200824907 九、發明說明 【發明所屬之技術領域】 本發明係關於適合作爲攜帶型資訊終端之顯示窗保護 板的耐擦傷性樹脂板、及作用其之攜帶型資訊終端的顯示 窗保護板。 【先前技術】 近來，行動電話和 PHS (Personal Handy-phone System，個人手提電話系統）等之攜帶型電話類隨著互聯 網的普及，乃以具有單純的聲音傳遞機能，加上顯示文字 資訊和影像資訊機能的攜帶型資訊終端型式被廣泛使用。 又，與此類攜帶型電話類不同，於住址冊等之機能兼具互 聯網機能和電子郵件機能的 PDA ( Personal Digital Assistant，個人數碼助理）亦被廣泛使用。本說明書中， 將此類行動電話和PHS、PDA等整理稱爲「攜帶型資訊終 端」。即，本說明書中所謂的「攜帶型資訊終端」係將具 有人可攜帶行走左右之大小，且具有顯示文字資訊和影像 資訊等所用之窗（顯示器）予以總稱。 此類攜帶型資訊終端中，經由液晶和EL (電致發光 )等之方式，顯示文字資訊和影像資訊，其顯示窗一般使 用透明樹脂製之物質作爲保護板（例如參照特開2002-6764號公報、特開 2004- 1 43 3 65號公報、特開 2004-299 1 99號公報）。其次，於此保護板，爲了防止表面損 傷，乃提案以硬化性塗料設置耐擦傷性的硬化被膜，又， -4- 200824907 亦提案令硬化性塗料中含有導電性微粒子，對於硬化被膜 賦予抗靜電性。 【發明內容】 上述硬化被膜爲於保護板的至少一面設置，且僅於單 面設置時，則將其面朝向表側（使用人直接察見且觸摸側 )即可，但僅於單面設置硬化被膜的保護板，若於高溫高 濕下長時間曝露，則具有易發生彎曲的問題。因此，硬化 被膜可設置於保護板之兩面，但此時，若以不含有導電性 微粒子的硬化性塗料進行兩硬化被膜的形成，則於押壓時 具有易割傷保護板的問題，另一方面，若以含有導電性微 粒子之硬化性塗料進行，則具有難取得充分之耐擦傷性的 問題。 於是，本發明者等人，對於開發出設置即使押壓亦難 裂開、且耐擦傷性高之硬化被膜之攜帶型資訊終端的顯示 窗保護板，進行致力檢討之結果，發現經由使用不含有導 電性微粒子之硬化性塗料進行一面硬化被膜的形成，且使 用含有導電性微粒子之硬化性塗料進行另一面硬化被膜的 形成，則可取得適合作爲具有上述所欲性能之攜帶型資訊 終端之顯示窗保護板的耐擦傷性樹脂板，並且達到完全本 發明。 即，本發明爲提供於樹脂基板之一面，以不含有導電 性微粒子之硬化性塗料形成硬化被膜，並於另一面，以含 有導電性微粒子之硬化性塗料形成硬化被膜爲其特徵的耐 -5- 200824907 擦傷性樹脂板。又，若根據本發明，則亦提供此耐擦傷性 樹脂板所構成之攜帶型資訊終端的顯示窗保護板。 本發明之耐擦傷性樹脂板爲具有即使押壓亦難裂開， 且耐擦傷性高的硬化被膜，經由將此耐擦傷性樹脂板使用 作爲攜帶型資訊終端的顯示窗保護板，則可有效保護其顯 示窗。 【實施方式】 作爲構成本發明之耐擦傷性樹脂之基板的樹脂，可列 舉例如，甲基丙烯酸樹脂、聚碳酸酯樹脂、聚苯乙烯樹脂 、苯乙烯-丙烯腈共聚物、三乙醯纖維素樹脂等。其中亦 以甲基丙烯酸樹脂，因爲透明性高，且剛性亦高，故適合 作爲構成基板的樹脂。 甲基丙烯酸樹脂爲以甲基丙烯酸酯作爲主體的聚合物 ，例如，可爲甲基丙烯酸酯的單聚物，且亦可爲甲基丙烯 酸酯50重量％以上與其他單體50重量％以下的共聚物。 共聚物之情況，甲基丙烯酸酯於全單體中所佔之比例較佳 爲70重量％以上，更佳爲90重量％以上。甲基丙烯酸酯 以甲基丙烯酸烷酯爲較佳使用，且特別以甲基丙烯酸甲酯 爲較佳使用。又，甲基丙烯酸酯以外之單體可列舉例如， 丙烯酸甲酯和丙烯酸乙酯般之丙烯酸酯、苯乙烯和甲基苯 乙烯般之芳香族烯基化合物、丙烯酸和甲基丙烯酸般之不 飽和羧酸、丙烯腈和甲基丙烯腈般之烯基氰胺化合物等。 樹脂基板爲通常之板（薄片）和薄膜般，表面爲平面 -6 - 200824907 者，且亦可爲凸透鏡和凸透鏡般，表面爲呈曲面者。又， 亦可於表面設置細凹凸等之微細構造。 樹脂基板視需要，亦可以染料和顏料等加以著色，且 亦可含有抗氧化劑和紫外線吸收劑、橡膠粒子等。樹脂基 板之厚度較佳爲0.1mm以上、且爲3.0mm以下。 本發明中’於樹脂基板之兩面形成硬化被膜作成耐擦 傷性樹脂板，此時，一面硬化被膜的形成爲使用不含有導 電性微粒子的硬化塗料〔以下，將此硬化性塗料稱爲塗料 (A)〕進行，另一面硬化被膜的形成爲使用含有導電性 微粒子的硬化性塗料〔以下，將此硬化性塗料稱爲塗料（ B )〕進行。如此，於表裏兩面分別使用不同之塗料（A )及（B )形成硬化被膜，則可取得具有即使押壓亦難裂 開、且耐擦傷性高之硬化被膜的耐擦傷性樹脂板。 於此耐擦傷性樹脂板中，通常，以塗料（A )所形成 的硬化被膜因不含有導電性微粒子，故比塗料（B )所形 成之硬化被膜的耐擦傷性優良，另一方面，以塗料（B) 所形成的硬化被膜因含有導電性微粒子，故比塗料（A ) 所形成之硬化被膜的抗靜電性和制電性優良。又，通常， 由塗料（A )形成之硬化被膜面側予以押壓之情況，比由 塗料（B )形成之硬化被膜面側予以押壓之情況，難裂開 。因此，將此耐擦傷性樹脂板使用作爲攜帶型資訊終端的 顯示窗保護板時，將塗料（A)形成之硬化被膜面朝向表 側（使用人爲直接察見且觸摸側），並將塗料（B )形成 之硬化被膜面朝向裏側（顯示器側），則可有效果地’即 200824907 使使用人觸摸，亦難造成損傷，且難裂開’又’附著塵埃 時，難擦拭的裏側經由其抗靜電性，則可作成難附著塵埃 〇 塗料（A )和（B )所含之硬化性化合物，以具有照 射電子射線和紫外線等之活化能量線而硬化之性質的化合 物爲較佳使用，特別以多官能（甲基）丙烯酸酯化合物爲 較佳使用。此處，所謂多官能（甲基）丙烯酸酯化合物， 係指分子中具有至少二個（甲基）丙烯醯氧基的化合物， 其中，亦以分子中具有三個以上、即至少三個（甲基）丙 烯醯氧基之化合物爲較佳使用。另外，於本說明書中，所 謂（甲基）丙烯醯氧基係指丙烯醯氧基或甲基丙烯醯氧基 ，此外，所謂（甲基）丙烯酸酯、（甲基）丙烯酸等時之 「（甲基）」亦爲同樣之意義。 多官能（甲基）丙烯酸酯化合物之例可列舉乙二醇二 (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、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、五甘油三（甲基）丙烯酸酯、季戊四 醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、 甘油三（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸 酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲 基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、三〔（ 甲基）丙烯醯氧乙基〕異氰脲酸酯、三季戊四醇八（甲基 )丙烯酸酯等。 -8 - 200824907 又，於磷腈化合物之磷腈環導入（甲基）丙烯醯氧基 之磷腈系（甲基）丙烯酸酯化合物；分子中具有至少二個 異氰酸酯基的聚異氰酸酯、與分子中具有至少一個（甲基 )丙烯醯氧基及羥基之多元醇化合反應所得的胺基甲酸酯 (甲基）丙烯酸酯化合物；分子中具有至少二個羧酸鹵基 之化合物、與分子中具有至少一個（甲基）丙烯醯氧基及 羥基之多元醇化合物反應所得的聚酯（甲基）丙烯酸酯化 合物；上述各化合物之二聚物和三聚物等之低聚物亦可使 用。此等多官能（甲基）丙烯酸酯化合物可分別單獨或混 合使用二種以上。 塗料（B )中所含之導電性微粒子可列舉例如，氧化 銻般之金屬氧化物、銦/錫之複合氧化物（ITO )、摻混 銻之氧化錫（ΑΤΟ )、摻混鉛之氧化錫（PTO )、銻/鋅 之複合氧化物等之各微粒子。 導電性微粒子以其粒徑爲0.0 0 1〜1 μηι爲佳。粒徑頗 小者，工業上生產困難，若使用粒徑頗大者，則因硬化被 膜的透明性降低故爲不佳。又，塗料（Β )中之導電性微 粒子的使用量，相對於硬化性化合物1 00重量份，以1〜 1 〇〇重量份爲佳。此使用量若頗少，則所得之耐擦傷性樹 脂板押壓時易裂開，又無法取得充分的抗靜電效果，若頗 多，則硬化被膜的耐擦傷性降低，且成膜性降低故爲不佳 〇 於塗料（A )和（Β )中，爲了調整黏度和硬化被膜 的厚度等，亦可含有溶劑。此溶劑可列舉例如’甲醇、乙 -9- 200824907 醇、1-丙醇、2-丙醇（異丙醇）、1-丁醇、2-丁醇（第二 丁醇）、2-甲基-卜丙醇（異丁醇）、2-甲基-2-丙醇（第 三丁醇）般之醇類、2-乙氧基乙醇、2-丁氧基乙醇、3-甲 氧基-1-丙醇、卜甲氧基-2-丙醇、1-乙氧基-2 _丙醇般之烷 氧醇類、雙丙酮醇般之酮醇類、丙酮、甲基乙基酮、甲基 異丁基酮般之酮類、甲苯、二甲苯般之芳香族烴類、醋酸 乙酯、醋酸丁酯般之酯類等。溶劑的使用量爲根據基板之 材質、形狀、塗佈方法、目的硬化被膜之厚度等而適當調 整，但通常，於塗料（A)中相對於硬化性化合物1〇〇重 量份，以2 0〜1 0 0 0 0重量份左右，於塗料（B )中相對於 硬化性化合物及導電性微粒子之合計量1 00重量份，爲 20〜10000重量份左右。 又，於塗料（A )和（B )中，視需要，亦可含有安 定劑、抗氧化劑、著色劑、勻塗劑等之添加劑。經由含有 勻塗劑，則可提高硬化被膜的平滑性和耐擦傷性。 勻塗劑以矽酮油爲較佳使用，其例可例舉二甲基矽酮 油、苯甲基矽酮油、烷基-芳烷基改質矽酮油、氟基矽酮 油、聚醚改質矽酮油、脂肪酸酯改質矽酮油、甲基氫矽酮 油、含有矽醇基之矽酮油、含有烷氧基之矽酮油、含有酚 基之矽酮油、甲基丙烯基改質矽酮油、胺基改質矽酮油、 羧酸改質矽酮油、卡必醇改質矽酮油、環氧改質矽酮油、 氫硫基改質矽酮油、氟改質矽酮油、聚醚改質矽酮油等。 此些矽酮油可分別單獨使用，且亦可倂用二種以上。 砂酮油之使用量，於塗料（A )中相對於硬化性化合 -10- 200824907 物100重量份，通常爲0.0 1〜20重量份，於塗料（B)中 相對於硬化性化合物及導電性微粒子的合計量1 00重量份 ，通常爲0.01〜20重量份。此使用量若頗少，則難察見 目的效果，若頗多，則因硬化被膜的強度降低，故爲不佳 〇 將以上說明之塗料（A )及（B )分別於樹脂基板的 單面塗佈後，視需要乾燥，其次，令所形成的塗膜硬化， 則可取得本發明之耐擦傷性樹脂板。另外，兩塗料之塗佈 硬化順序爲任意的，且亦可同時進行。 塗料（A )和（B )之塗佈爲視需要於單面施以光罩 ，例如，以微照相凹版塗層後，滾筒滾層法、浸塗法、旋 塗法、型板塗層法、澆鑄轉印法、流塗法、噴霧塗層法等 之方法則可進行。 塗膜之硬化爲經由照射活化能量線，適當進行。活化 能量線可列舉例如，電子射線、紫外線、可見光線等，並 且根據硬化性化合物的種類適當選擇。於使用紫外線和可 見光線作爲活化能量線之情形中，通常使用光聚合引發劑 〇 光聚合引發劑可列舉例如，乙醯苯、乙醯苯苄基縮酮 、蒽醌、1- ( 4-異丙苯基）-2-羥基甲基丙烷酮、咔 哩、咕噸酮、4 -氯基二苯酮、4，4，-二胺基二苯酮、〗，卜二 甲氧基脫氧苯偶姻、3,3’-二甲基_4_甲氧基二苯酮、噻噸 酮、2,2 -二甲氧基-2 -苯基乙苯、ι·(4一十二院苯基）·2_ 羥基-2-甲基丙烷-1-酮、2 -甲基-1-〔 4-(甲硫基）苯基〕_ -11 - 200824907 2-嗎啉基丙烷-卜酮、三苯胺、2,4,6·三甲基苯甲醯二苯基 氧化膦、1-羥基環己基苯基酮、2-羥基-2-甲基-1_苯基丙 烷-1-酮、芴酮、芴、苯甲醛、苯偶姻乙醚、苯偶姻丙醚 、二苯酮 '密蚩酮、3-甲基乙醯苯、3,3’，4,4’-四-第三丁 基過氧羰基二苯酮（ΒΤΤΒ) 、2-(二甲胺基）-1-〔4-( 嗎啉基）苯基〕-2-(苯甲基）-l_丁酮、4-苯甲醯- 4’·甲基 二苯硫、苄基等。 光聚合引發劑亦可與色素增感劑組合使用。色素增感 劑可列舉例如咕噸、噻噸、香豆素、酮基香豆素化合物等 。光聚合引發劑與色素增感劑的組合可列舉例如ΒΤΤΒ與 咕噸的組合、ΒΤΤΒ與噻噸的組合、ΒΤΤΒ與香豆素的組 合、ΒΤΤΒ與酮基香豆素的組合等。 上述的光聚合引發劑因已市售，故可使用此類市售品 。市售的光聚合引發劑可列舉例如分別由 Ciba Specialty • Chemicals (股）所販售之 “IRGACURE 651”、 “IRGACURE 184”、“IRGACURE 500”、“IRGACURE 1 000” 、“IRGACURE 2959”、“DAROCUR 1173”、“IRGACURE 907”、“IRGACURE 369”、“IRGACURE 1 700”、“IRGACURE 1 800”、“IRGACURE 819”、及 “IRGACURE 7 84”、分別由 日本化藥（股）所販售之“KAYACURE ITX”、“KAYACURE DETX-S”、“KAYACURE BP-100”、“KAYACURE BMS”、 及 “KAYACURE 2-EAQ”等。 使用光聚合引發劑時，其使用量相對於硬化性化合物 1〇〇重量份，通常爲0.1重量份以上。其使用量若頗少， -12- 200824907 則相比於未使用光聚合引發劑之情況，硬化速度有變大的 傾向。另外，光聚合引發劑之使用量的上限，相對於硬化 性化合物1 00重量份，通常爲1 〇重量份左右。 又，活化能量線的強度和照射時間爲根據硬化性化合 物之種類和其塗膜厚度等而適當調整。活化能量線可於惰 性氣體氛圍氣中照射，且此惰性氣體可使用氮氣和氬氣等 如此所形成之硬化被膜的厚度分別爲1〜1 Ομπι爲佳 ，更佳爲2〜6μηι。此厚度若頗小，則耐擦傷性不夠充分 ，若頗大，則於高溫高濕下曝露時，易發生裂痕。硬化被 膜之厚度可經由調整樹脂基板表面塗佈之硬化性塗料每面 積的份量、和硬化性塗料中所含之固形成分的濃度而加以 調整。 如此所得之本發明的耐擦傷性樹脂板，具有即使押壓 亦難裂開、且耐擦傷性高的硬化被膜，可適合使用作爲行 動電話等所代表之攜帶型資訊終端的顯示窗保護板。又’ 亦可使用作爲數碼相機和掌上型攝錄機等之取景部、攜帶 型遊戲機的顯示窗保護板等之要求耐擦傷性領域的各種構 材。 由本發明之耐擦傷性樹脂板，製作攜帶型資訊終端之 顯示窗保護板上，首先，視需要進行印刷、挖孔等之加工 ，且切斷處理至必要的大小即可。其後，較佳如先前所述 若將塗料（A )所設置之硬化被膜面作爲表側’並且安裝 至攜帶型資訊終端的顯示窗，則可有效保護此顯示窗。 -13- 200824907 實施例 以下，示出本發明之實施例，但本發明不被其所限定 。例中，表示含量或使用量之％及份’只要無特別記述則 爲重量基準。又，物性的測定方法或評價方法爲如下。 〔硬化被膜之厚度〕 使用膜厚測定裝置〔Filmetrics公司的F-20〕測定 〔表面電阻〕 根據ASTM D-257測定。 〔耐擦傷性試驗〕 使用鋼棉#0000，以20 00g/ 4 cm2之荷重以10次來回 、1 5 0次來回、以下、以1 0 0次來回刻紋至可目視確認損 傷爲止摩擦，並以其來回次數予以評價。 〔押壓試驗〕 於外徑60x1 00mm、內徑3 0x50mm之金屬製框，配置 5 5x8 5mm的試驗片，並以具有直徑10mm之球狀尖端的金 屬棒，以1 〇mm/ min之速度押壓試驗片的中央，測定試 驗片破壞的強度。試驗爲實施3次，並以其平均値視爲測 定結果。 又，塗料（A )及（B )爲分別如下處理調製。 〔塗料（A )之調製〕 將作爲硬化性化合物之二季戊四醇六丙烯酸酯1 5份 及季戊四醇四丙烯酸酯15份、光聚合引發劑〔Ciba Specialty Chemicals (股）之 IRGACURE 184〕1.5 份、及 -14- 200824907 作爲溶劑之異丁醇34份及1-甲氧基-2-丙醇34份混合’ 調製塗料（A )。 〔塗料（B )之調製〕 將摻混銻之氧化錫（粒徑〇· 05〜0.5 μπι) 15重量份、 作爲硬化性化合物之二季戊四醇六丙烯酸酯7.5份及季戊 四醇四丙烯酸酯7.5份，光聚合引發劑〔Ciba Specialty Chemicals (股）之 IRG A CURE 184〕0.8 份、及作爲溶劑 之1-甲氧基-2-丙醇69份混合，調製塗料（Β )。 實施例1 將塗料（Α)，於厚度2mm、大小100mmx60mm之甲 基丙烯酸樹脂板〔住友化學（股）之Sumipex E〕的單面 以流塗法塗佈後，於室溫乾燥5分鐘，再於50 °C乾燥7 分鐘，於甲基丙烯酸樹脂板的表面形成塗膜。其次，使用 120W的高壓水銀燈照射0.5J/cm2的紫外線，令塗膜硬 化，形成厚度3.5 μιη的硬化被膜。其次，僅於形成此硬化 被膜面之反側面，將塗料（Β )以流塗法塗佈後，以室溫 乾燥1分鐘，再以50°C乾燥2分鐘，於甲基丙烯酸樹脂 板的表面形成塗膜。其次，使用120W的高壓水銀燈照射 0.5 J/ cm2的紫外線，令塗膜硬化，形成厚度2.3 μιη的硬 化被膜。如此處理所得之耐擦傷性樹脂板的表面電阻及耐 擦傷性試驗及押壓試驗的結果示於表1。另外，押壓試驗 爲以塗料（Α)形成硬化被膜之面作爲上面進行評價。 -15- 200824907 比較例1 將塗料（A)，於厚度2mm、大小100mmx60mm之甲 基丙烯酸樹脂板〔住友化學（股）之Sumipex E〕的兩面 以浸塗法塗佈後，於室溫乾燥5分鐘，再於50 °C乾燥7 分鐘，於甲基丙烯酸樹脂板的表面形成塗膜。其次，使用 120W的高壓水銀燈照射0.5J/cm2的紫外線，令塗膜硬 化，取得硬化被膜之厚度爲3 ·2μπι的耐擦傷性樹脂板。此 耐擦傷性樹脂板之表面電阻及耐擦傷性試驗及押壓試驗的 結果示於表1。另外，此耐擦傷性樹脂板若切削，則察見 附著許多切削粉。 比較例2 除了使用塗料（Β )代替塗料（A )以外，進行與比 較例1同樣之操作，取得硬化被膜之厚度爲2.8 μηι的耐擦 傷性樹脂板。此耐擦傷性樹脂板之表面電阻及耐擦傷性試 驗及押壓試驗的結果示於表！。 -16- 200824907 表1 例 評價面 硬化被膜厚度 (μπι) 表面電阻 (Ω) 耐擦傷性試驗 (來回次數） 押壓試驗 (kgf) 實施例1 塗料（A)面 3.5 1015< 950 26.5 塗料（B)面 2.3 5.8x10s 150 比較例1 塗料（A)面 *3.2 1015< 950 24.1 塗料（A)面 3.2 1015< 950 比較例2 塗料（B)面 2.8 5·8χ108 150 27.1 塗料（B)面 2.8 3·1χ108 150 產業上之可利用性 本發明之耐擦傷性樹脂板爲具有即使押壓亦難裂開、 且耐擦傷性高的硬化被膜，並且經由將此耐擦傷性樹脂板 使用作爲攜帶型資訊終端的顯示窗保護板，則可有效保護 此顯示窗。 -17-[Technical Field] The present invention relates to a scratch-resistant resin sheet suitable as a display window protection panel for a portable information terminal, and a display window protection panel for a portable information terminal. [Prior Art] Recently, mobile phones such as mobile phones and PHS (Personal Handy-phone System) have become a simple voice transmission function with display of text information and images. Portable information terminal types of information functions are widely used. In addition, unlike such portable telephones, PDAs (Personal Digital Assistants), which have both Internet functions and e-mail functions, are widely used. In this manual, such mobile phones and PHS, PDA, etc. are referred to as "portable information terminals". In other words, the "portable information terminal" in the present specification is a general name for a window (display) that can be carried by a person who can carry a left and right size and which displays text information and video information. In such a portable information terminal, text information and video information are displayed via liquid crystal and EL (electroluminescence), and the display window is generally made of a transparent resin as a protective plate (for example, refer to JP-A-2002-6764 Japanese Patent Laid-Open Publication No. 2004- 1 43 3 65 and JP-A-2004-299 1 99. In addition, in order to prevent surface damage, it is proposed to provide a scratch-resistant hardened film with a curable coating, and -4- 200824907 also proposes to contain conductive fine particles in the curable coating, and to provide antistatic to the cured film. Sex. [Description of the Invention] The cured film is provided on at least one surface of the protective sheet, and when it is provided on only one side, the surface thereof faces the front side (the side directly visible to the user and the touch side), but the hardening is provided only on one side. When the protective sheet of the film is exposed to high temperature and high humidity for a long period of time, there is a problem that bending tends to occur. Therefore, the hardened film can be provided on both sides of the protective sheet. However, when the hardened coating is formed of a curable coating material containing no conductive fine particles, the cured film has a problem of easily cutting the protective sheet when pressed. On the other hand, when it is carried out with a curable coating material containing conductive fine particles, it is difficult to obtain sufficient scratch resistance. Then, the inventors of the present invention have made efforts to review the display window protection panel of the portable information terminal which is provided with a hardened film which is hard to be cracked even if it is pressed, and which is resistant to scratches, and found that it is not contained by use. When the curable coating material of the conductive fine particles is formed into one surface, and the other surface hardening film is formed using the curable coating material containing the conductive fine particles, a display window suitable as a portable information terminal having the above desired performance can be obtained. The scratch resistant resin sheet of the protective sheet is achieved and is fully in accordance with the present invention. In other words, the present invention provides a cured film which is provided on one surface of a resin substrate and which is formed of a curable coating material containing no conductive fine particles, and which is characterized by a curable coating film containing conductive fine particles. - 200824907 Abrasion resin board. Further, according to the present invention, a display window protection panel of the portable information terminal constituted by the scratch-resistant resin sheet is also provided. The scratch-resistant resin sheet of the present invention is a hardened film which is hard to be cracked even if pressed, and has high scratch resistance, and can be effectively used by using the scratch-resistant resin sheet as a display window protection sheet of a portable information terminal. Protect its display window. [Embodiment] Examples of the resin constituting the substrate of the scratch-resistant resin of the present invention include a methacrylic resin, a polycarbonate resin, a polystyrene resin, a styrene-acrylonitrile copolymer, and triacetyl cellulose. Resin, etc. Among them, methacrylic resin is suitable as a resin constituting a substrate because of its high transparency and high rigidity. The methacrylic resin is a polymer mainly composed of methacrylate, and may be, for example, a monomer of methacrylate, and may be 50% by weight or more of methacrylate and 50% by weight or less of other monomers. Copolymer. In the case of the copolymer, the proportion of the methacrylate in the total monomer is preferably 70% by weight or more, more preferably 90% by weight or more. Methacrylate Alkyl methacrylate is preferably used, and methyl methacrylate is particularly preferably used. Further, examples of the monomer other than the methacrylate include, for example, acrylates such as methyl acrylate and ethyl acrylate, aromatic alkenyl compounds such as styrene and methylstyrene, and unsaturated acrylic acid and methacrylic acid. A carboxylic acid, an acrylonitrile, a methacrylonitrile-like alkenyl cyanamide compound, and the like. The resin substrate is a normal plate (sheet) and a film, and the surface is a flat surface -6 - 200824907, and may be a convex lens or a convex lens, and the surface is a curved surface. Further, a fine structure such as fine unevenness may be provided on the surface. The resin substrate may be colored by a dye, a pigment or the like as needed, and may contain an antioxidant, an ultraviolet absorber, rubber particles or the like. The thickness of the resin substrate is preferably 0.1 mm or more and 3.0 mm or less. In the present invention, a hardened film is formed on both surfaces of a resin substrate to form a scratch-resistant resin sheet. In this case, the cured film is formed into a hardened coating material containing no conductive fine particles (hereinafter, the curable paint is referred to as a paint (A). The curing of the other surface is carried out by using a curable coating containing conductive fine particles (hereinafter, this curable coating is referred to as a coating (B)). By forming a hardened film by using different coating materials (A) and (B) on both sides of the front and back sides, it is possible to obtain a scratch-resistant resin sheet having a cured film which is hard to be cracked even if pressed and has high scratch resistance. In the scratch-resistant resin sheet, the cured film formed of the coating material (A) usually has excellent scratch resistance than the cured film formed of the coating material (B) because it does not contain conductive fine particles. Since the hardened film formed by the coating material (B) contains conductive fine particles, the hardened film formed of the coating material (A) is excellent in antistatic property and electrical conductivity. In addition, in the case where the surface of the hardened film formed by the coating material (A) is pressed, it is harder to crack than when the surface of the hardened film formed by the coating material (B) is pressed. Therefore, when the scratch-resistant resin sheet is used as the display window protection sheet of the portable information terminal, the hardened film surface formed by the coating material (A) faces the front side (the person directly sees and touches the side), and the paint is applied ( B) The formed hardened film surface faces toward the back side (display side), which can be effective. That is, 200824907 makes it difficult for the user to touch, and it is difficult to crack, and when it is attached to dust, the back side that is difficult to wipe is resistant. Electrostatic properties can be used as a curable compound contained in the dust-repellent coatings (A) and (B), and a compound having a property of being cured by irradiation with an active energy ray such as an electron beam or ultraviolet rays is preferably used. A polyfunctional (meth) acrylate compound is preferably used. Here, the polyfunctional (meth) acrylate compound refers to a compound having at least two (meth) acryloxy groups in the molecule, and also has three or more, that is, at least three in the molecule. A compound of a propylene oxy group is preferably used. In the present specification, the term "(meth)acryloxyloxy group" means a propylene methoxy group or a methacryloxy group, and the term "(meth) acrylate or (meth) acrylate" ( Methyl) is also of the same meaning. Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, and 1,6-hexane diol di(meth) acrylate. , neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaglycerol tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, tris[(methyl) propylene oxy oxy] isocyanurate, tripentaerythritol octa (meth) acrylate, and the like. -8 - 200824907 Further, a phosphazene-based (meth) acrylate compound having a (meth) propylene oxime group introduced into a phosphazene ring of a phosphazene compound; a polyisocyanate having at least two isocyanate groups in the molecule, and a molecule a urethane (meth) acrylate compound obtained by a polyol reaction of at least one (meth) acryloxy group and a hydroxyl group; a compound having at least two carboxylic acid halide groups in the molecule, and having a molecule A polyester (meth) acrylate compound obtained by reacting at least one (meth) acryloxy group and a hydroxyl group polyol compound; an oligomer of a dimer or a trimer of each of the above compounds may also be used. These polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more kinds. Examples of the conductive fine particles contained in the coating material (B) include a metal oxide of cerium oxide, a composite oxide of indium/tin (ITO), tin oxide doped with cerium, and tin oxide doped with lead. Each of the fine particles of (PTO), cerium/zinc composite oxide. The conductive fine particles preferably have a particle diameter of 0.01 1 to 1 μηι. If the particle size is small, industrial production is difficult, and if a large particle size is used, the transparency of the cured film is lowered, which is not preferable. Further, the amount of the conductive fine particles used in the coating material is preferably 1 to 1 part by weight based on 100 parts by weight of the curable compound. If the amount of use is small, the resulting scratch-resistant resin sheet is easily cracked when pressed, and a sufficient antistatic effect cannot be obtained. If the amount is large, the scratch resistance of the cured film is lowered, and the film formability is lowered. In the case of the coatings (A) and (Β), the solvent may be contained in order to adjust the viscosity and the thickness of the cured film. The solvent may, for example, be 'methanol, ethyl-9-200824907 alcohol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol (second butanol), 2-methyl - propanol (isobutanol), 2-methyl-2-propanol (tertiary butanol) alcohol, 2-ethoxyethanol, 2-butoxyethanol, 3-methoxy- 1-propanol, b-methoxy-2-propanol, 1-ethoxy-2-propanol-like alkoxy alcohols, diacetone alcohol-like ketones, acetone, methyl ethyl ketone, A A ketone like isobutyl ketone, an aromatic hydrocarbon such as toluene or xylene, an ester of ethyl acetate or a butyl acetate. The amount of the solvent to be used is appropriately adjusted depending on the material, the shape, the coating method, the thickness of the target cured film, and the like. However, in general, in the coating material (A), the weight ratio of the curable compound is 20%. In the coating material (B), the total amount of the coating material (B) is about 20 to 10,000 parts by weight based on 100 parts by weight of the total amount of the curable compound and the conductive fine particles. Further, in the coating materials (A) and (B), additives such as a stabilizer, an antioxidant, a colorant, and a leveling agent may be contained as needed. By containing a leveling agent, the smoothness and scratch resistance of the hardened film can be improved. The leveling agent is preferably used as an anthrone oil, and examples thereof include dimethyl fluorenone oil, benzyl ketone oil, alkyl-aralkyl modified fluorenone oil, fluoro fluorenone oil, and poly Ether-modified anthrone oil, fatty acid ester modified anthrone oil, methyl hydroquinone oil, anthrone-containing anthrone oil, alkoxy-containing anthrone oil, phenol-based anthrone oil, A Propylene-based modified fluorenone oil, amine-modified fluorenone oil, carboxylic acid modified fluorenone oil, carbitol modified fluorenone oil, epoxy modified fluorenone oil, thiol-modified fluorenone oil , fluorine modified ketone oil, polyether modified ketone oil and so on. These fluorenone oils may be used alone or in combination of two or more. The amount of the kerosene oil used is usually 0.011 to 20 parts by weight based on 100 parts by weight of the hardening compound -10- 200824907 in the coating material (A), relative to the curable compound and conductivity in the coating material (B). The total amount of the fine particles is 100 parts by weight, usually 0.01 to 20 parts by weight. If the amount of use is small, it is difficult to see the intended effect. If there are many, the strength of the cured film is lowered, so it is not preferable. The coatings (A) and (B) described above are respectively on one side of the resin substrate. After the application, drying is carried out as needed, and secondly, the formed coating film is cured to obtain the scratch-resistant resin sheet of the present invention. Further, the coating hardening order of the two coating materials is arbitrary and can also be carried out simultaneously. Coating of coatings (A) and (B) is carried out on a single side as needed, for example, after micro-gravure coating, roller roll method, dip coating method, spin coating method, stencil coating method, casting A method such as a transfer method, a flow coating method, or a spray coating method can be carried out. The hardening of the coating film is carried out as appropriate by activating the energy ray through irradiation. The activation energy ray may, for example, be an electron beam, an ultraviolet ray, a visible ray or the like, and may be appropriately selected depending on the type of the curable compound. In the case where ultraviolet rays and visible rays are used as the active energy ray, the photopolymerization initiator photopolymerization initiator is usually used, for example, acetophenone, acetophenone ketal, hydrazine, 1-(4-iso) Propyl phenyl)-2-hydroxymethylpropanone, hydrazine, xanthone, 4-chlorobenzophenone, 4,4,-diaminobenzophenone, 〗 〖, dimethoxy oxy phenylene Margin, 3,3'-dimethyl-4_methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylethylbenzene, ι·(4-12 phenyl) 2· hydroxy-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]_-11 - 200824907 2-morpholinylpropane-buxone, triphenylamine , 2,4,6·trimethylbenzimidium diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 phenylpropan-1-one, anthrone, Bismuth, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone dextran, 3-methyl acetophenone, 3,3', 4,4'-tetra-tert-butylperoxy Carbonyl benzophenone (oxime), 2-(dimethylamino)-1-[4-(morpholino)phenyl]-2-(phenylmethyl)-l-butanone, 4-benzylformamide- 4'·methyl two Sulfur, a benzyl group and the like. The photopolymerization initiator can also be used in combination with a dye sensitizer. Examples of the dye sensitizer include xanthene, thioxanthene, coumarin, and ketocoumarin compound. The combination of the photopolymerization initiator and the dye sensitizer may, for example, be a combination of hydrazine and xanthene, a combination of hydrazine and thioxan, a combination of hydrazine and coumarin, or a combination of hydrazine and keto coumarin. Since the above photopolymerization initiator is commercially available, such a commercially available product can be used. Commercially available photopolymerization initiators include, for example, "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1 000", "IRGACURE 2959", and "" sold by Ciba Specialty Chemicals, respectively. DAROCUR 1173”, “IRGACURE 907”, “IRGACURE 369”, “IRGACURE 1 700”, “IRGACURE 1 800”, “IRGACURE 819”, and “IRGACURE 7 84”, respectively sold by Nippon Chemical Co., Ltd. “KAYACURE ITX”, “KAYACURE DETX-S”, “KAYACURE BP-100”, “KAYACURE BMS”, and “KAYACURE 2-EAQ”. When a photopolymerization initiator is used, the amount thereof is usually 0.1 part by weight or more based on 1 part by weight of the curable compound. If the amount used is relatively small, -12-200824907 tends to have a higher curing rate than when a photopolymerization initiator is not used. In addition, the upper limit of the amount of use of the photopolymerization initiator is usually about 1 part by weight based on 100 parts by weight of the curable compound. Further, the intensity of the active energy ray and the irradiation time are appropriately adjusted depending on the type of the curable compound, the thickness of the coating film, and the like. The activation energy ray can be irradiated in an inert gas atmosphere, and the inert gas can be made of nitrogen gas or argon gas. The thickness of the hardened film thus formed is preferably 1 to 1 Ομπι, more preferably 2 to 6 μm. If the thickness is small, the scratch resistance is insufficient, and if it is large, cracks are likely to occur when exposed to high temperature and high humidity. The thickness of the cured film can be adjusted by adjusting the amount of each side of the curable coating applied to the surface of the resin substrate and the concentration of the solid component contained in the curable coating. The scratch-resistant resin sheet of the present invention thus obtained has a cured film which is hard to be cracked even if pressed, and has high scratch resistance, and can be suitably used as a display window protection sheet of a portable information terminal represented by a mobile phone or the like. Further, various materials in the field of scratch resistance, such as a viewfinder for a digital camera and a palm-sized camcorder, and a display window protection panel for a portable game machine, can be used. The display window protection panel of the portable information terminal is produced from the scratch-resistant resin sheet of the present invention. First, it is necessary to perform processing such as printing, digging, and the like, and the cutting process can be performed to a necessary size. Thereafter, it is preferable to protect the display window by installing the hardened film surface provided by the coating (A) as the front side as shown in the foregoing and mounting it to the display window of the portable information terminal. -13 - 200824907 EXAMPLES Hereinafter, examples of the invention are shown, but the invention is not limited thereto. In the examples, the % and the parts of the content or the amount used are based on weight unless otherwise specified. Moreover, the measuring method or evaluation method of physical properties is as follows. [Thickness of Hardened Film] Measured by a film thickness measuring device [F-20 of Filmetrics Co., Ltd.] [Surface Resistance] Measured in accordance with ASTM D-257. [Scratch resistance test] Using steel wool #0000, with a load of 20 00g / 4 cm2, 10 round trips, 150 round trips, below, and 100 rounds back and forth until the damage can be visually confirmed. It is evaluated by the number of round trips. [Pressure test] A test piece of 5 5x8 5mm was placed in a metal frame with an outer diameter of 60x1 00mm and an inner diameter of 30x50mm, and was pressed at a speed of 1 〇mm/min with a metal rod having a spherical tip with a diameter of 10 mm. The center of the test piece was pressed, and the strength of the test piece was measured. The test was carried out 3 times and the average enthalpy was regarded as the measurement result. Further, the coatings (A) and (B) were prepared and treated as follows. [Preparation of Coating (A)] 15 parts of dipentaerythritol hexaacrylate as a curable compound, 15 parts of pentaerythritol tetraacrylate, and 1.5 parts of a photopolymerization initiator [IRGACURE 184 of Ciba Specialty Chemicals], and - 14- 200824907 As a solvent, 34 parts of isobutanol and 34 parts of 1-methoxy-2-propanol were mixed to prepare a coating (A). [Preparation of Coating (B)] 15 parts by weight of tin oxide (particle diameter 05 05~0.5 μπι) blended with bismuth, 7.5 parts of dipentaerythritol hexaacrylate as a curable compound, and 7.5 parts of pentaerythritol tetraacrylate. 0.8 parts of a polymerization initiator [IRG A CURE 184 of Ciba Specialty Chemicals Co., Ltd.] and 69 parts of 1-methoxy-2-propanol as a solvent were mixed to prepare a coating material (Β). Example 1 A coating material was applied by a flow coating method on one side of a methacrylic resin sheet (Sumipex E) of a thickness of 2 mm and a size of 100 mm x 60 mm, and dried at room temperature for 5 minutes. After drying at 50 ° C for 7 minutes, a coating film was formed on the surface of the methacrylic resin sheet. Next, an ultraviolet ray of 0.5 J/cm 2 was irradiated with a 120 W high-pressure mercury lamp to harden the coating film to form a hardened film having a thickness of 3.5 μm. Next, the coating (Β) was applied by a flow coating method only after forming the reverse side of the hardened film surface, and then dried at room temperature for 1 minute and then dried at 50 ° C for 2 minutes on the surface of the methacrylic resin sheet. A coating film is formed. Next, a high-pressure mercury lamp of 120 W was used to irradiate ultraviolet rays of 0.5 J/cm 2 to harden the coating film to form a hard coating film having a thickness of 2.3 μm. The surface resistance and scratch resistance test and the results of the pressing test of the scratch-resistant resin sheet obtained in this manner are shown in Table 1. Further, the pressing test was performed by forming the surface of the hardened film with a paint (Α) as the above. -15- 200824907 Comparative Example 1 The coating (A) was applied by dip coating on both sides of a methacrylic resin sheet (Sumipex E) of a thickness of 2 mm and a size of 100 mm x 60 mm, and then dried at room temperature. In a minute, it was further dried at 50 ° C for 7 minutes to form a coating film on the surface of the methacrylic resin sheet. Then, a high-pressure mercury lamp of 120 W was used to irradiate ultraviolet rays of 0.5 J/cm 2 to harden the coating film, and a scratch-resistant resin sheet having a thickness of 3 · 2 μm was obtained. The results of the surface resistance and scratch resistance test and the pressing test of the scratch-resistant resin sheet are shown in Table 1. Further, if the scratch-resistant resin sheet is cut, it is observed that many cutting powders are attached. Comparative Example 2 A scratch-resistant resin sheet having a thickness of the cured film of 2.8 μm was obtained in the same manner as in Comparative Example 1, except that the coating material (?) was used instead of the coating material (A). The results of the surface resistance and scratch resistance test and the pressing test of this scratch-resistant resin sheet are shown in the table! . -16- 200824907 Table 1 Example Evaluation of surface hardened film thickness (μπι) Surface resistance (Ω) Scratch resistance test (number of round trips) Pressing test (kgf) Example 1 Coating (A) surface 3.5 1015 < 950 26.5 Coating (B Face 2.3 5.8x10s 150 Comparative Example 1 Coating (A) Noodle *3.2 1015 < 950 24.1 Coating (A) Noodle 3.2 1015 < 950 Comparative Example 2 Coating (B) Surface 2.8 5·8χ108 150 27.1 Coating (B) Surface 2.8 3 1χ108 150 Industrial Applicability The scratch-resistant resin sheet of the present invention is a hardened film which is hard to be cracked even if pressed, and has high scratch resistance, and is used as a portable type information by using the scratch-resistant resin sheet. The display window protection board of the terminal can effectively protect the display window. -17-