CN107614618A - 树脂添加剂组合物及使用其的合成树脂组合物 - Google Patents
树脂添加剂组合物及使用其的合成树脂组合物 Download PDFInfo
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- CN107614618A CN107614618A CN201680026808.4A CN201680026808A CN107614618A CN 107614618 A CN107614618 A CN 107614618A CN 201680026808 A CN201680026808 A CN 201680026808A CN 107614618 A CN107614618 A CN 107614618A
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- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K5/13—Phenols; Phenolates
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- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
本发明提供树脂添加剂组合物及使用其的合成树脂组合物,所述树脂添加剂组合物含有特定的磷酸酯金属盐,即使制成颗粒形状时在树脂中的分散性也优异,配混于树脂时可得到期望的物性改良效果。一种树脂添加剂组合物,其相对于2,2’‑亚甲基双(4,6‑二叔丁基苯基)磷酸酯钠(A)100质量份,含有通式(1)所示的磷酸酯锂盐化合物(B)25~400质量份和通式(2)所示的脂肪酸金属盐(C)10~300质量份。相对于(A)成分和(B)成分的总量100质量份,(C)成分的配混量为10质量份~50质量份。
Description
技术领域
本发明涉及含有特定的磷酸酯金属盐的树脂添加剂组合物,详细而言,本发明涉及树脂添加剂组合物、及使用其的合成树脂组合物,对于所述树脂添加剂组合物,含有磷酸酯金属盐,且含有特定的锂盐的化合物作为结晶成核剂成分,进而含有脂肪酸金属盐,由此提高了树脂中的分散性。
背景技术
聚乙烯、聚丙烯、聚丁烯-1等聚烯烃系树脂、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯系高分子、聚酰胺系高分子等合成树脂的加热成型后的结晶化速度慢。因此,存在加工时的成型周期长等的问题,在此基础上,由于在成型后所进行的结晶化而使成型物变形。
已知这些缺点源自于合成树脂的结晶性,通过生成多个微细的结晶而能够得以解决。作为生成多个微细的结晶的方法,已知提高结晶化温度、或添加结晶成核剂、结晶化促进剂等。
作为结晶成核剂,已知例如有苯甲酸钠、4-叔丁基苯甲酸铝盐、己二酸钠和2-双环[2.2.1]戊烷-2,3-二羧酸钠等羧酸金属盐、双(4-叔丁基苯基)磷酸酯钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠和2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂等磷酸酯金属盐、二苄叉基山梨糖醇、双(甲基苄叉基)山梨糖醇、双(3,4-二甲基苄叉基)山梨糖醇、双(p-乙基苄叉基)山梨糖醇、和双(二甲基苄叉基)山梨糖醇等多元醇衍生物、N,N’,N”-三[2-甲基环己基]-1,2,3-丙烷三甲酰胺、N,N’,N”-三环己基-1,3,5-苯基三甲酰胺、N,N’-二环己基萘二甲酰胺、1,3,5-三(2,2-二甲基丙酰胺)苯等酰胺化合物等。
这些当中,2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠如专利文献1~3所记载的那样,已知作为合成树脂的物性改善效果高的结晶成核剂而被广泛使用。
另外,专利文献4中提出了一种结晶成核剂组合物,其含有2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯的铝盐和脂肪族有机酸金属盐。
2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠的形状为粉末,但使用粉末会担心由漂浮粉尘导致的操作安全性。另外,也存在根据各种用途而必需以任意的配混量均匀地配混多种树脂添加剂这样的问题。因此,从计量性和操作性的观点出发,对于将各种树脂添加剂成型为颗粒形状而成的树脂添加剂组合物的期望高。例如,专利文献5、6中提出了使用了2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠的树脂添加剂组合物。
现有技术文献
专利文献
专利文献1:日本特开昭58-1736号公报
专利文献2:日本特开昭59-184252号公报
专利文献3:日本特开昭63-108063号公报
专利文献4:日本特开2002-338820号公报
专利文献5:日本特开2001-123021号公报
专利文献6:日本特开2004-292710号公报
发明内容
发明要解决的问题
复合制造商中,通常向颗粒形状的树脂中配混树脂添加剂来进行成型加工,但使用粉末形状的树脂添加剂时,与颗粒形状的树脂的比重差大,因此难以将它们均匀地混合。特别是,2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠是难以分散在树脂中的化合物,因此要求对分散性进行改良。
另外,将2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠成型为颗粒形状的树脂添加剂组合物时,也存在在树脂中的分散性恶化而变得难以得到期望的物性,需要进行大量添加这样的问题。
迄今为止,进行了提高2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠的分散性的研究,但尚未得到令人满意的成果。
因此,本发明的目的在于提供树脂添加剂组合物及使用其的合成树脂组合物,所述树脂添加剂组合物含有特定的磷酸酯金属盐,即使制成颗粒形状时在树脂中的分散性也优异,配混于树脂时可得到期望的物性改良效果。
用于解决问题的方案
本发明人等进行了深入研究,结果发现,相对于2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠,混合特定的锂盐的化合物和脂肪酸金属盐,从而可以解决上述问题,以至完成了本发明。
关于本发明的树脂添加剂组合物,其特征在于,相对于2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠(A)100质量份,含有下述通式(1)所示的磷酸酯锂盐化合物(B)25~400质量份和下述通式(2)所示的脂肪酸金属盐(C)10~300质量份,
相对于(A)成分和(B)成分的总量100质量份,(C)成分的配混量在10质量份~50质量份的范围内。
(式(1)中,R1~R4表示直链或具有支链的碳原子数1~8的烷基,R5表示碳原子数1~4的烷叉基)
(式(2)中,R6表示无取代或被羟基取代的碳原子数1~40的脂肪族基团,M表示金属原子,n为1~4的整数、表示M的金属原子的价数)
本发明的树脂添加剂组合物优选以相对于总量为10质量%~50质量%的方式进一步含有酚系抗氧化剂(D)。
本发明的树脂添加剂组合物优选具有颗粒形状。
关于本发明的合成树脂组合物,其特征在于,相对于合成树脂100质量份,在(A)成分和(B)成分的总量为0.001~5质量份的范围内含有上述本发明的树脂添加剂组合物。
另外,本发明优选前述合成树脂为聚烯烃系树脂的合成树脂组合物。
发明的效果
根据本发明,能够实现树脂添加剂组合物及使用其的合成树脂组合物,所述树脂添加剂组合物含有特定的磷酸酯金属盐,即使制成颗粒形状时在树脂中的分散性也优异,配混于树脂时可得到期望的物性改良效果。
具体实施方式
以下对本发明的实施方式进行详细说明。
[磷酸酯锂盐化合物(B)]
本发明中使用的磷酸酯锂盐化合物是下述通式(1)所示的化合物。
(式(1)中,R1~R4表示直链或具有支链的碳原子数1~8的烷基,R5表示碳原子数1~4的烷叉基)
作为通式(1)中的R1~R4所示的直链或具有支链的碳原子数1~8的烷基,例如可以列举出:甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基、戊基、叔戊基、己基、庚基、辛基、异辛基、叔辛基、2-乙基己基等。本发明中特别优选叔丁基。
作为通式(1)中的R5所示的碳原子数1~4的烷叉基,例如可以列举出:甲叉基、乙叉基、丙叉基、丁叉基等。
作为通式(1)所示的磷酸酯锂盐化合物的具体结构,例如可以列举出下述化合物。但是,本发明不受以下化合物的限制。
本发明中,磷酸酯锂盐化合物(B)的用量相对于2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠(A)100质量份为25~400质量份、优选为50~100质量份。磷酸酯锂盐化合物(B)的用量不在25~400质量份的范围内时,有时无法得到本发明的效果。
[脂肪酸金属盐(C)]
本发明中使用的脂肪酸金属盐(C)是下述通式(2)所示的化合物。
(式(2)中,R6表示无取代或被羟基取代的碳原子数1~40的脂肪族基团,M表示金属原子,n为1~4的整数、表示M的金属原子的价数)
通式(2)中,作为R6所示的、碳原子数1~40的脂肪族基团,可列举出:烷基、烯基、导入了2个以上不饱和键的烷基等烃基,也可以被羟基取代,也可以具有支链。
具体而言,可列举出:乙酸、丙酸、丁酸、戊酸、异戊酸、己酸、庚酸、辛酸、壬酸、癸酸、2-乙基己烷酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、十六烷酸、十七烷酸、硬脂酸、十九烷酸、花生酸、二十一烷酸、山萮酸、二十三烷酸、二十四烷酸、蜡酸、褐煤酸、蜂花酸等饱和脂肪酸;4-癸烯酸、4-十二碳烯酸、棕榈油酸、α-亚麻酸、亚油酸、γ-亚麻酸、十八碳四烯酸、岩芹酸、油酸、反油酸、异油酸、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等直链不饱和脂肪酸;均苯三酸等芳香族脂肪酸。本发明中,优选碳原子数7~21的脂肪族基团、特别优选肉豆蔻酸、硬脂酸、12-羟基硬脂酸等饱和脂肪酸。
通式(2)中,M所示的金属原子可以列举出碱金属、镁、钙、锶、钡、钛、锰、铁、锌、硅、锆、钇、钡或铪等。这些当中,尤其可优选使用钠、锂、钾等碱金属。
本发明中,作为脂肪酸金属盐(C),根据性能良好且较容易获得,可优选列举出硬脂酸锂、硬脂酸钠、硬脂酸镁、硬脂酸锌、硬脂酸铝、肉豆蔻酸锂、山萮酸镁、12-羟基硬脂酸锂等,更优选列举出肉豆蔻酸锂、硬脂酸锂、12-羟基硬脂酸锂等。
上述脂肪酸金属盐可以利用如下方法来制造,所述方法为:使羧酸化合物与金属氢氧化物进行反应,然后进行水洗、脱水、干燥的合成方法(复分解法);不使用水的情况下直接进行反应的合成法(直接法)。
脂肪酸金属盐(C)的用量相对于2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠(A)100质量份为10~300质量份、优选为20~200质量份,相对于(A)成分和(B)成分的总量100质量份,需要在10质量份~50质量份的范围内。相对于(A)成分和(B)成分的总量100质量份,脂肪酸金属盐(C)的用量少于10质量份时,有时无法得到本发明的效果,多于50质量份时,有时会抑制结晶成核剂成分的性能(成核剂效果)。
对于本发明的树脂添加剂组合物,在不显著损害本发明的效果的范围内,除了上述(A)~(C)成分以外还可以含有任意公知的树脂添加剂,例如,酚系抗氧化剂、磷系抗氧化剂、硫醚系抗氧化剂、紫外线吸收剂、受阻胺化合物、除了上述(A)成分和(B)成分以外的结晶成核剂、阻燃剂、阻燃助剂、润滑剂、填充材料、金属皂、水滑石类、抗静电剂、颜料、染料等。另外,公知的树脂添加剂也可以与本发明的树脂添加剂组合物分开配混在合成树脂中。
本发明的树脂添加剂组合物特别优选进一步含有酚系抗氧化剂(D)。
[酚系抗氧化剂(D)]
本发明中使用的酚系抗氧化剂是在其分子结构中包含酚骨架的公知的抗氧化剂。具体而言,可列举出:2,6-二叔丁基-对甲酚、2,6-二苯基-4-十八烷氧基苯酚、硬脂基(3,5-二叔丁基-4-羟基苯基)丙酸酯、二硬脂基(3,5-二叔丁基-4-羟基苄基)膦酸酯、十三烷基-3,5-二叔丁基-4-羟基苄基硫代乙酸酯、硫代二亚乙基双[(3,5-二叔丁基-4-羟基苯基)丙酸酯]、4,4’-硫代双(6-叔丁基-间甲酚)、2-辛硫基-4,6-二(3,5-二叔丁基-4-羟基苯氧基)-均三嗪、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、双[3,3-双(4-羟基-3-叔丁基苯基)丁酸]二醇酯、4,4’-亚丁基双(4,6-二叔丁基苯酚)、2,2’-亚乙基双(4,6-二叔丁基苯酚)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、双[2-叔丁基-4-甲基-6-(2-羟基-3-叔丁基-5-甲基苄基)苯基]对苯二甲酸酯、1,3,5-三(2,6-二甲基-3-羟基-4-叔丁基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,3,5-三[(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基]异氰脲酸酯、四[3-(3’,5’-二叔丁基-4’-羟基苯基)炔丙氧基甲基]甲烷、2-叔丁基-4-甲基-6-(2-丙烯酰氧基-3-叔丁基-5-甲基苄基)苯酚、3,9-双[2-(3-叔丁基-4-羟基-5-甲基氢化肉桂酰氧基)-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷、三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]等。
这些当中,尤其四[3-(3,5-二叔丁基-4-羟基苯基)炔丙氧基甲基]甲烷因对聚烯烃树脂赋予优异的抗氧化效果,且容易将树脂添加剂组合物成型为颗粒形状,故而优选。
酚系抗氧化剂的用量优选以相对于树脂添加剂组合物的总量在10质量%~50质量%的范围内的方式进行调整。通过将酚系抗氧化剂的用量设为10质量%以上,从而容易成型为颗粒,且容易维持颗粒形状。另外,通过将酚系抗氧化剂的用量设为50质量%以下,从而能够在不阻碍(A)成分和(B)成分带来的结晶成核剂的作用效果的情况下更好地得到本发明的效果。
作为磷系抗氧化剂,可列举出:三苯基亚磷酸酯、二异辛基亚磷酸酯、三亚磷酸庚基(二丙二醇)酯、三异癸基亚磷酸酯、二苯基异辛基亚磷酸酯、二异辛基苯基亚磷酸酯、二苯基十三烷基亚磷酸酯、三异辛基亚磷酸酯、三月桂基亚磷酸酯、二苯基亚磷酸酯、三(二丙二醇)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、二油基氢化亚磷酸酯、三月桂基三硫代亚磷酸酯、双(十三烷基)亚磷酸酯、三(异癸基)亚磷酸酯、三(十三烷基)亚磷酸酯、二苯基癸基亚磷酸酯、二壬基苯基双(壬基苯基)亚磷酸酯、聚(二丙二醇)苯基亚磷酸酯、四苯基二丙二醇二亚磷酸酯、三壬基苯基亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、三(2,4-二叔丁基-5-甲基苯基)亚磷酸酯、三〔2-叔丁基-4-(3-叔丁基-4-羟基-5-甲基苯基硫代)-5-甲基苯基〕亚磷酸酯、三(癸基)亚磷酸酯、辛基二苯基亚磷酸酯、二(癸基)单苯基亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、二硬脂基季戊四醇与硬脂酸钙盐的混合物、烷基(C10)双酚A亚磷酸酯、二(十三烷基)季戊四醇二亚磷酸酯、二(壬基苯基)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯、四苯基-四(十三烷基)季戊四醇四亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、四(十三烷基)异亚丙基联苯酚二亚磷酸酯、四(十三烷基)-4,4’-正亚丁基双(2-叔丁基-5-甲基苯酚)二亚磷酸酯、六(十三烷基)-1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷三亚磷酸酯、四(2,4-二叔丁基苯基)亚联苯基二亚磷酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、(1-甲基-1-丙烯基-3-亚基)三(1,1-二甲基乙基)-5-甲基-4,1-亚苯基)六(十三烷基)亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-2-乙基己基亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-十八烷基亚磷酸酯、2,2’-亚乙基双(4,6-二叔丁基苯基)氟亚磷酸酯、4,4’-亚丁基双(3-甲基-6-叔丁基苯基双十三烷基)亚磷酸酯、三(2-〔(2,4,8,10-四-叔丁基二苯并〔d,f〕〔1,3,2〕二氧磷杂七环-6-基)氧基〕乙基)胺、3,9-双(4-壬基苯氧基)-2,4,8,10-四氧-3,9-二磷杂螺[5,5]十一烷、2,4,6-三叔丁基苯基-2-丁基-2-乙基-1,3-丙二醇亚磷酸酯、聚4,4’-异亚丙基联苯酚C12-15醇亚磷酸酯等。
磷系抗氧化剂的优选用量相对于合成树脂100质量份为0.001~10质量份、更优选为0.01~0.5质量份的范围。
作为硫醚系抗氧化剂,例如可列举出:四[亚甲基-3-(月桂基硫代)丙酸酯]甲烷、双(甲基-4-[3-正烷基(C12/C14)硫代丙酰氧基]5-叔丁基苯基)硫醚、双十三烷基-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’-硫代双(6-叔丁基-间甲酚)、2,2’-硫代双(6-叔丁基-对甲酚)、二硬脂基-二硫醚等。
硫醚系抗氧化剂的优选用量相对于合成树脂100质量份为0.001~10质量份、更优选为0.01~0.5质量份的范围。
作为紫外线吸收剂,例如可列举出:2,4-二羟基二苯甲酮、5,5’-亚甲基双(2-羟基-4-甲氧基二苯甲酮)等2-羟基二苯甲酮类;2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)-5-氯代苯并三唑、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯代苯并三唑、2-(2-羟基-3,5-二枯基苯基)苯并三唑、2,2’-亚甲基双(4-叔辛基-6-苯并三唑基苯酚)、2-(2-羟基-3-叔丁基-5-羧基苯基)苯并三唑的聚乙二醇酯、2-〔2-羟基-3-(2-丙烯酰氧基乙基)-5-甲基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔辛基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕-5-氯代苯并三唑、2-〔2-羟基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔丁基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔戊基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔丁基-5-(3-甲基丙烯酰氧基丙基)苯基〕-5-氯代苯并三唑、2-〔2-羟基-4-(2-甲基丙烯酰氧基甲基)苯基〕苯并三唑、2-〔2-羟基-4-(3-甲基丙烯酰氧基-2-羟基丙基)苯基〕苯并三唑、2-〔2-羟基-4-(3-甲基丙烯酰氧基丙基)苯基〕苯并三唑等2-(2-羟基苯基)苯并三唑类;水杨酸苯酯、间苯二酚单苯甲酸酯、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、辛基(3,5-二叔丁基-4-羟基)苯甲酸酯、十二烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十四烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十六烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十八烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、二十二烷基(3,5-二叔丁基-4-羟基)苯甲酸酯等苯甲酸酯类;2-乙基-2’-乙氧基草酰替苯胺、2-乙氧基-4’-十二烷基草酰替苯胺等取代草酰替苯胺类;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(对甲氧基苯基)丙烯酸酯等氰基丙烯酸酯类;各种金属盐或金属螯合物、特别是镍、铬的盐、或螯合物类等。
紫外线吸收剂的优选用量相对于合成树脂100质量份为0.001~5质量份、更优选为0.005~0.5质量份的范围。
作为受阻胺化合物,例如可列举出: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-哌啶基苯甲酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、双(2,2,6,6-四甲基-4-哌啶基)·二(十三烷基)-1,2,3,4-丁烷四甲酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四甲酸酯、双(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二叔丁基-4-羟基苄基)丙二酸酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-吗啉基-均三嗪缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-叔辛基氨基-均三嗪缩聚物、1,5,8,12-四〔2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8,12-四氮杂十二烷、1,5,8,12-四〔2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8-12-四氮杂十二烷、1,6,11-三〔2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基)-均三嗪-6-基〕氨基十一烷、1,6,11-三〔2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基)-均三嗪-6-基〕氨基十一烷、双{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}癸烷二酮酸酯、双{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基)碳酸酯、CibaSpecialty Chemicals Inc.制TINUVIN NOR 371等。
受阻胺化合物的优选用量相对于合成树脂100质量份为0.001~5质量份、更优选为0.005~0.5质量份的范围。
作为除了(A)成分和(B)成分以外的结晶成核剂,例如可以列举出:苯甲酸钠、4-叔丁基苯甲酸铝盐、己二酸钠和双环[2.2.1]庚烷-2,3-二羧酸二钠等羧酸金属盐、二亚苄基山梨糖醇、双(甲基亚苄基)山梨糖醇、双(3,4-二甲基亚苄基)山梨糖醇、双(对乙基亚苄基)山梨糖醇和双(二甲基亚苄基)山梨糖醇等多元醇衍生物、N,N’,N”-三[2-甲基环己基]-1,2,3-丙烷三甲酰胺、N,N’,N”-三环己基-1,3,5-苯三甲酰胺、N,N’-二环己基萘二甲酰胺、1,3,5-三(二甲基异丙基氨基)苯等酰胺化合物等。
结晶成核剂的优选用量相对于合成树脂100质量份,包含(A)成分和(B)成分的总量为0.001~5质量份、更优选为0.005~0.5质量份的范围。
作为阻燃剂,例如可以列举出:磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯基)酯、磷酸甲苯二苯酯、甲苯基-2,6-二(二甲苯基)磷酸酯、间苯二酚双(二苯基磷酸酯)、(1-甲基亚乙基)-4,1-亚苯基四苯基二磷酸酯、1,3-亚苯基四(2,6-二甲基苯基)磷酸酯、ADEKA株式会社制造的商品名ADK STAB FP-500、ADEKA株式会社制造的商品名ADK STAB FP-600、ADEKA株式会社制造的商品名ADK STAB FP-800等芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙基酯、苯基膦酸(1-丁烯基)酯等膦酸酯、二苯基次膦酸苯酯、二苯基次膦酸甲酯、9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物衍生物等次膦酸酯、双(2-烯丙基苯氧基)膦腈、二甲苯基膦腈等膦腈化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜勒胺、聚磷酸铵、磷酸哌嗪、焦磷酸哌嗪、聚磷酸哌嗪、含磷的乙烯基苄基化合物以及红磷等磷系阻燃剂、氢氧化镁、氢氧化铝等金属氢氧化物、溴化双酚A型环氧树脂、溴化苯酚酚醛清漆型环氧树脂、六溴苯、五溴甲苯、亚乙基双(五溴苯基)、亚乙基双四溴酞酰亚胺、1,2-二溴-4-(1,2-二溴乙基)环己烷、四溴环辛烷、六溴环十二烷、双(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯和2,4,6-三(三溴苯氧基)-1,3,5-三嗪、三溴苯基马来酰亚胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴双酚A型二甲基丙烯酸酯、丙烯酸五溴苄酯和溴化苯乙烯等溴系阻燃剂等。这些阻燃剂优选与氟树脂等防滴剂、多元醇、水滑石等阻燃助剂组合使用。
阻燃剂的优选用量相对于合成树脂100质量份为1~50质量份、更优选为10~30质量份的范围。
润滑剂以对成型体表面赋予润滑性,提高防划痕效果为目的而添加。作为润滑剂,例如可列举出:油酸酰胺、芥酸酰胺等不饱和脂肪酸酰胺;山萮酸酰胺、硬脂酸酰胺等饱和脂肪酸酰胺、硬脂酸丁酯、硬脂醇、硬脂酸甘油单酯、失水山梨醇单棕榈酸酯、失水山梨醇单硬脂酸酯、甘露糖醇、硬脂酸、硬化蓖麻油、硬脂酸酰胺、油酸酰胺、亚乙基二硬脂酸酰胺等。它们可以单独使用一种,也可以同时使用两种以上。
润滑剂的优选用量相对于合成树脂100质量份为0.01~2质量份、更优选为0.03~0.5质量份的范围。
作为填充剂,例如可以列举出:滑石、云母、碳酸钙、氧化钙、氢氧化钙、碳酸镁、氢氧化镁、氧化镁、硫酸镁、氢氧化铝、硫酸钡、玻璃粉末、玻璃纤维、黏土、白云石、云母、二氧化硅、氧化铝、钛酸钾晶须、硅灰石、纤维状碱式硫酸镁等,可以适宜选择粒径(纤维状的情况为纤维径、纤维长度和长径比)来使用。另外,填充剂可以根据需要使用经表面处理了的物质。
填充剂的优选用量相对于合成树脂100质量份为0.01~80质量份、更优选为1~50质量份的范围。
作为金属皂,可使用镁、钙、铝、锌等金属与月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸等饱和或不饱和脂肪酸的盐。
金属皂的优选用量相对于合成树脂100质量份为金属皂0.001~10质量份、更优选为0.01~5质量份的范围。
作为水滑石类,是天然物、作为合成物已知的由镁、铝、羟基、碳酸基和任意结晶水形成的复合盐化合物,可列举出:镁或铝的一部分用碱金属、锌等其它金属置换而成的物质;羟基、碳酸基用其它阴离子基置换而成的物质,具体而言,例如可列举出由下述通式(3)表示的水滑石的金属置换为碱金属而成的物质。另外,作为Al-Li系水滑石类,也可以使用由下述通式(4)表示的化合物。
Mgx1Znx2A12(OH)2(x1+x2)+4(CO3)pH2O (3)
此处,通式(3)中,x1和x2分别表示满足下述式表示的条件的数,
0≤x2/x1<10,2≤x1+x2≤20,p表示0或正数。
[Li1/3A12/3(OH)2]·[Aq- 1/3q·pH2O] (4)
此处,通式(4)中,Aq-表示q价的阴离子,p表示0或正数。
另外,也可以为水滑石类中的碳酸阴离子的一部分用其它阴离子置换而成的物质。
水滑石类可以为结晶水脱水而成的物质,也可以为用硬脂酸等高级脂肪酸、油酸碱金属盐等高级脂肪酸金属盐、十二烷基苯磺酸碱金属盐等有机磺酸金属盐、高级脂肪酸酰胺、高级脂肪酸酯或蜡等被覆而成的物质。
水滑石类可以为天然物也可以为合成物。作为该化合物的合成方法,可列举出:日本特公昭46-2280号公报、日本特公昭50-30039号公报、日本特公昭51-29129号公报、日本特公平3-36839号公报、日本特开昭61-174270号公报、日本特开平5-179052号公报等中记载的公知的方法。另外,前述水滑石类可以不受其晶体结构、晶体颗粒等的限制而使用。
水滑石类的优选用量相对于合成树脂100质量份为0.001~5质量份、更优选为0.05~3质量份的范围。
作为抗静电剂,例如可列举出:脂肪酸季铵离子、多胺季盐等阳离子系抗静电剂;高级醇磷酸酯盐、高级醇EO加成物、聚乙二醇脂肪酸酯、阴离子型的烷基磺酸盐、高级醇硫酸酯盐、高级醇环氧乙烷加成物硫酸酯盐、高级醇环氧乙烷加成物磷酸酯盐等阴离子系抗静电剂;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非离子系抗静电剂;烷基二甲基氨基乙酸甜菜碱等两性型烷基甜菜碱、咪唑啉型两性活性剂等两性抗静电剂。该抗静电剂可以单独使用,另外,也可以组合两种以上抗静电剂来使用。
抗静电剂的优选用量相对于合成树脂100质量份为0.03~2质量份、更优选为0.1~0.8质量份的范围。
作为颜料,可以使用市售的颜料,例如可列举出:颜料红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;颜料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;颜料黄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;颜料绿7、10、36;颜料蓝15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、56、60、61、62、64;颜料紫1、19、23、27、29、30、32、37、40、50等。
作为染料,可列举出:偶氮染料、蒽醌染料、靛类染料、三芳基甲烷染料、氧杂蒽染料、茜素染料、吖啶染料、均二苯代乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲达胺染料、噁嗪染料、酞菁染料、花青染料等,这些也可以混合多个来使用。
本发明的树脂添加剂组合物优选具有颗粒形状。作为具有颗粒形状的树脂添加剂组合物的制造方法,可以在熔融状态的酚系抗氧化剂的存在下对混合上述(A)成分~(C)成分和酚系抗氧化剂、及根据需要任意包含的其它添加剂而成的混合物进行混合来制造。加工条件、加工机器等可以没有任何限定地使用公知一般的加工方法、加工机器。
作为具体的制造方法,可列举出圆盘造粒法、挤出法等。本发明中,优选大量生产容易、且颗粒的形状维持优异的挤出法。另外,挤出法中的加工温度优选酚系抗氧化剂的熔点以上、且熔点加上50℃的范围内。低于酚系抗氧化剂的熔点时,有时颗粒的形状的稳定性不够,高于酚系抗氧化剂的熔点加上50℃时,有时树脂添加剂组合物的流动性变大,变得难以成型。
(粉化率)
本发明的具有颗粒形状的树脂添加剂组合物优选在输送时能够维持产品形状。具体而言,期望的是:向500ml塑料容器中加入不会通过筛孔为1.39mm的筛的试样100g,以振幅40mm、振动速度300循环/分钟振动4小时后,通过筛孔1.39mm的筛的试样优选低于1质量%、更优选低于0.5质量%。
关于本发明的合成树脂组合物,相对于合成树脂100质量份,以(A)成分和(B)成分的总量在0.001~5质量份的范围内、优选在0.005~0.5质量份的范围内含有上述本发明的树脂添加剂组合物。(A)成分和(B)成分的总量少于上述范围时,有时无法得到结晶成核剂的效果,多于上述范围时,有时无法得到对应于添加量的效果而不经济,另外,有时会出现在成型品的表面而损害外观。在任意情况下均无法得到本发明所期望的效果。
将本发明的树脂添加剂组合物配混于合成树脂来进行成型时,可以使用公知的成型方法进行成型。例如,合成树脂为热塑性树脂时,可以使用注射成型法、挤出成型法、吹塑成型法、真空成型法、吹胀成型法、压延成型法、搪塑成型法、浸渍成型法、发泡成型法等来得到成型品。
另外,合成树脂为可使用热、光、辐射线和其它方式进行固化的固化性树脂时,可以使用压缩成型法、注射成型法、低压成型法、层压成型法等来得到成型品。
作为本发明中的合成树脂,例如可以列举出:聚丙烯、高密度聚乙烯、低密度聚乙烯、直链低密度聚乙烯、聚丁烯-1、聚-3-甲基戊烯等α-烯烃聚合物;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-丙烯共聚物等聚烯烃和它们的共聚物;聚氯乙烯、聚偏氯乙烯、氯化聚乙烯、氯化聚丙烯、聚偏氟乙烯、氯化橡胶、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏氯乙烯共聚物、氯乙烯-偏氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-马来酸酯共聚物、氯乙烯-环己基马来酰亚胺共聚物等含卤素树脂;石油树脂;香豆酮树脂;聚苯乙烯;聚乙酸乙烯酯;丙烯酸类树脂;苯乙烯和/或α-甲基苯乙烯与其它单体(例如,马来酸酐、苯基马来酰亚胺、甲基丙烯酸甲酯、丁二烯、丙烯腈等)的共聚物(例如,AS树脂、ABS树脂、MBS树脂、耐热ABS树脂等);聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯醇缩丁醛、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等直链聚酯;聚苯醚、聚己内酰胺、聚己二酰己二胺等聚酰胺;聚碳酸酯、聚碳酸酯/ABS树脂、支链聚碳酸酯、聚缩醛、聚苯硫醚、聚氨酯、三乙酸纤维素、纤维系树脂等热塑性树脂和它们的混合物;酚醛树脂、尿素树脂、三聚氰胺树脂、环氧树脂、不饱和聚酯树脂等热固化性树脂。进而,也可以是异戊橡胶、丁二烯橡胶、丙烯腈-丁二烯共聚橡胶、苯乙烯-丁二烯共聚橡胶等弹性体。这些合成树脂可以单独使用,或者也可以混合两种以上来使用。
作为本发明中使用的合成树脂,选自乙烯均聚物、丙烯均聚物、乙烯/丙烯嵌段或无规共聚物、除了乙烯以外的α-烯烃/丙烯嵌段或无规共聚物、及这些聚合物的混合物的聚烯烃系树脂使本发明的效果变得显著,故而优选。
作为本发明的合成树脂组合物的用途,可列举出:保险杠、减震器、仪表板等汽车材料、冰箱、洗衣机、吸尘器等的壳体用途、餐具、水桶、洗浴用品等家庭用品、玩具等杂货品、容器类等储藏、保存用容器等成型品、薄膜、纤维等。
实施例
以下列举实施例对本发明进行更具体地说明,但本发明不受以下实施例等的任何限制。
相对于熔体流动速率25g/10分钟的聚丙烯嵌段共聚物100质量份,使用亨舍尔混合器(Mitsui Mining Co.,Ltd.制、产品名FM200;搅拌翼转速1000rpm,1分钟)混合作为酚系抗氧化剂的四[亚甲基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯]甲烷0.1质量份、作为磷系抗氧化剂的三(2,4-二叔丁基苯基)亚磷酸酯0.1质量份、作为中和剂的硬脂酸钙0.05质量份、及下述表1或表2所示的树脂添加剂组合物,然后使用双螺杆挤出机(PCM-30;Ikegai Corporation制)在240℃、螺杆速度160rpm的加工条件下进行造粒,得到合成树脂组合物的颗粒。
(弯曲模量)
使用得到的颗粒,通过注射成型机(EC100-2A;Toshiba Machinery Co.,Ltd.制),在注射温度230℃、模具温度50℃的条件下进行注射成型,得到宽度10mm、长度80mm、厚度4mm的试验片。对试验片进行注射成型后,立即在槽内温度为23℃的恒温槽中静置48小时以上,然后使用弯曲试验机测定了弯曲模量。
将这些结果示于下述表1。
(结晶化温度)
切取少量得到的颗粒,使用差示扫描热量测定器(Diamond PerkinElmer公司制),测定了结晶化温度。作为测定方法,以50℃/分钟的速度从室温升温至230℃,保持10分钟后以-10℃/分钟的速度冷却至50℃,在由此得到的图中,将吸热反应达到峰顶时的温度作为结晶化温度。
将这些结果示于下述表2。
[表1]
*1)化合物A:2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠
*2)化合物B:2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂
*3)LIM:肉豆蔻酸锂
*4)比较化合物1:双[2,2’亚甲基双(4,6-二叔丁基苯基)磷酸酯]羟基铝
*5)比较化合物2:苯甲酸钠
根据比较例1-3~1-5,在欠缺本发明的树脂添加剂组合物的(A)成分、(B)成分和(C)成分中任一者的情况下,物性的改良效果差。另外,根据比较例1-2,将(B)成分变更为与本发明的树脂添加剂组合物不同的成核剂的情况下,物性的改良效果也差。
相对于这些结果,能够确认到:本发明的实施例的树脂添加剂组合物的物性改良效果均优异。
[表2]
根据表2中的比较例2-2~2-4,能够确认到:与单独配混了化合物A的情况相比,本发明的各实施例的树脂添加剂组合物改善树脂的结晶化温度的效果高。
接着,关于树脂添加剂组合物,评价了颗粒形状的情况和粉末形状的情况的影响。
相对于在230℃下的熔体流动速率为25g/10分钟的聚丙烯嵌段共聚物100质量份,配混下述表3所示的树脂添加剂组合物,并实施了5分钟手动搅拌,然后使用双螺杆挤出机(PCM-30;Ikegai Corporation制)在240℃、螺杆速度160rpm的加工条件下进行造粒,得到合成树脂组合物的颗粒。
利用得到的颗粒,使用注射成型机(EC100-2A;Toshiba Machinery Co.,Ltd.制),在注射温度230℃、模具温度50℃的条件下进行注射成型,得到宽度10mm、长度80mm、厚度4mm的试验片。对试验片进行注射成型,然后立即在槽内温度为23℃的恒温槽中放置48小时以上,然后依据ISO178的试验方法测定了弯曲模量。将这些结果示于下述表3。
[表3]
根据比较例3-2,相对于颗粒形状的聚丙烯嵌段共聚物100质量份,仅配混了化合物A0.05质量份的情况几乎未得到成核剂的效果。相对与此,能够确认到:相对于颗粒形状的聚丙烯嵌段共聚物,本发明的各实施例的树脂添加剂组合物即使为低添加量也能够赋予成核剂效果。
接着,对将本发明的树脂添加剂组合物用于颗粒状的树脂添加剂组合物时的效果进行说明。
(制造实施例1)
2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠9.5质量%
2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂9.5质量%
肉豆蔻酸锂9.5质量%
酚系抗氧化剂:四[3-(3,5-二叔丁基-4-羟基苯基)炔丙氧基甲基]甲烷28.6质量%
磷系抗氧化剂:三(2,4-二叔丁基苯基)亚磷酸酯28.6质量%
催化失活剂:硬脂酸钙14.3质量%
根据上述配方,使用亨舍尔混合器(FM200;Mitsui Mining Co.,Ltd.制)在1000rpm、1分钟的条件下对它们进行混合,然后使用双螺杆挤出机(PCM-30;IkegaiCorporation制)在料筒温度设定:试样导入部30℃、中央部130℃、产品排出口附近100℃、挤出螺杆转速60rpm的加工条件下制造了颗粒形状的树脂添加剂组合物。
需要说明的是,该树脂添加剂组合物的配方内容相当于实施例1-4中评价的树脂添加剂组合物。
(制造比较例1)
2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠28.5质量%
酚系抗氧化剂:四[3-(3,5-二叔丁基-4-羟基苯基)炔丙氧基甲基]甲烷28.6质量%
磷系抗氧化剂:三(2,4-二叔丁基苯基)亚磷酸酯28.6质量%
催化失活剂:硬脂酸钙14.3质量%
根据上述配方,使用亨舍尔混合器(FM200;Mitsui Mining Co.,Ltd.制)在1000rpm、1分钟的条件下对它们进行混合,然后使用双螺杆挤出机(PCM-30;IkegaiCorporation制)在料筒温度设定:试样导入部30℃、中央部130℃、产品排出口附近100℃、挤出螺杆转速60rpm的加工条件下制造了颗粒形状的树脂添加剂组合物。
(制造比较例2)
2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂28.5质量%
酚系抗氧化剂:四[3-(3,5-二叔丁基-4-羟基苯基)炔丙氧基甲基]甲烷28.6质量%
磷系抗氧化剂:三(2,4-二叔丁基苯基)亚磷酸酯28.6质量%
催化失活剂:硬脂酸钙14.3质量%
根据上述配方,使用亨舍尔混合器(FM200;Mitsui Mining Co.,Ltd.制)在1000rpm、1分钟的条件下对它们进行混合,然后使用双螺杆挤出机(PCM-30;IkegaiCorporation制)在料筒温度设定:试样导入部30℃、中央部130℃、产品排出口附近100℃、挤出螺杆转速60rpm的加工条件下制造了颗粒形状的树脂添加剂组合物。
(制造实施例2)
(试验试样A的制造)
相对于230℃下的熔体流动速率8g/10分钟的均聚聚丙烯100质量份,以2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂和肉豆蔻酸锂的总计为0.1质量份的方式加入制造实施例1中制造的树脂添加剂组合物的颗粒并进行处理,使用双螺杆挤出机(PCM-30;Ikegai Corporation制)在240℃、螺杆速度160rpm的加工条件下进行造粒,得到合成树脂组合物的颗粒(试验试样A:颗粒形状)。
另外,在相同条件下对与在制造实施例1中制造的颗粒相同成分的粉末的树脂添加剂组合物进行造粒,得到合成树脂组合物的颗粒(试验试样A:粉末)。
(制造比较例3)
(试验试样B的制造)
将制造实施例1中制造的树脂添加剂组合物的颗粒变更为在制造比较例1中得到的树脂添加剂组合物的颗粒,以2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠为0.1质量份方式进行添加,除此以外与制造实施例2同样地制造了合成树脂组合物的颗粒(试验试样B:颗粒形状)。
另外,在相同条件下对与在制造比较例1中制造的颗粒相同成分的粉末的树脂添加剂组合物进行造粒,得到合成树脂组合物的颗粒(试验试样B:粉末)。
(制造比较例4)
(试验试样C的制造)
将制造实施例1中制造的树脂添加剂组合物的颗粒变更为在制造比较例2中得到的树脂添加剂组合物的颗粒,以2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂为0.1质量份方式进行添加,除此以外与制造实施例2同样地制造了合成树脂组合物的颗粒(试验试样C:颗粒形状)。
另外,在相同条件下对与在制造比较例2中制造的颗粒相同成分的粉末的树脂添加剂组合物进行造粒,得到合成树脂组合物的颗粒(试验试样C:粉末)。
(弯曲模量)
通过注射成型机(EC100-2A;Toshiba Machinery Co.,Ltd.制)在注射温度230℃、模具温度50℃的条件下对上述得到的颗粒进行注射成型,制造尺寸80mm×10mm×4mm的试验片,在23℃的恒温槽中静置48小时以上,然后依据ISO178测定了试验片的弯曲模量(MPa)。分别将这些结果示于下述表4。
(载荷挠曲温度(HDT))
通过注射成型机(EC100-2A;Toshiba Machinery Co.,Ltd.制)在注射温度230℃、模具温度50℃的条件下对上述得到的颗粒进行注射成型,制造尺寸80mm×10mm×4mm的试验片,在23℃的恒温槽中静置48小时以上,然后依据ISO75(载荷1.8MPa)测定了试验片的载荷挠曲温度(℃)。分别将这些结果示于下述表4。
需要说明的是,下述表4中的数值表示质量份。
[表4]
*6)AO-60:四[3-(3,5-二叔丁基-4-羟基苯基)炔丙氧基甲基]甲烷
*7)2112:三(2,4-二叔丁基苯基)亚磷酸酯
*8)Ca-St:硬脂酸钙
根据制造比较例3、4,作为结晶成核剂成分仅含有(A)成分或(B)成分的颗粒形状的树脂添加剂组合物与配混了粉末状的树脂添加剂组合物的情况相比,物性的降低显著。
相对于此,根据制造实施例2,能够确认到:本发明的颗粒形状的树脂添加剂组合物不逊色于配混了粉末状的树脂添加剂组合物时的物性,树脂中的分散性优异。
Claims (5)
1.一种树脂添加剂组合物,其特征在于,相对于2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠(A)100质量份,含有下述通式(1)所示的磷酸酯锂盐化合物(B)25~400质量份和下述通式(2)所示的脂肪酸金属盐(C)10~300质量份,
相对于(A)成分和(B)成分的总量100质量份,(C)成分的配混量在10质量份~50质量份的范围内,
式(1)中,R1~R4表示直链或具有支链的碳原子数1~8的烷基,R5表示碳原子数1~4的烷叉基,
式(2)中,R6表示无取代或被羟基取代的碳原子数1~40的脂肪族基团,M表示金属原子,n为1~4的整数、表示M的金属原子的价数。
2.根据权利要求1所述的树脂添加剂组合物,其中,进而以相对于总量为10质量%~50质量%的方式含有酚系抗氧化剂(D)。
3.根据权利要求2所述的树脂添加剂组合物,其为颗粒形状。
4.一种合成树脂组合物,其特征在于,相对于合成树脂100质量份,在(A)成分和(B)成分的总量为0.001~5质量份的范围内含有权利要求1所述的树脂添加剂组合物。
5.根据权利要求4所述的合成树脂组合物,其中,所述合成树脂为聚烯烃系树脂。
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