JP5494231B2 - Titanium dioxide particles and method for producing the same - Google Patents
Titanium dioxide particles and method for producing the same Download PDFInfo
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- JP5494231B2 JP5494231B2 JP2010118648A JP2010118648A JP5494231B2 JP 5494231 B2 JP5494231 B2 JP 5494231B2 JP 2010118648 A JP2010118648 A JP 2010118648A JP 2010118648 A JP2010118648 A JP 2010118648A JP 5494231 B2 JP5494231 B2 JP 5494231B2
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- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 217
- 239000002245 particle Substances 0.000 title claims description 126
- 239000004408 titanium dioxide Substances 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011164 primary particle Substances 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 18
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010304 firing Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000001186 cumulative effect Effects 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- -1 hexametaphosphate Chemical compound 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- VIESAWGOYVNHLV-UHFFFAOYSA-N 1,3-dihydropyrrol-2-one Chemical compound O=C1CC=CN1 VIESAWGOYVNHLV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000010333 wet classification Methods 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 229960002816 potassium chloride Drugs 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 229940093914 potassium sulfate Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940073490 sodium glutamate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、二酸化チタン粒子及びその製造方法に関する。 The present invention relates to titanium dioxide particles and a method for producing the same.
酸化チタン（二酸化チタン：ＴｉＯ２）は、白色顔料や紫外線散乱剤などの原料として広く使用されている物質である。酸化チタンは、アナタース（アナターゼ：Ａｎａｔａｓｅ）型、ルチル（Ｒｕｔｉｌｅ）型、ブルカイト（Ｂｒｏｏｋｉｔｅ）型の３種の結晶形態を採り得ることが知られているが、なかでもアナタース型酸化チタンは、触媒、光触媒、電子材料などの原料として工業的に有用な物質である。 Titanium oxide (titanium dioxide: TiO 2 ) is a substance that is widely used as a raw material for white pigments and ultraviolet scattering agents. It is known that titanium oxide can take three types of crystal forms of anatase (anatase) type, rutile type, and brookite type. Among these, anatase type titanium oxide is a catalyst, Industrially useful as a raw material for photocatalysts and electronic materials.
アナタース型二酸化チタンとしては、市販のものも含め、一次粒子径が０．３μｍ以下のものが知られている（例えば特許文献１参照）。一次粒子の凝集体（二次粒子）として、粒径の大きな二酸化チタンも存在する（例えば特許文献２参照）。また、ルチル型としては、粒径の大きなものも知られている。 As the anatase type titanium dioxide, those having a primary particle diameter of 0.3 μm or less are known including those on the market (see, for example, Patent Document 1). There is also titanium dioxide having a large particle size as an aggregate (secondary particle) of primary particles (see, for example, Patent Document 2). In addition, a rutile type having a large particle size is also known.
また、アナタース型二酸化チタンを得るために、水酸化チタンにリン酸塩を添加してルチル型への転移を抑制する方法も知られているが（例えば、特許文献３）、一方、リン酸塩は一次粒子の成長を妨げる働きも有している。従って、得られるアナタース型二酸化チタンは、やはり一次粒子径が０．３μｍ以下の小粒径のものである。 In addition, in order to obtain anatase type titanium dioxide, a method of suppressing the transition to the rutile type by adding a phosphate to titanium hydroxide is also known (for example, Patent Document 3). Also has a function of hindering the growth of primary particles. Therefore, the obtained anatase-type titanium dioxide has a small particle size with a primary particle size of 0.3 μm or less.
粒径の大きなアナタース型二酸化チタンを得るのが困難であった一番の理由は、一般的に知られているように、一定温度を超えるとアナタース型からルチル型への転移が進行することにある。二酸化チタンの一次粒子径を成長させるには、通常高温での焼成が必要である。そのため、一次粒子径の大きな二酸化チタンとしては、ルチル型以外のものを得ることは困難であると一般的には考えられてきた。 The main reason why it was difficult to obtain anatase-type titanium dioxide with a large particle size was that the transition from anatase-type to rutile-type progressed above a certain temperature, as is generally known. is there. In order to grow the primary particle diameter of titanium dioxide, firing at a high temperature is usually required. Therefore, it has been generally considered that it is difficult to obtain a titanium dioxide having a large primary particle size other than the rutile type.
加えて、粒子を成長させるために高温で焼成すると、焼成物は粒子同士が焼結し、粒子形状や粒度分布が不ぞろいとなるという問題があった。さらに焼成物は非常に硬く粉砕が困難であり、簡便な方法で工業的に有用な粉体を得るのは困難であった。 In addition, when fired at a high temperature to grow the particles, the fired product has a problem that the particles are sintered with each other and the particle shape and particle size distribution are uneven. Further, the fired product is very hard and difficult to grind, and it is difficult to obtain industrially useful powder by a simple method.
上記のような事情を踏まえ、本願発明は、ルチル型の存在量が極めて少ないアナタース型二酸化チタン粒子であって、一次粒子径が比較的大きく、粒度分布のバラつきが少ない、工業的にも有用な二酸化チタン粒子を提供することを目的とする。 In light of the circumstances as described above, the present invention is anatase-type titanium dioxide particles having an extremely small rutile-type abundance, which has a relatively large primary particle size and little variation in particle size distribution, and is industrially useful. An object is to provide titanium dioxide particles.
すなわち本発明の第一の態様は、
結晶構造がアナタース型であり、
電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍであり、
その粒度分布はＤ９０／Ｄ１０で３．０以下である
二酸化チタン粒子に関する。
That is, the first aspect of the present invention is:
The crystal structure is anatase type,
The primary particle diameter by measuring the fixed direction diameter with an electron microscope is 0.5 μm to 5.0 μm,
The particle size distribution relates to titanium dioxide particles having a D90 / D10 of 3.0 or less.
好ましい実施形態においては、上記二酸化チタン粒子が含有する全二酸化チタン成分中の、ルチル型結晶の含有率は１０．０質量％以下である。 In preferable embodiment, the content rate of a rutile type crystal | crystallization in the total titanium dioxide component which the said titanium dioxide particle contains is 10.0 mass% or less.
別の好ましい実施形態において、上記二酸化チタン粒子は、結晶構造がアナタース型の二酸化チタン１００質量部と、
Ｐ２Ｏ５換算で０．５〜１０．０質量部のリンとを含有する粒子状組成物である。
In another preferred embodiment, the titanium dioxide particles have a crystal structure of 100 parts by mass of anatase-type titanium dioxide,
It is a particulate composition containing 0.5 to 10.0 parts by mass of phosphorus in terms of P 2 O 5 .
本発明の第二の態様は、（ａ）ＴｉＯ２として１００質量部の水酸化チタンに、Ｎａ、Ｋ及びＣｓからなる群から選択される少なくとも１種のアルカリ金属化合物を、アルカリ金属酸化物として総量で１．０〜１１．０質量部添加して、混合する工程と、
（ｂ）リン酸又はその塩を、Ｐ２Ｏ５として０．５〜１０．０質量部添加し、混合する工程と、
（ｃ）得られた混合物を７５０〜１２００℃で焼成して、二酸化チタンを得る工程と
を含む、上記二酸化チタン粒子を製造する方法に関する。
According to a second aspect of the present invention, (a) 100 parts by mass of titanium hydroxide as TiO 2 and at least one alkali metal compound selected from the group consisting of Na, K and Cs as an alkali metal oxide Adding 1.0 to 11.0 parts by mass in a total amount and mixing,
(B) adding 0.5 to 10.0 parts by mass of phosphoric acid or a salt thereof as P 2 O 5 and mixing;
(C) It is related with the method of manufacturing the said titanium dioxide particle including baking the obtained mixture at 750-1200 degreeC, and obtaining a titanium dioxide.
本発明の二酸化チタン粒子の製造方法は、高温での焼成を経てもルチル型への転移がほとんど起こらない、という利点を有する。その結果得られる本発明の二酸化チタン粒子は、一次粒子径が０．５μｍ〜５．０μｍであるという、従来のアナタース型二酸化チタンよりも大きな粒径を有し、かつ粒子形状や粒径の均一性が高いアナタース型二酸化チタン粒子である。このような二酸化チタン粒子は塗料や光触媒材料等への適用が期待でき、工業的に有用である。 The method for producing titanium dioxide particles of the present invention has the advantage that almost no transition to the rutile type occurs even after firing at a high temperature. The resulting titanium dioxide particles of the present invention have a primary particle size of 0.5 μm to 5.0 μm, a particle size larger than that of conventional anatase-type titanium dioxide, and a uniform particle shape and particle size. It is anatase type titanium dioxide particles with high properties. Such titanium dioxide particles can be expected to be applied to paints, photocatalyst materials and the like, and are industrially useful.
以下に本発明を詳述する。
上述の通り、本発明のアナタース型二酸化チタン粒子は、（１）結晶構造がアナタース型であること、（２）電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍであること、（３）粒度分布はＤ９０／Ｄ１０で３．０以下であること、といった特徴を有している。
The present invention is described in detail below.
As described above, the anatase-type titanium dioxide particles of the present invention have (1) a crystal structure of anatase type, and (2) a primary particle diameter of 0.5 μm to 5 μm by measuring a unidirectional diameter with an electron microscope. 0.03 μm, and (3) the particle size distribution is D90 / D10 of 3.0 or less.
二酸化チタンの結晶型には、ルチル型、アナタース（アナターゼ）型、ブルッカイト型の３種類があり、このうち工業的に利用されているのはルチル型とアナタース型の２種類である。上述のように、二酸化チタンの一次粒子を成長させるためには、高温での焼成が必要であるが、アナタース型二酸化チタンは、一定温度以上の高温下ではより熱的に安定なルチル型に転移するという性質を本質的に有している。またこの転移は不可逆反応であり、一旦ルチル型に転移してしまうと、再度アナタース型に戻ることはない。このように、低温で安定なアナタース型の結晶構造を維持したまま、高温において一次粒子を成長させることは一般的には困難である。 There are three types of crystal forms of titanium dioxide: rutile type, anatase (anatase) type, and brookite type. Of these, two types are used industrially: rutile type and anatase type. As mentioned above, in order to grow the primary particles of titanium dioxide, firing at a high temperature is necessary, but anatase-type titanium dioxide transitions to a more thermally stable rutile type at a high temperature above a certain temperature. It has the nature of This transfer is an irreversible reaction, and once transferred to the rutile type, it does not return to the anatase type again. As described above, it is generally difficult to grow primary particles at a high temperature while maintaining a stable anatase-type crystal structure at a low temperature.
本発明者らは、アナタース型二酸化チタンの原料である水酸化チタンを焼成する際、特定の成分を添加することで、ルチル型への転移の抑制と、粒子の成長が両立することを見出した。具体的に以下に説明する。 The inventors of the present invention have found that, when a titanium hydroxide which is a raw material for anatase-type titanium dioxide is fired, addition of a specific component makes it possible to suppress the transition to the rutile type and to grow the particles. . This will be specifically described below.
（本発明のアナタース型二酸化チタン粒子及びその製造方法）
本発明のアナタース型二酸化チタンは、（ａ）ＴｉＯ２として１００質量部の水酸化チタンに、Ｎａ、Ｋ及びＣｓからなる群から選択される少なくとも１種のアルカリ金属の化合物を、アルカリ金属酸化物として総量で１．０〜１１．０質量部添加して、混合する工程と、（ｂ）リン酸又はその塩を、Ｐ２Ｏ５として０．５〜１０．０質量部添加し、混合する工程と、（ｃ）得られた混合物を７５０〜１２００℃で焼成して、二酸化チタンを得る工程とを含む。この方法により、電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍであって、その粒度分布はＤ９０／Ｄ１０で３．０以下であるアナタース型二酸化チタン粒子を得ることができる。このようにして得られるアナタース型二酸化チタン粒子及び該二酸化チタン粒子を製造する方法は、それぞれ本発明の一態様を構成する。
(Anatase type titanium dioxide particles of the present invention and production method thereof)
The anatase-type titanium dioxide of the present invention comprises (a) 100 parts by mass of titanium hydroxide as TiO 2 and at least one alkali metal compound selected from the group consisting of Na, K and Cs. Adding 1.0 to 11.0 parts by mass in total and mixing, and (b) adding 0.5 to 10.0 parts by mass of phosphoric acid or a salt thereof as P 2 O 5 and mixing. And (c) firing the obtained mixture at 750 to 1200 ° C. to obtain titanium dioxide. By this method, anatase-type titanium dioxide particles having a primary particle diameter of 0.5 μm to 5.0 μm by measuring a fixed direction diameter with an electron microscope and a particle size distribution of D90 / D10 of 3.0 or less. Can be obtained. The anatase-type titanium dioxide particles thus obtained and the method for producing the titanium dioxide particles each constitute one aspect of the present invention.
工程（ａ）においては、二酸化チタンの原料である水酸化チタンに、Ｎａ、Ｋ及びＣｓからなる群から選択される少なくとも１種のアルカリ金属の化合物を添加し、混合する。 In step (a), at least one alkali metal compound selected from the group consisting of Na, K and Cs is added to and mixed with titanium hydroxide which is a raw material of titanium dioxide.
水酸化チタンとは、一般的に、組成式：Ｈ２ＴｉＯ３で表される化合物である。「メタチタン酸」、または単に「チタン酸」と呼ばれることもあり、化学式では、ＴｉＯ（ＯＨ）２等のように表される公知の化合物である。 Titanium hydroxide is generally a compound represented by the composition formula: H 2 TiO 3 . It is sometimes called “metatitanic acid” or simply “titanic acid”, and is a known compound represented by a chemical formula such as TiO (OH) 2 .
工程（ａ）で添加する化合物に含まれる、Ｎａ、Ｋ、Ｃｓというアルカリ金属は、二酸化チタンを焼成するときに、融剤として作用し、一次粒子の成長を促進させる物質であるものと推測される。 The alkali metals Na, K, and Cs contained in the compound added in step (a) are presumed to be substances that act as a fluxing agent and promote the growth of primary particles when titanium dioxide is baked. The
上記アルカリ金属の化合物は特に限定されないが、例えば水酸化ナトリウム、塩化ナトリウム、硫酸ナトリウム、硫酸水素ナトリウム、硝酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、ギ酸ナトリウム、酢酸ナトリウム、チオ硫酸ナトリウム、クエン酸ナトリウム、シュウ酸ナトリウム、グルタミン酸ナトリウム、アスコルビン酸ナトリウム等のナトリウム塩、水酸化カリウム、塩化カリウム、硫酸カリウム、硫酸水素カリウム、硝酸カリウム、炭酸カリウム、炭酸水素カリウム、酢酸カリウム、クエン酸カリウム、シュウ酸カリウム等のカリウム塩、水酸化セシウム、塩化セシウム、硫酸セシウム、硝酸セシウム、炭酸セシウム等のセシウム塩が挙げられる。なかでも、塩化ナトリウム、塩化カリウム、塩化セシウム等の塩化物、硫酸ナトリウム、硫酸カリウム、硫酸セシウム等の硫酸塩が入手が容易な点で好ましい。 The alkali metal compound is not particularly limited. For example, sodium hydroxide, sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium nitrate, sodium carbonate, sodium hydrogen carbonate, sodium formate, sodium acetate, sodium thiosulfate, sodium citrate, Sodium salts such as sodium oxalate, sodium glutamate, sodium ascorbate, potassium hydroxide, potassium chloride, potassium sulfate, potassium hydrogen sulfate, potassium nitrate, potassium carbonate, potassium bicarbonate, potassium acetate, potassium citrate, potassium oxalate, etc. Examples thereof include cesium salts such as potassium salt, cesium hydroxide, cesium chloride, cesium sulfate, cesium nitrate, and cesium carbonate. Of these, chlorides such as sodium chloride, potassium chloride, and cesium chloride, and sulfates such as sodium sulfate, potassium sulfate, and cesium sulfate are preferable because they are easily available.
アルカリ金属の化合物の添加量は、アルカリ金属酸化物として、即ちアルカリ金属の酸化物に換算した質量として、ＴｉＯ２として１００質量部の水酸化チタンに対して総量で１．０〜１１．０質量部添加する。上記添加量は、好ましくは１．０〜５．０質量部であり、より好ましくは１．０〜３．０質量部である。 The addition amount of the alkali metal compound is 1.0 to 11.0 mass in total with respect to 100 parts by mass of titanium hydroxide as TiO 2 as the mass converted to the alkali metal oxide, that is, the alkali metal oxide. Add part. The addition amount is preferably 1.0 to 5.0 parts by mass, and more preferably 1.0 to 3.0 parts by mass.
混合方法は特に限定されず、例えば回転翼や回転槽、ミキサー、ボールミル等の公知の混合機を用いて、乾式又は湿式で混合すれば良い。 The mixing method is not particularly limited. For example, the mixing method may be dry or wet using a known mixer such as a rotary blade, a rotary tank, a mixer, or a ball mill.
工程（ｂ）は、リン酸又はその塩を、ＴｉＯ２として１００質量部の水酸化チタンに対してＰ２Ｏ５として０．５〜１０．０質量部添加し、混合する工程である。 Step (b), a phosphoric acid or a salt thereof, is added 0.5 to 10.0 parts by weight P 2 O 5 with respect to titanium hydroxide 100 parts by weight TiO 2, a step of mixing.
本発明は、上記アルカリ金属の化合物と、リン酸又はその塩を組み合わせることにより、粒子の成長を促進させる効果と、ルチル化抑制効果を両立し、比較的大きな粒径を有するアナタース型二酸化チタンを提供するものである。その結果、通常の知見からは製造が困難であった、アナタース型で、かつ一次粒子径が０．５μｍ以上、という二酸化チタン粒子を提供することができるという優れた利点を有している。 The present invention combines an alkali metal compound and phosphoric acid or a salt thereof to achieve an anatase-type titanium dioxide that has both an effect of promoting particle growth and a rutile-inhibiting effect and has a relatively large particle size. It is to provide. As a result, it has an excellent advantage that titanium dioxide particles having an anatase type and a primary particle diameter of 0.5 μm or more, which are difficult to produce from ordinary knowledge, can be provided.
本発明でいう、「リン酸又はその塩」には、リン酸、リン酸二水素塩、リン酸水素塩、リン酸塩の他、無水リン酸やヘキサメタリン酸塩、トリポリリン酸塩、ピロリン酸塩などの縮合リン酸塩が含まれる。 In the present invention, “phosphoric acid or a salt thereof” includes phosphoric acid, dihydrogen phosphate, hydrogen phosphate, phosphate, phosphoric anhydride, hexametaphosphate, tripolyphosphate, pyrophosphate Condensed phosphates such as
上記リン酸二水素塩、リン酸水素塩、リン酸塩としては、特に限定されないが、水溶性の塩が好ましい。水溶性のリン酸二水素塩、リン酸水素塩、リン酸塩としては、特に限定されないが、例えばリン酸二水素ナトリウム、リン酸水素ナトリウム、リン酸ナトリウム、リン酸二水素カリウム、リン酸水素カリウム、及びリン酸カリウム等のアルカリ金属塩、リン酸二水素アンモニウム、リン酸水素アンモニウム、及びリン酸アンモニウム等のアンモニウム塩が挙げられる。 Although it does not specifically limit as said dihydrogen phosphate, hydrogen phosphate, and phosphate, A water-soluble salt is preferable. Although it does not specifically limit as water-soluble dihydrogen phosphate, hydrogen phosphate, phosphate, for example, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, hydrogen phosphate Examples include potassium and alkali metal salts such as potassium phosphate, and ammonium salts such as ammonium dihydrogen phosphate, ammonium hydrogen phosphate, and ammonium phosphate.
上記リン酸、リン酸二水素塩、リン酸水素塩、リン酸塩の中でもリン酸が特に好ましい。 Of the phosphoric acid, dihydrogen phosphate, hydrogen phosphate, and phosphate, phosphoric acid is particularly preferable.
上記リン酸又はその塩の添加量は、ＴｉＯ２として１００質量部の水酸化チタンに対してＰ２Ｏ５として０．５〜１０．０質量部である。上記添加量は、好ましくは０．７〜５．０質量部であり、より好ましくは０．９〜３．０質量部である。 The addition amount of the phosphoric acid or salt thereof is 0.5 to 10.0 parts by weight P 2 O 5 with respect to titanium hydroxide 100 parts by weight TiO 2. The addition amount is preferably 0.7 to 5.0 parts by mass, and more preferably 0.9 to 3.0 parts by mass.
本発明においては、工程（ａ）と工程（ｂ）の順序は特に限定されず、先に工程（ａ）を行ってもよいし、先に工程（ｂ）を行ってもよい。 In the present invention, the order of the step (a) and the step (b) is not particularly limited, and the step (a) may be performed first, or the step (b) may be performed first.
上記工程（ａ）と工程（ｂ）においては、必要に応じて各種添加剤を更に添加してもよい。添加剤としては、特に限定されないが、硫酸（Ｈ２ＳＯ４）、硫酸チタニル（ＴｉＯＳＯ４）、硫酸アンモニウム（（ＮＨ４）２ＳＯ４）、酸性硫酸アンモニウム（（ＮＨ４）ＨＳＯ４）等が挙げられる。これらの成分を添加することにより、低温での焼結を抑止することが期待できる。 In the step (a) and the step (b), various additives may be further added as necessary. The additive is not particularly limited, and examples thereof include sulfuric acid (H 2 SO 4 ), titanyl sulfate (TiOSO 4 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), and acidic ammonium sulfate ((NH 4 ) HSO 4 ). . By adding these components, it can be expected to suppress sintering at low temperatures.
工程（ａ）、（ｂ）は、無溶媒で行ってもよく、溶媒存在下で行ってもよい。使用できる溶媒としては、特に限定されないが、水、及び水溶性有機溶媒、例えばメタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール等のアルコール類、エチレングリコール、ジエチレングリコール、グリセリン等の多価アルコール類、Ｎ−メチルピロリドン等のピロリドン系溶媒、アセトン等のケトン系溶媒等が挙げられる。中でも、塩の溶解性が高いことや、安価であることから水が好ましい。 Steps (a) and (b) may be performed without a solvent or in the presence of a solvent. Although it does not specifically limit as a solvent which can be used, Water and water-soluble organic solvents, For example, Alcohols, such as methanol, ethanol, n-propanol, i-propanol, Polyhydric alcohols, such as ethylene glycol, diethylene glycol, glycerol, N -Pyrrolidone solvents such as methylpyrrolidone, ketone solvents such as acetone, and the like. Of these, water is preferable because of its high solubility in salt and low cost.
工程（ｃ）は、上記方法によって得られた混合物を、７５０〜１２００℃で焼成して、二酸化チタンを得る工程である。上述したように、水酸化チタンに、特定のアルカリ金属の水溶性塩と、水溶性リン酸塩とを混合して焼成を行うことにより、粒子の成長に必要な７５０〜１２００℃の高温で焼成しても、ルチル型の発生を抑制することができる。その結果、アナタース型の、比較的大きな一次粒子径を有する二酸化チタンを得ることができる。 Step (c) is a step of obtaining titanium dioxide by firing the mixture obtained by the above method at 750 to 1200 ° C. As described above, a specific alkali metal water-soluble salt and a water-soluble phosphate are mixed with titanium hydroxide and fired, and then fired at a high temperature of 750 to 1200 ° C. necessary for particle growth. Even so, the generation of the rutile type can be suppressed. As a result, anatase-type titanium dioxide having a relatively large primary particle size can be obtained.
本発明の製造方法における焼成温度は、７５０〜１２００℃である。焼成温度の下限は、好ましくは８００℃、より好ましくは８５０℃である。また上限は好ましくは１１００℃、より好ましくは１０００℃である。 The firing temperature in the production method of the present invention is 750 to 1200 ° C. The lower limit of the firing temperature is preferably 800 ° C, more preferably 850 ° C. The upper limit is preferably 1100 ° C, more preferably 1000 ° C.
焼成した粉末は必要に応じて粉砕を行っても良い。粉砕の方法は特に限定されず、自動乳鉢粉砕、ハンマーミル粉砕、流体エネルギーミル粉砕、媒体にリパルプしてのビーズミル粉砕等が挙げられる。 The fired powder may be pulverized as necessary. The method of pulverization is not particularly limited, and examples thereof include automatic mortar pulverization, hammer mill pulverization, fluid energy mill pulverization, and bead mill pulverization by repulping the medium.
リパルプは適当な媒体中に懸濁させ、懸濁液を形成する。使用できる媒体としては、特に限定されないが、水、及び水溶性有機溶媒、例えばメタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール等のアルコール類、エチレングリコール、ジエチレングリコール、グリセリン等の多価アルコール類、Ｎ−メチルピロリドン等のピロリドン系溶媒、アセトン等のケトン系溶媒等が挙げられる。中でも、塩の溶解性が高いことや、安価であることから水が好ましい。 The repulp is suspended in a suitable medium to form a suspension. Although it does not specifically limit as a medium which can be used, Water and water-soluble organic solvents, For example, Alcohols, such as methanol, ethanol, n-propanol, i-propanol, Polyhydric alcohols, such as ethylene glycol, diethylene glycol, glycerol, N -Pyrrolidone solvents such as methylpyrrolidone, ketone solvents such as acetone, and the like. Of these, water is preferable because of its high solubility in salt and low cost.
更に、湿式分級を行っても良い。湿式分級の方法は限定されず、篩、デカンテーション等が挙げられる。 Furthermore, wet classification may be performed. The wet classification method is not limited, and examples thereof include sieving and decantation.
懸濁液から粒子を分離する方法については特に限定されず、常圧での濾過、減圧濾過、遠心分離、デカンテーションなどの公知の方法によって分離することができる。 The method for separating the particles from the suspension is not particularly limited, and the particles can be separated by a known method such as filtration at normal pressure, filtration under reduced pressure, centrifugation, decantation or the like.
（本発明の二酸化チタン粒子）
本発明の二酸化チタン粒子は、アナタース型結晶構造を有し、電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍであって、その粒度分布はＤ９０／Ｄ１０で３．０以下である二酸化チタン粒子である。
(Titanium dioxide particles of the present invention)
The titanium dioxide particles of the present invention have an anatase type crystal structure, and the primary particle diameter measured by measuring the unidirectional diameter with an electron microscope is 0.5 μm to 5.0 μm, and the particle size distribution is D90 / D10. It is a titanium dioxide particle which is 3.0 or less.
このような二酸化チタン粒子を得るための方法は特に限定されないが、一例としては、上述の方法を採用することができる。 Although the method for obtaining such titanium dioxide particles is not particularly limited, the above-described method can be employed as an example.
本発明の二酸化チタン粒子は、アナタース型の二酸化チタン粒子である。本発明の二酸化チタン粒子は、好ましくは、二酸化チタン粒子が含有する全二酸化チタン成分中の、ルチル型結晶の割合（以下、ＲＣ（ルチルコンテント）とも称する）が１０．０質量％以下の、実質的にアナタース型単相からなる二酸化チタン粒子である。 The titanium dioxide particles of the present invention are anatase-type titanium dioxide particles. The titanium dioxide particles of the present invention preferably have a substantially rutile crystal ratio (hereinafter also referred to as RC (rutile content)) of 10.0% by mass or less in the total titanium dioxide component contained in the titanium dioxide particles. In particular, it is a titanium dioxide particle comprising an anatase type single phase.
ＲＣは、銅管球をもつＸ線回折装置により分析したアナタース型酸化チタン粉末の回折ピーク（面指数１０１）のピーク高さＩＡとルチル型酸化チタン粉末の回折ピーク（面指数１１０）のピーク高さＩＲを比較することにより、決定することができる。具体的には、ＲＣは、次式（Ａ）により求めることができる。
ＲＣ（％）＝ＩＲ×１．３２／（ＩＲ×１．３２＋ＩＡ）×１００ （Ａ）
アナタース型酸化チタン粉末の回折ピーク（面指数１０１）のピーク高さＩＡは、ルチル型酸化チタン粉末の回折ピーク（面指数１１０）のピーク高さＩＲよりも１．３２倍大きい値として検出されるため、上記計算式ではＩＲに１．３２の係数を乗じる。なお単位は質量％である。
RC is the peak of the peak height I A and rutile type titanium oxide powder diffraction peaks of a diffraction peak of anatase-type titanium oxide powder was analyzed by X-ray diffraction apparatus having a copper tube (plane index 101) (plane index 110) by comparing the height I R, it can be determined. Specifically, RC can be obtained by the following equation (A).
RC (%) = I R × 1.32 / (I R × 1.32 + I A) × 100 (A)
Peak height I A of the diffraction peak (plane index 101) of anatase type titanium oxide powder is detected as 1.32 times greater than the peak height I R of the diffraction peak of the rutile type titanium oxide powder (plane index 110) to be multiplied by a factor of 1.32 to I R in the above formula. The unit is mass%.
特に限定されないが、上記Ｘ線回折装置の例としてはＸ線回折装置（ＵｌｔｉｍａＩＩＩ、リガク社製）が挙げられる。 Although not particularly limited, an example of the X-ray diffractometer is an X-ray diffractometer (UltimaIII, manufactured by Rigaku Corporation).
二酸化チタン粒子が含有する全二酸化チタン成分中の、ルチル型結晶の割合（ＲＣ）は、１０．０質量％以下であるのが好ましく、５．０質量％以下であるのがより好ましく、３．０質量％以下であるのがさらに好ましく、１．０質量％以下であるのが特に好ましい。ＲＣが低いほど結晶中のアナタース型の割合が高くなるため、より均一な結晶となる点で好ましい。 The ratio (RC) of rutile crystals in the total titanium dioxide component contained in the titanium dioxide particles is preferably 10.0% by mass or less, more preferably 5.0% by mass or less. The content is more preferably 0% by mass or less, and particularly preferably 1.0% by mass or less. The lower the RC, the higher the ratio of anatase type in the crystal, which is preferable in terms of obtaining a more uniform crystal.
本発明の二酸化チタン粒子は、電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍである。ここで「一次粒子」とは、粉末を構成する最も小さい粒子のことをいう。また一次粒子が凝集した状態の粒子を「二次粒子」といい、一次粒子とは区別する。 The titanium dioxide particles of the present invention have a primary particle size of 0.5 μm to 5.0 μm as measured by measuring the fixed direction diameter with an electron microscope. Here, “primary particles” refer to the smallest particles constituting the powder. The particles in which the primary particles are aggregated are called “secondary particles” and are distinguished from the primary particles.
本明細書において、「一次粒子径」とは、走査型電子顕微鏡写真（ＳＥＭ）写真の１万倍視野での定方向径（粒子を挟む一定方向の二本の平行線の間隔）で定義される粒子径（μｍ）であって、ＳＥＭ写真内の一次粒子１５０〜１０００個の定方向径を計測し、その累積分布の平均値を求めたものである。なお、凝集粒子に関しては、その粒子を一次粒子に分割して定方向径を計測する。 In this specification, “primary particle diameter” is defined as a constant direction diameter (interval between two parallel lines in a fixed direction across a particle) in a 10,000 times field of view of a scanning electron micrograph (SEM) photograph. The particle diameter (μm) of the primary particle in the SEM photograph was measured, and the average diameter of the cumulative distribution was determined. In addition, regarding agglomerated particles, the fixed direction diameter is measured by dividing the particles into primary particles.
本発明の二酸化チタン粒子は、上記一次粒子径が０．５μｍ〜５．０μｍである。好ましくは０．６μｍ〜３．０μｍ、より好ましくは０．７μｍ〜２．０μｍである。 The titanium dioxide particles of the present invention have a primary particle diameter of 0.5 μm to 5.0 μm. Preferably they are 0.6 micrometer-3.0 micrometers, More preferably, they are 0.7 micrometer-2.0 micrometers.
上述のように、従来のアナタース型二酸化チタン粒子は、平均一次粒子径が０．３μｍ以下の微細な粒子しか得られていなかった。また一次粒子の集合体である二次粒子としては比較的大きな粒子径のものも存在していたが、凝集性が高いため、取り扱いにくいという問題があった。また、一次粒子の集合体の場合には、粒子間に界面が存在するため、成型等に用いれば、その界面において物性のギャップが生じ、均一性が損なわれる可能性があった。本発明の二酸化チタン粒子は、一次粒子そのものが従来品よりも大きいため、一次粒子径が小さいが故に生じていた従来品の問題点を解決できるものである。 As described above, the conventional anatase-type titanium dioxide particles had only fine particles having an average primary particle diameter of 0.3 μm or less. In addition, secondary particles, which are aggregates of primary particles, have a relatively large particle size, but have a problem that they are difficult to handle because of their high cohesion. Further, in the case of an aggregate of primary particles, an interface exists between the particles. Therefore, when used for molding or the like, there is a possibility that a physical property gap occurs at the interface and the uniformity is impaired. The titanium dioxide particles of the present invention can solve the problems of the conventional products that are caused by the small primary particle size because the primary particles themselves are larger than the conventional products.
また本発明の二酸化チタン粒子は、その粒度分布が、Ｄ９０／Ｄ１０で３．０以下であるという特徴を有している。いいかえれば、粒子径の均一性が高い二酸化チタン粒子である。 Moreover, the titanium dioxide particles of the present invention have a feature that the particle size distribution is 3.0 or less in D90 / D10. In other words, it is titanium dioxide particles having a high uniformity in particle diameter.
本願明細書における、Ｄ９０／Ｄ１０とは一次粒子の粒度分布から求められる粒度分布のシャープさを示す指標であり、以下の様に求められる。 In the present specification, D90 / D10 is an index indicating the sharpness of the particle size distribution obtained from the particle size distribution of the primary particles, and is obtained as follows.
まず一次粒子径は、走査型電子顕微鏡（ＳＥＭ、特に限定されないが、例えばＪＳＭ−５４００、日本電子社製等）により、写真の１万倍視野での定方向径（粒子を挟む一定方向の二本の平行線の間隔）で定義される粒子径（μｍ）を計測する。定方向径は、ＳＥＭ写真内の一次粒子１５０〜１０００個程度について計測を行い、その累積分布の平均値を求める。凝集粒子に関しては、その粒子を一次粒子に分割して定方向径を計測する。 First, the primary particle size is determined by a scanning electron microscope (SEM, although not particularly limited, for example, JSM-5400, manufactured by JEOL Ltd.) and the like, with a fixed direction diameter (two directions in a fixed direction across the particle) in a 10,000 times field of view. The particle diameter (μm) defined by the interval between the parallel lines of the book is measured. The fixed direction diameter is measured for about 150 to 1000 primary particles in the SEM photograph, and the average value of the cumulative distribution is obtained. As for the aggregated particles, the particles are divided into primary particles, and the fixed direction diameter is measured.
その結果から、Ｄ１０とＤ９０を求める。Ｄ１０とは、長さ基準での１０％積算粒径、Ｄ９０とは長さ基準での９０％積算粒径を意味する。 From the result, D10 and D90 are obtained. D10 means a 10% cumulative particle diameter based on the length, and D90 means a 90% cumulative particle diameter based on the length.
粒度分布のシャープさの指標として、Ｄ９０／Ｄ１０の比を算出する。この値が大きい程粒度分布がブロードであることを意味し、この値が小さい程粒度分布がシャープであることを意味する。 A ratio of D90 / D10 is calculated as an index of the sharpness of the particle size distribution. A larger value means that the particle size distribution is broader, and a smaller value means that the particle size distribution is sharper.
上記二酸化チタン粒子は、好ましくは、結晶構造がアナタース型の二酸化チタン１００質量部と、Ｐ２Ｏ５換算で０．５〜１０．０質量部のリンとを含有する粒子状組成物である。 The titanium dioxide particles are preferably a particulate composition containing 100 parts by mass of anatase-type titanium dioxide having a crystal structure and 0.5 to 10.0 parts by mass of phosphorus in terms of P 2 O 5 .
二酸化チタン粒子中のリン含有量は、アナタース型の二酸化チタン１００質量部に対してＰ２Ｏ５換算で０．５〜１０．０質量部であり、好ましくは、０．７〜５．０質量部、より好ましくは、０．９〜３．０質量部である。このような量のリンを含むことによって、高温焼成を経ても、ルチル型への転移がほぼ抑制された二酸化チタン粒子状組成物を得ることができる。 The phosphorus content in the titanium dioxide particles is 0.5 to 10.0 parts by mass, preferably 0.7 to 5.0 parts by mass in terms of P 2 O 5 with respect to 100 parts by mass of anatase-type titanium dioxide. Parts, more preferably 0.9 to 3.0 parts by mass. By including such an amount of phosphorus, it is possible to obtain a titanium dioxide particulate composition in which the transition to the rutile type is substantially suppressed even after high-temperature firing.
本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお下記実施例・比較例において、特に断りの無い限り、「部」は「質量部」を、「％」は「質量％」を意味する。 EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.
（用語の説明及び測定方法）
［ＲＣ（ルチルコンテント）］
ＲＣ（ルチルコンテント）は、銅管球をもつＸ線回折装置（ＵｌｔｉｍａＩＩＩ、リガク社製）により分析したアナタース型酸化チタン粉末の回折ピーク（面指数１０１）のピーク高さＩＡとルチル型酸化チタン粉末の回折ピーク（面指数１１０）のピーク高さＩＲを比較することにより、決定した。
(Explanation of terms and measurement method)
[RC (rutile content)]
RC (rutile content) is, X-rays diffraction apparatus having a copper tube (UltimaIII, manufactured by Rigaku Corporation) peak height I A and rutile-type titanium oxide of the diffraction peak of anatase-type titanium oxide powder was analyzed by (plane index 101) by comparing the peak heights I R of the diffraction peak of the powder (plane index 110) were determined.
ＲＣは、次式により求めた。
ＲＣ（％）＝ＩＲ×１．３２／（ＩＲ×１．３２＋ＩＡ）×１００
アナタース型酸化チタン粉末の回折ピーク（面指数１０１）のピーク高さＩＡは、ルチル型酸化チタン粉末の回折ピーク（面指数１１０）のピーク高さＩＲよりも１．３２倍大きい値として検出されるため、上記計算式ではＩＲに１．３２の係数を乗じた。なお単位は質量％である。
RC was calculated by the following equation.
RC (%) = I R × 1.32 / (I R × 1.32 + I A) × 100
Peak height I A of the diffraction peak (plane index 101) of anatase type titanium oxide powder is detected as 1.32 times greater than the peak height I R of the diffraction peak of the rutile type titanium oxide powder (plane index 110) to be, multiplied by a factor of 1.32 to I R in the above formula. The unit is mass%.
［一次粒子径］
一次粒子径は、走査型電子顕微鏡（ＳＥＭ、ＪＳＭ−５４００、日本電子社製）写真の１万倍視野での定方向径（粒子を挟む一定方向の二本の平行線の間隔）で定義される粒子径（μｍ）であって、ＳＥＭ写真内の一次粒子１５０〜１０００個の定方向径を計測し、その累積分布の平均値を求めた。なお凝集粒子に関しては、その粒子を一次粒子に分割して定方向径を計測した。その結果から、Ｄ１０とＤ９０を求めた。ここでＤ１０とは、長さ基準での１０％積算粒径、Ｄ９０とは長さ基準での９０％積算粒径を意味する。
[Primary particle size]
The primary particle diameter is defined by a fixed direction diameter (interval between two parallel lines in a certain direction across the particle) in a 10,000 times field of view of a scanning electron microscope (SEM, JSM-5400, manufactured by JEOL Ltd.). The particle diameter (μm) was measured, and the fixed direction diameter of 150 to 1000 primary particles in the SEM photograph was measured, and the average value of the cumulative distribution was obtained. In addition, about the aggregated particle, the particle | grain was divided | segmented into the primary particle and the fixed direction diameter was measured. From the results, D10 and D90 were determined. Here, D10 means 10% cumulative particle diameter on the basis of length, and D90 means 90% cumulative particle diameter on the basis of length.
［粒度分布のシャープさ（Ｄ９０／Ｄ１０）］
粒度分布のシャープさの指標として、Ｄ９０／Ｄ１０の値を示した。この値が大きい程粒度分布がブロードであることを意味し、この値が小さい程粒度分布がシャープであることを意味する。
[Sharpness of particle size distribution (D90 / D10)]
A value of D90 / D10 was shown as an index of the sharpness of the particle size distribution. A larger value means that the particle size distribution is broader, and a smaller value means that the particle size distribution is sharper.
［凝集粒子径］
凝集粒子径は、レーザー回折／散乱式粒度分布測定装置により求めた。下記実施例及び比較例において、凝集粒子径は体積基準での５０％積算粒径（メジアン径）を示した。凝集粒子径を計測する装置としては、レーザー回折／散乱式粒度分布測定装置（ＬＡ−７５０、堀場製作所社製）を用いた。
[Agglomerated particle size]
The agglomerated particle diameter was determined with a laser diffraction / scattering particle size distribution analyzer. In the following examples and comparative examples, the aggregated particle diameter is a 50% cumulative particle diameter (median diameter) on a volume basis. As a device for measuring the aggregated particle size, a laser diffraction / scattering particle size distribution measuring device (LA-750, manufactured by Horiba, Ltd.) was used.
［易粉砕性（凝集粒子径／一次粒子径）］
易粉砕性の指標として、一次粒子径と凝集粒子径の比（凝集粒子径／一次粒子径）を示した。この値が小さいほど易粉砕性であり、この値が大きいほど難粉砕性であることを意味する。
[Easily pulverized (aggregated particle size / primary particle size)]
As an easy grindability index, the ratio between the primary particle size and the aggregated particle size (aggregated particle size / primary particle size) was shown. The smaller the value, the easier the grindability, and the larger the value, the harder the grindability.
（実施例１）
水酸化チタン（堺化学工業社製）をＴｉＯ２として５０ｇ（ＴｉＯ２として１００質量部）量り取り、外径１５０ｍｍ、容量４００ｍｌの磁製蒸発皿に入れ、１０１ｇ／ｌの硫酸チタニル水溶液を２４．７５ｍｌ（ＴｉＯ２として５．０質量部）、１７質量％のリン酸を４．２６ｇ（Ｐ２Ｏ５として１．０質量部）、４０ｇ／ｌのＫ２ＳＯ４水溶液を１２．５ｍｌ（Ｋ２Ｏとして１．０質量部）、４０ｇ／ｌのＮａ２ＳＯ４水溶液を１２．５ｍｌ（Ｎａ２Ｏとして１．０質量部）、２００ｇ／ｌの硫酸アンモニウム水溶液を１２．５ｍｌ（（ＮＨ４）２ＳＯ４として５．０質量部）、３０質量％の硫酸を８．３３ｇ（Ｈ２ＳＯ４として５．０質量部）を順次添加した。次に、この磁製蒸発皿を蒸気で加熱し、乳棒で良く混ぜながら蒸発乾固させた。続いて、取り出した乾燥粉８０ｇを容量２８０ｍｌの坩堝に入れ９００℃で３０分間静置焼成を行った。焼成した粉末４５ｇを自動乳鉢（日陶科学株式会社製）で２０分間粉砕し、粉砕粉４０ｇを純水４００ｍｌにリパルプし３０分間攪拌し、３２５メッシュ（目開き４５μｍ）の篩に通し、篩下のリパルプ液をブフナー漏斗に移してろ過し、純水２リットルで通水洗浄し、１２０℃で１２時間乾燥することにより酸化チタン粉末を得た。
Example 1
Weigh 50 g of titanium hydroxide (manufactured by Sakai Chemical Industry Co., Ltd.) as TiO 2 (100 parts by mass as TiO 2 ), put it in a magnetic evaporating dish with an outer diameter of 150 mm and a capacity of 400 ml, and add 101 g / l of titanyl sulfate aqueous solution 24. 75 ml (5.0 parts by mass as TiO 2 ), 4.26 g of phosphoric acid at 17% by mass (1.0 part by mass as P 2 O 5 ), and 12.5 ml of 40 g / l aqueous K 2 SO 4 solution (K 1.0 parts by weight 2 O), 12.5 ml of aqueous Na 2 SO 4 in 40 g / l (1.0 parts by Na 2 O), ammonium sulfate aqueous solution of 200g / l 12.5ml ((NH 4 ) 2 SO 4 ( 5.0 parts by mass) and 30% by mass of sulfuric acid (8.33 g) (H 2 SO 4 as 5.0 parts by mass) were sequentially added. Next, this porcelain evaporating dish was heated with steam and evaporated to dryness while mixing well with a pestle. Subsequently, 80 g of the dried powder taken out was placed in a crucible having a capacity of 280 ml and subjected to stationary baking at 900 ° C. for 30 minutes. 45g of the baked powder was pulverized for 20 minutes in an automatic mortar (manufactured by Nissho Science Co., Ltd.), 40g of the pulverized powder was repulped into 400ml of pure water, stirred for 30 minutes, passed through a 325 mesh (opening 45µm) sieve, Was transferred to a Buchner funnel, filtered, washed with 2 liters of pure water and dried at 120 ° C. for 12 hours to obtain titanium oxide powder.
得られた粉末を走査型電子顕微鏡により観察し、一次粒子径を計測し、Ｄ９０、Ｄ１０、（Ｄ９０／Ｄ１０）を求めた。またＸ線回折装置により固体粒子の結晶構造およびＲＣを評価した。さらにレーザー回折／散乱式粒度分布測定装置により、凝集粒子径、及び易粉砕性（凝集粒子径／一次粒子径）を計測した。その結果を表１に示す。 The obtained powder was observed with a scanning electron microscope, the primary particle diameter was measured, and D90, D10, and (D90 / D10) were obtained. The crystal structure and RC of the solid particles were evaluated by an X-ray diffractometer. Furthermore, the aggregated particle diameter and easy grindability (aggregated particle diameter / primary particle diameter) were measured with a laser diffraction / scattering particle size distribution measuring apparatus. The results are shown in Table 1.
（実施例２〜７、及び比較例１〜２、５〜９）
下記表１に示す配合及び焼成温度に変更した以外は実施例１と同様にして酸化チタン粉末を得た。得られた各酸化チタン粉末の試料について、実施例１と同様の物性を計測した。結果を表１に示す。
(Examples 2-7 and Comparative Examples 1-2, 5-9)
Titanium oxide powder was obtained in the same manner as in Example 1 except that the composition and firing temperature shown in Table 1 were changed. About the sample of each obtained titanium oxide powder, the physical property similar to Example 1 was measured. The results are shown in Table 1.
（比較例３）
水酸化チタン（堺化学工業社製）をＴｉＯ２として５０ｇ（ＴｉＯ２として１００質量部）量り取り、外径１５０ｍｍ、容量：４００ｍｌの磁製蒸発皿に入れ、１７質量％のリン酸を１．９２ｇ（Ｐ２Ｏ５として０．４５質量部）、４０ｇ／ｌのＫ２ＳＯ４水溶液を４ｍｌ（Ｋ２Ｏとして０．３２質量部）を順次添加した。次に、この磁製蒸発皿を蒸気で加熱し、乳棒で良く混ぜながら蒸発乾固させた。続いて、取り出した乾燥粉６０ｇを容量２８０ｍｌの坩堝に入れ、９００℃で３０分間静置焼成を行った。焼成した粉末４５ｇを自動乳鉢（日陶科学株式会社製）で４０分間粉砕し、酸化チタン粉末を得た。
(Comparative Example 3)
Weigh 50 g of titanium hydroxide (manufactured by Sakai Chemical Industry Co., Ltd.) as TiO 2 (100 parts by mass as TiO 2 ), put it in a magnetic evaporating dish with an outer diameter of 150 mm and a capacity of 400 ml, and add 17% by mass of phosphoric acid. 92 g (P 2 O 5 0.45 parts by weight) were successively added K 2 SO 4 aqueous solution 40 g / l 4 ml of (0.32 parts by weight K 2 O). Next, this porcelain evaporating dish was heated with steam and evaporated to dryness while mixing well with a pestle. Subsequently, 60 g of the taken-out dry powder was put into a crucible having a capacity of 280 ml and subjected to stationary baking at 900 ° C. for 30 minutes. 45 g of the baked powder was pulverized for 40 minutes in an automatic mortar (manufactured by Nippon Ceramic Science Co., Ltd.) to obtain titanium oxide powder.
得られた粉末を走査型電子顕微鏡により観察し、一次粒子径を計測し、Ｄ９０、Ｄ１０、（Ｄ９０／Ｄ１０）を求めた。またＸ線回折装置により固体粒子の結晶構造およびＲＣを評価した。さらにレーザー回折／散乱式粒度分布測定装置により、凝集粒子径、及び易粉砕性（凝集粒子径／一次粒子径）を計測した。その結果を表１に示す。 The obtained powder was observed with a scanning electron microscope, the primary particle diameter was measured, and D90, D10, and (D90 / D10) were obtained. The crystal structure and RC of the solid particles were evaluated by an X-ray diffractometer. Furthermore, the aggregated particle diameter and easy grindability (aggregated particle diameter / primary particle diameter) were measured with a laser diffraction / scattering particle size distribution measuring apparatus. The results are shown in Table 1.
（比較例４）
焼成温度を１０００℃にした以外は比較例３と同様にして酸化チタン粉末を得た。得られた酸化チタン粉末を分析した。結果を表１に示す。
(Comparative Example 4)
Titanium oxide powder was obtained in the same manner as in Comparative Example 3 except that the firing temperature was 1000 ° C. The obtained titanium oxide powder was analyzed. The results are shown in Table 1.
表１中の水酸化チタンの添加量はＴｉＯ２としての質量を表す。また他の成分の添加量は、水酸化チタンのＴｉＯ２としての添加量を１００質量部とした場合の添加量（質量部）を表している。この場合、硫酸チタニルの量はＴｉＯ２としての量を、リン酸はＰ２Ｏ５としての量を、Ｋ２ＳＯ４はＫ２Ｏとしての量を、Ｎａ２ＳＯ４はＮａ２Ｏとしての量をそれぞれ表す。また硫酸アンモニウム水溶液は、（ＮＨ４）２ＳＯ４としての正味量（質量部）を、硫酸はＨ２ＳＯ４としての正味量（質量部）を意味する。 The amount of titanium hydroxide added in Table 1 represents the mass as TiO 2 . The amount of the other components represent the addition amount when the added amount of 100 parts by weight as TiO 2 of titanium hydroxide (mass parts). In this case, the amount of the amount of TiO 2 in titanyl sulfate, the amount of phosphoric acid as P 2 O 5, K 2 SO 4 is the amount of the K 2 O, Na 2 SO 4 is as Na 2 O Each represents a quantity. In addition, the ammonium sulfate aqueous solution means a net amount (parts by mass) as (NH 4 ) 2 SO 4 , and sulfuric acid means a net amount (parts by mass) as H 2 SO 4 .
（表１の説明）
表１の実施例１〜７の様に、
・リンをＰ２Ｏ５として０．５〜１０．０質量部、
・アルカリ金属（Ｋ、Ｎａ、Ｃｓ）を酸化物換算で１．０〜１１．０質量部を添加し、
・蒸発乾固した粉末を７５０〜１２００℃で焼成する
ことにより、所望の二酸化チタン粒子を得ることができる。得られる酸化チタンは、アナタース型で、一次粒子径が０．５〜５．０μｍであり、粒度分布がシャープで、易粉砕性を有する。更に、硫酸チタニル、硫酸アンモニウム、硫酸を任意に加えても、本発明の二酸化チタン粒子を得ることができる。
(Explanation of Table 1)
As in Examples 1-7 in Table 1,
-0.5 to 10.0 parts by mass of phosphorus as P 2 O 5
-Add 1.0-11.0 parts by mass of alkali metal (K, Na, Cs) in terms of oxide,
-Desired titanium dioxide particles can be obtained by baking the evaporated and dried powder at 750 to 1200 ° C. The obtained titanium oxide is anatase type, has a primary particle size of 0.5 to 5.0 μm, a sharp particle size distribution, and easily grindability. Furthermore, the titanium dioxide particles of the present invention can be obtained by optionally adding titanyl sulfate, ammonium sulfate, or sulfuric acid.
表１の比較例１の様に、焼成温度が低いと粒子が十分に成長しないことに加え、粒度分布がブロードで、難粉砕性となった。一方、比較例２のように、焼成温度が高いとルチル化が進行した。この場合、リンやカリウム、ナトリウム源を加えてもルチル化は抑制できなかった。また二酸化チタン粒子は難粉砕性であった。 As in Comparative Example 1 of Table 1, when the firing temperature was low, the particles did not grow sufficiently, and the particle size distribution was broad, making it difficult to grind. On the other hand, as in Comparative Example 2, when the firing temperature was high, rutileization proceeded. In this case, even when phosphorus, potassium or sodium sources were added, rutile formation could not be suppressed. The titanium dioxide particles were hardly pulverizable.
また、表１の比較例３、４の様に、一般的なアナタース型顔料のリン、カリウム添加の場合（水酸化チタン１００質量部（ＴｉＯ２として）に対し、リンはＰ２Ｏ５として０．５質量部以下、カリウムはＫ２Ｏとして０．５質量部以下）は、焼成温度が９００℃では粒子が十分に成長しない。また、焼成温度が１０００℃ではルチル化が進行する。 In addition, as in Comparative Examples 3 and 4 in Table 1, in the case of adding phosphorus and potassium as a general anatase pigment (100 parts by mass of titanium hydroxide (as TiO 2 )), phosphorus is 0 as P 2 O 5. 0.5 parts by mass or less and potassium is 0.5 parts by mass or less as K 2 O), the particles do not grow sufficiently at a firing temperature of 900 ° C. Further, when the firing temperature is 1000 ° C., rutileization proceeds.
また、表１の比較例５の様に、リンを添加しない場合は、粒子は成長するが、ルチル化が抑制できず、粒度分布はブロードで、難粉砕性となった。 In addition, as in Comparative Example 5 in Table 1, when phosphorus was not added, the particles grew, but rutileization could not be suppressed, the particle size distribution was broad, and it became difficult to grind.
逆に、表１の比較例６の様に、リンがＰ２Ｏ５として１０．０質量部を超える場合は粒子が成長せず、この場合も難粉砕性となった。 On the contrary, as shown in Comparative Example 6 in Table 1, when phosphorus exceeds 10.0 parts by mass as P 2 O 5 , the particles did not grow, and in this case, it became difficult to grind.
また、表１の比較例７の様に、アルカリ金属が酸化物換算で１．０質量部未満の場合は、十分に粒子が成長しなかった。 In addition, as in Comparative Example 7 in Table 1, when the alkali metal was less than 1.0 part by mass in terms of oxide, the particles did not grow sufficiently.
逆に、表１の比較例８の様に、アルカリ金属が酸化物換算で１１．０質量部を超える場合は、粒度分布がブロードで、難粉砕性となった。 Conversely, as in Comparative Example 8 in Table 1, when the alkali metal exceeded 11.0 parts by mass in terms of oxide, the particle size distribution was broad and it became difficult to grind.
また、表１の比較例９の様に、リン及びアルカリ金属を添加しない場合はルチル化が抑制できず、粒度分布がブロードで、難粉砕性となった。 Further, as in Comparative Example 9 of Table 1, when phosphorus and alkali metal were not added, rutileization could not be suppressed, the particle size distribution was broad, and it became difficult to grind.
Claims (4)
電子顕微鏡にて定方向径を計測することによる一次粒子径が０．５μｍ〜５．０μｍであり、
その粒度分布はＤ９０／Ｄ１０で３．０以下である
二酸化チタン粒子。 The crystal structure is anatase type,
The primary particle diameter by measuring the fixed direction diameter with an electron microscope is 0.5 μm to 5.0 μm,
Titanium dioxide particles whose particle size distribution is 3.0 or less in D90 / D10.
Ｐ２Ｏ５換算で０．５〜１０．０質量部のリンとを含有する粒子状組成物である
請求項１又は２記載の二酸化チタン粒子。 The titanium dioxide particles have a crystal structure of 100 mass parts of anatase type titanium dioxide,
Terms of P 2 O 5 in a particulate composition containing the phosphorus 0.5 to 10.0 parts by claim 1 or 2 titanium dioxide particles according.
（ｂ）リン酸又はその塩を、Ｐ２Ｏ５として０．５〜１０．０質量部添加し、混合する工程と、
（ｃ）得られた混合物を７５０〜１２００℃で焼成して、二酸化チタンを得る工程と
を含む、請求項１〜３項のいずれか一項に記載の二酸化チタン粒子を製造する方法。 (A) 100 parts by mass of titanium hydroxide as TiO 2 and at least one alkali metal compound selected from the group consisting of Na, K and Cs in a total amount of 1.0 to 11.0 as an alkali metal oxide Adding a mass part and mixing,
(B) adding 0.5 to 10.0 parts by mass of phosphoric acid or a salt thereof as P 2 O 5 and mixing;
(C) The method of manufacturing the titanium dioxide particle as described in any one of Claims 1-3 including the process of baking the obtained mixture at 750-1200 degreeC, and obtaining a titanium dioxide.
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