JP6087389B2 - Tetragonal zirconium oxide nanoparticles, method for producing the same, dispersion, and resin composite - Google Patents
Tetragonal zirconium oxide nanoparticles, method for producing the same, dispersion, and resin composite Download PDFInfo
- Publication number
- JP6087389B2 JP6087389B2 JP2015112828A JP2015112828A JP6087389B2 JP 6087389 B2 JP6087389 B2 JP 6087389B2 JP 2015112828 A JP2015112828 A JP 2015112828A JP 2015112828 A JP2015112828 A JP 2015112828A JP 6087389 B2 JP6087389 B2 JP 6087389B2
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- JP
- Japan
- Prior art keywords
- zirconium oxide
- oxide nanoparticles
- carboxylic acid
- tetragonal
- tetragonal zirconium
- Prior art date
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims description 75
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 71
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 67
- 239000002105 nanoparticle Substances 0.000 title claims description 59
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- 239000006185 dispersion Substances 0.000 title description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 21
- -1 amine compound Chemical class 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 16
- 230000000087 stabilizing effect Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 4
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000013078 crystal Substances 0.000 description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
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- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 description 3
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- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- AIQRTHPXPDTMBQ-UHFFFAOYSA-K yttrium(3+);triacetate;tetrahydrate Chemical compound O.O.O.O.[Y+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AIQRTHPXPDTMBQ-UHFFFAOYSA-K 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Description
本発明は、正方晶酸化ジルコニウムナノ粒子、その製造方法、正方晶酸化ジルコニウムナノ粒子分散体および正方晶酸化ジルコニウムナノ粒子が均一分散した樹脂複合体に関する。 The present invention relates to tetragonal zirconium oxide nanoparticles, a production method thereof, a tetragonal zirconium oxide nanoparticle dispersion, and a resin composite in which tetragonal zirconium oxide nanoparticles are uniformly dispersed.
近年、金属酸化物のナノ粒子は、光学材料、電子部品材料、磁気記録材料、触媒材料、紫外線や近赤外吸収材料など様々な材料の高機能化や高性能化に寄与するものとして非常に注目されている。 In recent years, nanoparticles of metal oxides have been very important as contributing to higher functionality and higher performance of various materials such as optical materials, electronic component materials, magnetic recording materials, catalyst materials, ultraviolet and near infrared absorbing materials. Attention has been paid.
例えば、特許文献１には、熱可塑性樹脂に無機酸化物微粒子を混合分散させて高屈折率で低分散の光学材料を製造する技術が開示されている。無機酸化物微粒子の一つであり、屈折率が高い酸化ジルコニウムナノ粒子をこのような技術に適用することにより高屈折率の光学材料を開発することが可能となる。 For example, Patent Document 1 discloses a technique for manufacturing an optical material having a high refractive index and a low dispersion by mixing and dispersing inorganic oxide fine particles in a thermoplastic resin. By applying zirconium oxide nanoparticles, which are one of inorganic oxide fine particles and having a high refractive index, to such a technique, it becomes possible to develop an optical material having a high refractive index.
従来、酸化ジルコニウム粉末は、工業的には、ジルコニウム塩水溶液を加水分解し、次いで、得られた水和ジルコニアを分離した後、仮焼する加水分解法（特許文献２）や、水和ジルコニア微粒子の懸濁液に、アンモニアを添加して固形物を沈殿させ、次いで、得られた水和ジルコニウムを分離し、仮焼する加水分解中和法（ 特許文献３） によって製造されている。 Conventionally, zirconium oxide powder is industrially hydrolyzed from an aqueous zirconium salt solution, then separated from the obtained hydrated zirconia and then calcined (Patent Document 2), or hydrated zirconia fine particles. The suspension is prepared by the hydrolysis neutralization method (Patent Document 3) in which ammonia is added to precipitate a solid, and then the obtained hydrated zirconium is separated and calcined.
また、ハロゲン化ジルコニウムを気化させ、この蒸気を、火炎中で反応させた後、酸化ジルコニウムに付着しているハロゲニドを熱処理により除去する方法（特許文献４）、ジルコニウム化合物の水溶液を、１００〜２２０℃ で水熱処理した後、乾燥及び熱処理することにより、０．１〜０．８μｍ の単分散球状超微粉粒子を製造する方法（特許文献５） 、水酸化ジルコニウムの仮焼物を、ジルコニア製のボールを備えた粉砕機により湿式粉砕して、平均粒径１μｍ以下に粉砕する方法（特許文献６）等が報告されている。 Further, after vaporizing zirconium halide and reacting this vapor in a flame, the halogenide adhering to the zirconium oxide is removed by heat treatment (Patent Document 4), and an aqueous solution of a zirconium compound is 100 to 220. A method of producing monodispersed spherical ultrafine particles of 0.1 to 0.8 μm by hydrothermal treatment at 0 ° C., followed by drying and heat treatment (Patent Document 5), a calcined product of zirconium hydroxide, a zirconia ball (Patent Document 6) and the like have been reported which are wet pulverized by a pulverizer equipped with a pulverizer and pulverized to an average particle size of 1 μm or less.
さらに、特許文献７には、ジルコニウム化合物を、亜臨界ないし超臨界状態の水を媒体として水熱反応させることにより、短時間での反応で、結晶構造を制御したナノサイズの酸化ジルコニウム結晶粒子の製造方法が開示されている。 Furthermore, Patent Document 7 discloses that nanosized zirconium oxide crystal particles whose crystal structure is controlled in a short time by allowing a zirconium compound to undergo a hydrothermal reaction using water in a subcritical or supercritical state as a medium. A manufacturing method is disclosed.
ところで、酸化ジルコニウムには、立方晶、単斜晶および正方晶の３種の結晶形が知られているが、正方晶の屈折率が高いため高屈折率光学材料用途には正方晶がより好ましい。 By the way, three kinds of crystal forms of cubic oxide, monoclinic crystal, and tetragonal crystal are known for zirconium oxide, but tetragonal crystal is more preferable for high refractive index optical material use because of its high refractive index. .
そこで、 特許文献８では、カルボン酸のジルコニウム複合体を水熱反応させ、その反応後の上澄み液のｐHを６〜８とすることによって、単斜晶を含まない正方晶酸化ジルコニウムナノ粒子が製造できるとしている。 Therefore, in Patent Document 8, tetragonal zirconium oxide nanoparticles containing no monoclinic crystals are produced by hydrothermal reaction of a zirconium complex of carboxylic acid and setting the pH of the supernatant after the reaction to 6-8. I can do it.
また、特許文献９には、ジルコニア（酸化ジルコニウム）０．９８〜０．９モルに対して希土類金属酸化物０．０２〜０．１モルを含有する安定化ジルコニア微粒子が開示され、その結晶化構造は正方晶であると記載されている。 Patent Document 9 discloses stabilized zirconia fine particles containing 0.02 to 0.1 mol of rare earth metal oxide with respect to 0.98 to 0.9 mol of zirconia (zirconium oxide). The structure is described as tetragonal.
さらに、特許文献１０には、分散粒径が１ｎｍ以上かつ２０ｎｍ以下の正方晶ジルコニア粒子を含有してなるジルコニア透明分散液が開示され、その分散体を利用して屈折率が高く、透明性に優れ、しかも機械的特性が向上した透明複合体を得ることができるとしている。 Furthermore, Patent Document 10 discloses a zirconia transparent dispersion liquid containing tetragonal zirconia particles having a dispersed particle diameter of 1 nm or more and 20 nm or less, and the dispersion is used to provide a high refractive index and make it transparent. It is said that a transparent composite with excellent mechanical properties can be obtained.
しかしながら、特許文献８で得られる正方晶酸化ジルコニウムは、カルボン酸に被覆されベンゼン、シクロヘキサン等の非極性溶媒には分散するとされているが、その分散状態の記載がなく、主として正方晶であると記載されていることから正方晶以外の結晶を含まないわけではない。また、比較的極性の高い溶媒やモノマーに分散させる場合は、さらに他の被覆剤で被覆する必要があるといった問題がある。 However, the tetragonal zirconium oxide obtained in Patent Document 8 is coated with a carboxylic acid and dispersed in a nonpolar solvent such as benzene and cyclohexane. However, there is no description of the dispersion state, and it is mainly tetragonal. Since it is described, it does not include crystals other than tetragonal crystals. In addition, when dispersed in a solvent or monomer having a relatively high polarity, there is a problem that it is necessary to coat with another coating agent.
特許文献９の安定化ジルコニア微粒子は正方晶のみからなるが、その製造にあたっては特殊な条件、すなわち亜臨界ないし超臨界状態の水を媒体として用いるため反応温度を３００〜４００℃、反応圧力を２０〜４０ＭＰａといった特殊な条件にする必要がある。 また、特許文献１０の正方晶ジルコニアは、実施例によると、オキシ塩化ジルコニウムの水溶液を希アンモニア水で処理してジルコニア前駆体スラリーとし、このスラリーに硫酸ナトリウム水溶液を加え、この混合物を１３０℃で乾燥、さらに５００℃で焼成して得られた混合物に水を加えてスラリーとし、それを遠心分離することによって精製、次いで乾燥させる、といった複雑で、大量のエネルギーを必要とする工程によって製造されるばかりでなく、その分散液は、多量の分散剤を使用して分散させる必要がある（例えば、その実施例１によるとジルコニア粒子１０ｇに対して３ｇの分散剤を加えている。）ため、ジルコニア粒子をモノマーに分散して重合させる場合など、その得られた樹脂複合体の物性への分散剤の影響が無視できないといった問題がある。 The stabilized zirconia fine particles of Patent Document 9 are composed only of tetragonal crystals, but in the production thereof, a reaction temperature of 300 to 400 ° C. and a reaction pressure of 20 are used because subcritical or supercritical water is used as a medium. It is necessary to use special conditions such as ˜40 MPa. In addition, according to the example, tetragonal zirconia of Patent Document 10 is obtained by treating an aqueous solution of zirconium oxychloride with dilute ammonia water to obtain a zirconia precursor slurry, adding an aqueous sodium sulfate solution to the slurry, and mixing the mixture at 130 ° C. Manufactured by a process that requires a large amount of energy, such as drying and further adding water to the mixture obtained by baking at 500 ° C. to form a slurry, which is purified by centrifuging and then dried. Not only that, but the dispersion needs to be dispersed using a large amount of a dispersant (for example, according to Example 1, 3 g of a dispersant is added to 10 g of zirconia particles), and thus zirconia is added. The influence of the dispersant on the physical properties of the resulting resin composite is negligible, such as when particles are dispersed in a monomer for polymerization. There is a Itoitta problem.
従って、本発明は、特殊なまたは複雑な工程を用いなくても得られる、正方晶のみで、かつ有機溶媒、モノマー等への分散性に優れた酸化ジルコニウムナノ粒子、その製造方法、その分散体および樹脂複合体を提供することを課題とする。 Accordingly, the present invention provides a zirconium oxide nanoparticle that is obtained without using a special or complicated process and is only tetragonal and excellent in dispersibility in an organic solvent, a monomer, etc., a production method thereof, and a dispersion thereof Another object is to provide a resin composite.
本発明者は、鋭意検討した結果、ジルコニウム−アミン錯体に対してある種の金属元素を安定化元素として用い、カルボン酸と混合して、水熱反応させることによって正方晶酸化ジルコニウムナノ粒子を製造できること、さらに、その得られたナノ粒子が有機溶媒等への分散性に優れることを見出し、本発明を完成した。 As a result of intensive studies, the inventor produced tetragonal zirconium oxide nanoparticles by using a certain metal element as a stabilizing element for the zirconium-amine complex, mixing with carboxylic acid, and causing a hydrothermal reaction. Further, the present inventors have found that the obtained nanoparticles are excellent in dispersibility in an organic solvent and the like, and completed the present invention.
すなわち、本発明は、
（１） アルミニウム、マグネシウム、チタン及び希土類元素から選ばれる少なくとも１種の安定化元素を含有し、脂肪族カルボン酸および水酸基含有脂肪族カルボン酸で表面処理されていることを特徴とする正方晶酸化ジルコニウムナノ粒子、
（２） 前記正方晶酸化ジルコニウムナノ粒子に含まれる安定化元素とジルコニウム元素の原子数比が１／９９以上１／１０以下であることを特徴とする（１）記載の正方晶酸化ジルコニウムナノ粒子、
（３） 前記安定化元素がイットリウムであることを特徴とする（１）または（２）記載の正方晶酸化ジルコニウムナノ粒子、
（４） 前記脂肪族カルボン酸および水酸基含有脂肪族カルボン酸の炭素数が、３以上２２以下であることを特徴とする請求項１から３のいずれかに記載の正方晶酸化ジルコニウムナノ粒子、
（５） （１）から（４）のいずれかに記載の正方晶酸化ジルコニウムナノ粒子を、有機溶媒、モノマーおよび重合性オリゴマーから選ばれた少なくとも一つを含有する分散媒中に分散してなることを特徴とする正方晶酸化ジルコニウム分散体
（６） （１）から（４）のいずれかに記載の正方晶酸化ジルコニウムナノ粒子を、樹脂中に分散してなることを特徴とする樹脂複合体、
（７） ジルコニウム−アミン錯体に、水と、アルミニウム、マグネシウム、チタンおよび希土類元素の塩またはアルコキシドから選ばれた少なくとも１種と、カルボン酸とを添加する工程、およびその得られた混合物を水熱反応に供する工程を含むことを特徴とする正方晶酸化ジルコニウムナノ粒子の製造方法、
（８） 前記ジルコニウム−アミン錯体がオキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、オキシ酢酸ジルコニウム、オキシ炭酸ジルコニウム、テトラアルコキシジルコニウムおよびその部分加水分解縮合物から選ばれた少なくとも１種とアミン化合物とから製造されることを特徴とする（７）記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（９） 前記テトラアルコキシジルコニウムの各アルコキシ基の炭素数が１以上５以下であることを特徴とする（８）記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（１０） 前記アミン化合物が非芳香族アミン化合物であることを特徴とする（８）または（９）に記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（１１） 前記非芳香族アミン化合物がアルカノールアミンであることを特徴とする（１０）記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（１２） 前記アルカノールアミンがトリエタノールアミンおよびジエタノールアミンから選ばれた少なくとも一つあることを特徴とする（１１）記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（１３） 前記カルボン酸が、脂肪族カルボン酸および水酸基含有脂肪族カルボン酸から選ばれた少なくとも１種であることを特徴とする（７）から（１２）のいずれかに記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
（１４） 前記脂肪族カルボン酸および水酸基含有脂肪族カルボン酸の炭素数が、３以上２２以下であることを特徴とする（１３）記載の正方晶酸化ジルコニウムナノ粒子の製造方法、
である。
That is, the present invention
(1) Tetragonal oxidation characterized in that it contains at least one stabilizing element selected from aluminum, magnesium, titanium and rare earth elements and is surface-treated with an aliphatic carboxylic acid and a hydroxyl group-containing aliphatic carboxylic acid. Zirconium nanoparticles,
(2) The tetragonal zirconium oxide nanoparticles according to (1), wherein the atomic ratio of the stabilizing element and the zirconium element contained in the tetragonal zirconium oxide nanoparticles is 1/99 or more and 1/10 or less. ,
(3) The tetragonal zirconium oxide nanoparticles according to (1) or (2), wherein the stabilizing element is yttrium.
(4) The tetragonal zirconium oxide nanoparticles according to any one of claims 1 to 3, wherein the aliphatic carboxylic acid and the hydroxyl group- containing aliphatic carboxylic acid have 3 to 22 carbon atoms,
(5) The tetragonal zirconium oxide nanoparticles according to any one of (1) to (4) are dispersed in a dispersion medium containing at least one selected from an organic solvent, a monomer, and a polymerizable oligomer. Tetragonal zirconium oxide dispersion (6) characterized in that the tetragonal zirconium oxide nanoparticles according to any one of (1) to (4) are dispersed in a resin. ,
(7) A step of adding water, at least one selected from a salt or alkoxide of aluminum, magnesium, titanium, and a rare earth element to a zirconium-amine complex, and a carboxylic acid, and the resulting mixture hydrothermally A method for producing tetragonal zirconium oxide nanoparticles, comprising a step of subjecting to a reaction;
(8) The zirconium-amine complex is produced from an amine compound and at least one selected from zirconium oxychloride, zirconium oxynitrate, zirconium oxyacetate, zirconium oxycarbonate, tetraalkoxyzirconium, and partial hydrolysis condensates thereof. (4) the method for producing tetragonal zirconium oxide nanoparticles according to (7) ,
(9) The method for producing tetragonal zirconium oxide nanoparticles according to (8 ), wherein each alkoxy group of the tetraalkoxyzirconium has 1 to 5 carbon atoms,
(10) The method for producing tetragonal zirconium oxide nanoparticles according to (8) or (9) , wherein the amine compound is a non-aromatic amine compound,
(11) The method for producing tetragonal zirconium oxide nanoparticles according to (10 ), wherein the non-aromatic amine compound is an alkanolamine,
(12) The method for producing tetragonal zirconium oxide nanoparticles according to (11 ), wherein the alkanolamine is at least one selected from triethanolamine and diethanolamine,
(13) The tetragonal zirconium oxide according to any one of (7) to (12) , wherein the carboxylic acid is at least one selected from an aliphatic carboxylic acid and a hydroxyl group- containing aliphatic carboxylic acid Production method of nanoparticles,
(14) The method for producing tetragonal zirconium oxide nanoparticles according to (13 ), wherein the aliphatic carboxylic acid and the hydroxyl group- containing aliphatic carboxylic acid have 3 to 22 carbon atoms,
It is.
本発明によれば、安定化元素を含有し、カルボン酸で表面処理された正方晶のみの酸化ジルコニウムナノ粒子を製造することができる。 また、この正方晶酸化ジルコニウムナノ粒子は分散剤を用いなくても、有機溶媒、モノマー、重合性オリゴマー、樹脂等への分散性に優れた分散体を与える。 従って、この正方晶酸化ジルコニウムナノ粒子をモノマーや重合性オリゴマーに分散させて重合させることによって、高屈折率で透明な材料を得ることが可能となるため、高屈折率レンズ材料、高屈折率ハードコート材料などへ適用できる。 また、樹脂中に分散させてそれらの樹脂に機能を付加したり、光学的または機械的物性を改良したりできる。 According to the present invention, tetragonal zirconium oxide nanoparticles containing a stabilizing element and surface-treated with carboxylic acid can be produced. Further, the tetragonal zirconium oxide nanoparticles give a dispersion excellent in dispersibility in an organic solvent, a monomer, a polymerizable oligomer, a resin or the like without using a dispersant. Therefore, it is possible to obtain a transparent material with a high refractive index by dispersing the tetragonal zirconium oxide nanoparticles in a monomer or a polymerizable oligomer and polymerizing them. Applicable to coating materials. Moreover, it can disperse | distribute in resin and can add a function to those resin, or an optical or mechanical property can be improved.
以下、本発明を実施するための形態を詳細に説明する。なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更実施の形態が可能である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that this embodiment is merely an embodiment for carrying out the present invention, and the present invention is not limited by this embodiment, and various modified embodiments can be made without departing from the gist of the present invention. Is possible.
本発明の正方晶酸化ジルコニウムナノ粒子の製造方法は、ジルコニウム−アミン錯体に、水と、アルミニウム、マグネシウム、チタンおよび希土類元素の塩またはアルコキシドから選ばれた少なくとも１種と、カルボン酸とを添加する工程、およびその得られた混合物を水熱反応に供する工程を含むことを特徴とする。 In the method for producing tetragonal zirconium oxide nanoparticles of the present invention, water, at least one selected from aluminum, magnesium, titanium and rare earth element salts or alkoxides, and a carboxylic acid are added to the zirconium-amine complex. And a step of subjecting the obtained mixture to a hydrothermal reaction.
本発明のジルコニウム−アミン錯体は、オキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、オキシ酢酸ジルコニウム、オキシ炭酸ジルコニウム、テトラアルコキシジルコニウム、テトラアルコキシジルコニウムの部分加水分解縮合物等のジルコニウム化合物とアミン化合物とから製造される。 The zirconium-amine complex of the present invention is produced from a zirconium compound such as zirconium oxychloride, zirconium oxynitrate, zirconium oxyacetate, zirconium oxycarbonate, tetraalkoxyzirconium, and a partial hydrolysis condensate of tetraalkoxyzirconium and an amine compound. .
本発明で用いるテトラアルコキシジルコニウムのアルコキシ基は、同一または異なっていてもよく、また枝分かれしていてもよい炭素数１から５のアルコキシ基が好ましく、ｎ−プロポキシ基またはｎ−ブトキシ基が適度の反応性を有し、入手しやすいことから特に好ましい。 The alkoxy groups of tetraalkoxyzirconium used in the present invention may be the same or different and may be branched, preferably an alkoxy group having 1 to 5 carbon atoms, and an n-propoxy group or n-butoxy group is suitable. It is particularly preferable because it has reactivity and is easily available.
テトラアルコキシジルコニウムの部分加水分解縮合物は、テトラアルコキシジルコニウムを部分加水分解して得られる、Ｚｒ−O−Ｚｒ結合を介して連なった２量体、３量体、４量体等のオリゴマーを形成した化合物であるが、このようなオリゴマーもテトラアルコキシジルコニウムと同様に用いることができる。 また、このようなオリゴマーは、場合によってはテトラアルコキシジルコニウム中にも含まれていることがある。 Partially hydrolyzed condensates of tetraalkoxyzirconium form oligomers such as dimers, trimers, and tetramers linked via Zr-O-Zr bonds, obtained by partial hydrolysis of tetraalkoxyzirconium. Such oligomers can also be used in the same manner as tetraalkoxyzirconium. Moreover, such an oligomer may be contained also in the tetraalkoxy zirconium depending on the case.
本発明で用いるアミン化合物としては、非芳香族アミンが用いられる。 非芳香族アミンとしては、脂肪族アミンがあげられる。 例えば、プロピルアミン、ブチルアミン、オクチルアミン等の１級アミン、ジエチルアミン、ジプロピルアミン、ジオクチルアミン等の２級アミン、トリメチルアミン、トリエチルアミン等の３級アミンが例示できる。 A non-aromatic amine is used as the amine compound used in the present invention. Non-aromatic amines include aliphatic amines. Examples thereof include primary amines such as propylamine, butylamine and octylamine, secondary amines such as diethylamine, dipropylamine and dioctylamine, and tertiary amines such as trimethylamine and triethylamine.
また、アミノ基を２個以上もつもの、例えば、エチレンジアミン、ジエチレントリアミン、トリメチレンジアミン、トリエチレンテトラミン、Ｎ，Ｎ‘−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、トリス（２−アミノエチル）アミン、テトラエチレンペンタミン等や、水酸基を持つもの、例えば、エタノールアミン、トリエタノールアミン、アミノエチルエタノールアミン等のアルカノールアミンも好適に使用できる。 Also, those having two or more amino groups, such as ethylenediamine, diethylenetriamine, trimethylenediamine, triethylenetetramine, N, N′-dimethylethylenediamine, N, N-dimethylethylenediamine, tris (2-aminoethyl) amine, tetra Ethylenepentamine and the like, and those having a hydroxyl group, for example, alkanolamines such as ethanolamine, triethanolamine, and aminoethylethanolamine can be suitably used.
さらに、アミノカルボン酸化合物、例えば、グリシン、アラニン、アスパラギン酸、リシン等のα−アミノ酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、Ｎ−（２−ヒドロキシエチル）エチレンジアミン−Ｎ，Ｎ’，Ｎ‘−三酢酸、トリエチレンテトラミン−Ｎ，Ｎ，Ｎ’，Ｎ‘’，Ｎ‘’’，Ｎ‘’‘−六酢酸、１，３−プロパンジアミン-Ｎ，Ｎ，Ｎ’，Ｎ‘−四酢酸等が使用できる。 Further, aminocarboxylic acid compounds such as α-amino acids such as glycine, alanine, aspartic acid, lysine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N- (2-hydroxyethyl) ethylenediamine-N, N ′, N′-3 Acetic acid, triethylenetetramine-N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, 1,3-propanediamine-N, N, N ′, N′-tetraacetic acid, etc. Can be used.
前記記載のアミン化合物の中では、水溶性で反応性が高いものが好ましく、脂肪族の総炭素数が２〜１２の１級、２級または３級のアルキルアミン、総炭素数が２〜１２のアルキレンジアミン、または総炭素数が２〜１２のアルカノールアミンが特に好ましく用いられる。 Among the above-described amine compounds, those that are water-soluble and highly reactive are preferable, and primary, secondary, or tertiary alkylamines having 2 to 12 total aliphatic carbon atoms, and 2 to 12 total carbon atoms. Are particularly preferably used, or alkanolamines having 2 to 12 carbon atoms in total.
好ましいアルカノールアミンの具体例として、トリエタノールアミン、ジエタノールアミン、トリイソプロパノールアミン、ジイソプロパノールアミン、メチルジエタノールアミン、エチルジエタノールアミン等の一種単独または二種以上の組み合わせが挙げられる。 これらのアルカノールアミンのうち、トリエタノールアミン、ジエタノールアミンおよびこれらの混合物が金属錯体の保存安定性をより高めることができるため、特に好ましい。 Specific examples of preferable alkanolamines include one kind alone or a combination of two or more kinds such as triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine, and ethyldiethanolamine. Of these alkanolamines, triethanolamine, diethanolamine and mixtures thereof are particularly preferred because they can further enhance the storage stability of the metal complex.
本発明で用いるアミン化合物の使用量は、オキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、オキシ酢酸ジルコニウム、オキシ炭酸ジルコニウムおよびテトラアルコキシジルコニウム等のジルコニウム化合物に対し１〜４倍モルである。 １倍モル未満では錯体の生成が不十分となり、４倍モル超では反応しないアミン化合物が残存する。 The amount of the amine compound used in the present invention is 1 to 4 times the molar amount of the zirconium compound such as zirconium oxychloride, zirconium oxynitrate, zirconium oxyacetate, zirconium oxycarbonate and tetraalkoxyzirconium. If it is less than 1 mol, complex formation is insufficient, and if it exceeds 4 mol, an amine compound that does not react remains.
次いで、得られたジルコニウム−アミン錯体に、水と、アルミニウム、マグネシウム、チタンおよび希土類元素の塩またはアルコキシドから選ばれた少なくとも１種と、カルボン酸とを加える。 その添加順序は特に定められるものではないが、混合の操作性を考慮すると、上記記載のとおりの順序が好ましい。 Next, water, at least one selected from a salt or alkoxide of aluminum, magnesium, titanium, and a rare earth element, and a carboxylic acid are added to the obtained zirconium-amine complex. The order of addition is not particularly defined, but the order as described above is preferable in consideration of the operability of mixing.
前記したアルミニウム、マグネシウム、チタンおよび希土類元素から選ばれた少なくとも１種は、安定化元素として作用する。 すなわち、得られた正方晶酸化ジルコニウムナノ粒子の安定化に寄与するものと考えられる。 これらは塩またはアルコキシドとして添加され、塩化物や硝酸塩等の水溶性塩または低級アルコキシドが好ましく用いられる。 例えば、安定化元素がアルミニウムであるときは、アルミニウムイソプロポキシドが、安定化元素がイットリウムであるときは、塩化イットリウムまたは酢酸イットリウムが好ましく用いられる。 これらの安定化元素は、通常、ジルコニウム元素に対して、原子数比で１／９９以上１／１０以下の範囲で用いられる。 At least one selected from the aforementioned aluminum, magnesium, titanium and rare earth elements acts as a stabilizing element. That is, it is thought that it contributes to stabilization of the obtained tetragonal zirconium oxide nanoparticles. These are added as salts or alkoxides, and water-soluble salts such as chlorides and nitrates or lower alkoxides are preferably used. For example, aluminum isopropoxide is preferably used when the stabilizing element is aluminum, and yttrium chloride or yttrium acetate is preferably used when the stabilizing element is yttrium. These stabilizing elements are usually used in an atomic ratio of 1/99 or more and 1/10 or less with respect to the zirconium element.
前記カルボン酸は、脂肪族カルボン酸が好ましく、飽和、不飽和を問わず、炭素数が３から２２の脂肪族カルボン酸または水酸基含有脂肪族カルボン酸から選ばれた少なくとも１種以上が好ましく用いられ、有機溶媒、モノマー等への分散性を考慮するとその炭素数は６〜２２が特に好ましい。 The carboxylic acid is preferably an aliphatic carboxylic acid, and at least one selected from an aliphatic carboxylic acid having 3 to 22 carbon atoms or a hydroxyl group-containing aliphatic carboxylic acid, whether saturated or unsaturated, is preferably used. In view of dispersibility in organic solvents, monomers, etc., the carbon number is particularly preferably 6-22.
脂肪族カルボン酸は、酸化ジルコニウムナノ粒子表面に疎水性を与え、その有機溶媒等中での分散安定性に寄与する。 また、水酸基含有脂肪族カルボン酸の水酸基は、特に分散媒がカルボニル基を有する有機溶媒、モノマーまたは重合性オリゴマーである場合に、そのカルボニル基との水素結合により分散体の安定性に寄与するものと考えられる。 The aliphatic carboxylic acid imparts hydrophobicity to the surface of the zirconium oxide nanoparticles and contributes to dispersion stability in an organic solvent or the like. The hydroxyl group of the hydroxyl group-containing aliphatic carboxylic acid contributes to the stability of the dispersion by hydrogen bonding with the carbonyl group, particularly when the dispersion medium is an organic solvent, monomer or polymerizable oligomer having a carbonyl group. it is conceivable that.
上記で得られた、ジルコニウム−アミン錯体に、水と、アルミニウム、マグネシウム、チタンおよび希土類元素の塩またはアルコキシドから選ばれた少なくとも１種と、カルボン酸とを加えた混合物を、水熱反応に供する。 A mixture obtained by adding water, at least one selected from a salt or alkoxide of aluminum, magnesium, titanium, and a rare earth element, and a carboxylic acid to the zirconium-amine complex obtained above is subjected to a hydrothermal reaction. .
本発明の水熱反応は、密閉容器中で１４０〜３００℃、好ましくは２００〜３００℃で行われる。 ２００℃未満では反応が遅いため（反応時間が２４時間を超える場合がある）実際的ではなく、３００℃を超えると装置が大掛かりなものとなる。 The hydrothermal reaction of the present invention is carried out at 140 to 300 ° C, preferably 200 to 300 ° C, in a sealed container. If the temperature is lower than 200 ° C, the reaction is slow (the reaction time may exceed 24 hours), which is not practical. If the temperature exceeds 300 ° C, the apparatus becomes large.
水熱反応後、定法により精製して本発明の正方晶酸化ジルコニウムナノ粒子を得ることができる。 例えば、反応液の上澄み液除去、濾過と溶媒洗浄、または溶媒中での超音波洗浄と遠心分離により精製し、乾燥することによって、白色粉末として本発明の正方晶酸化ジルコニウムナノ粒子を得ることができる。 After the hydrothermal reaction, the tetragonal zirconium oxide nanoparticles of the present invention can be obtained by purification by a conventional method. For example, the tetragonal zirconium oxide nanoparticles of the present invention can be obtained as a white powder by removing the supernatant from the reaction solution, purifying by filtration and solvent washing, or ultrasonic washing and centrifugation in a solvent and drying. it can.
上記では、正方晶酸化ジルコニウムナノ粒子の製造方法を、ジルコニウム−アミン錯体の製造、得られたジルコニウム−アミン錯体への安定化元素含有化合物およびカルボン酸の添加、水熱反応、そして精製といった工程で逐次的に説明してきたが、後記実施例５のように、一度にこれらの化合物を混合し、水熱反応、次いで精製といった工程でも製造可能である。 In the above, the method for producing tetragonal zirconium oxide nanoparticles is performed in the steps of producing a zirconium-amine complex, adding a stabilizing element-containing compound and a carboxylic acid to the obtained zirconium-amine complex, hydrothermal reaction, and purification. Although described sequentially, it can also be produced by mixing these compounds at once, hydrothermal reaction, and then purification, as in Example 5 below.
このようにして得られた正方晶酸化ジルコニウムナノ粒子は、正方晶のみで粒子径が数ｎｍ〜数１０ｎｍの単分散したものとなるが、その平均粒子径は１〜２０ｎｍが好ましく、分散体の透明性を考慮すると１〜１０ｎｍがより好ましい。
なお、本発明において、平均粒子径は、粉末Ｘ 線回折データから結晶子サイズをＳｃｈｅｒｒｅｒ式により求め、その値と同等であるとした。 図２には、後記実施例４の透過電子顕微鏡での観察結果を示しているが、殆ど全ての粒子が１０ｎｍ以下で凝集も見られない。 実際、実施例４において透過電子顕微鏡の観察から無作為に１００個の粒子を選び、その長径と短径の二軸平均値から求めた値の平均値と前述の結晶子サイズとを比較すると、前者では４．３６ｎｍ、後者では４．１ｎｍと、ほぼ同等の数値が得られている。
The tetragonal zirconium oxide nanoparticles obtained in this way are only tetragonal and monodispersed with a particle diameter of several nanometers to several tens of nanometers, and the average particle diameter is preferably 1 to 20 nm. In consideration of transparency, 1 to 10 nm is more preferable.
In the present invention, the average particle size is equivalent to the crystallite size obtained from the X-ray powder diffraction data by the Scherrer equation. FIG. 2 shows the observation result with a transmission electron microscope of Example 4 to be described later. Almost all the particles are 10 nm or less and no aggregation is observed. In fact, 100 particles were randomly selected from observation with a transmission electron microscope in Example 4, and the average value of the values obtained from the biaxial average values of the major axis and the minor axis was compared with the crystallite size described above. The former is 4.36 nm, and the latter is 4.1 nm.
本発明の正方晶酸化ジルコニウムナノ粒子は、アルミニウム、マグネシウム、チタン及び希土類元素から選ばれる少なくとも１種の安定化元素を含有し、カルボン酸で表面処理されている。前記安定化元素の含有量はその添加量に従って、ジルコニウム元素との原子数比で１／９９以上１／１０以下が好ましい。 １／９９未満では安定化元素の効果が不十分なため正方晶以外の結晶が生成するといった問題があり、１／１０を超えるとその効果が飽和するため無駄になるばかりでなく屈折率低下の要因となるため好ましくない。 The tetragonal zirconium oxide nanoparticles of the present invention contain at least one stabilizing element selected from aluminum, magnesium, titanium and rare earth elements, and are surface-treated with carboxylic acid. The content of the stabilizing element is preferably 1/99 or more and 1/10 or less in the atomic ratio with the zirconium element according to the addition amount. If it is less than 1/99, there is a problem that crystals other than tetragonal crystals are generated because the effect of the stabilizing element is insufficient, and if it exceeds 1/10, the effect is saturated and not only wasted, but also the refractive index decreased. Since it becomes a factor, it is not preferable.
また、カルボン酸による表面処理量は、得られた正方晶酸化ジルコニウムナノ粒子に対して５質量％以上３０質量％以下である。 ５質量％未満では有機溶媒、モノマー等への分散性が不十分で、３０質量％を超えると屈折率低下が著しくなるため好ましくない。 ここで、カルボン酸の表面処理量は、窒素雰囲気下４０℃／分の速度で９００℃まで昇温したときの質量減少率とした。 Moreover, the surface treatment amount by carboxylic acid is 5 mass% or more and 30 mass% or less with respect to the obtained tetragonal zirconium oxide nanoparticle. If it is less than 5% by mass, dispersibility in an organic solvent, a monomer or the like is insufficient, and if it exceeds 30% by mass, the refractive index is significantly lowered, which is not preferable. Here, the surface treatment amount of the carboxylic acid was defined as a mass reduction rate when the temperature was raised to 900 ° C. at a rate of 40 ° C./min in a nitrogen atmosphere.
さらに、本発明の正方晶酸化ジルコニウムナノ粒子は、その表面が疎水化され、凝集しにくいため、有機溶媒、モノマー、樹脂等への分散性に優れている。 従って、例えば超音波ホモジナイザーを用いることにより有機溶媒中に容易に均一分散させることができるばかりでなく、モノマーや重合性オリゴマーに分散させてから重合させたり、樹脂に分散させたりすることによって正方晶酸化ジルコニウムナノ粒子が樹脂中に微分散した樹脂複合体を得ることができる。 なお、本発明の正方晶酸化ジルコニウム分散体および樹脂複合体には、その目的に応じて酸化防止剤、離型剤、重合開始剤、染顔料、分散剤等を含有してもよい。 Furthermore, the tetragonal zirconium oxide nanoparticles of the present invention are excellent in dispersibility in organic solvents, monomers, resins, and the like because the surfaces thereof are hydrophobized and hardly aggregate. Therefore, for example, by using an ultrasonic homogenizer, not only can it be easily and uniformly dispersed in an organic solvent, but it can also be dispersed in a monomer or polymerizable oligomer and then polymerized or dispersed in a resin to form a tetragonal crystal. A resin composite in which zirconium oxide nanoparticles are finely dispersed in the resin can be obtained. The tetragonal zirconium oxide dispersion and resin composite of the present invention may contain an antioxidant, a release agent, a polymerization initiator, a dye / pigment, a dispersant and the like depending on the purpose.
前記の有機溶媒としては、例えば、エタノール、２−プロパノール、ブタノール、オクタノール、シクロヘキサノール等のアルコール類、酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、γ−ブチロラクトン等のエステル類、ジエチルエーテル、テトラヒドロフラン、エチレングリールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジオキサン等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミド類が好適に用いられ、これらの溶媒のうち１ 種または２ 種以上を用いることができる。 Examples of the organic solvent include alcohols such as ethanol, 2-propanol, butanol, octanol, and cyclohexanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ- Esters such as butyrolactone, diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dioxane ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone , Ketones such as acetylacetone and cyclohexanone, benzene, tolu Aromatic hydrocarbons such as ethylene, xylene and ethylbenzene, and amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone are preferably used, and one or more of these solvents are used. be able to.
前記のモノマーおよび重合性オリゴマーとしては、ラジカル重合性、縮重合性、開環重合性等のいずれであっても使用できる。 例えば、ラジカル重合性のモノマーとしては、アクリル酸メチル、メタクリル酸メチル等の（メタ）アクリル系モノマー、グリシジル基、イソシアネート基、ビニルエーテル基等の反応性官能基を持つ（メタ）アクリル系モノマー、スチレン等のビニル系モノマー等、縮重合性のモノマーとしてはポリアミドやポリエステルを形成するモノマー、ポリイソシアネートとポリオールおよびポリチオールとの組み合わせ等、開環重合性のモノマーとしてはエポキシ系モノマー等が好適に使用できる。 また、重合性オリゴマーとしては、ウレタンアクリレート系オリゴマー、エポキシアクリレート系オリゴマー、アクリレート系オリゴマー等が好適に使用できる。 As the monomer and polymerizable oligomer, any of radical polymerizable, polycondensable, ring-opening polymerizable and the like can be used. For example, radical polymerizable monomers include (meth) acrylic monomers such as methyl acrylate and methyl methacrylate, (meth) acrylic monomers having reactive functional groups such as glycidyl groups, isocyanate groups, vinyl ether groups, and styrene. As the polycondensation monomer, such as vinyl monomers such as polyamides and polyesters, a combination of polyisocyanate, polyol and polythiol, etc., as ring-opening polymerization monomers, epoxy monomers can be preferably used. . Moreover, as the polymerizable oligomer, urethane acrylate oligomer, epoxy acrylate oligomer, acrylate oligomer, and the like can be suitably used.
本発明の正方晶酸化ジルコニウムナノ粒子を、モノマーまたは重合性オリゴマーに分散させてから重合させたり、樹脂中に分散させることによって樹脂複合体を得ることができる。 本発明の正方晶酸化ジルコニウムナノ粒子は、分散性に優れるため高屈折率で透明性を要求される用途、機械的物性を向上させる用途等に好適に用いられる。
ここで、本発明の正方晶酸化ジルコニウムナノ粒子を分散させる樹脂としては、熱可塑性樹脂、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリ乳酸、ポリエチレンテレフタレート等のポリエステル、ポリアミド、ポリ（メタ）アクリレート、ポリフェニレンエーテル、ポリウレタン、ポリスチレン、環状ポリオレフィン、ポリカーボネートなどから選ばれた１種または２種以上が好ましく用いられる。
A resin composite can be obtained by dispersing the tetragonal zirconium oxide nanoparticles of the present invention in a monomer or a polymerizable oligomer and then dispersing in a resin. Since the tetragonal zirconium oxide nanoparticles of the present invention are excellent in dispersibility, they are suitably used for applications requiring high refractive index and transparency, improving mechanical properties, and the like.
Here, as the resin for dispersing the tetragonal zirconium oxide nanoparticles of the present invention, thermoplastic resins such as polyolefins such as polyethylene and polypropylene, polyesters such as polylactic acid and polyethylene terephthalate, polyamides, poly (meth) acrylates, and polyphenylenes are used. One or more selected from ether, polyurethane, polystyrene, cyclic polyolefin, polycarbonate and the like are preferably used.
以下に実施例及び比較例を示して本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。 なお、実施例および比較例中の％ は質量％を意味する。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these. In addition,% in an Example and a comparative example means the mass%.
本発明において酸化ジルコニウムナノ粒子の結晶構造は、Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ社製、Ｘ’Ｐｅｒｔ ＰＲＯ ＭＲＤ）を用い、測定条件を、Ｘ線管電圧４５ｋＶ、Ｘ線管電電流４０ｍＡ、走査範囲２ θは１０．０−６５．０°とし、Ｘ 線回折測定の２θ＝２８．２ 付近の（１１−１） 面の単斜晶による回折強度と、３０．２付近の（１１１） 面の正方晶による回折強度を比較することによって単斜晶と正方晶の生成比率とした。 In the present invention, the crystal structure of the zirconium oxide nanoparticles is measured using an X-ray diffractometer (manufactured by PANalytical, X'Pert PRO MRD), measuring conditions are an X-ray tube voltage of 45 kV, an X-ray tube current of 40 mA, a scanning range of 2 θ is 10.0-65.0 °, X-ray diffraction measurement of diffraction intensity due to monoclinic crystal of (11-1) plane near 2θ = 28.2, and square of (111) plane near 30.2 By comparing the diffraction intensities of the crystals, the production ratio of monoclinic crystals and tetragonal crystals was determined.
正方晶酸化ジルコニウム粒子の平均粒子径は、前記の結晶構造測定結果を用い、２θが３０．２付近の（１１１） 面の正方晶による解析強度からその半価幅βを求め、下記数式１のＳｃｈｅｒｒｅｒ式において、Ｓｃｈｅｒｒｅｒ定数Ｋを０．９、Ｘ線管球の波長λを１．５４０５６として結晶子サイズＤを求め、その値とした。 The average particle diameter of the tetragonal zirconium oxide particles is obtained from the above-mentioned crystal structure measurement result, and the half-value width β is obtained from the analytical strength of the tetragonal crystal of (111) face where 2θ is around 30.2. In the Scherrer equation, the crystallite size D was determined by setting the Scherrer constant K to 0.9 and the X-ray tube wavelength λ to 1.54056.
（数１）
Ｄ＝Ｋ ・λ／（β・ｃｏｓθ）
(Equation 1)
D = K · λ / (β · cos θ)
また、有機溶媒またはモノマー中での分散性は、合成した酸化ジルコニウム粒子に１０％濃度になるように種々の有機溶媒またはモノマーを添加し、超音波洗浄器（ヴェルヴォクリーア社製３周波超音波洗浄器 ＶＳ−１００ＩＩＩ）による数分の処理後、目視により、透明なものを○、半透明なものを△、白濁または沈降するものを×として評価した。 In addition, dispersibility in an organic solvent or a monomer is such that various organic solvents or monomers are added to the synthesized zirconium oxide particles so as to have a concentration of 10%, and an ultrasonic cleaner (3 frequency ultrasonic wave manufactured by Velvo Crea) is used. After a few minutes of treatment with the washer VS-100III), the transparent product was evaluated as ○, the translucent product as Δ, and the white turbidity or sedimentation as ×.
（実施例１）
トリエタノールアミン７．４ｇに８５％テトラ−ｎ−ブトキシジルコニウム１０．９ｇを添加し撹拌した。これに蒸留水を２４．０ｇ、塩化イットリウム６水和物を０．３６ｇ添加し撹拌を続けた。 次いで蒸留水２４．０ｇおよびラウリン酸３．０ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。水熱処理後、上澄み液を除去し、白色沈殿物をメタノールで超音波洗浄器を用いて分散後遠心分離し、上澄み液を再度除去した。 この洗浄工程を３回繰り返した後、室温で一昼夜真空乾燥を行い、３．５８ｇの白色粉末を得た。 カルボン酸の表面処理量は、ＰｅｒｋｉｎＥｌｍｅｒ社製の熱質量測定装置Ｐｙｌｉｓ１TGAにより、窒素雰囲気下４０℃／分の速度で９００℃まで昇温した質量減少率から１７．１３％であった。
Example 1
10.9 g of 85% tetra-n-butoxyzirconium was added to 7.4 g of triethanolamine and stirred. Distilled water (24.0 g) and yttrium chloride hexahydrate (0.36 g) were added thereto, and stirring was continued. Next, 24.0 g of distilled water and 3.0 g of lauric acid were further added, and the mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After the hydrothermal treatment, the supernatant was removed, and the white precipitate was dispersed with methanol using an ultrasonic cleaner and then centrifuged, and the supernatant was removed again. After repeating this washing process three times, vacuum drying was performed at room temperature for a whole day and night to obtain 3.58 g of white powder. The surface treatment amount of the carboxylic acid was 17.13% from the mass reduction rate increased to 900 ° C. at a rate of 40 ° C./min in a nitrogen atmosphere by a thermal mass measuring device Pylis1 TGA manufactured by PerkinElmer.
（実施例２）
トリエタノールアミン７．４ｇに８５％テトラ−ｎ−ブトキシジルコニウム１０．９ｇを添加し撹拌した。 これに蒸留水を１８．０ｇ、塩化イットリウム６水和物を０．３６ｇ添加し撹拌を続けた。 次いで蒸留水３０．０ｇ、ラウリン酸２．７ｇおよび１２−ヒドロキシステアリン酸２．２ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により３．６４ｇの白色粉末を得た。 ＰＡＮａｌｙｔｉｃａｌ社製蛍光X線分析装置Ｅｐｓｉｌｏｎ５を用いて測定したところ、イットリウムの含有量は、全金属量に対し４．２６％であった。 また、カルボン酸の表面処理量は実施例１と同様に測定して１９．０３％であった。
(Example 2)
10.9 g of 85% tetra-n-butoxyzirconium was added to 7.4 g of triethanolamine and stirred. Distilled water (18.0 g) and yttrium chloride hexahydrate (0.36 g) were added thereto, and stirring was continued. Next, 30.0 g of distilled water, 2.7 g of lauric acid and 2.2 g of 12-hydroxystearic acid were further added, and this mixture was subjected to hydrothermal treatment at 290 ° C. for 2 hours in an autoclave. After hydrothermal treatment, the supernatant was removed, and 3.64 g of white powder was obtained by the same washing and drying steps as in Example 1. When measured using an X-ray fluorescence analyzer Epsilon 5 manufactured by PANalytical, the yttrium content was 4.26% with respect to the total metal content. The surface treatment amount of carboxylic acid was 19.03% as measured in the same manner as in Example 1.
（実施例３）
トリエタノールアミン７．４ｇに８５％テトラ−ｎ−ブトキシジルコニウム１０．９ｇを添加し撹拌した。 これに蒸留水を２４．０ｇ、アルミニウムイソプロポキシド０．２４ｇを添加し撹拌を続けた。 次いで蒸留水２４．０ｇ、ラウリン酸２．４ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により３．３９ｇの白色粉末を得た。 実施例２と同様に金属含量分析および質量減少率を測定したところ、アルミニウムの含有量は３．６６％、カルボン酸の表面処理量は１２．２７％であった。
(Example 3)
10.9 g of 85% tetra-n-butoxyzirconium was added to 7.4 g of triethanolamine and stirred. Distilled water (24.0 g) and aluminum isopropoxide (0.24 g) were added thereto, and stirring was continued. Next, 24.0 g of distilled water and 2.4 g of lauric acid were further added, and the mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After the hydrothermal treatment, the supernatant was removed, and 3.39 g of white powder was obtained by the same washing and drying steps as in Example 1. When the metal content analysis and mass reduction rate were measured in the same manner as in Example 2, the aluminum content was 3.66% and the carboxylic acid surface treatment amount was 12.27%.
（実施例４）
トリエタノールアミン７．４ｇに８５％テトラ−ｎ−ブトキシジルコニウム１０．９ｇを添加し撹拌した。これに蒸留水を１８．０ｇ、塩化イットリウム６水和物を０．３６ｇ添加し撹拌を続けた。 次いで蒸留水３０．０ｇおよびオクタン酸２．８ｇ、１２−ヒドロキシステアリン酸２．２ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により３．６４ｇの白色粉末を得た。 ここで得られた粉末について電解放出型分析透過電子顕微鏡（トプコンテクノハウスEM００２ＢＦ）による測定結果を図２として載せたが、ここから無作為に１００個の粒子を選び、その長径と短径の二軸平均値から求めた１００個の平均値は４．３６ｎｍとなり、Ｓｃｈｅｒｒｅｒ式から算出された結晶子サイズ４．１ｎｍとほぼ同等であることが確認できた。 また、実施例１と同様に測定された質量減少率から、カルボン酸の表面処理量は１９．０３％であった。
Example 4
10.9 g of 85% tetra-n-butoxyzirconium was added to 7.4 g of triethanolamine and stirred. Distilled water (18.0 g) and yttrium chloride hexahydrate (0.36 g) were added thereto, and stirring was continued. Next, 30.0 g of distilled water, 2.8 g of octanoic acid, and 2.2 g of 12-hydroxystearic acid were further added, and this mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After hydrothermal treatment, the supernatant was removed, and 3.64 g of white powder was obtained by the same washing and drying steps as in Example 1. FIG. 2 shows the measurement results of the powder obtained here by using an electrolytic emission analytical transmission electron microscope (Topcon Technohouse EM002BF). From this, 100 particles were randomly selected, and the major and minor diameters were selected. The average value of 100 pieces obtained from the axial average value was 4.36 nm, which was confirmed to be substantially equivalent to the crystallite size of 4.1 nm calculated from the Scherrer equation. Moreover, from the mass decreasing rate measured similarly to Example 1, the surface treatment amount of carboxylic acid was 19.03%.
（実施例５）
トリエタノールアミン７．４ｇ、オクタン酸２．８ｇおよび１２−ヒドロキシステアリン酸２．２ｇを含有する溶液に、オキシ塩化ジルコニウム８水和物７．６ｇ、酢酸イットリウム４水和物０．３６ｇおよび蒸留水４８．０ｇの混合溶液を添加し、次いで、２８ｗｔ％アンモニア水溶液を６ｍL添加した。 得られた混合物をオートクレーブ中で２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により３．５８ｇの白色粉末を得た。 実施例２と同様に金属含量分析および質量減少率を測定したところ、イットリウムの含有量は４．０４％、カルボン酸の表面処理量は２０．７４％であった。
(Example 5)
In a solution containing 7.4 g of triethanolamine, 2.8 g of octanoic acid and 2.2 g of 12-hydroxystearic acid, 7.6 g of zirconium oxychloride octahydrate, 0.36 g of yttrium acetate tetrahydrate and distilled water 48.0 g of the mixed solution was added, and then 6 mL of 28 wt% aqueous ammonia solution was added. The obtained mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After the hydrothermal treatment, the supernatant was removed, and 3.58 g of white powder was obtained by the same washing and drying steps as in Example 1. When the metal content analysis and mass reduction rate were measured in the same manner as in Example 2, the yttrium content was 4.04% and the surface treatment amount of carboxylic acid was 20.74%.
（比較例１）
トリエタノールアミン７．４ｇに８５％テトラ−ｎ−ブトキシジルコニウム１０．９ｇを添加し撹拌した。これに蒸留水を２４．０ｇ添加し撹拌を続けた。 次いで蒸留水２４．０ｇおよびラウリン酸２．４ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により３．３２ｇの白色粉末を得た。
(Comparative Example 1)
10.9 g of 85% tetra-n-butoxyzirconium was added to 7.4 g of triethanolamine and stirred. Distilled water (24.0 g) was added thereto and stirring was continued. Next, 24.0 g of distilled water and 2.4 g of lauric acid were further added, and the mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After the hydrothermal treatment, the supernatant liquid was removed, and 3.32 g of white powder was obtained by the same washing and drying steps as in Example 1.
（比較例２）
トリエタノールアミン４．５ｇに８５％テトラ−ｎ−ブトキシジルコニウム６．８ｇを添加し撹拌した。 これに蒸留水を３０．０ｇ添加し撹拌を続けた。 この混合液にさらに塩酸水３０ｇをｐＨ＝５．２０になるように添加し白色ゲルを得た。 このゲルをオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、実施例１と同様の洗浄、乾燥工程により１．６９ｇの白色粉末を得た。
(Comparative Example 2)
To 4.5 g of triethanolamine, 6.8 g of 85% tetra-n-butoxyzirconium was added and stirred. 30.0 g of distilled water was added thereto and stirring was continued. To this mixed solution was further added 30 g of hydrochloric acid so that the pH was 5.20 to obtain a white gel. This gel was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After hydrothermal treatment, 1.69 g of white powder was obtained by the same washing and drying steps as in Example 1.
（比較例３）
８５％テトラ−ｎ−ブトキシジルコニウム６．８ｇに蒸留水を３０．０ｇ添加した。 これに蒸留水３０．０ｇおよびラウリン酸１．５ｇをさらに添加し、この混合液をオートクレーブで２９０℃、２時間の水熱処理を行った。 水熱処理後、上澄み液を除去し、実施例１と同様の洗浄、乾燥工程により２．０４ｇの白色粉末を得た。 実施例１と同様に質量減少率を測定したところ、カルボン酸の表面処理量は２５．８１％であった。
(Comparative Example 3)
30.0 g of distilled water was added to 6.8 g of 85% tetra-n-butoxyzirconium. Distilled water (30.0 g) and lauric acid (1.5 g) were further added thereto, and the mixture was hydrothermally treated at 290 ° C. for 2 hours in an autoclave. After the hydrothermal treatment, the supernatant liquid was removed, and 2.04 g of white powder was obtained by the same washing and drying steps as in Example 1. When the mass reduction rate was measured in the same manner as in Example 1, the surface treatment amount of carboxylic acid was 25.81%.
実施例１〜５および比較例１〜３で得られた酸化ジルコニウム粒子の粒子径、正方晶と単斜晶の生成比率および有機溶媒またはモノマー中での分散性を表１に記載した。 Table 1 shows the particle diameters of the zirconium oxide particles obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the formation ratio of tetragonal crystals and monoclinic crystals, and the dispersibility in organic solvents or monomers.
表１から実施例の酸化ジルコニウム粒子は正方晶のみで有機溶媒等への分散性に優れていることが分かる。 また、図１の実施例１および比較例１のＸ線回折図に示したとおり、２θ＝２８．２ 付近の回折強度（単斜晶）と、３０．２付近の回折強度（正方晶）とを比較することにより、実施例１の正方晶率が１００％で、比較例1には単斜晶が混在していることが確認できた。 It can be seen from Table 1 that the zirconium oxide particles of the examples are only tetragonal and excellent in dispersibility in an organic solvent or the like. Further, as shown in the X-ray diffraction diagrams of Example 1 and Comparative Example 1 in FIG. 1, the diffraction intensity around 2θ = 28.2 (monoclinic crystal) and the diffraction intensity around 30.2 (tetragonal crystal) It was confirmed that the tetragonal ratio in Example 1 was 100% and that monoclinic crystals were mixed in Comparative Example 1.
（製造例１）
ｎ−ブチルメタアクリレート、トルエン混合溶液中に実施例１の正方晶酸化ジルコニウムナノ粒子を、光重合開始剤の存在下に、乾燥後の酸化ジルコニウム含量が５０ｗｔ％となる配合でスピンコートし光重合させた。 膜厚モニター（大塚電子社製：ＦＥ−３００ＵＶ）を用いて屈折率を算出したところ、屈折率１．６１７の透明な塗布膜であった。
(Production Example 1)
Photopolymerization is carried out by spin-coating the tetragonal zirconium oxide nanoparticles of Example 1 in a mixed solution of n-butyl methacrylate and toluene in the presence of a photopolymerization initiator so that the zirconium oxide content after drying is 50 wt%. I let you. When the refractive index was calculated using a film thickness monitor (manufactured by Otsuka Electronics Co., Ltd .: FE-300UV), it was a transparent coating film having a refractive index of 1.617.
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