JP2014201495A - Rare earth phosphate powder and production method of the same, and fluid dispersion including the powder - Google Patents
Rare earth phosphate powder and production method of the same, and fluid dispersion including the powder Download PDFInfo
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- JP2014201495A JP2014201495A JP2013079911A JP2013079911A JP2014201495A JP 2014201495 A JP2014201495 A JP 2014201495A JP 2013079911 A JP2013079911 A JP 2013079911A JP 2013079911 A JP2013079911 A JP 2013079911A JP 2014201495 A JP2014201495 A JP 2014201495A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 110
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 101
- 239000010452 phosphate Substances 0.000 title claims abstract description 94
- -1 Rare earth phosphate Chemical class 0.000 title claims abstract description 92
- 239000006185 dispersion Substances 0.000 title claims abstract description 80
- 239000000843 powder Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000012530 fluid Substances 0.000 title abstract 2
- 239000002245 particle Substances 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001186 cumulative effect Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 238000000691 measurement method Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000002612 dispersion medium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 91
- 230000003287 optical effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000003002 pH adjusting agent Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 229910052765 Lutetium Inorganic materials 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 239000007771 core particle Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- OWNMACFMOIQGAC-UHFFFAOYSA-K lutetium(3+);phosphate Chemical compound [Lu+3].[O-]P([O-])([O-])=O OWNMACFMOIQGAC-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical group [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本発明は、希土類リン酸塩粉末及びその製造方法に関する。また本発明は、希土類リン酸塩粉末を含む分散液に関する。 The present invention relates to a rare earth phosphate powder and a method for producing the same. The present invention also relates to a dispersion containing rare earth phosphate powder.
希土類リン酸塩は、燐光を発することが知られている。この特性を生かし、希土類リン酸塩は、三色蛍光ランプ、液晶ディスプレイ用バックライト、プラズマディスプレイ等の分野で利用されている。また、希土類リン酸塩は、可視光の波長領域を含む紫外光から赤外光の波長領域において屈折率及びアッベ数が高い材料であることが知られている。これらの特性を生かし、希土類リン酸塩は光学材料としても利用されている。 Rare earth phosphates are known to emit phosphorescence. Taking advantage of this property, rare earth phosphates are used in fields such as three-color fluorescent lamps, backlights for liquid crystal displays, and plasma displays. Further, it is known that rare earth phosphate is a material having a high refractive index and Abbe number in the wavelength range from ultraviolet light to infrared light including the visible light wavelength region. Taking advantage of these characteristics, rare earth phosphates are also used as optical materials.
例えば特許文献１には、セリウム、テルビウム及びランタンから選択される少なくとも１つの希土類元素のリン酸塩を含む懸濁液が記載されている。このリン酸塩は、モナザイト型の少なくとも２５ｎｍの平均サイズを有する等方性で単結晶の一次粒子が凝集してなる二次粒子からなる。この二次粒子は、４００ｎｍ以下の平均サイズを有するものである。 For example, Patent Document 1 describes a suspension containing a phosphate of at least one rare earth element selected from cerium, terbium and lanthanum. This phosphate is composed of secondary particles formed by agglomeration of primary particles of an isotropic single crystal having an average size of at least 25 nm of monazite type. The secondary particles have an average size of 400 nm or less.
特許文献２には、ＢＥＴ比表面積が１０〜２００ｍ2／ｇである希土類リン酸塩からなる粒子を含む水性分散液が記載されている。粒子はその最大粒径Ｄmaxが１００ｎｍ以下であり、該水性分散液はそのｐＨが１以上５未満であり、該粒子の濃度が５〜５０質量％である。同文献には、この水性分散液を基板の表面に塗布して塗膜を形成し、該塗膜を乾燥させて透明薄膜を得ることも記載されている。 Patent Document 2 describes an aqueous dispersion containing particles made of rare earth phosphate having a BET specific surface area of 10 to 200 m 2 / g. The particles have a maximum particle size D max of 100 nm or less, the aqueous dispersion has a pH of 1 or more and less than 5, and the concentration of the particles is 5 to 50% by mass. This document also describes that this aqueous dispersion is applied to the surface of a substrate to form a coating film, and the coating film is dried to obtain a transparent thin film.
しかし、媒質である希土類リン酸塩が高度に単分散した状態になっており、かつ透明性が一層高い分散液がますます要求されている。 However, there is an increasing demand for dispersions in which the rare earth phosphate as a medium is in a highly monodispersed state and has higher transparency.
本発明の課題は、前述した従来技術よりも各種の性能が一層向上した希土類リン酸塩粉末及びその製造方法並びに該粉末を含む分散液を提供することにある。 An object of the present invention is to provide a rare earth phosphate powder having various performances further improved as compared with the above-described prior art, a production method thereof, and a dispersion containing the powder.
本発明は、窒素吸着法で測定した比表面積が１０ｍ2／ｇ以上２００ｍ2／ｇ以下であり、
レーザー回折散乱式粒度分布測定法による累積体積９９．９９容量％における体積累積粒径Ｄ99.99が１μｍ以上１００μｍ以下である希土類リン酸塩粉末を提供するものである。
In the present invention, the specific surface area measured by a nitrogen adsorption method is 10 m 2 / g or more and 200 m 2 / g or less,
The present invention provides a rare earth phosphate powder having a volume cumulative particle diameter D 99.99 at a cumulative volume of 99.99% by volume by a laser diffraction / scattering particle size distribution measurement method of 1 μm or more and 100 μm or less.
また本発明は、前記の粉末の好適な製造方法として、希土類元素源を含む水溶液と、リン酸根を含む水溶液とを同時添加して、希土類リン酸塩を生成させる工程を含む希土類リン酸塩粉末の製造方法を提供するものである。 Moreover, the present invention provides a rare earth phosphate powder comprising a step of forming a rare earth phosphate by simultaneously adding an aqueous solution containing a rare earth element source and an aqueous solution containing a phosphate group as a preferred method for producing the powder. The manufacturing method of this is provided.
更に本発明は、前記の希土類リン酸塩粉末が分散媒中に分散してなる分散液を提供するものである。 Furthermore, the present invention provides a dispersion obtained by dispersing the rare earth phosphate powder in a dispersion medium.
本発明の希土類リン酸塩粉末は、これを分散媒に分散させると、該粉末の濃度が高い場合であっても分散性が高く、かつ長期保存しても沈殿の生成が生じづらい安定性の高い分散液が得られる。この分散液は透明性が高いものでもある。 When the rare earth phosphate powder of the present invention is dispersed in a dispersion medium, it is highly dispersible even when the concentration of the powder is high, and stable even when stored for a long time. A high dispersion is obtained. This dispersion is also highly transparent.
以下本発明を、その好ましい実施形態に基づき説明する。本発明の希土類リン酸塩粉末は、ＬｎＰＯ4（Ｌｎは少なくとも１種の希土類元素を表す。以下「Ｌｎ」というときには、この意味で用いられる。）で表される希土類リン酸塩からなる粒子の集合体である。以下の説明において、「希土類リン酸塩粉末」というときには、文脈に応じ、希土類リン酸塩からなる粒子の集合体である粉末そのものを指す場合と、該粉末を構成する個々の粒子を指す場合とがある。希土類リン酸塩は一般に高屈折率でかつ高アッベ数を有する材料である。したがって、希土類リン酸塩粉末は、光学レンズ等の光学材料を製造するための原料として好適なものである。なお、本明細書に言うリン酸塩とはオルトリン酸塩のことである。オルトリン酸塩には正塩、リン酸水素塩及びリン酸二水素塩が知られているところ、本発明で用いられる希土類リン酸塩はオルトリン酸の正塩である。 Hereinafter, the present invention will be described based on preferred embodiments thereof. The rare earth phosphate powder of the present invention is a particle comprising a rare earth phosphate represented by LnPO 4 (Ln represents at least one kind of rare earth element; hereinafter referred to as “Ln” in this sense). It is an aggregate. In the following description, when referring to “rare earth phosphate powder”, depending on the context, it refers to the powder itself, which is an aggregate of particles composed of rare earth phosphate, and to the individual particles constituting the powder. There is. Rare earth phosphate is generally a material having a high refractive index and a high Abbe number. Therefore, the rare earth phosphate powder is suitable as a raw material for producing an optical material such as an optical lens. In addition, the phosphate mentioned in this specification is an orthophosphate. Orthophosphates, hydrogen phosphates and dihydrogen phosphates are known as orthophosphates, and the rare earth phosphates used in the present invention are orthophosphates.
ＬｎＰＯ4で表される希土類リン酸塩における希土類元素には、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕがある。これらのうち、リン酸塩の屈折率及びアッベ数が特に高いことから、Ｙ、Ｌａ、Ｇｄ、Ｙｂ及びＬｕから選択される希土類元素を用いることが好ましい。 The rare earth elements in the rare earth phosphate represented by LnPO 4 include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. is there. Among these, since the refractive index and Abbe number of phosphate are particularly high, it is preferable to use a rare earth element selected from Y, La, Gd, Yb and Lu.
本発明で用いる希土類リン酸塩は、結晶性のものであってもよく、あるいはアモルファス（非晶質）のものであってもよい。希土類リン酸塩が結晶性のものである場合、その結晶系としては正方晶又は単斜晶であることが光学的な特性が有利になる点から好ましい。 The rare earth phosphate used in the present invention may be crystalline or amorphous (amorphous). When the rare earth phosphate is crystalline, the crystal system is preferably tetragonal or monoclinic from the viewpoint of advantageous optical characteristics.
希土類元素のリン酸塩については、ゼノタイム構造、モナザイト構造及びラブドフェーン構造の結晶構造が知られている。一般に、リン酸塩中に主としてＬｕ、Ｙｂ又はＹなどが含まれる場合には、そのリン酸塩は正方晶のゼノタイム構造を取る。主としてＧｄ又はＬａなどが含まれる場合には、単斜晶のモナザイト構造を取る。また、希土類元素のリン酸塩が水和物である場合には、六方晶のラブドフェーン構造を取る。希土類元素のリン酸塩を光学レンズに応用する場合、高屈折率であることが重要となることが多いところ、ラブドフェーン構造は水分子を含む影響で他の結晶構造と比較して屈折率が低いなど光学的な特性が不利になることが考えられる。更に水和物である場合、経時安定性に問題がある可能性がある。このような理由から希土類元素のリン酸塩は、その結晶構造が正方晶又は単斜晶であることが好ましい。また希土類元素のリン酸塩は、これらの結晶構造を取る代わりにアモルファスであってもよい。 As for rare earth element phosphates, crystal structures of a xenotime structure, a monazite structure, and a rubbed phene structure are known. In general, when Lu, Yb, Y or the like is mainly contained in the phosphate, the phosphate has a tetragonal xenotime structure. When Gd or La is mainly contained, a monoclinic monazite structure is adopted. Further, when the rare earth element phosphate is a hydrate, it takes a hexagonal rubbed phene structure. When applying rare earth phosphates to optical lenses, it is often important to have a high refractive index. However, the rubbed ferne structure has a refractive index compared to other crystal structures due to the influence of water molecules. It is considered that the optical characteristics are disadvantageous such as low. Furthermore, in the case of a hydrate, there may be a problem with stability over time. For these reasons, the rare earth element phosphate preferably has a tetragonal or monoclinic crystal structure. The rare earth element phosphate may be amorphous instead of taking these crystal structures.
本発明の希土類リン酸塩粉末は、窒素吸着法で測定した比表面積が１０ｍ2／ｇ以上２００ｍ2／ｇ以下のものである。この範囲内の比表面積を有する希土類リン酸塩粒子を用いることで、該粒子が微粒であっても該粒子を高濃度で安定的に分散媒に分散可能であることが、本発明者らの検討の結果判明した。特に、希土類リン酸塩粉末の比表面積が好ましくは２０ｍ2／ｇ以上２００ｍ2／ｇ以下、更に好ましくは３０ｍ2／ｇ以上２００ｍ2／ｇ以下であると、希土類リン酸塩粉末を一層高濃度で一層安定的に高分散させることができる。 The rare earth phosphate powder of the present invention has a specific surface area measured by a nitrogen adsorption method of 10 m 2 / g or more and 200 m 2 / g or less. By using rare earth phosphate particles having a specific surface area within this range, even if the particles are fine particles, it is possible to stably disperse the particles in a dispersion medium at a high concentration. It became clear as a result of examination. In particular, when the specific surface area of the rare earth phosphate powder is preferably 20 m 2 / g or more and 200 m 2 / g or less, more preferably 30 m 2 / g or more and 200 m 2 / g or less, the rare earth phosphate powder has a higher concentration. And can be dispersed more stably.
本発明において前記の比表面積は、例えば島津製作所社製の「フローソーブ２３００」を用い、窒素吸着法で測定することができる。測定粉末の量は０．３ｇとし、予備脱気条件は大気圧下、１２０℃で１０分間とした。 In the present invention, the specific surface area can be measured by a nitrogen adsorption method using, for example, “Flowsorb 2300” manufactured by Shimadzu Corporation. The amount of the measured powder was 0.3 g, and the preliminary degassing conditions were 10 minutes at 120 ° C. under atmospheric pressure.
本発明の希土類リン酸塩粉末が分散媒に高度に分散可能になるためには、希土類リン酸塩粉末の粒子径が重要となる。この観点から本発明者が検討したところ、レーザー回折散乱式粒度分布測定法による累積体積９９．９９容量％における体積累積粒径Ｄ99.99を特定の範囲に設定することが重要であることが判明した。詳細には、Ｄ99.99を１μｍ以上１００μｍ以下に設定することが重要である。レーザー回折散乱式粒度分布測定装置は堀場製作所社製のＬＡ９２０などで測定できる。Ｄ99.99が１００μｍを超えると、簡便な粉砕により高度にナノ粒子が分散した単分散液を得られることができない。例えば、粗粉砕機と微粉砕機が必要になり、Ｄ99.99の下限値に特に制限はなく、小さければ小さいほど好ましいが、１μｍ程度にＤ99.99が小さくなれば、分散液の透明性を十分に高くすることができる原料粉末となる。これらの観点から、Ｄ99.99は1μｍ以上１００μｍ以下であることが好ましく、１μｍ以上８０μｍ以下であることが更に好ましい。 In order for the rare earth phosphate powder of the present invention to be highly dispersible in the dispersion medium, the particle size of the rare earth phosphate powder is important. From this point of view, the present inventors have examined that it is important to set the volume cumulative particle diameter D 99.99 at a cumulative volume of 99.99% by volume by a laser diffraction / scattering particle size distribution measurement method within a specific range. . Specifically, it is important to set D 99.99 to 1 μm or more and 100 μm or less. The laser diffraction / scattering particle size distribution measuring apparatus can be measured by LA920 manufactured by Horiba, Ltd. When D 99.99 exceeds 100 μm, a monodispersed liquid in which nanoparticles are highly dispersed cannot be obtained by simple pulverization. For example, a coarse pulverizer and a fine pulverizer are required, and the lower limit value of D 99.99 is not particularly limited. The smaller the value, the better. However, when D 99.99 is reduced to about 1 μm, the transparency of the dispersion is sufficiently high. The raw material powder can be increased. From these viewpoints, D 99.99 is preferably 1 μm or more and 100 μm or less, and more preferably 1 μm or more and 80 μm or less.
なお、本発明において、レーザー回折散乱式粒度分布測定法による累積体積１００容量％における体積累積粒径Ｄ100でなく、Ｄ99.99で表した理由は、測定機器の仕様上、Ｄ100の正確な測定が困難であることによるものである。 In the present invention, the reason why D 99.99 is expressed instead of the volume cumulative particle diameter D 100 at a cumulative volume of 100 vol% by the laser diffraction / scattering particle size distribution measurement method is that D 100 is an accurate measurement due to the specifications of the measuring instrument. This is because of the difficulty.
本発明の希土類リン酸塩粉末は外力の作用によって容易に解砕される点にも特徴の一つを有する。この特徴によって、本発明の希土類リン酸塩粉末は、分散媒中に単分散しやすくなる。解砕の程度の尺度として、例えば超音波の照射前後におけるＤ99.99の変化の程度を採用した場合、超音波を照射した後のＤ99.99の値が、超音波照射前のＤ99.99の値に対して０．７５以下であることが好ましく、０．７０以下であることが好ましく、０．６５以下であることが更に好ましい。このような特徴を有する本発明の希土類リン酸塩粉末は、例えば後述する方法によって製造することができる。超音波の照射条件は、２２．５ｋＨｚ、３０Ｗ及び３分間とする。超音波の照射は、レーザー回折散乱式粒度分布測定装置の循環系に付帯された超音波装置で照射される。 The rare earth phosphate powder of the present invention is also characterized by being easily crushed by the action of external force. Due to this feature, the rare earth phosphate powder of the present invention is easily monodispersed in the dispersion medium. For example, when the degree of change of D 99.99 before and after ultrasonic irradiation is adopted as a measure of the degree of crushing, the value of D 99.99 after ultrasonic irradiation is compared to the value of D 99.99 before ultrasonic irradiation. Is preferably 0.75 or less, more preferably 0.70 or less, and still more preferably 0.65 or less. The rare earth phosphate powder of the present invention having such characteristics can be produced, for example, by the method described later. The ultrasonic irradiation conditions are 22.5 kHz, 30 W, and 3 minutes. The ultrasonic irradiation is performed by an ultrasonic apparatus attached to the circulation system of the laser diffraction / scattering particle size distribution measuring apparatus.
本発明の希土類リン酸塩粉末は、その形状として、例えば球状、多面体状、針状などの形状を採用し得る。特に、希土類リン酸塩粒子が球状であると、該粒子を含む分散液から光学レンズを製造する場合に、該光学レンズに複屈折が生じにくくなる点から好ましい。 The rare earth phosphate powder of the present invention may adopt, for example, a spherical shape, a polyhedral shape, or a needle shape. In particular, when the rare earth phosphate particles are spherical, when an optical lens is produced from a dispersion containing the particles, birefringence is less likely to occur in the optical lens.
本発明の希土類リン酸塩粉末は、その結晶子径が４５ｎｍ以下であることが好ましく、３０ｎｍ以下であることが更に好ましく、１０ｎｍ以下であることが一層好ましい。結晶子径がこの範囲である希土類リン酸塩粉末は、これを光学材料として用いた場合に複屈折が生じにくくなる。この範囲の結晶子径を有する希土類リン酸塩粉末は、例えば後述する方法によって製造することができる。結晶子径は、粉末Ｘ線回折法によって測定される。詳細には、Ｘ線回折装置（リガク社製 RINT-TTR III）を用い、試料を専用のガラスホルダーに充填し、50kＶ−３００ｍＡの電圧−電流を印加して発生させたＣｕ Ｋα線によって、サンプリング角０．０２°、走査速度４．０°／ｍｉｎの条件で測定した。測定結果を用いてＸＲＤ解析ソフトウエアＪＡＤＥにより結晶子径を求めた。 The rare earth phosphate powder of the present invention preferably has a crystallite diameter of 45 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less. A rare earth phosphate powder having a crystallite diameter in this range is less likely to cause birefringence when used as an optical material. The rare earth phosphate powder having a crystallite diameter in this range can be produced, for example, by the method described later. The crystallite diameter is measured by a powder X-ray diffraction method. Specifically, using an X-ray diffractometer (RINT-TTR III manufactured by Rigaku Corporation), a sample is filled in a dedicated glass holder, and sampling is performed by Cu Kα rays generated by applying a voltage-current of 50 kV-300 mA. The measurement was performed under the conditions of an angle of 0.02 ° and a scanning speed of 4.0 ° / min. The crystallite diameter was determined by XRD analysis software JADE using the measurement results.
次に、本発明の希土類リン酸塩粉末の好適な製造工程について説明する。希土類リン酸塩粉末は、１種又は２種以上の希土類元素源を含む水溶液と、リン酸根を含む水溶液とを混合して、１種又は２種以上の希土類リン酸塩の沈殿を生じさせることで得られる。この沈殿は必要に応じて焼成工程に付され、その結晶化度が高められる。また、結晶子径が調整される。 Next, the suitable manufacturing process of the rare earth phosphate powder of this invention is demonstrated. The rare earth phosphate powder is formed by mixing an aqueous solution containing one or more rare earth element sources and an aqueous solution containing a phosphate radical to cause precipitation of one or more rare earth phosphates. It is obtained by. This precipitation is subjected to a baking step as necessary to increase its crystallinity. In addition, the crystallite diameter is adjusted.
希土類元素源を含む水溶液としては、該水溶液中における希土類元素の濃度が、０．０１〜１．５ｍｏｌ／リットル、特に０．０１〜１ｍｏｌ／リットル、とりわけ０．０１〜０．５ｍｏｌ／リットルのものを用いることが好ましい。この水溶液中において希土類元素は三価のイオンの状態になっているか、又は三価のイオンに配位子が配位した錯イオンの状態になっていることが好ましい。希土類元素源を含む水溶液を調製するためには、例えば硝酸水溶液に希土類酸化物（例えばＬｎ2Ｏ3等）を添加してこれを溶解させればよい。 The aqueous solution containing the rare earth element source has a rare earth element concentration of 0.01 to 1.5 mol / liter, particularly 0.01 to 1 mol / liter, especially 0.01 to 0.5 mol / liter in the aqueous solution. Is preferably used. In this aqueous solution, the rare earth element is preferably in a trivalent ion state or in a complex ion state in which a ligand is coordinated to the trivalent ion. In order to prepare an aqueous solution containing a rare earth element source, for example, a rare earth oxide (for example, Ln 2 O 3 or the like) may be added to an aqueous nitric acid solution and dissolved.
リン酸根を含む水溶液においては、該水溶液中におけるリン酸化学種の合計の濃度を、０．０１〜３ｍｏｌ／リットル、特に０．０１〜１ｍｏｌ／リットル、とりわけ０．０１〜０．５ｍｏｌ／リットルとすることが好ましい。ｐＨ調整のために、アルカリ種を添加することもできる。アルカリ種としては、例えばアンモニア、炭酸水素アンモニウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム、エチルアミン、プロピルアミン、水酸化ナトリウム、水酸化カリウム等の塩基性化合物を用いることができる。 In an aqueous solution containing a phosphate group, the total concentration of phosphoric acid species in the aqueous solution is 0.01 to 3 mol / liter, particularly 0.01 to 1 mol / liter, especially 0.01 to 0.5 mol / liter. It is preferable to do. An alkali species can also be added for pH adjustment. As the alkali species, for example, basic compounds such as ammonia, ammonium hydrogen carbonate, ammonium carbonate, sodium hydrogen carbonate, sodium carbonate, ethylamine, propylamine, sodium hydroxide and potassium hydroxide can be used.
希土類元素源を含む水溶液とリン酸根を含む水溶液は、リン酸イオン／希土類元素イオンのモル比が０．５〜１０、特に１〜１０、とりわけ１〜５となるように混合することが、効率よく沈殿生成物が得られる点から好ましい。 It is efficient that the aqueous solution containing the rare earth element source and the aqueous solution containing the phosphate radical are mixed so that the molar ratio of phosphate ions / rare earth element ions is 0.5 to 10, particularly 1 to 10, especially 1 to 5. This is preferable because a precipitated product is often obtained.
本製造方法においては、希土類元素源を含む水溶液と、リン酸根を含む水溶液との混合を、両者を同時添加して行う。この操作を行うことで、外力の作用によって容易に解砕可能な希土類リン酸塩粉末が得られることが本発明者らの検討の結果判明した。これに対して、両者を同時添加しない場合には、分散媒に高分散可能な希土類リン酸塩粉末が得られる場合はあるものの、該粉末は外力の作用による解砕が容易に生じないものとなる。 In this production method, the aqueous solution containing the rare earth element source and the aqueous solution containing the phosphate radical are mixed and added at the same time. As a result of the study by the present inventors, it was found that a rare earth phosphate powder that can be easily crushed by the action of an external force can be obtained by performing this operation. On the other hand, when both are not added at the same time, a rare earth phosphate powder that can be highly dispersed in a dispersion medium may be obtained, but the powder is not easily crushed by the action of external force. Become.
本製造方法において同時添加とは、一の容器中に、一方の液と他方の液とを同時に添加して両者を混合することを言う。尤も、一方の液と他方の液との添加開始時期及び／又は添加完了時期が完全に一致していることは要せず、装置の性能や操作条件の振れ等に起因して、意図せず不可避的に添加開始時期及び／又は添加完了時期にずれが生じる場合は許容される。したがって、容器中に蓄えられた一方の液に、他方の液を添加する操作、例えば特許文献２の実施例に記載の操作は同時添加とは言わない。 In this production method, simultaneous addition means that one liquid and the other liquid are simultaneously added and mixed in one container. However, it is not necessary that the addition start timing and / or the addition completion timing of one liquid and the other liquid completely coincide with each other. Inevitably, a deviation occurs in the addition start timing and / or the completion timing of addition. Therefore, the operation of adding the other liquid to one liquid stored in the container, for example, the operation described in the example of Patent Document 2, is not said to be simultaneous addition.
希土類元素源を含む水溶液と、リン酸根を含む水溶液とを同時添加する場合には、両者を高剪断条件下に同時添加することが好ましい。高剪断条件下に同時添加することで、外力の作用によって容易に解砕可能な希土類リン酸塩粉末が一層得られやすいという利点がある。 When the aqueous solution containing the rare earth element source and the aqueous solution containing the phosphate radical are added simultaneously, it is preferable to add both of them simultaneously under high shear conditions. The simultaneous addition under high shear conditions has the advantage that a rare earth phosphate powder that can be easily crushed by the action of external force is more easily obtained.
希土類元素源を含む水溶液と、リン酸根を含む水溶液とを高剪断条件下に同時添加には、例えば各種ホモジナイザーや、高水圧式湿式ジェットミルを用いることができる。特にホモジナイザー中で両水溶液を同時添加することが、外力の作用によって容易に解砕可能な希土類リン酸塩粉末が一層得られやすいので好ましい。 For simultaneous addition of an aqueous solution containing a rare earth element source and an aqueous solution containing a phosphate group under high shear conditions, for example, various homogenizers or a high hydraulic wet jet mill can be used. In particular, it is preferable to add both aqueous solutions simultaneously in a homogenizer because rare earth phosphate powder that can be easily crushed by the action of external force can be obtained more easily.
希土類リン酸塩の生成においては、反応によって生成した核粒子の成長を妨げる物質が反応系内に存在しないことが好ましい。そのような物質が反応系に存在すると、生成した核粒子の成長が阻害され、得られる希土類リン酸塩の一次粒子径が過度に小さくなり、比表面積が過度に大きくなってしまうことがある。一次粒子径が過度に小さくなることは、希土類リン酸塩の表面活性が過度に高くなって、意図しない溶解析出反応が起こり、分散液中での安定性が低下する点からも有利とは言ない。生成した核粒子の成長を妨げる物質としては、例えばクエン酸などが挙げられる。クエン酸は、生成した核粒子の表面に吸着して、該粒子がそれ以上大きくなることを阻害する。別の側面として、クエン酸を用いることは、反応後の廃液中のＢＯＤ（Biochemical Oxygen Demand）が高くなり、廃液処理を経済的に行えない点から有利ではない。 In the production of the rare earth phosphate, it is preferable that a substance that prevents the growth of the core particles produced by the reaction does not exist in the reaction system. When such a substance is present in the reaction system, the growth of the produced core particles is inhibited, and the primary particle diameter of the obtained rare earth phosphate may be excessively decreased and the specific surface area may be excessively increased. An excessively small primary particle size is also advantageous in that the surface activity of the rare earth phosphate becomes excessively high, an unintended dissolution and precipitation reaction occurs, and the stability in the dispersion is lowered. Absent. Examples of the substance that hinders the growth of the generated core particles include citric acid. Citric acid is adsorbed on the surface of the produced core particles and inhibits the particles from becoming larger. As another aspect, the use of citric acid is not advantageous because BOD (Biochemical Oxygen Demand) in the waste liquid after the reaction becomes high and waste liquid treatment cannot be economically performed.
希土類元素源を含む水溶液と、リン酸根を含む水溶液とを混合して得られる反応系のｐＨは、沈殿生成物の形態へ影響を及ぼす。この理由は次のとおりである。リン酸イオンはｐＨによって形態が変化する。例えばアンモニアをｐＨ調整剤として用いた場合、ｐＨ＜４ではＨ2ＰＯ4 -の存在が支配的になる。ｐＨが４〜８では、Ｈ2ＰＯ4 -及びＨＰＯ4 2-の存在が支配的になる。ｐＨ＞８ではＨＰＯ4 2-及びＰＯ4 3-の存在が支配的になる。希土類元素イオンとリン酸イオンとの反応において、低ｐＨで生じるＨ2ＰＯ4 -と希土類元素イオンとの反応ではＬｎＨＰＯ4が生成しやすい。一方、高ｐＨで生じるＰＯ4 3-と希土類元素イオンとの反応ではＬｎＰＯ4が生成しやすい（永長久彦著「溶液を反応場とする無機合成」培風館（２０００年））。 The pH of the reaction system obtained by mixing the aqueous solution containing the rare earth element source and the aqueous solution containing the phosphate radical affects the form of the precipitated product. The reason for this is as follows. The form of phosphate ions changes with pH. For example, when ammonia is used as a pH adjuster, the presence of H 2 PO 4 − is dominant at pH <4. When the pH is 4 to 8, the presence of H 2 PO 4 − and HPO 4 2− becomes dominant. At pH> 8, the presence of HPO 4 2- and PO 4 3- is dominant. In the reaction between rare earth element ions and phosphate ions, LnHPO 4 is likely to be generated in the reaction between H 2 PO 4 − generated at low pH and rare earth element ions. On the other hand, LnPO 4 is likely to be formed by the reaction between PO 4 3− and rare earth element ions generated at high pH (Hisashi Naganaga, “Inorganic synthesis using solution as reaction field” Bafukan (2000)).
また沈殿生成物は、混合時の温度によっても変化する。この観点から、反応温度は好ましくは２０〜１００℃である。一般的な傾向として、反応温度が高くなると、結晶性の希土類リン酸塩が得られやすくなり、かつその結晶性が高くなる。結晶性が高い場合には、以下に説明する焼成工程が不要となるので、一層簡便な手法で希土類リン酸塩を得ることができる。 The precipitated product also changes depending on the temperature at the time of mixing. From this viewpoint, the reaction temperature is preferably 20 to 100 ° C. As a general tendency, when the reaction temperature is increased, a crystalline rare earth phosphate is easily obtained and the crystallinity thereof is increased. When the crystallinity is high, the firing step described below is not necessary, so that the rare earth phosphate can be obtained by a simpler method.
以上のようにして希土類リン酸塩が得られたら、これを常法に従い固液分離した後、１回又は複数回水洗する。水洗は、液の導電率が例えば２０００μＳ／ｃｍ以下になるまで行うことが好ましい。 When the rare earth phosphate is obtained as described above, this is subjected to solid-liquid separation according to a conventional method and then washed with water once or a plurality of times. Washing with water is preferably performed until the electrical conductivity of the liquid reaches, for example, 2000 μS / cm or less.
沈殿生成物がアモルファスである場合、これを結晶性のものにするために焼成を行うことが好ましい。焼成は、大気中等の含酸素雰囲気で行うことができる。その場合の焼成条件は、焼成温度が好ましくは３００〜１０００℃であり、更に好ましくは４００〜１０００℃である。この温度範囲を採用することで、目的とする比表面積や結晶子径を有する希土類リン酸塩粉末を容易に得ることができる。焼成温度が過度に高くなると、焼結が進行して粒子の比表面積が低下する傾向にある。焼成時間は、焼成温度がこの範囲内であることを条件として、好ましくは１〜２０時間、更に好ましくは１〜１０時間である。 When the precipitated product is amorphous, it is preferable to perform calcination to make it crystalline. Firing can be performed in an oxygen-containing atmosphere such as the air. The firing condition in that case is preferably a firing temperature of 300 to 1000 ° C, more preferably 400 to 1000 ° C. By adopting this temperature range, it is possible to easily obtain a rare earth phosphate powder having a target specific surface area and crystallite diameter. If the firing temperature is excessively high, sintering proceeds and the specific surface area of the particles tends to decrease. The firing time is preferably 1 to 20 hours, more preferably 1 to 10 hours, provided that the firing temperature is within this range.
以上のとおりにして得られた本発明の希土類リン酸塩粉末は、これをこのまま乾燥状態で用いてもよく、あるいは分散媒中に分散させた分散液の状態で用いてもよい。特筆すべきは、先に述べたとおりの比表面積及びＤ99.99を有する本発明の希土類リン酸塩粉末は、分散媒への分散性が良好であることである。特に、本発明の希土類リン酸塩粉末は、外力の作用によって解砕されやすいものなので、このことに起因して、希土類リン酸塩粉末が単分散した分散液を容易に得ることができる。また、分散質である希土類リン酸塩粉末を、沈殿を生じることなく高濃度で分散させることができる。例えば、希土類リン酸塩粉末の濃度が好ましくは５〜５０質量％という高濃度のものとなる。更に好ましい濃度は５〜４０質量％であり、一層好ましい濃度は５〜３０質量％であり、更に一層好ましい濃度は５〜２０質量％であり、とりわけ好ましい濃度は７〜１５質量％である。かかる高濃度の水分散液は、該水分散液の塗布によって例えば光学レンズを製造する場合に、塗布の回数を少なくしても所望の厚みを有する薄膜を形成できる点から有利である。 The rare earth phosphate powder of the present invention obtained as described above may be used in a dry state as it is, or may be used in the state of a dispersion dispersed in a dispersion medium. It should be noted that the rare earth phosphate powder of the present invention having the specific surface area and D 99.99 as described above has good dispersibility in the dispersion medium. In particular, since the rare earth phosphate powder of the present invention is easily crushed by the action of external force, it is possible to easily obtain a dispersion in which the rare earth phosphate powder is monodispersed. Further, the rare earth phosphate powder as a dispersoid can be dispersed at a high concentration without causing precipitation. For example, the concentration of the rare earth phosphate powder is preferably as high as 5 to 50% by mass. A more preferable concentration is 5 to 40% by mass, a more preferable concentration is 5 to 30% by mass, an even more preferable concentration is 5 to 20% by mass, and a particularly preferable concentration is 7 to 15% by mass. Such a high concentration aqueous dispersion is advantageous in that, for example, when an optical lens is produced by application of the aqueous dispersion, a thin film having a desired thickness can be formed even if the number of times of application is reduced.
分散液は、希土類リン酸塩を１種含むものであってもよく、必要に応じ２種以上含むものであってもよい。いずれの場合であっても、この分散液は、高屈折率でかつ高アッベ数を有する材料である希土類リン酸塩粉末を含有しているので、かかる材料を含む本発明の水分散液は、光学レンズ等の光学材料を製造するための原料として好適なものである。 The dispersion may contain one kind of rare earth phosphate or may contain two or more kinds as required. In any case, since the dispersion contains rare earth phosphate powder that is a material having a high refractive index and a high Abbe number, the aqueous dispersion of the present invention containing such a material is It is suitable as a raw material for producing an optical material such as an optical lens.
分散液は、希土類リン酸塩粉末に加え、高屈折率を有する金属酸化物の粉末を更に含んでいてもよい。そのような金属酸化物としては、例えばＭｇ、Ｃａ、Ｔｉ、Ｚｎ、Ｚｒ、Ｔａ、Ｎｂ、Ｇａ、Ｇｅ、Ｓｎ、Ｉｎ、Ｈｆ、Ｙ、ランタノイド（Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）などの金属の酸化物が挙げられる。これらの金属酸化物は、１種又は２種以上を用いることができる。これらの金属酸化物は、分散液に含まれる固形分としての粒子全体に対して、０．１〜５０質量％程度用いることができる。尤も、分散液は、分散媒の種類によらず、希土類リン酸塩粉末以外の固形成分を含んでいないことが望ましい。 The dispersion may further contain a metal oxide powder having a high refractive index in addition to the rare earth phosphate powder. Examples of such metal oxides include Mg, Ca, Ti, Zn, Zr, Ta, Nb, Ga, Ge, Sn, In, Hf, Y, and lanthanoids (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and other metal oxides. These metal oxides can be used alone or in combination of two or more. These metal oxides can be used in an amount of about 0.1 to 50% by mass with respect to the entire particles as solids contained in the dispersion. However, it is desirable that the dispersion does not contain a solid component other than the rare earth phosphate powder regardless of the type of the dispersion medium.
分散液の分散媒としては、水又は有機溶媒を用いることができる。有機溶媒としては、水溶性有機溶媒及び非水溶性有機溶媒の双方を用いることができる。水溶性有機溶媒を用いる場合には、水と混合してなる混合溶媒としても用いることができる。いずれの分散媒を用いた場合でも、分散液は高透明性を有するものとなる。 As a dispersion medium of the dispersion liquid, water or an organic solvent can be used. As the organic solvent, both a water-soluble organic solvent and a water-insoluble organic solvent can be used. When a water-soluble organic solvent is used, it can also be used as a mixed solvent formed by mixing with water. Regardless of which dispersion medium is used, the dispersion has high transparency.
水溶性有機溶媒としては、例えばモノアルコール、多価アルコール、ケトン、エステル、アミン、チオール、ピロリドン系等で水と相溶できる溶媒を用いることができる。一方、非水溶性有機溶媒としては、例えば飽和又は不飽和の炭化水素系化合物やハロゲン化炭化水素とその環状化合物、長鎖のモノアルコールや多価アルコール、及び芳香族系化合物等に代表される水と相溶しない有機溶媒を用いることができる。これらの有機溶媒は、１種を単独で、又は２種以上を組み合わせて用いることができる。前記ケトン類としては、例えばアセトン、メチルエチルケトン、ジエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、イソホロンなどが挙げられる。 As the water-soluble organic solvent, for example, a solvent compatible with water such as monoalcohol, polyhydric alcohol, ketone, ester, amine, thiol, and pyrrolidone can be used. On the other hand, examples of the water-insoluble organic solvent include saturated or unsaturated hydrocarbon compounds, halogenated hydrocarbons and cyclic compounds thereof, long-chain monoalcohols and polyhydric alcohols, and aromatic compounds. An organic solvent that is incompatible with water can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone.
分散液は、長期間保存したときの安定性が高いものであることによっても特徴づけられる。例えば、室温下に１ヶ月間保存しても沈殿が生じない程度の安定性を有している。 Dispersions are also characterized by their high stability when stored for long periods of time. For example, it has a stability that does not cause precipitation even when stored for 1 month at room temperature.
分散液の安定性を高めるために、該分散液が水性分散液（すなわち分散媒として水、又は水と水溶性有機溶媒との混合溶媒を用いた分散液）の場合には、該水性分散液のｐＨを酸性側の特定の範囲又はアルカリ性側の特定の範囲に設定することが好ましい。酸性側については、水性分散液のｐＨを好ましくは１以上５未満に設定し、更に好ましくは２以上５未満、一層好ましくは２以上４以下に設定する。酸性側において水性分散液のｐＨを１以上に設定することで、希土類リン酸塩が溶解してしまうことを効果的に防止できる。また、ｐＨを５未満に設定することで、希土類リン酸塩粉末を高度に分散させることが容易となる。アルカリ性側については、水性分散液のｐＨを好ましくは９．１以上１４以下に設定し、更に好ましくは９．１以上１３．５以下、一層好ましくは９．１以上１３以下に設定する。アルカリ性側において水性分散液のｐＨを９．１以上の設定することで、希土類リン酸塩粉末を高度に分散させることが容易となる。また、ｐＨを１４以下に設定することで、希土類リン酸塩が水酸化物イオンと意図せず反応することによる粒子表面の変質を効果的に防止できる。これらのｐＨは、水性分散液の保存中又は使用時における温度での値のことである。 In order to increase the stability of the dispersion, when the dispersion is an aqueous dispersion (that is, a dispersion using water or a mixed solvent of water and a water-soluble organic solvent), the aqueous dispersion It is preferable to set the pH of a specific range on the acidic side or a specific range on the alkaline side. On the acidic side, the pH of the aqueous dispersion is preferably set to 1 or more and less than 5, more preferably 2 or more and less than 5, and still more preferably 2 or more and 4 or less. By setting the pH of the aqueous dispersion to 1 or more on the acidic side, it is possible to effectively prevent the rare earth phosphate from being dissolved. Moreover, it becomes easy to disperse | distribute rare earth phosphate powder highly by setting pH to less than 5. For the alkaline side, the pH of the aqueous dispersion is preferably set to 9.1 to 14, more preferably 9.1 to 13.5, and still more preferably 9.1 to 13. By setting the pH of the aqueous dispersion to 9.1 or more on the alkaline side, it becomes easy to highly disperse the rare earth phosphate powder. In addition, by setting the pH to 14 or less, it is possible to effectively prevent alteration of the particle surface due to unintentional reaction of rare earth phosphate with hydroxide ions. These pH values are values at temperatures during storage or use of the aqueous dispersion.
水性分散液のｐＨを上述の範囲内に調整するためには、水性分散液にｐＨ調整剤を添加すればよい。酸性側で用いられるｐＨ調整剤としては、例えば各種の有機酸や無機酸を用いることができる。有機酸としては例えば酢酸、ギ酸及びプロピオン酸などが挙げられる。無機酸としては、例えばフッ酸、硝酸、塩酸及び硫酸などが挙げられる。これらの有機酸や無機酸は、１種を単独で又は２種以上を組み合わせて用いることができる。アルカリ性側で用いられるｐＨ調整剤としては、各種の水酸化物、アルキルアミン及びアンモニア水等を用いることができる。水酸化物としては例えば水酸化テトラメチルアンモニウム等の水酸化テトラアルキルアンモニウム、水酸化ナトリウムや水酸化カリウム等のアルカリ金属の水酸化物が挙げられる。アルキルアミンとしては、ｐＨ調整のしやすさに応じてモノアルキルアミン、ジアルキルアミン及びトリアルキルアミンのいずれをも用いることができる。アルキルアミンにおけるアルキル基としては、例えば同一の又は異なる、炭素数１〜４の低級アルキル基（メチル基やエチル基等）を用いることができる。これら水酸化物、アルキルアミン及びアンモニア水等は、１種を単独で又は２種以上を組み合わせて用いることができる。以上の各種のｐＨ調整剤の水性分散液への添加量は、水性分散液のｐＨが上述の範囲となるような量とすればよい。 In order to adjust the pH of the aqueous dispersion within the above range, a pH adjuster may be added to the aqueous dispersion. As the pH adjuster used on the acidic side, for example, various organic acids and inorganic acids can be used. Examples of the organic acid include acetic acid, formic acid and propionic acid. Examples of inorganic acids include hydrofluoric acid, nitric acid, hydrochloric acid, and sulfuric acid. These organic acids and inorganic acids can be used singly or in combination of two or more. As the pH adjuster used on the alkaline side, various hydroxides, alkylamines, aqueous ammonia and the like can be used. Examples of the hydroxide include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. As the alkylamine, any of monoalkylamine, dialkylamine and trialkylamine can be used depending on the ease of pH adjustment. As the alkyl group in the alkylamine, for example, the same or different lower alkyl group having 1 to 4 carbon atoms (such as a methyl group or an ethyl group) can be used. These hydroxides, alkylamines, aqueous ammonia and the like can be used singly or in combination of two or more. The amount of the above various pH adjusting agents added to the aqueous dispersion may be an amount such that the pH of the aqueous dispersion is in the above range.
分散媒が非水溶性有機溶媒のみからなる分散液、すなわち油性分散液の場合には、長期間保存したときの安定性を高める観点から、該油性分散液中に分散剤を含有させることが好ましい。分散剤としては、例えば、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤、両性界面活性剤、Ｓｉ，Ｔｉ，Ｚｒ，Ａｌなどの各種カップリング剤及びキレート剤等を用いることができる。これらの分散剤は１種を単独で、又は２種以上を組み合わせて用いることができる。これらの分散剤のうち、特にアニオン系界面活性剤、カップリング剤、キレート剤を用いることが、ナノ粒子表面に強固に結合又は配位し分散液の長期安定性の点から好ましい。分散液に占める分散剤の割合は、０．１質量％以上４０質量％以下であることが好ましく、１質量％以上３０質量％以下であることが更に好ましい。 In the case where the dispersion medium is a dispersion composed of only a water-insoluble organic solvent, that is, an oily dispersion, it is preferable to contain a dispersant in the oily dispersion from the viewpoint of enhancing the stability when stored for a long period of time. . As the dispersant, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, various coupling agents such as Si, Ti, Zr, and Al, and chelating agents should be used. Can do. These dispersants can be used alone or in combination of two or more. Of these dispersants, it is particularly preferable to use an anionic surfactant, a coupling agent, and a chelating agent from the viewpoint of long-term stability of the dispersion liquid because they are firmly bonded or coordinated to the nanoparticle surface. The proportion of the dispersing agent in the dispersion is preferably 0.1% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 30% by mass or less.
分散液は、可視光の波長領域（４００〜８００ｎｍ）において高透明性であることによっても特徴づけられる。詳細には、可視光の波長領域における透過率が、光路長１ｃｍのセルを用いて測定したとき好ましくは５０％以上、更に好ましくは８０％以上、一層好ましくは９０％以上という高透明性のものである。このように透明性の高い分散液を用いて塗膜を形成すると、乾燥後の塗膜の透明性が極めて高くなる。したがって、分散液は、可視光の波長領域において高屈折率及び低波長分散性を有する透明膜の製造に非常に有用である。可視光の波長領域において高屈折率及び低波長分散性を有する透明膜は、例えばシート状レンズを始めとして、光学レンズの薄型化に寄与する。分散液の透明性は、例えば（株）日立ハイテクノロジー社製の分光光度計Ｕ−４０００によって測定することができる。 The dispersion is also characterized by being highly transparent in the visible wavelength region (400-800 nm). In detail, when the transmittance in the wavelength region of visible light is measured using a cell having an optical path length of 1 cm, the transparency is preferably 50% or more, more preferably 80% or more, more preferably 90% or more. It is. Thus, when a coating film is formed using a highly transparent dispersion liquid, the transparency of the coating film after drying becomes extremely high. Therefore, the dispersion is very useful for the production of a transparent film having a high refractive index and low wavelength dispersion in the visible light wavelength region. A transparent film having a high refractive index and low wavelength dispersion in the visible light wavelength region contributes to a reduction in the thickness of optical lenses such as sheet lenses. The transparency of the dispersion can be measured, for example, with a spectrophotometer U-4000 manufactured by Hitachi High-Technology Corporation.
分散液は、例えば、希土類リン酸塩粉末と分散媒とを混合してスラリーとなし、ビーズミル等のメディアミルによって湿式粉砕を行うことで製造することができる。使用するビーズとしては、例えばジルコニアビーズやアルミナビーズ等が挙げられる。この場合、水性分散液を調製するときには、各種のｐＨ調整剤をスラリーに添加して粉砕操作を行うことで、希土類リン酸塩粉末を単分散状態に近づけやすくなる。一方、油性分散液を調製するときには、各種の分散剤をスラリーに添加して粉砕操作を行うことで、希土類リン酸塩粉末を単分散状態に近づけやすくなる。 The dispersion can be produced, for example, by mixing a rare earth phosphate powder and a dispersion medium to form a slurry, and performing wet pulverization using a media mill such as a bead mill. Examples of the beads to be used include zirconia beads and alumina beads. In this case, when preparing the aqueous dispersion, it is easy to bring the rare earth phosphate powder closer to a monodispersed state by adding various pH adjusters to the slurry and performing a pulverization operation. On the other hand, when preparing an oil-based dispersion, it is easy to bring the rare earth phosphate powder closer to a monodispersed state by adding various dispersants to the slurry and performing a pulverization operation.
前記のｐＨ調整剤としては、液のｐＨを好ましくは１以上５未満、更に好ましくは２以上５未満、一層好ましくは２以上４以下に調整できるものを用いることが好ましい。そのようなｐＨ調整剤としては、例えば、先に述べた有機酸や無機酸を用いることができる。また、液のｐＨを好ましくは９．１以上１４以下、更に好ましくは９．１以上１３．５以下、一層好ましくは９．１以上１３以下に調整できるものを用いることが好ましい。そのようなｐＨ調整剤としては、例えば、先に述べた各種の水酸化物を用いることが好ましい。 As the pH adjuster, it is preferable to use one that can adjust the pH of the liquid to preferably 1 or more and less than 5, more preferably 2 or more and less than 5, and still more preferably 2 or more and 4 or less. As such a pH adjuster, for example, the organic acids and inorganic acids described above can be used. In addition, it is preferable to use a liquid whose pH can be adjusted to preferably 9.1 to 14, more preferably 9.1 to 13.5, and still more preferably 9.1 to 13. As such a pH adjuster, it is preferable to use, for example, the various hydroxides described above.
前記のｐＨ調整剤は、これを湿式粉砕時にスラリーに添加することに代えて、湿式粉砕して得られた水性分散液に添加してもよい。ｐＨ調整剤を水性分散液に添加する場合、その添加量は、水性分散液のｐＨが、好ましくは上述の範囲内となるようにする。なお、湿式粉砕によって希土類リン酸塩粒子に新たな表面が生じ、該表面が酸又はアルカリと反応する結果、液のｐＨが変動することがある。したがって、湿式粉砕時にｐＨ調整剤を添加する場合には、湿式粉砕におけるｐＨの変動を見越してｐＨ調整剤の添加量を決定することが好ましい。 The pH adjusting agent may be added to an aqueous dispersion obtained by wet grinding instead of adding it to the slurry during wet grinding. When the pH adjuster is added to the aqueous dispersion, the added amount is such that the pH of the aqueous dispersion is preferably within the above-mentioned range. Note that a new surface is generated in the rare earth phosphate particles by wet pulverization, and the pH of the liquid may fluctuate as a result of the surface reacting with acid or alkali. Therefore, when adding a pH adjuster at the time of wet pulverization, it is preferable to determine the addition amount of the pH adjuster in anticipation of fluctuations in pH during wet pulverization.
湿式粉砕後、液とビーズとを分離し、更にメンブランフィルターによって粗粒を除去することで、目的とする分散液が得られる。このようにして得られた分散液は無色透明であり、可視光の透過率が高いものである。また、長期間保存しても沈殿の生じない安定なものである。 After the wet pulverization, the liquid and the beads are separated, and the coarse particles are removed by a membrane filter to obtain a target dispersion. The dispersion thus obtained is colorless and transparent and has a high visible light transmittance. Moreover, it is stable and does not cause precipitation even when stored for a long time.
このようにして得られた分散液は、それに含まれる希土類リン酸塩が有する高屈折率及び低波長分散性や、分散液が有する可視光に対する透明性を利用して、各種の光学材料や電子材料に用いることができる。例えば、レンズ等の光学系部品、反射防止膜、赤外線透過膜等に用いることができる。具体的には、分散液を各種の基板、例えば透明基板やレンズ等の表面に塗布して塗膜を形成し、該塗膜を乾燥させることで、高透明性、高屈折率及び低波長分散性を有する薄膜を形成することができる。乾燥後の薄膜を、必要に応じて不活性雰囲気下、大気等の酸化性雰囲気下又は弱還元性雰囲気下（例えば爆発限界濃度以下の含水素雰囲気下）に焼成してもよい。この薄膜は、レンズの屈折率を更に高めるために、あるいは薄型レンズそのものとして有用である。更に分散液は、それに含まれる希土類リン酸塩粉末が樹脂中に分散されてなる樹脂レンズの原料としても好適に用いられる。 The dispersion obtained in this way can be used for various optical materials and electrons by utilizing the high refractive index and low wavelength dispersibility of the rare earth phosphate contained therein and the transparency to visible light of the dispersion. Can be used for materials. For example, it can be used for optical system parts such as lenses, antireflection films, infrared transmission films and the like. Specifically, the dispersion is applied to the surface of various substrates, such as transparent substrates and lenses, to form a coating film, and the coating film is dried to provide high transparency, high refractive index, and low wavelength dispersion. A thin film having properties can be formed. The dried thin film may be fired as necessary under an inert atmosphere, an oxidizing atmosphere such as air, or a weakly reducing atmosphere (for example, a hydrogen-containing atmosphere having an explosion limit concentration or less). This thin film is useful for further increasing the refractive index of the lens or as a thin lens itself. Further, the dispersion is also suitably used as a raw material for a resin lens in which a rare earth phosphate powder contained therein is dispersed in a resin.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “mass%”.
〔実施例１〕
（１）リン酸ルテチウム粉末及びそれを含む水性分散液の製造
１） ガラス容器に水３７０ｇを計量し、８０℃に加温した。
２） １）へ８５％硝酸（和光社製）１４．４ｇを添加した。
３） ２）へＬｕ2Ｏ3（日本イットリウム社製）７．４ｇを添加し、完全に溶解させ室温（２５℃）まで冷却した。
４） 別のガラス容器に水３９０ｇ、２５％リン酸５．３ｇ、２５％アンモニア水９．３ｇを添加した。
５） ３）の溶液と４）の溶液をそれぞれ１０ｍＬ／ｍｉｎでホモジナイザーへ送液し、ホモジナイザー中に同時添加して混合した。ホモジナイザーの回転数は２００００ｒｐｍに設定し、反応液のｐＨは０．９〜１．６であった。
６） 混合終了後、沈殿物をデカンテーション洗浄により、上澄みの導電率が１００μＳ／ｃｍ以下になるまで洗浄を行った。
７） 洗浄終了後、減圧濾過で固液分離した。
８） ７）を大気中で１２０℃×５ｈ乾燥させ、白色粉末を得た。
９） ８）を大気中８００℃×５ｈ焼成した。
１０） ９）で得られた焼成粉末のＸＲＤ測定を行ったところ、正方晶のＬｕＰＯ4のピークが確認された。
１１） レーザー回折散乱法による粒度分布測定結果と、ＸＲＤによる（２００）面の結晶子径と、窒素吸着法による比表面積の測定結果を表１にまとめる。粒度分布測定は、超音波の照射前後において行った。超音波装置としては、レーザー回折散乱式粒度分布測定装置（ＨＯＲＩＢＡ製 ＬＡ−９２０）の測定循環系に付帯のインラインの超音波による照射を行った。超音波の照射条件は、上述したとおりである。
１２） 水性分散液の調製は次のとおりに行った。５０ｍＬの樹脂製容器に、１０）で得られたＬｕＰＯ4粉末２．０ｇと、１％テトラメチルアンモニウムハイドライド水溶液２３ｇ、０．１ｍｍφジルコニアビーズ１００ｇを入れ、ペイントシェーカーによる粉砕を行った。
１３） 固液分離後、０．２μｍのメンブランフィルターに通し、粗粒の除去を行った。
１４） １３）で得られたスラリーは無色透明であり、λ＝６５０ｎｍの赤色レーザーポインターを照射したところチンダル現象が見られ、粒子が高分散していることを確認した。
１５） １４）の液を少量測り取り、２００℃で乾燥させたときの固形分濃度は１２％であり、ガラス質の透明な固形分が残存していた。
１６） １４）の液の透過率を測定したところ、可視光域（λ＝４００〜８００ｎｍ）に吸収がないことを確認し、λ＝５５５ｎｍにおける透過率は８２％であり、透明性が高いことを確認した。ｐＨは１２であった。
１７） この液を常温で１ヶ月間保存しても沈殿を生じることがなく、高分散状態を維持したままであった。これらの結果をまとめて表２に示す。
[Example 1]
(1) Production of lutetium phosphate powder and aqueous dispersion containing it 1) 370 g of water was weighed into a glass container and heated to 80 ° C.
2) 14.4 g of 85% nitric acid (manufactured by Wako) was added to 1).
3) 7.4 g of Lu 2 O 3 (manufactured by Nippon Yttrium Co., Ltd.) was added to 2), completely dissolved, and cooled to room temperature (25 ° C.).
4) To another glass container, 390 g of water, 5.3 g of 25% phosphoric acid, and 9.3 g of 25% aqueous ammonia were added.
5) The solution of 3) and the solution of 4) were each sent to a homogenizer at 10 mL / min, and were simultaneously added and mixed in the homogenizer. The rotation speed of the homogenizer was set to 20000 rpm, and the pH of the reaction solution was 0.9 to 1.6.
6) After completion of the mixing, the precipitate was washed by decantation washing until the supernatant conductivity became 100 μS / cm or less.
7) After washing, solid-liquid separation was performed by vacuum filtration.
8) 7) was dried in air at 120 ° C. for 5 hours to obtain a white powder.
9) Baked 8) in the air at 800 ° C. for 5 hours.
10) When XRD measurement of the calcined powder obtained in 9) was performed, a peak of tetragonal LuPO 4 was confirmed.
11) Table 1 summarizes the particle size distribution measurement result by the laser diffraction scattering method, the crystallite diameter of the (200) plane by XRD, and the measurement result of the specific surface area by the nitrogen adsorption method. The particle size distribution was measured before and after the ultrasonic irradiation. As an ultrasonic device, irradiation by an in-line ultrasonic wave was performed on a measurement circulation system of a laser diffraction / scattering particle size distribution measuring device (LA-920 manufactured by HORIBA). The ultrasonic irradiation conditions are as described above.
12) The aqueous dispersion was prepared as follows. In a 50 mL resin container, 2.0 g of the LuPO 4 powder obtained in 10), 23 g of a 1% tetramethylammonium hydride aqueous solution, and 100 g of 0.1 mmφ zirconia beads were placed and pulverized with a paint shaker.
13) After the solid-liquid separation, coarse particles were removed by passing through a 0.2 μm membrane filter.
14) The slurry obtained in 13) was colorless and transparent. When irradiated with a red laser pointer with λ = 650 nm, a Tyndall phenomenon was observed, and it was confirmed that the particles were highly dispersed.
15) A small amount of the solution of 14) was measured and dried at 200 ° C., the solid content concentration was 12%, and a glassy transparent solid content remained.
16) When the transmittance of the liquid of 14) was measured, it was confirmed that there was no absorption in the visible light region (λ = 400 to 800 nm), the transmittance at λ = 555 nm was 82%, and the transparency was high. It was confirmed. The pH was 12.
17) Even if this liquid was stored at room temperature for 1 month, no precipitation occurred and the highly dispersed state was maintained. These results are summarized in Table 2.
〔実施例２〕
本実施例では、油性分散液の調製を行った。
１８） ５０ｍＬの樹脂製容器に、９）で得られたＬｕＰＯ4粒子３．０ｇと、メチルイソブチルケトン（ＭＩＢＫ）２６．４ｇと、リン酸エステル系アニオン性界面活性剤）と、０．１ｍｍφジルコニアビーズ１３５ｇを入れ、ペイントシェーカーによる粉砕を行った。この界面活性剤としては、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１３１，１６３４２−１６３４３（２００９）に記載のものを用いた。
１９） 固液分離後、０．２μｍのメンブランフィルターに通し、粗粒の除去を行った。
２０） １９）で得られたスラリーは無色透明であり、λ＝６５０ｎｍの赤色レーザーポインターを照射したところチンダル現象が見られ、粒子が高分散していることを確認した。
２１） １９）の液を少量測り取り、２００℃で乾燥させたときの固形分濃度は１１％であり、ガラス質の透明な固形分が残存していた。
２２） １９）の液の透過率を測定したところ、可視光域（λ＝４００〜８００ｎｍ）に吸収がないことを確認し、λ＝５５５ｎｍにおける透過率は６７％であり、透明性が高いことを確認した。
２３） この液を常温中、１ヶ月間保存しても沈殿を生じることがなく、高分散状態を維持したままであった。これらの結果をまとめて表２に示す。
[Example 2]
In this example, an oily dispersion was prepared.
18) In a 50 mL resin container, 3.0 g of LuPO 4 particles obtained in 9), 26.4 g of methyl isobutyl ketone (MIBK), phosphate anionic surfactant), 0.1 mmφ zirconia 135 g of beads were placed and pulverized with a paint shaker. As this surfactant, J.M. Am. Chem. Soc. 131, 16342-16343 (2009).
19) After the solid-liquid separation, coarse particles were removed by passing through a 0.2 μm membrane filter.
20) The slurry obtained in 19) was colorless and transparent. When irradiated with a red laser pointer of λ = 650 nm, a Tyndall phenomenon was observed, and it was confirmed that the particles were highly dispersed.
21) A small amount of the solution of 19) was measured and dried at 200 ° C., the solid content concentration was 11%, and a glassy transparent solid content remained.
22) When the transmittance of the liquid of 19) was measured, it was confirmed that there was no absorption in the visible light region (λ = 400 to 800 nm), the transmittance at λ = 555 nm was 67%, and the transparency was high. It was confirmed.
23) Even if this liquid was stored at room temperature for 1 month, no precipitation occurred and the highly dispersed state was maintained. These results are summarized in Table 2.
〔実施例３〕
本実施例では水性分散液の調製を行った。
２４） ５０ｍＬの樹脂製容器に、９）で得られたＬｕＰＯ4粒子２．０ｇと、純水２３ｇと、酢酸１．２ｇと、０．１ｍｍφのジルコニアビーズ１００ｇを入れてペイントシェーカーによる粉砕を行った。
２５） 固液分離後、０．２μｍのメンブランフィルターに通し、粗粒の除去を行った。
２６） ２５）で得られたスラリーは無色透明であり、λ＝６５０ｎｍの赤色レーザーポインターを照射したところチンダル現象が見られ、粒子が高分散していることを確認した。
２７） ２５）の液を少量測り取り、２００℃で乾燥させたときの固形分濃度は９％であり、ガラス質の透明な固形分が残存していた。
２８） ２５）の液の透過率を測定したところ、可視光域（λ＝４００〜８００ｎｍ）に吸収がないことを確認し、λ＝５５５ｎｍにおける透過率は８３％であり、透明性が高いことを確認した。ｐＨは３であった。
２９） この液を常温中、１ヶ月間保存しても沈殿を生じることがなく、高分散状態を維持したままであった。これらの結果をまとめて表２に示す。
Example 3
In this example, an aqueous dispersion was prepared.
24) Place 2.0 g of LuPO 4 particles obtained in 9), 23 g of pure water, 1.2 g of acetic acid, and 100 g of 0.1 mmφ zirconia beads in a 50 mL resin container, and perform pulverization with a paint shaker. It was.
25) After the solid-liquid separation, coarse particles were removed through a 0.2 μm membrane filter.
26) The slurry obtained in 25) was colorless and transparent. When irradiated with a red laser pointer of λ = 650 nm, a Tyndall phenomenon was observed, and it was confirmed that the particles were highly dispersed.
27) A small amount of the solution of 25) was measured and dried at 200 ° C., the solid content concentration was 9%, and a glassy transparent solid content remained.
28) When the transmittance of the liquid in 25) was measured, it was confirmed that there was no absorption in the visible light region (λ = 400 to 800 nm), and the transmittance at λ = 555 nm was 83% and the transparency was high. It was confirmed. The pH was 3.
29) Even if this solution was stored at room temperature for 1 month, no precipitation occurred and the highly dispersed state was maintained. These results are summarized in Table 2.
〔比較例１〕
本比較例では油性分散液の調製を行った。
３０） 実施例１の９）で得られた粉末を実施例２のアニオン性界面活性剤を添加しない以外は、実施例２と同様にして油性分散液の調製を試みた。しかし、粒子が直ちに沈殿してしまい単分散液を得ることができなかった。
[Comparative Example 1]
In this comparative example, an oily dispersion was prepared.
30) An oily dispersion was prepared in the same manner as in Example 2, except that the powder obtained in 9) of Example 1 was not added with the anionic surfactant of Example 2. However, the particles immediately precipitated and a monodispersed liquid could not be obtained.
〔比較例２〕
本比較例では油性分散液の調製を行った。
３１） 実施例１の８）で得られた粉末を大気中１０５０℃×５ｈ焼成した。
３２） ３１）で得られた焼成粉末のＸＲＤ測定を行ったところ、ＬｕＰＯ4ピークが確認された。
３３） レーザー回折散乱法による粒度分布測定結果とＸＲＤによる結晶子径及び窒素吸着法による比表面積の測定結果を表１にまとめる。粒度分布測定は、超音波の照射前後において行った。超音波装置としては、実施例１と同様のものを用いた。超音波の照射条件も実施例１と同じである。
３４） 実施例２と同様にして油性分散液の調製を試みた。しかし、粒子が直ちに沈殿してしまい単分散液を得ることができなかった。
[Comparative Example 2]
In this comparative example, an oily dispersion was prepared.
31) The powder obtained in 8) of Example 1 was baked in air at 1050 ° C. for 5 hours.
32) When the XRD measurement of the baked powder obtained in 31) was performed, a LuPO 4 peak was confirmed.
33) Table 1 summarizes the particle size distribution measurement results by the laser diffraction scattering method, the crystallite diameter by XRD, and the measurement results of the specific surface area by the nitrogen adsorption method. The particle size distribution was measured before and after the ultrasonic irradiation. As the ultrasonic device, the same one as in Example 1 was used. Ultrasonic irradiation conditions are also the same as in the first embodiment.
34) An oily dispersion was prepared in the same manner as in Example 2. However, the particles immediately precipitated and a monodispersed liquid could not be obtained.
〔比較例２〕
本比較例では水性分散液の調製を行った。
３５） 比較例２の３１）で得られた粉を用いて、実施例３）と同様にして油性分散液の調製を試みた。しかし、粒子が直ちに沈殿してしまい単分散液を得ることができなかった。
[Comparative Example 2]
In this comparative example, an aqueous dispersion was prepared.
35) An oily dispersion was prepared in the same manner as in Example 3) using the powder obtained in 31) of Comparative Example 2. However, the particles immediately precipitated and a monodispersed liquid could not be obtained.
表１及び表２に示す結果から明らかなとおり、各実施例で用いた希土類リン酸塩粉末から分散液を調製すると、その分散液は透明性が高く、かつ希土類リン酸塩粉末を安定して分散できるものであることが判る。 As is apparent from the results shown in Tables 1 and 2, when a dispersion was prepared from the rare earth phosphate powder used in each example, the dispersion was highly transparent and the rare earth phosphate powder was stabilized. It can be seen that it can be dispersed.
Claims (8)
レーザー回折散乱式粒度分布測定法による累積体積９９．９９容量％における体積累積粒径Ｄ99.99が１μｍ以上１００μｍ以下である希土類リン酸塩粉末。 The specific surface area measured by the nitrogen adsorption method is 10 m 2 / g or more and 200 m 2 / g or less,
A rare earth phosphate powder having a volume cumulative particle size D 99.99 of 1 to 100 μm at a cumulative volume of 99.99% by volume measured by a laser diffraction / scattering particle size distribution measurement method.
希土類元素源を含む水溶液と、リン酸根を含む水溶液とを同時添加して、希土類リン酸塩を生成させる工程を含む希土類リン酸塩粉末の製造方法。 A method for producing a rare earth phosphate powder according to any one of claims 1 to 3,
A method for producing a rare earth phosphate powder comprising a step of simultaneously adding an aqueous solution containing a rare earth element source and an aqueous solution containing a phosphate group to form a rare earth phosphate.
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