200937471 九、發明說明 【發明所屬之技術領域】 本發明係有關用以被覆按鍵開關之層合樹脂體。 【先前技術】 行動電話、數位相機、電子記事本、遙控器、個人電 腦之鍵盤爲首，如工業用或醫療用精密機械等中使用之按 H 鍵開關或觸控式感應器按鍵開關之按鍵開關隨著機器本體 之薄形化進展之結果，已漸趨向小而薄。當按健開關變小 時，可動部分之間隙調整變得困難，按鍵自身會因連續使 用而歪斜，容易發生朝機器內側押入之困擾。又，由於最 近趨向防水規格，故按鍵與本體之間隙越來越小，亦有於 機器本體內側進行張起橡膠等之加工之辦法，但按鍵無法 早期運轉，於設計安排上，有本體必須變大而容易發生不 合宜之情況。 Q 爲解決該等問題，已對按鍵開關進行被覆加以探討， 例如特開2005-3 1 0540號公報（專利文獻1)揭示有使用 丙烯酸樹脂薄膜作爲按鍵開關之被覆構件。此文獻中記載 之被覆構件，係由丙烯酸薄膜與補強樹脂薄膜所構成，該 丙烯酸薄膜係由略平坦之基底部與自該基底部突出之凸部 所構成’藉由黏著劑將該基底部與該補強樹脂薄膜予以黏 著。如此，於將該補強樹脂薄膜黏著於該基底部並層合， 於製造時切斷基底部之際、於遭受強烈衝擊之際或於使用 時按鍵變形之際，均難以對該基底部產生割痕。 -4- 200937471 【發明內容】 [發明欲解決之課題] 如此文獻中所揭示，若使用丙烯酸薄膜作爲按鍵開關 之被覆材’就不易產生傷痕之方面雖爲有利，但於機器落 下時、接觸物品之際’有容易產生割痕之問題。又，此被 覆構件於凸部未層合有補強樹脂薄膜，該凸部偶有容易割 裂之情況。原本丙烯酸薄膜之剛性高，相反地其柔軟性差 ’就合於如按鍵般之深度形狀而成形而言有困難。具體而 言’於凸部成形時，無法耐受所施加之應力而易於發生龜 裂’又’於凸部形成後亦容易殘留歪斜產生割裂。又，薄 膜若薄薄地成形時雖可防使龜裂，但成形物之強韌性不足 ，按鍵因按押時之壓力亦有發生割裂之可能性。 此種狀況下，本發明之目的係提供一種難以產生傷痕 且難以被割裂之按鍵開關之被覆構件。 [用以解決問題之手段] ◎ 本發明人等積極探討之結果，發現藉由採用特定之層 合樹脂體作爲按鍵開關之被覆構件，可達成上述目的，因 而完成本發明。亦即，本發明提供一種按鍵開關被覆用層 合樹脂體，其特徵爲在聚碳酸酯樹脂層之至少一面上層合 有丙烯酸樹脂層，且聚碳酸酯樹脂層之厚度爲總厚度之 5 0%以上。 [發明效果] -5- 200937471 本發明之按鍵開關被覆用層合樹脂體因難以產生傷痕 且難以被割裂，故可有效地被覆按鍵開關。 【實施方式】 本發明之層合樹脂體係在聚碳酸酯樹脂層之至少一面 上層合有丙烯酸樹脂層，而可使用於被覆按鍵開關者。 作爲構成聚碳酸酯之聚碳酸酯樹脂舉例有例如藉由使 〇 二價酚與羰基化劑以界面聚縮合法或熔融酯交換法等反應 而得者以外’亦可舉例有藉由使聚碳酸酯預聚物以固相酯 交換法等距合而得者、藉由使環狀碳酸酯化合物以開環聚 合法聚合而得者。 作爲二價酚’舉例有例如氫醌、間苯二酚、4，4，-二羥 基聯苯、雙（4-羥基苯基）甲烷、雙{ (4_羥基_3，5_二甲 基）苯基}甲烷、1，1-雙（4-羥基苯基）乙烷、U1-雙（4-羥基苯基）-1-苯基乙烷、2，2-雙（4-羥基苯基）丙烷（通 Ο 稱雙酚A )、2,2-雙{( 4-羥基-3·甲基）苯基}丙烷、2,2-雙{ (4-羥基·3,5-二甲基）苯基}丙烷、2,2_雙{ (4_羥基_ 3,5·二溴）苯基}丙烷、2,2·雙{(3_異丙基_4_羥基）苯基} 丙烷、2，2-雙{ (4-羥基-3-苯基）苯基}丙烷、2,2-雙（4-淫基苯基）丁院、2,2 -雙（4 -羥基苯基）-3 -甲基丁院、 2,2-雙（4-羥基苯基）-3,3_二甲基丁烷、2,4_雙（4_羥基 苯基）-2-甲基丁烷、2,2-雙（4-羥基苯基）戊烷、2,2-雙 (4-羥基苯基）-4·甲基戊烷、1，1_雙（4_羥基苯基）環己 烷、1，1_雙（4-羥基苯基）-4-異丙基環己烷、-雙（4- -6 - 200937471 羥基苯基）-3,3,5-三甲基環己烷、9,9-雙（4-羥基苯基） 芴、9,9-雙{(4-羥基-3-甲基）苯基}芴、α，α’_雙（4·羥 基苯基）-鄰-二異丙基苯、雙（4 -經基苯基）-間-二異丙基苯、α，α’-雙（4-羥基苯基）-對-二異丙基苯、 1，3-雙（4-羥基苯基）-5,7-二甲基金剛烷、4,4，-二羥基二 苯基楓、4,4’-二羥基二苯基亞楓、4,4’-二羥基二苯基硫醚 、4,4’-二羥基二苯基酮、4,4’-二羥基二苯基醚、4,4，-二 羥基二苯基酯等，依據需要可使用該等兩種以上。 @ 其中，較好單獨或使用兩種以上之選自雙酚A、2,2-雙{ (4-羥基-3-甲基）苯基}丙烷、2，2-雙（4-羥基苯基） 丁烷、2,2-雙（4·羥基苯基）-3-甲基丁烷、2，2-雙（4-羥 基苯基）-3,3-二甲基丁烷、2,4-雙（4-羥基苯基）-4-甲基 戊烷、1，1-雙（4-羥基苯基）-3,3,5-三甲基環己烷及α, α’-雙（4-羥基苯基）-間-二異丙基苯之二價酚，尤其， 可單獨使用雙酚Α或較好倂用1,1-雙（4-羥基苯基）-3,3,5-三甲基環己烷及選自雙酚A、2,2-雙{ ( 4-羥基-3-甲 ◎ 基）苯基}丙烷及α，α 雙（4-羥基苯基）-間-二異丙基苯 之一種以上之二價酚。 作爲羰基化劑，舉例有例如，如碳醯氯之羰基鹵化物 ，如二苯基碳酸酯之碳酸酯，如二價酚之二鹵甲酸酯之鹵 甲酸酯等，依據需要亦可以該等兩種以上使用。 構成丙烯酸樹脂層之丙烯酸樹脂，可使用一般之甲基 丙烯酸樹脂。甲基丙烯酸樹脂係以甲基丙烯酸甲酯作爲主 要成分者，具體而言，可爲甲基丙烯酸甲酯單位含有50 200937471 重量％以上，較好70重量％以上之甲丙烯酸甲酯樹脂，亦 可爲甲基丙烯酸甲酯100重量％之甲基丙烯酸甲酯之均聚 物，亦可爲甲基丙烯酸甲酯與其他單體之共聚物。 可與甲基丙烯酸甲酯共聚合之其他單體之例，舉例有 如甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸環己酯 、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸2-乙基 己酯、甲基丙烯酸2-羥基乙酯之甲基丙烯酸甲酯以外之甲 ❹ 基丙烯酸酯類，或如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苄酯、丙烯酸2-乙基己酯、丙烯酸2-羥基乙酯之丙烯酸酯類。又，亦可舉 例有苯乙烯或經取代苯乙烯類，例如如氯苯乙烯、溴苯乙 烯之鹵化苯乙烯類，或如乙烯基甲苯、α -甲基苯乙烯之 烷基苯乙烯類等。再者，亦舉例有如甲基丙烯酸、丙烯酸 之不飽和酸類、丙烯腈、甲基丙烯腈、馬來酸酐、苯基馬 來醯亞胺、環己基馬來醯亞胺等。該等與甲基丙烯酸甲酯 φ 共聚合之其他單體可個別單獨使用，亦可組合兩種以上使 用。 丙烯酸樹脂亦可摻雜橡膠狀聚合物使用。作爲橡膠狀 聚合物之例，舉例有丙烯酸系多層構造聚合物、或於5〜8 0 重量份橡膠狀聚合物中接枝聚合有如丙烯酸系不飽和單體 之乙烯性不飽和單體20〜95重量份之接枝共聚物等。丙烯 酸系多層構造聚合物宜爲內部存在橡膠彈性層或彈性聚合 物層爲20〜60重量％左右，最外部具有硬質層者，再者亦 可爲最內層含有硬質層之構造者。 -8- 200937471 橡膠層或彈性聚合物層宜爲玻璃轉移點（Tg)爲小於 25 °C之丙烯酸系聚合物之層，具體而言，宜爲使選自丙烯 酸低級烷酯、甲基丙烯酸低級烷酯、丙烯酸低級烷氧基烷 酯、丙烯酸氰基乙酯、丙烯醯胺、丙烯酸羥基低級烷酯、 甲基丙烯酸羥基低級烷酯、丙烯酸及甲基丙烯酸之單官能 基單體之一種以上，以如甲基丙烯酸烯丙酯之多官能基單 體予以交聯之聚合物層。 硬質層宜爲Tg爲25 °C以上之丙烯酸系聚合物之層， 具體而言’宜爲以具有碳數1〜4個之烷基之甲基丙烯酸烷 酯單獨或作爲主成分而聚合者。以甲基丙烯酸烷酯作爲主 成分之共聚物時，作爲共聚合成分，可使用如其他甲基丙 烯酸烷酯與丙烯酸烷酯、苯乙烯、經取代苯乙烯、丙烯腈 、甲基丙烯腈之單官能基單體，亦可爲進而加入多官能基 單體之交聯聚合物。 丙烯酸系多層構造聚合物舉例爲特公昭55_27576號 公報、特開平6-80739號公報、特開昭49-232922號公報 等所記載者。 於5〜80重量份之橡膠狀聚合物中接枝聚合乙烯性不 飽和單體20〜95重量份之接枝共聚物中，作爲橡膠狀聚合 物’可使用例如如聚丁二烯橡膠、丙烯腈/ 丁二烯共聚物 橡膠、苯乙烯/ 丁二烯共聚物橡膠之二烯系橡膠，如聚丙 稀酸丁酯、聚丙烯酸丙酯 '聚丙烯酸2_乙基己酯之丙烯酸 系橡膠’乙稀/非共軛二烯系橡膠等。又，於此橡膠狀聚 合物中接枝共聚合所用之乙烯性單體，舉例有例如乙烯、 -9- 200937471 丙烯腈、（甲基）丙烯酸烷酯等。該等接枝共聚物爲例如 特開昭55- 1 475 1 4號公報、特公昭47_9740號公報等所記 載。 於丙烯酸樹脂中分散橡膠狀聚合物時之分散比例，對 於丙烯酸樹脂100重量份，通常爲3〜150重量份，較好爲 5〜50重量份。橡膠狀聚合物之量若過多，則表面硬度降低 而較不佳。 0 又，聚碳酸酯樹脂層及丙烯酸樹脂層分別可依據需要 亦可添加例如光擴散劑、消艷劑、染料、光安定劑、紫外 線吸收劑、抗氧化劑、離型劑、難燃劑、抗靜電劑等之添 加劑之一種或兩種以上。 本發明之層合樹脂體，可藉由使聚碳酸酯樹脂層與丙 烯酸樹脂層以共押出成形而層合一體化而較佳地製造。此 共押出成形’係使用兩台或三台單軸或雙軸押出機，使聚 碳酸酯樹脂層之材料與丙烯酸樹脂層之材料分別熔融混練 ❹ 後’透過給料器模嘴或多歧管模嘴等加以層合藉此而進行 ’經層合一體化之熔融層合樹脂體可例如使用輥捏合機加 以冷卻固化而作成層合樹脂體。藉由共押出成形所製造之 層合樹脂體’相較於使用黏著劑或接著劑予以貼合而製造 之層合樹脂體，就易於二次型成爲按鍵狀方面而言爲較好 。共押出成形之際，以使聚碳酸酯樹脂層與丙烯酸樹脂層 鄰接之方式，加以共押出成形則更佳。 本發明之層合樹脂體可爲僅於聚碳酸酯樹脂層之單面 層合丙烯酸樹脂層而成之兩層構造，亦可爲於聚碳酸酯兩 -10- 200937471 面上層合丙烯酸樹脂層之三層構造者，但三層構造者，隨 著丙烯酸樹脂層厚度及丙烯酸樹脂種類而異，有面衝擊性 降低易產生割裂之情況，故以兩層構造者較佳。 本發明之層合樹脂體通常爲薄片狀乃至於薄膜狀，其 厚度通常爲 0.2~2mm，更好爲 0.3〜1mm，又更好爲 0.3~0.7mm，因此，本發明之層合樹脂體中，聚碳酸酯樹 脂層厚度爲全體厚度之50%以上，較好爲70%以上，更好 爲80%以上。如此，藉由使聚碳酸酯樹脂層厚度成爲特定 q 比例以上，層合樹脂體變得更難以割裂。又，聚碳酸酯樹 脂層厚度，相對於全體厚度，通常爲95%以下，更好爲 90 %以下。 於重視丙烯酸樹脂層表面硬度之情況，其厚度較好爲 10μιη以上。又，三層構造之情況，兩層丙烯酸層厚度可 互爲相同亦可互爲不同。200937471 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a laminated resin body for covering a push button switch. [Prior Art] Mobile phones, digital cameras, electronic notebooks, remote controls, and personal computer keyboards, such as buttons for H-switches or touch-sensitive sensor buttons used in industrial or medical precision machinery. As the result of the thinning of the machine body, the switch has gradually become smaller and thinner. When the push switch is made smaller, the gap adjustment of the movable portion becomes difficult, and the button itself is skewed due to continuous use, which is liable to cause intrusion into the inside of the machine. Moreover, due to the recent trend toward waterproof specifications, the gap between the button and the body is getting smaller and smaller, and there is also a method of processing the rubber on the inside of the machine body, but the button cannot be operated early, and the design must have a body It becomes bigger and prone to inappropriate situations. In order to solve such a problem, the key switch has been described. For example, JP-A-2005-3 1 0540 (Patent Document 1) discloses a coated member using an acrylic resin film as a push button switch. The covering member described in this document is composed of an acrylic film and a reinforcing resin film which is composed of a slightly flat base portion and a convex portion protruding from the base portion. The base portion is adhered by an adhesive. The reinforcing resin film is adhered. In this manner, when the reinforcing resin film is adhered to the base portion and laminated, it is difficult to cut the base portion when the base portion is cut at the time of production, when a strong impact is applied, or when the button is deformed during use. mark. -4- 200937471 [Disclosed] [Problems to be Solved by the Invention] As disclosed in the literature, it is advantageous to use an acrylic film as a covering material for a push button switch, which is advantageous in that it is less likely to cause scratches, but when the machine is dropped, the article is contacted. At the time of 'there is a problem that is prone to cuts. Further, in the covering member, a reinforcing resin film is not laminated on the convex portion, and the convex portion may occasionally be easily cut. The original acrylic film has high rigidity, and conversely, its softness is difficult to form in combination with a deep shape like a button. Specifically, when the convex portion is formed, the applied stress is not able to withstand the crack and the crack is likely to occur. Further, after the convex portion is formed, the skew is likely to remain. Further, when the film is formed thin, it is possible to prevent cracking, but the toughness of the molded product is insufficient, and the button may be split due to the pressure at the time of pressing. Under such circumstances, an object of the present invention is to provide a covering member of a push button switch which is less likely to cause scratches and which is difficult to be separated. [Means for Solving the Problem] The present inventors have found that the above object can be attained by using a specific laminated resin body as a covering member of a push switch, and the present invention has been completed. That is, the present invention provides a laminated resin body for key switch coating, characterized in that an acrylic resin layer is laminated on at least one side of a polycarbonate resin layer, and the thickness of the polycarbonate resin layer is 50% of the total thickness. the above. [Effect of the Invention] -5-200937471 The laminated resin body for the push button switch of the present invention is less likely to be scratched and is difficult to be separated, so that the push button switch can be effectively covered. [Embodiment] The laminated resin system of the present invention has an acrylic resin layer laminated on at least one side of a polycarbonate resin layer, and can be used for a cover button switch. The polycarbonate resin constituting the polycarbonate is exemplified by, for example, a reaction in which a quinone divalent phenol and a carbonylating agent are reacted by an interfacial polycondensation method or a melt transesterification method. The ester prepolymer is obtained by a solid phase transesterification method, and is obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. Examples of the divalent phenols include, for example, hydroquinone, resorcin, 4,4,-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, and bis{(4-hydroxy-3,5-dimethyl Phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, U1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl) Propane (by bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl Phenyl}propane, 2,2_bis{(4-hydroxy-3,5-dibromo)phenyl}propane, 2,2·bis{(3-isopropyl-4-yl)phenyl}propane , 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-mercaptophenyl)butyl, 2,2-bis(4-hydroxyphenyl) -3 -methylbutyl, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane , 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4.methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane Alkane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, -bis(4- -6 - 200937471 hydroxyphenyl)-3,3,5-trimethylcyclohexane 9,9-bis (4-hydroxyl) ), 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'_bis(4.hydroxyphenyl)-o-diisopropylbenzene, bis (4) -Phenylphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)- 5,7-dimethyl adamantane, 4,4,-dihydroxydiphenyl maple, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenyl sulfide, 4, 4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4,-dihydroxydiphenyl ester, etc., 2 or more types can be used as needed. @ Among them, it is preferred to use bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl) alone or in combination of two or more. Butane, 2,2-bis(4.hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4 - bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α,α'-double ( Divalent phenol of 4-hydroxyphenyl)-m-diisopropylbenzene, in particular, bisphenol hydrazine alone or preferably 1,1-bis(4-hydroxyphenyl)-3,3,5 -trimethylcyclohexane and selected from bisphenol A, 2,2-bis{(4-hydroxy-3-methylphenyl)phenyl}propane and α,α bis(4-hydroxyphenyl)-inter- More than one divalent phenol of diisopropylbenzene. As the carbonylating agent, for example, a carbonyl halide such as carbonium chloride, such as a carbonate of diphenyl carbonate, such as a haloformate of a divalent phenol dihaloformate, etc., may be used as needed. More than two types are used. As the acrylic resin constituting the acrylic resin layer, a general methacrylic resin can be used. The methacrylic resin is methyl methacrylate as a main component, and specifically, the methyl methacrylate unit may contain 50 200937471% by weight or more, preferably 70% by weight or more of methyl methacrylate resin. It is a homopolymer of 100% by weight of methyl methacrylate of methyl methacrylate, and may also be a copolymer of methyl methacrylate and other monomers. Examples of other monomers copolymerizable with methyl methacrylate include, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, and A 2-methylhexyl acrylate, a methyl methacrylate other than methyl methacrylate of 2-hydroxyethyl methacrylate, or a methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate. , acrylate of acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate acrylate. Further, examples thereof include styrene or substituted styrenes such as halogenated styrenes such as chlorostyrene and bromostyrene, or alkylstyrenes such as vinyl toluene and ?-methylstyrene. Further, examples thereof include methacrylic acid, unsaturated acids of acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like. These other monomers copolymerized with methyl methacrylate φ may be used singly or in combination of two or more. The acrylic resin can also be used by doping a rubbery polymer. As an example of the rubbery polymer, an acrylic multilayer structure polymer or an ethylenically unsaturated monomer such as an acrylic unsaturated monomer grafted and polymerized in 5 to 80 parts by weight of a rubbery polymer is exemplified. Parts by weight of the graft copolymer and the like. The acrylic acid-based multilayer structure polymer preferably has a rubber elastic layer or an elastic polymer layer of about 20 to 60% by weight, and has a hard layer on the outermost side, and may also be a structure in which the innermost layer contains a hard layer. -8- 200937471 The rubber layer or the elastic polymer layer is preferably a layer of an acrylic polymer having a glass transition point (Tg) of less than 25 ° C. Specifically, it is preferably a lower alkyl acrylate or methacrylic acid lower grade. One or more of an alkyl ester, a lower alkyl alkoxylate, a cyanoethyl acrylate, an acrylamide, a hydroxy hydroxy lower alkyl ester, a hydroxy lower alkyl methacrylate, a monofunctional monomer of acrylic acid and methacrylic acid, A polymer layer crosslinked with a polyfunctional monomer such as allyl methacrylate. The hard layer is preferably a layer of an acrylic polymer having a Tg of 25 ° C or higher. Specifically, it is preferably polymerized by using an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, alone or as a main component. When a copolymer having alkyl methacrylate as a main component is used, as the copolymerization component, for example, other alkyl methacrylate and alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile may be used. The functional group monomer may also be a crosslinked polymer to which a polyfunctional monomer is further added. The acryl-based multilayer structure polymer is described in, for example, JP-A-55-27576, JP-A-6-80739, JP-A-49-232922, and the like. The graft copolymer of 20 to 95 parts by weight of the ethylenically unsaturated monomer is graft polymerized in 5 to 80 parts by weight of the rubbery polymer, and as the rubbery polymer, for example, polybutadiene rubber or propylene can be used. Nitrile/butadiene copolymer rubber, styrene/butadiene copolymer rubber diene rubber, such as polybutyl acrylate, poly acrylate acrylate 2-ethylhexyl acrylate rubber 'B A dilute/non-conjugated diene rubber or the like. Further, examples of the vinyl monomer used for graft copolymerization in the rubbery polymer include, for example, ethylene, -9-200937471 acrylonitrile, alkyl (meth)acrylate, and the like. The graft copolymers are described, for example, in Japanese Laid-Open Patent Publication No. SHO-55-147, No. 4,475, and the like. The dispersion ratio in the case where the rubbery polymer is dispersed in the acrylic resin is usually from 3 to 150 parts by weight, preferably from 5 to 50 parts by weight, per 100 parts by weight of the acrylic resin. If the amount of the rubbery polymer is too large, the surface hardness is lowered and it is not preferable. 0 Further, the polycarbonate resin layer and the acrylic resin layer may be added, for example, as a light diffusing agent, a deodorant, a dye, a light stabilizer, an ultraviolet absorber, an antioxidant, a release agent, a flame retardant, and an anti-anti-inflammatory agent, respectively. One or two or more kinds of additives such as an electrostatic agent. The laminated resin body of the present invention can be preferably produced by laminating and integrating a polycarbonate resin layer and an acrylic resin layer by co-extrusion molding. The co-extrusion forming method uses two or three single-axis or two-axis extruding machines to melt and knead the material of the polycarbonate resin layer and the material of the acrylic resin layer respectively, and then pass through the feeder nozzle or the multi-manifold mold. The melt-laminated resin body which is laminated by the nozzle or the like can be cooled and solidified by, for example, a roll kneader to form a laminated resin body. It is preferable that the laminated resin body produced by the co-extrusion molding is bonded to the laminated resin body produced by bonding with an adhesive or an adhesive, and it is easy to make the secondary type into a button shape. When the total extrusion molding is carried out, it is more preferable to perform co-extrusion molding so that the polycarbonate resin layer and the acrylic resin layer are adjacent to each other. The laminated resin body of the present invention may have a two-layer structure in which an acrylic resin layer is laminated on only one side of a polycarbonate resin layer, or may be an acrylic resin layer laminated on a polycarbonate--10-200937471 surface. The three-layer structure, but the three-layer structure differs depending on the thickness of the acrylic resin layer and the type of the acrylic resin, and the surface impact resistance is liable to be split, so that a two-layer structure is preferable. The laminated resin body of the present invention is usually in the form of a sheet or a film, and its thickness is usually 0.2 to 2 mm, more preferably 0.3 to 1 mm, still more preferably 0.3 to 0.7 mm, and therefore, in the laminated resin body of the present invention The polycarbonate resin layer has a thickness of 50% or more, preferably 70% or more, more preferably 80% or more. As described above, by setting the thickness of the polycarbonate resin layer to a specific q ratio or more, the laminated resin body becomes more difficult to be split. Further, the thickness of the polycarbonate resin layer is usually 95% or less, more preferably 90% or less, based on the entire thickness. When the surface hardness of the acrylic resin layer is emphasized, the thickness thereof is preferably 10 μm or more. Moreover, in the case of a three-layer structure, the thickness of the two layers of acrylic layers may be the same or different from each other.
如此所得之本發明層合樹脂體，可使用作爲例如行動 電話或攜帶用音樂播放器等之按鍵開關之被覆構件。又， Q 亦可使用作爲觸控感應器按鍵開關之被覆材料。再者，亦 可使用作爲兼有該等按鍵開關被覆功能之液晶或有機EL 面板之保護被覆構件。 本發明之層合樹脂體使用作爲按鍵開關之被覆構件時 ，宜例如依據需要，進行如熱成形之二次成形、印刷、開 孔等加工，切斷成特定形狀乃至特定大小之處理。具體而 言，例如，於本發明之被覆用層合樹脂體之一部分上，形 成爲於外側面爲丙烯酸樹脂層之表面，內部形狀形爲對應 -11 - 200937471 於按鍵開關外形之凸部，將該凸部周圍切斷成特定尺寸形 成略平坦之基底部。 如此，可獲得由本發明之按鍵開關用被覆層合樹脂體 所構成之具有略平坦基底部與自該基底部突出、外側面爲 丙烯酸樹脂層表面、內部形狀爲對應於按鍵開關外形之凸 部之按鍵開關被覆構件。 接著，使用所得之按鍵開關被覆構件，若爲兩層構造 Φ 之層合樹脂體，通常較好以丙烯酸樹脂層成爲表側（外側 :與人接觸之側）之方式，被覆按鍵開關。又，爲三層構 造之層合樹脂體時，於丙層丙烯酸樹脂層厚度互爲不同之 情況，較好以厚度較大一方之丙烯酸樹脂層作爲表側之方 式，被覆按鍵開關。 由如此本發明之層合樹脂體被覆按鍵開關，藉此可於 按鍵開關表面上形成不易產生傷痕且難以被割裂之被覆層 。又，亦具有防水及防塵效果。 Ο [實施例] 以下，雖顯示本發明之實施例，但本發明不限定於該 等。各例中之押出裝置構成及評價方法如下。 [押出裝置之構成] 押出機（1):螺桿直徑65mm，單軸，附有通風孔（ 東芝機械（股）製） 押出機（2) ••螺桿直徑45mm，單軸，附有通風孔（ -12- 200937471 曰立造船（股）製） 給料器：兩種三層及兩種兩層分配（日立造船（股） 製）。 模嘴：T型模嘴，唇部寬度l4〇〇mm，唇部間隔lmm (曰立造船（股）製）。 輥：拋光輥3根，橫型 [評價方法] 於布施真空（股）製之熱成形機（型式：CUPF-1015-PWB)中設置 1 80 x 250mm開口部，群集切割成 220 x 3 10mm之樹脂板（於l〇〇°C乾燥20小時者），使用ΙΟΟχ 50mm之高lOOnm突起成形用木製模型，在180°C之成形 溫度進行突起成形。此時，於兩層構成之板之情況，以使 丙烯酸樹脂層成爲頂部外側（未與突起木製模型接觸之面 )之方式進行成形。所得之突起成形品頂部之鉛筆硬度’ 依據JIS K5400，以lkg荷重加以測定。又，所得之突起 成形品頂部作爲上部頂板而放置，自高度lm使5〇〇克鐵 球落下，藉此進行落球試驗，無割裂時記爲〇，有割裂者 參考例1 (橡膠狀聚合物之製造） 依據特公昭5 5 -27576號公報所記載之方法’製造二 層構造丙烯酸系多層彈性體。亦即，於內容積5升之玻璃 製反應容器內’裝入離子交換水1700克、碳酸鈉〇.7克 200937471 及過硫酸鈉0.3克’於氮氣氣流中攪拌後，添加二辛基磺 基琥珀酸鈉（花王（股）製之PEREX OT-P ;陰離子性界 面活性劑）4.46克、離子交換水15〇克、甲基丙烯酸甲酯 150克及甲基丙烯酸烯丙酯〇.3克，升溫至75它繼續攪拌 150分鐘。接著，將丙烯酸丁酯689克、苯乙烯162克及 甲基丙烯酸烯丙酯17克之混合物，以及過硫酸鈉0·85克 、二辛基磺基琥珀酸鈉（同上）7.4克及離子交換水50克 0 之混合物’自不同入口逾90分鐘內添加，進而繼續聚合 90分鐘。隨後，再將丙烯酸甲酯326克及丙烯酸乙酯14 克之混合物，與溶解有過硫酸鈉0.34克之離子交換水30 克之溶液，由不同入口以30分鐘內添加。添加結束後， 再保持60分鐘此聚合完成。所得之乳膠投入〇.5重量％氯 化鋁水溶液中’使聚合物凝集。將其以溫水洗淨5次後， 加以乾燥，獲得丙烯酸系多層彈性體。 Q 實施例1〜4 聚碳酸酯樹脂[住友道（股）製之CARIBAR 301-10] 以押出機（1)，丙烯酸樹脂[甲基丙烯酸甲酯/丙烯酸甲酯 = 9 8/2 (重量比）之共聚物]以押出機（2)，分別邊加熱邊 熔融混練，於給料器中層合一體化，以熔融狀態自Τ型模 嘴押出，於拋光輥上冷卻，獲得表1所示構成之兩層樹脂 板。所得之板評價結果示於表1。 實施例5~6 -14 - 200937471 聚碳酸酯樹脂[住友道（股）製之CARIBAR 301-10] 以押出機（1)，丙烯酸樹脂[甲基丙烯酸甲酯/丙烯酸甲酯 = 96/4 (重量比）之共聚物（折射率1.49 ) 70重量份中， 添加參考例1所得之丙烯酸系多層彈性體3 0重量份所得 之甲基丙烯酸樹脂組成物]以押出機（2)，分別邊加熱邊 熔融混練，於給料器中層合一體化，以熔融狀態自T型模 嘴押出，於拋光輥上冷卻，獲得表1所示構成之三層樹脂 板。所得之板評價結果示於表1。 @ 比較例1 於實施例2中，更換各押出機原料之丙烯酸樹脂與聚 碳酸酯樹脂，獲得表1所示構成之兩層樹脂板。所得之板 評價結果示於表1。 比較例2 於實施例6中，更換各押出機原料之丙烯酸樹脂與聚 Q 碳酸酯樹脂，獲得表1所示構成之三層樹脂板。所得之板 評價結果示於表1。 比較例3 於實施例3中，停止押出機（1 )，獲得僅丙烯酸樹 脂層之單層板。所得之板評價結果示於表1。 比較例4 -15- 200937471 於實施例3中，停止押出機（2)，獲得僅聚碳酸酯 樹脂層之單層板。所得之板評價結果示於表1。 表1 總厚度（μιη) 層構成 厚度（μπι) 鉛筆硬度 落球試驗 實施例1 800 PC/PMMA 720/80 2Η 〇 實施例2 800 PC/PMMA 760/40 Η 〇 實施例3 500 PC/PMMA 430/70 2Η 〇 實施例4 400 PC/PMMA 360/40 Η 〇 實施例5 800 PMMA/PC/PMMA 80/640/80 Η 〇 實施例6 500 PMMA/PC/PMMA 50/400/50 F 〇 實施例7 300 PMMA/PC/PMMA 40/220/40 F 〇 比較例1 800 PMMA/PC 760/40 3Η X 比較例2 500 PC/PMMA/PC 50/400/50 2Β 〇 比較例3 500 PMMA 500 3Η X 比較例4 500 PC 500 3Β 〇As the laminated resin body of the present invention thus obtained, a covering member such as a push button switch such as a mobile phone or a portable music player can be used. Also, Q can also be used as a covering material for the touch sensor button switch. Further, a protective covering member which is a liquid crystal or an organic EL panel having the function of covering the key switch can also be used. When the laminated resin body of the present invention is used as a covering member for a push button switch, it is preferable to carry out processing such as secondary forming, printing, and opening, such as thermoforming, to cut into a specific shape or a specific size, as needed. Specifically, for example, in one portion of the laminated resin body for coating of the present invention, the outer surface is formed as a surface of an acrylic resin layer, and the inner shape is a convex portion corresponding to the shape of the button switch of -11 - 200937471, The periphery of the convex portion is cut into a specific size to form a slightly flat base portion. As described above, the coated laminated resin body for a push button switch of the present invention can have a slightly flat base portion and protrude from the base portion, the outer surface of which is the surface of the acrylic resin layer, and the inner shape of which is a convex portion corresponding to the shape of the push switch. The key switch covers the member. Next, using the obtained key switch cover member, in the case of a laminated resin body having a two-layer structure Φ, it is preferable to cover the push button switch so that the acrylic resin layer is on the front side (outside: the side in contact with the person). Further, in the case of a laminated resin body having a three-layer structure, when the thickness of the acrylic layer of the acryl layer is different from each other, it is preferable to cover the key switch with the acrylic resin layer having the larger thickness as the front side. According to the laminated resin body of the present invention, the push button switch is coated, whereby a coating layer which is less likely to be scratched and which is difficult to be cut can be formed on the surface of the push switch. Also, it has waterproof and dustproof effects. [Examples] Hereinafter, the examples of the present invention are shown, but the present invention is not limited thereto. The composition and evaluation method of the extrusion device in each example are as follows. [Composition of the extrusion device] Extruder (1): Screw diameter 65mm, single shaft, with ventilation holes (Toshiba Machine Co., Ltd.) Extruder (2) • Screw diameter 45mm, single shaft, with ventilation holes ( -12- 200937471 造立造造(股)) Feeder: Two three-layer and two-layer two-layer distribution (Hitachi Shipbuilding Co., Ltd.). Mold mouth: T-shaped die mouth, lip width l4〇〇mm, lip interval lmm (stand-alone shipbuilding (stock) system). Roller: 3 polishing rolls, horizontal type [Evaluation method] Set the 1 80 x 250mm opening in the thermoforming machine (type: CUPF-1015-PWB) made by Buche vacuum (stock), and cut it into 220 x 3 10mm. A resin plate (dried at 100 ° C for 20 hours) was subjected to protrusion molding at a molding temperature of 180 ° C using a wooden mold having a height of 100 mm and a thickness of 100 nm. In this case, in the case of a two-layered plate, the acrylic resin layer is formed so that the acrylic resin layer is on the outer side of the top surface (the surface which is not in contact with the raised wooden mold). The pencil hardness of the top of the obtained protrusion molded article was measured in accordance with JIS K5400 at a lkg load. Further, the top of the obtained projection molded article was placed as an upper top plate, and 5 gram of iron balls were dropped from the height lm, thereby performing a ball drop test, which was marked as 〇 when there was no split, and a cracked reference example 1 (rubbery polymer) Manufactured according to the method described in Japanese Patent Publication No. 5-5-27576, a two-layer structure acrylic multilayer elastic body is produced. That is, after adding 1700 g of ion-exchanged water, sodium carbonate 〇.7 g of 200937471 and 0.3 g of sodium persulfate in a glass reaction vessel having an internal volume of 5 liters, a dioctylsulfo group was added after stirring in a nitrogen gas stream. Sodium succinate (PEREX OT-P made by Kao (stock); anionic surfactant) 4.46 g, ion exchange water 15 g, methyl methacrylate 150 g and allyl methacrylate 〇. 3 g, Warm to 75 and it continues to stir for 150 minutes. Next, a mixture of 689 g of butyl acrylate, 162 g of styrene and 17 g of allyl methacrylate, and 0.85 g of sodium persulfate, 7.4 g of sodium dioctylsulfosuccinate (ibid.) and ion-exchanged water. A mixture of 50 grams of 0 was added over 90 minutes from different inlets and polymerization continued for 90 minutes. Subsequently, a mixture of 326 g of methyl acrylate and 14 g of ethyl acrylate and a solution of 30 g of ion-exchanged water in which 0.34 g of sodium persulfate was dissolved were added from different inlets over 30 minutes. After the end of the addition, the polymerization was completed for another 60 minutes. The obtained latex was put into a 5% by weight aqueous solution of aluminum chloride to cause the polymer to aggregate. After washing with warm water for 5 times, it was dried to obtain an acrylic multilayer elastomer. Q Example 1 to 4 Polycarbonate Resin [CARIBAR 301-10 manufactured by Sumitomo Co., Ltd.] Extrusion machine (1), acrylic resin [methyl methacrylate / methyl acrylate = 9 8/2 (weight ratio) The copolymer (2) was melted and kneaded by heating, and laminated and integrated in a feeder, and extruded in a molten state from a die-type die, and cooled on a polishing roll to obtain the composition shown in Table 1. Two layers of resin board. The obtained board evaluation results are shown in Table 1. Example 5~6 -14 - 200937471 Polycarbonate Resin [CARIBAR 301-10 manufactured by Sumitomo Co., Ltd.] with extruder (1), acrylic resin [methyl methacrylate / methyl acrylate = 96/4 ( Copolymer (refractive index: 1.49) 70 parts by weight, the obtained methacrylic resin composition obtained by adding 30 parts by weight of the acrylic multilayer elastomer obtained in Reference Example 1 was heated by an extruder (2) The mixture was melt-kneaded, laminated and integrated in a feeder, extruded from a T-die in a molten state, and cooled on a polishing roll to obtain a three-layer resin sheet having the composition shown in Table 1. The obtained board evaluation results are shown in Table 1. @Comparative Example 1 In Example 2, an acrylic resin and a polycarbonate resin of each extruder raw material were exchanged to obtain two resin sheets having the constitution shown in Table 1. The obtained board evaluation results are shown in Table 1. Comparative Example 2 In Example 6, the acrylic resin and the poly Q carbonate resin of each of the extruder materials were replaced, and a three-layer resin sheet having the composition shown in Table 1 was obtained. The obtained board evaluation results are shown in Table 1. Comparative Example 3 In Example 3, the extruder (1) was stopped to obtain a single-layer board of only the acrylic resin layer. The obtained board evaluation results are shown in Table 1. Comparative Example 4 -15- 200937471 In Example 3, the extruding machine (2) was stopped to obtain a single-layered plate of only a polycarbonate resin layer. The obtained board evaluation results are shown in Table 1. Table 1 Total Thickness (μιη) Layer Composition Thickness (μπι) Pencil Hardness Falling Ball Test Example 1 800 PC/PMMA 720/80 2Η 〇 Example 2 800 PC/PMMA 760/40 Η 〇 Example 3 500 PC/PMMA 430/ 70 2Η 〇 Example 4 400 PC/PMMA 360/40 Η Example 5 800 PMMA/PC/PMMA 80/640/80 Η 〇 Example 6 500 PMMA/PC/PMMA 50/400/50 F 〇 Example 7 300 PMMA/PC/PMMA 40/220/40 F 〇Comparative Example 1 800 PMMA/PC 760/40 3Η X Comparative Example 2 500 PC/PMMA/PC 50/400/50 2Β 〇Comparative Example 3 500 PMMA 500 3Η X Comparison Example 4 500 PC 500 3Β 〇
表1中，PC表示聚碳酸酯樹脂層，PMMA表示丙烯 φ 酸樹脂層。 -16-In Table 1, PC represents a polycarbonate resin layer, and PMMA represents a propylene φ acid resin layer. -16-