201100248 六、發明說明： 【發明所屬之技術領域】 本發明關於適合作爲顯示器保護板及攜帶型資訊終端 之顯示窗保護板之耐擦傷性樹脂板、及使用其之顯示器保 護板及攜帶型資訊終端之顯示窗保護板。 1J 術 技 前 先 0 向來，作爲顯示器等的保護板，使用耐擦傷性樹脂板 。耐擦傷性樹脂板係在透明樹脂基板的表面上形成具耐擦 傷性（硬塗性）的硬化被膜所成。如此的耐擦傷性樹脂板 ’若長期持續使用，則會變色。即，以往的耐擦傷性樹脂 板係耐候性不充分。 專利文獻1及2中記載液晶顯示器蓋用的耐擦傷性樹脂 板。此耐擦傷性樹脂板係以在聚碳酸酯樹脂層的一面上層 合指定厚度的丙烯酸樹脂層所成的層合體當作基板，藉由 Q 在前述丙烯酸樹脂層上形成硬化被膜，以提高表面硬度及 耐衝撃性。又，專利文獻1及2中記載爲了長期間保持耐候 性，在前述丙烯酸樹脂層中含有指定量的紫外線吸收劑。 然而，專利文獻1及2中記載的耐擦傷性樹脂板之耐候 性係未必充分。爲了提高耐擦傷性樹脂板的耐候性，亦考 慮增加所添加的紫外線吸收劑量。然而，若增加紫外線吸 收劑量，雖然耐候性提高，但是表面硬度降低。 先前技術文獻 專利文獻 -5- 201100248 [專利文獻1]特開2006-103169號公報 [專利文獻2]特開2007-237700號公報 【發明內容】 [發明所欲解決的問題] 本發明之課題爲提供一邊維持表面硬度，一邊具有優 異耐候性的耐擦傷性樹脂板，及使用其之顯示器保護板及 攜帶型資訊終端之顯示窗保護板。 [解決問題的手段] 本發明的耐擦傷性樹脂板係由以下的構成所成。 (1 ) 一種耐擦傷性樹脂板，其係由樹脂基板與形成 在其表面上的硬化被膜所成之耐擦傷性樹脂板，前述樹脂 基板係由聚碳酸酯樹脂層與至少層合在其一面上的丙烯酸 樹脂層所成，前述聚碳酸酯樹脂層及丙烯酸樹脂層皆含有 紫外線吸收劑，前述丙烯酸樹脂層每1 m2的紫外線吸收劑 之含量爲0.005〜lg，而且前述樹脂基板每im2的紫外線吸 收劑之含量爲〇·5〜2g，前述硬化被膜係至少形成在前述 丙烯酸樹脂層之表面上。 (2 )如前述（1 )記載之耐擦傷性樹脂板，其中前述 樹脂基板係由聚碳酸酯樹脂層與層合在其兩面的丙烯酸樹 脂層所成。 (3 )如前述（1 )或（2 )記載之耐擦傷性樹脂板， 其中前述硬化被膜係由含有在分子中至少具有3個（甲基 -6- 201100248 )丙烯醯氧基的化合物之硬化性塗料組成物所形成的被膜 〇 本發明的顯示器保護板係由前述（1 )〜（3 )中任一 項記載之耐擦傷性樹脂板所成。 本發明的攜帶型資訊終端之顯示窗保護板係由前述（ 1 )〜（3 )中任一項記載之耐擦傷性樹脂板所成。 再者，本發明中的前述「攜帶型資訊終端」係人可攜 π 行的程度之大小，意味具有用於顯示文字資訊或圖像資訊 Ο 等的窗（顯示器）之終端的總稱，例如可舉出攜帶電話或 PHS ( Personal Handy-phone System ) 、PDA ( Personal201100248 VI. Description of the Invention: [Technical Field] The present invention relates to a scratch-resistant resin board suitable as a display protection panel for a display protection board and a portable information terminal, and a display protection board and a portable information terminal using the same Display window protection board. Before the 1J technique, the first 0-way is used as a protective plate for a display, etc., and a scratch-resistant resin plate is used. The scratch-resistant resin sheet is formed by forming a hardened film having scratch resistance (hard coating property) on the surface of the transparent resin substrate. Such a scratch-resistant resin sheet □ discolors if it is used continuously for a long period of time. That is, the conventional scratch-resistant resin sheet is insufficient in weather resistance. Patent Documents 1 and 2 describe scratch-resistant resin sheets for liquid crystal display covers. The scratch-resistant resin sheet is obtained by laminating a laminate of a predetermined thickness of an acrylic resin layer on one surface of a polycarbonate resin layer as a substrate, and forming a hardened film on the acrylic resin layer by Q to improve surface hardness. And resistance to punching. Further, in Patent Documents 1 and 2, it is described that a predetermined amount of the ultraviolet absorber is contained in the acrylic resin layer in order to maintain weather resistance for a long period of time. However, the weather resistance of the scratch-resistant resin sheet described in Patent Documents 1 and 2 is not necessarily sufficient. In order to improve the weather resistance of the scratch-resistant resin sheet, it is also considered to increase the amount of the ultraviolet absorbing agent to be added. However, if the ultraviolet absorbing amount is increased, although the weather resistance is improved, the surface hardness is lowered. [Patent Document 1] JP-A-2007-237700 [Patent Document 2] JP-A-2007-237700 (Summary of the Invention) [Problems to be Solved by the Invention] The subject of the present invention is A scratch-resistant resin sheet having excellent weather resistance while maintaining surface hardness, and a display protection sheet using the display protection panel and the portable information terminal. [Means for Solving the Problem] The scratch-resistant resin sheet of the present invention is composed of the following constitution. (1) A scratch-resistant resin sheet which is a scratch-resistant resin sheet formed of a resin substrate and a cured film formed on a surface thereof, wherein the resin substrate is laminated on at least one side of a polycarbonate resin layer In the upper acrylic resin layer, the polycarbonate resin layer and the acrylic resin layer each contain an ultraviolet absorber, and the content of the ultraviolet absorber per 1 m 2 of the acrylic resin layer is 0.005 to lg, and the ultraviolet resin per im2 of the resin substrate The content of the absorbent is 〇·5 to 2 g, and the hardened film is formed on at least the surface of the acrylic resin layer. (2) The scratch-resistant resin sheet according to the above (1), wherein the resin substrate is formed of a polycarbonate resin layer and an acrylic resin layer laminated on both surfaces thereof. (3) The scratch-resistant resin sheet according to the above (1) or (2), wherein the hardening film is hardened by a compound containing at least three (methyl-6-201100248) acryloxy groups in the molecule. The film protective sheet of the present invention is formed of the scratch-resistant resin sheet according to any one of the above (1) to (3). The display window protection panel of the portable information terminal of the present invention is formed by the scratch-resistant resin sheet according to any one of the above (1) to (3). Furthermore, the above-mentioned "portable information terminal" in the present invention is a general term for a terminal that can carry a π line, and means a terminal having a window (display) for displaying text information or image information, etc., for example, Give a mobile phone or PHS (Personal Handy-phone System), PDA (Personal
Digital Assistant)等。 [發明的效果] 本發明的耐擦傷性樹脂板係可一邊維持表面硬度，一 邊顯示長期優異的耐候性。因此，藉由使用此耐擦傷性樹 Q脂板當作顯示器保護板，尤其攜帶型資訊終端之顯示窗保 護板，可長期有效地保護其顯示器（顯示窗）。 式 方 施 [實施發明的形態] 本發明的耐擦傷性樹脂板係由樹脂基板與形成在其表 面上的硬化被膜所成。前述樹脂基板係由聚碳酸酯樹脂層 與至少層合在其一面上的丙烯酸樹脂層之層合體所成。藉 此，前述樹脂基板係表面硬度及耐衝撃性優異，而且即使 201100248 被擠壓也不易破裂。 作爲構成前述聚碳酸酯樹脂層的聚碳酸酯樹脂’例如 可舉出藉由界面聚縮合法、熔融酯交換法等使1種以上的 二價酚與1種以上的羰基化劑反應而得之聚合物，藉由固 相酯交換法等使碳酸酯預聚物聚合而得之聚合物，藉由開 環聚合法使環狀碳酸酯化合物聚合而得之聚合物等。 作爲前述二價酚，例如可舉出氫醌、間苯二酚、4,4’-二羥基聯苯、雙（4-羥苯基）甲烷、雙{(4-羥基-3,5-二甲基） 苯基}甲烷、1，1-雙（4_羥苯基）乙烷、1，1-雙（4-羥苯基）-1-苯基乙烷、2,2-雙（4-羥苯基）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）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-羥苯基）丁烷、2,2-雙（4-羥苯基-3-甲基丁 烷、2,2-雙（4-羥苯基）-3,3-二甲基丁烷、2,4-雙（4-羥苯基）-2-甲基丁烷、2,2-雙（4-羥苯基）戊烷、2,2-雙（4-羥苯基）-4-甲基戊烷、1,1-雙（心羥苯基）環己烷、1，1_雙（4-羥苯基）-4-異丙基環己烷、1，1-雙（4_羥苯基）-3,3,5-三甲基環己烷、 9,9-雙（4-羥苯基）蒹、9,9-雙{(4-羥基-3-甲基）苯基}莽、 α，α’-雙（4 -羥苯基）-〇 -二異丙基苯、α，α，-雙（4 -羥苯基）-m-二異丙基苯、α，α’-雙（4-羥苯基）_p-二異丙基苯、ι，3-雙（4-羥苯基）-5,7-二甲基金剛烷、4,4，-二羥基二苯基楓、4,4，-二羥基二苯基亞颯、4,4’-二羥基二苯基硫化物、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 -8 - 201100248 等。 其中，較佳爲單獨或使用2種以上的由雙酚A、2 {(4-羥基-3-甲基）苯基）丙院、2,2_雙（4_經苯基）丁院、 雙（4 -經苯基）-3 -甲基丁院、2,2'雙（4_經苯基）-3,3 -二 丁烷、2,2-雙（4-羥苯基）-4-甲基戊烷、1，1-雙（4-羥苯 3,3,5-三甲基環己烷及α，α’-雙（4-羥苯基）_m-二異丙基 組成族群所選出的價酸’特佳爲由雙酚A的均聚物 酚AM 1，1-雙（4-羥苯基）-3,3,5-三甲基環己烷的共聚合 〇 雙酚A與2,2-雙{(4-羥基-3-甲基）苯基}丙烷及 苯基）-m-二異丙基苯所組成族群所選出的1種以上之 酚之共聚合物。 作爲前述羰基化劑，例如可舉出光氣等的羰基鹵 酸二苯酯等的碳酸酯、二價酚的二鹵甲酸酯等的鹵甲 等。 作爲構成前述丙烯酸樹脂層的丙烯酸樹脂，一般 Q 甲基丙烯酸樹脂。甲基丙烯酸樹脂係可爲甲基丙烯酸 均聚物，也可爲甲基丙烯酸甲酯和與該甲基丙烯酸甲 共聚合的1種以上之其它單體的共聚物。於甲基丙烯 脂爲與甲基丙烯酸甲基可共聚合的1種以上之其它單 共聚物時，甲基丙烯酸樹脂較佳爲以甲基丙烯酸甲酯 當作主成分，具體地較佳含有50重量％以上的甲基丙 甲酯單位，更佳含有70重量％以上的甲基丙烯酸甲酯 〇 作爲與前述甲基丙烯酸甲酯可共聚合的其它單體 ，2-雙 2,2-甲基 基）-苯所 、雙 物、 〔4-羥 二價 、碳 酸酯 使用 甲酯 酯可 酸樹 體的 單位 烯酸 單位 ，例 -9 - 201100248 如可舉出甲基丙烯酸乙酯、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-羥乙酯等的甲基丙烯酸甲酯以 外之甲基丙烯酸酯類，或丙烯酸甲酯、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-羥乙酯等的丙烯酸酯類。又，亦 可舉出苯乙烯或取代苯乙烯類，例如氯苯乙烯、溴苯乙烯 等的鹵化苯乙烯類，或乙烯基甲苯、α-甲基苯乙烯等的烷 基苯乙烯類。再者，也可舉出甲基丙烯酸、丙烯酸等的不 fΊ 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。 前述聚碳酸酯樹脂層及丙烯酸樹脂層含有任丨種以上 的紫外線吸收劑。作爲前述紫外線吸收劑，例如可舉出苯 并二唑系、二苯甲酮系、水楊酸苯酯系、三π并系的紫外線 吸收劑等。 作爲前述苯并三唑系紫外線吸收劑，例如可舉出2_ ( 5 -甲基-2-羥苯基）苯并三唑、2-[2 -羥基- 3,5 -雙（α，α -二甲 ❹ 基节基）苯基]-2Η-苯并三唑、2_ ( 2，-羥基_5，_tert_辛基苯 基）苯并三唑、12-亞甲基雙[4- ( 1，1，3,3-四亞甲基丁基 )-6- ( 2H-苯并三唑-2_基）酚]等。作爲前述二苯甲酮系 紫外線吸收劑’例如可舉出2_羥基-4-辛氧基二苯甲酮、 2’4 —經基—本甲酮、2_經基-4-甲氧基-4’-氯二苯甲酮、 2,2-二羥基甲氧基二苯甲酮、2,2-二羥基_4,4，_二甲氧基 二苯甲酮等。作爲前述水楊酸苯酯系紫外線吸收劑，例如 -10 - 201100248 可舉出水楊酸對第三-丁基苯酯等。作爲前述三畊系紫外線 吸收劑，例如可舉出2,4 -二苯基-6- (2 -羥基-4 -甲氧基苯基 )-1，3,5-三畊、2,4-二苯基-6-(2-羥基-4-乙氧基苯基）_ 1，3,5-三畊、2,4-二苯基-(2-羥基-4-丙氧基苯基）-:1,3,5-三畊、2,4-二苯基-(2-羥基-4-丁氧基苯基）-I，3,5 —三畊、 2,4-二苯基-6-(2-羥基-4-丁氧基苯基）-1，3,5_三畊、2,4-二苯基-6- (2-羥基-4-己氧基苯基）_1，3,5-三畊、2,4-二苯 基-6- ( 2-羥基-4-辛氧基苯基）-1，3,5-三畊、2,4-二苯基-6-(2-羥基-4-十二氧基苯基）-1,3，5-三畊、2,4-二苯基- 6-( 2-經基-4-卞氧基苯基）-1,3,5 -二Π并、2,4 -二苯基-6- ( 2-經 基-4· 丁氧基乙氧基）-I,3,5-三畊等。 聚碳酸酯樹脂層中所含有的紫外線吸收劑與丙烯酸樹 脂層中所含有紫外線吸收劑係可互相相同或不同。 本發明中的紫外線吸收劑係不限定於前述所例示的紫 外線吸收劑’而包含各種眾所周知的紫外線吸收劑。 此處，前述丙烯酸樹脂層每1 m2的紫外線吸收劑之含 量爲0.0 0 5〜1 g ’而且前述樹脂基板每i m2的紫外線吸收劑 之含量爲〇_ 5〜2g。藉此’本發明的耐擦傷性樹脂板可一 邊維持表面硬度，一邊顯示長期優異的耐候性。 即’於前述丙烯酸樹脂層的表面上，如後述地形成硬 化被膜。丙烯酸樹脂層中的紫外線吸收劑之含量若太多， 則丙烯酸樹脂層的剛性會降低，隨此所得之耐擦傷性樹脂 板的表面硬度亦會降低。本發明的耐擦傷性樹脂板，由於 丙烯酸樹脂層中的紫外線吸收劑之含量在前述範圍內，故 -11 - 201100248 可維持表面硬度。又，爲了顯示長期安定的耐候性，樹脂 基板全體的紫外線吸收劑量係重要。本發明的耐擦傷性樹 脂板，由於樹脂基板全體中的紫外線吸收劑之含量在前述 範圍內，故可顯示長期安定的耐候性。 前述丙烯酸樹脂層及前述樹脂基板中的紫外線吸收劑 之含量若太少，則所得之耐擦傷性樹脂板的耐候性會變不 充分。前述樹脂基板中的紫外線吸收劑之含量若太多，則 得不到與其相衡的效果，變經濟上不利。前述聚碳酸酯樹 脂層中的紫外線吸收劑之含量較佳爲5 0 0〜3 0 0 0 p p m，前述 丙烯酸樹脂層中的紫外線吸收劑之含量較佳爲1 00〜 1 OOOOppm 〇 前述聚碳酸酯樹脂層及丙烯酸樹脂層各自可含有光擴 散劑、消光劑、染料、光安定劑、抗氧化劑、脫模劑、難 燃劑、抗靜電劑等的1種以上之添加劑。 前述樹脂基板通常爲薄片狀或薄膜狀，其厚度通常爲 0.3〜3mm，較佳爲0.3〜2mm，更佳爲0.4〜1.5mm。於樹 脂基板中，前述丙烯酸樹脂層的厚度通常爲50〜120μπα， 較佳爲60〜110 μηι，更佳爲70〜1〇〇 μιη。丙烯酸樹脂層的 厚度愈小，則耐擦傷性樹脂板的耐衝撃性愈升高，而且即 使耐擦傷性樹·脂板被擠壓，也有不易破裂的傾向，但是丙 烯酸樹脂層的厚度若太小，則耐擦傷性樹脂板的表面硬度 會降低。又，丙烯酸樹脂層的厚度若太大，則耐擦傷性樹 脂板的耐衝撃性會降低。 樹脂基板亦可爲僅在聚碳酸酯樹脂層的一面上層合有 -12- 201100248 丙烯酸樹脂層之2層構造層合體，也可爲在聚碳酸酯樹脂 層的兩面層合有丙嫌酸樹脂層之3層構造層合體。從耐擦 傷性樹脂板的耐環境性，例如從暴露於高溫下或高濕下時 不易翹曲之點來看，較佳爲在聚碳酸酯樹脂層的兩面層合 有丙烯酸樹脂層的樹脂基板。於3層構造的情況中，兩面 的丙烯酸樹脂層只要各自的丙烯酸樹脂層每lm2的紫外線 吸收劑之含量爲0.00 5〜lg，則其組成及厚度可爲互相相 同或不同。例如，於兩面的丙烯酸樹脂層之中，當一方含 0 有橡膠粒子時，另一方可含有或可不含有橡膠粒子。 如此的樹脂基板係可藉由共壓出成形將聚碳酸酯樹脂 層與丙烯酸樹脂層層合一體化而製造。此共壓出成形係可 藉由使用2台或3台的一軸或二軸之擠壓機，將聚碳酸酯樹 脂層的材料與丙烯酸樹脂層的材料各自熔融混煉後，通過 供料頭式（feedblock)模頭或多歧管（multi-manifold) 模頭等來層合而進行。經層合一體化的熔融層合樹脂體， Q例如可使用輥單元來進行冷卻固化。共壓出成形所製造的 樹脂基板，與使用黏著劑或接著劑所貼合而製造的樹脂基 板相比，係容易二次成形。 前述硬化被膜係至少形成在前述丙烯酸樹脂層表面上 。於聚碳酸酯樹脂層的兩面層合有丙烯酸樹脂層時，前述 硬化被膜係形成在至少一面的丙烯酸樹脂層表面上。因此 ，作爲本發明的耐擦傷性樹脂板之層構成，可舉出下述（ i )〜（i v )。 (i )硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層 -13- 201100248 (ii )硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層/硬化 被膜 (iii )硬化被膜/丙烯酸樹脂層/聚碳酸酯樹脂層/丙烯 酸樹脂層 (iv)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 再者，於樹脂基板的兩面形成硬化被膜時，兩面的硬 化被膜之組成及厚度係可互相相同或不同。 形成硬化被膜用的硬化性塗料組成物，係含有能帶來 耐擦傷性的1種以上之硬化性化合物當作必要成分，視需 要可含有硬化觸媒、導電性粒子、溶劑、均平劑、安定化 劑、抗氧化劑、著色劑等。 作爲前述硬化性化合物，例如可舉出丙烯酸酯化合物 、胺基甲酸乙酯丙烯酸酯化合物、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 聚合系丙烯酸酯化合物、脂環式環氧樹脂、縮水甘油醚環 氧樹脂、乙烯醚化合物、氧雜環丁烷化合物等。其中，從 硬化被膜的耐擦傷性之點來看，較佳爲多官能丙烯酸酯化 合物 '多官能胺基甲酸乙酯丙烯酸酯化合物、多官能環氧 丙烯酸酯化合物等的自由基聚合系硬化性化合物、烷氧基 矽烷、烷基烷氧基矽烷等的熱聚合系硬化性化合物。此等 硬化性化合物較佳爲藉由照射電子線、輻射線、紫外線等 的能量線而硬化的化合物，或藉由加熱而硬化的化合物。 特佳的硬化性化合物係在分子中具有至少3個（甲基 -14- 201100248 )丙烯醯氧基的化合物。此處，（甲基）丙烯醯氧基係指 丙烯醯氧基或甲基丙烯醯氧基，此外於本說明書中，稱爲 (甲基）丙烯酸酯、（甲基）丙烯酸等時的「（甲基）」 亦是同樣的意思。 作爲分子中具有至少3個（甲基）丙烯醯氧基的化合 物，例如可舉出如三羥甲基丙烷三（甲基）丙烯酸酯、三 羥甲基乙烷三（甲基）丙烯酸酯、甘油三（甲基）丙烯酸 酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇三-或四_( 〇 甲基）丙烯酸酯、二季戊四醇三-或四-、五-或六-(甲基 )丙烯酸酯、三季戊四醇四-、五-、六-或七-(甲基）丙 烯酸酯的3價以上之多元醇的聚（甲基）丙烯酸酯；對在 分子中具有至少2個異氰酸酯基的化合物，使具有羥基的 (甲基）丙烯酸酯以相對於異氰酸酯基而言羥基爲等莫耳 以上的比例進行反應而得之具有3個以上（甲基）丙烯醯 氧基的胺基甲酸乙酯（甲基）丙烯酸酯[例如由二異氰酸 q酯與季戊四醇三（甲基）丙烯酸酯之反應得到6官能的胺 基甲酸乙酯（甲基）丙烯酸酯];三（2-羥乙基）異氰尿酸 的三（甲基）丙烯酸酯。再者，此處例示單體，可直接使 用此等單體，但例如也可使用2聚物、3聚物等的寡聚物。 又，亦可倂用單體與寡聚物。 作爲在分子中具有至少3個（甲基）丙烯醯氧基的化 合物之市售品，例如可舉出新中村化學工業（股）的“NK hard M101”（胺基甲酸乙酯丙烯酸酯系）、“NK酯A-TMM-3L”（季戊四醇三丙烯酸酯）、“NK酯A-TMMT”（季戊四 -15- 201100248 醇四丙烯酸酯）、“ΝΚ酯A-9530”（二季戊四醇五丙烯酸酯 )及NK酯A-DPH”（二季戊四醇六丙烯酸酯）、日本化藥（ 股）的“KAYARAD DPCA”（二季戊四醇六丙烯酸酯）、 SANNOPCO(股）的“Nopocure 200”系列、大日本油墨化學 工業（股）的“Unidic”系列等。 再者，使用在分子中具有至少3個（甲基）丙烯醯氧 基的化合物當作硬化性化合物時，視需要亦可倂用其它硬 化性化合物，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）丙烯酸酯等之在分子中具有2個（甲 基）丙烯醯氧基的化合物。於倂用其它硬化性化合物時， 相對於1〇〇重量份的在分子中具有至少3個（甲基）丙烯醯 氧基的化合物而言，其它硬化性化合物的使用量通常較佳 爲20重量份以下。 以紫外線使硬化性塗料組成物硬化時，較佳爲使用1 種以上的光聚合引發劑當作硬化觸媒。作爲前述光聚合引 發劑，例如可舉出苯偶醯、二苯甲酮或其衍生物、噻噸酮 類、苄基二甲基縮酮類、α-羥基烷基苯酮類、羥基酮類、 胺基烷基苯酮類、醯基磷氧化物類等。相對於100重量份 的硬化性化合物而言，光聚合引發劑的使用量通常爲〇. 1 〜5重量份。Digital Assistant) and so on. [Effect of the invention] The scratch-resistant resin sheet of the present invention exhibits long-term excellent weather resistance while maintaining the surface hardness. Therefore, by using the scratch-resistant tree Q-fat board as a display protection board, particularly the display window protection board of the portable information terminal, the display (display window) can be effectively protected for a long period of time. [Form of the Invention] The scratch-resistant resin sheet of the present invention is formed of a resin substrate and a cured film formed on the surface thereof. The resin substrate is formed of a laminate of a polycarbonate resin layer and an acrylic resin layer laminated on at least one side thereof. Therefore, the resin substrate is excellent in surface hardness and impact resistance, and is not easily broken even if it is pressed at 201100248. The polycarbonate resin constituting the polycarbonate resin layer is obtained by, for example, reacting one or more kinds of divalent phenols with one or more kinds of carbonylating agents by an interfacial polycondensation method, a melt transesterification method, or the like. The polymer is a polymer obtained by polymerizing a carbonate prepolymer by a solid phase transesterification method or the like, and a polymer obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. Examples of the divalent phenol include hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, and bis{(4-hydroxy-3,5-di). Methyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-dual (4 -Hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-.methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-di Methyl)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-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(hydroxyphenyl)cyclohexane 1,1_bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9 ,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-double (4-hydroxyphenyl)-indole-diisopropylbenzene, α,α,-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl) )_p-diisopropylbenzene, iota, 3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4,-dihydroxydiphenyl maple, 4,4,-di Hydroxydiphenylarylene, 4,4'-dihydroxydiphenyl sulfide, 4,4,-dihydroxydiphenyl ketone '4,4'-dihydroxydiphenyl ether' 4,4,-two Hydroxydiphenyl ester-8 - 201100248, etc. Among them, it is preferred to use bisphenol A, 2 {(4-hydroxy-3-methyl)phenyl) propyl broth, 2, 2 _ alone or in combination. Bis (4-phenyl) butyl, bis(4-phenyl)-3-methyldin, 2,2'bis(4-phenyl)-3,3-dibutane, 2, 2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxybenzene 3,3,5-trimethylcyclohexane and α,α'-bis(4- The valeric acid selected from the group consisting of hydroxyphenyl)_m-diisopropyl is particularly preferred as the homopolymer phenol AM 1,1-bis(4-hydroxyphenyl)-3,3,5- from bisphenol A. Copolymerization of trimethylcyclohexane with bisphenol A and 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane and phenyl)-m-diisopropylbenzene A copolymer of more than one phenol selected by the ethnic group. Examples of the carbonylating agent include a carbonate such as diphenyl carbonyl halide such as phosgene, and a halogenated group such as a dihaloformate of a divalent phenol. As the acrylic resin constituting the acrylic resin layer, a Q methacrylic resin is generally used. The methacrylic resin may be a methacrylic acid homopolymer or a copolymer of methyl methacrylate and one or more other monomers copolymerized with the methacrylic acid. When the methacrylic acid ester is one or more other single copolymers copolymerizable with the methyl methacrylate group, the methacrylic resin preferably has methyl methacrylate as a main component, and specifically preferably contains 50. More than 100% by weight of methyl propyl methyl ester unit, more preferably 70% by weight or more of methyl methacrylate oxime as other monomer copolymerizable with the aforementioned methyl methacrylate, 2-bis 2,2-methyl Base)-benzene, di-, benzylic acid, methacrylic acid, methyl methacrylate, methacrylic acid, methyl methacrylate, methacrylic acid Methyl methacrylate other than butyl ester, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, etc. Acrylates, or acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc. . Further, examples thereof include styrene or substituted styrenes such as halogenated styrenes such as chlorostyrene and bromostyrene, and alkylstyrenes such as vinyltoluene and ?-methylstyrene. Further, a non-fluorene-saturated acid such as methacrylic acid or acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide or cyclohexylmaleimide may be mentioned. The polycarbonate resin layer and the acrylic resin layer contain any of ultraviolet rays or more. Examples of the ultraviolet absorber include a benzobisazole type, a benzophenone type, a phenyl salicylate type, and a triple π-type ultraviolet absorber. Examples of the benzotriazole-based ultraviolet absorber include 2-(5-methyl-2-hydroxyphenyl)benzotriazole and 2-[2-hydroxy-3,5-bis(α,α- Dimethyl hydrazino)phenyl]-2-indole-benzotriazole, 2_(2,-hydroxy-5,_tert-octylphenyl)benzotriazole, 12-methylenebis[4-( 1 , 1,3,3-tetramethylenebutyl)-6-(2H-benzotriazol-2-yl)phenol] and the like. Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-octyloxybenzophenone, 2'4-pyridyl-methanone, and 2-pyridyl-4-methoxy. -4'-chlorobenzophenone, 2,2-dihydroxymethoxybenzophenone, 2,2-dihydroxy-4,4,4-dimethoxybenzophenone, and the like. Examples of the phenyl salicylate-based ultraviolet absorber include, for example, -10 - 201100248, salicylic acid-p-tert-butylphenyl ester and the like. Examples of the three-till ultraviolet absorber include 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-three tillage, 2,4- Diphenyl-6-(2-hydroxy-4-ethoxyphenyl)_ 1,3,5-trin, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl) -: 1,3,5-three tillage, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-I,3,5-three tillage, 2,4-diphenyl- 6-(2-hydroxy-4-butoxyphenyl)-1,3,5_three tillage, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)_1, 3,5-three tillage, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-three tillage, 2,4-diphenyl-6- (2-hydroxy-4-dodecylphenyl)-1,3,5-three tillage, 2,4-diphenyl-6-(2-pyridyl-4-decyloxyphenyl)-1 , 3,5-diindolo, 2,4-diphenyl-6-(2-amino-4·butoxyethoxy)-I, 3,5-three tillage, and the like. The ultraviolet absorber contained in the polycarbonate resin layer and the ultraviolet absorber contained in the acrylic resin layer may be the same or different from each other. The ultraviolet absorber in the present invention is not limited to the ultraviolet absorber exemplified above, and includes various well-known ultraviolet absorbers. Here, the content of the ultraviolet absorber per 1 m 2 of the acrylic resin layer is 0.02 to 1 g ', and the content of the ultraviolet absorber per i m 2 of the resin substrate is 〇 5 to 2 g. By the fact, the scratch-resistant resin sheet of the present invention exhibits long-term excellent weather resistance while maintaining the surface hardness. That is, a hard coating film is formed on the surface of the acrylic resin layer as will be described later. If the content of the ultraviolet absorber in the acrylic resin layer is too large, the rigidity of the acrylic resin layer is lowered, and the surface hardness of the resulting scratch-resistant resin sheet is also lowered. In the scratch-resistant resin sheet of the present invention, since the content of the ultraviolet absorber in the acrylic resin layer is within the above range, the surface hardness can be maintained from -11 to 201100248. Further, in order to exhibit long-term stability and weather resistance, the ultraviolet absorbing dose of the entire resin substrate is important. In the scratch-resistant resin sheet of the present invention, since the content of the ultraviolet absorber in the entire resin substrate is within the above range, it is possible to exhibit long-term stability and weather resistance. When the content of the ultraviolet absorber in the acrylic resin layer and the resin substrate is too small, the weather resistance of the resulting scratch-resistant resin sheet may become insufficient. If the content of the ultraviolet absorber in the resin substrate is too large, the effect of the balance is not obtained, which is economically disadvantageous. The content of the ultraviolet absorber in the polycarbonate resin layer is preferably from 50,000 to 30,000 ppm, and the content of the ultraviolet absorber in the acrylic resin layer is preferably from 100 to 1 OOO ppm. Each of the resin layer and the acrylic resin layer may contain one or more additives such as a light diffusing agent, a matting agent, a dye, a photostabilizer, an antioxidant, a releasing agent, a flame retardant, and an antistatic agent. The resin substrate is usually in the form of a sheet or a film, and its thickness is usually 0.3 to 3 mm, preferably 0.3 to 2 mm, more preferably 0.4 to 1.5 mm. In the resin substrate, the thickness of the acrylic resin layer is usually 50 to 120 μπα, preferably 60 to 110 μηι, more preferably 70 to 1 μm. The smaller the thickness of the acrylic resin layer, the higher the impact resistance of the scratch-resistant resin sheet, and the tendency of the scratch-resistant resin sheet to be broken even if the scratch-resistant tree/lipid sheet is pressed, but the thickness of the acrylic resin layer is too small. The surface hardness of the scratch-resistant resin sheet is lowered. Further, if the thickness of the acrylic resin layer is too large, the scratch resistance of the scratch-resistant resin sheet is lowered. The resin substrate may be a two-layer structure laminate in which only the -12-201100248 acrylic resin layer is laminated on one surface of the polycarbonate resin layer, or a double-sided acrylic resin layer may be laminated on both sides of the polycarbonate resin layer. The three-layer structural laminate. From the viewpoint of environmental resistance of the scratch-resistant resin sheet, for example, from the viewpoint of being difficult to warp when exposed to high temperature or high humidity, a resin substrate in which an acrylic resin layer is laminated on both sides of the polycarbonate resin layer is preferred. . In the case of the three-layer structure, the acrylic resin layer on both sides may have the same or different composition and thickness as long as the content of the ultraviolet absorber per lm2 of the respective acrylic resin layers is 0.005 to lg. For example, in the acrylic resin layer on both sides, when one contains 0 rubber particles, the other may or may not contain rubber particles. Such a resin substrate can be produced by laminating and integrating a polycarbonate resin layer and an acrylic resin layer by co-extrusion molding. The co-extrusion molding system can melt and knead the material of the polycarbonate resin layer and the material of the acrylic resin layer by using two or three one-axis or two-axis extruders, and then pass through the supply head type. A (feedblock) die or a multi-manifold die or the like is laminated. The laminated laminated resin body Q can be cooled and solidified by, for example, a roll unit. The resin substrate produced by the co-extrusion molding is more easily formed than the resin substrate produced by bonding with an adhesive or an adhesive. The hardened film is formed on at least the surface of the aforementioned acrylic resin layer. When the acrylic resin layer is laminated on both surfaces of the polycarbonate resin layer, the cured film is formed on the surface of at least one surface of the acrylic resin layer. Therefore, the layer constitution of the scratch-resistant resin sheet of the present invention includes the following (i) to (i v ). (i) hardened film/acrylic resin layer/polycarbonate resin layer-13- 201100248 (ii) hardened film/acrylic resin layer/polycarbonate resin layer/hardened film (iii) hardened film/acrylic resin layer/polycarbonate Resin layer/acrylic resin layer (iv) hardened film/acrylic resin layer/polycarbonate resin layer/acrylic resin layer/hardened film. When a hardened film is formed on both surfaces of a resin substrate, the composition and thickness of the cured film on both sides are Can be the same or different from each other. The curable coating composition for forming a cured film contains one or more kinds of curable compounds capable of imparting scratch resistance as an essential component, and may contain a curing catalyst, conductive particles, a solvent, a leveling agent, and the like, if necessary. An stabilizer, an antioxidant, a colorant, and the like. Examples of the curable compound include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, and a copolymer acrylate compound. , alicyclic epoxy resin, glycidyl ether epoxy resin, vinyl ether compound, oxetane compound, and the like. Among them, from the viewpoint of scratch resistance of the cured film, a radical polymerizable curable compound such as a polyfunctional acrylate compound 'polyfunctional urethane acrylate compound or a polyfunctional epoxy acrylate compound is preferable. A thermopolymerizable curable compound such as an alkoxydecane or an alkyl alkoxysilane. These hardening compounds are preferably compounds which are hardened by irradiation with energy rays such as electron beams, radiation, ultraviolet rays, or the like, or compounds which are hardened by heating. A particularly preferred curable compound is a compound having at least three (methyl-14-201100248) acryloxy groups in the molecule. Here, the (meth)acryloxy group is an acryloxy group or a methacryloxy group, and in the present specification, when it is called (meth)acrylate, (meth)acrylic acid, etc. Methyl) has the same meaning. Examples of the compound having at least three (meth) propylene fluorenyloxy groups in the molecule include, for example, trimethylolpropane tri(meth)acrylate and trishydroxymethylethane tri(meth)acrylate. Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri- or tetra-(indolyl) acrylate, dipentaerythritol tri- or tetra-, penta- or hexa-(meth)acrylic acid a poly(meth) acrylate of a trivalent or higher polyvalent alcohol of an ester, tripentaerythritol tetra-, penta-, hexa- or hepta-(meth) acrylate; a compound having at least 2 isocyanate groups in the molecule, A metal urethane having three or more (meth) propylene decyloxy groups obtained by reacting a (meth) acrylate having a hydroxyl group with a hydroxyl group of at least a molar ratio with respect to an isocyanate group Acrylate [for example, reaction of q-diisocyanate with pentaerythritol tri(meth)acrylate to give 6-functional ethyl urethane (meth) acrylate]; tris(2-hydroxyethyl) Tris(meth)acrylate of cyanuric acid. Further, although the monomers are exemplified herein, such monomers may be used as they are, but for example, oligomers such as a dimer or a trimer may be used. Further, monomers and oligomers can also be used. As a commercial item of the compound which has at least three (meth) propylene methoxyl groups in a molecule, the "NK hard M101" ( urethane acrylate type) of the Nakamura Nakamura Chemical Industry Co., Ltd. is mentioned, for example. "NK ester A-TMM-3L" (pentaerythritol triacrylate), "NK ester A-TMMT" (penta tetra-15-201100248 alcohol tetraacrylate), "decyl ester A-9530" (dipentaerythritol pentaacrylic acid) Ester) and NK ester A-DPH" (dipentaerythritol hexaacrylate), "KAYARAD DPCA" (dipentaerythritol hexaacrylate) of Nippon Kayaku Co., Ltd., "Nopocure 200" series of SANNOPCO (share), Dainippon ink "Unidic" series of the chemical industry, etc. Further, when a compound having at least three (meth) acryloxy groups in the molecule is used as the curable compound, other curable compounds may be used as needed. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid Ester and the like have 2 (methyl) propyl groups in the molecule a compound of an oximeoxy group. When a other curable compound is used, the use of other curable compounds is relative to 1 part by weight of a compound having at least 3 (meth) acryloxy groups in the molecule. When the curable coating composition is cured by ultraviolet rays, it is preferred to use one or more kinds of photopolymerization initiators as the curing catalyst. Examples of the photopolymerization initiator include the photopolymerization initiator. Benzene oxime, benzophenone or its derivatives, thioxanthone, benzyl dimethyl ketal, α-hydroxyalkyl phenone, hydroxy ketone, aminoalkyl phenone, sulfhydryl The amount of the photopolymerization initiator to be used is usually 0.1 to 5 parts by weight based on 100 parts by weight of the curable compound.
作爲光聚合引發劑的市售品，例如可舉出汽巴特殊化 學品（股）的 “IRGACURE 651”、“IRGACURE 184”、 “IRGACURE 5 00” 、 “IRGACURE 1 000” 、 “IRGACURE -16- 201100248 2959” 、 “DAROCUR 117 3” 、 “IRGACURE 907” 、As a commercial item of a photoinitiator, for example, "IRGACURE 651", "IRGACURE 184", "IRGACURE 5 00", "IRGACURE 1 000", "IRGACURE -16-" of Ciba Specialty Chemicals (Shares) can be cited. 201100248 2959", "DAROCUR 117 3", "IRGACURE 907",
“IRGACURE 3 69” 、 “IRGACURE 1 700” 、 “IRGACURE 1 800” 、 “IRGACURE 819” 、 “IRGACURE 784” 等的 IRGACURE (伊爾加起爾）系歹IJ及DAROCUR (達若起爾） 系歹IJ、日本化藥（股）的 “KAYACURE ITX”、“KAYACURE DETX-S”、“KAYACURE BP-100”、 “ K A Y A C U REB M S，，、 “KAYACURE 2-EAQ”等的KAYACURE (卡亞起爾）系歹IJ等 ο 藉由使硬化性塗料組成物含有導電性粒子，所得到的 硬化被膜具有抗靜電性。作爲前述導電性粒子，例如較佳 爲銻-錫複合氧化物、含磷的氧化錫、氧化銻、銻-鋅複合 氧化物、氧化鈦、銦-錫複合氧化物（ΙΤΟ )等的無機粒子 〇 導電性粒子的平均粒徑通常爲〇·5 μπι以下，從硬化被 膜的抗靜電性或透明性之點來看’平均粒徑較佳爲 Ο.ΟΟΙμηι以上，較佳爲Ο.ίμηι以下’更佳爲0.05μιη以下。導 電性粒子的平均粒徑愈小，愈可降低耐擦傷性樹脂板的霧 度，而可提高透明性。 相對於1〇〇重量份的硬化性化合物而言，導電性粒子 的含量通常爲2〜50重量份，較佳爲3〜20重量份。導電性 粒子的含量愈多’則硬化被膜的抗砰電性有愈提高的傾向 ，導電性粒子的含量若太多’則硬化被膜的透明性會降低 。又，導電性粒子的含量若太少’則難以得到添加導電性 粒子所致的效果。 -17- 201100248 導電性粒子例如可藉由氣相分解法、電槳蒸發 氧化物分解法、共沈澱法、水熱法等來製造。又， 粒子的表面例如可經非離子系界面活性劑、陽離子 活性劑、陰離子系界面活性劑、矽系偶合劑、鋁系 等所表面處理。 硬化性塗料組成物以其黏度調整等爲目的，尤 化性塗料組成物含有導電性粒子時，以導電性微粒 散爲目的，較佳爲含有溶劑。於調製含有導電性粒 劑的硬化性塗料組成物之情況中，使導電性粒子分 劑中後，此分散液亦可與硬化性化合物混合，於混 性化合物與溶劑後，也可使導電性粒子分散在此混 〇 前述溶劑係可溶解硬化性化合物，而且較佳爲 性塗料組成物的塗佈後能容易揮發者。當硬化性塗 物含有導電性粒子時，較佳爲可使導電性微粒子分 劑。作爲如此的溶劑，可舉出二丙酮醇、甲醇、乙 丙醇、異丁醇、2_甲氧基乙醇、2-乙氧基乙醇、2-乙醇、甲氧基-2-丙醇等的醇類、丙酮、甲基乙基 基異丁基酮、二丙酮醇般的酮類、甲苯、二甲苯等 族烴類、醋酸乙酯、醋酸丁酯等的酯類、水等。溶 量係可配合硬化性化合物的性質形狀等來適宜調整 硬化性塗料組成物係可含有1種以上的均平劑 均平劑，較佳爲聚矽氧油。作爲聚矽氧油’可舉出 聚矽氧油、苯基甲基聚矽氧油、烷基•芳烷基改性 法、烷 導電性 系界面 偶合劑 其當硬 子的分 子及溶 散在溶 合硬化 合液中 在硬化 料組成 散的溶 醇、異 丁氧基 酮、甲 的芳香 劑的含 〇 。作爲 二甲基 聚矽氧 -18* 201100248 油、氟聚矽氧油、聚醚改性聚矽氧油、脂肪酸醋改性聚砍 氧油、甲基氫聚矽氧油、含矽烷醇基的聚矽氧油、含烷氧 基的聚矽氧油、含酚基的聚矽氧油、甲基丙稀酸改性聚砍 氧油、胺基改性聚矽氧油、羧酸改性聚矽氧油、卡必醇改 性聚砂氧油'環氧基改性聚砂氧油、疏基改性聚砂氧油' 氟改性聚矽氧油、聚醚改性聚矽氧油等。相對於10 0重量 份的硬化性化合物而言，均平劑的含量通常爲〇·01〜5重 量份。 〇 作爲均平劑的市售品，例如可舉出東麗·道康寧•聚 砂氧（股）的 “SH200-1 00CS、“SH28PA”、“SH29PA”、 “SH30PA”、“ST83PA”、“ST80PA，，、“ S T9 7 P A’，及 “ S T 8 6 P A，， ，BYK 化學•日本（股）的 “BYK-302”、“BYK-307”、“BYK-320” 及 “BYK-330” 等。 將如此所得之硬化性塗料組成物塗佈在至少一面的丙 烯酸樹脂層表面上，以當作硬化性塗膜，接著使硬化性塗 Q膜硬化，以成爲硬化被膜，而得到本發明的耐擦傷性樹脂 板。 硬化性塗料組成物的塗佈例如可藉由桿塗法、微凹槽 輥塗佈法、輥塗法、流塗法、浸塗法、旋塗法、口模式塗 佈法、噴塗法等的塗佈法來進行。硬化性塗膜的硬化係可 按照硬化性塗料組成物的種類，藉由能量線的照射或加熱 來進行。 藉由能量線的照射來使硬化性塗膜硬化時，作爲能量 線’例如可舉出紫外線、電子線、輻射線等，其強度、照 19- 201100248 射時間等的條件係可按照硬化性塗料組成物的種類來適宜 選擇。又，藉由加熱使硬化性塗膜硬化時，其溫度、時間 等的條件係可按照硬化性塗料組成物的種類來適宜選擇， 加熱溫度爲了不引起樹脂基板發生變形，一般較佳爲 1 0(TC以下。於硬化性塗料組成物含有溶劑時，在硬化性 塗料組成物的塗佈後，使溶劑揮發後，可使硬化性塗膜進 行硬化，也可同時進行溶劑的揮發與硬化性塗膜的硬化。 硬化被膜的厚度較佳爲0.5〜50 μιη，更佳爲1〜20 μπι 。硬化被膜的厚度愈小，則有愈不易發生龜裂的傾向，但 若太小’則耐擦傷性會變不充分。又，若太大，則暴露於 高溫高濕下時，變容易發生龜裂。 於本發明的耐擦傷性樹脂板中，按照需要，對其表面 ’可藉由塗覆法、濺鑛、真空蒸鍍法等來施予防反射處理 。又’爲了賦予防反射效果，於本發明的耐擦傷性樹脂板 的一面或兩面，亦可貼合另途製作的防反射性之薄片。 本發明的耐擦傷性樹脂板係表面硬度及耐衝撃性優異 ’而且即使進行擠壓也不易破裂，顯示長期優異的耐候性 ’故可用於各種用途。其中，本發明的耐擦傷性樹脂板係 適用作爲顯示器保護板。作爲被保護的顯示器之種類，例 如可舉出CRT顯不器、液晶顯不器、電槳顯示器、EL顯75 器等。又’作爲被保護的顯示器之用途，例如可舉出電視 、電腦等的監視器、攜帶式電話、P H S、P D A等的攜帶型 貝訊終端之顯示窗、數位照相機、手持型攝影等的取景部 、擴帶型遊戲機的顯示窗等。 -20- 201100248 本發明的耐擦傷性樹脂板係特別適用作爲液晶顯示器 、EL顯示器等的攜帶型資訊終端之顯示窗保護板。本發明 的耐擦傷性樹脂板’在作爲攜帶電話，尤其含顯示窗的顯 示部’不使用時被折疊，而具有操作按鈕部被覆蓋的構造 之攜帶電話的顯示窗保護板，係發揮有利的效果。 爲了由本發明的耐擦傷性樹脂板來製作顯示器保護板 ’首先按照需要進行印刷、開孔等的加工，裁切成所需要 的大小。然後，若安裝於顯示器，則可有效地保護顯示器 。於該情況下，僅在樹脂基板的一面上形成有硬化被膜的 耐擦傷性樹脂板’較佳係以形成有硬化被膜的側成爲表側 (視覺辨識側）’以沒有形成硬化被膜的側成爲裏側（顯 示器側）的方式進行安裝。又，於僅在聚碳酸酯樹脂層的 一面上形成有丙烯酸樹脂層的樹脂基板之兩面，形成有硬 化被膜的耐擦傷性樹脂板，較佳係以丙烯酸樹脂層側成爲 表側，以聚碳酸酯樹脂層側成爲裏側的方式進行安裝。 以下藉由實施例來更詳細說明本發明，惟本發明不受 此等實施例所限定。再者，以下的實施例中，％及份只要 沒有特別的記載，則以重量爲基準。 [實施例1〜5及比較例1、2] <耐擦傷性樹脂板的製作> (樹脂基板的製作） 樹脂基板之製作時所使用的材料係如以下。 •聚碳酸酯樹脂Μ主友DOW(股）製的「Calibre 301」 -21 - 201100248 •甲基丙烯酸樹脂：使用由97.8%的甲基丙烯酸甲酯 與2.2%的丙烯酸甲酯所成的單體之經由整體聚合所得的熱 塑性聚合物（玻璃轉移溫度1 〇4°C )的九粒。再者，該玻 璃轉移溫度係依照JIS K712 1 :1 987 ’藉由差示掃描熱量測 定以1 〇°C/分鐘的加熱速度所求得之外推玻璃轉移開始溫 度。 •紫外線吸收劑（A ):苯并三唑系紫外線吸收劑之 住友化學（股）製的「Sumisorp 340」。 •紫外線吸收劑（B ):苯并三唑系紫外線吸收劑之（ 股）ADEKA製的「LA3 1」。 首先，各自以表1中所示之比例，於聚碳酸酯樹脂中 添加紫外線吸收劑（A )，於甲基丙烯酸樹脂中添加紫外 線吸收劑（B )，藉由超級混合機來進行混合。其次，各 自以擠壓機來進行熔融混煉，通過供料頭將兩者層合，通 過設定溫度265 °C的T型模頭進行壓出。將所得之薄膜狀物 夾入一對表面爲平滑的金屬製輥之間，進行成形·冷卻’ 在厚度43 0μπι的聚碳酸酯樹脂層之一面上層合厚度70μηι的 甲基丙烯酸樹脂層，以製作總厚度5 00μπι的由2層構成所成 的樹脂基板。 (硬化性塗料組成物的調製） 混合2 8份的二季戊四醇六丙烯酸酯[新中村化學工業（ 股）製的「ΝΚ酯A-DPH」]、1份的光聚合引發劑[汽巴特殊 -22- 201100248 化學品（股）製的「IRGACURE 184」]、8份的五氧化銻微粒 子溶膠[日揮觸媒化成（股）製的「ELCOM-7514」；固體成 分濃度20%]、32份的1-甲氧基-2-丙醇、32份的異丁醇及 〇· 04 5份的聚矽氧油[東麗•道康寧·聚矽氧（股）製的「 SH2 8PA」]’以調製硬化性塗料組成物。 (耐擦傷性樹脂板的製作） 將前述所得之樹脂基板裁切成1 〇 〇 m m X 6 0 m m的大小， ❹ 藉由浸漬法在兩面形成硬化性塗料的塗膜。接著，在室溫 乾燥1分鐘，再於45 °C的熱風烘箱內乾燥3分間以使溶劑揮 發後，對此塗膜，使用120W的高壓水銀燈照射0.5J/Cm2的 紫外線而使硬化，得到厚度3 μχη的硬化被膜分別形成在甲 基丙烯酸樹脂層表面及聚碳酸酯樹脂層表面上的耐擦傷性 樹脂板。再者，所得之耐擦傷性樹脂板的硬化被膜之厚度 ，係使用膜厚測定裝置[Filmetrics公司製的F-20]來測定。 Q 對此耐擦傷性樹脂板，進行以下的評價，表1中顯示其結 果。 <評價> (耐候性） 所得之耐擦傷性樹脂板的耐候性，係以陽光氣候計（ 條件：雨，環境溫度：63 °C )來進行評價，由式：（Yl4〇〇 )-(YIG )來算出初期的黃色度（YIQ )與400小時後的黃 色度（YI4GG )之差：ΔΥΙ。此ΛΥΙ的値愈小，則表示耐候 -23- 201100248 性愈優異。前述變黃度係使用島津製作所（股）的分光光度 計「U V - 3 1 0 0 P C」來測定。 (鉛筆硬度） 依據JIS K 5600來測定所得之耐擦傷性樹脂板中的甲 基丙烯酸樹脂層側之硬化被膜表面的鉛筆硬度。 -24- 201100248 ο ο 評價結果 鉛筆硬度 工 寸 工 寸 工 寸 I 4H 工 CQ I OJ I 寸 耐候性3) ΔΥΙ i__ OJ Γ™ 0) CO o 0) CO r- T— cd ^400 ! 00 寸 寸· ΙΟ (0 寸’ lO 00 寸 卜 CD <〇 6 CD 6 (D d CD 6 (0 d ό CO ό 二觀旨麵賴成 .s E勸： r-替 J® ^ ne ®纏\ « ^ ^ M S 1. 125 1. 103 I I I 1. 109 l 1. 081 1. 130 1. 093 0. 028 甲基丙烯酸樹脂層 每1m2的 紫外線吸收劑量 (g/m2) 0. 007 0. 028 0. 077 10 CO 6 d I 1. 05 0. 028 紫外線吸收劑(B)2) (ppm) 100 I 400 1100 5000 10000 I 15000 i 400 聚碳酸酯樹脂層 紫外線吸收劑(A)” (ppm) 2600 2500 2400 1700 I 1000 i loo ! o 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例2 08丄 §ΙΛ)：ΙΛν - M^MS迤 ¢50 寸：0§ΙΛ*Μ€1«δβΙ®:0ΙΛ(ε 「13」saY33as) (ζ 「0寸Co&01S」§戤(^)»^«州>(1, -25- 201100248 如由表1可明知’聚碳酸酯樹脂層及甲基丙烯 脂層皆含有紫外線吸收劑，甲基丙烯酸樹脂層每1 外線吸收劑之含量爲0.005〜Ig，而且樹脂基板每1 外線吸收劑之含量爲〇. 5〜2 g之實施例1〜5，係較t 還耐候性優異，較比較例1還鉛筆硬度高。 另一方面，於甲基丙烯酸樹脂層每lm2的紫外 劑之含量多於lg的比較例1中，顯示鉛筆硬度差的 又，於聚碳酸酯樹脂層不含紫外線吸收劑，樹脂 lm2的紫外線吸收劑之含量少於0.5 g的比較例2，顯 性差的結果。 再者，對實施例1〜5及比較例1、2的各耐擦傷 板中的甲基丙烯酸樹脂層側之硬化被膜表面’使用 #0000[日本鋼絲棉（股）製]，施加5 00g/cm2的荷重而 次，目視觀察有無損傷。結果，在任一耐擦傷性樹 皆沒有損傷，顯示耐擦傷性優異的結果° 酸酯樹 m2的紫 m2的紫 L較例2 線吸收 結果。 基板每 示耐候 性樹脂 鋼絲棉 往返20 脂板中 -26-IRGACURE 伊IJ and DAROCUR systems for "IRGACURE 3 69", "IRGACURE 1 700", "IRGACURE 1 800", "IRGACURE 819", "IRGACURE 784", etc. KAYACURE of "IKA", "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACU REB MS,", "KAYACURE 2-EAQ", etc. by IJ, Nippon Kayaku Co., Ltd. In the case where the curable coating composition contains conductive particles, the obtained cured film has antistatic properties. As the conductive particles, for example, a bismuth-tin composite oxide or a phosphorus-containing tin oxide is preferable. The inorganic particles of the cerium oxide, the cerium-zinc composite oxide, the titanium oxide, the indium-tin composite oxide (ΙΤΟ), and the like have an average particle diameter of 〇·5 μm or less, and the antistatic property of the cured film. Or the point of transparency, the average particle diameter is preferably Ο.ΟΟΙμηι or more, preferably Ο.ίμηι or less 'more preferably 0.05 μmη or less. The smaller the average particle diameter of the conductive particles, the lower the scratch resistance. Resin board haze The content of the conductive particles is usually 2 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 1 part by weight of the curable compound. The more the content of the conductive particles is' Then, the electric repellency of the hardened film tends to increase, and if the content of the conductive particles is too large, the transparency of the cured film is lowered. If the content of the conductive particles is too small, it is difficult to obtain conductive particles. -17- 201100248 The conductive particles can be produced, for example, by a gas phase decomposition method, an electric pad evaporation oxide decomposition method, a coprecipitation method, a hydrothermal method, etc. Further, the surface of the particles can be, for example, non-ionized. It is a surface treatment of a surfactant, a cationic active agent, an anionic surfactant, a lanthanide coupling agent, or an aluminum system. The curable coating composition is designed to have viscosity adjustment, and the composition of the coating material contains conductive particles. In the case of dispersing conductive particles, it is preferred to contain a solvent. In the case of preparing a curable coating composition containing conductive granules, the conductive particles are dispersed in the mixture. The dispersion may be mixed with the curable compound, and after the mixed compound and the solvent, the conductive particles may be dispersed in the solvent-soluble hardenable compound, and preferably after coating of the coating composition When the curable coating contains conductive particles, it is preferred to disperse the conductive fine particles. Examples of such a solvent include diacetone alcohol, methanol, ethylene propanol, isobutanol, and 2 Alcohols such as methoxyethanol, 2-ethoxyethanol, 2-ethanol, methoxy-2-propanol, acetone, methyl ethyl isobutyl ketone, diacetone alcohol-like ketones, a hydrocarbon such as toluene or xylene; an ester such as ethyl acetate or butyl acetate; or water. The solvent amount can be appropriately adjusted in accordance with the nature and shape of the curable compound. The curable coating composition may contain one or more leveling agent leveling agents, preferably polyfluorene oil. Examples of the polyoxygenated oil include polyoxyxane oil, phenylmethylpolyphosphonium oil, alkyl aralkyl modification method, and alkyne conductive interface coupling agent. In the combined hardening liquid, the sputum containing the dissolved alcohol, the isobutoxy ketone, and the aromatic fragrant agent in the hardened material is dispersed. As dimethyl polyfluorene-18* 201100248 oil, fluoropolyoxy sulfonate, polyether modified polyoxyxide oil, fatty acid vinegar modified polyoxygenated oil, methyl hydrogen polyoxyl oil, stanol-containing Polyoxygenated oil, alkoxy-containing polyoxygenated oil, phenolic-containing polyoxygenated oil, methyl acrylate-modified polysulfate oil, amine-modified polyoxyxene oil, carboxylic acid modified poly Oxygenated oil, carbitol modified polysilicate oil 'epoxy modified polysilicic acid oil, sulphur modified polysilicic acid oil' fluorine modified polyoxylized oil, polyether modified polyoxyxene oil, etc. . The content of the leveling agent is usually from 〇01 to 5 parts by weight based on 100 parts by weight of the curable compound.市 As a commercial product of the leveling agent, for example, "SH200-1 00CS, "SH28PA", "SH29PA", "SH30PA", "ST83PA", and "ST80PA" of Toray Dow Corning Polysilicate Co., Ltd. ,,, "S T9 7 P A', and "ST 8 6 PA,, , BYK Chemical, Japan, "BYK-302", "BYK-307", "BYK-320" and "BYK-330" " Wait. The curable coating composition thus obtained is applied onto the surface of at least one side of the acrylic resin layer to serve as a curable coating film, and then the curable coating Q film is cured to form a hardened film to obtain the scratch resistance of the present invention. Resin board. The coating of the curable coating composition can be, for example, by a bar coating method, a micro-groove roll coating method, a roll coating method, a flow coating method, a dip coating method, a spin coating method, a die coating method, a spray coating method, or the like. The coating method is carried out. The curing of the curable coating film can be carried out by irradiation or heating of the energy ray according to the type of the curable coating composition. When the curable coating film is cured by the irradiation of the energy ray, the energy ray 'equivalently, for example, ultraviolet rays, electron beams, radiation, etc., and the conditions such as the strength and the irradiation time of 19-201100248 can be made according to the curable coating. The type of the composition is appropriately selected. Further, when the curable coating film is cured by heating, conditions such as temperature and time can be appropriately selected depending on the type of the curable coating composition, and the heating temperature is generally preferably 10 in order not to cause deformation of the resin substrate. (TC or less. When the curable coating composition contains a solvent, after the coating of the curable coating composition, the solvent is volatilized, the curable coating film can be cured, and the solvent can be volatilized and cured. Hardening of the film. The thickness of the cured film is preferably from 0.5 to 50 μm, more preferably from 1 to 20 μm. The smaller the thickness of the cured film, the less likely it is to crack, but if it is too small, it is scratch resistant. If it is too large, it will be susceptible to cracking when exposed to high temperature and high humidity. In the scratch-resistant resin sheet of the present invention, the surface thereof can be coated by a coating method as needed. Anti-reflection treatment is applied by sputtering, vacuum evaporation, etc. In order to impart an anti-reflection effect, one or both sides of the scratch-resistant resin sheet of the present invention may be bonded to an anti-reflective sheet produced separately. The scratch-resistant resin sheet of the present invention is excellent in surface hardness and impact resistance, and is not easily broken even when extruded, and exhibits long-term excellent weather resistance. Therefore, it can be used in various applications. Among them, the scratch-resistant resin sheet of the present invention is used. It is suitable as a display protection board. As a type of protected display, for example, a CRT display, a liquid crystal display, an electric paddle display, an EL display 75, etc. can be cited as the use of the protected display, for example, A monitor such as a monitor such as a television or a computer, a portable telephone, a display window of a portable Beixun terminal such as a PHS or a PDA, a digital camera, a framing portion such as a handheld camera, and a display window of a tape-type game machine are provided. 20-201100248 The scratch-resistant resin sheet of the present invention is particularly suitable as a display window protection board for a portable information terminal such as a liquid crystal display or an EL display. The scratch-resistant resin sheet of the present invention is used as a portable telephone, particularly including a display window. The display portion of the display unit that is folded when not in use and has a structure in which the operation button portion is covered is used. In order to produce the display protection plate from the scratch-resistant resin sheet of the present invention, first, printing, opening, and the like are performed as needed, and the size is cut to a desired size. Then, if it is mounted on the display, it can be effectively In this case, the scratch-resistant resin sheet on which the hardened film is formed only on one surface of the resin substrate is preferably such that the side on which the cured film is formed becomes the front side (visible side) to form a hardened film. The side is placed on the back side (display side). Further, on both sides of the resin substrate on which the acrylic resin layer is formed on one surface of the polycarbonate resin layer, a scratch-resistant resin sheet having a cured film is formed. The acrylic resin layer side is referred to as the front side, and the polycarbonate resin layer side is attached to the inner side. The present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. Further, in the following examples, % and parts are based on weight unless otherwise specified. [Examples 1 to 5 and Comparative Examples 1 and 2] <Preparation of scratch-resistant resin sheet> (Production of resin substrate) The materials used in the production of the resin substrate are as follows. • "Calibre 301" made by Polycarbonate Resin Μ DOW (-) - 21 - 201100248 • Methacrylic resin: a monomer made of 97.8% methyl methacrylate and 2.2% methyl acrylate Nine particles of the resulting thermoplastic polymer (glass transition temperature of 1 〇 4 ° C) were polymerized as a whole. Further, the glass transition temperature was determined by extrapolating the glass transition start temperature by a differential scanning calorimetry at a heating rate of 1 〇 ° C / min in accordance with JIS K712 1 : 1 987 '. • UV absorber (A): Sumisorp 340 by Sumitomo Chemical Co., Ltd., a benzotriazole-based UV absorber. • UV absorber (B): “LA3 1” manufactured by ADEKA, a benzotriazole-based UV absorber. First, each of the ultraviolet absorbers (A) was added to the polycarbonate resin in the ratio shown in Table 1, and the ultraviolet absorber (B) was added to the methacrylic resin, and the mixture was mixed by a super mixer. Next, each was melt-kneaded by an extruder, and the two were laminated by a supply head, and extruded by a T-die having a set temperature of 265 °C. The obtained film material was sandwiched between a pair of smooth metal rolls, and molded and cooled. A methacrylic resin layer having a thickness of 70 μm was laminated on one surface of a polycarbonate resin layer having a thickness of 43 μm to prepare a film. A resin substrate composed of two layers having a total thickness of 50,000 μm. (Preparation of a hardenable coating composition) Mixing 28 parts of dipentaerythritol hexaacrylate ["Nippon Ethylene A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd.], 1 part of a photopolymerization initiator [Ciba special- 22- 201100248 "IRGACURE 184" manufactured by Chemicals Co., Ltd., 8 parts of ruthenium pentoxide granule sol [ELCOM-7514" manufactured by Nippon Kasei Chemical Co., Ltd.; solid concentration 20%], 32 parts 1-methoxy-2-propanol, 32 parts of isobutanol, and 〇·04 5 parts of polyoxo-oxygen oil [Toray Dow Corning Polyethylene Oxide (SH2 8PA)] A hardenable coating composition. (Production of scratch-resistant resin sheet) The resin substrate obtained above was cut into a size of 1 〇 〇 m m X 60 m m, and a coating film of a curable coating material was formed on both surfaces by a dipping method. Then, it was dried at room temperature for 1 minute, and then dried in a hot air oven at 45 ° C for 3 minutes to volatilize the solvent, and then the coating film was irradiated with ultraviolet light of 0.5 J/cm 2 by a 120 W high-pressure mercury lamp to obtain a thickness. A 3 μχη hardened film is formed on the surface of the methacrylic resin layer and the scratch-resistant resin sheet on the surface of the polycarbonate resin layer, respectively. Further, the thickness of the cured film of the obtained scratch-resistant resin sheet was measured using a film thickness measuring device [F-20 manufactured by Filmetrics Co., Ltd.]. Q The following evaluation was performed on the scratch-resistant resin sheet, and the results are shown in Table 1. <Evaluation> (Weather resistance) The weather resistance of the obtained scratch-resistant resin sheet was evaluated by a sunlight weather condition (condition: rain, ambient temperature: 63 ° C), and the formula: (Yl4〇〇)- (YIG) to calculate the difference between the initial yellowness (YIQ) and the yellowness after 400 hours (YI4GG): ΔΥΙ. The smaller the sputum, the better the weather resistance -23- 201100248. The yellowing degree was measured using a spectrophotometer "U V - 3 1 0 0 P C" of Shimadzu Corporation. (Pencil Hardness) The pencil hardness of the surface of the cured film on the side of the methacrylic resin layer in the obtained scratch-resistant resin sheet was measured in accordance with JIS K 5600. -24- 201100248 ο ο Evaluation results Pencil hardness work inch inch inch I 4H work CQ I OJ I inch weather resistance 3) ΔΥΙ i__ OJ ΓTM 0) CO o 0) CO r- T- cd ^400 ! 00 inch · ΙΟ (0 inch ' lO 00 inch CD < 〇 6 CD 6 (D d CD 6 (0 d ό CO ό 二观面面赖成.s E persuasion: r- for J® ^ ne ® wrapped \ « ^ ^ MS 1. 125 1. 103 III 1. 109 l 1. 081 1. 130 1. 093 0. 028 methacrylic resin layer UV absorption dose per 1 m2 (g/m2) 0. 007 0. 028 0. 077 10 CO 6 d I 1. 05 0. 028 UV absorber (B) 2) (ppm) 100 I 400 1100 5000 10000 I 15000 i 400 Polycarbonate resin layer UV absorber (A)” (ppm) 2600 2500 2400 1700 I 1000 i loo ! o Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 08丄§ΙΛ): ΙΛν - M^MS迤¢50 Inch: 0§ΙΛ*Μ €1«δβΙ®:0ΙΛ(ε "13"saY33as) (ζ "0" Co&01S"§戤(^)»^«州>(1, -25- 201100248 As can be seen from Table 1 'Polycarbonate Both the ester resin layer and the methacrylic acid layer contain an ultraviolet absorber, and each methacrylic resin layer 1 The content of the external absorbent is 0.005 to 1 g, and the content of the absorbent per 1 line of the resin substrate is 〇. 5 to 2 g of the examples 1 to 5, which is excellent in weather resistance, and the pencil hardness is higher than that of the comparative example 1. On the other hand, in Comparative Example 1 in which the content of the ultraviolet ray of the methacrylic resin layer per lm2 is more than lg, the difference in pencil hardness is shown, and the ultraviolet absorbing agent is not contained in the polycarbonate resin layer, and the resin lm2 is In Comparative Example 2 in which the content of the ultraviolet absorber was less than 0.5 g, the result was poor. The cured film on the side of the methacrylic resin layer in each of the scratch-resistant sheets of Examples 1 to 5 and Comparative Examples 1 and 2 was obtained. On the surface, #0000 [made by Japanese steel wool (manufactured by Japan Steel Co., Ltd.) was applied, and a load of 500 g/cm 2 was applied thereto, and the presence or absence of damage was visually observed. As a result, no damage was observed in any of the scratch-resistant trees, and the result of excellent scratch resistance was exhibited. The purple L of the purple m2 of the acid ester tree m2 is lower than the absorption result of the second example. The substrate shows the weatherable resin steel wire round-trip 20 fat plate -26-