200948607 六、發明說明： 【發明所屬之技術領域】 本發明有關耐擦傷性樹脂板及其用途。 . 【先前技術】 近年來，行動電話（mobile telephone )或 PHS (200948607 VI. Description of the Invention: [Technical Field to Which the Invention Is Alonged] The present invention relates to a scratch resistant resin sheet and use thereof. [Prior Art] In recent years, mobile telephone or PHS (
Personal Handy-phone System )(個人電話系統））等的 Φ 攜帶型電話類，在隨著網際網路（internet )的普及，已 成爲單純的語音傳達功能之外尙具有顯示文字資訊或影像 ' 資訊之功能之攜帶型資訊終端機而廣泛普及。又，除此種 攜帶型電話類之外，尙有一種住址名簿等的功能上兼具網 際網路功能或電子信箱功能之 PDA ( Personal Digital Assistant )(個人數位助理））亦在廣泛使用。本說明書 中，則將此種行動電話或PHS、PDA等總括稱呼爲“攜帶 型資訊終端機”。亦即，本說明書中所稱呼之“攜帶型資訊 β 終端機”係本身爲人類能攜帶行走之程度的大小，而具有 爲能顯示文字資訊或影像資訊等之用的視窗（window )者 , 之總稱。 _ 此等攜帶型資訊終端機中，係藉由液晶或EL (電場 發光）等的方式，而作成能顯示文字資訊或影像資訊之方 式者’其顯示視窗，則作爲保護板而一般採用透明樹脂製 者’其中’因透明性之故，甲基丙烯酸樹脂很適合使用（ 例如，參考日本專利特開2 0 0 2 - 6 7 6 4號公報、日本專利特 開2004-143365號公報、日本專利特開2004-299199號公 200948607 報）。並且，此種保護板上，爲防止表面的刮傷起見，提 案有使用硬化性塗料以設置耐擦傷性（硬敷層性）的硬化 被膜之作法。 【發明內容】 _ 在來所提案之攜帶型資訊終端機的顯示視窗保護板， 係因抗環境性（environment proof)不一定足夠之故，例 如，經長時間曝露在高溫度高濕度下時，有容易發生反翹 © 或硬化被膜之裂痕等的問題。又，製造時的加工性不一定 足夠，例如，亦有切割（cutting )時容易附著切屑等灰塵 ’ 之問題。 本發明之目的在於提供一種抗環境性或加工性優異， 作爲攜帶型資訊終端機的顯示視窗保護板好用的耐擦傷性 樹脂板。 本發明，提供下述手段。 〔1〕一種耐擦傷性樹脂板，係由基板及硬化被膜所 ® 成之耐擦傷性樹脂板，其特徵爲：該基板係於聚碳酸酯樹 脂層的至少一邊的面上層合有丙烯酸樹脂層而成，如該基 - 板爲僅於該聚碳酸酯樹脂層的一邊的面上層合有該丙烯酸 _ 樹脂層者時，則於該丙烯酸樹脂層之上形成有含有導電性 粒子之硬化被膜而成，如該基板爲於該聚碳酸酯樹脂層的 兩邊的面上層合有該丙烯酸樹脂層者時，則於其至少一邊 的丙烯酸樹脂層之上形成有含有導電性粒子之硬化被膜而 成。 -6- 200948607 〔2〕如前述〔1〕記載之耐擦傷性樹脂板，其中基板 係於聚碳酸酯樹脂層的一邊的面上層合有丙烯酸樹脂層而 成者。 〔3〕如前述〔2〕記載之耐擦傷性樹脂板，其中於聚 . 碳酸酯樹脂層的面之中，於未層合有丙烯酸樹脂層之面上 _ ，形成有硬化被膜。 〔4〕在前述〔3〕記載之耐擦傷性樹脂板，其中經形 〇 成於聚碳酸酯樹脂層上之硬化被膜，係含有導電性粒子者 〇 〔5〕如前述〔3〕或〔4〕記載之耐擦傷性樹脂板， 其中經形成於聚碳酸酯樹脂層上之硬化被膜的折射率η與 聚碳酸酯樹脂層的折射率ns，係在如下式 | n-ns | ^0.01 的關係。 〔6〕如前述〔3〕至〔5〕之任一項記載之耐擦傷性 ® 樹脂板，其中經形成於聚碳酸酯樹脂層上之硬化被膜中所 含之導電性粒子，係選自銻·錫複合氧化物、銻-鋅複合酸 - 化物以及含磷之氧化錫所成群者。 〔7〕如前述〔1〕至〔6〕之任一項記載之耐擦傷性 樹脂板’其中經形成於丙烯酸樹脂層上之硬化被膜中所含 之導電性粒子，係氧化銻。 〔8〕一種攜帶型資訊終端機之顯示視窗保護板，其 特徵爲：由前述〔1〕至〔7〕之任一項記載之耐擦傷性樹 脂板所成。 200948607 〔9〕一種顯示器之保護板，其特徵爲：由前述〔1〕 至〔7〕之任一項記載之耐擦傷性樹脂板所成。 本發明之耐擦傷性樹脂板，係抗環境性優異、加工性 亦優異者，如將該耐擦傷性樹脂板作爲顯示器保護板，特 別是作成攜帶型資訊終端機之顯示視窗保護板使用時，則 可有效保護其顯示視窗。 〔發明之最佳實施形態〕 本發明之耐擦傷性樹脂板，係將於聚碳酸酯樹脂層的 至少一邊的面上層合有丙烯酸樹脂層所成之層合板作爲基 板，如係丙烯酸樹脂層僅經層合於聚碳酸酯樹脂層的一邊 的面上所成之基板時，則於其丙烯酸樹脂層之上形成有含 有導電性粒子之硬化性被膜而成者，如係丙烯酸樹脂層經 層合於聚碳酸酯樹脂層的兩邊的面上所成之基板時，則於 其至少一邊的丙烯酸樹脂之上，形成有含有導電性粒子之 硬化被膜而成者。 構成聚碳酸酯樹脂層之聚碳酸酯樹脂而言，除例如使 二元苯酣與羰基化劑（carbonylation agent)依界面縮聚 法（interfacial polycondensation)法或熔融醋交換法（ fusion ester interchange)等進行反應以製得者之外，尙 可舉：使碳酸酯預聚合物（carbonate prepolymer)依固態 醋交換法（solid state ester interchange)等進行聚合以製 得者，使環狀碳酸酯化合物依開環聚合法（ring-opening polymerization)進行聚環合以製得者等。 200948607 二元苯酚而言，可列舉：氫醌、雷瑣辛（resorcin ) 、4,4’-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、1,1-雙（4-羥基苯基）-1-苯基乙烷、2,2_雙（4-羥基苯基）丙 . 烷（通稱雙酚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-3,5-二溴代）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-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）-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、1，1-雙（4-羥基苯基）-3,3,5-三甲基環己烷、9,9-雙（ 4-羥基苯基）弗（fluorene) 、9,9-雙{ (4-基-3-甲基） ® 苯基}苐、α,α’-雙（4-羥基苯基）鄰二異丙基苯、α, α 雙（4-羥基苯基）間二異丙基等、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’-二羥基二苯基亞碾、 4,4’-二羥基苯基硫化物、4,4’-二羥基二苯基甲酮、4,4’-二羥基二苯基醚、4,4’-二羥基二苯基酯等，並亦可按照需 要採用此等的2種以上。 其中，較佳爲採用選自：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 -9- 200948607 (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' 2,2-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以及^^，_雙（4-羥 基苯基）間二異丙基苯二元苯酚以單獨或2種以上之方式 ，特佳爲雙酚A的單獨使用、或1，1-雙（4 -羥基苯基）- _ 3,5,5-三甲基環己烷、與選自雙酚a、2,2-雙{ (4-羥基-3·甲基）苯基}丙烷以及〇：,〇：’-雙（4-羥基苯基）間二異 丙基苯之1種以上的二元苯酚的倂用。 © 碳基化劑而言，可例舉：如碳酸氯（phosgen )等的 羰基鹵化物、如二苯基碳酸酯等碳酸酯、二元苯酚的二鹵 甲酸酯等的鹵甲酸酯（halo formate )等，並亦可按照需 要採用此等的2種以上。 構成丙烯酸樹脂層之丙烯酸樹脂而言，一般可採用甲 基丙烯酸樹脂。甲基丙烯酸樹脂，較佳爲以甲基丙烯酸甲 酯作爲主成分者，具體而言，通常含有甲基丙烯酸甲酯單 元50重量％以上、較佳爲含有甲基丙烯酸甲酯樹脂7〇重 ® 量％以上，亦可爲甲基丙烯酸甲酯單元1〇〇重量％的甲基 丙烯酸甲酯單獨聚合物’亦可爲與甲基丙烯酸甲酯與其他 · 單體的共聚物。 - 能與甲基丙烯酸甲酯進行共聚合之其他單體的例而言 ，可例舉：如甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙 烯酸環己酯、甲基丙嫌酸苯酯、甲基丙嫌酸节醋、甲基丙 烯酸2-乙基己酯、甲基丙烯酸2-經基乙酯般之甲基丙嫌酸 甲酯以外的甲基丙嫌酸酯類或如丙嫌酸甲醋、丙稀酸乙醋 -10- 200948607 、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-羥基乙酯般的丙烯酸酯類 。又，苯乙烯或取代苯乙烯類，例如，如氯苯乙烯、溴苯 乙烯般的鹵化苯乙烯類、或如乙烯基甲苯、α -甲基苯乙 - 烯般的烷基苯乙烯類等。再者，亦可例舉：如甲基丙烯酸 _ 、丙烯酸般的不飽和酸酯、丙烯腈、甲基丙烯腈、馬來酸 酐、苯基馬來醯胺、環己基馬來醯胺等。能與此等甲基丙 © 烯酸甲酯進行共聚合之其他單體，可以分別單獨方式使用 ，亦可組合2種以上之方式使用。 丙烯酸樹脂中亦可摻合（blend )橡膠狀聚合物使用 。橡膠狀聚合物的例子而言，可舉：丙烯酸系多層結構聚 合物、或對5至80重量份的橡膠狀聚合物使如丙烯酸系 不飽和單體般的乙烯性不飽和單體2 0至9 5重量份進行接 枝聚合（graft polymerization)而成之接枝共聚物等。丙 烯酸系多層結構聚合物，較佳爲使橡膠彈性之層或彈性物 ( elastomer )之層內在20至60重量％程度者，較佳爲最 外層具有硬質層者，再者，作爲最內層而含有硬質層之構 - 造者亦可。 . 橡膠彈性的層或彈性物之層，較佳爲玻璃化溫度（Tg )在25 °C以下的丙烯酸系聚合物之層，具體而言，較佳爲 使選自低級烷基丙烯酸酯、低級烷基甲基丙烯酸酯、低級 烷氧基烷基丙烯酸酯、氰基乙基丙烯酸酯、丙烯醯胺、羥 基低級烷基丙烯酸酯、羥基低級烷基甲基丙烯酸酯、丙烯 酸以及甲基丙烯酸酯之單官能單體的1種以上，使用如烯 -11 - 200948607 丙基甲基丙烯酸酯般的多官能單體進行交聯所成之聚合物 之層。 硬質層，較佳爲Tg在25 °c以上的丙烯酸系聚合物之 層，具體而言，較佳爲使具有碳酸1至4個的烷基之烷基 甲基丙烯酸酯按單獨方式或作爲主成分之方式進行聚合物 者。如以烷基甲基丙烯酸酯作爲主成分而作成共聚合物時 ，共聚合成分而言，可採用其他烷基甲基丙烯酸酯或如烷 基丙烯酸酯、苯乙烯、取代苯乙烯、丙烯腈、甲基丙烯腈 © 般的單官能單體，再者，亦可添加多官能單體而作成交聯 聚合物。 丙烯酸系多層構造聚合物，係經記載於例如，日本專 利特公昭5 5-27576號公報、日本專利特開平6-80739號公 報、曰本專利特開昭49-23292號公報等中。 於對5至80重量份的橡膠狀聚合物使乙烯性不飽和 單體20至95重量份進行接枝聚合而成之接枝共聚物中， 橡膠狀聚合物而言，例如，可採用：如聚丁二烯橡膠、丙 〇 烯腈/ 丁二烯共聚物橡膠、苯乙烯/ 丁二烯共聚物橡膠般 的二烯烴系橡膠，如聚丁基丙烯酸酯、聚丙基丙烯酸酯、 - 聚-2-乙基己基丙烯酸酯般的丙烯酸系橡膠、乙烯/丙烯/ 非共軛二烯烴系橡膠等。又，使此橡膠狀聚合物進行接枝 共聚合所用之乙烯性不飽和單體而言，可例舉：苯乙烯、 丙嫌腈、烷基（甲基）丙烯酸酯等。此等接枝共聚物，係 經記載於例如，日本專利特開昭5 5 _丨4 7 5丨4號公報、日本 專利特公昭47-974〇號公報等中。 -12- 200948607 丙烯酸樹脂中使橡膠狀聚合物分散時的分散比例，係 對丙烯酸樹脂1〇〇重量份，通常爲3至150重量份、較佳 爲5至50重量份。如橡膠狀聚合物之量過多時，則表面 硬度將降低而不宜。 - 再者，聚碳酸酯樹脂層及丙烯酸樹脂層中，可按需要 而分別添加例如，光擴散劑、平光劑（flatting agent )、 染料、光穩定劑、紫外線吸收劑、抗氧化劑、脫模劑、難 Ο 燃劑、抗靜電劑等的添加劑1種或2種以上。 本發明之耐擦傷性樹脂板的基板，如使聚碳酸酯樹脂 層與丙嫌酸樹脂層，依共擠壓成型（coextruding moulding )進行層合一體化，即可順利製造。此種共擠壓成型，係 採用2部或3部的單軸或雙軸的擠壓機（extruder)，將 聚碳酸酯樹脂層的材料與丙烯酸樹脂層的材料分別加以熔 融混練後，介由給料部件（feed block)或多岐管式模頭 (multimanifold die)而層合即可實施，經層合一體化之 β 熔融層合樹脂體，例如使用軋輥組合件（roll unit)使其 冷卻固化即可。使用共擠壓成型所製造之基板，係由於較 - 藉由使用黏附劑（adhesive)或膠黏劑（tackifier)之貼 合所製造之基板，爲容易進行如鈕扣（button)狀等之二 次成型之故較佳。 基板，通常爲片材（sheet )狀或薄膜（film )狀者， 其厚度，通常爲0.3至3mm、較佳爲0.3至2mm、更佳爲 0.4至1.5mm者。並且’於基板上，丙烯酸樹脂層的厚度 ，通常作成爲60至110/zm、更佳爲70至lOOym。如此 -13- 200948607 方式設定丙烯酸樹脂層的厚度，則基板更不易破裂且可獲 得足夠的表面硬度。 基板，可爲僅於聚碳酸酯樹脂的單面上層合有丙烯酸 樹脂層所成之2層構造者，亦可爲於聚碳酸酯樹脂層的兩 面上層合有丙烯酸樹脂層所成之3層構造者，惟3層構造 _ 者，因丙烯酸樹脂的厚度或丙烯酸樹脂的種類，而面衝擊 性（plane impaction ability)降低以致容易破裂之故，較 佳爲2層構造者。 © 如重視丙烯酸樹脂層的表面硬度時，則較佳爲將其厚 度作成50 y m以上。再者，如在3層構造的情形，則兩層 丙烯酸層的厚度，可互爲相同或不相同。 於基板表面，將形成耐擦傷性的硬化被膜。在此，硬 化被膜可形成於基板的兩面，亦可僅形成於單面。 因而，耐擦傷性樹脂板的層構成的典型的例而言，可 舉·· (1)硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層、 (2)硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層/硬化 〇 被膜、（3)硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層 /丙烯酸樹脂層、（4)硬化被膜/丙烯酸樹脂層/聚碳 - 酸酯樹脂層/丙烯酸樹脂層/硬化被膜。 丙烯酸樹脂層上所形成之硬化被膜，與聚碳酸酯樹脂 層上所形成之硬化被膜，可爲相同或不相同。 爲形成硬化被膜所用之硬化性塗料，係以能賦與耐擦 傷性之各種硬化性化合物作爲主成分，按照需要而混合有 溶劑、導電性粒子、硬化觸媒等者’惟爲將形成於丙烯酸 -14- 200948607 樹脂層上之硬化被膜用的硬化性塗料中，導電性粒子係必 需之物。 首先，就硬化性化合物加以說明。硬化性化合物而言 ，從丙烯酸酯化合物、聚胺酯丙烯酸酯化合物、環氧丙烯 . 酸酯化合物、羧基改性環氧丙烯酸酯化合物、聚酯丙烯酸 酯化合物、共聚合系丙烯酸酯、脂環式環氧樹脂、縮水甘 油基醚環氧樹脂、乙烯基醚化合物、氧雜環丁烷（oxetane © )化合物等之中，採用具有能賦與耐擦傷性效果者即可。 其中，作爲能賦與高的耐擦傷性之硬化性化合物，可例舉 :多官能丙烯酸酯化合物、多官能聚酯丙烯酸酯化合物、 多官能環氧丙烯酸酯化合物等、自由基引發聚合系的硬化 性化合物、或烷氧基矽烷、烷基烷氧基矽烷等、熱引發聚 合系的硬化性化合物。此等硬化性化合物，係例如，藉由 電子射線、放射線、紫外線等的能量標線（energy liine ) 之照射而硬化、或者藉由加熱而硬化者。此等硬化性化合 ® 物，可分別以單獨方式使用，亦可組合複數種化合物之方 式使用。 此等硬化性化合物之中，較佳者爲分子中至少具有3 . 個（甲基）丙烯醯氧基之化合物。在此，（甲基）丙烯醯 氧基，係指丙烯醯氧基或者甲基丙烯醯氧基之意。此外， 本說明書中，（甲基）丙烯酸酯、（甲基）丙烯酸等中之 ^ (甲基）」亦爲同樣意義。 分子中至少具有三個（甲基）丙烯醯氧基之硬化性化 合物而言，可例舉：三羥甲基丙烷三（甲基）丙烯酸酯、 -15- 200948607 三羥甲基乙烷三（甲基）丙烯酸酯、甘油三（甲基）丙烯 酸酯、新戊三醇三（甲基）丙烯酸酯、異戊四醇三或四（ 甲基）丙烯酸酯、二異戊四醇三、四、五或六（甲基）丙 烯酸酯、三異戊四醇四、五、六、或七（甲基）丙烯酸酯 般的3元以上的多元醇的聚（甲基）丙烯酸酯；對分子內 至少具有2個異氰酸酯基之化合物，使具有羥基之（甲基 )丙烯酸酯單體，按對異氰酸酯基，羥基能成爲等莫耳之 — 比例進行反應而製得，而1分子中的（甲基）丙烯醯氧基 ❿ 的數成爲3個以上之胺基甲酸乙酯（甲基）丙烯酸酯〔例 如，因二異氰酸酯與異戊四醇三（甲基）丙烯酸酯的反應 ，即可製得3至6官能基的胺基甲酸乙酯（甲基）丙烯酸 酯〕；參（2-羥基乙基）三聚異氰酸的三（甲基）丙烯酸 酯等。在此，係以單體例示者，惟可將此單體直接使用， 亦可使用成爲例如，二聚物、三聚物等的低聚物之形態者 。又，亦可倂用單體與低聚物。此等（甲基）丙烯酸酯化 合物，可分別以單獨使用或者混合2種以上使用。 © 由於至少具有3個（甲基）丙烯醯氧基之硬化性化合 物中，亦有在市售者之故，亦可採用此種市售品。市售品 - 而言，可例舉：“NK哈得Μ1 01 ”〔新中村化學工業（股） 製品、胺基甲酸乙酯丙烯酸酯系〕、“ΝΚ埃斯特爾八-TMM-3 L”〔新中村化學工業（股）製品、異戊四醇三丙烯 酸酯〕、“ΝΚ埃斯特爾Α-ΤΜΜΤ”〔新中村化學工業（股 )製品、異戊四醇四丙烯酸酯〕、“ΝΚ埃斯特爾Α-9 5 3 0” 〔新中村化學工業（股）製品、二異戊四醇五丙烯酸酯〕 -16- 200948607 、“ NK埃斯特爾a-DPH”〔新中村化學工業（股）製品、 二異戊四醇六丙烯酸酯〕、“KAYARAD DPCA”〔曰本化藥 (股）製品、二異戊四醇六丙烯酸酯〕、“諾布可裘亞 200”系列〔燦諾布科（股）製品〕、“優尼狄克，，系列〔大 - 曰本油墨化學工業（股）製品〕等。 _ 再者’分子中至少具有3個（甲基）丙烯醯基之化合 物’可與此外的硬化性化合物，可與例如，乙二醇二（甲 © 基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、1,6-己二 醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯般 之分子中具有2個（甲基）丙烯醯氧基之化合物一起採用 ’唯其量係對分子中至少具有3個（甲基）丙烯醯氧基之 化合物100重量份，通常在20重量份爲止。 如藉由紫外線而使硬化性塗料硬化之情形，則使用光 聚合引發劑。光聚合引發劑而言，可例舉：二苯基酮（ benzil)、二苯基酮（benzo phenone)或其衍生物、噻噸 ® 酮（thioxanthone )類、苄基二甲基縮酮類、羥基烷基 苯酮類、羥基甲酮類、胺基烷基苯酮類、醯基氧化膦類等 - 。光聚合引發劑的添加量，係對硬化性化合物1 00重量份 . ，一般在〇.1至5重量份的範圍。 此等光聚合引發劑，係除可分別單獨使用之外，多半 可混合2種以上使用。又，由於此等各種光聚合引發劑係 有在市售之故，可使用此種市售品。市售的光聚合引發劑 而言，可例舉：“IRGACURE (伊爾加裘亞）651”、 “IRGACURE 184”、“IRGACURE 5 0 0”、“IRGACURE 1 000” -17- 200948607 、“IRGACURE 2959”、“D ARO CUR (達羅裘亞）1 1 7 3’，、 “IRGACURE 907”、“IRGACURE 369”、“IRGACURE 1 700” 、“IRGACURE 1 800”、“1RGACURE 819，，、“IRGACURE 784”〔以上的 IRGACURE (伊爾加裘亞）系列及 DAROCUR (達羅裘亞）系歹IJ ，係由千葉.特殊化學品（ . 股）所銷售〕、“KAYACURE (卡雅裘亞）ITX”、 “KAYACURE DETX-S”、“KAYACURE BP-100”、“KAYACURE BMS”、“KAYACURE 2-EAQ”〔以上的 KAYACURE (卡雅 ❿ 裘亞）系列，係由日本化藥（股）所銷售〕等。 又，於本發明，爲將形成於丙烯酸樹脂層上之硬化被 膜用的硬化性塗料中添加導電性粒子。爲此所用之導電性 粒子而言，可例舉：銻-錫複合氧化物、含磷之氧化錫、 氧化銻、銻-鋅複合氧化物、氧化鈦、銦-錫複合氧化物（ ITO)等的無機粒子。其中，較佳爲氧化銻。 如調配導電性粒子時，其粒徑，能按粒子種類而加以 適當選擇，通常使用〇. 5 /z m以下者，惟從所得硬化被膜 € 的加工性或透明性的觀點來看，以平均粒徑計，較佳爲 O.OOlyC/m以上 0.1//m以下者、更佳爲 0.001//m以上 0.0 0 5 // m以下者。如導電性粒子的平均粒徑過大時，則可 - 能所得耐擦傷性樹脂板的霧狀（haze )增大，以致透明性 降低。又，導電性粒子的使用量，係對硬化性化合物1 〇〇 重量份，通常爲2至50重量份程度、較佳爲3至20重量 份程度。如其量過少時，則加工性改善效果減退。又，如 其量過多時，則可能降低硬化被膜的透明性。 -18- 200948607 此種導電粒子，係可利用例如，汽相分解法（vapor decomposition )、電漿蒸發法（plasma evaporation )、烷 氧化物分解法（alkoxide decomposition)、共沈澱法（ co-precipitation )、水熱反應法（hydro-thermal reaction )等製造。又，導電性粒子表面，可經以例如非離子系表 面活性劑、陽離子系表面活性劑、陰離子系表面活性劑、 聚砂氧系偶合劑（silicone coupling agent)、鋁系偶合劑 (aluminum coupling agent)等施加表面處理。 硬化性塗料中，以塗料的黏度調整爲目的而使用稀釋 溶劑，特別是將添加導電性粒子時，通常爲其分散而使用 。如使用導電性粒子、且使用溶劑時，例如，可於混合導 電性粒子與溶劑以使導電性粒子分散於溶劑中後，再與硬 化性化合物，亦可於硬化性化合物與溶劑混合後，再對此 導電性子以進行混合。 溶劑，祇要是能溶解硬化性化合物，且在塗佈後能揮 發者即可，又，如作爲塗料成分而採用導電性粒子時，祇 要能使其分散者即可。可例舉：如雙丙酮醇、甲醇、乙醇 、異丙醇、異丁醇、2-甲氧乙醇、2-乙氧乙醇、2-丁氧乙 醇、1-甲氧-2-丙醇般的醇類，如丙酮、甲基乙基甲酮、甲 基異丁基甲酮、雙丙酮醇般的酮類，如甲苯、二甲苯般的 芳香族烴類，如醋酸乙酯、醋酸丁酯般的酯類，水等。於 硬化性塗料中之溶劑的使用量並無特別的限定，可視硬化 性化合物的性狀等，而以適當量使用。 又，於此硬化性塗料中，亦可添加周知的調平劑（ -19- 200948607 leveling agent)。調平劑而言，可例示：聚砂氧油（ silicone oil)系者等。聚矽氧油而言，可使用通常者，具 體而言，可例示：二甲基矽氧油、苯基甲基矽氧油、烷基 •芳烷基改性矽氧油、氟代矽氧油、聚醚改性矽氧油、脂 肪酸酯改性矽氧油、甲基氫代矽氧油、含矽烷醇（silanol . )之矽氧油、含烷氧基之矽氧油、含苯酚之矽氧油、甲基 丙烯基改性矽氧油、胺基改性矽氧油、羧酸改性矽氧油、 甲醇（carbinol )改性矽氧油、乙氧基改性矽氧油、锍基 © 改性矽氧油、氟改性矽氧油、聚醚改性矽氧油等。由於此 等調平劑係有在市售之故，可採用市售品。市售的調平劑 而言，可歹！J 舉：“SH200- 1 OOcs”、“SH28PA”、“SH29PA，，、 “SH30PA”、“ST83PA”、“ST80PA”、“ST97PA”、“ST86PA”Personal Handy-phone System (Personal Telephone System), etc. Φ Portable telephones, with the popularity of the Internet, have become a simple voice communication function with display text information or video information. It is widely used as a portable information terminal. Further, in addition to such a portable type of telephone, a PDA (Personal Digital Assistant) having a function of an Internet address or an e-mail function, such as an address book, is widely used. In this specification, such a mobile phone, PHS, PDA, etc. are collectively referred to as "portable information terminal". That is, the "portable information beta terminal" referred to in the present specification is itself a size that can be carried by a human being, and has a window for displaying text information or video information, etc. General name. _ In these portable information terminals, a method of displaying text information or video information by means of liquid crystal or EL (electric field illumination) is used as a display window, and a transparent resin is generally used as a protective plate. The methacrylic resin is very suitable for use because of the transparency (for example, refer to Japanese Patent Laid-Open Publication No. 2000-276, Japanese Patent Laid-Open No. 2004-143365, Japanese Patent Special open 2004-299199 public 200948607 report). Further, in order to prevent scratching of the surface, such a protective sheet has a method of using a curable coating material to provide a hardened film having scratch resistance (hard coating property). SUMMARY OF THE INVENTION _ The display window protection board of the portable information terminal proposed by the present invention is not necessarily sufficient for environmental proof, for example, when exposed to high temperature and high humidity for a long time, There is a problem that it is prone to cracking or cracking of the film. Further, the workability at the time of production is not necessarily sufficient, and for example, there is a problem that dust such as chips is easily adhered during cutting. SUMMARY OF THE INVENTION An object of the present invention is to provide a scratch-resistant resin sheet which is excellent in environmental resistance and processability and is useful as a display window protection panel for a portable information terminal. The present invention provides the following means. [1] A scratch-resistant resin sheet which is a scratch-resistant resin sheet made of a substrate and a cured film, characterized in that the substrate is laminated with an acrylic resin layer on at least one surface of the polycarbonate resin layer. When the base plate is formed by laminating the acrylic resin layer on only one side of the polycarbonate resin layer, a cured film containing conductive particles is formed on the acrylic resin layer. When the substrate is formed by laminating the acrylic resin layer on both sides of the polycarbonate resin layer, a cured film containing conductive particles is formed on at least one of the acrylic resin layers. [6] The scratch-resistant resin sheet according to the above [1], wherein the substrate is formed by laminating an acrylic resin layer on one surface of the polycarbonate resin layer. [3] The scratch-resistant resin sheet according to the above [2], wherein a hardened film is formed on a surface of the polyacetate resin layer on a surface on which the acrylic resin layer is not laminated. [4] The scratch-resistant resin sheet according to the above [3], wherein the hardened film which is formed on the polycarbonate resin layer is a conductive film, and the conductive particles are as described above [5] or [4] The scratch-resistant resin sheet according to the above, wherein the refractive index η of the cured film formed on the polycarbonate resin layer and the refractive index ns of the polycarbonate resin layer are as follows: n-ns | ^0.01 . [6] The scratch-resistant® resin sheet according to any one of the above [3], wherein the conductive particles contained in the cured film formed on the polycarbonate resin layer are selected from the group consisting of 锑• Groups of tin composite oxides, bismuth-zinc complex acid compounds, and phosphorus-containing tin oxides. [7] The scratch-resistant resin sheet according to any one of the above [1] to [6] wherein the conductive particles contained in the cured film formed on the acrylic resin layer are cerium oxide. [8] A display window protection panel of a portable information terminal, which is characterized in that it is formed by the scratch-resistant resin board according to any one of the above [1] to [7]. [Claim] A protective sheet for a display, which is obtained by the scratch-resistant resin sheet according to any one of the above [1] to [7]. The scratch-resistant resin sheet of the present invention is excellent in environmental resistance and excellent in workability, and when the scratch-resistant resin sheet is used as a display protection sheet, particularly when used as a display window protection sheet of a portable information terminal machine, It can effectively protect its display window. BEST MODE FOR CARRYING OUT THE INVENTION The scratch-resistant resin sheet of the present invention is a laminate obtained by laminating an acrylic resin layer on at least one surface of a polycarbonate resin layer, and is an acrylic resin layer only. When a substrate formed on one surface of a polycarbonate resin layer is laminated, a curable film containing conductive particles is formed on the acrylic resin layer, and the acrylic resin layer is laminated. In the case of a substrate formed on both surfaces of the polycarbonate resin layer, a cured film containing conductive particles is formed on at least one of the acrylic resins. The polycarbonate resin constituting the polycarbonate resin layer is subjected to, for example, an interfacial polycondensation method or a fusion ester interchange method, in addition to a diphenyl hydrazine and a carbonylation agent. In addition to the reaction, the carbonic acid prepolymer is polymerized by solid state ester interchange or the like to obtain a cyclic carbonate compound. Ring-opening polymerization is carried out by polycyclization to obtain a product or the like. 200948607 Dibasic phenol, for example, hydroquinone, resorcin, 4,4'-hydroxybiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5- Dimethylphenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2_bis (4 -Hydroxyphenyl)propane. (Also known as 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- Hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis (4) -hydroxyphenyl)-3-methylbutane, 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-hydroxyl Phenyl)cyclohexane, 1,1 bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl Cyclohexane, 9,9-bis(4-hydroxyphenyl) ) fluorene, 9,9-bis{(4-yl-3-methyl) ® phenyl} fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α, Α-bis(4-hydroxyphenyl)-diisopropyl or the like, α,α bis(4-hydroxy-phenyl)-p-isopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5, 7-Dimethyl adamantane, 4,4'-dihydroxydiphenyl maple, 4,4'-dihydroxydiphenyl argon, 4,4'-dihydroxyphenyl sulfide, 4,4'- Dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., and two or more of these may be used as needed. It is selected from the group consisting of: bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-double -9- 200948607 (4-Hydroxyphenyl)-3-methylbutyl, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane 2,2-bis(4- Hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and ^^,_bis(4-hydroxyphenyl) The m-diisopropylbenzene diphenol is used alone or in combination of two or more, particularly preferably bisphenol A, 1,1-bis(4-hydroxyphenyl)-_3,5,5-trimethylcyclohexane, and selected from bisphenol a, 2,2-bis{(4-hydroxy-3.methyl) Phenyl}propane and hydrazine: 〇: '-bis(4-hydroxyphenyl)-diisopropylbenzene is used in combination with one or more kinds of dihydric phenols. The carbonization agent may, for example, be a carbonyl halide such as phosgen, a carbonate such as diphenyl carbonate or a dihaloformate of a dihydric phenol. Halo formate), etc., and two or more of these may be used as needed. As the acrylic resin constituting the acrylic resin layer, a methacrylic resin is generally used. The methacrylic resin is preferably a component containing methyl methacrylate as a main component, and specifically contains 50% by weight or more of a methyl methacrylate unit, preferably a methyl methacrylate resin. The amount of the methyl methacrylate unit may be a copolymer of methyl methacrylate and other monomers. - Examples of other monomers copolymerizable with methyl methacrylate, such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methacrylic acid benzene Ethyl ester, methyl propyl sulphate vinegar, 2-ethylhexyl methacrylate, methacrylic acid 2-methyl propyl methacrylate Acidic vinegar, acetoacetate -10-200948607, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate class. Further, styrene or a substituted styrene, for example, a halogenated styrene such as chlorostyrene or bromostyrene, or an alkylstyrene such as vinyltoluene or ?-methylphenylene. Further, examples thereof include methacrylic acid _, acrylic acid unsaturated acid ester, acrylonitrile, methacrylonitrile, maleic anhydride, phenyl maleimide, cyclohexylmaleamide and the like. The other monomers which can be copolymerized with the methyl methacrylate or the ethyl methacrylate may be used singly or in combination of two or more. The acrylic resin may also be blended with a rubbery polymer. Examples of the rubbery polymer include an acrylic multilayer polymer or 5 to 80 parts by weight of a rubbery polymer to give an ethylenically unsaturated monomer such as an acrylic unsaturated monomer 20 to 9.5 parts by weight of a graft copolymer obtained by graft polymerization. The acrylic multi-layer polymer preferably has a rubber elastic layer or an elastomer layer of 20 to 60% by weight, preferably the outermost layer has a hard layer, and further, as the innermost layer. It consists of a hard layer - the maker can also. The layer of the rubber elastic layer or the layer of the elastic material is preferably a layer of an acrylic polymer having a glass transition temperature (Tg) of 25 ° C or less. Specifically, it is preferably selected from the group consisting of lower alkyl acrylates and lower grades. Alkyl methacrylate, lower alkoxyalkyl acrylate, cyanoethyl acrylate, acrylamide, hydroxy lower alkyl acrylate, hydroxy lower alkyl methacrylate, acrylic acid and methacrylate One or more kinds of monofunctional monomers are a layer of a polymer obtained by crosslinking a polyfunctional monomer such as ene-11 - 200948607 propyl methacrylate. The hard layer is preferably a layer of an acrylic polymer having a Tg of 25 ° C or more. Specifically, it is preferred to use an alkyl methacrylate having an alkyl group having 1 to 4 carbonic acids in a separate manner or as a main The composition of the polymer is carried out in a manner. When a copolymer is formed by using an alkyl methacrylate as a main component, other alkyl methacrylates such as alkyl acrylate, styrene, substituted styrene, acrylonitrile, or the like may be used as the copolymer component. A methacrylonitrile-like monofunctional monomer, or a polyfunctional monomer may be added as a cross-linked polymer. The acryl-type multilayer structure polymer is described in, for example, Japanese Patent Publication No. 5-5-27576, Japanese Patent Application Laid-Open No. Hei No. Hei. In the graft copolymer obtained by graft-polymerizing from 20 to 80 parts by weight of the rubbery polymer to 20 to 95 parts by weight of the ethylenically unsaturated monomer, for the rubbery polymer, for example, Polybutadiene rubber, acrylonitrile/butadiene copolymer rubber, styrene/butadiene copolymer rubber-like diene rubber, such as polybutyl acrylate, polypropyl acrylate, - poly-2 - Ethylhexyl acrylate-like acrylic rubber, ethylene/propylene/non-conjugated diene-based rubber, and the like. Further, the ethylenically unsaturated monomer used for the graft copolymerization of the rubbery polymer may, for example, be styrene, a acrylonitrile or an alkyl (meth)acrylate. Such a graft copolymer is described in, for example, Japanese Laid-Open Patent Publication No. SHO-5-5-5, No. 4, No. 47-974, and the like. -12- 200948607 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 part by weight of the acrylic resin. If the amount of the rubbery polymer is too large, the surface hardness will be lowered. Further, in the polycarbonate resin layer and the acrylic resin layer, for example, a light diffusing agent, a flatting agent, a dye, a light stabilizer, an ultraviolet absorber, an antioxidant, and a release agent may be added as needed. It is difficult to use one or more kinds of additives such as a fuel and an antistatic agent. The substrate of the scratch-resistant resin sheet of the present invention can be smoothly produced by laminating and integrating the polycarbonate resin layer and the acrylic acid resin layer by coextruding moulding. In this co-extrusion molding, a two- or three-part uniaxial or biaxial extruder is used, and the material of the polycarbonate resin layer and the material of the acrylic resin layer are separately melted and kneaded, and then The laminate can be implemented by laminating a feed block or a multimanifold die, and the laminated melted laminated resin body is cooled and solidified, for example, by using a roll unit. can. The substrate produced by the co-extrusion molding is made of a substrate which is made by bonding using an adhesive or a tackifier, and is easily subjected to a button-like shape or the like. It is preferred for molding. The substrate, usually in the form of a sheet or a film, has a thickness of usually 0.3 to 3 mm, preferably 0.3 to 2 mm, more preferably 0.4 to 1.5 mm. Further, the thickness of the acrylic resin layer on the substrate is usually 60 to 110 / zm, more preferably 70 to 100 μm. Thus, the thickness of the acrylic resin layer is set in the manner of -13-200948607, the substrate is less likely to be broken and sufficient surface hardness can be obtained. The substrate may be a two-layer structure in which an acrylic resin layer is laminated on one surface of a polycarbonate resin alone, or a three-layer structure in which an acrylic resin layer is laminated on both surfaces of a polycarbonate resin layer. However, the three-layer structure is preferably a two-layer structure because of the thickness of the acrylic resin or the type of the acrylic resin, and the plane impaction ability is lowered to cause cracking. © When the surface hardness of the acrylic resin layer is important, it is preferable to set the thickness to 50 μm or more. Further, as in the case of the three-layer structure, the thicknesses of the two acrylic layers may be the same or different from each other. On the surface of the substrate, a scratch-resistant hardened film is formed. Here, the hard film may be formed on both sides of the substrate or may be formed only on one side. Therefore, typical examples of the layer structure of the scratch-resistant resin sheet include (1) a cured film/acrylic resin layer/polycarbonate resin layer, and (2) a cured film/acrylic resin layer/polycarbonate. Resin layer/hardened tantalum film, (3) hardened film/acrylic resin layer/polycarbonate resin layer/acrylic resin layer, (4) hardened film/acrylic resin layer/polycarbonate resin layer/acrylic resin layer/hardened Membrane. The hardened film formed on the acrylic resin layer may be the same as or different from the hardened film formed on the polycarbonate resin layer. The curable coating material used for forming the cured film is made of a curable compound which imparts scratch resistance as a main component, and if necessary, a solvent, a conductive particle, a curing catalyst, etc. are mixed as needed. -14- 200948607 Among the curable coating materials for the hardened film on the resin layer, conductive particles are essential. First, the curable compound will be described. For the curable compound, an acrylate compound, a polyurethane acrylate compound, an epoxy propylene compound, a carboxyl modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate, an alicyclic epoxy Among the resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane © compounds, and the like, those having a scratch-resistant effect can be used. Among them, examples of the curable compound capable of imparting high scratch resistance include a polyfunctional acrylate compound, a polyfunctional polyester acrylate compound, a polyfunctional epoxy acrylate compound, and the like, and a radical-initiated polymerization system hardening. A compound, or an alkoxydecane, an alkyl alkoxy decane, or the like, or a thermally initiating polymerizable curable compound. These curable compounds are, for example, hardened by irradiation with an energy ray such as an electron beam, radiation, or ultraviolet rays, or hardened by heating. These hardening compounds can be used in a separate manner or in combination with a plurality of compounds. Among these curable compounds, a compound having at least three (meth) acryloxy groups in the molecule is preferred. Here, the (meth) propylene oxime means the propylene oxime group or the methacryloxy group. In addition, in the present specification, ^(methyl)" in (meth) acrylate, (meth)acrylic acid or the like also has the same meaning. The hardening compound having at least three (meth)acryloxyl groups in the molecule may, for example, be trimethylolpropane tri(meth)acrylate, -15-200948607 trimethylolethane tris( Methyl) acrylate, glycerol tri(meth) acrylate, neopentyl tris (tri) acrylate, isovaerythritol tri or tetra (meth) acrylate, diisopentaerythritol three, four, a poly(meth)acrylate of a polyhydric alcohol having a valence of 3 or more of five or six (meth) acrylates, triisopentaerythritol, tetra, penta, hexa, or hepta (meth) acrylate; A compound having two isocyanate groups, which is obtained by reacting a (meth) acrylate monomer having a hydroxyl group with a ratio of an isocyanate group and a hydroxyl group to a molar ratio, and (meth) in one molecule The number of propylene oxime oxime is three or more ethyl urethane (meth) acrylates (for example, by reacting diisocyanate with pentaerythritol tri(meth) acrylate, 3 to 6-functional ethyl urethane (meth) acrylate]; Tris(meth)acrylate of bis(2-hydroxyethyl)trimeric isocyanate. Here, the monomer is exemplified, but the monomer may be used as it is, or a form of an oligomer such as a dimer or a trimer may be used. Further, monomers and oligomers can also be used. These (meth) acrylate compounds may be used alone or in combination of two or more. © Since it is a sclerosing compound having at least three (meth) acryloxy groups, it is also commercially available, and such a commercially available product can also be used. Commercial product - for example, "NK Had Μ 1 01" [New Nakamura Chemical Industry Co., Ltd. product, urethane acrylate system], "ΝΚ埃斯特尔八-TMM-3 L "[Xinzhongcun Chemical Industry Co., Ltd. product, isoprenol triacrylate], "ΝΚ埃斯特尔Α-ΤΜΜΤ" [Xinzhongcun Chemical Industry Co., Ltd., isoprenol tetraacrylate], " ΝΚEsterel Α-9 5 3 0” [Xinzhongcun Chemical Industry Co., Ltd. product, diisopentaerythritol pentaacrylate] -16- 200948607, "NK Estelle a-DPH" [Xinzhongcun Chemical Industrial (stock) products, diisopentyl alcohol hexaacrylate], "KAYARAD DPCA" [Sakamoto Chemicals (stock) products, diisopentyl alcohol hexaacrylate], "Nobukya Asia 200" series [ Cannobco (stock) products], "Unitek, series [Large - 曰本墨化学工业(股)products], etc. _ _ 'There are at least 3 (meth) acrylonitrile groups in the molecule The compound 'may be combined with a further curable compound, for example, ethylene glycol di(meth) acrylate, diethyl Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate-like molecule having two (meth)acryloxy groups The compound is used together with 100 parts by weight of the compound having at least three (meth)acryloxyl groups in the molecule, usually in an amount of 20 parts by weight. For example, when the curable coating is cured by ultraviolet rays, Further, a photopolymerization initiator is used. The photopolymerization initiator may, for example, be benzil, benzophenone or a derivative thereof, thioxanthone or benzyl group. Dimethyl ketals, hydroxyalkyl phenones, hydroxy ketones, aminoalkyl benzophenones, fluorenyl phosphine oxides, etc. - The amount of photopolymerization initiator added is 1 to 00 for hardening compounds. In the range of 1. 1 to 5 parts by weight, the photopolymerization initiators may be used alone or in combination of two or more. In addition, various photopolymerization initiators may be used. It is commercially available and can be used. Commercially available light. The polymerization initiator may, for example, be "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1 000" -17-200948607, "IRGACURE 2959", " D ARO CUR 1 1 7 3',, "IRGACURE 907", "IRGACURE 369", "IRGACURE 1 700", "IRGACURE 1 800", "1RGACURE 819,," "IRGACURE 784" [above IRGACURE series and DAROCUR 歹IJ, sold by Chiba. Special chemicals (.), "KAYACURE ITX", "KAYACURE" DETX-S", "KAYACURE BP-100", "KAYACURE BMS", "KAYACURE 2-EAQ" (the above KAYACURE series, sold by Nippon Kayaku Co., Ltd.), etc. Further, in the present invention, conductive particles are added to the curable coating material for the cured film formed on the acrylic resin layer. The conductive particles used for this purpose include a bismuth-tin composite oxide, a phosphorus-containing tin oxide, a cerium oxide, a cerium-zinc composite oxide, a titanium oxide, an indium-tin composite oxide (ITO), and the like. Inorganic particles. Among them, cerium oxide is preferred. When the conductive particles are blended, the particle size can be appropriately selected according to the type of the particles, and it is usually used in the range of 〇. 5 /zm or less, but the average particle size is obtained from the viewpoint of workability or transparency of the obtained cured film. The diameter is preferably 0.10 or more and 0.1//m or less, more preferably 0.001//m or more and 0.05 5 //m or less. When the average particle diameter of the conductive particles is too large, the haze of the resulting scratch-resistant resin sheet can be increased, so that the transparency is lowered. Further, the amount of the conductive particles used is usually from 2 to 50 parts by weight, preferably from 3 to 20 parts by weight, based on 1 part by weight of the curable compound. If the amount is too small, the effect of improving the workability is degraded. Further, if the amount is too large, the transparency of the cured film may be lowered. -18- 200948607 Such conductive particles can be, for example, vapor decomposition, plasma evaporation, alkoxide decomposition, co-precipitation. Manufactured by hydro-thermal reaction or the like. Further, the surface of the conductive particles may be, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone coupling agent, or an aluminum coupling agent. ) etc. Apply surface treatment. In the curable coating, a dilute solvent is used for the purpose of adjusting the viscosity of the coating material, and in particular, when the conductive particles are added, it is usually used for dispersion. When conductive particles are used and a solvent is used, for example, the conductive particles and the solvent may be mixed to disperse the conductive particles in a solvent, and then the curable compound may be mixed with the curable compound and the solvent, and then The conductive species are mixed for this purpose. The solvent is not particularly limited as long as it can dissolve the curable compound and can be volatilized after coating. When the conductive particles are used as the coating component, they can be dispersed. For example, diacetone alcohol, methanol, ethanol, isopropanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol Alcohols, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol-like ketones, such as toluene, xylene-like aromatic hydrocarbons, such as ethyl acetate, butyl acetate ester Class, water, etc. The amount of the solvent to be used in the curable coating material is not particularly limited, and may be used in an appropriate amount depending on the properties of the curable compound. Further, a well-known leveling agent (-19-200948607 leveling agent) may be added to the curable coating material. The leveling agent may, for example, be a silicone oil or the like. As the polyoxygenated oil, a general one can be used, and specifically, dimethyl sulfonium oil, phenyl methyl sulfonium oil, alkyl aralkyl modified fluorinated oil, fluoro oxirane can be exemplified. Oil, polyether modified helium oxide oil, fatty acid ester modified helium oxide oil, methyl hydrogen oxime oil, sulfonium containing silanol, alkoxy-containing fluorinated oil, phenol Oxygen oil, methacryl-modified helium oxide oil, amine-modified helium-oxygen oil, carboxylic acid-modified helium-oxygen oil, methanol (carbinol) modified helium-oxygen oil, ethoxy-modified helium-oxygen oil,锍 base © modified decane oil, fluorine modified oxime oil, polyether modified oxime oil and so on. Since these leveling agents are commercially available, commercially available products can be used. Commercially available leveling agent, it can be awkward! J: "SH200- 1 OOcs", "SH28PA", "SH29PA,," "SH30PA", "ST83PA", "ST80PA", "ST97PA", "ST86PA"
〔以上均由東麗•陶康寧·聚矽氧（股）所銷售〕等。此 等調平劑，可分別以單獨方式使用，亦混合2種以上使用 。調平劑的使用量，可按照硬化性塗料的特性而適當選擇 ，唯一般而言，對硬化性化合物100重量份，爲0.01至5 G 重量份之程度。 再者，硬化性塗料中，亦可含有穩定化劑、抗氧化劑 - 、著色劑等添加劑。 _ 如此方式，於硬化性化合物中經按照需要混合導電性 粒子、溶劑、調平劑、光聚合引發劑等所得之硬化塗料， 如塗佈於基板表面而作成硬化性塗膜，並接著使其硬化， 則可作成表面上形成有耐擦傷性的硬化被膜之耐擦傷性樹 脂板。 -20- 200948607 如基板上塗佈硬化性塗料而作成硬化性塗膜時，則可 利用例如，鑲條塗佈法（bar coating )、微凹輥塗佈法（ micro gra vure coating)、輥塗法（roll coating)、流挺 塗佈法（flow coating )、浸漬塗佈法（dip coatiing )、 . 旋塗法（spin coating )、壓模塗佈法（spray coating )等 周知的塗佈方法塗佈。如此，將於基板表面形成硬化性塗 膜。然後，按照硬化性塗料的種類，照射紫外線、電子射 © 線等的能量標線、或加熱，藉以使硬化性塗膜硬化，即可 形成耐擦傷性的硬化被膜。 照射能量標線而使其硬化時的能量標線而言，可例舉 :紫外線、電子射線、放射線等，其強度或照射時間，則 按照所採用之硬化性塗料的種類而適當選擇。又，利用加 熱而使其硬化時的加熱溫度或加熱時間等，可按照所採用 之硬化性塗料的種類而適當選擇，惟在加熱硬化時，在防 止基板的變形等之下，一般在100 °c以下的溫度爲宜。如 ® 硬化性塗料含有溶劑時，則可於塗佈後，在使溶劑揮發後 使硬化性塗膜硬化，亦可同時進行溶劑的揮發與硬化性塗 . 膜的硬化。 將形成於聚碳酸酯樹脂層上之硬化被膜，其硬化被膜 的折射率η與聚碳酸酯樹脂層的折射率ns，較佳爲在下述 式 | n-ns| ^0.01 的關係。如此種折射率差在0.0 1以上時，則因在硬化被 膜與聚碳酸酯樹脂層間的光的干擾而發生彩虹花紋，故外 -21 - 200948607 觀上不宜。 如欲調整硬化被膜的折射率爲上述式的範圍時，則可 將分子中具有芳香族環或鹵素原子之具有（甲基）丙烯醯 氧基之化合物作爲硬化性化合物的一部分使用，或者，使 高折射率的有機或無機粒子分散於硬化被膜中，或藉由其 · 兩者的倂用而實施。其中，由於容易調整折射率之故，較 佳爲採用使高折射率的無機粒子分散之方法。 高折射率的無機粒子而言，可例舉：如氧化鈦、氧化 © 錫、氧化銻、氧化銦、氧化銷、氧化鋅般的金屬氧化物粒 子，如銻-鋅複合氧化物、銻-錫複合氧化物、銦-錫複合氧 化物般的複合金屬氧化物粒子，如含磷之氧化錫般的複合 氧化物粒子等。其中，氧化銻、銻-鋅複合氧化物、銻-錫 複合氧化物、銦-錫複合氧化物、含磷之氧化錫等的導電 性粒子，係由於不僅折射率的調整，同時亦能賦與加工性 之故較佳，其中，較佳爲銻-錫複合氧化物、銻-鋅複合氧 化物、含磷之氧化錫。 Θ 高折射率粒子的添加量，係按照欲獲得之折射率或膜 的強度而適當決定者。又，高折射率粒子的粒徑，以平均 - 粒徑計，通常爲0.001至〇.3"m、較佳爲0.001至0.1/zm 、更佳爲0.001至0.05// m。如高折射率粒子的平均粒徑 過大時，則可能所得耐擦傷性樹脂板的霧狀增大，以致透 明性降低。 硬化被膜的厚度，較佳爲0.5至50//m程度、更佳爲 1至20 程度。如硬化被膜的厚度過厚時，則容易發生 -22- 200948607 龜裂，如過薄時，則可能耐擦傷性不足夠。 對所得之耐擦傷性樹脂板，亦可於其表面依塗佈層法 (coating )或灘鏟法（sputtering )、真空蒸鍍法（ vacuum evaporatin)等周知的方法施加防反射處理（anti- - reflection treatment )。又，亦能將另外新製作之防反射 性片材貼合於上述耐擦傷性樹脂板的單面或兩面，以賦與 防反射效果。 © 如此所得耐擦傷性樹脂，係由於抗環境性優異、加工 性亦優異之故，可用於各種用途上，其中作爲行動電話等 的攜帶型資訊終端機很好用者，惟其他數位攝影機（ digital camera)或方便型視訊攝影機（handy type vedeo camera )等的取景器（finder )部、攜帶型遊戲機（game player )的顯示視窗保護板等，或家庭用或業務用的電視 的畫面保護板等，不僅作爲攜帶型資訊終端機，亦可作爲 其他攜帶型顯示機器或設置型的顯示機器作爲對象之顯示 ® 器保護板使用。尤其本發明之耐擦傷性樹脂板，可作爲行 動電話’特別是含有顯示視窗之顯示部，不在使用時折疊 - 而成爲能覆蓋操作鍵部之構造之行動電話的顯示視窗保護 板而發揮有利的效果。 如欲從本發明之耐擦傷性樹脂製作顯示器保護時，則 首先按照需要’進行印刷、穿孔等加工，並進行切割處理 爲所需太小即可。然後’裝配於顯示器上即可作成耐擦傷 性高的顯示器。 -23- 200948607 【實施方式】 〔實施例〕 以下，將舉出實施例以更詳細說明本發明內容，惟本 發明並不因此等實施例而有所限定。例子中，表示含量及 使用量之％及份，除非特別註明’爲重量基準者。 〔基板之製作〕 將聚碳酸酯樹脂（住友陶宇（股）製，佳利巴3 0 1 -1 0 〇 、折射率1.5 8 5 )，使用40mm φ 單軸擠壓機加以熔融混 練，又將丙烯酸樹脂（住友（股）製須美配克斯MH)， 使用20πιιηφ 單軸擠壓機加以熔融混練，並介由給料部件 而加以2層化，接著，介由Τ型模頭（die )而加以擠出 ，按兩面能完全接觸於拋光輥筒（polyshing roll)之方式 冷卻，製得厚度〇.5mm的多層基板。此時，丙烯酸樹脂的 厚度，作成70//m。[The above are all sold by Toray Tao Kangning, Polyoxane (shares)] and so on. These leveling agents can be used separately or in combination of two or more. The amount of the leveling agent to be used can be appropriately selected in accordance with the properties of the curable coating material, and is generally from 0.01 to 5 G by weight per 100 parts by weight of the curable compound. Further, the curable coating material may contain additives such as a stabilizer, an antioxidant, and a colorant. _ In such a manner, a hardened coating obtained by mixing conductive particles, a solvent, a leveling agent, a photopolymerization initiator, or the like, as needed, in a curable compound, for example, is applied to a surface of a substrate to form a curable coating film, and then When it is hardened, it is possible to form a scratch-resistant resin sheet having a hardened film having a scratch resistance formed on its surface. -20- 200948607 When a curable coating film is applied to a substrate to form a curable coating film, for example, bar coating, micro gra vure coating, and roll coating can be used. Well-known coating methods such as roll coating, flow coating, dip coating, drap coat coating, spray coating, etc. cloth. Thus, a curable coating film is formed on the surface of the substrate. Then, the curable coating film is cured by irradiation with an energy ray such as an ultraviolet ray or an electron ray or the like according to the type of the curable coating material, whereby a scratch-resistant cured film can be formed. The energy line when the energy reticle is irradiated and hardened is exemplified by ultraviolet rays, electron rays, radiation, etc., and the strength or irradiation time is appropriately selected depending on the type of the curable coating material to be used. Moreover, the heating temperature, the heating time, and the like when it is cured by heating can be appropriately selected depending on the type of the curable coating material to be used, but in the case of heat curing, it is generally 100 ° under the deformation of the substrate. The temperature below c is preferred. For example, when the curable coating contains a solvent, the curable coating film may be cured after the solvent is volatilized, and the solvent may be volatilized and cured. The film may be cured. The cured film formed on the polycarbonate resin layer has a refractive index η of the cured film and a refractive index ns of the polycarbonate resin layer, preferably in the following formula: n - ns | ^ 0.01 . When the refractive index difference is 0.01 or more, a rainbow pattern is generated due to interference between the cured film and the polycarbonate resin layer, so that it is not preferable. When the refractive index of the hardened film is adjusted to the range of the above formula, a compound having a (meth) acryloxy group having an aromatic ring or a halogen atom in the molecule may be used as a part of the curable compound, or The organic or inorganic particles having a high refractive index are dispersed in the cured film or by the use of both. Among them, since it is easy to adjust the refractive index, it is preferred to employ a method of dispersing inorganic particles having a high refractive index. The inorganic particles having a high refractive index may, for example, be a metal oxide particle such as titanium oxide, tin oxide, antimony oxide, indium oxide, antimony oxide or zinc oxide, such as a bismuth-zinc composite oxide or bismuth-tin. A composite oxide or a composite metal oxide particle such as an indium-tin composite oxide, such as a composite oxide particle such as a phosphorus-containing tin oxide. Among them, conductive particles such as cerium oxide, lanthanum-zinc composite oxide, lanthanum-tin composite oxide, indium-tin composite oxide, and phosphorus-containing tin oxide are not only adjusted in refractive index but also imparted The processability is preferred, and among them, a bismuth-tin composite oxide, a bismuth-zinc composite oxide, and a phosphorus-containing tin oxide are preferable. Θ The amount of the high refractive index particles to be added is appropriately determined depending on the refractive index to be obtained or the strength of the film. Further, the particle diameter of the high refractive index particles is usually 0.001 to 3.3 " m, preferably 0.001 to 0.1/zm, more preferably 0.001 to 0.05//m, in terms of the average particle diameter. If the average particle diameter of the high refractive index particles is too large, the mist of the resulting scratch-resistant resin sheet may increase, so that the transparency is lowered. The thickness of the hardened film is preferably from 0.5 to 50/m, more preferably from 1 to 20. If the thickness of the hardened film is too thick, it is prone to -22-200948607 cracking. If it is too thin, the scratch resistance may not be sufficient. The obtained scratch-resistant resin sheet may also be subjected to anti-reflection treatment (anti-- by a known method such as coating, sputtering, or vacuum evaporatin on the surface thereof. Reflection treatment ). Further, it is also possible to bond another newly produced antireflective sheet to one side or both sides of the above-mentioned scratch-resistant resin sheet to impart an antireflection effect. © The scratch-resistant resin thus obtained is excellent in environmental resistance and excellent in workability, and can be used in various applications. Among them, a portable information terminal such as a mobile phone is well used, but other digital cameras (digital) Camera) or a viewfinder unit such as a handy type vedeo camera, a display window protection board for a game player, or a screen protector for a home or business TV. It can be used not only as a portable information terminal but also as a display controller for other portable display devices or set-up display devices. In particular, the scratch-resistant resin sheet of the present invention can be advantageously used as a display window protection panel for a mobile phone which is a display unit including a display window and which is not folded at the time of use, and which can cover the operation key portion. effect. When the display is to be protected from the scratch-resistant resin of the present invention, it is first necessary to perform processing such as printing, perforation, and the like, and the cutting treatment is required to be too small. Then, by mounting on the display, a display with high scratch resistance can be produced. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the examples, the percentages and parts of the content and the amount used are indicated unless otherwise stated as the basis of the weight. [Production of Substrate] Polycarbonate resin (made by Sumitomo Taoyu Co., Ltd., Jialiba 3 0 1 -1 0 〇, refractive index 1.5 8 5 ), melted and kneaded using a 40 mm φ single-axis extruder, The acrylic resin (Sumitomo) was melt-kneaded using a 20 πιηηφ uniaxial extruder and layered by a feeding member, followed by a die-type die (die). It was extruded and cooled in such a manner that both sides were completely in contact with a polyshing roll to obtain a multilayer substrate having a thickness of 55 mm. At this time, the thickness of the acrylic resin was 70/m.
G 〔硬化性塗料（b 1 )的調製〕 混合二異戊四醇六丙烯酸酯（新中村化學工業（股） - 的“NK酯A-DPH”〕28份、光聚合引發劑〔千葉特殊化學 品（股）的IRGACURE 184〕1份、五氧化銻微粒的溶膠 〔觸媒化成工業（股）的ELCOM-7514;固體成分濃度 2 0%〕8份、1-甲氧-2-丙醇32份、異丁醇32份以及聚矽 氧油〔東麗•陶康寧·聚矽氧（股）的“SH28PA，，〕0·045 份，以調製硬化性塗料（b 1 )。 -24- 200948607 〔硬化性塗料（b2 )的調製〕 混合二異戊四醇六丙烯酸酯（新中村化學工 的“NK酯A-DPH”〕1 3.5份、光聚合引發劑〔千 . 學品（股）的IRGACURE 184〕1份、磷摻雜（c 化錫（平均粒徑16.5份、1-甲氧-2-丙国 以及聚矽氧油〔東麗•陶康寧·聚矽氧1 〇 “ S Η 2 8 P A ”〕0 · 0 2份，以調製硬化性塗料（b 2 )。 〔硬化性塗料（b3 )的調製〕 混合二異戊四醇六丙烯酸酯（新中村化學工 的“NK酯A-DPH”〕30份、1-甲氧-2-丙醇35份 35份、光聚合引發劑〔千葉特殊化學品 IRGACURE 184〕2份、以及聚矽氧油〔東麗· 聚矽氧（股）的“SH28PA”〕0.045份，以調製硬 〔實施例1〕 將基板切割爲10cmx6cm大小，使用Ν〇·220 佈機（bar coater)於丙烯酸樹脂層上形成硬化 bl)的塗膜。接著，在室溫下乾燥1分鐘，再於 風烘箱（oven )內乾燥i 〇分鐘以使溶劑揮發後 膜’使用120W (瓦特）的高壓水銀燈，照射〇 )/ cm2的紫外線以使其硬化，製得於單面（丙 業（股） 葉特殊化 oped )氧 【69份、 股）的 業（股） 、異丙醇 :股）的 陶康寧· 化性塗料 的鑲條塗 性塗料（ 45°C的熱 ，對此塗 _ 5 J (焦耳 烯酸樹脂 -25- 200948607 上）具有硬化被膜之耐擦傷性樹脂板。硬化被膜的折射率 爲1.5 3 8。就該耐擦傷性樹脂板進行下述的評價，並將其 結果，表示於表1中。 〔透明性〕 . 依照JIS K736 1 - 1測定全光線穿透係數（total light transmission factor) (Tt)，並依照 JIS K 7136 測定霧 狀（Η )。 ® 〔硬化被膜之厚度〕 採用膜厚測定裝置〔Filmetrics社製、F-20〕所測定 者。 〔耐擦傷性〕 在 500g/cm2的荷重下，使鋼絲綿（steel wool) #0000來回100次。此時，鋼絲綿的形狀，係作成2cm四 € 方的正方形（面積4cm2 )，作成與其邊成爲平行之方式 纖維並列之狀態。又，來回距離作成l〇cm (單程5cm) - ，按1來回1秒鐘的速度，使其往該纖維方向來回。1〇〇 次來回後，以目視觀察表面的受傷情形，並依下列4階段 加以評價。 A :無受傷 B : 1至2條傷 C : 3至10條傷 -26- 200948607 D : 1 0條以上的傷 〔表面電阻〕 依照ASTM-D257所測定者。 〔加工性〕 採用銑刀銑鏤機（fraise rooter )(朝日美佳羅（股 〇 )製、FR 500)切割試驗片，並以目視觀察其切割面及周 邊的切屑的附著情形，將無切削的附著者作成〇、切屑的 附著少者作成△、切屑的附著多者作成X ° 〔外觀〕 作成按螢光燈的光能映照基材表面之方式以觀表面的 反射光，將未見彩虹花紋者作成〇、彩虹花紋顯眼者作成 X ° ❹ 〔持久鍾曲試驗（permanent camber test)〕 裁切7cmx5cm的試驗片並在85°C的環境下放置3天 後，按四角能浮上之方式將試驗片配置於水平的面上，並 測定其高度，並將與試驗前同樣方式所測定之値的差的最 大値作爲翹曲量。 〔加壓強度〕 於外徑60mmxl00mm、內徑30mmx50mm的金屬製框 -27- 200948607 上，按聚碳酸酯樹脂層能成爲下側之方式配置55mm X 85mm的試驗片，並使用具有直徑10mm的球狀前端之金 屬棒，依10mm/分鐘的速度按壓試驗片中央，以測定試 驗片會破壞之強度。實施其試驗3次，取其平均値爲測定 結果。 〔實施例2〕 切割基板爲l〇cmx6cm的大小後浸漬於硬化性塗料（ © bl)中，採用定速捲上裝置依5 mm/秒的速度捲上，藉以 於其兩表面形成硬化性塗料的塗膜。接著，在室溫下乾燥 1分鐘，再於45 °C的熱風烘箱內乾燥10分鐘以使溶劑揮 發後，對此塗膜，採用120W的高壓水銀燈，照射0.5J/ cm2的紫外線使其硬化，製得兩面上具有硬化被膜之耐擦 傷性樹脂板。就該耐擦傷性樹脂板，進行與實施例1同樣 的評價，並將其結果，表示於表1中。 〔實施例3〕 於按與實施例1同樣方式所得耐擦傷性樹脂板上，使 用N 〇 · 2 0的鑲條塗佈機於聚碳酸酯樹脂層上形成硬化性塗 料（b2)的塗膜。接著，在室溫下乾燥1分鐘，再於45 °C 的熱風烘箱內乾燥10分鐘以使溶劑揮發後，對此塗膜， 使用l2〇W的高壓水銀燈，照射0.5J/ cm2的紫外線以使 其硬化，製得於兩面具有硬化被膜之耐擦傷性樹脂板。聚 碳酸酯樹脂層上的硬化被膜的折射率爲1.584。就該耐擦 -28- 200948607 傷性樹脂板進行與實施例1同樣的評價，並將其結果，表 示於表1中。 〔比較例1〕 - 除不用硬化性塗料（bl)而採用硬化性塗料（b3)以 . 外’其餘則按與實施例1同樣方式，製得於單面上具有硬 化被膜之耐擦傷性樹脂板。就該耐擦傷性樹脂板進行與實 Ο 施例1同樣的評價，並將其結果，表示於表1中。 〔比較例2〕 除不用硬化性塗料（b 1 )而採用硬化性塗料（b 3 )以 外’其餘則按與實施例2同樣方式，製得於兩面上具有硬 化被膜之耐擦傷性樹脂板。就該耐擦傷性樹脂板進行與實 施例1同樣的評價’並將其結果，表示於表1中。 -29- 200948607 表1 例 硬化性塗料 Tt (%) (全光線 穿透係數) Η (%) (霧狀) 膜厚("m) 耐擦傷性 表面電阻 (Ω〇 加 工 性 外 觀 持久 翹曲 (mm) 加壓 強度 (kgf) PMMA 側 PC 側 PMMA 側 PC 側 PMMA 側 PC 側 PMMA 側 PC 側 實施例1 bl _ 90.3 0.4 3.4 _ A D 2χ10π 1015^ Δ 〇 1.2 79 實施例2 bl bl 90.5 0.3 3.2 3.3 A A 2x10" 2x10" 〇 X 1.0 21 實施例3 bl b2 89.6 0.5 3.2 2.8 A A ΙχΙΟ11 6xl09 〇 〇 1.1 24 比較例1 b3 • 90.6 0.3 3.5 A D 1015^ 1015^ X 〇 1.3 76 比較例2 b3 b3 90.7 0.2 3.6 3.4 A A 1015^ 1015^ X 〇 1.2 20G [Preparation of curable coating (b 1 )] Mixed diisopentaerythritol hexaacrylate ("Nano Nakamura Chemical Industry Co., Ltd. - "NK ester A-DPH") 28 parts, photopolymerization initiator [Chiba special chemistry 1 part of IRGACURE 184] of product (stock), sol of pentoxide pentoxide particles (ELCOM-7514 of catalytic polymerization industry); 8 parts of solid content concentration of 2%, 1-methoxy-2-propanol 32 32 parts of isobutanol and 0.045 parts of "SH28PA,," of Toray Taokangning and Polyoxane (shares) to prepare hardenable coatings (b 1 ). -24- 200948607 [Preparation of Curable Coating (b2)] Mixed diisopentaerythritol hexaacrylate ("Nippon Chemical Co., Ltd." "NK ester A-DPH") 1 3.5 parts, photopolymerization initiator [千千学学品) 1 part of IRGACURE 184], phosphorus doped (c tin (average particle size 16.5 parts, 1-methoxy-2-propenium and polyoxygenated oil [Dongli·Tao Kangning·Polyoxime 1 〇" S Η 2 8 PA ”] 0 · 0 2 parts to prepare hardenable coating (b 2 ). [Preparation of hardenable coating (b3)] Mixing diisopentaerythritol hexaacrylate (Naka Nakamura Chemical's “N 30 parts of K ester A-DPH"], 35 parts of 35 parts of 1-methoxy-2-propanol, 2 parts of photopolymerization initiator [Igly special chemical IRGACURE 184], and polyfluorene oxide [Toray · Poly 0.045 parts of "SH28PA" of oxygen (strand) was prepared by modulating hard [Example 1] The substrate was cut into a size of 10 cm x 6 cm, and a coating film of hardening bl was formed on the acrylic resin layer using a bar coater. Then, it was dried at room temperature for 1 minute, and then dried in an air oven for 1 minute to allow the solvent to evaporate. The film was irradiated with a 120 W (watt) high-pressure mercury lamp to irradiate the ultraviolet rays of 〇)/cm2 to harden it. , made of a single-sided (acrylic (share) leaf specialized oped) oxygen [69 parts, shares) of the industry (shares), isopropyl alcohol: shares of Tao Kangning chemical coatings coating coating ( The heat of 45 ° C is coated with a scratch-resistant resin sheet of a hardened film, and the refractive index of the hardened film is 1.5 3 8. The scratch-resistant resin sheet is used. The following evaluations were carried out, and the results are shown in Table 1. [Transparency] . According to JIS K736 1 - 1 The total light transmission factor (Tt) was measured, and the haze (Η) was measured in accordance with JIS K 7136. ® [Thickness of the cured film] Using a film thickness measuring device [Filmetrics, F-20] Measurer. [Scratch resistance] Steel wool #0000 was returned 100 times under a load of 500 g/cm2. At this time, the shape of the steel wool was made into a square of 2 cm square (area 4 cm 2 ), and the fibers were arranged in parallel with the sides thereof. Also, the back and forth distance is made l〇cm (one way 5cm) -, and the speed of 1 round back and forth is 1 second, and it is made to go back and forth in the direction of the fiber. After 1 round trip, the surface injuries were visually observed and evaluated in the following four stages. A : No injury B : 1 to 2 injuries C : 3 to 10 injuries -26- 200948607 D : 10 or more injuries [Surface resistance] Measured in accordance with ASTM-D257. [Processability] The test piece was cut with a fraise rooter (Asahi Mikaro (shares), FR 500), and the adhesion of the cutting surface and the surrounding chips was visually observed, and the cutting was performed without cutting. When the attachment is made into a sputum, the adhesion of the swarf is small, and the adhesion of the swarf is made to X ° [Appearance] The light reflected from the surface of the substrate by the light energy of the fluorescent lamp is reflected by the surface of the substrate, and no rainbow pattern is observed. The person who made the 〇, rainbow pattern is made X ° ❹ [permanent camber test] Cut the test piece of 7cmx5cm and place it in the environment of 85 °C for 3 days, then test it according to the four corners The sheet was placed on a horizontal surface, and its height was measured, and the maximum enthalpy of the difference in enthalpy measured in the same manner as before the test was taken as the amount of warpage. [Pressure strength] A test piece of 55 mm X 85 mm was placed on the metal frame -27-200948607 having an outer diameter of 60 mm x 100 mm and an inner diameter of 30 mm x 50 mm, and a ball having a diameter of 10 mm was used so that the polycarbonate resin layer could be the lower side. The metal rod at the front end pressed the center of the test piece at a speed of 10 mm/min to measure the strength at which the test piece was broken. The test was carried out 3 times, and the average enthalpy was taken as the measurement result. [Example 2] The dicing substrate was sized to a size of 10 cm x 6 cm, and then immersed in a curable coating (© bl), and wound up at a speed of 5 mm/sec by a constant-speed winding device to form a hardenable coating on both surfaces thereof. Coating film. Then, it was dried at room temperature for 1 minute, and then dried in a hot air oven at 45 ° C for 10 minutes to volatilize the solvent, and then the coating film was cured by irradiating an ultraviolet ray of 0.5 J/cm 2 with a 120 W high-pressure mercury lamp. A scratch-resistant resin sheet having a hardened film on both sides was obtained. The same evaluation as in Example 1 was carried out on the scratch-resistant resin sheet, and the results are shown in Table 1. [Example 3] A coating film of a curable coating material (b2) was formed on a polycarbonate resin layer using a N 2200 strip coater on a scratch-resistant resin sheet obtained in the same manner as in Example 1. . Then, it was dried at room temperature for 1 minute, and further dried in a hot air oven at 45 ° C for 10 minutes to volatilize the solvent, and then the coating film was irradiated with ultraviolet rays of 0.5 J/cm 2 using a high pressure mercury lamp of l 2 〇W to make It is hardened to obtain a scratch-resistant resin sheet having a hardened film on both sides. The refractive index of the cured film on the polycarbonate resin layer was 1.584. The same evaluation as in Example 1 was carried out on the scratch-resistant -28-200948607, and the results are shown in Table 1. [Comparative Example 1] - A curable coating material having a hardened film on one side was obtained in the same manner as in Example 1 except that the curable coating material (b3) was used instead of the curable coating material (b1). board. The same evaluation as in the Example 1 was carried out on the scratch-resistant resin sheet, and the results are shown in Table 1. [Comparative Example 2] A scratch-resistant resin sheet having a hardened film on both surfaces was obtained in the same manner as in Example 2 except that the curable coating material (b 1 ) was used instead of the curable coating material (b 1 ). The same evaluation as in Example 1 was carried out on the scratch-resistant resin sheet, and the results are shown in Table 1. -29- 200948607 Table 1 Example of hardening coating Tt (%) (total light penetration coefficient) Η (%) (mist) film thickness ("m) scratch resistance surface resistance (Ω〇 processability appearance long-lasting warpage (mm) Pressurization strength (kgf) PMMA side PC side PMMA side PC side PMMA side PC side PMMA side PC side Example 1 bl _ 90.3 0.4 3.4 _ AD 2χ10π 1015^ Δ 〇 1.2 79 Example 2 bl bl 90.5 0.3 3.2 3.3 AA 2x10"2x10" 〇X 1.0 21 Example 3 bl b2 89.6 0.5 3.2 2.8 AA ΙχΙΟ11 6xl09 〇〇1.1 24 Comparative Example 1 b3 • 90.6 0.3 3.5 AD 1015^ 1015^ X 〇1.3 76 Comparative Example 2 b3 b3 90.7 0.2 3.6 3.4 AA 1015^ 1015^ X 〇1.2 20
〔註〕PMMA側：丙烯酸樹脂層側 PC側：聚碳酸酯樹脂側 〔產業上之利用可能性〕 本發明之耐擦傷性樹脂，係抗環境性優異、加工性亦 優異者，如將該耐擦傷性樹脂板作爲顯示器保護板，特別 是作爲滯帶型資訊終端機的顯示視窗保護板使用時，則可 有效保護其顯示視窗。 ❹ -30-[Note] PMMA side: Acrylic resin layer side PC side: Polycarbonate resin side [Industrial use possibility] The scratch-resistant resin of the present invention is excellent in environmental resistance and excellent in workability, such as resistance When the scratch-resistant resin board is used as a display protection board, particularly when it is used as a display window protection board of a hysteresis type information terminal, the display window can be effectively protected. ❹ -30-