200906614 九、發明說明 【發明所屬之技術領域】 本發明係關於具有透明性，且氧、水蒸氣等之阻氣性 ，特別於高濕度下之阻氣性優良之阻氣薄膜等的阻氣性層 合物。 【先前技術】 近年，作爲對於氧或水蒸氣等之阻擋性材料，乃注目 於薄膜基材將氧化矽、氧化鋁等之無機氧化物，以真空蒸 鍍法、濺鍍法、離子電鍍法、化學氣相成長法等所形成的 透明阻氣薄膜。 此透明阻氣薄膜，一般係爲在透明性、剛性優良的雙 軸延拉聚酯薄膜所構成的基材面上，蒸鍍無機氧化物的薄 膜，故就其原樣下，蒸鍍層於使用時的摩擦等弱，使用作 爲包裝用薄膜時，於後加工之印刷和層合時，或於內容物 之充塡時，經由磨擦和延伸令無機氧化物產生裂痕且阻氣 性降低。 另一方面，已提案將具有阻氣性之聚乙烯醇、乙烯· 乙烯醇共聚物層合至雙軸延拉薄膜基材的方法（例如，專 利文獻1 )，或將聚乙烯醇與聚（甲基）丙烯酸之組成物 覆被至雙軸延拉薄膜基材的方法（例如，專利文獻2)。 但是，層合聚乙烯醇而成的阻氣薄膜，於高濕度下之阻氣 性降低，且聚乙烯醇與聚（甲基）丙烯酸之組成物，於充 分進行酯化，提高薄膜之阻氣性上，必須於高溫下長時間 -5- 200906614 加熱’於生產性上具有問題’又，於高濕度下之阻氣性不 夠充分。又’經由高溫下長時間反應令薄膜著色，損害外 觀，故於食品包裝用上必須加以改善。 另一方面，聚乙烯醇與聚（甲基）丙烯酸之組成物於 酯化上必須於高溫下長時間反應，故提案於聚丙烯酸中添 加異氰酸酯化合物等之交聯劑成分的方法（例如，專利文 獻3 )，並進一步與金屬離子反應的方法（例如，專利文 獻4)等，但於此類方法中，以交聯劑成分將聚丙烯酸交 聯上，亦如實施例所記載般，必須於1 80〜200 °C下高溫處 理5分鐘。 更且，於基材層（X )中，含有紅外線吸收光譜中 1700 cm — 1附近之羧酸基uC = 0爲基準的吸光度A〇與1520 cm — 1附近之羧酸酯離子之i；C = 0爲基準的吸光度A之比（ A0/A )爲未達0.25之不飽和羧酸化合物多價金屬鹽之聚合 物（a)的層（Y)所構成的阻氣薄膜，但進一步追求提高 阻氣性（專利文獻5 )。 專利文獻1 :特開昭6 0 - 1 5 7 8 3 0號公報（申請專利範圍 ) 專利文獻2 :專利第3203287號公報（申請項1 ) 專利文獻3:特開2001-310425號公報（申請項1 '實 施例1 ) 專利文獻4:特開2003-171419號公報（申請項卜表1 專利文獻5 : W02005/108440 (申請項1) 200906614 【發明內容】 (發明所欲解決之課題） 於是，本發明爲以取得具有透明性，且氧、二氧化碳 氣體、水蒸氣等之阻氣性’特別於高濕度下之阻氣性優良 之阻氣薄膜等的阻氣性層合物爲其目的。 (解決課題之手段） 本發明爲例如由以下之（1 )〜（5 )所構成。 (1 ) 一種阻氣性層合物，其特徵爲對基材層（X )層 合至少二層含有不飽和羧酸化合物多價金屬鹽之聚合物（ a )的層（Y )。 (2 )如（1 )記載之阻氣性層合物，其中，該層（Y )之至少一層爲含有乙烯醇系聚合物（b)。 (3 )如（1 )或（2 )記載之阻氣性層合物，其中， 於該基材層（X)與該層（Y)之間，該層（Y)與該層（ Y )之間或層（Y )之最外側，再層合無機蒸鍍層（Z )。 (4 )如（2 )或（3 )記載之阻氣性層合物，其中’ 該層（Υ)之多數層中的二層爲相互鄰接，其一層（Υ) 之乙烯醇系聚合物（b)的含有比例爲比另一層（γ)之乙 烯醇系聚合物的含有比例低。 (5 )如（1 )〜（4 )中任一項之阻氣性層合物，其 中’於該基材層（X)之反側表面再層合保護層（U)。 200906614 (發明之效果） 若根據本發明，經由使用二層以上含有不飽和羧酸化 合物多價金屬鹽之聚合物（a )的層（Y )所構成的阻氣性 層’作爲阻氣薄膜等之阻氣性層合物，不僅可取得高濕度 下之阻氣性特別優良之薄膜等之層合物，並且將此等層作 成含有不飽和羧酸化合物多價金屬鹽之聚合物（a)及乙 烯醇系聚合物（b )的層（Y )，則不僅可提供阻氣性，且 亦可提供耐衝擊性優良之阻氣薄膜等之阻氣性層合物。 【實施方式】 阻氣薄膜等之阻氣性層合物 本發明所用之阻氣薄膜等之阻氣性層合物，係關於基 材層（X)具有至少二層以上含有不飽和羧酸化合物多價 金屬鹽之聚合物（a)的層（Y)爲其特徵之阻氣薄膜等的 阻氣性層合物。 本發明之阻氣性層合物中，阻氣薄膜之厚度爲根據用 途而取得各種決定。通常，基材層（X)之厚度爲5〜5〇〇 較佳爲5〜100/zm，更佳爲9〜20ym’含有不飽和 羧酸化合物多價金屬鹽之聚合物（a)之層（Y)厚度爲 0-01〜100μ m，較佳爲0.05〜50/z m，更佳爲〇.1〜1〇# m ，又，使用無機蒸鍍層（Z)時其厚度爲0.001〜1〇ym’ 較佳爲0.005〜5// m，阻氣薄膜全體的厚度爲20〜750// m ，更佳爲25〜430 nm之範圍。 200906614 基材層（x) 本發明之阻氣性層合物中，構成阻氣薄膜之基材層（ X )，可無特別限定使用熱可塑性樹脂所構成的薄膜、薄 片、膠帶等。熱可塑性樹脂爲各種公知的熱可塑性樹脂， 可例示例如，聚烯烴（聚乙烯、聚丙烯、聚4-甲基-1-戊烯 、聚丁烯等）、聚酯（聚對苯二甲酸乙二酯、聚對苯二甲 酸丁二酯、聚萘二甲酸乙二酯等）、聚醯胺（尼龍-6、尼 龍-66、聚己二醯間苯伸二甲胺等）、聚氯乙烯、聚醯亞 胺、乙烯•醋酸乙烯酯共聚物或其鹼化物、聚乙烯醇、聚 丙烯腈、聚碳酸酯、聚苯乙烯、離聚物、或其混合物等。 其中，聚丙烯、聚酯、聚醯胺等爲延伸性、透明性良好之 熱可塑性樹脂爲佳，且特別以聚對苯二甲酸乙二酯及聚萘 二曱酸乙二酯等之聚酯因阻氣性、耐熱性等優良’故爲佳 〇 本發明之較佳態樣之一爲基材層（X)爲含有無機微 粒子之層的阻氣薄膜。 含有無機微粒子之基材層（X-1) 含有無機微粒子之基材層（X-1 ) ’通常配合〇.5〜10 重量％無機微粒子之丙烯系聚合物所構成的層爲佳。丙烯 系聚合物除了丙烯單聚物以外’可使用丙烯作爲主成分之 與乙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯等之烯 烴的二元至三元無規共聚物、分段共聚物等。無機微粒子 若其平均粒徑爲〇」〜1 ο V m左右，則無特別限定可利用。 -9- 200906614 可列舉例如，碳酸鈣、二氧化鈦、硫酸鋇、硫酸鎂、二氧 化矽、雲母、合成雲母、明礬、沸石等。彼等視需要亦可 將表面以各種聚合物予以塗敷。 此等無機微粒子之形狀可利用球狀、板狀、鱗片狀、 針狀等各種縱橫比之物質。 此等基材層（X)可使用無延拉，至少於單軸方向上 延伸者等之任一者，且經延拉之基材層爲耐熱性、剛性、 透明性及阻氣性優良。又，此等基材層（X)爲了改良與 層（Y)的接黏性，亦可將其表面，例如，進行電暈處理 、火焰處理、電漿處理、塗底處理、電漿塗敷處理、火焰 處理等之表面活化處理。 含有聚合物（a)之層（Y) 於基材層（X)之單面或兩面至少設置2層以上的層（ Y)、以含有不飽和羧酸化合物多價金屬鹽之聚合物（a) 的層（Y )爲佳。 不飽和羧酸化合物多價金屬鹽之聚合物（a) 不飽和羧酸化合物多價金屬鹽之聚合物（a )爲經由 令不飽和羧酸多價金屬鹽聚合而取得。 不飽和羧酸化合物 形成聚合物（a )所用之不飽和羧酸化合物多價金屬 鹽的不飽和羧酸化合物，爲丙烯酸、甲基丙烯酸、順丁烯 -10- 200906614 二酸、衣康酸等之具有α、/3 -乙烯性不飽和基的羧酸化 合物，聚合度爲未達20，較佳爲單體或聚合度1〇以下之聚 合物。使用聚合度爲超過20的聚合物（高分子化合物）時 ，擔心與後述之多價金屬化合物無法完全形成鹽，其結果 ，擔心該金屬鹽聚合所得之層於高濕度下的阻氣性差。此 等不飽和羧酸化合物可爲一種且亦可爲二種以上之混合物 〇 此等不飽和羧酸化合物中，亦以單體爲多價金屬化合 物可輕易形成完全中和之鹽，將該鹽聚合所得之聚合物層 於基材層的至少單面層合而成之阻氣薄膜等之阻氣性層合 物，因爲於高濕度下之阻氣性特別優良故爲佳。 多價金屬化合物 形成本發明之不飽和羧酸化合物多價金屬鹽之成分的 多價金屬化合物，係爲屬於周期表之2Α〜7Α族、1Β〜3Β 族及8族的金屬及金屬化合物，具體而言，爲鎂（Mg)、 鈣（Ca)、緦（Sr)、鋇（Ba)、鐵（Fe)、鈷（Co)、 鎳（Ni ) '銅（Cu )、鋅（Zn )、鋁（A1 )等之二價以上 的金屬，此等金屬的氧化物、氫氧化物、齒化物、碳酸鹽 、磷酸鹽、亞磷酸鹽、次磷酸鹽、硫酸或亞硫酸鹽等。此 等金屬化合物中，亦以二價之金屬化合物爲佳，特別以氧 化鎂、氧化鈣、氧化鋇、氧化鋅、氫氧化鎂、、氫氧化鈣 、氫氧化鋇、氫氧化鋅等爲佳。使用此等二價金屬化合物 時，與前述不飽和羧酸化合物之鹽進行聚合所得膜於高濕 -11 - 200906614 度下的阻氣性特優。此等多價金屬 ，且僅使用一種亦可，亦可倂用二 化合物亦以Mg、Ca、Zn、Ba及A1， 不飽和羧酸化合物多價金屬鹽 構成本發明所用之不飽和羧酸 合物（a )之成分的不飽和羧酸化 前述聚合度爲未滿20之不飽和羧酸 化合物之鹽。此等不飽和羧酸化合 且亦可爲二種以上之k合物。此類 金屬鹽中，特別以（甲基）丙烯酸 熱水性優良故爲佳。 本發明中含有聚合物（a)之乃 明目的之範圍中，亦可含有聚乙燒 物、聚乙烯吡咯烷酮、聚乙烯基乙 乙基亞胺、澱粉、阿拉伯膠、甲基 物、丙烯酸酯聚合物、乙烯•丙儲 酯、乙烯•醋酸乙烯酯共聚物、聚 高分子量化合物等、滑劑、增滑劑 、防霧劑、顏料、染料、無機或有 劑，且爲了改良與後述基材之濕潤 有各種界面活性劑等。此等其他成 〇。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于Laminate. [Prior Art] In recent years, as a barrier material for oxygen or water vapor, attention has been paid to an inorganic oxide such as cerium oxide or aluminum oxide on a film substrate by vacuum evaporation, sputtering, ion plating, or the like. A transparent gas barrier film formed by a chemical vapor phase growth method or the like. The transparent gas barrier film is generally formed by vapor-depositing an inorganic oxide film on a substrate surface composed of a biaxially stretched polyester film excellent in transparency and rigidity, so that the vapor deposition layer is used as it is. When the film is used as a film for packaging, when printing and lamination are performed in post-processing, or when the content is filled, cracks are generated in the inorganic oxide via friction and stretching, and gas barrier properties are lowered. On the other hand, a method of laminating a gas barrier polyvinyl alcohol, an ethylene vinyl alcohol copolymer to a biaxially stretched film substrate (for example, Patent Document 1), or a polyvinyl alcohol and a poly(polyethylene) has been proposed. A method of coating a composition of a methyl methacrylate onto a biaxially stretched film substrate (for example, Patent Document 2). However, the gas barrier film formed by laminating polyvinyl alcohol has a low gas barrier property under high humidity, and the composition of polyvinyl alcohol and poly(meth)acrylic acid is sufficiently esterified to increase the gas barrier of the film. Sexually, it must be heated at a high temperature for a long time -5 - 200906614 to 'have problems in productivity', and the gas barrier properties under high humidity are not sufficient. Further, the film is colored by a long-term reaction at a high temperature, which impairs the appearance, and therefore must be improved in food packaging. On the other hand, since the composition of polyvinyl alcohol and poly(meth)acrylic acid must be reacted at a high temperature for a long period of time in esterification, a method of adding a crosslinking agent component such as an isocyanate compound to polyacrylic acid is proposed (for example, a patent) Document 3), and a method of further reacting with a metal ion (for example, Patent Document 4), etc., but in such a method, the polyacrylic acid is crosslinked by a crosslinking agent component, as described in the examples, 1 80~200 °C for 5 minutes at high temperature. Further, in the base material layer (X), the absorbance A 〇 based on the carboxylic acid group uC = 0 in the vicinity of 1700 cm -1 in the infrared absorption spectrum and the carboxylate ion in the vicinity of 1520 cm -1; The ratio of the absorbance A of the reference 0 (A0/A) is a gas barrier film composed of the layer (Y) of the polymer (a) of the polyvalent metal salt of the unsaturated carboxylic acid compound of less than 0.25, but further improvement is sought. Gas barrier property (Patent Document 5). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2001-310425 (Application No.) [Embodiment 1] Patent Document 4: JP-A-2003-171419 (Application No. 1) Patent Document 5: W02005/108440 (Application 1) 200906614 [Summary of the Invention] The present invention is directed to a gas barrier laminate which is excellent in gas barrier properties such as oxygen, carbon dioxide gas, and water vapor, and which is excellent in gas barrier properties under high humidity. (Means for Solving the Problem) The present invention is constituted, for example, by the following (1) to (5). (1) A gas barrier layer characterized by laminating at least two layers of a base material layer (X) A layer (Y) of the polymer (a) of the polyvalent metal salt of the unsaturated carboxylic acid compound. (2) The gas barrier laminate according to (1), wherein at least one layer of the layer (Y) contains ethylene. (3) The gas barrier laminate according to (1) or (2), wherein the base is Between the layer (X) and the layer (Y), between the layer (Y) and the layer (Y) or at the outermost side of the layer (Y), the inorganic vapor-deposited layer (Z) is laminated. (4) (2) The gas barrier layered composition according to (3), wherein two of the plurality of layers of the layer are adjacent to each other, and the proportion of the vinyl alcohol polymer (b) of one layer (Υ) is The gas barrier layer of any one of (1) to (4), wherein the substrate layer (X) The protective layer (U) is laminated on the reverse side surface. 200906614 (Effect of the invention) According to the present invention, a layer (Y) of a polymer (a) containing two or more layers of a polyvalent metal salt of an unsaturated carboxylic acid compound is used. The gas barrier layer formed as a gas barrier layer such as a gas barrier film can obtain not only a laminate of a film excellent in gas barrier properties under high humidity but also such a layer. The polymer (a) of the polyvalent metal salt of the saturated carboxylic acid compound and the layer (Y) of the vinyl alcohol polymer (b) provide not only gas barrier properties but also excellent impact resistance. The gas barrier layer of a gas barrier film or the like. The gas barrier layer of the gas barrier film or the like used in the present invention relates to a substrate layer ( X) a gas barrier layer having a layer (Y) of at least two or more layers of a polymer (a) containing a polyvalent metal salt of an unsaturated carboxylic acid compound, and a gas barrier film characterized by the gas barrier film of the present invention. In the laminate, the thickness of the gas barrier film is determined depending on the application. Usually, the thickness of the substrate layer (X) is 5 to 5 Å, preferably 5 to 100 / zm, more preferably 9 to 20 ym. The layer (Y) of the polymer (a) containing a polyvalent metal salt of an unsaturated carboxylic acid compound has a thickness of from 0 to 100 μm, preferably from 0.05 to 50/zm, more preferably 〇.1 to 1〇# m Further, when the inorganic deposited layer (Z) is used, the thickness thereof is 0.001 to 1 〇 ym', preferably 0.005 to 5 / / m, and the total thickness of the gas barrier film is 20 to 750 / / m, more preferably 25 to 430. The range of nm. 200906614 Base material layer (x) In the gas barrier layered composition of the present invention, the base material layer (X) constituting the gas barrier film is not particularly limited, and a film, a sheet, a tape, or the like which is made of a thermoplastic resin is not particularly limited. The thermoplastic resin is various known thermoplastic resins, and examples thereof include polyolefin (polyethylene, polypropylene, poly-4-methyl-1-pentene, polybutene, etc.), and polyester (polyethylene terephthalate). Diester, polybutylene terephthalate, polyethylene naphthalate, etc.), polydecylamine (nylon-6, nylon-66, polyhexamethylene benzene dimethylamine, etc.), polyvinyl chloride, Polyimine, ethylene-vinyl acetate copolymer or its alkali compound, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. Among them, polypropylene, polyester, polyamide, and the like are preferably thermoplastic resins having excellent elongation and transparency, and particularly polyesters such as polyethylene terephthalate and polyethylene naphthalate. It is preferable that one of the preferable aspects of the present invention is that the base material layer (X) is a gas barrier film containing a layer of inorganic fine particles. The base material layer (X-1) containing inorganic fine particles is preferably a layer composed of a base material layer (X-1)' containing inorganic fine particles, and usually a propylene polymer having 5 to 10% by weight of inorganic fine particles. In addition to a propylene monomer, a propylene-based polymer may be a olefin having ethylene as a main component and an olefin such as ethylene, 1-butene, 1-pentene, 1-hexene or 4-methyl-1-pentene. Yuan to ternary random copolymer, segmented copolymer, and the like. The inorganic fine particles are not particularly limited as long as they have an average particle diameter of about 〇"~1 ο V m . -9-200906614 Examples thereof include calcium carbonate, titanium oxide, barium sulfate, magnesium sulfate, cerium oxide, mica, synthetic mica, alum, zeolite, and the like. They may also coat the surface with various polymers as needed. The shape of the inorganic fine particles can be various kinds of aspect ratios such as a spherical shape, a plate shape, a scale shape, and a needle shape. These base material layers (X) can be used without any stretching, at least in the uniaxial direction, and the base material which is stretched is excellent in heat resistance, rigidity, transparency, and gas barrier properties. Further, in order to improve the adhesion to the layer (Y), the substrate layer (X) may be subjected to corona treatment, flame treatment, plasma treatment, primer treatment, plasma coating, for example, on the surface thereof. Surface activation treatment of treatment, flame treatment, and the like. Layer (Y) containing polymer (a) A layer (Y) having at least two layers or more on one or both sides of the base material layer (X), and a polymer containing a polyvalent metal salt of an unsaturated carboxylic acid compound (a) The layer (Y) is preferred. Polymer of a polyvalent metal salt of an unsaturated carboxylic acid compound (a) A polymer (a) of a polyvalent metal salt of an unsaturated carboxylic acid compound is obtained by polymerizing a polyvalent metal salt of an unsaturated carboxylic acid. The unsaturated carboxylic acid compound forms an unsaturated carboxylic acid compound of a polyvalent metal salt of an unsaturated carboxylic acid compound used in the polymer (a), and is acrylic acid, methacrylic acid, cis-butene-10-200906614 diacid, itaconic acid, etc. The carboxylic acid compound having an α,/3-ethylenically unsaturated group has a degree of polymerization of less than 20, preferably a monomer or a polymer having a polymerization degree of 1 Å or less. When a polymer (polymer compound) having a degree of polymerization of more than 20 is used, there is a concern that a salt cannot be formed completely with a polyvalent metal compound described later, and as a result, it is feared that the layer obtained by polymerization of the metal salt is inferior in gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds. Among these unsaturated carboxylic acid compounds, a salt which is a polyvalent metal compound can easily form a completely neutralized salt. The gas barrier layer such as a gas barrier film obtained by laminating at least one side of the base layer of the polymer layer obtained by the polymerization is preferably excellent in gas barrier properties under high humidity. a polyvalent metal compound which forms a component of the polyvalent metal salt of the unsaturated carboxylic acid compound of the present invention, which is a metal and a metal compound belonging to the group 2Α~7Α, 1Β3Β, and 8 of the periodic table, specifically In terms of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni) 'copper (Cu), zinc (Zn), aluminum A metal having a divalent or higher value such as (A1), an oxide, a hydroxide, a tooth, a carbonate, a phosphate, a phosphite, a hypophosphite, a sulfuric acid or a sulfite of the metal. Among these metal compounds, a divalent metal compound is also preferred, and particularly preferably magnesium oxide, calcium oxide, cerium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide or zinc hydroxide. When such a divalent metal compound is used, the film obtained by polymerization with the salt of the above unsaturated carboxylic acid compound is excellent in gas barrier properties at a high humidity of -11 - 200906614. These polyvalent metals may be used alone or in combination with two compounds, Mg, Ca, Zn, Ba and A1, and the unsaturated carboxylic acid compound polyvalent metal salt constitutes the unsaturated carboxylic acid used in the present invention. The unsaturated carboxylic acid of the component (a) is a salt of the unsaturated carboxylic acid compound having a degree of polymerization of less than 20. These unsaturated carboxylic acids may be combined with two or more kinds of k compounds. Among these metal salts, in particular, (meth)acrylic acid is preferred because it has excellent hot water properties. The polymer (a) of the present invention may also contain polyethene, polyvinylpyrrolidone, polyvinylethylethylimine, starch, gum arabic, methyl ester, acrylate polymerization in the range of the purpose of the purpose of the invention. , ethylene/propylene ester, ethylene/vinyl acetate copolymer, poly-high molecular weight compound, etc., slip agent, slip agent, antifogging agent, pigment, dye, inorganic or organic agent, and for improvement and substrate described later Wet various kinds of surfactants and the like. These other achievements
其中，乙烯醇系聚合物（b) I 化合物可使用至少一種 種以上。此等多價金屬 特別以Zn爲佳。 化合物多價金屬鹽之聚 合物多價金屬鹽，係爲 化合物與前述多價金屬 物多價金屬鹽可爲一種 不飽和羧酸化合物多價 鋅所得之聚合物層的耐 I ( Y)，於不損害本發 醇、乙烯•乙烯醇共聚 醚、聚丙烯醯胺、聚伸 纖維素等之水溶性聚合 酸共聚物、聚醋酸乙烯 酯、聚胺基甲酸酯等之 、防黏劑、防帶靜電劑 機之充塡劑等各種添加 性、密黏性等，亦可含 分之比例可視必要改變 i易塗敷至基材層（X) -12- 200906614 ，且阻氣性亦優良’故期望倂用。 即，含有本發明之聚合物（a)的層（Y)爲由不飽和 羧酸化合物多價金屬鹽之聚合物（a)及乙儲醇系聚合物 (b )所構成爲佳。 乙烯醇聚合物（b ) 此類乙烯醇系聚合物，爲聚乙烯醇、乙烯-乙烯醇共 聚物、改性乙烯醇系聚合物等。聚乙烯醇若爲可混合則無 特別問題，較佳之聚合度爲100〜3000，更且爲200〜2500 ，最佳爲3 0 0〜2 0 0 0之範圍。若爲此範圍’易作成水溶液 塗敷至基材層且延伸性、阻氣性亦佳，鹼化度爲9 0 %以上 ，較佳爲9 5 %以上，若爲此範圍則阻氣性良好。又，由於 耐水性和延伸性，亦可使用含有烯烴之聚乙烯醇。烯烴含 量爲0〜25莫耳％，較佳爲1〜20莫耳％’更且爲2〜16莫耳 %之烯烴爲碳數4以下者爲佳，可列舉乙烯、丙烯、正丁烯 、異丁烯等，於耐水性方面而言以乙烯爲最佳。 又，乙烯醇系聚合物的較佳例爲改性乙烯醇系聚合物 改性乙烯醇系聚合物（b 1 ) 改性乙烯醇系聚合物（bl)可列舉於乙烯醇系聚合物 (b ) ’將各種公知之具有反應性之基（反應性基）經由 加成、取代、或酯化等結合反應性基且改性者，將醋酸乙 嫌醋等之乙烯酯與具有反應性基之不飽和化合物共聚所得 -13- 200906614 之共聚物予以鹼化者等。此等反應性聚合基可列舉（甲基 )丙烯酸酯基、（甲基）丙烯醯基、（甲基）丙烯醯胺基 、乙烯基、烯丙基、苯乙烯基、硫醇基、甲矽烷基、乙醯 乙醯基、環氧基等。反應性基之份量可適當決定，但若作 爲基體之乙烯醇系聚合物的OH基份量變少，則擔心乙烯 醇系聚合物本身所具有的阻氣性受損，故通常，反應性基 之份量爲0.001〜50莫耳％之範圍（反應性基與OH基之合 計爲1〇〇莫耳％)。 改性乙烯醇系聚合物（b 1 )的製法可列舉對乙烯醇系 聚合物（b )，將各種公知之具有反應性之基（反應性基 )經由加成、取代或酯化等結合反應性基且改性者，將醋 酸乙烯酯等之乙烯酯與具有反應性基之不飽和化合物共聚 所得之共聚物予以鹼化者等，且聚合物只要分子內具有反 應性基，則無限定。 改性乙烯醇系聚合物（bl)通常可使用聚合度爲100 〜3000’較佳爲300〜2000之範圍者。又，與不飽和羧酸 化合物多價金屬鹽（a )倂用所得聚合物之阻氣性觀點而 言，較佳使用鹼化度爲7 0〜9 9 · 9 %高者，特別以8 5〜9 9.9 % 者爲佳。 又’改性乙烯醇系聚合物（b 1 )較佳爲於水、低級醇 '有機溶劑等中具有溶解性者，特別以溶於水或水-低級 醇系混合溶劑者爲佳。 經由使用此些反應性基所改性之改性乙烯醇系聚合物 (b 1 )作爲成分之一，則可在與不飽和羧酸化合物多價金 -14- 200906614 屬鹽（a )混合聚合時，取得改性乙烯醇系聚合物（b 1 ) 與不飽和羧酸化合物多價金屬鹽（a )之至少一部分爲作 成任何鍵結之聚合物所構成，於低濕度下之阻氣性經改良 的層（Y )。 此類改性乙烯醇系聚合物（b 1 )的具體例，可例示例 如，將作爲基體之乙烯醇系聚合物的一部分OH基與丙烯 酸、甲基丙烯酸、順丁烯二酸、反丁烯二酸、衣康酸等之 具有α、/3乙烯性不飽和基的羧酸化合物或其衍生物反應 導入（甲基）丙烯酸酯基而成的（甲基）丙烯酸酯基改性 乙烯醇系聚合物（bli):令具有異硫脲鎗鹽和硫羥酸酯 之乙烯基單體與醋酸乙烯酯共聚，且所得之聚合物以酸和 鹼分解作成硫醇基的方法，根據高分子反應，於乙烯醇系 聚合物之側鏈導入反應性官能基的方法，於硫羥酸存在下 將乙烯酯類聚合，並將所得之聚合物鹼化僅於分子終端導 入硫醇基的方法等所得，於作爲基體之乙烯醇系聚合物的 一部分OH基中具有硫醇基（-SH基）之硫醇基改性乙烯醇 系聚合物（blii):對乙烯醇系聚合物或含有羧基或羥基 之醋酸乙烯醇系聚合物使用有機基鹵矽烷、有機基乙醯氧 基矽烷、有機基烷氧基矽烷等之甲矽烷基化劑予以後改性 並加成甲矽烷基的方法，或令醋酸乙烯酯與乙烯基矽烷、 (甲基）丙烯醯胺-烷基矽烷等之含有甲矽烷基之烯烴性 不飽和化合物的共聚物鹼化，於分子內導入烷氧基甲矽烷 基、醯氧基甲矽烷基或其水解物之矽烷醇基或其鹽等之甲 矽烷基的方法等所得，於作爲基體之乙烯醇系聚合物的一 -15- 200906614 部分OH基中具有二甲氧基砂院基、三乙氧基砂院基等之 二ί兀興基砂院基、二锻承!砂院基等之甲砂院基改性乙嫌醇 系聚合物（b Π i i ) ’令乙稀醇系聚合物於醋酸溶劑中分散 ，並於其中添加乙醯基乙烯酮的方法，令乙儲醇系聚合物 於一甲基甲醯胺’或一吗院等之溶劑中預先溶解，並於其 中添加乙醯基乙烯酮的方法’及令乙烯醇系聚合物直接接 觸乙醯基乙烯酮氣體或液狀乙醯基乙锦酮的方法等所得， 於作爲基體之乙烯醇系聚合物的一·部分OH基中具有乙醯 乙醯基之乙醯乙醯基改性乙烯醇系聚合物（bliv):經由 具有其他反應性官能基之單體與醋酸乙烯酯共聚後鹼化， 於側鏈導入反應性官能基的方法，根據高分子反應，於聚 乙烯醇之側鏈導入反應性官能基的方法，利用鏈移動反應 於終端導入反應性官能基的方法等各種公知方法，於分子 內，加成（甲基）丙烯醯胺基、烯丙基、乙烯基、苯乙烯 基、分子內雙鍵、乙烯醚基等之其他自由基聚合基而成的 改性乙烯醇系聚合物’加成環氧基、縮水甘油醚基等之陽 離子聚合基而成的改性乙烯醇系聚合物等。 此等改性乙烯醇系聚合物（b 1 )中，亦以使用（甲基 )丙烯酸酯基改性乙烯醇系聚合物（b 1 i )所得之聚合物 所成之層，於高濕度下及低濕度下之阻氣性.（阻氧性）優 良，且熱水處理後之阻氣性（耐熱水性）亦無降低，具有 柔軟性’又，此類層所形成的層合物，其中亦以將薄膜使 用於包裝材等之情形，具有改良熱封強度的特徵。 -16- 200906614 (甲基）丙烯酸酯基改性乙烯醇系聚合物（b 1 i ) 作爲前述（甲基）丙烯酸酯基改性乙烯醇系聚合物（ bli )，較佳爲（甲基）丙烯醯基的份量（與-OH基的對比 ;酯化率）爲〇 . 〇 〇 1〜5 0 %，更佳爲0 · 1〜4 0 %之範圍。酯化 率未達0.001 %者則擔心所得層（Y )的耐熱水性、柔軟性 等未被改良，另一方面，超過5 0%者則擔心所得層（Y ) 的耐熱水性、氧阻擋性等未被改良。 本發明之（甲基）丙烯酸酯改性乙烯醇系聚合物（ bli)爲例如，令乙烯醇系共聚物與（甲基）丙烯酸或（ 甲基）丙烯酸鹵化物、（甲基）丙烯酸酐、（甲基）丙烯 酸酯等之（甲基）丙烯酸衍生物，例如於布朗斯台德酸、 布朗斯台德鹼、路易士酸、路易士鹼、金屬化合物等之觸 媒存在下或非存在下反應而取得。又，令乙烯醇系共聚物 ，與例如（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸2-異氰乙酯等之分子內具有與乙烯醇系共聚物之OH基反應 之官能基的（甲基）丙烯酸衍生物反應，亦可將（甲基） 丙烯酸酯基間接導入乙烯醇系共聚物中。 硫醇基改性乙烯醇系聚合物（b 1 ii ) 作爲前述硫醇基改性乙烯醇系聚合物（b 1 ii )，可爲 令具有異硫脲鎗鹽和硫羥酸酯之乙烯基單體與醋酸乙烯酯 共聚，且所得之聚合物以酸和鹼分解作成硫醇基的方法， 根據高分子反應，於聚乙烯醇系聚合物之側鏈導入反應性 官能基的方法，於包含具有-COSH基之有機硫羥酸之硫醇 -17- 200906614 醋酸、硫醇丙酸、硫醇丁酸等之硫醇羧酸存在下，令甲酸 乙烯酯、醋酸乙烯酯、醋酸乙烯酯、支鏈烷烴酸乙烯酯、 月桂酸乙烯酯、硬脂酸乙烯酯等之乙烯酯類聚合，並將所 得之聚合物鹼化則可僅於分子之終端導入硫醇基的方法等 公知方法於分子內賦予硫醇基的聚合物，通常，硫醇基改 性率爲在0 . 1〜5 0莫耳％之範圍。 作爲此等硫醇基改性乙烯醇系聚合物（b 1 ii )，例如 ’由（股）Curale以Curale M Polymer之商品名所製造， 販售的「M-115」及「M-205」。 甲矽烷基改性乙烯醇系聚合物（b 1 iii ) 作爲前述甲矽烷基改性乙烯醇系聚合物（b 1 iii )，可 列舉令乙烯醇系聚合物或含有羧基或羥基之醋酸乙烯醇系 聚合物’使用三甲基氯矽烷、二甲基二氯矽烷、甲基三氯 矽烷、乙烯基三氯矽烷、二苯基二氯矽烷等之有機基鹵素 矽烷、三甲基乙醯氧基矽烷、二甲基二乙醯氧基矽烷等之 有機基乙醯氧基矽烷或三甲氧基矽烷、二甲基二甲氧基砂 烷等之有機基烷氧基矽烷等之甲矽烷基化劑予以後改性並 且加成甲矽烷基的方法，或令醋酸乙烯酯與例如，乙稀基 三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三（石-甲 氧乙氧基）砂院、乙稀基三乙酿氧基砂院、稀丙基三甲氧 基砂院、烯丙基三乙醯氧基砂院、乙儲基甲基二甲氧基砂 院、乙烯基二甲基甲氧基矽院、乙烯基甲基二乙氧基砂院 、乙烯基二甲基乙氧基矽烷、乙烯基甲基二乙醯氧基矽烷 -18- 200906614 、乙烯基二甲基乙醯氧基矽烷、乙烯基異丁基二甲氧基矽 烷、乙烯基三異丙氧基矽烷、乙烯基三丁氧基矽烷、乙烯 基三己氧基矽烷、乙烯基甲氧基二乙氧基矽烷、乙烯基二 甲氧基辛氧基矽烷等之乙烯基矽烷、或3-(甲基）丙烯醯 胺-丙基三甲氧基矽烷、3-(甲基）丙烯醯胺-丙基三乙氧 基矽烷、3-(甲基）丙烯醯胺-丙基三（/3 -甲氧乙氧基） 矽烷、2-(甲基）丙烯醯胺-2-甲基丙基三甲氧基矽烷、2-(甲基）丙烯醯胺-2-甲基乙基三甲氧基矽烷、N- (2-(甲 基）丙烯醯胺乙基）胺丙基三甲氧基矽烷、3-(甲基）丙 烯醯胺-丙基三乙醯氧基矽烷、2-(甲基）丙烯醯胺-乙基 三甲氧基矽烷、1-(甲基）丙烯醯胺-甲基三甲氧基矽烷、 3-(甲基）丙烯醯胺-丙基甲基二甲氧基矽烷、3-(甲基） 丙烯醯胺-丙基二甲基甲氧基矽烷、3-(N-甲基-(甲基） 丙烯醯胺）丙基三甲氧基矽烷、3-((甲基）丙烯醯胺基-甲氧基）-3-羥丙基三甲氧基矽烷、3-((甲基）丙烯醯胺 基-甲氧基）-丙基三甲氧基矽烷等之（甲基）丙烯醯胺-烷 基矽烷等之含有甲矽烷基之烯烴性不飽和化合物的共聚物 鹼化之方法等所得之分子內具有烷氧基甲矽烷基、醯氧基 甲矽烷基或其水解物之矽烷醇基或其鹽等之具有甲矽烷基 的聚合物等。此等甲矽烷基之改性量通常爲在0.1〜50莫 耳％之範圍。 作爲此等甲矽烷基改性乙烯醇系聚合物（b 1 iii )，例 如，由（股）Curale以Curale R Polymer之商品名所製造， 販售的「R-1130」、「R-2105」及「R-2130」。 -19- 200906614 乙酿乙醯基改性乙烯醇系聚合物（b 1 iv ) 作爲則述乙醯乙醯基改性乙烯醇系聚合物（b丨i v )， 係於則述乙烯醇系聚合物之溶液、分散液或粉末中添加液 狀或氣體狀之乙醯基乙烯酮反應所得者，通常，乙醯乙醯 化度爲1〜1〇莫耳％，較佳爲3〜5莫耳％之範圍。 作爲此等乙醯乙醯基改性乙稀醇系聚合物（bliv) ’ 例如’由日本合成化學工業（股）以「G〇sefimer Z1 00」 ’同「Z200」，同「Z200H」及同「Z210」之商品名所製 造、販售。 又’此等改性乙烯醇系聚合物較佳爲於水、低級醇、 有機溶劑中具有溶解性者，特別以溶解於水-低級醇系混 合溶劑者爲佳。 於含有此等改性乙烯醇系聚合物之乙烯醇系聚合物的 水溶液中，水以外之溶劑，例如甲醇、乙醇、異丙醇等之 醇類、丙嗣、甲基乙基酮等之酮類，或其他乙醚、四氫呋 喃等視需要，亦可組合加入1種或2種以上。又，於聚乙烯 醇系聚合物中，在不阻礙本發明特徵之範圍中可加入濕潤 性改善劑、防帶靜電劑，其他各種添加劑。 倂用此等乙烯醇系聚合物（b)時，含有本發明聚合 物（a)之層（Y)，一般通常由不飽和羧酸化合物多價金 屬鹽之聚合物（a)爲1〜99莫耳％，乙烯醇系聚合物（b) 爲1〜99莫耳％所構成。 其中亦以不飽和羧酸化合物多價金屬鹽之聚合物（a -20- 200906614 )60〜98重量％、乙烯醇系聚合物（b)爲2〜40重量。/〇, 特別以（a) 70〜95重量％ ’（ b) 5〜30重量％ (( a)及 (b )之合計視爲1 〇 〇重量％ )爲佳。 阻氣薄膜之製造方法 本發明之阻氣性層合物中，作爲製造阻氣薄膜的方法 ，爲對未延拉或已延拉的基材層（X)，將含有聚合度爲 未達20之不飽和羧酸化合物多價金屬鹽的溶液（a)塗佈 後，聚合不飽和羧酸化合物多價金屬鹽，形成含有不飽和 羧酸化合物多價金屬鹽之聚合物（a)的層（Y)之方法。 作成含有聚合度爲未達20之不飽和羧酸化合物多價金 屬鹽之溶液（s )的方法，係預先令前述不飽和羧酸化合 物與前述多價金屬化合物反應，作成不飽和羧酸化合物之 多價金屬鹽後，作成溶液亦可，且於溶劑中直接溶解前述 不飽和羧酸化合物和前述多價金屬化合物，作成多價金屬 鹽之溶液亦可。 本發明之阻氣薄膜的製造方法，於溶劑中直接溶解前 述不飽和羧酸化合物和前述多價金屬化合物之情形，即， 使用含有前述不飽和羧酸化合物和前述多價金屬化合物之 溶液之情形，相對於前述不飽和羧酸化合物，添加超過 0.3化學當量比份量之前述多價金屬化合物爲佳。使用多 價金屬化合物之添加量爲0 · 3化學當量比以下之混合溶液 之情形，成爲游離羧酸基含量多的聚合物層，結果，擔心 成爲阻氣性低的延拉薄膜。又，多價金屬化合物之添加量 -21 - 200906614 並無特別限定之上限，但多價金屬化合物之添加量若超過 1化學當量比，則未反應的多價金屬化合物變多，故通常 ，以5化學當量比以下，較佳爲2化學當量比以下即充分。 另外，本發明中的化學當量比，係表示多價金屬化合 物相對於不飽和羧酸化合物的化學當量比’並且根據下式 所算出之値。 化學當量比=(多價金屬化合物之莫耳數）X(多價金屬化 合物之價數）/不飽和羧酸化合物所含之羧基的莫耳數 例如，令作爲多價金屬化合物之氫氧化鈣（分子量74 克/莫耳）37克，作爲不飽和羧酸化合物之丙烯酸單體（ 分子量70克/莫耳）72克混合時的化學當量比視爲1。 又，使用不飽和羧酸化合物與多價金屬化合物之混合 溶液之情形，通常，在不飽和羧酸化合物與多價金屬化合 物溶於溶劑之間，形成不飽和羧酸化合物的多價金屬鹽， 但爲了確實形成多價金屬鹽，以混合1分鐘以上爲佳。 不飽和羧酸化合物多價金屬鹽之溶液所用的溶劑，可 列舉水、甲醇、乙醇、異丙醇等之低級醇或丙酮、甲基乙 基酮等之有機溶劑或其混合溶劑，但以水爲最佳。 於基材層（X)之表面塗佈不飽和竣酸化合物多價金 屬鹽之溶液（S )的方法，可採用各種公知的方法，例如 ’於基材層表面塗佈該溶液的方法，於該溶液中浸漬基材 層的方法’於基材層表面噴霧該溶液的方法，以刷毛等予 -22- 200906614 以塗佈之方法等。 於薄膜狀之基材層（X)上塗佈含有不飽和羧酸 物之多價金屬鹽之溶液（s )的方法，例如’使用空 塗層器、直接照相凹版塗層器、照相凹版膠印、弧形 凹版塗層器、逆照相凹版及噴射管嘴方式等之照相凹 層器、頂餵式逆塗層器、底餵式逆塗層器及管嘴餵送 塗層器等之逆輥塗層器、五根輥塗層器、唇式塗層器 塗層器、棒逆塗層器、型板塗層器等各種公知的塗佈 且不飽和羧酸化合物多價金屬鹽之溶液（S)中（固 分）的份量若爲〇.〇5〜10 g/m2，較佳爲0.1〜5 g/m2即 令不飽和羧酸化合物多價金屬鹽溶解時，在不損 發明目的之範圍中，亦可添加（甲基）丙烯酸甲酯、 基）丙烯酸乙酯等之其他不飽和羧酸（二）酯化合物 酸乙烯酯等之乙烯酯化合物等之單體或低分子量化合 滑劑、增滑劑、防黏劑、防帶靜電劑、防霧劑、顏料 料、無機或有機充塡劑等之各種添加劑，且爲了改良 材層的濕潤性’亦可添加各種界面活性劑等。 令基材層（X )所形成（塗佈）之不飽和羧酸化 多價金屬鹽溶液（塗佈層）聚合上，可根據各種公知 法’具體而言可列舉例如，照射電離放射線或加熱等 法。 使用電離放射線之情形，若波長領域爲0.000 1 一 nm範圍之能量線，則無特別限定，此類能量線可列舉 線、yS射線、7射線、X射線、可見光線、紫外線、 化合 氣、 照相 版塗 式逆 、棒 機， 形成 可。 害本 (甲 、醋 物、 、染 與基 合物 之方 之方 -800 α射 電子 -23- 200906614 射線等。此等電離放射線中，亦以波長領域爲4 〇 〇〜8 0 0 nm範圍之可見光線、50〜400 nm範圍之紫外線及0·01〜 0.002 nm範圍之電子射線，因操作容易，且裝置亦普及故 爲佳。 使用可見光線及紫外線作爲電離放射線之情形，必須 於不飽和羧酸化合物多價金屬鹽之溶液中添加光聚合啓始 劑。光聚合啓始劑可使用公知物質，可列舉例如，2 _羥基― 2 -甲基-1-苯基-丙院-1-酮（Ciba Specialty Chemicals 公司 製商品名；Darocure-1 173 ) 、1-羥基-環己基-苯基酮（ C i b a S p e c i a 11 y C h e m i c a 1 s 公司製 商品名；Irugacure 1 84 )、雙（2,4,6-三甲基苯甲醯）-苯基氧化膦（ciba Specialty Chemicals公司製 商品名；Irugacure 8 1 9 ) 、1 - [4-(2-羥乙氧基）苯基]-2-羥基-2-甲基-1-丙烷-1-酮（ Ciba Specialty Chemicals公司製商品名；I r u g a c u r e 2 9 5 9 )、a-羥基酮、醯基氧化膦、4 -甲基二苯酮及2,4,6-三甲 基二苯酮之混合物（Lanbelity Chemical Specialty公司製 商品名；Esacure KT046 ) 、Esacure KT 55 ( LanbelityAmong them, at least one kind of the vinyl alcohol polymer (b) I compound can be used. These polyvalent metals are particularly preferably Zn. The polymer polyvalent metal salt of the compound polyvalent metal salt is a compound (I) capable of being a polyvalent metal salt of the above polyvalent metal, which may be an unsaturated carboxylic acid compound obtained by multivalent zinc. It does not damage the water-soluble polymeric acid copolymer, polyvinyl acetate, polyurethane, etc. of the hair alcohol, ethylene vinyl alcohol copolyether, polypropylene decylamine, cellulose dispersion, etc., anti-adhesive agent, anti-adhesion agent Various additives, adhesiveness, etc. of the electrostatic agent with an electrostatic agent, and the proportion of the content may be changed to the substrate layer (X) -12-200906614, and the gas barrier property is also excellent. Therefore, it is expected to be used. Namely, the layer (Y) containing the polymer (a) of the present invention is preferably composed of a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt and a glycol storage alcohol polymer (b). Vinyl alcohol polymer (b) The vinyl alcohol polymer is a polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, a modified vinyl alcohol polymer or the like. The polyvinyl alcohol is not particularly problematic if it is miscible, and preferably has a polymerization degree of from 100 to 3,000, more preferably from 200 to 2,500, most preferably from 30,000 to 2,000. If the range is 'easy to be applied to the substrate layer and the elongation and gas barrier properties are good, the degree of alkalinity is 90% or more, preferably 95% or more. If the range is good, the gas barrier property is good. . Further, polyvinyl alcohol containing an olefin can also be used due to water resistance and elongation. The olefin content is 0 to 25 mol%, preferably 1 to 20 mol%, and more preferably 2 to 16 mol%, and the olefin is preferably 4 or less, and examples thereof include ethylene, propylene, and n-butene. Isobutylene and the like are preferably ethylene in terms of water resistance. Further, a preferred example of the vinyl alcohol polymer is a modified vinyl alcohol polymer-modified vinyl alcohol polymer (b 1 ). The modified vinyl alcohol polymer (bl) is exemplified by a vinyl alcohol polymer (b). 'A variety of well-known reactive groups (reactive groups) are bonded to a reactive group via addition, substitution, or esterification, etc., and a vinyl ester such as ethyl acetate or the like has a reactive group. The copolymer obtained by copolymerizing an unsaturated compound -13 to 200906614 is alkalized or the like. Examples of such a reactive polymer group include a (meth) acrylate group, a (meth) acryl fluorenyl group, a (meth) acryl amide group, a vinyl group, an allyl group, a styryl group, a thiol group, and a decane. Base, ethyl hydrazide, epoxy group, and the like. The amount of the reactive group can be appropriately determined. However, when the amount of the OH group of the vinyl alcohol polymer as the matrix is small, the gas barrier property of the vinyl alcohol polymer itself is impaired, and therefore, the reactive group is usually used. The amount is in the range of 0.001 to 50 mol% (the total of the reactive group and the OH group is 1 mol%). The method for producing the modified vinyl alcohol polymer (b 1 ) includes a vinyl alcohol polymer (b), and various known reactive groups (reactive groups) are subjected to a bonding reaction such as addition, substitution or esterification. The copolymer obtained by copolymerizing a vinyl ester such as vinyl acetate with an unsaturated compound having a reactive group is alkalized, and the polymer is not limited as long as it has a reactive group in the molecule. The modified vinyl alcohol polymer (b1) can be usually used in a range of a polymerization degree of from 100 to 3,000', preferably from 300 to 2,000. Further, from the viewpoint of gas barrier properties of the polyvalent metal salt (a) of the unsaturated carboxylic acid compound, it is preferred to use a degree of alkalinity of 70 to 9 9 · 9 %, particularly 8 5 . ~9 9.9 % are better. Further, the modified vinyl alcohol polymer (b 1 ) is preferably one having solubility in water, a lower alcohol 'organic solvent or the like, and particularly preferably a water-soluble or water-lower alcohol-based mixed solvent. By using the modified vinyl alcohol-based polymer (b 1 ) modified by using such a reactive group as one of the components, it can be mixed and polymerized with the unsaturated carboxylic acid compound polyvalent gold-14-200906614 genus salt (a). At the time of obtaining a modified vinyl alcohol polymer (b 1 ) and at least a part of the polyvalent metal salt (a) of the unsaturated carboxylic acid compound, a polymer which is formed by any bonding, and a gas barrier property under low humidity Improved layer (Y). Specific examples of such a modified vinyl alcohol-based polymer (b 1 ) include, for example, a part of an OH group of a vinyl alcohol-based polymer as a matrix, and acrylic acid, methacrylic acid, maleic acid, and anti-butene. (Meth) acrylate-modified vinyl alcohol obtained by reacting a carboxylic acid compound having an α, /3 ethylenically unsaturated group such as diacid or itaconic acid or a derivative thereof into a (meth) acrylate group Polymer (bli): a method in which a vinyl monomer having an isothiourea salt and a thiol ester is copolymerized with vinyl acetate, and the obtained polymer is decomposed into a thiol group by acid and alkali, according to a polymer reaction. a method of introducing a reactive functional group into a side chain of a vinyl alcohol-based polymer, polymerizing a vinyl ester in the presence of a thiol acid, and alkalizing the obtained polymer to a method of introducing a thiol group only at a molecular terminal. A thiol group-modified vinyl alcohol polymer (blii) having a thiol group (-SH group) in a part of an OH group of a vinyl alcohol-based polymer as a matrix: a vinyl alcohol-based polymer or a carboxyl group or a hydroxyl group The vinyl acetate polymer is organic A method for post-modifying a methylation alkylating agent such as a halothane, an organoethoxy decane or an organoalkoxy decane, and adding a methoxyalkyl group, or a vinyl acetate and a vinyl decane, Alkylation of a copolymer of a methoxyl-alkyl group-containing olefinic unsaturated compound such as acrylamide-alkyl decane, and alkane in which alkoxymethyl sulfonyl group, decyl methoxyalkyl group or a hydrolyzate thereof is introduced in a molecule. A method for obtaining a methoxyalkyl group such as an alcohol group or a salt thereof, or the like, and a dimethoxy sand-based, triethoxy sand-based base in a -15-200906614 partial OH group of a vinyl alcohol-based polymer as a matrix. Etc. 兀 兀 基 基 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂 砂And a method of adding ethyl ketone ketene thereto, preliminarily dissolving the ethyl alcohol-based polymer in a solvent such as monomethylcarbamide or a hospital, and adding an ethyl ketene thereto 'And the vinyl alcohol polymer is directly contacted with ethyl ketene gas or liquid ethyl hydrazine The ethyl ketamine-modified vinyl alcohol-based polymer (bliv) having an ethyl oxime group in a part of the OH group of the vinyl alcohol-based polymer as a matrix obtained by the method of the methicone, etc. a method in which a monomer of another reactive functional group is copolymerized with vinyl acetate, alkalized, a reactive functional group is introduced into a side chain, and a reactive functional group is introduced into a side chain of polyvinyl alcohol according to a polymer reaction, and a chain is used. Various known methods such as a method of introducing a reactive functional group by a terminal reaction, and adding (meth)acrylamide, allyl, vinyl, styryl, intramolecular double bond, vinyl ether group in the molecule. A modified vinyl alcohol-based polymer obtained by adding a radical polymerizable group such as a radical polymerizable group, or a modified vinyl alcohol-based polymer obtained by adding a cationic polymer group such as an epoxy group or a glycidyl ether group. In the modified vinyl alcohol polymer (b 1 ), a layer obtained by using a polymer obtained by modifying a (meth) acrylate group-modified vinyl alcohol polymer (b 1 i ) under high humidity And gas barrier properties under low humidity. (Oxygen barrier property) is excellent, and the gas barrier property (hot water resistance) after hot water treatment is not lowered, and has a softness, and a laminate formed by such a layer, wherein Also, in the case where the film is used for a packaging material or the like, it has a feature of improving heat seal strength. -16- 200906614 (meth)acrylate-modified vinyl alcohol polymer (b 1 i ) as the (meth)acrylate-modified vinyl alcohol polymer (bli), preferably (methyl) The amount of the acrylonitrile group (compared with the -OH group; the esterification rate) is 〇1 to 50%, more preferably 0. 1 to 40%. When the esterification rate is less than 0.001%, the hot water resistance and flexibility of the obtained layer (Y) are not improved. On the other hand, if it exceeds 50%, the hot water resistance and oxygen barrier properties of the obtained layer (Y) are feared. Not improved. The (meth) acrylate-modified vinyl alcohol-based polymer (bli) of the present invention is, for example, a vinyl alcohol-based copolymer, (meth)acrylic acid or (meth)acrylic acid halide, (meth)acrylic anhydride, (meth)acrylic acid derivatives such as (meth) acrylate, for example, in the presence or absence of a catalyst such as Bronsted acid, Bronsted alkali, Lewis acid, Lewis base, metal compound or the like Obtained by reaction. Further, the vinyl alcohol-based copolymer has a functional group reactive with an OH group of a vinyl alcohol-based copolymer in a molecule such as glycidyl (meth)acrylate or 2-isocyanoethyl (meth)acrylate. The (meth)acrylic acid derivative may be reacted, and the (meth) acrylate group may be indirectly introduced into the vinyl alcohol-based copolymer. a thiol group-modified vinyl alcohol-based polymer (b 1 ii ) as the aforementioned thiol-modified vinyl alcohol-based polymer (b 1 ii ), which can be a vinyl having an isothiourea salt and a thiol ester a method in which a monomer is copolymerized with vinyl acetate, and the obtained polymer is decomposed into a thiol group by acid and alkali, and a reactive functional group is introduced into a side chain of the polyvinyl alcohol-based polymer according to a polymer reaction. Mercaptan with -COSH-based organic thiol-17-200906614 Acetate, vinyl thiolate, vinyl acetate, vinyl acetate A method in which a vinyl ester of a vinyl alkanoate, a vinyl laurate or a vinyl stearate is polymerized, and the obtained polymer is alkalized, and a thiol group can be introduced only at a terminal of a molecule, and the like can be carried out in a molecule. The thiol group-containing polymer usually has a thiol group modification ratio in the range of 0.1 to 50% by mole. As such thiol-modified vinyl alcohol-based polymer (b 1 ii ), for example, "M-115" and "M-205" which are sold under the trade name of Curale M Polymer by Curale. The methacrylate-modified vinyl alcohol-based polymer (b 1 iii ) is exemplified as the vinyl hydride-modified vinyl alcohol-based polymer (b 1 iii ), and the vinyl alcohol-based polymer or vinyl acetate having a carboxyl group or a hydroxyl group. The polymer 'is an organohalogen decane such as trimethylchlorodecane, dimethyldichlorodecane, methyltrichlorodecane, vinyltrichlorodecane or diphenyldichlorodecane, or trimethylacetoxy. a mercaptan alkylating agent such as an organic ethoxy decane such as decane or dimethyldiethoxy decane or an organoalkoxy decane such as trimethoxy decane or dimethyl dimethoxy sulane. a method of post-modification and addition of a methoxyalkyl group, or a vinyl acetate with, for example, ethylene trimethoxy decane, vinyl triethoxy decane, vinyl tris(石-methoxyethoxy) sand Institute, Ethylene-based triethyl ethoxylate sand, D-propyl trimethoxy sand, allyl triethoxy silicate sand, B storage methyl dimethoxy sand, vinyl dimethyl Methoxy brothel, vinyl methyl diethoxy sand yard, vinyl dimethyl ethoxy decane, B Methyldiethoxymethoxydecane-18- 200906614, vinyl dimethyl ethoxy decane, vinyl isobutyl dimethoxy decane, vinyl triisopropoxy decane, vinyl tributoxy Vinyl decane such as decane, vinyl trihexyloxydecane, vinyl methoxydiethoxy decane, vinyl dimethoxyoctyloxydecane, or 3-(meth) acrylamide-propyl Trimethoxy decane, 3-(meth) acrylamide-propyl triethoxy decane, 3-(methyl) acrylamide-propyl tris (/3 - methoxyethoxy) decane, 2 -(Meth) acrylamide-methyl methacrylate trimethyl decane, 2-(methyl) acrylamide oxime-2-methylethyltrimethoxy decane, N-(2-(methyl) Acrylamide ethyl)aminopropyltrimethoxydecane, 3-(meth)acrylamide-propyltriethoxydecane, 2-(meth)acrylamide-ethyltrimethoxydecane, 1-(Meth)acrylamide-methyltrimethoxydecane, 3-(meth)acrylamide-propylmethyldimethoxydecane, 3-(methyl)acrylamide-propyl Methyl methoxy decane, 3-(N-methyl-(methyl) propylene oxime Amine) propyltrimethoxydecane, 3-((meth)acrylamido-methoxy)-3-hydroxypropyltrimethoxydecane, 3-((meth)acrylamido-methoxy a method of basifying a copolymer of a methacrylic acid-containing olefinic unsaturated compound such as (meth) acrylamide-alkyl decane such as propyl trimethoxy decane, etc. A polymer having a germyl group, such as a decyl alcohol group, a decyl alcohol group or a stanol group of a hydrolyzate thereof or a salt thereof. The amount of modification of such a germyl group is usually in the range of 0.1 to 50 mol%. As such a methyl decyl-modified vinyl alcohol-based polymer (b 1 iii ), for example, "R-1130" and "R-2105", which are manufactured by Curale R Polymer under the trade name of Curale, are sold. "R-2130". -19- 200906614 Ethylene-based modified vinyl alcohol-based polymer (b 1 iv ) is described as an ethylene-vinyl modified polymer (b丨iv), which is described in the description of vinyl alcohol polymerization. A solution obtained by adding a liquid or gaseous ethyl ketone to a solution, a dispersion or a powder, usually having an oxime degree of from 1 to 1% by mole, preferably from 3 to 5 moles. The range of %. As such acetamethylene-based modified ethylene-based polymer (bliv) 'for example' from Japan Synthetic Chemical Industry Co., Ltd. with "G〇sefimer Z1 00" 'with "Z200", with "Z200H" and The product name of "Z210" is manufactured and sold. Further, the modified vinyl alcohol-based polymer preferably has solubility in water, a lower alcohol or an organic solvent, and is particularly preferably dissolved in a water-lower alcohol-based mixed solvent. In an aqueous solution of a vinyl alcohol polymer containing such a modified vinyl alcohol polymer, a solvent other than water, for example, an alcohol such as methanol, ethanol or isopropyl alcohol, or a ketone such as methyl ketone or methyl ethyl ketone. The type, or other diethyl ether, tetrahydrofuran, etc. may be added in combination of one type or two or more types as needed. Further, in the polyvinyl alcohol-based polymer, a moisturizing agent, an antistatic agent, and other various additives may be added to the extent that the characteristics of the present invention are not inhibited. When the vinyl alcohol-based polymer (b) is used, the layer (Y) containing the polymer (a) of the present invention is generally usually composed of a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt of 1 to 99. The molar %, the vinyl alcohol polymer (b) is composed of 1 to 99 mol%. Further, the polymer of the polyvalent metal salt of the unsaturated carboxylic acid compound (a -20-200906614) is 60 to 98% by weight, and the vinyl alcohol polymer (b) is 2 to 40 parts by weight. /〇, particularly preferably (a) 70 to 95% by weight of ‘(b) 5 to 30% by weight (the total of (a) and (b) is regarded as 1 〇 〇% by weight). Method for producing gas barrier film In the gas barrier layered composition of the present invention, as a method for producing a gas barrier film, the substrate layer (X) which is not stretched or stretched is contained to have a polymerization degree of less than 20 After coating (a) of the solution of the unsaturated carboxylic acid compound polyvalent metal salt, the polyvalent metal salt of the unsaturated carboxylic acid compound is polymerized to form a layer of the polymer (a) containing the polyvalent metal salt of the unsaturated carboxylic acid compound ( Y) method. A method of preparing a solution (s) containing a polyvalent metal salt of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20, wherein the unsaturated carboxylic acid compound is reacted with the polyvalent metal compound to form an unsaturated carboxylic acid compound. After the polyvalent metal salt, a solution may be prepared, and the unsaturated carboxylic acid compound and the polyvalent metal compound may be directly dissolved in a solvent to form a solution of a polyvalent metal salt. In the method for producing a gas barrier film of the present invention, the unsaturated carboxylic acid compound and the polyvalent metal compound are directly dissolved in a solvent, that is, a solution containing the aforementioned unsaturated carboxylic acid compound and the above polyvalent metal compound is used. It is preferred to add the above-mentioned polyvalent metal compound in an amount of more than 0.3 stoichiometric equivalents to the above unsaturated carboxylic acid compound. When a mixed solution having a polyvalent metal compound added in an amount of 0. 3 stoichiometric ratio or less is used, a polymer layer having a large content of a free carboxylic acid group is obtained, and as a result, a delayed film having a low gas barrier property is feared. Further, the amount of the polyvalent metal compound to be added is not particularly limited. However, when the amount of the polyvalent metal compound added exceeds 1 stoichiometric ratio, the amount of unreacted polyvalent metal compound increases, so usually The chemical equivalent ratio is preferably 5 or less, preferably 2 chemical equivalents or less. Further, the stoichiometric ratio in the present invention is a stoichiometric ratio of a polyvalent metal compound to an unsaturated carboxylic acid compound and is calculated according to the following formula. Chemical equivalent ratio = (molar number of polyvalent metal compound) X (valent number of polyvalent metal compound) / molar number of carboxyl group contained in unsaturated carboxylic acid compound, for example, calcium hydroxide as a polyvalent metal compound (molecular weight: 74 g/mole) 37 g, and the stoichiometric ratio when the acrylic monomer (molecular weight 70 g/mole) of 72 g of the unsaturated carboxylic acid compound was mixed was regarded as 1. Further, in the case of using a mixed solution of an unsaturated carboxylic acid compound and a polyvalent metal compound, usually, a polyvalent metal salt of an unsaturated carboxylic acid compound is formed between an unsaturated carboxylic acid compound and a polyvalent metal compound dissolved in a solvent. However, in order to form a polyvalent metal salt, it is preferred to mix for 1 minute or more. The solvent used for the solution of the polyvalent metal salt of the unsaturated carboxylic acid compound may, for example, be a lower alcohol such as water, methanol, ethanol or isopropyl alcohol or an organic solvent such as acetone or methyl ethyl ketone or a mixed solvent thereof. For the best. A method of applying a solution (S) of an unsaturated phthalic acid compound polyvalent metal salt to the surface of the substrate layer (X) may be carried out by various known methods, such as a method of coating the surface of the substrate layer with a solution. The method of immersing the base material layer in the solution is a method of spraying the solution on the surface of the base material layer, and the method of coating is carried out by bristles, etc., in -22-200906614. A method of coating a solution (s) containing a polyvalent metal salt of an unsaturated carboxylic acid on a film-form substrate layer (X), such as 'using an empty coater, a direct gravure coater, gravure offset printing Reverse roller such as eccentric gravure coater, reverse gravure and spray nozzle method, such as photographic notch, top feed reverse coater, bottom feed reverse coater and nozzle feed coater Various known coated and unsaturated carboxylic acid compound polyvalent metal salt solutions such as coater, five roll coater, lip coater coater, rod reverse coater, stencil coater, etc. When the amount of the (solid) component in S) is 〇.〇5 to 10 g/m2, preferably 0.1 to 5 g/m2, when the polyvalent metal salt of the unsaturated carboxylic acid compound is dissolved, the range of the object of the invention is not impaired. In addition, a monomer or a low molecular weight compounding agent such as a vinyl ester compound such as another unsaturated carboxylic acid (di) acrylate compound such as methyl (meth) acrylate or ethyl acrylate may be added. Various additives such as slip agent, anti-sticking agent, antistatic agent, antifogging agent, pigment material, inorganic or organic filling agent Agent, and the material layer in order to improve wettability 'may be added various surfactants or the like. The unsaturated carboxylated polyvalent metal salt solution (coating layer) formed (coated) by the base layer (X) is polymerized, and specific examples thereof include, for example, irradiation with ionizing radiation or heating. law. In the case of using ionizing radiation, if the wavelength field is an energy line in the range of 0.000 1 to nm, there is no particular limitation, and such an energy line may be a line, a yS ray, a 7 ray, an X ray, a visible ray, an ultraviolet ray, a combined gas, or a photograph. The plate type is reversed and the bar machine is formed. The damage (A, vinegar, dye, and the side of the compound -800 α 射 -23- 200906614 ray, etc.. In these ionizing radiation, also in the wavelength range of 4 〇〇 ~ 800 nm range The visible light, the ultraviolet light in the range of 50 to 400 nm, and the electron beam in the range of 0·01 to 0.002 nm are preferred because of easy operation and popularization of the device. When visible light and ultraviolet rays are used as ionizing radiation, it must be unsaturated. A photopolymerization initiator is added to the solution of the carboxylic acid compound polyvalent metal salt. A known substance can be used as the photopolymerization initiator, and, for example, 2 _hydroxy-2-methyl-1-phenyl-propyl-1- Ketone (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.; Darocure-1 173), 1-hydroxy-cyclohexyl-phenyl ketone (trade name, manufactured by Ciba S pecia 11 y C hemica 1 s; Irugacure 1 84), double (2) , 4,6-trimethylbenzhydrazide)-phenylphosphine oxide (trade name: ciba Specialty Chemicals, Irukacure 8 1 9 ), 1-[4-(2-hydroxyethoxy)phenyl]-2 -hydroxy-2-methyl-1-propan-1-one (trade name, manufactured by Ciba Specialty Chemicals; Ir Ugacure 2 9 5 9 ), a mixture of a-hydroxyketone, decylphosphine oxide, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name, manufactured by Lanbelity Chemical Specialty; Esacure KT046) ), Esacure KT 55 ( Lanbelity
Chemical Specialty) 、2,4,6 -三甲基苯甲醯二苯基氧化膦 (Lamuson Fire Chemical公司製商品名；Speedcure ΤΡΟ )之商品名所製造、販售的自由基聚合啓始劑。 更且，爲了提高聚合度或聚合速度，可添加聚合促進 劑，可列舉例如，Ν,Ν-二甲胺基（甲基）丙烯酸乙酯、N-(甲基）丙烯醯嗎啉等。 照射電離放射線進行本聚合時，通常，令電離放射線 -24- 200906614 之照射量爲1〜1000 mJ/cm2，較佳爲5〜300 以1 0〜2 0 0 m J / c m 2之範圍爲佳。經由令照射 ，則可安定取得聚合率爲8 0 %以上，較佳爲 氣薄膜等之阻氣性層合物。 本發明之阻氣性層合物中，阻氣薄膜老 )視爲（X)，含有聚合物（a)之層（γ) (Y2 )、 （ Y3 )、 （ Y4 )，則可例示 (X)/(Y')/(Y2) (Χ)/(Υ1)/(Υ2)/(Υ3) (Χ)/(Υ1)/(Υ2)/(Υ3)/(γ4) 等所示之層合構造。 另外，（Υ1) 、 （ Υ2) 、 （ Υ3) 、 ( 聚合物（a )的含量可彼此相同、或相異亦 所含之聚合物（b)的含量亦可彼此相同、或 於本發明之阻氣薄膜等之阻氣性層合物 (X)與含有聚合物（a)之層之間， (a)之層（Y)的外側進行設置無機蒸鍍層 此等阻氣薄膜等之阻氣性層合物，於基 成第1層之層（Y)後，再形成第2層之層（ 〇 於設置2層以上之層（γ)時，各層（γ 相同’且各個構造’例如，不飽和羧酸化合 m J / c m2，特別 量爲此類範圍 90%以上之阻 :以基材層（X 視爲（Y1 )、 )分別所含之 可。又，各層 相異亦可。 中，於基材層 或含有聚合物 (Z)亦可。 :材層（X)形 γ )則可製造 )的構造可爲 物多價金屬鹽 -25- 200906614 之聚合物（a )與乙烯醇系聚合物（b )的組成比例，其種 類亦可改變。 例如，亦可例示令複數層（Y)中的乙烯醇系聚合物 (b )的比例依序減少’並將接至後述無機蒸鍍層（Z )的 層（γ)，作成實質上不含有乙烯醇系聚合物（b)之層的 態樣。 無機蒸鍍層（Z ) 無機蒸鍍層（Z )可無特別限定，利用以往已知作爲 薄膜等之蒸鍍層者。其中，期望其表面爲平滑的蒸鍍膜。 例如，含有鋁、鋅、銦、矽及錫等元素及視需要含有此等 金屬與氧之膜。於其中，氧可提高膜的透明性。此類無機 蒸鍍可使用CVD法、PVD膜、濺鍍法、電漿CVD法、CAT-CVD法等乾式製膜法形成。無機蒸鍍膜之厚度（每1層之 厚度）爲0.1〜1000 nm，其中可在5〜500 nm，更佳爲30 〜2 0 0 nm之範圍適當選擇。無機蒸鍍膜之厚度爲薄時，阻 氣薄膜之氧氣的阻擋性不足，厚時，則於蒸鍍層中易造成 裂痕。Chemical Specialty) A radical polymerization initiator which is manufactured and sold under the trade name of 2,4,6-trimethylbenzimidium diphenylphosphine oxide (trade name of Lamuson Fire Chemical Co., Ltd.; Speedcure®). Further, in order to increase the degree of polymerization or the polymerization rate, a polymerization accelerator may be added, and examples thereof include hydrazine, hydrazine-dimethylaminoethyl (meth)acrylate, and N-(methyl)propene morpholine. When irradiating the ionizing radiation to carry out the polymerization, generally, the irradiation amount of the ionizing radiation -24-200906614 is 1 to 1000 mJ/cm 2 , preferably 5 to 300, preferably 10 to 2 0 0 m J / cm 2 . . By the irradiation, the polymerization rate is preferably 80% or more, and a gas barrier layer such as a gas film is preferable. In the gas barrier laminate of the present invention, the gas barrier film is considered to be (X), and the layer (γ) (Y2), (Y3), (Y4) containing the polymer (a) can be exemplified (X). )/(Y')/(Y2) (Χ)/(Υ1)/(Υ2)/(Υ3) (Χ)/(Υ1)/(Υ2)/(Υ3)/(γ4) structure. Further, the contents of the polymer (b) which may be the same as or different from each other (Υ1), (Υ2), (Υ3), (the polymer (a) may be the same as each other or in the present invention a gas barrier layer (X) such as a gas barrier film and a layer containing the polymer (a), and a gas barrier film or the like which is provided on the outer side of the layer (Y) of (a) is provided with a gas barrier film or the like. a layered layer, after forming a layer (Y) of the first layer, and then forming a layer of the second layer (when a layer (γ) of two or more layers is provided, each layer (γ is the same 'and each structure' is, for example, not The saturated carboxylic acid is combined with m J / c m2, and the specific amount is a resistance of 90% or more in such a range: it may be contained in the substrate layer (X is regarded as (Y1), ), and the layers may be different. The substrate layer or the polymer (Z) may be: the material layer (X) shape γ) may be manufactured as a structure of the polyvalent metal salt-25-200906614 polymer (a) and vinyl alcohol The composition ratio of the polymer (b) may vary depending on the composition. For example, the ratio of the vinyl alcohol polymer (b) in the plurality of layers (Y) may be reduced sequentially and will be followed. The layer (γ) of the inorganic deposited layer (Z) is formed as a layer which does not substantially contain the layer of the vinyl alcohol polymer (b). The inorganic deposited layer (Z) The inorganic deposited layer (Z) is not particularly limited and can be utilized. Conventionally, it is known as a vapor deposition layer such as a film. Among them, a vapor-deposited film having a smooth surface is desired. For example, it contains an element such as aluminum, zinc, indium, antimony or tin, and a film containing such a metal and oxygen as necessary. Oxygen can improve the transparency of the film. Such inorganic vapor deposition can be formed by a dry film forming method such as a CVD method, a PVD film, a sputtering method, a plasma CVD method, or a CAT-CVD method. The thickness of the inorganic deposited film (per 1 The thickness of the layer is 0.1 to 1000 nm, and it can be appropriately selected in the range of 5 to 500 nm, more preferably 30 to 200 nm. When the thickness of the inorganic vapor deposition film is thin, the oxygen barrier of the gas barrier film is insufficient. When it is thick, it is easy to cause cracks in the vapor deposition layer.
層合無機蒸鍍層（Z )之阻氣薄膜的態樣，若將基材 層（X)簡述爲（X)、含有聚合物（a)之層（Y)簡述 爲（Y1 )、 （ Y2 )、 （ Y3 )、無機蒸鍍層（Z )簡述爲（Z )，則可例示以 -26- 200906614 (Χ)/(Ζ)/(Υ,)/(γ2) (Χ)/(Υ])/(Υ2)/(Ζ) (Χ)/(Ζ)/(Υ1)/(γ2)/(γ3) 等所示之層合構造。 另外，（Υ1) 、（Υ2) 、（Υ3)分別所含之聚合物（ a )的含量可彼此相同、或相異亦可。又，各層所含之聚 合物（b )的含量亦可彼此相同、或相異亦可。 此等阻氣薄膜於基材層（X )預先設置無機蒸鍍層（z )後，形成第1層之層（Y )，再形成第2層之層（Y )則 可製造。或者，於基材層（X)，形成第1層之層（Y)， 其後設置無機蒸鍍層（Z)，再形成第2層之層（Y)則可 製造。 於本發明之其他態樣中，含有聚合物（a )之層（γ ) 的複數層中之二層可彼此鄰接進行層合。此時，其一層之 乙烯醇系聚合物（b)的比例較另一層之乙烯醇系聚合物 的比例低，作成實質上不含有的態樣，且期望降低該乙嫌 醇系聚合物的比例，或者令實質上不含有情形之層（γ ) 鄰接至無機蒸鍍層（Z)。 併用此等含有乙烯醇系聚合物（b)之層（Y)時，其 一層（Y)之構成通常爲由不飽和羧酸化合物多價金屬鹽 之聚合物（a )爲1〜99重量％，乙烯醇系聚合物（b )爲1 〜99重量％所構成，其中亦以（a)爲60〜98重量％， （b )爲2〜4 0重量％，特別以（a )爲7 0〜9 5重量％， （ b )爲 -27- 200906614 5〜30重量％ ( (a)及（b)之合計爲100重量 〇 例如，一層（γ)與另一層（Y’）之各層 系聚合物（b)的濃度比率，期望一層（Y)的 另一層（Y，）之濃度比率的1/2以下’其中亦J 特佳爲實質上不含有之層所構成。 保護層 於本發明之阻氣薄膜等之阻氣性層合物中 )側的最外層期望設置可保護層（Y)的保護層 保護層（U)可列舉環氧樹脂、不飽和聚 樹脂、脲•蜜胺樹脂、聚胺基甲酸酯樹脂、聚 胺基樹脂、聚醯亞胺等之熱硬化性樹脂、聚烯 、聚丙烯、聚4-甲基-1-戊烯、聚丁烯等）、聚 二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘甲 )、聚醯胺（尼龍-6、尼龍-66、聚己二醯間苯 )、聚氯乙烯、聚醯亞胺、乙烯•醋酸乙烯酯 鹼化物、聚乙烯醇、聚丙烯腈、聚碳酸酯、聚 聚物、或其混合物等之熱可塑性樹脂等所構成 保護層（U)可直接層合至層（γ)，且亦可 層劑等之接黏劑予以層合。 保護層（U)之其他的適當例爲含有前述 的基材層（X-1 )。 經由使用含有前述無機微粒子之基材層（ %)爲適當 中的乙烯醇 濃度比率爲 义1/3以下， 1，於層（Y r ( u )。 酯樹脂、酚 矽氧樹脂、 烴（聚乙烯 酯（聚對苯 酸乙二酯等 伸二甲胺等 共聚物或其 苯乙烯、離 之層。此等 透過增黏塗 無機微粒子 :χ-ι )作爲 -28- 200906614 保護層，則可作成隱蔽性優良之阻氣薄膜等的層合物。 含有此等無機微粒子之保護層（U)可使用無延拉、 於至少一軸方向上延拉者等之任一者。經延拉的保護層（ U )爲耐熱性、剛性、透明性及阻氣性優良。 又，此等保護層（U)，爲了改良與阻氣薄膜等之阻 氣性層合物的接黏性，可將其表面，例如，進行電暈處理 、火焰處理、電漿處理、塗底處理、電漿塗敷處理、火焰 處理等之表面活化處理。 以下記述本發明之阻氣薄膜等之阻氣性層合物例。但 ，若保護層（U )簡述爲（U )，則可例示以 (X)/(Y1)/(Y2)/(U) (X)/(Y')/(Y2)/(Y3)/(U) (X)/(Y1)/(Z)/(Y2)/(U) (X)/(Z)/(Y')/(Y2)/(U) (X)/(Y1)/(Y2)/(Z)/(U) 等所示之層合構造。 另外’ （Y1) 、（Y2) 、（Y3)分別所含之聚合物（ a)的含量可彼此相同、或相異亦可。又，各層所含之聚 合物（b )的含量亦可彼此相同、或相異亦可。 又，本發明之阻氣性層合物中，於阻氣薄膜，經由對 基材層（X)之面層合熱熔黏層，則可取得適合作爲可熱 封包裝用薄膜的阻氣薄膜。此類熱熔黏層通常爲將作爲熱 -29- 200906614 熔黏層之公知的乙烯、丙烯、丁烯_丨、己嫌_丨、4 戊烯-1、辛烯-1等之α -烯烴單獨或共聚物、高壓扫 聚乙烯、線狀低密度聚乙烯（所謂L L D ρ Ε )、高g 烯、聚丙烯、聚丙烯無規共聚物、聚丁烯、聚4_Ef 嫌-1、低結晶性或非晶性之乙稀•丙稀無規共聚杉 •丁烯-1無規共聚物、丙烯.丁烯-1無規共聚物等 烴單獨或二種以上之組成物、乙嫌.醋酸乙稀酯尹 EVA)、乙烯·（甲基）丙烯酸共聚物或其金屬屋 與聚烯烴之組成物等所得之層。 其中，亦以高壓法低密度聚乙嫌、線狀低密g (所謂LLDPE )、高密度聚乙烯等之乙烯系聚合彩 熱熔黏層爲低溫熱封性、熱封強度等優良，故爲佳 又，此類熱熔黏層爲視需要，於本發明之阻葬 設置之層（Y )側的最外層，以保護層（U )型另 置亦可。 此等熱熔黏層亦可透過接黏劑等層合，且亦π 合。 實施例 其次，列舉實施例更加具體說明本發明，但 要不超過其要旨，則不被此些實施例所限制。 實施例及比較例中的物性値等可根據以下的 求出。 -甲基· i低密度 〉度聚乙 I基•戊 J、乙烯 ;之聚綠 ?聚物（ !、EVA :聚乙烯 ί所得之 〇 ,薄膜所 進行設 '直接層 發明只 價方法 -30- 200906614 <評價方法> (1 )多層薄膜之作成：於厚度50 // m之線狀低密度聚 乙烯薄膜（東Sero公司製商品名：T.U.X FCS)的單面， 將胺基甲酸酯系接黏劑（聚胺基甲酸酯系接黏劑（三化學 Polyurethane公司製商品名：Take 1 ac A3 1 0 ) : 1 2 重量份 ，異氰酸酯系硬化劑（三井化學Polyurethane公司製商品 名：Takenate A3 ) : 1重量份及醋酸乙酯：7重量份）塗佈 ’乾燥後，貼合實施例、比較例所得之阻氣性層合薄膜的 丙烯酸鋅聚合物層面（乾式層合），取得多層薄膜。 又，厚度7〇//m之無延拉聚丙烯薄膜（東Sero公司製 商品名：RXC·2 1 )的單面，將酯系接黏劑（聚酯系接黏劑 (二井化學Polyurethane公司製商品名：Takelac A525) :9重量份、異氰酸酯系硬化劑（三井化學P〇1yUrethane公 司製商品名：Takenate A52 ) : 1重量份及醋酸乙酯：7.5 重量份）塗佈，乾燥後，貼合實施例、比較例所得之阻氣 性層合薄膜的丙烯酸鋅聚合物層面（乾式層合），取得多 層薄膜。 (2)甑餾處理：上述方法所得之與無延拉聚丙烯薄 膜貼合的多層薄膜，以無延拉聚丙烯薄膜爲內面般回折， 並將二邊熱封作成袋狀後，加入水40cc作爲內容物，並將 另一邊熱封作成袋（三角熱封袋），將其以高溫高壓甑餾 殺菌裝置以1 2 PC，30分鐘之條件進行甑餾處理。甑餾處 理後’抽出內容物之水，取得甑餾處理後的多層薄膜。 (3 )透氧度[ml/(m2 · day . MPa)]:將上述方法所得 -31 - 200906614 之多層薄膜’使用Mocon公司製OX-TRAN 2/2 1 ML ’根據 JI S K 7 1 2 6，以溫度2 0 °C，濕度9 0 % R · Η .之條件測定。 (4 )水蒸氣穿透度[g/(m2 · day)]:將多層薄膜以線狀 低密度聚乙烯薄膜面爲內側般回折，並將二邊熱封作成袋 狀後，加入氯化鈣作爲內容物，並將另一邊熱封’作成表 面積爲0.01 m2般之袋（三角熱封袋），將其以4(TC ， 90%R.H.之條件放置3日，並以其重量差測定水蒸氣穿透度 <溶液（si )之製作> 將丙烯酸鋅水溶液[淺田化學公司製，濃度30重量％ ( 丙烯酸成分：20重量％，鋅成分10重量％ )]以固形成分比 率9 8.0重量％，以甲醇稀釋至2 5重量％之光聚合啓始劑[1 -(4-(2-羥乙氧基）苯基]-2-羥基-2-甲基-1-丙烷-1-酮（ Ciba Specialty Chemicals公司製商品名：I r u g a c ur e 2 9 5 9 )]以固形成分比率1 . 3重量％，及界面活性劑（花王公司 製商品名：Emalgen 120 )以固形成分比率0.7重量％般混 合’製作丙烯酸鋅溶液（si)。 <溶液（s2 )之製作> 於丙烯酸鋅與丙烯酸酯基改性聚乙烯醇的混合水溶液 濃度14重量％ (丙烯酸鋅成分：12重量％，丙烯酸酯基改 性聚乙烯醇成分2重量％ )]中混合上述丙烯酸鋅之溶液（ sl) ’並將丙烯酸鋅成分以固形成分比率88.5重量％，丙 -32- 200906614 烯酸酯基改性聚乙烯醇成分以固形成分比率9·7重量。/。，光 聚合啓始劑以固形成分比率1 2重量％，界面活性劑以固形 成分比率〇 · 6重量％混合，製作丙烯酸鋅與丙烯酸酯基改性 聚乙烯醇所構成的溶液（s2 )。 實施例1 於厚度12// m之氧化鋁蒸鍍聚酯薄膜（東sero公司製 商品名；TL-PET Η )的蒸鍍面，將上述之丙烯酸鋅溶液（ si)使用棒塗層法’令塗佈量爲固形成分1.2 g/m2般塗佈 ，立即使用紫外線照射裝置（EYE Graphic公司製EYE GRANDAGE 型式 ECS 301 G1 )，以照度：180 mW/cm2，積 算光量：180 m〗/cm2之條件對塗佈面照射紫外線令其聚合 形成層。更且’於此層上將上述丙烯酸鋅與丙烯酸酯基改 性聚乙烯醇之混合溶液（s2 )以塗佈量1.2 g/m2塗佈，並 以丙烯酸鋅溶液（s 1 )塗佈時同樣之條件照射UV令其聚合 ，設置含有改性聚乙嫌醇之層。如此取得，不含有丙稀酸 酯基改性聚乙烯醇之層與含有層二層層合的阻氣性層合薄 膜。所得之層合薄膜以上述記載之方法評價之結果示於表 實施例2 除了將不含有丙烯酸酯基改性聚乙烯醇層之丙烯酸鋅 溶液（s 1 )以固形成分〇 . 7 g/m2般塗佈以外’同實施例！處 理’取得層合薄膜。所得之層合薄膜以上述5己載之方法評 -33- 200906614 價之結果示於表1。 實施例3 除了將不含有丙烯酸酯基改性聚乙烯醇層之丙 溶液（s 1 )以固形成分0.4 g/m2般塗佈以外，同實ί 理，取得層合薄膜。所得之層合薄膜以上述記載之 價之結果示於表1。 實施例4 除了於聚酯薄膜（Unichica公司製商品名； PET 1 2 )的電暈處理面塗佈以外，同實施例3處理 層合薄膜。所得之層合薄膜以上述記載之方法評價 示於表1。 比較例1 除了塗佈丙烯酸鋅溶液（S1 )，且未塗佈丙烯 丙烯酸酯基改性聚乙烯醇的混合溶液（s2 )，僅形 酸鋅之聚合物層以外，同實施例3處理，取得層合 將其以上述記載之方法評價之結果示於表1。 比較例2 除了未塗佈丙烯酸鋅溶液（s 1 )，且塗佈丙烯 丙烯酸酯基改性聚乙烯醇的混合溶液（s2 )，僅形 丙烯酸酯基改性聚乙烯醇之層以外，同實施例1處 燦酸鋅 g例1處 方法評When the gas barrier film of the inorganic vapor-deposited layer (Z) is laminated, the substrate layer (X) is briefly described as (X), and the layer (Y) containing the polymer (a) is briefly described as (Y1), ( Y2), (Y3), and the inorganic vapor-deposited layer (Z) are briefly described as (Z), and exemplified by -26-200906614 (Χ)/(Ζ)/(Υ,)/(γ2) (Χ)/(Υ ]) / (Υ2) / (Ζ) (Χ) / (Ζ) / (Υ1) / (γ2) / (γ3) The laminated structure shown. Further, the content of the polymer (a) contained in each of (Υ1), (Υ2), and (Υ3) may be the same as or different from each other. Further, the content of the polymer (b) contained in each layer may be the same as or different from each other. These gas barrier films can be produced by previously providing the inorganic vapor deposited layer (z) on the base material layer (X) to form the first layer (Y) and then forming the second layer (Y). Alternatively, a layer (Y) of the first layer may be formed on the base material layer (X), and then an inorganic vapor-deposited layer (Z) may be provided, and a layer (Y) of the second layer may be formed. In other aspects of the invention, two of the plurality of layers comprising layer ([gamma] of polymer (a) may be laminated adjacent to one another. In this case, the ratio of the vinyl alcohol polymer (b) in one layer is lower than the ratio of the vinyl alcohol polymer in the other layer, and it is substantially not contained, and it is desirable to reduce the proportion of the ethyl alcohol polymer. Or, the layer (γ) which is substantially free of the case is adjacent to the inorganic deposited layer (Z). When the layer (Y) containing the vinyl alcohol polymer (b) is used in combination, the layer (Y) is usually composed of the polymer (a) of the polyvalent metal salt of the unsaturated carboxylic acid compound in an amount of from 1 to 99% by weight. The vinyl alcohol polymer (b) is composed of 1 to 99% by weight, wherein (a) is 60 to 98% by weight, (b) is 2 to 40% by weight, and particularly (a) is 7 0. ～ 5% by weight, (b) is -27-200906614 5 to 30% by weight (the total of (a) and (b) is 100% 〇 For example, one layer (γ) and the other layer (Y') are polymerized. The concentration ratio of the substance (b) is preferably 1/2 or less of the concentration ratio of the other layer (Y) of one layer (Y), wherein it is also preferably a layer which is substantially not contained. The protective layer is in the present invention. In the gas barrier laminate of a gas barrier film or the like, the outermost layer of the side is desirably provided with a protective layer (Y). The protective layer (U) may be an epoxy resin, an unsaturated poly resin, a urea melamine resin, or the like. Polyurethane resin, polyamine-based resin, thermosetting resin such as polyimine, polyene, polypropylene, poly 4-methyl-1-pentene, polybutene, etc., polydimethylene Ethylene glycol diester, polybutylene terephthalate, polynaphthyl), polyamidamine (nylon-6, nylon-66, polyhexamethylene benzene), polyvinyl chloride, polyimine, ethylene The protective layer (U) composed of a thermoplastic resin such as vinyl acetate alkali, polyvinyl alcohol, polyacrylonitrile, polycarbonate, a polymer, or a mixture thereof may be directly laminated to the layer (γ), and Adhesives such as layering agents are laminated. Other suitable examples of the protective layer (U) include the above-mentioned base material layer (X-1). By using the base material layer (%) containing the inorganic fine particles as appropriate, the vinyl alcohol concentration ratio is 1/3 or less, 1, and the layer (Y r ( u ). Ester resin, phenolphthalein, resin (hydrocarbon) a vinyl ester (polyethylene terephthalate or the like, such as a copolymer of dimethylamine or a styrene thereof, or a layer thereof. These are coated with an inorganic fine particle: χ-ι) as a protective layer of -28-200906614, which can be prepared. A laminate of a gas barrier film or the like which is excellent in concealability. The protective layer (U) containing such inorganic fine particles can be either stretched or stretched in at least one axial direction. (U) is excellent in heat resistance, rigidity, transparency, and gas barrier properties. Further, the protective layer (U) may be modified to improve the adhesion to a gas barrier laminate such as a gas barrier film. For example, a surface activation treatment such as a corona treatment, a flame treatment, a plasma treatment, a primer treatment, a plasma coating treatment, or a flame treatment is performed. Examples of gas barrier laminates such as a gas barrier film of the present invention are described below. However, if the protective layer (U) is briefly described as (U), it can be exemplified by (X) /(Y1)/(Y2)/(U) (X)/(Y')/(Y2)/(Y3)/(U) (X)/(Y1)/(Z)/(Y2)/(U ) Laminated structure shown by (X) / (Z) / (Y') / (Y2) / (U) (X) / (Y1) / (Y2) / (Z) / (U). The content of the polymer (a) contained in (Y1), (Y2), and (Y3) may be the same as or different from each other. Further, the content of the polymer (b) contained in each layer may be the same as each other. Further, in the gas barrier laminate of the present invention, the gas barrier film can be obtained as a heat sealable package by laminating a heat-fusible layer on the surface of the base material layer (X). A gas barrier film of a film. Such a hot-melt adhesive layer is generally known as ethylene, propylene, butene, bismuth, tetrapentene-1, octene which will be used as a hot-melt layer of heat -29-200906614. -1 or the like α-olefin alone or copolymer, high-pressure sweep polyethylene, linear low-density polyethylene (so-called LLD ρ Ε ), high-g-ene, polypropylene, polypropylene random copolymer, polybutene, poly 4_Ef A mixture of ethylene, propylene, propylene, butene-1, random copolymer, propylene, butene-1 random copolymer, or a mixture of two or more, which is suspected to be -1, low crystalline or amorphous. Material, B a layer obtained by a vinyl acetate (EVA), an ethylene/(meth)acrylic acid copolymer or a metal house thereof and a composition of a polyolefin, etc. Among them, a high-pressure method, a low-density polyethylene, and a linear low-density (LLDPE), high-density polyethylene, etc., the ethylene-based polymeric color hot-melt adhesive layer is excellent in low-temperature heat-sealing property, heat-sealing strength, etc., and such a hot-melt adhesive layer is required in the present invention. The outermost layer on the layer (Y) side of the funeral layer may be replaced by a protective layer (U). These hot-melt adhesive layers can also be laminated by an adhesive or the like, and are also π-bonded. EXAMPLES Next, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. The physical properties and the like in the examples and the comparative examples can be obtained by the following. -Methyl·i low density>degree of polyethyl I group • pentane J, ethylene; poly-green polymer (!, EVA: polyethylene obtained by ί, the film is set to 'direct layer invention price only method -30 - 200906614 <Evaluation method> (1) Preparation of a multilayer film: on one side of a linear low-density polyethylene film (trade name: TUX FCS, manufactured by Toro Sero Co., Ltd.) having a thickness of 50 // m, an aminocarboxylic acid Ester-based adhesive (polyurethane adhesive (trade name: Take 1 ac A3 1 0, manufactured by San Chemical Polyurethane Co., Ltd.): 12 parts by weight, isocyanate-based hardener (trade name of Mitsui Chemicals Polyurethane Co., Ltd.) :Takenate A3 ) : 1 part by weight and ethyl acetate: 7 parts by weight) After coating, after drying, the zinc acrylate polymer layer (dry lamination) of the gas barrier laminate film obtained in the examples and the comparative examples was bonded. A multilayer film is obtained. Further, a one-side non-stretched polypropylene film (trade name: RXC·2 1 manufactured by Toro Sero Co., Ltd.) having a thickness of 7 〇//m is an ester-based adhesive (polyester adhesive ( Product name: Takelac A525) manufactured by Mitsui Chemicals Polyurethane Co., Ltd.: 9 parts by weight, isocyanate-based hardening (Mitsubishi Chemical P〇1yUrethane Co., Ltd., trade name: Takenate A52): 1 part by weight and ethyl acetate: 7.5 parts by weight), after drying, the acrylic film of the gas barrier laminate film obtained in the examples and the comparative examples was bonded. The zinc polymer layer (dry lamination) is used to obtain a multilayer film. (2) Retorting treatment: The multilayer film obtained by the above method and bonded to the non-stretched polypropylene film is folded back like a non-stretched polypropylene film. After heat sealing the two sides into a bag shape, 40 cc of water was added as a content, and the other side was heat-sealed into a bag (triangular heat-sealing bag), which was subjected to a high-temperature and high-pressure retort sterilization device at 1 2 PC for 30 minutes. The conditions are subjected to a retort treatment. After the retort treatment, the water of the content is extracted to obtain a multilayer film after the retort treatment. (3) Oxygen permeability [ml/(m2 · day. MPa)]: obtained by the above method - 31 - 200906614 The multilayer film 'Using OX-TRAN 2/2 1 ML' manufactured by Mocon Co., Ltd. is measured according to JI SK 7 1 2 6, with a temperature of 20 ° C and a humidity of 90% R · Η. (4) Water vapor permeability [g/(m2 · day)]: thin film with low density polyethylene The film surface is folded back inside, and the two sides are heat-sealed into a bag shape, calcium chloride is added as a content, and the other side is heat-sealed to form a bag having a surface area of 0.01 m2 (triangular heat-sealing bag), and The product was placed at 4 (TC, 90% RH for 3 days, and the water vapor permeability was measured by the difference in weight < Preparation of solution (si) > A zinc acrylate aqueous solution [manufactured by Asada Chemical Co., Ltd., concentration: 30% by weight ( Acrylic component: 20% by weight, zinc component 10% by weight)] Photopolymerization initiator [1 -(4-(2-hydroxyethoxy) diluted to 95% by weight in methanol at a solid content ratio of 98.0% by weight) a phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: I rugac ur e 2 9 5 9 ) manufactured by Ciba Specialty Chemicals Co., Ltd.) in a solid content ratio of 1.3% by weight, The surfactant (manufactured by Kao Corporation: Emalgen 120) was mixed in a solid content ratio of 0.7% by weight to prepare a zinc acrylate solution (si). <Preparation of Solution (s2)> Mixed aqueous solution concentration of zinc acrylate and acrylate-modified polyvinyl alcohol 14% by weight (zinc acrylate component: 12% by weight, acrylate-modified polyvinyl alcohol component 2% by weight) The above zinc acrylate solution ( sl) was mixed with the zinc acrylate component at a solid content ratio of 88.5 wt%, and the C-32-200906614 acrylate-modified polyvinyl alcohol component was a solid content ratio of 9.7 wt. /. The photopolymerization initiator was mixed at a solid content ratio of 12% by weight, and the surfactant was mixed at a solid content ratio of 〇 · 6 wt% to prepare a solution (s2 ) of zinc acrylate and acrylate-modified polyvinyl alcohol. Example 1 The above-mentioned zinc acrylate solution (si) was subjected to a bar coating method on a vapor deposition surface of an alumina vapor-deposited polyester film (trade name, manufactured by Toray Sero Co., Ltd.; TL-PET®) having a thickness of 12/m. The coating amount was applied as a solid component of 1.2 g/m2, and immediately an ultraviolet irradiation device (EYE GRANDAGE type ECS 301 G1 manufactured by EYE Graphic Co., Ltd.) was used, and the illuminance was 180 mW/cm2, and the integrated light amount was 180 m/cm2. Conditions The irradiated surface is irradiated with ultraviolet rays to polymerize it to form a layer. Further, 'the above mixed solution of zinc acrylate and acrylate-modified polyvinyl alcohol (s2 ) was applied at a coating amount of 1.2 g/m 2 on the layer, and the same was applied when the zinc acrylate solution (s 1 ) was applied. The condition is irradiated with UV to polymerize it, and a layer containing the modified polyethyl alcohol is provided. Thus, a gas barrier laminated film which does not contain a layer of the acrylate-modified polyvinyl alcohol and which is laminated with the two layers of the layer is obtained. The results of the evaluation of the obtained laminated film by the method described above are shown in Table Example 2 except that the zinc acrylate solution (s 1 ) containing no acrylate-modified polyvinyl alcohol layer was solidified to form a basis. 7 g/m 2 Apply the same as the same embodiment! Process 'to obtain a laminated film. The obtained laminate film is shown in Table 1 as a result of the above-mentioned method of 5 -10. Example 3 A laminate film was obtained in the same manner as in the case where the propylene solution (s 1 ) containing no acrylate-modified polyvinyl alcohol layer was coated at a solid content of 0.4 g/m 2 . The obtained laminated film is shown in Table 1 as a result of the above-described price. Example 4 A laminated film was treated in the same manner as in Example 3 except that the surface of the polyester film (trade name of the company Unichica; PET 1 2) was applied to the corona-treated surface. The obtained laminated film was evaluated in Table 1 by the method described above. Comparative Example 1 The same procedure as in Example 3 was carried out except that the zinc acrylate solution (S1) was applied and the mixed solution (s2) of the acryl acrylate-modified polyvinyl alcohol was not applied, except for the polymer layer of the zinc citrate. The results of lamination by the method described above are shown in Table 1. Comparative Example 2 Except that the zinc acrylate solution (s 1 ) was not applied, and the mixed solution (s2 ) of the acryl acrylate-modified polyvinyl alcohol was applied, and only the layer of the acrylate-modified polyvinyl alcohol was used, the same was carried out. Example 1 method of zinc sulphate g
Enblet ，取得 之結果 酸鋅與 成丙烯 薄膜。 酸鋅與 成含有 理，取 -34- 200906614 得層合薄膜。將其以上述記載之方法評價之結果示於表1 比較例3 除了於聚酯薄膜（Unichica公司製商品名；Enblet P E T 1 2 )的電暈處理面塗佈以外，同比較例2處理，取得 層合薄膜。將其以上述記載之方法評價之結果示於表1。 比較例4 將厚度12/zm之氧化鋁蒸鍍聚酯薄膜（東Sero公司製 商品名：TL-P ET Η )以上述記載之方法評價之結果示於表 [表1] 例 基材 塗佈量 (g/m2) 透氧度 [ml/(m2 · day · MPa)] 水蒸氣穿透度 [g/(m2 · day)] 丙烯酸 鋅之聚 合物之層 含有丙烯酸鋅 之聚合物及丙 烯酸酯基改性 PVA之層 未處理 121〇C甑餾 處理後 未處理 實施例1 TL-PET Η 1.2 1.2 0.4 0.8 0.3 實施例2 TL-PET Η 0.7 1.2 0.3 0.9 0.5 實施例3 TL-PET Η 0.4 1.2 0.4 0.7 0.6 實施例4 PET 0.4 1.2 1.0 2.7 8.5 比較例1 TL-PET Η 0.4 0.0 1.3 3.5 1.0 比較例2 TL-PET Η 0.0 1.2 0.3 2.5 0.3 比較例3 PET 0.0 1.2 1.1 5.5 8.6 比較例4 TL-PET H — — 10 30 1.2 -35- 200906614 如表1所闡明般，將丙烯酸鋅聚合物之層與含有丙烯 酸鋅之聚合物與丙烯酸酯改性聚乙烯醇之層鄰接層合的阻 擋薄膜（實施例1〜3 )，與使用氧化鋁蒸鍍聚酯薄膜作爲 基材（比較例4)相比較，顯示出透氧度及水蒸氣穿透度 優良之値。若與僅有丙烯酸鋅聚合物之層之情形（比較例 1 )相比較，則透氧度、水蒸氣穿透度爲優良。若與僅含 有丙烯酸鋅之聚合物與丙烯酸酯基改性聚乙烯醇之層之情 形（比較例2 )相比較，則可知甑餾處理後之阻擋性非常 優良。又，以基材作成聚酯薄膜之情形，含有丙烯酸酯基 改性聚乙烯醇之層與不含有層鄰接層合的阻擋薄膜（實施 例4 )，與僅含有丙烯酸鋅之聚合物與丙烯酸酯改性聚乙 烯醇之層之情形（比較例3 )相比較，可知甑餾處理後的 透氧度優良。 (產業上之可利用性） 本發明之阻氣薄膜爲經由使用多數含有不飽和羧酸化 合物多價金屬鹽之聚合物（a)之層（Y)，則可令高濕度 下的阻氣性特別優良，活用此類特徵，則可使用於各種用 途。 又，於保護層使用含有無機微粒子之白色薄膜時，可 作成隱蔽性良好的阻氣薄膜。 活用此類特徵’本發明之阻氣薄膜亦可適當使用於乾 燥食品、飲料、煮沸甑餾食品、補助食品等之包裝材料， 其中特別以要求高阻氣性之內容物的食品包裝材爲首、洗 -36- 200906614 髮精、洗劑、入浴劑、芳香劑等之盥洗用製品之包裝材料 、粉體、顆粒狀、錠劑等之醫藥品、輸液袋爲首之液狀醫 藥品、醫療用具之包裝袋及包裝容器構材等之醫療用途、 硬碟、配線基盤、印刷基盤等之電子構件包材、液晶顯示 器、電獎顯示器、無機•有機EL顯示器、電子報紙等之平 面顯示器用阻擋材、其他電子材料用之阻擋材、真空隔熱 材用阻擋材、墨水筒等之工業製品的包裝材等之各式各樣 製品的包I材料、或雷不封糾 歧φ, 队 4革子材枓、精饴構件、醫藥品爲首之 氧氣穿透及厭濕材料的保護材。 -37-Enblet, the result obtained is a zinc acid and a propylene film. The zinc hydride is formed into a film, and the laminated film is obtained from -34 to 200906614. The results of the evaluation by the method described above are shown in Table 1. Comparative Example 3 was treated in the same manner as in Comparative Example 2 except that it was applied to a corona-treated surface of a polyester film (trade name of Unichica Co., Ltd.; Enblet PET 1 2 ). Laminated film. The results of the evaluation by the methods described above are shown in Table 1. Comparative Example 4 The alumina vapor-deposited polyester film (trade name: TL-P ET 制 manufactured by Toro Sero Co., Ltd.) having a thickness of 12/zm was evaluated by the method described above. [Table 1] Example substrate coating Amount (g/m2) Oxygen permeability [ml/(m2 · day · MPa)] Water vapor permeability [g/(m2 · day)] The layer of the zinc acrylate polymer contains zinc acrylate polymer and acrylate The layer of the base-modified PVA was not treated. 121 〇C retort treatment, untreated Example 1 TL-PET Η 1.2 1.2 0.4 0.8 0.3 Example 2 TL-PET Η 0.7 1.2 0.3 0.9 0.5 Example 3 TL-PET Η 0.4 1.2 0.4 0.7 0.6 Example 4 PET 0.4 1.2 1.0 2.7 8.5 Comparative Example 1 TL-PET Η 0.4 0.0 1.3 3.5 1.0 Comparative Example 2 TL-PET Η 0.0 1.2 0.3 2.5 0.3 Comparative Example 3 PET 0.0 1.2 1.1 5.5 8.6 Comparative Example 4 TL- PET H — — 10 30 1.2 -35- 200906614 A barrier film in which a layer of a zinc acrylate polymer and a layer containing a zinc acrylate polymer and an acrylate-modified polyvinyl alcohol are laminated adjacently as illustrated in Table 1 Examples 1 to 3) showed oxygen permeability as compared with the use of an alumina vapor-deposited polyester film as a substrate (Comparative Example 4). The Zhi and excellent water vapor penetration. When compared with the case where only the layer of the zinc acrylate polymer was used (Comparative Example 1), the oxygen permeability and the water vapor permeability were excellent. When compared with the case where only the layer containing the zinc acrylate polymer and the acrylate-based modified polyvinyl alcohol (Comparative Example 2) was used, it was found that the barrier property after the retorting treatment was extremely excellent. Further, in the case where the substrate is formed into a polyester film, the layer containing the acrylate-modified polyvinyl alcohol is laminated adjacent to the layer containing no layer (Example 4), and the polymer containing only zinc acrylate and the acrylate. In the case of the layer of the modified polyvinyl alcohol (Comparative Example 3), it was found that the oxygen permeability after the rectification treatment was excellent. (Industrial Applicability) The gas barrier film of the present invention is a gas barrier property at a high humidity by using a layer (Y) of a polymer (a) containing a large amount of a polyvalent metal salt of an unsaturated carboxylic acid compound. It is particularly excellent, and it can be used for various purposes by utilizing such characteristics. Further, when a white film containing inorganic fine particles is used for the protective layer, a gas barrier film having good concealability can be obtained. The gas barrier film of the present invention can also be suitably used for packaging materials such as dried foods, beverages, boiled foods, and supplementary foods, among which food packaging materials requiring high gas barrier properties are particularly preferred. , Wash-36- 200906614 Packaging materials, powders, granules, lozenges, etc., liquid medicines, medical products, such as hair powder, lotion, bathing agent, fragrance, etc. For medical applications such as packaging bags and packaging materials, electronic components such as hard disks, wiring boards, and printing substrates, liquid crystal displays, electric award displays, inorganic/organic EL displays, electronic newspapers, etc. Materials, barrier materials for other electronic materials, barrier materials for vacuum insulation materials, packaging materials for industrial products such as ink cartridges, etc., package I materials, or ray unblocking φ, team 4 leather Substrate 饴, fine 饴 components, pharmaceuticals, oxygen penetrating and protective materials for anaesthetic materials. -37-