200937472 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用於可攜式電話等之通信終端、各種儀 器、個人電腦輸入用之鍵盤（keyboard )、遙控器等之操作部 的鍵盤（keypad)用之薄膜。 【先前技術】 近年來，一種由熱塑性聚胺基甲酸酯、聚對苯二甲酸乙 二醇酯、聚酯彈性體等樹脂所製造之薄膜所構成的鍵盤用之 〇 薄膜所獲得之鍵盤，經將鍵頂（key top )(按鈕鍵（button key ))加以黏著、印刷或印刷黏著等所製造之鍵控片（key sheet )已被廣泛地使用於可攜式電話等之通信終端、各種計量儀 器、個人電腦輸入用之鍵盤、遙控器等之操作部，且有一些 有關此等之鍵控片的技術已爲眾所皆知（參閱例如發明專利 文獻1及2等）。此外，在用於構成該鍵盤的鍵盤用之薄膜 的原材料中，由於具有適度的柔軟感或優越的緩衝性（ cushioning )及高耐久性，因此以熱塑性聚胺基甲酸酯爲特別 ® 適用，並且一些關於以此等熱塑性聚胺基甲酸酯作爲原材料 的鍵盤用之薄膜的技術已爲眾所皆知。 例如，已有提案一種藉由以至少使用選自六亞甲基二異 氰酸酯或氫化二苯甲烷二異氰酸酯之異氰酸酯及多元醇作爲 合成成份所合成得之熱塑性聚胺基甲酸酯樹脂來構成用於積 層於聚矽氧橡膠等作成爲鍵盤所需要之鍵盤用表面材，以製 成具有優越的柔軟觸感、不會發生發黃、且耐水性、耐熱性 高、物性之降低少的聚胺基甲酸酯製造之表面材的方法（參 閱發明專利文獻3)。 200937472 此外，已知有一種將以六亞甲基二異氰酸酯爲主成份之 有機二異氰酸酯、以聚碳酸酯二醇爲主成份之高分子多元醇 、及以碳數爲2至10之脂肪族二醇爲主成份之鏈段增長劑（ chain extender)進行反應所獲得之樹脂切粒，將其加以熔融 成型所獲得之熱塑性聚胺基甲酸酯樹脂片加以熱成型所獲得 之聚胺基甲酸酯樹脂所製造之鍵盤係可顯現具有優越的二次 成型性、耐油酸性、抗變色性、透明性、印刷適性（參閱發 明專利文獻4 ;然而，由具體揭述於發明專利文獻4之熱塑性 0 聚胺基甲酸酯所構成之薄膜在23 °C伸長100%時的拉伸應力 (M1()Q)係即使爲高者（合成實施例3之聚胺基甲酸酯）充 其量也僅爲約8 MPa)。 然而，在使用鍵盤用之薄膜製造鍵盤或鍵控片時，大部 份係塗佈黏著劑或印刷印墨並使其固化或固定、或與由其他 之樹脂所構成的層積層而需要實施加熱處理。然而，由於先 前的以熱塑性聚胺基甲酸酯所製造之鍵盤用之薄膜的拉伸應 力較小，特別是在施加爲使黏著劑或印刷印墨加以固化或固 〇 定、或與由其他之樹脂所構成的層積層之加熱處理時，則容 易發生由於耐熱性不足的薄膜之翹曲（warping)或收縮等之 不良現象、或薄膜彼此膠著等問題。當發生此等之薄膜的翹 曲或收縮、及薄膜彼此膠著時，則將造成將所獲得之鍵控片 配置於可攜式電話等之最終製品的預定位置時等，卻因需要 以人工將其加以平坦化後始能嵌進或要求特殊裝置等而降低 最終製品之生產性，或因經常發生無法用作爲鍵控片或鍵盤 之不良品而降低良率之問題。因此，熱塑性聚胺基甲酸酯雖 然具有如上所述之適度的柔軟感或優越的緩衝性及高耐久性 200937472 ’但是目前以其爲原材料作爲鍵盤用之薄膜時，則其使用範 圍仍然受限’以致正需要解決如上所述之問題。特別是近年 來在可攜式電話方面，爲重視設計性之薄型化更進一步的進 展，使得鍵控片或鍵盤也有要求更爲薄型者之傾向，因此一 直強烈地需要解決如上所述之問題。 此外’先前之由以熱塑性聚胺基甲酸酯爲首的樹脂所製 造之薄膜所構成的鍵盤用之薄膜，由於如上所述的拉伸應力 較小且爲柔軟，已提案一種爲保持所獲得之鍵控片的形狀等 Ο 之目的而積層框架片（frame sheet )之技術。例如，已提案 一種在具備由比較柔軟的熱塑性聚胺基甲酸酯（在23°C伸長 100%時的拉伸應力（Mbo)爲約7 MPa)等所禱成之樹脂薄 膜基片（鍵盤）、配置於基片之鍵頂、以及具備特定的印刷 黏著層之鍵控片中，以固定並補強該鍵頂（按鈕鍵）爲目的 而積層框架片之技術（參閱發明專利文獻5)。 然而，當積層框架片時，則會造成最終製品的可攜式電 ® 話等之輕量化或縮小化之達成有困難，且製程將趨於煩雜之 問題。 (發明專利文獻1 )特開第2004-327307號公報 (發明專利文獻2)特開第2004- 1 1 1 25 8號公報 (發明專利文獻3 )特開第2005-25960號公報 (發明專利文獻4)國際公開第2004/106401號小冊子 (發明專利文獻5 )特開第2007-668 1 8號公報 200937472 【發明内容】 〔所欲解決之技術問題〕 本發明係爲解決如上所述問題所達成，而以提供一種具 有優越的非膠黏性（non-tackiness )、使用性（handling capability)、耐熱性及尺寸精確度之穩定性，同時特別是即 使由於爲固化或固定黏著劑或印刷印墨時等而實施加熱處理 ，也不會發生翹曲或收縮等之不良現象、或薄膜彼此膠著等 問題之鍵盤用之薄膜作爲其技術問題。此外，提供一種可用 ❹ 於製造即使不使用框架片等之補強材也可保持形狀之可達成 可攜式電話等之最終製品之輕量化或縮小化且也可簡化製程 之鍵盤或鍵控片之鍵盤用之薄膜爲其技術問題。並且，本發 明係以提供一種至少包括由該鍵盤用之薄膜所構成的層之鍵 盤，以及至少具有該鍵盤及鍵頂之鍵控片爲其技術問題。 〔解決問題之技術方法〕 爲解決如上所述技術問題，本發明之發明人等經重覆進 〇 行各種檢討結果發現：在由熱塑性聚胺基甲酸酯形成鍵盤用 之薄膜時，則將該薄膜在23t伸長100%時的拉伸應力（00 )〔在下文中，有時候則將「在23 t伸長100%時的拉伸應力 (Miqq)」只稱爲「拉伸應力（tensile stress) (Μι〇。）」。 〕設定爲特定的範圍，藉此則不僅可改善在加熱處理時或處 理後的薄膜之翹曲，在後步驟之加工製程通過性也將趨於良 好，且也可提高生產良率。此外，本發明之發明人等也發現 :只要使用如上所述之鍵盤用之薄膜，在製造鍵盤或鍵控片 200937472 時’則不再需要補強材，甚至可達成可攜式電話等之最終製 品之輕量化或縮小化、也可簡化製程。並且，根據此等觀點 而重覆進行檢討結果終於達成本發明。 亦即，本發明係關於： (ο —種鍵盤用之薄膜，其係由高分子多元醇、有機聚異 氰酸酯及鏈段增長劑進行反應所獲得之熱塑性聚胺基 甲酸酯單獨構成、或由主要由該熱塑性聚胺基甲酸酯 所組成之熱塑性聚胺基甲酸酯組成物所構成，且在23 〇 °c伸長100%時的拉伸應力（M! 〇〇)爲18 MPa以上； (2) 如第（1)項所述之鍵盤用之薄膜，其中在該熱塑性聚 胺基甲酵酯之源於異氰酸酯基之氮原子的含率爲4.5. 質量％以上； (3) 如第（1)或（2)項所述之鍵盤用之薄膜，其中該有 機聚異氰酸酯係主要由4,4’-二苯甲烷二異氰酸酯所組 成； (4) 如第（1)至（3)項中任一項所述之鍵盤用之薄膜， Ο 其中該鏈段增長劑係主要由1，4-丁二醇所組成； (5) 如第（1)至（4)項中任一項所述之鍵盤用之薄膜， 其中高分子多元醇之數量平均分子量爲5 00至8,000; (6) 如第（1)至（5)項中任一項所述之鍵盤用之薄膜， 其之厚度爲20至3 00 ym; (7) —種鍵盤，其係至少包括由如第（1)至（6)項中任 一項所述之鍵盤用之薄膜所構成的層； (8) —種鍵控片’其係至少具有如第（7)項所述之鍵盤及 鍵頂。 200937472 〔發明之功效〕 若根據本發明，則可獲得具有優越的非膠黏性、使用性 、耐熱性及尺寸精確度之穩定性，同時特別是即使由於在爲 固化或固定黏著劑或印刷印墨時等而實施加熱處理時，則也 可獲得不會發生翹曲或收縮等之不良現象、或薄膜彼此膠著 等之問題的鍵盤用之薄膜。若根據本發明之鍵盤用之薄膜， 則可獲得即使不使用框架片等之補強材也可保持形狀，且可 達成可攜式電話等之最終製品之輕量化或縮小化、也可簡化 φ 製程之鍵盤或鍵控片。 【實施方式】 > 在下文中，則將詳細地說明本發明。 本發明之鍵盤用之薄膜係由高分子多元醇、有機聚異氰 酸酯及鏈段增長劑進行反應所獲得之熱塑性聚胺基甲酸酯單 獨構成、或由主要由該熱塑性聚胺基甲酸酯所組成之熱塑性 聚胺基甲酸酯組成物所構成。 在本發明中所使用的高分子多元醇係可使用傳統慣用於 〇 製造聚胺基甲酸酯之任一高分子多元醇。此等「高分子多元 醇」的實例係包括：聚酯多元醇、聚醚多元醇、聚碳酸酯多 元醇、聚酯-聚碳酸酯多元醇、聚烯烴系多元醇、也可加以氫 化之共軛二烯聚合物系多元醇、蓖麻油系多元醇、乙烯基聚 合物系多元醇等。此等高分子多元醇係可單獨使用一種或其 兩種以上倂用。其中，高分子多元醇係適合使用聚酯多元醇 、聚醚多元醇、聚碳酸酯多元醇中之一種或兩種以上，較佳 爲聚酯多元醇和/或聚醚多元醇，更佳爲使用聚酯二醇和/或聚 醚二醇。 200937472 如上所述之「聚酯多元醇」係包括：例如，根據慣用方 法將多元醇成份與多元羧酸、其酯、酐等之酯形成性衍生物 等之多元羧酸成份加以直接酯化反應或酯交換反應所獲得之 聚酯多元醇；以多元醇作爲引發劑而將內酯加以開環聚合所 獲得之聚酯多元醇等。 使用於製造聚酯多元醇之「多元醇成份」係可使用一般 在製造聚酯時所使用者，其係包括：例如，乙二醇、二甘醇 、三甘醇、丙二醇、1,3-丙二醇、2-甲基-1，3-丙二醇、2,2-二 〇 乙基-1，3-丙二醇、1，3-丁 二醇、1，4-丁 二醇、2-甲基-1,4-丁二 醇、新戊二醇、1,5-戊二醇、3-甲基-1，5-戊二醇、1，6-己二醇 、1，7-庚二醇、1，8-辛二醇、2-甲基-1，8-辛二醇、2,7-二甲基 -1，8-辛二醇、1，9-壬二醇、2-甲基-1,9-壬二醇、2,8-二甲基-1，9-壬二醇、1，10-癸二醇等之「碳數爲2至15之脂肪族二醇」； 1，4-環己二醇、環己烷二甲醇、環辛烷二甲醇、二甲基環辛烷 二甲醇等之「脂環式二醇」；1,4-雙（Θ-羥基乙氧基）苯等 之「芳香族二元醇等之每一分子具有2個羥基之二醇」；三 〇 羥甲基丙烷、三羥甲基乙烷、甘油、1，2,6-己三醇、新戊四醇 、二甘油等之「每一分子具有3個以上羥基之多元醇」等。 在製造聚酯多元醇時，此等之多元醇係可單獨使用或兩種以 上併用。在此等之中，由於可製成爲非膠黏性，且具有優越 的熔融成型性（melt-mold ability)、以拉伸應力或撕裂強度 (tear strength)所代表之優越的力學特性、及優越的耐熱性 之熱塑性聚胺基甲酸酯，因此較佳爲使用1，4_ 丁二醇、3·甲基 -1，5-戊二醇、1，6-己二醇、1，8-辛二醇等之碳數爲4至10之 脂肪族二醇，更佳爲使用1，4-丁二醇、1，6-己二醇、1，8-辛二 -10- 200937472 醇等之碳數爲4至10之直鏈狀脂肪族二醇。 使用於製造聚酯多元醇之「多元羧酸成份」係可使用一 般在製造聚酯時所使用者，其係包括：例如，琥珀酸（丁二 酸）、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、泌脂酸 (癸二酸）、十二烷二酸、甲基琥珀酸、2-甲基戊二酸、3-甲基戊二酸、三甲基己二酸、2-甲基辛烷二甲酸、3,8-二甲基 癸烷二酸、3,7-二甲基癸烷二甲酸等之「碳數爲4至12之脂 肪族二羧酸」；環己烷二甲酸、二聚酸、氫化二聚酸等之「 0 脂環式二羧酸」：對苯二甲酸、間苯二甲酸、鄰苯二甲酸、 萘二甲酸等之「芳香族二羧酸」；偏苯三酸（1，2,4-苯三甲酸 )、焦蜜石酸（1，2,4,5-苯四甲酸）等之「三官能以上之多元 羧酸」；或此等之酯形成性衍生物等。此等之多元羧酸成份 係可單獨使用或兩種以上倂用。其中，由於可製成爲非膠黏 性，且具有優越的熔融成型性、以拉伸應力或撕裂強度所代 表之優越的力學特性、及優越的耐熱性之熱塑性聚胺基甲酸 酯，因此較佳爲碳數爲6至12之脂肪族二羧酸，更佳爲己二 〇 酸、壬二酸、泌脂酸（癸二酸），特佳爲己二酸。 此外，使用於製造聚酯多元醇之「內酯」係包括：ε-己 內酯、/5-甲基- (5-戊內酯等。 如上所述之「聚醚多元醇」係包括：例如，在多元醇之 存在下，將環狀醚加以開環聚合所獲得之聚乙二醇、聚丙二 醇、聚四亞甲基二醇、聚（甲基四亞甲基二醇）等，且可使 用此等中之一種或兩種以上。其中，由於可製成爲非膠黏性 ，且具有優越的熔融成型性、以拉伸應力或撕裂強度所代表 之優越的力學特性、及優越的耐熱性之熱塑性聚胺基甲酸酯 -11 - 200937472 ，因此適合使用聚四亞甲基二醇和/或聚（甲基四亞甲基二醇 )° 如上所述之「聚碳酸酯多元醇」係可列舉：例如，將多 元醇成份與碳酸二烷基酯、碳酸伸烷基酯、碳酸二芳基酯等 之碳酸酯化合物進行反應所獲得者。使用於製造聚碳酸酯多 元醇之多元醇成份係可使用前文例示作爲可使用於製造聚酯 多元醇之成份的多元醇成份。此外，「碳酸二烷基酯」係可 列舉：碳酸二甲酯、碳酸二乙酯等；「碳酸伸烷基酯」係可 〇 列舉：碳酸伸乙酯等；「碳酸二芳基酯」係包括：碳酸二苯 酯等。 如上所述之「聚酯-聚碳酸酯多元醇」係可列舉：例如， 將多元醇成份、多元羧酸成份及碳酸酯化合物同時進行反應 所獲得者，或預先分別合成如上所述之聚酯多元醇及聚碳酸 酯多元醇，接著使此等與碳酸酯化合物進行反應，或與多元 醇成份及多元羧酸成份進行反應所獲得者等。 如上所述之「高分子多元醇」的具體實例係可列舉：例 〇 如，聚（己二酸1，4-四亞甲酯）二醇、聚（己二酸3-甲基-1，5- 五亞甲酯）二醇、聚（ε-己內酯）二醇、聚四亞甲基二醇等 〇 高分子多元醇之數量平均分子量較佳爲在500至8,000 之範圍內，更佳爲在600至5，000之範圍內，特佳爲在800 至3，000之範圍內。藉由使用具有該範圍之數量平均分子量 的高分子多元醇，則可獲得爲非膠黏性，且具有優越的熔融 成型性、以拉伸應力或撕裂強度所代表之優越的力學特性、 及優越的耐熱性之熱塑性聚胺基甲酸酯。此外’在本說明書 -12- 200937472 中之高分子多元醇之數量平均分子量係根據JIS Κ 1557之 準則測定之經基値（hydroxyl value)所計算得之數量平均 分子量。 可在本發明使用之有機聚異氰酸酯係可使用傳統慣用於 製造聚胺基甲酸酯之任一有機聚異氰酸酯。此等「有機聚異 氰酸酯」的實例係可列舉：例如，4,4 二苯甲烷二異氰酸酯 、伸甲苯基二異氰酸酯、伸苯基二異氰酸酯、伸茬基二異氰 酸酯、1，5-伸萘基二異氰酸酯、3,3’-二氯-4,4’-二苯甲烷二異 〇 氰酸酯等之「芳香族二異氰酸酯」；六亞甲基二異氰酸酯、 異佛酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、氫化伸 茬基二異氰酸酯等之「脂肪族或環式二異氰酸酯」等。此 等之有機聚異氰酸酯係可單獨使用一種或其兩種以上倂用。 其中，由於可製成爲非膠黏性，且具有優越的熔融成型性、 以拉伸應力或撕裂強度所代表之優越的力學特性、及優越的 耐熱性之熱塑性聚胺基甲酸酯，因此較佳爲主要由4,4’-二苯 甲烷二異氰酸酯所組成（較佳爲含有5 0莫耳％以上，尤佳爲 ❹ 80莫耳％以上，更佳爲95莫耳％以上，特佳爲1〇〇莫耳％) 〇 在本發明使用之鏈段增長劑係可使用傳統慣用於製造聚 胺基甲酸酯之任一鏈段增長劑。此等「鏈段增長劑」的實例 係可列舉：乙二醇、丙二醇、1，4-丁二醇、1，6-己二醇、1，4-雙羥基乙氧基）苯、1,4-環己二醇、對苯二甲酸雙（冷_ 羥基乙基）酯、伸茬基二醇等之「二醇類」；肼（聯胺：hydrazine )、伸乙基二胺、伸丙基二胺、伸茬基二胺、異佛酮二胺、 峨畊或其之衍生物、伸苯基二胺、伸甲苯基二胺、二甲苯二 -13- 200937472 胺、己二酸二醯肼、間苯二甲酸二醯肼等之「二胺類」：胺 基乙基醇、胺基丙基醇等之「胺基醇類」等。此等鏈段增長 劑係可單獨使用一種或其兩種以上倂用。在此等之中，由於 可製成爲非膠黏性，且具有優越的熔融成型性、以拉伸應力 或撕裂強度所代表之優越的力學特性、及優越的耐熱性之熱 塑性聚胺基甲酸酯，因此鏈段增長劑較佳爲主要由碳數爲2 至1 〇之脂肪族二醇所組成（較佳爲含有50莫耳％以上，尤佳 爲80莫耳％以上，更佳爲95莫耳％以上，特佳爲100莫耳％ 〇 );且更佳爲主要由1,4-丁二醇所組成（較佳爲含有50莫耳 %以上’尤佳爲80莫耳％以上，更佳爲95莫耳％以上，特佳 爲100莫耳❶/❶）。 將如前所述之高分子多元醇、有機聚異氰酸酯及鏈段增 長劑進行反應以製造熱塑性聚胺基甲酸酯時，各成份之混合 比率係應在考慮欲賦予作爲目的之熱塑性聚胺基甲酸酯的硬 度、力學性能等而適當地決定，但是較佳爲以能使存在於反 應系統中的活性氫原子：異氰酸酯基之莫耳比爲在1: 0.9至 © 1·1之範圍內的比率使用各成份，更佳爲以能成爲1 : 0.95至 1.05的比率使用各成份。藉由以如上所述之比率使用各成份 ，則可獲得爲非膠黏性，且具有優越的熔融成型性、以拉伸 應力或撕裂強度所代表之優越的力學特性、及優越的耐熱性 之熱塑性聚胺基甲酸酯。 熱塑性聚胺基甲酸酯之製造方法係並無特殊的限制，可 使用高分子多元醇、有機聚異氰酸酯及鏈段增長劑，並且採 用任何一種習知的胺基甲酸酯化反應技術來進行，可採用預 聚合物法（prepolymer process)或一步法（one-shot process -14- 200937472 )中之任一者。在此等之中，較佳爲在實質地並無溶劑存在 下加以熔融聚合，特別是更佳爲採用使用多軸螺桿型擠壓機 之連續式熔融聚合法。熔融聚合時之聚合溫度較佳爲在180 至280°C之範圍內。 將如上所述之高分子多元醇、有機聚異氰酸酯及鏈段增 長劑加以反應以獲得熱塑性聚胺基甲酸酯時，可使用胺基甲 酸酯化反應觸媒。該胺基甲酸酯化反應觸媒之種類，並無特 殊的限制，可使用傳統慣用於製造熱塑性聚胺基甲酸酯的胺 φ 基甲酸酯化反應觸媒中之任一者。此等之「胺基甲酸酯化反 應觸媒」的實例係包括：選自有機錫系化合物、有機鋅系化 今物、有機鉍系化合物、有機鈦系化合物、有機锆系化合物 、胺系化合物中之至少一種化合物等。胺基甲酸酯化反應觸 媒係可單獨使用一種或其兩種以上倂用。 在如上所述之熱塑性聚胺基甲酸酯中源於異氰酸酯基之 氮原子的含率較佳爲4.5質量％以上。具有該範圍之源於異氰 酸酯基之氮原子的含率之熱塑性聚胺基甲酸酯係可製成爲非 〇 膠黏性，且具有優越的熔融成型性、以拉伸應力或撕裂強度 所代表之優越的力學特性、及優越的耐熱性者。在熱塑性聚 胺基甲酸酯中源於異氰酸酯基之氮原子的含率較佳爲4.5至 6.5質量％，更佳爲4.6至6.0質量％，特佳爲4.7至5.7質量 %，最佳爲4.8至5.5質量％。 如上所述之熱塑性聚胺基甲酸酯的固有黏度（對數黏度 :inherent viscosity)，以在30°C下測定將該熱塑性聚胺基 甲酸酯溶解於N，N-二甲基甲醯胺（DMF)成濃度爲0.5 g/dl 之溶液所獲得之値計，則較佳爲0.7至1.5 dl/g，更佳爲0.8 -15- 200937472 至1.4 dl/g，特佳爲0.9至1.3 dl/g。含有該範圍的固有黏度 之熱塑性聚胺基甲酸酯薄膜係可製成爲非膠黏性，且具有優 越的熔融成型性、以拉伸應力或撕裂強度所代表之優越的力 學特性、及優越的耐熱性者。此外，在本說明書中之熱塑性 聚胺基甲酸酯的固有黏度（7? i„h )係意謂根據下列實施例所 揭述之方法測定之値。 如上所述之熱塑性聚胺基甲酸酯之ASTM D硬度較佳爲 52以上，更佳爲55以上，特佳爲58以上。具有該範圍的ASTM 0 D硬度之熱塑性聚胺基甲酸酯係可製成爲非膠黏性，且具有 優越的熔融成型性、以拉伸應力或撕裂強度所代表之優越的 力學特性、及優越的耐熱性者。此外，在本說明書中之熱塑 性聚胺基甲酸酯之ASTM D硬度係根據ASTM D2240之準則 所測定之値。 本發明之鍵盤用之薄膜係由如上所述之熱塑性聚胺基甲 酸酯單獨構成、或由主要由該熱塑性聚胺基甲酸酯所組成之 熱塑性聚胺基甲酸酯組成物所構成。在熱塑性聚胺基甲酸酯 〇 組成物中之該熱塑性聚胺基甲酸酯的含率較佳爲5 0質量％以 上，更佳爲8 0質量％以上，特佳爲9 5質量％以上。 在如上所述之熱塑性聚胺基甲酸酯組成物中，在不至於 損及本發明之功效範圍内，視需要可含有脫模劑、補強劑、 著色劑、難燃劑、紫外線吸收劑、抗氧化劑、耐候性改良劑 、耐光性改良劑、提高耐水解性劑、防霉劑、抗菌劑、穩定 劑、胺基甲酸酯化反應觸媒去活化劑等之各種添加劑；玻璃 纖維、聚酯纖維等之各種纖維；滑石、二氧化矽等之無機物 ;各種偶合劑；除了該熱塑性聚胺基甲酸酯以外之其他樹脂 -16- 200937472 等之任意成份。在熱塑性聚胺基甲酸酯組成物中之此等任意 成份的含率較佳爲50質量％以下，更佳爲20質量％以下，特 佳爲5質量％以下。 本發明之鍵盤用之薄膜的拉伸應力係必須爲18 MPa以上。藉由使用鍵盤用之薄膜爲具有如上所述範圍的拉 伸應力（M1G())，則可製成爲經加熱處理也不至於發生翹曲 或收縮等之不良現象、或薄膜彼此之膠著等，並且，可提供 即使不使用補強材也可保持形狀之鍵盤或鍵控片。鍵盤用之 0 薄膜的拉伸應力（M! 〇〇)較佳爲18至30 MPa，更佳爲18至 2 5 MPa。此外，在本說明書中所謂的「拉伸應力（Mi〇〇)」 係根據JIS K 73 1 1 - 1 995之準則所測定之値。 藉由使用具有特定的拉伸應力之如上所述熱塑 性聚胺基甲酸酯作爲用於構成鍵盤用之薄膜，則可容易地使 得本發明之鍵盤用之薄膜的拉伸應力控制在如上所 述範圍。亦即，若在由該熱塑性聚胺基甲酸酯單獨構成本發 明之鍵盤用之薄膜的情況時，則使用具有與欲賦予鍵盤用之 Ο 薄膜的拉伸應力（Μ1ϋ())相同的拉伸應力（Μμο)之熱塑性聚 胺基甲酸酯即可。該熱塑性聚胺基甲酸酯，只要其爲如上所 述藉由高分子多元醇、有機聚異氰酸酯及鏈段增長劑進行反 應所獲得者，且其之拉伸應力（M1Q())爲在該範圍者時，則 並無特殊的限制，但是爲使熱塑性聚胺基甲酸酯，甚至爲使 所製得之鍵盤用之薄膜的拉伸應力（M1Q())更確實地符合該 範圍，則可使用之熱塑性聚胺基甲酸酯的具體實例係包括： (i) 將聚（己二酸1，4-四亞甲酯）二醇、4,4’-二苯甲烷二 異氰酸酯及1,4-丁二醇進行反應所獲得之源於異氰酸 -17- 200937472 酯基之氮原子的含率爲4.8質量％以上之熱塑性聚胺基 甲酸酯； (ii) 將聚（己二酸3-甲基-1，5-五亞甲酯）二醇、4,4’-二苯 甲烷二異氰酸酯及1，4-丁二醇進行反應所獲得之源於 異氰酸酯基之氮原子的含率爲4.7質量％以上之熱塑性 聚胺基甲酸酯； (iii) 將聚（ε-己內酯）二醇、4，4’-二苯甲烷二異氰酸酯 及1，4-丁二醇進行反應所獲得之源於異氰酸酯基之氮 0 原子的含率爲4.9質量％以上之熱塑性聚胺基甲酸酯； 以及 (iv) 選自由將聚四亞甲基二醇、4,4’·二苯甲烷二-氰酸酯 及1,4-丁二醇進行反應所獲得之源於異氰酸酯基之氮 原子的含率爲5.1質量％以上之熱塑性聚胺基甲酸酯所 組成的族群中之至少一種熱塑性聚胺基甲酸酯等。 此外，若在由如上所述之熱塑性聚胺基甲酸酯組成物構 成本發明之鍵盤用之薄膜的情況時，則藉由在考慮及如上所 © 述任意成份之種類或混合量下使用具有特定的拉伸應力（ Μ ! 〇〇 )之熱塑性聚胺基甲酸酯，則可容易地控制鍵盤用之薄 膜的拉伸應力（M1Q。）在該範圍。 本發明之鍵盤用之薄膜之製造方法，並無特殊的限制， 可使用藉由高分子多元醇、有機聚異氰酸酯及鏈段增長劑進 行反應所獲得之熱塑性聚胺基甲酸酯，並採用習知的薄膜化 製造技術中之任一者，例如可採用擠壓成型、射出成型、吹 塑薄膜成型、壓延成型或加壓成型等之任一者。在此等之中 ，較佳爲採用擠壓成型或吹塑薄膜成型，特別是更佳爲採用 -18- 200937472 使用單軸螺桿型擠壓機之擠壓成型或吹塑薄膜成型。在此情 形下，單軸螺桿型擠壓機之機筒溫度較佳爲在180至23〇°C之 範圍內。 本發明之鍵盤用之薄膜的厚度係並無特殊的限制，可根 據在熱塑性聚胺基甲酸酯中源於異氰酸酯基之氮原子的含率 或該熱塑性聚胺基甲酸酯之硬度、或所製得之鍵盤用之薄膜 的拉伸應力（等之値來加以調整，但是從薄膜之製造 容易性、耐熱性、後加工之製程通過性等的觀點來考慮，則 Q 較佳爲20至300/zm，更佳爲30至200/zm，特佳爲40至150 (1 m。 本發明之鍵盤用之薄膜，雖然可直接使用以製成由該鍵 Λ 盤用之薄膜所構成之單獨層所構成的鍵盤，但是也可藉由本 發明之鍵盤用之薄膜與其他層積層所獲得之積層物來構成鍵 盤。用於構成該其他層之原材料係包括：聚酯、聚醯胺、聚 碳酸酯、聚矽氧、熱塑性聚胺基甲酸酯、熱硬化性聚胺基甲 酸酯、聚烯烴等之樹脂；金屬；紙；綿布等。此外，該鍵盤 Ο 可具有將由塗料、印墨所構成的層、或由黏著劑、底漆（primer )所構成的層等作爲如上所述之其他層。 在形成如上所述之由塗料、印墨所構成的層、或由黏著 劑或底漆所構成的層等時，則較佳爲實施加熱處理。該加熱 處理之溫度係可例示例如40至120°C。此外，加熱處理之時 間係可例示例如1 〇秒鐘至3小時。 對於本發明之鍵盤用之薄膜的單獨層、或藉由本發明之 鍵盤用之薄膜與其他層積層所獲得之積層物，視需要以裁切 、沖裁、切削等加工成所要之尺寸、形狀，藉此則可用於 -19- 200937472 製造鍵盤。此外，對於鍵盤也可以硏磨或雷射等形成吾所欲 之溝或穴等。其他，在鍵盤也可設置：用於配設鍵頂之凹凸 :用於配設按壓用設置於鍵控片下面之鍵開關（key switch) 的壓子之凹凸；用於配設讓鍵盤本身擁有鍵頂或壓子等功能 之凹凸等之各種凹凸。此等之凹凸係經對於本發明之鍵盤用 之薄膜的單獨層、或藉由本發明之鍵盤用之薄膜與其他層積 層所獲得之積層物實施壓縮成型（加壓成型）、真空成型等 即可形成。 φ 藉由在如上所述鍵盤之特定的位置配設按鈕鍵等之鍵頂 等，則可製成爲具有該鍵盤及鍵頂之鍵控片。此外，在鍵控 片除了該鍵頂以外，，也可具有壓子等。對於鍵盤配設鍵頂或 壓子等係可使用化學反應型黏著劑（以氰基丙烯酸酯爲成份 之黏著劑等）或UV (紫外線）黏著劑等之黏著劑來實施。 藉由使用本發明之鍵盤用之薄膜所獲得之鍵盤或鍵控片 係適合用作爲可攜式電話等之通信終端、各種計量儀器、個 人電腦輸入用之鍵盤、構成遙控器等之操作部構件。 © 《實施例》 在下文中，則就本發明以實施例更具體地加以說明，但 是本發明並不受限於此等實施例。此外，在實施例及比較例 中之熱塑性聚胺基甲酸酯的熔融黏度、固有黏度及ASTMD 硬度、以及鍵盤用之薄膜的拉伸應力（M1QQ )及耐熱性係以 下列方法測定或評估。 〈熱塑性聚胺基甲酸酯之熔融黏度〉 使用高化型流動度試驗儀（Koka-type flow tester)(島 津製作所股份有限公司（Shimadzu Corporation)製造），將 -20- 200937472 經在80°C下加以減壓乾燥（10 ton·以下）2小時所獲得之熱 塑性聚胺基甲酸酯的熔融黏度係在荷重爲490.3 N( 50 kgf) 、嘴尺寸=直徑1毫米x長度10毫米、溫度200°C之條件下進 行測定。 〈熱塑性聚胺基甲酸酯之固有黏度〉 對於每1克之藉由如下所述之實施例或比較例所獲得之 鍵盤用之薄膜加入200毫升之N，N-二甲基甲醯胺（DMF )， 在室溫下攪拌24小時後加以過濾分離以回收DMF溶液。若 Q 產生不溶物時，則對於該不溶物再加入200毫升之DMF並重 覆進行三次的攪拌1小時後加以過濾分離之操作。將回收之 濾轉合倂在一起，從濾液餾出DMF後，在室溫下加以真空乾 燥24小時，然後測定所獲得聚胺基甲酸酯成份之質量，以確 認包含在鍵盤用之薄膜中之熱塑性聚胺基甲酸酯之約1 00%已 被萃取。此外，若萃取率爲不超過約100%時，則判斷其爲未 萃取部份係因熱塑性聚胺基甲酸酯之分子量非常高以致不溶 於DMF者而從固有黏度之測定對象排除。 © 將經萃取之熱塑性聚胺基甲酸酯再度溶解於DMF以使其 濃度成爲 〇.5 g/dl，然後使用烏伯樓德型黏度計（ Ubbelodhe-type viscometer )測定該熱塑性聚胺基甲酸酯之 DMF溶液在3 0°C之流下時間，並以下式計算得熱塑性聚胺基 甲酸酯的固有黏度（77inh)。 熱塑性聚胺基甲酸酯的固有黏度（7?inh) =〔 ln(t/t〇)〕/c 〔式中，t係代表熱塑性聚胺基甲酸酯之DMF溶液之流下時 間（秒鐘），U係代表溶劑（DMF )之流下時間（秒鐘），C 係代表熱塑性聚胺基甲酸酯之DMF溶液之濃度（g/dl )。〕 -21 - 200937472 〈熱塑性聚胺基甲酸酯之ASTMD硬度〉 使用經將表面加以拋光成鏡面之模具，將如下所述之實 施例或比較例所製造之熱塑性聚胺基甲酸酯加以射出成型（ 機筒溫度爲185至210°c、模具溫度爲30°C )以製造圓板狀 之成型品（直徑爲120毫米、厚度爲2毫米），然後使用經 將三片所獲得圓板狀之成型品疊合所獲得者，並根據ASTM D2240之準則測定成型品（熱塑性聚胺基甲酸酯）之ASTM D 硬度。 〇 〈鍵盤用之薄膜之拉伸應力〉 由藉由如下所述之實施例或比較例所獲得之鍵盤用之薄 膜製造在JISK 7311-1 995準則所規定之啞鈴狀試驗片（中央 部之寬度爲 5 毫米）。使用 INSTRON Japan Company Limited 製造之「INSTRON 5 5 66」，在溫度23°C及拉伸速度爲3 00毫 米/分鐘之條件下測定該啞鈴狀試驗片在伸長100%時的拉伸 應力，並將其作爲鍵盤用之薄膜的拉伸應力（M1GQ)。 〈鍵盤用之薄膜之耐熱性〉 © 將藉由如下所述之實施例或比較例所獲得之鍵盤用之薄 膜製造50片試驗片（縱100毫米X橫100毫米）。對於此等 50片之試驗片的各片，在中央部將網印油墨（screen ink)( 日本帝國油墨製造股份有限公司（Teikoku Printing Inks Mfg. Co.，Ltd.)製造之「IPX Screen Ink」）塗佈成縱50毫米χ橫 50毫米之正方形狀，然後在90°C之熱風乾燥機中放置1小時 。觀察熱風乾燥處理後之試驗片的狀態，而以如下所述之判 定基準評估試驗片之耐熱性，並將其作爲鍵盤用之薄膜的耐 熱性。 -22- 200937472 (耐熱性之評估基準） 3: 在試驗片之總數量（50片），網印油墨塗佈部並 未發生任何翹曲或收縮，且維持平滑性： 2: 在網印油墨塗佈部並未發生翹曲或收縮，且維持 平滑性之試驗片的片數爲46至49片（在1至4 片之試驗片可觀測到在網印油墨塗佈部之翹曲或 收縮）； 1: 在網印油墨塗佈部並未發生翹曲或收縮，且維持 〇 平滑性之試驗片的片數爲45片以下（在5片以上 之試驗片可觀測到在網印油墨塗佈部之翹曲或收 縮）。 在實施例及比較例所使用之各成份的代表符號係如下所 示： (高分子多元醇）[Technical Field] The present invention relates to a keyboard for an operation unit used for a communication terminal such as a portable telephone, various instruments, a keyboard for inputting a personal computer, a remote controller, and the like ( Keypad) film. [Prior Art] In recent years, a keyboard obtained by using a film made of a film made of a resin such as a thermoplastic polyurethane, a polyethylene terephthalate or a polyester elastomer, has been obtained. A key sheet manufactured by sticking, printing, or printing a key top (button key) has been widely used in communication terminals such as portable telephones, and various types. The operation unit of a measuring instrument, a keyboard for inputting a personal computer, a remote controller, and the like, and some techniques relating to such a keying sheet are well known (see, for example, Patent Documents 1 and 2). Further, in the raw material of the film for the keyboard for constituting the keyboard, the thermoplastic polyurethane is particularly suitable for use because of moderate softness, superior cushioning, and high durability. And some techniques for the use of such thermoplastic polyester urethane as a raw material for a keyboard have been known. For example, it has been proposed to form a thermoplastic polyurethane resin obtained by using at least an isocyanate selected from hexamethylene diisocyanate or hydrogenated diphenylmethane diisocyanate and a polyol as a synthetic component. It is laminated on a surface material for a keyboard which is required for a keyboard, and is made of a polyamine group which has a superior soft touch, does not cause yellowing, and has high water resistance, heat resistance, and low physical properties. A method of producing a surface material of a formic acid ester (see Patent Document 3 of the invention). 200937472 In addition, an organic diisocyanate containing hexamethylene diisocyanate as a main component, a polymer polyol mainly composed of a polycarbonate diol, and an aliphatic dimer having a carbon number of 2 to 10 are known. a resin granule obtained by reacting a chain extender containing an alcohol as a main component, and a polyamino carboxylic acid obtained by thermoforming a thermoplastic urethane resin sheet obtained by melt molding The keyboard system manufactured by the ester resin can exhibit superior secondary moldability, oil resistance, discoloration resistance, transparency, and printability (see Patent Document 4; however, the thermoplastic material disclosed in Patent Document 4 is specifically disclosed. The tensile stress (M1()Q) of the film composed of the polyurethane at 100% elongation at 23 ° C is even higher (the polyurethane of Synthesis Example 3) is only About 8 MPa). However, when a keyboard or a key sheet is manufactured using a film for a keyboard, most of the adhesive or printing ink is applied and cured or fixed, or a laminated layer composed of other resins is required to be heated. deal with. However, since the film for the keyboard made of the prior thermoplastic polyurethane has a small tensile stress, especially when applied to cure or fix the adhesive or the printing ink, or with other In the heat treatment of the laminated layer composed of the resin, problems such as warping or shrinkage of the film having insufficient heat resistance, or adhesion of the films to each other are likely to occur. When the warpage or shrinkage of the film occurs and the films are glued to each other, the keyed sheet obtained is disposed at a predetermined position of the final product of the portable telephone or the like, but is manually After flattening, it can be embedded or require special equipment or the like to reduce the productivity of the final product, or the problem of lowering the yield due to the inability to use the defective product as a key sheet or a keyboard. Therefore, the thermoplastic polyurethane has a moderate softness or superior cushioning property and high durability as described above. However, when it is currently used as a raw material for a keyboard, its use range is still limited. 'There is a need to solve the problem as described above. In particular, in recent years, in terms of portable telephones, in order to further advance the design thinning, the key sheet or the keyboard has a tendency to be thinner, and therefore there is a strong need to solve the above problems. Further, a film for a keyboard composed of a film made of a resin such as a thermoplastic polyurethane has a small tensile stress and a softness as described above, and a proposal has been proposed to maintain it. The technique of laminating a frame sheet for the purpose of the shape of the keying sheet. For example, a resin film substrate (keyboard) having a prayer made of a relatively soft thermoplastic polyurethane (a tensile stress (Mbo) at 100% elongation at 23 ° C) of about 7 MPa has been proposed. The technique of laminating the frame sheet for the purpose of fixing and reinforcing the key top (button button) in the key top of the substrate and the key sheet having the specific printing adhesive layer (see Patent Document 5). However, when the laminated frame is laminated, it is difficult to achieve weight reduction or reduction of the portable electronic product of the final product, and the process tends to be cumbersome. (Patent Document 1) Japanese Laid-Open Patent Publication No. 2004-327307 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2004-119 4) International Publication No. 2004/106401 (Invention Patent Document 5) Japanese Laid-Open Patent Publication No. 2007-668 No. 18 No. 200937472 [Draft of the Invention] [Technical Problem to be Solved] The present invention has been made to solve the above problems. To provide a superior non-tackiness, handling capability, heat resistance and dimensional accuracy stability, especially even due to curing or fixing adhesives or printing inks. A film for a keyboard which does not cause a problem such as warpage or shrinkage or a problem in which the films are stuck to each other is a technical problem as long as the heat treatment is performed. Further, there is provided a keyboard or keyed sheet which can be used for manufacturing a lightweight or reduced final product capable of achieving a portable telephone or the like even without using a reinforcing member such as a frame sheet, and which can also simplify the process. The film used in the keyboard is a technical problem. Further, the present invention is a technical problem of providing a keyboard including at least a layer composed of a film for the keyboard, and a key sheet having at least the keyboard and the key top. [Technical method for solving the problem] In order to solve the technical problems as described above, the inventors of the present invention have repeatedly reviewed various results and found that when a film for a keyboard is formed from a thermoplastic polyurethane, The tensile stress (00) of the film at 100% elongation at 23 t [hereinafter, sometimes, the "tensile stress at 300% elongation at 23 t (Miqq)" is simply referred to as "tensile stress". (Μι〇.)". The setting is set to a specific range, whereby not only the warpage of the film during the heat treatment or after the treatment can be improved, but also the passability of the processing in the subsequent step tends to be good, and the production yield can be improved. In addition, the inventors of the present invention have also found that as long as the film for the keyboard as described above is used, when the keyboard or the keying piece 200937472 is manufactured, the reinforcing material is no longer needed, and even the final product of the portable telephone or the like can be achieved. Lighter or smaller, it also simplifies the process. Further, the present invention has been finally achieved by repeating the review results based on these viewpoints. That is, the present invention relates to: (a) a film for a keyboard, which is composed of a thermoplastic polyol obtained by reacting a polymer polyol, an organic polyisocyanate, and a segment extender, or It is mainly composed of a thermoplastic polyurethane composition composed of the thermoplastic polyurethane, and has a tensile stress (M! 〇〇) of 18 MPa or more when the elongation at 100 ° C is 100%; (2) The film for a keyboard according to Item (1), wherein a content of the nitrogen atom derived from the isocyanate group in the thermoplastic polyamidyl ester is 4. 5. (3) The film for a keyboard according to the item (1) or (2), wherein the organic polyisocyanate is mainly composed of 4,4'-diphenylmethane diisocyanate; The film for a keyboard according to any one of (1) to (3), wherein the segment growth agent is mainly composed of 1,4-butanediol; (5) as in (1) to The film for a keyboard according to any one of the preceding claims, wherein the polymer polyol has a number average molecular weight of from 500 to 8,000; (6) as described in any one of items (1) to (5) A film for a keyboard having a thickness of 20 to 300 ym; (7) a keyboard comprising at least the film for a keyboard according to any one of (1) to (6) (8) A keying sheet having at least a keyboard and a key top as described in item (7). 200937472 [Effects of the Invention] According to the present invention, stability with superior non-adhesiveness, usability, heat resistance and dimensional accuracy can be obtained, particularly even due to curing or fixing of adhesives or printing marks. When the heat treatment is performed in the case of ink or the like, a film for a keyboard which does not cause a problem such as warpage or shrinkage or a problem in which the films are stuck to each other can be obtained. According to the film for a keyboard of the present invention, it is possible to maintain the shape even without using a reinforcing member such as a frame sheet, and it is possible to achieve weight reduction or reduction of the final product such as a portable telephone, and to simplify the φ process. Keyboard or keying piece. [Embodiment] > Hereinafter, the present invention will be described in detail. The film for the keyboard of the present invention is composed of a thermoplastic polyurethane obtained by reacting a polymer polyol, an organic polyisocyanate and a segment extender, or is mainly composed of the thermoplastic polyurethane. The composition consists of a thermoplastic polyurethane composition. The polymer polyol used in the present invention may be any polymer polyol conventionally used for the production of polyurethanes. Examples of such "polymer polyols" include polyester polyols, polyether polyols, polycarbonate polyols, polyester-polycarbonate polyols, polyolefin polyols, and hydrogenation. The conjugated diene polymer is a polyol, a castor oil-based polyol, a vinyl polymer-based polyol, or the like. These polymer polyols may be used alone or in combination of two or more. Among them, the polymer polyol is preferably one or more selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols, preferably polyester polyols and/or polyether polyols, more preferably used. Polyester diol and/or polyether diol. 200937472 The "polyester polyol" as described above includes, for example, a direct esterification reaction of a polyhydric carboxylic acid component such as an ester-forming derivative of a polyhydric carboxylic acid, an ester thereof, or an anhydride, according to a conventional method. Or a polyester polyol obtained by a transesterification reaction; a polyester polyol obtained by subjecting a lactone to ring-opening polymerization using a polyhydric alcohol as an initiator. The "polyol component" used in the manufacture of the polyester polyol can be generally used in the manufacture of polyesters, including, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3- Propylene glycol, 2-methyl-1,3-propanediol, 2,2-diethylidene-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2-methyl-1 , 9-decanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-nonanediol, etc. "an aliphatic diol having 2 to 15 carbon atoms"; 1,4- "Cycloaliphatic diol" such as cyclohexanediol, cyclohexanedimethanol, cyclooctane dimethanol, dimethylcyclooctane dimethanol, etc.; 1,4-bis(anthracene-hydroxyethoxy)benzene "A diol having two hydroxyl groups per molecule such as an aromatic diol"; trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanetriol, neopentyl Alcohol, diglycerin, etc. "Each molecule has 3 The above polyol of a hydroxyl group" and the like. In the production of the polyester polyol, these polyols may be used singly or in combination of two or more. Among these, it can be made non-adhesive, and has excellent melt-mold ability, superior mechanical properties represented by tensile stress or tear strength, and Superior heat-resistant thermoplastic polyurethane, so it is preferred to use 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8- An aliphatic diol having 4 to 10 carbon atoms such as octanediol, more preferably 1,4-butanediol, 1,6-hexanediol, 1,8-octane-10--10-37,372472 alcohol or the like A linear aliphatic diol having a carbon number of 4 to 10. The "polycarboxylic acid component" used in the manufacture of the polyester polyol can be generally used in the manufacture of polyesters, including, for example, succinic acid (succinic acid), glutaric acid, adipic acid, and gly. Diacid, suberic acid, azelaic acid, lipoic acid (sebacic acid), dodecanedioic acid, methyl succinic acid, 2-methylglutaric acid, 3-methylglutaric acid, trimethyl "Adicarboxylic acid having 4 to 12 carbon atoms, such as adipic acid, 2-methyloctane dicarboxylic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane dicarboxylic acid, etc. "acid"; "0 alicyclic dicarboxylic acid" such as cyclohexanedicarboxylic acid, dimer acid, hydrogenated dimer acid, etc.: terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc. "Aromatic dicarboxylic acid"; "trimethylene or higher polycarboxylic acid" such as trimellitic acid (1,2,4-benzenetricarboxylic acid) or pyroghuric acid (1,2,4,5-benzenetetracarboxylic acid) Or such ester-forming derivatives and the like. These polycarboxylic acid components may be used singly or in combination of two or more. Among them, since it can be made into a non-adhesive property, and has excellent melt moldability, superior mechanical properties represented by tensile stress or tear strength, and superior heat resistance of thermoplastic polyurethane, It is preferably an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, more preferably adipiconic acid, sebacic acid or lipoic acid (sebacic acid), and particularly preferably adipic acid. Further, the "lactone" used in the production of the polyester polyol includes ε-caprolactone, /5-methyl-(5-valerolactone, etc. The "polyether polyol" as described above includes: For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(methyltetramethylene glycol), etc. obtained by ring-opening polymerization of a cyclic ether in the presence of a polyhydric alcohol, and the like One or more of these may be used, among which, it may be made non-adhesive, and has excellent melt moldability, superior mechanical properties represented by tensile stress or tear strength, and superiority. Heat-resistant thermoplastic polyurethane-11 - 200937472, therefore suitable for use of polytetramethylene glycol and / or poly (methyltetramethylene glycol) ° "polycarbonate polyol" as described above For example, a polyol component is obtained by reacting a polyol component with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate or a diaryl carbonate, and is used for producing a polycarbonate polyol. The ingredients can be used as examples to make polyester polyols The polyol component of the component. The "dialkyl carbonate" may, for example, be dimethyl carbonate or diethyl carbonate; and the "alkyl carbonate" may be exemplified by ethyl carbonate and the like; The "diaryl ester" includes diphenyl carbonate, etc. The "polyester-polycarbonate polyol" as described above may, for example, be a reaction of a polyol component, a polycarboxylic acid component, and a carbonate compound. The obtained ones are obtained by separately synthesizing the polyester polyol and the polycarbonate polyol as described above, and then reacting them with the carbonate compound or reacting with the polyol component and the polycarboxylic acid component. Specific examples of the "polymer polyol" as described above include, for example, poly(1,4-tetramethylene adipate) diol, poly(adipic acid 3-methyl-1). The number average molecular weight of the fluorene polymer polyol such as 5-5-methylene methoxide diol, poly(ε-caprolactone) diol or polytetramethylene glycol is preferably in the range of 500 to 8,000. More preferably in the range of 600 to 5,000, especially in the range of 800 to 3,0 Within the range of 00. By using a polymer polyol having a number average molecular weight in this range, it can be obtained as non-adhesive, and has excellent melt moldability and superiority represented by tensile stress or tear strength. Thermoplastic polyurethane having superior mechanical properties and superior heat resistance. Further, the number average molecular weight of the polymer polyol in the present specification -12-200937472 is based on the basis of JIS Κ 1557 ( Hydroxyl value) The number average molecular weight calculated. The organic polyisocyanate which can be used in the present invention can be any conventional organic polyisocyanate which is conventionally used for the production of polyurethanes. Examples of such "organic polyisocyanates" are For example, 4,4 diphenylmethane diisocyanate, tolyl diisocyanate, phenyl diisocyanate, decyl diisocyanate, 1,5-naphthyl diisocyanate, 3,3'-dichloro- "Aromatic diisocyanate" such as 4,4'-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl Diisocyanate, hydrogenated extending crop-yl diisocyanate, etc. 'or a cyclic aliphatic diisocyanate "and the like. These organic polyisocyanates may be used alone or in combination of two or more. Among them, since it can be made into a non-adhesive property, and has excellent melt moldability, superior mechanical properties represented by tensile stress or tear strength, and superior heat resistance of thermoplastic polyurethane, Preferably, it is mainly composed of 4,4'-diphenylmethane diisocyanate (preferably containing 50% by mole or more, particularly preferably ❹80% by mole or more, more preferably 95% by mole or more, particularly preferably It is a chain extender used in the present invention. Any of the segmental growth agents conventionally used for the manufacture of polyurethanes can be used. Examples of such "segment growth agents" include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-dihydroxyethoxy)benzene, and 1, "Glycols" such as 4-cyclohexanediol, bis(cold-hydroxyethyl)terephthalate, decyl diol, etc.; hydrazine (hydrazine), ethylenediamine, and propylene Diamine, decyldiamine, isophorone diamine, sorghum or its derivatives, phenylenediamine, tolyldiamine, xylene di-13- 200937472 amine, diammonium adipate "Diamines" such as hydrazine and diisophthalic acid: "amino alcohols" such as aminoethyl alcohol and aminopropyl alcohol. These segment growth agents may be used alone or in combination of two or more. Among these, thermoplastic polyurethanes which are non-adhesive and have excellent melt formability, superior mechanical properties represented by tensile stress or tear strength, and superior heat resistance The acid ester, therefore, the segment growth agent is preferably composed mainly of an aliphatic diol having a carbon number of 2 to 1 Torr (preferably containing 50 mol% or more, particularly preferably 80 mol% or more, more preferably 95% or more, particularly preferably 100% by mole; and more preferably composed mainly of 1,4-butanediol (preferably containing 50% by mole or more), particularly preferably 80% by mole or more More preferably 95% or more, especially 100% ❶/❶). When a polymer polyol, an organic polyisocyanate, and a segment extender as described above are reacted to produce a thermoplastic polyurethane, the mixing ratio of each component should be considered in consideration of the intended purpose of imparting a thermoplastic polyamine group. The hardness, mechanical properties and the like of the formate are appropriately determined, but it is preferably such that the molar ratio of the active hydrogen atom:isocyanate group present in the reaction system is 1:0. The ratio of 9 to ©1·1 is the ratio of each component, and more preferably it can be 1:0. 95 to 1. The ratio of 05 uses each component. By using the components in the ratios as described above, it is possible to obtain non-adhesive properties, and to have excellent melt moldability, superior mechanical properties represented by tensile stress or tear strength, and superior heat resistance. Thermoplastic polyurethane. The method for producing the thermoplastic polyurethane is not particularly limited, and a polymer polyol, an organic polyisocyanate, and a segment extender can be used, and any conventional urethanation reaction technique can be used. Any one of a prepolymer process or a one-shot process (14-200937472) may be employed. Among these, it is preferred to carry out melt polymerization in the substantial absence of a solvent, and more preferably to use a continuous melt polymerization method using a multiaxial screw type extruder. The polymerization temperature in the melt polymerization is preferably in the range of from 180 to 280 °C. When a polymer polyol, an organic polyisocyanate, and a segment extender as described above are reacted to obtain a thermoplastic polyurethane, a urethanization catalyst can be used. The kind of the urethanization catalyst is not particularly limited, and any of the amine phthalate reaction catalysts conventionally used for the production of thermoplastic polyurethanes can be used. Examples of such "urementation catalyst" include: an organotin compound, an organic zinc compound, an organic lanthanide compound, an organic titanium compound, an organic zirconium compound, and an amine system. At least one compound or the like of the compounds. The urethanation catalyst system may be used alone or in combination of two or more. The content of the nitrogen atom derived from the isocyanate group in the thermoplastic polyurethane as described above is preferably 4. 5 mass% or more. The thermoplastic polyurethane having the content of the nitrogen atom derived from the isocyanate group in this range can be made into a non-rubbery adhesive property and has excellent melt formability, represented by tensile stress or tear strength. Excellent mechanical properties and superior heat resistance. The content of the nitrogen atom derived from the isocyanate group in the thermoplastic polyurethane is preferably 4. 5 to 6. 5 mass%, more preferably 4. 6 to 6. 0% by mass, especially good 4. 7 to 5. 7% by mass, the best is 4. 8 to 5. 5 mass%. The intrinsic viscosity (inherent viscosity) of the thermoplastic polyurethane as described above, the thermoplastic polyurethane was dissolved in N,N-dimethylformamide at 30 ° C as measured (DMF) concentration is 0. The enthalpy obtained by the solution of 5 g/dl is preferably 0. 7 to 1. 5 dl / g, more preferably 0. 8 -15- 200937472 to 1. 4 dl / g, especially good 0. 9 to 1. 3 dl/g. The thermoplastic polyurethane film containing the intrinsic viscosity of this range can be made non-adhesive, and has excellent melt formability, superior mechanical properties represented by tensile stress or tear strength, and superiority. The heat resistance. Further, the intrinsic viscosity (7? i?h) of the thermoplastic polyurethane in the present specification means the measurement according to the method disclosed in the following examples. The thermoplastic polyurethane as described above The ASTM D hardness of the ester is preferably 52 or more, more preferably 55 or more, and particularly preferably 58 or more. The thermoplastic polyurethane having the ASTM 0 D hardness of this range can be made non-adhesive and has Excellent melt moldability, superior mechanical properties represented by tensile stress or tear strength, and superior heat resistance. In addition, the ASTM D hardness of the thermoplastic polyurethane in this specification is based on ASTM. The film for use in the keyboard of the present invention is composed of a thermoplastic polyurethane as described above, or a thermoplastic polyamine group mainly composed of the thermoplastic polyurethane. The content of the thermoplastic polyurethane in the thermoplastic polyurethane composition is preferably 50% by mass or more, more preferably 80% by mass or more. Particularly good is 9.5 mass% or more. The thermoplastic polyurethane composition described above may contain a release agent, a reinforcing agent, a coloring agent, a flame retardant, a UV absorber, and an anti-resistant agent as needed within the range of not impairing the efficacy of the present invention. Various additives such as an oxidizing agent, a weathering improver, a light resistance improver, a hydrolysis resistance improving agent, an antifungal agent, an antibacterial agent, a stabilizer, a urethanization catalyst deactivator, etc.; glass fiber, polyester Various fibers such as fibers; inorganic substances such as talc and cerium oxide; various coupling agents; and any other components other than the thermoplastic polyurethane--16-200937472, etc. Composition in thermoplastic polyurethane The content of the optional component is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 5% by mass or less. The tensile stress of the film for a keyboard of the present invention must be 18 MPa. In the above, the film for use with the keyboard is a tensile stress (M1G()) having the above range, and it can be made into a heat-treated process without causing warpage or shrinkage, or the glue of the films. And, a keyboard or a key sheet which can maintain a shape even without using a reinforcing material. The tensile stress (M! 〇〇) of the film for the keyboard is preferably 18 to 30 MPa, more preferably 18 to Further, the "tensile stress (Mi〇〇)" referred to in the present specification is a ruthenium measured according to the criteria of JIS K 73 1 1 - 1 995. By using a thermoplastic polyurethane having a specific tensile stress as described above as a film for constituting a keyboard, the tensile stress of the film for a keyboard of the present invention can be easily controlled as described above. range. That is, in the case where the film for a keyboard of the present invention is separately composed of the thermoplastic polyurethane, the same tensile stress (Μ1ϋ()) as that of the film to be imparted to the keyboard is used. A thermoplastic polyurethane having a tensile stress (Μμο) can be used. The thermoplastic polyurethane is obtained as long as it is reacted by a polymer polyol, an organic polyisocyanate, and a segment extender as described above, and the tensile stress (M1Q()) thereof is In the range, there is no particular limitation, but in order to make the thermoplastic polyurethane even more positively conform to the tensile stress (M1Q()) of the film for the keyboard produced, Specific examples of thermoplastic polyurethanes that can be used include: (i) poly(1,4-tetramethylene adipate) diol, 4,4'-diphenylmethane diisocyanate, and 1, The content of the nitrogen atom derived from the isocyanate-17-200937472 ester group obtained by the reaction of 4-butanediol is 4. 8% by mass or more of thermoplastic polyurethane; (ii) poly(3-methyl-1,5-pentamethylene adipate) diol, 4,4'-diphenylmethane diisocyanate and The content of the nitrogen atom derived from the isocyanate group obtained by the reaction of 1,4-butanediol is 4. 7% by mass or more of thermoplastic polyurethane; (iii) obtained by reacting poly(ε-caprolactone) diol, 4,4'-diphenylmethane diisocyanate and 1,4-butanediol The content of the nitrogen atom derived from the isocyanate group is 4. 9 mass% or more of thermoplastic polyurethane; and (iv) optional polytetramethylene glycol, 4,4'-diphenylmethane di-cyanate and 1,4-butanediol The content of the nitrogen atom derived from the isocyanate group obtained by the reaction is 5. At least one thermoplastic polyurethane or the like of the group consisting of 1% by mass or more of the thermoplastic polyurethane. Further, in the case where the thermoplastic polyurethane urethane composition as described above is used as the film for the keyboard of the present invention, it is used by considering the kind or mixing amount of any component as described above. The tensile stress (M1Q.) of the film for the keyboard can be easily controlled by the specific tensile stress (??) of the thermoplastic polyurethane. The method for producing the film for a keyboard of the present invention is not particularly limited, and a thermoplastic polyurethane obtained by reacting a polymer polyol, an organic polyisocyanate, and a segment growth agent can be used, and Any of the known thin film formation techniques may be, for example, extrusion molding, injection molding, blown film molding, calender molding, or press molding. Among these, extrusion molding or blown film molding is preferred, and particularly, extrusion molding or blown film molding using a uniaxial screw type extruder of -18-200937472 is preferred. In this case, the barrel temperature of the single-shaft screw type extruder is preferably in the range of 180 to 23 °C. The thickness of the film for the keyboard of the present invention is not particularly limited, and may be based on the content of the nitrogen atom derived from the isocyanate group in the thermoplastic polyurethane or the hardness of the thermoplastic polyurethane, or The tensile stress of the film for the keyboard to be obtained is adjusted, and the Q is preferably 20 to 20 from the viewpoints of ease of production of the film, heat resistance, process passability of post-processing, and the like. 300/zm, more preferably 30 to 200/zm, particularly preferably 40 to 150 (1 m. The film for a keyboard of the present invention, although it can be used directly to form a film composed of the film for the key disk a keyboard composed of layers, but the keyboard obtained by the keyboard of the present invention and other laminated layers can be used to form a keyboard. The raw materials for constituting the other layers include: polyester, polyamide, and polycarbonate. a resin such as an ester, a polyoxymethylene, a thermoplastic polyurethane, a thermosetting polyurethane, a polyolefin, or the like; a metal; a paper; a cotton cloth, etc. Further, the keyboard Ο may have a coating, an ink, and the like. The layer formed, or by the adhesive, primer The layer formed by the primer is used as the other layer as described above. When forming a layer composed of a coating material, an ink, or a layer composed of an adhesive or a primer as described above, it is preferably The heat treatment is carried out, and the temperature of the heat treatment is exemplified by, for example, 40 to 120 ° C. Further, the heat treatment time can be exemplified by, for example, 1 Torr to 3 hours. For the separate layer of the film for the keyboard of the present invention, or The laminate obtained by the film for the keyboard of the present invention and other laminated layers can be processed into a desired size and shape by cutting, punching, cutting, etc., and can be used for manufacturing a keyboard from -19 to 200937472. For the keyboard, you can also honing or laser to form the ditch or hole, etc. Others, the keyboard can also be set: used to arrange the top and bottom of the key: for the setting of the pressing, set under the keying piece The unevenness of the pressure switch of the key switch; the various concavities and convexities for arranging the bumps of the keyboard itself, such as a key top or a press, etc. These concavities and convexities are used for the film for the keyboard of the present invention. Separate layer, or borrow The film for a keyboard of the present invention and the laminate obtained by the other laminated layer can be formed by compression molding (pressure molding), vacuum molding, etc. φ by arranging a button or the like at a specific position of the keyboard as described above. The key top or the like can be made as a key control piece having the keyboard and the key top. In addition, in addition to the key top, the key control piece can also have a presser, etc. For the keyboard, a key top or a press is provided. It can be carried out using an adhesive such as a chemically reactive adhesive (adhesive based on cyanoacrylate) or a UV (ultraviolet) adhesive, etc. A keyboard or key obtained by using the film for a keyboard of the present invention. The control sheet is suitable for use as a communication terminal such as a portable telephone, various measuring instruments, a keyboard for inputting a personal computer, and an operation unit member constituting a remote controller. © "Embodiment" Hereinafter, the present invention is an embodiment. More specifically, the present invention is not limited to the embodiments. Further, the melt viscosity, the intrinsic viscosity and the ASTMD hardness of the thermoplastic polyurethane in the examples and the comparative examples, and the tensile stress (M1QQ) and heat resistance of the film for a keyboard were measured or evaluated by the following methods. <The Melt Viscosity of Thermoplastic Polyurethane> Using a Koka-type flow tester (Shimadzu Corporation), -20-200937472 at 80 °C The thermoplastic polyurethane obtained by drying under reduced pressure (10 ton·below) for 2 hours has a melt viscosity of 490. 3 N (50 kgf), mouth size = diameter 1 mm x length 10 mm, temperature 200 ° C. <Intrinsic Viscosity of Thermoplastic Polyurethane> 200 ml of N,N-dimethylformamide (DMF) was added per 1 g of a film for a keyboard obtained by the following Examples or Comparative Examples. After stirring at room temperature for 24 hours, it was separated by filtration to recover a DMF solution. When Q insoluble matter is formed, 200 ml of DMF is further added to the insoluble matter, and the mixture is stirred three times for 1 hour, and then subjected to filtration and separation. The recovered filtrates were combined together, and DMF was distilled off from the filtrate, and vacuum-dried at room temperature for 24 hours, and then the mass of the obtained polyurethane component was measured to confirm inclusion in the film for keyboard. About 100% of the thermoplastic polyurethane has been extracted. Further, if the extraction ratio is not more than about 100%, it is judged that the unextracted portion is excluded from the measurement of the intrinsic viscosity because the molecular weight of the thermoplastic polyurethane is so high that it is insoluble in DMF. © Re-dissolve the extracted thermoplastic polyurethane in DMF to make it a concentration of 〇. 5 g / dl, and then using a Ubbelodhe-type viscometer to determine the temperature of the thermoplastic polyurethane in DMF solution at 30 ° C, and calculate the thermoplastic polyamine The intrinsic viscosity of formate (77 inh). Intrinsic viscosity of thermoplastic polyurethane (7?inh) = [ln(t/t〇)]/c [wherein t represents the flow time of the thermoplastic polyurethane in DMF solution (seconds) U, represents the flow time (seconds) of the solvent (DMF), and C represents the concentration (g/dl) of the thermoplastic urethane DMF solution. -21 - 200937472 <ASTMD Hardness of Thermoplastic Polyurethane> The thermoplastic polyurethane produced in the examples or comparative examples described below was injected using a mold which was polished to a mirror surface. Molding (barrel temperature: 185 to 210 ° C, mold temperature: 30 ° C) to produce a round-shaped molded article (diameter: 120 mm, thickness: 2 mm), and then use a circular plate obtained by three pieces The molded article was obtained by laminating, and the ASTM D hardness of the molded article (thermoplastic polyurethane) was measured in accordance with the guidelines of ASTM D2240.拉伸 <Tensile stress of film for keyboard> A dumbbell-shaped test piece (the width of the center portion) prescribed by the guidelines of JIS K 7311-1 995 is manufactured from a film for a keyboard obtained by the following examples or comparative examples. It is 5 mm). The tensile stress of the dumbbell-shaped test piece at 100% elongation was measured using "INSTRON 5 5 66" manufactured by INSTRON Japan Company Limited at a temperature of 23 ° C and a tensile speed of 300 mm / min. It is used as a tensile stress (M1GQ) for a film for a keyboard. <Heat resistance of film for keyboard> © 50 test pieces (100 mm in length × 100 mm in width) were produced by a film for a keyboard obtained in Examples or Comparative Examples described below. For each of the 50 test pieces, a screen ink was placed at the center (Teikoku Printing Inks Mfg. Co. ,Ltd. The "IPX Screen Ink" manufactured was applied in a square shape of 50 mm in length and 50 mm in width, and then placed in a hot air dryer at 90 ° C for 1 hour. The state of the test piece after the hot air drying treatment was observed, and the heat resistance of the test piece was evaluated on the basis of the following criteria, and this was used as the heat resistance of the film for the keyboard. -22- 200937472 (Evaluation criteria for heat resistance) 3: In the total number of test pieces (50 pieces), the screen printing ink coating portion did not undergo any warpage or shrinkage, and the smoothness was maintained: 2: In-screen printing ink The coating portion did not warp or shrink, and the number of test pieces for maintaining smoothness was 46 to 49 pieces (the warpage or shrinkage of the screen printing ink coating portion was observed in the test pieces of 1 to 4 pieces). 1: 1: There is no warpage or shrinkage in the screen printing ink application portion, and the number of test pieces for maintaining the smoothness of the flaw is 45 or less (in the test piece of 5 or more sheets, the ink can be observed in the screen printing ink) Warpage or shrinkage of the cloth.) Representative symbols of the components used in the examples and comparative examples are as follows: (polymer polyol)
POH-1 ： 將3-甲基-1，5-戊二醇與己二酸進行反應所製 造，每一分子之經基數（hydroxyl number) 爲2.00、且數量平均分子量爲1，500之聚酯 二醇 POH-2： 將1,4-丁二醇與己二酸進行反應所製造，每 一分子之羥基數爲2.00、且數量平均分子量 爲1，000之聚酯二醇 P0H-3 ： 將1，4-丁二醇與己二酸進行反應所製造，每 一分子之羥基數爲2.00、且數量平均分子量 爲2,000之聚酯二醇 POH-4： 每一分子之羥基數爲2.00、且數量平均分子 -23- 200937472 量爲1，〇〇〇之聚四亞甲基二醇 POH-5: 每一分子之羥基數爲2.00、且數量平均分子 量爲1，〇〇〇之聚（ε-己內酯）二醇 ΡΟΗ-6： 以3-甲基-1，5-戊二醇與1,6-己二醇之混合物 (〔3-甲基-1,5-戊二醇之莫耳數〕：〔ΐ，6-己二醇之莫耳數〕=9: 1)作爲多元醇成份之 每一分子之羥基數爲2.00、且數量平均分子 量爲1，〇〇〇之聚碳酸酯二醇 ❹ （有機聚異氰酸酯） MDI ： 4,4’-二苯甲烷二異氰酸酯 HDI： 六亞甲基二異氰酸酯 、 (鏈段增長劑） BD: 1，4-丁二醇 〔實施例1〕 (1)熱塑性聚胺基甲酸酯（PU-1)之製造 將高分子多元醇（ΡΟΗ-1)、有機聚異氰酸酯（MDI)及 © 鏈段增長劑（BD ) ’以POH-1 : MDI: BD之莫耳比爲1.0 : 6.1: 5.1 (源於異氰酸酯基之氮原子的含率爲4·9質量％)且 使此等之合計供應量爲200克/分鐘連續供應至以同軸方向旋 轉之雙螺桿型擠壓機（單徑爲30毫米Φ、L/D = 36 ;加熱區係 分成前部、中央部、後部之三區域）之加熱區的前部’並在 聚合溫度260°C之條件下進行連續式熔融聚合來實施聚胺基 甲酸酯之形成反應。所獲得之熔融物係以股條狀連續地擠壓 入水中，接著以製粒機加以切斷以獲得切粒。所獲得之切粒 在95°C下加以除濕乾燥4小時’以獲得熱塑性聚胺基甲酸酯 -24- 200937472 (PU-1)。以如上所述方法測定所獲得之熱塑性聚胺基甲酸 酯（PU-1 )的熔融黏度及ASTM D硬度。結果係如表1所示 〇 (2)鍵盤用之薄膜之製造 將藉由如上所述第（1)項所獲得之熱塑性聚胺基甲酸酯 (PU-1)供應至裝設T-模之單軸螺桿型擠壓機（機筒直徑爲 25毫米φ、機筒溫度爲180至2 00°C、模具溫度爲200°C )之 供應口，由T-模以薄膜狀擠壓出於30°C之冷卻輥上，並經冷 0 卻後加以捲取以製造厚度爲lOOym之鍵盤用之薄膜。使用所 獲得之鍵盤用之薄膜，以如上所述之方法測定包含在其之熱 塑性聚胺基甲酸酯的固有黏度、該鍵@用之薄膜的拉伸應力 (Mmo)及耐熱性。結果係如表1所示。 〔實施例2至5〕 (1) 熱塑性聚胺基甲酸酯（PU-2至PU-5 )之製造 除了以如下表1所示之比率使用高分子多元醇（P0H-2 至P0H-5)、有機聚異氰酸酯（MDI)及鏈段增長劑（BD) Ο 以外，其餘則以與實施例1相同的方式製造熱塑性聚胺基甲 酸酯（PU_2至PU-5 )。將所獲得之各熱塑性聚胺基甲酸酯（ PU-2至PU-5)以如上所述之方法測定熔融黏度及ASTM D硬 度。結果係如表1所示。 (2) 鍵盤用之薄膜之製造 使用藉由如上所述第（1)項所獲得之熱塑性聚胺基甲酸 酯（PU-2至PU-5 )，並以與實施例1相同的方式製造厚度爲 lOO/zm之鍵盤用之薄膜。使用所獲得之鍵盤用之薄膜以如上 所述之方法測定包含在其之熱塑性聚胺基甲酸酯的固有黏度 -25- 200937472 、該鍵盤用之薄膜的拉伸應力（〇〇)及耐熱性。結果係如 表1所示。 表1 實施例1 實施例2 實施例3 實施例4 實施例5 〔熱塑性聚胺基甲酸醋〕 PU-1 PU-2 PU-3 PU-4 PU-5 高肝多元醇 讎 POH-1 POH-2 POH-3 POH-4 POH-5 艱比 1.0 1.0 1.0 1.0 1.0 有機聚異氰酸酯 _ MDI MDI MDI MDI MDI 莫耳比 6.1 3.7 7.9 4.4 3.9 鏈段增長劑 _ BD BD BD BD BD 莫耳比 5.1 2.7 6.9 3.4 2.9 源於異氰酸醋基之氮原子 質量％ 的含率 4.9 4.8 4.8 5.1 4.9 熔融黏度 Pa'· s 3,200 1,600 1,100 3,300 3,000 固有黏度 dl/g 1.0 0.9 0.9 1.0 0.9 ASTM D硬度 53 58 60 56 59 [鍵盤用之薄膜] MPa 拉伸應力（M100) 22 18 19 18 19 耐熱性 3 3 3 3 3POH-1 : A polyester obtained by reacting 3-methyl-1,5-pentanediol with adipic acid, having a hydroxyl number of 2.00 per molecule and a number average molecular weight of 1,500. Glycol POH-2: A polyester diol P0H-3 prepared by reacting 1,4-butanediol with adipic acid, having a hydroxyl number of 2.00 per molecule and a number average molecular weight of 1,000: a polyester diol POH-4 having a hydroxyl group number of 2.00 and a number average molecular weight of 2,000 per mole of 1,4-butanediol and adipic acid: the number of hydroxyl groups per molecule is 2.00, and The number average molecular molecule -23- 200937472 is 1, the polytetramethylene glycol POH-5: the hydroxyl number per molecule is 2.00, and the number average molecular weight is 1, 〇〇〇 poly (ε- Caprolactone)diol ΡΟΗ-6: a mixture of 3-methyl-1,5-pentanediol and 1,6-hexanediol ([3-methyl-1,5-pentanediol) Number: [ΐ, the molar number of 6-hexanediol] = 9: 1) As the polyol component, the number of hydroxyl groups per molecule is 2.00, and the number average molecular weight is 1, Alcohol (organic Isocyanate) MDI : 4,4'-diphenylmethane diisocyanate HDI: hexamethylene diisocyanate, (segment growth agent) BD: 1,4-butanediol [Example 1] (1) Thermoplastic polyamine group The production of formate (PU-1) is based on the molecular weight of POH-1 : MDI: BD for polymer polyol (ΡΟΗ-1), organic polyisocyanate (MDI) and © segment extender (BD). 1.0 : 6.1: 5.1 (the content of the nitrogen atom derived from the isocyanate group is 4.9 mass%) and the total supply of these is 200 g/min continuously supplied to the twin-screw type extruder which rotates in the coaxial direction. (The single diameter is 30 mm Φ, L/D = 36; the heating zone is divided into the front part of the heating zone of the front, the central part, and the rear part) and the continuous melting is carried out at a polymerization temperature of 260 °C. Polymerization is carried out to carry out a formation reaction of a polyurethane. The obtained melt was continuously extruded into water in the form of strands, followed by cutting with a granulator to obtain pellets. The obtained pellets were dehumidified and dried at 95 ° C for 4 hours to obtain a thermoplastic polyurethane-24-200937472 (PU-1). The melt viscosity and ASTM D hardness of the obtained thermoplastic polyurethane (PU-1) were measured by the method described above. The results are as shown in Table 1. The manufacture of the film for the keyboard of the keyboard (2) is supplied to the T-die by the thermoplastic polyurethane (PU-1) obtained in the above item (1). The supply port of the single-shaft screw type extruder (barrel diameter 25 mm φ, barrel temperature 180 to 200 ° C, mold temperature 200 ° C) is extruded by a T-die in a film shape. On a chill roll of 30 ° C, and after cold 0, it was taken up to produce a film for a keyboard having a thickness of 100 μm. Using the obtained film for a keyboard, the intrinsic viscosity of the thermoplastic polyurethane contained therein, the tensile stress (Mmo) of the film for the bond, and the heat resistance were measured by the method described above. The results are shown in Table 1. [Examples 2 to 5] (1) Production of Thermoplastic Polyurethane (PU-2 to PU-5) Polymer polyols (P0H-2 to P0H-5) were used in the ratios shown in Table 1 below. Thermoplastic polyurethane (PU_2 to PU-5) was produced in the same manner as in Example 1, except for organic polyisocyanate (MDI) and chain extender (BD). Each of the obtained thermoplastic polyurethanes (PU-2 to PU-5) was measured for melt viscosity and ASTM D hardness as described above. The results are shown in Table 1. (2) The film for a keyboard is manufactured by using the thermoplastic polyurethane (PU-2 to PU-5) obtained in the above item (1), and manufactured in the same manner as in the embodiment 1. A film for a keyboard having a thickness of 100/zm. Using the obtained film for a keyboard, the intrinsic viscosity of the thermoplastic polyurethane contained therein is measured as described above -25-200937472, the tensile stress (〇〇) and heat resistance of the film for the keyboard . The results are shown in Table 1. Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 [Thermoplastic polyurethane urethane] PU-1 PU-2 PU-3 PU-4 PU-5 High liver polyol 雠POH-1 POH- 2 POH-3 POH-4 POH-5 Difficult ratio 1.0 1.0 1.0 1.0 1.0 Organic polyisocyanate _ MDI MDI MDI MDI MDI Mobi 6.1 3.7 7.9 4.4 3.9 Chain extender _ BD BD BD BD BD Moerby 5.1 2.7 6.9 3.4 2.9 Content of nitrogen atomic mass derived from isocyanate group 4.9 4.8 4.8 5.1 4.9 Melt viscosity Pa'· s 3,200 1,600 1,100 3,300 3,000 Intrinsic viscosity dl/g 1.0 0.9 0.9 1.0 0.9 ASTM D hardness 53 58 60 56 59 [Film for keyboard] MPa Tensile stress (M100) 22 18 19 18 19 Heat resistance 3 3 3 3 3
〔比較例1至4〕 (1)熱塑性聚胺基甲酸酯（PU-6至PU-9)之製造 除了以如下表2所示之比率使用高分子多元醇（ΡΟΗ-1 、ΡΟΗ-2或ΡΟΗ-4)、有機聚異氰酸酯（MDI)及鏈段增長劑 (BD )以外，其餘則以與實施例1相同的方式製造熱塑性聚 胺基甲酸酯（PU-6至PU-9)。將所獲得之各熱塑性聚胺基甲 酸酯（PU-6至PU-9 )以如上所述之方法測定熔融黏度及ASTM D硬度。結果係如表2所示。 (2)鍵盤用之薄膜之製造 使用藉由如上所述第（1)項所獲得之熱塑性聚胺基甲酸 -26- 200937472 酯（Ρϋ-6至PU-9)，並以與實施例1相同的方式製造厚度爲 l〇〇//m之鍵盤用之薄膜。使用所獲得之鍵盤用之薄膜以如上 所述之方法測定包含在其之熱塑性聚胺基甲酸酯的固有黏度 、該鍵盤用之薄膜的拉伸應力（)及耐熱性。結果係如 表2所示。 〔比較例5〕 (1 )熱塑性聚胺基甲酸酯（PU-10)之製造 將高分子多元醇（POH-6)、有機聚異氰酸酯（HDI)及 Q 鏈段增長劑（BD)，以POH-6: HDI: BD之莫耳比爲1.0: 4.2: 3.2 (源於異氰酸酯基之氮原子的含率爲5.9質量％)且 使此等之合計供應量爲78克/分鐘連續供應至以同軸方向旋 丨， 轉之雙螺桿型擠壓機（單徑爲30毫米φ、L/D = 36 ;加熱區係 分成前部、中央部、後部之三區域）之加熱區的前部，並在 聚合溫度19(TC之條件下進行連續式熔融聚合來實施聚胺基 甲酸酯之形成反應。所獲得之熔融物係以股條狀連續地擠壓 入水中，接著以製粒機加以切斷以獲得切粒。所獲得之切粒 Ο 在60°C下加以除濕乾燥4小時，以獲得熱塑性聚胺基甲酸酯 (PU-10)。以如上所述方法測定所獲得之熱塑性聚胺基甲酸 酯（PU-10)的熔融黏度及ASTM D硬度。結果係如表2所示 。此外，使用該熱塑性聚胺基甲酸酯（PU-10)，以與在熱塑 性聚胺基甲酸酯之ASTM D硬度之測定方法之項所揭述者相 同的方式製造圓板狀之成型品（直徑爲120毫米、厚度爲2 毫米），然後使用經疊合三片所獲得之圓板狀成型品，並根 據JISK 7311-1995之準則進行使用A型硬度計的硬度試驗， 結果則爲98。 -27- 200937472 (2)鍵盤用之薄膜之製造 使用藉由如上所述第（1)項所所獲得之熱塑性聚胺基甲 酸酯（PU-10)，並以與實施例1相同的方式製造厚度爲100 之鍵盤用之薄膜。使用所獲得之鍵盤用之薄膜以如上所 述之方法測定包含在其之熱塑性聚胺基甲酸酯的固有黏度、 該鍵盤用之薄膜的拉伸應力（M1Q())及耐熱性。結果係如表2 所示。 表2 比較例1 比較例2 比_3 比較例4 比較例5 〔熱塑性聚胺基甲酸酯〕 PU-6 PU-7 PU-8 PU-9 PU-10 髙分子多元醇 麵 POH-1 POH-2 POH-2 POH-4 POH-6 莫耳比 1.0 1.0 1.0 1.0 1.0 有機聚異氰酸酯 觀 MDI MDI MDI MDI MDI 莫耳比 4.5 2.1 3.1 3.4 4.2 鏈段增長劑 麵 BD BD BD BD BD 莫耳比 3.5 1.1 2.1 2.4 3.2 源於異氰酸酯基之氮原子 質量％ 的含率 4.3 3.6 4.4 4.6 5.9 熔融黏度 Pa-s 2,500 13〇〇 1,800 3,000 1,500 固有黏度 dl/g 0.9 1.0 0.9 1.0 0.7 ASTMD硬度 42 42 51 45 46 C鍵盤用之薄膜：） MPa 拉伸應力（M100) 10 6 12 11 13 耐熱性 1 1 2 1 1[Comparative Examples 1 to 4] (1) Production of Thermoplastic Polyurethane (PU-6 to PU-9) Polymer polyols (ΡΟΗ-1, ΡΟΗ-2) were used in the ratios shown in Table 2 below. Further, thermoplastic urethane (PU-6 to PU-9) was produced in the same manner as in Example 1 except for ΡΟΗ-4), organic polyisocyanate (MDI) and chain extender (BD). Each of the obtained thermoplastic polyurethanes (PU-6 to PU-9) was measured for melt viscosity and ASTM D hardness as described above. The results are shown in Table 2. (2) Production of a film for a keyboard The thermoplastic polyurethane -26-200937472 ester (Ρϋ-6 to PU-9) obtained by the above item (1) is used, and is the same as in the first embodiment. The method is to manufacture a film for a keyboard having a thickness of l〇〇//m. Using the obtained film for a keyboard, the intrinsic viscosity of the thermoplastic urethane contained therein, the tensile stress () of the film for the keyboard, and heat resistance were measured by the method described above. The results are shown in Table 2. [Comparative Example 5] (1) Production of thermoplastic polyurethane (PU-10) A polymer polyol (POH-6), an organic polyisocyanate (HDI), and a Q segment growth agent (BD) were used. POH-6: HDI: The molar ratio of BD is 1.0: 4.2: 3.2 (the content of the nitrogen atom derived from the isocyanate group is 5.9% by mass) and the total supply of these is continuously supplied to 78 g/min. Rotating in the coaxial direction, rotating the twin-screw extruder (single diameter is 30 mm φ, L/D = 36; the heating zone is divided into the front, the central part, the rear three areas) of the front of the heating zone, and The continuous melt polymerization is carried out under the conditions of polymerization temperature 19 (TC) to carry out the formation reaction of the polyurethane. The obtained melt is continuously extruded into water in the form of strands, followed by cutting with a granulator. The pellet was obtained by pulverization. The obtained pelletized granules were dehumidified and dried at 60 ° C for 4 hours to obtain a thermoplastic polyurethane (PU-10). The obtained thermoplastic polyamine was measured by the method described above. The melt viscosity of the urethane (PU-10) and the ASTM D hardness. The results are shown in Table 2. In addition, the thermoplastic polyurethane was used. The acid ester (PU-10) was molded into a disk-shaped molded article (diameter 120 mm, thickness 2) in the same manner as described in the measurement method of ASTM D hardness of thermoplastic polyurethane. Mm), then using a round plate-shaped molded product obtained by laminating three sheets, and using a hardness test using a type A durometer according to the guidelines of JIS K 7311-1995, the result is 98. -27- 200937472 (2) Keyboard For the production of the film, a thermoplastic polyurethane obtained by the above item (1) (PU-10) was used, and a keyboard having a thickness of 100 was produced in the same manner as in Example 1. The film was obtained by using the obtained film for a keyboard, and the intrinsic viscosity of the thermoplastic polyurethane contained therein, the tensile stress (M1Q()) of the film for the keyboard, and heat resistance were measured by the method described above. The results are shown in Table 2. Table 2 Comparative Example 1 Comparative Example 2 Ratio_3 Comparative Example 4 Comparative Example 5 [Thermoplastic polyurethane] PU-6 PU-7 PU-8 PU-9 PU-10 髙Molecular Polyol Surface POH-1 POH-2 POH-2 POH-4 POH-6 Mohr Ratio 1.0 1.0 1.0 1.0 1.0 Organic Polyisocyanate View MDI MDI MDI MDI MDI Molby 4.5 2.1 3.1 3.4 4.2 Chain Growth Agent BD BD BD BD BD Mobi 3.5 1.1 2.1 2.4 3.2 The content of nitrogen atomic % derived from isocyanate groups 4.3 3.6 4.4 4.6 5.9 Melting Viscosity Pa-s 2,500 13〇〇1,800 3,000 1,500 Intrinsic viscosity dl/g 0.9 1.0 0.9 1.0 0.7 ASTMD hardness 42 42 51 45 46 C Film for keyboard:) MPa Tensile stress (M100) 10 6 12 11 13 Heat resistance 1 1 2 1 1
由表1及2可了解到：拉伸應力（M1G〇)爲符合本發明 所規定條件的實施例1至5之鍵盤用之薄膜，係即使經由網 印油墨塗佈後的90°C、1小時之熱風乾燥處理，在網印油墨 塗佈部並未發生任何翹曲或收縮而維持著平滑性，因此，具 有對於鍵盤用之薄膜所要求之優越的耐熱性。與此相對，拉 -28 - 200937472 伸應力並未符合本發明之規定條件的比較例1至5 之鍵盤用之薄膜，卻因塗佈網印油墨後的90°C、1小時之熱 風乾燥處理而在多數試驗片係可觀測到在網印油墨塗佈部之 翹曲或收縮，以及並未具有對鍵盤用之薄膜所要求之優越的 耐熱性。 〔產業上之利用可能性〕 若根據本發明，則可提供一種具有優越的非膠黏性、使 用性、耐熱性及尺寸精確度之穩定性，同時特別是即使由於 0 在爲固化或固定黏著劑或印刷印墨時等而實施加熱處理’也 不會發生翹曲或收縮等之不良現象、或薄膜彼此膠著等問題 之鍵盤用之薄膜。若根據本發明之鍵盤用之薄膜，則可解決 當在可攜式電話等之最終製品之規定位置配置鍵控片等時必 須以人工將其平坦化後再嵌進或要求特殊裝置等而降低最終 製品的生產性之問題，或因經常發生無法用作爲鍵控片或鍵 盤的不良品而降低良率之問題，且也可達成鍵控片或鍵盤之 薄型化。此外，若根據本發明之鍵盤用之薄膜，則可提供一 〇 種即使不使用框架片等之補強材也可保持形狀之鍵盤或鍵控 片，因此可達成最終製品之輕量化或縮小化、也可簡化製程 〇 【圖式簡單說明】 無。 【主要元件符號說明】 無。 -29-It can be understood from Tables 1 and 2 that the tensile stress (M1G〇) is a film for the keyboards of Examples 1 to 5 in accordance with the conditions specified in the present invention, even after coating at 90 ° C, 1 via screen printing ink. The hot air drying treatment of the hour does not cause any warpage or shrinkage in the screen printing ink application portion, and maintains smoothness. Therefore, it has excellent heat resistance required for the film for a keyboard. On the other hand, the film for the keyboard of Comparative Examples 1 to 5 in which the tensile stress did not conform to the conditions specified in the present invention was dried at 90 ° C for 1 hour after application of the screen printing ink. On the basis of the test piece, the warpage or shrinkage of the screen printing ink coating portion was observed, and the superior heat resistance required for the film for the keyboard was not obtained. [Industrial Applicability] According to the present invention, it is possible to provide a superior non-adhesive property, usability, heat resistance and dimensional accuracy stability, especially even if it is cured or fixed due to 0 A film for a keyboard for performing a heat treatment at the time of printing an ink or the like, and which does not cause problems such as warpage or shrinkage, or adhesion of the films to each other. According to the film for a keyboard of the present invention, it is possible to solve the problem that when a key sheet or the like is disposed at a predetermined position of a final product such as a portable telephone, it is necessary to manually flatten it, embed it, or require a special device or the like. The problem of the productivity of the final product, or the problem that the yield cannot be reduced as a defective product of the key sheet or the keyboard, and the thinning of the key sheet or the keyboard can be achieved. Further, according to the film for a keyboard of the present invention, it is possible to provide a keyboard or a key sheet which can maintain a shape even without using a reinforcing member such as a frame sheet, thereby achieving weight reduction or reduction of the final product. It also simplifies the process 〇 [Simple diagram description] None. [Main component symbol description] None. -29-