201136995 六、發明說明： 【發明所屬之技術領域】 本發明係關於含有聚矽氧烷之電極保護膜形成劑、電 極保護膜及具該電極保護膜之電子裝置。尤其關於液晶顯 示元件可使用的電極保護膜形成劑、電極保護膜及具該電 極保護膜之液晶顯示元件。 【先前技術】 液晶顯示元件的製造中，以透明電極之絕緣、保護爲 目的而在透明電極與液晶配向膜之間形成氧化物被膜。氧 化物被膜之形成方法已知蒸鍍法、濺鍍法等代表的氣相法 與使用氧化物被膜形成用塗佈液的塗佈法。其中，由生產 性或對大型基板的被膜形成容易度來看，多使用塗佈法。 塗佈液方面，已知四烷氧基矽烷之水解物及與其他金屬烷 氧化物或金屬螯合物化合物之複合物。使用金屬烷氧化物 調製塗佈液的場合，一般金屬烷氧化物除去矽則水解速度 快、反應控制困難。因此，以調整烷氧化物的水解速度爲 目的，而嘗試使乙醯丙酮等螯合物化劑作用。但，一般被 螯合物化的化合物，熱分解溫度變高、期望在450°C以上 燒成。（例如專利文獻1作參考。） 另外的方法方面，二氧化矽-二氧化鈦系塗佈液中， 嘗試藉由在矽烷氧化物與鈦烷氧化物的水解物中添加無機 酸，不使用螯合物化等安定化手段而成爲透明塗佈劑。此 場合至少需要3 0 0 °C以上之燒成。（例如專利文獻2作參 201136995 考。） 又，在最近亦提案塑膠LCD或電子紙等在基材上使 用塑膠板或塑膠薄膜之顯示器，追求即使在200°C以下的 低溫亦可獲得足夠硬度，且上層配向劑可無缺陷塗佈。 [先前技術文獻] [專利文獻] [專利文獻1 ]特_昭63-25 8959號公報 [專利文獻2 ]特開昭55_25487號公報 【發明內容】 [發明所欲解決課題] 在上述專利文獻1及專利文獻2之方法，在200°C以 下的燒成溫度難以得到足夠硬度的電極保護膜。而且，在 電極保護膜之上層形成液晶配向膜時，配向膜有產生龜裂 或針孔之問題。 在本發明，係以提供即使在1 50°C以下的低溫燒成時 ，可形成足夠硬度的電極保護膜之電極保護膜形成劑、電 極保護膜及具該電極保護膜之電子裝置爲目的。尤其用於 液晶顯示元件之場合，以提供於電極保護膜之上層可形成 抑制龜裂或針孔產生之液晶配向膜的電極保護膜形成劑爲 目的。 [解決課題之手段] -6 - 201136995 本發明者們係基於上述狀況努力硏究結果，而完成本 發明。 亦即，本發明之主要課題如以下： 1· 一種以含有含式（1)所表示之烷氧基矽烷及式（2)所 表不之院氧基砂院所組成群中選出之至少1種之化合物之 烷氧基矽烷進行聚縮合而得到的聚矽氧烷爲特徵之電極保 護膜形成劑。 R1{Si(OR2)3}P (1) (R1爲以脲基所取代的碳原子數1〜12之烴基，R2爲碳 原子數1〜5之烷基，p爲1或2之整數） (R3)nSi(OR4)4-〇 (2) (R3爲可以氫原子、或雜原子、鹵素原子、乙烯基、胺 基、環氧丙氧基、锍基、甲基丙烯醯氧基、異氰酸酯基或 丙烯醯氧基取代的碳原子數1〜8之烴基，R4爲碳原子數 1〜5之烷基，且η爲0〜3之整數。） 2. 式（2)中之η爲0的四烷氧基矽烷之上述1記載之電 極保護膜形成劑。 3. 前述式（1)所表示之烷氧基矽烷在全烷氧基矽烷中含 0.5〜60莫耳％ ’且前述式（2)所表示之烷氧基矽烷在全 烷氧基矽烷中含40〜99.5莫耳％的上述1或2記載之電極 201136995 保護膜形成劑》 4 .前述式（1 )所妻 氧基矽烷、r -脲3 氧基矽烷所成組群 項記載之電極保護 5 .將上述1〜4中 並進行燒成而得到 6 ·將上述1〜4中 基板，且在室溫〜 極保護膜之形成方 7. 燒成溫度爲100-成方法。 8. 具有上述5記載 9 .具有上述5記載 [發明效果] 因本發明之電 150°C以下之低溫彳 板等耐熱性低的基 形成的電極保護膜 。因此，即使爲在 示特性優異的液晶 I示之烷氧基矽烷係由r -脲基丙基三乙 I丙基三甲氧基矽烷及r-脲基丙基三丙 中選出之至少1種的上述1〜3中任一 膜形成劑。 任一項記載之液晶配向劑塗佈於基板， 電極保護膜。 任一項記載之電極保護膜形成劑塗佈於 1 20 °c之溫度下乾燥後、進行燒成的電 法。 〜180°C的上述6記載之電極保護膜之形 之電極保護膜之電子裝置。 之電極保護膜之液晶顯示元件。 極保護膜形成劑所得到的電極保護膜在 更化條件具有足夠硬度，可適用塑膠基 板。又，用於液晶顯示元件之場合，在 上可形成抑制龜裂或針孔之液晶配向膜 塑膠基板等耐熱性低的基板亦可用於顯 顯示元件之製造。 [實施發明之最佳形態] -8 - 201136995 本發明之電極保護膜形成劑之 之聚砂氧烷。因此，即使在1〇〇> 形成具有足夠硬度之電極保護膜。 以往，矽氧烷聚合物或氧化物 物薄膜在燒成溫度低之場合，塗膜 分解。因此’用於液晶顯示元件之 特性相異的聚醯亞胺系配向膜足夠 測爲形成配向膜時龜裂或針孔產生 由於電極保護膜形成劑含脲基，不 之親和性提升、可抑制龜裂或針孔 護膜形成劑在1 00〜1 5 0 °c的低溫 爲充分硬化者。 以下對本發明進行詳細說明。 〔聚矽氧烷〕 本發明之電極保護膜形成劑;i 示之烷氧基矽烷之烷氧基矽烷進行 烷。 R'{Si(OR2)3}p (1) 式（1 )中，R1爲以脲基所取· 烴基，詳細爲碳原子數1〜1 2之烴 所取代的基。R 1較佳爲以脲基所® 最大特徵係含有具脲基 / 150 °C所謂的低溫亦可 前驅物質所形成的氧化 中殘存的院氧基未充分 場合，無法得到與界面 親和性、密著性，可推 之原因。在本發明，藉 僅與聚醯亞胺系配向劑 ，亦認爲即使將電極保 進行燒成之場合，可成 含有下述式（1 )所表 聚縮合而得到的聚矽氧 尤的碳原子數1〜12之 基之任意氫原子被脲基 代的碳原子數1〜7的 -9- 201136995 烴基。R2爲碳原子數1〜5之烷基，較佳爲碳原子數係1 〜3之烷基，更佳爲甲基或乙基。p爲1或2之整數。R1 、R2可爲直鏈構造或具有分支構造。 式（1)所表示之烷氧基矽烷中，p爲1之場合係式 (1-1)所表示之烷氧基矽烷。 R'Si(〇R2)3 (1-1) 又’ P爲2之場合係式（1-2)所表示之烷氧基矽烷 (R2〇)3Si-R'-Si(OR2)3 (1-2) 雖舉例式（1 -1 )所表示之烷氧基矽烷之具體例，但 不限於此等。可舉例如7-脲基丙基三乙氧基矽烷、r -脲 基丙基三甲氧基矽烷、r -脲基丙基三丙氧基矽烷、（R )-心1-苯基乙基->^’-三乙氧基矽烷基丙基脲、（11)-：^-1-苯基乙基-Ν’ -三甲氧基矽烷基丙基脲等。 其中’ 7·脲基丙基三乙氧基砂院、或脲基丙基三 甲氧基矽烷因作爲市售品取得容易，而特別佳。 雖舉例式（1-2)所表示之烷氧基矽烷之具體例，但 不限於此等。可舉例如雙〔3-(三乙氧基矽烷基）丙基〕 脲、雙〔3-(三乙氧基矽烷基）乙基〕脲、雙〔3_ (三甲 氧基矽烷基）丙基〕脲、雙〔3_(三丙氧基矽烷基）丙基 -10- 201136995 〕脲等。其中，雙〔3-(三乙氧基矽烷基）丙基〕脲因作 爲市售品取得容易，故特別佳。 式（1 )所表示之烷氧基矽烷，在得到電極保護膜形 成劑使用的全烷氧基矽烷中，未達0.5莫耳％之場合有無 法得到良好液晶配向膜之印刷性之情形，故以〇 · 5莫耳％ 以上爲佳。更佳爲1 · 0莫耳％以上。又更佳爲2 . 〇莫耳％以 上》又’超過60莫耳％之場合，因形成的電極保護膜有 未充分硬化之情形，故以60莫耳％以下爲佳。更佳爲50 莫耳％以下。又更佳爲4 0莫耳％以下。 又’本發明之電極保護膜形成劑可使式（1)所表示 之烷氧基矽烷與含下述式（2)所表示之烷氧基矽烷之至 少1種之垸氧基砂院進行聚縮合而得到。 (R3)nSi(OR4)4-n (2) (R3爲可以氫原子、或雜原子、鹵素原子、乙烯基、胺 基、環氧丙氧基、锍基、甲基丙烯醯氧基、異氰酸酯基或 丙烯醯氧基取代的碳原子數1〜8、較佳爲碳原子數1〜6 之烴基，R4爲碳原子數1〜5、較佳爲1〜3之烷基，且η 爲0〜3、較佳爲0〜2之整數。） 式（2)所表示之烷氧基矽烷之R3爲可以氫原子、或 雜原子、鹵素原子、乙烯基、胺基、環氧丙氧基、巯基、 甲基丙烯醯氧基、異氰酸酯基或丙烯醯氧基取代的碳原子 數1〜8、較佳爲碳原子數1〜6之烴基。R4與上述R2同 -11 - 201136995 義，較佳範圍亦相同。R3之例方面，爲脂肪族烴；脂肪 族環、芳香族環或雜環般環構造；不飽和鍵結；可含氧原 子、氮原子、硫原子等雜原子等、亦可具分支構造的碳原 子數係1〜6之有機基。此外R3亦可以鹵素原子、乙烯基 、胺基、環氧丙氧基、毓基、甲基丙烯醯氧基、異氰酸酯 基、丙烯醯氧基等取代。 以下舉例如此之式（2)所表示之烷氧基矽烷之具體 例，但不限於此。 式（2)之烷氧基矽烷中，R3爲氫原子時之烷氧基矽 烷之具體例，如三甲氧基矽烷、三乙氧基矽烷、三丙氧基 矽烷、三丁氧基矽烷等。 又，其他的式（2)之烷氧基矽烷之具體例，如甲基 三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、 乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽 烷、甲基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3·胺 基丙基三乙氧基矽烷、N-2(胺基乙基）3-胺基丙基三乙 氧基矽烷、N_2 (胺基乙基）3-胺基丙基三甲氧基矽烷、 3- ( 2-胺基乙基胺基丙基）三甲氧基矽烷、3-( 2-胺基乙 基胺基丙基）三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧 基矽烷、2- ( 2-胺基乙基硫代乙基）三乙氧基矽烷、3-巯 基丙基三乙氧基矽烷、毓基甲基三甲氧基矽烷、乙烯基三 乙氧基矽烷 '乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷 、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧 基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、 -12- 201136995 3 -丙烯醯氧基丙基三乙氧基矽烷、3 -異氰酸酯丙基三乙氧 基矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、 溴丙基三乙氧基矽烷、3-巯基丙基三甲氧基矽烷、二甲基 二乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二乙氧基矽 烷、二乙基二甲氧基矽烷、二苯基二甲氧基矽烷、二苯基 二乙氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3—胺基 丙基二甲基乙氧基矽烷、三甲基乙氧基矽烷、三甲基甲氧 基矽烷等。 本發明之電極保護膜形成劑在與基板之密著性、膜之 硬度、上層液晶配向膜之印刷性等不損及本發明之效果範 圍內，亦可具有如此特定有機基一種或數種。 式（2)所表示之烷氧基矽烷中，n爲〇的烷氧基矽 烷係四烷氧基矽烷。四烷氧基矽烷因容易與式（1)所表 示之烷氧基矽烷縮合，宜用以獲得本發明之聚矽氧烷。 如此之式（2)中η爲0的烷氧基矽烷方面，以四甲 氧基矽烷、四乙氧基矽烷、四丙氧基矽烷或四丁氧基矽烷 更佳，四甲氧基矽烷或四乙氧基矽烷特別佳》 倂用式（2)所表示之烷氧基矽烷時，在爲得到電極 保護膜形成劑而使用的全烷氧基矽烷中，式（2)所表示 之烷氧基矽烷以40〜99.5莫耳％爲佳。更佳爲50〜99.5 莫耳％。又更佳爲6 0〜9 9.5莫耳％。 在本發明’電極保護膜形成劑以式（1)所表示之烷 氧基矽烷與式（2)所表示之烷氧基矽烷所選出的至少1 種之化合物進行聚縮合而得到的聚矽氧烷爲佳。 -13- 201136995 本發明之電極保護膜形成劑，在膜之硬度、上層液晶 配向膜之印刷性等不損及本發明之效果範圍內，可如此般 使用一種或倂用數種之烷氧基矽烷。 〔聚矽氧烷之製造方法〕 本發明使用的得到聚矽氧烷之方法雖並未特別限定， 在本發明中，可使以上述式（1)之烷氧基矽烷爲必須成 分的烷氧基矽烷在有機溶劑中進行縮合而得。通常聚矽氧 烷’可如此使烷氧基矽烷聚縮合後，做成於有機溶劑中均 一溶解的溶液。 本發明中之聚縮合方法，可舉例如使上述烷氧基矽烷 在醇或二醇等溶劑中進行水解.縮合之方法。此時，水解 •縮合反應可爲部分水解及完全水解任一。完全水解之場 合，理論上添加烷氧基矽烷中全烷氧化物基的0.5倍莫耳 之水即可’但通常以加入比〇 . 5倍莫耳更過量之水爲佳。 本發明中，上述反應所使用水量，雖可依所期望而適 宜選擇’通常以烷氧基矽烷中全烷氧基的0.5〜2.5倍莫 耳爲佳，更佳爲0.75〜1.5倍莫耳^ 又’通常以促進水解·縮合反應爲目的，可使用鹽酸 、硫酸、硝酸、乙酸、甲酸、草酸、馬來酸、富馬酸等酸 :氨、甲基胺、乙基胺、乙醇胺、三乙基胺等鹼；鹽酸、 硫酸 '硝酸等金屬鹽等觸媒》此外藉由加熱溶解有烷氧基 矽烷的溶液’進而促進水解•縮合反應亦爲一般的。此時 ，加熱溫度及加熱時間可依所期望適宜選擇。例如在5 〇 -14- 201136995 °C、24小時加熱·攪拌、迴流下、1小時加熱.攪拌等方 法。 又，另外的方法方面，可舉例如將烷氧基矽烷、溶劑 及甲酸、草酸、馬來酸、富馬酸等有機酸的混合物加熱使 聚縮合之方法。例如將烷氧基矽烷、溶劑及草酸的混合物 加熱後聚縮合之方法。具體上，預先於醇中加入草酸做成 草酸的醇溶液後，在加熱該溶液之狀態混合烷氧基矽烷之 方法。此時，使用的草酸的量對烷氧基矽烷具有的全烷氧 基的1莫耳而言以0.2〜2莫耳爲佳。此方法中之加熱可 在液溫5 0〜1 8 0 °C下進行。較佳爲以不引起溶液蒸發、揮 散等之方式，在迴流下加熱數十分〜十數小時之方法。 得到聚矽氧烷時，使用多種烷氧基矽烷之場合，可使 用多種之烷氧基矽烷預先混合的混合物，或依序混合多種 之烷氧基矽烷使用。 使烷氧基矽烷聚縮合時所使用的溶劑（以下、亦稱聚 合溶劑）爲可將烷氧基矽烷溶解者即可，並無特別限制。 又，即使不溶解烷氧基矽烷之場合，可伴隨烷氧基矽烷之 聚縮合反應進行而溶解者即可。一般來說，因烷氧基矽烷 之聚縮合反應而生成醇，而可使用醇類、二醇類、二醇醚 類、或與醇類相溶性良好的有機溶劑》 如此聚合溶劑之具體例方面，可舉例如甲醇、乙醇、 丙醇、丁醇，二丙酮醇等醇類；.乙二醇、二乙二醇、丙二 醇、二丙二醇、己二醇、1,3 -丙烷二醇、1,2 -丁烷二醇、 1,3-丁烷二醇、1，4-丁烷二醇、2,3-丁烷二醇、1，2-戊烷二 -15- 201136995 醇、1，3-戊烷二醇、1，4-戊烷二醇、戊烷二醇、2,4-戊 烷二醇、2，3-戊烷二醇、1 ’ 6-己烷二醇等二醇類；乙二醇 單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單 丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙 基醚、乙二醇二丁基醚、二乙二醇單甲基醚、二乙二醇單 乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二 醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二 乙二醇二丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙 二醇單丙基醚、丙二醇單丁基醚、丙二醇二甲基酸、丙二 醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚等二醇醚 類；N -甲基-2 -D比咯院酬、N，N -二甲基甲酸胺' Ν,Ν -二甲 基乙醯胺、丁內酯、二甲基亞颯、四甲基尿素、六甲 基磷酸三醯胺、m-甲酚等。 本發明中，可混合上述聚合溶劑多種使用。 上述方法所得到的聚矽氧烷之聚合溶液（以下、亦稱 聚合溶液。）’一般係使換算作爲原料加入的全烷氧基矽 院之砂原子爲Si〇2的濃度（以下、稱爲Si〇2換算濃度。 )在20質量％以下。藉由在該濃度範圍選擇任意濃度， 可抑制膠體生成、得到均質的溶液。 本發明中，可直接使上述方法所得到的聚矽氧烷之聚 合溶液作爲電極保護膜形成劑，或因應必要使上述方法所 得到的溶液濃縮、加入溶劑後稀釋，或取代爲其他溶劑後 ，用作爲電極保護膜形成劑。 此時，使用的溶劑（以下、亦稱添加溶劑,），可與聚 -16- 201136995 合溶劑相同、或爲另外溶劑。該添加溶劑，在聚矽氧烷均 一溶解範圍內，並不特別限定，可一種或多種任意選擇使 用。 該添加溶劑之具體例方面，除上述聚合溶劑的例子所 舉溶劑外，尙可舉例如丙酮、甲基乙基酮、甲基異丁基酮 等酮類；乙酸甲酯、乙酸乙酯、乳酸乙酯等酯類等。 此等溶劑，可提升在電極保護膜形成劑之黏度的調整 、或在旋轉塗佈、柔版印刷、噴射塗佈、狹縫塗佈等將電 極保護膜形成劑塗佈於基板上時的塗佈性。 〔其他成分〕 本發明中，在不損及本發明之效果範圍內，亦可含有 上述聚矽氧烷以外的其他成分，例如無機微粒子、金屬氧 院（metalloxane)寡聚物、金屬氧院聚合物、平坦劑、進 而界面活性劑等成分。 無機微粒子，以二氧化矽微粒子、氧化鋁微粒子、二 氧化鈦微粒子、或氟化鎂微粒子等微粒子爲佳，尤以膠體 溶液狀態者爲佳。該膠體溶液，可爲無機微粒子分散在分 散媒者、或市售品之膠體溶液。本發明中，藉由含有無機 微粒子，可調整形成硬化被膜之表面形狀及折射率、賦予 其他機能。無機微粒子，以其平均粒徑在0.001〜0.2 μχη 爲佳，又更佳爲0.001〜0.1 μΐΏ。無機微粒子的平均粒徑超 過0.2 μιη時，有使用調製塗佈液所形成的硬化被膜之透明 性降低之情形。 -17- 201136995 無機微粒子的分散媒，可舉例如水及有機溶劑。膠體 溶液，由電極保護膜形成劑之安定性觀點來看’以PH或 pKa調整爲1〜1〇爲佳。pH或pKa更佳爲2〜7。 膠體溶液的分散媒所用之有機溶劑’可舉例如甲醇、 丙醇、丁醇、乙二醇、丙二醇、丁烷二醇、戊烷二醇、己 二醇、二乙二醇、二丙二醇、乙二醇單丙基醚等醇類；甲 基乙基酮、甲基異丁基酮等酮類；甲苯、二甲苯等芳香族 烴類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等 醯胺類；乙酸乙酯、乙酸丁酯、r-丁內酯等酯類；四氫 呋喃、1，4-二噁烷等醚類。此等中，以醇類及酮類爲佳。 此等有機溶劑可單獨或2種以上混合作爲分散媒使用。 金屬氧烷寡聚物、及金屬氧烷聚合物，可使用矽、鈦 、鋁、鉬、銻、鉍、錫、銦、鋅等單獨或複合氧化物前驅 物。金屬氧烷寡聚物、及金屬氧烷聚合物，可爲市售品， 或由金屬烷氧化物、硝酸鹽、鹽酸鹽、羧酸鹽等單體藉由 以水解等常法處理而得到者。 市售品的金屬氧烷寡聚物、及金屬氧烷聚合物之具體 例方面，可舉例如COLCOAT CO.，Ltd製的甲基砂酸酯 51、甲基矽酸酯53A、乙基矽酸酯40、乙基矽酸酯48、 EMS_485、SS-101等矽氧烷寡聚物或矽氧烷聚合物、關東 化學公司製的鈦-η-丁氧化物四聚物等titan〇xane寡聚物 。此等可單獨或2種以上混合使用。 又’平坦劑及界面活性劑等，可使用習知者，尤其市 售品因取得容易而較佳。 -18- 201136995 又，於聚矽氧烷混合上述其他成分之方法，可與聚矽 氧烷同時或在之後，並無特別限制。 〔電極保護膜〕 將本發明之電極保護膜形成劑塗佈於電極或附電極基 材，進行熱硬化，可得到所期望的電極保護膜。電極保護 膜形成劑之塗佈方法，可採用習知或周知之方法》例如可 採用浸漬法、流塗法、噴塗法、棒塗法、凹版塗佈法、輥 塗佈法、刀塗佈法、浮刀塗佈法、柔版印刷法、噴射塗佈 法、狹縫塗佈法等。此等中，柔版印刷法、狹縫塗佈法、 噴射塗佈法、噴敷法、及凹版塗佈法中，可形成良好塗膜 〇 此時，使用基材，可舉例如塑膠；玻璃；ΑΤΟ、FTO (fluorine-doped tin oxide) 、ITO、IZO 等附透明電極玻 璃；陶瓷等基材。塑膠，可舉例如聚碳酸酯、聚（甲基） 丙烯酸酯、聚醚颯、聚芳酯、聚胺基甲酸乙酯、聚楓、聚 醚、聚醚酮、聚烯烴、聚乙烯對苯二甲酸酯、聚丙烯腈、 三醋酸纖維素、二醋酸纖維素、醋酸丁酸纖維素等。基材 形狀，可舉例如板或薄膜等。 電極保護膜形成劑’一般於塗佈前使用過濾器等進行 過濾。 基材上所形成的塗膜，在室溫〜120。(：的溫度、較佳 爲6 0〜9 0 °C使乾燥後，較佳在溫度1 〇 〇〜1 8 〇。〇、又更佳 爲1 5 0〜1 8 0 °C下進行熱硬化。此時，乾燥所需時間在3 〇 -19- 201136995 秒鐘以上即可，但1 〇分鐘以下爲足夠。 熱硬化所需時間雖可適宜選擇，但5分鐘以上即可。 選擇低硬化溫度之場合，因使硬化時間增長而易於得到具 充分硬度的電極保護膜。 又，本發明之電極保護膜形成劑，即使在溫度超過 1 80°C之硬化溫度，亦可得到具充分硬度之硬化被膜。 又，在熱硬化前，使用水銀燈、金屬鹵素燈、氙氣燈 、準分子燈等來照射能量線（紫外線等）亦爲有效。藉由 對乾燥塗膜照射能fl線，可進而使硬化溫度降低、提高被 膜之硬度。能量線照射量可因應必要適宜選擇，但通常以 數百〜數千m〗/cm2爲宜。 本發明之電極保護膜，因對該被膜上之液晶配向材的 印刷性良好，可形成抑制龜裂或針孔的液晶配向膜。 因此，本發明之電極保護膜形成劑，因可形成具有如 上述特性之電極保護膜，在提高液晶顯示元件之顯示特性 非常有用。 【實施方式】 [實施例] 以下、爲實施例與比較例，將本發明具體說明’但本 發明不限於下述實施例。 本實施例中，使用化合物的縮寫如下。 TEOS :四乙氧基矽烷 APS : 3-胺基丙基三乙氧基矽烷 -20- 201136995 GPS : 3-環氧丙氧基丙基三甲氧基矽烷 MPS: 3-锍基丙基三甲氧基矽烷 UPS: 3-脲基丙基三乙氧基矽烷 MPMS: 3-甲基丙烯醯氧基丙基三甲氧基矽烷 TET :四乙氧基鈦 AN :硝酸鋁九水合物 HG :己二醇（別名：2-甲基-2,4-戊烷二醇） PGME :丙二醇單甲基醚（別名：1-甲氧基-2-丙醇） BCS : 丁基溶纖劑（別名：1-丁氧基-2-乙醇） PB :丙二醇單丁基醚（別名·· 1-丁氧基-2-丙醇） Ν Μ P : N -甲基-2 -吡咯烷酮 l，4-BDO : 1，4-丁 烷二醇 MeOH :甲醇 EtOH :乙醇 〔合成例1〕 在附溫度計、及迴流管之200mL的四口反應燒瓶中 ，加入MeOH39.0g，藉由攪拌下於該MeOH平均少量加 入草酸18.0g，調製草酸的甲醇溶液。接著，使該溶液加 熱至其迴流溫度爲止，於迴流下的該溶液中將四乙氧基矽 烷 1 〇.4g、APS 1 · 1 g、GPS2.4g、MPS 1.0g、含 UPS92% 之甲 醇溶液8.6g(UPS含量：7.9g)與Me〇H19.5g的混合物 花45分鐘滴下。滴下完畢後，亦在迴流下持續加熱5小 時後，經冷卻而調製聚矽氧烷之溶液（L 1 )。 -21 - 201136995 進一步在3.00ml燒瓶中，混合聚矽氧烷溶液L1之 l〇〇g、與作爲溶劑的 HG64.0g、NMP48.0g、及 1,4-BDO32.0g。接著，以NEW旋轉蒸發器（東京理化器械公 司製、NE-1 )在60°C、邊慢慢減壓至20mmHg ( 2.67kPa )爲止邊將溶劑餾去，得到184.0g之溶劑取代爲NMP的 溶液（以下、亦稱取代溶液。）。之後，將該取代溶液 184.0g與PGME16.0g混合後，得到Si02換算固形分濃度 爲3質量％之聚矽氧烷溶液（LA1 )。 〔合成例2〕 在附溫度計、及迴流管之200ml四口反應燒瓶中，加 入 MeOH34.8g、TEOS27.8g、及含 UPS92%之甲醇溶液 9.6g ( UPS含量：8.8g)後，進行攪拌而調製烷氧基矽烷 單體之溶液。於該溶液，將預先混合MeOH17.64g、水 9.00g及作爲觸媒之草酸1.50g的溶液，在室溫下花費30 分鐘滴下，滴下完畢後在30分室溫下進行攪拌。之後， 迴流下進行1小時加熱後，放冷而得到Si02換算固形分 濃度爲10質量％之聚矽氧烷溶液。 對得到的聚矽氧烷溶液30.0g混合HG35.0g與 BCS3 5.0g，得到Si02換算固形分濃度爲3質量％之聚矽 氧烷稀釋溶液（LA2)。 〔合成例3〕 在附溫度計、及迴流管之200ml四口反應燒瓶中，加 -22- 201136995 入PGME31.8g與TEOS33.0g後，進行攪拌而調製烷氧基 矽烷單體之溶液。於該溶液’將預先混合PGME15.9g、水 15.0g及作爲觸媒之草酸〇.2g之溶液’在室溫下花費30 分鐘滴下，滴下完畢後進行30分鐘室溫下之攪拌。之後 ，迴流下、30分鐘加熱後，添加混合含UPS92%之甲醇溶 液 2.4g(UPS 含量：2.2g)、及 PGME1.8g 之溶液’進一 步迴流下、3 〇分鐘加熱後’放冷而得到S i Ο 2換算固形分 濃度爲1 〇質量％之聚矽氧院溶液° 對得到的聚矽氧烷溶液30.0g’混合PGME60.0g、及 HGlO.Og，而得到Si02換算固形分濃度爲3質量％之聚矽 氧烷稀釋溶液（LA3 )。 〔合成例4〕 在附溫度計、及迴流管之200ml四口反應燒瓶中’加 入 PGME31.5g 與 TEOS31.2g、及 MPMS2.1g 後’進行攪 拌而調製烷氧基矽烷單體之溶液。於該溶液’將預先混合 PGME15.7g、水15.0g及作爲觸媒之草酸〇.3g之溶液，在 室溫下花費3〇分鐘滴下’滴下完畢後進行30分鐘室溫下 之攪拌。之後，迴流下、30分鐘加熱後，加入混合含 UPS92%之甲醇溶液 2.4g(UPS含量：2.2g)、及 PGME1.8g之溶液，進一步迴流下、30分鐘加熱後’放冷 而得到Si02換算固形分濃度爲1〇質量％之聚矽氧烷溶液 〇 對得到的聚矽氧烷溶液30.0g’混合PGME60.0g、及 -23- 201136995 HGlO.Og，而得到Si〇2換算固形分濃度爲3質量％之聚矽 氧烷稀釋溶液（LA4 )。 〔合成例5〕 在附溫度計、及迴流管之200ml四口反應燒瓶中’加 入HG20.6g、BCS6.9g、及TEOS37.5g後’進行攪拌而調 製烷氧基矽烷單體之溶液。於該溶液’將預先混合 HG10.3g、BCS3.4g、水10.8g及作爲觸媒之草酸〇.5g之 溶液，在室溫下花費30分鐘滴下，滴下完畢後進行30分 鐘室溫下之搅拌。之後’迴流下、3 0分鐘加熱後’加入 混合含UPS92%之甲醇溶液5.8g(UPS含量：5.3g)、 HG3.2g、及BCSl.lg之溶液，進一步迴流下、30分鐘加 熱後，放冷而得到Si〇2換算固形分濃度爲12質量％之聚 矽氧烷溶液。 對得到的聚矽氧烷溶液 30.0g ’混合 HG41.9g、 BCS7.1g及PB40.9g，而得到Si02換算固形分濃度爲3質 量°/。之聚砂氧垸稀釋溶液（LA5)。 〔合成例6〕 將合成例2所得到的聚砂氧院溶液LA2之90g、與膠 體二氧化矽微粒子（製品名：甲醇二氧化矽溶膠、日產化 學工業公司製；Si02換算固形分濃度爲30質量％) 3.0g 、及MeOH7.0g在室溫下、進行30分鐘攪拌後，得到 Si 〇2換算固形分濃度爲3質量％之聚矽氧烷稀釋溶液（ -24- 201136995 LA6 )。 〔比較合成例1〕 在附溫度計、及迴流管之200mL的四口反應燒瓶中 ，加入EtOH40.3g，攪拌下、於該Et0H中少量平均添加 草酸18.0g，以調製草酸的乙醇溶液。接著’使該溶液加 熱至其迴流溫度爲止，迴流下的該溶液中，使TE0S 2〇. 8g 與EtOH20.8g的混合物花費45分鐘滴下。滴下完畢後’ 亦在迴流下持續加熱5小時後’經冷卻而調製聚矽氧烷之 溶液。 進一步在300ml燒瓶中，混合該聚矽氧烷溶液10〇g 、作爲溶劑之 HG64.0g、NMP48.0g、及 l,4-BDO32.0g。 接著，以NEW旋轉蒸發器（東京理化器械公司製、NE-1 )在60°C邊緩慢減壓至20mmHg ( 2.67kPa)邊將溶劑餾 去後’得到184.0g之取代溶液。之後，於該取代溶液 1 84.0g中混合pGME16.〇g後，得到Si02換算固形分濃度 爲3質量％之聚矽氧烷溶液（LB1 )。 〔比較合成例2〕 在附溫度計、及迴流管之2 0 0 m 1四口反應燒瓶中，加 入HG23_7g、BCS7.9g、及TEOS41.7g後，進行攪拌而調 製院氧基砂院單體之溶液。於該溶液，將預先混合 HG11.8g、BCS3.9g、水l〇.8g及作爲觸媒之草酸〇.2g之 溶液’在室溫下花費30分鐘滴下，滴下完畢後進行30分 -25- 201136995 鐘室溫下之攪拌。之後，迴流下、60分鐘加熱後，放冷 而得到Si02換算固形分濃度爲12質量％之聚矽氧烷溶液 〇 對得到的聚矽氧烷溶液 30.0g，混合 HG55.2g ' BCS9.2g及PB5 5.6g，而得到Si02換算固形分濃度爲3質 量％之聚矽氧烷稀釋溶液（LB2)。 〔比較合成例3〕 於3 00ml燒瓶中加入純水2.5g、乙醇64.8g及作爲觸 媒之 AN 2.7g，搅拌後得到均一溶液。於該溶液加入 TEOS 14.3g，在室溫進行30分鐘攪拌。之後，添加TET 1 5 · 7 g，在室溫進行3 0分鐘攪拌。使該溶液作爲使溶劑取 代爲HG前的溶液（取代前溶液）。 進一步在300ml燒瓶中，混合得到的取代前溶液的 24.0g、與HG2 5.8 7g。接著，以NEW旋轉蒸發器（東京 理化器械公司製' NE-1 )在60°C邊慢慢減壓至20mmHg (2.67kPa )邊將溶劑餾去後，得到28.9g之取代溶液。 之後，於取代溶液2 8 9 g中混合P G Μ E 1 1 · 1 g後，得到 Si〇2換算固形分濃度爲3質量％之聚欽砂氧院溶液（LB3 〔電極保護膜之評估〕 對得到的溶液（LA1〜LA6 )、及（LB1〜LB3 )所形 成的電極保護膜，使用後述方法評估鉛筆硬度、水接觸角 -26- 201136995 及液晶配向膜印刷性。結果如表1。 [表1] 塗佈液 例 水接觸角 鉛筆硬度 液晶配向膜印刷< k SE-3140 SE-7492 SE-5291 L A1 實施例1 50.8。 6H 〇 〇 〇 L A2 實施例2 51.2° 6H 〇 〇 〇 L A3 實施例3 42· 9° 6H 〇 〇 〇 L A4 實施例4 61 _ 2。 6H 〇 〇 〇 L A5 實施例5 43,0° 6H 〇 〇 〇 L A6 實施例6 44. 0° 5H 〇 〇 〇 L B 1 比較例1 60. 7° 3H r 〇 Δ X L B 2 比較例2 63. 1° 3H Γ〇 Δ X L B 3 比較例3 57. 1° 3H 〇 〇 Δ 由表1結果，本發明所得電極保護膜，即使在1 50°c 以下之低溫硬化溫度，顯示有一般將其被膜用作液晶顯示 元件之電極保護膜（絕緣膜）場合所需充分硬度5H以上 之鉛筆硬度。 而且，在該被膜上，不僅使用聚醯胺酸型，在使用可 溶性聚醯亞胺型之液晶配向劑時，亦具有無龜裂或針孔的 優異成膜性。 〔鉛筆硬度〕 將合成例（LA1〜LA6 )、及比較合成例（LB1〜LB3 )之聚矽氧烷溶液（塗佈液）使用層析盤（倉敷紡績公司 製、孔徑0.45μπι)進行過濾。之後，滴下於厚度0.7mm 的附ITO玻璃基板（ITO膜厚爲140nm )上，使用旋轉塗 佈機（Mikasa公司製、1H-DX2 )，以旋轉數300rpm進 行5秒鐘預備旋轉後，以旋轉數2000〜5000rpm進行20 秒鐘旋轉形成塗膜。接著，在溫度80 °C的加熱板上使進 -27- 201136995 行3分鐘乾燥後，在加熱板上、硬化溫度爲1 5 0 °C進行1 5 分鐘加熱後得到硬化被膜。使得到的硬化被膜之鉛筆硬度 依據試驗法（JIS K5 400 )進行測定。 〔水接觸角〕 使用協和界面科學公司製的自動接觸角計CA-Z型， 測定將純水3毫公升滴下時的接觸角。又，使用基板的態 樣與保護膜之作製方法與〔鉛筆硬度〕測定場合時相同。 〔液晶配向膜印刷性〕 在與上述〔鉛筆硬度〕同樣方法形成之硬化被膜上， 使用 S15型印刷機（IINUMA GAUGE製作所公司製、 Anilox Roll ( 3 00# )、凸版（網點 400L 30% 75°))，塗 佈液晶配向劑（日產化學工業公司製、桑愛巴（登錄商標 )SE-3140 0735 (商品名；聚醯胺酸型）、SE-7492 062M (商品名；聚醯胺酸/可溶性聚醯亞胺混合型）、SE-529 1 062B (商品名；可溶性聚醯亞胺型））。之後，在溫度 8 0°C的加熱板上進行3分鐘乾燥後形成液晶配向膜。使形 成液晶配向膜以目視觀察，液晶配向膜無龜裂、針孔及不 均之良好場合爲〇、有針孔或不均之場合爲△、產生龜裂 而在基板上無法充分成膜之狀態爲X。 [產業上之利用性] 本發明之電極保護膜形成劑，在柔版印刷法、狹@塗 -28- 201136995 佈法、噴射塗佈法、噴敷法、及凹版塗佈法的塗膜形成能 力優異、且在低溫可形成能充分硬化之電極保護膜。進一 步，所形成電極保護膜可在其上層形成抑制龜裂或針孔之 液晶配向膜。因此，尤其在使用必需低溫燒成之塑膠基板 的液晶顯示装置、或液晶方式之電子紙等電極保護膜上有 用。 又，引用2009年12月02日申請的日本專利2009-2 746 62號的說明書、申請專利範圍、及摘要的全部內容 於此，作爲本發明之說明書之揭示內容° -29-[Technical Field] The present invention relates to an electrode protective film forming agent containing a polyoxyalkylene oxide, an electrode protective film, and an electronic device having the electrode protective film. In particular, an electrode protective film forming agent, an electrode protective film, and a liquid crystal display element having the electrode protective film which can be used for a liquid crystal display element. [Prior Art] In the production of a liquid crystal display device, an oxide film is formed between a transparent electrode and a liquid crystal alignment film for the purpose of insulating and protecting a transparent electrode. As a method of forming the oxide film, a vapor phase method such as a vapor deposition method or a sputtering method and a coating method using a coating liquid for forming an oxide film are known. Among them, the coating method is often used in view of productivity or ease of formation of a large-sized substrate. As the coating liquid, a hydrolyzate of tetraalkoxynonane and a complex with other metal alkoxide or metal chelate compound are known. When a coating liquid is prepared by using a metal alkoxide, the metal alkoxide is generally removed, and the hydrolysis rate is high and the reaction control is difficult. Therefore, in order to adjust the hydrolysis rate of the alkoxide, it is attempted to act as a chelating agent such as acetamidineacetone. However, a compound which is generally chelated has a high thermal decomposition temperature and is expected to be calcined at 450 ° C or higher. (For example, Patent Document 1 is a reference.) In another method, in the ceria-titania-based coating liquid, an attempt is made to add a mineral acid in a hydrolyzate of a decane oxide and a titanium alkoxide without using a chelate compound. It becomes a transparent coating agent by means of stabilization. In this case, at least 300 °C or more is required for firing. (For example, Patent Document 2 is referred to as 201136995.) In addition, a display using a plastic plate or a plastic film on a substrate such as a plastic LCD or an electronic paper has recently been proposed, and it is desired to obtain sufficient hardness even at a low temperature of 200 ° C or lower. And the upper alignment agent can be coated without defects. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 55-35487 (Patent Document 2) [Problems to be Solved by the Invention] Patent Document 1 Further, in the method of Patent Document 2, it is difficult to obtain an electrode protective film having a sufficient hardness at a firing temperature of 200 ° C or lower. Further, when a liquid crystal alignment film is formed on the upper layer of the electrode protective film, the alignment film has a problem that cracks or pinholes are generated. In the present invention, an electrode protective film forming agent, an electrode protective film, and an electronic device having the electrode protective film which can form an electrode protective film having sufficient hardness even when fired at a low temperature of 150 ° C or lower are provided. In particular, in the case of a liquid crystal display device, an electrode protective film forming agent which is provided on the upper layer of the electrode protective film to form a liquid crystal alignment film which suppresses generation of cracks or pinholes is used. [Means for Solving the Problem] -6 - 201136995 The inventors of the present invention have completed the present invention based on the above-described situation and efforts to study the results. That is, the main subject of the present invention is as follows: 1. A method comprising at least one selected from the group consisting of an alkoxydecane represented by the formula (1) and an alkoxy sand chamber represented by the formula (2). An electrode protective film forming agent characterized by polycondensation obtained by polycondensation of alkoxysilane of a compound. R1{Si(OR2)3}P (1) (R1 is a hydrocarbon group having 1 to 12 carbon atoms substituted by a urea group, R2 is an alkyl group having 1 to 5 carbon atoms, and p is an integer of 1 or 2) (R3)nSi(OR4)4-〇(2) (R3 is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amine group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate a hydrocarbon group having 1 to 8 carbon atoms substituted with a propylene oxime group, R 4 is an alkyl group having 1 to 5 carbon atoms, and η is an integer of 0 to 3. (2) η is 0 in the formula (2) The electrode protective film forming agent according to the above 1, which is a tetraalkoxy decane. 3. The alkoxydecane represented by the above formula (1) contains 0.5 to 60 mol% in the peralkoxydecane, and the alkoxydecane represented by the above formula (2) is contained in the peralkoxydecane. 40 to 99.5 mol% of the electrode of the above 1 or 2, 201136995 Protective film forming agent. 4. Electrode protection according to the group of the above formula (1), oxy oxane and r-urea 3 oxy decane. The above-mentioned 1 to 4 were fired to obtain 6 · the above-mentioned 1 to 4 medium substrate, and the formation of the protective film at room temperature to the end point 7. The firing temperature was 100-forming method. 8. The above-mentioned 5 is described. [Effect of the invention] The electrode protective film formed of a base having low heat resistance such as a low-temperature slab having a temperature of 150 ° C or less according to the present invention. Therefore, at least one selected from the group consisting of r-ureidopropyltriethylidenepropyltrimethoxydecane and r-ureidopropyltripropane is an alkoxydecane represented by liquid crystal I having excellent properties. Any of the above film forming agents 1 to 3. Any one of the liquid crystal alignment agents described above is applied to a substrate and an electrode protective film. The electrode protective film forming agent according to any one of the inventions is applied after being dried at a temperature of 1 20 ° C and then calcined. An electronic device for an electrode protective film having the shape of the electrode protective film described in the above-mentioned 6 at 180 °C. The liquid crystal display element of the electrode protective film. The electrode protective film obtained by the extremely protective film forming agent has sufficient hardness in the modification condition and can be applied to a plastic substrate. Further, in the case of a liquid crystal display device, a liquid crystal alignment film which suppresses cracks or pinholes can be formed, and a substrate having low heat resistance such as a plastic substrate can be used for the production of display elements. [Best Mode for Carrying Out the Invention] -8 - 201136995 The polyoxymethane of the electrode protective film forming agent of the present invention. Therefore, an electrode protective film having sufficient hardness is formed even at 1 Å. Conventionally, when a firing temperature is low, a film of a siloxane polymer or an oxide film is decomposed. Therefore, the polyimine-based alignment film having different characteristics for the liquid crystal display element is sufficient to detect cracks or pinholes when the alignment film is formed. Since the electrode protective film-forming agent contains a urea group, the affinity is improved and the suppression is suppressed. The crack or pinhole film forming agent is sufficiently hardened at a low temperature of 1 00 to 1 500 °C. The invention is described in detail below. [Polyoxyalkylene] The electrode protective film forming agent of the present invention; i. Alkoxydecane of alkoxydecane is described as an alkane. R'{Si(OR2)3}p (1) In the formula (1), R1 is a group in which a hydrocarbon group is taken from a urea group and is substituted by a hydrocarbon having 1 to 12 carbon atoms in detail. R 1 is preferably a urea-based group having a maximum characteristic of having a urea group/150 ° C, a so-called low temperature or a precursor substance remaining in the oxidation of the precursor substance, and the affinity for the interface is not sufficient, and the interface affinity is not obtained. Sexuality can be the reason. In the present invention, it is considered that the polyfluorene-based alignment agent can be formed into a polyfluorene-containing carbon obtained by condensation condensation of the following formula (1) even when the electrode is fired. Any hydrogen atom having a number of atoms of 1 to 12 is a -9-201136995 hydrocarbon group having 1 to 7 carbon atoms by a urea group. R2 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. p is an integer of 1 or 2. R1 and R2 may have a linear structure or have a branched structure. In the alkoxydecane represented by the formula (1), when p is 1, the alkoxydecane represented by the formula (1-1). R'Si(〇R2)3 (1-1) Further, when P is 2, the alkoxydecane (R2〇) 3Si-R'-Si(OR2)3 (1) represented by the formula (1-2) -2) Specific examples of the alkoxydecane represented by the formula (1-1) are not limited thereto. For example, 7-ureidopropyltriethoxydecane, r-ureidopropyltrimethoxydecane, r-ureidopropyltripropoxydecane, (R)-heart 1-phenylethyl- >^'-triethoxydecylpropylurea, (11)-:^-1-phenylethyl-hydrazone-trimethoxydecylpropylurea, and the like. Among them, '7-ureidopropyltriethoxylate sandstone or ureidopropyltrimethoxydecane is particularly preferable because it is easily obtained as a commercial product. Specific examples of the alkoxydecane represented by the formula (1-2) are not limited thereto. For example, bis[3-(triethoxydecyl)propyl]urea, bis[3-(triethoxydecyl)ethyl]urea, bis[3-(trimethoxydecyl)propyl] Urea, bis[3_(tripropoxydecylalkyl)propyl-10-201136995] urea, and the like. Among them, bis[3-(triethoxydecyl)propyl]urea is particularly preferred because it is easily obtained as a commercially available product. When the alkoxy decane represented by the formula (1) is less than 0.5 mol% in the peralkoxy decane used for the electrode protective film forming agent, the printability of the liquid crystal alignment film is not obtained, so It is better to use 〇·5 mol% or more. More preferably, it is more than 1% by mole. Further, it is more preferably 2. When the amount of 〇mol is more than 60% by mole, the electrode protective film formed is not sufficiently cured, so it is preferably 60 mol% or less. More preferably 50% by mole or less. More preferably, it is 40% or less. Further, the electrode protective film forming agent of the present invention can be polymerized with at least one alkoxysilane represented by the formula (1) and at least one of the alkoxysilanes represented by the following formula (2). Obtained by condensation. (R3)nSi(OR4)4-n (2) (R3 is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amine group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, substituted with a propylene methoxy group, and R 4 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and η is 0. 〜3, preferably an integer of 0 to 2.) R3 of the alkoxydecane represented by the formula (2) is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amine group, a glycidoxy group, The hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, substituted by a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group. R4 is the same as R2 above and -11 - 201136995, and the preferred range is also the same. In the case of R3, it is an aliphatic hydrocarbon; an aliphatic ring, an aromatic ring or a heterocyclic ring structure; an unsaturated bond; it may contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or may have a branched structure. The number of carbon atoms is an organic group of 1 to 6. Further, R3 may be substituted by a halogen atom, a vinyl group, an amine group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate group, an acryloxy group or the like. Specific examples of the alkoxydecane represented by the formula (2) are exemplified below, but are not limited thereto. In the alkoxydecane of the formula (2), specific examples of the alkoxy decane in the case where R3 is a hydrogen atom are, for example, trimethoxydecane, triethoxydecane, tripropoxydecane or tributoxydecane. Further, specific examples of the other alkoxydecane of the formula (2), such as methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and propyl group. Trimethoxydecane, propyltriethoxydecane, methyltripropoxydecane, 3-aminopropyltrimethoxydecane, 3·aminopropyltriethoxydecane, N-2 (amino group) Ethyl) 3-aminopropyltriethoxydecane, N 2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxy Decane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl) Triethoxy decane, 3-mercaptopropyltriethoxy decane, decylmethyltrimethoxy decane, vinyl triethoxy decane 'vinyl trimethoxy decane, allyl triethoxy decane , 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, -12-201136995 3 - propylene methoxypropyl triethyl Baseline, 3-isocyanate propyltriethoxydecane, trifluoropropyltrimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane , dimethyldiethoxydecane, dimethyldimethoxydecane, diethyldiethoxydecane, diethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiene Ethoxy decane, 3-aminopropylmethyldiethoxy decane, 3-aminopropyldimethylethoxy decane, trimethylethoxy decane, trimethylmethoxydecane, and the like. The electrode protective film forming agent of the present invention may have one or more of the specific organic groups in such a manner that the adhesion to the substrate, the hardness of the film, and the printability of the upper liquid crystal alignment film are not impaired in the effects of the present invention. In the alkoxydecane represented by the formula (2), n is a fluorene alkoxy decane tetraalkoxy decane. The tetraalkoxydecane is preferably condensed with the alkoxydecane represented by the formula (1), and is preferably used to obtain the polyoxyalkylene of the present invention. In the case of the alkoxydecane wherein η is 0 in the formula (2), tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane is more preferable, tetramethoxy decane or When the alkoxy decane represented by the formula (2) is used, the alkoxy group represented by the formula (2) in the peralkoxy decane used for obtaining the electrode protective film forming agent. The decane is preferably 40 to 99.5 mol%. More preferably 50~99.5% by mole. It is better for 6 0 to 9 9.5 mol%. In the present invention, the electrode protective film forming agent is obtained by polycondensation of at least one compound selected from the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (2). Alkane is preferred. -13-201136995 The electrode protective film forming agent of the present invention can be used in one or more kinds of alkoxy groups in the range of the hardness of the film and the printability of the upper liquid crystal alignment film without impairing the effects of the present invention. Decane. [Method for Producing Polyoxane] The method for obtaining a polyoxyalkylene used in the present invention is not particularly limited, and in the present invention, an alkoxy group having an alkoxysilane of the above formula (1) as an essential component can be used. The decane is obtained by condensation in an organic solvent. Usually, the polyoxane ' can be obtained by polycondensing the alkoxy decane to form a solution which is uniformly dissolved in an organic solvent. The polycondensation method in the present invention may, for example, be a method in which the alkoxydecane is hydrolyzed and condensed in a solvent such as an alcohol or a diol. At this time, the hydrolysis/condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times moles of water of the all alkoxide groups in the alkoxydecane, but it is usually preferred to add more than 5 times the molar excess of water. In the present invention, the amount of water used in the above reaction may be appropriately selected as desired. Usually, 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane is used, and more preferably 0.75 to 1.5 times moles. Further, for the purpose of promoting hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid may be used: ammonia, methylamine, ethylamine, ethanolamine, triethylamine A base such as a base amine; a catalyst such as a metal salt such as hydrochloric acid or sulfuric acid 'nitric acid>> and a solution in which alkoxysilane is dissolved by heating' further promotes a hydrolysis/condensation reaction. At this time, the heating temperature and the heating time can be appropriately selected as desired. For example, at 5 〇 -14 - 201136995 ° C, heating, stirring, refluxing, heating for 1 hour, stirring, etc., for 24 hours. Further, as another method, for example, a method in which a mixture of an alkoxysilane, a solvent, and an organic acid such as formic acid, oxalic acid, maleic acid or fumaric acid is heated to be polycondensed can be mentioned. For example, a method in which a mixture of alkoxydecane, a solvent and oxalic acid is heated and then condensed. Specifically, a method in which an alkoxysilane is mixed in a state in which the solution is heated by adding oxalic acid to an alcohol solution of oxalic acid in advance is added. In this case, the amount of oxalic acid used is preferably 0.2 to 2 moles per 1 mole of the alkoxy group of the alkoxydecane. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. Preferably, the method is heated at reflux for a period of from ten to ten hours in a manner that does not cause evaporation or volatilization of the solution. When a polyoxyalkylene oxide is obtained, a plurality of alkoxysilanes may be used, and a mixture of a plurality of alkoxysilanes may be used in advance, or a plurality of alkoxysilanes may be sequentially mixed. The solvent (hereinafter, also referred to as a polymerization solvent) used in the polycondensation of the alkoxydecane is not particularly limited as long as it can dissolve the alkoxysilane. Further, even when the alkoxysilane is not dissolved, it may be dissolved by the polymerization reaction of the alkoxydecane. In general, an alcohol is formed by a polycondensation reaction of an alkoxydecane, and an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with an alcohol can be used. For example, alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanedi-15- 201136995 alcohol, 1,3 - glycols such as pentanediol, 1,4-pentanediol, pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1'6-hexanediol, etc. ; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, B Glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl acid, propylene glycol diethyl ether, propylene glycol dipropyl ether, Glycol ethers such as propylene glycol dibutyl ether; N-methyl-2 -D ratio, N,N-dimethylformate 'Ν, Ν-dimethylacetamide, butyrolactone, two Methyl hydrazine, tetramethyl urea, trimethylamine hexamethylphosphate, m-cresol, and the like. In the present invention, the above-mentioned polymerization solvent may be used in combination. The polymerization solution of the polyoxyalkylene obtained by the above method (hereinafter, also referred to as a polymerization solution) is generally a concentration of Si〇2 in a sand atom of a total alkoxy oxime which is added as a raw material (hereinafter referred to as The concentration of Si〇2 is .20% by mass or less. By selecting an arbitrary concentration in this concentration range, colloid formation can be suppressed and a homogeneous solution can be obtained. In the present invention, the polymerization solution of the polyoxyalkylene obtained by the above method may be directly used as an electrode protective film forming agent, or the solution obtained by the above method may be concentrated, added to a solvent, diluted, or substituted with another solvent, if necessary. Used as an electrode protective film forming agent. In this case, the solvent to be used (hereinafter, also referred to as an additive solvent) may be the same as the poly-16-201136995 solvent or may be another solvent. The solvent to be added is not particularly limited in the range in which the polyoxane is uniformly dissolved, and may be used arbitrarily or in combination. Specific examples of the solvent to be added include, in addition to the solvent of the above-mentioned polymerization solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate, ethyl acetate, and lactic acid; Ester such as ethyl ester. Such a solvent can improve the viscosity of the electrode protective film forming agent or the coating of the electrode protective film forming agent on the substrate by spin coating, flexographic printing, spray coating, slit coating, or the like. Cloth. [Other components] In the present invention, other components than the above polysiloxane, such as inorganic fine particles, metalloxane oligomers, and metal oxide polymerization, may be contained within the range of the effects of the present invention. A component such as a substance, a flat agent, or a surfactant. The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium dioxide fine particles or magnesium fluoride fine particles, and particularly preferably in a colloidal solution state. The colloidal solution may be a colloidal solution in which inorganic fine particles are dispersed in a dispersion medium or a commercial product. In the present invention, by containing inorganic fine particles, the surface shape and refractive index of the cured film can be adjusted to impart other functions. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 μχη, more preferably 0.001 to 0.1 μΐΏ. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by using the preparation coating liquid may be lowered. -17- 201136995 The dispersion medium of the inorganic fine particles may, for example, be water or an organic solvent. The colloidal solution is preferably adjusted to a pH of 1 to 1 by pH or pKa from the viewpoint of stability of the electrode protective film forming agent. The pH or pKa is more preferably 2 to 7. The organic solvent used for the dispersion medium of the colloidal solution may, for example, be methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, or B. Alcohols such as diol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, An amide such as N-methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or r-butyrolactone; or an ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium. As the metal oxyalkylene oligomer and the metal oxyalkylene polymer, a single or composite oxide precursor such as ruthenium, titanium, aluminum, molybdenum, niobium, tantalum, tin, indium or zinc can be used. The metalloxane oligomer and the metalloxane polymer may be commercially available or may be obtained by a usual treatment such as hydrolysis of a metal alkoxide, a nitrate, a hydrochloride or a carboxylate. By. Specific examples of the commercially available metal oxyalkylene oligomer and the metal oxyalkylene polymer include methyl oxalate 51, methyl phthalate 53A, and ethyl decanoic acid manufactured by COLCOAT CO., Ltd. Titanx xane oligomerization such as ester 40, ethyl phthalate 48, EMS_485, SS-101, etc., or a cesium alkoxide polymer, or a titanium-η-butoxide tetramer made by Kanto Chemical Co., Ltd. Things. These may be used alone or in combination of two or more. Further, a flatner, a surfactant, or the like can be used, and a commercially available product is particularly preferable because it is easy to obtain. -18- 201136995 Further, the method of mixing the above other components with polyoxymethane is not particularly limited as long as it is followed by or after the polysiloxane. [Electrode protective film] The electrode protective film forming agent of the present invention is applied to an electrode or an electrode-attached substrate and thermally cured to obtain a desired electrode protective film. The coating method of the electrode protective film forming agent may be a conventional or well-known method, for example, a dipping method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a roll coating method, or a knife coating method. , a floating knife coating method, a flexographic printing method, a spray coating method, a slit coating method, and the like. In the above, in the flexographic printing method, the slit coating method, the spray coating method, the spray coating method, and the gravure coating method, a good coating film can be formed. In this case, a substrate is used, for example, plastic; glass ; ΑΤΟ, FTO (fluorine-doped tin oxide), ITO, IZO, etc. with transparent electrode glass; ceramics and other substrates. Plastics, for example, polycarbonate, poly(meth) acrylate, polyether oxime, polyarylate, polyurethane, poly maple, polyether, polyether ketone, polyolefin, polyethylene terephthalate Formate, polyacrylonitrile, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, and the like. The shape of the substrate may, for example, be a plate or a film. The electrode protective film forming agent 'is generally filtered using a filter or the like before coating. The coating film formed on the substrate was at room temperature ~120. (The temperature of the temperature is preferably 60 to 90 ° C. After drying, it is preferably at a temperature of 1 〇〇 to 18 〇. 〇, and more preferably 1 to 5 0 to 18 ° C for thermal hardening. At this time, the drying time can be from 3 〇-19 to 201136995 seconds, but less than 1 〇 minutes is sufficient. The time required for heat curing can be appropriately selected, but it can be more than 5 minutes. Select low hardening temperature In the case of the electrode protective film forming agent of the present invention, the electrode protective film forming agent of the present invention can be hardened with sufficient hardness even at a curing temperature of more than 180 ° C. Further, it is also effective to irradiate an energy ray (ultraviolet rays, etc.) with a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, etc. before thermosetting. By irradiating a dry coating film with a fl line, it is possible to harden it. The temperature is lowered to increase the hardness of the film. The amount of energy line irradiation can be appropriately selected as necessary, but it is usually in the range of several hundred to several thousand m/cm2. The electrode protective film of the present invention is due to the liquid crystal alignment material on the film. Good printability, can be formed In the electrode protective film forming agent of the present invention, the electrode protective film having the above characteristics can be formed, and it is very useful to improve the display characteristics of the liquid crystal display element. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. However, the present invention is not limited to the following examples. In the present examples, the abbreviations of the compounds used are as follows. TEOS: tetraethoxydecane APS: 3-amine Propyltriethoxydecane-20- 201136995 GPS : 3-glycidoxypropyltrimethoxydecane MPS: 3-mercaptopropyltrimethoxydecane UPS: 3-ureidopropyltriethoxy Base decane MPMS: 3-methacryloxypropyltrimethoxydecane TET: tetraethoxytitanium AN: aluminum nitrate nonahydrate HG: hexanediol (alias: 2-methyl-2,4-pentyl) Alkanediol) PGME: propylene glycol monomethyl ether (alias: 1-methoxy-2-propanol) BCS: butyl cellosolve (alias: 1-butoxy-2-ethanol) PB: propylene glycol monobutyl ether (alias · 1-butoxy-2-propanol) Ν Μ P : N-methyl-2-pyrrolidone l,4-BDO : 1,4-butanediol MeO H: methanol EtOH: ethanol [Synthesis Example 1] To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 39.0 g of MeOH was added, and 18.0 g of oxalic acid was added thereto in an average amount by stirring under stirring to prepare methanol of oxalic acid. Then, the solution is heated to its reflux temperature, and tetraethoxy decane 1 〇.4 g, APS 1 · 1 g, GPS 2.4 g, MPS 1.0 g, and 92% of UPS are contained in the solution under reflux. A mixture of 8.6 g of methanol solution (UPS content: 7.9 g) and Me〇H 19.5 g was dropped for 45 minutes. After the completion of the dropwise addition, the mixture was further heated under reflux for 5 hours, and then cooled to prepare a solution (L 1 ) of polyoxyalkylene. -21 - 201136995 Further, in a 3.00 ml flask, 1 μg of the polyoxyalkylene solution L1, 64.0 g of HG as a solvent, 48.0 g of NMP, and 32.0 g of 1,4-BDO were mixed. Then, the solvent was distilled off by a NEW rotary evaporator (manufactured by Tokyo Chemical and Chemical Co., Ltd., NE-1) at 60 ° C while gradually reducing the pressure to 20 mmHg (2.67 kPa) to obtain 184.0 g of a solvent instead of NMP. Solution (hereinafter, also referred to as a replacement solution). Thereafter, 184.0 g of the substitution solution and 16.0 g of PGME were mixed, and a polyoxydeoxygenane solution (LA1) having a solid concentration of SiO 2 of 3% by mass was obtained. [Synthesis Example 2] In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 34.8 g of MeOH, 27.8 g of TEOS, and 9.6 g of a methanol solution containing UPS 92% (UPS content: 8.8 g) were added, followed by stirring. A solution of the alkoxydecane monomer is prepared. To the solution, a solution of 17.64 g of MeOH, 9.00 g of water, and 1.50 g of oxalic acid as a catalyst was mixed, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxymethane solution having a solid concentration of 10% by mass in terms of SiO 2 . 30.0 g of the obtained polyoxane solution was mixed with 5.0 g of HG and 5.0 g of BCS3 to obtain a polysiloxane diluted solution (LA2) having a solid concentration of SiO 2 of 3% by mass. [Synthesis Example 3] A 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube was charged with -22-201136995 to 31.8 g of PGME and 33.0 g of TEOS, followed by stirring to prepare a solution of an alkoxy decane monomer. In the solution, a solution of 15.9 g of PGME, 15.0 g of water, and 2 g of oxalic acid oxalate as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, stirring was carried out at room temperature for 30 minutes. Thereafter, after heating under reflux for 30 minutes, 2.4 g of a methanol solution containing UPS 92% (UPS content: 2.2 g) and a solution of PGME 1.8 g were added, and further heated under reflux for 3 minutes, and then cooled to obtain S. i Ο 2 conversion of a solid concentration of 1 〇 mass% of a polyoxoxy solution ° 30.0g of the obtained polyaluminoxane solution 'mixed PGME 60.0g, and HGlO.Og, to obtain a solid concentration of SiO 2 conversion of 3 masses % polyoxane diluted solution (LA3). [Synthesis Example 4] A solution of alkoxydecane monomer was prepared by adding "31.5 g of PGME, 31.2 g of TEOS, and 2.1 g of MPMS" to a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. In the solution, a solution of 15.7 g of PGME, 15.0 g of water, and 3 g of oxalic acid oxalate as a catalyst was mixed in advance, and it was dropped at room temperature for 3 minutes. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Then, after heating under reflux for 30 minutes, a solution containing 2.4 g of a UPS containing 92% of UPS (UPS content: 2.2 g) and a solution of 1.8 g of PGME was added, and further heated under reflux for 30 minutes, and then cooled to obtain a SiO 2 conversion. The polypyroxane solution having a solid concentration of 1% by mass is obtained by mixing 30.0 g of the obtained polyoxane solution with 60.0 g of PGME and -23-201136995 HG10.Og to obtain a solid concentration of Si〇2. 3 mass% of a polyoxyalkylene diluted solution (LA4). [Synthesis Example 5] A solution of alkoxysilane monomer was prepared by adding HG 20.6 g, BCS 6.9 g, and TEOS 37.5 g to a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. In the solution, a solution of HG 10.3 g, BCS 3.4 g, water 10.8 g, and oxalic acid oxalate as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, stirring was performed at room temperature for 30 minutes. . After that, 'after reflux, after heating for 30 minutes', a solution of 5.8 g (UPS content: 5.3 g), HG 3.2 g, and BCSl.g of a methanol solution containing 92% of UPS was added, and further heated under reflux for 30 minutes. A polysiloxane solution having a solid concentration of 12% by mass in terms of Si〇2 was obtained by cooling. The obtained polyoxydecane solution was mixed with 30.0 g of HG, 41.9 g of HG, 7.1 g of BCS and 40.9 g of PB to obtain a solid content concentration of SiO 2 in terms of SiO 2 . The polythene oxide diluted solution (LA5). [Synthesis Example 6] 90 g of the polyoxalate solution LA2 obtained in Synthesis Example 2 and colloidal ceria microparticles (product name: methanol ceria sol, manufactured by Nissan Chemical Industries Co., Ltd.; SiO2 conversion solid concentration was 30 After the mixture was stirred at room temperature for 30 minutes at a temperature of 3.0 g and MeOH 7.0 g, a dioxane diluted solution (-24-201136995 LA6) having a solid concentration of 3% by mass in terms of Si 〇 2 was obtained. [Comparative Synthesis Example 1] To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 40.3 g of EtOH was added, and 18.0 g of oxalic acid was added in a small amount to the Et0H under stirring to prepare an ethanol solution of oxalic acid. Then, the solution was heated to the reflux temperature, and the mixture under reflux was allowed to drip with a mixture of TEOS 2〇·8 g and EtOH 20.8 g for 45 minutes. After the completion of the dropping, the mixture was further heated under reflux for 5 hours, and the solution of polyoxyalkylene was prepared by cooling. Further, 10 μg of the polyoxyalkylene solution, 64.0 g of HG as a solvent, 48.0 g of NMP, and 32.0 g of 1,4-BDO were mixed in a 300 ml flask. Then, a NEW rotary evaporator (manufactured by Tokyo Chemical Industry Co., Ltd., NE-1) was gradually reduced in pressure to 20 mmHg (2.67 kPa) at 60 ° C to distill off the solvent, and 184.0 g of a substitution solution was obtained. Thereafter, pGME16.〇g was mixed in 1 84.0 g of the substitution solution to obtain a polyoxysilane solution (LB1) having a solid concentration of SiO 2 of 3% by mass. [Comparative Synthesis Example 2] HG23_7g, BCS7.9g, and TEOS41.7g were added to a 200 mm reaction flask equipped with a thermometer and a reflux tube, and then stirred to prepare a monomer of the oxygen sand chamber. Solution. In this solution, HG11.8g, BCS3.9g, water l〇.8g, and a solution of oxalic acid oxalate. 2g as a catalyst were mixed in advance for 30 minutes at room temperature, and 30 minutes to 25 minutes after the completion of the dropwise addition. 201136995 Stirring at room temperature. After that, the mixture was heated under reflux for 60 minutes, and then allowed to cool to obtain a polyoxane solution having a solid concentration of 12% by mass in SiO 2 to obtain 30.0 g of the obtained polyoxane solution, and HG 55.2 g 'BCS 9.2 g and HG were mixed. PB5 was 5.6 g, and a polyoxane diluted solution (LB2) having a solid concentration of SiO 2 of 3% by mass was obtained. [Comparative Synthesis Example 3] 2.5 g of pure water, 64.8 g of ethanol, and 2.7 g of AN as a catalyst were placed in a 300 ml flask, and stirred to obtain a uniform solution. To the solution was added 14.3 g of TEOS, and the mixture was stirred at room temperature for 30 minutes. Thereafter, TET 1 5 · 7 g was added, and stirring was carried out for 30 minutes at room temperature. This solution was used as a solution (pre-substitution solution) before the solvent was replaced by HG. Further, 24.0 g of the obtained pre-substituting solution and 5.8 g of HG2 were mixed in a 300 ml flask. Then, the solvent was distilled off while slowly reducing the pressure to 20 mmHg (2.67 kPa) at 60 ° C using a NEW rotary evaporator (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain 28.9 g of a substitution solution. Then, after mixing PG Μ E 1 1 · 1 g in the substitution solution of 2 8 9 g, a polyxamidine solution (the evaluation of the electrode protective film) of the solid concentration of Si 〇 2 in terms of 3% by mass was obtained. The electrode protective films formed of the obtained solutions (LA1 to LA6) and (LB1 to LB3) were evaluated for pencil hardness, water contact angle -26 to 201136995, and liquid crystal alignment film printability by the method described later. The results are shown in Table 1. 1] Coating liquid, water contact angle, pencil hardness, liquid crystal alignment film printing < k SE-3140 SE-7492 SE-5291 L A1 Example 1 50.8. 6H 〇 〇 〇 L A2 Example 2 51.2° 6H 〇 〇 〇 L A3 Example 3 42· 9° 6H 〇 〇 〇 L A4 Example 4 61 _ 2. 6H 〇〇〇L A5 Example 5 43,0° 6H 〇〇〇L A6 Example 6 44. 0° 5H 〇〇〇LB 1 Comparative Example 1 60. 7° 3H r 〇Δ XLB 2 Comparative Example 2 63. 1° 3H Γ〇Δ XLB 3 Comparative Example 3 57. 1° 3H 〇〇Δ As a result of Table 1, the electrode protective film obtained by the present invention exhibits a film for general use even at a low-temperature curing temperature of 150 ° C or less. In the case of an electrode protective film (insulating film) for a liquid crystal display element, a pencil hardness of 5H or more is required. Further, on the film, not only a polylysine type but also a liquid phase alignment agent of a soluble polyimine type is used, and excellent film formability without cracks or pinholes is also obtained. [Pencil hardness] The polysiloxane solution (coating liquid) of the synthesis examples (LA1 to LA6) and the comparative synthesis examples (LB1 to LB3) was filtered using a chromatography disk (manufactured by Kurabo Industries, Ltd., pore size: 0.45 μm). After that, it was dropped on an ITO glass substrate (ITO film thickness: 140 nm) having a thickness of 0.7 mm, and was rotated by a spin coater (manufactured by Mikasa Co., Ltd., 1H-DX2) at a rotation number of 300 rpm for 5 seconds. The coating film was formed by rotating at 2000 to 5000 rpm for 20 seconds. Subsequently, the mixture was dried on a hot plate at a temperature of 80 ° C for 3 minutes, and then heated on a hot plate at a curing temperature of 150 ° C for 15 minutes to obtain a cured film. The pencil hardness of the obtained hardened film was measured in accordance with the test method (JIS K5 400). [Water contact angle] The contact angle when 3 liters of pure water was dropped was measured using an automatic contact angle meter CA-Z type manufactured by Kyowa Interface Science Co., Ltd. Further, the method of using the substrate and the method of producing the protective film are the same as those in the case of measuring [pencil hardness]. [Liquid alignment film printability] On the cured film formed by the method similar to the above [pencil hardness], an S15 type printing machine (II, manufactured by IINUMA GAUGE Co., Ltd., Anilox Roll (300 00#), letterpress (network dot 400L 30% 75°) was used. )), coated with liquid crystal alignment agent (manufactured by Nissan Chemical Industries Co., Ltd., Sang Aiba (registered trademark) SE-3140 0735 (trade name; polyglycolic acid type), SE-7492 062M (trade name; polyglycine/ Soluble polyimine mixed type), SE-529 1 062B (trade name; soluble polyimine type)). Thereafter, the film was dried on a hot plate at a temperature of 80 ° C for 3 minutes to form a liquid crystal alignment film. When the liquid crystal alignment film is formed and visually observed, the liquid crystal alignment film is free from cracks, pinholes, and unevenness. In the case where there is a pinhole or unevenness, it is Δ, cracking occurs, and the film cannot be sufficiently formed on the substrate. The status is X. [Industrial Applicability] The electrode protective film forming agent of the present invention is formed by a flexographic printing method, a coating method of a coating method, a spray coating method, a spray coating method, and a gravure coating method. It has excellent ability and can form an electrode protective film which can be sufficiently hardened at a low temperature. Further, the electrode protective film formed can form a liquid crystal alignment film which suppresses cracks or pinholes in the upper layer. Therefore, it is useful particularly for use in an electrode protective film such as a liquid crystal display device which is required to be fired at a low temperature, or an electronic paper such as a liquid crystal type. Further, the entire contents of the specification, the patent application, and the abstract of Japanese Patent Application No. 2009-2 746 62, filed on Dec.