JP2010202456A - Production method of fine particle - Google Patents
Production method of fine particle Download PDFInfo
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- JP2010202456A JP2010202456A JP2009049723A JP2009049723A JP2010202456A JP 2010202456 A JP2010202456 A JP 2010202456A JP 2009049723 A JP2009049723 A JP 2009049723A JP 2009049723 A JP2009049723 A JP 2009049723A JP 2010202456 A JP2010202456 A JP 2010202456A
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- fine particles
- oxide
- metal oxide
- visible light
- metal
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- 239000010419 fine particle Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004038 photonic crystal Substances 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 20
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- -1 titanium alkoxides Chemical class 0.000 description 10
- 239000010936 titanium Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
この発明は、均一な粒径を有する金属酸化物微粒子を簡便に製造することができる方法に関するものである。 The present invention relates to a method capable of easily producing metal oxide fine particles having a uniform particle diameter.
従来、二酸化チタン（ＴｉＯ２）、二酸化ケイ素（ＳｉＯ２）、酸化タンタル（Ｔａ２Ｏ５）、酸化ジルコニウム（ＺｒＯ２）、酸化亜鉛（ＺｎＯ）、酸化タングステン（ＷＯ３）等の金属酸化物のコロイド結晶がフォトニック結晶として機能することが明らかとなっている（特許文献１）。 Conventionally, metal oxides such as titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconium oxide (ZrO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), etc. It has been revealed that colloidal crystals function as photonic crystals (Patent Document 1).
上記の金属酸化物からなるコロイド粒子がフォトニック結晶として機能するためには、粒径が良く揃っていることが必要である。しかしながら、これらの金属酸化物について再現性よく粒径の揃ったコロイド粒子を得る方法は知られていない。 In order for the colloidal particles made of the above metal oxide to function as a photonic crystal, it is necessary that the particle diameters are well aligned. However, there is no known method for obtaining colloidal particles having a uniform particle size with good reproducibility for these metal oxides.
そこで本発明は、均一な粒径を有する金属酸化物微粒子を簡便に製造することができる方法を提供すべく図ったものである。 Therefore, the present invention is intended to provide a method by which metal oxide fine particles having a uniform particle diameter can be easily produced.
すなわち本発明に係る微粒子製造方法は、金属酸化物からなる微粒子を製造する方法であって、溶媒中の金属アルコキシドに可視光のみを照射する工程を有することを特徴とする。なお、本発明において「可視光のみを照射する」とは、実質的に可視光のみを照射することを意味し、金属アルコキシドの加水分解に影響が及ばない程度の紫外光や赤外光等が混入している場合も含むものである。 That is, the method for producing fine particles according to the present invention is a method for producing fine particles comprising a metal oxide, and includes a step of irradiating only a visible light to a metal alkoxide in a solvent. In the present invention, “irradiating only visible light” means substantially irradiating only visible light, such as ultraviolet light or infrared light that does not affect the hydrolysis of the metal alkoxide. This includes cases where they are mixed.
このようなものであれば、可視光を照射することにより、ゾルゲル法における金属アルコキシドの加水分解が適度に促進されて、ゾルが安定した状態で生成され、得られる微粒子の粒径を均一に揃えることができる。 In such a case, by irradiating visible light, the hydrolysis of the metal alkoxide in the sol-gel method is moderately accelerated, the sol is generated in a stable state, and the particle diameters of the resulting fine particles are made uniform. be able to.
前記金属酸化物としては、例えば、二酸化チタン、二酸化ケイ素、酸化タンタル、酸化ジルコニウム、酸化亜鉛、酸化タングステン等が挙げられる。 Examples of the metal oxide include titanium dioxide, silicon dioxide, tantalum oxide, zirconium oxide, zinc oxide, and tungsten oxide.
前記可視光としては、例えば、赤色光が用いられる。 As the visible light, for example, red light is used.
本発明に係る微粒子製造方法により得られた金属酸化物からなる微粒子が溶媒中に分散してなるフォトニック結晶もまた、本発明の１つである。 A photonic crystal in which fine particles made of a metal oxide obtained by the fine particle production method according to the present invention are dispersed in a solvent is also one aspect of the present invention.
このように本発明によれば、均一な粒径を有する金属酸化物微粒子を簡便に再現性よく製造することができる。 Thus, according to the present invention, metal oxide fine particles having a uniform particle size can be easily produced with good reproducibility.
以下に本発明を詳述する。 The present invention is described in detail below.
本発明は、金属酸化物からなる微粒子を製造する方法であるが、前記金属酸化物としては特に限定されず、例えば、二酸化チタン、二酸化ケイ素、酸化タンタル、酸化ジルコニウム、酸化亜鉛、酸化タングステン等の半導体が挙げられる。 The present invention is a method for producing fine particles comprising a metal oxide, but the metal oxide is not particularly limited, and examples thereof include titanium dioxide, silicon dioxide, tantalum oxide, zirconium oxide, zinc oxide, and tungsten oxide. A semiconductor is mentioned.
本発明は、金属アルコキシドの加水分解によってゾルを生成するゾルゲル法を用いた方法であり、溶媒中の金属アルコキシドに可視光を照射する工程を有しているものである。 The present invention is a method using a sol-gel method in which a sol is generated by hydrolysis of a metal alkoxide, and includes a step of irradiating a metal alkoxide in a solvent with visible light.
前記金属アルコキシドとしては、例えば、Ｔｉ（ＯＣＨ３）４、Ｔｉ（ＯＣ２Ｈ５）４、Ｔｉ（ＯＣ３Ｈ７−ｉ）４、Ｔｉ（ＯＣ４Ｈ９）４等のチタンアルコキシド；Ｔｉ［ＯＳｉ（ＣＨ３）３］４、Ｔｉ［ＯＳｉ（Ｃ２Ｈ５）３］４等のテトラキストリアルキルシロキシチタン；Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、Ｓｉ（ＯＣ３Ｈ７−ｉ）４、Ｓｉ（ＯＣ４Ｈ９−ｔ）４等のケイ素アルコキシド；Ｚｒ（ＯＣＨ３）４、Ｚｒ（ＯＣ２Ｈ５）４、Ｚｒ（ＯＣ３Ｈ７）４、Ｚｒ（ＯＣ４Ｈ９）４等のジルコニウムアルコキシド；Ｔａ（ＯＣＨ３）５、Ｔａ（ＯＣ２Ｈ５）５、Ｔａ（ＯＣ３Ｈ７−ｉ）５、Ｔａ（ＯＣ４Ｈ９）５等のタンタルアルコキシド；Ｗ（ＯＣＨ３）６、Ｗ（ＯＣ２Ｈ５）６、Ｗ（ＯＣ３Ｈ７−ｉ）６、Ｗ（ＯＣ４Ｈ９）６等のタングステンアルコキシド；Ｚｎ（ＯＣ２Ｈ５）２等の亜鉛アルコキシド；等が挙げられる。これらの金属アルコキシドは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the metal alkoxide include titanium alkoxides such as Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 -i) 4 , Ti (OC 4 H 9 ) 4 ; Tetrakistrialkylsiloxytitanium such as OSi (CH 3 ) 3 ] 4 , Ti [OSi (C 2 H 5 ) 3 ] 4 ; Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7- i) 4 , silicon alkoxide such as Si (OC 4 H 9 -t) 4 ; Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (OC 3 H 7 ) 4 , Zr (OC 4 Zirconium alkoxides such as H 9 ) 4 ; tantalum alkoxides such as Ta (OCH 3 ) 5 , Ta (OC 2 H 5 ) 5 , Ta (OC 3 H 7 -i) 5 , Ta (OC 4 H 9 ) 5 ; W (O CH 3) 6, W (OC 2 H 5) 6, W (OC 3 H 7 -i) 6, W (OC 4 H 9) 6 such as tungsten alkoxide; Zn (OC 2 H 5) 2 and zinc alkoxides And the like. These metal alkoxides may be used alone or in combination of two or more.
前記溶媒としては、有機溶媒と水との混合液が挙げられる。前記有機溶媒としては、例えば、メタノール、エタノール、２−プロパノール、グリセリン等のアルコール系溶媒；塩化メチレン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒；ヘキサン、シクロヘキサン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒；テトラヒドロフラン、ジエチルエーテル、ジオキサン等のエーテル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；ジメチルホルムアミド、Ｎ−メチルピロリドン等のアミド系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒；メチルポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタンシロキサン、メチルフェニルポリシロキサン等のシリコーン等；が挙げられる。これらの溶媒は１種を単独で用いてもよく、２種以上を併用してもよい。 As said solvent, the liquid mixture of an organic solvent and water is mentioned. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, 2-propanol, and glycerin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and chlorobenzene; carbonization such as hexane, cyclohexane, benzene, toluene, and xylene. Hydrogen solvents; ether solvents such as tetrahydrofuran, diethyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; And silicones such as methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, and methylphenylpolysiloxane. These solvents may be used alone or in combination of two or more.
また、前記溶媒には酸を添加してもよい。当該酸としては、塩酸、硝酸、ホウ酸、ホウフッ化水素酸等の無機酸；酢酸、ギ酸、シュウ酸、炭酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、メタンスルホン酸等の有機酸等；ジフェニルヨードニウムヘキサフルオロホスフェート、トリフェニルホスホニウムヘキサフルオロホスフェート等の光照射によって酸を発生する光酸発生剤；が挙げられる。 An acid may be added to the solvent. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid; organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc .; diphenyl And photoacid generators that generate an acid upon irradiation with light, such as iodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate.
これらの酸を前記溶媒に添加すると、当該酸が、前記金属アルコキシドの加水分解物が凝結してできた沈殿を再び分散させる解膠剤として、また、前記金属アルコキシドを加水分解、脱水架橋してコロイド粒子を製造するための触媒及び生成したコロイド粒子の分散剤として機能する。 When these acids are added to the solvent, the acid acts as a deflocculant for redispersing the precipitate formed by condensation of the hydrolyzate of the metal alkoxide, and the metal alkoxide is hydrolyzed and dehydrated and crosslinked. It functions as a catalyst for producing colloidal particles and a dispersant for the produced colloidal particles.
前記可視光としては、３８０〜８１０ｎｍの光を意味し、例えば、赤色光（６４０〜８１０ｎｍ）が好適に用いられる。 As said visible light, the light of 380-810 nm is meant, for example, red light (640-810 nm) is used suitably.
本発明において、溶媒中の金属アルコキシドに可視光を照射する以外の工程は特に限定されず、一般的なゾルゲル法と同じであってよい。 In the present invention, the steps other than irradiating the metal alkoxide in the solvent with visible light are not particularly limited, and may be the same as a general sol-gel method.
本発明に係る微粒子製造方法により得られた金属酸化物からなる微粒子を水や有機溶媒等に分散させることにより、当該微粒子が周期的に配列したコロイド結晶、すなわち、屈折率が周期的に変化するフォトニック結晶が得られる。 By dispersing fine particles made of a metal oxide obtained by the fine particle production method according to the present invention in water, an organic solvent, or the like, a colloidal crystal in which the fine particles are periodically arranged, that is, the refractive index changes periodically. A photonic crystal is obtained.
前記有機溶媒としては、例えば、ジメチルホルムアミド等のホルムアミド類や、エチレングリコール等のアルコール類等が挙げられる。 Examples of the organic solvent include formamides such as dimethylformamide, alcohols such as ethylene glycol, and the like.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
＜二酸化チタン微粒子の製造＞
３Ｌビーカーにグリセリン９００ｇを量り採り、これに２−プロパノール１５００ｇ及び塩酸（６×１０−５Ｍ）３０ｍＬを添加して、攪拌後、超音波を５分間照射した。
<Manufacture of titanium dioxide fine particles>
900 g of glycerin was weighed out into a 3 L beaker, 1500 g of 2-propanol and 30 mL of hydrochloric acid (6 × 10 −5 M) were added thereto, and after stirring, ultrasonic waves were irradiated for 5 minutes.
次いで、得られた混合液をマグネチックスターラで攪拌しながらチタン酸テトライソプロピル（Ｔｉ（ＯＣ３Ｈ７−ｉ）４）６０ｍＬを滴下し、その後、室温で１日間放置した。この際、実施例１においては、赤色ＬＥＤ（ピーク波長６３０ｎｍ）を光源として用いて赤色光を照射しながら放置し、比較例１においては、紫外ＬＥＤ（ピーク波長３７５ｎｍ）（５分経過後は水銀灯）を光源として用いて紫外線を照射しながら放置し、比較例２においては、暗状態下で放置した。 Next, 60 mL of tetraisopropyl titanate (Ti (OC 3 H 7 -i) 4 ) was dropped while stirring the obtained mixed liquid with a magnetic stirrer, and then left at room temperature for 1 day. At this time, in Example 1, a red LED (peak wavelength: 630 nm) was used as a light source and left to irradiate red light. In Comparative Example 1, an ultraviolet LED (peak wavelength: 375 nm) (after 5 minutes, a mercury lamp ) Was used as a light source while being irradiated with ultraviolet rays, and in Comparative Example 2, it was left in a dark state.
次に、生じた沈澱を除去し、上澄み液を更に７日間室温で放置した。 Next, the generated precipitate was removed, and the supernatant was further allowed to stand at room temperature for 7 days.
得られた沈澱を水で洗浄し、５００℃で乾燥・焼結して二酸化チタンの微粒子を得た。 The obtained precipitate was washed with water, dried and sintered at 500 ° C. to obtain fine particles of titanium dioxide.
＜結果＞
結果を表１にまとめた。更に、図１に実施例及び比較例で得られた微粒子の粒径の範囲を示し、図２に波長６５０ｎｍの赤色レーザを光源としてシリコンフォトダイオード（ＳＰＤ）の出力電圧に基づく上澄み液の透過率の経時変化を示し、図３に実施例１で得られた微粒子の走査型電子顕微鏡写真を、図４に比較例１で得られた微粒子の走査型電子顕微鏡写真を、図５に比較例２で得られた微粒子の走査型電子顕微鏡写真を示した。
<Result>
The results are summarized in Table 1. Further, FIG. 1 shows the range of the particle size of the fine particles obtained in the examples and comparative examples, and FIG. 2 shows the transmittance of the supernatant liquid based on the output voltage of the silicon photodiode (SPD) using a red laser having a wavelength of 650 nm as a light source. FIG. 3 shows a scanning electron micrograph of the fine particles obtained in Example 1, FIG. 4 shows a scanning electron micrograph of the fine particles obtained in Comparative Example 1, and FIG. Scanning electron micrographs of the fine particles obtained in 1 were shown.
図３に示すように、赤色光を照射しながらチタン酸テトライソプロピルの加水分解を進行させた場合（実施例１）は、粒径が良く揃った二酸化チタン微粒子が得られたが、図４や図５に示すように、紫外光を照射したり（比較例１）、暗状態下に放置したり（比較例２）した場合は、歪な形状の粒子が多く、粒径も不揃いであった。 As shown in FIG. 3, when the hydrolysis of tetraisopropyl titanate was allowed to proceed while irradiating red light (Example 1), fine titanium dioxide particles having a uniform particle size were obtained. As shown in FIG. 5, when ultraviolet light was irradiated (Comparative Example 1) or left in a dark state (Comparative Example 2), there were many distorted particles and the particle sizes were uneven. .
また、図２に示した上澄み液の透過率の経時変化からわかるように、紫外光を照射した場合（比較例１）は、熟成・粒成長が極めて迅速に進み、一方、暗状態下に放置した場合（比較例２）は、熟成・粒成長の進行が極めてゆっくりであった。そして、赤色光を照射した場合（実施例１）はこれらの中間の速度で熟成・粒成長が進行したことがわかった。このため、金属アルコキシドを加水分解して含水酸化物ゾルを調製する際に光を照射すると、得られた含水酸化物ゾルの熟成・粒成長速度が速くなるが、紫外光を照射すると熟成・粒成長速度が速すぎて粒径が不均一になり、紫外光より長波長である可視光を照射すると適度な速度で熟成・粒成長が進行し、均一な粒径を有する二酸化チタン微粒子が得られると推測される。 In addition, as can be seen from the change with time in the transmittance of the supernatant liquid shown in FIG. 2, when ultraviolet light was irradiated (Comparative Example 1), ripening and grain growth proceeded very rapidly, while leaving in a dark state. In the case (Comparative Example 2), the progress of ripening and grain growth was extremely slow. When red light was irradiated (Example 1), it was found that aging and grain growth proceeded at an intermediate speed. Therefore, when light is irradiated when hydrolyzing a metal alkoxide to prepare a hydrous oxide sol, the aging and grain growth rate of the obtained hydrous oxide sol increases. When the growth rate is too high, the particle size becomes non-uniform, and when visible light having a longer wavelength than ultraviolet light is irradiated, ripening and grain growth proceed at an appropriate rate, and titanium dioxide fine particles having a uniform particle size are obtained. It is guessed.
本発明によって得られた金属酸化物微粒子を用いることにより、有機フォトニック結晶を得ることができる。 An organic photonic crystal can be obtained by using the metal oxide fine particles obtained by the present invention.
Claims (4)
溶媒中の金属アルコキシドに可視光のみを照射する工程を有することを特徴とする微粒子製造方法。 A method for producing fine particles comprising a metal oxide,
A method for producing fine particles, comprising a step of irradiating only a visible light to a metal alkoxide in a solvent.
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| JP2000157874A (en) * | 1998-09-21 | 2000-06-13 | Agency Of Ind Science & Technol | Titanium oxide photocatalyst and production thereof |
| JP2004109178A (en) * | 2002-09-13 | 2004-04-08 | Kawamura Inst Of Chem Res | Colloidal crystal and its manufacturing method |
| JP2004226891A (en) * | 2003-01-27 | 2004-08-12 | Bando Chem Ind Ltd | Colloidal solution, colloidal crystal, and fixed colloidal crystal |
| JP2005272157A (en) * | 2004-03-23 | 2005-10-06 | Japan Science & Technology Agency | Method for producing oxide semiconductor thin film by irradiation with laser light |
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| JP2000157874A (en) * | 1998-09-21 | 2000-06-13 | Agency Of Ind Science & Technol | Titanium oxide photocatalyst and production thereof |
| JP2004109178A (en) * | 2002-09-13 | 2004-04-08 | Kawamura Inst Of Chem Res | Colloidal crystal and its manufacturing method |
| JP2004226891A (en) * | 2003-01-27 | 2004-08-12 | Bando Chem Ind Ltd | Colloidal solution, colloidal crystal, and fixed colloidal crystal |
| JP2005272157A (en) * | 2004-03-23 | 2005-10-06 | Japan Science & Technology Agency | Method for producing oxide semiconductor thin film by irradiation with laser light |
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