201235211 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種於聚碳酸酯樹脂層的雙面層合有甲 基丙烯酸酯樹脂層之層合體、以及使用其之耐擦傷性樹脂 板、顯示器用保護板及觸控式面板用保護板》 【先前技術】， 專利文獻1記載一種耐擦傷性樹脂板，其耐衝撃性及 表面硬度優異，適用於顯示器用保護板或行動型資訊終端 機的顯示窗保護板。具體而言，專利文獻1記載之耐擦傷 性樹脂板，其係以於聚碳酸酯樹脂層的雙面皆層合有含有 橡膠粒子，且厚度相同的丙烯酸酯樹脂層之層合體作爲基 板，其各個丙烯酸酯樹脂層的表面形成有硬化被膜。 上述之層合體及耐擦傷性樹脂板較佳爲具有較高耐衝 撃性及較高表面硬度者。201235211 VI. [Technical Field] The present invention relates to a laminate in which a methacrylate resin layer is laminated on both sides of a polycarbonate resin layer, and a scratch-resistant resin sheet using the same, Protective sheet for display and protective sheet for touch panel. [Prior Art] Patent Document 1 describes a scratch-resistant resin sheet which is excellent in punching resistance and surface hardness and is suitable for a protective sheet for a display or a mobile information terminal. Display window protection board. Specifically, the scratch-resistant resin sheet described in Patent Document 1 is obtained by laminating a laminate of acrylate resin layers having rubber particles and having the same thickness on both sides of the polycarbonate resin layer as a substrate. A hardened film is formed on the surface of each acrylate resin layer. The above laminate and the scratch-resistant resin sheet are preferably those having high impact resistance and high surface hardness.
專利文獻 1 : JP2010-23444A 【發明內容】 發明所欲解決之課題 本發明之課題在於提供一種具有較高耐衝撃性及較高 表面硬度之層合體、以及使用其之耐擦傷性樹脂板、顯示 器用保護板及觸控式面板用保護板。 用以解決課題之手段 -5- 201235211 本發明者爲了解決上述課題而致力硏究，結果發現以 下構成所形成之解決手段，而完成本發明》 (1) 一種層合體，其特徵在於：於聚碳酸酯樹脂層的 單面層合有含橡膠粒子之甲基丙烯酸酯樹脂層（A)，於另 一面層合有含橡膠粒子之甲基丙烯酸酯樹脂層（B)，當上 述甲基丙烯酸酯樹脂層（A)的厚度設爲t(A)、上述甲基丙 烯酸酯樹脂層（B)的厚度設爲t(B)時，t(A)>t(B)。 (2) 如上述（1)之層合體，其中上述t(A)與t(B)的比 (t(A)/t(B))爲 1.2 以上。 (3) 如上述（1)或（2)之層合體，其中上述t(A)爲50〜 200μηι，上述 t(B)爲 10 〜150μιηβ (4) 如上述（1)〜（3)中任一項之層合體，其中上述 t(A)與t(B)的總計厚度爲層合體整體厚度的50%以下。 (5) 如上述（1)〜（4)中任一項之層合體，其中層合體 整體厚度爲0.3〜3mm。 (6) 如上述（1)〜（5)中任一項之層合體，其中上述聚 碳酸酯樹脂層、甲基丙烯酸酯樹脂層（A)及甲基丙烯酸酯 樹脂層（B)係藉由共擠壓成形而層合。 (7) —種耐擦傷性樹脂板，其係含有上述（1)〜（6)中 任一項之層合體，上述甲基丙烯酸酯樹脂層（A)的表面進 一步形成有硬化被膜。 (8) —種耐擦傷性樹脂板，其係含有上述（1)〜（6)中 任一項之層合體，上述甲基丙烯酸酯樹脂層（B)的表面進 一步形成有硬化被膜。 -6- 201235211 (9) 如上述（7)之耐擦傷性樹脂板，其中上述甲基丙 儲酸酯樹脂層（B)的表面進一步形成有硬化被膜。 (10) —種顯示器用保護板，其係使用上述（7)〜（9)中 任一項之耐擦傷性樹脂扳，甲基丙烯酸酯樹脂層（A)係面 向視認者側設置。 (11) 一種觸控式面板用保護板，其係使用上述（7)〜 (9)中任一項之耐擦傷性樹脂板，甲基丙烯酸酯樹脂層（A) 係面向視認者側設置。 發明效果 本發明之層合體其耐衝撃性與表面硬度優異，若將使 用有該層合體之耐擦傷性樹脂板用作顯示器或觸控式面板 的保護板，則可使該等受到有效保護。 【實施方式】 本發明之層合體’係於聚碳酸酯樹脂層的單面層合有 含橡膠粒子之甲基丙烯酸酯樹脂層（A)，於另一面層合有 含橡膠粒子之甲基丙烯酸酯樹脂層（B)。 構成上述聚碳酸酯樹脂層之聚碳酸酯樹脂係一般作爲 聚碳酸酯樹脂之樹脂，只要是可製造作爲本發明目的之層 合體之樹脂則無特別限制。上述聚碳酸酯樹脂可列舉例如 藉由二元酚與羰基化劑利用界面聚縮合法或熔融酯交換法 等進行反應所獲得之樹脂、碳酸酯預聚物利用固態酯交換 法等進行聚合所獲得之樹脂、環狀碳酸酯化合物利用開環 201235211 聚合法進行聚合所獲得之樹脂等。 上述一元酣係通常作爲二元酚之化合物，其係用於製 造聚碳酸酯樹脂，只要是可製造達成本發明目的之層合體 之二兀酚則無特別限制’可列舉例如氫醌、間苯二酚、 4,4’_二羥聯苯、雙（4-羥苯基）甲烷、雙{(4-羥基-3,5-二甲 基）苯基}甲烷、1，1-雙（4-羥苯基）乙烷、羥苯基）-卜苯乙院、2,2-雙（4-羥苯基）丙烷（通稱雙酚a)、2,2-雙 {(4-羥基-3-甲基）苯基}丙烷、2,2-雙{(4-羥基-3,5-二甲基） 苯基}丙烷、2,2-雙{(4-羥基-3,5-二溴）苯基}丙烷、2,2-雙 {(3-異丙基<4-羥基）苯基}丙烷、2,2-雙{(4-羥基-3-苯基）苯 基}丙烷、2,2-雙（4-羥苯基）丁烷、2,2-雙（4-羥苯基）-3-甲 基丁烷、2,2-雙（4-羥苯基）-3,3-二甲基丁烷、2,4-雙（4-羥 苯基）-2_甲基丁烷、2,2 -雙（4-羥苯基）戊烷、2,2-雙（4-羥苯 基）-4-甲基戊烷、1,1-雙（4-羥苯基）環己烷、1，1·雙（4_羥苯 基）-4-異丙基環己烷、1，1-雙（4-羥苯基）-3,3,5-三甲基環己 烷、9,9-雙（4-羥苯基）莽、9,9-雙{(4-羥基-3-甲基）苯基}蔣 、α，α’-雙（4-羥苯基）-〇二異丙苯、α，α’-雙（4-羥苯基）-m-二異丙苯、α,α’-雙（4-羥苯基）-p-二異丙苯、1,3-雙（4-羥苯 基）-5,7-二甲基金剛烷、4,4’-二羥基二苯颯、4,4’-二羥基 二苯亞碾、4,4’-二羥基二苯硫醚、4,4’-二羥基二苯酮、 4,4’-二羥基二苯醚、4，4’-羥基二苯酯等。二元酚可單獨 使用或組合使用2種以上。 其中，較佳爲單獨使用選自雙酚A、2,2-雙{(4-羥基-3-甲基）苯基}丙烷、2,2-雙（4-羥苯基）丁烷、2,2·雙（4-羥苯 201235211 基）-3-甲基丁烷、2,2-雙（4-羥苯基）-3,3-二甲基丁烷、2,2-雙（4-羥苯基）-4-甲基戊烷、1，1-雙（4-羥苯基）-3,3,5-三甲 基環己烷及α,α’-雙（4-羥苯基）-m-二異丙苯所構成之群中 之二元酚，或組合使用2種以上。特別是以單獨使用雙酚 A較佳，或以組合使用選自雙酚 A、1,1-雙（4-羥苯基）-3,3,5-三甲基環己烷、雙酚A、2,2-雙{(4-羥基-3-甲基）苯 基}丙烷及α，α’-雙（4-羥苯基）-m-二異丙苯所構成之群中之 1種以上的二元酚較佳。 上述羰基化劑係一般作爲羰基化劑之化合物，只要是 可製造本發明相關之聚碳酸酯樹脂之羰基化劑則無特別限 制，可列舉例如光氣（P h 〇 S g e n e)等碳基鹵化物.、二苯基碳 酸酯等碳酸酯、二元酚之二鹵甲酸酯（dihaloformate)等鹵 甲酸酯等，亦可視需要使用該等2種以上。 另一方面，上述甲基丙烯酸酯樹脂層（A)係使用甲基 丙烯酸酯樹脂組成物（a)來形成，上述甲基丙烯酸酯樹脂 層（B)係使用甲基丙烯酸酯樹脂組成物（b)來形成。該等甲 基丙烯酸酯樹脂組成物（a)、（b)皆含有樹脂成分之甲基丙 烯酸酯樹脂。上述甲基丙烯酸酯樹脂係一般作爲甲基丙烯 酸酯樹脂之樹脂，只要是可獲得作爲本發明目的之層合體 則無特別限制，通常可爲以甲基丙烯酸甲酯單元爲主成分 之樹脂，更具體而言以通常含有50重量％以上之甲基丙 烯酸甲酯單元，較佳爲含有70重量％以上之甲基丙烯酸 甲酯樹脂爲宜，亦可爲甲基丙烯酸甲酯單元1〇〇重量％之 甲基丙烯酸甲酯同元聚合物，亦可爲由甲基丙烯酸甲酯與 -9- 201235211 可與該甲基丙烯酸甲酯進行共聚合之其他單體所構成之共 聚物。 可與甲基丙烯酸甲酯進行共聚合之上述其他單體，只 要可獲得作爲本發明目的之層合體則無特別限制，可列舉 例如甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸環己 酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸 2-乙基己酯、甲基丙烯酸2-羥乙酯等甲基丙烯酸甲酯以外 的甲基丙烯酸酯類；丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸 2-乙基己酯、丙烯酸2-羥乙酯等丙烯酸酯類等。此外，苯 乙烯或取代苯乙烯類可列舉例如氯苯乙烯、溴苯乙烯等鹵 化苯乙烯類；甲苯乙烯、α-甲苯乙烯等烷基苯乙烯類等。 此外，亦可列舉甲基丙烯酸、丙烯酸等不飽和酸類；丙烯 腈、甲基丙烯腈、馬來酸酐、苯基馬來亞醯胺、環己基馬 來亞醯胺等。可與該等甲基丙烯酸甲酯進行共聚合之其他 單體可分別單獨使用，亦可組合使用2種以上。其中，甲 基丙烯酸酯樹脂組成物（a)、（b)所含有之甲基丙烯酸酯樹 脂的組成可互爲相同，亦可不同。 此外，甲基丙烯酸酯樹脂組成物（a)、（b)皆含有作爲 必要成分之橡膠粒子。該橡膠粒子只要可獲得作爲本發明 目的之層合體則無特別限制，可列舉例如丙烯酸系多層構 造聚合物、或5〜80重量份之橡膠狀聚合物與丙烯酸系不 飽和單體等乙烯性不飽和單體20〜95重量份進行接枝聚 合所獲得之接枝共聚物等。 -10- 201235211 上述丙烯酸系多層構造聚合物較佳爲內含彈性體層 20〜60重量％左右者，最外層較佳爲具有硬質層者，此外 最內層亦可具有硬質層。 上述彈性體層較佳爲玻璃轉移點（Tg)低於25。(：之丙烯 酸系聚合物層’具體而言較佳爲由單官能單體（其選自低 級烷基丙烯酸酯、低級烷基甲基丙烯酸酯' 低級烷氧基烷 基丙烯酸酯、氰乙基丙烯酸酯、丙烯醯胺、羥基低級烷基 丙烯酸酯、羥基低級烷基甲基丙烯酸酯、丙烯酸及甲基丙 烯酸所構成之群中之1種以上）與烯丙基甲基丙烯酸酯等 多官能單體進行交聯所構成之聚合物層》 上述低級烷基丙烯酸酯等中之低級烷基可列舉例如甲 基、乙基、丙基、異丙基、丁基、t-丁基、戊基、己基等 碳數1〜6之直鏈或分支之烷基，上述低級烷氧基烷基丙 烯酸酯中之低級烷氧基可列舉例如甲氧基、乙氧基、丙氧 基、異丙氧基、丁氧基、t -丁氧基、戊氧基、己氧基等碳 數1〜6之直鏈或分支之烷氧基。此外，當以上述單官能 單體作爲主成分來獲得共聚物時，共聚合成分亦可與例如 苯乙烯、取代苯乙烯等其他單官能單體進行共聚合。 上述硬質層較佳爲Tg爲25 t以上之丙烯酸系聚合物 層，具體而言較佳爲以具有碳數1〜4之烷基之烷基甲基 丙烯酸酯單獨、或以其爲主成分進行聚合而成之層。上述 碳數1〜4之烷基可列舉例如甲基、乙基、丙基、異丙基 、丁基、t-丁基等直鏈或分支之烷基。 當以具有碳數1〜4之烷基之烷基甲基丙烯酸酯作爲 -11 - 201235211 主成分來獲得共聚物時’共聚合成分亦可使用其他烷基甲 基丙烯酸酯或烷基丙烯酸酯、苯乙烯、取代苯乙烯、丙燒 腈、甲基丙烯腈等單官能單體’此外亦可添加烯丙基甲基 丙烯酸酯等多官能單體成爲交聯聚合物。上述烷基甲基丙 烯酸酯等中之烷基可列舉例如與上述低級烷基所例示者相 同碳數1〜6之直鏈或分支之烷基等。 上述丙烯酸系多層構造聚合物係記載於例如jp5 5 _ 27576B 、 JP6-80739A 、 JP49-23292A 等。 5〜80重量份之橡膠狀聚合物與乙烯性不飽和單體2〇 〜95重量份進行接枝聚合所獲得之上述接枝共聚物中， 橡膠狀聚合物可列舉例如聚丁二烯橡膠、丙烯腈/ 丁二烯 共聚物橡膠、苯乙烯/ 丁二烯共聚物橡膠等二烯系橡膠； 聚丁基丙烯酸酯、聚丙基丙烯酸酯、聚-2-乙基己基丙烯 酸酯等丙烯酸系橡膠；乙烯/丙烯/非共軛二烯系橡膠等^ 此外’用以與該橡膠狀聚合物進行接枝共聚合之乙烯性單 體可列舉例如苯乙烯、丙烯腈、烷基（甲基）丙烯酸酯等。 該等接枝共聚物係記載於例如：ΓΡ55-147514Α、JP47-9740B等。其中，甲基丙烯酸酯樹脂組成物（a)、（b)所含 有之橡膠粒子的組成可互爲相同，亦可不同。 橡膠粒子的含量，只要可獲得作爲本發明目的之層合 體則無特別限制，以甲基丙烯酸酯樹脂及橡膠粒子合計 100重量％爲基準較佳爲3〜20重量％，更佳爲5〜15重 量％。若橡膠粒子的含量過少則耐衝撃性會有降低的傾向 ’而若橡膠粒子的含量過多則表面硬度會有降低的傾向， -12- 201235211 故不佳。其中，甲基丙烯酸酯樹脂組成物（a)、（b)所含有 之橡膠粒子的比例可互爲相同，亦可不同。 聚碳酸酯樹脂層、甲基丙烯酸酯樹脂層（A)、（B)亦可 分別視需要添加例如光擴散劑、消光劑、染料、光安定劑 、紫外線吸收劑、抗氧化劑、脫瘼劑、阻燃劑、抗靜電劑 等添加劑1種或2種以上。 本發明之層合體通常爲片狀或膜狀，其製造方法只要 可獲得作爲本發明目的之層合體則無特別限制，可較佳地 藉由將聚碳酸酯樹脂層、甲基丙烯酸酯樹脂層（A)及甲基 丙烯酸酯樹脂層（B)進行共擠壓成形使其層合而一體化的 方式製造。該共擠壓成形，可藉由使用3台之單軸或二軸 的擠壓機分別將聚碳酸酯樹脂、甲基丙烯酸酯樹脂組成物 (a)及甲基丙烯酸酯樹脂組成物（b)熔融混練，然後透過分 流器（feed block)模具或多管模具等加以層合的方式進行 ’層合一體化之熔融層合體可使用例如輥單元進行冷卻固 化。 其中’當甲基丙烯酸酯樹脂組成物（a)、（b)的組成互 爲相同時’亦可使用2台之單軸或二軸的擠壓機分別將聚 碳酸酯樹脂於一側的擠壓機、將甲基丙烯酸酯樹脂組成物 (a)、（b)—同於另一側的擠壓機進行熔融混練。藉由共擠 壓成形所製造之層合體，與藉由使用黏著劑或接著劑之貼 合所製造之層合體相比，以易於二次成形的觀點而言較佳 〇 於此’可於上述層合體之至少一側之面形成硬化被膜[Problem to be Solved by the Invention] The object of the present invention is to provide a laminate having high impact resistance and high surface hardness, and a scratch resistant resin sheet and display using the same. Use protective plates and protective panels for touch panels. MEANS TO SOLVE THE PROBLEM-5-201235211 The present inventors have made an effort to solve the above problems, and as a result, have found a solution to the following constitution, and have completed the present invention. (1) A laminate characterized in that it is concentrated A methacrylate resin layer (A) containing rubber particles is laminated on one side of the carbonate resin layer, and a methacrylate resin layer (B) containing rubber particles is laminated on the other surface, when the above methacrylate is used. When the thickness of the resin layer (A) is t (A) and the thickness of the methacrylate resin layer (B) is t (B), t (A) > t (B). (2) The laminate according to the above (1), wherein the ratio of t(A) to t(B) (t(A)/t(B)) is 1.2 or more. (3) The laminate according to the above (1) or (2), wherein the above t(A) is 50 to 200 μm, and the above t(B) is 10 to 150 μm β (4) as in the above (1) to (3) A laminate in which the total thickness of the above t(A) and t(B) is 50% or less of the entire thickness of the laminate. (5) The laminate according to any one of the above (1) to (4) wherein the laminate has a total thickness of 0.3 to 3 mm. The laminate of any one of the above-mentioned (1) to (5), wherein the polycarbonate resin layer, the methacrylate resin layer (A) and the methacrylate resin layer (B) are Co-extruded and laminated. (7) A layer of the above-mentioned (1) to (6), wherein the surface of the methacrylate resin layer (A) is further formed with a cured film. (8) A scratch-resistant resin sheet comprising the laminate according to any one of the above (1) to (6), wherein a surface of the methacrylate resin layer (B) is further formed with a cured film. -6-201235211 (9) The scratch-resistant resin sheet according to the above (7), wherein the surface of the methyl acrylate acid ester resin layer (B) is further formed with a hardened film. (10) A protective sheet for a display, which is obtained by using the scratch-resistant resin of any one of the above (7) to (9), and the methacrylate resin layer (A) is provided on the side of the viewer. (11) A protective sheet for a touch panel, which is obtained by using the scratch-resistant resin sheet according to any one of the above (7) to (9), wherein the methacrylate resin layer (A) is provided on the side facing the viewer. EFFECTS OF THE INVENTION The laminate of the present invention is excellent in punching resistance and surface hardness, and if the scratch-resistant resin sheet using the laminate is used as a protective sheet for a display or a touch panel, the sheet can be effectively protected. [Embodiment] The laminate of the present invention is characterized in that a methacrylate resin layer (A) containing rubber particles is laminated on one side of a polycarbonate resin layer, and methacrylic acid containing rubber particles is laminated on the other side. Ester resin layer (B). The polycarbonate resin constituting the polycarbonate resin layer is generally a resin of a polycarbonate resin, and is not particularly limited as long as it is a resin which can produce a laminate which is the object of the present invention. The polycarbonate resin can be obtained, for example, by a resin obtained by a reaction between a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid transesterification method or the like. The resin and the cyclic carbonate compound are obtained by polymerization using a ring-opening 201235211 polymerization method. The above-mentioned monoterpene is usually a compound of a dihydric phenol, which is used for the production of a polycarbonate resin, and is not particularly limited as long as it is a binder capable of producing a laminate for achieving the object of the present invention, and examples thereof include hydroquinone and m-benzene. Diphenol, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-double (4 -hydroxyphenyl)ethane, hydroxyphenyl)- phenylene, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol a), 2,2-bis{(4-hydroxy-3) -methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dibromo Phenyl}propane, 2,2-bis{(3-isopropyl<4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3, 3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-dual (4 -hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1 bis(4-hydroxyphenyl)-4-isopropylcyclohexane 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-double {(4- Hydroxy-3-methyl)phenyl}Jiang, α,α'-bis(4-hydroxyphenyl)-indole diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diiso Propylene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4 '-Dihydroxydiphenyl hydrazine, 4,4'-dihydroxydiphenyl arylene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy Diphenyl ether, 4,4'-hydroxydiphenyl ester, and the like. The dihydric phenol may be used singly or in combination of two or more. Among them, it is preferred to use bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2 separately. , 2·bis(4-hydroxybenzene 201235211 yl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-dual (4 -hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α,α'-bis(4-hydroxybenzene) The dihydric phenol in the group consisting of -m-diisopropylbenzene or two or more types may be used in combination. In particular, it is preferred to use bisphenol A alone or in combination with bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bisphenol A. One of a group consisting of 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene The above dihydric phenol is preferred. The carbonylating agent is generally a compound of a carbonylating agent, and is not particularly limited as long as it is a carbonylating agent capable of producing the polycarbonate resin of the present invention, and examples thereof include carbon-based halogenation such as phosgene (Ph 〇S gene). Two or more kinds of these may be used as needed, such as a carbonate such as a diphenyl carbonate or a dihaloformate such as a dihaloformate. On the other hand, the methacrylate resin layer (A) is formed using a methacrylate resin composition (a), and the methacrylate resin layer (B) is a methacrylate resin composition (b). ) to form. Each of the methacrylate resin compositions (a) and (b) contains a methacrylate resin of a resin component. The methacrylate resin is generally a resin of a methacrylate resin, and is not particularly limited as long as it can obtain a laminate which is an object of the present invention, and is usually a resin containing a methyl methacrylate unit as a main component. Specifically, it is preferable to contain 50% by weight or more of a methyl methacrylate unit, preferably 70% by weight or more of a methyl methacrylate resin, or may be a methyl methacrylate unit of 1% by weight. The methyl methacrylate homopolymer may also be a copolymer composed of methyl methacrylate and other monomers copolymerizable with the methyl methacrylate -9-201235211. The above other monomer which can be copolymerized with methyl methacrylate is not particularly limited as long as the laminate which is the object of the present invention can be obtained, and examples thereof include ethyl methacrylate, butyl methacrylate, and methacrylic acid ring. a methacrylate other than methyl methacrylate such as hexyl ester, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate or 2-hydroxyethyl methacrylate; Ester, acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and the like. Further, examples of the styrene or substituted styrene include halogenated styrenes such as chlorostyrene and bromostyrene; alkylstyrenes such as styrene and α-methylstyrene; and the like. Further, unsaturated acids such as methacrylic acid and acrylic acid; acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide or the like may be mentioned. The other monomers which can be copolymerized with the methyl methacrylate may be used alone or in combination of two or more. Here, the composition of the methacrylate resin contained in the methacrylate resin compositions (a) and (b) may be the same or different. Further, the methacrylate resin compositions (a) and (b) each contain rubber particles as an essential component. The rubber particles are not particularly limited as long as the laminate of the present invention is obtained, and examples thereof include an acrylic multilayer structure polymer, or 5 to 80 parts by weight of a rubber-like polymer and an acrylic unsaturated monomer. 20 to 95 parts by weight of the saturated monomer, a graft copolymer obtained by graft polymerization or the like. -10- 201235211 The acrylic multilayer structure polymer preferably has an elastomer layer of about 20 to 60% by weight, and the outermost layer preferably has a hard layer, and the innermost layer may have a hard layer. The above elastomer layer preferably has a glass transition point (Tg) of less than 25. (The acrylic polymer layer ' is specifically preferably a monofunctional monomer (which is selected from the group consisting of lower alkyl acrylate, lower alkyl methacrylate 'lower alkoxyalkyl acrylate, cyanoethyl Acrylate, acrylamide, hydroxy lower alkyl acrylate, hydroxy lower alkyl methacrylate, one or more of a group consisting of acrylic acid and methacrylic acid) and a polyfunctional single such as allyl methacrylate The polymer layer formed by cross-linking the body. The lower alkyl group in the lower alkyl acrylate or the like may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group or a pentyl group. a straight or branched alkyl group having a carbon number of 1 to 6 or the like, and a lower alkoxy group in the above lower alkoxyalkyl acrylate may, for example, be a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group. a linear or branched alkoxy group having a carbon number of 1 to 6 such as a butoxy group, a t-butoxy group, a pentyloxy group or a hexyloxy group. Further, when the above monofunctional monomer is used as a main component, a copolymer is obtained. When the copolymerization component is also compatible with, for example, styrene, substituted styrene, etc. The functional group is copolymerized. The hard layer is preferably an acrylic polymer layer having a Tg of 25 t or more, and specifically, an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is preferably used alone. Or a layer obtained by polymerizing the main component. The alkyl group having 1 to 4 carbon atoms may, for example, be a straight chain or a branch such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group. When an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is used as a main component of -11 - 201235211 to obtain a copolymer, the copolymerization component may also use other alkyl methacrylate or alkane. A monofunctional monomer such as acrylate, styrene, substituted styrene, acrylonitrile or methacrylonitrile may be added as a cross-linking polymer by adding a polyfunctional monomer such as allyl methacrylate. Examples of the alkyl group in the methacrylate or the like include a linear or branched alkyl group having the same carbon number of 1 to 6 as those exemplified as the above lower alkyl group. The acrylic multilayer structure polymer is described, for example, as jp5 5 _ 27576B, JP6-80739A, JP49-23292A, etc. 5~80 weight In the above graft copolymer obtained by graft-polymerizing a rubbery polymer and an ethylenically unsaturated monomer in an amount of from 2 to 95 parts by weight, the rubbery polymer may, for example, be a polybutadiene rubber or an acrylonitrile/butyl group. Diene rubber such as diene copolymer rubber or styrene/butadiene copolymer rubber; acrylic rubber such as polybutyl acrylate, polypropyl acrylate or poly-2-ethylhexyl acrylate; ethylene/propylene/ Non-conjugated diene rubber, etc. Further, the vinyl monomer to be graft-copolymerized with the rubbery polymer may, for example, be styrene, acrylonitrile or alkyl (meth)acrylate. The graft copolymer is, for example, ΓΡ55-147514Α, JP47-9740B, etc. The composition of the rubber particles contained in the methacrylate resin compositions (a) and (b) may be the same or different. The content of the rubber particles is not particularly limited as long as the laminate of the present invention is obtained, and is preferably 3 to 20% by weight, more preferably 5 to 15% based on 100% by weight based on the total of the methacrylate resin and the rubber particles. weight%. When the content of the rubber particles is too small, the impact resistance tends to decrease. When the content of the rubber particles is too large, the surface hardness tends to decrease, and -12-201235211 is not preferable. Here, the ratio of the rubber particles contained in the methacrylate resin compositions (a) and (b) may be the same or different. The polycarbonate resin layer or the methacrylate resin layers (A) and (B) may be optionally added with, for example, a light diffusing agent, a matting agent, a dye, a photostabilizer, an ultraviolet absorber, an antioxidant, a deodorant, or the like. One or more additives such as a flame retardant and an antistatic agent. The laminate of the present invention is usually in the form of a sheet or a film, and the production method thereof is not particularly limited as long as the laminate which is the object of the present invention is obtained, and a polycarbonate resin layer or a methacrylate resin layer can be preferably used. (A) and the methacrylate resin layer (B) are produced by co-extrusion molding, lamination and integration. In the co-extrusion molding, the polycarbonate resin, the methacrylate resin composition (a) and the methacrylate resin composition (b) can be respectively used by using three single-axis or two-axis extruders. The melt-kneading is carried out by laminating a feed block mold or a multi-tube mold or the like, and the laminated integrated melt laminate can be cooled and solidified using, for example, a roll unit. Wherein 'when the compositions of the methacrylate resin compositions (a) and (b) are identical to each other', the squeezing of the polycarbonate resin on one side can also be carried out using two uniaxial or two-axis extruders, respectively. The press and the methacrylate resin compositions (a) and (b) were melt-kneaded together with the extruder on the other side. The laminate produced by the co-extrusion molding is preferable to the laminate produced by the bonding using an adhesive or an adhesive, from the viewpoint of easy secondary molding. Forming a hardened film on at least one side of the laminate
S -13- 201235211 以獲得耐擦傷性樹脂板，當使用該耐擦傷性樹脂板作爲顯 示器或觸控式面板的保護板時，該耐擦傷性樹脂板係以甲 基丙烯酸酯樹脂層（A)朝向外側（視認者側）、甲基丙烯酸 酯樹脂層（B)朝向內側（顯示器側·觸控式面板側）的方式 使用。因此，甲基丙烯酸酯樹脂層（A)、（B)當中，朝向視 認者側之甲基丙烯酸酯樹脂層（A)容易受到外部之衝撃或 負荷等。 本發明之層合體，當甲基丙烯酸酯樹脂層（A)的厚度 設爲t(A)、甲基丙烯酸酯樹脂層（B)的厚度設爲t(B)時， 上述t(A)及t(B)係構成具有t(A)>t(B)的關係。藉此，容 易受到外部之衝撃或負荷等之甲基丙烯酸酯樹脂層（A)的 厚度t(A)變大，結果使層合體的耐衝撃性及表面硬度提升 上述t(A)與t(B)之間的層厚比（t(A)/t(B))較佳爲1.2 以上，更佳爲1.5以上。藉此，因甲基丙烯酸酯樹脂層 (A)的厚度t(A)充分大於甲基丙烯酸酯樹脂層（B)的厚度 t(B)，故層合體的耐衝撃性及表面硬度會確實提升。層厚 比（t(A)/t(B))的上限値並無特別限定，通常爲3.0以下左 右。 上述t(A)較佳爲50〜200μιη，更佳爲60〜120μπι，上 述t(B)較佳爲1〇〜150μηι，更佳爲30〜60μπι，最佳爲40 〜60μιη，於該數値範圍內較佳爲t(A)、t(B)具有t(A) > t(B)之關係。相對於此，若上述t(A)、t(B)過小則表面硬 度會有降低的傾向，若上述t(A)、t(B)過大則層合體的耐 -14- 201235211 熱性或耐衝撃性會有降低之虞’故不佳。 上述t(A)與t(B)之間合計厚度較佳爲層合體整體的厚 度的50%以下。若t(A)、t(B)之合計厚度過大則聚碳酸酯 樹脂層整體的厚度會變大，伴隨其之層合體的耐熱性或耐 衝撃性會有降低之虞，故不佳。 層合體整體的厚度較佳爲0·3〜3mm’更佳爲〇_4〜 3mm，最佳爲0.5〜2mm。該層合體整體的厚度、或上述 甲基丙烯酸酯樹脂層（A)、（B)的厚度t(A)、t(B)、及聚碳 酸酯樹脂層的厚度均可藉由從模具擠壓出之熔融層合體的 厚度、及夾入該熔融層合體之輥的間隔等進行調整。 另一方面，上述層合體可適合使用作爲耐擦傷性樹脂 板用之樹脂基板。接著針對本發明之耐擦傷性樹脂板進行 說明。本發明之耐擦傷性樹脂板係於上述層合體之至少一 側之面形成有硬化被膜。 該耐擦傷性樹脂板較佳爲於層合體之甲基丙烯酸酯樹 脂層（A)的表面形成有硬化被膜’更佳爲除了該表面，於 甲基丙烯酸酯樹脂層（B)的表面亦形成有硬化被膜。藉此 ，可提升耐擦傷性樹脂板的耐擦傷性。 此外，亦可僅於甲基丙烯酸酯樹脂層（B)的表面形成 硬化被膜。 耐擦傷性樹脂板的層構成，可列舉下述⑴〜（iii)。 (i)硬化被膜/甲基丙烯酸酯樹脂層（A)/聚碳酸酯樹脂 層/甲基丙烯酸酯樹脂層（B) (Π)甲基丙烯酸酯樹脂層（A)/聚碳酸酯樹脂層/甲基丙 -15- 201235211 烯酸酯樹脂層（B)/硬化被膜 (iii)硬化被膜/甲基丙烯酸酯樹脂層（A)/聚碳酸酯樹脂 層/甲基丙烯酸酯樹脂層（B)/硬化被膜 其中，當上述層合體的雙面形成硬化被膜時，雙面之 硬化被膜的組成或厚度可互爲相同，亦可不同。 上述硬化被膜可藉由塗佈硬化性塗料組成物並使其硬 化而形成。該硬化性塗料組成物係以賦予耐擦傷性之硬化 性化合物作爲必要成分，視需要含有例如硬化觸媒、導電 性粒子、溶劑、調平劑、安定化劑、抗氧化劑、著色劑等 之組成物》 上述硬化性化合物可列舉例如丙烯酸酯化合物、胺基 甲酸酯丙烯酸酯化合物、環氧基丙烯酸酯化合物、羧基改 質環氧基丙烯酸酯化合物、聚酯丙烯酸酯化合物、共聚合 系丙烯酸酯化合物、脂環式環氧樹脂、縮水甘油醚環氧樹 脂、乙烯醚化合物、氧雜環丁烷化合物等。其中，從硬化 被膜的耐擦傷性的觀點而言，較佳爲使用多官能丙烯酸酯 化合物、多官能胺基甲酸酯丙烯酸酯化合物、多官能環氧 基丙烯酸酯化合物等自由基聚合系之硬化性化合物，·或可 較佳使用烷氧基矽烷、烷基烷氧基矽烷等熱聚合系之硬化 性化合物等。該等硬化性化合物可爲藉由例如照射電子線 '放射線、紫外線等能量線而硬化者，亦可爲藉由加熱而 硬化者。該等硬化性化合物可分別單獨使用，亦可組合使 用複數種化合物。 特佳之硬化性化合物係於分子中具有至少3個（甲基） -16- 201235211 丙烯醯氧基之化合物。於此，所謂（甲基）丙烯醯氧基意指 丙烯醯氧基或甲基丙烯醯氧基，其他在本說明書中指（甲 基）丙烯酸酯、（甲基）丙烯酸等時之「（甲基）」意義亦同。 於分子中至少具有3個（甲基）丙烯醯氧基之上述化合 物可列舉例如三羥甲基丙烷三（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、五甘油 三（甲基）丙烯酸酯、新戊四醇三或四（甲基）丙烯酸酯、二 新戊四醇三、四、五或六（甲基）丙烯酸酯、三新戊四醇四 、五、六或七（甲基）丙烯酸酯之3價以上多元醇之聚（甲 基）丙烯酸酯；於分子中具有異氰酸基至少2個之化合物 中，將具有羥基之（甲基）丙烯酸酯以相對於異氰酸基之羥 基爲等莫耳以上之比例進行反應而獲得之分子中（甲基）丙 烯醯氧基的個數爲3個以上之胺基甲酸酯（甲基）丙烯酸酯 〔例如藉由二異氰酸酯與新戊四醇三（甲基）丙烯酸酯之反 應而獲得6官能之胺基甲酸酯（甲基）丙烯酸酯〕；三（2-羥 乙基）異三聚氰酸之三（甲基）丙烯酸酯等。其中，此處雖 係例示單體，但除了可直接使用該等單體，亦可使用例如 形成爲2倍體、3倍體等寡聚物的形態者。此外，亦可倂 用單體與寡聚物。該等（甲基）丙烯酸酯化合物可分別單獨 使用，或混合使用2種以上。 於分子中至少具有3個（甲基）丙烯醯氧基之上述化合 物可使用市售之化合物，具體例可列舉例如皆爲新中村化 學工業（股）製之“NK HARD M101(商品名）”（胺基甲酸酯丙 烯酸酯系）、“NK ESTER A-TMM-3L(商品名），，（新戊四醇三 -17- 201235211 丙烯酸酯）、“NK ESTER Α-ΤΜΜΤ(商品名）”（新戊四醇四丙 烯酸酯）、“NK ESTER Α-953 0(商品名）”（二新戊四醇五丙 烯酸酯）及“NK ESTER A-DPH(商品名）”（二新戊四醇六丙 烯酸酯）、日本化藥（股）製之“KAYARAD DPCA(商品名）’’（ 二新戊四醇六丙烯酸酯）、SAN NOPCO(股）製之“NOPCO CURE 200(商品名）”系列、大日本油墨化學工業（股）製之 “UNIDIC(商品名）”系列等。 其中，當使用於分子中至少具有3個（甲基）丙烯醯氧 基之化合物作爲硬化性化合物時，亦可視需要倂用其他硬 化性化合物，例如乙二醇二（甲基）丙烯酸酯、二乙二醇二 (甲基）丙烯酸酯、1，6-己烷二醇二（甲基）丙烯酸酯、新戊 二醇二（甲基）丙烯酸酯之於分子中具有2個（甲基）丙烯醯 氧基之化合物，其使用量相對於分子中至少具有3個（甲 基）丙烯醯氧基之化合物100重量份通常爲20重量份。 當上述硬化性塗料組成物利用紫外線使其硬化時，可 使用光聚合起始劑作爲硬化觸媒。該光聚合起始劑可列舉 例如苯甲基、二苯基酮或其衍生物、噻吨酮類、苯甲基二 甲基縮酮類、α-羥烷基苯酮類、羥基酮類、胺烷基苯酮類 、醯基氧化膦類等，視需要亦可使用該等2種以上。光聚 合起始劑的使用量相對於硬化性化合物100重量份通常爲 0.1〜5重量份。 上述光聚合起始劑可使用市售者，具體例可列舉例如 皆爲 Ciba Specialty Chemicals(股）製之 “IRGACURE 65 1 ( 商品名）”、“IRGACURE 184(商品名）”' “IRGACURE 5 00( 201235211 商品名）”、“IRGACURE 1 000(商品名）”、“IRGACURE 2959(商品名）”、“DAROCUR 1173(商品名）”、“IRGACURE 907(商品名）”、“IRGACURE 3 69(商品名）”、“IRGACURE 1 700(商品名）”、“IRGACURE 1 8 00(商品名）”、 “IRGACURE 8 1 9(商品名）”、“IRGACURE 784(商品名）”等 IRGACURE系列及DAROCUR系列；皆爲日本化藥（股）製 之 “KAYACURE ITX(商品名）”、“KAYACURE DETX-S(商 品名）” 、“KAYACURE ΒΡ-100(商 品名）’’ ' “KAYACUREBMS(商品名），，、“KAYACURE 2-EAQ(商品名 )”等KAYACURE系列等。 藉由使上述硬化性塗料組成物含有導電性粒子，可賦 予硬化被膜抗靜電性。上述導電性粒子可較佳使用例如 銻-錫複合氧化物、含磷氧化錫、五氧化銻等氧化銻、銻_ 鋅複合氧化物、氧化鈦、銦-錫複合氧化物（ITO)之無機粒 子。上述導電性粒子亦可以固體成分濃度爲10〜30重量 %左右的溶膠形態來使用。 上述導電性粒子的粒徑通常爲0.5 μιη以下，而從硬化 被膜的抗靜電性或透明性的觀點而言，以平均粒徑表示較 佳爲 Ο.ΟΟΙμιη以上，此外較佳爲 Ο.ίμηι以下，更佳爲 0.0 5 μιη以下。導電性粒子的平均粒徑越小，越可降低耐 擦傷性樹脂板的霧値，而可提升透明性。 上述導電性粒子的使用量，相對於硬化性化合物1 〇〇 重量份通常爲2〜50重量份，較佳爲3〜20重量份。導電 性粒子的使用量越多，硬化被膜的抗靜電性越有提升的傾 -19 - 201235211 向，但若導電性粒子的使用量過多則硬化被膜的透明性會 降低，故不佳。 上述導電性粒子可藉由例如氣相分解法、電漿蒸發法 、烷氧化物分解法、共沉澱法、熱液法等製造。此外，導 電性粒子的表面亦可利用例如非離子系界面活性劑、陽離 子系界面活性劑、陰離子系界面活性劑、矽系偶合劑、鋁 系偶合劑等進行表面處理》 上述硬化性塗料組成物中，在其黏度調整等目的方面 ，較佳爲含有溶劑，特別是當含有導電性粒子時，爲了使 其分散較佳爲含有溶劑。當調製含有導電粒子及溶劑之硬 化性塗料組成物時，例如可混合導電性粒子及溶劑使溶劑 中分散導電性粒子，然後再於該分散液混合硬化性化合物 ，亦可於硬化性化合物與溶劑混合後，再於該混合液中分 散導電性粒子。 上述溶劑較佳爲可溶解硬化性化合物，且塗佈後容易 揮發，此外當塗料成分使用導電性粒子時，較佳爲可使其 分散之溶劑。上述溶劑可列舉例如二丙酮醇、甲醇、乙醇 、異丙醇、異丁醇、2-甲氧乙醇、2-乙氧乙醇、2-丁氧乙 醇' 1-甲氧基-2 -丙醇之醇類；丙嗣、甲乙嗣、甲基異丁 酮、二丙酮醇之酮類；甲苯、二甲苯之芳香族烴類；醋酸 乙酯、醋酸丁酯之酯類；水等。溶劑的使用量可配合硬化 性化合物的性狀等而適當調整。 當上述硬化性塗料組成物含有調平劑時，較佳爲使用 聚矽氧油，其例可列舉二甲基聚矽氧油 '苯甲基聚矽氧油 -20- 201235211 、烷基·芳烷基改質聚矽氧油、氟基聚矽氧油、聚醚改質 聚矽氧油、脂肪酸酯改質聚矽氧油、甲基氫聚矽氧油、含 矽醇基聚矽氧油、含烷氧基聚矽氧油、含酚基聚矽氧油、 甲基丙烯基改質聚矽氧油、胺基改質聚矽氧油、碳酸改質 聚矽氧油、甲醇改質聚矽氧油、環氧基改質聚矽氧油、硫 醇改質聚矽氧油、氟改質聚矽氧油、聚醚改質聚矽氧油等 。該等調平劑可分別單獨使用，亦可混合使用2種類以上 。調平劑的使用量相對於硬化性化合物1 00重量份通常爲 0.01〜5重量份。 上述調平劑可使用市售者，具體例可列舉例如皆爲 Dow Corning Toray Silicone Corporation(股）製之 “SH200-100cs(商品名）”、“SH28PA(商品名）”、“SH29PA(商品名）” 、“SH30PA(商品名），，、“ST83PA(商品名），’、“ST80PA(商 品名）”、“ST97PA(商品名）”及“ST86PA(商品名）”、皆爲 BYK Japan(股）製之 “BYK-302(商品名）”、“BYK-3 07(商品 名）”、“BYK-320(商品名）”及“BYK-3 30(商品名）”等。 將上述所獲得之硬化性塗料組成物塗佈於上述層合體 之至少一側之面，形成硬化性塗膜，接著使其硬化形成硬 化被膜，藉此獲得耐擦傷性樹脂板。硬化性塗料的塗佈可 藉由例如棒塗法、微凹版塗佈法、輥塗法、淋塗法、浸漬 塗佈法、旋塗法、模具塗佈法、噴塗法等塗佈法來進行。 硬化性塗膜的硬化可視硬化性塗料組成物的種類進行能量 線的照射或加熱等。 藉由能量線的照射使其硬化時的能量線例如可列舉紫 -21 - 201235211 外線、電子線、放射線等，其強度或照射時間等條件係視 硬化性塗料組成物的種類而適當選擇。此外，藉由加熱使 之硬化時，其溫度或時間等條件係視硬化性塗料組成物的 種類而適當選擇，爲了不使樹脂基板發生變形，加熱溫度 —般而言較佳爲loot以下。當硬化性塗料組成物含有溶 劑時，可於塗佈後、溶劑揮發後使硬化性塗膜硬化，亦可 同時進行溶劑的揮發與硬化性塗膜的硬化。 上述硬化被膜的厚度較佳爲0.5〜50μπι，更佳爲1〜 2〇μηι »雖然硬化被膜的厚度越小有越不容易發生龜裂的 傾向，但若過小則耐擦傷性會不足，故不佳。 所得之耐擦傷性樹脂板亦可視需要於其表面利用塗佈 法或濺鍍法、真空蒸鑄法等實施抗反射處理。此外，亦可 將額外製作之抗反射性片貼合於耐擦傷性樹脂板的單面或 雙面來賦予抗反射效果。 如此一來，所得之耐擦傷性樹脂板，其耐衝撃性與表 面硬度優異，故可用於各種用途，其中可較佳用作保護板 ，更具體而言，可較佳用於顯示器保護板、顯示窗保護板 及觸控式面板保護板。 受保護之顯示器的種類可列舉例如CRT顯示器、液 晶顯示器' 電漿顯示器、EL顯示器等。此外，受保護之 顯示器的用途可列舉例如電視或電腦螢幕、行動電話或 PHS(Personal Handy-phone System) 、 PD A(Personal Digital Assistant)等行動型資訊終端機的顯示窗、數位攝 影機或手持型視訊攝影機的取景部、行動型遊戲機的顯示 -22- 201235211 窗等。 受保護之觸控式面板的用途可列舉例如汽車導航系統 或行動型資訊終端機、產業機械等操作的面板、個人電腦 的畫面、行動型遊戲機等的觸控式面板等。 從本發明之耐擦傷性樹脂板來製造顯示器保護板及觸 控式面板保護板等保護板之方法，只要是可製造作爲本發 明目的之保護板之方法則無特別限制，例如首先可視需要 於耐擦傷性樹脂板進行印刷、穿孔等加工，再裁切處理成 需要的大小。然後將其設置於顯示器或觸控式面板，則可 有效保護顯示器及觸控式面板。此時，係以甲基丙烯酸酯 樹脂層（A)成爲外側（視認者側），甲基丙烯酸酯樹脂層（B) 成爲內側（顯示器側•觸控式面板側）的方式設置。 以下藉由實施例對本發明進行進一步詳細說明，但本 發明並無侷限於該等實施例。此外，以下實施例中表示含 量或使用量之％及份，若無特別註明則爲重量基準。 實施例及比較例中，用以製造層合體及耐擦傷性樹脂 板之使用材料係如下所述。 •聚碳酸酯樹脂：使用住友陶氏（股）製之「CALIBRE 301-10(商品名）」。 •甲基丙烯酸酯樹脂：使用甲基丙烯酸甲酯97.8%與 丙烯酸甲酯2.2%所構成之單體藉由塊狀聚合而獲得之熱 塑性聚合物（玻璃轉移溫度l〇4°C)之小粒。其中，該玻璃 轉移溫度係依照JIS K7 1 2 1 : 1 987，利用示差掃描熱量測 定於加熱速度1 0°C /分所求得之外差玻璃轉移起始溫度。 -23- 201235211 •橡膠粒子：使用藉由乳化聚合法而得之橡膠粒子， 其具有三層構造，最內層爲甲基丙烯酸甲酯93.8%與丙烯 酸甲酯6%與甲基丙烯酸烯丙酯0.2%所構成之單體藉由聚 合而獲得之硬質聚合物，中間層爲丙烯酸丁酯81 %與苯乙 烯17%與甲基丙烯酸烯丙酯2%所構成之單體藉由聚合而 獲得之彈性聚合物，最外層爲甲基丙烯酸甲酯94%與丙烯 酸甲酯6%所構成之單體藉由聚合而獲得之硬質聚合物。 最內層、中間層、最外層的重量比爲35: 45: 20。 •硬化性塗料：使用混合有二新戊四醇六丙烯酸酯〔 新中村化學工業（股）製之「NK ESTER A-DPH(商品名）」 25 份、光聚合起始劑〔Ciba Specialty Chemicals(股）製 之「IRGACURE 184(商品名）」〕2份、五氧化銻微粒子溶 膠〔觸媒化成工業（股）製之「ELCOMV-4514(商品名）」； 固體成分濃度20%、平均粒子徑低於〇· Ιμιη〕1〇份（固體 成分2份）、1-甲氧基-2-丙醇24份、異丁醇24份、及二 丙酮醇1 5份而調製成之硬化性塗料。 〔實施例1、2及比較例1〜3〕 〔層合體的製作〕 首先，在甲基丙烯酸酯樹脂層（Α)及（Β)的形成材料方 面，係調製出甲基丙烯酸酯樹脂組成物（a)及（b)。具體而 言，係將甲基丙烯酸酯樹脂與橡膠粒子依照以下所示之比 例以超級混合機進行混合，再以二軸擠壓機於240 °C進行 熔融混練，而獲得甲基丙烯酸酯樹脂與橡膠粒子所構成之 -24- 201235211 甲基丙烯酸酯樹脂組成物（a)及（b)之小粒。 實施例1、2及比較例1、2:以甲基丙烯酸醋樹脂 86%及橡膠粒子14%的比例混合。 比較例3:以甲基丙烯酸酯樹脂94%及橡膠粒子6% 的比例混合。 接著，利用直徑65mm φ 之單軸擠壓機〔東芝機械（ 股）〕將聚碳酸酯樹脂於265 °C進行加以’並利用直：徑 45mm φ之單軸擠壓機〔日立造船（股）〕將甲基丙嫌酸醋 樹脂組成物（a)、（b)同時於25 5 °C加以熔融，透過多管型模 具於260°C進行擠壓，使得於聚碳酸酯樹脂層的單面層合 有甲基丙烯酸酯樹脂層（A)、於另一面層合有甲基丙烯酸 酯樹脂層（B)。 接著，將擠壓出之膜狀物夾進一對表面平滑之金屬製 輥之間進行成形冷卻以形成表1所示之厚度，而獲得表1 所示之厚度之3層構成之層合體，該層合體於聚碳酸酯樹 脂層的單面層合有甲基丙烯酸酯樹脂層（A)、於另一面層 合有甲基丙烯酸酯樹脂層（B)。 〔耐擦傷性樹脂板的製作〕 首先，將所得之層合體裁切成l〇〇mmx80mm的大小 ，利用浸漬法於層合體的雙面形成硬化性塗料的塗膜。接 著，於室溫乾燥1分鐘，再於5 〇°C的熱風烘箱內乾燥3分 鐘使溶劑揮發，然後使用1 20W的高壓水銀燈對該塗膜照 射0.5 J/cm2的紫外線使其硬化，而獲得於層合體的雙面形 -25- 201235211 成有厚度3 ·5μιη硬化被膜之耐擦傷性樹脂板。該耐擦傷性 樹脂板的雙面之硬化被膜的組成及厚度互爲相同。 〔評價〕 針對獲得之耐擦傷性樹脂板，對耐衝撃性（落球強度） 及表面硬度（鉛筆硬度）進行評價。各評價方法係如以下所 示，同時其結果示於表1。 <耐衝撃性（落球強度）> 首先，從耐擦傷性樹脂板切割出試驗片。該試驗片， 其形狀係設爲85mmx65mm，以甲基丙烯酸酯樹脂層（Α)作 爲落球面。 接著，將外形尺寸 85mm><65mm、內形尺寸 47mmx35mm、厚度1 mm的金屬製模箱配置於甲基丙烯酸 酯樹脂層（A)側，將外形尺寸8 5 m m X 6 5 m m、內形尺寸 47mmx35mm、厚度2mm的金屬製模箱配置於甲基丙稀酸 酯樹脂層（B)側，然後以該等金屬製模箱夾住試驗片，並 於其下配置85mmx65mm之厚度1mm的丙烯酸板，進而 再於其下配置85mrnx65mm的金屬板，然後固定試驗片使 甲基丙烯酸酯樹脂層（A)朝向上方。 接著，將重量36g直徑20mm φ的金屬球從l〇〇cm的 高度往試驗片的中央落下。此時，將試驗片未被破壞者評 價爲〇，試驗片被破壞者評價爲X。 -26- 201235211 <表面硬度（鉛筆硬度）> 以甲基丙烯酸酯樹脂層（A)或（B)作爲測定面，依照 JIS K5600進行測定。S -13- 201235211 To obtain a scratch-resistant resin sheet, the scratch-resistant resin sheet is a methacrylate resin layer (A) when the scratch-resistant resin sheet is used as a protective sheet for a display or a touch panel. The methacrylate resin layer (B) faces the inside (the display side and the touch panel side) toward the outside (the viewer side). Therefore, among the methacrylate resin layers (A) and (B), the methacrylate resin layer (A) facing the viewer side is easily subjected to external rinsing or load. In the laminate of the present invention, when the thickness of the methacrylate resin layer (A) is t (A) and the thickness of the methacrylate resin layer (B) is t (B), the above t (A) and t(B) constitutes a relationship having t(A) > t(B). As a result, the thickness t (A) of the methacrylate resin layer (A) which is easily subjected to external pressure or load, etc., is increased, and as a result, the impact resistance and surface hardness of the laminate are improved by the above t(A) and t ( The layer thickness ratio (t(A)/t(B)) between B) is preferably 1.2 or more, more preferably 1.5 or more. Thereby, since the thickness t (A) of the methacrylate resin layer (A) is sufficiently larger than the thickness t (B) of the methacrylate resin layer (B), the impact resistance and surface hardness of the laminate are surely improved. . The upper limit 层 of the layer thickness ratio (t(A)/t(B)) is not particularly limited, but is usually about 3.0 or less. The above t(A) is preferably 50 to 200 μm, more preferably 60 to 120 μm, and the above t(B) is preferably 1 to 150 μm, more preferably 30 to 60 μm, and most preferably 40 to 60 μm. Preferably, t(A) and t(B) have a relationship of t(A) > t(B) in the range. On the other hand, if the above t(A) and t(B) are too small, the surface hardness tends to decrease, and if the above t(A) and t(B) are too large, the laminate is resistant to heat or resistance to -14-201235211. Sex will be reduced, so it is not good. The total thickness between t(A) and t(B) is preferably 50% or less of the thickness of the entire laminate. When the total thickness of t(A) and t(B) is too large, the thickness of the entire polycarbonate resin layer becomes large, and the heat resistance and the crater resistance of the laminate are lowered, which is not preferable. The thickness of the laminate as a whole is preferably from 0.3 to 3 mm', more preferably from 〇4 to 3 mm, most preferably from 0.5 to 2 mm. The thickness of the entire laminate, or the thicknesses of the methacrylate resin layers (A) and (B), t (A), t (B), and the thickness of the polycarbonate resin layer can be extruded from the mold. The thickness of the molten laminate and the interval between the rolls sandwiching the molten laminate are adjusted. On the other hand, the above laminate can be suitably used as a resin substrate for a scratch-resistant resin sheet. Next, the scratch-resistant resin sheet of the present invention will be described. The scratch-resistant resin sheet of the present invention has a cured film formed on at least one side of the laminate. The scratch-resistant resin sheet is preferably formed with a cured film on the surface of the methacrylate resin layer (A) of the laminate. More preferably, the surface is formed on the surface of the methacrylate resin layer (B). There is a hardened film. Thereby, the scratch resistance of the scratch resistant resin sheet can be improved. Further, a hardened film may be formed only on the surface of the methacrylate resin layer (B). The layer constitution of the scratch-resistant resin sheet is as follows (1) to (iii). (i) Hardened film/methacrylate resin layer (A) / polycarbonate resin layer / methacrylate resin layer (B) (Π) methacrylate resin layer (A) / polycarbonate resin layer / Methyl propyl-15- 201235211 acrylate resin layer (B) / hardened film (iii) hardened film / methacrylate resin layer (A) / polycarbonate resin layer / methacrylate resin layer (B) / In the cured film, when the cured film is formed on both surfaces of the laminate, the composition or thickness of the cured film on both sides may be the same or different. The hardened film can be formed by applying a hardenable coating composition and hardening it. The curable coating composition contains, as an essential component, a curable compound which imparts scratch resistance, and optionally contains, for example, a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, and the like. Examples of the curable compound include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxy-modified epoxy acrylate compound, a polyester acrylate compound, and a copolymer acrylate. A compound, an alicyclic epoxy resin, a glycidyl ether epoxy resin, a vinyl ether compound, an oxetane compound, or the like. Among them, from the viewpoint of scratch resistance of the cured film, it is preferred to use a radical polymerization system such as a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, or a polyfunctional epoxy acrylate compound. As the compound, a thermopolymerizable curable compound such as an alkoxydecane or an alkyl alkoxysilane can be preferably used. These curable compounds may be cured by, for example, irradiation with an energy ray such as 'radiation or ultraviolet rays, or may be hardened by heating. These curable compounds may be used singly or in combination of a plurality of compounds. A particularly preferred sclerosing compound is a compound having at least three (meth)-16-201235211 acryloxy groups in the molecule. Here, the (meth) propylene fluorenyloxy group means an acryloxy group or a methacryloxy group, and the other means (meth) acrylate, (meth)acrylic acid, etc. )) The same meaning. Examples of the above compound having at least three (meth)acryloxycarbonyl groups in the molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and glycerin. (meth) acrylate, pentaglycerol tri(meth) acrylate, neopentyl alcohol tri or tetra (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth) acrylate, a poly(meth) acrylate of a trivalent or higher polyhydric alcohol of tetrapentaerythritol tetrakis, penta, hexa or hepta (meth) acrylate; and a compound having at least two isocyanato groups in the molecule, The number of (meth)acryloxy groups in the molecule obtained by reacting a hydroxyl group (meth) acrylate with a hydroxyl group of the isocyanate group at a molar ratio or more is three or more amine groups. Acid ester (meth) acrylate [for example, by reaction of diisocyanate with neopentyl alcohol tri(meth) acrylate to obtain a 6-functional urethane (meth) acrylate]; Hydroxyethyl) tris(meth)acrylate of iso-cyanuric acid or the like. Here, although the monomer is exemplified, a monomer such as a diploid or a triploid may be used in addition to the monomer. In addition, monomers and oligomers can also be used. These (meth) acrylate compounds may be used alone or in combination of two or more. For the above-mentioned compound having at least three (meth) acryloxy groups in the molecule, a commercially available compound can be used, and specific examples thereof include "NK HARD M101 (trade name)" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (urethane acrylate), "NK ESTER A-TMM-3L (trade name), (neopentitol III-17-201235211 acrylate), "NK ESTER Α-ΤΜΜΤ (trade name)" (neopentitol tetraacrylate), "NK ESTER Α-953 0 (trade name)" (dipentaerythritol pentaacrylate) and "NK ESTER A-DPH (trade name)" (dipopentaerythritol) "6-acrylate", "KAYARAD DPCA (trade name)" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., "NOPCO CURE 200 (trade name)" series manufactured by SAN NOPCO Co., Ltd. The "UNIDIC (trade name)" series produced by Dainippon Ink Chemical Industry Co., Ltd. Wherein, when a compound having at least three (meth) propylene oxime groups in the molecule is used as the curable compound, other curable compounds such as ethylene glycol di(meth) acrylate, two may be used as needed. Ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate having two (meth)acrylic groups in the molecule The methoxy group-containing compound is used in an amount of usually 20 parts by weight based on 100 parts by weight of the compound having at least three (meth) acryloxy groups in the molecule. When the above-mentioned curable coating composition is cured by ultraviolet rays, a photopolymerization initiator can be used as the curing catalyst. Examples of the photopolymerization initiator include benzyl, diphenyl ketone or a derivative thereof, thioxanthone, benzyl dimethyl ketal, α-hydroxyalkyl phenone, and hydroxyketone. Two or more kinds of these may be used as needed, such as an amine alkyl phenone or a fluorenyl phosphine oxide. The amount of the photopolymerization initiator to be used is usually 0.1 to 5 parts by weight based on 100 parts by weight of the curable compound. The above-mentioned photopolymerization initiator can be used, and specific examples thereof include "IRGACURE 65 1 (trade name)" and "IRGACURE 184 (trade name)" "IRGACURE 5 00", both manufactured by Ciba Specialty Chemicals Co., Ltd. (201235211 product name)", "IRGACURE 1 000 (product name)", "IRGACURE 2959 (product name)", "DAROCUR 1173 (product name)", "IRGACURE 907 (product name)", "IRGACURE 3 69 (product IRGACURE series and DAROCUR series, such as "IRGACURE 1 700 (trade name)", "IRGACURE 1 8 00 (trade name)", "IRGACURE 8 1 9 (product name)", "IRGACURE 784 (trade name)" "KAYACURE ITX (trade name)", "KAYACURE DETX-S (trade name)", "KAYACURE ΒΡ-100 (trade name)"' '"KAYACUREBMS (trade name), manufactured by Nippon Kayaku Co., Ltd. , KAYACURE series such as "KAYACURE 2-EAQ (trade name)". When the curable coating composition contains conductive particles, the antistatic property of the cured film can be imparted. As the conductive particles, for example, an antimony-tin composite oxide, a phosphorus-containing tin oxide, a tantalum pentoxide or the like, an antimony oxide, a niobium-zinc composite oxide, a titanium oxide, or an indium-tin composite oxide (ITO) inorganic particle can be preferably used. . The conductive particles may be used in the form of a sol having a solid concentration of about 10 to 30% by weight. The particle size of the conductive particles is usually 0.5 μm or less, and from the viewpoint of antistatic property and transparency of the cured film, the average particle diameter is preferably Ο.ΟΟΙμη or more, and more preferably Ο.ίμηι or less. More preferably, it is 0.0 5 μιη or less. The smaller the average particle diameter of the conductive particles, the lower the haze of the scratch-resistant resin sheet, and the transparency can be improved. The amount of the conductive particles used is usually 2 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 1 part by weight of the curable compound. The more the amount of the conductive particles used is, the more the antistatic property of the cured film is increased. However, if the amount of the conductive particles used is too large, the transparency of the cured film is lowered, which is not preferable. The conductive particles can be produced, for example, by a gas phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method, or the like. Further, the surface of the conductive particles may be surface-treated by, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an oxime coupling agent, or an aluminum coupling agent. Among them, a solvent is preferably used for the purpose of viscosity adjustment or the like, and particularly when conductive particles are contained, it is preferred to contain a solvent in order to disperse it. When a curable coating composition containing conductive particles and a solvent is prepared, for example, conductive particles and a solvent may be mixed to disperse the conductive particles in a solvent, and then the curable compound may be mixed in the dispersion, and the curable compound and the solvent may be mixed. After mixing, the conductive particles are further dispersed in the mixed solution. The solvent is preferably a soluble curable compound and is easily volatilized after coating. Further, when the conductive component is used as the coating component, a solvent which can be dispersed is preferred. Examples of the solvent include diacetone alcohol, methanol, ethanol, isopropanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol '1-methoxy-2-propanol. Alcohols; ketones, methyl ethyl hydrazine, methyl isobutyl ketone, ketones of diacetone alcohol; aromatic hydrocarbons of toluene and xylene; esters of ethyl acetate and butyl acetate; water, etc. The amount of the solvent to be used can be appropriately adjusted in accordance with the properties of the curable compound and the like. When the above-mentioned curable coating composition contains a leveling agent, it is preferred to use a polyoxygenated oil, and examples thereof include dimethylpolyphthalene oil 'benzyl polyoxyxene oil-20-201235211, and an alkyl group. Alkyl modified polyoxygenated oil, fluorine-based polyoxygenated oil, polyether modified polyoxygenated oil, fatty acid ester modified polyoxygenated oil, methyl hydrogenated polyoxygenated oil, sterol-containing polyoxynoxy Oil, alkoxy-containing polyoxygenated oil, phenol-containing polyoxygenated oil, methacryl-based modified polyoxygenated oil, amine-based modified polyoxygenated oil, carbonated modified polyoxygenated oil, methanol modified Polyoxygenated oil, epoxy modified polyoxygenated oil, thiol modified polyoxygenated oil, fluorine modified polyoxyxide oil, polyether modified polyoxyxide oil, and the like. These leveling agents may be used singly or in combination of two or more types. The amount of the leveling agent used is usually 0.01 to 5 parts by weight based on 100 parts by weight of the curable compound. The above-mentioned leveling agent can be used, and specific examples thereof include "SH200-100cs (trade name)", "SH28PA (trade name)", and "SH29PA (trade name), all manufactured by Dow Corning Toray Silicone Corporation. ), "SH30PA (product name),", "ST83PA (product name), ', "ST80PA (product name)", "ST97PA (product name)", and "ST86PA (product name)" are all BYK Japan ( "BYK-302 (trade name)", "BYK-3 07 (product name)", "BYK-320 (product name)", and "BYK-3 30 (product name)", etc. The curable coating composition obtained above is applied onto at least one side of the laminate to form a curable coating film, which is then cured to form a hard coating film, thereby obtaining a scratch-resistant resin sheet. The application of the curable coating material can be carried out by, for example, a bar coating method, a micro gravure coating method, a roll coating method, a shower coating method, a dip coating method, a spin coating method, a die coating method, a spray coating method, or the like. . The curing of the curable coating film may be performed by irradiation or heating of the energy ray depending on the type of the curable coating composition. The energy line at the time of hardening by the irradiation of the energy ray is, for example, an external line such as violet - 21 - 201235211, an electron beam, or a radiation. The conditions such as the strength and the irradiation time are appropriately selected depending on the type of the curable coating composition. Further, when it is hardened by heating, conditions such as temperature and time are appropriately selected depending on the type of the curable coating composition, and in order not to deform the resin substrate, the heating temperature is preferably preferably less than or less. When the curable coating composition contains a solvent, the curable coating film can be cured after the coating and the solvent is volatilized, and the volatilization of the solvent and the hardening of the curable coating film can be simultaneously performed. The thickness of the hardened film is preferably from 0.5 to 50 μm, more preferably from 1 to 2 〇μηι. Although the thickness of the cured film is smaller, the crack tends to be less likely to occur, but if it is too small, the scratch resistance is insufficient, so good. The obtained scratch-resistant resin sheet may be subjected to an anti-reflection treatment by a coating method, a sputtering method, a vacuum casting method, or the like, as needed. Further, an additional anti-reflective sheet may be attached to one side or both sides of the scratch-resistant resin sheet to impart an anti-reflection effect. In this way, the obtained scratch-resistant resin sheet is excellent in punching resistance and surface hardness, and thus can be used for various purposes, among which it can be preferably used as a protective sheet, and more specifically, it can be preferably used for a display protection board. Display window protection board and touch panel protection board. Examples of the type of protected display include a CRT display, a liquid crystal display, a plasma display, an EL display, and the like. In addition, the use of the protected display may be, for example, a display window of a mobile information terminal such as a television or a computer screen, a mobile phone or a PHS (Personal Handy-phone System), a PD A (Personal Digital Assistant), a digital camera, or a handheld type. The viewfinder of the video camera and the display of the action type game console -22- 201235211 window. The use of the touch panel to be protected includes, for example, a car navigation system, a mobile information terminal, an operation panel such as an industrial machine, a screen of a personal computer, a touch panel such as a mobile game machine, and the like. The method of manufacturing a protective sheet such as a display protective sheet and a touch panel protective sheet from the scratch-resistant resin sheet of the present invention is not particularly limited as long as it can produce a protective sheet which is an object of the present invention, for example, firstly, it can be used as needed. The scratch-resistant resin sheet is processed by printing, perforation, etc., and then cut into a desired size. Then set it on the display or touch panel to effectively protect the display and touch panel. In this case, the methacrylate resin layer (A) is provided on the outer side (the viewer side), and the methacrylate resin layer (B) is provided on the inner side (display side or touch panel side). The invention is further illustrated by the following examples, but the invention is not limited to the examples. Further, the following examples show % and parts of the content or the amount used, and are not based on weight unless otherwise specified. In the examples and comparative examples, the materials used for producing the laminate and the scratch-resistant resin sheet are as follows. • Polycarbonate resin: "CALIBRE 301-10 (trade name)" manufactured by Sumitomo Dow. • Methacrylate resin: a pellet of a thermoplastic polymer (glass transition temperature: 10 ° C) obtained by bulk polymerization using a monomer composed of 97.8% of methyl methacrylate and 2.2% of methyl acrylate. Here, the glass transition temperature was determined by using a differential scanning calorimeter at a heating rate of 10 ° C /min in accordance with JIS K7 1 2 1 : 1 987. -23- 201235211 • Rubber particles: rubber particles obtained by emulsion polymerization, which have a three-layer structure, the innermost layer being methyl methacrylate 93.8% and methyl acrylate 6% and allyl methacrylate 0.2% of the monomer composed of a rigid polymer obtained by polymerization, the intermediate layer is obtained by polymerization of a monomer composed of butyl acrylate 81% and styrene 17% and methacrylic acid allyl ester 2%. The elastic polymer, the outermost layer is a hard polymer obtained by polymerization of a monomer composed of methyl methacrylate 94% and 6% methyl acrylate. The weight ratio of the innermost layer, the middle layer and the outermost layer is 35:45:20. • Curing coating: 25 parts of “NK ESTER A-DPH (trade name)”, which is made of Nippon Chemical Industry Co., Ltd., mixed with photopolymerization initiator [Ciba Specialty Chemicals ( 2 parts of "IRGACURE 184 (trade name)" manufactured by the company, "ELCOMV-4514 (trade name)" manufactured by Catalyst Chemicals Co., Ltd.; solid content concentration 20%, average particle diameter A curable coating prepared by dissolving less than 1 part (2 parts solids), 24 parts of 1-methoxy-2-propanol, 24 parts of isobutanol, and 15 parts of diacetone alcohol. [Examples 1, 2 and Comparative Examples 1 to 3] [Preparation of a laminate] First, a methacrylate resin composition was prepared in terms of a material for forming a methacrylate resin layer (Α) and (Β). (a) and (b). Specifically, the methacrylate resin and the rubber particles are mixed in a super mixer according to the ratio shown below, and then melt-kneaded at 240 ° C in a two-axis extruder to obtain a methacrylate resin and Rubber particles composed of -24-201235211 methacrylate resin compositions (a) and (b) small particles. Examples 1, 2 and Comparative Examples 1 and 2 were mixed at a ratio of 86% of methacrylic resin and 14% of rubber particles. Comparative Example 3: Mixed with a ratio of 94% of methacrylate resin and 6% of rubber particles. Next, a polycarbonate resin was applied at 265 °C using a single-axis extruder (Toshiba Machine Co., Ltd.) having a diameter of 65 mm φ and using a straight shaft: a 45 mm φ single-axis extruder [Hitachi Shipbuilding Co., Ltd. The methyl acrylate vinegar resin compositions (a) and (b) are simultaneously melted at 25 5 ° C and extruded through a multi-tube mold at 260 ° C to make one side of the polycarbonate resin layer. The methacrylate resin layer (A) was laminated, and the methacrylate resin layer (B) was laminated on the other surface. Next, the extruded film was sandwiched between a pair of smooth-surfaced metal rolls to form a cooling to form the thickness shown in Table 1, and a laminate of three layers having the thickness shown in Table 1 was obtained. The laminate has a methacrylate resin layer (A) laminated on one side of the polycarbonate resin layer and a methacrylate resin layer (B) on the other side. [Preparation of scratch-resistant resin sheet] First, the obtained laminate was cut into a size of 100 mm x 80 mm, and a coating film of a curable coating material was formed on both surfaces of the laminate by a dipping method. Then, it was dried at room temperature for 1 minute, and then dried in a hot air oven at 5 ° C for 3 minutes to evaporate the solvent, and then the coating film was irradiated with an ultraviolet ray of 0.5 J/cm 2 using a high pressure mercury lamp of 1200 W to harden it. In the double-sided shape of the laminate - 25-201235211, a scratch-resistant resin sheet having a thickness of 3 · 5 μm is hardened. The composition and thickness of the double-sided cured film of the scratch-resistant resin sheet are the same. [Evaluation] With respect to the obtained scratch-resistant resin sheet, the impact resistance (falling strength) and the surface hardness (pencil hardness) were evaluated. Each evaluation method is as follows, and the results are shown in Table 1. <Plastic resistance (falling ball strength)> First, a test piece was cut out from a scratch-resistant resin plate. The test piece was set to have a shape of 85 mm x 65 mm, and a methacrylate resin layer (Α) was used as a falling spherical surface. Next, a metal mold box having an outer dimension of 85 mm >< 65 mm, an inner dimension of 47 mm x 35 mm, and a thickness of 1 mm was placed on the side of the methacrylate resin layer (A) to have an outer dimension of 8 5 mm X 6 5 mm and an inner shape. A metal mold box having a size of 47 mm x 35 mm and a thickness of 2 mm is disposed on the side of the methyl acrylate resin layer (B), and then the test piece is sandwiched by the metal mold box, and an acrylic plate having a thickness of 1 mm of 85 mm x 65 mm is disposed thereunder. Further, a metal plate of 85 mrnx 65 mm was placed thereunder, and then the test piece was fixed so that the methacrylate resin layer (A) was directed upward. Next, a weight of 36 g of a metal ball having a diameter of 20 mm φ was dropped from the height of l〇〇cm toward the center of the test piece. At this time, the test piece was evaluated as 〇 without being damaged, and the test piece was evaluated as X by the destroyer. -26-201235211 <Surface hardness (pencil hardness)> The methacrylate resin layer (A) or (B) was used as a measurement surface and measured in accordance with JIS K5600.
-27- 201235211 【Ifi fi IffiJ 陛 槲 m imJ m E 谳 S5 m is 變S m β- X OJ X CM X 00 I C0 X ΰιπ C〇3 U 變s m B- 工 C9 工 C0 X CM 工 C0 工 耐衝擊性 (落球強度） 〇 〇 X X X 整體的厚度 (jam) 507 514 507 511 517 層厚比 t(A)/t(B) in oi 00 r- 寸 d σ> d ο τ- 厚度("m) 癍£ 娱^ ⑥S 潮豳 B- CO <N 寸 106 寸 CO 狸 Ιί 菱s §幽 B- 106 CO 寸 σ> in (D CO 1豳 勘加3 磐i 358 398 358 388 444 實施例1 實施例2 比較例1 比較例2 比較例3 -28- 201235211 由表1明顯可知，實施例1及2於耐衝撃性及表面硬 度兩者皆優異。相對於此，甲基丙烯酸酯樹脂層（A)、（B) 的厚度t(A)、t(B)具有t(A)< t(B)的關係之比較例1〜3顯 示耐衝撃性不佳的結果。此外，比較例3顯示表面硬度不 佳的結果。其理由被推測係由於甲基丙烯酸酯樹脂層（A) 、（B)的厚度UA)、t(B)爲薄所致。 .3:; -29--27- 201235211 [Ifi fi IffiJ 陛槲m imJ m E 谳S5 m is change S m β- X OJ X CM X 00 I C0 X ΰιπ C〇3 U change sm B- work C9 work C0 X CM work C0 work Impact resistance (falling ball strength) 〇〇XXX Overall thickness (jam) 507 514 507 511 517 Layer thickness ratio t(A)/t(B) in oi 00 r- inch d σ> d ο τ- thickness (" m) 娱乐 娱乐 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 -28-201235211 It is apparent from Table 1 that Examples 1 and 2 are excellent in both the punching resistance and the surface hardness. In contrast, the methacrylate resin layer Comparative Examples 1 to 3 in which the thicknesses t (A) and (B) of (A) and (B) have a relationship of t (A) < t (B) showed poor results in resistance to punching. 3 shows the result of poor surface hardness. The reason is presumed to be due to the fact that the thicknesses UA) and t(B) of the methacrylate resin layers (A) and (B) are thin. .3:; -29-