JP2006143535A - Zirconia sol and its manufacturing method - Google Patents
Zirconia sol and its manufacturing method Download PDFInfo
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- JP2006143535A JP2006143535A JP2004336595A JP2004336595A JP2006143535A JP 2006143535 A JP2006143535 A JP 2006143535A JP 2004336595 A JP2004336595 A JP 2004336595A JP 2004336595 A JP2004336595 A JP 2004336595A JP 2006143535 A JP2006143535 A JP 2006143535A
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- zirconia
- zirconia sol
- sol
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- zirconium hydroxide
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 381
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 99
- 239000006185 dispersion Substances 0.000 claims abstract description 91
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000003630 growth substance Substances 0.000 claims abstract description 25
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 18
- 239000010419 fine particle Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract 1
- 239000000017 hydrogel Substances 0.000 description 53
- 238000002242 deionisation method Methods 0.000 description 33
- 239000012528 membrane Substances 0.000 description 30
- 238000000108 ultra-filtration Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000003957 anion exchange resin Substances 0.000 description 27
- 239000000126 substance Substances 0.000 description 22
- 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 description 20
- 238000003917 TEM image Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 239000011362 coarse particle Substances 0.000 description 16
- 239000003729 cation exchange resin Substances 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 13
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 13
- 239000001630 malic acid Substances 0.000 description 13
- 235000011090 malic acid Nutrition 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003754 zirconium Chemical class 0.000 description 3
- -1 zirconium alkoxides Chemical class 0.000 description 3
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 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
- 150000007522 mineralic acids Chemical class 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- 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
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
本発明は、安定性に優れたコロイド領域のジルコニアゾルおよび該ジルコニアゾルを製造する方法に関する。 The present invention relates to a colloidal zirconia sol excellent in stability and a method for producing the zirconia sol.
従来、シリカ、アルミナ、チタニア、ジルコニア、酸化亜鉛、五酸化アンチモン、酸化セリウム、酸化スズ、シリカ・アルミナ、シリカ・ジルコニアなどのコロイド粒子が知られており、光学材料として屈折率を調整するために被膜等に配合して用いられている。
例えば、シリカは低屈折材料として、アルミナは中程度の屈折率材料として、チタニア、ジルコニア等は高屈折率材料として用いられている。このとき、チタニアゾルは高屈折率である点では優れているものの、分散安定性や、用法、用途によっては酸化チタンの光触媒活性のために耐光性、耐候性等に問題があった。このため、他の成分、例えばシリカ成分などを複合化することによって分散安定性や、耐光性、耐候性等を向上させることが行われているが、複合化成分によっては屈折率を低下させることになることに加えて、光触媒活性を完全に抑制することが困難で、このため耐光性、耐候性等が不充分となることがあった。
Conventionally, colloidal particles such as silica, alumina, titania, zirconia, zinc oxide, antimony pentoxide, cerium oxide, tin oxide, silica-alumina, silica-zirconia, etc. are known, and to adjust the refractive index as an optical material It is blended and used for coatings.
For example, silica is used as a low refractive index material, alumina is used as a medium refractive index material, and titania, zirconia, and the like are used as high refractive index materials. At this time, although titania sol is excellent in that it has a high refractive index, there are problems in light resistance, weather resistance, and the like due to the dispersion stability, photocatalytic activity of titanium oxide depending on the usage and application. For this reason, it has been attempted to improve dispersion stability, light resistance, weather resistance, etc. by combining other components, such as silica components, but depending on the composite component, the refractive index can be lowered. In addition to this, it is difficult to completely suppress the photocatalytic activity, so that the light resistance, weather resistance, etc. may be insufficient.
一方、ジルコニアゾルは光触媒活性を実質的に持たず、耐光性、耐候性等に優れており、従来より、ジルコニアゾルの製造方法としては、オキシ塩化ジルコニウム等の水溶性ジルコニウム塩を含む水溶液を加水分解させる方法が知られている。
さらに、特開平６−１６６５１９号公報（特許文献１）には、水溶性ジルコニウム塩を含む水溶液を陰イオン交換樹脂と接触させて、該ジルコニウム塩の陰イオンを水酸基イオンとイオン交換することにより粘調なゲル状物質を得、得られたゲル状物質を水に分散させると共に酢酸等の有機酸を添加するジルコニアゾルの製造方法が記載されている。
また、特開平５−２４８４４号公報（特許文献２）には、水酸化ジルコニウムと酸とを含むスラリー状の混合物の酸濃度を制御して加熱処理する水和ジルコニアゾルの製造方法が記載され、酸として、塩酸、硝酸、硫酸等の無機酸、酢酸、クエン酸等の有機酸が挙げられている。
しかしながら、特許文献１または特許文献２のように、水酸化ジルコニウムのような加水分解物およびジルコニウム水酸化物ゲルに、酢酸、クエン酸等の有機酸または無機酸を添加してジルコニアゾルを調製しても、均一な粒子径分布を有し、安定性に優れたコロイド領域のジルコニアゾルを得ることは困難であった。
On the other hand, zirconia sol has substantially no photocatalytic activity and is excellent in light resistance, weather resistance and the like. Conventionally, as a method for producing zirconia sol, an aqueous solution containing a water-soluble zirconium salt such as zirconium oxychloride is hydrolyzed. A method of decomposing is known.
Further, JP-A-6-166519 (Patent Document 1) discloses that an aqueous solution containing a water-soluble zirconium salt is brought into contact with an anion exchange resin, and the anion of the zirconium salt is ion-exchanged with a hydroxyl ion. A method for producing a zirconia sol is described, in which a smooth gel-like substance is obtained, and the obtained gel-like substance is dispersed in water and an organic acid such as acetic acid is added.
JP-A-5-24844 (Patent Document 2) describes a method for producing a hydrated zirconia sol in which the acid concentration of a slurry-like mixture containing zirconium hydroxide and an acid is controlled and heat-treated, Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid and citric acid.
However, as in Patent Document 1 or Patent Document 2, a zirconia sol is prepared by adding an organic acid or inorganic acid such as acetic acid or citric acid to a hydrolyzate such as zirconium hydroxide and a zirconium hydroxide gel. However, it is difficult to obtain a colloidal zirconia sol having a uniform particle size distribution and excellent stability.
特公平６−６５６１０号公報（特許文献３）には、炭酸ジルコニルアンモニウムと特定のキレート化剤とを反応させ、得られる反応生成物を６０〜３００℃で加熱加水分解してジルコニアゾルを製造する方法が開示されており、得られたｐＨ７付近のジルコニアゾルは長期安定で、ｐＨ６〜１４の範囲で使用してもゲル化が起きない中性ないし塩基性タイプの無機バインダー等として好適に使用できることが記載されている。特許文献３には、ジルコニアゾル粒子の粒子径および粒子径分布については記載されておらず、如何なる粒子径および粒子径分布を有するものであるか不明であるが、少なくとも酸性域における安定性に優れたコロイド領域のジルコニアゾルではない。
本発明は、均一な粒子径分布を有し、安定性（特に酸性域における安定性）に優れたコロイド領域のジルコニアゾルおよびこれを製造することを発明が解決しようとする課題とするものである。 The present invention has an object to be solved by the present invention to produce a colloidal zirconia sol having a uniform particle size distribution and excellent stability (especially in the acidic region), and the production thereof. .
本発明に係るジルコニアゾルの製造方法は平均粒子径が５〜１００ｎｍの範囲にあるジルコニア微粒子が分散したゾルを製造する方法であって、下記の工程（ａ）〜（ｅ）からなることを特徴とする。
（ａ）粒子成長調整剤の存在下、ジルコニウム化合物水溶液にアルカリ水溶液を加えてジルコニウム水酸化物ゲルの分散液を調製する工程
（ｂ）前記ジルコニウム水酸化物ゲルを洗浄する工程
（ｃ）前記洗浄したジルコニウム水酸化物ゲルの分散液を熟成する工程
（ｄ）前記熟成したジルコニウム水酸化物ゲルを洗浄する工程
（ｅ）粒子成長調整剤の存在下、前記洗浄したジルコニウム水酸化物ゲルの分散液を水熱処理する工程
The method for producing a zirconia sol according to the present invention is a method for producing a sol in which zirconia fine particles having an average particle diameter in the range of 5 to 100 nm are dispersed, and comprises the following steps (a) to (e): And
(A) A step of preparing a dispersion of a zirconium hydroxide gel by adding an alkaline aqueous solution to a zirconium compound aqueous solution in the presence of a particle growth regulator (b) a step of washing the zirconium hydroxide gel (c) the washing (D) a step of rinsing the aged zirconium hydroxide gel; (e) a step of washing the aged zirconium hydroxide gel; and (e) a dispersion of the washed zirconium hydroxide gel in the presence of a particle growth regulator. Hydrothermal treatment process
前記ゾルのｐＨは３〜５の範囲にあることが好ましい。
前記工程（ｅ）で得られたジルコニア微粒子分散ゾルは、濃縮または希釈することができる。
前記粒子成長調整剤はカルボン酸またはヒドロキシカルボン酸であることが好ましい。
前記水熱処理を１００〜２５０℃の温度範囲で行うことが好ましい。
前記工程（ｅ）を繰り返し行うことが好ましく、工程（ｅ）と共に工程（ｄ）を繰り返し行うことが好ましい。
前記（ｂ）工程でジルコニウム水酸化物ゲル分散液の電導度を２０μＳ／ｃｍ以下とすることが好ましく、前記（ｅ）工程でジルコニアゾルの電導度を２００μＳ／ｃｍ以下とすることが好ましい。
前記工程（ｅ）または前記繰り返し実施した工程（ｅ）の後、ジルコニアゾルを乾燥し、３００〜８００℃の範囲で焼成し、得られたジルコニア微粉末を再び分散液に分散させることが好ましい。
The pH of the sol is preferably in the range of 3-5.
The zirconia fine particle-dispersed sol obtained in the step (e) can be concentrated or diluted.
The particle growth regulator is preferably a carboxylic acid or a hydroxycarboxylic acid.
The hydrothermal treatment is preferably performed in a temperature range of 100 to 250 ° C.
The step (e) is preferably repeated, and the step (d) is preferably repeated together with the step (e).
In the step (b), the conductivity of the zirconium hydroxide gel dispersion is preferably 20 μS / cm or less, and in the step (e), the conductivity of the zirconia sol is preferably 200 μS / cm or less.
After the step (e) or the repeated step (e), it is preferable that the zirconia sol is dried and fired in the range of 300 to 800 ° C., and the obtained zirconia fine powder is dispersed again in the dispersion.
本発明に係るジルコニアゾルは、平均粒子径が５〜１００ｎｍの範囲にあり、結晶子径が５〜４０ｎｍの範囲にあるジルコニア粒子が分散したジルコニア酸性ゾルである。
また、本発明に係るジルコニアゾルは、前記したいずれかのジルコニアゾルの製造方法によって得られた、結晶子径が５〜４０ｎｍの範囲にあるジルコニア粒子が分散したジルコニア酸性ゾルである。該酸性ゾルのｐＨは３〜５の範囲にあることが好ましい。
The zirconia sol according to the present invention is a zirconia acidic sol in which zirconia particles having an average particle diameter in the range of 5 to 100 nm and a crystallite diameter in the range of 5 to 40 nm are dispersed.
The zirconia sol according to the present invention is a zirconia acidic sol in which zirconia particles having a crystallite diameter in the range of 5 to 40 nm are dispersed, which is obtained by any one of the above-described zirconia sol production methods. The pH of the acidic sol is preferably in the range of 3-5.
本発明によれば、粒子径が比較的小さく、均一な粒子径分布を有し、非凝集体で、分散性、安定性に優れたジルコニアゾルを製造することができる。また、このジルコニアゾルは、透明性、耐光性、耐候性等に優れるので、光学材料等における、高屈折率材料、屈折率調整剤等として好適である。 According to the present invention, it is possible to produce a zirconia sol having a relatively small particle size, a uniform particle size distribution, a non-aggregate, and excellent dispersibility and stability. Moreover, since this zirconia sol is excellent in transparency, light resistance, weather resistance, etc., it is suitable as a high refractive index material, a refractive index adjusting agent, etc. in optical materials.
以下、本発明のジルコニアゾルの製造方法を工程順に説明する。
工程（ａ）
本発明に用いるジルコニウム化合物としては塩化ジルコニウム（ＺrＣｌ2）、オキシ塩化ジルコニウム（ＺrＯＣｌ2）、硝酸ジルコニウム、硝酸ジルコニル、硫酸ジルコニウム、炭酸ジルコニウム、酢酸ジルコニウム等の他、ジルコニウムアルコキシド等が挙げられる。
先ず、ジルコニウム化合物の水溶液を調製する。このときのジルコニウム化合物水溶液の濃度は、ＺrＯ2に換算して０.１〜５重量％、さらには０.２〜３重量％の範囲にあることが好ましい。該濃度が０.１重量％未満の場合は、収率、生産効率が低く、一方、該濃度が５重量％を越えると、得られるジルコニアゾルの粒子径が不均一となる傾向がある。
Hereinafter, the manufacturing method of the zirconia sol of this invention is demonstrated in order of a process.
Step (a)
Zirconium compounds used in the present invention include zirconium chloride (ZrCl 2 ), zirconium oxychloride (ZrOCl 2 ), zirconium nitrate, zirconyl nitrate, zirconium sulfate, zirconium carbonate, zirconium acetate and the like, as well as zirconium alkoxides.
First, an aqueous solution of a zirconium compound is prepared. The concentration of the zirconium compound aqueous solution at this time is preferably in the range of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight in terms of ZrO 2 . When the concentration is less than 0.1% by weight, the yield and production efficiency are low. On the other hand, when the concentration exceeds 5% by weight, the particle size of the resulting zirconia sol tends to be non-uniform.
本発明に用いる粒子成長調整剤としては、カルボン酸、カルボン酸塩、またはヒドロキシカルボン酸、ヒドロキシカルボン酸塩が用いられる。
具体的には、蟻酸、酢酸、蓚酸、アクリル酸（不飽和カルボン酸）、グルコン酸等のモノカルボン酸およびモノカルボン酸塩、リンゴ酸、シュウ酸、マロン酸、コハク酸、グルタール酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、などの多価カルボン酸および多価カルボン酸塩等が挙げられる。
また、α−乳酸、β−乳酸、γ−ヒドロキシ吉草酸、グリセリン酸、酒石酸、クエン酸、トロパ酸、ベンジル酸のヒドロキシカルボン酸およびヒドロキシカルボン酸塩が挙げられる。
As the particle growth regulator used in the present invention, carboxylic acid, carboxylate, hydroxycarboxylic acid, or hydroxycarboxylate is used.
Specifically, monocarboxylic acids and monocarboxylic acid salts such as formic acid, acetic acid, succinic acid, acrylic acid (unsaturated carboxylic acid), gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid And polyvalent carboxylic acids such as sebacic acid, maleic acid, fumaric acid, and phthalic acid, and polyvalent carboxylic acid salts.
Further, α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid, hydroxycarboxylic acid and hydroxycarboxylate of benzylic acid can be mentioned.
工程（ａ）では、ジルコニウム化合物水溶液に前記粒子成長調整剤または粒子成長調整剤の水溶液を混合する。このときのジルコニウム化合物のモル数（Ｚm）と粒子成長調整剤のモル数（Ｃm）とのモル比（Ｃm／Ｚm）は０.０１〜１、さらには０.１〜０.５の範囲にあることが好ましい。モル比が０.０１未満の場合は、粗大なジルコニウム水酸化物ヒドロゲルが生成したり、不均一なジルコニウム水酸化物ヒドロゲルが生成し、このため、後述する工程（ｅ）で水熱処理して得られるジルコニアゾルの粒子径が不均一であったり、平均粒子径が１００ｎｍ以下とならないことがある。一方、前記モル比が１を越えてもさらに粒子径を均一にしたり、平均粒子径を小さく抑制する効果がさらに向上することもなく、加えて経済性が低下する問題がある。 In the step (a), the particle growth regulator or an aqueous solution of the particle growth regulator is mixed with the zirconium compound aqueous solution. At this time, the molar ratio (Cm / Zm) between the number of moles of zirconium compound (Zm) and the number of moles of grain growth regulator (Cm) is in the range of 0.01 to 1, more preferably 0.1 to 0.5. Preferably there is. When the molar ratio is less than 0.01, a coarse zirconium hydroxide hydrogel is formed or a heterogeneous zirconium hydroxide hydrogel is formed. Therefore, it is obtained by hydrothermal treatment in the step (e) described later. The particle diameter of the zirconia sol to be produced may not be uniform or the average particle diameter may not be 100 nm or less. On the other hand, even if the molar ratio exceeds 1, there is a problem that the particle size is not made uniform or the effect of suppressing the average particle size is not further improved, and the economy is lowered.
ついで、粒子成長調整剤を含むジルコニウム化合物水溶液を充分に撹拌しながら、これにアルカリ水溶液を加える。
アルカリ水溶液としては、ＮaＯＨ水溶液、ＫＯＨ水溶液等のアルカリ金属塩の水溶液の他、アンモニア水、有機アミン水溶液などの塩基性水溶液を用いることができる。
アルカリ水溶液はジルコニウム化合物水溶液のｐＨが３〜１２、さらには４〜１１の範囲となるように添加する。ｐＨが３未満の場合は、ジルコニウム化合物の加水分解が不充分となったり、後述する工程（ｂ）での洗浄が困難となることがあり、一方、ｐＨが１２を越えても後述する工程（ｂ）での洗浄が困難となることがある。
なお、アルカリ水溶液を添加する際のジルコニウム化合物水溶液の温度は特に制限はないが、通常１０〜５０℃、さらには１５〜４０℃の範囲にあることが好ましい。
Next, an aqueous alkali compound solution is added to the zirconium compound aqueous solution containing the particle growth regulator while sufficiently stirring.
As the alkaline aqueous solution, an aqueous solution of an alkali metal salt such as an aqueous NaOH solution or an aqueous KOH solution, or a basic aqueous solution such as aqueous ammonia or organic amine can be used.
The aqueous alkali solution is added so that the zirconium compound aqueous solution has a pH of 3 to 12, more preferably 4 to 11. When the pH is less than 3, the hydrolysis of the zirconium compound may be insufficient, or washing in the step (b) described later may be difficult. On the other hand, even if the pH exceeds 12, the step described later ( Cleaning in b) may be difficult.
In addition, the temperature of the zirconium compound aqueous solution when adding the alkaline aqueous solution is not particularly limited, but it is usually preferably in the range of 10 to 50 ° C, more preferably 15 to 40 ° C.
工程（ｂ）
次いで、生成したジルコニウム水酸化物ヒドロゲルの分散液を洗浄する。
洗浄方法としては、陽イオン、陰イオン、あるいは塩を除去できれば特に制限はなく、従来公知の方法を採用することができ、例えば、限外濾過膜法、濾過分離法、遠心分離濾過法、イオン交換樹脂法等が挙げられる。
なかでもイオン交換樹脂法は洗浄後のイオン濃度を効果的に低下させることができるので好ましい。この場合、予め限外濾過膜法で洗浄した後、イオン交換樹脂法で洗浄すると効率的である。イオン交換樹脂としては、両イオン交換樹脂を用いるか、陽イオン交換樹脂と陰イオン交換樹脂とを順次用いることができる。
Step (b)
Next, the produced dispersion of zirconium hydroxide hydrogel is washed.
The washing method is not particularly limited as long as it can remove cations, anions, or salts, and a conventionally known method can be adopted. For example, an ultrafiltration membrane method, a filtration separation method, a centrifugal filtration method, an ion Examples include the exchange resin method.
Among these, the ion exchange resin method is preferable because the ion concentration after washing can be effectively reduced. In this case, it is efficient to wash with an ion exchange resin method after washing with an ultrafiltration membrane method in advance. As the ion exchange resin, both ion exchange resins can be used, or a cation exchange resin and an anion exchange resin can be sequentially used.
洗浄後の電導度は２０μＳ／ｃｍ以下、さらには１０μＳ／ｃｍ以下であることが好ましい。洗浄後の電導度が２０μＳ／ｃｍを越えると、粒子成長調整剤の効果が充分得られないか、得られるジルコニアゾルの粒子径分布が不均一となる傾向がある。
また、このときの洗浄ジルコニウム水酸化物ヒドロゲル分散液のｐＨは概ね５〜８の範囲である。
The conductivity after washing is preferably 20 μS / cm or less, more preferably 10 μS / cm or less. When the electric conductivity after washing exceeds 20 μS / cm, the effect of the particle growth regulator cannot be obtained sufficiently, or the particle size distribution of the obtained zirconia sol tends to be non-uniform.
Further, the pH of the washed zirconium hydroxide hydrogel dispersion at this time is approximately in the range of 5-8.
工程（ｃ）
ついで、前記洗浄したジルコニウム水酸化物ゲルを熟成する。
工程（ｂ）で得た洗浄ジルコニウム水酸化物ヒドロゲル分散液の濃度はＺrＯ2に換算して０.１〜２０重量％、さらには０.２〜１５重量％、特に０.５〜１０重量％の範囲に調整することが好ましい。この濃度が０.１重量％未満の場合は、粒子径分布は均一になるものの収率、生産効率が低下する問題がある。一方、濃度が２０重量％を越えると、得られるジルコニアゾルに凝集体が生成することがある。
この濃度を調整したジルコニウム水酸化物ヒドロゲル分散液を充分に撹拌しながら昇温して熟成する。該分散液は昇温する前または昇温中に超音波を照射するなどしてジルコニウム水酸化物ヒドロゲルの凝集体をできるだけ分散させておくことが好ましい。ジルコニウム水酸化物ヒドロゲルの凝集体を分散させておくと、得られるジルコニアゾルに粗大粒子が存在することがなく、また粒子径分布がより均一なジルコニアゾルが得られる傾向がある。
Step (c)
Next, the washed zirconium hydroxide gel is aged.
The concentration of the washed zirconium hydroxide hydrogel dispersion obtained in step (b) is 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, especially 0.5 to 10% by weight in terms of ZrO 2. It is preferable to adjust to the range. When this concentration is less than 0.1% by weight, the particle size distribution becomes uniform, but there is a problem that the yield and production efficiency are lowered. On the other hand, if the concentration exceeds 20% by weight, aggregates may be formed in the resulting zirconia sol.
The zirconium hydroxide hydrogel dispersion having this concentration adjusted is aged by heating while sufficiently stirring. It is preferable to disperse the zirconium hydroxide hydrogel aggregate as much as possible by irradiating ultrasonic waves before or during the temperature rise. When the aggregate of the zirconium hydroxide hydrogel is dispersed, coarse particles are not present in the obtained zirconia sol, and a zirconia sol having a more uniform particle size distribution tends to be obtained.
熟成温度は１００〜２５０℃、さらには１２０〜２００℃の範囲にあることが好ましい。１００℃未満の場合は、粒子成長に長時間を要したり、所望の屈折率あるいは所望の粒子径のジルコニアゾルを得ることが困難となることがある。熟成温度が２５０℃を越えても粒子成長時間がさらに短くなる効果は小さく、場合によっては粒子径分布が不均一になったり、粗大な粒子が生成することがある。
なお、熟成時間は特に制限はなく、熟成温度によって異なるが、通常０.５〜１２時間である。
The aging temperature is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the temperature is lower than 100 ° C., it may take a long time for particle growth, or it may be difficult to obtain a zirconia sol having a desired refractive index or a desired particle diameter. Even if the aging temperature exceeds 250 ° C., the effect of further shortening the particle growth time is small, and in some cases, the particle size distribution may be non-uniform or coarse particles may be generated.
The aging time is not particularly limited and varies depending on the aging temperature, but is usually 0.5 to 12 hours.
工程（ｄ）
ついで、工程（ｃ）で得られた熟成したジルコニウム水酸化物ヒドロゲルの分散液を洗浄する。洗浄方法としては、限外濾過膜法が好ましい。また、必要に応じて限外濾過膜法による洗浄の前および／または後にイオン交換樹脂による洗浄を行うこともできる。イオン交換樹脂法は洗浄後のイオン濃度を効果的に低下させることができるので好ましい。
ここで得られるゲル分散液の電導度は概ね２００μＳ／ｃｍ以下であることが好ましい。また、ゲル分散液のｐＨは概ね３〜５の範囲であることが好ましい。電導度およびｐＨが前記範囲にあるとゲル分散液は安定性に優れている。
Step (d)
Next, the aged dispersion of zirconium hydroxide hydrogel obtained in step (c) is washed. As a washing method, an ultrafiltration membrane method is preferable. Further, if necessary, washing with an ion exchange resin can be performed before and / or after washing by the ultrafiltration membrane method. The ion exchange resin method is preferable because the ion concentration after washing can be effectively reduced.
The electric conductivity of the gel dispersion obtained here is preferably about 200 μS / cm or less. Further, the pH of the gel dispersion is preferably in the range of 3 to 5. When the electrical conductivity and pH are in the above ranges, the gel dispersion is excellent in stability.
工程（ｅ）
ついで、粒子成長調整剤の存在下、前記洗浄したジルコニウム水酸化物ゲルの分散液を水熱処理する。
洗浄したジルコニウム水酸化物ヒドロゲル分散液に粒子成長調整剤または粒子成長調整剤水溶液を添加する。粒子成長調整剤としては前記したと同様のものを用いることができる。
このときの粒子成長調整剤の添加量は、ジルコニウム水酸化物ヒドロゲル分散液中のＺrＯ2のモル数（Ｚmc）と粒子成長調整剤のモル数（Ｃmc）とのモル比Ｃmc／Ｚmcは０.０５〜０.８、さらには０.１〜０.５の範囲にあることが好ましい。前記モル比Ｃmc／Ｚmcが０.０５未満の場合は、得られるジルコニアゾル中に凝集体が生成したり、平均粒子径が１００ｎｍ以下のジルコニアゾルを得るのが困難となることがある。前記モル比Ｃmc／Ｚmcが０.８を越えると、粒子成長あるいは結晶化が大きく抑制されるために所望の粒子径に成長させるのに長時間を要したり、結晶化（結晶子径の成長）が不充分なためか所望の屈折率あるいは所望の粒子径のジルコニアゾルを得ることが困難となることがある。
Step (e)
Next, the washed zirconium hydroxide gel dispersion is hydrothermally treated in the presence of a particle growth regulator.
A particle growth regulator or a particle growth regulator aqueous solution is added to the washed zirconium hydroxide hydrogel dispersion. As the particle growth regulator, the same ones as described above can be used.
The amount of the particle growth regulator added at this time is such that the molar ratio Cmc / Zmc between the number of moles of ZrO 2 in the zirconium hydroxide hydrogel dispersion (Zmc) and the number of moles of the grain growth regulator (Cmc) is 0. It is preferably in the range of 05 to 0.8, more preferably 0.1 to 0.5. When the molar ratio Cmc / Zmc is less than 0.05, aggregates may be generated in the obtained zirconia sol, or it may be difficult to obtain a zirconia sol having an average particle size of 100 nm or less. If the molar ratio Cmc / Zmc exceeds 0.8, particle growth or crystallization is greatly suppressed, so that it takes a long time to grow to a desired particle size or crystallization (growth of crystallite size). ) Is insufficient, it may be difficult to obtain a zirconia sol having a desired refractive index or a desired particle size.
ついで、粒子成長調整剤を含む洗浄したジルコニウム水酸化物ヒドロゲル分散液を充分に撹拌しながら昇温して、水熱処理をする。
水熱処理温度は１００〜２５０℃、さらには１２０〜２００℃の範囲にあることが好ましい。水熱処理温度が１００℃未満の場合は、結晶化および粒子成長に長時間を要したり、屈折率の高いジルコニア粒子の分散したゾルを得ることが困難となることがある。水熱処理温度が２５０℃を越えても結晶化および粒子成長時間がさらに短くなる効果は小さく、場合によっては粒子径分布が不均一になったり、粗大な粒子が生成することがある。
なお、水熱処理時間は特に制限はなく、処理温度によって異なるが、通常０.５〜１２時間である。
Next, the washed zirconium hydroxide hydrogel dispersion containing the particle growth regulator is heated with sufficient agitation to perform hydrothermal treatment.
The hydrothermal treatment temperature is preferably in the range of 100 to 250 ° C, more preferably 120 to 200 ° C. When the hydrothermal treatment temperature is less than 100 ° C., it may take a long time for crystallization and particle growth, or it may be difficult to obtain a sol in which zirconia particles having a high refractive index are dispersed. Even if the hydrothermal treatment temperature exceeds 250 ° C., the effect of further shortening the crystallization and particle growth time is small, and in some cases, the particle size distribution may be non-uniform or coarse particles may be generated.
The hydrothermal treatment time is not particularly limited and is usually 0.5 to 12 hours, although it varies depending on the treatment temperature.
工程（ｅ）で得られたジルコニアゾルは、そのまま用いることもできるが、必要に応じて、濃縮または希釈して用いることができる。
濃縮する方法として、従来公知の方法を採用することができ、例えば、ロータリーエバポレーター等で加熱濃縮してもよく、さらには減圧下で加熱濃縮してもよく、限外濾過膜法で濃縮することもできる。
このようにして得られたジルコニアゾルの電導度は２００μＳ／ｃｍ以下、さらには１００μＳ／ｃｍ以下であることが好ましい。ジルコニアゾルの電導度が２００μＳ／ｃｍを越えると、安定性が不充分となることがある。また、このときのジルコニアゾルのｐＨは概ね３〜５の範囲である。
Although the zirconia sol obtained in the step (e) can be used as it is, it can be concentrated or diluted as necessary.
As a method of concentration, a conventionally known method can be employed. For example, it may be concentrated by heating with a rotary evaporator or the like, or further concentrated under reduced pressure, or concentrated by an ultrafiltration membrane method. You can also.
The conductivity of the zirconia sol thus obtained is preferably 200 μS / cm or less, more preferably 100 μS / cm or less. When the conductivity of the zirconia sol exceeds 200 μS / cm, the stability may be insufficient. Further, the pH of the zirconia sol at this time is approximately in the range of 3 to 5.
本発明のジルコニアゾルの製造方法では、前記工程（ｅ）の後、工程（ｄ）および／または工程（ｅ）を繰り返し実施することができる。
繰り返し行う工程（ｄ）の洗浄方法と工程（ｅ）の熟成方法とは、前記したと同様に行うことができる。工程（ｄ）を繰り返し行うことによって安定性が向上し、工程（ｅ）を繰り返し行うことによって結晶性の向上、結晶子径の成長効果が得られる。
前記工程（ｄ）および／または（ｅ）工程を繰り返し実施した後のジルコニアゾルの電導度は１００μＳ／ｃｍ以下、ｐＨは概ね３〜４の範囲であることが好ましい。ジルコニアゾルの電導度およびｐＨがこの範囲にあるとジルコニアゾルはさらに安定性に優れている。
In the manufacturing method of the zirconia sol of this invention, a process (d) and / or a process (e) can be repeatedly implemented after the said process (e).
The washing method in the repeated step (d) and the aging method in the step (e) can be performed in the same manner as described above. By repeating the step (d), the stability is improved, and by repeating the step (e), the crystallinity is improved and the effect of growing the crystallite diameter is obtained.
It is preferable that the electric conductivity of the zirconia sol after repeating the step (d) and / or the step (e) is 100 μS / cm or less, and the pH is approximately in the range of 3-4. When the conductivity and pH of the zirconia sol are in this range, the zirconia sol is further excellent in stability.
さらに、本発明のジルコニアゾルの製造方法では、前記工程（ｅ）または前記繰り返し実施した工程（ｅ）の後、ジルコニアゾルを乾燥し、３００〜８００℃、より好ましくは５００〜７００℃の範囲で焼成し、微粉末を再び分散液に分散させてジルコニアゾルとすることができる。
乾燥方法としては従来公知の方法を採用することができ、例えば、ロータリーエバポレーターを用いて、あるいは加熱して濃縮し、通常１００℃〜２００℃で乾燥して分散媒を除去する。
乾燥したジルコニア微粉末の焼成温度が３００℃未満の場合は、前記工程（ｅ）、必要に応じて工程（ｅ）を繰り返した場合と結晶度があまり変わらない。焼成温度が８００℃を超えると、結晶度は高くなるが粒子径、結晶子径が大きくなり過ぎて用途が限定される。例えば、分散安定性、透明性等が低下し、被膜の強度あるいは透明性を必要とする被膜の形成には不向きである。
Furthermore, in the manufacturing method of the zirconia sol of this invention, after the said process (e) or the said repeatedly implemented process (e), a zirconia sol is dried, 300-800 degreeC, More preferably, it is the range of 500-700 degreeC. After baking, the fine powder can be dispersed again in the dispersion to form a zirconia sol.
As a drying method, a conventionally known method can be employed. For example, the solution is concentrated by using a rotary evaporator or by heating, and usually dried at 100 ° C. to 200 ° C. to remove the dispersion medium.
When the calcination temperature of the dried zirconia fine powder is less than 300 ° C., the crystallinity is not so different from the case where the step (e) and the step (e) are repeated as necessary. If the firing temperature exceeds 800 ° C., the crystallinity increases, but the particle diameter and crystallite diameter become too large, limiting the application. For example, the dispersion stability, transparency and the like are lowered, and it is not suitable for forming a film that requires the strength or transparency of the film.
焼成したジルコニア微粉末は分散媒に分散させ、必要に応じて分散機にて分散させて、ジルコニアゾルを得ることができる。
分散媒としては、水および／または有機溶媒を用いることができ、有機溶媒としてはアルコール類、グリコール類、エステル類、エーテル類、ケトン類等が挙げられる。
焼成したジルコニア微粉末の分散液の濃度は所望の濃度に調整することができるが、通常５〜３０重量％の範囲で用いられる。
また、必要に応じて分散機にて分散させる場合、ジルコニア微粉末の分散液の濃度は、分散機の種類によっても異なるが、５〜３０重量％、さらには１０〜２５重量％の範囲にあることが好ましい。分散液の濃度が５重量％未満の場合は、分散効率が悪くなり、場合によっては未分散の凝集物が残ることがある。一方、分散液の濃度が３０重量％を超えると、分散した粒子が再凝集を起こすことがあり、高分散のジルコニアゾルが得られない場合がある。
The calcined zirconia fine powder can be dispersed in a dispersion medium and dispersed with a disperser as necessary to obtain a zirconia sol.
As the dispersion medium, water and / or an organic solvent can be used. Examples of the organic solvent include alcohols, glycols, esters, ethers, and ketones.
Although the density | concentration of the dispersion liquid of the baked zirconia fine powder can be adjusted to a desired density | concentration, it is normally used in 5-30 weight%.
Moreover, when it disperse | distributes with a disperser as needed, although the density | concentration of the dispersion liquid of a zirconia fine powder changes also with the kind of disperser, it exists in the range of 5-30 weight%, Furthermore, 10-25 weight%. It is preferable. When the concentration of the dispersion is less than 5% by weight, the dispersion efficiency is deteriorated, and in some cases, undispersed aggregates may remain. On the other hand, when the concentration of the dispersion exceeds 30% by weight, the dispersed particles may reaggregate, and a highly dispersed zirconia sol may not be obtained.
このようにして得られたジルコニアゾルの平均粒子径は５〜１００ｎｍ、さらには１０〜５０ｎｍの範囲にあることが好ましい。平均粒子径が５ｎｍ未満の場合は、ジルコニアの結晶化が不充分なためか屈折率が低下する傾向にある。平均粒子径が１００ｎｍを越えるものは得たとしても、ジルコニアゾルが白濁したり透明性が低く、用途に制限がある。
なお、上記ジルコニアゾルの平均粒子径は、透過型電子顕微鏡写真（ＴＥＭ）を撮影し、５０個の粒子について粒子径を測定し、これを平均して求めることができる。
The average particle diameter of the zirconia sol thus obtained is preferably 5 to 100 nm, more preferably 10 to 50 nm. When the average particle diameter is less than 5 nm, the refractive index tends to decrease because of insufficient crystallization of zirconia. Even if an average particle diameter exceeding 100 nm is obtained, the zirconia sol becomes cloudy or has low transparency, and there is a limit to applications.
The average particle size of the zirconia sol can be determined by taking a transmission electron micrograph (TEM), measuring the particle size of 50 particles, and averaging the particle sizes.
ジルコニアゾルの分散質であるジルコニア粒子の結晶子径は５〜４０ｎｍ、さらには１０〜３０ｎｍの範囲にあることが好ましい。結晶子径が５ｎｍ未満の場合は、結晶化、屈折率共に不充分であり、また、分散安定性も不充分となることがある。結晶子径が４０ｎｍを超えるものは、得られるゾルの透明性が低下し、用途に制限がある。
なお、結晶子径は、Ｘ線回折により、メインピーク（ミラー指数ｈ＝−１、ｋ=１ 、ｌ=１ ）の半価幅（β）より、Ｓｃｈｅｒｒｅｒの式Ｄ＝λ／βｃｏｓθ（Ｄ：結晶子径（Å）、λ＝Ｘ線波長（Å）、θ＝反射角）より求めることができる。
The crystallite diameter of the zirconia particles that are the dispersoid of the zirconia sol is preferably in the range of 5 to 40 nm, more preferably 10 to 30 nm. When the crystallite diameter is less than 5 nm, crystallization and refractive index are insufficient, and dispersion stability may be insufficient. When the crystallite diameter exceeds 40 nm, the transparency of the obtained sol is lowered, and the use is limited.
The crystallite diameter is determined by X-ray diffraction from the half width (β) of the main peak (Miller index h = −1, k = 1, 1 = 1), Scherrer's formula D = λ / βcos θ (D: It can be determined from the crystallite diameter (Å), λ = X-ray wavelength (Å), and θ = reflection angle).
本発明で得られた上記水を分散媒とするジルコニアゾルは、必要に応じてアルコール、グリコール、エステル、エーテル、ケトン等の有機溶媒に置換してジルコニアオルガノゾルとすることもできる。このようなジルコニアオルガノゾルは、例えば、樹脂基材あるいは光学材料として、樹脂レンズ基材等のハードコート膜の屈折率調整剤、反射防止膜等に好適に用いることができる。
本発明係るジルコニアゾルの製造方法で得られたジルコニアゾルは、標準屈折率液法で測定した屈折率が１.７〜２.２の範囲にある。
The zirconia sol using the water as a dispersion medium obtained in the present invention may be substituted with an organic solvent such as alcohol, glycol, ester, ether, ketone or the like as necessary to obtain a zirconia organosol. Such a zirconia organosol can be suitably used, for example, as a resin base material or an optical material, for a refractive index adjuster of a hard coat film such as a resin lens base material, an antireflection film, or the like.
The zirconia sol obtained by the method for producing a zirconia sol according to the present invention has a refractive index measured by a standard refractive index liquid method in the range of 1.7 to 2.2.
つぎに、本発明に係るジルコニアゾルは、平均粒子径が５〜１００ｎｍの範囲にあり、結晶子径が５〜４０ｎｍの範囲にあるジルコニア粒子が分散したものである。ジルコニア粒子の平均粒子径および結晶子径が前記範囲にあれば、ジルコニア粒子の粒子径分布が均一で、分散安定性に優れ、結晶性が高く高屈折率である。
平均粒子径のより好ましい範囲は１０〜５０ｎｍであり、結晶子径のより好ましい範囲は１０〜３０ｎｍである。このようなジルコニアゾルは、前記した本発明に係るジルコニアゾルの製造方法により得られる。
Next, the zirconia sol according to the present invention is obtained by dispersing zirconia particles having an average particle diameter in the range of 5 to 100 nm and a crystallite diameter in the range of 5 to 40 nm. If the average particle diameter and crystallite diameter of the zirconia particles are within the above ranges, the particle size distribution of the zirconia particles is uniform, excellent in dispersion stability, high in crystallinity and high refractive index.
A more preferable range of the average particle diameter is 10 to 50 nm, and a more preferable range of the crystallite diameter is 10 to 30 nm. Such a zirconia sol can be obtained by the above-described method for producing a zirconia sol according to the present invention.
ジルコニアゾル(1)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解し、これにリンゴ酸２．７ｇ（Ｃm／Ｚm＝０.１）を添加し、ついで、濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１０.５、温度は１９℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は１０μＳ／ｃｍ、ｐＨは６であった。
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
Preparation of zirconia sol (1) 65.5 g of zirconium oxychloride octahydrate ( ZrOCl 2 .8H 2 O) was dissolved in 2432 g of pure water, and 2.7 g of malic acid (Cm / Zm = 0.1) was added thereto. Then, 313 g of a 10 wt% KOH aqueous solution was added to prepare a zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%). At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1 wt%) had an electric conductivity of 10 μS / cm and a pH of 6.
Subsequently, the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, then filled in an autoclave and aged at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は１６μＳ／ｃｍ、ｐＨは３．９であった。
ついで、上記熟成し、洗浄した分散液をＺrＯ2濃度１重量％に調整し、これに濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０．１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は４７μＳ／ｃｍ、ｐＨは３.４であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(1)を調製した。得られたジルコニアゾル(1)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(1)の平均粒子径、結晶子径、ｐＨおよび電導度を測定し、調製条件と共に結果を表１〜表３に示した。また、屈折率を以下の方法で測定し、結果を表３に示した。
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. The electric conductivity at this time was 16 μS / cm, and the pH was 3.9.
Next, the above ripened and washed dispersion was adjusted to a ZrO 2 concentration of 1% by weight, 134 g of malic acid aqueous solution having a concentration of 2% by weight (Cmc / Zmc = 0.10) was added thereto, and ultrasonic waves were irradiated for 1 hour. After the hydrogel was dispersed, the autoclave was filled and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 47 μS / cm, and the pH was 3.4.
Thereafter, it was concentrated to prepare a zirconia sol (1) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (1), coarse particles and fine particles were not observed. The average particle diameter, crystallite diameter, pH and conductivity of zirconia sol (1) were measured, and the results are shown in Tables 1 to 3 together with the preparation conditions. The refractive index was measured by the following method, and the results are shown in Table 3.
屈折率の測定
（１）ジルコニアゾルをエバポレーターに採り、分散媒を蒸発させる。
（２）１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折率液を２，３滴ガラス基板状に滴下し、これにジルコニア粉末を混合する。
（４）上記（３）の操作を種々の標準屈折率液で行い、混合液が透明になったときの標準屈折率液の屈折率をジルコニア粒子の屈折率とする。
Refractive index measurement (1) A zirconia sol is taken in an evaporator and the dispersion medium is evaporated.
(2) Dry at 120 ° C. to obtain a powder.
(3) A standard refractive index liquid having a known refractive index is dropped in the form of a few drops of glass substrate, and zirconia powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive index liquids, and the refractive index of the standard refractive index liquid when the mixed liquid becomes transparent is set as the refractive index of the zirconia particles.
（特徴：工程（ｅ）のモル比０．０５）
ジルコニアゾル(2)の調製
実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％のリンゴ酸水溶液６７ｇ（Ｃmc／Ｚmc＝０．０５）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は４００μＳ／ｃｍ、ｐＨは３．６０であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は３０μＳ／ｃｍ、ｐＨは４，２であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(2)を調製した。得られたジルコニアゾル(2)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(2)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: molar ratio of step (e) 0.05)
Preparation of zirconia sol (2) A dispersion of 1% by weight of ZrO 2 ripened and washed in the same manner as in Example 1 was prepared, and 67 g of malic acid aqueous solution having a concentration of 2% by weight (Cmc / Zmc = 0. 05) was added and ultrasonic waves were applied for 1 hour to disperse the hydrogel, and then the autoclave was filled and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 400 μS / cm and the pH was 3.60.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 30 μS / cm and the pH was 4,2.
Thereafter, it was concentrated to prepare a zirconia sol (2) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (2), coarse particles and fine particles were not observed. The average particle diameter, refractive index, crystallite diameter, pH and conductivity of zirconia sol (2) were measured, and the results are shown in Table 3.
（特徴：工程（ｅ）のモル比０．５０）
ジルコニアゾル(3)の調製
実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％のリンゴ酸水溶液６７０ｇ（Ｃmc／Ｚmc＝０．５）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は２２００μＳ／ｃｍ、ｐＨは２．１０であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は１８０μＳ／ｃｍ、ｐＨは２．９であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(3)を調製した。得られたジルコニアゾル(3)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(3)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: molar ratio of step (e) 0.50)
Preparation of zirconia sol (3) A matured and washed dispersion of ZrO 2 having a concentration of 1% by weight was prepared in the same manner as in Example 1, and 670 g of a malic acid aqueous solution having a concentration of 2% by weight (Cmc / Zmc = 0. 5) was added and ultrasonic waves were applied for 1 hour to disperse the hydrogel, and then the autoclave was filled and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 2200 μS / cm and the pH was 2.10.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 180 μS / cm and the pH was 2.9.
Thereafter, it was concentrated to prepare a zirconia sol (3) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (3), coarse particles and fine particles were not observed. The average particle diameter, refractive index, crystallite diameter, pH and conductivity of zirconia sol (3) were measured, and the results are shown in Table 3.
（特徴：工程（ａ）のモル比０．０５）
ジルコニアゾル(4)の調製
実施例１において、リンゴ酸１．４ｇ（Ｃm／Ｚm＝０．０５）を添加した以外は同様にしてジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１１、温度は１９℃であった。
ついで、限外濾過膜法での洗浄、陽イオン交換樹脂による脱イオン、陰イオン交換樹脂による脱イオンを行った。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は３.０μＳ／ｃｍ、ｐＨは７.０であった。
ついで、実施例１と同様にして熟成した。熟成により得られたジルコニアゾルは、電導度は３２０μＳ／ｃｍ、ｐＨは３．２であった。
ついで、陰イオン交換樹脂による脱イオンと限外濾過膜法による洗浄を行った。このときの電導度は４５μＳ／ｃｍ、ｐＨは４．３であった。
(Feature: molar ratio of step (a) 0.05)
Preparation of zirconia sol (4) In Example 1, a zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%) was prepared in the same manner except that 1.4 g of malic acid (Cm / Zm = 0.05) was added. Prepared. The pH of the dispersion at this time was 11, and the temperature was 19 ° C.
Subsequently, washing with an ultrafiltration membrane method, deionization with a cation exchange resin, and deionization with an anion exchange resin were performed. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1% by weight) had an electric conductivity of 3.0 μS / cm and a pH of 7.0.
Subsequently, aging was carried out in the same manner as in Example 1. The zirconia sol obtained by aging had an electric conductivity of 320 μS / cm and a pH of 3.2.
Subsequently, deionization with an anion exchange resin and washing by an ultrafiltration membrane method were performed. At this time, the conductivity was 45 μS / cm and the pH was 4.3.
ついで、実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０．１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６３０μＳ／ｃｍ、ｐＨは２．５８であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は４２μＳ／ｃｍ、ｐＨは３．６であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(4)を調製した。得られたジルコニアゾル(4)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(4)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, a ripened and washed ZrO 2 concentration 1 wt% dispersion was prepared in the same manner as in Example 1, and 134 g of a 2 wt% malic acid aqueous solution (Cmc / Zmc = 0.10) was added thereto. After the hydrogel was dispersed by irradiating with ultrasonic waves for 1 hour, it was filled in an autoclave and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 630 μS / cm and the pH was 2.58.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 42 μS / cm, and the pH was 3.6.
Thereafter, it was concentrated to prepare a zirconia sol (4) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (4), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (4) were measured, and the results are shown in Table 3.
（特徴：工程（ａ）のモル比０．５）
ジルコニアゾル(5)の調製
実施例１において、リンゴ酸１３．４ｇ（Ｃm／Ｚm＝０.５）を添加した以外は同様にしてジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは８．０、温度は２０℃であった。
ついで、限外濾過膜法での洗浄、陽イオン交換樹脂による脱イオン、陰イオン交換樹脂による脱イオンを行った。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は２０μＳ／ｃｍ、ｐＨは５．５であった。
ついで、実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０.１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６９０μＳ／ｃｍ、ｐＨは２．４１であった。
(Feature: molar ratio of step (a) 0.5)
Preparation of zirconia sol (5) In Example 1, except that 13.4 g of malic acid (Cm / Zm = 0.5) was added, a zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1% by weight) was prepared. Prepared. At this time, the pH of the dispersion was 8.0, and the temperature was 20 ° C.
Subsequently, washing with an ultrafiltration membrane method, deionization with a cation exchange resin, and deionization with an anion exchange resin were performed. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1% by weight) had an electric conductivity of 20 μS / cm and a pH of 5.5.
Next, a matured and washed dispersion of ZrO 2 concentration 1 wt% was prepared in the same manner as in Example 1, and 134 g of a 2 wt% malic acid aqueous solution (Cmc / Zmc = 0.10) was added thereto. After the hydrogel was dispersed by irradiating with ultrasonic waves for 1 hour, it was filled in an autoclave and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 690 μS / cm, and the pH was 2.41.
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は６０μＳ／ｃｍ、ｐＨは３．１であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(5)を調製した。得られたジルコニアゾル(5)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(5)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. The electric conductivity at this time was 60 μS / cm, and the pH was 3.1.
Thereafter, it was concentrated to prepare a zirconia sol (5) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (5), coarse particles and fine particles were not observed. The average particle diameter, refractive index, crystallite diameter, pH and conductivity of zirconia sol (5) were measured, and the results are shown in Table 3.
（特徴：工程（ａ）の調整剤はクエン酸）
ジルコニアゾル(6)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解し、これにクエン酸酸一水和物７.７ｇ（Ｃm／Ｚm＝０.１）を添加し、ついで、濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１０.５、温度は１９℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は１５μＳ／ｃｍ、ｐＨは５．８であった。
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は６６０μＳ／ｃｍ、ｐＨは２.４５であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は１９μＳ／ｃｍ、ｐＨは３．８であった。
(Characteristic: The adjusting agent in step (a) is citric acid)
Preparation of Zirconia Sol (6) 65.5 g of zirconium oxychloride octahydrate ( ZrOCl 2 .8H 2 O) was dissolved in 2432 g of pure water, and 7.7 g of citric acid monohydrate (Cm / Zm = 0) 0.1) was added, and then 313 g of a 10 wt% KOH aqueous solution was added to prepare a zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%). At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1 wt%) had an electric conductivity of 15 μS / cm and a pH of 5.8.
Subsequently, the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, then filled in an autoclave and aged at 200 ° C. for 2 hours. At this time, the conductivity was 660 μS / cm, and the pH was 2.45.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the electric conductivity was 19 μS / cm and the pH was 3.8.
ついで、実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％のクエン酸水溶液２１０ｇ（Ｃmc／Ｚmc＝０．１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は５０μＳ／ｃｍ、ｐＨは３.４であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(6)を調製した。得られたジルコニアゾル(6)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(6)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, an aged and washed dispersion of ZrO 2 having a concentration of 1% by weight was prepared in the same manner as in Example 1, and 210 g of an aqueous citric acid solution having a concentration of 2% by weight (Cmc / Zmc = 0.10) was added thereto. After the hydrogel was dispersed by irradiating with ultrasonic waves for 1 hour, it was filled in an autoclave and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the electric conductivity was 50 μS / cm and the pH was 3.4.
Thereafter, it was concentrated to prepare a zirconia sol (6) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (6), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (6) were measured, and the results are shown in Table 3.
（特徴：工程（ａ）の調整剤は酒石酸）
ジルコニアゾル(7)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解し、これに酒石酸３ｇ（Ｃm／Ｚm＝０.１）を添加し、ついで、濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１０.５、温度は１９℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は３.６μＳ／ｃｍ、ｐＨは７.０であった。
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は６５５μＳ／ｃｍ、ｐＨは２.５０であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は２０μＳ／ｃｍ、ｐＨは３.７であった。
(Characteristic: The regulator in step (a) is tartaric acid)
Preparation of zirconia sol (7) 65.5 g of zirconium oxychloride octahydrate ( ZrOCl 2 .8H 2 O) was dissolved in 2432 g of pure water, and 3 g of tartaric acid (Cm / Zm = 0.1) was added thereto. Then, 313 g of a 10 wt% KOH aqueous solution was added to prepare a zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%). At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The conductivity of the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1% by weight) thus obtained was 3.6 μS / cm, and the pH was 7.0.
Subsequently, the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, then filled in an autoclave and aged at 200 ° C. for 2 hours. At this time, the conductivity was 655 μS / cm and the pH was 2.50.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the electric conductivity was 20 μS / cm and the pH was 3.7.
ついで、実施例１と同様にして熟成し、洗浄したＺrＯ2濃度１重量％の分散液を調整し、これに濃度２重量％の酒石酸水溶液１５０ｇ（Ｃmc／Ｚmc＝０．１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は５４μＳ／ｃｍ、ｐＨは３．３であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(7)を調製した。得られたジルコニアゾル(7)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(7)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, an aged and washed dispersion of ZrO 2 having a concentration of 1% by weight was prepared in the same manner as in Example 1, and 150 g of an aqueous tartaric acid solution having a concentration of 2% by weight (Cmc / Zmc = 0.10) was added thereto. The hydrogel was dispersed by sonication for 1 hour, then filled in an autoclave, and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. The electric conductivity at this time was 54 μS / cm, and the pH was 3.3.
Thereafter, it was concentrated to prepare a zirconia sol (7) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (7), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (7) were measured, and the results are shown in Table 3.
（特徴：実施例１で工程（ｄ）、工程（ｅ）の反復）
ジルコニアゾル(8)の調製
実施例１と同様にしてジルコニアゾル(1)を調製した。ついで、ジルコニアゾル(1)をＺrＯ2濃度１重量％に希釈し、これに濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０.１０）を加え、オートクレーブに充填し、２００℃で２時間水熱処理した。このときの電導度は７００μＳ／ｃｍ、ｐＨは２．４２であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は５２μＳ／ｃｍ、ｐＨは３．６であった。その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(8)を調製した。得られたジルコニアゾル(8)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(8)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Repeating steps (d) and (e) in Example 1)
Preparation of zirconia sol (8) A zirconia sol (1) was prepared in the same manner as in Example 1. Next, zirconia sol (1) was diluted to a ZrO 2 concentration of 1% by weight, and 134 g of malic acid aqueous solution (Cmc / Zmc = 0.10) having a concentration of 2% by weight was added thereto. Hydrothermal treatment was performed for an hour. At this time, the electric conductivity was 700 μS / cm and the pH was 2.42.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the electric conductivity was 52 μS / cm and the pH was 3.6. Thereafter, it was concentrated to prepare a zirconia sol (8) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (8), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (8) were measured, and the results are shown in Table 3.
（特徴：実施例５で工程（ｄ）、工程（ｅ）の反復）
ジルコニアゾル(9)の調製
実施例５と同様にしてジルコニアゾル(5)を調製した。ついで、ジルコニアゾル(5)をＺrＯ2濃度１重量％に希釈し、これに濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０.１０）を加え、オートクレーブに充填し、２００℃で２時間水熱処理した。このときの電導度は７３０μＳ／ｃｍ、ｐＨは２．３５であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は６５μＳ／ｃｍ、ｐＨは３．０であった。その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(9)を調製した。得られたジルコニアゾル(9)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(9)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Repeating step (d) and step (e) in Example 5)
Preparation of zirconia sol (9) A zirconia sol (5) was prepared in the same manner as in Example 5. Next, the zirconia sol (5) was diluted to a ZrO 2 concentration of 1% by weight, 134 g of malic acid aqueous solution having a concentration of 2% by weight (Cmc / Zmc = 0.10) was added to the zirconia sol (5), and the autoclave was filled. Hydrothermal treatment was performed for an hour. At this time, the electric conductivity was 730 μS / cm and the pH was 2.35.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 65 μS / cm and the pH was 3.0. Thereafter, it was concentrated to prepare a zirconia sol (9) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (9), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (9) were measured, and the results are shown in Table 3.
（特徴：実施例１で焼成工程実施）
ジルコニアゾル(10)の調製
実施例１と同様にしてジルコニアゾル(1)を調製した。ついで、ジルコニアゾル(1)をロータリーエバポレーターを用いて濃縮し、１２０℃で２時間乾燥してジルコニア微粉末を得た。
ついで、ジルコニア微粉末を６５０℃で２時間焼成した。焼成したジルコニア微粉末を水に分散させ、ＺrＯ2濃度１５重量％の分散液とし、分散機（カンペ（株）製：BATCH SAND）にて分散させ、ついで、希釈してＺrＯ2濃度２．９重量％のジルコニアゾル(10)を調製した。得られたジルコニアゾル(10)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(10)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Implementation of firing process in Example 1)
Preparation of zirconia sol (10) A zirconia sol (1) was prepared in the same manner as in Example 1. Subsequently, the zirconia sol (1) was concentrated using a rotary evaporator and dried at 120 ° C. for 2 hours to obtain a fine zirconia powder.
Next, the zirconia fine powder was fired at 650 ° C. for 2 hours. The calcined zirconia fine powder is dispersed in water to form a dispersion having a ZrO 2 concentration of 15% by weight, dispersed in a disperser (manufactured by Campe Co., Ltd .: BATCH SAND), and then diluted to obtain a ZrO 2 concentration of 2.9. A weight percent zirconia sol (10) was prepared. In TEM observation of the obtained zirconia sol (10), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (10) were measured, and the results are shown in Table 3.
（特徴：実施例７で焼成工程実施）
ジルコニアゾル(11)の調製
実施例７と同様にしてジルコニアゾル(7)を調製した。ついで、ジルコニアゾル(7)をロータリーエバポレーターを用いて濃縮し、１２０℃で２時間乾燥してジルコニア微粉末を得た。
ついで、ジルコニア微粉末を６５０℃で２時間焼成した。焼成したジルコニア微粉末を水に分散させ、ＺrＯ2濃度１５重量％の分散液とし、分散機（カンペ（株）製：BATCH SAND）にて分散させ、ついで、希釈してＺrＯ2濃度２．９重量％のジルコニアゾル(11)を調製した。得られたジルコニアゾル(11)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(11)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Implementation of firing process in Example 7)
Preparation of zirconia sol (11) A zirconia sol (7) was prepared in the same manner as in Example 7. Subsequently, the zirconia sol (7) was concentrated using a rotary evaporator and dried at 120 ° C. for 2 hours to obtain a fine zirconia powder.
Next, the zirconia fine powder was fired at 650 ° C. for 2 hours. The calcined zirconia fine powder is dispersed in water to form a dispersion having a ZrO 2 concentration of 15% by weight, dispersed in a disperser (manufactured by Campe Co., Ltd .: BATCH SAND), and then diluted to obtain a ZrO 2 concentration of 2.9. A weight percent zirconia sol (11) was prepared. In TEM observation of the obtained zirconia sol (11), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (11) were measured, and the results are shown in Table 3.
（特徴：実施例８で焼成工程実施）
ジルコニアゾル(12)の調製
実施例８と同様にしてジルコニアゾル(8)を調製した。ついで、ジルコニアゾル(8)をロータリーエバポレーターを用いて濃縮し、１２０℃で２時間乾燥してジルコニア微粉末を得た。
ついで、ジルコニア微粉末を６５０℃で２時間焼成した。焼成したジルコニア微粉末を水に分散させ、ＺrＯ2濃度１５重量％の分散液とし、分散機（カンペ（株）製：BATCH SAND）にて分散させ、ついで、希釈してＺrＯ2濃度２．９重量％のジルコニアゾル(12)を調製した。得られたジルコニアゾル(12)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(12)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Implementation of firing process in Example 8)
Preparation of zirconia sol (12) A zirconia sol (8) was prepared in the same manner as in Example 8. Subsequently, the zirconia sol (8) was concentrated using a rotary evaporator and dried at 120 ° C. for 2 hours to obtain a fine zirconia powder.
Next, the zirconia fine powder was fired at 650 ° C. for 2 hours. The calcined zirconia fine powder is dispersed in water to form a dispersion having a ZrO 2 concentration of 15% by weight, dispersed in a disperser (manufactured by Campe Co., Ltd .: BATCH SAND), and then diluted to obtain a ZrO 2 concentration of 2.9. A weight percent zirconia sol (12) was prepared. In TEM observation of the obtained zirconia sol (12), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (12) were measured, and the results are shown in Table 3.
（特徴：実施例１で粒子成長調整剤無添加）
ジルコニアゾル(R1)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解した水溶液に濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１２.０、温度は２０℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は３.５μＳ／ｃｍ、ｐＨは７.３であった。
(Feature: No grain growth regulator added in Example 1)
Preparation of zirconia sol (R1)
Zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1) was added to an aqueous solution prepared by dissolving 65.5 g of zirconium oxychloride octahydrate (ZrOCl 2 .8H 2 O) in 2432 g of pure water. % By weight) was prepared. At this time, the pH of the dispersion was 12.0, and the temperature was 20 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1% by weight) had an electric conductivity of 3.5 μS / cm and a pH of 7.3.
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理した。水熱処理によりジルコニアゾルが得られたが、電導度は２００μＳ／ｃｍ、ｐＨは４．８であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は１μＳ／ｃｍ、ｐＨは６．８であった。その後、濃縮してジルコニアゾル(R1)を調製した。得られたジルコニアゾル(R1)のＴＥＭ観察では約４０ｎｍの一次粒子が凝集した平均粒子径が１１５ｎｍの二次粒子であった。
ジルコニアゾル(R1)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1% by weight) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, then filled in an autoclave, and hydrothermally treated at 200 ° C. for 2 hours. A zirconia sol was obtained by hydrothermal treatment, but the conductivity was 200 μS / cm and the pH was 4.8.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 1 μS / cm and the pH was 6.8. Thereafter, it was concentrated to prepare zirconia sol (R1). In the TEM observation of the obtained zirconia sol (R1), it was secondary particles having an average particle diameter of 115 nm in which primary particles of about 40 nm were aggregated.
The average particle diameter, refractive index, crystallite diameter, pH and conductivity of zirconia sol (R1) were measured, and the results are shown in Table 3.
（特徴：実施例１で熟成工程だけ粒子成長調整剤を添加）
ジルコニアゾル(R2)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解した水溶液に濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１２.０、温度は２０℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は３.５μＳ／ｃｍ、ｐＨは７.３であった。
(Characteristic: Addition of particle growth regulator only in the aging step in Example 1)
Preparation of zirconia sol (R2) Zirconium hydroxide hydrogel was prepared by adding 313 g of 10 wt% KOH aqueous solution to an aqueous solution in which 65.5 g of zirconium oxychloride octahydrate ( ZrOCl 2 .8H 2 O) was dissolved in 2432 g of pure water. A dispersion (ZrO 2 concentration 1% by weight) was prepared. At this time, the pH of the dispersion was 12.0, and the temperature was 20 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1% by weight) had an electric conductivity of 3.5 μS / cm and a pH of 7.3.
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に濃度２重量％のリンゴ酸水溶液１３４ｇ（Ｃmc／Ｚmc＝０.１０）を加え、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理した。水熱処理によりジルコニアゾルが得られたが、電導度は６５０μＳ／ｃｍ、ｐＨは２.６５であった。
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は５０μＳ／ｃｍ、ｐＨは３.４５であった。その後、濃縮してジルコニアゾル(R2)を調製した。得られたジルコニアゾル(R2)のＴＥＭ観察では約２５ｎｍの一次粒子が凝集した平均粒子径が１０５ｎｍの二次粒子であった。
ジルコニアゾル(R2)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, 134 g of malic acid aqueous solution (Cmc / Zmc = 0.10) having a concentration of 2% by weight was added to the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1% by weight), and ultrasonic waves were irradiated for 1 hour to After the dispersion treatment, the autoclave was filled and hydrothermally treated at 200 ° C. for 2 hours. A zirconia sol was obtained by hydrothermal treatment, but the conductivity was 650 μS / cm and the pH was 2.65.
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the electric conductivity was 50 μS / cm and the pH was 3.45. Thereafter, it was concentrated to prepare zirconia sol (R2). In the TEM observation of the obtained zirconia sol (R2), it was secondary particles having an average particle diameter of 105 nm in which primary particles of about 25 nm were aggregated.
The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (R2) were measured, and the results are shown in Table 3.
（特徴：特許文献３の実施例１を追試）
ジルコニアゾル(R3)の調製
炭酸ジルコニウムアンモニウム水溶液（ＺrＯ2濃度１３重量％）１３００ｇを調製し、これに、撹拌下グリコール酸１０４０ｇを徐々に添加した。ついで、徐々に昇温し、１００℃で１５時間維持し、ついで常温に冷却した。このときジルコニア微粒子分散液のｐＨは７であった。ついで、希釈してＺrＯ2濃度２．９重量％のジルコニアゾル(R3)を調製した。
得られたジルコニアゾル(R3)のＴＥＭ観察では、２〜８ｎｍ程度の微粒子が２〜４個連結し、かつ粗大な凝集体が観察された。
ジルコニアゾル(R3)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
(Feature: Reexamination of Example 1 of Patent Document 3)
Preparation of Zirconia Sol (R3) 1300 g of ammonium zirconium carbonate aqueous solution (ZrO 2 concentration 13 wt%) was prepared, and 1040 g of glycolic acid was gradually added thereto with stirring. Then, the temperature was gradually raised, maintained at 100 ° C. for 15 hours, and then cooled to room temperature. At this time, the pH of the zirconia fine particle dispersion was 7. Subsequently, it was diluted to prepare a zirconia sol (R3) having a ZrO 2 concentration of 2.9% by weight.
In TEM observation of the obtained zirconia sol (R3), 2 to 4 fine particles of about 2 to 8 nm were linked and coarse aggregates were observed.
The average particle diameter, refractive index, crystallite diameter, pH and conductivity of zirconia sol (R3) were measured, and the results are shown in Table 3.
（特徴：実施例１で工程（ａ）だけ粒子成長調整剤を添加）
ジルコニアゾル(R4)の調製
純水２４３２ｇにオキシ塩化ジルコニウム８水塩（ＺrＯＣｌ2・８Ｈ2Ｏ）６５.５ｇを溶解し、これにリンゴ酸２．７ｇ（Ｃm／Ｚm＝０.１）を添加し、ついで、濃度１０重量％のＫＯＨ水溶液３１３ｇを添加してジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１０.５、温度は１９℃であった。
ついで、限外濾過膜法で電導度が２８０μＳ／ｃｍになるまで洗浄した。つぎに、このジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして得られた洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）の電導度は１０μＳ／ｃｍ、ｐＨは６であった。
ついで、洗浄ジルコニウム水酸化物ヒドロゲル分散液（ＺrＯ2濃度１重量％）に、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
(Characteristic: Addition of particle growth regulator only in step (a) in Example 1)
Preparation of zirconia sol (R4)
Dissolve 65.5 g of zirconium oxychloride octahydrate (ZrOCl 2 .8H 2 O) in 2432 g of pure water, add 2.7 g of malic acid (Cm / Zm = 0.1), and then add a concentration of 10 wt. A zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1% by weight) was prepared by adding 313 g of an aqueous KOH solution. At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.
Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 95 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO 2 concentration: 1% by weight) for deionization. Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO 2 concentration 1 wt%) had an electric conductivity of 10 μS / cm and a pH of 6.
Subsequently, the washed zirconium hydroxide hydrogel dispersion (ZrO 2 concentration 1 wt%) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, then filled in an autoclave and aged at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.
ついで、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は４７μＳ／ｃｍ、ｐＨは３.４であった。
ついで、熟成し、洗浄した分散液をＺrＯ2濃度１重量％に調整し、超音波を１時間照射してヒドロゲルの分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。このとき、電導度は６４０μＳ／ｃｍ、ｐＨは２.５３であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１１０ｇを加えて脱イオンを行い、ついで純水３７５０ｇを供給しながら限外濾過膜法で洗浄した。このときの電導度は４７μＳ／ｃｍ、ｐＨは３.４であった。
その後、濃縮してＺrＯ2濃度２．９重量％のジルコニアゾル(R4)を調製した。得られたジルコニアゾル(R4)のＴＥＭ観察では粗大粒子および微細粒子が認められなかった。ジルコニアゾル(R4)の平均粒子径、屈折率、結晶子径、ｐＨおよび電導度を測定し、結果を表３に示した。
Next, 110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added for deionization, followed by washing with an ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 47 μS / cm, and the pH was 3.4.
Next, the aged and washed dispersion was adjusted to a ZrO 2 concentration of 1% by weight, subjected to ultrasonic treatment for 1 hour to disperse the hydrogel, filled in an autoclave, and hydrothermally treated at 200 ° C. for 2 hours. . At this time, the conductivity was 640 μS / cm and the pH was 2.53.
110 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion for deionization, followed by washing with ultrafiltration membrane method while supplying 3750 g of pure water. At this time, the conductivity was 47 μS / cm, and the pH was 3.4.
Thereafter, it was concentrated to prepare a zirconia sol (R4) having a ZrO 2 concentration of 2.9% by weight. In TEM observation of the obtained zirconia sol (R4), coarse particles and fine particles were not observed. The average particle size, refractive index, crystallite size, pH and conductivity of zirconia sol (R4) were measured, and the results are shown in Table 3.
Claims (13)
（ａ）粒子成長調整剤の存在下、ジルコニウム化合物水溶液にアルカリ水溶液を加えてジルコニウム水酸化物ゲルの分散液を調製する工程
（ｂ）前記ジルコニウム水酸化物ゲルを洗浄する工程
（ｃ）前記洗浄したジルコニウム水酸化物ゲルの分散液を熟成する工程
（ｄ）前記熟成したジルコニウム水酸化物ゲルを洗浄する工程
（ｅ）粒子成長調整剤の存在下、前記洗浄したジルコニウム水酸化物ゲルの分散液を水熱処理する工程 A method for producing a sol in which zirconia fine particles having an average particle diameter in the range of 5 to 100 nm are dispersed, comprising the following steps (a) to (e).
(A) A step of preparing a dispersion of a zirconium hydroxide gel by adding an alkaline aqueous solution to a zirconium compound aqueous solution in the presence of a particle growth regulator (b) a step of washing the zirconium hydroxide gel (c) the washing (D) a step of rinsing the aged zirconium hydroxide gel; (e) a step of washing the aged zirconium hydroxide gel; and (e) a dispersion of the washed zirconium hydroxide gel in the presence of a particle growth regulator. Hydrothermal treatment process
The zirconia acidic sol according to claim 11 or 12, wherein the sol has a pH of 3 to 5.
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| JP2020033196A (en) * | 2018-08-27 | 2020-03-05 | 堺化学工業株式会社 | Method for producing aqueous dispersion and organic solvent dispersion of zirconium oxide particles |
| WO2020045165A1 (en) * | 2018-08-27 | 2020-03-05 | 堺化学工業株式会社 | Method for producing aqueous dispersion and organic solvent dispersion of zirconium oxide particles |
| WO2023013289A1 (en) * | 2021-08-04 | 2023-02-09 | 三井金属鉱業株式会社 | Zirconic acid solution, method for producing same, zirconium oxide powder, and method for producing same |
| JP7345078B2 (en) | 2021-08-04 | 2023-09-14 | 三井金属鉱業株式会社 | Zirconium acid solution and its manufacturing method, zirconium oxide powder and its manufacturing method |
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