TW201808812A - Phosphonate modified metal oxide particle - Google Patents

Phosphonate modified metal oxide particle Download PDF

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TW201808812A
TW201808812A TW106119103A TW106119103A TW201808812A TW 201808812 A TW201808812 A TW 201808812A TW 106119103 A TW106119103 A TW 106119103A TW 106119103 A TW106119103 A TW 106119103A TW 201808812 A TW201808812 A TW 201808812A
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metal oxide
oxide particles
particles
tio
organic
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扈楠
王瑾菲
羽賀滿
陳紅宇
袁橋 饒
翼 章
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陶氏全球科技責任有限公司
羅門哈斯電子材料有限公司
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Abstract

Phosphonate group modified metal oxide particles, a method for forming the phosphonate group modified metal oxide particles and a material containing the phosphonate group modified metal oxide particles are disclosed. The metal oxide particles have low crystallinity and provide materials with high refractive indices (RIs) and high transparency.

Description

經膦酸酯基改質之金屬氧化物粒子 Metal oxide particles modified by phosphonate groups

本發明大體上涉及經膦酸酯基改質之金屬氧化物粒子、形成所述經膦酸酯基改質之金屬氧化物粒子之方法及含有所述經膦酸酯基改質之金屬氧化物粒子之材料。詳言之，本發明涉及具有低結晶度之經膦酸酯基改質之金屬氧化物粒子，其容易分散於有機材料中且提供具有高折射率(RI)及高透明度之有機材料。 The present invention generally relates to a phosphonate-modified metal oxide particle, a method of forming the phosphonate-modified metal oxide particle, and a metal oxide containing the phosphonate-modified material The material of the particles. In particular, the present invention relates to phosphonate-modified metal oxide particles having low crystallinity which are easily dispersed in an organic material and which provide an organic material having a high refractive index (RI) and high transparency.

電子組件通常由有機塗層材料覆蓋以防止其氧化或腐蝕。舉例而言，氧化銦錫(ITO)已用作觸摸屏面板上之透明電極，且亦藉由有機塗層材料塗佈。通常，將ITO電極安裝於玻璃基板上，接著將絕緣材料作為保護層塗覆於ITO電極上。通常，將丙烯酸或聚矽氧烷型聚合物組合物用於ITO電極之絕緣層，但此等絕緣層通常使ITO電極為可見的。原因在於此等絕緣層之折射率(RI)(1.5-1.6)及ITO電極之RI(1.8-2.2)非常不同，且RI之差異引起絕緣層與ITO電極之間的接口上之強光反射，從而使得ITO電極可見。光反射顯著降低顯示器之透光率且引起顯示器之相應較低的可見效能。為避免此問題，一種解決方案為使用具有與ITO電極相同或非常類似之RI值的絕緣層。另一解決方案為在ITO電極 與頂塗層(最外部絕緣層)之間形成抗反射層(一類絕緣層)，其中抗反射層具有ITO電極之RI與頂塗層之間的RI中間RI(1.7-1.9)。因此，需要RI比原始絕緣材料之RI高的絕緣層。 Electronic components are typically covered by an organic coating material to prevent oxidation or corrosion. For example, indium tin oxide (ITO) has been used as a transparent electrode on a touch screen panel and is also coated by an organic coating material. Usually, an ITO electrode is mounted on a glass substrate, and then an insulating material is applied as a protective layer on the ITO electrode. Typically, an acrylic or polyoxyalkylene type polymer composition is used for the insulating layer of the ITO electrode, but such insulating layers typically make the ITO electrode visible. The reason is that the refractive index (RI) (1.5-1.6) of the insulating layer and the RI (1.8-2.2) of the ITO electrode are very different, and the difference in RI causes strong light reflection on the interface between the insulating layer and the ITO electrode, Thereby the ITO electrode is visible. Light reflection significantly reduces the light transmission of the display and results in a correspondingly lower visible performance of the display. To avoid this problem, one solution is to use an insulating layer having the same or very similar RI value as the ITO electrode. Another solution is at the ITO electrode An antireflection layer (an insulating layer) is formed between the top coat (the outermost insulating layer), wherein the antireflection layer has an RI intermediate RI (1.7-1.9) between the RI of the ITO electrode and the top coat. Therefore, an insulating layer having a higher RI than the original insulating material is required.

在有機材料中添加諸如氧化鈦(TiO2)及氧化鋯(ZrO2)之金屬氧化物粒子以提高有機材料之RI。一些先前技術參考文獻揭示包括金屬氧化物粒子之有機材料，例如US6,521,677B、US201030174904A、WO2008/0588849A、JP4,917,196B、WO2012/058271A、US8,133,931B、US8,530,545B及US6,329,058B。 Metal oxide particles such as titanium oxide (TiO 2 ) and zirconium oxide (ZrO 2 ) are added to the organic material to increase the RI of the organic material. Some prior art references disclose organic materials including metal oxide particles, such as US 6,521,677 B, US 201030174904 A, WO 2008/0588849 A, JP 4,917,196 B, WO 2012/058271 A, US 8,133,931 B, US 8,530,545 B, and US 6,329,058B .

具有大直徑之金屬氧化物粒子會降低有機材料之透明度，因為導向有機材料之光會被此類大粒子反射。另外，即使使用具有小直徑之金屬氧化物粒子，但此類金屬氧化物粒子趨向於在有機材料中聚結。此等聚結之金屬氧化物粒子表現得如同大粒子一般，且亦降低有機材料之透明度。因此，仍需要具有小直徑及容易分散於有機材料中之能力之金屬氧化物粒子。 Metal oxide particles having a large diameter reduce the transparency of the organic material because light directed to the organic material is reflected by such large particles. In addition, even if metal oxide particles having a small diameter are used, such metal oxide particles tend to coalesce in an organic material. These coalesced metal oxide particles behave like large particles and also reduce the transparency of the organic material. Therefore, there is still a need for metal oxide particles having a small diameter and the ability to be easily dispersed in an organic material.

本發明提供一種經具有至少一個膦酸酯基之有機化合物改質之金屬氧化物粒子，由此會阻止金屬氧化物在有機材料中聚結。 The present invention provides a metal oxide particle modified with an organic compound having at least one phosphonate group, thereby preventing the metal oxide from coalescing in the organic material.

本發明之一個態樣涉及一種結晶度為60%或更小之金屬氧化物粒子，其中粒子之表面經(a)具有至少一個膦酸酯基之有機化合物及視情況存在之(b)有機矽烷化合物改質。 One aspect of the invention relates to a metal oxide particle having a crystallinity of 60% or less, wherein the surface of the particle is via (a) an organic compound having at least one phosphonate group and optionally (b) an organic decane Compound modification.

在另一態樣中，本發明涉及形成金屬氧化物粒子 之方法，所述方法包括以下步驟：(a)使金屬醇鹽於溶液中縮合以形成結晶度為60%或更小之金屬氧化物粒子，(b)使金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸以將金屬氧化物粒子改質，及(c)視情況使經有機化合物改質之金屬氧化物粒子與有機矽烷化合物接觸。 In another aspect, the invention relates to the formation of metal oxide particles A method comprising the steps of: (a) condensing a metal alkoxide in a solution to form metal oxide particles having a crystallinity of 60% or less, and (b) causing the metal oxide particles to have at least one phosphine The organic compound of the acid ester group is contacted to modify the metal oxide particles, and (c) the metal oxide particles modified by the organic compound are optionally contacted with the organic decane compound.

在又一態樣中，本發明涉及一種包括聚合物及金屬氧化物粒子之聚合物材料。 In yet another aspect, the present invention is directed to a polymeric material comprising a polymer and metal oxide particles.

在其他態樣中，本發明係關於一種包括金屬氧化物粒子之輻射敏感組合物，及由所述組合物形成之材料。 In other aspects, the invention is directed to a radiation-sensitive composition comprising metal oxide particles, and a material formed from the composition.

在另一態樣中，本發明涉及一種獲自以下步驟之反應產物：(a)使金屬醇鹽與酸接觸以形成金屬氧化物粒子，及(b)使金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸，接著(c)視情況使經有機化合物改質之金屬氧化物粒子與有機矽烷化合物接觸。 In another aspect, the invention relates to a reaction product obtained by: (a) contacting a metal alkoxide with an acid to form metal oxide particles, and (b) causing the metal oxide particles to have at least one phosphine The organic compound of the acid ester group is contacted, and then (c) the metal oxide particles modified with the organic compound are contacted with the organic decane compound as the case may be.

圖1為實例1中所獲得之金屬氧化物粒子之量與RI之間的相關性。 Figure 1 is a correlation between the amount of metal oxide particles obtained in Example 1 and RI.

圖2為實例2中所獲得之無氯三甲基矽烷處理之金屬氧化物粒子之NMR圖。 2 is an NMR chart of the chlorine-free trimethylnonane-treated metal oxide particles obtained in Example 2.

圖3為實例2中所獲得之無氯三甲基矽烷處理之金屬氧化物粒子之NMR圖。 Figure 3 is a NMR chart of the chlorine-free trimethylnonane-treated metal oxide particles obtained in Example 2.

圖4為實例11中所獲得之矽晶圓上之顯影圖。 4 is a developed view on a germanium wafer obtained in Example 11.

在本申請案中，詞語「(甲基)丙烯酸酯」包含丙 烯酸酯與甲基丙烯酸酯。在本申請案中，經具有至少一個膦酸酯基之有機化合物改質之金屬氧化物粒子亦稱為「經膦酸酯基改質之金屬氧化物粒子」。 In the present application, the word "(meth) acrylate" contains C Ethyl esters and methacrylates. In the present application, metal oxide particles modified with an organic compound having at least one phosphonate group are also referred to as "phosphonate-modified metal oxide particles".

本發明中所用之金屬氧化物粒子結晶度之為60或更小。一般而言，金屬氧化物粒子在粒子之表面上具有許多羥基。結晶度為60或更小之粒子表面上的羥基數高於結晶度大於60之粒子表面上的羥基數。因此，為選擇此類結晶度低之金屬氧化物粒子，可如隨後所揭示在粒子表面上實施足夠表面處理。另外，結晶度低之金屬氧化物粒子於有機溶劑中之聚結程度一般小於結晶度高之金屬氧化物粒子，因此結晶度低之粒子可容易分散於有機材料中。 The metal oxide particles used in the present invention have a crystallinity of 60 or less. In general, metal oxide particles have a plurality of hydroxyl groups on the surface of the particles. The number of hydroxyl groups on the surface of the particles having a crystallinity of 60 or less is higher than the number of hydroxyl groups on the surface of the particles having a crystallinity of more than 60. Therefore, in order to select such metal oxide particles having low crystallinity, sufficient surface treatment can be carried out on the surface of the particles as disclosed later. Further, since the degree of coalescence of the metal oxide particles having a low crystallinity in an organic solvent is generally smaller than that of the metal oxide particles having a high degree of crystallinity, particles having a low crystallinity can be easily dispersed in the organic material.

本發明中所用之金屬氧化物粒子之結晶度較佳為55或更小，更佳50或更小。金屬氧化物粒子之結晶度可如下分析並計算：i)與鐵金屬粉末製備以金屬氧化物粒子之重量計50：50混合物樣品，ii)藉由使用Cu-Kα輻射之X射線繞射在20與52度(2θ)之間分別使用0.05度步幅間隔及12秒計數時間掃描50：50混合物樣品，iii)測定銳鈦礦(101)、(103)、(004)、(112)及(200)之峰面積且計算樣品之面積總和(A銳鈦礦)，iv)測定鐵峰之峰面積(Ai)，v)計算樣品之銳鈦礦峰面積與鐵峰面積之比率(A銳鈦礦/Ai=Rexp)，vi)製備金屬氧化物粒子之參考物作為銳鈦礦標準物，且實施與上文相同之方法。接著計算標準物之銳鈦礦峰面積與鐵峰面積之比率(A銳鈦礦-標準物/Ai=Rstd)，vii)計算以上Rexp及Rstd之比率以確定金屬氧化物粒子之結晶度(銳鈦礦之Wt%)。對於參考物(銳鈦礦標準物)，可使用具有已知結晶度之市售金 屬氧化物粒子，諸如來自Aldrich Chemical之目錄號23203-3。提及表1中所示之以下公式以計算金屬氧化物粒子之結晶度。 The metal oxide particles used in the present invention preferably have a crystallinity of 55 or less, more preferably 50 or less. The crystallinity of the metal oxide particles can be analyzed and calculated as follows: i) preparing a 50:50 mixture sample with iron metal powder by weight of the metal oxide particles, ii) X-ray diffraction by using Cu- Kα radiation Between 20 and 52 degrees (2θ), a 50:50 mixture sample is scanned using a 0.05 degree step interval and a 12 second count time, and iii) anatase (101), (103), (004), (112) and (200) peak area and calculate the sum of the area of the sample (A anatase ), iv) determine the peak area of the iron peak (A i ), v) calculate the ratio of the anatase peak area to the iron peak area of the sample (A sharp Titanium ore / A i =R exp ), vi) A reference material for preparing metal oxide particles is prepared as an anatase standard, and the same method as above is carried out. Next, calculate the ratio of the anatase peak area to the iron peak area of the standard (A anatase - standard / A i = R std ), vii) calculate the ratio of R exp and R std above to determine the metal oxide particle Crystallinity (Wt% of anatase). For reference materials (anatase standards), commercially available metal oxide particles having known crystallinity can be used, such as catalog number 23203-3 from Aldrich Chemical. The following formula shown in Table 1 is referred to to calculate the crystallinity of the metal oxide particles.

結晶度低之金屬氧化物粒子在粒子表面上具有許多羥基。結晶度低之金屬氧化物粒子表面上之羥基數大於結晶度高之金屬氧化物粒子。原因在於金屬氧化物粒子之合成通常藉由金屬氧化物前驅體之連續水解及縮合反應實施。舉例而言，氧化鈦(TiO2)粒子由鈦醇鹽(TiO2之前驅體)藉由連續水解及縮合反應來製備。合成之TiO2粒子在粒子中具有許多-Ti-O-Ti-鍵結構。同時，鈦前驅體之未反應之醇鹽基團在TiO2粒子中變為羥基。高度縮合之TiO2粒子在粒子中具有大量-Ti-O-Ti-鍵結構，因此彼等TiO2粒子具有少量殘餘羥基。因為由以上方法所量測，高度縮合之TiO2粒子具有高結晶度，所以結晶度高之金屬氧化物粒子具有少量羥基。相反，低縮合之TiO2粒子為結晶度低之TiO2粒子，且此等粒子 具有大量殘餘羥基。 The metal oxide particles having a low crystallinity have many hydroxyl groups on the surface of the particles. The number of hydroxyl groups on the surface of the metal oxide particles having a low degree of crystallinity is larger than the metal oxide particles having a high degree of crystallinity. The reason is that the synthesis of metal oxide particles is usually carried out by continuous hydrolysis and condensation reaction of a metal oxide precursor. For example, titanium oxide (TiO 2 ) particles are prepared from titanium alkoxide (TiO 2 precursor) by continuous hydrolysis and condensation reactions. The synthesized TiO 2 particles have a plurality of -Ti-O-Ti-bond structures in the particles. At the same time, the unreacted alkoxide groups of the titanium precursor become hydroxyl groups in the TiO 2 particles. The highly condensed TiO 2 particles have a large amount of -Ti-O-Ti-bond structure in the particles, and thus the TiO 2 particles have a small amount of residual hydroxyl groups. Since the highly condensed TiO 2 particles have high crystallinity as measured by the above method, the metal oxide particles having a high degree of crystallinity have a small amount of hydroxyl groups. In contrast, the low condensation TiO 2 particles are TiO 2 particles having a low crystallinity, and these particles have a large amount of residual hydroxyl groups.

本發明中所用之金屬氧化物粒子較佳選自包括TiO2、ZrO2及氧化鉿中之至少一者的金屬氧化物粒子。更佳地，金屬氧化物粒子為TiO2粒子。金屬氧化物粒子可包括兩種或更多種金屬氧化物。 The metal oxide particles used in the present invention are preferably selected from metal oxide particles including at least one of TiO 2 , ZrO 2 and cerium oxide. More preferably, the metal oxide particles are TiO 2 particles. The metal oxide particles may include two or more metal oxides.

本發明中所用之金屬氧化物粒子經具有至少一個膦酸酯基之有機化合物改質。因為粒子之表面經有機化合物改質，所以經膦酸酯基改質之金屬氧化物粒子可分散於有機溶劑與有機材料(諸如聚合物材料)中。詳言之，本發明之經膦酸酯基改質之金屬氧化物粒子可分散於通常用於電子材料之有機溶劑中。不受理論束縛，但本發明之本發明人認為有機化合物之膦酸酯基與金屬氧化物粒子表面上之羥基反應，且連接至金屬氧化物粒子表面之此等有機化合物防止此等粒子彼此聚結。因為結晶度低之金屬氧化物粒子具有許多羥基，大量有機化合物可與此類粒子表面上之羥基反應。 The metal oxide particles used in the present invention are modified with an organic compound having at least one phosphonate group. Since the surface of the particles is modified by an organic compound, the phosphonate-modified metal oxide particles can be dispersed in an organic solvent and an organic material such as a polymer material. In particular, the phosphonate-modified metal oxide particles of the present invention can be dispersed in an organic solvent commonly used in electronic materials. Without being bound by theory, the inventors of the present invention believe that the phosphonate group of the organic compound reacts with the hydroxyl group on the surface of the metal oxide particle, and the organic compound attached to the surface of the metal oxide particle prevents the particles from aggregating with each other. Knot. Since metal oxide particles having a low crystallinity have many hydroxyl groups, a large amount of organic compounds can react with hydroxyl groups on the surface of such particles.

較佳地，具有至少一個膦酸酯基之有機化合物具有丙烯酸酯或甲基丙烯酸酯基。不受理論束縛，但本發明之本發明人認為金屬氧化物粒子表面上之丙烯酸酯基或甲基丙烯酸酯基與有機溶劑，尤其用於電子材料之有機溶劑(諸如PGME及PGMEA)具有親和力，因此經彼等有機化合物改質之金屬氧化物粒子可充分分散於有機溶劑中。 Preferably, the organic compound having at least one phosphonate group has an acrylate or methacrylate group. Without being bound by theory, the inventors of the present invention believe that the acrylate or methacrylate group on the surface of the metal oxide particles has an affinity with an organic solvent, particularly an organic solvent for electronic materials such as PGME and PGMEA. Therefore, the metal oxide particles modified by their organic compounds can be sufficiently dispersed in an organic solvent.

連接至金屬氧化物粒子表面之具有至少一個膦酸酯基之有機化合物的量較佳為每平方奈米金屬氧化物粒子之表面大於0.78，更佳每平方奈米0.80或更多(/nm2)。其可藉由金屬氧化物粒子之直徑、密度及重量分率計算。當金屬 氧化物粒子為TiO2粒子時，以下公式為計算所連接之有機化合物之量的實例。 The amount of the organic compound having at least one phosphonate group attached to the surface of the metal oxide particles is preferably more than 0.78 per square nanometer of metal oxide particles, more preferably 0.80 or more per square nanometer (/nm 2 ) ). It can be calculated by the diameter, density and weight fraction of the metal oxide particles. When the metal oxide particles are TiO 2 particles, the following formula is an example of calculating the amount of the organic compound to be attached.

在公式中，dTiO2為TiO2粒子之粒徑，且其可藉由DLS分析。ρ TiO2 為自氣體比重計得到之TiO2粒子之密度(載氣為氦氣)。WtTiO2-EMP為TiO2粒子之重量分率且其可獲自TGA結果。MEMP為TiO2粒子之分子量且為210.12g/mol。Na為Avogadro常數6.022×1023mol-1。 In the formula, TiO 2 particle diameter of the particles, and which may be analyzed by DLS d TiO2. ρ TiO2 is obtained from the specific gravity of the density of the gas meter of the TiO 2 particles (carrier gas was helium). Wt TiO2-EMP is the weight fraction of TiO 2 particles and it can be obtained from TGA results. M EMP is the molecular weight of the TiO 2 particles and is 210.12 g/mol. Na is an Avogadro constant of 6.022 × 10 23 mol -1 .

金屬氧化物粒子表面上殘餘羥基與連接之有機化合物之量的比率可藉由NMR光譜分析並計算。 The ratio of the amount of residual hydroxyl groups on the surface of the metal oxide particles to the amount of the attached organic compound can be analyzed and calculated by NMR spectroscopy.

金屬氧化物粒子可在用具有至少一個膦酸酯基之有機化合物處理之後進一步用有機矽烷化合物處理。有機矽烷化合物與經膦酸酯基改質之金屬氧化物粒子表面上之殘餘羥基反應。用此類有機矽烷化合物進行表面處理會減少經膦酸酯基改質之金屬氧化物粒子表面上殘餘羥基之數目，且彼等金屬氧化物粒子更容易分散於有機溶劑中且有機材料與不經有機矽烷化合物處理之金屬氧化物粒子相當。較佳地，與用有機矽烷化合物處理前之殘餘羥基之數目相比，金屬氧化物粒子表面上殘餘羥基之數目為1/20或更少。更佳地，與用有機矽烷化合物處理前之殘餘羥基相比，金屬氧化物粒子表面上之殘餘羥基為1/50或更少。 The metal oxide particles can be further treated with an organodecane compound after treatment with an organic compound having at least one phosphonate group. The organodecane compound is reacted with residual hydroxyl groups on the surface of the phosphonate-modified metal oxide particles. Surface treatment with such organodecane compounds reduces the number of residual hydroxyl groups on the surface of the phosphonate-modified metal oxide particles, and these metal oxide particles are more easily dispersed in an organic solvent and the organic materials are not The metal oxide particles treated with the organodecane compound are equivalent. Preferably, the number of residual hydroxyl groups on the surface of the metal oxide particles is 1/20 or less compared to the number of residual hydroxyl groups before treatment with the organodecane compound. More preferably, the residual hydroxyl groups on the surface of the metal oxide particles are 1/50 or less as compared with the residual hydroxyl groups before treatment with the organodecane compound.

當將金屬氧化物粒子用有機矽烷化合物處理，接著藉由具有至少一個膦酸酯基之有機化合物處理時，金屬氧化物粒子表面上具有至少一個膦酸酯基之有機化合物與有機 矽烷化合物之莫耳比為99：1至1：1，較佳20：1至2：1。 When the metal oxide particles are treated with an organic decane compound, followed by treatment with an organic compound having at least one phosphonate group, the organic oxide compound having at least one phosphonate group on the surface of the metal oxide particles and the organic The molar ratio of the decane compound is from 99:1 to 1:1, preferably from 20:1 to 2:1.

本發明之經膦酸酯基改質之金屬氧化物粒子之直徑具有一定直徑範圍(分佈)。80%粒子之直徑為0.5至150nm。較佳地，80%粒子之直徑為1至100nm，更佳1至50nm。最佳地，80%粒子之直徑為1至10nm。直徑可在室溫下藉由動態光散射(DLS)方法使用DLS分析儀(例如Malvern Zetasizer Nano ZS)來量測。較小粒徑使包括粒子之有機材料具有較高透明度。 The phosphonate-modified metal oxide particles of the present invention have a diameter range (distribution). 80% of the particles have a diameter of 0.5 to 150 nm. Preferably, 80% of the particles have a diameter of from 1 to 100 nm, more preferably from 1 to 50 nm. Most preferably, 80% of the particles have a diameter of from 1 to 10 nm. The diameter can be measured at room temperature by a dynamic light scattering (DLS) method using a DLS analyzer (eg, Malvern Zetasizer Nano ZS). The smaller particle size gives the organic material comprising the particles a higher transparency.

形成經膦酸酯基改質之金屬氧化物粒子之方法包括以下三個步驟：(a)使於金屬醇鹽溶液中縮合以形成結晶度為60%或更小之金屬氧化物粒子，(b)使金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸以改質金屬氧化物粒子，及視情況(c)使經膦酸酯基改質之金屬氧化物粒子與有機矽烷化合物接觸。 The method of forming a phosphonate-modified metal oxide particle comprises the following three steps: (a) condensing in a metal alkoxide solution to form a metal oxide particle having a crystallinity of 60% or less, (b) Contacting the metal oxide particles with an organic compound having at least one phosphonate group to modify the metal oxide particles, and optionally contacting the phosphonate-modified metal oxide particles with the organodecane compound, as the case may be (c) .

步驟(a) Step (a)

第一步驟為於溶劑中縮合金屬醇鹽以形成結晶度為60%或更小之金屬氧化物粒子。金屬醇鹽之實例包含(但不限於)四丁氧基鈦、四乙氧基鈦、四甲氧基鈦、四丁氧基鋯、四乙氧基鋯、正丙醇鋯、異丙醇鋯及乙醇鉿。溶劑可為水或水及其他有機溶劑之混合物。 The first step is to condense the metal alkoxide in a solvent to form metal oxide particles having a crystallinity of 60% or less. Examples of metal alkoxides include, but are not limited to, titanium tetrabutoxide, titanium tetraethoxide, titanium tetramethoxide, zirconium tetrabutoxide, zirconium tetraethoxide, zirconium n-propoxide, zirconium isopropoxide And ethanol hydrazine. The solvent can be water or a mixture of water and other organic solvents.

通常，金屬醇鹽之縮合在水解催化劑(酸或鹼)存在下於水中進行。於水中之縮合反應在此項技術中理解為水解及縮合反應。其亦稱為溶液凝膠反應。溶液中金屬醇鹽之濃度為150至400g/L，較佳200至350g/L，更佳250至300g/L。作為催化劑之酸可為有機酸或無機酸。此類酸之實 例包含(但不限於)鹽酸、硫酸、甲酸及乙酸。溶液中酸之濃度為2.5至12.0g/L，較佳4.5至8.5g/L。A可使用鹼而非酸作為水解催化劑。當使用鹼作為水解催化劑時，其於溶液中之濃度可根據此項技術之技術知識來決定。視情況，可講諸如甲醇、乙醇或丁醇之溶劑添加於溶液中。 Usually, the condensation of the metal alkoxide is carried out in water in the presence of a hydrolysis catalyst (acid or base). Condensation reactions in water are understood in the art to be hydrolysis and condensation reactions. It is also known as a solution gel reaction. The concentration of the metal alkoxide in the solution is from 150 to 400 g/L, preferably from 200 to 350 g/L, more preferably from 250 to 300 g/L. The acid as a catalyst may be an organic acid or an inorganic acid. Such acid Examples include, but are not limited to, hydrochloric acid, sulfuric acid, formic acid, and acetic acid. The concentration of the acid in the solution is from 2.5 to 12.0 g/L, preferably from 4.5 to 8.5 g/L. A can use a base instead of an acid as a hydrolysis catalyst. When a base is used as the hydrolysis catalyst, its concentration in the solution can be determined according to the technical knowledge of the art. Optionally, a solvent such as methanol, ethanol or butanol may be added to the solution.

反應溫度為30℃至80℃，較佳為60℃至80℃。縮合反應在攪拌下進行。反應時間為1.5小時至5小時，較佳為3至4小時。隨著縮合反應進行，金屬氧化物粒子之尺寸變得更大。當獲得具有所需粒度之金屬氧化物粒子時，第一步驟完成。如上文所提及，粒度(粒子之直徑)可藉由DLS來量測。 The reaction temperature is from 30 ° C to 80 ° C, preferably from 60 ° C to 80 ° C. The condensation reaction is carried out under stirring. The reaction time is from 1.5 hours to 5 hours, preferably from 3 to 4 hours. As the condensation reaction proceeds, the size of the metal oxide particles becomes larger. When a metal oxide particle having a desired particle size is obtained, the first step is completed. As mentioned above, the particle size (diameter of the particles) can be measured by DLS.

步驟(b) Step (b)

第二步驟為使金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸以改質金屬氧化物粒子。具有至少一個膦酸酯基之有機化合物之實例包含(但不限於)(甲基)丙烯酸伸烷酯磷酸酯，諸如甲基丙烯酸伸乙酯磷酸酯及丙烯酸伸乙酯磷酸酯；及聚(氧化烯)(甲基)丙烯酸酯磷酸酯，諸如以下式(1)至(3)中所揭示。 The second step is to contact the metal oxide particles with an organic compound having at least one phosphonate group to modify the metal oxide particles. Examples of organic compounds having at least one phosphonate group include, but are not limited to, alkyl (meth) acrylate phosphates such as ethyl methacrylate and ethyl acrylate; and poly(oxidation) (Alkenyl) (meth) acrylate phosphate, such as disclosed in the following formulas (1) to (3).

在式(1)至(3)中，n為1至20之整數。 In the formulae (1) to (3), n is an integer of 1 to 20.

如實例中所揭示，乙烯基膦酸不可個別地用於本發明之表面處理，因為用化合物處理之金屬氧化物粒子不分散於用於電子材料之聚合物材料的有機溶劑中。 As disclosed in the examples, vinylphosphonic acid cannot be used individually for the surface treatment of the present invention because the metal oxide particles treated with the compound are not dispersed in the organic solvent of the polymer material for the electronic material.

具有至少一個膦酸酯基之有機化合物的量可根據與用於步驟(a)之金屬醇鹽之重量比決定。金屬醇鹽與具有至少一個膦酸酯基之有機化合物的重量比為10：1至1：10，較佳5：1至1：2。藉由任何已知方法使金屬氧化物粒子與有機化合物接觸，例如在攪拌下將金屬氧化物粒子及有機化合物於諸如水之溶劑中混合。反應溫度為60℃至150℃，較佳為80℃至120℃。反應時間為0.25至12小時，較佳為1至4小時。 The amount of the organic compound having at least one phosphonate group can be determined according to the weight ratio of the metal alkoxide used in the step (a). The weight ratio of the metal alkoxide to the organic compound having at least one phosphonate group is from 10:1 to 1:10, preferably from 5:1 to 1:2. The metal oxide particles are contacted with the organic compound by any known method, for example, by mixing the metal oxide particles and the organic compound in a solvent such as water under stirring. The reaction temperature is from 60 ° C to 150 ° C, preferably from 80 ° C to 120 ° C. The reaction time is 0.25 to 12 hours, preferably 1 to 4 hours.

步驟(c) Step (c)

第三步驟視情況存在且使經膦酸酯基改質之金屬氧化物粒子與有機矽烷化合物接觸。有機矽烷化合物之實例包含(但不限於)三烷基氯矽烷，諸如三甲基氯矽烷、三乙基氯矽烷及三丙基氯矽烷；及矽氮烷，諸如六甲基二矽氮烷。有機矽烷化合物之量可根據與用於步驟(a)中之金屬醇鹽之重量比決定。金屬醇鹽與有機矽烷化合物之重量比為20：1至1：10，較佳10：1至1：1。藉由任何已知方法使經膦酸酯基改質之金屬氧化物粒子與矽烷化合物接觸，例如在攪拌下將經膦酸酯改質之金屬氧化物粒子及有機矽烷化合物於諸如水之溶劑中混合。反應溫度為30℃至150℃，較佳為50℃至120℃。反應時間為0.5至8小時，較佳為1至2小時。 The third step is optionally present and the phosphonate-modified metal oxide particles are contacted with the organodecane compound. Examples of organodecane compounds include, but are not limited to, trialkylchlorosilanes such as trimethylchlorodecane, triethylchlorodecane, and tripropylchlorodecane; and decazanes such as hexamethyldioxane. The amount of the organodecane compound can be determined according to the weight ratio of the metal alkoxide used in the step (a). The weight ratio of the metal alkoxide to the organodecane compound is from 20:1 to 1:10, preferably from 10:1 to 1:1. The phosphonate-modified metal oxide particles are contacted with a decane compound by any known method, for example, the phosphonate-modified metal oxide particles and the organodecane compound are dissolved in a solvent such as water under stirring. mixing. The reaction temperature is from 30 ° C to 150 ° C, preferably from 50 ° C to 120 ° C. The reaction time is from 0.5 to 8 hours, preferably from 1 to 2 hours.

將所獲得之反應產物冷卻至室溫，接著視情況老化(靜置)12至24小時。當將諸如水之溶劑用於步驟(b) 及/或步驟(c)中時，反應產物之溶劑可交換為用於輻射敏感組合物之另一溶劑。用於輻射敏感組合物之溶劑之實例包含(但不限於)丙二醇單甲醚(PGME)、丙二醇苯基醚丙二醇單甲醚乙酸酯(PGMEA)、1-丙氧基-2-丙醇、乳酸乙酯、2-羥基異丁酸甲酯及環己酮。 The obtained reaction product was cooled to room temperature, followed by aging (standing) for 12 to 24 hours. When a solvent such as water is used in step (b) And/or in step (c), the solvent of the reaction product can be exchanged for another solvent for the radiation-sensitive composition. Examples of solvents for radiation-sensitive compositions include, but are not limited to, propylene glycol monomethyl ether (PGME), propylene glycol phenyl ether propylene glycol monomethyl ether acetate (PGMEA), 1-propoxy-2-propanol, Ethyl lactate, methyl 2-hydroxyisobutyrate and cyclohexanone.

本發明之一個態樣為包括聚合物及經膦酸酯基改質之金屬氧化物粒子之聚合物材料。聚合物亦稱為黏合劑。聚合物之實例包含(但不限於)丙烯酸型聚合物、甲基丙烯酸型聚合物、矽氧烷型聚合物、環氧樹脂、聚酯、聚烯烴、酚醛清漆樹脂、聚苯乙烯及聚胺基甲酸酯。彼等聚合物中之詞語「型」包含由兩種或更多種不同單體形成之共聚物及由所述單體之酯形成之聚合物。舉例而言，『丙烯酸型聚合物』包含由丙烯酸及至少一種其他單體形成之共聚物，以及由諸如丙烯酸甲酯之丙烯酸酯形成之聚合物。此外，若樹脂由苯乙烯及至少一種其他單體形成，則「聚苯乙烯」包含任何樹脂。若樹脂包括環氧基，則「環氧樹脂」意謂任何樹脂。 One aspect of the invention is a polymeric material comprising a polymer and a phosphonate-modified metal oxide particle. Polymers are also known as binders. Examples of polymers include, but are not limited to, acrylic polymers, methacrylic polymers, siloxane polymers, epoxies, polyesters, polyolefins, novolac resins, polystyrenes, and polyamines. Formate. The term "type" in such polymers encompasses copolymers formed from two or more different monomers and polymers formed from esters of the monomers. For example, "acrylic polymer" includes a copolymer formed of acrylic acid and at least one other monomer, and a polymer formed of an acrylate such as methyl acrylate. Further, if the resin is formed of styrene and at least one other monomer, the "polystyrene" contains any resin. If the resin includes an epoxy group, "epoxy resin" means any resin.

聚合物材料可為模製產物、膜或任何其他形式。聚合物材料可為形成於物件上之膜。可使用任何物件。物件之實例包含(但不限於)塑膠、金屬、玻璃及電子組件，諸如ITO電極、佈線材料及玻璃或矽基板。當於物件上形成膜時，製備包括聚合物、經膦酸酯基改質之金屬氧化物粒子及視情況存在之溶劑之組合物，接著可藉由諸如旋塗之任何已知方法將組合物塗佈於物件上。視情況乾燥組合物以蒸發溶劑。 The polymeric material can be a molded product, a film, or any other form. The polymeric material can be a film formed on the article. Any object can be used. Examples of articles include, but are not limited to, plastic, metal, glass, and electronic components such as ITO electrodes, wiring materials, and glass or germanium substrates. When a film is formed on the article, a composition comprising a polymer, a phosphonate-modified metal oxide particle, and optionally a solvent is prepared, which can then be applied by any known method such as spin coating. Coated on the object. The composition is dried as appropriate to evaporate the solvent.

聚合物材料中經膦酸酯基改質之金屬氧化物粒 子之量可為0.1至80wt%，較佳5至70wt%。當經膦酸酯基改質之金屬氧化物粒子含於聚合物材料中之量為0.1至80wt%時，包含經膦酸酯基改質之金屬氧化物粒子之聚合物材料的RI為1.65至2.0。當將有機材料用作ITO電極之有機塗層材料時，含有粒子之聚合物材料之RI較佳為1.7至1.9。 Metal oxide particles modified by phosphonate groups in polymer materials The amount may be from 0.1 to 80% by weight, preferably from 5 to 70% by weight. When the phosphonate-modified metal oxide particles are contained in the polymer material in an amount of from 0.1 to 80% by weight, the RI of the polymer material comprising the phosphonate-modified metal oxide particles is 1.65 to 2.0. When an organic material is used as the organic coating material of the ITO electrode, the RI of the polymer material containing particles is preferably from 1.7 to 1.9.

本發明之輻射敏感組合物包括上文所揭示之經膦酸酯基改質之金屬氧化物粒子。一般而言，存在兩個類型之輻射敏感組合物，亦即正型輻射敏感組合物及負型輻射敏感組合物。正型輻射敏感組合物意謂形成膜，其中暴露於輻射之膜部分可溶於諸如鹼性溶液之顯影組合物之組合物，而負型輻射敏感組合物形成膜，其中暴露之部分不可溶於顯影組合物。本發明之輻射敏感組合物可為正型輻射敏感組合物或負型輻射敏感組合物。輻射敏感組合物之配方可根據一般熟習此項技術者之知識而決定。負型輻射敏感組合物之實例揭示於下文中。 The radiation-sensitive composition of the present invention comprises the phosphonate-modified metal oxide particles disclosed above. In general, there are two types of radiation-sensitive compositions, namely positive-type radiation-sensitive compositions and negative-type radiation-sensitive compositions. A positive-type radiation-sensitive composition means forming a film in which a portion of the film exposed to radiation is soluble in a composition of a developing composition such as an alkaline solution, and a negative-type radiation-sensitive composition forms a film in which the exposed portion is insoluble Developing the composition. The radiation-sensitive composition of the present invention may be a positive-type radiation-sensitive composition or a negative-type radiation-sensitive composition. The formulation of the radiation-sensitive composition can be determined based on the knowledge of those of ordinary skill in the art. Examples of negative radiation sensitive compositions are disclosed below.

通常，負型輻射敏感組合物包括輻射可固化樹脂、光引發劑、溶劑及添加劑。輻射可固化樹脂為藉由輻射暴露交聯且形成樹脂之單體或寡聚物。其亦稱為多官能單體。形成鹼溶性樹脂之輻射可固化樹脂較佳。輻射可固化樹脂包含(但不限於)具有環氧基、氧雜環丁烷基、乙烯基、硫醇基或丙烯醯基之化合物。輻射可固化樹脂之實例包含(但不限於)丙烯酸胺基甲酸酯、丙烯酸聚酯、氧雜環丁烷樹脂、聚矽氧烷及環氧丙烯酸酯。輻射可固化樹脂之量為以輻射敏感組合物之固體含量計0至70wt%，較佳5至60wt%。 Generally, negative radiation sensitive compositions include radiation curable resins, photoinitiators, solvents, and additives. The radiation curable resin is a monomer or oligomer which is crosslinked by radiation exposure and forms a resin. It is also known as a polyfunctional monomer. A radiation curable resin which forms an alkali-soluble resin is preferred. Radiation curable resins include, but are not limited to, compounds having an epoxy group, an oxetane group, a vinyl group, a thiol group, or an acrylonitrile group. Examples of radiation curable resins include, but are not limited to, urethane acrylates, acrylic polyesters, oxetane resins, polyoxyalkylenes, and epoxy acrylates. The amount of the radiation curable resin is from 0 to 70% by weight, preferably from 5 to 60% by weight, based on the solid content of the radiation-sensitive composition.

可使用任何已知光引發劑(PI)，諸如肟酯型光 引發劑、烷基苯酮型光引發劑及陽離子型光引發劑，諸如鋶鹽或錪鹽。PI之實例包含(但不限於)Irgacure OXE-01、Irgacure OXE-02、Irgacure 379、Irgacure 651、Irgacure 127及Irgacure 907。組合物中PI之量為以輻射敏感組合物之固體含量計0.001至5.0wt%，較佳0.01至3.0wt%。 Any known photoinitiator (PI) can be used, such as oxime type light An initiator, an alkylphenone type photoinitiator, and a cationic photoinitiator such as a phosphonium salt or a phosphonium salt. Examples of PI include, but are not limited to, Irgacure OXE-01, Irgacure OXE-02, Irgacure 379, Irgacure 651, Irgacure 127, and Irgacure 907. The amount of PI in the composition is from 0.001 to 5.0% by weight, preferably from 0.01 to 3.0% by weight, based on the solids content of the radiation-sensitive composition.

本發明之輻射敏感組合物可包括至少一種溶劑。溶劑之實例包括(但不限於)丙二醇單甲醚(PGME)、丙二醇苯基醚丙二醇單甲醚乙酸酯(PGMEA)、1-丙氧基-2-丙醇、乳酸乙酯、2-羥基異丁酸甲酯及環己酮。溶劑之總量為以輻射敏感組合物之固體含量計25至900wt%，較佳150至400wt%。 The radiation-sensitive composition of the present invention may comprise at least one solvent. Examples of the solvent include, but are not limited to, propylene glycol monomethyl ether (PGME), propylene glycol phenyl ether propylene glycol monomethyl ether acetate (PGMEA), 1-propoxy-2-propanol, ethyl lactate, 2-hydroxyl Methyl isobutyrate and cyclohexanone. The total amount of solvent is from 25 to 900% by weight, preferably from 150 to 400% by weight, based on the solids content of the radiation-sensitive composition.

用於本發明之輻射敏感組合物中之添加劑的實例包含(但不限於)抑制劑、分散劑及著色化合物，諸如染料、顏料或碳黑。 Examples of additives for use in the radiation-sensitive compositions of the present invention include, but are not limited to, inhibitors, dispersants, and coloring compounds such as dyes, pigments, or carbon black.

輻射敏感組合物可藉由任何已知方法，例如將組合物旋塗、滾塗及噴霧於電子組件上，或將電子組件浸漬於組合物中而塗覆於諸如電子組件之物件。 The radiation-sensitive composition can be applied to an article such as an electronic component by any known method, such as spin coating, rolling and spraying the composition onto an electronic component, or immersing the electronic component in the composition.

接著使輻射敏感組合物曝光以使組合物固化。曝光可藉由紫外光或可見光進行。使用圖案遮罩進行曝光以在物件上獲得所要圖案。接著，藉由稱為顯影劑之顯影組合物移除未曝光區域。可以使用任何已知顯影劑。當固化組合物為鹼溶性的時，鹼性顯影劑較佳。此類顯影劑之實例包含(但不限於)包括氫氧化鉀、氫氧化鈉、氫氧化四甲基銨及氫氧化四丁基銨之鹼性溶液。視情況，可將經曝光之化合物進一步加熱至80℃至250℃保持3分鐘至2小時。 The radiation sensitive composition is then exposed to cure the composition. Exposure can be carried out by ultraviolet light or visible light. Exposure is performed using a pattern mask to obtain the desired pattern on the object. Next, the unexposed areas are removed by a developing composition called a developer. Any known developer can be used. The alkaline developer is preferred when the cured composition is alkali soluble. Examples of such developers include, but are not limited to, alkaline solutions including potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide. The exposed compound may be further heated to 80 ° C to 250 ° C for 3 minutes to 2 hours, as the case may be.

如上文所揭示，輻射敏感組合物藉由曝光、顯影及視情況存在之進一步加熱形成硬化材料(固化材料)。硬化材料可用於形成電子組件上之絕緣層(有機塗層)。絕緣層包含抗反射層。電子組件之實例包含(但不限於)用於LCD裝置、OLED裝置及觸摸屏感測器面板之ITO電極及ITO電極之佈線材料。佈線材料包含銅、銀及含有銅或銀之金屬合金。當由本發明組合物形成之硬化材料為透明或半透明的時，硬化材料因其具有高RI故尤其適用於於ITO電極上形成絕緣層。 As disclosed above, the radiation-sensitive composition forms a hardened material (cured material) by exposure, development, and, where appropriate, further heating. The hardened material can be used to form an insulating layer (organic coating) on the electronic component. The insulating layer contains an anti-reflection layer. Examples of electronic components include, but are not limited to, wiring materials for ITO electrodes and ITO electrodes for LCD devices, OLED devices, and touch screen sensor panels. The wiring material contains copper, silver, and a metal alloy containing copper or silver. When the hardening material formed from the composition of the present invention is transparent or translucent, the hardening material is particularly suitable for forming an insulating layer on the ITO electrode because of its high RI.

實例Instance

將表2中所示之原材料用於實例中。 The raw materials shown in Table 2 were used in the examples.

實例1(本發明實例) Example 1 (example of the invention)

將150g鈦丁醇、25.5g己酸、50mL 1-丁醇之混合物添加至Parr反應器中且加以攪拌。將去離子(DI)水(14.0g)添 加至反應器中。在室溫下攪拌溶液0.5小時。之後，在135℃下加熱溶液2.5小時。觀測到TiO2粒子。 A mixture of 150 g of titanium butanol, 25.5 g of hexanoic acid, and 50 mL of 1-butanol was added to the Parr reactor and stirred. Deionized (DI) water (14.0 g) was added to the reactor. The solution was stirred at room temperature for 0.5 hours. Thereafter, the solution was heated at 135 ° C for 2.5 hours. TiO 2 particles were observed.

將甲基丙烯酸伸乙酯磷酸酯(EMP，21.5g)溶解於21.5gPGMEA中且添加至含有TiO2粒子溶液之反應器中。在115℃下加熱溶液1小時且冷卻至室溫。獲得經EMP改質之TiO2粒子(TiO2-EMP粒子)。 Ethyl methacrylate phosphate (EMP, 21.5 g) was dissolved in 21.5 g of PGMEA and added to a reactor containing a solution of TiO 2 particles. The solution was heated at 115 ° C for 1 hour and cooled to room temperature. EMP-modified TiO 2 particles (TiO 2 -EMP particles) were obtained.

將氯三甲基矽烷(5.0g)添加至含有TiO2-EMP粒子溶液之以上反應器中且在60℃至80℃下加熱溶液1小時以與TiO2-EMP粒子表面上之羥基反應。獲得經EMP及氯三甲基矽烷改質之TiO2粒子(TiO2-EMP/CMS粒子)。 The chloro trimethyl Silane (5.0 g) was added to the particles containing TiO 2 -EMP or more of the reactor was heated solution for 1 hour and the hydroxyl groups on the surface of the TiO 2 -EMP particles and reacted at 60 deg.] C to 80 ℃. TiO 2 particles (TiO 2 -EMP/CMS particles) modified with EMP and chlorotrimethyl decane were obtained.

將正己烷(3倍反應溶液體積)添加至溶液中以使獲得之TiO2-EMP/CMS粒子沈澱。藉由離心收集沈澱物且再溶解於PGMEA中。獲得淡黃色透明分散液。分散液稱為固體含量為35wt%之TiO2-EMP/CMS。 N-hexane (3 times the reaction solution volume) was added to the solution to precipitate the obtained TiO 2 -EMP/CMS particles. The precipitate was collected by centrifugation and redissolved in PGMEA. A light yellow transparent dispersion was obtained. The dispersion was referred to as TiO 2 -EMP/CMS having a solids content of 35 wt%.

分析 analysis

晶體結構 Crystal structure

藉由X射線繞射(XRD)檢查晶體結構。用配備有銅旋轉陽極、經調整得到Cu Kα輻射之繞射光束單色器及閃爍偵測器之Bruker D8 ADVANCE繞射儀進行XRD量測。 The crystal structure was examined by X-ray diffraction (XRD). XRD measurements were performed on a Bruker D8 ADVANCE diffractometer equipped with a copper rotating anode, a diffracted beam monochromator with adjusted Cu Ka radiation, and a scintillation detector.

X射線繞射圖案指示TiO2-EMP/CMS粒子之晶體結構為銳鈦礦。 The X-ray diffraction pattern indicates that the crystal structure of the TiO 2 -EMP/CMS particles is anatase.

粒度 granularity

TiO2-EMP/CMS粒子之粒度藉由動態光散射(DLS，Malvern Zetasizer Nano ZS)來量測。使用分散於2-丁酮中之TiO2-EMP/CMS粒子分析其粒度。DLS曲線指示 TiO2-EMP/CMS粒子之粒徑範圍為1.5至7nm。 The particle size of the TiO 2 -EMP/CMS particles was measured by dynamic light scattering (DLS, Malvern Zetasizer Nano ZS). The particle size was analyzed using TiO 2 -EMP/CMS particles dispersed in 2-butanone. The DLS curve indicates that the TiO 2 -EMP/CMS particles have a particle size ranging from 1.5 to 7 nm.

P31 NMR P 31 NMR

TiO2-EMP/CMS粒子之膦酸酯基之化學環境藉由P31 NMR來量測。比較TiO2-EMP/CMS粒子與EMP之P31 NMR峰。使用分散於甲基乙基酮中之TiO2-EMP/CMS。NMR資料顯示在TiO2-EMP/CMS粒子樣品中EMP之游離膦酸酯基的尖銳峰消失，因此幾乎所有EMP分子均已連接至TiO2表面。 The chemical environment of the phosphonate group of the TiO 2 -EMP/CMS particles was measured by P 31 NMR. The P 31 NMR peaks of TiO 2 -EMP/CMS particles and EMP were compared. TiO 2 -EMP/CMS dispersed in methyl ethyl ketone was used. NMR data show that the free phosphonate group of EMP sharp peaks disappear TiO 2 -EMP / CMS particle sample, so almost all EMP molecules 2 are connected to the surface of TiO.

有機組合物含量 Organic composition content

TiO2-EMP/CMS粒子之有機組合物藉由熱重分析(TGA)偵測。TGA曲線指示TiO2-EMP/CMS粒子中有機材料之含量為21.3wt%。 The organic composition of TiO 2 -EMP/CMS particles was detected by thermogravimetric analysis (TGA). The TGA curve indicates that the content of the organic material in the TiO 2 -EMP/CMS particles is 21.3 wt%.

結晶度 Crystallinity

參看US6329058B量測TiO2粒子之結晶度。在50℃下乾燥EMP處理前之二氧化鈦漿料隔夜。使用研缽及研杵研磨獲得之二氧化鈦粉末。用配備有銅旋轉陽極、經調整得到Cu Kα輻射之繞射光束單色器及閃爍偵測器之Bruker D8 ADVANCE繞射儀進行X射線繞射。 See US6329058B for the measurement of crystallinity of TiO 2 particles. The titanium dioxide slurry before the EMP treatment was dried overnight at 50 °C. The titanium dioxide powder obtained by grinding using a mortar and pestle. X-ray diffraction was performed using a Bruker D8 ADVANCE diffractometer equipped with a copper rotating anode, a diffracted beam monochromator with adjusted Cu Ka radiation, and a scintillation detector.

各粒子樣品與鐵金屬粉末製備成以重量計50：50之混合物且在20與52度之間使用0.05度步幅間隔及12秒計數時間進行掃描。藉由擬合觀測到之資料的曲線確定銳鈦礦(101)、(103)、(004)、(112)及(200)之最大峰面積及鐵之最大峰面積。使用Gaussian峰形狀模型及線性本底進行曲線擬合。計算各未知物之銳鈦礦峰面積(A銳鈦礦)(視為上文所指示之個別比重之總和)與鐵(Ai)峰面積之比率(Rexp)。亦掃描自Aldrich Chemical以目錄號23203-3出售之參考物銳 鈦礦標準物，得到類似參考值(Rstd)。藉由儀器如下使用Rexp與Rstd之比率計算本發明之晶體金屬氧化物粒子中銳鈦礦形式之重量百分比：A銳鈦礦=A(101)+A(103)+A(004)+A(112)+A(200)(個別銳鈦礦峰面積之總和) Each particle sample was prepared as a 50:50 mixture by weight with iron metal powder and scanned between 20 and 52 degrees using a 0.05 degree step interval and a 12 second count time. The maximum peak area of anatase (101), (103), (004), (112), and (200) and the maximum peak area of iron are determined by fitting the curve of the observed data. Curve fitting was performed using a Gaussian peak shape model and a linear background. The ratio of the anatase peak area (A anatase ) of each unknown (as the sum of the individual specific gravity indicated above) to the area of the iron (A i ) peak (R exp ) was calculated. A reference anatase standard sold by Aldrich Chemical under catalog number 23203-3 was also scanned to give a similar reference value (R std ). The weight percentage of the anatase form of the crystalline metal oxide particles of the present invention is calculated by the instrument using the ratio of R exp to R std as follows: A anatase = A (101) + A (103) + A ( 004) + A (112) + A (200) (sum of individual anatase peak areas)

Ai(鐵峰之面積) A i (area of iron peak)

Rexp=A銳鈦礦/Ai(未知物之銳鈦礦峰面積與鐵峰面積之比率) R exp =A anatase / A i (the ratio of the anatase peak area to the iron peak area of the unknown)

Rstd=A銳鈦礦-標準物/Ai-std(標準銳鈦礦之銳鈦礦峰面積與鐵峰面積之比率) R std =A anatase - standard / A i-std (ratio of anatase peak area to iron peak area of standard anatase)

銳鈦礦之Wt%=(Rexp/Rstd)*100(晶體銳鈦礦之重量百分比) Anatase Wt%=(R exp /R std )*100 (weight percentage of crystalline anatase)

TiO2粒子之結晶度為約50%。 The crystallinity of the TiO 2 particles is about 50%.

使丙烯酸光阻劑MSP5727及TiO2-EMP/CMS於PGMEA中之分散液以各種重量比混合且藉由旋塗澆鑄於矽晶圓上。分析無水MSP5727/TiO2-EMP/CMS膜之折射率(在550nm下)。如圖1中所示，膜之RI以函數TiO2-EMP/CMS含量而增加。 Acrylic resist MSP5727 and TiO 2 -EMP / CMS dispersed in PGMEA was mixed at various weight ratios and cast by spin coating onto silicon wafers. The refractive index of the anhydrous MSP 5727/TiO 2 -EMP/CMS film (at 550 nm) was analyzed. As shown in Figure 1, the RI of the film increased with a function of TiO 2 -EMP/CMS content.

實例2 Example 2

進行與實例1相同之程序，但其中改用PAM-100(45.0g)替代EMP(21.5g)。用PAM-100處理之TiO2粒子稱為TiO2-PAM-100粒子，而用PAM-100處理之TiO2粒子接著用CMS處理稱為TiO2-PAM-100/CMS粒子。由TGA結果得到TiO2-PAM/CMS粒子之有機物含量為57.6wt%。 The same procedure as in Example 1 was carried out, except that PAM-100 (45.0 g) was used instead of EMP (21.5 g). The TiO 2 particles treated with PAM-100 are referred to as TiO 2 -PAM-100 particles, while the TiO 2 particles treated with PAM-100 are then treated with CMS as TiO 2 -PAM-100/CMS particles. The organic content of the TiO 2 -PAM/CMS particles obtained from the TGA results was 57.6 wt%.

藉由1H NMR(Bruker AVANCE III 400MHz光譜儀)檢查TiO2-PAM-100粒子及TiO2-PAM-100/CMS粒子表面 上羥基之量。測試條件如下： The amount of hydroxyl groups on the surface of the TiO 2 -PAM-100 particles and the TiO 2 -PAM-100/CMS particles was examined by 1 H NMR (Bruker AVANCE III 400 MHz spectrometer). The test conditions are as follows:

溫度：室溫 Temperature: room temperature

共振頻率：400.1MHz Resonance frequency: 400.1MHz

探針：5mm BBI Probe: 5mm BBI

圖2為TiO2-PAM-100之NMR資料，而圖3為TiO2-PAM-100/CMS之NMR資料。參見圖2，在1H NMR光譜中在1.35ppm處有明顯Ti-OH峰。(參考文獻：Eiden-Assmann,S.；Widoniak,J.；Maret,G.,Chem Mater 2004,16(1),6-11)將來自C=C雙鍵之質子設定為內標物，Ti-OH之完整值為42，此意謂TiO2表面上Ti-OH與PAM-100之莫耳比為42：1。參見圖3，1.35ppm處之Ti-OH峰幾乎消失。其完整值僅為0.5。此時，TiO2表面上TiOH與PAM-100之莫耳比僅為0.5：1。因此，在CMS處理之後，粒子表面上羥基之量減小至CMS處理前之約1/84。 2 is NMR data of TiO 2 -PAM-100, and FIG. 3 is NMR data of TiO 2 -PAM-100/CMS. Referring to Figure 2, there was a significant Ti-OH peak at 1.35 ppm in the 1 H NMR spectrum. (Reference: Eiden-Assmann, S.; Widoniak, J.; Maret, G., Chem Mater 2004, 16(1), 6-11) Setting protons from C=C double bonds as internal standards, Ti The complete value of -OH is 42, which means that the molar ratio of Ti-OH to PAM-100 on the surface of TiO 2 is 42:1. Referring to Figure 3, the Ti-OH peak at 1.35 ppm almost disappeared. Its full value is only 0.5. At this time, the molar ratio of TiOH to PAM-100 on the surface of TiO 2 was only 0.5:1. Therefore, after CMS treatment, the amount of hydroxyl groups on the surface of the particles was reduced to about 1/84 before the CMS treatment.

實例3(比較實例) Example 3 (comparative example)

進行與實例1相同之程序，但其中改用VPA(18.0g)替代EMP(21.5g)。將獲得之TiO2粒子與有機溶劑混合。粒子根本不會分散於PGMEA、PGME及NMP中。 The same procedure as in Example 1 was carried out, except that VPA (18.0 g) was used instead of EMP (21.5 g). The obtained TiO 2 particles are mixed with an organic solvent. Particles are not dispersed at all in PGMEA, PGME, and NMP.

實例4(比較實例) Example 4 (comparative example)

進行與實例1相同之程序，但其中改用商品化銳鈦礦TiO2粒子替代合成之TiO2粒子。獲得之粒子稱為TiO2(市售)-EMP/CMS。計算TiO2粒子中每單位表面之所連接之EMP數且與實例1中所獲得之TiO2-EMP/CMS相比。 The same procedure as in Example 1 was carried out, except that commercialized anatase TiO 2 particles were used instead of the synthesized TiO 2 particles. The particles obtained are referred to as TiO 2 (commercially available) - EMP/CMS. The number of connected EMP per unit surface in the TiO 2 particles was calculated and compared with the TiO 2 -EMP/CMS obtained in Example 1.

TiO2粒子中每單位表面之連接之EMP數等於(n) The number of EMPs per unit surface of TiO 2 particles is equal to (n)

其中d TiO2 為粒徑。商品化銳鈦礦TiO2之直徑由供應商Aladdin提供。ρ TiO2 為自氣體比重計得到之TiO2粒子之密度(載氣為氦氣)。重量分率Wt TiO2-EMP 獲自TGA結果。M EMP 為分子量210.12g/mol。Na為Avogadro常數6.022×1023mol-1。 Wherein d TiO2 is a particle size. The diameter of the commercial anatase TiO 2 is supplied by the supplier Aladdin. ρ TiO2 is obtained from the specific gravity of the density of the gas meter of the TiO 2 particles (carrier gas was helium). The weight fraction Wt TiO2-EMP was obtained from the TGA results. M EMP is a molecular weight of 210.12 g/mol. Na is an Avogadro constant of 6.022 × 10 23 mol -1 .

實例5至11 Examples 5 to 11

對於實例5至10，如表4中所示製備包括實例1中所獲得之TiO2-EMP/CMS粒子、輻射敏感丙烯酸聚合物(DPHA，或DPHA及羧酸功能化樹脂)、光引發劑、抑制劑及ADP之組合物。 For Examples 5 to 10, the TiO 2 -EMP/CMS particles obtained in Example 1 were prepared as shown in Table 4, a radiation-sensitive acrylic polymer (DPHA, or DPHA and a carboxylic acid functionalized resin), a photoinitiator, A combination of an inhibitor and ADP.

在玻璃基板上旋塗組合物。調節旋塗速度以在軟烘烤過程之後獲得1.8μm薄膜厚度。在塗佈工具之接近加熱板上進行120秒的90℃軟烘烤。藉由光干擾法(Lambda-A VL-M6000-LS，Screen)量測薄膜厚度。對經塗佈基板進行曝光及顯影步驟。藉由寬頻接近性曝光工具(MA-1200，Dainippon Kaken)在600mJ/cm2曝光劑量下將經塗佈之基板曝光。藉由i-線感測器(UV-M03A，Orc Manufacturing Co.)量測累計曝光能量。為了獲得光圖案，使用光遮罩(Multitone測試圖案遮罩，Benchmark Technologies)。在曝光過程之後，藉由2.38wt% TMAH(氫氧化四甲基銨)水溶液使基板顯影60秒。在水沖洗及旋轉乾燥過程之後，在對流烘箱中進行60 分鐘的120℃硬烘烤固化。使用橢偏儀量測所獲得之膜在550nm下之折射率。值亦示於表4中。不含TiO2-EMP/CMS粒子之膜在550nm下之RI為1.523。 The composition was spin coated on a glass substrate. The spin coating speed was adjusted to obtain a film thickness of 1.8 μm after the soft baking process. A soft baking at 90 ° C for 120 seconds was performed on the adjacent hot plate of the coating tool. The film thickness was measured by a light interference method (Lambda-A VL-M6000-LS, Screen). The coated substrate is subjected to an exposure and development step. The coated substrate was exposed to a 600 mJ/cm 2 exposure dose by a broadband proximity exposure tool (MA-1200, Dainippon Kaken). The cumulative exposure energy was measured by an i-line sensor (UV-M03A, Orc Manufacturing Co.). In order to obtain a light pattern, a light mask (Multitone test pattern mask, Benchmark Technologies) was used. After the exposure process, the substrate was developed by a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution for 60 seconds. After the water rinse and spin drying process, a 120 °C hard bake cure was carried out in a convection oven for 60 minutes. The refractive index of the obtained film at 550 nm was measured using an ellipsometer. Values are also shown in Table 4. The film containing no TiO 2 -EMP/CMS particles had an RI of 1.523 at 550 nm.

對於實例11，重複與實例8相同之方法，但使用矽晶圓替代玻璃基板。藉由共焦顯微鏡(H300，Lasertec Co.)SEM相片獲得之光學影像示於圖4中。 For Example 11, the same method as in Example 8 was repeated except that a ruthenium wafer was used instead of the glass substrate. An optical image obtained by SEM photograph of a confocal microscope (H300, Lasertec Co.) is shown in Fig. 4.

Claims (10)

一種金屬氧化物粒子，其具有60%或更小之結晶度，其中所述粒子之表面經(a)具有至少一個膦酸酯基之有機化合物及視情況存在之(b)有機矽烷化合物改質。 a metal oxide particle having a crystallinity of 60% or less, wherein the surface of the particle is modified by (a) an organic compound having at least one phosphonate group and optionally (b) an organic decane compound . 如申請專利範圍第1項所述的金屬氧化物，其中所述有機化合物與所述有機矽烷化合物之莫耳比為99：1至1：1。 The metal oxide according to claim 1, wherein the molar ratio of the organic compound to the organodecane compound is from 99:1 to 1:1. 如申請專利範圍第1項所述的金屬氧化物粒子，其中所述金屬氧化物為氧化鈦及氧化鋯中之至少一者。 The metal oxide particle according to claim 1, wherein the metal oxide is at least one of titanium oxide and zirconium oxide. 如申請專利範圍第1項所述的金屬氧化物粒子，其中所述有機化合物係選自甲基丙烯酸伸乙酯磷酸酯及聚(氧化烯)甲基丙烯酸酯。 The metal oxide particles according to claim 1, wherein the organic compound is selected from the group consisting of ethyl methacrylate and poly(oxyalkylene) methacrylate. 如申請專利範圍第1項所述的金屬氧化物粒子，其中所述有機矽烷為三烷基氯矽烷。 The metal oxide particle according to claim 1, wherein the organodecane is a trialkylchlorodecane. 一種形成如申請專利範圍第1項所述的金屬氧化物粒子之方法，所述方法包括以下步驟：(a)使金屬醇鹽於溶液中縮合以形成結晶度為60%或更小之金屬氧化物粒子，(b)使所述金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸以將所述金屬氧化物粒子改質，及(c)視情況使所述經有機化合物改質之金屬氧化物粒子與有機矽烷化合物接觸。 A method of forming metal oxide particles according to claim 1, wherein the method comprises the steps of: (a) condensing a metal alkoxide in a solution to form a metal oxide having a crystallinity of 60% or less Particles, (b) contacting the metal oxide particles with an organic compound having at least one phosphonate group to modify the metal oxide particles, and (c) modifying the organic compound as appropriate The metal oxide particles are contacted with an organodecane compound. 一種聚合物材料，其包括聚合物及如申請專利範圍第1項所述的金屬氧化物粒子。 A polymer material comprising a polymer and metal oxide particles as described in claim 1 of the patent application. 一種輻射敏感組合物，其包括如申請專利範圍第1項所述的金屬氧化物粒子。 A radiation-sensitive composition comprising the metal oxide particles of claim 1 of the patent application. 一種材料，其由如申請專利範圍第8項所述的輻射敏感組合物形成。 A material formed from the radiation-sensitive composition of claim 8 of the patent application. 一種反應產物，其由以下步驟獲得：(a)使金屬醇鹽與酸接觸以形成金屬氧化物粒子，及(b)使所述金屬氧化物粒子與具有至少一個膦酸酯基之有機化合物接觸，接著(c)視情況使所述經有機化合物改質之金屬氧化物粒子與有機矽烷化合物接觸。 a reaction product obtained by (a) contacting a metal alkoxide with an acid to form metal oxide particles, and (b) contacting the metal oxide particles with an organic compound having at least one phosphonate group Next, (c) contacting the organic compound-modified metal oxide particles with an organic decane compound as appropriate.
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