201219484 六、發明説明： 【發明所屬之技術領域】 本發明係’-種拉伸強度、f曲強度、衝擊強度等 特性優異，纖維素纖維粉末之分散性優異之聚縮^脂組: 物及其製造方法。 ' 【先前技術】 聚縮醛樹脂係於機械特性、熱特性、電氣特性、滑動性 成形性等方面具有優異之特性’主要作為結構材料或機構零 件等而廣泛地使用於電氣設備、汽車零件、精密機械零料 中。隨著聚縮_脂之領域之擴大，有要求特性越來越 高度化、複合化、特殊化之傾向。其中，為了使用可再生資 源或改善特性，係持續研究使纖維素系物質與聚端騎脂複 合化而成之材料。 於日本專利特開平3_217447號公報中，揭示有於聚縮磁 Μ脂中s周配紙漿而成之聚縮醛樹脂組成物。此處，雖顯禾有 機械強度、耐熱性、燃燒性(燃燒時之樹脂滴落）等之改善， 但於該材料之調整方法中，通常難以使紙漿均勻且安定地分 散於樹腊中’於實際應用上難以製造材料。 又’於日本專利特開2010-150313號公報中，揭示有調配 &細给樹月曰與特定鬆密度(bulk density)之纖維狀纖維素系 物i而成之聚縮醛樹脂組成物。此處，由於使用纖維狀纖維 素系物質’故而可獲得纖維狀纖維素系物質之凝聚較受抑制 100136255 4 201219484 之結果，但所獲得之材料之彎曲彈性率較低，且機械特性之 改善不充分。又，對於拉伸強度、彎曲強度、衝擊強度等物 性之改善未作任何揭示。 【發明内容】 於先前所習知之技術中，如上所述般難以使機械特性之改 善與纖維素系物質之分散性並存，從而迫切期待進一步之改 善。本發明之目的在於：解決該等問題，提供一種拉伸強度、 4曲強度衝擊強度等機械特性優異，纖維素纖維粉末之分 散性優異之聚縮醛樹脂組成物及其製造方法。 本發明者等人’為了解決上述問題而進行了潛心研究，結 果發現，藉由併用特定選擇之聚縮醛樹脂作為基礎樹脂，且 於其中調配特定選擇之纖維素纖維粉末，進而併用調配受阻 紛系抗氧化劑與特定之含氮化合物，可獲得可解決上述問題 並達成目的之聚、_樹脂組成物，從而完成本發明。 即’本發明提供一種聚縮賴脂組成物，其係相對於⑷ 使二哺99.9〜9〇·〇重量％與單官能環狀醚〇卜1〇 〇重量％ 共聚合而獲得之直鏈聚祕樹脂丨⑽重量份，含有下述者而 成.（b)使二领99.89〜89.0重量％、單官能環狀醚〇卜1〇 〇 重里/〇及g此基數為2〜4之多官能縮水甘油醚化合物Ο." 〜1·〇重1%共聚合而獲得之分枝聚縮搭樹月旨〇1〜5〇重量 份；⑷縱橫比為5〜25、平均纖維長為15〇〜35〇㈣之纖 、隹素、·戴搞末1G〜15G重量份；⑷受阻酴系抗氧化劑〇〇1 100136255 201219484 〜3重量份；（e)自胺基三讲化合物、胍胺化合物、醯肼化合 物及聚醯胺中選擇之至少一種含氮化合物0.01〜3重量份。 (發明效果） 本發明之聚縮醛樹脂組成物係拉伸強度、彎曲強度、衝擊 強度等機械特性優異，並且纖維素纖維粉末之分散性亦優 異，可適用於與汽車零件、電氣、電子零件、雜貨、文具類 等相關之成形品中。 【實施方式】 以下針對本發明之聚縮醛樹脂組成物及其製造方法進行 詳細地說明。 構成本發明聚縮醛樹脂組成物之主要成分為如下所述。 <(a)直鏈聚縮醛樹脂> 於本發明中所使用之⑻成分之聚縮醛樹脂係使三。等烷 99.9〜90.0重量％與單官能環狀鱗0.1〜10.0重量％共聚合 而獲得之直鏈聚縮酿樹脂。 (a)成分之直鏈聚縮醛樹脂係藉由使曱醛之環狀三聚體， 即三。号烷與單官能環狀醚共聚合而製造，通常藉由水解而去 除末端之不安定部分，從而相對於熱分解而安定化。 於本發明中，將包含-C-0-C-單位而形成環狀結構之化合 物總稱為單官能環狀醚，且亦包含稱為環狀曱縮醛之化合物 群。於本發明中，於該單官能環狀醚中使用藉由與三11号烷之 共聚合而可於(a)直鏈聚縮醛樹脂之分子中導入C2〜C6左 100136255 6 201219484 右之氧伸烷基單位之化合物，例如可列舉：環氧乙烷、環氧 丙烷、環氧丁烷、環氧環己烷、表氯醇、表溴醇、苯環氧乙 烷、氧雜環丁烷、3,3-雙（氯曱基）氧雜環丁烷、四氫呋喃、 三氧雜環庚烷、1,3-二°号烷、1,3-二氧雜環戊烷、丙二醇曱 縮醛、二乙二醇曱縮醛、三乙二醇曱縮醛、1，4-丁二醇曱縮 醛、1,5-戊二醇曱縮醛、1,6-己二醇曱縮醛等。 該等單官能環狀醚可單獨使用或組合二種以上使用。尤佳 為環氧乙烷、1，3-二氧雜環戊烷、1,4-丁二醇曱縮醛、二乙 二醇曱縮醛等單官能環狀醚。 該等單官能環狀醚之共聚合比例係相對於三噚烷9 9.9〜 90.0重量％，為0.1〜10.0重量％，較佳為相對於三噚烷99.7 〜93.0重量％，為0.3〜7.0重量％。藉此所獲得之(a)直鏈聚 縮醛樹脂較佳為於分子中以該程度之比例包含源自於該單 官能環狀醚之單位。於單官能環狀醚之共聚合比例較少之情 形時，本發明聚縮醛樹脂組成物之基礎，即（a)直鏈聚縮醛 樹脂之熱安定性等容易變為不充分者，於單官能環狀醚之共 聚合比例較多之情形時，（a)直鏈聚縮醛樹脂之機械特性變 為不充分者。 (a)成分之聚縮醛樹脂之熔融指數較佳係以10〜50g/10分 鐘之範圍較為良好。於熔融指數過小及過大之情形時，存在 無法充分獲得本發明效果之情況。再者，熔融指數係依據 ASTM-D1238，於 190°C、2.16 kgf(21.2 N)之條件下所測定 100136255 7 201219484 之值。 < (b)分枝聚縮酸樹脂> 於本發明中所使用之（b)成分之聚縮醛樹脂係使三哼烷 99.89〜89.0重量％與單官能環狀醚0.1〜10.0重量％及官能 基數為2〜4之多官能縮水甘油醚化合物0.01〜1.0重量％共 聚合而獲得之分枝聚縮醛樹脂。 (b)成分之分枝聚縮醛樹脂係藉由使三噚烷與單官能環狀 醚及官能基數為2〜4之多官能縮水甘油醚化合物共聚合而 製造，通常藉由水解去除末端之不安定部分，從而相對於熱 分解而安定化。 作為於(b)成分之分枝聚縮醛樹脂之製造中所使用之單官 能環狀醚，可同樣地使用於上述(a)成分之聚縮醛樹脂中所 使用之物質。尤佳為環氧乙烷、1,3-二氧雜環戊烷、1，4-丁 二醇曱縮醛、二乙二醇曱縮醛等單官能環狀醚。 所謂於(b)成分之分枝聚縮醛樹脂之製造中所使用之官能 基數為2〜4之多官能縮水甘油化合物，係於1分子中具 有2〜4個縮水甘油趟單位之化合物，較佳為自乙二醇二縮 水甘油醚、丙二醇二縮水甘油醚、1,4- 丁二醇二縮水甘油 醚、己二醇二縮水甘油醚、間苯二酚二縮水甘油醚、雙酚A 二縮水甘油Μ、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘 油醚、聚丁二醇二縮水甘油醚等2官能縮水甘油醚化合物； 三輕曱基丙烧三縮水甘油醚、甘油三縮水甘油醚等3官能縮 100136255 8 201219484 水甘油醚化合物；季戊四醇四縮水甘油_等4官能縮水甘油 醚化合物所組成之群組中選擇之一種或兩種以上。其中，尤 佳為三羥曱基丙烷三縮水甘油醚、甘油三縮水甘油醚、季戊 四醇四縮水甘油醚等之於1分子中具有3至4個縮水甘油醚 單位之化合物。 於本發明中，用作(b)成分之分枝聚縮醛樹脂係相對於三嘮 烷99.89〜89.0重量％，使上述單官能環狀醚以0.1〜10.0重 量％、上述多官能縮水甘油醚化合物以0.01〜1.0重量％之 比例共聚合而獲得者，較佳為相對於三噚烷99.67〜92.3重 量％，使上述單官能環狀醚以0.3〜7.0重量％、上述多官能 縮水甘油醚化合物以0.03〜0.7重量％之比例共聚合而獲得 者。 於單官能環狀醚之比例較少之情形時，（b)分枝聚縮醛樹 脂之熱安定性等容易變為不充分者，於單官能環狀醚之比例 較多之情形時，（b)分枝聚縮醛樹脂之機械特性變為不充分 者。又，於多官能縮水甘油醚化合物之共聚合比例較少之情 形時，所獲得之(b)分枝聚縮醛樹脂對改善聚縮醛樹脂組成 物之機械特性之幫助程度變得不充分，相反地，於多官能縮 水甘油醚化合物之共聚合比例較多之情形時，所獲得之(b) 分枝聚縮醛樹脂之流動性變為不充分者，對纖維素纖維粉末 之分散性造成不良影響，因而欠佳。 於本發明中，（b)成分之分枝聚縮醛樹脂之熔融指數較佳 100136255 9 201219484 係以讀〜Η) _分鐘之範圍較為良好。於溶融指數 及過大之情料，存在無法充分獲得本發較果之情況 者，熔融指數係依據ASTM_D1238，於19〇ΐ、2 16 N)之條件下所測定之值。 '2 於本發財，（b)成分之紐聚之概量係 於⑻成分之直鏈聚縮醛樹脂1〇〇重量份，為〇」〜 旦 份’較佳為0.5〜20重量份，再佳為卜1〇重量 里 成分之分枝聚祕樹脂之調配量低重量份之情 聚祕樹脂組成物之機械特性之改善變得不充分嗜高於 50重量份之情科，纖維素纖轉末之分散性會惡化了因 而欠佳。 Μ < (c)纖維素纖維粉末> 於2明中所使用之⑷纖維素纖維係將 料而製成粉末軸者，1 ^為原 7〜20。W …以比為5〜25。尤佳之縱橫比為 、C、·戴維素纖維粉末之縱橫比低於5之情形時’聚 =組:物之機械特性之改善變得不充分，於高於；5 者，縱^比可藉由根播 彳主丹 掃H m SEM(Scanning Electron Microscope > W式電子1 貞微鏡)或光學賴叙觀“败。 又’（0纖維素纖維粉末之 尤佳為 180〜320 150-350 ^ m , 低於⑼二維素纖維粉末之平均纖維長 月」寺’聚祕樹脂組成物之機械特性之 100136255 201219484 改錢得不充分，於高於35〇 _之情形時，存在纖維素 纖維粉末之分散性惡化，又，聚祕樹脂組成物之分解會進 =兄’因而欠佳。再者’平均纖維長可藉由根據SEM 或光予顯微鏡之觀察而測定。 又’於本發财，作為所制之⑷纖維錢維粉末，較 佳^纖維素純度為98〜赚。者，尤佳為α纖維素純度為 99〜1_之_者。如此藉由使“纖維素純度較高之纖 維素纖維粉末，而顿得熱钱料純異之聚祕樹脂組 成物。於使用α纖維钱衫充分之纖維素纖維粉末之情形 時，存在所獲得之㈣賴餘成物m生變為不充分 者，且因樹脂之分解而難以製造之情況。 於本發明巾’⑷纖維素纖隸末之調配4係相對於⑷直 鍵聚縮搭樹脂100重量份’為10〜15〇重量份，較佳為1〇 〜150重量份。於(C)纖維素纖維粉末之調配量低於重量 份之情形時，聚縮醛樹脂組成物之機械特性之改善變得不充 分，於高於150重量份之情形時，纖維素纖維粉末之分散性 會惡化，因而欠佳。 < (d)受阻酴系抗氧化劑> 本發明之聚縮醛樹脂組成物係藉由使用（d)受阻紛系化合 物’而可安定地獲得機械特性之改善。作為（d)受阻盼系化 合物，可列舉：單環式受阻酚化合物(例如2,6-二-第三丁基 -對曱紛等）；利用包含烴基或硫原子之基所連結之多環式受 100136255 11 201219484 阻酚化合物（例如：2,2’-亞曱基雙(4-曱基-6-第三丁基苯酚）、 4,4’-亞甲基雙(2,6-二-第三丁基苯酚）、1，1，3-三(2-曱基-4-羥 基-5-第三丁基苯基）丁烷、4,4’-亞丁基雙(3-曱基-6-第三丁基 苯酚）、1，3,5-三甲基-2,4,6-三（3,5-二-第三丁基-4-羥基苄基） 苯、4,4’-硫代雙(3-甲基-6-第三丁基苯酚）等）；具有酿基或醯 胺基之受阻酚化合物（例如：3-(4'-羥基-3’，5’-二-第三丁基苯 基）丙酸正十八烷基酯、2-(4'-羥基-3’，5’-二-第三丁基苯基）丙 酸正十八烷基酯、1，6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基 苯基）丙酸酯]、三乙二醇-雙[3-(3-第三丁基-5-曱基-4-羥基苯 基）丙酸酯]、季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基） 丙酸酯]、3,9-雙{2-[3-(3-第三丁基-4-羥基-5-曱基苯基）丙醯 氧基]-1，1-二曱基乙基}-2,4,8,10-四氧雜螺[5.5]十一烷、2-第 三丁基-6-(3’-第三丁基-5'-曱基-2’-羥基苄基)-4-曱基苯基丙 烯酸酯、2-[1-(2-羥基-3,5-二-第三戊基苯基）乙基]-4,6-二-第 三戊基苯基丙烯酸酯、3,5-二-第三丁基-4-羥基苄基膦酸二-正十八烷基酯、N，N’-六亞曱基雙（3,5-二-第三丁基-4-羥基-二苯丙醯胺、Ν,Ν’-伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基) 丙醯胺]、Ν,Ν’-四亞甲基雙[3-(3,5-二-第三丁基-4-羥基苯基） 丙醯胺]、Ν,Ν’-六亞甲基雙[3-(3,5-二-第三丁基-4-羥基苯基） 丙醯胺]、Ν,Ν'-伸乙基雙[3-(3-第三丁基-5-曱基-4-羥基苯基） 丙醯胺]、Ν，Ν'-六亞曱基雙[3-(3-第三丁基-5-曱基-4-羥基苯 基）丙醯胺]、Ν,Ν’-雙[3-(3,5-二-第三丁基-4-羥基苯基）丙醯基] 100136255 12 201219484 肼、Ν,Ν’-雙[3-(3-第二丁美 s ^ 一 卜一 1暴-5_甲基-4-羥基苯基）丙醯基]肼、 一’ ’ -’帛二丁基-4_經基节基）異三聚氰酸g旨、H5-三(4-第三丁基趣基_2,6_二甲鲜基)異三聚氰酸醋等）。 於本毛月中（d)雙阻盼系抗氧化劑可單獨使用或組合二 種以上使用。該調配比例係相對於⑻直鏈聚祕樹脂議 重量份’為〇.01〜3重量份，較佳為0.02〜1重量份。 < (e)含氮化合物> 本&月之聚㈣樹脂組成物係藉由使用⑷自胺基三讲化 。物胍胺化。物、醯肼化合物及聚驢胺中選擇之至少一種 3氮化a @可^^地獲得機械特性之改善，溶融安定性 亦提高。 作為胺基三。井化合物，可列舉：三聚氛胺或其衍生物[三 聚氰胺、三聚氰胺縮合物（蜜白胺、蜜勒胺、六聚氰胺(meii〇n)) 等]、胍胺或其衍生物、及胺基三销脂[三聚氰胺之共縮合 樹脂（二聚氰胺-甲醛樹脂、苯酚_三聚氰胺樹脂、三聚氰胺_ 苯酚-甲醛樹脂、笨并胍胺-三聚氰胺樹脂、芳香族聚胺_三聚 氰胺樹脂等）、胍胺之共縮合樹脂等]等。 作為胍胺化合物’可列舉：脂肪族胍胺化合物（單胍胺類、 伸烧基雙脈胺類寻），脂壞族脈胺系化合物（單脈胺類等）；芳 香族胍胺系化合物[單胍胺類（苯并胍胺及其官能基取代物 等）、α-或々·萘并胍胺及該等之官能基取代衍生物、聚胍胺 類、芳烷基或伸芳烷基胍胺類等];含雜原子胍胺系化合物 100136255 13 201219484 [含縮醛基胍胺類、含四氧雜螺環胍胺類（CTU-胍胺、CMTU-胍胺等）、含異三聚氰酸環胍胺類、含咪唑環胍胺類等]等。 又，亦包含上述之三聚氰胺、三聚氰胺衍生物、胍胺系化合 物之烷氧基甲基經由胺基所取代之化合物等。 作為醯肼化合物，可列舉：脂肪族羧酸醯肼系化合物（硬 脂酸醯肼、12-羥基硬脂酸醯肼、癸二酸二醯肼、十二烷二 酸二醯肼、二十烷二酸二醯肼等）；脂環族羧酸醯肼系化合 物（1,3-雙（肼基羰乙基)-5-異丙基乙内醯脲等）；芳香族羧酸 醯肼系化合物（4-羥基-3,5-二-第三丁基苯基苯甲酸醯肼、1-萘曱醯肼、2-萘甲醯肼、間苯二曱酸二醯肼、2,6-萘二曱酸 二醯肼等）；含雜原子羧酸醯肼系化合物；聚合體型羧酸醯 肼系化合物等。 作為聚醯胺，包含下述者：由二胺與二羧酸所衍生之聚醯 胺；將胺基羧酸、視需要之二胺及/或二羧酸併用所獲得之 聚醯胺；藉由將内醯胺與視需要之二胺及/或二羧酸併用所 衍生之聚醯胺。又，亦包含藉由兩種以上不同之聚醯胺形成 成分所形成之共聚合聚醯胺。 作為具體的聚醯胺之例，可列舉：聚醯胺3、聚醯胺4、 聚醯胺46、聚醯胺6、聚醯胺66、聚醯胺610、聚醯胺612、 聚醯胺11、聚醯胺12等脂肪族聚醯胺；由芳香族二羧酸(例 如對苯二曱酸及/或間苯二曱酸）與脂肪族二胺（例如六亞曱 基二胺)所獲得之聚醯胺；由脂肪族二羧酸(例如己二酸)與芳 100136255 14 201219484 香族二胺(例如間苯二甲基二胺)所獲得之聚醯胺；由芳香族 及脂肪族二羧酸（例如對苯二甲酸與己二酸）與脂肪=二胺 (例如六亞曱基二胺）所獲得之聚醯胺及該等之共聚物等。 又，亦可使用聚_硬鏈段與除㈣成分等以外:键段所 鍵結而成之聚醯胺系嵌段共聚合體。 (e)自胺基三讲化合物、胍胺化合物、醯肼化合物及聚酿胺 中選擇之含氮化合物可單獨使用或組合二種以上使用。該調 配比例係相對於(a)直鏈聚縮醛樹脂1〇〇重量份，為〇 〜3 重量份，較佳為0.02〜1重量份。 <(f)加工助劑〉 本發明之聚祕繼旨組成物，係藉纟使肖（f)自長鍵脂肪 酸、長鏈脂肪酸之衍生物、長鏈脂肪族醇、聚氧伸烷基二醇、 稀烴系躐及聚石夕氧化合物中選擇之至少一種加工助而^ 安定地獲得機械特性之改善，熔融加工性亦提高’因而較佳 為調配(f)加工助劑。 長鏈脂肪酸可為飽和脂肪酸或亦可為不飽和脂肪酸。又， 亦可使用其一部分之氫原子經羥基等取代基所取代者。作為 此種長鏈脂肪酸，可例示：碳數10以上之一價或二價脂肪 酸、碳數10以上之一價不飽和脂肪酸、碳數1〇以上之二價 脂肪酸(二元脂肪酸）。於上述脂肪酸中亦包含分子内具有一 個或數個羥基之脂肪酸。 於長鏈脂肪酸之衍生物中，包含脂肪酸酯及脂肪酸醯胺 100136255 15 201219484 等。 作為脂肪酸酯，可列舉上述長鏈脂肪酸與醇之酯。其結構 並無特別限制，可使用之直鏈狀或分枝狀脂肪酸酯之任意 者。作為脂肪酸酯之具體例，可列舉：乙二醇單或二棕櫚酸 酯、乙二醇單或二硬脂酸酯、乙二醇單或二莶樹酸酯、乙二 醇單或二褐煤酸酯、甘油單至三棕櫚酸酯、甘油單至三硬脂 酸酯、甘油單至三茶樹酸醋、甘油單至三褐煤酸醋、季戊四 醇單至四棕櫚酸酯、季戊四醇單至四硬脂酸酯、季戊四醇單 至四窬樹酸酯、季戊四醇單至四褐煤酸酯、聚甘油三硬脂酸 酯、三羥曱基丙烷單棕櫚酸酯、季戊四醇單十一烷酸酯、山 梨糖醇酐單硬脂酸酯、聚伸烷基二醇（聚乙二醇、聚丙二醇 等）之單或二月桂酸酯、單或二棕櫚酸酯、單或二硬脂酸酯、 單或二窬樹酸酯、單或二褐煤酸酯、單或二油酸酯、單或二 亞麻油酸s旨等。 作為脂肪酸醯胺之例，可例示：癸酸醯胺、月桂酸醯胺、 肉豆蔻酸醯胺、棕櫚酸醯胺、硬脂酸醯胺、花生酸醯胺、窬 樹酸醯胺、褐煤酸醯胺等飽和脂肪酸之一級酸醯胺；油酸醯 胺等不飽和脂肪酸之一級酸醯胺；硬脂基硬脂酸醯胺、硬脂 基油酸醯胺等飽和及/或不飽和脂肪酸與單胺之二級酸醯 胺；乙二胺-二棕櫚酸醯胺、乙二胺-二硬脂酸醯胺（伸乙基雙 硬脂醯胺）、六亞曱基二胺-二硬脂酸醯胺、乙二胺-二窬樹酸 醯胺、乙二胺-二褐煤酸醯胺、乙二胺-二油酸醯胺、乙二胺 100136255 16 201219484 -二芥子酸醯胺等，進而可例示具有於乙二胺-(硬脂酸醯胺) 油酸醯胺等伸烷基二胺之胺基位置鍵結有不同醯基之結構 之雙醯胺等。 作為長鏈脂肪族醇，可列舉：月桂醇、肉豆蔻醇、鯨蠟醇、 油醇、硬脂醇、茶樹醇等。 作為上述聚氧伸烷基二醇，可列舉：伸烷基二醇（乙二醇、 丙二醇、丁二醇等伸烷基二醇筝)之均聚合體或共聚合體、 該等之衍生物等。 作為聚氧伸烷基二醇之具體例，可列舉：聚乙二醇、聚丙 二醇、聚丁二醇等聚氧伸烷基二醇、聚氧乙烯-聚氧丙烯共 聚合體（無規或嵌段共聚合體等）、聚氧乙烯聚氧丙烯甘油 醚、聚氧乙烯聚氧丙烯單丁基醚等共聚合體等。該等之中， 較佳為具有氧伸乙基單位之聚合體，例如聚乙二醇、聚氧乙 烯聚氧丙烯共聚合體及該等之衍生物等。聚氧伸烷基二醇之 平均分子量為3χ102〜ΙχΙΟ6，較佳為ΙχΙΟ3〜ΙχΙΟ5左右。 作為上述烯烴系蠟，可列舉：低分子量之聚烯烴（例如： 低分子量聚乙烯、低分子量聚丙烯、乙烯與α-烯烴之低分 子量共聚合體等）、氧化型聚乙烯蠟等。 於上述聚矽氧系化合物中，包含（聚）有機矽氧烷等。作為 (聚）有機矽氧烷，可例示：二烷基矽氧烷(二曱基矽氧烷等）、 烷基芳基矽氧烷(苯基甲基矽氧烷等）、二芳基矽氧烷(二苯基 矽氧烷等）等單有機矽氧烷、該等之均聚合體（聚二曱基矽氧 100136255 17 201219484 再者，聚有機矽 烧聚苯基曱基石夕氧燒等）或共聚合體等。 氧炫亦可為低聚物。 =於⑻有機錢⑥巾’亦包含於分子末端或主键中具 广、氧基、經基、燒氧基、•基、胺基或取代胺基(二烧基 月女基等），基、乙稀基、（甲基）丙烯《等取代基之改質（聚) 有機矽氧烷等。 於本發明中，並非必須娜(f)自長鏈脂肪酸、長鏈脂肪酸 之付生物、長鏈脂肪族醇、聚氧伸烷基二醇、烯烴系蠟及聚 矽氧化合物中選擇之至少一種加工助劑，但為了賦予良好之 加工性，進而為了根據良好之加工性而達成安定之機械特性 及優異之表面性狀，較佳為調配該加工助劑，上述化合物可 單獨使用或組合二種以上使用。於調配加工助劑之情形時之 調配比例係相對於(a)直鏈聚縮醛樹脂1〇〇重量份，較佳為 0,01〜3重量份，尤佳為〇.〇5〜1重量份。 <聚縮醛樹脂組成物之製備方法> 於本發明中，上述聚縮醛樹脂組成物之製備方法之具體態 樣並無特別限定’ 一般而言可藉由作為合成樹脂組成物或其 成形品之製備法之公知的設備與方法而製備。即，可混合必 需之成分’並使用擠出機或其他溶融混練裝置進行混練而製 備為成形用顆粒。又，亦可使用數個擠出機或其他熔融混練 裝置。於本發明中，就機械特性之改善與纖維素纖維粉末之 分散性並存之觀點而言，擠出機尤佳為使用雙軸擠出機。就 100136255 18 201219484 機械特性之改善與纖維素纖維粉末之分散性並存之觀點而 言，尤佳為下述製造方法：使用可側進料之雙轴擠出機，自 擠出機之側方以獨立於其他原料之方式供給（C)纖維素纖維 粉末而進行熔融混練之製造方法。 於本發明之聚縮醛樹脂組成物之製備時，可使用改善聚縮 醛樹脂與(C)纖維素纖維粉末之密著性之物質。此處，作為 改善密著性之物質，可列舉：異氰酸酯化合物、異硫氰酸酯 化合物、及該等之改質體異氰酸酯化合物、熱可塑性聚胺基 曱酸酯樹脂、α,/3-單烯烴性不飽和羧酸之酸酐之聚合體及 共聚合體、硼酸化合物等。 進而，為了根據目標用途而改善其物性，於本發明之組成 物中可調配公知之各種添加物。若例示添加物之例，則可列 舉：各種著色劑、潤滑劑、成核劑、界面活性劑、異質聚合 體、有機高分子改良劑及無機、有機、金屬等之纖維狀、粉 粒狀、板狀之填充劑，可混合使用該等之一種或兩種以上。 <聚縮醛樹脂組成物之成形方法及用途> 本發明之聚縮醛樹脂組成物可利用先前公知之成形方法 (例如射出成形、擠出成形、加壓成形、吹塑成形、真空成 形、發泡成形、旋轉成形、氣體注射成形等方法）而成形為 各種成形品。尤其適宜的是射出成形。又，該等成形品可利 用於汽車零件、電氣、電子零件、建材、生活相關零件、裝 飾相關零件、醫用相關零件等各種用途中。 100136255 19 201219484 具體而5，作為汽車零件，可列舉：内把手、燃料儲物箱 開啟器、安全帶扣、輔助包裝材料、各種開關、按趣、操作 桿、線夾等内飾零件；錶盤、連接器等電氣系統零件；音響 叹備或π車導航設備等車載電氣、電子零件；與以車窗調節 器之載板為代表之金屬接觸之零件、m貞致動器零件、車鏡 零件、到水n馬㈣統零件、燃㈣統之零件等機構零件等。 作為電氣、電子零件，可列舉：利用聚縮_脂成形品所 構成，並且存在多個金屬接點之設備之零件或構件，例如： 音響設備、視頻設備’或電話機、影印機、傳真機、文字處 理機、計算機等OA(⑽ee Aut。刪‘，辦公自動化)設備； 玩具類之零件或構件，具體而言可列舉：底板、齒輪、操作 桿、凸輪、滑輪、軸承等。 進而’可適用於照明器具、建具、配管、活栓、水龍頭、 盟洗室周邊t請零件等建材、配管零件；知件類、文直、潤 唇膏、口、mm淨水器、切料、喷霧容器、 氣溶膠容器、普通容器、注射針之托架等廣泛之生活相關零 件、裝飾相關零件、醫用相關零件。 [實施例] 以下基於實施例而更加具體地說明本發明，但本發明不受 該等實施例之限定。 [實施例1、2、比較例1〜3] 以表1所示之比例’將⑷直鏈聚祕樹月旨、（b)分枝聚縮 100136255 201219484 搭樹月曰（C)纖維素纖維粉末、⑷受阻酉分系抗氧化劑、⑷含 氮化合物及(f)加卫助劑利用雙軸擠出機進躲融混練而製 備顆粒狀之聚縮酸樹脂組成物^再者，⑷纖維素纖維粉末 係自雙軸擠出機之側方獨立地由進料器供給並混合。使用所 獲得之顆粒’藉由射出成形機而成形為既定之試驗>{，並進 行試驗評估。將結果示於表i。 [使用成分] 所使用之成分之詳細說明係如下所述。 (a)直鏈聚縮醛樹脂 (a-Ι)使二°等燒96.5重量j Q 一 , 里/〇與1，3-一氣雜環戊烷3 5重量％ 共聚合而獲得之直鏈聚縮酸樹 言月曰炫融指數=27 g/ΙΟ分鐘 (Poly Plastics股份有限公司製造） (b)分枝聚縮醛樹脂 1，3-二氧雜環戍烷17重量％ 0.1重量％共聚合而獲得之分 g’l〇 分鐘(Poly Plastics 股份 (b-Ι)使二α号烧98.2重量％與 及三經曱基丙烧三縮水甘油轉 枝聚縮醛樹脂，熔融指數 有限公司製造） (c)纖維素纖維粉末 15 ’平均纖維長3〇〇 # m， 〜90 g/L(Rettenmaier 公司 (c-l)ARBOCEL BC200，縱横比 α纖維素純度99.5% ’备比重％ 製造） 以下’平均纖維長5〇μηι (c-2)KC Flock W-200，縱横比 2 100136255 201219484 以下，a纖維素純度99%以上，鬆比重300〜360 g/L(Nippon Paper Chemicals Co.，Ltd 製造） (d)受阻酚系抗氧化劑 (d-1)季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基）丙酸酯] ⑷含氮化合物 (e-Ι)三聚氰胺 (f)加工助劑 (f-Ι)伸乙基雙硬脂醯胺 [擠出條件] 擠出機·· TEX-30a(L/D=38.5)，日本製鋼所公司製造 螺桿旋轉數：129rpm 滾筒溫度：C2=160°C，C3 〜Cll.D=200t： [成形條件] 成形機：ROBOSHOT S2000U00B，螺桿徑 28 mm，Fanuc 公司製造201219484 6. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention is a polycondensation group which is excellent in characteristics such as tensile strength, f-bend strength, and impact strength, and excellent in dispersibility of cellulose fiber powder: Its manufacturing method. [Prior Art] Polyacetal resin has excellent properties in terms of mechanical properties, thermal properties, electrical properties, and slidability, and is widely used as a structural material or a mechanical component in electrical equipment and automotive parts. Precision machinery and materials. With the expansion of the field of polycondensation and lipids, there is a tendency to require more and more highly specialized, complex, and specialized features. Among them, in order to use renewable resources or to improve characteristics, materials for the synthesis of cellulose-based materials and poly-capacity have been continuously studied. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Here, although there is improvement in mechanical strength, heat resistance, flammability (resin dripping during burning), etc., in the method of adjusting the material, it is generally difficult to uniformly and stably disperse the pulp in the tree wax. It is difficult to manufacture materials in practical applications. Further, Japanese Laid-Open Patent Publication No. 2010-150313 discloses a polyacetal resin composition prepared by blending & finely giving a fibrous cellulose system i with a tree density and a bulk density. Here, since the fibrous cellulose-based material is used, the aggregation of the fibrous cellulose-based material can be suppressed as a result of suppression of 100,136,255 4 201219484, but the obtained material has a low flexural modulus and an improvement in mechanical properties. full. Further, the improvement in physical properties such as tensile strength, bending strength, and impact strength is not disclosed. DISCLOSURE OF THE INVENTION In the prior art, as described above, it is difficult to improve the mechanical properties and the dispersibility of the cellulose-based material, and further improvement is eagerly desired. An object of the present invention is to provide a polyacetal resin composition which is excellent in mechanical properties such as tensile strength and flexural strength and has excellent dispersibility in cellulose fiber powder, and a method for producing the same. The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that by using a specific selected polyacetal resin as a base resin and blending a specific selected cellulose fiber powder therein, the blending is hindered. The present invention can be accomplished by using an antioxidant and a specific nitrogen-containing compound to obtain a poly- and resin composition which can solve the above problems and achieve the object. That is, the present invention provides a poly-lysate composition which is obtained by copolymerizing (4) a weight of 99.9 to 9 〇·〇 by weight of a monofunctional cyclic ether and 1% by weight of a monofunctional cyclic ether. (10) parts by weight of the resin, containing the following: (b) making the two collars 99.89~89.0% by weight, monofunctional cyclic ether 〇 〇〇 〇〇 〇〇 里 〇 g g g 〇 〇 〇 〇 〇 〇 此 此Glycidyl ether compound Ο." 〜1·〇1% copolymerization obtained by branching polycondensation of the tree 〇1~5〇 parts by weight; (4) aspect ratio of 5~25, average fiber length of 15〇 ~35〇(4), fiber, glutinin, daisha, 1G~15G parts by weight; (4) hindered lanthanide antioxidant 〇〇1 100136255 201219484~3 parts by weight; (e) from amino-based compound, guanamine compound, The at least one nitrogen-containing compound selected from the group consisting of ruthenium compounds and polyamines is 0.01 to 3 parts by weight. (Effect of the Invention) The polyacetal resin composition of the present invention is excellent in mechanical properties such as tensile strength, flexural strength, and impact strength, and is excellent in dispersibility of cellulose fiber powder, and is applicable to automotive parts, electrical and electronic parts. , molded goods such as groceries, stationery, etc. [Embodiment] Hereinafter, the polyacetal resin composition of the present invention and a method for producing the same will be described in detail. The main components constituting the polyacetal resin composition of the present invention are as follows. <(a) Linear polyacetal resin> The polyacetal resin of the component (8) used in the present invention is three. A linear polycondensation resin obtained by copolymerizing an alkane of 99.9 to 90.0% by weight with a monofunctional cyclic scale of 0.1 to 10.0% by weight. The linear polyacetal resin of the component (a) is a cyclic trimer of furfural, that is, three. The alkane is produced by copolymerization with a monofunctional cyclic ether, and is usually stabilized by thermal decomposition by removing the unstable portion of the terminal by hydrolysis. In the present invention, a compound containing a -C-0-C- unit to form a cyclic structure is collectively referred to as a monofunctional cyclic ether, and also includes a compound group called a cyclic acetal. In the present invention, in the monofunctional cyclic ether, a copolymer of (a) a linear polyacetal resin can be introduced into the molecule of the (a) linear polyacetal resin by the copolymerization with the No. 3 11 alkane. 100136255 6 201219484 Right Oxygen Examples of the alkylene unit compound include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, phenylethylene oxide, and oxetane. , 3,3-bis(chloroindenyl)oxetane, tetrahydrofuran, trioxepane, 1,3-dioxane, 1,3-dioxolane, propylene glycol acetal , diethylene glycol acetal, triethylene glycol acetal, 1,4-butanediol acetal, 1,5-pentanediol acetal, 1,6-hexanediol acetal, etc. . These monofunctional cyclic ethers may be used singly or in combination of two or more. More preferably, it is a monofunctional cyclic ether such as ethylene oxide, 1,3-dioxolane, 1,4-butanediol acetal or diethylene glycol acetal. The copolymerization ratio of the monofunctional cyclic ethers is from 0.1 to 10.0% by weight, relative to trioxane, from 9 to 10.0% by weight, preferably from 99.7 to 93.0% by weight, based on trioxane, from 0.3 to 7.0% by weight. %. The (a) linear polyacetal resin thus obtained preferably contains a unit derived from the monofunctional cyclic ether in a ratio to the extent of the molecule. When the copolymerization ratio of the monofunctional cyclic ether is small, the basis of the polyacetal resin composition of the present invention, that is, the thermal stability of the (a) linear polyacetal resin is likely to be insufficient, When the copolymerization ratio of the monofunctional cyclic ether is large, the mechanical properties of the (a) linear polyacetal resin are insufficient. The melt index of the polyacetal resin of the component (a) is preferably in the range of 10 to 50 g/10 minutes. When the melt index is too small or too large, there is a case where the effect of the present invention cannot be sufficiently obtained. Further, the melt index is determined according to ASTM-D1238 at 190 ° C, 2.16 kgf (21.2 N), and the value of 100136255 7 201219484 is determined. <(b) Branched polyacetal resin> The polyacetal resin of the component (b) used in the present invention has a trioxane of 99.89 to 89.0% by weight and a monofunctional cyclic ether of 0.1 to 10.0% by weight. And a branched polyacetal resin obtained by copolymerization of 0.01 to 1.0% by weight of a polyfunctional glycidyl ether compound having a functional group of 2 to 4. The branched polyacetal resin of the component (b) is produced by copolymerizing trioxane with a monofunctional cyclic ether and a polyfunctional glycidyl ether compound having a functional group number of 2 to 4, usually by hydrolysis to remove the terminal. The part is unstable and stabilized with respect to thermal decomposition. The monofunctional cyclic ether used in the production of the branched polyacetal resin of the component (b) can be similarly used for the polyacetal resin of the above component (a). More preferably, it is a monofunctional cyclic ether such as ethylene oxide, 1,3-dioxolane, 1,4-butanediol acetal or diethylene glycol acetal. The polyfunctional glycidol compound having a functional group number of 2 to 4 used in the production of the branched polyacetal resin of the component (b) is a compound having 2 to 4 glycidinium units per molecule.佳 is from ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A a bifunctional glycidyl ether compound such as glycidol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or polybutylene glycol diglycidyl ether; trisodium sulfonate triglycidyl ether, glycerol tricondensate One or more selected from the group consisting of trifunctional condensed glycerol ether 100136255 8 201219484 glyceryl ether compound; pentaerythritol tetraglycidyl _ and other tetrafunctional glycidyl ether compounds. Among them, a compound having 3 to 4 glycidyl ether units in one molecule, such as trihydroxydecylpropane triglycidyl ether, glycerol triglycidyl ether or pentaerythritol tetraglycidyl ether, is preferable. In the present invention, the branched polyacetal resin used as the component (b) is 99.89 to 89.0% by weight based on trioxane, and the above-mentioned monofunctional cyclic ether is 0.1 to 10.0% by weight based on the above polyfunctional glycidyl ether. The compound is obtained by copolymerization in a ratio of 0.01 to 1.0% by weight, preferably 99.67 to 92.3% by weight based on trioxane, and the above-mentioned monofunctional cyclic ether is 0.3 to 7.0% by weight based on the above polyfunctional glycidyl ether compound. It is obtained by copolymerization in a ratio of 0.03 to 0.7% by weight. When the ratio of the monofunctional cyclic ether is small, the thermal stability of the (b) branched polyacetal resin is likely to be insufficient, and when the ratio of the monofunctional cyclic ether is large, b) The mechanical properties of the branched polyacetal resin become insufficient. Further, when the copolymerization ratio of the polyfunctional glycidyl ether compound is small, the obtained (b) branched polyacetal resin is insufficient in improving the mechanical properties of the polyacetal resin composition. On the other hand, when the copolymerization ratio of the polyfunctional glycidyl ether compound is large, the fluidity of the obtained (b) branched polyacetal resin becomes insufficient, resulting in dispersibility of the cellulose fiber powder. Bad effects, and thus poor. In the present invention, the melt index of the branched polyacetal resin of the component (b) is preferably 100136255 9 201219484, and the range of _ minutes is relatively good. In the case of the melt index and the excessive material, there is a case where the result of the present invention cannot be sufficiently obtained, and the melt index is a value measured under the conditions of 19〇ΐ, 2 16 N) according to ASTM_D1238. '2 In this case, the amount of the component (b) is based on the linear polyacetal resin of component (8), and is preferably 0.5 to 20 parts by weight. The amount of the branching poly-resin of the composition of the weight of the material is low, the improvement of the mechanical properties of the poly-resin composition becomes insufficient, the habit of more than 50 parts by weight, the cellulose fiber The dispersibility at the end will deteriorate and thus be poor. Μ < (c) Cellulose fiber powder> The cellulose fiber of the (4) cellulose fiber used in the above description is made into a powder axis, and 1 ^ is the original 7 to 20. W ... is 5 to 25 in ratio. When the aspect ratio of the C/Davilin fiber powder is less than 5, the 'poly= group: the improvement of the mechanical properties of the object becomes insufficient, above 5;根 根 H m m m m Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan Scan ^ m , less than (9) the average fiber length of the two-dimensional fiber powder, the mechanical properties of the polymer composition of the polymer compound 100136255 201219484, the money is not sufficient, in the case of more than 35 〇, there is cellulose fiber The dispersibility of the powder deteriorates, and the decomposition of the poly-resin composition will be inferior. Therefore, the average fiber length can be determined by observation according to SEM or light microscopy. As the prepared (4) fiber Qianwei powder, it is preferred that the cellulose purity is 98~ earned. Especially, the purity of α cellulose is 99~1_. Thus by making "the cellulose has higher purity." The cellulose fiber powder, and the hot resin material is pure and different. In the case of a cellulose fiber powder which is sufficiently used in an alpha fiber jersey, there is a case where the obtained (4) sufficiency m is insufficient, and it is difficult to manufacture due to decomposition of the resin. The blending of the fiber ends is 4 to 15 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the (4) direct-bonding polycondensation resin. The amount of the cellulose fiber powder in (C) is low. In the case of parts by weight, the improvement of the mechanical properties of the polyacetal resin composition is insufficient, and when it is more than 150 parts by weight, the dispersibility of the cellulose fiber powder is deteriorated, which is not preferable. d) hindered lanthanide antioxidant> The polyacetal resin composition of the present invention can stably obtain an improvement in mechanical properties by using (d) a hindered compound. As the (d) hindered compound, Listed: monocyclic hindered phenol compounds (for example, 2,6-di-t-butyl-p-quinone, etc.); polycyclic formulas bonded by a group containing a hydrocarbon group or a sulfur atom, 100136255 11 201219484, a phenolic compound (for example) :2,2'-Amidene bis (4-mercapto-6-third Phenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 1,1,3-tris(2-mercapto-4-hydroxy-5-t-butyl Phenyl)butane, 4,4'-butylenebis(3-indolyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5 -di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-thiobis(3-methyl-6-tert-butylphenol), etc.; hindered with a thiol or amidino group Phenolic compounds (for example: n-octadecyl 3-(4'-hydroxy-3',5'-di-t-butylphenyl)propanoate, 2-(4'-hydroxy-3',5' -di-t-butylphenyl)propenyl octadecyl propionate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propane Acid ester], triethylene glycol-bis[3-(3-tert-butyl-5-fluorenyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di- Tributyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-fluorenylphenyl)propenyloxy] -1,1-didecylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane,2-tert-butyl-6-(3'-tert-butyl-5 '-Mercapto-2'-hydroxybenzyl)-4-mercaptophenyl acrylate, 2-[1-(2-hydroxyl) -3,5-di-p-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, 3,5-di-tert-butyl-4-hydroxybenzylphosphine Di-n-octadecyl acid, N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-diphenylpropionamide, hydrazine, hydrazine--ethyl Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamine], hydrazine, Ν'-tetramethylene bis[3-(3,5-di-third butyl) 4-hydroxyphenyl) propylamine], hydrazine, Ν'-hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide], hydrazine ,Ν'-Extended ethyl bis[3-(3-tert-butyl-5-fluorenyl-4-hydroxyphenyl)propanamine], hydrazine, Ν'-hexamethylene bis[3-(3 -T-butyl-5-mercapto-4-hydroxyphenyl)propanamine], hydrazine, Ν'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propane醯基] 100136255 12 201219484 肼, Ν, Ν '-double [3-(3-second dingmei s ^ 卜一一暴-5_methyl-4-hydroxyphenyl) propyl hydrazine] 肼, one ' '-'帛 Dibutyl-4_ via benzyl) isocyanuric acid, H5-tris(4-t-butylbutyl 2,6-dimethyl fresh) isomeric cyanide Sour vinegar, etc.). In the present month, (d) the double-anti-antioxidant may be used singly or in combination of two or more. The blending ratio is 〇.01 to 3 parts by weight, preferably 0.02 to 1 part by weight, based on the (8) linear polyester resin. <(e) Nitrogen-containing compound> The present & month poly(tetra) resin composition is derived from the amine group by using (4). Amidoxime. At least one selected from the group consisting of a compound, a ruthenium compound and a polyamidamine 3 is abbreviated to obtain an improvement in mechanical properties and an improved stability of the melt. As the amine group III. The well compound may, for example, be a trimeric amine or a derivative thereof [melamine, a melamine condensate (melamine, melem, melamine), etc.], a guanamine or a derivative thereof, and Amine triester [melamine co-condensation resin (melamine-formaldehyde resin, phenol_melamine resin, melamine_phenol-formaldehyde resin, stupid amine-melamine resin, aromatic polyamine_melamine resin, etc.), a co-condensation resin of guanamine, etc.]. Examples of the guanamine compound include aliphatic guanamine compounds (monodecylamines, extended alkylamines), liposteroids (monoamines, etc.); and aromatic amides. [monodecylamines (benzoguanamine and its functional substituents, etc.), α- or 々naphthylamine and such functional substituted derivatives, polyamines, aralkyl or aralkylenes Base amines, etc.]; hetero atom-containing guanamine compounds 100136255 13 201219484 [Acetal-containing guanamines, tetraoxospiroguanamines (CTU-guanamine, CMTU-decylamine, etc.), Trictanyl cyanamide, imidazole ring amide, etc.]. Further, the above-mentioned melamine, a melamine derivative, a compound in which an alkoxymethyl group of a guanamine compound is substituted with an amine group, and the like are also included. Examples of the ruthenium compound include an aliphatic carboxylic acid lanthanide compound (barium stearate, bismuth 12-hydroxystearate, diterpene azelaic acid, didodecanedioic acid dioxime, twenty Bismuth alkanoic acid, etc.); alicyclic carboxylic acid lanthanide compound (1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin, etc.); aromatic carboxylic acid hydrazine Compound (4-hydroxy-3,5-di-t-butylphenylbenzoate oxime, 1-naphthoquinone, 2-naphthoquinone, dim-benzoic acid dioxime, 2,6 - an anthraquinone dicarboxylate or the like; a ruthenium compound containing a hetero atom; a ruthenium carboxylate compound or the like. As the polyamine, the polyamine which is derived from a diamine and a dicarboxylic acid; the polyamine obtained by using an aminocarboxylic acid, optionally a diamine and/or a dicarboxylic acid; A polydecylamine derived from the combination of an indoleamine and optionally a diamine and/or a dicarboxylic acid. Further, it also comprises a copolymerized polyamine formed by two or more different polyamine forming components. As specific examples of the polyamine, polyamine 3, polyamine 4, polyamine 46, polyamine 6, polyamide 66, polyamide 610, polyamide 612, polyamine 11. An aliphatic polyamine such as polyamine 12; an aromatic dicarboxylic acid (for example, terephthalic acid and/or isophthalic acid) and an aliphatic diamine (for example, hexamethylenediamine) The obtained polyamine; a polyamine obtained from an aliphatic dicarboxylic acid (for example, adipic acid) and an aromatic 100136255 14 201219484 aromatic diamine (for example, m-xylylenediamine); from aromatic and aliphatic Polyamides obtained from dicarboxylic acids (e.g., terephthalic acid and adipic acid) and fats = diamines (e.g., hexamethylenediamine), copolymers thereof, and the like. Further, a poly-area-based block copolymer in which a poly-hard segment and a (four) component are bonded to each other: a bond segment may be used. (e) The nitrogen-containing compounds selected from the group consisting of an amine-based compound, a guanamine compound, an anthraquinone compound, and a polybrene may be used singly or in combination of two or more. The blending ratio is 〇 3 parts by weight, preferably 0.02 to 1 part by weight, per part by weight of the (a) linear polyacetal resin. <(f) Processing Aids> The composition of the present invention is based on the composition of a long-chain fatty acid, a long-chain fatty acid derivative, a long-chain aliphatic alcohol, and a polyoxyalkylene group. At least one of the selection of the diol, the dilute hydrocarbon system and the polyoxo compound aids in the improvement of the mechanical properties and the melt processability is improved. Thus, it is preferred to formulate (f) a processing aid. The long chain fatty acid may be a saturated fatty acid or may be an unsaturated fatty acid. Further, a part of the hydrogen atom may be replaced by a substituent such as a hydroxyl group. The long-chain fatty acid may, for example, be a monovalent or divalent fatty acid having a carbon number of 10 or more, a monovalent unsaturated fatty acid having a carbon number of 10 or more, or a divalent fatty acid (dibasic fatty acid) having a carbon number of 1 or more. The above fatty acid also contains a fatty acid having one or several hydroxyl groups in the molecule. The derivative of the long-chain fatty acid includes a fatty acid ester and a fatty acid decylamine 100136255 15 201219484 and the like. The fatty acid ester may, for example, be an ester of the above long-chain fatty acid and an alcohol. The structure is not particularly limited, and any of linear or branched fatty acid esters can be used. Specific examples of the fatty acid esters include ethylene glycol mono or dipalmitate, ethylene glycol mono or distearate, ethylene glycol mono or diphthalate, ethylene glycol mono- or di-brown coal. Acid esters, glycerol mono-to-trical palmitate, glycerol mono-tristearate, glycerol mono-to-three tea vinegar, glycerol mono-to-three montanic acid vinegar, pentaerythritol mono-tetrapalmitate, pentaerythritol mono-to-tetrastearyl Acid ester, pentaerythritol mono-tetradecanoate, pentaerythritol mono- to tetra-montanate, polyglyceryl tristearate, trishydroxypropyl propane monopalmitate, pentaerythritol monoundecanoate, sorbitan Monostearate, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) of mono or dilaurate, mono or dipalmitate, mono or distearate, mono or diterpenoid Acid esters, mono or di-montanate, mono or dioleate, mono or dilinoleic acid s. Examples of the fatty acid guanamine include decyl citrate, decyl laurate, decyl myristate, decyl palmitate, decylamine stearate, decyl amide, decyl phthalate, montanic acid. a fatty acid monoamine acid such as guanamine; a fatty acid amide such as oleic acid decylamine; a saturated and/or unsaturated fatty acid such as stearyl stearate or stearyl oleate Monoamine acid amide; ethylenediamine-dipalmitate decylamine, ethylenediamine-distearate decylamine (ethyl bis-stearylamine), hexamethylenediamine-di-stearyl Acid amide, ethylenediamine-antimonic acid amide, ethylenediamine-nimelite decylamine, ethylenediamine-nioleate decylamine, ethylenediamine 100136255 16 201219484 - erucic acid decylamine, etc. A bis-guanamine or the like having a structure in which an amine group of an alkylenediamine such as ethylenediamine-(stearate decylamine) oleate is bonded with a different fluorenyl group can be exemplified. Examples of the long-chain aliphatic alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, and tea tree alcohol. Examples of the polyoxyalkylene glycol include a homopolymer or a copolymer of an alkyl diol (such as an alkylene glycol such as ethylene glycol, propylene glycol or butylene glycol), and the like. . Specific examples of the polyoxyalkylene glycol include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polyoxyethylene-polyoxypropylene copolymers (random or embedded). a copolymer such as a segment copolymer or the like, a polyoxyethylene polyoxypropylene glyceryl ether, a polyoxyethylene polyoxypropylene monobutyl ether or the like. Among these, a polymer having an oxygen-extended ethyl unit such as polyethylene glycol, a polyoxyethylene polyoxypropylene copolymer, and the like are preferable. The polyoxyalkylene glycol has an average molecular weight of from 3χ102 to ΙχΙΟ6, preferably from about ΙχΙΟ3 to ΙχΙΟ5. The olefin-based wax may, for example, be a low molecular weight polyolefin (for example, a low molecular weight polyethylene, a low molecular weight polypropylene, a low molecular weight copolymer of ethylene and an α-olefin, or the like) or an oxidized polyethylene wax. The polyfluorene-based compound contains (poly)organosiloxane or the like. The (poly)organooxane may, for example, be a dialkyl decane (such as a dimercapto oxane), an alkyl aryl siloxane (such as a phenylmethyl decane), or a diaryl fluorene. a monoorganosiloxane such as oxyalkylene (diphenyl sulfoxane) or the like, or a homopolymer of the same (polydidecyloxyl 100136255 17 201219484, polyorgano-indene polyphenyl fluorene, oxy-oxygen, etc. ) or a copolymer or the like. Oxygen can also be an oligomer. = (8) Organic money 6 towels' also contained in the molecular end or primary bond with a broad, oxy, thiol, alkoxy, base, amine or substituted amine group (dialkyl group, etc.), A modified (poly)organosiloxane such as an ethylene group or a (meth) propylene "substituent." In the present invention, it is not necessary to select at least one of long-chain fatty acids, long-chain fatty acid-paying organisms, long-chain aliphatic alcohols, polyoxyalkylene glycols, olefin-based waxes, and polyoxynitrides. A processing aid, in order to impart good workability, and to achieve stable mechanical properties and excellent surface properties in accordance with good processability, it is preferred to formulate the processing aid, and the above compounds may be used alone or in combination of two or more. use. In the case of formulating the processing aid, the blending ratio is 1 part by weight, preferably 0,01 to 3 parts by weight, more preferably 〇.〇5~1 by weight, based on 1 part by weight of the (a) linear polyacetal resin. Share. <Preparation method of polyacetal resin composition> In the present invention, the specific aspect of the method for producing the polyacetal resin composition is not particularly limited 'generally, it can be used as a synthetic resin composition or It is prepared by a known apparatus and method for preparing a molded article. That is, the necessary components can be mixed and kneaded using an extruder or another melt kneading device to prepare pellets for molding. Also, several extruders or other melt kneading devices can be used. In the present invention, the extruder is particularly preferably a twin-screw extruder from the viewpoint of the improvement of the mechanical properties and the dispersibility of the cellulose fiber powder. From the viewpoint of the improvement of the mechanical properties and the dispersibility of the cellulose fiber powder, it is particularly preferable to use a biaxial extruder which can be fed side by side, from the side of the extruder. A production method in which (C) cellulose fiber powder is supplied and melt-kneaded independently of other raw materials. In the preparation of the polyacetal resin composition of the present invention, a substance which improves the adhesion of the polyacetal resin to the (C) cellulose fiber powder can be used. Here, examples of the substance for improving the adhesion include an isocyanate compound, an isothiocyanate compound, and the modified isocyanate compound, a thermoplastic polyamine phthalate resin, and α,/3- A polymer, a copolymer, a boric acid compound, or the like of an acid anhydride of an olefinic unsaturated carboxylic acid. Further, in order to improve the physical properties according to the intended use, various known additives can be blended in the composition of the present invention. Examples of the additives include various coloring agents, lubricants, nucleating agents, surfactants, heteropolymers, organic polymer modifiers, and inorganic, organic, and metal fibers, powders, and the like. A plate-shaped filler may be used in combination of one or more of these. <Forming Method and Use of Polyacetal Resin Composition> The polyacetal resin composition of the present invention can be formed by a conventionally known forming method (e.g., injection molding, extrusion molding, press molding, blow molding, vacuum forming). Forming into various molded articles by methods such as foam molding, rotational molding, and gas injection molding. Particularly suitable is injection molding. Further, these molded articles can be used in various applications such as automobile parts, electric and electronic parts, building materials, living related parts, decorative related parts, and medical related parts. 100136255 19 201219484 Specifically, 5, as automotive parts, can be cited: internal handles, fuel storage box openers, seat belt buckles, auxiliary packaging materials, various switches, buttons, interiors such as joysticks, clamps, etc.; dials, Electrical system components such as connectors; automotive electrical and electronic components such as acoustic sighs or π car navigation devices; metal contact parts represented by carrier plates of window regulators, m贞 actuator parts, mirror parts, To the water n horse (four) system parts, fuel (four) system parts and other institutional parts. Examples of the electric and electronic components include parts or components of a device that is formed of a polycondensation-lipid molded article and has a plurality of metal contacts, such as: an audio device, a video device, or a telephone, a photocopier, a facsimile machine, OA ((10)ee Aut. Delete, office automation) equipment such as word processor, computer, etc.; parts or components of toys, specifically, a bottom plate, a gear, an operating lever, a cam, a pulley, a bearing, and the like. Furthermore, it can be applied to building materials and piping parts such as lighting fixtures, building tools, piping, stopcocks, faucets, parts around the toilet room, etc.; knowledgeable parts, straight, lip balm, mouth, mm water purifier, cutting material, spray A wide range of life-related parts, decorative related parts, and medical related parts such as fog containers, aerosol containers, ordinary containers, and syringe holders. [Examples] Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited by the examples. [Examples 1 and 2, Comparative Examples 1 to 3] In the ratios shown in Table 1, (4) linear polycondensation tree, (b) branch polycondensation 100136255 201219484 tree planting (C) cellulose fiber Powder, (4) hindered bismuth antioxidant, (4) nitrogen-containing compound, and (f) auxiliaries are prepared by using a twin-screw extruder to prepare a granulated polyacetal resin composition. (4) Cellulose The fiber powder is supplied and mixed independently from the side of the twin screw extruder by the feeder. The obtained particles were formed into a predetermined test > by an injection molding machine, and subjected to test evaluation. The results are shown in Table i. [Ingredients] The detailed description of the ingredients used is as follows. (a) Linear polyacetal resin (a-Ι) is a linear polycondensation obtained by copolymerization of 96.5 wt% j, 里/〇 and 1,3-pentacyclic pentane 35 wt%. Acid-reducing tree 曰月曰炫融指数=27 g/ΙΟ minute (manufactured by Poly Plastics Co., Ltd.) (b) Branched polyacetal resin 1,3-dioxanone 17% by weight 0.1% by weight copolymerization And the obtained points are g'l〇 minutes (Poly Plastics shares (b-Ι) makes the second alpha burned 98.2% by weight and the tri-sulfonic acid-triglycerin-trans-polyacetal resin, manufactured by Melt Index Co., Ltd.) (c) Cellulose fiber powder 15 'Average fiber length 3 〇〇# m, ~90 g/L (Rettenmaier (cl) ARBOCEL BC200, aspect ratio α cellulose purity 99.5% 'Prepared specific gravity %) The following 'average fiber Length 5〇μηι (c-2) KC Flock W-200, aspect ratio 2 100136255 201219484 Below, a cellulose purity is 99% or more, and pine specific gravity is 300 to 360 g/L (manufactured by Nippon Paper Chemicals Co., Ltd.) (d Hindered phenolic antioxidant (d-1) pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (4) nitrogen-containing compound (e-Ι) melamine (f) Processing aid (f-Ι)-extended ethyl bis-lipid amide [Extrusion conditions] Extruder ·· TEX-30a (L/D=38.5), manufactured by Nippon Steel Works Co., Ltd. Screw rotation number: 129 rpm Roller temperature: C2=160°C, C3~Cll.D=200t: [Forming conditions] Forming machine: ROBOSHOT S2000U00B, screw diameter 28 mm, manufactured by Fanuc
汽缸溫度：200°C 模具溫度：90°C(水溫調節） [試驗方法] 試驗方法之詳細說明係如下所述。 (1)拉伸強度、拉伸伸長度(破裂應變） ’評估拉伸強度 根據以IS0527]、2所規定之評估基準 (MPa)、拉伸伸長度(％)。 100136255 22 201219484 (2) 彎曲彈性率、彎曲強度 依據IS0178，測定彎曲強度(MPa)、彎曲彈性率（MPa)。 (3) 夏比衝擊強度(缺口） 依據IS0179/leA，測定夏比衝擊強度(缺口）(kJ/m2)。 (4) 外觀評估 目視觀察依據IS0178之彎曲試驗片之外觀 [表1] 項目 單位 實施例1 實施例2 比較例1 比較例2 比較例3 組成 a-1 重量份 100 100 100 100 100 b-1 重量份 1.45 7.69 1.46 c-1 重量份 43.1 43.1 43.1 c-2 重量份 43.9 43.9 d-1 重量份 0.25 0.25 0.25 0.37 0.37 e-1 重量份 0.15 0.15 0.15 0.22 0.22 f-1 重量份 0.18 0.18 0.18 0.26 0.26 物性評估 拉伸強度 MPa 65.2 67.0 61.8 50.8 52.2 拉伸伸長度 % 3.3 3.2 3.1 2.4 2.6 彎曲強度 MPa 106.8 106.9 100.7 89.0 90.7 彎曲彈性率 MPa 4953 5015 4926 4911 5042 夏比衝擊強度(缺口） kJ/m2 3.4 3.2 2.9 2.9 30 纖維素纖維粉末之 分散性(目視觀察） 良好 良好 良好 良好 良好 組成物(實施例1、2)與未調配⑻分枝聚祕樹脂之比較例】 相比’尤其是拉伸強度、彎曲、衝擊強度提高，並分別 具有較高之值。又，由比較例2與比較例3之比較中得知， 於纖維素纖祕末未滿足本發明要件之情料，雖亦調配⑻ 分枝聚縮賴脂，並發現彎曲賴率之改善，但拉伸強度、 100136255 23 201219484 彎曲強度、衝擊強度之值較低。 再者，於各實施例及比較财，對於未調配⑴加工助劑之 情形時之組成物㈣樣地製備並評估，其具有與分別對應之 實施例及比較例㈣之機械雜(拉伸特性、f曲特性、衝 擊特性等)(並未特別記载於表1)。為了使炫融加卫安定，並 確保成形品之品質之安定性、均—性，較理想的是調配⑺ 加工助劑，因此於表1中係顯示調配⑴加工助劑之組成物之 結果’但如上所述’ *表丨係明確可知本發明之對於改善機 械特性之效果’尤其是經由（b)分枝聚祕樹脂之調配與纖 維素纖維粉末之選擇所產生之效果。 100136255 24Cylinder temperature: 200 ° C Mold temperature: 90 ° C (water temperature adjustment) [Test method] The detailed description of the test method is as follows. (1) Tensile strength and tensile elongation (fracture strain) 'Evaluation of tensile strength According to the evaluation criteria (MPa) and tensile elongation (%) specified in IS0527], 2. 100136255 22 201219484 (2) Flexural modulus and flexural strength According to IS0178, the flexural strength (MPa) and the flexural modulus (MPa) were measured. (3) Charpy impact strength (notch) Charpy impact strength (notch) (kJ/m2) was measured according to IS0179/leA. (4) Appearance evaluation Visual observation The appearance of the bending test piece according to IS0178 [Table 1] Item Unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition a-1 Part by weight 100 100 100 100 100 b-1 Parts by weight 1.45 7.69 1.46 c-1 parts by weight 43.1 43.1 43.1 c-2 parts by weight 43.9 43.9 d-1 parts by weight 0.25 0.25 0.25 0.37 0.37 e-1 parts by weight 0.15 0.15 0.15 0.22 0.22 f-1 parts by weight 0.18 0.18 0.18 0.26 0.26 Physical property evaluation Tensile strength MPa 65.2 67.0 61.8 50.8 52.2 Tensile elongation % 3.3 3.2 3.1 2.4 2.6 Bending strength MPa 106.8 106.9 100.7 89.0 90.7 Flexural modulus MPa 4953 5015 4926 4911 5042 Charpy impact strength (notch) kJ/m2 3.4 3.2 2.9 2.9 30 Dispersibility of Cellulose Fiber Powder (Visually Observed) Good Good Good Good Good Composition (Examples 1, 2) and Unmixed (8) Branched Polyester Resin Comparative Example] In particular, tensile strength, The bending and impact strength are increased and have higher values, respectively. Further, from the comparison between Comparative Example 2 and Comparative Example 3, it was found that the cellulose fiber was not satisfied with the requirements of the present invention, and although (8) branched polycondensation was also prepared, and the improvement of the bending rate was found, However, the tensile strength, 100136255 23 201219484 bending strength, impact strength value is lower. Further, in each of the examples and comparative examples, the composition (4) in the case where the processing aid was not formulated (1) was prepared and evaluated, and had mechanical impurities (tensile characteristics) corresponding to the respective examples and comparative examples (4). , f-curve characteristics, impact characteristics, etc.) (not specifically described in Table 1). In order to ensure the stability of the smelting and cooling, and to ensure the stability and uniformity of the quality of the molded product, it is desirable to formulate (7) processing aids. Therefore, in Table 1, the results of the composition of the processing aid (1) of the processing aid are shown. However, as described above, the '* 丨 明确 明确 明确 明确 明确 明确 明确 明确 明确 明确 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 100136255 24