JP2015182929A - Method for producing zirconia sol - Google Patents
Method for producing zirconia sol Download PDFInfo
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- JP2015182929A JP2015182929A JP2014061920A JP2014061920A JP2015182929A JP 2015182929 A JP2015182929 A JP 2015182929A JP 2014061920 A JP2014061920 A JP 2014061920A JP 2014061920 A JP2014061920 A JP 2014061920A JP 2015182929 A JP2015182929 A JP 2015182929A
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- zirconia sol
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000011033 desalting Methods 0.000 claims abstract description 11
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- -1 amine compound Chemical class 0.000 claims description 21
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 abstract description 14
- 239000010408 film Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 238000000108 ultra-filtration Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 229960002303 citric acid monohydrate Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 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
- 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 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 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 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CPOUUWYFNYIYLQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;hydroxide Chemical compound [OH-].CC(C)[N+](C(C)C)(C(C)C)C(C)C CPOUUWYFNYIYLQ-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide 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
- 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
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Abstract
Description
本発明は、ジルコニアゾルの製造方法に関する。 The present invention relates to a method for producing a zirconia sol.
ジルコニアは光学材料、研磨剤、触媒、酸素イオン導電体等、様々な用途に使用されており、とりわけナノレベルで分散したジルコニアゾルは基材に塗布することで透明薄膜が得られるため、単独、または塗料樹脂や無機バインダーと組み合わせることで、高屈折率薄膜やハードコート材料として利用されている。 Zirconia is used for various applications such as optical materials, abrasives, catalysts, oxygen ion conductors, etc.In particular, since a zirconia sol dispersed at a nano level can be obtained by applying it to a substrate, Or, it is used as a high refractive index thin film or a hard coat material by combining with a paint resin or an inorganic binder.
特許文献１には、炭酸ジルコニルアンモニウム水溶液にオキシカルボン酸等のキレート化剤を添加し反応させた後、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いる。 Patent Document 1 discloses a method of producing a zirconia sol by adding a chelating agent such as oxycarboxylic acid to a zirconylammonium carbonate aqueous solution and reacting it, followed by heat hydrolysis at 60 to 300 ° C.
しかしながら、特許文献１記載の製造方法では、特許文献１の実施例１に記載されているように加熱加水分解時に激しく発泡するため、工業的製造において必ずしも適したものではなかった。 However, the production method described in Patent Document 1 is not necessarily suitable for industrial production because it foams vigorously at the time of heat hydrolysis as described in Example 1 of Patent Document 1.
本発明は、中性〜アルカリ性領域で安定性と透明性に優れ、基材への密着性が高く、さらに膜硬度の高い薄膜が得られるジルコニアゾルを簡便に製造する方法の開発を課題とするものである。 It is an object of the present invention to develop a method for easily producing a zirconia sol that is excellent in stability and transparency in a neutral to alkaline region, has high adhesion to a base material, and provides a thin film with high film hardness. Is.
本発明は、ヒドロキシカルボン酸、アンモニア及び／又は水溶性アミン化合物に加えて、炭酸水素イオン及び／又は炭酸イオンを用い、これらを巧みな順序で添加することによって、製造時における発泡を抑制することに成功し、上記課題を解決したものである。 The present invention uses hydrogen carbonate ions and / or carbonate ions in addition to hydroxycarboxylic acid, ammonia and / or water-soluble amine compounds and adds them in a skillful order to suppress foaming during production. Successfully solved the above problems.
即ち、本発明は下記の通りである。
［１］下記の工程（１）〜（３）を包含することを特徴とするジルコニアゾルの製造方法。
（１）水溶性ジルコニウム化合物とヒドロキシカルボン酸の混合水溶液と、アンモニア及び／又は水溶性アミン化合物とを混合し中和させて、ジルコニアゲルを生成させる第一工程。
（２）上記ジルコニアゲルを脱塩し、脱塩ジルコニアゲルを得る第二工程。
（３）上記脱塩ジルコニアゲルを、炭酸水素イオン及び／又は炭酸イオンの存在下で加熱する第三工程。
［２］前記ジルコニアゾル中のヒドロキシカルボン酸と、アンモニア及び／又は水溶性アミン化合物の各割合の範囲が、ヒドロキシカルボン酸／ZrO2（モル比）＝0.01〜0.5であり、
（アンモニア＋水溶性アミン化合物）／ZrO2（モル比）＝0.25〜3である上記［１］記載のジルコニアゾルの製造方法。
［３］前記第三工程における加熱前の炭酸水素イオン及び／又は炭酸イオンの存在割合の範囲が、（炭酸水素イオン＋炭酸イオン）／ZrO2（モル比）＝0.05〜3である上記［１］又は［２］記載のジルコニアゾルの製造方法。
［４］前記炭酸水素イオンが炭酸水素アンモニウムに由来するものであり、前記炭酸イオンが炭酸アンモニウムに由来するものである上記［１］〜［３］のいずれか１項記載のジルコニアゾルの製造方法。
［５］前記第三工程の加熱が40〜100℃の範囲でおこなわれる上記［１］〜［４］のいずれか１項記載のジルコニアゾルの製造方法。
［６］前記ジルコニアゾルの結晶形が非晶質である上記［１］〜［５］のいずれか１項記載のジルコニアゾルの製造方法。
［７］前記ジルコニアゾルのpHが6〜13の範囲である上記［１］〜［６］のいずれか１項記載のジルコニアゾルの製造方法。
［８］上記［１］〜［７］のいずれか１項記載の製造方法によって製造されたジルコニアゾル。
That is, the present invention is as follows.
[1] A method for producing a zirconia sol, comprising the following steps (1) to (3):
(1) A first step in which a mixed aqueous solution of a water-soluble zirconium compound and a hydroxycarboxylic acid and ammonia and / or a water-soluble amine compound are mixed and neutralized to produce a zirconia gel.
(2) A second step of desalting the zirconia gel to obtain a desalted zirconia gel.
(3) A third step of heating the desalted zirconia gel in the presence of hydrogen carbonate ions and / or carbonate ions.
[2] The range of each ratio of hydroxycarboxylic acid and ammonia and / or water-soluble amine compound in the zirconia sol is hydroxycarboxylic acid / ZrO 2 (molar ratio) = 0.01 to 0.5,
(Ammonia + water-soluble amine compound) / ZrO 2 (molar ratio) = 0.25-3, The method for producing a zirconia sol according to [1] above.
[3] The range of the hydrogen carbonate ion and / or carbonate ion existing ratio before heating in the third step is (hydrogen carbonate ion + carbonate ion) / ZrO 2 (molar ratio) = 0.05 to 3 above [1] ] Or the manufacturing method of the zirconia sol of [2].
[4] The method for producing a zirconia sol according to any one of [1] to [3], wherein the hydrogen carbonate ions are derived from ammonium hydrogen carbonate, and the carbonate ions are derived from ammonium carbonate. .
[5] The method for producing a zirconia sol according to any one of [1] to [4], wherein the heating in the third step is performed in a range of 40 to 100 ° C.
[6] The method for producing a zirconia sol according to any one of the above [1] to [5], wherein the crystal form of the zirconia sol is amorphous.
[7] The method for producing a zirconia sol according to any one of the above [1] to [6], wherein the pH of the zirconia sol is in the range of 6 to 13.
[8] A zirconia sol produced by the production method according to any one of [1] to [7].
本発明のジルコニアゾルは、中性からアルカリ性領域において安定性に優れ、透明性の高いものである。また、基材との密着性に優れているために塗膜形成が容易であり、さらに得られる薄膜の膜硬度が高いため、無機バインダーやコーティング剤、あるいは光学材料等に好適に用いることができる。
The zirconia sol of the present invention has excellent stability and high transparency in a neutral to alkaline region. In addition, it is easy to form a coating film because of its excellent adhesion to the substrate, and since the film thickness of the resulting thin film is high, it can be suitably used for inorganic binders, coating agents, optical materials, etc. .
以下、本発明の実施形態の一例であるジルコニアゾルの製造方法について詳細に説明する。 Hereinafter, the manufacturing method of the zirconia sol which is an example of embodiment of this invention is demonstrated in detail.
本実施形態に係るジルコニアゾル（以下、「本ゾル」という。）の製造方法は、下記の工程（１）〜（３）を包含することを特徴とするものである。
（１）水溶性ジルコニウム化合物とヒドロキシカルボン酸の混合水溶液と、アンモニア及び／又は水溶性アミン化合物とを混合し中和させて、ジルコニアゲルを生成させる第一工程。
（２）上記ジルコニアゲルを脱塩し、脱塩ジルコニアゲルを得る第二工程。
（３）上記脱塩ジルコニアゲルを、炭酸水素イオン及び／又は炭酸イオンの存在下で加熱する第三工程。
The manufacturing method of the zirconia sol (henceforth "this sol") concerning this embodiment includes the following process (1)-(3), It is characterized by the above-mentioned.
(1) A first step in which a mixed aqueous solution of a water-soluble zirconium compound and a hydroxycarboxylic acid and ammonia and / or a water-soluble amine compound are mixed and neutralized to produce a zirconia gel.
(2) A second step of desalting the zirconia gel to obtain a desalted zirconia gel.
(3) A third step of heating the desalted zirconia gel in the presence of hydrogen carbonate ions and / or carbonate ions.
水溶性ジルコニウム化合物としては、オキシ塩化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、塩化ジルコニウム等が挙げられるがこれらに限定されるものではない。 Examples of the water-soluble zirconium compound include, but are not limited to, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium chloride and the like.
ヒドロキシカルボン酸としては、クエン酸、リンゴ酸、酒石酸、乳酸、グリセリン酸、グリコール酸などが挙げられ、このうち１種類だけでもあるいは２種類以上を用いてもよい。上記の中でも特にクエン酸が本ゾルを安定化させる効果が高いために好ましい。 Examples of the hydroxycarboxylic acid include citric acid, malic acid, tartaric acid, lactic acid, glyceric acid, and glycolic acid. Among these, only one kind or two or more kinds may be used. Among these, citric acid is particularly preferable because of its high effect of stabilizing the sol.
先ず、水溶性ジルコニウム化合物とヒドロキシカルボン酸の混合水溶液を調製する。調製方法に特に制限は無く、両化合物が溶解するように濃度、撹拌等の諸条件を適宜設定すればよい。 First, a mixed aqueous solution of a water-soluble zirconium compound and a hydroxycarboxylic acid is prepared. The preparation method is not particularly limited, and various conditions such as concentration and stirring may be set as appropriate so that both compounds are dissolved.
水溶性アミン化合物としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン、ジエチルアミン、トリエチルアミン、プロピルアミン、イソプロピルアミン、ブチルアミン、イソブチルアミン、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトライソプロピルアンモニウム、水酸化テトラブチルアンモニウム、コリン等を例示することができる。 Water-soluble amine compounds include monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide And tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, choline and the like.
アンモニアと水溶性アミン化合物のうち、本ゾルの機能として低温での高密着性を付与したい場合には、乾燥により容易に揮発するアンモニアを選択することが好ましい。 Among ammonia and a water-soluble amine compound, it is preferable to select ammonia that volatilizes easily by drying when it is desired to provide high adhesion at a low temperature as a function of the sol.
第一工程では、水溶性ジルコニウム化合物とヒドロキシカルボン酸の混合水溶液と、アンモニア及び／又は水溶性アミン化合物とを混合し中和させて、ジルコニアゲルを生成させる。混合し中和させる方法に特に制限は無く、撹拌強度、撹拌時間等の諸条件を適宜設定すればよい。また、混合時の温度に関しては、液状態を保つことができれば特段制限はない。 In the first step, a mixed aqueous solution of a water-soluble zirconium compound and a hydroxycarboxylic acid and ammonia and / or a water-soluble amine compound are mixed and neutralized to produce a zirconia gel. There is no restriction | limiting in particular in the method to mix and neutralize, What is necessary is just to set various conditions, such as stirring intensity | strength and stirring time suitably. Further, the temperature at the time of mixing is not particularly limited as long as the liquid state can be maintained.
水溶性ジルコニウム化合物、ヒドロキシカルボン酸、並びに、アンモニア及び／又は水溶性アミン化合物の量比については、上記混合による中和反応によりジルコニアゲルが生成するように適宜設定すればよい。 What is necessary is just to set suitably about the quantity ratio of a water-soluble zirconium compound, hydroxycarboxylic acid, and ammonia and / or a water-soluble amine compound so that a zirconia gel may be produced | generated by the neutralization reaction by the said mixing.
ここで、水溶性ジルコニウム化合物とヒドロキシカルボン酸との量比についての一例を示すと、本ゾル中においてヒドロキシカルボン酸／ZrO2（モル比）＝0.01〜0.5の範囲となるように設定することが好ましい。本ゾル中において、上記モル比が0.01を下回っていると十分にゾル化されていない場合があり、また、0.5を上回るほどに含有されているとジルコニウム成分の一部が第二工程の脱塩時にろ液に排出されて収率が低下している場合がある。 Here, as an example of the quantitative ratio between the water-soluble zirconium compound and the hydroxycarboxylic acid, it is possible to set the hydroxycarboxylic acid / ZrO 2 (molar ratio) = 0.01 to 0.5 in the sol. preferable. In this sol, if the molar ratio is less than 0.01, it may not be sufficiently solated, and if it is contained in excess of 0.5, part of the zirconium component is desalted in the second step. Sometimes it is discharged into the filtrate and the yield is reduced.
次に、水溶性ジルコニウム化合物とアンモニア及び／又は水溶性アミン化合物との量比についての一例を示すと、本ゾル中において（アンモニア＋水溶性アミン化合物）／ZrO2（モル比）＝0.25〜3の範囲となるように設定することが好ましい。本ゾル中において、上記モル比が0.25を下回っていると本ゾルの粘度が高くなる傾向にあり、また、3を上回っていると本ゾルが不安定化する傾向にある。 Next, an example of the quantitative ratio of the water-soluble zirconium compound to ammonia and / or the water-soluble amine compound is shown as (ammonia + water-soluble amine compound) / ZrO 2 (molar ratio) = 0.25 to 3 in this sol. It is preferable to set so as to be in the range. In the sol, when the molar ratio is less than 0.25, the viscosity of the sol tends to be high, and when it exceeds 3, the sol tends to be unstable.
また、ジルコニアゲルの濃度について云えば、ZrO2として0.1〜10質量％の範囲が好適である。上記濃度が0.1質量％を下回ると濃度が低いために生産効率が低下し、また、10質量％を上回ると反応時の撹拌が困難になる場合がある。 In terms of the concentration of zirconia gel, ZrO 2 is preferably in the range of 0.1 to 10% by mass. If the concentration is less than 0.1% by mass, the production efficiency is lowered because the concentration is low, and if it exceeds 10% by mass, stirring during the reaction may be difficult.
次に、第二工程では、第一工程で得られたジルコニアゲルを脱塩する。
脱塩は、副生塩や余分なイオン性成分が除去できればその方法に特に制限はなく、遠心分離、ヌッチェろ過等により固液分離した後に純水でリパルプ洗浄する方法、水を添加しながら限外ろ過膜、ロータリーフィルター等で洗浄する方法、イオン交換樹脂で脱塩する方法等を例示できる。この中でも特に限外ろ過洗浄が好ましい。
Next, in the second step, the zirconia gel obtained in the first step is desalted.
Desalting is not particularly limited as long as by-product salts and excess ionic components can be removed. The method includes solid-liquid separation by centrifugation, Nutsche filtration, etc., and repulp washing with pure water. Examples thereof include a method of washing with an outer filtration membrane, a rotary filter and the like, a method of desalting with an ion exchange resin, and the like. Of these, ultrafiltration washing is particularly preferred.
脱塩が不十分であると、第三工程における加熱処理でゾルが得られない恐れがあり、また、ゾルが得られたとしても粗大な粒子になる恐れがある。脱塩の目安としては、限外ろ過洗浄の場合を例に挙げると、ろ液ECが1mS/cm未満になるまで洗浄することが好ましい。脱塩後の脱塩ジルコニアゲルの好適な例は、酸化ジルコニウム（ZrO2）に対して、ヒドロキシカルボン酸をモル比で0.01〜0.5の範囲で含有し、アンモニア及び／又は水溶性アミン化合物をモル比で0.25〜3の範囲で含有し、pHがおおよそ8〜10の範囲のものである。 If the desalting is insufficient, the sol may not be obtained by the heat treatment in the third step, and even if the sol is obtained, coarse particles may be obtained. As an example of desalting, taking the case of ultrafiltration washing as an example, washing is preferably performed until the filtrate EC becomes less than 1 mS / cm. A suitable example of the desalted zirconia gel after desalting is that the zirconium oxide (ZrO 2 ) contains hydroxycarboxylic acid in a molar ratio in the range of 0.01 to 0.5, and contains ammonia and / or a water-soluble amine compound in a molar ratio. The ratio is in the range of 0.25 to 3, and the pH is in the range of about 8 to 10.
次いで、第三工程では、第二工程で得られた脱塩ジルコニアゲルを、炭酸水素イオン及び／又は炭酸イオンの存在下で加熱する。 Next, in the third step, the desalted zirconia gel obtained in the second step is heated in the presence of bicarbonate ions and / or carbonate ions.
炭酸水素イオン及び／又は炭酸イオンは、加熱時において、ジルコニアゲルを解膠する目的で存在させるものである。炭酸水素イオン及び／又は炭酸イオンを脱塩ジルコニアゲル中に存在させる方法としては、脱塩ジルコニアゲルに炭酸ガスを吹き込む方法やドライアイスを添加する方法の他に、水中で炭酸水素イオンを生成する化合物及び／又は炭酸イオンを生成する化合物を脱塩ジルコニアゲルに添加してもよい。当該化合物は、脱塩ジルコニアゲルに直接添加しても、また、当該化合物の水溶液を調製してから脱塩ジルコニアゲルに添加してもよい。当該化合物としては、本ゾルの分散状態を悪化させないものであれば特に制限は無く、例えば、炭酸水素ナトリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸カリウム、炭酸水素アンモニウム、炭酸アンモニウム等を挙げることができ、これらのうち炭酸水素アンモニウム、炭酸アンモニウムが好ましい。 Hydrogen carbonate ions and / or carbonate ions are present for the purpose of peptizing the zirconia gel during heating. As a method for causing hydrogen carbonate ions and / or carbonate ions to exist in the desalted zirconia gel, in addition to a method of blowing carbon dioxide into the desalted zirconia gel and a method of adding dry ice, hydrogen carbonate ions are generated in water. A compound and / or a compound that generates carbonate ions may be added to the desalted zirconia gel. The compound may be added directly to the desalted zirconia gel or may be added to the desalted zirconia gel after preparing an aqueous solution of the compound. The compound is not particularly limited as long as it does not deteriorate the dispersion state of the sol, and examples thereof include sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, ammonium hydrogen carbonate, ammonium carbonate and the like. Of these, ammonium hydrogen carbonate and ammonium carbonate are preferred.
炭酸水素イオン及び／又は炭酸イオンは、加熱前の脱塩ジルコニアゲル中において、（炭酸水素イオン＋炭酸イオン）／ZrO2（モル比）＝0.05〜3の範囲となるように含有させることが好ましい。上記モル比が0.05を下回ると沈殿物や濁りを生じる恐れがあり、また、3を上回って添加しても添加量に見合う効果が得られないため経済的でない。上記範囲は、0.1〜3の範囲がより好ましい。 Hydrogen carbonate ions and / or carbonate ions are preferably contained in the desalted zirconia gel before heating so as to be in the range of (hydrogen carbonate ions + carbonate ions) / ZrO 2 (molar ratio) = 0.05-3. . If the molar ratio is less than 0.05, a precipitate or turbidity may be generated, and even if it is added in excess of 3, an effect commensurate with the amount added cannot be obtained, which is not economical. As for the said range, the range of 0.1-3 is more preferable.
加熱の条件については特に限定されないが、本ゾルとして、基材への密着性が高く、膜硬度の高い薄膜が得られるものを製造するためには、40〜100℃の範囲で加熱することが好ましい。加熱温度が上記範囲内であれば、本ゾルに係る製造事例のほとんどの場合において、本ゾルを乾燥させた乾燥物の粉末Ｘ線回折分析で特定の回折ピークが検出されないため、結晶形は非晶質と解析される。また、加熱温度が上記範囲内の場合には、粘度上昇や沈殿の発生等の問題が生じにくい本ゾルを得ることができる。 The heating conditions are not particularly limited, but in order to produce a sol having a high adhesion to the base material and a thin film with high film hardness, heating in the range of 40 to 100 ° C. is required. preferable. If the heating temperature is within the above range, in most of the production examples related to the present sol, a specific diffraction peak is not detected by powder X-ray diffraction analysis of the dried product obtained by drying the present sol. Analyzed as crystalline. In addition, when the heating temperature is within the above range, the present sol can be obtained in which problems such as increase in viscosity and occurrence of precipitation are unlikely to occur.
本ゾルの結晶形が非晶質である場合は、とりわけ、基材への密着性が高く、また、膜硬度の高い薄膜が得られる。この理由は定かではないが、結晶質である場合に比べて非晶質である場合はゾルの表面に水酸基が多く存在し、これが基材への密着性を高め、また、薄膜として塗布したときには、乾燥時の水酸基の脱水縮合反応が硬化作用として働くために膜硬度の高い薄膜が得られると推察される。 When the crystalline form of the sol is amorphous, a thin film having high adhesion to the substrate and high film hardness can be obtained. The reason for this is not clear, but when it is amorphous as compared to crystalline, there are many hydroxyl groups on the surface of the sol, which improves adhesion to the substrate, and when applied as a thin film It is presumed that a thin film with high film hardness can be obtained because the dehydration condensation reaction of hydroxyl groups during drying works as a curing action.
尚、加熱時間については、加熱温度も考慮して、目的とする本ゾルの特性に応じて適宜設定すればよい。加熱条件の一例は、60〜90℃で1〜5時間である。一方、加熱温度が100℃を上回ると、結晶化が進行し易くなるため、基材への密着性や膜硬度が低下する傾向となる。 The heating time may be appropriately set according to the intended characteristics of the present sol in consideration of the heating temperature. An example of heating conditions is 60 to 90 ° C. for 1 to 5 hours. On the other hand, when the heating temperature exceeds 100 ° C., crystallization is likely to proceed, so that the adhesion to the substrate and the film hardness tend to decrease.
また、本ゾルのpHについては、pHが6〜13の範囲となるように原料を選択し、その配合量を設定することが好ましい態様の１つである。pHが上記範囲内であれば、沈殿が発生しにくいため、長期安定性を確保することができる。 Moreover, about the pH of this sol, it is one of the preferable aspects that a raw material is selected so that pH may become the range of 6-13, and the compounding quantity is set. If the pH is within the above range, precipitation is unlikely to occur, and long-term stability can be ensured.
第三工程後に、必要に応じて、さらに脱塩処理してもよい。脱塩処理方法としては、上述の第二工程で例記した方法から選択することが好ましい。 After the third step, a desalting treatment may be further performed as necessary. The desalting method is preferably selected from the methods exemplified in the second step.
また、本ゾルは、通常ZrO2として2〜20質量％の範囲で製造することが好ましい。2質量％未満では塗布液として利用するのに十分な濃度とはいい難く、製造上、輸送上も経済的でない。一方、20質量％を超えると保存安定性が低下する場合がある。 The present sols is preferably manufactured in a range of 2 to 20 wt% as a normal ZrO 2. If it is less than 2% by mass, it is difficult to say that the concentration is sufficient for use as a coating solution, and it is not economical in terms of production and transportation. On the other hand, if it exceeds 20% by mass, the storage stability may decrease.
以上の製造方法により、本ゾルを得ることができる。
本ゾルの結晶形が非晶質であり、本ゾル中のヒドロキシカルボン酸／ZrO2（モル比）が0.05〜0.35の範囲内であり、且つ、（アンモニア＋水溶性アミン化合物）／ZrO2（モル比）が0.25〜3の範囲内である場合に、とりわけ、中性〜アルカリ性領域で安定性と透明性に優れ、また、基材への密着性が高く、さらに塗膜にしたときに膜硬度の高い薄膜を得ることが可能となる。また、当該場合の本ゾルの物性値の好適な一例としては、本ゾルのZrO2濃度を5％に調整したときに、透過率が85％以上、且つ、Hazeが10％以下であり、さらに、より好適な物性値を示すときは、透過率が90％以上、且つ、Hazeが5％以下である。
The present sol can be obtained by the above production method.
The crystalline form of the sol is amorphous, the hydroxycarboxylic acid / ZrO 2 (molar ratio) in the sol is in the range of 0.05 to 0.35, and (ammonia + water-soluble amine compound) / ZrO 2 ( When the molar ratio is in the range of 0.25 to 3, it is excellent in stability and transparency, particularly in the neutral to alkaline region, and has high adhesion to the substrate. A thin film having high hardness can be obtained. In addition, as a suitable example of the physical property value of the present sol in this case, when the ZrO 2 concentration of the present sol is adjusted to 5%, the transmittance is 85% or more and Haze is 10% or less. When a more suitable physical property value is exhibited, the transmittance is 90% or more and Haze is 5% or less.
本ゾルを金属、セラミックス、ガラス、プラスチック等の各種基材上に塗布し乾燥させることによって膜硬度の高い薄膜を得ることができる。塗布の方法としては、刷毛塗り、スプレー塗布、スピンコート、ディップコート、ロールコート、グラビアコート、バーコートなど各種の公知の塗布方法が適用できる。また、乾燥方法は公知の方法を用いればよく、乾燥温度としては、例えば、室温以上で乾燥させればよい。膜硬度としては、例えば、鉛筆による引っかき硬度を求めるJIS K5600-5-4に従って測定したときに、100℃乾燥でHB以上を示すことが好ましく、また、300℃以上での乾燥では2H以上を示すことが好ましく、より好ましくは6H以上である。 A thin film with high film hardness can be obtained by applying this sol on various substrates such as metal, ceramics, glass, plastic and drying. As a coating method, various known coating methods such as brush coating, spray coating, spin coating, dip coating, roll coating, gravure coating, and bar coating can be applied. Moreover, what is necessary is just to use a well-known method as a drying method, and should just dry at room temperature or more as drying temperature, for example. As the film hardness, for example, when measured in accordance with JIS K5600-5-4 to determine the scratch hardness with a pencil, it is preferably HB or higher when dried at 100 ° C., and 2H or higher when dried at 300 ° C. or higher. More preferably, it is 6H or more.
以下に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらに制限されるものではない。尚、実施例において％は、特に断らない限り全て質量％を示す。 EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In Examples, “%” means “% by mass” unless otherwise specified.
〔実施例１〕
純水3621gとオキシ塩化ジルコニウム（ZrO2濃度：21.1％）379.1gを混合し、これにクエン酸一水和物40.9gを添加して混合液を作製した。この混合液に、20％アンモニア水220.7gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液の電気伝導度（EC）が110μS/cm以下になるまで洗浄し、脱塩ジルコニアゲル（ZrO2濃度：6.6％、EC：4.5mS/cm、pH8.1）を得た。
次に、脱塩ジルコニアゲル500gに炭酸水素アンモニウム5.3g（炭酸水素イオン／ZrO2のモル比＝0.25）を添加し、これを90℃で1時間加熱することによって無色透明なジルコニアゾルを得た。
[Example 1]
3621 g of pure water and 379.1 g of zirconium oxychloride (ZrO 2 concentration: 21.1%) were mixed, and 40.9 g of citric acid monohydrate was added thereto to prepare a mixed solution. To this mixed solution, 220.7 g of 20% aqueous ammonia was added with stirring to produce a zirconia gel. Next, the filtrate was washed until the electrical conductivity (EC) of the filtrate became 110 μS / cm or less using an ultrafiltration device, and desalted zirconia gel (ZrO 2 concentration: 6.6%, EC: 4.5 mS / cm, pH 8.1) )
Next, 5.3 g of ammonium hydrogen carbonate (hydrogen carbonate ion / ZrO 2 molar ratio = 0.25) was added to 500 g of desalted zirconia gel, and this was heated at 90 ° C. for 1 hour to obtain a colorless and transparent zirconia sol. .
〔実施例２〕
純水3620gとオキシ塩化ジルコニウム（ZrO2濃度：21.1％）600gを混合し、これにクエン酸一水和物54gを添加して混合液を作製した。この混合液に、19％アンモニア水367gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが100μS/cm以下になるまで洗浄し、脱塩ジルコニアゲル（ZrO2濃度：6.3％、EC：1.3mS/cm、pH8.4）を得た。
次に、脱塩ジルコニアゲル800gに炭酸水素アンモニウム26g（炭酸水素イオン／ZrO2のモル比＝0.80）を添加し、これを70℃で1時間加熱した後、限外ろ過装置を用いてろ液ECが300μS/cmになるまでろ過・濃縮を行うことによって、無色透明なジルコニアゾルを得た。
[Example 2]
3620 g of pure water and 600 g of zirconium oxychloride (ZrO 2 concentration: 21.1%) were mixed, and 54 g of citric acid monohydrate was added thereto to prepare a mixed solution. To this mixture, 367 g of 19% aqueous ammonia was added with stirring to produce a zirconia gel. Subsequently, the filtrate EC was washed until the filtrate EC became 100 μS / cm or less using an ultrafiltration device to obtain a desalted zirconia gel (ZrO 2 concentration: 6.3%, EC: 1.3 mS / cm, pH 8.4).
Next, 26 g of ammonium hydrogen carbonate (hydrogen carbonate ion / ZrO 2 molar ratio = 0.80) was added to 800 g of desalted zirconia gel, and this was heated at 70 ° C. for 1 hour, and then filtrate EC using an ultrafiltration device. By filtering and concentrating to a concentration of 300 μS / cm, a colorless and transparent zirconia sol was obtained.
〔実施例３〕
純水3020gとオキシ塩化ジルコニウム（ZrO2濃度：21.1％）500gを混合し、これにクエン酸一水和物36gを添加して混合液を作製した。この混合液に、22％アンモニア水268gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが100μS/cm以下になるまで洗浄し、脱塩ジルコニアゲル（ZrO2濃度：5.5％、EC：0.6mS/cm、pH8.2）を得た。
次に、脱塩ジルコニアゲル760gに炭酸水素アンモニウム63g（炭酸水素イオン／ZrO2のモル比＝2.3）を添加し、これを70℃で2時間加熱することによって、無色透明なジルコニアゾルを得た。
Example 3
3020 g of pure water and 500 g of zirconium oxychloride (ZrO 2 concentration: 21.1%) were mixed, and 36 g of citric acid monohydrate was added thereto to prepare a mixed solution. To this mixture, 268 g of 22% aqueous ammonia was added with stirring to produce a zirconia gel. Subsequently, the filtrate EC was washed until the filtrate EC became 100 μS / cm or less using an ultrafiltration device to obtain a desalted zirconia gel (ZrO 2 concentration: 5.5%, EC: 0.6 mS / cm, pH 8.2).
Next, 63 g of ammonium hydrogen carbonate (molar ratio of hydrogen carbonate ion / ZrO 2 = 2.3) was added to 760 g of desalted zirconia gel, and this was heated at 70 ° C. for 2 hours to obtain a colorless and transparent zirconia sol. .
〔実施例４〕
純水1150gとオキシ塩化ジルコニウム（ZrO2濃度：20.2％）200gを混合し、これにリンゴ酸22gを添加して混合液を作製した。この混合液に、20％アンモニア水110gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが100μS/cm以下になるまで洗浄し、脱塩ジルコニアゲル（ZrO2濃度：3.8％、EC：2.4mS/cm、pH7.2）を得た。
次に、脱塩ジルコニアゲル500gに炭酸アンモニウム12g（炭酸イオン／ZrO2のモル比＝0.8）を添加し、これを90℃で1時間加熱することによって無色透明なジルコニアゾルを得た。
Example 4
1150 g of pure water and 200 g of zirconium oxychloride (ZrO 2 concentration: 20.2%) were mixed, and 22 g of malic acid was added thereto to prepare a mixed solution. To this mixed solution, 110 g of 20% aqueous ammonia was added with stirring to produce a zirconia gel. Subsequently, the filtrate EC was washed until the filtrate EC became 100 μS / cm or less using an ultrafiltration device to obtain a desalted zirconia gel (ZrO 2 concentration: 3.8%, EC: 2.4 mS / cm, pH 7.2).
Next, 12 g of ammonium carbonate (carbonate ion / ZrO 2 molar ratio = 0.8) was added to 500 g of desalted zirconia gel, and this was heated at 90 ° C. for 1 hour to obtain a colorless and transparent zirconia sol.
〔実施例５〕
純水860gとオキシ塩化ジルコニウム（ZrO2濃度：20.2％）150gを混合し、これにクエン酸一水和物16gを添加して混合液を作製した。この混合液に、25％水酸化テトラメチルアンモニウム水溶液228gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが110μS/cm以下になるまで洗浄し、脱塩ジルコニアゲル（ZrO2濃度：5.2％、EC：3.6mS/cm、pH8.8）を得た。
次に、脱塩ジルコニアゲル500gに炭酸アンモニウム5.1g（炭酸イオン／ZrO2のモル比＝0.25）を添加し、これを90℃で1時間加熱することによって、無色透明なジルコニアゾルを得た。
Example 5
860 g of pure water and 150 g of zirconium oxychloride (ZrO 2 concentration: 20.2%) were mixed, and 16 g of citric acid monohydrate was added thereto to prepare a mixed solution. To this mixed solution, 228 g of 25% tetramethylammonium hydroxide aqueous solution was added with stirring to produce a zirconia gel. Subsequently, the filtrate EC was washed until the filtrate EC became 110 μS / cm or less using an ultrafiltration device to obtain a desalted zirconia gel (ZrO 2 concentration: 5.2%, EC: 3.6 mS / cm, pH 8.8).
Next, 5.1 g of ammonium carbonate (molar ratio of carbonate ion / ZrO 2 = 0.25) was added to 500 g of desalted zirconia gel, and this was heated at 90 ° C. for 1 hour to obtain a colorless and transparent zirconia sol.
〔比較例１〕
純水1508gとオキシ塩化ジルコニウム（ZrO2濃度：21.1％）250gを混合した。この混合液に、20％アンモニア水144gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが110μS/cm以下になるまで洗浄し、脱塩ジルコニアゲルを得た。
次に、脱塩ジルコニアゲル1000ｇに炭酸水素アンモニウム4.2g（炭酸水素イオン／ZrO2のモル比＝0.25）を添加し、これを90℃で1時間加熱したが、ゾルは得られなかった。
[Comparative Example 1]
1508 g of pure water and 250 g of zirconium oxychloride (ZrO 2 concentration: 21.1%) were mixed. To this mixed solution, 144 g of 20% aqueous ammonia was added with stirring to produce a zirconia gel. Subsequently, it was washed using an ultrafiltration device until the filtrate EC became 110 μS / cm or less to obtain a desalted zirconia gel.
Next, 4.2 g of ammonium hydrogen carbonate (molar ratio of hydrogen carbonate ion / ZrO 2 = 0.25) was added to 1000 g of desalted zirconia gel, and this was heated at 90 ° C. for 1 hour, but no sol was obtained.
〔比較例２〕
純水1508gとオキシ塩化ジルコニウム（ZrO2濃度：21.1％）250gを混合した。この混合液に、20％アンモニア水144gを撹拌下で添加し、ジルコニアゲルを生成させた。次いで、限外ろ過装置を用いてろ液ECが110μS/cm以下になるまで洗浄し、脱塩ジルコニアゲルを得た。
次に、脱塩ジルコニアゲル500gにクエン酸一水和物6.8ｇ、炭酸水素アンモニウム2.1g（炭酸水素イオン／ZrO2のモル比＝0.25）を添加し、これを90℃で1時間加熱したが、ゾルは得られなかった。
[Comparative Example 2]
1508 g of pure water and 250 g of zirconium oxychloride (ZrO 2 concentration: 21.1%) were mixed. To this mixed solution, 144 g of 20% aqueous ammonia was added with stirring to produce a zirconia gel. Subsequently, it was washed using an ultrafiltration device until the filtrate EC became 110 μS / cm or less to obtain a desalted zirconia gel.
Next, 6.8 g of citric acid monohydrate and 2.1 g of ammonium hydrogen carbonate (molar ratio of hydrogen carbonate ion / ZrO 2 = 0.25) were added to 500 g of desalted zirconia gel, and this was heated at 90 ° C. for 1 hour. The sol was not obtained.
〈分析〉
上記実施例と比較例で得られた各ゾル（以下、「ゾル」という）を以下の方法により分析した。
<analysis>
Each sol (hereinafter referred to as “sol”) obtained in the above Examples and Comparative Examples was analyzed by the following method.
[ヒドロキシカルボン酸量]
ゾルのヒドロキシカルボン酸量は、ゾル中のジルコニア成分を沈殿させた後、その上澄み液を島津製作所(株)製 高速液体クロマトグラフ LC-2010Cで測定することによって求めた。
[Amount of hydroxycarboxylic acid]
The amount of hydroxycarboxylic acid in the sol was determined by precipitating the zirconia component in the sol and then measuring the supernatant with a high performance liquid chromatograph LC-2010C manufactured by Shimadzu Corporation.
[アンモニア量]
ゾルのアンモニア量は、Tecator社製 ケルダール自動蒸留滴定装置 ケルテック 2300により測定した窒素量から求めた。
[Ammonia amount]
The amount of ammonia in the sol was determined from the amount of nitrogen measured with a Kjeldahl automatic distillation titrator Keltec 2300 manufactured by Tecator.
[水溶性アミン化合物量]
ゾルの水溶性アミン化合物量は、島津製作所（株）製 全有機体炭素計 TOC-Vにて測定した全有機炭素量（TOC）（％）からヒドロキシカルボン酸に由来する炭素量 CA（％）を引いた後、下式から計算した。
式）水溶性アミン化合物量＝（TOC−CA）÷（水溶性アミン化合物の炭素数×炭素の原子量）×水溶性アミン化合物の分子量
[Amount of water-soluble amine compound]
The amount of water-soluble amine compound in the sol is calculated from the total organic carbon amount (TOC) (%) measured by Shimadzu Corporation Total Organic Carbon Meter TOC-V CA A (% ) And then calculated from the following formula.
Formula) Amount of water-soluble amine compound = (TOC-C A ) ÷ (carbon number of water-soluble amine compound x atomic weight of carbon) x molecular weight of water-soluble amine compound
[Haze率と全光線透過率]
Haze率と全光線透過率は、ゾルを純水でZrO2濃度5％に調整した後、光路長10mmのガラスセルに入れ、日本電色工業(株)製 色度・濁度測定器 COH400で測定した。
[Haze rate and total light transmittance]
Haze rate and total light transmittance were adjusted to 5% ZrO 2 concentration with pure water, and then placed in a glass cell with an optical path length of 10 mm. Using COH400, a chromaticity / turbidity measuring instrument manufactured by Nippon Denshoku Industries Co., Ltd. It was measured.
[薄膜硬度]
ゾルをイオン交換水でZrO2濃度5％に希釈したものを塗布液とし、これをミカサ製スピンコーター1H-DX２を用いてスライドガラスにスピンコート(1000rpm、10秒)し、100℃で10分乾燥させることによって薄膜を得た。 薄膜硬度は、JIS K5600-5-4に従い、HEIDON製 表面性測定機 HEIDON-14を用いて測定した。
[Thin film hardness]
A sol diluted with ion-exchanged water to a ZrO 2 concentration of 5% is used as a coating solution, and this is spin-coated (1000 rpm, 10 seconds) on a slide glass using a Mikasa spin coater 1H-DX2, and 10 minutes at 100 ° C. A thin film was obtained by drying. The thin film hardness was measured according to JIS K5600-5-4 using a HEIDON surface property measuring instrument HEIDON-14.
[結晶構造]
結晶構造はゾルを100℃で乾燥させたものを島津製作所(株)製 Ｘ線回折装置 XRD-7000で測定して解析した。実施例１で得られたジルコニアゾルのXRDパターンを図１に示した。
図１より、結晶形は非晶質であることが分かった。
[Crystal structure]
The crystal structure was analyzed by measuring a sol dried at 100 ° C. with an X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation. The XRD pattern of the zirconia sol obtained in Example 1 is shown in FIG.
From FIG. 1, it was found that the crystal form was amorphous.
表１と表２に、ゾルの分析結果を示した。表１と表２の結果より、実施例１〜５で得られたゾルは透明性が高い非晶質のジルコニアゾルであり、また、高い薄膜硬度が得られるものであることが分かった。 Tables 1 and 2 show the sol analysis results. From the results of Tables 1 and 2, it was found that the sols obtained in Examples 1 to 5 were amorphous zirconia sols having high transparency and high thin film hardness.
Claims (8)
（１）水溶性ジルコニウム化合物とヒドロキシカルボン酸の混合水溶液と、アンモニア及び／又は水溶性アミン化合物とを混合し中和させて、ジルコニアゲルを生成させる第一工程。
（２）上記ジルコニアゲルを脱塩し、脱塩ジルコニアゲルを得る第二工程。
（３）上記脱塩ジルコニアゲルを、炭酸水素イオン及び／又は炭酸イオンの存在下で加熱する第三工程。 The manufacturing method of the zirconia sol characterized by including the following process (1)-(3).
(1) A first step in which a mixed aqueous solution of a water-soluble zirconium compound and a hydroxycarboxylic acid and ammonia and / or a water-soluble amine compound are mixed and neutralized to produce a zirconia gel.
(2) A second step of desalting the zirconia gel to obtain a desalted zirconia gel.
(3) A third step of heating the desalted zirconia gel in the presence of hydrogen carbonate ions and / or carbonate ions.
ヒドロキシカルボン酸／ZrO2（モル比）＝0.01〜0.5であり、
（アンモニア＋水溶性アミン化合物）／ZrO2（モル比）＝0.25〜3である
請求項１記載のジルコニアゾルの製造方法。 The range of each proportion of hydroxycarboxylic acid and ammonia and / or water-soluble amine compound in the zirconia sol,
Hydroxycarboxylic acid / ZrO 2 (molar ratio) = 0.01 to 0.5,
The method for producing a zirconia sol according to claim 1, wherein (ammonia + water-soluble amine compound) / ZrO 2 (molar ratio) = 0.25-3.
（炭酸水素イオン＋炭酸イオン）／ZrO2（モル比）＝0.05〜3である
請求項１又は２記載のジルコニアゾルの製造方法。 The range of the hydrogen carbonate ion and / or carbonate ion existing ratio before heating in the third step,
The method for producing a zirconia sol according to claim 1 or 2, wherein (hydrogen carbonate ion + carbonate ion) / ZrO 2 (molar ratio) = 0.05-3.
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| JPWO2023013289A1 (en) * | 2021-08-04 | 2023-02-09 | ||
| 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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