200948895 六、發明說明： 【發明所屬之技術領域】 本發明係關於以非齒素系之難燃性材料所構成，且在 高溫下之形狀保持性、拉伸特性優異的管及熱收縮管。 【先前技術】 使用於電子設備、OA設備、音響、影像、DVD等民 生用電子設備，車輛、船舶等領域的各種零件、內部配線 等，爲了防水、防塵、絕緣等要求，有藉由使用難燃性管 〇 等進行密接包裝而予以保護之情形存在。 使用於此種密接包裝之難燃性管，爲了由於零件溫度 上昇而不使起火起見，因而謀求在UL規格的垂直燃燒試 驗VW-1可合格的難燃性。習知在難燃性材料方面，於軟 質聚氯化乙烯組成物或聚乙烯或乙烯-丙烯酸乙酯共聚 物、乙烯-乙酸乙烯酯共聚物等乙烯基系聚合物，雖有使用 配合了溴系或氯系難燃劑之難燃性樹脂組成物，然而此種 難燃性材料，在燒毀（burnout)處理時因會有發生鹵化氫氣 © 體的問題，故就有謀求不含鹵素化合物之所謂非_素難燃 性樹脂材料之替代品。 一方面，在對上述設備等纜線或配線等之保護所使用 之管，謀求可撓性優異之物，即使在高溫下亦謀求可保持 拉伸強度、延伸之物》又，亦有在插入有被包裝物的管之 狀態下進行加工、變形之情形。因此，在使用於該等用途 之管，關於上述難燃性之規格不僅爲充裕，而且亦必須合 乎於高溫下之拉伸強度、延伸、耐熱變形性的UL規格。 200948895 在非鹵素系難燃性樹脂材料方面，係在聚乙烯或乙烯_ 丙烯酸乙酯共聚物、乙烯-乙酸乙烯酯共聚物等配合有氫氧 化鋁或氫氧化鎂等金屬氫氧化物系難燃劑的材料已臻實用 化。但是’若欲對UL規格之垂直燃燒試驗VW_1達到合格， 必須大量添加金屬氫氧化物系難燃劑，一方面，若配合大 量金屬氫氧化物系難燃劑時，會使機械特性降低，而無法 謀求難燃性與機械特性之並存。 使用金屬氫氧化物系難燃劑，使機械特性與難燃性並 存之管方面，在例如日本特開平7-145288號公報（專利文 獻1)有揭示，相對於含有乙烯-乙酸乙烯酯系共聚物之基質 聚合物100質量份，以含有金屬水合物150至230質量份 及發泡劑0.1至20質量份之難燃性樹脂組成物所構成，進 而經交聯的管。 上述難燃性管，在含有發泡劑，而配合大量金屬氫氧 化物系難燃劑，亦可確保抗張力0.7kg/mm2以上、100%以 上。但是在專利文獻1，並無關於在高溫下之拉伸特性、 強度之評價，此種難燃性材料，就耐熱性、耐熱變形性等 點而言，並無法滿足UL規格。 磷酸酯等磷系難燃劑雖爲已知，其難燃效果並非充 分，仍然有著若無法大量配合，則無法獲得可滿足之難燃 性等的問題。 爲要減低難燃劑之含量，作爲基質聚合物係使用到難 燃性聚合物之非鹵素系難燃性材料的開發正在進行中。 例如由SABIC創新塑膠日本合同會公司（舊名：日本GE塑 200948895 膠）所販售之柔軟No ryl作爲基質聚合物，係使用聚苯醚與 苯乙烯系樹脂或苯乙烯系熱塑性彈性體之混合物，並配合 磷酸酯系難燃劑。根據聚苯醚與聚烯烴樹脂比較難燃性爲 高’因可減低難燃劑之添加量，而且因伴隨難燃劑的大量 添加而可抑制拉伸特性降低，故在一部分的等級可作爲電 線被覆材料使用。但是，在耐熱性之點並非充分，尤其是 爲了密接包裝用，欲作爲熱收縮管使用時，在擴徑處理時 會有無法保持形狀，或在熱收縮步驟或被包裝物之加工步 β 驟造成熔融之情形。 又，在日本特開2007-197615號公報（專利文獻2)有提 案：實質上並不含有磷系難燃劑，使用氮系難燃劑，作爲 基質聚合物’使用聚苯醚樹脂及熱塑性彈性體，進而配合 有交聯助劑之非鹵素系難燃性樹脂組成物。 [專利文獻1]日本特開平7-145288號公報 [專利文獻2]日本特開2007-197615號公報 【發明内容】 〇 胃 [發明欲解決課題] 但是，在專利文獻2揭示之非鹵素系難燃性樹脂組成 物’其意圖在於作爲電線、纜線之被覆材的利用，並無作 爲管之評價。在適用於管之情形，關於在加熱下擴徑處理 後之形狀保持、高溫下之拉伸特性、耐熱變形性，要滿足 UL規格有困難，故謀求更進一步之改善。 本發明係鑑於此種情事而完成者，其目的之所在，在 於提供一種可滿足難燃性、高溫下拉伸特性、耐熱變形性 200948895 的非鹵素系之難燃性管。 [解決課題之手段] 的基質聚合物 有機化合物3 份之難燃性樹 形成，其中上 乙烯系熱塑性 g 7 0質量％。 不飽和單體之 性不飽和單體 性不飽和單體 物或乙烯-α烯 之含有率爲〇 乙烯系熱塑性 丨爲佳，該磷系 系有機化合物 ，在加熱下擴 本發明之難燃性管係使每100質量份 中，含有磷系難燃劑5至100質量份、氮系 至80質量份、及多官能性單體1至20質量 脂組成物，其成形爲管狀後，照射電子束而 述基質聚合物含有聚苯醚5至80質量％、苯 彈性體20至95質量％、及烯烴系聚合物〇i β 該烯烴系聚合物方面，以烯烴與乙烯性 共聚物爲佳，更佳爲含有聚烯烴嵌段與乙烯 之聚合物嵌段的嵌段共聚物，或烯烴與乙烯 之共聚物或將聚烯烴之側鏈以乙烯基系聚合 烴共聚物經接枝化之接枝共聚物。 又，在基質聚合物中，該烯烴系聚合物 質量％之情形，以聚苯醚5至80質量％、苯 彈性體95至20質量％爲佳。 ® 該多官能性單體以具有碳-碳雙鍵之單體 難燃劑，以縮合磷酸之酯或銨鹽爲佳，該氮 以含胺基及/或醯亞胺基單位之化合物爲佳。 本發明之熱收縮管係將上述本發明之管 徑後，予以冷卻固定而成。 [發明效果] 本發明之難燃性管係使拉伸特性及難燃性並存之物， 進而藉由電子束照射所致交聯效果可得優異耐熱性、耐熱 200948895 變形性。因具有此種優異特性，故將本發明之難燃 加熱下擴徑後，就進行冷卻固定所得本發明之熱收 亦與本發明之難燃性管相同，具有優異拉伸特性、難 耐熱性、耐熱變形性。 [發明內容] 本發明之實施形態係說明如下，而在此所揭示 形態，吾人應考量全部重點均有例示而並無作任何 本發明之範圍，係以申請專利範圍表示，其用意均 申請專利範圍均等的意義及在該範圍內所作所有之丨 <難燃性樹脂組成物> 首先就爲本發明難燃性管之材料的樹脂組成物 明。 作爲本發明之難燃性樹脂管材料所使用之樹 物’係每100質量份之基質聚合物含有磷系難燃劑5 質量份、氮系有機化合物3至80質量份、及多官能 1至20質量份，其中上述基質聚合物含有：聚苯醚 5至80質量％，苯乙烯系熱塑性彈性體20至95質】 烯烴系聚合物〇至70質量％。 (1)基質聚合物 難燃性樹脂組成物之基質聚合物組成係聚苯酸 5至80質量％、苯乙烯系熱塑性彈性體20至95質』 烯烴系聚合物〇至70質量％，在不含烯烴系聚合 形’則宜爲聚苯醚系樹脂5至80質量％、苯乙烯系 彈性體95至20質量％。 性管在 縮管， 燃性、 的實施 限制。 含有與 變更。 加以說 脂組成 至100 性單體 系樹脂 I %，及 系樹脂 I %、及 物之情 熱塑性 200948895 聚苯醚係指將以甲醇與酚爲原料所合成的2,6-二甲苯 酚進行氧化聚合所得之樹脂。在本發明所用之聚苯醚系樹 脂方面，並非只是聚苯醚，亦可例舉以順丁烯二酸酐等改 性的改性聚苯醚，或該等與聚苯乙烯樹脂、聚醯胺樹脂、 聚酯樹脂、聚丙烯樹脂經熔融掺合的聚合物合金等。聚苯 醚樹脂與聚苯乙烯之聚合物合金，與苯乙烯系熱塑性彈性 體之相溶性優異，因可提高擠壓加工性，故可適當使用》 本發明所使用之苯乙烯系熱塑性彈性體係聚苯乙烯嵌 〇 段與橡膠成分嵌段之嵌段共聚物。聚丁二烯、聚異戊二烯 等橡膠成分嵌段與聚苯乙烯嵌段之二嵌段共聚物、三嵌段 共聚物，進而可使用該等氫化聚合物或部分氫化聚合物、 順丁烯二酸酐改性彈性體、環氧改性彈性體、芳香族乙烯 基系熱塑性彈性體等。具體言之，可例舉苯乙烯-異丁烯-苯乙烯共聚物、苯乙烯-乙烯共聚物、苯乙烯-乙烯丙烯共 聚物、苯乙烯-乙烯丁烯-苯乙烯共聚物、苯乙烯-乙烯丙烯-苯乙烯共聚物、苯乙烯-異戊二烯共聚物、苯乙烯-乙烯-異 ® 戊二烯共聚物、苯乙烯·異戊二烯-苯乙烯共聚物、苯乙烯-丁二烯共聚物等。 此種苯乙烯系熱塑性彈性體，對拉伸裂斷延伸之提高 爲有用。苯乙烯系熱塑性彈性體中苯乙烯含有率’由與延 伸及聚苯醚的相溶性之點而言，宜爲10至70重量％。 本發明所使用之烯烴系聚合物係指’除了一或兩種以 上烯烴之聚合物以外，尙有烯烴與不飽和單體之無規共聚 物、嵌段共聚物、接枝共聚物之意。 200948895 嵌段共聚物方面，可例舉具有由聚烯烴嵌段與不飽和 單體所成聚合物嵌段的共聚物，聚烯烴嵌段並非限定於一 種烯烴單體之聚合物嵌段，而可爲兩種以上烯烴單體之聚 合物嵌段。又’聚烯烴嵌段，除了聚合烯烴單體而形成以 外，尙可在二烯烴單體，三烯烴單體等具有複數個雙鍵的 單體之聚合後，藉由氫化來形成。 就乙烯性不飽和單體之聚合物嵌段，並非僅由一種不 飽和單體所成聚合物嵌段，亦可爲兩種以上共聚性單體之 ❹聚合物嵌段。 接枝共聚物方面，係使聚烯烴，或烯烴與不飽和單體 之無規共聚物、嵌段共聚物作爲主鏈，在側鏈使不飽和單 體之同元聚合物、無規共聚物、嵌段共聚物進行接枝化之 物。 在構成上述聚烯烴嵌段或聚烯烴之烯烴單位方面，可 使用乙烯、丙烯、1-丁烯、異丁烯、戊烯、己烯等。 不飽和單體方面，可使用丙烯酸、甲基丙烯酸、甲基 ❹ 丙烯酸甲酯、巴豆酸、酞酸（酐）、順丁烯二酸（酐）、伊康酸 (酐）等不飽和酸類或其碳數1至8之單烷酯或與環氧丙醇 之酯；甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、戊酸乙烯 酯等脂肪酸之乙烯酯；苯乙烯、烯丙苯等芳香族乙烯基化 合物；丙烯酸腈、丙烯腈苯乙烯、甲基丙烯酸腈等氰化乙 烯基類等。 因此，本發明烯烴系聚合物之具體例方面，可例舉以 超低密度聚乙烯、低密度聚乙烯、中密度聚乙烯、直鏈狀 -10- 200948895 低密度聚乙烯、高密度聚乙烯等聚乙烯、聚丙嫌、乙嫌-α 烯烴共聚物、烯烴系熱塑性彈性體、乙烯-乙酸乙嫌醋共聚 物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸共聚物、 乙烯·甲基丙烯酸甲酯共聚物、乙烯-丙烯酸甲酯共聚物、 苯乙烯-乙烯丁烯-烯烴結晶嵌段共聚物、主鏈爲聚烯烴（例 如聚乙烯或聚丙烯）或烯烴與乙烯性不飽和單體之共聚物 (例如乙烯·甲基丙烯酸環氧丙酯共聚物、乙烯-丙烯酸乙酯 共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯丙烯酸酯-順 〇 丁烯二酸酐共聚物），在側鏈使乙烯基系聚合物（例如將聚 苯乙烯、聚甲基丙烯酸甲酯、或丙烯腈-苯乙烯共聚物 '聚 乙酸乙烯酯、聚丙烯酸曱酯、聚丙烯酸乙酯、聚丙烯酸丁 醋、聚丙烯酸以金屬離子進行中和之物等）或乙烯-α烯烴共 聚物（例如乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚 物、乙烯·甲基丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚 物、乙烯-丙烯酸丁酯共聚物、乙烯-丙烯橡膠、乙烯丙烯 酸橡膠、乙烯·甲基丙烯酸環氧丙酯共聚物、乙烯-丙烯酸 ❹ 甲酯-甲基丙烯酸環氧丙酯共聚物、乙烯-丙烯酸共聚物、 乙烯-甲基丙烯酸共聚物、乙烯離子鍵聚合物或將該等以順 丁嫌一酸肝等改性之聚合物等）進行接枝化的接枝共聚物 等。此種烯烴系聚合物亦與上述苯乙烯系熱塑性彈性體相 同可發揮難燃性。 在基質聚合物中，上述各聚合物（聚苯醚系樹脂、苯乙 烯系熱塑性彈性體、烯烴系聚合物）之含有率係聚苯醚系樹 脂5至80質量％、苯乙烯系熱塑性彈性體2〇至95質量％、 -11- 200948895 及烯烴系聚合物0至70質量％。烯烴系聚合物之含有率爲 〇質量％之情形、宜爲以聚苯醚系樹脂：苯乙烯系熱塑性彈 性體=5: 95 至 80: 20。 在基質聚合物中若烯烴系聚合物之含有率比70質量％ 爲多時，相對地必須使難燃性更爲優異之苯乙烯系熱塑性 彈性體之含有率減少，則會傾向於難燃性降低。又，聚苯 醚樹脂之含有比率過少，苯乙烯系熱塑性彈性體之含有比 率過多時，則難燃性傾向於無法滿足。一方面，聚苯醚系 © 樹脂之含有比率過大、苯乙烯系熱塑性彈性體、烯烴系聚 合物之含有比率過小時，則傾向於無法滿足拉伸特性。 (2)磷系難燃劑 在本發明所使用之磷系難燃劑方面，可例舉鄰磷酸 酯；焦磷酸、聚磷酸、偏磷酸、超磷酸等分子中具有分枝 Ρ04基的交聯構造，或磷酸鹽結合成直鏈狀、環狀的縮合 磷酸的有機酯或銨鹽；膦酸酯；次膦酸酯等》該等中，以 使用縮合磷酸之有機酯或銨鹽爲佳，亦可使用分子內具有 • 0Η基之物。 具體言之，可例舉磷酸三甲酯、磷酸三乙酯、磷酸三 苯酯、磷酸三環氧丙酯、磷酸三苯二甲基（xylenyl)酯、磷 酸甲酚基苯酯、磷酸甲酚基2,6-苯二甲酯、磷酸2-乙基己 基二苯酯、1，3-伸苯基雙（二苯基磷酸酯）、1，3-伸苯基雙（二 -2,6_苯二甲基磷酸酯）、1，2-伸苯基雙（二-2,6-苯二甲基磷 酸酯）、雙酚A雙（二苯基磷酸酯）、磷酸間苯二酚雙二苯酯、 磷酸辛基二苯酯、二伸乙基乙基酯磷酸酯、二羥基伸丙基 -12- 200948895 丁基酯憐酸醋、伸乙基二鈉醋磷酸鹽、碟酸三級丁基苯基 二苯酯、磷酸雙-(三級丁基苯基）苯酯、磷酸參（三級丁基苯 基）醋、碟酸異丙基苯基二苯醋、憐酸雙_(異丙基苯基）二苯 醋、磷酸參（異丙基苯基）二苯醋、憐酸參（異丙基苯基）醋、 磷酸參（2-乙基己基）酯、磷酸參（丁氧基乙基）酯、磷酸參異 丁酯等之磷酸酯；膦酸甲酯、甲基膦酸二甲酯、甲基鱗酸 二乙酯、膦酸乙酯、膦酸丙酯、膦酸丁酯、膦酸2_甲基_ 丙酯、膦酸三級丁酯、膦酸2,3 -二甲基丁酯、膦酸辛醋、 © 膦酸苯酯等膦酸酯；次膦酸二乙酯、次膦酸甲基乙醋、次 膦酸苯酯、次膦酸二乙基苯酯、次膦酸二苯酯等次膦酸酯； 二異癸基新戊四醇二亞磷酸醋（phosphite)或9,10 -二氫-9 ' 氧雜-10-碟菲（phosphaphenanthrene)-lO-氧化物、三光公司 製 HCA-HQ、SANKO-220、Μ-Ester、BCA 等之環狀有機碟 化合物、聚磷酸銨、磷酸三聚氟胺、聚磷酸三聚氰胺、焦 磷酸三聚氰胺、磷酸甲脒（guanyl)脲、磷酸胍、ADECA公 司銷售之 Adecastab FP2100J 或 Adecastab FP2200、Ciba © 特用化學品公司製FLMESTAB NOR116FF等之磷與氮之化 合物。該等磷系難燃劑可混合一種或兩種以上使用。 如以上之磷系化合物亦可使用三聚氰胺或三聚氰酸三 聚氰胺酯、脂肪酸、矽烷偶合劑等經表面化之物。在與基 質聚合物混合時，藉由配合表面處理劑之完全摻合 (integral blend)亦可進行表面處理。 磷系難燃劑係對每基質聚合物1〇〇質量份含有5至100 質量份。在小於5質量份，則難以確保難燃性’而超過100 -13- 200948895 質量份時，則無法滿足耐熱變形性。 (3) 氮系有機化合物 在氮系有機化合物方面，以使用三聚氰酸、三聚氰胺、 三嗪等衍生物或加成物爲佳，具體言之可使用三聚氰胺樹 脂、三聚氰酸三聚氰胺酯、異三聚氰酸、異三聚氰酸酯衍 生物、加成物等。該等中，宜爲使用分子內含有胺基及/或 醯亞胺基單位之三聚氰胺、三聚氰酸三聚氰胺酯。此種氮 系有機化合物之機制雖無法得知，然而藉由與磷系難燃劑 〇 之倂用，並不會導致拉伸特性大幅降低，而可確保可合乎 UL規格的VW-1試驗之合格等級的難燃性。 如以上之氮系有機化合物，可以胺基矽烷偶合劑、乙 烯基矽烷偶合劑、環氧基矽烷偶合劑、甲基丙烯醯氧基矽 烷偶合劑等矽烷偶合劑；以硬脂酸、油酸等高級脂肪酸進 行表面處理亦可。亦可預先進行表面處理，基質聚合物、 與其他成分之配合，藉由在混合時配合表面處理劑而可進 行表面處理》 ® 氮系有機化合物係對每基質聚合物100質量份含有3 至80質量份。在小於3質量份時，則無法獲得與磷系化合 物之倂用所致難燃效果，若較80質量份爲多時，則拉伸裂 斷延伸降低，亦無法確保初期的拉伸特性。 (4) 多官能性單體 多官能性單體方面，宜爲使用單丙烯酸酯系、二丙烯 酸酯系、三丙烯酸酯系、單甲基丙烯酸酯系、二甲基丙烯 酸酯系、三甲基丙烯酸酯系、異三聚氰酸三烯丙酯系、三 -14- .200948895 聚氰酸三烯丙酯系等之分子內具有複數個碳-碳雙鍵的單 體。由交聯性之點而言，宜爲使用三甲基丙烯酸三羥甲基 丙酯等之三甲基丙烯酸酯系單體。此種多官能性單體，藉 由電子束照射’可與含於基質聚合物的二烯部分進行乙烯 基聚合反應’而可期待對髙溫下之物性提高極爲有用。 多官能性單體係對每基質聚合物100質量份含有1至 20質量份。在小於1質量份，並無法獲得交聯效果，使得 高溫下之拉伸特性降低變的顯著，又在高溫下之熱變形亦 大。一方面’超過20質量份時、會有未反應之單體殘存之 虞，成爲難燃性降低之原因。 (5)其他成分 在不損及難燃性、耐熱變形性、拉伸特性、體積比電 阻（resistibility)之範圍，亦可添加氫氧化鋁、氫氧化鎂、 氫氧化鈣等金屬氫氧化物或三氧化銻、錫酸鋅、羥基錫酸 鋅鹽、硼酸鋅、磷酸硼等難燃劑。 在本發明所使用之難燃性樹脂組成物，進而在不損及 難燃性或機械強度之範圍，於各種特性改善之目的下，可 摻合聚烯烴熱塑性彈性體、聚酯熱塑性彈性體、聚胺甲酸 乙酯熱塑性彈性體等之其他熱塑性彈性體；耐衝擊性聚苯 乙烯、丙烯腈-苯乙烯樹脂、ABS樹脂等之苯乙烯系樹脂； EPDM、丙烯酸乙烯酯橡膠、丙烯酸橡膠、腈橡膠等之橡膠； 耐綸、聚對苯二甲酸丁二醇酯（PBT)、聚對酞酸乙二酯、聚 鄰苯二酸乙烯酯、聚苯基硫化物等各種聚合物。 又，亦可配合抗氧化劑、潤滑劑、加工穩定助劑、著 -15- 200948895 色劑、發泡劑、補強劑、塡充劑、加硫劑、金屬惰性劑、 矽烷偶合劑等之各種添加劑。 將如以上之成分配合以每一設定量，藉由使用單軸擠 壓型混合機、加壓捏合機、班伯里混合器等既知熔融混合 機進行混合而可調製。 <難燃性管> 本發明之難燃性管係將具有上述組成之難燃性樹脂組 成物進行擠壓成形成爲管狀所形成的管狀成形品，在此成 © 形品進行電子束照射之物。 吾人認爲藉由電子束照射，介由多官能性單體，而可 使基質聚合物交聯。接著，藉由交聯而可抑制在熱塑性彈 性體高溫下之彈性體性的降低，藉此，吾人認爲則變得能 確保在髙溫下的拉伸特性。又，藉由交聯所致部分的網狀 構造化，亦可抑制熱變形，因高溫處理亦無法熔融，而可 保持形狀。 難燃性管之尺寸並無特別限定，通常宜爲壁厚1.0mm ® 以下，更佳爲〇 . 8 mm以下》 在擠壓成形之際，一次調製難燃性樹脂組成物，在製 造具有設定組成的樹脂顆粒後，宜爲供應該樹脂顆粒於擠 壓成形機。 擠壓機之種類並無特別限定，可爲螺旋式、非螺旋式 之任一種，較佳爲螺旋式。螺旋之種類亦無特別限定，而 全長L與圓筒孔徑D之比（L/D)，通常宜爲24至28左右。 所使用之電子束方面，則有加速電子束或γ線、X線、 -16- 200948895 α線、紫外線等。而就線源利用之簡便性或電離輻射線之 透過厚度、交聯處理之速度等，由工業上利用之觀點而言， 最好係利用加速電子束。 加速電子束之加速電壓，可以管層壁厚，爲管材料之 樹脂組成物的組成予以適宜設定。例如在厚度0.2mm至 0.4mm壁厚之管，加速電壓可在3 00keV至3MeV之間選 定。照射線量方面，並無特別限定，通常爲20至5 OOkGy。 <熱收縮管> ® 本發明之熱收縮管係將上述本發明之難燃性管在加熱 下擴徑後，予以冷卻固定之物。 擴徑處理係將上述管狀成形品在加熱至基質聚合物軟 化溫度以上溫度的狀態，藉由於管內導入壓縮空氣等之方 法，膨脹爲設定之外徑後，藉由冷卻並固定形狀而可獲得。 擴徑宜爲在原來內徑之2至4倍左右。 本發明之管，耐熱性優異，即使在高溫下亦不熔融， 而可進行擴徑處理，可保持已擴徑之形狀。 ¥ 本發明之熱收縮管，因具有優異耐熱性，故再次藉由 在軟化溫度左右，具體言之，藉由在1〇〇至250°c之加熱 處理，於不致熔融下，而可收縮成原來形狀。因此，將欲 保護、包裝之電子零件、纜線等被包裝物插入管內之狀態 下，藉由100至25(TC之加熱處理而可使被包裝物密接包 裝》[Technical Field] The present invention relates to a tube and a heat shrinkable tube which are composed of a non-dentate-based flame retardant material and which are excellent in shape retention and tensile properties at high temperatures. [Prior Art] It is used in electronic equipment such as electronic equipment, OA equipment, audio, video, DVD, etc., various parts in the fields of vehicles and ships, internal wiring, etc., and it is difficult to use for waterproof, dustproof, and insulation requirements. A situation in which a flammable tube or the like is protected by an intimate package is present. The flame-retardant tube used in such a close-package is required to have a flame retardancy which is acceptable in the vertical burning test VW-1 of the UL standard in order to prevent the fire from rising due to the increase in the temperature of the component. In the case of a flame retardant material, a soft polyvinyl chloride composition or a vinyl polymer such as polyethylene or an ethylene-ethyl acrylate copolymer or an ethylene-vinyl acetate copolymer is used in combination with a bromine system. Or a flame retardant resin composition of a chlorine-based flame retardant. However, such a flame-retardant material has a problem of generating a halogenated hydrogen gas during a burnout process, so that there is a demand for a halogen-free compound. A substitute for non-virulent flame retardant resin materials. On the other hand, in the tube used for the protection of the cable or the wiring such as the above-mentioned equipment, it is excellent in flexibility, and it is required to maintain the tensile strength and the elongation even at a high temperature. It is processed and deformed in the state of the tube of the packaged object. Therefore, in the tubes used for such applications, the specifications for the above-mentioned flame retardancy are not only sufficient, but also conform to the UL specifications of tensile strength, elongation, and heat deformation resistance at high temperatures. 200948895 In the case of non-halogen-based flame retardant resin materials, it is difficult to burn a metal hydroxide such as aluminum hydroxide or ethylene-ethyl acrylate copolymer or ethylene-vinyl acetate copolymer with aluminum hydroxide or magnesium hydroxide. The material of the agent has been put into practical use. However, if the vertical burning test VW_1 of the UL specification is to be qualified, a metal hydroxide-based flame retardant must be added in a large amount. On the other hand, if a large amount of metal hydroxide-based flame retardant is blended, the mechanical properties are lowered. It is impossible to seek the coexistence of flame retardancy and mechanical properties. For example, Japanese Laid-Open Patent Publication No. Hei. 7-145288 (Patent Document 1) discloses a copolymer containing ethylene-vinyl acetate-based copolymer, and a metal hydroxide-based flame retardant is used. 100 parts by mass of the matrix polymer of the material is composed of a flame retardant resin composition containing 150 to 230 parts by mass of the metal hydrate and 0.1 to 20 parts by mass of the foaming agent, and further a crosslinked tube. The flame retardant tube contains a foaming agent and is blended with a large amount of a metal hydroxide-based flame retardant to ensure a tensile strength of 0.7 kg/mm2 or more and 100% or more. However, in Patent Document 1, there is no evaluation of tensile properties and strength at high temperatures, and such a flame retardant material does not satisfy the UL standard in terms of heat resistance and heat deformation resistance. Although a phosphorus-based flame retardant such as a phosphate ester is known, its flame retardant effect is not sufficient, and if it cannot be sufficiently mixed, it is difficult to obtain a flame retardancy which can be satisfied. In order to reduce the content of the flame retardant, development of a non-halogen flame retardant material using a flame retardant polymer as a matrix polymer is underway. For example, the soft Noryl sold by SABIC Innovative Plastics Japan Contracting Company (former name: Japan GE Plastic 200948895) is a matrix polymer using a mixture of polyphenylene ether and styrene resin or styrene thermoplastic elastomer. And with phosphate ester flame retardant. According to the fact that the polyphenylene ether and the polyolefin resin are relatively high in flame retardancy, the amount of the flame retardant can be reduced, and the tensile property can be suppressed by the addition of a large amount of the flame retardant, so that the grade can be used as a wire. Used as a covering material. However, the point of heat resistance is not sufficient, especially for the purpose of close-packing. When it is used as a heat shrinkable tube, it may not be able to maintain the shape during the expansion process, or in the heat shrinking step or the processing step of the packaged material. Causes melting. Further, JP-A-2007-197615 (Patent Document 2) proposes that a phosphorus-based flame retardant is not substantially contained, a nitrogen-based flame retardant is used, and a polyphenylene ether resin and a thermoplastic elastomer are used as a matrix polymer. A non-halogen flame retardant resin composition containing a crosslinking assistant. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2007-197615 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2007-197615 [Summary of the Invention] [Inventive Problem] However, the non-halogen system disclosed in Patent Document 2 is difficult. The flammable resin composition 'is intended to be used as a covering material for electric wires and cables, and is not evaluated as a tube. In the case of being applied to a pipe, it is difficult to satisfy the UL specification after the shape retention after the diameter expansion treatment under heating, the tensile property at a high temperature, and the heat deformation resistance, so that further improvement is required. The present invention has been made in view of such circumstances, and its object is to provide a non-halogen flame retardant tube which can satisfy flame retardancy, high temperature tensile properties, and heat deformation resistance 200948895. [Means for Solving the Problem] The matrix polymer organic compound was formed into three parts of a flame retardant tree in which the upper vinyl thermoplastic g was 70% by mass. The content of the unsaturated monomer-unsaturated monomeric unsaturated monomer or the ethylene-α-olefin is preferably a fluorinated ethylene-based thermoplastic compound, and the phosphorus-based organic compound expands the flame retardancy of the invention under heating. The piping system contains 5 to 100 parts by mass of the phosphorus-based flame retardant, nitrogen to 80 parts by mass, and 1 to 20 parts by mass of the polyfunctional monomer per 100 parts by mass, which is formed into a tubular shape and irradiated with electrons. The matrix polymer contains 5 to 80% by mass of polyphenylene ether, 20 to 95% by mass of benzene elastomer, and olefin polymer 〇i β. The olefin polymer is preferably an olefin or an ethylene copolymer. More preferably, it is a block copolymer containing a polymer block of a polyolefin block and ethylene, or a copolymer of an olefin and ethylene or grafting a side chain of a polyolefin with a vinyl-based polymerized hydrocarbon copolymer. Copolymer. Further, in the case of the matrix polymer, the mass % of the olefin polymer is preferably from 5 to 80% by mass of the polyphenylene ether and from 95 to 20% by mass based on the benzene elastomer. ® The polyfunctional monomer is a monomer flame retardant having a carbon-carbon double bond, preferably a condensed phosphoric acid ester or ammonium salt, and the nitrogen is preferably a compound containing an amine group and/or a quinone group. . The heat shrinkable tube of the present invention is obtained by cooling and fixing the above-described tube diameter of the present invention. [Effect of the Invention] The flame-retardant tube of the present invention has excellent heat resistance and heat resistance by the cross-linking effect by the electron beam irradiation, and the heat-resistant and heat-resistant 200948895 deformability. Because of such excellent characteristics, the heat shrinkage of the present invention obtained by expanding the diameter under the flame-retardant heating of the present invention is also the same as that of the flame-retardant tube of the present invention, and has excellent tensile properties and heat resistance. Heat deformation resistance. [Embodiment] The embodiments of the present invention are described below, and the scope of the present invention should be construed as being illustrative and not limiting as to the scope of the present invention. The meaning of the range is uniform and all the defects made in this range <flammable resin composition> First, the resin composition of the material of the flame retardant tube of the present invention is shown. The tree used as the flame-retardant resin tube material of the present invention contains 5 parts by mass of a phosphorus-based flame retardant, 3 to 80 parts by mass of a nitrogen-based organic compound, and 1 to 100 parts by mass per 100 parts by mass of the matrix polymer. 20 parts by mass, wherein the above-mentioned matrix polymer contains: from 5 to 80% by mass of the polyphenylene ether, and from 20 to 95% by mass of the styrene-based thermoplastic elastomer to 70% by mass of the olefin-based polymer. (1) The matrix polymer composition of the matrix polymer flame-retardant resin composition is 5 to 80% by mass of polyphenylene acid, 20 to 95% by mass of styrene-based thermoplastic elastomer, and 70% by mass of olefin-based polymer, The olefin-containing polymerization form is preferably from 5 to 80% by mass of the polyphenylene ether-based resin and from 95 to 20% by mass of the styrene-based elastomer. The tube is limited in the implementation of the tube, flammability, and flammability. Contains and changes. It is said that the fat composition is 100% single-system resin I%, and the resin I%, and the thermoplasticity of the product 200948895 Polyphenylene ether refers to the oxidation of 2,6-xylenol synthesized from methanol and phenol. The resulting resin was polymerized. The polyphenylene ether-based resin used in the present invention is not only a polyphenylene ether, but also a modified polyphenylene ether modified with maleic anhydride or the like, or a polystyrene resin or a polydecylamine. A resin alloy, a polyester resin, a polymer alloy in which a polypropylene resin is melt-blended, or the like. The polymer alloy of polyphenylene ether resin and polystyrene is excellent in compatibility with a styrene-based thermoplastic elastomer, and since extrusion workability can be improved, the styrene-based thermoplastic elastomer system used in the present invention can be suitably used. A block copolymer of a block of styrene inlaid with a rubber component. a diblock copolymer or a triblock copolymer of a rubber component block such as polybutadiene or polyisoprene and a polystyrene block, and further, a hydrogenated polymer or a partially hydrogenated polymer or a cis-butene may be used. An dianhydride-modified elastomer, an epoxy-modified elastomer, an aromatic vinyl-based thermoplastic elastomer, or the like. Specifically, a styrene-isobutylene-styrene copolymer, a styrene-ethylene copolymer, a styrene-ethylene propylene copolymer, a styrene-ethylene butylene-styrene copolymer, a styrene-ethylene propylene- Styrene copolymer, styrene-isoprene copolymer, styrene-ethylene-iso-pentadiene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene copolymer, etc. . Such a styrene-based thermoplastic elastomer is useful for the improvement of tensile crack elongation. The styrene content in the styrene-based thermoplastic elastomer is preferably from 10 to 70% by weight from the viewpoint of compatibility with the elongation and polyphenylene ether. The olefin-based polymer used in the present invention means a random copolymer, a block copolymer or a graft copolymer of an olefin and an unsaturated monomer, in addition to a polymer of one or two or more olefins. 200948895 In terms of block copolymer, a copolymer having a polymer block formed by a polyolefin block and an unsaturated monomer may be exemplified, and the polyolefin block is not limited to a polymer block of an olefin monomer, but may be It is a polymer block of two or more olefin monomers. Further, the polyolefin block may be formed by hydrogenation after polymerization of a monomer having a plurality of double bonds such as a diene monomer or a triene monomer, in addition to formation of an olefin monomer. The polymer block of the ethylenically unsaturated monomer is not a polymer block formed of only one type of unsaturated monomer, and may be a ruthenium polymer block of two or more kinds of copolymerizable monomers. In the aspect of graft copolymer, a polyolefin, or a random copolymer of an olefin and an unsaturated monomer, a block copolymer as a main chain, a homopolymer of a unsaturated monomer in a side chain, a random copolymer The block copolymer is grafted. As the olefin unit constituting the above polyolefin block or polyolefin, ethylene, propylene, 1-butene, isobutylene, pentene, hexene or the like can be used. As the unsaturated monomer, unsaturated acids such as acrylic acid, methacrylic acid, methyl hydrazine methyl acrylate, crotonic acid, citric acid (anhydride), maleic acid (anhydride), and itaconic acid (anhydride) may be used. a monoalkyl ester having 1 to 8 carbon atoms or an ester with epoxy propanol; a vinyl ester of a fatty acid such as vinyl formate, vinyl acetate, vinyl propionate or vinyl valerate; aroma such as styrene or allylic benzene; a vinyl compound; a vinyl cyanide such as acrylonitrile, acrylonitrile styrene or methacrylonitrile. Therefore, specific examples of the olefin-based polymer of the present invention include ultra low density polyethylene, low density polyethylene, medium density polyethylene, linear -10-200948895 low density polyethylene, high density polyethylene, and the like. Polyethylene, polypropylene, B-alpha olefin copolymer, olefin thermoplastic elastomer, ethylene-acetate vinegar copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene·methacrylic acid Methyl ester copolymer, ethylene-methyl acrylate copolymer, styrene-ethylene butene-olefin crystalline block copolymer, main chain of polyolefin (such as polyethylene or polypropylene) or olefin and ethylenically unsaturated monomer Copolymer (for example, ethylene·glycidyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-ethylene acrylate-cis-butenedi anhydride copolymer), on the side The chain is a vinyl polymer (for example, polystyrene, polymethyl methacrylate, or acrylonitrile-styrene copolymer 'polyvinyl acetate, polyethyl acrylate, polyethyl acrylate, polypropylene) Acidic butyl vinegar, polyacrylic acid neutralized with metal ions, etc.) or ethylene-α olefin copolymer (for example, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene methyl methacrylate copolymer) , ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene acrylic rubber, ethylene·glycidyl methacrylate copolymer, ethylene-methyl acrylate-methacrylic acid epoxy Grafting of a propyl ester copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene ionomer or a polymer modified with a cisplatin or the like, etc. Copolymers, etc. Such an olefin-based polymer also exhibits flame retardancy similarly to the above styrene-based thermoplastic elastomer. In the matrix polymer, the content of each of the above polymers (polyphenylene ether resin, styrene thermoplastic elastomer, olefin polymer) is 5 to 80% by mass of the polyphenylene ether resin, and the styrene thermoplastic elastomer 2〇 to 95% by mass, -11-200948895 and olefin-based polymer 0 to 70% by mass. When the content of the olefin polymer is 〇% by mass, it is preferably a polyphenylene ether resin: styrene thermoplastic elastomer = 5: 95 to 80: 20. When the content ratio of the olefin-based polymer is more than 70% by mass in the matrix polymer, it is necessary to reduce the content of the styrene-based thermoplastic elastomer which is more excellent in flame retardancy, and it tends to be flame retardant. reduce. Further, when the content ratio of the polyphenylene ether resin is too small and the content ratio of the styrene-based thermoplastic elastomer is too large, the flame retardancy tends to be unsatisfactory. On the other hand, when the content ratio of the polyphenylene ether-based resin is too large, and the content ratio of the styrene-based thermoplastic elastomer or the olefin-based polymer is too small, the tensile properties tend not to be satisfied. (2) Phosphorus-based flame retardant In the case of the phosphorus-based flame retardant used in the present invention, an orthophosphate; a cross-linking having a branched fluorenyl group in a molecule such as pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid or superphosphoric acid; a structure, or a phosphate or a combination of a linear or cyclic organic ester or ammonium salt of a condensed phosphoric acid; a phosphonate; a phosphinate; etc., wherein an organic ester or an ammonium salt of a condensed phosphoric acid is preferably used. It is also possible to use a substance having a ?? group in the molecule. Specifically, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triglycidyl phosphate, xylenyl ester, cresyl phenyl phosphate, cresol phosphate can be exemplified. 2,6-benzenedicarboxylate, 2-ethylhexyldiphenyl phosphate, 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6 _ Benzyl dimethyl phosphate), 1,2-phenylene bis(di-2,6-benzenedimethyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol double Diphenyl ester, octyl diphenyl phosphate, diethyl ethyl ester phosphate, dihydroxypropyl propyl-12- 200948895 butyl ester vinegar, ethyl disodium ethate phosphate, three grades of acid Butyl phenyl diphenyl ester, bis-(tri-butylphenyl)phenyl phosphate, glycerol (tri-butylphenyl) vinegar, isopropylphenyl diphenyl vinegar, pity bis ( Isopropyl phenyl) diphenyl vinegar, ginseng (isopropylphenyl) diphenyl vinegar, p-acid isopropyl (isopropyl phenyl) vinegar, ginseng (2-ethylhexyl) phosphate, glycerin Phosphate of oxyethyl) ester, isobutyl phosphate, etc.; methyl phosphonate, Dimethyl methylphosphonate, diethyl methyl sulphate, ethyl phosphonate, propyl phosphonate, butyl phosphonate, 2-methyl-propyl phosphinate, tertiary butyl phosphonate, phosphonic acid Phosphonic acid esters such as 2,3-dimethylbutyl ester, phosphonic acid vinegar, phenyl phosphonate; diethyl phosphinate, methyl phosphinate, phenyl phosphinate, diethyl phosphinate Phosphine esters such as phenyl phenyl esters and diphenyl phosphinates; phosphite or 9,10-dihydro-9 'oxa-10-anthene phenanthrene (phosphaphenanthrene) )-lO-oxide, HCA-HQ, SANKO-220, Μ-Ester, BCA, etc., cyclic organic dish compounds, ammonium polyphosphate, tripolyfluorophosphate, melamine polyphosphate, melamine pyrophosphate, phosphoric acid A compound of phosphorus and nitrogen such as guanyl urea, strontium phosphate, Adecastab FP2100J or Adecastab FP2200 sold by ADECA, and FLMESTAB NOR116FF manufactured by Ciba © Specialty Chemicals. These phosphorus-based flame retardants may be used alone or in combination of two or more. As the above phosphorus compound, a surface-formed material such as melamine or melamine cyanurate, a fatty acid or a decane coupling agent may be used. When mixed with the base polymer, surface treatment can also be carried out by integral blending with a surface treatment agent. The phosphorus-based flame retardant is contained in an amount of 5 to 100 parts by mass per 1 part by mass of the matrix polymer. When the amount is less than 5 parts by mass, it is difficult to ensure the flame retardancy, and when it exceeds 100 -13 to 200948895 parts by mass, the heat deformation resistance cannot be satisfied. (3) Nitrogen-based organic compounds In terms of nitrogen-based organic compounds, it is preferred to use a derivative or an adduct such as cyanuric acid, melamine or triazine, and in particular, a melamine resin or a melamine cyanurate may be used. Iso-cyanuric acid, isomeric cyanurate derivatives, adducts, and the like. Among these, it is preferred to use melamine or melamine cyanurate containing an amine group and/or a quinone imine unit in the molecule. Although the mechanism of such a nitrogen-based organic compound is not known, the use of a phosphorus-based flame retardant does not cause a significant decrease in tensile properties, and a VW-1 test that can meet UL specifications can be ensured. The flame retardancy of the qualified grade. The nitrogen-based organic compound may be a decane coupling agent such as an amino decane coupling agent, a vinyl decane coupling agent, an epoxy decane coupling agent or a methacryloxy decane coupling agent; or a stearic acid or oleic acid; Higher fatty acids can also be surface treated. Surface treatment can also be carried out in advance, and the matrix polymer and other components can be surface-treated by mixing with a surface treatment agent. The nitrogen-based organic compound contains 3 to 80 parts per 100 parts by mass of the matrix polymer. Parts by mass. When the amount is less than 3 parts by mass, the flame retardant effect due to the use of the phosphorus compound is not obtained. When the amount is more than 80 parts by mass, the tensile elongation at break is lowered, and the initial tensile properties are not secured. (4) In terms of the polyfunctional monomer polyfunctional monomer, it is preferred to use a monoacrylate type, a diacrylate type, a triacrylate type, a monomethacrylate type, a dimethacrylate type, and a trimethyl group. A monomer having a plurality of carbon-carbon double bonds in a molecule such as an acrylate-based, triallyl cyanurate-based or a tris--14-200948895 polycyanate. From the viewpoint of crosslinkability, it is preferred to use a trimethacrylate monomer such as trimethylolpropyl methacrylate. Such a polyfunctional monomer can be expected to be polymer-polymerized with a diene portion contained in a matrix polymer by electron beam irradiation, and is expected to be extremely useful for improving physical properties at temperatures. The polyfunctional single system contains 1 to 20 parts by mass per 100 parts by mass of the matrix polymer. When the amount is less than 1 part by mass, the crosslinking effect is not obtained, so that the deterioration of the tensile property at a high temperature becomes remarkable, and the thermal deformation at a high temperature is also large. On the other hand, when it exceeds 20 parts by mass, unreacted monomers remain, which causes a decrease in flame retardancy. (5) Other components may be added with metal hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide, without impairing flame retardancy, heat deformation resistance, tensile properties, and volume resistivity. A flame retardant such as antimony trioxide, zinc stannate, zinc hydroxystannate, zinc borate or boron phosphate. The flame-retardant resin composition used in the present invention can be blended with a polyolefin thermoplastic elastomer, a polyester thermoplastic elastomer, and the like, without impairing the range of flame retardancy or mechanical strength, for various characteristics. Other thermoplastic elastomers such as polyurethane thermoplastic elastomer; styrene resin such as impact resistant polystyrene, acrylonitrile-styrene resin, ABS resin; EPDM, vinyl acrylate rubber, acrylic rubber, nitrile rubber Rubber, etc.; various polymers such as nylon, polybutylene terephthalate (PBT), polyethylene terephthalate, poly(vinyl phthalate), polyphenyl sulfide. In addition, it can also be combined with antioxidants, lubricants, processing stabilizers, various additives such as -15-200948895 colorant, foaming agent, reinforcing agent, chelating agent, sulfurizing agent, metal inert agent, decane coupling agent, etc. . The components as described above are blended at a predetermined amount, and can be prepared by mixing using a melt mixer such as a uniaxial extrusion type mixer, a pressure kneader, a Banbury mixer or the like. <Flameable tube> The flame-retardant tube of the present invention is obtained by extrusion-molding a flame-retardant resin composition having the above-described composition into a tubular molded article formed into a tubular shape, and electron beam irradiation is performed thereon. Things. It is believed that the matrix polymer can be crosslinked by electron beam irradiation through a polyfunctional monomer. Then, by the crosslinking, the decrease in the elastomeric properties at a high temperature of the thermoplastic elastomer can be suppressed, and therefore, it is considered that the tensile properties at the temperature of the enthalpy can be ensured. Further, by the partial network structure due to cross-linking, it is also possible to suppress thermal deformation, and it is impossible to melt due to high-temperature treatment, and the shape can be maintained. The size of the flame-retardant tube is not particularly limited, and it is usually preferably 1.0 mm or less, more preferably 8. 8 mm or less. In the case of extrusion molding, the flame retardant resin composition is prepared at one time, and has a setting in manufacturing. After the resin pellets are composed, it is preferred to supply the resin pellets to an extrusion molding machine. The type of the extruder is not particularly limited and may be either a spiral type or a non-helical type, and is preferably a spiral type. The type of the helix is not particularly limited, and the ratio of the total length L to the cylindrical aperture D (L/D) is usually about 24 to 28. In terms of the electron beam used, there are an accelerated electron beam or a gamma ray, an X-ray, a -16-200948895 alpha line, an ultraviolet ray, or the like. The ease of use of the line source, the transmission thickness of the ionizing radiation, the speed of the crosslinking treatment, etc., from the viewpoint of industrial use, it is preferable to use an accelerated electron beam. The accelerating voltage of the electron beam is accelerated, and the wall thickness of the tube layer can be appropriately set for the composition of the resin composition of the tube material. For example, in a tube having a thickness of 0.2 mm to 0.4 mm, the accelerating voltage can be selected from 300 keV to 3 MeV. The amount of irradiation line is not particularly limited and is usually 20 to 50,000 kGy. <Heat-shrinkable tube> The heat-shrinkable tube of the present invention is obtained by expanding the diameter of the flame-retardant tube of the present invention under heating and then cooling it. In the diameter expansion treatment, the tubular molded article is heated to a temperature higher than the softening temperature of the matrix polymer, and is expanded into a set outer diameter by introducing compressed air or the like into the tube, and then obtained by cooling and fixing the shape. . The diameter expansion should be about 2 to 4 times the original inner diameter. The tube of the present invention is excellent in heat resistance, and does not melt even at a high temperature, and can be expanded in diameter to maintain the shape of the expanded diameter. ¥ The heat-shrinkable tube of the present invention has excellent heat resistance, so that it can be shrunk again by a heat treatment temperature, in particular, by heat treatment at 1 to 250 ° C without melting. Original shape. Therefore, in the state where the packaged object such as the electronic component or the cable to be protected or packaged is inserted into the tube, the packaged article can be closely packed by heat treatment of 100 to 25 (TC).
藉由熱收縮處理而收縮之管，與擴徑處理前之管具有 相同程度的拉伸特性，即使在加熱條件下亦可保持以UL -17- 200948895 規格所求得的拉伸特性。因此，本發明之熱收縮性管可作 爲以電子零件或纜線等的被包裝物之防濕、防水、防塵、 絕緣等爲目的之保護包裝材來加以利用。 【實施方式】 實施本發明之最佳形態係以實施例加以說明。實施例 並非限定本發明之範圍。 此外，在以下之實施例中，「份」者除非事先告知則指 「質量份」之意。 ® [測定評價方法] 首先，就以下之實施例所進行之測定評價之方法來加 以說明。 (1) 拉伸特性 關於管，進行拉伸試驗（拉伸速度=500mm/分、標距 (gauge length) = 20mm)，使拉伸強度（MPa)與拉伸裂斷延伸 (%)以各3份試料來測定，求得該等之平均値。拉伸強度 10.4MPa以上且拉伸裂斷延伸150%以上則爲合格等級。 翁 (2) 耐熱性 將管在設定成158 t的傳動烤爐中放置168小時（7日） 後’進行上述（1)拉伸試驗。若加熱處理後之拉伸強度 7.3MPa以上、延伸1〇0%以上時則爲合格等級。 (3) 難燃性 在UL規格224記載的VW-1垂直難燃試驗就5份試料 進行試驗。試驗係對各試料重複進行五次的15秒著火的情 形’在60秒以內熄滅（extinction)，而敷於下部的脫脂綿並 -18- .200948895 不因燃燒掉下物而隨之起火（catchingfire)，在安 上部的牛皮紙燃燒，或並不燒焦者則爲合格等級， 表示。在5份中，連1份都無法爲合格等級之情 不合格「NG」表示。 (4) 耐加熱變形性 準照JIS C3 005進行。將內徑7.0mm之金屬 內，裝入設定於1 40°C的恆溫槽，經1小時預熱。1 將0 9.5mm之夾具抵接（press against)於管，擺」 ® 負荷。在施加負荷之狀態下測定放置1小時後 度，計算相對於變形前厚度的滯留率（retention)。 爲5 0%以上時則爲合格等級。 此外，在進行擴徑-熱收縮處理的熱收縮管 形，於熱收縮處理之際，預先插入內徑7.0mm之 爲金屬棒插入管，將此金屬棒插入管在恆溫槽預 負荷並測定放置一小時後之厚度。 (5) 熱震（heat shock)試驗 g% W 在設定於250°C之傳動烤爐內，使管加熱4 出，捲繞成與管外徑相同徑的金屬棒，並觀察管 外觀上，若無特別變化則爲合格等級，以「0K」 〔難燃性樹脂組成物之調製及管之製成〕 實施例管No.1至15 : 如表1所示，將聚苯醚系樹脂1或2、苯乙 性彈性體1或2、烯烴系聚合物1至4、磷系化合1 氮系化合物1或2、多官能性單體1或2配合表1 裝於試料 以「OK」 形，則以 棒插入管 小時後， :500g 之 的管層厚 若滯留率 評價之情 金屬棒成 熱，施加 小時後取 外觀。在 表示。 烯系熱塑 物1至3、 .所示量。 -19- 200948895 進而相對於基質聚合物（聚苯醚系樹脂、苯乙烯系熱塑性彈 性體及烯烴系聚合物之合計）1〇〇份，配合以油酸醯胺0.5 份、新戊四醇-肆〔3-(3,5-二三級丁基-4-羥基苯基）丙酸酯〕 3份，將由以設定鑄模溫度28CTC之二軸混合機進行捏合所 得捏合物之股線（strand)使用製粒機（pelletizer)，獲得各樹 脂組成物No.l至15之樹脂顆粒。 使用已調製之樹脂組成物No.1至15之顆粒，使用熔 融擠壓機（45mm φ、L/D = 24、壓縮比2.5、螺桿螺紋總長度 ❿ 型（full flight type)) ’於擠壓溫度260°C，將內徑7.0mm、 厚壁0_3mm之管狀成形品進行擠壓成形。在所得之管照射 加速電壓2.0 M eV之電子束2 5 OkGy，進而，關於No.7至 15之管，則進行擴徑-熱收縮處理，製作出管Νο·ι至15。 No.7至15係相當於使熱收縮管熱收縮之物。 在此，擴徑-熱收縮處理係指，在設定於16(TC之恒溫 槽放置3分鐘並預熱後，藉由使壓縮空氣饋入管內而可擴 徑至內徑14mm爲止，馬上自恆溫槽取出，進行水冷並使 魯 形狀固定。藉由擴徑處理所得熱收縮管在160°C進行3分 鐘加熱，而進行收縮至原來尺寸（內徑7mm)爲止。 就已製作之管No.l至15，根據上述評價方法，測定 拉伸特性、耐熱性、難燃性、耐熱變形性、熱震試驗並評 價之。結果如表1所示。 比較例管N 〇 . 1 6至2 6 : 除了使樹脂組成物之配合組成變更成爲表2所示以 外’其他與上述實施例將相同並經調製的各樹脂組成物 -20- 200948895 Νο·16至26之樹脂顆粒，與上述實施例相同進行擠壓成 形’獲得內徑7.0mm、壁厚0.3 mm之管狀成形品。將Νο.16 至21' 23、26之管，僅以表2所示量照射加速電壓2.〇MeV 之電子束，進而就Νο.16至21、23、26之管，則進行與上 述實施例相同之擴徑-熱收縮處理》 關於如以上方式製作之管Νο.16至26，根據上述評價 方法’測定並評價拉伸特性、耐熱性、難燃性、加熱變形 _ 性、熱震試驗。測定結果如表2所示。 此外，表1及表2中之化合物係如下述。The tube which is shrunk by the heat shrinkage treatment has the same tensile properties as the tube before the diameter expansion treatment, and the tensile properties obtained in the UL-17-200948895 specification can be maintained even under heating conditions. Therefore, the heat-shrinkable tube of the present invention can be utilized as a protective packaging material for the purpose of preventing moisture, water, dust, and insulation of a packaged object such as an electronic component or a cable. [Embodiment] The best mode for carrying out the invention will be described by way of examples. The examples are not intended to limit the scope of the invention. Further, in the following embodiments, "parts" means "mass parts" unless otherwise notified. ® [Measurement Evaluation Method] First, the method of measurement and evaluation performed in the following examples will be described. (1) Tensile properties Regarding the tube, a tensile test (tensile speed = 500 mm/min, gauge length = 20 mm) was carried out, and the tensile strength (MPa) and the tensile elongation (%) were each Three samples were measured to determine the average enthalpy of the samples. The tensile strength is 10.4 MPa or more and the tensile elongation at break is 150% or more. Weng (2) Heat resistance After the tube was placed in a transmission oven set at 158 t for 168 hours (7 days), the above (1) tensile test was carried out. If the tensile strength after heat treatment is 7.3 MPa or more and the elongation is 1 〇 0% or more, it is a pass grade. (3) Flame retardancy The VW-1 vertical flame retardant test described in UL Specification 224 was tested on 5 samples. The test system repeated five times of 15 seconds of ignition on each sample 'extinction within 60 seconds, and applied to the lower part of the skim cotton and -18-.200948895 does not catch fire due to burning off (catchingfire ), in the upper part of the kraft paper burning, or not burnt is a qualified grade, said. In 5 out of 5, even one of the items cannot be qualified. The unqualified "NG" is indicated. (4) Resistance to heat deformation Refer to JIS C3 005. A metal having an inner diameter of 7.0 mm was placed in a thermostat set at 1400 ° C and preheated for 1 hour. 1 Abut the 0 9.5mm clamp against the tube and the load ® load. The degree of retention after deposition for 1 hour was measured in a state where a load was applied, and the retention with respect to the thickness before deformation was calculated. When it is more than 50%, it is a pass level. In addition, in the heat shrinkable tube shape of the diameter expansion-heat shrinkage treatment, a metal rod insertion tube having an inner diameter of 7.0 mm was inserted in advance at the time of heat shrinkage treatment, and the metal rod was inserted into the tube to be preloaded in the constant temperature bath and measured and placed. The thickness after one hour. (5) Heat shock test g% W In a drive oven set at 250 ° C, the tube is heated 4 times, wound into a metal rod of the same diameter as the outer diameter of the tube, and the appearance of the tube is observed. If there is no special change, it is a qualified grade, with "0K" [Preparation of flame retardant resin composition and tube production] Example No. 1 to 15: As shown in Table 1, polyphenylene ether resin 1 Or 2, styrene-butadiene elastomer 1 or 2, olefin-based polymer 1 to 4, phosphorus-based compound 1 nitrogen-based compound 1 or 2, and polyfunctional monomer 1 or 2 are attached to the sample in an "OK" shape. Then, after the rod is inserted into the tube, the thickness of the tube layer of 500 g is evaluated as the retention rate of the metal rod, and the appearance is taken after the application of the hour. In the indication. The amount of the olefinic thermoplastics 1 to 3, . -19- 200948895 Further, in combination with a matrix polymer (a total of a polyphenylene ether resin, a styrene thermoplastic elastomer, and an olefin polymer), 0.5 part by weight of decyl oleate, and pentaerythritol - 3 parts of 肆[3-(3,5-ditriphenylbutyl-4-hydroxyphenyl)propionate], and the strand of the kneaded product obtained by kneading with a two-axis mixer set at a mold temperature of 28 CTC Resin particles of each of the resin compositions No. 1 to 15 were obtained using a pelletizer. Using the pellets of the prepared resin compositions No. 1 to 15, using a melt extruder (45 mm φ, L/D = 24, compression ratio 2.5, total flight type) At a temperature of 260 ° C, a tubular molded article having an inner diameter of 7.0 mm and a thick wall of 0 to 3 mm was extrusion-molded. The obtained tube was irradiated with an electron beam 2 5 OkGy having an acceleration voltage of 2.0 M eV, and further, the tubes of Nos. 7 to 15 were subjected to an expansion-heat shrinkage treatment to produce a tube Νο·ι to 15. Nos. 7 to 15 correspond to those which heat-shrink the heat shrinkable tube. Here, the diameter expansion-heat shrinkage treatment means that after being placed in a thermostat bath of TC for 3 minutes and preheating, the compressed air can be expanded into the tube to expand the diameter to an inner diameter of 14 mm. The groove was taken out, water-cooled, and the shape of the ruthenium was fixed. The heat-shrinkable tube obtained by the diameter expansion treatment was heated at 160 ° C for 3 minutes, and was shrunk to the original size (inner diameter 7 mm). From the above evaluation methods, tensile properties, heat resistance, flame retardancy, heat deformation resistance, and thermal shock test were measured and evaluated. The results are shown in Table 1. Comparative Example Tube N 〇. 16 to 2 6 : The resin pellets of the respective resin compositions -20-200948895 Νο·16 to 26 which were the same as those of the above-described examples and which were prepared in the same manner as in the above-described examples were carried out except that the composition of the resin composition was changed to that shown in Table 2. Extruded to obtain a tubular molded article having an inner diameter of 7.0 mm and a wall thickness of 0.3 mm. The tubes of Νο.16 to 21' 23, 26 were irradiated with an electron beam of an acceleration voltage of 2. 〇MeV only in the amounts shown in Table 2. And then the tube of Νο.16 to 21, 23, 26, and the above implementation The same diameter-heat shrinkage treatment. Regarding the tubes Νο. 16 to 26 produced as described above, tensile properties, heat resistance, flame retardancy, heat deformation, and thermal shock test were measured and evaluated according to the above evaluation method. The measurement results are shown in Table 2. Further, the compounds in Tables 1 and 2 are as follows.
*1:聚苯醚1:三菱工程塑膠公司製PX-100L :聚苯醚2 :旭化成化學公司製之Zylon Χ9102 此係聚苯醚樹脂與聚苯乙烯樹脂之完全相溶系聚合物 合金。 :苯乙烯系彈性體1 :旭化成化學公司製之tuftec H1041 此係苯乙烯-乙烯丁烯-苯乙烯共聚物，苯乙烯含有率 g 3 0質量％。 *4:苯乙烯系彈性體2:旭化成化學公司製之SOE-SS9000 此係氫化SBR。 :磷系化合物1 : Ciba公司製之MELAPUR200 此係聚磷酸三聚氰胺，平均粒徑4μιη、磷含有率13質 量％、氮含有率43質量％ ^ *6:磷系化合物2:大八化學工業公司之ΡΧ-2 00 此係縮合磷酸酯，磷含有率9.0質量％。*1: Polyphenylene ether 1: PX-100L manufactured by Mitsubishi Engineering Plastics Co., Ltd.: Polyphenylene ether 2: Zylon Χ9102 manufactured by Asahi Kasei Chemicals Co., Ltd. This is a completely compatible polymer alloy of polyphenylene ether resin and polystyrene resin. : Styrene-based elastomer 1 : Tuftec H1041 manufactured by Asahi Kasei Chemicals Co., Ltd. This is a styrene-ethylene butylene-styrene copolymer having a styrene content of g 3 0% by mass. *4: Styrene-based elastomer 2: SOE-SS9000 manufactured by Asahi Kasei Chemicals Co., Ltd. This is a hydrogenated SBR. : Phosphorus compound 1 : MELAPUR 200 manufactured by Ciba Co., Ltd. This is a melamine polyphosphate having an average particle diameter of 4 μm, a phosphorus content of 13% by mass, and a nitrogen content of 43% by mass. ^6: Phosphorus compound 2: Da Ba Chemical Industry Co., Ltd. ΡΧ-2 00 This is a condensed phosphate ester having a phosphorus content of 9.0% by mass.
*7:磷系化合物3:三光公司製之BCA -21- 200948895 此係環狀有機磷化合物。 *8:氮系化合物1:堺化學工業公司製之STABIACE MC-5S 此係三聚氰酸三聚氰胺酯（平均粒徑〇·5μιη)。 *9:氮系化合物2:三菱化學公司製之三聚氰胺 *10:多官能性單體1:新中村化學工業公司製之ΝΚ酯ΤΜΡΤ 三甲基丙烯酸三羥甲基丙酯 *11:多官能性單體2:日本化成公司製之Taic(異三聚氰酸 三烯丙酯） ❹ *12:烯烴系聚合物1 :日本聚乙烯製之Respearl A1150。 此係乙烯-丙烯酸乙酯共聚物（丙烯酸乙酯含有率15質 量°/〇、MFR0.8(190°C、負荷 2.16kg))。 *13 :烯烴系聚合物2 :杜邦公司製之Elvaloy 11 25 AC。此係 乙烯-丙烯酸甲酯共聚物（丙烯酸甲酯含有率27質量％、 MFR0.6(190°C、負荷 2.16kg))。 *14 :烯烴系聚合物3 : JSR公司製之Dynaron4600P。此係 苯乙烯-乙烯丁烯-烯烴結晶嵌段共聚物。 ¥ *15:烯烴系聚合物4:曰本油脂公司製之ModeperAllOO。 此係主鏈爲低密度聚乙烯使聚苯乙烯進行接枝化之聚 合物》 -22- 200948895*7: Phosphorus compound 3: BCA-21-200948895 manufactured by Sanko Co., Ltd. This is a cyclic organophosphorus compound. *8: Nitrogen-based compound 1: STABIACE MC-5S manufactured by Sigma Chemical Industry Co., Ltd. This is melamine cyanurate (average particle size 〇·5 μmη). *9: Nitrogen-based compound 2: Melamine manufactured by Mitsubishi Chemical Corporation *10: Polyfunctional monomer 1: oxime ester manufactured by Shin-Nakamura Chemical Co., Ltd. Trimethylolpropyl trimethacrylate*11: Polyfunctionality Monomer 2: Taic (triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd. *12: Olefin polymer 1: Respearl A1150 made of Japanese polyethylene. This was an ethylene-ethyl acrylate copolymer (ethyl acrylate content: 15 mass ° / 〇, MFR 0.8 (190 ° C, load 2.16 kg)). *13: Olefin polymer 2: Elvaloy 11 25 AC manufactured by DuPont. This is an ethylene-methyl acrylate copolymer (methyl acrylate content: 27% by mass, MFR 0.6 (190 ° C, load: 2.16 kg)). *14: Olefin polymer 3: Dynaron 4600P manufactured by JSR. This is a styrene-ethylene butene-olefin crystalline block copolymer. ¥ *15: Olefin polymer 4: Modeper AllOO manufactured by Sakamoto Oil Co., Ltd. The main chain of this series is a polymer obtained by grafting polystyrene with low density polyethylene. -22- 200948895
1 Ο 1 1 1 〇 1 1 1 \〇 1 o CN W- 异 «Π cs oo »—H cs o o (N Os un 1 1 1 1 沄 1 1 1 w-> 1 o vr> 〇i W- vn cn cs o o 8 <N 〇 〇 oo on 1 1 沄 1 〇 1 1 异 1 1 VO 1 o m cs ο o o a\ 04 〇 〇 s CN 异 1 irj JO 1 I 1 1 1 导 1 o vn 1 1 ο a\ g <N § 〇 CN o 〇 in tn 1 1 1 导 1 异 1 1 1 in vn 1 o ir> <N ο cn <N CN o tn 〇 o oo o 1 1 〇 1 1 1 1 IQ 1 纪 1 m 1 CN o o4 CN S CS o 异 o CO <N 〇 o g 〇\ 1 穿 8 1 1 1 1 1 1 1 1 cn … 1 〇 tn cs 擗 ir> vn 〇\ o w o oo 1 〇 1 1 1 1 1 1 1 1 vn 1 o CN 〇 cn <N vn cs cs 艺 o o s 卜 ο 1 1 1 1 1 1 异 1 1 iQ 1 1 泛 CN 蚺 in g CN o vr> v〇 <s o o ON vr> VO 1 穿 S 1 1 1 1 1 1 1 1 m vn 1 〇 cs 1 〇 cs w-> CN <N T—H o w o in 00 异 1 1 % 1 1 1 1 1 m 1 g 1 卜 1 o vr> CS 1 s oo ir^ w-> 〇 〇 o νη 1 1 1 1 1 1 1 1 1 oo 1 o u〇 CS 1 对 CO VO i _ 1 c5 o 〇 l〇 VO cn 1 〇 1 1 1 1 1 1 异 1 异 1 1 s CN 1 un g CN o cs cs o o o g (N 1 ν〇 1 i 1 1 1 1 1 异 1 o 1 〇 w-> 1 m oo <N p CN o o ir> ON 产H ο 1 S, 1 1 1 1 1 1 1 irj 1 1 vr^ 〇 m cs 1 〇 o 〇5 o v〇 OJ o 〇 實施例獅· I /*—Ν «' ^ 2(*2) Nw/ 2(*4) I 1(*12) I 2(*13) I 3(*14) 1 4(*15) I ·***N tp 2(*6) 3(*7) y—S oo 2(*9) 1 i(no I 2(*11) 電子線照射量(kGy) 擴徑-熱収縮處理 拉伸強度(MPa) 延伸(％) 拉伸強度(MPa) | 延伸(％) 難燃性 縝 m 耐熱變形性(滯留率9fc) 聚苯醚 苯乙稀系 彈性體 翅Φ 磷系 化雜 氮系 化合物 ^ m mQC l^wB ¢0 g^- ^ m f： #d m m m 2009488951 Ο 1 1 1 〇1 1 1 \〇1 o CN W- 异«Π cs oo »—H cs oo (N Os un 1 1 1 1 沄1 1 1 w-> 1 o vr> 〇i W- Vn cn cs oo 8 <N 〇〇oo on 1 1 沄1 〇1 1 different 1 1 VO 1 om cs ο ooa\ 04 〇〇s CN different 1 irj JO 1 I 1 1 1 lead 1 o vn 1 1 ο a\ g <N § 〇CN o 〇in tn 1 1 1 derivative 1 different 1 1 1 in vn 1 o ir><N ο cn <N CN o tn 〇o oo o 1 1 〇1 1 1 1 IQ 1 1 m 1 CN o o4 CN S CS o iso o CO <N 〇og 〇\ 1 wear 8 1 1 1 1 1 1 1 1 cn ... 1 〇tn cs 擗ir> vn 〇\ owo oo 1 〇 1 1 1 1 1 1 1 1 vn 1 o CN 〇cn <N vn cs cs art oos ο 1 1 1 1 1 1 different 1 1 iQ 1 1 pan CN 蚺in g CN o vr>v〇<soo ON vr> VO 1 wears S 1 1 1 1 1 1 1 1 m vn 1 〇cs 1 〇cs w-> CN <NT-H owo in 00 is different 1 1 % 1 1 1 1 1 m 1 g 1 1 o vr> CS 1 s oo ir^ w-> 〇〇o νη 1 1 1 1 1 1 1 1 1 oo 1 ou〇CS 1 to CO VO i _ 1 c5 o 〇l〇VO cn 1 〇1 1 1 1 1 1 different 1 different 1 1 s CN 1 un g CN o Cs cs ooog (N 1 ν〇1 i 1 1 1 1 1 iso 1 o 1 〇w-> 1 m oo <N p CN oo ir> ON H ο 1 S, 1 1 1 1 1 1 1 irj 1 1 vr^ 〇m cs 1 〇o 〇5 ov〇OJ o 〇Example Lion · I /*—Ν «' ^ 2(*2) Nw/ 2(*4) I 1(*12) I 2( *13) I 3(*14) 1 4(*15) I ·***N tp 2(*6) 3(*7) y—S oo 2(*9) 1 i(no I 2(*11 ) Electron line irradiation (kGy) Expansion diameter - heat shrinkage treatment Tensile strength (MPa) Extension (%) Tensile strength (MPa) | Extension (%) Flame retardancy 缜m Heat deformation resistance (residence rate 9fc) Polyphenylene Ether styrene elastomeric wing Φ Phosphorus-based nitrogen compound ^ m mQC l^wB ¢0 g^- ^ mf: #dmmm 200948895
Ό CS 1 o 1 l〇 1 1 1 s 1 1 1 1 〇 CN Οί ψ ( CN δ ο ΟΟ cs 1 s o 1 1 1 1 1 1 1 1 1 1 S 1 〇 CN CO Ώ 1—^ 〇 wS CM g ϋ 2； Μ ο ο 1 o s 1 1 1 1 1 1 1 1 cn 1 1〇 〇 1 〇6 1-H 泛 m 溶融| 溶融 〇 溶融 ο CO CN 1 o 1 1 1 1 1 1 1 1 CN 1 〇 >-n CS w xr^ οό c<\ ο «—Η vn Ο 2； 破裂 〇〇 σ\ CS CN 异 1 1 § 1 1 1 1 1 1 1 1 1 〇 <N 1 ο (Ν CN 1 溶融 溶融 Μ 〇 溶融 jo 1 穿 s 1 1 1 1 1 1 1 1 1 Ο cs ο ιη CN 1 ο 8 CS § 〇 § 异 1 1 g 1 1 1 1 1 VO 1 1 1 Ο ι—Η 异 1 ( W-) wS «—Η g 〇 ο § a\ 1 1 1 1 1 1 1 1 〇 1-H 1 1 〇〇 1 Ο (Ν ο irj § CS Ο Μ ο oo 异 1 1 g 1 1 1 1 1 CO 1 g 1 卜 1 ο ι〇 σ\ 1—Η g cs Ο aj o ο 之 〇 JQ 二 cn 1 〇\ 1 1 1 1 1 没 1 1 1 1 1 〇〇 <Ν S »-Η 沄 cn vn <N ο 2： Μ 〇 v〇 I & 1 IQ 1 1 1 1 1 1 1 1 1 Ο CS 1/Ί R O ON cs w ο 破裂 ΟΟ ΟΝ 比較例管No· 2(*2) 1(*3) 2(*4) 1(*12) 2(*13) 3(*14) 4(*15) 1(*5) 2(*6) 3(*7) 1(*8) 2(*9) 1(*10) 2(*11) 電子線照射量(kGy) 擴徑-熱收縮處理 拉伸強度(MPa) 延伸(％) 拉伸強度(MPa) 延伸(％) 難燃性 熱震 耐熱變形性(滯留率％) 聚苯醚 味 « m κι m 浒靜; m <n 涯嵌 磷系 化雜 氮系 化合物 m 拉伸 特性 m m m I 200948895 參考管No.3 1，32 : S ABIC創新塑膠合同會公司製之柔軟Noryl樹脂化合物 與上述實施例相同予以擠壓成形，獲得管狀成形品。將所 得之管與實施例1相同進行電子束照射，進而進行擴徑-熱 收縮處理，來製作管No.3 1，32。關於製成的管，係根據上 述評價方法，測定拉伸特性、耐熱性、難燃性、耐熱變形 性、熱震並評價之。結果如表3所示。 【表3】 參考管No. 31 32 WCD801-BK1066 100 _ WCD891A-BK1066 — 100 電子束照射量(kGy) 250 250 擴徑-熱雌處理 有 有 拉. 拉伸強度(MPa) 17.0 19.0 伸 延伸(％) 230 280 特 性 耐 拉伸強度(MPa) 20.0 22.0 熱 延伸(％) 70 80 性 難燃性 NG NG 熱震 熔融 熔融 耐熱變形(滯留率％) 12 15Ό CS 1 o 1 l〇1 1 1 s 1 1 1 1 〇CN Ο ψ ψ ( CN δ ο ΟΟ cs 1 so 1 1 1 1 1 1 1 1 1 S 1 〇CN CO Ώ 1—^ 〇wS CM g ϋ ; ; 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 >-n CS w xr^ οό c<\ ο «—Η vn Ο 2; rupture 〇〇σ\ CS CN 11 1 § 1 1 1 1 1 1 1 1 1 〇<N 1 ο (Ν CN 1 Melt melt Μ 〇 melt jo 1 wear s 1 1 1 1 1 1 1 1 1 Ο cs ο ιη CN 1 ο 8 CS § 〇§ 1 1 g 1 1 1 1 1 VO 1 1 1 Ο ι—Η 1 W-) wS «—Η g 〇ο § a\ 1 1 1 1 1 1 1 1 〇1-H 1 1 〇〇1 Ο (Ν ο irj § CS Ο Μ ο oo 1 1 g 1 1 1 1 1 CO 1 g 1 卜 1 ο ι〇σ\ 1—Η g cs Ο aj o ο 〇 JQ 2 cn 1 〇 \ 1 1 1 1 1 No 1 1 1 1 1 〇〇<Ν S »-Η 沄cn Vn <N ο 2: Μ 〇v〇I & 1 IQ 1 1 1 1 1 1 1 1 1 Ο CS 1/Ί RO ON cs w ο Rupture ΟΟ ΟΝ Comparative example tube No 2 (*2) 1 ( *3) 2(*4) 1(*12) 2(*13) 3(*14) 4(*15) 1(*5) 2(*6) 3(*7) 1(*8) 2(*9) 1(*10) 2(*11) Electron wire irradiation amount (kGy) Expansion diameter - heat shrinkage treatment Tensile strength (MPa) Extension (%) Tensile strength (MPa) Extension (%) Flame retardant thermal shock resistance to heat deformation (% retention) Polyphenylene ether « m κι m 浒静; m <n 临 磷 Phosphorus-based nitrogen compound m Tensile property mmm I 200948895 Reference tube No. 3 1,32 : The soft Noryl resin compound manufactured by S ABIC Innovation Plastics Co., Ltd. was extruded in the same manner as in the above examples to obtain a tubular molded article. The obtained tube was subjected to electron beam irradiation in the same manner as in Example 1, and further subjected to diameter expansion-heat shrinkage treatment to produce tube No. 3 1,32. The produced tube was evaluated for tensile properties, heat resistance, flame retardancy, heat deformation resistance, and thermal shock according to the above evaluation method. The results are shown in Table 3. [Table 3] Reference tube No. 31 32 WCD801-BK1066 100 _ WCD891A-BK1066 — 100 Electron beam irradiation (kGy) 250 250 Expansion diameter - hot female treatment has pull. Tensile strength (MPa) 17.0 19.0 Extension extension ( %) 230 280 Characteristic tensile strength (MPa) 20.0 22.0 Thermal elongation (%) 70 80 Non-flammable NG NG Thermal shock Melt-melting Heat-resistant deformation (% retention) 12 15
No .1至9均爲含有聚苯醚5至80質量％及苯乙烯系熱塑 性彈性體95至20質量％之基質聚合物，該基質聚合物每 100質量份含有：磷系難燃劑5至100質量份、氮系有機 化合物3至80質量份、及多官能性單體丨至20質量份之 難燃性樹脂組成物作爲材料，藉由電子束照射而予以交聯 之管，拉伸特性、難燃性、耐熱性、耐熱變形性、熱震試 -25- 200948895 驗爲合格等級。又，No.10至15在作爲基質聚合物，在使 用到聚苯醚20至40質量％、苯乙烯系熱塑性彈性體20至 30質量％、烯烴系聚合物40至50質量％之掺合的情形，藉 由電子束照射所交聯之管的拉伸特性、難燃性、耐熱性、 耐熱變形性、熱震試驗均爲合格等級。No.7、8、9在爲各 自No .1、3、6之管與材料的樹脂組成物爲相同。在比較各 自對應的管之評價結果時，根據擴徑-熱收縮處理，其特性 幾乎並不降低，可保持處理前之特性爲自明。 ® No.24係不進行電子束照射之管，No.22係不含有多官 能性單體的樹脂組成物所構成的管。在耐熱性試驗、熱震 試驗管均熔融，並無法保持形狀。該等因並不進行電子束 照射，或因不含有多官能性單體，故無法獲得電子束照射 所致交聯效果，且無法耐受高溫加熱處理。因此，在以高 溫加熱處理爲前提之熱收縮管方面，並無法使用。 由於多官能性單體含量過多（No.23)，在基質聚合物中若 聚苯醚之含有率過低（No.17)，磷系難燃劑之含量過少 ® (No. 18)，聚烯烴系樹脂過多（No .26)時，並無法滿足難燃性。 一方面，在基質聚合物中聚苯醚與苯乙烯系熱塑性彈性 體之含有比率爲適當，且含有適量磷系難燃劑、多官能性 單體，即使進行電子束照射所致交聯處理’在氮化合物含 有3質量份之情形（No .6)雖可滿足難燃性’然而在只含有 氮系化合物1質量份之情形（No. 21)則並無法滿足難燃性。 由此可知，氮化合物與磷系難燃劑之倂用’爲了確保難燃 性極爲有用爲自明。 -26- 200948895 藉由使磷系難燃劑之含量變大（No.19)，或在基質聚合 中藉由使聚苯醚之含有比率提高（No. 1 6)，即使不含有氮 合物雖可滿足難燃性，然而由於磷系化合物之含量增大 得加熱處理所致變形量變大（No. 19)，由於聚苯醚之含有 率增大（No. 16)，因高溫加熱而使延伸過度降低而無法確 耐熱性、熱震試驗之合格等級。 又，在No.25於基質聚合物中使聚苯醚與苯乙烯系熱 性彈性體之含有比率在本發明之範圍內，進而配合適當 ® 的氮系化合物、多官能性單體，而可獲得交聯效果，而 震試驗爲合格，但在高溫下之延伸、耐熱變形性則劣化 一方面，No.21係減低氮系化合物量，增加磷系化合物 含量，而可獲得交聯效果之物。雖然均無法滿足難燃性 然而爲了確保在高溫下之延伸、耐熱變形性，則以1〇〇 以下的磷系化合物較有用爲自明。 進而，由No.4與Νο·19之比較可知，在使用到不含 烴系聚合物的基質聚合物之情形，爲了保持難燃性盥耐 0 性，在高溫之強度，則在基質聚合物中使聚苯醚與苯乙 系彈性體之含有比率（聚苯醚：苯乙烯系彈性體）在5: 至80: 20之範圍，進而藉由氮系化合物與磷系化合物之 用，而可抑制難燃劑之含量總量較有效爲自明。 由No.20與Νο.5之比較可知，氮系化合物之含量過 時延伸傾向於降低，氮系化合物之含量在90質量份亦無 確保初期之拉伸特性。由拉伸特性之點而言，考慮到憐 化合物與氮系化合物之含量均衡有其必要爲自明。 物 化 使 比 保 塑 量 熱 Ο 之 9 份 烯 熱 烯 95 倂 多 法 系 •27- 200948895 此外，由表3可知，在使用到柔軟Noryl之 法滿足管中難燃性，即使進行電子束照射亦無 效果，而在熱震試驗進行熔融，形狀保持造成困 高溫處理後之變形亦變大。 【產業上利用可能性】 本發明之管、熱收縮管，係可滿足UL規格 驗難燃性之非鹵素型之管，而且，即使在高溫 UL規格之拉伸特性、強度、耐熱變形，故； ^ (electronic equipment)、辦公室自動化 OA 機器 視、DVD、藍光（Blu-Ray)等民生用電子設備類 舶等內部配線或零件之保護所使用之管，進而 包裝、保護用之熱收縮管來使用。 【圖式簡單說明】 無。 【主要元件符號說明】No. 1 to 9 are each a matrix polymer containing 5 to 80% by mass of polyphenylene ether and 95 to 20% by mass of a styrene-based thermoplastic elastomer, and the matrix polymer contains: phosphorus-based flame retardant 5 to 100 parts by mass. 100 parts by mass, a nitrogen-based organic compound of 3 to 80 parts by mass, and a polyfunctional monomer 丨 to 20 parts by mass of a flame retardant resin composition as a material, a tube crosslinked by electron beam irradiation, tensile characteristics , flame retardancy, heat resistance, heat deformation resistance, thermal shock test -25,48,895,895. Further, No. 10 to 15 are blended as a matrix polymer in an amount of 20 to 40% by mass of the polyphenylene ether, 20 to 30% by mass of the styrene-based thermoplastic elastomer, and 40 to 50% by mass of the olefin-based polymer. In the case, the tensile properties, flame retardancy, heat resistance, heat deformation resistance, and thermal shock test of the tube crosslinked by electron beam irradiation are all acceptable levels. No. 7, 8, and 9 are the same as the resin composition of the tube and the material of No. 1, 3, and 6. When the evaluation results of the respective tubes are compared, the characteristics are hardly lowered according to the diameter expansion-heat shrinkage treatment, and the characteristics before the treatment can be kept self-evident. ® No. 24 is a tube that does not emit electron beams, and No. 22 is a tube that does not contain a resin composition of a multi-functional monomer. In the heat resistance test and the thermal shock test tube, the tubes were melted and the shape could not be maintained. Since the electron beam irradiation is not performed or the polyfunctional monomer is not contained, the crosslinking effect by the electron beam irradiation cannot be obtained, and the high-temperature heat treatment cannot be tolerated. Therefore, it is not possible to use a heat shrinkable tube which is premised on high-temperature heat treatment. Due to the excessive content of polyfunctional monomer (No. 23), if the content of polyphenylene ether in the matrix polymer is too low (No. 17), the content of the phosphorus-based flame retardant is too low (No. 18), When the amount of the olefin resin is too large (No. 26), the flame retardancy cannot be satisfied. On the one hand, the content ratio of the polyphenylene ether to the styrene-based thermoplastic elastomer in the matrix polymer is appropriate, and an appropriate amount of the phosphorus-based flame retardant and the polyfunctional monomer are contained, and the crosslinking treatment is performed even by electron beam irradiation. In the case where the nitrogen compound contains 3 parts by mass (No. 6), the flame retardancy is satisfied. However, in the case where only 1 part by mass of the nitrogen-based compound is contained (No. 21), the flame retardancy cannot be satisfied. From this, it is understood that the use of a nitrogen compound and a phosphorus-based flame retardant is very useful for ensuring flame retardancy. -26- 200948895 By increasing the content of the phosphorus-based flame retardant (No. 19), or by increasing the content ratio of the polyphenylene ether in the matrix polymerization (No. 16), even if it does not contain the nitrogen compound Although the flame retardancy is satisfied, the amount of deformation of the phosphorus-based compound increases due to the increase in the content of the phosphorus-based compound (No. 19), and the content of the polyphenylene ether increases (No. 16), which is caused by high-temperature heating. The elongation is excessively lowered and the heat resistance and the thermal shock test are not acceptable. Further, in No. 25, the content ratio of the polyphenylene ether to the styrene-based thermal elastomer in the matrix polymer is within the range of the present invention, and further, a suitable nitrogen compound or polyfunctional monomer is obtained. The cross-linking effect is acceptable, but the vibration test is acceptable, but the elongation at high temperature and the heat deformation resistance are deteriorated. On the other hand, No. 21 is a substance which reduces the amount of the nitrogen-based compound and increases the content of the phosphorus-based compound to obtain a crosslinking effect. Although it is difficult to satisfy the flame retardancy, in order to ensure elongation at a high temperature and heat deformation resistance, a phosphorus-based compound of 1 Torr or less is more self-evident. Further, from the comparison between No. 4 and Νο·19, it is understood that in the case of using a matrix polymer containing no hydrocarbon-based polymer, in order to maintain flame resistance and resistance to zero, the strength at high temperature is in the matrix polymer. The content ratio of the polyphenylene ether to the styrene-based elastomer (polyphenylene ether: styrene-based elastomer) is in the range of 5: to 80: 20, and is further used by the nitrogen-based compound and the phosphorus-based compound. It is self-evident that the total amount of the flame retardant is suppressed. From the comparison between No. 20 and Νο. 5, it is found that the content of the nitrogen-based compound tends to decrease over time, and the content of the nitrogen-based compound does not ensure the initial tensile properties at 90 parts by mass. From the viewpoint of the tensile properties, it is necessary to consider the balance between the pity compound and the nitrogen compound. Physicochemically, it is more than 9 parts of enephene 95 倂 法 • • • 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 It has no effect, and the deformation after melting in the thermal shock test and the shape retention causes the high temperature treatment to become high. [Industrial Applicability] The tube and the heat-shrinkable tube of the present invention are non-halogen type tubes which can meet the UL standard for determining flame retardancy, and even in the high temperature UL specification, the tensile properties, strength, and heat deformation are caused. ^ (electronic equipment), office automation OA machine vision, DVD, Blu-ray (Blu-Ray) and other electronic equipment such as the use of internal wiring or parts of the protection of the tube, and then the packaging and protection of the heat shrinkable tube use. [Simple description of the diagram] None. [Main component symbol description]
Anr 無0 ❹ 情形，並無 法獲得交聯 難的狀態， 之VW-1試 下因可滿足 &電子設備 、音響、影 、車輛、船 可作爲密接 -28-Anr has no 0 ❹ In case, it is impossible to obtain a difficult state of cross-linking. The VW-1 test can be used to meet the requirements of electronic equipment, audio, video, vehicles, and ships.