201041946 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉纖維素纖維所強化，且兼具高剛性與優越 之熱傳導性、滑動性、制振性等，不會如無機填充材所形成 之強化材料般發生比重增大或灰分增加的聚縮藤樹脂組成 物。 【先前技術】 聚縮醛樹脂係具有機械特性、熱特性、電特性、滑動性、 成形性等優越特性，主要作為構造材料或機構零件而廣泛使 用於電氣機器、汽車零件、精密機械零件等。隨著聚縮醛樹 脂的利用領域擴大，其要求特性有逐漸高度化、複合化、特 殊化的傾向。 例如，為了提升聚縮醛樹脂之強度或剛性，一般有如調配 玻璃系無機填充材等之強化材的方法，但此方法所得之聚縮 搭樹脂組成物的比重變高，亦有於焚燒後殘留大量灰分（焚 燒殘潰）的問題。又，聚縮搭樹脂原本具有之滑動性等之特 長大幅損失。再者，近年來，在機構零件等之精密化的進展 中，有時除了強度或剛性之提升以外，尚要求熱傳導性或制 振性等之改良，但藉由調配玻璃系無機填充材等之強化材的 方法將難以對應此要求。 對於上述問題，日本專利特開平3-217447號公報中揭示 有於聚縮醛樹脂中調配了紙漿的聚縮醛樹脂組成物，並顯示 4 099111393 201041946 改善了機械強度、耐熱性、燃燒性(燃燒時之樹脂滴落）等。 然而’此方法中，聚縮醛樹脂與紙漿的混合容易不充分，而 難以得到穩定並優越的特性，實用上並不適合。又，此日本 專利特開平3-217447號公報中，對於聚縮醛樹脂組成物之 熱傳導性、滑動性、制振性等之改善並無任何教示。 另外’日本專利特開2007-084713號公報係提供一種用於 » 付到含有經解纖之纖維素纖維的熱可塑性樹脂組成物的製 〇 造方法，但此日本專利特開2007-084713號公報中，並無有 關聚縮崎脂組成物之具體記載，且不僅是強度或剛性之提 .升對於改善熱傳導性、滑動性、制振性等，並兼具此等特 性的樹脂1 且成物並無任何揭示。 另外，日本專利特開平3-28260號公報所記載之發明中， 係對於聚縮醛樹脂少量地調配由微結晶纖維素及纖維質性 纖維素所組成群選出之就劑，以m祕樹脂之熱穩定 性，但此發明中，聚縮醛樹脂組成物之剛性、熱傳導性、滑 動性、制振性等之改良均未達成。 * 【發明内容】 . ^知的技術中，係如上述般，無法得到兼具剛性、熱傳導 性、滑祕、制振性，且低比重、低灰分之聚祕樹脂組成 物。 本發明之目的在於解決此等問題，提供兼具優越之剛性、 熱傳導性、滑紐、制振性，減重且灰分亦較少的聚祕 099111393 5 201041946 樹脂組成物及其成形品。 凡 荨人為了解決上述問題而潛心研究，結果發現， 藉由在_脂中組合調配特定之纖維填充材與添加 d貝]可解决上述問題而㈣能達成目的之聚、_樹脂組成 物及其成形品，遂完成本發明。 亦即本冑明係提供一種含有下述者而成之纖維素纖維強 化聚縮酸樹脂組成物與其成形品： (a) 相對於聚縮醛樹脂1〇〇重量份，含有 (b) 經解纖之纖維素纖維10〜150重量份； (C)受阻酚系抗氧化劑0.01〜3重量份；及 (自如基二α井化合物、胍胺(叩⑽啦丨加)化合物、肼化 合物及聚酿胺之至少1種含氮化合物G.G1〜3重量份。 本务明之纖維素纖維強化聚縮搭樹脂組成物係剛性、低比 .重：低灰分、熱傳導性、滑動性、性優越，適合用於有 關車零件、電氣•電变 【實施方式】” “牛、㈣、文具類等的成形品。 =下詳細㈣本發明之聚__組成物。 =本發日以聚祕則旨組成物的主要齡係如以下所 <(a)聚縮醛樹月旨> 以氧基亞曱基(-OCH2-)作為主要 以實質上僅由氧基亞甲基單位之 (a)成分之聚縮醛樹脂係 構成單位的高分子化合物， 099111393 6 201041946 重複單位所構成的聚縮，雜、含純基亞甲基單位以外 之乂、他’、單體單位的聚縮駿共聚物為代表性樹脂。再者，聚 祕樹脂t’亦含㈣岐分技義成分歧卿成成分進 灯共聚合而導人了分技構造或交聯構造的共聚物，或具有由 氧基亞f基之重複單位所構成之聚合物單位與其他聚合物 單位的嵌段共聚物或接枝共聚鮮。此韓祕樹脂可單獨 使用或組合二種以上使用。 一般而β，聚縮醛均聚物係藉曱醛酐或三。山（甲醛之環狀 三聚物）之聚合而製造，通常藉由將其末端進行酯化，而對 熱分解呈穩定化。 ^ 對此’聚縮醛共聚物一般係藉由使甲醛或一般式 (2 )η[弋中η表示3以上之整數]所示之甲越之環狀寡聚 物(例士 — ώ)、與壤狀酸或環狀甲酸等之共單體進行共聚合 〇 而找’通*财解以去除末端之不穩定部分而使其對 解呈穩定化。 ” 作為聚縮’聚物之主㈣，可舉例等，通 常使用三咄。 m /、單體中包括環狀醚、環氧丙基醚化合物、環狀曱醛、 衣狀酉曰(例如/3内内酯等）、乙烯基化合物(例如笨乙婦、 醚等）等。 乍為裒狀喊，可舉例如環氧乙烧、環氧兩烧、環氧丁烧、 衣氧％己燒、表氣醇、表溴醇、環氧苯〔稀、氧雜環丁烧 099111393 7 201041946 (〇\6131^)、3,3-雙（氯曱基）氧雜環丁烷、四氫呋喃、三噚庚 環(trioxepane)、1,3-二11 号烧等。 作為環氧丙基醚化合物，可舉例如烷基或芳基環氧丙基醚 (例如曱基環氧丙基醚、乙基環氧丙基醚、苯基環氧丙基醚、 萘基環氧丙基醚等）、伸烷二醇二環氧丙基醚或多伸烷二醇 二環氧丙基醚（例如乙二醇二環氧丙基醚、三乙二醇二環氧 丙基醚、丁二醇二環氧丙基醚等）、烷基或芳基環氧丙基醇 等。 作為環氧曱醛，可舉例如1,3-二哼烷、丙二醇曱醛、二乙 二醇曱醛、三乙二醇曱醛、1,4-丁二醇曱醛、1,5-戊二醇曱 醛、1,6-己二醇曱醛等。 此等共單體可單獨使用或組合二種以上使用。此等共單體 中，通常使用環狀醚及/或環狀甲醛，特佳為環氧乙烷等之 環狀醚，或1，3-二哼烷、1,4-丁二醇曱醛、二乙二醇曱醛等 之環狀甲醛。 此等共單體(例如環狀醚及/或環狀曱醛)單位的比例，係相 對於聚縮醛樹脂整體，一般為0.1〜20重量％之範圍、較佳 0.5〜20重量％、更佳0.5〜15重量％(特佳1〜10重量％)左右。 (a)成分之聚縮醛樹脂的熔融指數並無特別限定，較佳為 1〜100g/10分鐘之範圍，特佳為5〜50g/10分鐘之範圍。熔融 指數過小及過大時，有無法充分得到本發明效果的情形。 又，熔融指數係根據 ASTM-D1238,依 190°C、2.16kgf(21.2N) 8 099111393 201041946 之條件下測定之值。 <(b)纖維素纖維> (b)成分之纖維素纖 者。纖維素纖維集合針、使纖維素纖維集合體經解纖 者，可為天然物或工業μ 。^^多數之纖維素纖維呈結合一體化 維、木材纖維、洋麻麻纖維、竹纖維、綿纖 椰纖維等之集合體。、、麻纖維、黃麻纖m纖維、201041946 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to strengthening by cellulose fibers, and has high rigidity and superior thermal conductivity, slidability, vibration damping property, etc., and is not as inorganic filler A polycene resin composition in which the specific gravity is increased or the ash is increased as in the formed reinforcing material. [Prior Art] The polyacetal resin has excellent properties such as mechanical properties, thermal properties, electrical properties, slidability, and formability, and is widely used as a structural material or a mechanical component for electrical equipment, automobile parts, and precision mechanical parts. With the expansion of the use of polyacetal resins, the required properties are gradually becoming higher, more complex, and more specialized. For example, in order to increase the strength or rigidity of the polyacetal resin, a method of blending a reinforcing material such as a glass-based inorganic filler is generally used. However, the specific gravity of the polycondensation resin composition obtained by this method becomes high, and remains after incineration. A large amount of ash (burning residue) problem. Further, the polycondensation resin originally has a large loss of the slidability and the like. In addition, in recent years, in addition to improvement in strength and rigidity, improvements in thermal conductivity and vibration resistance are required, but glass-based inorganic fillers are required to be blended. The method of strengthening the material will be difficult to meet this requirement. In the above-mentioned problem, a polyacetal resin composition in which a pulp is blended in a polyacetal resin is disclosed in Japanese Patent Laid-Open No. Hei No. 3-217447, and it is shown that 4 099111393 201041946 improves mechanical strength, heat resistance, and flammability (combustion). When the resin drops, etc.). However, in this method, the mixing of the polyacetal resin and the pulp is not sufficient, and it is difficult to obtain stable and superior characteristics, which is not suitable for practical use. Further, in Japanese Laid-Open Patent Publication No. Hei-3-217447, there is no suggestion for improvement of thermal conductivity, slidability, vibration damping property, and the like of the polyacetal resin composition. In addition, Japanese Laid-Open Patent Publication No. 2007-084713 provides a method for producing a thermoplastic resin composition containing a defibrated cellulose fiber, but the Japanese Patent Laid-Open Publication No. 2007-084713 There is no specific description about the polycondensate composition, and it is not only the strength or the rigidity. It is a resin 1 which has such characteristics as the heat conductivity, the slidability, the vibration damping property, and the like. There is no disclosure. In the invention described in Japanese Laid-Open Patent Publication No. Hei. No. 3-28260, a small amount of a polyacetal resin is selected from a group consisting of microcrystalline cellulose and cellulosic cellulose. Thermal stability. However, in the present invention, improvements in rigidity, thermal conductivity, slidability, vibration damping property, and the like of the polyacetal resin composition have not been achieved. * [Invention] In the above-mentioned technique, as described above, it is impossible to obtain a polymylon resin composition which has rigidity, thermal conductivity, slipperiness, vibration damping property, and low specific gravity and low ash. SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a resin composition and a molded article thereof which have excellent rigidity, thermal conductivity, sliding strength, vibration damping property, weight loss and less ash. In order to solve the above problems, the monks have studied hard and found that the above problems can be solved by combining the specific fiber fillers and the addition of d shells in the _fat. (4) The purpose of the polymerization, the _resin composition and its The molded article is completed by the present invention. In other words, the present invention provides a cellulose fiber-reinforced polyacetal resin composition and a molded article thereof comprising: (a) (b) a solution of 1 part by weight of the polyacetal resin; 10 to 150 parts by weight of the cellulose fiber of the fiber; (C) 0.01 to 3 parts by weight of the hindered phenol-based antioxidant; and (freely, the compound of the bismuth a-α compound, the guanamine (叩), the ruthenium compound, and the poly-brew At least one nitrogen-containing compound of the amine, G.G1 to 3 parts by weight. The cellulose fiber-reinforced polycondensation resin composition of the present invention has rigidity, low ratio, weight: low ash, thermal conductivity, slidability, and superiority, and is suitable for For the car parts, electrical and electrical changes [embodiment] "" cattle, (four), stationery, etc. molded products. = below detailed (four) the composition of the present invention __ composition of the present day to gather The main age of the substance is as follows (<(a) polyacetal tree)> The oxyindenyl group (-OCH2-) is mainly composed of the (a) component substantially only by the oxymethylene unit. Polyacetal resin is a polymer compound of a unit, 099111393 6 201041946 Polycondensation composed of repeating units Miscellaneous, containing pure benzylene units other than 乂, he', monomer unit poly condensed copolymer is a representative resin. In addition, poly-myster resin t' also contains (four) 岐 技 技 分歧 分歧 分歧Copolymerization of the lamp leads to a copolymer of a sub-structure or a cross-linked structure, or a block copolymer or graft copolymerization of a polymer unit composed of repeating units of an oxy-f-group and other polymer units The above-mentioned Korean resin may be used singly or in combination of two or more. In general, β, a polyacetal homopolymer is produced by polymerization of furfural or tris. (a cyclic trimer of formaldehyde), usually borrowed. The end of the esterification is stabilized by thermal decomposition. ^ This polyacetal copolymer is generally represented by formaldehyde or general formula (2) η [where η represents an integer of 3 or more] The oligo-oligomer of the genus of the genus (the scorpion- ώ), and the co-polymerization of the sulphuric acid or the cyclic formic acid, etc. Stabilization of the solution." As the main (4) of the polycondensation polymer, for example, three turns are usually used. m /, the monomer includes a cyclic ether, a epoxidized propyl ether compound, a cyclic acetal, a phthalic acid (for example, /3 lactone, etc.), a vinyl compound (such as a stupid woman, an ether, etc.)乍 裒 , , , , , , , , , , , , , , , , 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧099111393 7 201041946 (〇\6131^), 3,3-bis(chloroindenyl)oxetane, tetrahydrofuran, trioxepane, 1,3-di 11 or the like. The ether compound may, for example, be an alkyl or aryl epoxypropyl ether (for example, decyl epoxypropyl ether, ethyl epoxidized propyl ether, phenyl epoxidized propyl ether, naphthyl epoxypropyl ether) Et.), alkylene glycol diepoxypropyl ether or polyalkylene glycol diepoxypropyl ether (eg ethylene glycol diepoxypropyl ether, triethylene glycol diepoxypropyl ether, dibutyl) An alcohol diethylene oxide propyl ether or the like, an alkyl group or an aryl epoxy propyl alcohol or the like. Examples of the epoxyfurfural include 1,3-dioxane, propylene glycol furfural, diethylene glycol furfural, triethylene glycol furfural, 1,4-butanediol furfural, and 1,5-pentyl. Glycol furfural, 1,6-hexanediol furfural, and the like. These comonomers may be used singly or in combination of two or more. Among these comonomers, a cyclic ether and/or a cyclic formaldehyde is usually used, and a cyclic ether such as ethylene oxide or the like, or a 1,3-dioxane or 1,4-butanediol furfural is preferably used. And cyclic formaldehyde such as diethylene glycol furfural. The ratio of the units of such comonomers (for example, cyclic ether and/or cyclic furfural) is generally 0.1 to 20% by weight, preferably 0.5 to 20% by weight, based on the total amount of the polyacetal resin. It is preferably 0.5 to 15% by weight (extraordinarily 1 to 10% by weight). The melt index of the polyacetal resin of the component (a) is not particularly limited, but is preferably in the range of 1 to 100 g/10 min, particularly preferably in the range of 5 to 50 g/10 min. 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 a value measured in accordance with ASTM-D1238 under the conditions of 190 ° C and 2.16 kgf (21.2 N) 8 099111393 201041946. <(b) Cellulose fiber> Cellulose fiber of component (b). The cellulose fibers are collected in a needle, and the cellulose fiber assembly is defibrated, and may be a natural product or an industrial μ. ^^ Most of the cellulose fibers are a combination of integrated, dimensional, wood fiber, kenaf fiber, bamboo fiber, cotton fiber and the like. , hemp fiber, jute fiber, fiber
纖維素纖維集合n 使解纖作業順利進行狀財亚無特職制，可在能夠 維素纖維集合體可舉^㈣料轉。其巾較佳形狀之纖 厚°.™〜，寬一長3·:左二 β於使用紙桌片的情況’亦可使用將紙漿片捲成圓筒狀者、 壓扁成細長板狀者、折疊成細長板狀片者等。又，亦可將紙 衆片暫時作成切斷物。例如，亦可使用厚Q l〜5mm、較佳 1〜3mm，寬2mm〜lcm、長3mm〜3cm左右的短片狀者或 一邊2mm〜lcm左右的四角形狀者。 纖維素纖維集合體之水分含有率較佳為2〇重量％以下、 更佳Π重量。/〇以下、再更佳b重量％以下。水分含有率若 為20重量％以下，則容易因摩擦熱發生而造成升溫，纖維 素纖維集合體易解纖而不殘留凝集物，故較佳。又，水八八 有率係藉由卡爾費雪法之水分測定等所求取。 形成纖維素纖維集合體之纖維素纖維係由熱穩定性高之 099111393 9 门 201041946 觀點而言，較佳細纖維素含有量較高者，更佳係_ 含有量80重量％以上’再更佳為85重量。/以卜， 〇上，特佳9〇 重量％以上。 纖維素纖維集合體之纖維素纖維的平均纖維徑較佳為 0.1〜1000/πη、更佳1〜500/xm、再更佳5〜2〇〇从坩、特佳 10〜50μιη。纖維素纖維之平均纖維長較佳為0 0^100 土 更佳0.01〜50mm、再更佳〇.i〜10mm、特佳〇卜5 • 111。纖維 素纖維之高I比（長度/徑）較佳為2〜1〇〇〇、承社。 又住j〜5〇〇、再 更佳5〜20G、特佳5〜⑽。又’纖維素纖維亦可藉偶合 有胺基、取代胺基、環氧基、環氧丙基等之官能基的石夕燒偶 合劑）予以表面處理。 作為將(b)成分之纖維素纖維所使用之纖維素纖維集合體 進行解纖的方法，可舉例如仙具有旋轉翼之混合器或 機等裝置的方法。例如’可將纖維素纖維集合體置入具有旋 轉翼之混合◎中’藉由進行高迷餅而進行解纖。混合器若 為具有旋轉翼作為攪拌手段即可，較佳為具有加溫手段者， 可使用例如三井鑛山（股）製漢歇爾混合器舰2_(容量 20L)或Kawata(股）製超級混合器SMv_2〇(容量2〇l)等。 旋轉翼通常為上翼與下翼之2片構成，或上翼、中間翼、 下翼之3片構成’其片數並無制約。攪拌時之旋轉翼之平均 周速較佳雜HMGOm/秒之㈣行祕、更佳係依平均 周速i 0〜90m/秒、再更佳係依平均周速i 〇〜8〇m/秒進行授掉。 099111393 201041946 纖維素纖維集合體之解、 音_飧隹入μ 纖可將例如能依目視確認到纖維 =:二_化成綿狀時作為處理結束時刻。旋轉翼之平 述般以變化成綿狀之時 =物嶋_讀維綱樣貞、形狀、尺 寸、投入謂而改變，故較佳係如上 點作為基準。 ⑻成刀之經解纖之纖維素纖維的含有量，係相對於⑻成 分之聚祕樹月旨100重量份，為ι〇〜ΐ5〇重量份，更佳15〜12〇 Ο 重ϊ份。在含有量過少及過多時，由於無法充分得到本發明 效果，故不佳。 <(c)受阻酚系抗氧化劑> 本發明所使用之(C)受阻酚系化合物，可舉例如：單環式 受阻紛化合物（例如2,6-二第三丁基_對曱紛等）、以烴基或含 有硫原子之基所連結的多環式受阻酚化合物（例如2,2’_亞曱 基雙(4-甲基-6-第三丁基酚）、4,4，-亞曱基雙(2,6_二第三丁基 〇 酚）、u，3-參(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-第三丁基酚）、1，3,5-三曱基_2,4,6_參(3,5_ , 二第三丁基-4-羥基苄基)笨、4,4,-硫雙(3-甲基_6-第三丁基酚) ’ 等）、具有酯基或醯胺基之受阻酚化合物（例如正十八烷基 -3·(4，-羥基-3，,5，-二第三丁基笨基）丙酸酯、正十八烷基 _2-(4，-經基-3’，5’-二第三丁基苯基）丙酸酯、I，6己一醇雙 [3-(3,5-二第三了基-4_經基苯基)丙酸醋]、三乙二醇-雙[3-(3_ 第三丁基-5-甲基冰經基笨基)丙酸醋]、季戍四醇肆[3_(3’5- 11 099111393 201041946 二第三丁基-4-羥基苯基）丙酸酯]、3,9-雙P-[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}-2,4,8,10-四氧螺[5.5]十一烷、2-第三丁基-6-(3’-第三丁基-5’-甲基-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、二正十八烷基 -3,5-二第三丁基-4-羥基苄基磷酸酯、Ν,Ν’-六亞甲基雙(3,5-二第三丁基-4-羥基-二氫桂皮醯胺、Ν,Ν’-伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基）丙醯胺]、Ν，Ν’-四亞曱基雙[3-(3,5-二第三丁基-4-羥基苯基）丙醯胺]、Ν,Ν’-六亞曱基雙[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’-六亞甲基雙[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]肼、Ν，Ν’-雙[3-(3-第三丁基-5-曱基-4-羥基苯基）丙醯基]肼、1，3,5-參(3,5-二第三丁基-4-羥 基苄基）三聚異氰酸酯、1,3,5-參(4-第三丁基-3-羥基-2,6-二 曱基苄基)三聚異氰酸酯等）。 本發明中，（c)受阻酚系抗氧化劑可單獨或組合二種以上 使用。其調配比例係相對於⑻聚縮醛樹脂100重量份為 0.01〜3重量份，較佳為0.02〜1重量份。在含有量過少或過 多時，由於無法充分得到本發明效果，故不佳。 另外，在調製本發明之聚縮醛樹脂組成物時，可將(c)受 阻酚系抗氧化劑對於(a)聚縮醛樹脂於任意階段進行混合， 12 099111393 201041946 特佳係在與上述之(b)纖維素纖維的混合前，將(c)受阻酚系 抗氧化劑預先以擠出機等溶融混合至(a)聚縮醛樹脂中的方 法。 <(d)含氮化合物> 本發明之聚縮醛樹脂組成物中’係調配(d)選自胺基三畊 化合物、脈胺化合物、肼化合物及聚醯胺之至少1種含氮化 合物。 〇 作為胺基二啡化合物，可舉例如三聚氰胺或其衍生物[三 *氰胺一聚氰胺縮合物（蜜白胺、蜜勒胺、melon)等]、胍 胺或其衍生物、及胺基三啡樹脂[三聚氰胺之共縮合樹脂（三 水氰胺—曱駿樹脂、盼-三聚氰胺拍子脂、三聚氰胺-紛-曱酸樹 脂、苯胍胺三聚氰胺樹脂、芳香族多胺-三聚氰胺樹脂等）、 脈胺之共縮合樹脂等]等。 作為脈胺化合物，可舉例如脂肪族胍胺化合物（單胍胺 〇 類、伸烧基雙胍胺類等）、脂環族胍胺系化合物（單胍胺類 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）、或仏萘胍胺及其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]、含雜原子之胍胺系化 合物[含縮醛基之胍胺類、含四氧螺環之胍胺類^了口-胍胺、 CMTU·胍胺等）、含異三聚氰酸基之胍胺類、含咪唑環之胍 胺類等]等。又，亦包括使上述三聚氰胺、三聚氰胺衍生物、 胍胺系化合物之烷氧基甲基取代為胺基的化合物等。 099111393 13 201041946 作為肼化合物，可舉例如脂肪族魏酸耕系化合物(硬脂酸 肼、12,基硬脂酸肼、癸二酸二肼、十二烧二酸二耕、二 十烧-肼等）、脂軸叛酸肼系化合物（I，〗·雙(耕基碳乙 基）5異丙基乙内醯脲等）、芳香族羰酸肼系化合物(4_輕基 -3,5_二第三丁基苯絲甲酸肼、1_萘酸肼、2·萘酸肼、異酞 西夂肼、2,6_萘二減二肼等）、含雜原子之羧酸肼系化合物、 聚合物型鲮酸肼系化合物等。 作為聚酿胺，係包括：由二胺與二敌酸所衍生之聚酸胺； 併用胺基紐、視需要之二胺及/或二驗而得的聚酿胺； 併用内i日、視需要之二胺及/或二㈣而衍生的聚酿胺。又， 亦&括由二種以上不同之聚醯胺形成成分所形成的共聚合 聚酿胺。 作為具體之«胺之例子，可舉例如：聚醯胺3、聚酿胺 4、聚醯胺46、聚醯胺6、輯胺66、聚醯胺61〇、聚醯胺 612、聚酿胺1卜聚醯胺12等之脂肪族聚醢胺，由芳香族 二羧酸(例如對苯二曱酸及/或異酞酸)與脂肪族二胺(例如六 亞曱基一胺)所得之聚醯胺’由脂肪族二鲮酸(例如己二酸) 與芳香族二胺(例如間茬二胺)所得之聚醯胺，由芳香族及脂 肪族二羧酸(例如對苯二甲酸與己二酸)與脂肪族二胺(例如 六亞曱基二胺）所得之聚醯胺，以及此等之共聚物等。又， 亦可使用使聚酿胺硬鏈段與聚醚成分等其他之軟鏈段經鍵 結的聚醯胺系嵌段共聚物。 099111393 14 201041946 (d)選自胺基三畊化合物、胍胺化合物、肼化合物及聚酿 胺之含氮化合物，可單獨或組合二種以上而使用。其調配比 例係相對於(a)聚縮醛樹脂1〇〇重量份，為〇.〇1〜3 里Ϊ：份、 較佳0.02〜1重量份。在含有量過少及過多時，由於無法充 分得到本發明效果，故不佳。 另外’在調製本發明之聚縮醛樹脂組成物時，（d)選自胺 基三讲化合物、胍胺化合物、肼化合物及聚醯胺之含氮化八The cellulose fiber collection n enables the defibration operation to proceed smoothly, and there is no special system for the production of the fiber. The preferred shape of the towel is thicker. TM~, the width of one is longer than 3: the second two is used in the case of using a paper table. 'When the pulp sheet is rolled into a cylindrical shape, the flattened into a slender plate can also be used. , folded into a slender plate, etc. Further, the paper piece may be temporarily made into a cut piece. For example, a short sheet having a thickness of Q l 5 mm, preferably 1 mm 3 mm, a width of 2 mm to 1 cm, a length of 3 mm to 3 cm, or a square shape of about 2 mm to 1 cm may be used. The water content of the cellulose fiber aggregate is preferably 2% by weight or less, more preferably Π. /〇 below, more preferably b% by weight or less. When the water content is 20% by weight or less, the temperature rises due to the occurrence of frictional heat, and the cellulose fiber assembly is easily defibrated without leaving aggregates, which is preferable. In addition, the rate of water is determined by the moisture measurement of the Karl Fischer method. The cellulose fiber forming the cellulose fiber assembly is made of a high thermal stability of 099111393 9 201041946. Preferably, the fine cellulose content is higher, and more preferably, the content is 80% by weight or more. It is 85 weight. /Yi Bu, 〇上, 特佳9〇% by weight or more. The cellulose fibers of the cellulose fiber assembly preferably have an average fiber diameter of 0.1 to 1000 / πη, more preferably 1 to 500 / xm, still more preferably 5 to 2 Å, and preferably 10 to 50 μm. The average fiber length of the cellulose fibers is preferably 0 0 ^ 100 soil, more preferably 0.01 to 50 mm, more preferably 〇. i ~ 10 mm, and particularly good 5 5 • 111. The high I ratio (length/diameter) of the cellulose fibers is preferably 2 to 1 Å, Chengshe. Also live j ~ 5 〇〇, then better 5 ~ 20G, especially good 5 ~ (10). Further, the cellulose fiber may be surface-treated by a coupling agent of a compound having an amine group, a substituted amino group, an epoxy group or a epoxy group. The method of defibrating the cellulose fiber assembly used for the cellulose fibers of the component (b) may, for example, be a method of using a device such as a mixer or a rotary wing. For example, the cellulose fiber assembly can be placed in a mixture having a rotating wing, and defibration can be carried out by performing a loaf cake. If the mixer has a rotating wing as a stirring means, preferably a heating means, for example, a Hanschel mixer ship 2_ (capacity 20L) or Kawata (unit) made by Mitsui Mining Co., Ltd. Mixer SMv_2〇 (capacity 2〇l) and so on. The rotor is usually composed of two pieces of the upper wing and the lower wing, or three pieces of the upper wing, the middle wing, and the lower wing. The number of the blades is not limited. The average peripheral speed of the rotating wing during mixing is preferably HMGOm/sec (4), the best is based on the average weekly speed i 0~90m/sec, and the better is based on the average weekly speed i 〇~8〇m/sec. Granted. 099111393 201041946 The solution of the cellulose fiber aggregate, the sound _ 飧隹 μ 纤 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 。 。 。 。 。 。 。 。 。 。 。 。 。 When the rotary wing is changed into a cotton-like shape, the object _ reading dimension, shape, size, and input are changed. Therefore, it is preferable to use the above point as a reference. (8) The content of the defibrated cellulose fiber of the knives is 100 parts by weight relative to the component of the (8) component, and is 〇 〇 ΐ 5 〇 by weight, more preferably 15 to 12 〇 Ο ϊ. When the content is too small or too large, the effect of the present invention cannot be sufficiently obtained, which is not preferable. <(c) Hindered Phenolic Antioxidant> The (C) hindered phenol-based compound used in the present invention may, for example, be a monocyclic hindered compound (for example, 2,6-di-t-butyl-p-quinone a polycyclic hindered phenol compound linked to a hydrocarbon group or a group containing a sulfur atom (for example, 2,2'-fluorenylene bis(4-methyl-6-tert-butylphenol), 4, 4, - anthracenyl bis (2,6-di-t-butyl decyl phenol), u, 3- gin (2-mercapto-4-hydroxy-5-tert-butylphenyl) butane, 4, 4' _Butylene bis(3-indolyl-6-t-butylphenol), 1,3,5-trimethyl 2,4,6-paran (3,5_, di-t-butyl-4-hydroxyl) Benzyl) stupid, 4,4,-thiobis(3-methyl-6-t-butylphenol) ', etc.), hindered phenolic compound having an ester group or a guanamine group (eg, n-octadecyl-3) · (4,-Hydroxy-3,5,-di-t-butylphenyl) propionate, n-octadecyl-2-(4,-carbamicin-3',5'-di-3rd Phenyl) propionate, I,6-hexanol bis[3-(3,5-di-t-thylene-4-ylphenyl)propionic acid vinegar], triethylene glycol-bis[3- (3_Tertibutyl-5-methyl glacial base) propionic acid vinegar], quaternary phosphonium tetraol [3_(3'5- 11 099111393 2010419 46 bis-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis-P-[3-(3-tert-butyl-4-hydroxy-5-mercaptophenyl)propanyloxy 1,1,1-dimercaptoethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-tert-butyl-6-(3'-tert-butyl- 5'-Methyl-2'-hydroxybenzyl)-4-mercaptophenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4 , 6-di-t-amyl phenyl acrylate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzyl phosphate, hydrazine, Ν'-hexamethylene double (3 ,5-di-t-butyl-4-hydroxy-dihydrocinnamate, hydrazine, Ν'-extended ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoid Amine], hydrazine, Ν'-tetradecyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide], hydrazine, Ν'-hexamethylene bis-[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propanamine], hydrazine, Ν'-extended ethyl bis[3-(3-tert-butyl-5-fluorenyl-4- Hydroxyphenyl) acrylamide], hydrazine, Ν'-hexamethylene bis[3-(3-tert-butyl-5-fluorenyl-4-hydroxyphenyl)propanamide], hydrazine, hydrazine -Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, fluorene, Ν'-bis[3-(3-t-butyl) -5-Mercapto-4-hydroxyphenyl)propanyl]anthracene, 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-triisocyanate, 1,3, 5- cis (4-tert-butyl-3-hydroxy-2,6-dimercaptobenzyl)trimeric isocyanate, etc.). In the present invention, the (c) hindered phenol-based antioxidant may be used singly or in combination of two or more. The blending ratio is 0.01 to 3 parts by weight, preferably 0.02 to 1 part by weight, per 100 parts by weight of the (8) polyacetal resin. When the content is too small or too large, the effect of the present invention cannot be sufficiently obtained, which is not preferable. Further, in the preparation of the polyacetal resin composition of the present invention, the (c) hindered phenol-based antioxidant may be mixed at any stage with respect to (a) the polyacetal resin, and 12 099111393 201041946 is particularly preferable to the above ( b) A method in which (c) a hindered phenol-based antioxidant is previously melt-mixed in an extruder or the like to (a) a polyacetal resin before mixing of the cellulose fibers. <(d) Nitrogen-containing compound> The polyacetal resin composition of the present invention is formulated (d) to be at least one nitrogen-containing compound selected from the group consisting of an amine tri-till compound, a pulsed amine compound, an anthraquinone compound, and a polydecylamine. Compound. The oxime compound may, for example, be melamine or a derivative thereof [three-cyanamide-melamine condensate (melamine, melem, melon) or the like], guanamine or a derivative thereof, and an amine. a sulphate resin [melamine, a melamine resin, a melamine resin, a melamine-melamine resin, a melamine melamine resin, an aromatic polyamine-melamine resin, etc.), a co-condensation resin such as an amine, etc.]. Examples of the amide compound include an aliphatic guanamine compound (monoguanamine oxime, or exobutyl phthalamide), an alicyclic guanamine compound (monoguanamine), and an aromatic amide compound. [monodecylamines (benzoguanamine and its functional group substitutions, etc.), or phthalocyanine and its functional substituted derivatives, polyfluorenes, amines, aralkyl or aralkyl groups Amines, etc., heteroatom-containing guanamine compounds [acetal-containing guanamines, tetraoxose-containing guanamines, oxime, CMTU, decylamine, etc.), heterotrimers A guanamine such as a cyanate group, an amide containing an imidazole ring, or the like. Further, a compound obtained by substituting an alkoxymethyl group of the above melamine, a melamine derivative or a guanamine compound into an amine group is also included. 099111393 13 201041946 As the ruthenium compound, for example, an aliphatic ferulic acid-based compound (ytterbium stearate, 12, bismuth stearate, bismuth subsalt, didecyl succinic acid, simmering, simmering and simmering) Etc.), lipid-axis retinoic acid-based compounds (I, 〗 〖Shuang (cultivated carbon ethyl) 5 isopropyl ethyl carbazide, etc.), aromatic carboxylic acid lanthanide compounds (4_light base-3,5_ Bismuth tributyl phthalate, bismuth 1-yle naphinate, bismuth 2-naphthoate, isoindole, 2,6-naphthalene dioxime, etc., carboxylic acid lanthanide compound containing a hetero atom, A polymer type bismuth citrate compound or the like. The polyamine can include: a polyamine derived from a diamine and a dicarboxylic acid; and an amine amine, an optional diamine and/or a second polyamine; A polyamine derived from a diamine and/or a di(tetra) is required. Further, &> includes a copolymerized polyamine formed from two or more different polyamine forming components. Specific examples of the amine include, for example, polyamine 3, polyamine 4, polyamine 46, polyamine 6, amidine 66, polyamine 61, polyamine 612, polyamine An aliphatic polyamine which is obtained from an aromatic dicarboxylic acid (for example, terephthalic acid and/or isodecanoic acid) and an aliphatic diamine (for example, hexamethylene monoamine). Polyamides are polyamines derived from aliphatic dicarboxylic acids (such as adipic acid) and aromatic diamines (such as m-diamine), from aromatic and aliphatic dicarboxylic acids (such as terephthalic acid). Polydecylamine obtained from adipic acid) and an aliphatic diamine such as hexamethylenediamine, and copolymers thereof and the like. Further, a polyamine-based block copolymer in which another hard segment such as a polystyrene hard segment and a polyether component is bonded may be used. 099111393 14 201041946 (d) A nitrogen-containing compound selected from the group consisting of an amine-based three-till compound, a guanamine compound, an anthraquinone compound, and a polyamine, and may be used singly or in combination of two or more. The compounding ratio is 1 part by weight of the (a) polyacetal resin, and is 0.02 to 1 part by weight, preferably 0.02 to 1 part by weight. When the content is too small and too large, the effect of the present invention cannot be sufficiently obtained, which is not preferable. Further, when the polyacetal resin composition of the present invention is prepared, (d) is selected from the group consisting of an amine-based compound, a guanamine compound, a ruthenium compound, and a polyamine.
物可在任意階段混合至（a)聚縮醛樹脂，但特佳係與上述（） 受阻酚系抗氧化劑同樣地’在與(b)纖維素纖維混合前，將(d) 含氮化合物預先以擠出機等溶融混合至(a)聚縮醛樹脂中的 方法。 <(e)金屬化合物> 本發明之聚縮醛樹脂組成物中，可進一步調配(e)選自鹼 金屬或鹼土金屬之氧化物、氫氧化物、無機酸鹽及羧酸鹽之 〇 至少一種金屬化合物。 作為驗金屬或鹼土金屬之氧化物，可舉例如Ca〇、MgO、 • Zn0專。作為驗金屬或驗土金屬之氫氧化物，可舉例如 • Li0H、Ca(0H)2、Mg(OH)2等。作為驗金屬或驗土金屬之無 機酸鹽，可舉例如碳酸鹽(Li2C03、Na2C03、K2c〇3、CaC03、 MgC〇3等）、硼酸鹽、磷酸鹽等。 另外’作為與驗金屬或驗土金屬形成叛酸鹽的有機叛酸， 可舉例如：飽和單羧酸(醋酸、丙酸、丁酸、異丁酸、戊酸、 099111393 15 201041946 異戊酸、三甲基乙酸、己酸、辛酸等）、飽和二羧酸(草酸、 丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二 酸等）、以及此等之含氧酸（乙醇酸、乳酸、甘油酸、羥基丁 酸、檸檬酸等）、不飽和單羧酸[(甲基）丙烯酸、丁烯酸、異 丁烯酸等]、不飽和二羧酸(順丁烯二酸、反丁烯二酸等）以及 此等之含氧酸（丙炔酸等），聚合性不飽和羧酸[(甲基）丙烯酸 等之聚合性不餘和單羧酸、聚合性不飽和多元羧酸（衣康 酸、順丁烯二酸、反丁烯二酸等）、多元幾酸之酸針或單酯（順 丁烯二酸單乙基酯等之單烷基酯等）等]與烴烯（6烯、丙烯等)The material may be mixed at any stage to (a) a polyacetal resin, but particularly preferably, in the same manner as the above-mentioned () hindered phenol-based antioxidant, (d) a nitrogen-containing compound is previously prepared before being mixed with the (b) cellulose fiber. A method of melt-mixing into an (a) polyacetal resin by an extruder or the like. <(e) Metal compound> The polyacetal resin composition of the present invention can be further formulated with (e) an oxide, a hydroxide, a mineral acid salt and a carboxylate selected from an alkali metal or an alkaline earth metal. At least one metal compound. Examples of the oxide of the metal or alkaline earth metal include Ca 〇, MgO, and Zn0. Examples of the metal hydroxide or the hydroxide of the soil-checking metal include LiOH, Ca(0H)2, Mg(OH)2, and the like. Examples of the inorganic acid of the metal or the soil-checking metal include carbonate (Li2C03, Na2C03, K2c3, CaC03, MgC3, etc.), borate, phosphate, and the like. In addition, as an organic tickacid which forms a tartrate with a metal or a soil test, for example, a saturated monocarboxylic acid (acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, 099111393 15 201041946 isovaleric acid, Trimethylacetic acid, caproic acid, caprylic acid, etc.), saturated dicarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, etc.), and Oxyacids (glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, citric acid, etc.), unsaturated monocarboxylic acids [(meth)acrylic acid, crotonic acid, methacrylic acid, etc.], unsaturated dicarboxylic acids ( a maleic acid, a fumaric acid, or the like, and an oxo acid (such as a propyric acid), a polymerizable unsaturated carboxylic acid, a polymerizable property such as (meth)acrylic acid, or a monocarboxylic acid, A polymerizable unsaturated polycarboxylic acid (itaconic acid, maleic acid, fumaric acid, etc.), an acid needle or a monoester of a polybasic acid (monoethyl maleate or the like) Ester, etc.) and hydrocarbons (6ene, propylene, etc.)
的共聚物等；作為所形成之羧酸金屬鹽，可舉例如：鹼金屬 有機羧酸鹽(檸檬酸鋰、擰檬酸鉀、檸檬酸鈉、硬脂酸鋰、 12-經基硬脂賴等）、驗土金屬有機羧酸鹽(醋酸^醋酸 鈣、擰檬酸鎂、檸檬酸鈣、硬脂酸鈣、硬脂酸鎂、12_^美 硬脂酸鎂、12經基硬脂_等）、離聚物樹脂(上述聚合= 飽和多元羧酸與烴烯之共聚物中所含有之羧美之至，丨、立 分被上述金屬之離子所中和的樹脂）等。 P 此等⑹金屬化合物f ’特佳為驗土金屬之氧化物、氣氧 化物、碳酸鹽及羧酸鹽。 用 此等⑷選自驗金屬或驗土金屬之氧化物、氫氧化物、益 機酸鹽及羧酸鹽之金屬化合物，可單獨或組合〗種以上而使 其較佳調配比例係相對於(a)聚端 醛樹脂100重量份 可 16 099111393 201041946 由0.0卜3重量份、特佳o.ow重量份中選擇。含有量過少 時’因⑷金屬化合物之調配所造成之對耐熱穩定性等的效 果無法充分表現’相&地在過多時，有損及本發明目標之剛 性等特性之虞，故不佳。本發明中，在調配⑷金屬化合物 時，可將⑷金屬化合物於任意階段混合至⑷聚祕樹脂， .但特㈣在與(b)纖維素纖維混合前，將(e)金屬化合物預先 以擠出機等溶融混合至(a)聚縮醛樹脂中的方法。 〇 <(f)加工助劑〉 本發明之聚縮搭樹脂組成物中，可進-步調配(f)選自長鏈 脂肪酸、長鏈脂肪酸之衍生物、聚氧伸烧二醇及聚錢化合 物的至少一種化合物作為加工助劑。 長鏈脂肪酸可為餘和脂肪酸，亦可為不飽和脂肪酸。又， 亦可使用使其—部分氫原子被經基等取代基所取代者。作為 此種長鏈脂崎，可例示碳數以上之1價或2價之脂肪 〇 I厌數1G以上之i價不飽和脂肪酸、碳數⑺以上之2 4貝月曰认(_元g夂性月旨肪酸）。上述脂肪酸中亦包括在分子 •具有1個或複數_基的脂肪酸。 • 長鏈㈣酸之衍生物中包括麟_旨及脂㈣酿胺等。 、為月曰肪&酉曰’可舉例如上述長Μ脂肪酸與醇的酿。其構 ^並無特別限制，可使用直鏈狀或分枝狀脂肪酸酷之任— 匕作為脂肪酸s旨之具體例，可舉例如··乙二醇單或二軟月旨 酉文酉曰乙一醇單或二硬脂酸酯、乙二醇單或二廿二酸酯、乙 099111393 17 201041946 二醇單或二廿八酸酯、甘油單至三軟脂酸酯、甘油單至三硬 脂酸酯、甘油單至三廿二酸酯、甘油單至三廿八酸酯、季戊 四醇單至四軟脂酸酯、季戊四醇單至四硬脂酸酯、季戊四醇 單至四廿二酸酯、季戊四醇單至四廿八酸酯、聚甘油三硬脂 酸酯、三經甲基丙烧單軟脂酸醋、季戊四醇單十一酸醋、山 犁醇酐單硬脂酸酯、聚伸烷二醇（聚乙二醇、聚丙二醇等）之 單或二月桂酸酯、單或二軟脂酸酯、單或二硬脂酸酯、單或 二廿二酸s旨、單或二廿八酸醋、單或二油酸醋、單或二亞麻 油酸酯等。 作為脂肪酸醯胺之例子，可舉例如：癸酸醯胺、月桂酸醯 胺、肉苴蔻酸醯胺、軟脂酸醯胺、硬脂酸醯胺、花生酸醯胺、 廿二酸醯胺、廿八酸醯胺等之飽和脂肪酸之1級酸醯胺，油 酸醯胺等之不飽和脂肪酸之1級酸醯胺，硬脂基硬脂酸醯 胺、硬脂基油酸醯胺等之飽和及/或不飽和脂肪酸與單胺的2 級酸醯胺，乙二胺-二軟脂酸醯胺、乙二胺-二硬脂酸醯胺（伸 乙基雙硬脂基醯胺）、六亞曱基二胺-二硬脂酸醯胺、乙二胺 -二廿酸醯胺、乙二胺-二廿八酸醯胺、乙二胺-二油酸醯胺、 乙二胺-二芥子酸醯胺等；進一步可例示乙二胺-(硬脂酸醯胺) 油酸醯胺等之具有在烷二胺之胺部位上鍵結了不同醯基之 構造的雙醯胺等。 作為上述聚氧伸烷二醇，可舉例如伸烷二醇（乙二醇、丙 二醇、丁二醇等之伸烧二醇等）之均聚物或共聚物、此等之 18 099111393 201041946 衍生物等。 >作為t氧伸燒二醇之具體例，可舉例如聚乙二醇、聚丙二 酉予聚丁—醇等之聚氧伸燒二醇、聚氧乙烯·聚氧丙燒共聚 物（’’、、規或讀共聚物等）、聚氧乙烯聚氧丙烯甘 乙稀聚氧_單丁基轉之共聚物等。此等之中，較佳2 有乳乙稀赌之聚合物，例如聚乙二醇、聚氧 丙 Ο Ο 共聚物及此等之衍生物等。聚氧伸烧二醇之平均= d 里為 (聚)有合物中’係包括(聚)有财纽等。作為 严f其戏，可例示二絲魏烧(二甲基錢燒等）、 :二:夕:之苯基甲基嫩等)、二芳基魏垸(二苯基 、_ 之單有機矽氧烷、此等之均聚物（聚二曱基矽氧 〃 A笨基甲基；^氧燒等）或共聚物等。又，聚有機石夕氧烧 亦可為寡聚物。 2 ’（聚）有機％氧燒中亦包括：在分子末端或主鍵上具 班氧基羥基、烷氧基、羧基、胺基或取代胺基(二烷基 等）醚基、乙烯基、（T基）丙烯醯基等之取代基的改質 (聚)有機矽氧烷等。 在本發明中調配(0加工助劑時，可將上述之選自長鏈脂肪 酸長鍵知肪酸之衍生物、聚氧伸烷二醇及聚矽氧的化合物 單獨或組合2種以上而使用。其較佳娜比㈣相對於(a) 聚縮醛树脂100重量份，為0.01〜3重量份、特佳0.02〜1重 099111393 19 201041946 麗伤在各有星過少時，無法得到作為力口工助劑之效果，相 反地在過夕k ’亦有損及加工性、或損及本發明原本目標之 效果之虞，故不佳。 、本發明中’纟調配此種⑺加工助劑時，可將⑴加工助劑 於任思階段混合至(a)聚祕細旨巾，但特佳係在與(b)纖維 素纖維混合μ ’將(f)加工助關先崎出機等溶融混合至 聚縮醛樹脂中的方法。 <(g)滑動性改良劑> 本發明之聚縮曝樹墙組成物中可進-步調配選自下述之 化口物作為滑動性改良劑：以從由不飽和叛酸及其之酸軒及 其等之何生物所組成群中選擇之至少1種進行改質的改質 烯辽系來合物、具有1級或2級胺基之伸烷二醇系聚合物、 烯寡聚物、實施了表面處理之無機填充劑等。又，上述 長鏈脂肪酸、長鍵脂肪酸之衍生物、聚氧伸烧二醇、聚石夕氧 化合物亦具有滑動性改善機能，而可調配作為滑動性 劑。 以從由不飽和叛酸及其之酸酐及其等之衍生物所組成群 中選擇之至少1種進行改質的改f烯烴系聚合物，係指將稀 烴系聚合物以從由不飽和羧酸及其之酸酐及其等之衍生物 所組成群中選擇之至少i種進行改質者的總稱。作為此處所 使用之烴烯系聚合物，可舉例如：乙烯、丙烯、丨_ 丁烯、1 己烯、1-庚烯、丨-辛烯、i-壬烯、丨_癸烯、丨_十二烯等之、 099111393 20 201041946 烯烴的均聚物，以及由此等之2種以上所構成的共聚物，以 及此等之烯烴與丙烯酸、曱基丙烯酸等之0：,/?-不飽和酸或 丙烯酸曱酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯 酸2-乙基己酯、丙烯酸羥乙基酯、曱基丙烯酸甲酯、曱基 丙烯酸乙酯、曱基丙烯酸丙酯、甲基丙烯酸丁酯、曱基丙烯 ' 酸2-乙基己酯、甲基丙烯酸羥乙基酯等之ce,/5-不飽和羧酸 ' S旨，1,4-己二烯、二環戊二烯、5-亞乙基-2-降稻烯、2,5-降 0 稻二烯等之非共軛二烯，丁二烯、異戊二烯、戊二烯等之共 軛二烯成分，α-曱基苯乙烯等之芳香族乙烯基化合物、含有 乙烯基曱基醚等之6烯基醚或此等之乙烯基系化合物的衍 生物等之共單體成分中之至少1種而成的無規、嵌段或接枝 共聚物等。 所謂改質烯烴系共聚物，係指將上述烯烴系聚合物以選自 由不飽和羧酸及其酸酐及其等之衍生物所組成群之至少一 Ο 種所改質者。作為較佳之改質烴烯系共聚物之具體例，可舉 例如以順丁烯二酸酐改質之聚乙烯、聚丙烯、乙烯-丙烯共 . 聚物、乙烯丙烯酸乙酯共聚物、乙烯丙烯酸甲酯共聚物、乙 , 烯曱基丙烯酸乙酯共聚物、乙烯曱基丙烯酸曱酯共聚物等。 所謂具有1級或2級胺基之伸烷二醇系聚合物，係指乙二 醇、丙二醇、丁二醇之均聚物或共聚物，於其末端或分子鏈 上具有1級或2級胺基之聚合物。進而亦可為形成與脂肪酸 的酯、與脂肪酸醇的醚等之經若干改質的聚合物。作為其例 21 099111393 201041946 子，係由聚乙二醇、聚丙二 所構成的共聚物，並具有至少構成單位 作為料聚物，主要可舉例:具基者等。 煙單獨、或使乙細與C3〜C2。之， 脂肪族烴。 D 口之構造的 作為實施了表面處理之益機殖 7夜石、雲母及氧化鋅等之 至少賴_、魏化合轉實施了表面處^ 佳可舉例如對選自碳㈣、欽酸_、碳酸鋇及氧化鋅之至^ 1種以脂肪酸Sl實施了表面處理者。此種無機填充劑並不依 存於粒子祕、纖_、高寬晴之雜，若域群中所舉 例之無機填充劑，則可使用任意物。 本發明中，在調配(幻滑動性改良劑時，可單獨或組合2 種以上之選自下述的化合物：上述以從由不飽和羧酸及其之 酸酐及其等之衍生物所組成群中選擇之至少1種進行改質 的改質烯烴系聚合物、具有1級或2級胺基之伸烷二醇系聚 合物、α-烯烴寡聚物、實施了表面處理之無機填充劑等。其 較佳調配比例係相對於⑻聚縮醛樹脂100重量份，為 0.01〜10重量份、特佳可自〇 〇2〜8重量份進行選擇。 本發明中，在調配此種(g)滑動性改良劑時’可將(g)滑動 性改良劑於任意階段混合至(a)聚縮醛樹脂中’特佳係在與(b) 纖維素纖維混合前，將(g)滑動性改良劑預先以擠出機等溶 22 099111393 201041946 融混合至(a)聚縮醛樹脂中的方法。 〈聚縮醛樹脂組成物之調製方法> 匕本發明之^_樹脂組成物，係相對於上述⑷聚縮駿樹 脂100重量份’含有(b)經解纖之纖維素纖維1〇〜15〇重量 份、（C)受阻紛系抗氧化劑〇 〇1〜3重量份、⑷選自胺基三喷 化合物、胍胺化合物、肼化合物及聚醯胺之至少丨種含氮化 .合物〇.〇卜3重量份，又更佳係進一步含有⑷選自驗金屬或 〇鹼土金屬之氧化物、氫氧化物、無機酸鹽及羧酸鹽之至少— 種金屬化合物〇.01〜3重量份、及/或觸自長鍵脂肪酸、長 鏈脂肪酸之衍生物、聚氧伸烧二醇及聚錢化合物之至少一 種的加工助』〇 〇1〜3重量份、及或⑻滑動性改良劑0.01〜 重量份，藉此予以調製。 本杳明中，上述聚縮醛樹脂組成物之調製方法的具體態樣 並”’、特⑺限定’可藉由—般合成樹脂組成物或其成形品之調 〇製法㈣知設備財法進行調製。亦即，將必衫分混合， :吏用單轴或雙轴之掩出機或其他之溶融混練裝置進行混 '東可@製作為成形成顆粒。又，亦可使用複數之擠出機或 其他之溶融混練震置。 本么月之聚縮酸樹脂組成物的調製時，特佳係將⑻纖維 ，戴=以外之调配成分，亦即（c)受阻酚系抗氧化劑、（d)含 氮化°物、選自較佳調配成分之⑷金屬化合物、（f)加工助 4及(g)/f祕改良劑等之丨種或2種以上，預先溶融混合 099111393 23 201041946 至(a)聚縮醛樹脂中，其後，將此溶融混合物與(b)纖維素纖 維及構成組成物之剩餘成分混合，予以溶融混練而調製目標 組成物的方法。 作為本發明之聚縮醛樹脂組成物之調製方法，係在具有旋 轉翼之混合器内進行纖維素纖維集合體之解纖，在(b)經解 纖之纖維素纖維中追加添加（a)聚縮醛樹脂及其他成分而進 行混合的方法；在具有旋轉翼之混合器或解纖機中進行纖維 素纖維集合體之解纖，將(b)經解纖之纖維素纖維移至另外 的混合器中並添加混合(a)聚縮醛樹脂及其他成分的方法； 或將(b)經解纖之纖維素纖維與(a)聚縮醛樹脂及其他成分以 擠出機進行混合的方法等。 其中，由本發明之效果、作業性及經濟性之觀點而言，特 佳係在具有旋轉翼之混合器内對(b)經解纖之纖維素纖維追 加添加（a)聚縮醛樹脂及其他成分而進行混合的方法。上述 方法中，藉由在混合器内使纖維素纖維集合體解纖，於其中 投入所需量之(a)聚縮醛樹脂及其他成分並進行高速攪拌， 而發生摩擦熱使混合器内升溫，故聚縮醛樹脂溶融，附著於 經解纖之纖維素纖維上，可直接得到纖維素纖維與聚縮醛樹 脂及其他成分的混合物。 對(b)經解纖之纖維素纖維中追加添加（a)聚縮醛樹脂及其 他成分而進行混合時，攪拌時之旋轉翼之平均周速較佳係以 10〜100m/秒之範圍進行攪拌，更佳係以平均周速10〜90m/ 24 099111393 201041946 秒、更佳係以平均周速10〜8〇m/秒進行攪拌。若繼續攪拌， 則混合器内之溫度上升’馬達的動力上升。較佳係配合此動 力上升及混合器内的溫度’慢慢或一口氣地使麟速度減低 而降低旋轉數，使平均職成為上親圍。又，為了輔助混 ^内之升溫’使纖維素纖維與聚祕樹脂之混合物製造變 .得容易’亦可藉加溫手段對混合器進行加溫。 、 斤知'之合物可藉冷卻使其固化。冷卻方法可舉例 〇如m合II内進行冷卻的方法、將混合物排出至連結於 上述此口為的另外混合器中再進行冷卻的方法等。特佳係將 此口物排出至連結於上述混合器的另外混合器中，—邊擾摔 、邊進仃冷’方法。較佳細冷卻時之旋轉翼之平均周速 為1 3〇111/秒之範圍進行擾拌，更佳係以平均周速2〜25m/ 秒、再更佳之平均周速3〜25m/秒進行授拌。 藉由此種處理，得到含有⑻聚縮越樹脂與⑻經解纖之纖 〇維素、I錢其他成分的雜⑯樹脂线物。所得之組成物雖 可直接使用，但亦可藉由粉碎機等進行造粒，及/或藉擠出 •機料行*喊練並料造粒後再使用。 . 在°周製本發明之聚縮搭樹脂組成物時，可使用改善 ⑽旨與(b)經解纖之齡素纖維之間之密黏性的物 ;此作為改善密黏性之物質，可舉例如—般式 〜〇(R . 2價之基）所示之異氰酸酯化合物、 S=C=N-R-Vr==P__0 /τ^ 〜S(R : 2價之基)所示之異硫氰酸酯化合物、 099111393 201041946 以及此等之改質物異氰酸酯化合物、熱可塑性聚胺基曱酸酯 樹脂、單烯烴性不飽和羧酸之酸酐的聚合物及共聚物 等。 作為異氰酸酯化合物之例子，可舉例如：4,4’-亞甲基雙（苯 基異氰酸酯）、2,4-曱苯二異氰酸酯、2,6-曱苯二異氰酸酯、 二曱苯二異氰酸酯、1，6-六亞甲基二異氰酸酯、異佛爾酮二 異氰酸酯、1，5-萘二異氰酸酯、2,2,4-三曱基六亞曱基二異氰 酸酯、2,4,4-三曱基六亞曱基二異氰酸酯，或作為異硫氰酸 西旨化合物之例的對應至上述異氰酸S旨化合物的二異硫續酸 酯，或作為改質物之此等的異氰酸酯化合物或異硫氰酸酯化 合物的二聚物、三聚物，進而為將異氰酸酯基以任意形式予 以保護的化合物等；此等任一者均有效。但若考慮溶融處理 等之變色度等各種性質、或操作上之安全性，則較佳為4,4’-亞曱基雙（苯基異氰酸酯）、異佛爾酮二異氰酸酯、1,5-萘二 異氰酸酯、1，6-六亞甲基二異氰酸酯、2,4-曱苯二異氰酸酯、 2,6-曱苯二異氰酸酯以及此等之二聚物、三聚物等之改質物 (或衍生物）。 另外，作為熱可塑性聚胺基曱酸酯樹脂的例子，可舉例如 ⑴二異氰酸酯化合物、（ii)分子量為500〜5000之高分子量多 元醇、（iii)以分子量為60〜500之低分子量多元醇及/或聚胺 作為構成成分的反應生成物等。 另外，作為α,/5-單烯烴性不飽和羧酸之酸酐的聚合物及共 26 099111393 201041946 聚物之例子’可舉例如順丁烯二酸酐等之不飽和羧酸之酸酐 的聚合物、苯乙烯系單聚物（例如苯乙烯、乙烯基甲苯、 曱基苯乙烯、氯苯乙烯等）與順丁烯二酸酐等之不飽和羧酸 之酸酐的共聚物、乙烯及/或丙稀系單體等與順丁稀二酸酐 等之不飽和羧酸之酸酐的共聚物等。As the formed metal carboxylate, for example, an alkali metal organic carboxylate (lithium citrate, potassium citrate, sodium citrate, lithium stearate, 12-base hard fat lysate) Etc.), soil test metal organic carboxylate (calcium acetate, calcium acetate, magnesium citrate, calcium citrate, calcium stearate, magnesium stearate, 12_^ magnesium stearate, 12-base hard fat _, etc. An ionomer resin (the above-mentioned polymerization = a carboxyl group contained in a copolymer of a saturated polyvalent carboxylic acid and a hydrocarbon alkene, a ruthenium, a resin in which a stand is neutralized by ions of the above metal), and the like. P (6) The metal compound f' is particularly preferably an oxide, gas oxide, carbonate or carboxylate of the soil. Using (4) a metal compound selected from the group consisting of oxides, hydroxides, proton salts and carboxylates of metal or soil-measuring metals, may be used alone or in combination to make a preferred ratio of ratios relative to ( a) 100 parts by weight of the polyalkaldehyde resin may be selected from 0.03 parts by weight, particularly preferably o. ow by weight. When the content is too small, the effect on the heat resistance stability due to the compounding of the (4) metal compound cannot be sufficiently exhibited. When the amount is too large, the properties such as the rigidity of the object of the present invention are impaired, which is not preferable. In the present invention, in formulating the (4) metal compound, the (4) metal compound may be mixed to (4) the poly-resin resin at any stage, but the (e) metal compound is preliminarily squeezed before being mixed with the (b) cellulose fiber. A method of melt mixing into a (a) polyacetal resin. 〇<(f) Processing Aid> The polycondensation resin composition of the present invention can be further formulated (f) selected from long chain fatty acids, derivatives of long chain fatty acids, polyoxyalkylene diols and poly At least one compound of the money compound is used as a processing aid. The long-chain fatty acid may be a residual fatty acid or an unsaturated fatty acid. Further, it is also possible to use a moiety in which a part of hydrogen atoms are replaced by a substituent such as a group. As such a long-chain sulphate, a monovalent or divalent fat 〇I having a carbon number of 1 or more and an i-valent unsaturated fatty acid having a number of 1 or more and a carbon number (7) or more can be exemplified (_yuan g夂) Sexuality is fatty acid). The above fatty acids also include fatty acids having one or a plurality of groups in the molecule. • Long-chain (tetra) acid derivatives include linoleum and lipids. For example, the above-mentioned long-selling fatty acids and alcohols can be mentioned. The structure is not particularly limited, and a straight-chain or branched fatty acid can be used as a specific example of the fatty acid s. For example, ethylene glycol mono- or di-soft-moon Alcohol mono or distearate, ethylene glycol mono or sebacate, B 099111393 17 201041946 diol mono or didecanoate, glycerol mono to tristearate, glycerol mono to tristearic acid Ester, glycerol mono-sebacate, glycerol mono-seicyl octaester, pentaerythritol mono-tetra-palpharate, pentaerythritol mono-tetrastearate, pentaerythritol mono-tetradecanoate, pentaerythritol single to Tetradecanoate, polyglyceryl tristearate, trimethyl methacrylate monostearic acid sulphate, pentaerythritol monodecanoic acid vinegar, sorbitol monostearate, polyalkylene glycol (polyalkylene glycol) Ethylene glycol, polypropylene glycol, etc.) of mono or dilaurate, mono or di-palmitate, mono or distearate, mono or dioxalic acid, mono or octadecanoic acid, single Or dioleic acid vinegar, mono or dilinoleic acid ester, and the like. Examples of the fatty acid decylamine include decyl citrate, decyl laurate, decyl citrate, decyl palmitate, decylamine stearate, decylamine aramide, and decyl decanoate. , a grade 1 acid amide of a saturated fatty acid such as decyl decanoate, a grade 1 acid amide of an unsaturated fatty acid such as oleic acid amide, stearyl stearate, stearyl oleate, etc. Grade 2 acid amides of saturated and/or unsaturated fatty acids with monoamines, decylamine diammonyl-nonyl-stearate, decylamine diammonium bis-stearate , hexamethylenediamine-nonyl stearate, ethylenediamine-nonyl decanoate, ethylenediamine-decylamine decylamine, ethylenediamine-nonoleate amide, ethylenediamine- Further, diammonium amide such as ethylenediamine-(decylamine oleate) decyl oleate or the like having a structure in which a different sulfhydryl group is bonded to an amine moiety of an alkyldiamine is exemplified. The polyoxyalkylene glycol may, for example, be a homopolymer or a copolymer of an alkylene glycol (such as ethylene glycol, propylene glycol or a butylene glycol such as butanediol), or the like, which is a derivative of the above-mentioned 18 099111393 201041946. Wait. > Specific examples of the t-oxygen-terminated diol include polyoxyethylene condensed diol such as polyethylene glycol, polypropylene dimer-polybutanol, and polyoxyethylene/polyoxypropylene copolymer (' ',, or read copolymers, etc., polyoxyethylene polyoxypropylene, ethylene oxide, polyoxy-monobutyl copolymer, and the like. Among them, preferred are polymers having a styrofoam, such as polyethylene glycol, polyoxypropylene oxime copolymers, and the like. The average of the polyoxyalkylene condensate = d is in the (poly) complex. The ‘system includes (poly) has a nucleus. As a play, it can be exemplified by the two-wire Wei-burn (dimethyl ketone, etc.), : two: eve: phenylmethyl-n-none, etc., and the diaryl-propionide (diphenyl, _ of the single organic oxime) An oxane, a homopolymer of this type (polydidecyl oxime oxime A), a copolymer or the like, etc. Further, the polyorgano oxyazepine may also be an oligomer. (Poly) organic % oxygen is also included in the molecular end or primary bond with an oxy-hydroxy group, an alkoxy group, a carboxyl group, an amine group or a substituted amine group (dialkyl group, etc.) ether group, vinyl group, (T group) a modified (poly)organosiloxane or the like of a substituent such as an acrylonitrile group. In the present invention, when the processing aid is used, the above-mentioned derivative selected from the long-chain fatty acid long-chain fatty acid can be used. The polyoxyalkylene glycol and the polyoxo-oxygen compound are used singly or in combination of two or more. The preferred ratio (iv) is 0.01 to 3 parts by weight, particularly preferably 0.02, based on 100 parts by weight of the (a) polyacetal resin. ~1重099111393 19 201041946 In the case of too few stars, it is impossible to obtain the effect as a sizing agent. On the contrary, it may also damage the workability or damage the present invention. The effect of the present object is not good. In the present invention, when the (7) processing aid is formulated, (1) the processing aid can be mixed in the stage of the application to (a) the fine secret towel, but it is particularly good. A method in which (b) a cellulose fiber is mixed with μ', and (f) is processed into a polyacetal resin by melt-blending, etc. <(g) Slidability improver> The exposed tree wall composition may be further formulated with a chemical substance selected from the group consisting of the following: a slidability improver: at least one selected from the group consisting of unsaturated tickic acid and its acid and its organisms One modified modified olefinic lysine compound, an alkylene glycol-based polymer having a primary or secondary amine group, an olefin oligomer, an inorganic filler subjected to surface treatment, and the like. Long-chain fatty acids, derivatives of long-chain fatty acids, polyoxy-ortho-diols, and polyoxo compounds also have a slidability improving function, and can be formulated as a sliding agent. At least one selected from the group consisting of such derivatives is a modified olefin polymer, which means that it will be diluted. The hydrocarbon-based polymer is a general term for upgrading from at least one selected from the group consisting of unsaturated carboxylic acids and their anhydrides and derivatives thereof. As the hydrocarbon-based polymer used herein, for example, Such as: ethylene, propylene, hydrazine _ butene, 1 hexene, 1-heptene, decene-octene, i-pinene, fluorene-nonene, fluorene-dodecene, etc., 099111393 20 201041946 olefin homopolymerization And a copolymer composed of two or more kinds thereof, and the like: 0:, /?-unsaturated acid or decyl acrylate, ethyl acrylate or propyl acrylate , butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, decyl propylene 'acid 2- Ethylhexyl ester, hydroxyethyl methacrylate, etc., ce,/5-unsaturated carboxylic acid' S, 1,4-hexadiene, dicyclopentadiene, 5-ethylene-2-nor Non-conjugated diene such as rice olefin, 2,5-nor 0 rice diene, conjugated diene component such as butadiene, isoprene or pentadiene, α-mercapto styrene, etc. a random, block or agglomerate of at least one of an aromatic vinyl compound, a 6-alkenyl ether such as vinyl decyl ether, or a derivative of a vinyl compound or the like Branch copolymers, etc. The modified olefin-based copolymer is one which is modified by at least one selected from the group consisting of unsaturated carboxylic acids and anhydrides thereof and derivatives thereof. Specific examples of the preferred modified hydrocarbon-based copolymer include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene ethyl acrylate copolymer, and ethylene acrylic acid modified with maleic anhydride. Ester copolymer, ethyl bromide ethyl acrylate copolymer, ethylene methacrylate oxime copolymer, and the like. The alkylene glycol-based polymer having a 1 or 2 amine group means a homopolymer or copolymer of ethylene glycol, propylene glycol or butylene glycol, and has a grade 1 or 2 at the end or molecular chain thereof. Amine based polymer. Further, it may be a polymer which is modified with an ester of a fatty acid or an ether of a fatty acid alcohol. As an example thereof, 21 099111393 201041946 is a copolymer composed of polyethylene glycol and polypropylene, and has at least a constituent unit as a polymer, and is mainly exemplified by a base or the like. Smoke alone, or make B fine with C3 ~ C2. , aliphatic hydrocarbons. The construction of the D port is carried out as a surface treatment, and it is at least a radix, a mica, a zinc oxide, etc., and the Weihuahe has been subjected to a surface. For example, the pair is selected from the group consisting of carbon (tetra) and acid. Between cesium carbonate and zinc oxide, one type of surface treatment is carried out with fatty acid S1. Such an inorganic filler does not depend on the particle secret, the fiber _, and the high-width smear, and any of the inorganic fillers exemplified in the domain group may be used. In the present invention, in the case of blending (the slidability improving agent, two or more compounds selected from the group consisting of the above-mentioned groups consisting of unsaturated carboxylic acids and their anhydrides and derivatives thereof may be used alone or in combination. At least one modified olefin-based polymer to be modified, an alkylene glycol-based polymer having a first- or second-order amine group, an α-olefin oligomer, an inorganic filler subjected to surface treatment, and the like The preferred blending ratio is selected from 0.01 to 10 parts by weight, particularly preferably from 2 to 8 parts by weight, based on 100 parts by weight of the (8) polyacetal resin. In the present invention, such (g) is formulated. In the case of the slidability improver, the (g) slidability improver can be mixed into (a) the polyacetal resin at any stage. 'It is better to improve the slidability before mixing with the (b) cellulose fiber. The method in which the agent is melted and mixed into the (a) polyacetal resin by an extruder or the like 22 099111393 201041946. <Preparation method of the polyacetal resin composition> The resin composition of the present invention is relative to The above (4) poly shrinkage resin 100 parts by weight 'containing (b) defibrated cellulose fibers 1 〇 15 〇 Parts, (C) are resistant to 1 to 3 parts by weight of antioxidants, and (4) are at least one selected from the group consisting of amine-based three-spray compounds, guanamine compounds, ruthenium compounds, and polyamines. Further preferably, (4) at least one metal compound selected from the group consisting of oxides, hydroxides, inorganic acid salts and carboxylates of metal or alkaline earth metals, 0.1 to 3 parts by weight, and / or 1 to 3 parts by weight of the processing aid of at least one of a long-chain fatty acid, a derivative of a long-chain fatty acid, a polyoxy-hydrogenated diol, and a polyvalent compound, and (8) a slidability improver 0.01 to weight In the present invention, the specific aspect of the preparation method of the polyacetal resin composition described above is defined by "the general composition of the resin composition or the molded article thereof". The system (4) knows the equipment and financial method to make the modulation. That is, the shirts are mixed, and the 单 单 单 双 或 或 或 或 或 或 或 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东 东It is also possible to use a plurality of extruders or other melt-mixing shakes. In the preparation of the polyacetal resin composition of this month, it is preferred to use (8) fiber, other than the compounding component, that is, (c) hindered phenol-based antioxidant, (d) nitride-containing material, selected from Preferably, the (4) metal compound, (f) the processing aid 4, and the (g)/f modifier are added or mixed, and the mixture is previously melted and mixed, and the mixture is mixed with 099111393 23 201041946 to (a) a polyacetal resin. Then, the molten mixture is mixed with (b) the cellulose fibers and the remaining components of the constituents, and the target composition is prepared by melt-kneading and kneading. The method for preparing the polyacetal resin composition of the present invention has a method of defibrating a cellulose fiber assembly in a mixer of a rotary wing, and adding (a) a polyacetal resin and other components to the (b) defibrated cellulose fiber, and mixing the same; Defibrating the cellulose fiber assembly in a mixer or defibrating machine, moving (b) the defibrated cellulose fiber to another mixer and adding (a) polyacetal resin and other components Method; or (b) defibrated cellulose fibers with (a) Acetal resin and other ingredients to the extruder mixing method. Among them, from the viewpoints of the effects, workability, and economy of the present invention, it is particularly preferable to add (a) a polyacetal resin and the like to (b) the defibrated cellulose fiber in a mixer having a rotary wing. A method of mixing components. In the above method, by dissolving the cellulose fiber assembly in a mixer, a desired amount of the (a) polyacetal resin and other components are put therein and stirred at a high speed, and friction heat is generated to heat the inside of the mixer. Therefore, the polyacetal resin is melted and adhered to the defibrated cellulose fiber, and a mixture of the cellulose fiber and the polyacetal resin and other components can be directly obtained. When (b) the (A) polyacetal resin and other components are additionally added to the defibrated cellulose fibers, the average peripheral speed of the rotating blades during stirring is preferably in the range of 10 to 100 m/sec. Stirring is preferably carried out at an average peripheral speed of 10 to 90 m / 24 099111393 201041946 seconds, more preferably at an average peripheral speed of 10 to 8 〇 m / sec. If the stirring is continued, the temperature in the mixer rises and the power of the motor rises. Preferably, the power is increased and the temperature in the mixer is slowed down or lowered in a slow manner to reduce the number of revolutions, so that the average job becomes a close parent. Further, in order to assist the temperature rise in the mixture, it is easy to manufacture the mixture of the cellulose fibers and the polymylon resin, and the mixer can be heated by means of heating. The compound can be solidified by cooling. The cooling method can be exemplified by a method of cooling in m and II, a method of discharging the mixture to another mixer connected to the above port, and cooling. The special product discharges the product into another mixer connected to the above mixer, which is a method of smashing and snagging. Preferably, the average peripheral speed of the rotating wing during the fine cooling is 1 3 〇 111 / sec., preferably, the average peripheral speed is 2 to 25 m / sec, and the average peripheral speed is 3 to 25 m / sec. Ingredients. By this treatment, a hetero 16 resin strand containing (8) a polycondensation resin and (8) a defibrated fibrin, and other components of I money was obtained. Although the obtained composition can be used as it is, it can also be granulated by a pulverizer or the like, and/or can be used by pulverizing and extruding the granules. When the polycondensation resin composition of the present invention is produced at a temperature of about 90°, it is possible to use a substance which improves the adhesion between (10) and (b) the defibrated aging fiber; For example, an isocyanate compound represented by the general formula ~ 〇 (R. 2 valent group), isothiocyanate represented by S = C = NR - Vr = = P__0 / τ^ ~ S (R: base of 2 valence) An acid ester compound, 099111393 201041946, and a modified polymer isocyanate compound, a thermoplastic polyamine phthalate resin, a polymer and a copolymer of an anhydride of a monoolefin unsaturated carboxylic acid, and the like. Examples of the isocyanate compound include 4,4'-methylenebis(phenyl isocyanate), 2,4-nonylbenzene diisocyanate, 2,6-nonyl diisocyanate, diphenylene diisocyanate, and 1 ,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-tridecylhexamethylene diisocyanate, 2,4,4-trimethyl Hexamethylene diisocyanate, or diisothiosulfonate corresponding to the above-mentioned compound of isocyanate S as an example of a compound of isothiocyanate, or an isocyanate compound or isothiocyanate as a modified substance The dimer or trimer of the acid ester compound is further a compound which protects the isocyanate group in an arbitrary form, and the like; and any of them is effective. However, in consideration of various properties such as discoloration degree in the melt treatment or the like, or operational safety, 4,4'-fluorenylene bis(phenyl isocyanate), isophorone diisocyanate, 1,5- are preferable. Naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4-nonyl diisocyanate, 2,6-nonyl diisocyanate, and modified (or derived) of such dimers, trimers, and the like ()). Further, examples of the thermoplastic polyamine phthalate resin include, for example, (1) a diisocyanate compound, (ii) a high molecular weight polyol having a molecular weight of 500 to 5,000, and (iii) a low molecular weight plural having a molecular weight of 60 to 500. An alcohol and/or a polyamine is used as a reaction product of a constituent component. Further, examples of the polymer of an acid anhydride of an α,/5-monoolefin unsaturated carboxylic acid and a total of 260 99111393 201041946 polymer include a polymer of an acid anhydride of an unsaturated carboxylic acid such as maleic anhydride, a copolymer of a styrene-based monomer (for example, styrene, vinyl toluene, mercaptostyrene, chlorostyrene, etc.) and an anhydride of an unsaturated carboxylic acid such as maleic anhydride, ethylene and/or propylene A copolymer of a monomer or the like with an acid anhydride of an unsaturated carboxylic acid such as cis-succinic anhydride or the like.
進而，為了配合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。若例示添加物之例子，可舉 例如各種者色对彳h劑、核劑、界面活性劑、異種聚合物、 有機高分子改良劑及無機、有機、金屬等之纖維狀、粉粒狀、 板狀的充填劑，此等可使用i種或混合2種以上使用。 另外，上述穩定劑、添加劑等之調配可於任意階段進行混 合’例如可添加至⑷聚祕樹脂t，或於樹脂組成物之調 整時添加’亦可在得到最終成形品前進行添加、混合。 <聚縮醛樹脂組成物之成形方法及用途> 本發明之聚祕樹脂組成物可藉習知之成形方法(例如射 出成形、擠出成形、壓縮成形、吹塑成形、真空成形、發泡 成形、旋轉成形、氣料射成料之方法) 品。又，此等成形品可利用至汽車零 料檀絲 电氣•雷子愛杜 建材、生活關係零件·化妝 d牛、 用途上。 相關係零件等各種 、油槽開啟器、安 夾等之内裝零件， 具體可舉例如：作為汽車零件之内把手 全帶扣、辅助圈、各種開關、雜、把手、 099111393 27 201041946 計量器、收集器等之電氣系統零件、音響機器或汽車導航機 器等之車用電氣•電子零件，車窗升降器之載板所代表之與 金屬接觸的零件、車門鎖促動器零件、鏡零件、雨刷馬達系 統零件、燃料系統之零件等之機構零件等。 作為電氣•電子零件，係由聚縮醛樹脂成形品所構成，且 多數存在著金屬接點的機器的零件或構材，例如音響機器、 錄影機器、或電話機、影印機、傳真機、文字處理器、電腦 等之OA機器、玩具類之零件或構材，具體可舉例如底盤、 齒輪、桿、凸輪、滑車、軸承等。 進而亦適合使用於照明器具、建具、配管、栓塞、水龍頭、 廁所周邊機器零件等之建材•配管零件、拉鏈類、文具、唇 膏•口紅容器、洗淨器、淨水器、喷霧喷嘴、喷霧容器、氣 溶膠容器、一般之容器、注射針之支托器等之廣泛的生活關 係零件•化妝關係零件•醫用關係零件中。 [實施例] 以下根據實施例更加詳細地說明本發明，但本發明並不受 此等實施例所限定。 尚且，實施例及比較例中所使用之成分及試驗方法的細 節，係如下述。 [使用成分] (a)聚縮酸·樹脂：Polyplastic(股）製 (a-Ι)溶融指數=9g/10分鐘 28 099111393 201041946 (a-2)熔融指數=27g/10分鐘 (a-3)熔融指數=45g/10分鐘 (b) 纖維素纖維集合體(解纖後使用） (b-Ι)木材紙漿片（曰本製紙集團製） (c) 受阻g分系抗氧化劑 (c-1)季戊四醇肆[3-(3,5-二第三丁基-4-羥基苯基）丙酸酯] (d) 含氮化合物 〇 (d-Ι)三聚氰胺 (e) 金屬化合物 (e-l)12-羥基硬脂酸鈣 (e-2)硬脂酸鈣 (e-3)氧化鎂 (e-4)氧化鋅 (e-5)碳酸鈣 O (f)加工助劑 (f-i)乙烯雙硬脂基醯胺 - (f-2)甘油單硬脂酸酯 (g)滑動性改良劑 (g-Ι)胺基改質聚乙二醇 (g-2)順丁烯二酸酐改質聚烯烴 (g-3)乙烯丙烯共聚物 (g-4)以脂肪酸酯進行了表面處理之碳酸鈣 29 099111393 201041946 [試驗方法] (1) 剛性（彎曲彈性係數） 根據IS0178，測定彎曲彈性係數(MPa)。 (2) 比重 藉試驗片之容積（測定因水中浸潰所造成的增加份）與試 驗片之重量予以算出。 (3) 灰分 將置入坩鍋的試料於電爐内以600°C燃燒2小時，測定燃 燒後之灰分(wt%)。 (4) 熱傳導性(熱傳導率） 藉熱指數法，測定熱傳導率(W/m · K)。熱傳導率高者顯 示熱傳導性優越。 (5) 滑動性(磨耗量） 根據JIS K7218，使用旋轉式摩擦磨耗試驗機，使同規格 A法指定之中空圓筒試驗片與鋼材（S45C)滑動，測定S45C 之磨耗量（g)。試驗係將樹脂側固定，旋轉S45C，依旋轉速 度150rpm、負重20kgf、試驗時間24小時的條件進行。又， 針對實施例23、比較例5，依旋轉數300rpm實施試驗，針 對樹脂側與S45C間之摩擦係數、S45C之磨耗量（g)及樹脂 側之磨耗量(g)分別進行測定。摩擦係數低、磨耗量少者顯 示優越的滑動性。 (6) 制振性(損失係數） 30 099111393 201041946 根據JIS G0602之中央支持定常加振法，測定頻率 1x102Hz下之知失係數(％)。損失係數高者顯示優越的制振 性。 [實施例1〜7] 預先於(a)聚縮醛樹脂中依表i之實施例丨〜7的比例混合(c) 受崎系抗氧化劑、（d)含氮化合物、⑷金屬化合物、⑴加 工助劑’以擠出機進行溶融混練，並分別調製含有⑻纖維 Ο 素纖維以外之成分的聚縮醛樹脂組成物。 將具有旋轉翼之加熱混合器（附有加熱器及溫度計，容量 200L)加溫至100。〇以上，投入⑻纖維素纖維集合體(木材紙 水片）以平均周速5〇m/秒進行授拌。在約經過2分鐘之時 點，纖維素纖維變化為綿狀。 接著於加熱混合器内由進料斗將預先調製之聚縮搭樹脂 組成物投入至混合器内，以平均周速5〇m/秒進行授掉。混 〇合器之溫度上升並達到⑽〜⑽。c，於此狀態下繼續授摔。 其後y吏平均周速降低至25m/秒之低速，繼續授摔後’ .打開—器之排出口，將混合物排出至所連接之冷卻混合器 .[附有以冷部水(20ΐ)所進行之水冷手段及溫度計，容量 中於冷卻混合器内以平均周速秒進行攪拌、冷 卻。其後’混合物固化，而得到固化物。 將CHb物以粉碎機粉碎後’以擠出機進行溶融混練，調製 顆粒狀之纖維素纖維強化聚祕樹脂組成物。使用所得之顆 099111393 31 201041946 粒藉射出成形機成 結果示於表丨。 疋n並進行試驗評價。 [比較例1] 將不含(b)纖維素 T ^ , 素義維之聚縮醛樹脂缸成胳以六主！ 例1之組成藉播 成物(依表1之比較 施例同樣的奸^彳了溶祕合Μ㈣配者)進行與實 1貝。比較例1中，將聚縮 、貫 或㈣時’物性亦未發生實質差里。^脂㈣取代為(a_2) 之結果的比較 .....°泉示於表1。由表i 成物係抑制 日H維素纖一自彳b I祕樹脂組 灰分上升、滑動性· I h 非強化之聚縮_旨組成物（比較例=振性之降低，並較 曲彈性係數）、熱傳導性。 ）項著提升了剛性（彎 [比較例2〜3 料度或哪之手段所使㈣玻璃纖維並 聽作⑼駿樹脂組成物。所調製之組成係如^之比 較例2及3 ’❹氧她卿酸E玻璃作為(b，_2)玻璃纖維。 比較例3巾’係作成騎慮賴配了麵纖料之穩定性、 加工性的組成。結果示於表i。藉由比對表i所示之實施例 與比較例2〜3(以及比較例υ，本發明之纖維素纖維強化聚 祕樹脂組成物並未發生如玻璃纖維強化聚祕樹脂組成 物（比較例2〜3)般的比重、灰分增大或滑動性、制振性之降 低，可知能極有效地作為提升剛性或熱傳導性的手段。 [比較例4] 32 099111393 201041946 預先於(a)聚縮醛樹脂中以表1之比較例4的比例混合(c) 文阻酚系抗氧化劑、（d)含氮化合物、（e)金屬化合物、（f)加 工助劑，以擠出機進行溶融混練，調製不含(b)纖維素纖維 之聚縮醛樹脂組成物。 將此聚縮醛樹脂組成物與未解纖之(b)纖維素纖維集合體 (木材紙漿片）於小型捏合機型溶融混練機(Lab〇 plast〇mill， 東洋精機製）内進行溶融混合。於聚縮醛樹脂内見到纖維素 〇 纖維之分散不良，故未實施其後的評價。 [實施例8〜11] 預先於(a)聚縮醛樹脂中依表2之實施例8〜u的比例混合 (c)受阻紛系抗氧化劑、⑷含氮化合物、⑴加工助劑，以播 出機進行溶融混練，並分別調製含有(b)纖維素纖維以外之 成分的聚縮醛樹脂組成物。 接著，與實施例1同樣地，將(b)纖維素纖維集合體(木材 G 紙漿片）投入至具有旋轉翼之加熱混合器中，纖維素纖維變 化為綿狀後，於由進料斗將預先調製之聚縮醛樹脂組成物投 ， 入至加熱混合器内，攪拌後，將混合物排出至所連接之冷卻 r . 混合器中’進行冷卻而得到固化物。進而，將固化物以粉碎 機粉碎後，以擠出機進行溶融混練，調製顆粒狀之纖維素纖 維強化聚縮醛樹脂組成物。使用所得之顆粒，藉射出成形機 成形為既定之試驗片，並進行試驗評價。將剛性（彎曲彈性 係數)之結果示於表2。 33 099111393 201041946 [實施例12〜22] 依與實施例11同樣的組成，在具有旋轉翼之加熱混合器 中投入(b)纖維素纖維集合體(木材紙漿片），在纖維素纖維變 化為綿狀後，將預先調製之聚縮醛樹脂組成物自進料斗投入 至加熱混合器内，攪拌後，將混合物排出至連接之冷卻混合 器中，藉冷卻而得到固化物。進而，將固化物以粉碎機粉碎。 接著，對所得之粉碎物，依既定組成添加實施例12〜22 所示的追加成分，以擠出機進行溶融混練，調製顆粒狀的纖 維素纖維強化聚縮醛樹脂組成物。使用所得之顆粒，藉射出 成形機成形為既定的試驗片，進行試驗評價。如表2〜3所示 之剛性（彎曲彈性係數）之結果，對剛性並無影響。另一方 面，藉由官能測試，確認到相較於未添加追加成分者，其使 成形等之溶融加工時之曱醛發生減低。 [實施例23] 於(a)聚縮醛樹脂中依表4之實施例23的比例混合(c)受阻 紛系抗氧化劑、（d)含氣化合物、（e)金屬化合物、（f)加工助 劑、（g)滑動性改良劑，以擠出機進行溶融混練，分別調製 含有（b)纖維素纖維以外之成分的聚縮醛樹脂組成物。 接著，與實施例1同樣地，將(b)纖維素纖維集合體(木材 紙漿片）投入至具有旋轉翼之加熱混合器中，在纖維素纖維 變化為綿狀後，將預先調製之聚縮醛樹脂組成物自進料斗投 入至加熱混合器内，攪拌後，將混合物排出至連接之冷卻混 34 099111393 201041946 合器中，藉冷卻而得到固化物。進而，將固化物以粉碎機粉 碎後，以擠出機進行溶融混練，調製顆粒狀的纖維素纖維強 化聚縮醛樹脂組成物。使用所得之顆粒，藉射出成形機成形 為既定的試驗片，進行試驗評價。結果不於表4。 [比較例5] 將不含(b)纖維素纖維之聚縮醛樹脂組成物(依表4之比較 • 例5之組成藉擠出機進行溶融混合而予以調配者）進行與實 〇 施例23同樣的評價。結果示於表4。由表4之結果的比較 可知，本發明之纖維素纖維強化聚縮醛樹脂組成物係滑動性 之降低(摩擦係數•磨耗量之顯著增加），並提升了剛性（彎曲 彈性係數）。尤其可知在高旋轉條件下亦依一定水準維持滑 動性。Further, in order to improve the physical properties in accordance with the intended use, various known additives can be blended in the composition of the present invention. Examples of the additive include, for example, various types of color-sensitive agents, nucleating agents, surfactants, heterogeneous polymers, organic polymer modifiers, and inorganic, organic, and metallic fibers, powders, and plates. These types of fillers can be used in combination of two or more kinds. Further, the above-mentioned stabilizer, additive or the like may be blended at any stage. For example, it may be added to (4) the polyester resin t or may be added during the adjustment of the resin composition. Alternatively, it may be added and mixed before the final molded article is obtained. <Forming method and use of polyacetal resin composition> The polyester resin composition of the present invention can be formed by a known molding method (for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foaming) Forming, rotary forming, gas injection method). In addition, these molded products can be used in automotive materials such as Tansi Electric • Lei Zi Ai Du Building Materials, Life Relations Parts, Makeup d Cows, and Applications. Various parts such as related parts, oil groove openers, and clamps, etc., for example, as the inner handle of the automobile parts, the full buckle, the auxiliary ring, various switches, miscellaneous, handles, 099111393 27 201041946 meter, collection Electrical and electronic components such as electrical system parts, audio equipment, or car navigation machines, metal-contact parts represented by the carrier of the window regulator, door lock actuator parts, mirror parts, and wiper motor Mechanism parts such as system parts, fuel system parts, etc. As electrical and electronic parts, it is made up of polyacetal resin molded products, and many parts or components of machines with metal contacts, such as audio equipment, video equipment, or telephones, photocopiers, fax machines, and word processing. For example, a chassis, a gear, a lever, a cam, a pulley, a bearing, etc., may be used for an OA machine such as a computer or a computer. Furthermore, it is also suitable for use in building materials, piping parts, zippers, stationery, lipsticks, lipstick containers, washers, water purifiers, spray nozzles, sprays, etc. for lighting fixtures, construction tools, piping, plugs, faucets, and toilet peripheral parts. A wide range of life-related parts such as fog containers, aerosol containers, general containers, and needle holders, cosmetic parts, and medical related parts. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples. Further, the details of the components and test methods used in the examples and comparative examples are as follows. [Ingredients] (a) Polycondensate/Resin: Polyplastic (a-Ι) melt index = 9 g/10 min 28 099111393 201041946 (a-2) Melt index = 27 g/10 min (a-3) Melt index = 45 g/10 min (b) Cellulose fiber assembly (used after defibration) (b-Ι) wood pulp sheet (manufactured by Sakamoto Paper Group Co., Ltd.) (c) Hindered g-series antioxidant (c-1) Pentaerythritol 肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (d) nitrogen-containing compound 〇(d-Ι)melamine (e) metal compound (el) 12-hydroxyl Calcium stearate (e-2) Calcium stearate (e-3) Magnesium oxide (e-4) Zinc oxide (e-5) Calcium carbonate O (f) Processing aid (fi) Ethylene bis-stearyl hydrazine Amine-(f-2) glycerol monostearate (g) slidability improver (g-Ι) amine-based modified polyethylene glycol (g-2) maleic anhydride modified polyolefin (g- 3) Ethylene propylene copolymer (g-4) Calcium carbonate surface-treated with a fatty acid ester 29 099111393 201041946 [Test method] (1) Rigidity (bending elastic modulus) The flexural modulus (MPa) was measured in accordance with IS0178. (2) Specific gravity Calculated by the volume of the test piece (measured by the increase in water immersion) and the weight of the test piece. (3) Ash The sample placed in the crucible was burned at 600 ° C for 2 hours in an electric furnace, and the ash (wt%) after burning was measured. (4) Thermal conductivity (thermal conductivity) The thermal conductivity (W/m · K) was measured by the heat index method. Those with high thermal conductivity show excellent thermal conductivity. (5) Slidability (abrasion amount) According to JIS K7218, a hollow cylindrical test piece specified in the same specification A method and a steel material (S45C) were slid by a rotary friction wear tester, and the abrasion amount (g) of S45C was measured. The test was carried out by fixing the resin side and rotating S45C under the conditions of a rotation speed of 150 rpm, a load of 20 kgf, and a test time of 24 hours. Further, in Example 23 and Comparative Example 5, the test was carried out at a rotation number of 300 rpm, and the friction coefficient between the resin side and S45C, the abrasion amount (g) of S45C, and the abrasion amount (g) on the resin side were measured. A low friction coefficient and a small amount of wear show superior slidability. (6) Momentum resistance (loss factor) 30 099111393 201041946 The loss coefficient (%) at a frequency of 1x102 Hz is measured according to the central support constant vibration method of JIS G0602. Those with a high loss factor show superior vibration damping. [Examples 1 to 7] The (a) polyacetal resin was previously mixed in the ratio of the examples 丨 to 7 in the following Table (c) the acene-based antioxidant, the (d) the nitrogen-containing compound, the (4) metal compound, and (1) The processing aid was melt-kneaded by an extruder, and a polyacetal resin composition containing a component other than the (8) fiber of the fiber was separately prepared. Heat the heated mixer with a rotating wing (with heater and thermometer, capacity 200L) to 100. In the above, the (8) cellulose fiber aggregate (wood paper water piece) was fed at an average peripheral speed of 5 〇 m / sec. At about 2 minutes, the cellulose fibers changed to a cottony state. Then, the pre-prepared polycondensation resin composition was introduced into the mixer by a feed hopper in a heating mixer, and was transferred at an average peripheral speed of 5 〇 m / sec. The temperature of the mixing coupler rises and reaches (10) ~ (10). c, continue to drop in this state. After that, the average weekly speed of y吏 is reduced to a low speed of 25m/sec. After the drop is continued, the outlet of the device is opened and the mixture is discharged to the connected cooling mixer. [With cold water (20ΐ) The water cooling means and the thermometer are carried out, and the capacity is stirred and cooled in the cooling mixer at an average peripheral speed of two seconds. Thereafter, the mixture was solidified to obtain a cured product. After the CHb was pulverized by a pulverizer, it was melt-kneaded by an extruder to prepare a granulated cellulose fiber reinforced polystyrene resin composition. Using the obtained granules 099111393 31 201041946, the pellets were injected into the forming machine and the results are shown in Table 丨.疋n and conduct a test evaluation. [Comparative Example 1] A polyacetal resin cylinder containing no (b) cellulose T ^ and Suyiwei was made into six mains! The composition of Example 1 is borrowed from the product (according to the comparison of Table 1 and the same traits of 施 彳 溶 溶 溶 溶 四 四 四 四 四 四 四 四 四 四 。 。 。 。 。 。 。 。 。 In Comparative Example 1, there was no substantial difference in the physical properties of the polycondensation, the coherence, or the (4). ^Comparison of the results of the substitution of (4) with (a_2) is shown in Table 1. From the table i, the system is inhibited by the H-dimensional fiber, the ash, the ash, the slidability, the I h, the non-reinforced polycondensation, the composition (comparative example = reduction in vibration, and flexibility) Coefficient), thermal conductivity. The item is improved in rigidity (bending [Comparative Example 2 to 3 or the means of (4) glass fiber and listening to (9) Chun resin composition. The composition of the modulation is as in Comparative Example 2 and 3 'Oxygen Her acid E glass was used as (b, _2) glass fiber. Comparative Example 3 towel was made into the composition of the stability and workability of the surface fiber. The results are shown in Table i. By comparison table i In the examples and Comparative Examples 2 to 3 (and the comparative examples, the cellulose fiber-reinforced poly-resin composition of the present invention did not have a specific gravity such as a glass fiber-reinforced poly-resin composition (Comparative Examples 2 to 3). The increase in ash content, or the decrease in slidability and vibration damping property can be used as a means for improving rigidity or thermal conductivity. [Comparative Example 4] 32 099111393 201041946 Pre-into (a) polyacetal resin, Table 1 The ratio of the comparative example 4 was mixed (c) a schistoscene-based antioxidant, (d) a nitrogen-containing compound, (e) a metal compound, and (f) a processing aid, and melt-kneaded in an extruder to prepare (b) Polyacetal resin composition of cellulose fibers. This polyacetal resin composition is unfibrilated (b The cellulose fiber aggregate (wood pulp sheet) is melted and mixed in a small kneading machine type kneading machine (Lab〇plast〇mill, Toyo Seiki). The dispersion of cellulose fiber is seen in the polyacetal resin. Therefore, the subsequent evaluation was not carried out. [Examples 8 to 11] The (a) polyacetal resin was mixed in advance in the ratio of Example 8 to u in Table 2 (c) the hindered antioxidants, and (4) the nitrogen-containing The compound and (1) processing aid were melt-kneaded by a dispenser, and a polyacetal resin composition containing (b) components other than the cellulose fibers was prepared, respectively. Next, in the same manner as in Example 1, (b) fiber was used. The fiber assembly (wood G pulp sheet) is put into a heating mixer having a rotary wing, and the cellulose fiber is changed into a cotton shape, and then the pre-prepared polyacetal resin composition is poured into the heating and mixing by the feed hopper. After stirring, the mixture is discharged to the connected cooling r. The mixture is cooled to obtain a cured product. Further, the solidified product is pulverized by a pulverizer, and then melted and kneaded by an extruder to prepare a granulated shape. Cellulose fiber The polyacetal resin composition was reinforced, and the obtained pellets were molded into a predetermined test piece by an injection molding machine, and subjected to test evaluation. The results of rigidity (bending elastic modulus) are shown in Table 2. 33 099111393 201041946 [Example 12 ～22] According to the same composition as in Example 11, (b) a cellulose fiber assembly (wood pulp sheet) was placed in a heating mixer having a rotary wing, and the cellulose fiber was changed into a cotton shape, and then prepared in advance. The polyacetal resin composition is introduced into the heating mixer from the hopper, and after stirring, the mixture is discharged to a connected cooling mixer, and cooled to obtain a cured product. Further, the cured product is pulverized by a pulverizer. In the obtained pulverized product, the additional components shown in Examples 12 to 22 were added in accordance with the predetermined composition, and the mixture was kneaded and kneaded in an extruder to prepare a pelletized cellulose fiber-reinforced polyacetal resin composition. Using the obtained pellets, it was molded into a predetermined test piece by an injection molding machine, and subjected to test evaluation. As a result of the rigidity (bending elastic modulus) shown in Tables 2 to 3, there is no influence on the rigidity. On the other hand, it was confirmed by a functional test that the amount of furfural during the melt processing such as molding was reduced as compared with the case where no additional component was added. [Example 23] The (a) polyacetal resin was mixed according to the ratio of Example 23 of Table 4 (c) hindered antioxidants, (d) gas-containing compound, (e) metal compound, (f) processing The auxiliary agent and (g) the slidability improver are melt-kneaded in an extruder to prepare a polyacetal resin composition containing the components other than the (b) cellulose fibers. Next, in the same manner as in the first embodiment, the (b) cellulose fiber aggregate (wood pulp sheet) was placed in a heating mixer having a rotary wing, and after the cellulose fibers were changed into a cotton shape, the pre-modulated polycondensation was carried out. The aldehyde resin composition was introduced into the heating mixer from the hopper, and after stirring, the mixture was discharged to a connected cooling mixture 34 099111393 201041946 and cooled to obtain a cured product. Further, the cured product was pulverized by a pulverizer, and then kneaded and kneaded by an extruder to prepare a granulated cellulose fiber-reinforced polyacetal resin composition. Using the obtained pellets, it was molded into a predetermined test piece by an injection molding machine, and subjected to test evaluation. The results are not shown in Table 4. [Comparative Example 5] A polyacetal resin composition containing no (b) cellulose fibers (compared according to Table 4, and the composition of Example 5 was blended by an extruder and blended) 23 same evaluation. The results are shown in Table 4. As is apparent from the comparison of the results of Table 4, the cellulose fiber-reinforced polyacetal resin composition of the present invention has a reduced slidability (a significant increase in friction coefficient and abrasion amount) and an increase in rigidity (bending elastic modulus). In particular, it is known that the slidability is maintained at a certain level under high rotation conditions.
35 099111393 201041946 〔11 比較例4* 8 1-Η 25.14 (細齡 025 Ο 0.10 0.18 1 1 I 1 1 1 财交例3 8 r—^ 25.16 030 8 c> § 5951 t—Η 0.412 0.906 tt#交例2 8 ι—Η 25.16 § 8 C5 0.10 0.18 5930 1.54 ί-Η 0.410 42.0 0.910 财交例1 8 r—< 025 1 0.10 0.18 2524 Ο 0386 s 1.729 额例7 8 ^-Η 108.94 025 0.03 0.10 0.18 7364 s C) 0.484 s 1.615 魏例6 8 67.04 § 1 0.10 0.18 6276 导· i 0.459 3 1.622 雜例5 8 43.10 § 8 C5 0.10 0.18 5140 8 C> 0.439 O 1.750 勤祕J4 8 67.04 § 8 c> 0.10 0.18 6354 τ-Η 0.09 0.466 00 (N 1.472 势fe例3 8 »-Η 43.10 025 0.03 0.10 0.18 4720 1.44 1 0.468 爸 1.616 雜例2 8 ϊ—Η 25.14 § 1 0.10 0.18 3985 § 0.425 y-^ 秘 | tmw 8 25.14 025 0.03 0.10 0.18 3690 T-H 0.02 0.416 o 1.735 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份1 重量份1 MPa wt% W/m.K W) DU ®c I 1 Η ώ 物I·生言啊賈 彎曲彈1生係數 -Ο t 鱗導晒專導率） ! 'δίί 継执lxltfHz下之損失係韵 ^ ^ 0 *35 099111393 201041946 〔11 Comparative Example 4* 8 1-Η 25.14 (fine age 025 Ο 0.10 0.18 1 1 I 1 1 1 financial exchange example 3 8 r-^ 25.16 030 8 c> § 5951 t-Η 0.412 0.906 tt#交Example 2 8 ι—Η 25.16 § 8 C5 0.10 0.18 5930 1.54 ί-Η 0.410 42.0 0.910 Example 1 8 r—< 025 1 0.10 0.18 2524 Ο 0386 s 1.729 Example 7 8 ^-Η 108.94 025 0.03 0.10 0.18 7364 s C) 0.484 s 1.615 Wei case 6 8 67.04 § 1 0.10 0.18 6276 Guide · i 0.459 3 1.622 Hybrid 5 8 43.10 § 8 C5 0.10 0.18 5140 8 C> 0.439 O 1.750 Diligence J4 8 67.04 § 8 c> 0.10 0.18 6354 τ-Η 0.09 0.466 00 (N 1.472 potential fe 3 8 »-Η 43.10 025 0.03 0.10 0.18 4720 1.44 1 0.468 Dad 1.616 Miscellaneous 2 8 ϊ-Η 25.14 § 1 0.10 0.18 3985 § 0.425 y-^ Secret | Tmw 8 25.14 025 0.03 0.10 0.18 3690 TH 0.02 0.416 o 1.735 parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight 1 part by weight 1 MPa wt% W/mK W) DU ®c I 1 Η ώ Matter I·Bearing 1 turned green scale factor -Ο t sun spot conductivity)! 'Δίί Ji performed under the lxltfHz loss based Yun ^ ^ 0 *
201041946 ο ο 【s 細列17 g 43.10 0.72 0.43 0.18 ^ X .i w\ A _ 0 4764 雜例16 g 43.10 0.72 0.15 0.18 (c~l)之 0.47重量 份 4820 實施例15 g 43.10 0.36 0.18 (c-1)之 0.11 重 量份、（d-1)之 0· 06重量份 4811 歡fei列14 g 43.10 0.36 0.15 oo C3 (cH)之 0.11 重量份 4841 實施例13 i 43.10 0.25 0.43 1 0.18 I (d-1)之 0.28 重量份 4707 倾例12 g 43.10 0.25 〇3 d 0.18 (d-1)之 0.06 重量份 4725 雜例11 g [43.10 | 0.25 0.15 I | 0.18 I 4730 i |實施例10 | g | 25.14 Π 1 0.25 j 0.15 0.18 4019 雜例9 s 43.10 | 1 0.25 丨 0.15 1 丨1 1 雜例8 | g | 25.14 I 1 0.25 1 | 0.15 I |重量份| 0.18 1 — MPa 1 4055 i重量份I 重量份I 重量份1 重量份1 重量份1 囬 滅 CO CO τ~|Η 1 C-I(^t) 1 1 d-l(^t) 1 組成内，追加 添加分 物龄啊賈 彎曲彈1·生得數 201041946 實施例22 〇 1—Η 43.10 0.25 0.15 0.14 0.18 4688 實施例21 〇 1 43.10 0.25 0.15 0.14 0.18 4699 實施例20 Ο ϊ-Η 43.10 0.25 0.15 0.14 0.18 4758 實施例19 100 43.10 0.25 0.15 0.14 0.18 4636 實施例18 Ο 43.10 1 0.25 0.15 0.14 0.18 4688 單位 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 MPa 項目 組成 (Ν cfj m 1 〇 e-Ι (追加添加成分） e-2(追加添加成分） e-3(追加添加成分） e-4(追加添加成分） e-5(追加添加成分） 2 物性評價 彎曲彈性係數 201041946 ο ο 〔寸<】 比較例5 〇 0.33 0.08 1.09 0.33 5.44 1.09 0.54 2200 0.17 r-H l-H 實施例23 〇 1-H 43.10 0.33 0.08 1.09 0.33 5.44 1.09 0.54 4122 0.18 m c5 rn 重量份 重量份 重量份 1重量份1 重量份 重量份 重量份 重量份 1重量份1 MPa bS) W) 項目 組成 (N ά A Τ—( Τ—Η cA ώ (Ν ώ m ώ 物性評價 彎曲彈性係數 滑動性(摩耗係數)* 滑動性(S45C摩耗量)* 滑動性(樹脂側摩耗量)* 世七寸 3 c^o(N< ux&ooe*201041946 ο ο [s series 17 g 43.10 0.72 0.43 0.18 ^ X .iw\ A _ 0 4764 Hybrid 16 g 43.10 0.72 0.15 0.18 (c~l) 0.47 parts by weight 4820 Example 15 g 43.10 0.36 0.18 (c- 1) 0.11 parts by weight, (d-1) 0·06 parts by weight 4811 福 fei column 14 g 43.10 0.36 0.15 oo C3 (cH) 0.11 parts by weight 4841 Example 13 i 43.10 0.25 0.43 1 0.18 I (d- 1) 0.28 parts by weight 4707 Pour 12 g 43.10 0.25 〇 3 d 0.18 (d-1) 0.06 parts by weight 4725 Exception 11 g [43.10 | 0.25 0.15 I | 0.18 I 4730 i | Example 10 | g | Π 1 0.25 j 0.15 0.18 4019 Hybrid 9 s 43.10 | 1 0.25 丨0.15 1 丨1 1 Hybrid 8 | g | 25.14 I 1 0.25 1 | 0.15 I | parts by weight | 0.18 1 — MPa 1 4055 i parts by weight I Parts I parts by weight 1 parts by weight 1 parts by weight 1 Back to CO CO τ~|Η 1 CI(^t) 1 1 dl(^t) 1 Within the composition, additional added material age ah Jia bending bomb 1 · Health number 201041946 Example 22 〇1—Η 43.10 0.25 0.15 0.14 0.18 4688 Example 21 〇1 43.10 0.25 0.15 0.14 0.18 4699 Example 20 Ο ϊ-Η 43.10 0.25 0.15 0.14 0.18 4758 Example 19 100 43.10 0.25 0.15 0.14 0.18 4636 Example 18 Ο 43.10 1 0.25 0.15 0.14 0.18 4688 parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight MPa Item composition (Ν cfj m 1 〇e-Ι (additional addition) e-2 (additional addition) e-3 (additional addition) e-4 (additional addition) e-5 (additional addition) 2 Physical property evaluation bending elastic modulus 201041946 ο ο [inch <] Comparative Example 5 〇0.33 0.08 1.09 0.33 5.44 1.09 0.54 2200 0.17 rH lH Example 23 〇1-H 43.10 0.33 0.08 1.09 0.33 5.44 1.09 0.54 4122 0.18 m c5 rn Parts by weight Parts by weight Part by weight Part by weight Part by weight Part by weight Part by weight Part by weight Part by weight 1 MPa bS) W) Item composition (N ά A Τ—( Τ—Η cA ώ (Ν ώ m 物 Physical property evaluation Bending elastic coefficient sliding Sex (wear factor) * Slidability (S45C wear) * Slidability (resin side wear) * Seven inches 3 c^o (N<ux&ooe*