557307557307
發明所屬技術範園 本發明係關於剛性高，潛變特性優良，而且表面硬度 高，滑動特性亦優的聚縮醛共聚物。 習知技術 聚縮醛樹脂在機械特性，熱特性、電氣特性、滑動性 、成型性等方面，具有優良特性，主要做爲構造材料或 機構零件等，廣用於電氣機器、汽車零件、精密機械零 件等，然而，隨著聚縮醛樹脂利用範圍的擴大，所要求 特性有愈來愈高度化，複合化，特殊化的傾向。此等要 求特性，是在聚縮醛樹脂維持固有的優良滑動性、外觀 等，又要求進一步提高剛性。針對如此要求，若單純以 提高剛性爲目的，一般是在聚縮醛樹脂充塡纖維狀塡料 等方法，但此方法因充塡纖維狀塡料等，有引起成型品 外觀不良或滑動特性降低等問題，而且更有韌性降低的 問題。另外，已知在聚縮醛共聚物中減少所要共聚合的 共聚單體量，可以提高剛性，而無損滑動性或外觀。可 是，在共聚單體減量之手段中，不但韌性會降低，也會 發生聚合物熱安定性降低的問題，必然無法應付要求。 經濟部智慧財產局員工消費合作社印製 有鑑於此等習知技術的問題，本發明人假設聚縮醛樹 脂爲維持本來具有的諸優良特性，同時改善剛性，則設 計以聚縮醛樹脂的聚合物骨架本身經改質的聚合物爲基 之樹脂組成物，應係掌握解決目的之重要關鍵。 關於此等聚縮醛樹脂的聚合物骨架本身之改質，日本 專利特開平3 - 1 70526號公報揭示之改質聚縮醛共聚物， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 五、發明說明（> ) 係由選自三噚烷、環氧乙烷、1，3 -二噚烷、1，3 -二噚庚 環、1，3，5 -三曙庚環、1，3，6 -三噚辛環之至少一種環醚 化合物，與選自縮水甘油基苯醚，氧化苯乙烯、縮水甘 油基萘醚之至少一化合物共聚合而得。可是此改質聚縮 醛共聚物，因結晶速度增大，成型性獲得改善。尤其以 高度再循環性爲目的，然而根據本發明等的硏究，此等 共聚物之熱安定性劣。 發明槪述 本發明之目的，在於解決上述課題，提供一種樹脂材 料，在維持聚縮醛樹脂具有的優良外觀，滑動性，熱安 定性等諸特性的同時，可改善剛性。 本發明人爲達成上述目的，潛心硏究結果，發現將特 定多官能化合物共聚合，導入支鏈•交聯構造同時控制 其末端基量之聚縮醛共聚物。可解決上述課題，而完成 本發明。 即，本發明係由（A )三噚烷，（B ) —分子中含有環氧基2 個以上之化合物0.0 005〜2重量份，和（C)三噚烷共聚性 環醚化合物0〜20重量份，共聚合而得，而總末端量爲1 5 〜150mmol/kg之聚縮醒共聚物及其製法。 發明之詳細說明 茲詳述本發明聚縮醛共聚物如下。本發明聚縮醛共聚 物係以（A)三噚烷和（B)—分子中具有環氧基2個以上之化 合物爲必要成份，最好再加（C)三噚烷共聚性環醚化合物 ，共聚合而得。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 557307 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 ) 本發明所用三噚烷（A )，係醛之滑狀三聚物，一般是在 酸性觸媒存在下，由甲醛水溶液反應而得，利用蒸餾等 方法加以精製使用。用於聚合之三噚烷，係液狀’其溫 度以65〜135°C爲佳。 其次，本發明所用（B)成份係一分子中含有環氧基2個 以上的化合物，其中尤以選自二縮水甘油醚化合物，三 縮水甘油醚化合物，四縮水甘油醚化合物組群爲佳。其 例有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 縮水甘油醚、雙酚A二縮水甘油醚、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 、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚，異 戊四醇四縮水甘油醚，山梨糖醇聚縮水甘油醚、山梨糖 醇酐聚縮水甘油醚、聚甘油聚縮水甘油醚、二甘油聚縮 水甘油醚等。此等化合物可單獨或二種以上倂用、可供 與三噚烷（A)共聚合。在本發明中，（B) —分子中含有環 氧基2個以上之化合物，相對於（A)三噚烷100重量份， 使用0.0005〜2重量份之範圍。以0.001〜1重量份範圍 爲佳，而以0 · 003〜0 · 5重量份範圍最好。此（B)成份用量 低於0 · 0005重量份時，難以獲得具有所欲目的特性之聚 縮醛共聚物，而超出2重量份時，所得聚縮醛共聚物的成 型加工性，耐衝擊性、表面特性降低，均不宜。 其次，本發明中三噚烷（A )共聚性環醚化合物（c )，有 環氧乙烷、環氧丙烷、表氯烷、表溴烷、氧化苯乙烯、 請 先 閱 讀 背 & 之 注 意 事 項再·!ί裝 頁 訂 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 557307 A7 B7 _ 五、發明說明（小） (請先閱讀背面之注意事項再填寫本頁) 二噚庚環、3，3 -雙（氯甲基）二噚庚環、四氫芙喃、三噚 辛環、1，3 -二噚茂烷、丙二醇甲醛、二乙二醇甲醛、三 乙二醇甲醛、1，4 -丁二醇甲醛、1，5 -戊二醇甲醛、1，6-己二醇甲醛等，其中以環氧乙烷、丨，3-二噚茂烷、二乙 二醇甲醛，1，4-丁二醇甲醛爲佳。此等環醚化合物（C)之 用量’要考慮到所得聚縮醛共聚物之剛性，耐藥品性等 ，相對於（A)三噚烷1〇〇重量份，使用一種或二種以上合 計0〜20重量份，以〇 . 〇 1〜1 5重量份爲佳，而以0 . 1〜1 0 重量份最好。Technical Field of the Invention The present invention relates to a polyacetal copolymer having high rigidity, excellent creep properties, high surface hardness, and excellent sliding properties. Known technology Polyacetal resin has excellent characteristics in terms of mechanical properties, thermal properties, electrical properties, sliding properties, moldability, etc., and is mainly used as construction materials or mechanism parts. It is widely used in electrical equipment, automotive parts, and precision machinery. Parts and the like, however, with the expansion of the range of use of polyacetal resins, the required characteristics tend to become more advanced, complex, and specialized. These properties require polyacetal resins to maintain excellent sliding properties, appearance, etc., and further increase rigidity. In response to such requirements, if the purpose is simply to increase the rigidity, it is generally a method of filling a fibrous material with a polyacetal resin. And other problems, and more reduced toughness. In addition, it is known that reducing the amount of comonomer to be copolymerized in a polyacetal copolymer can increase rigidity without impairing sliding properties or appearance. However, in the method of reducing the comonomer, not only the toughness will be reduced, but also the problem that the thermal stability of the polymer is reduced will inevitably be unable to meet the requirements. In view of the problems of these conventional technologies, the inventors of the Intellectual Property Bureau of the Ministry of Economic Affairs have printed the polyacetal resin in order to maintain the excellent properties and improve rigidity. The modified polymer-based resin composition of the physical skeleton itself should be the key to mastering the purpose. Regarding the modification of the polymer skeleton itself of these polyacetal resins, the modified polyacetal copolymer disclosed in Japanese Patent Laid-Open No. 3-1 70526, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 5. Description of the invention (>) is selected from the group consisting of trioxane, ethylene oxide, 1,3-dioxane, 1,3-difluorene heptane, 1,3,5 -three At least one cyclic ether compound of the succinyl ring and the 1,3,6-triamidine ring is copolymerized with at least one compound selected from the group consisting of glycidyl phenyl ether, styrene oxide, and glycidyl naphthyl ether. However, this modified polyacetal copolymer has improved moldability due to an increase in crystallization speed. Especially for the purpose of high recyclability, according to the investigation of the present invention and the like, the thermal stability of these copolymers is poor. DISCLOSURE OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a resin material which can improve rigidity while maintaining various properties such as excellent appearance, sliding properties, and thermal stability of a polyacetal resin. In order to achieve the above-mentioned object, the present inventors diligently researched the results, and found that a polyacetal copolymer in which a specific polyfunctional compound is copolymerized and a branched-chain crosslinked structure is controlled while controlling the amount of terminal groups. The above problems can be solved and the present invention has been completed. That is, the present invention consists of (A) trioxane, (B)-a compound containing two or more epoxy groups in the molecule, 0.0 005 to 2 parts by weight, and (C) a trioxane copolymerizable cyclic ether compound 0 to 20 A part by weight is obtained by copolymerization, and a polycondensation copolymer having a total terminal amount of 15 to 150 mmol / kg and a preparation method thereof. DETAILED DESCRIPTION OF THE INVENTION The polyacetal copolymer of the present invention is described in detail below. The polyacetal copolymer of the present invention is composed of (A) trioxane and (B) —a compound having two or more epoxy groups in the molecule as an essential component, and it is preferable to add (C) a trioxane copolymerizable cyclic ether compound. , Derived from copolymerization. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557307 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Trioxane (A) used in the present invention The slip-like terpolymer of aldehyde is generally obtained by the reaction of an aqueous formaldehyde solution in the presence of an acidic catalyst, and is purified by distillation or other methods. The trioxane used for polymerization is in a liquid state, and its temperature is preferably 65 to 135 ° C. Next, the component (B) used in the present invention is a compound containing two or more epoxy groups in one molecule, and among them, it is particularly preferably selected from the group consisting of a diglycidyl ether compound, a triglycidyl ether compound, and a tetraglycidyl ether compound. Examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, hexanediol diglycidyl ether, resorcinol glycidyl ether, and bisphenol A diglycidyl ether. Glyceryl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, isoprene tetraol Glyceryl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, and the like. These compounds can be used alone or in combination of two or more, and can be copolymerized with trioxane (A). In the present invention, (B) — a compound containing two or more epoxy groups in a molecule, in a range of 0.0005 to 2 parts by weight based on 100 parts by weight of (A) trioxane. A range of 0.001 to 1 part by weight is preferable, and a range of 0. 003 to 0. 5 part by weight is most preferable. When the amount of the component (B) is less than 0.0005 parts by weight, it is difficult to obtain a polyacetal copolymer having desired characteristics. When it exceeds 2 parts by weight, the molding processability and impact resistance of the obtained polyacetal copolymer are difficult. , Surface properties are not suitable. Secondly, in the present invention, the trioxane (A) copolymerizable cyclic ether compound (c) includes ethylene oxide, propylene oxide, epichlorohydrin, epibromoalkane, and styrene oxide. Please read back & Matters again! Ί The size of the bound paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 557307 A7 B7 _ 5. Description of the invention (small) (Please read the precautions on the back before filling in this page ) Di-Heptane ring, 3,3-Bis (chloromethyl) di-Heptane ring, Tetrahydrofuran, Tris (Hydroxyoctyl ring), 1,3-Di-Hydrocenane, Propylene glycol formaldehyde, Diethylene glycol formaldehyde, Tris Ethylene glycol formaldehyde, 1,4-butanediol formaldehyde, 1,5-pentanediol formaldehyde, 1,6-hexanediol formaldehyde, etc., among which ethylene oxide, Ethylene glycol formaldehyde and 1,4-butanediol formaldehyde are preferred. The amount of these cyclic ether compounds (C) is used in consideration of the rigidity and chemical resistance of the obtained polyacetal copolymer. One or two or more kinds are used in total with respect to 100 parts by weight of (A) trioxane. ~ 20 parts by weight, preferably 0.01 to 15 parts by weight, and most preferably 0.1 to 10 parts by weight.
經濟部智慧財產局員工消費合作社印製 在本發明聚縮醛共聚物製造中，其特徵爲在上述成份 之外’可倂用分子量調節成份，調節末端基量。分子量 調節成份係不形成不安定末端之鏈轉移劑，可以甲醛、 甲氧基甲醛、二甲氧基甲醛、三甲氧基甲醛、氧伸甲基 二正丁醚等具有烷氧基之化合物等爲例。本發明中藉調 節此等分子量調節劑之使用量，以調節所生成聚縮醛共 聚物的總末端基量爲15〜150mmol/kg，以20〜100mmol/kg 爲佳。總末端基量太少時，流動性顯著惡化，射出成型 等加工非常困難。而總末端基量過多時，熔體黏度明顯 降低，在擠壓等製造步驟中，無法形成片顆粒，或發明 韌性顯著降低，均不宜。 爲製造上述由單體成份和共聚單體成份構成之本發明 聚縮醛共聚物，所用觸媒一般爲陽離子聚合觸媒。具體 例有四氯化鉛、四氯化錫、四氯化鈦、三氯化鋁、氯化 鋅、三氯化釩、三氯化銻、五氟化磷、五氟化銻、三氟 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 5573〇7 A7 B7 經濟部智慧財產局員工消費合作社印製 i、發明說明（r) 化硼、三氟化硼二乙醚化物，三氟化硼二丁醚化物，三 氟化硼二噚烷化物、三氟化硼二酐化物、三氟化硼三 乙胺複合物等三氟化硼配位化合物，過氯酸、乙醯基過 氯酸鹽、三級丁基過氯酸鹽、羥基乙酸、三氯乙酸、三 氟乙酸、對甲苯磺酸等無機酸和有機酸，三乙基四氯硼 酸羊、三苯基六氯銻酸甲酯、烯丙基六氯磷酸重氮鹽、 烯丙基四氯硼酸重氮鹽等複合氯化物，二乙基鋅、三乙 基鋁、二乙基氯化鋁等烷基金屬鹽，異性聚合酸，同素 聚合酸等一種或二種以上。其中以三氟化硼，三氟化硼 二乙醚化物，三氟化硼二丁醚化物、三氟化硼三乙胺複 合物等三氟化硼配位化合物爲佳。此等陽離子聚合觸媒 可就此使用，亦可以有機溶劑等預先烯釋，其調製方法 無特別限制。 本發明聚縮醛共聚物之製法雖無特別限定，但一般係 使用液化（A )三噚烷，上述（B ) —分子中有環氧基2個以上 之化合物，（C)以環醚化合物爲主的陽離聚合觸媒，進 行塊狀聚合以獲得固體粉塊狀聚合物。聚合裝置無特別 限制，可使用已知裝置，分批式、連續式等各種方法均 可。又，聚合溫度以保持65 - 1 3 5°C爲佳。 聚合後的觸媒失活，是在聚合反應後，於聚合機排出 的生成反應物，或聚合機中之反應生成物，添加鹼式化 合物或其水溶液等爲之。將聚合觸媒中和失活所用鹼式 化合物，可用氨，或三乙胺、三丁胺、三乙醇胺、三丁 醇胺等胺類，或鹼金屬、鹼土金屬之氫氧化物類，及其 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) F-裝 • ϋ ·ϋPrinted by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the production of the polyacetal copolymer of the present invention, it is characterized in that in addition to the above components, a molecular weight adjusting component can be used to adjust the amount of terminal groups. The molecular weight adjusting component is a chain transfer agent that does not form a unstable terminal, and can be formaldehyde, methoxy formaldehyde, dimethoxy formaldehyde, trimethoxy formaldehyde, oxymethyl di-n-butyl ether and other compounds having an alkoxy group. example. In the present invention, the amount of these molecular weight regulators is adjusted to adjust the total terminal group amount of the polyacetal copolymer to be 15 to 150 mmol / kg, and preferably 20 to 100 mmol / kg. When the total end group amount is too small, the fluidity is significantly deteriorated, and processing such as injection molding is very difficult. When the total amount of terminal groups is too large, the melt viscosity is significantly reduced. In the manufacturing steps such as extrusion, it is not possible to form pellets, or the invention significantly reduces the toughness, which is not suitable. In order to produce the above-mentioned polyacetal copolymer of the present invention composed of monomer components and comonomer components, the catalyst used is generally a cationic polymerization catalyst. Specific examples are lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, phosphorus pentafluoride, antimony pentafluoride, and trifluorobenzyl. Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 5573〇7 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i. Description of invention (r) Boron trioxide, boron trifluoride diethyl etherate , Boron trifluoride dibutyl etherate, boron trifluoride dioxane, boron trifluoride dianhydride, boron trifluoride triethylamine complex and other boron trifluoride complexes, perchloric acid, ethyl Inorganic and organic acids such as fluorenyl perchlorate, tertiary butyl perchlorate, glycolic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, triethyltetrachloroborate, triphenylhexadecane Compound chlorides such as methyl chloroantimonate, allyl hexachlorophosphate diazonium salt, allyl tetrachloroborate diazonium salt, and alkyl metals such as diethylzinc, triethylaluminum, and diethylaluminum chloride One or two or more kinds of salt, heteropolymeric acid, and homopolymeric acid. Among them, boron trifluoride complexes such as boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, and boron trifluoride triethylamine complex are preferred. These cationic polymerization catalysts may be used as they are, and they may be previously released by an organic solvent or the like, and the preparation method thereof is not particularly limited. Although the production method of the polyacetal copolymer of the present invention is not particularly limited, generally, liquefied (A) trioxane is used. The above (B)-the compound having two or more epoxy groups in the molecule, (C) is a cyclic ether compound The main cationic polymerization catalyst was subjected to block polymerization to obtain a solid powder block polymer. The polymerization apparatus is not particularly limited, and a known apparatus may be used, and various methods such as a batch method and a continuous method may be used. The polymerization temperature is preferably maintained at 65-1 3 5 ° C. The deactivation of the catalyst after the polymerization is to generate a reaction product discharged from the polymerization machine after the polymerization reaction or a reaction product in the polymerization machine by adding a basic compound or an aqueous solution thereof. The basic compound used for neutralizing and deactivating the polymerization catalyst may be ammonia, or amines such as triethylamine, tributylamine, triethanolamine, tributanolamine, or hydroxides of alkali metals, alkaline earth metals, and the like. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) F-pack • ϋ · ϋ
557307 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（^) 他已知觸媒失活劑。另外，聚合反應後，對生成物迅速 加此等水溶液，使其失活爲佳。經此聚合方法和失活方 法後，必要時可按習知方法進行淨洗，未反應單體之分 離回收、乾燥等。此外，必要時可按已知方法進行安定 化處理，將不安定末端部分解除去或利用安定物質把不 安定末端封鎖等，可配合必要之各種安定劑爲之。於此 所用安定劑，有受阻酚系化合物、含氮化合物、鹼金屬 或鹼土金屬之氫氧化物，無機鹽，羧酸鹽之任一種或二 種以上。 上述所得聚縮醛共聚物，其重量.平均分子量以10,000 〜500,000爲佳，而以20, 000〜150,000最好。關於末端 基，以利用1H-NMR測得半縮甲醛量在0〜4mmol/kg爲佳。 而以0〜2mmol/kg最好。若超過4mmol/kg，隨成型等聚 合物分解，會產生發泡等問題。爲控制半縮甲醛末端基量 於上述範圍，提供聚合的單體、共聚單體總量中之雜質 ，尤其是水份，以在20ppm以下爲宜，而以lOppm以下最 好。 此外，本發明聚縮醛共聚物，可視需要添加對熱塑型 樹脂之一般添加劑，例如染料、顏料等著色劑，滑劑， 成型劑，離型劑，去靜電劑、界面活性劑，或有機高分 子材料，無機或有機纖維狀、粉狀、板狀塡料一種或二 種以上。 實施例 茲以實施例具體說明本發明如下，惟本發明不限於此 (請先閱讀背面之注意事項#|填寫本頁) 1 裝 訂· .if- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 557307 A7 ___ B7 五、發明說明（7 ) 等實施例。又，實施例中的評鑑係以下述方法進行。 拉力強度 使用射出成型機，成型啞呤型試片，根據ASTM 0638方 法進行測量。 撓曲彈件率 使用射出成型機，成型試片，根據ASTM方法進行測 量。 末端基分析 將物性評鑑用聚合物，溶入六氟異丙醇d2，進行1Η-NMR測定。由各末端相對應高峰面積加以定量。 實施例1-10 使用連續式混合反應機，包括斷面爲雙圓部份重疊形 狀之筒部，外側附設流通熱（冷）媒的夾套，以及附設槳 片之轉動軸，附設槳片之二支轉動軸分別以1 5 0 r p m轉動 ，同時按表1所示比例添加（A )三噚烷、（B ) —分子中有環 氧基2個以上之化合物，（C)環醚化合物，再將分子量調 節劑之甲醛，同時和觸媒之三氟化硼0 . 005重量份，連續 供應至聚合機，進行塊狀聚合。又，單體中所含水份， 在實施例1-9爲4ppm，實施例10爲15ppm。從聚合機排 出的反應生成物迅速通過破碎機，添加含三乙胺〇 · 05重 量％的60°C水溶液，使觸媒失活。再經分離，洗淨，乾 燥後，得粗製聚縮醛基聚物。其次，相對於此粗製聚縮 醛共聚物100重量份，添加三乙胺5重量％水溶液4重量 份，異戊四醇基肆[3 - ( 3，5 -二（三段丁基卜4 -羥苯基）丙酸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項寫本頁) 、訂· -丨線〕 經濟部智慧財產局員工消費合作社印製 5573〇7 A7 B7 I、發明說明（β) 酯]Ο . 3重量份，在雙螺桿壓出機，於2 1 0 °C熔混，除去不 安定部份。所得聚縮醛共聚物，以六氟異丙醇d2爲溶劑 ，利用NMR測量，確認其構造爲共聚合組成。 上述方法所得聚縮醛共聚物1 00重量份，添加安定劑異 戊四醇基肆[3-(3, 5-二（三段丁基）-4 -羥苯基）丙酸酯] 〇 . 03重量份，和三聚氰胺〇 . 1 5重量份，於雙螺桿壓出機， 在21 0°C熔混，得片顆粒狀聚縮醛共聚物。按前述方法 評鑑，評鑑結果如表1所示。 比較1 - 5 在比較例卜3，不用（B ) —分子中有環氧基2個以上之 化合物，而比較例4 - 5，係改變甲醛基，由此調製之聚縮 醛共聚物，和實施例同樣製得片顆粒狀聚縮醛共聚物，並 加以評鑑。結果如表1所示。 (請先閱讀背面之注意事項㈣填寫本頁) 裝 · 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 557307 A7 B7 經濟部智慧財產局員工消費合作社印製557307 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (^) He knows catalyst inactivating agents. After the polymerization reaction, it is preferable to quickly add these aqueous solutions to the product to deactivate it. After the polymerization method and the deactivation method, if necessary, it can be cleaned according to conventional methods, and the unreacted monomers can be separated and recovered, and dried. In addition, if necessary, a stabilization process can be performed according to a known method to remove the unstable end portion or use a stable substance to block the unstable end, etc., and various stabilizers can be used as necessary. The stabilizers used herein include any one or two or more of hindered phenol compounds, nitrogen compounds, hydroxides of alkali metals or alkaline earth metals, inorganic salts, and carboxylic acid salts. The weight-average molecular weight of the obtained polyacetal copolymer is preferably 10,000 to 500,000, and more preferably 20,000 to 150,000. As for the terminal group, the amount of hemiformal measured by 1H-NMR is preferably 0 to 4 mmol / kg. And 0 ~ 2mmol / kg is the best. If it exceeds 4 mmol / kg, problems such as foaming occur due to decomposition of the polymer such as molding. In order to control the amount of hemiformal terminal groups in the above range, it is preferable to provide impurities in the total amount of polymerized monomers and comonomers, especially moisture, below 20 ppm, and most preferably below 10 ppm. In addition, the polyacetal copolymer of the present invention may be added with general additives to thermoplastic resins, such as dyes, pigments and other colorants, slippers, molding agents, release agents, destaticizers, surfactants, or organics. Polymer materials, inorganic or organic fibrous, powdery, plate-shaped materials, one or two or more. EXAMPLES The present invention is described in detail in the following examples, but the present invention is not limited to this (please read the precautions on the back # | Fill this page first) 1 Binding · .if- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557307 A7 ___ B7 5. Examples of invention (7). The evaluation in the examples was performed by the following method. Tensile strength Using an injection molding machine, a durin-type test piece was formed and measured according to the ASTM 0638 method. Deflection spring rate Using an injection molding machine, a test piece was formed and measured according to the ASTM method. End group analysis The polymer for evaluating physical properties was dissolved in hexafluoroisopropanol d2, and 1H-NMR measurement was performed. It is quantified by the corresponding peak area at each end. Embodiment 1-10 A continuous mixing reactor is used, which includes a cylindrical section with a double-circular cross section, a jacket with a hot (cold) medium flowing on the outside, a rotating shaft with a paddle, and a paddle with a paddle. The two rotating shafts are rotated at 150 rpm, and at the same time, (A) trioxane and (B)-compounds having more than two epoxy groups in the molecule, (C) cyclic ether compounds, Then, the formaldehyde of the molecular weight regulator and 0.0005 part by weight of the boron trifluoride of the catalyst were continuously supplied to the polymerization machine to perform block polymerization. The water content in the monomer was 4 ppm in Example 1-9 and 15 ppm in Example 10. The reaction product discharged from the polymerization machine quickly passed the crusher, and a 60 ° C aqueous solution containing 0.05% by weight of triethylamine was added to deactivate the catalyst. After separation, washing and drying, a crude polyacetal-based polymer was obtained. Next, based on 100 parts by weight of the crude polyacetal copolymer, 4 parts by weight of a 5% by weight aqueous solution of triethylamine was added, and the isopentaerythritol group [3-(3,5-di (tris-butylbutyl 4-hydroxybenzene Base) Propionate This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back to write this page), order ·-line] Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed 5573〇7 A7 B7 I, Description of the Invention (β) Ester] 0.3 parts by weight, melt-mixed in a twin-screw extruder at 210 ° C to remove unstable parts. The resulting polyacetal copolymer Using hexafluoroisopropanol d2 as a solvent, the structure was confirmed to be a copolymerized composition by NMR measurement. 100 parts by weight of the polyacetal copolymer obtained by the above method was added with a stabilizer isopentaerythritol group [3- (3 , 5-bis (tris-butyl) -4-hydroxyphenyl) propionate] 0.03 parts by weight, and 0.1 15 parts by weight of melamine, melt-mixed in a twin-screw extruder at 21 0 ° C to obtain Sheet granular polyacetal copolymer. Assessed according to the method described above, the evaluation results are shown in Table 1. Comparison 1-5 In Comparative Example 3, no (B) In the molecule, there are two or more epoxy groups, and Comparative Examples 4 to 5 are polyacetal copolymers prepared by changing the formaldehyde group, and pelletized polyacetal copolymers are prepared in the same manner as in the examples. The results are shown in Table 1. (Please read the precautions on the back and fill in this page first.) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. This paper is printed in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 557307 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
557307 A7 B7 _ 五、發明說明（β ) 註：表中縮寫和詳細名稱 BDGE: 1，4-丁二醇二縮水甘油醚 PETGE :異戊四醇四縮水甘油醚 TPTGE :三羥甲基丙烷三縮水甘油醚 GTGE :甘油三縮水甘油醚 DO : 1 ,3-三噚茂烷 *1 :成型時有發泡現象。因空隙、物性稍不安定 *2 ：黏度高，無法成型 * 3 :黏度過低，無法由壓出機調製片顆粒 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）557307 A7 B7 _ V. Description of the invention (β) Note: Abbreviations and detailed names in the table BDGE: 1,4-butanediol diglycidyl ether PETGE: isopentaerythritol tetraglycidyl ether TPTGE: trimethylolpropane tri Glycidyl ether GTGE: glycerol triglycidyl ether DO: 1,3-trimethylenelocane * 1: foaming during molding. Slightly unstable because of voids and physical properties A4 size (210 X 297 mm)