CN110016122A - 树脂组合物与导热材料的形成方法 - Google Patents

树脂组合物与导热材料的形成方法 Download PDF

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CN110016122A
CN110016122A CN201810933700.4A CN201810933700A CN110016122A CN 110016122 A CN110016122 A CN 110016122A CN 201810933700 A CN201810933700 A CN 201810933700A CN 110016122 A CN110016122 A CN 110016122A
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epoxy resin
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刘彦群
王闵仟
曹翔雁
邱国展
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Abstract

本公开提供导热材料的形成方法,包括:混合1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体,以形成树脂组合物;以及加热硬化树脂组合物,以形成导热材料。

Description

树脂组合物与导热材料的形成方法
【技术领域】
本公开涉及导热材料,更特别涉及导热材料所用的树脂组合物。
【背景技术】
为了应对未来5G以及IoT网通时代的来临,电子产品往薄型化以及高功率方面设计,而热界面材料在整体模组设计中扮演非常关键的角色。为了增加元件及散热片间的热传递效率,热界面材料需具热导和热阻抗特性。
现有热界面材料的树脂组合物多以硅氧烷树脂为主,再添加高导热填充物如氧化铝或氮化硼等陶瓷粉末以增进热传导率,再制成薄片、衬垫、带状、或薄膜。为了使热界面材料具有更佳的热传导值,导热填充物的添加量通常会大于总组成的85wt%。导热填充物越多,热传导值则越高。然而随着导热填充物添加量提高,树脂组合物的特性常难以显现,因此热界面材料有电子绝缘性不佳,且柔软性、机械强度、或耐热性特性不足等问题。最重要的是,上述热界面材料不能进行整卷式的涂布,只能以热压方式进行加工,而大幅限制其用途。
为了克服因添加过多导热填充物而降低材料的绝缘与机械特性等问题,目前亟需导热、绝缘、与可涂布的树脂组合物。
【发明内容】
本公开一实施例提供树脂组合物,包括:1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体。
本公开一实施例提供导热材料的形成方法,包括:混合1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体,以形成树脂组合物;以及加热硬化树脂组合物,以形成导热材料。
【具体实施方式】
本公开一实施例提供树脂组合物,包括:1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体。若(b)脂环族环氧树脂单体的比例过高,则导热系数不佳。若(b)脂环族环氧树脂单体的比例过低,则组合物的相容性下降。若(c)脂肪族环氧树脂单体的比例过高,则机械特性与导热系数皆下降。若(c)脂肪族环氧树脂单体的比例过低,则组合物的柔软性下降。
在一实施例中,(a)芳香族环氧树脂单体的结构为:其中Ar为 R1为-CH2-、-C(CH3)2-、-CH=CH-、-CH=C(CH3)-、-O-、-C≡C-、-C=CH-CO-、-COO-、-CONH-、或-CO-。每一R2各自为H、卤素、或C1-8烷基。在一些实施例中,(a)芳香族环氧树脂单体的结构为
在一实施例中,(b)脂环族环氧树脂单体的结构为:
Cy为 R3为-CH2-、-C(CH3)2-、-CH=CH-、-CH=C(CH3)-、-O-、-C≡C-、-C=CH-CO-、-COO-、-CONH-、或-CO-。每一R4各自为H、卤素、或C1-8烷基。在一些实施例中,(b)脂环族环氧树脂单体的结构为
在一些实施例中,(c)脂肪族环氧树脂单体的结构为:R为C1-6直链状烷撑基(亚烷基),且直链状烷撑基上取代有氢或C1-8烷基。在一些实施例中,(c)脂肪族环氧树脂单体的结构为
在一些实施例中,上述树脂组合物还包括(d)胺类硬化剂。(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的环氧基与(d)胺类硬化剂的胺基之间的摩尔比可介于1:1至2:1之间。
在一些实施例中,(d)胺类硬化剂的结构为H2N-R5-NH2或H2N-Ar’-O-R6-O-Ar’-NH2。R5
R11为C1-6烷撑基,且n’=1至10之间。R7为单键、-O-、-SO2-、-CH2-、-(CH2)2-、或-C(CF3)2-。每一R8各自为H、卤素、或C1-8烷基。R6 R9为单键、-O-、-SO2-、或-C(CF3)2-。每一R10各自为H、卤素、或C1-8烷基。N为3至12的整数。Ar’为 上述(d)胺类硬化剂可包含脂环族胺类硬化剂、芳香族胺类硬化剂、与脂肪族胺类硬化剂。在一实施例中,(d)胺类硬化剂为脂环族胺类硬化剂与芳香族胺类硬化剂的组合时,可进一步提升树脂组合物硬化后的导热系数。
在一些实施例中,上述树脂组合物还包括(e)导热填充物,且(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的总重与(e)导热填充物的重量之间的比例介于70:30至5:95之间。若(e)导热填充物的比例过高,则会影响树脂组合物硬化后的物性如可挠性与绝缘特性。上述(e)导热填充物可为金属、金属氧化物、金属氮化物、陶瓷、碳材、或上述的组合。举例来说,(e)导热填充物可为铜、金、镍、银、铝、或上述的合金、氧化铝、氧化镁、氧化锌、氧化铍、氮化硼、氮化铝、碳化硅、碳化钨、钻石、石墨、碳纤、纳米碳管、或上述的组合。在一实施例中,(e)导热填充物为氧化铝。
本公开一实施例亦提供导热材料的形成方法,包括:混合1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体,以形成树脂组合物;以及加热硬化树脂组合物,以形成导热材料。在一些实施例中,树脂组合物还包括(d)胺类硬化剂。(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的环氧基与(d)胺类硬化剂的胺基之间的摩尔比介于1:1至2:1之间。在一些实施例中,(d)胺类硬化剂包括脂环族胺类硬化剂与芳香族胺类硬化剂的组合。在一些实施例中,树脂组合物还包括(e)导热填充物,且(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的总重与(e)导热填充物的重量之间的比例介于70:30至5:95之间。
为了让本公开的上述和其他目的、特征、和优点能更明显易懂,下文特举数个实施例配合所附图示,作详细说明如下:
实施例
下述实施例采用的环氧树脂单体与胺类硬化剂的代称、名称、与结构如表1所示:
表1
下述实施例形成的导热材料的导热系数的测量标准为ASTM-E1461、体积电阻的测量标准为ASTM-D257、而破坏电压的测量标准为ASTM-D149。
实施例1
取5g的脂肪族环氧树脂单体NEO,与4.264g的脂环族胺类硬化剂JER-113混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例2
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO及脂环族环氧树脂单体epalloy 5000(摩尔比=8:2)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例3
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO与脂环族环氧树脂单体epalloy 5000(摩尔比=6:4)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例4
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO与脂环族环氧树脂单体epalloy 5000(摩尔比=5:5)。其余硬化剂种类与用量及硬化条件与实施例1类似。
表2
由表2的比较可知,脂肪族环氧树脂单体NEO与脂环族环氧树脂单体epalloy 5000的组合形成的导热材料,比单用脂肪族环氧树脂单体NEO的导热材料具有更高的导热系数与破坏电压。
实施例5
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO及脂环族环氧树脂单体YX8000(摩尔比=8:2)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例6
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO及脂环族环氧树脂单体YX8000(摩尔比=7:3)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例7
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO及脂环族环氧树脂单体YX8000(摩尔比=6:4)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例8
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO及脂环族环氧树脂单体YX8000(摩尔比=5:5)。其余硬化剂种类与用量及硬化条件与实施例1类似。
表3
由表3的比较可知,脂肪族环氧树脂单体NEO与脂环族环氧树脂单体YX8000的组合中,NEO与YX8000的比例为6:4时,形成的导热材料具有较高的导热系数、体积电阻、与破坏电压。
实施例9
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=7:2:1)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例10
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=6:1:3)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例11
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例12
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=5:2:3)。其余硬化剂种类与用量及硬化条件与实施例1类似。
表4
由表2与表4的比较可知,脂肪族环氧树脂单体NEO、脂环族环氧树脂单体epalloy5000、与芳香族环氧树脂单体YX4000的组合形成的导热材料,比脂肪族环氧树脂单体NEO与脂环族环氧树脂单体epalloy 5000形成的导热材料具有较高的导热系数。
实施例13
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=7:2:1)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例14
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=6:1:3)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例15
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)。其余硬化剂种类与用量及硬化条件与实施例1类似。
实施例16
与实施例1类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:2:3)。其余硬化剂种类与用量及硬化条件与实施例1类似。
表5
由表3与表5的比较可知,脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、与芳香族环氧树脂单体YX4000的组合形成的导热材料,比脂肪族环氧树脂单体NEO与脂环族环氧树脂单体YX8000的组合形成的导热材料具有较高的导热系数。
实施例17
取5g的环氧树脂单体如脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、芳香族环氧树脂单体YX4000(摩尔比=5:1:4),以及1.148g的脂环族胺类硬化剂JER-113与0.954g的芳香族胺类硬化剂DDM(摩尔比=1:1)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例18
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.022g的芳香族胺类硬化剂DDE(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例19
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.359g的芳香族胺类硬化剂CUAHARD-MED(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例20
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.089g的芳香族胺类硬化剂MDA(摩尔比=1:1)。其余硬化条件与实施例17类似。
表6
由表5的实施例15与表6的比较可知,脂环族胺类硬化剂JER-113以及芳香族胺类硬化剂的组合,可提高导热材料的导热系数。
实施例21
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.195g的芳香族胺类硬化剂DDS(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例22
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.407g的芳香族胺类硬化剂TPE-Q(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例23
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.771g的芳香族胺类硬化剂BAPB(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例24
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.022g的芳香族胺类硬化剂m-Tolidine(摩尔比=1:1)。其余硬化条件与实施例17类似。
表7
由表5的实施例15与表7的比较可知,脂环族胺类硬化剂JER-113以及芳香族胺类硬化剂的组合,可提高导热材料的导热系数或破坏电压。
实施例25
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及0.550g的脂环族胺类硬化剂CHD(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例26
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.013g的脂环族胺类硬化剂DACH(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例27
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.718g的芳香族胺类硬化剂CUA-4(摩尔比=1:1)。其余硬化条件与实施例17类似。
实施例28
与实施例17类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及2.349g的芳香族胺类硬化剂ELASMER 250P(摩尔比=1:1)。其余硬化条件与实施例17类似。
表8
由表5的实施例15与表8的比较可知,脂环族胺类硬化剂JER-113以及芳香族胺类硬化剂的组合,可提高导热材料的导热系数。
实施例29
取5g的脂肪族环氧树脂单体BUT,与3.870g的脂环族胺类硬化剂JER-113混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例30
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体epalloy 5000(摩尔比=8:2)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例31
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体epalloy 5000(摩尔比=6:4)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例32
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体epalloy 5000(摩尔比=5:5)。其余硬化剂种类与用量及硬化条件与实施例29类似。
表9
由表9的比较可知,脂肪族环氧树脂单体BUT与脂环族环氧树脂单体epalloy 5000的组合形成的导热材料,比单用脂肪族环氧树脂单体BUT的导热材料具有更高的导热系数与破坏电压。
实施例33
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000(摩尔比=8:2)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例34
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000(摩尔比=7:3)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例35
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000(摩尔比=6:4)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例36
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000(摩尔比=5:5)。其余硬化剂种类与用量及硬化条件与实施例29类似。
表10
由表10的比较可知,在脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000的组合中,YX8000的比例越高,则形成的导热材料具有较高的导热系数与破坏电压。
实施例37
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=7:2:1)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例38
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=6:1:3)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例39
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例40
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体epalloy 5000、及芳香族环氧树脂单体YX4000(摩尔比=5:2:3)。其余硬化剂种类与用量及硬化条件与实施例29类似。
表11
由表9与表11的比较可知,脂肪族环氧树脂单体BUT、脂环族环氧树脂单体epalloy5000、与芳香族环氧树脂单体YX4000的组合形成的导热材料,比脂肪族环氧树脂单体BUT与脂环族环氧树脂单体epalloy 5000的组合形成的导热材料具有较高的导热系数。
实施例41
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=7:2:1)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例42
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=6:1:3)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例43
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)。其余硬化剂种类与用量及硬化条件与实施例29类似。
实施例44
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:2:3)。其余硬化剂种类与用量及硬化条件与实施例29类似。
表12
由表10与表12的比较可知,脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、与芳香族环氧树脂单体YX4000的组合形成的导热材料,比脂肪族环氧树脂单体BUT与脂环族环氧树脂单体YX8000的组合形成的导热材料具有较高的导热系数。
实施例45
取5g的环氧树脂单体如脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4),与1.117g的脂环族胺类硬化剂JER-113以及0.929g的芳香族胺类硬化剂DDM(摩尔比=1:1)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例46
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及0.995g的芳香族胺类硬化剂DDE(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例47
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.323g的芳香族胺类硬化剂CUAHARD-MED(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例48
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.060g的芳香族胺类硬化剂MDA(摩尔比=1:1)。其余硬化条件与实施例45类似。
表13
由表12的实施例43与表13的比较可知,脂环族胺类硬化剂JER-113以及某些芳香族胺类硬化剂(如DDE与CUAHARD-MED)的组合,可提高导热材料的导热系数。
实施例49
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.163g的芳香族胺类硬化剂DDS(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例50
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.370g的芳香族胺类硬化剂TPE-Q(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例51
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.724g的芳香族胺类硬化剂BAPB(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例52
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及0.995g的芳香族胺类硬化剂m-Tolidine(摩尔比=1:1)。其余硬化条件与实施例45类似。
表14
由表12的实施例43与表14的比较可知,脂环族胺类硬化剂JER-113以及某些芳香族胺类硬化剂(如BAPB)的组合,可提高导热材料的导热系数。
实施例53
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及0.535g的脂环族胺类硬化剂CHD(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例54
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及0.986g的脂环族胺类硬化剂DACH(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例55
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.673g的芳香族胺类硬化剂CUA-4(摩尔比=1:1)。其余硬化条件与实施例45类似。
实施例56
与实施例45类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及2.286g的芳香族胺类硬化剂ELASMER 250P(摩尔比=1:1)。其余硬化条件与实施例45类似。
表15
由表12的实施例43与表15的比较可知,两种胺类硬化剂的组合,可提高导热材料的导热系数。
比较例1
取5g的芳香族环氧树脂828与1.642g的芳香族胺类硬化剂DDS混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
比较例2
取5g的脂肪族环氧树脂NEO与4.264g的脂环族胺类硬化剂JER-113混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
比较例3
取5g的脂肪族环氧树脂BUT与3.870g的脂环族胺类硬化剂JER-113混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
表16
由表16可知,单一环氧树脂单体与单一胺类硬化剂的组合形成的导热材料,其导热系数低。
实施例57
取5g的环氧树脂单体如脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)、2.295g的脂环族胺类硬化剂JER-113、与29.18g的高导热填充物Al2O3(占导热材料的80wt%)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例58
与实施例57类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及1.771g的芳香族胺类硬化剂BAPB(摩尔比=1:1)。其余硬化条件与实施例57类似。
实施例59
与实施例57类似,差别在于胺类硬化剂改为1.148g的脂环族胺类硬化剂JER-113以及2.349g的芳香族胺类硬化剂ELASMER 250P(摩尔比=1:1)。其余硬化条件与实施例57类似。
表17
由表17的比较可知,高导热填充物可提高导热材料的导热系数。另一方面,脂环族胺类硬化剂以及芳香族胺类硬化剂的组合,可进一步提高导热材料的导热系数。
实施例60
取5g的环氧树脂单体如脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)、2.234g的脂环族胺类硬化剂JER-113、与28.936g的高导热填充物Al2O3(占导热材料的80wt%)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例61
与实施例60类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及1.724g的芳香族胺类硬化剂BAPB(摩尔比=1:1)。其余硬化条件与实施例60类似。
实施例62
与实施例60类似,差别在于胺类硬化剂改为1.117g的脂环族胺类硬化剂JER-113以及2.286g的芳香族胺类硬化剂ELASMER 250P(摩尔比=1:1)。其余硬化条件与实施例60类似。
表18
由表18的比较可知,高导热填充物可提高导热材料的导热系数。另一方面,脂环族胺类硬化剂以及芳香族胺类硬化剂的组合,可进一步提高导热材料的导热系数。
实施例63
取5g的环氧树脂单体如脂肪族环氧树脂单体NEO、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=5:1:4)、1.148g的脂环族胺类硬化剂JER-113及2.349g的芳香族胺类硬化剂ELASMER 250P、与56.865g的高导热填充物Al2O3(占导热材料的87wt%)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
实施例64
与实施例63类似,差别在于高导热填充物Al2O3的用量改为112.89g(93wt%)。其余硬化条件与实施例63类似。
实施例65
与实施例63类似,差别在于高导热填充物Al2O3的用量改为161.443g(95wt%)。其余硬化条件与实施例63类似。
表19
由表19可知,增加高导热填充物的比例可增加高导热材料的导热系数。
比较例4
取5g的环氧树脂如芳香族环氧树脂单体828、1.642g的芳香族胺类硬化剂DDS、与26.568g的高导热填充物Al2O3(占导热材料的80wt%)混合均匀后,置于150℃的烘箱中1小时使其硬化,得到导热材料。
表20
比较例5
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=8.9:0.1:1)。其余硬化剂种类与用量与实施例29类似。上述组合物在硬化前即有不相容的问题如相分离,因此未进一步硬化。
比较例6
与实施例29类似,差别在于5g的环氧树脂单体改为脂肪族环氧树脂单体BUT、脂环族环氧树脂单体YX8000、及芳香族环氧树脂单体YX4000(摩尔比=0.5:1:1)。其余硬化剂种类与用量及硬化条件与实施例29类似。上述组合物硬化后形成的样品刚硬脆裂,无法测量其性质。
表21
虽然本公开已以数个实施例揭露如上,然其并非用以限定本公开,任何本技术领域的技术人员在不脱离本公开的精神和范围内,应可作任意的更动与润饰,因此本公开的保护范围应以所附权利要求书所界定的范围为准。

Claims (13)

1.一种树脂组合物,包括:
1摩尔份的(a)芳香族环氧树脂单体;
0.25至1摩尔份的(b)脂环族环氧树脂单体;以及
1至9摩尔份的(c)脂肪族环氧树脂单体。
2.如权利要求1所述的树脂组合物,其中(a)芳香族环氧树脂单体的结构为:
其中Ar为
R1为-CH2-、-C(CH3)2-、-CH=CH-、-CH=C(CH3)-、-O-、-C≡C-、-C=CH-CO-、-COO-、-CONH-、或-CO-;以及
每一R2各自为H、卤素、或C1-8烷基。
3.如权利要求1所述的树脂组合物,其中(b)脂环族环氧树脂单体的结构为:
其中Cy为
R3为-CH2-、-C(CH3)2-、-CH=CH-、-CH=C(CH3)-、-O-、-C≡C-、-C=CH-CO-、-COO-、-CONH-、或-CO-;以及
每一R4各自为H、卤素、或C1-8烷基。
4.如权利要求1所述的树脂组合物,其中(c)脂肪族环氧树脂单体的结构为:
其中R为C1-6直链状烷撑基,且直链状烷撑基上取代有氢或C1-8烷基。
5.如权利要求1所述的树脂组合物,还包括(d)胺类硬化剂,其中(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的环氧基与(d)胺类硬化剂的胺基之间的摩尔比为1:1至2:1。
6.如权利要求5所述的树脂组合物,其中(d)胺类硬化剂的结构为:
H2N-R5-NH2或H2N-Ar’-O-R6-O-Ar’-NH2
其中R5 R11为C1-6烷撑基,且n’=1至10之间;
R7为单键、-O-、-SO2-、-CH2-、-(CH2)2-、或-C(CF3)2-;以及
每一R8各自为H、卤素、或C1-8烷基;
其中R6
R9为单键、-O-、-SO2-、或-C(CF3)2-;
每一R10各自为H、卤素、或C1-8烷基;
n为3至12的整数;以及
Ar’为
7.如权利要求5所述的树脂组合物,其中(d)胺类硬化剂包括脂环族胺类硬化剂与芳香族胺类硬化剂的组合。
8.如权利要求1所述的树脂组合物,还包括(e)导热填充物,其中(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的总重与(e)导热填充物的重量之间的比例为70:30至5:95。
9.如权利要求8所述的树脂组合物,其中(e)导热填充物包括金属、金属氧化物、陶瓷、碳材、或上述的组合。
10.一种导热材料的形成方法,包括:
混合1摩尔份的(a)芳香族环氧树脂单体;0.25至1摩尔份的(b)脂环族环氧树脂单体;以及1至9摩尔份的(c)脂肪族环氧树脂单体,以形成树脂组合物;以及
加热硬化该树脂组合物,以形成导热材料。
11.如权利要求10所述的导热材料的形成方法,其中该树脂组合物还包括(d)胺类硬化剂,其中(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的环氧基与(d)胺类硬化剂的胺基之间的摩尔比为1:1至2:1。
12.如权利要求11所述的导热材料的形成方法,其中(d)胺类硬化剂包括脂环族胺类硬化剂与芳香族胺类硬化剂的组合。
13.如权利要求10所述的导热材料的形成方法,其中该树脂组合物还包括(e)导热填充物,其中(a)芳香族环氧树脂单体、(b)脂环族环氧树脂单体和(c)脂肪族环氧树脂单体的总重与(e)导热填充物的重量之间的比例为70:30至5:95。
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