201124490 六、發明說明 【發明所屬之技術領域】 本發明係有關一種保存安定性優異的導電性微粒子分 散液、含導電性微粒子之光硬化性組成物及由該組成物所 得的含導電性微粒子之硬化膜，更詳言之，係有關在塑 膠、金屬、木材、紙、玻璃、石板等之各種基材表面上形 成透明性優異且具有抗靜電機能之含導電性微粒子之硬化 膜所得的光硬化性組成物、由該組成物所得的透明性優異 且具有抗靜電機能之硬化膜，及調製該光硬化性組成物時 所使用的保存安定性優異的導電性微粒子分散液。 【先前技術】 近年來’爲防止各種基材之表面刮傷（擦傷）或防止污 染時之保護塗佈材料、或印刷油墨之接著材料，要求具有 優異的塗佈性，且可在各種基材表面上形成硬度、耐擦傷 性、耐摩擦性、低翹曲性、密接性、透明性、耐藥品性、 塗膜面之外觀等優異的硬化膜之硬化性組成物。 另外，使用於平坦面板顯示裝置、觸控板、塑膠光學 零件等之用途時’除上述要求外，更爲要求可形成透明性 優異且具有抗靜電機能之透明導電膜等硬化膜的硬化性組 成物。 此外’於液晶顯示裝置、陰極管顯示裝置等之影像顯 示裝置及光學製品中’係使用防止反射膜（硬化膜）。該防 止反射膜除具有高透明性及低反射率之特性外，被要求具[Technical Field] The present invention relates to a conductive fine particle dispersion excellent in storage stability, a photocurable composition containing conductive fine particles, and conductive fine particles obtained from the composition. The hardened film, more specifically, is a photohardening obtained by forming a cured film containing conductive fine particles having excellent transparency and antistatic function on the surface of various substrates such as plastic, metal, wood, paper, glass, slate, and the like. The conductive composition, the cured film which is excellent in transparency and has an antistatic function, and the conductive fine particle dispersion liquid which is excellent in storage stability used when preparing the photocurable composition. [Prior Art] In recent years, in order to prevent surface scratching (scratching) of various substrates or to prevent contamination, the coating material or the printing ink is required to have excellent coating properties and can be used in various substrates. A curable composition of a cured film excellent in hardness, scratch resistance, abrasion resistance, low warpage, adhesion, transparency, chemical resistance, and appearance of a coating film surface is formed on the surface. In addition, when used in applications such as flat panel display devices, touch panels, and plastic optical components, in addition to the above requirements, it is required to form a hardenable film of a cured film such as a transparent conductive film having excellent transparency and antistatic function. Things. Further, in the image display device and the optical product such as a liquid crystal display device or a cathode tube display device, an antireflection film (cured film) is used. The anti-reflection film is required to have high transparency and low reflectivity.
C -5- 201124490 有耐擦傷性及防止灰塵或垃圾等異物附著的機能。因此， 防止反射膜之高折射率層，除高透明性及高折射率特性 外，被要求具有優異的耐擦傷性及抗靜電特性。 其次’賦予該硬化膜具有抗靜電機能之方法，已知有 在硬化性組成物中添加界面活性劑、導電性聚合物或主要 由金屬氧化物所形成的導電性微粒子等之方法，特別是考 慮製作具有永久抗靜電效果之膜爲目的時，一般而言使用 添加導電性微粒子的方法。該添加導電性微粒子之方法， 係在樹脂溶液或溶劑中配合螯合劑，且在該配合物中分散 無機氧化物的方法（例如參照專利文獻1及2)。 [習知技術文獻] [專利文獻] [專利文獻1]日本特開2001-139,847號公報 [專利文獻2]日本特開2001-139,889號公報 【發明內容】 有關上述用途所使用的導電性微粒子分散液及其硬化 性組成物，被要求導電性微粒子之粒徑小且分散液之保存 安定性優異。上述專利文獻1及2中記載的螯合劑，由於 與金屬形成金屬螯合物，會有在分散處理過程中被使用的 金屬製機器或塗佈機材被腐蝕的問題。 本發明係有鑑於上述問題者，以提供（1 )可在基材表 面上形成透明性優異且同時具有抗靜電機能之硬化膜，在 分散處理過程中使用的金屬製機器或塗佈機材不會被腐蝕 -6- 201124490 的含導電性微粒子之光硬化性組成物，（2)由該含導電性 微粒子之光硬化性組成物所得的透明導電膜等之各種硬化 膜，（3)具有由該含導電性微粒子之光硬化性組成物所得 的硬化膜之顯示裝置，以及（4)調製該含導電性微粒子之 光硬化性組成物時所使用的保存安定性優異的導電性微粒 子分散液爲目的。 本發明人等爲達成上述各種目的時，再三深入硏究檢 討的結果，發現藉由在分散媒中分散導電性微粒子及金屬 錯合物，可得保存安定性優異的導電性微粒子分散液，此 外，發現藉由使用該導電性微粒子分散液，可得在分散處 理過程中不會有金屬製機器或塗佈機材被腐蝕的含導電性 微粒子之光硬化性組成物，遂而完成本發明。 換言之，本發明之導電性微粒子分散液，其特徵爲由 導電性微粒子、金屬錯合物及分散媒所成，較佳者每100 質量份之導電性微粒子中，金屬錯合物之含量爲2〜45質 量份，分散媒之含量爲40〜1000質量份。 另外，於本發明中，除透明導電特性外，尙企求高折 射率特性’該導電性微粒子分散液，其特徵爲由折射率爲 1 .8以上之高折射率微粒子、導電性微粒子、不含烷氧化 物之金屬錯合物及分散媒所成，水分爲3質量％以下，較 佳者每1 00質量份高折射率微粒子中，導電性微粒子之含 量爲30〜900質量份，金屬錯合物之含量爲3〜450質量 份及分散媒之含量爲60〜9000質量份。 其次’本發明之含導電性微粒子之光硬化性組成物， 201124490 其特徵爲由導電性微粒子、金屬錯合物、活性能量線硬化 性化合物、光聚合引發劑及分散媒所成，較佳者每1 00質 量份導電性微粒子中，金屬錯合物之含量爲2〜45質量 份，分散媒之含量爲40〜1 000質量份，活性能量線硬化 性化合物之含有量爲10〜1000質量份，且每100質量份 活性能量線硬化性化合物中，光聚合引發劑之含量爲0.1 〜2 0質量份β 而且，於本發明中被要求高折射率特性之透明導電膜 形成用之含導電性微粒子的光硬化性組成物，其特徵爲由 折射率爲1 . 8以上之高折射率微粒子、導電性微粒子、不 含烷氧化物之金屬錯合物、活性能量線硬化性化合物、光 聚合引發劑及分散媒所成，水分爲3質量％以下，較佳者 每1 〇〇質量份高折射率微粒子中，導電性微粒子之含量爲 30〜900質量份，金屬錯合物之含量爲3〜450質量份， 分散媒之含量爲60〜70000質量份及活性能量線硬化性化 合物之含量爲14〜1 0000質量份，且每1〇〇質量份該活性 能量線硬化性化合物中，光聚合引發劑之含量爲0. 1〜2 0 質量份。 此外’本發明之含導電性微粒子之硬化膜，其特徵爲 在基材上塗佈或印刷上述之含導電性微粒子之光硬化性組 成物，予以硬化所得者，較佳者折射率爲1.4 5〜1 . 9 0，光 透過率爲75%以上’霾度爲2.0%以下，且表面電阻値爲 1012Ω/□以下。 而且，於本發明中，被要求高折射率特性之透明導電 -8 - 201124490 膜形成用之含導電性微粒子的硬化膜，其特徵爲在基材上 塗佈或印刷上述之透明導電膜形成用之含導電性微粒子之 光硬化性組成物，予以硬化所得者，較佳者折射率爲1 . 5 5 〜1.90，光透過率爲85%以上，霾度爲1.5%以下，且表面 電阻値爲1〇12Ω/□以下。 [發明效果] 藉由本發明，可提供（1 )分散液之保存安定性優異的 導電性微粒子分散液，（2)可在基材表面上形成透明性優 異且具有抗靜電機能之硬化膜，在分散處理過程中所使用 的金屬製機器或塗佈機材不會被腐蝕的含導電性微粒子之 光硬化性組成物，以及（3 )由該組成物所得的透明優異且 具有抗靜電機能之含導電性微粒子之硬化膜。 此外，藉由本發明，可提供（1 )可在基材表面上形成 透明性優異且具有高折射率、抗靜電機能之透明導電膜， 在分散處理過程中使用的金屬製機器或塗佈機材不會被腐 蝕的光硬化性透明導電膜形成用組成物，（2)由該透明導 電膜形成用組成物所得的透明性優異且具有高折射率及抗 靜電機能之透明導電膜，（3)具有該透明導電膜之顯示裝 置，以及（4)調製該透明導電膜形成用組成物時所使用的 保存安定性優異的分散液。 [爲實施發明時之最佳形態] 於下述中，具體地說明本發明之實施形態。 -9 - 201124490 本發明之導電性微粒子分散液，含有導電性微粒子、 金屬錯合物及分散媒。有關本發明所使用的導電性微粒子 之形狀，沒有特別的限制。導電性微粒子之導電性，係體 積電阻値爲1 〇7Ω · cm以下，較佳者爲103Ω · cm以下。此 外，有關導電性微粒子之尺寸大小，通常使用一次粒徑爲 1〜500nm者，較佳者爲10〜l〇〇nm。 另外，於本發明中透明導電膜等特別被要求具有高折 射率特性時，其導電性微粒子分散液係含有折射率爲1.8 以上之高折射率微粒子、導電性微粒子、不含烷氧化物之 金屬錯合物及分散媒，水分爲3質量％以下。有關本發明 所使用的高折射率微粒子及導電性微粒子之形狀，沒有特 別的限制。而且，有關高折射率微粒子及導電性微粒子之 尺寸大小，通常可使用一次粒徑爲1〜500nm者，較佳者 爲 10 〜100nm〇 有關本發明所使用的導電性微粒子之種類，只要是可 達成目的者即可，沒有特別的限制，可使用市售品等之習 知品。例如可使用ITO、ΑΤΟ、氧化錫、氧化鋅、氧化 銦、銻酸鋅及五氧化銻等之金屬氧化物或構成此等金屬氧 化物之金屬的氫氧化物。有關氧化錫，亦可使用摻雜有磷 等元素者。而且，有關氧化鋅，亦可使用摻雜有鎵或鋁 者。此外，亦可爲金、銀、銅、鉛、鋁等之金屬微粒子及 有機導電性微粒子。此等之導電性微粒子，可僅使用1 種，亦可倂用2種以上。 而且’本發明中於透明導電膜等之特別被要求高折射 -10- 201124490 率特性的用途時之導電性微粒子分散液中所配合 率微粒子，爲控制所形成的透明導電膜之折射率 者’以使用折射率爲1 · 8〜3.0之金屬氧化物 且’在各文獻中記載有各高折射率微粒子之折射 原有之値。使用折射率未達1 . 8之高折射率微粒 法製得高折射率之膜，此外，使用折射率超過3 射率微粒子時，會有膜之透明性降低的傾向。有 所使用的高折射率微粒子之種類，只要是可達成 可，沒有特別的限制，可使用市售品等之習知品 可使用氧化锆（η = 2·2)、氧化鈦（n = 2.76)及氧化 等。此等之高折射率微粒子，可僅使用1種，亦 種以上。 於本發明之導電性微粒子分散液中，除上述 微粒子及特別被要求高折射率特性之用途時所配 射率微粒子外，在分散媒中配合金屬錯合物。該 物，由於於分散液中作爲分散劑之機能，可製得 保存安定性優異的導電性微粒子分散液。而且， 物幾乎完全沒有使分散過程中所使用的金屬製機 機材被腐蝕的情形。 本發明所使用的金屬錯合物，係由選自锆、 錳、鐵、鈷、鎳、銅、鈀、鋁、鋅、銦、錫及鈾 金屬（就分散液之色味少而言，較佳者例如選自 鋁、鋅、銦及錫所成群之金屬），與選自β-二酮 配位子（較佳者爲選自三甲基乙醯基三氟化丙酮 的高折射 時所添加 較佳。而 率爲材料 子時，無 • 〇之高折 關本發明 目的者即 。例如， 铈（=2.2) 可倂用2 之導電性 合的高折 金屬錯合 分散液之 金屬錯合 器或塗佈 鈦、鉻、 所成群之 锆、鈦、 所成群的 、乙醯基 -11 - 201124490 丙酮、三氟化乙醯基丙酮及六氟化乙醯基丙 位子）所成，更佳者爲不含烷氧化物之金屬 不含烷氧化物之金屬錯合物時，烷氧化物與 水分或空氣中之水分進行經時反應，會有導 散液及透明導電膜形成用之含導電性微粒子 成物的保存安定性及膜特性降低的傾向。 於本發明中，有關於透明導電膜等之特 射率特性的用途時所配合的金屬錯合物， 化物之金屬錯合物。使用不含烷氧化物之金 烷氧化物與溶劑中所含的水分或空氣中之水 應，會有導電性微粒子分散液及透明導電膜 導電性微粒子之光硬化性組成物的保存安定 低的情形。 而且，以更爲提高分散液之保存安定性 可另外添加其他的分散劑作爲分散助劑。該 類，沒有特別的限制，該分散劑例如以具有 基構造之磷酸酯系非離子型分散劑。 本發明所使用的分散媒，例如水、甲醇 醇、正丁醇、2-丁醇、辛醇等之醇類；丙酮 甲基異丁酮、環己酮、4-羥基-4-甲基-2-戊 醋酸乙酯、醋酸丁酯、乳酸乙酯、γ-丁內酯 醚乙酸酯、丙二醇單乙醚乙酸酯等之酯類 醚、二乙二醇單丁醚等之醚類；苯、甲苯、 等之芳香族烴類：二甲基甲醯胺、Ν,Ν-二甲 酮所成群的配 錯合物。使用 溶劑中所含的 電性微粒子分 之光硬化性組 別被要求高折 使用不含烷氧 屬錯合物時， 分進行經時反 形成用之含有 性及膜特性降 爲目的時’亦 分散助劑之種 聚氧化乙烯烷 、乙醇、異丙 、甲基乙酮、 酮等之酮類； 、丙二醇單甲 :乙二醇單甲 二甲苯、乙苯 基乙醯基乙醯 -12- 201124490 胺、N -甲基吡啶烷酮等之醯胺類等。於此等之中，以乙 醇、異丙醇、正丁醇、2-丁醇、甲基乙酮、甲基異丁酮、 環己酮、4·羥基-4-甲基-2-戊酮、醋酸乙酯、醋酸丁酯、 甲苯、二甲苯、乙苯較佳，以甲基乙酮、丁醇、二甲苯、 乙苯、甲苯更佳。於本發明中，可單獨使用一種，亦可倂 用二種以上作爲分散媒。 於本發明中，有關於透明導電膜等之特別被要求高折 射率特性的用途時所配合的分散媒，爲防止導電性微粒子 分散液或透明導電膜形成用之含導電性微粒子之光硬化性 組成物中所含的微粒子之粒徑產生經時性變大時，所含的 水份量爲3質量％以下，較佳者爲1質量％以下，更佳者 爲0.5質量％以下。 於本發明之導電性微粒子分散液中/各成份之配合比 例可視導電性微粒子分散液之用途而定予以適當設定，每 100質量份導電性微粒子中，金屬錯合物之含量爲2〜45 質量份、較佳者爲5〜20質量份，分散媒之含量爲4〇〜 1 000質量份、較佳者爲60〜600質量份。金屬錯合物之 量較上述之下限値更少時，導電性微粒子之分散變得不 佳，較上述之上限値更多時，金屬錯合物不溶解於分散媒 中而產生沉澱情形。而且，分散媒之量較上述之下限値更 少時，金屬錯合物之溶解、導電性微粒子之分散變得不充 分，較上述之上限値更多時，導電性微粒子分散液之濃度 過薄時，變得沒有實用價値。 此外，於本發明中透明導電膜等之特別被要求高折射 -13- 201124490 率特性的用途時之導電性微粒子分散液中，每1 00質量份 高折射率微粒子中，導電性微粒子之含量爲30〜900質量 份（較佳者爲40〜5 00質量份），金屬錯合物之含量爲3〜 45 0質量份（較佳者爲7〜200質量份），分散媒之含量爲 60〜9000質量份（較佳者爲10〜5000質量份）。導電性微 粒子之量較上述之下限値更少時，所形成的膜之折射率變 高，惟導電性降低。反之，導電性微粒子之量較上述之上 限値更高時，所形成的膜之導電性變高，惟折射率降低。 另外，金屬錯合物之量較上述之下限値更少時，高折射率 微粒子及導電性微粒子之分散性變得不佳，較上述之上限 値更多時，金屬錯合物不會溶解於分散媒中而產生沉澱情 形。而且，分散媒之量較上述之下限値更少時，金屬錯合 物之溶解、高折射率及導電性微粒子之分散變得不充分， 較上述之上限値更多時，高折射率微粒子及導電性微粒子 之濃度過薄，變得沒有實用價値。 本發明之導電性微粒子分散液，係藉由以任意順序添 加導電性微粒子、金屬錯合物及分散媒，以及特別被要求 高折射率特性之用途時所配合的高折射率微粒子，且進行 充分混合而製得。通常，在使金屬錯合物溶解的分散媒中 分散導電性微粒子或高折射率微粒子予以製造。亦可於進 行分散操作前，進行預分散操作。預分散操作係可於溶解 有金屬錯合物之分散媒中，以分散器等進行攪拌且慢慢地 添加導電性微粒子或高折射率微粒子，以目視確認沒有導 電性微粒子或高折射率微粒子之塊狀物爲止進行均勻地攪 -14- 201124490 拌。而且，配合有高折射率微粒子時，亦可預先調製由高 折射率微粒子、金屬錯合物及分散媒所成的分散液，與由 導電性微粒子、金屬錯合物及分散媒所成的分散液，然 後，混合此等之分散液予以製造。 導電性微粒子或高折射率微粒子之分散操作，可使用 油漆攪拌器、球磨機、砂磨機、離心磨機（Centrimill) 等。於分散操作時，以使用玻璃珠、锆珠等之分散珠較 佳。珠徑沒有特別的限制，通常約爲0 · 05〜1 mm，較佳者 爲0.〇5〜〇.65nm。配合有高折射率微粒子時，更佳者爲 0.08 〜0.65nm、最佳者爲 0.08 〜0_5mm。 於本發明之導電性微粒子分散液中，導電性微粒子或 高折射率微粒子之粒徑，中徑以1 20nm以下較佳、更佳 者爲80nm以下。中徑爲該値以上時，會有由含導電性微 粒子之光硬化性組成物所得的含導電性微粒子之硬化膜的 霾度變高的傾向。 本發明之導電性微粒子分散液，經過長時間後導電性 微粒子或高折射率微粒子仍安定地分散，而且，由於不含 會使金屬腐蝕的乙醯基丙酮等時，故可保管於金屬製容器 中〇 本發明之導電性微粒子分散液，可包含於保護膜形成 用組成物、防止反射膜形成用組成物、接著劑、密封材 料 '接著材料等使用，特別是適合形成具有抗靜電機能之 防止反射膜的組成物使用。 本發明之含導電性微粒子的光硬化性組成物，含有導 -15- 201124490 電性微粒子、金屬錯合物、活性能量線硬化性化合物、光 聚合引發劑及分散媒，導電性微粒子、金屬錯合物及分散 媒如上所述。 而且，本發明之透明導電膜形成用之含導電性微粒子 的光硬化性組成物，含有折射率爲1. 8以上的高折射率微 粒子、導電性微粒子、不含烷氧化物之金屬錯合物、活性 能量線硬化性化合物、光聚合引發劑及分散媒，水分爲3 質量％以下，高折射率微粒子 '導電性微粒子及分散媒如 上所述8 此外，於本發明之含導電性微粒子的光硬化性組成物 中，爲賦予硬化膜之耐擦傷性、耐摩擦性、低翹曲性、密 接性、透明性、折射率、耐藥品性、抗靜電性時，可使用 除上述導電性微粒子外之微粒子。有關微粒子之種類，只 要是可達成目的者即可，沒有特別的限制，可使用市售品 等之習知品。例如，氧化锆、氧化鈦、氧化鋁及氧化矽等 之無機微粒子或有機微粒子等。此等之微粒子，可僅使用 1種，亦可2種以上倂用。 本發明中使用的活性能量線硬化性化合物，例如可爲 游離基聚合性單體、游離基聚合性低聚物等。 游離基聚合性單體之具體例，如（甲基）丙烯酸甲酯、 (甲基）丙烯酸乙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸 2-乙基己酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸環己酯、 (甲基）丙稀酸四氫呋喃酯、（甲基）丙稀酸2 -經基乙醋、（甲 基）丙烯酸2-羥基丙酯、單（甲基）丙烯酸聚乙二醇酯、單 -16- 201124490 (甲基）丙烯酸甲氧基聚乙二醇酯、單（甲基）丙烯酸聚丙二 醇酯、單（甲基）丙烯酸聚乙二醇聚丙二醇酯、單（甲基）丙 烯酸聚乙二醇聚四甲二醇酯、（甲基）丙烯酸環氧丙酯等之 單官能（甲基）丙烯酸酯；二（甲基）丙烯酸乙二醇酯、二（甲 基）丙烯酸二乙二醇酯、二（甲基）丙烯酸三乙二醇酯、二 (甲基）丙烯酸四乙二醇酯、二（甲基）丙烯酸聚乙二醇酯、 二（甲基）丙烯酸聚丙二醇酯、二（甲基）丙烯酸新戊醇酯、 二（甲基）丙烯酸烯丙酯、二（甲基）丙烯酸雙酚A酯、二（甲 基）丙烯酸氧化乙烯改性雙酚A酯、二（甲基）丙烯酸聚氧 化乙烯改性雙酚A酯、二（甲基）丙烯酸氧化乙烯改性雙酚 S酯、二（甲基）丙烯酸雙酚S酯、二（甲基）丙烯酸I，4-丁 二醇酯、二（甲基）丙烯酸1，3-丁二醇酯等之二官能（甲基） 丙烯酸酯；三（甲基）丙烯酸三羥甲基丙烷酯、三（甲基）丙 烯酸丙三醇酯、三（甲基）丙烯酸季戊四醇酯、四（甲基）丙 烯酸季戊四醇酯、三（甲基）丙烯酸乙烯改性三羥甲基丙烷 酯、五（甲基）丙烯酸二季戊四醇酯、六（甲基）丙烯酸二季 戊四醇酯等之三官能以上的（甲基）丙烯酸乙酯；苯乙烯、 乙烯基甲苯、醋酸乙烯酯、N-乙烯基吡咯烷酮、丙烯腈、 烯丙醇等之游離基聚合性單體。 另外，游離基聚合性低聚物之具體例，如聚酯（甲基） 丙烯酸酯、聚胺基甲酸酯（甲基）丙烯酸酯、（甲基）丙烯酸 環氧酯、聚醚（甲基）丙烯酸酯、低聚（甲基）丙烯酸酯、烷 基化（甲基）丙烯酸酯、（甲基）丙烯酸多元醇酯、聚矽氧（甲 基）丙烯酸酯等之至少具有1個（甲基）丙烯醯基之預聚 -17- 201124490 物。更佳的游離基聚合性低聚物，爲聚酯、環氧基、聚胺 基甲酸酯之各（甲基）丙烯酸酯。於本發明中，活性能量線 硬化性化合物可單獨一種使用，亦可二種以上倂用。 於本發明之含導電性微粒子的光硬化性組成物中，由 於含有光聚引發劑（光增感劑），故可以少量的活性能量線 照射’使含導電性微粒子之光硬化性組成物硬化。 本發明使用的光聚合引發劑（光增感劑），例如1 -羥基 環己基苯酮、二苯甲酮、苯甲基二甲酮、苯偶因甲醚、苯 偶因乙醚、p-氯化二苯甲酮、4_苯甲醯基-4-甲基二苯基硫 醚、2-苯甲基-2_二甲基胺基-1-(4-嗎啉基苯基）-丁酮-1,2-甲基-1-[4-(甲基硫代）苯基]-2-嗎啉基丙酮-1。光聚合引發 劑可單獨一種使用，亦可二種以上倂用。 於本發明之含導電性微粒子的光硬化性組成物中，各 成份之配合比例可視含導電性微粒子之光硬化性組成物的 用途而定予以適當設定，每100質量份導電性微粒子中， 金屬錯合物之含量以2〜45質量份較佳（更佳者爲5〜20 質量份），分散媒之含量以40〜1000質量份較佳（更佳者 爲6 0〜6 0 0質量份），活性能量線硬化性化合物之含量以 10〜1 000質量份較佳（更佳者爲25〜150質量份），且每 1 0 0質量份活性能量線硬化性化合物中，光聚合引發劑之 含量以0· 1〜20質量份較佳（更佳者爲1〜15質量份）。 此處，金屬錯合物之量較上述下限値更少時，會有導 電性微粒子之分散性不佳的傾向，較上述上限値更多時， 會有金屬錯合物沒有溶解於分散媒中而產生沉澱的情形。 -18- 201124490 分散媒之量較上述下限値更少時，會有金屬錯合物溶解、 導電性微粒子之分散性變得不充分的傾向，較上述上限値 更多時’導電性微粒子分散液之濃度過薄時，導電性微粒 子之添加效果變得不充分的傾向。活性能量線硬化性化合 物之量較上述下限値過少時，會有硬化膜之折射率變高， 透明性降低的傾向’較上述上限値更多時，不易使硬化膜 之折射率變成企求程度之高値。而且，光聚合引發劑之量 較上述下限値更少時，會有光硬化性組成物之硬化速度降 低的傾向，較上述上限値更多時，無法得到符合的效果。 此外’透明導電膜形成用之含導電性微粒子的光硬化 性組成物，每1 00質量份高折射率微粒子中，導電性微粒 子之含量以30〜900質量份較佳（更佳者爲40〜500質量 份）’金屬錯合物之含量以3〜45 0質量份較佳（更佳者爲7 〜200質量份），分散媒之含量以6〇〜70000質量份較佳 (更佳者爲100〜5 0000質量份），活性能量線硬化性化合 物之含量以丨4〜1 0000質量份較佳（更佳者爲35〜2000質 量份），且每1 00質量份活性能量線硬化性化合物中，光 聚合引發劑之含量以〇_1〜20質量份較佳（更佳者爲1〜1 5 質量份）。 於該透明導電膜形成用之含導電性微粒子的光硬化性 組成物中，導電性微粒子之量較上述下限値更少時，導電 性降低。反之，導電性微粒子之量較上述上限値更高時， 所形成的膜之導電性變高，折射率降低。金屬錯合物之量 較上述下限値更少時，會有高折射率微粒子及導電性微粒 -19- 201124490 子之分散不佳的傾向，較上述上限値更多時，會有金屬錯 合物沒有溶解於分散媒中而產生沉澱的情形。分散媒之量 較上述下限値更少時，會有金屬錯合物之溶解、高折射率 微粒子及導電性微粒子之分散變得不佳的傾向，較上述上 限値更多時，光硬化性組成物之濃度過薄，變得不具實用 價値。活性能量線硬化性化合物之量較上述下限値更少 時’會有透明導電膜之折射率變高，透明性降低的傾向， 較上述上限値更多時，透明導電膜之折射率無法達到企求 程度的高値，且抗靜電機能變得不充分。而且，光聚合引 發劑之量較上述下限値更少時，會有光硬化性組成物之硬 化速度降低的傾向，較上述上限値過多時，無法得到符合 的效果。 而且’於本發明之含導電性微粒子的光硬化性組成物 中’在不會損害其目的之範圍內，亦可配合除上述外之慣 用的各種添加劑。該添加劑例如禁止聚合劑、硬化觸媒、 抗氧化劑、整平劑、偶合劑等。 本發明之含導電性微粒子的光硬化性組成物，可塗佈 或印刷於塑膠（聚碳酸酯、聚甲基丙烯酸甲酯、聚苯乙 嫌、聚醋、聚烯烴、環氧樹脂、蜜胺樹脂、三乙醯基纖維 素樹脂、聚對苯二甲酸乙烯酯、ABS樹脂、AS樹脂、原 疲稀系樹脂等）、金屬、木材、紙、玻璃、石板等之各種 基材表面上’且予以硬化形成膜，例如使用於塑膠光學零 件' 觸控板、薄膜型液晶元件、塑膠容器、作爲建築內裝 材料之床材、壁材、人工大埋石等之防止刮傷（擦傷）或防 -20- 201124490 止污染時之保護塗佈材料；薄膜型液晶元件、觸控板、塑 膠光學零件等之防止反射膜；各種基材之接著劑、密封材 料；印刷油墨之接著材料等’特別是可適合使用於形成具 有抗靜電機能之防止反射膜的組成物。此外，配合有高折 射率微粒子之含導電性微粒子的光硬化性組成物時，特別 是可適合使用於形成高折射率之透明導電膜。 將含導電性微粒子之光硬化性組成物塗佈或印刷於基 材時’可以例如輥塗佈、旋轉塗佈、篩網印刷等之方法進 行。視其所需’進行加熱’使分散媒（溶劑）蒸發，使塗膜 乾燥’然後，照射活性能量線（紫外線或電子線）。活性能 量線源可使用低壓水銀燈、高壓水銀燈、金屬鹵素化燈、 贏氣燈、準分子雷射、色素雷射等之紫外線源，及電子線 加速裝置。活性能量線之照射量，以紫外線時爲5 〇〜 3000mJ/cm2，電子線時爲〇_2〜l〇〇〇pC/cm2之範圍內爲 宜。藉由該活性能量線照射，使上述活性能量線硬化性化 合物聚合’且形成以樹脂結合導電性微粒子之膜。一般而 言’該膜之膜厚以〇·1〜ΙΟ.Ομιη之範圍內較佳。 使以本發明之導電性微粒子分散液所調製的含導電性 微粒子之光硬化性組成物硬化所得的本發明之含導電性微 粒子的硬化膜’導電性微粒子均勻地分散於硬化膜內，可 控制折射率、透明高、霾度低，具體而言折射率爲丨45〜 1.90、光透過率爲75 %以上、霾度爲2.0%以下，且表面電 阻値爲1 0Ι2Ω/□以下。 而且，於本發明中，使企求高折射率特性之透明導電 -21 - 201124490 膜形成用之含導電性微粒子的組成物硬化所得的本發明透 明導電膜，在透明導電膜內均勻地分散高折射率微粒子及 導電性微粒子，可控制折射率，且折射率高、透明性高、 霾度低，具體而言折射率爲1.55〜1.90、光透過率爲85% 以上、霾度爲1.5%以下，且表面電阻値爲1012Ω/□以 下。爲控制折射率時，可調整高折射率微粒子及導電性微 粒子之量與活性能量線硬化性化合物之量的比例。透明導 電膜可使用於導電性防止反射材料或顯示裝置之顯示面 等。 【實施方式】 於下述中，藉由實施例及比較例具體地說明本發明。 而且，於實施例及比較例中，「份」全部爲「質量份」。 [實施例] [實施例1〜5及比較例1〜2 ] 實施例1〜5及比較例1〜2所使用的成分，如下所 述。 <導電性微粒子> ΑΤΟ(折射率2.0、體積電阻値lOQ.cm、一次粒徑 0.0 5 μηι) ΙΤΟ(折射率2.0、體積電阻値0.02Ω · cm、一次粒徑 0.04 μηι) -22- 201124490 氧化錫（折射率2.0、體積電阻値1 00Ω · cm、一次粒 徑 0 · 0 6 μ m) 氧化鋅（折射率1 . 9 5、體積電阻値1 0 0Ω · cm、一次粒 徑 0.0 6μηι) <無機微粒子> 氧化鋁（折射率1 · 7 6、一次粒徑〇 . 〇 4 μ m ) <金屬錯合物> 乙醯基乙酸锆[Zr(C5H7〇2)4] 乙醯基乙酸鈦[Ti(C5H702)4] 乙醯基乙酸鋅[Zn(C5H702)2] 雙乙醯基乙酸二丁基錫[(C4H9)2Sn(C5H702)2] <分散助劑> BYK(股）製、BYK-142 <活性能量線硬化性化合物>C -5- 201124490 It is resistant to abrasion and foreign matter such as dust or garbage. Therefore, the high refractive index layer of the antireflection film is required to have excellent scratch resistance and antistatic properties in addition to high transparency and high refractive index characteristics. Next, a method of imparting an antistatic function to the cured film is known, and a method of adding a surfactant, a conductive polymer, or a conductive fine particle mainly composed of a metal oxide to the curable composition is known, and in particular, For the purpose of producing a film having a permanent antistatic effect, a method of adding conductive fine particles is generally used. The method of adding the conductive fine particles is a method in which a chelating agent is blended in a resin solution or a solvent, and an inorganic oxide is dispersed in the complex (see, for example, Patent Documents 1 and 2). [Patent Document] [Patent Document 1] JP-A-2001-139, 847 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2001-139,889. The liquid and its curable composition are required to have a small particle diameter of the conductive fine particles and excellent storage stability of the dispersion. The chelating agents described in the above Patent Documents 1 and 2 have a problem that the metal device or the coating material used in the dispersion treatment is corroded due to the formation of a metal chelate compound with the metal. The present invention has been made in view of the above problems, and provides (1) a cured film which is excellent in transparency and has an antistatic function on the surface of a substrate, and the metal machine or the coating machine used in the dispersion process does not (2) various cured films such as a transparent conductive film obtained from the photocurable composition containing the conductive fine particles, (3) having the photocurable composition containing conductive fine particles, which is corroded-6-201124490, and (3) For the purpose of the display device of the cured film obtained by the photocurable composition containing the conductive fine particles, and (4) the conductive fine particle dispersion liquid having excellent storage stability used for preparing the photocurable composition containing the conductive fine particles . In order to achieve the above-mentioned various objectives, the present inventors have found that the conductive fine particles and the metal complex are dispersed in the dispersion medium, and it is found that the conductive fine particle dispersion having excellent stability can be obtained. It has been found that by using the conductive fine particle dispersion liquid, a photocurable composition containing conductive fine particles which is not corroded by a metal machine or a coating material during the dispersion treatment can be obtained, and the present invention has been completed. In other words, the conductive fine particle dispersion of the present invention is characterized by being composed of conductive fine particles, a metal complex, and a dispersion medium. Preferably, the content of the metal complex is 2 per 100 parts by mass of the conductive fine particles. To 45 parts by mass, the content of the dispersion medium is 40 to 1000 parts by mass. Further, in the present invention, in addition to the transparent conductive property, the conductive fine particle dispersion liquid having high refractive index characteristics is characterized in that the high refractive index fine particles having a refractive index of 1.8 or more and the conductive fine particles are not contained. The metal oxide complex of the alkoxide and the dispersion medium are formed, and the water content is 3% by mass or less. Preferably, the content of the conductive fine particles is 30 to 900 parts by mass per 100 parts by mass of the high refractive index fine particles, and the metal is misaligned. The content of the substance is from 3 to 450 parts by mass and the content of the dispersion medium is from 60 to 9000 parts by mass. Next, the photocurable composition containing conductive fine particles of the present invention, 201124490, is characterized by being composed of conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, preferably The content of the metal complex is 2 to 45 parts by mass, the content of the dispersion medium is 40 to 1,000 parts by mass, and the content of the active energy ray-curable compound is 10 to 1000 parts by mass per 100 parts by mass of the conductive fine particles. In the active energy ray-curable compound, the content of the photopolymerization initiator is 0.1 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound, and the conductive property for forming a transparent conductive film having high refractive index characteristics is required in the present invention. A photocurable composition of microparticles characterized by high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, a metal oxide complex containing no alkoxide, an active energy ray-curable compound, and photopolymerization initiation The content of the water and the dispersion medium is 3% by mass or less, and preferably, the content of the conductive fine particles is from 30 to 900 parts by mass per 1 part by mass of the high refractive index fine particles. The content of the complex is 3 to 450 parts by mass, the content of the dispersion medium is 60 to 70,000 parts by mass, and the content of the active energy ray-curable compound is 14 to 10,000 parts by mass, and the active energy per 1 part by mass 1〜2 0质量份。 The content of the photopolymerization initiator is 0. 1~2 0 parts by mass. Further, the cured film containing conductive fine particles of the present invention is characterized in that the photocurable composition containing the above-mentioned conductive fine particles is applied or printed on a substrate, and is cured, preferably having a refractive index of 1.4 5 . 〜1.90, the light transmittance is 75% or more, the twist is 2.0% or less, and the surface resistance 値 is 1012 Ω/□ or less. Further, in the present invention, a cured film containing conductive fine particles for forming a transparent conductive -8 - 201124490 film having high refractive index characteristics is characterized in that the above transparent conductive film is formed by coating or printing on a substrate. The photocurable composition containing conductive fine particles is preferably cured, and preferably has a refractive index of 1.55 to 1.90, a light transmittance of 85% or more, a twist of 1.5% or less, and a surface resistance of 値. 1〇12Ω/□ or less. [Effect of the Invention] According to the present invention, (1) a conductive fine particle dispersion liquid excellent in storage stability of a dispersion liquid, and (2) a cured film having excellent transparency and antistatic function can be formed on the surface of the substrate. a photocurable composition containing conductive fine particles which is not corroded by a metal machine or a coating machine used in the dispersion treatment process, and (3) a transparent and excellent antistatic function obtained from the composition A hardened film of fine particles. Further, according to the present invention, it is possible to provide (1) a transparent conductive film which is excellent in transparency and has high refractive index and antistatic function on the surface of the substrate, and the metal machine or coating machine used in the dispersion process is not (2) a transparent conductive film having excellent transparency and high refractive index and antistatic function, which is obtained by forming a composition for forming a photocurable transparent conductive film which is corroded, and (3) having The display device of the transparent conductive film and (4) a dispersion liquid excellent in storage stability used when preparing the composition for forming a transparent conductive film. [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be specifically described. -9 - 201124490 The conductive fine particle dispersion of the present invention contains conductive fine particles, a metal complex, and a dispersion medium. The shape of the conductive fine particles used in the present invention is not particularly limited. The conductivity of the conductive fine particles is such that the volume resistivity is 1 〇 7 Ω · cm or less, preferably 103 Ω · cm or less. Further, as for the size of the conductive fine particles, a primary particle diameter of 1 to 500 nm is usually used, preferably 10 to 1 nm. Further, in the present invention, when a transparent conductive film or the like is required to have high refractive index characteristics, the conductive fine particle dispersion liquid contains high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and metal containing no alkoxide. The complex compound and the dispersion medium have a water content of 3% by mass or less. The shape of the high refractive index fine particles and the conductive fine particles used in the present invention is not particularly limited. Further, as for the size of the high refractive index fine particles and the conductive fine particles, a primary particle diameter of 1 to 500 nm, preferably 10 to 100 nm, may be used, and the type of the conductive fine particles used in the present invention may be used as long as it is In order to achieve the objective, there is no particular limitation, and a conventional product such as a commercially available product can be used. For example, a metal oxide such as ITO, ruthenium, tin oxide, zinc oxide, indium oxide, zinc ruthenate or ruthenium pentoxide or a hydroxide constituting a metal of such a metal oxide can be used. For tin oxide, an element doped with phosphorus or the like can also be used. Moreover, regarding zinc oxide, those doped with gallium or aluminum may also be used. Further, it may be metal fine particles such as gold, silver, copper, lead, or aluminum, and organic conductive fine particles. These conductive fine particles may be used alone or in combination of two or more. Further, in the present invention, in the case of a transparent conductive film or the like which is particularly required to have a high refractive index of the use of the high refractive index, the ratio of the fine particles in the conductive fine particle dispersion is to control the refractive index of the formed transparent conductive film. A metal oxide having a refractive index of 1 · 8 to 3.0 is used and 'the refractive index of each high refractive index fine particle is described in each document. A film having a high refractive index is obtained by using a high refractive index fine particle method having a refractive index of less than 1.8, and when a fine particle having a refractive index exceeding a third transmittance is used, the transparency of the film tends to be lowered. The type of the high refractive index fine particles to be used is not particularly limited as long as it can be achieved, and a conventional product such as a commercially available product can be used, and zirconium oxide (η = 2·2) and titanium oxide (n = 2.76) can be used. Oxidation, etc. These high refractive index fine particles may be used alone or in combination of two or more. In the conductive fine particle dispersion of the present invention, a metal complex is blended in a dispersion medium in addition to the above-mentioned fine particles and the fine particles having a high refractive index property. This product is capable of producing a conductive fine particle dispersion excellent in stability and stability by functioning as a dispersing agent in the dispersion. Moreover, there is almost no case where the metal machine used in the dispersion process is corroded. The metal complex used in the present invention is selected from the group consisting of zirconium, manganese, iron, cobalt, nickel, copper, palladium, aluminum, zinc, indium, tin and uranium metal (in terms of the coloriness of the dispersion, Preferred for example, a metal selected from the group consisting of aluminum, zinc, indium, and tin), and a high refractive index selected from the group consisting of a β-diketone ligand (preferably selected from the group consisting of trimethylethyl fluorenyl fluoride) The addition is preferred, and when the ratio is a material, the object of the present invention is not high. For example, 铈(=2.2) can be used for the metal of the conductive high-fold metal-miscible dispersion of 2 Misaligner or coated with titanium, chromium, groups of zirconium, titanium, groups of acetyl -11 - 201124490 acetone, trifluoroacetic acid acetone and hexamethylene hexafluoride In the case of a metal oxide containing no alkoxide, the alkoxide is reacted with moisture or water in the air to form a dispersing liquid and a transparent conductive film. The storage stability and film properties of the conductive fine particle-containing product tend to be lowered. In the present invention, there is a metal complex compound and a metal complex compound which are blended in the use of the radioactive property of a transparent conductive film or the like. When the alkoxide containing no alkoxide and the water contained in the solvent or the water in the air are used, the storage fineness of the photocurable composition of the conductive fine particle dispersion and the transparent conductive film conductive fine particles is low. situation. Further, in order to further improve the storage stability of the dispersion, another dispersant may be additionally added as a dispersing aid. In this case, there is no particular limitation, and the dispersant is, for example, a phosphate-based nonionic dispersant having a basic structure. The dispersing medium used in the present invention, for example, an alcohol such as water, methanol alcohol, n-butanol, 2-butanol or octanol; acetone methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl- Ethyl esters of ethyl 2-pentanoacetate, butyl acetate, ethyl lactate, γ-butyrolactone acetate, propylene glycol monoethyl ether acetate, ethers such as diethylene glycol monobutyl ether; Aromatic hydrocarbons such as toluene or the like: complex complexes of dimethylformamide, hydrazine, and hydrazine-dimethyl ketone. When the photocurable group of the electric microparticles contained in the solvent is required to be used in a high-definition manner, when the alkoxy-containing complex is not used, the content of the anti-formation and the film properties are reduced. a ketone of polyoxyethylene alkyl, ethanol, isopropyl, methyl ethyl ketone, ketone, etc.; a propylene glycol monomethyl group: ethylene glycol monomethylidene, ethyl phenyl acetonitrile hydrazine-12- 201124490 Amines such as amines and N-methylpyridinone. Among these, ethanol, isopropanol, n-butanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4 hydroxy-4-methyl-2-pentanone Ethyl acetate, butyl acetate, toluene, xylene and ethylbenzene are preferred, and methyl ethyl ketone, butanol, xylene, ethylbenzene and toluene are more preferred. In the present invention, one type may be used alone or two or more types may be used as the dispersion medium. In the present invention, the dispersing medium to be used in the case where the transparent conductive film or the like is required to have a high refractive index characteristic, and the photocuring property of the conductive microparticles for preventing the formation of the conductive fine particle dispersion or the transparent conductive film When the particle diameter of the fine particles contained in the composition is increased over time, the amount of water contained is 3% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass or less. In the conductive fine particle dispersion of the present invention, the mixing ratio of each component can be appropriately set depending on the use of the conductive fine particle dispersion, and the content of the metal complex is 2 to 45 mass per 100 parts by mass of the conductive fine particles. The portion is preferably 5 to 20 parts by mass, and the content of the dispersion medium is 4 to 1 000 parts by mass, preferably 60 to 600 parts by mass. When the amount of the metal complex is less than the above lower limit 値, the dispersion of the conductive fine particles becomes poor, and when the upper limit 値 is more than the above, the metal complex does not dissolve in the dispersion medium to cause precipitation. Further, when the amount of the dispersion medium is less than the lower limit 値, the dissolution of the metal complex and the dispersion of the conductive fine particles are insufficient, and when the amount is larger than the upper limit 値, the concentration of the conductive fine particle dispersion is too thin. At the time, there is no practical price. Further, in the conductive fine particle dispersion liquid of the transparent conductive film or the like which is particularly required to have a high refractive index-13-201124490 rate characteristic, the content of the conductive fine particles per 100 parts by mass of the high refractive index fine particles is 30 to 900 parts by mass (preferably 40 to 500 parts by mass), the content of the metal complex is 3 to 45 parts by mass (preferably 7 to 200 parts by mass), and the content of the dispersion medium is 60 to 9000 parts by mass (preferably 10 to 5000 parts by mass). When the amount of the conductive fine particles is less than the above lower limit 値, the refractive index of the formed film becomes high, but the conductivity is lowered. On the other hand, when the amount of the conductive fine particles is higher than the above upper limit, the conductivity of the formed film becomes high, but the refractive index is lowered. Further, when the amount of the metal complex is less than the above lower limit 値, the dispersibility of the high refractive index fine particles and the conductive fine particles becomes poor, and when the amount is larger than the above upper limit 金属, the metal complex does not dissolve in Precipitation occurs in the dispersion medium. Further, when the amount of the dispersion medium is less than the above lower limit 値, dissolution of the metal complex, high refractive index, and dispersion of the conductive fine particles are insufficient, and when the upper limit 値 is more than the above, the high refractive index fine particles and The concentration of the conductive fine particles is too thin, and there is no practical price. The conductive fine particle dispersion of the present invention is prepared by adding conductive fine particles, a metal complex, a dispersion medium, and a high refractive index fine particle to be used in a case where high refractive index characteristics are particularly required. Made by mixing. Usually, conductive fine particles or high refractive index fine particles are dispersed in a dispersion medium in which a metal complex is dissolved. It is also possible to carry out a pre-dispersion operation before the dispersion operation. In the dispersion medium in which the metal complex is dissolved, the conductive fine particles or the high refractive index fine particles are gradually added by stirring with a disperser or the like, and it is visually confirmed that there is no conductive fine particles or high refractive index fine particles. Stir until the block is evenly mixed -14-2424490. Further, when high refractive index fine particles are blended, a dispersion liquid composed of high refractive index fine particles, a metal complex, and a dispersion medium can be prepared in advance and dispersed by conductive fine particles, a metal complex, and a dispersion medium. The liquid is then prepared by mixing the dispersions. For the dispersion operation of the conductive fine particles or the high refractive index fine particles, a paint mixer, a ball mill, a sand mill, a centrifugal mill (Centrimill) or the like can be used. In the dispersion operation, it is preferred to use dispersed beads such as glass beads, zirconium beads or the like. The bead diameter is not particularly limited and is usually about 0. 05 to 1 mm, preferably 0. 〇 5 to 〇. 65 nm. When a high refractive index fine particle is blended, it is more preferably 0.08 to 0.65 nm, and most preferably 0.08 to 0_5 mm. In the conductive fine particle dispersion of the present invention, the particle diameter of the conductive fine particles or the high refractive index fine particles is preferably 1 to 20 nm or less, more preferably 80 nm or less. When the median diameter is more than this, the degree of twist of the cured film containing conductive fine particles obtained from the photocurable composition containing conductive fine particles tends to be high. In the conductive fine particle dispersion liquid of the present invention, the conductive fine particles or the high refractive index fine particles are stably dispersed after a long period of time, and since the ethylene acetylacetone which corrodes the metal is not contained, it can be stored in a metal container. The conductive fine particle dispersion of the present invention can be used in a composition for forming a protective film, a composition for preventing formation of a reflective film, an adhesive, a sealing material, a bonding material, and the like, and is particularly suitable for forming an antistatic function. The composition of the reflective film is used. The photocurable composition containing conductive fine particles of the present invention contains conductive fine particles of -15-201124490, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, and conductive fine particles and metal The compound and the dispersion medium are as described above. Further, the photocurable composition containing conductive fine particles for forming a transparent conductive film of the present invention contains high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and metal complex containing no alkoxide. The active energy ray-curable compound, the photopolymerization initiator, and the dispersion medium have a water content of 3% by mass or less, and the high refractive index fine particles 'conductive fine particles and a dispersion medium are as described above. 8 Further, the light containing the conductive fine particles of the present invention In the curable composition, in order to impart scratch resistance, abrasion resistance, low warpage, adhesion, transparency, refractive index, chemical resistance, and antistatic property to the cured film, in addition to the above conductive fine particles, Microparticles. As for the kind of the fine particles, it is only necessary to achieve the purpose, and there is no particular limitation, and a conventional product such as a commercially available product can be used. For example, inorganic fine particles such as zirconia, titanium oxide, aluminum oxide, and cerium oxide, or organic fine particles. These fine particles may be used alone or in combination of two or more. The active energy ray-curable compound used in the present invention may be, for example, a radical polymerizable monomer or a radical polymerizable oligomer. Specific examples of the radical polymerizable monomer are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A) Butyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofuran (meth) acrylate, (meth) acrylate 2 - ethyl acetonate, 2-hydroxypropyl (meth) acrylate, Poly(ethylene glycol) mono(meth)acrylate, mono-16-201124490 methoxypolyethylene glycol (meth)acrylate, polypropylene (meth)acrylate, mono(meth)acrylate a monofunctional (meth) acrylate such as an alcohol polypropylene glycol ester, a polyethylene glycol poly(ethylene glycol) polytetramethylene glycol ester, or a glycidyl (meth) acrylate; Alcohol ester, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , polypropylene (di)poly(ethylene) acrylate, neopentyl bis (meth) acrylate, di(methyl) propyl Acid allyl ester, bisphenol A di(meth)acrylate, oxyethylene modified bisphenol A di(meth)acrylate, poly(ethylene oxide) modified bisphenol A di(meth)acrylate, di(A) Ethylene oxide oxyethylene modified bisphenol S ester, bis(meth)acrylic acid bisphenol S ester, di(meth)acrylic acid I,4-butylene glycol ester, di(meth)acrylic acid 1,3-butyl a difunctional (meth) acrylate such as an alcohol ester; trimethylolpropane tris(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetrakis(methyl) a trifunctional or higher (meth) group such as pentaerythritol acrylate, trimethylolpropane tris(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ethyl acrylate; a radically polymerizable monomer of styrene, vinyl toluene, vinyl acetate, N-vinyl pyrrolidone, acrylonitrile, allyl alcohol or the like. Further, specific examples of the radical polymerizable oligomer, such as polyester (meth) acrylate, polyurethane (meth) acrylate, (meth) acrylate epoxy, polyether (methyl At least one of acrylate, oligo(meth) acrylate, alkylated (meth) acrylate, (meth) acrylate polyol, poly methoxy (meth) acrylate, etc. Prepolymerized propylene-based -17- 201124490. More preferably, the radical polymerizable oligomer is a (meth) acrylate of a polyester, an epoxy group or a polyurethane. In the present invention, the active energy ray-curable compound may be used alone or in combination of two or more. In the photocurable composition containing conductive fine particles of the present invention, since a photopolymerization initiator (photosensitizer) is contained, a small amount of active energy ray irradiation can be used to harden the photocurable composition containing conductive fine particles. . Photopolymerization initiator (photosensitizer) used in the present invention, for example, 1-hydroxycyclohexyl benzophenone, benzophenone, benzyl dimethyl ketone, benzoin methyl ether, benzoin ether, p-chloride Benzophenone, 4-benzylidene-4-methyldiphenyl sulfide, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Keto-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1. The photopolymerization initiator may be used singly or in combination of two or more. In the photocurable composition containing conductive fine particles of the present invention, the blending ratio of each component can be appropriately set depending on the use of the photocurable composition containing conductive fine particles, and metal is contained per 100 parts by mass of the conductive fine particles. The content of the complex compound is preferably 2 to 45 parts by mass (more preferably 5 to 20 parts by mass), and the content of the dispersion medium is preferably 40 to 1000 parts by mass (more preferably 60 to 600 parts by mass). The content of the active energy ray-curable compound is preferably from 10 to 1,000 parts by mass (more preferably from 25 to 150 parts by mass), and per 100 parts by mass of the active energy ray-curable compound, a photopolymerization initiator The content is preferably from 0.1 to 20 parts by mass (more preferably from 1 to 15 parts by mass). Here, when the amount of the metal complex is less than the lower limit 値, the dispersibility of the conductive fine particles tends to be poor, and when the amount is larger than the upper limit 値, the metal complex is not dissolved in the dispersion medium. The situation of precipitation occurs. -18- 201124490 When the amount of the dispersion medium is less than the lower limit 値, the metal complex dissolves and the dispersibility of the conductive fine particles tends to be insufficient. When the amount of the dispersion medium is more than the above upper limit 导电, the conductive fine particle dispersion When the concentration is too small, the effect of adding conductive fine particles tends to be insufficient. When the amount of the active energy ray-curable compound is less than the above lower limit, the refractive index of the cured film becomes high, and the transparency tends to decrease. When the amount is more than the upper limit 値, the refractive index of the cured film is less likely to be desired. Sorghum. Further, when the amount of the photopolymerization initiator is less than the above lower limit 値, the curing rate of the photocurable composition tends to decrease, and when it is more than the above upper limit ,, a satisfactory effect cannot be obtained. Further, in the photocurable composition containing conductive fine particles for forming a transparent conductive film, the content of the conductive fine particles per 100 parts by mass of the high refractive index fine particles is preferably 30 to 900 parts by mass (more preferably 40 to 40). The content of the metal complex is preferably from 3 to 45 parts by mass (more preferably from 7 to 200 parts by mass), and the content of the dispersion medium is preferably from 6 to 70,000 parts by mass (more preferably, 100 to 50,000 parts by mass), the content of the active energy ray-curable compound is preferably 4 to 1,000,000 parts by mass (more preferably 35 to 2000 parts by mass), and the active energy ray-curable compound per 100 parts by mass The content of the photopolymerization initiator is preferably from ～1 to 20 parts by mass (more preferably from 1 to 15 parts by mass). In the photocurable composition containing conductive fine particles for forming the transparent conductive film, when the amount of the conductive fine particles is less than the lower limit 値, the conductivity is lowered. On the other hand, when the amount of the conductive fine particles is higher than the above upper limit 値, the conductivity of the formed film becomes high, and the refractive index is lowered. When the amount of the metal complex is less than the above lower limit 値, there is a tendency that the high refractive index fine particles and the conductive fine particles -19-201124490 are poorly dispersed, and when there is more than the above upper limit 会有, there is a metal complex. There is no dissolution in the dispersion medium to cause precipitation. When the amount of the dispersion medium is less than the lower limit 値, the dissolution of the metal complex, the dispersion of the high refractive index fine particles and the conductive fine particles tend to be poor, and the photocurable composition is more than the upper limit 値. The concentration of the substance is too thin to become practical. When the amount of the active energy ray-curable compound is less than the above lower limit ', the refractive index of the transparent conductive film increases, and the transparency tends to decrease. When the amount is higher than the upper limit 値, the refractive index of the transparent conductive film cannot be achieved. The degree is high and the antistatic function becomes insufficient. Further, when the amount of the photopolymerization initiator is less than the above lower limit ,, the hardening rate of the photocurable composition tends to decrease, and when it is too large as compared with the above upper limit ,, a satisfactory effect cannot be obtained. Further, in the photocurable composition containing conductive fine particles of the present invention, various additives other than the above may be blended insofar as the object is not impaired. The additive is, for example, a polymerization agent, a curing catalyst, an antioxidant, a leveling agent, a coupling agent, or the like. The photocurable composition containing conductive fine particles of the present invention can be coated or printed on plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyacetate, polyolefin, epoxy resin, melamine). Resin, triethyl fluorenyl cellulose resin, polyethylene terephthalate, ABS resin, AS resin, raw squeezing resin, etc.), metal, wood, paper, glass, slate, etc. Hardened to form a film, for example, used in plastic optical parts 'touchpads, thin film type liquid crystal elements, plastic containers, bed materials for building interior materials, wall materials, artificial large stones, etc. to prevent scratches (scratches) or -20- 201124490 Protective coating materials for pollution-preventing; anti-reflection coatings for film-type liquid crystal elements, touch panels, plastic optical parts, etc.; adhesives and sealing materials for various substrates; adhesive materials for printing inks, etc. It can be suitably used for forming a composition having an antistatic property antireflection film. Further, when a photocurable composition containing conductive fine particles having a high refractive index fine particle is blended, it is particularly preferably used for forming a transparent conductive film having a high refractive index. When the photocurable composition containing conductive fine particles is applied or printed on a substrate, it can be carried out, for example, by roll coating, spin coating, screen printing or the like. The dispersion medium (solvent) is evaporated as needed to evaporate the coating film, and then the active energy ray (ultraviolet rays or electron beams) is irradiated. The active energy source can use a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halogen lamp, a win-win lamp, an excimer laser, a pigment laser, and the like, and an electron beam acceleration device. The irradiation amount of the active energy ray is preferably 5 〇 to 3000 mJ/cm 2 in the case of ultraviolet rays, and is preferably in the range of 〇 2 to l 〇〇〇 pC/cm 2 in the case of the electron beam. The active energy ray-curable compound is polymerized by irradiation with the active energy ray to form a film in which conductive fine particles are bonded by a resin. In general, the film thickness of the film is preferably in the range of 〇·1 to ΙΟ.Ομιη. The conductive fine particles containing the conductive fine particles of the present invention obtained by curing the photocurable composition containing conductive fine particles prepared by the conductive fine particle dispersion of the present invention are uniformly dispersed in the cured film, and are controllable The refractive index, the transparency is high, and the twist is low. Specifically, the refractive index is 丨45 to 1.90, the light transmittance is 75% or more, the twist is 2.0% or less, and the surface resistance 値 is 10 Ι 2 Ω/□ or less. Further, in the present invention, the transparent conductive film of the present invention obtained by curing the composition containing conductive fine particles for forming a transparent conductive-21-201124490 film having high refractive index characteristics uniformly disperses high refractive index in the transparent conductive film. The fine particles and the conductive fine particles can control the refractive index, have a high refractive index, have high transparency, and have low twist. Specifically, the refractive index is 1.55 to 1.90, the light transmittance is 85% or more, and the twist is 1.5% or less. And the surface resistance 値 is 1012 Ω / □ or less. In order to control the refractive index, the ratio of the amount of the high refractive index fine particles and the conductive fine particles to the amount of the active energy ray-curable compound can be adjusted. The transparent conductive film can be used for a conductive antireflection material or a display surface of a display device or the like. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. Moreover, in the examples and comparative examples, "parts" are all "parts by mass". [Examples] [Examples 1 to 5 and Comparative Examples 1 to 2] The components used in Examples 1 to 5 and Comparative Examples 1 and 2 were as follows. <Electrically conductive fine particles> ΑΤΟ (refractive index 2.0, volume resistance 値 lOQ.cm, primary particle diameter 0.0 5 μηι) ΙΤΟ (refractive index 2.0, volume resistance 値 0.02 Ω · cm, primary particle diameter 0.04 μηι) -22- 201124490 Tin oxide (refractive index 2.0, volume resistance 値1 00 Ω · cm, primary particle size 0 · 0 6 μ m) Zinc oxide (refractive index 1.95, volume resistance 値1 0 0Ω · cm, primary particle size 0.0 6μηι <Inorganic Fine Particles> Alumina (refractive index 1 · 7 6 , primary particle diameter 〇. 〇 4 μ m ) <metal complex > zirconium acetylate [Zr(C5H7〇2)4] B Titanium thioglycolate [Ti(C5H702)4] Zinc acetylacetate [Zn(C5H702)2] Dibutyltin diacetate [(C4H9)2Sn(C5H702)2] <Dispersing aid> BYK ), BYK-142 <Active Energy Ray Hardening Compound>
日本化藥（股）製、KAYARAD DPHA <光聚合引發劑>Nippon Kayaku Co., Ltd., KAYARAD DPHA <Photopolymerization Initiator>
Chiba .Speciality - Chemicals(股）製、IRGACURE 184 <螯合劑> -23- 201124490Chiba .Speciality - Chemicals, IRGACURE 184 <chelating agent> -23- 201124490
Daicel Chemical Industry(股）製、乙醯基丙酮 [實施例1 ] 在容器內以相對於1 〇〇份氧化錫，全量加入20份之 乙醯基乙酸鉻、250份之甲基乙酮及400份之玻璃珠之 量’以手動混合器進行混練3小時。於混練後，取出玻璃 珠，製得分散液。在該分散液中加入4 3份之D Ρ Η A、2份 之IRGACURE 184及65份之甲基乙酮，製得光硬化性組 成物。使用棒塗佈器，將該光硬化性組成物塗佈於膜厚 ΙΟΟμπι之PET薄膜（東洋紡（股）製 A4100)上，使有機溶劑 蒸發後，在空氣中使用高壓水銀燈照射3 00mJ/cm2之光， 製作厚度3 μιη之透明導電膜。膜之製作係於光硬化性組 成物後及6個月後進行。 [實施例2] 在容器內以相對於1〇〇份ΑΤΟ，全量加入10份之乙 醯基乙酸鈦、10份之ΒΥΚ-142、250份之2-丁醇及400 份之玻璃珠之量，以手動混合器進行混練3小時。於混練 後，取出玻璃珠，製得分散液。在該分散液中加入43份 之DPHA、2份之IRGACURE 184及65份之2-丁醇，製 得光硬化性組成物。然後，藉由與實施例1相同的方法， 製作厚度3μιη之透明導電膜》 [實施例3] -24- 201124490 在容器內以相對於1 00份ΑΤΟ，全量加入 乙醯基乙酸二丁基錫、25份之2-丁醇及400份 之量，以手動混合器進行混練3小時。於混練後 璃珠，製得分散液。在該分散液中加入43份之 份之IRGACURE 184及65份之2-丁醇，製得光 成物。然後，藉由與實施例1相同的方法，製作 之透明導電膜。 [實施例4] 在容器內以相對於50份 ΑΤΟ，全量加入 ΙΤΟ、10份之雙乙醯基乙酸二丁基錫、250份之 4〇〇份之玻璃珠之量，以手動混合器進行混練3 混練後，取出玻璃珠，製得分散液。在該分散 4 3 份之 DPHA、2 份之 IRGACURE 184 及 65 醇，製得光硬化性組成物。然後，藉由與實施例 方法，製作厚度3μηι之透明導電膜。 [實施例5] 在容器內以相對於60份ΙΤΟ，全量加入40 鋁、25份之雙乙醯基乙酸二丁基錫、2 5 0份之 4〇〇份之玻璃珠之量，以手動混合器進行混練3 混練後，取出玻璃珠，製得分散液。在該分散 67 份之 DPHA、6.7 份之 IRGACURE 184 及 170 醇’製得光硬化性組成物。然後，藉由與實施例 1 〇份之雙 之玻璃珠 ，取出玻 DPHA、2 硬化性組 厚度3 μ m 50份之 2-丁醇及 小時。於 液中加入 丨分之2-丁 1相同的 份之氧化 2 - 丁醇及 小時。於 液中加入 份之2-丁 1相同的 -25- 201124490 方法，製作厚度3 μηι之透明導電膜。 [比較例1 ] 20份 [，以 ^黏情 在容器內以相對於1 00份之氧化錫，全量加入 之ΒΥΚ-142、2 50份之2-丁醇及400份之玻璃珠之 手動混合器進行混練3小時。於混練中分散液有 形。 [比較例2] 乙醯 3 μηι 除在容器內添加20份之乙醯基丙酮取代20份 基乙酸鈦外，藉由與實施例2相同的方法，製作厚 之透明導電膜。 <評估方法> (1) 無機微粒子之中徑 硬化 :)製 管於 使分散於以實施例及比較例所製作的分散液及光 組成物之無機微粒子的中徑，使用日機裝（ft Microtrac粒度分布計，於製作後、3個月後（保 40°C)、6個月後（保管於40°C)以下述條件進行測定。 電色 値係 -26- 201124490 (3) 表面電阻値 有關實施例及比較例所得的透明導電膜，以三菱化學 股份有限公司製之H i r e s t a IP M C P - Η T 2 6 0進行測定。 (4) 折射率 有關實施例及比較例所得的透明導電膜’以Atag〇製 阿貝（Abbe)折射計DRM4(20°C)進行測定。 (5) 金屬製容器之腐蝕狀態 將實施例及比較例所製作的分散液加入不銹鋼容器 (S U S 3 0 4 ; F e - C r- N i系不銹鋼製）中’以目視評估靜置1個 月後之不銹鋼容器的腐蝕狀態° 上述各測定結果、評估結果與各組成物之組成’皆如 表1所示。 -27- 201124490 【r—|谳】 鎰 CM ATO 1 1 s σ> ιο in CO in CO 83.4 σ> d 5x 1010 1.59 τ— Sn02 1 1 1 1 1 1 1 1 1 I I I m m κ to ! ITO 雙乙醯基乙酸 二丁基錫 捱 1 CM 1—· 卜 CO CO 87.5 . _ 1 1 χ ίο1' 00 ιη τ— 鹿 寸 | ATO/1TO 雙乙醯基乙酸 二丁基錫 摧 〇 1 csi in LO LO to l〇 84.7 00 ο 3Χ106 g CO 1 ATO 雙乙醯基乙酸 二丁基錫 躲 〇 1 g 〇 s 80.8 p 7Χ107 1.60 m csi ATO 乙醯基乙酸鈦 〇 1 in ιο s s 81.0 σ> d 5x 107 1.59 摧 Sn02 乙酸基乙酸錯 摧 .S 1 CO σ> to 5 g 83.0 σ> ο 1 Χ109 1.60 摧 1 導電性微粒子 金屬齡物之種類 有無分散助劑 mm g| si 2陲 迄領 Μ 起|i； S1E sw 葙饀 驿κι •N If u % £_ is g_ t—^ «C™f is 初期値 | 3個月後 I i 6個月後 | 透過率(％) mm%) 表面電阻値(Ω Ο) 折射率 金屬製容器之腐臟態 中徑(nm) -28- 201124490 由表1所示之數據可知，含有金屬錯合物時（實施例 1〜5)，與是否含有分散助劑無關，可得具有優異的保存 安定性之分散液，即使保管於金屬製容器時，仍沒有金屬 容器被腐蝕的狀態。另外，塗佈使用實施例1〜5所得的 分散液之光硬化性組成物所得的透明導電膜，折射率爲 1.45〜1.90、透過率爲75%、霾度爲2.0以下、表面電阻 値爲1012Ω/□以下、具有抗靜電機能、高透明性且導電性 優異。沒有添加金屬錯合物時（比較例1 )，分散困難而無 法製得均勻的分散液。而且，使添加乙醯基丙酮、經分散 的分散液（比較例2)保存於金屬製容器時，確認有顯著的 容器之腐蝕狀態。 於下述中，藉由實施例及參考例，具體說明本發明被 要求高折射率特性的用途之導電性微粒子分散液、透明導 電膜形成用之含導電性微粒子的組成物及透明導電膜。而 且，於實施例及比較例中，「份」全部爲「質量份」。 [實施例6〜1 1及參考例1〜6] 實施例6〜1 1及參考例1〜6中使用的成分，如下所 述。 <高折射率微粒子> 氧化锆（折射率2.2、一次粒徑0.02μηι) 氧化鈦（折射率2.76、一次粒徑0.02μιη) -29- 201124490 <導電性微粒子> ΑΤΟ(折射率2.0、體積電阻値10Ω · cm、一次粒徑 0.0 6 μηι) 氧化錫（折射率2.0、體積電阻値100Ω · cm、一次粒 徑 0 · 0 6 μ m) 氧化鋅（折射率1 ·95、體積電阻値100Ω · cm、一次粒 徑 0 · 0 6 μ m) <金屬錯合物> 乙醯基乙酸锆[Zr(C5H7 02)4] 乙醯基乙酸鈦[Ti(C5H7 02)4] 乙醯基乙酸鋁[A1(C5H702)3 ] 乙醯基乙酸鋅[Zn(C5H702)2] 乙醯基乙酸銦[In(C5H7 02)3 ] 雙乙醯基乙酸二丁基錫[(C4H9)2Sn(C5H702)2] 單乙醯基乙酸三丁氧基銷[(C4H90)3Zr(C5H702)2] <分散助劑> BYK(股）製、BYK-142 <活性能量線硬化性化合物>Daicel Chemical Industry Co., Ltd., Acetylacetone [Example 1] In a container, 20 parts of chromium acetoxyacetate, 250 parts of methyl ethyl ketone and 400 were added in total with respect to 1 part of tin oxide. The amount of glass beads was mixed by hand mixer for 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 4 3 parts of D Ρ Η A, 2 parts of IRGACURE 184 and 65 parts of methyl ethyl ketone were added to prepare a photocurable composition. The photocurable composition was applied onto a PET film (A4100 manufactured by Toyobo Co., Ltd.) having a film thickness of πμπι using a bar coater, and the organic solvent was evaporated, and then irradiated with 300 gJ/cm 2 in a high-pressure mercury lamp in the air. Light, a transparent conductive film having a thickness of 3 μm was produced. The film was produced after the photocurable composition and after 6 months. [Example 2] A total amount of 10 parts of titanium acetylate, 10 parts of cesium-142, 250 parts of 2-butanol, and 400 parts of glass beads were added in a container with respect to 1 part of mash. Mix with a hand mixer for 3 hours. After the kneading, the glass beads were taken out to obtain a dispersion. To the dispersion were added 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanol to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1 [Example 3] -24- 201124490 In a container, dibutyltin acetate was added in a total amount relative to 100 parts of hydrazine, 25 The 2-butanol and 400 parts were mixed in a hand mixer for 3 hours. After the mixing, the beads were prepared to obtain a dispersion. To the dispersion, 43 parts by weight of IRGACURE 184 and 65 parts of 2-butanol were added to prepare a photopolymer. Then, a transparent conductive film was produced by the same method as in Example 1. [Example 4] In a container, the amount of bismuth, 10 parts of dibutyltin bisacetate, and 250 parts of 4 parts of glass beads were added in a total amount with respect to 50 parts of hydrazine, and kneaded by a hand mixer. After the kneading, the glass beads were taken out to prepare a dispersion. A photocurable composition was obtained by dispersing 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 alcohol. Then, a transparent conductive film having a thickness of 3 μm was produced by the method of the embodiment. [Example 5] In a container, a total amount of 40 aluminum, 25 parts of dibutyltin bis-acetoxyacetate, and 250 parts of 4 parts of glass beads were added in a total amount with respect to 60 parts of hydrazine to a manual mixer. After kneading 3 and kneading, the glass beads were taken out to obtain a dispersion. A photocurable composition was obtained by dispersing 67 parts of DPHA, 6.7 parts of IRGACURE 184 and 170 alcohol. Then, by using the glass beads of the same size as in Example 1, the glassy DPHA, 2 sclerosing group, 3 μm, 50 parts of 2-butanol, and the hour were taken out. Add the same portion of 2-butanol 2-butanol and hour to the solution. A transparent conductive film having a thickness of 3 μηι was prepared by adding the same 2-25-201124490 method to the liquid. [Comparative Example 1] 20 parts [, in a container, in a container with respect to 100 parts of tin oxide, a total amount of ΒΥΚ-142, 2 50 parts of 2-butanol and 400 parts of glass beads manually mixed The machine was mixed for 3 hours. The dispersion is viscous during mixing. [Comparative Example 2] Ethylene 3 μηι A thick transparent conductive film was produced in the same manner as in Example 2 except that 20 parts of acetalacetone was added in place of 20 parts of titanium acetate. <Evaluation Method> (1) In-situ hardening of the inorganic fine particles: () The tube was used to make the median diameter of the inorganic fine particles dispersed in the dispersion liquid and the optical composition produced in the examples and the comparative examples, and used in a daily machine ( The ft Microtrac particle size distribution meter was measured after 3 months (after 40 ° C) and after 6 months (stored at 40 ° C) under the following conditions: Electrochromic -26-26- 201124490 (3) Surface The transparent conductive film obtained in the examples and the comparative examples was measured by H iresta IP MCP - Η T 2 60 manufactured by Mitsubishi Chemical Corporation. (4) Refractive index Related to transparent conductive materials obtained in Examples and Comparative Examples The film was measured by an Abe (Abbe) refractometer DRM4 (20 ° C). (5) Corrosion state of the metal container The dispersions prepared in the examples and the comparative examples were placed in a stainless steel container (SUS 3 0 4 ; F e - C r- N i series stainless steel) 'Visually evaluate the corrosion state of the stainless steel container after standing for one month. ° The above measurement results, evaluation results and composition of each composition' are as shown in Table 1. -27- 201124490 [r-|谳] 镒CM ATO 1 1 s σ> ιο in CO in CO 83.4 σ> d 5x 1010 1.59 τ— Sn02 1 1 1 1 1 1 1 1 1 III mm κ to ! ITO Dibutyl thioglycolate 1 CM 1—· Bu CO CO 87.5 _ 1 1 χ ίο1' 00 ιη τ — Deer inch | ATO/1TO Dibutyltin diacetate detoxification 1 csi in LO LO to l〇84.7 00 ο 3Χ106 g CO 1 ATO Dibutyltin diacetate 〇1 g 〇s 80.8 p 7Χ107 1.60 m csi ATO Acetylacetate Titanium 〇 1 in ιο ss 81.0 σ> d 5x 107 1.59 Destroy Sn02 Acetate acetate wrong. S 1 CO σ> to 5 g 83.0 σ> ο 1 Χ109 1.60 Destroy 1 Conductive microparticles Age of metal ages with or without dispersing aids mm g| si 2陲 领领Μ |i; S1E sw 葙饀驿κι •N If u % £_ is g_ t—^ «CTM f is initial 値 | 3 months later I i 6 months later | Transmittance (%) mm%) Surface resistance 値 (Ω Ο) Refractive index metal container viscous medium diameter (nm) -28- 201124490 The data shown in Table 1 shows that when a metal complex is contained (Examples 1 to 5), it is excellent in preservation regardless of whether or not a dispersing aid is contained. The stable dispersion does not have a metal container corroded even when it is stored in a metal container. Further, the transparent conductive film obtained by applying the photocurable composition of the dispersion liquids obtained in Examples 1 to 5 had a refractive index of 1.45 to 1.90, a transmittance of 75%, a twist of 2.0 or less, and a surface resistance 値 of 1012 Ω. /□ Below, it has antistatic function, high transparency and excellent electrical conductivity. When no metal complex was added (Comparative Example 1), dispersion was difficult and a uniform dispersion could not be obtained. Further, when the ethyl isopropyl acetal and the dispersed dispersion (Comparative Example 2) were placed in a metal container, it was confirmed that there was a significant corrosion state of the container. In the following, the conductive fine particle dispersion liquid to which the high refractive index property is required, the conductive fine particle-containing composition for forming a transparent conductive film, and the transparent conductive film of the present invention will be specifically described by way of examples and reference examples. Moreover, in the examples and comparative examples, "parts" are all "mass parts". [Examples 6 to 1 1 and Reference Examples 1 to 6] The components used in Examples 6 to 1 1 and Reference Examples 1 to 6 were as follows. <High refractive index fine particles> Zirconium oxide (refractive index 2.2, primary particle diameter 0.02 μηι) Titanium oxide (refractive index 2.76, primary particle diameter 0.02 μιη) -29- 201124490 <Electrically conductive fine particles> ΑΤΟ (refractive index 2.0 , volume resistance 値10Ω · cm, primary particle size 0.0 6 μηι) tin oxide (refractive index 2.0, volume resistance 値100Ω · cm, primary particle size 0 · 0 6 μ m) zinc oxide (refractive index 1 · 95, volume resistance)値100Ω · cm, primary particle size 0 · 0 6 μ m) <metal complex> Zirconium ethoxide acetate [Zr(C5H7 02)4] Titanium acetate acetate [Ti(C5H7 02)4] B Aluminum thioglycolate [A1(C5H702)3] Zinc acetoxyacetate [Zn(C5H702)2] Indium acetoxyacetate [In(C5H7 02)3 ] Dibutyltin diacetate [(C4H9)2Sn (C5H702 2] monobutoxyacetic acid tributoxyl pin [(C4H90)3Zr(C5H702)2] <dispersion aid> BYK (manufactured by BYK), BYK-142 <active energy ray-curable compound>
日本化藥（股）製、KAYARAD DPHA <光聚合引發劑> -30- 201124490Nippon Kayaku Co., Ltd., KAYARAD DPHA <Photopolymerization Initiator> -30- 201124490
Chiba .Speciality - Chemicals(股）製、IRGACURE 184 <螯合劑> D a i c e 1 C h e m i c a 1 I n d u s t r y (股）製、乙醯基丙酮 [實施例6] 在容器內以相對於1 00份氧化锆，全量加入1 00份氧 化錫、40份之乙醯基乙酸锆、5 00份之2-丁醇及800份 之玻璃珠之量，以手動混合器進行混練7小時。於混練 後，取出玻璃珠，製得分散液。在該分散液中加入86份 之 DPHA、4.3 份之 IRGACURE 184 及 130 份之 2-丁醇， 製得光硬化性組成物。使用輥塗佈器，將該光硬化性組成 物塗佈於膜厚ΙΟΟμηι之PET薄膜（東洋紡（股）製 A4100) 上，使有機溶劑蒸發後，在空氣中使用高壓水銀燈照射 300mJ/Cm2之光，製作厚度3μηι之透明導電膜。膜之製作 係於光硬化性組成物後及6個月後進行。 [實施例7] 在容器內以相對於1 00份氧化鈦，全量加入43份之 ΑΤΟ、0.6份之乙醯基乙酸鈦、14.3份之 ΒΥΚ-142、500 份之2-丁醇及8 00份之玻璃珠之量加入全部成分，以手 動混合器進行混練7小時。於混練後，取出玻璃珠，製得 分散液。在該分散液中加入143份之DPHA、7.2份之 IRGACURE 184及160份之2-丁醇，製得光硬化性組成 -31 - 201124490 物。然後，藉由與實施例6相同的方法，製作厚 之透明導電膜。 [實施例8] 在容器內以相對於1〇〇份ΑΤΟ，全量加入233 化錫、33份之乙醯基乙酸鋁、8 80份之2_丁醇及 之玻璃珠之量，以手動混合器進行混練7小時。 後，取出玻璃珠，製得分散液。在該分散液中加入 之 DPHA、7.2 份之 IRGACURE 184 及 160 份之 2 製得光硬化性組成物。然後，藉由與實施例6相 法，製作厚度3μηι之透明導電膜。 [實施例9] 在容器內以相對於100份氧化駄，全量加入1 氧化鋅、20份之乙醯基乙酸鋅、500份之2-丁醇 份之玻璃珠之量，以手動混合器進行混練7小時。 後，取出玻璃珠，製得分散液。在該分散液中加入 之 DPHA、4.3 份之 IRGACURE 184 及 130 份之 2 製得光硬化性組成物。然後，藉由與實施例6相 法，製作厚度3 μπι之透明導電膜。 [實施例10] 除添加20份之雙乙醯基乙酸二丁基錫取代2〇 醯基乙酸鋅外，藉由與實施例9相同的處理，製作 度 3 μΐϋ 份之氧 8 00份 於混練 143份 -丁醇， 同的方 〇〇份之 及800 於混練 86份 •丁醇， 同的方 份之乙 厚度爲 -32- 201124490 3μπι之透明導電膜。 [實施例1 1 ] 除添加20份之乙醯基乙酸銦取代20份之乙醯基乙酸 鋅外，藉由與實施例9相同的處理，製作厚度爲3μιη之 透明導電膜。 [參考例1 ] 在容器內以相對於1 〇〇份氧化鉻，全量加入1 〇〇份之 氧化錫、20份之ΒΥΚ-142、60份之2-丁醇及800份之玻 璃珠之量，以手動混合器進行混練7小時。於混練中，分 散液產生增黏情形。 [參考例2] 除添加6份之乙醯基丙酮取代6份之乙醯基乙酸鈦 外，藉由與實施例7相同的處理，製作厚度爲3μη!之透 明導電膜。 [參考例3] 在容器內全量加入1〇〇份氧化錫、1〇份之乙醯基乙 酸鈦、6 0 0份之2 - 丁醇及8 0 0份之玻璃珠之量，以手動混 合器進行混練7小時。於混練後，取出玻璃珠，製得分散 液。在該分散液中加入 150份之 DPHA、5 份之 IRGACURE 1 84及100份之2-丁醇，製得光硬化性組成 -33- 201124490 物。然後，藉由與實施例6相同的方法，製作厚度 之透明導電膜。 3 μιη [參考例4] 在容器內全量加入100份氧化鉻、10份之乙醯 酸锆、2 70份之2_丁醇及400份之玻璃珠之量加入全 分，以手動混合器進行混練7小時。於混練後，取出 珠，製得分散液。在該分散液中加入43份之DPHA 份之IRGACURE 184及60份之2 -丁醇，製得光硬化 成物。然後，藉由與實施例6相同的方法，製作厚度 之透明導電膜。 基乙 部成 玻璃 、2.2 性組 3 μηι [參考例5] 除添加40份之單乙醯基乙酸三丁氧基鉻取代40 乙醯基乙酸锆外，藉由與實施例6相同的處理，製作 爲3μπι之透明導電膜。 份之 厚度 [參考例6 ] 除添加40份之單乙醯基乙酸三丁氧基銷取代40 乙醯基乙酸鉻，添加90份之水與410份之2-丁醇 5 0 0份之2 - 丁醇外，藉由與實施例6相同的處理，製 度爲3 μηι之透明導電膜。 份之 取代 作厚 <評估方法> -34- 201124490 另外，無機微粒子及高折射率微粒子之中徑、透明導 電膜之透過率、霾度、表面電阻値、折射率及金屬製容器 之腐蝕狀態，與實施例1〜6相同地進行。 上述之各測定結果、評估結果，與各組成物之組成， 皆如表2所示。 201124490 【3嗽】 參考例 | 2γ02 SnOa 1 u Klifi 獅 fl树 ίΌΗ 晬"1 聒 100 s 1 (0 <D N 9. 3 〇 I 320 I 1 500 I o e I 290 I I 600 I (0 to CO ό 5X10" 40 ω 5. 0 6X10" 00 (Ο m U) ZrOj 1 Sn07 I κι细 mm Γ〇Η ¢11] m ^ 100 1 ? t in o 0. 5 寸 ο 〇 (0 in 〇> 1 200 (0 I —_102 . I 丨.195 I φ ω 00 6 3X10® (0 α ο 3Χ1010 ： Φ (0 Τ· 雔 兮 心〇2 1 1 乙醯基乙酸鉻 j 1 ο 1 n 0. 3 0. 2 in r> O n η CO n to α> 1 0·6 I >1Χ10’4 α> C0 L 〇· 5 ι -1 >1 X1014 ι 卜 Γ) 1 Sn02 I !乙醢基乙酸鈦 1 蘼 1 ffi導憊性St粒子 it KS2 蚊 1 if d 0. 3 Ν •t o 10 o U) U) 寸 ο (A s ο CO CM 1 ΧΊΟ11 η ο O 9X10,0 寸 U> 埋 IN L 丁叫1 1 ATO I I m D (0 143 M o 0. 09 g o r»· CM r- 00 tn U> <〇 o ΙΟ φ ο 7x10” ΙΟ CD - 5 X1011 C0 Φ - -^_1 Sn02 | ι 擗 100 I 1 1 0. 4 ο 6 I 1 t 1 I I 1 1 1 I 1 I I 實施例 二 Ti〇2 1 2nO | 埔思t ss Ν1ΚΪ 堆 1 100 [________ s t (0 00 0. 2 0. 2 α> ΙΑ CM U) u> (〇 o U) 〇) U) 10 Φ ιΰ α> ο 1 ΧΙΟ9 (0 00 to 6 6 x 10β ι 守 r* m 〇 ! Ti〇2 1 ! ZnO | rOES 埔埔 AH h0)1 CKS m 100 s 1 ω φ < 0 0. 2 S U) tn 兮 s CO IA Φ (D » 1_2ι9_1 X (0 ο o 3 X Τ0β r* 0> 1 τί〇2 1 ! ZnO | 賴 r〇N] m 100 8 l *〇 CO 0. 2 0. 08 (Τ) (D in 嘮 « iO o U) s (0 ω Ο X (0 φ 1__1 2x10° < 琏 0D Ν 9 Ν ! sn〇2 | 蝴纽 teas rOKJ 躲 233 n n 1 143 0. 2 6 r- h* o h* w o r〇· m Γ- ό 1 χιοΐ0 r* 00 i__1 4ΧΊ〇'° Φ (0 产 堆 1__ΐί??_1 1 ATO I ι乙醢基 |乙技灶 1_ η (0 l 143 CO d 0. 2 s r» in o ω tn U) in (O Μ (0 (Ω οο ο 5X10” 10 ω 3X10” ω Φ m <〇 1__叫 _ 1 1 Sn〇2 | Ν3Κ) 蘼 丨 100 L. ______ § 1 to α> N d r- d U) (0 s 〇〇 (0 <D (0 r> ω C0 1_9ιΐ_1 5x10® ω C0 r- d 7X10* Φ Φ m 1 1 高折射率Λ粒子 ι f 畀《性微粒子 ι 金鵰错合物之腳 | 有無分畋助劑 1 11 |β i®S i^S IS 掛6H 11 teg ii 滋e 跺領 see H- IS is ll §« 忠〇 茈N3 田M %s »s II 分敗液水份*(«0 光硬化性組成物水份Λ(%) I初期姐I | 3個月後1 | 6佃月後| 1初期値1 I 3個月後| 1 6個月後1 ι初期値ι 1初期值ι 初期值 1 6個月後1 1 6個月後1 6個月後 I 折射串 I I金雇製容器之《独狀賅q 分敗液中徑 (om) 光硬化性組成物 中 tS(wn) Γ透過率(％) ι 1 a 度<%) 1 表面電粗値 (ΩΟ ,_ 厂透s率(¾) 1 「β度(知 ι 表面霉阻值 1ΩΟ_ -36- 201124490 由表2所示之數據可知，含有金屬錯合物時（實施例 6〜11)，與是否含有分散助劑無關，可得具有優異的保存 安定性的分散液，即使保管於金屬製容器時，仍沒有金屬 製容器被腐蝕的狀態。另外，塗佈使用實施例6〜1 1所得 的分散液之光硬化性組成物所得的透明導電膜，折射率爲 1.55〜1.90、透過率爲85%以上、霾度爲1.5%以下、表面 電阻値爲〗0Ι2Ω/□以下、具有高折射率、高透明性且導電 性優異。沒有添加金屬錯合物時（參考例1 )，分散困難而 無法製得均勻的分散液。而且，使添加乙醯基丙酮、經分 散的分散液（參考例2)保存於金屬製容器時，確認有顯著 的容器腐蝕狀態。沒有添加高折射率微粒子時（參考例 3)’無法製得滿足高折射率、高透明性及導電性等全部特 性之膜。沒有添加導電性微粒子時（參考例4)，確認膜不 具導電性。含有烷氧化物作爲金屬錯合物時（參考例5及 6) ’粒徑經時變大，膜特性亦大爲變化。而且，含有很多 水時（參考例6)，確認粒徑顯著增大。 -37-Chiba.Speciality - Chemicals, IRGACURE 184 < Chelating Agent> D aice 1 C hemica 1 I ndustry, acetal acetone [Example 6] Oxidized in a container with respect to 100 parts Zirconium was added in an amount of 100 parts of tin oxide, 40 parts of zirconium ethoxide, 500 parts of 2-butanol, and 800 parts of glass beads in a total amount, and kneaded in a hand mixer for 7 hours. After the kneading, the glass beads were taken out to obtain a dispersion. To the dispersion were added 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanol to obtain a photocurable composition. The photocurable composition was applied onto a PET film (A4100 manufactured by Toyobo Co., Ltd.) having a film thickness of ΙΟΟμηι using a roll coater to evaporate the organic solvent, and then irradiated with 300 mJ/cm 2 of light in a high-pressure mercury lamp in the air. A transparent conductive film having a thickness of 3 μm was produced. The film was produced after the photocurable composition and after 6 months. [Example 7] In a container, 43 parts of ruthenium, 0.6 parts of titanium acetylate acetate, 14.3 parts of ruthenium-142, 500 parts of 2-butanol, and 8 00 were added in total to 100 parts of titanium oxide. The amount of the glass beads was added to the whole ingredients, and the mixture was kneaded in a hand mixer for 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanol were added to prepare a photocurable composition -31 - 201124490. Then, a thick transparent conductive film was produced in the same manner as in Example 6. [Example 8] In a container, a total amount of 233 tin, 33 parts of aluminum acetoxyacetate, 880 parts of 2-butanol, and glass beads were added in an amount of 1 part by weight to be manually mixed. The machine was mixed for 7 hours. Thereafter, the glass beads were taken out to prepare a dispersion. A photocurable composition was prepared by adding DPHA, 7.2 parts of IRGACURE 184 and 160 parts of the dispersion. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6. [Example 9] In a container, a total amount of zinc oxide, 20 parts of zinc acetoxyacetate, and 500 parts of 2-butanol glass beads were added in a total amount with respect to 100 parts of cerium oxide, and the mixture was carried out by a hand mixer. Mix for 7 hours. Thereafter, the glass beads were taken out to prepare a dispersion. A photocurable composition was prepared by adding DPHA, 4.3 parts of IRGACURE 184 and 130 parts of the dispersion. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6. [Example 10] Except that 20 parts of dibutyltin diacetate was used in place of zinc thioglycolate, by the same treatment as in Example 9, 80 parts of oxygen of 3 μM parts was prepared for 143 parts by kneading. - Butanol, the same square and 800 in a mixture of 86 parts of butanol, the same thickness of B is -32- 201124490 3μπι transparent conductive film. [Example 1 1] A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 9 except that 20 parts of indium acetylacetate was added in place of 20 parts of zinc acetoxyacetate. [Reference Example 1] In a container, a total amount of tin oxide, 20 parts of strontium-142, 60 parts of 2-butanol, and 800 parts of glass beads were added in an amount relative to 1 part of chromium oxide. The mixture was mixed for 7 hours with a manual mixer. In the mixing process, the dispersion produces a viscosity-increasing condition. [Reference Example 2] A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 7 except that 6 parts of acetaminoacetone was used instead of 6 parts of titanium acetoxyacetate. [Reference Example 3] A total amount of 1 part of tin oxide, 1 part of titanium acetoxyacetate, 20,000 parts of 2-butanol, and 80 parts of glass beads were added in a container to be manually mixed. The machine was mixed for 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 150 parts of DPHA, 5 parts of IRGACURE 1 84 and 100 parts of 2-butanol were added to prepare a photocurable composition -33 - 201124490. Then, a transparent conductive film having a thickness was produced in the same manner as in Example 6. 3 μηη [Reference Example 4] Add 100 parts of chromium oxide, 10 parts of zirconium citrate, 2 70 parts of 2-butanol and 400 parts of glass beads to the whole amount in the container, and add the whole amount by hand mixer. Mix for 7 hours. After the kneading, the beads were taken out to obtain a dispersion. To the dispersion, 43 parts of DPHA portion of IRGACURE 184 and 60 parts of 2-butanol were added to prepare a photocured product. Then, a transparent conductive film having a thickness was produced in the same manner as in Example 6. The base part was made into glass, and the 2.2 group of 3 μηι [Reference Example 5] was produced by the same treatment as in Example 6 except that 40 parts of monobutylglycolic acid tributoxy chromium was substituted for 40 acetonitrile zirconium acetate. It is a transparent conductive film of 3 μm. The thickness of the portion [Reference Example 6] In addition to adding 40 parts of monobutoxyacetic acid tributoxyl pin to replace 40 ethoxylated chromium acetate, adding 90 parts of water and 410 parts of 2-butanol 500 parts 2 In the same manner as in Example 6, except for butanol, the system was a transparent conductive film of 3 μη. Substituting for thickness <evaluation method> -34- 201124490 In addition, the diameter of the inorganic fine particles and the high refractive index fine particles, the transmittance of the transparent conductive film, the twist, the surface resistance 値, the refractive index, and the corrosion of the metal container The state was carried out in the same manner as in Examples 1 to 6. The above measurement results, evaluation results, and composition of each composition are shown in Table 2. 201124490 [3嗽] Reference example | 2γ02 SnOa 1 u Klifi lion fl tree ΌΗ 晬"1 聒100 s 1 (0 <DN 9. 3 〇I 320 I 1 500 I oe I 290 II 600 I (0 to CO ό 5X10" 40 ω 5. 0 6X10" 00 (Ο m U) ZrOj 1 Sn07 I κι细mm Γ〇Η ¢11] m ^ 100 1 ? t in o 0. 5 inch ο 〇 (0 in 〇> 1 200 (0 I —_102 . I 丨.195 I φ ω 00 6 3X10® (0 α ο 3Χ1010 : Φ (0 Τ·雔兮心〇2 1 1 Ethyl acetate chrome j 1 ο 1 n 0. 3 0 2 in r> O n η CO n to α> 1 0·6 I >1Χ10'4 α> C0 L 〇· 5 ι -1 >1 X1014 ι 卜Γ) 1 Sn02 I ! 1 蘼1 ffi St St St particles it KS2 Mosquito 1 if d 0. 3 Ν • to 10 o U) U) inch ο (A s ο CO CM 1 ΧΊΟ11 η ο O 9X10, 0 inch U> buried IN L Called 1 1 ATO II m D (0 143 M o 0. 09 gor»· CM r- 00 tn U><〇o ΙΟ φ ο 7x10” ΙΟ CD - 5 X1011 C0 Φ - -^_1 Sn02 | ι 擗100 I 1 1 0. 4 ο 6 I 1 t 1 II 1 1 1 I 1 II Example 2 Ti〇2 1 2nO | 思思t ss Ν1ΚΪ heap 1 100 [________ st (0 00 0. 2 0. 2 α≫ CM CM U) u> (〇o U) 〇) U) 10 Φ ιΰ α> ο 1 ΧΙΟ9 (0 00 to 6 6 x 10β ι 守 r* m 〇! Ti〇2 1 ! ZnO | rOES AH h0)1 CKS m 100 s 1 ω φ < 0 0. 2 SU) tn 兮s CO IA Φ (D » 1_2ι9_1 X (0 ο o 3 X Τ0β r* 0> 1 τί〇2 1 ! ZnO | r〇N] m 100 8 l *〇CO 0. 2 0. 08 (Τ) (D in 唠« iO o U) s (0 ω Ο X (0 φ 1__1 2x10° < 琏0D Ν 9 Ν ! sn 〇2 | 蝶纽 teas rOKJ hide 233 nn 1 143 0. 2 6 r- h* oh* wor〇· m Γ- ό 1 χιοΐ0 r* 00 i__1 4ΧΊ〇'° Φ (0 heap 1__ΐί??_1 1 ATO I 醢乙醢基|乙技灶1_ η (0 l 143 CO d 0. 2 sr» in o ω tn U) in (O Μ (0 (Ω οο ο 5X10" 10 ω 3X10" ω Φ m <〇 1__叫_ 1 1 Sn〇2 | Ν3Κ) 蘼丨100 L. ______ § 1 to α> N d r- d U) (0 s 〇〇(0 <D (0 r> ω C0 1_9ιΐ_1 5x10® ω C0 r- d 7X10* Φ Φ m 1 1 High refractive index Λparticle ι f 畀 "Sexual microparticles ι Golden sculpt complex foot | With or without bismuth auxiliaries 1 11 |β i®S i^S IS hang 6H 11 Teg ii 滋e 跺 collar see H- IS is ll §« 〇茈N3 Tian M %s »s II Fractional water* («0 photohardenable composition water Λ (%) I initial sister I | 3 months later 1 | 6 months later | 1 initial 値 1 I 3 months later | 1 6 months later 1 ι initial 値ι 1 initial value ι initial value 1 6 months after 1 1 6 months after 1 6 months I refracted string II gold hiring container赅q split medium diameter (om) light hardening composition tS(wn) Γ transmittance (%) ι 1 a degree <%) 1 surface electric rough (ΩΟ, _ factory penetration rate (3⁄4) 1 "β degree (Immediate surface mold resistance value 1 Ω Ο - -36- 201124490 From the data shown in Table 2, it is known that when a metal complex is contained (Examples 6 to 11), regardless of whether or not a dispersing aid is contained, The excellent dispersion-preserving dispersion does not have a metal container corroded even when it is stored in a metal container. Further, the transparent conductive film obtained by applying the photocurable composition of the dispersion liquid obtained in Examples 6 to 1 1 has a refractive index of 1.55 to 1.90, a transmittance of 85% or more, a twist of 1.5% or less, and surface resistance.値 is Ι0Ι2 Ω/□ or less, has high refractive index, high transparency, and is excellent in electrical conductivity. When no metal complex was added (Reference Example 1), the dispersion was difficult and a uniform dispersion could not be obtained. Further, when the dispersion liquid (reference example 2) to which ethyl acetonylacetate was added and stored in a metal container was stored, it was confirmed that there was a significant corrosion state of the container. When the high refractive index fine particles were not added (Reference Example 3), it was impossible to obtain a film satisfying all the characteristics such as high refractive index, high transparency, and electrical conductivity. When no conductive fine particles were added (Reference Example 4), it was confirmed that the film was not electrically conductive. When an alkoxide is contained as a metal complex (Reference Examples 5 and 6), the particle diameter becomes large with time, and the film properties greatly change. Further, when a large amount of water was contained (Reference Example 6), it was confirmed that the particle diameter was remarkably increased. -37-