CN111094514A - 组合物及阻燃性树脂组合物 - Google Patents
组合物及阻燃性树脂组合物 Download PDFInfo
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- CN111094514A CN111094514A CN201880056743.7A CN201880056743A CN111094514A CN 111094514 A CN111094514 A CN 111094514A CN 201880056743 A CN201880056743 A CN 201880056743A CN 111094514 A CN111094514 A CN 111094514A
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Abstract
本发明的组合物含有(A)磷酸胺盐和(B)氰脲酸三聚氰胺。本发明的组合物优选上述(A)成分含有下述(A‑1)及(A‑2)。(A‑1)成分:选自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺构成的组中的至少一种三聚氰胺盐;(A‑2)成分:选自由正磷酸哌嗪、焦磷酸哌嗪及多磷酸哌嗪构成的组中的至少一种哌嗪盐。根据本发明,能够提供通过与树脂混合,可得到给予防滴落效果、能够对该树脂赋予优异的阻燃性、并且表面平滑性良好的成形品的组合物。
Description
技术领域
本发明涉及具有磷酸胺盐及氰脲酸三聚氰胺的组合物及配合了该组合物的阻燃性树脂组合物。
背景技术
以往,合成树脂由于其优异的化学特性、机械特性而被广泛用于建筑材料、汽车部件、包装用材料、农业用材料、家电制品的外壳材料、玩具等。但是,大多数的合成树脂为可燃性物质,根据用途而阻燃化是不可或缺的。作为阻燃化方法,单独或组合使用卤素系阻燃剂、以红磷或多磷酸铵等多磷酸系阻燃剂为代表的无机磷系阻燃剂、以三芳基磷酸酯化合物为代表的有机磷系阻燃剂、金属氢氧化物或作为阻燃助剂的氧化锑、三聚氰胺化合物是众所周知的。
特别是已知有以多磷酸或焦磷酸与含氮化合物的盐作为主要成分的、通过在燃烧时形成表面膨胀层(Intumescent)而抑制分解产物的扩散或传热来发挥阻燃性的膨胀系阻燃剂。这样的阻燃剂例如记载于专利文献1中。
在专利文献2中,公开了含有磷化合物和三聚氰胺与氰脲酸的反应产物的阻燃剂。但是,该阻燃剂中包含20质量%左右的氰脲酸三聚氰胺,从树脂物性的降低或经济的观点出发存在问题。
在专利文献3中,公开了一种阻燃性树脂组合物,其含有用偶联剂进行了表面处理的氰脲酸三聚氰胺。在该阻燃性树脂组合物中,相对于树脂配合有10质量%左右的进行了表面处理的氰脲酸三聚氰胺,从树脂的机械特性的降低或经济的观点出发存在问题。
在专利文献4中,公开了一种阻燃性树脂组合物,其是在聚烯烃系树脂中添加无机物即氢氧化镁和有机硅聚合物及氰脲酸三聚氰胺而成的。然而,该阻燃性树脂组合物由于含有30质量%左右的氰脲酸三聚氰胺作为阻燃剂,进而无机物的合计量也为70质量%左右,所以不仅在阻燃性能方面存在问题,而且在加工性或成形品的表面平滑性方面也存在问题。
现有技术文献
专利文献
专利文献1:US2014/200292A1
专利文献2:WO2014/080821A1
专利文献3:日本特开2003-226798号公报
专利文献4:日本特开2000-178386号公报
发明内容
在使用树脂材料的各种用途中对防火性的要求在提高,伴随于此,对树脂组合物所要求的阻燃性能的水平也变得日益提高。
然而,上述的以往的阻燃剂在防滴落效果方面并不充分。
本发明的课题在于提供通过与树脂混合从而能够给予防滴落效果、对该树脂赋予优异的阻燃性的组合物、及含有该组合物和树脂且发挥优异的阻燃性的阻燃性树脂组合物。
本发明人们对解决上述课题的构成进行了深入研究,结果发现,通过将胺的磷酸盐和氰脲酸三聚氰胺组合而得到的组合物与树脂混合,从而体现出优异的表面平滑性及防滴落效果。
本发明基于上述的见解,提供含有(A)磷酸胺盐和(B)氰脲酸三聚氰胺的组合物。
另外,本发明提供含有树脂及上述组合物的阻燃性树脂组合物及其成形体。
另外,本发明提供一种树脂的阻燃化方法,其包含:将含有上述(A)成分及上述(B)成分的组合物与树脂进行混合。
进而,本发明提供含有上述(A)成分及上述(B)成分的组合物作为阻燃剂的用途。
具体实施方式
以下,对本发明基于其优选的实施方式进行详细说明。
需要说明的是,在以下的说明中,所谓阻燃性是指下述性质:物质不易着火,另外即使着火而持续燃烧,其速度也非常慢,或者之后会自己熄灭,优选是指具有按照实施例中记载的UL-94V标准的燃烧等级中的至少V-2的等级,更优选是指具有V-1或V-0的等级。所谓阻燃剂组合物是指含有一种以上阻燃剂的组合物。所谓阻燃性树脂组合物是指具有上述的阻燃性、并且含有至少一种合成树脂的组合物。
本发明的组合物在含有上述(A)成分及上述(B)成分这点上具有特征之一。
首先,对本发明的组合物中包含的(A)成分即磷酸胺盐进行说明。所谓磷酸胺盐是磷酸与胺的盐。
本发明中所谓磷酸是指五氧化二磷水合而形成的酸,具体而言,可列举出正磷酸、焦磷酸及多磷酸。这些磷酸可以分别单独使用,或者也可以将两种以上组合使用。
作为胺,对其种类没有特别限制,可列举出例如芳香族胺及杂环式脂肪族胺。这些胺可以分别单独使用,或者也可以将两种以上组合使用。
作为芳香族胺,可列举出例如在芳香族烃环上键合有1或2个以上的氨基的化合物。该芳香族烃环中的1或2个以上的碳原子有时被例如氮、氧或硫等杂原子取代。作为在芳香族烃环上键合有1或2个以上的氨基的芳香族胺,可列举出例如苯胺或苯二胺等。另一方面,作为芳香族烃环中的1或2个以上的碳原子被杂原子取代的芳香族胺,可列举出例如具有1个氮原子作为杂原子的化合物即氨基吡啶、具有2个氮原子作为杂原子的化合物即氨基吡嗪、具有3个氮原子作为杂原子的化合物即氨基三嗪等。特别优选使用具有3个氮原子作为杂原子的化合物即氨基三嗪,尤其优选使用具有3个氨基的三嗪即三聚氰胺。
作为杂环式脂肪族胺,可列举出例如5元环的杂环式脂肪族胺及6元环的杂环式脂肪族胺。
作为5元环的杂环式脂肪族胺,可列举出例如包含1个氮原子的5元环的杂环式脂肪族胺及包含2个氮原子的5元环的杂环式脂肪族胺。作为包含1个氮原子的5元环的杂环式脂肪族胺,可列举出例如吡咯烷。作为包含2个氮原子的5元环的杂环式脂肪族胺,可列举出吡唑烷。另一方面,作为6元环的杂环式脂肪族胺,可列举出例如包含1个氮原子的6元环的杂环式脂肪族胺及包含2个氮原子的6元环的杂环式脂肪族胺。作为包含1个氮原子的6元环的杂环式脂肪族胺,可列举出例如哌啶。作为包含2个氮原子的6元环的杂环式脂肪族胺,可列举出例如哌嗪。在本发明中,作为杂环式胺,优选使用包含2个氮原子的6元环的杂环式脂肪族胺,尤其优选使用哌嗪。
在本发明的组合物中,作为(A)成分使用的磷酸胺盐优选含有(A-1)成分:选自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺构成的组中的至少一种三聚氰胺盐;和(A-2)成分:选自由正磷酸哌嗪、焦磷酸哌嗪及多磷酸哌嗪构成的组中的至少一种哌嗪盐。
本发明的组合物中作为(A-1)成分使用的三聚氰胺盐选自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺构成的组中。这些三聚氰胺盐有仅使用一种的情况,也有以两种以上的混合物使用的情况。它们中,从阻燃性、操作性、保存稳定性的方面出发,优选使用焦磷酸三聚氰胺。在将三聚氰胺盐以混合物使用的情况下,优选该混合物中的焦磷酸三聚氰胺的以质量基准计的含有比例最高。
这些磷酸与三聚氰胺的盐可以通过使各自对应的磷酸或磷酸盐与三聚氰胺反应来获得。特别是本发明的(A-1)成分中使用的三聚氰胺盐优选为使正磷酸三聚氰胺加热缩合而得到的焦磷酸三聚氰胺或多磷酸三聚氰胺,特别优选为焦磷酸三聚氰胺。
本发明的组合物中作为(A-2)成分使用的哌嗪盐选自由正磷酸哌嗪、焦磷酸哌嗪及多磷酸哌嗪构成的组中。这些哌嗪盐有仅使用一种的情况,也有以两种以上的混合物使用的情况。它们中,从阻燃性、操作性、保存稳定性的方面出发,优选使用焦磷酸哌嗪,在将哌嗪盐以混合物使用的情况下,优选该混合物中的焦磷酸哌嗪的以质量基准计的含有比例最高。
这些磷酸与哌嗪的盐可以通过使各自对应的磷酸或磷酸盐与哌嗪反应来获得。特别是本发明的(A-2)成分中使用的哌嗪盐优选为使正磷酸哌嗪加热缩合而得到的焦磷酸哌嗪或多磷酸哌嗪,特别优选为焦磷酸哌嗪。
本发明的组合物中包含的(A)成分优选仅包含(A-1)成分及(A-2)成分。该情况下,(A)成分中的(A-1)成分的含量相对于(A)成分100质量份优选为10~50质量份,更优选为20~50质量份。(A)成分中的(A-2)成分的含量相对于(A)成分100质量份优选为90~50质量份,更优选为80~50质量份。
另外,本发明的组合物中,(A)成分的合计量优选为70~99.9质量%,更优选为80~99质量%。(A)成分的含量为70质量%以上从提高滴落效果的方面出发优选,为99.9质量%以下从确保其他的任意成分量而提高本发明的效果的方面出发优选。本发明的组合物中的以(A-1)成分即三聚氰胺盐及(A-2)成分即哌嗪盐为代表的(A)成分即磷酸胺盐的含量可以通过离子色谱法进行测定。
接着,对本发明的组合物的(B)成分进行说明。
本发明的组合物中的(B)成分即氰脲酸三聚氰胺为三聚氰胺与氰脲酸的有机盐。
作为氰脲酸三聚氰胺,可以使用市售品。作为氰脲酸三聚氰胺的市售品,可列举出例如日产化学工业株式会社的MC-4000、MC-4500、MC-6000等。
作为氰脲酸三聚氰胺的制造方法,可列举出公知的方法。例如公开于日本特开平7-188193号公报或日本特开平7-149739号公报等中。
在本发明的组合物中,上述(B)成分的含量相对于上述(A)成分100质量份优选为0.1~20质量份,从阻燃性的方面出发,优选为0.5~20质量份,更优选为1~20质量份,进一步优选为3~10质量份。通过将(B)成分的含量设定为0.1质量份以上,具有防滴落、膨胀层形成的优点。另一方面,通过将(B)成分的含量设定为20质量份以下,从加工时的机械污染及加工成形性的方面出发具有优点。
在本发明的组合物中,上述(B)成分的含量可以通过例如红外光谱法、气相色谱法、气相色谱法-质量分析法等来测定。
在本发明的组合物中可以进一步含有氧化锌(ZnO)(以下,也将该成分称为“(C)成分”。)。
上述氧化锌作为阻燃助剂发挥功能。该氧化锌有时进行表面处理。氧化锌可以使用市售品,可列举出例如氧化锌1等级(三井金属矿业株式会社制)、部分覆膜型氧化锌(三井金属矿业株式会社制)、Nano Fine 50(平均粒径为0.02μm的超微粒子氧化锌:堺化学工业株式会社制)、Nano Fine K(平均粒径为0.02μm的经硅酸锌覆膜的超微粒子氧化锌:堺化学工业株式会社制)等。
在本发明的组合物中,上述(C)成分即氧化锌的含量从阻燃性的方面出发,相对于上述(A)成分100质量份优选为0.01~10质量份,更优选为0.5~8质量份,进一步优选为1~5质量份。通过将氧化锌的含量设定为0.01质量份以上,阻燃性变得更加良好。另一方面,通过将氧化锌的含量设定为10质量份以下,不易对加工性产生不良影响。
本发明的组合物从防止阻燃剂粉末凝聚、谋求保存稳定性提高和在合成树脂中的分散性提高或阻燃性提高的方面出发,优选进一步含有选自硅油、环氧系偶联剂、水滑石及润滑剂中的至少一种((D)成分)。
作为硅油的例子,可列举出聚硅氧烷的侧链、末端全部为甲基的二甲基硅油、聚硅氧烷的侧链、末端为甲基、其侧链的一部分为苯基的甲基苯基硅油、聚硅氧烷的侧链、末端为甲基、该侧链的一部分为氢的甲基氢硅油等、或它们的共聚物,另外还可以使用在它们的侧链和/或末端的一部分中导入了有机基团的胺改性、环氧改性、脂环式环氧改性、羧基改性、甲醇改性、巯基改性、聚醚改性、长链烷基改性、氟烷基改性、高级脂肪酸酯改性、高级脂肪酸酰胺改性、硅烷醇改性、二醇改性、苯酚改性和/或芳烷基改性的改性硅油。
若列举出上述硅油的具体例子,则作为二甲基硅油,可列举出KF-96(信越化学株式会社制)、KF-965(信越化学株式会社制)、KF-968(信越化学株式会社制)等,作为甲基氢硅油,可列举出KF-99(信越化学株式会社制)、KF-9901(信越化学株式会社)、HMS-151(Gelest公司制)、HMS-071(Gelest公司制)、HMS-301(Gelest公司制)、DMS-H21(Gelest公司制)等,作为甲基苯基硅油的例子,可列举出KF-50(信越化学株式会社制)、KF-53(信越化学株式会社制)、KF-54(信越化学株式会社制)、KF-56(信越化学株式会社制)等,作为环氧改性品,可列举出例如X-22-343(信越化学株式会社制)、X-22-2000(信越化学株式会社制)、KF-101(信越化学株式会社制)、KF-102(信越化学株式会社制)、KF-1001(信越化学株式会社制),作为羧基改性品,可列举出例如X-22-3701E(信越化学株式会社制),作为甲醇改性品,可列举出例如X-22-4039(信越化学株式会社制)、X-22-4015(信越化学株式会社制),作为胺改性品,可列举出例如KF-393(信越化学株式会社制)等。
在本发明的组合物中,硅油中,从防止阻燃剂粉末凝聚、保存稳定性的提高和在合成树脂中的分散性提高的方面出发,优选为甲基氢硅油。
环氧系偶联剂具有防止阻燃剂粉末的凝聚、用于保存稳定性的提高、或赋予耐水性、耐热性的功能。作为环氧系偶联剂,可列举出例如通式A-(CH2)k-Si(OR)3所表示的化合物且具有环氧基的化合物。A为环氧基,k表示1~3的数,R表示甲基或乙基。作为这里所谓的环氧基,可列举出环氧丙氧基或3,4-环氧环己基。
作为环氧系偶联剂的具体例子,例如作为具有环氧基的硅烷偶联剂,可列举出2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、环氧丙氧基辛基三甲氧基硅烷等。
所谓水滑石是作为天然物或合成物而已知的包含镁、铝、羟基、碳酸根及任意的结晶水的复合盐化合物,可列举出将镁或铝的一部分用碱金属或锌等其他金属置换而得到的物质或将羟基、碳酸根用其他阴离子基取代而得到的物质。具体而言,可列举出例如下述式(3)所表示的水滑石、或将该式(3)所表示的水滑石的金属置换成碱金属而得到的物质。另外,作为Al-Li系的水滑石,也可以使用式(4)所表示的化合物。
[化学式1]
Mgx1Znx2Al2(OH)2(x1+x2)+4(CO3)·pH2O (3)
(式中,x1及x2各自表示满足下述式所表示的条件的数,p表示0或正的数。0≤x2/x1<10,2≤x1+x2≤20。)
[化学式2]
[Li1/3Al2/3(OH)2][Aq- 1/3q·pH2O] (4)
(式中,Aq-表示q价的阴离子,p表示0或正的数。)
另外,上述水滑石中的碳酸根阴离子有时将一部分用其他阴离子取代。
上述水滑石也可以是将结晶水脱水而得到的物质,有时被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覆盖。
作为润滑剂,可列举出液体石蜡、天然石蜡、微晶蜡、合成石蜡、低分子量聚乙烯、聚乙烯蜡等纯烃系润滑剂;卤代烃系润滑剂;高级脂肪酸、羟基脂肪酸等脂肪酸系润滑剂;脂肪酸酰胺、双脂肪酸酰胺等脂肪酸酰胺系润滑剂;脂肪酸的低级醇酯、甘油酯等脂肪酸的多元醇酯、脂肪酸的聚乙二醇酯、脂肪酸的脂肪醇酯(酯蜡)等酯系润滑剂;金属皂、脂肪醇、多元醇、聚乙二醇、聚甘油、脂肪酸与多元醇的部分酯、脂肪酸与聚乙二醇、聚甘油的部分酯系的润滑剂、硅油、矿物油等。润滑剂可以单独使用一种,也可以将两种以上一并使用。
从阻燃性提高的方面出发,在本发明的组合物中含有选自硅油、环氧系偶联剂、水滑石及润滑剂中的至少一种((D)成分)的情况下,本发明的组合物中,从有效地发挥含有上述的E成分的效果的观点出发,E成分的含量相对于上述(A)成分100质量份优选为0.01~5质量份,更优选为0.01~3质量份。
特别是从提高由含有硅油带来的上述效果的方面出发,本发明的组合物中含有硅油时的硅油的含量相对于上述(A)成分100质量份优选为0.01~3质量份,更优选为0.1~1质量份。
特别是从提高由含有环氧系偶联剂带来的上述效果的方面出发,本发明的组合物中含有环氧系偶联剂时的环氧系偶联剂的含量相对于上述(A)成分100质量份优选为0.01~3质量份,更优选为0.1~1质量份。
特别是从提高由含有水滑石带来的上述效果的方面出发,本发明的组合物中含有水滑石时的水滑石的含量相对于上述(A)成分100质量份优选为0.01~5质量份,更优选为0.1~0.5质量份。
从提高由含有润滑剂带来的上述效果的方面出发,本发明的组合物中含有润滑剂时的润滑剂的含量相对于上述(A)成分100质量份优选为0.01~3质量份,更优选为0.1~0.5质量份。
本发明中使用的组合物中,根据需要可以配合酚系抗氧化剂、亚磷酸酯系抗氧化剂、硫醚系抗氧化剂、其他的抗氧化剂、成核剂、紫外线吸收剂、光稳定剂、增塑剂、填充剂、脂肪酸金属盐、抗静电剂、颜料、染料等。
这些成分可以预先配合到本发明的组合物中,可以在与合成树脂配合时配合到合成树脂中。优选通过配合它们而将合成树脂稳定化。
作为上述酚系抗氧化剂,可列举出例如2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2-叔丁基-4,6-二甲基苯酚、苯乙烯化苯酚、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、2,2’-硫代双-(6-叔丁基-4-甲基苯酚)、2,2’-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-甲基-4,6-双(辛基硫基甲基)苯酚、2,2’-异亚丁基双(4,6-二甲基苯酚)、异辛基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、N,N’-己烷-1,6-二基双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、2,2’-草酰胺基-双[乙基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯、2,2’-亚乙基双(4,6-二叔丁基苯酚)、3,5-二叔丁基-4-羟基-苯丙烷酸及C13-15烷基的酯、2,5-二叔戊基对苯二酚、受阻酚的聚合物(Adeka Palmarole公司制的商品名AO.OH.98)、2,2’-亚甲基双[6-(1-甲基环己基)-对甲酚]、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二叔戊基苯基丙烯酸酯、6-[3-(3-叔丁基-4-羟基-5-甲基)丙氧基]-2,4,8,10-四叔丁基苯并[d,f][1,3,2]-二噁磷杂庚英、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸酯]钙盐、5,7-双(1,1-二甲基乙基)-3-羟基-2(3H)-苯并呋喃酮与邻二甲苯的反应产物、2,6-二叔丁基-4-(4,6-双(辛硫基)-1,3,5-三嗪-2-基氨基)苯酚、DL-α-生育酚(维他命E)、2,6-双(α-甲基苄基)-4-甲基苯酚、双[3,3-双-(4’-羟基-3’-叔丁基-苯基)丁烷酸]二醇酯、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-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)-s-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(2,6-二叔丁基苯酚)、4,4’-亚丁基双(6-叔丁基-3-甲基苯酚)、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[亚甲基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯]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-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]-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[3-叔-4-羟基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、棕榈基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、肉豆蔻基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、月桂基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺等3-(3,5-二烷基-4-羟基苯基)丙酸衍生物等。这些酚系抗氧化剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些酚系抗氧化剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.01~1.0质量份。
上述亚磷酸酯系抗氧化剂可列举出例如亚磷酸三苯酯、亚磷酸二异辛酯、七(二丙二醇)三亚磷酸酯、亚磷酸三异癸酯、亚磷酸二苯基异辛基酯、亚磷酸二异辛基苯基酯、亚磷酸二苯基十三烷基酯、亚磷酸三异辛基酯、亚磷酸三月桂酯、亚磷酸二苯酯、三(二丙二醇)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、二油基亚磷酸氢酯、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-甲基苯硫基)-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)异亚丙基二苯酚二亚磷酸酯、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)联苯撑二亚膦酸酯、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-叔丁基苯基二(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〕二噁磷杂庚英-6-基)氧基〕乙基)胺、3,9-双(4-壬基苯氧基)-2,4,8,10-四氧杂-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、4,4’-异亚丙基二苯酚C12-15醇亚磷酸酯、3,9-双(2,6-二叔丁基-4-甲基苯基)-3,9-双-二磷杂-2,4,8,10-四氧杂-3,9-二磷杂螺[5,5]十一烷、二苯基(异癸基)亚磷酸酯、联苯二苯基亚磷酸酯等。这些亚磷酸酯系抗氧化剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些亚磷酸酯系抗氧化剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.01~1.0质量份。
上述硫醚系抗氧化剂可列举出例如3,3’-硫代二丙酸、烷基(C12-14)硫代丙酸、二(月桂基)-3,3’-硫代二丙酸酯、3,3’-硫代双丙酸二(十三烷基)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、二(十八烷基)-3,3’-硫代二丙酸酯、月桂基硬脂基硫代二丙酸酯、四[亚甲基-3-(十二烷基硫代)丙酸酯]甲烷、硫代双(2-叔丁基-5-甲基-4,1-亚苯基)双(3-(十二烷基硫代)丙酸酯)、2,2’-硫代二亚乙基双(3-氨基丁烯酸酯)、4,6-双(辛硫基甲基)-邻甲酚、2,2’-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、2,2’-硫代双(6-叔丁基-对甲酚)、2-乙基己基-(3,5-二叔丁基-4-羟基苄基)硫代乙酸酯、4,4’-硫代双(6-叔丁基-3-甲基苯酚)、4,4’-硫代双(4-甲基-6-叔丁基苯酚)、4,4’-[硫代双(亚甲基)]双(2-叔丁基-6-甲基-1-羟基苄基)、双(4,6-二叔丁基苯酚-2-基)硫醚、十三烷基-3,5-二叔丁基-4-羟基苄基硫代乙酸酯、1,4-双(辛硫基甲基)-6-甲基苯酚、2,4-双(十二烷基硫代甲基)-6-甲基苯酚、二硬脂基-二硫醚、双(甲基-4-[3-正烷基(C12/C14)硫代丙酰氧基]5-叔丁基苯基)硫醚等。这些硫醚系抗氧化剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些硫醚系抗氧化剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.01~1.0质量份。
上述其他的抗氧化剂可列举出例如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-(酰基氧基苯基)苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(4-羟基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-{4-(2-羟基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二叔-2-氧代-2,3-二氢苯并呋喃-3-基)苯氧基)乙氧基)-6-氧代己基-6-((6-羟基己酰基)氧基)己酸酯、5-二叔丁基-3-(4-((15-羟基-3,6,9,13-四氧杂十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等苯并呋喃化合物等。这些其他的抗氧化剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些其他的抗氧化剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.01~1.0质量份。
作为上述成核剂,可列举出例如苯甲酸钠、4-叔丁基苯甲酸铝盐、己二酸钠、二环[2.2.1]庚烷-2,3-二羧酸二钠等羧酸金属盐、双(4-叔丁基苯基)磷酸钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸锂等磷酸酯金属盐、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、双(二甲基亚苄基)山梨糖醇、1,2,3-三脱氧-4,6:5,7-双-O-((4-丙基苯基)亚甲基)-壬醇、1,3:2,4-双(对甲基亚苄基)山梨糖醇、1,3:2,4-双-O-亚苄基-D-山梨糖醇(二亚苄基山梨糖醇)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(二甲基异丙酰基氨基)苯等酰胺化合物等。这些成核剂可以单独使用一种,也可以将两种以上一并使用。在与树脂配合时,这些成核剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.01~1.0质量份。
上述紫外线吸收剂可列举出例如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)、2-羟基-4-正辛氧基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-十二烷氧基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮等二苯甲酮系、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-氯苯并三唑、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑、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〕苯并三唑等苯并三唑系、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、山萮基(3,5-二叔丁基-4-羟基)苯甲酸酯等苯甲酸酯系、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、2-乙基-2’-乙氧基-5’-叔丁基-草酰替苯胺等取代草酰替苯胺系、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、四(α-氰基-β,β-二苯基丙烯酰氧基甲基)甲烷等氰基丙烯酸酯系、2-(2-羟基-4-(2-(2-乙基己酰氧基)乙基氧基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三(2-羟基-4-己基氧基-3-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己基氧基苯酚、2-(4,6-二(1,1′-联苯)4-基)-1,3,5-三嗪-2-基)-5-(2-乙基己基氧基)苯酚等三嗪系。这些紫外线吸收剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些紫外线吸收剂的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.05~0.5质量份。
上述光稳定剂可列举出例如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-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、双(2,2,6,6-四甲基-4-哌啶基)/二(十三烷基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四羧酸酯、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-吗啉代-s-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-s-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)-s-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)-s-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)-s-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)-s-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}癸二酸酯、双{4-(2,2,6,6-四甲基-1-十一烷基氧基)哌啶基}碳酸酯、Ciba Specialty Chemicals制TINUVINNOR 371、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、1,2,3,4-丁烷四羧酸、与2,2-双(羟基甲基)-1,3-丙二醇及3-羟基-2,2-二甲基丙醛的聚合物、1,2,2,6,6-五甲基-4-哌啶基酯、1,3-双(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、双(1-辛基氧基-2,2,6,6-五甲基-4-哌啶基)癸二酸酯、聚[[6-[(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亚氨基]-1,6-己烷二基[(2,2,6,6-四甲基-4-哌啶基)亚氨基]])等。这些光稳定剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些光稳定剂的使用量在阻燃性树脂组合物100质量份中,优选为0.001~5质量份,更优选为0.005~0.5质量份。
作为上述增塑剂,可列举出例如环氧化大豆油、环氧化亚麻仁油、环氧化脂肪酸辛基酯等环氧系、甲基丙烯酸酯系、二羧酸与多元醇的缩聚物、多元羧酸与多元醇的缩聚物等聚酯系、二羧酸与多元醇与亚烷基二醇的缩聚物、二羧酸与多元醇与亚芳基二醇的缩聚物、多元羧酸与多元醇与亚烷基二醇的缩聚物、多元羧酸与多元醇与亚芳基二醇的缩聚物等聚醚酯系、己二酸酯、琥珀酸酯等脂肪族酯系、邻苯二甲酸酯、对苯二甲酸酯、偏苯三酸酯、均苯四甲酸酯、苯甲酸酯等芳香族酯系等。这些增塑剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些增塑剂的使用量在阻燃性树脂组合物100质量份中优选为0.1~500质量份,更优选为1~100质量份。
上述填充剂可列举出例如滑石、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、粘土、白云石、云母、二氧化硅、氧化铝、钛酸钾晶须、硅灰石、纤维状硫氧化镁、蒙脱石等,可以适当选择使用粒径(在纤维状中为纤维径或纤维长及长宽比)。这些填充剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些填充剂的使用量在阻燃性树脂组合物100质量份中优选为1~100质量份,更优选为3~80质量份。
作为上述脂肪酸金属盐的脂肪酸,可列举出例如癸酸、2-乙基己酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、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、三十烷酸等饱和脂肪酸、4-癸烯酸、4-十二烯酸、棕榈烯酸、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、均苯三甲酸等芳香族脂肪酸,特别优选肉豆蔻酸、硬脂酸、12-羟基硬脂酸等饱和脂肪酸。作为脂肪酸金属盐的金属,可列举出例如碱金属、镁、钙、锶、钡、钛、锰、铁、锌、硅、锆、钇、钡或铪等,特别优选钠、锂、钾等碱金属。这些脂肪酸金属盐可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些脂肪酸金属盐的使用量在阻燃性树脂组合物100质量份中优选为0.001~5质量份,更优选为0.05~3质量份。
上述抗静电剂可列举出例如脂肪酸季铵离子盐、季聚胺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、烷基二甲基氨基醋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。这些抗静电剂可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些抗静电剂的使用量在阻燃性树脂组合物100质量份中优选为0.01~20质量份,更优选为3~10质量份。
上述颜料也可以使用市售的颜料,可列举出例如颜料红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。这些颜料可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些颜料的使用量在阻燃性树脂组合物100质量份中优选为0.0001~10质量份。
上述染料也可以使用市售的染料,可列举出例如偶氮染料、蒽醌染料、靛类染料、三芳基甲烷染料、呫吨染料、茜素染料、吖啶染料、芪染料、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、花青染料等染料等。这些染料可以单独使用一种,也可以将两种以上一并使用。
在与树脂配合时,这些染料的使用量在阻燃性树脂组合物100质量份中优选为0.0001~10质量份。
为了得到本发明的组合物,只要将必须成分的(A)及(B)成分及根据需要添加的(C)~(D)成分、以及进一步根据需要添加的其他任意成分混合即可,混合中可以使用各种混合机。也可以在混合时加热。若列举出可使用的混合机的例子,则可列举出摇摆(turbula)混合机、亨舍尔混合机、螺条式搅拌机、V型混合机、W型混合机、高速混合机、诺塔混合机等。
本发明的组合物对树脂的阻燃化有效果,作为树脂用组合物(有时也称为“树脂用添加剂”)、特别是阻燃剂是有用的。本发明的组合物优选通过将其与树脂配合,制成阻燃性树脂组合物(以下,也称为本发明的阻燃性树脂组合物)而使用。
作为通过本发明的组合物而阻燃化的树脂,可列举出热塑性树脂及热固性树脂等合成树脂。具体而言,作为热塑性树脂,可列举出聚烯烃系树脂、含生物质的聚烯烃系树脂、含卤素树脂、芳香族聚酯树脂、直链聚酯树脂、分解性脂肪族、聚酰胺树脂、纤维素酯系树脂;聚碳酸酯树脂、聚氨酯树脂、聚苯醚系树脂、聚苯硫醚系树脂、丙烯酸系树脂等热塑性树脂及它们的共混物。另一方面,作为热固性树脂,可列举出酚醛树脂、尿素树脂、三聚氰胺树脂、环氧树脂、不饱和聚酯树脂等。
作为通过本发明的组合物而阻燃化的其它的合成树脂,还可列举出烯烃系热塑性弹性体、苯乙烯系热塑性弹性体、聚酯系热塑性弹性体、腈系热塑性弹性体、尼龙系热塑性弹性体、氯乙烯系热塑性弹性体、聚酰胺系热塑性弹性体、聚氨酯系热塑性弹性体等。
这些树脂可以使用一种,也可以使用两种以上。另外树脂有时被合金化。
本发明中使用的树脂分子量、聚合度、密度、软化点、不溶成分在溶剂中的比例、立构规整性的程度、催化剂残渣的有无、作为原料的单体的种类或配合比率、聚合催化剂的种类(例如齐格勒催化剂、茂金属催化剂等)等如何,都可以使用。
以上的各种树脂中,从能够赋予优异的阻燃性的方面出发,优选聚烯烃系树脂或聚氨酯系热塑性弹性体。作为聚烯烃系树脂,可列举出例如聚乙烯、低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、聚丙烯、均聚丙烯、无规共聚物聚丙烯、嵌段共聚物聚丙烯、抗冲击共聚物聚丙烯、高抗冲击共聚物聚丙烯、等规聚丙烯、间规聚丙烯、半等规聚丙烯、马来酸酐改性聚丙烯、聚丁烯、环烯烃聚合物、立构嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等α-烯烃聚合物、乙烯/丙烯嵌段或无规共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-醋酸乙烯酯共聚物等α-烯烃共聚物等。
另外,作为聚氨酯系热塑性弹性体,可列举出热塑性聚氨酯树脂(TPU)。热塑性聚氨酯树脂(TPU)为分子结构中具有氨基甲酸酯基(-NHCOO-)的橡胶状弹性体,包含被称为软链段的容易活动的长链部分和被称为硬链段的结晶性极强的部分,一般使用多元醇、二异氰酸酯、及扩链剂来制备。
另外,热塑性聚氨酯树脂根据其成形方法,可以大致分为以液状注入模具中并使其固化反应的浇注类型、与以往的橡胶同样在辊混炼后进行压制成形的类型及可以与一般热塑性树脂同样地加工的类型,但本发明中,并不将它们进行区别。
作为上述热塑性聚氨酯树脂的具体例子,可列举出酯(内酯)系聚氨酯共聚物、酯(己二酸酯)系聚氨酯共聚物、醚系聚氨酯共聚物、碳酸酯系聚氨酯共聚物、醚·酯系聚氨酯共聚物,这些热塑性聚氨酯树脂(TPU)可以单独使用,也可以组合使用。
在本发明的阻燃性树脂组合物中,树脂的含量优选为50~99.9质量%,更优选为60~90质量%。另外,在阻燃性树脂组合物含有本发明的组合物作为阻燃剂组合物的情况下,相对于树脂100质量份,优选含有10质量份~400质量份的该阻燃剂组合物,更优选为20~80质量份。通过将阻燃剂组合物的含量设定为10质量份以上,可发挥充分的阻燃性,通过设定为400质量份以下,树脂本来的物性变得不易受损。
对于本发明的阻燃性树脂组合物,通过将其成形,能够得到阻燃性优异的成形品。成形方法没有特别限定,但可列举出挤出加工、压延加工、注射成形、辊轧、压缩成形、吹塑成形等,可以制造树脂板、片材、膜、异形品等各种形状的成形品。
本发明的阻燃性树脂组合物及其成形体可以用于电气·电子·通信、电子与工程、农林水产、矿业、建设、食品、纤维、衣类、医疗、煤炭、石油、橡胶、皮革、汽车、精密设备、木材、建材、土木、家具、印刷、乐器等广泛的产业领域。更具体而言,可以用于打印机、电脑、文字处理机、键盘、PDA(小型信息终端机)、电话机、复印机、传真、ECR(电子式收银机)、计算器、电子笔记本、卡、架子、文具等办公用品、OA设备、洗衣机、冰箱、吸尘器、微波炉、照明器具、游戏机、电熨斗、被炉等家电设备、TV、VTR、摄像机、收录机、录音机、微型磁盘、CD播放器、扩音器、液晶显示器等AV设备、连接器、继电器、电容器、开关、印刷基板、线圈骨架、半导体密封材料、LED密封材料、电线、电缆、变压器、偏转轭、配电盘、钟表等电气/电子部件及通信设备、OA设备等的箱体(框架、框体、外壳、外包装)或部件、汽车内外装饰材料的用途中。其中特别适宜用于电线等电子部件或汽车内外装饰构件等汽车部件。
进而,本发明的阻燃性树脂组合物及其成形体被用于座位(填充物、内饰件等)、带、顶篷、活顶车顶篷、扶手、车门内饰、后杂物箱、地毯、垫子、遮阳板、轮毂装饰罩、垫子罩、安全气囊、绝缘材料、吊环、吊环带、电线被覆材料、电绝缘材料、涂料、涂布材料、外部装潢材料、地板材料、角壁、地毯、壁纸、壁装饰材料、外装饰材料、内装饰材料、屋顶材料、甲板材料、壁材、柱材、铺板、围墙的材料、骨架及造型、窗户及门的型材、木瓦、板壁、阳台、露台、防音板、绝热板、窗户材料等汽车、混合动力车、电动车、车辆、船舶、航空器、建筑物、住宅及建筑用材料、或土木材料、衣料、窗帘、床单、胶合板、合成纤维板、绒毯、玄关垫、片材、桶、管、容器、眼镜、包、盒子、护目镜、滑雪板、球拍、帐篷、乐器等生活用品、体育用品等各种用途。
实施例
以下,通过实施例对本发明更详细地进行说明。但是,本发明并不受以下的实施例的任何限制。需要说明的是,以下的表1~2中的数值的单位为质量份。
<组合物的制备>
将下述表1及2中记载的成分中的除树脂以外的成分以该成分表中记载的比例配合,使用亨舍尔混合机进行混合。但是,在添加环氧系偶联剂、润滑剂或硅油的情况下,在将其他成分预混合后,添加环氧系偶联剂、润滑剂或硅油并使用亨舍尔混合机进行混合,得到组合物。
<阻燃性树脂组合物的制备>
·实施例1~15及比较例1~4
在热塑性聚氨酯树脂(BASF制Elastollan 1185A)100质量份中配合硬脂酸钙0.1质量份、甘油单硬脂酸酯0.3质量份、四[3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯]甲烷0.1质量份、2,2’-亚甲基双(4,6-二叔丁基苯基)-2-乙基己基亚磷酸酯0.1质量份,利用亨舍尔混合机进行预混合而得到热塑性聚氨酯树脂组合物。相对于所得到的热塑性聚氨酯树脂组合物,以表中记载的质量份配合表1或2中所示的组合物,用亨舍尔混合机混合而得到阻燃性树脂组合物。
·实施例16~20及比较例5~8
在聚丙烯(依据JIS K7210测定的载荷为2.16kg、230℃下的熔体流动速率=8g/10min)100质量份中配合硬脂酸钙(高级脂肪酸金属盐)0.1质量份、四[3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯]甲烷(酚系抗氧化剂)0.1质量份、三(2,4-二叔丁基苯基)亚磷酸酯(磷系抗氧化剂)0.1质量份,利用亨舍尔混合机进行预混合而得到聚丙烯树脂组合物。相对于所得到的聚丙烯树脂组合物,以表中记载的质量份配合表1或表2中所示的组合物,用亨舍尔混合机混合而得到阻燃性树脂组合物。
将上述得到的各树脂组合物通过以下的方法制作粒料,由该粒料制作阻燃性评价用试验片,对于该评价片,供于以下的阻燃性评价及表面平滑性评价。将其结果示于表1及表2中。
[评价]
<阻燃性评价>
将含有热塑性聚氨酯树脂的实施例1~15的树脂组合物及比较例1~4的树脂组合物使用双螺杆挤出成形机(株式会社日本制钢所制:TEX-30α)以将料筒温度设定为190~200℃及螺杆速度为150rpm的条件进行熔融混炼。将从模头喷出的股线通过冷却浴进行冷却,通过利用造粒机进行切断,制作树脂组合物的粒料。
将含有聚丙烯树脂的实施例16~20的树脂组合物及比较例5~8的树脂组合物使用双螺杆挤出成形机(株式会社日本制钢所制:TEX-30α)以料筒温度为220~230℃及螺杆速度150rpm的条件进行熔融混炼。将从模头喷出的股线通过冷却浴进行冷却,通过利用造粒机进行切断,制作树脂组合物的粒料。
将上述得到的树脂组合物的粒料使用日精树脂工业社制:NEX-80进行注射成形,得到长度为127mm、宽度为12.7mm、厚度为1.6mm的阻燃性评价用试验片。对于实施例1~13及比较例,将螺杆设定温度设定为200℃,将模具温度设定为40℃。对于实施例14~16及比较例7~12,将螺杆设定温度设定为230℃,将模具温度设定为40℃。
将所得到的试验片依据ISO1210进行了20mm垂直燃烧试验(UL-94V)。具体而言,将试验片垂直地保持,对下端用燃烧器的火接焰10秒钟后,移除火焰,测定试验片上点着的火熄灭的时间。接着,在火熄灭的同时进行10秒钟第二次的接焰,与第一次同样地测定点着的火熄灭的时间。另外,同时还对试验片下面的棉花是否因为落下的火种而着火进行评价。根据第一次和第二次的燃烧时间、棉花有无着火等,按照UL-94V标准来确定燃烧等级。对于燃烧等级,V-0为最高,按照V-1、V-2的顺序阻燃性降低。将不符合V-0~V-2的等级中的任一者的情况设定为NR。本发明中能体现防滴落效果的情况为V-2以上,优选达成V-0。
<表面平滑性>
通过下述基准来评价所得到的试验片的表面平滑性。
○:试验片的表面平滑且光滑
×:试验片的表面有一点点不光滑
如由表1中所示的结果表明的那样,在将含有(A)成分、(B)成分的组合物配合到树脂中的各实施例中,判断UL-94V试验中的树脂的阻燃性评价及表面平滑性评价提高。特别是在(A)成分含有(A-1)成分及(A-2)成分的情况下,阻燃性评价变得更良好。
与此相对,如表2中所示的那样,在没有使用(A)成分的情况下(比较例No.1、比较例No.5),阻燃性及表面平滑性不充分,在不使用(B)成分的情况下(比较例No.2~4、比较例No.6~8),表面平滑性不充分。
因此,判断本发明的组合物能够对树脂赋予高的阻燃性及表面平滑性,作为阻燃剂优异。
产业上的可利用性
根据本发明,通过与树脂混合,能够提供可得到给予防滴落效果、能够对该树脂赋予优异的阻燃性、并且表面平滑性良好的成形品的组合物及含有该组合物和树脂、发挥优异的阻燃性的阻燃性树脂组合物。
Claims (10)
1.一种组合物,其含有(A)磷酸胺盐和(B)氰脲酸三聚氰胺。
2.根据权利要求1所述的组合物,其中,所述(A)成分含有下述(A-1)及(A-2),
(A-1)成分:选自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺构成的组中的至少一种三聚氰胺盐。
(A-2)成分:选自由正磷酸哌嗪、焦磷酸哌嗪及多磷酸哌嗪构成的组中的至少一种哌嗪盐。
3.根据权利要求2所述的组合物,其中,相对于所述(A-1)成分与(A-2)成分的合计100质量份,含有0.1~20质量份的所述(B)成分。
4.根据权利要求1~3中任一项所述的组合物,其中,相对于所述(A)成分100质量份进一步含有0.01~10质量份的(C)氧化锌。
5.根据权利要求1~4中任一项所述的组合物,其中,相对于所述(A)成分100质量份进一步含有0.01~5质量份的(D)成分即选自由硅油、环氧系偶联剂、水滑石及润滑剂构成的组中的至少一种。
6.一种阻燃剂,其含有权利要求1~5中任一项所述的组合物。
7.一种阻燃性树脂组合物,其相对于树脂100质量份含有10~400质量份的权利要求6所述的阻燃剂。
8.一种成形品,其是权利要求7所述的阻燃性树脂组合物的成形品。
9.一种树脂的阻燃化方法,其包含:将含有磷酸胺盐(A)和氰脲酸三聚氰胺(B)的组合物与树脂混合。
10.含有磷酸胺盐(A)和氰脲酸三聚氰胺(B)的组合物作为阻燃剂的用途。
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US11691043B2 (en) | 2021-01-06 | 2023-07-04 | Shandong University Of Science And Technology | Multi-functional plugging agent for coal mine and preparation method thereof |
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US20200224100A1 (en) | 2020-07-16 |
EP3683288B1 (en) | 2023-06-07 |
TW201920409A (zh) | 2019-06-01 |
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JP7109455B2 (ja) | 2022-07-29 |
EP3683288A4 (en) | 2021-05-26 |
JPWO2019054155A1 (ja) | 2020-11-05 |
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