200815290 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種礦物阻燃劑之製造。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，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。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、熱塑性模塑物、牆板、地板材料 等。ATH典型使用來改良此等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】 本發明係關於一種用來製造ATH顆粒的方法，其包括： 硏磨乾燥漿體以製造出經硏磨乾燥的ATH顆粒；及選 擇性 去黏聚該經硏磨乾燥的ATH顆粒以製造出ATH產物顆 粒； 其中該漿體包含範圍從約1至約85重量％(以漿體的總 重量爲準）具有d5。在範圍從約1.5至3.5微米之ATH顆粒， 200815290 其中該ATH產物顆粒具有孔半徑中位數（“ r5()” ）在範圍從 約0.09至約〇·33微米。 在另一個具體實施例中，本發明係關於一種用來製造 ΑΤΗ顆粒的方法，其包括： 硏磨乾燥漿體以製造出經硏磨乾燥的ΑΤΗ顆粒；及選 擇性 去黏聚該經硏磨乾燥的ΑΤΗ顆粒以製造出ΑΤΗ產物顆 粒； 其中該漿體包含範圍從約1至約3 5重量％ (以漿體的總 重量爲準）具有d5。在範圍從約1.5至約3.5微米之ΑΤΗ顆 粒’其中該ATH產物顆粒顆粒具有r5。在範圍從約〇.〇9至 約0.3 3微米。 在另一個具體實施例中，本發明係關於一種用來製造 ATH顆粒的方法，其包括： 硏磨乾燥漿體以製造出經硏磨乾燥的ATH顆粒；及選 擇性 去黏聚該經硏磨乾燥的ATH顆粒以製造出ATH產物顆 企丄 · 松， 其中該漿體包含範圍從約1至約85重量％(以漿體的總 重量爲準）具有d5。在範圍從約1.5至3.5微米之A TH顆粒， 其中此ATH產物顆粒的特徵爲具有： 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 200815290 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，本發明者咸信（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顆粒之形態而 定，且關於此點，本發明者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，本發明者咸信（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顆粒的形態改良。 再次，關於此點，本發明者咸信（然而不意欲由理論所 限制）此經改良的形態可歸因於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，本發明者咸信 對所提供的聚合物分子來說，具有較高結構化的黏聚物之 ATH產物包含更多及較大的孔且似乎更難以溼潤，而導致 胃 在捏合機（如Buss Κο-捏合機或雙螺旋擠壓器或已在技藝 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，本發明者已發現 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 化合行爲改良（即，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’本發明者已發現本發明之方法特別良好適合於製造出 -7- 200815290 具有這些特徵的ATH。 漿體 在本發明的一個具體實施例中，硏磨乾燥包含ΑΤΉ顆 粒之漿體以製造出經硏磨乾燥的ΑΤΗ顆粒。此漿體典型包 含範圍從約1至約85重量％的ΑΤΗ顆粒，更典型在範圍從 約25至約85重量％，全部以漿體之總重量爲準。在較佳的 具體實施例中，此漿體包含範圍從約40至約70重量％的 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。 在其它較佳的具體實施例中，此漿體包含範圍從約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。在仍然其它較佳 的具體實施例中，此漿體包含範圍從約25至約50重量％ 之ΑΤΗ顆粒，更佳的範圍從約30至約45重量％之ΑΤΗ顆 粒，二者以相同基礎爲準。 、 在本發明之實行中，所使用的漿體可從任何使用來產 ® 生ΑΤΗ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ΑΤΗ顆粒之方法獲得漿體。在典型的具體實施 例中，從下列方法獲得漿體，其包括將氫氧化鋁粗產物溶 解在苛性鹼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 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1.55 : 1。爲了從鋁酸鈉液體中沉澱出 ΑΤΗ顆粒，將ΑΤΗ籽粒顆粒加入至鋁酸鈉液體，其量範圍 200815290 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ΑΤΗ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ΑΤΗ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小時或此外直到Na2〇至Al2〇3的莫耳濃度比率 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 Φ 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。可在再漿體化之前，以水（較佳爲 去鹽水）清洗濾餅一次或在某些具體實施例中多於一次。在 硏磨乾燥之前，可以水再漿體化此濾餅以形成漿體，或在 較佳的具體實施例中，將至少一種（較佳僅有一種）分散劑 加入至濾餅以形成漿體。應注意的是，以水與分散劑之組 合來再漿體化濾餅亦在本發明的範圍內。合適於使用在本 文的分散劑之非爲限制的實例包括聚丙烯酸鹽、有機酸、 ® 萘磺酸鹽/甲醛濃縮物、脂肪-醇-聚乙二醇-醚、聚丙烯-環 氧乙烷、聚乙二醇·酯、聚胺-環氧乙烷、磷酸鹽、聚乙烯 醇。在此具體實施例中，此漿體的剩餘物（即，不包含ATH 顆粒及分散劑）典型爲水，然而可從沉澱物中顯現出某些試 劑、污染物等等。 在某些具體實施例中，於漿體中之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 佳的具體實施例中，於漿體中之ATH顆粒具有BET在範圍 200815290 從約1.5至約2.5平方公尺/克。 在漿體中的ATH顆粒之特徵典型進一步可爲具有d5。 在範圍從約1.8至約3.5微米。在較佳的具體實施例中，在 漿體中的ΑΤΉ顆粒具有ch。在範圍從約1.8至約2.5微米， 其比由本發明所製造的ATH產物顆粒粗糙。 在其它具體實施例中，於漿體中之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，於漿體中之ATH顆粒具有BET在範圍從約 • 5至約7平方公尺/克。在漿體中的ATH顆粒之進一步特徵 可爲具有d5。在範圍從約1.5至約2.5微米。在較佳的具體 實施例中，於漿體中之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，於漿體中的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，於漿體中之ATH顆粒具有BET在範圍 從約9至約12平方公尺/克。在漿體中的ath顆粒之進一 ® 步特徵可爲具有d5。在範圍從約1.5至約2.0微米。在較佳 的具體實施例中，於漿體中之ATH顆粒具有d5〇在範圍從 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ATH產物顆粒粗糙意謂著在漿體中的ATH顆粒之 d5。値的上限通常比由本發明所製造之經乾式硏磨的ATH 顆粒之dw的上限大至少約ο.〗微米。 關於此點’本發明者咸信（然而不意欲由理論所限制） -10- 200815290 由本發明所製造的ATH產物顆粒之改良的形態至少部分可 歸因於使用來沉澱ΑΤΗ的方法。因此，雖然硏磨乾燥技術 已在技藝中熟知，關於此點，本發明者已發現藉由使用描 述於本文之沉澱及過濾方法（包括較佳具體實施例）與描述 於本文的硏磨乾燥方法一起，可容易地製造出具有改良的 形態之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漿體以產生經硏 # 磨乾燥的ΑΤΗ顆粒，且讓其選擇性接受去黏聚。如於本文 中所使用之「硏磨乾燥」（mill-drying)及「經硏磨乾燥」 (mill-dried)意謂著漿體在硏磨乾燥單元中以紊流的熱空氣 流乾燥。此硏磨乾燥單元包括結實安裝在以高圓周速.度轉 動的實體傳動軸上之轉片。旋轉移動與高空氣輸入聯結會 將流過的熱空氣轉換成極快速的空氣渦流，其會帶起欲乾 燥的漿體、加速其且分佈及乾燥此漿體。在已完全乾燥之 後，ATH顆粒經由紊流空氣傳輸出磨粉機及藉由使用習知 ® 的過濾器系統來分離·熱空氣與蒸氣。在本發明的另一個具 體實施例中，在已完全乾燥之後，ATH顆粒經由紊流空氣 傳輸通過空氣分類器（其已整合至磨粉機中），然後經由紊 • 流空氣傳輸出磨粉機及藉由使用習知的過濾器系統來分離 熱空氣與蒸氣。 使用來乾燥漿體的熱空氣之輸入量典型大於約3,000 Bm3/h，較佳大於約至約5,000 Bm3/h，更佳從約3,000 Bm3/h 至約 40,0(ί〇 Bm3/h 及最佳從約 5,000 Bm3/h 至約 30,000 •11- 200815290200815290 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the manufacture of a mineral 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 pellets have been found to be used as fillers in many materials such as, for example, plastics, rubber, thermosets, ® 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 moldings, wallboard, flooring materials, and the like. ATH 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, the need for a modified/modified ATH rating has increased and the current method has failed to produce all of these ratings. 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 for making ATH particles comprising: honing a dried slurry to produce honed and dried ATH particles; and selectively deagglomerating the honed and dried ATH The granules are used to produce ATH product particles; wherein the slurry comprises from about 1 to about 85% by weight, based on the total weight of the slurry, having d5. ATH particles ranging from about 1.5 to 3.5 microns, 200815290 wherein the ATH product particles have a median pore radius ("r5()") ranging from about 0.09 to about 〇33 microns. In another embodiment, the present invention is directed to a method for making cerium particles comprising: honing a dried slurry to produce honed dry cerium particles; and selectively deagglomerating the honing The dried cerium particles are used to produce cerium product particles; wherein the slurry comprises from about 1 to about 35 weight percent (based on the total weight of the slurry) having d5. The particles of the ATH product particles have r5 in the range of from about 1.5 to about 3.5 microns. The range is from about 〇.〇9 to about 0.33 microns. In another embodiment, the present invention is directed to a method for making ATH particles, comprising: honing a dried slurry to produce honed and dried ATH particles; and selectively deagglomerating the honed The dried ATH particles are used to produce an ATH product, wherein the slurry comprises from about 1 to about 85% by weight, based on the total weight of the slurry, having d5. A TH particles in the range 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. / gram; or b) BET specific surface area from about 6 to about 9 square meters / gram; and Vmax from 200815290 about 400 to about 600 cubic millimeters / gram; or c) BET specific surface area from about 9 to about 15 square meters / gram; and Vmax from about 300 to about 700 cubic millimeters / gram. [Embodiment] In this regard, the inventors of the present invention (but not intending to be bound by theory) have the wetting ability of the ATH particles wetted by the resin depending on the form of the ATH particles, and the inventors have unexpectedly concerned about this point. It has been found that ATH particles having improved wetting ability (relative to the ATH particles currently available) can be produced by using the method of the present invention. In this regard, the inventors of the present invention (but 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 inventors of the present invention (but not intended to be bound by theory) 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 a higher structured cohesive polymer contains more and larger pores and appears to be more difficult to wet, resulting in gastric kneading. Machines (such as Buss Κο-kneader or twin screw extruders or other machines that are well known in the art and used for this purpose) are difficult during compounding (higher motor power pattern changes). Thus, in this regard, the inventors have discovered that the mediators characterized by a smaller pore size and/or a lower total pore volume are associated with improved ability to wet the polymeric material, thereby causing a combination Behavioral improvement (i.e., the engine (motor) used to compound a flame retardant resin containing an enamel-filling 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 ATH having these characteristics from -7 to 200815290. Slurry In one embodiment of the invention, the slurry comprising the cerium particles is honed to produce honed and dried cerium particles. The slurry typically comprises from about 1 to about 85% by weight of cerium particles, more typically in the range of from about 25 to about 85% by weight, all based on the total weight of the slurry. In a preferred embodiment, the slurry 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 preferred embodiments, the slurry 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 preferred embodiments, the slurry comprises cerium particles ranging from about 25 to about 50 weight percent, more preferably from about 30 to about 45 weight percent cerium particles, both on the same basis. quasi. In the practice of the present invention, the slurry used can be obtained from any method of producing the granules. Preferably, the slurry is obtained from a process comprising the production of ruthenium particles by precipitation and filtration. In a typical embodiment, a slurry is obtained from a process comprising dissolving a crude aluminum hydroxide in caustic to form a sodium aluminate liquid, cooling and filtering thereby forming in this exemplary embodiment. Useful sodium aluminate liquid. The sodium aluminate liquid thus produced typically has a molar concentration ratio of Na2? to Al??3 ranging from about 1.4:1 to about 1.55:1. In order to precipitate the cerium particles from the sodium aluminate liquid, the cerium grain particles are added to the sodium aluminate liquid in an amount ranging from 2008 to 15290 from about 1 gram of ATH grain particles per liter of sodium aluminate liquid to about 3 grams per liter of sodium aluminate liquid. The kernel particles are mashed to form a method mixture. The barium 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 further until the molar concentration ratio of Na2〇 to Al2〇3 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 is variable and falls within the range of Φ described above. The obtained ATH suspension is then filtered and washed to remove impurities therefrom to form a filter cake. The filter cake may be washed once with water (preferably desalinated water) or more than once in some embodiments prior to repulping. The filter cake may be reslurryed with water to form a slurry prior to honing and drying, or in a preferred embodiment, at least one, preferably only one, dispersant is added to the filter cake to form a slurry. . It should be noted that it is also within the scope of the invention to re-slurry the filter cake with a combination of water and dispersant. Non-limiting examples of suitable dispersing agents for use herein include polyacrylates, organic acids, ® naphthalene sulfonate/formaldehyde concentrates, fat-alcohol-polyethylene glycol-ethers, polypropylene-ethylene oxides. , polyethylene glycol ester, polyamine-ethylene oxide, phosphate, polyvinyl alcohol. In this particular embodiment, the remainder of the slurry (i.e., containing no ATH particles and dispersant) is typically water, although certain agents, contaminants, and the like may be apparent from the precipitate. In some embodiments, the ATH particles in the slurry 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, the ATH particles in the slurry have a BET in the range of from about 1.5 to about 2.5 square meters per gram in the range of 200815290. The characteristics of the ATH particles in the slurry are typically further characterized by having d5. In the range from about 1.8 to about 3.5 microns. In a preferred embodiment, the ruthenium particles in the slurry have ch. It ranges from about 1.8 to about 2.5 microns which is coarser than the ATH product particles made by the present invention. In other embodiments, the ATH particles in the slurry 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 slurry have a BET ranging from about 5. 5 to about 7 square meters per gram. A further feature of the ATH particles in the slurry can be d5. In the range from about 1.5 to about 2.5 microns. In a preferred embodiment, the ATH particles in the slurry 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 slurry are characterized by having a BET ranging from about 8.0 to about 14 square meters per gram. In a preferred embodiment, the ATH particles in the slurry have a BET in the range of from about 9 to about 12 square meters per gram. The further step feature of the ath particles in the slurry can have a d5. In the range from about 1.5 to about 2.0 microns. In a preferred embodiment, the ATH particles in the slurry have a d5 〇 ranging from about 1.25 to about 1.8 microns which is coarser than the ATH product particles produced by the present invention. Rougher than the ATH product particles means d5 of the ATH particles in the slurry. The upper limit of 値 is generally at least about ο. μm greater than the upper limit of dw of the dry honed ATH particles produced by the present invention. In this regard, the inventors' letter (but not intended to be limited by theory) -10- 200815290 The improved morphology of the ATH product particles produced by the present invention is at least in part attributable to the method of precipitating strontium. Thus, while honing and drying techniques are well known in the art, in this regard, the inventors have discovered that by using the precipitation and filtration methods described herein (including preferred embodiments) and the honing drying methods described herein, Together, the ruthenium product particles having an improved morphology can be readily produced, as described below. Honing Drying As discussed above, the present invention involves honing a dried slurry to produce a mash-dried cerium particle that is selectively subjected to de-agglomeration. As used herein, "mill-drying" and "mill-dried" means that the slurry is dried in a honing drying unit by a turbulent flow of hot air. The honing drying unit includes a rotor that is sturdyly mounted on a solid drive shaft that rotates at a high peripheral speed. Rotating movement in conjunction with high air input converts the flowing hot air into a very fast air vortex that brings up the slurry to be dried, accelerates it, and distributes and dries the slurry. After it has completely dried, the ATH particles are transported out of the mill via turbulent air and separated by hot air and steam using a conventional filter system. In another embodiment of the invention, after it has been completely dried, the ATH particles are transported via turbulent air through an air classifier (which has been integrated into the mill) and then transported through the turbulent air to the mill. And separating hot air and steam by using a conventional filter system. The input of hot air used to dry the slurry is typically greater than about 3,000 Bm3/h, preferably greater than about 5,000 Bm3/h, more preferably from about 3,000 Bm3/h to about 40,0 (ί Bm3/h and Best from about 5,000 Bm3/h to about 30,000 •11- 200815290
Bm3/h。 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 雷諾（Reynolds)數大於約3,000。 使用來硏磨乾燥漿體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150°C至約5 5 0°C，最佳的範圍從約270°C 至約500°C。 漿體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，然後在漿體 中之起始ATH顆粒。典型來說，經硏磨乾燥的ATH之BET 比在漿體中的ATH顆粒大多於約10%。ATH產物顆粒之BET 比在漿體中的ATH顆粒大在範圍從約10%至約40%較佳。 ATH產物顆粒之BET.比在漿體中的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ATH產物顆粒可「直接」 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ATH顆粒在樹脂中之性能。因此， ATH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ATH顆粒中 -12- 200815290 之黏聚物數目或黏聚程度可藉由讓此經硏磨乾燥的ATH顆 粒接受進一步去黏聚加工步驟來減低。 去黏聚 去黏聚意謂著讓經硏磨乾燥的ΑΤΗ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產物顆粒中的黏聚物數目），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d5〇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ΑΤΉ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d5〇範圍從經硏磨乾 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產物顆粒者。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 -13- .200815290 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 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。 故电形態的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 9 80測量） • 範圍從約1至約35% ; BET比表面積（如利用DIN-66 1 32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。 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（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，本發明者咸信（然而不意欲由理論所 限制）此改良的形態可歸因於於此所製造之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 ® 發明者咸信對所提供的聚合物分子來說，具有較高結構化 的凝聚物之ΑΤΉ包含更多及較大孔且似乎更難以溼潤，而 導致在捏合機（如Buss Κο-捏合機或雙螺旋擠壓器或已在 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，本發明者已發 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ΑΤΗ產物顆粒（當與現在可獲得的ΑΤΗ 比較時），此與改良由聚合材料潤溼（當與現在可獲得的ΑΤΗ -14- 200815290 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ΑΤΗ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。 由本發明所製造的ΑΤΗ產物顆粒在約1 000巴下之^。 及孔體積比（“ VmaV’）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明所製造 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 伯設備（Carlo Erb a Strumentazione)之波羅西計 (PorosimeterUOOO,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0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 粒之孔尺寸。使用第二測試操作，因爲本發明者觀察到具 有體積V。的汞量會在擠壓出之後（即，在壓力釋放至周壓 之後）餘留在ATH顆粒的樣品中。因此，η。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 -15- •200815290 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ρ(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圍 壓力。使用來自第一測試操作的相同ΑΤΗ樣品（無雜質）進 行第二侵入測試操作（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。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) Φ 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ATH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侵入測試測中，根據 式n2rcos(0)/p來計算出孔半徑r，其中0爲潤溼角度， r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Θ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 製之經標準化的操作孔體積比，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1〇〇%且將特別 的ATH之其它體積比除以此最大値。在5 0 %相對孔體積比 -16- •200815290 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 (即，發明1)之孔半徑中位數 Γ5。爲0.33微米。 使用根據本發明所製造的ATH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ATH產物顆 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ΑΤΗ產物顆粒之在範圍從約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，r5〇在範圍從約0.185至約0.325微米，更 佳的範圍從約0.185至約0.25微米。在仍然其它較佳的具 體實施例中，η。在範圍從約0.09至約0.21微米，更佳的 範圍從約0.0 9至約0.1 6 5微米。 由本發明所製造的 ΑΤΗ產物顆粒其特徵亦可爲具有 Vmax(即，在約1000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3 90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550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 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 -17- •200815290 油性（如利用ISO 7 87-5: 1 9 80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2 3至約3 0 %，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 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-661 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ΑΤΗ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ATH產物顆粒具有BET 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 -18- 200815290 d5。在範圍從約0.5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A ΤΗ產物顆粒具有 cho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ΑΤΗ產物顆粒具有d5〇在範圍從約0.9至約1.8微米，更 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 064L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。）。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 裝置內部參數。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60秒。在已進行背景 測量之後，將.欲分析之約75至約100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5 00克卡爾岡（Calgon)(可從KMF雷伯化學 (1^13 0：^1^11^6)購得）與3升〇八乙？0；^5 311(可從貝斯拂（3八3?) 購得）製備濃縮物來製備。此溶液以去離子水構成至1 〇升。 採取此原始1 0升的1 00毫升且依次以去離子水進一步稀釋 至1 0升，及將此最後溶液使用作爲上述描述的水分散劑溶 -19- 200815290 液。 使用ATH產物顆粒作爲阻燃劑 根據本發明所製造的ΑΤΗ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ΑΤΗ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 • 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 m W 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、EV.A(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- -20- 200815290 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。 本發明者已發現藉由在合成樹脂中使用根據本發明的 ATH產物顆粒作爲阻燃劑，含氫氧化鋁之合成樹脂可達成 較好的化合性能。藉由化合器、製造等較好的化合性能被 高度期望，以便用含ATH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ATH產物顆粒，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 的A Τ Η產物顆粒之合成樹脂所需要的化合機器（如b u s s Ko-捏合機或雙螺旋擠壓器）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2 0重量％至約7 0重量％ (以相同基礎爲準）。在最佳 的具體實施例中，阻燃量從約3 0重量％至約6 5重量％的 ΑΤΗ產物顆粒（以相同基礎爲準）。 -21- 200815290 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-、乙烯基-或烷基矽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；發泡劑； 除味劑；熱安定劑；抗氧化劑；抗靜電劑；強化劑；金屬 清除劑或鈍化劑；衝擊改質劑；加工助劑；脫模助劑，潤 Φ 滑劑；抗阻塞劑；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求。 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 W 合：Buss Ko-捏合機、內部混合器、法拉爾（Farrel)連續混 合器或雙螺旋擠壓器，或在某些實例亦可爲單螺旋擠壓器 或二個輥筒磨粉機。然後，若如此想要的話，可在隨後的 製程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等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，諸如拉伸加工、壓花加工、塗布、印刷、電鍍、 -22- 200815290 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、阻隔板、 金屬材料或石材。但是，此經捏合的混合物亦可經充氣膨 脹模塑、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 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， 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。 【實施方式】 下列實例將闡明本發明，但其不意欲以任何方式來限 制。 -23- 200815290 實例 、 描述在下列實例中的η。及V…如上所述般使用波羅西 計2000推導自汞孔隙度測量法。除非其它方面有所指出， 否則d5〇、BET、吸油性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。 ⑩實施例1 爲了形成漿體，將合適的分散劑安替普雷斯（Antiprex)® A40(可從西巴（Ciba)®商業購得）量加入至ATH濾餅（其具有 固體含量55重量％)，從而形成具有黏度約150厘泊的漿體。 以28 0升/小時之速率將漿體進料至乾式硏磨機。在乾式硏 磨之前，於濾餅中的氫氧化鋁具有BET比表面積3.7平方公 尺/克及粒徑中位數2.0微米。此硏磨在包括空氣流速於範圍 從3 000-3 5 00 Bm3/h、溫度於範圍從400-450°C及轉片速度55 ®公尺/秒之條件下操作。 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)〇L-104 LE(由馬丁 斯沃克（Martinswerk)GmbH 製 造）之產物性質及競爭性氫氧化鋁等級“競爭性”之產物 性質亦顯示在表1中。 -24- 200815290 表1 孔半徑中位數 最大孔體積比Vmax 粒徑中位數ds。 比BET表面 (“放”） (微米） (立方毫米傲 (微米） (平方公尺度） 比較的ΑΊΉ OL-104 LE 0.419 529 1.83 3.2 競爭性 0.353 504 1.52 3.2 本發明的ATH 0.325 440 1.90 4.0 如可在表1中看見，本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及本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愛 斯扣林（Escorene)®UlUa UL00328與來自愛松莫比爾之 LLDPE等級LL 1001 XV —起、可從Albemarle®股份（有限）公 司商業購得的愛森諾斯（Ethanox)®310抗氧化劑及來自狄估 沙（Degussa)的胺基矽烷戴那西蘭（Dynasylan)AMEO之混合 物。以25公斤/小時之輸入量與所選擇的溫度設定及螺旋速 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。 -25- 200815290 表2 Phr (每百份總樹脂的份數） 愛斯扣林Ultra UL00328 80 LL1001XV 20 氫氧化鋁 150 AMEO矽烷 1.6 愛森諾斯310 0.6 在形成阻燃劑樹脂調配物時，在Buss化合之前首先於 鼓中混合AMEO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BUSS捏合機的第一輸入 口，且將剩餘的50%氫氧化鋁進料至Buss捏合機的第二進 料埠中。將排出擠壓器垂直安裝在Buss Ko-捏合機邊緣且 具有螺旋尺寸70毫米。第4圖顯示出排出擠壓器之馬達對 等級編號1之本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GmbH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 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0 -26- 200815290 【圖式簡單說明】 第1圖顯示出在第二侵入測試操作及ATH等級編號 1(根據本發明的ATH)之孔體積比V與所施加的壓力之函 數，且與標準等級比較。 第2圖顯示出在第二侵入測試操作及ATH等級編號 1(根據本發明的ATH)其對孔半徑r與孔體積比V繪圖，且 與標準等級比較。 第3圖顯示出ATH等級編號1(根據本發明的ATH)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 用之本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OL-104 LE之功率圖形。 【主要元件符號說明】 • 。 \\ •27-Bm3/h. 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, more preferably greater than 70 meters per second, and most preferably in the range. 70 meters / sec to about 140 meters / sec. 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 slurry 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 150 ° C to about 550 ° C, with an optimum range from about 270 ° C to about 500 ° C. The honing of the slurry 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 slurry. Typically, the BET of the honed and dried ATH is mostly about 10% greater than the ATH particles in the slurry. The BET ratio of the ATH product particles is preferably in the range of from about 10% to about 40% greater than the ATH particles in the slurry. The BET of the ATH product particles is preferably greater than the ATH particles in the slurry from about _10% to about 25%. In many applications, the resulting ATH product particles can be used "directly." However, in some embodiments, the honed and dried ATH particles are further processed to reduce or, in certain embodiments, eliminate the cohesive material. Viscosity is common in ATH particle manufacturing processes and its presence can adversely affect the performance of ATH particles in the resin in certain applications. Therefore, ATH manufacturers are highly eager to reduce the better elimination of the binder. In the practice of the present invention, the number of cohesomers or the degree of cohesion present in the honed and dried ATH particles from -12 to 200815290 can be subjected to further deagglomeration processing steps by allowing the honed and dried ATH particles to undergo further deagglomeration processing steps. reduce. De-agglomeration means that the honed and dried cerium particles are subjected to further treatment, wherein the number of viscous or the degree of cohesion present in the honed and dried cerium particles is reduced (ie, present in the honing) The number of binders in the dried cerium particles is greater than the number of binders present in the cerium product particles, substantially eliminated in certain embodiments, and slightly reduced in size of the honed and dried granules. . By "minorly reduced particle size" is meant that the d5 ΑΤΗ of the ruthenium product particles is greater than or equal to 90% of the honed dry ruthenium particles. The remaining properties of the honed dry ATH particles are the same or substantially the same as the ruthenium product particles produced by de-bonding the honed and dried ATH particles. In a preferred embodiment, the dry honed ATH d5 〇 ranges from about 90% to about 95% of the honed dried ATH granules, more preferably about 95% of the honed and dried ATH granules. Up to about 99% range. Any of the well known techniques for effectively reducing the binder can be used to achieve the reduction of the presence of the binder 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 classify ATH product particles using gravity, centrifugal force, inertial force, or any combination thereof. 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 easily be selected from -13.200815290 to include a suitable screen and/or The sorter for the mesh. 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 the knowledge of the general techniques of the art and the desired properties of the final ATH product particles can be readily selected to best suit the particular application. mill. Thus, the ATH product particles of the electrical form generally, the process of the invention can be used to produce ATH product particles having the following properties: oil absorption (as measured using ISO 7 87 -5: 1 9 80) • ranging from about 1 to About 35%; BET specific surface area (as measured by DIN-66 1 32) ranges from about 1 to 15 square meters per gram; and d5 〇 ranges from about 0.5 to 2.5 microns. 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 inventor of the present inventor has a higher degree of structured agglomerates for the polymer molecules provided, which contain more and larger pores and appear to be more difficult to wet, resulting in a kneading machine (eg Difficulty in the compounding process (higher motor power pattern change) in the Buss Κο-kneader or twin screw extruder or other machines which are well known in the art and which have been used for this purpose. In this regard, the inventors have discovered that the process of the present invention produces ruthenium product particles characterized by a smaller median pore size and/or a lower total pore volume (when compared to currently available ruthenium), This is related to the improvement of the ATH product particles which are wetted by the polymeric material (when compared to the currently available ΑΤΗ-14-200815290 granules), thus resulting in improved compositing behavior, i.e., the use of hydrazine-containing granules The flame retardant resin of the agent has less variation in the power pattern of the engine (motor) of the machine. The ruthenium product particles produced by the present invention are at about 1 000 bar. And pore volume ratio ("VmaV') can be derived from mercury porosity measurement. The theory of mercury porosity measurement is that non-reactive, non-wetting liquid will not penetrate the pore until sufficient pressure is applied to force it into The physical principle is based on the fact that the higher the pressure required for the liquid to enter the pore, the smaller the pore size. It has been found that the smaller pore size and/or the lower total pore volume ratio and the ATH product particles produced by the present invention. The better wetting ability is related to each other. The pore size of the ATH product particles produced by the present invention can be determined from the Porometer UOOO from Italy by Carlo Erb a Strumentazione (derived from mercury pores). According to the data of the measurement method, according to the manual of the Baltic 2000, the following equation is used to calculate the hole radius r from the measurement. Pressure P: r = -2 r cos( 0 )/p, where 0 is wetting The angle and r are the surface tension. The measurement used in the measurement method used herein is 141.3° and r is set to 480 dynes/cm. In order to improve the reproducibility of the measurement method, as described in the Baltic 2000 In the manual Typically, the second ATH intrusion test operation was performed to calculate the pore size of the ATH product particles. The second test operation was used because the inventors observed that the amount of mercury having a volume V would be after extrusion (ie, after pressure is released to After the partial pressure, it remains in the sample of the ATH particles. Therefore, η can be derived from this data, as will be explained below with reference to Figures 1, 2 and 3. In the first test operation, as in -15-200815290, a sample of the ATH product particles produced by the present invention, and measuring the pore volume as a function of the applied intrusion pressure ρ (using a maximum pressure of 1000 bar) is described. Release pressure and allow it to reach ambient pressure after completing the first test operation. Use the same sputum sample from the first test operation (no impurities) for the second intrusion test operation (according to the Handbook of Boroisi 2000), where The measurement of the pore volume ratio V(p) of the two test operations uses the volume V. As a new starting volume, then the second test operation is set to zero. In the second intrusion test operation, the sample is again sampled. The pore volume ratio V(p) Φ is measured as a function of the applied intrusion pressure (using a maximum pressure of 1 000 bar). Figure 1 shows the ATH manufactured according to the invention in a second intrusion test operation (level number 1) The pore volume ratio V is as a function of the applied pressure and is compared to the now commercially available ATH 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 by Boroisi 2000, the hole radius r is calculated according to the formula n2rcos(0)/p, where 0 is the wetting angle, r is the surface tension and P is the intrusion pressure. For all ® r measurements taken in this paper, use 141.3° Θ値 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 operating hole 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 1〇〇% and the other volume ratio of the special ATH is divided by the maximum 値. The pore radius at the 50% relative pore volume ratio -16- •200815290 is defined herein as the median radius r5 of the pore radius. . For example, according to Fig. 3, the hole radius median Γ5 of ATH (i.e., Invention 1) according to the present invention. It is 0.33 microns. The procedure described above was repeated using a sample of ATH product particles made in accordance with the present invention, and it has been found that the ATH product particles 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 ruthenium product particles produced by the present invention range from about 0.20 to about + 0.33 microns, more preferably from about 〇2 to about 0.3 microns. In other preferred embodiments, r5 is in the range of 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, η. It ranges from about 0.09 to about 0.21 microns, more preferably from about 0.09 to about 0.165 microns. The ruthenium product particles produced by the present invention may also be characterized as having a Vmax (i.e., a maximum pore volume ratio of about 1000 bar) ranging 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 3 90 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 550 cubic millimeters per gram. In still other preferred embodiments, Vmax ranges from about 300 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 a -17--200815290 oiliness (as measured using ISO 7 87-5: 1 9 80) 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 2 3 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 still other preferred embodiments, the ATH product particles produced by the present invention are characterized by oil absorption in the range of from about 25 to about 35 %, more preferably in the range of 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-661 32) ranging 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 to 5 to about 5.5. Square meters / gram. In other preferred embodiments, the ruthenium 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 meters / gram. In still other preferred embodiments, the ATH product particles produced by the present invention have a BET 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 kilometers. Ruler / gram. The ATH product particles produced by the present invention may also be characterized as having -18-200815290 d5. In the range from about 0.5 to 2.5 microns. In a preferred embodiment, the ATH product particles produced by the present invention have a d5 〇 ranging from about 1.5 to about 2.5 microns, more preferably from about 1, 8 to about 2.2 microns. In other preferred embodiments, the A bismuth product particles produced by the present invention have a cho ranging from about 1.3 to about 2.0 microns, more preferably from about 1.4 to about 1.8 microns. In still other preferred embodiments, the ruthenium product particles produced by the present invention have a d5 〇 ranging from about 0.9 to about 1.8 microns, more preferably from about 1.1 to about 1.5 microns. ^ It should be noted that all particle diameter metrics (i.e., d5.) disclosed herein are measured using laser diffraction using a Cilas 1 064L laser spectrometer from Quantachrome. In general, the procedure used herein to measure d5〇 can be carried out by first introducing a suitable aqueous dispersion solution (formulation see below) into the sample preparation vessel of the apparatus. Then select the standard measurement called “Particle Expert” and also select the measurement model “Range 1” and then select the internal parameters of the device applied to the expected particle size distribution. It should be noted that during the measurement, the sample is typically exposed to ultrasound for about 60 seconds during the dispersion and during the measurement. After the background measurement has been carried out, about 75 to about 100 mg of the sample to be analyzed is placed in a sample container containing the water/dispersant solution and measurement is started. This water/dispersant solution can be obtained by first from 500 grams of Calgon (available from KMF Rebecca Chemical (1^13 0: ^1^11^6)) and 3 liters of octopus? 0; ^5 311 (available from Beth(R) (3-8??)) to prepare a concentrate to prepare. This solution consisted of deionized water to 1 liter. This original 10 liters of 100 ml was taken and further diluted to 10 liters with deionized water in that order, and this final solution was used as the aqueous dispersant -19-200815290 described above. Use of ATH product particles as a flame retardant The ruthenium product particles produced in accordance with the present invention can be used as a flame retardant in various synthetic resins. Non-limiting examples of thermoplastic resins using dry honed niobium particles have been found to include polyethylene, ethylene-propylene copolymers, polymers and copolymers of C2 to C8 olefins (alpha-olefins) such as polybutene, poly (4-methylpentene-1) or an analog thereof), a copolymer of these olefins and dienes, an ethylene-acrylate copolymer, polystyrene, ABS resin, AAS resin, AS resin, MBS resin, Ethylene·vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl chloride-vinyl acetate graft polymer resin, vinylidene chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-propylene Copolymers, vinyl acetate resins, phenoxy resins 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, poly m W butadiene rubber, acrylic rubber, silicone rubber, fluoroelastomer, NBR and chlorosulfonated polyethylene. Further included are polymer suspensions (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, EV.A (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 olefin (α-olefin) Polymers and copolymers such as polybutene and poly(4--20-200815290 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 compounding properties by using the ATH product particles according to the present invention as a flame retardant in a synthetic resin. It is highly desirable to have a better compounding property by a compounder, a manufacturing process, etc., in order to produce a highly flame-retardant compound and a final extruded or molded article using a synthetic resin containing ATH product particles. Highly ambiguous is meant to contain ATH product particles that are flame retardant, as discussed below. The preferred compounding property means a change in the degree of energy in a compounding machine (e.g., a buss Ko-kneader or a twin screw extruder) required for mixing a synthetic resin containing the A Τ product particles produced according to the present invention. A compounding machine having a smaller amplitude than a synthetic resin containing conventional cerium 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. / Thus, in a particular embodiment, the invention relates to a flame retardant polymer formulation comprising at least one synthetic resin selected from the above description (in only some embodiments) and a flame retardant amount The ruthenium product particles produced in accordance with the present invention; and extruded and/or molded articles made 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 7 0% by weight (subject to the same basis). In the most preferred embodiment, the amount of flame retardant is from about 30% by weight to about 6% by weight of the ruthenium product particles, whichever is the same. -21- 200815290 This 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-, vinyl- or alkyl decane or maleic acid graft polymer; sodium stearate or calcium stearate; organic peroxide; dye; pigment; sputum; foaming agent; Agent; heat stabilizer; antioxidant; antistatic agent; strengthening agent; metal scavenger or passivating agent; impact modifier; processing aid; mold release aid, lubricant Φ slip agent; 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. The proportions of other optional additives are well known and can be varied to suit the needs of any provided condition. The method of incorporating and incorporating the components of the flame retardant polymer formulation is not critical to the invention and can be any method 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 Ko-Kneader, Internal Mixer, Farrel Continuous Mixer or Double Screw Extrusion Alternatively, or in some instances, a single screw extruder or two roller mills. Then, if so desired, the flame retardant polymer formulation can be molded in a subsequent processing step. 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 fabrication, such as drawing, embossing, coating, printing, electroplating, -22-200815290 perforation or cutting. The molded article may also be fixed to a material other than the flame retardant polymer formulation of the present invention, such as gypsum board, wood, barrier, 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, a 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. The flame retardant resin formulation is then heated to a molten state in an extruder, and then the molten flame retardant resin formulation is extruded through a selected mold to form an extruded article or coated for use, for example, for data transfer. Metal wire or fiberglass. 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 preferred embodiments of the present invention contemplate that the full range discussed herein includes ranges from any lower amount to any higher amount. For example, when discussing the oil absorption of dry-honed ATH particles, the range of considerations is from about 30% to about 32%, from about 19% to about 25%, from about 21% to about 27%, etc. And the like are within the scope of the invention. [Embodiment] The following examples will illustrate the invention, but are not intended to be limiting in any way. -23- 200815290 Examples, describe η in the following examples. And V... Derived from the mercury porosimetry using the Porosi 2000 as described above. Unless otherwise stated, d5〇, BET, oil absorption, etc. are all measured according to the techniques described above. Similarly, the term "inventive ATH" as used in the examples is intended to mean 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. 10 Example 1 To form a slurry, a suitable dispersant, Antiprex® A40 (commercially available from Ciba®), was added to the ATH filter cake (which has a solids content of 55 weights). %) to form a slurry having a viscosity of about 150 centipoise. The slurry was fed to a dry honing machine at a rate of 280 liters per hour. Prior to dry honing, the aluminum hydroxide in the filter cake had a BET specific surface area of 3.7 square meters per gram and a median particle size of 2.0 microns. This honing operation is carried out under conditions including a flow rate of air ranging from 3 000 to 3 00 Bm 3 /h, a temperature ranging from 400 to 450 ° C and a rotor speed of 55 ® m / s. 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® L-104 LE (manufactured by Martinswerk GmbH) and the product properties of the competitive aluminum hydroxide grade “competitive” are also shown in Table 1. . -24- 200815290 Table 1 Median Hole Radius Maximum Hole Volume Ratio Vmax Particle size median ds. ΑΊΉ OL-104 LE 0.419 529 1.83 3.2 Competitive 0.353 504 1.52 3.2 BET 0.325 440 1.90 4.0 Compared to BET surface ("put") (micron) (cubic millimeter (micron) (square metric)) As seen in Table 1, the aluminum hydroxide grade of the present invention (ATH made according to the present invention) has the lowest median pore radius and the lowest maximum pore volume ratio. Example 2 The aluminum hydroxide particles of Comparative Example 1 were used, respectively. Nobel OL-104 LE and the aluminum hydroxide grade of the present invention form a flame retardant resin formulation. The synthetic resin used is EVA Espresso® UlUa UL00328 from ExxonMobil and comes from Essence Mobil's LLDPE grade LL 1001 XV, Ethanox® 310 antioxidant commercially available from Albemarle®, Inc., and amine decane from Degussa A mixture of Dynasylan AMEO. At a 25 kg/hr input with the selected temperature setting and spiral speed, using a general method well known to those skilled in the art, at 46 mm Booth. These components were mixed on a kneader (L/D ratio = 11). The amount of each component used in formulating the flame retardant resin formulation is detailed in Table 2 below. -25- 200815290 Table 2 Phr ( Parts per 100 parts of total resin) Aussie Ultra UL00328 80 LL1001XV 20 Aluminium hydroxide 150 AMEO decane 1.6 Aisensos 310 0.6 When forming a flame retardant resin formulation, first mix in the drum before the Buss compound The total amount of AMEO decane and Ethanox® 310 and synthetic resin. Depending on the loss in the gravity feeder, the resin/decane/antioxidant mixture is fed to the first of the BUSS kneader together with a total of 50% aluminum hydroxide. The inlet port was fed and the remaining 50% aluminum hydroxide was fed into the second feed crucible of the Buss kneader. The discharge extruder was mounted vertically on the edge of the Buss Ko-kneader and had a helix size of 70 mm. The power diagram of the aluminum hydroxide of the present invention showing the discharge extruder is shown in Figure 1. Figure 5 shows the motor of the discharge extruder versus the aluminum hydroxide grade OL produced by Martins Walker GmbH. -104 LE power graph. As in the 4th and As illustrated in Figure 5, when the aluminum hydroxide particles according to the present invention are used in a flame retardant resin formulation, the energy (power) pattern change of the discharge extruder is significantly reduced. As described above, the lower energy level Variations allow for higher input and/or more uniform (homogeneous) flame retardant resin formulations 0 -26- 200815290 [Simplified Schematic] Figure 1 shows the second intrusion test operation and ATH grade number 1 ( The pore volume ratio V of ATH) according to the invention is a function of the applied pressure and is compared to a standard grade. Figure 2 shows the second intrusion test operation and ATH class number 1 (ATH according to the invention) plotted against hole radius r to hole volume ratio V and compared to the standard level. Figure 3 shows the normalized pore volume ratio of ATH grade number 1 (ATH according to the invention) and compared to the standard grade, which is set by setting the maximum pore volume ratio for each ATH grade to 1 〇〇 %, and the other specific volume of the matching ATH grade is divided by the maximum 値. Fig. 4 shows the power pattern of the aluminum hydroxide grade of the present invention used in the first embodiment of the motor of the discharge extruder. Figure 5 shows the power pattern of the motor of the discharge extruder for the comparative aluminum hydroxide grade OL-104 LE used in Example 1. [Main component symbol description] • . \\ •27-