201142498 六、發明說明： 【發明所屬之技術領域】 本發明關於塗料、塗覆等所用的光硬化性樹脂組成物 ，及具有其硬化皮膜之物品、其製造方法，更詳細而言係 關於高硬度且透明性、抗靜電性、保存安定性、在濕熱條 件下對基材的密接性優異，而且在藉由光照射硬化之際， 不會因塗佈生產線的搬送速度之關係而發生白化的樹脂組 成物，及具有其硬化皮膜之物品、其製造方法。 【先前技術】 聚甲基丙烯酸甲酯樹脂、聚碳酸酯樹脂、聚苯乙烯樹 脂、環狀聚烯烴樹脂、聚對苯二甲酸乙二酯樹脂、三乙醯 纖維素樹脂等的合成樹脂係具有輕量·透明性·易加工性 等的優點。因此，如此的合成樹脂近年來係利用於CD、 DVD等的光碟、液晶、EL面板等的顯示窗、各種機能性薄 膜等的各種領域。爲了提高彼等的表面耐擦傷性，一般將 透明且具有耐擦傷性的硬塗層形成在媒體的記錄及/或再 生光束入射側表面。 硬塗層的形成係將在分子中具有2個以上的（甲基） 丙烯醯基等之光反應性基的化合物，或將具有（甲基）丙 烯醯基等的光反應性基之烷氧基矽烷，在鹼性觸媒存在下 水解縮合而成之籠型構造的矽氧烷化合物（日本特開 2002-3634 1 4號公報、日本特開2004- 1 43449號公報：專利 文獻1、2)，或含有具光反應性基的烷氧基矽烷與膠態矽 -5- 201142498 石之反應物等的組成物塗佈於媒體表面，對其照射紫外線 等的活性能量線以使硬化而進行。以提高此等的抗靜電性 爲目的’檢討各種抗靜電劑的添加。有提出聚醚改性聚矽 氧與過氯酸鋰的反應物（日本特開平5-320625號公報：專 利文獻3) ’或多官能丙烯酸與過氯酸鋰的反應物（曰本 發明專利第3 67 3 5 90號公報：專利文獻4 )，多官能丙烯酸 酯與（CF3S02) 2NLi的混合物（日本特開平9-278831號公 報、日本特開200 1 -2 8 8325號公報：專利文獻5、6 )，但 耐擦傷性不充分。 因此’以改善耐擦傷性爲目的，有提出矽石及矽烷水 解物與（CF3S02) 2NLi的混合物（日本特開2005-146110 號公報、日本特開2006-70120號公報、曰本特開2008-222951號公報：專利文獻7〜9)，但由於含有溶劑，故硬 化之際必須有處理溶劑的設備，而有設備成本負擔變大的 問題。 [先行技術文獻] [專利文獻] [專利文獻1]曰本特開2002-363414號公報 [專利文獻2]日本特開20044 43449號公報 [專利文獻3]日本特開平5_3 20625號公報 [專利文獻4]日本發明專利第3 673 5 90號公報 [專利文獻5]日本特開平9_2 7 8 83 1號公報 [專利文獻6]日本特開2〇〇1·288325號公報 [專利文獻7]日本特開2〇〇5·146110號公報 201142498 [專利文獻8]日本特開2〇〇6_7〇12〇號公報 [專利文獻9]日本特開2〇〇8_222951號公報 【發明內容】 發明所欲解決的問題 本發明係鑒於上述情事而完成者，目的爲提供高硬度 且透明性、抗靜電性、保存安定性、耐濕熱性、在濕熱條 件下對基材的密接性優異，而且在藉由光照射硬化之際， 不會因塗佈生產線的搬送速度之關係而發生白化的光硬化 性樹脂組成物，及具有其硬化皮膜之物品、其製造方法。 解決問題的手段 本發明者們爲了達成上述目的，重複專心致力的檢討 ，結果發現一種含有特定比例之（1)平均粒徑爲80nm以 下的無機氧化物微粒子、（2)含有3個以上的（甲基）丙 烯酸基之化合物、（3)含有1個或2個（甲基）丙烯酸基 之化合物、（4)下述所示的脂肪族胺系離子性化合物、 (5)下述所示的鋰系離子性化合物及（6)自由基系光聚 合引發劑的光硬化性樹脂組成物，係保存安定性優異，在 藉由光照射硬化之際，不會因塗佈生產線的搬送速度之關 係而發生白化；使該組成物硬化所成之皮膜，在濕熱條件 下對支持基體的密接性良好，透明性高，耐擦傷性、抗靜 電性優異》又，此時，該光硬化性樹脂組成物係可適合在 實質上不含有溶劑的狀態下使用，而達成本發明。 201142498 因此，本發明提供下述所示之光硬化性樹脂組成物及 具有其硬化皮膜之物品、其製造方法。 [申請專利範圍第1項] 1.—種光硬化性樹脂組成物，其係含有以下者所成： (1 )平均粒徑爲80nm以下的無機氧化物微粒子， (2) 含有3個以上的（甲基）丙烯酸基之化合物， (3) 含有1個或2個（甲基）丙烯酸基之化合物， (4 ) Ι^Ι12Ι13Ι14Ν + Χ- ( R1、R2、R3、R4 係由 CH3、 C2H5、C2H4OCH3、C6H13、C8H17中選出的基，各自的基可 相同或不同；X係由N(S02CF3) 2、BF4、PF6中選出的基 )所示的離子性化合物， (5 ) Li + Y_ ( Y 係由 C104、SO2CF3 ' SO2C2F5 ' N ( S〇2CF3) 2、n(so2c2f5) 2、BF4、PF6 中選出的基）所示 的離子性化合物， (6)自由基系光聚合引發劑， 於（1) 、 （2) 、（3)成分的合計100質量份中，（ 1)成分爲25〜70質量份，（2)成分爲20〜70質量份，（ 3)成分爲5〜30質量份，相對於（1) (2) (3)成分的 合計1〇〇質量份而言，（4)成分爲0.05〜3質量份，（5) 成分爲0.1〜7質量份，（6)成分爲1〜8質量份。 [申請專利範圍第2項] 如申請專利範圍第1項之光硬化性樹脂組成物，其中 (Π成分的平均粒徑爲80nm以下的無機氧化物微粒子係 矽石微粒子。 -8- 201142498 [申請專利範圍第3項] 如申請專利範圍第2項之光硬化性樹脂組成物，其中 矽石微粒子係經含有（甲基）丙烯酸基的矽烷偶合劑處理 者。 [申請專利範圍第4項] 如申請專利範圍第1〜3項中任一項之光硬化性樹脂組 成物，其實質上不含有溶劑，且在25°C的黏度爲300mPa· s以下。 [申請專利範圍第5項] 如申請專利範圍第1〜4項中任一項之光硬化性樹脂組 成物，其係在（2)成分及/或（3)成分中預先分散有（1 )成分的混合物中，混合（4) 、 （5)及（6)成分所成 〇 [申請專利範圍第6項] 一種物品，其特徵爲形成有如申請專利範圍第1〜5項 中任一項之光硬化性樹脂組成物的硬化皮膜，全光線透過 率爲85%以上，霧度爲2%以下，依照ASTM D 1044的塔柏 (Taber)磨損試驗之荷重500g、100轉時的霧度之變化率 爲8%以下，表面電阻値爲ΐχΐ〇15ω以下。 [申請專利範圍第7項] 如申請專利範圍第6項之物品，其中形成有硬化皮膜 的物品係由含有5 0質量％以上的聚碳酸酯之樹脂組成物所 成型者。 [申請專利範圍第8項] -9- 201142498 —種物品之製造方法，其特徵爲用微凹版法在被處理 物品上塗佈如申請專利範圍第1〜5項中任一項之光硬化性 樹脂組成物，以紫外線照射使硬化而在上述被處理物品上 形成硬化皮膜。 發明的效果 本發明的光硬化性樹脂組成物係藉由對含（甲基）丙 烯酸基的化合物中所分散的無機氧化物微粒子，混合特定 量的脂肪族胺系離子性化合物與鋰系離子性化合物，而因 無機氧化物微粒子與離子性化合物的相乘效果，有助於抗 靜電性與分散穩定性的兩者之效果，即使實質上不摻合溶 劑，也可得到保存安定性良好，透明性高，耐磨損性、抗 靜電性、在濕熱條件下的密接性優異之皮膜。 【實施方式】 實施發明的形態 本發明的光硬化性樹脂組成物含有： (1 )平均粒徑爲80nm以下的無機氧化物微粒子、 (2) 含有3個以上的（甲基）丙烯酸基之化合物、 (3) 含有1個或2個（甲基）丙烯酸基之化合物、 (4 )脂肪族胺系離子性化合物、 (5 )鋰系離子性化合物、 (6)自由基系光聚合引發劑。 -10- 201142498 (1 )無機氧化物微粒子 本發明的（1 )無機氧化物微粒子例如是Si、Ti 、Zn、Zr、In、Sn、Sb、Ce、Fe等的氧化物微粒子、 等複合氧化物微粒子等。作爲金屬氧化物微粒子，具 例如可舉出矽石、氧化鋁、氧化锆、二氧化鈦、氧化 的微粒子。 此等無機氧化物微粒子的平均粒徑爲80nm以下， 爲50nm以下。若使用比8〇nm大者，則穩定性變差， 皮膜上看到粒狀的異物，或損害透明性。再者，其下 常爲10nm以上。又，本發明中，平均粒徑係可藉由動 散射光子相關法的粒度分布測定裝置進行測定。 特佳的無機氧化物微粒子係矽石微粒子，若平均 爲5 Onm以下則更佳。又，矽石微粒子亦可使用能期待 射率等效果的中空、多孔質者。於矽石微粒子之中， 使用經具有活性能量線反應性基的水解性矽烷化合物 面修飾者。如此的反應性矽石微粒子係在藉由使組成 化之際的活性能量線照射，發生交聯反應，固定於聚 基質中。 此處，作爲具有活性能量線反應性基的水解性矽 合物，可舉出含有（甲基）丙烯酸基的矽烷偶合劑， 地可例示γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ·甲 烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基 矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧 、Α1 或此 體地 姉等 較佳 會在 限通 態光 粒徑 低折 較宜 所表 物硬 合物 烷化 具體 基丙 三氯 甲基 基丙 -11 - 201142498 基甲基二氯矽烷、γ-甲基丙烯醯氧基丙基二甲基甲氧基矽 烷、γ-甲基丙烯醯氧基丙基二甲基乙氧基矽烷、γ-甲基丙 烯醯氧基丙基二甲基氯矽烷、γ-丙烯醯氧基丙基三甲氧基 矽烷、γ-丙烯醯氧基丙基三乙氧基矽烷、丙烯醯氧基丙 基三氯矽烷、γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙 烯醯氧基丙基甲基二乙氧基矽烷、γ-丙烯醯氧基丙基甲基 二氯矽烷、γ-丙烯醯氧基丙基二甲基甲氧基矽烷、γ-丙烯 醯氧基丙基二甲基乙氧基矽烷、γ-丙烯醯氧基丙基二甲基 氯矽烷、γ-丙烯醯氧基甲基三甲氧基矽烷、γ-丙烯醯氧基 甲基三乙氧基矽烷、γ·丙烯醯氧基甲基三氯矽烷、γ-丙烯 醯氧基甲基甲基二甲氧基矽烷、γ-丙烯醯氧基甲基甲基二 乙氧基矽烷、γ-丙烯醯氧基甲基甲基二氯矽烷、γ-丙烯醯 氧基甲基二甲基甲氧基矽烷、γ-丙烯醯氧基甲基二甲基乙 氧基矽烷、γ-丙烯醯氧基甲基二甲基氯矽烷。 又’具有活性能量線反應性基的水解性矽烷化合物之 表面修飾量，對於粒子而言較佳爲0.1〜10質量％，更佳爲 〇 · 5〜8質量％，特佳爲1〜5質量％。 作爲藉由具有活性能量線反應性基的水解性矽烷化合 物進行表面修飾之方法，可舉出在矽石微粒子存在下，將 具有活性能量線反應性基的水解性矽烷化合物水解之方法 ’該情況下所副生成的具有活性能量線反應性基的水解性 矽烷化合物之水解物，會使保存安定性變差，或成爲使硬 度降低的原因等，故必須消除彼等。 較佳爲使用將此等（1)無機氧化物微粒子在一次粒 -12- 201142498 子的狀態下分散在後述之（2)含有3個以上的（甲基）丙 烯酸基之化合物、（3)含有1個或2個（甲基）丙烯酸基 之化合物中者，藉由以1次粒子存在，可得到透明性等之 外觀良好的皮膜。 具體地，可舉出使用分散劑或分散機器，將無機氧化 物微粒子物理地分散於含（甲基）丙烯酸基的化合物中之 方法，或於分散有無機氧化物微粒子的溶液中添加含（甲 基）丙烯酸基的化合物後，餾去本來的分散劑之方法。 (2)含有3個以上的（甲基）丙烯酸基之化合物 本發明之（2)含有3個以上的（甲基）丙烯酸基之化 合物，係由（1)無機氧化物微粒子及（3)含有1個或2個 (甲基）丙烯酸基之化合物以及硬化性成分的主成分所構 成者，形成在硬化後所得之皮膜的基質。含有3個以上的 (甲基）丙烯酸基之化合物，係使（1)成分的無機氧化 物微粒子分散同時爲黏結劑成分，藉由該化合物，可得到 耐磨損性優異、高硬度之硬化物。 (2)成分之含有（甲基）丙烯酸基的化合物，係在 分子內具有3個以上的（甲基）丙烯酸基之化合物，例如 亦可舉出三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇四 (甲基）丙烯酸酯、甲氧基化季戊四醇四（甲基）丙烯酸 酯、乙氧基化季戊四醇四（甲基）丙烯酸酯、貳三羥甲基 丙烷四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸 酯、季戊四醇三（甲基）丙烯酸酯、三丙烯酸化異三聚氰 -13- 201142498 酸酯等。又，亦可列舉3官能以上的胺基 、聚酯丙烯酸酯、具有活性能量線反應性 化合物之水解縮合物等的聚合物成分，但 定。 此等化合物係可僅使用1種，也可倂用 (3)含有1個或2個（甲基）丙烯酸基 本發明的（3)含有1個或2個（甲基 合物，係與（1 )無機氧化物微粒子及（： 的（甲基）丙烯酸基之化合物一同作爲硬 分，且形成在硬化後所得之皮膜的基質者 特別地，其係使組成物的黏度降低用 使與聚甲基丙烯酸甲酯樹脂、聚碳酸酯樹 脂 '環狀聚烯烴樹脂、聚對苯二甲酸乙二 纖維素樹脂等的密接性提高用之成分》 (3)成分爲了使組成物的黏度降低 爲lOOmPa. s以下，特佳爲50mPa. s以下 別的限制，但通常爲ImPa . s以上。再者 轉式黏度計進行測定（以下相同）。 此含有（甲基）丙烯酸基的化合物， 性提高，較佳爲在分子內具有羥基、環氧 。又，皮膚刺激性PII値較佳爲4.0以上。] 的皮府刺激性PII値係可由文獻等來調查。 例如，可舉出（甲基）丙烯酸羥乙酯 甲酸酯丙烯酸酯 基的水解性矽烷 未必受此等所限 2種以上。 之化合物 )丙烯酸基之化 2 )含有3個以上 化性成分的主成 〇 的成分，同時係 脂、聚苯乙烯樹 醋樹脂、三乙醯 ，在2 5 °C的黏度 。下限係沒有特 ，黏度係可藉旋 尤其爲了使密接 基等的官能基者 者，各化合物 (甲基）丙烯 -14- 201142498 酸環氧丙酯、（甲基）丙烯酸四氫糠酯、1，6-己二醇二（ 甲基）丙烯酸酯 '三乙二醇二（甲基）丙烯酸酯、二丙烯 酸化異三聚氰酸酯 '環氧乙烷改性雙酚A二（甲基）丙烯 酸酯等，但未必受此等所限定。 此等化合物係可僅使用1種，也可倂用2種以上》 在（1)成分與（2)成分和（3)成分的合計1〇〇質量 份中’ （1)成分的摻合量爲25〜70質量份，較佳爲35〜 60質量份，在（1)成分與（2)成分和（3)成分的合計 100質量份中’ （2)成分的摻合量爲20〜70質量份，較佳 爲30〜55質量份，在（1)成分與（2)成分和（3)成分 的合計100質量份中，（3 )成分的摻合量爲5〜30質量份 ，較佳爲10〜20質量份。 在（1)成分與（2)成分和（3)成分的合計100質量 份中，若（1 )成分的摻合量未達2 5質量份，則硬度降低 ，得不到充分的耐磨損性，若超過7〇質量份，則皮膜的外 觀變差。又，（2)成分的摻合量若未達20質量份，則分 散穩定性差，皮膜外觀變差，若超過70質量份，則硬度降 低。（3 )成分的摻合量若未達5質量份，則密接性變差， 若超過30質量份，則硬度降低。 (4 )脂肪族胺系離子性化合物 本發明中，（4 ) RjR^RSR/N + X— ( R1、R2、R3、R4 係 由 CH3、C2H5、C2H4OCH3、C6H13、C8H17 中選出的基，各 自的基可相同或不同；X係由N(S02CF3) 2、BF4、PFd -15- 201142498 選出的基）所示的脂肪族胺系離子性化合物，係使用作爲 相溶性及溶解性良好的抗靜電劑。又，具有分散性改善的 效果，故藉由添加而可抑制保存時的凝聚或沈降，更且在 光照射的硬化之際，可防止因塗佈生產線的搬送速度之關 係而皮膜發生白化。於此等之中，特佳爲常溫（通常5〜 4 0°C，尤其25°C )下爲液體的脂肪族胺系離子性化合物。 此處 ’ R1〜R4 係由 CH3、C2H5、C2H4OCH3、C6HI3、 C8H17中選出的基，各自的基可相同或不同。又，X係由n (SO2CF3 ) 2、BF4、PF6 中選出的基。作爲 i^Wr/n+X· 所示的脂肪族胺系離子性化合物，具體地可舉出下述者等 〇 (C2H5) 4N + BF4-、( ch3 ) ( C2H5 ) 3N + BF4·、( ch3 )(C2H5 ) 2 ( C2H4OCH3 ) n + bf4·、（ ch3) 3 ( C6H13 ) N + BF4-、( CH3 ) ( CgHi 7 ) 3N + BF4' ' ( C2H5 ) 4N + PF6- ' (CH3 ) ( C2H5 ) 3n + pf6-、 ( CH3 ) ( C2H5 ) 2 ( C2H4OCH3 ) N + PF6-、( ch3 ) 3 ( C6H 丨 3) N + PF6·、( ch3 ) (C 8 H 1 7 ) 3N + PF 6* ' (C2H5) 4N+ ( CF3SO2) 2N ' ' (CH3) (C2H5 ) 3n+ ( CF3S02 ) 2N-、 ( ch3 ) ( C2H5 ) 2 ( C2H4OCH3 ) N+ ( CF3SO2 ) 2N·、( CH3 ) 3 ( C6H,3 ) N+ ( CF3SO2) 2N、 ( C H 3 ) ( C 8 H 1 7 ) 3 N+ ( C F3 S O 2 ) 2N ' 相對於（1)成分與（2)成分和（3)成分的合計100 質量份而言，（4)成分的摻合量爲〇·〇5〜3質量份，較佳 爲0.1〜2.5質量份，特佳爲0.1〜2質量份。摻合量若過少 ，則得不到抗靜電效果，更且穩定性亦變差。摻合量若過 -16- 201142498 多，則硬度降低。 (5 )鋰系離子性化合物 於本發明中，（5 ) Li + Y- ( Y係由C104、 S02C2F5 ' N ( SO2CF3 ) 2、N ( SO2C2F5) 2 ' BF4 出的基）所示的鋰系離子性化合物’係與脂肪族 性化合物同樣地，使用作爲相溶性及溶解性良好 劑。又，具有分散性改善的效果，故藉由添加而 存時的凝聚或沈降，更且在光照射的硬化之際’ 塗佈生產線的搬送速度之關係而皮膜發生白化。 作爲Li + Υ·所示的鋰系離子性化合物，具體 下述者等。201142498 6. Technical Field of the Invention The present invention relates to a photocurable resin composition for coating, coating, and the like, and an article having the same, a method for producing the same, and more particularly to high hardness. Further, it is excellent in transparency, antistatic property, storage stability, adhesion to a substrate under wet heat conditions, and resin which is whitened by the relationship of the transfer speed of the coating line when it is cured by light irradiation. A composition, an article having the hardened film, and a method of producing the same. [Prior Art] A synthetic resin such as a polymethyl methacrylate resin, a polycarbonate resin, a polystyrene resin, a cyclic polyolefin resin, a polyethylene terephthalate resin, or a triacetyl cellulose resin has Lightweight, transparent, and easy to process. Therefore, such a synthetic resin has been used in various fields such as a disc such as a CD or a DVD, a display window such as a liquid crystal or an EL panel, and various functional thin films. In order to improve their surface scratch resistance, a transparent and scratch-resistant hard coat layer is generally formed on the recording and/or reproducing beam incident side surface of the medium. The formation of the hard coat layer is a compound having two or more photoreactive groups such as (meth) acryl fluorenyl groups in the molecule, or an alkoxy group having a photoreactive group such as a (meth) acryl fluorenyl group. A decyl alkane compound having a cage structure which is hydrolyzed and condensed in the presence of a basic catalyst (Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. Or a composition containing a photoreactive group-containing alkoxy decane and a colloidal 矽-5-201142498 stone reactant, which is applied to a surface of a medium, and irradiated with an active energy ray such as ultraviolet rays to harden it. . In order to improve the antistatic properties of these, the addition of various antistatic agents was reviewed. There is a reaction product of polyether-modified polyfluorene oxide and lithium perchlorate (Japanese Patent Laid-Open No. Hei 5-320625: Patent Document 3) 'or a reaction product of polyfunctional acrylic acid and lithium perchlorate (the present invention patent) Japanese Patent Laid-Open Publication No. Hei 9-278831, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. 6), but the scratch resistance is not sufficient. Therefore, in order to improve the scratch resistance, a mixture of vermiculite and decane hydrolyzate and (CF3S02) 2NLi has been proposed (JP-A-2005-146110, JP-A-2006-70120, and Sakamoto Kaikai 2008- Japanese Patent Publication No. 222951 (Patent Documents 7 to 9). However, since a solvent is contained, it is necessary to have a device for treating a solvent at the time of curing, and there is a problem that the equipment cost burden is increased. [Patent Document 1] [Patent Document 1] JP-A-2002-363414 [Patent Document 2] JP-A-2004-43449 [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei 5-3 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Problem The present invention has been made in view of the above circumstances, and an object thereof is to provide high hardness, transparency, antistatic property, storage stability, heat and humidity resistance, excellent adhesion to a substrate under moist heat conditions, and irradiation by light. In the case of hardening, a photocurable resin composition which does not become whitened due to the transfer speed of the coating line, an article having the cured film, and a method for producing the same. Means for Solving the Problems In order to achieve the above object, the inventors of the present invention have repeatedly conducted an intensive review and found that (1) inorganic oxide fine particles having a specific particle diameter of 80 nm or less and (2) containing three or more (a) (meth)acrylic acid-based compound, (3) compound containing one or two (meth)acrylic groups, (4) an aliphatic amine-based ionic compound shown below, (5) shown below The photocurable resin composition of the lithium-based ionic compound and the (6) radical photopolymerization initiator is excellent in storage stability, and is not affected by the transfer speed of the coating line when it is cured by light irradiation. And whitening occurs; the film formed by curing the composition is excellent in adhesion to the support substrate under moist heat conditions, and has high transparency, excellent scratch resistance and antistatic property. Further, at this time, the photocurable resin composition The present invention can be suitably used in a state where it does not substantially contain a solvent. Thus, the present invention provides a photocurable resin composition shown below, an article having the cured film, and a method for producing the same. [Patent Application No. 1] 1. A photocurable resin composition comprising the following: (1) inorganic oxide fine particles having an average particle diameter of 80 nm or less, and (2) containing three or more a (meth)acrylic group-based compound, (3) a compound containing one or two (meth)acrylic groups, (4) Ι^Ι12Ι13Ι14Ν + Χ- (R1, R2, R3, R4 are derived from CH3, C2H5, The groups selected from C2H4OCH3, C6H13, and C8H17 may be the same or different; X is an ionic compound represented by N(S02CF3) 2, BF4, and PF6, (5) Li + Y_ (Y An ionic compound represented by C104, SO2CF3 'SO2C2F5 'N (S〇2CF3) 2, n (so2c2f5) 2, BF4, PF6 selected), (6) a radical photopolymerization initiator, In the total of 100 parts by mass of the components (1) and (3), the component (1) is 25 to 70 parts by mass, the component (2) is 20 to 70 parts by mass, and the component (3) is 5 to 30 parts by mass. With respect to the total of 1 part by mass of the components (1), (2) and (3), the component (4) is 0.05 to 3 parts by mass, and the component (5) is 0.1 to 7 parts by mass, and the component (6) is 1 to 8 quality Copies. [Application No. 2] The photocurable resin composition of the first aspect of the invention, wherein the inorganic oxide fine particles having an average particle diameter of 80% or less are fine particles of vermiculite. -8- 201142498 [Application The third aspect of the invention is the photocurable resin composition according to claim 2, wherein the vermiculite fine particles are treated by a (meth)acrylic group-containing decane coupling agent. [Application No. 4] The photocurable resin composition according to any one of claims 1 to 3, which does not substantially contain a solvent, and has a viscosity at 25 ° C of 300 mPa·s or less. [Application No. 5] The photocurable resin composition according to any one of the items 1 to 4, wherein the component (1) is preliminarily dispersed in the component (2) and/or the component (3), and the mixture is mixed (4). (5) and (6) components are formed [Applicable Patent No. 6] An article characterized by being formed into a cured film of a photocurable resin composition according to any one of claims 1 to 5, The total light transmittance is 85% or more, and the haze is 2%. The load of the Taber abrasion test according to ASTM D 1044 is 500 g, the change rate of haze at 100 rpm is 8% or less, and the surface resistance 値 is ΐχΐ〇 15 ω or less. [Application No. 7] The article of the sixth aspect of the invention, wherein the article formed with the hardened film is formed of a resin composition containing 50% by mass or more of polycarbonate. [Application No. 8] -9- 201142498 - Article And a photocurable resin composition according to any one of claims 1 to 5, which is cured by ultraviolet irradiation and is cured in the article to be treated. The surface of the photocurable resin composition of the present invention is obtained by mixing a specific amount of an aliphatic amine-based ionic compound with inorganic oxide fine particles dispersed in a (meth)acrylic group-containing compound. And a lithium-based ionic compound, and the synergistic effect of the inorganic oxide fine particles and the ionic compound contributes to the effects of both antistatic property and dispersion stability, even if substantially When the solvent is blended, a film having excellent storage stability, high transparency, abrasion resistance, antistatic property, and excellent adhesion under wet heat conditions can be obtained. [Embodiment] Embodiment of the invention The photocurability of the invention The resin composition contains: (1) inorganic oxide fine particles having an average particle diameter of 80 nm or less, (2) a compound containing three or more (meth)acrylic groups, and (3) one or two (methyl) groups. Acrylic group-based compound, (4) aliphatic amine-based ionic compound, (5) lithium-based ionic compound, and (6) radical photopolymerization initiator. -10- 201142498 (1) Inorganic oxide fine particles of the present invention (1) The inorganic oxide fine particles are, for example, oxide fine particles of Si, Ti, Zn, Zr, In, Sn, Sb, Ce, Fe, or the like, or composite oxide fine particles. Examples of the metal oxide fine particles include vermiculite, alumina, zirconia, titania, and oxidized fine particles. The inorganic oxide fine particles have an average particle diameter of 80 nm or less and 50 nm or less. When the ratio is larger than 8 〇 nm, the stability is deteriorated, and a particulate foreign matter is observed on the film or the transparency is impaired. Further, it is usually 10 nm or more. Further, in the present invention, the average particle diameter can be measured by a particle size distribution measuring apparatus using a moving scattered photon correlation method. Particularly preferred inorganic oxide fine particles are fine particles of vermiculite, and if the average is 5 Onm or less, it is more preferable. Further, as the fine particles of the vermiculite, a hollow or porous one which can achieve an effect such as a rate of radiation can be used. Among the vermiculite fine particles, those modified with a hydrolyzable decane compound having an active energy ray-reactive group are used. Such a reactive vermiculite fine particle system is subjected to a crosslinking reaction by irradiation with an active energy ray at the time of composition, and is fixed in a polyplast. Here, examples of the hydrolyzable conjugate having an active energy ray-reactive group include a (meth)acrylic group-containing decane coupling agent, and γ-methacryloxypropyltrimethoxy decane can be exemplified. , γ·Methoxy oxypropyl triethoxy decane, γ-methyl propylene methoxy propyl decane, γ-methyl propylene methoxy propyl methyl dimethoxy decane, γ-acryl hydrazine Oxypropyl propyl diethoxy decane, γ-methyl propylene oxime, oxime 1 or this body lanthanum, etc., preferably have a low refractive index in the light state of the pass-through state. Propyltrichloromethylpropylpropane-11 - 201142498 methyl dichloromethane, γ-methyl propylene methoxypropyl dimethyl methoxy decane, γ-methyl propylene methoxy propyl dimethyl Ethoxy decane, γ-methyl propylene methoxy propyl dimethyl chloro decane, γ-propylene methoxy propyl trimethoxy decane, γ-propylene methoxy propyl triethoxy decane, propylene oxime Oxypropyl propyl trichloromethane, γ-propylene methoxy propyl methyl dimethoxy decane, γ-propylene methoxy propyl methyl diethoxy decane, γ-propyl醯-methoxypropylmethyldichlorodecane, γ-propylene methoxypropyl dimethyl methoxy decane, γ-acryloxypropyl dimethyl ethoxy decane, γ-propylene methoxy propyl Methyl chlorochloromethane, γ-propylene methoxymethyl trimethoxy decane, γ-propylene methoxymethyl triethoxy decane, γ· propylene methoxymethyl trichloro decane, γ-acryl hydrazine Oxymethylmethyldimethoxydecane, γ-acryloxymethylmethyldiethoxydecane, γ-acryloxymethylmethyldichlorodecane, γ-acryloxymethyloxymethyl Dimethyl methoxy decane, γ-propylene methoxymethyl dimethyl ethoxy decane, γ-propylene methoxymethyl dimethyl chloro decane. Further, the amount of surface modification of the hydrolyzable decane compound having an active energy ray-reactive group is preferably from 0.1 to 10% by mass, more preferably from 5% to 8% by mass, particularly preferably from 1 to 5 by mass. %. A method of surface-modifying a hydrolyzable decane compound having an active energy ray-reactive group includes a method of hydrolyzing a hydrolyzable decane compound having an active energy ray-reactive group in the presence of vermiculite fine particles. The hydrolyzate of the hydrolyzable decane compound having an active energy ray-reactive group formed by the next generation may deteriorate storage stability or cause a decrease in hardness, and so it is necessary to eliminate them. It is preferred to use the (1) inorganic oxide fine particles dispersed in a state of primary particles -12 to 201142498 in the state of (2) a compound containing three or more (meth)acrylic groups, and (3) containing Among the one or two (meth)acrylic group-containing compounds, a film having a good appearance such as transparency can be obtained by the presence of primary particles. Specifically, a method of physically dispersing inorganic oxide fine particles in a (meth)acrylic group-containing compound using a dispersing agent or a dispersing device, or adding a solution to a solution in which inorganic oxide fine particles are dispersed may be mentioned. After the acrylic group-based compound, the original dispersant is distilled off. (2) A compound containing three or more (meth)acrylic groups (2) A compound containing three or more (meth)acrylic groups, (1) inorganic oxide fine particles and (3) One or two (meth)acrylic-based compounds and a main component of the curable component form a matrix of the film obtained after curing. The compound containing three or more (meth)acrylic groups is obtained by dispersing the inorganic oxide fine particles of the component (1) as a binder component, and by using the compound, a cured product having excellent abrasion resistance and high hardness can be obtained. . (2) The (meth)acrylic group-containing compound of the component is a compound having three or more (meth)acrylic groups in the molecule, and for example, trimethylolpropane tri(meth)acrylate may also be mentioned. , pentaerythritol tetra (meth) acrylate, methoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, decyl hydroxymethyl propane tetra (meth) acrylate, Dipentaerythritol hexa(meth) acrylate, pentaerythritol tri(meth) acrylate, triacrylated iso-cyanide-13- 201142498 acid ester, and the like. Further, a polymer component such as a trifunctional or higher amine group, a polyester acrylate, or a hydrolysis condensate having an active energy ray-reactive compound may be used. These compounds may be used alone or in combination with (3) one or two (meth)acrylic acid basic inventions (3) containing one or two (methyl compounds, with (1) The inorganic oxide fine particles and the (meth)acrylic group-containing compound together as a hard component, and formed into a matrix of the film obtained after hardening, in particular, the viscosity of the composition is lowered to make polymethyl group A component for improving the adhesion between a methyl acrylate resin, a polycarbonate resin, a cyclic polyolefin resin, and a polyethylene terephthalate resin. (3) A component is used to reduce the viscosity of the composition to 100 mPa. In the following, it is particularly preferably 50 mPa·s or less, but it is usually equal to or less than ImPa.s. Further, the measurement is carried out by a rotary viscometer (the same applies hereinafter). The compound containing a (meth)acryl group is improved in properties. In order to have a hydroxyl group and an epoxy in the molecule, the skin irritation PII is preferably 4.0 or more. The Pifu stimulating PII oxime system can be investigated by literature, etc. For example, hydroxyethyl (meth)acrylate can be mentioned. Hydrolyzability of ester acrylate group The decane is not necessarily limited to two or more of these. The compound is a acrylate group; 2) a component containing three or more chemical components, and a resin, a polystyrene tree vinegar resin, and a triacetone. 2 5 °C viscosity. The lower limit is not particularly limited, and the viscosity can be rotated, especially for the functional group such as a bonding group, each compound (meth) propylene-14- 201142498 acid propyl acrylate, (meth) methacrylate, 1 ,6-hexanediol di(meth)acrylate 'triethylene glycol di(meth)acrylate, diacrylated isocyanurate' ethylene oxide modified bisphenol A di(methyl) Acrylate, etc., but not necessarily limited by these. These compounds may be used alone or in combination of two or more. In the total of 1 part by mass of the component (1) and the component (2) and the component (3), the amount of the component (1) is blended. It is 25 to 70 parts by mass, preferably 35 to 60 parts by mass, and the amount of the component (2) is 20 to 70 in the total of 100 parts by mass of the component (1) and the component (2) and the component (3). The mass part is preferably 30 to 55 parts by mass, and the blending amount of the component (3) is 5 to 30 parts by mass in 100 parts by mass of the total of the component (1) and the component (2) and the component (3). Good for 10 to 20 parts by mass. When the blending amount of the component (1) is less than 25 parts by mass in the total of 100 parts by mass of the component (1) and the component (2) and the component (3), the hardness is lowered, and sufficient wear resistance is not obtained. If it exceeds 7 parts by mass, the appearance of the film deteriorates. In addition, when the amount of the component (2) is less than 20 parts by mass, the dispersion stability is poor, and the appearance of the film is deteriorated. When the amount is more than 70 parts by mass, the hardness is lowered. When the blending amount of the component (3) is less than 5 parts by mass, the adhesion is deteriorated, and if it exceeds 30 parts by mass, the hardness is lowered. (4) Aliphatic amine-based ionic compound In the present invention, (4) RjR^RSR/N + X- (R1, R2, R3, and R4 are selected from CH3, C2H5, C2H4OCH3, C6H13, and C8H17, respectively. The bases may be the same or different; X is an aliphatic amine-based ionic compound represented by N(S02CF3) 2, BF4, PFd -15- 201142498, and is used as an antistatic having good compatibility and solubility. Agent. Further, since it has an effect of improving the dispersibility, it is possible to suppress aggregation or sedimentation during storage by addition, and it is possible to prevent whitening of the film due to the relationship between the transfer speed of the coating line and the curing of the light. Among these, an aliphatic amine-based ionic compound which is liquid at normal temperature (usually 5 to 40 ° C, especially 25 ° C) is particularly preferred. Here, 'R1 to R4' are selected from CH3, C2H5, C2H4OCH3, C6HI3, and C8H17, and the respective groups may be the same or different. Further, X is a group selected from n (SO2CF3) 2, BF4, and PF6. Specific examples of the aliphatic amine-based ionic compound represented by i^Wr/n+X· include the following: (C2H5) 4N + BF4-, (ch3) (C2H5) 3N + BF4·, ( Ch3 )(C2H5 ) 2 ( C2H4OCH3 ) n + bf4·, ( ch3 ) 3 ( C6H13 ) N + BF4-, ( CH3 ) ( CgHi 7 ) 3N + BF4 ' ' ( C2H5 ) 4N + PF6- ' (CH3 ) ( C2H5) 3n + pf6-, (CH3) ( C2H5 ) 2 ( C2H4OCH3 ) N + PF6-, ( ch3 ) 3 ( C6H 丨 3 ) N + PF6 ·, ( ch3 ) (C 8 H 1 7 ) 3N + PF 6 * '(C2H5) 4N+ ( CF3SO2) 2N ' ' (CH3) (C2H5 ) 3n+ ( CF3S02 ) 2N-, ( ch3 ) ( C2H5 ) 2 ( C2H4OCH3 ) N+ ( CF3SO2 ) 2N·, ( CH3 ) 3 ( C6H, 3 N + ( CF3SO2) 2N, (CH 3 ) ( C 8 H 1 7 ) 3 N+ ( C F3 SO 2 ) 2N ' with respect to 100 parts by mass of the total of the component (1), the component (2), and the component (3) In other words, the blending amount of the component (4) is 5 to 3 parts by mass, preferably 0.1 to 2.5 parts by mass, particularly preferably 0.1 to 2 parts by mass. If the blending amount is too small, an antistatic effect is not obtained, and stability is also deteriorated. If the blending amount is more than -16 to 201142498, the hardness is lowered. (5) Lithium-based ionic compound In the present invention, (5) Li + Y- (Y is a lithium-based system represented by C104, S02C2F5 'N (SO2CF3) 2, N (SO2C2F5) 2 'BF4) The ionic compound 'is used as a compatibility and solubility good agent similarly to an aliphatic compound. In addition, since the effect of the dispersibility is improved, the film is whitened by the aggregation or sedimentation at the time of the addition, and the relationship between the transfer speed of the coating line and the transfer speed of the coating line. Specific examples of the lithium-based ionic compound represented by Li + Υ· are as follows.
Li + Cl〇4.、Li + S02CF3·、Li + S〇2C2F5·、Li + N )2.、Li + N ( S02C2F5) 2·、Li + BF4·、Li + PF6· 相對於（1)成分與（2)成分和（3)成分β 質量份而言，（5)成分的摻合量爲0.1〜7質量 爲0.2〜5質量份，特佳爲0.5〜4質量份。摻合量 則得不到抗靜電效果，而且在紫外線照射時皮膜 更且安定性亦變差。摻合量若過多，則硬度降低 倂用（4) 、（5)成分的離子性化合物而使 各自單獨使用時相比，即使無溶劑皮膜成型性亦 得到表面平滑性、透明性優異的皮膜，確認密接 又’可降低表面電阻値，可得到抗靜電性優異的 S02CF3、 、pf6中選 胺系離子 的抗靜電 可抑制保 可防止因 地可舉出 (so2cf3 勺合計100 份，較佳 若過少， 會白化， 〇 用時，與 優異，可 性優異。 皮膜。 -17- 201142498 (6)自由基系光聚合引發劑 於本發明的組成物中，含有（6)自由基系光聚合引 發劑。作爲自由基系光聚合引發劑，可由苯乙酮系、苯偶 姻系、醯基膦氧化物系、二苯基酮系、噻吨酮系等通常者 中選擇。具體地，可舉出二苯基酮、苯偶醯、米其勒酮、 噻吨酮衍生物、苯偶姻乙基醚、二乙氧基苯乙酮、苄基二 甲基縮嗣、2 -經基-2 -甲基苯丙嗣、1-經基環己基苯基嗣、 2 -經基-2 -甲基-1-苯基丙院-1-酮、2，2-二甲氧基-1,2-二苯 基乙烷-1-酮、1-[4-(2-羥基乙氧基）-苯基]-2-羥基-2-甲 基-1-丙烷-1-酮、2-羥基- l-{4-[4-(2-羥基-2-甲基-丙醯基 )-苄基]苯基}-2-甲基-丙烷-1-酮、氧基苯基乙酸2-[2-氧 代-2-苯基乙醯氧基乙氧基]乙酯與氧基苯基乙酸2- (2-羥 基乙氧基）乙酯的混合物、醯基膦氧化物衍生物、2 -甲基-1-(4-(甲硫基）本基）-2 -嗎琳基丙院-1-酿、4 -苯甲醜 基-4’-甲基二苯基硫化物、2,4,6-三甲基苯甲醯基二苯基膦 等。 此等係可單獨使用，也可組合2種以上使用。於此等 之中，從表面硬化性良好之點來看，較佳爲苄基二甲基縮 酮、1-翔基環己基苯基酮、2 -經基-2 -甲基-1-苯基丙院-1_ 酮、2-甲基-1-(4-(甲硫基）苯基）-2-嗎啉基丙烷-1-酮 、4 -苯甲醯基_4’_甲基二苯基硫化物、2,4,6 -三甲基苯甲醯 基二苯基膦。 相對於（1)成分與（2)成分和（3)成分的合計100 質量份而言，自由基系光聚合引發劑的摻合量爲1〜8質量 -18- 201142498 份，較佳爲2〜6質量份。摻合量若過少則硬化性變差，若 過多則密接性降低。 於本發明的光硬化·性樹脂組成物中，在不損害本發明 目的之範圔內，視需要亦可更含有（4) ，（5)成分以外 的離子性化合物、矽烷偶合劑、聚合抑制劑、抗氧化劑、 紫外線吸收劑、光安定劑、消泡劑、均平劑、表面張力降 低劑等，但較佳爲實質上不含有溶劑。此處，所謂的實質 上不含有，就是意味在組成物中容許含有3質量％以下，尤 其1質量％以下之比例。 本發明的組成物係可依照常用方法將上述各成分均勻 混合而得，但於本發明中，宜將上述（1)成分與（2)成 分或（3)成分預先混合，將此與剩餘的成分混合。 再者’較佳爲將此等組成物在25 °C的黏度調整至 3 00mPa. s以下，尤其220mPa. s以下。黏度若過高，則塗 佈作業性變差，容易發生筋狀斑等。再者，本組成物在 25°C的黏度較佳爲10mPa· s以上。 本發明的光硬化性樹脂組成物係藉由在表面上需要耐 磨損性、抗靜電性之賦予的物品，具體地在由含有5 0質量 %以上、尤其70〜100質量％的聚碳酸酯的樹脂組成物所成 型的物品’如再生專用光碟、光記錄碟、光磁性記錄碟等 的光資訊媒體之表面，更詳細而言爲在記錄或再生光束入 射側表面’或在光學透鏡、光學濾波器、防反射膜 '防反 射膜下層膜’及在液晶顯示器、CRT顯示器、電漿顯示器 、EL顯示器等的各種顯示元件等的表面上塗佈，成爲硬化 -19- 201142498 皮膜，藉以可賦予此等表面的耐擦傷性、防污性，具有此 硬化皮膜的物品係可成爲耐擦傷性、耐磨損性及抗靜電性 優異者。 具體地，能成爲得到以濁度計（NDH2000，日本電色 工業製）所測定的全光線透過率爲85 %以上，及霧度爲2% 以下，依照ASTM D1 044的塔柏磨損試驗之荷重500g、100 轉時的霧度之變化率爲8%以下，以超絕緣計（東亞電波工 業（股）製SM-8210)所測定的表面電阻値爲1χ1〇15Ω以下 之特性者。 作爲形成上述光硬化性樹脂組成物的皮膜之方法，可 舉出藉由輥塗法、旋塗法、桿塗法、微凹版法等來製作皮 膜，於此等之中，較佳爲藉由微凹版法進行塗佈，藉由紫 外線照射進行硬化而製作皮膜。所形成的皮膜之膜厚更佳 爲0.1〜50μιη，特佳爲0.5〜30μπι的範圍。膜厚若過薄，則 耐磨損性會降低，而若過厚，則耐龜裂性會降低。 作爲使光硬化性樹脂組成物硬化用的光源，通常使用 含有200〜45 Onm範圍的波長之光的光源、例如高壓水銀燈 、超高壓水銀燈、無電極燈、金屬鹵化物燈、氙燈、碳弧 燈等。照射量係沒有特別的限制，但較佳爲1 0〜 5,000mJ/cm2，特佳爲20〜2,000mj/cm2。光照射機所致的 硬化係有分批式與輸送帶式，較佳爲生產性高的輸送帶式 。硬化時間通常爲〇 . 0 1〜6 0秒，較佳爲0 · 1〜1 0秒。當時的 塗佈生產線之搬送速度係沒有特別的限制，但較佳爲0. 1 〜40m/min，特佳爲1〜20m/min的範圍。搬送速度若慢則 -20- 201142498 生產性差，若快則搬送時有容易發生損傷的問題。 成型爲上述物品的樹脂組成物中所用的聚碳酸酯，較 佳爲藉由溶液法或熔融法使二價酚與碳酸酯前驅物反應而 製造的芳香族聚碳酸酯樹脂，作爲二價酚的代表例，可舉 出2,2-雙（4-羥基苯基）丙烷（通稱雙酚A) 、1,1-雙（4-羥基苯基）乙烷、1,1-雙（4-羥基苯基）環己烷、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、雙（4-羥基苯基）硫化物、雙（4-羥基苯 基）颯、1，1_雙（4-羥基-3-甲基苯基）環己烷、2,2-雙（ 4-羥基-3-甲基苯基）丙烷及2，2’-甲基- 4,4’-二苯基二醇等 。較佳的二價酚爲雙（4-羥基苯基）烷系，特佳爲雙酚A 〇 作爲碳酸酯前驅物，可舉出羰基鹵、碳酸酯、鹵甲酸 酯等，具體地可舉出光氣、碳酸二苯酯、二價酚的二鹵甲 酸酯等。 於製造聚碳酸酯樹脂時，上述二價酚可爲單獨或倂用 2種以上，而且視需要可使用分子量調節劑、分枝劑、觸 媒等。 聚碳酸酯樹脂的分子量以黏度平均分子量表示爲 l.oxio4 〜10.0X104，較佳爲 1.5X104 〜4.5X104，更佳爲 1·8χ1 04〜3.〇xl 04。本發明所言的黏度平均分子量係由在 20°C將0.7g聚碳酸酯樹脂溶解於100ml二氯甲烷中之溶液所 求得的比黏度（tlsp)插入下式而求得者。 η5ρ/ο = [η] + 0.45 χ [η]2ο (但[η]爲極限黏度） -21 - 201142498 [η] = 1.23 x 1 〇·4Μ° 83 c= 0.7 又，於成形成爲物品的樹脂組成物中’視需要亦可摻 合添加劑，例如亞磷酸酯、磷酸酯、膦酸酯等的熱安定劑 (0.001〜0.1質量％ )、三唑系、苯乙酮系、水楊酸酯系 等的紫外線吸收劑（0.1〜〇.7質量％ )、四溴雙酚A、四溴 雙酚A的低分子量聚碳酸酯、十溴二苯基醚等的難燃劑（3 〜1 5質量％ )、著色劑、螢光增白劑等。 〔實施例〕 以下顯示實施例及比較例來具體說明本發明，惟本發 明不受下述的實施例所限制。再者，於下述例中，黏度係 以旋轉黏度計所測定之値》 [實施例1 ] 混合80質量份的分散有γ_甲基丙烯醯氧基丙基三甲氧 基矽烷處理矽石之乙氧基化季戊四醇四丙烯酸酯（以下， S-PETTA;矽石濃度50質量％，矽石粒徑30nm) 、2〇質量 份的己二醇二丙烯酸酯（以下，HDODA，PII値5.5) 、0.2 質量份的（CH3 ) ( C8H17 ) 3N+ ( CF3S02 ) 2N* (以下， MTOTFSI ) 、1.8 質量份的 Li+ ( CF3S02 ) 2Ν·(以下，Li + Cl〇4., Li + S02CF3·, Li + S〇2C2F5·, Li + N )2, Li + N ( S02C2F5) 2·, Li + BF4·, Li + PF6· relative to (1) The blending amount of the component (5) is from 0.2 to 5 parts by mass, preferably from 0.5 to 5 parts by mass, particularly preferably from 0.5 to 4 parts by mass, based on the (2) component and the (3) component. The blending amount does not give an antistatic effect, and the film is more stable and unstable when irradiated with ultraviolet rays. When the amount of the mixture is too large, the hardness is lowered, and the ionic compound of the components (4) and (5) is used, and the film having excellent surface smoothness and transparency is obtained even when the solvent-free film formability is used. It is confirmed that the adhesion can be reduced, and the surface resistance can be reduced. The antistatic property of the selective amine-based ions of S02CF3 and pf6, which are excellent in antistatic properties, can be suppressed. The total number of so2cf3 spoons is 100 (preferably too small) (6) A radical photopolymerization initiator contains (6) a radical photopolymerization initiator in the composition of the present invention. -17- 201142498 (6) A radical photopolymerization initiator The radical photopolymerization initiator may be selected from the group consisting of acetophenone-based, benzoin-based, mercaptophosphine-based, diphenylketone, and thioxanthone. Diphenyl ketone, benzophenone, mitoxone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-cyano-2 Methamphetil, 1-cyclohexylphenyl fluorene, 2-cyano-2-methyl-1 -Phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-l-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl }-2-Methyl-propan-1-one, 2-[2-oxo-2-phenylethenyloxyethoxy]ethyl oxyphenylacetate and 2-(2-phenyloxyphenylacetate) a mixture of -hydroxyethoxy)ethyl ester, a mercaptophosphine oxide derivative, 2-methyl-1-(4-(methylthio)benzyl)-2 - phenanthrene 4-Benzyl acetamido-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzhydryldiphenylphosphine, etc. These may be used singly or in combination of two or more. Among these, from the viewpoint of good surface hardenability, benzyldimethylketal, 1-cylcyclohexyl phenyl ketone, 2-cyano-2-methyl-1 is preferable. -Phenylpropanoid-1_ ketone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylpropan-1-one, 4-benzylidene-yl- 4'-A Diphenyl sulfide, 2,4,6-trimethylbenzimidyl diphenylphosphine. Relative to the total of (1) component and (2) component and (3) component The blending amount of the radical photopolymerization initiator is from 1 to 8 masses -18 to 201142498 parts, preferably from 2 to 6 parts by mass. If the blending amount is too small, the hardenability deteriorates, and if too much, the adhesion is poor. In the photohardenable resin composition of the present invention, an ionic compound other than the components (4) and (5) or a decane coupling agent may be further contained as needed within the scope of the object of the present invention. A polymerization inhibitor, an antioxidant, an ultraviolet absorber, a photostabilizer, an antifoaming agent, a leveling agent, a surface tension reducing agent, etc., but preferably does not substantially contain a solvent. Here, the term "substantially not contained" means that the composition is allowed to contain 3% by mass or less, particularly preferably 1% by mass or less. The composition of the present invention can be obtained by uniformly mixing the above components according to a usual method. However, in the present invention, it is preferred to premix the above component (1) with the component (2) or (3), and the remaining Ingredients are mixed. Further, it is preferable to adjust the viscosity of the compositions at 25 ° C to 300 mPa·s or less, especially 220 mPa·s or less. If the viscosity is too high, the coating workability is deteriorated, and tendon spots are likely to occur. Further, the viscosity of the composition at 25 ° C is preferably 10 mPa·s or more. The photocurable resin composition of the present invention is an article which is required to impart abrasion resistance and antistatic property on the surface, specifically, a polycarbonate containing 50% by mass or more, particularly 70 to 100% by mass. The article formed by the resin composition is such as a surface of an optical information medium such as a reproduction-only optical disk, an optical recording disk, a magneto-optical recording disk, or the like, more specifically, on the incident side surface of the recording or reproducing beam' or in an optical lens or optical The filter, the anti-reflection film 'anti-reflection film underlayer film', and the surface of various display elements such as a liquid crystal display, a CRT display, a plasma display, and an EL display are coated, and the film is cured -19-201142498, thereby giving The scratch resistance and the antifouling property of these surfaces, and the article having such a hardened film can be excellent in scratch resistance, abrasion resistance, and antistatic property. Specifically, it is possible to obtain a total light transmittance of 85% or more and a haze of 2% or less as measured by a turbidity meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the load of the Taber abrasion test according to ASTM D1 044. The change rate of haze at 500 g and 100 rpm is 8% or less, and the surface resistance 测定 measured by a super insulation meter (SM-8210 manufactured by Toa Denshi Kogyo Co., Ltd.) is 1 χ 1 〇 15 Ω or less. The method of forming the film of the photocurable resin composition may be a film formed by a roll coating method, a spin coating method, a rod coating method, a micro gravure method, or the like. The micro gravure method was applied, and the film was formed by hardening by ultraviolet irradiation. The film thickness of the formed film is more preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 30 μm. If the film thickness is too thin, the abrasion resistance is lowered, and if it is too thick, the crack resistance is lowered. As a light source for curing the photocurable resin composition, a light source containing light having a wavelength in the range of 200 to 45 Onm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, or a carbon arc lamp is generally used. Wait. The irradiation amount is not particularly limited, but is preferably from 10 to 5,000 mJ/cm 2 , particularly preferably from 20 to 2,000 mJ/cm 2 . The hardening by the light irradiation machine is a batch type and a conveyor belt type, and is preferably a highly productive conveyor belt type. The hardening time is usually 〇 0 1 to 60 seconds, preferably 0 · 1 to 1 0 seconds. The conveying speed of the coating line at that time is not particularly limited, but is preferably from 0.1 to 40 m/min, particularly preferably from 1 to 20 m/min. If the transport speed is slow, -20- 201142498 The productivity is poor. If it is fast, there is a problem that it is easy to be damaged when transported. The polycarbonate used for molding the resin composition of the above article is preferably an aromatic polycarbonate resin produced by reacting a divalent phenol with a carbonate precursor by a solution method or a melt method, as a divalent phenol. Representative examples include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, and 1,1-bis(4-hydroxyl). Phenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, Bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)fluorene, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis (4- Hydroxy-3-methylphenyl)propane and 2,2'-methyl-4,4'-diphenyl diol and the like. A preferred divalent phenol is a bis(4-hydroxyphenyl)alkane, particularly preferably a bisphenol A oxime as a carbonate precursor, and examples thereof include a carbonyl halide, a carbonate, a haloformate, and the like. A phosgene, a diphenyl carbonate, a dihaloform of a divalent phenol, or the like. In the production of the polycarbonate resin, the divalent phenol may be used alone or in combination of two or more kinds, and a molecular weight modifier, a branching agent, a catalyst or the like may be used as needed. The molecular weight of the polycarbonate resin is expressed by a viscosity average molecular weight of 1.oxio4 to 10.0X104, preferably 1.5X104 to 4.5X104, more preferably 1·8χ1 04~3.〇xl 04. The viscosity average molecular weight as used in the present invention is determined by inserting a specific viscosity (tlsp) obtained by dissolving a solution of 0.7 g of a polycarbonate resin in 100 ml of dichloromethane at 20 ° C into the following formula. Η5ρ/ο = [η] + 0.45 χ [η]2ο (but [η] is the ultimate viscosity) -21 - 201142498 [η] = 1.23 x 1 〇·4Μ° 83 c= 0.7 Also, the resin that is formed into an article In the composition, an additive such as a thermal stabilizer (0.001 to 0.1% by mass) such as a phosphite, a phosphate, or a phosphonate, a triazole system, an acetophenone system, or a salicylate system may be blended as needed. A UV absorber (0.1 to 7.7% by mass), a tetrabromobisphenol A, a low molecular weight polycarbonate of tetrabromobisphenol A, a flame retardant such as decabromodiphenyl ether (3 to 15 mass) %), colorant, fluorescent whitening agent, and the like. [Examples] The present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited by the examples described below. Further, in the following examples, the viscosity was measured by a rotational viscometer. [Example 1] 80 parts by mass of yttrium-methacryloxypropyltrimethoxysilane dispersed with vermiculite was mixed. Ethoxylated pentaerythritol tetraacrylate (hereinafter, S-PETTA; vermiculite concentration: 50% by mass, vermiculite particle size: 30 nm), and two parts by mass of hexanediol diacrylate (hereinafter, HDODA, PII 値 5.5), 0.2 parts by mass of (CH3) (C8H17) 3N+ (CF3S02) 2N* (hereinafter, MTOTFSI) and 1.8 parts by mass of Li+ (CF3S02) 2Ν· (hereinafter,
LiTFSI) 、3 質量份的 Dar〇CUre 1173(以下，D1173; 2 -羥 基-2-甲基-I-苯基丙烷-i-酮，自由基系光聚合引發劑， CIBA特殊化學品公司製，商品名），而得到在25^的黏度 -22- 201142498 爲193 mPa . s之光硬化性樹脂.組成物。藉由微凹版輥塗佈 法（康井精機公司製支數200)，以厚度成爲5 μπι的方式， 將此光硬化性樹脂組成物塗佈於芳香族聚碳酸酯薄膜（由 雙酚Α與光氣所製造的黏度平均分子量2.3x1 〇4之芳香族聚 碳酸酯薄膜；寬度140mm，厚度92μιη)上，接著使用具有 160W高壓水銀燈的輸送帶式紫外線照射裝置（ EYEGRAPHICS公司製）來製作硬化皮膜。當時的條件係 搬送速度2m/min ’累計照射量爲l，〇〇〇mJ/cm2 »使用所得 之透明皮膜，進行下述所示的評估。表1中顯示此等的結 果0 保存安定性= 於4 0。(：、1 4日後，目視判斷是否有沈降物’藉由下述 基準進行評估。 〇：無沈降物 X :有沈降物 皮膜透明性： 根據JIS K 7105，使用濁度計（NDH2000，日本電色 工業製）來測定已硬化的膜’評估全光線透過率、霧度（ haze )。作爲白化的基準，將實用上沒有問題的全光線透 過率85%以上、霧度2%以下當作合格。 耐擦傷性、耐磨損性： -23- 201142498 根據ASTM D 1044，使用塔柏磨損試驗機（使用磨損 輪CS-10F)，進行硬化皮膜的磨損試驗（ 500g荷重，100轉 )，使用濁度計（NDH2000,日本電色工業製）來測定磨 損試驗前後的硬化皮膜之霧度，將磨損試驗後的霧度-磨 損試驗前的霧度當作△霧度（△霧度爲8以下時係耐擦傷性 、耐磨損性良好）。 表面電阻値= 使用超絕緣計（東亞電波工業（股）製SM-8210 )， 在25°C、5 0%RH的環境下測定。 濕熱密接性： 在6 0°C、95%RH的環境下放置240小時後，於常溫放 置24小時後，根據JIS K 5400，在塗佈面製作10x10的棋盤 格，貼上赛珞玢膠帶，向上方拉起，確認剝離狀況。 〇：無異常 X :棋盤格的1 /3以上剝離的地方爲1格以上 於塔柏磨損試驗中，△霧度爲4且耐磨損性亦高。又 ，表面電阻値爲低到1χ1〇Ι2Ω。 [實施例2〜8及比較例1〜12] 同樣地，如以下述表1、2所示，替換摻合量而得到膜 ，進行評估。表1、2中顯示此等的結果。 -24- 201142498 【表1】 (質量份) 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 S-PETTA 80 80 80 80 80 80 80 90 S-PETTA-2 HDODA 20 20 20 20 20 20 20 10 MTOTFSI 0· 2 0· 2 0· 2 0 2 0. 1 1. 8 0. 2 0. 2 LiTFSI 1· 8 0. 9 3. 6 6 1. 8 1. 8 1. 8 1. 8 D1173 3 3 3 3 3 3 5 3 矽石量(質量％) 38 38 37 37 38 38 37 43 黏度(mPa . s) 193 181 237 265 185 230 220 284 評估結果 保存穩定性 〇 〇 〇 〇 〇 〇 〇 〇 全光線透過率(%) 92 92 92 92 92 92 92 92 Haze(%) 0. 4 1. 4 0· 2 0. 2 1. 8 0· 2 0· 2 0. 3 耐擦傷性-耐摩損性 Δ霧度(％) 4 3 6 7 4 6 3 3 表面電阻(Ω) 1X1012 1X1012 6X1011 1X1011 3X1012 6X109 1X1012 1X1012 濕熱密接性 〇 〇 〇 〇 〇 〇 〇 〇 S-PETTA:分散有γ-甲基丙烯醯氧基丙基三甲氧基矽 烷處理矽石的乙氧基化季戊四醇四丙烯酸酯，矽石濃度50 質量％，矽石粒徑30nm S-PETTA-2 ：分散有γ-甲基丙烯醯氧基丙基三甲氧基 矽烷處理矽石的乙氧基化季戊四醇四丙烯酸酯，矽石濃度 50質量％，砂石粒徑120nm HDODA:己二醇二丙烯酸酯 MTOTFSI ： ( CH3 ) ( C8Hi7 ) 3N+(CF3S02) 2N +LiTFSI), 3 parts by mass of Dar〇CUre 1173 (hereinafter, D1173; 2-hydroxy-2-methyl-I-phenylpropane-i-one, a radical photopolymerization initiator, manufactured by CIBA Specialty Chemicals Co., Ltd., The product name), and the viscosity at 25^-22- 201142498 is 193 mPa. s light curable resin. Composition. The photocurable resin composition was applied to an aromatic polycarbonate film by a micro-gravure roll coating method (manufactured by Kane Seiki Co., Ltd., 200) to a thickness of 5 μm (by bisphenol oxime and A sulphur gas having a viscosity average molecular weight of 2.3×1 〇4, an aromatic polycarbonate film, a width of 140 mm, and a thickness of 92 μm, followed by a conveyor belt type ultraviolet ray irradiation apparatus (manufactured by EYEGRAPHICS Co., Ltd.) having a 160 W high-pressure mercury lamp to produce a hardened film. . The conditions at that time were a transport speed of 2 m/min. The cumulative exposure amount was 1, and 所得mJ/cm2 » was obtained using the obtained transparent film, and the evaluation shown below was performed. The results of these 0 are shown in Table 1. The preservation stability = at 40. (:, after 14 days, visually judge whether there is sediment)' Evaluation by the following criteria. 〇: no sediment X: sedimentation film transparency: According to JIS K 7105, turbidity meter (NDH2000, Nippon Electric Co., Ltd.) In the measurement of the cured film, the total light transmittance and the haze are evaluated. As a basis for whitening, the total light transmittance of practically no problem is 85% or more and the haze is 2% or less. Scratch resistance, abrasion resistance: -23- 201142498 According to ASTM D 1044, using a Taber abrasion tester (using the wear wheel CS-10F), the abrasion test of the hardened film (500 g load, 100 rpm), using turbidity A haze (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze of the hardened film before and after the abrasion test, and the haze before the abrasion-wear test after the abrasion test was regarded as the Δ haze (when the haze was 8 or less) It is excellent in abrasion resistance and abrasion resistance. Surface resistance 値 = Ultra-insulation meter (SM-8210, manufactured by Toa Dentsu Kogyo Co., Ltd.), measured at 25 ° C, 50% RH. : Place 240 at 60 ° C, 95% RH After the lapse of 24 hours at room temperature, a 10x10 checkerboard was prepared on the coated surface according to JIS K 5400, and the celluloid tape was attached and pulled up to confirm the peeling condition. 〇: No abnormality X: checkerboard The peeling point of 1 / 3 or more is 1 or more in the Taber abrasion test, the haze is 4 and the abrasion resistance is also high. Further, the surface resistance 値 is as low as 1 χ 1 〇Ι 2 Ω. [Examples 2 to 8 and Comparative Examples 1 to 12] Similarly, as shown in the following Tables 1 and 2, the film was obtained by substituting the blending amount, and the results were evaluated. The results are shown in Tables 1 and 2. -24- 201142498 [Table 1] ( Parts by mass) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 S-PETTA 80 80 80 80 80 80 80 90 S-PETTA-2 HDODA 20 20 20 20 20 20 20 10 MTOTFSI 0· 2 0· 2 0· 2 0 2 0. 1 1. 8 0. 2 0. 2 LiTFSI 1· 8 0. 9 3. 6 6 1. 8 1. 8 1. 8 1. 8 D1173 3 3 3 3 3 3 5 3 Amount of vermiculite (% by mass) 38 38 37 37 38 38 37 43 Viscosity (mPa. s) 193 181 237 265 185 230 220 284 Evaluation results Storage stability〇〇〇〇〇〇〇〇Light transmittance (%) 92 92 92 92 92 92 92 92 Haze(%) 0. 4 1. 4 0· 2 0. 2 1. 8 0· 2 0· 2 0. 3 Scratch resistance - wear resistance Δ Haze (%) 4 3 6 7 4 6 3 3 Surface resistance (Ω) 1X1012 1X1012 6X1011 1X1011 3X1012 6X109 1X1012 1X1012 Wet heat bonding 〇〇〇〇〇〇〇〇S-PETTA: γ-methyl propylene oxide dispersed Ethoxylated pentaerythritol tetraacrylate of vermiculite treated with propyltrimethoxydecane, vermiculite concentration 50% by mass, vermiculite particle size 30nm S-PETTA-2: γ-methylpropenyloxypropyl group dispersed Trimethoxysilane treatment of vermiculite ethoxylated pentaerythritol tetraacrylate, vermiculite concentration 50% by mass, sand particle size 120nm HDODA: hexanediol diacrylate MTOTFSI : ( CH3 ) ( C8Hi7 ) 3N + ( CF3S02 ) 2N +
LiTFSI ： Li+ ( CF3S02 ) 2N· D1173 : Darocure 1173，2-羥基-2 -甲基-1-苯基丙烷-1-酮，CIBA特殊化學品公司製，商品名 -25- 201142498 【表2】LiTFSI : Li+ ( CF3S02 ) 2N· D1173 : Darocure 1173, 2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by CIBA Specialty Chemicals, trade name -25- 201142498 [Table 2]
摻合量(質量份） 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 比較例 8 比較例 9 比較例 10 比較例 11 比較例 12 S-PETTA 80 80 80 80 80 80 80 40 60 100 S-PETTA-2 80 100 _ HDODA 20 20 20 20 20 20 20 60 40 20 MTOTFSI 0. 2 0. 2 0. 02 4 0. 2 0. 2 0. 2 0· 2 0. 2 0. 2 0. 2 LiTFSI 0. 05 8 1. 8 1. 8 1. 8 1. 8 1. 8 1· 8 1. 8 1. 8 1. 8 D1173 3 3 3 3 3 10 0. 5 3 3 3 3 3 矽石;MS%) 39 39 36 38 37 36 39 19 29 48 38 48 黏度(mPa.s) 170 215 285 184 240 201 182 45 72 370 168 305 評估結果 保存穏定性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 全光線透過率(％) 92 92 92 92 92 92 91 91 91 91 88 87 Haze(%) 6 5 0. 2 0. 5 0. 3 0. 6 .0· 4 0. 5 0. 5 0. 7 2. 2 2. 4 耐擦傷性·耐摩損性 Δ霧度（％) 3 3 9 3 10 2 15 12 10 4 5 5 表面電阻(Ω) >1X10^ 1X1012 5X109 4X1015 3X105 1X1012 1X1012 1X1012 2X1012 2X1012 2X1012 2X1012 濕熱密接性 〇 〇 X 〇 X X 〇 〇 〇 X 〇 X -26-Blending amount (parts by mass) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 S-PETTA 80 80 80 80 80 80 80 40 60 100 S-PETTA-2 80 100 _ HDODA 20 20 20 20 20 20 20 60 40 20 MTOTFSI 0. 2 0. 2 0. 02 4 0. 2 0. 2 0. 2 0· 2 0. 2 0. 2 0. 2 LiTFSI 0. 05 8 1. 8 1. 8 1. 8 1. 8 1. 8 1· 8 1. 8 1. 8 1. 8 D1173 3 3 3 3 3 10 0. 5 3 3 3 3 3 vermiculite; MS%) 39 39 36 38 37 36 39 19 29 48 38 48 Viscosity (mPa.s) 170 215 285 184 240 201 182 45 72 370 168 305 Evaluation results Preservation stability 〇〇〇〇〇〇X total light transmittance (%) 92 92 92 92 92 92 91 91 91 91 88 87 Haze(%) 6 5 0. 2 0. 5 0. 3 0. 6 .0· 4 0. 5 0. 5 0. 7 2. 2 2. 4 Scratch resistance and abrasion resistance Δ Haze (%) 3 3 9 3 10 2 15 12 10 4 5 5 Surface resistance (Ω) >1X10^ 1X1012 5X109 4X1015 3X105 1X1012 1X1012 1X1012 2X1012 2X1012 2X1012 2X1012 Wet heat bonding 〇〇X 〇XX 〇〇〇X 〇X -26-