200815195 九、發明說明： 【發明所屬之技術領域】 本發明係關於防污性薄膜及其製法，更詳言之’係關 於具有油性污物等不會附著之防污性表面之防污性薄膜及 其製法。 【先前技術】 污染物質在材料表面附著所引起之「污物」係由於污 染之進行，不僅損及美觀，亦使材料表面具有之機能降低。 因此，爲了「防污」，必須使污染物質之附著（相互作用）降 低。污染物質之附著降低一般係藉由材料表面之親水化或 撥油化來達成。 以往，作爲具有撥水性及防污性之薄膜，係使用在其 最表面將氟化合物層予以濕式塗布（濕式成膜），而具有撥 水性與防污性之物（例如專利文獻1参照。）。然而，有機 物之表面塗層的表面硬度及耐久性低，因此該等之改良係 爲必要。 爲了解決此種問題，檢討使用具有優異撥水性與防污 性、表面能量小之二氧化矽層，該二氧化矽層係可預期上 述表面硬度及耐久性之改良。然而，將具有撥水性與防污 性之二氧化矽層在支撐體上塗布Μ，而得具有撥水性及防 污性之薄膜時，由於二氧化矽層之表面能量小，而有與支 撐體之間的密接力變小的問題點。 爲了改善支撐體與表面二氧化矽層之密接性，有提案 在支撐體與表面二氧化矽層之間，設置碳含量小於2 0原子 %之密接二氧化矽層作爲中間層（例如参照專利文獻 200815195 2。）。該方法係藉由將表面能量大之密接二氧化矽 於表面二氧化矽層與支撐體之間，而改良支撐體與 氧化矽層之密接性，然而該密接性尙稱不上充分， 於碳含量導致表面能量、撥水性、防污性係大幅變 此有其調製爲困難之問題點。 【專利文獻1】特開2000-2841 02號公報 【專利文獻2】特開2002-1 1 3805號公報 【發明內容】 φ 【發明所欲解決之課題】 因此，因此有對於支撐體的密接性優異且具備 油處理面，具有高防污性及其持續性之防污性薄膜 法的需求。 【解決課題之手段】 本發明者等對於含有在支撐體上直接結合之接 物鏈、與藉由金屬醇鹽之加水分解及縮聚合反應所 交聯構造之有機-無機複合層加以鑽硏探討，根據將 φ -無機複合層適當地用於防污性薄膜而完成本發明。 本發明的第1觀點係提供一種防污性薄膜，本 防污性薄膜，其係具有支撐體與有機-無機複合層， Λ 有機-無機複合層表面施以撥水撥油處理所構成，其 機-無機複合層係在直接結合至該支撐體表面的接 物鏈所構成的接枝聚合物層中，含有選自 Si、Ti、 之元素的醇鹽之加水分解及縮聚合所形成之交聯構 前記接枝聚合物鏈係以藉由在支撐體表面經發 始種作爲起點的聚合反應所生成之物爲佳。又，前 層設置 表面二 更且由 化，因 撥水撥 及其製 枝聚合 形成的 該有機 發明之 且對該 中該有 枝聚合 Zr、AI 造。 生之開 記接枝 200815195 聚合物鏈係以在其鏈中具有選自於Si、Ti、Zr、AI之元素 的醇鹽基、及/或醯胺基者爲佳。更佳爲前記接枝聚合物鏈 係以具有極性基，較佳爲具有醯胺基之構造單位、與具有 矽烷偶合基等選自於Si、Ti、Zr、A丨之元素的醇鹽基之構 造單位的共聚物爲較佳之態樣。 本發明之第2觀點爲提供一種防污性薄膜之製法，本 發明之防污性薄膜之製法係具有下列步驟：生成直接結合 至支撐體表面之接枝聚合物鏈，形成該接枝聚合物鏈所構 成之接枝聚合物層之步驟；在該接枝聚合物層中，進行選 自於Si、Ti、Zr、AI之元素的醇鹽之加水分解及縮聚合的 交聯反應，以形成有機-無機複合層之步驟；與對該有機-無機複合層表面施以撥水撥油處理之步驟。 【發明效果】 本發明爲提供一種對支撐體之密接性優異、具備撥水 撥油處理面，且具有高防污性及其持續性之防污性薄膜及 其製法。 【實施方式】 【實施發明之最佳形態】 以下，詳細說明本發明。又，在本說明書中「〜」係表 示包含其前後所記載之數値的最小値及最大値之範圍。 本發明之防污性薄膜係具有支撐體與有機-無機複合 層’且對該有機-無機複合層表面施以撥水撥油處理所構 成’其中該有機-無機複合層係在直接結合至該支撐體表面 的接枝聚合物鏈所構成的接枝聚合物層中，含有選自S i、 Ti、Zr、AI之元素的醇鹽之加水分解及縮聚合所形成之交 200815195 聯構造。 本發明之防污性薄膜，從反應性、化合物之取得容易 性而言，以形成使用S i之醇鹽的交聯構造爲較佳。 如前述之藉由醇鹽之加水分解及縮聚合所形成的交聯 構造，在本發明以下適當地稱爲「溶膠膠體交聯構造」。 此種本發明之防污性薄膜係藉由下述本發明之防污性 薄膜之製法所製造。即，本發明之防污性薄膜之製法係適 合使用具有下列步驟之方法爲佳：生成直、接結合至支撐體 H 表面之接枝聚合物鏈，形成該接枝聚合物鏈所構成之接枝 聚合物層之步驟，〔以下適當地稱爲「接枝聚合物層形成步 驟」〕；在該接枝聚合物層中，進行選自於Si、Ti、Zr、AI 之元素的醇鹽之加水分解及縮聚合的交聯反應，以形成有 機-無機複合層之步驟〔以下適當地稱爲「有機-無機複合 層形成步驟」〕：與對該有機-無機複合層表面施以撥水撥油 處理之步驟〔以下適當地稱爲「撥水撥油處理步驟」〕。 本發明之作用雖不明確，惟推定如下。 • 本發明中之有機-無機複合層係含有直接結合至該支 撐體表面的接枝聚合物鏈（有機成分）、與藉由選自Si、Ti、 Zr、AI之元素的醇鹽之加水分解及縮聚合所形成之交聯構 造（無機成分）所構成。該有機-無機複合層雖然是薄層，但 是耐摩耗性増大且具有高耐久性。 尤其是接枝聚合物鏈具有極性基的情況下，藉由其極 性基之機能而形成與交聯構造間的極性相互作用，可變爲 強度及耐久性優異之有機-無機複合層。更且，接枝聚合物 鏈爲在其鏈中具有選自於Si、Ti、Zr、A1之元素的醇鹽基 200815195 的情況下，在該接枝聚合物鏈與交聯構造之間形成共價 鍵，有機-無機複合層之強度及耐久性提升。更且，該有機 -無機複合層中之交聯構造係具有起因於選自Si、Ti、Zr、 AI之元素的醇鹽之反應性基，藉由在該反應性基與用於撥 水撥油處理之化合物之間形成共價鍵，可得對支撐體之密 接性優良的撥水撥油處理面。其結果，推定可得到具有高 防污性及其持續性之防污性薄膜。 ' 以下依序說明「接枝聚合物層形成步驟」、「有機-無機 複合層形成步驟」、及「撥水撥油處理步驟」。 <接枝聚合物層形成步驟> 在本步驟，生成直接結合至支撐體表面之接枝聚合物 鏈，形成該接枝聚合物鏈所構成之接枝聚合物層。 生成直接結合至支撐體表面之接枝聚合物鏈的方法， (1)將支撐體作爲基點，使具有可聚合之雙鍵的化合物進行 表面接枝聚合，生成接枝聚合物鏈之方法（以下適當地稱爲 「方法1」）、（2)使具有與支撐體反應之官能基的聚合物、 與支撐體表面進行化學鍵結，生成接枝聚合物鏈之方法（以 下適當地稱爲「方法2」）。 以下說明該2個方法。 (1)將支撐體作爲基點，使具有可聚合之雙鍵的化合物 進行表面接枝聚合，生成接枝聚合物鏈之方法（方法1 ) 方法1係通常稱爲表面接枝聚合之方法。表面接枝聚 合法係以電漿照射、光照射、加熱等方法，在支撐體表面 上賦予活性種，將此活性種作爲基點，使以與支撐體相接 的形式來配置之具有可聚合雙鍵之化合物進行重合之方 200815195 法。若根據該方法，生成之接枝聚合物鏈末端係直接結合 至支撐體表面並固定。 爲實施本發明之表面接枝聚合法，可任意使用文獻記 載之公知方法。例如，在新高分子實驗學1 0、高分子學會 編、1 994年、共立出版（股）發行、ΡΊ 35記載光接枝聚合法、 電漿照射接枝聚合法作爲表面接枝聚合法。又，吸着技術 便覧、NTS(股）、竹内監修、1 999.2發行、p203、p 695記 載Y線、電子線等放射線照射接枝聚合法。光接枝聚合法 • 之具體方法，可使用特開昭 63-92658號公報、特開平 1 0-296895號公報及特開平11-119413號公報所記載之方 法。關於電漿照射接枝聚合法、放射線照射接枝聚合法， 可適當地使用記載於上述記載之文獻、及丫.Ikada et al， Macromolecules vo 1.19、第 1804 頁（1986)等之方法。 具體而言，在以電漿或電子線處理表面發生活性種之 自由基，之後藉由使具有該活性種之支撐體表面與具有可 聚合雙鍵的化合物（例如單體）反應，可使PET等高分子表 φ 面生成接枝聚合物鏈。 光接枝聚合，除了上述記載之文獻以外，亦可如特開 昭53-1 7407號公報（關西油漆）、特開2000-21 231 3號公報 (大日本油墨）所記載，藉由在薄膜支撐體之表面塗布光聚 合性組成物，使自由基聚合化合物接觸光照射予以實施。 藉由方法1生成接枝聚合物鏈時有用之化合物必須具 有可聚合之雙鍵。又，考慮到與在後述之有機-無機複合層 形成步驟中所形成之溶膠膠體交聯構造之極性相互作用之 形成性時，以具有可聚合之雙鍵且具有極性基之化合物爲 -10- 200815195 佳。更且，考慮到在後述有機-無機複合層形成步驟所形成 之溶膠膠體交聯構造之間形成共價鍵時，以具有可聚合之 雙鍵且具有特定元素醇鹽基之化合物爲佳。 適用於方法1之化合物，在分子内具有雙鍵、視需要 具有極性基及/或特定元素醇鹽基時，聚合物、低聚合物、 單體，可使用該等中任一化合物。在本發明中有用化合物 之一個爲具有極性基之單體。 關於具有本發明中有用之極性基之單體，可列舉銨、 鱗等具有正荷電之單體、或磺酸基、羧基、磷酸基、膦酸 基等具有負荷電或負荷電解離而得的酸性基之單體，亦可 使用其他例如羥基、醯胺基、磺醯胺基、烷氧基、氰基、 等具有非離子性基之極性基之單體。 本發明中，具有特別有用之極性基之單體的具體例， 可列舉以下單體。例如，可使用（甲基）丙烯酸或其鹼金屬 鹽及胺鹽、伊康酸或其鹼金屬鹽及胺基酸鹽、烯丙基胺或 其鹵化氫酸鹽、3-乙烯基丙酸或其鹼金屬鹽及胺鹽、乙烯 基磺酸或其鹼金屬鹽及胺鹽、苯乙烯磺酸或其鹼金屬鹽及 胺鹽、2-磺乙烯（甲基）丙烯酸酯、3-磺丙烯（甲基）丙烯酸酯 或其鹼金屬鹽及胺鹽、2 -丙烯醯胺-2 -甲基丙烷磺酸歲其鹼 金屬鹽及胺鹽、醯胺基磷氧基聚乙二醇單（甲基）丙烯酸酯 或該等之鹽、2-二甲基胺基乙基（甲基）丙烯酸酯或其鹵化 氫酸鹽、3-三甲基銨丙基（甲基）丙烯酸酯、3-三甲基銨丙基 (甲基）丙烯醯胺、N,N，N-三甲基-N-(2-羥基-3-甲基丙烯醯 基氧基丙基）氯化銨等。又，2-羥基乙基（甲基）丙烯酸酯、（甲 基）丙烯醯胺、N-單羥甲基（甲基）丙烯醯胺、N-二羥甲基（甲 200815195 基）丙烯醯胺、N-乙烯基吡咯啶酮、N-乙烯基乙醯 乙二醇單（甲基）丙烯酸酯等亦有用。 本發明有用之具有極性基之大分子單體可J “新高分子實驗學2、高分子之合成·反應”高分子 共立出版（股）1 9 9 5中記載之合成法而得者。又， 他著“巨單體之化學與工業”IPC、1 989中亦詳細 體而言，使用丙烯酸、丙烯醯胺、2-丙烯醯胺-2-磺酸、N-乙烯基乙醯醯胺等上述具體地記載之具 φ 之單體，根據文獻記載之方法可合成具有極性基 單體。 本發明使用之具有極性基之大分子單體之中 用者爲由丙烯酸、甲基丙烯酸等含有羧基之單體 分子單體，由2-丙烯醯胺-2-甲基丙烷磺酸、苯乙 及其鹽之單體衍生之磺酸系大分子單體，丙烯醯 丙烯醯胺等之醯胺系大分子單體，由N-乙烯基乙 N -乙烯基甲醯胺等之N -乙烯基羧酸醯胺單體衍 φ 系大分子單體，由羥基乙基甲基丙烯酸酯、羥基 酸酯、甘油單甲基丙烯酸酯等含有羥基之單體衍 子單體，由甲氧基乙基丙烯酸酯、甲氧基聚乙二 酯、聚乙二醇丙烯酸酯等含有烷氧基或環氧乙烷 衍生之大分子單體。又，具有聚乙二醇鏈或聚丙 單體亦可用來作爲本發明大分子單體。 該等大分子單體中，從形成與後述有機-無機 成步驟中所形成之溶膠膠體交聯構造之極性相互 之點而言，以使用具有醯胺基之大分子單體作爲 醯胺、聚 以是藉由 學會編、 在山下雄 記載。具 甲基丙烷 有極性基 之大分子 ，特別有 衍生之大 烯磺酸、 胺、甲基 醯醯胺、 生之醯胺 乙基丙烯 生之大分 醇丙烯酸 基之單體 二醇鏈之 複合層形 作用爲強 極性基爲 -12- 200815195 佳0 該等大分子單體之中有用之分子量爲400〜1〇萬之範 圍、較佳範圍爲1 000〜5萬、特佳範圍爲1 500〜2萬之範圍。 又’本發明中接枝聚合物鏈係如先前所述，已在其鏈 中具有選自於Si、Ti、Zr、AI之元素的醇鹽基（以下適當地 稱爲特定兀素醇鹽基）者爲佳。該特定元素醇鹽基係經由與 後述交聯劑（金屬醇鹽）之加水分解及縮聚合反應，而形成 共價鍵之置換基。由於此種接枝聚合物鏈係具有特定元素 醇鹽基，因此可在後述有機-無機複合層形成步驟中所形成 之溶膠膠體交聯構造與接枝聚合物鏈之間形成共價鍵。 使用方法1之表面接枝聚合法的情況下，以使用具有 特定元素醇鹽基之單體或大分子單體爲佳。代表性地列舉 矽烷偶合基作爲該特定元素醇鹽基以具體説明。在本發明 適合之矽烷偶合基可例示下述一般式（I)所示之官能基。 一般式（丨） (R1)m(〇R2)3-m—SI— 一般式（I)中，R1及R2係分別獨立地表示氫原子、或 碳數8以下之羥基，m表示0〜2之整數。 R1及R2係表示羥基時之羥基，可列舉烷基、芳基等， 以碳數8以下之直鏈、分岐或環状烷基爲佳。具體而言， 可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛 基、異丙基、異丁基、s-丁基、t_丁基、異戊基、新戊基、 1-甲基丁基、異己基、2 -乙基己基、2 -甲基己基、環戊基 等0 -13- 200815195 R1及R2從效果及取得容易性之觀點而言，較佳爲氫 原子、甲基或乙基。 一般式⑴所示之具有官能基之單體，可列舉（3-丙烯醯 氧基丙基）三甲氧基矽烷、（3-丙烯醯氧基丙基）二甲基甲氧 基矽烷、（3-丙烯醯氧基丙基）甲基二甲氧基矽烷、（甲基丙 烯醯氧基甲基）二甲基乙氧基矽烷、（甲基丙烯醯氧基甲基） 乙氧基矽烷、（甲基丙烯醯氧基甲基）三甲氧基矽烷、（甲基 丙烯醯氧基丙基）二甲基乙氧基矽烷、（甲基丙烯醯氧基丙 Φ 基）二甲基甲氧基矽烷、（甲基丙烯醯氧基丙基）甲基二乙氧 基矽烷、（甲基丙烯醯氧基丙基）乙氧基矽烷、（甲基丙烯醯 氧基丙基）三異丙基矽烷、甲基丙烯醯氧基丙基（參甲氧基 乙氧基）矽烷等。 本發明中，使用方法1的情況下，以使用具有極性基 之單體或大分子單體、與具有矽烷偶合基等特定元素醇鹽 基之單體或大分子單體，以表面接枝聚合法進行共重合， 生成接枝聚合物鏈爲佳。其中，以使用具有醯胺基之單體 φ 或大分子單體作爲極性基爲更佳。 (2)使具有與支撐體反應之官能基的聚合物、與支撐體 表面進行化學鍵結，生成接枝聚合物鏈之方法（方法2) 在方法2中，可使用在主鏈末端或側鏈具有與支撐體 反應之官能基的聚合物，使該官能基與支撐體表面之官能 基進行化學反應，以生成接枝聚合物鏈。與支撐體反應之 官能基，只要是可與支撐體表面之官能基反應者，並無特 別限定，可列舉例如烷氧基矽烷之類的矽烷偶合基、異氰 酸酯基、胺基、羥基、羧基、磺酸基、磷酸基、環氧基、 -14- 200815195 烯丙基、甲基丙烯醯基、丙烯醯基等。 j 作爲在主鏈末端或側鏈具有與支撐體反應之官能基之 聚合物特別有用之化合物爲：在聚合物末端具有三烷氧基 矽烷基之聚合物、在聚合物末端具有胺基之聚合物、在聚 合物末端具有羧基之聚合物、在聚合物末端具有環氧基聚 合物、在聚合物末端具有異氰酸酯基之聚合物。 又，此時所使用之聚合物更佳爲具有極性基，具有極 性基之聚合物，具體而言可列舉聚丙烯酸、聚甲基丙烯酸、 # 聚苯乙烯磺酸、聚-2-丙烯醯胺-2-甲基丙烷磺酸及該等之 鹽、聚丙烯醯胺、聚乙烯基乙醯醯胺等。該等以外，亦可 使用在前述方法（1)所使用之具有極性基之單體的聚合 物、或含具有極性基之單體的共聚物。 又，從形成與後述有機-無機複合層形成步驟中所形成 之溶膠膠體交聯構造的極性相互作用爲強之點而言，以使 相具有醯胺基之聚合物作爲極性基爲佳。 另一方面，在主鏈末端或側鏈具有與支撐體反應之官 φ 能基之聚合物更佳爲具有選自於Si、Ti、Ζιγ、AI之元素的 醇鹽基（特定元素醇鹽基）。藉由使用該聚合物，可在生成 的接枝聚合物鏈中導入特定元素醇鹽基。藉由使此種接枝 聚合物鏈具有特定元素醇鹽基，可在後述有機-無機複合層 形成步驟中所形成之溶膠膠體交聯構造與接枝聚合物鏈之 間形成共價鍵。 在本發明中，在主鏈末端或側鏈具有與支撐體反應之 官能基之聚合物以具有醯胺基與特定元素醇鹽基兩方兩者 極性基作爲係特佳。 -15- 200815195 本發明中’與溶膠膠體交聯構造之極性相互作用的形 成性'共價鍵之形成性之點而言，用上述方法所生成之接 枝聚合物鏈中，以具有醯胺基及/或特定元素醇鹽基爲佳。 在本發明接枝聚合物鏈中醯胺基之較佳導入量爲 10mol %〜90mol%之範圍，又，特定元素醇鹽基之導入量以 1 0 m ο I %〜9 0 m ο I %之範圍爲佳。 在本發明，接枝聚合物鏈以在其鏈中具有上述極性 基、特定元素醇鹽基者爲佳，惟除該等基以外，亦可導入 # 交聯性基或聚合性基等，用此等基以在接枝聚合物鏈間形 成交聯構造。 (支撐體） 本發明中支撐體可任意使用具有機械的強度、尺寸安 定性之物，惟在防污性薄膜必須要有透過性的情況下，較 佳爲使用具有透明性之薄膜。/ 作爲支撐體使用之薄膜，具體而言可列舉聚對苯二甲 酸乙二酯薄膜、聚對苯二甲酸乙二酯系共重合聚酯薄膜、 φ 聚萘酸乙二酯薄膜等聚酯薄膜；耐綸66薄膜、耐綸6薄膜、 間苯二甲基二胺共重合聚醯胺薄膜等聚醯胺薄膜；聚丙烯 薄膜、聚乙烯薄膜、乙烯-丙烯共聚物薄膜等聚烯烴薄膜； 聚亞胺薄膜；聚醯胺亞胺薄膜；聚乙烯醇薄膜；乙烯-乙烯 醇共聚物薄膜；聚伸苯基薄膜；聚颯薄膜；聚伸苯基硫薄 膜等。該等其中，從成本性能、透明性等觀點而言，以聚 對苯二甲酸乙二酯薄膜等聚酯薄膜、聚乙烯薄膜、聚丙烯 薄膜等聚烯烴薄膜爲佳。該等薄膜可爲延伸、未延伸之任 一者，可單獨使用，亦可積層相異性質之薄膜使用。 -16 - 200815195 關於作爲支撐體用之薄膜，只要不損及本發明之效果 並無限制，可含有各種添加劑或安定劑，亦可經塗布。可 *用之添加劑，可列舉例如抗氧化劑、抗靜電劑、紫外線防 止劑、可塑劑、滑劑、熱安定劑等。又，該薄膜亦可施行 電暈處理、電漿處理、輝光放電處理、離子沖罐 (b 〇 m b a r d m e n t)處理、藥品處理、溶劑處理、粗面化處理 等表面處理。 支撐體之厚度考慮包裝材料等使用目的之適性，可適 φ 宜地設定，並不受特別限制，惟從一般實用之觀點而言， 較佳爲3μΓΠ~ 1mm之範圍，從可撓性或加工性之觀點而言， 以10μηι〜300pm之範圍爲更佳。 支撐體爲藉由其本身賦予能量，而發生活性種之物 時，其可直接使用，惟以良好效率進行形成接枝聚合物鏈 之開始種的發生爲目的，亦可在支撐體表面包括具有聚合 引發能之表面層。 具有聚合引發能之表面層，以含有低分子或高分子之 φ 聚合引發劑的層爲佳。其中，從安定性、耐久性之觀點而 言，較佳爲藉由交聯反應將聚合引發劑固定化所構成之聚 合引發層；更佳爲藉由交聯反應將在側鏈具有聚合引發能 之官能基及交聯性基之聚合物固定化所構成之聚合引發 層。 關於藉由交聯反應將在側鏈具有聚合引發能之官能基 及交聯性基之聚合物固定化所構成之聚合引發層，詳細記 載於特開2004-161995號公報中段落編號〔0011〕~〔 0169〕 之記載，該聚合引發層可適用於本發明。 -17- 200815195 <有機-無機複合層形成步驟> 在本步驟·，於以前述接枝聚合物層形成步驟所得之接 枝聚合物層中，進行選自於Si、Ti、Zr、AI之元素的醇鹽 之加水分解及縮聚合的交聯反應，而形成有機-無機複合 層。 簡言之，本發明中有機-無機複合層爲包含接枝聚合物 鏈構成之有機成分、與藉由進行選自於Si、Ti、Zr、AI之 元素的醇鹽之加水分解及縮聚合的交聯反應形成之交聯構 φ 造（溶膠膠體交聯構造）所構成的無機成分之層。 首先，本步驟爲使用形成藉由進行選自於Si、Ti、Zr、 AI之元素的醇鹽之加水分解及縮聚合的交聯反應所形成之 交聯構造的化合物（以下有時單獨稱爲「交聯劑」），形成 本發明中溶膠膠體交聯構造爲佳。 本發明中交聯劑，可使用例如下述一般式（丨丨）所表示之 化合物。 下述一般式（II)所表示之化合物係接枝聚合物鏈具有 φ 特定元素醇鹽基的情形，藉由該特定元素醇鹽基與加水分 解及縮聚合，在接枝聚合物鏈與溶膠膠體交聯構造之間可 形成共價鍵。藉此，可形成強固之有機-無機複合層。 一般式（丨丨1 (R6)m-X-(〇R7)4-m 一般式（I I)中，R6表示氫原子、烷基、或芳基，R7表示 烷基或芳基，X表示Si、AhTi或Zr，m表示〇〜2之整數。 R6及R7係表示烷基的情況下，其碳數較佳爲1至4。 -18- 200815195 烷基或芳基亦可具有置換基，可導入之置換基可列舉 子、胺基、锍基等。 又，該化合物爲低分子化合物，以分子量1 〇 〇 〇以 佳。 以下列舉一般式（M)所表示之化合物的具體例，惟 明並不受該等所限定。 X爲S i時，即，在加水分解性化合物中含矽之物 列舉例如三甲氧基矽烷、乙氧基矽烷、三丙氧基矽烷 φ 甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、甲基三 基矽烷、乙基乙氧基矽烷、丙基三甲氧基矽烷、甲基 基矽烷、乙基乙氧基矽烷、丙基乙氧基矽烷、二甲基 氧基矽烷、二乙基二乙氧基矽烷、γ-氯丙基乙氧基矽煩 锍基丙基三甲氧基矽烷、Y-锍基丙基乙氧基矽烷、Y-丙基乙氧基矽烷、苯基三甲氧基矽烷、苯基乙氧基矽 苯基三丙氧基矽烷、二苯基二甲氧基矽烷、二苯基二 基矽烷等。 φ 該等之中特佳者，可列舉四甲氧基矽烷、四乙氧 烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷、甲基乙 矽烷、乙基乙氧基矽烷、二甲基二乙氧基矽烷、苯基 氧基矽烷、苯基乙氧基矽烷、二苯基二甲氧基矽烷、 基二乙氧基砂院等。 又，X爲AI時，即，在加水分解性化合物中含鋁2 可列舉例如三甲氧基鋁酸鹽、三乙氧基鋁酸鹽、三丙 鋁酸鹽、四乙氧基鋁酸鹽等。 X爲Ti時，即，含鈦之物可列舉例如三甲氧基鈦酉 鹵原 下爲 本發 ，可 、四 甲氧 乙氧 二甲 :、Y- 胺基 院、 乙氧 基矽 氧基 三甲 二苯 :物， 氧基 隻鹽、 -19 · 200815195 四甲氧基鈦酸鹽、三乙氧基鈦酸鹽、四乙氧基鈦酸鹽、四 丙氧基鈦酸鹽、氯三甲氧基鈦酸鹽、氯三乙氧基鈦酸鹽、 乙基三甲氧基鈦酸鹽、甲基三乙氧基鈦酸鹽、乙基三乙氧 基鈦酸鹽、二乙基二乙氧基鈦酸鹽、苯基三甲氧基鈦酸鹽、 苯基三乙氧基鈦酸鹽等。 X爲Zr時，即，含锆之物可列舉例如前述含鈦之物所 例示之化合物相對應的鉻酸鹽。 關於使用此種交聯劑在接枝聚合物層中形成溶膠膠體 # 交聯構造，可使用將該交聯劑溶解於乙醇等溶媒後，視需 要添加觸媒等來調製塗布液組成物，將其在接枝聚合物層 上塗布、加熱、乾燥之方法。藉由該方法，交聯劑係藉由 加水分解及重縮合，而形成溶膠膠體交聯構造。 在此，加熱溫度與加熱時間只要是可除去塗布液中之 溶媒、形成強固的皮膜之溫度與時間，並無特別限制，惟 從製造適性等點，較佳爲加熱溫度爲2 0 0 °c以下，加熱時 間（交聯時間）爲1小時以内爲佳。 φ 塗布液組成物中交聯劑之含有量可因應形成之溶膠膠 體交聯構造的量應加以決定，惟從形成之有機-無機複合層 的表面硬度及對支撐體的密接性之觀點而言，通常以5〜50 質量％之範圍爲佳，以10〜40質量％之範圍爲更佳。 又，接.枝聚合物鏈在其鏈中具有特定元素醇鹽基時， 塗布液組成物中交聯劑之含有量，柑對於特定元素醇鹽 基，以調整成交聯劑中交聯性基爲5mol%以上爲佳，更佳 爲1 0 m ο I %以上。 此時，交聯劑之含有量的上限只要是可與特定元素醇 -20- 200815195 鹽基充分交聯之範圍内，並無特別限制，惟添加大量過剩 時，由於不參與交聯之交聯劑，形成之有機-無機複合層有 發生沾黏等問題的可能性。 調製前記塗布液組成物時所用之溶媒，只要是能將交 聯劑及其他成分均勻地溶解、分散之物，並無特別限制， 惟以例如甲醇、乙醇、水等水系溶媒爲佳。 又，關於前記塗布液組成物，爲了促進交聯劑之加水 分解及重縮合反應，以倂用酸性觸媒或鹼性觸媒爲佳，在 φ 實用上、可以較佳反應效率的情況下，觸媒係爲必須。該 觸媒，可直接使用酸、或鹼性化合物，或使用將其溶解於 水或醇等溶媒之物（以下分別稱爲酸性觸媒、鹼性觸媒）。 將觸媒溶解於溶媒時的濃度並無特別限定，可因應所用之 酸或鹼性化合物的特性、觸媒期望之含有量等加以適當地 選擇，惟濃度高時，有加水分解、重縮合速度變快的傾向。 但使用濃度高之鹼性觸媒時，由於有塗布液組成物中生成 沈殿物的情形，因此使用鹼性觸媒時，期望其濃度係以水 φ 溶液之濃度換算爲1 N以下。 酸性觸媒或鹼性觸媒的種類並無特別限定，惟在必須 使用濃度濃之觸媒時，以乾燥後在塗膜中幾乎不殘留之元 素所構成之觸媒爲佳。具體而言，酸性觸媒，可列舉鹽酸 等鹵化氫、硝酸、硫酸、亞硫酸、硫化氫、過鹽素酸、過 酸化氫、碳酸、甲酸或乙酸等羧酸、其RCOOH所表之構 造式的R以其他元素或置換基所置換之置換羧酸、苯磺酸 等磺酸等；鹼性觸媒，可列舉氨水等氨性鹽基、乙基胺、 苯胺等胺類等。 -21- 200815195 又，關於該塗布液組成物’只要不損及本發明效果並 無特別限制，可因應目的使用各種添加劑。例如，未提升 塗布液之均勻性，可添加界面活性劑等。 又，在本發明中，亦可用以下方法形成接枝聚合物層、 及有機-無機複合層。即，可列舉例如除了前述之極性基與 特定元素醇鹽基，調製更含有在主鏈末端或側鏈具有與支 撐體反應之官能基之聚合物、交聯劑、及觸媒的塗布液組 成物，將其以電漿或電子線等處理，在表面發生活性種之 • 自由基的支撐體上塗布、加熱、乾燥之方法。 關於該方法，藉由反應具有前記聚合物之與支撐體反 應之官能基、與支撐體，在支撐體生成直接結合之接枝聚 合物，形成接枝聚合物層。又，使塗布液組成物加熱、乾 燥時，交聯劑發生加水分解及縮聚合反應，可在接枝聚合 物層中形成交聯構造。簡言之，若藉由此方法，藉由調製 塗布液組成物，並將其塗布、加熱、乾燥之一連串步驟， 可一同形成接枝聚合物層與有機-無機複合層。 Φ 又，在調製該塗布液組成物時，亦可含有別種親水性 聚合物。親水性聚合物可藉由聚合以下單體而得：具有用 來形成先前列舉之接枝聚合物鏈有用之極性基的單體。親 水性聚合物之含有量以固形分換算，以1 0質量％以上、小 於50質量％爲佳。含有量成爲50質量％以上時，有膜強度 降低的傾向，又，小於1 0質量％時，有皮膜特性降低，且 在膜發生裂痕等可能性，任一者均爲不佳。 如以上所述’本發明中有機-無機複合層的形成係利用 溶膠膠體法。關於溶膠膠體法，在作花濟夫「溶膠-凝膠法 -22- 200815195 0科學」（股）Agne承風社（刊）（1 988年〕、平島硯「最新溶 膠-凝膠法之機能性薄膜作成技術」總合技術 Center(刊）（1 992年）等成書等有詳細記述，該等記載之方 法可適用於本發明中有機-無機複合層的形成。 該有機-無機複合層之膜厚可根據防污性薄膜之用途 等加以選擇，惟通常以 0·1μητν〜10μηη之範圍爲較佳， 0.5μηι〜10μηη之範圍爲更佳。藉由該膜厚之範圍，可得對 支撐體之密接性及可撓性優異之防污性薄膜，且無捲曲之 • 發生、可撓性或耐屈曲性之降低，因而較佳。 <撥水撥油處理步驟> 本步驟係在以前述有機-無機複合層形成步驟所得之 有機-無機複合層表面施行撥水撥油處理。 本發明中用於撥水撥油處理之化合物（撥水劑）、處理 方法並無特別限制，惟以在有機-無機複合層表面賦予氟或 烷基者爲佳。該撥水撥油處理較佳係使用，例如矽烷基化 劑、鈦酸酯偶合劑、烷基鋁等有機金屬化合物。 φ 由於該等化合物可在本發明之交聯構造之間形成共價 鍵，因此撥水撥油處理面與支撐體之密接性變得優異。 矽烷基化劑爲在對本發明中溶膠膠體交聯構造具有親 和性或反應性之加水分解性矽烷基上，使含有烷基、芳基、 氟之氟烷基等予以結合的化合物；結合至矽之加水分解性 基，可列舉烷氧基、鹵原子、乙醯氧基、矽氮烷等。具體 而言，以使用全氟烷基矽烷化合物、烷基矽烷化合物爲佳。 又，由於撥水撥油處理面的臨界傾斜角過小，水滴會 變得容易滾落，因此宜使用聚二甲基矽氧烷化合物作爲撥 -23- 200815195 水劑。撥水撥油處理面之臨界傾斜角，係在水平放置之防 污性薄膜表面上放置一定量之水滴開始滾動時板的傾斜角 度。撥水劑係視需要由加水分解供應至撥水層之塗布。 如上述撥水劑之表面處理係以噴灑法、流塗法、旋塗 法、浸漬提升法等塗布、以液相吸着法等進行表面吸着。 經撥水劑處理之表面在乾燥後以3 0 0 °C以下之溫度、 較佳爲1 0 0 °C〜2 5 0 °C，進行1 〇分鐘〜1小時加熱處理。 在有機-無機複合層表面，撥水劑係形成單分子層顯示 Φ 撥水性能，又，由於撥水劑之厚度即使大於1 0 n m，效果亦 不會變高，因此熱處理後撥水撥油處理層之較佳厚度爲 1nm〜10nm 〇 如上所述，本發明之防污性薄膜爲撥水撥油處理面與 有機-無機複合層之密接性、及有機-無機複合層與支撐體 之密接性優異，其結果爲撥水撥油處理面與支撐體之密接 性變得優異。因此，本發明之防污性薄膜爲防污性優良且 其持續性優異。 φ 【實施例】 以下，舉出實施例具體說明本發明，惟本發明並不受 該等所限制。 [實施例1] <基材A之製作> 使用膜厚188μΓΤΐ之2軸延伸聚對苯二甲酸乙二酯薄膜 (Α41 00、東洋紡（股）社製），使用平版磁控管濺鍍裝置（芝 浦Eletech製CFS-10-EP70)作爲輝光處理裝置，以下述條 件進行氧輝光處理，得到P ET支撐體。 -24- 200815195 -氧輝光處理條件- 初期真空：1 .2x1 0_3Pa 氧壓力：〇.9Pa RF 輝光：1 .5kW 處理時間：6 0 s e c <接枝聚合物層之形成1> 接著，將Ν,Ν -二甲基丙烯醯胺、甲基丙烯醯氧基丙基 乙氧基矽烷、乙醇混合溶液（Ν,Ν -二甲基丙烯醯胺··甲基丙 φ 烯醯氧基丙基乙氧基矽烷=1:1(莫耳比）、濃度：50質量％) 予以氮起泡（〇^〇96〇|31|131}丨1叩）。將上述卩日丁支撐體在該 混合溶液以70。(：浸漬7小時。將浸漬後之PET支撐體以乙 醇充分洗淨，在其構造内，具有特定元素醇鹽基之矽烷偶 合基及醯胺基之接枝聚合物鏈係直接結合至支撐體表面’ 而形成接枝聚合物層。把該具有接枝聚合物層之PET支撐 體當作支撐體A。 <有機-無機複合層之形成1> φ 在所得之支撐體A，塗布將含有以下量之乙醇、水、 四乙氧基矽烷、及磷酸的塗布液組成物1在室溫攪拌24 小時之物，藉由以1 00 °C、1 〇分鐘加熱乾燥形成有機-無機 複合層，得到有機-無機複合（hybrid)薄膜A。 •塗布液組成物1 - •四乙氧基矽烷〔交聯劑〕..............〇.9g •乙醇·.·................................…··......................3.7g • 7jc...........................................8.7 g •磷酸水溶液（0.8 5 %水溶液）…..............1 .3g -25- 200815195 <撥水撥油處理> 將所得之有機-無機複合薄膜 A在 〇. 1臂<。， 貝迤。/〇之 1H，1H,2H，2H全氟癸基三氯矽烷·己烷溶液浸漬1〇分鐘 拿起後，藉由加熱乾燥（1 〇 0 °C、3 0 m i η)而得到防污性 丨土溥膜 Α。形成之撥水撥油處理層與有機-無機複合層之總摩 500nm 〇 [實施例2] 在實施例1之 <有機-無機複合層之形成1>中。除7將 在有機-無機複合層之形成所使用之塗布液組成物1所含％ 四乙氧基矽烷〇.9g以四甲氧基鈦酸鹽1 .〇g代替以外，以 與實施例1同樣的方法得到防污性薄膜B。 [實施例3] 在實施例1之 <有機-無機複合層之形成1>中。除了將 在有機-無機複合層之形成所使用之塗布液組成物1所含的 四乙氧基矽烷0.9g以四甲氧基鉻酸鹽i.6g代替以外，以 與實施例1同樣的方法得到防污性薄膜C。 [實施例4] 在實施例1之<有機-無機複合層之形成1>中。除了將 在有機-無機複合層之形成所使用之塗布液組成物1所含的 四乙氧基矽烷0.9 g以三甲氧基鋁酸鹽〇 . 7 g代替以外，以 與實施例1同樣的方法得到防污性薄膜D。 [實施例5] 將實施例1中<接枝聚合物層之形成1>變更爲下述< 接枝聚合物層之形成2>而製作支撐體B，更將 <有機-無機 複合層之形成1>中所用的支撐體A變更爲支撐體B來製作 -26- 200815195 有機-無機複合薄膜B以外，以與實施例1同樣的方法得到 防污性薄膜E。 <接枝聚合物層之形成2> 將丙烯醯胺水溶液（濃度·· 50質量％)予以氮起泡。將用 於實施例1之PET支撐體在該水溶液中以70°C浸漬7小 時。將浸漬後之PET支撐體以蒸留水充分洗淨，在其構造 内，具有醯胺基之接枝聚合物鏈係直接結合至支撐體表面 而形成接枝聚合物層。把該具有接枝聚合物層之PET支撐 φ 體當作支撐體B。 [實施例6】 <接枝聚合物層之形成3> 將甲基丙烯醯氧基丙基乙氧基矽烷·乙醇溶液（濃 度：50質量。/。）予以氮起泡。將實施例1所用之PET支撐體 在該溶液以70°C浸漬7小時。將浸漬後之PET支撐體以蒸 留水充分洗淨，在其構造内，具有特定元素醇鹽基之矽烷 偶合基的接枝聚合物鏈係直接結合至支撐體表面，而形成 φ 接枝聚合物層。把該具有接枝聚合物層之PET支撐體當作 支撐體C。 <有機-無機複合層之形成2> 在所得之支撐體C上塗布將含有以下的量之2-丙醇' 水、四乙氧基矽烷、及磷酸之塗布液組成物2在室溫攪拌 5小時之物，藉由1 0 0 °C、1 0分鐘加熱乾燥形成有機-無機 複合層，得到有機-無機複合薄膜C。 -塗布液組成物2 - -27- 200815195 • 2-丙醇..............................8 g ‘·四乙氧基矽烷[交聯劑]..........1 · 〇 g •水....................................1 · 〇 g •磷酸水溶液（〇. 8 5 %水溶液）.….1. 〇 g <撥水撥油處理> 在所得之有機-無機複合薄膜c上進行與實施例1之< 撥水撥油處理 > 同樣的處理，得到防污性薄膜F。 形成之撥水撥油處理層與有機-無機複合層之總厚度 爲 1.2μηη。 [比較例1】 將 2-(全氟丁基）乙基丙烯酸酯（Azmax(股）社 製）0.5g、與1-甲氧基-2-丙醇（和光純藥工業（股）社製）〇.5g 混合作爲均勻溶液。將實施例1所用之PET支撐體在溶液 以70°C浸漬7小時。將浸漬後之卩£丁支撐體以乙醇充分洗 淨，在其構造内，含氟原子接枝聚合物鏈（疎水性接枝聚合 物鏈）係直接結合至支撐體表面，得到防污性薄膜G。 [比較例2] 除了將實施例1中所用的支撐體（接枝聚合物層PET 支撐體）A以聚對苯二甲酸乙二酯代替以外，以與實施例1 同樣的方法得到防污性薄膜Η。 〔防污性薄膜之性能評價〕 對實施例1~6、比較例1、2之防污性薄膜Α〜Η進行 如下之性能評價。結果示於下述表1。 1 .撥水性之評價[Technical Field] The present invention relates to an antifouling film and a method for producing the same, and more particularly to an antifouling film having an antifouling surface which does not adhere to oily dirt or the like. And its method of production. [Prior Art] The "dirt" caused by the adhesion of pollutants on the surface of the material is not only detrimental to the appearance but also the function of the surface of the material. Therefore, in order to "anti-fouling", it is necessary to reduce the adhesion (interaction) of pollutants. The reduction in the adhesion of contaminants is generally achieved by hydrophilization or oiling of the surface of the material. Conventionally, as a film having water repellency and antifouling properties, a fluorine compound layer is wet-coated (wet film formation) on the outermost surface thereof, and water repellency and antifouling property are used (for example, Patent Document 1 refers to .). However, the surface coating of the organic material has a low surface hardness and durability, and therefore such improvement is necessary. In order to solve such a problem, it is reviewed to use a cerium oxide layer having excellent water repellency and antifouling property and having a small surface energy, and the cerium oxide layer can be expected to have an improvement in surface hardness and durability. However, when the ruthenium dioxide layer having water repellency and antifouling property is coated on the support to obtain a film having water repellency and antifouling property, the surface energy of the ruthenium dioxide layer is small, and the support is provided. The problem is that the adhesion between the two becomes smaller. In order to improve the adhesion between the support and the surface ceria layer, it is proposed to provide a close-packed ceria layer having a carbon content of less than 20% by atom as an intermediate layer between the support and the surface ceria layer (for example, refer to the patent document) 200815195 2.). The method improves the adhesion between the support and the ruthenium oxide layer by bonding the cerium oxide to the surface of the ruthenium dioxide layer and the support layer, but the adhesion is not sufficient, and the carbon is not sufficient. The content causes the surface energy, water repellency, and antifouling properties to be greatly changed. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2000-1841 No. 2002-A No. 2002-1 1 3805 [Invention] φ [Problems to be Solved by the Invention] Therefore, there is adhesion to a support. Excellent and oil-treated surface, with high antifouling properties and a continuous antifouling film method. [Means for Solving the Problem] The inventors of the present invention have studied the organic-inorganic composite layer containing a graft chain directly bonded to a support and a crosslinked structure by hydrolysis and condensation polymerization of a metal alkoxide. The present invention has been completed in accordance with the use of the φ-inorganic composite layer as appropriate for the antifouling film. According to a first aspect of the present invention, an antifouling film comprising a support and an organic-inorganic composite layer, and a surface of the organic-inorganic composite layer is subjected to a water-repellent treatment, wherein the antifouling film is provided. The inorganic-composite layer is formed by the hydrolysis and condensation polymerization of an alkoxide selected from the group consisting of elements of Si, Ti, in a graft polymer layer composed of a binder chain directly bonded to the surface of the support. The pre-coupling graft polymer chain is preferably formed by a polymerization reaction having a starting species on the surface of the support as a starting point. Further, the front layer is provided with the surface of the second surface, which is formed by the dialing and its branching polymerization, and is made of the branched polymer Zr and AI. Biopolymer grafting 200815195 The polymer chain is preferably an alkoxide group having an element selected from Si, Ti, Zr, AI in its chain, and/or a guanamine group. More preferably, the graft polymer chain has a polar group, preferably a structural unit having a mercapto group, and an alkoxide group having an element selected from Si, Ti, Zr, and A having a decane coupling group. Copolymers of structural units are preferred. A second aspect of the present invention provides a method for producing an antifouling film, wherein the antifouling film of the present invention has the following steps of: forming a graft polymer chain directly bonded to a surface of a support to form the graft polymer; a step of grafting a polymer layer composed of a chain; in the graft polymer layer, a crosslinking reaction of hydrolyzing and polycondensation of an alkoxide selected from elements of Si, Ti, Zr, AI is performed to form a step of the organic-inorganic composite layer; and a step of applying a water-repellent oil treatment to the surface of the organic-inorganic composite layer. [Effect of the Invention] The present invention provides an antifouling film which is excellent in adhesion to a support, has a water repellent treatment surface, and has high antifouling properties and durability. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. Further, in the present specification, "~" means a range including the minimum 値 and the maximum 値 of the number described before and after. The antifouling film of the present invention has a support and an organic-inorganic composite layer' and is subjected to a water-repellent treatment of the surface of the organic-inorganic composite layer, wherein the organic-inorganic composite layer is directly bonded to the The graft polymer layer composed of the graft polymer chain on the surface of the support contains a 200815195 joint structure formed by hydrolysis and condensation polymerization of an alkoxide of an element selected from the group consisting of Si, Ti, Zr, and AI. The antifouling film of the present invention is preferably a crosslinked structure in which an alkoxide using Si is formed in terms of reactivity and ease of obtaining the compound. The crosslinked structure formed by the hydrolysis and polycondensation of an alkoxide as described above is appropriately referred to as a "sol colloid crosslinked structure" hereinafter. The antifouling film of the present invention is produced by the following method for producing an antifouling film of the present invention. That is, the method for producing an antifouling film of the present invention is preferably a method having the following steps: forming a graft polymer chain which is directly bonded to the surface of the support H to form a graft polymer chain. a step of grafting the polymer layer, hereinafter suitably referred to as "graft polymer layer forming step"; in the graft polymer layer, performing an alkoxide of an element selected from the group consisting of Si, Ti, Zr, and AI a step of adding a water-decomposing and polycondensation crosslinking reaction to form an organic-inorganic composite layer (hereinafter referred to as "organic-inorganic composite layer forming step" as appropriate): applying water dialing to the surface of the organic-inorganic composite layer The oil treatment step (hereinafter referred to as "water draining oil treatment step" as appropriate). Although the effect of the present invention is not clear, it is presumed as follows. • The organic-inorganic composite layer of the present invention contains a graft polymer chain (organic component) directly bonded to the surface of the support, and hydrolysis with an alkoxide of an element selected from the group consisting of Si, Ti, Zr, and AI. And a crosslinked structure (inorganic component) formed by polycondensation polymerization. Although the organic-inorganic composite layer is a thin layer, it has high abrasion resistance and high durability. In particular, when the graft polymer chain has a polar group, the polar interaction with the crosslinked structure is formed by the function of the polar group, and the organic-inorganic composite layer excellent in strength and durability can be obtained. Further, in the case where the graft polymer chain is an alkoxide group 200815195 having an element selected from Si, Ti, Zr, and A1 in its chain, a total is formed between the graft polymer chain and the crosslinked structure. The valence bond and the strength and durability of the organic-inorganic composite layer are improved. Furthermore, the crosslinked structure in the organic-inorganic composite layer has a reactive group derived from an alkoxide of an element selected from the group consisting of Si, Ti, Zr, and AI, by using the reactive group and for dialing A covalent bond is formed between the oil-treated compounds to obtain a water-repellent oil-repellent treatment surface excellent in adhesion to the support. As a result, it is estimated that an antifouling film having high antifouling properties and its durability can be obtained. The following describes the "graft polymer layer forming step", "organic-inorganic composite layer forming step", and "water-repellent oil-repellent treatment step". <Graft Polymer Layer Forming Step> In this step, a graft polymer chain directly bonded to the surface of the support is formed to form a graft polymer layer composed of the graft polymer chain. A method of producing a graft polymer chain directly bonded to a surface of a support, (1) a method of surface graft polymerization of a compound having a polymerizable double bond by using a support as a base point to form a graft polymer chain (hereinafter A method in which a polymer having a functional group reactive with a support is chemically bonded to a surface of a support to form a graft polymer chain (hereinafter referred to as "method 1" as appropriate) 2"). The two methods will be described below. (1) A method in which a compound having a polymerizable double bond is subjected to surface graft polymerization to form a graft polymer chain by using a support as a base point (Method 1) The method 1 is generally called a method of surface graft polymerization. The surface graft polymerization method imparts an active species to the surface of the support by means of plasma irradiation, light irradiation, heating, etc., and uses the active species as a base point to have a polymerizable double in a form in contact with the support. The compound of the bond is superposed on the side of the 200815195 method. According to this method, the end of the graft polymer chain formed is directly bonded to the surface of the support and fixed. In order to carry out the surface graft polymerization method of the present invention, a known method described in the literature can be arbitrarily used. For example, in the new polymer experiment 10, the Institute of Polymer Science, the 1994 publication, the publication of the Keli publication, the photo-graft polymerization method, and the plasma irradiation graft polymerization method are used as the surface graft polymerization method. In addition, sorption techniques, notes, NTS (stock), Takeuchi supervision, 1 999.2 release, p203, p 695 record Y-line, electron beam and other radiation irradiation graft polymerization. The photo-grafting polymerization method is a method described in JP-A-63-92658, JP-A-H09-296895, and JP-A-11-119413. The plasma irradiation graft polymerization method or the radiation irradiation graft polymerization method can be suitably used in the above-described documents, and the methods described in 丫. Ikada et al, Macromolecules vo 1.19, p. 1804 (1986). Specifically, the radical of the active species is generated by treating the surface with a plasma or electron beam, and then the PET can be reacted by reacting the surface of the support having the active species with a compound having a polymerizable double bond (for example, a monomer). The polymer φ surface is formed into a graft polymer chain. In addition to the above-mentioned documents, the photo-grafting polymerization can also be described in JP-A-53-1-7407 (Kansai Paint) and JP-A-2000-21231 (Daily Ink). The surface of the support is coated with a photopolymerizable composition, and the radically polymerized compound is exposed to light irradiation. The compound useful in the formation of the graft polymer chain by the method 1 must have a polymerizable double bond. Further, in consideration of the formation of a polar interaction with the sol colloid crosslinked structure formed in the organic-inorganic composite layer forming step described later, the compound having a polymerizable double bond and having a polar group is -10- 200815195 Good. Further, in view of the formation of a covalent bond between the sol colloid crosslinked structures formed by the organic-inorganic composite layer forming step described later, a compound having a polymerizable double bond and having a specific element alkoxide group is preferred. The compound suitable for the method 1 may have any of these compounds when it has a double bond in the molecule, if necessary, a polar group and/or a specific element alkoxide group, a polymer, a low polymer, or a monomer. One of the compounds useful in the present invention is a monomer having a polar group. Examples of the monomer having a polar group useful in the present invention include a positively charged monomer such as ammonium or scaly, or a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group, which are obtained by charging or load electrolysis. As the monomer of the acidic group, other monomers having a nonionic group such as a hydroxyl group, a decylamino group, a sulfonylamino group, an alkoxy group, a cyano group or the like can also be used. In the present invention, specific examples of the monomer having a particularly useful polar group include the following monomers. For example, (meth)acrylic acid or an alkali metal salt thereof and an amine salt, itaconic acid or an alkali metal salt thereof and an amine acid salt, allylamine or a hydrogen halide thereof, 3-vinylpropionic acid or An alkali metal salt and an amine salt thereof, a vinyl sulfonic acid or an alkali metal salt thereof and an amine salt, a styrene sulfonic acid or an alkali metal salt thereof and an amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropene ( Methyl) acrylate or its alkali metal salt and amine salt, 2-propenylamine-2 -methylpropane sulfonate alkali metal salt and amine salt, decyl phosphorusoxy polyethylene glycol mono (methyl Acrylate or such salt, 2-dimethylaminoethyl (meth) acrylate or its hydrogen halide, 3-trimethylammonium propyl (meth) acrylate, 3-trimethyl Alkyl ammonium propyl (meth) acrylamide, N, N, N-trimethyl-N-(2-hydroxy-3-methylpropenyloxypropyl) ammonium chloride, and the like. Further, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (methyl 200815195) acrylamide N-vinylpyrrolidone, N-vinylethylene glycol mono(meth)acrylate, and the like are also useful. The macromonomer having a polar group useful in the present invention can be obtained by the synthesis method described in "New Polymer Experiment 2, Polymer Synthesis/Reaction" Polymer Co-published (US) 1959. In addition, he is in the "Chemical and Industrial of Giant Monomers" IPC, 1 989, in detail, using acrylic acid, acrylamide, 2-propenylamine-2-sulfonic acid, N-vinylacetamide The monomer having φ, which is specifically described above, can be synthesized by a method described in the literature. The macromonomer having a polar group used in the present invention is a monomer monomer having a carboxyl group such as acrylic acid or methacrylic acid, and 2-propenylamine-2-methylpropanesulfonic acid or phenylethyl a sulfonic acid-based macromonomer derived from a monomer of a salt thereof, an amide-based macromonomer such as acrylonitrile acrylamide, or an N-vinyl group such as N-vinylethyl N-vinylcarbamide The carboxylic acid decylamine monomer is a macromonomer derived from a hydroxyl group-containing monomer derivative monomer such as hydroxyethyl methacrylate, hydroxy acid ester or glycerol monomethacrylate, and is composed of a methoxyethyl group. An alkoxy or ethylene oxide-derived macromonomer such as acrylate, methoxypolyethylene glycol, polyethylene glycol acrylate or the like. Further, a polyethylene glycol chain or a polypropylene monomer can also be used as the macromonomer of the present invention. Among these macromonomers, a macromonomer having a mercapto group is used as a mercapto group, and a macromolecule having a mercapto group is formed from a point of mutual formation of a colloidal crosslinked structure formed in the organic-inorganic forming step described later. Therefore, by learning to compile, it is recorded in Yamashita. a macromolecule having a polar group of methyl propane, particularly a composite layer of a derivatized olefinic sulfonic acid, an amine, a methyl decylamine, a raw guanamine ethyl propylene, a macroalcoholic acryl-based monomeric diol chain The shape is a strong polar group of -12-200815195. The useful molecular weight of these macromonomers is 400~1 million, the preferred range is 1 000~50,000, and the particularly good range is 1 500~ The range of 20,000. Further, the graft polymer chain in the present invention has an alkoxide group having an element selected from the group consisting of Si, Ti, Zr, and AI in its chain as described previously (hereinafter appropriately referred to as a specific halogen alkoxide group) ) is better. The specific element alkoxide group forms a substituent of a covalent bond via hydrolysis and condensation polymerization with a crosslinking agent (metal alkoxide) described later. Since such a graft polymer chain has a specific element alkoxide group, a covalent bond can be formed between the sol colloid crosslinked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer chain. In the case of the surface graft polymerization method using the method 1, it is preferred to use a monomer or a macromonomer having a specific element alkoxide group. A decane coupling group is typically exemplified as the specific element alkoxide group for specific description. The functional group represented by the following general formula (I) can be exemplified as the decane coupling group which is suitable for the present invention. General formula (丨) (R1)m(〇R2)3-m-SI— In the general formula (I), R1 and R2 each independently represent a hydrogen atom or a hydroxyl group having a carbon number of 8 or less, and m represents 0 to 2; The integer. R1 and R2 are a hydroxyl group in the case of a hydroxyl group, and examples thereof include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferred. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group. , neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. 0 -13- 200815195 R1 and R2 are from the viewpoint of effect and ease of availability, It is preferably a hydrogen atom, a methyl group or an ethyl group. The monomer having a functional group represented by the general formula (1) includes (3-acryloxypropyl)trimethoxynonane, (3-acryloxypropyl)dimethylmethoxydecane, (3). - propylene methoxy propyl) methyl dimethoxy decane, (methacryloxymethyl) dimethyl ethoxy decane, (methacryloxymethyl) ethoxy decane, ( Methyl propylene methoxymethyl) trimethoxy decane, (methacryloxypropyl) dimethyl ethoxy decane, (methacryloxypropyl propyl meth) dimethyl methoxy decane , (methacryloxypropyl) methyl diethoxy decane, (methacryloxypropyl) ethoxy decane, (methacryloxypropyl) triisopropyl decane, Methyl propylene methoxy propyl (methethoxy ethoxy) decane, and the like. In the present invention, in the case of using the method 1, a monomer or a macromonomer having a polar group or a macromonomer having a specific element alkoxide group such as a decane coupling group is used for surface graft polymerization. The method is co-coincident to form a graft polymer chain. Among them, it is more preferable to use a monomer φ having a guanamine group or a macromonomer as a polar group. (2) A method of chemically bonding a polymer having a functional group reactive with a support to a surface of a support to form a graft polymer chain (Method 2) In Method 2, it may be used at the end of the main chain or at the side chain A polymer having a functional group reactive with a support chemically reacts the functional group with a functional group on the surface of the support to form a graft polymer chain. The functional group which reacts with the support is not particularly limited as long as it can react with the functional group on the surface of the support, and examples thereof include a decane coupling group such as alkoxydecane, an isocyanate group, an amine group, a hydroxyl group, and a carboxyl group. Sulfonic acid group, phosphoric acid group, epoxy group, -14-200815195 allyl group, methacryl fluorenyl group, acryl fluorenyl group and the like. j A compound which is particularly useful as a polymer having a functional group reactive with a support at a terminal or a side chain of a main chain is a polymer having a trialkoxyalkyl group at a polymer terminal and an amine group at a polymer terminal. A polymer having a carboxyl group at the polymer end, an epoxy polymer at the polymer end, and a polymer having an isocyanate group at the polymer end. Further, the polymer used at this time is more preferably a polymer having a polar group and having a polar group, and specific examples thereof include polyacrylic acid, polymethacrylic acid, #polystyrenesulfonic acid, and poly-2-propenylamine. 2-methylpropane sulfonic acid and such salts, polyacrylamide, polyvinylacetamide, and the like. In addition to these, a polymer having a monomer having a polar group used in the above method (1) or a copolymer containing a monomer having a polar group may be used. Further, in order to form a strong polar interaction with the sol colloid crosslinked structure formed in the step of forming the organic-inorganic composite layer to be described later, it is preferred that the polymer having a guanamine group as a polar group. On the other hand, the polymer having a φ energy group reactive with the support at the end of the main chain or the side chain is more preferably an alkoxide group having an element selected from the group consisting of Si, Ti, Ζ γ, and AI (specific element alkoxide group) ). By using the polymer, a specific element alkoxide group can be introduced into the resulting graft polymer chain. By having such a graft polymer chain having a specific element alkoxide group, a covalent bond can be formed between the sol colloid crosslinked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer chain. In the present invention, a polymer having a functional group reactive with a support at a terminal end or a side chain of the main chain is particularly preferred as a polar group having both a mercapto group and a specific element alkoxide group. -15- 200815195 In the present invention, the point of formation of a covalent bond of a polar interaction with a sol colloid crosslinked structure, the graft polymer chain produced by the above method has a decylamine The base and/or the specific element alkoxide group is preferred. The preferred introduction amount of the guanamine group in the graft polymer chain of the present invention is in the range of 10 mol% to 90 mol%, and the introduction amount of the specific element alkoxide group is 10 m ο I % 〜 9 0 m ο I % The range is good. In the present invention, it is preferred that the graft polymer chain has a polar group or a specific element alkoxide group in the chain, and in addition to the groups, a crosslinkable group or a polymerizable group may be introduced. These groups form a crosslinked structure between the graft polymer chains. (Support) In the present invention, a material having mechanical strength and dimensional stability can be arbitrarily used. However, in the case where the antifouling film is required to have permeability, it is preferred to use a film having transparency. / As the film to be used as the support, specifically, a polyester film such as a polyethylene terephthalate film, a polyethylene terephthalate copolyligated polyester film, or a φ polybutylene naphthalate film may be used. Polyamide film such as nylon 66 film, nylon 6 film, m-xylylenediamine copolyhide polyimide film; polyolefin film such as polypropylene film, polyethylene film, ethylene-propylene copolymer film; Imine film; polyimine film; polyvinyl alcohol film; ethylene-vinyl alcohol copolymer film; polyphenylene film; polyfluorene film; polyphenylene sulfide film. Among these, a polyolefin film such as a polyester film such as a polyethylene terephthalate film, a polyethylene film or a polypropylene film is preferable from the viewpoints of cost performance, transparency, and the like. These films may be either extended or unstretched, and may be used alone or as a film of a different nature. -16 - 200815195 The film used as the support is not limited to the effect of the present invention, and may contain various additives or stabilizers or may be applied. The additives which can be used include, for example, an antioxidant, an antistatic agent, an ultraviolet ray preventive agent, a plasticizer, a slip agent, a heat stabilizer, and the like. Further, the film may be subjected to surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion treatment (b 〇 m b a r d m e n t) treatment, drug treatment, solvent treatment, and roughening treatment. The thickness of the support is considered to be suitable for the purpose of use of the packaging material, and is suitably set to be φ, and is not particularly limited, but from the viewpoint of general practical use, it is preferably in the range of 3 μΓΠ to 1 mm, from flexibility or processing. From the viewpoint of sex, it is more preferably in the range of 10 μm to 300 pm. The support is a material which is energized by itself, and when the active species is produced, it can be used as it is, but for the purpose of forming a starting species of the graft polymer chain with good efficiency, it may also have a surface on the support body. The surface layer of the polymerization initiation energy. A surface layer having a polymerization initiation energy is preferably a layer containing a low molecular weight or high molecular weight φ polymerization initiator. Among them, from the viewpoint of stability and durability, a polymerization initiating layer composed of a polymerization initiator immobilized by a crosslinking reaction is preferred; more preferably, a crosslinking initiation reaction is carried out in the side chain by a crosslinking reaction. The polymerization initiating layer composed of the polymer of the functional group and the crosslinkable group is immobilized. A polymerization initiating layer comprising a polymer having a functional group and a crosslinkable group having a polymerization initiation energy in a side chain by a crosslinking reaction is described in detail in paragraph number [0011] of JP-A-2004-161995. As described in ~[0169], the polymerization initiating layer can be suitably used in the present invention. -17- 200815195 <Organic-Inorganic Composite Layer Forming Step> In this step, an alcohol selected from elements of Si, Ti, Zr, AI is subjected to the graft polymer layer obtained in the graft polymer layer forming step. The cross-linking reaction of the salt by hydrolysis and condensation polymerization forms an organic-inorganic composite layer. In short, the organic-inorganic composite layer of the present invention is an organic component composed of a graft polymer chain, and is hydrolyzed and polycondensed by an alkoxide of an element selected from Si, Ti, Zr, and AI. A layer of an inorganic component composed of a crosslinked structure φ (sol-gel crosslinked structure) formed by a crosslinking reaction. First, this step is a compound having a crosslinked structure formed by a crosslinking reaction of hydrolyzing and polycondensation of an alkoxide selected from elements of Si, Ti, Zr, and AI (hereinafter sometimes referred to individually as The "crosslinking agent" is preferred to form the sol colloid crosslinked structure in the present invention. In the crosslinking agent of the present invention, for example, a compound represented by the following general formula (丨丨) can be used. The compound represented by the following general formula (II) is a case where the graft polymer chain has a specific element alkoxide group, and the specific element alkoxide group is hydrolyzed and polycondensed, and the polymer chain and the sol are grafted. A covalent bond can be formed between the colloidal crosslinked structures. Thereby, a strong organic-inorganic composite layer can be formed. General formula (丨丨1 (R6)mX-(〇R7)4-m In general formula (II), R6 represents a hydrogen atom, an alkyl group or an aryl group, R7 represents an alkyl group or an aryl group, and X represents Si, AhTi. Or Zr, m represents an integer of 〇~2. When R6 and R7 represent an alkyl group, the carbon number thereof is preferably from 1 to 4. -18- 200815195 The alkyl group or the aryl group may have a substituent group and may be introduced. Further, the substituent is a low molecular compound and preferably has a molecular weight of 1 。. Specific examples of the compound represented by the general formula (M) are listed below, When X is S i , that is, the hydrazine-containing substance in the hydrolyzable compound is exemplified by, for example, trimethoxy decane, ethoxy decane, tripropoxy decane φ methoxy decane, tetraethoxy group. Decane, tetrapropoxydecane, methyltridecane, ethylethoxydecane, propyltrimethoxydecane, methyl decane, ethyl ethoxy decane, propyl ethoxy decane, dimethyl Oxydecane, diethyldiethoxydecane, γ-chloropropylethoxy oxime propyl propyl trimethoxy decane, Y-mercaptopropyl propyl Oxydecane, Y-propylethoxydecane, phenyltrimethoxydecane, phenylethoxyphosphonium phenyltripropoxydecane, diphenyldimethoxydecane, diphenyldidecane, etc. φ Among the above-mentioned ones, tetramethoxy decane, tetraethoxy hydride, methyl trimethoxy decane, ethyl trimethoxy decane, methyl ethane oxime, ethyl ethoxy decane, and Methyl diethoxy decane, phenyl ethoxy decane, phenyl ethoxy decane, diphenyl dimethoxy decane, bis ethoxy sand, etc. Further, when X is AI, that is, adding water Examples of the aluminum-containing compound 2 in the decomposable compound include trimethoxyaluminate, triethoxyaluminate, tripropylaluminate, tetraethoxyaluminate, etc. When X is Ti, that is, titanium-containing The substance may, for example, be a trimethoxytitanium halide, which is a hair, a tetramethoxy methoxy:, a Y-amine, an ethoxy methoxy trimethylbenzene, an oxy-only salt, -19 · 200815195 Tetramethoxytitanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorine trichloride Oxytitanate, ethyltrimethoxytitanate, methyltriethoxytitanate, ethyltriethoxytitanate, diethyldiethoxytitanate,phenyltrimethoxy A titanate, a phenyl triethoxy titanate, etc. When X is Zr, the zirconium-containing substance may, for example, be a chromate corresponding to the compound exemplified above for the titanium-containing substance. The cross-linking agent forms a sol colloid # crosslinked structure in the graft polymer layer, and after dissolving the cross-linking agent in a solvent such as ethanol, a catalyst or the like may be added as needed to prepare a coating liquid composition, which is grafted. A method of coating, heating, and drying on a polymer layer. By this method, the crosslinking agent is hydrolyzed and recondensed to form a sol colloid crosslinked structure. Here, the heating temperature and the heating time are not particularly limited as long as the temperature and time at which the solvent in the coating liquid can be removed and the strong film is formed, but the heating temperature is preferably 200 ° C from the viewpoint of production suitability and the like. Hereinafter, the heating time (crosslinking time) is preferably within 1 hour. The content of the crosslinking agent in the composition of the φ coating liquid can be determined in accordance with the amount of the sol colloid crosslinked structure formed, from the viewpoint of the surface hardness of the formed organic-inorganic composite layer and the adhesion to the support. It is usually in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass. Further, when the branched polymer chain has a specific element alkoxide group in its chain, the content of the crosslinking agent in the coating liquid composition, and the specific alkoxide group of the orange to adjust the crosslinkable group in the crosslinking agent It is preferably 5 mol% or more, more preferably 10 m ο I% or more. In this case, the upper limit of the content of the crosslinking agent is not particularly limited as long as it is sufficiently crosslinkable with the specific element alcohol-20-200815195 base, but when a large excess is added, cross-linking is not involved in crosslinking. The organic-inorganic composite layer formed has the possibility of problems such as sticking. The solvent to be used in the preparation of the coating liquid composition is not particularly limited as long as it can uniformly dissolve and disperse the crosslinking agent and other components, and is preferably an aqueous solvent such as methanol, ethanol or water. Further, in order to promote the hydrolysis and recondensation reaction of the crosslinking agent, it is preferable to use an acidic catalyst or an alkaline catalyst for the pre-coating liquid composition, and in the case where φ is practical and the reaction efficiency is preferable, Catalyst is a must. As the catalyst, an acid or a basic compound can be used as it is, or a solvent (hereinafter referred to as an acidic catalyst or an alkaline catalyst) which is dissolved in a solvent such as water or alcohol. The concentration at which the catalyst is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound to be used, the desired content of the catalyst, and the like. However, when the concentration is high, hydrolysis rate and recondensation rate are possible. The tendency to get faster. However, when a high-concentration alkaline catalyst is used, since a sediment is formed in the coating liquid composition, when an alkaline catalyst is used, the concentration is desirably converted to 1 N or less in terms of the concentration of the water φ solution. The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, it is preferred to use a catalyst composed of an element which hardly remains in the coating film after drying. Specific examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, persalt acid, hydrogen peroxide, carbonic acid, formic acid or acetic acid, and the structural formula of RCOOH. The R is a sulfonic acid or a sulfonic acid such as benzenesulfonic acid, which is replaced by another element or a substituent. The basic catalyst may, for example, be an amine group such as ammonia or an amine such as ethylamine or aniline. Further, the coating liquid composition 'is not particularly limited as long as the effects of the present invention are not impaired, and various additives can be used depending on the purpose. For example, a surfactant or the like may be added without improving the uniformity of the coating liquid. Further, in the present invention, the graft polymer layer and the organic-inorganic composite layer may be formed by the following method. In other words, for example, a coating liquid containing a polymer, a crosslinking agent, and a catalyst having a functional group reactive with a support at a terminal end or a side chain of the main chain or a side chain in addition to the above-mentioned polar group and a specific element alkoxide group may be mentioned. A method in which it is treated by plasma or electron beam, and coated, heated, and dried on a support having a radical of a reactive species on the surface. In this method, a graft polymer layer is formed by reacting a functional group having a pre-recorded polymer with a support and a support to form a graft polymer directly bonded to the support. Further, when the coating liquid composition is heated and dried, the crosslinking agent undergoes hydrolysis and condensation polymerization to form a crosslinked structure in the graft polymer layer. In short, by this method, a graft polymer layer and an organic-inorganic composite layer can be formed together by preparing a coating liquid composition, and coating, heating, and drying a series of steps. Φ Further, when the coating liquid composition is prepared, it may contain another hydrophilic polymer. The hydrophilic polymer can be obtained by polymerizing a monomer having a polar group useful for forming the previously listed graft polymer chain. The content of the hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content is 50% by mass or more, the film strength tends to decrease. When the content is less than 10% by mass, the film properties are lowered, and cracks may occur in the film, and any of them may be inferior. As described above, the formation of the organic-inorganic composite layer in the present invention utilizes the sol colloid method. About the sol colloid method, the function of the latest sol-gel method in the sol-gel method "sol-gel method-22-200815195 0 science" (share) Agne Chengfengshe (published) (1 988), Hirashima The film forming technique is described in detail in the book, et al., et al. (1992), and the methods described above can be applied to the formation of the organic-inorganic composite layer in the present invention. The film thickness can be selected according to the use of the antifouling film, etc., but it is usually in the range of 0·1 μητν 10 10 μηη, and the range of 0.5 μηη to 10 μηη is more preferable. By the range of the film thickness, it is possible to obtain a film thickness It is preferable that the anti-fouling film having excellent adhesion and flexibility is excellent in curl generation, flexibility, and buckling resistance. <Water-repellent oil-repellent treatment step> This step is carried out by water-repellent oil-repellent treatment on the surface of the organic-inorganic composite layer obtained by the above-described organic-inorganic composite layer formation step. The compound (water repellent) and the treatment method for the water-repellent treatment in the present invention are not particularly limited, but it is preferred to impart fluorine or an alkyl group to the surface of the organic-inorganic composite layer. The water repellency treatment is preferably carried out using an organometallic compound such as a hydrazine alkylating agent, a titanate coupling agent or an alkyl aluminum. φ Since these compounds form a covalent bond between the crosslinked structures of the present invention, the adhesion between the water-repellent oil-treated surface and the support becomes excellent. The oximation agent is a compound which combines an alkyl group, an aryl group, a fluorine-containing fluoroalkyl group or the like on a hydrolyzable alkylene group having affinity or reactivity with respect to the sol colloid crosslinked structure of the present invention; Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an ethoxy group, and a decane. Specifically, a perfluoroalkyl decane compound or an alkyl decane compound is preferably used. Further, since the critical inclination angle of the water-repellent oil-treated surface is too small, the water droplets may become easily rolled off, and therefore it is preferable to use a polydimethylsiloxane compound as the water agent of -23-200815195. The critical tilt angle of the water-repellent oil treatment surface is the inclination angle of the board when a certain amount of water droplets are placed on the surface of the horizontally disposed anti-fouling film to start rolling. The water-repellent agent is supplied to the water-repellent layer by hydrolysis. The surface treatment of the water repellent is carried out by a spray method, a flow coating method, a spin coating method, a dipping lifting method, or the like, and is subjected to surface adsorption by a liquid phase adsorption method or the like. The surface treated with the water repellent is dried at a temperature of 300 ° C or lower, preferably at 100 ° C to 250 ° C, for 1 Torr to 1 hour after drying. On the surface of the organic-inorganic composite layer, the water-repellent agent forms a monomolecular layer to exhibit the Φ water-repellent property, and since the thickness of the water-repellent agent is even greater than 10 nm, the effect does not become high, so the water-repellent oil is removed after the heat treatment. The preferred thickness of the treated layer is 1 nm to 10 nm. As described above, the antifouling film of the present invention has the adhesion between the water-repellent oil-treated surface and the organic-inorganic composite layer, and the adhesion between the organic-inorganic composite layer and the support. The result is excellent, and as a result, the adhesion between the water-repellent oil-treated surface and the support is excellent. Therefore, the antifouling film of the present invention is excellent in antifouling property and excellent in durability. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. [Example 1] <Production of Substrate A> A 2-axis-stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) having a film thickness of 188 μm was used, and a lithographic magnetron sputtering apparatus (manufactured by Shiba Eletech Co., Ltd.) was used. CFS-10-EP70) As a glow processing apparatus, oxygen glow treatment was performed under the following conditions to obtain a P ET support. -24- 200815195 - Oxygen glow treatment conditions - Initial vacuum: 1.2x1 0_3Pa Oxygen pressure: 〇.9Pa RF Glow: 1.5 kW Processing time: 6 0 s e c <Formation of graft polymer layer 1> Next, a mixed solution of ruthenium, osmium-dimethylpropenamide, methacryloxypropyl ethoxy decane, and ethanol (Ν, Ν-dimethylpropene) Amidoxime··methylpropane φ allyloxypropyl ethoxy decane=1:1 (mole ratio), concentration: 50% by mass) Nitrogen foaming (〇^〇96〇|31|131}丨1叩). The above-mentioned ruthenium support was placed at 70 in the mixed solution. (: immersion for 7 hours. The impregnated PET support is sufficiently washed with ethanol, and within its structure, the decane coupling group having a specific element alkoxide group and the graft polymer chain of the guanamine group are directly bonded to the support. The surface is formed to form a graft polymer layer. The PET support having the graft polymer layer is used as the support A. <Formation of organic-inorganic composite layer 1> φ In the obtained support A, a coating liquid composition 1 containing ethanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was applied and stirred at room temperature for 24 hours. The organic-inorganic composite layer was obtained by heating and drying at 100 ° C for 1 minute to obtain an organic-inorganic hybrid film A. • Coating liquid composition 1 - • Tetraethoxy decane [crosslinking agent]..............〇9g • Ethanol···.......... .......................................................3.7g • 7jc...........................................8.7 g • Aqueous phosphoric acid solution ( 0.8 5 % aqueous solution).................1.3g -25- 200815195 <Water-repellent oil treatment> The obtained organic-inorganic composite film A is at 〇. 1 arm <. , Bessie. /〇1H, 1H, 2H, 2H perfluorodecyltrichlorodecane·hexane solution, immersed for 1 minute, picked up, and dried by heating (1 〇0 °C, 3 0 mi η) to obtain antifouling property丨土溥膜Α. The total friction of the water-repellent oil-repellent treatment layer and the organic-inorganic composite layer formed is 500 nm 实施 [Example 2] In Example 1 <Formation of organic-inorganic composite layer 1>. In addition to the substitution of 7 in the coating liquid composition 1 used for the formation of the organic-inorganic composite layer, tetraethoxy decane ruthenium. 9 g is replaced by tetramethoxy titanate 1. 〇g, and Example 1 The antifouling film B was obtained in the same manner. [Example 3] In Example 1 <Formation of organic-inorganic composite layer 1>. In the same manner as in Example 1, except that 0.9 g of tetraethoxynonane contained in the coating liquid composition 1 used for the formation of the organic-inorganic composite layer was replaced with tetramethoxychromate i.6 g. The antifouling film C was obtained. [Embodiment 4] In Embodiment 1 <Formation of organic-inorganic composite layer 1>. The same method as in Example 1 except that 0.9 g of tetraethoxynonane contained in the coating liquid composition 1 used for the formation of the organic-inorganic composite layer was replaced by trimethoxyaluminate 〇. 7 g. The antifouling film D was obtained. [Example 5] In Example 1, <Formation of graft polymer layer 1><Formation of grafted polymer layer 2> to produce support B, more The antifouling film E was obtained in the same manner as in Example 1 except that the support A used in the formation of the organic-inorganic composite layer was changed to the support B to prepare the organic-inorganic composite film B of -26-200815195. . <Formation of graft polymer layer 2> An aqueous solution of acrylamide (concentration··50 mass%) was bubbled with nitrogen. The PET support used in Example 1 was immersed in the aqueous solution at 70 ° C for 7 hours. The impregnated PET support is sufficiently washed with distilled water, and within its structure, the graft polymer chain having a mercapto group is directly bonded to the surface of the support to form a graft polymer layer. The PET support φ body having the graft polymer layer was used as the support B. [Example 6] <Formation of graft polymer layer 3> A solution of methacryloxypropyl ethoxy methoxy decane·ethanol (concentration: 50 mass%) was bubbled with nitrogen. The PET support used in Example 1 was immersed in the solution at 70 ° C for 7 hours. The impregnated PET support is sufficiently washed with distilled water. Within its structure, the graft polymer chain having a specific element alkoxide-based decane coupling group is directly bonded to the surface of the support to form a φ graft polymer. Floor. The PET support having the graft polymer layer was used as the support C. <Formation of Organic-Inorganic Composite Layer 2> The resulting support C was coated with a coating liquid composition 2 containing 2-propanol 'water, tetraethoxy decane, and phosphoric acid in an amount of the following at room temperature. After 5 hours, the organic-inorganic composite layer was formed by heating and drying at 100 ° C for 10 minutes to obtain an organic-inorganic composite film C. - Coating liquid composition 2 - -27- 200815195 • 2-propanol..............................8 g '· Tetraethoxydecane [crosslinking agent]..........1 · 〇g •Water........................ ............1 · 〇g • Aqueous phosphoric acid solution (〇. 8 5 % aqueous solution).....1. 〇g <Water-repellent oil-repellent treatment> The organic-inorganic composite film c obtained was subjected to the same as in Example 1. < Water-repellent oil treatment > The same treatment was carried out to obtain an antifouling film F. The total thickness of the water-repellent oil-repellent treatment layer and the organic-inorganic composite layer formed was 1.2 μηη. [Comparative Example 1] 0.5 g of 2-(perfluorobutyl)ethyl acrylate (manufactured by Azmax Co., Ltd.) and 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) ) 〇. 5g mixed as a homogeneous solution. The PET support used in Example 1 was immersed in a solution at 70 ° C for 7 hours. The impregnated butyl support is sufficiently washed with ethanol, and within the structure, the fluorine atom-grafted polymer chain (hydrophobic graft polymer chain) is directly bonded to the surface of the support to obtain an antifouling film. G. [Comparative Example 2] Antifouling property was obtained in the same manner as in Example 1 except that the support (graft polymer layer PET support) A used in Example 1 was replaced with polyethylene terephthalate. Film Η. [Evaluation of the performance of the antifouling film] The antifouling films of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated for the following properties. The results are shown in Table 1 below. 1. Evaluation of water repellency
對防污性薄膜Α〜Η之撥水撥油處理面（防污性薄膜G -28- 200815195 係直接結合含氟原子之接枝聚合物鏈構成的面），用協和界 面科學（股）製之CA-Z，測定在純水滴下後、20秒後之角 度。水滴接觸角爲150°以上者作爲A。結果示於表1。 2 .密接性之評價 根據JIS K5400，對防污性薄膜A~H之撥水撥油處理 面（防污性薄膜G係直接結合含氟原子之接枝聚合物鏈構 成的面），旋轉切片機切成1 0 0塊1 m m角方塊，壓著賽珞 玢管（Nichiban(股）製、註冊商標）後，以30000mm/min之 # 速度實施3次90度之剝離試驗。評價係以測定剝離試驗後 殘餘之升目數來進行。結果示於表1。 3.防污性之評價 3. 1初期防污性之評價 對防污性薄膜A〜Η之撥水撥油處理面（防污性薄膜G 係直接結合含氟原子之接枝聚合物鏈構成的面），用速乾性 油性油墨（zebra製、「Macky」（註冊商標））寫字。接著，將 該用字旭化成社製「Bemkoton」（註冊商標）乾淨的擦拭至 φ 擦去，測定擦拭次數。結果示於表1。 3.1 2反覆防污性之評價 用旭化成社製「B e m k 〇 t ο η」（註冊商標）、將防污性薄. 膜Α〜Η之撥水撥油處理面（防污性薄膜G係直接結合含氟 原子之接枝聚合物鏈構成的面）強烈擦拭500次後，在其表 面以速乾性油性油墨（Zebra製、「Macky」（註冊商標））寫 字，顯示其擦去之次數。結果示於表1。 -29- 200815195 表1 防污性薄膜 撥水性 密接性 防污性 初期防污性反覆防污性 實施例1 防污性薄膜A A 100/100 4 3 實施例2 防污性薄膜B A 100/100 3 3 實施例3 防污性薄膜C A 100/100 4 3 實施例4 防污性薄膜D A 100/100 4 3 實施例5 防污性薄膜E A 98/100 3 3 實施例6 防污性薄膜F A 100/100 4 3 比較例1 防污性薄膜G A 100/100 5 未擦拭 比較例2 防污性薄膜Η A 5/100 4 未擦拭 由表1之結果，具有有機-無機複合層之實施例的防污 性薄膜A〜F係撥水性、及與支撐體與撥水撥油處理層之密 接性良好。又，實施例之防污性薄膜A〜F爲初期防污性、 及防污性優異。由該等可明白本發明之防污性薄膜爲防污 性及其持續性優異。 【産業上之可利用性】 本發明之防污性薄膜適合適應於CRT、LCD、PDP、 FED等顯示器、碰觸板、玻璃、桌子、化妝合板等、更且 CD、DVD等記錄媒體之表面保護薄膜等。 日本出願2006-182291之揭示，根據參照其全體倂入 本說明書。在本說明書所記載之全部文獻、專利申請案、 及技術規格係藉由參照各種文獻、專利申請案、及技術規 格具體地各種記載之情形同樣地在本說明書中参照。 【圖式簡單說明】 >fTTT； Μ 【元件符號說明】 無 -30-For the antifouling film Α~Η, the water-repellent treatment surface (anti-fouling film G -28- 200815195 is a surface directly composed of a fluorine-containing atom-grafted polymer chain), using the Concord Interface Science CA-Z, measured at an angle of 20 seconds after pure water drop. The contact angle of the water droplet is 150° or more as A. The results are shown in Table 1. 2. Evaluation of Adhesiveness According to JIS K5400, the water-repellent treatment surface of the antifouling film A to H (the surface of the antifouling film G directly bonded to the graft polymer chain of fluorine atom) is rotated and sliced. The machine was cut into 10 0 mm square blocks, and after pressing the celluloid tube (Nichiban Co., Ltd., registered trademark), three 90-degree peeling tests were performed at a speed of 30000 mm/min. The evaluation was carried out by measuring the number of rises remaining after the peeling test. The results are shown in Table 1. 3. Evaluation of antifouling property 3. Evaluation of initial antifouling property The antifouling film A to 拨 water repellent treatment surface (antifouling film G is directly bonded to a fluorine atom-containing graft polymer chain) In the case of a quick-drying oily ink (made by Zebra, "Macky" (registered trademark)). Next, the word "Bemkoton" (registered trademark) manufactured by Asahi Kasei Co., Ltd. was wiped cleanly to φ, and the number of wiping was measured. The results are shown in Table 1. 3.1 2 Evaluation of the anti-fouling property by the Asahi Kasei Co., Ltd. "B emk 〇t ο η" (registered trademark), the anti-fouling property is thin. The membrane Α Η Η 拨 拨 拨 拨 ( ( After the surface was strongly rubbed 500 times with the surface of the graft polymer chain containing a fluorine atom, the surface was printed with a quick-drying oil-based ink ("Macky" (registered trademark), manufactured by Zebra), and the number of times of wiping off was shown. The results are shown in Table 1. -29- 200815195 Table 1 Antifouling film water-repellent adhesion Antifouling property Initial antifouling property Antifouling property Example 1 Antifouling film AA 100/100 4 3 Example 2 Antifouling film BA 100/100 3 3 Example 3 Antifouling film CA 100/100 4 3 Example 4 Antifouling film DA 100/100 4 3 Example 5 Antifouling film EA 98/100 3 3 Example 6 Antifouling film FA 100/ 100 4 3 Comparative Example 1 Antifouling film GA 100/100 5 Unwiped Comparative Example 2 Antifouling film Η A 5/100 4 The antifouling of the example having the organic-inorganic composite layer was not wiped as a result of Table 1. The film A to F is water-repellent, and has good adhesion to the support and the water-repellent oil-repellent treatment layer. Further, the antifouling films A to F of the examples are excellent in initial antifouling properties and antifouling properties. It is understood from these that the antifouling film of the present invention is excellent in antifouling properties and sustainability. [Industrial Applicability] The antifouling film of the present invention is suitable for use on a surface of a recording medium such as a CRT, an LCD, a PDP, or an FED, a touch panel, a glass, a table, a makeup plywood, or the like, and a recording medium such as a CD or a DVD. Protective film, etc. Japanese Patent Application No. 2006-182291, the entire disclosure of which is incorporated herein by reference. All the documents, patent applications, and technical specifications described in the specification are referred to in the specification in the same manner as the various documents, patent applications, and technical specifications. [Simple description of the diagram] >fTTT; Μ [Description of component symbols] None -30-