201004801 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，行動電話或 PHS( Personal Handy-phone System，個人電話系統）等的攜帶型電話類，係在隨著網 φ 際網路（Internet )的普及，除作爲單純的語音傳達功能 之外’尙具有能顯示文字資訊或影像資訊之功能之攜帶式 資訊終端機而廣泛普及。又，除此種攜帶型電話類之外， 尙在住址名簿等功能外倂持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 廣範在使用。本說明書中，則將此等行動電話或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“攜帶型資訊終端機”，係指本身爲一般人能隨身攜 φ 帶之程度的大小，而具有能顯示文字資訊或影像資訊等用 的視窗者之總稱。 此等攜帶型資訊終端機，係藉由液晶或EL ( electroluminescence ’ 電致 發光） 等 方式而 作成能 顯示文 字資訊 或影像資訊者’惟爲其顯示視窗，則作爲保護板而一般採 用透明樹脂製者’其中由於透明性之故甲基丙烯酸樹脂板 很適合使用。並且，於此保護板上，爲防止表面之刮擦起 見，有一種藉由硬化性塗料而設置耐擦傷性（硬敷層性） 的硬化被膜之提案（參考日本專利特開2002-6764號公報 201004801 、日本專利特開 2004- 1 43 365號公報、日本專利特開 2004-2991 99 號公報）。 【發明內容】 將成爲攜帶型資訊終端機的顯示視窗保護板的基板， 係從生產性的觀點來看，藉由熱塑性樹脂的擠壓成型而製 造較爲有利，惟如於熱塑性樹脂的擠壓板上設置硬化被膜 時，則其硬化被膜的耐擦傷性爲不一定足夠者。 於是，本發明人，爲開發一種以熱塑性樹脂的擠出板 (extruding plate )作爲基板，作爲具有耐擦傷性高的硬 化被膜之攜帶型資訊終端機的顯示視窗保護板很適用的耐 擦傷性樹脂板起見，專心硏究。 本發明提供下述手段。 〔1〕一種耐擦傷性樹脂板，其特徵爲，將熱塑性樹 脂擠壓成型所成而於面內的阻滯値（retardation value ) 爲15nm以下之擠出板的至少一邊的面上，形成有硬化被 膜而成。 〔2〕如前項〔1〕記載之耐擦傷性樹脂板，其中熱塑 性樹脂爲甲基丙烯酸樹脂。 〔3〕如前項〔1〕或〔2〕記載之耐擦傷性樹脂板， 其中擠出板的厚度爲0.2至3mm。 〔4〕如前項〔1〕至〔3〕之任一項記載之耐擦傷性 樹脂板，其中硬化被膜，係由含有分子中至少具有3個（ 甲基）丙烯醯氧基之化合物之硬化性塗料所形成者。 -6- 201004801 〔5〕如前項〔1〕至〔4〕之任一項記載之耐擦傷性 樹脂板’其中硬化被膜，係由含有導電性粒子之硬化性塗 料所形成者。 〔6〕如前項〔1〕至〔5〕的任一項記載之耐擦傷性 樹脂板，其中擠出板，係將由模具（die)所擠出之熔融 熱塑性樹脂夾入於至少1支爲彈性輥（resilient roll)之 2支輥間成型而成者。 φ 〔 7〕如前項〔1〕至〔6〕之任一項記載之耐擦傷性 樹脂板，其中擠出板，係經以較構成擠出板之熱塑性樹脂 的玻璃轉移溫度爲低3至25 °C的溫度下熱處理者。 〔8〕一種攜帶型資訊終端機之顯示視窗保護板，其 特徵爲由前項〔1〕至〔7〕之任一項記載之耐擦傷性樹脂 板所成。 〔9〕一種顯示器用保護板，其特徵爲：由前項〔1〕 至〔7〕之任一項記載之耐擦傷性樹脂板所成。 • 如採用本發明，則可容易製得具有耐擦傷性高的硬化 被膜之耐擦傷性樹脂板，並如將該耐擦傷性樹脂板作爲顯 示器用保護板，特別是作爲攜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。 〔發明之最佳實施形態〕 本發明之耐擦傷性樹脂板，係將經擠壓成型熱塑性樹 脂所成擠出板作爲基板，並於其至少一邊的面上形成有硬 化被膜而成者。而且，上述擠出板，係其面內的阻滯値爲 -7- 201004801 15nm以下者。 熱塑性樹脂而言，可例舉：甲基丙烯酸樹脂、聚酯樹 脂、聚碳酸酯樹脂、聚環狀烯烴樹脂、聚苯乙烯樹脂、苯 乙烯-甲基丙烯酸酯共聚合物（MS樹脂）、丙烯腈-苯乙 烯共聚合物（AS樹脂）、聚氟化亞乙烯樹脂（PVDF樹脂 )等的透明樹脂。其種類，可適當加以選擇，惟特別是甲 基丙烯酸樹脂很適合使用。 甲基丙烯酸樹脂，係以甲基丙烯酸酯作爲主體之聚合 物，可爲甲基丙烯酸酯的單獨聚合物，亦可爲甲基丙烯酸 酯50重量％以下與此外的單體50重量％以下的共聚物。 在此，作爲甲基丙烯酸酯而言，通常採用甲基丙烯酸的烷 基酯。 甲基丙烯酸樹脂的較佳的單體組成，係以全單體爲基 準計，甲基丙烯酸烷酯在50至100重量％、丙烯酸烷酯在 〇至50重量％，此外的單體在0至49重量％，更佳爲甲基 丙烯酸烷酯在50至99.9重量％、丙烯酸烷酯在0.1至50 重量％，此外的單體在〇至49重量％。 在此，作爲甲基丙烯酸烷酯的例而言，可例舉：甲基 丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙 烯酸2-乙基己酯等，其烷基的碳數通常爲1至8、較佳爲 1至4。其中甲基丙烯酸甲酯很適合使用。 又，作爲丙烯酸烷酯的例而言，可例舉：丙烯酸甲酯 、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等，其烷 基的碳數通常爲1至8、較佳爲1至4。 -8- 201004801 又’甲基丙烯酸烷酯及丙烯酸烷酯以外的單體，可爲 單官能單體’亦即分子內具有1個聚合性的碳-碳雙鍵之 化合物，亦可爲多官能單體，亦即分子內至少具有2個以 上之聚合性的碳-碳雙鍵之化合物，惟單官能單體很適合 使用。並且’作爲此種單官能單體而言，可例舉：如苯乙 烯、〇：-甲基苯乙烯、乙烯基甲苯般的芳香族烯基化合物 ，如丙烯腈、甲基丙烯腈般的烯基氰化合物，如丙烯酸、 甲基丙烯酸般的不飽和竣酸、馬來酸酐、N-取代馬來酿亞 胺等。 再者，使甲基丙烯酸甲酯的單獨聚合物，或者甲基丙 烯酸甲酯與甲基丙烯酸及/或丙烯酸的共聚物進行環化反 應，以使具有戊二酸酐構造〔式（1)〕或戊二醯亞胺構 造〔式（2)〕之聚合物，亦可作爲甲基丙烯酸樹脂使用201004801 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 phones such as mobile phones or PHS (Personal Handy-phone System) have become popular in the Internet, except for the simple voice transmission. In addition to the functions, it is widely used as a portable information terminal having the function of displaying text information or image information. In addition, in addition to such portable telephones, PDAs (Personal Digital Assistants), which maintain Internet functions or e-mail functions in addition to functions such as address book, are also widely used. In this specification, these mobile phones, PHS, PDA, etc. are collectively referred to as "portable information terminal devices". In other words, the term "portable information terminal" as used in this specification refers to a general name for a window that can display text information or video information, such as the size that an average person can carry with him. These portable information terminals are made of liquid crystal or EL (electroluminescence 'electroluminescence), etc., which can display text information or video information, but only as a display window, they are generally made of transparent resin as a protective sheet. Among them, methacrylic resin sheets are suitable for use due to transparency. Further, on the protective plate, in order to prevent scratching of the surface, there is a proposal of providing a hardened film having scratch resistance (hard coating property) by a curable coating material (refer to Japanese Patent Laid-Open No. 2002-6764) Japanese Patent Publication No. 2004-04801, Japanese Patent Laid-Open No. 2004-143, No. 365, and Japanese Patent Laid-Open No. 2004-2991. SUMMARY OF THE INVENTION A substrate to be a display window protection panel of a portable information terminal is advantageously produced by extrusion molding of a thermoplastic resin from the viewpoint of productivity, for example, extrusion of a thermoplastic resin. When the hardened film is provided on the board, the scratch resistance of the hardened film is not necessarily sufficient. Then, the present inventors have developed a scratch-resistant resin which is suitable for use as a display window protection plate of a portable information terminal having a high-scratch-resistant hardened film as a substrate by using an extruded plate of a thermoplastic resin as a substrate. See you from the board and concentrate on it. The present invention provides the following means. [1] A scratch-resistant resin sheet characterized in that at least one side of an extrusion plate having a retardation value of 15 nm or less formed by extrusion molding of a thermoplastic resin is formed. Hardened film is formed. [2] The scratch-resistant resin sheet according to [1], wherein the thermoplastic resin is a methacrylic resin. [3] The scratch-resistant resin sheet according to [1] or [2], wherein the extruded sheet has a thickness of 0.2 to 3 mm. [4] The scratch-resistant resin sheet according to any one of [1] to [3] wherein the hardened film is made of a hardening property containing a compound having at least three (meth)acryloxy groups in the molecule. The paint is formed. [6] The scratch-resistant resin sheet of any one of the above-mentioned items [1] to [4] wherein the cured film is formed of a curable coating containing conductive particles. [6] The scratch-resistant resin sheet according to any one of [1] to [5] wherein the extruded sheet is formed by sandwiching a molten thermoplastic resin extruded from a die into at least one of the elastic sheets. Formed between two rolls of a resilient roll. The scratch-resistant resin sheet according to any one of the items [1] to [6] wherein the extruded sheet is at a temperature of 3 to 25 lower than the glass transition temperature of the thermoplastic resin constituting the extruded sheet. Heat treated at a temperature of °C. [8] A display window protection panel of a portable information terminal, which is characterized in that it is formed of a scratch-resistant resin sheet according to any one of the items [1] to [7]. [9] A protective sheet for a display, which is obtained by the scratch-resistant resin sheet according to any one of the items [1] to [7]. • According to the present invention, a scratch-resistant resin sheet having a hardened film having high scratch resistance can be easily produced, and the scratch-resistant resin sheet can be used as a protective sheet for a display, particularly as a portable information terminal. When the window protection board is used, it can effectively protect its display window. BEST MODE FOR CARRYING OUT THE INVENTION The scratch-resistant resin sheet of the present invention is obtained by using an extruded sheet formed by extrusion molding a thermoplastic resin as a substrate and a hard coating film formed on at least one surface thereof. Further, the above-mentioned extruded sheet has a retardation 面 in the plane of -7 - 201004801 15 nm or less. The thermoplastic resin may, for example, be a methacrylic resin, a polyester resin, a polycarbonate resin, a polycyclic olefin resin, a polystyrene resin, a styrene-methacrylate copolymer (MS resin), or propylene. A transparent resin such as a nitrile-styrene copolymer (AS resin) or a polyvinylidene fluoride resin (PVDF resin). The type can be appropriately selected, but in particular, a methacrylic resin is suitable for use. The methacrylic resin is a polymer mainly composed of methacrylate, and may be a single polymer of methacrylate, or may be copolymerized with 50% by weight or less of methacrylate and 50% by weight or less of other monomers. Things. Here, as the methacrylate, an alkyl ester of methacrylic acid is usually used. The preferred monomer composition of the methacrylic resin is based on the total monomer, the alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is at 50% by weight, and the monomer is 0 to 49% by weight, more preferably 50 to 99.9% by weight of the alkyl methacrylate, 0.1 to 50% by weight of the alkyl acrylate, and further monomer of 〇 to 49% by weight. Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like, and an alkyl group thereof. The carbon number is usually from 1 to 8, preferably from 1 to 4. Among them, methyl methacrylate is very suitable for use. Further, examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, and the alkyl group has a carbon number of usually 1 to 8, preferably. It is 1 to 4. -8- 201004801 Further, the monomer other than the alkyl methacrylate and the alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or may be a polyfunctional compound. A monomer, that is, a compound having at least two or more polymerizable carbon-carbon double bonds in a molecule, but a monofunctional monomer is suitably used. And 'as such a monofunctional monomer, an aromatic alkenyl compound such as styrene, fluorene:-methylstyrene or vinyltoluene, such as acrylonitrile or methacrylonitrile. A cyano compound such as acrylic acid, methacrylic acid, unsaturated citric acid, maleic anhydride, N-substituted maleimide, and the like. Further, a single polymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and/or acrylic acid is subjected to a cyclization reaction to have a glutaric anhydride structure [formula (1)] or a polymer of the pentanediamine structure [formula (2)], which can also be used as a methacrylic resin
(1) (2) 式（1)中，R1表示氫原子或甲基、R2表示氫原子或 甲基。式（2)中’R3表示氫原子或甲基、R4表示氫原子 或甲基、R5表示氫原子或取代基，作爲此取代基的例而言 ，可舉：如甲基、乙基般的烷基，如環己基般的環烷基， 如苯基般的芳基’如苄基般的芳烷基’其碳數通常爲1至 20程度。 -9- 201004801 又’作爲多官能單體的例而言，可舉：如乙二醇二甲 基丙嫌酸酯、丁二醇二甲基丙烯酸酯、三羥甲基丙烷三丙 烯酸酯般的多元醇的聚不飽和羧酸酯，如丙烯酸烯丙酯、 甲基丙烯酸烯丙酯，如肉桂酸烯丙酯般的不飽和羧酸的鏈 烯基酯’如酞酸二烯丙酯、馬來酸二烯丙酯、三烯丙基三 聚氰酸酯、三烯丙基異三聚氰酸酯般的有機多元酸的聚鏈 烯基酯’如二乙烯基苯般的芳香族聚鏈烯基化合物等。 在此’上述的甲基丙烯酸烷酯、丙烯酸烷酯、以及此 等以外的單體，分別按需要，可採用其等的2種以上。 甲基丙烯酸樹脂，從擠出板的耐熱性的觀點來看，較 佳爲其玻璃轉移溫度在60°C以上者，更佳爲在80°C以上 者。該玻璃轉移溫度，如調整單體種類或其比例，即可適 當加以設定。 甲基丙稀酸樹脂，如藉由懸浮聚合（suspension polymerization ) ' 乳化聚合（emulsion polymerization) 、塊狀聚合（bulk polymerization )等的方法而使其單體 成分進行聚合，即可調製。此時，爲獲得適當的玻璃轉移 溫度起見，又爲獲得能顯示對合適的擠出板的成型性之黏 度起見，較佳爲在聚合時使用鏈轉移劑（chain transfer agent )。鏈轉移劑的量，則按照單體的種類或其比例而適 當決定即可。 於熱塑性樹脂中，亦可調配其他成分而作爲樹脂組成 物使用。作爲此種調配成分而言，可例舉：如橡膠粒子、 染料或顏料般的著色劑、抗氧劑、紫外線吸收劑等。特別 -10- 201004801 是在甲基丙烯酸樹脂的情形，如調配橡膠粒子時，則由於 擠出板的而耐衝擊性或柔軟性可獲提升而難於裂開之故很 合適。 可調配於熱塑性樹脂、特別是甲基丙烯酸樹脂之橡膠 粒子而言，例如’可採用丙烯酸系、丁二烯系、苯乙烯_ 丁 —嫌系等的各種橡膠，其中，從耐天候性（weathering )的觀點來看’丙烯酸系橡膠粒子很適合使用。丙烯酸系 φ 橡膠粒子而言，例如，可使用由如丙烯酸丁酯般的以丙烯 酸烷酯作爲主體之彈性聚合物所成單層構造者，或於由以 甲基丙烯酸甲酯作爲主體之硬質聚合物所成內層周圍，設 置有由如丙烯酸丁酯般的以丙烯酸烷基作爲主體之彈性聚 合物所成外層之多層構造者。再者，於上述彈性聚合物中 ，一般少量共聚合有多官能單體。 又，於上述彈性聚合物周圍設置有由以甲基丙烯酸甲 酯作爲主體之硬質聚合物所成最外層之多層構造者，亦有 φ 利使用。可列舉：於由以如丙烯酸丁酯般的丙烯酸烷酯作 爲主體之彈性聚合物所成的內層周圍，設置有由以甲基丙 烯酸甲酯作爲主體之硬質聚合物層之二層構造者，或於由 以甲基丙烯酸甲酯作爲主體之硬質聚合物所成內層周圍， 設置由以如丙烯酸丁酯般的丙烯酸烷酯作爲主體之彈性聚 合物所成中間層’再於其周圍’設置有由以甲基丙烯酸甲 酯作爲主體之硬質聚合物所成外層之三層構造者。此種多 層構造的橡膠粒子’係經揭示於例如’日本專利特公昭 5 5-2 75 76號公報中。特別是，上述之三層構造者很合適， -11 - 201004801 日本專利特公昭5 5 -2 75 76號公報的實施例3所記載者， 係很合適的組成之一。 可調配於熱塑性樹脂之橡膠粒子而言，從表面硬度或 耐衝擊性、表面平滑性的觀點來看，平均粒徑爲〇.〇5至 0.4 // m者很適合使用。如橡膠粒子的平均粒徑過小時，則 擠出板的表面硬度不足夠，或擠出板會變脆。另一方面， 如橡膠粒子的平均粒徑過大時，則可能影響擠出板的表面 平滑性。橡膠粒子，一般而言，可藉由乳化聚合而製造， 其時，如調節乳化劑的添加量或單體的飼給量節，則可控 制平均粒徑爲所需要之値。 如於熱塑性樹脂中調配橡膠粒子時，則兩者的比例， 較佳爲以兩者合計爲1 〇〇重量份計，作成熱塑性樹脂爲50 至95重量份、橡膠粒子爲5至50重量份。如橡膠粒子的 量過少時，則擠出板的耐衝擊性或柔軟性不會充分獲改善 ，如過多時，擠出板的表面硬度或剛性會不足夠之故不宜 〇 如將上述熱塑性樹脂加以擠壓成型，則可獲得將成爲 本發明之耐擦傷性樹脂板的基板之擠出板。擠壓成型，具 體而言，可藉由如T形模具（T-die )法或吹塑成型（ inflation )法般的熔融擠出法實施。所得擠出板表面可爲 平滑，亦可設置有細微的凹凸。如欲賦與平滑性或凹凸形 狀時，則將熱塑性樹脂從例如T型模具熔融擠出’並使所 得板狀物的至少單面接觸於輥筒（Γ〇11)或皮帶（belt)以 進行製板之方法’由於能獲得表面性狀良好的板材之故很 -12- 201004801 合適。尤其是，從提升擠出板的平滑性或形狀賦與的精密 性之觀點來看，較佳爲使將熱塑性樹脂熔融擠出所得板狀 物的兩面接觸於輥筒或皮帶表面以進行成型之方法。此時 所使用之輥筒或皮帶，均屬於金屬製爲宜。因而，較佳形 態而言，可舉：將熱塑性樹脂從T型模具熔融擠出機，使 其與至少1支鏡面輕筒（mirror plane roll)接觸，更佳爲 使其與2支鏡面輥筒接觸面而在夾入之狀態下進行成型之 參 方法。 又，擠出板，需要時亦可作成多層構成者。可例舉： 含有橡膠粒子之甲基丙烯酸樹脂與不含有橡膠粒子之甲基 丙烯酸樹脂所成之多層構造，玻璃轉移溫度不相同的複數 種甲基丙烯酸樹脂的多層構造，甲基丙烯酸樹脂與如聚碳 酸酯樹脂般的甲基丙烯酸樹脂以外的熱塑性樹脂所成之多 層構造等。 欲製造此種多層構造的擠出板時，則可採用例如複數 φ 部擠壓機，與具有爲將從此所擠出之樹脂加以層合之用的 多岐管（multimanifold)方式或給料部件（feed block) 方式等機構之周知的多層擠壓機。 擠出板的厚度，通常爲0.2至3mm、較佳爲0.25至 2.5mm。如厚度過薄時，則可能作爲顯示器用保護板的基 板之強度或剛性不足夠，又，如厚度過厚時，則可能作爲 顯示器用保護板的基板之設計（design )上不適當。再者 ，如將擠出板作爲顯示器用保護板的基板使用時，則可配 合其顯示視窗的表面形狀而按平面形狀，或具有曲面之形 -13- 201004801 狀適用。 爲製造本發明中所需要之面內的阻滯値在15nm以下 的擠出板時，祗要是如前所述，當從T形模具所擠出之熔 融熱塑性樹脂夾入2支輥筒間進行成型者，則作爲其至少 1支輥筒而採用彈性輥，以面使熔融熱塑性樹脂的兩面接 觸於輥筒並通過之方法，係由於能減少成型時的歪斜，並 減少強度或熱收縮性的各向異性（anisotropy)之故，爲 製造面內的阻滯値小的擠壓板材上很合適的方法。作爲彈 性輥而言，金屬彈性輥，例如，具備有豎輥（shaft roll ) ，與按能覆蓋該豎輥的外周面之方式所配置，而接觸於熔 融熱塑性樹脂之圓筒形的金屬製薄膜，於此等豎輥與金屬 製薄膜之間封入有水或油等經控制溫度之流體者，或經於 橡膠輥表面繞捲金屬皮帶者很適合採用。又，於採用2支 高剛性的金屬輥之方法中，如調整金屬輥間的壓力、各金 屬輥的溫度、擠壓成型時的生產速度等，亦可將所得擠出 板的面內的阻滯値爲15nm以下。 再者，即使在面內的阻滯値爲15nm以上之擠出板， 如在既定溫度下進行加熱處理，仍可使面內的阻滯値作成 爲15nm以下。該加熱處理的溫度，較佳爲較構成擠出板 之熱塑性樹脂的玻璃轉移溫度爲低3至25°C程度的溫度。 又，處理時間可適當選擇，惟通常爲30分鐘至24小時。 加熱方法亦可適當選擇，可例舉··靜置於熱風循環烘箱（ oven )內之方法，或藉由紅外線等的加熱器的輻射熱而加 熱之方法。其中，由於可同時處理大量擠出板之故，靜置 -14- 201004801 於熱風循環烘箱內之方法很適合採用。於熱風循環烘箱內 靜置擠壓板材之方法而言，可以單獨靜置1片，亦可以重 疊複數片同時靜置。又，亦可作成對所靜置之擠出板施加 荷重以防止變形之發生之方式。荷重可適當選擇，惟爲防 止面內發生荷重分佈起見，較佳爲按能成爲均等的壓力之 方式設定荷重。荷重亦可適當選擇，惟通常爲0.001至 0.1kg/ cm2程度。於既定時間的加熱處理後，則需要將擠 φ 出板冷卻至室溫。冷卻方法並不特別加以限定，可立即取 出擠出板，並解除荷重後加以冷卻，亦可在施加荷重之下 徐冷至室溫後再取出擠出板。欲降低面內的阻滯値時，則 更佳爲採用後者的方法。進行徐冷時，其溫度變化速度並 不特別加以限定，惟通常爲2至3 0 °C /小時。 於如此所得面內的阻滯値爲1 5 nm以下之擠壓板材的 至少一邊的面上形成硬化被膜之結果，可製得具有耐擦傷 性高的硬化被膜之本發明之耐擦傷性樹脂板。爲形成硬化 〇 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，經混有溶劑、導電性粒 子、硬化觸媒等者。 首先，如就硬化性化合物說明時，從丙烯酸酯、胺基 甲酸乙酯丙烯酸酯、環氧基丙烯酸酯、羧基改性環氧基丙 烯酸酯、聚酯丙烯酸酯、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 之效果者即可。其中，作爲能帶來高的耐擦性之硬化性化 -15- 201004801 合物，可舉：多官能丙烯酸酯系、多官能胺基甲酸乙酯丙 烯酸酯系、多官能環氧基丙烯酸酯系等，自由基聚合系的 硬化性化合物、或烷氧基矽烷、烷基烷氧基矽烷等，熱聚 合性的硬化性化合物。此等硬化性化合物，係例如，因電 子射線、放射線、紫外線等能量標線（energy line )之照 射而硬化，或因加熱而硬化者。此時硬化性化合物，可以 分別單獨使用，亦可組合複數種化合物使用。 此等硬化性化合物之中較佳者，係分子中至少具有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。其他， 本說明書中，稱爲（甲基）丙烯酸酯' (甲基）丙烯酸等 時的「（甲基）」亦爲同樣意義。 分子中至少具有3個（甲基）丙烯醯氧基之硬化性化 合物而言’可例舉：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、新戊三醇三（甲基）丙烯酸酯、異戊四醇三或四 (甲基）丙烯酸酯、二異戊四醇三或四、五或六（甲基） 丙烯酸酯、三異戊四醇四、五、六、或七（甲基）丙條酸 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，對異氰酸酯基按羥基能成爲等莫耳以 上之比例進行反應所製得’而1分子中的（甲基）丙稀酸 氧基的數成爲3個以上之胺基甲酸乙酯（甲基）丙烯酸醋 〔例如’可藉由二異氰酸酯與異戊四醇三（甲基）丙嫌酸 -16- 201004801 酯的反應，而製得3至6官能的胺基甲酸乙酯（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。在此所例示者僅爲單體，而此等可直接以單體 使用，亦可使用成爲例如，二聚物、三聚物等形態者。又 ，亦可倂用單體與低聚物。 由於至少具有3個（甲基）丙烯醯氧基之硬化性化合 物當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：“NH硬體M101”〔新中村化學工業（股） 製品，胺基甲酸乙酯系〕、“NK酯A-TMM-3L”〔新中村 化學工業（股）製品、異戊四醇三丙烯酸酯〕、“NK酯 A-TMMT”〔新中村化學工業（股）製品、異戊四醇四丙烯 酸酯〕、“ NK酯A-9530”〔新中村化學工業（股）製品、 二異戊四醇五丙烯酸酯〕、“NK酯A-DPH”〔新中村化學 工業（股）製品、二異戊四醇六丙烯酸酯〕、“KAYARAD DPCA”〔日本化藥（股）製品、二異戊四醇六丙烯酸酯〕 、“Nopcocure 200” 系列〔Sannopco (股）製品〕、〔 “Unidic”系列〔大日本油墨化學工業（股）製品等。 至少具有3個（甲基）丙烯醯氧基之化合物，較佳爲 對硬化性塗料的固體成分每1 〇〇重量份，按能佔有50重 量份以上，甚至60重量份以上之方式使用。如至少具有3 個（甲基）丙烯醯氧基之硬化性化合物的含量在50重量 份以下時，則可能表面硬度成爲不足夠。 除以上所說明之分子中至少具有3個（甲基）丙烯醯 氧基之化合物以外，亦可將例如，如下述之各種混合物作 -17- 201004801 爲硬化性化合物使用。此等，可舉至少具有3個（甲基） 丙烯醯氧基之化合物倂用。 如丙二酸/三羥甲基乙烷/(甲基）丙烯酸、丙二酸 /三羥甲基丙烷/(甲基）丙烯酸、丙二酸/甘油/(甲 基）丙烯酸 '丙二酸/異戊四醇/(甲基）丙烯酸、琥珀 酸/三羥甲基丙烷/(甲基）丙烯酸、琥珀酸/甘油/ ( 甲基）丙烯酸、琥珀酸/異戊四醇/(甲基）丙烯酸、己 二酸/三羥甲基乙烷/(甲基）丙烯酸、己二酸/三羥甲 基丙烷/(甲基）丙烯酸、己二酸/甘油/(甲基）丙烯 酸、己二酸/異戊四醇/(甲基）丙烯酸、戊二酸/三羥 甲基乙烷/(甲基）丙烯酸、戊二酸/三羥甲基丙烷/ ( 甲基）丙烯酸、戊二酸/甘油/(甲基）丙烯酸、戊二酸 /異戊四醇/(甲基）丙烯酸、癸二酸/三羥甲基乙烷/ (甲基）丙烯酸、癸二酸/三羥甲基丙烷/(甲基）丙烯 酸、癸二酸/甘油/(甲基）丙烯酸、癸二酸/異戊四醇 /(甲基）丙烯酸、富馬酸/三羥甲基乙烷/(甲基）丙 烯酸、富馬酸/三羥甲基丙烷/(甲基）丙烯酸、富馬酸 /甘油/(甲基）丙烯酸、富馬酸/異戊四醇/(甲基） 丙烯酸、衣康酸/三羥甲基丙烷/(甲基）丙烯酸、衣康 酸/異戊四醇/(甲基）丙烯酸、馬來酸酐/三羥甲基乙 烷/(甲基）丙烯酸、馬來酸酐/甘油/(甲基）丙烯酸 般的化合物的組合所成之飽和或不飽和有機二元酸與（甲 基）丙烯酸的混合聚酯等。 如以紫外線使硬化性塗料硬化時，則使用光聚合引發 -18- 201004801 劑。光聚合引發劑而言，可例舉：二苯基乙二酮、二苯基 酮或其衍生物、唾噸酮（thi〇xanthone )類、节基二甲基 縮酮類、α-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，係一般 對硬化性化合物1 〇〇重量份，在〇· 1至5重量份的範圍。 此等光聚合引發劑，除分別可以單獨使用之外，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，可採用此種市售品。市售品的光聚合引發 劑而言，可例舉：“IRGACURE (伊爾佳裘亞）651”、 “IRGACURE 184”、“IRGACURE 500”、“IRGACURE 1 000” 、“IRGACURE 295 9”、“DAROCUR (達羅裘亞）1173”、 “IRGACURE 907”、“IRGACURE 3 6 9”、“IRGACURE 1 700” 、“IRGACURE 1 800”、“IRGACURE 819”、“IRGACURE 784”〔以上的 IRGACURE (伊爾佳裘亞）系列及 DACOCUR (達羅裘亞）系列，係由千葉特殊化學品（股） 所銷售〕、“KAYACURE (佳雅裘亞）ITX”、“KAYACURE DETX-S”、“KAYACURE BP-100”、“KAYACUREBMS”、 “KAYACURE 2-EAQ”〔以上的 KAYACURE (佳雅裘亞） 系列，係由日本化藥（股）所銷售）等。 又，於本發明中，爲對硬化被膜賦帶與電防止性起見 ，可於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：摻雜（doped )有銻之氧化鍚、摻雜 有磷之氧化鍚、氧化銻、銻酸鋅、氧化鈦、IT〇(銦鍚氧 化物）等的無機粒子。 -19- 201004801 如調配導電性粒子時，其粒徑，能視粒子的種類而適 當選擇，通常可使用0.5 /zm以下者，惟從所得硬化被膜 的帶電防止性或透明性的觀點來看，以平均粒徑計，較佳 爲0.001/zm以上0.1/zm以下者，更佳爲以上 0.0 5 以下者。如導電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 )增大而透明性降低。 又，導電性粒子的使用量，係對硬化性化合物1 00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，則帶電防止性改善效果不足夠。又，如 其量過多時，則可能會降低硬化被膜的透明性。 此種導電性粒子，可依例如，汽相裂煉法（vapor phase cracking)、電獎蒸發法（plasma evaporation)、 院氧化物分解法（alkoxide de-composition)、共沈澱法 (co-precipitation)、水熱反應法（hydrothermal reaction method )等製造。又，導電性粒子的表面，可爲例如，經 以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、聚矽氧系偶合劑、鋁系偶合劑等表面處理者 〇 爲硬化性塗料’以塗料的黏度調整爲目的，而採用稀 釋溶劑’特別是在添加導電性粒子時，爲其分散需要如此 。如採用導電性粒子’且採用溶劑時，則可在例如，混合 導電性粒子及溶劑以使導電性粒子分散於溶劑中後，進行 與硬化性化合物之混合，亦可在混合硬化性化合物與溶劑 後，對此添加導電性粒子再進行混合。 -20- 201004801 溶劑，祗要是能溶解硬化性化合物，且能在塗佈後揮 發者均可採用，又如作爲塗料成分而採用導電性粒子時， 祗要是能使其分散者均可採用。可列舉：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、 3-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使用量上並無特別加以限定 ，可配合硬化性化合物的性狀而以適當的量使用。 又，於此硬化性塗料中，亦可添加周知的調平劑（ leveling agent)。調平劑而言，可例示：聚砍氧油（ silicone oil)系者。聚矽氧油而言，可使用通常者，可具 體例示：二甲基聚矽氧油、苯基甲基聚矽氧油、烷基•芳 烷基改性聚矽氧油、含氟聚矽氧油、聚酯改性聚矽氧油、 脂肪酸酯改性聚矽氧油、甲基氫聚矽氧油、含矽烷醇（ silanol )之聚矽氧油、甲基丙烯酸改性聚矽氧油、胺基改 性聚矽氧油、羧酸改性聚矽氧油、甲醇（carbinol )改性 聚矽氧油、環氧變性聚矽氧油、锍基改性聚矽氧油、氟素 改性聚矽氧油、聚酯改性聚矽氧等。由於此等調平劑有在 市售之故，可採用市售品。市售的調平劑而言，可列舉： “SH200-1 〇〇cs”、“SH28PA”、“SH29PA”、 “SH30PA”、 “ST83PA”、“ST80PA”、“ST97PA”、“ST86PA’’〔以上均由 東麗•道寧•聚矽氧（股）所銷售〕等。此等調平劑可以 分別單獨使用’亦可混合2種以上使用。調平劑的使用量 -21 - 201004801 ，可按照硬化性塗料的特性而適當選擇，一般對硬化性化 合物100重量份，爲0.01至5重量份程度。 如此方式，經於硬化性化合物中，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硬化性塗料 ，如塗佈於前述擠出板表面以作成硬化性塗膜，接著，使 其硬化，即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。 如於前述擠出板上塗佈硬化性塗料以作成硬化性塗膜 時，則可利用鑲條塗佈法（bar coating)、微凹輥塗佈法 (micro-gravure coating )、輥塗法（roll coating )、流 诞塗佈法（flow coating)法、浸漬塗佈法（dip coating) 、旋塗法（spin coating)、壓模塗佈法（die coating)、 噴霧塗佈法（spray coating )等周知的塗佈方法加以塗佈 。如此，則可於前述擠出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。 照射能量標線以使其硬化時的能量射線而言，可例舉 :紫外線、電子射線、放射線等，而其強度或照射時間等 則可按照所用之硬化性塗料的種類而適當選擇。又，利用 加熱以使其硬化時的加熱溫度或加熱溫度等，則可按照所 用之硬化性塗料的種類而適當選擇，惟在加熱硬化的情形 ，則爲防止作爲基材之擠出板之變形’ 一般在1 〇〇°c以下 的溫度爲宜。如硬化性塗料含有溶劑時，則可於塗佈之後 -22- 201004801 ’使溶劑揮發後進行硬化性塗膜之硬化，亦可同時進行溶 劑的揮發及硬化性塗膜的硬化。在此，如溶劑的揮發，亦 即塗膜的乾燥不充分時’則一般所得硬化被膜的耐擦傷性 容易成爲不足夠，惟如採用本發明時，由於將前述所定的 擠出板採用爲基板之故’可容易形成耐擦傷性高的硬化被 膜。 硬化被膜的厚度’較佳爲0.5至50//m程度、更佳爲 0 1至2〇ym程度。如硬化被膜的厚度過厚時，則容易發生 龜裂，如過薄時，則可能耐擦傷性不足夠。 於所得耐擦傷性樹脂板，亦可於其表面藉由塗層法（ coating )或濺鑛法（sputtering )、真空沉積法（vaCuum deposition )等周知的方法而施加防反射處理（antireflection treatment ) 。亦能將另外所製作之防反射性的 片材貼合於上述耐擦傷性樹脂板的單面或雙面，以賦與防 止反射之效果。 φ 如此所製得之耐擦傷性樹脂板，係具有耐擦傷性高的 硬化被膜，故可用於各種用途，其中，作爲行動電話等的 攜帶型資訊終端機的顯示視窗保護板很適合者，其他，數 位攝影機（digital camera )或方便型視訊攝影機（handy type video 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，或者，家庭用及 業務用的電視畫面保護板等，不僅攜帶型資訊終端機，亦 可作爲其攜帶型顯示機器或設置型的顯示機作爲對象之顯 示器用保護板使用。尤其本發明之耐擦傷性樹脂板，係作 -23- 201004801 爲行動電話，特別是包含顯示視窗之顯示部，在不使用時 折疊而作成覆蓋操作鈕扣（operating button)部之構成之 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板，製作顯示器用保護 板時，則首先按照需要進行印刷、鑽孔等加工而依所需大 小加以裁斷處理即可。然後，裝配於顯示器上時，則可作 成耐擦傷性高的顯示器。 【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制。例中，表示含量或者 使用量之％及份，除非特別備註，係重量基準之意。又， 擠出板的面內阻滯値（以下，簡記「Re」），係採用自動 雙折射計（automatic double refration meter)〔王子計測 器（股）製的KOB RA-CCD/ X〕測定者。 〔擠出板（A1 )之調製〕 使用65 mm φ單軸擠壓機〔東芝機械（股）製〕以實 施甲基丙烯酸樹脂粒料（pollet )〔住友化學（股）製的 速美倍克斯EX，玻璃轉移溫度97°C〕之熔融混練並介由 T型模具（T-die)而擠出，按兩面能完全接觸於2支高剛 性的金屬製拋光輥筒（Polishing roll)之方式加以冷卻’ 製得厚度1.0mm的擠出板（A1 )。 -24- 201004801 〔擠出板（A2 )之調製〕 使用65mm φ單軸擠壓機〔東芝機械（股）製〕以實 施添加有橡膠之耐衝擊性甲基丙烯酸樹脂粒料〔住友化學 (股）製的Sumipex HT-55X，玻璃轉移溫度94°C〕之熔 融混練並介由T型口模具而擠出，按兩面能完全接觸於2 支高剛性的金屬製拋光輥筒之方式加以冷卻，製得厚度 • 0.5mm的濟出板（A2 )。 〔擠出板（A3 )之調製〕 使用65mm φ單軸擠壓機〔東芝機械（股）製〕以實 施甲基丙烯酸樹脂粒料〔住友化學（股）製的速美倍克斯 EX，玻璃轉移溫度97°C〕之熔融混練並介由T型模具而 擠出，夾持於1支高剛性的金屬製拋光輥筒與經於1支橡 膠輥筒（rubber roll )上捲附金屬套筒（metal sleep )所 0 成之金屬彈性輥之間，按熔融樹脂的兩面能完全相接觸之 方式加以冷卻，製得厚度1.0mm的擠出板（A3 )。 〔硬化性塗料（B1)之調製〕 混合二異戊四醇六丙烯酸酯〔由新中村化學工業（股 )所銷售之“NK酯A-DPH”〕30份、1-甲氧-2-丙醇20份 、2-乙氧乙醇50份、光聚合引發劑〔由千葉特殊化學品 (股）所銷售之“IRGACURE 1 84”〕2份、以及聚矽氧油〔 由東麗•道寧•聚矽氧（股）所銷售之“SH2 8 PA”〕0.04 5 -25- 201004801 份，以調製硬化性塗料（B 1 )。 〔硬化性塗料（B2 )之調製〕 混合二異戊四醇六丙烯酸酯〔由新中村化學工業（股 )所銷售之“NK酯A-DPH”〕27.7份、光聚合引發劑〔千 葉特殊化學品（股）的IRGACURE 184〕1.5份、五氧化 銻微粒溶膠〔觸媒化成工業（股）的ELCOM-7514;固體 成分濃度20%〕12份、異丁醇29.4份、卜甲氧-2-丙醇 29.4份、以及聚矽氧油〔由東麗•道寧•聚矽氧（股）所 銷售之“SH28PA”〕0.045份，以調製硬化性塗料（B2 )。 〔實施例1〕 (1)擠出板之加熱處理 將擠出板（A1)裁切爲200mmx300mm的大小，重疊 5片後靜置於8(TC的熱風循環烘箱中，按能成爲均等的壓 力之方式施加l〇kg的荷重（0.017 kg/cm2)，並靜置8 小時。然後，在施加荷重之狀態下，按l〇t： /小時的速度 ，冷卻至室溫。 (2 )耐擦傷性樹脂板之製作 於硬化性塗料（B1 )中’浸漬在上述（n中所得之 加熱處理後的擠出板（A1 ) ( Re 5.4nm),依5mm/秒的 速度拉上，藉以兩面塗佈硬化性塗料後，在室溫下乾燥1 分鐘，以形成塗膜於擠出板表面。接著，於以^的熱風烘 -26- 201004801 箱內乾燥1 〇分鐘以使溶劑揮發機，採用1 20W (瓦特）的 高壓水銀燈，對此塗膜照射0.5J (焦耳）/ cm2的紫外線 以使其硬化，製得耐擦傷性樹脂板。就此耐擦傷性樹脂板 ，進行下列評價，並將其結果表示於表1中。 〔全光線穿透係數（total light transmission factor) ( Tt )及霧化haze (H)〕 • 依照JIS K736 1 - 1進行全光線穿透率（Tt)之測定， 並依照JIS K7136進行霧狀（Η)之測定。 〔硬化被膜之厚度〕 採用高速顯微測厚儀（high speed micro film thickness meter)〔大塚電子（股）製，MS-2000〕進行測定。 〔鉛筆硬度試驗（pencil test)〕 φ 依照JIS Κ5600進行測定。 〔表面電阻率〕 依照ASTM-D257進行測定。 〔實施例2〕 除將熱風循環烘箱的溫度從80°C變更爲90°C以外， 其餘則按與實施例1(1)同樣操作，實施擠出板（A1) 的加熱處理。採用該加熱處理後的擠出板（Al) (Re -27- 201004801 2.8nm )，實施與實施例1 ( 2 )同樣操作，製得耐擦傷性 樹脂板。就此耐擦傷性樹脂板’進行與實施例1同樣的評 價，並將其結果示於表1中。 〔比較例1〕 將擠出板（A1)裁切爲200mmx300mm的大小，在不 實施加熱處理之下（Re 15.8 nm)，實施與實施例1(2) 同樣操作，製得耐擦傷性樹脂板。就此耐擦傷性樹脂板， 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〕 除不用擠出板（A1)而採用擠出板（A2)以外，其 餘則按與實施例1 ( 1 )同樣的操作，實施擠出板（A2 ) 的加熱處理。採用該加熱處理後的擠出板（A2) (Re 1 0.1 nm )，實施與實施例1 ( 2 )同樣操作，製得耐擦傷性 樹脂板。就此耐擦傷性樹脂板，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4〕 除不用擠出板（A1)而採用擠出板（A2)，且將熱 風循環烘箱的溫度從80°C變更爲90°C以外，其餘則按與 實施例1(1)同樣操作，實施擠出板（A2)的加熱處理 。採用該加熱處理後的擠出板（A2 ) ( Re 2.7nm )，實施 與實施例1 (2)同樣操作，製得耐擦傷性樹脂板。就此耐 -28- 201004801 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。 〔比較例2〕 將擠出板（A2)裁切爲200mmx300nim的大小，在不 實施加熱處理之下（尺6 19.〇11111)，實施與實施例1(2) 同樣操作，製得耐擦傷性樹脂板。就此耐擦傷性樹脂板， ^ 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5〕 將擠出板（A3)裁切爲200mmx300mm的大小，在不 實施加熱處理之下（Re 6.5nm )，實施與實施例（2)同 樣操作，製得耐擦傷性樹脂板。就此耐擦傷性樹脂板，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6〕 除按照與實施例1(1)同樣的操作以實施擠出板（ A1)的加熱處理，並採用該加熱處理後的擠出板（A1) (Re 5.3nm)，且不用硬化性塗料（B1)而採用硬化性塗 料（B2 )以外，其餘則實施與實施例1 ( 2 )同樣的操作 ’製得耐擦傷性樹脂板。就此耐擦傷性樹脂板，進行與實 施例1同樣的評價，並將其結果表示於表1中。 〔比較例3〕 -29- 201004801 除將擠出板（A1)裁切爲200mmx3 00mm的大小’在 不實施加熱處理之下（Re 16.4nm )，不用硬化性塗料（ B1)而採用硬化性塗料（B2)以外，其餘則實施與實施例 1 (2)同樣的操作，製得耐擦傷性樹脂板。就此耐擦傷性 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。 表1 Re (nm) 膜厚 (μ m) Tr (%、 H (%) 鉛筆 硬度試驗 表面電阻率 (Ω /〇) 實施例1 5.4 3.2 91 5 0.3 5H 1015^ 實施例2 2.8 3.4 _1L5 0.3 5H 1〇15< 比較例1 15.8 3.3 _ 91.5 0.2 4H 1015< 實施例3 10.1 3.3 91 2 0.4 3H 1015^ 實施例4 2.7 3.2 —------- —1L2 _J 0.5 3H 1015^ 比較例2 19.0 3.3 91.2 0.5 2H 1015^ 實施例5 6.5 3.4 91.5 0.3 5H 1〇15^ 實施例6 5.3 3.6 91 3 0.5 5H 2x10" 比較例3 16.4 3.5 91 ^ 0.5 4H 2xl〇n -----—(1) (2) In the formula (1), R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or a methyl group. In the formula (2), 'R3 represents a hydrogen atom or a methyl group, R4 represents a hydrogen atom or a methyl group, and R5 represents a hydrogen atom or a substituent. Examples of the substituent include a methyl group and an ethyl group. An alkyl group such as a cyclohexyl cycloalkyl group such as a phenyl-like aryl group such as a benzyl-like aralkyl group has a carbon number of usually from 1 to 20. -9- 201004801 Further, examples of the polyfunctional monomer include, for example, ethylene glycol dimethyl propylene acrylate, butane diol dimethacrylate, and trimethylolpropane triacrylate. Polyunsaturated carboxylic acid esters of polyhydric alcohols, such as allyl acrylate, allyl methacrylate, alkenyl esters of unsaturated carboxylic acids such as allyl cinnamate such as diallyl citrate, horse A polyalkenyl ester of an organic polybasic acid like diallyl allylate, triallyl cyanurate or triallyl isocyanurate, such as a divinylbenzene-like aromatic polychain Alkenyl compound and the like. Here, the above-mentioned alkyl methacrylate, alkyl acrylate, and the like may be used in combination of two or more kinds as needed. The methacrylic resin is preferably one having a glass transition temperature of 60 ° C or more, more preferably 80 ° C or more, from the viewpoint of heat resistance of the extruded sheet. The glass transition temperature, such as adjusting the monomer type or its ratio, can be appropriately set. The methyl acrylate resin can be prepared by, for example, suspension polymerization, emulsion polymerization or bulk polymerization. At this time, in order to obtain a suitable glass transition temperature, in order to obtain a viscosity which exhibits moldability to a suitable extruded sheet, it is preferred to use a chain transfer agent at the time of polymerization. The amount of the chain transfer agent may be appropriately determined depending on the kind of the monomer or the ratio thereof. In the thermoplastic resin, other components may be blended and used as a resin composition. As such a compounding component, a coloring agent such as a rubber particle, a dye or a pigment, an antioxidant, an ultraviolet absorber, or the like can be exemplified. Special -10- 201004801 In the case of methacrylic resin, if rubber particles are blended, it is suitable because the impact resistance or softness of the extruded sheet can be improved and it is difficult to crack. For rubber particles which can be blended with a thermoplastic resin, in particular, a methacrylic resin, for example, various rubbers such as acrylic, butadiene, styrene, and styrene can be used, among which weathering resistance (weathering) From the point of view, 'acrylic rubber particles are very suitable for use. For the acrylic φ rubber particles, for example, a single layer structure composed of an elastic polymer such as butyl acrylate as a main component, or a hard polymerization mainly composed of methyl methacrylate may be used. Around the inner layer of the object, a multilayer structure composed of an outer layer of an elastic polymer such as butyl acrylate as a main component is provided. Further, in the above elastic polymer, a small amount of a polyfunctional monomer is generally copolymerized. Further, a multilayer structure comprising a hard polymer mainly composed of methyl methacrylate as a main layer is provided around the elastic polymer, and is also used. A two-layer structure comprising a hard polymer layer mainly composed of methyl methacrylate is provided around an inner layer made of an elastic polymer mainly composed of an alkyl acrylate such as butyl acrylate. Or an intermediate layer formed of an elastomeric polymer such as butyl acrylate as a main component is formed around the inner layer of the hard polymer mainly composed of methyl methacrylate. There is a three-layer structure composed of an outer layer of a hard polymer mainly composed of methyl methacrylate. The rubber particles of such a multi-layer structure are disclosed in, for example, Japanese Patent Publication No. Sho 5 5-2 75 76. In particular, the above-described three-layer structure is suitable, and one of the compositions described in the third embodiment of the Japanese Patent Publication No. Sho-5-5-7576 is one of the most suitable compositions. The rubber particles which can be blended with the thermoplastic resin have an average particle diameter of from the viewpoint of surface hardness or impact resistance and surface smoothness. 〇5 to 0. 4 // m is very suitable for use. If the average particle diameter of the rubber particles is too small, the surface hardness of the extruded sheet is insufficient, or the extruded sheet becomes brittle. On the other hand, if the average particle diameter of the rubber particles is too large, the surface smoothness of the extruded sheet may be affected. The rubber particles are generally produced by emulsion polymerization, and when the amount of the emulsifier added or the feed amount of the monomer is adjusted, the average particle diameter can be controlled to be a desired enthalpy. When the rubber particles are blended in the thermoplastic resin, the ratio of the two is preferably from 50 to 95 parts by weight, and from 5 to 50 parts by weight, based on the total weight of the thermoplastic resin. If the amount of the rubber particles is too small, the impact resistance or flexibility of the extruded sheet may not be sufficiently improved. If the amount is too large, the surface hardness or rigidity of the extruded sheet may not be sufficient, so that it is not preferable to apply the above thermoplastic resin. By extrusion molding, an extruded sheet which becomes a substrate of the scratch-resistant resin sheet of the present invention can be obtained. Extrusion molding can be carried out, in particular, by a melt extrusion method such as a T-die method or a blow molding method. The surface of the resulting extruded sheet may be smooth or provided with fine irregularities. If a smooth or concave-convex shape is to be imparted, the thermoplastic resin is melt extruded from, for example, a T-die and the at least one side of the resulting sheet is brought into contact with a roll (Γ〇11) or a belt (belt). The method of making a plate is suitable because it can obtain a sheet with good surface properties. -12- 201004801 is suitable. In particular, from the viewpoint of improving the smoothness of the extruded sheet or the precision imparted by the shape, it is preferred that both sides of the sheet obtained by melt-extruding the thermoplastic resin are brought into contact with the surface of the roll or belt for molding. method. The rollers or belts used at this time are all made of metal. Therefore, in a preferred embodiment, the thermoplastic resin is melted from the T-die melter to be in contact with at least one mirror plane roll, and more preferably it is combined with two mirror rollers. A method of forming a contact surface while being sandwiched. Further, the extruded plate may be formed into a multilayer structure as needed. A multilayer structure of a methacrylic resin containing rubber particles and a methacrylic resin containing no rubber particles, a multilayer structure of a plurality of methacrylic resins having different glass transition temperatures, a methacrylic resin and the like A multilayer structure formed of a thermoplastic resin other than a methacrylic resin such as a polycarbonate resin. In order to manufacture such a multi-layered extruded sheet, for example, a plurality of φ-section extruders can be used, and a multimanifold method or a feed member having a laminate for extruding the resin to be extruded therefrom. Block) A well-known multi-layer extruder for mechanisms such as the method. The thickness of the extruded plate is usually 0. 2 to 3 mm, preferably 0. 25 to 2. 5mm. If the thickness is too thin, the strength or rigidity of the substrate as the protective sheet for the display may be insufficient, and if the thickness is too thick, the design of the substrate as the protective sheet for the display may be inappropriate. Further, when the extruded plate is used as a substrate for a protective sheet for a display, it can be used in the shape of a flat surface or a curved surface in the shape of a surface of the display window, or in the form of a curved surface - 13 - 201004801. In order to produce the in-plane retardation enthalpy of 15 nm or less required in the present invention, as described above, when the molten thermoplastic resin extruded from the T-die is sandwiched between two rolls, The molder uses an elastic roller as the at least one roller to contact the two sides of the molten thermoplastic resin to the roller and pass the method, thereby reducing the skew during molding and reducing the strength or heat shrinkage. Anisotropy is a suitable method for producing extruded sheets with a small retardation in the plane. As the elastic roller, the metal elastic roller is provided, for example, with a shaft roll and a cylindrical metal film which is disposed so as to cover the outer peripheral surface of the vertical roller and is in contact with the molten thermoplastic resin. It is suitable to use a fluid having a controlled temperature such as water or oil between the vertical roller and the metal film, or to wind the metal belt on the surface of the rubber roller. Moreover, in the method of using two high-rigidity metal rolls, such as adjusting the pressure between the metal rolls, the temperature of each metal roll, the production speed at the time of extrusion molding, etc., the in-plane resistance of the obtained extruded plate can also be obtained. The hysteresis is 15 nm or less. Further, even in the case where the in-plane retardation enthalpy is 15 nm or more, if the heat treatment is carried out at a predetermined temperature, the in-plane retardation can be made 15 nm or less. The temperature of the heat treatment is preferably a temperature which is about 3 to 25 ° C lower than the glass transition temperature of the thermoplastic resin constituting the extruded sheet. Also, the processing time can be appropriately selected, but it is usually 30 minutes to 24 hours. The heating method may be appropriately selected, and may be, for example, a method of standing in a hot air circulation oven or a method of heating by a radiant heat of a heater such as infrared rays. Among them, since a large number of extrusion plates can be processed at the same time, the method of standing still in the hot air circulation oven is suitable for use. In the method of standing the extruded sheet in a hot air circulating oven, one piece may be left alone, or a plurality of pieces may be stacked while being allowed to stand. Further, it is also possible to apply a load to the standing extruded plate to prevent the occurrence of deformation. The load can be appropriately selected, but it is preferable to set the load in such a manner that the pressure can be equalized in order to prevent the load distribution in the surface. The load can also be appropriately selected, but usually 0. 001 to 0. 1kg/cm2 level. After the heat treatment for a given period of time, it is necessary to cool the extruded plate to room temperature. The cooling method is not particularly limited, and the extruded sheet can be taken out immediately, and the load can be cooled after being released, or the extruded sheet can be taken out after being cooled to room temperature under an applied load. When it is desired to reduce the in-plane retardation, it is better to use the latter method. When the cold is performed, the temperature change rate is not particularly limited, but is usually 2 to 30 ° C / hour. As a result of forming a hardened film on the surface of at least one side of the extruded sheet having a retardation of 15 nm or less, the scratch-resistant resin sheet of the present invention having a hardened film having high scratch resistance can be obtained. . The curable coating material used for forming the hardened ruthenium film is mainly composed of various curable compounds which impart scratch resistance, and if necessary, a solvent, a conductive particle, a curing catalyst or the like is mixed. First, as described for the curable compound, from acrylate, urethane acrylate, epoxy acrylate, carboxyl modified epoxy acrylate, polyester acrylate, copolymer acrylate, alicyclic Among the epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds, and the like, those having an effect of imparting scratch resistance can be used. Among them, as a sclerosing -15-201004801 compound which can provide high rubbing resistance, a polyfunctional acrylate type, a polyfunctional urethane acrylate type, and a polyfunctional epoxy acrylate type are mentioned. A curable compound which is a radical polymerization type, or a thermopolymerizable curable compound, such as an alkoxy decane or an alkyl alkoxy decane. These curable compounds are, for example, hardened by irradiation with an energy line such as an electron beam, radiation, or ultraviolet rays, or hardened by heating. In this case, the curable compounds may be used singly or in combination of a plurality of compounds. Preferred among these curable compounds are compounds having at least three (meth)acryloxy groups in the molecule. Here, the (meth) propylene oxime means the propylene oxime group or the methacryloxy group. In the present specification, "(meth)" in the case of (meth) acrylate (meth) acrylate or the like is also of the same meaning. A curable compound having at least three (meth) acryloxy groups in the molecule can be exemplified by, for example, trimethylolpropane tri(meth)acrylate or trishydroxymethylethane tris(methyl). Acrylate, glycerol tri(meth) acrylate, neopentyl tris (tri) acrylate, pentaerythritol tri or tetra (meth) acrylate, diisopentaerythritol three or four, five or six a poly(meth)acrylate of a polyhydric alcohol having a (meth) acrylate, a triisotetraol tetrakis, a penta, a hexa- or a hepta-(methyl) glyceride-like ternary ester or more; a compound of two isocyanate groups, wherein a (meth) acrylate monomer having a hydroxyl group is obtained by reacting an isocyanate group at a ratio of a hydroxyl group to a molar ratio of more than a molar amount, and (meth) propylene in one molecule The number of acid oxygen groups is three or more ethyl urethane (meth) acrylates (for example, 'reaction by diisocyanate with isobaric alcohol tris(methyl) propyl sulphate-16-201004801 ester, And 3 to 6-functional ethyl urethane (meth) acrylate]: 2-hydroxyethyl) isocyanurate tri (meth) acrylate and the like. The exemplified here is only a monomer, and these may be used as a monomer, or may be, for example, a form such as a dimer or a trimer. Further, monomers and oligomers can also be used. Since a curable compound having at least three (meth) acryloxy groups is also commercially available, such a commercially available product can also be used. For the commercial product, "NH hardware M101" (New Nakamura Chemical Industry Co., Ltd. product, ethyl urethane system), "NK ester A-TMM-3L" (New Nakamura Chemical Industry Co., Ltd.) ), product, pentaerythritol triacrylate], "NK ester A-TMMT" [Xinzhongcun Chemical Industry Co., Ltd., isopentenol tetraacrylate], "NK ester A-9530" [Xinzhongcun Chemical Industry (stock) product, diisopentyl alcohol pentaacrylate], "NK ester A-DPH" [Xinzhongcun Chemical Industry Co., Ltd. product, diisopentyl alcohol hexaacrylate], "KAYARAD DPCA" [Japanese chemical (stock) product, diisopentyl alcohol hexaacrylate], "Nopcocure 200" series [Sannopco (stock) products], ["Unidic" series [Dainippon ink chemical industry (stock) products. The compound having at least three (meth) acryloxy groups is preferably used in an amount of 50 parts by weight or more, or even 60 parts by weight or more per 1 part by weight of the solid content of the curable coating material. When the content of the curable compound having at least three (meth) acryloxy groups is 50 parts by weight or less, the surface hardness may be insufficient. In addition to the compound having at least three (meth) acryloxy groups in the above-described molecules, for example, various mixtures described below may be used as the curable compound as -17-201004801. These may be used for compounds having at least three (meth)acryloxy groups. Such as malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerol / (meth) acrylic acid 'malonic acid / Isopentanol/(meth)acrylic acid, succinic acid/trimethylolpropane/(meth)acrylic acid, succinic acid/glycerol/(meth)acrylic acid, succinic acid/isoamyltetraol/(meth)acrylic acid , adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerol / (meth) acrylic acid, adipic acid / Isopentanol/(meth)acrylic acid, glutaric acid/trimethylolethane/(meth)acrylic acid, glutaric acid/trimethylolpropane/(meth)acrylic acid, glutaric acid/glycerol/ (Meth)acrylic acid, glutaric acid/isopentitol/(meth)acrylic acid, sebacic acid/trimethylolethane/(meth)acrylic acid, sebacic acid/trimethylolpropane/(A) Acrylic acid, azelaic acid/glycerol/(meth)acrylic acid, sebacic acid/isopentaerythritol/(meth)acrylic acid, fumaric acid/trimethylolethane/(meth)acrylic acid, fuma Acid/trimethylolpropane/(meth)acrylic acid, Horse acid/glycerol/(meth)acrylic acid, fumaric acid/isopentaerythritol/(meth)acrylic acid, itaconic acid/trimethylolpropane/(meth)acrylic acid, itaconic acid/isopentaerythritol Saturated or unsaturated organic binary formed by a combination of /(meth)acrylic acid, maleic anhydride/trimethylolethane/(meth)acrylic acid, maleic anhydride/glycerol/(meth)acrylic acid-like compound A mixed polyester of an acid and (meth)acrylic acid. When the curable coating is cured by ultraviolet rays, photopolymerization is used to induce -18-201004801. The photopolymerization initiator may, for example, be diphenylethylenedione, diphenylketone or a derivative thereof, thixoxanthone, benzyl ketal, or α-hydroxyalkane. Benzophenones, hydroxymethyl ketones, aminoalkyl benzophenones, fluorenyl phosphine oxides, and the like. The amount of the photopolymerization initiator to be added is usually in the range of from 1 to 5 parts by weight based on 1 part by weight of the curable compound. These photopolymerization initiators may be used alone or in combination of two or more. Further, since such various photopolymerization initiators are commercially available, such commercially available products can be used. The photopolymerization initiator of the commercial product may, for example, be "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1 000", "IRGACURE 295 9", " DAROCUR 1173", "IRGACURE 907", "IRGACURE 3 6 9", "IRGACURE 1 700", "IRGACURE 1 800", "IRGACURE 819", "IRGACURE 784" (above IRGACURE (Ill) "Jiaiya" series and DACOCUR series are sold by Chiba Special Chemicals Co., Ltd., "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP- 100", "KAYACUREBMS", "KAYACURE 2-EAQ" (the above KAYACURE series, sold by Nippon Kayaku Co., Ltd.). Further, in the present invention, in order to impart adhesion to the cured film and electrical prevention, conductive particles may be added to the curable coating material. The conductive particles used for this purpose may, for example, be doped with antimony oxide, antimony doped with phosphorus, antimony oxide, antimony zinc oxide, titanium oxide, IT antimony (indium antimony oxide) Inorganic particles. -19- 201004801 When the conductive particles are blended, the particle size can be appropriately selected depending on the type of the particles, and usually 0. 5 /zm or less, from the viewpoint of the charge prevention property or transparency of the obtained cured film, it is preferably 0. 001/zm or more 0. 1/zm or less, more preferably above. 0 5 The following. When the average particle diameter of the conductive particles is too large, the haze of the obtained scratch-resistant resin sheet may increase and the transparency may decrease. Further, the conductive particles are used in an amount of about 1 to 50 parts by weight, preferably from 2 to 50 parts by weight, preferably from 3 to 20 parts by weight, per 100 parts by weight of the curable compound. If the amount is too small, the effect of improving the electrification prevention effect is insufficient. Further, if the amount is too large, the transparency of the cured film may be lowered. Such conductive particles may be, for example, vapor phase cracking, plasma evaporation, alkoxide de-composition, or co-precipitation. Manufactured by a hydrothermal reaction method or the like. Further, the surface of the conductive particles may be, for example, a surface treatment agent such as a nonionic surfactant, a cationic surfactant, an anionic surfactant, a polyoxygen coupling agent, or an aluminum coupling agent. The curable coating is intended to adjust the viscosity of the coating, and the dilution solvent is used, especially when the conductive particles are added. When a conductive particle is 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 mixed with the curable compound, or the curable compound and the solvent may be mixed. Thereafter, conductive particles are added thereto and mixed. -20- 201004801 Solvents, if they can dissolve hardenable compounds, can be used after being sprayed, and when conductive particles are used as coating components, they can be used as dispersions. For example, diacetone alcohol, methanol, ethanol, isopropanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 3-butoxyethanol, 1-methoxy-2-propanol-like alcohol 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 esters , water, etc. The amount of the solvent used in the curable coating material is not particularly limited, and may be used in an appropriate amount in accordance with the properties of the curable compound. Further, a well-known leveling agent may be added to the curable coating material. The leveling agent can be exemplified by a silicone oil. As the polyoxygenated oil, a general one can be used, and specific examples thereof include dimethylpolyphthalic acid oil, phenylmethylpolyphosphoric acid oil, alkyl aralkyl modified polyoxygenated oil, and fluorine-containing polyfluorene. Oxygen oil, polyester modified polyoxyxide oil, fatty acid ester modified polyoxygenated oil, methyl hydrogen polyoxygenated oil, polyanthracene oil containing stanol, methacrylic modified polyoxyl Oil, amine modified polyoxyxide oil, carboxylic acid modified polyoxyxide oil, methanol (carbinol) modified polyoxyxene oil, epoxy modified polyoxyxene oil, sulfhydryl modified polyoxyxene oil, fluorin Modified polyoxyxide oil, polyester modified polyfluorene oxide, and the like. Since these leveling agents are commercially available, commercially available products can be used. Commercially available leveling agents include: "SH200-1 〇〇cs", "SH28PA", "SH29PA", "SH30PA", "ST83PA", "ST80PA", "ST97PA", "ST86PA"' All of the above are sold by Toray Dow Corning Co., Ltd., etc. These leveling agents can be used alone or in combination of two or more. The amount of leveling agent used - 21 - 201004801, It is appropriately selected according to the characteristics of the curable coating, and is generally 0% by weight of the curable compound. 01 to 5 parts by weight. In this manner, a curable coating material obtained by mixing conductive particles, a solvent, a leveling agent, a photopolymerization initiator, or the like, as needed, is applied to the surface of the extrusion plate to form a curable coating film, and then By hardening it, it is set as the scratch-resistant resin board which formed the hardening film of the abrasion resistance on the surface. When a curable coating material is applied to the above-mentioned extrusion plate to form a curable coating film, a bar coating method, a micro-gravure coating method, a roll coating method ( Roll coating ), flow coating method, dip coating method, spin coating method, die coating method, spray coating method The coating method is applied by a known method. Thus, a curable coating film can be formed on the surface of the extrusion plate. Then, an anti-scratch hardened film is formed by irradiating an energy ray such as an ultraviolet ray or an electron ray or heating to cure the curable coating film according to the type of the curable coating material. The energy ray which is irradiated with the energy reticle for curing is exemplified by ultraviolet rays, electron rays, radiation, etc., and the strength, irradiation time, and the like can be appropriately selected depending on the type of the curable coating material to be used. Further, the heating temperature or the heating temperature at the time of curing 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, the deformation of the extrusion sheet as the substrate is prevented. ' Generally, the temperature below 1 〇〇 °c is appropriate. When the curable coating contains a solvent, the curable coating film may be volatilized after the coating is -22-201004801', and the solvent may be volatilized and the curable coating film may be cured at the same time. Here, if the volatilization of the solvent, that is, when the drying of the coating film is insufficient, the scratch resistance of the generally obtained cured film is likely to be insufficient. However, when the present invention is used, the above-mentioned extruded plate is used as the substrate. Therefore, it is easy to form a hardened film having high scratch resistance. The thickness of the hardened film is preferably '0. 5 to 50 / / m, more preferably 0 1 to 2 〇 ym. If the thickness of the hardened film is too thick, cracking is likely to occur, and if it is too thin, scratch resistance may be insufficient. The obtained scratch-resistant resin sheet may be subjected to an antireflection treatment by a known method such as coating, sputtering, or vaCuum deposition on the surface thereof. It is also possible to bond the separately prepared antireflective sheet to one side or both sides of the above-mentioned scratch resistant resin sheet to impart an antireflection effect. φ The scratch-resistant resin sheet thus obtained is a hardened film having high scratch resistance, and can be used for various purposes. Among them, a display window protection board for a portable information terminal such as a mobile phone is suitable. , a finder unit such as a digital camera or a handy type video camera, a display window protection board for a game player, or the like for home use and business use. A television screen protection board or the like can be used not only as a portable information terminal but also as a display protection board for a portable display device or a display type display device. In particular, the scratch-resistant resin sheet of the present invention is a mobile phone of -23-201004801, in particular, a display unit including a display window, which is folded to form a mobile phone that covers an operating button portion when not in use. Display the window protection board and play a beneficial effect. When a protective sheet for a display is to be produced from the scratch-resistant resin sheet of the present invention, it is first necessary to perform processing such as printing, drilling, etc., and to cut it according to the required size. Then, when mounted on a monitor, it can be used as a display with high scratch resistance. [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 or the amount used are unless otherwise noted. In addition, the in-plane retardation of the extrusion plate (hereinafter, abbreviated as "Re") is measured by an automatic double refration meter (KOB RA-CCD/X manufactured by Oji Scientific Instruments Co., Ltd.). . [Preparation of Extrusion Plate (A1)] Using a 65 mm φ single-axis extruder (manufactured by Toshiba Machine Co., Ltd.) to carry out methacrylic resin pellets (Polet) [Sumitomo Chemical Co., Ltd. EX, glass transfer temperature 97 ° C] melt kneading and extrusion through a T-die, two sides can be completely in contact with two high-rigidity metal polishing rolls (Polishing roll) Cooled 'to make a thickness of 1. 0 mm extruded plate (A1). -24- 201004801 [Preparation of Extrusion Plate (A2)] Using a 65mm φ single-axis extruder (manufactured by Toshiba Machine Co., Ltd.) to carry rubber-impregnated methacrylic resin pellets [Sumitomo Chemical Co., Ltd. The Sumipex HT-55X, which has a glass transition temperature of 94 ° C, is melt-kneaded and extruded through a T-die, which is cooled in such a way that it can be completely contacted with two high-rigidity metal polishing rolls. Made thickness • 0. 5mm sheet (A2). [Preparation of the extruded sheet (A3)] Using a 65 mm φ uniaxial extruder (manufactured by Toshiba Machine Co., Ltd.) to carry out methacrylic resin pellets [Sumitomo Chemical Co., Ltd. Melt-kneading at a transfer temperature of 97 ° C] and extrusion through a T-die, sandwiched between a high-rigidity metal polishing roll and a metal sleeve wound on a rubber roll (metal sleep) between the metal elastic rolls, the two sides of the molten resin can be completely contacted to cool, to obtain a thickness of 1. 0 mm extruded plate (A3). [Preparation of Curable Coating (B1)] Mixed diisopentaerythritol hexaacrylate ["NK ester A-DPH" sold by Shin-Nakamura Chemical Industry Co., Ltd.] 30 parts, 1-methoxy-2-propene 20 parts of alcohol, 50 parts of 2-ethoxyethanol, 2 parts of photopolymerization initiator [IRGACURE 1 84" sold by Chiba Special Chemicals Co., Ltd., and polyoxygenated oil [by Toray Downing • "SH2 8 PA" sold by polyoxyl (shares)]0. 04 5 -25- 201004801 parts to prepare hardenable coating (B 1 ). [Preparation of Curable Coating (B2)] Mixed diisopentaerythritol hexaacrylate ["NK ester A-DPH" sold by Shin-Nakamura Chemical Industry Co., Ltd.] 27. 7 parts, photopolymerization initiator [IRGACURE 184 of Chiba Special Chemicals Co., Ltd.] 1. 5 parts, bismuth pentoxide sol (ELCOM-7514 of Catalyst Chemical Industry Co., Ltd.; solid concentration 20%) 12 parts, isobutanol 29. 4 parts, methoxy-2-propanol 29. 4 parts, and polyoxygenated oil ("SH28PA" sold by Toray Dow Corning Co., Ltd.) 0. 045 parts to prepare a hardenable coating (B2). [Example 1] (1) Heat treatment of extruded sheet The extruded sheet (A1) was cut into a size of 200 mm x 300 mm, and 5 sheets were overlapped and then placed in a hot air circulating oven of 8 (TC), and the pressure was equalized. The way to apply a load of l〇kg (0. 017 kg/cm2) and allowed to stand for 8 hours. Then, while applying a load, it was cooled to room temperature at a rate of l〇t: /hour. (2) Production of a scratch-resistant resin sheet In the curable coating material (B1), immersed in the above-mentioned (a1) heat-treated extrusion sheet (A1) (Re 5. 4 nm), pulled at a speed of 5 mm/sec, and after applying the curable coating on both sides, it was dried at room temperature for 1 minute to form a coating film on the surface of the extrusion plate. Next, dry in a hot air bake -26-201004801 box for 1 以 minutes to make the solvent volatilizer, using a high pressure mercury lamp of 1 20W (watt), the film is irradiated with 0. 5J (Joules) / cm2 of ultraviolet rays to harden them to produce a scratch-resistant resin sheet. With respect to this scratch-resistant resin sheet, the following evaluations were carried out, and the results are shown in Table 1. [total light transmission factor (Tt) and atomized haze (H)] • The total light transmittance (Tt) is measured in accordance with JIS K736 1-1, and is fogged in accordance with JIS K7136 ( Η) Determination. [Thickness of Hardened Film] The measurement was carried out by using a high speed micro film thickness meter (manufactured by Otsuka Electronics Co., Ltd., MS-2000). [Pencil test] φ was measured in accordance with JIS Κ 5600. [Surface resistivity] Measured in accordance with ASTM-D257. [Example 2] The heat treatment of the extrusion plate (A1) was carried out in the same manner as in Example 1 (1) except that the temperature of the hot air circulation oven was changed from 80 °C to 90 °C. The heat-treated extruded sheet (Al) was used (Re -27- 201004801 2. 8 nm), in the same manner as in Example 1 (2), a scratch-resistant resin sheet was obtained. The same evaluation as in Example 1 was carried out on this scratch-resistant resin sheet, and the results are shown in Table 1. [Comparative Example 1] The extruded plate (A1) was cut to a size of 200 mm x 300 mm without being subjected to heat treatment (Re 15. 8 nm), in the same manner as in Example 1 (2), a scratch-resistant resin sheet 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] Except that the extruded sheet (A2) was used without using the extruded sheet (A1), the heat treatment of the extruded sheet (A2) was carried out in the same manner as in Example 1 (1). The heat-treated extruded sheet (A2) (Re 1 0. 1 nm), in the same manner as in Example 1 (2), a scratch-resistant resin sheet 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 4] Extrusion plate (A2) was used except that the extruded plate (A1) was not used, and the temperature of the hot air circulating oven was changed from 80 °C to 90 °C, and the rest was in accordance with Example 1 (1). In the same manner, the heat treatment of the extruded plate (A2) was carried out. Using the heat-treated extrusion plate (A2) (Re 2. 7 nm), the same procedure as in Example 1 (2) was carried out to obtain a scratch-resistant resin sheet. In this case, the same evaluation as in Example 1 was carried out for the scratch-resistant resin sheet ‘, and the results are shown in Table 1. [Comparative Example 2] The extruded plate (A2) was cut to a size of 200 mm x 300 nim without being subjected to heat treatment (foot 6 19. 〇11111), in the same manner as in Example 1 (2), a scratch-resistant resin sheet 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 5] The extruded sheet (A3) was cut to a size of 200 mm x 300 mm without heat treatment (Re 6. 5 nm), the same operation as in the example (2) was carried out to obtain a scratch-resistant resin sheet. 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 6] The heat treatment of the extruded sheet (A1) was carried out in the same manner as in Example 1 (1), and the heat-treated extruded sheet (A1) was used (Re 5. The scratch-resistant resin sheet was produced in the same manner as in Example 1 (2) except that the curable coating material (B1) was used without using the curable coating material (B1). The same evaluation as in Example 1 was carried out on the scratch-resistant resin sheet, and the results are shown in Table 1. [Comparative Example 3] -29- 201004801 Except that the extruded sheet (A1) was cut to a size of 200 mm x 3 00 mm' without heat treatment (Re 16. 4 nm), except that the curable coating material (B1) was used instead of the curable coating material (B2), the same operation as in Example 1 (2) was carried out to obtain a scratch-resistant resin sheet. The same evaluation as in Example 1 was carried out on the scratch-resistant resin sheet, and the results are shown in Table 1. Table 1 Re (nm) film thickness (μ m) Tr (%, H (%) pencil hardness test surface resistivity (Ω / 〇) Example 1 5. 4 3. 2 91 5 0. 3 5H 1015^ Example 2 2. 8 3. 4 _1L5 0. 3 5H 1〇15 < Comparative Example 1 15.8 3.3 _ 91.5 0.2 4H 1015 <Example 3 10.1 3.3 91 2 0.4 3H 1015^ Example 4 2.7 3.2 —------- —1L2 _J 0.5 3H 1015^ Comparative Example 2 19.0 3.3 91.2 0.5 2H 1015^ Example 5 6.5 3.4 91.5 0.3 5H 1〇15^ Example 6 5.3 3.6 91 3 0.5 5H 2x10" Comparative Example 3 16.4 3.5 91 ^ 0.5 4H 2xl〇n ------
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