201037028 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種經改質之聚曱醛，尤其關於一種添 加自由基捕捉劑來提升熱安定性的聚曱搭。 【先前技術】 聚曱酿是以[CH20]-為重複單元之聚合體，屬高結晶 性向熔點的聚合物。由於其分子結構之關係，因此熱安定 性較差，受熱時會有曱醛或甲醛類低分子量釋出，對塑膠 造成裂解。故業界有時會以共聚反應的方式改質聚曱酸， 提升其熱安定性。例如可以與環醚類如環氧乙烷或二氧戊 環（l，3-dioxolane)共聚合。由於光聚合體中僅小量的碳_碳 (C-C)共聚合鍵即可提升聚曱醛熱安定性，因此可被業界採 用。例如在歐洲專利Ep. 128739 ( 1984)中以三氧雜環乙 烷(tri〇Xane)共聚合。第二種改質方式可採用末端基的羥基 改以醚基或酯基取代。例如使用曱氧基(meth〇xy)或乙醯基 (acetyl)則可降低受熱分解。例如美國專利4097453即 是將具聚甲醚之不穩定羥基將其醚化（etherificati〇n)而 達到穩定效果。然無論業界是採用第一種方式以共聚合方 式或第二種方式以曱氧基或乙醯基末端基取代較不穩定 的經基方式’但仍受限於其分子結構本身仍易於自行氧化 裂解（autoxidation)效應，尤其亞曱基(methylene)上的氫原 子易受鄰近氧原子之穩定效應而易受自由基攻擊，造成氧 化裂解。聚曱醛的自動氧化裂解機構文獻中已有廣泛研究 並建立了很好的基礎。如Didina等人在J.Polym.Sci.Polym. 4/21 201037028201037028 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a modified polyfurfural, and more particularly to a polyaddition which adds a radical scavenger to enhance thermal stability. [Prior Art] Polymerization is a polymer having a repeating unit of [CH20]-, which is a polymer having a high crystallinity to a melting point. Due to its molecular structure, thermal stability is poor, and low molecular weight release of furfural or formaldehyde occurs when heated, causing cracking of the plastic. Therefore, the industry sometimes upgrades polyphthalic acid by means of copolymerization to enhance its thermal stability. For example, it can be copolymerized with a cyclic ether such as ethylene oxide or 1,3-dioxolane. Since only a small amount of carbon-carbon (C-C) copolymerization bond in the photopolymer can enhance the thermal stability of polyacetal, it can be used in the industry. For example, in European Patent Ep. 128739 (1984), it is copolymerized with trioxane (tri〇Xane). The second modification can be carried out by replacing the hydroxyl group of the terminal group with an ether group or an ester group. For example, the use of a methoxy group (meth〇xy) or an ethyl acetyl group can reduce thermal decomposition. For example, U.S. Patent No. 4,094,453, which is an ethereal hydroxy group with a polymethyl ether, is etherified to achieve a stabilizing effect. However, whether the industry adopts the first method to replace the less stable warp-based method with a decyloxy or acetyl end group in the copolymerization mode or the second method, it is still limited by its molecular structure itself and is still easy to oxidize itself. The autoxidation effect, especially the hydrogen atom on the methylene, is susceptible to the stabilizing effect of adjacent oxygen atoms and is susceptible to free radical attack, resulting in oxidative cleavage. The automatic oxidative cleavage mechanism of polyfurfural has been extensively studied in the literature and established a good foundation. Such as Didina et al. at J. Polym. Sci. Polym. 4/21 201037028
Lett. Ed. 16 (1967) P2277報導主要裂解氧化產物中約含甲 醛80至90%，甲酸約含7至9%，另有低量的一氧化碳及 二氧化碳被觀察到。其中以自由基所造成裂解為聚甲醛受 熱分解之主因，因此控制自由基生成也成為穩定聚甲醛熱 安定性之重要手段之一。 常用的控制自由基生成方式為加入抗氧化劑來捕捉 自由基之生成。如阻盼系抗氧化劑（hindered phenolic antioxiants)抑制自由基氧化程式之進行。這類常用阻紛系 〇 之自由基捕捉劑有1，1-二（3,5-叔丁基-2-羥基苯基）乙烷 [l，l-bis(3,5-tert-butyl-2-hydroxyphenyl)ethane]、異戊四醇 四（3-(3,5-二叔丁基-4-羥基苯基））丙酸酯（CAS No.229-722-6)、三乙二醇二(3-(3-叔丁基-5-甲基-4-羥基苯 基)）丙酸酯（CAS No.36443-68-2)、三（3,5-二叔丁基-4-羥 基节 基） 三異 氫 脈酸醋 [l,3,5-tris-(3,5-di-tert-butyl-4-hydroxy benzyl)isocyanurate]、1,6-六亞甲基二（3-(3,5-二叔丁基-4-◎ 經 基苯基））丙 酸醋 [1,6-hexamethylene bis-3-(3,5-di-tert-butyl-4-dydroxy phenyl)propionate] ' Ν,Ν-六亞甲基二-3,5-二叔丁基-4-羥基氧化肉桂醯胺（CAS No. 245-442-7)、4,4’-亞曱基二（2,6-二叔丁基苯酚）[4,4， -methylene(2,6-di-tert-butylphenol)]、/3-(3,5-:*T*-4-羥基苯基）丙酸十八酯（CAS No. 218-216-0)、2,2’ -亞甲 基-二 （4-曱基-6-叔丁基苯酚）[2,2 ’ -methylene-bis(4-methyl-6-tert_butyl phenol)、1,3,5-三甲 基-2,4,6-三（3,5_二叔丁基-4-羥基苄基）苯 5/21 201037028 [l,3,5-tris(3,5-di-tert-4-hydroxyphenyl)mesitylene ' 1,1,3-三（5 ’ -叔丁基-4 ’ -羥基-2 ’ -曱基苯基）丁烷 [l,l,3-tris(5 ’ -tert-butyl-4 ’ -hydroxy-2 ’ methylphenyl)butane]、2,4’ -二甲基-6’ -叔丁基苯基-亞 曱基-6-叔丁基-4-曱基·苯基丙烯酸酯（CAS No. 61167-58-6)等。上述苯酚系自由基捕捉劑中最常用於聚 曱醛為異戊曱醇四（3-(3,5-二叔丁基-4-羥基苯基））丙酸酯 及三乙二醇二[3-(3-叔丁基-5-甲基-4-羥基苯基)]丙酸酯二 者。例如於日本專利 JP57179245(1982)、 JP01275652(1989) 、 JP02028240(1990) 、 JP06240102(1994) 、 JP06207080(1994)及美國專利 US2004176508(2004)中皆有使用阻酚系（hindered phenols)自由基捕捉劑來達到延長聚曱醛熱安定性之效 果。然而聚曱醛作為工程塑料’無論是汽車、航空、精密 儀器、產業機械等則需要更高的剛性、強度及熱穩定性才 能符合材料科學日益嚴苛的條件要求。 【發明内容】 有鑑於此，本發明為解決上述技術問題，並提供—種 添加自由基捕捉劑來提升熱安定性的聚曱酸。 為了達到上述目的，本發明提出一種經改質以提高熱 安定性的聚曱醛，其中將雙組份以上之自由基捕捉劑添^ 於聚曱醛中。本發明所用的雙組份自由基捕捉劑包括以 1，3,5-二曱基-2,4,6-三（3,5-二叔丁基_4_羥基节基）笨為主 的自由基捕捉劑以及選自異戊四醇_四（3_(3,5_二叔丁基 6/21 201037028 說基苯基））丙酸酯或二（3,5-二叔丁基_4_經基苄基）二異 氰脲酸酯或/9 -(3,5-二叔丁基-4-羥基-苯基）丙酸十八酯其 中一個組成雙組份或含上述至少二組份以上之自由基捕 捉劑。 根據一較佳實施例，將雙組份以上之自由基捕捉劑添 加於該聚甲醛中，該雙組份自由基捕捉劑包括二種或兩種 以上選自由1，3,5-二曱基-2,4,6-三（3,5-二叔丁基_4_羥基苄 基）苯、異戊四醇-四（3-(3,5-二叔丁基_4_羥基苯基））丙 〇酸酯或二（3,5-二叔丁基-4-羥基苄基）三異氰脲酸酯及冷 -(3,5-二叔丁基-4-羥基-苯基）丙酸十八酯所組成之族群者。 根據一較佳實施例，經添加雙組份自由基捕捉劑改質 以提高熱安定性的聚甲醛，其中該雙組份自由基捕捉劑為 阻盼系抗氧化劑（hindered phenolic antioxidants )。 根據一較佳實施例，經雙組份自由基捕捉劑改質以提 高熱安定性的聚甲醛裡，該雙組份自由基捕捉劑的其中一 組份為1，3,5-三曱基-2,4,6-三（3,5-二叔丁基-4-羥基苄基） ❹苯，而另一組份為異戊四醇-四（3-(3,5-二叔丁基_4_羥基笨 基））丙酸酯、三（3,5-二叔丁基-4·羥基苄基）三異氰脲酸 酿或/5-(3,5-二叔丁基-4-羥基-苯基）丙酸十八酯三者其中 -— 〇 根據一較佳實施例，經雙組份自由基捕捉劑改質以提 高熱安定性的聚甲醛裡，其中1,3,5-三曱基-2,4,6-三（3,5-二叔丁基-4-羥基苄基）苯的含量為至少1重量％以上而另 一組份（異戊四醇-四（3-(3,5-二叔丁基-4-羥基苯基））丙 酸酯、三（3,5-二叔丁基-4-羥基苄基）三異氰脲酸酯或/3 7/21 201037028 -(3,5-二叔丁基_4_羥基-苯基）丙酸十八酯三者其中之一）的 含量為至少10重量％。 根據一較佳實施例，經雙組份自由基捕捉劑改質以提 高熱安定性的聚曱醛裡，其中一組份（u，5_三甲基_2,4,6_ 二（3,5-二叔丁基_4_羥基苄基）苯）相對於另一組份（異 戊四醇-四（3-(3,5-二叔丁基-4-羥基苯基））丙酸酯、三（3,5_ 二叔丁基-4-羥基苄基）三異氟脲酸酯或点_(3,5_二叔丁基 -4-羥基_苯基）丙酸十八酯三者其中之一）的比例為 1:99-90:10，較佳為 5:95-60:40，最佳為 1〇:9〇_4〇:6〇。 ^ 根據一較佳實施例，經雙組份自由基捕捉劑改質以提 ' 高熱安定性的聚甲醛裡，其中該雙組份自由基捕捉劑加入 聚曱醛的數量不超過聚曱醛的5重量％，較佳為聚曱醛的 0.5重量％。 根據一較佳實施例，經雙組份自由基捕捉劑改質以提 咼熱女疋性的聚曱路裡，另包括一種或一種以上選自二次 填系抗氧化劑、紫外線吸收劑、甲酸捕捉劑或甲酸捕捉劑。 ^根據一較佳實施例，經雙組份自由基捕捉劑改質以提❹ 高熱安定性的聚甲醛裡，其中該甲醛捕捉劑為16-六亞甲 基雙（N，N-二曱基氨基脲）。 ’ 以上之概述與接下來的詳細說明及附圖，皆是為了能 進一步说明本發明為達成預定目的所採取之方式、^段及 功效。而有關本發明的其他目的及優點，將在後續的說明 及圖式中加以闡述。 【實施方式】 8/21 201037028 本發明即是針對聚甲醛熱穩定性之進一步強化，提出 一自由基捕捉劑之新穎配方。 本發明系於聚甲醛中添加以1，3,5-三甲基-2,4,6-三 (3,5-二叔丁基-4-羥基苄基）苯為主的自由基捕捉劑並搭 配異戊四醇-四（3-(3,5-二叔丁基-4-羥基苯基））丙酸酯或 二（3,5-二叔丁基-4-羥基苄基三異氰脲酸酯或厶_(3,5_二叔 丁基-4-羥基-苯基）丙酸十八酯組成雙組份或含上述至少二 組份以上之自由基捕捉劑來提升聚甲醛熱安定性。 Ο 當以I3,5-三甲基-2,4,6-三（3,5-二叔丁基-4-羥基苄 基）本為主的自由基捕捉劑用於聚甲酿時，聚甲酸之熱穩 定性可大幅提高約20%。此功效大大不同於上述專利中所 述單組份自由基捕捉劑，且效能亦明顯高於單組份捕捉 劑，生產成本也可有效降低。 本發明中所用的雙組份自由基捕捉劑係指二種選自 阻酚系抗氧化劑的組份。在本發明中，其中一個阻酚系抗 氧化劑組份以1，3,5-三曱基-2,4,6-三（3,5-二叔丁基-4-羥基 〇苄基）苯為主的自由基捕捉劑為例說明，而另一個阻酚系 抗氧化劑則以一選自由異戊四醇_四（3_(3,5_二叔丁基_4_ 羥基苯基））丙酸酯、三（3,5-二叔丁基_4_羥基苄基）三異 氰脲酸酯及石_(3,5-二叔丁基-4·羥基-苯基）丙酸十八酯所 組成之族群者為例說明。 该以1，3,5·二甲基-2,4,6-三（3,5-二叔丁基_4_羥基苄 基）苯為主的自由基捕捉劑為例的阻酚系抗氧化劑的使用 比例為至少1重量％。該選自由異戊四醇_四（3_(3,5·二叔 丁基-4-羥基苯基））丙酸酯、三（3,5_二叔丁基_4_羥基苄基） 9/21 201037028 =異氱腺酸醋及石_(3,5_二叔丁基+羥基_苯基）丙酸十八 西曰所組成之族群者的使用比例為至少1 〇重量％。二者配 方比例介於99:1至10:90之間，較佳介於95:5至4〇:6〇。 同時考慮聚甲醛生產成本與效能之下，則兩者自由基捕捉 劑最佳比例為90:10至60:40。 然而，自由基捕捉劑於聚曱醛添加量相對於1〇〇份重 量之聚甲_約含〇 〇1至3重量份數的自由基捕捉劑。本 發明所提出的雙組份自由基捕捉劑除可以與上述阻酚系 自由基捕捉劑形成雙組份以上自由基捕捉劑外，並有時會 搭配磷系抗氧化劑或紫外線吸收劑或曱醛捕捉劑或甲酸 捕捉劑或無機填料等。 常用的磷系抗氧化劑有亞磷酸三苯酯、亞磷酸三（2,4_ 二叔丁基苯）酯（CAS No. 250-709-6)、四（2,4-二叔丁基 苯基）-4,4’ -聯苯基雙磷酸酯（pep_q)、季戊四醇雙亞礙 酸二（2,4-二叔丁基苯苯基）醋（casNo._247-952-5 )及 季戊四醇雙亞磷酸（十八）酯（CAS No. 223-276-6)等。 本發明所使用的自由基捕捉劑可與紫外線吸收劑並 用’亦有增進聚甲酸耐候強度。常用的紫外線吸收劑以苯 並三嗤為主’例如包括，2-(2，-羥基-3，-叔丁基-5，-甲 基苯基-5-氯代苯並三唑（CAS No· 223-445-4)、2-(2氫-笨並三°坐_2_基)-4,6-二叔戊基苯酚（CAS_No. 247-384-8)、 2-(2’ -羥基-5-曱基苯基）苯並三唑（CAS No. 219-470-5)、 2-苯並三唑_2_基_4,6_二叔丁基苯酚（CAS No. 223-346-6) ’ 2-(2氫-苯並三唑-2-羥基）-4-(叔丁基-6-仲丁 基）苯酚（〇八81^〇.253-037-1)、2-(2，-羥基-5，-叔辛基 10/21 201037028 苯基）苯並三唑（CAS No. 221-573-5)、2-(2氫-苯並三唑-2-羥基）-4,6-二（1-曱基-1-苯基乙基）苯酚（CAS No. 274-570-6 )、2,2 ’ -亞曱基雙（6-(2氫苯並三唑-2-基）-4-(1，1，3,3_ 四曱基丁基））苯酚（CAS No. 103597-45-1 )、2-(2氫苯並三唑-2-基)-6-十二烷基-4-甲基 苯酚（CASNo.23328-53-2)及 2-(2，-羥基-3，-異丙苯基 -5’-叔辛基苯基）苯並三唑（CAS No. 73936_91-1 )等。但 也可使用非苯並三唑的紫外線吸收劑，例如N- (2-乙氧基 〇 苯基）-N’-( 2-乙基苯基）草醯二胺（Sanduvor VSU)、2_(4,6_ 二苯基-1,3,5-三嗪-2-經基)-5-己氧基苯盼(Tinuvin 1577)、 2-[4,6-雙（2,4-二曱苯基）-2-(l，3,5-三嗪基)]-5-辛基氧基苯 酚（Cytec UV-1164)，或聚-[[6-(1，1，3,3，-四曱基丁基)-亞氨 基]-1，3,5-三嗪-2,4·二基-[2-(2,2,6,6-四甲基呱啶基]-氨基]-亞己基-[4-(2,2,6,6-四甲基呱啶基）]·亞氨基（CAS No. 71878-19-8)等。 本發明所述之曱醛捕捉劑為三聚氰胺，水合胼衍生 €)物，例如1，6-六亞甲基雙（N，N-二甲基氨基脲） [1,6-hexamethylene bis(N,N-dimethyl semicarbazide)](CAS No. 69938-76-7)]或 1，1，Γ，1’-四甲基_4,4’·（亞甲基二苯基） 一 乳基脈 [l，l，l’，l’-tetramethyl-4,4’-(methylene-di-phenylene)disemi-carbazide](CAS No. 85095-61-0)等或尿素、雙氣胺、三聚 氰胺、苯胺、苯胺衍生物例如4,4’ -二叔丁基二苯基酚 (4,4’ _di-tert-octyldiphenyl amine)、曱醛縮合物、聚丙烯 酸胺或聚酸胺中的一種或多種混合物，其中以三聚氰胺、 11/21 201037028 尿素、苯衍生物或水合胼衍生物為較佳的甲醛捕捉劑。 至於曱酸捕捉劑’較佳採用驗金屬或驗土金屬的氮氧 化物或無機酸鹽類，例如鈉、鉀、鎮、約、辞的览氧化物 或上述所述驗土金屬之無機酸鹽。無機填料亦可添加於聚 甲醛中，以增加其強度。在此所述之無機填料可為滑1 粉、二硫化鉬或氮化硼或天然蒙脫土或彿石等。 本發明所提出藉由雙組份自由基捕捉劑來改質聚甲 醛的方法包括：將100重量份數的聚曱醛樹脂、〇 〇1至2 重量份數的 三甲基·2,4,6_^3,5_4Τ&_4__¥ 〇 基）苯、0.01至3.0重量份數的異戊四醇__四（3_(3,5_二叔 丁基-4-羥基笨基））丙酸酯或三（3,5_二叔丁基_4_羥基苄基^ 三異氰脲酸酯、0.01至2.0重量份數的甲醛捕捉工二二 至2.0重量份數的甲酸捕捉劑、〇 〇1至1〇 〇無機填料，按 比例加入混合機混合均句後，經單或雙螺桿壓出機擠壓 出，擠壓溫度為18〇至26(rc，溶融混煉，較佳溫度為22〇 至230t。壓出後造粒即得本發明之聚曱酸樹脂。再將所 得的聚甲賴脂取約20毫克當作樣品於熱重量損失測定〇 儀測定其加工安定性。至於本發明聚曱醛熱安定性測試是 將制粒後的聚甲醛再行壓片或射出成型，然後放入14〇t 的熱風烘箱。觀察2%重量損失所需的時間。 本發明所使用的聚曱醛是以台灣寶理公司所生產的 POM-M90(抗拉強度：62MPa)為主。自由基捕捉劑、紫 外線吸收劑為台灣雙鍵化工公司所製造。曱醛捕捉劑中 除，16-/、亞曱基雙(N，N-一 曱.基氣基腺）[l，6-lieinamethylene bis(N，N-dimethyl semicarbazide)](CAS Νο·69938-76-7)及 12/21 201037028 1，1，Γ，1’-四甲基·4,4’_ (亞曱基二苯基）二氨基脲 [1,1, Γ, Γ -tetramethyl-4,4 ,-(methylene-di-phenylene)disemi carbazide](CAS No. 85095-61-0)由台灣雙鍵化工公司生產 外，其餘甲醛捕捉劑、曱酸捕捉劑及無機填料均由商業上 取得。擠壓機型號SHJ-20由南京杰恩特公司製造，射出 成型機機型Y-450-lS-p則由台灣嗌達公司製造，耐候試驗 機（QUV)機型為 QUV accelerated weathering tester，由 Q-PANEL 製造。 〇 表1所列為本發明之實施例與比較例的測試結果。表 中顯示本發明之雙組份或雙組份以上自由基捕捉劑比傳 統單組份自由基捕捉劑在聚甲醛中更能使聚曱醛受熱安 定化。而本發明的結果顯示1，3,5-三甲基-2,4,6-二（3,5_二 叙丁基-4-經基苯基）笨添加量越高，則聚甲酸熱安定性越 高（實施例1、2及3 )。添加共安定劑如紫外線安定劑（實 施例7)可進一步強化耐候性。實施例中所得結果明顯優 於現行工業上使用的自由基捕捉劑（比較例8、9、10)， 〇大大提升聚曱醛工業性能。 實施例1 將100重量份數聚曱醛（抗拉強度：62 MPa)與由〇 2 重量份數的1，3,5-三曱基-2,4,6-三（3,5-二叔丁基-4-經基节 基）苯、0.3重量份數的異戊四醇-四（3-(3,5-二叔丁基_4_ 羥基苯基））丙酸酯組成的雙組份自由基捕捉劑及〇15重 量份數的1，6-六亞甲基雙（Ν,Ν-二甲基氨基脲）、〇·3重量 份數的碳酸鈣、0.3重量份數的沸石於混合機内混合均句 後，送入排氣式雙螺桿擠壓機。料筒溫度為220¾的條件 13/21 201037028 下熔化混煉押出造粒後，再經射出成型機製成標準試片測 定其性能，測定結果如表1所示。 實施例2 配方如實施例1所示，但不同的是將〇.2重量份數的 1,3,5-二甲基-2,4,6-二（3,5-二叔丁基-4-經基节基）苯改降 成〇·〇5重量份數，而0.3重量份數的異戊四醇_四（3_(3,5· 二叔丁基-4-羥基苯基））丙酸酯增加至0.45重量份數。於 混合機内混合均勻後，送入排氣式雙螺桿擠壓機。料筒溫 度為220°C的條件下熔化混煉押出造粒後，再經射出成型 ^ 機製成標準試片測定其性能，測定結果如表丨所示。 ' 1 實施例3 配方如實施例1所示，但不同的是將〇2重量份數的 1，3,5-三甲基-2,4,6-三（3,5-二叔丁基_4_羥基苄基）苯改增 加成0.3重量份數，而〇.3重量份數的異戊四醇_四（3_(3,5曰_ 二叔丁基_4_羥基苯基））丙酸酯則降至〇 2重量份數。於混 合機内混合均勻後’送入排氣式雙螺桿擠壓機。料筒溫度 為220t：的條件下炫化混煉押出造粒後，再經射出成型機❹ 製成標準s式片測定其性能，測定結果如表1所示。 實施例4 配方如實施例1所示，但不同的是將〇3重量份數的 異戊四曰醇-四（3_(3,5_二叔丁基_4_經基苯基））丙酸醋改以 錄3重罝份數的三(3,5_二叔丁基冰經基苯基)三異氣脈酸 :代。於混合機内混合均勻後，送人排氣式雙螺桿擠壓 機。科请溫度為22(TC的條件下稼化混煉押出造粒後，再 經射出成型機製成標準試片測定其性能，測定結果如表^ 14/21 201037028 實施例5 配方如實施例1所示，但不同的是將0.3重量份數的 異戊四醇-四（3-(3,5-二叔丁基_4_羥基苯基））丙酸酯改成 〇·3重量份數的石-(3,5-二叔丁基_4-羥基-苯基）丙酸十八 酯。於混合機内混合均勻後，送入排氣式雙螺桿擠壓機。 料筒溫度為220°C的條件下熔化混煉押出造粒後，再經射 出成型機製成標準試片測定其性能，測定結果如表丨所示。 〇 實施例6 將100重量份數聚甲醛（抗拉強度：62MPa)與由〇1 重量份數的1，3,5-二甲基-2,4,6-三（3,5-二叔丁基_4_羥基苄 基）苯、0.1重量份數的三（3,5-二叔丁基羥基苯基）三異 氰脲酸、0.3重量份數的異戊四醇_四（3_(3,5_二叔丁基 羥基苯基））丙酸酯組成的三組份自由基捕捉劑，及〇 重量份數的1，6·六亞甲基雙（N，N_二甲基氨基脲）、〇3重 量份數的碳酸鈣及0.3重量份數的沸石於混合機内混合均 〇勻後’送入排氣式«螺桿擠壓機。才斗筒溫度為22(rc.的條 件下熔化混煉押出造粒後，再經射出成型機製成標準試片 測定其性能，測定結果如表丨所示。 實施例7 配方如實施例1所示，另加入〇.3重量份數的2_(2，· 羥基-5-甲基苯基）苯並三唑（CASN〇. 219 47〇_5)，於混合 機内混合均勻後，送入排氣式雙螺桿擠壓機。料筒溫度為 220C的條件下溶化混煉押出造粒後，再經射出成型 成標準試片測定其性能，測定結果如表1所示。 15/21 201037028 比較例8 將100重量份數聚曱醛（抗拉強度：62 MPa)與0.5 重量份數異戊四醇•四（3-(3,5-二叔丁基_4-羥基苯基））丙 酸酯的單組份自由基捕捉劑，及0.15重量份數的丨，6_六亞 甲基雙（N，N-二曱基氨基脲）、0.3重量份數的碳酸約及〇.3 重量份數的沸石於混合機内混合均勻後，送入排氣式雙螺 桿擠壓機。料筒溫度為220°C的條件下熔化混煉押出造粒 後’再經射出成型機製成標準試片測定其性能，測定结果 如表1所示。 比較例9 配方如比較例8，但僅將〇.5重量份數的異戊四醇-四 (3-(3,5-二叔丁基-4-羥基苯基））丙酸酯以〇 5重量份數的 二乙二醇二（3-(3-叔丁基_5_甲基_4_羥基苯基））丙酸酯取 代，於混合機内混合均勻後，送入排氣式雙螺桿擠壓機。 料筒溫度為220°C的條件下熔化混煉押出造粒後，再經射 出成型機製成標準試片測定其性能，測定結果如表丨所示。 比較例10 配方如比較例8，但僅將〇.5重量份數的異戊四醇_四 (3-(3,5-二叔丁基-4-羥基苯基））丙酸酯以〇·5重量份數的 /5-(3,5-二叔丁基-4-羥基苯基）丙酸十八酯取代，於混合機 内混合均勻後’送入排氣式雙螺桿擠壓機。料筒溫度為2加 C的條件下熔化混煉押出造粒後，再經射出成型機製成根 準試片測定其性能，測定結果如表1所示。 X不 16/21 201037028 表1 熱重量分析儀 10%重量損失所需時間 (分鐘） 烘箱老化（140°C ) 2%重量損失所需 時間（天數） 黃變指標（YI)值 200小時QUV照 射（50〇C) 實施例1 132 94 12.5 實施例2 125 87 21.4 實施例3 134 96 12.3 實施例4 123 84 15.6 實施例5 116 82 21.4 實施例6 129 89 14.4 實施例7 132 95 11.6 比較例8 75 66 29.9 比較例9 108 79 23.4 比較例10 64 66 44.1 惟，以上所述，僅為本發明的具體實施例之詳細說明 及圖式而已，並非用以限制本發明，本發明之所有範圍應 以下述之申請專利範圍為準，任何熟悉該項技藝者在本發 明之領域内，可輕易思及之變化或修飾皆可涵蓋在以下本 案所界定之專利範圍。 【圖式簡單說明】 無 17/21 201037028 【主要元件符號說明】Lett. Ed. 16 (1967) P2277 reports that the main cracked oxidation product contains about 80 to 90% of formaldehyde, and formic acid contains about 7 to 9%, and low amounts of carbon monoxide and carbon dioxide are observed. Among them, the cracking caused by free radicals is the main cause of thermal decomposition of polyoxymethylene, so controlling the generation of free radicals has become one of the important means to stabilize the thermal stability of polyoxymethylene. The commonly used method of controlling free radical generation is to add antioxidants to capture the formation of free radicals. For example, hindered phenolic antioxiants inhibit the free radical oxidation process. The free radical scavengers of this type of commonly used rhodium are 1,1-bis(3,5-tert-butyl-2-hydroxyphenyl)ethane [l,l-bis(3,5-tert-butyl-) 2-hydroxyphenyl)ethane], pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate (CAS No. 229-722-6), triethylene glycol Bis(3-(3-tert-butyl-5-methyl-4-hydroxyphenyl))propionate (CAS No. 36443-68-2), tris(3,5-di-tert-butyl-4- Hydroxy-based hydroxy] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzylisocyanurate], 1,6-hexamethylenedi(3- (3,5-di-tert-butyl-4- benzene, phenylacetic acid) (1,6-hexamethylene bis-3-(3,5-di-tert-butyl-4-dydroxy phenyl)propionate] 'Ν,Ν-hexamethylenedi-3,5-di-tert-butyl-4-hydroxy-oxidized cinnamylamine (CAS No. 245-442-7), 4,4'-arylene II (2, 6-di-tert-butylphenol) [4,4, -methylene(2,6-di-tert-butylphenol)], /3-(3,5-:*T*-4-hydroxyphenyl)propionic acid Octaester (CAS No. 218-216-0), 2,2'-methylene-bis(4-mercapto-6-tert-butylphenol) [2,2 ' -methylene-bis(4-methyl- 6-tert_butyl phenol), 1,3,5-trimethyl-2,4, 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene 5/21 201037028 [l,3,5-tris(3,5-di-tert-4-hydroxyphenyl)mesitylene ' 1,1 ,3-tris(5'-tert-butyl-4'-hydroxy-2'-nonylphenyl)butane [l,l,3-tris(5 '-tert-butyl-4 '-hydroxy-2 ' Methylphenyl)butane], 2,4'-dimethyl-6'-tert-butylphenyl-arylene-6-tert-butyl-4-mercapto-phenyl acrylate (CAS No. 61167-58- 6) Wait. Among the above phenolic radical scavengers, the most commonly used polyacetal is isoamyl alcohol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate and triethylene glycol di [ Both 3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)]propionate. Hindered phenols radical scavengers are used in, for example, Japanese Patent Nos. JP57179245 (1982), JP01275652 (1989), JP02028240 (1990), JP06240102 (1994), JP06207080 (1994), and US2004176508 (2004). To achieve the effect of prolonging the thermal stability of polyacetal. However, polyfurfural as an engineering plastic, whether it is automotive, aerospace, precision instruments, industrial machinery, etc., requires higher rigidity, strength and thermal stability to meet the increasingly stringent requirements of materials science. SUMMARY OF THE INVENTION In view of the above, the present invention solves the above technical problems and provides a polyphthalic acid which is added with a radical scavenger to improve thermal stability. In order to achieve the above object, the present invention proposes a polyfurfural which is modified to improve thermal stability, wherein a two-component or more radical scavenger is added to polyacetal. The two-component radical scavenger used in the present invention comprises 1,3,5-dimercapto-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyl-based) stupid a radical scavenger and a solution selected from the group consisting of isopentanol _tetra (3_(3,5-di-tert-butyl 6/21 201037028 phenyl)) propionate or bis(3,5-di-tert-butyl _4) _Phenylbenzyl)diisocyanurate or octadecyl 9-(3,5-di-tert-butyl-4-hydroxy-phenyl)propanoate, one of which constitutes a two-component or contains at least two groups More than one free radical scavenger. According to a preferred embodiment, a two-component or more radical scavenger is added to the polyoxymethylene, and the two-component radical scavenger comprises two or more selected from the group consisting of 1,3,5-didecyl. -2,4,6-tris(3,5-di-tert-butyl-4-ylhydroxybenzyl)benzene, isovaleryl-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) )) Propionate or bis(3,5-di-tert-butyl-4-hydroxybenzyl)triisocyanurate and cold-(3,5-di-tert-butyl-4-hydroxy-phenyl) A group of octadecyl propionate. According to a preferred embodiment, the two-component free radical scavenger is modified to enhance the thermal stability of the polyoxymethylene, wherein the two-component free radical scavenger is hindered phenolic antioxidants. According to a preferred embodiment, in the polyoxymethylene modified by the two-component radical scavenger to improve thermal stability, one of the components of the two-component radical scavenger is 1,3,5-trimethyl -2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) indole, and the other component is isopentanol-tetrakis(3-(3,5-di-tert-butyl) _4_hydroxyphenyl))propionate, tris(3,5-di-tert-butyl-4.hydroxybenzyl)triisocyanuric acid or /5-(3,5-di-tert-butyl- Among the three-hydroxy-phenyl)propionate octadecyl esters, wherein, according to a preferred embodiment, the two-component free radical scavenger is modified to improve the thermal stability of the polyoxymethylene, wherein 1, 3, The content of 5-trimercapto-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene is at least 1% by weight or more and the other component (Isopentaerythritol-Four (3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)triisocyanurate or /3 7/21 201037028 - One of the three (3,5-di-tert-butyl-4-hydroxy-phenyl)propionate octadecyl esters is present in an amount of at least 10% by weight. According to a preferred embodiment, the two component free radical scavenger is modified to enhance the thermal stability of the polyfurfural, one of which is a component (u,5_trimethyl-2,4,6_2 (3, 5-di-tert-butyl-4-ylhydroxybenzyl)benzene) relative to another component (isopentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propanoic acid Ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)triisofluorourate or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate The ratio of one of them is 1:99-90:10, preferably 5:95-60:40, and most preferably 1〇: 9〇_4〇: 6〇. According to a preferred embodiment, the two-component free radical scavenger is modified to provide a high thermal stability polyoxymethylene, wherein the amount of the two-component free radical scavenger added to the polyfurfural does not exceed that of the polyfurfural. 5% by weight, preferably 0.5% by weight of polyfurfural. According to a preferred embodiment, the two-component free radical scavenger is modified to enhance the hot scorpion polypyracement, and further comprises one or more selected from the group consisting of secondary-filled antioxidants, ultraviolet absorbers, and formic acid. Capture agent or formic acid capture agent. According to a preferred embodiment, the two component free radical scavenger is modified to enhance the high thermal stability of the polyoxymethylene, wherein the formaldehyde scavenger is 16-hexamethylene double (N,N-didecyl) Semicarbazide). The above summary, the following detailed description and the annexed drawings are intended to further illustrate the manner, the Other objects and advantages of the present invention will be described in the following description and drawings. [Embodiment] 8/21 201037028 The present invention is directed to further strengthening the thermal stability of polyoxymethylene, and proposes a novel formulation of a radical scavenger. The invention adds a radical scavenger mainly composed of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene to polyoxymethylene. And with pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate or bis(3,5-di-tert-butyl-4-hydroxybenzyl triiso) Cyanurate or octadecyl (3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid constituting a two-component or a radical scavenger containing at least two components or more to enhance polyoxymethylene Thermal stability. Ο When I3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-based radical scavenger is used for poly-methyl At the time of brewing, the thermal stability of polyformic acid can be greatly improved by about 20%. This effect is greatly different from the one-component radical scavenger described in the above patent, and the performance is also significantly higher than the single-component scavenger, and the production cost can also be The two-component radical scavenger used in the present invention refers to two components selected from the group consisting of hindered phenol-based antioxidants. In the present invention, one of the phenol-resistant antioxidant components is 1, 3, 5 - Triterpene-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyindoleyl)benzene The base scavenger is exemplified, and the other phenolic antioxidant is selected from the group consisting of isopentanol_tetrakis(3_(3,5-di-tert-butyl-4-hydroxyphenyl)) propionate, three (3,5-di-tert-butyl-4-ylhydroxybenzyl)triisocyanurate and octadecyl (3,5-di-tert-butyl-4.hydroxy-phenyl)propanoate The group of people is taken as an example. The radical scavenger mainly composed of 1,3,5·dimethyl-2,4,6-tris(3,5-di-tert-butyl-4-yl-2-benzyl)benzene is The phenolic antioxidant is used in an amount of at least 1% by weight. The selected one is selected from the group consisting of isopentanol _tetrakis(3_(3,5·di-tert-butyl-4-hydroxyphenyl))propionate, three ( 3,5-di-tert-butyl-4-ylhydroxybenzyl) 9/21 201037028=Isoleic acid vinegar and stone _(3,5-di-tert-butyl+hydroxy-phenyl)propanoic acid octadecide The proportion of the constituents is at least 1% by weight. The ratio of the formula is between 99:1 and 10:90, preferably between 95:5 and 4:6. Considering the production cost of polyformaldehyde Under the performance, the optimal ratio of the two radical scavengers is 90:10 to 60:40. However, the amount of free radical scavenger added to the polyacetal 1 part by weight of polymethyl _ about 1 to 3 parts by weight of a radical scavenger. The two-component radical scavenger proposed by the present invention can be formed with the above-mentioned phenol-resistant radical scavenger In addition to the two-component free radical scavenger, it is sometimes combined with a phosphorus-based antioxidant or a UV-absorbing agent or a furfural-trapping agent or a formic acid scavenger or an inorganic filler. The commonly used phosphorus-based antioxidant is triphenyl phosphite. Tris(2,4-di-tert-butylphenyl) phosphite (CAS No. 250-709-6), tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl bisphosphate (pep_q), pentaerythritol bis- bis(2,4-di-tert-butylphenyl) vinegar (casNo._247-952-5) and pentaerythritol diphosphite (octadecyl) (CAS No. 223-276 -6) Wait. The radical scavenger used in the present invention can be used in combination with an ultraviolet absorber to enhance the weather resistance of polyformic acid. Commonly used ultraviolet absorbers are mainly benzotriazines', for example, 2-(2,-hydroxy-3,-tert-butyl-5,-methylphenyl-5-chlorobenzotriazole (CAS No) · 223-445-4), 2-(2-hydrogen-stupid and tris- sitting 2_yl)-4,6-di-tert-amylphenol (CAS_No. 247-384-8), 2-(2' - Hydroxy-5-nonylphenyl)benzotriazole (CAS No. 219-470-5), 2-benzotriazole-2-yl-4,6-di-tert-butylphenol (CAS No. 223- 346-6) '2-(2H-benzotriazol-2-hydroxy)-4-(tert-butyl-6-sec-butyl)phenol (〇八81^〇.253-037-1), 2 -(2,-hydroxy-5,-tert-octyl 10/21 201037028 phenyl)benzotriazole (CAS No. 221-573-5), 2-(2-hydrogen-benzotriazole-2-hydroxyl) -4,6-bis(1-mercapto-1-phenylethyl)phenol (CAS No. 274-570-6 ), 2,2 '-indolyl bis(6-(2-hydrobenzotriazole) -2-yl)-4-(1,1,3,3_tetradecylbutyl))phenol (CAS No. 103597-45-1), 2-(2-hydrobenzotriazol-2-yl)- 6-dodecyl-4-methylphenol (CAS No. 23328-53-2) and 2-(2,-hydroxy-3,-isopropylphenyl-5'-tert-octylphenyl)benzotriene Oxazole (CAS No. 73936_91-1), etc., but non-benzotriazole can also be used. UV absorbers such as N-(2-ethoxyindolephenyl)-N'-(2-ethylphenyl)oxalyldiamine (Sanduvor VSU), 2_(4,6-diphenyl-1,3 , 5-triazin-2-yl)-5-hexyloxybenzene (Tinuvin 1577), 2-[4,6-bis(2,4-diphenylene)-2-(l,3, 5-triazinyl)]-5-octyloxyphenol (Cytec UV-1164), or poly-[[6-(1,1,3,3,-tetradecylbutyl)-imino]- 1,3,5-triazine-2,4·diyl-[2-(2,2,6,6-tetramethylacridinyl)-amino]-hexylene-[4-(2,2, 6,6-tetramethylacridinyl)]-imino (CAS No. 71878-19-8), etc. The furfural capture agent of the present invention is melamine, hydrazine hydrate derivative, such as 1,6 - hexamethylene bis(N,N-dimethyl semicarbazide) (CAS No. 69938-76-7)] or 1,1,Γ ,1'-tetramethyl-4,4'-(methylenediphenyl)-milk-based [l,l,l',l'-tetramethyl-4,4'-(methylene-di-phenylene) Disemi-carbazide] (CAS No. 85095-61-0) or the like or urea, diamine, melamine, aniline, aniline derivatives such as 4,4'-di-tert-butyldiphenylphenol (4,4' _di- Ter a mixture of one or more of t-octyldiphenyl amine), furfural condensate, polyacrylamide or polyamine, wherein melamine, 11/21 201037028 urea, benzene derivative or hydrazine hydrate derivative is preferred as a formaldehyde scavenger . As for the citric acid scavenger, it is preferred to use a metal oxide or a mineral acid salt of a metal or soil tester, such as sodium, potassium, town, or an alloy of the earth or a mineral acid salt of the soil of the soil described above. . Inorganic fillers may also be added to the polyformaldehyde to increase its strength. The inorganic filler described herein may be slippery powder, molybdenum disulfide or boron nitride or natural montmorillonite or buddha. The method for modifying polyoxymethylene by the two-component radical scavenger according to the present invention comprises: 100 parts by weight of polyacetal resin, 1 to 2 parts by weight of trimethyl-2,4, 6_^3,5_4Τ&_4__¥ mercapto)benzene, 0.01 to 3.0 parts by weight of pentaerythritol __tetrakis(3_(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or Tris(3,5-di-tert-butyl-4-ylhydroxybenzyl triisocyanurate, 0.01 to 2.0 parts by weight of formaldehyde trapping 22 to 2.0 parts by weight of formic acid scavenger, 〇〇1 to 1〇〇Inorganic filler, added to the mixing machine in proportion, and then extruded through a single or twin-screw extruder, the extrusion temperature is 18〇 to 26 (rc, melt-kneading, preferably 22〇 to 230t. After the extrusion, granulation is carried out to obtain the polyphthalic acid resin of the present invention, and about 20 mg of the obtained polymethyl lysate is used as a sample to determine the processing stability of the sample by thermal weight loss measurement. The aldehyde thermal stability test is to press or granulate the granulated polyoxymethylene into a hot air oven of 14 Torr, and observe the time required for 2% weight loss. The polyacetal used is mainly POM-M90 (tensile strength: 62 MPa) produced by Taiwan Polyplastics Co., Ltd. The radical scavenger and ultraviolet absorber are manufactured by Taiwan Double Bond Chemical Co., Ltd. , 16-/, 曱 曱 双 (N, N- semi 基 基 [) [l, 6-lieinamethylene bis (N, N-dimethyl semicarbazide)] (CAS Νο·69938-76-7) and 12 /21 201037028 1,1,Γ,1'-tetramethyl·4,4'_(indenyldiphenyl)diaminourea [1,1, Γ, Γ-tetramethyl-4,4 ,-(methylene -di-phenylene)disemi carbazide] (CAS No. 85095-61-0) is produced by Taiwan Double Bond Chemical Co., Ltd., and the rest of the formaldehyde trapping agent, citric acid scavenger and inorganic filler are commercially available. Extrusion machine model SHJ -20 is manufactured by Nanjing Jieente Company. The injection molding machine model Y-450-lS-p is manufactured by Taiwan Minda Co., Ltd., and the weathering test machine (QUV) model is QUV accelerated weathering tester, manufactured by Q-PANEL. Table 1 lists the test results of the examples and comparative examples of the present invention. The table shows that the two-component or two-component free radical scavenger of the present invention is freer than the conventional one-component. The base scavenger further enhances the thermal stability of the polyfurfural in the polyoxymethylene. The results of the present invention show 1,3,5-trimethyl-2,4,6-di(3,5-bis-butylene- The higher the amount of 4-phenylphenyl) added, the higher the thermal stability of the polyformic acid (Examples 1, 2 and 3). The addition of a co-stabilizer such as an ultraviolet stabilizer (Example 7) further enhances weather resistance. The results obtained in the examples were significantly superior to the free radical scavengers currently used in the industry (Comparative Examples 8, 9, 10), and the industrial properties of polyacetal were greatly enhanced. Example 1 100 parts by weight of polyacetal (tensile strength: 62 MPa) and 1,3,5-trimethyl-2,4,6-tris (3,5-di) from 2 parts by weight of hydrazine Two groups of tert-butyl-4-trans)phenyl and 0.3 parts by weight of pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate a free radical scavenger and 15 parts by weight of 1,6-hexamethylenebis(indole, fluorenyl-dimethylcarbazone), 3 parts by weight of calcium carbonate, 0.3 parts by weight of zeolite After mixing the homologous sentences in the mixer, it is sent to a vented twin-screw extruder. The condition of barrel temperature is 2202⁄4 13/21 201037028 After melt-kneading and granulation, the performance is determined by a standard test piece prepared by an injection molding machine. The measurement results are shown in Table 1. Example 2 The formulation was as shown in Example 1, but the difference was that 2 parts by weight of 1,3,5-dimethyl-2,4,6-di(3,5-di-tert-butyl- 4- via base group) benzene is reduced to 5 parts by weight of 〇·〇, and 0.3 parts by weight of isopentaerythrol_tetrakis(3_(3,5·di-tert-butyl-4-hydroxyphenyl)) The propionate was increased to 0.45 parts by weight. After mixing in a mixer, it is fed into a vented twin-screw extruder. After the barrel temperature was 220 ° C, the mixture was melted and kneaded and granulated, and then the properties were measured by injection molding into a standard test piece. The measurement results are shown in Table 。. '1 Example 3 The formulation was as shown in Example 1, except that 2 parts by weight of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl) was used. _4_Hydroxybenzyl) benzene is increased to 0.3 parts by weight, and 重量.3 parts by weight of pentaerythritol _ tetra (3_(3,5曰_di-tert-butyl-4-hydroxyphenyl)) The propionate is reduced to 2 parts by weight. After being uniformly mixed in the mixer, it is sent to a vented twin-screw extruder. After the barrel temperature was 220t:, the smelting was mixed and granulated, and then the performance was measured by an injection molding machine. The measurement results are shown in Table 1. Example 4 The formulation was as shown in Example 1, but the difference was that 3 parts by weight of isovaleryl-tetrakis(3_(3,5-di-tert-butyl-4-yl)-phenyl)propyl The vinegar was changed to a three-fold aliquot of tris(3,5-di-tert-butyl glacial phenyl)triiso-hydrogen acid: generation. After mixing in a mixer, it is sent to a vented twin-screw extruder. The temperature is 22 (the conditions of TC under the conditions of mashing and granulation, and then made into a standard test piece by the injection molding machine to determine its performance, the measurement results are shown in Table 14 / 21 201037028 Example 5 Formulation as Example 1 Show, but the difference is that 0.3 parts by weight of isopentamyl-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is changed to 〇·3 parts by weight Stone-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid octadecyl ester. After mixing in a mixer, it is sent to a vented twin-screw extruder. The barrel temperature is 220°. After the conditions of C, the melt-kneading and granulation were carried out, and then the properties were measured by an injection molding machine to obtain a standard test piece, and the measurement results are shown in Table 〇 Example 6 100 parts by weight of polyoxymethylene (tensile strength: 62 MPa) with 1 part by weight of 1,3,5-dimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 0.1 parts by weight Tris(3,5-di-tert-butylhydroxyphenyl)triisocyanuric acid, 0.3 parts by weight of pentaerythritol_tetrakis(3_(3,5-di-tert-butylhydroxyphenyl))propionate a three-component free radical trapping agent, and a weight fraction of 11,6· Methylene bis(N,N-dimethyl semicarbazide), 重量3 parts by weight of calcium carbonate and 0.3 parts by weight of zeolite are mixed in a mixer and then sent to a vented «screw extruder After the temperature of the barrel is 22 (rc.), the mixture is melted and kneaded and granulated, and then the performance is measured by an injection molding machine to prepare a standard test piece. The measurement results are shown in Table . Example 7 Formulation as Example As shown in Fig. 1, 3 parts by weight of 2_(2,·hydroxy-5-methylphenyl)benzotriazole (CASN〇. 219 47〇_5) was added, and the mixture was uniformly mixed in a mixer. In-exhaust twin-screw extruder. After the temperature of the cylinder is 220C, the mixture is melted and granulated, and then the product is tested into a standard test piece to measure its performance. The measurement results are shown in Table 1. 15/21 201037028 Comparative Example 8 100 parts by weight of polyacetal (tensile strength: 62 MPa) and 0.5 parts by weight of isopentanol•tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)) a one-component free radical scavenger of propionate, and 0.15 parts by weight of hydrazine, 6-hexamethylene bis(N,N-dimercaptosemicarbazide), 0.3 parts by weight of carbonic acid and about 〇.3 The parts by weight of the zeolite are uniformly mixed in the mixer, and then sent to a vented twin-screw extruder. The temperature of the barrel is 220 ° C, and the mixture is melted and granulated, and then granulated. The sheet was measured for its properties, and the results of the measurement are shown in Table 1. Comparative Example 9 The formulation was as in Comparative Example 8, except that only 0.5 parts by weight of pentaerythritol-tetrakis(3-(3,5-di-tert-butyl) was used. -4-hydroxyphenyl))propionate is substituted with 5 parts by weight of diethylene glycol bis(3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate, After being uniformly mixed in the mixer, it is sent to a vented twin-screw extruder. After the barrel temperature was 220 ° C, the mixture was melted and kneaded and granulated, and then subjected to an injection molding machine to prepare a standard test piece to measure its performance. The measurement results are shown in Table 。. Comparative Example 10 The formulation was as in Comparative Example 8, except that only 5 parts by weight of isopentaerythrol_tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate was obtained. 5 parts by weight of octadecyl/5-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was substituted and uniformly mixed in a mixer to be fed to a vented twin-screw extruder. After the barrel temperature was 2 plus C, the mixture was melted and kneaded, and then granulated, and then subjected to an injection molding machine to measure the performance. The measurement results are shown in Table 1. X No 16/21 201037028 Table 1 Time required for 10% weight loss of thermogravimetric analyzer (minutes) Oven aging (140 °C) Time required for 2% weight loss (days) Yellow variable index (YI) value 200 hours QUV irradiation (50〇C) Example 1 132 94 12.5 Example 2 125 87 21.4 Example 3 134 96 12.3 Example 4 123 84 15.6 Example 5 116 82 21.4 Example 6 129 89 14.4 Example 7 132 95 11.6 Comparative Example 8 75 66 29.9 Comparative Example 9 108 79 23.4 Comparative Example 10 64 66 44.1 However, the above is only the detailed description and the drawings of the specific embodiments of the present invention, and is not intended to limit the present invention. The scope of the patents defined in the following paragraphs is intended to be within the scope of the present invention. [Simple description of the diagram] None 17/21 201037028 [Description of main component symbols]