TW201802603A - 被鍍覆層形成用組成物、帶被鍍覆層前驅體層的膜、帶圖案狀被鍍覆層的膜、導電性膜、觸控面板 - Google Patents
被鍍覆層形成用組成物、帶被鍍覆層前驅體層的膜、帶圖案狀被鍍覆層的膜、導電性膜、觸控面板 Download PDFInfo
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- TW201802603A TW201802603A TW106107871A TW106107871A TW201802603A TW 201802603 A TW201802603 A TW 201802603A TW 106107871 A TW106107871 A TW 106107871A TW 106107871 A TW106107871 A TW 106107871A TW 201802603 A TW201802603 A TW 201802603A
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Abstract
本發明的課題在於提供一種可形成鹼耐性優異的被鍍覆層、於藉由低曝光量的曝光而形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的被鍍覆層形成用組成物、帶被鍍覆層前驅體層的膜、帶圖案狀被鍍覆層的膜、導電性膜及觸控面板。本發明的被鍍覆層形成用組成物包含:具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體。
Description
本發明是有關於一種被鍍覆層形成用組成物、帶被鍍覆層前驅體層的膜、帶圖案狀被鍍覆層的膜、導電性膜、及觸控面板。
於基板上配置有導電膜(導電性細線)的導電性膜用於多種用途。尤其近年來,隨著觸控面板於行動電話及可攜式遊戲設備等中的搭載率的上升,能進行多點檢測的靜電電容方式的觸控面板感測器用的導電性膜的需求急速擴大。
關於此種導電膜的形成,例如提出有使用圖案狀被鍍覆層的方法。 例如,於專利文獻1中,作為導電膜的形成方法,記載有「一種導電膜的形成方法,其包括:(a)於有機樹脂基板上形成樹脂層(樹脂層A)的步驟,所述樹脂層(樹脂層A)含有自由基聚合性化合物與熱硬化性樹脂,且包含70℃下的凝膠化時間為60分鐘以下的熱硬化性樹脂組成物;(b)形成樹脂層(樹脂層B)的步驟,所述樹脂層(樹脂層B)含有具有與無電解鍍覆觸媒或其前驅體進行相互作用的官能基的樹脂、自由基產生劑、及自由基聚合性化合物,且可吸附無電解鍍覆觸媒或其前驅體;(c)將無電解鍍覆觸媒或其前驅體賦予至可吸附無電解鍍覆觸媒或其前驅體的層(樹脂層B)的步驟;以及(d)進行無電解鍍覆而形成無電解鍍覆膜的步驟。」。 作為用以形成作為鍍覆膜的基底的圖案狀被鍍覆層即樹脂層B的樹脂組成物,於所述專利文獻1的實施例10中揭示有一種包含聚丙烯酸與作為二官能單體的N,N'-亞甲基雙(丙烯醯胺)的丙烯酸樹脂組成物。此外,為了形成圖案狀被鍍覆層,而對所述丙烯酸樹脂組成物的層實施曝光處理。 [現有技術文獻] [專利文獻]
[專利文獻1]日本專利特開2009-218509號公報
[發明所欲解決之課題] 另一方面,近年來要求提升導電膜的生產性,於如專利文獻1般實施曝光處理的情況下,期望以低曝光量來形成所期望的導電膜。 本發明者等人對如專利文獻1的實施例10中所記載般的包含二官能單體的丙烯酸樹脂組成物(被鍍覆層形成用組成物)進行了研究。具體而言,發現:於對所述被鍍覆層形成用組成物進行曝光時,若其曝光量小,則對於對所述被鍍覆層形成用組成物進行曝光及顯影所形成的圖案狀被鍍覆層而言,即便實施鍍覆處理,亦存在鍍覆不析出的情況(換言之,存在無法形成金屬層的情況)。 另外,於鍍覆處理時,有時使用銅鍍覆液等高鹼性的鍍覆液。於被鍍覆層對鹼的耐性(以下亦稱為「鹼耐性」)差的情況下,若對該被鍍覆層應用高鹼性的鍍覆液,則所述被鍍覆層自基板剝離,而無法於基板上形成金屬層。因此,被鍍覆層形成用組成物亦要求可形成鹼耐性優異的被鍍覆層。
因此,本發明的課題在於提供一種可形成鹼耐性優異的被鍍覆層、且於藉由低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的被鍍覆層形成用組成物。 另外,本發明的課題在於提供一種使用被鍍覆層形成用組成物所形成的帶被鍍覆層前驅體層的膜。 進而,本發明的課題在於提供一種使用所述帶被鍍覆層前驅體層的膜所形成的帶圖案狀被鍍覆層的膜、以及使用該帶圖案狀被鍍覆層的膜的導電性膜及觸控面板。 [解決課題之手段]
本發明者等人為了達成所述課題而進行了努力研究,結果發現:藉由被鍍覆層形成用組成物包含具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體,而可解決所述課題,從而完成了本發明。 即,發現藉由以下構成而可達成所述目的。
(1)一種被鍍覆層形成用組成物,其包含:具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及 具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體。 (2) 如(1)所述的被鍍覆層形成用組成物,其中所述與鍍覆觸媒或其前驅體進行相互作用的基為羧基。 (3)如(1)或(2)所述的被鍍覆層形成用組成物,其更包含界面活性劑。 (4)如(1)~(3)中任一項所述的被鍍覆層形成用組成物,其中所述多官能單體相對於所述聚合物的含量以質量比計超過1。 (5) 一種帶被鍍覆層前驅體層的膜,其具有:基板、及配置於所述基板上的藉由如(1)~(4)中任一項所述的被鍍覆層形成用組成物而形成的被鍍覆層前驅體層。 (6) 如(5)所述的帶被鍍覆層前驅體層的膜,其中於所述基板與所述被鍍覆層前驅體層之間具有中間層。 (7) 一種帶圖案狀被鍍覆層的膜,其是藉由使(5)或(6)所述的帶被鍍覆層前驅體層的膜中的所述被鍍覆層前驅體層進行曝光以硬化形成圖案狀,且具有基板與圖案狀被鍍覆層。 (8) 一種導電性膜,其是於如(7)所述的帶圖案狀被鍍覆層的膜的所述圖案狀被鍍覆層上積層金屬層而成。 (9) 一種觸控面板,其包含如(8)所述的導電性膜。 [發明的效果]
根據本發明,可提供一種可形成鹼耐性優異的被鍍覆層、且於藉由低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的被鍍覆層形成用組成物。 另外,根據本發明,可提供一種使用所述被鍍覆層形成用組成物所形成的帶被鍍覆層前驅體層的膜。 進而,根據本發明,可提供一種使用所述帶被鍍覆層前驅體層的膜所形成的帶圖案狀被鍍覆層的膜、以及使用該帶圖案狀被鍍覆層的膜的導電性膜及觸控面板。
以下,對本發明進行詳細說明。 以下所記載的構成要件的說明有時是基於本發明的代表性實施態樣而成,本發明並不限定於此種實施態樣。 此外,本說明書中,使用「~」所表示的數值範圍是指含有「~」的前後所記載的數值作為下限值以及上限值的範圍。 另外,本說明書中的「光化射線」或「放射線」例如是指水銀燈的明線光譜、以準分子雷射為代表的遠紫外線、極紫外線(極紫外(Extreme Ultraviolet,EUV)光)、X射線、及電子束(electron beam,EB)等。另外,本說明書中,光是指光化射線或放射線。 另外,只要事先無特別說明,則本說明書中的「曝光」不僅包含利用水銀燈、以準分子雷射為代表的遠紫外線、極紫外線、X射線、及EUV光等進行的曝光,利用電子束及離子束等粒子束進行的描繪亦包含於曝光中。
〔被鍍覆層形成用組成物〕 本發明的被鍍覆層形成用組成物包含: 具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及 具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體。 本發明的被鍍覆層形成用組成物藉由所述的構成,鹼耐性優異,且於藉由低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層。 其詳細情況並不明確,如以下般進行推測。 本發明的被鍍覆層形成用組成物的特徵在於包含具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體的方面。 所述具有三個以上的丙烯醯胺基或甲基丙烯醯胺基(以下亦稱為「(甲基)丙烯醯胺基」)的多官能單體藉由曝光而進行交聯硬化,形成緻密的網格,並將具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物籠絡保持於該網格內。因此,所形成的被鍍覆層作為鍍覆用的觸媒或其前驅體的吸附基底而發揮功能。 另外,藉由該多官能單體所形成的被鍍覆層的鹼耐性優異。因此,所述被鍍覆層於藉由高鹼性的鍍覆液進行鍍覆處理時,不易自基板剝離。結果,可於被鍍覆層上形成金屬層。 進而,藉由曝光而將具有三個以上的(甲基)丙烯醯胺基的多官能單體硬化所形成的膜,與藉由曝光而將(甲基)丙烯醯胺基的二官能單體硬化所形成的膜相比較而言,於藉由低曝光進行的曝光後,於顯影時亦不易流動。即,於以低曝光對包含具有三個以上的(甲基)丙烯醯胺基的多官能單體的被鍍覆層形成用組成物進行曝光的情況下,所形成的膜於顯影時不易流動,結果,認為可將具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物良好地保持於網格內。藉此,於藉由低曝光量的曝光來形成被鍍覆層的情況下,亦可於被鍍覆層上形成金屬層。 以下,首先對本發明的被鍍覆層形成用組成物的各成分進行說明。
<具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物> 被鍍覆層形成用組成物包含具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物。 具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物可於其結構中具有聚合性官能基,就使本發明的效果更優異的觀點而言,較佳為不具有聚合性官能基。 此外,所謂「不具有聚合性官能基」,是指聚合物中實質上不具有聚合性官能基,聚合性官能基較佳為於聚合物總質量中為0.1質量%以下,更佳為0.01質量%以下。下限並無特別限制,為0質量%。 另外,聚合性官能基為藉由能量賦予而可形成化學鍵的官能基,例如可列舉自由基聚合性基及陽離子聚合性官能基等。作為聚合性官能基,例如可列舉:丙烯酸酯基(丙烯醯氧基)、甲基丙烯酸酯基(甲基丙烯醯氧基)、衣康酸酯基、丁烯酸酯基、異丁烯酸酯基、及馬來酸酯基等不飽和羧酸酯基,此外可列舉苯乙烯基、乙烯基、丙烯醯胺基、及甲基丙烯醯胺基等。
所謂與鍍覆觸媒或其前驅體進行相互作用的基(以下亦稱為「相互作用性基」),是指可與賦予至被鍍覆層的鍍覆觸媒或其前驅體(例如金屬或金屬離子)進行相互作用的官能基。作為具體的相互作用性基,例如可使用:能與鍍覆觸媒或其前驅體形成靜電相互作用的官能基、以及能與鍍覆觸媒或其前驅體形成配位的含氮官能基、含硫官能基、及含氧官能基等。 作為相互作用性基,更具體而言,可列舉:胺基、醯胺基、醯亞胺基、脲基、三級胺基、銨基、脒基、三嗪環、三唑環、苯并三唑基、咪唑基、苯并咪唑基、喹啉基、吡啶基、嘧啶基、吡嗪基、喹唑啉基、喹噁啉基、嘌呤基、三嗪基、哌啶基、哌嗪基、吡咯啶基、吡唑基、苯胺基、含有烷基胺結構的基、含有異三聚氰酸結構的基、硝基、亞硝基、偶氮基、重氮基、疊氮基、氰基、及氰酸酯基等含氮官能基;醚基、羥基、酚性羥基、羧基、碳酸酯基、羰基、酯基、含有N-氧化物結構的基、含有S-氧化物結構的基、及含有N-羥基結構的基等含氧官能基;噻吩基、硫醇基、硫脲基、三聚硫氰酸基、苯并噻唑基、巰基三嗪基、硫醚(thioether)基、硫氧基、亞碸基、碸基、硫醚(sulfite)基、含有磺醯亞胺結構的基、含有氧化鋶鹽結構的基、磺酸基、及含有磺酸酯結構的基等含硫官能基;膦酸酯基、磷醯胺基、膦基、及含有磷酸酯結構的基等含磷官能基;含有氯原子及溴原子等鹵素原子的基等,於可採取鹽結構的官能基中亦可使用該些的鹽。 其中,就極性高、對鍍覆觸媒或其前驅體的吸附能力高的方面而言,較佳為羧基、磺酸基、磷酸基、及硼酸基等離子性極性基,醚基,或氰基。另外,就可與對鍍覆觸媒或其前驅體的吸附能力同時賦予顯影性的觀點而言,更佳為羧基或磺酸基,就為適度的酸性(不分解其他官能基)的觀點而言,進而佳為羧基。 另外,亦可於聚合物中含有兩種以上的相互作用性基。
具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物並無特別限定,例如可列舉具有作為下述式(2)而示出的重複單元(A)的聚合物。
所述式(2)中,R21
表示氫原子、或者經取代或未經取代的烷基(例如甲基、乙基、丙基、及丁基等)。此外,取代基的種類並無特別限制,可列舉:甲氧基、氯原子、溴原子、或氟原子等。
作為R21
,較佳為氫原子、甲基、或經溴原子取代的甲基。
所述式(2)中,X表示單鍵、或者經取代或未經取代的二價有機基。此外,取代基的種類並無特別限制,可列舉:甲氧基、氯原子、溴原子、或氟原子等。 作為二價有機基,可列舉:經取代或未經取代的二價脂肪族烴基(較佳為碳原子數1~8。例如亞甲基、伸乙基、及伸丙基等伸烷基)、經取代或未經取代的二價芳香族烴基(較佳為碳原子數6~12。例如伸苯基)、-O-、-S-、-SO2
-、-N(R)-(R:烷基(較佳為碳原子數1~8))、-CO-、-NH-、-COO-、-CONH-、或者將該些組合而成的基(例如伸烷基氧基、伸烷基氧基羰基、或伸烷基羰基氧基等)等。
就聚合物的合成容易、金屬層的密接性更優異的方面而言,X較佳為單鍵、酯基(-COO-)、醯胺基(-CONH-)、醚基(-O-)、或者經取代或未經取代的二價芳香族烴基,更佳為單鍵、酯基(-COO-)、或醯胺基(-CONH-)。
所述式(2)中,L21
表示單鍵、或者經取代或未經取代的二價有機基。作為經取代或未經取代的二價有機基的定義,與所述X所表示的經取代或未經取代的二價有機基相同。
就金屬層的密接性更優異的方面而言,L21
較佳為單鍵、或者經取代或未經取代的二價脂肪族烴基、經取代或未經取代的二價芳香族烴基、或者將該些組合而成的基。其中,L21
更佳為單鍵、或者總碳原子數1~15的或者經取代或未經取代的二價有機基。此外,二價有機基較佳為未經取代。此外,此處所謂總碳原子數,是指L21
所表示的經取代或未經取代的二價有機基中所含的總碳原子數。
所述式(2)中,W表示相互作用性基。相互作用性基的定義如上所述。
所述中,就合成容易的方面而言,作為所述聚合物,較佳為聚(甲基)丙烯酸。此外,本發明中,所謂(甲基)丙烯酸是包含丙烯酸及甲基丙烯酸這兩者的概念。
就對鍍覆觸媒或其前驅體的吸附性的觀點而言,相對於聚合物中的所有重複單元,所述相互作用性基單元(重複單元(A))的含量較佳為5莫耳%~100莫耳%,更佳為10莫耳%~100莫耳%。 此外,聚合物亦可含有所述重複單元(A)以外的其他重複單元,例如,可列舉源自不含相互作用性基的公知的單體(例如,苯乙烯單體、烯烴單體、或丙烯酸單體等)的重複單元。
具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的重量平均分子量並無特別限制,就溶解性等操作性更優異的方面而言,較佳為1000以上且70萬以下,更佳為1000以上且50萬以下,進而佳為2000以上且20萬以下。尤其,就聚合感度的觀點而言,進而佳為20000以上。 該些聚合物可利用公知的方法來製造。
具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的重量平均分子量可使用凝膠滲透層析法(gel permeation chromatography,GPC)進行確認。即,為了藉由GPC來求出具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的重量平均分子量,只要基於對事先已知分子量的多種各不相同的多個聚合物(例如聚苯乙烯),於相同條件下進行測定而得的滯留時間(retention time)與分子量的關係的校準曲線進行算出即可。 此外,作為GPC測定方法,更具體而言,可使對象物溶解於四氫呋喃(tetrahydrofuran,THF),使用高速GPC裝置(例如HLC-8220GPC(東曹股份有限公司製造)),藉由聚苯乙烯換算而算出。此外,GPC測定的條件如下所述。 管柱:東曹公司製造的TSK-GEL SuperH 管柱溫度:40℃ 流速:1 mL/分鐘 溶離液:THF
被鍍覆層形成用組成物中,具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的含量並無特別限制,就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,相對於組成物中的總固體成分100質量%,較佳為20質量%以上,更佳為25質量%以上。上限並無特別限制,較佳為70質量%以下,更佳為60質量%以下,進而佳為45質量%以下。
<具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體> 本發明的被鍍覆層形成用組成物包含具有三個以上的(甲基)丙烯醯胺基的多官能單體。
具有三個以上的(甲基)丙烯醯胺基的多官能單體(以下亦稱為「多官能單體」)只要具有三個以上的(甲基)丙烯醯胺基即可,就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,(甲基)丙烯醯胺基的數量較佳為3~8,更佳為4~6。 另外,多官能單體的分子量並無特別限制,就進一步提升反應性、進一步抑制硬化收縮的觀點而言,較佳為200~1500,更佳為250~1000。即,藉由將多官能單體的分子量設為200以上,可進一步抑制硬化收縮的產生。另一方面,藉由將多官能單體的分子量設為1500以下,可進一步抑制由擴散速度的降低所引起的反應性降低。 此外,多官能單體中亦可含有所述相互作用性基。
作為多官能單體的較佳態樣之一,就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,可列舉式(X)所表示的化合物。
式(X)中,Q表示n價連結基,Ra
表示氫原子或甲基。n表示3以上的整數。
Ra
表示氫原子或甲基,較佳為氫原子。 Q的價數n為3以上,較佳為3~6。 作為Q所表示的n價連結基,例如可列舉將式(1A)所表示的基、式(1B)所表示的基、
芳香族基、或雜環基、或者選自該些基中的一種以上,與選自-NH-、-NR(R:表示烷基)-、-O-、-S-、羰基、伸烷基、伸烯基、伸炔基、及伸環烷基中的一種以上組合而成的基。
關於式(X)所表示的化合物,可適宜地參照日本專利特開2013-43946號公報的段落[0019]~段落[0034]、及日本專利特開2013-43945號公報的段落[0070]~段落[0080]等的記載。
作為式(X)所表示的化合物的較佳態樣,就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,可列舉式(Y)所表示的化合物。
式(Y)中,R1
各自獨立地表示氫原子或甲基。R2
各自獨立地表示碳原子數2~4的直鏈或分支的伸烷基。其中,於R2
中,不採取鍵結於R2
的兩端的氧原子與氮原子鍵結於R2
的同一碳原子的結構。R3
各自獨立地表示二價連結基。k表示2或3。x、y及z各自獨立地表示0~6的整數,x+y+z滿足0~18。
R2
表示碳原子數2~4的直鏈或分支的伸烷基。多個R2
可相互相同,亦可不同。R2
較佳為碳原子數3~4的伸烷基,更佳為碳原子數3的伸烷基,進而佳為碳原子數3的直鏈伸烷基。R2
的伸烷基亦可進而具有取代基,作為該取代基,可列舉芳基、或烷氧基等。 其中,於R2
中,不採取鍵結於R2
的兩端的氧原子與氮原子鍵結於R2
的同一碳原子的結構。R2
為連結氧原子與(甲基)丙烯醯胺基的氮原子的直鏈或分支的伸烷基,於該伸烷基採取分支結構的情況下,亦考慮採取兩端的氧原子與(甲基)丙烯醯胺基的氮原子鍵結於伸烷基中的同一碳原子的-O-C-N-結構(半胺縮醛(hemiaminal)結構)。但是,式(Y)所表示的化合物中不含此種結構的化合物。
作為R3
的二價連結基,可列舉伸烷基、伸芳基、雜環基、或包含該些的組合的基等,較佳為伸烷基。此外,於二價連結基含有伸烷基的情況下,該伸烷基中亦可更含有選自-O-、-S-、及NRb
-中的至少一種基。 Rb
表示氫原子或碳原子數1~4的烷基。
x、y及z各自獨立地表示0~6的整數,較佳為0~5的整數,更佳為0~3的整數。x+y+z滿足0~18,較佳為0~15,更佳為0~9。
就被鍍覆層前驅體層的硬化速度優異的觀點等而言,更佳為下述式(4)所表示的多官能單體。 下述式(4)所表示的多官能單體例如可利用日本專利第5486536號公報中記載的製造方法來製造。
所述式(4)中,R表示氫原子或甲基。於所述式(4)中,多個R可相互相同,亦可不同。
被鍍覆層形成用組成物中,多官能單體的含量並無特別限制,就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,相對於組成物中的總固體成分100質量%,較佳為30質量%以上,更佳為40質量%以上,進而佳為50質量%以上。上限並無特別限制,較佳為75質量%以下,更佳為70質量%以下。
就於藉由更低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層的觀點而言,多官能單體相對於具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的含量以質量比計,較佳為超過1,更佳為2以上。所述質量比的上限並無特別限制,可列舉20以下。
<聚合起始劑> 被鍍覆層形成用組成物較佳為含有界面活性劑。藉由被鍍覆層形成用組成物中含有聚合起始劑,更有效率地進行曝光處理時的聚合性官能基間的反應。 聚合起始劑並無特別限制,可使用公知的聚合起始劑(所謂的光聚合起始劑)等。作為聚合起始劑的例子,可列舉:二苯甲酮類、苯乙酮類、α-胺基苯烷基酮類、安息香類、酮類、硫雜蒽酮類、苯偶醯類、苯偶醯縮酮類、肟酯類、蒽酮(anthrone)類、一硫化四甲基秋蘭姆類、雙醯基氧化膦類、醯基氧化膦類、蒽醌類、或偶氮化合物等、或者該些的衍生物。 被鍍覆層形成用組成物中的聚合起始劑的含量並無特別限制,就圖案狀被鍍覆層的硬化性的方面而言,相對於多官能單體的總含有量100質量%,較佳為0.1質量%~20質量%,更佳為1質量%~10質量%。
<溶劑> 就操作性的方面而言,被鍍覆層形成用組成物中較佳為含有溶劑。 可使用的溶劑並無特別限定,例如可列舉:水;甲醇、乙醇、丙醇、乙二醇、1-甲氧基-2-丙醇、甘油、及丙二醇單甲醚等醇系溶劑;乙酸等酸;丙酮、甲基乙基酮、及環己酮等酮系溶劑;甲醯胺、二甲基乙醯胺、及N-甲基吡咯啶酮等醯胺系溶劑;乙腈、及丙腈等腈系溶劑;乙酸甲酯、及乙酸乙酯等酯系溶劑;碳酸二甲酯、及碳酸二乙酯等碳酸酯系溶劑;除此以外,亦可列舉:醚系溶劑、二醇系溶劑、胺系溶劑、硫醇系溶劑、及鹵素系溶劑等。 其中,較佳為醇系溶劑、醯胺系溶劑、酮系溶劑、腈系溶劑、及碳酸酯系溶劑。 被鍍覆層形成用組成物中的溶劑的含量並無特別限制,相對於組成物總量,較佳為50質量%~98質量%,更佳為70質量%~98質量%。若為所述範圍內,則組成物的操作性優異,容易進行圖案狀被鍍覆層的層厚的控制。
<界面活性劑> 被鍍覆層形成用組成物中較佳為含有界面活性劑。藉由於被鍍覆層形成用組成物中含有界面活性劑,可抑制由所述被鍍覆層形成用組成物所形成的被鍍覆層前驅體層、與曝光時賦予至被鍍覆層前驅體層的非曝光區域的光罩的過度貼附。即,於曝光後將光罩卸下時,除光罩的去除性優異以外,亦可抑制被鍍覆層前驅體層的一部分附著於光罩。
作為界面活性劑,可使用:氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑及矽酮系界面活性劑等各種界面活性劑。該些界面活性劑中,就所述效果得到進一步發揮的方面而言,較佳為氟系界面活性劑及矽酮系界面活性劑,更佳為氟系界面活性劑。界面活性劑可僅使用一種,亦可將兩種以上加以組合。
作為氟系界面活性劑,例如可列舉:W-AHE及W-AHI(以上,富士軟片(Fujifilm)(股)製造),美佳法(Megafac)F171、美佳法(Megafac)F172、美佳法(Megafac)F173、美佳法(Megafac)F176、美佳法(Megafac)F177、美佳法(Megafac)F141、美佳法(Megafac)F142、美佳法(Megafac)F143、美佳法(Megafac)F144、美佳法(Megafac)R30、美佳法(Megafac)F437、美佳法(Megafac)F475、美佳法(Megafac)F479、美佳法(Megafac)F482、美佳法(Megafac)F554、美佳法(Megafac)F780及美佳法(Megafac)F781F(以上,迪愛生(DIC)(股)製造),弗拉德(Fluorad)FC430、弗拉德(Fluorad)FC431及弗拉德(Fluorad)FC171(以上,住友3M(股)製造),沙福隆(Surflon)S-382、沙福隆(Surflon)SC-101、沙福隆(Surflon)SC-103、沙福隆(Surflon)SC-104、沙福隆(Surflon)SC-105、沙福隆(Surflon)SC1068、沙福隆(Surflon)SC-381、沙福隆(Surflon)SC-383、沙福隆(Surflon)S393及沙福隆(Surflon)KH-40(以上,旭硝子(股)製造),PF636、PF656、PF6320、PF6520、PF7002(歐諾法(OMNOVA)公司製造)等。
所述矽酮系界面活性劑中可使用市售品,例如可列舉:東麗矽酮(Toray Silicone)DC3PA、東麗矽酮(Toray Silicone)SH7PA、東麗矽酮(Toray Silicone)DC11PA、東麗矽酮(Toray Silicone)SH21PA、東麗矽酮(Toray Silicone)SH28PA、東麗矽酮(Toray Silicone)SH29PA、東麗矽酮(Toray Silicone)SH30PA及東麗矽酮(Toray Silicone)SH8400(以上,東麗道康寧(Toray Dow Corning)(股)製造),TSF-4440、TSF-4300、TSF-4445、TSF-4460及TSF-4452(以上,邁圖高新材料(Momentive Performance Materials)公司製造),KP341、KF6001及KF6002(以上,信越矽酮(股)製造),畢克(BYK)307、畢克(BYK)323及畢克(BYK)330(以上,畢克化學(BYK-Chemie)公司製造)等。
被鍍覆層形成用組成物中的界面活性劑的含量並無特別限制,相對於組成物總量,較佳為0.01質量%~1.5質量%,更佳為0.01質量%~1質量%。
<其他添加劑> 被鍍覆層形成用組成物中亦可視需要添加其他添加劑(例如增感劑、硬化劑、聚合抑制劑、抗氧化劑、抗靜電劑、紫外線吸收劑、填料、粒子、阻燃劑、潤滑劑、以及塑化劑等)。
〔帶被鍍覆層前驅體層的膜、帶圖案狀被鍍覆層的膜及導電性膜〕 以下,對本發明的導電性膜進行詳細敘述,同時亦對本發明的帶被鍍覆層前驅體層的膜及帶圖案狀被鍍覆層的膜進行詳細敘述。 本發明的導電性膜具有:基板、形成於基板上的圖案狀被鍍覆層、及藉由鍍覆處理而積層於圖案狀被鍍覆層表面的金屬層。 本發明的導電性膜可藉由具有下述步驟1及步驟2的製造方法而製作。 步驟1:於基板上,藉由所述被鍍覆層形成用組成物而形成被鍍覆層前驅體層後,對該被鍍覆層前驅體層實施圖案曝光而以圖案狀進行硬化,藉此而形成圖案狀被鍍覆層的圖案狀被鍍覆層形成步驟; 步驟2:藉由鍍覆處理而於圖案狀被鍍覆層上形成金屬層的金屬層形成步驟 此外,本說明書中,將具有基板、及基板上所形成的被鍍覆前驅體層的膜稱為「帶被鍍覆層前驅體層的膜」,將經過所述步驟1而獲得的膜稱為「帶圖案狀被鍍覆層的膜」。
圖1為表示本發明的導電性膜的實施形態的一例的剖面示意圖。圖1的導電性膜100具有:基板12、配置於基板12上的圖案狀被鍍覆層20、及配置於圖案狀被鍍覆層20上的金屬層22。 以下,將導電性膜100的製造方法作為一例,參照圖式進行說明。另外,同時亦對本發明的帶被鍍覆層前驅體層的膜的製造方法、及本發明的帶圖案狀被鍍覆層的膜的製造方法進行說明。此外,本發明的實施形態並不限於以下示出的態樣。
<基板> 基板只要為具有兩個主面、且支撐後述的圖案狀被鍍覆層者,則其種類並無特別限制。作為基板,較佳為絕緣基板,更具體而言,可列舉樹脂基板、陶瓷基板、及玻璃基板等。 作為樹脂基板的材料,例如可列舉:聚醚碸系樹脂、聚(甲基)丙烯酸系樹脂、聚胺基甲酸酯系樹脂、聚酯系樹脂(例如聚對苯二甲酸乙二酯、或聚萘二甲酸乙二酯等)、聚碳酸酯系樹脂、聚碸系樹脂、聚醯胺系樹脂、聚烯丙酸酯(polyallylate)系樹脂、聚烯烴系樹脂、纖維素系樹脂、聚氯乙烯系樹脂、及環烯烴系樹脂等。其中,較佳為聚酯系樹脂(例如聚對苯二甲酸乙二酯、或聚萘二甲酸乙二酯等)、或聚烯烴系樹脂。 基板的厚度(mm)並無特別限制,就操作性及薄型化的平衡的方面而言,較佳為0.01 mm~2 mm,更佳為0.02 mm~0.1 mm。 另外,基板較佳為適當地透過光。具體而言,基板的總光線透過率較佳為85%~100%。 另外,基板亦可為多層結構,例如亦可包含功能性膜作為其中一層。此外,亦可基板自身為功能性膜。雖無特別限定,但作為功能性膜的例子,可列舉:偏光板、相位差膜、覆蓋塑膠、硬塗膜、阻擋膜、黏著膜、電磁波屏蔽膜、發熱膜、天線膜、及觸控面板以外的元件用配線膜等。 尤其,作為用於與觸控面板相關的液晶單元中的功能性膜的具體例,偏光板可列舉NPF系列(日東電工公司製造)或HLC2系列(三立子(SANRITZ)公司製造)等,相位差膜可列舉WV膜(富士軟片公司製造)等,覆蓋塑膠可列舉范恩德(FAINDE)(大日本印刷製造)、特諾羅伊(Technolloy)(住友化學製造)、尤皮隆(Iupilon)(三菱瓦斯化學製造)、西普拉斯(Silplus)(新日鐵住金製造)、奧爾加(ORGA)(日本合成化學製造)或昭拉雅(SHORAYAL)(昭和電工製造)等,硬塗膜可列舉H系列(琳得科(Lintec)公司製造)、FHC系列(東山軟片公司製造)或KB膜(木本(KIMOTO)公司製造)等。該些亦可於各功能性膜的表面上形成圖案狀被鍍覆層。 另外,於偏光板及相位差膜中,存在如日本專利特開2007-26426號公報中所記載般使用纖維素三乙酸酯的情況,就對於鍍覆製程的耐性的觀點而言,亦可將纖維素三乙酸酯變更為環烯烴(共)聚合物而使用,例如可列舉瑞諾(Zeonor)(日本瑞翁(ZEON)製造)等。
[步驟1:圖案狀被鍍覆層形成步驟] 步驟1是對藉由被鍍覆層形成用組成物所形成的塗膜,以圖案狀進行曝光,將圖案狀被鍍覆層形成於基板上的步驟,所述被鍍覆層形成用組成物包含具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及具有三個以上的(甲基)丙烯醯胺基的多官能單體。 更具體而言,為如下步驟:首先,如圖2A所示,製作於基板12上形成被鍍覆層形成用組成物的塗膜(相當於被鍍覆層前驅體層)30而成的帶被鍍覆層前驅體層的膜10,繼而,如圖2B所示,介隔光罩25,如黑色箭頭所示般對塗膜30以圖案狀進行曝光,藉此促進聚合性基(例如具有三個以上的(甲基)丙烯醯胺基的多官能單體中所含的(甲基)丙烯醯胺基)的反應而進行硬化,然後,將未曝光區域去除而獲得圖案狀被鍍覆層20(圖2C)。 藉由所述步驟而形成的帶圖案狀被鍍覆層的膜50的圖案狀被鍍覆層20根據相互作用性基的功能,於後述的步驟2中吸附(附著)鍍覆觸媒或其前驅體。即,圖案狀被鍍覆層作為鍍覆觸媒或其前驅體的良好的接收層而發揮功能。另外,聚合性官能基藉由基於曝光的硬化處理而用於化合物彼此的結合,從而可獲得硬度優異的圖案狀被鍍覆層。
步驟1中,首先,於基板上配置被鍍覆層前驅體層。其方法並無特別限制,例如可列舉使所述被鍍覆層形成用組成物接觸於基板上,形成被鍍覆層形成用組成物的塗膜的方法。作為該方法,例如可列舉將所述被鍍覆層形成用組成物塗佈於基板上的方法(塗佈法)。 於塗佈法的情況下,將被鍍覆層形成用組成物塗佈於基板上的方法並無特別限制,可使用公知的方法(例如棒塗法、旋塗法、模塗法、及浸塗法等)。 就操作性及製造效率的觀點而言,較佳為將被鍍覆層形成用組成物塗佈於基板上,視需要進行乾燥處理而形成塗膜的態樣。 此外,乾燥處理的條件並無特別限制,就生產性更優異的方面而言,較佳為於室溫~220℃(較佳為50℃~120℃)下實施1分鐘~30分鐘(較佳為1分鐘~10分鐘)。
對基板上的塗膜以圖案狀進行曝光的方法並無特別限制,例如可列舉照射光化射線或放射線的方法。作為利用光化射線的照射,可使用利用UV(紫外線)燈、及可見光線等的光照射等。作為光源,例如可列舉水銀燈、金屬鹵化物燈、氙燈、化學燈、及碳弧燈等。另外,作為放射線,可列舉電子束、X射線、離子束、及遠紅外線等。 作為對基板上的塗膜以圖案狀進行曝光的具體的態樣,可較佳地列舉:利用紅外線雷射的掃描曝光、使用遮罩的氙放電燈等的高照度閃光曝光、或使用遮罩的紅外線燈曝光等。藉由對塗膜進行曝光,塗膜中的化合物中所含的聚合性官能基活性化,化合物間產生交聯,而進行層的硬化。 作為曝光時間,根據化合物的反應性及光源而不同,通常為10秒~300秒。作為曝光能量(曝光量),只要為20 mJ/cm2
~300 mJ/cm2
左右即可,較佳為50 mJ/cm2
~100 mJ/cm2
的範圍。
其次,將塗膜中的未曝光區域去除而形成圖案狀被鍍覆層。 所述去除方法並無特別限制,根據所使用的化合物來適宜地選擇最佳的方法。例如,可列舉使用鹼性溶液(較佳為pH:13.0~13.8)作為顯影液的方法。於使用鹼性溶液將未曝光區域去除的情況下,可列舉將具有經曝光的塗膜的基板浸漬於溶液中的方法(浸漬方法)、或者於具有經曝光的塗膜的基板上塗佈顯影液的方法(塗佈方法)等,較佳為浸漬方法。於浸漬方法的情況下,作為浸漬時間,就生產性及作業性等的觀點而言,較佳為1分鐘~30分鐘左右。 另外,作為其他方法,可列舉將溶解所使用的化合物的溶劑作為顯影液而浸漬於其中的方法。
<圖案狀被鍍覆層> 藉由所述處理而形成的圖案狀被鍍覆層的厚度並無特別限制,就生產性的方面而言,較佳為0.01 μm~10 μm,更佳為0.2 μm~5 μm,進而佳為0.3 μm~1.0 μm。 圖案狀被鍍覆層的圖案形狀並無特別限制,根據欲形成後述的金屬層的部位進行調整,例如可列舉網格圖案等。於網格圖案的情況下,網格圖案內的格子(開口部)的一邊的長度W較佳為800 μm以下,更佳為600 μm以下,較佳為50 μm以上,更佳為400 μm以上。此外,格子的形狀並無特別限制,可設為大致菱形的形狀,或多邊形狀(例如三角形、四邊形、六邊形)。另外,除了直線狀以外,一邊的形狀亦可為彎曲形狀,亦可設為圓弧狀。 另外,圖案狀被鍍覆層的線寬並無特別限制,就配置於圖案狀被鍍覆層上的金屬層的低電阻性的方面而言,較佳為30 μm以下,更佳為15 μm以下,進而佳為10 μm以下,特佳為9 μm以下,最佳為7 μm以下。另一方面,其下限較佳為0.5 μm以上,更佳為1.0 μm以上。
[步驟2:金屬層形成步驟] 步驟2是將鍍覆觸媒或其前驅體賦予至所述步驟1中所形成的圖案狀被鍍覆層,對賦予有鍍覆觸媒或其前驅體的圖案狀被鍍覆層進行鍍覆處理而於圖案狀被鍍覆層上形成金屬層的步驟。如圖2D所示,藉由實施本步驟,而於圖案狀被鍍覆層20上配置金屬層22,從而獲得導電性膜100。 以下,分開來說明將鍍覆觸媒或其前驅體賦予至圖案狀被鍍覆層的步驟(步驟2-1)、與對賦予有鍍覆觸媒或其前驅體的圖案狀被鍍覆層進行鍍覆處理的步驟(步驟2-2)。
(步驟2-1:觸媒賦予步驟) 本步驟中,首先,將鍍覆觸媒或其前驅體賦予至圖案狀被鍍覆層。源自所述具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物的相互作用性基根據其功能而附著(吸附)所賦予的鍍覆觸媒或其前驅體。更具體而言,將鍍覆觸媒或其前驅體賦予至圖案狀被鍍覆層中及圖案狀被鍍覆層表面上。 鍍覆觸媒或其前驅體作為鍍覆處理的觸媒或電極而發揮功能。因此,根據鍍覆處理的種類來適宜地決定所使用的鍍覆觸媒或其前驅體的種類。 此外,所使用的鍍覆觸媒或其前驅體較佳為無電解鍍覆觸媒或其前驅體。
若於本步驟中所使用的鍍覆觸媒成為鍍覆時的活性核,則無論何種觸媒均可使用。具體而言,可列舉具有自觸媒還原反應的觸媒能力的金屬(作為可進行離子化傾向低於Ni的無電解鍍覆的金屬而已知者)等。具體而言,可列舉:鈀(Pd)、銀(Ag)、銅(Cu)、鎳(Ni)、鉑(Pt)、金(Au)、或鈷(Co)等。其中,就觸媒能力的高低而言,特佳為銀(Ag)、鈀(Pd)、鉑(Pt)、或銅(Cu)。 亦可使用金屬膠體來作為該鍍覆觸媒。 所謂於本步驟中使用的鍍覆觸媒前驅體,若為藉由化學反應而可成為鍍覆觸媒者,則可無特別限制地使用。主要使用作為所述鍍覆觸媒而列舉的金屬的金屬離子。作為鍍覆觸媒前驅體的金屬離子藉由還原反應而成為作為鍍覆觸媒的0價金屬。作為鍍覆觸媒前驅體的金屬離子亦可於被賦予至圖案狀被鍍覆層之後、浸漬於鍍覆浴之前,另外藉由還原反應而變化為0價金屬來作為鍍覆觸媒。另外,亦可於保持鍍覆觸媒前驅體的狀態下浸漬於鍍覆浴,並藉由鍍覆浴中的還原劑而變化為金屬(鍍覆觸媒)。 金屬離子較佳為使用金屬鹽而賦予至圖案狀被鍍覆層。作為所使用的金屬鹽,只要為溶解於適當的溶劑中而解離為金屬離子與鹼(陰離子)者則並無特別限制,可列舉:M(NO3
)n
、MCln
、M2/n
(SO4
)、及M3/n
(PO4
)(M表示n價金屬原子)等。作為金屬離子,可較佳地使用所述金屬鹽解離而成者。作為具體例,例如可列舉:銀(Ag)離子、銅(Cu)離子、鋁(Al)離子、鎳(Ni)離子、鈷(Co)離子、鐵(Fe)離子、及鈀(Pd)離子,其中,較佳為能進行多牙配位者,尤其,就能進行配位的官能基的種類數及觸媒能力的方面而言,較佳為銀(Ag)離子或鈀(Pd)離子。
作為將金屬離子賦予至圖案狀被鍍覆層的方法,例如只要製備含有將金屬鹽於適當的溶劑中溶解、解離的金屬離子的溶液,並將所述溶液塗佈於圖案狀被鍍覆層上,或者將形成有圖案狀被鍍覆層的基板浸漬於所述溶液中即可。 作為所述溶劑,可適宜地使用水或有機溶劑。作為有機溶劑,較佳為可滲透於圖案狀被鍍覆層中的溶劑,例如可使用:丙酮、乙醯乙酸甲酯、乙醯乙酸乙酯、乙二醇二乙酸酯、環己酮、乙醯丙酮、苯乙酮、2-(1-環己烯基)環己酮、丙二醇二乙酸酯、甘油三乙酸酯、二乙二醇二乙酸酯、二噁烷、N-甲基吡咯啶酮、碳酸二甲酯、及二甲基溶纖劑等。
溶液中的鍍覆觸媒或其前驅體的濃度並無特別限制,較佳為0.001質量%~50質量%,更佳為0.005質量%~30質量%。 另外,作為接觸時間,較佳為30秒~24小時左右,更佳為1分鐘~1小時左右。
關於圖案狀被鍍覆層的鍍覆觸媒或其前驅體的吸附量,根據使用的鍍覆浴種、觸媒金屬種、圖案狀被鍍覆層的相互作用性基種、及使用方法等而不同,就鍍覆的析出性的觀點而言,較佳為5 mg/m2
~1000 mg/m2
,更佳為10 mg/m2
~800 mg/m2
,進而佳為20 mg/m2
~600 mg/m2
。
(步驟2-2:鍍覆處理步驟) 其次,對賦予有鍍覆觸媒或其前驅體的圖案狀被鍍覆層進行鍍覆處理。 鍍覆處理的方法並無特別限制,例如可列舉無電解鍍覆處理或電解鍍覆處理(電鍍處理)。本步驟中,可單獨實施無電解鍍覆處理,亦可於實施無電解鍍覆處理後進而實施電解鍍覆處理。 此外,於本說明書中,所謂的銀鏡反應是作為所述無電解鍍覆處理的一種而含有。如此,例如可藉由銀鏡反應等而使所附著的金屬離子還原,從而形成所期望的圖案狀的金屬層,進而亦可於其後實施電解鍍覆處理。 以下,對無電解鍍覆處理、以及電解鍍覆處理的程序進行詳細敘述。
所謂無電解鍍覆處理,是指使用溶解有欲以鍍覆的方式析出的金屬離子的溶液,藉由化學反應而使金屬析出的操作。 本步驟中的無電解鍍覆處理例如是對包括賦予有金屬離子的圖案狀被鍍覆層的基板進行水洗而去除多餘的金屬離子後,浸漬於無電解鍍覆浴中來進行。作為所使用的無電解鍍覆浴,可使用公知的無電解鍍覆浴。此外,於無電解鍍覆浴中,進行金屬離子的還原,緊接著進行無電解鍍覆。 圖案狀被鍍覆層中的金屬離子的還原亦能夠與使用所述般的無電解鍍覆液的態樣不同,準備觸媒活性化液(還原液)而作為無電解鍍覆處理前的另一步驟而進行。觸媒活性化液是溶解可將金屬離子還原成0價金屬的還原劑的液體,還原劑相對於液體總體的濃度較佳為0.1質量%~50質量%,更佳為1質量%~30質量%。作為還原劑,可使用硼氫化鈉或二甲胺硼烷般的硼系還原劑、甲醛、及次磷酸等還原劑。 於浸漬時,較佳為於施加攪拌或搖動的同時進行浸漬。
作為通常的無電解鍍覆浴的組成,除溶劑(例如水)以外,主要含有1.鍍覆用的金屬離子、2.還原劑、3.提升金屬離子的穩定性的添加劑(穩定劑)。除該些以外,亦可於該鍍覆浴中含有鍍覆浴的穩定劑等公知的添加劑。 作為無電解鍍覆浴中所使用的有機溶劑,需要為能於水的溶劑,就該方面而言,較佳為丙酮等酮類,或者甲醇、乙醇及異丙醇等醇類。作為無電解鍍覆浴中所使用的金屬的種類,已知有銅、錫、鉛、鎳、金、銀、鈀、及銠,其中,就導電性的觀點而言,較佳為銅、銀、或金,更佳為銅。另外,根據所述金屬來選擇最佳的還原劑、添加劑。 作為於無電解鍍覆浴中的浸漬時間,較佳為1分鐘~6小時左右,更佳為1分鐘~3小時左右。
所謂電解鍍覆處理,是指使用溶解有欲以鍍覆的方式析出的金屬離子的溶液,藉由電流而使金屬析出的操作。 此外,如上所述,於本步驟中,可於所述無電解鍍覆處理之後,視需要進行電解鍍覆處理。於此種態樣中,能適宜地調整所形成的圖案狀的金屬層的厚度。 作為電解鍍覆的方法,可使用現有公知的方法。此外,作為電解鍍覆中所使用的金屬,可列舉:銅、鉻、鉛、鎳、金、銀、錫、及鋅等,就導電性的觀點而言,較佳為銅、金、或銀,更佳為銅。 另外,藉由電解鍍覆而獲得的金屬層的膜厚可藉由調整鍍覆浴中所含的金屬濃度、或電流密度等而進行控制。
藉由所述程序而形成的金屬層的厚度並無特別限制,根據使用目的而適宜地選擇最佳的厚度,就導電特性的方面而言,較佳為0.1 μm以上,更佳為0.5 μm以上,進而佳為1 μm~30 μm。 另外,構成金屬層的金屬的種類並無特別限制,例如可列舉:銅、鉻、鉛、鎳、金、銀、錫、及鋅等,就導電性的觀點而言,較佳為銅、金、或銀,更佳為銅或銀。 金屬層的圖案形狀並無特別限制,由於金屬層配置於圖案狀被鍍覆層上,故根據圖案狀被鍍覆層的圖案形狀進行調整,例如可列舉網格圖案等。網格圖案的金屬層可較佳地用作觸控面板中的感測器電極。於金屬層的圖案形狀為網格圖案的情況下,網格圖案內的格子(開口部)的一邊的長度W的範圍、格子的形狀的較佳態樣、及金屬層的線寬與所述圖案狀被鍍覆層的態樣相同。
(中間層) 作為所述導電性膜的實施形態的另一例,亦可於基板上更包含中間層。更具體而言,如圖3的導電性膜100'所示,亦可於基板12上進而鄰接配置中間層40。藉由於基板與圖案狀被鍍覆層之間配置中間層,兩者的密接性進一步提升。
中間層的厚度並無特別限制,通常較佳為0.01 μm~100 μm,更佳為0.05 μm~20 μm,進而佳為0.05 μm~10 μm。 中間層的材料並無特別限制,較佳為與基板的密接性良好的樹脂。作為樹脂的具體例,例如可為熱硬化性樹脂,亦可為熱塑性樹脂,另外亦可為該些的混合物,例如,作為熱硬化性樹脂,可列舉:環氧樹脂、酚樹脂、聚醯亞胺樹脂、聚酯樹脂、雙馬來醯亞胺樹脂、聚烯烴系樹脂、及異氰酸酯系樹脂等。作為熱塑性樹脂,例如可列舉:苯氧基樹脂、聚醚碸、聚碸、聚苯碸、聚苯硫醚、聚苯醚、聚醚醯亞胺、及丙烯腈-丁二烯-苯乙烯共聚物(Acrylonitrile-Butadiene-Styrene copolymer,ABS)樹脂等。 熱塑性樹脂與熱硬化性樹脂分別可單獨使用,亦可併用兩種以上。另外,亦可使用含有氰基的樹脂,具體而言,亦可使用ABS樹脂、或日本專利特開2010-84196號的〔0039〕~〔0063〕中記載的「含有在側鏈具有氰基的單元的聚合物」。 另外,亦可使用NBR橡膠(丙烯腈丁二烯橡膠(acrylonitrile butadiene rubber))、或SBR橡膠(苯乙烯丁二烯橡膠(styrene butadiene rubber))等橡膠成分。
作為構成中間層的材料的較佳態樣之一,可列舉具有可氫化的共軛二烯化合物單元的聚合物。所謂共軛二烯化合物單元,是指源自共軛二烯化合物的重複單元。作為共軛二烯化合物,只要為具有含有藉由一個單鍵而隔開的兩個碳-碳雙鍵的分子結構的化合物則並無特別限制。 作為源自共軛二烯化合物的重複單元的較佳態樣之一,可列舉藉由具有丁二烯骨架的化合物發生聚合反應而生成的重複單元。 所述共軛二烯化合物單元亦可氫化,於含有氫化的共軛二烯化合物單元的情況下,金屬層的密接性進一步提升而較佳。即,源自共軛二烯化合物的重複單元中的雙鍵亦可氫化。 具有可氫化的共軛二烯化合物單元的聚合物中亦可含有所述相互作用性基。 作為該聚合物的較佳態樣,可列舉:丙烯腈丁二烯橡膠(NBR)、含羧酸基的腈橡膠(XNBR)、丙烯腈-丁二烯-異戊二烯橡膠(acrylonitrile butadiene isoprene rubber,NBIR)、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、或該些的氫化產物(例如氫化丙烯腈丁二烯橡膠(hydrogenated nitrile butadiene rubber)(別名:氫化腈橡膠(HNBR)))等。
中間層中亦可含有其他添加劑(例如增感劑、抗氧化劑、抗靜電劑、紫外線吸收劑、填料、粒子、阻燃劑、界面活性劑、潤滑劑、及塑化劑等)。
中間層的形成方法並無特別限制,可列舉:將所使用的樹脂於基板上進行層壓的方法;或者將所需成分溶解於能溶解該成分的溶劑中,藉由塗佈等方法於基板表面上進行塗佈、及乾燥的方法等。 塗佈方法中的加熱溫度與時間只要選擇可將塗佈溶劑充分乾燥的條件即可,就製造適應性的方面而言,較佳為加熱溫度為200℃以下、時間為60分鐘以內的範圍的加熱條件,更佳為加熱溫度為40℃~100℃、時間為20分鐘以內的範圍的加熱條件。此外,所使用的溶劑是根據所使用的樹脂來適宜地選擇最佳的溶劑(例如環己酮或甲基乙基酮)。
於使用配置有所述中間層的基板的情況下,藉由於中間層上實施所述步驟1及步驟2,而可獲得所期望的導電性膜。
〔用途〕 具有藉由所述處理而獲得的金屬層的導電性膜可應用於多種用途,可應用於觸控面板(或觸控面板感測器)、半導體晶片、各種電性配線板、撓性印刷電路(Flexible Printed Circuits,FPC)、覆晶薄膜(Chip on Film,COF)、捲帶式自動接合(Tape Automated Bonding,TAB)、天線、多層配線基板、以及主機板等多種用途。其中,較佳為用於觸控面板感測器(靜電電容式觸控面板感測器)。於將所述導電性積層體用於觸控面板感測器的情況下,導電性膜中的金屬層作為觸控面板感測器中的檢測電極或引出配線而發揮功能。 此外,於本說明書中,將使觸控面板感測器、各種顯示裝置(例如液晶顯示裝置、有機電致發光(Electro-Luminescence,EL)顯示裝置)組合而成者稱為觸控面板。觸控面板可較佳地列舉所謂的靜電電容式觸控面板。 [實施例]
以下,基於實施例來對本發明進一步進行詳細說明。以下的實施例中所示的材料、使用量、比例、處理內容、及處理程序等只要不脫離本發明的主旨則可適宜地進行變更。因此,本發明的範圍不應受到以下所示的實施例限定性地解釋。 此外,於下述實施例中,「%」及「份」表示質量基準。
〔實施例1〕 (被鍍覆層形成用組成物的製備) 於異丙醇中,以3:7的固體成分質量比添加作為聚合物的聚丙烯酸(黏度為8000 cp~12000 cp(此外,1 cp=1 mPa·s)、重量平均分子量為37萬、和光純藥工業股份有限公司製造)、及作為多官能單體的下述結構的四官能丙烯醯胺A(其中,結構式中的R為氫)來製備溶液,接著,以相對於所述多官能單體而言含量成為5質量%的方式將肟系聚合起始劑(豔佳固(irgacure)OXE、日本巴斯夫(BASF Japan)公司製造)添加至所述溶液。繼而,於添加有肟系聚合起始劑的溶液中,以相對於組成物總質量而言的濃度成為0.02質量%的方式添加作為界面活性劑的W-AHE(富士軟片股份優選公司製造),從而製備實施例1的被鍍覆層形成用組成物。此外,被鍍覆層形成用組成物中,異丙醇的含量為90質量%。
<鍍覆析出的最低曝光量的評價> 使用實施例1的被鍍覆層形成用組成物,藉由以下所示的方法來進行鍍覆析出的最低曝光量的評價。 藉由棒塗機將實施例1的被鍍覆層形成用組成物塗佈於厚度為50 μm的聚酯膜(A4300:東洋紡股份有限公司製造)上後,使塗佈有被鍍覆層形成用組成物的聚酯膜於80℃下乾燥3分鐘,藉此而於聚酯膜上形成厚度約為0.5 μm的塗膜。 對於所獲得的塗膜,使用平行曝光機,改變曝光量而以形成步進楔(step-wedge)狀的圖像形狀的方式照射365 nm的波長的光,進行曝光。繼而,利用1質量%的碳酸鈉水溶液對經過曝光處理的膜進行顯影處理。
然後,對經過顯影處理的膜進行水洗,使具有經水洗的膜的聚酯膜於30℃的Pd觸媒賦予液(R&H公司製造)中浸漬5分鐘。其次,對自Pd觸媒賦予液取出的聚酯膜進行水洗,然後,將該聚酯膜浸漬於30℃的金屬觸媒還原液(R&H公司製造)中。其次,再次對自Pd觸媒賦予液取出的聚酯膜進行水洗,然後,使該聚酯膜於30℃的銅鍍覆液(R&H公司製造)中浸漬15分鐘。 此外,所述銅鍍覆液(R&H公司製造)為鹼性的鍍覆液。
藉由目視觀察經過所述方法而獲得的膜,而對鍍覆開始析出的最低曝光量進行評價。數值越小,則表示可藉由更低的曝光量來形成金屬層。將結果示於表1中。 此外,於比較例3中,金屬層未析出。
(金屬層(金屬配線)的形成) 使用實施例1的被鍍覆層形成用組成物,藉由下述順序而製作於基板上積層有圖案狀被鍍覆層並於該圖案狀被鍍覆層的表面積層有金屬層(金屬配線)的導電性膜。
首先,藉由棒塗機將實施例1的被鍍覆層形成用組成物塗佈於厚度為50 μm的聚酯膜(A4300:東洋紡股份有限公司製造)上後,使塗佈有被鍍覆層形成用組成物的聚酯膜於80℃下乾燥3分鐘,藉此而形成被鍍覆層前驅體層(厚度約為0.5 μm)。對於所獲得的被鍍覆層前驅體層,介隔光罩,使用平行曝光機,以成為所述鍍覆析出的最低曝光量的評價中的曝光量的方式照射365 nm的波長的光。 繼而,利用1質量%的碳酸鈉水溶液對曝光後的被鍍覆層前驅體層進行顯影處理,獲得圖案狀被鍍覆層。然後,對具有圖案狀被鍍覆層的聚酯膜進行水洗,然後,將該聚酯膜於30℃的Pd觸媒賦予液(R&H公司製造)中浸漬5分鐘。其次,對自Pd觸媒賦予液取出的聚酯膜進行水洗,然後,將該聚酯膜浸漬於30℃的金屬觸媒還原液(R&H公司製造)中。其次,再次對自Pd觸媒賦予液取出的聚酯膜進行水洗,然後,使該聚酯膜於30℃的銅鍍覆液(R&H公司製造)中浸漬15分鐘。 此外,所述銅鍍覆液(R&H公司製造)如上所述為鹼性的鍍覆液。
<鹼耐性評價> 藉由目視觀察所獲得的金屬配線,而對圖案狀被鍍覆層的鹼耐性進行評價。評價基準如下所述。 「A」:整個圖案區域被銅鍍覆被覆。 「B」:雖然銅鍍覆的被覆並非整個圖案區域,但超過整個圖案區域的50面積%。 「C」:銅鍍覆的被覆為整個圖案區域的50面積%以下。 將結果示於表1中。
<貼附性評價> 於所述金屬配線的形成中,於曝光結束後對被鍍覆層前驅體層與光罩的貼附性進行評價。貼附性具體而言是藉由如下方式進行評價:於曝光結束後,將樣品膜自光罩剝去,以目視來觀察剝去樣品膜後的光罩。評價基準如下所述。 「A」:不存在被鍍覆層前驅體層的構成成分轉印至光罩 「B」:存在被鍍覆層前驅體層的構成成分轉印至光罩 將結果示於表1中。
〔實施例2〕 將聚合物與多官能單體的固體成分質量比設為4:6,除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔實施例3〕 將聚合物與多官能單體的固體成分質量比設為5:5,除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔實施例4〕 將聚合物與多官能單體的固體成分比率設為6:4,除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔實施例5〕 不添加界面活性劑,除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔實施例6〕 將聚合物設為多磷酸(PCAS公司製造),除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔比較例1〕 將多官能單體設為N-異丙基丙烯醯胺(和光純藥工業股份有限公司製造),除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔比較例2〕 將多官能單體設為1,4-二丙烯醯基哌嗪(和光純藥工業股份有限公司製造),除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
〔比較例3〕 將多官能單體設為二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)(DPHA、西格瑪奧德里奇(Sigma-Aldrich)公司製造),除此以外與實施例1同樣地進行而獲得被鍍覆層形成用組成物。 另外,與實施例1同樣地進行所獲得的被鍍覆層形成用組成物的最低曝光量、鹼耐性、及貼附性的評價。將結果示於表1中。
確認到:若使用實施例的被鍍覆層形成用組成物,則均可形成鹼耐性優異的被鍍覆層、且於藉由低曝光量的曝光來形成被鍍覆層的情況下亦可於被鍍覆層上形成金屬層。 另外,根據實施例1~實施例4的對比而確認到:藉由將多官能單體相對於聚合物的含量設為以質量比計超過1(較佳為2以上),鍍覆析出的最低曝光量變得更低。 另外,根據實施例1與實施例6的對比而確認到:於聚合物具有羧基的情況下,鍍覆析出的最低曝光量變得更低。
另外,根據實施例5與實施例1的對比而確認到:藉由被鍍覆層形成用組成物含有界面活性劑,可減少曝光後的光罩的貼附,換言之,可改善貼附性。
另一方面,比較例的被鍍覆層形成用組成物未滿足所期望的性能。
<膠帶密接性評價(膠帶剝離試驗)> 進而,對於使用實施例1的被鍍覆層形成用組成物如上所述般製作而成的金屬層(金屬配線),藉由下述方法來實施膠帶密接性評價(膠帶剝離試驗)。 另外,對於與實施例1同樣地,使用實施例2~實施例6、比較例1~比較例3的被鍍覆層形成用組成物如上所述般製作而成的金屬層(金屬配線),亦實施膠帶密接性評價(膠帶剝離試驗)。將結果示於表2中。
(評價方法及基準) 於將黏著膠帶(商品名:賽璐膠帶(Cellotape)(註冊商標)、米其邦(Nichiban)公司製造)貼附於基板上的形成有金屬圖案的區域後,立刻剝去。目視觀察有無金屬層轉印至剝去的膠帶,依照下述評價基準來評價金屬層的密接性。將結果示於表2中。 「A」:未觀察到金屬層轉印至膠帶 「B」:觀察到金屬層轉印至膠帶
另外,如下所示,製作於基板與圖案狀被鍍覆層之間具有中間層的實施例7及實施例8的導電性膜,藉由相同的方法來實施所述膠帶密接性評價。將結果示於表2中。
〔實施例7〕 將使氫化丙烯腈丁二烯橡膠吉特珀(Zetpol)0020(日本瑞翁(ZEON)製造)100 g溶解於環戊酮(東京化成製造)900 g中所得的液體設為中間層形成用組成物。繼而,將中間層形成用組成物以成為2 μm的膜厚的方式塗佈於厚度為50 μm的聚酯膜(A4300:東洋紡股份有限公司製造)上後,對塗佈有中間層形成用組成物的聚酯膜進行乾燥,藉此而形成中間層的塗膜。 進而,藉由與實施例1相同的順序,使用實施例1的被鍍覆層形成用組成物,於以上所製作的中間層上以0.5 μm的膜厚設置被鍍覆層前驅體層後,製作積層有圖案狀被鍍覆層並於該圖案狀被鍍覆層的表面積層有金屬層(金屬配線)的導電性膜。 使用所獲得的導電性膜來實施所述膠帶密接性評價。將結果示於表2中。
〔實施例8〕 將實施例1的被鍍覆層形成用組成物設為實施例2的被鍍覆層形成用組成物,除此以外,藉由與實施例7相同的方法來製作實施例8的導電性膜,實施所述膠帶密接性評價。將結果示於表2中。
如表2所示,確認到:如實施例7及實施例8般,藉由於基板與圖案狀被鍍覆層之間設置中間層,可使金屬層對基板的密接性更優異。
10‧‧‧帶被鍍覆層前驅體層的膜
12‧‧‧基板
20‧‧‧圖案狀被鍍覆層
22‧‧‧金屬層
25‧‧‧光罩
30‧‧‧塗膜(被鍍覆層前驅體層)
40‧‧‧中間層
50‧‧‧帶圖案狀被鍍覆層的膜
100、100'‧‧‧導電性膜
12‧‧‧基板
20‧‧‧圖案狀被鍍覆層
22‧‧‧金屬層
25‧‧‧光罩
30‧‧‧塗膜(被鍍覆層前驅體層)
40‧‧‧中間層
50‧‧‧帶圖案狀被鍍覆層的膜
100、100'‧‧‧導電性膜
圖1為示意性地表示本發明的導電性膜的實施形態的一例的剖面圖。 圖2A為示意性地表示獲得帶被鍍覆層前驅體層的膜10的步驟的一例的剖面圖。 圖2B為示意性地表示藉由曝光將帶被鍍覆層前驅體層的膜10中的塗膜30硬化的步驟的一例的剖面圖。 圖2C為示意性地表示獲得帶圖案狀被鍍覆層的膜50的步驟的一例的剖面圖。 圖2D為示意性地表示於圖案狀被鍍覆層20上形成金屬層22而獲得導電性膜100的步驟的一例的剖面圖。 圖3為示意性地表示本發明的導電性膜的實施形態的另一例的剖面圖。
12‧‧‧基板
20‧‧‧圖案狀被鍍覆層
22‧‧‧金屬層
100‧‧‧導電性膜
Claims (9)
- 一種被鍍覆層形成用組成物,其包含:具有與鍍覆觸媒或其前驅體進行相互作用的基的聚合物、及 具有三個以上的丙烯醯胺基或甲基丙烯醯胺基的多官能單體。
- 如申請專利範圍第1項所述的被鍍覆層形成用組成物,其中所述與鍍覆觸媒或其前驅體進行相互作用的基為羧基。
- 如申請專利範圍第1項或第2項所述的被鍍覆層形成用組成物,其更包含界面活性劑。
- 如申請專利範圍第1項或第2項所述的被鍍覆層形成用組成物,其中所述多官能單體相對於所述聚合物的含量以質量比計超過1。
- 一種帶被鍍覆層前驅體層的膜,其具有:基板、及配置於所述基板上的藉由如申請專利範圍第1項至第4項中任一項所述的被鍍覆層形成用組成物而形成的被鍍覆層前驅體層。
- 如申請專利範圍第5項所述的帶被鍍覆層前驅體層的膜,其中於所述基板與所述被鍍覆層前驅體層之間具有中間層。
- 一種帶圖案狀被鍍覆層的膜,其是藉由使申請專利範圍第5項或第6項所述的帶被鍍覆層前驅體層的膜中的所述被鍍覆層前驅體層進行曝光以硬化形成圖案狀,且具有基板與圖案狀被鍍覆層。
- 一種導電性膜,其是於如申請專利範圍第7項所述的帶圖案狀被鍍覆層的膜的所述圖案狀被鍍覆層上積層金屬層而成。
- 一種觸控面板,其包含如申請專利範圍第8項所述的導電性膜。
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CN111902567A (zh) * | 2018-03-26 | 2020-11-06 | 富士胶片株式会社 | 前体薄膜、附被镀覆层基板、导电性薄膜、触摸面板传感器、触摸面板、导电性薄膜的制造方法及被镀覆层形成用组合物 |
CN111936665A (zh) * | 2018-03-26 | 2020-11-13 | 富士胶片株式会社 | 前体薄膜、附被镀覆层基板、导电性薄膜、触摸面板传感器、触摸面板、导电性薄膜的制造方法及被镀覆层形成用组合物 |
TWI795599B (zh) * | 2018-09-28 | 2023-03-11 | 日商富士軟片股份有限公司 | 導電性構件、觸控面板感測器、觸控面板、成形體之製造方法 |
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JP2009218509A (ja) | 2008-03-12 | 2009-09-24 | Fujifilm Corp | 導電膜の形成方法及びプリント配線板の製造方法 |
JP5241304B2 (ja) * | 2008-04-23 | 2013-07-17 | 富士フイルム株式会社 | 表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の作製方法、及び金属パターン材料 |
JP5258489B2 (ja) | 2008-09-30 | 2013-08-07 | 富士フイルム株式会社 | 金属膜形成方法 |
JP5486536B2 (ja) | 2011-03-30 | 2014-05-07 | 富士フイルム株式会社 | 重合性化合物 |
JP5591771B2 (ja) | 2011-08-24 | 2014-09-17 | 富士フイルム株式会社 | インクセット及び画像形成方法 |
JP5501311B2 (ja) | 2011-08-24 | 2014-05-21 | 富士フイルム株式会社 | インク組成物、インクセット、及び画像形成方法 |
EP3156886A4 (en) * | 2014-06-10 | 2017-06-21 | Fujifilm Corporation | Electrically-conductive laminate for touchscreen, touchscreen, and transparent electrically-conductive laminate |
WO2016159136A1 (ja) * | 2015-03-31 | 2016-10-06 | 富士フイルム株式会社 | 被めっき層形成用組成物、被めっき層前駆体層付きフィルム、パターン状被めっき層付きフィルム、導電性フィルム、タッチパネル |
WO2016181824A1 (ja) * | 2015-05-11 | 2016-11-17 | 富士フイルム株式会社 | 導電性積層体の製造方法、導電性積層体、被めっき層前駆体層付き基板、被めっき層付き基板、タッチセンサー |
JP6388558B2 (ja) * | 2015-05-29 | 2018-09-12 | 富士フイルム株式会社 | 導電性フィルム、タッチパネルセンサー、および、タッチパネル |
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CN111902567A (zh) * | 2018-03-26 | 2020-11-06 | 富士胶片株式会社 | 前体薄膜、附被镀覆层基板、导电性薄膜、触摸面板传感器、触摸面板、导电性薄膜的制造方法及被镀覆层形成用组合物 |
CN111936665A (zh) * | 2018-03-26 | 2020-11-13 | 富士胶片株式会社 | 前体薄膜、附被镀覆层基板、导电性薄膜、触摸面板传感器、触摸面板、导电性薄膜的制造方法及被镀覆层形成用组合物 |
US11561631B2 (en) | 2018-03-26 | 2023-01-24 | Fujifilm Corporation | Precursor film, substrate with plated layer, conductive film, touch panel sensor, touch panel, method for producing conductive film, and composition for forming plated layer |
TWI795599B (zh) * | 2018-09-28 | 2023-03-11 | 日商富士軟片股份有限公司 | 導電性構件、觸控面板感測器、觸控面板、成形體之製造方法 |
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