200812912 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種無機阻燃劑之製造。更特別的是， 本發明係關於一種新穎的氫氧化鋁阻燃劑之製造方法。 【先前技術】 * 氫氧化鋁具有多種可替代的名稱諸如鋁水合物、鋁三 水合物等等，但是通常指爲ATH。ATH顆粒已發現使用在 許多材料中作爲充塡劑，諸如例如塑膠、橡膠、熱固性塑 膠、紙等等。這些產物已發現使用在多種商業應用上，諸 如電線及電纜化合物、輸送帶、熱塑性鑄塑物、牆板、地 板材料等等。ΑΤΉ典型使用來改良此些材料的阻燃性且亦 作用爲煙抑制劑。 ATH之合成及製造方法已在技藝中熟知。但是，對製 得修改的ATH等級之需求增加，且現在的方法未能產生出 全部這些等級。因此，當對製得修改的ATH等級之需求增 加時，對製造出這些等級的方法之需求亦增加。 【發明內容】 本發明係關於一種ATH顆粒的製造方法，其包括： 硏磨乾燥過濾器濕濾餅以產生經硏磨乾燥的 ATH顆 粒；及選擇性 去黏聚此經硏磨乾燥的ATH顆粒以產生ATH產物顆 粒； 其中該過濾器濕濾餅包含範圍從約25至約85重量 %(以過濾器濕濾餅的總重量爲準）具有d5〇範圍從約1.5至 3.5微米的ATH顆粒，及其中此ATH產物穎粒具有孔半徑 200812912 中位數（「η。」）範圍從約Q· 09至約0.33微米。 在另一個具體實施例中，本發明係關於一種用來製造 經硏磨乾燥的ATH顆粒之方法，其包括： 硏磨乾燥過濾器濕濾餅以產生經硏磨乾燥的ATH顆 粒；及選擇性 去黏聚此經硏磨乾燥的ATH顆粒以產生ATH產物顆 虫丄 · 松， 其中該過濾器濕濾餅包含範圍從約25至約85重量 % (以過濾器濕濾餅的總重量爲準）具有cho範圍從約1. 5至 3.5微米的ATH顆粒，其中此ATH產物顆粒之特徵爲具有： a) BET比表面積從約3至約6平方公尺/克；及Vmax從 約390至約480立方毫米/克；或 b) BET比表面積從約6至約9平方公尺/克；及Vmax從 約400至約600立方毫米/克；或 c) BET比表面積從約9至約15平方公尺/克；及Vmax 從約300至約700立方毫米/克。 【實施方式】 關於此點，本發明家咸信（然而不意欲由理論所限 制）ATH顆粒由樹脂潤溼的潤溼能力依ATH顆粒之形態學 而定，且關於此點，本發明家已意外地發現藉由使用本發 明之方法可製造出具有改良的潤溼能力（相對於現在可獲 得的ATH顆粒）之ATH顆粒。關於此點，本發明家咸信（然 而不意欲由理論所限制）此經改良的潤溼能力可歸因於由 揭示於本文的方法所製造之ATH顆粒的形態學改良。 再次，關於此點，本發明家咸信（然而不意欲由理論所 200812912 限制）此經改良的形態學可歸因於ATH產物顆粒之總孔體 積比及/或孔半徑中位數（「r5〇」）。關於此點，本發明家咸 信對所提供的聚合物分子來說，具有較高結構化的聚集物 之ATH產物包含更多及較大的孔且似乎更難以溼潤，而導 致在捏合機（如布斯高（Buss Ko)捏合機或雙螺旋槳擠壓器 或已在技藝中熟知及使用於此目的之其它機器）中化合期 間困難（較高的馬達功率圖形變化）。因此，關於此點，本 發明家已發現特徵爲較小的孔尺寸中位數及/或較低的總 孔體積之ΑΤΗ充塡劑與改良由聚合材料潤溼的能力相互關 連，因此造成合成行爲改良（S卩，使用來化合包含ΑΤΗ充塡 劑之阻燃樹脂的化合機器之引擎（馬達）的功率圖形變化較 少）。關於此點，本發明家已發現本發明之方法特別良好適 合於製造出具有這些特徵的ΑΤΗ。 濾餅 在本發明的一個具體實施例中，經硏磨乾燥包含ΑΤΗ 顆粒之過濾器濕濾餅（於本文中有時簡單指爲濾餅）以產生 經硏磨乾燥的ΑΤΗ顆粒。濾餅典型包含範圍從約25至約 85重量％的ΑΤΗ顆粒，以濾餅之總重量爲準。在較佳的具 體實施例中，濾餅包含範圍從約40至約70重量％之ΑΤΗ 顆粒，更佳的範圍從約55至約65重量％之ΑΤΗ顆粒，二 者以相同基礎爲準。 在其它具體實施例中，濾餅包含範圍從約40至約60 重量％的ΑΤΗ顆粒，更佳的範圍從約45至約55重量％之 ΑΤΗ顆粒，二者以相同基礎爲準。在仍然其它具體實施例 中，濾餅包含範圍從約25至約50重量％的ΑΤΗ顆粒，更 200812912 佳的範圍從約30至約45重量％之ATH顆粒，二者以相同 基礎爲準。 在本發明之實行中，所使用的濾餅可從任何使用來產 生AΤΗ顆粒之方法獲得。較佳的是，從包括透過沉澱及過 濾來製造出ATH顆粒之方法獲得濾餅。在典型的具體實施 例中，從下列方法獲得濾餅，其包括將粗產物氫氧化鋁溶 解在苛性鈉中以形成鋁酸鈉液體，將其冷卻及過濾因此形 成在此典型的具體實施例中有用之鋁酸鈉液體。從而製造 0 之鋁酸鈉液體典型具有Na2〇對Al2〇3的莫耳濃度比率在範 圍從約1.4 : 1至約1 · 5 5 : 1。爲了從鋁酸鈉液體中沉澱出 ATH顆粒，將ATH籽粒顆粒加入至銘酸鈉液體，其量範圍 從每升鋁酸鈉液體約1克ATH籽粒顆粒至每升鋁酸鈉液體 約3克ΑΤΉ籽粒顆粒，從而形成方法混合物。當鋁酸鈉液 體在液體溫度從約45至約80°C時，將ATH籽粒顆粒加入 至鋁酸鈉液體。在加入ATH籽粒顆粒之後，攪拌此方法混 合物約100小時或替換地直到Na2〇至AhCh的莫耳濃度比 0 率在範圍從約2.2 ·· 1至約3.5 : 1，從而形成ATH懸浮液。 所獲得的ATH懸浮液典型包含從約80至約160克/升的 ATH，以懸浮液爲準。但是，ATH濃度可變化而落在上述 描述的範圍內。然後，過濾所獲得之ATH懸浮液及清洗以 由彼移除雜質，從而形成濾餅。在濾餅經硏磨乾燥之前， 可以水（較佳爲去鹽水）清洗其一次或在某些具體實施例中 多於一次。 在某些具體實施例中，於濾餅中之ATH顆粒的特徵爲 通常具有BET在範圍從約1 ·0至約4.0平方公尺/克。在較 200812912 佳的具體實施例中，於濾餅中之ΑΤΉ顆粒具有BET在範圍 從約1.5至約2.5平方公尺/克。在濾餅中的ATH顆粒亦可 具有進一步特徵爲d5。在範圍從約1.8至約3.5微米。在較 佳的具體實施例中，於濾餅中之ATH顆粒具有d5Q在範圍 從約1.8至約2.5微米，其比由本發明所產生的ATH產物 顆粒粗糙。 在其它具體實施例中，於濾餅中之ATH顆粒的特徵爲 具有BET在範圍從約4.0至約8.0平方公尺/克。在較佳的 具體實施例中，於濾餅中之ATH顆粒具有BET在範圍從約 5至約7平方公尺/克。在濾餅中的ATH顆粒可具有進一步 特徵爲具有d5。在範圍從約1.5至約2.5微米。在較佳的具 體實施例中，於濾餅中之ATH顆粒具有d5。在範圍從約1.6 至約2.0微米，其比由本發明所製造的ATH產物顆粒粗糙。 在仍然其它具體實施例中，於濾餅中的ATH顆粒之特 徵爲具有BET在範圍從約8.0至約14平方公尺/克。在較 佳的具體實施例中，於濾餅中之ATH顆粒具有BET在範圍 從約9 .至約12平方公尺/克。在濾餅中的ATH顆粒可具有 進一步特徵爲具有dr〇在範圍從約1.5至約2.0微米。在較 佳的具體實施例中，於濾餅中之ATH顆粒具有d5。在範圍 從約1·5至約1.8微米，其比由本發明所製造的ATH產物 顆粒粗糙。 比ΑΤΗ產物顆粒粗糙意謂著在濾餅中的ΑΤΗ顆粒之 eh。値的上限通常比由本發明所製造的ΑΤΗ產物顆粒之d5。 的上限高至少約〇 · 2微米。 關於此點，本發明家咸信（然而不意欲由理論所限制） 200812912 由本發明所製造的ATH產物顆粒之改良的形態: 可歸因於使用來沉澱ΑΤΗ的方法。因此，雖然 術已在技藝中熟知，關於此點，本發明家已發 描述於本文之沉澱及過濾方法（包括較佳具體· 述於本文的硏磨乾燥方法一起，可容易地製造 的形態學之ΑΤΗ產物顆粒，如描述在下列。 硏磨乾燥 如上述所討論，本發明包括硏磨乾燥濾餅 磨乾燥的ΑΤΗ顆粒，且讓其選擇性接受去黏聚 中所使用之「硏磨乾燥」及「經硏磨乾燥」意 硏磨乾燥單元中以紊流的熱空氣流乾燥。此硏 包括堅固安裝在以高圓周速度轉動的實體傳 片。與咼空氣輸,入相關的旋轉移動會將流過的 成極快速的空氣渦流，其會帶起欲乾燥的混合 且分佈及乾燥此混合物。在已完全乾燥之後， 的ΑΤΗ顆粒經由紊流空氣傳輸出磨粉機及藉由 過濾器系統來分離熱空氣與蒸氣。在本發明的 實施例中，在已完全乾燥之後，經乾式硏磨的 由紊流空氣傳輸通過空氣分類器（其已整合至 然後經由紊流空氣傳輸出磨粉機及藉由使用習 系統來分離熱空氣與蒸氣。 使用來乾燥濾餅的熱空氣之輸入量典型b Bm3/h，較佳大於約至約5,000 Bm3/h ,更佳從約 至約40,000 Bm3/h及最佳從約5,000 Bm3/h Bm3/h 〇 至少部分 硏磨乾燥技 現藉由使用 f施例）與描 出具有改良 以產生經硏 。如於本文 謂著濾餅在 磨乾燥單元 動軸上之轉 熱空氣轉換 物、加速其 經乾式硏磨 使用習知的 另一個具體 ATH顆粒經 磨粉機中）， [知的過濾器 k於約3，0 0 0 3,000 Bm3/h 至約 30,000 -10- 200812912 爲了達成此高輸入量，硏磨乾燥單元的轉片典型具有 圓周速度大於約40公尺/秒，較佳大於約60公尺/秒，更佳 大於70公尺/秒及最佳在範圍約70公尺/秒至約140公尺/ 秒。高馬達旋轉速度及高熱空氣輸入量造成熱空氣流具有 大於約3,000的雷諾（Reynolds)數。 ： 使用來硏磨乾燥濾餅的熱空氣流溫度通常高於約150 °C，較佳高於約270°C。在更佳的具體實施例中，熱空氣流 之溫度範圍從約15〇°C至約5 5 0°C，最佳的範圍從約270°C I 至約 500°C。 濾餅之硏磨乾燥產生出具有較大的BET比表面積（如 由DIN-66 1 32測量）之經硏磨乾燥的ATH顆粒，然後在濾餅 中之起始ATH顆粒。典型來說，經硏磨乾燥的ATH之BET 比在濾餅中的ATH顆粒大多於約10%。經硏磨乾燥的ATH 之BET比在濾餅中的ATH顆粒大在範圍從約10%至約40% 較佳。經硏磨乾燥的ATH顆粒之BET比在濾餅中的ATH 顆粒大在範圍從約10%至約25 %更佳。 在許多應用中，從而製造之經硏磨乾燥的ATH顆粒可 「直接」般使用。但是，在某些具體實施例中，經硏磨乾 燥的ATH顆粒經進一步加工以減低或在某些具體實施例中 消除黏聚物。黏聚物在ATH顆粒製造方法中常見，且其存 在可及在某些應用中有害地影響ΑΤΗ顆粒在樹脂中之性 能。因此，ΑΤΗ製造者高度想要減低較佳消除黏聚物。 在本發明之實行上，存在於經硏磨乾燥的ΑΤΗ顆粒中 之黏聚物數目或黏聚程度可藉由讓此經硏磨乾燥的ΑΤΗ顆 粒接受進一步去黏聚加工步驟來減低。 -11- 200812912 去黏聚200812912 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the manufacture of an inorganic flame retardant. More particularly, the present invention relates to a novel method of making an aluminum hydroxide flame retardant. [Prior Art] * Aluminum hydroxide has various alternative names such as aluminum hydrate, aluminum trihydrate, etc., but is generally referred to as ATH. ATH particles have been found to be used as fillers in many materials such as, for example, plastics, rubber, thermoset plastics, paper, and the like. These products have been found to be used in a variety of commercial applications such as wire and cable compounds, conveyor belts, thermoplastic castings, wallboard, flooring materials and the like. Tantalum is typically used to improve the flame retardancy of such materials and also acts as a smoke suppressant. The synthesis and manufacturing methods of ATH are well known in the art. However, there is an increasing demand for modified ATH grades, and current methods fail to produce all of these grades. Therefore, as the need to produce modified ATH ratings increases, so does the need to create these grades. SUMMARY OF THE INVENTION The present invention is directed to a method of making ATH particles, comprising: honing a dry filter wet cake to produce honed and dried ATH particles; and selectively deagglomerating the honed and dried ATH particles To produce ATH product particles; wherein the filter wet cake comprises from about 25 to about 85% by weight (based on the total weight of the filter wet cake) having ATH particles having a d5 〇 ranging from about 1.5 to 3.5 microns, And the ATH product of the ATH product has a pore radius of 200812912 median ("η.") ranging from about Q·09 to about 0.33 μm. In another embodiment, the present invention is directed to a method for making honed and dried ATH particles, comprising: honing a dry filter wet cake to produce honed and dried ATH particles; and De-agglomerating the dried ATH granules to produce the ATH product worms, wherein the filter wet cake comprises from about 25 to about 85% by weight (based on the total weight of the filter wet cake) Having ATH particles having a cho ranging from about 1.5 to 3.5 microns, wherein the ATH product particles are characterized by: a) a BET specific surface area from about 3 to about 6 square meters per gram; and a Vmax from about 390 to about 480 cubic millimeters per gram; or b) BET specific surface area from about 6 to about 9 square meters per gram; and Vmax from about 400 to about 600 cubic millimeters per gram; or c) BET specific surface area from about 9 to about 15 square Metric/gram; and Vmax from about 300 to about 700 cubic millimeters per gram. [Embodiment] In this regard, the inventors of the present invention (but not intended to be limited by theory) the wetting ability of the ATH particles to be wetted by the resin depends on the morphology of the ATH particles, and in this regard, the inventor has It has been unexpectedly discovered that ATH particles having improved wetting ability (relative to the currently available ATH particles) can be produced by using the method of the present invention. In this regard, the inventors of the present invention (and are not intended to be bound by theory) this improved wetting ability can be attributed to the morphological improvement of the ATH particles produced by the methods disclosed herein. Again, in this regard, the inventor's Xianxin (though not intended to be limited by Theory 200812912) this modified morphology can be attributed to the total pore volume ratio of the ATH product particles and/or the median pore radius ("r5 〇"). In this regard, the inventors of the present invention believe that the ATH product with higher structured aggregates contains more and larger pores and appears to be more difficult to wet, resulting in a kneading machine (for the polymer molecules provided). Difficulty (higher motor power pattern change) during compounding, such as a Buss Ko kneader or twin propeller extruder or other machine that is well known in the art and used for this purpose. Thus, in this regard, the inventors have discovered that the sputum-filling agent characterized by a smaller median pore size and/or a lower total pore volume correlates with improved ability to wet the polymeric material, thereby causing synthesis Behavioral improvement (ie, the engine (motor) used to compound a flame retardant resin containing an antimony agent has less power pattern change). In this regard, the inventors have found that the method of the present invention is particularly well suited for the manufacture of crucibles having these characteristics. Filter Cake In one embodiment of the invention, a filter wet cake comprising cerium particles (sometimes referred to herein simply as a filter cake) is honed to produce honed dried cerium particles. The filter cake typically comprises from about 25 to about 85% by weight of cerium particles, based on the total weight of the filter cake. In a preferred embodiment, the filter cake comprises cerium particles ranging from about 40 to about 70 weight percent, more preferably from about 55 to about 65 weight percent cerium particles, both of which are based on the same basis. In other embodiments, the filter cake comprises cerium particles ranging from about 40 to about 60 weight percent, more preferably from about 45 to about 55 weight percent cerium particles, which are based on the same basis. In still other embodiments, the filter cake comprises cerium particles ranging from about 25 to about 50 weight percent, more preferably from 2008 to 30 weight percent ATH particles, whichever is the same. In the practice of the present invention, the filter cake used can be obtained from any method used to produce A ΤΗ particles. Preferably, the filter cake is obtained from a process comprising the manufacture of ATH particles by precipitation and filtration. In a typical embodiment, a filter cake is obtained from the following process comprising dissolving the crude product aluminum hydroxide in caustic soda to form a sodium aluminate liquid, cooling and filtering thereby forming in this exemplary embodiment Useful sodium aluminate liquid. Thus, the sodium aluminate liquid produced by 0 typically has a molar concentration ratio of Na2? to Al??3 ranging from about 1.4:1 to about 155. In order to precipitate ATH particles from the sodium aluminate liquid, the ATH grain particles are added to the sodium sulphate liquid in an amount ranging from about 1 gram of ATH grain particles per liter of sodium aluminate liquid to about 3 grams per liter of sodium aluminate liquid. Grain particles, thereby forming a method mixture. The ATH grain particles are added to the sodium aluminate liquid when the sodium aluminate liquid is at a liquid temperature of from about 45 to about 80 °C. After the addition of the ATH grain particles, the mixture of the process is stirred for about 100 hours or alternatively until the molar concentration ratio of Na2〇 to AhCh ranges from about 2.2··1 to about 3.5:1 to form an ATH suspension. The ATH suspension obtained typically comprises from about 80 to about 160 grams per liter of ATH, based on the suspension. However, the ATH concentration can vary and fall within the ranges described above. The obtained ATH suspension is then filtered and washed to remove impurities to form a filter cake. The filter cake may be washed once with water (preferably desalinated water) or more than once in some embodiments before the filter cake is honed and dried. In some embodiments, the ATH particles in the filter cake are characterized by having a BET in the range of from about 1 +/- 0 to about 4.0 square meters per gram. In a preferred embodiment of 200812912, the ruthenium particles in the filter cake have a BET ranging from about 1.5 to about 2.5 square meters per gram. The ATH particles in the filter cake may also have the further feature d5. In the range from about 1.8 to about 3.5 microns. In a preferred embodiment, the ATH particles in the filter cake have a d5Q in the range of from about 1.8 to about 2.5 microns which is coarser than the ATH product particles produced by the present invention. In other embodiments, the ATH particles in the filter cake are characterized by having a BET ranging from about 4.0 to about 8.0 square meters per gram. In a preferred embodiment, the ATH particles in the filter cake have a BET in the range of from about 5 to about 7 square meters per gram. The ATH particles in the filter cake may be further characterized as having d5. In the range from about 1.5 to about 2.5 microns. In a preferred embodiment, the ATH particles in the filter cake have a d5. It ranges from about 1.6 to about 2.0 microns which is coarser than the ATH product particles produced by the present invention. In still other embodiments, the ATH particles in the filter cake have a characteristic of having a BET ranging from about 8.0 to about 14 square meters per gram. In a preferred embodiment, the ATH particles in the filter cake have a BET ranging from about 9 to about 12 square meters per gram. The ATH particles in the filter cake can be further characterized as having a dr 〇 ranging from about 1.5 to about 2.0 microns. In a preferred embodiment, the ATH particles in the filter cake have a d5. It ranges from about 1. 5 to about 1.8 microns which is coarser than the ATH product particles produced by the present invention. Rougher than the ruthenium product particles means the eh of the ruthenium particles in the filter cake. The upper limit of ruthenium is generally greater than d5 of the ruthenium product particles produced by the present invention. The upper limit is at least about 2 μm. In this regard, the inventors of the present invention (but are not intended to be limited by theory) 200812912 Improved morphology of ATH product particles made by the present invention: A method attributable to the use of precipitated ruthenium. Thus, although the technique is well known in the art, in this regard, the inventors have described the precipitation and filtration methods described herein (including the preferred tangential drying methods described herein, morphologies that can be readily fabricated) The product granules are as described below. Honing Drying As discussed above, the present invention comprises honing and drying the filter cake to dry the ruthenium granules and allowing them to selectively undergo "drying" used in deagglomeration. And "honed and dried" means that the drying unit is dried by a turbulent flow of hot air. This includes a solid transfer that is sturdyly mounted at a high peripheral speed. The rotational movement associated with the air input will a rapidly vortex of air that flows through, which brings the mixture to be dried and distributes and dries the mixture. After it has completely dried, the ruthenium particles are transported out of the mill via turbulent air and through the filter system. Separating hot air from steam. In an embodiment of the invention, the dry honed air is passed through the air classifier after it has been completely dried (which has been integrated) Transferring the mill through turbulent air and separating the hot air and steam by using a conventional system. The input of hot air used to dry the filter cake is typically b Bm3 / h, preferably greater than about 5,000 Bm3 / h, More preferably from about 40,000 Bm3/h and preferably from about 5,000 Bm3/h Bm3/h 〇 at least partially honing and drying techniques are now improved by using the f example) to produce warp. The filter cake is rotated on the moving shaft of the drying unit to accelerate the dry honing using another conventional ATH granule through a conventional mill, [the known filter k is about 3,0 0 0 3,000 Bm3/h to approximately 30,000 -10- 200812912 To achieve this high input, the rotor of the honing drying unit typically has a peripheral speed greater than about 40 meters per second, preferably greater than about 60 meters per second. Preferably greater than 70 meters per second and optimally in the range of from about 70 meters per second to about 140 meters per second. The high motor rotational speed and high hot air input cause the hot air flow to have a Reynolds number greater than about 3,000. : The temperature of the hot air stream used to honed the dried filter cake is typically above about 150 ° C, preferably above about 270 ° C. In a more preferred embodiment, the temperature of the hot air stream ranges from about 15 ° C to about 550 ° C, with an optimum range from about 270 ° C to about 500 ° C. The honing of the filter cake produces a honed and dried ATH granule having a large BET specific surface area (as measured by DIN-66 1 32) and then the starting ATH granules in the filter cake. Typically, the BET of the honed and dried ATH is mostly about 10% greater than the ATH particles in the filter cake. The BET of the honed and dried ATH is preferably in the range of from about 10% to about 40% greater than the ATH particles in the filter cake. The BET ratio of the honed and dried ATH particles is preferably from about 10% to about 25% greater than the ATH particles in the filter cake. In many applications, the honed and dried ATH granules thus produced can be used "directly". However, in some embodiments, the honed dry ATH particles are further processed to reduce or, in some embodiments, eliminate the binder. Viscosity is common in ATH particle manufacturing processes and has the potential to detrimentally affect the performance of the ruthenium particles in the resin in certain applications. Therefore, the manufacturer of the crucible is highly tempted to reduce the better elimination of the binder. In the practice of the present invention, the number or degree of cohesiveness present in the honed and dried cerium particles can be reduced by subjecting the honed and dried cerium particles to further deagglomerating processing steps. -11- 200812912 to stick together
去黏聚意謂著讓經硏磨乾燥的ATH顆粒接受進一步處 理，其中存在於經硏磨乾燥的ΑΤΗ顆粒中之黏聚物數目或 黏聚程度減低（即，存在於經硏磨乾燥的ΑΤΗ顆粒中之黏聚 物數目大於存在於ΑΤΗ產物穎粒中的黏聚物數目），在某些 具體實施例中實質上消除，且在經硏磨乾燥的ΑΤΗ之顆粒 尺寸上些微減低。「少量縮減粒徑」意謂著ΑΤΗ產物顆粒 、的d5。大於或等於經硏磨乾燥之ΑΤΗ顆粒的90%。經硏磨 ^ 乾燥的ATH顆粒之剩餘性質與從去黏聚經硏磨乾燥的ATH 顆粒所製造之ATH產物顆粒相同或實質上相同。在較佳的 具體實施例中，經乾式硏磨的ATH之d5。範圍從經硏磨乾 燥的ATH顆粒之約90 %至約95%，更佳在經硏磨乾燥的ATH 顆粒之約95%至約99%的範圍內。 可使用任何已熟知能有效減低黏聚物的技術來達成減 少存在於經硏磨乾燥的ATH顆粒中之黏聚物。在較佳的具 體實施例中，透過使用空氣分類器或栓磨（pin mill)來達成 去黏聚。在某些具體實施例中，透過使用一或多個栓磨， ^ 在其它具體實施例中，一或多個空氣分類器來達成去黏聚。 合適於使用在本文中的空氣分類器包括使用重力、離 心力、慣性力量或其任何組合來分類 ATH產物顆粒的那 些。這些分類器之使用已在技藝中熟知，且具有在技藝中 的一般技術及想要的最後ATH產物尺寸之知識的人士可容 易地選擇出包含合適的篩網及/或篩孔之分類器。 合適於使用在本文中的栓磨包括乾式及溼式栓磨。如 空氣分類器一般，栓磨之使用已在技藝中熟知，及具有在 -12- 200812912 、 技藝中的一般技術及想要的最後ATH產物顆粒性質之知識 的人士可容易地選擇出符合特別應用之最好的栓磨。 浓电形態學的ATH產物顆粒 通常來說，本發明之方法可使用來製造出具有下列性 質的ATH產物顆粒：吸油性（如利用ISO 7 87_5 : 1 980測量） 範圍從約1至約35% ; BET比表面積（如利用DIN-66 132測 量）範圍從約1至15平方公尺/克；及d5〇範圍從約0.5至 2.5微米。 0 但是，本發明之方法特別良好適合於製造出具有改良 的形態學（當與現在可獲得的ATH顆粒比較時）之ATH產物 顆粒。再次，關於此點，本發明家咸信（然而不意欲由理論 所限制）此改良的形態學可歸因於於此製造之 ATH產物顆 粒的總孔體積比及/或孔半徑中位數（「r5。」）。關於此點， 本發明家咸信對所提供的聚合物分子來說，具有較高結構 化的聚集物之ATH包含更多及較大孔且似乎更難以溼潤， 而導致在捏合機（如布斯高捏合機或雙螺旋槳擠壓器或已 在技藝中熟知且已使用於此目的之其它機器）中化合期間 困難（較高的馬達功率圖形變化）。關於此點，本發明家已 發現本發明之方法製造出特徵爲較小的孔尺寸中位數及/ 或較低的總孔體積之 ATH產物顆粒（當與現在可獲得的 ATH比較時），此與改良由聚合材料潤溼（當與現在可獲得 的ATH顆粒比較時）之ATH產物顆粒有相互關連，因此， 導致改良化合行爲，即，使用來化合包含ATH產物顆粒充 塡劑的阻燃樹脂之化合機器的引擎（馬達）之功率圖形的變 化較少。 -13- 200812912 由本發明所製造的ATH產物顆粒在約1000巴下之η。 及孔體積比（「Vmax」）可推導自汞孔隙度測量法。汞孔隙度 測量法的理論以非反應性、非潤溼性液體將不會滲透過孔 直到施加足夠的壓力以強迫其進入之物理原理爲基礎。因 此，液體進入孔所需要的壓力愈高，孔尺寸愈小。已發現 較小的孔尺寸及/或較低的總孔體積比與由本發朋所製造 的ATH產物顆粒有較好的潤溼能力相互關連。由本發明所 製造的ATH產物顆粒之孔尺寸可使用來自意大’利的卡羅咢 0 伯設備（C a r 1 〇 Erba S t r u m e n t a z i o n e)之波羅西計 (Porosimeter)2000，從推導自汞孔隙度測量法的資料來計算 出。根據波羅西計2000的手冊，使用下列方程式來從測量 壓力P計算出孔半徑r ·· r = -2 r cos( 0 )/p，其中Θ爲潤溼 角度及r爲表面張力。於本文中所採用的測量法所使用的 0値爲141.3°及r設定爲480達因/公分。 爲了改良測量法的再現能力，如描述在波羅西計2000 的手冊中般，從第二ATH侵入測試操作來計算ATH產物顆 0 粒之孔尺寸。使用第二測試操作，因爲本發明家觀察到具 有體積V 〇的录量會在擠壓出之後（即，在壓力釋放至周壓 之後）餘留在ATH顆粒的樣品中。因此，r5。可推導自此資 料，如將在下列隨著參考至第1、2及3圖來解釋。 在第一測試操作中，如在波羅西計2000之手冊中所描 述般製備由本發明所製造的ATH產物顆粒之樣品，及測量 孔體積如爲所施加的侵入壓力p(使用最大壓力1000巴）之 函數。釋放壓力及在完成第一測試操作之後讓其到達周 壓。使用來自第一測試操作的相同ATH樣品（無雜質）進行 -14- .200812912 第二侵入測試操作（根據波羅西計2000的手冊），其中第二 測試操作的孔體積比V(p)之測量採用體積V〇作爲新的起始 體積，然後對第二測試操作設定成歸零。 在第二侵入測試操作中，再次進行樣品的孔體積比V (p) 測量如爲所施加的侵入壓力（使用最大壓力1 000巴）之函 數。第1圖顯示出在第二侵入測試操作中根據本發明所製 造的ATH(等級編號1)之孔體積比V如爲所施加的壓力之函 數，且與現在可商業購得的A TH產物比較。在約1000巴 ^ (即，最大壓力使用在測量）下之孔體積於本文中指爲Vmax。 藉由波羅西計2000，從第二ATH侵入測試操作中，根 據式r = -2 r c〇s( 0 )/p來計算出孔半徑r，其中0爲潤溼角 度，7爲表面張力及p爲侵入壓力。對在本文中所採取的 全部r測量來說，使用141.3°的0値及將r設定成480 達因/公分。從而將孔體積比對孔半徑r繪圖。第2圖顯示 出在第二侵入測試操作（使用相同樣品）中，對孔半徑r繪製 之孔體積比V。 第3圖顯示出在第二侵入測試操作中，對孔半徑r繪 製之經標準化的孔體積比，即，在此曲線中，將第二侵入 測試操作之最大孔體積比（vmax)設定成100%且將特別的 ATH之其它比體積除以此最大値。在50%相對孔體積比處 的孔半徑於本文中定義爲孔半徑中位數r5。。例如，根據第 3圖，根據本發明的ATH (SP，發明）之孔半徑中位數η。爲 0.33微米。 使用根據本發明所製造的ΑΤΗ產物顆粒之樣品來重覆 上述描述的程序，且已發現由本發明所製造之ΑΤΗ產物顆 -15- 200812912 粒具有η。（即，在50%相對孔體積比處的孔半徑）在範圍從 約0.09至約0.33微米。在本發明的較佳具體實施例中，由 本發明所製造的ATH產物顆粒之r5〇在範圍從約0.20至約 0.33微米，更佳的範圍從約〇.2至約0.3微米。在其它較佳 的具體實施例中，r5。在範圍從約0.185至約0.3 25微米，更 佳的範圍從約〇. 1 8 5至約0.2 5微米。在仍然其它較佳的具 體實施例中，r5〇在範圍從約0.09至約0.21微米，更佳的 範圍從約0.09至約0.165微米。 φ 由本發明所製造的 ATH產物顆粒其特徵亦可爲具有De-agglomeration means that the honed and dried ATH granules are subjected to further treatment, wherein the number of cohesive or the degree of cohesiveness present in the honed and dried cerium particles is reduced (i.e., present in the honed dry mash) The number of cohesive particles in the granules is greater than the number of viscous polymers present in the granules of the cerium product. In some embodiments, it is substantially eliminated and the particle size of the honed and dried mash is slightly reduced. "Small amount of reduced particle size" means d5 of the product particles. Greater than or equal to 90% of the honed and dried ruthenium particles. The remaining properties of the honed ATH particles are the same or substantially the same as the ATH product particles produced from the de-agglomerated honed dry ATH particles. In a preferred embodiment, dry honed d5 of ATH. It ranges from about 90% to about 95% of the honed dry ATH particles, more preferably from about 95% to about 99% of the honed and dried ATH particles. Any of the well known techniques for effectively reducing the binder can be used to achieve the reduction of the binder present in the honed and dried ATH particles. In a preferred embodiment, de-agglomeration is achieved by the use of an air classifier or pin mill. In some embodiments, de-agglomeration is achieved by using one or more bolting, ^ in other embodiments, one or more air classifiers. Air classifiers suitable for use herein include those that use gravity, centrifugation, inertial forces, or any combination thereof to classify ATH product particles. The use of these classifiers is well known in the art, and those having the general skill in the art and the knowledge of the desired final ATH product size can readily select a classifier containing suitable screens and/or screen openings. Suitable for use in the bolting herein includes dry and wet bolting. As is generally the case with air classifiers, the use of bolting is well known in the art, and those having knowledge of the general techniques of the art from -12-200812912, and the desired final ATH product particle properties can be readily selected for special applications. The best bolting. Concentrated Electromorphic ATH Product Particles Generally, the process of the present invention can be used to produce ATH product particles having the following properties: oil absorption (as measured using ISO 7 87_5: 1 980) ranging from about 1 to about 35% The BET specific surface area (as measured by DIN-66 132) ranges from about 1 to 15 square meters per gram; and d5 〇 ranges from about 0.5 to 2.5 microns. 0 However, the process of the present invention is particularly well suited for the manufacture of ATH product particles having improved morphology (when compared to currently available ATH particles). Again, in this regard, the inventors of the present invention (but not intended to be bound by theory) may be attributed to the total pore volume ratio and/or median pore radius of the ATH product particles produced herein ( "r5."). In this regard, the inventors of the present invention believe that the ATH with higher structured aggregates of the polymer molecules provided contains more and larger pores and seems to be more difficult to wet, resulting in a kneading machine (such as cloth). Difficult (higher motor power pattern changes) during the combination of the Sco kneader or twin propeller extruder or other machines that are well known in the art and have been used for this purpose. In this regard, the inventors have discovered that the method of the present invention produces ATH product particles characterized by a smaller median pore size and/or a lower total pore volume (when compared to the currently available ATH), This is related to the improvement of the ATH product particles which are wetted by the polymeric material (when compared to the currently available ATH particles) and, therefore, result in improved compounding behavior, i.e., the use of a flame retardant comprising a ATH product particle-filling agent. The power pattern of the engine (motor) of the resin compounding machine is less changed. -13- 200812912 ATH product particles produced by the present invention have a η of about 1000 bar. And the pore volume ratio ("Vmax") can be derived from the mercury porosity measurement method. The theory of mercury porosimetry is based on the physical principle that non-reactive, non-wetting liquids will not penetrate the pores until sufficient pressure is applied to force them into. Therefore, the higher the pressure required for liquid to enter the orifice, the smaller the pore size. It has been found that smaller pore sizes and/or lower total pore volume ratios correlate with better wetting ability of the ATH product particles produced by the present inventors. The pore size of the ATH product particles produced by the present invention can be derived from mercury porosity using a Porosimeter 2000 from the ar 1 〇Erba S trumentazione. The data of the measurement method is calculated. According to the Handbook of Boroisi 2000, the following equation is used to calculate the hole radius r ·· r = -2 r cos( 0 )/p from the measured pressure P, where Θ is the wetting angle and r is the surface tension. The measurement used in the measurement used herein is 141.3° and r is set to 480 dynes/cm. In order to improve the reproducibility of the measurement method, the hole size of the ATH product 0 was calculated from the second ATH intrusion test operation as described in the Handbook of the Baltic 2000. A second test operation was used because the inventors observed that the volume with volume V 会 would remain in the sample of ATH particles after extrusion (i.e., after pressure is released to the peripheral pressure). Therefore, r5. This information can be derived from the following, as will be explained below with reference to Figures 1, 2 and 3. In a first test operation, a sample of the ATH product particles produced by the present invention is prepared as described in the Handbook of the Perotometer 2000, and the pore volume is measured as the applied intrusion pressure p (using a maximum pressure of 1000 bar) ) function. Release the pressure and allow it to reach the ambient pressure after completing the first test procedure. The same ATH sample from the first test operation (no impurities) was used for the 14-.200812912 second intrusion test operation (according to the Handbook of the Perosi 2000), where the pore volume ratio of the second test operation was V(p) The measurement uses the volume V〇 as the new starting volume and then sets the second test operation to zero. In the second intrusion test operation, the pore volume ratio V (p) of the sample is again measured as a function of the applied intrusion pressure (using a maximum pressure of 1 000 bar). Figure 1 shows the pore volume ratio V of ATH (grade number 1) produced in accordance with the present invention as a function of applied pressure in a second intrusion test operation, and compared to the currently commercially available A TH product. . The pore volume at about 1000 bar ^ (i.e., the maximum pressure used in the measurement) is referred to herein as Vmax. From the second ATH intrusion test operation, the hole radius r is calculated according to the formula r = -2 rc〇s( 0 )/p by the Borosi meter 2000, where 0 is the wetting angle and 7 is the surface tension and p is the intrusive pressure. For all r measurements taken in this paper, use 14 ° 14 ° and set r to 480 dynes/cm. The pore volume ratio is thus plotted against the pore radius r. Figure 2 shows the pore volume ratio V plotted against the hole radius r in the second intrusion test operation (using the same sample). Figure 3 shows the normalized pore volume ratio plotted against the hole radius r in the second intrusion test operation, i.e., in this curve, the maximum pore volume ratio (vmax) of the second intrusion test operation is set to 100. % and divide the other specific volume of the special ATH by this maximum. The pore radius at a 50% relative pore volume ratio is defined herein as the pore radius median r5. . For example, according to Fig. 3, the median η of the hole radius of ATH (SP, invention) according to the present invention. It is 0.33 microns. The procedure described above was repeated using a sample of the ruthenium product particles produced in accordance with the present invention, and it has been found that the ruthenium product -15-200812912 granules produced by the present invention have η. (i.e., the pore radius at a 50% relative pore volume ratio) ranges from about 0.09 to about 0.33 microns. In a preferred embodiment of the invention, the ATH product particles produced by the present invention have a r5 〇 ranging from about 0.20 to about 0.33 microns, more preferably from about 0.2 to about 0.3 microns. In other preferred embodiments, r5. It ranges from about 0.185 to about 0.325 microns, more preferably from about 0.185 to about 0.25 microns. In still other preferred embodiments, r5〇 ranges from about 0.09 to about 0.21 microns, more preferably from about 0.09 to about 0.165 microns. φ The ATH product particles produced by the present invention may also be characterized as having
Vmax (即，在約1〇〇〇巴下之最大孔體積比）在範圍從約300 至約700立方毫米/克。在本發明的較佳具體實施例中，由 本發明所製造的ATH產物顆粒之Vmax在範圍從約390至約 480立方毫米/克，更佳的範圍從約410至約450立方毫米/ 克。在其它較佳的具體實施例中，Vmax在範圍從約400至 約600立方毫米/克，更佳的範圍從約450至約5 50立方毫 米/克。在更其它較佳的具體實施例中，Vmax在範圍從約300 φ 至約700立方毫米/克，更佳的範圍從約350至約5 50立方 毫米/克。 由本發明所製造的ATH產物顆粒其特徵亦可爲具有吸 油性（如利用ISO 787-5: 1 980測量）在範圍從約1至約35%。 在某些較佳的具體實施例中，由本發明所製造的ATH產物 顆粒其特徵爲具有吸油性在範圍從約23至約30%，更佳的 範圍從約25%至約28%。在其它較佳的具體實施例中，由 本發明所製造的ATH產物顆粒其特徵爲具有吸油性在範圍 從約25 %至約32%，更佳的範圍從約26%至約30%。在更其 -16- 200812912 它較佳的具體實施例中，由本發明所製造的ATH產物顆粒 其特徵爲具有吸油性.在範圍從約2 5至約3 5 %，更佳的範圍 從約27 %至約32%。在其它具體實施例中，由本發明所製 造的ATH產物顆粒之吸油性在範圍從約19%至約23%，及 在仍然其它具體實施例中，由本發明所製造的ATH產物顆 粒之吸油性在範圍從約2 1 %至約2 5 %。 由本發明所製造的ATH產物顆粒其特徵亦可爲具有 BET比表面積（如利用DIN-66 1 32測量）在範圍從約1至15 平方公尺/克。在較佳的具體實施例中，由本發明所製造的 ATH產物顆粒具有BET比表面積在範圍從約3至約6平方 公尺/克，更佳的範圍從約3.5至約5.5平方公尺/克。’在其 它較佳的具體實施例中，由本發明所製造的ATH產物顆粒 具有BET比表面積在範圍從約6至約9平方公尺/克，更佳 的範圍從約6 · 5至約8.5平方公尺/克。在仍然其它較佳的 具體實施例中，由本發明所製造的A.TH產物顆粒具有3ET 比表面積在範圍從約9至約1 5平方公尺/克，更佳的範圍 從約10.5至約12.5平方公尺/克。 由本發明所製造的ATH產物顆粒其特徵亦可爲具有 dw在範圍從約〇·5至2.5微米。在較佳的具體實施例中， 由本發明所製造的ATH產物顆粒具有d5〇在範圍從約1.5 至約2 · 5微米，更佳的範圍從約1 · 8至約2 · 2微米。在其它 較佳具體實施例中，由本發明所製造的ATH產物顆粒具有 d5◦在範圍從約1.3至約2.0微米，更佳的範圍從約1.4至約 1.8微米。在仍然其它較佳具體實施例中，由本發明所製造 的ATH產物顆粒具有d5。在範圍從約0.9至約1.8微米，更 200812912 佳的範圍從約1 · 1至約1. 5微米。 應注意的是，使用來自康塔（Quantachrome)的Cilas 1 0 64L雷射光譜儀，利用雷射繞射來測量於本文中所揭示 的全部顆粒直徑度量（即，d5〇。通常來說，於本文中使用 來度量d5 〇的程序可藉由首先將合適的水分散劑溶液（製劑 參見下列）引進裝置的樣品製備容器中來實行。然後選擇稱 爲「顆粒專家」（Particle Expert)的標準測量，亦選擇測量 模型「範圍1」，然後選擇施加至預計的顆粒尺寸分佈之 φ 裝置內部參激。應注意的是，在測量期間，樣品於分散期 間及於測量期間典型曝露至超音波約6 0秒。在已進行背景 測量之後，將欲分析之約75至約1 00毫克的樣品放置在含 有水/分散劑溶液之樣品容器中及開始測量。此水/分散劑溶 液可藉由首先從500克卡爾岡（Calgon)(可從KMF雷伯化學 (Labor chemie)購得）與 3 升 CAL Poly salt(可從貝斯拂（BASF) 購得）製備濃縮物來製備。此溶液以去離子水構成至1 0升。 採取此原始10升的100毫升且依次以去離子水進一步稀釋 至10升，及將此最後溶液使用作爲上述描述的水分散劑溶 液。 使用ATH產物顆粒作爲阻燃劑_ 根據本發明所製造的ATH產物顆粒可使用在多種合成 樹脂中作爲阻燃劑。已發現使用經乾式硏磨的ΑΤΉ顆粒之 熱塑性樹脂的非爲限制實例包括聚乙烯、乙烯-丙烯共聚 物、C2至C8烯烴（α -烯烴）的聚合物及共聚物（諸如聚丁烯、 聚（4-甲基戊烯-1)或其類似物）、這些烯烴及二烯的共聚 物、乙烯-丙烯酸酯共聚物、聚苯乙烯、ABS樹脂、AAS樹 -18- 200812912 脂、AS樹脂、MBS樹脂、乙烯-氯乙烯共聚物樹脂、乙烯_ 醋酸乙烯酯共聚物樹脂、乙烯-氯乙烯-醋酸乙烯酯接枝聚 合物樹脂、偏二氯乙烯、聚氯乙烯、氯化的聚乙烯、氯乙 烯-丙烯共聚物、醋酸乙烯酯樹脂、苯氧基樹脂及其類似 物。合適的合成樹脂之進一步實例包括熱固性樹脂，諸如 環氧樹脂、酚樹脂、蜜胺樹脂、不飽和聚酯樹脂、醇酸樹 脂及尿素樹脂；及亦包括天然或合成橡膠，諸如EPDM、丁 基橡膠、異戊二烯橡膠、SBR、NIR、胺基甲酸酯橡膠、聚 ^ 丁二烯橡膠、丙烯酸橡膠、矽氧橡膠、氟彈性體、NBR及 氯磺酸化的聚乙烯。進一步包括的有聚合物懸浮液（乳膠）。 較佳的是，此合成樹脂爲以聚乙烯爲基礎的樹脂，諸 如高密度聚乙烯、低密度聚乙烯、線性低密度聚乙烯、超 極低密度聚乙烯、EVA(乙烯-醋酸乙烯酯樹脂）、EEA(乙烯-丙烯酸乙酯樹脂）、EMA(乙烯-丙烯酸甲酯共聚物樹脂）、 EAA(乙烯-丙烯酸共聚物樹脂）及超高分子量聚乙烯；及C2 至C8烯烴（α -烯烴）的聚合物及共聚物，諸如聚丁烯及聚（4-甲基戊烯-1)、聚氯乙烯及橡膠。在更佳的具體實施例中， 此合成樹脂爲以聚乙烯爲基礎的樹脂。 本發明家已發現藉由在合成樹脂中使用根據本發明的 ΑΤΗ產物顆粒作爲阻燃劑，含氫氧化鋁之合成樹脂可達成 較好的合成性能。較好的化合性能高度由該等化合器、製 造等等想要，以便用含ΑΤΗ產物顆粒的合成樹脂來製造出 高度塡充阻燃的化合物及最後擠壓或模塑物件。高度塡充 意謂著包含阻燃量的ΑΤΗ產物顆粒那些，如討論在下列。 較好的化合性能意謂著在混合包含根據本發明所製造 -19- 200812912 的ATH產物顆粒之合成樹脂所需要的合成機器（如布斯高 捏合機或雙螺旋槳擠壓器）中之能量程度的變化振幅小於 混合包含習知ΑΤΗ顆粒的合成樹脂之那些化合機器。能量 程度的變化較小允許欲混合或擠壓之含ΑΤΗ產物顆粒的合 成樹脂有較高的輸入量及/或更均勻（均質）的材料。 因此，在一個具體實施例中，本發明係關於一種阻燃 聚合物調配物，其包含至少一種選自於上述描述的那些之 合成樹脂（在某些具體實施例中僅有一種）及阻燃量之根據 φ 本發明所製造的ΑΤΗ產物顆粒；及從此阻燃聚合物調配物 所製得之擠壓及/或模塑物件。 阻燃量的ΑΤΗ產物顆粒通常意謂著在範圍從約5重量 %至約9 0重量％內（以阻燃聚合物調配物的重量爲準）及更 佳從約20重量％至約70重量％(以相同基礎爲準）。在最佳 的具體實施例中，阻燃量從約30重量％至約65重量％的 ΑΤΗ產物顆粒（以相同基礎爲準）。 此阻燃聚合物調配物亦可包含其它在技藝中通常使用 $ 的添加劑。合適於使用在本發明的阻燃聚合物調配物中之 其它添加劑之非爲限制的實例包括擠壓助劑，諸如聚乙烯 蠟、以Si爲基礎的擠壓助劑、脂肪酸類；耦合劑，諸如胺 基-、乙燒基-或院基较烷或馬來酸接枝聚合物；硬脂酸鈉 或硬脂酸鈣；有機過氧化物；染料；顏料；充塡劑；吹泡 劑；防臭劑；熱安定劑；抗氧化劑；抗靜電劑；補強劑； 金屬清除劑或去活化劑；衝擊改質劑；加工助劑；脫模助 劑、潤滑劑；防阻塞劑；其它阻燃劑；UV安定劑；塑化劑； 流動助劑；及其類似物。若必要時，亦可在阻燃聚合物調 -20- 200812912 配物中包含成核劑，諸如矽酸鈣或靛藍。其它可選擇的添 加劑之比例已習知及可改變以適合任何所提供的狀況之需 進行摻入及加入阻燃聚合物調配物組分的方法對本發 明來說非爲關鍵且可爲任何已在技藝中熟知之方法，只要 所選擇的方法包括實質上均勻混合。例如，上述的每種組 分及可選擇的添加劑（若使用的話）可使用下列機器來混 合：布斯高捏合機、內部混合器、法拉爾（Farrel)連續混合 φ 器或雙螺旋槳擠壓器，或在某些實例亦可爲單螺旋槳擠壓 器或二個輥筒磨粉機。然後，若如此想要的話，可在隨後 的方法步驟中模塑此阻燃‘聚合物調配物。在某些具體實施 例中，可使用裝置來完全混合此些組分以形成阻燃聚合物 調配物，且亦用此阻燃聚合物調配物來模塑出物件。再者， 此阻燃劑聚合物調配物之模塑物件可在製造之後使用於下 列應用中，諸如拉伸處理、壓花處理、塗布、印刷、電鍍、 穿孔或切割。此模塑物件亦可固定至除了本發明之阻燃劑 ^ 聚合物調配物外的材料上，諸如石膏板、木頭、木心板（block board)、金屬材料或石材。但是，此經捏合的混合物亦可經 充氣模塑、注射模塑、擠壓模塑、吹製模塑、壓製模塑、 轉動模塑或壓延模塑。 在擠壓物件的實例中，可使用任何已熟知對上述描述 的合成樹脂混合物有效之擠壓技術。在一個典型的技術 中，於化合機器中化合合成樹脂、氫氧化鋁顆粒及可選擇 的組分（若選擇的話），以形成如上所述之阻燃劑樹脂調配 物。然後，在擠壓器中將阻燃劑樹脂調配物加熱至熔融狀 -21- 200812912 態，然後讓熔融的阻燃劑樹脂調配物擠壓通過所選擇的模 具以形成擠壓物件或以塗布例如使用來資料傳輸的金屬電 線或玻璃纖維。 上述描述係有關於本發明的數個具體實施例。熟習該 項技術者將了解可設計出其它等效設備來實行本發明之精 神。亦應該注意的是，本發明的較佳具體實施例思量到於 本文所討論之全部範圍包括從任何較低量至任何較高量的 範圍。例如，當討論經乾式硏磨的ATH顆粒之吸油性時， jp 經考量的範圍從約3 0 %至約3 2 %、約1 9 %至約2 5 %、約2 1 % 至約27 %等等皆在本發明之範圍內。 下列實例將闡明本發明，但其不意欲以任何方式來限 制。 實例 描述在下列實例中的η。及Vmax如上所述般使用波羅西 計2000推導自汞孔隙度測量法。除非其它方面有指出，否 則d5。、BET、吸油性等等全部皆根據上述描述的技術來測 • 量。同樣地，如在實例中所使用的名稱「發明之ATH」意 欲指爲根據本發明所製造的ATH，及「比較的ATH」、「競 爭性」及「比較的」意欲指爲可商業購得之ATH及非根據 本發明來製造。 實施例1 將具有固體含量50重量％的ATH濾餅以280升/小時 之速率直接進料至乾式硏磨機。在乾式硏磨之前，於濾餅 中的氫氧化鋁具有BET比表面積3.0平方公尺/克及粒徑中 -22- 200812912 位數2.3 8微米。在下列之條件下、操作硏磨，包括空氣流速 在3 000-3 5 00 Bm3/h之間，溫度400-450°C及轉片速度55公 尺/秒。 在硏磨之後，從熱空氣流經由空氣過濾器系統收集經 硏磨乾燥的氫氧化鋁顆粒。所回收的氫氧化鋁顆粒之產物 性質包含在下列表1中。 比較的氫氧化鋁等級馬丁諾（Martinal)OL-104 LE(由馬 丁斯沃克（Martinswerk)公司製造）之產物性質及競爭性氫氧 I 化鋁等級「競爭性」之產物性質亦顯示在表1中。 表1 孔半徑中位數 (%，，）(微米） 最大孔體積比 V臟(立方毫米痴 粒徑中位數 d5〇(微米） 比BET表面 (平方公尺/克） 比較的ATH OL-104LE 0.419 529 1.83 3.2 競爭性 0.353 504 1.52 3.2 發明的ATH 0.33 466 1.80 3.7 如可在表1中看見，發明的氫氧化鋁等級（根據本發明 所製造之ATH)具有最低孔半徑中位數及最低最大孔體積 比。 實例2 分別使用實例1之比較的氫氧化鋁顆粒馬丁諾OL-104 LE及發明的氫氧化鋁等級來形成阻燃劑樹脂調配物。所使 用的合成樹脂爲來自愛松莫比爾（ExxonMobil)的 EVA Escorene®Ultra UL00328與來自愛松莫比爾之LLDPE等級 LL1001XV —起、可從 Albemarle®股份（有限）公司 -23- 200812912 (Albemarle® Corporation)商業購得的 Ethanox®3 1 0 抗氧化 劑及來自狄估沙（Degussa)的胺基矽烷戴那西蘭 (D y n a s y 1 a n) A Μ E 0之混合物。以2 5公斤/小時之輸入量與所 選擇的溫度設定及螺旋槳速度，使用由熟知此技藝者所熟 知的一般方式，在46毫米布斯高捏合機（L/D比率=11)上混 合此些組分。在配製阻燃劑樹脂調配物時所使用的每種組 分之量詳述在下列表2中。 表 2Vmax (i.e., the maximum pore volume ratio at about 1 bar) ranges from about 300 to about 700 cubic millimeters per gram. In a preferred embodiment of the invention, the Vmax of the ATH product particles produced by the present invention ranges from about 390 to about 480 cubic millimeters per gram, more preferably from about 410 to about 450 cubic millimeters per gram. In other preferred embodiments, Vmax ranges from about 400 to about 600 cubic millimeters per gram, more preferably from about 450 to about 5 50 cubic millimeters per gram. In still other preferred embodiments, Vmax ranges from about 300 φ to about 700 cubic millimeters per gram, more preferably from about 350 to about 5 50 cubic millimeters per gram. The ATH product particles produced by the present invention may also be characterized as having oil absorbing properties (as measured using ISO 787-5: 1 980) ranging from about 1 to about 35%. In certain preferred embodiments, the ATH product particles produced by the present invention are characterized by having oil absorbing properties ranging from about 23 to about 30%, more preferably from about 25% to about 28%. In other preferred embodiments, the ATH product particles produced by the present invention are characterized by having oil absorbing properties ranging from about 25% to about 32%, more preferably from about 26% to about 30%. In its preferred embodiment, further from -16 to 200812912, the ATH product particles produced by the present invention are characterized by oil absorbing properties, ranging from about 25 to about 35 percent, more preferably from about 27 % to about 32%. In other embodiments, the oil absorption of the ATH product particles produced by the present invention ranges from about 19% to about 23%, and in still other embodiments, the oil absorption of the ATH product particles produced by the present invention is The range is from about 21% to about 25%. The ATH product particles produced by the present invention may also be characterized as having a BET specific surface area (as measured by DIN-66 1 32) in the range of from about 1 to 15 square meters per gram. In a preferred embodiment, the ATH product particles produced by the present invention have a BET specific surface area ranging from about 3 to about 6 square meters per gram, more preferably from about 3.5 to about 5.5 square meters per gram. . In other preferred embodiments, the ATH product particles produced by the present invention have a BET specific surface area ranging from about 6 to about 9 square meters per gram, more preferably from about 6.5 to about 8.5 square. Metric / gram. In still other preferred embodiments, the A.TH product particles produced by the present invention have a 3ET specific surface area ranging from about 9 to about 15 square meters per gram, more preferably from about 10.5 to about 12.5. Square meters / gram. The ATH product particles produced by the present invention may also be characterized as having dw ranging from about 〇·5 to 2.5 microns. In a preferred embodiment, the ATH product particles produced by the present invention have a d5 〇 in the range of from about 1.5 to about 2.5 microns, more preferably in the range of from about 1.8 to about 2<2> In other preferred embodiments, the ATH product particles produced by the present invention have a d5 ◦ in the range of from about 1.3 to about 2.0 microns, more preferably in the range of from about 1.4 to about 1.8 microns. In still other preferred embodiments, the ATH product particles produced by the present invention have d5. 5微米。 In the range of from about 0.9 to about 1.8 microns, more preferably from 2008 to 1212. It should be noted that all particle diameter metrics disclosed herein are measured using laser diffraction using a Cilas 1 0 64L laser spectrometer from Quantachrome (ie, d5 〇. Generally speaking, in this paper The procedure used to measure d5 可 can be carried out by first introducing a suitable aqueous dispersion solution (see the formulation below) into the sample preparation vessel of the apparatus. Then select a standard measurement called Particle Expert. Also select the measurement model "Range 1" and then select the internal symmetry of the φ device applied to the expected particle size distribution. It should be noted that during the measurement, the sample is typically exposed to the ultrasonic wave during the dispersion and during the measurement. After the background measurement has been taken, place about 75 to about 100 mg of the sample to be analyzed in a sample container containing the water/dispersant solution and start measuring. This water/dispersant solution can be obtained from 500 first. Prepare a concentrate by preparing a concentrate from Calgon (available from KMF chemie) and 3 liters of CAL Poly salt (available from BASF) This solution was made up to 10 liters of deionized water. 100 ml of this original 10 liters was taken and further diluted to 10 liters with deionized water in that order, and this final solution was used as the aqueous dispersant solution described above. Granules as Flame Retardants ATH product particles produced in accordance with the present invention can be used as flame retardants in a variety of synthetic resins. Non-limiting examples of thermoplastic resins using dry honed niobium particles have been found to include polyethylene, ethylene. - a copolymer of propylene copolymer, C2 to C8 olefin (α-olefin) and a copolymer (such as polybutene, poly(4-methylpentene-1) or the like), copolymerization of these olefins and dienes , ethylene-acrylate copolymer, polystyrene, ABS resin, AAS tree-18- 200812912 grease, AS resin, MBS resin, ethylene-vinyl chloride copolymer resin, ethylene_vinyl acetate copolymer resin, ethylene-chlorine Ethylene-vinyl acetate graft polymer resin, vinylidene chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-propylene copolymer, vinyl acetate resin, phenoxy resin and the like. Further examples of suitable synthetic resins include thermosetting resins such as epoxy resins, phenol resins, melamine resins, unsaturated polyester resins, alkyd resins and urea resins; and also natural or synthetic rubbers such as EPDM, butyl rubber. , isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, silicone rubber, fluoroelastomer, NBR and chlorosulfonated polyethylene. Further included in the polymerization Suspension (latex). Preferably, the synthetic resin is a polyethylene based resin such as high density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, EVA ( Ethylene-vinyl acetate resin), EEA (ethylene-ethyl acrylate resin), EMA (ethylene-methyl acrylate copolymer resin), EAA (ethylene-acrylic copolymer resin) and ultrahigh molecular weight polyethylene; and C2 to C8 Polymers and copolymers of olefins (α-olefins) such as polybutene and poly(4-methylpentene-1), polyvinyl chloride and rubber. In a more preferred embodiment, the synthetic resin is a polyethylene based resin. The present inventors have found that a synthetic resin containing aluminum hydroxide can achieve better synthesis performance by using the cerium product particles according to the present invention as a flame retardant in a synthetic resin. The preferred compounding properties are highly desirable by such combiners, manufactures, etc., in order to produce highly flame-retardant compounds and finally extruded or molded articles from synthetic resins containing cerium product particles. Highly ambiguous means those containing fluorinated amounts of hydrazine product particles as discussed below. The preferred compounding property means the degree of energy in a synthetic machine (such as a Boothoff kneader or twin propeller extruder) required for mixing a synthetic resin comprising ATH product particles manufactured in accordance with the present invention from -19 to 200812912. The variation amplitude is smaller than those of the synthetic resin which mixes the synthetic resin containing the conventional ruthenium particles. A small change in the degree of energy allows the synthetic resin containing the cerium product particles to be mixed or extruded to have a higher input and/or more uniform (homogeneous) material. Accordingly, in one embodiment, the present invention is directed to a flame retardant polymer formulation comprising at least one synthetic resin selected from the ones described above (in only some embodiments) and flame retardant The amount of the ruthenium product particles produced according to the invention according to φ; and the extruded and/or molded article obtained from the flame retardant polymer formulation. The flame retardant amount of the cerium product particles generally means ranging from about 5% by weight to about 90% by weight (based on the weight of the flame retardant polymer formulation) and more preferably from about 20% by weight to about 70% by weight. % (whichever is the same). In the most preferred embodiment, the amount of flame retardant is from about 30% by weight to about 65% by weight of the ruthenium product particles, whichever is the same. The flame retardant polymer formulation may also contain other additives commonly used in the art. Non-limiting examples of other additives suitable for use in the flame retardant polymer formulations of the present invention include extrusion aids such as polyethylene waxes, Si-based extrusion aids, fatty acids; coupling agents, Such as amine-, ethionyl- or agglomerate than alkane or maleic acid graft polymer; sodium stearate or calcium stearate; organic peroxide; dye; pigment; sputum; Deodorant; heat stabilizer; antioxidant; antistatic agent; reinforcing agent; metal scavenger or deactivator; impact modifier; processing aid; mold release aid, lubricant; anti-blocking agent; UV stabilizer; plasticizer; flow aid; and the like. If necessary, a nucleating agent such as calcium citrate or indigo may also be included in the flame retardant polymer formulation -20-200812912. The ratio of other optional additives is well known and can be varied to suit any of the conditions provided. The method of incorporating and incorporating the components of the flame retardant polymer formulation is not critical to the invention and can be any Methods well known in the art, as long as the method selected includes substantially uniform mixing. For example, each of the above components and optional additives (if used) can be mixed using the following machines: Buss high kneader, internal mixer, Farrel continuous mixing φ or twin propeller extruder Or, in some instances, a single propeller extruder or two roller mills. This flame retardant 'polymer formulation can then be molded in a subsequent method step if so desired. In some embodiments, the device can be used to thoroughly mix the components to form a flame retardant polymer formulation, and the flame retardant polymer formulation is also used to mold the article. Further, the molded article of the flame retardant polymer formulation can be used in the following applications after manufacture, such as stretching treatment, embossing treatment, coating, printing, plating, perforating or cutting. The molded article may also be fixed to a material other than the flame retardant polymer composition of the present invention, such as gypsum board, wood, block board, metal material or stone. However, the kneaded mixture may also be subjected to inflation molding, injection molding, extrusion molding, blow molding, compression molding, rotational molding or calender molding. In the case of the extruded article, any extrusion technique which is well known to be effective for the synthetic resin mixture described above can be used. In a typical technique, synthetic resin, aluminum hydroxide particles, and optional components, if selected, are combined in a compounding machine to form a flame retardant resin formulation as described above. Then, the flame retardant resin formulation is heated to a molten state in the extruder - 21-12912912, and then the molten flame retardant resin formulation is extruded through the selected mold to form an extruded article or to coat, for example Use metal wires or fiberglass for data transmission. The above description is directed to several specific embodiments of the invention. Those skilled in the art will appreciate that other equivalent devices can be devised to practice the spirit of the present invention. It should also be noted that the preferred embodiments of the present invention contemplate that the full range discussed herein includes any range from any lower amount to any higher amount. For example, when discussing the oil absorption of dry-honed ATH particles, jp is considered to range from about 30% to about 32%, from about 19% to about 25%, from about 21% to about 27%. And the like are within the scope of the invention. The following examples are illustrative of the invention, but are not intended to be limiting in any way. Examples Describe η in the following examples. And Vmax was derived from the mercury porosimetry using the Brooklyn 2000 as described above. Unless otherwise stated, otherwise d5. , BET, oil absorption, etc. are all measured according to the techniques described above. Similarly, the term "the invention of ATH" as used in the examples is intended to mean that ATH manufactured in accordance with the present invention, and "compared ATH", "competitive" and "comparative" are intended to be commercially available. ATH and not manufactured in accordance with the present invention. Example 1 An ATH filter cake having a solid content of 50% by weight was directly fed to a dry honing machine at a rate of 280 liters/hour. Prior to dry honing, the aluminum hydroxide in the filter cake has a BET specific surface area of 3.0 square meters per gram and a particle size of -22-200812912 digits of 2.38 microns. The honing was carried out under the following conditions, including an air flow rate of 3 000-3 5 00 Bm 3 /h, a temperature of 400-450 ° C and a rotor speed of 55 ft / sec. After honing, the honed and dried aluminum hydroxide particles are collected from the hot air stream via an air filter system. The product properties of the recovered aluminum hydroxide particles are contained in Table 1 below. The product properties of the comparative aluminum hydroxide grade Martinal OL-104 LE (manufactured by Martinswerk) and the competitive properties of the competitive aluminum hydroxide grade "competitive" are also shown in Table 1. in. Table 1 Median hole radius (%,,) (micron) Maximum pore volume ratio V dirty (cubic mm median diameter d5 〇 (micron) BET OL compared to BET surface (m ^ 2 / gram) 104LE 0.419 529 1.83 3.2 Competitiveness 0.353 504 1.52 3.2 Inventive ATH 0.33 466 1.80 3.7 As can be seen in Table 1, the inventive aluminum hydroxide grade (ATH manufactured according to the invention) has the lowest median and lowest hole radius Maximum pore volume ratio. Example 2 A flame retardant resin formulation was formed using the aluminum hydroxide particles Martino OL-104 LE of Comparative Example 1 and the inventive aluminum hydroxide grade, respectively. The synthetic resin used was from Aissonmo. ExxonMobil's EVA Escorene® Ultra UL00328 and Ethanox® 3 1 0 commercially available from Albemarle® -23- 200812912 (Albemarle® Corporation) from Esson Mobile's LLDPE grade LL1001XV. Antioxidant and a mixture of amino decane, D ynasy 1 an, A Μ E 0 from Degussa, with an input of 25 kg/hr and selected temperature setting and propeller speed These components are mixed on a 46 mm Booth high kneader (L/D ratio = 11) using a general manner well known to those skilled in the art. Each of the materials used in formulating the flame retardant resin formulation The amounts of the components are detailed in Table 2 below.
Phr(每百份總樹脂的份數） Escorene Ultra UL00328 80 LL1001XV 20 氫氧化鋁 150 AME0矽烷 1.6 愛森諾斯3 1 0 0.6 在形成阻燃劑樹脂調配物時，在布斯化合之前首先於 鼓中混合ΑΜΕ0矽烷及Ethanox®310與合成樹脂的總量。 依在重力進料器中的損失，將樹脂/矽烷/抗氧化劑混合物與 總量 50%的氫氧化鋁一起進料至布斯捏合機的第一輸入 口，且將剩餘的50%氫氧化鋁進料至布斯捏合機的第二進 料璋中。將排出擠壓器垂直安裝在布斯局捏合機邊緣且具 有螺旋槳尺寸7 0毫米。第4圖顯示出排出擠壓器之馬達對 等級編號1之發明的氫氧化鋁之功率圖形。第5圖顯示出 排出擠壓器之馬達對由馬丁斯沃克公司所製造之比較的氫 氧化鋁等級OL-104 LE之功率圖形。 如在第4及5圖中所闡明，當將根據本發明之氫氧化 -24- 200812912 鋁顆粒使用在阻燃劑樹脂調配物時，排出擠壓器的能量（功 率）圖形變化明顯減低。如上述所描述，較小的能量程度變 化允許較高的輸入量及/或更均勻（均質）的阻燃劑樹脂調配 物。 【圖式簡單說明】 第1圖顯示出在第二侵入測試操作中根據本發明的 ATH(「發明」）之孔體積比V如爲所施加的壓力之函數，且 與標準等級比較。 φ 第2圖顯示出在第二侵入測試操作中根據本發明的 ATH(「發明」）其對孔半徑r繪製之孔體積比v，且與標準 等級比較。 第3圖顯示出根據本發明的ATH(「發明」）之經標準 化的孔體積比且與標準等級比較，此曲線圖藉由將每個 ATH等級之最大孔體積比設定爲1〇〇%，及將相符合的ath 等級之其它比體積除以此最大値而產生。 第4圖顯示出排出擠壓器的馬達對在實施例1中所使 0 用之發明的氫氧化鋁等級之功率圖形。 第5圖顯示出排出擠壓器的馬達對在實施例1中所使 用之比較的氫氧化鋁等級0 L -1 0 4 L E之功率圖形。 【主要元件符號說明】 無0Phr (parts per hundred parts of total resin) Escorene Ultra UL00328 80 LL1001XV 20 Aluminium hydroxide 150 AME0 decane 1.6 Essennos 3 1 0 0.6 When forming a flame retardant resin formulation, first on the drum before the Booth combination Mix the total amount of decane and Ethanox® 310 with synthetic resin. Depending on the loss in the gravity feeder, the resin/decane/antioxidant mixture is fed to the first input of the Buss kneader together with a total of 50% aluminum hydroxide, and the remaining 50% aluminum hydroxide Feed to the second feed port of the Booth kneader. The discharge extruder was mounted vertically on the edge of the Booth kneader and had a propeller size of 70 mm. Fig. 4 is a graph showing the power of the aluminum hydroxide of the invention of the class No. 1 which discharges the extruder. Figure 5 shows the power pattern of the motor of the discharge extruder versus the comparative alumina grade OL-104 LE manufactured by Martins Walker. As illustrated in Figures 4 and 5, when the aluminum hydroxide -24-200812912 aluminum particles according to the present invention are used in a flame retardant resin formulation, the energy (power) pattern change of the discharge extruder is remarkably reduced. As described above, a smaller change in energy level allows for a higher input and/or more uniform (homogeneous) flame retardant resin formulation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the pore volume ratio V of the ATH ("Invention") according to the present invention as a function of the applied pressure in the second intrusion test operation, and is compared with the standard grade. φ Figure 2 shows the pore volume ratio v plotted against the hole radius r of the ATH ("Invention") according to the present invention in the second intrusion test operation, and compared with the standard grade. Figure 3 shows the normalized pore volume ratio of ATH ("Invention") according to the present invention and compared to a standard grade by setting the maximum pore volume ratio of each ATH grade to 1%, And the other specific volume of the matching ath grade is divided by the maximum enthalpy. Fig. 4 is a graph showing the power pattern of the aluminum hydroxide grade of the invention for the discharge of the extruder to the invention used in the first embodiment. Figure 5 shows the power pattern of the motor of the discharge extruder for the comparative aluminum hydroxide grade 0 L -1 0 4 L E used in Example 1. [Main component symbol description] No 0