TW201107439A - Pressure sensitive adhesive composition for electrically conductive member, and a laminate made by using such composition - Google Patents
Pressure sensitive adhesive composition for electrically conductive member, and a laminate made by using such composition Download PDFInfo
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201107439 六、發明說明: 【發明所屬之技術領域】 ,而ΐ發,:有關導電構件用感壓式接著劑組成物,更詳 :用二導ΐ構:在觸控式面板等所使用之導電構件之接著 物而錢㈣Μ壓式接著劑組成物,以及仙該組成 物而成的導電構件用成厭a > # κ 控式面板用薄Γ壓式接著劑薄片'積層趙、以及觸 【先前技術】 在個人電腦或電視等各種製品邁向普及化,尤其在電 子記事本、行動電話等也逐漸邁向小型化下,液晶顯示農 置係作為任何電子機器之顯示裝置而被廣泛地利用。在如 此之液晶顯示裝置等之中’有該顯示晝面會發揮作為觸控 式面板用薄片之機能,操作者以手指碰觸該顯示晝面上之 預定處而指定操作,亦即具有所謂的觸控式面板用模組者。 在觸控式面板之結構中,玻璃基板或透明樹脂基板、 與以no t透明導電膜或金屬電路為首之導電構件,係萨 由感壓式接著劑層來黏貼。由該玻璃基板或透明樹P基ς /感,接著劑層/透明電極(導電構件)所構成:積屏 體’右放置在南溫下或向溫高濕條件下,則在感 劑層與被黏體之黏貼界面會產生氣泡(發泡),.合 自被黏體浮起’或是會剝離。因此’針對所使用:咸:: 接著劑,一直以來就試著改良成使其即使在嚴t戸咸式 不會產生發泡、浮起、剝離。 可衣境下也 並且,對於上述錢式接著顚,要求在_離方向 322162 3 201107439 施加強力時亦不會剝離的高接著力。 . 直到目前為止,對於上述感壓式接著劑層,一直是進 行主要以丙烯酸系樹脂作為基材的感壓式接著劑的使用的 « 檢討(專利文獻1、2)。 使用以丙烯酸系樹脂作為基材的感壓式接著劑時,為 了提高與前述導電構件之接著性,有必要在基材樹脂中導 入酸基。然而,所導入之酸基會腐蝕作為被黏體的導電構 件,而引起運作不良等。 又,已經針對以胺酯尿素(urethane-urea)樹脂作為基 材之感壓式接著劑的各種用途上的應用進行過檢討。但 是,有關如上述的表現高接著性或應用於導電構件之檢 討,到目前為止則完全未曾進行過(專利文獻3、4、5)。 [先前技術文獻] (專利文獻) 專利文獻1 :日本特開2006-45315號公報 專利文獻2:日本特開2008-120864號公報 專利文獻3 :日本特開2002-121256號公報 專利文獻4:日本特開2002-38119號公報 專利文獻5 :日本特開2003-137963號公報 【發明内容】 (發明欲解決之課題) 本發明之目的是提供一種導電構件用感壓式接著劑組 成物,其在以ITO為首之透明導電膜或金屬電路等導電構 件中,不會引起因腐蝕而造成之運作不良等,在高溫或是 4 322162 201107439 南溫南濕條件下也不容易產生發泡或剝離, •劑耐性或良好之加工性,進而有高的接著性。之可塑 , 本發明人等為了解決上述課題,經過專心研办 果,發現藉由以下所示之感壓式接著劑組成物^之結 述目的,遂而完成本發明。 運成上 亦即,第1之本發明是有關:一種導電構件用感壓式 接著劑組成物,其含有重量平均分子量(Mw)為5〇,⑽〇 ^ 200’ 000之胺酯尿素樹脂、與相對於前述胺酯尿素樹脂 (A)100重量份而為01至3重量份之硬化劑(B);其中, 刖述胺酯尿素樹脂(A)是由使多元醇與多異氰酸酯 (polyis〇Cyanate,也稱聚異氰酸酯)(b)反應而得之胺酯預 聚物(urethane prepolymer)與多胺基化合物(c)反應而成 者。 第2之本發明是有關:如第1之本發明之導電構件用 感壓式接著劑組成物,其中,多異氰酸酯(b)之使用量在前 述胺酯尿素樹脂(A)之合成原料1〇〇重量%中佔有8至23重 量%,前述多胺基化合物(c)之使用量在前述胺酯尿素樹脂 (A)之合成原料1〇〇重量%中佔有0.5至8重量%。 第3之本發明是有關:如第1或第2之本發明之導電 構件用感壓式接著劑組成物,其中,多元醇(a)包含具有聚 丙二醇骨幹之多元醇。 第4之本發明是有關:如第1至第3中任一項之本發 明之導電構件用感壓式接著劑組成物,其中,硬化劑(B) 包含選自由六亞甲基二異氰酸酯三羥甲基丙烷加成體、六 322162 5 201107439 亞甲基二異氰酸酯三聚異氰酸酯 (hexamethylendiisocyanateisocyanurate)體、六亞甲基 二異氰酸酯縮二脲體、及伸笨二甲基二異氰酸酯三羥甲基 丙烷加成體所成群組中之至少1個。 第5之本發明是有關:如第1至第4中任一項之本發 明之導電構件用感壓式接著劑組成物,其中,相對於胺自旨 尿素樹脂(A)100重量份,含有0.1至1.〇重量份之選自由 3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三乙 氧基矽烷、及具有咪唑基之矽烷偶合劑所成群組中之任何 1種以上。 第6之本發明是有關:—種導電構件用感壓式接著性 薄片,其含有薄片狀基材、與在前述薄片狀基材之單面或 兩面上所形成之感壓式接著劑層,其中,前述感壓式接著 劑層1 系由第1至第5中任1之本發明之導電構件用感壓 式^者劑組成物所形成者。亦即,第6之本㈣是有關一 種導電構件用感塵式接著性薄片,其係將由第ι至第 任-項之本發蚊冑電構件肖錢式接 :感壓式接著劑層形成在薄片狀基材之單面或= 第7之本發明是有關:一種積層體 或透明料構件、與在前 “有導電構件 =::=本: 組成物所形成者。亦即,第7之本發 322162 6 201107439 其係在導電構件上積層由第1至第5中任一項之本發明之 導電構件用感壓式接著劑組成物所形成之感壓式接著劑層 . 而成者。 第8之本發明是有關:如第7之本發明的積層體,其 中,導電構件為透明導電祺或金屬電路。 第9及第10之本發明是有關:一種觸控式面板用薄 片,其分別具有第7或第8之本發明的積層體。 【實施方式】 藉由本發明可提供一種在以ΙΤ0為首之透明導電膜或 金屬電路等導電構件中,不會引起因腐餘而造成之運作不 良等,财熱性及财濕熱性優良,其有良好之可塑劑耐性或 良好之加工性,進而具有高接著性之導電構件用感壓式接 著劑組成物(以下’亦簡單記為「感壓式接著·成 「接著劑組成物」)。 首先’對於胺醋尿素樹脂(A)進行說明。胺酉旨尿素樹脂 (A)是由使多元醇(a)與多異氰酸酯(b)反應而得之胺酯預 聚物與多胺基化合物(c)反應而成,且重量平均分子量 為50,000至200, 000之樹脂。 作為使用之多元醇(a)者可使用習知者,可列舉如.聚 醚多元醇類、聚酯多元醇類、聚碳酸酯多元醇類、此等之 共聚合物、及其他之二醇(glycol)類等。以下所述之具體 化合物也可使用複數種之組合。 作為聚醚多元醇類者’可使用習知的聚鍵多元醇。例 如可使用:環氧丙烷(propylene oxide)、四氣咬喃、淨氧 322162 7 201107439 =私環氧τ財環纽之聚合物、共聚合物、及接枝共 、口,己二醇、F基己二醇、庚二醇、辛二醇、或此等 物的藉由縮合而成之聚醚多元醇類等具有2個以上 類加成環氧 又可使用經由在雙紛Α或雙紛F等雙紛 乙烧等環氧烧而成之二醇類。 作為聚酯多元醇類者,可使用習知的聚酯多元醇。 為聚酯多元醇者,例如可使用多官能醇成分與二元酸成分 經縮合反應而成的聚酯多元醇。 作為多官能醇成分者,可列舉如:乙二醇、丙二醇、 一丙一醇、二乙二醇、三乙二醇、丁二醇、1,6-己二醇、 3-甲基-1,5-戊二醇、3, 3, _二經甲基庚烧、聚氧乙二醇 (P〇ly〇Xyethyle_㈣)、聚氧丙二醇、1,3-丁二醇 丁二醇、新^二醇、辛二醇、丁基乙基戊二醇、2_乙基心— 己-醇、環己二醇、雙盼A、伽F等具有2她基的化 合物,又可列舉如:甘油、三經甲基丙烧、季戊四醇 (pentaerythri to 1)等具有3個以上羥基的化合物。 作為二元酸成分者,可列舉:對苯二曱酸、己二酸、 壬二酸、癸二酸、鄰苯二甲酸酐、間苯二甲酸、偏苯三甲 酸等脂肪族或芳香族二元酸。 又,也可使用:藉由万-丁内s旨、沒-丙内醋、丁内 酉曰、r-戊内醋、ά-戊内酯、卜己内酯、[己内酯、 庚内g旨、α-曱基-β-丙内醋等内醋類等環狀醋化合物的開 環聚合而得之聚酯多元醇。 8 322162 201107439 作為聚碳酸酯多元醇類者,可使用習知之聚碳酸酯多 • 元醇,其係在其分子中具有下述通式[1]所示之結構者。 . 通式[1]: -[-O-R^O-CO-]^ (式中,R1表示2價有機殘基,m表示!以上之整數)。 聚碳酸酯多元醇係藉由例如(1)二醇或雙酚與碳酸酯 之反應、(2)使二醇或雙酚在鹼存在下與光氣進行作用之反 應等而獲得。 在(1)之製法中所使用之碳酸酯,具體上可列舉如:碳 酸二甲酉旨、碳酸二乙醋、碳酸二苯醋、碳酸伸乙醋、碳酸 伸丙酯等。 在(1)及(2)之製法中所使用之二醇或雙酚,也可使用 如.乙二醇、丙二醇、二丙二醇、二乙二醇、三乙二醇、 丁二醇、3-甲基-l,5-戊二醇、2-甲基-辛二醇、3 3,_ 二羥甲基庚烷、聚氧乙二醇、聚氧丙二醇、丙二醇、丨,3_ 丁二醇、1,4-丁二醇、1,5-戊二醇、1>6_己二醇、19_壬 二醇、新戊二醇、辛二醇、丁基乙基戊二醇、2_乙基_丨,3_ 己二醇、環己二醇;或雙酚A、或雙酚F等雙酚類;在雙 酚類經加成環氧乙烷、環氧丙烷等環氧烷而成之雙酚類; 等。此等化合物可使用1種或2種以上之混合物。 、作為聚碳酸酯多元醇之市售品者,可使用〖虹虹奶股 份有限公司之Kuraray P〇ly〇l C系列。其中,pMHC_1〇5〇、 PMHC-2050、C-1090、C-2090、C-1065N、C-2065N、C-1015N、 C-2015N有柔軟性,作為胺酯尿素樹脂(A)之原料,可與具 322162 9 201107439 有聚丙二醇骨幹的多元醇適合併用。 作為其他二醇類者,可列舉如:乙二醇、二乙二醇、 三乙二醇、丁二醇、丙二醇、1,6-己二醇、新戊二醇、環 己烷二甲醇等具有2個羥基的化合物。 又,甘油、三羥曱基丙烧、三經曱基乙燒、季戊四醇、 山梨糖醇、曱基葡糠苷(methylglucoside)等具有3個以上 羥基的化合物也可作為多元醇(a)使用。 又,作為其他之二醇類者,亦可使用含有至少1個離 子性官能基之多元醇。離子性基可列舉如:羧基、磷酸基、 績酸基、1級至3級胺基、4級錢基、鱗(phosphonium)基、 及4級疏(sulfonium)基等。 含有至少1個離子性官能基之多元醇,從將本發明中 所含之胺酯尿素樹脂(A)水性化、或是將胺酯預聚物合成時 之反應速度加速的觀點,更進一步從提高成膜性等之觀點 來看也為適用’但是’另一方面,在胺g旨尿素樹脂(A)中導 入離子性基,尤其離子性基為酸基時,恐怕會腐蝕透明導 電膜或金屬電路。因此,含有至少丨個離子性官能基之多 元醇係因應需要而使用,此時也以不使用必要量以上者為 佳,並以完全不使用者為特佳。 例如,使用具有羧基之多元醇作為含有至少丨個離子 性官能基之多元醇時,可在胺酯尿素樹脂(A)中導入羧基, 並且可將此羧基作為與後述之硬化劑(c)之反應點而使用。 含有至少1個離子性官能基之多元醇,可列舉如:如 一羥甲基丙酸或二羥甲基丁酸等二氧基羧酸等。 322162 10 201107439 在感壓式接著劑層之透明性及接著力等方面 料素樹脂⑴之多元醇⑷者,以制具有聚丙二醇= 夕元醇為佳,在使用之多元醇⑷的合計量剛重 中,具有聚丙二醇骨幹之多轉之量,從確保充分之接著° ί"生觀點而言以50重土 _ 夏虿/°以上為佳,以50至1〇〇重量%為較 佳,以100重量%為更佳。 夕兀醇(a)之數平均分子量,從確㈣壓式接著劑之接 著力的觀點而言,卩咖以上為佳,從確保感壓式接著劑 之耐熱性的觀點而言,以在4, _以下為佳,更佳是i,_ 至3’議。多元醇(a)之數平均分子量太小時,會導致樹脂 中㈣醋及尿素結合濃度之增加,接著力有下降之情形, =一方面’太大時,t導致賦予感壓式接著劑凝聚力之胺 醋結合及尿素結合之降低,感Μ式接著劑之财熱性會有損 害之情形。 、 &上述多元醇(a)’為了滿足作為感壓式接著劑組成物之 性能’以適當選擇而使胺酯尿素樹脂(A)之玻璃移轉溫度 (Tg)在〇至-80 c者為佳。又,玻璃移轉溫度是使用DSC(示 差掃描熱量計)求得之值。 作為夕異氰酸酯(b)者,可使用以往習知者,可列舉 如·芳香族多異氰酸酯、脂肪族多異氰酸酯、芳香脂肪族 多異氰酸酯、脂環族多異氰酸酯等。以下所述之具體化合 物也可使用複數種之組合。 作為芳香族多異氰酸酯者,可列舉如:1,3-伸苯基二 異氰酸酯、4,4’—二苯基二異氰酸酯、1,4-伸苯基二異氰酸 322162 201107439 酉曰4’4 一笨基甲烧一異氰酸酯、2, 4-伸曱苯基二異氰酸 酉曰2, 6一伸曱苯基二異氰酸酯、4, 4, _甲苯胺二異氰酸酯、 ^6-三異氰酸酯甲苯、u 3,卜三異氰酸酯苯、二(曱氧基 苯胺)二異氰酸醋、4,4,_二苯基醚二異驗醋、4,4,,4,,_ 三苯基曱烷三異氰酸酯等。 作為脂肪族多異氰酸酯者,可列舉如:三亞甲基二異 氰酉文8曰四亞曱基二異氰酸酯、六亞曱基二異氰酸酯(別 名· HDI)、五亞甲基二異氰酸酯、丨,2_伸丙基二異氰酸酯、 曱基二異f酸酯、2,4,4_三曱基六亞甲基二異氰酸酯等。 作為芳香族多異氰酸酯者,可列舉如:〇,_二異氰 酉夂酉曰1,3-一曱基苯、ω,ω’_:異氰酸酿'4—二曱基苯、 ω,ω’ 一二異氰酸醋-1,4'二乙基苯、1,4-四曱基苯二甲基 二異氰酸S旨、1,3—四甲基伸苯二甲基二異氰酸酉旨等。 作為脂環族多異氰酸酉旨者,可以列舉如:異佛爾綱二 異氰酸則別名心…仏環狀二異氰酸^^環 己烧-異氰沾、1,4-¾己燒二異氰酸醋、甲基_2,4_環己 烧二異氰酸酯、甲基_2,6'環己院二異氰酸醋、4,4,-亞曱 基雙(環己基異氰酸醋)、u-雙(異氰酸醋甲基)環己院等。 可將上述多異級g旨(b)之三經甲基丙烧加成體、 酸醋環之三聚物等予以部分併用。也可使用 ^基^夕異她旨(別名:PAPI)、萘二異氰酸醋、及 1專之夕/氰酸㈣f物等。又,作為多異氰_改質物 者,可使用:具有碳化-β, 一亞胺(carbodiimide)基、脲二酮 322162 12 201107439 (uretdione)基、脲酮亞胺(uretonimine)基、已與水反應 • 之縮二脲(biuret)基、三聚異氰酸酯基中任丨種基或2種 以上此等基的改質物。多元醇與二異氰酸酯之反應物也可 作為多異氰酸酯(b)使用。 作為本發明中之多異氰酸酯(b)者,當使用如4, 4,-二 苯基曱烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二 異氰酸酯(別名:IPDI)、伸苯二曱基二異氰酸酯' 4,4, 一 亞曱基雙(環己基二異氰酸酯)(別名:加氫MDI)等無黃變 型、或是難黃變型之多異氰酸酯化合物時,從耐候性之觀 點而言為佳。 又,作為上述之多異氰酸酯(1})者,從接著劑組成物的 透明性或反應性之控制的觀點而言,以使用異佛爾酮二異 氰酸酯(別名:IPDI)為佳。 ' 多異氰酸酯(b)之使用量,亦即饋入量,從維持感壓式 接著劑之凝聚力並賦予耐久性之觀點而言,在胺酯尿素樹 脂(A)l〇〇重量%中,係以8重量%以上為佳,從防止樹脂之 柔軟性的下降並確保充分之接著力之觀點而言,以23重量 /〇以下為佳’更佳是10至21重量%。在此,「胺g旨尿素樹脂 (A)100重量%中」若換而言之即為「胺醋尿素樹脂⑴之合 成原料100重量%中」,係指在胺酯尿素樹脂(A)之合成中所 使用的多元醇(a)、多異氰酸酯(b)、多胺基化合物(c)、及 因應必要使用之反應停止劑(d)的合計1〇〇重量%中之音 (以^下之記載中也為同樣意思)。總之,使用多元醇(a)、^ 異鼠酸酯(b)、多胺基化合物(c)、及反應停止劑(d)時之反 322162 13 201107439 應停止劑(d)的合計loo重量%中的多異氰酸酯(b)之量(使 用量或饋入量)係以8至23重量%為佳。 其次,針對本發明中使用的多胺基化合物(c)進行說 明。該多胺基化合物(c)是具有2個以上胺基的化合物,可 使用公知的化合物。藉由使用具有2個以上胺基的化合 物,可賦予感壓式接著劑之接著力,更可同時達成耐久性。 以下所述之具體化合物,也可使用複數種之組合。 具體上可例示如:伸乙二胺、三亞甲基二胺、四亞甲 基一胺、五亞曱基一胺、六亞曱基二胺'、三伸乙四胺、二 伸乙二胺、二胺基丙烧、2, 2,4-三曱基六亞甲基二胺、2_ 羥基乙基伸乙二胺、N-(2-羥基乙基)伸丙二胺、(2-羥基乙 基伸丙基)二胺、(二-2-羥基乙基伸乙基)二胺、(二_2_羥 基乙基伸丙基)二胺、(2-羥基丙基伸乙基)二胺、(二_2_ 沒基丙基伸乙基)二胺、派卩井(piperazidine)等脂肪族多 胺; 異佛爾酮二胺、二環己基曱烷-4, 4’-二胺等脂環式多 胺; 伸苯二胺、伸苯二甲基二胺、2, 4-伸甲笨二胺、2,6-伸曱苯二胺、二乙基曱苯二胺、3, 3’ -二氯-4, 4,-二胺基二 笨基甲烷、4, 4’-雙-(二級丁基)二苯基曱烷等芳香族二 胺;以及 將二聚酸(dimer acid)之竣基轉化為胺基之二聚物二 胺(dimer diamine)、在末端具有一級或二級胺基之樹枝狀 聚合物等。 14 322162 201107439 再者,作為多胺基化合物(c)者,也可使用在兩末端具 有丙氧基胺且如下述通式[2]所示的聚氧烷二醇二胺等。 , 通式[2]: H2N-CH2-CH2-CH2-0-(C(nH2ln-0)„-CH2-CH2-CH2-NH2 (式中’m是2至4之任意整數,n表示2至50之任意整數)。 作為本發明中使用的多胺基化合物(c)者,從反應之控 制方面而&,特別是以由具有2個以上一級胺基之化合物 (cl)與乙烯性不飽和化合物(c2)進行邁克加成反應 (Michael addition)而成之化合物(c3)為佳,又,作為乙 烯性不飽和化合物(C2)者,從對胺酯尿素樹脂(…之交聯點 導入方面而言,以使用具有羥基之乙烯性不飽和化合物為 佳。 作為具有2個以上一級胺基之化合物者,可使用 上述之具有2個以上胺基之化合物,尤其是異佛爾酮二 胺、2’2, 4-三甲基六亞曱基二胺、六亞曱基二胺,係因容 易控制邁克加成反應,且使用由邁克加成反應得到之化合 物(c3)而得之胺酯尿素樹脂的透明性優良,故而為佳。 乙烯性不飽和化合物(C2)中,作為具有羥基之乙烯性 不餘和化合物者,例如可列舉:(甲基)丙烯酸2—羥基乙酯、 (甲基)丙稀酸2-經基丙酯、(甲基)丙烯酸4-羥基丁酯、甘 油車(甲基)丙烯酸醋、4-經基乙稀基苯、1-乙炔基環己 醇、烯丙醇; 曰本 Daicel 化學工業製 piaccel FA、Placcel FA2D、201107439 VI. Description of the invention: [Technical field to which the invention pertains], and bursts: a composition of a pressure-sensitive adhesive for a conductive member, more specifically: a two-conductor structure: a conductive layer used in a touch panel or the like The adhesive of the component and the (4) pressure-sensitive adhesive composition, and the conductive member formed by the composition of the composition are used for the abdomen a ># κ control panel with a thin pressure-type adhesive sheet 'layered Zhao, and touch Prior Art] Various products such as personal computers and televisions are becoming more popular, especially in electronic notebooks and mobile phones, and the liquid crystal display system is widely used as a display device for any electronic device. . In such a liquid crystal display device or the like, the function of the display panel is to function as a sheet for a touch panel, and the operator specifies the operation by touching a predetermined portion of the display panel with a finger, that is, having a so-called The module for the touch panel. In the structure of the touch panel, a glass substrate or a transparent resin substrate, and a conductive member including a no t transparent conductive film or a metal circuit are adhered by a pressure-sensitive adhesive layer. The glass substrate or the transparent tree P base/feel, the adhesive layer/transparent electrode (conductive member): the screen body is placed right at the south temperature or under the condition of warm and high humidity, and then in the sensor layer The adhering interface of the adherend will generate bubbles (foaming), and the self-adhesive will float or will peel off. Therefore, it is used for the purpose of: salty:: the following agent has been tried to improve it so that it does not cause foaming, floating, or peeling even in the case of strict saltiness. Also in the clothing environment, and for the above-mentioned money type, it is required to have a high adhesion force which does not peel off when a strong force is applied in the direction 322162 3 201107439. In the above-mentioned pressure-sensitive adhesive layer, the use of a pressure-sensitive adhesive mainly using an acrylic resin as a base material has been carried out until now (Patent Documents 1 and 2). When a pressure-sensitive adhesive having an acrylic resin as a substrate is used, in order to improve the adhesion to the conductive member, it is necessary to introduce an acid group into the base resin. However, the introduced acid group corrodes the conductive member as the adherend, causing malfunction and the like. Further, it has been reviewed for various applications of a pressure-sensitive adhesive using an urethane-urea resin as a base material. However, the above-mentioned high-performance adhesion or the application to the conductive member has not been performed so far (Patent Documents 3, 4, and 5). [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. 2008-120864. [Problem to be Solved by the Invention] An object of the present invention is to provide a pressure-sensitive adhesive composition for a conductive member, which is In a conductive member such as a transparent conductive film or a metal circuit such as ITO, it does not cause malfunction due to corrosion, and it is not easy to cause foaming or peeling under high temperature or 4 322162 201107439. Agent resistance or good processability, and thus high adhesion. In order to solve the above problems, the present inventors have found that the present invention has been accomplished by the purpose of the following description of the pressure-sensitive adhesive composition shown below. In the first aspect of the invention, the invention relates to a pressure-sensitive adhesive composition for a conductive member, which comprises an amine ester urea resin having a weight average molecular weight (Mw) of 5 Å, (10) 〇 200 200 000, And a curing agent (B) in an amount of from 01 to 3 parts by weight relative to 100 parts by weight of the aforementioned amine ester urea resin (A); wherein the amine ester urea resin (A) is made of a polyhydric alcohol and a polyisocyanate (polyis〇) (Cyanate, also known as polyisocyanate) (b) The reaction of the urethane prepolymer with the polyamine compound (c). According to a second aspect of the invention, there is provided the pressure-sensitive adhesive composition for a conductive member according to the first aspect of the invention, wherein the polyisocyanate (b) is used in an amount of the synthetic raw material of the amine ester urea resin (A). The amount of the above-mentioned polyamine-based compound (c) is from 0.5 to 8% by weight based on 1% by weight of the synthetic raw material of the above-mentioned amine ester urea resin (A). The present invention relates to a pressure-sensitive adhesive composition for a conductive member according to the first or second aspect of the present invention, wherein the polyol (a) comprises a polyol having a polypropylene glycol backbone. The present invention relates to the pressure-sensitive adhesive composition for a conductive member of the present invention according to any one of the first to third aspect, wherein the hardener (B) comprises a component selected from the group consisting of hexamethylene diisocyanate Hydroxymethylpropane adduct, six 322162 5 201107439 methylene diisocyanate trimeric isocyanate (hexamethylendiisocyanateisocyanurate), hexamethylene diisocyanate biuret, and dimethyl diisocyanate trimethylolpropane At least one of the adult groups. The present invention relates to a pressure-sensitive adhesive composition for a conductive member of the present invention according to any one of the first to fourth aspect, which is characterized in that it contains 100 parts by weight of the amine-based urea resin (A). 0.1 to 1. 〇 by weight of a group selected from the group consisting of 3-glycidoxypropyltrimethoxydecane, 3-isocyanatopropyltriethoxydecane, and a decane coupling agent having an imidazole group Any one or more of them. According to a sixth aspect of the invention, there is provided a pressure-sensitive adhesive sheet for a conductive member, comprising a sheet-like base material and a pressure-sensitive adhesive layer formed on one surface or both surfaces of the sheet-like base material, The pressure-sensitive adhesive layer 1 is formed of the pressure-sensitive composition for a conductive member of the present invention according to any one of the first to fifth aspects. That is, the sixth item (4) relates to a dust-sensitive adhesive sheet for a conductive member, which is formed by the iv-to-first item of the present mosquito-repellent electrical component: a pressure-sensitive adhesive layer is formed. On the one side of the sheet-like substrate or = the seventh aspect of the invention relates to: a laminate or a transparent member, and the former "having a conductive member =::=: a composition formed by the composition. That is, the seventh The present invention is a pressure-sensitive adhesive layer formed by laminating a pressure-sensitive adhesive composition for a conductive member of the present invention according to any one of the first to fifth embodiments on a conductive member. According to a seventh aspect of the invention, the laminated body of the present invention, wherein the conductive member is a transparent conductive iridium or a metal circuit. The invention of the ninth and tenth aspects relates to: a touch panel sheet, Each of the laminated bodies of the present invention according to the seventh or eighth aspect of the present invention is provided. The present invention can provide a conductive member such as a transparent conductive film or a metal circuit such as ΙΤ0, which does not cause corrosion due to corrosion. Poor operation, etc., good fortune and wealth, good fortune A good pressure-sensitive adhesive composition or a good adhesiveness, and a pressure-sensitive adhesive composition for a conductive member having high adhesion (hereinafter, simply referred to as "pressure-sensitive adhesive composition" as an "adhesive composition"). First, the amine acetal urea resin (A) will be described. The amine-based urea resin (A) is obtained by reacting an amine ester prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b) with a polyamine-based compound (c), and has a weight average molecular weight of 50,000 to 200,000 resin. As the polyol (a) to be used, those skilled in the art can be used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, copolymers thereof, and other diols. (glycol) class and so on. A specific combination of the following may also be used as a specific compound. As the polyether polyol, a conventional poly-bond polyol can be used. For example, it can be used: propylene oxide, propylene oxide, net oxygen 322162 7 201107439 = polymer of private epoxy oxime ring, copolymer, and graft co-, hexane, F a polyether polyol obtained by condensing hexylene glycol, heptanediol, octanediol, or the like, and having two or more kinds of addition-type epoxy resins, which can be used in a double or double F and other diols such as Ethylene Baked. As the polyester polyol, a conventional polyester polyol can be used. As the polyester polyol, for example, a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component can be used. Examples of the polyfunctional alcohol component include ethylene glycol, propylene glycol, monopropanol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, and 3-methyl-1. , 5-pentanediol, 3, 3, _ dimethyl ketone, polyoxyethylene glycol (P〇ly〇Xyethyle_(tetra)), polyoxypropylene glycol, 1,3-butanediol butanediol, new ^ two Alcohol, octanediol, butyl ethyl pentanediol, 2-ethyl ethyl hexanol, cyclohexanediol, bis, A, gamma F and the like having a compound of 2, such as: glycerin, A compound having three or more hydroxyl groups, such as methylpropane or pentaerythri to 1. Examples of the dibasic acid component include aliphatic or aromatic compounds such as terephthalic acid, adipic acid, sebacic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Yuan acid. In addition, it can also be used: by wan-butan s, no-propanol vinegar, butyrolactone, r-pentane vinegar, ά-valerolactone, pucaprolactone, [caprolactone, Gengene A polyester polyol obtained by ring-opening polymerization of a cyclic vinegar such as an internal vinegar such as α-mercapto-β-propionyl vinegar. 8 322162 201107439 As a polycarbonate polyol, a conventional polycarbonate polyhydric alcohol having a structure represented by the following formula [1] in its molecule can be used. General formula [1]: -[-O-R^O-CO-]^ (wherein R1 represents a divalent organic residue, and m represents an integer of !). The polycarbonate polyol is obtained, for example, by reacting (1) a diol or a bisphenol with a carbonate, and (2) reacting a diol or a bisphenol with phosgene in the presence of a base. Specific examples of the carbonate used in the production method of (1) include dimethyl carbonate, diethylene carbonate, diphenyl vinegar, ethylene carbonate, and propyl carbonate. The diol or bisphenol used in the processes of (1) and (2) may also be used, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 3- Methyl-1,5-pentanediol, 2-methyl-octanediol, 3 3,-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propylene glycol, hydrazine, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1>6-hexanediol, 19-decanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2_B Base _ 丨, 3 _ hexanediol, cyclohexane diol; or bisphenol A, or bisphenol F bisphenols; in the bisphenols are added to ethylene oxide, propylene oxide and other alkylene oxide Bisphenols; etc. These compounds may be used alone or in combination of two or more. As a commercial product of polycarbonate polyol, the Kuraray P〇ly〇l C series of Honghong Milk Co., Ltd. can be used. Among them, pMHC_1〇5〇, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, C-2015N have softness and can be used as a raw material of the amine ester urea resin (A). It is suitable for use with a polyol having a polypropylene glycol backbone of 322162 9 201107439. Examples of other glycols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimethanol, and the like. A compound having two hydroxyl groups. Further, a compound having three or more hydroxyl groups such as glycerin, trishydroxypropylpropane, triacetinyl, pentaerythritol, sorbitol or methylglucoside can also be used as the polyol (a). Further, as other glycols, a polyol containing at least one ionic functional group can also be used. Examples of the ionic group include a carboxyl group, a phosphoric acid group, a creidic acid group, a first- to third-order amine group, a 4-carbon group, a phosphonium group, and a sulfonium group. The polyol containing at least one ionic functional group further increases the reaction rate when the amine ester urea resin (A) contained in the present invention is aqueous or the amine ester prepolymer is synthesized. It is also applicable from the viewpoint of improving film formability, etc. On the other hand, when an amine group is introduced into the urea resin (A), especially when the ionic group is an acid group, the transparent conductive film may be corroded or Metal circuit. Therefore, a polyol containing at least one ionic functional group is used as needed. In this case, it is preferable not to use a necessary amount or more, and it is particularly preferable that it is not used at all. For example, when a polyol having a carboxyl group is used as the polyol having at least one ionic functional group, a carboxyl group can be introduced into the amine ester urea resin (A), and this carboxyl group can be used as a hardener (c) to be described later. Use at the reaction point. The polyhydric alcohol containing at least one ionic functional group may, for example, be a dioxycarboxylic acid such as monomethylolpropionic acid or dimethylolbutanoic acid. 322162 10 201107439 In the case of the polyol (4) of the resin (1) in terms of transparency and adhesion of the pressure-sensitive adhesive layer, it is preferred to have polypropylene glycol = oxime, and the total amount of polyol (4) used is just In the middle of the weight, the amount of the polypropylene glycol backbone is more than 50% soil _ 虿 虿 ° ί 生 生 生 生 生 生 生 生 生 生 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 More preferably, it is 100% by weight. The number average molecular weight of the ceramyl alcohol (a) is preferably from the viewpoint of the adhesion of the (four) pressure-sensitive adhesive, and from the viewpoint of ensuring the heat resistance of the pressure-sensitive adhesive, at 4 , _ below is better, better is i, _ to 3'. If the average molecular weight of the polyol (a) is too small, it will lead to an increase in the concentration of (iv) vinegar and urea in the resin, and then the force will decrease. On the one hand, when it is too large, t will cause the cohesive force of the pressure-sensitive adhesive. The combination of amine vinegar and urea reduces the heat of the sensitizing adhesive. & The above polyol (a) 'in order to satisfy the performance as a pressure-sensitive adhesive composition', the glass transition temperature (Tg) of the amine ester urea resin (A) is appropriately selected from 〇 to -80 c It is better. Further, the glass transition temperature is a value obtained by using a DSC (differential scanning calorimeter). As the oxime isocyanate (b), conventionally used ones may be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. The specific compounds described below may also be used in combination of plural kinds. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, and 1,4-phenylene diisocyanate 322162 201107439 酉曰4'4 a succinil-based mono-isocyanate, 2, 4-anthracene phenyl diisocyanate 2, 6-indene phenyl diisocyanate, 4, 4, _toluidine diisocyanate, ^6-triisocyanate toluene, u 3, triisoisocyanate benzene, bis(decyloxyaniline) diisocyanate, 4,4,_diphenyl ether diisoacetate, 4,4,,4,,_ triphenyldecane triisocyanate Wait. Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate 8 曰 tetradecyl diisocyanate, hexamethylene diisocyanate (alias HDI), pentamethylene diisocyanate, hydrazine, 2 _ propyl diisocyanate, decyl diiso-f-ester, 2,4,4-tridecyl hexamethylene diisocyanate, and the like. As the aromatic polyisocyanate, for example, 〇, _ diisocyanide 1,3- fluorenyl benzene, ω, ω'_: isocyanate 4'-diphenyl benzene, ω, ω'-I-Isocyanic acid vinegar-1,4' diethyl benzene, 1,4-tetradecyl benzene dimethyl diisocyanate S, 1,3 - tetramethyl benzoyl diiso Cyanate is intended. As the alicyclic polyisocyanate, for example, the isophora diisocyanate is nicknamed... 仏 cyclic diisocyanate ^^cyclohexene-isocyanide, 1,4-3⁄4 Ethylene diisocyanate, methyl 2,4_cyclohexene diisocyanate, methyl 2,6' cyclohexan diisocyanate, 4,4,-arylene di(cyclohexyl) Cyanate vinegar), u-bis (isocyanate methyl) ring homes and the like. The above-mentioned multi-different g(b) tris may be partially used in combination with a methyl propylene-fired adduct, an acid vinegar ring trimer or the like. It is also possible to use a radical basis (alias: PAPI), naphthalene diisocyanate vinegar, and a special ionic/cyanic acid (tetra)f material. Further, as the polyisocyanate-modified substance, it is possible to use: carbonized-β, carbodiimide group, uretdione 322162 12 201107439 (uretdione) group, uretonimine group, and water Reaction • Biuret group, trimeric isocyanate group, or a modified substance of two or more of these groups. The reactant of the polyol and the diisocyanate can also be used as the polyisocyanate (b). As the polyisocyanate (b) in the present invention, when, for example, 4,4,-diphenyldecane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (alias: IPDI), and benzophenone are used. When it is a non-yellowing or non-yellowing polyisocyanate compound such as fluorenyl diisocyanate '4,4, monodecyl bis(cyclohexyl diisocyanate) (alias: hydrogenated MDI), from the viewpoint of weather resistance It is better. Further, as the above polyisocyanate (1}), isophorone diisocyanate (alias: IPDI) is preferably used from the viewpoint of control of transparency or reactivity of the adhesive composition. 'The amount of polyisocyanate (b) used, that is, the amount of feed, is from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and imparting durability, in the weight percent of the amine ester urea resin (A) The amount is preferably 8% by weight or more, and more preferably 23% by weight or less, more preferably 10% to 21% by weight, from the viewpoint of preventing deterioration of flexibility of the resin and ensuring sufficient adhesion. Here, "in the case of 100 g% of the amine resin (A) in the case of the amine g", it is "100% by weight of the synthetic raw material of the amine vinegar urea resin (1)", which means the urea resin (A). The total of 1% by weight of the polyol (a), the polyisocyanate (b), the polyamine compound (c), and the reaction stopper (d) used in the synthesis (in the case of The same is true in the description.) In summary, the use of polyol (a), isopic acid ester (b), polyamine based compound (c), and reaction stop agent (d) when the reverse 322162 13 201107439 should stop agent (d) total loo weight% The amount (usage or feed amount) of the polyisocyanate (b) is preferably from 8 to 23% by weight. Next, the polyamine-based compound (c) used in the present invention will be described. The polyamine-based compound (c) is a compound having two or more amine groups, and a known compound can be used. By using a compound having two or more amine groups, the adhesion of the pressure-sensitive adhesive can be imparted, and durability can be simultaneously achieved. The specific compounds described below may also be used in combination of plural kinds. Specifically, for example, ethylenediamine, trimethylenediamine, tetramethylenemonoamine, pentadecylamine, hexamethylenediamine, triamethylenetetramine, diethylenediamine , diaminopropane, 2,2,4-trimercaptohexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethyl) Propyl propyl)diamine, (di-2-hydroxyethylexene)diamine, (di-2-hydroxyethyl)propylamine, (2-hydroxypropylethylidene)diamine, (di) 2_ propyl propyl ethyl) diamine, piperazidine and other aliphatic polyamine; isophorone diamine, dicyclohexyl decane-4, 4 '-diamine and other alicyclic polyamine; Phenylenediamine, benzoyldiamine, 2,4-extended methylamine, 2,6-extension phenylenediamine, diethylphenylphenylenediamine, 3,3'-dichloro-4 An aromatic diamine such as 4,-diaminodiphenylmethane, 4,4'-bis-(dibutyl)diphenylnonane; and conversion of a thiol group of a dimer acid to An amine dimer diamine, a dendrimer having a primary or secondary amine group at the terminal, and the like. Further, as the polyamine-based compound (c), a polyoxyalkylene glycol diamine having a propoxyamine at both terminals and having the following formula [2] can also be used. , General formula [2]: H2N-CH2-CH2-CH2-0-(C(nH2ln-0)„-CH2-CH2-CH2-NH2 (wherein m is an arbitrary integer from 2 to 4, and n represents 2 to Any of the integers of 50. As the polyamine-based compound (c) used in the present invention, from the viewpoint of the control of the reaction, in particular, the compound (cl) having two or more primary amino groups and the ethyl group are not The saturated compound (c2) is preferably a compound (c3) obtained by a Michael addition reaction, and, as an ethylenically unsaturated compound (C2), is introduced from a crosslinking point of an amine ester urea resin (... In particular, it is preferred to use an ethylenically unsaturated compound having a hydroxyl group. As a compound having two or more primary amino groups, the above compound having two or more amine groups, particularly isophorone diamine, can be used. 2'2,4-trimethylhexamethylenediamine, hexamethylenediamine, an amine obtained by easily controlling the Michael addition reaction and using the compound (c3) obtained by the Michael addition reaction The ester urea resin is excellent in transparency, and is preferably used as an ethyl group having a hydroxyl group in the ethylenically unsaturated compound (C2). Examples of the compound and the compound include 2-hydroxyethyl (meth)acrylate, 2-propylpropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin ( Methyl)acrylic acid vinegar, 4-vinylidene benzene, 1-ethynylcyclohexanol, allyl alcohol; 曰本Daicel Chemical Industry piaccel FA, Placcel FA2D,
Placcel FA3、Placcel FA5、Placcel FA10L、Placcel FM1D、 15 322162 201107439Placcel FA3, Placcel FA5, Placcel FA10L, Placcel FM1D, 15 322162 201107439
Placcel FM2D、Placcel FM3、Placcel FM3X、Placcel FM5、Placcel FM2D, Placcel FM3, Placcel FM3X, Placcel FM5,
Placcel FM5L等具有在末端有羥基之聚酯鏈的不飽和化合 物; 聚乙二醇(甲基)丙烯酸酯、聚丙二醇(曱基)丙烯酸 酯、聚四亞曱基二醇(曱基)丙浠酸酯、六乙二醇(曱基)丙 烯酸酯等具有在末端有羥基之聚醚鏈的不飽和化合物。 雖可將上述化合物單獨或組合2種以上使用,但特別 是從與後述之硬化劑(B)的反應性、及感壓式接著劑之光學 特性等方面而言,以使用丙烯酸4-羥基丁酯為佳。 在乙烯性不飽和化合物(C2)中,作為不具有羥基者, 可列舉如·(曱基)丙烯酸曱醋、(曱基)丙稀酸乙酉旨、(甲基) 丙烯酸丙酯、(曱基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲 基)丙烯酸2-乙基己酯、(曱基)丙烯酸庚酯、(甲基)丙烯 酉文己酉曰、(曱基)丙稀酸辛醋、(甲基)丙烯酸壬酯、(曱基) 丙烯酸癸酯、(曱基)丙烯酸十一碳烷酯、(曱基)丙烯酸十 二碳烷酯、(甲基)丙烯酸十三碳烷酯、(曱基)丙烯酸十四 碳烷酯、(甲基)丙烯酸十五碳烷酯、(曱基)丙烯酸十六碳 烷酯、(甲基)丙烯酸十七碳烷酯、(甲基)丙烯酸十八碳烷 酉曰(甲基)丙晞酸十九碳烧醋、(甲基)丙烯酸二十碳院醋、 (甲基)丙烯酸二十一碳烷酯、(甲基)丙烯酸二十二碳烷酯 等碳數1至22之(甲基)丙稀酸院酯。以極性之調節作為目 的時,較佳為具有碳數2至10,更佳為具有碳數2至8之 烷基的含烷基之丙烯酸酯,或對應之曱基丙烯酸酯。以塗 平性之調節等為目的時,以碳數6以上為佳。 322162 16 201107439 又’作為乙稀性不飽和化合物(c2)者,可併用:甲氧 基聚乙一醇(曱基)丙坤酸酉旨、乙氧基聚乙二醇(甲基)丙稀 酸酉旨、丙氧基聚乙二醇(甲基)丙烯酸g旨、正丁氧基聚乙二 醇(甲基)丙烯酸酯、正戊氧基聚乙二醇(甲基)丙烯酸醋、 苯氧基聚乙二醇(曱基)丙稀酸醋、曱氧基聚四亞曱基二醇 (甲基)丙烯酸酯、苯氧基四乙二醇(曱基)丙烯酸酯、甲氧 基六乙二醇(曱基)丙烯酸酯等烷氧基聚烷二醇單(曱基)丙 烯酸酯類或是苯氧基聚烷二醇單(甲基)丙烯酸酯類; 醋酸乙烯酯、酪酸乙烯酯、丙酸乙烯酯、己酸乙烯醋、 辛酸乙烯酯 '月桂酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙婦 酯等脂肪酸乙烯酯類; 丁基乙烯基醚、乙基乙烯基醚等乙烯基醚類; 1-己烯、1-辛烯、1-癸烯、1-十二碳烯、卜十四碳烯、 1-十六碳烯等0:-烯烴類; 馬來酸、富馬酸、衣康酸、檸康酸(citrac〇nicacid;)、 或是此等之烷基或烯基單酯、鄰苯二甲酸^一(曱基)丙烯醯 氧基乙基單酯、間苯二曱酸(曱基)丙烯醯氧基乙基單 酯、對苯二曱酸万一(曱基)丙烯醯氧基乙基單酯、琥珀酸谷 -(曱基)丙烯醯氧基乙基單酯、丙烯酸、曱基丙烯酸'巴豆 酸、肉桂酸等含有羧基之不飽和化合物類; 含有醯胺基之不飽和化合物、含有二烧基胺基之不飽 和化合物、含有四級銨鹽基之不飽和化合物等含有氮之不 飽和化合物類。 作為含有醯胺基之不飽和化合物者,可列舉如:(曱基) 17 322162 201107439 丙烯醯胺、N-羥曱基(曱基)丙烯醯胺、N-曱氧基曱基一(曱 基)丙烯醯胺、N-乙氧基曱基—(甲基)丙烯醯胺、N_丙氧基 甲基-(曱基)丙烯醯胺、N-丁氧基曱基-(曱基)丙烯醯胺、 N-戊氧基曱基-(曱基)丙烯醯胺、N, N-二(羥曱基)丙烯醯 胺、N-羥曱基-N-曱氧基曱基-(曱基)丙烯醯胺、n,N-二(甲 氧基曱基)丙烯醯胺、N-乙氧基曱基-N-曱氧基曱基曱基丙 烯醯胺、N,N-二(乙氧基甲基)丙烯醯胺、N-乙氧基曱基-N-丙氧基甲基曱基丙烯醯胺、N,N-二(丙氧基曱基)丙烯醯 胺、N-丁氧基曱基-N-(丙氧基曱基)曱基丙烯醯胺、n,N-二(丁氧基曱基)丙烯醯胺、N-丁氧基曱基-N-(曱氧基曱基) 甲基丙烯醯胺、N,N-二(戊氧基曱基)丙烯醯胺、N-甲氧基 曱基-N-(戊氧基曱基)甲基丙烯醯胺等。 作為含有二烷基胺基之不飽和化合物者,可列舉如: (曱基)丙烯酸二曱基胺基乙酯、(曱基)丙烯酸二乙基胺基 乙酯、(甲基)丙烯酸二丁基胺基乙酯、(曱基)丙烯酸二丙 基胺基乙酯、(曱基)丙烯酸曱基乙基胺基乙酯、二曱基胺 基笨乙烯、二乙基胺基苯乙烯等。 作為含有四級銨鹽基之不飽和化合物者,係藉由將上 述含有一烧基胺基之不飽和化合物進行四級敍化而得。具 有Cr、Br' Γ之鹵離子或QS〇3_(Q :碳數1至12之烷基) 作為相對離子(counterion)的含有四級銨鹽基之不飽和化 合物’可列舉如:(曱基)丙烯酸二曱基胺基乙基曱基氯化 鹽、二曱基-3-(1-(甲基)丙稀醯胺-1,1-二曱基丙基)氯化 銨、三甲基-3-(1-(曱基)丙烯醯胺丙基)氯化銨、及三曱基 18 322162 201107439 -3-(1-(甲基)丙烯醯胺一 M_二甲基乙基)氣化銨等。 又,作為乙稀性不飽和化合物(c2)者,也可併用:(甲 基)丙烯酸全氟甲基甲酯、(甲基)丙烯酸全氟乙基甲酯、(甲 基)丙烯酸2-全氟丁基乙酯、(甲基)丙烯酸2_全氟己基乙 酯、(甲基)丙烯酸2-全氟辛基乙酯、(甲基)丙烯酸2_全氟 異壬基乙酯、(甲基)丙烯酸2-全氟壬基乙酯、(甲基)丙烯 酉文2-全氟癸基乙酯、(甲基)丙烯酸全氟丙基丙酯、(甲基) 丙烯酸全氟辛基丙酯、(甲基)丙烯酸全氟辛基戊酯、(甲基) 丙烯酸全氟辛基十一碳烷酯等具有碳數丨至2〇之全氟烷基 的(曱基)丙烯酸全氟烷酯類; 全氟丁基乙烯、全氟己基乙烯、全氟辛基乙烯、全氟 癸基乙烯等全氟烷基烯烴類等含有全氟烷基之不飽和化合 物; 乙烯基三氣矽烷、乙烯基參(沒-甲氧基乙氧基)矽烷、 乙稀基二乙氧基石夕烧、(曱基)丙烯酿氧丙基三曱氧基石夕 烧等具有烧氧基石夕院基之不飽和化合物及其衍生物; 丙烯酸縮水甘油酯、丙烯酸3, 4-環氧基環己酯等含有 環氧基之不飽和化合物; 醋酸烯丙酯、稀丙基苯、烯丙基氰等烯丙基化合物; 乙烯基氰、乙烯基環己烷、乙烯基曱基酮、苯乙稀、 α-曱基苯乙烯、2-曱基苯乙烯、氯苯乙烯等乙烯基化合物; 乙块、乙快基本、乙快基曱本等乙快基化合物;等。 在具有2個以上一級胺基之化合物(ci)與乙烯性不飽 和化合物(c2)之邁克加成反應中,係具有2個以上一級胺 322162 19 201107439 基之化合物(cl)中的胺基之活性氫1莫耳、與乙烯性不飽 和化合物(c2)中之乙烯性不飽和基1莫耳進行反應。由於 具有2個以上一級胺基之化合物(ci)中之胺基,對於具有 電子吸引性基之化合物的乙烯性不飽和基容易進行邁克加 成,故乙烯性不飽和化合物(c2)係以(甲基)丙烯酸系化合 物為佳’尤其從邁克加成反應之效率的觀點而言,以丙稀 酸酯系化合物為最佳。 對於具有2個以上一級胺基之化合物(cl)使乙烯性不 飽和化合物(C2)進行邁克加成反應而得之化合物(c3)之合 成方法,可直接利用關於邁克加成反應的習知方法。當乙 烯性不飽和化合物(c2)為(曱基)丙烯酸系化合物時,尤其 在為丙烯酸酯系化合物等時,因應需求而在醇等觸媒下於 10至lOOt進行反應。雖也隨著使用之乙烯性不飽和化合 物(c2)的種類不同而異,但以4〇至8(rc之反應溫度為佳。 反應溫度太高時,因為會產生酯醯胺交換反應故而不佳。 當乙烯性不飽和化合物(C2)不具有電子吸引性基時, ’欠成可在金屬觸媒之存在下反應,此時,若在觸媒之存在 下一面加熱一面在60至1〇(rc反應,則變成有適當之反應 速度,故而為佳。 “ 合成用之溶劑是可使用也可不使用,其種類並無特別 限定’可使用曱基乙基嗣、曱苯、丙_、苯等f知之溶劑。 使用溶劑時之溶液濃度以在2〇重量%以上為佳,更佳是在 50重量%以上。比此更稀薄時,由於反應不易進行故 佳。 322162 20 201107439 反應時間係隨使用之乙烯性不飽和化合物(C 2)之種類 不同而異’但在30分鐘至5小時即終止。 對於具有2個以上一級胺基之化合物(cl)加成的乙烯 性不飽和化合物(C2)的比率,係以使在經邁克加成反應而 成之化合物(c3)中至少殘存2個一級或二級胺基的方式, 相對於具有2個以上一級胺基之化合物(cl)所具有的一級 胺基1莫耳,以〇. 1至1 〇莫耳之比率為佳,更佳是〇. 2 至1. 〇莫耳之比率,使乙烯性不飽和化合物(c2)中的乙烯 性不飽和基進行反應為佳。乙烯性不飽和基之量若少於該 篁時,會有得不到導入乙烯性不飽和化合物(c2)之效果的 情形,更進一步因降低保存安定性故而不佳,但另一方面, 即使多於該量也不會對反應有利。 多胺基化合物(c)之使用量,在胺酯尿素樹脂(A)1〇〇 重量%中,從維持感壓式接著劑之凝集力並賦予耐久性之觀 點而言,以0.5重量%以上為佳,從防止樹脂柔軟 蝴充分接著力之觀點而言,以在8重伽下= f疋2至5重量%。總之’使用多元醇(a)、多異氰酸酯(乜)、 多胺基化合物⑷、及反應停止劑⑷時之反應停止劑⑷ 计100重量%中,多胺基化合物(C)之量(使用量或饋入 量)以0. 5至8重量%為佳。 *胺醋尿素樹脂⑷雖料由末端為異氰酸基之胺醋預 聚口物與多胺基化合物⑹反應而得者,但可另因應需要而 =作為反齡止劑⑷之單胺基化合物進行反應。亦即,在 否成胺酯尿素樹脂⑴之時,為了控制分子量、或是在與胺 322162 21 201107439 酯尿素樹脂(A)末端之未反應而殘留之異氰酸基進行反應 並使樹脂之反應活性成為安定化之目的下,可使用反應^ 止劑(d)。此時之胺酯尿素樹脂(A)是藉由對於將多元醇(a) 與多異氰酸酯(b)反應而得之胺酯預聚物,使多胺基化合物 (c)與反應停止劑(d)進行反應而成者。 作為反應停止劑(d)者,例如,除了二乙基胺、二正丁 基胺、一正辛基胺、一%>己基胺、一異壬基胺等二院基胺 類之外,可使用: 單乙醇胺、二乙醇胺、2-胺基-2-曱基―丨-丙醇、三(經 曱基)胺基曱院、2-胺基-2-乙基-1,3-丙二醇等具有經基之 單胺; Α 單曱基肼(monomethylhydrazine)、1,卜二甲美耕、节 基肼等院基肼類、甲醯肼(formhydrazide)、乙醯月桂 醯肼等醯肼類; ^二曱基-以-丙烧二胺^二乙基-^丙烧二 胺等具有三級胺基與一級胺基的化合物; r-胺基丙基三乙氧基魏等具有燒氧基魏基的單 胺基化合物。X ’只具有i個—級或二級胺基的胺基化合 物也可作為反應停止劑使用。 σ 即使上述之反應停止劑⑷之中,使用如2_胺基、 基-丙醇等具有羥基之單胺基化合物時,即可獲 基的保存安定性敎之職尿素樹脂。再者,末端是^ 之胺醋尿雜1旨,_«可料錢述硬_⑻之反I 點使用’故而為佳。又’在為具有減之單胺時,胺基二 322162 22 201107439 羥基兩方雖可與胺酯預聚物之末端異氰酸基反應,但以胺 基之反應性較高,而會優先地與異氰酸基反應。 使用上述反應停止劑(d)時的使用量,在胺酯尿素樹脂 (A)100重量%中,從確保樹脂之反應安定性之觀點而言, 以0. 05重量%以上為佳,從適當控制樹脂之重量平均分子 量(Mw)並確保感壓式接著劑之耐久性之觀點而言,以在2 重量%以下為佳。 又,對於如此所得之胺酯尿素樹脂(A)的羥基,可使環 狀酯化合物及/或環狀醚化合物進行開環加成而進行改 質。 關於本發明中使用之胺酯尿素樹脂(A)的製造方法,首 先,使多元醇(a)與多異氰酸酯(b)反應,而製作具有至少 1個異氰酸基之胺酯預聚物。其次,使所得之胺酯預聚物 與多胺基化合物(c)與因應需求之反應停止劑(d)反應,即 可製作胺酯尿素樹脂(A)。 在合成胺酯預聚物時,可使用習知之觸媒。可列舉如: 三級胺系化合物、有機金屬系化合物等。 作為三級胺系化合物者,可列舉如:三乙基胺、三伸 乙二胺、N,Ν’-二曱基苄基胺、N-曱基嗎啉、二氮雜雙環十 一碳烯(別名:DBU)等,可單獨使用,亦可組合2種以上而 使用。 作為有機金屬系化合物者,可列舉如:錫系化合物、 及非錫系化合物。 作為錫系化合物者,可列舉如:二氯化二丁基錫、氧 23 322162 201107439 化二丁基錫、二溴化二丁基錫、二馬來酸二丁基錫、二月 桂酸二丁基錫(別名:DBTDL)、二醋酸二丁基錫、硫化二丁 基錫、硫化三丁基錫、氧化三丁基錫、醋酸三丁基錫、乙 氧化三乙基錫、乙氧化三丁基錫、氧化二辛基錫、氣化三 丁基錫、三氯醋酸三丁基錫、二月桂酸二辛基錫(別名: D0TDL)、2-乙基己酸錫等。 作為非錫系化合物者,可以列舉如:二氣化二丁基鈦、 鈦酸四丁酯(tetrabutyl titanate)、三氣化丁氧基鈦等鈦 系;油酸鉛、2-乙基己酸鉛、安息香酸鉛、環烷酸鉛(lead naphthenate)等鉛系;2-乙基己酸鐵、乙醯丙酮酸鐵等鐵 系;安息香酸鈷、2-乙基己酸鈷等鈷系;環烷酸鋅、2-乙 基己酸鋅等鋅系;環烷酸锆等。 上述觸媒之中,二月桂酸二丁基錫(別名:DBTDL)、二 月桂酸二辛基錫(別名:D0TDL)、2-乙基己酸錫等,係從反 應性及衛生性之觀點而言為佳者。 上述三級胺系化合物、有機金屬化合物等觸媒,可單 獨使用也可併用,尤其當併用聚酯二醇類與聚醚二醇類作 為多元醇成分時,藉由併用二月桂酸二丁基錫與2-乙基己 酸錫,因為可得到安定性均勻之胺酯預聚物,故而為佳。 在合成胺酯預聚物時所使用之有機金屬化合物觸媒, 係在胺酯預聚物與多胺基化合物(c)反應時,可顯著地促進 反應。異氰酸基與胺基之反應原本即為非常快速,但在有 機金屬化合物觸媒之存在下,會更加促進反應,而有難以 控制之情形。此時,若存在有螯合化合物,則藉由使螯合 24 322162 201107439 化合物與有機金屬化合物觸媒形成螯合,而可調整有機金 屬化合物觸媒之觸媒能’能容易地控制與多胺基化合物(c) 之反應。 作為此螯合化合物者,可列舉如:乙醯丙酮、二曱基 乙二肟(dimethylglyoxime)、8-羥基喹啉(oxine)、雙硫腙 (dithizone)、如伸乙二胺四醋酸(別名:EDTA)等聚胺基氧 酸、如棒樣酸等氧基幾酸、縮合破酸等。在螯合化合物之 中,乙醯丙酮係因可溶於有機溶劑中,有揮發性,且必要 的話可容易除去,故而為佳。 上述螯合化合物若沒有特別除去的話,反應後也會殘 留在胺酯尿素樹脂(A)中。含有上述胺酯尿素樹脂(A)之本 發明之導電構件用感壓式接著劑組成物,雖含有硬化杰 (B) ’但此時,螯合化合物也可調整胺酯尿素樹脂(A)與硬 化劑(B)之反應速度,結果可獲得保存安定性優異之導電構 件用感壓式接著劑組成物。 在合成上述胺酯預聚物時’能適當使用習知的溶劑。 溶劑的使用可發揮使控制反應變容易之作用。在如此目的 下所使用之溶劑,可列舉如:甲基乙基酮、醋酸乙g旨、甲 苯、二曱苯、丙酮、笨、二噚烷、乙腈、四氫呋喃、二乙 二醇醇二甲醚(diglyme)、二曱基亞石風(dimethyl sulfoxide)、N-甲基吡咯啶酮、N-甲基甲醯胺(^贴处^ formamide)等。從胺酯尿素樹脂(A)之溶解性、溶劑的、弗 點、多胺基化合物(c)的溶解性等觀點而言,尤其以醋酸乙 酯、甲苯、曱基乙基酮、或此等之混合溶劑為佳。使用、、容 201107439 劑時之胺輯預聚物反應系内之濃度,樹脂固形份係以5〇至 95重量%為佳,更佳是60至90重量%,此濃度過低時反應 性會過度降低而不佳。 合成胺酯預聚物之胺酯化反應,可有各種方法,大致 區分成以下之2種方法。 [i ]將夕元醇(a)與多異氰酸酯(b)、加上溶劑、及觸媒予以 全部饋入並使其反應的方法。 [i i ]將多元醇(a)與溶劑饋入燒瓶中,於其中滴下多異氰酸 酯(b)後’因應必要添加觸媒並使其反應的方法。 精後控制反應時是以[i i ]之方法為宜。 得到胺酯預聚物之胺酯化反應溫度,以在12(rc以下 為佳,更佳是50至110艽。比120。(:高時,反應速度之控 制變困難,難以得到具有預定之重量平均分子量與結構之 胺酯預聚物。因此,胺酯化反應係以在觸媒之存在下於5〇 至110°C進行1至20小時為佳。 多元醇(a)與多異氰酸酯(b)之配合比率,是隨化合物 之反應性、3價以上之化合物的存在比率、所得樹脂之用 途等而有很大的變化。胺酯預聚物因為具有至少i個異氰 酸基’故相對於多元醇(a)中之羥基丨莫耳,多異氰酸酯(b) 中的異氰酸基必須多於i莫耳,而以丨〇1至4〇〇莫耳為 佳,以1.02至2.00莫耳之範圍内為更合適。 如上所得之作為含有異氰酸基之化合物的胺醋預聚物 中的異氰酸基、好胺基化合物⑹所具有的—級或二級胺 基之尿素化反應,係大致區分成以下之2種方法。 322162 26 201107439 [iii] 將胺酯預聚物饋入燒瓶中,滴下多胺基化合物(c)並 使其反應的方法。 [iv] 將多胺基化合物(c)饋入燒瓶中,滴下胺酯預聚物並使 其反應的方法。 若反應中沒有問題的話,則以操作容易之[i i i ]之方法 為佳。 尿素化反應之溫度係以在100°C以下為佳,更佳是在 70°C以下。當即使是在70°C中之反應速度也快速而導致不 能適當地控制反應時,則以50°C以下更佳。高於100°C時, 反應速度之控制變得困難,很難得到具有預定之重量平均 分子量與結構之胺酯尿素樹脂(A)。又,使用醇系溶劑作為 多胺基化合物(c)之合成溶劑時,當滴下多胺基化合物(c) 時,將反應系内之溫度先設在50°C以下,以先設在40°C以 下為更佳。 反應停止劑(d)之使用量,在與多胺基化合物(c)混合 添加時、與單獨最後添加時是不同的,在混合添加時,相 對於胺酯預聚物中之異氰酸基1莫耳,以使用令反應停止 劑(d)中之胺基成為0. 5莫耳以下之量為佳,以使用令其成 為0. 3莫耳以下之量為更佳。另一方面,單獨最後添加反 應停止劑(d)時,相對於最終存在之異氰酸基1莫耳,反應 停止劑(d)中之胺基係以在0. 5至3. 0莫耳為佳,尤其在以 胺酯尿素樹脂(A)之安定化作為目的時,以在1至3. 0莫耳 為佳。反應停止劑(d)之使用量在上述範圍外時,有可能看 到成膜性降低或是變著色等不良影響的情形。 27 322162 201107439 反應之終點係依據由滴定所得之異氰酸酯%之測定、。 是由IR測定所得之異氰酸酯波峰之消失來判定。 气 具有羧基或三級胺基之胺酯尿素樹脂(A)係因為I 水中分散或是溶解’故可藉由習知的方法而離子化: 胺酯尿素樹脂(A)之分子量是藉由Gpc(凝膠滲透層冷 法)所得之換算成標準聚苯乙烯的重量平均分子量,必二^ 有 50, 000 至 200, 000。而以 70, 〇〇〇 至 18〇, 〇〇〇 為佳,^ 佳是在80, 000至150, 000。該重量平均分子量未達5〇,〇⑽ 時,感壓式接著劑之耐久性與光學機能維持性的平衡會變 差,另一方面,該重量平均分子量超過2〇〇, 〇〇〇時,則接 著力會下降、或是黏度太高而導致處理變難。 所得胺酯尿素樹脂(A)之溶液黏度並無特別限定,依據 樹脂之用途來選擇,而以固形份5〇重量%且3〇〇〇至 2500〇mpa· s(25t)者為佳。胺酯尿素樹脂(A)之溶液黏度 過高時,接著劑組成物的塗布加工可能會有困難,又,過 低時有不能製成有充分分子量之樹脂的情形。 其次,針對硬化劑(B)進行說明。本發明之感壓式 劑組成物的特徵仙對於上述㈣尿素樹脂⑴⑽重量 X含有硬化劑⑻G. 1 1 3重量份。同時,接著劑組成物 3有複數種之胺酯尿素樹脂(A),也可含有複數種之硬化 劑(B)。 在士述胺酯尿素樹脂(A)中存在之反應性官能基,可列 牛如皂基羧基等。因此,在本發明中使用之硬化劑(b) 所具有的官能基’可列舉如:異氰酸基、環氧基、烧氧基 322162 28 201107439 石夕烧基、羥曱基、氮丙咬(aziridine)基、碳化二亞胺基等。 作為硬化劑(B )者,可列舉如:多異氰酸S旨化合物、多 官能環氧基化合物、高分子量聚碳化二亞胺類、含N-羥曱 基之化合物、多官能氮丙β定化合物、金屬螯合物等,其中, 為了有效地發揮作為硬化劑之作用,以在分子内具有2個 以上可與胺酯尿素樹脂(Α)之羥基反應的官能基的化合物 為適用,係因交聯反應後之接著性及對被覆層之密著性優 良,而為適合使用。 作為多異氰酸酯化合物者,只要是在分子内具有複數 個異氰酸基之化合物就可以,並無特別限定。作為多異氰 酸酯化合物之例子者,可列舉如:伸甲苯二異氰酸酯、六 亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、伸苯二曱基二 異氰酸酯、加氫伸苯二曱基二異氰酸酯、二苯基曱烷二異 氰酸酯、加氫二苯基曱烷二異氰酸酯、四曱基伸苯二曱基 二異氰酸酯、萘二異氰酸酯、三苯基曱烷二異氰酸酯、聚 曱基聚苯基二異氰酸酯等多異氰酸酯化合物、及此等多異 氰酸酯化合物與三羥曱基丙烷等多元醇化合物的加成體、 此等多異氰酸酯化合物之縮二脲體或三聚異氰酸酯體,再 者,此等多異氰酸酯化合物與習知之聚醚多元醇或聚酯多 元醇、丙烯醯基多元醇、聚丁二烯多元醇、聚異戊二烯多 元醇等之加成體等。 多官能環氧基化合物只要是在分子内有複數個環氧基 之化合物即可,無特別之限制。作為多官能環氧基化合物 者,例如可列舉:乙二醇二縮水甘油醚、聚乙二醇二縮水 29 322162 201107439 甘油醚、1,6-己二醇二縮水甘油醚、雙酚A_環氧氣丙烷 (epichlorohydrin)型環氧樹脂、N,N,N,,Ν’ -四縮水甘油基 -間-笨二曱胺、雙⑼川一二縮水甘油基胺基曱基)環己 烷、Ν,Ν-二縮水甘油基苯胺、Ν,Ν_二縮水甘油基甲苯胺等。 作為高分子量聚碳化二亞胺類者,可列舉日清紡績股 份公司之Carbodilite系列。其中以Carb〇diHte v 〇1、 〇3、05、07、09係因與有機溶劑之相溶性優良而為佳。 作為多官能氮丙咬化合物者,列舉如:2, 2, _雙經基甲 基丁醇參[3-0-氮丙啶基)丙酸酯]、4,4, _雙(伸乙基亞胺 基羰基胺基)二苯基甲烷等。 作為金屬螯合物者,列舉如:鋁、鐵、銅、鋅、錫、 欽、錄、錄、鎮、飢、鉻、及錯等多價金屬與乙酿丙嗣或 乙醯醋酸乙酯之配位化合物等。 上述硬化劑(B)可單獨使用或併用。作為上述硬化劑(B) 者,從反應性或適用期(pot life)之觀點而言,以多異氰 酸酯化合物為佳,又從感壓式接著劑層之光學特性、再從 财發泡剝離性等來看,尤其以六亞甲基二異氛酸醋三經甲 基丙燒加成體、六亞甲基二異氛酸醋三聚異氛酸醋體、六 亞甲基一異氰酸_二腺體、或是伸苯二〒基二異氛酸酯 二羥甲基丙炫加成體為佳。 本發明之感塵式接著劑組成物之特徵,係相對於胺酯 尿素樹脂(A)1GG重量份,含有硬化劑⑻0.〗至3重量份。 ^者’以含有硬化劑⑽.2至U重量份為較佳。硬化劑 )之量超過3重量份時,由感愿式接著劑組成物所形成之 322162 30 201107439 感壓式接著劑層的交聯結構會變密,感壓式接著劑層的黏 性(tackiness)有降低之傾向,對被黏體之接著性會下降。 另一方面,硬化劑(B)之量未達0. 1重量份時,由於得不到 充分之交聯結構,故凝聚力會下降,财熱性、财濕熱性會 降低。 藉由胺酯尿素樹脂(A)之反應性官能基與上述硬化劑 (B)中之官能基的反應,胺酯尿素樹脂(A)會三次元交聯, 不僅確保與各種基材或被黏體之密著性,且亦可提升在比 以往更嚴苛之條件下之耐熱性及耐濕熱性。因此,本案發 明之接著劑組成物可以特別適合作為導電構件用途而使 用。 本發明之感壓式接著劑組成物若以提高耐濕熱性為目 的,也可含有具有烷氧基矽烷基之矽烷偶合劑。矽烷偶合 劑在感壓式接著劑層中尤其容易形成傾斜結構,而局部存 在於接著劑層表面,被認為尤其對提高耐濕熱特性或提高 接著力方面特別會發揮效果。 作為石夕烧偶合劑者可使用習知者。例如可列舉:7 -(曱 基)丙稀酿氧基曱基三曱氧基石夕烧、7 -(曱基)丙稀酿氧基 丙基三甲氧基石夕烧、7_(曱基)丙稀酿氧基丙基三乙氧基石夕 烧、7_(曱基)丙烯醯氧基丙基三丁氧基石夕烧、7_(曱基) 丙烯醯氧基丙基曱基二曱氧基矽烷、7-(甲基)丙烯醢氧基 丙基甲基二乙氧基矽烷等具有(曱基)丙烯醯氧基與烷氧基 之矽烷化合物; 乙稀基三甲氧基石夕烧、乙稀基三乙氧基石夕烧、乙稀基 31 322162 201107439 三丁氧基碎烧、乙稀基曱基二曱氧基石夕烧等具有乙稀基之 烧氧基梦烧; 5-己烯基三甲氧基矽烷、9-癸烯基三曱氧基矽烷、苯 乙烤基三甲氧基石夕烧等院氧基石夕烧; 7-胺基丙基三甲氧基矽烷、T-胺基丙基三乙氧基矽 烧、7"_胺基丙基曱基二曱氧基石夕烧、7_胺基丙基甲基二 乙氧基石夕烧等具有胺基烧基與烧氧基之石夕烧; r-M基丙基三甲氧基矽烷、r-Μ基丙基三乙氧基矽 烷、r-M基丙基曱基二曱氧基矽烷、巯基丙基曱基二 乙氧基梦烧、基曱基苯基乙基三曱氧基梦院、疏基曱 基三曱氧基矽烷、6-巯基己基三甲氧基矽烷、10-M基癸基 三曱氧基矽烷等具有Μ基之化合物; IS-1000、ΙΑ-100Α、ΙΜ-1000、SP-10(日鑛金屬股份公 司製)等具有咪唑基之化合物; 四曱氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁 氧基矽烷等四烷氧基矽烷; 3-縮水甘油氧基丙基三曱氧基石夕院、3-縮水甘油氧基 丙基甲基二曱氧基矽烷、2-(3,4-環氧基環己基)乙基三甲 氧基矽烷、3-氯丙基甲基二曱氧基矽烷、3-氯丙基三曱氧 基矽烷、苯基三曱氧基矽烷、六曱基矽氮烷、二苯基二甲 氧基石夕烧、1,3, 5-參(3-三甲氧基石夕炫基丙基)三聚異氰酸 酉旨、乙稀基參(2 -曱氧基乙氧基)石夕烧、Ν_(2 -胺基乙基)-3-胺基丙基曱基二曱氧基發烧、Ν-(2-胺基乙基)-3-胺基丙基 三曱氧基矽烷、3-異氰酸基丙基三乙氧基矽烷等。 32 322162 201107439 此等之任何1種以上係可單獨使用,也可混合複數種 而使用。 ' 在上述矽烷偶合劑中,從提高耐熱/耐濕熱特性之方 面而:,以使用3-異氣酸基丙基三乙氧基石夕烧、或3_縮水 甘油氧基丙基二甲氧基石夕烧、或具有味嗤基之石夕院偶合劑 為佳。尤其當使用3-異氰酸基丙基三乙氧基矽烷或 IM-1_ (含有咪哇基之石夕燒;3 (咪唾+基)—2_曱基丙酸 3 (二甲氧基矽烷基)丙酯與其部分水解反應生成物的混合 物)時,可得到能特別提高加工性、耐可塑劑性、耐執/耐 濕熱性,且對導電構件有特別高的接著力之感壓式接著劑 組成物。 使用上述矽烷偶合劑時,相對於胺酯尿素樹脂(Α)ι〇〇 重量份,為了得到充分之耐濕熱特性及提高接著力之效 ^,以使用0.1重量份以上為佳,另一方面,即使使用太 多量也得不到更好之效果,且還有接著力會下降之情形, 故以在1.0重量份以下之範圍來使用為佳。 本發明之感壓式接著劑組成物,因應需要,也可併用 其他之樹脂,例如丙烯酸系樹脂、聚酯樹脂、胺基樹脂、 每氧樹脂、聚胺醋樹脂。再者,因應用途,也可調配有機 /無機之顏料、充填劑、著色劑、紫外線吸收 劑、消泡劑、光安定劑等添加劑。 '^ 使用本發明之感壓式接著劑組成物的導電構件(導電 ί·生構件),只要是具有導電性的構件即無特別限定,可列 舉.由ΙΤ0或ΑΤ0等透明導電膜、金屬蒸鍍薄膜、金屬粒 322162 33 201107439 子所形成的導電金屬電路等。 使用本發明之感壓式接著劑組成物,可得到含有感壓 式接著劑層與薄片狀基材之積層製品(以下,稱為「導電構 件用感壓式接著性薄片」或「感壓式接著性薄片」)。例如, 在各種薄片狀基材之單面或兩面,藉由將本發明之感壓式 接著劑組成物予以塗布、乾燥、硬化,可得到該導電構件 用感壓式接著性薄片。構成感壓式接著性薄片之感壓式接 著劑層,因為是「感壓式」,故在室溫左右具有黏性。 塗布接著劑組成物時,可添加適當之液狀媒體,例如 醋酸乙酯、曱苯、曱基乙基酮、異丙醇、其他之烴類溶劑 等有機溶劑或再添加水而調整黏度,並可將接著劑組成物 加熱而使黏度下降。但是,當大量添加水或醇等時,因為 有可能引起胺酯尿素樹脂(A)與硬化劑(B)之反應抑制,故 需要注意。 作為薄片狀基材者,並無特別限定,可列舉如:玻璃 紙(cellophane)、各種塑膠薄片、橡膠、發泡體、棉布、 橡膠被覆布、樹脂含浸布、玻璃板、金屬板、木材、偏光 板等光學薄膜等平坦形狀者。又,可單獨使用各種基材, 也可使用經積層複數者而成的多層狀態者。再者,也可使 用表面經剝離處理者、或經抗靜電處理者。 各種塑膠薄片也稱為各種塑膠薄膜,可列舉如:聚乙 烯醇薄膜或三乙酸纖維素薄膜、聚丙烯、聚乙烯、聚環烯 烴、乙烯-醋酸乙烯酯共聚合物等聚烯烴系樹脂之薄膜;聚 對苯二曱酸乙二酯、聚對苯二甲酸丁二酯、聚萘二曱酸乙 34 322162 201107439 一 §曰等聚酯系樹脂之薄膜;聚碳酸酯系樹脂薄膜;聚降冰 片烯系樹脂薄膜;聚芳酸酯(p〇lyarylate)系樹脂薄膜;丙 稀夂糸料月日薄膜,t本硫越(polyphenylene sulfide)樹脂 薄膜,聚笨乙烯樹脂薄膜;乙烯系樹脂薄膜;聚醯胺系樹 脂薄膜;聚醯亞胺系樹脂薄膜;環氧系樹脂、環烯烴系樹 脂薄膜等。 依據通常方法,以適當方法將接著劑組成物塗布在上 述薄片狀基材後,當接著劑組成物含有有機溶劑或水等液 狀媒體時則除去液狀媒體,或是當感壓式接著劑組成物不 含有會揮發之液狀媒體時則將熔融狀態之接著劑層冷卻並 固化,而可在薄片狀基材上形成接著劑層。感壓式接著劑 層之厚度係以0.1_至250 /zm為佳’以20/zm至2〇〇;czm 更佳。未達〇. l#m則得不到充分之接著力,但即使超過 250 a m ’接著力等特性亦多半不會更加提高。 將接著劑組成物塗布在薄片狀基材之方法,並無特別 限定,可列舉如:線棒(Meyerbar)、塗布機(appHcat〇d、 刷毛、喷霧、輥筒、凹版塗布機、模具塗布機(diec〇ater)、 唇型塗布機、逗號式塗布機(comma coater)、刀片式塗布 機、反向塗料器(reverse coater)、旋轉式塗布機等各種 之塗布方法。接著劑層之乾燥方法,並無特別限定,可列 舉如:利用熱風乾燥、紅外線或減壓法者。乾燥條件是隨 接著劑組成物之硬化形態、膜厚、及選擇之溶劑而不同, 通常以在60至1801左右之熱風加熱即可。 將由上述本發明之感壓式接著劑組成物所形成之感壓 322162 ί: 35 201107439 ^者薄膜、破璃等為首之透明光學 構件上,可形成積層體。本發明之積層體=之導電 構件或透明光學構材上制有由^ & 思之導電 劑組成物所形成之感_劑層者。著 膜或金屬電路等導電構件上積層感壓式接著劑it士才Γ =:性之觀點而言是特別有效。在感壓式;著綱之 面進行剝離處理過之薄片狀基材。 隹八表 、該積層體可藉由例如下述方法而獲得:⑴在經剝離處 里過之薄片狀基材的剝離處理面上將感壓式接著劑組成物 予以塗布、乾燥後,再將以PET薄膜、玻璃等為首之透明 光學構材或是薄片狀之導電構件積層在感壓式接著劑層表 面(此稱為轉印塗布法);或是(2)在以PET薄膜、玻璃等為 首之透明光學構材或是薄片狀之導電構件上,將感壓式接 著劑組成物予以塗布、乾燥後,在感壓式接著劑層之表面 積層經剝離處理過之薄片狀基材的剝離處理面(此稱為直 接塗布法)。 — 例如,從如「經剝離處理過之薄片狀基材/感壓式接 著;=Jf/透明光學構材」之結構的積層體中,將覆蓋感壓 式接著^表面的經剝離處理過之薄片狀基材予以剝離 ,將感壓式接著劑層黏貼在薄片狀之導電構件(ΙΤ0等透 日月導:膜或金屬電路等導電構件)上,藉此而可得到如「透 " 材/感壓式接著劑層/導電構件」之結構的觸控 36 322162 201107439 式面板用薄片。又,户 接著劑層/薄片狀之;理過之薄片/感壓式 路等導電構件)」之結構轉電膜或金屬電 層表面的經制離處理過構之之:=:覆蓋感壓式接著劑 式接著鮮黏貼h #基材予以剝離後,將感壓 光與構材二八Γ 、明光學構件,藉此而可得到如「透明 先予構材/感壓式处月 面板用薄片。 心,導電構件」之結構的觸控式 之用:並之導電構件用感壓式接著性薄片或積層體 uwm制’除了上述觸控式面板之外,也可以 2於液aam、電漿顯示器、電極周邊構件等各種電 子相關構件或保護薄膜之用途。 實施例 、下藉由貫知例更具體说明本發明,但本發明之權 利範圍並不侷限在以下之實施例。同時,實施例中之「份」 及「%」在無特別聲明時係表示「重量份」及「重量%」。 δ成例4至25所得之各樹脂的重量平均分子量(Mw) 是依據以下之方法求得。 <重量平均分子量(Mw)測定>An unsaturated compound having a polyester chain having a hydroxyl group at the terminal, such as Placcel FM5L; polyethylene glycol (meth) acrylate, polypropylene glycol (mercapto) acrylate, polytetradecylene diol (fluorenyl) hydrazine An unsaturated compound having a polyether chain having a hydroxyl group at a terminal, such as an acid ester or hexaethylene glycol (mercapto) acrylate. The above-mentioned compounds may be used alone or in combination of two or more. In particular, 4-hydroxybutyl acrylate is used in terms of reactivity with a curing agent (B) to be described later and optical properties of a pressure-sensitive adhesive. Esters are preferred. In the ethylenically unsaturated compound (C2), those having no hydroxyl group include, for example, fluorene vinegar, (mercapto) acrylic acid, propyl (meth) acrylate, and fluorenyl group. ) butyl acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (meth) propylene hydrazine, (fluorenyl) propylene Acidic vinegar, decyl (meth) acrylate, decyl acrylate, undecyl (decyl) acrylate, dodecyl (meth) acrylate, tridecane (meth) acrylate Ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (methyl) Octadecyl decyl acrylate (methyl) propionic acid, nineteen carbon vinegar, (meth) acrylate, twenty carbon vinegar, (meth) acrylate, hexadecane, (meth) acrylate A (meth) acrylic acid ester having a carbon number of 1 to 22 such as a dialkyl alkoxide. When the polarity is adjusted, it is preferably an alkyl group-containing acrylate having a carbon number of 2 to 10, more preferably an alkyl group having 2 to 8 carbon atoms, or a corresponding mercapto acrylate. For the purpose of adjustment of the coating property, etc., it is preferable to use a carbon number of 6 or more. 322162 16 201107439 Also as 'ethylenically unsaturated compound (c2), can be used together: methoxypolyethyl alcohol (mercapto) benzium sulphate, ethoxypolyethylene glycol (meth) acrylate 、, propoxy polyethylene glycol (meth)acrylic acid g, n-butoxy polyethylene glycol (meth) acrylate, n-pentyloxy polyethylene glycol (meth) acrylate vinegar, phenoxy Polyethylene glycol (mercapto) acrylic acid vinegar, decyloxy polytetradecyl diol (meth) acrylate, phenoxytetraethylene glycol (mercapto) acrylate, methoxy hexaethyl Alkoxy polyalkylene glycol mono(mercapto) acrylate such as diol (mercapto) acrylate or phenoxy polyalkylene glycol mono (meth) acrylate; vinyl acetate, vinyl butyrate, Vinyl propionate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl palmitate, ethyl palmitate, etc.; vinyl esters such as butyl vinyl ether and ethyl vinyl ether; Ethers; 1-hexene, 1-octene, 1-decene, 1-dodecene, tetradecene, 1-hexadecene, etc. 0:-olefins; Acid, fumaric acid, itaconic acid, citrac nic acid; or an alkyl or alkenyl monoester, phthalic acid Monoester, isophthalic acid (fluorenyl) propylene oxiranyl ethyl monoester, terephthalic acid, fluorenyloxyethyl monoester, succinic acid, glutamic acid a carboxyl group-containing unsaturated compound such as a methoxyethyl monoester, an acrylic acid, a methacrylic acid 'crotonic acid or a cinnamic acid; an unsaturated compound containing a guanamine group; an unsaturated compound containing a dialkylamino group; The ammonium salt-based unsaturated compound or the like contains a nitrogen-containing unsaturated compound. As the unsaturated compound containing a guanamine group, for example, (mercapto) 17 322162 201107439 acrylamide, N-hydroxydecyl (decyl) acrylamide, N-decyloxy fluorenyl (fluorenyl) ) acrylamide, N-ethoxymercapto-(meth) acrylamide, N-propoxymethyl-(mercapto) acrylamide, N-butoxy fluorenyl-(fluorenyl) propylene Indoleamine, N-pentyloxyindenyl-(indenyl)propenylamine, N,N-bis(hydroxyindole)propenylamine, N-hydroxyindenyl-N-decyloxyindenyl-(fluorenyl) Acrylamide, n,N-bis(methoxyindenyl)propenylamine, N-ethoxyindolyl-N-decyloxymercaptopropenylamine, N,N-di(ethoxylate) Methyl) acrylamide, N-ethoxyindolyl-N-propoxymethylmercaptopropenylamine, N,N-bis(propoxyfluorenyl)propenylamine, N-butoxy Nonyl-N-(propoxycarbonyl)mercaptopropenylamine, n,N-bis(butoxyfluorenyl)propenylamine, N-butoxyindolyl-N-(decyloxyfluorenyl) And methacrylamide, N,N-bis(pentyloxyindenyl) acrylamide, N-methoxyindenyl-N-(pentyloxyindenyl)methacrylamide, and the like. Examples of the unsaturated compound containing a dialkylamine group include didecylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutyl (meth) acrylate. Alkylaminoethyl ester, dipropylaminoethyl (mercapto)acrylate, decylethylaminoethyl (mercapto) acrylate, dinonylamino styrene, diethylamino styrene, and the like. The unsaturated compound containing a quaternary ammonium salt group is obtained by subjecting the above unsaturated group containing an alkyl group to a four-stage classification. A halogen compound having a Cr, Br' Γ or QS 〇 3 _ (Q: an alkyl group having 1 to 12 carbon atoms) as a relative ion (a quaternary ammonium salt group-containing unsaturated compound) may be exemplified by: Didecylaminoethyl decyl acrylate, dimercapto-3-(1-(methyl) acrylamide-1,1-dimercaptopropyl) ammonium chloride, trimethyl -3-(1-(indenyl) acrylamidopropyl) ammonium chloride, and triterpene 18 322162 201107439 -3-(1-(methyl) acrylamide-M-dimethylethyl) gas Ammonium and the like. Further, as the ethylenically unsaturated compound (c2), a combination of: (meth)acrylic acid perfluoromethyl methyl ester, (meth)acrylic acid perfluoroethyl methyl ester, and (meth)acrylic acid 2-all may be used in combination. Fluoryl butyl ethyl ester, 2 - perfluorohexyl ethyl (meth) acrylate, 2- perfluorooctyl ethyl (meth) acrylate, 2 - perfluoroisodecyl ethyl (meth) acrylate, (A) 2-acrylic acid 2-perfluorodecyl ethyl ester, (meth) propylene hydrazine 2-perfluorodecyl ethyl ester, (fluoro) propyl (meth) acrylate, perfluorooctyl propyl (meth) acrylate (mercapto)acrylic perfluoroalkane having a perfluoroalkyl group having a carbon number of 丨 to 2〇, such as ester, perfluorooctyl amyl (meth)acrylate, perfluorooctylundecyl (meth)acrylate Ester; perfluoroalkyl-containing unsaturated compounds such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, etc.; perfluoroalkyl-containing unsaturated compounds; vinyl trioxane, ethylene Base ginseng (no-methoxyethoxy) decane, ethylene diethoxy zeshi, (indenyl) propylene oxypropyl trioxane, etc. An unsaturated compound containing an alkylene oxide group and a derivative thereof; an epoxy group-containing unsaturated compound such as glycidyl acrylate or 3, 4-epoxycyclohexyl acrylate; allyl acetate and a propyl group Allyl compound such as benzene or allyl cyanide; vinyl cyanide, vinyl cyclohexane, vinyl decyl ketone, styrene, α-mercapto styrene, 2-mercapto styrene, chlorostyrene, etc. Vinyl compound; B block, B fast basic, B quick base 等 and other B-based compounds; In the Michael addition reaction of the compound (ci) having two or more primary amino groups and the ethylenically unsaturated compound (c2), the amine group in the compound (cl) having two or more primary amines 322162 19 201107439 The active hydrogen is 1 mol, and reacts with the ethylenically unsaturated group 1 mol in the ethylenically unsaturated compound (c2). Since the ethylenic group in the compound (ci) having two or more primary amino groups is easily subjected to Michael addition to the ethylenically unsaturated group of the compound having an electron attracting group, the ethylenically unsaturated compound (c2) is ( The methyl)acrylic compound is preferred. From the viewpoint of the efficiency of the Michael addition reaction, an acrylate compound is preferred. For the synthesis method of the compound (c3) obtained by subjecting the ethylenically unsaturated compound (C2) to a Michael addition reaction with a compound (cl) having two or more primary amino groups, a conventional method for the Michael addition reaction can be directly used. . When the ethylenically unsaturated compound (c2) is a (fluorenyl)acrylic compound, in particular, when it is an acrylate-based compound or the like, the reaction is carried out at 10 to 100 t under a catalyst such as an alcohol depending on the demand. Although it varies depending on the type of the ethylenically unsaturated compound (c2) to be used, it is preferably 4 to 8 (the reaction temperature of rc is preferred. When the reaction temperature is too high, the ester oxime exchange reaction is not produced. When the ethylenically unsaturated compound (C2) does not have an electron attracting group, the 'under-forming can be reacted in the presence of a metal catalyst. At this time, if it is heated in the presence of a catalyst, it is heated at 60 to 1 Torr. (The rc reaction is preferably carried out at a suitable reaction rate. "The solvent for the synthesis may or may not be used, and the type thereof is not particularly limited." Acetylethyl hydrazine, anthracene benzene, propyl benzene, benzene, etc. may be used. The solvent concentration in the case of using a solvent is preferably 2% by weight or more, more preferably 50% by weight or more. When it is thinner than this, it is preferable because the reaction is difficult to proceed. 322162 20 201107439 Reaction time is used The type of the ethylenically unsaturated compound (C 2 ) is different, but is terminated at 30 minutes to 5 hours. The ethylenically unsaturated compound (C2) is added to the compound (cl) having two or more primary amino groups. Ratio a method in which at least two primary or secondary amine groups remain in the compound (c3) which is reacted by the Michael addition reaction, and the primary amine group which is present in the compound (cl) having two or more primary amino groups Ear, to 〇. 1 to 1 〇 Mo Er ratio is better, better is 〇. 2 to 1. The molar ratio of oxime is preferably such that the ethylenically unsaturated group in the ethylenically unsaturated compound (c2) is reacted. When the amount of the ethylenically unsaturated group is less than the amount of the oxime, the effect of introducing the ethylenically unsaturated compound (c2) may not be obtained, and further, the storage stability may be lowered, but on the other hand, even if More than this amount is not advantageous for the reaction. The amount of the polyamine-based compound (c) used is from 0% by weight of the amine ester urea resin (A), from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and imparting durability. It is preferably 5% by weight or more, and from the viewpoint of preventing the resin from being soft and having a sufficient adhesion, it is at 8 deg. g = f 疋 2 to 5% by weight. In summary, the amount of the polyamine compound (C) in the 100% by weight of the reaction stopper (4) when the polyol (a), the polyisocyanate (乜), the polyamine compound (4), and the reaction stopper (4) are used (the amount used) Or feed amount) to 0. 5 to 8 wt% is preferred. * Amine vinegar urea resin (4) is obtained by reacting an amine vinegar prepolymerized mouth having an isocyanate group with a polyamine compound (6), but may be used as a single amine group as a reverse ageing agent (4). The compound is reacted. That is, in the case of the amine ester urea resin (1), in order to control the molecular weight, or react with an isocyanate group remaining unreacted with the amine 322162 21 201107439 ester urea resin (A), and reacting the resin The reaction inhibitor (d) can be used for the purpose of stability. The amine ester urea resin (A) at this time is a polyamine compound (c) and a reaction stopper (d) by reacting an amino ester prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b). ) The reaction is made. As the reaction-stopping agent (d), for example, in addition to a di-terminated amine such as diethylamine, di-n-butylamine, mono-n-octylamine, mono->hexylamine or monoisodecylamine, Can be used: monoethanolamine, diethanolamine, 2-amino-2-mercapto-purin-propanol, tris(fluorenyl)amine broth, 2-amino-2-ethyl-1,3-propanediol Monoamines having a sulfhydryl group; mono monomethylhydrazine, 1, dimethylene glutinous, glutinous hydrazine, etc., formhydrazide, acetaminophen, etc. ; ^Dimercapto---propane-diamine^diethyl--propane-succinimide and other compounds having a tertiary amino group and a primary amine group; r-aminopropyltriethoxy Wei et al. A monoamine compound of the carbaryl group. An amine compound having only one or two amine groups of X ' can also be used as a reaction stopper. σ Even if a monoamine compound having a hydroxyl group such as 2-amino group or propyl-propanol is used among the above-mentioned reaction stopper (4), the urea resin which retains the stability of the base can be obtained. Furthermore, the end is the amine vinegar urinary hydration, and the _« can be used as the hard _ (8). In addition, in the case of a reduced monoamine, the amine group 322162 22 201107439 hydroxyl group can react with the terminal isocyanate group of the amine ester prepolymer, but the reactivity with the amine group is higher, and preferentially Reacts with an isocyanate group. In the case of using the above-mentioned reaction stopper (d), the amount of the amine ester urea resin (A) is from 100% by weight, and from the viewpoint of ensuring the reaction stability of the resin, it is 0. It is preferably 0% by weight or more, and more preferably 2% by weight or less from the viewpoint of appropriately controlling the weight average molecular weight (Mw) of the resin and ensuring the durability of the pressure-sensitive adhesive. Further, the hydroxyl group of the amine ester urea resin (A) thus obtained can be modified by ring-opening addition of a cyclic ester compound and/or a cyclic ether compound. In the method for producing the amine ester urea resin (A) used in the present invention, first, the polyol (a) and the polyisocyanate (b) are reacted to prepare an amine ester prepolymer having at least one isocyanate group. Next, an amine ester urea resin (A) can be produced by reacting the obtained amine ester prepolymer with the polyamine compound (c) and the reaction stopper (d) according to the demand. In the synthesis of the amine ester prepolymer, a conventional catalyst can be used. Examples thereof include a tertiary amine compound and an organometallic compound. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, Ν'-dimercaptobenzylamine, N-mercaptomorpholine, diazabicycloundecene. (alias: DBU), etc., may be used singly or in combination of two or more. Examples of the organometallic compound include a tin-based compound and a non-tin-based compound. Examples of the tin-based compound include dibutyltin dichloride, oxygen 23 322162 201107439 dibutyltin dichloride, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (alias: DBTDL), diacetic acid. Dibutyltin, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxylate, tributyltin ethoxylate, dioctyltin oxide, tributyltin oxide, tributyltin trichloride, dilaurin Dioctyltin acid (alias: D0TDL), tin 2-ethylhexanoate, and the like. Examples of the non-tin-based compound include titanium such as dibutyltitanium dihydride, tetrabutyl titanate, and tri-gasified butoxytitanium; lead oleate and 2-ethylhexanoic acid; Lead, lead benzoate, lead naphthenate, etc.; iron such as iron 2-ethylhexanoate or iron acetylacetonate; cobalt such as cobalt benzoate or cobalt 2-ethylhexanoate; Zinc such as zinc naphthenate or zinc 2-ethylhexanoate; zirconium naphthenate. Among the above catalysts, dibutyltin dilaurate (alias: DBTDL), dioctyltin dilaurate (alias: D0TDL), tin 2-ethylhexanoate, etc., from the viewpoint of reactivity and hygiene Be good. The catalyst such as the above-mentioned tertiary amine compound or organometallic compound may be used singly or in combination, and in particular, when a polyester diol and a polyether diol are used in combination as a polyol component, by using dibutyltin dilaurate in combination with Tin-ethyl 2-ethylhexanoate is preferred because it can provide an amine ester prepolymer having a stable stability. The organometallic compound catalyst used in the synthesis of the amine ester prepolymer can significantly promote the reaction when the amine ester prepolymer is reacted with the polyamine compound (c). The reaction of the isocyanate group with the amine group is originally very rapid, but in the presence of the organic metal compound catalyst, the reaction is more promoted, and it is difficult to control. At this time, if a chelating compound is present, the chelate of the organometallic compound catalyst can be adjusted to easily control the polyamine by chelation of the chelate 24 322162 201107439 compound with the organometallic compound catalyst. The reaction of the base compound (c). As such a chelate compound, for example, acetamidine acetone, dimethylglyoxime, 8-oxoquinoline (oxine), dithizone (dithizone), such as ethylenediaminetetraacetic acid (alias) : EDTA) and the like, such as polyamino oxyacids, oxyacids such as bar acid, condensed acid, and the like. Among the chelating compounds, acetamidine is preferred because it is soluble in an organic solvent, is volatile, and can be easily removed if necessary. If the chelate compound is not specifically removed, it remains in the amine ester urea resin (A) after the reaction. The pressure-sensitive adhesive composition for a conductive member of the present invention containing the above-mentioned amine ester urea resin (A) contains hardening (B) 'but at this time, the chelating compound can also adjust the amine ester urea resin (A) and The reaction rate of the curing agent (B) results in a pressure-sensitive adhesive composition for a conductive member excellent in storage stability. A conventional solvent can be suitably used in the synthesis of the above amine ester prepolymer. The use of a solvent serves to facilitate the control of the reaction. Examples of the solvent to be used for such a purpose include methyl ethyl ketone, ethyl acetate, toluene, diphenylbenzene, acetone, stupid, dioxane, acetonitrile, tetrahydrofuran, diethylene glycol dimethyl ether. (diglyme), dimethyl sulfoxide, N-methylpyrrolidone, N-methylformamide (wherein formamide). From the viewpoints of solubility of the urethane urea resin (A), solvent, fulcrum, solubility of the polyamine compound (c), etc., especially ethyl acetate, toluene, mercaptoethyl ketone, or the like A mixed solvent is preferred. When using the concentration in the amine prepolymer reaction system of the 201107439 agent, the solid content of the resin is preferably from 5 to 95% by weight, more preferably from 60 to 90% by weight, and the reactivity is too low when the concentration is too low. Excessive reduction is not good. The amine esterification reaction of the synthetic amine ester prepolymer can be roughly classified into the following two methods by various methods. [i] A method in which all of the oligomer (a) and the polyisocyanate (b), a solvent, and a catalyst are fed in and reacted. [i i ] A method in which a polyol (a) and a solvent are fed into a flask, and the polyisocyanate (b) is dropped thereto, and a catalyst is added and reacted as necessary. It is preferable to control the reaction after the fineness by the method of [i i ]. The amine esterification reaction temperature of the amine ester prepolymer is obtained at a temperature of 12 (sec or less, more preferably 50 to 110 Torr. Ratio: 120. (When high, the control of the reaction rate becomes difficult, and it is difficult to obtain a predetermined one. The amine-ester prepolymer having a weight average molecular weight and structure. Therefore, the amine esterification reaction is preferably carried out at from 5 Torr to 110 ° C for 1 to 20 hours in the presence of a catalyst. Polyol (a) and polyisocyanate ( b) The compounding ratio varies greatly depending on the reactivity of the compound, the ratio of the compound having a trivalent or higher value, the use of the obtained resin, etc. The amine ester prepolymer has at least i isocyanate groups. The isocyanate group in the polyisocyanate (b) must be more than i mole relative to the hydroxy oxime in the polyol (a), and preferably 丨〇1 to 4 〇〇mol, to 1. 02 to 2. 00 Moel's range is more suitable. The urea group reaction of the isocyanate group and the amine group of the amine vinegar prepolymer obtained as the above-mentioned compound containing the isocyanate group as the above-mentioned amine-based compound (6) is roughly classified into the following 2 methods. 322162 26 201107439 [iii] A method in which an amine ester prepolymer is fed into a flask, and the polyamine compound (c) is dropped and allowed to react. [iv] A method in which the polyamine-based compound (c) is fed into a flask, and the amine ester prepolymer is dropped and allowed to react. If there is no problem in the reaction, it is preferable to use the method [i i i ] which is easy to handle. The temperature of the ureaification reaction is preferably 100 ° C or lower, more preferably 70 ° C or lower. When the reaction rate is rapid even at 70 ° C, the reaction cannot be appropriately controlled, and it is more preferably 50 ° C or less. Above 100 °C, the control of the reaction rate becomes difficult, and it is difficult to obtain an amine ester urea resin (A) having a predetermined weight average molecular weight and structure. Further, when an alcohol-based solvent is used as the synthetic solvent of the polyamine-based compound (c), when the polyamine-based compound (c) is dropped, the temperature in the reaction system is first set at 50 ° C or lower, and is set at 40 ° first. Below C is better. The amount of the reaction-stopping agent (d) used is different when it is mixed with the polyamine-based compound (c), and when it is added last, and when added, the isocyanate group in the amine ester prepolymer is added. 1 mole, in order to use the amine in the reaction stop agent (d) to become 0. The amount below 5 moles is better, so that it is used to make it 0. The amount below 3 moles is better. On the other hand, when the reaction stopper (d) is finally added alone, the amine group in the reaction stopper (d) is at 0. 5 to 3. 0 mole is preferred, especially when the stability of the amine ester urea resin (A) is used, in the range of 1 to 3. 0 Mo is better. When the amount of the reaction-stopping agent (d) is outside the above range, there is a possibility that the film forming property is lowered or the coloring is adversely affected. 27 322162 201107439 The end point of the reaction is based on the determination of the % isocyanate obtained by titration. It is judged by the disappearance of the isocyanate peak obtained by IR measurement. The amine ester urea resin (A) having a carboxyl group or a tertiary amine group is ionized by a conventional method because I is dispersed or dissolved in water: The molecular weight of the amine ester urea resin (A) is by Gpc (The gel permeation layer cold method) The weight average molecular weight obtained by converting into standard polystyrene must be from 50,000 to 200,000. For 70, 〇〇〇 to 18〇, 〇〇〇 is better, and ^ is better at 80,000 to 150,000. When the weight average molecular weight is less than 5 Å, the balance between the durability of the pressure-sensitive adhesive and the optical function maintenance property is deteriorated when 〇(10), and on the other hand, the weight average molecular weight exceeds 2 〇〇, 〇〇〇, Then the force will drop, or the viscosity will be too high and the processing will become difficult. The solution viscosity of the obtained amine ester urea resin (A) is not particularly limited and is selected depending on the use of the resin, and is preferably 5 wt% by weight and 3 Torr to 2500 〇mpa·s (25 t). When the solution viscosity of the amine ester urea resin (A) is too high, the coating process of the adhesive composition may be difficult, and when it is too low, a resin having a sufficient molecular weight may not be formed. Next, the hardener (B) will be described. The characteristic composition of the pressure sensitive agent of the present invention contains a hardener (8) G for the weight of the above (4) urea resin (1) (10). 1 1 3 parts by weight. Meanwhile, the adhesive composition 3 has a plurality of amine ester urea resins (A), and may also contain a plurality of hardeners (B). The reactive functional group present in the amine resin urea resin (A) may be a bovine such as a soap group or the like. Therefore, the functional group ' which the hardener (b) used in the present invention has may be, for example, an isocyanato group, an epoxy group, an alkoxy group 322162 28 201107439, a sulfhydryl group, a hydroxy group, a nitrogen propylene group (aziridine) group, carbodiimide group, and the like. Examples of the curing agent (B) include polyisocyanate S compounds, polyfunctional epoxy compounds, high molecular weight polycarbodiimides, N-hydroxyindole-containing compounds, and polyfunctional nitrogen-propylene beta. In order to effectively exhibit the function as a curing agent, a compound having two or more functional groups reactive with a hydroxyl group of an amine ester urea resin in the molecule is suitable. It is suitable for use because it has excellent adhesion to the crosslinking reaction and adhesion to the coating layer. The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanato groups in the molecule. Examples of the polyisocyanate compound include, for example, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzoyl diisocyanate, hydrogenated benzodidecyl diisocyanate, and Polyisocyanates such as phenyldecane diisocyanate, hydrogenated diphenylnonane diisocyanate, tetradecylphenylene diisocyanate, naphthalene diisocyanate, triphenyldecane diisocyanate, polydecyl polyphenyl diisocyanate a compound, an adduct of such a polyisocyanate compound and a polyhydric alcohol compound such as trishydroxypropylpropane, a biuret or a trimeric isocyanate of the polyisocyanate compound, and further, such polyisocyanate compounds and conventionally known An adduct of a polyether polyol or a polyester polyol, an acryl-based polyol, a polybutadiene polyol, a polyisoprene polyol, or the like. The polyfunctional epoxy compound is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether and polyethylene glycol dicondensate 29 322162 201107439 glyceryl ether, 1,6-hexanediol diglycidyl ether, bisphenol A_ ring Epoxyhydrin type epoxy resin, N, N, N, Ν'-tetraglycidyl-m-stactylamine, bis(9)-glycidylamino fluorenyl) cyclohexane, hydrazine , Ν-diglycidyl aniline, hydrazine, hydrazine _ diglycidyl toluidine and the like. As the high molecular weight polycarbodiimide, the Carbodilite series of Nisshinbo Co., Ltd. can be cited. Among them, Carb〇diHte v 〇1, 〇3, 05, 07, and 09 are excellent in compatibility with an organic solvent. As the polyfunctional nitrogen-cyanide compound, for example, 2, 2, bis-bis-methylbutanol gin [3-0-aziridine) propionate], 4, 4, _ bis (ethyl) Iminocarbonylamino)diphenylmethane and the like. As metal chelates, for example, aluminum, iron, copper, zinc, tin, chin, recorded, recorded, town, hunger, chromium, and wrong polyvalent metals and ethyl acetonitrile or ethyl acetate Coordination compounds, etc. The above hardener (B) may be used singly or in combination. As the above-mentioned curing agent (B), from the viewpoint of reactivity or pot life, it is preferable to use a polyisocyanate compound, and also from the optical characteristics of the pressure-sensitive adhesive layer, and further from the foaming property. Etc., especially the hexamethylene diiso-acid vinegar trimethyl propylene hydride addition, hexamethylene diisocyanate trimeric oleic acid hexahydrate, hexamethylene monoisocyanate _ two glands, or benzodiazepine diisocyanate dimethylol propyl daddy addition is preferred. The composition of the dust-sensitive adhesive of the present invention is characterized in that it contains a hardener (8) with respect to 1 part by weight of the amine ester urea resin (A). 〗 to 3 parts by weight. ^者' to contain hardener (10). 2 to U parts by weight are preferred. When the amount of the hardener) exceeds 3 parts by weight, the crosslinked structure of the 322162 30 201107439 pressure-sensitive adhesive layer formed by the composition of the resistive adhesive becomes dense, and the adhesiveness of the pressure-sensitive adhesive layer (tackiness) There is a tendency to decrease, and the adhesion to the adherend will decrease. On the other hand, the amount of hardener (B) is less than 0. When the amount is 1 part by weight, since a sufficient crosslinked structure is not obtained, the cohesive force is lowered, and the heat and the heat and the heat and the heat are lowered. By reacting the reactive functional group of the amine ester urea resin (A) with the functional group in the above hardener (B), the amine ester urea resin (A) is crosslinked three times, not only ensuring adhesion to various substrates or The adhesion of the body can also improve the heat resistance and heat and humidity resistance under more severe conditions than before. Therefore, the adhesive composition of the present invention can be particularly suitably used as a conductive member. The pressure-sensitive adhesive composition of the present invention may contain a decane coupling agent having an alkoxyalkylalkyl group for the purpose of improving moist heat resistance. The decane coupling agent particularly tends to form an inclined structure in the pressure-sensitive adhesive layer, and is locally present on the surface of the adhesive layer, and is considered to have an effect particularly in terms of improving moisture-heat resistance characteristics or improving the subsequent force. As a Shi Xi siu coupler, a conventional person can be used. For example, 7-(indenyl) propylene oxy decyl tridecyloxy oxysphate, 7-(indenyl) propylene oxypropyltrimethoxy sulphur, 7-(indenyl) propylene Styrene oxypropyl triethoxylate, 7-(fluorenyl) propylene methoxy propyl tributoxide, 7-(fluorenyl) propylene methoxy propyl decyl decyl decane, 7 a decane compound having a (fluorenyl) propylene fluorenyloxy group and an alkoxy group such as (meth) propylene methoxy propyl methyl diethoxy decane; ethylene trimethoxy zeoxime, ethylene triethyl ethane Oxygen stone, Ethyl group 31 322162 201107439 Tributoxy calcination, Ethyl decyl decyl oxycarbazide, etc. Ethyloxycarbamate with ethylene group; 5-hexenyltrimethoxydecane , 9-nonenyl trimethoxy decane, phenethyl bake-based trimethoxy zexi-sinter, etc.; 7-aminopropyltrimethoxydecane, T-aminopropyltriethoxysulfonium Calcined, 7"-aminopropyl fluorenyl dimethoxy oxy-stone, 7-aminopropylmethyldiethoxy sulphur, etc. having an amine group and an alkoxy group; rM-based Trimethoxy hydrazine , r-mercaptopropyltriethoxydecane, rM-propyl propyl decyl decyloxydecane, decyl propyl decyl diethoxy carbaryl, fluorenyl phenylethyl tributary a compound having a mercapto group such as a sulfhydryl decyloxydecane, a 6-fluorenyl hexyl methoxy decane or a 10-M fluorenyl decyloxy decane; IS-1000, ΙΑ-100 Α, ΙΜ-1000, a compound having an imidazole group such as SP-10 (manufactured by Nippon Mining Co., Ltd.); a tetraalkoxynonane such as tetradecyloxydecane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane; Glycidoxypropyltrimethoxy oxime, 3-glycidoxypropylmethyldimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3 - chloropropylmethyl decyloxydecane, 3-chloropropyltrimethoxy decane, phenyltrimethoxy decane, hexamethylene decazinane, diphenyldimethoxy oxalate, 1, 3, 5-paraxyl (3-trimethoxyxanthyl propyl) trimeric isocyanate, ethylene thiophene (2-methoxyethoxy), Ν ( (2 -Amino B 3-aminopropyl decyl dimethoxy group Calcined, fluorenyl-(2-aminoethyl)-3-aminopropyltrimethoxy decane, 3-isocyanatopropyltriethoxydecane, and the like. 32 322162 201107439 Any one or more of these may be used singly or in combination of plural kinds. 'In the above decane coupling agent, from the viewpoint of improving heat resistance/moisture-and-heat resistance: using 3-isoxyl propyl triethoxylate or 3-glycidoxypropyl dimethoxy stone Xi Xia, or Shi Xi Yuan coupling agent with a miso base is preferred. Especially when using 3-isocyanatopropyltriethoxydecane or IM-1_ (containing imidate), 3 (imidin + yl)-2-indolyl propionic acid 3 (dimethoxy) When a mixture of a decylalkyl propyl ester and a partial hydrolysis reaction product thereof is obtained, a pressure-sensitive type which can particularly improve workability, plasticizer resistance, resistance to heat/heat and heat resistance, and which has a particularly high adhesion to a conductive member can be obtained. The composition of the agent. When the above decane coupling agent is used, it is used in an amount of 0 parts by weight in order to obtain sufficient moisture-heat resistance and adhesion resistance with respect to the weight of the amine ester urea resin (Α). More than 1 part by weight is preferred. On the other hand, even if too much is used, no better effect can be obtained, and there is a case where the adhesion force is lowered, so that it is 1. It is preferred to use in the range of 0 parts by weight or less. The pressure-sensitive adhesive composition of the present invention may be used in combination with other resins such as an acrylic resin, a polyester resin, an amine resin, an oxygen resin, and a polyurethane resin, if necessary. Further, depending on the application, organic/inorganic pigments, fillers, colorants, ultraviolet absorbers, antifoaming agents, light stabilizers and the like may be added. '^ The conductive member (conductive material) which uses the pressure-sensitive adhesive composition of the present invention is not particularly limited as long as it is a conductive member, and can be listed. A conductive metal circuit formed of a transparent conductive film such as ΙΤ0 or ΑΤ0, a metal evaporated film, or a metal particle 322162 33 201107439. By using the pressure-sensitive adhesive composition of the present invention, a laminate product comprising a pressure-sensitive adhesive layer and a sheet-like base material (hereinafter referred to as "pressure-sensitive adhesive sheet for a conductive member" or "pressure-sensitive type" can be obtained. Follow-up sheet"). For example, the pressure-sensitive adhesive sheet for a conductive member can be obtained by applying, drying and hardening the pressure-sensitive adhesive composition of the present invention on one surface or both surfaces of various sheet-like substrates. Since the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet is "sensitive", it has viscosity at room temperature. When applying the composition of the adhesive, a suitable liquid medium such as an organic solvent such as ethyl acetate, toluene, mercaptoethyl ketone, isopropyl alcohol or another hydrocarbon solvent may be added or water may be added to adjust the viscosity, and The adhesive composition can be heated to lower the viscosity. However, when a large amount of water or an alcohol or the like is added, it is necessary to take care because the reaction between the amine ester urea resin (A) and the hardener (B) may be inhibited. The sheet-like substrate is not particularly limited, and examples thereof include cellophane, various plastic sheets, rubber, foam, cotton, rubber-coated cloth, resin impregnated cloth, glass plate, metal plate, wood, and polarized light. A flat shape such as an optical film such as a plate. Further, various substrates may be used alone, or a multilayered state in which a plurality of layers are laminated may be used. Further, a surface peeling treatment or an antistatic treatment can also be used. Various plastic sheets are also called various plastic films, and examples thereof include films of polyvinyl alcohol film or cellulose triacetate film, polyolefin resin such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer. Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate B 34 322162 201107439 A film of polyester resin such as 曰 ;; polycarbonate resin film; poly borneol Ethylene resin film; polyarrylate resin film; acrylonitrile film, polyphenylene sulfide resin film, polystyrene resin film; vinyl resin film; A guanamine-based resin film; a polyimide-based resin film; an epoxy resin, a cycloolefin resin film, or the like. According to a usual method, after applying the adhesive composition to the above-mentioned sheet-like substrate by an appropriate method, when the adhesive composition contains an organic solvent or a liquid medium such as water, the liquid medium is removed, or when the pressure-sensitive adhesive is used When the composition does not contain a liquid medium which volatilizes, the adhesive layer in a molten state is cooled and solidified, and an adhesive layer can be formed on the sheet-form substrate. The thickness of the pressure-sensitive adhesive layer is 0. 1_ to 250 /zm is better than 20/zm to 2〇〇; czm is better. Not up to 〇. l#m does not have sufficient adhesion, but even if it exceeds 250 a m', the characteristics such as force will not increase. The method of applying the adhesive composition to the sheet-like base material is not particularly limited, and examples thereof include a wire rod (Meyer bar), a coater (appHcat〇d, a bristles, a spray, a roll, a gravure coater, and a die coating). Various coating methods such as diec〇ater, lip coater, comma coater, blade coater, reverse coater, rotary coater, etc. Drying of the adhesive layer The method is not particularly limited, and examples thereof include drying by hot air, infrared rays, or decompression. The drying conditions vary depending on the hardening form of the adhesive composition, the film thickness, and the solvent to be selected, and are usually in the range of 60 to 1801. The hot air may be heated by the left and right hot air. The laminate of the pressure-sensitive adhesive composition of the present invention may be formed by a pressure-sensitive adhesive 322162 355: 35 201107439, which is a transparent optical member such as a film or a glass. The conductive member or the transparent optical member of the laminated body = is formed of a sensory layer formed of a conductive agent composition of a conductive material, and a laminated layer is formed on a conductive member such as a film or a metal circuit. The following agent is particularly effective in the viewpoint of sex. The sheet-like substrate which has been subjected to the peeling treatment on the surface of the pressure-sensitive type; the surface of the sheet can be obtained by, for example, the following method. And obtaining: (1) applying and drying the pressure-sensitive adhesive composition on the peeling-treated surface of the sheet-like substrate which has passed through the peeling place, and then transparent optical member such as PET film or glass The sheet-like conductive member is laminated on the surface of the pressure-sensitive adhesive layer (this is referred to as a transfer coating method); or (2) on a transparent optical member such as a PET film or glass, or a sheet-like conductive member. After the pressure-sensitive adhesive composition is applied and dried, the surface of the pressure-sensitive adhesive layer is subjected to a release treatment of the sheet-like substrate (referred to as a direct coating method). The peeled-treated flaky base covering the surface of the pressure-sensitive adhesive layer is laminated from a laminate having a structure of "sheet-treated substrate/pressure-sensitive adhesive; = Jf/transparent optical member" Stripped material, pressure-sensitive adhesive Adhered to a sheet-like conductive member (such as a conductive member such as a film or a metal circuit), whereby a structure such as a "transparent" material/pressure-sensitive adhesive layer/conductive member can be obtained. Touch 36 322162 201107439 type panel sheet. Also, household adhesive layer / sheet-like; rationalized sheet / pressure-sensitive circuit and other conductive members)" structure of the transfer film or metal layer surface of the separation process Over-constructed: =: Covering the pressure-sensitive adhesive type followed by fresh bonding h #Substrate is peeled off, and the sensitized light and the member are made of octagonal and optical components, thereby obtaining The structure/pressure-sensitive type of the monthly panel sheet. The structure of the core, the conductive member is used for the touch type: and the conductive member is made of the pressure-sensitive adhesive sheet or the laminated body uwm' except for the above-mentioned touch panel In addition, it can also be used for various electronic related components such as liquid aam, plasma display, and electrode peripheral members, or protective films. The invention is further illustrated by the following examples, but the scope of the invention is not limited to the following examples. In the meantime, "parts" and "%" in the examples indicate "parts by weight" and "% by weight" unless otherwise stated. The weight average molecular weight (Mw) of each of the resins obtained in δ Examples 4 to 25 was determined by the following method. <Measurement of weight average molecular weight (Mw)>
Mw之測定是使用Tosho股份公司製GPC (凝膠滲透層析 儀)「HPC-8020」。GPC是將溶解於溶劑(THF ;四氫呋喃)中 之物質藉由分子大小之差異而進行分離定量之液體層析 法,重量平均分子量(Mw)之決定是以聚苯乙烯換算來進行。 <多胺基化合物(c)之合成> 合成例1 322162 37 201107439 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗(dropping funnel)之4 口燒瓶中,饋入異佛爾酮 二胺(IPDA)25. 0份、甲苯25. 0份。在室溫下,滴入丙烯 酸4-經基丁酯19. 1份、丙烯酸丁酯18. 8份。滴完後,在 80°C反應2小時,然後加入曱苯37. 9份。再加入醋酸乙酯, 將固形份調整到50%者當作化合物(1)溶液。 合成例2 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入異佛爾酮二胺(ipda)40.0 份、曱笨40. 〇份。在室溫下,滴入丙烯酸4-羥基丁酯67. 8 份。滴完後’在8(TC反應2小時,然後加入曱苯67. 8份。 再加入醋酸乙酯,將固形份調整到50%者當作化合物(2)溶 液。 合成例3 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入異佛爾酮二胺(IPDA)30.〇 份、曱苯30. 0份。在室溫下,滴入丙烯酸2-羥基乙酯18. 4 份、丙烯酸乙酯17. 6份。滴完後,在8(TC反應2小時, 然後加入甲苯36. 0份。再加入醋酸乙醋,將固形份調整到 5 0%者當作化合物(3)溶液。 <胺酯尿素樹脂(A)之合成> 合成例4 在具備授拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入SannixPP-2000(2官能聚丙 38 322162 201107439 -酵,三洋化成工業股份公司製)79〇份、異佛 酸酯U0份、甲笨225份、作為觸媒之二月桂酸二辛= 0.075份,使溫度徐徐上昇到⑽。c為止,進行反應2小時。 冷卻到40°C,加入醋酸乙酯787份、乙醯丙酮2 5份後, 將化合物(1)溶液48. 7份在1小時内滴入,進一步熟成j 小時。以滴定確認異氰酸基之殘量後,加入2_胺基_2_甲 基丙醇2. 3份及醋酸乙酯1〇〇份,當確認到ir圖譜之nc〇 特性吸收(2, 270cm1)消失時,將反應終止。該胺酯尿素樹 脂(A-1)之重量平均分子量Mw是115, 〇〇〇。 <胺酯尿素樹脂之合成> 合成例5至21 依據表1所示之調配比例,以與合成例4相同之方法而獲 得胺酯尿素樹脂(A-2)至(A-18)。 39 322162 201107439 CSJ i <〇 Α-9 409 T- CO 59.9 S 0.05 CO CO CO CO 47.4 ir> 95000 I <〇 ai 00 CO I Φ ΓΑ=8Ί 442 57.8 tr> CM 0.042 CO m esi 44.9 LO 〇 〇 105000 CO 一 o Ϊ Φ Α-7 498 l 52.4 I G〇 CO 0.046 317 00 csi 1 32.1 I o 91000 CSJ σι 00 CNJ a> φ Α-6 I 439 | CO tr> CM 0.042 374 彳 CO (D o I 125000 1 1 t2.1 __1 σ> 00 <〇 1 Α-5 1 T" in 49.5 lO CM 0.042 00 n i〇 csi 55.1 Csi o 95000 σ> CNJ in 卜 4〇 1 Α-4 I 439 CO in CM *·— 0.042 290 in csi 28.5 ir> d o 175000 11.9 GO csi CO <0 1 Α-5 I T-* m CO I 48.9 I 100 0.033 卜 CO OJ T· O) 〇> CO csi o 72000 I .12.0_I CSI ψ— ΙΑ <〇 I A-2 1 I___379 I CO <D o 0.037 σ> CM CO CM CNJ 卜 o 95000 13.1 Φ 1 A-1 I 790__I 〇 > IO CM CSJ 1 0.075 1 卜 lO oi L 48.7 | CO cvi o It 5000 L 12.0 1 CD csi AJtrr ΡΡ600 I PP1000 PP2000 PP3000 PP4000 PE-62 PTMG P-2010 C-2090 IIPDI I HMDI $4 DOTDL I DBTDL I醋酸乙醋」 键 0 Ϊ CO ¥ 4〇 ;〇 IPDA AMP 'n Ί 醋酸乙酯 1 重量平均分子量(Mw) | 多異氰酸酯(b)之重量% I 多胺基化合物(c)之重量% Βς 荜 避 多元醇 (a) 多異r酷 藏 紱 觸媒 溶劑 多胺基化合 物(c)溶液 反應停止劑 (e) 紱 胺酯化 反應 (胺酯預 聚物之 合成) 尿素化 反應 40 322162 201107439 CNll1—< eg : 噠 A-18 | 1 790 1 〇 225 | 0.033 1 卜 GO LO Ο 55.6 1 CSJ d s CSI 214300 1 11.9 I s 卜 1 < ΙΟ CO 48.9 o ▼— 0.033 CO CNJ csl in CO o 42300 12.0 <〇 Ο ο § A-16 σ> CD CO 30.7 in CO 0.06 r- W 对 s s s 62000 P- cd 11.53 CO ϊ A-15 223 m CSJ CO 00 0.06 m 〇 in co 110 § s 85000 1 30.6 1 13.48 卜 ϊ I A-14 | 589 <〇 CO CO T·· 0.06 1 803.6 1 3.12 1 78.3 | in CO 200 96600 1 20.3 1 4.94 <〇 i I A-13 I § 1 30.4 j 62.5 0.02 in CSJ csi σ> o 97000 1 11·8 1 5 in i A-12 219 1 3Ϊ-2 | CO CO 0.02 CM evi ΙΟ d 92000 12.1 卜 c\i ϊ A-11 208 Csi 〇> in 0.05 410 CM oi 00 CM 1 60000 1 I 25.1 __I 17.4 CO i A-10 CO csl CO l〇 in 0.05 OJ CM csi 95000 15.6 10.9 柴 荜 PP600 PP1000 PP2000 PP3000 IPP4000 1 PE-62 PTMG P-2010 C-2090 IIPDI I HMDI ¢- DOTDL DBTDL 溜 〇 趣 饍 0 Μ φ J δ δ IPDA AMP 械1 h Ί 溫 0 链 4D 1 重量平均分子量(Mw) 多異氰酸醋(b)之重量% 多胺基化合物(c)之重量% 多元醇 (a) 多異(f)酸醋 溶劑 觸媒 溶劑 多胺基化合 物(C)溶液 w 给3 胺酯化 反應 (胺酯預 聚物之 合成) 尿素化 反應 41 322162 201107439 表1中之省略符號,分別表示以下所述者。 PP600 : Sannix PP-600(2官能聚丙二醇,三洋化成工業 股份公司製,數平均分子量:587) PP1000 : Sannix PP-1000(2官能聚丙二醇,三洋化成工業 股份公司製,數平均分子量:1020) PP2000 : Sannix PP-2000C2官能聚丙二醇,三洋化成工業 股份公司製,數平均分子量:1996) PP3000 : Sannix PP-3000C2官能聚丙二醇,三洋化成工業 股份公司製,數平均分子量:3032) PP4000 : Sannix PP-4000C2官能聚丙二醇,三洋化成工業 股份公司製,數平均分子量:4007) PE-62 : NEWPOLPE-62C丙二醇與乙二醇之共聚合物,三洋 化成工業股份公司製,數平均分子量:2550) PTMG : PTMG-3000(2官能聚四亞曱基二醇,保土谷化學 工業製,數平均分子量:2921 ) P-2010 : Kuraray Polyol P-2010(2 官能聚酯多元醇, Kuraray股份公司製,數平均分子量:1962) C-2090 : Kuraray Polyol 02090(2 官能聚碳酸酯多元 醇,Kuraray股份公司製,數平均分子量:2011) IPDI : 異佛爾酮二異氰酸酯 HMDI : 六亞甲基二異氰酸酯 D0TDL : 二月桂酸二辛基錫 DBTDL : 二月桂酸二丁基錫 IPDA : 異佛爾酮二胺 42 322162 201107439 AMP: 2-胺基-2-甲基丙醇 <胺酯尿素樹脂之合成> 合成例22 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入聚酯多元醇P-1010C2官能聚 酯多元醇,Kuraray股份公司製)68份、聚醚多元醇G-3000B (3官能多元醇,旭電化股份公司製)265份、曱苯125份、 作為觸媒之2-乙基己酸鐵0. 03份、環烷酸鉛0. 04份,在 使液體充分均勻後,將六亞甲基二異氰酸酯(住友拜耳股份 公司製)24份在1小時内滴下。在90°C下進行3小時反應。 當確認到IR圖譜之NC0特性吸收(2, 270CHT1)消失時,將反 應終止。加入曱苯115份而得到胺酷尿素樹脂(A-19)。該 胺酯尿素樹脂(A-19)之重量平均分子量Mw是50, 000。 <丙烯酸系樹脂之合成> 合成例23 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入丙烯酸丁酯95. 8份、丙烯酸 1.5份、醋酸乙酯150份,在氮氣替換下加熱到70°C為止, 然後添加偶氮二異丁腈0. 15份並開始聚合。在開始聚合後 3小時起,每隔1小時,到5小時後為止分別添加偶氮二 異丁腈0. 15份,然後再聚合2小時。之後,追加醋酸乙酯 150份,使聚合終止,得到丙烯酸系樹脂(A-20)。該丙烯 酸系樹脂(A-20)之重量平均分子量Mw是790, 000。 <丙烯酸系樹脂之合成> 43 322162 201107439 合成例24 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 ’ 滴液漏斗之4 口燒瓶中’饋入丙烯酸丁酯97. 7份、丙稀酸 2-羥基乙酯1.5份、醋酸乙酯15〇份,在氮氣替換下加熱 到7〇°C為止,然後添加偶氮二異丁腈〇. 15份並使聚合開 始。在開始聚合後3小時起,每隔1小時,到5小時後為 止分別添加偶氮二異丁腈〇. 15份,再聚合2小時。之後, 追加醋酸乙酯150份,使聚合終止,得到丙烯酸系樹脂 (A-21)。該丙歸酸系樹脂(a-21)之重量平均分子量Mw是 840, 〇〇〇。 <丙烯酸系樹脂之合成> 合成例25 在具備攪拌機、回流冷卻管、氮氣導入管、溫度計、 滴液漏斗之4 口燒瓶中,饋入丙烯酸丁酯89. 9份、丙烯酸 10. 〇份、丙烯酸4-羥基丁酯〇. 1份、醋酸乙酯63份、丙 酮1〇〇份,在氮氣替換下加熱到65。0:為止,然後添加偶氮 二異丁腈0. 03份並使聚合開始。在開始聚合後6小時後添 加偶氮二異丁腈0.2份,再聚合6小時。之後,追加醋酸 乙醋45份’使聚合終止’得到丙烯酸系樹脂(A_22)。該丙 烯酸系樹脂(A-22)之重量平均分子量勛是910, 000。 實施例1至23 相對於合成例4至19所得之樹脂(a-ι)至(A-16)的固 形份100份,將硬化劑、矽烷偶合劑依照表2而調配後, 得到導電構件用感壓式接著劑組成物。 322162 201107439 比較例1至9 相對於合成例4、20 2S於^ , W主々所得之樹脂(A-l)、(A-17) 至(Α-22)的固形份10〇份,將旆 , UU伤將硬化劑、金屬去活化劑(metal deaCtlVatQr)、錢偶合劑依照表3而調配後,得到導電 構件用感壓式接著劑組成物。 將上述感壓式接著劑組成物以乾燥後的厚度成為# :之方式塗布在經剝離處理過之聚§旨薄膜(以下,稱「剝離 、在1〇〇(:乾燥2分鐘,形成感壓式接著劑層。 以後,在感壓式接著劑層減__厚的聚對苯二甲酸 乙二酯薄膜(PET薄膜)。直呤,胺& 、)/、-人將所得積層體在溫度23°C- 相對濕度5 0%之條件下孰点彳 卜熟成1週(暗反應),進行接著劑層 之反應’得到導電構件用感壓式接著性薄片。 <接著力之評估方法> 將上述感壓式接著劑薄片裁剪成寬度25mm ,將剝離薄 膜剝開,並將路出之感壓式接著劑層分別在23<Jc_5〇%RH下 黏貼於厚度l00//m之pET薄膜、聚碳酸酯(pc)板'玻璃板、 具有ΙΤ0透明導電膜之pET薄膜上,在依據JIS z 0237而 、·’5·幸昆同壓合後’在5 〇 c環境下施加〇. 5MPa之壓力並維持 15分鐘而得試驗片。壓合24小時後,在2;rc_5〇%RH環境 下’使用剝離試驗器,以18〇度剝離、拉伸速度300mm/ 分鐘’將感壓式接著劑薄片從各被黏體上剝離,測定接著 力。 評估基準是如下所述。 6 ·接者力是在35N/25mm以上。 45 322162 201107439 » 5 ·接著力未達35N/25mm且在25N/25mm以上。 4 :接著力未達25N/25mm且在l5N/25mm以上。 3 :接著力未達15N/25mm且在5N/25mm以上。 2 :接著力未達5N/25mm且在1Ν/25ππη以上。 ' 1 .接著力未達lN/25mm。 <耐熱/耐濕熱性之評估方法> 關於耐熱/耐濕熱之評估,係將上述感壓式接著性薄 片裁剪成寬度1 OOmmx長度100mm,並將剝離薄膜剝開,黏 貼在玻璃板上且固定,在5(TC環境下施加〇.5MPa之壓力 並維持20分鐘,製作具有PET薄膜/感壓式接著劑層/玻 璃板之層結構的試驗片。在8〇 C _相對濕度〇%(耐熱性)、 或60°C-相對濕度95%(耐濕熱性)下放置500小時後,以目 視觀察浮起剝離、發泡之情形。 關於財熱/耐濕熱性,以下述3個階級之評估基準評 估。 〇:完全看不出浮起剝離、發泡’實用上完全沒問題。 △:雖看出有若干浮起剝離、發泡,但實用上沒問題。 X :全面性之浮起剝離、發泡,不可實用。 <耐發泡剝離性之評估方法> 關於耐發泡剝離性之評估,係將上述感壓式接著性薄 片裁剪成寬度lOOmmx長度100mm ’並將剝離薄膜剝離,黏 貼在聚碳酸酯(PC)板上且固定’在50°C環境下施加〇. 5MPa 之壓力並維持20分鐘,製作具有PET薄膜/感壓式接著劑 層/PC板之層結構的試驗片。將上述試驗片在8〇。〇之焕箱 322162 46 201107439 中進行熱處理24小時(耐熱性試驗)。 在該财熱性試驗後,以目視觀察試驗片之接著界面(感 •壓式接著劑層與PC板之界面),完全看不出「氣泡」或「浮 起」者判定為「〇」,可認出些微之「氣泡」或「浮起」者 判定為「△」,可顯著認出「氣泡」或「浮起」者判定為「X」。 右5平估在△以上,則在實用上沒有問題。 <腐蝕性之評估方法〉 關於腐餘性之評估,係在具有膜厚5之ΙΤ0透明導 電膜的PET薄骐(寬度40imi,長度160mm)中之ΙΤ0透明導 ,膜上’將裁剪成寬度40匪、長度100顏之上述感壓式接 著丨生薄片經剝開剝離薄膜後予以黏貼並固定,在5(TC環境 下知^ 〇· 5MPa之壓力並維持20分鐘,製作具有PET薄膜 /感1壓式接著劑層/ITO薄膜之層結構的試驗片(觸控式面 板用薄片)。在該試驗片之兩端連繫電極,測定初期之電阻 [一菱化予(股)製,Laresta-GPMCP-T600]。再將試驗片 在85°C—相對濕度90%下放置500小時後,與前述同樣地測 疋經時後之電阻值。 電阻變化率(經時後之電阻值/初期之電阻值)未達 U者記為「〇」,在丨.2以上且未達丨.5者記為「△」, ^ 5以上者記為rx」。若評估在△以上,則判斷為實用上 沒有問題’在導電構件中不會引起不良運作。 又’使用含有Ag粉之導電性糊膏的金屬電路來替代 ΙΤ0透明導電膜,針對其同樣地進行腐蝕性之評估。 <耐可塑劑性之評估方法> 47 322162 201107439 關於耐可塑劑性之評估,係將上述感壓式接著性薄片 裁剪成寬度lOOmmx長度l〇〇mm,並將剝離薄膜剝離,黏貼 在聚碳酸酯(PC)板上且固定,在5(TC環境下施加0.5MPa 之壓力並維持20分鐘,製作具有PET薄膜/感壓式接著劑 層/PC板之層結構的試驗片。將該試驗片浸潰在可塑劑(油 酸)中並取出後,再將試驗片在85°C-相對濕度90%中放置 24小時後’以目視觀察該試驗片之接著界面(感壓式接著 劑層與PC板之界面)。以5(完全觀察不到浮起或剝離)至1 (觀察到有顯者的浮起或剝離)之評估基準來評估。亦即, 評估如下,若評價在3以上(觀察到浮起或剝離之區域未達 全體之10%)的話’則實用上沒有問題。 5:完全觀察不到浮起或剝離。 4 :觀察到浮起或剝離之區域未達全體的5%,實用上 沒有問題。 3:觀察到浮起或剝離之區域為全體的5%以上且未達 10%,實用上沒有問題。 2:觀察到浮起或剝離之區域為全體的1〇%以上且未 達20%,實用上有問題。 1:觀察到浮起或剝離之區域為全體的20%以上,實用 上有問題。 <加工性之評估方法> 關於加工性之評估’係將上述感壓式接著性薄片裁剪 成寬度lOOmmx長度100mm,並將經40°C-60Kg/cm2壓合1 小時後之接著劑層的播出狀態,以5(觀察不到接著劑層的 48 322162 201107439 擠出)至U觀逡s丨士 評估。亦HP,有顯著的接著劑層的擠出)之評估基準來 未達fl ^ 、°平估如下,若評價在2以上(接著劑層的擠出 的話’職用上沒有問題。 •觀察不到接著劑層的擠出。 4 ·雖觀察到未達〇. imm之接著劑層的擠出,但實用 上沒有問題。 3 ·雖觀察到0. 1 mm以上且未達0. 3mm之接著劑層的 擠出,但實用上沒有問題。 2 ·雖觀察到0. 3mm以上且未達0. 5mm之接著劑層的 擠出,但實用上沒有問題。 1 :觀察到0.5mm以上之接著劑層的擠出,實用上有 問題。 49 322162 201107439 i 〇The measurement of Mw was carried out using GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosho Co., Ltd. GPC is a liquid chromatography method in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by a difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene. <Synthesis of Polyamine-Based Compound (c)> Synthesis Example 1 322162 37 201107439 In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel, 0份。 Toluene ketone diamine (IPDA) 25.0 parts, toluene 25.0 parts.份份份份。 18. I. 5份。 After the completion of the reaction, the reaction was carried out at 80 ° C for 2 hours, then added toluene benzene 37. 9 parts. Further, ethyl acetate was added, and the solid content was adjusted to 50% as a solution of the compound (1). Synthesis Example 2 In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a dropping funnel, 40.0 parts of isophorone diamine (ipda) and 40 parts of hydrazine were fed. 8 parts of 4-hydroxybutyl acrylate was added dropwise at room temperature. After the completion of the dropwise solution, the reaction was carried out at 8 (TC for 2 hours, then 67.6 parts of toluene was added. Further, ethyl acetate was added, and the solid content was adjusted to 50% as a solution of the compound (2). Synthesis Example 3 In the case of a mixer, In a 4-neck flask of a reflux cooling tube, a nitrogen inlet tube, a thermometer, and a dropping funnel, a mixture of isophorone diamine (IPDA) 30. hydrazine and hydrazine benzene was added in an amount of 30. 0 parts. 2-hydroxyethyl ester 18.4 parts, ethyl acrylate 17.6 parts. After the completion of the dropwise addition, at 8 (TC reaction for 2 hours, then added toluene 36.0 parts. Then add ethyl acetate, adjust the solid content to 5 0% is used as a solution of the compound (3). <Synthesis of the amine ester urea resin (A)> Synthesis Example 4 A 4-necked flask equipped with a mixer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel In the process, we fed 79% of Sannix PP-2000 (2-functional polypropylene 38 322162 201107439 - yeast, manufactured by Sanyo Chemical Industry Co., Ltd.), U0 parts of isophorate, 225 parts of Azure, and dioxin as a catalyst. 0.075 parts, the temperature was slowly raised to (10). c, the reaction was carried out for 2 hours. Cooled to 40 ° C, 787 parts of ethyl acetate was added. After 2 parts of acetonitrile, 4 parts of the compound (1) solution was added dropwise over 1 hour, and further matured for 1 hour. After confirming the residual amount of the isocyanate group by titration, 2-amino group 2 was added. _Methylpropanol 2.3 parts and ethyl acetate 1 part, when it is confirmed that the ir 〇 characteristic absorption (2, 270cm1) disappears, the reaction is terminated. The amine ester urea resin (A-1) The weight average molecular weight Mw was 115, 〇〇〇. <Synthesis of Amine Ester Urea Resin> Synthesis Examples 5 to 21 According to the blending ratio shown in Table 1, an amine ester urea resin was obtained in the same manner as in Synthesis Example 4. (A-2) to (A-18). 39 322162 201107439 CSJ i <〇Α-9 409 T-CO 59.9 S 0.05 CO CO CO CO 47.4 ir> 95000 I <〇ai 00 CO I Φ ΓΑ=8Ί 442 57.8 tr> CM 0.042 CO m esi 44.9 LO 〇〇105000 CO a o Ϊ Φ Α-7 498 l 52.4 IG〇CO 0.046 317 00 csi 1 32.1 I o 91000 CSJ σι 00 CNJ a> φ Α-6 I 439 | CO tr> CM 0.042 374 彳CO (D o I 125000 1 1 t2.1 __1 σ> 00 <〇1 Α-5 1 T" in 49.5 lO CM 0.042 00 ni〇csi 55.1 Csi o 95000 σ> CNJ in 卜4〇1 Α-4 I 439 CO in CM *·- 0.042 290 in csi 28.5 ir> do 175000 11.9 GO csi CO <0 1 Α- 5 I T-* m CO I 48.9 I 100 0.033 卜CO OJ T· O) 〇> CO csi o 72000 I .12.0_I CSI ψ— ΙΑ <〇I A-2 1 I___379 I CO <D o 0.037 σ> CM CO CM CNJ 卜o 95000 13.1 Φ 1 A-1 I 790__I 〇> IO CM CSJ 1 0.075 1 卜 lO oi L 48.7 | CO cvi o It 5000 L 12.0 1 CD csi AJtrr ΡΡ600 I PP1000 PP2000 PP3000 PP4000 PE -62 PTMG P-2010 C-2090 IIPDI I HMDI $4 DOTDL I DBTDL I Acetate" Key 0 Ϊ CO ¥ 4〇;〇IPDA AMP 'n ΊEthyl acetate 1 Weight average molecular weight (Mw) | Polyisocyanate (b % by weight I % by weight of polyamine-based compound (c) Βς Avoid polyol (a) polyiso-r-thorium catalyst solvent polyamine-based compound (c) solution reaction stop agent (e) guanamine esterification Reaction (synthesis of amine ester prepolymer) ureaification reaction 40 322162 201107439 CNll1—< e g : 哒A-18 | 1 790 1 〇225 | 0.033 1 卜 GO LO Ο 55.6 1 CSJ ds CSI 214300 1 11.9 I s 卜 1 < ΙΟ CO 48.9 o ▼— 0.033 CO CNJ csl in CO o 42300 12.0 < ο ο § A-16 σ> CD CO 30.7 in CO 0.06 r- W vs sss 62000 P- cd 11.53 CO ϊ A-15 223 m CSJ CO 00 0.06 m 〇in co 110 § s 85000 1 30.6 1 13.48 Divination I A-14 | 589 <〇CO CO T·· 0.06 1 803.6 1 3.12 1 78.3 | in CO 200 96600 1 20.3 1 4.94 <〇i I A-13 I § 1 30.4 j 62.5 0.02 in CSJ csi σ> o 97000 1 11·8 1 5 in i A-12 219 1 3Ϊ-2 | CO CO 0.02 CM evi ΙΟ d 92000 12.1 卜 c\i ϊ A-11 208 Csi 〇> in 0.05 410 CM oi 00 CM 1 60000 1 I 25.1 __I 17.4 CO i A-10 CO csl CO l〇in 0.05 OJ CM csi 95000 15.6 10.9 Chai Mite PP600 PP1000 PP2000 PP3000 IPP4000 1 PE-62 PTMG P-2010 C-2090 IIPDI I HMDI ¢- DOTDL DBTDL Fun meal 0 Μ φ J δ δ IPDA AMP machine 1 h Ί temperature 0 Chain 4D 1 Weight average molecular weight (Mw) Polyisocyanate (b) Weight % Polyamine based compound (c) Weight % Polyol (a) Polyiso(f) acid vinegar solvent catalyst solvent polyamine compound (C) Solution w to 3 amine esterification reaction (synthesis of amine ester prepolymer) ureatization reaction 41 322162 201107439 The abbreviations in Table 1 indicate the following. PP600 : Sannix PP-600 (2-functional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 587) PP1000 : Sannix PP-1000 (2-functional polypropylene glycol, manufactured by Sanyo Chemical Industry Co., Ltd., number average molecular weight: 1020) PP2000 : Sannix PP-2000C2-functional polypropylene glycol, manufactured by Sanyo Chemical Industry Co., Ltd., number average molecular weight: 1996) PP3000 : Sannix PP-3000C2 functional polypropylene glycol, manufactured by Sanyo Chemical Industry Co., Ltd., number average molecular weight: 3032) PP4000 : Sannix PP -4000C2 functional polypropylene glycol, manufactured by Sanyo Chemical Industry Co., Ltd., number average molecular weight: 4007) PE-62 : NEWPOLPE-62C copolypolymer of propylene glycol and ethylene glycol, manufactured by Sanyo Chemical Industry Co., Ltd., number average molecular weight: 2550) PTMG : PTMG-3000 (2-functional polytetradecyl diol, manufactured by Hodogaya Chemical Industry Co., Ltd., number average molecular weight: 2921) P-2010 : Kuraray Polyol P-2010 (2-functional polyester polyol, manufactured by Kuraray Co., Ltd., number Average molecular weight: 1962) C-2090 : Kuraray Polyol 02090 (2-functional polycarbonate polyol, manufactured by Kuraray Co., Ltd., number average molecular weight: 2011) I PDI : Isophorone diisocyanate HMDI : Hexamethylene diisocyanate D0TDL : Dioctyltin dilaurate DBTDL : Dibutyltin dilaurate IPDA : Isophorone diamine 42 322162 201107439 AMP: 2-Amino- Synthesis of 2-methylpropanol <amine ester urea resin> Synthesis Example 22 A polyester polyol P- was fed into a 4-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a dropping funnel. 1010C2-functional polyester polyol, manufactured by Kuraray Co., Ltd., 68 parts, polyether polyol G-3000B (3 functional polyol, manufactured by Asahi Kasei Co., Ltd.) 265 parts, 125 parts of toluene, 2-ethyl as a catalyst After the liquid was sufficiently homogeneous, 24 parts of hexamethylene diisocyanate (manufactured by Sumitomo Bayer AG) was dropped over 1 hour. The reaction was carried out at 90 ° C for 3 hours. When it is confirmed that the NC0 characteristic absorption (2, 270CHT1) of the IR spectrum disappears, the reaction is terminated. 115 parts of toluene was added to obtain an amine cool urea resin (A-19). The weight average molecular weight Mw of the urethane urea resin (A-19) was 50,000. <Synthesis of Acrylic Resin> Synthesis Example 23 Into a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a dropping funnel, 95.8 parts of butyl acrylate, 1.5 parts of acrylic acid, and acetic acid were fed. 150 parts of ethyl ester, heated to 70 ° C under a nitrogen atmosphere, then added azobisisobutyronitrile 0.15 parts and began to polymerize. 15 parts of the azobisisobutyronitrile was added every 1 hour to 5 hours after the start of the polymerization, and then polymerization was further carried out for 2 hours. Thereafter, 150 parts of ethyl acetate was added to terminate the polymerization to obtain an acrylic resin (A-20). The weight average molecular weight Mw of the acrylic resin (A-20) was 790,000. <Synthesis of Acrylic Resin> 43 322162 201107439 Synthesis Example 24 butyl acrylate was fed into a 4-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, a thermometer, and a dropping funnel 97. 7 parts, C 1.5 parts of dihydroxyethyl 2-hydroxyethyl ester and 15 parts of ethyl acetate were heated to 7 ° C under nitrogen substitution, then azobisisobutyronitrile was added. 15 parts and polymerization was started. Three hours after the start of the polymerization, azobisisobutyronitrile ruthenium was added every 1 hour to 5 hours, and further polymerization was carried out for 2 hours. Thereafter, 150 parts of ethyl acetate was added to terminate the polymerization to obtain an acrylic resin (A-21). The weight average molecular weight Mw of the acryl acid resin (a-21) was 840, 〇〇〇. <Synthesis of Acrylic Resin> Synthesis Example 25 In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a dropping funnel, 8.9 parts of butyl acrylate was fed, and acrylic acid was used.份份。 。 。 。 。 。 。 。 。 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份The polymerization begins. After 6 hours from the start of the polymerization, 0.2 part of azobisisobutyronitrile was added, followed by polymerization for 6 hours. Thereafter, 45 parts of ethyl acetate was added to "end the polymerization" to obtain an acrylic resin (A-22). The weight average molecular weight of the acrylic resin (A-22) was 910,000. Examples 1 to 23 With respect to 100 parts of the solid parts of the resins (a-ι) to (A-16) obtained in Synthesis Examples 4 to 19, the curing agent and the decane coupling agent were blended in accordance with Table 2 to obtain a conductive member. A pressure sensitive adhesive composition. 322162 201107439 Comparative Examples 1 to 9 Relative to Synthesis Example 4, 20 2S, the resin (Al), (A-17) to (Α-22) obtained by the main enthalpy, the solid content of 10 parts, 旆, UU The wound hardening agent, the metal deactivating agent (metal deaCtlVatQr), and the money coupling agent were blended in accordance with Table 3, and a pressure-sensitive adhesive composition for a conductive member was obtained. The pressure-sensitive adhesive composition is applied to the peeled-treated polycrystalline film by a thickness of #: (hereinafter, it is referred to as "peeling, at 1 〇〇 (: drying for 2 minutes, forming a pressure-sensitive pressure) a layer of adhesive. Later, the pressure-sensitive adhesive layer is reduced by __ thick polyethylene terephthalate film (PET film). Straight 呤, amine &, /, / - people will be the laminated body At a temperature of 23 ° C - a relative humidity of 50%, the mixture was aged for 1 week (dark reaction), and the reaction of the adhesive layer was carried out to obtain a pressure-sensitive adhesive sheet for a conductive member. > The pressure-sensitive adhesive sheet was cut into a width of 25 mm, the release film was peeled off, and the pressure-sensitive adhesive layer of the road was adhered to pET having a thickness of l00//m at 23 < Jc_5〇% RH, respectively. Film, polycarbonate (pc) plate 'glass plate, pET film with ΙΤ0 transparent conductive film, in accordance with JIS z 0237, · '5 · Xing Kun with the same press 'applied in 5 〇 c environment. The test piece was obtained by maintaining the pressure of 5 MPa for 15 minutes. After pressing for 24 hours, in the environment of 2; rc_5 〇 % RH The pressure-sensitive adhesive sheet was peeled off from each adherend by a peeling tester at a peeling speed of 18 mm and a tensile speed of 300 mm/min. The adhesion was measured. The evaluation criteria are as follows. Above 35N/25mm. 45 322162 201107439 » 5 · The force is not 35N/25mm and is above 25N/25mm. 4: The force is less than 25N/25mm and is above l5N/25mm. 3: The force is less than 15N/ 25mm and 5N/25mm or more. 2: The bonding force is less than 5N/25mm and is above 1Ν/25ππη. '1. The force is not up to lN/25mm. <Evaluation method of heat/moisture resistance> The evaluation of the heat and humidity resistance is performed by cutting the pressure-sensitive adhesive sheet into a width of 100 mm and a length of 100 mm, peeling off the peeling film, adhering to the glass plate and fixing it, and applying a pressure of 5 MPa in a 5 (TC environment). The test piece having a layer structure of a PET film/pressure-sensitive adhesive layer/glass plate was prepared for 20 minutes at 8 〇C _ relative humidity 〇% (heat resistance), or 60 ° C - relative humidity 95% (resistant After standing for 500 hours under damp heat, the situation of floating peeling and foaming was observed by visual observation. Sexuality is evaluated based on the evaluation criteria of the following three classes. 〇: The floating peeling and foaming are not seen at all. There is no problem in practical use. △: Although there are some floating peeling and foaming, there is no problem in practical use. X: Comprehensive lifting, peeling, foaming, and not practical. <Evaluation method of foaming peeling resistance> Regarding evaluation of foaming peeling resistance, the above pressure-sensitive adhesive sheet is cut into a width of 100 mmx The length of the film is 100 mm', and the release film is peeled off, adhered to a polycarbonate (PC) plate, and fixed at a pressure of 5 MPa at 50 ° C for 20 minutes to prepare a PET film/pressure-sensitive adhesive layer. Test piece of the layer structure of the /PC board. The above test piece was placed at 8 inches. Heat treatment was carried out for 24 hours (heat resistance test) in 〇 焕 焕 box 322162 46 201107439. After the thermal test, the interface of the test piece (the interface between the pressure-sensitive adhesive layer and the PC board) was visually observed, and the "bubble" or "floating" was not found at all. Those who recognize a slight "bubble" or "float" are judged as "△", and it is possible to recognize that "bubble" or "floating" is judged as "X". If the right 5 is estimated to be above Δ, there is no problem in practical use. <Evaluation method of corrosiveness> The evaluation of the corrosion margin is carried out in a PET thin crucible (width 40 imi, length 160 mm) having a film thickness of 5 透明 0 transparent conductive film, and the film is cut into a width. 40 匪, length 100 颜 of the above pressure-sensitive type, then the slab is peeled off and peeled off the film, then adhered and fixed, in 5 (TC environment under the pressure of 5 MPa and maintained for 20 minutes, made with PET film / sense a test piece of a layer structure of a pressure-sensitive adhesive layer/ITO film (a sheet for a touch panel). The electrodes were connected to both ends of the test piece, and the initial resistance was measured. [Imitated by Yuling Chemical Co., Ltd., Laresta -GPMCP-T600]. After the test piece was allowed to stand at 85 ° C - 90% relative humidity for 500 hours, the resistance value after the lapse of time was measured in the same manner as above. Resistance change rate (resistance after time / initial value) If the resistance is less than U, it is marked as "〇", and if it is less than or equal to 5, it is marked as "△", and if it is above 5, it is written as rx". If the evaluation is above △, it is judged as There is no problem in practical use 'Does not cause bad operation in conductive members. Also 'Use Ag powder The metal circuit of the electric paste is used instead of the ΙΤ0 transparent conductive film, and the corrosivity evaluation is performed for the same. <Evaluation method of plasticizer resistance> 47 322162 201107439 The evaluation of the plasticizer resistance is based on the above The pressure-sensitive adhesive sheet was cut into a width of 100 mm×length l〇〇mm, and the release film was peeled off, adhered to a polycarbonate (PC) plate and fixed, and a pressure of 0.5 MPa was applied in a 5 (TC environment for 20 minutes). A test piece having a layer structure of a PET film/pressure-sensitive adhesive layer/PC board was prepared. The test piece was dipped in a plasticizer (oleic acid) and taken out, and then the test piece was at 85 ° C - relative humidity After standing for 24 hours in 90%, 'visually observed the interface of the test piece (the interface between the pressure-sensitive adhesive layer and the PC plate). 5 (completely no floating or peeling was observed) to 1 (observed to be observed) The evaluation criteria of the person's floating or peeling are evaluated. That is, the evaluation is as follows. If the evaluation is above 3 (the area where the floating or peeling is observed is not up to 10% of the total), then there is no practical problem. No floating or peeling was observed at all. 4 : Observation The area where the float or peeling is not reached 5% of the total, and there is no problem in practical use. 3: The area where the float or peeling is observed is 5% or more of the whole and less than 10%, and there is no problem in practical use. The area to be lifted or peeled off is 1% or more and less than 20% of the total, and there is a problem in practical use. 1: The area where the floating or peeling is observed is 20% or more of the total, and there is a problem in practical use. Evaluation Method > Regarding the evaluation of the processability, the pressure-sensitive adhesive sheet was cut into a width of 100 mm×100 mm in length, and the broadcast state of the adhesive layer was pressed after being pressed at 40° C. to 60 Kg/cm 2 for 1 hour. It was evaluated by 5 (extrusion of the adhesive layer 48 322162 201107439) to the U 逡s gentleman. Also, HP, there is a significant evaluation of the extrusion of the adhesive layer. The evaluation criteria are not as high as fl ^, and the evaluation is as follows. If the evaluation is above 2 (the extrusion of the adhesive layer is used, there is no problem in the job.) The adhesive of 0. 1 mm or more and less than 0. 3 mm of the adhesive was observed. The adhesive was not observed. Extrusion of the layer, but practically no problem. 2) Although the extrusion of the adhesive layer of 0.3 mm or more and less than 0.5 mm was observed, there was no problem in practical use. The extrusion of the layer is practically problematic. 49 322162 201107439 i 〇
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Od «ϋκ 13d/0h 00. ob 笮砌球 ii难魄苜 ti逭趄 l^Hl^ ¢1¾樹 is.|g 50 322162 201107439 co< 比較例9 1 < m to CO L___c-2」 in I 寸 co CM 〇 〇 〇 〇 〇 寸 寸 比較例8 CD 0.05 CSJ 6 ΙΟ ο I in 寸 甘 X X X 〇 〇 CM 比較例7 A-22 L B-6 J 1.10 in d I in ΙΟ 寸 CO 〇 〇 〇 X X CO 比較例6 A-21 〇 c\i L c-2___J m d I 寸 兮 co co X X X 〇 〇 CO 比較例5 A-21 1 B-6 J 0.05 L c-2__J ir> o I ΙΟ LO 寸 CO o 〇 X X X 寸 CO 比較例4 A-20 1 b-6 I I 0.05 I I C-2 I ir> o o \ri 寸 兮 co co X < < X X 寸 co 比較例3 A-19 CD in — C-1 ΙΩ o I CM CM CM X X < 〇 〇 寸 比較例2 A-18 <|RW m T" d esj o in d I 兮 寸 CO CSi 〇 〇 < 〇 〇 to 寸 比較例1 A-17 L J o CO L_ C-2__J ir> o I CO CO » in 寸 X X < < < CO 1 樹脂 1 硬化劑 r 添加量 tM I BTZM I I PET 膜 | Ο Q. 玻璃I IITO/PETI 玻璃 玻璃 ο QL I_ΠΌI ιμπτ Μ 1 加工性 接著力 I 耐熱性 I 耐濕熱性 ι耐發泡剝離性 腐钱性 w 斟 51 322162 201107439 表2及表3中之省略符號,分別表示以下所述者。 B-1 .六亞甲基二異氰酸酯三羥甲基丙烷加成體 B-2 :六亞甲基二異氰酸酯三聚異氰酸酯體 B-3 :六亞甲基二異氰酸酯縮二脲體 .B一4 .伸苯二曱基二異氰酸酯三羥甲基丙烷加成體 B-5 ·伸曱笨基二異氰酸酯三羥曱基丙烷加成體 B-6:環氧系硬化劑(Tetrad_x,三菱瓦斯化學股份公司製) C-1 : 3-縮水甘油氧基丙基三曱氧基矽烷 C-2 : 3-異氰酸基丙基三乙氧基矽烷 C-3MM-1000(含有咪唑基之矽烷偶合劑,日鑛金屬股份公 司製) BTZM :金屬去活性劑(共同藥品股份公司製) ΙΤ0/ΡΕΤ :具有ΙΤ0透明導電膜之pet薄膜 如表2之實施例1至23所示,可知本發明之導電構件 用感壓式接著劑組成物有高的接著力、耐熱性'耐濕熱性、 可塑劑耐性、加工性,同時對於IT〇透明導電膜或金屬電 路有優異之耐腐姓性。另-方面,在表3之比較例i至9 則未取得各物性之平衡,尤其看到很多在腐蝕性方面產生 問題者。尤其對於以導電構件為首之各種被黏體有高的接 著力並且耐熱性與腐蝕性優良,係可藉由本案發明而實現 的重要特性。 【圖式簡單說明】 〇 【主要元件符號說明】 322162 52Od «ϋκ 13d/0h 00. ob 笮 笮 ii ii ii 魄苜 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | Inch co CM 〇〇〇〇〇 inch inch comparison example 8 CD 0.05 CSJ 6 ΙΟ ο I in inch XXX 〇〇 CM Comparative Example 7 A-22 L B-6 J 1.10 in d I in ΙΟ inch CO 〇〇〇 XX CO Comparative Example 6 A-21 〇c\i L c-2___J md I inch 兮co co XXX 〇〇CO Comparative Example 5 A-21 1 B-6 J 0.05 L c-2__J ir> o I ΙΟ LO inch CO o 〇 XXX inch CO Comparative Example 4 A-20 1 b-6 II 0.05 II C-2 I ir> oo \ri inch 兮co co X << XX inch co Comparative Example 3 A-19 CD in — C-1 ΙΩ o I CM CM CM XX < 比较 comparison example 2 A-18 <|RW m T" d esj o in d I CO CO CSi 〇〇 < 〇〇 to inch comparison example 1 A-17 LJ o CO L_ C-2__J ir> o I CO CO » in inch XX <<< CO 1 Resin 1 Hardener r Addition amount tM I BTZM II PET film | Ο Q. Glass I IITO/PETI glass glass ο QL I_ΠΌI Ιμπτ Μ 1 Processability Next force I Heat resistance I Heat and humidity resistance ι foaming peeling resistance corrosion of money pour w 201 107 439 51 322 162 Table 2 and Table 3, the abbreviations, the following represent the person. B-1. Hexamethylene diisocyanate Trimethylolpropane adduct B-2: Hexamethylene diisocyanate trimer isocyanate B-3: Hexamethylene diisocyanate biuret. B-4 Benzene diisocyanate diisocyanate trimethylolpropane adduct B-5 · 曱 基 二 diisocyanate trihydrocarbyl propane adduct B-6: epoxy hardener (Tetrad_x, Mitsubishi Gas Chemicals Company made) C-1 : 3-glycidoxypropyl trimethoxy decane C-2 : 3-isocyanatopropyl triethoxy decane C-3MM-1000 (imidazole-based decane coupling agent) , manufactured by Nippon Mining Co., Ltd.) BTZM: Metal Deactivator (manufactured by Co-Pharmaceutical Co., Ltd.) ΙΤ0/ΡΕΤ: PET film having ΙΤ0 transparent conductive film is shown in Examples 1 to 23 of Table 2, and the conductive of the present invention is known. The pressure-sensitive adhesive composition for members has high adhesion, heat resistance, heat and humidity resistance, plasticizer resistance, and processability, and has excellent corrosion resistance to IT conductive transparent conductive films or metal circuits. On the other hand, in Comparative Examples i to 9 of Table 3, the balance of physical properties was not obtained, and in particular, many people who had problems in corrosion were observed. In particular, it has high adhesion to various adherends including conductive members and is excellent in heat resistance and corrosion resistance, and is an important characteristic that can be achieved by the present invention. [Simple description of the diagram] 〇 [Explanation of main component symbols] 322162 52
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