JP6825556B2 - Barium titanate particle powder, dispersions and coatings containing the powder - Google Patents
Barium titanate particle powder, dispersions and coatings containing the powder Download PDFInfo
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- JP6825556B2 JP6825556B2 JP2017503710A JP2017503710A JP6825556B2 JP 6825556 B2 JP6825556 B2 JP 6825556B2 JP 2017503710 A JP2017503710 A JP 2017503710A JP 2017503710 A JP2017503710 A JP 2017503710A JP 6825556 B2 JP6825556 B2 JP 6825556B2
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- JP
- Japan
- Prior art keywords
- barium titanate
- particle powder
- titanate particle
- compound
- powder according
- 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.)
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- 239000002245 particle Substances 0.000 title claims description 188
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 145
- 229910002113 barium titanate Inorganic materials 0.000 title claims description 145
- 239000000843 powder Substances 0.000 title claims description 129
- 238000000576 coating method Methods 0.000 title claims description 26
- 239000006185 dispersion Substances 0.000 title claims description 20
- -1 aluminum compound Chemical class 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 25
- 229910001422 barium ion Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 150000003609 titanium compounds Chemical class 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 150000003464 sulfur compounds Chemical class 0.000 claims description 7
- 150000003755 zirconium compounds Chemical class 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- 238000010828 elution Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000002270 dispersing agent Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003016 phosphoric acids Chemical class 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 150000003748 yttrium compounds Chemical class 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- XEJNLUBEFCNORG-UHFFFAOYSA-N ditridecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCC XEJNLUBEFCNORG-UHFFFAOYSA-N 0.000 description 2
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical class COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- HVGAPIUWXUVICC-UHFFFAOYSA-N 6-methylheptan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-] HVGAPIUWXUVICC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
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- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Description
本発明は、微細であるがために成膜した際に高い透明性を有し、粒度分布がシャープで、分散を阻害するＢａイオン溶出量が少ないチタン酸バリウム粒子粉末を提供することを目的とするものである。 An object of the present invention is to provide a barium titanate particle powder which has high transparency when formed due to its fineness, has a sharp particle size distribution, and has a small amount of Ba ion elution that inhibits dispersion. To do.
高い誘電率を有するチタン酸バリウムは、積層セラミックコンデンサなどの誘電材料として広く用いられている。 Barium titanate, which has a high dielectric constant, is widely used as a dielectric material for multilayer ceramic capacitors and the like.
一方、各種ディスプレーなどに用いられる光学フィルムに対して、透明樹脂にジルコニアなどの無機粒子フィラーを添加し誘電率や屈折率を制御することが行われている。液晶ディスプレー制御用ＴＦＴにおいても、低電力化のため、絶縁膜などの材料として微粒子かつ高誘電率なものが求められている。 On the other hand, the dielectric constant and the refractive index are controlled by adding an inorganic particle filler such as zirconia to a transparent resin for an optical film used for various displays and the like. Even in TFTs for controlling liquid crystal displays, fine particles and high dielectric constants are required as materials for insulating films and the like in order to reduce power consumption.
例えば、ＴＦＴにおいては、パターニングのためエッチングなどの処理に晒されることがある。溶出するＢａイオンが多いと、粉体と酸性の官能基を持つ分散剤、バインダー、樹脂等有機成分が接触した際、望ましくない反応が起きてしまい、各有機成分の働きを鈍らせ、目的とする透明性が高い塗膜が出来ないという弊害の可能性がある。 For example, a TFT may be exposed to a process such as etching for patterning. If a large amount of Ba ions are eluted, an undesired reaction will occur when the powder and organic components such as a dispersant having an acidic functional group, a binder, and a resin come into contact with each other, and the action of each organic component will be blunted. There is a possibility that a highly transparent coating film cannot be formed.
そこで、チタン酸バリウムを前記光学用途に用いるため、粒径を微細化して透明性を確保するとともに、Ｂａイオン溶出量が小さく、誘電率・屈折率の大きなチタン酸バリウム粒子粉末を得ることが求められている。 Therefore, in order to use barium titanate for the above optical applications, it is required to obtain barium titanate particle powder having a small particle size to ensure transparency, a small amount of Ba ion elution, and a large dielectric constant and refractive index. Has been done.
誘電体フィルムを形成するには粒径が小さく、不要な不純物が少ないものが電気的特性が良いことは、公知の事実であり、そのためにチタン酸バリウムを合成から設計することはいくつかの先行技術で明らかである（特許文献１）。引用文献1には、粒度分布の狭いチタン酸バリウムが記載されているが、光学用としてはいまだ十分とは言い難い。 It is a well-known fact that a material having a small particle size and few unnecessary impurities has good electrical properties for forming a dielectric film, and therefore, designing barium titanate from synthesis has some prior art. It is clear in the technique (Patent Document 1). Although barium titanate having a narrow particle size distribution is described in Cited Document 1, it cannot be said that it is sufficient for optical use.
またペロブスカイト化合物の表面を被覆した技術を開示した先行文献もあるが、シリカで被覆した特許文献２はあくまで分散安定性を目的に被覆処理されたものであり、シリカにバリウムの溶出を防止する効果があることは何ら記載されていない。 In addition, although there is a prior document that discloses a technique for coating the surface of a perovskite compound, Patent Document 2 coated with silica is only coated for the purpose of dispersion stability, and has an effect of preventing the elution of barium into silica. There is no mention of it.
エッチングなどの手法で、ＢａＴｉＯ３粒子表層をＢａプアにして元素を添加する特許文献もあるが（特許文献３、４）、これは添加物との反応性を向上させる措置であり、溶出に関しては当業者といえどもこの文献からこの効果を類推することは出来ない。また特許文献５にはチタン酸バリウムが幅広い化学量論比で存在するような記載があるが、Ｂａプアなものを用いることが好適であることは何ら考慮されていない。There is also a patent document in which an element is added by making the surface layer of BaTiO 3 particles Ba-poor by a method such as etching (Patent Documents 3 and 4), but this is a measure for improving the reactivity with the additive, and regarding elution. Even those skilled in the art cannot infer this effect from this document. Further, although there is a description in Patent Document 5 that barium titanate exists in a wide stoichiometric ratio, it is not considered at all that it is preferable to use a barium titanate.
前記諸特性を満たすチタン酸バリウム粒子粉末は現在最も要求されているところであるが、未だ得られていない。 Barium titanate particle powder satisfying the above properties is currently the most sought after, but has not yet been obtained.
そこで、本発明では、成膜した際に高い透明性を有するフィルム等の作製に好適な、微小でありながら、Ｂａイオン溶出量が少なく、粒度分布がシャープなチタン酸バリウム粒子粉末を提供することを技術的課題とするものである。 Therefore, the present invention provides a barium titanate particle powder having a small amount of Ba ions and a sharp particle size distribution, which is suitable for producing a film having high transparency when formed into a film. Is a technical issue.
前記技術的課題は、次のとおりの本発明によって達成できる。 The technical subject can be achieved by the present invention as follows.
即ち、本発明は、平均粒径が１０ｎｍ以上６０ｎｍ以下であって、粒度分布の標準偏差を平均粒径で除した値が０．３５以下かつ粉体から水溶媒に溶出するＢａイオンの量が１０００ｐｐｍ以下であり、Ｂａ／Ｔｉ比が０．７５０〜０．９６２モル比であるチタン酸バリウム粒子である（本発明１）。 That is, in the present invention, the average particle size is 10 nm or more and 60 nm or less, the value obtained by dividing the standard deviation of the particle size distribution by the average particle size is 0.35 or less, and the amount of Ba ions eluted from the powder into the aqueous solvent is Barium titanate particles having a Ba / Ti ratio of 0.750 to 0.962 mol and a Ba / Ti ratio of 1000 ppm or less (the present invention 1).
また、本発明は、粒子表面が、Ｓｉ化合物、チタン化合物、ジルコニウム化合物、アルミニウム化合物、イットリウム化合物、硫黄化合物及びリン酸化合物から選ばれる少なくとも一種の表面被覆物で被覆された本発明１記載のチタン酸バリウム粒子粉末である（本発明２）。 Further, the present invention relates to the titanium according to the present invention 1, wherein the particle surface is coated with at least one surface coating selected from a Si compound, a titanium compound, a zirconium compound, an aluminum compound, an yttrium compound, a sulfur compound and a phosphoric acid compound. It is a barium acid acid particle powder (the present invention 2).
また、本発明は、本発明２記載の表面被覆物の被覆量が、Ｓｉ化合物はＳｉＯ２換算で、チタン化合物は炭素換算で、その他は各元素換算で０．０５〜５．０重量％であるチタン酸バリウム粒子粉末である（本発明３）。Further, in the present invention, the coating amount of the surface coating material according to the present invention 2 is 0.05 to 5.0% by weight in terms of SiO 2 for Si compounds, carbon equivalent for titanium compounds, and 0.05 to 5.0% by weight for each element. A barium titanate particle powder (3 of the present invention).
また、本発明は１００〜５００℃の温度範囲で熱処理して得られた本発明１記載のチタン酸バリウム粒子である（本発明５）。 Further, the present invention is the barium titanate particles according to the present invention 1 obtained by heat treatment in a temperature range of 100 to 500 ° C. (the present invention 5).
本発明に係るチタン酸バリウム粒子粉末は、微細な粒子でありながら、Ｂａイオン溶出量が少なく、高い誘電率を有するので、光学材料用として好適である。 The barium titanate particle powder according to the present invention is suitable for an optical material because it is a fine particle but has a small amount of Ba ions eluted and has a high dielectric constant.
本発明の構成を詳述すれば、次の通りである。 The configuration of the present invention will be described in detail as follows.
本発明に係るチタン酸バリウム粒子粉末の一次粒子の平均粒径（ｘ）は１０〜６０ｎｍである。一次粒子の平均粒径を前記範囲に制御することによって、透明性に優れたチタン酸バリウム粒子粉末とすることができる。好ましい一次粒子の平均粒径は１０〜５８ｎｍであり、より好ましくは１０〜５５ｎｍである。 The average particle size (x) of the primary particles of the barium titanate particle powder according to the present invention is 10 to 60 nm. By controlling the average particle size of the primary particles within the above range, barium titanate particle powder having excellent transparency can be obtained. The average particle size of the primary particles is preferably 10 to 58 nm, more preferably 10 to 55 nm.
本発明に係るチタン酸バリウム粒子粉末から水溶媒に溶出するＢａイオンの量は１０００ｐｐｍ以下である。水溶媒に溶出するＢａイオンの量が１０００ｐｐｍを超える場合、チタン酸バリウム粒子を含有する分散体において、分散剤の機能を阻害し、その結果、塗膜としたときの透明性が低下する。好ましくは９００ｐｐｍ以下であり、より好ましくは８００ｐｐｍ以下である。チタン酸バリウム粒子粉末の一次粒子の平均粒径が小さくなるほど、比表面積が大きくなり、且つ結晶性も低下する傾向であったので、Ｂａ溶出量も増える傾向にあった。なお、チタン酸バリウム粒子粉末から水溶媒に溶出するＢａイオンの量は後述する評価方法によって算出した。 The amount of Ba ions eluted from the barium titanate particle powder according to the present invention into an aqueous solvent is 1000 ppm or less. When the amount of Ba ions eluted in the aqueous solvent exceeds 1000 ppm, the function of the dispersant is inhibited in the dispersion containing barium titanate particles, and as a result, the transparency of the coating film is lowered. It is preferably 900 ppm or less, and more preferably 800 ppm or less. As the average particle size of the primary particles of the barium titanate particle powder became smaller, the specific surface area tended to increase and the crystallinity tended to decrease, so that the Ba elution amount also tended to increase. The amount of Ba ions eluted from the barium titanate particle powder into the aqueous solvent was calculated by the evaluation method described later.
本発明に係るチタン酸バリウム粒子粉末の一次粒子の変動係数（粒度分布（σ）を一次粒子の平均粒径（ｘ）で除した値）は０．３５以下である。変動係数の下限値は、通常０．２である。前記数値が前記範囲内に制御されることによって、粒度分布に優れたチタン酸バリウム粒子粉末となる。好ましくは０．２０〜０．３４８であり、より好ましくは０．２０〜０．３０である。 The coefficient of variation of the primary particles of the barium titanate particle powder according to the present invention (value obtained by dividing the particle size distribution (σ) by the average particle size (x) of the primary particles) is 0.35 or less. The lower limit of the coefficient of variation is usually 0.2. By controlling the numerical value within the above range, the barium titanate particle powder having an excellent particle size distribution can be obtained. It is preferably 0.25 to 0.348, and more preferably 0.25 to 0.30.
本発明に係るチタン酸バリウム粒子粉末の粒子表面は、Ｓｉ化合物、チタン化合物、ジルコニウム化合物、アルミニウム化合物、イットリウム化合物、硫黄化合物及びリン酸化合物から選ばれる少なくとも一種の表面被覆物で被覆されていてもよい。 Even if the particle surface of the barium titanate particle powder according to the present invention is coated with at least one surface coating selected from Si compound, titanium compound, zirconium compound, aluminum compound, yttrium compound, sulfur compound and phosphoric acid compound. Good.
本発明に係るチタン酸バリウム粒子粉末の粒子表面を被覆する前記各化合物には、バリウムの溶出を抑える効果があるため、Ｂａイオンの溶出低減、分散性向上に効果的に機能する。また、Ｂａイオンの溶出低減には後述の水洗を行うことにより達成できるが、粒子表面を被覆することにより、その水洗工程が不完全でもＢａイオンの溶出低減を達成できる。 Since each of the compounds covering the particle surface of the barium titanate particle powder according to the present invention has an effect of suppressing the elution of barium, it effectively functions to reduce the elution of Ba ions and improve the dispersibility. Further, the elution reduction of Ba ions can be achieved by performing the washing with water described later, but by coating the particle surface, the elution reduction of Ba ions can be achieved even if the washing step is incomplete.
Ｓｉ化合物としては、Ｓｉを含有する無機化合物としては水ガラスやその他ケイ酸塩が好ましく、また、Ｓｉを含有する有機化合物としては、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン及びデシルトリエトキシシラン等のアルコキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ―アミノプロピルトリエトキシシラン、γ―グリシドキシプロピルトリメトキシシラン、γ―メルカプトプロピルトリメトキシシラン、γ―メタクロイルオキシプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、ｐ−スチリルトリメトキシシラン、ｐ−スチリルトリエトキシシラン、ｐ−スチリルトリクロルシシラン、ｐ−スチリルトリフェノキシシラン等のシラン系カップリング剤、ポリシロキサン、メチルハイドロジェンポリシロキサン、変性ポリシロキサン等のオルガノポリシロキサン等、シランモノマー等のシラン化合物が用いられる。また、チタン化合物、ジルコニウム化合物、アルミニウム化合物、イットリウム化合物から選ばれる一種以上の化合物としては、各元素の有機化合物および／または無機化合物を用いればよく、硫黄化合物としては硫酸根が好ましく、リン酸化合物としては各種リン酸化合物が好ましい。なお、チタン化合物、ジルコニウム化合物、アルミニウム化合物、イットリウム化合物、硫黄化合物、リン酸化合物から選ばれる一種以上の化合物では焼結を抑制する効果も期待できる。 As the Si compound, water glass or other silicate is preferable as the Si-containing inorganic compound, and methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, or diphenyl as the Si-containing organic compound. Diethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxy. Alkoxysilanes such as silane, octyltriethoxysilane and decyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-methacloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, p-styryltri Silane-based coupling agents such as ethoxysilane, p-styryltrichloricsilane, p-styryltriphenoxysilane, organopolysiloxane such as polysiloxane, methylhydrogenpolysiloxane, and modified polysiloxane, and silane compounds such as silane monomer. Used. Further, as one or more compounds selected from titanium compounds, zirconium compounds, aluminum compounds, and yttrium compounds, organic compounds and / or inorganic compounds of each element may be used, and sulfate roots are preferable as sulfur compounds, and phosphoric acid compounds are preferable. Various phosphoric acid compounds are preferable. In addition, one or more compounds selected from titanium compounds, zirconium compounds, aluminum compounds, yttrium compounds, sulfur compounds, and phosphoric acid compounds can be expected to have an effect of suppressing sintering.
前記表面被覆物の被覆量は、Ｓｉ化合物はＳｉＯ２換算で、チタン化合物は炭素換算で、アルミニウム化合物、イットリウム化合物、硫黄化合物及びリン酸化合物は各元素換算で０．０５〜５．０重量％が好ましい。より好ましくは０．１〜４．５重量％である。The coating amount of the surface coating is 0.05 to 5.0% by weight in terms of SiO 2 for Si compounds, carbon conversion for titanium compounds, and 0.05 to 5.0% by weight for aluminum compounds, yttrium compounds, sulfur compounds, and phosphoric acid compounds. Is preferable. More preferably, it is 0.1 to 4.5% by weight.
本発明に係るチタン酸バリウム粒子粉末は、後述する評価方法で測定した比誘電率が３００以上である。比誘電率の上限は通常２０００である。チタン酸バリウム粒子粉末の誘電率が前記範囲に制御されることによって、粒子成長が抑えられた微粒子を得ることができる。より好ましい比誘電率は３５０以上、更により好ましくは３５０〜１５００である。 The barium titanate particle powder according to the present invention has a relative permittivity of 300 or more as measured by an evaluation method described later. The upper limit of the relative permittivity is usually 2000. By controlling the dielectric constant of the barium titanate particle powder within the above range, fine particles with suppressed particle growth can be obtained. A more preferable relative permittivity is 350 or more, and even more preferably 350 to 1500.
本発明に係るチタン酸バリウム粒子粉末の結晶性は、格子定数のａ軸長（ａ）及びｃ軸長（ｃ）を用いて格子定数比ｃ／ａで示した場合に、１．００３未満が好ましい。格子定数比ｃ／ａが１．００３以上のチタン酸バリウム粒子粉末は本発明の粒径では工業的に製造することが困難である。 The crystallinity of the barium titanate particle powder according to the present invention is less than 1.003 when indicated by the lattice constant ratio c / a using the a-axis length (a) and c-axis length (c) of the lattice constants. preferable. Barium titanate particle powder having a lattice constant ratio c / a of 1.003 or more is difficult to industrially produce with the particle size of the present invention.
本発明に係るチタン酸バリウム粒子粉末の比表面積は２０〜８０ｍ２／ｇが好ましい。２０ｍ２／ｇ未満の場合には、粒子粉末が粗大となり、粒子相互間で焼結が生じた粒子となっており、バインダを混合する場合に、分散性が損なわれやすい。比表面積値が８０ｍ２／ｇを超えるチタン酸バリウム粒子粉末を工業的に生産することは困難である。より好ましいＢＥＴ比表面積は２５〜８０ｍ２／ｇであり、更により好ましくは３０〜７５ｍ２／ｇである。The specific surface area of the barium titanate particle powder according to the present invention is preferably 20 to 80 m 2 / g. If it is less than 20 m 2 / g, the particle powder becomes coarse and the particles are sintered between the particles, and the dispersibility is easily impaired when the binder is mixed. It is difficult to industrially produce barium titanate particle powder having a specific surface area value of more than 80 m 2 / g. A more preferable BET specific surface area is 25 to 80 m 2 / g, and even more preferably 30 to 75 m 2 / g.
本発明に係るチタン酸バリウム粒子粉末のＢａ／Ｔｉ比は０．７５０〜１．０００が好ましい。Ｂａ／Ｔｉ比を前記範囲に制御することによって高い誘電特性を有するチタン酸バリウム粒子粉末が得られる。より好ましくは０．７７０〜０．９９０、更により好ましくは０．７８０〜０．９８０である。 The Ba / Ti ratio of the barium titanate particle powder according to the present invention is preferably 0.750 to 1.000. By controlling the Ba / Ti ratio within the above range, barium titanate particle powder having high dielectric properties can be obtained. It is more preferably 0.770 to 0.990, and even more preferably 0.780 to 0.980.
本発明に係るチタン酸バリウム粒子粉末の粒子形状は球形又は粒状が好ましい。球状以外の形状では粒子同士の接触が点接触にならず、分散性が低下したり、粒子のエッジが塗膜の平滑性を低下させる可能性がある。 The particle shape of the barium titanate particle powder according to the present invention is preferably spherical or granular. In a shape other than the spherical shape, the contact between the particles does not become a point contact, and the dispersibility may be lowered, or the edges of the particles may lower the smoothness of the coating film.
次に、本発明に係るチタン酸バリウム粒子粉末の製造方法について述べる。 Next, a method for producing barium titanate particle powder according to the present invention will be described.
本発明に係るチタン酸バリウム粒子粉末は、あらかじめ水熱反応によって作製した平均粒径が１０〜６０ｎｍのチタン酸バリウム粒子粉末を水洗し、溶出Ｂａ分を取り除いておく。すなわち、水熱法によってチタン酸バリウム粒子粉末を生成することが好ましい。 In the barium titanate particle powder according to the present invention, the barium titanate particle powder having an average particle size of 10 to 60 nm prepared in advance by a hydrothermal reaction is washed with water to remove the eluted Ba component. That is, it is preferable to produce barium titanate particle powder by a hydrothermal method.
本発明において、水熱反応は特に限定されるものではないが、例えば、水酸化バリウム水溶液を塩化チタン水溶液に滴下・中和して水酸化チタンコロイドを得、次いで、前記水酸化チタンコロイドを水酸化バリウム水溶液に投入し、得られた混合溶液を加熱してチタン酸バリウムを生成する。冷却、水洗した後、密閉容器中、６５〜２５０℃の温度範囲で水熱処理を行い、水洗、乾燥、粉砕して得ることができる。 In the present invention, the hydrothermal reaction is not particularly limited. For example, a barium hydroxide aqueous solution is dropped and neutralized in a titanium chloride aqueous solution to obtain a titanium hydroxide colloid, and then the titanium hydroxide colloid is watered. It is put into an aqueous solution of barium oxide, and the obtained mixed solution is heated to produce barium titanate. After cooling and washing with water, it can be obtained by performing hydrothermal treatment in a closed container in a temperature range of 65 to 250 ° C., washing with water, drying and pulverizing.
水熱反応では、反応温度、濃度、ｐＨなどを変化させることによって大きさの異なるチタン酸バリウムを製造することができる。 In the hydrothermal reaction, barium titanate having different sizes can be produced by changing the reaction temperature, concentration, pH and the like.
水熱反応によって得られたチタン酸バリウムの平均粒径は１０〜６０ｎｍが好ましい。 The average particle size of barium titanate obtained by the hydrothermal reaction is preferably 10 to 60 nm.
水熱反応により作製したチタン酸バリウム粒子（粒径：１０〜６０ｎｍ）をＢａ／Ｔｉ比が０．７５０〜１．０００の範囲になるまで洗浄することにより、本発明の目的とするチタン酸バリウム粒子粉末を得ることができる。より好ましくは０．７７０〜０．９９０、更により好ましくは０．７８０〜０．９８０である。洗浄条件を制御することによって、チタン酸バリウム粒子の耐酸性や誘電率を制御することができる。洗浄条件の制御としては、例えば、Ｂａイオンが認められなくなるまで水洗し（例えば、水洗ろ液の電気伝導度が１００μＳ／ｃｍ以下）、さらに温水でｐＨ＝７となるまで洗浄することなどが挙げられる。 Barium titanate, which is the object of the present invention, is obtained by washing barium titanate particles (particle size: 10 to 60 nm) produced by a hydrothermal reaction until the Ba / Ti ratio is in the range of 0.750 to 1.000. Particle powder can be obtained. It is more preferably 0.770 to 0.990, and even more preferably 0.780 to 0.980. By controlling the cleaning conditions, the acid resistance and dielectric constant of the barium titanate particles can be controlled. Control of the washing conditions includes, for example, washing with water until Ba ions are no longer recognized (for example, the electric conductivity of the washing liquid is 100 μS / cm or less), and further washing with warm water until pH = 7. Be done.
また、Ｂａ溶液とＴｉ溶液を均一混合、より具体的には、Ｂａ溶液中に投入されるＴｉ溶液の投入口を複数にすることにより、粒子の変動係数（粒度分布の標準偏差を平均粒径で除した値）が０．３５以下に制御することが出来る。 Further, by uniformly mixing the Ba solution and the Ti solution, more specifically, by making the number of inlets of the Ti solution charged into the Ba solution multiple, the coefficient of variation of the particles (the standard deviation of the particle size distribution is the average particle size). The value divided by) can be controlled to 0.35 or less.
また、本発明に係るチタン酸バリウム粒子粉末を１００〜５００℃の温度範囲で熱処理することで、粒度分布や分散性は損なわず、更に高い誘電率を有するチタン酸バリウム粒子粉末を得ることができる。 Further, by heat-treating the barium titanate particle powder according to the present invention in the temperature range of 100 to 500 ° C., the barium titanate particle powder having a higher dielectric constant can be obtained without impairing the particle size distribution and dispersibility. ..
次に、本発明に係る分散体について述べる。 Next, the dispersion according to the present invention will be described.
本発明における分散媒体としては、水系及び溶剤系のいずれをも用いることができる。 As the dispersion medium in the present invention, either an aqueous system or a solvent system can be used.
水系分散体の分散媒体としては、水、もしくは、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール等のアルコール系溶剤；メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ等のグリコールエーテル系溶剤；ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のオキシエチレン又はオキシプロピレン付加重合体；エチレングリコール、プロピレングリコール、１，２，６−ヘキサントリオール等のアルキレングリコール；グリセリン、２−ピロリドン等の水溶性有機溶剤を用いることができる。これらの水系分散体用の分散媒体は、目的とする用途に応じて１種又は２種以上を混合して用いることができる。 As the dispersion medium of the aqueous dispersion, water or an alcohol solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol; a glycol ether solvent such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve; Oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; alkylene glycols such as ethylene glycol, propylene glycol, 1,2,6-hexanetriol; glycerin , 2-Pyrrolidone and other water-soluble organic solvents can be used. As the dispersion medium for these aqueous dispersions, one kind or a mixture of two or more kinds can be used depending on the intended use.
溶剤系分散体用の分散媒体としては、トルエン、キシレン等の芳香族炭化水素；メチルエチルケトン、シクロヘキサノン等のケトン類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類；エチレングリコールモノメチルエーテル、エチレングルコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のエーテルアルコール類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエーテルアセテート類；酢酸エチル、酢酸ブチル、酢酸イソブチル等の酢酸エステル類；乳酸メチルエステル、乳酸エチルエステル、乳酸プロピルエステル等の乳酸エステル類；エチレンカーボネート、プロピレンカーボネート、γ−ブチロラクトン等の環状エステル類及び各種モノマー等を用いることができる。これらの溶剤系分散体用の分散媒体は、目的とする用途に応じて１種又は２種以上を混合して用いることができる。 As the dispersion medium for the solvent-based dispersion, aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. Classes: Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl Ether acetates such as ether acetate and propylene glycol monoethyl ether acetate; Acetate esters such as ethyl acetate, butyl acetate and isobutyl acetate; Lactic acid esters such as lactic acid methyl ester, lactic acid ethyl ester and lactic acid propyl ester; Ethylene carbonate and propylene Cyclic esters such as carbonate and γ-butyrolactone and various monomers can be used. As the dispersion medium for these solvent-based dispersions, one kind or a mixture of two or more kinds can be used depending on the intended use.
本発明に係る分散体を製造するために用いる分散機としては特に限定されるものではなく、粉体層にせん断力、衝撃力、圧縮力、及び／または摩擦力を加えることのできる装置が好ましく、例えば、ローラーミル、高速回転ミル、分級機内蔵型高速回転ミル、ボールミル、媒体攪拌式ミル、気流式粉砕機、圧密せん断ミル、コロイドミル、ロールミル等を用いることができる。 The disperser used for producing the dispersion according to the present invention is not particularly limited, and a device capable of applying a shearing force, an impact force, a compressive force, and / or a frictional force to the powder layer is preferable. For example, a roller mill, a high-speed rotary mill, a high-speed rotary mill with a built-in classifier, a ball mill, a medium stirring mill, an air flow crusher, a compact shear mill, a colloid mill, a roll mill and the like can be used.
本発明に係る分散体は、チタン酸バリウム粒子粉末を分散体構成基材１００重量部に対して０．１〜６０重量部含有し、好ましくは０．５〜５０重量部、より好ましくは１〜４０重量部含有している。チタン酸バリウム粒子粉末の分散体の構成基材としては、上記チタン酸バリウム粒子粉末の他に、分散媒体からなり、必要に応じて分散剤、添加剤（樹脂、消泡剤、助剤等）等を添加することもできる。
本発明における分散剤としては、使用するチタン酸バリウム粒子粉末や分散媒体の種類に応じて適宜選択して使用することができ、アルコキシシラン、シラン系カップリング剤及びオルガノポリシロキサン等の有機ケイ素化合物、チタネート系カップリング剤等の有機チタン化合物、アルミネート系カップリング剤等の有機アルミ化合物、ジルコネート系のカップリング剤等の有機ジルコニウム化合物、界面活性剤あるいは高分子分散剤等を用いることができ、これらは１種または２種以上を混合して用いることができる。The dispersion according to the present invention contains barium titanate particle powder in an amount of 0.1 to 60 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 1 part by weight, based on 100 parts by weight of the dispersion constituent base material. Contains 40 parts by weight. The constituent base material of the dispersion of barium titanate particle powder is composed of a dispersion medium in addition to the above-mentioned barium titanate particle powder, and if necessary, a dispersant and additives (resin, defoamer, auxiliary agent, etc.). Etc. can also be added.
The dispersant in the present invention can be appropriately selected and used according to the type of barium titanate particle powder to be used and the dispersion medium, and is an organosilicon compound such as an alkoxysilane, a silane coupling agent, and an organopolysiloxane. , Organic titanium compounds such as titanate-based coupling agents, organic aluminum compounds such as aluminate-based coupling agents, organic zirconium compounds such as zirconeate-based coupling agents, surfactants, polymer dispersants, etc. can be used. , These can be used alone or in admixture of two or more.
上記有機ケイ素化合物としては、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、ブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、テトラエトキシシラン及びテトラメトキシシラン等のアルコキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ―アミノプロピルトリエトキシシラン、γ―グリシドキシプロピルトリメトキシシラン、γ―メルカプトプロピルトリメトキシシラン、γ―メタクロイルオキシプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−クロロプロピルトリメトキシシラン等のシラン系カップリング剤、ポリシロキサン、メチルハイドロジェンポリシロキサン、変性ポリシロキサン等のオルガノポリシロキサン等が挙げられる。 Examples of the organic silicon compound include methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, and octyltriethoxysilane. Alkoxysilanes such as silane, tetraethoxysilane and tetramethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, Silane-based couplings such as γ-methacloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-chloropropyltrimethoxysilane. Examples thereof include agents, polysiloxanes, methylhydrogenpolysiloxanes, modified polysiloxanes and other organopolysiloxanes.
上記有機チタン化合物としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、イソプロピルトリ（Ｎ−アミノエチル・アミノエチル）チタネート、トリス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルジオクチルパイロホスフェートチタネート、イソプロピルトリス（ドデシルベンゼンスルフォニル）チタネート、チタンテトラノルマルブトキシド、チタンテトラ−２−エチルヘキソキシド、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスファイトチタネート、テトラオクチルビス（ジトリデシルホスフェイト）チタネート、テトラ（２−２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスフェイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート等が挙げられる。 Examples of the organic titanium compound include isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, isopropyltri (N-aminoethyl / aminoethyl) titanate, and tris (dioctylpyrophosphate). ) Ethylene titanate, isopropyldioctylpyrophosphate titanate, isopropyltris (dodecylbenzenesulfonyl) titanate, titanium tetranormalbutoxide, titanium tetra-2-ethylhexoxide, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecyl) Phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, tetraoctylbis (ditridecylphosphate) titanate, tetra (2-2-diallyloxymethyl-1- Examples thereof include butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.
上記有機アルミ化合物としては、アセトアルコキシアルミニウムジイソプロピレート、アルミニウムジイソプロボキシモノエチルアセトアセテート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネート等が挙げられる。 Examples of the organic aluminum compound include acetalkoxyaluminum diisopropyrate, aluminum diisoproboxymonoethylacetate, aluminumtrisethylacetate, and aluminumtrisacetylacetonate.
上記有機ジルコニウム化合物としては、ジルコニウムテトラキスアセチルアセトネート、ジルコニウムジブトキシビスアセチルアセトネート、ジルコニウムテトラキスエチルアセトアセテート、ジルコニウムトリブトキシモノエチルアセトアセテート、ジルコニウムトリブトキシアセチルアセトネート等が挙げられる。 Examples of the organic zirconium compound include zirconium tetrakis acetyl acetonate, zirconium dibutoxybis acetyl acetonate, zirconium tetrakis ethyl acetoacetate, zirconium tributoxymonoethyl acetoacetate, and zirconium tributoxyacetyl acetonate.
上記界面活性剤としては、脂肪酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリールエーテル等のポリエチレングリコール型非イオン界面活性剤、ソルビタン脂肪酸エステル等の多価アルコール型非イオン界面活性剤等のノニオン性界面活性剤；アミン塩型カチオン系界面活性剤、第４級アンモニウム塩型カチオン系界面活性剤等のカオチン性界面活性剤；アルキルジメチルアミノ酢酸ベタインなどのアルキルベタイン、アルキルイミダゾリンなどの両性界面活性剤が挙げられる。 Examples of the surfactant include anionic surfactants such as fatty acid salts, sulfate ester salts, sulfonates and phosphate ester salts; polyethylene glycol type nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene aryl ether. Nonionic surfactants such as agents, polyhydric alcohol-type nonionic surfactants such as sorbitan fatty acid esters; chaotic surfactants such as amine salt-type cationic surfactants and quaternary ammonium salt-type cationic surfactants. Agents: Alkyl betaines such as alkyldimethylaminoacetic acid betaines and amphoteric surfactants such as alkyl imidazolines.
高分子分散剤としては、スチレン−アクリル酸共重合体、スチレン−マレイン酸共重合体、ポリカルボン酸及びその塩等を用いることができる。 As the polymer dispersant, a styrene-acrylic acid copolymer, a styrene-maleic acid copolymer, a polycarboxylic acid, a salt thereof, or the like can be used.
分散剤の添加量は、分散体中のチタン酸バリウム粒子粉末の総表面積に依存すると共に、チタン酸バリウム粒子粉末の分散体の用途及び分散剤の種類に応じて適宜調製すればよいが、一般的には、分散媒中のチタン酸バリウム粒子粉末に対して分散剤を０．０１〜１００重量％添加することによって、チタン酸バリウム粒子粉末を分散媒体中に均一且つ微細に分散させることができると共に、分散安定性も改善することができる。また、上記分散剤は、分散媒体に直接添加する他に、チタン酸バリウム粒子粉末に予め処理しておいてもよい。 The amount of the dispersant added depends on the total surface area of the barium titanate particle powder in the dispersion, and may be appropriately prepared according to the use of the dispersion of the barium titanate particle powder and the type of the dispersant. Specifically, by adding 0.01 to 100% by weight of the dispersant to the barium titanate particle powder in the dispersion medium, the barium titanate particle powder can be uniformly and finely dispersed in the dispersion medium. At the same time, the dispersion stability can be improved. In addition to being added directly to the dispersion medium, the dispersant may be pretreated with barium titanate particle powder.
次に、本発明に係る塗膜について述べる。 Next, the coating film according to the present invention will be described.
本発明に係る塗膜（またはシート）の作成は前述の分散体に樹脂を添加し、混合した後、バーコーターやスピンコーターなどのコーターを使用してＰＥＴフィルムなどのフィルム上に形成する。
使用する樹脂はアクリル樹脂、シリコーン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリメチルメタクリレート（ＰＭＭＡ）、ポリスチレン（ＰＳ）、ポリカーボネート（ＰＣ）等が一般的に用いられる。To prepare the coating film (or sheet) according to the present invention, a resin is added to the above-mentioned dispersion, mixed, and then formed on a film such as a PET film using a coater such as a bar coater or a spin coater.
As the resin to be used, acrylic resin, silicone resin, epoxy resin, polyester resin, polyimide resin, polymethylmethacrylate (PMMA), polystyrene (PS), polycarbonate (PC) and the like are generally used.
本発明に係る塗膜またはシートの全光線透過率は、好ましくは８５％以上、より好ましくは８８％以上であり、ヘイズは２％以下、好ましくは１％以下である。 The total light transmittance of the coating film or sheet according to the present invention is preferably 85% or more, more preferably 88% or more, and the haze is 2% or less, preferably 1% or less.
＜作用＞
本発明では、非常に微細な粒子でありながら、Ｂａイオン溶出量が少なく、高い誘電率を有し、耐酸性が高いチタン酸バリウム粒子粉末が得られている。透明性が求められる膜に用いられる粒子は、微細粒子であることのみならず、粒度分布がシャープである必要があり、本発明に係るチタン酸バリウム粒子粉末は、その条件を満たしている。固相法やシュウ酸塩法等によって得られる従来のチタン酸バリウム粒子では粉砕して超微細になったとしても粒度分布がブロードであり、この用途には不適である。<Action>
In the present invention, barium titanate particle powder having a small amount of Ba ion elution, a high dielectric constant, and high acid resistance is obtained, although it is a very fine particle. The particles used for the film for which transparency is required must not only be fine particles but also have a sharp particle size distribution, and the barium titanate particle powder according to the present invention satisfies this condition. Conventional barium titanate particles obtained by the solid-phase method, the oxalate method, or the like have a broad particle size distribution even if they are pulverized to become ultrafine, and are not suitable for this application.
微粒子合成に有利な水熱法においては、始めからＢａ欠損を生じさせるような粒子設計を行い、十分な洗浄で不要な化合物を一度取り除くのも一つの方法であり、これにより所望の特性を得ることができる。 In the hydrothermal method, which is advantageous for fine particle synthesis, one method is to design the particles so as to cause Ba deficiency from the beginning and remove unnecessary compounds once by sufficient washing, thereby obtaining desired properties. be able to.
また、本発明によれば、シリカなどの表面処理をすることで、よりＢａイオンの溶出量を低減することが出来る。さらには粒成長を起こさない温度で焼成しても、よりＢａイオンの溶出量が少なく、且つ、良好な屈折率・誘電率をもつチタン酸バリウム粒子が得られる。 Further, according to the present invention, the elution amount of Ba ions can be further reduced by surface-treating silica or the like. Further, even when firing at a temperature at which grain growth does not occur, barium titanate particles having a smaller amount of Ba ions eluted and having a good refractive index and dielectric constant can be obtained.
本発明の代表的な実施の形態は、次のとおりである。 Typical embodiments of the present invention are as follows.
チタン酸バリウム粒子粉末の一次粒子の平均粒径（ｘ）は、走査型電子顕微鏡（（株）日立製作所Ｓ−４３００）によって観察した写真（倍率５万倍）について、約５００個の粒子から粒子径を計測するとともに、粒度分布（σ）を求めた。変動係数は、前記粒度分布（σ）を前記一次粒子の平均粒径（ｘ）で除した値である（表１中の粒度分布（σ／ｘ）は変動係数を表す）。 The average particle size (x) of the primary particles of barium titanate particle powder is obtained from about 500 particles in a photograph (magnification: 50,000 times) observed by a scanning electron microscope (Hitachi Co., Ltd. S-4300). The diameter was measured and the particle size distribution (σ) was determined. The coefficient of variation is a value obtained by dividing the particle size distribution (σ) by the average particle size (x) of the primary particles (the particle size distribution (σ / x) in Table 1 represents the coefficient of variation).
チタン酸バリウム粒子粉末について、粉末Ｘ線回折で評価し、格子定数のｃ／ａ比、（１１１）面の半値幅（ＦＷＨＭ）を測定した。 The barium titanate particle powder was evaluated by powder X-ray diffraction, and the c / a ratio of the lattice constant and the full width at half maximum (FWHM) of the (111) plane were measured.
比表面積値はＢＥＴ法により測定した値で示した。 The specific surface area value is shown as a value measured by the BET method.
Ｂａ／Ｔｉ組成比は、「蛍光Ｘ線分析装置Ｓｉｍｕｌｔｉｘ１２」（（株）リガク製）を使用して測定した。 The Ba / Ti composition ratio was measured using a "fluorescent X-ray analyzer Simultix 12" (manufactured by Rigaku Co., Ltd.).
Ｂａ溶出濃度は５ｇのチタン酸バリウム粒子粉末を１００ｃｃの純水に分散させ、７分間煮沸した後、室温まで冷却して濾過し、その濾液をＩＣＰ発光分光分析装置（セイコー電子ＳＰＳ４００）で測定した。得られたＢａ濃度を２０倍した値を、粉体から水溶媒に溶出するＢａイオンの量、即ち、Ｂａ溶出量とした。 The Ba elution concentration was 5 g of barium titanate particle powder dispersed in 100 cc of pure water, boiled for 7 minutes, cooled to room temperature and filtered, and the filtrate was measured by an ICP emission spectrophotometer (Seiko Electronics SPS400). .. The value obtained by multiplying the obtained Ba concentration by 20 was defined as the amount of Ba ions eluted from the powder into the aqueous solvent, that is, the amount of Ba eluted.
チタン酸バリウム粒子粉末の表面被覆物の含有量は表面被覆元素の種類に応じた測定方法にて定量した。すなわち、Ｓｉ化合物に関しては蛍光Ｘ線測定装置（リガク ＳＭＸ６）、リン酸化合物、アルミニウム化合物、イットリウム化合物に関してはＩＣＰ発光分光分析装置（セイコー電子ＳＰＳ４００）、硫黄化合物は炭素‐硫黄分析装置（堀場製作所
ＥＭＩＡ−９２０）にて各被覆元素の含有量を測定した。また、Ｔｉ化合物に関してはチタン酸バリウム粒子粉末自体のＴｉ量との区別ができないことから、チタン酸バリウム粒子粉末への表面被覆前後の炭素量を炭素−硫黄分析装置（堀場製作所 ＥＭＩＡ−９２０）にて測定して、炭素量の差（表面処理後のＣ量−表面処理前のＣ量）により表面被覆物の含有量の定量を行った。The content of the surface coating of barium titanate particle powder was quantified by a measuring method according to the type of surface coating element. That is, a fluorescent X-ray measuring device (Rigaku SMX6) for Si compounds, an ICP emission spectroscopic analyzer (Seiko Electronics SPS400) for phosphoric acid compounds and aluminum compounds, and a carbon-sulfur analyzer for sulfur compounds (Horiba Seisakusho EMIA). The content of each coating element was measured in −920). In addition, since it is not possible to distinguish the Ti compound from the Ti content of the barium titanate particle powder itself, the carbon content before and after the surface coating on the barium titanate particle powder was applied to a carbon-sulfur analyzer (Horiba Seisakusho EMIA-920). The content of the surface coating was quantified based on the difference in carbon content (C amount after surface treatment-C amount before surface treatment).
チタン酸バリウム粒子粉末の比誘電率は下記評価方法によって測定した。 The relative permittivity of the barium titanate particle powder was measured by the following evaluation method.
即ち、チタン酸バリウム粒子粉末２．５ｇと濃度３ｗｔ％のポリビニルアルコール（ＰＶＡ）水溶液０．５ｇとを混合したものを、１００ｋｇ／ｃｍ２の圧力で圧粉し、直径２５ｍｍ、厚さ１〜２ｍｍの円盤状圧粉体を作製した。圧粉体は水分を含むため、５０℃の乾燥空気中に１２時間以上放置した。
乾燥後の圧粉体の重量と体積から、チタン酸バリウム粒子粉末、ＰＶＡおよび空隙の体積比率を求めた。なお、圧粉体は、チタン酸バリウム粒子粉末が４１〜５５ｖｏｌ％、ＰＶＡが０．１〜３ｖｏｌ％、残部が空隙となるように調整した。
得られた圧粉体について、Ａｇｉｌｅｎｔ社製インピーダンスアナライザー Ｅ４９９１Ａおよび誘電率測定フィクスチャー１６４５３Ａにより、室温約２５℃、湿度約４０％ＲＨの環境下で１０ＭＨｚにおける誘電率を測定した。得られた誘電率の測定結果には、チタン酸バリウム粒子粉末、ＰＶＡおよび空隙の各成分からの寄与を含んでいるため、本発明では対数混合則を用いて測定値からチタン酸バリウムのみの寄与を見積もった。また、表面被覆されたチタン酸バリウム粒子の誘電率は、表面処理成分も含めて複合粒子としての誘電率を対数混合則により見積もった。That is, a mixture of 2.5 g of barium titanate particle powder and 0.5 g of an aqueous solution of polyvinyl alcohol (PVA) having a concentration of 3 wt% was compacted at a pressure of 100 kg / cm 2 to have a diameter of 25 mm and a thickness of 1 to 2 mm. A disk-shaped green compact was prepared. Since the green compact contains water, it was left in dry air at 50 ° C. for 12 hours or more.
From the weight and volume of the green compact after drying, the volume ratio of barium titanate particle powder, PVA and voids was determined. The green compact was adjusted so that the barium titanate particle powder was 41 to 55 vol%, the PVA was 0.1 to 3 vol%, and the balance was void.
The obtained green compact was measured for dielectric constant at 10 MHz in an environment of room temperature of about 25 ° C. and humidity of about 40% RH by using an impedance analyzer E4991A manufactured by Agent and a permittivity measurement fixture 16453A. Since the obtained measurement result of the dielectric constant includes contributions from each component of barium titanate particle powder, PVA, and voids, in the present invention, the contribution of barium titanate only from the measured values using the logarithmic mixing law. Was estimated. In addition, the permittivity of the surface-coated barium titanate particles was estimated by the logarithmic mixing rule as the dielectric constant of the composite particles including the surface treatment component.
［実施例１］
水酸化バリウム八水塩（関東化学（株）製、９７％Ｂａ（ＯＨ）２・８Ｈ２Ｏ試薬特級）１．１２ｋｇを水に溶解、精製したものを、塩化チタン水溶液６８８ｇに滴下・中和して水酸化チタンコロイドを得た。次に、水酸化バリウム八水塩１．２８ｋｇを水に溶解、精製したものを温度７０℃、ｐＨ１２．５で窒素雰囲気の水熱反応容器中に保持した。次に、前記水酸化チタンコロイドを前記水酸化バリウム水溶液に２分間かけて投入した。該混合溶液を１００℃で０．７５時間かけて水熱反応を行ってチタン酸バリウムを生成した。室温まで冷却した後、ヌッチェで濾液にＢａイオンが認められなくなるまで水洗し、さらに温水でｐＨ＝７となるまで洗浄した。その後、濾過、１５０℃で乾燥を行ってチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末のＢａ／Ｔｉ比は０．８７４モル比であり、平均粒径は３３ｎｍであった。得られたチタン酸バリウム粒子粉末の電子顕微鏡写真を図１に示す。[Example 1]
Barium hydroxide octahydrate (Kanto Chemical Co., Ltd., 97% Ba (OH) 2 · 8H 2 O guaranteed reagent) dissolved 1.12kg of water, those purified, dropwise, neutralized chloride aqueous solution of titanium 688g To obtain a titanium hydroxide colloid. Next, 1.28 kg of barium hydroxide octahydrate was dissolved in water, and the purified product was kept in a hydrothermal reaction vessel in a nitrogen atmosphere at a temperature of 70 ° C. and a pH of 12.5. Next, the titanium hydroxide colloid was added to the barium hydroxide aqueous solution over 2 minutes. The mixed solution was hydrothermally reacted at 100 ° C. for 0.75 hours to produce barium titanate. After cooling to room temperature, the filtrate was washed with water until no Ba ions were observed in the filtrate, and further washed with warm water until pH = 7. Then, it was filtered and dried at 150 degreeC to obtain barium titanate particle powder. The obtained barium titanate particle powder had a Ba / Ti ratio of 0.874 mol and an average particle size of 33 nm. An electron micrograph of the obtained barium titanate particle powder is shown in FIG.
［実施例２］
実施例１に対し、水熱反応の反応時間を８時間に変更し、洗浄ｐＨを６．５として、Ｂａ／Ｔｉ比は０．９６２モル比で平均粒径が５２ｎｍのチタン酸バリウム粒子粉末を得た。水熱反応条件の負荷を高めることで、平均粒径は増加し、高いＢａ／Ｔｉ組成比のチタン酸バリウム粒子粉末であった。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 2]
Barium titanate particle powder having a Ba / Ti ratio of 0.962 mol and an average particle size of 52 nm was prepared by changing the reaction time of the hydrothermal reaction to 8 hours and setting the washing pH to 6.5 with respect to Example 1. Obtained. By increasing the load under the hydrothermal reaction conditions, the average particle size was increased, and the barium titanate particle powder having a high Ba / Ti composition ratio was obtained. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例３］
実施例１に対し、水熱反応の反応温度を７０℃に変更し、洗浄ｐＨを６．５として平均粒径が１６ｎｍのチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 3]
With respect to Example 1, the reaction temperature of the hydrothermal reaction was changed to 70 ° C., the washing pH was 6.5, and barium titanate particle powder having an average particle size of 16 nm was obtained. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例４］
実施例１で得られたチタン酸バリウム粒子粉末を少量の水で解膠し、撹拌しながら３号ケイ酸ナトリウム溶液（水ガラス３号）をチタン酸バリウムに対し１重量％で添加し、酢酸でｐＨを６．５に調整して、ヌッチェで濾液にＢａイオンが認められなくなるまで水洗し、濾過、乾燥を行ってＢａ／Ｔｉ比が０．７９０モル比のチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末について実施例１と同様にして評価を行った。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 4]
The barium titanate particle powder obtained in Example 1 was deflated with a small amount of water, and a No. 3 sodium silicate solution (water glass No. 3) was added in an amount of 1% by weight based on barium titanate while stirring to obtain acetic acid. The pH was adjusted to 6.5, and the filtrate was washed with water until no Ba ions were observed, filtered, and dried to obtain barium titanate particle powder having a Ba / Ti ratio of 0.790 mol. .. The obtained barium titanate particle powder was evaluated in the same manner as in Example 1. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例５］
実施例１で得られたチタン酸バリウム粒子粉末にアルキルシラン系シランカップリング剤（商品名：ＴＳＬ−８２４１）を５重量％混合機で撹拌しながら添加して表面処理したチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 5]
A surface-treated barium titanate particle powder was prepared by adding an alkylsilane-based silane coupling agent (trade name: TSL-8241) to the barium titanate particle powder obtained in Example 1 with stirring with a 5% by weight mixer. Obtained. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例６］
実施例１のチタン酸バリウム粒子粉末を３００℃の温度下で熱処理した。得られたチタン酸バリウム粒子粉末について、誘電率、ｃ／ａ比、半値幅、Ｂａ溶出量および比表面積を、実施例１に記載と同様の方法で評価を行った。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 6]
The barium titanate particle powder of Example 1 was heat-treated at a temperature of 300 ° C. The obtained barium titanate particle powder was evaluated for dielectric constant, c / a ratio, full width at half maximum, Ba elution amount and specific surface area in the same manner as described in Example 1. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例７］
実施例２のチタン酸バリウム粒子粉末を５００℃の温度下で熱処理した。得られたチタン酸バリウム粒子粉末について、誘電率、ｃ／ａ比、半値幅、Ｂａ溶出量および比表面積を、実施例１に記載と同様の方法で評価を行った。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 7]
The barium titanate particle powder of Example 2 was heat-treated at a temperature of 500 ° C. The obtained barium titanate particle powder was evaluated for dielectric constant, c / a ratio, full width at half maximum, Ba elution amount and specific surface area in the same manner as described in Example 1. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例８］
実施例１のチタン酸バリウム粒子粉末を５００℃の温度下で熱処理し、得られた被処理チタン酸バリウム粒子粉末を１５重量％の濃度で純水に解膠し、得られたスラリーをヌッチェで濾液にＢａイオンが認められなくなるまで水洗し、さらに温水でｐＨ＝７となるまで洗浄した。その後、濾過、乾燥を行ってチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 8]
The barium titanate particle powder of Example 1 was heat-treated at a temperature of 500 ° C., the obtained barium titanate particle powder to be treated was pulverized in pure water at a concentration of 15% by weight, and the obtained slurry was washed with Nutche. The filtrate was washed with water until no Ba ions were observed, and further washed with warm water until pH = 7. Then, it was filtered and dried to obtain barium titanate particle powder. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例９］
水酸化バリウム八水塩（関東化学（株）製、９７％Ｂａ（ＯＨ）２・８Ｈ２Ｏ試薬特級）１．１２ｋｇを水に溶解、精製したものを、塩化チタン水溶液６８８ｇに滴下・中和して水酸化チタンコロイドを得た。次に、水酸化バリウム八水塩１．２８ｋｇを水に溶解、精製したものを温度７０℃、ｐＨ１２．５で窒素雰囲気の水熱反応容器中に保持した。次に、前記水酸化チタンコロイドを前記水酸化バリウム水溶液に２分間かけて投入した。該混合溶液を１００℃で０．７５時間かけて水熱反応を行ってチタン酸バリウムを生成した。室温まで冷却した後、ヌッチェで濾液を９００μＳ／ｃｍまで水洗した後、硫酸アルミニウムをアルミニウム換算で１重量％、徐々に添加してコーティングした。その後、濾過、乾燥を行ってアルミニウム化合物で被覆したチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 9]
Barium hydroxide octahydrate (Kanto Chemical Co., Ltd., 97% Ba (OH) 2 · 8H 2 O guaranteed reagent) dissolved 1.12kg of water, those purified, dropwise, neutralized chloride aqueous solution of titanium 688g To obtain a titanium hydroxide colloid. Next, 1.28 kg of barium hydroxide octahydrate was dissolved in water, and the purified product was kept in a hydrothermal reaction vessel in a nitrogen atmosphere at a temperature of 70 ° C. and a pH of 12.5. Next, the titanium hydroxide colloid was added to the barium hydroxide aqueous solution over 2 minutes. The mixed solution was hydrothermally reacted at 100 ° C. for 0.75 hours to produce barium titanate. After cooling to room temperature, the filtrate was washed with water to 900 μS / cm with Nutche, and then aluminum sulfate was gradually added in an amount of 1% by weight in terms of aluminum for coating. Then, it was filtered and dried to obtain barium titanate particle powder coated with an aluminum compound. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１０］
添加剤を塩化イットリウムにした以外は実施例９と同様の手法でイットリウム化合物で被覆されたチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 10]
Barium titanate particle powder coated with an yttrium compound was obtained in the same manner as in Example 9 except that the additive was yttrium chloride. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１１］
添加剤を硫酸ナトリウムにし、添加量を硫黄換算０．１ｗｔ％にする以外は実施例９と同様の手法で硫酸根で被覆されたチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 11]
Barium titanate particle powder coated with sulfate root was obtained by the same method as in Example 9 except that the additive was sodium sulfate and the addition amount was 0.1 wt% in terms of sulfur. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１２］
添加剤をリン酸にした以外は実施例９と同様の手法でリン酸で被覆されたチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 12]
Barium titanate particle powder coated with phosphoric acid was obtained in the same manner as in Example 9 except that the additive was phosphoric acid. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１３］
実施例１で得られたチタン酸バリウム粒子粉末に有機チタン化合物 テトライソプロピルビス（ジオクチルホスファイト）チタネートを表面処理前後のＣ量差が０．５重量％となるように混合機で撹拌しながら添加して表面処理したチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 13]
To the barium titanate particle powder obtained in Example 1, the organic titanium compound tetraisopropylbis (dioctylphosphite) titanate was added while stirring with a mixer so that the difference in C amount before and after the surface treatment was 0.5% by weight. The surface-treated barium titanate particle powder was obtained. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１４］
実施例１で得られたチタン酸バリウム粒子粉末に有機チタン化合物 テトライソプロピルビス（ジオクチルホスファイト）チタネートを表面処理前後のＣ量差が１重量％となるように混合機で撹拌しながら添加して表面処理したチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Example 14]
To the barium titanate particle powder obtained in Example 1, the organic titanium compound tetraisopropylbis (dioctylphosphite) titanate was added while stirring with a mixer so that the difference in C amount before and after the surface treatment was 1% by weight. A surface-treated barium titanate particle powder was obtained. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［比較例１］
実施例１の途中の工程で得られた水熱反応後のチタン酸バリウム含有スラリーを少量の水で水洗し、乾燥させてチタン酸バリウム粒子粉末を得た。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Comparative Example 1]
The barium titanate-containing slurry obtained in the middle step of Example 1 after the hydrothermal reaction was washed with a small amount of water and dried to obtain barium titanate particle powder. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［比較例２］
実施例１で得られた平均粒径が３３ｎｍのチタン酸バリウム粒子粉末を７００℃の温度下で熱処理し、誘電率、ｃ／ａ比、半値幅および比表面積を、実施例１に記載と同様の方法で評価を行った。高温での熱処理により、比誘電率が大きく増加しているが、平均粒径も大きく増加している。そのため、後述する比較例５から明らかなように、シートにおける全光線透過率およびヘイズが悪化する。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Comparative Example 2]
The barium titanate particle powder having an average particle size of 33 nm obtained in Example 1 is heat-treated at a temperature of 700 ° C., and the dielectric constant, c / a ratio, half width and specific surface area are the same as those described in Example 1. The evaluation was performed by the method of. Due to the heat treatment at high temperature, the relative permittivity is greatly increased, but the average particle size is also greatly increased. Therefore, as is clear from Comparative Example 5 described later, the total light transmittance and haze of the sheet deteriorate. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［比較例３］
固相法により作製されたチタン酸バリウム粒子粉末について、誘電率、ｃ／ａ比、半値幅、Ｂａ溶出量および比表面積を、実施例１に記載と同様の方法で評価を行った。得られたチタン酸バリウム粒子粉末の諸特性を表１に示す。[Comparative Example 3]
The dielectric constant, c / a ratio, half width, Ba elution amount, and specific surface area of the barium titanate particle powder produced by the solid phase method were evaluated by the same method as described in Example 1. Table 1 shows various characteristics of the obtained barium titanate particle powder.
［実施例１５］
実施例１で得られたチタン酸バリウム粒子粉末を縦型ビーズミル（コトブキ技研工業株式会社製「ウルトラアペックスミル ＵＡＭ−０５」）のジルコニア製０．５リットル攪拌容器にジルコニアビーズ（粒径５０μｍ）を攪拌容器の７０ｖｏｌ％になるように入れ、分散剤としてＥＤ１５３（楠本化成製）、溶媒のＰＧＭＥＡを混合した溶液を添加し、循環させながら１時間分散させて、チタン酸バリウム粒子粉末の分散体を得た。
［実施例１６］
得られた分散体を、アクリル樹脂（ＳＢ−１９３岐阜セラツク製）と、チタン酸バリウム／バインダ（分散剤含む）＝６／４の割合にて混合し、バーコーターにて、ルミラーＵ−４６（東レ製）上に塗布し、膜厚＝３μｍ程度の塗膜を作製した。[Example 15]
Barium titanate particle powder obtained in Example 1 was placed in a 0.5 liter stirring container made of zirconia in a vertical bead mill (“Ultra Apex Mill UAM-05” manufactured by Kotobuki Engineering & Research Co., Ltd.) with zirconia beads (particle size 50 μm). Add a solution containing ED153 (manufactured by Kusumoto Kasei) as a dispersant and PGMEA as a solvent to make up to 70 vol% of the stirring container, and disperse for 1 hour while circulating to obtain a dispersion of barium titanate particle powder. Obtained.
[Example 16]
The obtained dispersion was mixed with an acrylic resin (manufactured by SB-193 Gifu Seratsk) at a ratio of barium titanate / binder (including dispersant) = 6/4, and Lumirer U-46 (with a bar coater). (Made by Toray) was applied to prepare a coating film having a film thickness of about 3 μm.
［実施例１７］
実施例３のチタン酸バリウム粒子粉末を実施例１５、実施例１６の方法に従い、シート化を行った。得られたシートの諸特性を表２に示す。[Example 17]
The barium titanate particle powder of Example 3 was sheeted according to the methods of Examples 15 and 16. Table 2 shows various characteristics of the obtained sheet.
［実施例１８］
実施例４のチタン酸バリウム粒子粉末を実施例１５、実施例１６の方法に従い、シート化を行った。得られたシートの諸特性を表２に示す。[Example 18]
The barium titanate particle powder of Example 4 was sheeted according to the methods of Examples 15 and 16. Table 2 shows various characteristics of the obtained sheet.
［実施例１９］
実施例６のチタン酸バリウム粒子粉末を実施例１５、実施例１６の方法に従い、シート化を行った。得られたシートの諸特性を表２に示す。[Example 19]
The barium titanate particle powder of Example 6 was sheeted according to the methods of Examples 15 and 16. Table 2 shows various characteristics of the obtained sheet.
［比較例４］
比較例１のチタン酸バリウム粒子粉末を実施例１５、実施例１６の方法に従い、シート化を行った。得られたシートの諸特性を表２に示す。[Comparative Example 4]
The barium titanate particle powder of Comparative Example 1 was sheeted according to the methods of Examples 15 and 16. Table 2 shows various characteristics of the obtained sheet.
［比較例５］
比較例２のチタン酸バリウム粒子粉末を実施例１５、実施例１６の方法に従い、シート化を行った。得られたシートの諸特性を表２に示す。[Comparative Example 5]
The barium titanate particle powder of Comparative Example 2 was sheeted according to the methods of Examples 15 and 16. Table 2 shows various characteristics of the obtained sheet.
表２から明らかなとおり、本発明に係るチタン酸バリウム粒子粉末（実施例）を用いた塗膜（実施例１６〜１９）では、全光透過率が８５％以上であって、ヘイズも１％以下であり、透明性に優れることが明らかになった。 As is clear from Table 2, in the coating film (Examples 16 to 19) using the barium titanate particle powder (Example) according to the present invention, the total light transmittance is 85% or more and the haze is 1%. It was revealed that it is excellent in transparency.
本発明に係るチタン酸バリウム粒子粉末は、凝集が抑制され分散性に優れているので、各種誘電材料に好適に用いることができる。特に積層セラミックコンデンサ用途として、ニッケルの内部電極層で焼結遅延を目的とした材料には好適で、特にニッケルが微細になると、本発明に係るチタン酸バリウム粒子粉末は殊に有用である。また、本発明に係るチタン酸バリウム粒子粉末は高い誘電率を有するので、チタン酸バリウム粒子粉末と透明樹脂を混合させる場合、従来よりもチタン酸バリウム粒子粉末の使用量を抑えることができると考えられ、光学フィルム用途に必要とされる透明性の確保が容易になる。 Since the barium titanate particle powder according to the present invention suppresses aggregation and has excellent dispersibility, it can be suitably used for various dielectric materials. In particular, it is suitable for a material for delaying sintering in the internal electrode layer of nickel as a multilayer ceramic capacitor application, and especially when nickel becomes fine, the barium titanate particle powder according to the present invention is particularly useful. Further, since the barium titanate particle powder according to the present invention has a high dielectric constant, it is considered that the amount of the barium titanate particle powder used can be reduced as compared with the conventional case when the barium titanate particle powder and the transparent resin are mixed. Therefore, it becomes easy to secure the transparency required for optical film applications.
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| JP5283995B2 (en) * | 2008-07-18 | 2013-09-04 | 日本化学工業株式会社 | Modified perovskite complex oxide, method for producing the same, and complex dielectric material |
| CN101712557A (en) * | 2008-09-30 | 2010-05-26 | Tdk株式会社 | Method for synthesizing powder and electronic component manufacturing mehtod |
| JP2010105904A (en) * | 2008-09-30 | 2010-05-13 | Tdk Corp | Fine particle synthesis method and electronic-component manufacturing method |
| CN102459083A (en) * | 2009-06-05 | 2012-05-16 | Cqv株式会社 | Barium titanate powder coated with an oxide layer, and a production method therefor |
| JP5663907B2 (en) | 2010-03-09 | 2015-02-04 | 株式会社村田製作所 | Manufacturing method of barium titanate ceramic |
| JP6368246B2 (en) | 2012-11-13 | 2018-08-01 | 関東電化工業株式会社 | Method for producing coated barium titanate fine particles |
| CN106458630A (en) * | 2014-06-13 | 2017-02-22 | 户田工业株式会社 | Barium titanate fine particle powder, dispersion, and coating film |
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