CN107428939A - 树脂组合物、粘接剂和密封剂 - Google Patents
树脂组合物、粘接剂和密封剂 Download PDFInfo
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- CN107428939A CN107428939A CN201680013356.6A CN201680013356A CN107428939A CN 107428939 A CN107428939 A CN 107428939A CN 201680013356 A CN201680013356 A CN 201680013356A CN 107428939 A CN107428939 A CN 107428939A
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Classifications
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Abstract
本发明提供光和热固化性的树脂组合物,能抑制固化后的树脂组合物在耐湿试验中的粘接强度的降低,且具有足够长的适用期。所述树脂组合物包含:(A)丙烯酸树脂;(B)用特定的化学式表示的、多官能的含氮杂环化合物;(C)潜在性固化剂;(D)自由基阻聚剂;以及(E)阴离子阻聚剂。优选树脂组合物还包含(F)具有缩水甘油基的丙烯酸树脂以外的化合物。
Description
技术领域
本发明涉及通过光和加热固化的树脂组合物。更具体地说,涉及通过光照射能够临时固定并能够通过加热正式固化的光和热固化性树脂组合物。
背景技术
通过紫外线(UV)照射临时固定并利用热量正式固化类型的粘接剂在很多领域中使用(例如专利文献1、2),特别是经常用于图像传感器模块用途。如果图像传感器的制造工序中变成高温,则由于图像传感器中使用的透镜等发生劣化,因此对于用于图像传感器的制造的粘接剂和密封材料,要求低温固化性。此外,从生产成本的方面出发,还同时要求短时间固化性。作为低温短时间固化型粘接剂,可以列举硫醇系粘接剂(例如专利文献3、4)。可是,对硫醇系粘接剂赋予UV固化性非常困难。因为具有UV固化性的丙烯酸树脂与硫醇树脂的固化反应,比丙烯酸树脂以外的树脂(例如环氧树脂)与硫醇树脂的固化反应更容易进行,所以适用期会缩短到实用上不能使用的水平。
本发明的发明人鉴于所述的问题,以提供具有足够长的适用期的光和加热固化性树脂组合物为目的,已开发了包含(A)丙烯酸树脂、(B)硫醇化合物、(C)潜在性固化剂、(D)自由基阻聚剂以及(E)阴离子阻聚剂的树脂组合物(专利文献5)。
现有技术文献
专利文献
专利文献1:日本专利公开公报特开2009-51954号
专利文献2:国际公开第2005/052021号
专利文献3:日本专利公开公报特开平6-211969号
专利文献4:日本专利公开公报特开平6-211970号
专利文献5:日本专利公报第4976575号
发明内容
本发明要解决的技术问题
可是本发明人发现了,所述的包含(A)丙烯酸树脂、(B)硫醇化合物、(C)潜在性固化剂、(D)自由基阻聚剂以及(E)阴离子阻聚剂的树脂组合物,在压力锅试验(PressureCooker Test:将固化后的树脂组合物保持在121℃、2个大气压、100%相对湿度的可靠性试验)等的耐湿试验中存在粘接强度降低的问题,不能用于高可靠性的用途。
本发明是鉴于所述的问题而做出的发明,本发明的目的是提供能抑制固化后的树脂组合物的耐湿试验中的粘接强度的降低并且具有足够长的适用期的光和热固化性树脂组合物。
解决技术问题的技术方案
本发明的发明人为解决所述的问题进行了专心研究,通过添加丙烯酸树脂、特定的多官能的含氮杂环化合物、潜在性固化剂、自由基阻聚剂和阴离子阻聚剂,得到了能抑制耐湿试验中的粘接强度的降低并且具有能担当实际使用水平的足够长的适用期的光和热固化性树脂组合物。
本发明涉及通过具有以下的构成而解决了所述问题的树脂组合物、粘接剂和密封剂。
〔1〕一种树脂组合物,其包含:
(A)丙烯酸树脂;
(B)用化学式(1)或化学式(2)表示的多官能的含氮杂环化合物;
[化学式1]
[化学式2]
(C)潜在性固化剂;
(D)自由基阻聚剂;以及
(E)阴离子阻聚剂。
〔2〕根据〔1〕所述的树脂组合物,其中,所述树脂组合物还包含(F)具有缩水甘油基的丙烯酸树脂以外的化合物。
〔3〕根据〔2〕所述的树脂组合物,其中,(F)成分是具有至少一个缩水甘油基的乙烯基化合物。
〔4〕根据〔2〕所述的树脂组合物,其中,(F)成分是具有至少一个缩水甘油基的聚丁二烯。
〔5〕根据〔1〕~〔4〕中任意一项所述的树脂组合物,其中,〔(B)成分的硫醇当量〕/〔(A)成分的丙烯酸当量〕为0.5~2.0。
〔6〕根据〔1〕~〔5〕中任意一项所述的树脂组合物,其中,相对于树脂组合物100质量份,(D)成分为0.0001~1.0质量份。
〔7〕根据〔1〕~〔6〕中任意一项所述的树脂组合物,其中,相对于(C)成分1质量份,(E)成分为0.001~1.0质量份。
〔8〕根据〔1〕~〔7〕中任意一项所述的树脂组合物,其中,(D)成分是从由N-亚硝基-N-苯基羟胺铝、三苯基膦、4-甲氧基苯酚和氢醌构成的组中选择的至少1种。
〔9〕根据〔1〕~〔8〕中任意一项所述的树脂组合物,其中,(E)成分是从由硼酸酯、铝螯合物和有机酸构成的组中选择的至少1种。
〔10〕一种粘接剂,其包含所述〔1〕~〔9〕中任意一项所述的树脂组合物。
〔11〕一种密封剂,其包含所述〔1〕~〔9〕中任意一项所述的树脂组合物。
发明效果
按照本发明〔1〕,能够提供能抑制固化后的树脂组合物的耐湿试验中的粘接强度的降低并且具有足够长的适用期的光和热固化性树脂组合物。
按照本发明〔10〕,能够得到由耐湿性优异的粘接剂制造的可靠性高的图像传感器模块等半导体元件。按照本发明〔11〕,利用耐湿性优异的密封剂,能够得到透镜等部件被密封的可靠性高的图像传感器模块等半导体元件。
具体实施方式
本发明的树脂组合物(以下称为树脂组合物)包含:(A)丙烯酸树脂;
(B)用化学式(1)或化学式(2)表示的多官能的含氮杂环化合物;
[化学式3]
[化学式4]
(C)潜在性固化剂;
(D)自由基阻聚剂;以及
(E)阴离子阻聚剂。
作为(A)成分的丙烯酸树脂,能够对固化后的树脂组合物赋予透明性和适当的硬度。所述(A)成分是丙烯酸酯单体和/或甲基丙烯酸酯单体、或者它们的低聚物。作为本发明能使用的丙烯酸酯单体和/或甲基丙烯酸酯单体、或者它们的低聚物,可以列举三(2-羟乙基)异氰脲酸酯的二丙烯酸酯和/或二甲基丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯和/或三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯和/或三甲基丙烯酸酯或者它们的低聚物、季戊四醇三丙烯酸酯和/或三甲基丙烯酸酯或者它们的低聚物、二季戊四醇的聚丙烯酸酯和/或聚甲基丙烯酸酯、三(丙烯酰氧基乙基)异氰脲酸酯、己内酯改性三(丙烯酰氧基乙基)异氰脲酸酯、己内酯改性三(甲基丙烯酰氧基乙基)异氰脲酸酯、烷基改性二季戊四醇的聚丙烯酸酯和/或聚甲基丙烯酸酯、己内酯改性二季戊四醇的聚丙烯酸酯和/或聚甲基丙烯酸酯等。作为(A)成分的市售品,可以列举ダイセル·オルネクス株式会社制的聚酯丙烯酸酯(品名:EBECRYL810)、东亚合成株式会社制的聚酯丙烯酸酯(品名:M7100)。(A)成分可以单独使用,也可以并用2种以上。
作为(B)成分的多官能的含氮杂环化合物,用化学式(1):
[化学式5]
或化学式(2):
[化学式6]
表示,在含氮杂环化合物的4个氮原子的各氮原子上,结合了作为官能基的(-CH2-CH2―SH)或(-CH2-CH2-CH2―SH)。在此,作为所述专利文献5中使用的硫醇化合物的季戊四醇四(3-巯基丙酸酯)、三羟甲基丙烷三(3-巯基丙酸酯)、二季戊四醇六(3-巯基丙酸酯)、季戊四醇四(3-巯基丁酸酯),都包含酯键,由于所述酯键容易加水分解,所以认为耐湿性差。与此相对,(B)成分不含酯键。作为(B)成分的市售品,可以列举四国化成工业制的硫醇甘脲衍生物。(B)成分可以单独使用,也可以并用2种。
所述(C)成分的潜在性固化剂是在室温下为不活性的状态并且通过加热活性化而作为固化促进剂发挥功能的化合物,例如可以列举常温下固体的咪唑化合物、胺化合物与环氧化合物的反应生成物(胺-环氧加成物系)等固体分散型胺加成物系潜在性固化促进剂、胺化合物与异氰酸酯化合物或尿素化合物的反应生成物(尿素型加成物系)等。
作为常温下固体的咪唑化合物,例如可以列举2-十七烷基咪唑、2-苯基-4,5-二羟基甲基咪唑、2-十一烷基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、2-苯基-4-苄基-5-羟基甲基咪唑、2,4-二氨基-6-(2-甲基咪唑基-(1))-乙基-S-三嗪、2,4-二氨基-6-(2′-甲基咪唑基-(1)′)-乙基-S-三嗪·异氰脲酸加成物、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-甲基咪唑-偏苯三酸酯、1-氰乙基-2-苯基咪唑-偏苯三酸酯、N-(2-甲基咪唑基-1-乙基)-尿素、N,N′-(2-甲基咪唑基-(1)-乙基)-己二酰二酰胺等,但是不限于这些物质。
作为用作固体分散型胺加成物系潜在性固化促进剂(胺-环氧加成物系)的制造原料的一种的环氧化合物,例如可以列举双酚A、双酚F、儿茶酚、间苯二酚等多元酚、或甘油和聚乙二醇这样的多元醇与环氧氯丙烷反应得到的聚缩水甘油醚;对羟基苯甲酸、β-羟基萘甲酸这样的羟基羧酸与环氧氯丙烷反应得到的缩水甘油醚酯;邻苯二甲酸、对苯二甲酸这样的多元羧酸与环氧氯丙烷反应得到的聚缩水甘油酯;4,4′-二氨基二苯基甲烷和间氨基苯酚等与环氧氯丙烷反应得到的缩水甘油胺化合物;以及环氧化酚醛树脂、环氧化甲酚酚醛树脂、环氧化聚烯烃等多官能性环氧化合物、以及丁基缩水甘油醚、苯基缩水甘油醚、甲基丙烯酸缩水甘油酯等单官能性环氧化合物等,但是不限于这些物质。
作为用作固体分散型胺加成物系潜在性固化促进剂的另一种制造原料的胺化合物,只要分子内具有1个以上能与环氧基加成反应的活性氢、且在分子内至少具有1个以上的从伯胺基、仲胺基和叔胺基中选择的官能基即可。这样的胺化合物如以下所示的例子,但是不限于这些物质。例如,可以列举二亚乙基三胺、三亚乙基四胺、正丙基胺、2-羟乙基氨基丙基胺、环己基胺、4,4′-二氨基-二环己基甲烷等脂肪族胺类;4,4′-二氨基二苯基甲烷、2-甲基苯胺等芳香族胺化合物;2-乙基-4-甲基咪唑、2-乙基-4-甲基咪唑啉、2,4-二甲基咪唑啉、哌啶、哌嗪等包含氮原子的杂环化合物等,但是不限于这些物质。
此外,其中,特别是分子内具有叔胺基的化合物,是能得到具有优异的固化促进能的潜在性固化促进剂的原料,作为这样的化合物的例子,例如可以列举二甲基氨基丙基胺、二乙基氨基丙基胺、二正丙基氨基丙基胺、二丁基氨基丙基胺、二甲基氨基乙基胺、二乙基氨基乙基胺、N-甲基哌嗪等胺化合物;2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑等咪唑化合物等分子内具有叔胺基的1级或2级胺类;2-二甲基氨基乙醇、1-甲基-2-二甲基氨基乙醇、1-苯氧基甲基-2-二甲基氨基乙醇、2-二乙基氨基乙醇、1-丁氧基甲基-2-二甲基氨基乙醇、1-(2-羟基-3-苯氧基丙基)-2-甲基咪唑、1-(2-羟基-3-苯氧基丙基)-2-乙基-4-甲基咪唑、1-(2-羟基-3-丁氧基丙基)-2-甲基咪唑、1-(2-羟基-3-丁氧基丙基)-2-乙基-4-甲基咪唑、1-(2-羟基-3-苯氧基丙基)-2-苯基咪唑啉、1-(2-羟基-3-丁氧基丙基)-2-甲基咪唑啉、2-(二甲基氨基甲基)苯酚、2,4,6-三(二甲基氨基甲基)苯酚、N-β-羟乙基吗啉、2-二甲基氨基乙烷硫醇、2-巯基吡啶、2-苯并咪唑、2-巯基苯并咪唑、2-巯基苯并噻唑、4-巯基吡啶、N,N-二甲基氨基苯甲酸、N,N-二甲基甘氨酸、烟碱酸、异烟碱酸、吡啶-2-羧酸、N,N-二甲基甘氨酰肼、N,N-二甲基丙酸酰肼、烟碱酸酰肼、异烟碱酸酰肼等分子内具有叔胺基的醇类、酚类、硫醇类、羧酸类和酰肼类等,但是不限于这些物质。
作为在固体分散型胺加成物系潜在性固化促进剂中用作另一种制造原料的异氰酸酯化合物,例如可以使用正丁基异氰酸酯、异丙基异氰酸酯、苯基异氰酸酯、苄基异氰酸酯等单官能异氰酸酯化合物;六亚甲基二异氰酸酯、甲苯二异氰酸酯、1,5-萘二异氰酸酯、二苯基甲烷-4,4′-二异氰酸酯、异佛尔酮二异氰酸酯、二甲苯二异氰酸酯、对苯二异氰酸酯、1,3,6-六亚甲基三异氰酸酯、二环庚烷三异氰酸酯等多官能异氰酸酯化合物;以及所述多官能异氰酸酯化合物与活性氢化合物的反应得到的包含末端异氰酸酯基的化合物等。作为这样的包含末端异氰酸酯基的化合物的示例,可以列举甲苯二异氰酸酯与三羟甲基丙烷的反应得到的具有末端异氰酸酯基的加成化合物、甲苯二异氰酸酯与季戊四醇的反应得到的具有末端异氰酸酯基的加成化合物等,但是不限于这些物质。
此外,作为尿素化合物,例如可以列举尿素、硫脲等,但是不限于这些物质。
能用于本发明的固体分散型潜在性固化促进剂,例如可以通过下述的方法容易地进行制备:按所述的(a)胺化合物与环氧化合物的2成分、(b)所述2成分与活性氢化合物的3成分、或(c)胺化合物与异氰酸酯化合物和/或尿素化合物的2成分或3成分的组合,取各成分并进行混合,在从室温至200℃的温度下反应后,冷却固化后粉碎,或者在甲基乙基酮、二恶烷、四氢呋喃等溶剂中反应,脱溶剂后,将固体成分粉碎。
作为所述的固体分散型潜在性固化促进剂的市售品的代表例,作为胺-环氧加成物系(胺加成物系),可以列举“アミキュアPN-23”(味の素ファインテクノ(株)商品名)、“アミキュアPN-40”(味の素ファインテクノ(株)商品名)、“アミキュアPN-50”(味の素ファインテクノ(株)商品名)、“ハードナーX-3661S”(エー·シー·アール(株)商品名)、“ハードナーX-3670S”(エー·シー·アール(株)商品名)、“ノバキュアHX-3742”(旭化成イーマテリアルズ(株)商品名)、“ノバキュアHX-3721”(旭化成イーマテリアルズ(株)商品名)、“FXR1121”(T&K TOKA(株)商品名)等,此外,作为尿素型加成物系,可以列举“フジキュアFXE-1000”(T&K TOKA(株)商品名)、“フジキュアFXR-1030”(T&K TOKA(株)商品名)等,但是不限于这些物质。(C)成分可以单独使用,也可以并用2种以上。
(D)成分的自由基阻聚剂,是为了提高树脂组合物保存时的稳定性而添加的物质,用于抑制不希望的自由基聚合反应的进行。(A)成分的丙烯酸树脂,有时以较小的概率从自身产生自由基,并将所述自由基作为基点进行不希望的自由基聚合反应。通过添加自由基阻聚剂,可以抑制这样的不希望的(A)成分的自由基聚合反应的进行。
(D)成分可以使用公知的物质,例如可以使用从由N-亚硝基-N-苯基羟胺铝、三苯基膦、4-甲氧基苯酚和氢醌构成的组中选择的至少1种。此外,还可以使用日本专利公开公报特开2010-117545号、日本专利公开公报特开2008-184514号等公开的公知的自由基阻聚剂。(D)成分可以单独使用,也可以并用2种以上。
作为(E)成分的阴离子阻聚剂,添加的目的是赋予树脂组合物保存时的稳定性、抑制不希望的(C)成分所含的氨基与(B)成分的反应。(C)成分可以包含的咪唑、叔胺具有氨基,所述氨基与(B)成分反应而开始聚合。尽管潜在性固化剂被设计为室温下难以发生氨基的反应,但是存在少许氨基在室温下与(B)成分反应的可能性。(E)成分具有在氨基与(B)成分反应前与所述氨基反应从而抑制不希望的氨基与(B)成分的反应的作用。
(E)成分可以使用公知的物质,例如可以使用从由硼酸酯、铝螯合物和有机酸构成的组中选择的至少1种。硼酸酯例如可以使用日本专利公开公报特开2011-026539号、日本专利公表公报再表2005/070991号公开的物质。铝螯合物例如可以使用日本专利公表公报再表2005/070991号公开的物质。有机酸例如可以使用日本专利公报4394281号公开的物质。作为(E)成分的市售品,可以列举硼酸三异丙酯、巴比妥酸等。(E)成分可以单独使用,也可以并用2种以上。
优选的是,树脂组合物的〔(B)成分的硫醇当量〕/〔(A)成分的丙烯酸当量〕为0.5~2.0;。(B)成分的硫醇当量是用(B)成分的分子量(化学式(1):382.6,化学式(2):438.7)除以1分子中的硫醇基的数量(4)得到的数(化学式(1):95.7,化学式(2):109.7)。丙烯酸树脂的当量与用丙烯酸树脂的分子量除以1分子中的丙烯酸基(或甲基丙烯酸基)的数量所得到的数相等。因此,〔(B)成分的硫醇当量〕/〔(A)成分的丙烯酸当量〕为0.5~2.0是指:〔(化学式(1)的95.7或化学式(2)的109.7)/(A)成分的丙烯酸当量〕为0.5~2.0,(A)成分的丙烯酸当量为188~250。通过将〔(B)成分的硫醇当量〕/〔(A)成分的丙烯酸当量〕设定在0.5~2.0的范围,丙烯酸和硫醇的规定量以上进行反应并成为坚固的固化物,因此能实现高粘接强度。
从树脂组合物的粘度的观点出发,优选的是,相对于树脂组合物100质量份,(A)成分为10~90质量份。
从树脂组合物的固化速度、适用期的观点出发,优选的是,相对于树脂组合物100质量份,(C)成分为0.1~40质量份。
优选的是,相对于树脂组合物100质量份,(D)成分为0.0001~1.0质量份,这样能够进一步提高树脂组合物的保存时的稳定性、进一步延长树脂组合物的适用期。
优选的是,相对于(C)成分1质量份,(E)成分为0.0001~1.0质量份,这样能进一步提高树脂组合物的保存时的稳定性、进一步延长树脂组合物的适用期。
优选的是,本发明的树脂组合物还包含(F)具有缩水甘油基的丙烯酸树脂以外的化合物。由于(F)成分通过加热基本不和(B)成分反应,所以和作为(E)成分的阴离子阻聚剂同样,能提高树脂组合物的保存时的稳定性。
从与(B)成分的反应性的观点出发,作为(F)成分,优选的是至少具有一个缩水甘油基的乙烯基化合物,至少具有一个缩水甘油基的聚丁二烯。作为至少具有一个缩水甘油基的聚丁二烯的市售品,可以列举ADEKA制的环氧化1,2-聚丁二烯。(F)成分可以单独使用,也可以并用2种以上。
从树脂组合物的适用期、UV固化性的观点出发,优选的是,相对于树脂组合物100质量份,(F)成分为1~50质量份。
优选的是,树脂组合物还包含作为(G)成分的自由基聚合引发剂。通过使树脂组合物包含(G)成分,能通过短时间的UV照射使树脂组合物固化。作为可以使用的自由基聚合引发剂,没有特别的限定,可以使用公知的物质。作为自由基聚合引发剂的具体例子,例如可以列举1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基丙烷-1-酮、二乙氧基苯乙酮、1-(4-异丙基苯基)-2-羟基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羟基-2-甲基丙烷-1-酮、4-(2-羟基乙氧基)-苯基(2-羟基-2-丙基)酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉丙烷-1、苯偶姻、安息香甲醚、安息香乙醚、安息香异丙醚、安息香正丁基醚、安息香苯基醚、安息香二甲基缩酮、二苯甲酮、苯甲酰基苯甲酸、苯甲酰基苯甲酸甲酯、4-苯基二苯甲酮、羟基二苯甲酮、丙烯酸化二苯甲酮、4-苯甲酰基-4’-甲基二苯硫醚、3,3’-二甲基-4-甲氧基二苯甲酮、噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、异丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮、2,4,6-三甲基苯甲酰基二苯基氧化膦、甲基苯基乙醛酸、苯偶酰、樟脑醌等。(G)成分可以单独使用,也可以并用2种以上。
在不损害本发明的目的的范围内,可以进一步根据需要,在树脂组合物中配合环氧树脂、碳黑、黑色氧化钛、二氧化硅填料、氧化铝填料、硅烷偶联剂、离子捕捉剂、均化剂、抗氧化剂、消泡剂、触变剂和其他的添加剂等。此外,在树脂组合物中还可以配合粘度调整剂、阻燃剂或溶剂等。在此,碳黑和黑色氧化钛可以用做遮光性赋予材料,从遮光性和UV固化性(固化深度)两立的观点出发,优选的是使用黑色氧化钛。作为黑色氧化钛,可以列举黑色氧化钛12S(三菱マテリアル电子化成株式会社制)、黑色氧化钛13M(三菱マテリアル株式会社制)、黑色氧化钛13M-C(三菱マテリアル株式会社制)、Tilack D(赤穂化成株式会社制)等,特别优选的是黑色氧化钛13M。
例如可以通过对(A)成分~(E)成分及其他添加剂等同时或分别边根据需要实施加热处理边进行搅拌、熔融、混合、分散来得到树脂组合物。作为所述的混合、搅拌、分散等的装置,没有特别的限定,可以使用具备搅拌、加热装置的擂溃机、亨舍尔混合机、三辊磨机、球磨机、行星式搅拌器、珠磨机等。此外,可以适当组合使用所述的装置。
这样得到的树脂组合物是光固化性和热固化性的树脂组合物。树脂组合物的热固化在用于图像传感器模块时,优选的是70~80℃。
本发明的树脂组合物,例如可以用作用于使部件同士接合的粘接剂或其原料。此外,所述树脂组合物例如可以用作电子零部件的密封剂或其原料。
实施例
以下,通过实施例来说明本发明,但是本发明不限于此。另外,在以下的实施例中,只要没有特别说明,份、%分别表示质量份、质量%。[实施例1~12,比较例1~6]
按照表1、2所示的配比,使用三辊磨机制备了树脂组合物。
<粘度,增粘率>
将制备后1小时以内的树脂组合物用E型粘度计(转子名称:3°×R9.7)测定了10rpm的值,测定了初期粘度。测定初期粘度后,在25℃/50%RH环境下放置24小时,再次测定粘度,计算出增粘率。在此,按照下述计算式计算出粘度增加率:
增粘率=〔(24小时后的粘度)-(初期粘度)〕/(初期粘度)×100
粘度优选的是0.1~100Pa,增粘率优选的是1.0~1.2。测定结果表示在表1~表2中。
<粘接强度>
将树脂组合物按的大小、125μm的厚度丝网印刷在玻璃板上,在印刷后的树脂组合物上放置3.2mm×1.6mm×0.45mm厚的氧化铝芯片,通过使承受有负荷的树脂组合物固化,制作出试验片(n=10)。此时的固化条件,在“仅为UV”的情况下,从氧化铝芯片放置面(表面)的反面(背面)以UV照射量2000mJ/cm2(UV波长:365nm,LED灯)进行照射;在“仅为加热”的情况下,在送风干燥机中加热80℃/60分钟;在“UV+加热”的情况下,在从氧化铝芯片放置面(表面)的反面(背面)以UV照射量2000mJ/cm2(UV波长:365nm,LED灯)照射后,在鼓风干燥机中加热80℃/60分钟。用アイコーエンジニアリング株式会社制的MODEL-1605HTP型强度试验机从侧面顶撞所述玻璃板上的氧化铝芯片,根据氧化铝芯片剥落时的数值计算出剪切强度。剪切强度优选的是3Kgf/Chip以上,更优选的是5Kgf/Chip以上。表1、表2中表示了测定结果(单位Kgf/Chip)。接着,针对实施例1~12、比较例2、4、6,对“UV+热固化”处理后的试验片进行压力锅试验(Pressure Cooker Test;以下称为PCT)(2atm,121℃,100%RH,1小时)后,同样计算出剪切强度。结果表示在表1、表2中(单位Kgf/Chip)。
[表1]
1)ダイセル·オルネクス制丙烯酸树脂(品名:EBECRYL810,丙烯酸当量:250g/eq)
2)东亚合成制丙烯酸树脂(品名:M7100,丙烯酸当量:188g/eq)
3)四国化成工业制甘脲衍生物(品名:TS-G(C2),硫醇当量:95.7g/eq)
4)四国化成工业制甘脲衍生物(品名:TS-G(C3),硫醇当量:109.7g/eq)
5)SC有机化学制季戊四醇四(3-巯基丙酸酯)(品名:PEMP,硫醇当量:122g/eq)
6)味の素ファインテクノ制潜在性固化剂(品名:PN-50)
7)T&K TOKA制潜在性固化剂(品名:FXR1121)
8)和光纯药制N-亚硝基-N-苯基羟胺铝
9)东京化成工业制三苯基膦
10)东京化成工业制硼酸三异丙酯
11)味の素ファインテクノ制铝螯合物(品名:AL-A)
12)东京化成工业制巴比妥酸
13)ADEKA制的具有缩水甘油基的聚丁二烯(品名:BF-1000)
14)四国化成工业制的具有缩水甘油基的乙烯基化合物(品名:DA-MGIC)
[表2]
从表1、2判明了:实施例1~12的所有的增粘率都在适当范围内,在各条件下测定的粘接强度也都高。与此相对,不含(E)成分的比较例1,在制作树脂组合物时发生了凝胶化。不含(D)成分的比较例2的增粘率差。不含(C)成分的比较例3,仅为加热时未固化。不含(B)成分的比较例4,在仅为UV或仅为加热时都未固化,PCT后的粘接强度显著降低。不含(A)成分的比较例5,在仅为UV或仅为加热时都未固化。替代(B)成分使用了硫醇化合物的比较例6,PCT后的粘接强度显著降低。
工业实用性
本发明是能够抑制固化后的树脂组合物在耐湿试验中的粘接强度的降低并且具有足够长的适用期的光和热固化性的树脂组合物,特别是作为粘接剂、密封剂,非常有用。
Claims (11)
1.一种树脂组合物,其特征在于,所述树脂组合物包含:
(A)丙烯酸树脂;
(B)用化学式(1)或化学式(2)表示的多官能的含氮杂环化合物;
(C)潜在性固化剂;
(D)自由基阻聚剂;以及
(E)阴离子阻聚剂。
2.根据权利要求1所述的树脂组合物,其特征在于,所述树脂组合物还包含(F)具有缩水甘油基的丙烯酸树脂以外的化合物。
3.根据权利要求2所述的树脂组合物,其特征在于,(F)成分是具有至少一个缩水甘油基的乙烯基化合物。
4.根据权利要求2所述的树脂组合物,其特征在于,(F)成分是具有至少一个缩水甘油基的聚丁二烯。
5.根据权利要求1~4中任意一项所述的树脂组合物,其特征在于,〔(B)成分的硫醇当量〕/〔(A)成分的丙烯酸当量〕为0.5~2.0。
6.根据权利要求1~5中任意一项所述的树脂组合物,其特征在于,相对于树脂组合物100质量份,(D)成分为0.0001~1.0质量份。
7.根据权利要求1~6中任意一项所述的树脂组合物,其特征在于,相对于(C)成分1质量份,(E)成分为0.001~1.0质量份。
8.根据权利要求1~7中任意一项所述的树脂组合物,其特征在于,(D)成分是从由N-亚硝基-N-苯基羟胺铝、三苯基膦、4-甲氧基苯酚和氢醌构成的组中选择的至少1种。
9.根据权利要求1~8中任意一项所述的树脂组合物,其特征在于,(E)成分是从由硼酸酯、铝螯合物和有机酸构成的组中选择的至少1种。
10.一种粘接剂,其特征在于,所述粘接剂包含权利要求1~9中任意一项所述的树脂组合物。
11.一种密封剂,其特征在于,所述密封剂包含权利要求1~9中任意一项所述的树脂组合物。
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| TW201641576A (zh) | 2016-12-01 |
| CN107428939B (zh) | 2019-11-22 |
| KR20170128268A (ko) | 2017-11-22 |
| US10221282B2 (en) | 2019-03-05 |
| PH12017501623A1 (en) | 2018-02-12 |
| PH12017501623B1 (en) | 2018-02-12 |
| KR102451905B1 (ko) | 2022-10-06 |
| US20180044478A1 (en) | 2018-02-15 |
| WO2016143777A1 (ja) | 2016-09-15 |
| JP6675380B2 (ja) | 2020-04-01 |
| SG11201707283SA (en) | 2017-10-30 |
| TWI672335B (zh) | 2019-09-21 |
| JPWO2016143777A1 (ja) | 2017-12-21 |
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