200811045 九、發明說明： 【發明所屬之技術領域】 本發明關於無機阻燃劑之製造。更特別地’本發 於一種用於製造具有改良熱安定性之氫氧化鋁阻燃劑 穎方法。 【先前技術】 氫氧化鋁具有多個不同之名稱，如水合鋁、三水 等，但是通常稱爲ATH。ATH顆粒有許多用途，如在 φ 種材料（例如紙、樹脂、橡膠、塑膠等）中之塡料。 產物可用於各種商業應用，如電纜及電線外皮、輸送 熱塑性模具、黏著劑等。ATH —般用於改良此材料之 性且亦作爲消煙劑。ATH亦常在用於製造印刷電路板 脂中作爲阻燃劑。因此ATH之熱安定性爲最終使用者 注意之品質。例如在印刷電路板應用中，用於建構板 層的熱安定性必須高到足以可無鉛焊接。 ATH之合成及製造方法在此技藝爲已知的。然而 φ ATH等級之需求漸增，而且現行方法無法製造所有這 級。因此隨訂製ATH等級之需求增加，用於製造這些 之方法的需求亦漸增。 【發明內容】 雖然實驗證據顯示ATH之熱安定性與ATH之總 含量有關，發明人在此已發現且相信，雖然不希望以 限制，本明發明ATH之改良熱安定性與不溶性鈉鹼含 關，其一般按總鈉鹼重量計爲總鈉鹼含量之約70至） 明關 的新 合鋁 許多 這些 帶、 阻燃 之樹 極爲 之夾 訂製 些等 等級 鈉鹼 理論 量有 与99 200811045 重量％範圍，其餘爲可溶性鈉鹼。 發明人亦相信，雖然不希望以理論限制，ATH顆粒對 樹脂之潤濕力視ATH顆粒之形態而定，而且發明人已意料 外地發現，使用本發明之方法可製造關於現有ATH具有改 良潤濕力之ATH顆粒。雖然不希望以理論限制，發明人相 信此改良潤濕力歸因於在此揭示方法所製造A Τ Η顆粒之形 態的改良。 發明人進一步相信，雖然不希望以理論限制，此改良 # 形態歸因於ΑΤΗ顆粒之總孔體積比及/或孔半徑中位數 (“r5〇”）。發明人相信，對於特定之聚合物分子，具有較高 結構化凝集體之ATH產物含更多及更大之孔且似乎更難以 潤濕，導致在如Buss Ko-捏合機之捏合機或雙螺桿擠壓機 或此技藝已知且用於此目的之其他機械中複合期間之困難 (馬達功率之變動較高）。因此發明人已發現，特徵爲孔 度中位數較小及/或總孔體積較小之ΑΤΗ塡料與對聚合材 料之改良潤濕力有關，因此造成改良之複合行爲，即用於 ^ 複合含ΑΤΗ塡料阻燃樹脂之複合機械的引擎（馬達）功率 變動較小。發明人已發現，本發明之方法特別適合用於製 造具有特徵之ΑΤΗ。 因此本發明關於一種包括硏磨乾燥過濾濕餅而製造經 硏磨乾燥ΑΤΗ顆粒（含黏聚物），然後將該經硏磨乾燥 ΑΤΗ顆粒去黏聚而製造ΑΤΗ產物顆粒之方法。在此具體實 施例中，過濾濕餅含約25至約85重量％範圍之ΑΤΗ顆粒 ，而且ΑΤΗ產物顆粒具有約0 · 0 9至約0 · 3 3微米範圍之孔 200811045 半徑中位數（“r5〇”）。 在另一個具體實施例中，本發明製造之ATH產物顆粒 具有約300至約700立方毫米/克範圍之Vmax，即在約1〇〇〇 巴之最大孔體積比’及/或約0·09至約0.33微米範圍之r50 ，即相對孔體積比5 0 %處之孔半徑，及一或多種，較佳爲 二或更多種，而且更佳爲三更多種，在某些具體實施例中 爲全部以下特徵：i)約〇·5至約2·5微米之d5(); ii)按經硏 磨乾燥ATH顆粒之總重量計爲小於約〇 · 4重量％之總鈉鹼 φ 含量；iii)按ISO 787-5 : 1 980測定爲小於約50%之吸油性； 及iv)按DIN-6 6132測定爲約1至約15平方米/克之表面積 比（BET)，其中經硏磨乾燥ATH顆粒之導電度在10重量％ 之ATH於水中測量小於約200 μ S/公分。 本發明製造之ΑΤΗ產物顆粒可在各種阻燃樹脂調配 物中作爲阻燃劑，其有時稱爲阻燃塡料或僅稱爲塡料。 在某些具體實施例中，本發明之ΑΤΗ產物顆粒進一步 特徵爲具有小於約〇. 1重量％之可溶性鈉鹼含量。 • 【實施方式】 應注意，在此揭示之所有粒徑測量，即d5G，係使用得 自Quantachrome之Cilas 1 064 L雷射光譜儀藉雷射繞射測 量。通常在此用於測量d5G之步驟可藉由首先將適當之水-分散劑溶液（製備參見以下）引入裝置之樣品製備容器中 而實行。然後選擇稱爲「顆粒專家」之標準測量，亦選擇 測量模型「範圍1」，然後選擇適用於預期粒度分布之裝置 內部參數。應注意，在測量期間，樣品一般在分散期間及 200811045 在測量期間暴露於超音波約60秒。在完成背景測量後，將 約75至約1 00毫克之欲測量樣品置於具水/分散劑溶液之 樣品容器中且開始測量。水/分散劑溶液可藉由首先由500 克得自KMF Laborchemie之Calgon與3公升得自BASF之 CAL Polysalt製備濃縮物而製備。將此溶液以去離子水組 成10公升。取此原始10公升之10 0毫升繼而以去離子水 進一步稀釋至10公升，及使用此最終溶液作爲上述水-分 散劑溶液。 ⑩ 濾餅 本發明將含ATH顆粒之過濾濕餅，有時僅稱爲濾餅， 硏磨乾燥以製造經硏磨乾燥ATH顆粒。濾餅一般含按濾餅 之總重量計爲約25至約85重量％範圍之ATH顆粒，在較 佳具體實施例中，濾餅含約40至約70重量％範圍之ATH 顆粒，更佳爲約55至約65重量％範圍之ATH顆粒，其均 爲相同之計算基礎。 在其他具體實施例中，濾餅含約40至約60重量％範 ^ 圍之ATH顆粒，更佳爲約45至約55重量％範圍之ATH顆 粒’其均爲相同之計算基礎。在又其他具體實施例中，濾 餅含約25至約50重量％範圍之ATH顆粒，更佳爲約30至 約45重量％範圍之ATH顆粒，其均爲相同之計算基礎。 用於本發明實務之濾餅可由任何用於製造ATH顆粒之 力 '法得到。較佳爲濾餅係由涉及經沉澱及過濾之製造ATH 顆粒的方法得到。在一個例示具體實施例中，濾餅係由一 β @括將粗氫氧化鋁溶於苛性鹼中以形成鋁酸鈉液，將其 200811045 冷卻及過濾，如此形成可用於此例示具體實施例之鋁酸鈉 液的方法得到。如此製造之鋁酸鈉液一般具有約〗.4 : i至約 1.55: 1範圍之Na2〇對Al2〇3莫耳比例。爲了由鋁酸鈉液沉 ® ATH顆粒，其將ATH籽粒以每公升鋁酸鈉液爲約〖克 ATH籽粒至每公升鋁酸鈉液爲約3克ATH籽粒範圍之量加 入鋁酸鈉液，如此形成方法混合物。在鋁酸鈉液爲約45至200811045 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the manufacture of inorganic flame retardants. More particularly, the present invention relates to a method for producing an aluminum hydroxide flame retardant having improved thermal stability. [Prior Art] Aluminum hydroxide has a number of different names, such as hydrated aluminum, trihydrate, etc., but is commonly referred to as ATH. ATH particles have many uses, such as those in φ materials (such as paper, resin, rubber, plastics, etc.). The product can be used in a variety of commercial applications such as cable and wire sheathing, thermoplastic molds, adhesives, and the like. ATH is generally used to improve the properties of this material and also as a smoke suppressant. ATH is also commonly used as a flame retardant in the manufacture of printed circuit board grease. Therefore, the thermal stability of ATH is the quality of the end user's attention. For example, in printed circuit board applications, the thermal stability used to build the slab must be high enough to lead-free soldering. The synthesis and manufacturing methods of ATH are known in the art. However, the demand for the φ ATH rating is increasing, and current methods cannot make all of this. As the demand for custom ATH grades increases, so does the need to manufacture these methods. SUMMARY OF THE INVENTION While experimental evidence indicates that the thermal stability of ATH is related to the total content of ATH, the inventors herein have discovered and believed that although it is not intended to be limiting, the improved thermal stability of invented ATH and the insoluble sodium-base are included. It is generally about 70% of the total sodium alkali content based on the total sodium alkali weight.) Many of these belts of Mingguan, many of the flame retardant trees are stapled to order some of the equivalent grades of sodium bases with 99 200811045 weight % range, the rest is soluble sodium base. The inventors also believe that although it is not desired to be bound by theory, the wetting force of the ATH particles to the resin depends on the morphology of the ATH particles, and the inventors have unexpectedly discovered that improved wetness can be produced with respect to existing ATH using the method of the present invention. ATH ATH particles. While not wishing to be bound by theory, the inventors believe that this improved wetting force is due to an improvement in the morphology of the A Τ particles produced by the methods disclosed herein. The inventors further believe that although not wishing to be bound by theory, this modified form is attributed to the total pore volume ratio of the ruthenium particles and/or the median pore radius ("r5"). The inventors believe that for a particular polymer molecule, the ATH product with a higher structured aggregate contains more and larger pores and appears to be more difficult to wet, resulting in a kneader or twin screw such as a Buss Ko-kneader. Diffuser (higher variation in motor power) during extrusion or other machines known in the art and used for this purpose. The inventors have therefore discovered that a material characterized by a small median pore size and/or a small total pore volume is associated with improved wetting force on the polymeric material, thus resulting in improved composite behavior, i.e., for compounding The engine (motor) of the composite machine containing the flame retardant resin has a small power variation. The inventors have found that the method of the present invention is particularly suitable for use in the manufacture of features. SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a method for producing ruthenium product particles by honing dry filtered wet cake to produce honed dry mash particles (containing a binder) and then deagglomerating the honed dry ruthenium particles. In this particular embodiment, the wet cake is filtered to contain cerium particles in the range of from about 25 to about 85% by weight, and the cerium product particles have a median radius of the hole 200811045 in the range of from about 0. 09 to about 0. 3 3 microns (" R5〇"). In another embodiment, the ATH product particles produced in accordance with the present invention have a Vmax in the range of from about 300 to about 700 cubic millimeters per gram, i.e., a maximum pore volume ratio of <RTIgt; R50 in the range of about 0.33 micrometers, i.e., the pore radius at a relative pore volume ratio of 50%, and one or more, preferably two or more, and more preferably three more, in some embodiments. All of the following characteristics: i) d5() from about 5 to about 2.5 microns; ii) less than about 〇·4% by weight of the total sodium alkali φ content based on the total weight of the honed dry ATH particles ; iii) an oil absorption of less than about 50% as determined by ISO 787-5:1 980; and iv) a surface area ratio (BET) of from about 1 to about 15 square meters per gram as determined by DIN-6 6132, wherein honing The conductivity of the dried ATH particles was less than about 200 μS/cm measured in 10 wt% ATH in water. The ruthenium product particles produced by the present invention can be used as flame retardants in various flame retardant resin formulations, sometimes referred to as flame retardant tanning or simply as tanning materials. In some embodiments, the bismuth product particles of the present invention are further characterized by having a soluble sodium alkali content of less than about 0.1% by weight. • [Embodiment] It should be noted that all particle size measurements disclosed herein, i.e., d5G, were measured by laser diffraction using a Cilas 1 064 L laser spectrometer from Quantachrome. The procedure generally used herein for measuring d5G can be carried out by first introducing a suitable water-dispersant solution (prepared as described 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 that are appropriate for the expected particle size distribution. It should be noted that during the measurement, the sample is typically exposed to the ultrasonic wave for about 60 seconds during the measurement and during the measurement period of 200811045. After the background measurement is completed, about 75 to about 100 mg of the sample to be measured is placed in a sample container with a water/dispersant solution and measurement is started. The water/dispersant solution can be prepared by first preparing a concentrate from 500 grams of Calgon from KMF Laborchemie and 3 liters of CAL Polysalt from BASF. This solution was made up of 10 liters of deionized water. The original 10 liters of 10 ml was taken and further diluted to 10 liters with deionized water, and the final solution was used as the above water-dispersant solution. 10 Filter Cake The present invention comprises a filtered wet cake comprising ATH particles, sometimes simply referred to as a filter cake, honed and dried to produce honed and dried ATH particles. The filter cake typically comprises from about 25 to about 85% by weight of ATH particles, based on the total weight of the filter cake. In a preferred embodiment, the filter cake contains from about 40 to about 70 weight percent ATH particles, more preferably ATH particles in the range of from about 55 to about 65 weight percent, which are all based on the same calculations. In other embodiments, the filter cake contains from about 40 to about 60 weight percent of the ATH particles, more preferably from about 45 to about 55 weight percent of the ATH particles' which are all based on the same calculations. In still other embodiments, the filter cake comprises from about 25 to about 50 weight percent ATH particles, more preferably from about 30 to about 45 weight percent ATH particles, which are all based on the same calculations. The filter cake used in the practice of the present invention can be obtained by any of the methods used to make ATH particles. Preferably, the filter cake is obtained by a process involving the manufacture of ATH particles by precipitation and filtration. In an exemplary embodiment, the filter cake is prepared by dissolving the crude aluminum hydroxide in caustic to form a sodium aluminate solution, cooling it and filtering it in 200811045, thus forming a specific embodiment for use in the exemplary embodiment. The method of sodium aluminate solution is obtained. The sodium aluminate solution thus produced generally has a Na2〇 to Al2〇3 molar ratio in the range of from about .4:i to about 1.55:1. For the sodium sulphate® ATH granules, the ATH grain is added to the sodium aluminate solution in an amount of about 3 grams of ATH grain per liter of sodium aluminate solution to about 3 grams of ATH grain per liter of sodium aluminate solution. The method mixture is thus formed. In sodium aluminate solution is about 45 to
約80°C之液溫時將ATH顆粒加入鋁酸鈉液。在加入ATH 籽粒之後，將方法混合物攪拌約1 〇 〇小時，或者直到N a2 Ο Φ 對Al2〇3莫耳比例爲約2.2:1至約3.5:1之範圍，如此形成 ATH懸浮液。所得ATH懸浮液一般包括按懸浮液計爲約8 〇 至約160克/公升之ATH。然而ATH濃度可改變以落在上述 範圍內。然後過濾及清洗所得ATH懸浮液以自其去除雜質 ，如此形成濾餅。在將濾餅硏磨乾燥前，其可以水（較佳 爲除鹽水）清洗一次，或在某些具體實施例中爲超過一次 〇 濾餅中之ATH顆粒 ^ 在某些具體實施例中，濾餅中ATH顆粒之BET爲約 1.0至約4·0平方米/克之範圍。在這些具體實施例中，其 較佳爲濾餅中之AT Η顆粒具有約1 · 5至約2 · 5平方米/克範 圍之BET。在這些具體實施例中，濾餅中之ΑΤΗ顆粒亦可 且較佳爲特徵爲約1.8至約3.5微米範圍，較佳爲約1.8至 約2.5微米範圍之d5e，其較在此製造之ATH產物顆粒粗。 在其他具體實施例中，濾餅中ATH顆粒之BET爲約 4·〇至約8·0平方米/克之範圍，較佳爲約5至約7平方米/ 200811045 克之範圍。在這些具體實施例中，濾餅中之ATH顆粒亦可 且較佳爲特徵爲約1.5至約2.5微米範圍，較佳爲約1.6至 約2.0微米範圍之d5()，其較在此製造之ΑΤΗ產物顆粒粗。 在又其他具體實施例中，濾餅中ATH顆粒之BET爲約 8.0至約14平方米/克之範圍，較佳爲約9至約12平方米/ 克之範圍。在這些具體實施例中，濾餅中之ATH顆粒亦可 且較佳爲特徵爲約1.5至約2·0微米範圍，較佳爲約1.5至 約1·8微米範圍之d5〇,其較在此製造之ΑΤΗ產物顆粒粗。 Φ 較ATH產物顆粒粗表示濾餅中ATH顆粒之d5G値的上 限通常爲較在此製造之ATH產物顆粒之d5G値的上限高至 少約0.2微米。 用於本發明之濾餅中的ATH顆粒亦可且較佳爲特徵爲 按濾餅中AT Η顆粒計爲小於約0 · 2重量％之總鈉驗含量。 在較佳具體實施例中，如果可溶性鈉鹼含量爲ΑΤΗ顆粒之 特徵，則總鈉鹼含量按濾餅中 ΑΤΗ顆粒之總重量計小於 〇 · 1 8重量％，更佳爲小於〇 · 1 2重量％。ΑΤΗ之總鈉鹼含量 0 可使用得自 Dtisseldorf/德國之 Dr· Bruno Lange GmbH 的 M7DC火燄光度計測量。在本發明中，ath顆粒之總鈉鹼 含量係藉由首先將1克之ATH顆粒加入石英玻璃碗中，然 後將3毫升之濃硫酸加入石英玻璃碗中，及以玻璃棒小心 地攪拌玻璃碗之內容物而測量。然後觀察混合物，而且如 果ATH結晶未完全溶解，則加入又3毫升之濃硫酸且再度 混合內容物。然後將碗在加熱板上加熱直到過量硫酸完全 蒸發。然後將石英玻璃碗之內容物冷卻至約室溫，及加入 -10 - 200811045 約50毫升之去離子水以溶解碗中之任何鹽。然後將碗之內 容物維持增溫約20分鐘直到鹽溶解。然後將玻璃碗之內容 物冷卻至約20 °C，轉移至500毫升量瓶中，然後將其充塡 去離子水且搖動均化。然後以火燄光度計分析5 00毫升量 瓶中溶液之ATH顆粒的總鈉鹼含量。 用於本發明之濾餅中的ATH顆粒亦可且較佳爲特徵爲 按濾餅中ATH顆粒計小於約0.1重量％之可溶性鈉鹼含量 '。在其他具體實施例中，濾餅中之ΑΤΉ顆粒可進一步特徵 # 爲具有大於約0.001至約0.1重量％範圍，在某些具體實施 例爲約0.02至約0.1重量％範圍之可溶性鈉鹼含量，其均 按濾餅中之ATH顆粒計。而在其他具體實施例中，ATH顆 粒可進一步特徵爲按濾餅中之ATH顆粒計具有約0.001至 小於0.04重量％範圍，在某些具體實施例爲約0.001至小 於0.03重量％範圍，在某些具體實施例爲約0.001至小於 (K 02重量％範圍之可溶性鈉鹼含量，其均爲相同之計算基 礎。可溶性鈉鹼含量係經火燄光度計測量。爲了測量可溶 • 性鈉鹼含量，其如下製備樣品之溶液：將20克之樣品轉移 至1 000毫升量瓶中，而且在約95 °c之水浴中以約25 0毫 升之去離子水瀝濾約45分鐘。然後將燒瓶冷卻至20°C， 以去離子水充塡至校正標記，及搖動均化。樣品沉降後在 ^ 瓶頸處形成透明溶液，而且藉過瀘針筒之助或使用離心機 可自燒瓶移除火燄光度計測量所需之溶液。 用於本發明實務之濾餅中的ATH顆粒亦可敘述爲具有 總鈉鹼含量之約70至約99.8重量％範圍的在此所述之不溶 -11- 200811045 性鈉鹼含量，其餘爲可溶性鈉鹼。發明人已意料外地發現 ，ATH之熱安定性與ATH之總鈉鹼含量有關。雖然實驗證 據顯示熱安定性與ATH之總鈉鹼含量有關，發明人相信， 雖然不希望以理論限制，本發明方法製造之ATH顆粒的改 良熱安定性與不溶性鈉鹼含量有關，其一般爲總鈉鹼含量 之約70至約99.8重量％範圍，其餘爲可溶性鈉鹼。在本發 明之某些具體實施例中，用於本發明實務之濾餅中的ATH 顆粒之總鈉鹼含量按濾餅中之ATH顆粒計一般爲小於約 0.20重量％之範圍，較佳爲小於約0.18重量％之範圍，更 佳爲小於約0.12重量％之範圍，其均爲相同之計算基礎。 在本發明之其他具體實施例中，用於本發明實務之濾餅中 的ATH顆粒之總鈉鹼含量按濾餅中之ATH顆粒計一般爲小 於約0.30重量％之範圍，較佳爲小於約〇·25重量％之範圍 ，更佳爲小於約0.20重量％之範圍，其均爲相同之計算基 礎。在本發明之又其他具體實施例中’用於本發明實務之 濾餅中的ATH顆粒之總鈉鹼含量按濾餅中之ATH顆粒計一 般爲小於約0.40重量％之範圍，較佳爲小於約〇·3〇重量％ 之範圍，更佳爲小於約〇·25重量％之範圍，其均爲相同之 計算基礎。 硏磨乾燥 如以上所討論，本發明涉及硏磨乾燥濾餅而製造經硏 磨乾燥ATH顆粒，其中濾餅中之ATH顆粒具有指定性質 ，如上所述。在此使用之「硏磨乾燥」及「乾燥硏磨」表 示濾餅在硏磨乾燥單元之擾流熱氣流中乾燥。硏磨乾燥單 -12- 200811045 元包括堅固地安裝在以高周速轉動之實心軸上的轉子。結 合高空氣輸出之轉動移動將流經之熱空氣轉化成極快之空 氣渦動，其帶動欲乾燥混合物（即濾餅），加速之，及分 布且乾燥混合物，如此製造經硏磨乾燥A Τ Η顆粒。在已完 全乾燥後將經硏磨乾燥ΑΤΗ顆粒經擾流空氣運出硏磨機， 而且較佳爲使用習知過濾器系統自熱空氣及蒸氣分離。在 本發明之另一個具體實施例中，在已完全乾燥後將經硏磨 乾燥ΑΤΗ顆粒經擾流空氣運輸通過整合至硏磨機中之空氣 • 分類機，然後經擾流空氣運出硏磨機，而且使用習知過濾 器系統自熱空氣及蒸氣分離。 用於乾燥瀘餅之熱空氣的輸出一般大於約3,000 Bm3/ 小時，較佳爲大於約5,000 Bm3/小時，更佳爲大於約3,000 Bm3/小時至約40,000 Bm3/小時，而且最佳爲約5,000 Bm3/ 小時至約30,000 Bm3/小時。 爲了達成此高輸出，硏磨乾燥單元之轉子一般具有大 於約40米/秒，較佳爲大於約60米/秒，更佳爲大於約70 ^ 米/秒，而且最佳爲約70米/秒至約140米/秒範圍之周速。 轉子之高轉速及高熱空氣輸出造成雷諾數大於約3,000之 熱氣流。 用於硏磨乾燥濾餅之熱氣流的溫度通常大於約1 5 0 °C ，較佳爲大於約27(TC。在一個更佳具體實施例中，熱氣 流之溫度爲約150°C至約55(TC之範圍，最佳爲約270°C至 約500°C之範圍。 在一個較佳具體實施例中，硏磨乾燥濾餅製造具有較 -13- 200811045 大BET表面積比之經硏磨乾燥ATH顆粒，如DIN-66132 所測定，然後成爲濾餅中之起始ATH顆粒。一般而言’經 硏磨乾燥ATH之BET大於濾餅中ATH顆粒超過約10%。 較佳爲經硏磨乾燥ATH之BET爲大於濾餅中ATH顆粒約 10%至約4 0%之範圍。更佳爲經硏磨乾燥ATH之BET爲大 於濾餅中ATH顆粒約10%至約25%之範圍。 如此製造之經硏磨乾燥ATH顆粒可「直接」用於許多 應用。然而在某些具體實施例中，其將經硏磨乾燥ATH顆 • 粒進一步處理以減少，或在某些具體實施例中黏聚。黏聚 物之形成在ATH顆粒製法中常見，而且其存在可及在某些 應用中確實有害地影響樹脂中ATH顆粒之性能。因此ATH 製造極希望減少，較佳爲排除黏聚物。 在本發明之實務中，存在於經硏磨乾燥ATH顆粒中之 黏聚物的數量或黏聚程度係藉由使經硏磨乾燥ATH顆粒接 受去黏聚處理而減少。 去黏聚作用 · ® 去黏聚表示使經硏磨乾燥ATH顆粒接受進一步處理 ，其中減少，在某些具體實施例中實質上排除存在於經硏 磨乾燥ATH顆粒中之黏聚物的數量或黏聚程度（即存在於 經硏磨乾燥ATH顆粒中之黏聚物的數量大於存在於ATH 產物顆粒中之黏聚物的數量），而經硏磨乾燥ΑΤΉ之粒度 減小極小。「少量縮減粒徑」表示ATH產物顆粒之d5〇大 於或等於經硏磨乾燥ATH顆粒之90%。在較佳具體實施例 中，經硏磨乾燥ATH之d5〇爲經硏磨乾燥ATH顆粒之約 -14- 200811045 9 0%至約95 %範圍，更佳爲在經硏磨乾燥ΑΤΗ顆粒之約95% •至約99%範圍內。 在本發明之實務中，經硏磨乾燥ATH顆粒中黏聚物之 數量或黏聚程度係使用空氣分類機或銷式硏磨機減少。適 合在此使用之空氣分類機包括使用重力、離心力、慣性力 、或其任何組合而將ATH產物顆粒分類者。使用這些分類 機在此技藝爲已知的，而且熟悉此技藝且熟知最終產物大 小者可易於選擇含適當網及/或篩之分類機。 • 適合在此使用之銷式硏磨機包括乾及濕銷式硏磨機。 如同空氣分類機，使用銷式硏磨機在此技藝爲已知的，而 且熟悉此技藝且熟知最終產物大小者可易於選擇最佳銷式 硏磨機而符合特定應用。 經硏磨乾燥ATH之去黏聚係在有效製造具有以下討 論之ATH產物顆粒的條件下進行。 依照本發明之ATH產物顆粒 通常本發明之方法製造通常特徵爲具有指定總孔體積 ® 比及/或孔半徑中位數（“r5〇”）之ATH產物顆粒，除了 一或多 種，較佳爲二或更多種，而且更佳爲三更多種，在某些具 體實施例中爲全部以下特徵：i)約〇·5至約2.5微米之d50 ;ii)按ATH產物顆粒之總重量計爲小於約0.4重量％之總 鈉鹼含量；iii)按ISO 7 87-5: 1 9 8 0測定爲小於約50%之吸油 性；及iv)按DIN-66 1 32測定爲約1至約15平方米/克之表 面積比（BET)，其中ATH產物顆粒之導電度在10重量％之 ATH於水中測量小於約200 pS/公分。 -15- 200811045 如上所述，發明人相信，對於特定之聚合物分子，具 有較高結構化凝集體之ATH顆粒含更多及更大之孔且似乎 更難以潤濕，導致在如Buss Κο-捏合機之捏合機或雙螺桿 擠壓機或此技藝已知且用於此目的之其他機械中複合期間 之困難（馬達功率之變動較高）。發明人已發現，本發明 之方法特別適合用於製造特徵爲孔度中位數較小及/或總 孔體積較小之ΑΤΗ產物顆粒，其與對聚合材料之改良潤濕 有關，因此造成改良之複合行爲，即用於複合含ΑΤΗ塡料 # 阻燃樹脂之複合機械的引擎（馬達）功率變動較小。 ΑΤΗ產物顆粒之r5G及在約1〇〇〇巴之孔體積比（“Vmax”) 可得自汞孔隙術。汞孔隙術之原理係基於非反應性、未潤 濕液體不穿透孔直到施加充分壓力以強迫其進入之物理原 理。因此液體進入孔所需之壓力越高，則孔度越小。其發 現較小之孔度及/或較低之總孔體積比與ATH產物顆粒之 較佳潤濕力有關。在此所製造ATH產物顆粒之孔度可使用 得自義大利 Carlo Erba Strum entazione 之 Porosimeter 20 00 ^ 由得自隶孔隙術之資料計算。依照P o r o s i m e t e r 2 0 0 0之手 冊，其使用以下方程式由測量之壓力 p計算孔半徑r : r = -2Ycos(e)/p;其中Θ爲潤濕角度及γ爲表面張力。在此採 用之測量係使用141.3°之Θ値且將γ設爲480達因/公分。 爲了改良測量之再現力，其由第二ΑΤΗ入侵測試計算 經硏磨乾燥ΑΤΗ顆粒之孔度，如Porosimeter 2000之手冊 所述。第二測試係因爲發明人觀察到在入侵後，即在將壓 力釋放至周圍壓力後，經硏磨乾燥ATH顆粒之樣品中殘留 -16- 200811045 體積爲Vo之汞量而使用。如此可由此資料得到r5G，如以 下所解釋。 在第一測試中，其如Porosimeter 2000之手冊所述而 製備本發明方法所製造ATH產物顆粒之樣品，及使用1000 巴之最大壓力測量孔體積如所施加入侵壓力P之函數。在 第一測試結束時釋放壓力且達到周圍壓力。實行利用得自 第一測試之相同純ATH產物顆粒樣品的第二入侵測試（依 照Porosimeter 2000之手冊），其中第二測試之孔體積比 • V(p)測量取體積V〇作爲新開始體積，然後對第二測試將其 設爲零。 在第二入侵測試中，再度使用1 000巴之最大壓力實行 樣品之孔體積比v(p)測量如所施加入侵壓力p之函數。在 此將在約1 000巴（即用於測量最大壓力）之孔體積稱爲 Vmax ° 由第二ATH產物顆粒入侵測試，藉Porosimeter 2000 依照公式r = -2YC〇S(e)/p計算孔半徑r;其中Θ爲潤濕角度， ® γ爲表面張力，及P爲入侵壓力。對於在此採用之所有r-測量均使用141 ·3°之Θ値且將γ設爲480達因/公分。如果需 要，則可將孔體積比相對孔半徑r繪圖而繪製產生之結果 。按定義，在此將相對孔體積比/ 5 〇%處之孔半徑稱爲孔體 積中位數r 5 〇。 對於r5D及Vmax之圖表，請參見美國臨時專利申請案 60/818,632 ； 60/818，633 ; 60/818，670 ; 60/815，515 ;及 60/8 1 8,426號，其均在此全部倂入作爲參考。 -17- 200811045 使用本發明方法所製造A Τ Η產物顆粒之樣品重複上 述步驟，而且發現如此製造之ΑΤΗ產物顆粒具有約〇·〇9 至約0.33微米範圍之r5G，即相對孔體積比50%處之孔半 徑。在本發明之某些具體實施例中，ATH產物顆粒之r50 爲約0·20至約0.33微米之範圍，較佳爲約〇·2至約〇·3微 米之範圍。在其他具體實施例中，r5G爲約0.185至約0.325 微米之範圍，較佳爲約0.185至約0.25微米之範圍。在又 其他較佳具體實施例中，r5G爲約〇· 09至約0.21微米之範 圍，更佳爲約0.09至約0.165微米之範圍。 本發明方法所製造ATH產物顆粒亦可特徵爲具有約 3 00至約700立方毫米/克範圍之Vmax，即在約1 000巴之 最大孔體積比。在本發明之某些具體實施例中，ATH產物 顆粒之Vmax爲約3 90至約480立方毫米/克之範圍，較佳 爲約410至約450立方毫米/克之範圍。在其他具體實施例 中，Vmax爲約400至約600立方毫米/克之範圍，較佳爲約 4 5 0至約5 5 0立方毫米/克之範圍。在又其他具體實施例中 ，Vmax爲約300至約700立方毫米/克之範圍，較佳爲約 3 5 0至約5 5 0立方毫米/克之範圍。 本發明方法所製造ATH產物顆粒亦可特徵爲具有按 I S Ο 7 8 7 - 5 : 1 9 8 0測定爲小於約5 0 %，有時在約1至約5 0 % 範圍之吸油性。在某些具體實施例中，本發明方法所製造 ATH產物顆粒特徵爲具有約23至約30%範圍，較佳爲約 24%至約2 9%範圍，更佳爲約25 %至約2 9%範圍之吸油性。 在其他具體實施例中’本發明方法所製造ΑΤΉ產物顆粒特 -18 - 200811045 徵爲具有約25%至約40%範圍，較佳爲約25%至約35%範 圍，更佳爲約26%至約30%範圍之吸油性。在又其他具體 實施例中，本發明方法所製造ATH產物顆粒特徵爲具有約 2 5 %至約5 0%範圍，較佳爲約26%至約40%範圍，更佳爲約 27%至約3 2%範圍之吸油性。在其他具體實施例中，本發明 方法所製造ATH產物顆粒之吸油性爲約19%至約23 %之範 圍，而且在又其他具體實施例中，所製造經硏磨乾燥ATH 顆粒之吸油性爲約21 %至約25 %之範圍。 # 本發明方法所製造ATH產物顆粒亦可特徵爲具有按 DIN-66 1 32測定爲約1至約15平方米/克範圍之BET表面 積比。在某些具體實施例中，本發明方法所製造ATH產物 顆粒具有約3至約6平方米/克範圍，較佳爲約3.5至約5.5 平方米/克範圍之BET表面積比。在其他具體實施例中，本 發明方法所製造ATH產物顆粒具有約6至約9平方米/克 範圍，較佳爲約6.5至約8.5平方米/克範圍之BET表面積 比。在又其他具體實施例中，本發明方法所製造ATH產物 ^ 顆粒具有約9至約15平方米/克範圍，較佳爲約10.5至約 1 2.5平方米/克範圍之BET表面積比。 本發明方法所製造ATH產物顆粒亦可特徵爲具有約 〇·5至2·5微米範圍之d5G。在某些具體實施例中，本發明 方法所製造ATH產物顆粒具有約1.5至約2.5微米範圍， 較佳爲約1·8至約2.2微米範圍之d5G。在其他具體實施例 中’本發明方法所製造ATH產物顆粒具有約1.3至約2.0 微米範圍，較佳爲約1.4至約1.8微米範圍之d5G。在又其 -19- 200811045 他具體實施例中，本發明方法所製造ATH產物顆粒具 〇·9至約1·8微米範圍，更佳爲約1.1至約1.5微米範 d 5 〇 〇 本發明方法所製造ATH產物顆粒亦可特徵爲具 ATH產物顆粒計爲小於約〇 . 4重量％之總鈉鹼含量。在 具體實施例中，如果可溶性鈉鹼含量爲A T Η產物顆粒 徵，則總鈉鹼含量小於約0.20重量％，較佳爲小於約 重量％，更佳爲小於約0.12重量％，其均按ΑΤΗ產物 # 之總重量計。在其他具體實施例中，如果可溶性鈉鹼 爲ΑΤΗ產物顆粒之特徵，則總鈉鹼含量按ΑΤΗ產物 之總重量計小於約〇 . 3 0，較佳爲小於約0 · 2 5重量％， 爲小於約0.20重量％。在其他具體實施例中，如果可 鈉鹼含量爲ΑΤΗ產物顆粒之特徵，則總鈉鹼含量按 產物顆粒之總重量計小於約〇·4〇，較佳爲小於約〇· 3〇 %，更佳爲小於約〇 · 2 5重量％。總鈉鹼含量可依照上 驟測量。 • 本發明方法所製造ΑΤΗ產物顆粒亦可特徵爲具 下表1、2及3所述之熱安定性。 有約 圍之 有按 某些 之特 0.18 顆粒 含量 顆粒 更佳 溶性 ΑΤΗ 重量 列步 有以 -20- 200811045 表1 1 wt.%TGA(0C) 2wt.%TGA(°C) 典型 210-225 220-235 較佳 210-220 220-230 更佳 214-218 224-228 表2 1 wt.%TGA(°C) 2wt.%TGA(°C) 典型 200-215 210-225 較佳 200-210 210-220 更佳 200-205 210-215 表3 1 wt.%TGA(°C) 2wt.%TGA(°C) 典型 195-210 205-220 較佳 195-205 205-215 更佳 195-200 205-210The ATH particles were added to the sodium aluminate solution at a liquid temperature of about 80 °C. After the addition of the ATH grain, the process mixture is stirred for about 1 Torr, or until the ratio of N a2 Ο Φ to Al 2 〇 3 mole is in the range of about 2.2:1 to about 3.5:1, thus forming an ATH suspension. The resulting ATH suspension typically comprises from about 8 Torr to about 160 grams per liter of ATH, based on the suspension. However, the ATH concentration can be varied to fall within the above range. The resulting ATH suspension is then filtered and washed to remove impurities therefrom, thus forming a filter cake. Before the filter cake is honed and dried, it may be washed once with water (preferably with demineralized water) or, in some embodiments, more than once with ATH particles in the mash cake. In some embodiments, The BET of the ATH particles in the cake ranges from about 1.0 to about 4·0 square meters per gram. In these embodiments, it is preferred that the AT ruthenium particles in the filter cake have a BET in the range of from about 1.5 to about 2.5 square meters per gram. In these embodiments, the ruthenium particles in the filter cake may also and preferably are characterized by a range of from about 1.8 to about 3.5 microns, preferably from about 1.8 to about 2.5 microns, which is the ATH product produced herein. The particles are coarse. In other embodiments, the BET of the ATH particles in the filter cake ranges from about 4 Torr to about 8.0 square meters per gram, preferably from about 5 to about 7 square meters per 200811045 grams. In these embodiments, the ATH particles in the filter cake may also and preferably are characterized by a range of from about 1.5 to about 2.5 microns, preferably from about 1.6 to about 2.0 microns, which is more than that produced herein. The ruthenium product particles are coarse. In still other embodiments, the BET of the ATH particles in the filter cake ranges from about 8.0 to about 14 square meters per gram, preferably from about 9 to about 12 square meters per gram. In these embodiments, the ATH particles in the filter cake may also and preferably are characterized by a range of from about 1.5 to about 2.0 microns, preferably from about 1.5 to about 1.8 microns, which is more The manufactured product particles were coarse. The Φ is larger than the ATH product particles, and the upper limit of the d5G ATH of the ATH particles in the filter cake is usually about 0.2 μm higher than the upper limit of the d5G ATH of the ATH product particles produced herein. The ATH particles used in the filter cake of the present invention may also and preferably be characterized as having a total sodium content of less than about 0.2% by weight based on the AT Η particles in the filter cake. In a preferred embodiment, if the soluble sodium alkali content is characteristic of the cerium particles, the total sodium alkali content is less than 〇·18% by weight, more preferably less than 〇·1 2 , based on the total weight of the cerium particles in the filter cake. weight%. The total sodium content of strontium is 0. It can be measured using an M7DC flame photometer from Dr. Bruno Lange GmbH, Dtisseldorf/Germany. In the present invention, the total sodium content of the ath particles is obtained by first adding 1 gram of ATH particles to a quartz glass bowl, then adding 3 ml of concentrated sulfuric acid to the quartz glass bowl, and carefully stirring the glass bowl with a glass rod. Measured by contents. The mixture was then observed, and if the ATH crystals were not completely dissolved, another 3 ml of concentrated sulfuric acid was added and the contents were again mixed. The bowl is then heated on a hot plate until excess sulfuric acid has completely evaporated. The contents of the quartz glass bowl are then cooled to about room temperature and about 50 milliliters of deionized water is added to dissolve the any salt in the bowl. The contents of the bowl are then allowed to warm for about 20 minutes until the salt dissolves. The contents of the glass bowl were then cooled to about 20 ° C, transferred to a 500 ml volumetric flask, then filled with deionized water and shaken to homogenize. The total sodium alkali content of the ATH particles of the solution in the 500 ml vial was then analyzed by flame photometry. The ATH particles used in the filter cake of the present invention may also and preferably are characterized by a soluble sodium alkali content of less than about 0.1% by weight based on the ATH particles in the filter cake. In other embodiments, the ruthenium particles in the filter cake may further be characterized by having a soluble sodium alkali content ranging from greater than about 0.001 to about 0.1 weight percent, and in certain embodiments from about 0.02 to about 0.1 weight percent, They are all based on the ATH particles in the filter cake. In still other embodiments, the ATH particles can be further characterized as having a range of from about 0.001 to less than 0.04 weight percent, and in some embodiments from about 0.001 to less than 0.03 weight percent, in certain embodiments, in the range of from about 0.001 to less than 0.03 weight percent. Some specific examples are from about 0.001 to less than (K 02% by weight of soluble sodium base content, which are all based on the same calculation. The soluble sodium alkali content is measured by a flame photometer. To measure the soluble sodium content, A sample solution was prepared as follows: 20 grams of the sample was transferred to a 1 000 ml volumetric flask and leached in about 25 ml of deionized water for about 45 minutes in a water bath of about 95 ° C. The flask was then cooled to 20 °C, fill with deionized water to the calibration mark, and shake to homogenize. After the sample settles, a clear solution is formed at the neck of the bottle, and the flame photometer can be removed from the flask by the help of a syringe or using a centrifuge. The desired solution. The ATH particles used in the filter cake of the practice of the present invention can also be described as having a total sodium content of from about 70 to about 99.8% by weight of the insoluble -11-200811045 sodium alkaloids described herein. The remainder is soluble sodium. The inventors have unexpectedly discovered that the thermal stability of ATH is related to the total sodium content of ATH. Although experimental evidence indicates that thermal stability is related to the total sodium content of ATH, the inventors believe that although not It is intended that, by theory, the improved thermal stability of the ATH particles produced by the process of the present invention is related to the insoluble sodium base content, which is generally in the range of from about 70 to about 99.8% by weight of the total sodium base content, with the balance being soluble sodium base. In some embodiments, the total sodium alkali content of the ATH particles used in the filter cake of the present invention is generally less than about 0.20% by weight, preferably less than about 0.18 by weight, based on the ATH particles in the filter cake. The range of %, more preferably less than about 0.12% by weight, is the same basis of calculation. In other embodiments of the invention, the total sodium content of the ATH particles used in the filter cake of the practice of the invention Generally, it is in the range of less than about 0.30% by weight, preferably less than about 〇25 % by weight, more preferably less than about 0.20% by weight, based on the ATH particles in the filter cake. The basis of calculation. In still other embodiments of the present invention, the total sodium alkali content of the ATH particles used in the filter cake of the present invention is generally less than about 0.40% by weight based on the ATH particles in the filter cake. Preferably, the range is less than about 〇·3〇% by weight, more preferably less than about 〇·25% by weight, which are all based on the same calculation basis. Honing Drying As discussed above, the present invention relates to honing and drying filter cakes. The honed and dried ATH granules are produced, wherein the ATH granules in the filter cake have the specified properties, as described above. The "honing and drying" and "dry honing" used herein means the turbulence of the filter cake in the honing and drying unit. Drying in a hot gas stream. Honing and drying single -12-200811045 includes a rotor that is firmly mounted on a solid shaft that rotates at a high peripheral speed. In combination with the rotational movement of the high air output, the hot air flowing through is converted into a very fast air whirl, which drives the mixture to be dried (ie the filter cake), accelerates, and distributes and drys the mixture, thus producing a honed dry A Τ Η Particles. The honed dry granules are transported out of the honing machine via the turbulent air after they have been completely dried, and are preferably separated from the hot air and steam using conventional filter systems. In another embodiment of the invention, the honed and dried ruthenium particles are transported through the turbulent air through a turbulent air that is integrated into the honing machine, and then transported through the turbulent air. Machine, and use a conventional filter system to separate from hot air and steam. The output of the hot air used to dry the cake is generally greater than about 3,000 Bm3/hour, preferably greater than about 5,000 Bm3/hour, more preferably greater than about 3,000 Bm3/hour to about 40,000 Bm3/hour, and most preferably about 5,000. Bm3 / hour to about 30,000 Bm3 / hour. To achieve this high output, the rotor of the honing and drying unit typically has a greater than about 40 meters per second, preferably greater than about 60 meters per second, more preferably greater than about 70 millimeters per second, and most preferably about 70 meters per second. The peripheral speed in the range of seconds to about 140 m/s. The high rotational speed of the rotor and the high hot air output result in a hot air flow with a Reynolds number greater than about 3,000. The temperature of the hot gas stream used to honed the dried filter cake is typically greater than about 150 ° C, preferably greater than about 27 (TC. In a more preferred embodiment, the temperature of the hot gas stream is from about 150 ° C to about 55 (the range of TC, preferably in the range of from about 270 ° C to about 500 ° C. In a preferred embodiment, the honed dry filter cake is honed to have a large BET surface area ratio of -13 to 200811045 The dried ATH particles, as determined by DIN-66132, then become the starting ATH particles in the filter cake. Generally, the BET of the honed dry ATH is greater than about 10% of the ATH particles in the filter cake. The BET of the dried ATH is greater than about 10% to about 40% of the ATH particles in the filter cake. More preferably, the BET of the ATH by dry honing is greater than about 10% to about 25% of the ATH particles in the filter cake. The honed dry ATH granules produced can be used "directly" for many applications. However, in some embodiments, the ATH dry ATH granules are further processed to reduce, or in some embodiments, Poly. The formation of cohesive polymers is common in ATH granules, and its presence is acceptable in some applications. The damage affects the properties of the ATH particles in the resin. Therefore, ATH is highly desirable to reduce, preferably to eliminate, the binder. In the practice of the present invention, the amount or cohesive of the cohes present in the honed and dried ATH particles The degree is reduced by subjecting the honed and dried ATH particles to a de-agglomeration process. De-agglomeration · De-agglomeration means that the honed dry ATH particles are subjected to further processing, wherein reduction, in some embodiments Substantially eliminating the amount or degree of cohesiveness present in the honed dry ATH particles (ie, the amount of cohes present in the honed dry ATH particles is greater than the amount of cohes present in the ATH product particles) The amount of honed dry mash has a very small particle size reduction. "Small amount of reduced particle size" means that the d5 ATH of the ATH product particles is greater than or equal to 90% of the honed dry ATH granules. In a preferred embodiment, The d5 crucible after honing and drying ATH is in the range of about -14 - 200811045 90% to about 95% of the honed and dried ATH granules, more preferably about 95% to about 99% of the honed and dried granules. In the practice of the present invention The amount or degree of cohesive mass in the honed dry ATH granules is reduced by the use of an air classifier or a pin honing machine. Air classifiers suitable for use herein include the use of gravity, centrifugal force, inertial force, or any combination thereof. While classifying ATH product particles, the use of these classifiers is known in the art, and those skilled in the art and familiar with the final product size can readily select a classifier containing a suitable mesh and/or screen. Pin honing machines include dry and wet pin honing machines. As with air classifiers, the use of pin honing machines is known in the art, and those skilled in the art and familiar with the final product size can easily select the best pin. A honing machine for specific applications. The de-agglomeration of the ATH by dry honing is carried out under conditions effective to produce ATH product particles having the following discussion. The ATH product particles in accordance with the present invention typically produce ATH product particles generally characterized by a specified total pore volume ratio and/or median pore radius ("r5"), in addition to one or more, preferably by the method of the present invention. Two or more, and more preferably three more, in some embodiments, all of the following features: i) d50 from about 5 to about 2.5 microns; ii) based on the total weight of the ATH product particles a total sodium alkali content of less than about 0.4% by weight; iii) an oil absorption of less than about 50% as determined by ISO 7 87-5: 1 890; and iv) from about 1 to about DIN-66 1 32 A surface area ratio (BET) of 15 square meters per gram, wherein the conductivity of the ATH product particles is less than about 200 pS/cm in water at 10% by weight of ATH. -15- 200811045 As noted above, the inventors believe that for a particular polymer molecule, ATH particles with a higher structured aggregate contain more and larger pores and appear to be more difficult to wet, resulting in, for example, Buss Κο- The kneading machine or twin-screw extruder of the kneader or the difficulty of compounding during the compounding of other machines known in the art and used for this purpose (higher variation in motor power). The inventors have found that the process of the invention is particularly suitable for the manufacture of ruthenium product particles characterized by a small median pore size and/or a small total pore volume, which is associated with improved wetting of the polymeric material, thus resulting in improved The composite behavior, that is, the engine (motor) used for composite composite materials containing the flame retardant resin has a small power variation. The r5G of the ruthenium product particles and the pore volume ratio ("Vmax") at about 1 〇〇〇 can be obtained from mercury porosimetry. The principle of mercury porosimetry is based on the physical principle that non-reactive, non-wetting liquid does not penetrate the pores until sufficient pressure is applied to force it into. Therefore, the higher the pressure required for the liquid to enter the hole, the smaller the porosity. It has been found that a smaller pore size and/or a lower total pore volume ratio is associated with a better wetting force of the ATH product particles. The porosity of the ATH product particles produced herein can be calculated using the Porosimeter 20 00 ^ from Italian Carlo Erba Strum entazione. According to the manual of P o r o s i m e t e r 2 0 0 0, the hole radius r is calculated from the measured pressure p using the following equation: r = -2Ycos(e)/p; where Θ is the wetting angle and γ is the surface tension. The measurement used here uses 141.3 ° and γ is set to 480 dynes/cm. In order to improve the reproducibility of the measurement, it is calculated by the second intrusion test to calculate the porosity of the dried ruthenium particles as described in the manual of Porosimeter 2000. The second test was used because the inventors observed that after the intrusion, that is, after releasing the pressure to the surrounding pressure, the amount of mercury remaining in the sample of the ATH-dried ATH particles was -16-200811045. Thus, r5G can be obtained from this data, as explained below. In a first test, a sample of the ATH product particles produced by the method of the present invention was prepared as described in the manual of Porosimeter 2000, and the pore volume was measured as a function of the applied intrusion pressure P using a maximum pressure of 1000 bar. At the end of the first test, the pressure is released and the ambient pressure is reached. A second intrusion test using the same pure ATH product particle sample from the first test (according to the manual of Porosimeter 2000) was carried out, wherein the pore volume ratio of the second test • V(p) measured the volume V〇 as the new starting volume, Then set it to zero for the second test. In the second intrusion test, the pore volume ratio v(p) of the sample was again measured as a function of the applied intrusion pressure p using a maximum pressure of 1 000 bar. Here, the pore volume at about 1 000 bar (ie for measuring the maximum pressure) is called Vmax °. The second ATH product particle intrusion test is performed, and the Porosmeter 2000 is used to calculate the hole according to the formula r = -2YC〇S(e)/p. Radius r; where Θ is the wetting angle, ® γ is the surface tension, and P is the intrusion pressure. For all r-measures used herein, 141 · 3° is used and γ is set to 480 dynes/cm. If necessary, the hole volume ratio can be plotted against the hole radius r to plot the resulting result. By definition, the pore radius at a relative pore volume ratio / 5 〇% is referred to herein as the pore volume median r 5 〇. For a graph of r5D and Vmax, see U.S. Provisional Patent Application Nos. 60/818,632; 60/818,633; 60/818,670; 60/815,515; and 60/8 1 8,426, all of which are hereby incorporated herein by reference. Into as a reference. -17- 200811045 The above procedure was repeated using a sample of the A Τ product particles produced by the method of the present invention, and it was found that the ruthenium product particles thus produced had r5G in the range of from about 〇·〇9 to about 0.33 μm, i.e., relative pore volume ratio of 50%. The radius of the hole. In certain embodiments of the invention, the ATH product particles have an r50 in the range of from about 0.20 to about 0.33 microns, preferably in the range of from about 〇2 to about 〇·3 microns. In other embodiments, r5G is in the range of from about 0.185 to about 0.325 microns, preferably from about 0.185 to about 0.25 microns. In still other preferred embodiments, r5G is in the range of from about 〇·09 to about 0.21 μm, more preferably in the range of from about 0.09 to about 0.165 μm. The ATH product particles produced by the process of the invention may also be characterized as having a Vmax in the range of from about 300 to about 700 cubic millimeters per gram, i.e., a maximum pore volume ratio of about 1 000 bar. In certain embodiments of the invention, the Vmax of the ATH product particles ranges from about 3 90 to about 480 cubic millimeters per gram, preferably from about 410 to about 450 cubic millimeters per gram. In other embodiments, Vmax is in the range of from about 400 to about 600 cubic millimeters per gram, preferably from about 460 to about 550 cubic millimeters per gram. In still other embodiments, Vmax is in the range of from about 300 to about 700 cubic millimeters per gram, preferably from about 305 to about 550 cubic millimeters per gram. The ATH product particles produced by the process of the invention may also be characterized as having an oil absorption of less than about 50%, and sometimes from about 1 to about 50%, as determined by I S Ο 7 8 7 - 5 : 1 890 . In certain embodiments, the ATH product particles produced by the process of the invention are characterized by having a range of from about 23 to about 30%, preferably from about 24% to about 2 9%, more preferably from about 25% to about 2 9 % oil absorption. In other embodiments, the oxime product particles produced by the process of the present invention have a range of from about 25% to about 40%, preferably from about 25% to about 35%, more preferably about 26%. Oil absorption up to about 30%. In still other embodiments, the ATH product particles produced by the process of the invention are characterized by having a range of from about 25% to about 50%, preferably from about 26% to about 40%, more preferably from about 27% to about 3 2% range of oil absorption. In other embodiments, the oil absorption of the ATH product particles produced by the process of the invention ranges from about 19% to about 23%, and in still other embodiments, the oil absorbing properties of the honed dry ATH particles are From about 21% to about 25%. The ATH product particles produced by the process of the invention may also be characterized as having a BET surface area ratio in the range of from about 1 to about 15 square meters per gram as measured by DIN-66 1 32. In certain embodiments, the ATH product particles produced by the process of the invention have a BET surface area ratio in the range of from about 3 to about 6 square meters per gram, preferably from about 3.5 to about 5.5 square meters per gram. In other embodiments, the ATH product particles produced by the process of the invention have a BET surface area ratio in the range of from about 6 to about 9 square meters per gram, preferably from about 6.5 to about 8.5 square meters per gram. In still other embodiments, the ATH product particles produced by the process of the invention have a BET surface area ratio in the range of from about 9 to about 15 square meters per gram, preferably from about 10.5 to about 1 2.5 square meters per gram. The ATH product particles produced by the process of the invention may also be characterized as having d5G in the range of from about 5 to about 2.5 microns. In certain embodiments, the ATH product particles produced by the process of the invention have a d5G in the range of from about 1.5 to about 2.5 microns, preferably from about 1.8 to about 2.2 microns. In other embodiments, the ATH product particles produced by the process of the invention have a d5G in the range of from about 1.3 to about 2.0 microns, preferably from about 1.4 to about 1.8 microns. In a further embodiment thereof, in its -19-200811045, the ATH product particles produced by the process of the invention have a range of from about 9 to about 1.8 microns, more preferably from about 1.1 to about 1.5 microns, and a method of the invention. The ATH product particles produced may also be characterized as having a total sodium base content of less than about 0.4% by weight based on the ATH product particles. In a particular embodiment, if the soluble sodium base content is AT Η product particle granules, the total sodium alkali content is less than about 0.20% by weight, preferably less than about 5% by weight, more preferably less than about 0.12% by weight, all of which are by weight. The total weight of the product #. In other embodiments, if the soluble sodium base is characteristic of the ruthenium product particles, the total sodium base content is less than about 0.30, preferably less than about 0.25 wt%, based on the total weight of the niobium product. Less than about 0.20% by weight. In other embodiments, if the sodium-sodium content is characteristic of the cerium product particles, the total sodium alkali content is less than about 〇·4〇, preferably less than about 〇·3〇%, based on the total weight of the product particles. Preferably, it is less than about 〇·25% by weight. The total sodium alkali content can be measured according to the above. • The ruthenium product particles produced by the process of the invention may also be characterized as having the thermal stability described in Tables 1, 2 and 3. There are some special particles with a content of 0.18 particles. The weight is listed as -20- 200811045. Table 1 1 wt.%TGA(0C) 2wt.%TGA(°C) Typical 210-225 220 -235 Preferably 210-220 220-230 Better 214-218 224-228 Table 2 1 wt.% TGA (°C) 2wt.% TGA (°C) Typical 200-215 210-225 Preferred 200-210 210 -220 Better 200-205 210-215 Table 3 1 wt.% TGA (°C) 2wt.% TGA (°C) Typical 195-210 205-220 Preferred 195-205 205-215 Better 195-200 205 -210
• 在此使用之熱安定性指ATH產物顆粒之水釋放，而且 可由數種熱分析方法直接評定，如熱重分析（”TGA”），及在 本發明中，ATH產物顆粒之熱安定性係經TGA測量。在測 量前，將ATH產物顆粒樣品在約105 °C之烤箱中乾燥4小 時以移除表面水分。然後以Mettler Toledo使用70微升銘 氧坩堝（起初重量爲約12毫克）在N2 (每分鐘70毫升） 下以如下之加熱速率實行TGA測量：30°C至150°C爲每分 鐘 10°C，150。(：至 3 5 0°C 爲每分鐘 1°C，3 5 0 °C 至60〇。(：爲每 -21- 200811045 分鐘10°C。ATH產物顆粒（如上所述而預先乾燥）之10八 溫度係在1重量％損失及2重量％損失（均按經硏磨乾燥 ΑΤΗ顆粒之重量計）處測量。應注意，上述TGA測量係使 用蓋子覆蓋坩堝而進行。 本發明方法所製造ΑΤΗ產物顆粒亦可特徵爲具有小 於約200 pS/公分範圍，在某些具體實施例中爲小於約150 pS/公分，而且在其他具體實施例中爲小於約100 pS/公分 之導電度。在其他具體實施例中，ATH產物顆粒之導電度 • 在約1〇至約45 pS/公分之範圍。應注意，所有之導電度測 量係對包括水與按溶液計爲約10重量％之經硏磨乾燥ATH 的溶液進行，如下所述。 導電度係使用得自 Weilheim/德國之 Wissenschaftlich-Technische-Werkstatten GmbH 的 MultiLab 540導電度測量儀藉以下步驟測量：將10克之欲 分析樣品與90毫升之去離子水（周溫）在1 00毫升錐形瓶 中以得自 Burgwedel/德國之 Gesellschaft for Labortechnik ® mbH的GFL 3015搖動裝置在最大效能搖動10分鐘。然後 將導電度電極浸於懸浮液中且測量導電度。 本發明方法所製造ATH產物顆粒亦可特徵爲具有按 經硏磨乾燥ATH顆粒計爲小於約〇. 1重量％之可溶性鈉鹼 含量。在其他具體實施例中，ATH產物顆粒可進一步特徵 爲具有大於約〇· 001至約〇·1重量％範圍，在某些具體實施 例中爲約〇 · 02至約0.1重量％範圍之可溶性鈉鹼含量，其 均按ΑΤΗ產物顆粒計。而在其他具體實施例中，ΑΤΗ產物 -22- 200811045 顆粒可進一步特徵爲具有約0.001至小於0.03重量％範圍 ，在某些具體實施例中爲約0.001至小於0.04重量％範圍 ，在其他具體實施例中爲約0.001至小於0.02重量％範圍 之可溶性鈉鹼含量，其均爲相同之計算基礎。可溶性鈉鹼 含量可依照上列步驟測量.。 本發明方法所製造ATH產物顆粒可且較佳爲特徵爲 不溶性鈉鹼含量。雖然實驗證據顯示 ATH之熱安定性與 ATH之總鈉鹼含量有關，發明人已發現且相信，雖然不希 # 望以理論限制，本發明方法所製造ATH產物顆粒之改良熱 安定性與不溶性鈉鹼含量有關。本發明ATH產物顆粒之不 溶性鈉鹼含量一般爲ATH產物顆粒之總鈉鹼含量的約70 至約99.8%之範圍，其餘爲可溶性鈉鹼。在本發明之某些 具體實施例中，ATH產物顆粒之總鈉鹼含量一般按ATH產 物顆粒計爲小於約〇·20重量％之範圍，較佳爲按ATH產物 顆粒計小於約〇. 1 8重量％之範圍，更佳爲按相同之計算基 礎小於約〇. 1 2重量％之範圍。在本發明之其他具體實施例 ® 中，ATH產物顆粒之總鈉鹼含量一般按ATH產物顆粒計爲 小於約〇.3〇重量％之範圍，較佳爲按ATH產物顆粒計小於 約0.25重量％之範圍，更佳爲按相同之計算基礎小於約 0.20重量％之範圍。在本發明之又其他具體實施例中，ATH 產物顆粒之總鈉鹼含量一般按 ATH產物顆粒計爲小於約 0.40重量％之範圍，較佳爲按ATH產物顆粒計小於約0.30 重量％之範圍，更佳爲按相同之計算基礎小於約0.25重量 %之範圍。 -23- 200811045 ATH產物顆粒之用涂 依照本發明之ΑΤΗ顆粒亦可在各種合成樹脂中作爲 阻燃劑。這些阻燃聚合物調配物一般包括至少一種合成樹 脂及阻燃量之依照本發明所製造ΑΤΗ產物顆粒。在某些應 用中，其可將阻燃聚合物調配物模塑及/或擠壓。 在某些應用中，阻燃量之ΑΤΗ產物顆粒通常爲按阻燃 聚合物調配物之重量計爲約5重量％至約9 0重量％之範圍 ，較佳爲按相同之計算基礎約20重量％至約70重量％之範 # 圍。在一個最佳具體實施例中，阻燃量按相同之計算基礎 爲經硏磨乾燥ΑΤΗ顆粒之約30重量％至約65重量％之範 圍。因此含依照本發明所製造ΑΤΗ產物顆粒之阻燃聚合物 調配物一般包括按阻燃聚合物調配物之重量計爲約10至 約95重量％範圍之至少一種合成樹脂，較佳爲阻燃聚合物 調配物之約30至約40重量％範圍，更佳爲按相同之計算 基礎約35至約70重量％範圍的至少一種合成樹脂。 其中可使用 ΑΤΗ產物顆粒之熱塑性樹脂的非限制實 ® 例包括聚乙烯、乙烯-丙烯共聚物、C2至C8烯烴（α-烯烴 )之聚合物與共聚物（如聚丁烯、聚（4-甲基戊烯-1)等 )、這些烯烴與二烯之共聚物、乙烯-丙烯酸酯共聚物、聚 苯乙烯、ABS樹脂、AAS樹脂、AS樹脂、厘83樹脂、乙 烯-氯乙烯共聚物樹脂、乙烯-乙酸乙烯酯共聚物樹脂、乙 烯-氯乙烯·乙酸乙烯酯接枝聚合物樹脂、氯亞乙烯、聚氯 乙烯、氯化聚乙烯、氯乙烯-丙烯共聚物、乙酸乙烯酯樹脂 、苯氧樹脂等。適當合成樹脂之進一步實例包括熱固性樹 •24- 200811045 脂，如環氧樹脂、酚樹脂、三聚氰胺樹脂、不飽和聚酯樹 脂、醇酸樹脂、與脲樹脂，及天然或合成橡膠，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、聚矽氧橡膠，亦包括氟彈 性體、NBR、與氯磺化聚乙烯。其進一步包括聚合懸浮液 (乳膠）。 較佳爲合成樹脂爲聚乙烯爲主樹脂，如高密度聚乙烯 、低密度聚乙烯、線形低密度聚乙烯、超低密度聚乙烯、 EVA (乙烯-乙酸乙烯酯樹脂）、EEA (乙烯-丙烯酸乙酯樹 φ 脂）、EM A (乙烯-丙烯酸甲酯共聚物樹脂）、E A A (乙烯 -丙烯酸共聚物樹脂）、與超高分子量聚乙烯；及〇：2至C8 烯烴（α-烯烴）之共聚物，如聚丁烯與聚（4-甲基戊烯-1 )，聚氯乙烯與橡膠。在一個更佳具體實施例中，合成樹 脂爲聚乙烯爲主樹脂。 阻燃聚合物調配物亦可含此技藝常用之其他添加劑。 適合用於本發明阻燃聚合物調配物之其他添加劑的非限制 實例包括擠壓助劑，如聚乙烯蠟、Si爲主擠壓助劑、脂肪 • 酸；偶合劑，如胺基-、乙烯基-或烷基矽烷或順丁烯二酸 接枝聚合物；硬脂酸鋇或硬脂酸鈣；有機過氧化物；染料 ;顏料；塡料；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；衝擊調節劑； 處理助劑；模具釋放助劑、潤滑劑；抗阻塞劑；其他阻燃 劑；UV安定劑；塑性劑；流動助劑等。如果需要，則晶核 生成劑（如矽酸鈣或靛藍）亦可包括於阻燃聚合物調配物 -25- 200811045 。其他選用添加劑之比例爲習知且可改變以符合任何特定 狀況所需。 阻燃聚合物調配物之成分的倂入及加入方法、及進行 模塑之方法對本發明並不重要，而且可爲任何此技藝已知 ，只要選擇之方法涉及均勻混合及模塑。例如可使用B u s s Κο-捏合機、內部混合器、Farrel連續混合器、或雙螺桿擠 壓器，或在某些情形及單螺桿擠壓器或二輥硏磨機，混合 各以上成分及選用添加劑（如果使用），然後在後續處理 Φ 步驟中模塑阻燃聚合物調配物。此外阻燃聚合物調配物之 模塑物件可在如拉伸處理、壓花處理、塗覆、印刷、電鍍 、穿孔、或切割之製造應用後使用。經捏合混合物亦可充 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。 在擠壓物件之情形，其可使用已知對用於阻燃聚合物 調配物之合成樹脂有效之任何擠壓技術。在一種例示技術 中，其在複合機中將合成樹脂、ATH產物顆粒與選用成分 ^ (如果選擇）複合以形成阻燃樹脂調配物。然後在擠壓機 中將阻燃樹脂調配物加熱至熔化狀態，然後將熔化之阻燃 樹脂調配物經選擇模擠壓以形成擠壓物件，或塗覆例如資 料傳輸用金屬線或玻璃纖維。 在某些具體實施例中，合成樹脂係選自環氧樹脂、酚 醛樹脂、含磷樹脂（如DOPO )、溴化環氧樹脂、不飽和 聚酯樹脂、與乙烯樹脂。在此具體實施例中，阻燃量之ATH 產物顆粒爲每百份樹脂約5至約200份（“phr”）ATH產物顆 -26- 200811045 粒之範圍。在較佳具體實施例中，阻燃調配物包括約1 5至 約1 00 phr，較佳爲約1 5至約75 phr，更佳爲約20至約55 phr之ATH產物顆粒。在此具體實施例中，阻燃聚合物調 配物亦可含常隨這些粒狀樹脂用於此技藝之添加劑。適合 用於此阻燃聚合物調配物之其他添加劑的非限制實例包括 例如溴、磷或氮爲主之其他阻燃劑；溶劑、固化劑，如硬 化劑或加速劑、分散劑或磷化合物，細微矽石、黏土、或 滑石。其他選用添加劑之比例爲習知且可改變以符合任何 Φ 特定狀況所需。此阻燃聚合物調配物之成分的較佳倂入及 加入方法爲高剪切混合。例如使用例如Silvers on Company 製造之頂部混合器剪切。進一步處理樹脂-塡料混合物至「 預漬體」階段然後硬化夾層爲此技藝之常見狀態且敘述於 文獻中，例如 McGraw-Hill Book Company 出版之 ”Handbook of Epoxide Resins”，其在此全部倂入作爲參考 〇 以上之說明係關於數個本發明之具體實施例。熟悉此 ® 技藝者應了解，其可設計帶有本發明精神之同樣有效的其 他方式。亦應注意，本發明之較佳具體實施例預期在此討 論之所有範圍包括任何較低量至任何較高量之範圍。例如 在討論ATH產物顆粒之吸油性時，其預期約30%至約32% 、約19%至約25%、約21%至約27%等之範圍均在本發明 之範圍內。 -27-• Thermal stability as used herein refers to the release of water from ATH product particles and can be directly assessed by several thermal analysis methods, such as thermogravimetric analysis ("TGA"), and in the present invention, the thermal stability of the ATH product particles. Measured by TGA. Samples of the ATH product granules were dried in an oven at about 105 °C for 4 hours to remove surface moisture prior to measurement. The TGA measurement was then carried out with Mettler Toledo using 70 microliters of oxysulfonate (initial weight of about 12 mg) at N2 (70 ml per minute) at a heating rate of 30 ° C to 150 ° C of 10 ° C per minute. , 150. (: to 3 50 ° C is 1 ° C per minute, 350 ° C to 60 ° C. (: 10 ° C per-21-200811045 minutes. 10 ATH product particles (pre-dried as described above) 10 The eight temperature system is measured at a loss of 1% by weight and a loss of 2% by weight (both by weight of the honed dry granules). It should be noted that the above TGA measurement is carried out using a lid covering the crucible. The hydrazine product produced by the method of the present invention The particles may also be characterized as having a range of less than about 200 pS/cm, in some embodiments less than about 150 pS/cm, and in other embodiments less than about 100 pS/cm. In the examples, the conductivity of the ATH product particles is in the range of from about 1 Torr to about 45 pS/cm. It should be noted that all conductivity measurements are honed and dried including water and about 10% by weight of the solution. The solution of ATH was carried out as follows. Conductivity was measured using a MultiLab 540 conductivity meter from Wissenschaftlich-Technische-Werkstatten GmbH in Weilheim/Germany by the following procedure: 10 g of sample to be analyzed and 90 ml of deionized water (Week temperature) Shake for 10 minutes at maximum efficiency in a 100 ml Erlenmeyer flask with a GFL 3015 shaker from Gersellschaft for Labortechnik ® mbH from Burgwedel/Germany. The conductivity electrode was then immersed in the suspension and the conductivity measured. The ATH product particles produced by the process of the present invention may also be characterized as having a soluble sodium base content of less than about 0.1% by weight based on honed dry ATH particles. In other embodiments, the ATH product particles may be further characterized as Having a range of soluble sodium alkalis in the range of from about 〇· 001 to about 1% by weight, in certain embodiments from about 〇·02 to about 0.1% by weight, based on the ruthenium product particles. In particular embodiments, the cerium product-22-200811045 granules can be further characterized as having a range of from about 0.001 to less than 0.03 weight percent, and in certain embodiments from about 0.001 to less than 0.04 weight percent, in other embodiments The soluble sodium alkali content in the range of about 0.001 to less than 0.02% by weight, which are all based on the same calculation. The soluble sodium alkali content can be measured according to the above steps. The ATH product particles produced by the method of the present invention can be and preferably characterized by an insoluble sodium-alkali content. Although experimental evidence indicates that the thermal stability of ATH is related to the total sodium alkali content of ATH, the inventors have discovered and believed that although not It is to be understood by theory that the improved thermal stability of the ATH product particles produced by the process of the present invention is related to the insoluble sodium base content. The insoluble sodium base content of the ATH product particles of the present invention is generally in the range of from about 70 to about 99.8% of the total sodium base content of the ATH product particles, with the balance being soluble sodium base. In some embodiments of the invention, the total sodium alkali content of the ATH product particles is generally less than about 20% by weight based on the ATH product particles, preferably less than about 〇. The range of % by weight, more preferably less than about 0.12% by weight on the same basis. In other embodiments of the present invention®, the total sodium base content of the ATH product particles is generally in the range of less than about 0.3% by weight based on the ATH product particles, preferably less than about 0.25% by weight based on the ATH product particles. The range, more preferably less than about 0.20% by weight on the same basis. In still other embodiments of the invention, the total sodium alkali content of the ATH product particles is generally in the range of less than about 0.40% by weight based on the ATH product particles, preferably less than about 0.30% by weight based on the ATH product particles. More preferably, it is less than about 0.25% by weight on the same basis. -23- 200811045 Coating of ATH product particles The ruthenium particles according to the present invention can also be used as a flame retardant in various synthetic resins. These flame retardant polymer formulations generally comprise at least one synthetic resin and a flame retardant amount of the ruthenium product particles produced in accordance with the present invention. In some applications, it can mold and/or extrude a flame retardant polymer formulation. In certain applications, the flame retardant amount of the cerium product particles is typically in the range of from about 5% by weight to about 90% by weight, based on the weight of the flame retardant polymer formulation, preferably about 20 weights on the same basis. % to about 70% by weight of the ##. In a preferred embodiment, the amount of flame retardant is on the same basis as the range of from about 30% by weight to about 65% by weight of the honed dry enamel granules. Accordingly, the flame retardant polymer formulation comprising the ruthenium product particles produced in accordance with the present invention generally comprises at least one synthetic resin, preferably flame retardant polymerization, in the range of from about 10 to about 95 weight percent, by weight of the flame retardant polymer formulation. The range of from about 30 to about 40% by weight of the formulation, more preferably from about 35 to about 70% by weight, based on the same basis, of at least one synthetic resin. Non-limiting examples of thermoplastic resins in which cerium product particles can be used include polyethylene, ethylene-propylene copolymers, polymers and copolymers of C2 to C8 olefins (α-olefins) (eg, polybutene, poly(4-) Methylpentene-1), etc., copolymer of these olefins and diene, ethylene-acrylate copolymer, polystyrene, ABS resin, AAS resin, AS resin, PCT resin, ethylene-vinyl chloride copolymer resin , ethylene-vinyl acetate copolymer resin, ethylene-vinyl chloride-vinyl acetate graft polymer resin, vinyl chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-propylene copolymer, vinyl acetate resin, benzene Oxygen resin, etc. Further examples of suitable synthetic resins include thermosetting trees • 24-200811045 fats such as epoxy resins, phenolic resins, melamine resins, unsaturated polyester resins, alkyd resins, and urea resins, and natural or synthetic rubbers such as EPDM, D. Base rubber, isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, polyoxyxene rubber, also include fluoroelastomer, NBR, and chlorosulfonated polyethylene. It further comprises a polymeric 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-acrylic acid) Ethyl tree φ lipid), EM A (ethylene-methyl acrylate copolymer resin), EAA (ethylene-acrylic acid copolymer resin), and ultrahigh molecular weight polyethylene; and 〇: 2 to C8 olefin (α-olefin) Copolymers 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 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 wax, Si as the primary extrusion aid, fat acid; coupling agents such as amine-, ethylene Base- or alkyl-decane or maleic acid graft polymer; barium stearate or calcium stearate; organic peroxide; dye; pigment; tanning agent; foaming agent; deodorant; Antioxidant; antistatic agent; strengthening agent; metal scavenger or passivating agent; impact modifier; processing aid; mold release aid, lubricant; anti-blocking agent; other flame retardant; UV stabilizer; plasticizer; Flow aids, etc. If desired, a nucleating agent such as calcium citrate or indigo may also be included in the flame retardant polymer formulation -25- 200811045. The ratio of other optional additives is conventional and can be varied to meet any particular condition. The method of incorporation and addition of the components of the flame retardant polymer formulation, and the method of molding are not critical to the invention, and can be known in any art as long as the method of selection involves uniform mixing and molding. For example, a B uss Κο-kneader, an internal mixer, a Farrel continuous mixer, or a twin-screw extruder, or in some cases a single-screw extruder or a two-roll honing machine, may be used to mix the above components and select The additive, if used, is then molded into a flame retardant polymer formulation in a subsequent processing Φ step. Further, the molded article of the flame retardant polymer formulation can be used after manufacturing applications such as stretching, embossing, coating, printing, plating, perforating, or cutting. 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 extruding articles, it is possible to use any extrusion technique known to be effective for synthetic resins for flame retardant polymer formulations. In one exemplary technique, a synthetic resin, ATH product particles are combined with an optional component ^ (if selected) in a compounding machine to form a flame retardant resin formulation. 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 selective die to form an extruded article, or coated with a metal wire or glass fiber such as a material for transport. In some embodiments, the synthetic resin is selected from the group consisting of epoxy resins, phenolic resins, phosphorus-containing resins (e.g., DOPO), brominated epoxy resins, unsaturated polyester resins, and vinyl resins. In this particular embodiment, the flame retardant amount of ATH product particles is in the range of from about 5 to about 200 parts ("phr") of ATH product particles -26 to 200811045 per hundred parts of resin. In a preferred embodiment, the flame retardant formulation comprises from about 15 to about 100 phr, preferably from about 15 to about 75 phr, more preferably from about 20 to about 55 phr of ATH product particles. In this embodiment, the flame retardant polymer formulation may also contain additives which are often used in the art with such particulate resins. Non-limiting examples of other additives suitable for use in this flame retardant polymer formulation include other flame retardants such as bromine, phosphorus or nitrogen; solvents, curing agents such as hardeners or accelerators, dispersants or phosphorus compounds, Fine vermiculite, clay, or talc. The ratio of other optional additives is conventional and can be varied to meet any Φ specific conditions. A preferred method of incorporation and addition of the components of the flame retardant polymer formulation is high shear mixing. For example, shearing is performed using an overhead mixer such as that manufactured by Silvers on Company. Further processing of the resin-tank mixture to the "pre-stain" stage and then hardening the interlayer is a common state of the art and is described in the literature, for example, "Handbook of Epoxide Resins" by McGraw-Hill Book Company, which is hereby incorporated. The above description is based on a number of specific embodiments of the invention. Those skilled in the art will appreciate that they can be designed to be equally effective in the spirit of the present invention. It should also be noted that the preferred embodiments of the present invention are intended to cover any range of any lower amount to any higher amount. For example, when discussing the oil absorption of ATH product particles, it is contemplated that ranges from about 30% to about 32%, from about 19% to about 25%, from about 21% to about 27%, etc., are within the scope of the invention. -27-