JP4633628B2 - Metal compounds having a new skeleton - Google Patents
Metal compounds having a new skeleton Download PDFInfo
- Publication number
- JP4633628B2 JP4633628B2 JP2005512453A JP2005512453A JP4633628B2 JP 4633628 B2 JP4633628 B2 JP 4633628B2 JP 2005512453 A JP2005512453 A JP 2005512453A JP 2005512453 A JP2005512453 A JP 2005512453A JP 4633628 B2 JP4633628 B2 JP 4633628B2
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- JP
- Japan
- Prior art keywords
- metal
- metal compound
- atom
- titanium
- alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000002736 metal compounds Chemical class 0.000 title claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 89
- 239000002184 metal Substances 0.000 claims description 89
- 150000004703 alkoxides Chemical class 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 125000004429 atom Chemical group 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 36
- 239000010408 film Substances 0.000 description 32
- 239000003960 organic solvent Substances 0.000 description 30
- -1 Titanium alkoxides Chemical class 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 229910044991 metal oxide Inorganic materials 0.000 description 19
- 150000004706 metal oxides Chemical class 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000010936 titanium Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 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 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
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- 239000004094 surface-active agent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
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- ONBWNNUYXGJKKD-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC ONBWNNUYXGJKKD-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Description
本発明は、金属酸化膜および化学吸着膜の形成材料や、有機−無機複合ハイブリッド材料等として有用な、新規結晶構造を有する金属化合物およびチタン化合物に関する。
従来技術：
従来、透明で均質な金属酸化物ゾルの製造方法として、１種若しくは２種以上の金属アルコキシドへの水の添加を−２０℃以下の温度で行うことを特徴とする金属酸化物前駆体ゾルの製造方法が知られている。（特開平１０−２９８７６９号公報を参照）
また、チタンテトラアルコキシドを、１．０倍モル〜１．７倍モルの水を用いて２０〜９０℃の温度で加水分解する、有機溶剤溶解性の高分子量のラダー状ポリチタノキサンの製造方法が知られている。この方法は、高分子量体においても有機溶剤に溶解し、繊密な薄膜を形成する高分子量のラダー状ポリチタノキサンを提供することを目的としている。（特開平１−１２９０３２号公報を参照）
また、水を加えて加熱することにより部分的に加水分解した金属塩１モルに対して、０．１〜２．０モルの水を含有するアルコール溶液を加え、加熱して金属塩を加水分解して金属水酸化物とし、脱水縮合した後、濃縮する金属酸化物前駆体溶液の製造方法が知られている。（特開２００１−３４２０１８号公報を参照）
しかし、上述したいずれの方法を用いて得られたゾル中の金属酸化物の構造は明らかでなかった。The present invention relates to a metal compound and a titanium compound having a novel crystal structure, which are useful as materials for forming metal oxide films and chemical adsorption films, organic-inorganic composite hybrid materials, and the like.
Conventional technology:
Conventionally, as a method for producing a transparent and homogeneous metal oxide sol, water is added to one or more metal alkoxides at a temperature of −20 ° C. or lower. Manufacturing methods are known. (See JP-A-10-298769)
Also known is a method for producing an organic solvent-soluble, high-molecular-weight ladder-type polytitanoxan that hydrolyzes titanium tetraalkoxide at a temperature of 20 to 90 ° C. using 1.0-fold mole to 1.7-fold mole of water. It has been. This method is intended to provide a high-molecular-weight ladder-like polytitanoxane that dissolves in an organic solvent even in a high-molecular-weight body and forms a fine thin film. (See Japanese Patent Laid-Open No. 1-129032)
Moreover, with respect to 1 mol of metal salts partially hydrolyzed by adding water and heating, an alcohol solution containing 0.1 to 2.0 mol of water is added and heated to hydrolyze the metal salt. There is known a method for producing a metal oxide precursor solution that is converted into a metal hydroxide, dehydrated and condensed, and then concentrated. (See JP 2001-342018 A)
However, the structure of the metal oxide in the sol obtained using any of the methods described above was not clear.
本発明は、金属酸化膜や化学吸着膜の形成用材料等として有用であり、酸や塩基によりｐＨを調整したり、分散安定化剤を添加しなくとも有機溶媒中で凝集することがない、新規な結晶構造を有する金属化合物を提供することを課題とする。
本発明者らは、チタンテトライソプロポキシドの有機溶媒溶液に、−２０℃以下の低温で所定量の水を滴下した後、自然昇温させ、次いで反応液を還流することで微粒子を得た。そして、得られた微粒子の結晶構造を種々の分析手段により解析したところ、この微粒子は、空間的に６つの金属原子が五角錐の頂点に位置する配置を２つ含む新規な結晶構造を有するチタン化合物であるという知見を得た。さらに、このような結晶構造を有する金属化合物は、（ｉ）粒子径が数ナノメートル程度の超微粒子であって、しかも粒子径分布が単分散であること、（ｉｉ）有機溶媒中に均一に分散させることができること、（ｉｉｉ）有機溶媒中で安定して存在すること、および（ｉｖ）金属酸化物膜および化学吸着膜の形成用材料、並びに有機−無機複合ハイブリッド材料として有用であることを見出し、本発明を完成するに至った。
かくして本発明の第１によれば、１分子内に、空間的に６つの金属原子が５角錐の頂点に位置する配置を２つ含む結晶構造を有することを特徴とする金属化合物が提供される。
本発明の金属化合物は、２つの五角錐が、該五角錐の１つの面を向けて対峙しているものであるのが好ましく、五角錐の１つの面が底面五角形同士であるものがより好ましく、五角錐の面が、一定の角度を持って対峙しているものがさらに好ましい。
本発明の金属化合物は、その結晶構造を構成する各金属原子が架橋型酸素原子によって架橋されているものであるのが好ましく、μ３型架橋酸素原子を含むものがより好ましい。
本発明の金属化合物は、アルコキシ基が結合している金属原子を含むものが好ましい。
本発明の金属化合物は、金属原子がチタン原子であるのが好ましい。
また、本発明の金属化合物は、式（１）：Ｍ（ＯＲ）ｎ（式中、Ｍは金属原子を表し、Ｒはアルキル基を表し、ｎは金属原子の原子価を表す。）で表される金属アルコキシド、この金属アルコキシドの２種以上を反応させることにより得られる複合アルコキシド、１種もしくは２種以上の金属アルコキシドと１種もしくは２種以上の金属塩との反応により得られる複合アルコキシド、またはこれらの２種以上の組み合わせの加水分解生成物であるのが好ましい。
本発明の第２によれば、前記金属化合物を該金属化合物に対し０．２５倍モル未満の水で処理して得られる分散質が提供される。
本発明の分散質は、有機溶媒中、酸、塩基、及び／または分散安定化剤の非存在下、前記金属化合物に対し０．２５倍モル未満の水を用いて得られるのが好ましく、金属−酸素結合を有する分散質であるのがより好ましい。
本発明によれば、酸や塩基によりｐＨを調整したり、分散安定化剤を添加しなくとも有機溶媒中で凝集することがない、新規な結晶構造を有する金属化合物が提供される。本発明の金属化合物は、金属酸化物膜や化学吸着膜の形成用材料、有機−無機複合ハイブリッド材料等として有用である。
以下、本発明の金属化合物およびチタン化合物について詳細に説明する。
（１）金属化合物
本発明第１は、１分子内に、空間的に６つの金属原子が五角錐の頂点に位置する配置を２つ含む結晶構造を有することを特徴とする金属化合物である。
本発明の金属化合物を構成する金属としては特に制限されないが、例えば、アルカリ金属、アルカリ土類金属、短周期型周期律表第ＩＩＩＢ族元素、同周期律表第ＩＶＢ族元素、同周期律表第ＶＢ族元素、遷移金属元素およびランタニド元素からなる群から選ばれる１種または２種以上が挙げられる。これらの中でも、金属酸化物膜および化学吸着膜の形成用材料、並びに複合ハイブリッド材料としての有用性の観点から、チタン、ジルコニウム、アルミニウム、ケイ素、ゲルマニウム、インジウム、スズ、タンタル、タングステン、亜鉛および鉛が好ましく、チタンが特に好ましい。
本発明の金属化合物は、１分子内に、空間的に６つの金属原子が５角錐の頂点に位置する配置を２つ含む結晶構造からなり、この五角錐の１つの面を向けて対峙している構造のものが好ましく、五角錐の面が、一定の角度を持って対峙しているものがさらに好ましい。
また本発明の金属化合物は、その結晶構造を構成する各金属原子が、互いに架橋型酸素原子によって架橋されているものが好ましい。架橋型酸素原子には、２つの金属原子のみと結合するμ２型架橋酸素原子、３つの金属原子と結合するμ３型架橋酸素原子、及び４つの金属原子と結合するμ４型架橋酸素原子等が存在し得るが、本発明の金属化合物は、少なくともμ３型架橋酸素原子を有するものが好ましい。
本発明の金属化合物は、金属原子が架橋型酸素原子により架橋され、さらにアルコキシ基が結合している金属原子を含むものが好ましい。アルコキシ基としては特に制限されないが、原料の入手容易性、生産効率等の点から、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基等の炭素数１〜４のアルコキシ基が好ましい。結合するアルコキシ基の数は特に制限されず、金属原子の種類や原子価、一分子中に含まれる金属原子の数等に依存する。また、アルコキシ基が複数個の場合、結合するアルコキシ基は全てが同一であっても、種類が異なっていてもよい。
本発明の金属化合物の基本骨格を図１に示す。図１において、１ａは紙面表側にある金属原子、１ｂは紙面奥側にある金属原子をそれぞれ表す。図１に示す基本骨格では、６つの金属原子が五角錐の頂点に位置する配置を２つ含む該五角錐の１つの面を向けて対峙している構造を有する。そして、この五角錐の１つの面が底面五角形同士であって、五角錐の面が一定の角度を保っている。この角度は、金属原子の大きさ等により定まるものであり、例えば、金属原子がチタン原子の場合には約３６°である。また、図１においては、分かりやすくするために金属原子同士を結んでいるが、実際には、各金属原子は架橋型酸素原子を介して結合していてもよい。
本発明の金属化合物は、１分子内に、空間的に６つの金属原子が五角錐の頂点に位置する配置を２つ含む結晶構造を有するものであれば、図１に示す基本骨格を有するものに限定されない。例えば、１分子内に、空間的に６つの金属原子が五角錐の頂点に位置する配置を２つ含む結晶構造を有するが、金属原子と金属原子との結合距離がすべて同じではないものや、１分子内に、空間的に６つの金属原子が五角錐の頂点に位置する配置を２つ含む結晶構造を有するが、五角錐の底面に位置する五角形が正五角形ではないもの等も本発明に含まれる。
（２）製造方法
本発明の金属化合物は、式（１）：Ｍ（ＯＲ）ｎで表される金属アルコキシド（以下、「金属アルコキシド」という。）、この金属アルコキシドを２種以上を反応させることにより得られる複合アルコキシド、１種もしくは２種以上の金属アルコキシドと１種もしくは２種以上の金属塩との反応により得られる複合アルコキシド、前記金属アルコキシドの２種以上の組み合わせ、前記複合アルコキシドの２種以上の組み合わせ、前記金属アルコキシドと複合アルコキシドとの組み合わせ（以下、「金属アルコキシド類」という。）を、有機溶媒中、所定量の水により部分的に加水分解することにより製造することができる。
式（１）で表される金属アルコキシドにおいて、式（１）中、Ｍは金属原子を表す。金属原子としては、チタン、ジルコニウム、アルミニウム、ケイ素、ゲルマニウム、インジウム、スズ、タンタル、亜鉛、タングステンおよび鉛からなる群から選ばれる１種以上が挙げられ、チタンが特に好ましい。Ｒはアルキル基を表す。アルキル基の炭素数は特に限定されないが、入手が容易であり、取扱い性にも優れることから、通常１〜１０、好ましくは１〜４である。また、ｎは金属原子の原子価を表す。
式（１）で表される金属アルコキシドの具体例としては、Ｔｉ（ＯＣＨ３）４、Ｔｉ（ＯＣ２Ｈ５）４、Ｔｉ（ＯＣ３Ｈ７−ｉ）４、Ｔｉ（ＯＣ４Ｈ９）４等のチタンアルコキシド；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；Ａｌ（ＯＣＨ３）３、Ａｌ（ＯＣ２Ｈ５）３、Ａｌ（ＯＣ３Ｈ７−ｉ）３、Ａｌ（ＯＣ４Ｈ９）３等のアルミニウムアルコキシド；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；Ｇｅ（ＯＣ２Ｈ５）４等のゲルマニウムアルコキシド；Ｉｎ（ＯＣＨ３）３、Ｉｎ（ＯＣ２Ｈ５）３、Ｉｎ（ＯＣ３Ｈ７−ｉ）３、Ｉｎ（ＯＣ４Ｈ９）３等のインジウムアルコキシド；Ｓｎ（ＯＣＨ３）４、Ｓｎ（ＯＣ２Ｈ５）４、Ｓｎ（ＯＣ３Ｈ７−ｉ）４、Ｓｎ（ＯＣ４Ｈ９）４等のスズアルコキシド；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；Ｐｂ（ＯＣ４Ｈ９）４等の鉛アルコキシド等が挙げられる。
２種以上の金属アルコキシド間の反応により得られる複合アルコキシドとしては、アルカリ金属またはアルカリ土類金属のアルコキシドと遷移金属のアルコキシドとの反応により得られる複合アルコキシド、第ＩＩＩＢ族元素の組合せにより錯塩の形で得られる複合アルコキシド等を例示することができる。
これら複合アルコキシドの具体例としては、ＢａＴｉ（ＯＲ）６、ＳｒＴｉ（ＯＲ）６、ＢａＺｒ（ＯＲ）６、ＳｒＺｒ（ＯＲ）６、ＬｉＮｂ（ＯＲ）６、ＬｉＴａ（ＯＲ）６、およびこれらの組合せ、ＬｉＶＯ（ＯＲ）４、ＭｇＡｌ２（ＯＲ）８、（ＲＯ）３ＳｉＯＡｌ（ＯＲ’）２、（ＲＯ）３ＳｉＯＴｉ（ＯＲ’）３、（ＲＯ）３ＳｉＯＺｒ（ＯＲ’）３、（ＲＯ）３ＳｉＯＢ（ＯＲ’）２、（ＲＯ）３ＳｉＯＮｂ（ＯＲ’）４、（ＲＯ）３ＳｉＯＴａ（ＯＲ’）４等のシリコンアルコキシドと前記金属アルコキシドとの反応物およびその縮重合物が挙げられる。ここで、Ｒは前記と同じ意味を表し、Ｒ’はＲと同様のアルキル基を表す。
１種もしくは２種以上の金属アルコキシドと１種もしくは２種以上の金属塩との反応により得られる複合アルコキシドとしては、金属塩と金属アルコキシドとの反応により得られる化合物を例示することができる。金属塩としては、塩化物、硝酸塩、硫酸塩、酢酸塩、ギ酸塩、シュウ酸塩等を使用できる。また、金属アルコキシドとして、上述した金属アルコキシドと同様のものが使用できる。
金属アルコキシド類は、適当な有機溶媒に溶解または分散させて使用する。有機溶媒中の金属アルコキシドの濃度は、急激な発熱を抑制し、撹拌が可能な流動性を有する範囲であれば特に限定されないが、通常５〜３０重量％である。
用いる有機溶媒としては、金属アルコキシド類の加水分解反応に対して不活性なものであれば特に制約されない。金属アルコキシド類の加水分解反応を低温で行うためには、低い凝固点、好ましくは０℃以下、より好ましくは−５０℃以下の凝固点を有するものが好適である。具体的には、エーテル系溶媒や芳香族炭化水素系溶媒等が挙げられる。
エーテル系溶媒としては、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジヘキシルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、テトラヒドロフラン、ジオキサン等が挙げられる。芳香族炭化水素系溶媒としては、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ジクロロベンゼン、クロロトルエン、ブロモベンゼン、クメン、テトラリン、ブチルベンゼン、シメン、ジエチルベンゼン、ペンチルベンゼン、ジペンチルベンゼン、酢酸ベンジル等が挙げられる。これらの溶媒は１種単独で、あるいは２種以上を混合して用いることができる。これらの中でも、本発明の金属化合物が収率よく得られることから、トルエン、テトラヒドロフランの使用が好ましい。
また、金属アルコキシド類が有機溶媒と均一に混合しない場合には、例えば、１，２−ビス−（２−エチルヘキシルオキシカルボニル）−１−エタンスルホン酸ナトリウム、ポリオキシエチレン（６）ノニルフェニルエーテル等の界面活性剤を添加したり、撹拌処理、超音波処理等を施し、溶液を均一にするのが好ましい。
有機溶媒の使用量は、金属アルコキシド１００重量部に対し、通常１０〜５，０００重量部、好ましくは１００〜３，０００重量部である。１０重量部未満では生成する微粒子が結合した状態で成長し、粒径制御が困難になる場合があり、一方５，０００重量部を超えると溶液が希薄すぎて、微粒子の生成が困難となるおそれがある。
金属アルコキシド類の加水分解に用いる水は、中性であれば特に制限されないが、副反応を抑制する観点から、不純物含有量の少ない純水、蒸留水またはイオン交換水が好ましい。
反応に関与する水の量は特に制限されないが、具体的には、金属アルコキシド類に対し０．５〜１．５倍モル、好ましくは０．５〜１．２５倍モル等を例示することができる。
水の添加方法としては、使用量の全量の水を連続的に添加する方法、および複数回に分割して添加する方法のいずれであってもよい。後述するように、水を複数回に分割して添加する場合には、添加するときの温度を変化させてもよい。例えば、第１回目の水の添加を−２５℃〜−２０℃で行い、２回目の添加を−８０℃〜−７０℃で行うことができる。
また、水は適当な有機溶媒に希釈して用いることもできる。有機溶媒に希釈した水を用いることで、水の滴下時における局部的な発熱を防止して、金属アルコキシドの均質な加水分解を行うことができる。水の希釈に用いる有機溶媒としては、水と相溶性のあるものが好ましい。例えば、メタノール、エタノール、イソプロピルアルコール、ｎ−プロピルアルコール、ｎ−ブチルアルコール等が挙げられる。
金属アルコキシドの水による加水分解反応においては、酸、塩基または分散安定化剤を添加してもよい。
酸および塩基は、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、金属アルコキシドおよび生成した金属アルコキシドの多量体等を加水分解、脱水縮合させてコロイド粒子等の分散質を製造するための触媒として、並びに生成した分散質の分散剤として機能するものであれば特に制限されない。
酸としては、例えば、塩酸、硝酸、ホウ酸、ホウフッ化水素酸等の鉱酸；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；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；等が挙げられる。塩基としては、例えば、トリエタノールアミン、トリエチルアミン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン、アンモニア、ジメチルホルムアミド、ホスフィン等が挙げられる。
分散安定化剤は、分散質を分散媒中に安定に分散させる効力を有する、解膠剤、保護コロイド、界面活性剤等の凝結防止剤等の剤をいう。その具体例としては、グリコール酸、グルコン酸、乳酸、酒石酸、クエン酸、リンゴ酸、コハク酸等の多価カルボン酸；ヒドロキシカルボン酸；ピロ燐酸、トリポリ燐酸等の燐酸；アセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸−ｎ−プロピル、アセト酢酸イソプロピル、アセト酢駿−ｎ−ブチル、アセト酢酸−ｓｅｃ−ブチル、アセト酢酸−ｔ−ブチル、２，４−ヘキサンジオン、２，４−ヘプタンジオン、３，５−ヘプタンジオン、２，４−オクタンジオン、２，４−ノナンジオン、５−メチル−ヘキサンジオン等の金属原子に対して強いキレート能力を有する多座配位子化合物；等が挙げられる。
金属アルコキシド類と水との加水分解反応を行う方法としては、（ａ）金属アルコキシド類の有機溶媒溶液に水を添加する方法、（ｂ）水と有機溶媒との混合溶媒中に、金属アルコキシド類を添加する方法等が挙げられるが、収率よく本発明の金属化合物を得ることができることから、（ａ）の方法が好ましい。なかでも、金属アルコキシド類を有機溶媒に溶解または分散させた溶液に、金属アルコキシド類に対し０．６倍モル〜１．２５倍モルの水を、−２０℃以下でゆっくりと添加し、反応液を自然昇温させた（第１工程）後、還流する（第２工程）方法が特に好ましい。
第１工程においては、金属アルコキシド類の低温加水分解反応が主に進行するものと考えられる。例えば、金属アルコキシド類としてチタンテトライソプロポキシドを使用する場合、第１工程により、ゆるい結晶類似かご型（鎖）構造（準安定化構造）を有する微粒子の分散液が得られる。得られる微粒子の粒子径は０．５〜１０ｎｍ、好ましくは１〜５ｎｍである。
水の滴下温度は、用いる金属アルコキシド類の安定性に依存する。通常、−２０℃以下の温度であれば特に問題はないが、金属アルコキシドの種類によっては、−５０℃〜−１００℃の温度範囲で行うことがより好ましい場合がある。このように低温で水を滴下することにより、微粒子状の本発明の金属化合物の分散液を得ることができる。
水の滴下時間は反応規模等によるが、通常１０分から３時間、好ましくは１５分から１時間である。滴下終了後においては、反応液を室温に昇温し、熟成のために１〜２４時間撹拌を続けるのが好ましい。
第２工程は、第１工程で得られた反応液を用いる有機溶媒の還流温度で還流することにより本発明化合物を得るものである。この工程においては、滴下した水が完全に加水分解に使用され、重縮合反応（脱水および脱アルコール反応）により本発明化合物が生成する。還流時間は特に制約はないが、通常３０分〜５時間、好ましくは、１〜３時間である。第２工程により得られる本発明の金属化合物を含む溶液は、平均粒径が１〜１０ｎｍ、粒径分布が０．１〜５０ｎｍの単分散の分散質であって、保存安定性に優れている。
該溶液を、室温以下の温度で静置すると結晶が析出してきて、本発明の金属化合物として単離するこができる。
単離された本発明の金属化合物結晶を、該金属化合物に対し０．２５倍モル未満の水で処理して新たな分散質を得ることができる。ここで得られる分散質は、前記第２工程で得られる金属化合物を含む溶液と同等の単分散で保存安定性に優れる分散質を形成する。該分散質は、有機溶媒中、酸、塩基、及び／または分散安定化剤の非存在下に調整した金属−酸素結合を有する分散質となる。
本発明の金属化合物は安定であり、各種有機溶媒に対する分散性に優れる。本発明の金属化合物は、単離した後に有機溶媒に分散させることにより、あるいは上述した製造方法により得られる反応液をそのまま用いることにより、以下に述べるように、金属酸化物膜や化学吸着膜の形成用材料、有機−無機複合ハイブリッドの材料として有用である。
すなわち、本発明の金属化合物を有機溶媒に分散してなる溶液を、基体に塗布または吹き付けすると基体上に金属酸化物膜を形成することができる。例えば、この溶液を基体上に塗布または吹き付け後、２００℃以下、好ましくは１５０℃以下の温度で加熱・乾燥し、成膜することにより製造することができる。加熱することで、溶媒を乾燥し、前記生成物の加水分解および脱水縮合を行う。加熱時間は、特に限定されないが、通常１〜１２０分の範囲である。
本発明の金属化合物の溶液中の濃度は、基板上に塗布可能な濃度であれば特に制限されず、塗布方法、設定膜厚により適宜設定することができる。一般的には、酸化物に換算した重量で５〜５０重量％の範囲である。
用いる有機溶媒としては、本発明の金属化合物の分散性に影響を与えない溶媒であれば特に制約はない。具体的には、前記本発明の金属化合物を製造する際に用いることができる溶媒として例示した溶媒が挙げられる。
本発明の金属化合物を含む溶液を用いて成膜した金属酸化物膜の膜表面は、平均粗さが１０ｎｍ以下、好ましくは５ｎｍ以下であって、平坦性に優れ、濡れ性、撥水性、保存安定性にも優れている。また、２００℃以下の温度で乾燥することにより成膜できるので、プラスチック基板上にも成膜することができる。すなわち、プラスチック基板上にも、炭素含有量が元素比で１０％以下の高密度の平滑な膜表面を有する金属酸化物膜を形成することができる。
基体に本発明の金属化合物を含む溶液を塗布する方法としては、特に制約はない。例えば、スピンコート法、デイップコート法、スプレーコート法、ロールコート法、スクリーン印刷法、オフセット印刷法等の公知の方法をいずれも使用することができる。なかでも、塗布時にパターニングできる、スクリーン印刷法やオフセット印刷法、ロールコート法が好ましく、大量生産を安価に行うことのできる、バーを用いるロールコート法、ギーサーを用いるロールコート法等のロールコート法がより好ましい。
本発明の金属化合物から金属酸化物薄膜を形成する場合においては、塗布被膜の加熱時および／又は加熱後に、光照射するのが好ましい。塗布被膜に紫外光もしくは可視光を照射する光源は、１５０ｎｍ〜７００ｎｍの波長の光を発生するものであれば、特に制約はない。例えば、超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、キセノンランプ、ハロゲンランプ、ナトリウムランプ等が挙げられる。好ましくは、超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、キセノンランプである。
また、フォトマスクを併用すれば透明導電性パターンを形成することができる。レーザー発振装置を使用することもできる。レーザー光を用いた場合、照射部分以外は金属酸化物とならないので、塗布時にスクリーン印刷等を用いることなく所望のパターンを形成することができる。
本発明の金属化合物を含む塗布液の反応を行った場合、金属酸化物の生成とともに金属水酸化物が残る。この金属−ＯＨ結合の吸収を考慮して、４００ｎｍ以下の紫外光を含む光を発生する装置を用いるのが好ましい。更に、脱水反応が進行して、メタロキサンネットワークが形成した場合、金属−Ｏ−金属結合の吸収は，金属−ＯＨ結合より短波長であるが、金属−Ｏ−金属結合を活性化することができる波長の光照射によって、金属酸化物の結晶化が促進する。照射時間は、特に限定されるものではないが、通常１分〜１２０時間である。
基体の材質や大きさに特に制限はない。基体の材質としては、金属、セラミックス、ガラス、プラスチック、紙、繊維、皮革等が挙げられる。基体の形状も、シート状、板状、フィルム状、立体物等いかなる形状であってもよい。また、すでに塗装した基体を用いることもできる。
また、本発明の金属化合物の有機溶媒分散液は、化学吸着膜形成用材料としても有用である。例えば、アルキルトリアルコキシシランやフルオロアルキルトリアルコキシシラン等の金属系界面活性剤の有機溶媒溶液に、本発明の金属化合物の有機溶媒分散液を所定量添加して化学吸着膜形成用溶液を調製し、このものをガラス基板等の基体上表面に塗布、乾燥することで、良好で緻密な単分子からなる化学吸着膜を形成することができる。化学吸着膜の形成に用いる基体としては特に制約されず、前記金属酸化物膜の形成に用いることができる基体として列記したものと同様のものが挙げられる。その他、本発明の金属化合物は、有機−無機複合ハイブリッド材料としても有用である。The present invention is useful as a material for forming a metal oxide film or a chemical adsorption film, and does not aggregate in an organic solvent without adjusting pH with an acid or base or adding a dispersion stabilizer. It is an object to provide a metal compound having a novel crystal structure.
The present inventors dropped a predetermined amount of water into an organic solvent solution of titanium tetraisopropoxide at a low temperature of −20 ° C. or lower, then naturally raised the temperature, and then refluxed the reaction solution to obtain fine particles. . Then, when the crystal structure of the obtained fine particles was analyzed by various analysis means, the fine particles were found to be titanium having a novel crystal structure including two arrangements in which six metal atoms are located at the apexes of pentagonal pyramids. The knowledge that it is a compound was obtained. Further, the metal compound having such a crystal structure is (i) ultrafine particles having a particle size of several nanometers, and the particle size distribution is monodisperse; (ii) uniformly in an organic solvent. It can be dispersed, (iii) it exists stably in an organic solvent, and (iv) it is useful as a material for forming a metal oxide film and a chemical adsorption film, and as an organic-inorganic composite hybrid material. The headline and the present invention were completed.
Thus, according to the first aspect of the present invention, there is provided a metal compound characterized by having a crystal structure containing two arrangements in which six metal atoms are located at the apexes of a pentagonal pyramid in one molecule. .
In the metal compound of the present invention, it is preferable that two pentagonal pyramids face each other with one surface of the pentagonal pyramid facing each other, and one surface of the pentagonal pyramid is more preferably a bottom pentagon. More preferably, the surfaces of the pentagonal pyramids face each other with a certain angle.
Metal compounds of the present invention preferably each metal atom is one that is crosslinked by a crosslinking type oxygen atoms constituting the crystal structure, those comprising mu 3 type bridging oxygen atom is more preferable.
The metal compound of the present invention preferably contains a metal atom to which an alkoxy group is bonded.
In the metal compound of the present invention, the metal atom is preferably a titanium atom.
The metal compound of the present invention is represented by the formula (1): M (OR) n (wherein M represents a metal atom, R represents an alkyl group, and n represents a valence of the metal atom). A metal alkoxide, a composite alkoxide obtained by reacting two or more of the metal alkoxides, a composite alkoxide obtained by reacting one or more metal alkoxides with one or more metal salts, Or it is preferable that it is a hydrolysis product of the combination of these 2 or more types.
According to a second aspect of the present invention, there is provided a dispersoid obtained by treating the metal compound with less than 0.25 moles of water relative to the metal compound.
The dispersoid of the present invention is preferably obtained by using less than 0.25 moles of water with respect to the metal compound in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent. -A dispersoid having an oxygen bond is more preferable.
ADVANTAGE OF THE INVENTION According to this invention, the metal compound which has a novel crystal structure which does not aggregate in an organic solvent, without adjusting pH with an acid or a base, or adding a dispersion stabilizer is provided. The metal compound of the present invention is useful as a material for forming a metal oxide film or a chemical adsorption film, an organic-inorganic composite hybrid material, or the like.
Hereinafter, the metal compound and titanium compound of the present invention will be described in detail.
(1) Metal Compound The first aspect of the present invention is a metal compound characterized by having a crystal structure including two arrangements in which six metal atoms are located at the apexes of a pentagonal pyramid in one molecule.
Although it does not restrict | limit especially as a metal which comprises the metal compound of this invention, For example, an alkali metal, alkaline-earth metal, a short period type periodic table group IIIB element, a periodic table group IVB element, a periodic table One type or two or more types selected from the group consisting of Group VB elements, transition metal elements and lanthanide elements can be mentioned. Among these, titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, tungsten, zinc, and lead from the viewpoint of usefulness as a material for forming metal oxide films and chemical adsorption films, and composite hybrid materials Is preferred, and titanium is particularly preferred.
The metal compound of the present invention is composed of a crystal structure containing two arrangements in which six metal atoms are located at the apex of a pentagonal pyramid in one molecule, facing each other facing one side of the pentagonal pyramid. It is preferable to have a structure in which the surfaces of the pentagonal pyramids face each other with a certain angle.
In addition, the metal compound of the present invention is preferably such that each metal atom constituting the crystal structure is cross-linked with a cross-linked oxygen atom. The bridging oxygen atom includes a μ 2 type bridging oxygen atom that binds to only two metal atoms, a μ 3 type bridging oxygen atom that binds to three metal atoms, and a μ 4 type bridging oxygen atom that binds to four metal atoms. However, the metal compound of the present invention preferably has at least a μ 3 type bridging oxygen atom.
The metal compound of the present invention preferably contains a metal atom in which a metal atom is crosslinked by a bridging oxygen atom and an alkoxy group is further bonded. Although it does not restrict | limit especially as an alkoxy group, C1-C4 alkoxy, such as a methoxy group, an ethoxy group, n-propoxy group, an isopropoxy group, n-butoxy group, from points, such as the availability of a raw material and production efficiency. Groups are preferred. The number of alkoxy groups to be bonded is not particularly limited, and depends on the type and valence of metal atoms, the number of metal atoms contained in one molecule, and the like. When there are a plurality of alkoxy groups, the bonded alkoxy groups may all be the same or of different types.
The basic skeleton of the metal compound of the present invention is shown in FIG. In FIG. 1, 1a represents a metal atom on the front side of the paper, and 1b represents a metal atom on the back side of the paper. The basic skeleton shown in FIG. 1 has a structure in which six metal atoms face each other with one face of the pentagonal pyramid including two arrangements located at the apex of the pentagonal pyramid. And one surface of this pentagonal pyramid is a bottom pentagon, and the surface of the pentagonal pyramid keeps a fixed angle. This angle is determined by the size of the metal atom or the like. For example, when the metal atom is a titanium atom, the angle is about 36 °. In FIG. 1, metal atoms are connected to each other for easy understanding, but actually, each metal atom may be bonded via a bridged oxygen atom.
The metal compound of the present invention has the basic skeleton shown in FIG. 1 as long as it has a crystal structure that includes two arrangements in which six metal atoms are located at the vertices of pentagonal pyramids in one molecule. It is not limited to. For example, one molecule has a crystal structure including two arrangements in which six metal atoms are spatially located at the vertices of a pentagonal pyramid, but the bond distances between the metal atoms and the metal atoms are not all the same, One molecule has a crystal structure including two arrangements in which six metal atoms are spatially located at the vertices of a pentagonal pyramid, but the pentagon located at the bottom of the pentagonal pyramid is not a regular pentagon, etc. included.
(2) Production Method The metal compound of the present invention comprises a metal alkoxide represented by the formula (1): M (OR) n (hereinafter referred to as “metal alkoxide”) and a reaction of two or more of the metal alkoxides. A composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts, a combination of two or more of the metal alkoxides, and two of the composite alkoxides The above combination, a combination of the metal alkoxide and the composite alkoxide (hereinafter referred to as “metal alkoxides”) can be produced by partial hydrolysis with a predetermined amount of water in an organic solvent.
In the metal alkoxide represented by the formula (1), in the formula (1), M represents a metal atom. Examples of the metal atom include one or more selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead, and titanium is particularly preferable. R represents an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 10, preferably 1 to 4 because it is easily available and has excellent handleability. N represents the valence of the metal atom.
Specific examples of the metal alkoxide represented by the formula (1) include Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 -i) 4 , Ti (OC 4 H 9 ). Titanium alkoxides such as 4 ; zirconium alkoxides such as Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (OC 3 H 7 ) 4 , Zr (OC 4 H 9 ) 4 ; Al (OCH 3 ) 3 , Al (OC 2 H 5 ) 3 , Al (OC 3 H 7 -i) 3 , Al (OC 4 H 9 ) 3 and other aluminum alkoxides; Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Silicon alkoxides such as Si (OC 3 H 7 -i) 4 , Si (OC 4 H 9 -t) 4 ; Germanium alkoxides such as Ge (OC 2 H 5 ) 4 ; In (OCH 3 ) 3 , In (OC 2) H 5) , In (OC 3 H 7 -i ) 3, In (OC 4 H 9) 3 such as indium alkoxide; Sn (OCH 3) 4, Sn (OC 2 H 5) 4, Sn (OC 3 H 7 -i) 4 , Sn (OC 4 H 9 ) 4 tin alkoxide; Ta (OCH 3 ) 5 , Ta (OC 2 H 5 ) 5 , Ta (OC 3 H 7 -i) 5 , Ta (OC 4 H 9 ) 5 Tungsten alkoxides such as W (OCH 3 ) 6 , W (OC 2 H 5 ) 6 , W (OC 3 H 7 -i) 6 , W (OC 4 H 9 ) 6, etc .; Zn (OC 2 H 5 ) zinc alkoxide such as 2 ; lead alkoxide such as Pb (OC 4 H 9 ) 4 and the like.
The composite alkoxide obtained by the reaction between two or more metal alkoxides includes a composite alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt form by a combination of Group IIIB elements. The composite alkoxide obtained by (1) can be illustrated.
Specific examples of these composite alkoxides, BaTi (OR) 6, SrTi (OR) 6, BaZr (OR) 6, SrZr (OR) 6, LiNb (OR) 6, LiTa (OR) 6, and combinations thereof, LiVO (OR) 4 , MgAl 2 (OR) 8 , (RO) 3 SiOAl (OR ′) 2 , (RO) 3 SiOTi (OR ′) 3 , (RO) 3 SiOZr (OR ′) 3 , (RO) 3 Examples thereof include a reaction product of a silicon alkoxide such as SiOB (OR ′) 2 , (RO) 3 SiONb (OR ′) 4 , (RO) 3 SiOTa (OR ′) 4 and the metal alkoxide, and a condensation polymer thereof. Here, R represents the same meaning as described above, and R ′ represents the same alkyl group as R.
Examples of the composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts include compounds obtained by reaction of metal salts with metal alkoxides. As the metal salt, chloride, nitrate, sulfate, acetate, formate, oxalate and the like can be used. Moreover, the same thing as the metal alkoxide mentioned above can be used as a metal alkoxide.
The metal alkoxide is used by dissolving or dispersing in a suitable organic solvent. The concentration of the metal alkoxide in the organic solvent is not particularly limited as long as it has a fluidity capable of suppressing rapid heat generation and can be stirred, but is usually 5 to 30% by weight.
The organic solvent to be used is not particularly limited as long as it is inert to the hydrolysis reaction of metal alkoxides. In order to carry out the hydrolysis reaction of metal alkoxides at a low temperature, those having a low freezing point, preferably 0 ° C. or lower, more preferably −50 ° C. or lower are suitable. Specific examples include ether solvents and aromatic hydrocarbon solvents.
Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran, dioxane and the like. Aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, chlorotoluene, bromobenzene, cumene, tetralin, butylbenzene, cymene, diethylbenzene, pentylbenzene, dipentylbenzene, benzyl acetate, etc. It is done. These solvents can be used alone or in combination of two or more. Among these, use of toluene or tetrahydrofuran is preferable because the metal compound of the present invention can be obtained with high yield.
When the metal alkoxide is not uniformly mixed with an organic solvent, for example, 1,2-bis- (2-ethylhexyloxycarbonyl) -1-ethanesulfonic acid sodium, polyoxyethylene (6) nonylphenyl ether, etc. It is preferable to make the solution uniform by adding a surfactant, stirring treatment, ultrasonic treatment or the like.
The amount of the organic solvent used is usually 10 to 5,000 parts by weight, preferably 100 to 3,000 parts by weight, based on 100 parts by weight of the metal alkoxide. If the amount is less than 10 parts by weight, the produced fine particles may grow in a combined state, and particle size control may be difficult. There is.
The water used for the hydrolysis of the metal alkoxide is not particularly limited as long as it is neutral, but pure water, distilled water or ion-exchanged water with a low impurity content is preferable from the viewpoint of suppressing side reactions.
The amount of water involved in the reaction is not particularly limited, but specifically, it may be 0.5 to 1.5 times mol, preferably 0.5 to 1.25 times mol, etc. relative to the metal alkoxide. it can.
As a method for adding water, any of a method of continuously adding the entire amount of water used and a method of adding a plurality of divided portions may be used. As will be described later, when water is added in a plurality of times, the temperature at the time of addition may be changed. For example, the first addition of water can be performed at −25 ° C. to −20 ° C., and the second addition can be performed at −80 ° C. to −70 ° C.
Moreover, water can also be diluted and used for a suitable organic solvent. By using diluted water in the organic solvent, local heat generation at the time of dropping of water can be prevented, and the metal alkoxide can be homogeneously hydrolyzed. As the organic solvent used for diluting water, those compatible with water are preferable. For example, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol and the like can be mentioned.
In the hydrolysis reaction of the metal alkoxide with water, an acid, a base, or a dispersion stabilizer may be added.
Acids and bases produce dispersoids such as colloidal particles by deflocculating and dehydrating metal alkoxides and produced metal alkoxides as deflocculating agents that re-disperse the precipitates formed by condensation. The catalyst is not particularly limited as long as it functions as a catalyst for the production and as a dispersant for the produced dispersoid.
Examples of the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borohydrofluoric acid; organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid; diphenyl And a photoacid generator that generates an acid by light irradiation, such as iodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate. Examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, phosphine and the like.
The dispersion stabilizer refers to an agent such as a flocculating agent, a protective colloid, a coagulation inhibitor such as a surfactant and the like, which has the effect of stably dispersing the dispersoid in the dispersion medium. Specific examples thereof include polyvalent carboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid, and succinic acid; hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid; acetylacetone, methyl acetoacetate, Ethyl acetoacetate, acetoacetate-n-propyl, isopropyl acetoacetate, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexanedione, 2,4-heptanedione , 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl-hexanedione and other multidentate ligand compounds having strong chelating ability against metal atoms; .
As a method for performing a hydrolysis reaction between a metal alkoxide and water, (a) a method of adding water to an organic solvent solution of the metal alkoxide, (b) a metal alkoxide in a mixed solvent of water and an organic solvent The method of (a) is preferable because the metal compound of the present invention can be obtained with good yield. In particular, 0.6 times to 1.25 times the amount of water with respect to the metal alkoxide is slowly added to a solution in which the metal alkoxide is dissolved or dispersed in an organic solvent at −20 ° C. or less, and the reaction solution is obtained. Particularly preferred is a method in which the temperature is naturally raised (first step) and then refluxed (second step).
In the first step, it is considered that the low temperature hydrolysis reaction of the metal alkoxide mainly proceeds. For example, when titanium tetraisopropoxide is used as the metal alkoxide, a dispersion of fine particles having a loose crystal-like cage (chain) structure (quasi-stabilized structure) is obtained in the first step. The particle diameter of the obtained fine particles is 0.5 to 10 nm, preferably 1 to 5 nm.
The dropping temperature of water depends on the stability of the metal alkoxide used. Usually, there is no particular problem as long as the temperature is −20 ° C. or lower, but depending on the type of metal alkoxide, it may be more preferable to carry out in a temperature range of −50 ° C. to −100 ° C. Thus, by dripping water at low temperature, the dispersion liquid of the metal compound of the present invention in the form of fine particles can be obtained.
The dropping time of water depends on the reaction scale and the like, but is usually 10 minutes to 3 hours, preferably 15 minutes to 1 hour. After completion of the dropwise addition, the reaction solution is preferably warmed to room temperature and stirred for 1 to 24 hours for aging.
In the second step, the compound of the present invention is obtained by refluxing at the reflux temperature of the organic solvent using the reaction solution obtained in the first step. In this step, the dropped water is completely used for hydrolysis, and the compound of the present invention is produced by a polycondensation reaction (dehydration and dealcoholization reaction). The reflux time is not particularly limited, but is usually 30 minutes to 5 hours, preferably 1 to 3 hours. The solution containing the metal compound of the present invention obtained in the second step is a monodisperse dispersoid having an average particle size of 1 to 10 nm and a particle size distribution of 0.1 to 50 nm, and has excellent storage stability. .
When the solution is allowed to stand at a temperature of room temperature or lower, crystals precipitate and can be isolated as the metal compound of the present invention.
The isolated metal compound crystal of the present invention can be treated with less than 0.25 moles of water relative to the metal compound to obtain a new dispersoid. The dispersoid obtained here forms a dispersoid that is monodisperse equivalent to the solution containing the metal compound obtained in the second step and has excellent storage stability. The dispersoid becomes a dispersoid having a metal-oxygen bond adjusted in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent.
The metal compound of the present invention is stable and excellent in dispersibility in various organic solvents. As described below, the metal compound of the present invention can be dispersed in an organic solvent after being isolated, or by using the reaction solution obtained by the above-described production method as it is, as described below. It is useful as a material for forming materials and organic-inorganic composite hybrids.
That is, when a solution obtained by dispersing the metal compound of the present invention in an organic solvent is applied or sprayed onto a substrate, a metal oxide film can be formed on the substrate. For example, it can be produced by applying or spraying this solution onto a substrate, followed by heating and drying at a temperature of 200 ° C. or lower, preferably 150 ° C. or lower, to form a film. By heating, the solvent is dried, and the product is hydrolyzed and dehydrated. The heating time is not particularly limited, but is usually in the range of 1 to 120 minutes.
The concentration of the metal compound of the present invention in the solution is not particularly limited as long as it can be applied onto the substrate, and can be appropriately set depending on the application method and the set film thickness. Generally, it is in the range of 5 to 50% by weight in terms of oxide.
The organic solvent to be used is not particularly limited as long as it does not affect the dispersibility of the metal compound of the present invention. Specifically, the solvent illustrated as a solvent which can be used when manufacturing the metal compound of the said this invention is mentioned.
The film surface of the metal oxide film formed using the solution containing the metal compound of the present invention has an average roughness of 10 nm or less, preferably 5 nm or less, excellent flatness, wettability, water repellency, and storage. Excellent stability. Moreover, since it can form into a film by drying at the temperature of 200 degrees C or less, it can also form into a film also on a plastic substrate. That is, a metal oxide film having a high-density smooth film surface with a carbon content of 10% or less can be formed on a plastic substrate.
There is no particular limitation on the method for applying the solution containing the metal compound of the present invention to the substrate. For example, any known method such as spin coating, dip coating, spray coating, roll coating, screen printing, or offset printing can be used. Among these, the screen printing method, offset printing method, and roll coating method, which can be patterned at the time of coating, are preferable, and mass production can be performed at low cost. Roll coating methods such as a roll coating method using a bar and a roll coating method using a guser. Is more preferable.
In the case of forming a metal oxide thin film from the metal compound of the present invention, it is preferable to irradiate with light during and / or after heating of the coating film. The light source for irradiating the coating film with ultraviolet light or visible light is not particularly limited as long as it generates light having a wavelength of 150 nm to 700 nm. For example, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, a sodium lamp, and the like can be given. An ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, and a xenon lamp are preferable.
Moreover, if a photomask is used in combination, a transparent conductive pattern can be formed. A laser oscillation device can also be used. When a laser beam is used, a metal oxide other than the irradiated portion does not become a metal oxide, so that a desired pattern can be formed without using screen printing or the like at the time of application.
When the reaction of the coating solution containing the metal compound of the present invention is carried out, the metal hydroxide remains with the formation of the metal oxide. In consideration of the absorption of the metal-OH bond, it is preferable to use an apparatus that generates light including ultraviolet light of 400 nm or less. Furthermore, when a metalloxane network is formed as the dehydration reaction proceeds, the absorption of the metal-O-metal bond is shorter than that of the metal-OH bond, but the metal-O-metal bond may be activated. Crystallization of the metal oxide is promoted by light irradiation with a wavelength that can be generated. Although irradiation time is not specifically limited, Usually, it is 1 minute-120 hours.
There are no particular restrictions on the material and size of the substrate. Examples of the material of the substrate include metal, ceramics, glass, plastic, paper, fiber, leather, and the like. The shape of the substrate may be any shape such as a sheet shape, a plate shape, a film shape, and a three-dimensional object. An already painted substrate can also be used.
Moreover, the organic solvent dispersion liquid of the metal compound of the present invention is also useful as a material for forming a chemical adsorption film. For example, a chemical adsorption film forming solution is prepared by adding a predetermined amount of an organic solvent dispersion of the metal compound of the present invention to an organic solvent solution of a metal surfactant such as alkyltrialkoxysilane or fluoroalkyltrialkoxysilane. By applying and drying this onto a surface of a substrate such as a glass substrate, a chemically adsorbed film composed of a good and dense single molecule can be formed. The substrate used for forming the chemisorbed film is not particularly limited, and examples thereof include those listed as substrates that can be used for forming the metal oxide film. In addition, the metal compound of the present invention is useful as an organic-inorganic composite hybrid material.
図１は、本発明の金属化合物の基本骨格を示した図である。
図２は、実施例１で得られたゾルの溶液の粒子径分布を測定したチャート図である。
図３は、実施例１で得られた結晶の１Ｈ−ＮＭＲを測定したチャート図である。
図４は、実施例１で得られた結晶中のユニットセルを構成する各分子構造を示す図である。
図５は、実施例１で得られた結晶中の分子配列を示す図である。
図６は、実施例２で得られた反応液のラマンスペクトルを測定したチャート図である。
図７は、実施例２で得られた反応液の１７Ｏ−ＮＭＲを測定したチャート図である。FIG. 1 is a diagram showing the basic skeleton of the metal compound of the present invention.
FIG. 2 is a chart showing the particle size distribution of the sol solution obtained in Example 1.
3 is a chart showing the 1 H-NMR measurement of the crystal obtained in Example 1. FIG.
FIG. 4 is a diagram showing each molecular structure constituting the unit cell in the crystal obtained in Example 1.
FIG. 5 is a diagram showing the molecular arrangement in the crystal obtained in Example 1.
6 is a chart showing the Raman spectrum of the reaction solution obtained in Example 2. FIG.
FIG. 7 is a chart obtained by measuring 17 O-NMR of the reaction solution obtained in Example 2.
以下、実施例を用いて本発明をさらに詳細に説明するが、本発明の範囲は実施例に限定されるものではない。なお、有機溶媒は、モレキュラーシーブス（４Ａ１／１６、和光純薬工業製）で乾燥したものを使用した。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the scope of the present invention is not limited to an Example. The organic solvent used was dried with molecular sieves (4A1 / 16, manufactured by Wako Pure Chemical Industries, Ltd.).
チタンテトライソプロポキシド（日本曹達（株）製Ａ−１：純度９９．９％、酸化チタン換算濃度２８重量％）１００ｇ（０．３５ｍｏｌ）を４つ口フラスコ中で、トルエン（ナカライテスク社製）３７０ｇに溶解し、窒素ガス置換した後に、ドライアイスを加えたメタノール浴で冷却し、−２０℃とした。別に調製したイソプロピルアルコール（ナカライテスク社製）５１．７ｇで希釈した蒸留水（ＡＤＢＡＮＴＥＣ ＧＳ−２００より採水）６．３７ｇ（Ｈ２Ｏ／Ｔｉ＝１．０ｍｏｌ／ｍｏｌ）の混合溶液を、−２５〜−２０℃で撹拌しながら３０分間で滴下した。滴下終了後、反応液の撹拌を継続しながら、１．５時間かけて徐々に室温まで自然昇温し、さらに、８０℃で２．５時間還流して、無色透明な酸化チタン換算濃度３０重量％のゾルの溶液を得た。この溶液の光透過率５０％の光の透過波長は３８５ｎｍであった。得られたゾル溶液の粒径を測定した。
（粒径）
得られたゾル溶液の粒径を、動的光散乱法（Ｍａｌｖｅｒｎ社製、ＨＰＰＳ）を用いてトルエン溶媒中、２５℃で測定した。測定した粒度分布を図２に示す。
ゾルは、図２に示すように、平均粒径１．２２ｎｍでシャープな単分散の粒度分布を示した。図２中、横軸は粒子径（ｎｍ）、縦軸はピーク強度（存在量）をそれぞれ示す。
次いで、反応液から析出した白色結晶を濾取し、真空乾燥した。得られた結晶の１Ｈ−ＮＭＲの測定およびＸ線構造解析を行った。
（１Ｈ−ＮＭＲ）
得られた結晶をＣ６Ｄ６に溶解させて、内部標準ＴＭＳとして測定した。測定した１Ｈ−ＮＭＲチャートを図３に示す。図３中、横軸はケミカルシフト（δｐｐｍ）を示す。
（Ｘ線結晶解析）
得られた結晶の分子構造および結晶構造は、Ｘ線構造解析装置（Ｒｉｇａｋｕイメージングプレート単結晶自動Ｘ線構造解析装置Ｒ−ＡＸＩＳ ＲＡＰＩＤ／ＬＳ）を用いて測定して決定した。構造解析精密化における最終のＲ値は０．０７であった。
組成式：Ｃ５４Ｈ１２６Ｏ３３Ｔｉ１２（分子量＝１８７７．９２）
結晶系：斜方晶系
格子定数：ａ＝２６．６９Å、ｂ＝２８．３５Å、ｃ＝２４．１６Å、α＝β＝γ＝９０°
上記測定結果より、本発明の結晶中には、１２個のチタン原子が酸素原子によって架橋されたかご状構造（かご状チタニア）に、１８個のイソプロポキシ基が結合した構造である結晶学的に異なる２種類の分子Ａ、Ｂから構成されているユニットセルが、存在することが分かった。かご状チタニアは、チタン原子を頂点とする２つの五角錐が、該五角錐の１つの面を向けて対峙し、この五角錐の１つの面が、底面五角形同士であって、前記五角錐の面が、約３６°の角度を持って対峙した構造を有している。
このユニットセルを構成する各分子の構造を図４に示す。図４中、１はチタン原子（黒い丸印）、２は酸素原子（灰色の丸印）、３は炭素原子（白い丸印）をそれぞれ表す。図４中、分子Ａ（ｍｏｌｅｃｕｌｅＡ）と分子Ｂ（ｍｏｌｅｃｕｌｅＢ）とは組成式が同じであり、互いに近似した構造を有する。各分子の粒子径は１．２〜１．３ｎｍである。なお、図４に示すものは紙面上側から見た図であり、１２個のチタン原子、チタン原子間を架橋する酸素原子および１８個のイソプロポキシ基の全ては表されていない。
得られた結晶の分子配列を図５に示す。図５に示すように、得られた結晶は分子Ａと分子Ｂとが交互に繰り返す構造を有しており、分子Ａと分子Ｂとの間には、溶媒であるトルエン分子４が取り込まれている。トルエン分子は、あたかもパテの如き役割を担っていると考えられる。
（参考例１）
実施例１で得られたゾルの溶液を、表面がオゾン処理されたポリエチレンテレフタレート基板（１０ｃｍ×１０ｃｍ、厚み５ｍｍ）上にＮｏ．３のバーコーターを用いて塗布し、１００℃で１０分間乾燥して、該基板上に金属酸化物膜を形成した。ＳＰＭ装置（セイコーインスツルメント社製、ＳＰＡ−４００（ＳＩＩ））を用いて該膜表面の形状を測定したところ、その表面の粗さは５ｎｍ以下であり、本発明の金属化合物の分散液から形成された金属酸化物膜は平滑であることが分かった。Titanium tetraisopropoxide (A-1 manufactured by Nippon Soda Co., Ltd .: purity 99.9%, titanium oxide equivalent concentration 28% by weight) 100 g (0.35 mol) in a four-necked flask, toluene (manufactured by Nacalai Tesque) ) After dissolving in 370 g and substituting with nitrogen gas, it was cooled in a methanol bath to which dry ice was added, and the temperature was set to -20 ° C. Separately prepared 6.37 g (H 2 O / Ti = 1.0 mol / mol) of a mixed solution of distilled water (collected from ADBANTEC GS-200) diluted with 51.7 g of isopropyl alcohol (manufactured by Nacalai Tesque) The mixture was added dropwise over 30 minutes while stirring at 25 to -20 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred and gradually warmed to room temperature over 1.5 hours, and further refluxed at 80 ° C. for 2.5 hours to obtain a colorless and transparent titanium oxide equivalent concentration of 30 wt. % Sol solution was obtained. The transmission wavelength of light with a light transmittance of 50% of this solution was 385 nm. The particle size of the obtained sol solution was measured.
(Particle size)
The particle size of the obtained sol solution was measured at 25 ° C. in a toluene solvent using a dynamic light scattering method (manufactured by Malvern, HPPS). The measured particle size distribution is shown in FIG.
As shown in FIG. 2, the sol showed a sharp monodisperse particle size distribution with an average particle size of 1.22 nm. In FIG. 2, the horizontal axis represents the particle diameter (nm), and the vertical axis represents the peak intensity (abundance).
Next, white crystals precipitated from the reaction solution were collected by filtration and dried in vacuo. 1 H-NMR measurement and X-ray structural analysis of the obtained crystal were performed.
(1 H-NMR)
The obtained crystals were dissolved in C 6 D 6 and measured as an internal standard TMS. The measured 1 H-NMR chart is shown in FIG. In FIG. 3, the horizontal axis indicates the chemical shift (δppm).
(X-ray crystal analysis)
The molecular structure and crystal structure of the obtained crystal were determined by measurement using an X-ray structure analyzer (Rigaku imaging plate single crystal automatic X-ray structure analyzer R-AXIS RAPID / LS). The final R value in the structural analysis refinement was 0.07.
Composition formula: C 54 H 126 O 33 Ti 12 (Molecular weight = 1877.92)
Crystalline system: orthorhombic system Lattice constants: a = 26.69Å, b = 28.35Å, c = 24.16Å, α = β = γ = 90 °
From the above measurement results, the crystal of the present invention has a crystallographic structure in which 18 isopropoxy groups are bonded to a cage structure (cage titania) in which 12 titanium atoms are bridged by oxygen atoms. It was found that there are unit cells composed of two different types of molecules A and B. In the cage-like titania, two pentagonal pyramids having a titanium atom as a vertex face each other with one surface of the pentagonal pyramid facing each other, and one surface of the pentagonal pyramid is a bottom pentagon, and the pentagonal pyramids The faces have a structure facing each other with an angle of about 36 °.
The structure of each molecule constituting this unit cell is shown in FIG. In FIG. 4, 1 represents a titanium atom (black circle), 2 represents an oxygen atom (gray circle), and 3 represents a carbon atom (white circle). In FIG. 4, the molecule A (molecule A) and the molecule B (molecule B) have the same composition formula and have structures close to each other. The particle diameter of each molecule is 1.2 to 1.3 nm. 4 is a view as seen from the upper side of the drawing, and does not show all 12 titanium atoms, oxygen atoms bridging between the titanium atoms, and 18 isopropoxy groups.
The molecular arrangement of the obtained crystal is shown in FIG. As shown in FIG. 5, the obtained crystal has a structure in which a molecule A and a molecule B are alternately repeated, and a toluene molecule 4 as a solvent is taken in between the molecule A and the molecule B. Yes. The toluene molecule is thought to play a role like putty.
(Reference Example 1)
The sol solution obtained in Example 1 was subjected to No. 1 on a polyethylene terephthalate substrate (10 cm × 10 cm,
実施例１で得られた反応液から析出した白色結晶を濾取し、真空乾燥して得られた結晶を、再びトルエン（ナカライテスク社製）に溶解し、窒素ガス置換した後、チタンアルコキシドに対し０．２５倍モルの水を加えて透明なゾル溶液を調整した。
得られたゾルの溶液の粒子は、平均粒子径５．２ｎｍでシャープな粒度分布を示した。
次いで、得られた反応液のラマンスペクトルを測定し、その結果を図６に示す。０．２５倍モルの水として１７Ｏ標識水を用い、反応液の１７Ｏ−ＮＭＲを測定し、その結果を図７に示す。The white crystals precipitated from the reaction solution obtained in Example 1 were collected by filtration and vacuum-dried. The crystals obtained by dissolving again in toluene (manufactured by Nacalai Tesque) were replaced with nitrogen gas, and then replaced with titanium alkoxide. On the other hand, a transparent sol solution was prepared by adding 0.25 moles of water.
The particles of the obtained sol solution showed a sharp particle size distribution with an average particle size of 5.2 nm.
Subsequently, the Raman spectrum of the obtained reaction liquid was measured, and the result is shown in FIG. Using 17 O-labeled water as 0.25-fold moles of water, 17 O-NMR of the reaction solution was measured, and the results are shown in FIG.
本発明によれば、酸や塩基によりｐＨを調整したり、分散安定化剤を添加しなくとも有機溶媒中で凝集することがない、新規な結晶構造を有する金属化合物が提供される。本発明の金属化合物は、金属酸化物膜や化学吸着膜の形成用材料、有機−無機複合ハイブリッド材料等として有用であり、産業上の利用価値は高いといえる。 ADVANTAGE OF THE INVENTION According to this invention, the metal compound which has a novel crystal structure which does not aggregate in an organic solvent, without adjusting pH with an acid or a base, or adding a dispersion stabilizer is provided. The metal compound of the present invention is useful as a material for forming a metal oxide film or a chemical adsorption film, an organic-inorganic composite hybrid material, and the like, and can be said to have high industrial utility value.
Claims (4)
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| JP2003156437 | 2003-06-02 | ||
| JP2003156437 | 2003-06-02 | ||
| JP2003158012 | 2003-06-03 | ||
| JP2003158012 | 2003-06-03 | ||
| PCT/JP2004/007914 WO2005012215A1 (en) | 2003-06-02 | 2004-06-01 | Metal compound having novel skeleton |
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| JPWO2005012215A1 JPWO2005012215A1 (en) | 2006-09-14 |
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| WO2013035672A1 (en) | 2011-09-05 | 2013-03-14 | 東ソー株式会社 | Film-forming material, group iv metal oxide film and vinylene diamide complex |
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| JP4585256B2 (en) * | 2004-09-06 | 2010-11-24 | 日本曹達株式会社 | Method for producing dispersion containing fine particles of titanium compound |
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| JPS6452786A (en) * | 1987-05-21 | 1989-02-28 | Nippon Soda Co | Cyclic titanoxane, production thereof and surface-treating agent |
| JPH01129032A (en) * | 1987-11-12 | 1989-05-22 | Nippon Soda Co Ltd | Ladderlike polytitanoxane and its production |
| JPH01230406A (en) * | 1988-03-11 | 1989-09-13 | Koroido Res:Kk | Production of viscous sol from metal alkoxide |
| JP2000086769A (en) * | 1998-09-14 | 2000-03-28 | Matsumoto Seiyaku Kogyo Kk | Production of soluble solid polytitanoxane and its derivative |
| JP2000264893A (en) * | 1999-01-14 | 2000-09-26 | Jsr Corp | Metal complex, production of metal complex, aqueous solution of metal complex and metal oxide |
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2004
- 2004-06-01 WO PCT/JP2004/007914 patent/WO2005012215A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452786A (en) * | 1987-05-21 | 1989-02-28 | Nippon Soda Co | Cyclic titanoxane, production thereof and surface-treating agent |
| JPH01129032A (en) * | 1987-11-12 | 1989-05-22 | Nippon Soda Co Ltd | Ladderlike polytitanoxane and its production |
| JPH01230406A (en) * | 1988-03-11 | 1989-09-13 | Koroido Res:Kk | Production of viscous sol from metal alkoxide |
| JP2000086769A (en) * | 1998-09-14 | 2000-03-28 | Matsumoto Seiyaku Kogyo Kk | Production of soluble solid polytitanoxane and its derivative |
| JP2000264893A (en) * | 1999-01-14 | 2000-09-26 | Jsr Corp | Metal complex, production of metal complex, aqueous solution of metal complex and metal oxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013035672A1 (en) | 2011-09-05 | 2013-03-14 | 東ソー株式会社 | Film-forming material, group iv metal oxide film and vinylene diamide complex |
| KR20140078614A (en) * | 2011-09-05 | 2014-06-25 | 도소 가부시키가이샤 | Film-forming material, group iv metal oxide film and vinylene diamide complex |
| US9371452B2 (en) | 2011-09-05 | 2016-06-21 | Tosoh Corporation | Film-forming material, group IV metal oxide film and vinylenediamide complex |
| KR101892786B1 (en) * | 2011-09-05 | 2018-08-28 | 도소 가부시키가이샤 | Film-forming material, group iv metal oxide film and vinylene diamide complex |
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| WO2005012215A1 (en) | 2005-02-10 |
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