CN1282697C - 热固性有机树脂组合物 - Google Patents

热固性有机树脂组合物 Download PDF

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CN1282697C
CN1282697C CNB028214749A CN02821474A CN1282697C CN 1282697 C CN1282697 C CN 1282697C CN B028214749 A CNB028214749 A CN B028214749A CN 02821474 A CN02821474 A CN 02821474A CN 1282697 C CN1282697 C CN 1282697C
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resin composition
composition
organic resin
work embodiment
weight part
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CN1578808A (zh
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岩井亮
脇田启二
白幡明彦
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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Abstract

热固性有机树脂组合物，包括(A)100重量份热固性有机树脂，和(B)0.01-100重量份用通式X-R1-Si(OR2)nR3-n 3(其中X是NCS-或SCN-，R1是亚烷基或亚烷氧基亚烷基，R2和R3是单价烃基，和下标n是1、2或3)表示的含硫氰基的有机烃氧基硅烷或含异硫氰基的有机烃氧基硅烷。该热固性有机树脂组合物具有优异的模塑性，和当固化时，对基体如金属显示出优异的粘合性。

Description

热固性有机树脂组合物
本发明涉及热固性有机树脂组合物，和更具体地，本发明涉及具有优异模塑性和当固化时，在基体如金属上显示优异粘合性的热固性有机树脂组合物。
已知配混含环氧的有机硅烷、含胺的有机烷氧基硅烷或含巯基的有机烷氧基硅烷与环氧树脂会改进它们的粘合性。例如，日本专利申请公报(公开)No.昭63-309566教导了一种具有改进粘合性的涂料材料组合物、它是通过配混硅烷偶联剂如3-环氧丙氧丙基甲基二乙氧基硅烷、N-苯基-3-aminuteso丙基三甲氧基硅烷和3-巯丙基三甲氧基硅烷与环氧树脂粉末涂料材料获得的。
此外，日本专利申请公报(公开)No.平2-185584教导了一种粘合剂组合物，它是通过配混3-巯丙基三甲氧基硅烷与环氧树脂而获得的。然而，通过添加含环氧的烷氧基硅烷获得的组合物的粘合性对基体如金属等未必充分，和取决于所打算的用途，这种组合物可能不是合适的。此外，在通过添加含胺的有机烷氧基硅烷或含巯基的有机烷氧基硅烷而获得的组合物中，环氧树脂的初始固化性受到严重损害。
另一方面，还已知含硫氰基的有机烷氧基硅烷和含所述含硫氰基有机烷氧基硅烷的有机橡胶组合物。例如，日本专利申请公报(公开)No.平4-277534教导了通过配混三元乙丙橡胶(EPDM)与硫氰基丙基三甲氧基硅烷而获得的组合物。在有机过氧化物存在下硫化之后，据说这种组合物产生物性很少劣化和压缩永久变形小的橡胶模制品。
另外，日本专利申请公报(公开)No.平5-214171教导了可硫化的有机橡胶组合物，它是通过配混硫氰基丙基三甲氧基硅烷与可硫化的有机橡胶，如天然橡胶(NR)、丁苯橡胶(SBR)、EPDM等而获得的。当在硫存在下硫化时，据说这些组合物产生物性较少劣化的橡胶模制品。
然而，还没有已知的热固性有机树脂组合物，其中将含硫氰基的有机烷氧基硅烷加入到热固性有机树脂中会改进所述有机树脂的模塑性和对与所述热固性有机树脂组合物接触的基体如金属的粘合性。
经过艰苦的努力，本发明者发现，若将环氧树脂与含硫氰基的有机烷氧基硅烷配混，则可解决以上所述的问题。此外，他们已发现，配混含硫氰基的有机烷氧基硅烷与热固性有机树脂，如酚醛树脂、酰亚胺树脂等，会导致它们的粘合性的改进。
本发明的目的是提供一种具有优异模塑性的热固性有机树脂组合物，在没有损害热固性有机树脂本身的固化性的情况下它会固化，和当固化时，对与所述热固性有机树脂组合物接触的基体如金属显示出优异的粘合性。
本发明涉及热固性有机树脂组合物，包括：(A)100重量份热固性有机树脂，和(B)0.01-100重量份用通式X-R1-Si(OR2)nR3 3-n(其中X是NCS-或SCN-，R1是亚烷基或亚烷氧基亚烷基，R2和R3是单价烃基，和下标n是1、2或3)表示的含硫氰基的有机烃氧基硅烷或含异硫氰基的有机烃氧基硅烷。
现进一步解释上述内容。对热固性有机树脂(A)的类型等没有特别限制，只要该热固性有机树脂在常温下是液体或固体且受热时会固化即可。
可以例举环氧树脂、酚醛树脂、甲醛树脂、二甲苯树脂、二甲苯-甲醛树脂、酮醛树脂、呋喃树脂、脲树脂、酰亚胺树脂、三聚氰胺树脂、醇酸树脂、不饱和聚酯树脂、苯胺树脂、磺酰胺树脂和硅氧烷树脂作为这种热固性有机树脂。在以上的树脂当中，优选环氧树脂、酚醛树脂和酰亚胺树脂。
组分(B)构成本发明组合物的主要特征并用于改进本发明组合物的模塑性和它对基体如金属的粘合性。组分(B)是用通式X-R1-Si(OR2)nR3 3-n(其中X是NCS-或SCN-，R1是亚烷基或亚烷氧基亚烷基，R2和R3是单价烃基，和下标n是1、2或3)表示的含硫氰基的有机烃氧基硅烷或含异硫氰基的有机烃氧基硅烷。
在以上通式中，R1的亚烷基可例举亚甲基、亚乙基、甲基亚甲基、亚丙基、甲基亚乙基和亚丁基。R1的亚烷氧基亚烷基可例举亚甲氧基亚甲基、亚甲氧基亚乙基、亚乙氧基亚乙基和亚乙氧基亚丙基。R1优选亚烷基。R2和R3的单价烃基可例举甲基、乙基、正丙基、异丙基和其它烷基；乙烯基、烯丙基、丁烯基和其它链烯基；和苯基、甲苯基、二甲苯基和其它芳基。R2和R3优选烷基。下标n是1、2或3，优选2和3。
组分(B)的含硫氰基的有机烃氧基硅烷或含异硫氰基的有机烃氧基硅烷可例举下述化合物：
NCS(CH2)3Si(OCH3)3
NCS(CH2)3Si(OCH2CH3)3
NCS(CH2)3Si[OCH(CH2)3]3
NCS(CH2)3Si[O(CH2)2CH3]3
NCS(CH2)3Si[O(CH2)3CH3]3
NCSCH2CH(CH3)CH2Si(OCH3)3
NCSCH2CH(CH3)CH2Si(OCH2CH3)3
SCN(CH2)3Si(OCH3)3
SCN(CH2)3Si(OCH2CH3)3
SCN(CH2)3Si[OCH(CH3)2]3
SCNCH2CH(CH3)CH2Si(OCH3)3
SCNCH2CH(CH3)CH2Si(OCH2CH3)3
SCNCH2CH(CH3)CH2Si[OCH(CH3)2]3
SCNCH2CH(CH3)CH2Si(O(CH2)3CH3)3
NCS(CH2)3SiCH3(OCH3)2
NCS(CH2)3SiCH3(OCH2CH3)2
NCS(CH2)3Si(OC6H5)3
NCSCH2CH(CH3)CH2SiCH3(OCH3)3
可将两种或多种组分(B)加入到组合物中。
若加入到组合物中的组分(B)的用量太小，则它对基体如金属的粘合性会劣化，和若太大，则它的机械性能会下降。由于该原因，其用量应当在0.01-100重量份范围内，和优选在0.1-50重量份范围内，以每100重量份的组分(A)计。
尽管本发明的组合物包括以上提及的组分(A)和组分(B)，但除了这些组分之外，已知将与组分(A)配混的各种添加剂可与之结合，例如促进组分(A)固化所使用的固化剂或固化促进剂、填料、增塑剂、增韧剂、颜料、热稳定剂、阻燃剂、抗氧剂、光敏剂、有机溶剂等。
固化剂或固化促进剂的一些实例包括伯和仲胺化合物、叔胺化合物；邻苯二甲酸酐、四氢邻苯二甲酸酐、和其它羧酸酐；咪唑化合物；可溶可熔酚醛树脂、甲酚可溶酚醛树脂；和其它线型酚醛树脂；有机铝化合物、有机锆化合物和其它有机金属化合物；膦和其它有机磷化合物；硼络合物化合物、有机铵盐、有机锍盐、有机过氧化物等。
固化剂的添加量优选0.1-30重量份，以每100重量份组分(A)计，用于固化环氧树脂的线型酚醛树脂的添加量优选为10-400重量份，以每100重量份环氧树脂计，和固化促进剂的添加量优选为0.01-10重量份，以每100重量份组分(A)计。
填料可例举玻璃纤维、石棉、氧化铝纤维、含氧化铝和二氧化硅的陶瓷纤维、硼纤维、氧化锆纤维、碳化硅纤维、金属纤维、聚酯纤维、芳族聚酰胺纤维、尼龙纤维、酚醛纤维、天然植物和动物纤维和其它纤维状填料；熔凝硅石、沉淀二氧化硅、煅制二氧化硅、焙烧二氧化硅、氧化锌、焙烧粘土、炭黑、玻璃珠、氧化铝、滑石、碳酸钙、粘土、氢氧化铝、硫酸钡、二氧化钛、氮化铝、碳化硅、氧化镁、氧化铍、高岭土、云母、氧化锆和其它粉状填料。
在非液态热固性有机树脂组合物中，填料的添加量优选为10-500重量份，以每100重量份组分(A)计，和在液态热固性有机树脂组合物中，添加量优选为0-50重量份，以每100重量份组分(A)计。
增塑剂和增韧剂可例举高级脂肪酸的金属盐、酯蜡、硅油、含有机官能团的硅油、硅橡胶和有机橡胶。
本发明的组合物包括以上所述的组分(A)和组分(B)，和可容易地通过将它们与以上所述的添加剂(视需要)均匀混合来制备。制备本发明组合物所使用的设备的一些实例包括连续混合挤出机、Ross混炼机、捏和混炼机、双辊开炼机等。另外，可在由本发明的组合物制造模制品过程中，使用适合于组分(A)的称为模塑方法的常规公知的方法，如压缩模塑、传递模塑、注模、灌封、浇注、涂覆等。
以上所述的本发明组合物具有优异的模塑性，和当固化时，对与所述组合物接触的基体如金属具有优异的粘合性。镍、铜、黄铜、铁、钢、不锈钢、铝、硬铝、钛和银例举作为金属，和玻璃、陶瓷、石头和半导体例举为基体。通过开发这些性能优点，可证明它例如在电子和电气组件或器件、机器、建筑物、汽车等中使用的密封剂、包装剂、涂布剂、粘合剂等中有用。
实施例
通过参考工作实施例，以下将详细地解释本发明的组合物。在工作实施例和对比例中使用的术语“粘度”是指在25℃下获得的值。另外，根据下述方法评价热固性有机树脂组合物的模塑性、粘合力(粘合性)和粘度变化率。
模塑性
通过测量热固性有机树脂组合物的螺线流动，评价其在压力下的模塑性。通过基于EMMI标准(EMMI-1-66)的试验，测量螺线流动。
粘合力(A)
通过将热固性有机树脂组合物夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在规定的温度和规定的压力下进行压缩模塑，制造用热固性有机树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。将样片的两块镍板的边缘分别固定在拉伸测试机的夹具上，并在垂直方向以50mm/min的速度牵引开，从而将镍板与有机树脂组合物的已固化产品剥离开。
随后，在热固性有机树脂组合物的已固化产品与镍板之间的断裂表面的状况进行目测。以下述方式表示结果。
◎：非常良好的粘合(在固化的热固性有机树脂层内出现的断裂。内聚破坏：100％)。
○：良好的粘合(出现部分界面剥离。内聚破坏：95％或更高)。
×：差的粘合(在已固化的有机树脂与镍板的界面处出现剥离。内聚破坏：50％或更低)。
粘合力(B)
通过将热固性有机树脂组合物夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在规定的温度和规定的压力下进行压缩模塑，制造用热固性有机树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。另外，以与上述相同的方式制造用热固性有机树脂组合物的已固化产品整体粘结的铜板组成的粘合样片。
将这些样片的两块镍板或两块铜板的边缘分别固定在拉伸测试机的夹具上，并在垂直方向以50mm/min的速度牵引开，从而将镍板或铜板与有机树脂组合物的已固化产品剥离开。测量剥离所要求的应力，并用作粘合强度(kgf/cm2)。
粘度变化率：
在制备之后，使热固性有机树脂组合物在23℃下放置24小时。测量其粘度增加程度并用作粘度变化率。粘度变化率＝(热固性有机树脂组合物放置24小时时的粘度-热固性有机树脂组合物在刚制备之后的粘度)×100/热固性有机树脂组合物在刚制备之后的粘度。
工作实施例1
使用在90℃下的加热辊，通过捏和35重量份酚醛树脂(获自Mitsui Chemicals，Inc.的可溶可熔酚醛树脂Mirex XLC-3L，软化点为70℃，羟基当量为170)、3重量份 3-硫氰基丙基三甲氧基硅烷{NCS(CH2)3Si(OCH3)3}、65重量份熔凝硅石粉末、4重量份六亚甲基四胺和1重量份巴西棕榈蜡，制备热固性酚醛树脂组合物。
精细粉化该组合物，并将粉化物质夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在175℃的温度和70kg/cm2的压力下加热3分钟，来进行压缩模塑。此后，为了完成固化，在180℃下加热组合物2小时，从而产生用酚醛树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。使用该样片，根据以上的粘合力(A)中所述的方法，测量热固性酚醛树脂组合物对镍板的粘合力，和结果列在表1中。
对比例1
以与工作实施例1相同的方式制备可溶可熔酚醛树脂组合物，所不同的是，添加3-环氧丙氧丙基三甲氧基硅烷，而不是工作实施例1中使用的3-硫氰基丙基三甲氧基硅烷。以与工作实施例1相同的方式测量组合物对镍板的粘合力，和结果列在表1中。
对比例2
以与工作实施例1相同的方式制备可溶可熔酚醛树脂组合物，所不同的是，不使用工作实施例1中的3-硫氰基丙基三甲氧基硅烷。以与工作实施例1相同的方式测量组合物对镍板的粘合力，和结果列在表1中。
表1
测量项目 工作实施例1 对比例1 对比例2
粘合力(A) ◎ × ×
工作实施例2
使用在90℃下的加热辊，通过捏合13重量份由40mol％CH3SiO3/2单元、10mol％C6H5(CH3)SiO2/2单元、40m0l％C6H5SiO3/2单元和10mol％(C6H5)2SiO2/2单元组成且含有5wt％直接键合到硅原子上的羟基的甲基苯基聚硅氧烷树脂、13重量份邻甲酚可溶酚醛环氧树脂(获自Nippon Kayaku Co.，Ltd.的EOCN-1020，软化点为80℃，环氧当量为220)、2重量份 3-异硫氰基丙基甲基二甲氧基硅烷{NCS(CH2)3SiCH3(OCH3)2}、74重量份熔凝硅石粉末、0.90重量份乙酰基丙酮酸铝和1重量份巴西棕榈蜡，制备热固性硅氧烷环氧树脂组合物。
测量热固性环氧树脂组合物的螺线流动。接下来，将该热固性环氧树脂组合物夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在175℃的温度和70kg/cm2的压力下加热2分钟，来进行压缩模塑。
此后，为了完成固化，在180℃下加热组合物12小时，从而产生用热固性有机树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。使用该样片，根据以上的粘合力(A)中所述的方法，测量热固性有机树脂组合物对镍板的粘合力，和结果列在表2中。
工作实施例3
以与工作实施例2相同的方式制备热固性环氧树脂组合物，所不同的是，添加3-异硫氰基丙基甲基三甲氧基硅烷{SCN(CH2)3Si(OCH3)3}，而不是工作实施例2中使用的3-硫氰基丙基甲基二甲氧基硅烷。以与工作实施例2相同的方式测量组合物的螺线流动，和它对镍板的粘合力，和结果列在表2中。
对比例3
以与工作实施例2相同的方式制备热固性环氧树脂组合物，所不同的是，添加3-巯丙基三甲氧基硅烷{HS(CH2)3Si(OCH3)3}，而不是工作实施例2中使用的3-硫氰基丙基甲基二甲氧基硅烷。以与工作实施例2相同的方式测量组合物的螺线流动，和它对镍板的粘合力，和结果列在表2中。
对比例4
以与工作实施例2相同的方式制备热固性环氧树脂组合物，所不同的是，不添加工作实施例2中使用的3-硫氰基丙基甲基二甲氧基硅烷。以与工作实施例2相同的方式测量组合物的螺线流动，和它对镍板的粘合力，和结果列在表2中。
                            表2
测量项目 工作实施例2 工作实施例3 对比例3 对比例4
螺线流动(英寸) 42 39 21 13
  粘合力(A) ◎ ○ ○ ×
工作实施例4
使用在90℃下的加热辊，通过捏和35重量份双马来酰亚胺三嗪型热固性聚酰亚胺树脂(获自Mitsuibishi Gas Chemical Co.，Ltd.)、4重量份3-硫氰基丙基三甲氧基硅烷{NCS(CH2)3Si(OCH3)3}、65重量份熔凝硅石粉末、1重量份巴西棕榈蜡和0.32重量份苯甲酸铝，制备热固性聚酰亚胺树脂组合物。测量该组合物的螺线流动。
随后，将该组合物夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在220℃的温度和70kg/cm2的压力下加热4分钟，来进行压缩模塑。此后，为了完成固化，在230℃下加热组合物3小时，从而产生用热固性聚酰亚胺树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。
使用该样片，根据以上的粘合力(A)中所述的方法，测量热固性聚酰亚胺树脂组合物对镍板的粘合力，和结果列在表3中。
对比例5
以与工作实施例4相同的方式制备热固性聚酰亚胺树脂组合物，所不同的是，不添加工作实施例4中使用的3-硫氰基丙基三甲氧基硅烷。以与工作实施例4相同的方式测量组合物的螺线流动，和它对镍板的粘合力，和结果列在表3中。
                 表3
测量项目 工作实施例4 对比例5
螺线流动(英寸) 52 43
粘合力(A) ◎ ×
工作实施例5
使用在90℃下的加热辊，通过捏合75重量份邻甲酚可溶酚醛环氧树脂(获自Nippon Kayaku Co.，Ltd.的EOCN-1020，软化点为80℃，环氧当量为220)、260重量份熔凝硅石、1重量份巴西棕榈蜡、35重量份可溶可熔酚醛树脂(获自Mitsui Chemicals，Inc.的Mirex XLC-3L，软化点为70℃，羟基当量为170)、0.6重量份三苯基膦和5重量份3-硫氰基丙基三甲氧基硅烷{NCS(CH2)3Si(OCH3)3}，制备热固性环氧树脂组合物。
测量该组合物的螺线流动。随后，将该组合物夹在两块镍板(长度5cm，宽度1cm，厚度0.5mm)之间，并在150℃的温度和70kg/cm2的压力下加热3分钟，进行压缩模塑。此后，为了完成固化，在180℃下加热组合物4小时，从而产生用热固性环氧树脂组合物的已固化产品整体粘结的镍板组成的粘合样片。使用该样片，根据以上的粘合力(A)中所述的方法，测量热固性环氧树脂组合物对镍板的粘合力，和结果列在表4中。
对比例6
以与工作实施例5相同的方式制备热固性环氧树脂组合物，所不同的是，添加3-环氧丙氧丙基三甲氧基硅烷，而不是工作实施例5中使用的3-硫氰基丙基三甲氧基硅烷。根据以上的粘合力(A)中所述的方法，测量组合物的螺线流动和它对镍板的粘合力，和结果列在表4中。
对比例7
以与工作实施例5相同的方式制备热固性环氧树脂组合物，所不同的是，不添加工作实施例5中使用的3-硫氰基丙基三甲氧基硅烷。根据以上的粘合力(A)中所述的方法，测量组合物的螺线流动和它对镍板的粘合力，和结果列在表4中。
                         表4
测量项目 工作实施例5 对比例6 对比例7
螺线流动(英寸) 55 53 52
粘合力(A) ◎ × ×
工作实施例6
在室温下，通过彻底混合20重量份液体环氧树脂(获自UnionCarbide的ERL-4221)、22重量份液体酸酐(3-和4-甲基六氢邻苯二甲酸酐)、0.3重量份辛酸锡和2重量份3-硫氰基丙基三甲氧基硅烷{NCS(CH2)3Si(OCH3)3}，并使混合物消泡，从而制备热固性液体环氧树脂组合物。测量组合物的粘度变化率。
随后，将该组合物夹在两块镍板或两块铜板(长度5cm，宽度1cm，厚度0.5mm)之间，并在120℃的温度和70kg/cm2的压力下加热3分钟，来进行压缩模塑。此后，为了完成固化，在150℃下加热组合物3小时，从而产生用热固性环氧树脂组合物的已固化产品整体粘结的镍板或铜板组成的粘合样片。使用该样片，根据以上的粘合力(B)中所述的方法，测量其粘合力，和结果列在表5中。
对比例8
以与工作实施例6相同的方式制备热固性液体环氧树脂组合物，所不同的是，添加3-巯丙基三甲氧基硅烷，而不是工作实施例6中使用的3-硫氰基丙基三甲氧基硅烷。根据以上的粘合力(B)中所述的方法，测量组合物的粘度变化率和粘合力，和结果列在表5中。
对比例9
以与工作实施例6相同的方式制备热固性液体环氧树脂组合物，所不同的是，添加3-环氧丙氧丙基三甲氧基硅烷，而不是工作实施例6中使用的3-硫氰基丙基三甲氧基硅烷。根据以上的粘合力(B)中所述的方法，测量组合物的粘度变化率和粘合力，和结果列在表5中。
对比例10
以与工作实施例6相同的方式制备热固性液体环氧树脂组合物，所不同的是，不添加工作实施例6中使用的3-硫氰基丙基三甲氧基硅烷。以与工作实施例6相同的方式固化该组合物。根据以上的粘合力(B)中所述的方法，测量组合物的粘度变化率和粘合力，和结果列在表5中。
                                   表5
测量项目 工作实施例6 对比例8 对比例9 对比例10
粘度变化率 2 不可能测量(出现凝胶) 13 4
粘合力(B)(kg/cm2)镍板铜板 182121 8589 6252 5953
由于本发明的热固性组合物包括100重量份组分(A)和0.01-100重量份组分(B)，即用通式X-R1-Si(OR2)nR3 3-n(其中X是NCS-或SCN-，R1是亚烷基或亚烷氧基亚烷基，R2和R3是单价烃基，和下标n是1、2或3)表示的含硫氰基的有机烃氧基硅烷或含异硫氰基的有机烃氧基硅烷，因此它具有优异的模塑性，和当固化时，对与所述热固性有机树脂组合物接触的基体如金属显示出优异的粘合性。

Claims (2)

1.热固性有机树脂组合物，包括：
(A)100重量份选自环氧树脂、酚醛树脂和酰亚胺树脂的热固性有机树脂，和(B)0.01-100重量份用通式X-R1-Si(OR2)nR3 3-n表示的含硫氰基的有机烷氧基硅烷或含异硫氰基的有机烷氧基硅烷，其中X是NCS-或SCN-，R1是亚烷基，R2和R3是烷基，和下标n是1、2或3。
2.权利要求1的热固性有机树脂组合物，其中组分(B)是3-硫氰基丙基三甲氧基硅烷、3-硫氰基丙基甲基二甲氧基硅烷或3-异硫氰基丙基三甲氧基硅烷。
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