TW201825402A - Zirconia based nanoparticles and method for producing same - Google Patents
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本發明關於一種新穎之單斜晶氧化鋯系奈米粒子及其製造方法。The present invention relates to a novel monoclinic zirconia-based nanoparticle and a method of producing the same.
背景技術 高折射率材料被使用於諸如透鏡、光學過濾器及抗反射材等各種光學零件上。舉透鏡作為一例，若是具有高折射率之透鏡，則可謀求與其相應之透鏡薄型化、輕量化、高解析度化等，製品將變得有利。Background Art High refractive index materials are used in various optical parts such as lenses, optical filters, and antireflection materials. As a lens, as a lens having a high refractive index, it is possible to reduce the thickness, weight, and resolution of the lens corresponding thereto, and the product is advantageous.
就高折射率材料而言，除了玻璃、陶瓷等透明性無機材料之外，已知有以透明性樹脂為基質並使高折射率粒子分散而得之複合材料，特別在低成本化、輕量化等觀點上，如前述般之複合材料甚是有利。In addition to a transparent inorganic material such as glass or ceramics, a high-refractive-index material is known as a composite material obtained by dispersing a high-refractive-index particle with a transparent resin as a matrix, and is particularly low in cost and weight. From a point of view, the composite material as described above is very advantageous.
就分散至複合材料中之高折射率粒子而言，舉例來說，目前採用氧化鈦、氧化鋯、氧化鋁等無機氧化物粒子。特別是氧化鈦、氧化鋯等具有高折射率(2.00以上)，但用作光學材料也需具有高透明性。亦即，需要更微細且安定之無機氧化物粒子。For the high refractive index particles dispersed in the composite material, for example, inorganic oxide particles such as titanium oxide, zirconium oxide, and aluminum oxide are currently used. In particular, titanium oxide, zirconium oxide, etc. have a high refractive index (2.00 or more), but it is also required to have high transparency as an optical material. That is, a finer and more stable inorganic oxide particle is required.
於此，就製造複合材料時之原料形態而言，無機氧化物粒子通常以業已分散於溶劑之分散液形式來提供。因此，要求分散液中各個粒子不發生凝集而可發揮高度分散狀態。從此種立場來看，最近為了開發出分散性等更優異之無機氧化物粒子或其分散液，刻正進行各種研究及提案。Here, in terms of the form of the raw material in the production of the composite material, the inorganic oxide particles are usually provided in the form of a dispersion which has been dispersed in a solvent. Therefore, it is required that each particle in the dispersion liquid does not agglomerate and can exhibit a highly dispersed state. From such a standpoint, various research and proposals have been made in order to develop more excellent inorganic oxide particles or dispersions thereof such as dispersibility.
舉例來說，已知一種氧化鋯系奈米粒子，其由2種以上之被覆劑所被覆，且為含有正方晶氧化鋯之氧化鋯奈米粒子，其特徵在於該被覆劑中之至少1種係如下式(I)所示者： R1 -COOH・・・(I) [式中，R1 表示碳數6以上之支鏈狀烴基]； 並且，式(I)所示被覆劑之外的至少1種被覆劑為下述者：具有多數個選自於由羥基、胺基、巰基、羧基、環氧基及烷氧基所構成群組中之至少1種官能基之物；具有乙烯基或苯基之物；矽烷偶合劑；或下式(II)所示之物： R2 -COOH・・・(II) [式中，R2 表示碳數6以上之直鏈狀烴基](專利文獻1)。For example, a zirconia-based nanoparticle which is coated with two or more kinds of coating agents and is a zirconia nanoparticle containing tetragonal zirconia is known, and at least one of the coating materials is used. In the formula (I): R 1 -COOH (I) wherein R 1 represents a branched hydrocarbon group having 6 or more carbon atoms; and, in addition to the coating agent represented by the formula (I) At least one coating agent is one having a plurality of at least one functional group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, a carboxyl group, an epoxy group, and an alkoxy group; Or a phenyl group; a decane coupling agent; or a compound represented by the following formula (II): R 2 -COOH (II) [wherein R 2 represents a linear hydrocarbon group having 6 or more carbon atoms] ( Patent Document 1).
此外，舉例來說，已知一種氧化鋯透明分散液，其特徵在於：含有分散粒徑為1nm以上且20nm以下之正方晶氧化鋯粒子(專利文獻2)。Further, for example, a transparent dispersion of zirconia is known, which comprises tetragonal zirconia particles having a dispersed particle diameter of 1 nm or more and 20 nm or less (Patent Document 2).
更進一步來說，目前已提出一種無機微粒子之分散溶液之製造方法，該無機微粒子之分散溶液係於溶劑中分散有一次粒子之平均粒徑為1nm以上且30nm以下的無機微粒子，其特徵在於：使用平均粒徑為15µm以上且30µm以下之珠粒來攪拌無機微粒子(一次粒子之平均粒徑為1nm以上30nm以下)以凝集狀態存在於溶劑中之混合溶劑同時施加超音波，藉此分散處理前述無機微粒子 (專利文獻3)。 先行技術文獻 專利文獻Furthermore, a method for producing a dispersion solution of inorganic fine particles in which inorganic fine particles having an average particle diameter of primary particles of 1 nm or more and 30 nm or less are dispersed in a solvent has been proposed, and is characterized in that: By using the beads having an average particle diameter of 15 μm or more and 30 μm or less to stir the inorganic fine particles (the average particle diameter of the primary particles is 1 nm or more and 30 nm or less), ultrasonic waves are simultaneously applied in a mixed state in a solvent in a coagulated state, thereby dispersing the aforementioned treatment. Inorganic fine particles (Patent Document 3). Advanced technical literature
[專利文獻1]日本專利第5030694號 [專利文獻2]日本特開2007-99931號公報 [專利文獻3]日本特開2010-23031號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-99931 [Patent Document 3] JP-A-2010-23931
發明概要 發明欲解決之課題 然而，該等習知技術之分散液中，氧化鋯奈米粒子不僅是單斜晶氧化鋯，也包含了正方晶相氧化鋯。由於氧化鋯之正方晶相為準安定相，而有在某些因素下會經時性地相變為單斜晶相之虞。一旦相變為單斜晶相而引發體積變化(特別是體積收縮)，結果將會對分散液所形成之塗膜的物性造成不良影響。更具體來說，以包含正方晶相之氧化鋯奈米粒子形成塗膜後，一旦膜中之正方晶相經時性地相變為單斜晶相，因體積變化而在塗膜中發生應變等，就結果而言，將有使物理特性降低之虞。SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, in the dispersions of the prior art, the zirconia nanoparticles are not only monoclinic zirconia but also tetragonal zirconia. Since the tetragonal phase of zirconia is a quasi-stable phase, there is a tendency to phase change into a monoclinic phase over time. Once the phase changes to a monoclinic phase and a volume change (especially volume shrinkage) is caused, the result is an adverse effect on the physical properties of the coating film formed by the dispersion. More specifically, after forming a coating film with zirconia nanoparticles containing a tetragonal phase, once the tetragonal phase in the film is phase-transformed into a monoclinic phase, strain occurs in the coating film due to volume change. Etc. As a result, there will be a flaw in reducing physical properties.
從此種觀點出發，含較少或實質上不含正方晶氧化鋯之氧化鋯奈米粒子可謂理想，但此種氧化鋯奈米粒子目前未至開發乃為現狀。From such a viewpoint, zirconia nanoparticles containing less or substantially no tetragonal zirconia are desirable, but such zirconia nanoparticles have not been developed until now.
因此，本發明之主要目的在於提供一種含較少或實質上不含正方晶氧化鋯之氧化鋯奈米粒子。 用以解決課題之手段Accordingly, it is a primary object of the present invention to provide a zirconia nanoparticle containing less or substantially no tetragonal zirconia. Means to solve the problem
本案發明人鑑於習知技術之問題點反覆精心研究，結果發現，起始材料使用特定之氧化鋯粉末並以特定方法製出之奈米粒子可達成上述目的，終至完成本發明。The inventors of the present invention have intensively studied in view of the problems of the prior art, and as a result, have found that the above materials can be achieved by using a specific zirconia powder and a nanoparticle produced by a specific method to complete the present invention.
亦即，本發明有關於下述氧化鋯系奈米粒子及其製造方法。 1.一種單斜晶氧化鋯系奈米粒子，係粒度分佈D50為20nm以下之氧化鋯微粒子，其特徵在於： (1)該氧化鋯微粒子含有氧化鋯單斜晶相；並且 (2)該氧化鋯微粒子利用粉末X射線繞射分析所得繞射圖案中，2θ=29.74~30.74度之範圍內實質上不存在繞射尖峰。 2.如前述第1項之單斜晶氧化鋯系奈米粒子，其氧化鋯單斜晶相之含量為90體積%以上。 3.如前述第1或2項之單斜晶氧化鋯系奈米粒子，其由氧化鋯微粒子構成之粉末之粒度分佈為單峰，且粒度分佈D90為30nm以下。 4.一種分散液，係於溶劑中分散有如前述第1至3項中任一項之單斜晶氧化鋯系奈米粒子。 5.如前述第4項之分散液，其更含有矽烷偶合劑及磷酸酯系分散劑。 6.一種單斜晶氧化鋯系奈米粒子之製造方法，係一從氧化鋯粉末製出如前述第1項之單斜晶氧化鋯系奈米粒子之方法，其特徵在於： (1)前述氧化鋯粉末之a)粒度分佈D50為900nm以下，b)氧化鋯單斜晶相之含量為90~95體積%，且氧化鋯正方晶相之含量為5~10體積%； (2)包含下述步驟：在粒度分佈D50為40μm以下之珠粒存在下，將前述氧化鋯粉末供予珠磨處理。 7.如前述第6項之製造方法，其珠磨處理係一在溶劑存在下進行實施之濕式珠磨處理。 8.如前述第7項之製造方法，其中溶劑中含有矽烷偶合劑及磷酸酯系分散劑。 9.如前述第6項之製造方法，其中前述珠粒為金屬珠粒及陶瓷珠粒中之至少1種。 10.如前述第6項之製造方法，其使用具有略呈球形之形狀的粒子作為前述珠粒。 11.如前述第6項之製造方法，其中氧化鋯粉末之BET比表面積為70m2 /g以上。 發明效果That is, the present invention relates to the following zirconia-based nanoparticles and a method for producing the same. A monoclinic zirconia-based nanoparticle, which is a zirconia fine particle having a particle size distribution D50 of 20 nm or less, characterized in that: (1) the zirconia fine particle contains a zirconia monoclinic phase; and (2) the oxidation In the diffraction pattern obtained by powder X-ray diffraction analysis of the zirconium fine particles, there is substantially no diffraction peak in the range of 2θ=29.74 to 30.74 degrees. 2. The monoclinic zirconia-based nanoparticles according to the above item 1, wherein the content of the zirconia monoclinic phase is 90% by volume or more. 3. The monoclinic zirconia-based nanoparticles according to the above item 1 or 2, wherein the powder composed of the zirconia fine particles has a single particle size distribution and a particle size distribution D90 of 30 nm or less. A dispersion liquid in which a monoclinic zirconia-based nanoparticle according to any one of items 1 to 3 above is dispersed in a solvent. 5. The dispersion according to item 4 above, which further comprises a decane coupling agent and a phosphate ester dispersing agent. A method for producing monoclinic zirconia-based nanoparticles, which is a method for producing monoclinic zirconia-based nanoparticles according to the above item 1 from zirconia powder, characterized in that: (1) The zirconia powder has a particle size distribution D50 of 900 nm or less, b) a zirconia monoclinic phase content of 90 to 95 vol%, and a zirconia tetragonal phase content of 5 to 10 vol%; (2) Step: The zirconia powder is subjected to bead mill treatment in the presence of beads having a particle size distribution D50 of 40 μm or less. 7. The method according to the above item 6, wherein the bead mill treatment is a wet bead mill treatment carried out in the presence of a solvent. 8. The method according to the above item 7, wherein the solvent contains a decane coupling agent and a phosphate ester dispersing agent. 9. The method according to the above 6, wherein the beads are at least one of metal beads and ceramic beads. 10. The production method according to the above item 6, which uses particles having a slightly spherical shape as the aforementioned beads. 11. The production method according to the above item 6, wherein the zirconia powder has a BET specific surface area of 70 m 2 /g or more. Effect of the invention
依據本發明，可提供一種含較少或實質上不含正方晶氧化鋯之氧化鋯奈米粒子。更具體來說，則可提供一種奈米粒子(單斜晶氧化鋯粒子)，其正方晶氧化鋯(準安定正方晶)較少或實質上不含正方晶氧化鋯，並且含有單斜晶氧化鋯。According to the present invention, a zirconia nanoparticle containing less or substantially no tetragonal zirconia may be provided. More specifically, it is possible to provide a nanoparticle (monoclinic zirconia particle) whose tetragonal zirconia (quasi-stabilized tetragonal crystal) is less or substantially free of tetragonal zirconia and contains monoclinic oxide zirconium.
此種特殊奈米粒子可有效抑制乃至於防止正方晶氧化鋯可能引起之伴隨相變而起之體積變動，因此使用將其分散在液相中而成之分散液所得塗膜亦可發揮高可靠性。Such a special nanoparticle can effectively suppress or even prevent the volume change caused by the phase transition of the tetragonal zirconia, so that the coating film obtained by dispersing the dispersion in the liquid phase can also exhibit high reliability. Sex.
此外，由於本發明之製造方法使用含正方晶氧化鋯之氧化鋯粒子作為起始材料並於特定之微細珠粒存在下將其進行珠磨處理，而可確實且有效地製出正方晶氧化鋯更少或實質不含正方晶氧化鋯且實質上由單斜晶氧化鋯構成之奈米粒子。Further, since the production method of the present invention uses the zirconia particles containing tetragonal zirconia as a starting material and subjecting it to a bead mill treatment in the presence of specific fine beads, the tetragonal zirconia can be surely and efficiently produced. Nanoparticles that are less or substantially free of tetragonal zirconia and consist essentially of monoclinic zirconia.
不僅如此，本發明之製造方法所得奈米粒子可得奈米等級下之微細分散狀態。其理由尚未確定，但推測係以如下之作用機制而實現。亦即，本發明之製造方法雖然使用包含正方晶相及單斜晶相兩者之氧化鋯來作為起始材料，其中即使包含了凝集粒子，製造過程中正方晶相相變為單斜晶相時，因體積變化所致之應變會發生於該凝集粒子中，凝集因該應變而解開，結果使得細粒化進行而發揮高分散性。Moreover, the nanoparticle obtained by the production method of the present invention can be obtained in a finely dispersed state at a nanometer level. The reason for this has not yet been determined, but it is speculated that it is achieved by the following mechanism of action. That is, the manufacturing method of the present invention uses zirconia containing both a tetragonal phase and a monoclinic phase as a starting material, wherein even if agglomerated particles are contained, the tetragonal phase changes into a monoclinic phase during the manufacturing process. In the case where the strain due to the volume change occurs in the aggregated particles, the aggregation is released by the strain, and as a result, the fine granulation proceeds to exhibit high dispersibility.
如前述，由於本發明之氧化鋯奈米粒子安定且可得高分散性，舉例來說，可適宜用作透鏡、光學過濾器及抗反射材等各種光學零件之原料。As described above, since the zirconia nanoparticle of the present invention is stable and highly dispersible, it can be suitably used as a raw material of various optical parts such as a lens, an optical filter, and an antireflection material.
用以實施發明之形態 1.氧化鋯系奈米粒子 本發明之單斜晶氧化鋯系奈米粒子(本發明奈米粒子)係粒度分佈D50為20nm以下之氧化鋯微粒子，其特徵在於： (1)該氧化鋯微粒子含有單斜晶相；並且 (2)該氧化鋯微粒子利用粉末X射線繞射分析所得繞射圖案中，2θ=29.74~30.74度實質上不存在繞射尖峰。The zirconia-based nanoparticle of the present invention The monoclinic zirconia-based nanoparticle of the present invention (the nanoparticle of the present invention) is a zirconia fine particle having a particle size distribution D50 of 20 nm or less, and is characterized in that: 1) The zirconia fine particles contain a monoclinic phase; and (2) the zirconia fine particles are substantially free from diffraction peaks in a diffraction pattern obtained by powder X-ray diffraction analysis at 2θ = 29.74 to 30.74 degrees.
本發明奈米粒子為結晶性氧化鋯粒子，且含有單斜晶相作為結晶相。氧化鋯單斜晶相之含量通常以90體積%以上為宜，尤宜為95~100體積%。亦即，本發明奈米粒子可在不妨礙本發明效果之範圍內含有正方晶氧化鋯以外之成分(例如其他結晶相、非晶相等)。The nanoparticle of the present invention is a crystalline zirconia particle and contains a monoclinic phase as a crystal phase. The content of the zirconia monoclinic phase is usually 90% by volume or more, and particularly preferably 95 to 100% by volume. That is, the nanoparticles of the present invention may contain components other than tetragonal zirconia (for example, other crystal phases and amorphous equivalent) within a range that does not impair the effects of the present invention.
就本發明奈米粒子之結晶相而言，其特徵在於：氧化鋯微粒子之粉末X射線繞射分析之繞射圖案中，2θ=29.74~30.74度內實質上不存在繞射尖峰。亦即，正方晶氧化鋯之繞射尖峰(101面)為2θ=30.24度，且繞射圖案上未能識別出正方晶氧化鋯之繞射尖峰一事為本發明奈米粒子之特徵之一。只要未能識別出此種繞射尖峰，本發明可接受含有極微量正方晶氧化鋯。另，就存在繞射尖峰之狀況而言，除了僅在2θ=29.74~30.74度之範圍內存在尖峰之情況之外，也包含跨2θ=29.74~30.74度之範圍內與其範圍外存在有寬幅尖峰的情況。The crystal phase of the nanoparticle of the present invention is characterized in that in the diffraction pattern of the powder X-ray diffraction analysis of the zirconia fine particles, there is substantially no diffraction peak in 2θ = 29.74 to 30.74 degrees. That is, the diffraction peak (101 face) of the tetragonal zirconia is 2θ=30.24 degrees, and the diffraction peak of the tetragonal zirconia is not recognized on the diffraction pattern, which is one of the characteristics of the nanoparticle of the present invention. As long as such diffraction peaks are not recognized, the present invention is acceptable to contain a very small amount of tetragonal zirconia. In addition, in the case of the diffraction peak, in addition to the case where there is only a peak in the range of 2θ=29.74~30.74 degrees, there is a wide range in the range of 2θ=29.74~30.74 degrees and outside the range. The situation of spikes.
另，本發明奈米粒子於利用拉曼分光法之分析中，也宜確認不到波數202cm-1 及267cm-1 之尖峰。進一步來說，本發明奈米粒子在由電子繞射所得強度曲線圖中，也宜確認不到源自正方晶之111t之尖峰。Further, in the analysis of the nanoparticles of the present invention by Raman spectroscopy, peaks of wave numbers of 202 cm -1 and 267 cm -1 are also not confirmed. Further, in the intensity profile obtained by the electron diffraction of the nanoparticle of the present invention, it is also preferable to confirm the peak of 111t derived from the tetragonal crystal.
可想見的是，本發明奈米粒子即使是奈米等級之粒子，仍因具有如同上述之結晶構造而在具有高安定性之同時亦對高分散性有所貢獻。It is conceivable that the nanoparticles of the present invention, even if they are nano-sized particles, have high stability and contribute to high dispersibility due to the crystal structure as described above.
本發明奈米粒子之粒度分佈D50(平均粒徑)為20nm以下，且宜為15nm以下。其下限值雖不具限定性，但通常可設為1nm程度。可藉由具有此種平均粒徑而有助於高透明性。The particle size distribution D50 (average particle diameter) of the nanoparticles of the present invention is 20 nm or less, and preferably 15 nm or less. Although the lower limit is not limited, it can usually be set to about 1 nm. It is possible to contribute to high transparency by having such an average particle diameter.
此外，本發明奈米粒子之粒度分佈雖不具限定性，但以呈單峰且粒度分佈D90為30nm以下(特別是25nm以下)尤佳。藉此，可在後述之分散液及其塗膜中更加發揮高安定性及透明性。Further, although the particle size distribution of the nanoparticles of the present invention is not limited, it is preferably a single peak and the particle size distribution D90 is 30 nm or less (particularly 25 nm or less). Thereby, high stability and transparency can be exhibited more in the dispersion liquid and the coating film mentioned later.
本發明奈米粒子宜具有相對較高之比表面積(BET法)。更具體來說，比表面積通常為70m2 /g以上，更宜為80m2 /g以上。另，比表面積之上限雖不具限定性，通常可設為200m2 /g左右。The nanoparticles of the present invention preferably have a relatively high specific surface area (BET method). More specifically, the specific surface area is usually 70 m 2 /g or more, more preferably 80 m 2 /g or more. Further, although the upper limit of the specific surface area is not limited, it is usually about 200 m 2 /g.
本發明奈米粒子基本上由氧化鋯(ZrO2 )構成，但可在不妨礙本發明效果之範圍內附著其他成分或與其他成分複合化。例如，以後述之製造方法製造本發明奈米粒子時，其製程中所添加之添加劑(諸如分散劑、偶合劑等)可附著於氧化鋯粒子或與其複合化。The nanoparticles of the present invention consist essentially of zirconia (ZrO 2 ), but other components may be attached or combined with other components within a range that does not impair the effects of the present invention. For example, when the nanoparticle of the present invention is produced by a production method described later, an additive (such as a dispersant, a coupling agent, or the like) added in the process may be attached to or composited with the zirconia particles.
本發明奈米粒子可呈現諸如乾燥粉末、分散液等中之任一形態，但本發明之單斜晶氧化鋯系奈米粒子(粉末)尤宜以分散於溶劑中之分散液形態來提供。此時，溶劑未特別受限，可舉例如：甲醇、乙醇、異丙醇、丁醇等醇系溶媒；酮、丙酮、甲乙酮、甲丙酮、甲基異丁酮等酮系溶劑；異丙醚、甲基賽璐蘇等醚系溶劑；丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯等二醇酯系溶劑。The nanoparticles of the present invention may be in any form such as a dry powder, a dispersion, etc., but the monoclinic zirconia-based nanoparticles (powder) of the present invention are particularly preferably provided in the form of a dispersion dispersed in a solvent. In this case, the solvent is not particularly limited, and examples thereof include an alcohol-based solvent such as methanol, ethanol, isopropanol or butanol; a ketone solvent such as ketone, acetone, methyl ethyl ketone, methyl acetone or methyl isobutyl ketone; and isopropyl ether; An ether solvent such as methyl acesulfame; a glycol ester solvent such as propylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate.
此外，可視需要而於上述分散液中添加各種添加劑。例如，可使用分散劑、偶合劑、分散輔劑等添加劑。Further, various additives may be added to the above dispersion as needed. For example, an additive such as a dispersing agent, a coupling agent, or a dispersion auxiliary agent can be used.
分散液中之本發明奈米粒子分散量(固體成分量)並未特別受限，可因應如所用溶劑之種類、所需黏度等予以適當設定。本發明尤宜在分散液中1~50重量%之範圍內設定分散量。The amount of dispersion (solid content) of the nanoparticles of the present invention in the dispersion is not particularly limited, and may be appropriately set depending on the kind of the solvent to be used, the desired viscosity, and the like. In the present invention, it is particularly preferable to set the dispersion amount in the range of 1 to 50% by weight in the dispersion.
2.單斜晶氧化鋯系奈米粒子之製造方法 本發明奈米粒子之製造方法並未特別受限，舉例來說可以如同下述之製造方法而適宜地製造。亦即，可適於採用下述製造方法：一種從氧化鋯粉末製造本發明奈米粒子之方法，其特徵在於： (1)前述氧化鋯粉末之a)粒度分佈D50為900nm以下，b)氧化鋯單斜晶相之含量為90~95體積%，且氧化鋯正方晶相之含量為5~10體積%； (2)包含下述步驟：在粒度分佈D50為40μm以下之珠粒存在下，將前述氧化鋯粉末供予珠磨處理(珠磨處理步驟)。2. Process for producing monoclinic zirconia-based nanoparticles The method for producing the nanoparticles of the present invention is not particularly limited, and can be suitably produced, for example, by the following production method. That is, it can be suitably employed in the following production method: a method for producing the nanoparticle of the present invention from zirconia powder, characterized in that: (1) the zirconia powder has a) particle size distribution D50 of 900 nm or less, b) oxidation The content of the zirconium monoclinic phase is 90 to 95% by volume, and the content of the zirconia tetragonal phase is 5 to 10% by volume; (2) comprising the following steps: in the presence of beads having a particle size distribution D50 of 40 μm or less, The aforementioned zirconia powder is supplied to a bead mill treatment (bead mill treatment step).
起始材料 本發明之製造方法係以起始材料使用氧化鋯粉末作為前提，該氧化鋯粉末係使用a)粒度分佈D50為900nm以下、b)氧化鋯單斜晶相之含量為90~95體積%且氧化鋯正方晶相之含量為5~10體積%之粉末。Starting material The manufacturing method of the present invention is based on the assumption that the starting material is zirconia powder, which uses a) a particle size distribution D50 of 900 nm or less, and b) a zirconia monoclinic phase content of 90 to 95 volumes. % and the content of the zirconia tetragonal phase is 5 to 10% by volume of the powder.
氧化鋯粉末使用前述D50為900nm以下之物。前述D50尤宜為800nm以下。此時，D50之下限值雖未受限，但通常為300nm左右，尤宜為400nm。因此，起始材料可使用含有氧化鋯凝集粒子之氧化鋯粉末。舉例來說，粒度分佈D50(二次粒子之平均粒徑)為400~700nm之氧化鋯粉末可適於用作起始材料。另，用作起始材料之氧化鋯粉末之一次粒子徑亦未受限，但通常可使用1~50nm左右(尤其是5~30nm)範圍內之氧化鋯粉末。換言之，也可使用諸如具有氧化鋯微晶徑5倍以上(尤其是10倍以上)範圍內之二次粒子徑(D50)的氧化鋯粉末。As the zirconia powder, the aforementioned D50 is 900 nm or less. The aforementioned D50 is particularly preferably 800 nm or less. At this time, although the lower limit of D50 is not limited, it is usually about 300 nm, and particularly preferably 400 nm. Therefore, the starting material may use zirconia powder containing zirconia agglomerated particles. For example, a zirconia powder having a particle size distribution D50 (average particle diameter of secondary particles) of 400 to 700 nm can be suitably used as a starting material. Further, the primary particle diameter of the zirconia powder used as the starting material is not limited, but zirconia powder in the range of about 1 to 50 nm (especially 5 to 30 nm) can be usually used. In other words, a zirconia powder such as a secondary particle diameter (D50) having a zirconia microcrystal diameter of 5 times or more (especially 10 times or more) may also be used.
起始材料之氧化鋯粉末可使用由結晶質氧化鋯粒子構成之物，尤其是使用氧化鋯單斜晶相之含量為90~95體積%且氧化鋯正方晶相之含量為5~10體積%之氧化鋯粉末。如此，藉由使用含特定量氧化鋯正方晶相之原料，可製得安定且更為微細之氧化鋯微粒子。The zirconia powder of the starting material may be composed of crystalline zirconia particles, in particular, the content of the zirconia monoclinic phase is 90 to 95% by volume and the content of the zirconia tetragonal phase is 5 to 10% by volume. Zirconia powder. Thus, by using a raw material containing a specific amount of zirconia tetragonal phase, stable and finer zirconia fine particles can be obtained.
此外，起始材料之氧化鋯粉末之比表面積亦未受限，但尤宜使用比表面積為70m2 /g以上(更宜80m2 /g以上)之粉末。藉由使用具有此種比表面積之氧化鋯粉末，可更確實地製得高分散性之奈米粒子。另，比表面積之上限雖不具限定性，但通常設為200m2 /g左右，尤宜設為150m2 /g。Further, the specific surface area of the zirconia powder of the starting material is not limited, but it is particularly preferable to use a powder having a specific surface area of 70 m 2 /g or more (more preferably 80 m 2 /g or more). By using zirconia powder having such a specific surface area, highly dispersible nanoparticles can be more reliably produced. Further, although the upper limit of the specific surface area is not limited, it is usually about 200 m 2 /g, and particularly preferably 150 m 2 /g.
具有此種結晶構造、物性等之氧化鋯粉末本身可使用習知或市售物。此外，亦可使用以習知製法合成出之氧化鋯粉末。例如，可適用以水解法、共沉法、中和法、烷氧化物法等液相法合成出之氧化鋯。特別就水解法而言，可藉由水解鋯鹽合成出水和氧化鋯溶膠後，將前述溶膠暫時加熱所得氧化鋯粉末等適宜地用作起始原料。如前述，本發明在無需使用特別之原料而可使用習知或市售之一般氧化鋯粉末作為原料之觀點上以及成本上均為有效方法。亦即，本發明之製造方法使用此種含有氧化鋯單斜晶相與氧化鋯正方晶相之氧化鋯粉末作為起始原料，可確實且有效率地製得單斜晶氧化鋯系奈米粒子，其繞射圖案之2θ=29.74~30.74度中實質上不存在繞射尖峰。A zirconia powder having such a crystal structure, physical properties and the like can be used by itself or a commercially available product. Further, a zirconia powder synthesized by a conventional method can also be used. For example, zirconia synthesized by a liquid phase method such as a hydrolysis method, a coprecipitation method, a neutralization method, or an alkoxide method can be applied. In particular, in the hydrolysis method, water and a zirconia sol can be synthesized by hydrolyzing a zirconium salt, and then the zirconia powder obtained by temporarily heating the sol is suitably used as a starting material. As described above, the present invention is an effective method from the viewpoint of the use of a conventional or commercially available general zirconia powder as a raw material without using a special raw material. That is, the production method of the present invention uses such a zirconia powder containing a zirconia monoclinic phase and a zirconia tetragonal phase as a starting material, and can obtain monoclinic zirconia-based nanoparticles reliably and efficiently. There is substantially no diffraction peak in the 2θ=29.74~30.74 degrees of the diffraction pattern.
珠磨處理步驟 珠磨處理步驟係於粒度分佈D50為40μm以下之珠粒存在下將前述氧化鋯粉末供予珠磨處理。Bead mill treatment step The bead mill treatment step is to subject the aforementioned zirconia powder to bead mill treatment in the presence of beads having a particle size distribution D50 of 40 μm or less.
用作媒介(粉碎媒體)之珠粒僅需使粒度分佈D50在40μm以下之範圍內即可，且宜為35μm以下，更宜為32μm以下，最宜30μm以下。上述D50超過40μm時，有無法獲得安定且分散性高之奈米粒子之虞。另，前述D50之下限值雖不具限定性，但通常設為1μm左右即可，尤宜為10μm左右，更宜為20μm左右。本發明可藉由使用此種相對微細之珠粒而更有效率且確實地調製出微細單斜晶氧化鋯系奈米粒子。The beads used as the medium (pulverizing medium) need only have a particle size distribution D50 of 40 μm or less, and preferably 35 μm or less, more preferably 32 μm or less, and most preferably 30 μm or less. When the above D50 exceeds 40 μm, there is a possibility that a stable and highly dispersible nanoparticle cannot be obtained. Further, although the lower limit of the D50 is not limited, it is usually about 1 μm, and is preferably about 10 μm, more preferably about 20 μm. The present invention can more efficiently and reliably prepare fine monoclinic zirconia-based nanoparticles by using such relatively fine beads.
珠粒之組成並未特別受限，可採用與習知珠磨機等所用珠粒同樣之材質。例如可適用氧化鋯、氧化鋁、氧化矽等氧化物系珠粒、鎳、銅、鎢、鋼等金屬系珠粒、氮化鈦、氮化矽等非氧化物系珠粒等之無機材料系珠粒。從減輕、防止雜質混入及混合效率性等觀點來看，尤宜使用氧化鋯珠粒。The composition of the beads is not particularly limited, and the same materials as those used in conventional bead mills and the like can be used. For example, oxide-based beads such as zirconia, alumina, or cerium oxide, metal-based beads such as nickel, copper, tungsten, and steel, and inorganic materials such as non-oxide beads such as titanium nitride or tantalum nitride can be used. Beads. From the viewpoints of mitigating, preventing the incorporation of impurities, and mixing efficiency, it is particularly preferable to use zirconia beads.
珠粒形狀通常宜使用略呈球狀之珠粒。此種球狀珠粒可使用習知或市售物。尤其可適用以電漿熔融法(熱電漿熔融法)調製出之球狀珠粒。電漿熔融法本為習知方法，可利用諸如日本特開2007-4090所揭方法等。亦即，於大氣壓中形成之電漿氣體環境內，以氣相狀態連續供給氧化鋯之原料粉末(例如以粉碎法調製出之粉末)，構成前述原料粉末之氧化鋯粒子表面熔融而使該粒子球狀化，之後可藉由包含對流下之該粒子吹噴冷卻氣體使該粒子急速冷卻之步驟的方法來製造球狀氧化鋯粒子。此種方法所得球狀氧化鋯粒子在其粒子形狀大致呈球狀且較少粗大粒子之觀點上有利。It is generally preferred to use a slightly spherical bead in the shape of the bead. Such spherical beads can be used conventionally or commercially. In particular, spherical beads prepared by a plasma melting method (thermoelectric plasma melting method) can be applied. The plasma melting method is a conventional method, and a method such as those disclosed in JP-A-2007-4090 can be utilized. That is, in the plasma gas atmosphere formed in the atmospheric pressure, the raw material powder of zirconia (for example, a powder prepared by a pulverization method) is continuously supplied in a vapor phase, and the surface of the zirconia particles constituting the raw material powder is melted to make the particles. Spheroidization, after which the spherical zirconia particles can be produced by a method comprising the step of rapidly cooling the particles by blowing a cooling gas under the convection. The spherical zirconia particles obtained by such a method are advantageous from the viewpoint of a particle shape of substantially spherical and less coarse particles.
珠粒之使用量並不具限定性，但一般而言，可視相對於填充珠粒之空間(通常是珠磨裝置中之粉碎室)容量的珠粒外觀體積比(珠粒填充率)來決定，因應珠磨裝置之型號等將珠粒填充率適當設在10~90%範圍內即可。因此，舉例來說，可設在50~70%範圍內，也可進一步設在40~60%範圍內。此外，舉例來說，亦如同後述實施例所示，珠粒使用熱電漿熔融法所得球狀氧化鋯珠粒時，亦可設成滿足上述珠粒填充率且相對於氧化鋯粉末100重量份前述珠粒為600~900重量份之範圍內。The amount of beads used is not limited, but in general, it can be determined by the volume ratio of the bead appearance (bead filling rate) relative to the volume of the space in which the beads are filled (usually the pulverizing chamber in the bead mill). The bead filling rate should be appropriately set within the range of 10 to 90% depending on the model of the bead mill. Therefore, for example, it may be set in the range of 50 to 70%, or may be further set in the range of 40 to 60%. Further, for example, as shown in the later-described examples, when the beads are obtained by using the thermo-plasma melting method, the spherical zirconia beads may be set to satisfy the above-described bead filling ratio and 100 parts by weight relative to the zirconia powder. The beads are in the range of 600 to 900 parts by weight.
珠磨處理係一以珠粒(粉碎媒體)所生剪切力或衝撃力來粉碎及分散起始材料之方法，例如可使用習知或市售之珠磨裝置來實施。因此，珠磨裝置之型號、形式亦未特別受限。舉例來說，設於珠磨裝置之攪拌器形狀亦不受限，例如碟型、銷型、單輥型等中之任一者皆可。此外，粉碎室(導管)可為縱型及橫型中之任一者。又，珠磨機之運作方式亦不具限定性，可為循環式、道次式、批次式等中之任一者。The bead mill treatment is a method of pulverizing and dispersing a starting material by a shearing force or a punching force generated by a bead (pulverizing medium), and can be carried out, for example, using a conventional or commercially available bead mill device. Therefore, the model and form of the bead mill are not particularly limited. For example, the shape of the agitator provided in the bead mill device is not limited, and may be any of a disc type, a pin type, a single roll type, and the like. Further, the pulverization chamber (catheter) may be either a vertical type or a horizontal type. Moreover, the operation mode of the bead mill is not limited, and may be any of a circulation type, a pass type, and a batch type.
市售之珠磨裝置只要可在本發明之條件下進行珠磨處理者即不具限定性。例如，也可使用Super Apex Mill(HIROSHIMA METAL & MACHINERY CO.,LTD.製)、Ultra Apex Mill (HIROSHIMA METAL & MACHINERY CO.,LTD.製)、Dual Apex mill (HIROSHIMA METAL & MACHINERY CO.,LTD.製)、MSC Mill(NIPPON COKE & ENGINEERING CO., LTD.製)、Nano Getter(Ashizawa Finetech Ltd.製)、MAX Nano Getter(Ashizawa Finetech Ltd.製)、LABSTAR Mini(Ashizawa Finetech Ltd.製)、JBM系列(JBM-B035、JBM-C020、JBM-C050、JBM-C200、JBM-C500、JBM-C1000、Waterspout-Combo、JBM-D500、JBM-D1000、JBM-D2000)(均為JUST NANOTECH CO., Ltd.製)。The commercially available bead mill device is not limited as long as it can be subjected to bead mill treatment under the conditions of the present invention. For example, Super Apex Mill (manufactured by HIROSHIMA METAL & MACHINERY CO., LTD.), Ultra Apex Mill (manufactured by HIROSHIMA METAL & MACHINERY CO., LTD.), and Dual Apex mill (HIROSHIMA METAL & MACHINERY CO., LTD.) can also be used. MSC Mill (manufactured by NIPPON COKE & ENGINEERING CO., LTD.), Nano Getter (manufactured by Ashizawa Finetech Ltd.), MAX Nano Getter (manufactured by Ashizawa Finetech Ltd.), LABSTAR Mini (manufactured by Ashizawa Finetech Ltd.), JBM Series (JBM-B035, JBM-C020, JBM-C050, JBM-C200, JBM-C500, JBM-C1000, Waterspout-Combo, JBM-D500, JBM-D1000, JBM-D2000) (both JUST NANOTECH CO., Ltd.).
就珠磨裝置之操作條件而言，以具備本發明製造方法之條件(使用特定起始材料及珠粒)為前提，可視所用氧化鋯粉末之性狀、溶劑種類、珠粒種類等來適當設定。舉例來說，本發明以設有攪拌器之珠磨裝置而言，通常可設定攪拌器周速5~20m/秒左右，特別是7~15m/秒。滯留時間(處理時間)一般設在5~25分鐘左右(特別是8~20分鐘)，但只要可確保所得氧化鋯微粒子(粉末)以X射線繞射分析所得繞射圖譜變得實質上無法識別出氧化鋯正方晶相所需之時間充分，並不特別受上述時間所制約。The operating conditions of the bead mill apparatus are appropriately set depending on the properties of the zirconia powder to be used, the type of the solvent, the type of the beads, and the like, provided that the conditions of the production method of the present invention (using a specific starting material and beads) are used. For example, in the present invention, the bead mill device provided with the agitator can generally set the peripheral speed of the agitator to about 5 to 20 m/sec, especially 7 to 15 m/sec. The residence time (treatment time) is generally set at about 5 to 25 minutes (especially 8 to 20 minutes), but it is ensured that the diffraction pattern obtained by X-ray diffraction analysis of the obtained zirconia fine particles (powder) becomes substantially unrecognizable. The time required to form the zirconia tetragonal phase is sufficient and is not particularly limited by the above time.
此外，本發明之珠磨處理可為乾式及濕式中任一者，尤宜採用濕式珠磨處理。此時，溶劑除了水之外，可使用諸如甲醇、乙醇、異丙醇、丁醇等醇系溶劑、酮、丙酮、甲乙酮、甲丙酮、甲基異丁酮等酮系溶劑、異丙醚、甲基賽璐蘇等醚系溶劑、丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯等二醇酯系溶劑等各種有機溶劑。Further, the bead mill treatment of the present invention may be either dry or wet, and it is preferred to employ a wet bead mill treatment. In this case, in addition to water, the solvent may be an alcohol solvent such as methanol, ethanol, isopropanol or butanol, a ketone solvent such as ketone, acetone, methyl ethyl ketone, methyl acetone or methyl isobutyl ketone, or isopropyl ether. Various organic solvents such as an ether solvent such as methyl acesulfame, a glycol ester solvent such as propylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate.
此外，珠磨處理時，除了溶劑之外，亦可視需要而摻合各種添加劑。例如，可摻合分散劑、偶合劑、黏合劑、分散助劑等各種添加劑。本發明尤宜在獲得高分散性等目的下使分散液中含有分散劑及偶合劑二者。Further, in the bead mill treatment, in addition to the solvent, various additives may be blended as needed. For example, various additives such as a dispersant, a coupling agent, a binder, and a dispersing aid may be blended. In the present invention, it is preferred to contain both a dispersing agent and a coupling agent in the dispersion liquid for the purpose of obtaining high dispersibility and the like.
分散劑可使用諸如非離子系、陰離子系、陽離子系等任一類型之分散劑，但本發明中以陰離子系分散劑尤佳。陰離子系分散劑尤可適用磷酸酯系分散劑。此等分散劑亦可使用市售品。As the dispersing agent, any type of dispersing agent such as a nonionic type, an anionic type, or a cationic type can be used, but an anionic dispersing agent is particularly preferable in the present invention. An anionic dispersant is particularly suitable for a phosphate ester dispersant. Commercially available products can also be used for such dispersing agents.
分散劑之添加量並未特別限定，通常可在相對於氧化鋯粉末100重量份為0.1~100重量份之範圍內視所用分散劑之種類等予以適當設定。因此，舉例來說，可設在相對於氧化鋯粉末100重量份為0.4~100重量份之範圍內，又可舉例如設在相對於氧化鋯粉末100重量份為0.5~20重量份之範圍內，更可進一舉例如設在相對於氧化鋯粉末100重量份為1~10重量份之範圍內。The amount of the dispersing agent to be added is not particularly limited, and may be appropriately set depending on the type of the dispersing agent to be used, and the like, in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the zirconia powder. Therefore, for example, it may be in the range of 0.4 to 100 parts by weight based on 100 parts by weight of the zirconia powder, and may be, for example, in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the zirconia powder. Further, for example, it is set to be in the range of 1 to 10 parts by weight based on 100 parts by weight of the zirconia powder.
偶合劑可舉例如矽烷偶合劑、鈦偶合劑等，本發明中尤適用矽烷偶合劑。 矽烷偶合劑並未特別受限，但可使用至少具有丙烯醯基或甲基丙烯醯基作為官能基之矽烷劑為宜。 作為一例，可舉如通式X3-n (CH3 )n Si-R-Y(但n=1或2，R表示伸乙基或伸丙基，X表示水解性基，Y表示官能基)所示矽烷偶合劑。前述水解性基X可例示如甲氧基、乙氧基、2-甲氧基乙氧基等烷氧基。前述官能基Y可例示如乙烯基、環氧基、苯乙烯基、脲基、丙烯醯基、甲基丙烯醯基、胺基、三聚異氰酸酯基、異氰酸酯基、巰基等。舉例來說，可適用上述通式中上述R為丙烯醯基或甲基丙烯醯基之矽烷偶合劑。此等矽烷偶合劑亦可使用市售品。The coupling agent may, for example, be a decane coupling agent or a titanium coupling agent. In the present invention, a decane coupling agent is particularly suitable. The decane coupling agent is not particularly limited, but a decane agent having at least an acryloyl group or a methacryl group as a functional group may be preferably used. As an example, a compound of the formula X 3-n (CH 3 ) n Si-RY (but n = 1 or 2, R represents an exoethyl or a propyl group, X represents a hydrolyzable group, and Y represents a functional group) A decane coupling agent. The hydrolyzable group X may, for example, be an alkoxy group such as a methoxy group, an ethoxy group or a 2-methoxyethoxy group. The functional group Y may, for example, be a vinyl group, an epoxy group, a styryl group, a ureido group, an acrylonitrile group, a methacryl fluorenyl group, an amine group, a trimer isocyanate group, an isocyanate group or a fluorenyl group. For example, a decane coupling agent in which R is an acrylonitrile group or a methacryl fluorenyl group in the above formula can be applied. Commercially available products can also be used for such decane coupling agents.
偶合劑之添加量並無特別限制，但一般而言，在相對於氧化鋯粉末100重量份為2~200重量份之範圍內，可視諸如所用分散劑之種類等而予以適當設定。因此，舉例來說，可設在相對於氧化鋯粉末100重量份為5~100重量份之範圍內，亦可設在相對於氧化鋯粉末100重量份為5~50重量份範圍內，更可進一步設在相對於氧化鋯粉末100重量份為10~20重量份之範圍內。In the range of 2 to 200 parts by weight based on 100 parts by weight of the zirconia powder, the amount of the coupling agent to be added is appropriately set, for example, depending on the type of the dispersing agent to be used. Therefore, for example, it may be in the range of 5 to 100 parts by weight based on 100 parts by weight of the zirconia powder, or may be in the range of 5 to 50 parts by weight based on 100 parts by weight of the zirconia powder, and more preferably Further, it is in the range of 10 to 20 parts by weight based on 100 parts by weight of the zirconia powder.
珠磨處理結束後，按常法與珠粒分離後，僅需回收氧化鋯系奈米粒子即可。此時，實施濕式珠磨處理時，可以前述溶劑中分散有氧化鋯系奈米粒子之分散液形態來回收。此時可視需要而將一部份或全部溶劑替換為其他溶劑，或進一步於溶劑中添加分散劑等。After the bead milling treatment is completed, it is only necessary to recover the zirconia-based nanoparticles after separation from the beads by the usual method. In this case, when the wet bead mill treatment is carried out, it can be recovered in the form of a dispersion in which the zirconia-based nanoparticles are dispersed in the solvent. At this time, some or all of the solvent may be replaced with another solvent as needed, or a dispersant or the like may be further added to the solvent.
3.氧化鋯系奈米粒子之使用 本發明之氧化鋯系奈米粒子可與習知之氧化鋯奈米粒子應用於同樣之用途上。3. Use of zirconia-based nanoparticles The zirconia-based nanoparticles of the present invention can be applied to the same applications as the conventional zirconia nanoparticles.
尤其是為了活用本發明奈米粒子之高度折射率等特長，舉例來說，可以透鏡、光學過濾器、抗反射材、硬塗材、折射率調整材等各種光學零件為中心，廣泛利用在各種用途上。亦即，可將本發明奈米粒子作為習知或市售光學零件之分散材(特別是高折射率粒子)來應用。此時，可單獨使用本發明之氧化鋯系奈米粒子，或者，也可在含有本發明之氧化鋯系奈米粒子及樹脂成分之複合材料形態下使用。就樹脂成分而言，亦可採用如同習知複合材料所採用之各種合成樹脂，例如聚酯樹脂、聚烯烴樹脂、聚醯胺樹脂、丙烯酸樹脂等。 實施例In particular, in order to utilize the characteristics such as the high refractive index of the nanoparticles of the present invention, for example, various optical components such as a lens, an optical filter, an antireflection material, a hard coating material, and a refractive index adjusting material can be widely used in various types. Use. That is, the nanoparticle of the present invention can be applied as a dispersion material (particularly, a high refractive index particle) of a conventional or commercially available optical component. In this case, the zirconia-based nanoparticles of the present invention may be used singly or in the form of a composite material containing the zirconia-based nanoparticles of the present invention and a resin component. As the resin component, various synthetic resins such as a polyester resin, a polyolefin resin, a polyamide resin, an acrylic resin and the like can be used as in the conventional composite material. Example
以下顯示實施例俾更具體說明本發明之特徵。但本發明之範圍不受實施例所侷限。The embodiments are shown below to more specifically illustrate the features of the present invention. However, the scope of the invention is not limited by the examples.
實施例1 (1)氧化鋯系奈米粒子分散液之調製 以下述方式調製出氧化鋯系奈米粒子分散於溶劑而成之分散液。起始材料之氧化鋯粉末使用市售品。此市售品之粒度分佈D50在0.4~0.7μm之範圍內，單斜晶相為94體積%且正方晶相為6體積%，比表面積為80m2 /g。將該氧化鋯粉末6g與添加劑(矽烷偶合劑0.9g及磷酸酯系分散劑0.3g)摻合至甲乙酮15g後，以珠磨裝置(批次式珠磨機，大研化學工業股份有限公司製)將所得混合液實施珠磨處理。上述裝置係由圖7所示結構所構成，使用了1個圖8所示單輥型攪拌器。珠粒使用市售之利用熱電漿熔融法而球狀化之氧化鋯珠粒(大研化學工業股份有限公司製「DZB」，粒度分佈D50為30μm)50g(相對於粉碎室之容積為44體積%)，令攪拌器周速10m/s，處理時間15分鐘。如此而獲得含有氧化鋯系奈米粒子之分散液。Example 1 (1) Preparation of zirconia-based nanoparticle dispersion liquid A dispersion liquid obtained by dispersing zirconia-based nanoparticles in a solvent was prepared in the following manner. Commercially available products are used as the zirconia powder of the starting material. The commercially available product has a particle size distribution D50 in the range of 0.4 to 0.7 μm, a monoclinic phase of 94% by volume and a tetragonal phase of 6% by volume, and a specific surface area of 80 m 2 /g. 6 g of the zirconia powder and an additive (0.9 g of a decane coupling agent and 0.3 g of a phosphate dispersing agent) were blended into 15 g of methyl ethyl ketone, and then a bead mill (a batch type bead mill, manufactured by Daisei Chemical Industry Co., Ltd.) The resulting mixture was subjected to a bead mill treatment. The above apparatus was constructed by the structure shown in Fig. 7, and one single-roller type agitator shown in Fig. 8 was used. For the beads, commercially available zirconia beads (DZB manufactured by Dayan Chemical Co., Ltd., particle size distribution D50 of 30 μm) which were spheroidized by a hot plasma melting method were used, 50 g (the volume with respect to the crushing chamber was 44 volumes). %), so that the stirrer has a peripheral speed of 10 m/s and a treatment time of 15 minutes. Thus, a dispersion containing zirconia-based nanoparticles was obtained.
茲將實施例1所用珠磨裝置之概略圖顯示於圖7。珠磨裝置10設有：a)用以收容珠粒11及被處理物(含分散介質)12之粉碎室(導管)13；b)配置於粉碎室13內之攪拌器14；c)使前述攪拌器14旋轉之馬達15；d)用以將馬達15之旋轉驅動力傳送到攪拌器14之軸16；及，e)收容冷卻粉碎室13外側之冷卻水18的冷卻水套17。冷卻水18流入冷卻水套17並吸收粉碎時發生之熱後，從冷卻水套17排出，放冷後回到冷卻水套17，以此方式循環。A schematic view of the bead mill apparatus used in Example 1 is shown in Fig. 7. The bead mill 10 is provided with: a) a pulverizing chamber (catheter) 13 for accommodating the beads 11 and the object to be treated (including the dispersion medium) 12; b) an agitator 14 disposed in the pulverizing chamber 13; c) The motor 15 that rotates the agitator 14; d) transmits the rotational driving force of the motor 15 to the shaft 16 of the agitator 14; and, e) receives the cooling water jacket 17 that cools the cooling water 18 outside the crushing chamber 13. The cooling water 18 flows into the cooling water jacket 17 and absorbs the heat generated during the pulverization, and is discharged from the cooling water jacket 17, and is cooled and returned to the cooling water jacket 17, and circulated in this manner.
攪拌器13係如圖8(a)所示，於中心軸之位置上，軸16安裝在攪拌器14上。圖8(b)係從圖8(a)之箭頭A方向觀視之圖。如圖8(b)所示，實施例使用之攪拌器14為接近風車形狀之單輥型，其藉由朝順時鐘(箭頭方向)旋轉來進行粉碎。The agitator 13 is attached to the agitator 14 at a position of the central axis as shown in Fig. 8(a). Fig. 8(b) is a view from the direction of arrow A of Fig. 8(a). As shown in Fig. 8(b), the agitator 14 used in the embodiment is a single roll type close to a windmill shape, and is pulverized by rotating in a clockwise direction (arrow direction).
(2)氧化鋯系奈米粒子之評價 針對所得分散液中之氧化鋯系奈米粒子調查結晶構造及粒度。(2) Evaluation of zirconia-based nanoparticles The crystal structure and particle size of the zirconia-based nanoparticles in the obtained dispersion were examined.
1)結晶構造 1-1)X射線繞射分析 針對將實施例1所得分散液乾燥而得之粉末，實施粉末X射線繞射分析。X射線繞射裝置使用「MiniFlex 600」(Rigaku Corporation製)。將其分析結果(顯示為「處理後」)顯示於圖1。另，為了比較而在圖1中一併顯示以同樣方式測定處理前之氧化鋯粉末(起始材料)的結果。如圖1所示，可知就實施例1所得氧化鋯系奈米粒子而言，繞射圖案中2θ=29.74~30.74度範圍內之繞射尖峰(特別是氧化鋯正方晶相之繞射尖峰)消失。1) Crystal structure 1-1) X-ray diffraction analysis A powder obtained by drying the dispersion obtained in Example 1 was subjected to powder X-ray diffraction analysis. The "MiniFlex 600" (manufactured by Rigaku Corporation) was used for the X-ray diffraction device. The analysis result (displayed as "after processing") is shown in Fig. 1. Further, for comparison, the results of measuring the zirconia powder (starting material) before the treatment in the same manner are shown together in Fig. 1. As shown in Fig. 1, it is understood that in the zirconia-based nanoparticles obtained in Example 1, a diffraction peak in the diffraction pattern in the range of 2θ = 29.74 to 30.74 degrees (particularly a diffraction peak of a zirconia tetragonal phase) disappear.
1-2)拉曼分光法分析 此外，也針對前述粉末調查拉曼分光法之結晶性。拉曼分光裝置使用「雷射拉曼顯微鏡RAMAN Touch」(Nanophoton Corporation製)，設為激發波長532nm、繞射格子2400gr/mm。將該拉曼圖譜(顯示為「處理後」)示於圖2。另，為了比較而在圖2中一併顯示以同樣方式測定處理前之氧化鋯粉末(起始材料)的結果。從圖2亦可明確得知，即使利用拉曼圖譜，實施例1所製造之氧化鋯系奈米粒子仍無源自氧化鋯正方晶相之波數202cm-1 及267cm-1 的尖峰。1-2) Raman spectroscopy analysis In addition, the crystallinity of the Raman spectroscopy method was also investigated for the above powder. The Raman spectroscopic device used "Raman Raman microscope RAMAN Touch" (manufactured by Nanophoton Corporation), and had an excitation wavelength of 532 nm and a diffraction grating of 2400 gr/mm. The Raman spectrum (shown as "after processing") is shown in Fig. 2. Further, for comparison, the results of measuring the zirconia powder (starting material) before the treatment in the same manner are shown together in Fig. 2 . As is clear from Fig. 2, even if the Raman pattern was used, the zirconia-based nanoparticles produced in Example 1 did not have a peak derived from the wave number of the zirconia tetragonal phase of 202 cm -1 and 267 cm -1 .
1-3)電子繞射分析 更進一步對前述粉末實施電子繞射分析。使用金微粒子作為面間隔參照用標準試料，從該標準試料之曲線取得長度資料。算出單斜晶及正方晶之最強線111m、111t之位置。茲將該電子繞射所得強度曲線示於圖3。圖3之上圖顯示處理前(起始材料)之結果，圖3之下圖顯示實施例1所得奈米粒子之結果。從圖3之結果亦可明確得知，處理後之奈米粒子不會確認到正方晶之111t之尖峰。1-3) Electron diffraction analysis Further, electronic diffraction analysis was performed on the aforementioned powder. Gold microparticles were used as a standard sample for surface spacing reference, and length data was obtained from the curve of the standard sample. Calculate the positions of the strongest lines 111m and 111t of the monoclinic and tetragonal crystals. The intensity curve obtained by this electron diffraction is shown in Fig. 3. The upper graph of Fig. 3 shows the results before the treatment (starting material), and the lower graph of Fig. 3 shows the results of the nanoparticles obtained in Example 1. It can also be clearly seen from the results of Fig. 3 that the treated nanoparticles do not recognize the sharp peak of 111t of the tetragonal crystal.
2)粒度 粒度測定使用動態光散射式粒度分佈測定裝置「Nanotrac Wave EX-150」(MicrotracBEL Corp.製)。粒度係測定體積基準之累積分佈D50及D90。茲將其結果示於圖4。從圖4之頻率分佈及累積分佈之結果亦可明確得知，粒度分佈(頻度分佈)呈單峰，D50約12nm，D90約20nm。 此外，調查粒度分佈D90、處理時間及正方晶/單斜晶之尖峰比(強度比)之關係。茲將結果示於圖5。如圖5所示，隨著氧化鋯單斜晶相增大，D90亦連動縮小。亦即，在氧化鋯正方晶相減少之同時，氧化鋯單斜晶相增加，因此變得較起始材料時之單斜晶相94體積%更多。此外，可從圖5之結果推察出，存在於起始材料中之正方晶相變為單斜晶時氧化鋯凝集粒子解開一事也對微細化有所助益，結果則是獲得高分散性。2) Particle size The particle size measurement was performed using a dynamic light scattering type particle size distribution measuring apparatus "Nanotrac Wave EX-150" (manufactured by MicrotracBEL Corp.). The particle size is the cumulative distribution of the volume basis D50 and D90. The results are shown in Figure 4. It can also be clearly seen from the results of the frequency distribution and the cumulative distribution of Fig. 4 that the particle size distribution (frequency distribution) is a single peak, D50 is about 12 nm, and D90 is about 20 nm. Further, the relationship between the particle size distribution D90, the treatment time, and the peak ratio (intensity ratio) of tetragonal/monoclinic crystals was investigated. The results are shown in Figure 5. As shown in Figure 5, as the zirconia monoclinic phase increases, D90 also shrinks. That is, while the zirconia tetragonal phase is reduced, the zirconia monoclinic phase increases, and thus becomes more than 94% by volume of the monoclinic phase at the time of the starting material. Further, it can be inferred from the results of Fig. 5 that the disintegration of the zirconia agglomerated particles when the tetragonal phase is changed to monoclinic in the starting material also contributes to the refinement, and as a result, high dispersibility is obtained. .
試驗例2 使用平均粒徑D50不同之氧化鋯珠粒，與實施例1同樣地調製出氧化鋯系奈米粒子(比較試料1及比較試料2)。與實施例1同樣地以X射線繞射分析來調查所得氧化鋯系奈米粒子之結晶相。氧化鋯珠粒分別使用了D50為50μm之珠粒(比較試料1使用者)、D50為100μm之珠粒(比較試料2使用者)。將其結果示於圖6。另，於圖6中一併顯示實施例1所得氧化鋯系奈米粒子之分析結果。 從圖6之結果亦可明確得知，實施例1之氧化鋯系奈米粒子(使用珠粒徑D50=30μm，圖6中之符號A)在2θ=29.74~30.74度範圍內不存在繞射尖峰。相對於此，以D50超過40μm之氧化鋯珠粒調製出之比較試料1(使用珠粒徑D50=50μm，圖6中之符號B)及比較試料2(使用珠粒徑D50=100μm，圖6中之符號C)則在2θ=29~30度之範圍(特別是2θ=29.74~30.74度之範圍)內出現些微繞射尖峰。Test Example 2 Zirconia-based nanoparticles (Comparative Sample 1 and Comparative Sample 2) were prepared in the same manner as in Example 1 except that zirconia beads having different average particle diameters D50 were used. The crystal phase of the obtained zirconia-based nanoparticles was examined by X-ray diffraction analysis in the same manner as in Example 1. As the zirconia beads, beads having a D50 of 50 μm (compared to the sample 1 user) and beads having a D50 of 100 μm (compared to the sample 2 user) were used. The result is shown in Fig. 6. Further, the analysis results of the zirconia-based nanoparticles obtained in Example 1 are shown together in Fig. 6. As is clear from the results of Fig. 6, the zirconia-based nanoparticles of Example 1 (using the bead diameter D50 = 30 μm, symbol A in Fig. 6) have no diffraction in the range of 2θ = 29.74 to 30.74 degrees. peak. On the other hand, the comparative sample 1 (using the bead diameter D50=50 μm, symbol B in FIG. 6) and the comparative sample 2 (using the bead diameter D50=100 μm) prepared by using zirconia beads having a D50 of more than 40 μm, FIG. 6 The symbol C) has some micro-diffraction spikes in the range of 2θ=29~30 degrees (especially in the range of 2θ=29.74~30.74 degrees).
試驗例3 與實施例1同樣調製出含氧化鋯系奈米粒子之分散液，調查從剛調製後至一定期間內之粒度分佈變化。將結果示於表1。Test Example 3 A dispersion liquid containing zirconia-based nanoparticles was prepared in the same manner as in Example 1, and the change in particle size distribution from the immediately after preparation to a certain period of time was examined. The results are shown in Table 1.
[表1]
從表1之結果可明確得知，含氧化鋯系奈米粒子之分散液在調製後經過約6個月後仍維持與當初(0天)大致相同之粒度分佈，具有優異之分散安定性。As is clear from the results of Table 1, the dispersion containing zirconia-based nanoparticles maintained a particle size distribution substantially the same as that of the original (day 0) after about 6 months from the preparation, and had excellent dispersion stability.
試驗例4 與實施例1同樣地調製出含氧化鋯系奈米粒子之分散液(分散液1)。此外，使用平均粒徑D50不同之氧化鋯珠粒，與實施例1同樣地調製出含氧化鋯系奈米粒子之分散液(比較分散液1及比較分散液2)。氧化鋯珠粒分別使用D50為100μm之珠粒(比較分散液1使用者)、D50為50μm之珠粒(比較分散液2使用者)。針對所得各分散液調查透射率及粒度分佈。透射率係以溶劑(MEK)作為空白試料(透射率100%)，測定令光路長為5mm時在測定波長600nm下之分光透射率。粒度分佈與實施例1以同樣方式測定。茲將此等結果示於表2。Test Example 4 A dispersion liquid containing zirconia-based nanoparticles (dispersion liquid 1) was prepared in the same manner as in Example 1. Further, a dispersion containing zirconia-based nanoparticles (Comparative Dispersion 1 and Comparative Dispersion 2) was prepared in the same manner as in Example 1 except that zirconia beads having different average particle diameters D50 were used. As the zirconia beads, beads having a D50 of 100 μm (compared to the user of the dispersion 1) and beads having a D50 of 50 μm (compared to the dispersion 2 user) were used. The transmittance and the particle size distribution were investigated for each of the obtained dispersions. The transmittance was measured by using a solvent (MEK) as a blank sample (transmittance: 100%), and measuring the spectral transmittance at a measurement wavelength of 600 nm when the optical path length was 5 mm. The particle size distribution was measured in the same manner as in Example 1. These results are shown in Table 2.
[表2]
從表2結果亦可明確得知，本發明之分散液1因微細且分散性優異而獲得了30%以上(尤其是35%以上)之高度透射率。相對於此，比較分散液1及2因含有相對較粗大之粒子，透射率變得較低。As is clear from the results of Table 2, the dispersion liquid 1 of the present invention has a high transmittance of 30% or more (especially 35% or more) because of its excellent fineness and dispersibility. On the other hand, the comparative dispersions 1 and 2 contain relatively coarse particles, and the transmittance becomes low.
10‧‧‧珠磨裝置10‧‧‧Bead mill
11‧‧‧珠粒11‧‧‧ beads
12‧‧‧被處理物12‧‧‧Processed objects
13‧‧‧粉碎室13‧‧‧Crushing room
14‧‧‧攪拌器14‧‧‧Agitator
15‧‧‧馬達15‧‧‧Motor
16‧‧‧軸16‧‧‧Axis
17‧‧‧冷卻水套17‧‧‧Cooling water jacket
18‧‧‧冷卻水18‧‧‧Cooling water
圖1係一顯示實施例1所得氧化鋯奈米粒子之X射線繞射分析結果之圖。 圖2係一顯示實施例1所得氧化鋯奈米粒子之拉曼分光分析之拉曼光譜之圖。 圖3顯示實施例1所得氧化鋯奈米粒子由電子繞射取得之強度曲線。 圖4係一顯示實施例1所得氧化鋯奈米粒子之粒度分佈之圖。 圖5為圖表，係就實施例1所得氧化鋯奈米粒子顯示其粒度分佈D90及[正方晶相(T相)/單斜晶相(M相)]之尖峰比與處理時間的關係。 圖6係一顯示使用不同粒徑氧化鋯珠粒所得各氧化鋯系奈米粒子之X射線繞射分析結果之圖(擴大圖)。 圖7顯示實施例1所用珠磨裝置之概略圖。 圖8顯示實施例1所用珠磨裝置使用之攪拌器之概略圖。Fig. 1 is a graph showing the results of X-ray diffraction analysis of the zirconia nanoparticles obtained in Example 1. Fig. 2 is a view showing the Raman spectrum of Raman spectroscopic analysis of the zirconia nanoparticles obtained in Example 1. Fig. 3 is a graph showing the intensity curve obtained by electron diffraction of the zirconia nanoparticles obtained in Example 1. Fig. 4 is a graph showing the particle size distribution of the zirconia nanoparticles obtained in Example 1. Fig. 5 is a graph showing the relationship between the peak ratio of the particle size distribution D90 and [the tetragonal phase (T phase) / monoclinic phase (M phase)] and the treatment time for the zirconia nanoparticles obtained in Example 1. Fig. 6 is a view showing an X-ray diffraction analysis result of each zirconia-based nanoparticle obtained by using zirconia beads having different particle diameters (enlarged view). Fig. 7 is a schematic view showing a bead mill apparatus used in Example 1. Fig. 8 is a schematic view showing a stirrer used in the bead mill apparatus used in Example 1.
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