TW201905136A - 丙烯酸樹脂組成物、黏著劑組成物、黏著片用基材及黏著片 - Google Patents
丙烯酸樹脂組成物、黏著劑組成物、黏著片用基材及黏著片Info
- Publication number
- TW201905136A TW201905136A TW107121437A TW107121437A TW201905136A TW 201905136 A TW201905136 A TW 201905136A TW 107121437 A TW107121437 A TW 107121437A TW 107121437 A TW107121437 A TW 107121437A TW 201905136 A TW201905136 A TW 201905136A
- Authority
- TW
- Taiwan
- Prior art keywords
- meth
- resin composition
- acrylic resin
- mass
- polymer
- Prior art date
Links
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Abstract
本發明提供一種具有高耐化性及高耐油性之丙烯酸樹脂組成物。其包含含有來自預定的單體的單元之聚合物,相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述預定的單體的單元之比例為40~99質量%,且將前述丙烯酸樹脂組成物浸漬於油酸24小時後的抗拉強度,為浸漬於油酸前的抗拉強度之值之50%以上。
Description
本發明係關於丙烯酸樹脂組成物、黏著劑組成物、黏著片用基材及黏著片。
丙烯酸樹脂在耐候性、耐久性、高透明性方面優異,又有非常多單體種類存在,因而使用於多種多樣的用途。其中尤以(甲基)丙烯酸烷酯作為同元聚合物時之玻璃轉移溫度(Tg)低,橡膠彈性優異,且聚合物自身展現黏性,因此多使用於丙烯酸橡膠、黏接劑、黏著劑領域中。(甲基)丙烯酸烷酯的聚合物多藉由溶液聚合法來製造。由此亦可知,該聚合物的溶解度參數與甲苯、乙酸乙酯、甲乙酮等一般的工業用有機溶劑相近,易溶解於這些有機溶劑。
近年,以智慧型手機、平板電腦為代表之行動設備急遽地普及。這些行動設備的顯示面板與機殼多藉由丙烯酸系的黏接劑、兩面黏著膠帶來黏接。又,該行動設備搭載有觸控面板,會以人的手指觸控而操作,或撥打電話時會接觸到人臉。若觸控面板接觸到人的手、臉,則皮脂、指脂等油性成分會附著到觸控面板上。該油性成分含有油酸等成分,該成分的SP值與工業用有機溶劑相近,會溶解一般的丙烯酸樹脂。若為工業用有機溶劑,因沸點低所以會於短時間內汽化,並不會給予黏接劑、黏著劑大的損傷,但油酸等的油成分沸點高,在生活環境中不會汽化而會殘留在電子設備內,因而給予黏接劑、黏著劑損傷。因此,使構件發生翻翹、剝離,使電子設備壽命減短。
又,建材、汽車、家電、大型電子設備等工業領域中使用的結構黏接用之兩面黏著膠帶,多使用柔軟性及應力追隨性優異的丙烯酸發泡體作為基材。然而,以建材而言,若清掃地板所需的洗劑、蠟等化學藥品附著到建材上,具有丙烯酸發泡體基材的兩面黏著膠帶會受損。以汽車的外裝零件等而言,有時會有被洗車時的洗劑、蠟、加油時的汽油等附著的情況,這些也會溶解一般的丙烯酸樹脂或使其膨潤。以家電而言,洗衣機的情況有時會有被衣物用洗劑、柔軟劑附著,若為微波爐、冰箱則會有被食用油附著的情況,又會因以人手接觸、操作而沾上指脂。如此,具有以一般的丙烯酸樹脂構成之丙烯酸發泡體基材的兩面黏著膠帶,會因化學藥品及油成分而受損,製品發生問題或壽命減短。
例如專利文獻1中,記載了藉由對於以特定的比例含有特定的丙烯酸多元醇樹脂、多官能光硬化性化合物及聚異氰酸酯化合物之光硬化性塗料組成物,進行丙烯酸多元醇樹脂與聚異氰酸酯化合物之胺甲酸乙酯鍵形成反應、以及多官能光硬化性化合物之藉由光聚合引發劑之自由基聚合反應之2種硬化反應,可得到耐化性高的塗料。又,專利文獻2及3中,記載了含有主要由丙烯酸正丁酯之單元構成的丙烯酸樹脂之樹脂組成物,對於油酸、人工皮脂液有耐受性。又,專利文獻4中,記載了含有主要由具有碳數1~6的烷基之(甲基)丙烯酸烷酯之單元構成的丙烯酸樹脂之黏著劑組成物,對於皮脂、化妝品有耐受性。
[先前技術文獻] [專利文獻]
[專利文獻1] 日本特開2016-37609號公報 [專利文獻2] 日本特開2009-215355號公報 [專利文獻3] 日本特開2013-100485號公報 [專利文獻4] 日本特開2017-57371號公報
[發明所欲解決之課題]
然而,就專利文獻1~4中記載的技術而言,耐化性及耐油性不充分,希望能有更進一步的改良。
本發明之目的在於提供一種具有高耐化性及高耐油性之丙烯酸樹脂組成物。又,目的在於提供由該丙烯酸樹脂組成物構成之黏著劑組成物、含有該丙烯酸樹脂組成物之黏著片用基材及黏著片。 [解決課題之手段]
本發明之丙烯酸樹脂組成物,
包含含有來自下式(1)表示之單體的單元之聚合物, 相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自下式(1)表示之單體的單元之比例為40~99質量%, 且將前述丙烯酸樹脂組成物浸漬於油酸24小時後的抗拉強度,為浸漬於油酸前的抗拉強度之值之50%以上; 下式(1)中,R1
表示氫原子或甲基,R2
表示碳數2~4的伸烷基,R3
表示碳數1~10的烷基,n表示1~20的整數。
[化1]
本發明之黏著劑組成物係由本發明之丙烯酸樹脂組成物構成。
本發明之黏著片用基材含有本發明之丙烯酸樹脂組成物。
本發明之黏著片含有本發明之黏著劑組成物,及/或含有本發明之黏著片用基材。 [發明之效果]
依據本發明,可提供具有高耐化性及高耐油性之丙烯酸樹脂組成物。又,可提供由該丙烯酸樹脂組成物構成之黏著劑組成物、含有該丙烯酸樹脂組成物之黏著片用基材及黏著片。
[丙烯酸樹脂組成物] 本發明之丙烯酸樹脂組成物,包含含有來自前述式(1)表示之單體的單元之聚合物。在此,相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述式(1)表示之單體的單元之比例為40~99質量%。又,將前述丙烯酸樹脂組成物浸漬於油酸24小時後的抗拉強度,為浸漬於油酸前的抗拉強度之值之50%以上。
本案發明者們,發現藉由使丙烯酸樹脂組成物含有之聚合物主要含有來自前述式(1)表示之單體的單元,可得到具有高耐化性及高耐油性的丙烯酸樹脂組成物。具體而言,藉由相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述式(1)表示之單體的單元之比例為40~99質量%,可使將丙烯酸樹脂組成物已浸漬於油酸24小時的情況下,該抗拉強度仍維持浸漬於油酸前的抗拉強度之值之50%以上。藉由丙烯酸樹脂組成物中含有之聚合物(丙烯酸樹脂)主要含有來自前述式(1)表示之單體的單元,丙烯酸樹脂之極性增高,該丙烯酸樹脂之溶解度係數,與化學藥品、油成分等之溶解度係數之間的差距增大。因此,推測丙烯酸樹脂組成物的耐化性及耐油性提升。
以下,針對本發明之丙烯酸樹脂組成物的實施形態進行說明。又,「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸。又,本發明之丙烯酸樹脂組成物,宜含有含來自前述式(1)表示之單體的單元之聚合物70質量%以上,又以含有80質量%以上更佳。
(式(1)表示的單體) 前述式(1)中,R1
表示氫原子或甲基。R2
表示碳數2~4的伸烷基,宜為碳數2或3的伸烷基,又以伸乙基更佳。R3
表示碳數1~10的烷基,宜為碳數1~5的烷基,又以碳數1~3的烷基更佳。n表示1~20的整數,宜為1~15的整數,又以1~10的整數更佳。
作為前述式(1)表示的單體之具體例,可列舉(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸甲氧基丁酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸乙氧基丙酯、(甲基)丙烯酸乙氧基丁酯等(甲基)丙烯酸烷氧基烷酯;(甲基)丙烯酸甲氧基二乙二酯、(甲基)丙烯酸甲氧基三乙二酯等(甲基)丙烯酸甲氧基(聚)乙二酯、(甲基)丙烯酸乙氧基二乙二酯、(甲基)丙烯酸乙氧基三乙二酯等(甲基)丙烯酸乙氧基(聚)乙二酯、(甲基)丙烯酸甲氧基二丙二酯、(甲基)丙烯酸甲氧基三丙二酯等(甲基)丙烯酸甲氧基(聚)丙二酯、(甲基)丙烯酸乙氧基二丙二酯、(甲基)丙烯酸乙氧基三丙二酯等(甲基)丙烯酸乙氧基(聚)丙二酯等(甲基)丙烯酸聚氧伸烷基二醇單烷基醚酯等。這些之中,考量耐化性及耐油性更優異的觀點,又宜為(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基(聚)乙二酯、(甲基)丙烯酸乙氧基(聚)乙二酯,又以(甲基)丙烯酸甲氧基乙酯更佳。尤其,丙烯酸2-甲氧基乙酯,其同元聚合物之Tg為-50℃之低,與常利用於丙烯酸系黏著劑成分的單體相近,因此作為黏著劑、黏接劑的成分係有用。這些單體可使用一種,亦可將兩種以上併用。
相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述式(1)表示之單體的單元之比例為40~99質量%,宜為45~95質量%,以50~92質量%更佳,又以55~90質量%更佳。於該比例未達40質量%的情況,耐化性及耐油性會降低。又,若該比例超過99質量%,以交聯為目的之來自反應性單體的單元之比例會相對地減少。又,該比例係表示將構成聚合物之全部的單體單元之作為單體的總質量設為100質量%時,聚合物含有的來自式(1)表示之單體的單元之就單體而言的質量之比例。關於後述其他的來自單體的單元之比例亦同。
((甲基)丙烯酸烷酯) 前述聚合物可更含有來自(甲基)丙烯酸烷酯的單元。藉由前述聚合物含有來自(甲基)丙烯酸烷酯的單元,可得到可能往多用途發展的丙烯酸樹脂組成物。作為(甲基)丙烯酸烷酯之具體例,可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸異己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸異十二烷酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯等。這些可使用一種,亦可將兩種以上併用。
相對於構成前述聚合物之全部單體單元100質量%,前述聚合物含有的來自前述(甲基)丙烯酸烷酯的單元之比例宜為0.1~40質量%,以5~35質量%更佳,又以10~30質量%更佳。藉由該比例為40質量%以下,可增加前述式(1)表示之來自單體的單元之比例,且丙烯酸樹脂組成物的耐化性及耐油性提升。
(含羧酸之(甲基)丙烯酸單體) 前述聚合物宜更含有來自含羧酸之(甲基)丙烯酸單體的單元。藉由前述聚合物含有來自含羧酸之(甲基)丙烯酸單體的單元,可使丙烯酸樹脂組成物的強度更加提升。作為含羧酸之(甲基)丙烯酸單體之具體例,可列舉(甲基)丙烯酸、(甲基)丙烯酸β-羧乙酯、伊康酸、巴豆酸、馬來酸、富馬酸等。這些之中,考量丙烯酸樹脂組成物的強度更高之觀點,更宜為(甲基)丙烯酸。這些可使用一種,亦可將兩種以上併用。
相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述含羧酸之(甲基)丙烯酸單體的單元之比例,宜為0.5~20質量%,以5~18質量%更佳,又以10~17質量%更佳,11~15質量%尤佳。藉由前述含羧酸之(甲基)丙烯酸單體之比例為0.5質量%以上,可使丙烯酸樹脂組成物的強度更加提升,又可賦予與環氧系交聯劑等交聯劑的反應點。
(含氮之丙烯酸單體) 前述聚合物宜更含有來自含氮之丙烯酸單體的單元。藉由前述聚合物含有來自含氮之丙烯酸單體的單元,可使丙烯酸樹脂組成物的強度及耐熱性提升,耐化性及耐油性亦提升。作為含氮之丙烯酸單體之具體例,可列舉(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺等N-烷基置換(甲基)丙烯醯胺;N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺等N,N-二烷基置換(甲基)丙烯醯胺;丙烯醯啉、乙烯基吡啶、N-乙烯基吡咯啶酮、(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等。這些之中,考量通用性、工業製品化之觀點,更宜為(甲基)丙烯醯胺、N-烷基置換(甲基)丙烯醯胺、N,N-二烷基置換(甲基)丙烯醯胺、丙烯醯啉。這些可使用一種,亦可將兩種以上併用。
相對於構成前述聚合物之全部單體單元100質量%,前述聚合物中含有的來自前述含氮之丙烯酸單體的單元之比例,宜為1~50質量%,以5~40質量%更佳,又以10~30質量%更佳。藉由該比例為1質量%以上,對樹脂改性有效。又,藉由該比例為50質量%以下,可將丙烯酸樹脂組成物適用於各式各樣的用途。
(其他單體) 前述聚合物中,除了前述來自單體的單元以外,例如可含有來自(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸-2-羥己酯、(甲基)丙烯酸與聚乙二醇或聚丙二醇之單酯等含有羥基的共聚合性單體等的單元。
(聚合方法) 含有上述單體的單體組成物之聚合方法無特別限制,例如溶液聚合、塊狀聚合、懸浮聚合、乳化聚合等各種聚合方法中,可使用光聚合或熱聚合等手段進行。更亦可使用利用如伽瑪射線的放射線為之聚合、電子束聚合。光聚合,例如在光聚合引發劑存在下,可對單體組成物以UV射線照射來進行。熱聚合,例如在熱聚合引發劑存在下,可將單體組成物加熱至50~200℃來進行。
(交聯劑) 本發明之丙烯酸樹脂組成物,考量可形成交聯結構的觀點,宜更含有交聯劑。作為交聯劑,考量與丙烯酸樹脂組成物之反應性的觀點,宜選自由多官能性(甲基)丙烯酸單體、多官能性(甲基)丙烯酸寡聚物、2官能以上的含環氧丙基之化合物、及2官能以上的含異氰酸酯基之化合物構成之群組中之至少一種的交聯劑。
作為多官能性(甲基)丙烯酸單體之具體例,可列舉三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯等。
作為多官能性(甲基)丙烯酸寡聚物之具體例,可列舉使(甲基)丙烯酸、含羥基之(甲基)丙烯酸酯對具有多個異氰酸酯基、環氧丙基之化合物反應而寡聚物化之胺甲酸乙酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。
作為2官能以上之含環氧丙基之化合物,可列舉1,3-雙(N,N-二環氧丙基胺甲基)環己烷、N,N,N’,N’-四環氧丙基間二甲苯二胺、N,N,N’,N’-四環氧丙基胺苯基甲烷、異氰尿酸三環氧丙酯、間-N,N-二環氧丙基胺苯環氧丙醚、N,N-二環氧丙基甲苯胺、N,N-二環氧丙基苯胺、季戊四醇聚環氧丙醚、1,6-己二醇二環氧丙醚等。
作為2官能以上之含異氰酸酯基化合物,可列舉甲苯二異氰酸酯(TDI)、氯伸苯二異氰酸酯、六亞甲基二異氰酸酯、四亞甲基二異氰酸酯、異佛酮二異氰酸酯、二苯基甲烷二異氰酸酯、經氫化的二苯基甲烷二異氰酸酯等異氰酸酯單體及將這些異氰酸酯單體附加三羥甲丙烷等而得之異氰酸酯化合物、三聚異氰酸酯化物、縮二脲型化合物、更進一步附加聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等之胺甲酸乙酯預聚合物型之異氰酸酯等。這些交聯劑可單獨使用一種,或可將二種以上組合使用。
丙烯酸樹脂組成物中之交聯劑的量,相對於100質量份之前述聚合物(聚合前之全部單體),宜為0.01~10質量份,以0.03~1質量份更佳,又以0.05~0.5質量份更佳。
(中空微填料) 本發明之丙烯酸樹脂組成物,考量賦予強度、質輕化之觀點。作為充填劑可含有中空微填料。作為中空微填料,可列舉中空玻璃珠、中空樹脂氣球等。這些之中,考量耐化性及耐油性之觀點更宜為中空玻璃珠。作為中空微填料之平均粒徑,宜為1~100μm,以10~50μm更佳。丙烯酸樹脂組成物中的中空微填料之含量,相對於100質量份之前述聚合物宜為2~50質量份,以5~30質量份更佳,又以10~20質量份更佳。又,為了提升向丙烯酸樹脂組成物之分散性,對於中空微填料可適當進行偶聯處理、硬脂酸處理等表面處理。
(阻燃劑) 本發明之丙烯酸樹脂組成物可含有阻燃劑。作為阻燃劑,可列舉聚磷酸銨、磷酸酯類等磷系阻燃劑、硫酸三聚氰胺、(聚合化)磷酸三聚氰胺等三聚氰胺系阻燃劑,金屬氫氧化物等。這些之中,又宜為聚磷酸銨。這些阻燃劑可使用一種,亦可將二種以上併用。也可藉由為了使耐水性提升之熱硬化性樹脂將這些阻燃劑被覆,亦可進行微膠囊化等表面處理。又,為了提升向丙烯酸樹脂組成物之分散性,可對於阻燃劑適當進行偶聯處理、硬脂酸處理等表面處理。
丙烯酸樹脂組成物中之阻燃劑的含量,依據所需的阻燃性程度有所差異,例如相對於100質量份之前述聚合物可為20~200質量份。又,伴隨阻燃劑含量的增加,黏著性會降低,因此宜使用能以較少量展現阻燃性之阻燃劑。
(導熱性粒子) 本發明之丙烯酸樹脂組成物可含有導熱性粒子。作為導熱性粒子,可列舉金屬粉、金屬氧化物、金屬氫氧化物、氮化硼、氮化矽、氮化碳等。這些導熱性粒子可使用一種,亦可將二種以上併用。導熱性粒子的平均粒徑宜為1~100μm,以10~50μm更佳。為了使向丙烯酸樹脂組成物之分散性提升,可對於導熱性粒子適當進行偶聯處理、硬脂酸處理等表面處理。
(其他添加劑) 本發明之丙烯酸樹脂組成物中可因應需要含有各種矽烷偶聯劑等添加劑。
(丙烯酸樹脂組成物之抗拉強度) 將本發明之丙烯酸樹脂組成物浸漬於油酸24小時後的抗拉強度為浸漬於油酸前的抗拉強度之值之50%以上,且宜為60%以上,又以70%以上更佳。藉由該比例(以下亦表示為維持率)為50%以上,丙烯酸樹脂組成物呈現高耐化性及耐油性。維持率之上限無特別限定,宜為較高較理想。又,本發明之丙烯酸樹脂組成物在常溫(15~25℃)中為固體,可測定抗拉強度。該抗拉強度係依據JIS K 7114測定的值,具體而言係藉由後述方法測定。本發明之丙烯酸樹脂組成物,不只對於油酸的耐受性良好,亦如後述實施例中所示,對於甲苯等其他的工業用溶劑、汽油等其他的油類,亦為相較於習知的丙烯酸樹脂組成物呈現更高的耐受性。
[黏著劑組成物、黏著片用基材及黏著片] 本發明之黏著劑組成物,係由本發明之丙烯酸樹脂組成物構成。本發明之黏著片用基材含有本發明之丙烯酸樹脂組成物。本發明之黏著片含有本發明之黏著劑組成物及/或本發明之黏著片用基材。
本發明之黏著片例如可由為支持體之黏著片用基材與該黏著片用基材上設有的由黏著劑組成物構成之黏著劑層(樹脂層)構成。該黏著片用基材及/或該黏著劑組成物為本發明之黏著片用基材及/或黏著劑組成物。黏著劑層,可只設在黏著片用基材之其中一面,亦可設在雙面。又,黏著劑層,可與黏著片用基材直接黏接,亦可經由底漆層間接地黏接。又,亦可於剝離片的一面設有本發明之黏著片,以使用時將該剝離片剝下之態樣的黏接用片的形式來使用。
本發明之黏著片用基材可含有本發明之丙烯酸樹脂組成物作為丙烯酸樹脂發泡體。作為丙烯酸樹脂發泡體之製造方法,例如在日本特開2012-153900號公報中,揭示了為低密度且氣泡細而平均地分散之丙烯酸樹脂發泡體黏著劑及其製造方法。又,作為其他方法,可舉出添加發泡劑而使其在製成片材時發泡、添加前述中空微填料進行製成片材等方法。使用本發明之黏著片用基材以外的黏著片用基材的情況,作為該黏著片用基材,可列舉聚酯、聚醯亞胺、聚烯烴等之各種膜、嫘縈、馬尼拉紙等之不織布、金屬箔、織布等。
由本發明之黏著劑組成物構成之黏著劑層的厚度無特別限定,例如可為0.1~5mm,宜為0.1~1mm。
本發明之黏著片,例如可適宜使用於電子設備元件、汽車零件、建築材等中之各構件的黏接。
[實施例]
[評估測試方法] 以下的評估項目係依據JIS K 7114「求出塑膠-液體化學藥品中的浸漬效果之測試方法」而進行。
<抗拉強度> 初始:將切成10mm×100mm的樹脂片,利用拉伸壓縮測試機以拉伸速度300mm/min拉伸,測定斷開時的強度。
各化學藥品(油成分)浸漬後:將切成10mm×100mm的樹脂片於23℃浸漬於各化學藥品(油酸、汽油、甲苯)中24小時,取出後立即利用拉伸壓縮測試機以拉伸速度300mm/min拉伸,測定斷開時的強度。
<尺寸變化率> 將切成10mm×100mm的樹脂片於23℃浸漬於各化學藥品(油酸、汽油、甲苯)中24小時,取出後立即測定試驗樣品的寬度,以下式算出尺寸變化率。
尺寸變化率=[(浸漬後之試驗樣品的寬度)-(浸漬前之試驗樣品的寬度(10mm))]/浸漬前之試驗樣品的寬度(10mm)×100(%)。
<質量變化率> 測定切成10mm×100mm之樹脂片的質量。然後,將該試驗樣品於23℃浸漬於各化學藥品(油酸、汽油、甲苯)中24小時,取出後立即擦去試驗樣品表面的學藥品並測定質量。利用下式算出自浸漬前起的質量變化率。
質量變化率=[(浸漬後之試驗樣品的質量)-(浸漬前之試驗樣品的質量)]/浸漬前之試驗樣品的質量×100(%)。
[實施例1] 於具備攪拌機、回流冷卻器、溫度計、UV燈及氮氣導入口的反應容器中,添加60.0質量份之丙烯酸2-甲氧基乙酯、27.5質量份之丙烯酸2-乙基己酯、12.5質量份之丙烯酸、0.01質量份之作為光聚合引發劑之Irgacure1173(商品名,BASF Japan製)、及0.01質量份之作為鏈轉移劑之正十二基硫醇,製備成單體組成物。藉由在氮氣環境下對該單體組成物照射UV光,使單體的一部分聚合,製備糖漿狀組成物。該糖漿狀組成物中之聚合物的濃度約為13質量%,該聚合物的重量平均分子量約為85萬。
相對於前述100質量份之糖漿狀組成物,添加0.1質量份之作為交聯劑之1,6-己二醇二丙烯酸酯(商品名:NK ester A-HD-N,新中村化學工業(股)製)、0.5質量份之作為光聚合引發劑之Irgacure1173(商品名,BASF Japan公司製),並均勻地攪拌。藉由脫泡操作去除攪拌混合時混入的空氣泡,製備塗佈液。
在表面經脫膜劑處理的厚度50μm之聚對苯二甲酸乙二酯(PET)膜上,以使獲得之樹脂層的厚度成為0.5mm的方式,塗佈前述塗佈液。在由前述塗佈液構成的層上,將厚度50μm的PET膜疊層後,照射紫外線,製成具有由本發明之丙烯酸樹脂組成物構成之樹脂層之樹脂片。針對該樹脂片,進行前述評估測試。結果示於表1。
[實施例2~8、比較例1~5] 除了將單體組成物中之單體的種類與量、交聯劑的種類與量變更為如表1以外,與實施例1同樣地製作樹脂片並評估。結果示於表1。
又,實施例2及5,以及比較例2中,相對於合計(獲得的聚合物)100質量份之糖漿狀組成物製備時之單體,添加15.0質量份之作為填充劑之為中空玻璃珠的玻璃氣球(商品名:Sphericel 34P30,Potters-Ballotini製,平均粒徑:35μm)。又,比較例4及5的汽油及甲苯浸漬後之抗拉強度之評價中,在設置於測定機前樹脂片便斷開,因此無法進行測定。
[實施例9] 在具備冷卻管、攪拌機及溫度計的反應容器內,將60.0質量份之丙烯酸2-甲氧基乙酯、27.5質量份之丙烯酸2-乙基己酯、12.5質量份之丙烯酸、及0.2質量份之作為聚合引發劑之2,2’-偶氮二異丁腈溶解於100質量份之乙酸乙酯。氮氣置換後,於68℃聚合4小時,更進一步添加0.2質量份之2,2’-偶氮二異丁腈,於80℃聚合2小時。獲得之溶液中的聚合物的濃度約為50質量%,該聚合物的重量平均分子量約為80萬。於該溶液添加0.08質量份之作為交聯劑的4官能環氧丙基化合物(商品名:Tetrad-X,三菱瓦斯化學(股)製),混合而製備塗佈液。
在表面經脫膜劑處理的厚度50μm之聚對苯二甲酸乙二酯(PET)膜上,以獲得之樹脂層的厚度成為0.1mm的方式,塗佈前述塗佈液,並利用乾燥機使其乾燥。將此步驟重複5次,使其疊層而使樹脂層的厚度成為0.5mm,製作具有由本發明之丙烯酸樹脂組成物構成的樹脂層之樹脂片。針對該樹脂片,進行前述評估測試。結果示於表1。
[表1]
2-MEA‧‧‧丙烯酸2-甲氧基乙酯
AM-90G‧‧‧丙烯酸甲氧基(聚)乙二酯(n=9)
2-EHA‧‧‧丙烯酸2-乙基己酯
n-BA‧‧‧丙烯酸正丁酯
AA‧‧‧丙烯酸
ACMO‧‧‧丙烯醯啉
HDDA‧‧‧1,6-己二醇二丙烯酸酯
Tetrad-X‧‧‧商品名,三菱瓦斯化學(股)製,N,N,N’,N’-四環氧丙基間二甲苯胺
Claims (14)
- 一種丙烯酸樹脂組成物,包含聚合物,該聚合物含有來自下式(1)表示之單體的單元, 相對於構成該聚合物之全部單體單元100質量%,該聚合物中含有的來自該式(1)表示之單體的單元之比例為40~99質量%, 且該丙烯酸樹脂組成物浸漬於油酸24小時後的抗拉強度,為浸漬於油酸前的抗拉強度之值之50%以上; 該式(1)中,R1 表示氫原子或甲基,R2 表示碳數2~4之伸烷基,R3 表示碳數1~10之烷基,n表示1~20的整數。 [化1]
- 如申請專利範圍第1項之丙烯酸樹脂組成物,更包含交聯劑。
- 如申請專利範圍第2項之丙烯酸樹脂組成物,其中,該交聯劑係選自由多官能性(甲基)丙烯酸單體、多官能性(甲基)丙烯酸寡聚物、2官能以上的含環氧丙基之化合物、及2官能以上的含異氰酸酯基之化合物構成之群組中之至少一種交聯劑。
- 如申請專利範圍第1至3項中任一項之丙烯酸樹脂組成物,該聚合物更含有來自(甲基)丙烯酸烷酯的單元, 且相對於構成該聚合物之全部單體單元100質量%,該聚合物中含有的來自該(甲基)丙烯酸烷酯的單元之比例為0.1~40質量%。
- 如申請專利範圍第1至3項中任一項之丙烯酸樹脂組成物,該聚合物更含有來自含羧酸之(甲基)丙烯酸單體的單元, 且相對於構成該聚合物之全部單體單元100質量%,該聚合物含有的來自該含羧酸之(甲基)丙烯酸單體的單元之比例為0.5~20質量%。
- 如申請專利範圍第5項之丙烯酸樹脂組成物,其中,該含羧酸之(甲基)丙烯酸單體為(甲基)丙烯酸。
- 如申請專利範圍第1至3項中任一項之丙烯酸樹脂組成物,其中,該式(1)表示的單體係選自由(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基(聚)乙二酯、及(甲基)丙烯酸乙氧基(聚)乙二酯構成之群組中之至少一種單體。
- 如申請專利範圍第1至3項中任一項之丙烯酸樹脂組成物,其中,該聚合物更含有來自含氮之丙烯酸單體的單元, 相對於構成該聚合物之全部單體單元100質量%,該聚合物含有的來自該含氮之丙烯酸單體的單元之比例為1~50質量%。
- 如申請專利範圍第8項之丙烯酸樹脂組成物,其中,該含氮之丙烯酸單體係選自由(甲基)丙烯醯胺、N-烷基置換(甲基)丙烯醯胺、N,N-二烷基置換(甲基)丙烯醯胺、及丙烯醯啉構成之群組中之至少一種單體。
- 如申請專利範圍第1至3項中任一項之丙烯酸樹脂組成物,更含有平均粒徑為1~100μm的中空微填料。
- 如申請專利範圍第10項之丙烯酸樹脂組成物,其中,該中空微填料為中空玻璃珠,且該中空微填料之含量相對於100質量份之該聚合物為2~50質量份。
- 一種黏著劑組成物,由如申請專利範圍第1至11項中任一項之丙烯酸樹脂組成物構成。
- 一種黏著片用基材,含有如申請專利範圍第1至11項中任一項之丙烯酸樹脂組成物。
- 一種黏著片,含有如申請專利範圍第12項之黏著劑組成物,及/或如申請專利範圍第13項之黏著片用基材。
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| TWI740799B (zh) * | 2019-04-16 | 2021-09-21 | 日商信越化學工業股份有限公司 | 附有黏著劑層的防塵薄膜框架、防塵薄膜組件、附有防塵薄膜組件的曝光原版、曝光方法、半導體裝置的製造方法、及液晶顯示板的製造方法 |
| US12116431B2 (en) | 2021-08-17 | 2024-10-15 | Industrial Technology Research Institute | Light-curing resin composition, three-dimensional object containing the same, and manufacturing method of three-dimensional object |
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| JP7276322B2 (ja) * | 2018-03-26 | 2023-05-18 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物、シール材、及びホース材 |
| KR102683875B1 (ko) * | 2019-02-19 | 2024-07-11 | 가부시키가이샤 데라오카 세이사쿠쇼 | 아크릴계 점착제 조성물 및 접착 테이프, 및 그 접착 테이프에 의해 고정된 광학 시트를 갖는 광학 장치 |
| JP7474118B2 (ja) * | 2019-05-30 | 2024-04-24 | 積水化学工業株式会社 | 粘着剤及び粘着テープ |
| CN116917426A (zh) * | 2021-03-11 | 2023-10-20 | 科巨希化学股份有限公司 | 涂料组合物、使用该涂料组合物的黏着性或非黏着性涂层、以及具备该涂层的积层体 |
| CN113429919A (zh) * | 2021-07-15 | 2021-09-24 | 宁波润禾高新材料科技股份有限公司 | 一种光固化丙烯酸发泡压敏胶的合成工艺 |
| KR102677695B1 (ko) * | 2022-05-09 | 2024-06-25 | 주식회사 티티티 | 점착제 조성물 및 이를 포함하는 점착성 가공품 |
| KR102677480B1 (ko) * | 2022-05-09 | 2024-06-25 | 주식회사 티티티 | 점착제 조성물 및 이를 포함하는 점착성 가공품 |
| JPWO2023248906A1 (zh) * | 2022-06-21 | 2023-12-28 |
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| JP4696280B2 (ja) | 1999-10-28 | 2011-06-08 | 綜研化学株式会社 | 耐湿粘着シートおよびその用途 |
| JP4788937B2 (ja) | 2001-05-07 | 2011-10-05 | 綜研化学株式会社 | 粘着剤組成物及び該組成物を用いたディスプレイ用粘着シート |
| JP2008115272A (ja) * | 2006-11-04 | 2008-05-22 | Nitto Denko Corp | 熱剥離性両面粘着シート及び被加工体の加工方法 |
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| US20110033720A1 (en) * | 2008-04-11 | 2011-02-10 | Jun Fujita | Transparent adhesive sheet and image display device including the same |
| JP4800363B2 (ja) * | 2008-09-26 | 2011-10-26 | 日東電工株式会社 | 光学部材貼り合わせ用粘着シート |
| JP2011148889A (ja) | 2010-01-21 | 2011-08-04 | Kansai Paint Co Ltd | 親水化処理剤 |
| JP5059137B2 (ja) | 2010-01-29 | 2012-10-24 | 大成ファインケミカル株式会社 | 帯電防止性ドライラミネート用水性接着剤 |
| JP6022884B2 (ja) | 2011-10-14 | 2016-11-09 | 日東電工株式会社 | 両面粘着テープ |
| JP2013199521A (ja) | 2012-03-23 | 2013-10-03 | Dexerials Corp | 光学用粘着シートを形成するための熱又は光硬化性樹脂組成物及び光学用粘着シート |
| EP2803712A1 (en) * | 2013-05-17 | 2014-11-19 | 3M Innovative Properties Company | Multilayer Pressure Sensitive Adhesive Assembly |
| JP6202958B2 (ja) * | 2013-09-13 | 2017-09-27 | 日東電工株式会社 | 粘着シート |
| JP6470523B2 (ja) * | 2014-08-08 | 2019-02-13 | 日東電工株式会社 | 粘着シート |
| JP2016069480A (ja) | 2014-09-29 | 2016-05-09 | ニチバン株式会社 | 粘着剤組成物 |
| CN106795415B (zh) | 2014-10-15 | 2019-04-02 | 综研化学株式会社 | 粘合剂层、带粘合剂层的偏振片和层叠体 |
| JP6113889B2 (ja) | 2015-09-18 | 2017-04-12 | 日東電工株式会社 | 粘着シート |
| JP6037485B2 (ja) | 2015-12-15 | 2016-12-07 | オリジン電気株式会社 | 熱及び光硬化性塗料組成物及び塗膜形成方法 |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI740799B (zh) * | 2019-04-16 | 2021-09-21 | 日商信越化學工業股份有限公司 | 附有黏著劑層的防塵薄膜框架、防塵薄膜組件、附有防塵薄膜組件的曝光原版、曝光方法、半導體裝置的製造方法、及液晶顯示板的製造方法 |
| US12116431B2 (en) | 2021-08-17 | 2024-10-15 | Industrial Technology Research Institute | Light-curing resin composition, three-dimensional object containing the same, and manufacturing method of three-dimensional object |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200020885A (ko) | 2020-02-26 |
| JP7364465B2 (ja) | 2023-10-18 |
| JPWO2018235217A1 (ja) | 2020-04-16 |
| US11958967B2 (en) | 2024-04-16 |
| TWI682020B (zh) | 2020-01-11 |
| WO2018235217A1 (ja) | 2018-12-27 |
| CN110770295A (zh) | 2020-02-07 |
| KR102285181B1 (ko) | 2021-08-02 |
| US20210147670A1 (en) | 2021-05-20 |
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