200812913 九、發明說明： 【發明所屬之技術領域】 本發明關於礦物阻燃劑之製造。更特別地’本發明關 於一種用於製造具有改良熱安定性之氫氧化鋁阻燃劑的新 穎方法。 【先前技術】 氫氧化鋁具有多個不同之名稱，如水合鋁、三水合鋁 等，但是通常稱爲ATH。ATH顆粒有許多用途，如在許多 Φ 種材料（例如紙、樹脂、橡膠、塑膠等）中之塡料。這些 產物可用於各種商業應用，如電纜及電線外皮、輸送帶、 熱塑性模具、黏著劑等。ATH —般用於改良此材料之阻燃 性且亦作爲消煙劑。ATH亦常在用於製造印刷電路板之樹 脂中作爲阻燃劑。因此ATH之熱安定性爲最終使用者極爲 注意之品質。例如在印刷電路板應用中，用於建構板之夾 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。然而訂製 ® A T Η等級之需求漸增，而且現行方法無法製造所有這些等 級。因此隨訂製A Τ Η等級之需求增加，用於製造這些等級 之方法的需求亦漸增。 【發明內容】 雖然實驗證據顯不ΑΤΗ之熱安定性與ΑΤΗ之總鈉鹼 含量有關’發明人在此已發現且相信，雖然不希望以理論 限制’本明發明A Τ Η之改良熱安定性與不溶性鈉鹼含量有 關，其一般按總鈉鹼重量計爲總鈉鹼含量之約7 〇至約9 9 200812913 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，A Τ Η顆粒對 樹脂之潤濕力視ΑΤΗ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ΑΤΗ具有改 良潤濕力之A Τ Η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ΑΤΗ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。 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ΑΤΗ產物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絲擠壓機或此技藝 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 胃 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。 因此在一個具體實施例中，本發明製造一種經乾式硏 磨AΤΗ顆粒，其具有約300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，及/或約〇.〇9至約 0.33微米範圍之r5Q，即相對孔體積比50%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 200812913 某些具體實施例中爲全部以下特徵：i)約0·5至約2.5微米 之d5G; ii)按經乾式硏磨ΑΤΗ顆粒之總重量計爲小於約〇.4 重量％之總鈉鹼含量；i i i)按I S Ο 7 8 7 - 5 : 1 9 8 0測定爲小於約 5 0%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)，其中經乾式硏磨ATH顆粒之導 電度在10重量％之ATH於水中測量小於約200 pS/公分。 在另一個具體實施例中，本發明關於一種阻燃樹脂調 配物，其包括本發明方法製造之經乾式硏磨ATH顆粒。 # 在某些具體實施例中，本發明之經乾式硏磨ATH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。 本發明亦關於一種用於製造經乾式硏磨ATH之方法 。此方法通常包括噴霧乾燥氫氧化鋁漿液或濾餅以製造經 噴霧乾燥氫氧化鋁顆粒，及乾式硏磨該經噴霧乾燥氫氧化 鋁顆粒，如此製造在此所述之經乾式硏磨ATH顆粒。 【實施方式】 應注意，在此揭示之所有粒徑測量，即d 5 〇値，係使 ® 用得自Quantachrome之Cilas 1064 L雷射光譜儀藉雷射繞 射測量。通常在此用於測量d5().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 200812913200812913 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the manufacture of mineral flame retardants. More particularly, the present invention relates to a novel process 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, aluminum trihydrate, etc., but is commonly referred to as ATH. ATH particles have many uses, such as those in many Φ materials (such as paper, resin, rubber, plastics, etc.). These products can be used in a variety of commercial applications such as cable and wire sheathing, conveyor belts, thermoplastic molds, adhesives and the like. ATH is generally used to improve the flame retardancy of this material and also as a smoke suppressant. ATH is also commonly used as a flame retardant in resins used in the manufacture of printed circuit boards. Therefore, the thermal stability of ATH is of great concern to the end user. For example, in printed circuit board applications, the thermal stability of the interlayer used to construct the board must be high enough to lead-free soldering. The synthesis and manufacturing methods of ATH are known in the art. However, the demand for custom ® A T Η grades is increasing, and current methods cannot make all of these grades. As the demand for custom A Τ Η grades increases, so does the demand for methods of manufacturing these grades. SUMMARY OF THE INVENTION Although the thermal stability of the experimental evidence is related to the total sodium alkali content of the cockroach, the inventors have discovered and believed here, although it is not desirable to theoretically limit the improved thermal stability of the invention A Τ Η It is related to the content of insoluble sodium alkali, which is generally in the range of about 7 〇 to about 9 9 200812913% by weight of the total sodium base, and the balance is soluble sodium base. The inventors also believe that although it is not desired to be bound by theory, the wetting force of the A Τ Η particles on the resin depends on the morphology of the granules, and the inventors have unexpectedly discovered that the method of the present invention can be used to make improvements with respect to existing bismuth. Wetting force A Τ Η 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 ruthenium 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. The inventors believe that for a particular polymer molecule, the ruthenium 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 in a Buss Κο-kneader. Diffuser (higher variation in motor power) during extrusion or other machines known in the art and used for this purpose. Accordingly, the inventors have 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, thereby resulting in improved composite behavior, i.e., for composite inclusion.引擎 The engine (motor) of the composite machine of the stomach material flame retardant resin has little change in power. The inventors have found that the method of the invention is particularly suitable for use in the manufacture of articles having characteristics. Thus, in one embodiment, the present invention produces a dry honed A ΤΗ particle 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, and/or about 〇.〇9 to r3Q in the range of about 0.33 μm, that is, a pore radius at a relative pore volume ratio of 50%, and one or more, preferably two or more, and more preferably three or more, in 200812913 In some embodiments, all of the following features are: i) d5G from about 0.5 to about 2.5 microns; ii) less than about 0.4% by weight total sodium alkali content based on the total weight of the dry honing particles; Iii) an oil absorption of less than about 50% as determined by IS Ο 7 8 7 - 5 : 1 9 8 ; and iv) a surface area ratio of from about 1 to about 15 square meters per gram as determined by DIN-66 1 32 (BET Wherein the conductivity of the dry honed ATH particles is less than about 200 pS/cm in water at 10% by weight of ATH. In another embodiment, the invention is directed to a flame retardant resin formulation comprising dry honed ATH particles produced by the process of the invention. # In certain embodiments, the dry honed ATH particles of the present invention are further characterized by having a soluble sodium alkali content of less than about 0.1% by weight. The invention also relates to a method for making a dry honed ATH. The method generally comprises spray drying an aluminum hydroxide slurry or filter cake to produce spray dried aluminum hydroxide particles, and dry honing the spray dried aluminum hydroxide particles, thus producing the dry honed ATH particles described herein. [Embodiment] It should be noted that all particle size measurements disclosed herein, i.e., d 5 〇値, were measured by laser diffraction using a Cilas 1064 L laser spectrometer from Quantachrome. The procedure generally used herein for measuring d5() 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 suitable 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 dispersion and during the measurement. After the background measurement is completed, about 75 to about 100 mg of the sample to be measured is placed in a water/dispersant solution.
液之樣品容器中且開始測量。水/分散劑溶液可藉由首先由 5 00克得自KMFLaborchemie之Calgon與3公升得自BASF 之C A L Ρ ο 1 y s a 11製備濃縮物而製備。將此溶液以去離子水 組成1 〇公升。取此原始1 〇公升之1 〇〇毫升繼而以去離子 水進一步稀釋至1 〇公升，及使用此最終溶液作爲上述水-分散劑溶液。 漿液及濾餅 本發明之一個具體實施例將含ATH顆粒之漿液或濾餅 Φ 噴霧乾燥以製造經噴霧乾燥ATH顆粒，然後將其乾式硏磨 ，如此製造經乾式硏磨ATH顆粒。一個較佳具體實施例將 漿液噴霧乾燥，而且另一個較佳具體實施例將濾餅噴霧乾 燥。 漿液或濾餅一般含按漿液或濾餅之總重量計爲約1至 約8 5重量％範圍之ATH顆粒。在某些具體實施例中，漿液 或濾餅含約25至約85重量％範圍之ATH顆粒，在其他具 體實施例中爲約40至約70重量％範圍之ATH顆粒，有時 ® 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，漿液或濾餅含約40至約 60重量％範圍之ATH顆粒，有時爲約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，漿液或濾餅含約25至約50重量％範圍之ATH顆 粒，有時爲約30至約45重量％範圍之ATH顆粒，其均爲 相同之計算基礎。Start the measurement in the sample container of the liquid. The water/dispersant solution can be prepared by first preparing a concentrate from 500 grams of Calgon from KMF Laborchemie and 3 liters of C A L Ρ ο 1 y s a 11 from BASF. This solution was made up of 1 liter of deionized water. One liter of the original 1 liter liter was taken and further diluted to 1 liter liter with deionized water, and the final solution was used as the above water-dispersant solution. Slurry and Filter Cake A specific embodiment of the invention spray-drys a slurry or filter cake Φ containing ATH particles to produce spray dried ATH particles which are then dry honed to produce dry honed ATH particles. A preferred embodiment sprays the slurry, and another preferred embodiment sprays the filter cake. The slurry or filter cake typically contains from about 1 to about 85 weight percent ATH particles, based on the total weight of the slurry or filter cake. In certain embodiments, the slurry or filter cake contains from about 25 to about 85% by weight of ATH particles, and in other embodiments from about 40 to about 70% by weight of ATH particles, sometimes from about 55. ATH particles in the range of up to about 65% by weight, which are all based on the same calculations. In other embodiments, the slurry or filter cake contains from about 40 to about 60 weight percent ATH particles, and sometimes from about 45 to about 55 weight percent ATH particles, which are all based on the same calculations. In still other embodiments, the slurry or filter cake contains from about 25 to about 50 weight percent ATH particles, and sometimes from about 30 to about 45 weight percent ATH particles, which are all based on the same calculations.
用於本發明實務之漿液或濾餅可由任何用於製造ATH 200812913 顆粒之方法得到。在某些具體實施例中，漿液或濾餅係由 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，漿液或濾餅係由一種包括將粗氫氧化鋁 溶於苛性鹼中以形成鋁酸鈉液，將其冷卻及過濾，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1.4:1至約1.55:1範圍之Na20 對Al2〇3莫耳比例。爲了由鋁酸鈉液沉澱ATH顆粒，其將 ATH籽粒以每公升鋁酸鈉液爲約1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Na20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 ΑΤΉ懸浮液一般包括按懸浮液計爲約8 0至約1 60克/公升 之ΑΤΗ。然而ΑΤΗ濃度可改變以落在上述範圍內。然後過 濾及清洗所得ΑΤΗ懸浮液以自其去除雜質，如此形成濾餅 • 。濾餅可以水（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。此濾餅然後可直接噴霧乾燥。 然而在某些具體實施例中，濾餅可以水再漿化形成漿 液，或在一個較佳具體實施例中，將至少一種（較佳爲僅 一種）分散劑加入濾餅形成ΑΤΗ濃度爲上述範圍之漿液。 應注意，以水與分散劑之組合將濾餅再漿化亦在本發明之 範圍內。適合在此使用之分散劑的非限制實例包括聚丙烯 酸酯、有機酸、萘磺酸酯/甲醛縮合物、脂肪醇-聚二醇醚 200812913 、聚丙烯-環氧乙烷、聚二醇酯、多胺-環氧乙烷、磷酸醋 、聚乙烯醇。如果漿液包括分散劑，則因爲分散劑之效應 ，漿液可含按漿液之總重量計爲至多約80重量％之ATH。 在此具體實施例中，其餘漿液或濾餅（即不包括ATH顆粒 及分散劑）一般爲水，雖然某些試劑、污染物等可能因沉 澱而存在。 雖然不希望以理論限制，發明人相信本發明方法製造 之AT Η顆粒的改良形態至少部份地歸因於用於沉澱AT Η之 Φ 方法。因此雖然乾式硏磨技術在此技藝爲已知的，發明人 已發現藉由使用在此所述之沉澱及過濾方法，包括較佳具 體實施例，及在此所述之乾式硏磨方法，可易於製造具有 改良形態之ΑΤΗ顆粒，如下所述。 漿液及/或濾餅中之ΑΤΗ顆粒 在某些具體實施例中，濾餅及/或漿液中 ΑΤΗ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，其較佳爲濾餅及/或漿液中之ATH顆粒具有約1 . 5至 W 約2.5平方米/克範圍之BET。在這些具體實施例中，濾餅 及/或漿液中之ATH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d5〇，其 較在此製造之經乾式硏磨ATH顆粒粗。 在其他具體實施例中，濾餅及/或漿液中 ATH顆粒之 BET爲約4.0至約8.0平方米/克之範圍，較佳爲約5至約 7平方米/克之範圍。在這些具體實施例中，瀘餅及/或漿液 中之ATH顆粒亦可且較佳爲特徵爲約1 . 5至約2.5微米範 -10- 200812913 圍，較佳爲約1.6至約2.0微米範圍之d5 ο，其較在此製造 之經乾式硏磨ΑΤΗ顆粒粗。 在又其他具體實施例中，濾餅及/或漿液中ΑΤΗ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，濾餅及/或 漿液中之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d5G，其較在此 製造之經乾式硏磨AT Η顆粒粗。 Φ 較經乾式硏磨ΑΤΗ顆粒粗表示濾餅及/或漿液中ΑΤΗ 顆粒之d5G値的上限通常爲較在此製造之經乾式硏磨ΑΤΗ 顆粒之d5G値的上限高至少約0.2微米。 用於本發明之漿液及/或濾餅中ATH顆粒亦可且較佳 爲特徵爲按漿液或濾餅中ATH顆粒計爲小於約0.2重量％ 之總鈉鹼含量。在較佳具體實施例中，如果可溶性鈉鹼含 量爲ATH顆粒之特徵，則總鈉鹼含量按漿液及/或濾餅中 ATH顆粒之總重量計小於0 · 1 8重量％，更佳爲小於〇 . 1 2重 量％。AT Η之總鈉鹼含量可使用得自D ii s s e 1 d 〇 r f /德國之D r. 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 -11- 200812913 卻至約室溫，及加入約5 0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2 0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5 00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500毫升量瓶中溶液之ATH顆粒的總鈉鹼含量。 用於本發明之漿液及/或濾餅中ATH顆粒亦可且較佳 爲特徵爲按漿液及/或濾餅中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，濾餅及/或漿液 # 中之ATH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0.0 2至約0.1重量％ 範圍之可溶性鈉鹼含量，其均按瀘餅及/或漿液中之ATH 顆粒計。而在其他具體實施例中，濾餅及/或漿液中之ATH 顆粒可進一步特徵爲具有約0.001至小於0.04重量％範圍 ，.在某些具體實施例爲約0 · 0 0 1至小於0.0 3重量％範圍， 在某些具體實施例爲約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 ^ 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2 0克之樣品轉移至1 〇 〇 〇毫升量瓶中 ，而且在約9 5 °C之水浴中以約2 5 0毫升之去離子水瀝濾約 4 5分鐘。然後將燒瓶冷卻至2 0 °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， 而且藉過濾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。 用於本發明實務之漿液及/或濾餅中AT Η顆粒亦可敘 -12- 200812913 述爲具有總鈉鹼含量之約70至約99.8重量％範圍的在此所 述之不溶性鈉鹼含量，其餘爲可溶性鈉鹼。雖然實驗證據 顯示熱安定性與AT Η之總鈉鹼含量有關，發明人相信，雖 然不希望以理論限制，本發明方法製造之經乾式硏磨ΑΤΗ 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，用於本發明實務之漿液 及/或濾餅中ΑΤΗ顆粒的總鈉鹼含量按漿液及/或濾餅中之 ® ΑΤΗ顆粒計一般爲小於約0·20重量％之範圍，較佳爲按漿 液及/或濾餅中之ΑΤΗ顆粒計小於約0.18重量％之範圍’ 按相同之計算基礎更佳爲小於約〇 · 1 2重量％之範圍。在本 發明之其他具體實施例中，用於本發明實務之漿液及/或濾 餅中ΑΤΗ顆粒的總鈉鹼含量按槳液及/或濾餅中之ΑΤΗ顆 粒計一般爲小於約〇 . 3 0重量％之範圍，較佳爲按漿液及/ 或濾餅中之ΑΤΗ顆粒計小於約〇 · 2 5重量％之範圍，按相同 之計算基礎更佳爲小於約〇·20重量％之範圍。在本發明之 ^ 又其他具體實施例中，用於本發明實務之漿液及/或濾餅中 AT Η顆粒的總鈉鹼含量按漿液及/或濾餅中之AT Η顆粒計 一般爲小於約〇 . 4 0重量％之範圍’較佳爲按漿液及/或濾餅 中之AT Η顆粒計小於約〇 · 3 0重量％之範圍，按相同之計算 基礎更佳爲小於約0.25重量％之範圍。 噴霧乾燥 噴霧乾燥爲一種常用於製造氫氧化鋁之技術。此技術 通常涉及A Τ Η進料（在此爲經硏磨Ατ Η漿液或濾餅）經 -13- 200812913 由使用噴嘴及/或轉動霧化器霧化。然後使經霧化進料接觸 熱氣，一般爲空氣’然後自熱氣流回收經噴霧乾燥ATH。 經霧化進料之接觸可在計數器中或以順流方式進行，而且 可控制氣體溫度、霧化、接觸、及氣體及/或經霧化進料之 流速，以製造具有所需產物性質之ATH顆粒。 經噴霧乾燥ATH之回收可經由使用如過濾之回收技 術達成’或僅在噴霧乾燥器中使經噴霧乾燥顆粒落下而收 集，其可在此移除，但是可使用任何適當之回收技術。較 ® 佳具體實施例藉由使其沉降而自噴霧乾燥器回收經噴霧乾 燥ATH，及螺絲輸送器由噴霧乾燥器回收之繼而藉壓縮空 氣經管線輸送至儲倉中。 噴霧乾燥條件爲習知且易由熟悉此技藝且熟知下述所 需ATH顆粒產物品質者選擇。這些條件通常包括一般爲 250至5 5 0°C間之入口溫度及一般爲105至150°C間之出口 空氣溫度。 然後使經噴霧乾燥ATH接受乾式硏磨。 ^ 乾式硏磨 乾式硏磨表示使經噴霧乾燥ATH接受進一步處理’其 中將經噴霧乾燥ATH予以少量縮減粒徑而使人1}1去黏聚 。「少量縮減粒徑」表示經乾式硏磨ATH之d5()爲噴霧乾 燥前漿液或濾餅中ATH之約4〇 %至約90%範圍。在較佳具 體實施例中，經乾式硏磨AT Η之d5〇爲噴霧乾燥前漿液或 濾餅中A T Η之約6 0 %至約8 0 %範圍，更佳爲噴霧乾燥前漿 液或濾餅中ΑΤΗ之約70%至約75 %範圍內。 -14- 200812913 用於乾式硏磨經噴霧乾燥ATH之硏磨機可選自此技 藝之任何乾式硏磨機。適當乾式硏磨機之非限制實例包括 球或介質硏磨機、圓錐式與迴轉式破碎機、碟式磨粉機、 膠體與輥式硏磨機、篩網式硏磨機與粒化機、鎚式與籠式 硏磨機、銷式與萬用硏磨機、撞擊式硏磨機與破碎機、顎 式破碎機、噴射與流體能量硏磨機、輥式破碎機、碟式硏 磨機、及垂直輥與乾燥盤、振動式硏磨機。 乾式硏磨經噴霧乾燥ATH而回收之經乾式硏磨ATH ^ 可經已知之任何分類技術分類，因爲視使用之乾式硏磨機 而定，在乾式硏磨期間可製造黏聚物。適當分類技術之非 限制實例包括空氣分類。應注意，某些硏磨機具有內建空 氣分類機；如果不爲此情形則可使用分別之空氣分類機。 如果在乾式硏磨中未使用銷式硏磨機，則經乾式硏磨ATH 可在一或多個銷式硏磨機中接受進一步處理。 經噴霧乾燥ATH之乾式硏磨係在有效製造具有在此 討論之性質的經乾式硏磨ATH顆粒之條件下進行。 • 依照本發明之經乾式硏蘑ATH顆粒 通常經噴霧乾燥ATH顆粒之乾式硏磨製造通常特徵 爲具有指定總孔體積比及/或孔半徑中位數（“r5Q”）之經乾 式硏磨ATH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d5〇; ii)按經乾式硏磨ATH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 8 7 - 5:1 9 8 0測定爲小於約 5 0 %之吸油性；及 i v)按 -15- 200812913 DIN-66 1 3 2測定爲約1至約15平方米/克之表面積比（BET) ，其中經乾式硏磨ATH顆粒之導電度在1〇重量％之ATH 於水中測量小於約200 gS/公分。 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A T Η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絲 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 # 之經乾式硏磨ΑΤΗ顆粒特徵爲孔度中位數較小及/或總孔 體積較小，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。 經噴霧乾燥ΑΤΉ顆粒之r5()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 胃 。其發現較小之孔度及/或較低之總孔體積比與經乾式硏磨 ATH顆粒之較佳潤濕力有關。經乾式硏磨ATH顆粒之孔度 可使用得自義大利 Carlo Erba Strumentazione 之 Porosimeter 2 000由得自隶孔隙術之資料計算。依照 Poro simeter 2 000之手冊，其使用以下方程式由測量之壓力 p計算孔半徑！·： r = -2YC〇S(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。 -16 - 200812913 爲了改良測量之再現力，其由第二ATH入侵測試計算 經乾式硏磨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，經乾式硏磨ATH顆粒之樣品中殘留 體積爲Vo之汞量而使用。如此可由此資料得到r5()，如以 下所解釋。 在第一測試中，其如Porosimeter 2000之手冊所述而 製備經乾式硏磨ATH顆粒之樣品，及使用1 000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 之相同純經乾式硏磨 ATH樣品的第二入侵測試（依照 Porosimeter 2 0 00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 〇〇〇巴（即用於測量最大壓力）之孔體積稱爲 V m a X 0 由第二經乾式硏磨 ATH入侵測試，藉 Porosimeter 2〇〇〇依照公式^-2丫〇〇8(0)/?計算孔半徑^;其中0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.Ρ之Θ値且將γ設爲48 0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50%處之孔半徑稱爲 -17- 200812913 孔體積中位數r 5 〇。 對於r5〇及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 6 0/8 1 8，426號，其均在此全部倂入作爲參考。 使用依照本發明經乾式硏磨ATH顆粒之樣品重複上 述步驟，而且發現經乾式硏磨ATH顆粒具有約0.09至約 0.3 3微米範圍之r 5 〇，即相對孔體積比5 0 %處之孔半徑。在 本發明之某些具體實施例中，經乾式硏磨ATH顆粒之r50 # 爲約0.2 0至約0.3 3微米之範圍，較佳爲約0.2至約0.3微 米之範圍。在其他具體實施例中，r 5 〇爲約0.1 8 5至約0.3 2 5 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，r5C爲約0.09至約0.21微米之範 圍，更佳爲約〇 · 〇 9至約0.1 6 5微米之範圍。 經乾式硏磨ATH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1〇〇〇巴之最大孔體積比 。在本發明之某些具體實施例中，經乾式硏磨ATH顆粒之 W 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450至約 5 50立方毫米/克之範圍。在又其他具體實施例中，Vmax爲 約3 0 0至約7 0 0立方毫米/克之範圍，較佳爲約3 5 〇至約5 5 0 立方毫米/克之範圍。 經乾式硏磨 ATH顆粒亦可特徵爲具有按 ISO 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 • 18 - 200812913 之吸油性。在某些具體實施例中，經乾式硏磨ATH顆粒特 徵崑具有約23至約30%範圍，較佳爲約24%至約2 9%範圍 ，更佳爲約2 5 %至約2 8 %範圍之吸油性。在其他具體實施 例中，經乾式硏磨ATH顆粒特徵爲具有約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，經乾式硏磨ATH 顆粒特徵爲具有約25%至約50%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，經乾式硏磨ATH顆粒之吸油性爲約1 9%至約 23 %之範圍，而且在又其他具體實施例中，所製造經乾式 硏磨ATH顆粒之吸油性爲約21 %至約25%之範圍。 經乾式硏磨ΑΤΉ顆粒亦可特徵爲具有按DIN-66 1 3 2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，經乾式硏磨ATH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B E T 表面積比。在其他具體實施例中，經乾式硏磨ATH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，經乾 式硏磨ATH顆粒具有約9至約15平方米/克範圍，較佳爲 約10·5至約12.5平方米/克範圍之BET表面積比。 經乾式硏磨ATH顆粒亦可特徵爲具有約0.5至2.5微 米範圍之d 5 〇。在某些具體實施例中，本發明製造之經乾式 硏磨ATH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d 5 〇。在其他具體實施例中，經乾式硏 -19- 200812913 磨ATH顆粒具有約1 . 3至約2 · 0微米範圍，較佳爲約 至約1.8微米範圍之d5〇。在又其他具體實施例中，經 硏磨ATH顆粒具有約0.9至約1 .8微米範圍，更佳爲靛 至約1.5微米範圍之d50。 經乾式硏磨ATH顆粒亦可特徵爲具有按經乾式 ATH顆粒計爲小於約0.4重量％之總鈉鹼含量。在某些 實施例中，如果可溶性鈉鹼含量爲經乾式硏磨ATH顆 特徵，則總鈉驗含量小於約0.2 0重量％，較佳爲小於約 ϋ 重量％，更佳爲小於約0.1 2重量％，其均按經乾式硏磨 顆粒之總重量計。在其他具體實施例中，如果可溶性 含量爲經乾式硏磨ΑΤΗ顆粒之特徵，則總鈉鹼含量按 式硏磨A Τ Η顆粒之總重量計小於約〇 . 3 0，較佳爲小 0 · 2 5重量％，更佳爲小於約〇 · 2 0重量％。在其他具體 例中，如果可溶性鈉鹼含量爲經乾式硏磨ΑΤΗ顆粒之 ，則總鈉鹼含量按經乾式硏磨ΑΤΗ顆粒之總重量計小 0 · 4 0，較佳爲小於約〇 · 3 0重量％，更佳爲小於約〇 · 2 5 W %。總鈉鹼含量可依照上列步驟測量。 經乾式硏磨ATH顆粒亦可特徵爲具有以下表！、 3所述之熱安定性。 1.4 乾式 硏磨 具體 粒之 0.18 ATH 鈉鹼 經乾 於約 實施 特徵 於約 重量 2及 -20- 200812913 表1 1 wt.%TGA(°C) 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 195-200 205-210 在此使用之熱安定性指經乾式硏磨ATH顆粒之水釋 Φ 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，經乾式硏磨ATH顆粒之熱安定性係經TGA 測量。在測量前，將經乾式硏磨ATH顆粒樣品在約1051： 之烤箱中乾燥4小時以移除表面水分。然後以Mettler Toledo使用70微升鋁氧坩堝（起初重量爲約12毫克）在 N 2 (每分鐘7 0毫升）下以如下之加熱速率實行τ G A測量 ·· 3 〇 °C至1 5 0 °C爲每分鐘1 〇。〇，1 5 0 °C至3 5 0 °C爲每分鐘1 °C，35〇°C至600°C爲每分鐘1〇。〇。經乾式硏磨ATH顆粒 (如上所述而預先乾燥）之T G A溫度係在1重量％損失及 -21 - 200812913 2重量％損失（均按經乾式硏磨A T Η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。 經乾式硏磨ATH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100pS/公分之導電度。在 其他具體實施例中，經乾式硏磨ATH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1 0重量％之經乾式硏磨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 Mult iLab 540導電度測量儀藉以下步驟測量：將1 〇克之欲 分析樣品與90毫升之去離子水（周圍溫度）在1〇〇毫升錐 形瓶中以得自 Burgwedel/德國之 Gesellschaft for Labortechnik mbH的GFL 3015搖動裝置在最大性能搖動 1 〇分鐘。然後將導電度電極浸於懸浮液中且測量導電度。 經乾式硏磨ATH顆粒亦可特徵爲具有按經乾式硏磨 A T Η顆粒計爲小於約0 · 1重量％之可溶性鈉鹼含量。在其他 具體實施例中，經乾式硏磨ΑΤΗ顆粒可進一步特徵爲具有 大於約0.001至約〇·1重量％範圍，在某些具體實施例中爲 約0 · 02至約0 · 1重量％範圍之可溶性鈉鹼含量，其均按經 乾式硏磨ΑΤΗ顆粒計。而在其他具體實施例中，經乾式硏 磨ΑΤΗ顆粒可進一步特徵爲具有約0.001至小於〇.〇3重量 %範圍，在某些具體實施例中爲約0.001至小於0.04重量％ -22- 200812913 範圍，在其他具體實施例中爲約0 · 0 0 1至小於〇 . 〇 2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。 經乾式硏磨ΑΤΗ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ΑΤΗ之熱安定性與ΑΤΗ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’本發明方法製造之經乾式硏磨ΑΤΗ顆粒的改良熱安定 性與不溶性鈉鹼含量有關。本發明經乾式硏磨ΑΤΗ顆粒之 ^ 不溶性鈉鹼含量一般爲經乾式硏磨ΑΤΗ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，經乾式硏磨ΑΤΗ顆粒之總鈉鹼含量 一般按經乾式硏磨A Τ Η計爲小於約0.2 0重量％之範圍，較 佳爲按經乾式硏磨ΑΤΗ計小於約0.18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，經乾式硏磨ΑΤΗ顆粒之總鈉鹼含量 一般按經乾式硏磨ΑΤΗ計爲小於約〇 · 3 0重量％之範圍，較 ^ 佳爲按經乾式硏磨ΑΤΗ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〇 · 2 〇重量％之範圍。在本發明 之又其他具體實施例中，經乾式硏磨ΑΤΗ顆粒之總鈉驗含 量一般按經乾式硏磨ΑΤΗ計爲小於約〇·4〇重量％之範圍’ 較佳爲按經乾式硏磨ΑΤΗ計小於約〇·3〇重量％之範圍’更 佳爲按相同之計算基礎小於約〇·25重量％之範圍。 經乾式硏磨ΑΤΗ之用途 依照本發明之經乾式硏磨ΑΤΗ顆粒可在各種合成樹 -23- 200812913 脂中作爲阻燃劑。因此在一個具體實施例中，本發明關於 一種包括至少一種，在某些具體實施例中爲僅一種合成樹 脂，及阻燃量之依照本發明經乾式硏磨ATH顆粒的阻燃聚 合物調配物，及由阻燃聚合物調配物製造之模塑及/或擠壓 物件。 阻燃量之經乾式硏磨ATH顆粒通常表示按阻燃聚合 物調配物之重量計爲約5重量％至約90重量％之範圍，較 佳爲按相同之計算基礎約20重量％至約90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 乾式硏磨ATH顆粒之約30重量％至約65重量％之範圍。 因此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1 0至約9 5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3 0至約4 0重量％範圍，更佳 爲按相同之計算基礎約3 5至約7 0重量％範圍的至少一種 合成樹脂。 其中可使用ATH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、MBS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脂，如 -24- •200812913 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EP DM、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 月旨）、EMA (乙烯-丙烯酸甲酯共聚物樹脂）、EAA (乙烯 -丙烯酸共聚物樹脂）、與超高分子量聚乙烯；及C2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、S i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- 200812913 。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Buss Ko-捏合機、內部混合器、Farrel連續混合器、或雙螺絲擠 壓器，或在某些情形及單螺絲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 • 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、經乾式硏磨ATH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，阻燃量之經 乾式硏磨A T Η顆粒爲每百份樹脂約5至約2 0 〇份（“ p h r ”） -26- 200812913 % * ATH之範圍。在較佳具體實施例中，阻燃調配物包括約1 5 至約100 phr，較佳爲約15至約75 phr，更佳爲約20至約 5 5 phr之經乾式硏磨ATH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S il ver son 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 ” Hand book of Epoxide Resins”，其在此全部倂入作爲參考 ο 以上之說明係關於數個本發明之具體實施例。熟悉此 A 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 在討論經乾式硏磨ΑΤΗ之吸油性時，其預期約3〇%至約 3 2%、約19%至約25%、約21 %至約2 7%等之範圍均在本發 明之範圍內。 -27-The slurry or filter cake used in the practice of the present invention can be obtained by any of the methods used to make ATH 200812913 pellets. In some embodiments, the slurry or filter cake is obtained by a process involving the manufacture of ATH particles by precipitation and filtration. In an exemplary embodiment, the slurry or filter cake is formed by a process comprising dissolving the crude aluminum hydroxide in caustic to form a sodium aluminate solution, cooling and filtering, thereby forming an aluminum that can be used in the exemplary embodiment herein. The sodium liquid method is obtained. The sodium aluminate solution so produced generally has a Na20 to Al2〇3 molar ratio ranging from about 1.4:1 to about 1.55:1. In order to precipitate ATH particles from a sodium aluminate solution, the ATH grain is added to the sodium aluminate solution in an amount of about 1 gram 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. The ATH particles are added to the sodium aluminate solution when the sodium aluminate solution is at a liquid temperature of from about 45 to about 80 °C. After the addition of the ATH kernel, the process mixture is stirred for about 1 hour, or until the Na20 to Al2〇3 molar ratio is in the range of from about 2.2:1 to about 3.5:1, thus forming an ATH suspension. The resulting hydrazine suspension typically comprises from about 80 to about 1 60 grams per liter by weight of the suspension. However, the cerium concentration may be varied to fall within the above range. The resulting ruthenium suspension is then filtered and washed to remove impurities therefrom, thus forming a filter cake. The filter cake may be washed once with water, preferably with demineralized water, or more than once in some embodiments. This filter cake can then be spray dried directly. In some embodiments, however, the filter cake may be repulped in water to form a slurry, or in a preferred embodiment, at least one (preferably only one) dispersant is added to the filter cake to form a cerium concentration within the above range. Slurry. It should be noted that it is also within the scope of the invention to repulse the filter cake in a combination of water and dispersant. Non-limiting examples of dispersants suitable for use herein include polyacrylates, organic acids, naphthalene sulfonate/formaldehyde condensates, fatty alcohol-polyglycol ethers 200812913, polypropylene-ethylene oxide, polyglycol esters, Polyamine-ethylene oxide, phosphoric acid vinegar, polyvinyl alcohol. If the slurry comprises a dispersing agent, the slurry may contain up to about 80% by weight of ATH, based on the total weight of the slurry, due to the effect of the dispersing agent. In this particular embodiment, the remaining slurry or filter cake (i.e., excluding ATH particles and dispersant) is typically water, although certain reagents, contaminants, and the like may be present as a result of precipitation. While not wishing to be bound by theory, the inventors believe that the improved morphology of the AT ruthenium particles produced by the process of the present invention is at least partially attributed to the Φ process for precipitating AT 。. Thus, while dry honing techniques are known in the art, the inventors have discovered that by using the precipitation and filtration methods described herein, including the preferred embodiments, and the dry honing methods described herein, It is easy to manufacture ruthenium particles having an improved morphology as described below. The ruthenium particles in the slurry and/or filter cake. In certain embodiments, the BET of the ruthenium particles in the filter cake and/or slurry ranges from about 1.0 to about 4.0 square meters per gram. In these embodiments, it is preferred that the ATH particles in the filter cake and/or slurry have a BET in the range of from about 1.5 to about 2.5 square meters per gram. In these embodiments, the ATH particles in the filter cake and/or slurry 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 more The dry honed ATH particles of this manufacture were coarse. In other embodiments, the BET of the ATH particles in the filter cake and/or slurry ranges from about 4.0 to about 8.0 square meters per gram, preferably from about 5 to about 7 square meters per gram. In these embodiments, the ATH particles in the cake and/or slurry may also preferably be characterized by a range of from about 1.5 to about 2.5 microns, from about 0.01 to about 12,129,13, preferably from about 1.6 to about 2.0 microns. D5 ο, which is coarser than the dry honing granules manufactured here. In still other embodiments, the BET of the ruthenium particles in the filter cake and/or slurry 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 and/or slurry may also and preferably have a d5G in the range of from about 1.5 to about 2.0 microns, preferably from about 1.5 to about 1.8 microns. The dry honed AT Η particles produced here are coarse. Φ The coarser than the dry honing granules, the upper limit of the d5G 値 of the granules in the filter cake and/or slurry is typically at least about 0.2 microns above the upper limit of the d5G 値 of the dry honed granules produced herein. The ATH particles used in the slurry and/or filter cake of the present invention may also and preferably are characterized by a total sodium alkali content of less than about 0.2% by weight based on the ATH particles in the slurry or filter cake. In a preferred embodiment, if the soluble sodium base content is characteristic of the ATH particles, the total sodium alkali content is less than 0 · 18% by weight, more preferably less than the total weight of the ATH particles in the slurry and/or filter cake. 〇. 1 2% by weight. The total sodium content of the AT can be measured using an M7DC flame photometer from D ii s s e 1 d 〇 r f / Dr. Bruno Lange GmbH, Germany. In the present invention, the total sodium alkali 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 -11-200812913 to about room temperature, and about 50 ml of deionized water is added to dissolve 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 vial, then filled with deionized water and shaken to homogenize. The total sodium base content of the ATH particles of the solution in the 500 ml volumetric flask was then analyzed by flame photometer. The ATH particles used in the slurry and/or filter cake of the present invention may also and preferably are characterized by a soluble sodium base content of less than about 0.1% by weight based on the ATH particles in the slurry and/or filter cake. In other embodiments, the ATH particles in the filter cake and/or slurry # can be further characterized as having a range from greater than about 0.001 to about 0.1% by weight, and in certain embodiments from about 0.02 to about 0.1% by weight. The soluble sodium base content, which is based on the ATH particles in the cake and/or slurry. In still other embodiments, the ATH particles in the filter cake and/or slurry can be further characterized as having a range of from about 0.001 to less than 0.04% by weight, and in certain embodiments from about 0. 0 0 1 to less than 0.03 The % by weight range, in some embodiments, is from about 0.001 to less than 0.02% by weight of the soluble sodium base content, which are all based on the same calculations. The soluble sodium alkali content ^ is measured by a flame photometer. To measure the soluble sodium base content, a sample solution was prepared as follows: 20 grams of the sample was transferred to a 1 inch milliliter vial, and about 250 ml of deionized water was used in a water bath at about 95 °C. Leach for about 4 5 minutes. The flask was then cooled to 20 ° C, filled with deionized water to the calibration mark, and shaken homogenized. After the sample settles, a clear solution is formed at the neck of the bottle, and the solution required for the measurement of the flame photometer can be removed from the flask by means of a filter cartridge or using a centrifuge. The AT Η granules used in the slurry and/or filter cake of the present invention are also described as having an insoluble sodium base content as described herein having a total sodium alkali content ranging from about 70 to about 99.8% by weight. The rest is soluble sodium base. Although experimental evidence indicates that thermal stability is related to the total sodium alkali content of AT, the inventors believe that although it is not desired to be bound by theory, the improved thermal stability of the dry honing granules produced by the method of the present invention is related to the insoluble sodium alkali content. It 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 certain embodiments of the invention, the total sodium alkali content of the cerium particles used in the slurry and/or filter cake of the present invention is generally less than about 0 based on the granules in the slurry and/or filter cake. The range of 20% by weight, preferably less than about 0.18% by weight based on the granules in the slurry and/or filter cake, is more preferably in the range of less than about 0.12% by weight on the same basis. In other embodiments of the present invention, the total sodium alkali content of the cerium particles used in the slurry and/or filter cake of the present invention is generally less than about 〇. 3 based on the cerium particles in the slurry and/or filter cake. The range of 0% by weight, preferably in the range of less than about 5% by weight based on the cerium particles in the slurry and/or filter cake, is more preferably less than about -20 % by weight based on the same calculation. In still other embodiments of the present invention, the total sodium alkali content of the AT Η particles in the slurry and/or filter cake used in the practice of the present invention is generally less than about 0.01% by weight of the AT Η particles in the slurry and/or filter cake. 4. The range of 40% by weight is preferably in the range of less than about 〇·30% by weight based on the AT Η particles in the slurry and/or the filter cake, and more preferably less than about 0.25% by weight based on the same calculation. range. Spray Drying Spray drying is a technique commonly used in the manufacture of aluminum hydroxide. This technique typically involves the A Τ Η feed (here the honed Α Η slurry or filter cake) is atomized by the use of a nozzle and/or a rotary atomizer via -13- 200812913. The atomized feed is then contacted with hot gas, typically air' and then spray dried ATH is recovered from the hot gas stream. The contacting of the atomized feed can be carried out in a counter or in a cocurrent manner, and the temperature of the gas, atomization, contact, and gas and/or the flow rate of the atomized feed can be controlled to produce an ATH having the desired product properties. Particles. The recovery of the spray dried ATH can be achieved by using a recovery technique such as filtration or by simply dropping the spray dried granules in a spray dryer, which can be removed there, but any suitable recovery technique can be used. The preferred embodiment of the present invention recovers the spray dried ATH from the spray dryer by allowing it to settle, and the screw conveyor is recovered by the spray dryer and then delivered to the storage bin via compressed air. Spray drying conditions are conventional and are readily selected by those skilled in the art and well known for the quality of the ATH particulate product desired below. These conditions typically include an inlet temperature of typically between 250 and 550 °C and an outlet air temperature of between 105 and 150 °C. The spray dried ATH is then subjected to dry honing. ^ Dry honing Dry honing means that the spray-dried ATH is subjected to further treatment, wherein a spray-dried ATH is used to reduce the particle size in a small amount to cause the human 1}1 to deagglomerate. "Small amount of reduced particle size" means d5 () by dry honing ATH is in the range of about 4% to about 90% of ATH in the spray drying slurry or filter cake. In a preferred embodiment, d5〇 of the dry honing AT 〇 is in the range of about 60% to about 80% of the AT Η in the spray drying slurry or the filter cake, more preferably the pre-spray drying slurry or filter cake. About 70% to about 75% of the lieutenant. -14- 200812913 The honing machine for dry honing spray-dried ATH can be selected from any dry honing machine of the art. Non-limiting examples of suitable dry honing machines include ball or media honing machines, conical and rotary crushers, dish mills, colloid and roller honing machines, screen honing machines and granulators, Hammer and cage honing machine, pin and universal honing machine, impact honing machine and crusher, jaw crusher, jet and fluid energy honing machine, roller crusher, disc honing machine And vertical rolls and drying discs, vibratory honing machines. Dry honing dry honing of ATH by spray drying of ATH can be classified by any of the known classification techniques, as it can be made during dry honing depending on the dry honing machine used. Non-limiting examples of appropriate classification techniques include air classification. It should be noted that some honing machines have built-in air sorters; if this is not the case, separate air sorters may be used. If a pin honing machine is not used in dry honing, the dry honing ATH can be further processed in one or more pin honing machines. The dry honing of the spray dried ATH is carried out under conditions effective to produce dry honed ATH particles having the properties discussed herein. • Dried oyster mushrooms ATH granules in accordance with the present invention are typically manufactured by dry honing of spray dried ATH granules, typically characterized by dry honing ATH with a specified total pore volume ratio and/or median pore radius ("r5Q"). The particles, in addition to one or more, preferably two or more, and more preferably three more, in some embodiments are all of the following features: i) d5 about 5 to about 2.5 microns. Ii) less than about 0.4% by weight total sodium alkali content based on the total weight of the dry honed ATH granules; iii) less than about 50% oil absorbing according to ISO 7 8 7 - 5:1 890 And iv) as determined by -15-200812913 DIN-66 1 3 2 to a surface area ratio (BET) of from about 1 to about 15 square meters per gram, wherein the dry-honed ATH particles have a conductivity of 1% by weight of ATH. The measurement in water is less than about 200 gS/cm. As noted above, the inventors believe that for certain polymer molecules, AT ruthenium particles with higher structured aggregates contain more and larger pores and appear to be more difficult to wet, resulting in, for example, a Buss Κο-kneader. Difficulty in the kneading machine or double screw extruder or other machines known in the art and used for this purpose (higher variation in motor power). The inventors have discovered that the dry honing particles of the present invention are characterized by a small median porosity and/or a small total pore volume which is associated with improved wetting of the polymeric material, thereby resulting in improved composite behavior. That is, the engine (motor) for the composite machine containing the composite flame retardant resin has a small power variation. The r5() of the spray dried cerium particles and the pore volume ratio ("Vmax") at about 1 mbar 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 is. 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 dry honed ATH particles. The porosity of the ATH granules by dry honing can be calculated using the Porosimeter 2 000 from the Italian Carlo Erba Strumentazione. According to the Poro simeter 2 000 manual, the hole radius is calculated from the measured pressure p using the following equation! ·: r = -2YC〇S(e)/p; where Θ is the wetting angle and γ is the surface tension. The measurement used here uses 141.3° and sets γ to 480 dynes/cm. -16 - 200812913 In order to improve the reproducibility of the measurement, the porosity of the dry honing particles is calculated by the second ATH intrusion test, as described in the manual of Porosimeter 2000. The second test was used because the inventors observed the amount of residual mercury in the sample of dry-honed ATH particles after the intrusion, i.e., after releasing the pressure to ambient pressure. Thus, r5() can be obtained from this data, as explained below. In the first test, a sample of dry honed ATH particles was prepared as described in the manual of Porosimeter 2000, and the pore volume was measured as a function of the applied invasive pressure P using a maximum pressure of 1 000 bar. At the end of the first test, the pressure is released and the ambient pressure is reached. Perform a second intrusion test using the same pure dry-honed ATH sample from the first test (according to the manual of Porosimeter 2000), where the second test has a pore volume ratio V(p) measured by taking the volume V〇 as a new Start volume and 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. In ® this will be at a volume of about 1 〇〇〇 (ie used to measure the maximum pressure) called V ma X 0 by the second dry honing ATH intrusion test, by Porosimeter 2〇〇〇 according to the formula ^-2丫〇〇8(0)/? Calculate the hole radius ^; where 0 is the wetting angle 'γ is the surface tension, and p is the intrusive pressure'. For all r-measures used herein, 141. Ρ is used and γ is set to 48 dynes/cm. If desired, the pore volume ratio can be plotted against the pore radius r to plot the resulting result. By definition, the radius of the hole at a relative pore volume ratio of 50% is referred to herein as the median r 5 孔 of the pore volume of -17-200812913. For a graph of r5〇 and Vmax, see US 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 incorporated herein by reference. reference. The above procedure was repeated using a sample of dry-honed ATH particles in accordance with the present invention, and it was found that the dry honed ATH particles have a r 5 范围 in the range of from about 0.09 to about 0.3 3 microns, i.e., a pore radius at a relative pore volume ratio of 50%. . In some embodiments of the invention, the r50# of the dry honed ATH particles ranges from about 0.20 to about 0.33 microns, preferably from about 0.2 to about 0.3 microns. In other embodiments, r 5 〇 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, r5C is in the range of from about 0.09 to about 0.21 microns, more preferably in the range of from about 〇 〇 9 to about 0.1 6 5 microns. The dry honing of the ATH particles can 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 bar. In some embodiments of the invention, the dry honing ATH particles have a W Vmax in the range of 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 450 to about 50 50 cubic millimeters per gram. In still other embodiments, Vmax is in the range of from about 300 to about 750 cubic millimeters per gram, preferably from about 3 5 Torr to about 550 cubic millimeters per gram. The dry honing ATH particles may also be characterized as having an oil absorption of less than about 50% as measured by ISO 7 8 7 - 5 : 1 890, and sometimes in the range of from about 1 to about 50% • 18 - 200812913. In some embodiments, the dry honed ATH particles feature a range of from about 23 to about 30%, preferably from about 24% to about 2 9%, more preferably from about 25% to about 28%. Range of oil absorption. In other embodiments, the dry honed ATH particles are characterized as having an oil absorption in the range of from about 25% to about 40%, preferably from about 25% to about 35%, more preferably from about 26% to about 30%. Sex. In still other embodiments, the dry honed ATH particles 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 32%. Oil absorption. In other embodiments, the oil absorbing properties of the dry honed ATH particles range from about 19.9% to about 23%, and in still other embodiments, the oil absorbing properties of the dry honed ATH particles are produced. It is in the range of about 21% to about 25%. The dry honing granules can 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-66 131. In some embodiments, the dry honed ATH particles have a B E T surface area ratio ranging 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 dry honed ATH particles 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 dry honed ATH particles 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 12.5 square meters per gram. The dry honing of the ATH particles can also be characterized as having d 5 范围 in the range of from about 0.5 to 2.5 microns. In certain embodiments, the dry honed ATH particles produced by the present invention have a d 5 范围 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 dry ATH -19-200812913 abrasive ATH particles have a d5 范围 in the range of from about 1.3 to about 2.0 microns, preferably from about to about 1.8 microns. In still other embodiments, the honed ATH particles have a range of from about 0.9 to about 1.8 microns, more preferably from about 1.5 to about d50. The dry honing of the ATH particles can also be characterized as having a total sodium alkali content of less than about 0.4% by weight based on dry ATH particles. In certain embodiments, if the soluble sodium alkali content is dry honed ATH characteristics, the total sodium content is less than about 0.20% by weight, preferably less than about 9% by weight, more preferably less than about 0.12 by weight. %, which are based on the total weight of the dry honing particles. In other embodiments, if the soluble content is characterized by dry honing of the granules, the total sodium alkali content is less than about 〇.30, preferably less than 0, based on the total weight of the 硏A Τ Η particles. 25% by weight, more preferably less than about 〇·20% by weight. In other specific examples, if the soluble sodium alkali content is dry honing granules, the total sodium alkali content is less than 0.440, preferably less than about 〇·3, based on the total weight of the dry honing granules. 0% by weight, more preferably less than about 〇·25 W%. The total sodium base content can be measured according to the procedure listed above. Dry honing of ATH particles can also be characterized as having the following table! 3, the thermal stability described. 1.4 Dry honing of specific granules 0.18 ATH Sodium base dried to about approx. 2 and -20- 200812913 Table 1 1 wt.% TGA (°C) 2wt% TGA (°C) Typical 210-225 220- 235 Preferred 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 Thermal stability as used herein refers to the release of water by dry honing of ATH particles, and can be directly assessed by several thermal analysis methods, such as thermogravimetric analysis (, TGA), and in the present invention, dry The thermal stability of the honed ATH granules was measured by TGA. The dry honed ATH granule samples were dried in an oven at about 1051 for 4 hours to remove surface moisture before measurement. Then 70 liters of aluminum was used with Mettler Toledo. Oxygen oxime (initial weight of about 12 mg) was carried out at N 2 (70 ml per minute) at a heating rate as follows: 3 〇 ° C to 150 ° C was 1 每 per minute. 1 5 0 °C 3 50 ° C is 1 ° C per minute, 35 ° ° C to 600 ° C is 1 每 per minute. 〇. Dry honing ATH granules (pre-dried as described above) TGA temperature is 1% by weight Loss and -21 - 200812913 2% by weight loss (both by weight of dry honed AT Η particles). It should be noted that the above TGA measurement is carried out using a lid covering 坩埚. Dry honing ATH particles can also be characterized To have 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 other embodiments, The dry honing ATH particles have a conductivity ranging from about 1 〇 to about 45 pS/cm. It should be noted that 'all conductivity measurements are dry ATH ATH including water and about 10% by weight of solution. Solution # was carried out as follows. Conductivity was measured using the Mult iLab 540 conductivity meter from Wissenschaftlich-Technische-Werkstatten GmbH in Weilheim/Germany by the following procedure: 1 gram of sample to be analyzed and 90 ml of deionized Water (week Temperature) GFL 3015 shaking device 1〇〇 ml Erlenmeyer flask at from Burgwedel / Germany by shaking Gesellschaft for Labortechnik mbH 1 billion minutes at maximum performance. The conductivity electrode was then immersed in the suspension and the conductivity was measured. The dry honing of the ATH particles can also be characterized as having a soluble sodium alkali content of less than about 0.1% by weight based on dry honed A T Η particles. In other embodiments, the dry honing particles can be further characterized as having a range from greater than about 0.001 to about 0.1% by weight, and in certain embodiments from about 0. 02 to about 0. 1% by weight. The soluble sodium alkali content is calculated by dry honing granules. In still other embodiments, the dry honing granules can be further characterized as having a range of from about 0.001 to less than 〇. 〇 3 wt%, and in certain embodiments from about 0.001 to less than 0.04 wt% -22- 200812913 The range, in other specific embodiments, is from about 0. 0 0 1 to less than 〇. 2% by weight of the soluble sodium base content, which are all based on the same calculation basis. The soluble sodium base content can be measured according to the procedure listed above. The dry honing of the granules can be and is preferably characterized by an insoluble sodium base content. Although experimental evidence indicates that the thermal stability of strontium is related to the total sodium content of strontium, the inventors have discovered and believed that although it is not desired to theoretically limit the improved thermal stability and insolubility of the dry honing granules produced by the method of the present invention. The sodium base content is related. The insoluble sodium base content of the dry honing granules of the present invention is generally in the range of from about 70 to about 99.8% of the total sodium alkali content of the dry honing granules, with the balance being soluble sodium base. In some embodiments of the present invention, the total sodium alkali content of the dry honing granules is generally less than about 0.20% by weight of dry honing A Τ ,, preferably by dry honing The range is less than about 0.18 wt%, more preferably less than about 0.12 wt% on the same basis. In other specific embodiments of the present invention, the total sodium alkali content of the dry honing granules is generally in the range of less than about 〇·30% by weight based on dry honing, which is preferably dry honing. The oxime is less than about 0.25 wt%, more preferably less than about 〇·2 〇 wt% on the same basis. In still other embodiments of the present invention, the total sodium content of the dry honing granules is generally in the range of less than about 〇·4 〇 wt% by dry honing ', preferably by dry honing. The range of less than about 〇·3〇% by weight is more preferably less than about 〇·25% by weight on the same basis. Use of dry honing 经 The dried honing granules according to the present invention can be used as a flame retardant in various synthetic tree -23-200812913 greases. Accordingly, in one embodiment, the present invention is directed to a flame retardant polymer formulation comprising at least one, in some embodiments, only one synthetic resin, and a flame retardant amount of dry honing ATH particles in accordance with the present invention. And molded and/or extruded articles made from flame retardant polymer formulations. The flame retardant dry honing ATH granules generally represent from about 5% by weight to about 90% by weight, preferably from about 20% by weight to about 90% by weight of the flame retardant polymer formulation. The range of % by weight. In a preferred embodiment, the amount of flame retardant is on the same basis as from about 30% to about 65% by weight of the dry honed ATH particles. Accordingly, the flame retardant polymer formulation generally comprises at least one synthetic resin in the range of from about 10 to about 95 weight percent, preferably from about 30% by weight of the flame retardant polymer formulation, preferably from about 30% to the flame retardant polymer formulation. A range of about 40% by weight, more preferably at least one synthetic resin in the range of from about 35 to about 70% by weight based on the same calculation basis. Non-limiting examples of thermoplastic resins in which ATH particles can be used include polymers and copolymers of polyethylene, ethylene-propylene copolymers, C2 to C8 olefins (alpha-olefins) (eg, polybutene, poly(4-A) Pyridyl-1), etc., copolymer of these olefins and diene, 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, vinyl chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-propylene copolymer, vinyl acetate resin, phenoxy resin Wait. Further examples of suitable synthetic resins include thermosetting resins such as -24-200812913 epoxy resins, phenol resins, melamine resins, unsaturated polyester resins, alkyd resins, and urea resins, and natural or synthetic rubbers such as EP DM, Butyl rubber, isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, polyoxyxene rubber, also include fluoroelastomers, NBR, and chlorosulfonated polyethylene. It further comprises a polymerization suspension (latex). Preferably, the synthetic resin is a polyethylene-based resin such as high density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, • EVA (ethylene). Vinyl acetate resin), EEA (ethylene-ethyl acrylate resin), EMA (ethylene-methyl acrylate copolymer resin), EAA (ethylene-acrylic copolymer resin), and ultrahigh molecular weight polyethylene; and C2 to A copolymer of C8 olefin (α-olefin) 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, S i as the primary extrusion aid, fatty acids; coupling agents such as amine-, ethylene Base- or alkyl decane or maleic acid graft polymer; strontium stearate or calcium stearate; organic peroxide; dye; pigment; sputum, 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; ; flow aids, etc. If desired, a nucleating agent such as calcium citrate or indigo may also be included in the flame retardant polymer formulation -25-200812913. 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 Buss Ko-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 various components and additives. (If used), then mold the flame retardant polymer formulation in a subsequent treatment 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, dry honed ATH granules, and optional ingredients (if selected) are compounded 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 data transmission. 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 embodiment, the flame retarded amount of dry honed A T Η particles is in the range of from about 5 to about 20 parts per hundred parts of resin (" p h r ") -26 - 200812913 % * ATH. 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 dry honed ATH granules. In this particular 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 the requirements of any particular situation. 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 the Silverson 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, "Hand book of Epoxide Resins" by McGraw-Hill Book Company, which is hereby incorporated herein by reference. The above description is directed to 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 dry honing, it is expected that the range of about 3% to about 32%, about 19% to about 25%, about 21% to about 27%, etc. is within the scope of the present invention. Inside. -27-