201041745 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種作為構成使用在行動電話等通訊終 端機、各種計測器、個人電腦輸入用鍵盤及遙控裝置之操 作部等之按鍵墊之素材有用之複合成形體。 【先前技術】 近年來，以由熱塑性聚胺酯（polyurethane)、聚對苯 二曱酸伸乙酯、聚酯彈性體等之樹脂製薄膜所組成之按鍵 墊用薄膜而得到之按鍵墊來接著、印刷或印刷接著鍵帽（按 鈕鍵）所製造之按鍵片材係廣泛地使用於行動電話等通訊 終端機、各種計測器、個人電腦輸入用鍵盤及遙控裝置等 之操作部，知道數種關聯到此種按鍵片材之技術（例如參考 專利文獻1及2)。此外，在構成前述按鍵墊之按鍵墊用薄 膜之素材中，由於具有適度之柔軟感及優異之緩衝性以外’ 還具有高度之耐久性，因此，以熱塑性聚胺酯特別適合， 也知道數種關於以此種熱塑性聚胺酯作為素材之按鍵墊用 薄膜之技術。 提議例如以至少由六亞曱基二異氰酸酯或氫化二苯基 曱烷二異氰酸酯選出之異氰酸酯和多元醇，作為合成成分 所合成之熱塑性聚胺酯，構成用以層積於矽酮（silicone) 橡膠等而成為按鍵墊之按鍵墊用表面材料，成為柔軟之觸 感優異、不引起黃變、耐水性、耐熱性變高且物性降低少 之聚胺酯製表面材料之方法（參考專利文獻3)。再者，已 有提案同樣的按鍵墊用表面材，藉由以末端具有羥基或胺 321943 201041745 ，之狀聚口物與一官能性異氰酸酯化合物反應所得之 聚胺s旨樹脂作為主成分之被覆材而形成之方法（專利文獻 4)，气耩由包含側鏈具有脂肪族不飽和烴基之胺醋聚合物、 有機虱I發氧院與虱梦烧基化（hydrosi lylation)觸媒之 被覆材而形成之方法（專利文獻5)。 此外’知道藉由將以六亞曱基二異氰酸酯作為主成分 之有機二異氰酸酯、以聚碳酸酯二元醇作為主成分之高分 〇 子多元醇和以碳數2至10之脂肪族二元醇作為主成分之鏈 延長劑發生反應所得到之樹脂顆粒予以熔融成形所成之熱 塑性聚胺酯樹脂片材進行熱成形而得到之聚胺酯樹脂製按 鍵墊係具有優異之二次成形性、财油酸性、耐變色性、透 明性、印刷適性等（參考專利文獻6)。 但是’在使用熱塑性聚胺酯等之樹脂製按鍵墊用薄膜 而製造按鍵墊或者按鍵片材之際，大多是塗佈矽酮系接著 ❹劑或印刷用油墨將其固化或固定，或者是層積於由矽酮樹 知所成之層之情況。但是’通常之熱塑性聚胺酯製之按鍵 塾用薄膜係表面活性不充分，因此，必須在事前，施行底 層塗料處理、電暈放電處理、電漿處理、臭氧處理、框架 處理等表面活化處理，作業效率變差。 作為不施行表面活化處理而將熱塑性樹脂和石夕酮樹脂 一體成形之技術，已知例如在使用射出成形機將聚碳酸醋、 ^丙埽、聚對苯二甲酸伸丁酯等熱塑性樹脂於模具空腔内 二人射出成形之後，在腔内形成之該熱塑性樹脂層上，二 _射出成形加成硬化型碎酮橡膠组成物，使其與石夕酮橡膠 321943 5 201041745 組成物在熱塑性樹脂之軟化點以上、未達熔點之溫度硬化， 而製造呈一體化地層積梦酮橡膠層和熱塑性樹脂層之複合 成形體之方法（參考專利文獻7)。但是，即使是該方法應 用在熱塑性聚胺酯和矽酮樹脂之複合成形體之製造，也無 法得到優異地接著熱塑性聚胺酯層和矽酮樹脂層之複合成 形體。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2004-327307號公報 [專利文獻2]日本特開2004-111258號公報 [專利文獻3]日本特開2005-25960號公報 [專利文獻4]日本特開2001-26648號公報 [專利文獻5]日本特開2001-26748號公報 [專利文獻6]國際公開第2004/106401號小冊 [專利文獻7]日本特開平8-174604號公報 【發明内容】 [發明之概要] [發明所欲解決的課題] 本發明係解決前述之問題，其目的係提供一種即使是 不施行表面活化處理，包含聚胺酯之構件和包含矽酮之構 件也充分接著之複合成形體，以及可使用該複合成形體製 造之按鍵墊或按鍵片材。 [用以解決課題的手段] 為了達成前述之目的，因此’本發明人們係重複地進 6 321943 201041745 订^種之檢討，結果發現，藉由在聚錢巾調配特定量之 特，平均粒徑之玻璃珠所獲得之聚胺醋組成物 ，與矽酮之 接著性優異，根據這些發現更加重複地進行檢討，而完成 本發明。 也就疋說，本發明係關於： 種複合成形體’係具有由相對於聚胺酯1〇〇質量份 3有0· 6貝量份以上的玻璃珠之聚胺酯組成物所成之聚胺 ❹酉旨系構件’與由梦_單獨所成或包含_為主之㈣組成 物所成之糊系構件，且該聚胺醋系構件與㈣系構件係 接觸之複合成形體， 其中，前述破璃珠之平均粒徑為3至45#m ; [2] 如上[1]所揭示之複合成形體，其中前述聚胺酯組成物 包含相對於聚胺酯1〇〇質量份為〇· 6至3〇質量份之玻璃 珠； [3] 如上述[1]或[2]所述之複合成形體，其中該聚胺酯酯 Ο係將高分子多元醇及有機多異氰酸醋予以反應所得之熱塑 性聚胺酯； [4] 如上述[1]至[3]中任一項所述之複合成形體，其中該 聚胺醋係將高分子多元醇、有機多I氰酸酷及鏈延長劑予 以反應所得之熱塑性聚胺醋； [5] 如上述[1]至[4]中任一項所述之複合成形體，其中該 汆氨ia中源自異氰酸酯基之氮原子的含有率為1·5至6質 量％; [6] 如上述[1]至[4]中任一項所述之複合成形體，其中該 7 321943 201041745 聚胺酯系構件為厚度2〇至300 //m之膜； [7] 如上述[1]至[7]中任一項所述之複合成形體，其中該 矽酮系構件係於該聚胺酯系構件上使硬化性矽酮組成物硬 化所形成者； [8] 如上述[7]所述之複合成形體，其中該硬化性矽酮組成 物包含.具有氫原子係結合於⑦原子之有機氫聚♦氧院以 及氫矽烷基化觸媒； [9] 一種按鍵墊，係由上述[丨]至[8]中任一項之複合成形 體所形成者； [10] -種按鍵片材，至少具有上述[9]之按鍵整及鍵帽。 [發明之效果] 藉由本發明，即使不施行表面活化處理亦可製造，亦 I獲得包含聚胺g旨之構件與包切酮之構件充分接著之複 。成开/體該複合成形體於製造按鍵塾或按鍵#材之際 別有用。 ' 【實施方式】 [發明之實施形態] 在以下，就本發明而詳細地進行說明。 本發明之複合成形體具有：於聚胺酯中含有玻璃珠之 :::組)成物所成之構件(以下’將該構件簡稱為聚二 所成或包含W主之魏组成 物所成之構件(以下’將該構件簡稱為「矽酮 广後，使該聚_旨系構件與㈣系構件接觸。」 L聚胺酯系構件] 321943 8 201041745 構成聚胺酯系構件之聚胺酯組成物中作為聚胺酯 者，可使用藉由將高子多元醇、有機多異氰酸酯以及視需 要之鏈延長劑予以反應所製造之熱塑性聚胺酯。 上述熱塑性聚胺酯的製造中所使用之高分子多元 醇，可使用聚胺酯製造中習知所使用之任一高分子多元 醇。相關高分子多元醇之例，例如可列舉聚酯多元醇、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、可氫化之共軛二烯烴聚合物系多元醇、箆麻 Ο 油系多元醇、乙烯基聚合物系多元醇等。這些高分子多元 醇可單獨使用1種，也可併用2種以上。其等之中，作為 高分子多元醇較佳是使用聚酯多元醇、聚醚多元醇、聚碳 酸酯多元醇中之1種或2種以上，更較佳是使用聚酯多元 醇及/或聚醚多元醇，再較佳是使用聚酯二元醇及/或聚醚 二元醇。 作為前述之聚酯多元醇，例如可列舉藉由按照常法， 〇將多元醇成分與多羧酸或其酯形成性衍生物（酯（低級烷基 西旨、芳基醋、碳酸醋等）、酐等）之多叛酸成分，直接地進 行酯化反應或酯交換反應所得到之聚酯多元醇、多元醇作 為起始劑，藉由使内酯進行開環聚合所得到之聚酯多元醇 等。 聚酯多元醇的製造中所使用之多元醇成分，可以使用 聚酯製造中一般使用者，例如可列舉乙二醇、二乙二醇、 三乙二醇、丙二醇、1, 3-丙二醇、2-甲基-1，3-丙二醇、2, 2-二乙基-1, 3-丙二醇、1, 3-丁二醇、1，4-丁二醇、2-甲基 9 321943 201041745 ’4 丁一醇、新戊二醇、戊二醇、3 醇、U-己二醇、庚二醇、以一辛二醇甲=，5-戊二 辛一醇、2, 7—二甲基义8〜辛二醇、U〜壬甲基-1，8— 一1，9—壬二醇、2,8~二甲基-1，9-壬二醇q 1〇八、2了基 數2至15之脂肪族二元醇Π，4-環己二醇:環二一醇等碳 環辛燒二基環辛燒二f =燒二甲醇、 ㈣韻乙氧基）苯等芳香族：元醇等每 個經基之二元醇、或者是三㈣基丙炫、刀子具有2 甘油、U，6-己炫三醇、季戊四醇、二：基=、 二3個以上之縣之多元醇等。在聚醋;二子 ΓΓ:可單獨使用1種，也可併用2種等之 裂強度等所代表之JL:T 拉伸應力或拉 聚胺t 予4_異、耐熱性亦優異之熱塑性 =胺日而"，較佳是使用U-丁二醇、3m5—戊二 醇醇1 6-己二醇和丨’ 8_辛二醇等碳數4至1〇之脂肪族二 70醇’更較佳是使用丁二醇、1，6-己二醇和！ 8一辛二 醇等碳數4至10之直鏈狀腊_二元醇。 聚酯多元醇的製造中所使用之多幾酸成分，可以使用 製造中一般使用者，例如可列舉琥朗、戊二酸、己 -酸、庚—酸、辛二酸、壬二酸、癸二酸、十二炫二酸、 甲基破賴、Μ基戊二酸、3~曱基戊二酸、三曱基己二 n曱基辛二甲基癸燒二酸、3上二甲基 癸院二酸等碳數4至12之脂肪族二舰丨環己炫二竣酸、 二聚酸、氫化二聚酸等脂環式二護酸；對苯二甲酸、間苯 10 321943 201041745 二甲酸、鄰苯二甲酸、萘二甲酸等芳香族二羧酸；偏苯三 甲酸；均苯四甲酸等3官能以上之多羧酸；或是其等之酯 形成性衍生物等。該等多羧酸成分可單獨使用1種，也可 併用2種以上。其等之中，由可獲得為非黏著性，且熔融 成形性、拉伸應力或拉裂強度等所代表之力學特性優異、 耐熱性亦優異之熱塑性聚胺酯而言，較佳是碳數4至12 之脂肪族二羧酸，更較佳是己二酸、壬二酸、癸二酸，再 較佳是己二酸。 〇 再者，聚酯多元醇的製造中所使用之内醋，例如可列 舉ε -己内酯、/9 -曱基- (5 -戊内酉旨等。 作為上述聚醚多元醇，例如可列舉在多元醇之存在 下，對於環狀醚進行開環聚合所得到之聚乙二醇、聚丙二 醇、聚四亞曱基二醇、聚（曱基四亞曱基二醇）等，可以使 用此等之中之1種或2種以上。其等之中，由可得到為非 黏著性且熔融成形性優異、以拉伸應力或拉裂強度所代表 〇之力學特性優異、耐熱性亦優異之熱塑性聚胺酯而言，較 佳是使用聚四亞甲基二醇及/或聚（甲基四亞甲基二醇）。 作為上述聚碳酸酯多元醇，例如可列舉藉由將多元醇 成分與碳酸二烷基酯、碳酸伸烷酯、碳酸二芳基酯等碳酸 酯化合物予以反應所得到者。作為聚碳酸酯多元醇的製造 中所使用之多元醇成分，可使用聚酯多元醇的製造中可使 用之成分所例示之多元醇成分。再者，作為碳酸二烷基酯 可列舉碳酸二曱基酯、碳酸二乙基酯等，作為碳酸伸烷酯 可列舉碳酸伸乙酯等，作為碳酸二芳基酯可列舉碳酸二苯 11 321943 201041745 基酯等。 作為上述聚酯聚碳酸酯多元醇，例如可列舉將多元醇 成分、聚緩酸醋成分與碳酸醋化合物’同時地予以反應所 製得者，或者分別合成上述之聚酯多元醇與聚碳酸酯多元 醇，其次使該等與碳酸酯化合物反應，或藉由將多元醇成 分與多羧酸成分予以反應所製得者等。 作為上述高分子多元醇之具體例，例如可列舉聚 (1,4-四亞曱基己二酸酯）二元醇、聚（3-曱基-1,5-五亞曱 基己二酸酯）二醇、聚（ε-己内酯）二元醇、聚四亞甲基二 醇等。 上述高分子多元醇的數平均分子量，較佳是500至 8, 000之範圍内、更較佳是600至5, 000之範圍内、再較 佳是800至3, 500之範圍内、更進一步較佳是850至1200、 特別較佳是900至1100、最較佳是1000。藉由使用具有該 範圍之數平均分子量之高分子多元醇，可得到為非黏著性 且熔融成形性、耐摩耗性、拉伸破斷強度等所代表之力學 特性、柔軟性、彎曲性、低殘留應變性等各種特性優異之 熱塑性聚胺酯。又，本說明書中，高分子多元醇之數平均 分子量係根據JI s Κ -15 5 7所測定之羥基價所算出之數平均 分子量。 再者，上述高分子多元醇之每1分子之羥基數，由可 得到熔融成形性、非黏著性、耐摩耗性、力學特性等更加 優異之熱塑性聚胺酯而言，較佳是2· 0至2. 1個之範圍内、 更較佳是2. 0至2. 07個之範圍内。 12 321943 201041745 上述熱塑性聚胺酯的製造中所使用之有機多異氮酸 酯，可使用在聚胺酯之製造中習知使用之任何一種有機多 異氰酸酯。相關有機多異氰酸酯，例如可列舉，—一^ 基甲院二異氰酸醋⑽…伸曱笨基二異氰酸醋、伸苯美二 異氰酸醋、伸苯二甲基二異氰酸酯、！，5_伸蔡基二異^ 13,3 -二氯-4,4’ —二苯基甲烧二異氰酸醋等芳香族_ 異氰酸醋；六亞甲基二異氰酸醋、異佛爾酮二異 〇 4’4’ -二環己基？烧二異級醋、氮化伸苯二甲基二^氰 酸醋等月旨肪族或腊環式二異氛酸醋等。該等有機多里氛 醋可單獨使用！種，也可併用2種以上。其等之卜、由可 得到為非黏著性且熔融成形性優異、力學特性優異、耐熱 性亦優異=聚胺醋而言，有機多異氰酸醋較佳是主要包: 4’4 一本基甲烧一異氰酸醋（較佳是包含5〇草耳0/、 上、更較佳是80莫耳％以上、再較佳是95莫耳％以上、特 別較佳是1〇〇莫耳％)。 熱塑性聚胺酯的製造時，必要時可併用鏈延長劑。作 為該鏈延長劑，可使用具有2個以上之活性氨原子之分子 量400以下之低分子化合物，具體而言，可列舉乙二醇、 丙二醇、u一丁二醇、I6一己二醇、U-雙經基乙氧 苯、1，4-環己二醇、雙（石-經乙基）對苯二f酸醋、伸 苯一甲基二醇等二元醇類；聯氨、乙二胺、丙二胺、伸苯 二甲基二胺、異佛爾酮二胺、哌哄或其衍生物、伸苯二胺、 伸甲苯基一胺、伸苯二甲基二胺、己二酸二酿拼、間苯二 甲酸二_等二胺類；胺基乙醇、胺基丙醇等胺基醇類等。 321943 13 201041745 該等鍵延長劑可單獨使用4，也可 之中，由可得到為非黏著性且 種乂上。其等 優異、对熱性亦優異之聚胺賴而古，綠性優異、力學特性 包含碳數2至1〇之脂肪族二元醇°(較，劑較佳是主要 上、更較佳是80莫耳％以上-疋包含50莫耳°“乂 別較佳是⑽莫耳％)，更較佳是^要^5莫耳％以上、特 佳是包含50莫耳％以上、3 ^4—丁二醇（較 是95莫耳％以上、转别虻杜 莫耳％以上、再較佳 旲斗/G以上特別較佳是100莫耳％)。 將前述之高分子多元醇、 二 鏈延長劑予以反庫而製进妖,夕異級醋及視需要之 合比率係考慮應韻予作為目 纟成"之遇 力學性能等而適度地決定，塑性聚胺酷之硬度、 性氫原子：異氣_基之子在於反應系之活 内之比例的方式使用各成分 佳^ 〇.9至h3之较圍 u之比例嫩;^分。… 分，错甶Μ上迷之比例使用各成 學特ΓΓ 以伸破斷延伸度等所代表之力 2、相性、彈性回復性等特性優異之熱塑性聚胺酉旨。 八熱塑性聚胺醋之製造方法係並無特別限制，可使用高 =子多元醇、有機多異氰動旨及視需要之鏈延長劑，採用 头之知:酯化反應技術之任何一種來進行，也可以採用預 聚合物法或一步法（one shot method)之任何一種。其等之 中，較佳是實質地於溶劑不存在下進行炼融聚合，特別更 車父佳是採用使用多軸螺旋型擠壓機之連續熔融聚合法。熔 融聚合時之聚合溫度較佳是180至28〇°c之範圍内。 321943 14 201041745 將上述之高分子多元醇、有機多異氰酸酯及視需要之 鏈延長劑予以反應而製造熱塑性聚胺酯時，亦可使用胺酯 化反應觸媒。該胺醋化反應觸媒之種類係並無特別限制，[Technical Field] The present invention relates to a material for a key pad that is used in a communication terminal such as a mobile phone, various measuring devices, a keyboard for inputting a personal computer, and an operation unit of a remote control device. Useful composite shaped body. [Prior Art] In recent years, a key pad obtained by using a film made of a resin film made of a thermoplastic resin such as polyurethane, polyethylene terephthalate or polyester elastomer is used to print and print. Or the button sheet manufactured by printing the keycap (button button) is widely used in communication terminals such as mobile phones, various measuring devices, keyboards for personal computer input, and remote control devices, and is known to be associated with several types. A technique of a button sheet (for example, refer to Patent Documents 1 and 2). In addition, in the material of the film for a button pad constituting the key pad, it has a high degree of durability because of its moderate softness and excellent cushioning property. Therefore, thermoplastic polyurethane is particularly suitable, and several kinds of The thermoplastic polyurethane is used as a material for a film for a key pad of a material. For example, an isocyanate and a polyhydric alcohol selected from at least a hexamethylene diisocyanate or a hydrogenated diphenyl decane diisocyanate, and a thermoplastic polyurethane synthesized as a synthetic component are proposed to be laminated on a silicone rubber or the like. The surface material for the key pad of the key pad is a method of forming a surface material of a polyurethane which is excellent in soft touch, does not cause yellowing, has high water resistance and heat resistance, and has little reduced physical properties (refer to Patent Document 3). Furthermore, the same surface material for the key pad has been proposed, and the polyamine s which is obtained by reacting a polyhydroxyl group having a hydroxyl group or an amine 321943 201041745 with a monofunctional isocyanate compound as a main component is used as a main component. In the method of forming (Patent Document 4), the gas is composed of an amine vinegar polymer having an aliphatic unsaturated hydrocarbon group in a side chain, a coating material of an organic oxime and a hydrosi lylation catalyst. Method of formation (Patent Document 5). Further, 'an organic diisocyanate having a hexamethylene diisocyanate as a main component, a high-density sulfonium polyol having a polycarbonate diol as a main component, and an aliphatic diol having a carbon number of 2 to 10 are known. The thermoplastic polyurethane resin sheet obtained by melt-molding the resin pellet obtained by the reaction of the chain extension agent as a main component is thermoformed, and the key pad of the polyurethane resin resin has excellent secondary formability, acidity, and resistance. Discoloration, transparency, printability, etc. (refer to Patent Document 6). However, when a button pad or a button sheet is produced by using a film for a button pad made of a resin such as thermoplastic polyurethane, it is often cured by an oxime-based enamel-based enamel or a printing ink, or laminated. The situation of the layer formed by the ketone tree. However, 'the usual thermoplastic polyurethane-based button film has insufficient surface activity. Therefore, it is necessary to perform surface activation treatment such as primer treatment, corona discharge treatment, plasma treatment, ozone treatment, frame treatment, etc. beforehand, and work efficiency. Getting worse. As a technique for integrally molding a thermoplastic resin and a linaloyl resin without performing a surface activation treatment, it is known to mold a thermoplastic resin such as polycarbonate, propylene carbonate or polybutylene terephthalate to a mold by using an injection molding machine. After the two persons in the cavity are injection-molded, on the thermoplastic resin layer formed in the cavity, the second addition-molded addition-hardening type ketone rubber composition is combined with the composition of the lithene ketone rubber 321943 5 201041745 in the thermoplastic resin. A method of forming a composite molded body in which a dream ketone rubber layer and a thermoplastic resin layer are integrally laminated (see Patent Document 7) is produced by curing at a temperature above the softening point and at a temperature less than the melting point. However, even if the method is applied to the production of a composite molded body of a thermoplastic polyurethane and an anthrone resin, a composite body excellent in adhesion to the thermoplastic polyurethane layer and the fluorenone resin layer cannot be obtained. [Patent Document 1] [Patent Document 1] JP-A-2004-327307 [Patent Document 2] JP-A-2004-111258 (Patent Document 3) JP-A-2005-25960 Japanese Patent Laid-Open No. 2001-26748 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2001-26748 [Patent Document 6] International Publication No. 2004/106401 (Patent Document 7) Japanese Patent Laid-Open No. Hei 8-174604 SUMMARY OF THE INVENTION [Summary of the Invention] [Problems to be Solved by the Invention] The present invention solves the aforementioned problems, and an object thereof is to provide a member including a polyurethane and a member containing an anthrone even without performing a surface activation treatment. The composite molded body which is sufficiently followed, and a key pad or key sheet which can be manufactured using the composite molded body. [Means for Solving the Problem] In order to achieve the above-mentioned purpose, the present inventors have repeatedly reviewed the classification of 6 321 943 201041745, and found that by arranging a specific amount of the special amount of the money towel, the average particle size The polyurethane hydrate composition obtained from the glass beads is excellent in adhesion to fluorenone, and the present invention has been completed by reviewing more repeatedly based on these findings. In other words, the present invention relates to a polycomposite composition comprising a polyurethane composition having a glass bead of 0.6 parts by mass or more based on 1 part by mass of the polyurethane. a composite member formed by contacting a member made of a composition composed of a dream or a composition containing _ as a main component, and the polyamine vine member and the (four) member are in contact with each other, wherein the glass beads are The composite molded body disclosed in the above [1], wherein the aforementioned polyurethane composition contains glass beads of 〇 6 to 3 parts by mass based on 1 part by mass of the polyurethane. [3] The composite formed body according to the above [1] or [2] wherein the polyurethane ester is a thermoplastic polyurethane obtained by reacting a polymer polyol and an organic polyisocyanate; [4] The composite formed body according to any one of [1], wherein the polyamine vinegar is a thermoplastic polyamine vinegar obtained by reacting a polymer polyol, an organic poly-I cyanate and a chain extender; The composite formed body according to any one of the above [1] to [4], wherein The composite molded body according to any one of the above [1] to [4] wherein the 7321943 201041745 polyurethane member is The composite formed body according to any one of the above-mentioned [1] to [7] wherein the fluorenone-based member is sclerosing on the polyurethane-based member. [8] The composite formed body according to the above [7], wherein the sclerosing fluorenone composition comprises: an organic hydrogen concentrating body having a hydrogen atom bonded to 7 atoms and A hydroquinone alkylation catalyst; [9] A key pad formed by the composite molded body of any one of the above [丨] to [8]; [10] - a button sheet having at least the above [9] ] The button and the key cap. [Effect of the Invention] According to the present invention, it can be produced without performing a surface activation treatment, and I can obtain a member comprising a polyamine g and a component of a ketamine. The opening/body of the composite formed body is useful when manufacturing the button 按键 or button #材. [Embodiment] [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. The composite formed article of the present invention has a member made of a glass bead::: group) in a polyurethane (hereinafter, the member is simply referred to as a component formed by a poly-dimer or a composition comprising a W-main. (The following is abbreviated as "the ketone is broadened, and the poly-member is brought into contact with the member of the (4) member." L-polyester-based member] 321943 8 201041745 The polyurethane composition constituting the polyurethane-based member may be used as a polyurethane. A thermoplastic polyurethane produced by reacting a high-powder polyol, an organic polyisocyanate, and an optional chain extender. The polymer polyol used in the production of the thermoplastic polyurethane can be used in the production of polyurethane. Any of the polymer polyols may, for example, be a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyester polycarbonate polyol, a polyolefin polyol, or the like. The hydrogenated conjugated diene polymer is a polyol, a ricin oil polyol, a vinyl polymer polyol, etc. These polymer polyols can be used alone. In the above, it is preferred to use one or two or more of a polyester polyol, a polyether polyol, and a polycarbonate polyol as the polymer polyol, and it is more preferred to use a polymer. Further, as the polyester polyol and/or the polyether polyol, it is preferred to use a polyester diol and/or a polyether diol. As the polyester polyol described above, for example, it can be exemplified by The alcohol component and the polycarboxylic acid or an ester-forming derivative thereof (ester (lower alkyl group, aryl vinegar, carbonated vinegar, etc.), anhydride, etc.) are directly subjected to esterification reaction or transesterification reaction. The obtained polyester polyol or polyol as a starter, a polyester polyol obtained by ring-opening polymerization of a lactone, etc. Polyol components used in the production of polyester polyols can be used as a polyhydric alcohol component. Typical users of ester production include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 2-methyl-1,3-propanediol, and 2,2-diethyl. -1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl 9 321943 201041745 '4 Dingyi , neopentyl glycol, pentanediol, 3 alcohol, U-hexanediol, heptanediol, monooctyl glycol methyl, 5-pentanediol, 2,7-dimethylyi 8~xin Glycol, U~壬methyl-1,8-mono-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol q 1〇8, 2 bases 2 to 15 fat Group diol oxime, 4-cyclohexane diol: cyclodienol and other carbocyclic octyl succinyl sulfonate succinic acid f f = burnt dimethanol, (tetra) rhythm ethoxy) benzene and other aromatic: monohydric alcohol, etc. A diol based on a base, or a tris(tetra)yl propyl sulphate, a knives having 2 glycerol, U,6-hexatriol, pentaerythritol, a di-base group, a polyhydric alcohol of two or more counties, etc. ; 二子ΓΓ: It can be used alone or in combination with two kinds of crack strengths such as JL: T tensile stress or pull polyamine t to 4_ different, heat resistance is also excellent thermoplastic = amine day and " Preferably, U-butanediol, 3m5-pentanediol alcohol 16-hexanediol, and 丨8-octanediol are used, and the aliphatic di-70 alcohol having a carbon number of 4 to 1 Å is more preferably used. Butylene glycol, 1,6-hexanediol and! A straight-chain wax-diol having a carbon number of 4 to 10 such as 8-octanediol. The acid component used in the production of the polyester polyol can be used as a general user in the production, and examples thereof include sulphate, glutaric acid, hexanoic acid, heptanoic acid, suberic acid, sebacic acid, and hydrazine. Diacid, dodecanedioic acid, methyl ruthenium, decyl glutaric acid, 3~ mercapto glutaric acid, trimethyl hexamethylene oxalyl dimethyl sulfonate, 3 dimethyl Auxiliary bismuth acid such as bismuth dicarboxylic acid, such as bismuth dicarboxylic acid, dimer acid, hydrogenated dimer acid, etc.; terephthalic acid, isophthalic acid 10 321943 201041745 An aromatic dicarboxylic acid such as formic acid, phthalic acid or naphthalene dicarboxylic acid; a trimellitic acid; a trifunctional or higher polycarboxylic acid such as pyromellitic acid; or an ester-forming derivative thereof. These polycarboxylic acid components may be used alone or in combination of two or more. Among these, a thermoplastic polyurethane which is excellent in mechanical properties and which is excellent in heat resistance, such as melt moldability, tensile stress, tensile strength, and the like, which is non-adhesive, is preferably a carbon number of 4 to The aliphatic dicarboxylic acid of 12 is more preferably adipic acid, sebacic acid, sebacic acid, and even more preferably adipic acid. Further, examples of the internal vinegar used in the production of the polyester polyol include ε-caprolactone and /9-fluorenyl-(5-pentane). The polyether polyol may be, for example, The polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(indenyltetradecylene glycol) obtained by subjecting a cyclic ether to ring-opening polymerization in the presence of a polyhydric alcohol can be used. One or two or more of these, etc. Among them, the non-adhesive property is excellent, the melt moldability is excellent, the mechanical properties represented by tensile stress or tensile strength are excellent, and the heat resistance is excellent. In the case of the thermoplastic polyurethane, polytetramethylene glycol and/or poly(methyltetramethylene glycol) is preferably used. As the above polycarbonate polyol, for example, a polyol component can be used. A carbonate compound such as a dialkyl carbonate, a alkyl carbonate or a diaryl carbonate is obtained by reacting a polyester compound such as a polyol polyol used for the production of a polycarbonate polyol. The polyol component exemplified by the ingredients that can be used. Examples of the dialkyl carbonate include dinonyl carbonate and diethyl carbonate. Examples of the alkyl carbonate include ethyl carbonate and the like. Examples of the diaryl carbonate include diphenyl carbonate 11 321943 201041745. Examples of the polyester polycarbonate polyol include those obtained by simultaneously reacting a polyol component, a polyamic acid vinegar component, and a carbonate acid compound, or separately synthesizing the above polyester polyol and The polycarbonate polyol is obtained by reacting the above with a carbonate compound or by reacting a polyol component with a polycarboxylic acid component. Specific examples of the polymer polyol include, for example, poly (1,4-tetradecyl adipate) diol, poly(3-mercapto-1,5-pentamethylene adipate) diol, poly(ε-caprolactone) A polyol, a polytetramethylene glycol, etc. The number average molecular weight of the above polymer polyol is preferably in the range of 500 to 8,000, more preferably in the range of 600 to 5,000, and still more preferably It is in the range of 800 to 3,500, more preferably 850 to 1200, particularly preferably It is 900 to 1100, and most preferably 1000. By using a polymer polyol having a number average molecular weight in the range, it is possible to obtain non-adhesive properties, such as melt formability, abrasion resistance, tensile breaking strength, and the like. A thermoplastic polyurethane having various properties such as mechanical properties, flexibility, flexibility, and low residual strain. Further, in the present specification, the number average molecular weight of the polymer polyol is a hydroxyl value measured according to JI s -15 -15 5 7 . In addition, the number of hydroxyl groups per molecule of the polymer polyol is higher than that of thermoplastic polyurethane which can provide melt moldability, non-adhesiveness, abrasion resistance, mechanical properties and the like. Preferably, it is in the range of 2. 0 to 2. 1 and more preferably in the range of 2.0 to 2. 07. 12 321943 201041745 The organic polyisocyanate used in the production of the above thermoplastic polyurethane can be any organic polyisocyanate conventionally used in the production of polyurethane. Related organic polyisocyanates, for example, can be exemplified by a group of ketone diisocyanate vinegar (10)... 曱 曱 二 二 diisocyanate vinegar, benzoic acid diisocyanate, benzoyl diisocyanate, , 5_ stretching Caiji diiso^ 13,3 -dichloro-4,4'-diphenylmethane diisocyanate vinegar and other aromatic _ isocyanic acid vine; hexamethylene diisocyanate, Isophorone diisoindole 4'4'-dicyclohexyl? Burning diiso-grade vinegar, nitriding benzodimethyl di- cyanuric acid vinegar, etc., such as a month of aliphatic or wax ring type diiso-acid vinegar. These organic currants can be used alone! Two or more types may be used in combination. The organic polyisocyanate is preferably a main package: 4'4 one, which is excellent in melt moldability, excellent in mechanical properties, and excellent in heat resistance. A base isocyanate acetoacetate (preferably comprising 5 ounces of grass 0/, upper, more preferably 80 mole% or more, still more preferably 95 mole% or more, particularly preferably 1 〇〇 mo ear%). In the production of a thermoplastic polyurethane, a chain extender may be used in combination if necessary. As the chain extender, a low molecular compound having a molecular weight of 400 or less having two or more active ammonia atoms can be used, and specific examples thereof include ethylene glycol, propylene glycol, u-butylene glycol, I6-hexanediol, and U-. Diol ethoxybenzene, 1,4-cyclohexanediol, bis(stone-ethyl)terephthalic acid vinegar, benzene monomethyl glycol and other glycols; hydrazine, ethylenediamine , propylenediamine, dimethylenediamine, isophorone diamine, piperazine or its derivatives, phenylenediamine, tolylamine, benzylenediamine, adipic acid Stuffed, isophthalic acid di-diamines, amine alcohols such as aminoethanol and aminopropanol. 321943 13 201041745 These key extenders can be used alone or in combination with non-adhesive properties. The polyamine which is excellent in heat resistance and excellent in heat, has excellent greenness, and the mechanical properties include an aliphatic diol having a carbon number of 2 to 1 Å (more preferably, the agent is mainly, more preferably 80). Mole% or more - 疋 contains 50 moles "" is preferably (10) mole %), more preferably ^ 5 moles or more, particularly preferably 50 moles or more, 3 ^ 4 - Butylene glycol (more than 95% by mole, more than 虻 Du Moer% or more, and even more preferably 旲 / / G or more is preferably 100% by mole). The aforementioned polymer polyol, two chain extension The agent is decontaminated into the demon, and the ratio of the vinegar to the yoghurt and the ratio of the needs are considered to be moderately determined as the mechanical properties of the syllabus, the hardness of the plastic polyamine, the hydrogen atom : 异 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Technical characteristics: It is a thermoplastic polyamine with excellent properties such as 2, phase, and elastic recovery which are represented by elongation and elongation. The production method is not particularly limited, and a high-sub polyol, an organic polyisocyanate, and an optional chain extender may be used, and any one of the first known esterification reaction techniques may be used, or prepolymerization may be employed. Any one of a method or a one shot method. Among them, it is preferred to carry out the smelting polymerization in the absence of a solvent, and in particular, the use of a multi-axis screw type extruder is adopted. Continuous melt polymerization. The polymerization temperature during melt polymerization is preferably in the range of 180 to 28 ° C. 321943 14 201041745 The above polymer polyol, organic polyisocyanate and, if necessary, chain extender are reacted to produce thermoplastic In the case of polyurethane, an amine esterification reaction catalyst can also be used. The type of the amine acetalization reaction catalyst is not particularly limited.
可使用習知使用於聚胺酯製造之胺酯化反應觸媒之任何一 種。相關胺醋化反應觸媒，例如可列舉由有機錫系化合物、 有機鋅系化合物、有機级系化合物、有機欽系化合物、有 機結系化合物、胺系化合物中選出之至少一種化合物等。 上述聚胺酯中源自異氰酸酯基之氮原子含有率較佳 是1.5至6質量%之範園内、更較佳是2至5質量%之範圍 内、再較佳是2. 5至5質量％之範圍内、尤其較佳是3至5 ^量％、特別較佳是4至5質量％。具有上述範圍之源自異 氰酸醋基之氮原子含有率之聚胺醋’與石夕酮之接著性優 異’並且’包含其等之聚胺_系構件為拉伸破斷強度或拉 伸破斷延伸度等所代表之力學雜、彎雜、彈性回復性、 耐熱性、電絕緣性等特性優異者。 上述聚胺S旨德㈣度以實施例揭示之方法測定時 較k於l’GGG至4，_pa· 3之範圍内、更較佳於 至3, 000Pa . s之範圍内。聚胺醋具有相關溶融黏度，可本 到溶融成雜優異、拉伸應力或㈣錢所代表之力料 性優異、、耐熱性亦優異之熱塑性聚賴之方面為有利的。 粒子成物係包含玻璃珠。玻璃珠通常為各伯 別=ί _。所使用之玻璃珠的種類崩 取得容易等觀點而言，較佳可使用軸混成祐 ime glass)所形成者。玻璃珠係可將微小的玻碎 321943 15 201041745 粉末吹入高溫纽中以浮遊狀‘㈣融而製造，亦可使用市 售者之樹脂用填充物。 使用玻璃珠的平均粒徑為3至45_範圍内者。玻璃 珠的平均粒徑未達3㈣、超過45_的情況中，聚胺醋系 構件與梦_構件之_以獲得充分的高接著強度。再 者，平均粒徑超過…_玻璃珠，使聚錢系構件的表 面凹凸變大而有外觀變差的傾向。麵珠时均粒徑較佳 為5至15’’更較佳為5至1Q//m。玻璃珠的平均粒徑為 _合範㈣’藉由相對於聚㈣為較少量的調配，可以 向接著強度接著聚胺S旨系構件射酮系構件。&，玻璃珠 的平均粒徑’係使用顯微鏡照相攝影玻璃珠，於所得照片 上㈣選擇5(M«璃珠’即可求出各個之最大徑的平均值 (50個最大徑的總和除以5〇之值）。 再者’作為玻璃珠，例如可使用含有通過使用網眼45 之師㈣振盪機之玻璃珠較佳為80質量％以上，更較佳為 95質量％以上者。 聚胺醋組成物中破璃珠的含有率，相對於聚胺醋⑽ 1量份fG·6/量份以上。_麵含轉㈣值更少 柃斤得之複σ成形體中聚胺酷系構件與石夕嗣系構件的接 ::度：低。再者’玻瑪珠的含有率過多時，藉由調配玻 类，伯i㈣胺_系構件與㈣系構件之接著強度提升效 丄旦於聚胺i旨系構件表面的凹凸變大而有外觀變差的 =向=㈣中玻璃珠的含有率，相對於聚胺錢〇質量 為〇. 6至30質量份的範圍内，更較佳為0.8至15 321943 16 201041745 質量份的範圍内，再較佳為U10質量份的範圍内。 構成本發明之複合成形體所具有之聚胺醋系構件之 聚胺酯組成物’可僅由上述之聚胺醋與破璃珠所成，亦可 進-步含有兩成分以外之其他成分。上述聚胺醋組成物中 上述聚胺醋與玻璃珠之合計含有率，較佳是5〇幻〇 %之範圍内、更較佳是80至刚質量％之範圍内、再較佳是 95至100質量％之範圍内、特別較佳是_質量％。 料上述聚細1與玻璃相外的其他成分，例如可列 舉脫模劑、補強劑、著色劑、難燃剩、紫外線吸收劑、氧 化防止劑、耐水解性提升劑、防黴劑、抗菌劑、安定 各=加劑；玻璃纖維、聚酉旨纖维等各種纖維；各種偶合 〇 ^發明之複合成形體所具有之上述聚胺酉旨系構件的製 2並無特別限制’可使用將上述之聚胺醋、玻璃珠 ”之甲』望所調配之其他成錢聽合姐融I練等所声 ，二胺s旨組_，亦可採用習知之成形技術之任-“ 二1 1例如藉由射出成形、擠壓成形、吹塑成形、吹穿 方法而成形為各種 取办 棒狀體、中空成形體1片材、薄膜、板片、管狀體、 錄模物許…各種各器、各種塊段狀成形體、各 成形、。上述成形方法中，較佳是採用射出成形、擠 廣機之掩壓成形或吹=开更較佳是採用使用單轴螺旋型擠 难擠壓機之圓筒溫声传最/。在該情況中’作為早軸螺旋 度係最好是180至230〇C之範圍内。 17 321943 201041745 [矽酮系構件] 可單獨由矽鯛所構X二::，形體所具有之矽鲷系構件 ，傅風，亦可由包含矽 成。上述㈣系構件令石夕綱的含 ^且成物所構 件與矽酮系構件之接著強产而a 由袄升聚胺酯系構 之範圍内、更較佳是8心質量=^ %至1〇〇貧量％之範圍 範圍内、再較佳是 间〇、符別較佳是〗〇〇暂旦 上述矽酮系組成物可 里°。 劑、補強劑、著色劑、成刀’例如可列舉脫模 劑、耐水解性提⑲丨 m、氧化防止 %獨战升劍、防黴劑、抗_ 加劑；玻璃纖維、聚酯纖 &劑寺各種添 無機物;各種偶合劑等等各種纖維;滑石、氧切等 地椹？成石夕嗣系構件切酮並無特別限制，由於可更问便 構成㈣系構件，較佳為硬化型石夕酮組成物。間便 進行成物’例如可使用⑴在常溫 成物、(=橡膠或石夕酮樹脂之常溫硬化型卿 加熱而進行硬化來成為石夕卿或石夕崎 業=甲基乙稀基石夕嗣等加熱硫化型石夕酉同橡膠組成物，由作 半2觀點而言’較佳是使用在硬化前呈柔軟之糊膏狀或 C動狀，理性優異之前述⑴之常温硬化型石夕·成 ’特別是在常溫硬化而成為賴橡膠之f溫硬化型石夕嗣 像膠組成物。 刖述（i)之常溫硬化型矽酮組成物中，有藉由空氣中 刀而硬化之1液型石夕_纟昇成物、藉由硬化劑而硬化之 18 321943 201041745 2液型梦酮組成物。一般而言’ 1液型之常溫硬化型梦酮組 成物係對於成形加工裝置或異種材料具有接著性’然而由 於有脫模性、處理性呈劣化之傾向，因此本發明中，較佳 是使用對於異種材料顯示優異之接著性且處理性優異之2 液型之常溫硬化型矽酮組成物’特別是2液型之常溫硬化 型矽酮橡膠組成物。 〇 〇 2液型之常溫硬化塑矽酮組成物係藉由導入於矽酮中 之官能基，大致分為縮合反應型和加成反應型之2種類。 縮合反應型係藉由錫化合物等觸媒而聚合羥基末端反應型 二有機基聚矽氧烷和烷氧基末端反應性二有機基聚石夕氧燒 者。另一方面，加成反應型係使用由鉑、把、銀、姥、锇、 訂等貴金屬化合物等所成之氫化矽烷基化觸媒，在常溫或 加熱下（在加熱之狀態下，一般為l5〇t以下之溫度。）， 使具有乙烯基等烯基之有機聚矽氧烷與具有結合於矽原子 之氫原子之有機氫聚矽氧烷（氫化聚矽氧烷）反應。 /本發明中，由於能夠順暢地製造聚胺酯系構件與矽酮 系構件之接㈣度提升之複合成雜，㈣是使用前述之 加成反應型之硬㈣㈣組成物。作為該加叙應型之硬 ^型：馳成物可使用⑷包含具有結合於石夕原子之氫原 聚錢絲氫魏基化觸叙硬化性㈣組成 聚石夕氧^⑷包含具有結合财原子之氫原子之有機氫 硬化型1具有絲之有機聚魏缺切録化觸媒之 成物中之有機氫種又（α)之硬化型矽酮組 ^ Α垸係具有烯基及/或絲之有機氫 321943 19 201041745 聚矽氧烷。 作為使用於上述)及（石）之硬化型矽綱έ且成物之 有機氫聚石夕氧燒，只m/且成物之 MU _ mi 要在1分子中具有1個以上之結合於 '、 里”之有機氫聚矽氧烷之任一者即 特 別限制。其等之中，作為有機氮聚石夕氧烧係，由柔軟^寺 !，：性特性、取得容易性、硬化性等觀點而；，較， 疋使用為-有機基聚石夕氧烧且藉由氮 :有機基《氧垸分子中_原子之 =個或2個以上之有機二氫議 土 將結合於二甲基聚石夕氧 权佐疋使用 上、特別是2至i 〇個置=為_子之甲基之^ 再者，作為上述⑷之石甲基氫聚石夕氧燒。 具有椒有機聚二 =二=使用之 無特別限制。其之任-者即可，並 由柔軟性、優異之弹性特：、:=之，氧炫， ;言’較佳是使用具有1個或2個以上二性等觀點 基之二有機聚石夕氧燒，、、、㈠於石夕原子之歸 烷分子中之石夕原子之甲 K吏用結合於二甲基聚石夕氧 置換成為稀基之上、特別是2至10個經 使用於上述（α)&(冷 虱聚石夕氧烧，以及使用於上更=型砂馳成物之有機 具有烯基之有機聚矽氧烷之：子旦：硬化型矽，組成物之 據本發明之複合成形體之用途等里使 別限制，可根 通s於各種用途者。 321943 20 201041745 使用於上述⑷及⑻之硬化型㈣組成物之 烧基化觸叙種_並無特_制，可以制習知 氫石夕烧基化觸媒之任何-種，例如可列舉n 之 锇、釕等貴金屬之錯化物；有機過氧 又、 等。轉之+ 乳物，偶I基化合物 、 B疋使用反應性高、處理性優異之包扭 化物’特収將氯化碰之醇溶液、氯二麵錯 而與含脂料不飽和烴基化合物配位者等、。文μ中和後 ΟAny of the amine esterification reaction catalysts conventionally used in the manufacture of polyurethanes can be used. The related amine acetalization reaction catalyst may, for example, be at least one selected from the group consisting of an organotin compound, an organic zinc compound, an organic grade compound, an organic compound, an organic compound, and an amine compound. The range of the content of the nitrogen atom derived from the isocyanate group is preferably in the range of from 1.5 to 6% by mass, more preferably from 2 to 5% by mass, even more preferably from 2. 5 to 5% by mass. The inside is particularly preferably from 3 to 5 % by volume, particularly preferably from 4 to 5% by mass. The polyamine vinegar having the nitrogen atom content of the isocyanate group having the above-mentioned range is excellent in adhesion to the oleanol and the polyamine-based member including the tensile breaking strength or stretching The characteristics such as mechanical complexity, bending, elastic recovery, heat resistance, and electrical insulation represented by the breaking elongation are excellent. The above polyamine S is determined to be in the range of l'GGG to 4, -pa·3, more preferably to 3,000 Pa·s, as measured by the method disclosed in the examples. The polyamine vinegar has an associated melt viscosity, and is advantageous in terms of excellent meltability, tensile stress, (4) excellent strength of the material represented by the money, and excellent heat resistance. The particle-forming system contains glass beads. Glass beads are usually the same as = ί _. From the viewpoint of easy disintegration of the type of glass beads to be used, it is preferable to use a shaft-mixed ime glass. The glass bead system can be used to blow a tiny glass of 321943 15 201041745 powder into a high temperature New Zealand to float in a floating state, and a resin filler for a commercial product can also be used. The glass beads are used in an average particle size ranging from 3 to 45 mm. In the case where the average particle diameter of the glass beads is less than 3 (four) and exceeds 45 Å, the polyurethane permeable member and the _ _ member are obtained to obtain a sufficiently high bonding strength. In addition, the average particle diameter exceeds the thickness of the glass beads, and the surface unevenness of the poly-money member tends to be large, which tends to deteriorate. The average particle diameter of the bead is preferably from 5 to 15'', more preferably from 5 to 1 Q/m. The average particle diameter of the glass beads is _following (four)', and the ketone-based member can be bonded to the subsequent strength of the polyamine S by a smaller amount of the composition with respect to the poly(tetra). &, the average particle size of the glass beads is obtained by using a microscope to photograph the glass beads. On the obtained photograph (4), 5 (M «glass beads' can be selected to obtain the average value of the maximum diameters (the sum of the 50 largest diameters divided by In addition, as the glass beads, for example, a glass bead containing a shaker using a mesh 45 (4) may preferably be used in an amount of 80% by mass or more, more preferably 95% by mass or more. The content of the glass beads in the vinegar composition is more than the amount of the fG·6/component of the polyamine vinegar (10) 1 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The connection of the components of the stone 嗣 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The amine i is intended to have a large unevenness on the surface of the member and the appearance is deteriorated. = The content of the glass beads in the direction = (4) is preferably in the range of 6 to 30 parts by mass, more preferably in the range of 6 to 30 parts by mass. 0.8 to 15 321943 16 201041745 Within the range of parts by mass, more preferably in the range of U 10 parts by mass. The polyurethane composition of the polyamine vinegar member which the composite molded body has may be formed only of the above-mentioned polyamine vinegar and the glass beads, and may further contain other components than the two components. The above polyamine vinegar composition The total content of the above polyamine vinegar and the glass beads is preferably in the range of 5 〇 〇 %, more preferably in the range of 80 to 9% by mass, still more preferably in the range of 95 to 100% by mass, It is particularly preferably _ mass%. The other components other than the above-mentioned fineness 1 and the glass phase include, for example, a release agent, a reinforcing agent, a coloring agent, a flame retardant residue, an ultraviolet absorber, an oxidation preventive agent, and an improvement in hydrolysis resistance. Agent, antifungal agent, antibacterial agent, diazepam = addition agent; various fibers such as glass fiber and polycrystalline fiber; and the above-mentioned polyamine enamel component of the composite molded body of the invention There is no special restriction 'the use of the above-mentioned polyamine vinegar, glass beads," which can be used to match the other aspects of the money, and the diamine s group, can also use the conventional forming technology.任任-"2 1 1 by injection molding, extrusion molding The blow molding and the blow-through method are formed into various rod-shaped bodies, hollow molded body 1 sheets, films, sheets, tubular bodies, and recording materials. Various devices, various block-shaped molded bodies, and moldings are formed. In the above-mentioned forming method, it is preferable to use the injection molding, the mask forming of the extruder or the blowing/opening, and it is more preferable to use the cylindrical temperature sound transmission using the single-axis spiral type extrusion extruder. In this case, 'as the early axis helicity system is preferably in the range of 180 to 230 〇 C. 17 321943 201041745 [Anthrone-based member] can be constructed solely by 矽鲷X::, the 矽鲷 system of the shape The member, Fu Feng, may also be composed of 矽成. The above-mentioned (4)-components make the components of Shi Xigang's inclusions and the components of the ketones and the ketone-keeling members stronger, and a is within the range of the swelled polyurethane structure. Preferably, it is within the range of 8 heart mass = ^ % to 1 〇〇 lean amount %, and more preferably 〇 〇 符 符 符 符 符 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 Agents, reinforcing agents, coloring agents, and forming knives include, for example, mold release agents, hydrolysis resistance, 19 丨m, oxidation prevention, singular warfare, antifungal agent, anti-additive; glass fiber, polyester fiber & Add a variety of inorganic substances; various coupling agents and other fibers; talc, oxygen cut and other mantle? The cutone of the Chengshixi system is not particularly limited, and since it is more desirable to constitute the (4) member, it is preferably a curable composition. For example, it is possible to use (1) a normal temperature product, (= rubber or a lyophilized resin, which is heated by a room temperature curing type to be hardened to become Shi Xiqing or Shi Xiqiye = methyl ethyl sulphate In the case of a heat-cured type of stone-like rubber composition, it is preferable to use a soft paste or a C-like shape before hardening, and the above-mentioned (1) room temperature hardening type Shi Xi· In particular, it is a composition of a thermosetting type of a sturdy rubber which is hardened at room temperature and has a hardening type of yttrium rubber. The room temperature hardening ketone composition (i) has a liquid which is hardened by a knife in the air. Type 夕夕_纟升成, hardened by a hardener 18 321943 201041745 2 liquid type dream ketone composition. In general, '1 liquid type of room temperature hardening type ketene composition for forming processing equipment or dissimilar materials In the present invention, it is preferable to use a two-liquid type room temperature curing type fluorenone composition which exhibits excellent adhesion to a dissimilar material and has excellent handleability. The object 'especially the 2-liquid type is hard at room temperature The composition of the oxime ketone rubber of the 〇〇2 liquid type is a functional group based on the ketone, and is roughly classified into two types of a condensation reaction type and an addition reaction type. The type is polymerized by a catalyst such as a tin compound to polymerize a hydroxyl-terminated reactive diorganopolyoxyalkylene oxide and an alkoxy-terminated reactive diorganopolyphosphorus. On the other hand, an addition reaction type is used. a hydrogenated ruthenium alkylation catalyst made of a platinum, a silver, a rhodium, a ruthenium, or a noble metal compound, etc., at a normal temperature or under heating (in a state of heating, generally a temperature of not more than 15 〇t), An organic polyoxyalkylene group such as a vinyl group or the like is reacted with an organic hydrogen polyoxyalkylene (hydrogenated polyoxyalkylene) having a hydrogen atom bonded to a halogen atom. / In the present invention, since the polyurethane member can be smoothly manufactured and (4) is a hard (four) (four) composition using the above-mentioned addition reaction type. As the additive type, the hard type can be used (4) contains a bond Shi Xi atomic hydrogen original Qian Qiansi Wei Kehua's catastrophic (4) composition of polychlorinated oxygen (4) contains an organic hydrogen sclerosing type 1 with a hydrogen atom bonded to a singular atom, and an organohydrogen species in the organic polyfluorination catalyzed catalyst (a) a hardened fluorenone group Α垸 an organic hydrogen having an alkenyl group and/or a silk 321943 19 201041745 a polyoxyalkylene. As a hardening type of scorpion used in the above) and (stone) The organic hydrogen polysulfide is oxidized, and only MU _ mi of the m/and the compound is particularly limited to have one or more organic hydrogen polyoxyalkylenes bonded to ', 里 in one molecule. In the case of the organic nitrogen polysulfide system, it is soft, and it is easy to obtain, and it is easy to obtain, and it is easy to obtain. From nitrogen: organic group "Oxygen oxime molecule _ atom = one or more than two organic dihydrogen collateral will be combined with dimethyl polychlorination, especially 2 to i 置 = Further, as the methyl group of the above-mentioned (4), it is a stone methyl hydrogen polysulfide of the above (4). There are no organic restrictions on the organic poly 2 of the pepper = two = use. It can be used as its own, and it is made of softness and excellent elasticity:::=, oxygen, and it is better to use two organic polystones with one or two or more views. Oxygen-fired,,,, (a) in the stone of the Shixia atom, the stone K of the stone atom is combined with the dimethyl group to form a thin base, especially 2 to 10 In the above (α) & (cold 虱 石 氧 氧 , 以及 以及 以及 , , , , , , , , , , , = = = = = = = = = = = = = = 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧The use of the composite molded article of the present invention is not limited, and can be used for various purposes. 321943 20 201041745 The alkylation type of the hardened (four) composition used in the above (4) and (8) _ no special _ Any one of the types of hydrogen catalyzed catalysts can be prepared, for example, a complex of a noble metal such as ruthenium or osmium; an organic peroxygen, etc., a carbamide, an even I-based compound And B疋 uses a high-reactivity, excellent handleability of the twisted compound's special chlorinated alcohol solution, chlorine diffractory and Unsaturated hydrocarbon compound material by complexing the like. Paper and after Ο μ
G 上述U)及⑷之硬化型矽_組成物 觸媒之含有量，於⑷魏—晚祕崎^燒基化 =具有結合於㈣子之氫原子之有機氫^ =對 lppm至1質量％左右，特別可為1〇 虱烷，較佳為 硬化型矽嗣組成物的情況中 〇卯m左右；於（沒: 氳原子之有機氫聚魏烧與具有=具有結合Μ原子之 計質量，較佳為1卿至1質量％左右t =機聚石夕氧燒之合 左右。 右特別可為10至5。0_ 又，上述硬化型矽酮組成物， 或印刷油墨。 ’為石夕_系之接著劑 本發明之複合成形體，可以 2個以上和矽蜩系構件之i或2個γ聚胺酯系構件之i或 具有聚胺Μ構件和_系構件固以上所組成，或者亦可 構件[例如，聚合物、構成聚胺^及由其他材料所成之 外之聚合物組成物、紙、布帛、金構件之聚胺_組成物以 之構件；以下，簡稱為「其他 jH、木材等所成 上。 、件」]之1者或2者以 201041745 /再者本發明之複合成形體中，聚胺酯系構件與矽酮 糸構件雖然接觸，但該接觸亦可為兩構件之至少一部分接 觸複°成形體具有2者以上之聚胺醋系構件及/或2者以 上之石夕酮系構件的情況中’亦可為至少1個聚胺醋系構件 至>、1個矽酮系構件為兩構件之至少一部分接觸。 本發明之複合成形體’較佳是使層狀聚胺醋系構件 [以下簡稱為「聚胺酯層」]與層狀矽酮系構件[以下，簡 稱為石夕鋼層」]接著層合者。此方式之複合成形體之層數 係並無特別限制，可以是2層構造體、3層構造體、4層構 體5層以上之構造體之任何一種。進一步地，在具有 聚胺酯層和石夕酮層之複合成形體中，在具有聚胺醋層、矽 _層與層狀之其他材料構件[以下，簡稱為「其他材料層」] 之情況中，聚胺酯層及/或矽酮層與其他材料層，可以接著 及層積於1個面之整個面，或者也可以連續或斷續地進行 接著層合（例如線接著、點接著、部分之面接著等）。 作為具有聚胺酯層和矽酮層之複合成形體之例，係例 如可列舉由聚胺酯層/矽酮層所成之2層構造體；由矽嗣層 /聚胺酯層/矽酮層所成之3層構造體；由聚胺酯層/矽g同層 /聚胺酯層所成之3層構造體；由聚胺酯層/矽酮層/聚胺酉旨 層/矽酮層所成之4層構造體；其他材料層（例如由紙、布 帛、金屬、其他聚合物等所成之層）/矽酮層/聚胺酯層所成 之3層構造體；由矽酮層/聚胺酯層/其他材料層（例如由 紙、布帛、金屬、其他聚合物等所成之層）所成之3層構造 體；矽酮層/聚胺酯層/矽酮層/聚胺酯層/其他材料層（例如 321943 22 201041745 由紙、布帛、金屬、其他聚合物等所成之層）所成之5層構 造體等。 在1個複合成形體中存在2個以上之聚胺酯層之情況 中，該2個以上之聚胺酯層，只要滿足上述聚胺酯系構件 之要件即可，可為全部是相同之層，或者所包含聚胺酯之 種類、含有量、層厚度等不同之層之任一者。 再者，1個複合成形體中存在2個以上之矽酮層之情 況中，該2個以上之矽酮層可為全部是相同之層，或者是 ◎ 不同之層之任一者。 經接著層合上述聚胺酯層和矽酮層之複合成形體中， 複合成形體之整體厚度、聚胺酯層厚度及矽酮層厚度並無 特別限制，可根據複合成形體之用途等而進行調整。 一般而言，由複合成形體之製造容易性、層間接著力 等觀點而言，聚胺酯層（1層）之厚度是10/zm以上、較佳 是20至3, 000 /zm之範圍内、更較佳是50至2, 000 # m之 〇 範圍内，而矽酮層（1層）之厚度是10/ζιη以上、較佳是20 至3, 000 /zm之範圍内、更較佳是50至2, 000 μ m之範圍内。 再者，由製造之容易性、耐熱性、後加工之步驟通過 性等觀點而言，聚胺酯層較佳是形成為膜狀。作為該膜之 厚度較佳是20至300 //m之範圍内、更較佳是30至200 //m 之範圍内、再較佳是40至150/zm之範圍内。 本發明之複合成形體之製造方法並無特別限定，由於 可容易地製造不實施表面活性處理而即提升聚胺酯系構件 與矽酮系構件的接著強度之複合成形體，較佳採用包含藉 23 321943 201041745 由於聚胺酯系構件上使硬化型矽酮組成物硬化而於聚胺酯 系構件上形成矽酮系構件之步驟的方法。於聚胺酯系構件 上上使硬化型矽酮組成物硬化之具體方法，並無特別限 制，例如可以採用在由聚胺酯系構件或由聚胺酯系構件和 其他材料構件所成之複合體之聚胺酯系構件上，被覆硬化 型矽酮組成物，進行硬化而製造複合成形體之方法；以聚 胺酯系構件配置（插入）於模具内之狀態，將硬化型矽酮組 成物在熔融下，填充於模具内，進行硬化使接著·一體化 之方法；在硬化型矽酮組成物為熱塑性之情況中，於聚胺 酯系構件上，擠壓硬化性矽酮組成物而接著•硬化•一體 化之方法等。再者，可以採用在聚胺酯系構件上塗佈作為 硬化性矽酮組成物之矽酮系接著劑或印刷油墨後，使其硬 化之方法。 再者，構成聚胺酯系構件之聚胺酯組成物與硬化型矽 酮組成物皆為熱塑性之情況，亦可藉由將聚胺酯組成物與 硬化型矽酮組成物共擠壓成形，使接著•硬化•一體化而 製造本發明之複合成形體。 本發明之複合成形體，可根據構成複合成形體之聚胺 酯系構件或矽酮系構件之性質，甚至根據構成複合成形體 之其他材料構件之材質或性質等，而使用於各種用途。例 如可以使用在儀器面板、中心面板、中央控制箱、門花邊、 墩柱、輔助夾鉗、把手、安全氣囊蓋等汽車内裝零件；隄 道等汽車外裝零件；使用於吸塵器保險桿、電冰箱接點、 相機夾鉗、電動工具夾鉗、家庭用調理器具、遙控器開關、 24 321943 201041745 0A機器之各種鍵帽、按鈕開關（使用於行動電話、家電製 品、汽車零件、通訊機器等）之各種按鍵片材或鍵盤、機架 等家電零件；水中眼鏡等運動用品；各種蓋子；以耐摩耗 性、密閉性、隔音性、防振性等作為目的之各種之附包裝 工業零件；捲曲電線被覆；帶子；軟管；管子；鞋底；手 錶帶；消音齒輪；輸送帶；層合品；各種容器；各種電機、 電子零件；各種機械零件；各種防振材料等。 ^ 其等之中，由於本發明之複合成形體，即使不施行表 Ο 面活化處理，也充分地接著聚胺酯系構件和石夕酮系構件， 因此，可以適合使用作為構成在行動電話等通訊終端機、 各種計測器、個人電腦輸入用鍵盤及遙控裝置之操作部等 用之按鍵墊之素材。該按鍵墊對於本發明之複合成形體， 較佳為接著層合聚胺酯層和矽酮層之複合成形體，根據需 要，藉由裁斷、沖裁、切削等，加工成為所要求之尺寸、 形狀即可製造。再者，亦可以在按鍵墊，藉由研削或雷射 〇等而形成所要求之溝槽或孔穴等。另外，亦可設置用以在 按鍵墊配置鍵帽（key top)之凹凸；用以配置將設置於按鍵 片材之下面之鍵盤開關予以按壓用之插梢之凹凸；設置用 以使得按鍵墊本身可以具有鍵帽或插梢等之功能之凹凸等 之各種凹凸。該等凹凸係可以藉由對於本發明之複合成形 體，施行壓縮成形（沖壓成形）、真空成形等而形成。 藉由在前述按鍵墊之規定位置配置按鈕鍵等之鍵帽 等，可成為具有前述按鍵墊及鍵帽之按鍵片材。再者，按 鍵片材除了前述之鍵帽以外，亦可以具有插梢等。鍵帽或 25 321943 201041745 ，梢等對㈣鍵墊之配置可以使用化學反 劑而進行0作為成分之接著劑等）或⑽接著劑等之接著 [實施例] 以下’藉由實施例而具體地說明本發明曰 明係並非由於這些實施例而受到任何限^。此^^本發 之實施例及比較例’聚胺I系構件和矽酮系構件之接：下 度及聚胺i旨軸減係藉由以下之方法而進行測，強 價。 < D平 (1) 熱塑性聚胺酯之熔融黏度： 使用高化式流速測驗器（島津製作所股份有限公司 製）’在荷重490.3N(50kgf)、喷嘴尺和直徑—長度 10mm、溫度200°C之條件下，測定在肋它減壓乾燥〇〇t〇rr 以下）2小時之熱塑性聚胺酯之熔融黏度。 (2) 聚胺酯系構件和矽酮系構件之接著強度： 使用以下之實施例和比較例得到之複合成形體，使用 島津製作所股份有限公司製之「自動圖形剩定裝置 IS-500D」，在室溫下、拉伸速度50mm/分鐘之條件，測定 在18 0度剝離试驗中剝離聚胺醋糸構件和發酮系構件時之 抵抗值（接著強度），作為接著性之指標。 以下，顯示關於以下之實施例及比較例所使用之化合 物之縮寫和内容。 《高分子多元醇》 ΡΟΗ ·· 1，4-丁二醇與己二酸反應而製造，每1分子之 321943 26 201041745 經基數為2.00、數平均分子量為1,000之聚（1，4-四亞曱 基己二酸酯）二醇。 《有機多異氰酸酯》 MDI: 4,4’ -二苯基甲烷二異氰酸酯 《鏈延長劑》 BD : 1，4-丁二醇 《胺酯化反應觸媒》 ^ SN :二乙酸二丁基錫 〇 《製造例1》 熱塑性聚胺酯的製造 將包含lOppm之胺酯化反應觸媒（SN)之高分子多元醇 (ΡΟΗ)、鏈延長劑（BD)和有機多異氰酸酯（MDI)，以ΡΟΗ : BD : MDI之莫耳比成為1. 00 : 2. 75 : 3. 75(源自異氰酸酯基 之氮原子含有率為4. 8質量％)且該等之合計供應量成為 200g/分鐘之方式，連續地供應至於同軸方向旋轉之二軸螺 Ο 旋型擠壓機（3Omm0、L/D=36 ;加熱區域係分成為前部、 中央部和後部之3個區域）之加熱區域之前部，在260°C， 連續熔融聚合而進行聚胺酯形成反應。所得到之熔融物， 呈線束狀地連續擠壓於水中，其次藉由造粒器進行切斷。 所得到顆粒在80°C，進行4小時之除濕乾燥，而製造熱塑 性聚胺酯。該熱塑性聚胺酯之熔融黏度以上述方法測定。 結果示於表1。 《實施例1至4、比較例1及2》 複合成形體之製造 27 321943 201041745 藉由進彳fU#“使由製造例i得到之聚胺醋 璃珠（Potters-Ballotini 公司製之「Γΐ5Γ?ίιι 、 ’材質；鈉鈣 混成玻璃’使用師振盡機時通過網眼^ 艮45#m的篩的玻璃珠 含有率：99質量％以上’平均粒徑32心）所得之膜之兩成分 之含有率，成為表I所示之值之方式，使用τ模型擠壓成 形機（25_、圓筒溫度18〇至2〇代、模溫度副。c)將並 溶融混練之後’擠壓至3(TC之冷啣滾筒上，進行冷卻而成 為膜（厚度1〇〇//πι) ’以大約2m/分鐘之捲繞速度捲繞該 膜，而製造由聚胺酯組成物所構成之膜。 接者，由得到之各膜（捲繞之膜）切出幅寬25腿、長度 100mm之试驗片。在該试驗片，塗佈大約以瓜厚度之液 狀硬化型石夕酮組成物（信越化學工業股份有限公司製之「信 越石夕酮KE-2030」（混合A液和B液之液體）），在i20°C之 熱風乾燥機中，放置3分鐘，得到由聚胺酯系構件和矽酮 系構件所構成之2層構造之複合成形體。使用得到之複合 成形體藉由前述之方法測定聚胺酯系構件與矽酮系構件之 接著強度。結果顯示於表1。 《實施例5至7》 複合成形體之製造 作為玻璃珠，使用Potters-Ballotini公司製之 「EMB-10」（材質；鈉鈣混成玻璃，使用篩振盪機時通過網 眼38//m的篩的玻璃珠含有率：100質量％，平均粒徑20 A m)、Potters-Bal lot ini 公司製之「EMB-20」（材質丨納 鈣混成玻璃，使用篩振盪機時通過網眼45/zm的篩的玻璃 28 321943 201041745 珠含有率：1〇〇質量％，平均粒徑10//m)或G The content of the hardening type 组成_composition catalyst of the above U) and (4) is (4) Wei-night Misaki = organic hydrogen having a hydrogen atom bonded to (four) ^ = 1 ppm to 1% by mass The left and right may be, in particular, 1 decane, preferably in the case of a hardened ruthenium composition, about 〇卯m; (not: the organic hydrogen of the ruthenium atom, and the quality of the Μ atom with a combination of Μ, It is preferably from about 1 to about 1% by mass. t = about concentrating on the concentrating gas. The right is particularly from 10 to 5.0. Further, the above-mentioned hardened fluorenone composition, or printing ink. The adhesive composition of the present invention may be composed of two or more i or two γ urethane-based members of the lanthanide member or a polyamine amide member and a _-based member, or may be a member. [For example, a polymer, a polymer composition constituting a polyamine, and a polymer composition other than a material, a paper, a cloth, or a polyamine-based composition of a gold member; hereinafter, simply referred to as "other jH, wood, etc." One or two of the above-mentioned parts, or one of the two parts, in 201041745 / in the composite molded body of the present invention, Although the ester-based member and the fluorenone oxime member are in contact with each other, the contact may be at least a part of the two members contacting the complex molded body having two or more polyamine vine-based members and/or two or more of the oleanyl-based members. In the case of 'at least one polyurethane-based member to>, one fluorenone-based member is in contact with at least a part of the two members. The composite formed body of the present invention is preferably a layered polyamine-based member. [hereinafter, simply referred to as "polyurethane layer"] and a layered fluorenone-based member (hereinafter, simply referred to as "Shixia steel layer"] are laminated. The number of layers of the composite molded body in this embodiment is not particularly limited, and may be 2 Any one of a layer structure, a three-layer structure, and a structure of five or more layers of a four-layer structure. Further, in a composite molded body having a polyurethane layer and a linoleic layer, a polyamine layer, 矽_ In the case of a layer and a layer of other material member [hereinafter, simply referred to as "other material layer"], the polyurethane layer and/or the fluorenone layer and the other material layer may be laminated and laminated on the entire surface of one surface, or It is also possible to carry out the subsequent lamination continuously or intermittently (for example Then, as a composite molded body having a polyurethane layer and an anthrone layer, for example, a two-layer structure composed of a polyurethane layer/anthrone layer; a three-layer structure composed of a polyurethane layer/an oxone layer; a three-layer structure composed of a polyurethane layer/矽g layer/polyurethane layer; a polyurethane layer/anthrone layer/polyamine layer/anthone a four-layer structure formed by layers; a three-layer structure made of other material layers (for example, layers made of paper, cloth, metal, other polymers, etc.)/anthrone layer/polyurethane layer; a three-layer structure of a polyurethane layer/other material layer (for example, a layer formed of paper, cloth, metal, other polymer, etc.); an anthrone layer/polyurethane layer/anthrone layer/polyurethane layer/other material layer ( For example, 321943 22 201041745 is a five-layer structure made of paper, cloth, metal, or other polymer. In the case where two or more polyurethane layers are present in one composite molded body, the two or more polyurethane layers may be all the same layers or contain polyurethanes as long as they satisfy the requirements of the above-mentioned polyurethane-based members. Any of different layers such as type, content, and layer thickness. Further, in the case where two or more fluorenone layers are present in one composite molded body, the two or more fluorenone layers may be all the same layer or ◎ different layers. In the composite molded body in which the polyurethane layer and the fluorenone layer are laminated, the overall thickness of the composite molded article, the thickness of the polyurethane layer, and the thickness of the fluorene ketone layer are not particularly limited, and can be adjusted according to the use of the composite molded article or the like. In general, the thickness of the polyurethane layer (one layer) is 10/zm or more, preferably 20 to 3,000 /zm, from the viewpoints of ease of production of the composite molded body, interlayer adhesion, and the like. Preferably, the thickness of the fluorenone layer (1 layer) is 10/ζιη or more, preferably 20 to 3,000 /zm, more preferably 50. Up to 2,000 μm. Further, the polyurethane layer is preferably formed into a film shape from the viewpoints of easiness of production, heat resistance, and processability of post-processing. The thickness of the film is preferably in the range of 20 to 300 //m, more preferably in the range of 30 to 200 //m, still more preferably in the range of 40 to 150/zm. The method for producing the composite molded article of the present invention is not particularly limited, and a composite molded body which does not carry out the surface active treatment, that is, the adhesive strength of the polyurethane-based member and the fluorenone-based member, can be easily produced, and it is preferable to include the borrowing 23 321943 201041745 A method of forming a fluorenone-based member on a polyurethane-based member by curing the hardened fluorenone composition on the polyurethane member. The specific method of hardening the hardened fluorenone composition on the polyurethane-based member is not particularly limited, and for example, it can be used on a polyurethane-based member composed of a polyurethane-based member or a composite of a polyurethane-based member and other material members. And a method of producing a composite molded body by curing the cured fluorenone composition; and arranging (inserting) the polyurethane component into a mold, and filling the cured fluorenone composition in a mold under melting; In the case where the curing type fluorenone composition is thermoplastic, the sclerosing fluorenone composition is extruded on the polyurethane member, followed by a method of hardening and integrating. Further, a method in which an oxime-based adhesive or a printing ink which is a sclerosing fluorenone composition is applied to a polyurethane member and then hardened can be used. Further, in the case where the polyurethane composition constituting the polyurethane-based member and the curable fluorenone composition are both thermoplastic, it may be co-extruded by forming the polyurethane composition and the hardened fluorenone composition, thereby enabling the subsequent hardening and integration. The composite formed article of the present invention is produced. The composite molded article of the present invention can be used in various applications depending on the properties of the polyurethane-based member or the fluorenone-based member constituting the composite molded article, or even the material or properties of other material members constituting the composite molded article. For example, it can be used in automobile panel parts such as instrument panel, center panel, central control box, door lace, pier column, auxiliary clamp, handle, airbag cover, etc.; automobile exterior parts such as causeway; used for vacuum cleaner bumper, electricity Refrigerator contacts, camera clamps, power tool clamps, household conditioning appliances, remote control switches, 24 321943 201041745 0A machine various keycaps, push button switches (used in mobile phones, home appliances, auto parts, communication machines, etc.) Various key sheets or keyboards, racks and other household appliances; water glasses and other sporting goods; various covers; various packaging industrial parts for the purpose of abrasion resistance, airtightness, sound insulation, vibration resistance, etc.; Cover; belt; hose; pipe; sole; watch belt; silencer gear; conveyor belt; laminate; various containers; various motors, electronic parts; various mechanical parts; various anti-vibration materials. In the composite molded article of the present invention, the polyurethane-based member and the oleanyl-based member are sufficiently adhered to each other without performing the surface activation treatment, and therefore, it can be suitably used as a communication terminal such as a mobile phone. The material of the button pad used for the machine, various measuring instruments, the keyboard for personal computer input, and the operation unit of the remote control device. The key pad of the present invention is preferably a composite molded body in which a polyurethane layer and an anthrone layer are laminated, and if necessary, processed into a desired size and shape by cutting, punching, cutting, or the like. Can be manufactured. Further, it is also possible to form desired grooves or cavities by grinding or laser licking on the key pad. In addition, a bumper for arranging a key top on the button pad may be disposed; and configured to configure a bump formed by pressing a keyboard switch disposed under the button sheet; and configured to make the button pad itself It is possible to have various irregularities such as a bump such as a key cap or a tip. These irregularities can be formed by subjecting the composite molded article of the present invention to compression molding (press molding), vacuum molding, or the like. By arranging a key cap or the like of a button key or the like at a predetermined position of the button pad, the button sheet having the button pad and the key cap can be obtained. Further, the key sheet may have a tip or the like in addition to the aforementioned key cap. Key cap or 25 321943 201041745, the tip or the like (four) key pad can be placed using a chemical counter-agent to carry out 0 as a component of an adhesive, etc.) or (10) an adhesive or the like. [Examples] Hereinafter, by way of example, It is to be understood that the invention is not limited by the embodiments. The examples of the present invention and the comparative example 'the combination of the polyamine I-based member and the fluorenone-based member: the lower degree and the polyamine i-axis reduction were measured by the following methods and were strong. < D flat (1) Melt viscosity of thermoplastic polyurethane: Using a high-speed flow rate tester (manufactured by Shimadzu Corporation), load 490.3N (50kgf), nozzle ruler and diameter - length 10mm, temperature 200 °C Under the conditions, the melt viscosity of the thermoplastic polyurethane was measured for 2 hours under the pressure of ribs to dry 〇〇t〇rr. (2) Adhesive strength of the polyurethane-based member and the fluorenone-based member: The composite molded body obtained by the following Examples and Comparative Examples was used in the "Automatic Pattern Retention Device IS-500D" manufactured by Shimadzu Corporation. The resistance value (adjacent strength) when the polyamine vinegar member and the ketone-based member were peeled off in the 180 degree peeling test was measured under the conditions of the temperature and the tensile speed of 50 mm/min, and was used as an index of the adhesion. Hereinafter, the abbreviations and contents of the compounds used in the following examples and comparative examples are shown. "Polymer Polyol" ΡΟΗ ·· 1,4-butanediol is produced by reacting with adipic acid, each of which is 321943 26 201041745 with a base number of 2.00 and a number average molecular weight of 1,000 (1,4-tetra Mercapto adipate) diol. "Organic polyisocyanate" MDI: 4,4'-diphenylmethane diisocyanate "chain extender" BD : 1,4-butanediol "amine esterification reaction catalyst" ^ SN : dibutyltin diacetate "manufacture Example 1 Production of Thermoplastic Polyurethane A polymer polyol (ΡΟΗ), a chain extender (BD), and an organic polyisocyanate (MDI) containing 10 ppm of an amine esterification reaction catalyst (SN), ΡΟΗ : BD : MDI The molar ratio becomes 1. 00: 2.75: 3.75 (the nitrogen atom content derived from the isocyanate group is 4.8 mass%), and the total supply amount becomes 200 g/min, and is continuously supplied to The two-axis screw in the coaxial direction, the rotary extruder (3Omm0, L/D=36; the heating zone is divided into three areas of the front, the center and the rear), at 260 ° C, The polyurethane formation reaction is carried out by continuous melt polymerization. The obtained melt was continuously extruded in water in a strand shape, and then cut by a granulator. The obtained pellets were dehumidified and dried at 80 ° C for 4 hours to produce a thermoplastic polyurethane. The melt viscosity of the thermoplastic polyurethane was measured by the above method. The results are shown in Table 1. <<Examples 1 to 4, Comparative Examples 1 and 2>> Production of composite molded body 27 321943 201041745 By using 彳fU# "The urethane glass beads obtained by the production example i ("5 Γ ί ί Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po Po , 'Materials; Sodium-calcium mixed glass' contains the glass beads of the sieve of the mesh ^45#m when the machine is used up, and the content of the two components of the obtained film is 99% by mass or more. The rate is the value shown in Table I, using a τ model extrusion molding machine (25_, cylinder temperature 18 〇 to 2 〇 generation, mold temperature pair. c) and then melt-mixed and then 'squeezed to 3 (TC The cold-rolling cylinder was cooled to form a film (thickness: 1 〇〇//πι). The film was wound at a winding speed of about 2 m/min to produce a film composed of a polyurethane composition. Each of the obtained films (the wound film) was cut out into a test piece having a width of 25 legs and a length of 100 mm. In the test piece, a liquid-like hardening type of lycopene composition having a thickness of about guar was applied (Shin-Etsu Chemical Industry) "Shin-Etsu ketone KE-2030" (mixed liquid A and liquid B), In a hot air dryer of i20 ° C, it was allowed to stand for 3 minutes to obtain a composite molded body having a two-layer structure composed of a polyurethane-based member and an fluorenone-based member. The obtained composite molded body was used to measure the polyurethane-based member and the method described above. The adhesive strength of the fluorenone-based member. The results are shown in Table 1. "Examples 5 to 7" Production of composite molded article As the glass beads, "EMB-10" (material; sodium-calcium mixed glass, manufactured by Potters-Ballotini Co., Ltd.) was used. When using a sieve shaker, the glass bead content of the sieve passing through the mesh 38//m is 100% by mass, the average particle diameter is 20 A m), and the "EMB-20" manufactured by Potters-Bal Lot ini Co., Ltd. Blended glass, glass through the mesh 45/zm sieve when using a sieve shaker 28 321943 201041745 Bead content: 1〇〇 mass%, average particle size 10//m)
Potters-Ballotini公司製之「GB210」（材質；納約混成 玻璃，使用篩振盪機時通過網眼45/zm的篩的玻璃珠含有 率：99質量％以上，平均粒徑18/zin)，取代"GB210" made of Potters-Ballotini (material; nano-mixed glass, glass bead content of mesh 45/zm sieve using sieve shaker: 99 mass% or more, average particle size 18/zin), replaced
Potters-Bal lotini公司製之「GB731」，所得膜中之熱塑 性聚胺酯與玻璃珠之含有率以成表1所示之值的方式乾式 掺合，其他與實施例1同樣操作，製造由聚胺酯所成之膜， ^ 進一步地獲得由聚胺酯系構件與矽酮系構件所成之2層構 〇 造的複合成形體。使用得到之複合成形體藉由前述之方法 測定聚胺酯系構件與矽酮系構件之接著強度。結果顯示於 表1。 《比較例3》 複合成形體之製造 作為玻璃珠，使用Potters-Ballotini公司製之 「GB301S」（材質；鈉約混成玻璃，平均粒徑50//Π1)，取 Ο 代Potters-Bal lotini公司製之「GB731」，所得膜中之熱 塑性聚胺酯與玻璃珠之含有率以成表1所示之值的方式乾 式摻合，其他與實施例1同樣操作，製造由聚胺酯所成之 膜，進一步地獲得由聚胺酯系構件與矽酮系構件所成之2 層構造的複合成形體。使用得到之複合成形體藉由前述之 方法測定聚胺酯系構件與矽酮系構件之接著強度。結果顯 示於表1。 《比車交例4、5》 複合成形體之製造 29 321943 201041745 使用氧化矽（TOSOH SILICA公司製，「Nipsil E743」， 平均粒徑1. 5“in)或氧化矽（TOSOH SILICA公司製，「Nipsil E200A」，平均粒徑2.5/zm)取代玻璃珠，所得膜中之熱塑 性聚胺酯與玻璃珠之含有率以成表1所示之值的方式乾式 摻合，其他與實施例1同樣操作，製造由聚胺酯所成之膜， 進一步地獲得由聚胺酯系構件與矽酮系構件所成之2層構 造的複合成形體。使用得到之複合成形體藉由前述之方法 測定聚胺酯系構件與矽酮系構件之接著強度。結果顯示於 表1。 表1 實施仞 比較伸 1 2 3 4 5 6 7 1 2 3 4 5 熱塑性聚胺酯 質量份 100 100 100 100 100 100 100 100 100 100 100 100 玻璃珠1 質量份 1.0 5.0 10 15 0.1 0.5 玻璃珠2 質量份 1.0 玻璃珠3 質量份 1.0 玻璃珠4 質量份 1.0 玻璃珠5 質量份 1.0 氧化矽1 質量份 1.0 氧化矽2 質量份 1.0 熱塑性聚胺酯 的熔融黏度 Pa * s 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 接著強度 g/cm 109 509 564 573 545 545 136 11 23 53 20 20 玻璃珠1 :玻璃珠GB731 (Potters-Ballotini公司製，平均粒子徑32//m) ik璃沐2 :玻璃滅EMB-l (j(Potters-Bal lotini公司製，平均粒子徑5私111) 玻璃珠3 :玻璃珠EMB-20(Potters-Ballotini公司製，平均粒子徑10以m) 玻璃沐4 ··玻璃沐GB210(Potters-Ballotini公司製，平均粒子徑18/im) 玻璃珠5 :玻璃珠GB301S(Potters-Ballotini公司製，平均粒子徑50^m) 氧化矽 1 : Nipsii E743(T0S0H SILICA 公司製，粒徑 1. 5/zm) 氧化矽 2 : Nipsil E200A(TOSOH SILICA 公司製，粒徑 2. 5仁 m) 實施例1至7之複合成形體具有透明性，無外觀的問 題，聚胺酯系構件與矽酮系構件具有充分高的接著強度。 相對於此，比較例1至5之複合成形體，聚胺酯系構件與 石夕嗣系構件之接著強度低，再者，比較例4及5之複合成 30 321943 201041745 形體為透明性消失，產生空穴等。 [產業上之可利用性] 根據本發明，不施行表面活化處理亦可製造，得到包 含聚胺酯之構件和包含矽酮之構件充分地接著之複合成形 體。該複合成形體係特別有用於作為構成使用在行動電話 等通訊終端機、各種計測器、個人電腦輸入用鍵盤及遙控 裝置之操作部等所用按鍵墊之素材。 本申請案係以在曰本申請之日本特願2009-083952作 ❹ 為基礎，這些内容係全部包含於本說明書。 【圖式簡單說明】 益 【主要元件符號說明】 無 31 321943"GB731" manufactured by Potters-Bal lotini Co., Ltd., the content of the thermoplastic polyurethane and the glass beads in the obtained film was dry blended so as to have the values shown in Table 1, and the same procedure as in Example 1 was carried out to produce a polyurethane. Film, ^ Further, a composite molded body made of a two-layer structure made of a polyurethane-based member and an anthrone-based member was obtained. Using the obtained composite molded body, the adhesive strength of the polyurethane-based member and the fluorenone-based member was measured by the aforementioned method. The results are shown in Table 1. Comparative Example 3 Production of a composite molded article As a glass bead, "GB301S" (material; sodium about mixed glass, average particle diameter 50//Π1) manufactured by Potters-Ballotini Co., Ltd. was used, and was manufactured by Potters-Bal lotini Co., Ltd. In "GB731", the content of the thermoplastic polyurethane and the glass beads in the obtained film was dry blended so as to have the values shown in Table 1, and the same procedure as in Example 1 was carried out to produce a film made of polyurethane, which was further obtained. A composite molded body having a two-layer structure composed of a polyurethane-based member and an fluorenone-based member. The adhesive strength of the polyurethane-based member and the fluorenone-based member was measured by the above method using the obtained composite molded article. The results are shown in Table 1. "Comparative example 4, 5" Manufacturing of composite molded bodies 29 321943 201041745 Using yttrium oxide ("Nipsil E743", manufactured by TOSOH SILICA Co., Ltd., average particle size 1. 5" in) or yttrium oxide (manufactured by TOSOH SILICA, " Nipsil E200A", an average particle diameter of 2.5 / zm) was substituted for the glass beads, and the content of the thermoplastic polyurethane and the glass beads in the obtained film was dry blended so as to have the values shown in Table 1, and the same operation as in Example 1 was carried out. Further, a composite formed of a two-layer structure composed of a polyurethane-based member and an fluorenone-based member was obtained from a film made of a polyurethane. Using the obtained composite molded body, the adhesive strength of the polyurethane-based member and the fluorenone-based member was measured by the aforementioned method. The results are shown in Table 1. Table 1 Example 仞Comparative extension 1 2 3 4 5 6 7 1 2 3 4 5 Thermoplastic polyurethane mass parts 100 100 100 100 100 100 100 100 100 100 100 100 100 Glass beads 1 part by mass 1.0 5.0 10 15 0.1 0.5 Glass beads 2 parts by mass 1.0 Glass beads 3 parts by mass 1.0 Glass beads 4 parts by mass 1.0 Glass beads 5 parts by mass 1.0 cerium oxide 1 parts by mass 1.0 cerium oxide 2 parts by mass 1.0 Melt viscosity of thermoplastic polyurethane Pa * s 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 2300 Next strength g/cm 109 509 564 573 545 545 136 11 23 53 20 20 Glass beads 1: Glass beads GB731 (Potters-Ballotini, average particle diameter 32//m) ik Glass 2: Glass extinguished EMB-l (j (manufactured by Potters-Bal lotini, average particle diameter 5 private 111) Glass beads 3: Glass beads EMB-20 (manufactured by Potters-Ballotini, average particle diameter 10 m) Glass Mu 4 ··Glass GB210 (Potters -Ballotini company, average particle diameter 18/im) Glass beads 5: Glass beads GB301S (Potters-Ballotini, average particle diameter 50^m) Cerium oxide 1: Nipsii E743 (T0S0H Manufactured by SILICA, particle size 1. 5/zm) yttrium oxide 2: Nipsil E200A (manufactured by TOSOH SILICA Co., Ltd., particle size 2. 5 ren m) The composite molded bodies of Examples 1 to 7 have transparency and no appearance problem. The polyurethane-based member and the fluorenone-based member have sufficiently high bonding strength. On the other hand, in the composite molded articles of Comparative Examples 1 to 5, the bonding strength between the polyurethane-based member and the lithium-based member is low, and Comparative Example 4 and 5 composited into 30 321943 201041745 The shape disappears from transparency, and voids are generated. [Industrial Applicability] According to the present invention, it can be produced without performing surface activation treatment, and a member containing polyurethane and a member containing an anthrone can be obtained. The composite molded body is sufficiently used as a material for a key pad used for a communication terminal such as a mobile phone, various measuring devices, a keyboard for inputting a personal computer, and an operation unit of a remote control device. The present application is based on Japanese Patent Application No. 2009-083952, the entire contents of which is incorporated herein by reference. [Simple description of the diagram] Benefits [Main component symbol description] None 31 321943