TW201714941A - 樹脂添加劑組成物及使用其之合成樹脂組成物 - Google Patents
樹脂添加劑組成物及使用其之合成樹脂組成物 Download PDFInfo
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- TW201714941A TW201714941A TW105126246A TW105126246A TW201714941A TW 201714941 A TW201714941 A TW 201714941A TW 105126246 A TW105126246 A TW 105126246A TW 105126246 A TW105126246 A TW 105126246A TW 201714941 A TW201714941 A TW 201714941A
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Abstract
本發明提供含有特定之磷酸酯金屬鹽,即使成為丸粒形狀時,於樹脂中之分散性亦優良,摻合於樹脂時可得到所期望之物性改良效果的樹脂添加劑組成物及使用其之合成樹脂組成物。一種樹脂添加劑組成物,其中相對於鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯(A)100質量份而言,含有通式(1)表示之磷酸酯鋰鹽化合物(B)25~400質量份及通式(2)表示之脂肪酸金屬鹽(C)10~300質量份。相對於(A)成分及(B)成分之合計量100質量份而言,(C)成分之摻合量為10質量份~50質量份。□□
Description
本發明係關於含有特定之磷酸酯金屬鹽的樹脂添加劑組成物,詳而言之,係關於含有磷酸酯金屬鹽、以及特定之鋰鹽化合物作為結晶核劑成分,進而藉由含有脂肪酸金屬鹽,而提高樹脂中之分散性的樹脂添加劑組成物、及使用其之合成樹脂組成物。
聚乙烯、聚丙烯、聚丁烯-1等之聚烯烴系樹脂;聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等之聚酯系高分子;聚醯胺系高分子等之合成樹脂,加熱成形後之結晶化速度緩慢。因此,係有加工時之成形循環長等之問題,此外,成形後亦有因結晶化進行,使成形物變形的情況。
此等之缺點係來自合成樹脂之結晶性者,已知藉由生成多數之微細的結晶而能夠解決。作為生成多數之微細的結晶之方法,已知有提高結晶化溫度、或添加結晶核劑或結晶化促進劑等。
作為結晶核劑,已知有例如安息香酸鈉、4-
tert-丁基安息香酸鋁鹽、己二酸鈉及2鈉雙環[2.2.1]庚烷-2,3-二羧酸酯等之羧酸金屬鹽;鈉雙(4-tert-丁基苯基)磷酸酯、鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯及鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯等之磷酸酯金屬鹽;二亞苄基山梨醇、雙(甲基亞苄基)山梨醇、雙(3,4-二甲基亞苄基)山梨醇、雙(p-乙基亞苄基)山梨醇、及雙(二甲基亞苄基)山梨醇等之多元醇衍生物;N,N’,N”-參[2-甲基環己基]-1,2,3-丙烷三羧醯胺、N,N’,N”-三環己基-1,3,5-苯三羧醯胺、N,N’-二環己基萘二羧醯胺、1,3,5-三(2,2-二甲基丙醯胺)苯等之醯胺化合物等。
此等之中,尤以鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯,如專利文獻1~3所記載,已知係作為合成樹脂之物性改善效果高的結晶核劑,而廣為被使用。
又,專利文獻4中,提出了含有鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯之鋁鹽及脂肪族有機酸金屬鹽的結晶核劑組成物。
鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯之形狀為粉末,但使用粉末會有浮游粉塵所致之作業安全性的顧慮。又,亦有必須依各種用途,以任意的摻合量均勻地摻合多品種之樹脂添加劑之問題。因此,由計量性及操作性的觀點而言,對於使各種樹脂添加劑成形為丸粒(pellet)形狀之樹脂添加劑組成物的需求高。例如,
專利文獻5、6中,提出使用了鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯之樹脂添加劑組成物。
[專利文獻1]日本特開昭58-1736號公報
[專利文獻2]日本特開昭59-184252號公報
[專利文獻3]日本特開昭63-108063號公報
[專利文獻4]日本特開2002-338820號公報
[專利文獻5]日本特開2001-123021號公報
[專利文獻6]日本特開2004-292710號公報
於化合物廠商,一般而言係於丸粒形狀之樹脂中摻合樹脂添加劑而進行成形加工,但使用粉末形狀之樹脂添加劑時,與丸粒形狀之樹脂的比重差為大,因此難以將此等均勻混合。特別是鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯,為不易於樹脂中分散之化合物,因此要求分散性的改良。
又,將鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯成形為丸粒形狀之樹脂添加劑組成物時,亦有於樹脂中之分散性惡化,變得不易得到所期望之物性,必
須多量添加的問題。
至今為止,雖有進行提高鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯之分散性的探討,但並非為能夠滿足者。
因而本發明之目的為提供含有特定之磷酸酯金屬鹽,即使成為丸粒形狀時,於樹脂中之分散性亦優良,摻合於樹脂時可得到所期望之物性改良效果的樹脂添加劑組成物及使用其之合成樹脂組成物。
本發明者等人重複探討的結果,發現藉由對鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯混合特定之鋰鹽的化合物及脂肪酸金屬鹽,可解決上述問題,而完成了本發明。
本發明之樹脂添加劑組成物,係相對於鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯(A)100質量份而言,含有下述通式(1)表示之磷酸酯鋰鹽化合物(B)25~400質量份及下述通式(2)表示之脂肪酸金屬鹽(C)10~300質量份的樹脂添加劑組成物,其特徵為
相對於(A)成分及(B)成分之合計量100質量份而言,(C)成分之摻合量,為10質量份~50質量份之範圍內。
本發明之樹脂添加劑組成物,較佳為進一步含有相對於總量而言,為10質量%~50質量%之酚系抗氧化劑(D)。
本發明之樹脂添加劑組成物,較佳為具有丸粒形狀者。
本發明之合成樹脂組成物,其特徵為相對於合成樹脂100質量份而言,於(A)成分及(B)成分之合計量為0.001~5質量份的範圍內含有上述本發明之樹脂添加劑組成物。
又,本發明中,較佳為前述合成樹脂為聚烯烴系樹脂之合成樹脂組成物。
依照本發明,可實現含有特定之磷酸酯金屬
鹽,即使成為丸粒形狀時,於樹脂中之分散性亦優良,摻合於樹脂時可得到所期望之物性改良效果的樹脂添加劑組成物及使用其之合成樹脂組成物。
以下,詳細說明本發明之實施形態。
本發明中使用之磷酸酯鋰鹽化合物,係下述通式(1)表示之化合物。
通式(1)中之R1~R4所表示的直鏈或具有分支之碳原子數1~8之烷基,可列舉例如甲基、乙基、丙基、異丙基、丁基、sec-丁基、tert-丁基、異丁基、戊基、tert-戊基、己基、庚基、辛基、異辛基、tert-辛基、2-乙基己基等。本發明中,特別以tert-丁基為佳。
通式(1)中的R5表示之碳原子數1~4之亞烷基,可列舉例如亞甲基、亞乙基、亞丙基、亞丁基等。
通式(1)表示之磷酸酯鋰鹽化合物之具體的構造,可列舉例如下述化合物。惟,本發明不受以下化合
物之限制。
本發明中,磷酸酯鋰鹽化合物(B)之使用量,相對於鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯(A)100質量份而言,係25~400質量份、較佳為50~100質量份。磷酸酯鋰鹽化合物(B)之使用量落在25~400質量份之範圍外時,可能有無法得到本發明之效果的情形。
本發明中所使用之脂肪酸金屬鹽(C),為下述通式(2)表示之化合物。
通式(2)中,R6所表示的碳原子數1~40之脂肪族基,可列舉烷基、烯基、經導入2個以上之不飽和鍵的烷基等之烴基,亦可經羥基取代,亦可具有分支。
具體而言,可列舉乙酸、丙酸、丁酸、戊
酸、異戊酸、己酸、庚酸、辛酸、壬酸、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、十七酸、硬脂酸、十九酸、二十酸、二十一酸、二十二酸、二十三酸、二十四酸、二十六酸、二十八酸、三十酸等之飽和脂肪酸;4-癸烯酸、4-十二烯酸、棕櫚油酸(palmitoleic acid)、α-次亞麻油酸、亞麻油酸、γ-次亞麻油酸、硬脂四烯酸、芹子酸(petroselinic acid)、油酸、反油酸(elaidic acid)、11-十八碳烯酸(vaccenic acid)、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等之直鏈不飽和脂肪酸;苯均三酸等之芳香族脂肪酸。本發明中,較佳為碳原子數7~21之脂肪族基;特別以肉豆蔻酸、硬脂酸、12-羥基硬脂酸等之飽和脂肪酸為佳。
通式(2)中,M表示之金屬原子,可列舉鹼金屬、鎂、鈣、鍶、鋇、鈦、錳、鐵、鋅、矽、鋯、釔、鋇或鉿等。此等之中,特佳為使用鈉、鋰、鉀等之鹼金屬。
本發明中,就脂肪酸金屬鹽(C)而言,由性能上良好且比較容易獲得的觀點,較佳為硬脂酸鋰、硬脂酸鈉、硬脂酸鎂、硬脂酸鋅、硬脂酸鋁、肉豆蔻酸鋰、二十二酸鎂、12-羥基硬脂酸鋰等;更佳可列舉肉豆蔻酸鋰、硬脂酸鋰、12-羥基硬脂酸鋰等。
上述脂肪酸金屬鹽,可藉由使羧酸化合物與金屬氫氧化物反應後,進行水洗、脫水、乾燥之合成方法(複分解法);或不使用水而直接反應的合成法(直接
法)來製造。
脂肪酸金屬鹽(C)之使用量,相對於鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯(A)100質量份而言,係10~300質量份、較佳為20~200質量份,且相對於(A)成分與(B)成分之合計量100質量份而言,需要於10質量份~50質量份之範圍內。脂肪酸金屬鹽(C)之使用量,相對於(A)成分與(B)成分之合計量100質量份而言,少於10質量份時,可能有無法得到本發明之效果的情形,多於50質量份時,可能有抑制結晶核劑成分之性能(核劑效果)的情形。
本發明之樹脂添加劑組成物,於上述(A)~(C)成分以外,於不顯著損及本發明之效果的範圍內,亦可任意含有公知之樹脂添加劑,例如酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑、紫外線吸收劑、受阻胺化合物、上述(A)成分及(B)成分以外之結晶核劑、阻燃劑、阻燃助劑、潤滑劑、填充材、金屬皂、水滑石類、抗靜電劑、顏料、染料等。又,公知之樹脂添加劑,亦可與本發明之樹脂添加劑組成物分別地,摻合於合成樹脂中。
特別地,本發明之樹脂添加劑組成物,較佳為進一步含有酚系抗氧化劑(D)。
本發明所使用之酚系抗氧化劑,係指其分子構造中包
含酚骨架之公知的抗氧化劑。具體而言,可列舉2,6-二第三丁基-p-甲酚、2,6-二苯基-4-十八烷氧基酚、硬脂基(3,5-二第三丁基-4-羥基苯基)丙酸酯、二硬脂基(3,5-二第三丁基-4-羥基苄基)膦酸酯、十三烷基.3,5-二第三丁基-4-羥基苄硫基乙酸酯、硫二伸乙基雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、4,4’-硫雙(6-第三丁基-m-甲酚)、2-辛硫基-4,6-二(3,5-二第三丁基-4-羥基苯氧基)-s-三嗪、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、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(4,6-二第三丁基酚)、2,2’-亞乙基雙(4,6-二第三丁基酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、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]對苯二甲酸酯、1,3,5-參(2,6-二甲基-3-羥基-4-第三丁基苄基)三聚異氰酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)三聚異氰酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]三聚異氰酸酯、肆[3-(3,5-二第三丁基-4-羥基苯基)丙炔氧基甲基]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)酚、3,9-雙[2-(3-第三丁基-4-羥基-5-甲基氫桂皮醯氧基)-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[β-(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等。
其中特別以肆[3-(3,5-二第三丁基-4-羥基苯基)丙炔
氧基甲基]甲烷,由於對聚烯烴樹脂賦予優良的抗氧化效果、且容易使樹脂添加劑組成物成形為丸粒形狀,故較佳。
酚系抗氧化劑之使用量,相對於樹脂添加劑組成物之總量而言,較佳調整為10質量%~50質量%之範圍內。藉由使酚系抗氧化劑之使用量為10質量%以上,容易成形為丸粒,而且容易維持丸粒形狀。又,藉由使酚系抗氧化劑之使用量為50質量%以下,不會阻礙(A)成分及(B)成分所致之結晶核劑的作用效果,可更良好地得到本發明之效果。
磷系抗氧化劑,可列舉例如亞磷酸三苯酯、亞磷酸二異辛酯、柒(二丙二醇)三亞磷酸酯、亞磷酸三異癸酯、亞磷酸二苯基異辛酯、亞磷酸二異辛基苯酯、亞磷酸二苯基十三烷酯、亞磷酸三異辛酯、亞磷酸三月桂酯、亞磷酸二苯酯、參(二丙二醇)亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、二油基氫亞磷酸酯、三月桂基三硫代亞磷酸酯、雙(十三烷基)亞磷酸酯、參(異癸基)亞磷酸酯、參(十三烷基)亞磷酸酯、亞磷酸二苯基癸酯、二壬基苯基雙(壬基苯基)亞磷酸酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙二醇二亞磷酸酯、參壬基苯基亞磷酸酯、參(2,4-二-tert-丁基苯基)亞磷酸酯、參(2,4-二-tert-丁基-5-甲基苯基)亞磷酸酯、參〔2-tert-丁基-4-(3-tert-丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基〕亞磷酸酯、三(癸基)亞磷酸酯、辛基二苯基亞磷酸酯、二
(癸基)單苯基亞磷酸酯、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-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三-tert-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、四苯基-四(十三烷基)季戊四醇四亞磷酸酯、雙(2,4-二-tert-丁基-6-甲基苯基)乙基亞磷酸酯、四(十三烷基)異亞丙基二酚二亞磷酸酯、四(十三烷基)-4,4’-n-亞丁基雙(2-tert-丁基-5-甲基酚)二亞磷酸酯、六(十三烷基)-1,1,3-參(2-甲基-4-羥基-5-tert-丁基苯基)丁烷三亞磷酸酯、肆(2,4-二-tert-丁基苯基)伸聯苯基二亞膦酸酯、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)參(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-tert-丁基苯基)-2-乙基己基亞磷酸酯、2,2’-亞甲基雙(4,6-二-tert-丁基苯基)-十八烷基亞磷酸酯、2,2’-亞乙基雙(4,6-二-tert-丁基苯基)氟亞磷酸酯、4,4’-亞丁基雙(3-甲基-6-tert-丁基苯基二-十三烷基)亞磷酸酯、參(2-〔(2,4,8,10-肆-tert-丁基二苯并〔d,f〕〔1,3,2〕二氧雜磷雜環庚三烯(phosphepine)-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[5,5]十一烷、2,4,6-三-tert-丁基苯基-
2-丁基-2-乙基-1,3-丙二醇亞磷酸酯、聚4,4’-異亞丙基二酚C12-15醇亞磷酸酯等。
磷系抗氧化劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.001~10質量份、更佳成為0.01~0.5質量份之範圍。
硫醚系抗氧化劑,可列舉例如肆[亞甲基-3-(月桂硫基)丙酸酯]甲烷、雙(甲基-4-[3-n-烷基(C12/C14)硫代丙醯氧基]5-tert-丁基苯基)硫醚、二-十三烷基-3,3’-硫代二丙酸酯、二月桂基-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯、月桂基/硬脂基硫代二丙酸酯、4,4’-硫雙(6-tert-丁基-m-甲酚)、2,2’-硫雙(6-tert-丁基-p-甲酚)、二硬脂基-二硫醚等。
硫醚系抗氧化劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.001~10質量份、更佳成為0.01~0.5質量份之範圍。
紫外線吸收劑,可列舉例如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)等之2-羥基二苯甲酮類;2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-tert-辛基苯基)苯并三唑、2-(2-羥基-3,5-二-tert-丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-tert-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-tert-辛基-6-苯并三唑基酚)、2-(2-羥基-3-tert-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-tert-丁基苯基〕苯并三唑、2-〔2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-辛基苯基〕苯并三唑、2-〔2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-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-tert-丁基-5-(2-甲基丙烯醯氧基乙基)苯基〕苯并三唑、2-〔2-羥基-3-tert-戊基-5-(2-甲基丙烯醯氧基乙基)苯基〕苯并三唑、2-〔2-羥基-3-tert-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〕苯并三唑等之2-(2-羥基苯基)苯并三唑類;水楊酸苯酯、間苯二酚單安息香酸酯、2,4-二-tert-丁基苯基-3,5-二-tert-丁基-4-羥基安息香酸酯、辛基(3,5-二-tert-丁基-4-羥基)安息香酸酯、十二烷基(3,5-二-tert-丁基-4-羥基)安息香酸酯、十四烷基(3,5-二-tert-丁基-4-羥基)安息香酸酯、十六烷基(3,5-二-tert-丁基-4-羥基)安息香酸酯、十八烷基(3,5-二-tert-丁基-4-羥基)安息香酸酯、二十二烷基(3,5-二-tert-丁基-4-羥基)安息香酸酯等之安息香酸酯類;2-乙基-2’-乙氧基草醯苯胺、2-乙氧-基-4’-十二烷基草醯苯胺等之取代草醯苯胺(substituted oxanilide)類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-
2-氰基-3-甲基-3-(p-甲氧基苯基)丙烯酸酯等之氰基丙烯酸酯類;各種金屬鹽、或金屬鉗合物,特別是鎳、鉻之鹽、或鉗合物類等。
紫外線吸收劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.001~5質量份、更佳成為0.005~0.5質量份之範圍。
受阻胺化合物,可列舉例如2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基安息香酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、肆(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、雙(2,2,6,6-四甲基-4-哌啶基).二(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二-tert-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/琥珀酸二乙酯縮聚合物、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-s-三嗪縮聚合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-tert-辛基胺基-s-三嗪縮聚合物、1,5,8,12-肆〔2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基〕-1,5,8,12-四氮雜十二烷、1,5,8,12-肆〔2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基〕-1,5,8-12-四氮雜十二烷、1,6,11-參
〔2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基〕胺基十一烷、1,6,11-參〔2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基〕胺基十一烷、雙{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}癸二酸酯、雙{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基)碳酸酯、Ciba Specialty Chemicals公司製TINUVIN NOR 371等。
受阻胺化合物之較佳使用量,相對於合成樹脂100質量份而言,係成為0.001~5質量份、更佳成為0.005~0.5質量份之範圍。
(A)成分及(B)成分以外之結晶核劑,可列舉例如安息香酸鈉、4-tert-丁基安息香酸鋁鹽、己二酸鈉及2鈉雙環[2.2.1]庚烷-2,3-二羧酸酯等之羧酸金屬鹽、二亞苄基山梨醇、雙(甲基亞苄基)山梨醇、雙(3,4-二甲基亞苄基)山梨醇、雙(p-乙基亞苄基)山梨醇、及雙(二甲基亞苄基)山梨醇等之多元醇衍生物、N,N’,N”-參[2-甲基環己基]-1,2,3-丙烷三羧醯胺、N,N’,N”-三環己基-1,3,5-苯三羧醯胺、N,N’-二環己基萘二羧醯胺、1,3,5-三(二甲基異丙醯基胺基)苯等之醯胺化合物等。
結晶核劑之較佳使用量,相對於合成樹脂100質量份而言,係包含(A)成分及(B)成分之合計量成為0.001~5質量份、更佳成為0.005~0.5質量份之範圍。
阻燃劑可列舉例如磷酸三苯酯、磷酸三甲苯酚酯、磷酸三-二甲苯酯、磷酸甲苯酚二苯酯、磷酸甲苯
酚-2,6-二-二甲苯酯、間苯二酚雙(二苯基磷酸酯)、(1-甲基亞乙基)-4,1-伸苯基四苯基二磷酸酯、1,3-伸苯基肆(2,6-二甲基苯基)磷酸酯、ADEKA股份有限公司製商品名Adekastub FP-500、ADEKA股份有限公司製商品名Adekastub FP-600、ADEKA股份有限公司製商品名Adekastub FP-800等之芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸(1-丁烯基)等之膦酸酯、二苯基次磷酸苯酯、二苯基次磷酸甲酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物衍生物等之次磷酸酯、雙(2-烯丙基苯氧基)膦氮烯、二甲苯酚基膦氮烯等之膦氮烯化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸銨、磷酸哌嗪、焦磷酸哌嗪、聚磷酸哌嗪、含磷之乙烯基苄基化合物及紅磷等之磷系阻燃劑、氫氧化鎂、氫氧化鋁等之金屬氫氧化物、溴化雙酚A型環氧樹脂、溴化酚酚醛清漆型環氧樹脂、六溴苯、五溴甲苯、伸乙基雙(五溴苯基)、伸乙基雙四溴鄰苯二甲醯亞胺、1,2-二溴-4-(1,2-二溴乙基)環己烷、四溴環辛烷、六溴環十二烷、雙(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯及2,4,6-參(三溴苯氧基)-1,3,5-三嗪、三溴苯基馬來醯亞胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴雙酚A型二甲基丙烯酸酯、丙烯酸五溴苄酯、及溴化苯乙烯等之溴系阻燃劑等。此等阻燃劑較佳為與氟樹脂等之滴流防止劑或多元醇、水滑石等之阻燃助劑合併使用。
阻燃劑之較佳使用量,相對於合成樹脂100質量份而言,係成為1~50質量份、更佳成為10~30質量份之範圍。
潤滑劑係以賦予成形體表面潤滑性,提高防止損傷效果為目的而添加。潤滑劑可列舉例如油酸醯胺、芥酸醯胺等之不飽和脂肪酸醯胺;二十二酸醯胺、硬脂酸醯胺等之飽和脂肪酸醯胺;硬脂酸丁酯、硬脂基醇、硬脂酸單甘油酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯、甘露醇、硬脂酸、硬化蓖麻油、硬脂酸醯胺、油酸醯胺、伸乙基雙硬脂酸醯胺等。此等可1種單獨使用、亦可合併使用2種以上。
潤滑劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.01~2質量份、更佳成為0.03~0.5質量份之範圍。
填充劑可列舉例如滑石、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、鈦酸鉀鬚晶、矽灰石、纖維狀硫酸氧鎂等,可適當選擇粒子徑(纖維狀時係纖維直徑或纖維長及縱橫比)來使用。又,填充劑可依需要使用經表面處理者。
填充劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.01~80質量份、更佳成為1~50質量份之範圍。
作為金屬皂,可使用鎂、鈣、鋁、鋅等之金屬;與月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、二十二酸、油酸等之飽和或不飽和脂肪酸之鹽。
金屬皂之較佳使用量,相對於合成樹脂100質量份而言,係金屬皂成為0.001~10質量份、更佳成為0.01~5質量份之範圍。
作為水滑石類,係由作為天然物或合成物而已知之鎂、鋁、羥基、碳酸基及任意之結晶水所成的複合鹽化合物,可列舉將鎂或鋁之一部分以鹼金屬或鋅等之其他金屬取代者或將羥基、碳酸基以其他陰離子基取代者,具體而言,可列舉例如將下述通式(3)表示之水滑石的金屬取代為鹼金屬者。又,就Al-Li系之水滑石類而言,亦可使用下述通式(4)表示之化合物。
Mgx1Znx2Al2(OH)2(x1+x2)+4(CO3)pH2O (3)
此處,通式(3)中,x1及x2分別表示滿足下述式0≦x2/x1<10,2≦x1+x2≦20表示的條件之數,p表示0或正數。
[Li1/3Al2/3(OH)2].[Aq- 1/3q.pH2O] (4)
此處,通式(4)中,Aq-表示q價之陰離子,p表示0或正數。
又,水滑石類中之碳酸陰離子,其一部分亦可經其他陰離子取代。
水滑石類可為將結晶水脫水者;亦可為經硬脂酸等之高級脂肪酸、油酸鹼金屬鹽等之高級脂肪酸金屬
鹽、十二烷基苯磺酸鹼金屬鹽等之有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等被覆者。
水滑石類可為天然物、亦可為合成品。該化合物之合成方法,可列舉日本特公昭46-2280號公報、日本特公昭50-30039號公報、日本特公昭51-29129號公報、日本特公平3-36839號公報、日本特開昭61-174270號公報、日本特開平5-179052號公報等記載的公知之方法。又,水滑石類可不限制其結晶構造、結晶粒子等地使用。
水滑石類之較佳使用量,相對於合成樹脂100質量份而言,係成為0.001~5質量份、更佳成為0.05~3質量份之範圍。
抗靜電劑可列舉例如脂肪酸四級銨離子鹽、多胺四級鹽等之陽離子系抗靜電劑;高級醇磷酸酯鹽、高級醇EO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之陰離子系抗靜電劑;多元醇脂肪酸酯、聚乙二醇磷酸酯、聚氧乙烯烷基烯丙基醚等之非離子系抗靜電劑;烷基二甲基胺基乙酸甜菜鹼等之兩性型烷基甜菜鹼、咪唑啉型兩性活性劑等之兩性抗靜電劑。該抗靜電劑可單獨使用,又,亦可組合2種以上之抗靜電劑使用。
抗靜電劑之較佳使用量,相對於合成樹脂100質量份而言,係成為0.03~2質量份、更佳成為0.1~0.8質量份之
範圍。
顏料亦可使用市售之顏料,例如可列舉Pigment Red 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;Pigment Orange 13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;Pigment Yellow 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;Pigment Green 7、10、36;Pigment Blue 15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、56、60、61、62、64;Pigment Violet 1、19、23、27、29、30、32、37、40、50等。
染料可列舉偶氮染料、蒽醌染料、靛藍類染料、三芳基甲烷染料、呫噸(xanthenes)染料、茜素染料、吖啶染料、二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、噁嗪染料、酞青素染料、花青染料等,此等亦可混合複數種使用。
本發明之樹脂添加劑組成物,較佳為具有丸粒形狀者。作為具有丸粒形狀之樹脂添加劑組成物之製造
方法,可藉由將上述(A)成分~(C)成分及酚系抗氧化劑;與依需要任意含有的其他添加劑混合而得的混合物,於熔解狀態之酚系抗氧化劑的存在下混合而製造。加工條件、加工機器等並無任何限定,可使用眾所週知一般的加工方法、加工機器。
具體的製造方法,可列舉圓盤製粒機(disk pelleter)法、擠出法等。本發明中,以大量生產容易,且維持丸粒形狀上優良之擠出法為佳。又,擠出法之加工溫度,較佳為酚系抗氧化劑之熔點以上、且熔點加50℃之範圍以內。低於酚系抗氧化劑之熔點時,可能有丸粒之形狀的安定性不足的情況,高於酚系抗氧化劑之熔點加50℃時,可能有樹脂添加劑組成物之流動性增大、成形困難的情況。
(粉化率)
本發明之具有丸粒形狀之樹脂添加劑組成物,較佳為於輸送時可維持製品形狀者。具體而言,將不會通過口徑1.39mm之篩的試樣置入100g於500ml塑膠容器中,以振幅40mm、振盪速度300循環/分鐘振盪4小時後,會通過口徑1.39mm之篩的試樣,較佳為未達1質量%、更佳為未達0.5質量%為佳。
本發明之合成樹脂組成物,相對於合成樹脂100質量份而言,係以(A)成分及(B)成分之合計量成為0.001~5質量份之範圍內、較佳成為0.005~0.5質量份
之範圍內的方式含有上述本發明之樹脂添加劑組成物。(A)成分及(B)成分之合計量少於上述範圍時,可能有得不到結晶核劑之效果的情況,多於上述範圍時,可能有得不到添加量所相應之效果,而變得不經濟的情況,又,可能有出現在成形品表面,損及外觀的情況。不管何者均無法得到本發明所期望的效果。
將本發明之樹脂添加劑組成物摻合於合成樹脂而成形時,可使用公知之成形方法成形。例如,合成樹脂為熱可塑性樹脂時,可使用射出成形法、擠出成形法、吹塑成形法、真空成形法、吹脹成形(inflation molding)法、壓延成形法、凝塑成形(slush molding)法、浸漬成形法、發泡成形法等來得到成形品。
又,合成樹脂為使用熱、光、放射線及其他而硬化的硬化性樹脂時,可使用壓縮成形法、射出成形法、低壓成形法、層合成形法等來得到成形品。
本發明中之合成樹脂,可列舉例如聚丙烯、高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯、聚丁烯-1、聚-3-甲基戊烯等之α-烯烴聚合物;乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-乙烯醇共聚物、乙烯-丙烯共聚物等之聚烯烴及此等之共聚物;聚氯乙烯、聚偏二氯乙烯、氯化聚乙烯、氯化聚丙烯、聚偏二氟乙烯、氯化橡膠、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏二氯乙烯共聚物、
氯乙烯-偏二氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-馬來酸酯共聚物、氯乙烯-環己基馬來醯亞胺共聚物等之含鹵素樹脂;石油樹脂;香豆酮樹脂;聚苯乙烯;聚乙酸乙烯酯;丙烯酸樹脂;苯乙烯及/或α-甲基苯乙烯與其他單體(例如馬來酸酐、苯基馬來醯亞胺、甲基丙烯酸甲酯、丁二烯、丙烯腈等)之共聚物(例如AS樹脂、ABS樹脂、MBS樹脂、耐熱ABS樹脂等);聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯基甲縮醛、聚乙烯基丁縮醛、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等之直鏈聚酯;聚苯醚、聚己內醯胺、聚六亞甲基己二醯胺等之聚醯胺;聚碳酸酯、聚碳酸酯/ABS樹脂、分支聚碳酸酯、聚縮醛、聚苯硫醚、聚胺基甲酸酯、三乙醯基纖維素、纖維系樹脂等之熱可塑性樹脂及此等之摻合物;酚樹脂、尿素樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等之熱硬化性樹脂。進一步地,亦可為異戊二烯橡膠、丁二烯橡膠、丙烯腈-丁二烯共聚合橡膠、苯乙烯-丁二烯共聚合橡膠等之彈性體。此等之合成樹脂可單獨使用、或亦可混合二種以上使用。
因為本發明之效果顯著,故作為本發明中使用之合成樹脂,較佳為由乙烯均聚物、丙烯均聚物、乙烯/丙烯嵌段或無規共聚物、乙烯以外之α-烯烴/丙烯嵌段或無規共聚物、及此等聚合物之混合物中選擇之聚烯烴系樹脂。
本發明之合成樹脂組成物之用途,可列舉保險桿、儀表、儀錶面板等之汽車材料、冷藏庫、洗衣機、
掃除機等之住宅用途;食器、水桶、入浴用品等之家庭用品;玩具等之雜貨品;儲槽類等之儲藏、保存用容器等之成形品;或薄膜、纖維等。
以下列舉實施例,以更具體說明本發明,但本發明不受以下實施例等的任何限制。
使用亨舍爾混合機(Henschel mixer)(三井礦山(股)製、製品名FM200;攪拌翼旋轉速度1000rpm,1分鐘),對於熔體流動速率25g/10min之聚丙烯嵌段共聚物100質量份,混合作為酚系抗氧化劑之肆[亞甲基-3-(3’,5’-二第三丁基-4’-羥基苯基)丙酸酯]甲烷0.1質量份、作為磷系抗氧化劑之參(2,4-二第三丁基苯基)亞磷酸酯0.1質量份、作為中和劑之硬脂酸鈣0.05質量份、及下述表1或表2記載之樹脂添加劑組成物後,使用二軸擠出機(PCM-30;(股)池貝製)於240℃、螺桿速度160rpm之加工條件進行造粒,得到合成樹脂組成物之丸粒。
(彎曲彈性率)
使用所得到之丸粒,以射出成型機(EC100-2A;東芝機械(股)製),於射出溫度230℃、模具溫度50℃之條件進行射出成形,得到寬10mm、長80mm、厚4mm之試驗片。試驗片係於射出成形後,立即於槽內溫度23℃
之恆溫槽中靜置48小時以上後,使用彎曲試驗機測定彎曲彈性率。
此等之結果示於下述表1。
(結晶化溫度)
切取少量所得之丸粒,使用示差掃描熱量測定器(Diamond PerkinElmer公司製),測定結晶化溫度。作為測定方法,係由室溫以50℃/min之速度昇溫至230℃,保持10分鐘後,以-10℃/min之速度冷卻至50℃,於所得到之圖中,以吸熱反應成為峰頂時的溫度作為結晶化溫度。
此等之結果示於下述表2。
由比較例1-3~1-5可知,本發明之樹脂添加劑組成物的(A)成分、(B)成分及(C)成分的任一者若有欠缺時,缺乏物性的改良效果。又,由比較例1-2可知,將(B)成分變更為與本發明之樹脂添加劑組成物不同的核劑時,可確認到亦缺乏物性的改良效果。
相對於此等,本發明之實施例之樹脂添加劑組成物,均可確認到物性改良效果為優良。
由表2中之比較例2-2~2-4可知,相較於單獨摻合化合物A的情況,本發明之各實施例的樹脂添加劑組成物,可確認到改善樹脂之結晶化溫度的效果高。
接著,關於樹脂添加劑組成物,評估丸粒形狀的情況與粉末形狀的情況之影響。
對於230℃之熔體流動速率為25g/10min的聚丙烯嵌段共聚物100質量份,摻合下述表3記載之樹脂添加劑組成物,實施5分鐘的手拌合後,使用二軸擠出機(PCM-30;(股)池貝製)於240℃、螺桿速度160rpm之加工條件進行造粒,得到合成樹脂組成物之丸粒。
藉由所得到之丸粒,使用射出成型機(EC100-2A;東芝機械(股)製),於射出溫度230℃、模具溫度50℃之條件進行射出成形,得到寬10mm、長80mm、厚4mm之試驗片。試驗片係於射出成形後,立即於槽內溫度23℃之恆溫槽中靜置48小時以上後,根據ISO178之試驗方法測定彎曲彈性率。此等之結果示於下述表3。
由比較例3-2可知,對於丸粒形狀之聚丙烯嵌段共聚物100質量份,僅摻合0.05質量份化合物A時,幾乎得不到核劑之效果。相對於此,本發明之各實施例的樹脂添加劑組成物,可確認到即使低添加量,亦可對丸粒形狀之聚丙烯嵌段共聚物賦予核劑效果。
接著,說明將本發明之樹脂添加劑組成物使用於丸粒狀之樹脂添加劑組成物時的效果。
(製造實施例1)
鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯 9.5質量%
鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯 9.5質量%
肉豆蔻酸鋰 9.5質量%
酚系抗氧化劑:肆[3-(3,5-二第三丁基-4-羥基苯基)丙炔氧基甲基]甲烷 28.6質量%
磷系抗氧化劑:參(2,4-二-tert-丁基苯基)亞磷酸酯 28.6質量%
觸媒失活劑:硬脂酸鈣 14.3質量%
依上述摻合量,使用亨舍爾混合機(FM200;三井礦山(股)製)將此等以1000rpm、1分鐘之條件混合後,使用二軸擠出機(PCM-30;(股)池貝製),以缸體溫度設定為試樣導入部30℃、中央部130℃、製品排出口附
近100℃、擠出螺桿旋轉數60rpm之加工條件,製造丸粒形狀之樹脂添加劑組成物。
再者,該樹脂添加劑組成物之摻合內容,係相當於實施例1-4中評估之樹脂添加劑組成物。
(製造比較例1)
鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯 28.5質量%
酚系抗氧化劑:肆[3-(3,5-二第三丁基-4-羥基苯基)丙炔氧基甲基]甲烷 28.6質量%
磷系抗氧化劑:參(2,4-二-tert-丁基苯基)亞磷酸酯 28.6質量%
觸媒失活劑:硬脂酸鈣 14.3質量%
依上述摻合量,使用亨舍爾混合機(FM200;三井礦山(股)製)將此等以1000rpm、1分鐘之條件混合後,使用二軸擠出機(PCM-30;(股)池貝製),以缸體溫度設定為試樣導入部30℃、中央部130℃、製品排出口附近100℃、擠出螺桿旋轉數60rpm之加工條件,製造丸粒形狀之樹脂添加劑組成物。
(製造比較例2)
鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯 28.5質量%
酚系抗氧化劑:肆[3-(3,5-二第三丁基-4-羥基苯基)
丙炔氧基甲基]甲烷 28.6質量%
磷系抗氧化劑:參(2,4-二-tert-丁基苯基)亞磷酸酯 28.6質量%
觸媒失活劑:硬脂酸鈣 14.3質量%
依上述摻合量,使用亨舍爾混合機(FM200;三井礦山(股)製)將此等以1000rpm、1分鐘之條件混合後,使用二軸擠出機(PCM-30;(股)池貝製),以缸體溫度設定為試樣導入部30℃、中央部130℃、製品排出口附近100℃、擠出螺桿旋轉數60rpm之加工條件,製造丸粒形狀之樹脂添加劑組成物。
(製造實施例2)
(試驗試樣A之製造)
對於230℃之熔體流動速率8g/10min的均聚丙烯100質量份,以鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯及肉豆蔻酸鋰的合計成為0.1質量份的方式,添加於製造實施例1中製造之樹脂添加劑組成物之丸粒,來進行操作,使用二軸擠出機(PCM-30;(股)池貝製),於240℃、螺桿速度160rpm之加工條件進行造粒,得到合成樹脂組成物之丸粒(試驗試樣A:丸粒形狀)。
又,以與於製造實施例1中製造之丸粒相同成分,將粉末之樹脂添加劑組成物於同一條件進行造粒,得到合成樹脂組成物之丸粒(試驗試樣A:粉末)。
(製造比較例3)
(試驗試樣B之製造)
除了將製造實施例1中製造之樹脂添加劑組成物之丸粒變更為製造比較例1中得到之樹脂添加劑組成物之丸粒,且以鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯成為0.1質量份的方式添加以外,係與製造實施例2相同地,製造合成樹脂組成物之丸粒(試驗試樣B:丸粒形狀)。
又,以與於製造比較例1中製造之丸粒相同成分,將粉末之樹脂添加劑組成物於同一條件進行造粒,得到合成樹脂組成物之丸粒(試驗試樣B:粉末)。
(製造比較例4)
(試驗試樣C之製造)
除了將製造實施例1中製造之樹脂添加劑組成物之丸粒變更為製造比較例2中得到之樹脂添加劑組成物之丸粒,且以鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯成為0.1質量份的方式添加以外,係與製造實施例2相同地,製造合成樹脂組成物之丸粒(試驗試樣C:丸粒形狀)。
又,以與於製造比較例2中製造之丸粒相同成分,將粉末之樹脂添加劑組成物於同一條件進行造粒,得到合成樹脂組成物之丸粒(試驗試樣C:粉末)。
(彎曲彈性率)
將上述所得之丸粒,以射出成型機(EC100-2A;東芝機械(股)製),於射出溫度230℃、模具溫度50℃之條件進行射出成形,製作尺寸80mm×10mm×4mm之試驗片,於23℃之恆溫槽中靜置48小時以上後,根據ISO178,測定試驗片之彎曲彈性率(MPa)。此等之結果各自示於下述表4。
(荷重撓曲溫度(HDT))
將上述所得到之丸粒,以射出成型機(EC100-2A;東芝機械(股)製),於射出溫度230℃、模具溫度50℃之條件進行射出成形,製作尺寸80mm×10mm×4mm之試驗片,於23℃之恆溫槽中靜置48小時以上後,根據ISO75(荷重1.8MPa),測定試驗片之荷重撓曲溫度(℃)。此等之結果各自示於下述表4。
再者,下述表4中之數值係表示質量份。
由製造比較例3、4可知,僅含有(A)成分或(B)成分作為結晶核劑成分的丸粒形狀之樹脂添加劑組成物中,相較於摻合粉末狀之樹脂添加劑組成物的情況,物性之降低顯著。
相對於此,由製造實施例2可知,本發明之丸粒形狀的樹脂添加劑組成物中,可確認到不遜色於摻合粉末狀之
樹脂添加劑組成物時的物性,樹脂中之分散性優良。
Claims (5)
- 一種樹脂添加劑組成物,其係相對於鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯(A)100質量份而言,含有下述通式(1)表示之磷酸酯鋰鹽化合物(B)25~400質量份及下述通式(2)表示之脂肪酸金屬鹽(C)10~300質量份的樹脂添加劑組成物,其特徵在於相對於(A)成分及(B)成分之合計量100質量份而言,(C)成分之摻合量,為10質量份~50質量份之範圍內;
(式(1)中,R1~R4表示直鏈或具有分支之碳原子數1~8之烷基,R5表示碳原子數1~4之亞烷基); (式(2)中,R6表示無取代或經羥基取代之碳原子數1~40之脂肪族基,M表示金屬原子,n為1~4之整數,且表示M之金屬原子的價數)。 - 如請求項1之樹脂添加劑組成物,其中進一步含有相對於總量而言,為10質量%~50質量%之酚系抗氧化劑(D)。
- 如請求項2之樹脂添加劑組成物,其係丸粒形狀。
- 一種合成樹脂組成物,其特徵在於,相對於合成樹脂100質量份而言,於(A)成分及(B)成分之合計量為0.001~5質量份的範圍內含有如請求項1之樹脂添加劑組成物。
- 如請求項4之合成樹脂組成物,其中前述合成樹脂為聚烯烴系樹脂。
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| TWI778225B (zh) * | 2018-02-15 | 2022-09-21 | 日商Adeka股份有限公司 | 粒狀成核劑、樹脂組成物、成形品及其製造方法 |
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| JP6513278B1 (ja) * | 2018-08-30 | 2019-05-15 | 株式会社Adeka | 組成物、これを含有する熱可塑性樹脂組成物およびその成形品 |
| CN109438753A (zh) * | 2018-10-17 | 2019-03-08 | 山西省化工研究所(有限公司) | 一种α成核剂组合物及其制备方法与应用 |
| JP6731128B1 (ja) * | 2020-03-16 | 2020-07-29 | 株式会社Adeka | 粒状核剤、樹脂組成物およびその製造方法ならびに成形品 |
| JP2023533727A (ja) * | 2020-07-01 | 2023-08-04 | セラニーズ・インターナショナル・コーポレーション | ポリマー組成物、および同組成物から作製される改良された機械的強度を有する膜 |
| WO2022014686A1 (ja) * | 2020-07-15 | 2022-01-20 | 株式会社Adeka | 添加剤組成物、これを含有する樹脂組成物およびその成形品 |
| CN114561043B (zh) * | 2022-04-07 | 2023-01-31 | 涿州市隽诚化工有限公司 | 一种聚丙烯成核剂组合物及其制备方法与应用 |
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| JP6885667B2 (ja) | 2021-06-16 |
| RU2018109473A (ru) | 2019-09-23 |
| WO2017029970A1 (ja) | 2017-02-23 |
| KR20220162831A (ko) | 2022-12-08 |
| AU2016309150A1 (en) | 2018-04-05 |
| CN107614618A (zh) | 2018-01-19 |
| BR112018003146B1 (pt) | 2022-01-25 |
| BR112018003146A2 (pt) | 2018-09-18 |
| CN107614618B (zh) | 2021-04-16 |
| TWI725043B (zh) | 2021-04-21 |
| EP3339376B1 (en) | 2024-09-25 |
| US20180230293A1 (en) | 2018-08-16 |
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