JPS63277687A - Production of metal-containing composition - Google Patents
Production of metal-containing compositionInfo
- Publication number
- JPS63277687A JPS63277687A JP11330887A JP11330887A JPS63277687A JP S63277687 A JPS63277687 A JP S63277687A JP 11330887 A JP11330887 A JP 11330887A JP 11330887 A JP11330887 A JP 11330887A JP S63277687 A JPS63277687 A JP S63277687A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- containing composition
- chloride
- alcohol
- halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 alcohol amine Chemical class 0.000 claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- 229910052738 indium Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 150000004820 halides Chemical class 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910001507 metal halide Inorganic materials 0.000 claims description 6
- 150000005309 metal halides Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 abstract description 6
- 239000012190 activator Substances 0.000 abstract description 3
- 150000002169 ethanolamines Chemical class 0.000 abstract 1
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 49
- 239000000243 solution Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 25
- 150000004703 alkoxides Chemical class 0.000 description 24
- 239000013078 crystal Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910001510 metal chloride Inorganic materials 0.000 description 15
- 235000019270 ammonium chloride Nutrition 0.000 description 14
- 239000010955 niobium Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052691 Erbium Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- KYCHGXYBBUEKJK-UHFFFAOYSA-K indium(3+);trichloride;hydrate Chemical compound O.Cl[In](Cl)Cl KYCHGXYBBUEKJK-UHFFFAOYSA-K 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DCCCFEFUTIRTMJ-UHFFFAOYSA-K O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ti+3] Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ti+3] DCCCFEFUTIRTMJ-UHFFFAOYSA-K 0.000 description 1
- FPMMWKFKHAUFES-UHFFFAOYSA-K O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[V+3] Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[V+3] FPMMWKFKHAUFES-UHFFFAOYSA-K 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- YCAUHXBLLQLUQV-UHFFFAOYSA-M [Cl-].[O-2].[V+3] Chemical compound [Cl-].[O-2].[V+3] YCAUHXBLLQLUQV-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- LIRSFCJKZQBJRK-UHFFFAOYSA-M antimony(3+);oxygen(2-);chloride Chemical compound [O-2].[Cl-].[Sb+3] LIRSFCJKZQBJRK-UHFFFAOYSA-M 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical class Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- UJBPGOAZQSYXNT-UHFFFAOYSA-K trichloroerbium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Er+3] UJBPGOAZQSYXNT-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、ＡＩ、Ｉｎ、Ｙ、ランタン系元素、Ｓｎ、Ｔ
ｉ、Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から選
択される１ｆ！または２種以上の金属元素を含み、アル
コールアミン類を配位子として含有する、安定で有機溶
媒に可溶な金属含有組成物を製造する方法に関するもの
である。[Detailed Description of the Invention] [Industrial Application Fields] The present invention is applicable to AI, In, Y, lanthanum-based elements, Sn, T
1f selected from the group consisting of i, Zr, Sb, V, Nb and Mn! Alternatively, the present invention relates to a method for producing a stable, organic solvent-soluble metal-containing composition containing two or more metal elements and an alcohol amine as a ligand.
［従来の技術］ ＡＩ、Ｉｎ、Ｙ、ランタン系元素、Ｓｎ。[Conventional technology] AI, In, Y, lanthanum-based elements, Sn.
Ｔｉ、Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎ等の金属を含む
金属アルコキシドのうち、Ｓｂ、Ｎｂなとのアルコキシ
ドは低級アルコールのアルコキシドにおいても液体状で
得られ、またＶ、Ｔｉ。Among metal alkoxides containing metals such as Ti, Zr, Sb, V, Nb, and Mn, alkoxides of Sb and Nb are also obtained in liquid form in alkoxides of lower alcohols, and V, Ti.
Ｚｒ、Ａ１などのアルコキシドについては、炭素数２〜
３以上のアルキル基を有するアルコキシドを液体状で得
ることができる。しかしながらこれらの金属アルコキシ
ドは空気中の水分によってさえもすみやかに加水分解を
受けるほど不安定であって、保存あるいは取扱いが困難
であり、また固体状で得られる金属アルコキシドの場合
でも、空気中の水分によっても同様に加水分解を受け、
さらに有機溶媒に対して難溶性であるため工業的に利用
しようとする場合様々の制約があった。For alkoxides such as Zr and A1, carbon atoms are 2 to
Alkoxides having three or more alkyl groups can be obtained in liquid form. However, these metal alkoxides are so unstable that they are easily hydrolyzed even by moisture in the air, making them difficult to store or handle. It is also hydrolyzed by
Furthermore, since it is poorly soluble in organic solvents, there are various restrictions when trying to use it industrially.
ところで液状で得られる金属アルコキシドあるいは有機
溶媒に溶解または希釈することのできる金属アルコキシ
ドについては、該溶液を加水分解することによってアル
コキシドを構成する金属の水酸化物、水和物あるいは酸
化物を微粉末状態で得ることができ、しかもこれらの金
属アルコキシドと反応するのは水だけであるので、生成
する微粉末中に他の金属イオンが不純物として混入する
可能性が少なく、またハロゲン化物イオンなどの陰イオ
ンが混入する可能性も少ないことから、高純度の微粉末
（以下、特記しない限り微粉末とは金属の水酸化物、水
和物または酸化物の微粉末を意味する）が得られるとい
う利点がある。By the way, for metal alkoxides obtained in liquid form or metal alkoxides that can be dissolved or diluted in organic solvents, the hydroxides, hydrates, or oxides of the metals constituting the alkoxide can be made into fine powder by hydrolyzing the solution. Moreover, since only water reacts with these metal alkoxides, there is little possibility that other metal ions will be mixed in as impurities in the fine powder produced, and anions such as halide ions can be obtained. The advantage is that there is less possibility of ion contamination, resulting in a highly pure fine powder (hereinafter, fine powder means fine powder of metal hydroxides, hydrates, or oxides, unless otherwise specified). There is.
従ってＡｔ、Ｉｎ、ｙ、ランタン系元素、Ｓｎ、Ｔｉ、
Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から選択さ
れる金属を含むアルコキシドについても、溶液状でしか
も空気中の水分等では加水分解を受けない安定なものと
して得ることができ、さらにはハロゲン化物イオンの如
き不純物を含まない高純度のものとして得ることができ
れば、それらの金属アルコキシドの加水分解あるいは熱
分解によって高純度の微粉末を容易に得ることができる
と考えられる。そしてそれらの微粉末は比較的低温、短
時間で焼結し得るという特徴を有しているので、蛍光体
製造分野における賦活剤としての微量添加材；金属材料
やセラミックス表面へのコーティング材、ＧＧＧなどの
機能性薄膜等の薄膜分野；セラミックスなどの焼結助剤
的な添加剤としであるいは金属材料などの高温酸化防止
用材料として有効に活用し得るものと期待される。Therefore, At, In, y, lanthanum elements, Sn, Ti,
Alkoxides containing metals selected from the group consisting of Zr, Sb, V, Nb, and Mn can also be obtained in the form of solutions and in a stable form that does not undergo hydrolysis in the presence of moisture in the air. If it can be obtained as a highly pure product that does not contain impurities such as compound ions, it is thought that a highly pure fine powder can be easily obtained by hydrolysis or thermal decomposition of these metal alkoxides. Since these fine powders have the characteristic of being able to be sintered at relatively low temperatures and in a short time, they can be used as trace additives as activators in the field of phosphor manufacturing; coating materials for metal materials and ceramic surfaces; It is expected that it can be effectively used in the field of thin films such as functional thin films; as a sintering aid additive for ceramics, etc., or as a material for high-temperature oxidation prevention of metal materials, etc.
［発明が解決しようとする問題点］
金属アルコキシドは金属とアルコール類との直接反応、
無水金属塩化物とアルコール類との反応等により得られ
ており、つまり水の不存在下で製造されるのが通例であ
る。現在市販されている金属アルコキシドの中で工業的
に製造されているのは、Ｂ、Ｓｉ、Ｔｉ、Ｚｒ及びＡ１
のアルコキシドだけであり、他のアルコキシドはＳｂ、
Ｚｎ。[Problems to be solved by the invention] Metal alkoxides require direct reaction between metals and alcohols;
It is obtained by a reaction between an anhydrous metal chloride and an alcohol, that is, it is usually produced in the absence of water. Among the metal alkoxides currently on the market, those that are industrially produced are B, Si, Ti, Zr, and A1.
is the only alkoxide, and the other alkoxides are Sb,
Zn.
Ｇａ、Ｖ、Ｔａ、Ｉｎなどが試薬品として入手し得るの
みであって工業的に量産されるまでには至っていない。Ga, V, Ta, In, etc. are only available as reagents and have not yet been industrially mass-produced.
しかもＳｔのアルコキシドを除いてどの金属アルコキシ
ドも、空気中の水分程度で簡単に加水分解を起こすため
その取扱いが非常に困難である。Moreover, all metal alkoxides except St alkoxide easily undergo hydrolysis when exposed to moisture in the air, making it extremely difficult to handle them.
また金属アルコキシドは一般に固体状のものが多く、し
かも有機溶媒に対して不溶性乃至難溶性のものが多いの
で、こうしたこともその使用範囲を狭める原因となって
いる。即ち固体状の金属アルコキシドをそのまま加水分
解した場合、生成物の粒子サイズが比較的大きくなるば
かりでなく均一な粒度分布のものが得られ難く、従って
微細で均一な粒度分布の加水分解物を得るためには金属
アルコキシド自体を安定な液状（溶液状を含む）で得る
ことが望まれるが、前述の如き従来の金属アルコキシド
はこうした要望を満たしていない。Further, metal alkoxides are generally solid, and many are insoluble or poorly soluble in organic solvents, which also causes a narrowing of the range of their use. That is, when a solid metal alkoxide is hydrolyzed as it is, not only the particle size of the product becomes relatively large, but also it is difficult to obtain a product with a uniform particle size distribution.Therefore, it is difficult to obtain a hydrolyzate with a fine and uniform particle size distribution. For this purpose, it is desired to obtain the metal alkoxide itself in a stable liquid form (including solution form), but the conventional metal alkoxides as described above do not meet this demand.
本発明は上記の様な事情に着目してなされたものであっ
て、その目的は、精製可能な溶液状でしかも空気中の水
分程度では簡単に加水分解を起こすよ゛うなことがなく
、長期にわたり優れた安定性を示す、ＡＩ、Ｉｎ、Ｙ、
ランタン系元素、Ｓｎ、Ｔｉ、Ｚｒ、Ｓｂ、Ｖ、Ｎｂお
よびＭｎよりなる群から選択され１種または２種以上の
金属元素を含み、且つアルコールアミン類を配位子とす
る金属含有組成物を製造する方法を提供しようとするも
のである。The present invention was made in view of the above-mentioned circumstances, and its purpose is to provide a solution that can be purified and that does not easily undergo hydrolysis when exposed to moisture in the air, and that can be used for a long period of time. AI, In, Y, which exhibits excellent stability over
A metal-containing composition containing one or more metal elements selected from the group consisting of lanthanum-based elements, Sn, Ti, Zr, Sb, V, Nb, and Mn, and having an alcohol amine as a ligand. The purpose is to provide a manufacturing method.
また本発明の他の目的は、上記のような金属含有組成物
を含む高純度のアルコール溶液を簡単に製造することの
できる方法を提供しようとするものである。Another object of the present invention is to provide a method for easily producing a high purity alcoholic solution containing the metal-containing composition as described above.
［問題点を解決するための手段］
上記の目的を達成することのできた本発明の方法は、Ａ
Ｉ、Ｉｎ、Ｙ、ランタン系元素、Ｓｎ。[Means for Solving the Problems] The method of the present invention that can achieve the above object is as follows: A.
I, In, Y, lanthanum-based elements, Sn.
Ｔｉ、Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から
選択される１種または２種以上の金属のハロゲン化物と
、アルコールアミン類の１種または２種以上とを、炭素
数１〜４のアルコールに溶解または懸濁させ、アンモニ
アの存在下で反応させるところに要旨を有するものであ
る。One or more metal halides selected from the group consisting of Ti, Zr, Sb, V, Nb and Mn and one or more alcohol amines having a carbon number of 1 to 4. The gist is that it is dissolved or suspended in alcohol and reacted in the presence of ammonia.
また本発明に係わる他の構成は、前述の様にして得られ
る反応液をイオン交換樹脂で処理し、夾雑イオンを除去
して高純度の金属含有組成物を得るところに要旨を有す
るものである。Another aspect of the present invention is that the reaction solution obtained as described above is treated with an ion exchange resin to remove contaminant ions and obtain a highly pure metal-containing composition. .
［作用］
本発明で使用される前記金属のハロゲン化物としては、
弗化物、塩化物、臭化物、沃化物があげられるが、工業
的に最も好ましいのは塩化物であるので、以下塩化物を
代表的に取り上げて説明を進める。[Function] The metal halide used in the present invention includes:
Examples include fluoride, chloride, bromide, and iodide, but since chloride is industrially most preferred, the following explanation will be based on chloride as a representative example.
尚本明細書で言う塩化物とは、結晶水を含む塩化物、酸
化塩化物あるいは結晶水を含む酸化塩化物を総称するも
のであり、また少量の炭酸根を含むものであってもよく
、これらの概念は塩化物以外のハロゲン化物についても
同様である。In addition, the chloride mentioned in this specification is a general term for chloride containing crystal water, oxidized chloride, or oxidized chloride containing crystal water, and may also contain a small amount of carbonate radical. These concepts also apply to halides other than chlorides.
本発明を実施するに当っては、ＡＩ、Ｉｎ。In carrying out the invention, AI, In.
Ｙ、ランタン系元素、Ｓｎ、Ｔｉ、Ｚｒ、Ｓｂ。Y, lanthanum-based elements, Sn, Ti, Zr, Sb.
Ｖ、ＮｂおよびＭｎよりなる群から選択される１種また
は２種以上の金属塩化物と、アルコールアミン類の１種
または２種以上とを、炭素数１〜４のアルコールに溶解
もしくは懸濁させ、アンモニアの存在下で反応が行なわ
れる。上記金属の塩化物はアルコールに対して比較的溶
解度が小さいが、一般的には炭素数１〜４のアルコール
ＩＪ２に対し０．１〜２モル、好ましくは０．２〜１モ
ルのアルコール溶液あるいは懸濁液として反応に供され
る。尚本発明者らが確認したところによると、該金属塩
化物は完全にアルコールに溶解させなければならない訳
ではなく、アルコール中に懸濁させた状態でも後のアン
モニアの存在下での反応は十分に進行する。One or more metal chlorides selected from the group consisting of V, Nb and Mn and one or more alcohol amines are dissolved or suspended in an alcohol having 1 to 4 carbon atoms. , the reaction is carried out in the presence of ammonia. The chlorides of the metals mentioned above have relatively low solubility in alcohol, but are generally 0.1 to 2 moles, preferably 0.2 to 1 mole, in alcohol solutions or It is subjected to the reaction as a suspension. Additionally, the inventors have confirmed that the metal chloride does not have to be completely dissolved in alcohol, and even if it is suspended in alcohol, the subsequent reaction in the presence of ammonia is sufficient. Proceed to.
該金属塩化物は従来公知の方法によって製造することが
できる０例えばＩｎ、Ｙ、ランタン系元素の塩化物は、
当該金属の酸化物を塩酸に溶解した後濃縮すると、結晶
水を含む塩化物として析出する。Ａ１の塩化物の場合、
塩化アルミニウム無水物を水に溶解するかあるいはアル
ミニウムを塩酸に溶解して塩化アルミニウムの濃水溶液
をつくり、さらに濃塩酸を加えて冷却しつつ、乾燥した
塩化水素ガスを吹込むと、白色結晶性の塩が析出するの
で、これを減圧乾燥すると６永和物として得ることがで
きる。Ｓｎ塩化物の場合はＳｎと塩酸との反応により、
またＺｒ塩化物の場合は含水酸化ジルコニウムの塩酸々
性水溶液を濃縮することにより、夫々８永和物として得
られる。アンチモンと塩素を反応させて得た塩化アンチ
モン（ＩＩＩ ’）と水を混合して放置すると、塩化酸
化アンチモン（ＩＩＩ）が得られる。■塩化物の場合、
酸化バナジウム（Ｖ）を水素で還元して得た酸化バナジ
ウム（Ｉｌｌ ）を濃塩酸に溶解し、塩化水素を吹込む
と、塩化バナジウム（ＩＩＩ ）の６永和物が結晶とし
て得られる。また酸化バナジウム（Ｖ）と炭素質の混合
物を塩素ガスと反応させると、三塩化酸化バナジウムが
得られ、酸化ニオブ（ｌ）と炭素質を混合し塩素ガスと
反応させると塩化酸化ニオブ（Ｖ）が得られる。さらに
Ｍｎ塩化物の場合は、炭酸マンガンを塩酸に溶解した後
濃縮すると、塩化マンガン（Ｉｆ）の４永和物が結晶と
して得られる。The metal chloride can be produced by a conventionally known method. For example, chlorides of In, Y, and lanthanum-based elements are:
When the oxide of the metal is dissolved in hydrochloric acid and concentrated, it precipitates as a chloride containing water of crystallization. In the case of A1 chloride,
By dissolving anhydrous aluminum chloride in water or dissolving aluminum in hydrochloric acid to make a concentrated aqueous solution of aluminum chloride, adding concentrated hydrochloric acid, cooling, and blowing in dry hydrogen chloride gas, a white crystalline solution is formed. Since the salt precipitates, it can be obtained as a 6-eternal product by drying it under reduced pressure. In the case of Sn chloride, by the reaction of Sn and hydrochloric acid,
In the case of Zr chloride, it can be obtained as an 8-eternal product by concentrating a hydrochloric-acidic aqueous solution of hydrous zirconium oxide. When antimony chloride (III') obtained by reacting antimony and chlorine is mixed with water and left to stand, antimony chloride oxide (III) is obtained. ■In the case of chloride,
When vanadium oxide (Ill) obtained by reducing vanadium (V) oxide with hydrogen is dissolved in concentrated hydrochloric acid and hydrogen chloride is blown into the solution, vanadium (III) chloride hexahydrate is obtained as a crystal. Also, when a mixture of vanadium (V) oxide and carbonaceous substance is reacted with chlorine gas, vanadium trichloride oxide is obtained, and when niobium (l) oxide and carbonaceous substance are mixed and reacted with chlorine gas, niobium (V) chloride oxide is obtained. is obtained. Furthermore, in the case of Mn chloride, when manganese carbonate is dissolved in hydrochloric acid and then concentrated, a four-estate product of manganese chloride (If) is obtained as a crystal.
本発明における一つの特徴は、上記のようにして調製し
た金属塩化物の１種以上と、アルコールアミン類の１種
または２種以上とを、炭素数１〜４を有するアルコール
に溶解または懸濁させ、アンモンニアの存在下で反応を
行なうところにあり、結晶水を含む金属塩化物を使用し
た場合でも、水により加水分解の可能な金属含有組成物
の製造が可能になった。またこれらの反応を行なう場合
、金属アルコキシド類にアルコールアミン類を後から添
加したのでは反応性が緩慢なものが多いため工業的製法
としては適切でなく、本発明の如く反応時にアルコール
アミン類を共存させることにより保存安定性、加水分解
性を自由に抑制し得る金属含有組成物を製造することが
可能となる。ここで使用されるアルコールアミン類は一
般式
ａ
［ただしＲ，、Ｒ２はｃｎＨ２ｎ、Ｉ、ｎはＯまたは１
〜４の整数］
で表わされるものであり、この中でもＲｌ ＋ Ｒ２
がＨであるモノエタノールアミン、ジェタノールアミン
あるいはトリエタノールアミンが特に好ましい。上記３
種のアルコールアミン類以外のアルコールアミンを使用
した場合、最終的に得られる溶液の保存安定性が悪く、
開放状態で数時間保存するだけで加水分解を起こして、
急速にゲル化する。One feature of the present invention is that one or more metal chlorides prepared as described above and one or more alcohol amines are dissolved or suspended in an alcohol having 1 to 4 carbon atoms. This method allows the reaction to be carried out in the presence of ammonia, making it possible to produce a metal-containing composition that can be hydrolyzed with water even when a metal chloride containing water of crystallization is used. Furthermore, when carrying out these reactions, adding alcohol amines to metal alkoxides afterward is often slow in reactivity and is therefore not suitable for industrial production. By allowing them to coexist, it becomes possible to produce a metal-containing composition whose storage stability and hydrolyzability can be freely suppressed. The alcohol amines used here have the general formula a [where R,, R2 is cnH2n, I, n are O or 1
~4 integer], among which Rl + R2
Monoethanolamine, jetanolamine or triethanolamine in which is H is particularly preferred. Above 3
If alcohol amines other than the alcohol amines used are used, the storage stability of the final solution may be poor;
Hydrolysis occurs just by storing it in an open state for a few hours,
Gels quickly.
アルコールアミンと金属塩化物との好ましいモル比は、
一般式ＭＣＩ、・ｍＲ２０（ただしＭは酸化数ｎの金属
元素、ｎは金属元素の酸化数、ｍは結晶水のモル数）で
表わされる金属塩化物の場合、１：０．５乃至１：ｎの
範囲、ＭＯＣＩｎ−、あるいはＭ ＯＣ１ｎ −２・ｍ
Ｈ，Ｏで表わされる酸化金属塩化物の場合、１：０．５
乃至１：（ｎ−２）の範囲であり、特に好ましいのは、
一般式ＭＣｌｎ−ｍＨ２Ｏで表わされる金属塩化物の場
合１：１乃至１：（ｎ−１）の範囲、ＭＯＣＩｏ−２あ
るいはＭＯＣ１ｎ−２・ｍＨ，Ｏで表わされる酸化金属
塩化物の場合１：１乃至１：（ｎ−３）の範囲である。The preferred molar ratio of alcohol amine to metal chloride is:
In the case of a metal chloride represented by the general formula MCI, ・mR20 (where M is a metal element with oxidation number n, n is oxidation number of the metal element, and m is the number of moles of crystal water), 1:0.5 to 1: range of n, MOCIn-, or MOC1n -2・m
In the case of oxidized metal chloride represented by H, O, 1:0.5
The range is from 1 to 1:(n-2), and particularly preferred is
In the case of a metal chloride represented by the general formula MCln-mH2O, the range is 1:1 to 1:(n-1), and in the case of an oxidized metal chloride represented by MOCIo-2 or MOC1n-2·mH,O, it is 1:1. The range is from 1 to 1:(n-3).
上記金属の塩化物とアルコールアミン類を上記比率で炭
素数１〜４のアルコールに溶解または懸濁させ、アンモ
ニアの存在下で反応を行なうと、アルコールアミン類を
配位子とする安定な金属含有組成物のアルコール溶液が
得られる。特にアルコールアミン類の量が、一般式ＭＣ
１ｎ””Ｒ２０で表わされる金属塩化物の場合、金属イ
オン１モルに対し１乃至（ｎ−１）モル、ＭＯＣｌ、、
あるいはＭ ＯＣ１ｎ−２” ｍ Ｈ２０で表わされる
酸化金属塩化物の場合金属イオン１モルに対して１乃至
（ｎ−３）モルであるとき、最も安定性の優れた溶液を
得ることができる。When the above metal chloride and alcohol amine are dissolved or suspended in an alcohol having 1 to 4 carbon atoms in the above ratio and reacted in the presence of ammonia, a stable metal-containing product with alcohol amine as a ligand can be obtained. An alcoholic solution of the composition is obtained. In particular, the amount of alcohol amines is determined by the general formula MC
In the case of a metal chloride represented by 1n""R20, 1 to (n-1) mol per mol of metal ion, MOCl,
Alternatively, in the case of an oxidized metal chloride represented by M OC1n-2" m H20, the most stable solution can be obtained when the amount is 1 to (n-3) mol per 1 mol of metal ions.
上記反応自体はアンモニアガスを導入しながら反応させ
る通常の方法が採用される。たとえば前記金属塩化物と
前記特定のアルコールアミン類のアルコール溶液あ・る
いは懸濁液にアンモニアガスを吹込む方法が最も一般的
である。導入するアンモニアの量は理論量よりやや過剰
、例えば一般式ＭＣ１ｎ−ｍＨ２Ｏで表わされる塩化物
１モルに対しくｎ＋０．５）〜（ｎ＋１．５）モルの割
合で用いるのが好ましい。また一般式Ｍ ＯＣ１ｎ−２
あるいはＭ ＯＣ１ｎ−２・ｍＨ２Ｏで表わされる酸化
塩化物１モルに対しくｎ−１，５） 〜（ｎ −０，５
’）モルの割合で用いるのが好ましい。但し、Ｍは酸化
数ｎの金属元素、ｍは結晶水のモル数を表わす。For the above reaction itself, a usual method is adopted in which the reaction is carried out while introducing ammonia gas. For example, the most common method is to blow ammonia gas into an alcohol solution or suspension of the metal chloride and the specific alcohol amine. It is preferable that the amount of ammonia introduced is slightly in excess of the theoretical amount, for example, in a ratio of n+0.5) to (n+1.5) moles per mole of chloride represented by the general formula MC1n-mH2O. Also, the general formula MOC1n-2
Or n-1,5) to (n-0,5
') is preferably used in molar proportions. However, M represents a metal element with an oxidation number n, and m represents the number of moles of crystal water.
この反応は発熱反応であり、反応の進行と共に温度が上
昇し同時に塩化アンモニウムが副生ずる。This reaction is an exothermic reaction, and as the reaction progresses, the temperature increases and at the same time ammonium chloride is produced as a by-product.
この塩化アンモニウムは、反応終了後冷却することによ
って一部析出するので、これを濾別することによって、
アルコールアミン類を配位子として含む金属含有組成物
の安定なアルコール溶液を得ることができる。This ammonium chloride is partially precipitated by cooling after the reaction is completed, so by filtering it out,
A stable alcohol solution of a metal-containing composition containing alcohol amines as a ligand can be obtained.
このようにして得られる金属含有組成物のアルコール溶
液は、ゲル化等を起こすこともなく長期にわたり安定で
あり、また空気中の水分によって簡単に加水分解を受け
るようなこともない。またこの溶液は、使用したアルコ
ール類と相溶性のある他の有機溶剤、例えばアルコール
類、ケトン類、芳香族炭化水素（例えばトルエン、ベン
ゼン、キシレン等）、クロロホルム等により希釈するこ
とができる。The alcoholic solution of the metal-containing composition thus obtained is stable over a long period of time without causing gelation or the like, and is not easily hydrolyzed by moisture in the air. This solution can also be diluted with other organic solvents that are compatible with the alcohol used, such as alcohols, ketones, aromatic hydrocarbons (such as toluene, benzene, xylene, etc.), chloroform, and the like.
ところで前述の様にして得られる金属含有組成物のアル
コール溶液中には、塩化アンモニウムを主とする塩化物
イオンが不純物として含まれているが、用途によっては
かかる塩化物イオンを除去し更に高純度のものとするこ
とが望まれる。塩化物イオンの除去法としては、蒸留法
、再結晶法等が一般的に考えられるが、金属アルコキシ
ドやアルコールアミン類を配位子とする金属含有組成物
は蒸気圧が非常に低いため真空蒸留による精製は困難で
あり、また有機溶媒を用いた再結晶法では塩化物イオン
の除去率の点で十分とは言い難い。By the way, the alcohol solution of the metal-containing composition obtained as described above contains chloride ions, mainly ammonium chloride, as impurities. It is desirable that the Distillation, recrystallization, etc. are generally considered methods for removing chloride ions, but metal-containing compositions with metal alkoxides or alcohol amines as ligands have extremely low vapor pressure, so vacuum distillation is recommended. Purification using organic solvents is difficult, and recrystallization using organic solvents is not sufficient in terms of removal rate of chloride ions.
本発明者らはこの様な処理法を採用することなく簡単な
操作で高純度の溶液を得る方法を確立すべく更に研究検
討を重ねた結果、上述のようにして得られる金属含有組
成物のアルコール溶液を陰イオン交換樹脂によって処理
すれば、該溶液中に存在する塩化物イオンの量を金属元
素１モルに対し１７１０００モル程度以下にまで減少さ
せ得ることを見出した。The present inventors conducted further research and study to establish a method for obtaining a high-purity solution with simple operations without employing such processing methods, and as a result, the metal-containing composition obtained as described above. It has been found that by treating an alcohol solution with an anion exchange resin, the amount of chloride ions present in the solution can be reduced to about 171,000 moles or less per mole of metal element.
即ち、本発明における今一つの特徴は、前述の様にして
得られる金属含有組成物のアルコール溶液を、イオン交
換樹脂で処理することによって不純イオンを除去し、高
純度の金属含有液状組成物を製造するところにある。That is, another feature of the present invention is that impurity ions are removed by treating the alcohol solution of the metal-containing composition obtained as described above with an ion exchange resin to produce a highly pure metal-containing liquid composition. It's there.
上記不純物除去に用いられるイオン交換樹脂としては、
得られる溶液中の主たる不純物・である塩化物イオンを
捕捉し除去し得る陰イオン交換樹脂であれば任意のもの
を使用することができるが、好ましいのは末端基が
Ｃ２Ｈ４０ＨＸ
である強塩基性陰イオン交換樹脂であり、特に好ましい
のは前者の末端基を有するものである。これらのイオン
交換樹脂は、アンバーライトＩ ＲＡ、アンバーリスト
Ａ、ダイヤイオンＳＡ。Ion exchange resins used for removing the above impurities include:
Any anion exchange resin can be used as long as it can capture and remove chloride ions, which are the main impurity in the resulting solution, but preferred is a strongly basic anion exchange resin whose terminal group is C2H40HX. Among the ion exchange resins, particularly preferred are those having the former terminal group. These ion exchange resins are Amberlyte I RA, Amberlyst A, and Diaion SA.
ＰＡ、ダウエックスＳＡＲ等の商標名のもとに市場で人
手することができる。It is available on the market under trade names such as PA and DOWEX SAR.
イオン交換樹脂処理は、前述のようにして製造したアル
コールアミンを配位子とする金属含有組成物のアルコー
ル溶液を、周知の方法で前記陰イオン交換樹脂と接触さ
せることにより実施される。最も一般的なのは、イオン
交換樹脂を充填したカラムに、前記金属含有組成物のア
ルコール溶液を通過させる方法である。純度を更に高め
る必要がある場合は、この精製操作を数回繰返してもよ
い。The ion exchange resin treatment is carried out by contacting the alcohol solution of the metal-containing composition containing alcohol amine as a ligand produced as described above with the anion exchange resin by a well-known method. The most common method is to pass an alcoholic solution of the metal-containing composition through a column filled with an ion exchange resin. If it is necessary to further increase the purity, this purification operation may be repeated several times.
このようなイオン交換樹脂処理を行なうことにより、溶
液中の塩化物イオンは金属イオン１モルに対し１７１０
００モル程度以下の如く顕著に減少し、極めて純度の高
い金属含有組成物を得ることができる。By performing such ion exchange resin treatment, the chloride ions in the solution are reduced to 1710 ions per mole of metal ions.
It is possible to obtain a metal-containing composition with extremely high purity.
以下実施例をあげて本発明を具体的に説明するが、本発
明はもとより下記の実施例によって制限を受けるもので
はない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited by the Examples below.
［実施例］
実施例１
酸化塩化ジルコニウム（ＩＶ）ＺｒＯＣｌ２ ・８Ｈ２
０の３２２ｇ（１モル）とモノエタノールアミン、ジェ
タノールアミンあるいはトリエタノールアミンの第１表
に示す量をメチルアルコール２Ｊ２に溶解または懸濁さ
せた後、アンモニアガスを０．２１Ｌ／分で８時間吹込
んだ。反応終了後室温まで冷却し、析出してくる塩化ア
ンモニウムの結晶を濾別することにより、ジルコニウム
含有組成物（生成物）のメチルアルコール溶液を得た。[Example] Example 1 Zirconium chloride oxide (IV) ZrOCl2 ・8H2
After dissolving or suspending 322 g (1 mol) of 0.0 and the amounts shown in Table 1 of monoethanolamine, jetanolamine, or triethanolamine in methyl alcohol 2J2, ammonia gas was added at 0.21 L/min for 8 hours. Infused. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain a methyl alcohol solution of the zirconium-containing composition (product).
この生成物の状態および保存安定性を第１表に示す。The condition and storage stability of this product are shown in Table 1.
（以下余市）、′、へ
＜４−Ｊ 、＝−＋−ｉ
ｓ；Ｈ−一一り
Ｎ ｉ 表 （ジルコニウム含有組成物）安定性
Δ：１〜２週間 Ｏ：１ケ月以内Ｏ：１ケ月以
上 −ニゲル状で得られるため対象から除外実施例
２
塩化アルミニウム・６水和物Ａ Ｉ Ｃ１ｓ ・６Ｈ２
０の２４ｔｇ（１モル）とモノエタノールアミン、ジェ
タノールアミンあるいはトリエタノールアミンの第２表
に示す量をエチルアルコール２１に溶解または懸濁させ
た後、アンモニアガスを０．２１Ｌ／分で８時間吹込ん
だ。反応終了後室温まで冷却し、析出してくる塩化アン
モニウムの結晶と一部の未反応物を濾別すると、アルミ
ニウム含有組成物（生成物）のエチルアルコール溶液が
得られた。(hereinafter referred to as Yoichi),',to<4-J,=-+-is;H-11N i Table (Zirconium-containing composition) Stability Δ: 1 to 2 weeks O: Within 1 month O: 1 - Excluded from the target because it is obtained in gelatinous form Example 2 Aluminum chloride hexahydrate A I C1s 6H2
After dissolving or suspending 24 tg (1 mol) of monoethanolamine, jetanolamine, or triethanolamine in the amount shown in Table 2 in ethyl alcohol 21, ammonia gas was added at 0.21 L/min for 8 hours. Infused. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals and some unreacted substances were filtered off to obtain an ethyl alcohol solution of the aluminum-containing composition (product).
この生成物の状態および保存安定性を第２表に示す。The condition and storage stability of this product are shown in Table 2.
・−５／′
第 ２ 表 （アルミニウム含有組成物）安定性
×：１週間以内 Δ：１〜２週間○：１ケ月以内
−ニゲル状で得られるため対象から除外実施例３
酸化エルビウムＥｒ２０ｓの１９２ｇ（０，５モル）を
、（１＋１）塩酸１．５℃に溶解した後濃縮する。冷却
すると、Ｅｒ、Ｏ，換算で１８５ｇの塩化エルビウム・
水和物が結晶として析出した。-5/' Table 2 (Aluminum-containing compositions) Stability
×: Within 1 week Δ: 1 to 2 weeks ○: Within 1 month
-Excluded from the scope because it is obtained in a gelatinous state Example 3 192 g (0.5 mol) of erbium oxide Er20s is dissolved in (1+1) hydrochloric acid at 1.5° C. and then concentrated. When cooled, 185g of erbium chloride in terms of Er, O,
A hydrate precipitated as crystals.
この結晶と、モノエタノールアミン、ジェタノールアミ
ン、あるいはトリエタノールアミンの第３表に示す量を
イソプロピルアルコール１．５ ＪＺに溶解し、アンモ
ニアガスを０．２Ｊｌ１分で９時間吹込んだ。反応終了
後室温まで冷却し、析出する塩化アンモニウムの結晶を
濾別すると、エルビウム含有組成物（生成物）のイソプ
ロピルアルコール溶液を得た。This crystal and the amounts of monoethanolamine, jetanolamine, or triethanolamine shown in Table 3 were dissolved in isopropyl alcohol 1.5 JZ, and ammonia gas was blown into the solution at a rate of 0.2 Jl per minute for 9 hours. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an isopropyl alcohol solution of the erbium-containing composition (product).
この生成物の状態および保存安定性を第３表に示す。The condition and storage stability of this product are shown in Table 3.
第 ３ 表 （エルビウム含有組成物）安定性
０：１ケ月以内 ◎：１ケ月以上比較例１
実施例３と同様にして得られた塩化エルビウム・水和物
を、アミン類を添加することなしに実施例３と同様に反
応させたところ、生成物は不安定なゲル状を呈しており
、溶液状としては得ることができなかった。Table 3 (Erbium-containing composition) Stability
0: Within 1 month ◎: More than 1 month Comparative Example 1 Erbium chloride hydrate obtained in the same manner as in Example 3 was reacted in the same manner as in Example 3 without adding amines. The product was in the form of an unstable gel and could not be obtained as a solution.
実施例４
酸化塩化ニオブＮｂ０Ｃ１３の２１５ｇ（１モル）とモ
ノエタノールアミン、ジェタノールアミンあるいはトリ
エタノールアミンの第４表に示す量をｎ−ブチルアルコ
ール２ｆｔに溶解または懸濁させ、アンモニアガスを０
．２ｆｌ１分で７時間吹込んだ。反応終了後室温まで冷
却し、析出する塩化アンモニウムの結晶を濾別すると、
ニオブ含有組成物（生成物）のｎ−ブチルアルコール溶
液が得られた。Example 4 215 g (1 mol) of niobium chloride oxide Nb0C13 and the amount of monoethanolamine, jetanolamine, or triethanolamine shown in Table 4 were dissolved or suspended in 2 ft of n-butyl alcohol, and ammonia gas was added to 0.
．． Bubbled at 2fl for 1 minute for 7 hours. After the reaction is complete, cool to room temperature and filter out the precipitated ammonium chloride crystals.
A solution of the niobium-containing composition (product) in n-butyl alcohol was obtained.
この生成物の状態および保存安定性を第４表に示す。The condition and storage stability of this product are shown in Table 4.
第 ４ 表 （ニオブ含有組成物）
安定性 Ｘ：１ｉ１１間以内 Δ：１〜２週間○
：１ケ月以内
実施例５
塩化マンガンＭｎＣＩ３ ・４Ｈ２０の１９８ｇ（１モ
ル）とモノエタノールアミ、ジェタノールアミンあるい
はトリエタノールアミンの第５表に示す量をメチルアル
コール１．５１に溶解させ、アンモニアガスを０．２１
Ｌ１分で７時間吹込んだ１反応終了後室温まで冷却し、
析出してくる塩化アンモニウムの結晶を濾別すると、マ
ンガン含有組成物（生成物）のメチルアルコール溶液が
得られた。Table 4 (Niobium-containing composition) Stability X: Within 1i11 Δ: 1 to 2 weeks ○
: within 1 month Example 5 198 g (1 mol) of manganese chloride MnCI3.4H20 and the amount of monoethanolamine, jetanolamine or triethanolamine shown in Table 5 were dissolved in 1.51 ml of methyl alcohol, and ammonia gas was added. 0.21
After completing one reaction in which the mixture was blown for 7 hours at L1 minute, it was cooled to room temperature.
When the precipitated ammonium chloride crystals were filtered off, a methyl alcohol solution of the manganese-containing composition (product) was obtained.
この生成物の状態および保存安定性を第５表に示す。The condition and storage stability of this product are shown in Table 5.
第 Ｓ 表 （マンガン含有組成物）安定性 Δ：
１〜２週間 ○：１ケ月以内Ｏ：１ケ月以上
実施例６
Ｉｎ、Ｏ，換算で１３９ｇ（０，５モル）含有する水酸
化インジウムの１９８８を、（１＋１）塩酸５００ｍ１
に溶解した後濃縮する。１昼夜放置すると、Ｉ ｎ２０
．換算で１３９ｇを含む塩化インジウム・水和物が得ら
れた。Table S (Manganese-containing composition) Stability Δ:
1 to 2 weeks ○: Within 1 month O: 1 month or more Example 6 Indium hydroxide 1988 containing 139 g (0.5 mol) of In, O, in terms of (1+1) hydrochloric acid 500 ml
Concentrate after dissolving in. If left for one day and night, I n20
．． Indium chloride hydrate containing 139 g in terms of conversion was obtained.
この塩化インジウムとモノエタノールアミン、ジェタノ
ールアミンあるいはトリエタノ−、ルアミンの第６表に
示す量をエチルアルコール１．５１に溶解させ、アンモ
ニアガスを０．２ｆｌ／分で９時間吹込んだ。反応終了
後室温まで冷却し、析出する塩化アンモニウムの結晶を
濾別すると、インジウム含有組成物（生成物）のエチル
アルコール溶液が得られた。This indium chloride and monoethanolamine, jetanolamine, or triethanolamine in the amounts shown in Table 6 were dissolved in 1.51 g of ethyl alcohol, and ammonia gas was blown in at 0.2 fl/min for 9 hours. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an ethyl alcohol solution of the indium-containing composition (product).
この生成物の状態および保存安定性を第６表に示す。The condition and storage stability of this product are shown in Table 6.
ｌ−１・二、−′１
゛越−′
第 ６ 表 （インジウム含有組成物）安定性
Ｘ・１遍間以内 Δ：１〜２週間Ｏｚｌケ月以内
Ｏ：１ケ月以上
実施例７
酸化塩化バナジウムＶＯｃ １ ｓ ノ１７３ ｇ （
１モル）とモノエタノールアミン、ジェタノールアミン
あるいはトリエタノールアミンの第７表に示す量をエチ
ルアルコール２１に溶解させ、アンモニアガスを０．２
ｆＬ１分で８時間吹込んだ。反応終了後室温まで放冷し
、析出する塩化アンモニウムの結晶を濾別すると、バナ
ジウム含有組成物（生成物）のエチルアルコール溶液が
得られた。Table 6 (Indium-containing compositions) Stability
Within X・1 hour Δ: Within 1 to 2 weeks Ozl month
O: 1 month or more Example 7 Vanadium oxide chloride VOc 1 s 173 g (
1 mole) and the amounts shown in Table 7 of monoethanolamine, jetanolamine or triethanolamine are dissolved in 21 mol of ethyl alcohol, and 0.2 mol of ammonia gas is dissolved.
It was injected for 8 hours at fL 1 minute. After the reaction was completed, the mixture was allowed to cool to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an ethyl alcohol solution of the vanadium-containing composition (product).
この生成物の状態および保存安定性を第７表に示す。The condition and storage stability of this product are shown in Table 7.
（以下余白す訊
“２−二・−４７・
第 ７ 表 （バナジウム含有組成物）安定性
×：１週間以内 Δ；１〜２週間Ｏ：ｌケ月以内
−ニゲル状で得られるため対象から除外比較例２
アミン類を添加しなかったほかは実施例４と全く同様の
操作を行なったところ、生成物は不安定なゲル状を呈し
、溶液として得ることはできなかった。(Hereinafter, blank spaces are used.) Table 7 (Vanadium-containing composition) Stability
×: Within 1 week Δ: 1 to 2 weeks O: Within 1 month
Comparative Example 2 Excluded from the scope because it was obtained in a gel-like form When the same operation as in Example 4 was performed except that no amines were added, the product exhibited an unstable gel-like form and could not be obtained as a solution. I couldn't.
実施例８
実施例３（塩化エルビウム１モルに対しモノエタノール
アミン１モルを使用したもの）により得たエルビウム含
有組成物のイソプロピルアルコール溶液の一部（液量５
００１１１で塩化物イオン２５０００１１ｇ、 Ｅ ｒ
２０ｓとして４７ｇを含有する）を、強塩基性陰イオン
交換樹脂［商品名：アンバーライトＩＲＡ−４１０（オ
ルガノ社製）］の充填された２０ｍｍφ、９５０＋ａｍ
Ｈのカラムに２．５ ｍ１７分の流速で通過させた。こ
れを５回繰返すことにより得られた液は、処理前に２５
０００ ｍｇであった塩化物イオン含有量が７ｍｇとな
り（酸化物換算当り０．０１４重量％、エルビウム１モ
ル当り８７１００００モル）、不純物である塩化物イオ
ンは大部分が除去されていた。Example 8 A portion of the isopropyl alcohol solution of the erbium-containing composition obtained in Example 3 (using 1 mol of monoethanolamine per 1 mol of erbium chloride) (liquid volume 5
00111 with 2500011 g of chloride ions, E r
20 mm φ, 950 + am filled with strong basic anion exchange resin [trade name: Amberlite IRA-410 (manufactured by Organo Co., Ltd.)]
It was passed through a column of H at a flow rate of 2.5 ml/17 min. The solution obtained by repeating this 5 times was
The chloride ion content, which was 000 mg, became 7 mg (0.014% by weight in terms of oxide, 8710000 mol per 1 mol of erbium), and most of the chloride ions as impurities were removed.
実施例９
実施例４（酸化塩化ニオブ１モルに対しトリエタノール
アミン２．０モルを使用したもの）により得られたニオ
ブ含有組成物のｎ−ブチルアルコール溶液の一部（液量
５００ｍ１で塩化物イオン２９５００１ｇ、 Ｎ ｂ
２０ ｓとして４０ｇを含有する）を、強塩基性陰イオ
ン交換樹脂［商品名：アンバーライトＩＲＡ−４１０（
オルガノ社製）］の充填された２０＋ａｍφ、９５０ｍ
ａ＋Ｈのカラムに２．５ ＋ａｌ／分の流速で通過させ
た。この操作を６回繰返すことにより得られた液は、処
理前に２８５００ｍｇであった塩化物イオン含有量が１
０ａ＋ｇとなり（酸化物換算で０．０２５重量％、ニオ
ブ１モル当り９／１００００モル）、不純物である塩化
物イオンは大部分が除去された。Example 9 A portion of the n-butyl alcohol solution of the niobium-containing composition obtained in Example 4 (using 2.0 mol of triethanolamine per 1 mol of niobium chloride oxide) (with a liquid volume of 500 ml) Ion 295001g, N b
(containing 40 g as 20 s) was added to a strongly basic anion exchange resin [trade name: Amberlite IRA-410 (
(manufactured by Organo)] filled with 20+amφ, 950m
It was passed through an a+H column at a flow rate of 2.5+al/min. By repeating this operation six times, the resulting liquid had a chloride ion content of 1, which was 28,500 mg before treatment.
0a+g (0.025% by weight in terms of oxide, 9/10000 mol per 1 mol of niobium), and most of the impurity chloride ions were removed.
実施例１０
実施例６と同様にして得た塩化インジウム・水和物のＩ
ｎ２Ｏ，換算１３９ｇ（０，５モル）と塩化第一錫・２
水和物２３ｇ（０，１モル）及びモノエタノールアミン
、ジェタノールアミンあるいはトリエタノールアミンの
第８表に示す量をエチルアルコール１．５１Ｌに溶解ま
たは懸濁させ、アンモニアガスを０．２ｆｌ１分で９時
間吹込んだ。反応終了後室温まで冷却し、析出する塩化
アンモニウムの結晶を濾別すると、インジウム−錫を含
む組成物（生成物）のエチルアルコール溶液が得られた
。Example 10 Indium chloride hydrate I obtained in the same manner as Example 6
n2O, equivalent 139g (0.5 mol) and stannous chloride.2
23 g (0.1 mol) of hydrate and the amount of monoethanolamine, jetanolamine or triethanolamine shown in Table 8 were dissolved or suspended in 1.51 L of ethyl alcohol, and 0.2 fl of ammonia gas was added for 1 minute. I blew it for 9 hours. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an ethyl alcohol solution of a composition (product) containing indium-tin.
この生成物の状態および保存安定性を第８表に示す。The condition and storage stability of this product are shown in Table 8.
第 ８ 表 （インジウム−錫含有組成物）安定
性 ×：１週間以内 Δ：１〜２週間Ｏ：１ケ月
以内 ◎：１ケ月以上
実施例１１
塩化第一錫・２水和物２２６ｇ （１モル）と酸化塩化
アンチモン（ＩＩＩ） １７．３ｇ （０，１モル）及
びモノエタノールアミン、ジェタノールアミンあるいは
トリエタノールアミンの第９表に示す量をエチルアルコ
ール３Ｉｌに懸濁させ、アンモニアガスを０．２１Ｌ／
分で８時間吹込んだ。反応終了後室温まで冷却し、析出
してくる塩化アンモニウムの結晶を濾別すると、錫−ア
ンチモンを含む組成物（生成物）のエチルアルコール溶
液が得られた。Table 8 (Indium-tin containing composition) Stability ×: Within 1 week Δ: 1 to 2 weeks O: Within 1 month ◎: Over 1 month Example 11 226 g (1 mol) of stannous chloride dihydrate ), 17.3 g (0.1 mol) of oxidized antimony(III) chloride, and the amounts shown in Table 9 of monoethanolamine, jetanolamine, or triethanolamine were suspended in 3 Il of ethyl alcohol, and 0.1 g of ammonia gas was added. 21L/
It blew for 8 hours in minutes. After the reaction was completed, the mixture was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an ethyl alcohol solution of a composition (product) containing tin-antimony.
この生成物の状態および保存安定性を第９表に示す。The condition and storage stability of this product are shown in Table 9.
゛すＪｌ、、′−−ご〆
第 ９ 表 （錫−アンチモン含有組成物）安定
性 ×：１ｉＪ１間以内 Δ：１〜２週間○：１
ケ月以内 ◎；１ケ月以上
−：ゲル状で得られるため対象から除外実施例１２
塩化イツトリウム・６水和物２０３ｇ（１モル）とモノ
エタノールアミン、ジェタノールアミンあるいはトリエ
タノールアミンの第１０表に示す量をメチルアルコール
１．５ ＩＬに溶解し、アンモニアガスを０．２Ｊ１／
分で８時間吹込んだ。反応終了後室温まで冷却し、塩化
アンモニウムの結晶を濾別すると、イツトリウム含有組
成物（生成物）のメチルアルコール溶液が得られた。Table 9 (Tin-antimony containing composition) Stability ×: Within 1iJ1 Δ: 1 to 2 weeks ○: 1
Within 1 month -: Excluded from the scope because it is obtained in gel form Dissolve the indicated amount in 1.5 IL of methyl alcohol, and add 0.2 J1/L of ammonia gas.
It blew for 8 hours in minutes. After the reaction was completed, the mixture was cooled to room temperature and ammonium chloride crystals were filtered off to obtain a methyl alcohol solution of the yttrium-containing composition (product).
この生成物の状態および保存安定性を第１０表に示す。The condition and storage stability of this product are shown in Table 10.
（以下余白）“゛已ｑ・１
■訃も
３４ １０ 表 （イツトリウム含有組成物）安定
性 Δ：１〜２週間 ○：１ケ月以内Ｏｆケ月以上
実施例１３
三塩化チタン・６水和物ｚａｚｇ （およそ１モル）と
モノエタノールアミン、ジェタノールアミンあるいはト
リエタノールアミンの第１１表に示す量をエチルアルコ
ールｔ、Ｓ ｊＺに溶解し、アンモニアガスを０．２１
Ｌ１分で８時間吹込んだ６反応終了後室温まで冷却し析
出する塩化アンモニウムの結晶を濾別すると、チタン含
有組成物（生成物）のエチルアルコール溶液が得られた
。(Margins below) “゛已q・1 ■Death 34 10 Table (Yttrium-containing composition) Stability Δ: 1 to 2 weeks ○: Less than 1 month Of more than 1 month Example 13 Titanium trichloride hexahydrate zazg (approximately 1 mole) and the amounts shown in Table 11 of monoethanolamine, jetanolamine, or triethanolamine were dissolved in ethyl alcohol, and 0.21 mole of ammonia gas was dissolved.
After completion of the 6 reactions in which the mixture was injected for 8 hours at L1 minute, it was cooled to room temperature and precipitated ammonium chloride crystals were filtered off to obtain an ethyl alcohol solution of the titanium-containing composition (product).
この生成物の状態および保存安定性を第１１表に示す。The condition and storage stability of this product are shown in Table 11.
第 １１ 表 （チタン含有組成物）安定性
Δ：１〜２週間 ○：１ケ月以内Ｏ：１ケ月以上
［発明の効果］
本発明は以上の様に構成されており、その効果を要約す
れば次の通りである。Table 11 (Titanium-containing composition) Stability
Δ: 1 to 2 weeks ○: Within 1 month O: 1 month or more [Effects of the Invention] The present invention is configured as described above, and its effects are summarized as follows.
（１）従来空気中の水分によってさえも加水分解を受け
るほど不安定であったＡＩ、Ｉｎ。(1) AI and In have traditionally been so unstable that they are subject to hydrolysis even by moisture in the air.
Ｙ、ランタン系元素、Ｓｎ、Ｔｉ、Ｚｒ。Y, lanthanum-based elements, Sn, Ti, Zr.
Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から選択される金
属含有組成物を、安定なアルコール溶液として得ること
が可能になった。It has become possible to obtain metal-containing compositions selected from the group consisting of Sb, V, Nb and Mn as stable alcohol solutions.
（２）該溶液状態の金属含有組成物をイオン交換樹脂で
処理すると、その純度を飛躍的に高めることがで包る。(2) When the metal-containing composition in a solution state is treated with an ion exchange resin, its purity can be dramatically increased.
（３）該金属含有組成物のアルコール溶液に水を加えて
加水分解すると、当該金属の酸化物、水酸化物、水和物
等からなる極めて純度の高い微粉末を得ることができ、
蛍光体製造分野における賦活剤としての微量添加物、ペ
ロブスカイト型酸化物などのニューセラミックス分野、
金属材料、セラミックス表面へのコーティング剤、ＧＧ
Ｇなどの機能性薄膜分野、セラミックスなどの焼結助剤
的な添加剤としであるいは金属材料などの高温酸化防止
用材料として極めて有効に活用することができる。(3) When water is added to an alcoholic solution of the metal-containing composition and hydrolyzed, extremely pure fine powder consisting of oxides, hydroxides, hydrates, etc. of the metal can be obtained;
Trace additives as activators in the phosphor manufacturing field, new ceramics fields such as perovskite oxides,
Coating agents for metal materials and ceramic surfaces, GG
It can be extremely effectively used in the field of functional thin films such as G, as a sintering aid additive for ceramics, and as a high-temperature oxidation prevention material for metal materials.
代理人 弁理士 浅 草 宋 三ｌ□；。ｖ鳳（ｐ
ｉ−≠
第１頁の絖きAgent: Patent attorney Asakusa Song Sanl□;. v Otori (p
i-≠ 1st page
Claims (6)
Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から選択さ
れる１種または２種以上の金属のハロゲン化物と、アル
コールアミン類の１種または２種以上とを、炭素数１〜
４のアルコールに溶解または懸濁させ、アンモニアの存
在下で反応させることを特徴とする金属含有組成物の製
造方法。(1) Al, In, Y, lanthanum-based elements, Sn, Ti,
One or more metal halides selected from the group consisting of Zr, Sb, V, Nb and Mn and one or more alcohol amines having 1 to 1 carbon atoms.
4. A method for producing a metal-containing composition, which comprises dissolving or suspending the metal-containing composition in alcohol and reacting it in the presence of ammonia.
、酸化ハロゲン化物、あるいは結晶水を含む酸化ハロゲ
ン化物である特許請求の範囲第１項記載の金属含有組成
物の製造方法。(2) The method for producing a metal-containing composition according to claim 1, wherein the metal halide is a halide containing water of crystallization, an oxidized halide, or an oxidized halide containing water of crystallization.
Ｈ＿２ＣＨ＿２ＯＨ）＿３ ［ただしＲ＿１、Ｒ＿２はＣｎＨ＿２＿ｎ＿＋＿１、ｎ
は０または１〜４の整数を表わす］ で表わされるエタノールアミン類である特許請求の範囲
第１または２項記載の金属含有組成物の製造方法。(3) Alcohol amines have the general formula a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ b) R_1N(CH_2CH_2OH)_2c) N(C
H_2CH_2OH)_3 [However, R_1, R_2 are CnH_2_n_+_1, n
represents 0 or an integer of 1 to 4] The method for producing a metal-containing composition according to claim 1 or 2, wherein the metal-containing composition is an ethanolamine represented by the following.
Ｚｒ、Ｓｂ、Ｖ、ＮｂおよびＭｎよりなる群から選択さ
れる１種または２種以上の金属のハロゲン化物と、アル
コールアミン類の１種または２種以上とを、炭素数１〜
４のアルコールに溶解または懸濁させ、アンモニアの存
在下で反応させた後、得られる溶液をイオン交換樹脂で
処理することを特徴とする金属含有組成物の製造方法。(4) Al, In, Y, lanthanum-based elements, Sn, Ti,
One or more metal halides selected from the group consisting of Zr, Sb, V, Nb and Mn and one or more alcohol amines having 1 to 1 carbon atoms.
4. A method for producing a metal-containing composition, which comprises dissolving or suspending the composition in alcohol and reacting it in the presence of ammonia, and then treating the resulting solution with an ion exchange resin.
物、酸化ハロゲン化物、あるいは結晶水を含む酸化ハロ
ゲン化物である特許請求の範囲第４項記載の金属含有組
成物の製造方法。(5) The method for producing a metal-containing composition according to claim 4, wherein the metal halide is a halide containing water of crystallization, an oxidized halide, or an oxidized halide containing water of crystallization.
Ｈ＿２ＣＨ＿２ＯＨ）＿３ ［ただしＲ＿１、Ｒ＿２はＣ＿ｎＨ＿２＿ｎ＿＋＿１、
ｎは０または１〜４の整数を表わす］ で表わされるエタノールアミン類である特許請求の範囲
第４または５項記載の金属含有組成物の製造方法。(6) Alcohol amines have the general formula a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ b) R_1N(CH_2CH_2OH)_2c) N(C
H_2CH_2OH)_3 [However, R_1 and R_2 are C_nH_2_n_+_1,
n represents 0 or an integer of 1 to 4] The method for producing a metal-containing composition according to claim 4 or 5, wherein the metal-containing composition is an ethanolamine represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11330887A JPH0819138B2 (en) | 1987-05-08 | 1987-05-08 | Method for producing metal-containing alcohol solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11330887A JPH0819138B2 (en) | 1987-05-08 | 1987-05-08 | Method for producing metal-containing alcohol solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63277687A true JPS63277687A (en) | 1988-11-15 |
| JPH0819138B2 JPH0819138B2 (en) | 1996-02-28 |
Family
ID=14608942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11330887A Expired - Fee Related JPH0819138B2 (en) | 1987-05-08 | 1987-05-08 | Method for producing metal-containing alcohol solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0819138B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019106A (en) * | 2006-07-11 | 2008-01-31 | Denso Corp | Method for producing metal oxide particle |
-
1987
- 1987-05-08 JP JP11330887A patent/JPH0819138B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019106A (en) * | 2006-07-11 | 2008-01-31 | Denso Corp | Method for producing metal oxide particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0819138B2 (en) | 1996-02-28 |
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