CN110819047B - 丙烯酸溶胶组合物 - Google Patents
丙烯酸溶胶组合物 Download PDFInfo
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- CN110819047B CN110819047B CN201910649270.8A CN201910649270A CN110819047B CN 110819047 B CN110819047 B CN 110819047B CN 201910649270 A CN201910649270 A CN 201910649270A CN 110819047 B CN110819047 B CN 110819047B
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- resin
- acrylic
- diisocyanate
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000012948 isocyanate Substances 0.000 claims abstract description 36
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 30
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 25
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- 239000003795 chemical substances by application Substances 0.000 claims description 12
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- 239000003505 polymerization initiator Substances 0.000 claims description 8
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明的目的在于提供能够减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的密封材料的物性下降、并且可抑制氧障碍的丙烯酸溶胶组合物。本发明的丙烯酸溶胶组合物含有丙烯酸类树脂、紫外线固化树脂、封端异氰酸酯树脂、及填充剂,其中,相对于上述丙烯酸类树脂100重量份,含有上述紫外线固化树脂80~150重量份、作为上述封端异氰酸酯树脂的胺类封端异氰酸酯树脂50~110重量份、作为上述填充剂的二氧化硅100~180重量份。
Description
技术领域
本发明涉及可被用作密封材料的丙烯酸溶胶组合物。更具体而言,涉及可被用作在通过紫外线照射而固化后进行热固化的密封材料的丙烯酸溶胶组合物。
背景技术
在将密封材料用于汽车的钢板接合部的情况下,要求能够不依赖于线路烧焊工序的条件而使用、可抑制空气膨胀等的密封材料。为此,以往已提出了能够通过基于紫外线照射的紫外线固化树脂的固化而使材料固定化的紫外线固化型密封材料(例如,参见专利文献1)。专利文献1的技术中,为了使紫外线固化型密封材料的透光率提高、即使是1~3mm的厚度也能够使紫外线照射至深部,作为填充剂而使用了二氧化硅。
现有技术文献
专利文献
专利文献1:日本特开2010-84105
发明内容
发明要解决的问题
上述紫外线固化型密封材料在基于紫外线照射的紫外线固化树脂的固化后进行烧焊工序。就以往的紫外线固化型密封材料而言,只要从紫外线固化开始到加热为止不会花费时间,则可以抑制住空气膨胀。然而,如果在高温高湿度气体氛围中从紫外线固化开始经过长时间,则会导致水分进入密封材料、由于作为填充剂使用的二氧化硅的凝聚而引起紫外线固化时的密封材料的物性下降。其结果,密封材料无法耐受加热时的空气膨胀而发生外观不良。
另外,紫外线固化树脂会通过光自由基聚合而发生交联,但如果长期放置则存在由于空气中的氧而引发氧障碍、交联密度降低而容易受到水分的影响的问题。
本发明正是考虑到这样的情况而完成的,目的在于提供能够减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的密封材料的物性下降、并且可抑制氧障碍的丙烯酸溶胶组合物。
解决问题的方法
本发明人为了解决上述课题而进行了深入研究,结果发现,通过使含有丙烯酸类树脂、紫外线固化树脂、封端异氰酸酯树脂、及作为填充剂的二氧化硅的丙烯酸溶胶组合物中,含有特定量的胺类封端异氰酸酯树脂作为上述封端异氰酸酯树脂,可得到能够减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的密封材料的物性下降、并且可抑制氧障碍的丙烯酸溶胶组合物。
本发明的丙烯酸溶胶组合物基于上述见解而完成,(1)其含有丙烯酸类树脂、紫外线固化树脂、封端异氰酸酯树脂、及填充剂,其中,相对于上述丙烯酸类树脂100重量份,含有上述紫外线固化树脂80~150重量份、作为上述封端异氰酸酯树脂的胺类封端异氰酸酯树脂50~110重量份、作为上述填充剂的二氧化硅100~180重量份。
(2)另外,在上述(1)所述的丙烯酸溶胶组合物中,作为上述填充剂,除了上述二氧化硅以外,还含有表面处理碳酸钙,且相对于上述丙烯酸类树脂100重量份,含有表面处理碳酸钙80~160重量份。
(3)另外,在上述(1)或(2)所述的丙烯酸溶胶组合物中,相对于上述丙烯酸类树脂100重量份,含有聚合引发剂1~10重量份、潜伏性固化剂10~80重量份。
本发明还提供一种丙烯酸溶胶组合物,其含有:丙烯酸类树脂、紫外线固化树脂、封端异氰酸酯树脂、及填充剂,其中,相对于所述丙烯酸类树脂100重量份,含有所述紫外线固化树脂80~150重量份、作为所述封端异氰酸酯树脂的胺类封端异氰酸酯树脂50~110重量份、作为所述填充剂的二氧化硅100~180重量份、潜伏性固化剂10~80重量份,作为所述紫外线固化树脂,使用脂肪族类氨基甲酸酯低聚物或芳香族类氨基甲酸酯低聚物,作为所述填充剂,除了所述二氧化硅以外,还含有表面处理碳酸钙。
发明的效果
对于本发明的丙烯酸溶胶组合物而言,能够减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的物性下降、并且可抑制氧障碍。
附图说明
图1是吸湿放置后膨胀性试验中使用的试验片的说明图。
附图标记说明
1 第1试验片
2 第2试验片
3 加入有玻璃珠的粘接剂
4 丙烯酸溶胶组合物
具体实施方式
对本发明的丙烯酸溶胶组合物的实施方式进行说明。
本实施方式中的丙烯酸溶胶组合物可以作为例如汽车的钢板接合部的密封材料、用于底盘、轮罩等车辆部分的底涂材料、用于储物柜面板、门下部、挡泥板等的抗破裂材料等使用。
本实施方式中的丙烯酸溶胶组合物被用作密封材料的情况下,通常以0.5~2.5mm左右的厚度使用(涂布)。为了使紫外线固化至密封材料的深部,需要提高透光性。因此,为了保持透光性,作为填充剂,可含有二氧化硅。
本实施方式的密封组合物含有丙烯酸类树脂、紫外线固化树脂、封端异氰酸酯树脂、及填充剂,其中,相对于上述丙烯酸类树脂100重量份,含有上述紫外线固化树脂80~150重量份、作为上述封端异氰酸酯树脂的胺类封端异氰酸酯树脂50~110重量份、作为上述填充剂的二氧化硅100~180重量份。
需要说明的是,本实施方式的密封组合物也可以根据需要而含有聚合引发剂、潜伏性固化剂。
作为上述丙烯酸类树脂,可使用例如:选自丙烯酸烷基酯、甲基丙烯酸烷基酯等中的单体的均聚物、共聚物等。作为单体,具体可使用:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸环己酯、丙烯酸苄酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯、甲基丙烯酸苄酯等。另外,作为共聚成分,可使用苯乙烯、α-甲基苯乙烯、甲基丙烯酸、丙烯酸、衣康酸、巴豆酸等。本类型是微粒形状,特别优选使用由核部及壳部构成的核-壳型。核部特别优选使用凝胶化迅速的甲基丙烯酸丁酯。
作为上述紫外线固化树脂,可以使用具有由异氰酸酯与多元醇反应而成的氨基甲酸酯结构、且分子末端具有丙烯酰基等自由基聚合性碳-碳双键的反应性氨基甲酸酯低聚物。
作为上述异氰酸酯,可以使用脂肪族类异氰酸酯或芳香族类异氰酸酯。
作为脂肪族类异氰酸酯,可使用:三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、2,4,4-或2,2,4-三甲基六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯。
作为芳香族类异氰酸酯,可使用:2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、3,3’-二甲基-4,4’-联苯二异氰酸酯、3,3’-二甲氧基-4,4’-联苯二异氰酸酯、3,3’-二氯-4,4’-联苯二异氰酸酯、1,5-萘二异氰酸酯、1,5-四氢萘二异氰酸酯、或上述的加合物、氰脲酸酯(nurate)体、缩二脲(biuret)体等。
此外,可使用异佛尔酮二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化苯二亚甲基二异氰酸酯、二聚酸二异氰酸酯等。
作为上述多元醇,在代表性的多元醇中,可使用聚醚多元醇、聚酯多元醇。作为聚醚多元醇,可使用例如:以乙二醇、二乙二醇、三乙二醇、丙二醇、三亚甲基二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、甘油、三羟甲基乙烷、三羟甲基丙烷、山梨糖醇、蔗糖、乌头糖、偏苯三酸、连苯三酸、磷酸、乙二胺、二亚乙基三胺、三异丙醇胺、连苯三酚、二羟基苯甲酸、羟基苯二甲酸、丙烷-1,2,3-三硫醇等至少具有2个活性氢原子的化合物的一种或两种以上为引发剂通过常规方法使环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯、表氯醇、四氢呋喃、环己烯等单体的一种或两种以上发生加成聚合而得到的那些、或以阳离子催化剂、质子酸、路易斯酸等为催化剂使上述单体发生开环聚合而得到的那些。
作为聚酯多元醇,可使用包括缩合聚酯多元醇、内酯类聚酯多元醇、聚碳酸酯二醇在内的聚酯多元醇等。
此外,在聚丁二烯类多元醇、聚烯烃类多元醇、聚醚多元醇中,可使用使单独的丙烯腈或丙烯腈与选自苯乙烯、丙烯酰胺、丙烯酸酯、甲基丙烯酸酯及乙酸乙烯酯中的至少一种的混合单体发生聚合或接枝聚合而成的聚合物多元醇等。
相对于丙烯酸类树脂100重量份,优选含有80~150重量份的紫外线固化树脂。这是由于,低于80重量份时,会导致紫外线固化变得不充分、发生膨胀,超过150重量份时,会导致粘度增高、涂布作业性变差。
作为上述聚合引发剂,可使用例如:苯偶姻类、烷基苯酮类(苯偶酰二甲缩酮、α-羟基烷基苯酮、α-氨基烷基苯酮等)、酰基氧化膦类(单酰基氧化膦、双酰基氧化膦等)、二茂钛类、肟酯类、羟基苯基乙酸酯类、二硫化四甲基秋兰姆等硫化合物等。
由于需要使紫外线固化进行至厚膜的深部,因此在聚合引发剂中,优选使用酰基氧化膦类化合物。另外,优选在酰基氧化膦类化合物中混合烷基苯酮类的α-羟基烷基苯酮类化合物。这是由于,能够谋求聚合效率的提高及表面固化的促进。另外,聚合引发剂也可以组合使用表面固化的促进与直到深部的固化的促进的双系统。
相对于丙烯酸类树脂100重量份,优选含有1~10重量份的聚合引发剂。这是由于,低于1重量份时,会导致紫外线固化变得不充分,超过10重量份时,会导致未反应物大量残留而引起涂膜性能降低。
作为上述潜伏性固化剂,可使用例如多胺类及改性物、芳香族胺类及改性物、酰肼类等。这些中,只要是在常温下是非活性的、而特别是会通过加温而活化并与异氰酸酯反应的固化剂则可以使用。
相对于丙烯酸类树脂100重量份,优选含有潜伏性固化剂10~80重量份、特别优选含有20~60重量份。这是由于,低于10重量份时,相对于被粘物的粘接性会变得不充分,超过80重量份时,会导致未反应物大量残留而引起涂膜性能降低。
就作为密合剂的胺类封端异氰酸酯树脂而言,优选使用含胺类封端异氰酸酯的氨基甲酸酯预聚物。含胺类封端异氰酸酯的氨基甲酸酯预聚物是使用胺类封端剂将使异氰酸酯、及聚醚多元醇、聚酯多元醇等多元醇反应而得到的聚氨酯的残存异氰酸酯进行封端而成的。
含封端异氰酸酯的氨基甲酸酯预聚物可以按照以下步骤制造。首先,使多元醇与过量的多异氰酸酯化合物反应而得到含末端NCO的氨基甲酸酯预聚物。
作为上述多元醇,在代表性的例子中可使用聚醚多元醇、聚酯多元醇。作为聚醚多元醇,可使用例如:以乙二醇、二乙二醇、三乙二醇、丙二醇、三亚甲基二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、甘油、三羟甲基乙烷、三羟甲基丙烷、山梨糖醇、蔗糖、乌头糖、偏苯三酸、连苯三酸、磷酸、乙二胺、二亚乙基三胺、三异丙醇胺、连苯三酚、二羟基苯甲酸、羟基苯二甲酸、丙烷-1,2,3-三硫醇等至少具有2个活性氢原子的化合物的一种或两种以上为引发剂通过常规方法使环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯、表氯醇、四氢呋喃、环己烯等单体的一种或两种以上发生加成聚合而得到的那些、或以阳离子催化剂、质子酸、路易斯酸等为催化剂使上述单体发生开环聚合而得到的那些。
作为聚酯多元醇,可使用包括缩合聚酯多元醇、内酯类聚酯多元醇、聚碳酸酯二醇的聚酯多元醇等。
此外,在聚丁二烯类多元醇、聚烯烃类多元醇、聚醚多元醇中,可使用使单独的丙烯腈或丙烯腈与选自苯乙烯、丙烯酰胺、丙烯酸酯、甲基丙烯酸酯及乙酸乙烯酯中的至少一种的混合单体发生聚合或接枝聚合而成的聚合物多元醇等。
作为上述多异氰酸酯化合物,可使用:三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、2,4,4-或2,2,4-三甲基六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯等脂肪族类异氰酸酯、1,3-环戊烷二异氰酸酯、1,6-己烷二异氰酸酯、1,4-环己烷二异氰酸酯、1,3-环己烷二异氰酸酯、4,4’-亚甲基双(环己基异氰酸酯)、甲基2,4-环己烷二异氰酸酯、甲基2,6-环己烷二异氰酸酯、1,4-双(异氰酸酯甲基)环己烷、1,3-双(异氰酸酯甲基)环己烷、间苯二异氰酸酯、对苯二异氰酸酯、4,4’-二苯基二异氰酸酯、1,5-萘二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、粗MDI、2,4-或2,6-甲苯二异氰酸酯、4,4’-甲苯胺二异氰酸酯、联茴香胺二异氰酸酯、4,4’-二苯基醚二异氰酸酯、1,3-或1,4-苯二亚甲基二异氰酸酯、ω,ω单位-二异氰酸酯-1,4-二乙基苯等芳香族类异氰酸酯等。此外,可使用异佛尔酮二异氰酸酯、氢化甲苯二异氰酸酯、氢化ジ苯基甲烷二异氰酸酯、氢化苯二亚甲基二异氰酸酯、二聚酸二异氰酸酯等。
接着,通过使含末端NCO的氨基甲酸酯预聚物与适当的胺类封端剂反应而将游离的NCO封端,从而得到目标的含胺类封端异氰酸酯的氨基甲酸酯预聚物。
作为上述胺类封端剂,可使用例如二环己胺等胺化合物。
相对于丙烯酸类树脂100重量份,优选含有胺类封端异氰酸酯树脂50~110重量份。这是由于,低于50重量份时,吸湿放置后会发生膨胀,超过110重量份时,会导致粘度上升、涂布作业性变差。
紫外线固化树脂在长期放置时,会由于空气中的氧而引发氧障碍、交联密度降低,此时,如果胺作为封端剂而结合,则胺会以碱性起作用,发挥出抑制紫外线固化树脂的氧障碍的效果。因此,紫外线固化树脂的交联密度得以保持,可保持紫外线固化时的物性。进一步,由于交联密度高,因此能够不易受到来自外部的水分的影响。
作为上述填充剂,二氧化硅是必要的,但除了二氧化硅以外,可使用例如碳酸钙、硫酸钡、粘土、硅藻土、滑石等无机填充剂。填充剂中除了二氧化硅以外,可以单独使用这些无机填充剂中的一种或组合使用两种以上。特别是,优选将透光性高的二氧化硅与表面处理碳酸钙组合使用。
在本实施方式中,填充剂是将二氧化硅与表面处理碳酸钙混合使用。这是由于,如果在高温高湿度气体氛围中长时间放置,则会由进入到密封材料中的水分而引起二氧化硅发生凝聚、导致紫外线固化时的密封材料的物性下降,而此时,通过将二氧化硅的一部分替换为表面处理碳酸钙,则可减少水分引起的二氧化硅的凝聚、减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的密封材料的物性下降。
相对于丙烯酸类树脂100重量份,优选含有二氧化硅100~180重量份。这是由于,低于100重量份时,会导致粘度降低,超过180重量份时,在吸湿放置后会发生膨胀。
相对于丙烯酸类树脂100重量份,优选含有表面处理碳酸钙80~160重量份。这是由于,低于80重量份时,吸湿放置后会发生膨胀,超过160重量份时,会导致紫外线的透过率下降、固化性降低。
实施例
以下,结合实施例对本发明的丙烯酸溶胶组合物进行更为具体的说明,但本发明在不超出其要点的范围内,并不受以下实施例的限定。
使用以下原料、按照表1及表2所示的配比制作了实施例1~10及比较例1~11的丙烯酸溶胶组合物。
[配合原料]
(1)丙烯酸类树脂:塑料溶胶用丙烯酸粉末(Mitsubishi Rayon(株)制DIANAL LP-3106)
(2)紫外线固化树脂
A:脂肪族类氨基甲酸酯低聚物(Sartomer公司制CN9002)
B:芳香族类氨基甲酸酯低聚物(Sartomer公司制CN978)
(3)聚合引发剂:双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(酰基氧化膦类)(BASF公司制IRGACURE819)
(4)潜伏性固化剂(粉体):多胺类((株)ADEKA制EH3731S)
(5)固化剂(液态):多胺类((株)ADEKA制QH7150)
(6)密合剂
x:含胺类封端异氰酸酯的氨基甲酸酯预聚物(Dow Chemical(株)制XMN3030)
y:含肟类封端异氰酸酯的氨基甲酸酯预聚物((株)ADEKA制QR9401-1)
z:聚酰胺(Cognis Japan(株)制Parsamide AP-10)
(7)填充剂:二氧化硅((株)Tokuyama制REOLOSIL)、表面处理碳酸钙(竹原化学工业(株)制Neolite SP)
(8)增塑剂:DINP((株)J-PLUS制)
[试验及评价方法]
对于上述实施例及比较例,在下述条件下进行了评价,并将其结果示于表1及表2。
(1)固化性:将各例以膜厚2mm涂布于100mm×100mm的钢板制试验片,经紫外线照射(照射条件:1000mJ/cm2)后,用手指按压并通过目测来确认其变形。
评价基准
○:手指上未附着丙烯酸溶胶组合物
×:手指上附着有丙烯酸溶胶组合物
(2)吸湿放置后膨胀性:在图1所示的100mm×50mm的钢板制第1试验片1上,将加入有粒径0.2mm玻璃珠的粘接剂3涂布成各留有5mm间隙地形成有5个连接而成的矩形的图案。接着,将丙烯酸溶胶组合物4以封堵上述间隙的方式以膜厚2mm涂布成直线状。在该第1试验片1上叠合100mm×30mm的钢板制第2试验片2。其后,经紫外线照射(照射条件:1000mJ/cm2)后,在30℃、80%RH的温湿度条件下放置了72小时。其后,于140℃进行30分钟烧焊,通过目测来确认有无膨胀。
评价基准
○:无膨胀
×:有膨胀
(3)缓慢升温钢板密合性:将各例以膜厚2mm、宽度10mm、长度100mm涂布于70mm×150mm的经过了电沉积涂覆的钢板制试验片,经紫外线照射(照射条件:1000mJ/cm2)后,花费24分钟升温至140℃,进一步进行了20分钟烧焊。其后,用指甲剥离而确认了与电沉积钢板的密合性。
评价基准
Cf:凝聚破坏
Af:界面破坏(包括仅一部分发生了界面破坏的情况)
(4)作业性:针对各例,于20℃以下使用SOD粘度计及2号毛细管进行了测定。
评价基准将15~25Pa·s视为合格
(5)稳定性:将各例分别准备500ml,测定了于35℃放置10日后的粘度变化。
评价基准将粘度变化率30%以下视为合格
(6)耐水涂料密合性:将各例以膜厚2mm、宽度50mm、长度100mm涂布于70mm×150mm的经过了电沉积涂覆的钢板制试验片,经紫外线照射(照射条件:1000mJ/cm2)后,涂布中间层涂料、表面层涂料及清漆罩面,于140℃进行了30分钟烧焊。其后,在40℃的恒温水槽中放置10日后,实施了棋盘格试验。
评价基准将0/100无剥离视为合格
(7)伸长率:将各例以涂膜2mm涂布于脱模纸上,经紫外线照射(照射条件:1000mJ/cm2)后,于140℃进行了60分钟烧焊。其后,以2号哑铃进行冲裁,并以拉伸速度50mm/min进行拉伸,计算出了断裂时的伸长率。
评价基准将伸长率150%以上视为合格
需要说明的是,上述(1)、(2)、(3)、(6)及(7)的紫外线照射中使用了Eye Graphics公司制“UVX-T3-405”,并将到对象为止的距离设为50mm。
将这样的实施例1~10及比较例1~11的评价结果示于表1及表2。
[表1]
[表2]
根据表1所示的实施例1~10的试验结果、和表2所示的比较例1~11的试验结果,在实施例的丙烯酸溶胶组合物的情况下,在(1)固化性、(2)吸湿放置后膨胀性、(3)缓慢升温钢板密合性、(4)作业性、(5)稳定性、(6)耐水涂料密合性、(7)伸长率的各项目中显示出了良好的试验结果,可以确认其能够减轻在高温高湿度气体氛围中长时间放置后由吸湿引起的物性下降、并且可抑制氧障碍。
Claims (3)
1.一种丙烯酸溶胶组合物,其含有:
丙烯酸类树脂、
紫外线固化树脂、
封端异氰酸酯树脂、及
填充剂,
其中,相对于所述丙烯酸类树脂100重量份,含有所述紫外线固化树脂80~150重量份、作为所述封端异氰酸酯树脂的胺类封端异氰酸酯树脂50~110重量份、作为所述填充剂的二氧化硅100~180重量份、潜伏性固化剂10~80重量份,
作为所述紫外线固化树脂,使用脂肪族类氨基甲酸酯低聚物或芳香族类氨基甲酸酯低聚物,
作为所述填充剂,除了所述二氧化硅以外,还含有表面处理碳酸钙。
2.根据权利要求1所述的丙烯酸溶胶组合物,其中,相对于所述丙烯酸类树脂100重量份,含有表面处理碳酸钙80~160重量份。
3.根据权利要求1或2所述的丙烯酸溶胶组合物,其中,相对于所述丙烯酸类树脂100重量份,含有聚合引发剂1~10重量份。
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US (1) | US20200048512A1 (zh) |
EP (1) | EP3608345B1 (zh) |
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JP7149245B2 (ja) | 2019-10-01 | 2022-10-06 | パーカーアサヒ株式会社 | 塩ビゾル系紫外線硬化型シーリング材 |
CN111690349A (zh) * | 2020-06-17 | 2020-09-22 | 成都市鑫晶密封材料科技有限公司 | 一种复合型密封胶及其制备方法和用途 |
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JP2004083665A (ja) * | 2002-08-23 | 2004-03-18 | Zeon Kasei Co Ltd | プラスチゾルおよび成形品 |
JP5279249B2 (ja) * | 2007-12-06 | 2013-09-04 | アイシン化工株式会社 | 熱可塑性樹脂ゾル組成物 |
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2018
- 2018-08-08 JP JP2018149354A patent/JP6811215B2/ja active Active
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2019
- 2019-07-18 CN CN201910649270.8A patent/CN110819047B/zh active Active
- 2019-07-19 EP EP19187312.4A patent/EP3608345B1/en active Active
- 2019-07-26 US US16/522,724 patent/US20200048512A1/en not_active Abandoned
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EP1137687A1 (de) * | 1998-10-12 | 2001-10-04 | BASF Coatings AG | Beschichtungsmittel, verfahren zu seiner herstellung und seine verwendung als decklack oder klarlack, insbesondere zur beschichtung von kunststoffen |
CN101250312A (zh) * | 2008-04-01 | 2008-08-27 | 长春依多科化工有限公司 | 一种发泡隔音型丙烯酸树脂车底保护塑溶胶及其制备方法 |
CN102304340A (zh) * | 2011-10-09 | 2012-01-04 | 北京天山新材料技术股份有限公司 | 双组份硅烷封端型密封粘接剂及其制备方法 |
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EP3608345B1 (en) | 2023-09-20 |
EP3608345A1 (en) | 2020-02-12 |
US20200048512A1 (en) | 2020-02-13 |
JP6811215B2 (ja) | 2021-01-13 |
JP2020023641A (ja) | 2020-02-13 |
CN110819047A (zh) | 2020-02-21 |
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