CN1930206B - 环氧粘合剂组合物 - Google Patents

环氧粘合剂组合物 Download PDF

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CN1930206B
CN1930206B CN2005800073567A CN200580007356A CN1930206B CN 1930206 B CN1930206 B CN 1930206B CN 2005800073567 A CN2005800073567 A CN 2005800073567A CN 200580007356 A CN200580007356 A CN 200580007356A CN 1930206 B CN1930206 B CN 1930206B
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A·卢茨
K·弗里克
C·格罗斯尼克尔
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Abstract

本发明涉及一种环氧粘合剂组合物,其含有a)第一种环氧树脂,b)第二种环氧树脂,其用丙烯腈-丁二烯橡胶改性,后者含有平均少于25重量%的丙烯腈,和c)增韧剂。组分b)和组分c)的总量为大于30%,以组合物的总重量计,组分c)对组分b)的重量比大于1∶1。本发明进一步涉及所述环氧粘合剂组合物在组装交通工具的部件中的应用。其还涉及一种交通工具,其中其部件用所述的环氧粘合剂组合物组装。

Description

环氧粘合剂组合物 
本发明涉及一种如权利要求1所述的环氧粘合剂组合物、如权利要求13所述的该环氧粘合剂组合物在交通工具的部件组装中的用途以及如权利要求14所述的交通工具。 
环氧粘合剂组合物是含有环氧树脂、固化剂和通常的促进剂的反应型粘合剂组合物。热活化时,环氧树脂的环氧基团与固化剂反应以通过加成聚合反应连结环氧树脂化合物来获得固化的产品。 
已知这种固化的产品具有良好的机械性能和优于其他反应型粘合剂的固化产品的耐化学性能。这些特征使环氧粘合剂组合物特别适用于其中必需满足严格的机械要求的苛求的应用,例如汽车工业。 
结构型环氧粘合剂以外的环氧粘合剂的固化产品,通常具有相对高的静态强度,例如高拉伸和搭接剪切强度。然而其动态强度即冲击剥离强度,通常较低。 
用于例如汽车、货车、机动卡车、卡车和火车的交通工具部件组装的粘合剂称为结构型粘合剂。这种结构型粘合剂的固化产品要经受高的静态和动态负载。为该目的,要将其他的柔韧剂和/或增韧剂加入到环氧粘合剂组合物中。 
结构型环氧粘合剂在多个专利申请中有所描述: 
EP-A-0 197 892描述了含有环氧树脂、包含氮气的增韧剂和促进剂的结构型粘合剂。该申请描述的问题是提供一种具有良好储存稳定性和高固化速率的结构型粘合剂。 
EP-A-0 308 664描述了含有与聚酚-终端的聚氨酯或聚脲相结合的丁二烯-丙烯腈共聚物的环氧粘合剂组合物。 
EP-A-0 353 190描述了含有与用官能化碳环芳族或芳脂族残基终端的聚醚、聚酯、聚硫酯或聚酰胺预聚物相结合的丁二烯-丙烯腈共聚物的环氧粘合剂组合物。 
EP-A-0 308 664和EP-A-0 353 190所述的技术称为Mühlhaupt技术。EP-A-0 308 664和EP-A-0 353 190所述的问题是改进固化产品的冲 击剥离强度(impact peel strength)。然而在低温时冲击剥离强度较低。 
WO 00/20483涉及一种组合物,其含有具有-30℃或更低的玻璃化转变温度的环氧化物反应性共聚物,和羧酸酸酐与二-或聚胺和聚酚或氨基苯酚的反应产物。 
WO 00/20483的固化产品在-40℃具有小于20N/mm的冲击剥离强度。 
由于交通工具通常要暴露在各种气候条件下,要求结构型粘合剂的固化产品在室温和低温时具有良好的机械性能。由于其在低温时较低的冲击剥离强度,上述已知的环氧粘合剂不能完全满足该要求。因此部件用上述已知的环氧粘合剂组装的交通工具不能完全符合安全要求,例如在碰撞测试中。 
上述已知的环氧粘合剂组合物的另一个缺点是其在中度和极度温度时在高强度金属上的相对低的冲击行为。由于该缺点,已知的环氧粘合剂组合物在组装高强度金属构造的部件中的应用收到限制。 
本发明的一个目的是提供一种环氧粘合剂组合物,其在固化时,产生在低至-40℃的低温时具有突出的机械性能,特别是高冲击剥离强度,同时保留室温时常规环氧粘合剂组合物的合意的机械性能的产品。 
本发明的另一个目的是提供一种环氧粘合剂组合物,其在固化时产生在高强度金属上具有高冲击剥离强度的产品。 
根据本发明,这些问题用权利要求1所述的组合物得以解决,该组合物含有: 
a)第一种环氧树脂, 
b)第二种环氧树脂,其用丙烯腈-丁二烯橡胶改性,后者含有平均少于25重量%的丙烯腈,和 
c)增韧剂, 
组分b)和组分c)的总量为大于30%,以组合物的总重量计,组分c)对组分b)的重量比大于1∶1。 
该组合物的优选实施方案在权利要求中定义。 
本发明的环氧粘合剂组合物固化时产生在室温时具有大于35N/mm和在-40℃时大于25N/mm的冲击剥离强度。显著改进的低温冲击强度使得该环氧粘合剂组合物可以用作结构型粘合剂,其在固化 时在使用的任何温度都具有高的耐碰撞性,满足最严格的安全要求。 
由于该改进的韧性,本发明的环氧粘合剂组合物的固化产品在高强度金属上具有优异的冲击剥离强度。使用本发明的环氧粘合剂组合物组装高强度金属部件使得获得的高强度金属构造物比用常规粘合剂粘合的构造物具有更高的负载。本发明的环氧粘合剂组合物在组装高强度金属部件中的适用性是高度期望的,这是由于高强度金属通过焊接的粘合通常不可行。 
除了改进的动态强度外,固化的环氧粘合剂组合物在-40℃到+80℃的温度范围内具有优良的静态强度。搭接剪切强度(lap shearstrength)高于25MPa,拉伸强度高于30MPa。其杨氏模量为大约1500MPa,断裂伸长率为大于10%。 
本发明的环氧粘合剂组合物在涂覆的钢上显示出优良的粘合性,例如在热浸涂、电镀和bonazinc钢、预处理的铝、镁和复合材料上。 
在本领域的技术人员已知的长期人工老化测试-如VDA、KKT、P1210和3C或短期人工老化测试(cataplasma)之后,本发明的环氧粘合剂组合物的强度值仅降低了20-30%。 
如权利要求1所述的第一种环氧树脂(组分a)可以是任何类型的环氧树脂,例如DER 330(低粘度、未稀释的双酚A液体环氧树脂)、DER 331(标准的、未稀释的、双酚A液体环氧树脂)或DER 671(低分子量固体环氧树脂),这些均为Dow Chemical Company的产品。第一种环氧树脂的优选例子是双酚的聚缩水甘油醚,例如2,2-双-(4-羟基苯基)-丙烷或双-(4-羟基苯基)-甲烷,或酚醛清漆(novolaks)的聚缩水甘油醚,其通过甲醛与酚反应形成、双酚A与具有缩水甘油基的脂族二醇的加合物。 
在一个优选的实施方案中,组分a)是至少两种不同环氧树脂的混合物。优选至少一种环氧树脂在室温时为液体。 
第二种环氧树脂用丙烯腈-丁二烯橡胶改性(组分b)。优选组分b)含有至少30重量%、优选至少40重量%的丙烯腈-丁二烯橡胶。丙烯腈-丁二烯橡胶优选为X8、X31或X8、X31和X13的任何混合物(其中X代表CTBN(羧基终端的丁二烯橡胶)类型的共聚物橡胶,术语“混合物”指的是“两种或三种组分的混合物”)。 
X8是含有17%的丙烯腈的CTBN类型的丙烯腈-丁二烯-橡胶。 
X13是含有26%的丙烯腈的CTBN类型的丙烯腈-丁二烯-橡胶。 
X31是含有10%的丙烯腈的CTBN类型的丙烯腈-丁二烯-橡胶。 
优选环氧粘合剂组合物含有少于20%、优选少于15%的丙烯腈,以丙烯腈-丁二烯橡胶的总重量计。 
组合物优选含有作为增韧剂(组分c)的具有通式I的化合物: 
Figure S05807356720060913D000041
其中m为1或2,n为2到6,R1为弹性预聚物在除去终端的异氰酸酯、氨基或羟基基团后的n-价的基团,弹性预聚物在环氧树脂中能够溶解或分散,W和X独立地为-O-或-NR3-,W和X中的至少一个为-NR3-,R2为聚酚或氨基苯酚在除去酚式羟基基团和任选的氨基基团后的m+1价的基团,R3为氢、C1到C6烷基或酚。 
关于通式I的增韧剂的详细描述见EP-A-0308664(第5页第14行至第13页第24行),在此并入其公开作为参考。 
在另一个优选的实施方案中,该组合物含有作为组分c)的具有通式II的化合物: 
其中p为1或2,q为2到6,Y为-O-、-S-或-NR6-,Z为选自-OH、-NHR6、-OCN、 
Figure S05807356720060913D000043
和 的基团,R4为羟基-、巯基-或氨基-终端的聚醚预聚物的残基或为羟基-、巯基-或氨基-终端的预聚、嵌段聚酯、聚硫酯或聚酰胺(polyamid)的残基,R5为碳环芳族或芳脂族(araliphatic)的p+1价的基团,基团Z直接键连到芳环上,R6为氢、C1到C6烷基或苯基,R7为甲基或氢。 
关于通式II的增韧剂的详细描述见EP-A-0 353 190(第3页第51行至第6页第62行),在此并入其公开作为参考。 
该组合物可以包括通式I的化合物和通式II的化合物的混合物作为组分c)。 
组分c)的例子为RAM A、RAM B或RAM C。RAM A、RAM B和RAM C是具有通式I的化合物,RAM A用烯丙基苯酚封端,RAM B用双酚A封端,RAM C用烷基酚封端。另一个例子是RAM 965,其是本领域技术人员所公知的。 
以组合物的总重量计,如果组分b)的量为14到20%,组分c)的量为18到28%,则获得特别良好的低温和在高强度钢上的冲击行为。 
如果环氧粘合剂组合物含有组分b)和组分c)的总量为至少35重量%、优选38重量%,则获得特别良好的结果。 
在另一个优选的实施方案中,组分c)对组分b)的重量比大于1.3∶1,优选大于1.5∶1。 
根据本发明的环氧粘合剂组合物可进一步包括添加剂,例如填料和促进剂,其对本领域技术人员是公知的。 
在一个优选的实施方案中,该组合物含有作为促进剂的沸点高于130℃的氮碱和为具有不饱和取代基的酚的加成聚合物的酚类聚合物的固体溶液。(术语“固体溶液”指的是组分以固体单相体系结合)。关于该促进剂的详细描述见EP-A-0 197 892(第7页第7行至第10页第28行),在此并入其公开作为参考。在这些促进剂中,特别优选本领域技术人员所公知的EP 796。 
环氧粘合剂组合物优选用于交通工具的部件的组装中,例如汽车、货车、机动卡车、卡车和火车。其也可以用于船只和飞行器的部件组装中。 
本发明的环氧粘合剂组合物优选在40°到65℃的温度使用。其可以用机器人通过使成旋涡地或喷射流动地作为标准珠粒手工或自动施用。固化在高于140℃的温度下开始。 
实施例 
环氧粘合剂组合物的制备
将7重量%的Struktol 3604(Schill & Seilacher)、7重量%的Struktol3914、11重量%的DER 330、20.2重量%的DER 331、16.3重量%的 DER 671、24重量%的增韧剂RAM B和0.2重量%的DW 0135 blue(Huntsman)在实验室行星式混合器中在90℃混合30分钟。然后,加入0.6重量%的例如环氧硅烷的粘合促进剂、4.3重量%的热解法二氧化硅(Aerosil;Degussa)和0.2重量%的润湿剂,将混合物在室温再搅拌30分钟。然后,加入4.2重量%的DICY(氰基胍,Airproducts)、0.75重量%的促进剂EP 796(Huntsman)和3.2重量%的胶凝化合物,将混合物在室温再搅拌15分钟。所有的混合步骤均在真空下进行。 
环氧粘合剂组合物的测试
在高于140℃的温度固化后,粘合剂本身显示出如下标准数值: 
E模量:大约1500MPa 
拉伸强度:大约35MPa 
伸长率:大约15% 
45℃时的粘度:158Pas 
45℃时的屈服点:47Pa 
搭接剪切(1.5mm;CRS 1403):>25MPa 
室温时的冲击剥离强度(1mm;CRS 1403):>35N/mm 
-40℃时的冲击剥离强度(1mm;CRS 1403):>25N/mm 
VDA测试在预处理的铝、热浸涂、电镀和bonazinc的涂覆钢上进行,其显示出强度仅下降20到30%。其他如KKT、P1210、3C和cataplasma的人工老化测试也显示出类似的结果。 
表1 低温冲击行为 
样品   室温时的冲  击剥离强度  (N/mm)  -40℃时的冲 击剥离强度 (N/mm)   组分b/量  重量%   组分c/量  重量%   组分c对组  分b的比
BM 1496C 2   53  43   Struktol  3914/20   RAM965/30   3∶2
C13   40  39   Struktol  3914/20   RAMB/30   3∶2
C14   32  29   Struktol  3914/15   RAMB/25   1.7∶1
C16   47  41   Struktol  3914/14   RAMB/28   2∶1
C18   37  40   Struktol  3914/12   RAMB/24   2∶1
C27   54  47   Struktol  3604/14   RAMB/28   2∶1
C29   51  30   Struktol  3914/14   RAMB/20   1.4∶1
C30(对比例)   30  12   Struktol  3914/15   RAMB/15   1∶1
C32   54  41   Struktol 3604  和3914/7,7   RAMB/24   1.7∶1
C39   42  47   Struktol 3604  和3914/7,7   RAM965/24   1.7∶1
C34(对比例)   42  19   Struktol 3614/  14   RAMB/24   1.7∶1
C36   43  45   Struktol  3914-1/14   RAMB/24   1.7∶1
C37   44  44   Struktol  3914-2/14   RAMB/24   1.7∶1
根据Mühlhaupt技术的对比结构型粘合剂   44  10   Struktol 3604/  14   RAM965/14   1∶1
根据Mühlhaupt技术的对比结构型粘合剂   38  13   Struktol 3614/  14   RAM965/14   1∶1
表1中,橡胶改性的环氧树脂(组分b)特征如下: 
Struktol 3604是由60%的双酚A的二缩水甘油醚(DGEBA)和40%的X8组成的橡胶改性的环氧树脂。 
Struktol 3614是由60%的DGEBA和40%的X13组成的橡胶改性的环氧树脂。 
Struktol 3914是由60%的DGEBA和40%的X31和X8混合物组成的橡胶改性的环氧树脂,其中X31∶X8=1∶1。 
Struktol 3914-1是由60%的DGEBA和40%的X31和X8混合物组成的橡胶改性的环氧树脂,其中X31∶X8=3∶1。 
Struktol 3914-2是由60%的DGEBA和40%的X31和X8混合物组成的橡胶改性的环氧树脂,其中X31∶X8=1∶3。 
根据ISO 11343测定冲击剥离强度的数值。 
如表1所示,本发明的环氧粘合剂组合物在-40℃比常规环氧粘合剂组合物具有显著更高的冲击剥离强度。 
表2 高强度钢上的冲击剥离强度:以N/mm为单位,室温 
  钢类型   BM 1496C 32  (根据本发明)   BM 1480  (对比例)   BM 1496V  (对比例)   BM 1040  (对比例)
  H300XD Z100,  1mm   43   36   33   15
  H400TD Z100,  1mm   42   34   31   14
  RAGAL600DP  Z100,1mm   31   29   21   8
  DOCOL 1000DP  ZE 75/75,  0.9mm   33   21   22   6
H300XD Z100、H400TD Z100、RAGAL600DP Z100、DOCOL1000DP ZE75/75是本领域技术人员所公知的高强度钢。如表2所示,本发明的环氧粘合剂组合物与已知的结构型粘合剂组合物相比,在高强度钢上显示出显著更高的冲击剥离强度。 
表3在高强度钢上的搭接剪切强度:以MPa为单位,室温 
  钢类型   BM 1496C 32  (根据本发明)   BM 1480  (对比例)   BM 1496V  (对比例)   BM 1040(对  比例)
  H300XD Z100,  1mm   32   33   34   39
  H400TD Z100,  1mm   31   38   37   37
  RAGAL600DP  Z100,1mm   34   35   35   35
  DOCOL 1000DP  ZE 75/75,  0.9mm   33   37   38   37
表3显示本发明的环氧粘合剂组合物保留了已知的结构型粘合剂组合物的搭接剪切强度值。 

Claims (14)

1.一种环氧粘合剂组合物,其含有:
a)第一种环氧树脂,其包括一种或多种双酚的聚缩水甘油醚、酚醛清漆的聚缩水甘油醚或双酚A与具有缩水甘油基的脂族二醇的加合物,
b)第二种环氧树脂,其用至少30重量%的丙烯腈-丁二烯橡胶改性,后者含有少于20重量%的丙烯腈,和
c)增韧剂,
组分b)和组分c)的总量为大于30%,以组合物的总重量计,组分c)对组分b)的重量比大于1.3∶1,并且固化的组合物在-40℃具有大于25N/mm的冲击剥离强度。
2.根据权利要求1所述的组合物,其含有作为组分c)的具有通式I的化合物
Figure FSB00000041523000011
其中m为1或2,n为2到6,R1为弹性预聚物在除去终端的异氰酸酯、氨基或羟基基团后的n-价的基团,弹性预聚物在环氧树脂中可以溶解或分散,W和X独立地为-O-或-NR3-,W和X中的至少一个为-NR3-,R2为聚酚或氨基苯酚在除去酚式羟基基团和任选的氨基基团后的m+1价的基团,R3为氢、C1到C6烷基或酚。
3.根据权利要求1所述的组合物,其含有作为组分c)的具有通式II的化合物
Figure FSB00000041523000012
其中p为1或2,q为2到6,Y为-O-、-S-或-NR6-,Z为选自-OH、-NHR6、-OCN、
Figure FSB00000041523000021
的基团,R4为羟基-、巯基-或氨基-终端的聚醚预聚物的残基或为羟基-、巯基-或氨基-终端的预聚、嵌段聚酯、聚硫酯或聚酰胺的残基,R5为碳环芳族或芳脂族的p+1价的基团,基团Z直接键连到芳环上,R6为氢、C1到C6烷基或苯基,R7为甲基或氢。
4.根据上述权利要求任一项所述的组合物,组分b)含有至少40重量%的丙烯腈-丁二烯橡胶。
5.根据权利要求1所述的组合物,组分b)含有三种不同的丙烯腈-丁二烯橡胶的混合物:
b1)含有10重量%的丙烯腈,
b2)含有17重量%的丙烯腈,和
b3)含有26重量%的丙烯腈。
6.根据权利要求1所述的组合物,其含有量为14到20%的组分b)和量为18到28%的组分c),以组合物的总重量计。
7.根据权利要求1所述的组合物,组分b)的丙烯腈-丁二烯橡胶含有少于15重量%的丙烯腈。
8.根据权利要求1所述的组合物,其含有总量为至少35重量%的组分b)和组分c)。
9.根据权利要求1所述的组合物,其中组分c)对组分b)的重量比大于1.5∶1。
10.根据权利要求1所述的组合物,组分a)为至少两种不同的环氧树脂的混合物。
11.根据权利要求1到10任一项所述的组合物,组分a)含有至少一种室温时为液体的环氧树脂。
12.根据权利要求1到10任一项所述的组合物,其中该组合物进一步包含氮碱和酚类聚合物的固体溶液,所述氮碱具有高于130℃的沸点和所述酚类聚合物是具有不饱和取代基的酚的加成聚合物,所述固体溶液用作促进剂。
13.根据权利要求1到10任一项所述的环氧粘合剂组合物在用于组装交通工具的部件中的用途。
14.一种交通工具,其部件用权利要求1-10任一项所述的环氧粘合剂组合物组装。
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EP1574537B2 (en) 2014-12-24
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WO2005095484A1 (en) 2005-10-13
DE602004004501T2 (de) 2007-11-15
EP1574537B1 (en) 2007-01-24
US7910656B2 (en) 2011-03-22
ES2276182T5 (es) 2015-04-10
KR20070021152A (ko) 2007-02-22
CN1930206A (zh) 2007-03-14
CA2553251A1 (en) 2005-10-13
JP2007528923A (ja) 2007-10-18
JP5102018B2 (ja) 2012-12-19
DE602004004501D1 (de) 2007-03-15
BRPI0506523A (pt) 2007-02-27
US20050209401A1 (en) 2005-09-22
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BRPI0506523B1 (pt) 2021-10-13
ES2276182T3 (es) 2007-06-16

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