TW201920409A - 組合物及難燃性樹脂組合物 - Google Patents
組合物及難燃性樹脂組合物 Download PDFInfo
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- TW201920409A TW201920409A TW107130809A TW107130809A TW201920409A TW 201920409 A TW201920409 A TW 201920409A TW 107130809 A TW107130809 A TW 107130809A TW 107130809 A TW107130809 A TW 107130809A TW 201920409 A TW201920409 A TW 201920409A
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Abstract
本發明之組合物含有(A)磷酸胺鹽及(B)氰尿酸三聚氰胺。本發明之組合物較佳為上述(A)成分含有下述(A-1)及(A-2)。 (A-1)成分:選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群中之至少一種三聚氰胺鹽 (A-2)成分:選自由正磷酸哌、焦磷酸哌及多磷酸哌所組成之群中之至少一種哌鹽。 根據本發明,可提供一種藉由混合於樹脂中而可賦予抗滴落效果,對該樹脂賦予優異之難燃性,且可獲得表面平滑性良好之成形品之組合物。
Description
本發明係關於一種含有磷酸胺鹽及氰尿酸三聚氰胺之組合物及調配有該組合物之難燃性樹脂組合物。
先前,合成樹脂因優異之化學、機械特性而被廣泛地用於建築材料、汽車零件、包裝用材料、農業用材料、家電製品之殼體材料、玩具等。然而,多數合成樹脂為可燃性物質,視用途而難燃化不可欠缺。作為難燃化方法,廣為大眾所知的是將鹵素系難燃劑、以赤磷或多磷酸銨等多磷酸系難燃劑為代表之無機磷系難燃劑、以三芳基磷酸酯化合物為代表之有機磷系難燃劑、金屬氫氧化物或作為難燃助劑之氧化銻、三聚氰胺化合物單獨或組合而使用。
尤其已知有一種膨脹系難燃劑,其係以多磷酸或焦磷酸及含氮化合物之鹽作為主成分,於燃燒時形成表面膨脹層(Intumescent),抑制分解產物之擴散或傳熱,藉此發揮難燃性。此種難燃劑例如記載於專利文獻1中。
於專利文獻2中,揭示有含有磷化合物、三聚氰胺、及氰尿酸之反應物之難燃劑。然而,於該難燃劑中含有20質量%左右之氰尿酸三聚氰胺,就樹脂物性之降低或經濟上之觀點而言存在問題。
於專利文獻3中,揭示有含有利用偶合劑進行過表面處理之氰尿酸三聚氰胺之難燃性樹脂組合物。於該難燃性樹脂組合物中,相對於樹脂調配10質量%左右之經表面處理之氰尿酸三聚氰胺,就樹脂之機械特性之降低或經濟上之觀點而言存在問題。
於專利文獻4中,揭示有於聚烯烴系樹脂中添加作為無機物之氫氧化鎂與聚矽氧聚合物、及氰尿酸三聚氰胺而成之難燃性樹脂組合物。然而,該難燃性樹脂組合物含有30質量%左右之氰尿酸三聚氰胺作為難燃劑,進而無機物之合計量亦為70質量%左右,故而不僅難燃性能,於加工性或成形品之表面平滑性之方面亦存在問題。 [先前技術文獻] [專利文獻]
[專利文獻1]US2014/200292A1 [專利文獻2]WO2014/080821A1 [專利文獻3]日本專利特開2003-226798號公報 [專利文獻4]日本專利特開2000-178386號公報
於使用樹脂材料之各種用途中,對防火性之要求不斷提高,隨之,對樹脂組合物所要求之難燃性能之水準亦越來越高。 然而,就抗滴落效果而言,上述先前之難燃劑並不充分。 本發明之課題在於提供一種藉由混合於樹脂中而可賦予抗滴落效果,對該樹脂賦予優異之難燃性之組合物,及含有該組合物與樹脂且發揮優異之難燃性之難燃性樹脂組合物。
本發明者等人努力研究解決上述課題之構成,結果發現:藉由將組合有胺之磷酸鹽與氰尿酸三聚氰胺之組合物混合於樹脂中,而表現優異之表面平滑性及抗滴落效果。 本發明係基於上述之見解者,提供一種組合物,其含有(A)磷酸胺鹽及(B)氰尿酸三聚氰胺。
又,本發明提供一種難燃性樹脂組合物及其成形體,該難燃性樹脂組合物含有樹脂及上述組合物。 又,本發明提供一種樹脂之難燃化方法,其係將含有上述(A)成分及上述(B)成分之組合物與樹脂進行混合。 進而,本發明提供一種組合物之用途,其係將含有上述(A)成分及上述(B)成分之組合物用作難燃劑。
以下,對本發明基於其較佳之實施形態詳細地進行說明。 再者,於以下之說明中,所謂難燃性,意指物質不易著火,又,即便著火而燃燒持續,其速度亦非常慢,或其後自熄之性質,較佳為意指具有實施例中記載之依據UL-94V標準之燃燒等級中之至少V-2之等級,更佳為意指具有V-1或V-0之等級。所謂難燃劑組合物,意指含有難燃劑之一種以上之組合物。所謂難燃性樹脂組合物,意指具有上述之難燃性且含有至少一種合成樹脂之組合物。
本發明之組合物於含有上述(A)成分及上述(B)成分之方面具有特徵之一。 首先,對本發明之組合物中所含之作為(A)成分之磷酸胺鹽進行說明。所謂磷酸胺鹽,係指磷酸與胺之鹽。 於本發明中,所謂磷酸,意指五氧化二磷進行水合而形成之酸,具體而言,可列舉正磷酸、焦磷酸及多磷酸。該等磷酸可分別單獨使用,或可將兩種以上組合而使用。 作為胺,其種類並無特別限制,例如可列舉芳香族胺及雜環式脂肪族胺。該等胺可分別單獨使用,或可將兩種以上組合而使用。
作為芳香族胺,例如可列舉於芳香族烴環上鍵結有1個或2個以上之胺基之化合物。該芳香族烴環中之1個或2個以上之碳原子有被例如氮、氧或硫等雜原子取代之情況。作為於芳香族烴環上鍵結有1個或2個以上之胺基之芳香族胺,例如可列舉苯胺或苯二胺等。另一方面,作為芳香族烴環中之1個或2個以上之碳原子被雜原子取代之芳香族胺,例如可列舉:具有1個氮原子作為雜原子之化合物之胺基吡啶、或具有2個氮原子作為雜原子之化合物之胺基吡、或具有3個氮原子作為雜原子之化合物之胺基三等。尤其可較佳地使用具有3個氮原子作為雜原子之化合物之胺基三,尤佳為使用作為具有3個胺基之三之三聚氰胺。
作為雜環式脂肪族胺,例如可列舉五員環之雜環式脂肪族胺及六員環之雜環式脂肪族胺。
作為五員環之雜環式脂肪族胺,例如可列舉包含1個氮原子之五員環之雜環式脂肪族胺及包含2個氮原子之五員環之雜環式脂肪族胺。作為包含1個氮原子之五員環之雜環式脂肪族胺,例如可列舉吡咯啶。作為包含2個氮原子之五員環之雜環式脂肪族胺,可列舉吡唑啶。另一方面,作為六員環之雜環式脂肪族胺,例如可列舉包含1個氮原子之六員環之雜環式脂肪族胺及包含2個氮原子之六員環之雜環式脂肪族胺。作為包含1個氮原子之六員環之雜環式脂肪族胺,例如可列舉哌啶。作為包含2個氮原子之六員環之雜環式脂肪族胺,例如可列舉哌。於本發明中,作為雜環式胺,較佳為使用包含2個氮原子之六員環之雜環式脂肪族胺,尤佳為使用哌。
於本發明之組合物中,用作(A)成分之磷酸胺鹽較佳為含有(A-1)成分:選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群中之至少一種三聚氰胺鹽及(A-2)成分:選自由正磷酸哌、焦磷酸哌及多磷酸哌所組成之群中之至少一種哌鹽。
於本發明之組合物中,用作(A-1)成分之三聚氰胺鹽係選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群。該等三聚氰胺鹽有時僅使用一種,亦有時以兩種以上之混合物之形式使用。該等中,就難燃性、處理性、保存穩定性之方面而言,較佳為使用焦磷酸三聚氰胺。於以混合物之形式使用三聚氰胺鹽之情形時,較佳為該混合物中之焦磷酸三聚氰胺之以質量基準計之含有比率最高。 該等磷酸與三聚氰胺之鹽可藉由使分別對應之磷酸或磷酸鹽與三聚氰胺反應而獲得。尤其本發明之(A-1)成分中所使用之三聚氰胺鹽較佳為使正磷酸三聚氰胺加熱縮合所獲得之焦磷酸三聚氰胺或多磷酸三聚氰胺,尤佳為焦磷酸三聚氰胺。
於本發明之組合物中,用作(A-2)成分之哌鹽係選自由正磷酸哌、焦磷酸哌及多磷酸哌所組成之群。該等哌鹽有時僅使用一種,亦有時以兩種以上之混合物之形式使用。該等中,就難燃性、處理性、保存穩定性之方面而言,較佳為使用焦磷酸哌,於以混合物之形式使用哌鹽之情形時,較佳為該混合物中之焦磷酸哌之以質量基準計之含有比率最高。 該等磷酸與哌之鹽可藉由使分別對應之磷酸或磷酸鹽與哌反應而獲得。尤其本發明之(A-2)成分中所使用之哌鹽較佳為使正磷酸哌加熱縮合所獲得之焦磷酸哌或多磷酸哌,尤佳為焦磷酸哌。
本發明之組合物中所含之(A)成分較佳為僅包含(A-1)成分及(A-2)成分。於該情形時,關於(A)成分中之(A-1)成分之含量,以(A)成分100質量份計,較佳為10~50質量份,更佳為20~50質量份。關於(A)成分中之(A-2)成分之含量,以(A)成分100質量份計,較佳為90~50質量份,更佳為80~50質量份。
又,於本發明之組合物中,(A)成分之合計量較佳為70~99.9質量%,更佳為80~99質量%。就提高滴落效果之方面而言,較佳為(A)成分之含量為70質量%以上,就確保其他任意成分量而提高本發明之效果之方面而言,較佳為99.9質量%以下。本發明之組合物中之作為(A-1)成分之三聚氰胺鹽及作為(A-2)成分之哌鹽所代表之作為(A)成分之磷酸胺鹽之含量可藉由離子層析法而測定。
其次,對本發明之組合物之(B)成分進行說明。 本發明之組合物中之作為(B)成分之氰尿酸三聚氰胺係三聚氰胺與氰尿酸之有機鹽。 作為氰尿酸三聚氰胺,可使用市售品。作為氰尿酸三聚氰胺之市售品,例如可列舉:日產化學工業(股)之MC-4000、MC-4500、MC-6000等。 作為氰尿酸三聚氰胺之製造方法,可列舉公知之方法。例如於日本專利特開平7-188193號公報或日本專利特開平7-149739號公報等中有所揭示。
於本發明之組合物中,關於上述(B)成分之含量,相對於上述(A)成分100質量份,較佳為0.1~20質量份,就難燃性之方面而言,較佳為0.5~20質量份,更佳為1~20質量份,進而較佳為3~10質量份。藉由將(B)成分之含量設定為0.1質量份以上,有抗滴落、表面膨脹層形成之優點。另一方面,藉由將(B)成分之含量設定為20質量份以下,就加工時之機械污染及加工成形性之方面而言具有優點。 於本發明之組合物中,上述(B)成分之含量例如可藉由紅外分光法、氣相層析法、氣相層析-質譜法等而測定。
於本發明之組合物中,可進而含有氧化鋅(ZnO)(以下,將該成分亦稱為「(C)成分」)。
上述氧化鋅係作為難燃助劑而發揮功能。該氧化鋅有經表面處理之情況。氧化鋅可使用市售品,例如可列舉:氧化鋅1種(三井金屬礦業(股)製造)、部分覆膜型氧化鋅(三井金屬礦業(股)製造)、Nanofine 50(平均粒徑0.02 μm之超微粒子氧化鋅:堺化學工業(股)製造)、Nanofine K(平均粒徑0.02 μm之經矽酸鋅覆膜之超微粒子氧化鋅:堺化學工業(股)製造)等。
於本發明之組合物中,關於作為上述(C)成分之氧化鋅之含量,就難燃性之方面而言,相對於上述(A)成分100質量份,較佳為0.01~10質量份,更佳為0.5~8質量份,進而較佳為1~5質量份。藉由將氧化鋅之含量設定為0.01質量份以上,而難燃性變得更良好。另一方面,藉由將氧化鋅之含量設定為10質量份以下,而不易對加工性產生不良影響。
就防止難燃劑粉末凝聚,謀求保存穩定性之提高、於合成樹脂中之分散性提高或難燃性提高之方面而言,本發明之組合物較佳為進而含有選自聚矽氧油、環氧系偶合劑、水滑石及潤滑劑中之至少一種((D)成分)。
作為聚矽氧油之例,可列舉:聚矽氧烷之側鏈、末端均為甲基之二甲基聚矽氧油、聚矽氧烷之側鏈、末端為甲基且其側鏈之一部分為苯基之甲基苯基聚矽氧油、聚矽氧烷之側鏈、末端為甲基且其側鏈之一部分為氫之甲基氫聚矽氧油等、或該等之共聚物,又,可使用於該等之側鏈及/或末端之一部分導入有有機基之經胺改性、環氧改性、脂環式環氧改性、羧基改性、甲醇改性、巰基改性、聚醚改性、長鏈烷基改性、氟烷基改性、高級脂肪酸酯改性、高級脂肪醯胺改性、矽烷醇改性、二醇改性、酚改性及/或芳烷基改性之改性聚矽氧油。
列舉上述聚矽氧油之具體例,作為二甲基聚矽氧油,可列舉:KF-96(信越化學(股)製造)、KF-965(信越化學(股)製造)、KF-968(信越化學(股)製造)等,作為甲基氫聚矽氧油,可列舉:KF-99(信越化學(股)製造)、KF-9901(信越化學(股))、HMS-151(Gelest公司製造)、HMS-071(Gelest公司製造)、HMS-301(Gelest公司製造)、DMS-H21(Gelest公司製造)等,作為甲基苯基聚矽氧油之例,可列舉:KF-50(信越化學(股)製造)、KF-53(信越化學(股)製造)、KF-54(信越化學(股)製造)、KF-56(信越化學(股)製造)等,作為環氧改性品,例如可列舉:X-22-343(信越化學(股)製造)、X-22-2000(信越化學(股)製造)、KF-101(信越化學(股)製造)、KF-102(信越化學(股)製造)、KF-1001(信越化學(股)製造),作為羧基改性品,例如可列舉:X-22-3701E(信越化學(股)製造),作為甲醇改性品,例如可列舉:X-22-4039(信越化學(股)製造)、X-22-4015(信越化學(股)製造),作為胺改性品,例如可列舉:KF-393(信越化學(股)製造)等。
於本發明之組合物中,聚矽氧油中,就防止難燃劑粉末凝聚,提高保存穩定性,及提高於合成樹脂中之分散性之方面而言,較佳為甲基氫聚矽氧油。
環氧系偶合劑具有防止難燃劑粉末之凝聚,用以提高保存穩定性,或賦予耐水性、耐熱性之功能。作為環氧系偶合劑,例如可列舉由通式A-(CH2
)k
-Si(OR)3
表示且具有環氧基之化合物。A為環氧基,k表示1~3之數,R表示甲基或乙基。作為此處所謂之環氧基,可列舉縮水甘油氧基或3,4-環氧環己基。 作為環氧系偶合劑之具體例,例如作為具有環氧基之矽烷偶合劑,可列舉:2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、縮水甘油氧基辛基三甲氧基矽烷等。
所謂水滑石,係指包含作為天然物或合成物所知之鎂、鋁、羥基、碳酸基及任意結晶水之複合鹽化合物,可列舉:鎂或鋁之一部分被鹼金屬或鋅等其他金屬取代而成者或羥基、碳酸基被其他陰離子基取代而成者。具體而言,例如可列舉:下述式(3)所表示之水滑石、或該式(3)所表示之水滑石之金屬被取代為鹼金屬而成者。又,作為Al-Li系水滑石,亦可使用式(4)所表示之化合物。
[化1]
(式中,x1及x2分別表示滿足下述式所表示之條件之數,p表示0或正數,0≦x2/x1<10,2≦x1+x2≦20)
[化2]
(式中,Aq-
表示q價之陰離子,p表示0或正數)
又,上述水滑石中之碳酸陰離子有一部分被其他陰離子取代之情況。 上述水滑石亦可為脫除結晶水者,有由硬脂酸等高級脂肪酸、油酸鹼金屬鹽等高級脂肪酸金屬鹽、十二烷基苯磺酸鹼金屬鹽等有機磺酸金屬鹽、高級脂肪醯胺、高級脂肪酸酯或蠟等被覆之情況。
作為潤滑劑,可列舉:液態石蠟、天然石蠟、微晶蠟、合成石蠟、低分子量聚乙烯、聚乙烯蠟等純烴系潤滑劑;鹵化烴系潤滑劑;高級脂肪酸、含氧脂肪酸等脂肪酸系潤滑劑;脂肪醯胺、雙脂肪醯胺等脂肪醯胺系潤滑劑;脂肪酸之低級醇酯、甘油酯等脂肪酸之多元醇酯、脂肪酸之聚二醇酯、脂肪酸之脂肪醇酯(酯蠟)等酯系潤滑劑;金屬皂、脂肪醇、多元醇、聚二醇、聚甘油、脂肪酸與多元醇之部分酯、脂肪酸與聚二醇、聚甘油之部分酯系潤滑劑、或聚矽氧油、礦物油等。潤滑劑可單獨使用一種,亦可併用兩種以上而使用。
就提高難燃性之方面而言,於在本發明之組合物中含有選自聚矽氧油、環氧系偶合劑、水滑石及潤滑劑中之至少一種((D)成分)之情形時,本發明之組合物中,就可有效地發揮含有上述E成分之效果之觀點而言,E成分之含量相對於上述(A)成分100質量份,較佳為0.01~5質量份,更佳為0.01~3質量份。
尤其是於本發明之組合物中含有聚矽氧油之情形之聚矽氧油之含量,就提高藉由含有聚矽氧油所獲得之上述效果之方面而言,相對於上述(A)成分100質量份,較佳為0.01~3質量份,更佳為0.1~1質量份。
尤其是於本發明之組合物中含有環氧系偶合劑之情形之環氧系偶合劑之含量,就提高藉由含有環氧系偶合劑所獲得之上述效果之方面而言,相對於上述(A)成分100質量份,較佳為0.01~3質量份,更佳為0.1~1質量份。
尤其是於本發明之組合物中含有水滑石之情形之水滑石之含量,就提高藉由含有水滑石所獲得之上述效果之方面而言,相對於上述(A)成分100質量份,較佳為0.01~5質量份,更佳為0.1~0.5質量份。
於本發明之組合物中含有潤滑劑之情形之潤滑劑之含量,就提高藉由含有潤滑劑所獲得之上述之效果之方面而言,相對於上述(A)成分100質量份,較佳為0.01~3質量份,更佳為0.1~0.5質量份。
於本發明中所使用之組合物中,可視需要調配酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑、其他抗氧化劑、成核劑、紫外線吸收劑、光穩定劑、塑化劑、填充劑、脂肪酸金屬鹽、抗靜電劑、顏料、染料等。 該等成分可預先調配於本發明之組合物中,可於調配於合成樹脂中時調配於合成樹脂中。較佳為藉由調配該等而使合成樹脂穩定化。
作為上述酚系抗氧化劑,例如可列舉:2,6-二第三丁基-4-甲基苯酚、2,6-二第三丁基-4-乙基苯酚、2-第三丁基-4,6-二甲基苯酚、苯乙烯化苯酚、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、2,2'-硫代雙-(6-第三丁基-4-甲基苯酚)、2,2'-硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2-甲基-4,6-雙(辛基硫基甲基)苯酚、2,2'-亞異丁基雙(4,6-二甲基苯酚)、3-(3,5-二第三丁基-4-羥基苯基)丙酸異辛酯、N,N'-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、2,2'-草醯胺-雙[乙基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、3-(3',5'-二第三丁基-4'-羥基苯基)丙酸2-乙基己酯、2,2'-伸乙基雙(4,6-二第三丁基苯酚)、3,5-二第三丁基-4-羥基-苯丙酸及C13-15烷基之酯、2,5-二第三戊基對苯二酚、受阻酚之聚合物(ADEKA PALMAROLE公司製造之商品名AO.OH.98)、2,2'-亞甲基雙[6-(1-甲基環己基)對甲酚]、丙烯酸2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯酯、丙烯酸2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯酯、6-[3-(3-第三丁基-4-羥基-5-甲基)丙氧基]-2,4,8,10-四第三丁基苯并[d,f][1,3,2]-二氧雜磷雜環庚烯(dioxaphosphobin)、六亞甲基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、雙[(3,5-二第三丁基-4-羥基苄基)膦酸單乙酯]鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)苯并呋喃酮與鄰二甲苯之反應產物、2,6-二第三丁基-4-(4,6-雙(辛硫基)-1,3,5-三-2-基胺基)苯酚、DL-a-生育酚(維生素E)、2,6-雙(α-甲基苄基)-4-甲基苯酚、雙[3,3-雙(4'-羥基-3'-第三丁基苯基)丁酸]二醇酯、2,6-二第三丁基對甲酚、2,6-二苯基-4-十八烷氧基苯酚、(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酯、(3,5-二第三丁基-4-羥基苄基)膦酸二硬脂酯、3,5-第三丁基-4-羥基苄基硫代乙酸十三烷基酯、硫代二伸乙基雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、4,4-硫代雙(6-第三丁基間甲酚)、2-辛硫基-4,6-二(3,5-二第三丁基-4-羥基苯氧基)均三、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]二醇酯、4,4'-亞丁基雙(2,6-二第三丁基苯酚)、4,4'-亞丁基雙(6-第三丁基-3-甲基苯酚)、2,2'-亞乙基雙(4,6-二第三丁基苯酚)、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、對苯二甲酸雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]酯、異氰尿酸1,3,5-三(2,6-二甲基-3-羥基-4-第三丁基苄基)酯、異氰尿酸1,3,5-三(3,5-二第三丁基-4-羥基苄基)酯、1,3,5-三(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、異氰尿酸1,3,5-三[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]酯、四[亞甲基-3-(3',5'-二第三丁基-4'-羥基苯基)丙酸酯]甲烷、2-第三丁基-4-甲基-6-(2-丙烯醯氧基-3-第三丁基-5-甲基苄基)苯酚、3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙[3-第三-4-羥基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、棕櫚基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、肉豆蔻基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、月桂基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺等之3-(3,5-二烷基-4-羥基苯基)丙酸衍生物等。該等酚系抗氧化劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等酚系抗氧化劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
上述亞磷酸酯系抗氧化劑例如可列舉:亞磷酸三苯酯、亞磷酸二異辛酯、七(二丙二醇)三亞磷酸酯、亞磷酸三異癸酯、亞磷酸二苯基異辛基酯、亞磷酸二異辛基苯基酯、亞磷酸二苯基十三烷基酯、亞磷酸三異辛酯、亞磷酸三月桂酯、亞磷酸二苯酯、三(二丙二醇)亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、氫亞磷酸二油酯、三硫代亞磷酸三月桂酯、亞磷酸雙(十三烷基)酯、亞磷酸三(異癸基)酯、亞磷酸三(十三烷基)酯、亞磷酸二苯基癸基酯、雙(壬基苯基)亞磷酸二壬基苯基酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙二醇二亞磷酸酯、亞磷酸三(壬基苯基)酯、亞磷酸三(2,4-二第三丁基苯基)酯、亞磷酸三(2,4-二第三丁基-5-甲基苯基)酯、亞磷酸三[2-第三丁基-4-(3-第三丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基]酯、亞磷酸三(癸基)酯、亞磷酸辛基二苯基酯、亞磷酸二(癸基)單苯基酯、二硬脂基季戊四醇二亞磷酸酯、二硬脂基季戊四醇與硬脂酸鈣鹽之混合物、烷基(C10)雙酚A亞磷酸酯、二(十三烷基)季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,4-二異丙苯基苯基)季戊四醇二亞磷酸酯、四(十三烷基)季戊四醇四亞磷酸四苯酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)乙基酯、亞異丙基二苯酚二亞磷酸四(十三烷基)酯、4,4'-正亞丁基雙(2-第三丁基-5-甲基苯酚)二亞磷酸四(十三烷基)酯、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸六(十三烷基)酯、伸聯苯基二亞磷酸四(2,4-二第三丁基苯基)酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、(1-甲基-1-丙烯基-3-亞基)三(1,1-二甲基乙基)-5-甲基-4,1-伸苯基)六(十三烷基)亞磷酸酯、2,2'-亞甲基雙(4,6-二第三丁基苯基)-2-乙基己基亞磷酸酯、2,2'-亞甲基雙(4,6-二第三丁基苯基)十八烷基亞磷酸酯、2,2'-亞乙基雙(4,6-二第三丁基苯基)氟亞磷酸酯、4,4'-亞丁基雙(3-甲基-6-第三丁基苯基二(十三烷基))亞磷酸酯、三(2-[(2,4,8,10-四第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯-6-基)氧基]乙基)胺、3,9-雙(4-壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺環[5,5]十一烷、2,4,6-三第三丁基苯基-2-丁基-2-乙基-1,3-丙二醇亞磷酸酯、4,4'-亞異丙基二苯酚C12-15醇亞磷酸酯、3,9-雙(2,6-二第三丁基-4-甲基苯基)-3,9-雙-二膦-2,4,8,10-四氧雜-3,9-二磷雜螺環[5,5]十一烷、亞磷酸二苯基(異癸基)酯、亞磷酸聯苯二苯酯等。該等亞磷酸酯系抗氧化劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等亞磷酸酯系抗氧化劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
上述硫醚系抗氧化劑例如可列舉:3,3'-硫代二丙酸、烷基(C12-14)硫代丙酸、3,3'-硫代二丙酸二(月桂基)酯、3,3'-硫代雙丙酸二(十三烷基)酯、3,3'-硫代二丙酸二(肉豆蔻基)酯、3,3'-硫代二丙酸二(硬脂基)酯、3,3'-硫代二丙酸二(十八烷基)酯、硫代二丙酸月桂硬脂酯、四[亞甲基-3-(十二烷基硫代)丙酸酯]甲烷、硫代雙(2-第三丁基-5-甲基-4,1-伸苯基)雙(3-(十二烷硫基)丙酸酯)、2,2'-硫代二伸乙基雙(3-胺基丁烯酯)、4,6-雙(辛硫基甲基)鄰甲酚、2,2'-硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,2'-硫代雙(6-第三丁基對甲酚)、(3,5-二第三丁基-4-羥基苄基)硫代乙酸2-乙基己酯、4,4'-硫代雙(6-第三丁基-3-甲基苯酚)、4,4'-硫代雙(4-甲基-6-第三丁基苯酚)、4,4'-[硫代雙(亞甲基)]雙(2-第三丁基-6-甲基-1-羥基苄基)、雙(4,6-二第三丁基苯酚-2-基)硫醚、(3,5-二第三丁基-4-羥基苄基)硫代乙酸十三烷基酯、1,4-雙(辛硫基甲基)-6-甲基苯酚、2,4-雙(十二烷硫基甲基)-6-甲基苯酚、二硬脂基二硫醚、雙(甲基-4-[3-正烷基(C12/C14)硫代丙醯氧基]5-第三丁基苯基)硫醚等。該等硫醚系抗氧化劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等硫醚系抗氧化劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
上述其他抗氧化劑例如可列舉:N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-辛基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十七烷基硝酮等硝酮化合物、3-芳基苯并呋喃-2(3H)-酮、3-(烷氧基苯基)苯并呋喃-2-酮、3-(醯氧基苯基)苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-(4-羥基苯基)-苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-{4-(2-羥基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二第三-2-側氧基-2,3-二氫苯并呋喃-3-基)苯氧基)乙氧基)-6-側氧基己基-6-((6-羥基己醯基)氧基)己酸酯、5-二第三丁基-3-(4-((15-羥基-3,6,9,13-四氧雜十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等苯并呋喃化合物等。該等其他抗氧化劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等其他抗氧化劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
作為上述成核劑,例如可列舉:苯甲酸鈉、4-第三丁基苯甲酸鋁鹽、己二酸鈉、雙環[2.2.1]庚烷-2,3-二羧酸二鈉等羧酸金屬鹽,雙(4-第三丁基苯基)磷酸酯鈉、2,2'-亞甲基雙(4,6-二第三丁基苯基)磷酸酯鈉、2,2'-亞甲基雙(4,6-二第三丁基苯基)磷酸酯鋰等磷酸酯金屬鹽,二亞苄基山梨糖醇、雙(甲基亞苄基)山梨糖醇、雙(3,4-二甲基亞苄基)山梨糖醇、雙(對乙基亞苄基)山梨糖醇、雙(二甲基亞苄基)山梨糖醇、1,2,3-三脫氧-4,6:5,7-雙-O-((4-丙基苯基)亞甲基)壬糖醇、1,3:2,4-雙(對甲基亞苄基)山梨糖醇、1,3:2,4-雙-O-亞苄基-D-葡萄糖醇(二亞苄基山梨糖醇)等多元醇衍生物,N,N',N''-三[2-甲基環己基]-1,2,3-丙烷三甲醯胺、N,N',N''-三環己基-1,3,5-苯三甲醯胺、N,N'-二環己基萘二甲醯胺、1,3,5-三(二甲基異丙醯基胺基)苯等醯胺化合物等。該等成核劑可單獨使用一種,亦可併用兩種以上而使用。關於該等成核劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
上述紫外線吸收劑例如可列舉:2,4-二羥基二苯甲酮、5,5'-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)、2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-十二烷氧基二苯甲酮、2,2'-二羥基-4-甲氧基二苯甲酮等二苯甲酮系,或2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)苯并三唑、2-(2-羥基-3,5-二第三丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯并三唑、2,2'-亞甲基雙(4-第三辛基-6-苯并三唑基苯酚)、2-(2-羥基-3-第三丁基-5-羧基苯基)苯并三唑之聚乙二醇酯、2-[2-羥基-3-(2-丙烯醯氧基乙基)-5-甲基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-第三丁基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-第三辛基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-第三丁基苯基]-5-氯苯并三唑、2-[2-羥基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-第三丁基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-第三戊基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-第三丁基-5-(3-甲基丙烯醯氧基丙基)苯基]-5-氯苯并三唑、2-[2-羥基-4-(2-甲基丙烯醯氧基甲基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基-2-羥基丙基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基丙基)苯基]苯并三唑等苯并三唑系,或水楊酸苯酯、間苯二酚單苯甲酸酯、(3,5-二第三丁基-4-羥基)苯甲酸2,4-二第三丁基苯酯、(3,5-二第三丁基-4-羥基)苯甲酸辛酯、(3,5-二第三丁基-4-羥基)苯甲酸十二烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十四烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十六烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十八烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸山崳酯等苯甲酸酯系,或2-乙基-2'-乙氧基草醯替苯胺、2-乙氧基-4'-十二烷基草醯替苯胺、2-乙基-2'-乙氧基-5'-第三丁基草醯替苯胺等取代草醯替苯胺系,或α-氰基-β,β-二苯基丙烯酸乙酯、2-氰基-3-甲基-3-(對甲氧基苯基)丙烯酸甲酯、四(α-氰基-β,β-二苯基丙烯醯氧基甲基)甲烷等氰基丙烯酸酯系,或2-(2-羥基-4-(2-(2-乙基己醯氧基)乙氧基)-4,6-二苯基-1,3,5-三、2,4,6-三(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2-(4,6-二苯基-1,3,5-三-2-基)-5-己氧基苯酚、2-(4,6-二(1,1'-聯苯基)4-基)-1,3,5-三-2-基)-5-(2-乙基己氧基)苯酚等三系。該等紫外線吸收劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等紫外線吸收劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.05~0.5質量份。
上述光穩定劑例如可列舉:硬脂酸2,2,6,6-四甲基-4-哌啶酯、硬脂酸1,2,2,6,6-五甲基-4-哌啶酯、苯甲酸2,2,6,6-四甲基-4-哌啶酯、癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸四(1,2,2,6,6-五甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸雙(2,2,6,6-四甲基-4-哌啶基)-二(十三烷基)酯、1,2,3,4-丁烷四羧酸雙(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)酯、雙(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二第三丁基-4-羥基苄基)丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/丁二酸二乙酯縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-嗎啉基均三縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-第三辛基胺基均三縮聚物、1,5,8,12-四[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)均三-6-基]-1,5,8,12-四氮雜十二烷、1,5,8,12-四[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)均三-6-基]-1,5,8-12-四氮雜十二烷、1,6,11-三[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)均三-6-基]胺基十一烷、1,6,11-三[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)均三-6-基]胺基十一烷、癸二酸雙{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}酯、碳酸雙{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基}酯、Ciba Specialty Chemicals製造之TINUVINNOR 371、甲基丙烯酸2,2,6,6-四甲基-4-哌啶酯、1,2,3,4-丁烷四羧酸、2,2-雙(羥基甲基)-1,3-丙二醇及3-羥基-2,2-二甲基丙醛之聚合物、1,2,2,6,6-五甲基-4-哌啶酯、1,3‐雙(2,2,6,6-四甲基哌啶-4-基)-2,4-二-十三烷基苯-1,2,3,4-四羧酸酯、癸二酸雙(1-辛氧基-2,2,6,6-五甲基-4-哌啶基)酯、聚[[6-[(1,1,3,3-四甲基丁基)胺基]-1,3,5-三-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]-1,6-己二基[(2,2,6,6-四甲基-4-哌啶基)亞胺基]])等。該等光穩定劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等光穩定劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.005~0.5質量份。
作為上述塑化劑,例如可列舉:環氧化大豆油、環氧化亞麻仁油、環氧化脂肪酸辛酯等環氧系,或甲基丙烯酸酯系,或二羧酸與多元醇之縮聚物、多元羧酸與多元醇之縮聚物等聚酯系,或二羧酸與多元醇與伸烷基二醇之縮聚物、二羧酸與多元醇與伸芳基二醇之縮聚物、多元羧酸與多元醇與伸烷基二醇之縮聚物、多元羧酸與多元醇與伸芳基二醇之縮聚物等聚醚酯系,或己二酸酯、丁二酸酯等脂肪族酯系,或鄰苯二甲酸酯、對苯二甲酸酯、偏苯三甲酸酯、均苯四甲酸酯、苯甲酸酯等芳香族酯系等。該等塑化劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等塑化劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.1~500質量份,更佳為1~100質量份。
上述填充劑例如可列舉:滑石、雲母、碳酸鈣、氧化鈣、氫氧化鈣、碳酸鎂、氫氧化鎂、氧化鎂、硫酸鎂、氫氧化鋁、硫酸鋇、玻璃粉末、玻璃纖維、黏土、白雲石、雲母、二氧化矽、氧化鋁、鈦酸鉀晶鬚、矽灰石、纖維狀鹼式硫酸鎂、蒙脫石等,可適當選擇粒徑(纖維狀時為纖維直徑或纖維長度及縱橫比)而使用。該等填充劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等填充劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為1~100質量份,更佳為3~80質量份。
作為上述脂肪酸金屬鹽之脂肪酸,例如可列舉:癸酸、2-乙基己酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕櫚酸、珠光子酸、硬脂酸、十九酸、花生酸、二十一酸、山萮酸、二十三酸、二十四酸、蠟酸(cerotic acid)、褐煤酸、蜜蠟酸等飽和脂肪酸,4-癸烯酸、4-十二碳烯酸、棕櫚油酸、α-次亞麻油酸、亞麻油酸、γ-次亞麻油酸、十八碳四烯酸、岩芹酸、油酸、反油酸、異油酸、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等直鏈不飽和脂肪酸,均苯三酸等芳香族脂肪酸,尤佳為肉豆蔻酸、硬脂酸、12-羥基硬脂酸等飽和脂肪酸。作為脂肪酸金屬鹽之金屬,例如可列舉:鹼金屬、鎂、鈣、鍶、鋇、鈦、錳、鐵、鋅、矽、鋯、釔、鋇或鉿等,尤佳為鈉、鋰、鉀等鹼金屬。該等脂肪酸金屬鹽可單獨使用一種,亦可併用兩種以上而使用。 關於該等脂肪酸金屬鹽之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.05~3質量份。
上述抗靜電劑例如可列舉:脂肪酸四級銨離子鹽、聚胺四級鹽等陽離子系抗靜電劑,或高級醇磷酸酯鹽、高級醇EO(ethylene oxide,環氧乙烷)加成物、聚乙二醇脂肪酸酯、陰離子型之烷基磺酸鹽、高級醇硫酸酯鹽、高級醇環氧乙烷加成物硫酸酯鹽、高級醇環氧乙烷加成物磷酸酯鹽等陰離子系抗靜電劑,或多元醇脂肪酸酯、聚二醇磷酸酯、聚氧乙烯烷基烯丙醚等非離子系抗靜電劑,或烷基二甲基胺基乙酸甜菜鹼等兩性型烷基甜菜鹼、咪唑啉型兩性活性劑等兩性抗靜電劑。該等抗靜電劑可單獨使用一種,亦可併用兩種以上而使用。 關於該等抗靜電劑之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.01~20質量份,更佳為3~10質量份。
上述顏料亦可使用市售之顏料,例如可列舉:顏料紅1、2、3、9、10、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;顏料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;顏料黃1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;顏料綠7、10、36;顏料藍15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、56、60、61、62、64;顏料紫1、19、23、27、29、30、32、37、40、50等。該等顏料可單獨使用一種,亦可併用兩種以上而使用。 關於該等顏料之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.0001~10質量份。
上述染料亦可使用市售之染料,例如可列舉:偶氮染料、蒽醌染料、靛藍染料、三芳基甲烷染料、染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁染料、酞菁染料、花青染料等染料等。該等染料可單獨使用一種,亦可併用兩種以上而使用。 關於該等染料之使用量,於調配於樹脂中時,於難燃性樹脂組合物100質量份中,較佳為0.0001~10質量份。
為了獲得本發明之組合物,只要將必需成分之(A)及(B)成分、及視需要之(C)~(D)成分、以及進而視需要之其他任意成分進行混合即可,混合時可使用各種混合機。於混合時可進行加熱。列舉可使用之混合機之例,可列舉:滾筒攪拌機、亨舍爾混合機、帶式摻合機、V型混合機、W型混合機、高速混合機、圓錐螺旋混合機等。
本發明之組合物對樹脂之難燃化有效果,作為樹脂用組合物(有時亦稱為「樹脂用添加劑」)、尤其作為難燃劑較為有用。本發明之組合物可藉由將其調配於樹脂中,而作為難燃性樹脂組合物(以下,亦稱為本發明之難燃性樹脂組合物)較佳地使用。
作為藉由本發明之組合物而難燃化之樹脂,可列舉熱塑性樹脂及熱硬化性樹脂等合成樹脂。具體而言,作為熱塑性樹脂,可列舉:聚烯烴系樹脂、含生質之聚烯烴系樹脂、含鹵素樹脂、芳香族聚酯樹脂、直鏈聚酯樹脂、降解性脂肪族、聚醯胺樹脂、纖維素酯系樹脂;聚碳酸酯樹脂、聚胺基甲酸酯樹脂、聚苯醚系樹脂、聚苯硫醚系樹脂、丙烯酸系樹脂等熱塑性樹脂及該等之摻合物。另一方面,作為熱硬化性樹脂,可列舉:酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等。 作為藉由本發明之組合物而難燃化之其他合成樹脂,亦可列舉:烯烴系熱塑性彈性體、苯乙烯系熱塑性彈性體、聚酯系熱塑性彈性體、腈系熱塑性彈性體、尼龍系熱塑性彈性體、氯乙烯系熱塑性彈性體、聚醯胺系熱塑性彈性體、聚胺基甲酸酯系熱塑性彈性體等。 該等樹脂可使用一種,亦可使用兩種以上。又,樹脂有經合金化之情況。
本發明中所使用之樹脂係無論分子量、聚合度、密度、軟化點、於溶劑中之不溶物之比率、立體規則性之程度、觸媒殘渣之有無、成為原料之單體之種類或調配比率、聚合觸媒之種類(例如,齊格勒觸媒、茂金屬觸媒等)等如何均可使用。
以上之各種樹脂中,就可賦予優異之難燃性之方面而言,較佳為聚烯烴系樹脂或聚胺基甲酸酯系熱塑性彈性體。作為聚烯烴系樹脂,例如可列舉:聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、高密度聚乙烯、聚丙烯、均聚丙烯、聚丙烯無規共聚物、聚丙烯嵌段共聚物、耐衝擊性聚丙烯共聚物、高耐衝擊性聚丙烯共聚物、等規聚丙烯、間規聚丙烯、半等規聚丙烯、順丁烯二酸酐改性聚丙烯、聚丁烯、環烯烴聚合物、立體嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等α-烯烴聚合物,乙烯/丙烯嵌段或無規共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-乙酸乙烯酯共聚物等α-烯烴共聚物等。
又,作為聚胺基甲酸酯系熱塑性彈性體,可列舉熱塑性聚胺基甲酸酯樹脂(TPU)。熱塑性聚胺基甲酸酯樹脂(TPU)係於分子結構中具有胺基甲酸酯基(-NHCOO-)之橡膠狀彈性體,包含稱為軟鏈段之容易移動之長鏈部分與稱為硬鏈段之結晶性極強之部分,通常可使用多元醇、二異氰酸酯、及鏈延長劑進行製備。
又,關於熱塑性聚胺基甲酸酯樹脂,可根據其成形方法,大致分為:以液狀注入至模具中進行硬化反應之澆鑄類型、與先前之橡膠同樣地於滾筒混練後進行加壓成形之類型及可與普通熱塑性樹脂同樣地加工之類型,但於本發明中,並不區別該等。
作為上述熱塑性聚胺基甲酸酯樹脂之具體例,可列舉:酯(內酯)系聚胺基甲酸酯共聚物、酯(己二酸酯)系聚胺基甲酸酯共聚物、醚系聚胺基甲酸酯共聚物、碳酸酯系聚胺基甲酸酯共聚物、醚-酯系聚胺基甲酸酯共聚物,該等熱塑性聚胺基甲酸酯樹脂(TPU)可單獨使用,亦可組合而使用。
於本發明之難燃性樹脂組合物中,樹脂之含量較佳為50~99.9質量%,更佳為60~90質量%。又,於難燃性樹脂組合物含有本發明之組合物作為難燃劑組合物之情形時,相對於樹脂100質量份,較佳為含有該難燃劑組合物10質量份~400質量份,更佳為20~80質量份。藉由將難燃劑組合物之含量設定為10質量份以上,可發揮充分之難燃性,藉由設定為400質量份以下,而不易損害樹脂原本之物性。
本發明之難燃性樹脂組合物可藉由將其成形,而獲得難燃性優異之成形品。成形方法並無特別限定,可列舉:擠出加工、軋光加工、射出成形、滾壓成形、壓縮成形、吹塑成形等,可製造樹脂板、片、膜、異形品等各種形狀之成形品。
本發明之難燃性樹脂組合物及其成形體可用於電氣/電子/通訊、電子&工程、農林水產、礦業、建設、食品、纖維、服裝、醫療、煤、石油、橡膠、皮革、汽車、精密機器、木材、建築材料、土木、傢俱、印刷、樂器等廣泛之產業領域。更具體而言,可用於印表機、電腦、文字處理機、鍵盤、PDA(小型資訊終端機)、電話機、影印機、傳真機、ECR(電子式現金出納機)、計算器、電子記事本、卡、支座、文具等商務、OA(Office Automatio,辦公自動化)設備、洗衣機、冰箱、吸塵器、微波爐、照明器具、遊戲機、熨斗、暖爐等家電設備、TV(Television,電視)、VTR(Video Tape Recorder,磁帶錄影機)、攝錄影機、收錄機、磁帶錄音機、迷你磁碟、CD(Compact Disc,光碟)播放器、揚聲器、液晶顯示器等AV(Audiovisual,視聽)設備、連接器、繼電器、冷凝器、開關、印刷基板、繞線管、半導體密封材料、LED(Light-Emitting Diode,發光二極體)密封材料、電線、纜線、變壓器、偏轉磁軛、分電盤、時鐘等電氣/電子零件及通訊設備、OA設備等之殼體(框、殼體、外罩、包裝)或零件、汽車內外飾材料之用途。其中,可尤佳地用於電線等電子零件或汽車內外飾構件等汽車零件中。
進而,本發明之難燃性樹脂組合物及其成形體可用於座位(填充物、面料等)、安全帶、車頂內飾、敞篷車頂、扶手、門飾板、後雜物箱、地毯、纖維氈、遮陽板、輪圈罩、車墊罩、安全氣囊、絕緣材料、吊環、吊環帶、電線被覆材料、電氣絕緣材料、塗料、塗佈材料、外罩材料、地板材料、牆角壁、地毯、壁紙、牆壁裝飾材料、外飾材料、內飾材料、屋頂材料、蓋板材料、牆體材料、支柱材料、踏板、柵欄之材料、骨架及裝飾線腳、窗及門形材料、瓦板、板壁、階面、陽台、隔音板、隔熱板、窗材等汽車、油電混合車、電動汽車、車輛、船舶、飛機、建築物、住宅及建築用材料,或土木材料、衣料、窗簾、床單、合板、合成纖維板、絨毯、玄關墊、薄板、桶、軟管、容器、眼鏡、包、箱、護目鏡、滑雪板、球拍、帳篷、樂器等生活用品、運動用品等各種用途。 [實施例]
以下,藉由實施例更詳細地說明本發明。然而,本發明並不受以下之實施例任何限制。再者,以下之表1~2中之數值之單位為質量份。
<組合物之製備> 將下述表1及2中記載之成分中之樹脂以外之成分以該成分表中記載之比率進行調配,使用亨舍爾混合機進行混合。其中,於添加環氧系偶合劑、潤滑劑或聚矽氧油之情形時,於將其他成分預混合後,添加環氧系偶合劑、潤滑劑或聚矽氧油並使用亨舍爾混合機進行混合,獲得組合物。
<難燃性樹脂組合物之製備> ・實施例1~15及比較例1~4 於熱塑性聚胺基甲酸酯樹脂(BASF製造之Elastollan 1185A)100質量份中調配硬脂酸鈣0.1質量份、甘油單硬脂酸酯0.3質量份、四[3-(3,5-二第三丁基-4-羥基苯基)丙酸甲酯]甲烷0.1質量份、2,2'-亞甲基雙(4,6-二第三丁基苯基)-2-乙基己基亞磷酸酯0.1質量份,藉由亨舍爾混合機進行預混合而獲得熱塑性聚胺基甲酸酯樹脂組合物。相對於所獲得之熱塑性聚胺基甲酸酯樹脂組合物,將表1或2所示之組合物調配表中記載之質量份,利用亨舍爾混合機進行混合而獲得難燃性樹脂組合物。
・實施例16~20及比較例5~8 於聚丙烯(依據JIS K7210所測定之負載2.16 kg、230℃下之熔體流動速率=8 g/10 min)100質量份中,調配硬脂酸鈣(高級脂肪酸金屬鹽)0.1質量份、四[3-(3,5-二第三丁基-4-羥基苯基)丙酸甲酯]甲烷(酚系抗氧化劑)0.1質量份、亞磷酸三(2,4-二第三丁基苯基)酯(磷系抗氧化劑)0.1質量份,藉由亨舍爾混合機進行預混合而獲得聚丙烯樹脂組合物。相對於所獲得之聚丙烯樹脂組合物,將表1或表2所示之組合物調配表中記載之質量份,利用亨舍爾混合機進行混合而獲得難燃性樹脂組合物。
針對上述所獲得之各樹脂組合物,藉由以下之方法而製作顆粒,由該顆粒製作難燃性評價用試片,將該評價片供於以下之難燃性評價及表面平滑性評價。將其結果示於表1及表2。
[評價] <難燃性評價> 使用雙軸擠出成形機(日本製鋼所股份有限公司製造之TEX-30α),將含有熱塑性聚胺基甲酸酯樹脂之實施例1~15之樹脂組合物及比較例1~4之樹脂組合物於料缸溫度190~200℃、及螺桿速度150 rpm之條件下進行熔融混練。將自模具所噴出之線料藉由冷卻浴進行冷卻,藉由造粒機進行切斷,製作樹脂組合物之顆粒。
使用雙軸擠出成形機(日本製鋼所股份有限公司製造之TEX-30α),將含有聚丙烯樹脂之實施例16~20之樹脂組合物及比較例5~8之樹脂組合物於料缸溫度220~230℃、及螺桿速度150 rpm之條件下進行熔融混練。將自模具所噴出之線料藉由冷卻浴進行冷卻,藉由造粒機進行切斷,製作樹脂組合物之顆粒。
使用日精樹脂工業公司製造之NEX-80,將上述所獲得之樹脂組合物之顆粒進行射出成形,獲得長度127 mm、寬度12.7 mm、厚度1.6 mm之難燃性評價用試片。關於實施例1~13及比較例,將螺桿設定溫度設為200℃,將模具溫度設為40℃。關於實施例14~16及比較例7~12,將螺桿設定溫度設為230℃,將模具溫度設為40℃。
依據ISO1210對所獲得之試片進行20 mm垂直燃燒試驗(UL-94V)。具體而言,將試片保持垂直,使下端接焰燃燒器之火10秒後移走火焰,測定試片所著火之火熄滅之時間。其次,於火熄滅之同時,進行10秒第2次之接焰,與第1次同樣地測定著火之火熄滅之時間。又,對於是否因掉落之火種而使試片下之棉絮著火,亦同時進行評價。由第1次與第2次之燃燒時間、棉絮著火之有無等,依據UL-94V標準標註燃燒等級。燃燒等級係V-0為最高者,隨著成為V-1、V-2,而難燃性降低。將不相當於V-0~V-2之等級之任一種者設為NR。本發明中發現抗滴落效果者係設為達成V-2以上、較佳為V-0者。
<表面平滑性> 依據下述基準評價所獲得之試片之表面平滑性。 ○:試片之表面平滑而光滑 ×:試片之表面有少許之粗澀 [表1]
[表2]
如由表1所示之結果明確,判斷於將含有(A)成分、(B)成分之組合物調配於樹脂中之各實施例中,UL-94V試驗下之樹脂之難燃性評價及表面平滑性評價提高。尤其於(A)成分含有(A-1)成分及(A-2)成分之情形時,難燃性評價變得更良好。 相對於此,如表2所示,於不使用(A)成分之情形(比較例No.1、比較例No.5)時,難燃性及表面平滑性不充分,於不使用(B)成分之情形(比較例No.2~4、比較例No.6~8)時,表面平滑性不充分。 因此,判斷本發明之組合物可對樹脂賦予較高之難燃性及表面平滑性,作為難燃劑優異。 [產業上之可利用性]
根據本發明,可提供一種藉由混合於樹脂中而可賦予抗滴落效果,對該樹脂賦予優異之難燃性,且可獲得表面平滑性良好之成形品之組合物,及含有該組合物與樹脂且發揮優異之難燃性之難燃性樹脂組合物。
Claims (10)
- 一種組合物,其含有(A)磷酸胺鹽及(B)氰尿酸三聚氰胺。
- 如請求項1之組合物,其中上述(A)成分含有下述(A-1)及(A-2), (A-1)成分:選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群中之至少一種三聚氰胺鹽; (A-2)成分:選自由正磷酸哌、焦磷酸哌及多磷酸哌所組成之群中之至少一種哌鹽。
- 如請求項2之組合物,其中相對於上述(A-1)成分與(A-2)成分之合計100質量份,含有0.1~20質量份之上述(B)成分。
- 如請求項1之組合物,其中相對於上述(A)成分100質量份,進而含有0.01~10質量份之(C)氧化鋅。
- 如請求項1之組合物,其中相對於上述(A)成分100質量份,進而含有0.01~5質量份之(D)成分:選自由聚矽氧油、環氧系偶合劑、水滑石及潤滑劑所組成之群中之至少一種。
- 一種難燃劑,其含有如請求項1之組合物。
- 一種難燃性樹脂組合物,其中相對於樹脂100質量份,含有10~400質量份之如請求項6之難燃劑。
- 一種成形品,其係如請求項7之難燃性樹脂組合物之成形品。
- 一種樹脂之難燃化方法,其係將含有磷酸胺鹽(A)及氰尿酸三聚氰胺(B)之組合物與樹脂進行混合。
- 一種組合物之用途,其係將含有磷酸胺鹽(A)及氰尿酸三聚氰胺(B)之組合物用作難燃劑。
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| CN120842832A (zh) * | 2025-07-16 | 2025-10-28 | 天津金山电线电缆股份有限公司 | 一种顶驱用动力屏蔽电缆绝缘保护层材料及其制备方法 |
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| JP3684585B2 (ja) | 1993-11-26 | 2005-08-17 | 日産化学工業株式会社 | メラミンシアヌレート顆粒およびその製造方法 |
| JP3118359B2 (ja) | 1993-12-27 | 2000-12-18 | 三井化学株式会社 | メラミンシアヌレートの製造方法 |
| JP2000178386A (ja) | 1998-12-14 | 2000-06-27 | Fujikura Ltd | ノンハロゲン難燃性樹脂組成物 |
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| JP2003226798A (ja) | 2002-02-06 | 2003-08-12 | Sumitomo Wiring Syst Ltd | 耐摩耗性耐熱難燃樹脂組成物およびそれにより被覆された電線 |
| JP2004010700A (ja) * | 2002-06-05 | 2004-01-15 | Gun Ei Chem Ind Co Ltd | 新規フェノール系樹脂、及びそれを硬化剤としたエポキシ樹脂組成物 |
| US7968629B2 (en) * | 2006-03-17 | 2011-06-28 | Mitsubishi Engineering-Plastics Corporation | Flame retardant polyamide resin composition and molded article |
| DE102007039560A1 (de) * | 2007-08-22 | 2009-02-26 | Clariant International Limited | Flammwidrige Kunststoff-Formmasse |
| JP5414168B2 (ja) * | 2007-11-14 | 2014-02-12 | 株式会社Adeka | 加工性の改善された難燃剤組成物、難燃性合成樹脂組成物及びその成形品 |
| US20120088102A1 (en) * | 2010-10-06 | 2012-04-12 | 3M Innovative Properties Company | Nonhalogenated flame retardant adhesives and tapes |
| WO2012161070A1 (ja) * | 2011-05-25 | 2012-11-29 | 堺化学工業株式会社 | 難燃剤及び難燃性樹脂組成物 |
| US9240260B2 (en) * | 2011-09-30 | 2016-01-19 | Adeka Corporation | Flame-retardant resin composition and electric wire using same |
| JP5926945B2 (ja) * | 2011-12-15 | 2016-05-25 | オカモト株式会社 | 難燃性合成樹脂フィルム及びその製造方法 |
| WO2014080821A1 (ja) | 2012-11-21 | 2014-05-30 | 堺化学工業株式会社 | 難燃剤及び難燃性樹脂組成物 |
| BR112015014031B1 (pt) * | 2012-12-17 | 2021-12-21 | Adeka Corporation | Composição de retardo de chamas e composição de resina sintética de retardo de chamas |
| CN105209576A (zh) * | 2013-08-21 | 2015-12-30 | 株式会社艾迪科 | 阻燃剂组合物和阻燃性合成树脂组合物 |
| JP6448370B2 (ja) * | 2015-01-08 | 2019-01-09 | 株式会社Adeka | 難燃剤組成物及び難燃性合成樹脂組成物 |
| WO2017179653A1 (ja) * | 2016-04-13 | 2017-10-19 | 株式会社カネカ | 強靭化エポキシ樹脂組成物 |
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| EP3683288B1 (en) | 2023-06-07 |
| EP3683288A4 (en) | 2021-05-26 |
| US20200224100A1 (en) | 2020-07-16 |
| WO2019054155A1 (ja) | 2019-03-21 |
| JPWO2019054155A1 (ja) | 2020-11-05 |
| CN111094514A (zh) | 2020-05-01 |
| JP7109455B2 (ja) | 2022-07-29 |
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