下面，基於優選的實施方式說明本發明。
本發明的粘著劑組合物，其特徵在於，其主劑是由含有（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體、（C）含有羧基的可共聚的單體、（D）聚亞烷基二醇單（甲基）丙烯酸酯單體、以及（E）不含羥基而含氮的乙烯基單體或者含有烷氧基的（甲基）丙烯酸烷基酯單體中的至少一種的共聚物的丙烯酸類聚合物構成，還含有（F）三官能以上的異氰酸酯化合物、（G）交聯阻滯劑、（H）交聯催化劑、（I）抗靜電劑、以及（J）聚醚改質矽氧烷化合物，前述丙烯酸類聚合物的酸值為0.01～8.0。
做為（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，可舉出：（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸異壬酯、（甲基）丙烯酸癸酯等。
做為（B）含有羥基的可共聚的單體，可以舉出：（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯等（甲基）丙烯酸羥基烷基酯類；N-羥基（甲基）丙烯醯胺、N-羥甲基（甲基）丙烯醯胺、N-羥乙基（甲基）丙烯醯胺等含有羥基的（甲基）丙烯醯胺類等。
優選上述（B）含有羥基的可共聚的單體是選自於由（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯、N-羥基（甲基）丙烯醯胺、N-羥甲基（甲基）丙烯醯胺、N-羥乙基（甲基）丙烯醯胺所組成的化合物組中的至少一種以上。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選含有0.1～5.0重量份的前述（B）含有羥基的可共聚的單體。
並且，在（B）含有羥基的可共聚的單體中，（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯和（甲基）丙烯酸4-羥基丁酯的合計量優選為低於1重量份（也允許不含有的情況），更優選為0～0.9重量份。
優選（C）含有羧基的可共聚的單體是選自於由（甲基）丙烯酸、（甲基）丙烯酸羧乙酯、（甲基）丙烯酸羧戊酯、2-（甲基）丙烯醯氧基乙基六氫鄰苯二甲酸、2-（甲基）丙烯醯氧基丙基六氫鄰苯二甲酸、2-（甲基）丙烯醯氧基乙基鄰苯二甲酸、2-（甲基）丙烯醯氧基乙基琥珀酸、2-（甲基）丙烯醯氧基乙基馬來酸、羧基聚己內酯單（甲基）丙烯酸酯、2-（甲基）丙烯醯氧基乙基四氫鄰苯二甲酸所組成的化合物組中的至少一種以上。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，（C）含有羧基的可共聚的單體的含量優選為0.35～1.0重量份，更優選為0.35～0.6重量份。
做為（D）聚亞烷基二醇單（甲基）丙烯酸酯單體，只要是聚亞烷基二醇所具有的多個羥基中的一個羥基被酯化為（甲基）丙烯酸酯的化合物即可。由於（甲基）丙烯酸酯基為聚合性基，因此能夠與主劑聚合物進行共聚。其他羥基，既可以保持OH的狀態，也可以成為甲醚、乙醚等的烷基醚，或者醋酸酯等飽和羧酸酯等。
做為聚亞烷基二醇所具有的亞烷基，可以舉出乙烯基、丙烯基、丁烯基等，但並不限定於這些。聚亞烷基二醇也可以是聚乙二醇、聚丙二醇、聚丁二醇等中的兩種以上的聚亞烷基二醇的共聚物。做為聚亞烷基二醇的共聚物，可以舉出聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇、聚乙二醇-聚丙二醇-聚丁二醇等，該共聚物可以是嵌段共聚物、無規共聚物。
做為（D）聚亞烷基二醇單（甲基）丙烯酸酯單體，優選為選自聚亞烷基二醇單（甲基）丙烯酸酯、甲氧基聚亞烷基二醇（甲基）丙烯酸酯、乙氧基聚亞烷基二醇（甲基）丙烯酸酯中的至少一種以上。
更具體而言，可以舉出：聚乙二醇-單（甲基）丙烯酸酯、聚丙二醇-單（甲基）丙烯酸酯、聚丁二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丙二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丁二醇-單（甲基）丙烯酸酯、聚丙二醇-聚丁二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丙二醇-聚丁二醇-單（甲基）丙烯酸酯；甲氧基聚乙二醇-（甲基）丙烯酸酯、甲氧基聚丙二醇-（甲基）丙烯酸酯、甲氧基聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯；乙氧基聚乙二醇-（甲基）丙烯酸酯、乙氧基聚丙二醇-（甲基）丙烯酸酯、乙氧基聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丙二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯等。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選含有1～20重量份的（D）聚亞烷基二醇單（甲基）丙烯酸酯單體。
在（E）中，做為（E-1）含氮的乙烯基單體，可以舉出：含有醯胺鍵的乙烯基單體、含有氨基的乙烯基單體、具有含氮的雜環結構的乙烯基單體等。更具體而言，可以舉出：N-乙烯基-2-吡咯烷酮、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基呱啶酮、N-乙烯基嘧啶、N-乙烯基呱嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-乙烯基嗎啉、N-乙烯基己內醯胺、N-乙烯基十二內醯胺等的具有N-乙烯基取代的雜環結構的環狀氮乙烯基化合物；N-（甲基）丙烯醯基嗎啉、N-（甲基）丙烯醯基呱嗪、N-（甲基）丙稀醯基氮丙啶、N-（甲基）丙烯醯基吖丁啶、N-（甲基）丙烯醯基吡咯烷、N-（甲基）丙烯醯基呱啶、N-（甲基）丙烯醯基氮雜環庚烷、N-（甲基）丙烯醯基氮雜環辛烷等的具有N-（甲基）丙烯醯基取代的雜環結構的環狀氮乙烯基化合物；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等具有在環內含有氮原子和乙烯基類不飽和鍵的雜環結構的環狀氮乙烯基化合物；（甲基）丙烯醯胺、N-甲基（甲基）丙烯醯胺、N-異丙基（甲基）丙烯醯胺、N-叔丁基（甲基）丙烯醯胺等未取代或者單烷基取代的（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、N,N-二丙基丙烯醯胺、N,N-二異丙基（甲基）丙烯醯胺、N,N-二丁基（甲基）丙烯醯胺、N-乙基-N-甲基（甲基）丙烯醯胺、N-甲基-N-丙基（甲基）丙烯醯胺、N-甲基-N-異丙基（甲基）丙烯醯胺等二烷基取代（甲基）丙烯醯胺；N,N-二甲基氨基甲基（甲基）丙烯酸酯、N,N-二甲基氨基乙基（甲基）丙烯酸酯、N,N-二甲基氨基丙基（甲基）丙烯酸酯、N,N-二甲基氨基異丙基（甲基）丙烯酸酯、N,N-二甲基氨基丁基（甲基）丙烯酸酯、N,N-二乙基氨基甲基（甲基）丙烯酸酯、N,N-二乙基氨基乙基（甲基）丙烯酸酯、N-乙基-N-甲基氨基乙基（甲基）丙烯酸酯、N-甲基-N-丙基氨基乙基（甲基）丙烯酸酯、N-甲基-N-異丙基氨基乙基（甲基）丙烯酸酯、N,N-二丁基氨基乙基（甲基）丙烯酸酯、叔丁基氨基乙基（甲基）丙烯酸酯等二烷基氨基（甲基）丙烯酸酯；N,N-二甲基氨基丙基（甲基）丙烯醯胺、N,N-二乙基氨基丙基（甲基）丙烯醯胺、N,N-二丙基氨基丙基（甲基）丙烯醯胺、N,N-二異丙基氨基丙基（甲基）丙烯醯胺、N-乙基-N-甲基氨基丙基（甲基）丙烯醯胺、N-甲基-N-丙基氨基丙基（甲基）丙烯醯胺、N-甲基-N-異丙基氨基丙基（甲基）丙烯醯胺等的N,N-二烷基取代氨基丙基（甲基）丙烯醯胺；N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基-N-甲基乙醯胺等N-乙烯基羧酸醯胺類；N-甲氧基甲基（甲基）丙烯醯胺、N-乙氧基乙基（甲基）丙烯醯胺、N-丁氧基甲基（甲基）丙烯醯胺、二丙酮丙烯醯胺、N,N-亞甲基雙（甲基）丙烯醯胺等（甲基）丙烯醯胺類；（甲基）丙烯腈等不飽和羧酸腈類；等。
做為（E-1）含氮的乙烯基單體，優選不含羥基，更優選不含羥基和羧基。做為這種單體，優選為上面例示的單體，例如：含有N,N-二烷基取代氨基、N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基-2-吡咯烷酮、N-乙烯基己內醯胺、N-乙烯基-2-呱啶酮等N-乙烯基取代內醯胺；N-（甲基）丙烯醯基嗎啉、N-（甲基）丙烯醯基吡咯烷等N-（甲基）丙烯醯基取代環狀胺類。
在（E）中，做為（E-2）含有烷氧基的（甲基）丙烯酸烷基酯單體，可以舉出：（甲基）丙烯酸2-甲氧基乙酯、（甲基）丙烯酸2-乙氧基乙酯、（甲基）丙烯酸2-丙氧基乙酯、（甲基）丙烯酸2-異丙氧基乙酯、（甲基）丙烯酸2-丁氧基乙酯、（甲基）丙烯酸2-甲氧基丙酯、（甲基）丙烯酸2-乙氧基丙酯、（甲基）丙烯酸2-丙氧基丙酯、（甲基）丙烯酸2-異丙氧基丙酯、（甲基）丙烯酸2-丁氧基丙酯、（甲基）丙烯酸3-甲氧基丙酯、（甲基）丙烯酸3-乙氧基丙酯、（甲基）丙烯酸3-丙氧基丙酯、（甲基）丙烯酸3-異丙氧基丙酯、（甲基）丙烯酸3-丁氧基丙酯、（甲基）丙烯酸4-甲氧基丁酯、（甲基）丙烯酸4-乙氧基丁酯、（甲基）丙烯酸4-丙氧基丁酯、（甲基）丙烯酸4-異丙氧基丁酯、（甲基）丙烯酸4-丁氧基丁酯等。
這些含有烷氧基的（甲基）丙烯酸烷基酯單體，具有（甲基）丙烯酸烷基酯中的烷基的原子被烷氧基取代的結構。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選（E-1）不含羥基而含氮的乙烯基單體或者（E-2）含有烷氧基的（甲基）丙烯酸烷基酯單體的含量為1～20重量份。對（E-1）不含羥基而含氮的乙烯基單體和（E-2）含有烷氧基的（甲基）丙烯酸烷基酯單體而言，既可以分別使用一種也可以併用兩種以上。
做為（F）三官能以上的異氰酸酯化合物，只要是在一分子中至少具有三個以上的異氰酸酯（NCO）基的聚異氰酸酯化合物即可。聚異氰酸酯化合物包括脂肪族類異氰酸酯、芳香族類異氰酸酯、非環式類異氰酸酯、脂環式類異氰酸酯等分類，本發明可以是其中的任意種類。做為聚異氰酸酯化合物的具體例子，可以舉出：六亞甲基二異氰酸酯（HDI）、異佛爾酮二異氰酸酯（IPDI）、三甲基六亞甲基二異氰酸酯（TMDI）等脂肪族類異氰酸酯化合物；二苯基甲烷二異氰酸酯（MDI）、苯二甲基二異氰酸酯（XDI）、氫化苯二甲基二異氰酸酯（H6XDI）、二甲基二亞苯基二異氰酸酯（TOID）、甲苯二異氰酸酯（TDI）等芳香族類異氰酸酯化合物。
做為三官能以上的異氰酸酯化合物，可以舉出：二異氰酸酯類（在一分子中具有兩個NCO基的化合物）的縮二脲改質體或異氰脲酸酯改質體，與三羥甲基丙烷（TMP）或甘油等三價以上的多元醇（在一分子中至少具有三個以上OH基的化合物）的加成物（多元醇改質體）等。
並且，做為本發明中使用的（F）三官能以上的異氰酸酯化合物，優選包括選自（F-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（F-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，其中，所述（F-1）第一脂肪族類異氰酸酯化合物組是由六亞甲基二異氰酸酯化合物的異氰脲酸酯、異佛爾酮二異氰酸酯化合物的異氰脲酸酯、六亞甲基二異氰酸酯化合物的加成物、異佛爾酮二異氰酸酯化合物的加成物、六亞甲基二異氰酸酯化合物的縮二脲、異佛爾酮二異氰酸酯化合物的縮二脲所組成；所述（F-2）第二芳香族類異氰酸酯化合物組是由甲苯二異氰酸酯化合物的異氰脲酸酯、苯二甲基二異氰酸酯化合物的異氰脲酸酯、氫化苯二甲基二異氰酸酯化合物的異氰脲酸酯、甲苯二異氰酸酯化合物的加成物、苯二甲基二異氰酸酯化合物的加成物、氫化苯二甲基二異氰酸酯化合物的加成物所組成。優選併用（F-1）第一脂肪族類異氰酸酯化合物組和（F-2）第二芳香族類異氰酸酯化合物組。在本發明中，做為（F）三官能以上的異氰酸酯化合物，藉由併用選自（F-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（F-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，能夠進一步改善低速剝離區域和高速剝離區域中的粘著力的平衡性。
另外，優選（F）三官能以上的異氰酸酯化合物包括選自前述（F-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自前述（F-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，並且相對於100重量份的前述共聚物，該（F）三官能以上的異氰酸酯化合物的合計含量為0.5～5.0重量份。另外，做為選自（F-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上與選自（F-2）第二芳香族類異氰酸酯化合物組中的至少一種以上的混合比率，以重量比計算優選為（F-1）:（F-2）在10% : 90%～90% : 10%的範圍內。
做為（G）交聯阻滯劑，可以舉出：乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油酯、乙醯乙酸月桂酯、乙醯乙酸硬脂醯酯等的β-酮酯；乙醯丙酮、2,4-己二酮、苯甲醯丙酮等的β-二酮。這些是酮烯醇互變異構化合物，在以聚異氰酸酯化合物做為交聯劑的粘著劑組合物中，藉由將交聯劑所具有的異氰酸酯基進行封閉，能夠抑制配合交聯劑後粘著劑組合物的粘度過度上升或凝膠化的現象，能夠延長粘著劑組合物的儲存期。
優選（G）交聯阻滯劑為酮烯醇互變異構化合物，特別優選為選自由乙醯丙酮、乙醯乙酸乙酯所組成的化合物組中的至少一種以上。
相對於100重量份的共聚物，優選（G）交聯阻滯劑的含量為1.0～5.0重量份。
在以聚異氰酸酯化合物做為交聯劑的情況下，（H）交聯催化劑只要是做為催化劑對前述共聚物和交聯劑的反應（交聯反應）發揮功能的物質即可，可以舉出：三級胺等的胺類化合物、有機錫化合物、有機鉛化合物、有機鋅化合物等有機金屬化合物等。
做為三級胺可以舉出：三烷基胺、N,N,N',N'-四烷基二胺、N,N-二烷基氨基醇、三乙烯二胺、嗎啉衍生物、呱嗪衍生物等。
做為有機錫化合物，可以舉出：二烷基錫氧化物、二烷基錫的脂肪酸鹽、亞錫的脂肪酸鹽等。
優選（H）交聯催化劑為有機錫化合物，特別優選為選自於由氧化二辛基錫、二月桂酸二辛基錫所組成的化合物組中的至少一種以上。
相對於100重量份的共聚物，優選（H）交聯催化劑的含量為0.01～0.5重量份。
優選（I）抗靜電劑是（I-1）熔點為30～80℃的離子化合物、或者（I-2）含有丙烯醯基的四級銨鹽型離子化合物。
在本發明中，做為（I）抗靜電劑，將（I-1）熔點為30～80℃的離子化合物添加於共聚物中，或者將（I-2）含有丙烯醯基的四級銨鹽型離子化合物共聚於共聚物中。推測由於這些（I）抗靜電劑的熔點低且具有長鏈烷基，因此，與丙烯酸共聚物的親和性高。
做為（I-1）熔點為30～80℃的離子化合物，是具有陽離子和陰離子的離子化合物，可以舉出：陽離子為吡啶鎓陽離子、咪唑鎓陽離子、嘧啶鎓陽離子、吡唑鎓陽離子、吡咯鎓陽離子、銨陽離子等的含氮鎓陽離子,或者鏻陽離子、鋶陽離子等，陰離子為六氟磷酸根（PF-6
）、硫氰酸根（SCN-
）、烷基苯磺酸根（RC6
H4
SO3 -
）、過氯酸根（ClO4-
）、四氟化硼酸根（BF4 -
）等的無機或有機陰離子的化合物。優選在常溫（例如30℃）下是固體，並藉由選擇烷基的鏈長、取代基的位置、個數等，能夠得到熔點為30～80℃的化合物。優選陽離子為四級氮鎓陽離子，可以舉出：1-烷基吡啶鎓（2～6位的碳原子既可以具有取代基也可以不具有取代基）等的四級吡啶鎓陽離子、1,3-二烷基咪唑鎓（2、4、5位的碳原子既可以具有取代基也可以不具有取代基）等的四級咪唑鎓陽離子、四烷基銨等的四級銨陽離子等。
相對於100重量份的共聚物，優選（I-1）熔點為30～80℃的離子化合物的含量為0.1～5.0重量份。
做為（I-2）含有丙烯醯基的四級銨鹽型離子化合物，是具有陽離子和陰離子的離子化合物，可以舉出：陽離子為（甲基）丙烯醯氧基烷基三烷基銨（R3
N+
-Cn
H2n
-OCOCQ＝CH2，其中，Q＝H或CH3
，R＝烷基）等的含有（甲基）丙烯醯基的四級銨離子；陰離子為六氟磷酸根（PF6 -
）、硫氰酸根（SCN-
）、有機磺酸根（RSO3 -
）、過氯酸根（ClO4 -
）、四氟化硼酸根（BF4 -
）、含F醯亞胺根（RF 2
N-
）等的無機或有機陰離子的化合物。做為含F醯亞胺根（
）的RF
，可以舉出三氟甲磺醯基、五氟乙磺醯基等的全氟烷基磺醯基、氟磺醯基。做為含F醯亞胺根，可以舉出雙(氟磺醯基)醯亞胺根〔(FSO2
)2
N-
〕、雙(三氟甲磺醯基)醯亞胺根〔(CF3
SO2
)2
N-
〕、雙(五氟乙磺醯基)醯亞胺根〔(C2
F5
SO2
)2
N-
〕等的雙磺醯基醯亞胺根。
（I-2）含有丙烯醯基的四級銨鹽型離子化合物，優選在共聚物中的共聚量為0.1～5.0重量%。
做為（I）抗靜電劑的具體例子，沒有特別限定，但做為（I-1）熔點為30～80℃的離子化合物的具體例子，可以舉出1-辛基吡啶鎓六氟磷酸鹽、1-壬基吡啶鎓六氟磷酸鹽、2-甲基-1-十二烷基吡啶鎓六氟磷酸鹽、1-辛基吡啶鎓十二烷基苯磺酸鹽、1-十二烷基吡啶鎓硫氰酸鹽、1-十二烷基吡啶鎓十二烷基苯磺酸鹽、4-甲基-1-辛基吡啶鎓六氟磷酸鹽等。另外，做為（I-2）含有丙烯醯基的四級銨鹽型離子化合物的具體例子，可以舉出二甲基氨基甲基（甲基）丙烯酸酯六氟磷酸甲基鹽〔(CH3
)3
N＋
CH2
OCOCQ＝CH2
•PF6 -
、其中，Q＝H或CH3
〕、二甲基氨基乙基（甲基）丙烯酸酯雙(三氟甲磺醯基)醯亞胺甲基鹽〔(CH3
)3
N＋
(CH2
)2
OCOCQ＝CH2
•(
)2
N-
，其中，Q＝H或CH3
〕、甲基丙烯酸二甲基氨基甲酯雙(氟磺醯基)醯亞胺甲基鹽〔(CH3
)3
N＋
CH2
OCOCQ＝CH2
•(FSO2
)2
N-
，其中，Q＝H或CH3
〕等。
（J）聚醚改質矽氧烷化合物是具有聚醚基的矽氧烷化合物，除了通常的矽氧烷單元（-SiR1 2
-O-）之外，還具有包含聚醚基的矽氧烷單元（-SiR1
(R2
O(R3
O)n
R4
)-O-）。在此，R1
表示一種或兩種以上的烷基或芳基；R2
和R3
表示一種或兩種以上的亞烷基；R4
表示一種或兩種以上的烷基、醯基等（末端基）。做為聚醚基可以舉出：聚氧化乙烯基（(C2
H4
O)n
）、聚氧化丙烯基（(C3
H6
O)n
）等聚氧化亞烷基。
優選（J）聚醚改質矽氧烷化合物是HLB值為7～12的聚醚改質矽氧烷化合物。另外，相對於100重量份的共聚物，優選（J）聚醚改質矽氧烷化合物的含量為0.01～0.5重量份，更優選為0.1～0.5重量份。
HLB是指例如JIS K3211（表面活性劑用語）等規定的親水親油平衡（親水性與親油性的比值）。
聚醚改質矽氧烷化合物，例如，可藉由如下方法獲得：藉由氫化矽烷化反應，使具有不飽和鍵和聚氧化亞烷基的有機化合物接枝在具有矽烷基的聚有機矽氧烷的主鏈而獲得。具體而言，可以舉出：二甲基矽氧烷-甲基（聚氧化乙烯）矽氧烷共聚物，二甲基矽氧烷-甲基（聚氧化乙烯）矽氧烷-甲基（聚氧化丙烯）矽氧烷共聚物，二甲基矽氧烷-甲基（聚氧化丙烯）矽氧烷共聚物等。
藉由將（J）聚醚改質矽氧烷化合物配合於粘著劑組合物，能夠改善粘著劑的粘著力和再加工性能。
並且，做為其他成分，可適當地配合含有烯化氧(alkylene oxide)的可共聚的（甲基）丙烯酸單體、（甲基）丙烯醯胺單體、二烷基取代丙烯醯胺單體、表面活性劑、固化促進劑、增塑劑、填充劑、固化阻滯劑、加工助劑、抗老化劑、抗氧化劑等公知的添加劑。這些既可以單獨使用，也可以組合兩種以上使用。
用於本發明的粘著劑組合物的主劑共聚物，可藉由使（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體、（C）含有羧基的可共聚的單體以及（D）聚亞烷基二醇單（甲基）丙烯酸酯單體進行聚合而合成。對共聚物的聚合方法沒有特別的限定，可以使用溶液聚合、乳化聚合等適當的聚合方法。
當做為（I）抗靜電劑使用（I-2）含有丙烯醯基的四級銨鹽型離子化合物時，用於本發明的粘著劑組合物的主劑共聚物，可藉由使（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體、（C）含有羧基的可共聚的單體、（D）聚亞烷基二醇單（甲基）丙烯酸酯單體以及（I-2）含有丙烯醯基的四級銨鹽型離子化合物進行聚合而合成。
本發明的粘著劑組合物，可藉由在上述共聚物中配合（F）三官能以上的異氰酸酯化合物、（G）交聯阻滯劑、（H）交聯催化劑、（I）抗靜電劑、（J）聚醚改質矽氧烷化合物、還有適當的任意添加劑來進行配製。此外，若已經將（I-2）含有丙烯醯基的四級銨鹽型離子化合物聚合於主劑共聚物中的情況下，對共聚物既可以進一步添加（I）抗靜電劑，也可以不添加（I）抗靜電劑。
優選前述共聚物為丙烯酸類聚合物，優選含有50～100重量%的（甲基）丙烯酸酯單體或者（甲基）丙烯酸、（甲基）丙烯醯胺類等丙烯酸類單體。
另外，優選丙烯酸類聚合物的酸值為0.01～8.0。由此，能夠改善污染性並且提高防止粘著劑殘留現象發生的性能。
在此，“酸值”是表示酸含量的指標之一，是以中和1g含有羧基的聚合物所需要的氫氧化鉀的mg數來表示。
優選使前述粘著劑組合物交聯而成的粘著劑層在低剝離速度0.3m/min下的粘著力為0.05～0.1N/25mm，在高剝離速度30m/min下的粘著力為1.0N/25mm以下。由此，能夠獲得粘著力隨剝離速度的變化小的性能，即使是在高速剝離的情況下也可以迅速剝離。並且，即使為了重新粘貼而暫時剝離表面保護膜時，也無需過大的力量，易於從被粘附體剝離。
優選使前述粘著劑組合物交聯而成的粘著劑層的表面電阻率在5.0×10+10
Ω/□以下，剝離靜電壓為±0～0.3kV。此外，在本發明中，所謂“±0～0.3kV”的意思是指“0～－0.3kV”和“0～＋0.3kV”、即“－0.3～＋0.3kV”。若表面電阻率大，則對剝離時因帶電而產生的靜電進行釋放的性能差，因此，藉由使表面電阻率足夠小，能夠降低伴隨從被粘附體剝離粘著劑層時發生的靜電所產生的剝離靜電壓，能夠抑制對被粘附體的電控制電路等的影響。
優選使本發明的粘著劑組合物交聯而成的粘著劑層（交聯後的粘著劑）的凝膠分率為95～100％。由於凝膠分率如此高，在低剝離速度的情況下粘著力不會變得過大，降低了從共聚物中溶出未聚合單體或寡聚物的現象，從而能夠改善再加工性、高溫/高濕下的耐久性，並抑制被粘附體的污染。
本發明的粘著膜是在樹脂膜的單面或雙面形成粘著劑層而成，所述粘著劑層是使本發明的粘著劑組合物交聯而成。另外，本發明的表面保護膜是在樹脂膜的單面形成粘著劑層而成，所述粘著劑層是使本發明的粘著劑組合物交聯而成。在本發明的粘著劑組合物中，由於以良好的平衡性配合有上述（A）～（J）的各成分，所以具有優良的抗靜電性能，在低剝離速度和高剝離速度下的粘著力的平衡性優良，並且耐久性能以及再加工性能（用原子筆隔著粘著劑層在表面保護膜上進行描繪後，沒有向被粘附體轉移污染）也優良。因此，可優選做為偏光板的表面保護膜用途來使用。
做為粘著劑層的基材膜、保護粘著面的剝離膜（隔膜），可以使用聚酯膜等樹脂膜等。
對基材膜而言，可在樹脂膜的與形成有粘著劑層一側相反的面上，實施以矽酮類、氟類的脫模劑或塗層劑、二氧化矽微粒等進行的防污處理，可實施以抗靜電劑的塗佈或混入等進行的抗靜電處理。
對剝離膜而言，在與粘著劑層的粘著面進行貼合一側的面上，實施以矽酮類、氟類的脫模劑等進行的脫模處理。
實施例
下面，基於實施例具體說明本發明。
<丙烯酸共聚物的製造>
[實施例1]
向配有攪拌器、溫度計、回流冷凝器和氮導入管的反應裝置中導入氮氣，從而用氮氣置換了反應裝置內的空氣。然後，向反應裝置中加入了100重量份的丙烯酸2-乙基己酯、0.9重量份的丙烯酸8-羥基辛酯、0.5重量份的丙烯酸、3重量份的聚乙二醇單丙烯酸酯、5重量份的N-乙烯基吡咯烷酮，並同時加入60重量份的溶劑（乙酸乙酯）。然後，經過2小時滴入0.1重量份的做為聚合反應起始劑的偶氮二異丁腈，在65℃下使其反應6小時，獲得了重均分子量為50萬的、用於實施例1的丙烯酸共聚物溶液1。取丙烯酸共聚物的一部分，做為後述的酸值測定試樣使用。
[實施例2～9和比較例1～4]
除了如表1中的（A）～（E）和（I-2）所述地分別調整了各單體的組成以外，與上述用於實施例1的丙烯酸共聚物溶液1同樣地進行操作，獲得了用於實施例2～9和比較例1～4中的丙烯酸共聚物溶液。
表1
<粘著劑組合物和表面保護膜的製造>
[實施例1]
對按照如上所述製造的實施例1的丙烯酸共聚物溶液1，加入1.5重量份1-辛基吡啶鎓六氟磷酸鹽、0.2重量份KF-351A（HLB＝12的聚醚改質矽氧烷化合物）、2.5重量份乙酰丙酮並進行攪拌後，加入1.0重量份Coronate HX （コロネートHX、六亞甲基二異氰酸酯化合物的異氰脲酸酯）、0.2重量份Coronate L（コロネートL、甲苯二異氰酸酯化合物與三羥甲基丙烷的加成物）、0.02重量份二月桂酸二辛基錫後攪拌混合，獲得了實施例1的粘著劑組合物。將該粘著劑組合物塗佈於由塗有矽酮樹脂的聚對苯二甲酸乙二酯（PET）膜構成的剝離膜上，然後在90℃下進行乾燥而去除溶劑，獲得了粘著劑層厚度為25μm的粘著片。
然後，準備一個面上實施有抗靜電處理和防污處理的聚對苯二甲酸乙二酯（PET）膜，並將粘著片轉移至該聚對苯二甲酸乙二酯（PET）膜的與實施有抗靜電處理和防污處理的面的相反面上，獲得了具有“實施有抗靜電處理和防污處理的PET膜/粘著劑層/剝離膜（塗有矽酮樹脂的PET膜）”的層疊構成的實施例1的表面保護膜。
[實施例2～9和比較例1～4]
除了如表2的（F）～（J）所述地分別調整了各添加劑的組成以外，與上述實施例1的表面保護膜同樣地進行操作，獲得了實施例2～9和比較1～4的表面保護膜。
表2
表1和表2是將表示各成分配合比的整個表分成兩個部分的表，括弧內的數值均表示以（A）組的合計重量設為100重量份而求出的各成分重量份的數值。另外，將與表1和表2中使用的各成分的縮寫對應的化合物名稱示於表3和表4中。此外，Coronate（コロネート、註冊商標）HX、Coronate HL和Coronate L是日本聚氨酯工業股份有限公司（Nippon Polyurethane Industry Co., Ltd.）的商品名稱，Takenate（タケネート、註冊商標）D-140N、D-127N、D-110N、D-120N是三井化學股份有限公司的商品名稱，KF-351A、KF-352A、KF-353、KF-640和X-22-6191是信越化學股份有限公司的商品名稱。
在表1中，將（I）抗靜電劑中的、共聚於共聚物中的（I-2）含有丙烯醯基的四級銨鹽型離子化合物和聚合後添加的（I-1）熔點為30～80℃的離子化合物，分別記載於不同的欄中。
表3
表4
<試驗方法和評價>
在23℃、50％RH的環境下，將實施例1～9和比較例1～4的表面保護膜老化7天後，剝掉剝離膜（塗有矽酮樹脂的PET膜），從而使粘著劑層外露，並做為測定凝膠分率和表面電阻率的試樣。
進而，將該粘著劑層外露的表面保護膜，經由粘著劑層貼合於已粘貼在液晶單元上的偏光板表面，放置1天後在50℃、5個大氣壓下進行高壓鍋處理20分鐘，進一步在室溫下放置12小時，將由此得到的表面保護膜做為測定粘著力、剝離靜電壓和耐久性的試樣。
<酸值>
丙烯酸類聚合物的酸值：將試樣溶解於溶劑（將二乙醚和乙醇以體積比2:1進行混合的溶劑）中，採用電位差自動滴定裝置（AT-610，京都電子工業股份有限公司製造），用濃度約0.1mol/L的氫氧化鉀乙醇溶液進行電位差滴定，測定了用於中和試樣所需的氫氧化鉀乙醇溶液的量。然後，根據下式來求出酸值。
酸值＝（B×f×5.611）/S
B＝滴定中使用的0.1mol/L氫氧化鉀乙醇溶液的量（mL）
f＝0.1mol/L氫氧化鉀乙醇溶液的係數
S＝試樣的固體成分的品質（g）
<凝膠分率>
準確地測量老化結束後、貼合偏光板之前的測定試樣的品質，並在甲苯中浸漬24小時後，通過200篩目的金屬絲網進行過濾。然後，在100℃下乾燥過濾物1小時後，準確地測量殘留物的品質，並根據下式計算出粘著劑層（交聯後的粘著劑）的凝膠分率。
凝膠分率（％）＝不溶部分品質（g）/粘著劑品質（g）×100
<粘著力>
採用拉伸試驗機，以低剝離速度（0.3m/min）和高剝離速度（30m/min），向180°方向剝離上述所得到的測定試樣（將25mm寬的表面保護膜貼合於偏光板表面而成的試樣），測定了剝離強度，並將該剝離強度做為粘著力。
<表面電阻率>
在老化後、貼合偏光板之前，剝掉剝離膜（塗有矽酮樹脂的PET膜）而使粘著劑層外露，採用電阻率儀HirestaUP- HT450（ハイレスタUP-HT450、三菱化學分析技術股份有限公司（Mitsubishi Chemical Analytech Co.,Ltd）製造），測定了粘著劑層的表面電阻率。
<剝離靜電壓>
採用高精度靜電感測器SK-035、SK-200（基恩士股份有限公司（Keyence Corporation）製造），測定當對上述所得到的測定試樣以30m/min的拉伸速度進行180°剝離時，偏光板帶電而產生的電壓（靜電壓），將測定值的最大值做為剝離靜電壓。
<再加工性>
用原子筆在上述得到的測定試樣的表面保護膜上進行描繪（載荷為500g、來回3次）後，從偏光板剝離表面保護膜，觀察偏光板的表面，確認沒有向偏光板轉移污染。評價目標基準：當沒有向偏光板轉移污染時評價為“○”；當確認沿著原子筆描繪的軌跡至少向局部轉移了污染時評價為“△”；當確認沿著原子筆描繪的軌跡有污染轉移並且從粘著劑表面也確認有粘著劑的脫離時評價為“×”。
<耐久性>
在60℃、90％RH環境下放置上述所得到的測定試樣250小時後，將其取出置於室溫下進一步地放置12小時，然後測定粘著力，確認與初期粘著力相比較沒有明顯的增加。評價目標基準：當試驗後的粘著力是初期粘著力的1.5倍以下的情況評價為“○”、超過1.5倍的情況評價為“×”。
將評價結果示於表5中。另外，在表面電阻率中，通過“mE+n”來表示“m×10+n
”（其中，m為任意的實數，n為正整數）。
表5
對實施例1～9的表面保護膜而言，在低剝離速度0.3m/min下的粘著力是0.05～0.1N/25mm，在高剝離速度30m/min下的粘著力是1.0N/25mm以下；表面電阻率在5.0×10+10
Ω/□以下，剝離靜電壓為±0～0.3kV；並且，在使用原子筆隔著粘著劑層在表面保護膜進行描繪後，沒有向被粘附體轉移污染，而且在60℃、90％RH的環境下予以250小時放置後的耐久性也是優良的。
即，同時滿足了如下全部的性能要求：（1）取得低剝離速度和高速剝離速度下的黏著力的平衡性；（2）防止粘著劑殘留的發生；（3）優異的抗靜電性能；以及（4）再加工性能。
另外，通過併用選自（F-1）第一脂肪族類異氰酸酯化合物組中的一種以上和選自（F-2）第二芳香族類異氰酸酯化合物組中的一種以上，能夠改善低速剝離區域和高速剝離區域的粘著力的平衡性。
對比較例1的表面保護膜而言，其凝膠分率為0、在低剝離速度0.3m/min和高剝離速度30m/min下的粘著力過大、再加工性和耐久性差，這可能是由於不包含（D）聚亞烷基二醇單（甲基）丙烯酸酯單體和（E）含氮的乙烯基單體或者含有烷氧基的（甲基）丙烯酸烷基酯單體和（F）異氰酸酯化合物的緣故。
對比較例2的表面保護膜而言，其在低剝離速度0.3m/min下的粘著力和高剝離速度30m/min下的粘著力過大、剝離靜電壓高、再加工性和耐久性差、且凝膠分率低，這可能是由於（B）含有羥基的單體過少、（D）聚亞烷基二醇單（甲基）丙烯酸酯單體過少、不包括（E）含氮的乙烯基單體或者含有烷氧基的（甲基）丙烯酸烷基酯單體、（J）聚醚改質矽氧烷化合物的HLB值過小的緣故。
對比較例3的表面保護膜而言，其儲存期過短，由於在塗佈前已進行了交聯，因此，無法進行塗佈，這可能是因（F）異氰酸酯化合物過多、未配合（G）交聯阻滯劑的緣故。
對比較例4的表面保護膜而言，即使不含有（H）交聯催化劑，其儲存期也過短，並由於在塗佈前已進行了交聯，因此無法進行塗佈，這可能是因（F）異氰酸酯化合物過多的緣故。
如上所述，在比較例1～4的表面保護膜中，無法同時滿足如下全部的性能要求：（1）取得低剝離速度和高剝離速度下的粘著力的平衡性；（2）防止粘著劑殘留的發生；（3）優異的抗靜電性能；以及（4）再加工性能。
產業利用性
基於本發明的粘著劑組成物，能夠滿足在現有技術中無法解決的對表面保護膜的粘著劑層所要求的全部性能，而且還能夠獲得優良的抗靜電性能、防止粘著劑殘留的發生。另外，由於本發明的表面保護膜改善了低速剝離區域和高速剝離區域中的粘著力的平衡性，因此，在產業上的利用價值大。
Hereinafter, the present invention will be described based on preferred embodiments.
The adhesive composition of the present invention is characterized in that the main component is a (meth) acrylate monomer having (C) an alkyl group having a C4 to C10 carbon number and (B) a hydroxyl group-containing copolymerizable group. Monomer, (C) carboxyl group-containing copolymerizable monomer, (D) polyalkylene glycol mono(meth)acrylate monomer, and (E) hydroxyl-free and nitrogen-containing vinyl monomer Or an acrylic polymer containing a copolymer of at least one of alkoxyalkyl (meth)acrylate alkyl ester monomers, further containing (F) a trifunctional or higher isocyanate compound, and (G) a crosslinking retarder. And (H) a crosslinking catalyst, (I) an antistatic agent, and (J) a polyether modified siloxane compound, wherein the acrylic polymer has an acid value of 0.01 to 8.0.
Examples of the (meth) acrylate monomer having a CA to C10 carbon atom as the (A) alkyl group include butyl (meth)acrylate, isobutyl (meth)acrylate, and (methyl). Amyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Ethyl methacrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, and the like.
Examples of the (B) hydroxyl group-containing copolymerizable monomer include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. (hydroxy) (meth) acrylate such as 2-hydroxyethyl (meth)acrylate; N-hydroxy(meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyl A (meth) acrylamide containing a hydroxyl group such as ethyl (meth) acrylamide.
Preferably, the (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Composition of 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide At least one or more of the compound groups.
The (B) hydroxyl group-containing copolymerizable monomer is preferably contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the (A) alkyl group-containing (meth) acrylate monomer having a C4 to C10 carbon number.
Further, in (B) a hydroxyl group-containing copolymerizable monomer, a total of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate The amount is preferably less than 1 part by weight (may not be contained), and more preferably 0 to 0.9 part by weight.
Preferably, the (C) carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(methyl)acrylonitrile. Ethyl hexahydrophthalic acid, 2-(methyl) propylene methoxypropyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate, 2-(A Acryloxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propylene decyloxy At least one or more of the compound groups consisting of ethyltetrahydrophthalic acid.
The content of the (C) carboxyl group-containing copolymerizable monomer is preferably 0.35 to 1.0 part by weight based on 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer. More preferably, it is 0.35-0.6 weight part.
As the (D) polyalkylene glycol mono(meth)acrylate monomer, as long as one of the plurality of hydroxyl groups of the polyalkylene glycol is esterified to (meth)acrylate The compound can be. Since the (meth) acrylate group is a polymerizable group, it can be copolymerized with the main agent polymer. The other hydroxyl group may be in the state of OH, or may be an alkyl ether such as methyl ether or diethyl ether or a saturated carboxylic acid ester such as acetate.
The alkylene group which the polyalkylene glycol has may be a vinyl group, a propenyl group or a butenyl group, but is not limited thereto. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the copolymer of polyalkylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-poly Butanediol or the like, the copolymer may be a block copolymer or a random copolymer.
As the (D) polyalkylene glycol mono (meth) acrylate monomer, preferably selected from polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (A At least one of acrylate and ethoxypolyalkylene glycol (meth) acrylate.
More specifically, polyethylene glycol mono- (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol - polypropylene glycol mono- (meth) acrylate, polyethylene glycol - polybutylene glycol - mono (meth) acrylate, polypropylene glycol - polybutylene glycol - mono (meth) acrylate, polyethylene glycol - polypropylene glycol - polybutylene glycol - mono (meth) acrylate; methoxy polyethylene glycol - (meth) acrylate, methoxy polypropylene glycol - (meth) acrylate, methoxy poly butyl Glycol-(meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-(meth) acrylate, methoxy-polyethylene glycol-polybutylene glycol-(meth) acrylate, Methoxy-polypropylene glycol-polybutylene glycol-(meth)acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate; ethoxypolyethylene glycol -(Meth)acrylate, ethoxypolypropylene glycol-(meth)acrylate, ethoxylated polybutylene glycol-(meth)acrylate, ethoxy-polyethylene glycol-polypropylene glycol-(A Acrylate, ethoxy-polyethylene glycol-polybutylene glycol-(meth) acrylate, ethoxy-polypropylene glycol-polybutylene glycol-(meth) acrylate, ethoxy-poly Ethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate or the like.
It is preferable to contain 1 to 20 parts by weight of (D) polyalkylene glycol mono (methyl) with respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer. ) acrylate monomer.
In (E), as the (E-1) nitrogen-containing vinyl monomer, a vinyl monomer containing a guanamine bond, a vinyl monomer containing an amino group, and a heterocyclic structure having a nitrogen-containing structure may be mentioned. Vinyl monomer and the like. More specifically, N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylacridone, N-vinylpyrimidine, N-vinylpyridazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N a cyclic nitrogen vinyl compound having an N-vinyl substituted heterocyclic ring structure such as vinyl dodecanoin; N-(meth)acryl hydrazinomorpholine, N-(methyl) acrylonitrile fluorene Pyrazine, N-(methyl) acrylonitrile aziridine, N-(methyl) propylene decylpyridinium, N-(methyl) propylene decyl pyrrolidine, N-(methyl) propylene fluorenyl a heterocyclic structure having an N-(meth)acrylinyl group-substituted heterocyclic ring such as acridine, N-(methyl)acrylonitrile-azetidene or N-(methyl)propenylazepane a cyclic nitrogen-vinyl compound; a cyclic nitrogen-oxyethylene having a heterocyclic structure containing a nitrogen atom and a vinyl-based unsaturated bond in the ring, such as N-cyclohexylmaleimide or N-phenylmaleimide. Base compound; (methyl) Unsubstituted or monoalkyl substituted such as anilide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide (Meth) acrylamide; N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, N,N-dipropyl acrylamide, N , N-diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-A Dialkyl substituted (meth) acrylamide such as N-propyl-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide; N, N-dimethyl Aminomethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, N,N-dimethylaminopropyl (meth) acrylate, N, N-di Methylaminoisopropyl (meth) acrylate, N,N-dimethylaminobutyl (meth) acrylate, N,N-diethylaminomethyl (meth) acrylate, N, N -Diethylaminoethyl (meth) acrylate, N-ethyl-N-methylaminoethyl (meth) acrylate, N-methyl-N-propylamino (meth) acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, tert-butylamino Dialkylamino (meth) acrylate such as methacrylic acid ester; N,N-dimethylaminopropyl (meth) acrylamide, N,N-diethylaminopropyl (methyl) Acrylamide, N,N-dipropylaminopropyl(meth)acrylamide, N,N-diisopropylaminopropyl(meth)acrylamide, N-ethyl-N-A Aminopropyl propyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) propylene N,N-dialkyl substituted aminopropyl (meth) acrylamide of guanamine or the like; N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamidine N-vinyl carboxylic acid amides such as amines; N-methoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxymethyl ( Methyl) acrylamide, diacetone acrylamide, N,N-methylenebis(meth) acrylamide, etc. (meth) propylene Amine; (meth) acrylonitrile, unsaturated carboxylic acid nitriles and the like; and the like.
As the (E-1) nitrogen-containing vinyl monomer, it preferably does not contain a hydroxyl group, and more preferably does not contain a hydroxyl group and a carboxyl group. As such a monomer, preferred are the monomers exemplified above, for example, an acrylic monomer containing an N,N-dialkyl substituted amino group, an N,N-dialkyl substituted guanamine group; N-vinyl- N-vinyl substituted indoleamine such as 2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-acridone; N-(methyl)propenylmorpholine, N-(methyl N-(meth)acrylinyl substituted cyclic amines such as acrylamidopyrrolidine.
In (E), as the (E-2) alkoxy group-containing (meth)acrylic acid alkyl ester monomer, 2-methoxyethyl (meth)acrylate and (methyl) may be mentioned. 2-ethoxyethyl acrylate, 2-propoxyethyl (meth)acrylate, 2-isopropoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, ( 2-Methoxypropyl methacrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxy propyl (meth) acrylate Ester, 2-butoxypropyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 3-propoxy (meth)acrylate Propyl propyl ester, 3-isopropoxypropyl (meth) acrylate, 3-butoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylate 4 Ethoxybutyl ester, 4-propoxybutyl (meth)acrylate, 4-isopropoxybutyl (meth)acrylate, 4-butoxybutyl (meth)acrylate, and the like.
These alkoxy group-containing alkyl (meth)acrylate monomers have a structure in which an atom of an alkyl group in an alkyl (meth)acrylate is substituted with an alkoxy group.
With respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 carbon atom, it is preferred that (E-1) a hydroxyl group-free vinyl monomer or (E- 2) The content of the alkyl (meth) acrylate monomer containing an alkoxy group is 1 to 20 parts by weight. For (E-1) a hydroxyl group-free vinyl monomer and (E-2) an alkoxy group-containing alkyl (meth)acrylate monomer, one type may be used alone or two types may be used together. More than one species.
The (F) trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule. The polyisocyanate compound includes a classification of an aliphatic isocyanate, an aromatic isocyanate, an acyclic isocyanate, an alicyclic isocyanate, and the like, and the present invention may be any of them. Specific examples of the polyisocyanate compound include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMDI). a compound; diphenylmethane diisocyanate (MDI), benzodimethyl diisocyanate (XDI), hydrogenated dimethyl diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), toluene diisocyanate ( An aromatic isocyanate compound such as TDI).
Examples of the trifunctional or higher isocyanate compound include a biuret modified or an isocyanurate modified body of a diisocyanate (a compound having two NCO groups in one molecule), and a trihydroxyl group. An adduct (polyol modified body) of a trivalent or higher polyvalent alcohol (a compound having at least three or more OH groups in one molecule) such as a propane (TMP) or glycerin.
Further, the (F) trifunctional or higher isocyanate compound used in the present invention preferably includes at least one selected from the group consisting of (F-1) first aliphatic isocyanate compounds and selected from (F-2) At least one or more of the group of diaromatic isocyanate compounds, wherein the (F-1) first aliphatic isocyanate compound group is an isocyanurate or isophorone derived from a hexamethylene diisocyanate compound Isocyanurate of an isocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, isophorone a biuret of a diisocyanate compound; the (F-2) second aromatic isocyanate compound group is an isocyanurate of a toluene diisocyanate compound, an isocyanuric acid of a benzene dimethylene diisocyanate compound An isocyanurate of an ester, a hydrogenated benzyl diisocyanate compound, an adduct of a toluene diisocyanate compound, an adduct of a benzene dimethylene diisocyanate compound, and hydrogenation An adduct of a benzenedimethyl diisocyanate compound. Preferably, (F-1) a first aliphatic isocyanate compound group and (F-2) a second aromatic isocyanate compound group are used in combination. In the present invention, as the (F) trifunctional or higher isocyanate compound, at least one selected from the group consisting of (F-1) a first aliphatic isocyanate compound and a second selected from (F-2) are used in combination. At least one or more of the aromatic isocyanate compound groups can further improve the balance of the adhesive force in the low-speed peeling region and the high-speed peeling region.
Further, it is preferable that the (F) trifunctional or higher isocyanate compound includes at least one selected from the group consisting of the above (F-1) first aliphatic isocyanate compound group and a second aromatic isocyanate compound selected from the above (F-2). At least one or more of the group, and the total content of the (F) trifunctional or higher isocyanate compound is from 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer. Further, as a mixing ratio of at least one or more selected from the group consisting of (F-1) a first aliphatic isocyanate compound group and at least one selected from the group consisting of (F-2) a second aromatic isocyanate compound, The weight ratio calculation is preferably (F-1): (F-2) in the range of 10%: 90% to 90%: 10%.
As the (G) cross-linking retarder, there may be mentioned ethyl acetonitrile acetate, ethyl acetate, octyl acetate, ethyl acetoacetate, lauryl acetate, and ethyl acetate. a β-ketoester such as an oxime ester; a β-diketone such as acetamidineacetone, 2,4-hexanedione or benzamidineacetone. These are ketoenol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group which the crosslinking agent has, it can suppress sticking after mixing a crosslinking agent. The phenomenon that the viscosity of the coating composition is excessively increased or gelled can prolong the storage period of the adhesive composition.
The (G) crosslinking retarder is preferably a ketoenol tautomer compound, and particularly preferably at least one selected from the group consisting of ethyl acetate and ethyl acetate.
The content of the (G) crosslinking retarder is preferably 1.0 to 5.0 parts by weight based on 100 parts by weight of the copolymer.
When the polyisocyanate compound is used as the crosslinking agent, the (H) crosslinking catalyst may be one which functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and may be mentioned. An amine compound such as a tertiary amine, an organotin compound such as an organotin compound, an organic lead compound or an organozinc compound.
Examples of the tertiary amine include trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylamino alcohol, triethylenediamine, and morpholine derivatives. Pyridazine derivatives and the like.
Examples of the organotin compound include a dialkyl tin oxide, a fatty acid salt of a dialkyl tin, a fatty acid salt of stannous, and the like.
The (H) crosslinking catalyst is preferably an organotin compound, and particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.
The content of the (H) crosslinking catalyst is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the copolymer.
Preferably, the (I) antistatic agent is (I-1) an ionic compound having a melting point of 30 to 80 ° C or (I-2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group.
In the present invention, as the (I) antistatic agent, (I-1) an ionic compound having a melting point of 30 to 80 ° C is added to the copolymer, or (I-2) a quaternary ammonium salt containing an acrylonitrile group. The salt type ionic compound is copolymerized in the copolymer. It is presumed that since these (I) antistatic agents have a low melting point and a long-chain alkyl group, they have high affinity with an acrylic copolymer.
The ionic compound having a melting point of 30 to 80 ° C (I-1) is an ionic compound having a cation and an anion, and examples thereof include a cation cation cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, and a pyrrole. cation, an ammonium cation such as a nitrogen-containing cation or a phosphonium cation, sulfonium cation, the anion is hexafluorophosphate (PF -6), thiocyanate (SCN -), alkyl sulfonate (RC 6 H 4 A compound of an inorganic or organic anion such as SO 3 - ), perchlorate (ClO 4- ) or tetrafluoroborate (BF 4 - ). It is preferably a solid at normal temperature (for example, 30 ° C), and a compound having a melting point of 30 to 80 ° C can be obtained by selecting the chain length of the alkyl group, the position and number of the substituent, and the like. The cation is preferably a quaternary nitrogen sulfonium cation, and examples thereof include a 4-alkylpyridinium cation such as 1-alkylpyridinium (having a substituent or a substituent at a carbon atom of 2 to 6), and 1,3. a quaternary imidazolium cation such as a dialkylimidazolium (a carbon atom at the 2, 4 or 5 position may have a substituent or a substituent), or a quaternary ammonium cation such as a tetraalkylammonium.
The content of the ionic compound having a melting point of (I-1) of 30 to 80 ° C is preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the copolymer.
As the (I-2) quaternary ammonium salt type ionic compound containing an acryl fluorenyl group, it is an ionic compound having a cation and an anion, and the cation is (meth) propylene decyloxyalkyltrialkylammonium ( R 3 N + -C n H 2n -OCOCQ=CH2, wherein Q=H or CH 3 , R=alkyl), etc., a quaternary ammonium ion containing a (meth) acrylonitrile group; an anion is a hexafluorophosphate (PF 6 - ), thiocyanate (SCN - ), organic sulfonate (RSO 3 - ), perchlorate (ClO 4 - ), tetrafluoroborate (BF 4 - ), F-containing imide ( A compound of an inorganic or organic anion such as R F 2 N - ). As a F-containing imine root ( The R F may, for example, be a perfluoroalkylsulfonyl group such as a trifluoromethanesulfonyl group or a pentafluoroethanesulfonyl group or a fluorosulfonyl group. As the F-containing imine root, bis(fluorosulfonyl) ruthenium [(FSO 2 ) 2 N - ], bis(trifluoromethanesulfonyl) fluorenylene ([CF 3] SO 2 ) 2 N - 〕, bis(sulfonyl sulfonyl) ruthenium root [(C 2 F 5 SO 2 ) 2 N - ), etc.
(I-2) A quaternary ammonium salt type ionic compound containing an acrylonitrile group, and the copolymerization amount in the copolymer is preferably 0.1 to 5.0% by weight.
Specific examples of the (I) antistatic agent are not particularly limited, but specific examples of the ionic compound having a melting point of (I-1) of 30 to 80 ° C include 1-octylpyridinium hexafluorophosphate. , 1-mercaptopyridinium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecane Pyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like. Further, specific examples of the quaternary ammonium salt type ionic compound containing (I-2) an acrylonitrile group include dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [(CH 3 ) 3 N + CH 2 OCOCQ=CH 2 • PF 6 - , wherein, Q=H or CH 3 ], dimethylaminoethyl (meth) acrylate bis(trifluoromethanesulfonyl) quinone imine Base salt [(CH 3 ) 3 N + (CH 2 ) 2 OCOCQ=CH 2 • ( 2 N - , wherein, Q=H or CH 3 ], dimethylaminomethyl methacrylate bis(fluorosulfonyl) quinone imine methyl salt [(CH 3 ) 3 N + CH 2 OCOCQ=CH 2 • (FSO 2 ) 2 N - , where Q = H or CH 3 〕 and so on.
(J) The polyether modified siloxane compound is a siloxane compound having a polyether group, and has a polyether group-containing oxime in addition to the usual siloxane unit (-SiR 1 2 -O-) Alkane unit (-SiR 1 (R 2 O(R 3 O) n R 4 )-O-). Here, R 1 represents one or two or more alkyl groups or aryl groups; R 2 and R 3 represent one or two or more alkylene groups; and R 4 represents one or two or more alkyl groups, fluorenyl groups and the like ( End base). The polyether group may, for example, be a polyoxyalkylene group such as a polyoxyethylene group ((C 2 H 4 O) n ) or a polyoxypropylene group ((C 3 H 6 O) n ).
Preferably, the (J) polyether modified oxirane compound is a polyether modified oxirane compound having an HLB value of from 7 to 12. Further, the content of the (J) polyether modified siloxane compound is preferably 0.01 to 0.5 part by weight, more preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the copolymer.
HLB is a predetermined hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) such as JIS K3211 (surfactant term).
The polyether modified oxoxane compound can be obtained, for example, by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group to a polyorganosiloxane having a decyl group by a hydrogenation oximation reaction. Obtained from the main chain of the alkane. Specifically, a dimethyl methoxy oxane-methyl (polyoxyethylene) decane copolymer, dimethyl methoxy oxane-methyl (polyoxyethylene) decane-methyl (poly) A propylene oxide) siloxane copolymer, a dimethyl methoxy oxane-methyl (polyoxypropylene) siloxane copolymer, or the like.
By blending the (J) polyether modified oxoxane compound with the adhesive composition, the adhesive strength and reworkability of the adhesive can be improved.
Further, as other components, a copolymerizable (meth)acrylic monomer, a (meth)acrylamide monomer, a dialkyl-substituted acrylamide monomer containing an alkylene oxide may be appropriately blended. A known additive such as a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, an anti-aging agent, and an antioxidant. These may be used alone or in combination of two or more.
The main agent copolymer used in the adhesive composition of the present invention may be a (meth) acrylate monomer having (C) an alkyl group having a C4 to C10 carbon number, and (B) a hydroxyl group-containing one. The copolymerized monomer, (C) a carboxyl group-containing copolymerizable monomer, and (D) a polyalkylene glycol mono(meth)acrylate monomer are polymerized and synthesized. The polymerization method of the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.
When (I) an acrylonitrile-containing quaternary ammonium salt type ionic compound is used as the (I) antistatic agent, the main agent copolymer used in the adhesive composition of the present invention can be made by (A) a (meth) acrylate monomer having an alkyl group having from C4 to C10, (B) a copolymerizable monomer having a hydroxyl group, (C) a carboxyl group-containing copolymerizable monomer, and (D) poly Asian The alkyl diol mono(meth) acrylate monomer and (I-2) a quaternary ammonium salt type ionic compound containing an acryl fluorenyl group are synthesized by polymerization.
In the adhesive composition of the present invention, (F) a trifunctional or higher isocyanate compound, (G) a crosslinking retarder, (H) a crosslinking catalyst, and (I) an antistatic agent may be blended in the above copolymer. And (J) a polyether modified oxoxane compound, and any suitable additives for formulation. Further, in the case where (I-2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group has been polymerized in the main agent copolymer, the (I) antistatic agent may or may not be further added to the copolymer. Add (I) an antistatic agent.
The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100% by weight of a (meth) acrylate monomer or an acrylic monomer such as (meth)acrylic acid or (meth)acrylamide.
Further, the acrylic polymer preferably has an acid value of 0.01 to 8.0. Thereby, it is possible to improve the staining property and improve the performance of preventing the occurrence of the adhesive residue.
Here, the "acid value" is one of the indexes indicating the acid content, and is expressed by the number of mg of potassium hydroxide required to neutralize 1 g of the carboxyl group-containing polymer.
Preferably, the adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition has an adhesive force at a low peeling speed of 0.3 m/min of 0.05 to 0.1 N/25 mm, and an adhesive force at a high peeling speed of 30 m/min of 1.0. N/25mm or less. Thereby, it is possible to obtain a performance in which the change in the adhesive force with the peeling speed is small, and it is possible to quickly peel off even in the case of high-speed peeling. Further, even if the surface protective film is temporarily peeled off for re-sticking, it does not require excessive force and is easily peeled off from the adherend.
The adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition preferably has a surface resistivity of 5.0 × 10 + 10 Ω / □ or less and a peeling static voltage of ± 0 to 0.3 kV. Further, in the present invention, "±0 to 0.3 kV" means "0 to -0.3 kV" and "0 to +0.3 kV", that is, "-0.3 to +0.3 kV". When the surface resistivity is large, the performance of releasing static electricity due to charging at the time of peeling is poor. Therefore, by making the surface resistivity sufficiently small, it is possible to reduce static electricity generated when the adhesive layer is peeled off from the adherend. The generated peeling static voltage can suppress the influence on the electric control circuit or the like of the adherend.
The adhesive layer (adhesive after crosslinking) obtained by crosslinking the pressure-sensitive adhesive composition of the present invention preferably has a gel fraction of 95 to 100%. Since the gel fraction is so high, the adhesion does not become excessive at a low peeling speed, and the phenomenon of eluting unpolymerized monomers or oligomers from the copolymer is lowered, so that reworkability and high temperature can be improved. Durability under high humidity and suppression of contamination by adherends.
The pressure-sensitive adhesive film of the present invention is obtained by forming an adhesive layer on one or both sides of a resin film which is obtained by crosslinking the pressure-sensitive adhesive composition of the present invention. Further, the surface protective film of the present invention is obtained by forming an adhesive layer on one surface of a resin film which is obtained by crosslinking the pressure-sensitive adhesive composition of the present invention. In the adhesive composition of the present invention, since the components (A) to (J) described above are blended with good balance, they have excellent antistatic properties and are sticky at a low peeling speed and a high peeling speed. The balance of the force is excellent, and the durability and the reworkability (the ink is not transferred to the adherend after being drawn on the surface protective film with the pen holder through the adhesive layer) is also excellent. Therefore, it can be preferably used as a surface protective film of a polarizing plate.
As the base film of the pressure-sensitive adhesive layer and the release film (separator) for protecting the adhesive surface, a resin film such as a polyester film or the like can be used.
The base film can be formed on the surface of the resin film opposite to the side on which the pressure-sensitive adhesive layer is formed by using an anthrone or a fluorine-based release agent, a coating agent, cerium oxide particles or the like. The antifouling treatment can be carried out by an antistatic treatment by application or mixing of an antistatic agent.
In the release film, a release treatment by a release agent such as an anthrone or a fluorine is carried out on the surface on the side where the adhesive surface of the pressure-sensitive adhesive layer is bonded.
EXAMPLES Hereinafter, the present invention will be specifically described based on examples.
<Manufacture of Acrylic Copolymer>
[Example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, thereby replacing the air in the reaction apparatus with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of 8-hydroxyoctyl acrylate, 0.5 parts by weight of acrylic acid, 3 parts by weight of polyethylene glycol monoacrylate, and 5 were added to the reaction apparatus. Parts by weight of N-vinylpyrrolidone and 60 parts by weight of a solvent (ethyl acetate) were simultaneously added. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain a weight average molecular weight of 500,000, which was used in the examples. 1 acrylic copolymer solution 1. A part of the acrylic copolymer was used as an acid value measurement sample to be described later.
[Examples 2 to 9 and Comparative Examples 1 to 4]
Except that the composition of each monomer was adjusted as described in (A) to (E) and (I-2) in Table 1, the operation was carried out in the same manner as in the above-described acrylic copolymer solution 1 used in Example 1, The acrylic copolymer solutions used in Examples 2 to 9 and Comparative Examples 1 to 4 were obtained.
Table 1
<Manufacture of Adhesive Composition and Surface Protective Film>
[Example 1]
To the acrylic copolymer solution 1 of Example 1 produced as described above, 1.5 parts by weight of 1-octylpyridinium hexafluorophosphate and 0.2 parts by weight of KF-351A (HB=12 polyether modified oxirane) were added. After compounding 2.5 parts by weight of acetylacetone and stirring, 1.0 part by weight of Coronate HX (isocyanuric acid ester of hexamethylene diisocyanate compound), 0.2 part by weight of Coronate L, and toluene diisocyanate were added. The compound and the trimethylolpropane adduct) and 0.02 parts by weight of dioctyltin dilaurate were stirred and mixed to obtain the adhesive composition of Example 1. The adhesive composition was applied onto a release film composed of a polyethylene terephthalate (PET) film coated with an fluorenone resin, and then dried at 90 ° C to remove the solvent to obtain adhesion. The adhesive layer had a thickness of 25 μm.
Then, a polyethylene terephthalate (PET) film having an antistatic treatment and an antifouling treatment on one surface is prepared, and the adhesive sheet is transferred to the polyethylene terephthalate (PET) film. On the opposite side of the surface on which the antistatic treatment and the antifouling treatment were carried out, a PET film/adhesive layer/release film (PET film coated with an anthrone resin) having antistatic treatment and antifouling treatment was obtained. The surface protective film of Example 1 which is laminated.
[Examples 2 to 9 and Comparative Examples 1 to 4]
Except that the composition of each additive was adjusted as described in (F) to (J) of Table 2, the same operation as the surface protective film of Example 1 was carried out, and Examples 2 to 9 and Comparative Examples 1 to 4 were obtained. Surface protection film.
Table 2
Table 1 and Table 2 are tables in which the entire table showing the mixing ratio of each component is divided into two parts, and the numerical values in the parentheses indicate the weights of the respective components obtained by setting the total weight of the group (A) to 100 parts by weight. Value. Further, the names of the compounds corresponding to the abbreviations of the respective components used in Tables 1 and 2 are shown in Tables 3 and 4. In addition, Coronate (registered trademark) HX, Coronate HL and Coronate L are trade names of Nippon Polyurethane Industry Co., Ltd., Takenate (registered trademark) D-140N, D- 127N, D-110N, and D-120N are trade names of Mitsui Chemicals Co., Ltd., and KF-351A, KF-352A, KF-353, KF-640, and X-22-6191 are trade names of Shin-Etsu Chemical Co., Ltd.
In Table 1, (I) the (I-2) quaternary ammonium salt type ionic compound containing an acryl oxime group copolymerized in the copolymer and the melting point of (I-1) added after polymerization in the (I) antistatic agent are The ionic compounds at 30 to 80 ° C are described in separate columns.
table 3
Table 4
<Test method and evaluation>
The surface protective films of Examples 1 to 9 and Comparative Examples 1 to 4 were aged for 7 days in an environment of 23 ° C and 50% RH, and then the release film (PET film coated with an anthrone resin) was peeled off to make it sticky. The coating layer was exposed and used as a sample for measuring the gel fraction and surface resistivity.
Further, the surface protective film exposed to the pressure-sensitive adhesive layer was bonded to the surface of the polarizing plate adhered to the liquid crystal cell via an adhesive layer, and left for 1 day, and then subjected to autoclave treatment at 50 ° C and 5 atm for 20 minutes. Further, it was allowed to stand at room temperature for 12 hours, and the surface protective film thus obtained was used as a sample for measuring adhesion, peeling static voltage, and durability.
<acid value>
Acid value of acrylic polymer: The sample is dissolved in a solvent (a solvent in which diethyl ether and ethanol are mixed at a volume ratio of 2:1), and an electric potential difference automatic titrator (AT-610, manufactured by Kyoto Electronics Industry Co., Ltd.) is used. The potentiometric titration was carried out with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol/L, and the amount of the potassium hydroxide ethanol solution required for neutralizing the sample was measured. Then, the acid value was determined according to the following formula.
Acid value = (B × f × 5.611) / S
B = amount of 0.1 mol/L potassium hydroxide ethanol solution used in the titration (mL)
f=0.1mol/L coefficient of potassium hydroxide ethanol solution
S = quality of the solid component of the sample (g)
<gel fraction>
The quality of the measurement sample after the aging was completed and before the polarizing plate was bonded was accurately measured, and after immersing in toluene for 24 hours, it was filtered through a 200 mesh mesh. Then, after drying the filtrate at 100 ° C for 1 hour, the quality of the residue was accurately measured, and the gel fraction of the adhesive layer (adhesive after crosslinking) was calculated according to the following formula.
Gel fraction (%) = insoluble portion quality (g) / adhesive quality (g) × 100
<adhesion>
Using a tensile tester, the above-obtained measurement sample was peeled off at a low peeling speed (0.3 m/min) and a high peeling speed (30 m/min) in a 180° direction (a 25 mm wide surface protective film was attached to the polarized light). The sample formed on the surface of the plate was measured for peel strength, and the peel strength was used as the adhesion.
<surface resistivity>
After aging, before peeling off the polarizing plate, peeling off the peeling film (PET film coated with fluorenone resin) to expose the adhesive layer, using a resistivity meter HirestaUP-HT450 (ハイレスタUP-HT450, Mitsubishi Chemical Analysis Technology Co., Ltd. The surface resistivity of the adhesive layer was measured by the company (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
<peeling static voltage>
Using a high-precision electrostatic sensor SK-035, SK-200 (manufactured by Keyence Corporation), the measurement sample obtained above was subjected to 180° peeling at a tensile speed of 30 m/min. At the time, the voltage (static voltage) generated when the polarizing plate is charged is used, and the maximum value of the measured value is taken as the peeling static voltage.
<Reworkability>
The surface protective film of the measurement sample obtained above was drawn with a ball pen (loading was 500 g, three times back and forth), and the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed, and it was confirmed that no contamination was transferred to the polarizing plate. Evaluation target criterion: when the contamination is not transferred to the polarizing plate, it is evaluated as "○"; when it is confirmed that the trajectory drawn along the atomic pen is at least partially transferred to the pollution, it is evaluated as "△"; when it is confirmed that the trajectory drawn along the atomic pen has The contamination was transferred and evaluated as "X" when the adhesion of the adhesive was also confirmed from the surface of the adhesive.
<Durability>
After the measurement sample obtained above was placed in an environment of 60 ° C and 90% RH for 250 hours, it was taken out and left at room temperature for further 12 hours, and then the adhesion was measured, and it was confirmed that there was no significant difference from the initial adhesion. increase. Evaluation target criterion: When the adhesion after the test was 1.5 times or less of the initial adhesion, it was evaluated as "○", and when it was more than 1.5 times, it was evaluated as "X".
The evaluation results are shown in Table 5. Further, the surface resistivity by "mE + n" to represent "m × 10 + n" (where, m is an arbitrary real numbers, n-is a positive integer).
table 5
The surface protective films of Examples 1 to 9 had an adhesive force at a low peeling speed of 0.3 m/min of 0.05 to 0.1 N/25 mm, and an adhesive force at a high peeling speed of 30 m/min of 1.0 N/25 mm or less. The surface resistivity is 5.0×10 +10 Ω/□ or less, and the peeling static voltage is ±0 to 0.3 kV; and, after being drawn on the surface protective film with the pen holder through the adhesive layer, it is not adhered to The body transfer was contaminated, and the durability after leaving it for 250 hours in an environment of 60 ° C and 90% RH was also excellent.
That is, all of the following performance requirements are satisfied: (1) achieving balance of adhesion at low peeling speed and high-speed peeling speed; (2) preventing occurrence of adhesive residue; (3) excellent antistatic property; And (4) reworkability.
In addition, by using one or more selected from the group consisting of (F-1) the first aliphatic isocyanate compound and one or more selected from the group consisting of the (F-2) second aromatic isocyanate compound, the low-speed peeling region and the low-speed peeling region can be improved. The balance of adhesion in the high speed peeling zone.
The surface protective film of Comparative Example 1 had a gel fraction of 0, an excessive adhesion at a low peeling speed of 0.3 m/min, and a high peeling speed of 30 m/min, and poor reworkability and durability, which may be Since (D) polyalkylene glycol mono(meth)acrylate monomer and (E) nitrogen-containing vinyl monomer or alkoxy-containing alkyl (meth)acrylate monomer are not contained and F) The reason for the isocyanate compound.
The surface protective film of Comparative Example 2 had an excessive adhesion at a low peeling speed of 0.3 m/min and a high peeling speed of 30 m/min, a high peeling static voltage, poor workability and durability, and The gel fraction is low, which may be due to (B) too little hydroxyl group-containing monomer, (D) polyalkylene glycol mono(meth)acrylate monomer too small, excluding (E) nitrogen-containing vinyl The HLB value of the monomer or the alkyl (meth) acrylate monomer containing the alkoxy group and the (J) polyether modified siloxane compound is too small.
The surface protective film of Comparative Example 3 had a short storage period, and since it was crosslinked before coating, coating could not be performed. This may be because the (F) isocyanate compound was excessive and uncoordinated (G). The reason for cross-linking retarders.
The surface protective film of Comparative Example 4 had a storage period too short even if it did not contain the (H) crosslinking catalyst, and since it was crosslinked before coating, coating could not be performed, which may be due to (F) Excessive isocyanate compound.
As described above, in the surface protective films of Comparative Examples 1 to 4, all of the following performance requirements could not be satisfied at the same time: (1) achieving a balance of adhesion at a low peeling speed and a high peeling speed; (2) preventing adhesion The occurrence of agent residues; (3) excellent antistatic properties; and (4) reworkability.
INDUSTRIAL APPLICABILITY The adhesive composition according to the present invention can satisfy all the properties required for the adhesive layer of the surface protective film which cannot be solved in the prior art, and can also obtain excellent antistatic properties and prevent adhesion. The occurrence of agent residues. Further, since the surface protective film of the present invention improves the balance of the adhesive force in the low-speed peeling region and the high-speed peeling region, it is industrially valuable.