1229036 ▲ 五、 發明說明 (1 ) 技 術 領 域 本 發 明 係 有關一種阻氣性優異的阻氣性薄膜。詳言之 ， 係有 關 一 種即使在高濕度下可保持極高阻氣性之阻氣 性 薄 膜 0 先前技 術 聚 丙 烯 薄 膜或聚對酞酸乙二酯薄膜、耐龍薄膜等之熱 塑 性 樹 脂 薄 膜，藉由優異的透明性、機械強度、加工適 性 製 袋 性 等二次加工性等，可廣泛地使用作爲包裝用 薄 膜 〇 以 賦 予 上 述薄膜具阻氧性等之阻氣性能爲目的時，可在 該 熱 塑 性 樹 脂薄膜之薄膜表面上積層偏二氯乙烯系樹脂、 或 聚 乙 烯 醇 系樹脂等之具有阻氣性的樹脂所成層。 然 而 偏 二氯乙烯系樹脂之阻氣性優異，惟氯系樹脂在 焚 燒 性或 廢 棄性方面係有缺點。而且，聚乙烯醇系樹脂在 乾 燥 狀 態 下 雖具有優異阻氧性，惟在高濕度下阻氧性會因 吸 濕 而 變 得 極端降低。 因 此 1 必 須進行交聯或改性處理、與其他化合物複合的 功夫 0 例如 日本特開昭56 - 4563號公報中掲示在熱塑性樹 脂 薄 膜 上 設 置由二氧化矽/聚乙烯醇系複合聚合物所成被 覆 層 之 阻 氣 性薄膜。此外，於特開平6- 1 92454號公報中 揭 示在 熱 塑 性樹脂薄膜上設置由金屬烷氧化物或金屬烷氧 化物 之 水 解 物、與聚乙烯醇等具有羥基之水溶性樹脂之複 合 物 所成 被 膜的阻氣性薄膜。 -3- 1229036 五、 發明說明 ( 2 ) 然 而 1 上 述 特 開昭56 - 4563號公報及特開平6 - 1 92454 號 公 報 中 記 載 的 阻氣性薄膜，企圖改善在高濕度下阻 氧 性 因 吸 濕 而 極 端 降 低的問題，特別是大於90MH之高濕 度 下 該 阻 氣 性 效 果 仍不夠充分。 另 外 在 由 上 述複合物所成的阻氣層中另改良阻氣 性 能 之 薄 膜 係如特 開2000-432 1 9號公報中揭示在熱塑 性 樹 脂 薄 膜 上 設 置 由 聚乙烯醇等具有羥基之水溶性樹脂、 >frrf 機 層 狀化 合 物 及金 屬烷氧化物之水解物所成被膜的阻氣 性 薄 膜 惟 該 阻 氣 性 薄膜中在高濕度下之阻氣性、以及設 有 密 封 層 後 在 熱 水中 沸騰後之阻氣性仍有待改善。 因 此 本 發 明 之目的係提供一種即使在大於90%RH 之 高 濕 度 下仍 具 有 極 爲優異的阻氣性、且於沸騰後之阻氣 性也 極 爲 優 異 的 阻 氣 性薄膜。 發 明 Z 掲 示 本 發 明 人 等 爲 達成上述目的，再三深入硏究檢討。 結 果 發 現在 基 材 層 上，特定條件下，在聚乙烯醇系樹脂 之 水 性 溶 液 中 分 散 有 層狀矽酸鹽存在下被覆由烷氧化矽水 解 所 得 的水性 溶 液 所成阻氣性被覆層、予以形成所得的阻 氣 層 與 習 知 提 案 具 相同成分之阻氣層不同，在該層狀矽 酸 鹽 之 層 間 確 認 有 以 烷氧化矽及/或其水解物爲基準的矽 存在 7 且 使作 爲 上 述 阻氣層內光散射大的構造體（散射體）之烷 氧 化矽 的 水 解 物 、層狀矽酸鹽、聚乙烯醇系樹脂等之 凝 聚 物 微 分 散 結 果 藉由上述阻氣層內光散射使散射體之分 -4- 散 1229036 五、發明說明（3) 狀態調整在特定範圍內，可極爲顯著地提高阻氣性，遂而 完成本發明。 因此，本發明提供一種阻氣性薄膜，其係爲含有由熱塑 性樹脂薄膜所成的基材層與由烷氧化矽之水解物、層狀矽 酸鹽和聚乙烯醇系樹脂所成的阻氣層之積層體，其中阻氣 層藉由光散射測定的散射體之回轉半徑（Rg)爲2.4μΐΏ以下 ，且在該阻氣層中所存在的層狀矽酸鹽之層間存在有烷氧 化矽及/或其水解物。 本發明另提供一種藉由在上述阻氣性薄膜之阻氣層之基 材層之積層面及反面上積層由低熔點熱塑性樹脂所成密封 層，即使在熱水中沸騰後仍具有以往所沒有的極爲優異阻 氣性之薄膜。 此外，於本發明中阻氣層中藉由光散射測定的散射體之 回轉半徑（Rg)係爲表示阻氣層中不均勻構造（光學不均性） 的指標，爲藉由Vv散射強度之幾尼葉標繪圖所求得的値 。詳言之，以使光散射的粒子（散射體）之回轉半徑爲Rg 時，散射強度I ( Q )在小角範圍（散射光譜Q在0附近）內以 下式表示。 I (q) = I (q = 0)exp (~Rg2q 2/3) . * - · 其中，對全部形狀之散射體而言成立，且藉由小角側之 幾尼葉標繪圖（lnlU) vs. Q2)之坡度、可求得散射體之 回轉半徑（Rg)(A. Guinier and G. Fournet，“Small-Angle Scattering of X-ray’’，J . Wiley & Sons，Inc· 1229036 五、發明說明（4) ，N.Y. ( 1 995，pp. 102))。 本發明阻氣性薄膜之Vv散射強度，與基材層之熱塑性 薄膜或視其所需設置的增黏塗層、密封層等之Vv強度相 比大很多。 另外，基材層之Vv散射係觀察強的方位角相關性（基材 之各向異性），惟本發明積層有阻氣層之阻氣性薄膜的Vv 散射與等方向之方位角沒有相關性。由上述可知，本發明 阻氣性薄膜之Vv散射可無視於基材層之散射、僅見來自 阻氣層之散射。 此外，阻氣層沒有光學各向異性、Vv散射可作爲僅來自 阻氣層之光學密度差的散射處理。因此，由含有基材層之 阻氣性薄膜的光散射測定，可評估阻氣層之不均勻性。 上述Rg係爲表示阻氣層中固體不均勻性的指標，Rg値 愈小時表示阻氣層中固體爲均勻的分散構造。 發明之實施形熊 本發明之阻氣性薄膜包含兩種形態。第一形態係爲藉 由積層由熱塑性樹脂薄膜所成基材層與由烷氧化矽之水 解物、層狀矽酸鹽及聚乙烯醇系樹脂所成阻氣層之積層 體，第二形態係爲於第一形態中在與積層阻氣層之基材 層的正面和反面上設置密封層之積層體。 本發明之阻氣性薄膜只要是具有上述層構成者即可、沒 有特別的限制，在最外層與層間亦可設置其他層。具體例 如作爲層間所設層之下述增黏塗層、黏合層等，以及例如 1229036 五、 發明說明 (5) 作 爲最 外 層 或層間設置的層之印刷層。 於本 發 明 中藉由上述阻氣層中 具有固體分散程度之光 散 射 測定 的 Rg爲2.4μιη以下、較 佳者爲2.3μπι以下係極 爲 重 要。 換言 之 Rg大於2.4μηι時， 以層狀矽酸鹽爲始的散 射 am 體 之分 散 狀 態不充分，不易製得 具有高阻氧性之阻氣性 薄 膜 。而 且 9 該散射體之分散狀態 不僅與藉由使層狀矽酸 鹽 微 分散 達 成的値、且與作爲其他 散射體所測定的聚乙烯 醇 系 樹脂 % 院 氧化矽之水解物等分 散狀態有關。 於本 發 明 之阻氣性薄膜中具有 藉由光散射測定的Rg 之 散射體 構 造 雖不爲明確，惟在層 狀矽酸鹽之配向散亂範 圍 > Rg係與其大小有關。阻氣層之微細構造藉由ΤΕΜ(透 過 電 子顯 微 鏡 )或下述FE-TEM(電界放射型透過電子顯微鏡） 觀 察時 可知層狀矽酸鹽在阻氣 層內部良好地平行配向 於 薄 膜面之 構 造，可確認在數μηι級 數週期下存在有層狀矽 酸 鹽 之配 向 散 亂（彎曲）的範圍，該 範圍爲光學不均勻構造 使 光 散射 〇 而 且，該範圍之大小可推測爲以光散射測定的 Rg 相 關。 換 言 之，Rg大時，層狀矽 酸鹽之配向散亂範圍大 其配向 散 亂 大、藉由層狀矽酸鹽 會產生阻氣性要件之迷 路 效 果、 或阻 氣層之均質性。反之 ，Rg小時，層狀矽酸鹽 之 配 向散 亂 範 圍小、且由於該配向 之散亂小、迷路效果大 阻 氣層 均 質 、阻氣性優異。特別 是本發明之阻氣性薄膜 9 由 於Rg : 爲 2.4μπι以下之極小値 -7- 、故可發揮優異的阻氣 性 1229036 五、發明說明（6) 〇 另外，本發明之阻氣性薄膜係於由上述烷氧化矽之水解 物、層狀矽酸鹽及聚乙烯醇系樹脂所成阻氣層中，在至少 部分上述層狀矽酸鹽之層間存在有烷氧化矽及/或其水解 物。本發明之阻氣性薄膜藉由具有該構造，伴隨上述散射 體之分散狀態、可發揮優異的阻氣性。 換言之，正確理由不爲明確，惟於上述阻氣層中藉由在 上述層狀矽酸鹽層間存在有烷氧化矽及/或其水解物，可 得層狀矽酸鹽之層間距離變大、且層狀矽酸鹽之飽和相的 比例小或聚乙烯醇系樹脂之飽和相的比例小等效果，結果 形成以2.4μηι以下之回轉半徑（Rg)表示的特定構造，可發 揮習知沒有的極高阻氣性。 於上述阻氣層中在層狀矽酸鹽之層間存在有烷氧化矽及 /或其水解物，係自阻氣層之截面使用超薄切薄片機切出 超薄切片，藉由具有STEM(掃描透過電子顯微鏡）機能之 FE-TEM(電界放射型透過電子顯微鏡）觀察、確認該層間之 存在，且藉由在上述FE-TEM所裝置的EDS(能量分散型X 線分析裝置）元素分析、可確認表示阻氣層中層狀矽酸鹽 起因之元素分散濃度、與矽分散濃度之圖樣（元素圖樣）。 1L式簡單說明： 第1圖係表示有關實施例1所得阻氣性薄膜之阻氣層構 造的藉由FE-TEM分析結果圖。 第2圖係表示有關本發明實施例1所得阻氣性薄膜之阻 1229036 五、發明說明（7) 氣層的層狀矽酸鹽構造藉由EDS分析結果圖。 藉由第1圖可確認層狀矽酸鹽以1〜2nm厚度微分散、 在薄膜面上可觀察到大約平行配列的構造，可確認存在於 層間。此時，其層間可知約爲10〜20nm。於本發明中存在 阻氣層中之層狀矽酸鹽層間視其種類不同而不同，一般以 5〜lOOnm較佳。 另外，第2(a)圖係爲藉由STEM之暗視野像，元素密度 高的部分較爲明亮（第1圖之FE-TEM像係明暗反轉）。第 2(b)及2(c)圖係表示銘及砍之元素繪圖結果及第2(a)圖 係表示以白線圍住的範圍元素繪圖結果。第2(b)圖之明亮 範圍係爲層狀矽酸鹽固有的含有元素之鋁分佈圖樣，與層 狀矽酸之分佈一致。此外，第2(c)圖係表示矽之分佈圖樣 ，可知在層狀矽酸鹽之層間（沒有觀察到鋁之範圍）中可強 烈地觀察到矽，因此可確認在層狀矽酸鹽之層間存在有烷 氧化矽及/或其水解物。 於本發明中，阻氣層間存在的水解物之比例無法由上述 分析特定，本發明之阻氣性薄膜以其製造條件推定幾乎所 有的烷氧化矽爲水解物者。 本發明之阻氣性薄膜藉由上述之構成，可製得以溫度 23°C、基材層側之濕度90%RH、密封層側之濕度90%RH中 測定的透氧度（Q ; m 1 / m2 · d a y · a t m )滿足下述式（1 )者，該 形態更佳。 Q = 2 . 5/(^/90 + (¾) (1) 1229036 五、發明說明（8) (其中，α係表示阻氣層之厚度（) ’ γ係表τκ阻氣性薄 膜之厚度（μπ〇) 而且，阻氣層表面設有密封層之本發明阻氣性薄膜在溫 度90°C之熱水中放置30分鐘後，可製得在溫度23°C、基 材層側之濕度90%RH、密封層側之濕度90%RH中測定的透 氧度（Q， ； inl/m2*day*atn〇滿足下述式（2)者，該形態更 佳。 Q’ S 1 0 ◦/ (γ/9 0 + a) (2) (其中，α係表示阻氣層之厚度（μπι)，γ係表示阻氣性薄 膜之厚度（μπι)) 於上述式（1 )、式（2 )中，阻氣層之厚度α係指由上述烷 氧化矽之水解物、層狀矽酸鹽及聚乙烯醇系樹脂、以及視 其所需添加的聚環氧乙烷、其他任意添加劑所成層之厚度 〇 該阻氣層之厚度沒有特別的限制，就考慮具有阻氣性、 防止處理時產生破裂情形時，一般爲〇 . 1〜1 〇μιη、較佳者 爲 0 · 5 〜3 μπι 0 另外，阻氣性薄膜之厚度係指積層上述阻氣層、基材層 及視其所需設置的密封層、增黏塗層等其他層之狀態下的 總厚度。 該阻氣性薄膜之厚度沒有特別的限制，一般爲5〜 200μπι、較佳者爲10〜l〇〇pm。 然後，上述式（1)、式（2)係爲以特定阻氣層之厚度與阻 -10- 1229036 五、發明說明（9) 氣性薄膜之厚度爲基準，使藉由本發明達成的透氧度範圍 各視其厚度變化而定修正係數之式。換言之，上述式中阻 氣層之厚度直接影響所得阻氣性薄膜之透氧度，另外含有 基材層、密封層、增黏塗層、黏合層等層之阻氣性薄膜的 影響大約以上述比例具有效果。 因此，具有由烷氧化矽之水解物、層狀矽酸鹽及聚乙烯 醇系樹脂所成阻氣層之習知阻氣性薄膜，阻氣層之厚度爲 0.4μπι、阻氣性薄膜之厚度爲54.4μιη時爲3.2ml/m2.day • a t m 0 該値係表示大於藉由本發明上述式求得阻氣性薄膜之透 氧度上限値的値，故可知本發明之阻氣薄膜具有習知相同 成分之阻氣性薄膜無法達成的極高阻氣性者。 而且，上述阻氣性薄膜之透氧度以HS K7126 B法爲基 準測定的値。 另外，使阻氣性薄膜在溫度90°C之熱水中放置30分鐘 後透氧度之測定係藉由於恆溫槽中溫度調整爲90°C之熱水 中使該阻氣性薄膜完全浸漬，經過30分鐘後取出、且擦 拭該薄膜表面之水後，實施上述透氧度測定的方法。 另外，本發明之阻氣性薄膜藉由小角X線散射測定垂直 於阻氣層中薄膜面之區域間距離dND爲6 .8nm以下，由於 使高濕度下極爲優異的阻氣性在另設有密封層時於熱水中 沸騰處理後保持更爲優異的阻氣性較佳。更佳者爲6 . 3nm 以下、最佳者爲5 . 8nm以下。此外，藉由小角X線散射測 -11- 1229036 五、發明說明（1〇) 定的阻氣層中薄膜面內方向之區域間距離dIP與上述dND之 比（dIP/dND)以1.0以上較佳、更佳者爲1.1以上。區域間 距離dND爲6.8nm以下、且dIP/dND爲1 .0以上時，由於使 設有密封層時在熱水中沸騰處理後仍可保持極爲優異的阻 氣性、故較佳。 而且，於本發明中藉由小角X線散射測定的阻氣層中區 域間距離dIP及dND係爲表示阻氣層之微細周期構造（密度 搖晃）的指標，表示小角X線散射之散射波峰位置（散射角 2Θ)可藉由布喇格之式（2d s ίηθ = λ，λ係爲X線之波長）求 得（L.H_ Sperling， “Polymeric Multicomponent Materials”， J. Wiley & Sons， Inc. ， Ν·Υ· (1997)， pp . 326 ) 0 此處，阻氣層中薄膜面內方向之區域間距離dIP可藉由 使X線垂直入射於薄膜面（through入射）所得透過法之小 角X線散射求得。而且，垂直於薄膜面之區域間距離dND 可藉由使X線自薄膜端面平行於薄膜面入射（edge入射）所 得透過法之小角X線散射求得。 此外，測定本發明阻氣性薄膜之小角X線散射縱截面圖 除自阻氣層散射外，包含自基材層之熱塑性樹脂薄膜散射 、中心束之邊緣、空氣散射、寄生散射等。此處，本發明 阻氣性薄膜使用的基材層薄膜、或具有與基材層同樣厚度 之相同材質的熱塑性樹脂薄膜之小角X線散射縱截面圖以 相同條件測定，且自本發明阻氣性薄膜之小角散射縱截面 •12- 1229036 五、發明說明（11) 圖拉出，可除去來自基材層熱塑性樹脂薄膜之散射、中心 束之邊緣、空氣散射、寄生散射等，求得僅來自阻氣層之 散射縱截面圖。自以該方法所得阻氣層之小角X線散射縱 截面圖的波峰位置求取區域間距離。 於本發明之阻氣性薄膜中藉由FE-TEM(電界放射型透過 電子顯微鏡）觀察阻氣層截面的結果，對層狀矽酸鹽之薄 膜厚度方向的層間約爲10〜20nm而言，由於藉由小角X 線散射求得的區域間距離小於1 〇nm、薄膜厚度方向、面內 方向亦爲相同程度之大小，故此處之阻氣層中主要爲烷氧 化矽水解物，區域間距離與烷氧化矽水解物之分散狀態或 分散粒徑有關。 換言之，正確理由不明，惟烷氧化矽水解物主要爲垂直 於薄膜面之微細緻密性，由於薄膜面內爲薄且平廣的構造 ，在高濕度下及設有密封層時熱水中沸騰後仍可發揮優異 的阻氣性。 於本發明阻氣性薄膜中基材層之材質只要是熱塑性樹脂 即可，沒有特別的限制，就使用於包裝用途時以具有透明 性者較佳。上述熱塑性樹脂例如乙烯單體、乙烯與丙烯、 1-丁烯、1-戊烯、1-己烯、4 -甲基-1-戊烯等1種或2種 以上α-烯烴之無規或嵌段共聚物、乙烯與醋酸乙烯酯、丙 烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯之1種 或2種以上無規或嵌段共聚物、丙烯單體、丙烯與丙烯以 外之1-丁烯、1-戊烯、卜己烯、4 -甲基-1-戊烯等1種或 -13- 1229036 五、發明說明（彳2) 2種以上α -烯烴之無規或嵌段共聚物、卜丁烯單體、離子 聚合物樹脂、以及此等聚合物之混合物等聚烯烴系樹脂； 石油樹脂、萜烯樹脂等之烴系樹脂；聚對酞酸乙二酯、聚 對酞酸丁二酯、聚萘二甲酸乙二酯等之聚酯系樹脂；耐龍 6、耐龍66、耐龍11、耐龍12、耐龍610、耐龍6/66、耐 龍6 / 6 1 0、耐龍MXD等聚醯胺系樹脂；聚甲基丙烯酸甲酯 等之丙烯酸系樹脂；聚苯乙烯、苯乙烯-丙烯腈共聚物、 苯乙烯-丙烯腈-丁二烯共聚物、聚丙烯腈等苯乙烯、丙烯 腈系樹脂；聚乙烯醇、乙烯-乙烯醇共聚物等聚乙烯醇系 樹脂；聚碳酸酯樹脂；聚縮酮樹脂；聚環氧乙烷樹脂；聚 楓樹脂；聚醯亞胺樹脂；聚醯胺醯亞胺樹脂等。此等可1 種或2種以上混合使用。 其中，於工業實施中以透明性、機械強度、包裝適性等 優異的聚烯烴系樹脂、聚酯系樹脂、聚醯胺系樹脂、苯乙 烯、丙烯腈系樹脂、聚乙烯醇系樹脂、聚碳酸酯系樹脂等 較佳，更佳者爲聚烯烴系樹脂、聚酯系樹脂、聚醯胺系樹 脂。 由此等較佳的熱塑性樹脂所成的基材層，表示其阻氧性 在濕度90%RH中測定的透氧度爲10ml/m2*dayatm以上 〇 上述熱塑性樹脂薄膜之製法可使用習知方法，沒有特別 的限制。具體而言可採用溶液鑄造法、T塑模法、管式法 、壓延法等習知方法。而且，就考慮機械物性等而言，上 -14- 1229036 五、發明說明（1 3 ) 述熱塑性樹脂薄膜以實施延伸處理較佳。延伸方法可採用 習知方法、沒有特別的限制，例如輥一軸延伸、壓延、逐 次二軸延伸、同時二軸延伸、管式延伸等。於此等延伸方 法中，就考慮厚度精度或機械物性等而言以逐次二軸延伸 、同時二軸延伸較佳。 另外，熱塑性樹脂薄膜之厚度沒有特別的限制，就考慮 所使用用途等予以適當選擇，在1〜200μπι之範圍中適當 選擇。其中，就延伸加工性、阻氣性、製袋加工性等而言 ，以5〜ΙΟΟμπι較佳、更佳者爲10〜50μηι。 此外，於上述熱塑性樹脂薄膜中，在不會損害本發明效 果下視其所需可配合抗靜電劑、防曇劑、防粘連劑、熱安 定劑、抗氧化劑、光安定劑、結晶核劑、平滑劑、紫外線 吸收劑、賦予平滑性及賦予防粘連性爲目的之界面活性劑 等習知添加劑。 由上述熱塑性樹脂薄膜所成的基材層，就考慮包裝用途 ，特別是作爲阻氣性薄膜使用時，以透明較佳。具體而言 霧度以15%以下較佳、更佳者爲10%以下。 於本發明之阻氣性薄膜中，阻氣層之一構成成分的聚乙 烯醇系樹脂可使用乙烯醇系聚合物及其衍生物。例如皂化 度75%以上之聚乙烯醇、全部羥基之40莫耳％以下經縮醛 化的聚乙烯醇、醇可溶改性聚乙烯醇、乙烯醇單位爲60 莫耳％以上乙烯-乙烯醇共聚物等之共聚合聚乙烯醇等較佳 。其中，皂化度75莫耳％以上之聚乙烯醇由於所得薄膜之 -15- 1229036 五、發明說明（14) 透明性或高濕度下之阻氣性良好，故更佳。 而且，上述聚乙烯醇系樹脂之聚合度，就考慮加工性時 ，以300〜5000較佳、更佳者爲500〜3500。 於本發明之阻氣性薄膜中阻氣層之一構成成分的烷氧化 矽之水解物中，包含烷氧化矽之部分或全部烷氧基藉由水 解之生成物、烷氧化矽之聚縮合物、該聚縮合物之部分或 全部烷氧基藉由水解之生成物、以及此等之各種混合物。 上述烷氧化矽只要是可形成水解物即可，沒有特別的限 制。具體而言例如可形成四甲氧基矽烷、四乙氧基矽烷、 甲基三甲氧基矽烷、乙基三甲氧基矽烷、丙基三甲氧基矽 烷、異丙基三甲氧基矽烷、丁基三甲氧基矽烷、環氧丙氧 基甲基三甲氧基矽烷、2 -環氧丙氧基乙基三甲氧基矽烷、 3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三丁 氧基矽烷、（3 ,4 -環氧基環己基）甲基三丙氧基矽烷、2-(3, 4 -環氧基環己基）乙基三甲氧基矽烷、3-(3,4 -環氧基 環己基）丙基三甲氧基矽烷、胺基甲基三乙氧基矽烷、2-胺基乙基三甲氧基矽烷、1 -胺基乙基三甲氧基矽烷、3 -胺 基丙基三甲氧基矽烷、3 -胺基丙基三乙氧基矽烷、N -胺基 甲基胺基甲基三甲氧基矽院、N-胺基甲基-3-胺基丙基三 甲氧基矽烷、Ν·(2_胺基乙基）-3-胺基丙基甲基二甲氧基 矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、N-β-(Ν-乙烯基苯甲基胺基乙基）-Ύ-胺基丙基三甲氧基矽烷 等水解物之烷氧化矽。 -16- 1229036 五、發明說明（15) 烷氧化矽聚縮合物及該縮合物中部分或全部烷氧基藉由 水解之生成物，包含上述烷氧化矽藉由水解，及同時引起 的脫水及/或脫醇之聚縮合反應所形成者。 於上述阻氣層中烷氧化矽之水解物，來自烷氧化矽之矽 對100重量份聚乙烯醇系樹脂而言以Si02換算存在有90 〜5 00重量份，較佳者爲100〜3 50重量份，更佳者爲1〇〇 〜250重量份，由於可發揮優異的阻氣性，故爲企求。 本發明阻氣性薄膜中阻氣層之一構成成分的層狀矽酸鹽 可使用習知者，沒有特別的限制。例如蒙脫石、拜來石、 綠脫石、皂石、鋰蒙脫石、富鎂蒙脫石、有機彭潤石、高 嶺土、地開石、埃洛石、纖蛇紋石、葉蛇紋石、深黃鈾礦 、鎳綠泥石、腎矽錳礦、鎂綠泥石、水砷鋁銅礦、水銻錳 礦、燧石、綠泥鎂鋁榴石、綠椎石、火硫銻銀礦、滑石、 鈣鋁黃長石、矽鋅礦、紅簾石、鐵滑石、雲母、白雲母、 多砂白雲石、伊利石、絹雲母、海綠石、綠磷石、霓輝正 長石、鈉雲母、金雲母、黑雲母、綠泥石、蛭石等。此等 大多爲天然礦物，惟亦可以藉由化學合成法製造者。 其中，使用蒙脫石所得的阻氣性薄膜具有優異阻氣性， 故較佳。 於上述阻氣層中層狀矽.酸鹽對100重量份聚乙烯醇系樹 脂而言爲10〜150重量份、較佳者爲20〜100重量份，由 於可發揮優異的阻氣性、故爲企求。 另外，上述阻氣層中對來自烷氧化矽之矽量（Si 02換算） -17- 1229036 五、發明說明（16) 而言層狀矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽 量）爲0.01〜1，較佳者爲0.1〜1，由於可發揮優異的阻 氣性，故較佳。 此外，於本發明之阻氣性薄膜中，阻氣層之成分只要是 由烷氧化矽之水解物、層狀矽酸鹽及聚乙烯醇系樹脂所成 者即可，沒有特別的限制，惟爲形成阻氣層時產生破裂、 且防止使用時薄膜變形時阻氣層產生破裂的情形時，除上 述成分外可配合聚環氧乙烷較佳。該聚環氧乙烷係平均分 子量愈高者、其效果愈佳，以平均分子量爲10萬以上較 佳、更佳者平均分子量爲50萬以上、最佳者平均分子量 爲20 0萬以上。 而且，該聚環氧乙烷之分子鏈末端可以爲羥基或經化學 修飾者，沒有特別的限制，通常以兩末端爲羥基者較佳。 上述聚環氧乙烷對100重量份聚乙烯醇系樹脂而言配合 0.1〜5重量份，較佳者爲0.5〜2重量份。 此外，構成本發明阻氣性薄膜之阻氣層的成分，在不會 損害本發明效果之範圍內可配合其他成分。 例如胺甲酸酯系交聯劑、異氰酸酯系交聯劑、蜜胺系交 聯劑、環氧系交聯劑等之交聯劑、矽烷系偶合劑、鈦系偶 合劑等之偶合劑、水性異氰酸酯、水性聚胺甲酸酯樹脂、 聚伸乙基亞胺、水性環氧酯等之水溶性增黏被覆劑、鋁系 有機化合物、锆系有機化合物等。 本發明具有極高阻氣性之阻氣性薄膜可藉由由烷氧化矽 -18- 1229036 五、發明說明（17) 之水解物、層狀矽酸鹽及乙烯醇系樹脂所成阻氣層藉由下 述方法形成於基材層上製得。 本發明之阻氣性薄膜，係使在pH値調整爲1〜5、較佳 者爲2〜4之聚乙烯醇系樹脂的水性溶液中分散有層狀矽 酸鹽存在下、使烷氧化矽水解所得的水性溶液所成的增黏 被覆劑被覆於基材薄膜上、予以乾燥製得。 於上述阻氣性薄膜之製法中詳述有關阻氣性被覆劑之適 當調製方法時，首先使預先分散有層狀矽酸鹽之聚乙烯醇 系樹脂之水性溶液藉由習知微分散裝置、例如超音波分散 、珠磨、球磨、輥磨、均混器、超混器、分散混合器、貫 通型高壓分散裝置、衝突型高壓分散裝置、多孔型高壓分 散裝置、擲球型高壓分散裝置、（衝突+貫通）型高壓分散 裝置、超高壓均混器等予以微分散。 於上述習知之微分散裝置中尤以均混器、超混器、分散 混合器、貫通型高壓分散裝置、衝突型高壓分散裝置、多 孔型高壓分散裝置、攤球型高壓分散裝置、（衝突+貫通） 型高壓分散裝置、超高壓均混器，可使層狀矽酸鹽形成良 好的分散狀態、且所得阻氣性薄膜之阻氣層中上述Rg調 整爲2.4μπι以下，故更佳。 另外，使用蒙脫石作爲層狀矽酸鹽時，所得阻氣性薄膜 之阻氣層中垂直於薄膜面之區域間距離dND以調整爲 6.8nm以下較佳。 爲調整上述水性溶液之溶劑可使用水/低元醇混合溶劑 -19- 1229036 五、發明說明（18) 。上述低元醇係爲碳數1〜3之醇，具體例如甲醇、乙醇 、正丙醇、或異丙醇。 而且，上述水/醇之混合比例在以重量比爲99/1〜20/80 之範圍內適當選擇。 上述水性溶液中聚乙烯醇系樹脂之濃度爲〇 · 1〜20%下可 適當地決定聚乙烯醇系樹脂/烷氧化矽之混合量，較佳者 對溶劑而言聚乙烯醇系樹脂之濃度採用在1〜1 0%之範圍內 聚乙烯醇系樹脂/烷氧化矽之混合量。 將上述分散有層狀矽酸鹽之聚乙烯醇系樹脂的水性溶液 之pH値調整於上述範圍的方法，由於使層狀矽酸鹽中之 交換性離子質子化的方法使烷氧化矽及/或其水解物在層 狀矽酸鹽之層間以高濃度存在、可充分廣佈於層狀矽酸鹽 之層間係極爲有效，適合本發明使用。該質子化使用藉由 陽離子交換樹脂或離子交換法予以離子交換。 例如，使用陽離子交換樹脂之質子化如使含有層狀矽酸 鹽之溶液與聚苯乙烯•磺酸型強酸性離子交換樹脂等之陽 離子交換樹脂交換形態。 而且，使用離子交換膜之質子化例如在陰極與陽極間使 陽離子交換膜及鬆配構造之較佳陰離子交換膜交互配列、 構成形成存在陰極之陰極室、存在陽極之陽極室、及於其 間形成數個隔室之電氣透析槽、且在陽極側具有陰離子交 換膜、在陰極側具有陽離子交換膜之室內使含有層狀矽酸 鹽之溶液供應給與該室鄰接的室內、進行電氣透析的方法 -20- 1229036 五、發明說明（19) =在陰極與陽極間使陽離子交換膜及兩極膜交互配列、構 成形成有存在陰極之陰極室、存在陽極之陽極室、及於其 間形成數個隔室之電氣透析槽，且在陽極側具有兩極膜、 在陰極側具有陽離子交換膜之室內使含有層狀矽酸鹽之溶 液以稀薄鹼水溶液爲較佳的電解質溶液供應給與該室鄰接 的室中、進行電氣透析的方法等。 其次’在pH値調整於上述範圍，使層狀矽酸鹽分散之 聚乙烯醇系樹脂之水性溶液中添加烷氧化矽、且在該分散 的層狀矽酸鹽存在下進行水解。 在使該層狀矽酸鹽分散含有的聚乙烯醇系樹脂之水性溶 液中烷氧化矽之水解係在上述水性溶液之pH値調整爲1〜 5、較佳者爲2〜4、且在水解觸媒存在下進行。層狀矽酸 鹽中之交換性離子藉由陽離子交換樹脂或離子交換膜予以 離子交換、質子化、且調整於上述pH之範圍時，該質子 化的層狀矽酸鹽本身可達成作爲水解觸媒之效果，例如於 烷氧化矽水解前使陽離子交換樹脂藉由過濾等方法除去至 系外時，仍可使烷氧化矽水解。 上述水解觸媒例如鹽酸、硝酸、硫酸、磷酸等之無機酸 、有機磷酸、甲酸、醋酸、醋酸酐、氯醋酸、丙酸、丁酸 、戊酸、乙二酸、丙二酸、琥珀酸、戊二酸、己二酸、乙 醇酸、乳酸、蘋果酸、酒石酸、檸檬酸、馬來酸、富馬酸 、衣康酸、苯甲酸、酞酸、異酞酸、對酞酸、水楊酸、肉 桂酸、尿酸、巴比土酸、對-甲苯磺酸等之有機酸、酸性 -21 - 1229036 五、發明說明（2〇 ) 陽離子交換樹脂。 其中，就考慮容易調整pH値或簡單觸媒除去處理或得 到阻氣層之透明性等而言，以酸性陽離子交換樹脂爲宜。 於上述水解中時間係爲決定水解程度因素之一，惟一般 而言調整爲上述pH値後、在常溫下爲1〜24小時、較佳 者爲2〜1 8小時、更佳者爲2〜1 2小時。 而且，於本發明之阻氣性薄膜中視其所需在阻氣層中所 添加的聚環氧乙烷亦可以在上述製造工程之任何處添加。 例如，使層狀矽酸鹽分散後，於烷氧化矽水解前添加、或 使烷氧化矽水解後添加。 上述製法中各成分之比例係以上述阻氣層所示比例決定 〇 於上述製法中就考慮阻氣性被覆劑之安定性、所得阻氣 層之著色、高濕度下具有良好阻氣性等而言，可在使烷氧 化矽水解前或後除去質子化的層狀矽酸鹽、將調整pH値 所使用的水解觸媒除去至系外。 於本發明中在烷氧化矽水解前或後除去質子化的層狀矽 酸鹽、將水解觸媒除去至系外的方法，沒有特別的限制。 例如爲離子交換樹脂時可藉由過濾等物理方法予以除去 。而且，使用無機酸或有機酸時，以採用可使來自該無機 酸或該有機酸之陰離子成分藉由羥基離子化的鹼性陰離子 交換樹脂予以離子交換成羥基離子，且藉由過濾除去至系 外的方法較佳。 -22- 1229036 五、發明說明（21) 於本發明中烷氧化矽之水解以進行至相分離的液相成均 勻相較佳，此時可以爲部分水解狀態、完全水解的狀態、 或烷氧化矽間之聚縮合反應狀態。 上述阻氣劑最終pH値調整爲1〜5之範圍內，就可防止 阻氣劑之凝膠化、防止形成阻氣層後之破裂、以及高濕度 下發揮良好的阻氣性而言較佳。 本發明阻氣性薄膜之製法中，阻氣層與基材層之積層可 藉由將上述阻氣性被覆劑被覆於基材層、予以乾燥的方法 進行。 有關將上述阻氣性被覆劑被覆於基材層之時間，可在進 行烷氧化矽之水解、且相分離的液相成均一相時予以被覆 。而且，就考慮所得阻氣層產生破裂及降低阻氣性而言， 以引起上述阻氣層變質爲止予以被覆較佳。 於本發明中上述阻氣性被覆劑之被覆方法，沒有特別的 限制，以可在高速薄膜被覆的溶液或溶劑分散被覆法較佳 。此等被覆法之具體例如輥被覆法、可逆輥被覆法、照相 凹版被覆法、噴霧被覆法、接觸被覆法、塑模被覆法、條 狀被覆法、棒被覆法、刮刀室倂用照相凹版被覆法、簾幕 被覆法等，使阻氣性被覆劑被覆熱塑性樹脂薄膜表面上之 方法。 於本發明中使基材層上之阻氣性被覆劑乾燥的方法可使 用習知的乾燥方法，沒有特別的限制。具體而言例如1種 或2種以上熱輥接觸法、熱媒（空氣、油等）接觸法、紅外 -23 - 1229036 五、發明說明（22) 線加熱法、微波加熱法等。於此等之中就考慮薄膜外觀等 之處理或乾燥效果等而言，以加熱空氣接觸法或紅外線加 熱法較佳。 上述阻氣性被覆劑之乾燥條件沒有特別的限制，就具有 考慮阻氣性或乾燥效率等而言，特別以採用60°C以上〜小 於基材之熔點的溫度範圍內較佳。另外，上述乾燥溫度以 80°C以上更佳、最佳者爲9(TC以上。此外，比基材層之熔 點低10°C之溫度以下較佳、更佳者爲低15°C以下之溫度。 上述乾燥時間就考慮阻氣性或乾燥效率等而言，以5秒 〜10分鐘較佳、更佳者爲10秒〜5分鐘。 上述乾燥前後視其所需可施予紫外線、X線、電子線等 之高能量照射。而且，就考慮更爲提高高濕度下之阻氣性 而言，在阻氣層上直接施予電暈放電處理或火焰電漿處理 等之表面處理。 於本發明中在基材層上被覆上述阻氣性被覆劑、且在上 述溫度下乾燥形成阻氣層後，另施予蝕刻處理的方法，由 於可得具有更優異阻氣性之阻氣性薄膜，故較佳。 上述蝕刻處理對發揮提高所得阻氣性薄膜之阻氣性、特 別是大於90%RH之高濕度下的阻氣性、以及在熱水中沸騰 處理後優異的阻氣性極具效果。蝕刻之條件可適當地決定 ，沒有特別的限制，通常在藉由蝕刻之基材層不會產生皺 摺、鬆弛等缺點之範圍內決定。 於本發明中在基材層上形成有上述阻氣層所成薄膜上在 -24- 1229036 五、發明說明（23) 溫度30〜80°C、相對濕度30%RH〜10 0%RH之氣氛下施予蝕 刻處理。在相對濕度爲30%RH〜100%RH之氣氛下進行鈾刻 處理，由於在熱水中沸騰處理後具有優異的阻氣性效果， 故較佳。相對濕度小於30MH時，蝕刻處理所得的阻氣性 薄膜在阻氣層上積層密封層之形態下會使沸騰處理後之阻 氣性降低。 本效果藉由在相對濕度爲30%RH以上之氣氛下進行蝕刻 處理，推斷具有使本發明所使用的阻氣性薄膜之阻氣層內 殘留有烷氧化矽之烷氧基水解或伴隨產生的聚縮合反應或 進行與聚乙烯醇系樹脂之氫鍵等、且使被覆層中自由體積 之縮小效果。 蝕刻處理時之溫度爲30〜80°C之範圍，若小於30°C時、 蝕刻所需時間變長。而且，若大於80°C時、因基材層本身 變形或吸濕致使印刷、製袋等之2次加工適性降低。 具體的蝕刻處理條件由於在上述蝕刻處理之條件範圍， 可在不會因蝕刻產生基材層之皺摺、鬆弛等缺點之範圍內 決定即可，就考慮即使在高濕度下具有極爲優異的阻氣性 、且於沸騰後仍具有優異的阻氣性時，以在溫度30〜80°C 、相對濕度30%RH〜100%RH之氣氛下進行蝕刻處理較佳， 以在溫度40〜80°C、相對濕度40%RH〜90%RH之氣氛下進 行蝕刻處理更佳。例如熱塑性樹脂薄膜爲二軸延伸聚丙烯 薄膜時選自於溫度30〜5(TC、相對濕度30%RH〜100%RH之 範圍，以在溫度40〜50°C、相對濕度40%RH〜90%RH之氣 -25- 1229036 五、發明說明（24) 氛下進行蝕刻處理更佳。溫度及相對濕度在不會使基材層 之皺摺、鬆弛等缺點的條件範圍內即可，設定較高時由於 可減低蝕刻所需日數，故較佳。 蝕刻所需日數可適當決定，就考慮生產性等而言例如設 .定爲1日〜1 0日範圍之上述溫度及相對濕度。 藉由上述條件進行蝕刻處理之方法，沒有特別的限制。 適當的方法例如有使在上述基材層上被覆阻氣性被覆劑、 乾燥的薄膜在設定溫度、相對濕度之恆溫恆濕室等蝕刻處 理的方法。另外，使薄膜捲成輥狀時，係使用使捲取張力 降低、阻氣性薄膜間設有空隙下、在恆溫恆濕室中蝕刻處 理的方法、或捲去取成輥狀時將水蒸氣噴霧於阻氣層、進 行蝕刻處理的方法等。 藉由進行上述蝕刻處理，可製得在溫度23°C、基材層側 之濕度90%RH、密封層側之濕度90%RH中測定的透氧度 (Q; ml/m2.day*atni)可滿足下述式（3)之阻氣性薄膜，於 本發明中以該形態較佳。 Q $ 2· 0/ (γ/g Ο + α) (3) (其中，α係表示阻氣層之厚度（μπι)、γ係表示阻氣性薄 膜之厚度（μπι))。 另外，於上述阻氣性薄膜中在與積層阻氣層之基材層的 積層面及反面上含有較構成該基材層之熱塑性樹脂的熔點 低之熱塑性樹脂所成密封層的積層體，可製得在溫度90°C 之熱水中放置30分鐘後、在溫度23°C、基材層側之濕度 -26- 1229036 五、發明說明（25) 90%RH、密封層側之濕度90%RH中測定的透氧度（Q，； ml/m2 • d a y · a t m )可滿足下述式（4 )之阻氣性薄膜，於本發明中 以該形態最佳。 Q’ S 6 0/ (γ/g Ο + α) (4) (其中，α係表示阻氣層之厚度（μπι)、γ係表示阻氣性薄 膜之厚度（μιη))。 於本發明中，爲更爲提高基材層與阻氣層之黏合性、 更爲提高所得阻氣性薄膜之阻氣性、耐久性時，以在積 層阻氣層之基材層表面上進行表面處理爲宜。 該表面處理可採用習知的表面處理方法，沒有特別的限 制。例如大氣中電暈放電處理、氮氣中電暈放電處理、碳 酸氣體中電暈放電處理、火焰電漿處理、紫外線處理、臭 氧處理、電子線處理、藉由激勵惰性氣體之電漿處理等表 面處理方法。而且，此等表面處理亦可以倂用處理。 另外，就考慮更爲提高上述基材層與阻氣層之黏合強度 而言，以採用於其間設置增黏塗層的方法較佳。 形成上述增黏塗層所使用的增黏被覆劑可採用習知者， 沒有特別的限制。例如異氰酸酯系、聚胺甲酸酯系、聚酯 系、聚伸乙基亞胺系、聚丁二烯系、聚烯烴系、鈦酸烷酯 系等增黏被覆劑。 此外，於本發明之阻氣性薄膜中，可以藉由上述方法所 得阻氣層之外層上以賦予加熱密封性、耐熱水性等爲目的 時可積層市售的聚烯烴、乙烯·醋酸乙烯酯共聚物、乙烯- -27- 1229036 五、發明說明（26) 甲基丙烯酸酯共聚物等之封閉層等。 發明之效果 藉由上述說明可知，本發明可提供一種於含有作爲阻 氣層之聚乙烯醇系樹脂與烷氧化矽水解物及層狀矽酸鹽 所成的阻氣性薄膜中，具有以往無法達成的極高阻氣性 的阻氣性薄膜。 而且，上述極爲優異的阻氣性係於在阻氣層上積層密封 層之形態中，使用聚乙烯醇系樹脂之阻氣層即使在熱水中 放置後可維持優異的阻氣性、更可達成達成與以往作爲阻 氣層所使用的偏二氯乙烯被覆薄膜之匹敵特性。 產業上之利用價値 因此，本發明阻氣性薄膜之用途對以作爲點心等之乾 燥食品爲始的好吃食品、生麵、帶餡的日本點心等中間 水分食品、佃煮物、醬菜、魚板、火腿、熱狗等之高水 物食品之阻氣性薄膜之廣泛用途而言極爲有用。 實施發明之最佳形態 於下述中以實施例及比較例說明本發明，惟本發明不 受此等實施例所限制。而且，藉由下述方法進行下述實 施例及比較例之薄膜物性。 (1)透氧度Q 以J IS K7126 B爲基準、使用透氧度測定裝置（Mo con公 司製；OX-TRAN100)測定。測定條件係溫度23t、基材層 側之濕度爲90%RH、阻氣層側之濕度爲90%RH。濕度係以 -28- 1229036 五、發明說明（27) 曰立計測器服務製精密濕度調整系統RH-3S型調整。 (2 )熱水處理後之透氧度Q 在積層有密封層之阻氣性薄膜上以阻氣層爲內面、且作 成封入有200ml水之15cmx 15cm大小的袋子。使該袋在 9 0 °C之熱水中浸漬30分鐘施予熱水處理。於熱水處理後 ，直接毀棄內容物、以水洗淨袋子後，在1 0分鐘以內使 阻氣性薄膜固定於透氧度測定裝置內。透氧度測定係以 JIS K71 26 B法基準、使用透氧度測定裝置（Mocon公司製 ;OX-TRAN1 00)測定。測定條件係氣體流量20ml/min、溫 度23°C、基材層測之濕度90%RH、密封層側之濕度90%RH 。濕度係以日立計測器服務製精密濕度調整系統 RH-3S 型調整。使熱水處理的阻氣性薄膜固定，於10分鐘後開 始測定透氧度，以測定開始後1小時後的透氧度評估作爲 熱水處理後之透氧度Q’。 (3)被覆性 使用小機械公司製試驗被覆器、被覆於熱塑性樹脂、並 予以乾燥、以形成阻氣層。 被覆方式：照相凹版被覆方式 乾燥方法：導輥半圓型熱風噴射噴嘴吹附式 (4 )藉由光散射之散射體回轉半徑Rg 使用大塚電子公司製光散射測定裝置DYNA-100、以下述 方法測定V v散射。 光源 ：5mW He-Ne雷射 -29- 1229036 五、發明說明（28) 角度範圍 ：1 .5〜30。 分檔器角度 ：〇·5° ND過濾器 ：〇· 1 檢測器 ：光子計算用光電子倍增管 此時，使薄膜之橫方向（垂直於機械方向之方向）與光散 射測定裝置之偏光子、檢測光子之偏光方向一致，使雷射 光以垂直薄膜方向入射、以進行散射強度測定。 散射體之回轉半徑Rg係使用附屬於同機器之軟體的幾 尼葉標繪圖計算、使幾尼葉標繪圖小角側之直線範圍藉由 最小二乘法類似、藉由其傾斜程度求取Rg。以任意15點 阻氣性薄膜求取、作爲此等之平均値。 (5) FE-TEM觀察及FDS分析 使薄膜以環氧樹脂包埋、硬化後，使用超切薄片機自阻 氣層截面採取厚度80nm之超薄切片。所得超薄切片藉由 具有STEM(掃描透過電子顯微鏡）機能之FE-TEM(電界放射 型透過電子顯微鏡 Phi 1ips Electron Optics公司製 Tecnai F20)觀察。而且，藉由在FE-TEM上裝置的EDS(能 量分散型X線分析裝置）、進行以C、0、A1、S i爲對象元 素之元素分散濃度及表示元素之分散濃度的元素標繪。 (6 )藉由小角X線散射之目標物間距離dIP及dND 在曰本電子公司製之X線散射裝置JDX- 3500中裝置小 角X線散射測定裝置，以下述方法測定透過法小角X線散 射0 -30 - 1229036 五、發明說明（29) 目標物 ··銅（Cu-Koc線） 管電壓·管電流：40kV-400mA 單色化 ：Ni過濾器 第 1 縫隙 ·· 0.30mmx 12mm 第 2 縫隙 ：0.20mmx 12mm 第3縫隙 ：使用 第 4 縫隙 ：0.20mmx20mm 第 5 係縫 ：0.15mmx20mm 檢測器 ：閃光儀 X線入射法 ：透過法（試料固定〇 ° ) 測定角度範圍 ：2 0 =0 . 3〜5 . 0 ° 分段角度 ：0.010° 計數時間 ：2 0秒 dIP之測定係使阻氣性薄膜之方向一致、切成15mmX 25 mm，重疊成厚度0.8〜1.0 mm (此處爲40張），使垂直於 薄膜面之X線入射（through入射），測定小角X線散射IIP 。而且，同樣地使基材層（或與基材層相同的厚度之同材 質）熱塑性樹脂薄膜重疊相同張數（此處爲40張），測定小 角X線散射IIP。。由自IIP引出IIP。所得阻氣層之through 入射散射標繪圖之波峰位置，求取範圍間距離。求取任意 5點之平均値。 另外，dND之測定係使阻氣性薄膜之方向一致、切成5mm X 15 mm，重疊成厚度4〜5mm (此處爲200張），以金屬製工 -31 - 1229036 五、發明說明（3〇) 具夾住、使薄膜平滑地固定，使薄膜面（薄膜試料之長邊） 與小角X線散射裝置之隙縫平行、使與薄膜面平行之X線 入射（edg e入射），測定小角X線散射IND。而且，同樣地 使基材層（或與基材層同等厚度之相同材質之）熱塑性樹脂 薄膜重疊相同張數（此處爲200張），測定小角X線散射 INDQ。由自IIP引出（基材薄膜厚度/阻氣性薄膜厚度）x IIP〇 所得阻氣層之edge入射散射標繪圖之波峰位置，求取範 圍間距離dND。求取任意5點之平均値。 實施例1 在70重量份水與30重量份乙醇之混合溶劑中，在70°C 下、使平均聚合度1700、鹼化率98%以上之聚乙烯醇以濃 度6.7重量％溶解，製得聚乙烯醇之6.7重量％溶液（簡稱 爲A液）。 在70重量份水與30重量份乙醇之混合溶劑中，加入濃 度3.3重量％作爲層狀矽酸鹽之蒙脫石（谷尼米耐（譯音）工 業（股）製、谷尼皮亞（譯音）G)，在60°C下攪拌且分散、製 得層狀矽酸鹽之3 · 3重量％分散溶液（簡稱爲B液）。 使以重量比1 : 1之比例混合上述A液與B液之溶液藉 由衝突型高壓分散裝置（（股）史奇羅機械製、HJP- 25030 ) 實施微分散化處理，製得含有聚乙烯醇3.3重量％及層狀 矽酸鹽1 · 7重量％之微分散溶液。在該微分散溶液中加入 珠子狀氫離子化的強酸性離子交換樹脂，將pH値調整爲 -32- 1229036 五、發明說明（31) 在該pH値經調整的微分散溶液中對100重量份聚乙烯 醇而言加入以來自烷氧化矽之矽量（S i 02換算）爲1 50重量 份四乙氧基矽烷，在室溫下約攪拌1 2小時以進行四乙氧 基矽烷之水解。然後，藉由過濾除去離子交換樹脂或塵埃 等異物，製得阻氣性被覆劑。所得阻氣性被覆劑之pH値 爲 3 · 8。 而且，該阻氣性被覆劑中之聚乙烯醇/層狀矽酸鹽之重 量份比爲1 00 / 50,對烷氧化矽之矽量（Si02換算）而言層狀 砂酸鹽的重量比（來自層狀砍酸鹽/院氧化砂之砂量）爲 0.33。 在厚度20 μηι經電暈放電處理的二軸延伸聚丙烯薄膜之 電暈放電處理面上以增黏被覆劑（東洋摩頓（譯音）製： AD33 5AE/CAT10L=10重量份/1.4重量份、在醋酸乙酯/甲 苯=1重量份/1重量份之混合溶劑中調整爲不揮發份6重 量％者）以增黏塗層之乾燥重量爲0.3g/m2下被覆，在 100 °C下熱風乾燥、製得被覆有增黏塗層之二軸延伸聚丙 .烯薄膜。 該被覆有增黏塗層之二軸延伸聚丙烯薄膜的增黏塗層上 被覆乾燥後阻氣層之厚度爲2.0 μιη之上述所得阻氣性被 覆劑，在120°C下熱風乾燥。然後，使所得被覆薄膜在相 對濕度80%RH、40°C下進行蝕刻處理4日，製得阻氣性薄 膜。所得阻氣性薄膜之阻氣層截面的FE-TEM照片如第1 圖所示，其EDS分析結果如第2圖所示。可確認在層狀矽 -33 - 1229036 五、發明說明（32) 酸鹽之層間存在有烷氧化矽及/或其水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例2 於實施例1中除使四乙氧基矽烷對100重量份聚乙烯醇 而言以來自烷氧化矽之矽量（Si02換算）爲127重量份外， 與實施例1相同地製得阻氣性被覆劑。而且，該阻氣性被 覆劑中之聚乙烯醇/層狀矽酸鹽之重量份比爲1 〇〇 / 50，對 烷氧化矽之矽量（S i 02換算）而言層狀矽酸鹽之重量比（來 自層狀矽酸鹽/烷氧化矽之矽量）爲0.39。與實施例1相同 地製得被覆薄膜後，使所得被覆薄膜在相對濕度80%RH、 40°C下進行蝕刻處理4日，製得阻氣性薄膜。所得阻氣性 薄膜之阻氣層以FE-TEM與EDS分析的結果，可確認在層 狀矽酸鹽之層間存在有烷氧化矽及/或其水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例3 於實施例1中除使四乙氧基矽烷對100重量份聚乙烯醇 而言以來自烷氧化矽之矽量（Si02換算）爲100重量份外， 與實施例1相同地製得阻氣性被覆劑。 而且，該阻氣性被覆劑中之聚乙烯醇/層狀矽酸鹽之重 量份比爲1 00 / 50，對烷氧化矽之矽量（Si02換算）而言層狀 矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0 · 50 〇 與實施例1相同地製得被覆薄膜後，使所得被覆薄膜在 -34- 1229036 五、發明說明（33) 相對濕度80%RH、40°C下進行蝕刻處理4日，製得阻氣性 薄膜。所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的 結果，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或 其水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例4 於實施例1中除使A液與B液以重量比2 /1之比例混合 ，且使四乙氧基矽烷對100重量份聚乙烯醇而言以來自烷 氧化矽之矽量（S i 02換算）爲1 50重量份外，與實施例1相 同地製得阻氣性被覆劑。 而且，該阻氣性被覆劑中之聚乙烯醇/層狀矽酸鹽之重 量份比爲100/25，對烷氧化矽之矽量（Si02換算）而言層狀 矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0 . 1 6。與實施例1相同地製得被覆薄膜後，使所得被覆薄 膜在相對濕度80%RH、40°C下進行蝕刻處理4日，製得阻 氣性薄膜。所得阻氣性薄膜之阻氣層以FE-TEM與EDS分 析的結果，可確認在層狀矽酸鹽之層間存在有烷氧化矽及 /或其水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例5 於實施例1中除使A液與B液以重量比1 / 1 . 7之比例混 合，且使四乙氧基矽烷對100重量份聚乙烯醇而言以來自 烷氧化矽之矽量（Si02換算）爲150重量分外，與實施例1 -35- 1229036 五、發明說明（34) 相同地製得阻氣性被覆劑。 而且，該阻氣性被覆劑中之聚乙烯醇/層狀矽酸鹽之重 量份比爲1 00 / 83，對烷氧化矽之矽量（Si02換算）而言層狀 矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0 · 5 6 〇 與實施例1相同地製得被覆薄膜後，使所得被覆薄膜在 相對濕度80%RH、40°C下進行蝕刻處理4日，製得阻氣性 薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例6 於實施例1中除使A液與B液以重量比1 / 2 . 5之比例混 合，且實施例1中除使四乙氧基矽烷對100重量份聚乙烯 醇而言以來自烷氧化矽之矽量（Si02換算）爲150重量份外 ，與實施例1相同地製得阻氣性被覆劑。 而且，該阻氣性被覆劑中之聚乙烯醇/層狀矽酸鹽之重 量份比爲1 00 / 1 25，對烷氧化矽之矽量（Si02換算）而言層 狀矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 〇 . 8 4。與實施例1相同地製得被覆薄膜後，使所得被覆薄 膜在相對濕度80%RH、40°C下進行蝕刻處理4日，製得阻 氣性薄膜。 -36 - 1229036 五、發明說明（35) 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例7 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入對100重量份聚乙烯醇而言爲1重量份平均分 子量400萬之聚乙烯醇外，與實施例1相同地製得阻氣性 被覆劑及阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例8 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入對1 00重量份聚乙烯醇而言爲1重量份平均分 子量400萬之聚乙烯醇、且以所定量添加氫離子化的強酸 性離子交換樹脂與1N-硝酸、在室溫下攪拌1小時以進行 四乙氧基矽烷之水解外，與實施例1相同地製得阻氣性被 覆劑。該阻氣性被覆劑之pH値爲2 . 2。 使用該阻氣性被覆劑，與實施例1相同地製得阻氣性薄 膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 -37- 1229036 五、發明說明（36) ’可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例9 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入對100重量份聚乙烯醇而言爲2重量份平均分 子量200萬之聚乙烯醇外，與實施例1相同地製得阻氣性 被覆劑及阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例10 除使實施例7所得的阻氣性被覆劑以乾燥後阻氣層厚 2·0μηι被覆於與實施例1相同的被覆有增黏塗層之二軸延 伸聚丙烯薄膜之增黏塗層上、100 °C下熱風乾燥外，與實 施例1相同地製得阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例11 除使實施例7所得的阻氣性被覆劑以乾燥後阻氣層厚 -38- 1229036 五、發明說明（37) 2 . Ομιη被覆於與實施例1相同的被覆有增黏塗層之二軸延 伸聚丙烯薄膜之增黏塗層上、8(TC下熱風乾燥，且在相對 濕度80%RH、40°C下進行蝕刻處理7日外，與實施例1相 同地製得阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例12 除使實施例7所得的阻氣性被覆劑以乾燥後阻氣層厚 2.0μηι被覆於與實施例1相同的被覆有增黏塗層之二軸延 伸聚丙烯薄膜之增黏塗層上、1〇〇 °C下熱風乾燥，且在相 對濕度80%RH、23°C下進行蝕刻處理14日外，與實施例1 相同地製得阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例13 在厚度20 μπι經電暈放電處理的二軸延伸聚丙烯薄膜之 電暈放電處理面上以增黏被覆劑（東洋摩頓（譯音）製、 AD3 3 5AE/CAT10L=10重量份/1重量份、在醋酸乙酯/甲苯 • = 1重量份/ 1重量份之混合溶劑中調整爲不揮發份6重量％ -39- 1229036 五、發明說明（38) 者）以增黏塗層之乾燥重量爲0.3g/m2下被覆，在10(TC下 熱風乾燥、製得被覆有增黏塗層之二軸延伸聚丙烯薄膜。 該被覆有增黏塗層之二軸延伸聚丙烯薄膜之增黏塗層上 被覆乾燥後阻氣層之厚度爲2.0 μπι之實施例7所得阻氣 性被覆劑，在120°C下熱風乾燥、製得被覆薄膜。 然後，使所得被覆薄膜在相對濕度80%RH、40°C下進行 蝕刻處理4日，製得阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM及EDS分析的結果 ，可確認在層狀矽酸鹽之層間存.在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例1 4 在厚度15 μΐΏ經電暈放電處理的二軸延伸聚丙烯薄膜之 電暈放電處理面上以增黏被覆劑（三井武田化學製、 Α32 10/A3070 = 3重量份/1重量份、以醋酸乙酯調整爲不 揮發份6重量％者）以增黏塗層之乾燥重量爲〇.3g/m2下被 覆，在100°C下熱風乾燥、製得被覆有增黏塗層之二軸延 伸聚丙烯薄膜。 該被覆有增黏塗層之二軸延伸聚丙烯薄膜之增黏塗層上 被覆乾燥後阻氣層之厚度爲2.0 μπι之實施例7所得阻氣 性被覆劑，在100°C下熱風乾燥、製得被覆薄膜。 然後，使所得被覆薄膜在相對濕度80%RH、40°C下進行 蝕刻處理4日，製得阻氣性薄膜。 -40- 1229036 五、發明說明（39) 所得阻氣性薄膜之阻氣層以FE-TEM及EDS分析的結果 ’可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例15 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入珠子狀氫離子化的強酸性離子交換樹脂，使pH 値調整爲3 · 0 ’該pH値經調整的微分散溶液中加入對1 〇〇 重量份聚乙烯醇而言來自烷氧化矽之矽量（Si 〇2換算）爲 1 5 0重量份之四乙氧基砂院，在室溫下攪拌2小時進行四 乙氧基矽烷之水解外，與實施例丨相同地製得阻氣性被覆 劑及阻氣性薄膜。所得阻氣性被覆劑之pH値爲3.0。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例16 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入珠子狀氫離子化的強酸性離子交換樹脂、使pH 値調整爲3 . 0，該pH値經調整的微分散溶液中加入對1 00 重量份聚乙烯醇而言來自烷氧化矽之矽量（Si 02換算）爲 150重量份之四乙氧基矽烷，在室溫下攪拌20小時進行四 乙氧基矽烷之水解外，與實施例1相同地製得阻氣性被覆 -41 - 1229036 五、發明說明（4〇) 劑及阻氣性薄膜。所得阻氣性被覆劑之pH値爲3 . 0。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例17 於實施例15中除在含有聚乙烯醇及層狀矽酸鹽之微分 散溶液中加入珠子狀氫離子化的強酸性離子交換樹脂、使 pH値調整爲2 . 4外，與實施例1 5相同地製得阻氣性被覆 劑及阻氣性薄膜。所得阻氣性被覆劑之pH値爲2 . 5。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例18 於實施例1 5中除在含有聚乙烯醇及層狀矽酸鹽之微分 散溶液中加入珠子狀氫離子化的強酸性離子交換樹脂、使 pH値調整爲2.4、且加入對100重量份聚乙烯醇而言爲1 重量平均分子量400萬之聚乙烯醇外，與實施例15相同 地製得阻氣性被覆劑及阻氣性薄膜。所得阻氣性被覆劑之 pH値爲2. 5。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 -42- 1229036 五、發明說明（41) 解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例19 於實施例1中除在含有聚乙烯醇及層狀矽酸鹽之微分散 溶液中加入珠子狀氫離子化的強酸性離子交換樹脂、使pH 値調整爲2.4，加入對1 00重量份聚乙烯醇而言1重量份 平均分子量400萬之聚乙烯醇。在該pH値調整、且加入 有聚乙烯醇之微分散溶液中加入對1 〇〇重量份聚乙烯醇而 言以來自烷氧化矽之矽量（Si02換算）爲230重量份之四乙 氧基矽烷，在室溫下攪拌2小時進行四乙氧基矽烷之水解 外，與實施例1相同地製得阻氣性被覆劑。所得阻氣性被 覆劑之pH値爲2 . 5。 而且，該阻氣性被覆劑中聚乙烯醇/層狀矽酸鹽之重量 份比爲1 00 / 50、對來自烷氧化矽之矽量（Si02換算）而言層 狀矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0.22。 使用該阻氣性被覆劑、與實施例1相同地以乾燥後阻氣 層厚度爲2.0μιη下被覆於增黏被覆劑之二軸延伸聚丙烯薄 膜之增黏塗層，在l〇〇°C下熱風乾燥。然後，使所得被覆 薄膜在80%RH、40°C下進行蝕刻處理，製得阻氣性薄膜。 所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結果 ，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其水 解物。 -43- 1229036 五、發明說明（42) 所得阻氣性薄膜之測定結果如表1所示。 實施例20 於實施例19中除加入對1〇〇重量份聚乙烯醇而言以來 自烷氧化矽之矽量（Si02換算）爲320重量份四乙氧基矽烷 外，與實施例1 9相同地製得阻氣性被覆劑及阻氣性薄膜 〇 而且，該阻氣性被覆劑中聚乙烯醇/層狀矽酸鹽之重量 份比爲100/50、對來自烷氧化矽之矽量（si〇2換算）而言層 狀矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0.16。所得阻氣性薄膜之阻氣層以fe-TEM與EDS分析的 結果，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或 其水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例21 於實施例1中使A液與B液以重量比2 /1之比例混合的 溶液藉由衝突型高壓分散裝置（（·股）史奇羅機械製、HJP-25030 )進行微分散化處理，製得含有4.4重量％聚乙烯醇 及1.1重量％層狀矽酸鹽之微分散溶液。在該微分散溶液 中加入珠子狀氫離子化的強酸性離子交換樹脂，將pH値 調整成2.6、加入對100重量份聚乙烯醇而言1重量份平 均分子量400萬之聚乙烯醇。在該pH値經調整、加入有 聚乙烯醇之微分散溶液中使四乙氧基矽烷以對100重量份 聚乙烯醇而言來自烷氧化矽之矽量（Si02換算）爲300重量 -44- 1229036 五、發明說明（43) 份加入，在室溫下攪拌2小時進行四乙氧基矽烷之水解外 ，與實施例1相同地製得阻氣性被覆劑。所得阻氣性被覆 劑之pH値爲2.8。 而且，該阻氣性被覆劑中聚乙烯醇/層狀矽酸鹽之重量 份比爲100/ 25、對來自烷氧化矽之矽量（Si02換算）而言層 狀矽酸鹽之重量比（來自層狀矽酸鹽/烷氧化矽之矽量）爲 0.08。 使用阻氣性被覆劑、以乾燥後之阻氣層厚度爲2.0 μιη 被覆於與實施例1相同被覆有增黏被覆劑之二軸延伸聚丙 烯薄膜之增黏塗層，在10(TC下熱風乾燥、製得被覆薄膜 〇 然後，使所得的被覆薄膜在相對濕度80%RH、4(TC下進 行蝕刻處理4日後，製得阻氣性薄膜。 使所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結 果，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其 水解物。 所得阻氣性薄膜之測定結果如表1所示。 實施例22 除使用實施例1 9所得的阻氣性被覆劑、以乾燥後之阻 氣層厚度爲1 · 0 μπι被覆於與實施例1相同被覆有增黏被 覆劑之二軸延伸聚丙烯薄膜之增黏塗層外，與實施例i 9 相同地製得被覆薄膜。 使所得阻氣性薄膜之阻氣層以FE-TEM與EDS分析的結 -45- 1229036 五、發明說明（44) 果，可確認在層狀矽酸鹽之層間存在有烷氧化矽及/或其 水解物。 所得阻氣性薄膜之測定結果如表1所示。 比較例1 在實施例1之A液中加入對1 〇〇重量份聚乙烯醇而言以 來自烷氧化矽之矽量（Si02換算）爲127重量份之珠子狀氫 離子化強酸性離子交換樹脂與四乙氧基矽烷，在室溫下進 行四乙氧基矽烷之水解、攪拌至均一相。然後，藉由過濾 除去離子交換樹脂或塵埃等之異物，製得阻氣性被覆劑。 所得阻氣性被覆劑爲透明液體、pH値爲4.2。使用該阻氣 性被覆劑、與實施例1相同地製得阻氣性薄膜。 所得阻氣性薄膜之測定結果如表1所示。 比較例2 除使實施例1所得含有聚乙烯醇及層狀矽酸鹽之微分散 溶液以乾燥後阻氣層厚度爲2 · 0 μπι被覆於與實施例1相 同的被覆有增黏被覆劑之二軸延伸聚丙烯薄膜之增黏塗層 ，在120°C下熱風乾燥外，於實施例1相同地製得阻氣性 薄膜。 所得阻氣性薄膜之測定結果如表1所示。 比較例3 在100重量份四乙氧基矽烷中加入40重量份1N-鹽酸， 在室溫下攪拌、使四乙氧基矽烷水解，製得四乙氧基矽烷 水解溶液。在實施例1所得含有聚乙烯醇及層狀矽酸鹽之 -46 - 1229036 五、發明說明（45) 微分散溶液中加入對丨00重量份聚乙烯醇而言以來自烷氧 化砂之砂量（Si〇2換算）爲丨27重量份之該四乙氧基矽烷水 解溶液’製得由聚乙烯醇、層狀矽酸鹽及四乙氧基矽烷水 解物所成的混合溶液。使用該混合溶液、與實施例i相同 地製得阻氣性薄膜。 所侍阻热丨生薄膜之測定結果如表1所示。 比較例4 於實施例1中加入對100重量份聚乙烯醇而言以來自烷 氧化矽之矽量（Si02換算）爲530重量份之四乙氧基矽烷， 在室溫下攪拌、進行四乙氧基矽烷之水解時，產生析出物 、無法製得阻氣性被覆劑。 - 47- 1229036 五、發明說明（46) 表1 實施例 透氧度Q (ml /m2 · day · atm) 2.5/(γ/90+α) (ml/m2 · day · atm) Rg (μηι) ^ND (nm) dip (nm) 實施例1 0.2 1.1 1.8 5.9 6.4 實施例2 0.8 1.1 1.9 5.9 6.1 實施例3 1.1 1.1 2.3 6.0 6.0 實施例4 0.9 1.1 1.9 6.0 6.0 實施例5 1.0 1.1 1.9 6.1 6.2 實施例6 1.0 1.1 1.9 6.1 6.1 實施例7 0.1 1.1 1.7 5.6 6.5 實施例8 0.8 1.1 2.1 5.8 6.4 實施例9 0.2 1.1 1.8 5.8 6.4 實施例10 0.2 1.1 1.8 5.6 6.6 實施例11 0.4 1.1 1.8 5.7 6.3 實施例12 0.4 1.1 1.8 5.7 6.2 實施例13 0.1 1.2 1.7 5.6 6.4 實施例14 0.3 1.1 1.8 5.9 6.4 實施例15 0.2 1.1 1.8 5.5 6.3 實施例16 0.3 1.1 1.9 6.0 6.3 實施例17 0.1 1.1 1.8 5.5 6.4 實施例18 0.1 1.1 1.8 5.5 6.4 實施例19 0.2 1.1 1.7 5.3 6.1 實施例20 0.2 1.1 1.7 5.6 6.3 實施例21 1.1 1.1 1.9 6.0 6.0 實施例22 0.3 2.0 1.8 5.3 6.1 比較例1 10 1.1 3.3 6.0 比較例2 40 1.1 3.2 比較例3 6.2 1.1 2.8 7.8 8.2 * :沒有檢測出1 〇nm以下之波峰位置 -48- 1229036 五、發明說明（47) 實施例23 在實施例1所得的阻氣性薄膜之阻氣層中以乾燥重量爲 2g/m2被覆乾性積層用黏合劑（東洋摩頓（譯音）公司製、 TM329/CAT-8B=1重量份/1重量份以醋酸乙酯溶劑調整成 不揮發份爲10重量％者）、在90°C下乾燥2分鐘後，在該 乾性積層用黏合劑面上藉由積層40μιη無延伸聚乙烯薄膜 ，製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例24 除使用實施例2所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例25 除使用實施例3所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例26 除使用實施例4所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例27 除使用實施例5所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 -49- 1229036 五、發明說明（48) 所得阻氣性薄膜之測定結果如表2所示。 實施例28 除使用實施例6所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例29 除使用實施例7所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例30 除使用實施例8所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例31 除使用實施例9所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例32 除使用實施例1 0所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例33 除使用實施例11所得阻氣性薄膜外，與實施例2 3相同 -50 - 1229036 五、發明說明（49) 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例34 除使用實施例1 2所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例35 除使用實施例1 3所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例36 除使用實施例1 4所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例37 除使用實施例1 5所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例38 除使用實施例1 6所得阻氣性薄膜外，與實施例23相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例39 -51 - 1229036 五、發明說明（5〇) 除使用實施例1 7所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例40 除使用實施例1 8所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例4 1 除使用實施例1 9所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例42 除使用實施例2 0所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例43 除使用實施例2 1所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 實施例44 除使用實施例2 2所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所乔：。 -52- 1229036 五、發明說明（51) 比較例5 除使用比較例1所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 比較例6 除使用比較例2所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 比較例7 除使用比較例3所得阻氣性薄膜外，與實施例2 3相同 地製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 參考例1 在22μπι之偏二氯乙烯被覆0ΡΡ薄膜（賴西魯（譯音）化學 工業製西奈西（譯音）ΚΟΡ品名：ΗΒ60)之偏二氯乙烯被覆 層上，與實施例23相同地被覆乾性積層用黏合劑並予以 乾燥，藉由在該黏合劑面上積層40μπι無延伸聚乙烯薄膜 ，製得無延伸聚乙烯薄膜積層阻氣性薄膜。 所得阻氣性薄膜之測定結果如表2所示。 -53- 1229036 五、發明說明（μ ) 表2 實施例 熱水處理後之透氧度Q’ 100/(γ/90+α) dND dIP (ml/m2 · day · atm) (ml/m2 · day · atm) (nm) (nm) 實施例23 8 37 5.9 6.4 實施例24 13 37 5.9 6.1 實施例25 20 37 6.0 6.0 實施例26 15 37 6.0 6.0 實施例27 20 37 6.1 6.2 實施例28 20 37 6.1 6.1 實施例29 5 37 5.6 6.5 實施例30 10 37 5.8 6.4 實施例31 7 37 5.8 6.4 實施例32 5 37 5.6 6.6 實施例33 6 37 5.7 6.3 實施例34 6 37 5.7 6.2 實施例35 5 38 5.6 6.4 實施例36 8 38 5.9 6.4 實施例37 3 37 5.5 6.3 實施例38 25 37 6.0 6.3 實施例39 3 37 5.5 6.4 實施例40 3 37 5.5 6.4 實施例41 1 37 5.3 6.1 實施例42 9 37 5.6 6.3 實施例43 21 37 6.0 6.0 實施例44 2 59 5.3 6.1 比較例5 200 37 6.0 比較例6 500 37 比較例7 90 37 7.8 8.2 參考例1 5 37 — — * :沒有檢測出1 〇nm以下之波峰位置 -54-1229036 ▲ V. Description of the invention (1) Technical field The present invention relates to a gas barrier film with excellent gas barrier properties. Specifically, it relates to a gas-barrier film that can maintain extremely high gas-barrier properties even under high humidity. 0 Prior art polypropylene films, polyethylene terephthalate films, and thermoplastic resin films such as nylon films, etc. It can be widely used as a packaging film from secondary processing properties such as excellent transparency, mechanical strength, processability, and bag-making properties. When the purpose is to provide the film with gas barrier properties such as oxygen barrier properties, the A thermoplastic resin film is formed by laminating a resin having gas barrier properties such as a vinylidene chloride-based resin or a polyvinyl alcohol-based resin. However, the vinylidene chloride resin has excellent gas barrier properties, but the chlorine resin has disadvantages in terms of incineration or disposal. In addition, although polyvinyl alcohol-based resins have excellent oxygen barrier properties in a dry state, the oxygen barrier properties under high humidity can be extremely reduced due to moisture absorption. Therefore, 1 must be cross-linked or modified to work with other compounds. 0 For example, Japanese Patent Laid-Open No. 56-4563 states that a thermoplastic resin film is provided with a silicon dioxide / polyvinyl alcohol composite polymer. Gas barrier film for coating. In addition, Japanese Patent Application Laid-Open No. 6-192454 discloses that a thermoplastic resin film is provided with a film formed of a metal alkoxide or a hydrolysate of a metal alkoxide, and a composite with a water-soluble resin having a hydroxyl group such as polyvinyl alcohol. Gas barrier film. -3- 1229036 V. Description of the Invention (2) However, 1 The gas barrier films described in JP-A-Sho 56-4563 and JP-A-Hei 6-92454 are intended to improve the oxygen-barrier properties under high humidity. Wet and extremely reduced problems, especially at high humidity above 90MH, the gas barrier effect is still insufficient. In addition, a film having another improved gas barrier performance in the gas barrier layer made of the above-mentioned compound is disclosed in, for example, Japanese Patent Laid-Open No. 2000-432 1-9, and a water-soluble resin having a hydroxyl group such as polyvinyl alcohol is provided on a thermoplastic resin film. 、 ≫ frrf Gas barrier film formed by organic layered compound and metal alkoxide hydrolysate, but the gas barrier property of the gas barrier film under high humidity and the sealing layer in hot water The gas barrier properties after boiling still need to be improved. Therefore, the object of the present invention is to provide a gas barrier film which has extremely excellent gas barrier properties even at a high humidity of more than 90% RH and has excellent gas barrier properties after boiling. The invention Z indicates that the inventors and the like have repeatedly conducted in-depth review to achieve the above purpose. As a result, it was found that a gas barrier coating layer formed by coating an aqueous solution obtained by hydrolyzing a silicon alkoxide in the presence of a layered silicate dispersed in an aqueous solution of a polyvinyl alcohol resin on a substrate layer under specific conditions, and applying The obtained gas barrier layer is different from the conventional gas barrier layer having the same composition, and the presence of silicon based on silicon alkoxide and / or its hydrolysate was confirmed between the layers of the layered silicate. Micro-dispersion of aggregates such as hydrolysates of silicon alkoxide, layered silicates, and polyvinyl alcohol resins in structures (scatterers) with large light scattering in the gas barrier layer results from the light scattering in the gas barrier layer. Scatterer's points -4- San 1229036 V. Description of the invention (3) The state adjustment is within a specific range, which can significantly improve the gas-barrier property and complete the present invention. Therefore, the present invention provides a gas barrier film comprising a substrate layer made of a thermoplastic resin film and a gas barrier made of a hydrolyzate of silicon alkoxide, a layered silicate, and a polyvinyl alcohol-based resin. The laminated body, in which the gas barrier layer has a radius of rotation (Rg) of the scattering body measured by light scattering of 2. 4 μΐΏ or less, and between the layers of the layered silicate present in the gas barrier layer, silicon alkoxide and / or a hydrolyzate thereof are present. The present invention further provides a sealing layer made of a low-melting thermoplastic resin by laminating the backing layer and the backing layer of the gas barrier layer of the gas barrier film with a low melting point thermoplastic resin. Film with excellent gas barrier properties. In addition, in the present invention, the radius of rotation (Rg) of a scatterer measured by light scattering in the gas barrier layer is an index indicating an uneven structure (optical heterogeneity) in the gas barrier layer, and is a measure of the intensity of scattering by Vv. The maggots obtained from the guinea-plot plot. Specifically, when the radius of rotation of the light-scattering particles (scatterers) is Rg, the scattering intensity I (Q) is expressed in the small-angle range (the scattering spectrum Q is near 0) by the following formula. I (q) = I (q = 0) exp (~ Rg2q 2/3). *-· Among them, it is true for the scatterer of all shapes, and it is indicated by the lnlU vs. Q2), the radius of rotation (Rg) (A. Guinier and G. Fournet, "Small-Angle Scattering of X-ray’ ’, J. Wiley & Sons, Inc. 1229036 V. Description of the Invention (4), N. Y. (1 995, pp. 102)). The Vv scattering strength of the gas barrier film of the present invention is much larger than the Vv strength of the thermoplastic film of the substrate layer or a tackifier coating, a sealing layer and the like provided as required. In addition, the Vv scattering of the substrate layer observes a strong azimuthal correlation (anisotropy of the substrate), but the Vv scattering of the gas barrier film laminated with the gas barrier layer of the present invention has no correlation with the azimuth of the iso-direction . From the above, it can be seen that the Vv scattering of the gas barrier film of the present invention can ignore the scattering of the substrate layer and only the scattering from the gas barrier layer. In addition, the gas barrier layer has no optical anisotropy, and Vv scattering can be used as a scattering treatment only from the difference in optical density from the gas barrier layer. Therefore, the light-scattering measurement of the gas-barrier film containing the substrate layer can evaluate the non-uniformity of the gas-barrier layer. The above-mentioned Rg is an index indicating the non-uniformity of the solids in the gas barrier layer, and the smaller the Rg 値 is, the more uniform the dispersed structure of the solids in the gas barrier layer is. Embodiments of the Invention The gas-barrier film of the present invention includes two forms. The first form is a laminate of a base material layer made of a thermoplastic resin film and a gas barrier layer made of a hydrolyzate of silicon alkoxide, a layered silicate, and a polyvinyl alcohol-based resin. In the first aspect, a laminated body in which a sealing layer is provided on the front surface and the reverse surface of the base material layer on which the gas barrier layer is laminated. The gas barrier film of the present invention is not particularly limited as long as it has the above-mentioned layer constitution, and other layers may be provided between the outermost layer and the layers. Specific examples include the following tackifying coatings, adhesive layers, etc. as layers set between layers, and, for example, 1229036 V. Description of the invention (5) Print layer as the outermost layer or the layer provided between layers. In the present invention, the Rg determined by light scattering with the degree of solid dispersion in the gas barrier layer is 2. Below 4μιη, the better is 2. Below 3μm is very important. In other words, Rg is greater than 2. At 4μηι, the dispersion state of the ammonium body starting from the layered silicate is insufficient, and it is not easy to produce a gas barrier film with high oxygen barrier properties. Moreover, the dispersion state of the scatterer is not only related to the dispersion state obtained by finely dispersing the layered silicate, but also to the dispersion state of the hydrolysate of the polyvinyl alcohol-based resin %% silicon oxide measured as other scatterers. The structure of the scatterer having Rg measured by light scattering in the gas-barrier film of the present invention is not clear, but the range of scattering of the alignment of the layered silicate is > Rg is related to its size. The microstructure of the gas barrier layer was observed by TEM (transmission electron microscope) or the following FE-TEM (electric field emission type transmission electron microscope) observation. The structure of the layered silicate in the gas barrier layer was well aligned parallel to the film surface. It can be confirmed that there is a range of scatter (bend) of the alignment of layered silicate in a period of several μηι series. This range is an optically uneven structure that scatters light. Moreover, the size of this range can be presumed to be light scattering. The measured Rg is correlated. In other words, when Rg is large, the range of the orientation dispersion of the layered silicate is large, the orientation dispersion is large, and the layered silicate will produce the stray effect of the gas barrier element, or the homogeneity of the gas barrier layer. Conversely, when the Rg is small, the range of the disorder of the layered silicate is small, and because of the small disorder of the orientation, the stray effect is large, and the gas barrier is homogeneous and excellent in gas barrier properties. In particular, the gas barrier film 9 of the present invention has an Rg of 2. Very small 値 -7- below 4μm, so it can exhibit excellent gas barrier properties 1229036 5. Description of the invention (6) 〇 In addition, the gas barrier film of the present invention is based on the hydrolyzate of silicon alkoxide and layered silicic acid. In the gas barrier layer formed by the salt and the polyvinyl alcohol-based resin, silicon alkoxide and / or a hydrolyzate thereof are present between at least a part of the layered silicate. By having such a structure, the gas barrier film of the present invention exhibits excellent gas barrier properties in accordance with the dispersion state of the scatterer. In other words, the correct reason is not clear, but in the above gas barrier layer, by the presence of silicon alkoxide and / or its hydrolysate between the layered silicate layers, the interlayer distance of the layered silicate becomes larger, And the effect of a small proportion of the saturated phase of the layered silicate or a small proportion of the saturated phase of the polyvinyl alcohol resin, the result is 2. A specific structure represented by a radius of gyration (Rg) of 4 μm or less can exhibit extremely high gas barrier properties that are not known. In the above gas barrier layer, there is silicon alkoxide and / or its hydrolysate between the layers of the layered silicate. The cross section of the gas barrier layer is cut out by using a thin slicer, and ultra-thin sections are cut out by using a STEM ( Scanning transmission electron microscope (FE-TEM) is used to observe and confirm the existence of the interlayer, and by EDS (energy dispersive X-ray analysis device) elemental analysis, A pattern (element pattern) showing the element dispersion concentration and the silicon dispersion concentration of the layered silicate in the gas barrier layer can be confirmed. The 1L formula is briefly explained. Fig. 1 is a diagram showing the results of FE-TEM analysis of the structure of the gas barrier layer of the gas barrier film obtained in Example 1. Figure 2 shows the resistance of the gas barrier film obtained in Example 1 of the present invention. 1229036 V. Explanation of the invention (7) The layered silicate structure of the gas layer is analyzed by EDS. From Fig. 1, it was confirmed that the layered silicate was finely dispersed at a thickness of 1 to 2 nm, and a structure of approximately parallel alignment was observed on the film surface, and it was confirmed that the layered silicate was present between the layers. At this time, the interlayer was found to be approximately 10 to 20 nm. In the present invention, the layered silicate layer in the gas barrier layer varies depending on the type, and generally it is preferably 5 to 100 nm. In addition, the second (a) image is a dark field image by STEM, and the portion with a high element density is brighter (the FE-TEM image in the first image is light-dark inversion). Figures 2 (b) and 2 (c) are the results of drawing the elements of the inscription and chopping, and Figure 2 (a) is the result of drawing the elements of the range surrounded by white lines. The bright range in Figure 2 (b) is the distribution pattern of element-containing aluminum inherent to layered silicate, which is consistent with the distribution of layered silicate. In addition, Figure 2 (c) shows the distribution pattern of silicon. It can be seen that silicon can be strongly observed in the layers of layered silicate (the range in which aluminum is not observed). Interlayer silicon alkoxide and / or its hydrolyzate exist. In the present invention, the proportion of the hydrolysate existing between the gas barrier layers cannot be specified from the above analysis, and the gas barrier film of the present invention is estimated to be almost all of the silicon alkoxide as a hydrolysate based on its manufacturing conditions. The gas barrier film of the present invention has the above-mentioned structure, and can produce an oxygen permeability (Q; m 1) measured at a temperature of 23 ° C, a humidity of 90% RH on the substrate layer side, and a humidity of 90% RH on the seal layer side. / m2 · day · atm) satisfies the following formula (1), and this form is more preferable. Q = 2. 5 / (^ / 90 + (¾) (1) 1229036 V. Description of the invention (8) (where α is the thickness of the gas barrier layer () 'γ is the thickness of the τκ gas barrier film (μπ〇) and The gas barrier film of the present invention provided with a sealing layer on the surface of the gas barrier layer is left in hot water at a temperature of 90 ° C for 30 minutes, and can be prepared at a temperature of 23 ° C, a humidity of 90% RH on the substrate layer side, and a seal. The oxygen permeability (Q,; inl / m2 * day * atn〇) measured at 90% RH in the layer side is more suitable if it satisfies the following formula (2). Q 'S 1 0 ◦ / (γ / 9 0 + a) (2) (where α is the thickness of the gas barrier layer (μπι), γ is the thickness of the gas barrier film (μπm)) In the above formulas (1) and (2), the gas barrier The thickness α of the layer refers to the thickness of the layer formed by the hydrolyzate of the above-mentioned silicon alkoxide, layered silicate and polyvinyl alcohol resin, and polyethylene oxide and other optional additives as needed. The thickness of the gas layer is not particularly limited. It is generally 0 when considering gas barrier properties and preventing cracking during processing. 1 ~ 1 〇μιη, preferably 0 · 5 ~ 3 μπι 0 In addition, the thickness of the gas barrier film refers to the lamination of the above gas barrier layer, the substrate layer, and a sealing layer and a thickening coating provided as required. The total thickness of the other layers. The thickness of the gas barrier film is not particularly limited, but is generally 5 to 200 μm, and preferably 10 to 100 μm. Then, the above formulas (1) and (2) are based on the thickness and resistance of a specific gas barrier layer -10- 1229036 V. Description of the invention (9) The thickness of the gas thin film is used as a reference to make the oxygen permeability achieved by the present invention The range of degrees depends on the formula of the correction coefficient depending on the thickness change. In other words, the thickness of the gas barrier layer in the above formula directly affects the oxygen permeability of the obtained gas barrier film. In addition, the influence of the gas barrier film containing the substrate layer, the sealing layer, the tackifying coating, the adhesive layer and the like is about Proportion has effect. Therefore, the conventional gas barrier film having a gas barrier layer formed from a hydrolyzate of silicon alkoxide, a layered silicate, and a polyvinyl alcohol-based resin has a thickness of 0. The thickness of 4μm, gas barrier film is 54. 3 at 4 μm. 2ml / m2. day • atm 0 This “値” means 値 greater than the upper limit 氧 of the oxygen permeability of the gas barrier film obtained by the above formula of the present invention. Therefore, it can be known that the gas barrier film of the present invention has a conventional gas barrier film of the same composition that cannot be achieved. Very high gas barrier. The oxygen permeability of the gas barrier film was measured based on the HS K7126 B method. In addition, the gas barrier film was placed in hot water at a temperature of 90 ° C for 30 minutes. The oxygen permeability was measured by completely impregnating the gas barrier film in hot water whose temperature was adjusted to 90 ° C in a thermostatic bath. After 30 minutes had elapsed, the water on the surface of the film was wiped, and then the method for measuring the oxygen permeability was carried out. In addition, the gas barrier film of the present invention measures the distance dND between the regions perpendicular to the film surface in the gas barrier layer by small-angle X-ray scattering to be 6. 8nm or less, because it has excellent gas barrier properties under high humidity, it is better to maintain more excellent gas barrier properties after boiling treatment in hot water when a separate sealing layer is provided. Better is 6. Below 3nm, the best is 5. 8nm or less. In addition, by small-angle X-ray scattering measurement -11-1229036 V. Invention description (10) The ratio of the distance dIP between the regions in the plane direction of the film in the gas barrier layer (dIP / dND) is 1. Above 0 is better and more is 1. 1 or more. The inter-area distance dND is 6. 8nm or less and dIP / dND is 1. When it is 0 or more, it is preferable because the extremely excellent gas barrier property can be maintained even after the sealing layer is boiled in hot water. Furthermore, in the present invention, the inter-area distances dIP and dND in the gas barrier layer measured by small-angle X-ray scattering are indicators of the fine periodic structure (density shaking) of the gas barrier layer, and represent the positions of the scattering peaks of the small-angle X-ray scattering. (Scattering angle 2Θ) can be obtained by Bragg's formula (2d s ίηθ = λ, where λ is the wavelength of X-ray) (L. H_ Sperling, "Polymeric Multicomponent Materials", J. Wiley & Sons, Inc. , Ν · Υ · (1997), pp. 326) Here, the inter-area distance dIP in the in-plane direction of the thin film in the gas barrier layer can be obtained by small-angle X-ray scattering obtained by a transmission method in which X-rays are perpendicularly incident on the film surface (through incident). In addition, the distance dND between the regions perpendicular to the film surface can be obtained by the small-angle X-ray scattering obtained by transmitting X-rays from the end face of the film parallel to the film surface (edge incidence). In addition, the small-angle X-ray scattering longitudinal cross-sectional view of the gas barrier film of the present invention was measured. In addition to the gas barrier layer scattering, the thermoplastic resin film scattering from the substrate layer, the center beam edge, air scattering, and parasitic scattering were included. Here, the small-angle X-ray scattering longitudinal cross-sectional view of the substrate layer film used in the gas barrier film of the present invention or a thermoplastic resin film having the same thickness as the substrate layer is measured under the same conditions, and from the gas barrier of the present invention Low-angle scattering longitudinal section of the thin film • 12-1229036 V. Explanation of the invention (11) The drawing can remove the scattering from the thermoplastic resin film of the substrate layer, the edge of the central beam, air scattering, and parasitic scattering. A longitudinal sectional view of a gas barrier layer. The inter-area distance was obtained from the peak position of the small-angle X-ray scattering longitudinal section of the gas barrier layer obtained by this method. As a result of observing the cross section of the gas barrier layer in the gas barrier film of the present invention by FE-TEM (transmission electron microscope), the interlayer thickness of the layered silicate film in the thickness direction is about 10 to 20 nm. Because the inter-area distance obtained by small-angle X-ray scattering is less than 10 nm, and the thickness direction and in-plane direction of the film are also the same degree, the gas barrier layer here is mainly an alkoxide hydrolysate, and the inter-area distance It is related to the dispersion state or particle size of the hydrolyzate of silicon alkoxide. In other words, the correct reason is unknown, but the hydrolyzate of alkoxide is mainly fine and dense perpendicular to the film surface. Because of the thin and flat structure inside the film surface, after boiling in hot water under high humidity and with a sealing layer Can still exert excellent gas barrier properties. The material of the base material layer in the gas-barrier film of the present invention is not particularly limited as long as it is a thermoplastic resin, and it is preferred to have transparency when used for packaging purposes. The above thermoplastic resins are, for example, random or two or more kinds of α-olefins such as ethylene monomer, ethylene and propylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene. Block copolymer, ethylene and vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, one or more random or block copolymers of methyl methacrylate, propylene monomer, propylene and other than propylene 1-butene, 1-pentene, dihexene, 4-methyl-1-pentene, etc. or -13-1229036 V. Description of the invention (彳 2) Random or embedded of 2 or more α-olefins Polyolefin resins such as segment copolymers, butylene monomers, ionic polymer resins, and mixtures of these polymers; hydrocarbon resins such as petroleum resins, terpene resins; polyethylene terephthalate, Polyester resins such as butyl phthalate and polyethylene naphthalate; Nylon 6, Nylon 66, Nylon 11, Nylon 12, Nylon 610, Nylon 6/66, Nylon 6 / 6 1 0, Polyamide resins such as Nylon MXD; acrylic resins such as polymethyl methacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butyl Styrene and acrylonitrile resins such as olefin copolymers and polyacrylonitrile; polyvinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers; polycarbonate resins; polyketal resins; polyethylene oxide resins; Poly maple resin; polyimide resin; polyimide resin; etc. These can be used singly or in combination of two or more kinds. Among them, polyolefin resins, polyester resins, polyamide resins, styrene, acrylonitrile resins, polyvinyl alcohol resins, and polycarbonates are excellent in transparency, mechanical strength, and packaging suitability. Ester-based resins and the like are preferred, and more preferred are polyolefin-based resins, polyester-based resins, and polyamide-based resins. The base material layer made of these preferred thermoplastic resins has an oxygen barrier property of 10 ml / m2 * dayatm or more as measured in a humidity of 90% RH. The above-mentioned thermoplastic resin film can be produced using conventional methods There are no special restrictions. Specifically, conventional methods such as a solution casting method, a T-molding method, a tube method, and a calendering method can be adopted. Moreover, in consideration of mechanical properties, etc., the above-mentioned -14-1229036 V. Description of the Invention (1 3) The thermoplastic resin film described above is preferably subjected to stretching treatment. The stretching method may be a conventional method without any particular limitation, such as roll uniaxial stretching, calendering, sequential biaxial stretching, simultaneous biaxial stretching, tubular stretching, and the like. Among these stretching methods, in terms of thickness accuracy, mechanical properties, etc., sequential biaxial stretching and simultaneous biaxial stretching are preferred. In addition, the thickness of the thermoplastic resin film is not particularly limited, and it is appropriately selected in consideration of the application to be used, and is appropriately selected from the range of 1 to 200 m. Among them, in terms of elongation processability, gas barrier property, and bag-making processability, 5 to 100 μm is preferable, and 10 to 50 μm is more preferable. In addition, in the above-mentioned thermoplastic resin film, antistatic agents, anti-moth agents, anti-blocking agents, heat stabilizers, antioxidants, light stabilizers, crystal nucleating agents, Conventional additives such as a smoothing agent, an ultraviolet absorber, and a surfactant for the purpose of imparting smoothness and blocking resistance. The base material layer made of the thermoplastic resin film is preferably transparent in consideration of packaging applications, especially when used as a gas barrier film. Specifically, the haze is preferably 15% or less, and more preferably 10% or less. In the gas-barrier film of the present invention, as the polyvinyl alcohol-based resin constituting one of the gas-barrier layers, a vinyl alcohol-based polymer and a derivative thereof can be used. For example, polyvinyl alcohol with a saponification degree of 75% or more, 40 mol% or less of all hydroxyl groups, acetalized polyvinyl alcohol, alcohol-soluble modified polyvinyl alcohol, and ethylene-vinyl alcohol with a vinyl alcohol unit of 60 mol% or more Copolymerized polyvinyl alcohol and the like are preferred. Among them, polyvinyl alcohol having a saponification degree of 75 mol% or more is better because of the obtained film. -15-1229036 V. Description of the invention (14) The transparency or the gas barrier property under high humidity is good, so it is better. In addition, when the degree of polymerization of the polyvinyl alcohol-based resin is considered in terms of processability, it is preferably 300 to 5000, and more preferably 500 to 3500. In the hydrolyzed product of silicon alkoxide, which is a constituent of the gas barrier layer in the gas barrier film of the present invention, a part or all of the alkoxy group containing silicon alkoxide is hydrolyzed, a polycondensate of silicon alkoxide Part of or all of the alkoxy groups of the polycondensate by hydrolysis, and various mixtures thereof. The above silicon alkoxide is not particularly limited as long as it can form a hydrolysate. Specifically, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, and butyltrimethylsilane can be formed. Oxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propyltributoxysilane, (3,4-epoxycyclohexyl) methyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 1-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminomethylaminomethyltrimethoxysilane, N-aminomethyl-3-amino Propyltrimethoxysilane, N · (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- β- (N-vinylbenzylaminoethyl) Hydrolyzate of silicon oxide alkoxy) -Ύ- aminopropyl trimethoxy Silane like. -16- 1229036 V. Description of the invention (15) Siloxane polycondensate and the product of hydrolysis of some or all of the alkoxy groups in the condensation product, including the above-mentioned silica alkoxide through hydrolysis, and the dehydration and / Or formed by polycondensation of dealcoholization. The hydrolyzate of silicon alkoxide in the above gas barrier layer, the silicon derived from silicon alkoxide has 90 to 5,000 parts by weight in terms of Si02 for 100 parts by weight of polyvinyl alcohol resin, and preferably 100 to 3 50 Part by weight, more preferably 100 to 250 parts by weight, is desirable because it can exhibit excellent gas barrier properties. The layered silicate, which is one of the constituents of the gas barrier layer in the gas barrier film of the present invention, can be used by those skilled in the art, and is not particularly limited. For example, montmorillonite, beryl, chlorite, saponite, hectorite, magnesium-rich montmorillonite, organic pennite, kaolin, geocline, halloysite, serpentine, leaf serpentine, dark yellow Uranium ore, nickel chlorite, kidney manganese ore, magnesite, hydroarsenite, aluminocopper ore, hydroantimony manganese ore, vermiculite, chlorite, magnesite, chlorite, pyrosulfite antimony silver ore, talc, calcareous aluminum Yellow feldspar, wurtzite, beadite, iron talc, mica, muscovite, sandy dolomite, illite, sericite, chlorite, green phosphorite, neon orthoclase, sodium mica, phlogopite, biotite , Chlorite, vermiculite, etc. These are mostly natural minerals, but they can also be produced by chemical synthesis. Among them, a gas barrier film obtained by using montmorillonite is preferable because it has excellent gas barrier properties. Layered silicon in the above gas barrier layer. The acid salt is 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin, and is desired because it exhibits excellent gas barrier properties. In addition, the amount of silicon derived from silicon alkoxide in the gas barrier layer (equivalent to Si 02) -17-1229036 V. Description of the invention (16) The weight ratio of layered silicate (from layered silicate / alkane) Silicon content of silicon oxide) is 0. 01 ~ 1, preferably 0. 1 to 1 are preferred because they exhibit excellent gas barrier properties. In addition, in the gas barrier film of the present invention, the components of the gas barrier layer are not particularly limited as long as they are formed of a hydrolyzate of silicon alkoxide, a layered silicate, and a polyvinyl alcohol-based resin. In order to prevent the occurrence of cracks when the gas barrier layer is formed, and to prevent the gas barrier layer from cracking when the film is deformed during use, it is preferable to add polyethylene oxide in addition to the above components. The higher the average molecular weight of the polyethylene oxide system, the better the effect. The average molecular weight is preferably 100,000 or more, the average molecular weight is more than 500,000, and the average molecular weight is more than 200,000. Moreover, the end of the molecular chain of the polyethylene oxide may be a hydroxyl group or a chemically modified one, which is not particularly limited, and generally one having hydroxyl groups at both ends is preferred. The polyethylene oxide is added to 0.1 parts by weight of 100 parts by weight of a polyvinyl alcohol-based resin. 1 ~ 5 parts by weight, preferably 0. 5 ~ 2 parts by weight. In addition, the components constituting the gas barrier layer of the gas barrier film of the present invention may be blended with other components so long as the effects of the present invention are not impaired. For example, urethane-based cross-linking agents, isocyanate-based cross-linking agents, melamine-based cross-linking agents, epoxy-based cross-linking agents, etc., silane-based coupling agents, titanium-based coupling agents, etc. Water-soluble viscosity-enhancing coating agents such as isocyanate, water-based polyurethane resin, polyethyleneimine, and water-based epoxy ester, aluminum-based organic compounds, zirconium-based organic compounds, and the like. The gas barrier film with extremely high gas barrier properties of the present invention can be formed by the hydrolyzate, layered silicate and vinyl alcohol-based resin of silicon alkoxide-18-1229036 V. Description of the invention (17) It was produced by forming on the base material layer by the following method. The gas-barrier film of the present invention is made of silicon alkoxide in the presence of a layered silicate dispersed in an aqueous solution of a polyvinyl alcohol-based resin whose pH is adjusted to 1 to 5, preferably 2 to 4. A thickening coating agent formed from the aqueous solution obtained by hydrolysis is coated on the substrate film and dried. When a suitable method for preparing a gas barrier coating agent is described in detail in the above method for manufacturing a gas barrier film, first, an aqueous solution of a polyvinyl alcohol-based resin in which a layered silicate is dispersed in advance is made by a conventional microdispersion device, For example, ultrasonic dispersion, bead mill, ball mill, roll mill, homomixer, supermixer, disperser mixer, penetrating high-pressure dispersing device, conflict high-pressure dispersing device, porous high-pressure dispersing device, throwing ball high-pressure dispersing device, (Collision + penetration) type high-pressure dispersing device, ultra-high pressure homomixer, etc. Among the above-mentioned conventional micro-dispersion devices, a homomixer, an ultra-mixer, a dispersing mixer, a through-type high-pressure dispersing device, a conflict-type high-pressure dispersing device, a porous high-pressure dispersing device, a ball-type high-pressure dispersing device, (conflict + Through-type high-pressure dispersing device and ultra-high-pressure homogenizer can make the layered silicate form a good dispersion state, and the above-mentioned Rg in the gas-barrier layer of the obtained gas-barrier film is adjusted to 2. 4μm or less is preferred. In addition, when montmorillonite is used as the layered silicate, the distance dND between the regions of the gas barrier layer of the obtained gas barrier film perpendicular to the film surface is adjusted to 6. 8nm or less is preferred. To adjust the solvent of the above-mentioned aqueous solution, a mixed solvent of water / lower alcohol can be used. -19-1229036 V. Description of the invention (18). The lower alcohol is an alcohol having 1 to 3 carbon atoms, and specific examples thereof include methanol, ethanol, n-propanol, and isopropanol. The mixing ratio of the water / alcohol is appropriately selected within a range of 99/1 to 20/80 by weight. When the concentration of the polyvinyl alcohol resin in the aqueous solution is 0.1 to 20%, the mixing amount of the polyvinyl alcohol resin / silicon alkoxide can be appropriately determined, and the concentration of the polyvinyl alcohol resin is preferred for the solvent. The mixed amount of polyvinyl alcohol-based resin / silicon oxide is used in the range of 1 to 10%. The method of adjusting the pH of the above-mentioned aqueous solution of the polyvinyl alcohol-based resin in which the layered silicate is dispersed is in the above range. The method of protonating the exchangeable ions in the layered silicate makes the silicon alkoxide and / Or its hydrolyzate is highly effective in the layered silicate layer and can be widely spread in the layered silicate layer, which is very effective and suitable for use in the present invention. This protonation is ion-exchanged using a cation exchange resin or an ion exchange method. For example, the protonation of a cation exchange resin is used, such as a cation exchange resin in which a solution containing a layered silicate is exchanged with a polystyrene • sulfonic acid type strongly acidic ion exchange resin. Furthermore, the protonation using an ion exchange membrane, for example, alternately arranges a cation exchange membrane and a preferred anion exchange membrane with a loose structure between the cathode and the anode, forms a cathode chamber in which a cathode is formed, an anode chamber in which an anode is formed, and is formed therebetween. Electrical dialysis tank with several compartments, an anion exchange membrane on the anode side, and a cation exchange membrane on the cathode side, a solution containing a layered silicate is supplied to a chamber adjacent to the chamber, and a method of performing electrical dialysis -20- 1229036 V. Description of the invention (19) = Alternate arrangement of cation exchange membrane and bipolar membrane between cathode and anode, constituting a cathode chamber in which a cathode is present, an anode chamber in which an anode is formed, and forming several compartments therebetween An electrodialysis tank, and a chamber having a bipolar membrane on the anode side and a cation exchange membrane on the cathode side, the solution containing the layered silicate is supplied to the chamber adjacent to the chamber with a dilute alkaline aqueous solution as the preferred electrolyte solution. , Methods of electrical dialysis, etc. Next, the pH is adjusted to the above range, silicon alkoxide is added to an aqueous solution of a polyvinyl alcohol-based resin in which the layered silicate is dispersed, and hydrolysis is performed in the presence of the dispersed layered silicate. The hydrolysis of the silicon alkoxide in the aqueous solution of the polyvinyl alcohol-based resin containing the layered silicate dispersed therein is adjusted to a pH of 1 to 5, preferably 2 to 4, and hydrolyzed. It is performed in the presence of a catalyst. When the exchangeable ions in the layered silicate are ion-exchanged with a cation exchange resin or an ion exchange membrane, protonated, and adjusted to the above pH range, the protonated layered silicate itself can be used as a hydrolytic catalyst. For example, when the cation exchange resin is removed to the outside of the system by filtration or the like before the silicon alkoxide is hydrolyzed, the silicon alkoxide can still be hydrolyzed. The aforementioned hydrolysis catalysts include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, organic phosphoric acid, formic acid, acetic acid, acetic anhydride, chloroacetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, maleic acid, fumaric acid, itaconic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid , Organic acids such as cinnamic acid, uric acid, barbituric acid, p-toluenesulfonic acid, etc., acidic -21-1229036 5. Description of the invention (20) Cation exchange resin. Among them, an acidic cation exchange resin is preferred in terms of easy adjustment of pH, simple catalyst removal treatment, and transparency of the gas barrier layer. In the above hydrolysis, time is one of the factors determining the degree of hydrolysis, but in general, after adjusting to the above pH, it is 1 to 24 hours at room temperature, preferably 2 to 18 hours, and more preferably 2 to 12 hours. Moreover, the polyethylene oxide added to the gas barrier layer in the gas barrier film of the present invention may be added at any place in the above-mentioned manufacturing process as necessary. For example, the layered silicate is dispersed and added before the hydrolysis of the silicon alkoxide, or it is added after the hydrolysis of the silicon alkoxide. The ratio of each component in the above manufacturing method is determined by the ratio shown in the above gas barrier layer. In the above manufacturing method, considering the stability of the gas barrier coating agent, the color of the obtained gas barrier layer, and good gas barrier properties under high humidity, etc. In other words, the protonated layered silicate can be removed before or after the hydrolyzation of the silicon alkoxide, and the hydrolysis catalyst used to adjust the pH can be removed from the system. In the present invention, the method of removing the protonated layered silicate before or after the hydrolysis of the silicon alkoxide and removing the hydrolysis catalyst outside the system is not particularly limited. For example, when it is an ion exchange resin, it can be removed by physical methods such as filtration. In addition, when an inorganic acid or an organic acid is used, a basic anion exchange resin that can ionize an anion component derived from the inorganic acid or the organic acid with a hydroxyl group is ion-exchanged to a hydroxyl ion, and is removed to a system by filtration. The external method is better. -22- 1229036 V. Description of the invention (21) In the present invention, the hydrolysis of silicon alkoxide is preferably carried out until the phase separated into a homogeneous liquid phase. At this time, it can be partially hydrolyzed, completely hydrolyzed, or alkoxylated State of polycondensation between silicon. The final pH of the gas barrier agent is adjusted to be within a range of 1 to 5, which is preferable in terms of preventing gelation of the gas barrier agent, preventing cracking after the gas barrier layer is formed, and exhibiting good gas barrier properties under high humidity. . In the method for producing a gas barrier film of the present invention, the lamination of the gas barrier layer and the substrate layer can be performed by coating the substrate layer with the gas barrier coating agent and drying it. The time for coating the above-mentioned gas barrier coating agent on the base material layer can be performed when hydrolysis of the silicon alkoxide is performed and the phase-separated liquid phase becomes a homogeneous phase. Furthermore, in consideration of the occurrence of cracks in the obtained gas barrier layer and reduction of the gas barrier property, it is preferable to cover the gas barrier layer until the deterioration of the gas barrier layer is caused. In the present invention, the coating method of the gas barrier coating agent is not particularly limited, and a solution or a solvent dispersion coating method which can be coated on a high-speed film is preferred. Specific examples of these coating methods include roll coating method, reversible roll coating method, gravure coating method, spray coating method, contact coating method, mold coating method, strip coating method, rod coating method, and photogravure coating on a doctor blade. Method, curtain coating method, and the like, a method in which a gas barrier coating agent covers the surface of a thermoplastic resin film. The method for drying the gas barrier coating agent on the substrate layer in the present invention may be a conventional drying method, and is not particularly limited. Specifically, for example, one or more heat roller contact methods, heat medium (air, oil, etc.) contact methods, infrared -23-1229036 V. Description of the invention (22) Wire heating method, microwave heating method, etc. Among these, a heated air contact method or an infrared heating method is preferred in terms of treatment of the appearance of the film, drying effect, and the like. The drying conditions of the gas barrier coating agent are not particularly limited, and it is particularly preferable to use a temperature range of 60 ° C or higher to less than the melting point of the substrate in consideration of gas barrier properties and drying efficiency. In addition, the above drying temperature is more preferably 80 ° C or more, and the most preferable is 9 ° C or more. In addition, the drying temperature is preferably 10 ° C or less below the melting point of the base material layer, and more preferably 15 ° C or less. Temperature. The above drying time is preferably from 5 seconds to 10 minutes, and more preferably from 10 seconds to 5 minutes in consideration of gas barrier properties and drying efficiency. Ultraviolet rays and X-rays may be applied before and after the drying as required. High-energy irradiation of electrons, electron beams, etc. In addition, in order to further improve the gas barrier properties under high humidity, a surface treatment such as corona discharge treatment or flame plasma treatment is directly applied to the gas barrier layer. In the invention, the method of coating the base material layer with the gas barrier coating agent and drying at the above temperature to form a gas barrier layer, and then applying an etching treatment, can obtain a gas barrier film having more excellent gas barrier properties. Therefore, the above-mentioned etching treatment is very effective for improving the gas barrier properties of the obtained gas barrier film, especially the gas barrier properties under high humidity of more than 90% RH, and excellent gas barrier properties after boiling treatment in hot water. Effect. Etching conditions can be appropriately determined, and there is no particular The limitation is usually determined within the range that defects such as wrinkles and slacks do not occur in the base material layer by etching. In the present invention, the film formed by forming the above gas barrier layer on the base material layer is at -24-1229036. 2. Description of the invention (23) Etching treatment is performed in an atmosphere with a temperature of 30 to 80 ° C and a relative humidity of 30% RH to 100% RH. Uranium etching is performed in an atmosphere with a relative humidity of 30% RH to 100% RH. Since it has excellent gas barrier effect after boiling in hot water, it is better. When the relative humidity is less than 30MH, the gas barrier film obtained by the etching process will cause the boiling process after the sealing layer is laminated on the gas barrier layer. This effect reduces the gas barrier properties of the alkoxide in the gas barrier layer of the gas barrier film used in the present invention by performing an etching treatment in an atmosphere having a relative humidity of 30% RH or more. Base hydrolysis or the accompanying polycondensation reaction or hydrogen bonding with polyvinyl alcohol resin, etc., and the effect of reducing the free volume in the coating layer. The temperature during the etching process is in the range of 30 ~ 80 ° C, if it is less than 30 At ° C, the time required for etching becomes longer Moreover, if it is higher than 80 ° C, the secondary processing suitability of printing, bag making, etc. is reduced due to deformation or moisture absorption of the base material layer. The specific etching treatment conditions are within the range of the above-mentioned etching treatment conditions, so that It can be determined within the range of defects such as wrinkles and sags of the base material layer caused by etching. When considering that it has extremely excellent gas barrier properties even under high humidity and still has excellent gas barrier properties after boiling, 30 ~ 80 ° C, relative humidity 30% RH ~ 100% RH, it is better to perform the etching treatment, and it is better to perform etching treatment in a temperature of 40 ~ 80 ° C, relative humidity 40% RH ~ 90% RH For example, when the thermoplastic resin film is a biaxially stretched polypropylene film, it is selected from the range of temperature 30 ~ 5 (TC, relative humidity 30% RH ~ 100% RH, so that the temperature is 40 ~ 50 ° C and relative humidity 40% RH ~ 90% RH gas-25-1229036 V. Description of the invention (24) It is better to carry out etching treatment under the atmosphere. The temperature and relative humidity may be within a range that does not cause defects such as wrinkling and slackening of the base material layer. A higher setting is preferable because the number of days required for etching can be reduced. The number of days required for etching can be determined as appropriate. The above-mentioned temperature and relative humidity are set in a range of 1 to 10 days. The method for performing the etching treatment under the above conditions is not particularly limited. A suitable method is, for example, a method of subjecting the above-mentioned base material layer to a gas barrier coating agent, and drying the film in a constant temperature and humidity chamber at a set temperature and relative humidity. In addition, when the film is rolled into a roll shape, a method of reducing the take-up tension, providing a gap between the gas-barrier films, and performing an etching treatment in a constant temperature and humidity chamber, or using water vapor when the film is rolled into a roll shape, is used. The method of spraying on a gas barrier layer, and performing an etching process. By performing the above-mentioned etching treatment, the oxygen permeability (Q; ml / m2.) Measured at a temperature of 23 ° C, a humidity of 90% RH on the substrate layer side, and a humidity of 90% RH on the sealing layer side can be obtained. day * atni) A gas-barrier film that satisfies the following formula (3), and this form is preferred in the present invention. Q $ 2 · 0 / (γ / g Ο + α) (3) (where α is the thickness of the gas barrier layer (μm), and γ is the thickness of the gas barrier film (μm)). In addition, in the above gas barrier film, a laminated body including a sealing layer made of a thermoplastic resin having a lower melting point than the thermoplastic resin constituting the base material layer may be included on the build-up layer and the back surface of the base material layer on which the gas barrier layer is laminated. After being left in hot water at a temperature of 90 ° C for 30 minutes, the humidity of the substrate layer side at a temperature of 23 ° C-26-1229036 V. Description of the invention (25) 90% RH, the humidity of the sealing layer side 90% The oxygen permeability (Q ,; ml / m2 • day · atm) measured in RH can satisfy a gas barrier film of the following formula (4), and this form is the best in the present invention. Q 'S 6 0 / (γ / g 0 + α) (4) (where α is the thickness (µm) of the gas barrier layer and γ is the thickness (µm) of the gas barrier film). In the present invention, in order to further improve the adhesion between the substrate layer and the gas barrier layer, and to further improve the gas barrier properties and durability of the obtained gas barrier film, it is performed on the surface of the substrate layer of the laminated gas barrier layer. Surface treatment is appropriate. This surface treatment can be performed by a conventional surface treatment method, and is not particularly limited. For example, corona discharge treatment in the atmosphere, corona discharge treatment in nitrogen, corona discharge treatment in carbonated gas, flame plasma treatment, ultraviolet treatment, ozone treatment, electron beam treatment, plasma treatment by energizing inert gas, etc. method. Moreover, these surface treatments can also be used as treatments. In addition, in consideration of further improving the adhesion strength between the substrate layer and the gas barrier layer, it is preferable to use a method in which a tackifier coating is provided therebetween. The tackifier coating agent used to form the above-mentioned tackifier coating may be a conventional one, and is not particularly limited. For example, an isocyanate-based, polyurethane-based, polyester-based, polyethylenimine-based, polybutadiene-based, polyolefin-based, or alkyl titanate-based thickening coating agent is used. In addition, in the gas barrier film of the present invention, a commercially available polyolefin and ethylene-vinyl acetate copolymer can be laminated on the outer layer of the gas barrier layer obtained by the above method to provide heat-sealing properties, hot water resistance, and the like. Material, ethylene -27-1229036 V. Description of the invention (26) Sealing layer of methacrylate copolymer, etc. Effect of the Invention As can be seen from the above description, the present invention can provide a gas barrier film made of a polyvinyl alcohol-based resin as a gas barrier layer, a silicon alkoxide hydrolysate, and a layered silicate. Achieved extremely high gas barrier film. In addition, the above-mentioned extremely excellent gas barrier properties are in a form in which a sealing layer is laminated on a gas barrier layer. A gas barrier layer using a polyvinyl alcohol-based resin can maintain excellent gas barrier properties even after being left in hot water. Achieving properties comparable to those of conventional vinylidene chloride coating films used as gas barriers. Industrial utilization price Therefore, the gas barrier film of the present invention is used for delicious foods starting from dry foods such as snacks, raw noodles, and intermediate moisture foods such as Japanese snacks with stuffing, soy sauce, pickles, and fish plates. , Ham, hot dog and other high-water food gas barrier film is extremely useful for a wide range of applications. Best Mode for Carrying Out the Invention The present invention will be described in the following examples and comparative examples, but the present invention is not limited to these examples. In addition, the physical properties of the films of the following examples and comparative examples were performed by the following methods. (1) The oxygen permeability Q was measured using J IS K7126 B as a reference, using an oxygen permeability measuring device (manufactured by Mocon Corporation; OX-TRAN100). The measurement conditions were a temperature of 23 t, a humidity of 90% RH on the substrate layer side, and a humidity of 90% RH on the gas barrier layer side. Humidity is adjusted by -28-1229036 V. Description of the invention (27) The precision humidity adjustment system RH-3S of the stand-by measuring instrument is adjusted. (2) Oxygen permeability Q after hot water treatment A bag having a size of 15 cm x 15 cm sealed with 200 ml of water is formed on the gas barrier film laminated with a sealing layer with the gas barrier layer as the inner surface. The bag was immersed in hot water at 90 ° C for 30 minutes and then subjected to hot water treatment. After the hot water treatment, the contents were directly discarded, the bag was washed with water, and the gas barrier film was fixed in the oxygen permeability measuring device within 10 minutes. The oxygen permeability measurement is based on the JIS K71 26 B method, using an oxygen permeability measuring device (manufactured by Mocon Corporation; OX-TRAN100). The measurement conditions were a gas flow rate of 20 ml / min, a temperature of 23 ° C, a humidity of 90% RH measured on the substrate layer, and a humidity of 90% RH on the seal layer side. Humidity is adjusted by Hitachi Meter Service Precision Humidity Adjustment System RH-3S. The gas barrier film treated with hot water was fixed, and the oxygen permeability measurement was started 10 minutes later. The oxygen permeability evaluation 1 hour after the measurement was started was taken as the oxygen permeability Q 'after the hot water treatment. (3) Coverability A test cover made by Koki Co., Ltd. was used, covered with a thermoplastic resin, and dried to form a gas barrier layer. Coating method: Photogravure coating method Drying method: Guide roller semi-circular hot-air jet nozzle spraying method (4) Radius Rg of scattering body by light scattering Scattering measurement device DYNA-100 manufactured by Otsuka Electronics Co., Ltd. V v scattering. Light source: 5mW He-Ne laser -29-1229036 V. Description of the invention (28) Angle range: 1. 5 ~ 30. Stepper angle: 0 · 5 ° ND filter: 0 · 1 Detector: Photon multiplier for photon calculation At this time, the transverse direction of the film (the direction perpendicular to the mechanical direction) and the polarizer of the light scattering measuring device, The polarization directions of the detection photons are the same, and the laser light is incident in the direction of the vertical film to measure the scattering intensity. The radius of revolution Rg of the scatterer is calculated using a guinea-pick plot attached to the software of the same machine, and the linear range of the small-angle side of the guinea-plot plot is similar by the least square method, and Rg is obtained by the degree of tilt. An arbitrary 15-point gas-barrier film was used as the average 値. (5) FE-TEM observation and FDS analysis After the film was embedded and hardened with epoxy resin, the ultra-thin slicer was used to take an ultra-thin slice with a thickness of 80 nm. The obtained ultra-thin section was observed by FE-TEM (electric field emission type transmission electron microscope Phi 1ips Electron Optics company Tecnai F20) having STEM (scanning transmission electron microscope) function. In addition, an EDS (energy dispersive X-ray analysis device) installed on the FE-TEM was used to plot the element dispersion concentration of C, 0, A1, and Si as the target elements and the element plotting the element dispersion concentration. (6) The small-angle X-ray scattering target distance dIP and dND are installed in a small-angle X-ray scattering measuring device in an X-ray scattering device JDX-3500 made by Japan Electronics Co., Ltd., and the small-angle X-ray scattering is measured by the following method. 0 -30-1229036 V. Description of the invention (29) Target ... Copper (Cu-Koc wire) Tube voltage and tube current: 40kV-400mA Monochromization: Ni filter 1st slit ·· 0. 30mmx 12mm 2nd gap: 0. 20mmx 12mm 3rd slot: use 4th slot: 0. 20mmx20mm 5th system seam: 0. 15mmx20mm Detector: Flasher X-ray incidence method: Transmission method (sample fixed 0 °) Measuring angle range: 2 0 = 0. 3 ~ 5. 0 ° segment angle: 0. 010 ° Counting time: 20 seconds The measurement of dIP is to make the direction of the gas barrier film consistent, cut into 15mmX 25 mm, and overlap to a thickness of 0. 8 ~ 1. 0 mm (here, 40 sheets), X-rays perpendicular to the film surface were incident (through incident), and small angle X-ray scattering IIP was measured. Then, the same number of sheets (here, 40 sheets) of the thermoplastic resin film of the base material layer (or the same material as the base material layer) were overlapped in the same manner, and the small angle X-ray scattering IIP was measured. . IIP is derived from IIP. The peak position of the through incident scattering plot of the obtained gas barrier layer was used to obtain the distance between the ranges. Find the average 値 of any 5 points. In addition, the measurement of dND is to make the direction of the gas barrier film consistent, cut into 5mm X 15 mm, and overlap to a thickness of 4 ~ 5mm (here, 200 sheets). Metalwork -31-1229036 V. Description of the invention (3 〇) Hold the film to fix the film smoothly, make the film surface (the long side of the film sample) parallel to the slit of the small-angle X-ray scattering device, and make the X-ray parallel to the film surface incident (edg e incidence), and measure the small angle X Line scattering IND. Then, the same number of sheets (here, 200 sheets) of the thermoplastic resin film of the base material layer (or the same material as the base material layer) were overlapped in the same manner, and the small-angle X-ray scattering INDQ was measured. The peak position of the edge incident scattering plot of the gas barrier layer obtained from the IIP (substrate film thickness / gas barrier film thickness) x IIP〇, and the range distance dND was obtained. Find the average 値 of any 5 points. Example 1 In a mixed solvent of 70 parts by weight of water and 30 parts by weight of ethanol, a polyvinyl alcohol having an average degree of polymerization of 1700 and an alkalinization rate of 98% or higher at a temperature of 70 ° C. was at a concentration of 6. 7% by weight was dissolved to obtain 6. 7% by weight solution (referred to as A solution). In a mixed solvent of 70 parts by weight of water and 30 parts by weight of ethanol, a concentration of 3. 3% by weight of montmorillonite as a layered silicate (manufactured by Gunimina Industrial Co., Ltd., Gnipia G), stirred and dispersed at 60 ° C to obtain a layered structure 3.3% by weight silicate dispersion solution (abbreviated as liquid B). A solution in which the above-mentioned liquids A and B were mixed at a ratio of 1: 1 by weight was subjected to a microdispersion treatment using a conflict-type high-pressure dispersing device (manufactured by Schiro Machinery, HJP-25030) to obtain a polyethylene-containing solution. Alcohol 3. 3% by weight and layered 1.7% by weight micro-dispersed solution of silicate. To this microdispersed solution was added a bead-like hydrogen ionized strongly acidic ion exchange resin, and the pH 値 was adjusted to -32-1229036. V. Description of the invention (31) 100 parts by weight of the pH 値 -adjusted microdispersed solution was added to For polyvinyl alcohol, the amount of silicon derived from silicon alkoxide (in terms of Si 02) is 150 parts by weight of tetraethoxysilane, and the mixture is stirred at room temperature for about 12 hours to hydrolyze the tetraethoxysilane. Then, foreign matter such as ion exchange resin or dust was removed by filtration to obtain a gas barrier coating agent. The pH 値 of the obtained gas barrier coating was 3 · 8. In addition, the weight ratio of polyvinyl alcohol / layered silicate in the gas barrier coating agent is 100/50, and the weight ratio of the layered oxalate to the silicon content of silicon alkoxide (in terms of SiO2) (The amount of sand from the layered cholate / sand oxide sand) is 0. 33. Corona discharge treated biaxially stretched polypropylene film with a thickness of 20 μηι is treated with a tackifier (made by Toyo Morton: AD33 5AE / CAT10L = 10 parts by weight / 1. 4 parts by weight, adjusted to a non-volatile content of 6% by weight in a mixed solvent of ethyl acetate / toluene = 1 part by weight / 1 part by weight) to dry the coating with a dry weight of 0. Covered at 3g / m2, dried in hot air at 100 ° C to obtain biaxially stretched polypropylene coated with a tackifying coating. Olefin film. The thickness of the gas barrier layer after the tackifier coating of the biaxially stretched polypropylene film covered with the tackifier coating is dried. The obtained gas barrier coating agent of 0 μm was dried in hot air at 120 ° C. Then, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. The FE-TEM photograph of the cross section of the gas barrier layer of the obtained gas barrier film is shown in Fig. 1, and the result of EDS analysis is shown in Fig. 2. It can be confirmed that layered silicon -33-1229036 V. Description of the invention (32) There is silicon alkoxide and / or its hydrolyzate between the layers of the acid salt. The measurement results of the obtained gas barrier film are shown in Table 1. Example 2 A tetraethoxysilane was prepared in the same manner as in Example 1 except that the amount of silicon derived from silicon alkoxide (in terms of SiO 2) was 127 parts by weight for 100 parts by weight of polyvinyl alcohol. Gas barrier coating agent. In addition, the weight ratio of polyvinyl alcohol / layered silicate in the gas barrier coating agent is 100/50, and the layered silicate is the silicon content of silicon alkoxide (in terms of Si02). The weight ratio (the amount of silicon from layered silicate / silicon alkoxide) is 0. 39. After a coating film was obtained in the same manner as in Example 1, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 3 A tetraethoxysilane was prepared in the same manner as in Example 1 except that the amount of silicon derived from silicon alkoxide (in terms of SiO 2) was 100 parts by weight for 100 parts by weight of polyvinyl alcohol. Gas barrier coating agent. In addition, the weight ratio of polyvinyl alcohol / layered silicate in the gas barrier coating agent is 100/50, and the weight ratio of the layered silicate to the silicon content of silicon alkoxide (equivalent to SiO2) (The amount of silicon derived from the layered silicate / silicon alkoxide) was 0. 50. After the coating film was prepared in the same manner as in Example 1, the obtained coating film was at -34-1229036. V. Description of the invention (33) Relative humidity Etching treatment was performed at 80% RH and 40 ° C for 4 days to obtain a gas barrier film. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or a hydrolyzate thereof existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 4 In Example 1, except that the A liquid and the B liquid were mixed at a ratio of 2/1 by weight, and tetraethoxysilane was added to 100 parts by weight of polyvinyl alcohol by the amount of silicon derived from silicon alkoxide ( Except for Si 02), except that it is 150 parts by weight, a gas barrier coating agent was obtained in the same manner as in Example 1. In addition, the weight ratio of polyvinyl alcohol / layered silicate in the gas barrier coating agent is 100/25, and the weight ratio of layered silicate to the silicon content of silicon alkoxide (in terms of SiO2) ( The amount of silicon from layered silicate / silicon alkoxide) is 0. 1 6. After a coating film was obtained in the same manner as in Example 1, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that the silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 5 In Example 1, except that the liquid A and the liquid B are made in a weight ratio of 1/1. The ratio of 7 is mixed, and the tetraethoxysilane is 100 parts by weight of polyvinyl alcohol, and the amount of silicon derived from silicon alkoxide (equivalent to SiO 2) is 150 parts by weight, and is the same as that in Examples 1 -35-1229036. V. Invention Explanation (34) A gas barrier coating agent was prepared in the same manner. In addition, the weight ratio of polyvinyl alcohol / layer silicate in the gas barrier coating agent is 1 00/83, and the weight ratio of the layer silicate to the silicon content of silicon alkoxide (in terms of SiO 2 conversion) (The amount of silicon derived from the layered silicate / silicon alkoxide) was 0.556. After the coating film was prepared in the same manner as in Example 1, the obtained coating film was etched at a relative humidity of 80% RH and 40 ° C. After 4 days of treatment, a gas barrier film was prepared. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 6 In Example 1, liquid A and liquid B were made at a weight ratio of 1/2. 5 was mixed, and in Example 1, it was the same as in Example 1 except that the amount of tetraethoxysilane to 100 parts by weight of polyvinyl alcohol was 150 parts by weight based on the amount of silicon derived from silicon alkoxide (Si02 equivalent). A gas barrier coating was obtained. In addition, the weight ratio of polyvinyl alcohol / layer silicate in the gas barrier coating agent is 1 00/1 25, and the weight of the layer silicate is based on the silicon content of the silicon alkoxide (in terms of SiO2). The ratio (the amount of silicon from the layered silicate / silicon alkoxide) is 0. 8 4. After a coating film was obtained in the same manner as in Example 1, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. -36-1229036 V. Explanation of the invention (35) The gas barrier layer of the obtained gas barrier film was analyzed by FE-TEM and EDS. It can be confirmed that there is silicon alkoxide and / or its hydrolysis between the layers of layered silicate. Thing. The measurement results of the obtained gas barrier film are shown in Table 1. Example 7 In Example 1 except that polyvinyl alcohol having a weight average molecular weight of 4 million was added to a microdispersed solution containing polyvinyl alcohol and layered silicate, and In Example 1, a gas barrier coating agent and a gas barrier film were obtained in the same manner. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 8 In Example 1, in addition to a microdispersed solution containing polyvinyl alcohol and layered silicate, polyvinyl alcohol having an average molecular weight of 4 million for 100 parts by weight of polyvinyl alcohol was added, and A gas barrier coating agent was prepared in the same manner as in Example 1 except that the hydrogenated ionized strongly acidic ion exchange resin and 1N-nitric acid were added at a predetermined amount, and the mixture was stirred at room temperature for 1 hour to perform hydrolysis of tetraethoxysilane. The gas barrier coating has a pH of 2. 2. Using this gas barrier coating agent, a gas barrier film was obtained in the same manner as in Example 1. FE-TEM and EDS analysis results of the gas barrier layer of the obtained gas barrier film-37-1229036 V. Description of the invention (36) 'It can be confirmed that there is silicon alkoxide and / or its hydrolysis between the layers of layered silicate Thing. The measurement results of the obtained gas barrier film are shown in Table 1. Example 9 In Example 1, except that polyvinyl alcohol having a weight average molecular weight of 2 million for 100 parts by weight of polyvinyl alcohol was added to a microdispersed solution containing polyvinyl alcohol and layered silicate, and In Example 1, a gas barrier coating agent and a gas barrier film were obtained in the same manner. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 10 Except that the gas barrier coating agent obtained in Example 7 was coated with a gas barrier layer having a thickness of 2 · 0 μm after drying, the same as that in Example 1 was used for the thickening coating of the biaxially stretched polypropylene film coated with a thickening coating. A gas barrier film was prepared in the same manner as in Example 1 except that the layer was dried by hot air at 100 ° C. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 11 Except that the gas-barrier coating agent obtained in Example 7 was dried to have a thick gas-barrier layer -38-1229036 V. Description of the invention (37) 2. Ομιη was coated on the same tackifying coating of the biaxially stretched polypropylene film coated with the tackifying coating as in Example 1, hot air drying at 8 ° C, and etching at a relative humidity of 80% RH and 40 ° C After 7 days of treatment, a gas barrier film was prepared in the same manner as in Example 1. As a result of gas barrier layer analysis of the obtained gas barrier film, FE-TEM and EDS analysis were performed, and it was confirmed that an alkane was present between the layers of the layered silicate Silicon oxide and / or its hydrolysate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 12 Except that the gas barrier coating agent obtained in Example 7 was dried, the gas barrier layer was thick 2. 0 μηι was coated on the same tackifying coating of the biaxially stretched polypropylene film coated with the tackifying coating as in Example 1, dried by hot air at 100 ° C, and at a relative humidity of 80% RH and 23 ° C A gas barrier film was produced in the same manner as in Example 1 except that the etching treatment was performed for 14 days. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 13 A corona discharge-treated surface of a corona discharge-treated biaxially stretched polypropylene film having a thickness of 20 μm was coated with a tackifier (manufactured by Toyo Morton, AD3 3 5AE / CAT10L = 10 parts by weight / 1 part by weight, adjusted to a non-volatile content of 6% by weight in a mixed solvent of ethyl acetate / toluene = 1 part by weight / 1 part by weight -39- 1229036 5. Inventive Note (38)) to thicken the coating Dry weight is 0. Covered at 3g / m2, dried by hot air at 10 ° C to obtain a biaxially stretched polypropylene film coated with a tackifying coating. The tacky coating of the biaxially stretched polypropylene film coated with a tackifying coating After the coating is dried, the thickness of the gas barrier layer is 2. The gas barrier coating agent obtained in Example 7 at 0 μm was dried in hot air at 120 ° C to prepare a coating film. Then, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. The gas barrier layer of the obtained gas barrier film was analyzed by FE-TEM and EDS. It was confirmed that the gas barrier layer existed between the layers of the layered silicate. In the presence of silicon alkoxide and / or its hydrolyzate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 14 4 A corona discharge-treated surface of a corona discharge-treated biaxially stretched polypropylene film having a thickness of 15 μΐΏ was coated with a tackifier (manufactured by Mitsui Takeda Chemical Co., A32 10 / A3070 = 3 parts by weight / 1 part by weight 2, adjusted to ethyl acetate to non-volatile content of 6% by weight) to dry weight of the thickening coating is 0. Covered at 3g / m2, dried in hot air at 100 ° C to obtain a biaxially stretched polypropylene film coated with a tackifier coating. The thickness of the gas barrier layer after the drying of the tackifying coating of the biaxially stretched polypropylene film covered with the tackifying coating is 2. The gas barrier coating agent obtained in Example 7 at 0 μm was dried in hot air at 100 ° C to prepare a coating film. Then, the obtained coating film was subjected to an etching treatment at a relative humidity of 80% RH and 40 ° C for 4 days to obtain a gas barrier film. -40-1229036 V. Description of the invention (39) The results of FE-TEM and EDS analysis of the gas barrier layer of the obtained gas barrier film 'can confirm the existence of silicon alkoxide and / or its hydrolysis between the layers of layered silicate Thing. The measurement results of the obtained gas barrier film are shown in Table 1. Example 15 In Example 1, except that a bead-like hydrogen ionized strongly acidic ion exchange resin was added to a microdispersed solution containing polyvinyl alcohol and layered silicate, the pH 値 was adjusted to 3 · 0 'this pH 値To the adjusted microdispersion solution, a tetraethoxy sand compound with a silicon content (Si02 equivalent) derived from silicon alkoxide of 1,000 parts by weight for polyvinyl alcohol is 150 parts by weight, and at room temperature A gas barrier coating agent and a gas barrier film were prepared in the same manner as in Example 丨 except that the tetraethoxysilane was hydrolyzed by stirring for 2 hours. The pH of the obtained gas barrier coating agent was 3. 0. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 16 In Example 1, except that a bead-like hydrogenated strongly acidic ion exchange resin was added to a microdispersed solution containing polyvinyl alcohol and layered silicate, the pH was adjusted to 3. 0. The pH 値 adjusted microdispersion solution was added with tetraethoxysilane at a room temperature of 150 parts by weight based on 100 parts by weight of polyvinyl alcohol derived from silicon alkoxide (Si02 equivalent). A gas-barrier coating -41-1229036 was prepared in the same manner as in Example 1 except that the tetraethoxysilane was hydrolyzed by stirring for 20 hours. 5. Description of the invention (40) and a gas-barrier film. The pH value of the obtained gas barrier coating agent was 3. 0. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 17 In Example 15, a bead-like hydrogen ionized strong acidic ion exchange resin was added to a microdispersion solution containing polyvinyl alcohol and layered silicate, and the pH was adjusted to 2. A gas barrier coating agent and a gas barrier film were prepared in the same manner as in Example 15 except for Example 4. The pH 値 of the obtained gas barrier coating was 2. 5. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 18 In Example 15 except that a bead-like hydrogen ionized strongly acidic ion exchange resin was added to a microdispersion solution containing polyvinyl alcohol and layered silicate, and the pH was adjusted to 2. 4. A gas-barrier coating agent and a gas-barrier film were prepared in the same manner as in Example 15 except that polyvinyl alcohol having a weight average molecular weight of 4 million was added to 100 parts by weight of polyvinyl alcohol. The pH of the obtained gas barrier coating agent was 2. 5. The gas barrier layer of the obtained gas barrier film was analyzed by FE-TEM and EDS, and it was confirmed that silicon alkoxide and / or its water existed between the layers of the layered silicate -42-1229036 V. Description of the invention (41) Solution. The measurement results of the obtained gas barrier film are shown in Table 1. Example 19 In Example 1, a bead-like hydrogen ionized strong acidic ion exchange resin was added to a microdispersed solution containing polyvinyl alcohol and layered silicate, and the pH was adjusted to 2. 4. Add 100 parts by weight of polyvinyl alcohol with an average molecular weight of 4 million to 100 parts by weight of polyvinyl alcohol. To the microdispersion solution adjusted by pH 値 and added with polyvinyl alcohol, a tetraethoxy group containing 230 parts by weight of silicon derived from silicon alkoxide (based on SiO2) for 1,000 parts by weight of polyvinyl alcohol was added. Silane was stirred at room temperature for 2 hours to perform hydrolysis of tetraethoxysilane, and a gas barrier coating agent was obtained in the same manner as in Example 1. The pH 値 of the obtained gas barrier coating was 2. 5. In addition, the weight ratio of polyvinyl alcohol / layer silicate in the gas barrier coating agent is 100/50, and the weight ratio of the layer silicate to the amount of silicon derived from silicon alkoxide (in terms of SiO2) (The amount of silicon from layered silicate / silicon alkoxide) is 0. twenty two. Using this gas barrier coating agent, the thickness of the gas barrier layer after drying was the same as in Example 1 to be 2. A tackifying coating of a biaxially stretched polypropylene film coated with a tackifying coating agent at 0 μm was dried at 100 ° C. in hot air. Then, the obtained coating film was subjected to an etching treatment at 80% RH and 40 ° C to obtain a gas barrier film. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. -43- 1229036 V. Description of the invention (42) The measurement results of the obtained gas barrier film are shown in Table 1. Example 20 The same as Example 19 was added to Example 19, except that 100 parts by weight of polyvinyl alcohol was converted to 320 parts by weight of tetraethoxysilane based on the amount of silicon derived from silicon alkoxide (SiO 2 equivalent). A gas barrier coating agent and a gas barrier film were prepared. Furthermore, the weight ratio of polyvinyl alcohol / layer silicate in the gas barrier coating agent was 100/50, and the amount of silicon derived from silicon alkoxide ( In terms of si〇2), the weight ratio of the layered silicate (the amount of silicon from the layered silicate / silicon alkoxide) is 0. 16. The gas barrier layer of the obtained gas barrier film was analyzed by fe-TEM and EDS. As a result, it was confirmed that silicon alkoxide and / or its hydrolysate existed between the layers of the layered silicate. The measurement results of the obtained gas barrier film are shown in Table 1. Example 21 The solution in which the A liquid and the B liquid were mixed in a weight ratio of 2/1 in Example 1 was finely dispersed by a conflict-type high-pressure dispersing device ((·) Schiro Machinery Co., Ltd., HJP-25030). Chemical treatment to produce 4. 4% by weight of polyvinyl alcohol and 1. 1% by weight micro-dispersed solution of layered silicate. To the microdispersed solution was added a bead-like hydrogen ionized strongly acidic ion exchange resin, and the pH was adjusted to 2. 6. Add 1 part by weight of polyvinyl alcohol with an average molecular weight of 4 million to 100 parts by weight of polyvinyl alcohol. In this pH-adjusted microdispersed solution with polyvinyl alcohol added, the amount of silicon derived from silicon alkoxide (equivalent to SiO 2) for 300 parts by weight of polyvinyl alcohol is 300 weight 1229036 V. Description of the invention (43) Part was added and stirred at room temperature for 2 hours to perform hydrolysis of tetraethoxysilane, and a gas barrier coating agent was prepared in the same manner as in Example 1. The pH value of the obtained gas barrier coating agent was 2. 8. In addition, the weight ratio of polyvinyl alcohol / layer silicate in the gas barrier coating agent is 100/25, and the weight ratio of layer silicate to the amount of silicon derived from silicon alkoxide (in terms of SiO2) ( The amount of silicon from layered silicate / silicon alkoxide) is 0. 08. Using a gas barrier coating, the thickness of the gas barrier layer after drying is 2. 0 μιη was coated with the same tackifying coating of the biaxially stretched polypropylene film coated with a tackifying coating agent as in Example 1, and dried by hot air at 10 ° C. to prepare a coating film. Then, the obtained coating film was relatively A gas barrier film was prepared after performing an etching treatment at a humidity of 80% RH and 4 ° C for 4 days. As a result of analyzing the gas barrier layer of the obtained gas barrier film by FE-TEM and EDS, it was confirmed that the layer was a silicate Silica alkoxide and / or its hydrolysate exist between the layers. The measurement results of the obtained gas barrier film are shown in Table 1. Example 22 Except the use of the gas barrier coating agent obtained in Example 19, the resistance after drying was used. The thickness of the gas layer is 1.0 μm, and the same film as in Example 1 is coated on the outside of the tackifying coating of the biaxially stretched polypropylene film coated with a tackifying coating agent, and a coated film is prepared in the same manner as in Example i 9. Analysis of gas barrier layer of gas film by FE-TEM and EDS -45-1229036 V. Description of the invention (44) As a result, it can be confirmed that there is silicon alkoxide and / or its hydrolyzate between the layers of layered silicate The measurement results of the obtained gas barrier film are shown in Table 1. Comparative Example 1 In the liquid A of Example 1, a bead-like hydrogen ionization strongly acidic ion exchange resin and tetraethoxylate in an amount of 127 parts by weight based on the amount of silicon derived from silicon alkoxide (in terms of SiO2) for 100 parts by weight of polyvinyl alcohol were added. Hydrolyze the tetraethoxysilane at room temperature and stir until homogeneous. Then, remove foreign matters such as ion exchange resin or dust by filtration to obtain a gas barrier coating agent. The obtained gas barrier coating agent It is a transparent liquid with a pH of 4. 2. Using this gas barrier coating agent, a gas barrier film was prepared in the same manner as in Example 1. The measurement results of the obtained gas barrier film are shown in Table 1. Comparative Example 2 Except that the microdispersed solution containing polyvinyl alcohol and layered silicate obtained in Example 1 was dried and the thickness of the gas barrier layer was 2 · 0 μm, it was coated with the same coating as the viscosity-increasing coating agent in Example 1. A gas-barrier film was prepared in the same manner as in Example 1 except that the tackifying coating of the biaxially stretched polypropylene film was dried by hot air at 120 ° C. The measurement results of the obtained gas barrier film are shown in Table 1. Comparative Example 3 40 parts by weight of 1N-hydrochloric acid was added to 100 parts by weight of tetraethoxysilane, and the mixture was stirred at room temperature to hydrolyze the tetraethoxysilane, thereby preparing a tetraethoxysilane hydrolysis solution. -46-1229036 containing polyvinyl alcohol and layered silicate obtained in Example 1 V. Description of the invention (45) The microdispersed solution was added with the amount of sand derived from alkoxide sand for 00 parts by weight of polyvinyl alcohol (Si02 conversion) is 27 parts by weight of the tetraethoxysilane hydrolyzate solution 'to prepare a mixed solution made of polyvinyl alcohol, layered silicate, and tetraethoxysilane hydrolysate. Using this mixed solution, a gas barrier film was obtained in the same manner as in Example i. Table 1 shows the measurement results of the resistive heat-generating films. Comparative Example 4 In Example 1, tetraethoxysilane was added in an amount of 530 parts by weight based on the amount of silicon derived from silicon alkoxide (in terms of Si02) to 100 parts by weight of polyvinyl alcohol. During the hydrolysis of oxysilane, precipitates are generated, and a gas barrier coating cannot be obtained. -47-1229036 V. Description of the invention (46) Table 1 Example Oxygen permeability Q (ml / m2 · day · atm) 2. 5 / (γ / 90 + α) (ml / m 2 day atm) Rg (μηι) ^ ND (nm) dip (nm) Example 10. twenty one. 1 1. 8 5. 9 6. 4 Example 2 0. 8 1. 1 1. 9 5. 9 6. 1 Example 3 1. 1 1. 1 2. 3 6. 0 6. 0 EXAMPLE 4 0. 9 1. 1 1. 9 6. 0 6. 0 Example 5 1. 0 1. 1 1. 9 6. 1 6. 2 Example 6 1. 0 1. 1 1. 9 6. 1 6. 1 Example 7 0. 1 1. 1 1. 7 5. 6 6. 5 Example 80. 8 1. 1 2. 1 5. 8 6. 4 Example 9 0. twenty one. 1 1. 8 5. 8 6. 4 Example 10 0. twenty one. 1 1. 8 5. 6 6. 6 Example 11 0. 4 1. 1 1. 8 5. 7 6. 3 Example 12 0. 4 1. 1 1. 8 5. 7 6. 2 Example 13 0. 1 1. twenty one. 7 5. 6 6. 4 Example 14 0. 3 1. 1 1. 8 5. 9 6. 4 Example 15 0. twenty one. 1 1. 8 5. 5 6. 3 Example 16 0. 3 1. 1 1. 9 6. 0 6. 3 Example 17 0. 1 1. 1 1. 8 5. 5 6. 4 Example 18 0. 1 1. 1 1. 8 5. 5 6. 4 Example 19 0. twenty one. 1 1. 7 5. 3 6. 1 Example 20 0. twenty one. 1 1. 7 5. 6 6. 3 Example 21 1. 1 1. 1 1. 9 6. 0 6. 0 Example 22 0. 3 2. 0 1. 8 5. 3 6. 1 Comparative Example 1 1. 1 3. 3 6. 0 Comparative Example 2 40 1. 1 3. 2 Comparative Example 3 6. twenty one. 1 2. 8 7. 8 8. 2 *: No peak position below 10 nm was detected -48-1229036 V. Description of the invention (47) Example 23 The gas barrier layer of the gas barrier film obtained in Example 1 was covered with a dry weight of 2 g / m2. Adhesive for dry lamination (manufactured by Toyo Morton Co., Ltd. TM329 / CAT-8B = 1 part by weight / 1 part by weight with ethyl acetate solvent adjusted to 10% by weight non-volatile) at 90 ° C After drying for 2 minutes, a 40 μm non-stretched polyethylene film was laminated on the adhesive layer for the dry laminate to prepare a non-stretched polyethylene film laminated gas barrier film. The measurement results of the obtained gas barrier film are shown in Table 2. Example 24 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 2 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 25 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 3 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 26 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 4 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 27 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 5 was used. -49- 1229036 V. Description of the invention (48) The measurement results of the obtained gas barrier film are shown in Table 2. Example 28 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 6 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 29 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 7 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 30 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 8 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 31 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 9 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 32 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 10 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 33 The same as Example 2 except that the gas barrier film obtained in Example 11 was used. -50-1229036 V. Description of the invention (49) A non-stretched polyethylene film laminated gas barrier film was prepared. The measurement results of the obtained gas barrier film are shown in Table 2. Example 34 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 12 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 35 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 13 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 36 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 14 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 37 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 15 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 38 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 16 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Examples 39 -51-1229036 5. Description of the invention (50) Except that the gas barrier film obtained in Example 17 was used, a non-stretched polyethylene film laminated gas barrier film was prepared in the same manner as in Example 23. The measurement results of the obtained gas barrier film are shown in Table 2. Example 40 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 18 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 4 1 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 2 3 except that the gas barrier film obtained in Example 19 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 42 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 20 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 43 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Example 21 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Example 44 A gas barrier film without a stretched polyethylene film was produced in the same manner as in Example 2 3, except that the gas barrier film obtained in Example 2 2 was used. The measurement results of the obtained gas barrier film are shown in Table 2. -52- 1229036 V. Description of the invention (51) Comparative example 5 A non-stretched polyethylene film laminated gas barrier film was produced in the same manner as in Example 2 except that the gas barrier film obtained in Comparative Example 1 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Comparative Example 6 A non-stretched polyethylene film-laminated gas barrier film was produced in the same manner as in Example 23 except that the gas barrier film obtained in Comparative Example 2 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Comparative Example 7 A non-stretched polyethylene film-laminated gas barrier film was produced in the same manner as in Examples 2 and 3 except that the gas barrier film obtained in Comparative Example 3 was used. The measurement results of the obtained gas barrier film are shown in Table 2. Reference Example 1 On a vinylidene chloride-coated layer of 22 μm vinylidene chloride-coated OPP film (Sinasi (transliteration) KOPP product name: ΗΒ60) manufactured by Laisiru Chemical Industries, the same dryness as in Example 23 An adhesive for lamination was laminated and dried, and a 40 μm non-stretched polyethylene film was laminated on the surface of the adhesive to obtain a non-stretched polyethylene film laminated gas barrier film. The measurement results of the obtained gas barrier film are shown in Table 2. -53- 1229036 V. Description of the invention (μ) Table 2 Oxygen permeability Q '100 / (γ / 90 + α) dND dIP (ml / m2 · day · atm) (ml / m2 · day atm) (nm) (nm) Example 23 8 37 5. 9 6. 4 Example 24 13 37 5. 9 6. 1 Example 25 20 37 6. 0 6. 0 Example 26 15 37 6. 0 6. 0 Example 27 20 37 6. 1 6. 2 Examples 28 20 37 6. 1 6. 1 Example 29 5 37 5. 6 6. 5 Example 30 10 37 5. 8 6. 4 Examples 31 7 37 5. 8 6. 4 Examples 32 5 37 5. 6 6. 6 Example 33 6 37 5. 7 6. 3 Examples 34 6 37 5. 7 6. 2 Examples 35 5 38 5. 6 6. 4 Examples 36 8 38 5. 9 6. 4 Example 37 3 37 5. 5 6. 3 Examples 38 25 37 6. 0 6. 3 Example 39 3 37 5. 5 6. 4 Example 40 3 37 5. 5 6. 4 Example 41 1 37 5. 3 6. 1 Example 42 9 37 5. 6 6. 3 Examples 43 21 37 6. 0 6. 0 Example 44 2 59 5. 3 6. 1 Comparative Example 5 200 37 6. 0 Comparative Example 6 500 37 Comparative Example 7 90 37 7. 8 8. 2 Reference example 1 5 37 — — *: No peak position below 10 nm was detected -54-