Specific examples of the anisotropic filler include a flaky boron nitride filler and a platy talc filler.
The aspect ratio of the anisotropic filler is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and particularly preferably 10 or more. The aspect ratio of the anisotropic filler is preferably 10000 or less. In this case, the orientation of the filler in the molded product can be more easily improved, and the function thereof can be easily improved. Specifically, not only is the dispersion state of the anisotropic filler in the dispersion liquid easily stabilized, but also the orientation of the anisotropic filler when a molded article is formed from the dispersion liquid is further improved, and a molded article having high physical properties of the F polymer and the anisotropic filler can be easily obtained.
The aspect ratio of the anisotropic filler is a value obtained by dividing the average particle diameter (D50) of the anisotropic filler by the average minor axis (average value of the length in the short side direction) of the anisotropic filler.
Specific examples of the anisotropic filler include fillers having an average short diameter of 1 μm or less or an average long diameter (average value of the length in the longitudinal direction) of 1 μm or more. Specific examples of the anisotropic filler include tabular talc fillers.
The anisotropic filler may have a single-layer structure or a multi-layer structure. As the anisotropic filler, a talc filler having a three-layer structure may be mentioned.
Preferred examples of the anisotropic filler include boron nitride fillers ("UHP" series manufactured by showa electric corporation, "HGP" series, "GP" series manufactured by electrochemical corporation (デンカ), and the like), and talc fillers ("SG" series manufactured by japan talc corporation (japanese タルク).
In this dispersion, the D50 of the F powder is less than the D50 of the anisotropic filler. That is, in the present dispersion, the affinity between the F powder and the anisotropic filler is improved by densely containing the fine particulate F powder, and the dispersion stability of the present dispersion is improved. In addition, the anisotropic filler is more uniformly dispersed in the molded product, and the physical properties thereof are more easily and clearly exhibited.
Specifically, it is preferable that the D50 of the F powder is 0.1 μm or more and less than 5 μm, and the D50 of the anisotropic filler is 1 μm or more and 25 μm or less.
A preferred form of the filler contained in the present dispersion liquid includes an anisotropic filler (hereinafter referred to as "anisotropic filler 1") and an inorganic filler (hereinafter referred to as "different filler") having an average particle diameter smaller than that of the anisotropic filler 1. In this case, the interaction between the fillers improves the dispersion stability of the present dispersion, balances the ability of forming a densely formed product with different fillers, and facilitates further improvement of various physical properties (water resistance, low linear expansion property, electrical properties, etc.) of the obtained formed product. The different filler may be an inorganic filler having an average particle diameter smaller than that of the anisotropic filler 1, and may be the same as or different from that of the anisotropic filler 1.
In a preferred embodiment, the anisotropic filler 1 preferably has an average particle diameter of more than 6 μm and not more than 15 μm, and the different fillers preferably have an average particle diameter of not less than 1 μm and not more than 6 μm. At this time, it is preferable that the anisotropic filler 1 is a boron nitride-containing filler and the different filler is a boron nitride-containing filler or a magnesium metasilicate filler (talc filler). The anisotropic filler 1 preferably has an aspect ratio of 10 or more, and the different fillers preferably have an aspect ratio of 40 or less, more preferably less than 10.
In this case, the different fillers promote the random orientation of the anisotropic filler in the obtained molded article, and the physical properties of the filler and the physical properties (adhesiveness, rigidity, etc.) of the molded article are easily balanced.
In a preferred embodiment, the anisotropic filler 1 preferably has an average particle diameter of more than 1 μm and not more than 15 μm, and the different fillers preferably have an average particle diameter of not less than 0.01 μm and less than 1 μm. At this time, it is preferable that the anisotropic filler 1 is a filler containing boron nitride and the different filler is a filler containing silicon oxide.
The silica-containing filler is preferably a silica filler or a magnesium metasilicate filler (talc filler). Further, it is preferable that the surface of the filler containing silicon oxide is surface-treated with a silane coupling agent.
The silica-containing filler is preferably substantially spherical. In this case, a dense molded product is easily formed. The substantially spherical shape means that the ratio of the minor axis to the major axis of the spherical particles is 0.7 or more and the ratio of the spherical particles to the major axis is 95% or more when observed by a Scanning Electron Microscope (SEM).
Specific examples of the silica-containing filler include roughly spherical silica fillers ("admafin" series produced by yadoma corporation (アドマテックス), spherical fused silica ("SFP" series produced by electrochemical corporation), hollow silica fillers ("E-speres" series produced by pacific cement corporation (pacific セメント)), "SiliNax" series produced by Nippon iron ore corporation (Nippon ), "eccosophers" series produced by Emason Corming corporation (エマーソン, アンド, カミング), and talc ("BST" series produced by Nippon talc corporation).
In this preferred embodiment, the different fillers promote the random orientation of the anisotropic filler 1 in the molded article, and the physical properties of the filler in the molded article and the physical properties of the molded article (such as adhesiveness, surface smoothness, and rigidity) are easily balanced. That is, the molded product tends to have high electrical characteristics and low linear expansion due to the partial disorder of the orientation of the anisotropic filler 1 in the molded product, the high or low level of the orientation of the filler, and rigidity, adhesiveness, and surface smoothness due to the disorder of the orientation of the filler.
Further, the filler of the preferred form may be contained in a state having a multimodal particle size distribution. In this case, the peak due to the present filler 1 is preferably the highest among the peaks in the particle size distribution, from the viewpoint of easy formation of a dense molded article. Specifically, the filler is preferably contained in a state having a bimodal particle size distribution in which a region of 6 μm or less and a region exceeding 6 μm each have a peak.
At least a part of the filler in the preferred form may be contained by adhering to the surface of the F powder, or may be contained by adhering at least a part of the F powder to the surface. In this case, it can be said that the dispersion liquid contains a composite of the F powder and the anisotropic filler 1, and the dispersion stability is further improved, and various physical properties (water resistance, low linear expansion property, electrical properties, and the like) of a molded product formed by the dispersion liquid are easily further improved.
In this preferred embodiment, the mass ratio of the content of the different filler to the content of the anisotropic filler 1 is preferably 0.1 or more, and more preferably 0.2 or more. The mass ratio is preferably 2 or less, more preferably 1 or less. In this case, the dispersion stability of the dispersion liquid and the physical properties of the molded article can be easily balanced.
The content of the anisotropic filler in the present dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 25% by mass or more. The content of the F powder is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less.
The content of the polymer F and the content of the anisotropic filler in the present dispersion are preferably 5% by mass or more. The sum of the contents of both is preferably 60% by mass or less. The dispersion liquid may contain the F polymer and the anisotropic filler at the above-mentioned high ratios (contents), respectively, and as described in the above-mentioned mechanism of action, the dispersion liquid is excellent in dispersion stability and a molded article having both of these physical properties is easily formed.
From the viewpoint of improving dispersion stability and handling properties, it is preferable that the present dispersion further contains a surfactant.
The surfactant is preferably a nonionic surfactant.
The hydrophilic site of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
The oxyalkylene group may be composed of one species of oxyalkylene group, or may be composed of 2 or more species of oxyalkylene groups. In the latter case, the different types of oxyalkylene groups may be arranged randomly or in blocks.
The oxyalkylene group is preferably an oxyethylene group.
The hydrophobic portion of the surfactant preferably has an ethynyl group, a polysiloxane group, a perfluoroalkyl group, or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene type surfactant, a silicone type surfactant, or a fluorine type surfactant, and more preferably a silicone type surfactant.
The fluorine-based surfactant is more preferably a fluorine-based surfactant having a hydroxyl group (particularly an alcoholic hydroxyl group) or an oxyalkylene group and a perfluoroalkyl group or a perfluoroalkenyl group.
Specific examples of the surfactant include "Ftergent" series (manufactured by Nippon Seikagaku K.K. (ネオス)), a "Surflon" series (manufactured by AGC Qing beauty chemical Co., Ltd. (AGC セイミケミカル)), "MEGA FACE" series (manufactured by DIC K.), "Unidyne" series (manufactured by Dajin Industrial Co., Ltd. (ダイキン K. )), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by Pickery Co., Ltd. (ビックケミー. ジャパン)), "KF-6011" and "KF-6043" (manufactured by shin chemical industries, Ltd. ( Co., Ltd.).
The content of the surfactant in the dispersion is preferably 1 to 15% by mass. In this case, the affinity between the components is improved, and the dispersion stability of the dispersion is more easily improved.
The liquid dispersion medium of the present invention is a liquid compound inert at 25 ℃ that functions as a dispersion medium for the F powder and the anisotropic filler. The liquid dispersion medium may be water or a nonaqueous dispersion medium. The number of the liquid dispersion medium may be 1 or 2 or more. In this case, it is preferable that different liquid compounds are compatible with each other.
The boiling point of the liquid dispersion medium is preferably 125-250 ℃. In this case, when a molded article is formed from the dispersion, the anisotropic filler is easily oriented, and the physical properties of the molded article are easily improved.
The liquid dispersion medium is preferably at least one liquid compound selected from the group consisting of amides, ketones, and esters, and more preferably N-methyl-2-pyrrolidone, γ -butyrolactone, cyclohexanone, and cyclopentanone, from the viewpoint of the dispersion stability of the dispersion liquid.
The content of the liquid dispersion medium in the present dispersion liquid is preferably 50% by mass or more, more preferably 60% by mass or more. The content of the liquid dispersion medium is preferably 90% by mass or less, more preferably 80% by mass or less.
The viscosity of the dispersion is preferably 50 mPas or more, more preferably 100 mPas or more. The viscosity of the dispersion is preferably 10000 mPas or less, more preferably 1000 mPas or less, and still more preferably 800 mPas or less.
The thixotropic ratio of the present dispersion is preferably 1.0 or more. The thixotropic ratio of the present dispersion is preferably 3.0 or less, more preferably 2.0 or less.
The component dispersion layer ratio of the present dispersion liquid is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. Here, the component dispersion layer ratio is a value calculated from the total height of the present dispersion and the height of the component dispersion layer in the spiral tube before and after the standing at 25 ℃ for 14 days by the following formula when the present dispersion (18mL) is charged in the spiral tube (internal volume: 30 mL).
Component dispersion layer ratio (%) (height of component dispersion layer)/(entire height of the present dispersion liquid) × 100
When no component dispersed layer was observed and no change in state was observed after standing, the entire height of the dispersion was unchanged, and the component dispersed layer ratio was 100%.
The dispersion liquid can be easily adjusted to the viscosity, thixotropy, or component dispersion layer ratio within the above-mentioned range by the above-mentioned action mechanism, and is excellent in handling properties.
The present dispersion may further contain another resin (polymer) different from the F polymer. The other resin may be a thermosetting resin or a thermoplastic resin.
Examples of the other resin include epoxy resins, maleimide resins, polyurethane resins, elastomers, polyimides, polyamide acids, polyamide imides, polyphenylene ethers, liquid crystal polyesters, and fluoropolymers other than the F polymer.
A preferred embodiment of the other resin may be a varnish of an aromatic polymer. The aromatic polymer is preferably an aromatic polyimide and an aromatic polyamic acid, and more preferably a thermoplastic aromatic polyimide. In this case, the molded article tends to exhibit remarkable physical properties of the F polymer and the anisotropic filler. In addition, when a molded article is formed from the dispersion, dusting of the F powder is also suppressed, and the adhesiveness is more easily improved.
The content of the aromatic polymer in the dispersion is preferably 1 to 30% by mass, more preferably 5 to 25% by mass. The mass ratio of the content of the aromatic polymer to the content of the F polymer is preferably 1.0 or less, and more preferably 0.1 to 0.7.
A preferable embodiment of the other resin is Polytetrafluoroethylene (PTFE) powder. In this case, the molded product tends to exhibit remarkable physical properties derived from PTFE (electrical properties such as low dielectric loss tangent). Further, since PTFE acts as a nucleating agent, the F polymer in the molded article tends to form fine crystals, the adhesiveness of the surface of the molded article is improved, and the adhesiveness is further improved. Further, the orientation of the filler in the molded product can be easily improved, and the function thereof can be easily improved.
The PTFE is preferably PTFE (low molecular weight PTFE) having a number average molecular weight (Mn) of 20 ten thousand or less as calculated from the following formula (1).
Mn＝2.1×1010×ΔHc-5.16···(1)
In the formula (1), Δ Hc represents the heat of crystallization (cal/g) of PTFE measured by differential scanning calorimetry.
The Mn of the low-molecular-weight PTFE is preferably 10 ten thousand or less, more preferably 5 ten thousand or less. The Mn of the low-molecular-weight PTFE is preferably 1 ten thousand or more.
The PTFE content in the dispersion is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. The mass ratio of the content of PTFE to the content of the F polymer is preferably 1.0 or less, more preferably 0.1 to 0.4.
The present dispersion liquid in the case of containing another resin may be produced by mixing the present dispersion liquid with powder of another resin, or may be produced by mixing the present dispersion liquid with a varnish containing another resin.
The dispersion liquid may contain additives such as a thixotropy imparting agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather-resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a viscosity adjusting agent, a flame retardant, and an isotropic filler, in addition to the above components.
The present dispersion can be prepared by mixing the F powder, the anisotropic filler and the liquid dispersion medium, and it is preferable to prepare a liquid composition containing the F powder and a liquid composition containing the anisotropic filler separately and then mix them.
A specific method for producing the present dispersion may be a method of mixing F powder, the anisotropic filler 1, a different filler, and a liquid dispersion medium. In the mixing, the powder F and the liquid dispersion medium may be mixed in advance to form a liquid composition, or the anisotropic filler 1 and the different fillers may be mixed in advance.
Examples of the mixer used for mixing include a mixer using a stirring blade, a henschel mixer, a ribbon blender, a rocking mixer, a vibrating mixer, and a rotary mixer, and specifically include a homomixer, a homogenizer, and a ball mill.
The mixing method may be either a batch method or a continuous method. The mixer for the batch mixing is preferably a henschel mixer, a pressure kneader, a banbury mixer, or a planetary mixer.
The mixing is preferably performed by stirring, more preferably by rotational stirring using a stirring blade.
The stirring speed is preferably 800rpm or more, more preferably 2000rpm or more. The stirring speed is preferably 10000rpm or less, more preferably 8000rpm or less. In this case, the F powder and the anisotropic filler are sheared, and the aggregate is easily broken, so that the present dispersion liquid having excellent dispersibility is easily obtained.
In addition, if the anisotropic filler is in the form of a scale or plate, the layered aggregate (secondary particles) of the anisotropic filler formed in general is easily broken efficiently and easily forms a card house structure, and thus the present dispersion liquid having good dispersibility is easily formed.
The molded article of the present invention (hereinafter referred to as "the present molded article") comprises a tetrafluoroethylene polymer containing PAVE units (hereinafter referred to as "PFA polymer") and an anisotropic filler having a mohs hardness of 4 or less. The PFA polymer is a polymer having a polar functional group or a polymer having no polar functional group and containing 2.0 to 5.0 mol% of PAVE unit relative to the whole units, and the proportion (content) of the anisotropic filler in the molded product is 10 mass% or more.
The shape of the molded article may be a layer, a plate or a block, and a layer is preferable. The thickness of the layered molding is preferably 150 μm or less. The layered molded article can be used for producing an impregnated article such as a film or a prepreg, a laminate, or the like.
The definition and the range of the anisotropic filler in the present shaped article include the same preferable forms as those of the anisotropic filler in the present dispersion liquid.
The type and range of the polar functional group of the PFA-based polymer in the present molded article include the same preferred forms as those of the F polymer. The PFA-based polymer is preferably the polymer (1) or the polymer (2).
The content of the anisotropic filler in the molded article is preferably 15 mass% or more, and more preferably 25 mass% or more. The content of the anisotropic filler is preferably 50% by mass or less, and more preferably 40% by mass or less.
The content of the PFA-based polymer in the molded article is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. The content of the PFA-based polymer is preferably 95% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. When the content of the PFA-based polymer is within this range, the physical properties of the PFA-based polymer tend to be remarkably exhibited in the present molded article. Furthermore, the anisotropic filler is inhibited from falling off from the molded article.
The present molding preferably further contains an aromatic polymer (particularly, aromatic polyimide) or PTFE. The definitions and ranges of the aromatic polymer and PTFE, respectively, and the mass ratios of the respective contents to the F polymer content in the present molded article are the same as those in the present dispersion.
The present molded article is preferably formed from the present dispersion. Specifically, when the dispersion is applied to the surface of a substrate and the liquid dispersion medium is removed, a layer containing the PFA-based polymer and the anisotropic filler (hereinafter referred to as "the present layer") as the present molded article can be easily formed on the surface of the substrate. More specifically, a laminate comprising a substrate and the present layer formed on the surface of the substrate can be obtained by applying the present dispersion to the surface of the substrate, heating the substrate to remove the liquid dispersion medium, and then heating to melt and burn the PFA-based polymer. The temperature in the former heating is preferably 120 to 200 ℃. The latter heating temperature is preferably 250 to 400 ℃, more preferably 300 to 380 ℃.
Examples of the substrate include a metal substrate (e.g., a metal foil of copper, nickel, aluminum, titanium, or an alloy thereof), a resin film (e.g., a film of polyimide, polyacrylate, polysulfone, polyarylsulfone, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystal polyester, or liquid crystal polyesteramide), and a prepreg (a precursor of a fiber-reinforced resin substrate).
The application of the present dispersion is preferably carried out by coating. Examples of the coating method include a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset coating method, a blade coating method, a kiss coating method, a bar coating method, a die coating method, a jet meyer bar coating method, and a comma coating method.
Examples of the heating method include a method using a heating furnace, a method using a forced air drying furnace, and a method of irradiating a heat ray such as infrared ray.
The thickness of the layer is preferably 0.1 to 150 μm. Specifically, if the substrate is a metal foil, the thickness of the layer is preferably 1 to 30 μm. If the substrate is a resin film, the thickness of the layer is preferably 1 to 150 μm, more preferably 10 to 50 μm.
The dispersion may be applied to only one surface of the substrate, or may be applied to both surfaces of the substrate. In the former case, a laminate including a substrate and the present layer on one surface of the substrate can be obtained, and in the latter case, a laminate including a substrate and the present layer on both surfaces of the substrate can be obtained. The latter laminate is less likely to warp and therefore has excellent workability in processing.
Specific examples of the laminate include a metal-clad laminate comprising a metal foil and the present layer on at least one surface of the metal foil, and a multilayer film comprising a polyimide film and the present layer on both surfaces of the polyimide film.
These laminates are excellent in various physical properties such as electrical properties and are suitable as printed circuit board materials and the like. Specifically, the laminate can be used for manufacturing a flexible printed circuit board or a rigid printed circuit board.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
1. Preparation of the ingredients
[ powder ]
Powder 1: comprising a main chain having 1X 10 carbon atoms and, in order, 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE units, NAH units and PPVE units6Powder (D50: 2.1 μm) of PFA-based polymer 1 (melting temperature: 300 ℃ C.) having 1000 carbonyl groups
Powder 2: comprising a main chain having 1X 10 carbon atoms and comprising 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order6Powder (D50: 1.8 μm) of PFA-based polymer 2 (melting temperature: 305 ℃ C.) having 40 carbonyl groups
Powder 3: powder comprising PFA-based Polymer 2 (D50: 5.3 μm)
Powder 4: powder comprising PTFE having a number average molecular weight of 2 ten thousand (D50: 3.2 μm)
[ Anisotropic Filler ]
Packing 1: scale-like filler formed of boron nitride (D50: 7.0 μm)
And (3) filler 2: scale-like filler formed of boron nitride (D50: 3.7 μm)
And (3) filler: scale-like filler formed of boron nitride (D50: 7.3 μm)
And (4) filler: a plate-like talc filler having a three-layer structure comprising a water-repellent layer, a hydrophilic layer and a water-repellent layer in this order (D50: 4.5 μm, average major axis: 5.1 μm, average minor axis: 0.2 μm, aspect ratio: 25, "SG-95" manufactured by Nippon Talc Co., Ltd.).
The Mohs hardness of the filler 1-3 is 2, and the Mohs hardness of the filler 4 is 1. Fillers 1, 2 and 4 are surface treated with a silane coupling agent.
[ liquid Dispersion Medium ]
NMP: n-methyl-2-pyrrolidone
[ surfactant ]
Surfactant 1: CH (CH)2＝C(CH3)C(O)OCH2CH2(CF2)6F and CH2＝C(CH3)C(O)(OCH2CH2)23OH copolymer, a nonionic polymer having a fluorine content of 35 mass%.
[ varnish of aromatic Polymer ]
Varnish 1: varnish (solid content concentration: 18% by mass) obtained by dissolving thermoplastic aromatic polyimide (PI1) in NMP
2. Production example of Dispersion
(example 1)
First, powder 1, varnish 1, surfactant 1, and NMP were put into a pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150rpm for 1 hour to prepare a composition. Then, filler 1, surfactant 1 and NMP were put into another pot, zirconia balls were put into the pot, and the pot was rolled at 150rpm for 1 hour to prepare a composition.
Subsequently, the two compositions were charged into another tank, and zirconia balls were charged into the tank. Thereafter, the pot was rolled at a rotation speed of 150rpm for 1 hour to obtain a dispersion 1 (viscosity: 400 mPas) containing the powder 1(11 parts by mass), the filler 1(11 parts by mass), PI1(7 parts by mass), the surfactant 1(4 parts by mass) and NMP (67 parts by mass).
(examples 2 to 9)
Dispersions 2 to 9 were obtained in the same manner as in example 1, except that the kinds and amounts of the powder, the filler, the varnish, the surfactant and the liquid dispersion medium were changed as shown in table 1 below.
(example 10)
A dispersion 10 was obtained in the same manner as in example 1, except that 3 parts by mass of filler 1 and 8 parts by mass of filler 2 were used instead of 11 parts by mass of filler 1.
[ Table 1]
The values in parentheses in the columns for the powder, filler and varnish types show the contents thereof in the dispersion (unit: mass%), respectively.
3. Production example of molded article
The dispersion 1 was applied to the surface of a long copper foil (thickness: 18 μm) by a bar coating method to form a wet film. Then, the metal foil on which the wet film was formed was passed through a drying oven at 120 ℃ for 5 minutes, and dried by heating to obtain a dry film. Thereafter, the dry film was heated at 380 ℃ for 3 minutes in a nitrogen oven. Thus, a laminate 1 having a metal foil and a polymer layer (thickness: 5 μm) as a molded article comprising a melt-sintered product of the powder 1 and the filler 1 on the surface thereof was produced.
Laminates 2 to 10 were obtained in the same manner as laminate 1 except that dispersions 2 to 10 were used instead of dispersion 1, respectively.
4. Evaluation of
4-1. Dispersion stability of Dispersion
After the dispersions 1 to 10 were stored at 25 ℃ in a container, the dispersibility thereof was visually observed, and the dispersion stability was evaluated according to the following criteria.
[ evaluation standards ]
Very good: no aggregates were found.
Good: the side walls of the vessel were observed to have fine agglomerates attached. And the mixture is evenly dispersed by gentle stirring.
And (delta): coagulates can also be seen settling at the bottom of the vessel. Shear is applied to stir and redisperse uniformly.
X: coagulates can also be seen settling at the bottom of the vessel. Even if shear is applied to stir, it is difficult to redisperse.
4-2 physical Properties of laminate
4-2-1. surface smoothness
The polymer layers of the laminates 1 to 9 were visually observed for smoothness of the surfaces thereof, and the surface smoothness was evaluated according to the following criteria.
[ evaluation standards ]
Good: the entire surface of the polymer layer is smooth.
And (delta): irregularities due to polymer or filler loss can be seen at the surface edges of the polymer layer.
X: irregularities due to the absence of the polymer or the inorganic filler can be seen on the entire surface of the polymer layer
4-2-2. coefficient of linear expansion
For the laminates 1 to 4, 9 and 10, 180mm square test pieces were cut out, and the linear expansion coefficient of the test pieces in the range of 25 to 260 ℃ was measured according to the measurement method specified in JIS C6471: 1995.
[ evaluation standards ]
Good: 30 ppm/DEG C or less.
X: above 30 ppm/DEG C.
4-2-3 dielectric loss tangent
The copper foils of the laminates 1 to 4, 9 and 10 were etched and removed with an iron chloride solution to prepare individual polymer layers, and the dielectric loss tangent (measurement frequency: 10GHz) of the polymer layers was measured by the SPDR (split dielectric resonance) method.
[ evaluation standards ]
Good: the dielectric loss tangent is less than 0.0010.
And (delta): the dielectric loss tangent is 0.0010 to 0.0025.
X: the dielectric loss tangent thereof exceeds 0.0025.
The results of the evaluations are summarized in Table 2 below.
[ Table 2]
5. Example of production of Dispersion (second)
(example 11)
First, powder 1, surfactant 1 and NMP were added to a pot and mixed, and stirred with a homomixer at 2000rpm for 1 hour to obtain a composition. In another pot, filler 1, surfactant 1 and NMP were charged and stirred at 2000rpm for 1 hour by a homomixer to obtain a composition. Subsequently, the two compositions were put into another tank and stirred with a homomixer at 2000rpm for 1 hour to obtain a dispersion liquid 11 (viscosity: 300 mPas, component dispersion layer rate: 80%) containing powder 1(11 parts by mass), filler 1(11 parts by mass), surfactant 1(4 parts by mass) and NMP (74 parts by mass).
(example 12)
A dispersion 12 (viscosity: 300 mPas, component dispersed layer rate: 50%) was obtained in the same manner as in example 11, except that an ultrasonic homogenizer not involving stirring by a stirring blade was used in place of the homogenizing disperser.
6. Production example of laminate (second)
The dispersion 11 was applied roll-to-roll by the gravure reversal method on the surface of an aluminum foil 18 μm thick to form a liquid coating. Then, the aluminum foil on which the liquid coating was formed was passed through a drying oven at 120 ℃ for 5 minutes, and dried by heating. Thereafter, the dry film was heated at 340 ℃ for 3 minutes in a far infrared oven under a nitrogen atmosphere. Thus, a laminate 11 was produced in which a polymer layer (thickness: 10 μm) was formed on the surface of the aluminum foil. A laminate 12 was produced in the same manner as in the laminate 11, except that the dispersion 12 was used instead of the dispersion 11.
As a result of observing the cross section of each laminate by SEM, the distribution state of filler 1 in the polymer layer of laminate 11 was denser than that of the polymer layer of laminate 12. In addition, the polymer layers of laminate 11 have a lower dielectric loss tangent than the polymer layers of laminate 12. The thermal conductivity and the bendability of the laminate 11 are superior to those of the laminate 12.
Industrial applicability of the invention
The dispersion liquid of the present invention has excellent dispersion stability, and can be used for producing molded articles (such as films, impregnated articles such as prepregs, laminated sheets, and coated materials) having physical properties based on an F polymer (PFA polymer) and properties based on an anisotropic filler. The molded article of the present invention is useful as an antenna member, a printed circuit board, an airplane member, an automobile member, a sports equipment, a food industry product, a paint, a cosmetic, or the like, and specifically, as a heat radiating member, an electric wire coating material (e.g., an airplane electric wire), an electrically insulating tape, an insulating tape for oil drilling, a material for a printed circuit board, a separation membrane (e.g., a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an ion exchange membrane, a dialysis membrane, or a gas separation membrane), an electrode adhesive (e.g., for a lithium secondary battery or a fuel cell), a copying roll, a furniture, an automobile instrument panel, a cover for a home appliance product, a sliding member (e.g., a load bearing, a sliding shaft, a valve, a bearing, a gear, a cam, a conveyor belt, or a food conveyor belt), a tool (e.g., a shovel, a file, a awl, or a saw), a boiler, a hopper, a pipe, an oven, a baking mold, a baking equipment, a food, or the like, An outer surface coating material for heat exchangers (fans, heat transfer tubes, etc.) of chutes, molds, toilets, container coating materials, cooling and heating devices, and the like.
Claims (15)
1. A dispersion liquid comprising a powder of a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit or a hexafluoropropylene-based unit, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium, wherein the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler.
2. The dispersion liquid according to claim 1, wherein the content of the tetrafluoroethylene polymer and the content of the anisotropic filler are both 5% by mass or more.
3. The dispersion liquid according to claim 1 or 2, wherein the anisotropic filler has a scale-like or plate-like shape.
4. The dispersion as claimed in any one of claims 1 to 3, wherein the anisotropic filler has an aspect ratio of 2 or more.
5. The dispersion as claimed in any one of claims 1 to 4, wherein the anisotropic filler is an anisotropic filler containing boron nitride or talc.
6. The dispersion as claimed in any one of claims 1 to 5, further comprising a polytetrafluoroethylene powder or an aromatic polymer.
7. The dispersion liquid according to any one of claims 1 to 6, wherein the component dispersion layer ratio is 60% or more.
8. A method for producing the dispersion according to any one of claims 1 to 7, wherein the powder, the anisotropic filler, an inorganic filler having an average particle diameter smaller than that of the anisotropic filler, and a liquid dispersion medium are mixed.
9. The production method according to claim 8, wherein the mixing is performed by stirring.
10. A molded article comprising a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit and an anisotropic filler having a Mohs hardness of 4 or less,
the tetrafluoroethylene polymer is a polymer having a polar functional group or a polymer having no polar functional group, which contains 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit based on the whole units, and the anisotropic filler accounts for 10 mass% or more of the molded article.
11. The formed article according to claim 10, wherein the aspect ratio of the anisotropic filler is 2 or more.
12. The molded article according to claim 11, wherein the anisotropic filler is a scale-like anisotropic filler containing boron nitride or a plate-like anisotropic filler containing talc.
13. The molded article according to any one of claims 9 to 12, wherein the anisotropic filler has an average particle diameter of 1 μm or more.
14. The molded article as claimed in any one of claims 9 to 13, further comprising polytetrafluoroethylene or an aromatic polymer.
15. The molded article according to any one of claims 9 to 14, wherein the molded article is a layered molded article having a thickness of 150 μm or less.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-221564 | 2019-12-06 | ||
| JP2019221564 | 2019-12-06 | ||
| JP2020-016436 | 2020-02-03 | ||
| JP2020016436 | 2020-02-03 | ||
| JP2020-077294 | 2020-04-24 | ||
| JP2020077294 | 2020-04-24 | ||
| JP2020-154348 | 2020-09-15 | ||
| JP2020154348 | 2020-09-15 | ||
| PCT/JP2020/044992 WO2021112164A1 (en) | 2019-12-06 | 2020-12-03 | Dispersion liquid, method for producing dispersion liquid, and molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114729171A true CN114729171A (en) | 2022-07-08 |
| CN114729171B CN114729171B (en) | 2024-04-05 |
Family
ID=76222423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080078871.9A Active CN114729171B (en) | 2019-12-06 | 2020-12-03 | Dispersion, method for producing dispersion, and molded article |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2021112164A1 (en) |
| KR (1) | KR20220113354A (en) |
| CN (1) | CN114729171B (en) |
| TW (1) | TW202130732A (en) |
| WO (1) | WO2021112164A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022019223A1 (en) * | 2020-07-21 | 2022-01-27 | Ａｇｃ株式会社 | Dispersion, composite particles, and method for producing composite particles |
| WO2023163025A1 (en) * | 2022-02-28 | 2023-08-31 | Ａｇｃ株式会社 | Composition |
| WO2023195377A1 (en) * | 2022-04-07 | 2023-10-12 | ダイキン工業株式会社 | Solid composition, circuit board, and method for producing solid composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5000875A (en) * | 1987-10-16 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Conductive filled fluoropolymers |
| US6518349B1 (en) * | 1999-03-31 | 2003-02-11 | E. I. Du Pont De Nemours And Company | Sprayable powder of non-fibrillatable fluoropolymer |
| EP2949701B1 (en) | 2013-01-24 | 2019-05-22 | Daikin Industries, Ltd. | Composition, and method for producing foam molded material and electric wire |
| KR102353961B1 (en) * | 2016-07-22 | 2022-01-21 | 에이지씨 가부시키가이샤 | Liquid composition and manufacturing method of film and laminate using the liquid composition |
-
2020
- 2020-12-03 WO PCT/JP2020/044992 patent/WO2021112164A1/en active Application Filing
- 2020-12-03 KR KR1020227013463A patent/KR20220113354A/en unknown
- 2020-12-03 CN CN202080078871.9A patent/CN114729171B/en active Active
- 2020-12-03 JP JP2021562707A patent/JPWO2021112164A1/ja active Pending
- 2020-12-04 TW TW109142815A patent/TW202130732A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN114729171B (en) | 2024-04-05 |
| TW202130732A (en) | 2021-08-16 |
| KR20220113354A (en) | 2022-08-12 |
| WO2021112164A1 (en) | 2021-06-10 |
| JPWO2021112164A1 (en) | 2021-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114729171B (en) | Dispersion, method for producing dispersion, and molded article | |
| CN114599712A (en) | Nonaqueous dispersion, method for producing laminate, and molded article | |
| KR20230126703A (en) | Aqueous dispersion and its preparation method | |
| WO2022149551A1 (en) | Method for producing tetrafluoroethylene-based polymer composition, composition, metal-clad laminate, and stretched sheet | |
| CN115667377A (en) | Method for producing dispersion liquid | |
| WO2021157507A1 (en) | Method for producing multilayer body and liquid composition | |
| CN115003749B (en) | Dispersion liquid | |
| JP2022061412A (en) | Production method of liquid composition and production method of laminate | |
| JP2022098733A (en) | Composition of tetrafluoroethylene polymer, liquid composition containing the same, and sheet | |
| CN115803390A (en) | Powder composition and composite particle | |
| JP7511109B2 (en) | Method for producing liquid composition, impregnated substrate, polymer-carrying substrate, and laminate | |
| JP7511117B2 (en) | Composite particles, method for producing composite particles, liquid composition, method for producing laminate, and method for producing film | |
| JP7511124B2 (en) | Method for producing dispersion and dispersion | |
| JP2022072333A (en) | Composition including tetrafluoroethylene polymer, liquid composition comprising the composition, laminate and film | |
| TW202319409A (en) | Composition | |
| WO2023163025A1 (en) | Composition | |
| JP2022061774A (en) | Manufacturing method of dispersion liquid and manufacturing method of laminated body | |
| JP2022069962A (en) | Dispersion and method for producing laminate | |
| JP2022163625A (en) | Method for producing modified dispersion liquid and dispersion liquid | |
| TW202208543A (en) | Dispersion, composite particles, and method for producing composite particles | |
| JP2023114334A (en) | Composition | |
| WO2023017811A1 (en) | Aqueous dispersion and method for producing laminate | |
| JP2022167052A (en) | liquid composition | |
| TW202323429A (en) | Liquid composition, laminate, and production methods therefor | |
| JP2023019614A (en) | Composition and production method of laminate having layer formed from composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |