JP2011020315A - Structure of gas-barrier composition and film equipped with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure of a gas-barrier composition which achieves gas-barrier properties and hot water resistance over a long period of time at high humidity and exerts excellent gas-barrier properties at an initial stage after manufacturing. <P>SOLUTION: A shaped composition (X) comprises a compound (A) having two or more hydroxy groups in a molecule, a polycarboxylic acid (B) and an alkali compound (C). The polycarboxylic acid (B) is composed of at least one selected from an ethylene-maleic acid copolymer (b1) and a 1,2,3,4-butane tetracarboxylic acid (b2). A mass ratio of the compound (A) with respect to the polycarboxylic acid (B), or (A)/(B) is 95/5 to 5/95. At least a part of the compound (A) and the polycarboxylic acid (B) are crosslinked. The shaped composition (X) is subjected to application treatment or impregnation treatment using an iodine compound (Y), and then to coating treatment or impregnation treatment using a metal compound (Z). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a gas barrier composition structure and a film provided with the structure.

  Thermoplastic resin films such as polyamide film and polyester film are excellent in strength, transparency, and moldability, and thus are used in a wide range of applications as packaging materials. However, since these thermoplastic resin films have a high permeability to gases such as oxygen, when they are used for packaging general foods, retort-treated foods, etc., these films are permeated while stored for a long period of time. Deterioration of food may occur due to oxygen and other gases. In order to solve these problems, a film having excellent gas barrier properties has been developed so as to ensure long-term storage of foods and the like.

  Patent Document 1 contains a compound having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid having a carboxyl group on each of consecutive 3 to 20 carbons, and an alkali compound. The composition in which the mass ratio of the polyvalent carboxylic acid is in the range of (compound) / (polyvalent carboxylic acid) = 95/5 to 5/95, and the compound and the polyvalent carboxylic acid are partially crosslinked. A gas barrier composition obtained by coating or impregnating with a metal compound is described.

JP 2005-146268 A

  When the gas barrier composition described in Patent Document 1 is used, a film excellent in long-term gas barrier properties and hot water resistance can be obtained. However, there are cases where it takes time until the gas barrier property is developed, and therefore a film capable of improving the gas barrier property immediately after production has been desired.

  The present invention solves the above-described problems, and not only can achieve long-term gas barrier properties and hot water resistance even under high humidity, but also has an excellent gas barrier property at an early stage after production. An object structure and a film including the structure are to be provided.

  As a result of intensive studies, the inventors applied a coating agent containing a specific resin composition to the surface of the film, treated the resin composition with an iodine compound, and further treated with a metal compound. The inventors have found that the above problems can be solved by forming a layer on the film surface, and have reached the present invention. That is, the gist of the present invention is as follows.

(1) having a tangified composition (X),
The composition (X) contains a compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C), and the polyvalent carboxylic acid (B) ) Is at least one selected from ethylene-maleic acid copolymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and compound (A) and polyvalent carboxylic acid ( B) has a mass ratio of (A) / (B) = 95/5 to 5/95, and at least a part of compound (A) and polyvalent carboxylic acid (B) is crosslinked,
The tangified composition (X) is subjected to a coating treatment or impregnation treatment using an iodine compound (Y) and then a coating treatment or impregnation treatment using a metal compound (Z). A gas barrier composition structure characterized by comprising:

  (2) The gas barrier composition structure according to (1), wherein the composition (X) contains an inorganic layered compound (D).

(3) A compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C), wherein the polyvalent carboxylic acid (B) is ethylene- It is at least one selected from maleic acid copolymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and the mass of compound (A) and polyvalent carboxylic acid (B) A tangible composition (X) in which the ratio is in the range of (A) / (B) = 95/5 to 5/95 and at least a part of the compound (A) and the polyvalent carboxylic acid (B) is crosslinked And
The tangified composition (X) is subjected to a coating treatment or an impregnation treatment using an iodine compound (Y), followed by a coating treatment or an impregnation treatment using a metal compound (Z). A method for producing a gas barrier composition structure.

  (4) The method for producing a gas barrier composition structure according to (3), wherein the composition (X) contains the inorganic layered compound (D).

  (5) A gas barrier film characterized in that a layer composed of the gas barrier composition structure according to (1) or (2) is provided on at least one surface of a thermoplastic resin film.

  (6) An inorganic layer is provided between the thermoplastic resin film and the layer composed of the gas barrier composition structure or on the surface side of the layer composed of the gas barrier composition structure. (5) The gas barrier film according to (5).

(7) A compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C), wherein the polyvalent carboxylic acid (B) is ethylene- It is at least one selected from the maleic acid copolymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and the mass ratio of the compound (A) and the polyvalent carboxylic acid (B) Is a range of (A) / (B) = 95/5 to 5/95, and a layer of the composition (X) in which at least a part of the compound (A) and the polyvalent carboxylic acid (B) is crosslinked , Formed on at least one side of the thermoplastic resin film,
The layer of the composition (X) is subjected to a coating treatment or an impregnation treatment using an iodine compound (Y), followed by a coating treatment or an impregnation treatment using a metal compound (Z). A method for producing a gas barrier film.

  (8) The method for producing a gas barrier film according to (7), wherein the composition (X) contains the inorganic layered compound (D).

  (9) The gas barrier according to (7) or (8), wherein an inorganic layer is provided between the thermoplastic resin film and the composition (X) layer or on the surface side of the composition (X) layer. For producing a conductive film.

  According to the present invention, a gas barrier composition having excellent gas barrier performance for a long time even under high humidity, excellent gas barrier performance even under hydrothermal conditions, and excellent gas barrier properties at an early stage after production. An object structure and a gas barrier film provided with this structure can be obtained. The gas barrier composition structure and the gas barrier film provided with the structure can be produced by a method with excellent productivity, and can be suitably used for food packaging films and the like.

Hereinafter, the present invention will be described in detail.
The gas barrier composition structure of the present invention is obtained by forming a composition (X) composed of the components (A) to (C) described later, and then treating the metal compound (Z) with an iodine compound (Y). The processing using was performed. Here, to make tangible means to make an originally intangible composition tangible, for example, by applying the composition to a substrate to form a layered body.

The composition (X) contains a compound (A) having two or more hydroxyl groups in the molecule. As this compound (A), any of a high molecular compound, an oligomer, and a low molecular compound may be sufficient.
Examples of the polymer compound include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyhydroxyethyl methacrylate, polysaccharides (polymer compounds in which 7 or more monosaccharides are polyglycosylated: starch, cellulose, galactomannan, carrageenan , Chitin, chitosan, etc.) and various polymer compounds modified with a hydroxyl group.

  Examples of the oligomer include oligosaccharides (having 3 to 6 monosaccharides having glycosyl bonds: raffinose, gentianose, etc.) and those having a short molecular chain in the above polymer compound.

Examples of the low molecular weight compound include ethylene glycol, diethylene glycol, monosaccharides (disaccharides, oligosaccharides, polysaccharides, and usually represented by C _m (H ₂ O) _n : glucose, galactose, mannose, Fructose, erythrose, arabinose, etc.), disaccharides (two monosaccharides with glycosyl bonds: maltose, lactose, sucrose, cellobiose, etc.), sugar alcohols (polyhydroxyalkanes obtained by reducing monosaccharides: Sorbitol, mannitol, dulcitol, xylitol, erythritol, glycerol, etc.). Furthermore, examples of the aromatic compound include catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), and the like.

  Among these, as the compound (A), polyvinyl alcohol, ethylene-vinyl alcohol copolymer and polysaccharide are preferable from the viewpoint of gas barrier properties, and polyvinyl alcohol is particularly preferable.

  In the compound (A), a part of the hydroxyl group is substituted by esterification, carboxymethylation, acetylation, phosphorylation, carboxylation, amination, allyl etherification, methyl etherification, carboxymethyl etherification, grafting, etc. It may be denatured. However, when the ratio of the hydroxyl group contained in the compound (A) is too low, the ester crosslinking density with the polyvalent carboxylic acid (B), which will be described later in detail, is lowered, and the gas barrier property may be insufficient. For this reason, the substitution rate of the hydroxyl group is preferably in the range of 0 to 50%, more preferably in the range of 0 to 30%, further preferably in the range of 0 to 20%, and 0 to 10%. It is particularly preferable that the range is

  The polyvinyl alcohol preferably used as the compound (A) can be obtained by a known method such as complete or partial saponification of a vinyl ester polymer. Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is most preferred industrially.

  It is also possible to copolymerize other vinyl compounds with the vinyl ester as long as the effects of the present invention are not impaired. Other vinyl monomers include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid and methacrylic acid and their esters, salts, anhydrides, amides and nitriles; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid. Examples include acids and salts thereof; α-olefins having 2 to 30 carbon atoms; alkyl vinyl ethers; vinyl pyrrolidones. However, if a large amount of the hydrophobic copolymer component is contained, the water solubility is impaired, resulting in inconvenience in the production of the composition (X). Therefore, the molar ratio of the vinyl alcohol unit to other vinyl compound units in the polyvinyl alcohol. Is preferably in the range of 10/90 to 100/0.

  As the saponification method, a known alkali saponification method or acid saponification method can be used, and among them, a method of alcoholysis using an alkali hydroxide in methanol is preferable. The degree of saponification is preferably closer to 100% from the viewpoint of gas barrier properties. If the degree of saponification is too low, the barrier performance will decrease. For this reason, the saponification degree is usually about 90% or more, preferably 95% or more, more preferably 99% or more. The average degree of polymerization of the vinyl ester polymer is preferably from 50 to 3000, more preferably from 80 to 2500, and even more preferably from 100 to 2000 from the viewpoint of the difficulty of polymerization and handleability.

  The polyvalent carboxylic acid (B) constituting the composition (X) is at least one selected from an ethylene-maleic acid copolymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2). Certain compounds can be used. Which is selected as the polyvalent carboxylic acid (B), as will be described later, in combination with the treatment of either coating or immersion using the metal compound (Z), simplicity, gas barrier properties, hot water resistance From the viewpoint of balance, etc., it may be appropriately selected so as to obtain an optimal combination.

  Among the polyvalent carboxylic acids (B), the ethylene-maleic acid copolymer (b1) is obtained by polymerizing maleic anhydride and ethylene by a known method such as solution radical polymerization. The obtained polymer preferably contains 10 mol% or more of maleic acid units. If the maleic acid unit is less than 10 mol%, the formation of a crosslinked structure by reaction with the hydroxyl group of the compound (A) tends to be insufficient and the gas barrier property tends to be lowered. The ethylene-maleic acid copolymer (b1) can be copolymerized with a small amount of other vinyl compounds within a range not impairing the effects of the present invention. Examples of such vinyl compounds include acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate; vinyl formate, vinyl acetate, and the like. Examples thereof include vinyl esters; olefins having 3 to 30 carbon atoms such as styrene, p-styrene sulfonic acid, propylene, and isobutylene; compounds having a reactive group that reacts with a hydroxyl group of PVA, and the like. In addition, the maleic acid unit in the ethylene-maleic acid copolymer (b1) may have a maleic anhydride structure, and these are described without particular distinction in this specification.

  Among the polyvalent carboxylic acids (B), the carboxyl group of 1,2,3,4-butanetetracarboxylic acid (b2) may be partially esterified or amidated to form an acid anhydride structure. It may be.

  In the composition (X), the mass ratio (A) / (B) between the compound (A) and the polyvalent carboxylic acid (B) needs to be in the range of 95/5 to 5/95, preferably Is in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, still more preferably in the range of 60/40 to 20/80, and particularly preferably 50/50 to The range is 20/80. When the compound (A) has a mass ratio of more than 95% or less than 5%, the gas barrier properties of the film particularly in a high humidity atmosphere are insufficient.

  The composition (X) contains an alkali compound (C). The alkali compound (C) is presumed to promote esterification of the compound (A) and the polyvalent carboxylic acid (B) by catalytic action.

  Examples of the alkali compound (C) include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; ammonium compounds such as ammonium hydroxide and organic ammonium hydroxide compounds; carbonates, Examples thereof include nitrites, nitrates, sulfites, sulfates, hydrochlorides, phosphates, phosphites, hypophosphites, and salts of organic metals and alkali metals such as acetates. Of these, alkali metal hydroxides such as sodium hydroxide and sodium hypophosphite are particularly preferable.

  In order for the alkali compound (C) to effectively promote esterification, the molar ratio (C) / (B) is 1/100 to 50/100 with respect to the carboxyl group of the polyvalent carboxylic acid (B). It is preferable to use in a range. The range is more preferably 2/100 to 40/100, and particularly preferably 2/100 to 30/100. If the molar ratio of the alkali compound (C) exceeds 50 with respect to the polyvalent carboxylic acid (B) 100 or is lower than 1, the resulting composition (X) may have insufficient gas barrier properties. is there. That is, when the molar ratio of the alkali compound (C) is low, the esterification catalytic effect is insufficient, and when it is high, the amount of carboxylic acid salt increases so that the amount of carboxylic acid that can contribute to esterification decreases. In any case, the gas barrier property of the resulting composition (X) may be insufficient.

  In the composition (X), it is necessary for the expression of the barrier property that at least a part of the compound (A) and the polyvalent carboxylic acid (B) is crosslinked by heat treatment or the like. The compound (A) and the polyvalent carboxylic acid (B) are cross-linked by the above-described ester bond, for example, by heat treatment.

The presence of the ester bond can be analyzed by coating the base material with the compound (A) and measuring the infrared spectrum of the coating layer by the ATR method. When the compound (A) and the polyvalent carboxylic acid (B) are cross-linked by an ester bond, the absorption peak of the carbonyl group in the polyvalent carboxylic acid (B) is shifted to the high wave number side. Therefore, a difference spectrum from the compound (A) to the polyvalent carboxylic acid (B) is taken, and the remaining absorption peak is defined as a peak derived from an ester bond. For example, taking a baseline limited to the region of 1600-1850 cm ⁻¹ , normalizing the absorbance of the peaks of the carbonyl groups of the compound (A) and the polyvalent carboxylic acid (B), so as not to fall below the baseline A peak difference spectrum is taken, and an absorption peak remaining at 1695 to 1800 cm ⁻¹ can be determined to be an ester bond-derived peak. For example, when the compound (A) and the polyvalent carboxylic acid (B) are polyvinyl alcohol and 1,2,3,4-butanetetracarboxylic acid, a difference spectrum is taken by the above method, and the remaining 1720 cm ⁻ It can be judged that the peak near ¹ is a peak derived from the carbonyl of the ester bond.

  As a method of heat treatment for crosslinking the compound (A) and the polyvalent carboxylic acid (B) with an ester bond, a non-contact heat treatment apparatus such as a hot air drier, a vacuum drier, an infrared heater, a hot roll, The method of using well-known apparatuses, such as contact-type heat processing apparatuses, such as a hot press machine, can be mentioned, These methods can also be used in combination. The heat treatment temperature varies depending on the thermal efficiency of the apparatus used, but is preferably 130 ° C. or higher in order to form an ester bridge in a short time, and more preferably 150 ° C. or higher in order to shorten the heat treatment time. . The heat treatment time is usually 1 second or longer, preferably 3 seconds or longer. If the heat treatment temperature is too low or the heat treatment time is too short, ester crosslinking may be insufficient and gas barrier properties may be insufficient.

In the present invention, the iodine compound (Y) for treating the tangified composition (X) is used in the form of an aqueous solution for the purpose of improving the permeability of the metal compound (Z) described later. Examples of the iodine compound (Y) include iodine, lithium iodide, potassium iodide, sodium iodide, ammonium iodide and the like. The iodine compound (Y) is preferably polyiodide ions in water, and examples of polyiodide ions include triiodide ions. The presence of triiodide ions can be confirmed by a blue-violet color due to the iodine starch reaction. Triiodide ions are obtained by mixing a salt that produces iodide ions with iodine. Although the density | concentration of an iodine compound (Y) is not specifically limited, From the point of the improvement effect of hot water resistance, it is preferable that an iodine atom is 1 * 10 < ^-5 > mol / L or more. On the other hand, if the concentration is too high, the appearance of the gas barrier composition may deteriorate, so the upper limit of the concentration is preferably 1 × 10 ⁻³ mol / L.

  The iodine compound (Y) is applied to the tangified composition (X) containing the above (A) to (C) (coating treatment), or the tangified composition (X) is applied. It is used by immersing (immersion treatment) in a solvent containing the iodine compound (Y). The coating treatment and the immersion treatment can be selected according to gas barrier characteristics and other purposes. Hereinafter, the composition (X) obtained by applying or dipping the iodine compound (Y) is referred to as “composition (X ′)”. The coating treatment is advantageous in that it can be performed relatively easily. On the other hand, the dipping treatment has a feature that the permeability of the metal compound (Z) described later can be further enhanced.

  Examples of the coating treatment of the iodine compound (Y) include a spraying method and a method using a known coater. As the coater, for example, an air knife coater, a kiss roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a dip coater, a die coater or the like can be used.

  The drying method for removing the solvent after coating is not particularly limited, but non-contact heat treatment devices such as hot air dryers, vacuum dryers, infrared heaters, and contact-type heat treatments such as hot rolls and heat presses. A known method using an apparatus can be used. A combination of these can also be used. The heat treatment temperature varies depending on the boiling point of the solvent used and the thermal efficiency of the apparatus, but is preferably 80 ° C. or higher in order to increase the drying efficiency. The drying time is usually 1 second or longer, preferably 3 seconds or longer.

  Next, the immersion treatment of the iodine compound (Y) will be described. In order to increase the efficiency of the immersion treatment, it is preferable to heat the solvent. At this time, the tangified composition (X) may be immersed in a solvent and then heated, or the tangified composition (X) may be immersed in a previously heated solvent. The temperature of the preferred solvent is in the range of 30 to 100 ° C, more preferably in the range of 60 to 95 ° C from the viewpoint of processing efficiency. If the temperature is too low, it takes a long time to obtain the penetration effect of the iodine compound (Y). If the temperature is too high, decomposition of the composition (X) may occur. The immersion treatment time is preferably 1 second to 1 minute. If the immersion treatment time is too short, the effect of improving the permeability of the metal compound (Z) described later will be insufficient, and if the immersion treatment time is too long, the production efficiency will deteriorate. Moreover, about the drying after an immersion process, the method similar to the case of the coating process mentioned above can be used suitably.

  For the purpose of improving hot water resistance and long-term wet heat resistance, the metal compound (Z) is applied or immersed in the composition (X ′) that has been treated with the iodine compound (Y). Either the coating treatment or the dipping treatment can be selected depending on the gas barrier characteristics and other purposes.

  Examples of the metal compound (Z) include alkali metals such as Li, Na and K, alkaline earth metals such as Ca and Mg, amphoteric metals such as Al, Zn and Sn, Ti, Zr, Fe, Co, Ni, Cu, Oxides of at least one metal selected from transition metals such as Mn; hydroxides; chlorides; inorganic salts such as nitrates, silicates, phosphates, hypophosphites, carbonates, oxysulfates; acetic acid Examples thereof include organic salts such as salts, stearates and oxyacetates. These metal salts and metal oxides may be a solid solution of two or more metals, or may be a layered compound. Among these metals, an oxide or a metal salt of at least one metal selected from alkaline earth metals, amphoteric metals and long-period type periodic table group 4A is preferable, and at least one selected from Ca, Mg, Al, Ti, and Zr. More preferred are two metal oxides and metal salts. More preferable examples include magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, and hydrotalcite. Of these, magnesium oxide and hydrotalcite, which are highly effective in improving hot water resistance, are particularly preferred.

When the metal compound (Z) is applied to the tangified composition (X ′), a method of applying a solution or dispersion of the metal compound (Z) is preferable. In this case, the solvent to be used is not particularly limited, and an organic solvent, water, or the like can be used, but alcohol or water is preferable from the viewpoint of the working environment, and water is particularly preferable. Although the density | concentration of the metal compound (Z) in a solvent is not specifically limited, From the point of the improvement effect of hot water resistance, it is preferable that a metal atom is 1 * 10 < ^-5 > mol / L or more. On the other hand, since the appearance of the gas barrier composition may be deteriorated when a liquid having a concentration that is too high is used, the upper limit of the concentration is preferably the saturation solubility of the metal compound (Z) to be used.

  After applying the metal compound (Z) to the composition (X ′), a protective layer can be laminated to protect the coated surface. The type of the protective layer may be appropriately selected according to the characteristics required for the surface of the gas barrier composition. For example, in the case where the gas barrier composition layer is the outermost surface, it is preferable to have excellent wear resistance. When another layer is laminated on the gas barrier composition layer, The thing excellent in adhesiveness can be selected. Examples of such a protective layer include thermosetting resins such as phenol resins, melamine resins, and epoxy resins; and thermoplastics such as olefin resins, acrylic resins, urethane resins, ionomer resins, polyester resins, polyamide resins, and fluorine resins. Resin etc. are mentioned. A water-soluble resin can also be used. Examples of water-soluble resins include resins having an anionic hydrophilic group such as polyacrylic acid and methyl vinyl ether-maleic anhydride copolymer; resins having a nonionic hydrophilic group such as starch, polyvinyl alcohol and polyoxymethylene; chitosan And resins having cationic hydrophilic groups such as polyethyleneimine and polyallylamine. These may use 2 or more types, and may be a copolymer with another resin component.

  Further, as a method for simultaneously performing the coating treatment and the protective layer forming treatment, a resin or a dispersion of the metal compound (Z) is used together with a resin used for the protective layer as a binder, and this is used as a composition (X ′ There is a method of coating on the surface. In this case, the mass ratio of the metal compound (Z) and the binder is preferably 1/1000 to 1000/1, and more preferably 1/100 to 100/1. If the mass ratio of the metal compound (Z) is less than 1/1000, the effect of improving the hot water resistance may be insufficient, and if the mass ratio of the metal compound (Z) exceeds 1000/1, the fixability after coating is poor. It may be insufficient.

The coating amount of the liquid containing the metal compound (Z) or, if necessary, a solvent or a binder is preferably 0.001 to 10 g / m ² with respect to the surface of the tangified composition (X ′), More preferably, it is 0.01-1 g / m < ² >. The layer applied to the surface of the composition (X ′) may be a continuous layer or a discontinuous layer.

  Although it does not specifically limit as a coating method of the liquid containing a metal compound (Z), The same coating method and drying method as the above-mentioned iodine compound (Y) can be used. The heat treatment temperature during drying varies depending on the boiling point of the solvent used and the thermal efficiency of the apparatus, but is preferably 80 ° C. or higher in order to increase the drying efficiency. The drying time is usually 1 second or longer, preferably 3 seconds or longer.

  Next, the dipping process in which the tangified composition (X ′) is immersed in the metal compound (Z) will be described. At this time, with respect to the type of solvent in which the metal compound (Z) is dissolved or dispersed and the concentration of the metal compound, the same conditions as in the case of the above-described coating treatment can be used.

  In order to increase the efficiency of the immersion treatment, it is preferable to heat the solvent. At this time, the tangified composition (X ′) may be immersed in a solvent and then heated, or the tangified composition (X ′) may be immersed in a previously heated solvent. . The temperature of a preferable solvent is in the range of 30 to 130 ° C, and more preferably in the range of 60 to 120 ° C from the viewpoint of processing efficiency. If the temperature is too low, it takes a long time to obtain the effect of hot water, and if the temperature is too high, the composition (X ′) may be decomposed. Moreover, it is preferable that immersion treatment time is 1 second-1 minute. When the immersion treatment time is too short, the effect of improving the hot water resistance is insufficient, and when the immersion treatment time is too long, the production efficiency is deteriorated. About the drying process after an immersion process, the method similar to the case of the coating process mentioned above can be used suitably.

  In order to further improve the gas barrier property, the inorganic layered compound (D) may be added to the composition (X) containing (A) to (C). The added amount of the inorganic layered compound (D) is preferably in a range where the value of (D) / [(A) + (B)] is 0.001 to 1.0 in terms of mass ratio. This value is more preferably 0.005 to 0.5, still more preferably 0.01 to 0.3, and particularly preferably 0.01 to 0.2. When the addition amount of the inorganic layered compound (D) is too small, that is, when the above value is less than 0.001, the effect of improving the gas barrier property is not recognized. In some cases, the appearance of the film obtained by laminating the composition (X) on the surface and the film formability during lamination may be deteriorated.

  The inorganic layered compound (D) refers to an inorganic compound in which unit crystal layers overlap to form a layered structure. In particular, those that swell and cleave in a solvent are preferred. For example, montmorillonite, beidellite, saponite, hectorite, sauconite, vermiculite, fluorite mica, muscovite, paragonite, phlogopite, biotite, lepidrite, margarite, clintonite, anandite, chlorite, donbasite, sudite, kukeite, clinochlore , Chamosite, nimite, tetrasilic mica, talc, pyrophyllite, nacrite, kaolinite, halloysite, chrysotile, sodium teniolite, xanthophyllite, antigolite, dickite, hydrotalcite and the like. Among these, swellable fluorine mica and montmorillonite are particularly preferable from the viewpoint of improving gas barrier properties. These inorganic layered compounds (D) may be naturally occurring, artificially synthesized or modified, or those treated with an organic substance such as an onium salt or those subjected to a firing treatment. It may be.

  A known catalyst can be added to the composition (X) for the purpose of promoting the esterification reaction. Examples of the catalyst used for this purpose include oxides, acetates and carbonates such as manganese, calcium, cobalt, magnesium, zinc, lead and antimony; organometallic compounds such as titanium, tin and lead; Hafnium (IV). Hafnium salts such as tetrahydrofuran and hafnium tert-butoxide; and diphenylammonium triflate.

The composition (X) has a heat stabilizer, an antioxidant, a pigment, a deterioration inhibitor, a weathering agent, a flame retardant, a plasticizer, a mold release agent, a lubricant, and a tackifier, as long as the properties are not significantly impaired. Etc. may be added. Examples of the heat stabilizer, antioxidant, and deterioration inhibitor include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, and mixtures thereof. Examples of the tackifier include synthetic resins such as C ₅ and C ₉ petroleum oil resins, xylene resins, coumarone indene resins and alkylphenol resins, and natural resins such as rosin and terpene. These may be modified products that have been subjected to hydrogenation, disproportionation, dimerization, esterification and the like. When used in an aqueous system, it is preferably used in the form of an emulsion from the viewpoint of mixing properties.

  The gas barrier film of the present invention forms the composition (X) by applying a coating agent mainly composed of the components (A) to (C) and a solvent to the base film and then performing a heat treatment. In addition, the composition (X) can be formed into a tangible form, further treated with an iodine compound (Y) to obtain a composition (X ′), and then treated with a metal compound (Z). . Hereinafter, the coating agent containing the components (A) to (C) and the solvent as main components is simply referred to as “coating agent”.

  The solvent used for the coating agent is preferably water from the viewpoint of the environment during film production. A small amount of an organic solvent such as alcohol can be added for the purpose of improving the solubility, shortening the drying process, and improving the stability of the solution.

  The coating agent may be prepared by a known method using a melting pot equipped with a stirrer. As the stirrer, known devices such as a homogenizer, a ball mill, and a high-pressure dispersion device can be used.

  The solution concentration when the coating agent is coated on the film is appropriately changed depending on the viscosity and reactivity of the solution, the specifications of the apparatus used, and the like. However, if the solution is too dilute, it is difficult to coat a layer having a sufficient thickness to exhibit gas barrier properties, and the subsequent drying process tends to take a long time. On the other hand, if the concentration of the solution is too high, there may be a problem in the mixing operation and storage stability. From such a viewpoint, the solid content concentration of the coating agent is preferably in the range of 5 to 60% by mass, and more preferably in the range of 10 to 50% by mass.

  Although the method of apply | coating a coating agent to a base film is not specifically limited, The same method as the coating method of the iodine compound (Y) and metal compound (Z) mentioned above can be used.

  As described above, a substrate film can be used as the substrate, and a sheet such as paper can also be used as the substrate.

  As described above, the gas barrier composition structure of the present invention can be applied to various kinds of materials by applying a coating agent to the base material and further performing treatment with the iodine compound (Y) and treatment with the metal compound (Z). It can be used effectively by being laminated on a substrate such as a film or paper. In particular, the gas barrier film of the present invention can be obtained by forming on a thermoplastic resin film.

  As the thermoplastic resin film for this purpose, polyamide resins such as nylon 6, nylon 66 and nylon 46; polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc. Aromatic polyester resin; liquid crystal polyester resin; polybutylene succinate, aliphatic polyester resin such as polylactic acid; polyolefin resin such as polypropylene and polyethylene; polyacetal, polycarbonate, polyarylate, polyphenylene sulfide, triacetyl cellulose, polyether ether ketone , Resins such as polysulfone, polyethersulfone, polyamideimide, polyetherimide, linear polyimide; It includes films made of a mixture of these. The laminated body of those films is also mentioned. Of the resins used in these films, polycarbonate and polyarylate are particularly preferable from the viewpoint of heat resistance and transparency, and polyethylene terephthalate is preferable from the viewpoint of heat resistance and economy. The film may be an unstretched film or a stretched film.

  When producing a film, for example, a thermoplastic resin is heated and melted by an extruder and extruded from a T die, and cooled and solidified by a cooling roll to obtain an unstretched film, or extruded from a circular die and cooled by water or air. To obtain an unstretched film. In the case of producing a stretched film, it is preferable to use a method in which the unstretched film is once wound up or continuously after the unstretched film is produced by the simultaneous biaxial stretching method or the sequential biaxial stretching method. In view of the mechanical properties of the film and the uniformity of its thickness, a method in which a flat film forming method using a T die and a tenter stretching method are combined is preferable.

  When forming a gas barrier composition layer by coating a film with a coating agent, after coating and drying on an unstretched film, it is supplied to a tenter-type stretching machine to simultaneously stretch the film in the running direction and the width direction. (Simultaneous biaxial stretching) and heat treatment can be performed. Alternatively, the film may be stretched in the running direction of the film using a multistage heat roll or the like, coated, dried, and then stretched in the width direction (sequential biaxial stretching) by a tenter type stretching machine. It is also possible to combine running direction stretching and subsequent simultaneous biaxial stretching with a tenter.

  In order to improve the adhesion between the film and the layer of the composition (X), the surface of the film may be subjected to treatment such as corona discharge or anchor coating.

  The thermoplastic resin film on which the gas barrier composition layer is formed is made of an inorganic material for the purpose of further improving gas barrier properties, forming electrodes, imparting conductivity, imparting antireflection properties, imparting heat rays or UV shielding. A layer may be formed. In this case, the inorganic layer may be formed between the thermoplastic resin film and the gas barrier composition layer, or may be formed on the upper surface of the gas barrier composition layer (the side opposite to the thermoplastic resin film). May be. At this time, one or both of the inorganic layer and the gas barrier composition layer may be formed in two or more layers. For example, these layers may be alternately provided to form a multilayer.

  If the inorganic substance which comprises such an inorganic substance layer is an inorganic substance, it will not restrict | limit in particular. For example, metals such as aluminum; metal oxides such as silicon oxide, aluminum oxide, tin oxide, ITO, and FTO; metal nitrides such as silicon nitride and aluminum nitride; diamond-like carbon; silver; iron oxide; Can be mentioned. Of these, silicon oxide is preferable.

  The method for forming the inorganic layer is not particularly limited, and physical vapor deposition (PVD) such as sol-gel method, vacuum deposition method, sputtering method, ion plating method; plasma chemical vapor deposition method, thermal chemical vapor deposition method Known methods such as a chemical vapor deposition method (CVD) such as a growth method; a plating method may be used. The thickness of the inorganic layer is not particularly limited, but is usually preferably 0.5 nm to 1000 nm, more preferably 1 nm to 100 nm, and particularly preferably 5 nm to 50 nm. When the thickness of the inorganic layer is 1000 nm or more, cracks are likely to occur due to bending or the like, and peeling at the interface is likely to occur. When the film thickness is 0.5 nm or less, the effect of improving the gas barrier property is not recognized.

  The thickness of the gas barrier composition layer in the gas barrier film of the present invention is desirably 0.03 μm or more in order to sufficiently enhance the gas barrier property of the film. There is no particular upper limit, but if it is too thick, the characteristics of the base film cannot be utilized. For this reason, it is desirable that it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 10 micrometers or less, More preferably, it is 5 micrometers or less.

The gas barrier composition structure of the present invention preferably has an oxygen permeability coefficient at 20 ° C. and 90% RH of 20 ml · μm / m ² · day · MPa or less, preferably 10 ml · μm / m ² · day · MPa or less. It is more preferable that it is 5 ml · μm / m ² · day · MPa or less.

  The gas barrier film of the present invention may be printed or laminated.

  The gas barrier film of the present invention can be used for various applications such as food packaging, organic EL, film-type solar cells, toiletry packaging, and pharmaceutical packaging.

Next, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited only to the following examples.
In the following examples and comparative examples, the gas barrier property is oxygen in an atmosphere of 20 ° C. and 90% relative humidity of a film sample immediately after production and a film sample after 30 ° C. × 90% RH × 3 months wet heat treatment. The transmittance was evaluated by measuring with an oxygen permeability meter (OX-TRAN 2/20) manufactured by Mocon.

Oxygen permeability coefficient P _C of the gas barrier layer was calculated using the following equation.
_{1 / Q F = 1 / Q} B + L / P C
However, Q _F : Oxygen permeability of gas barrier film (ml / m ² · day · MPa)
Q _B : Oxygen permeability of thermoplastic resin film (ml / m ² · day · MPa)
P _C : Oxygen permeability coefficient of gas barrier layer (ml · μm / m ² · day · MPa)
L: Gas barrier layer thickness (μm)
It is. The oxygen permeability of the polyethylene terephthalate (PET) film having a thickness of 12 μm is 900 ml / m ² · day · MPa, and the oxygen permeability of the nylon 6 film having a thickness of 15 μm is 400 ml / m ² · day · MPa. The oxygen permeability of the 100 μm polycarbonate film (PC) was 9500 ml / m ² · day · MPa.

  Evaluation of hot water resistance was carried out by immersing a sample 3 days after production in 90 ° C hot water (ion exchange water) for 30 minutes, wiping off the moisture, and measuring the oxygen permeability in an atmosphere of 20 ° C and 90% relative humidity. It evaluated by measuring with the oxygen permeability measuring device (OX-TRAN 2/20) made from a manufacturer.

[Preparation of each solution]
(A) Preparation of aqueous polyvinyl alcohol solution (I) 3.00 g of polyvinyl alcohol (UF100 manufactured by Unitika Chemical Co., Ltd., degree of polymerization 1000, degree of saponification 99.4) was added to and dissolved in 27.00 g of water. I).

(B) Preparation of ethylene-maleic acid copolymer aqueous solution (II) having a neutralization degree of 10% (alkali compound: sodium hydroxide) Sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was added to 93.1 g of water. .54 g and ethylene-maleic acid copolymer (Aldrich) 9.8 g were added, and this was heated and dissolved to obtain a 10% by mass aqueous solution (II).

(C) Preparation of 1,2,3,4-butanetetracarboxylic acid aqueous solution (III) having a neutralization degree of 15% (alkali compound: sodium hydroxide) Sodium hydroxide (made by Wako Pure Chemical Industries, Ltd.) was added to 97.2 g of water. , Reagent special grade) 1.0 g and 1,2,3,4-butanetetracarboxylic acid (Wako Pure Chemical Industries, Ltd., reagent grade 1) 9.8 g were added, dissolved, and dissolved in a 10 mass% aqueous solution (III). It was.

(D) Preparation of iodine compound solution (IV) 0.25 part of iodine was added to 100 parts of a 0.066 mass% aqueous solution of potassium iodide and stirred to obtain an iodine compound solution (IV).

Example 1
The aqueous solution (I) (3.0 g) and the solution (II) (7.4 g) were mixed and stirred, and the mass ratio of polyvinyl alcohol to ethylene-maleic acid copolymer was 30/70, and the solid content concentration was 10% by mass. A coating agent was prepared.

This coating agent is coated with a Mayer bar on a corona surface treatment of nylon 6 film (Emblem ON15, thickness 15 μm, manufactured by Unitika Co., Ltd.) as a base material so that the coating thickness after drying becomes about 1 μm. And dried for 2 minutes, and then heat treated at 200 ° C. for 30 seconds to make it tangible. Next, an iodine compound solution (IV) at 40 ° C. as an iodine compound was applied to the gas barrier coat surface thus formed by a direct gravure method, and then dried at 100 ° C. for 2 minutes. Further, an aqueous solution of magnesium oxide (Micromag 3-150, manufactured by Kyowa Chemical Industry Co., Ltd.) as a metal compound was coated on the gas barrier coat surface with a Mayer bar so as to be 0.9 g / m ² and dried at 100 ° C. for 2 minutes. .

The coated film obtained immediately after production had an oxygen permeability of 3 ml / m ² · day · MPa at 20 ° C. and 90% RH, and the oxygen permeability coefficient of the coated layer was 3 ml · μm / m ² · day · MPa. It was. The oxygen permeability coefficient of the coat layer after storing this coat film at 30 ° C. × 90% RH for 3 months was 3 ml · μm / m ² · day · MPa. In addition, the film has an oxygen permeability coefficient of 3 ml · μm / m ² · day · MPa at 20 ° C. and 90% RH after hydrothermal treatment at 90 ° C. for 30 minutes, and has excellent gas barrier properties. Indicated.

  Details of the coated film of Example 1 are shown in Table 1.

Example 2
A 3% aqueous dispersion of montmorillonite (Kunimine Industry Co., Ltd. Kunipia F) was added to the coating agent used in Example 1, and the mass ratio of polyvinyl alcohol, ethylene-maleic acid copolymer and montmorillonite was 30/70 / A coating agent having a solid content of 9% by mass was prepared. Other than that was the same as Example 1. Thereby, the coated film of Example 2 was obtained. The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this coated film.

Example 3
Compared to Example 1, the substrate was changed to polycarbonate (LEXAN, manufactured by Japan Easy Plastics Co., Ltd., thickness 100 μm), and the metal compound was changed to calcium hydroxide (Wako Pure Chemical Industries, Ltd., reagent grade). Other than that was carried out similarly to Example 1, and obtained the coat film. Table 1 shows the details of this coated film.

Example 4
The coating agent used in Example 1 was coated on a corona surface of a biaxially stretched polyethylene terephthalate film (Embret PET12 manufactured by Unitika Ltd., thickness 12 μm) with a Meyer bar so that the coating thickness after drying was about 1 μm. After coating and drying at 100 ° C. for 2 minutes, heat treatment was performed at 220 ° C. for 30 seconds. Then, after being immersed in iodine compound solution (IV) for 30 seconds, dried at 100 ° C. for 2 minutes, and further immersed in 0.1% aqueous dispersion of 50 ° C. calcium carbonate as a metal compound for 30 seconds. And dried at 100 ° C. for 2 minutes. Details of the obtained coated film are shown in Table 1.

Example 5
The coating agent used in Example 1 was coated with a Mayer bar on a corona surface treatment of nylon 6 film (Emblem ON15 manufactured by Unitika, thickness 15 μm) so that the coating thickness after drying was about 1 μm. After drying at 2 ° C. for 2 minutes, heat treatment was performed at 200 ° C. for 30 seconds. Subsequently, after being immersed in iodine compound solution (IV) for 30 seconds, dried at 100 ° C. for 2 minutes, and further, an aqueous dispersion of magnesium hydroxide (made by Ishizu Pharmaceutical Co., Ltd., grade 1) as a metal compound on the gas barrier coat surface. Was coated with a Mayer bar to 0.7 g / m ² and dried at 100 ° C. for 2 minutes. Details of the obtained coated film are shown in Table 1.

Example 6
Instead of the magnesium oxide aqueous dispersion of Example 1, an aqueous dispersion (total solid content concentration of 10% by mass) containing the following metal compound (hydrotalcite) and a binder at a solid content mass ratio of 90/10 was used. Using. Other than that was carried out similarly to Example 1, and obtained the coating agent and the coated film. The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Metal compound: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ / 4H ₂ O (Kyowa Chemical Industry Kyoward, KW-500)
Binder: Urethane emulsion (M60 Takeda Chemical W6010)

Example 7
Instead of the aqueous polyvinyl alcohol solution (I) described above, a solution was prepared using an ethylene-vinyl alcohol copolymer (Exeval AQ-4105 manufactured by Kuraray Co., Ltd.). Other than that was carried out similarly to Example 1, and obtained the coating agent and the coated film. The obtained film was transparent and excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Example 8
The polyvinyl alcohol aqueous solution (I) (4.2 g) and the ethylene-maleic acid copolymer aqueous solution (III) (10.8 g) are mixed and stirred, and the polyvinyl alcohol and 1,2,3,4-butanetetracarboxylic acid are mixed. A coating agent having a mass ratio with the acid of 30/70 and a solid content concentration of 10% by mass was prepared.

This coating agent is coated with a Mayer bar on a corona surface treatment of a biaxially stretched polyester film (Embret PET12, thickness 12 μm manufactured by Unitika Ltd.) so that the coating thickness after drying is about 1 μm. After drying for 30 minutes, it was heat treated at 220 ° C. for 30 seconds to make it tangible. Thereafter, this was immersed in iodine compound solution (IV) for 10 seconds, dried at 100 ° C. for 2 minutes, and further, magnesium oxide as a metal compound (Micromag 3-150, manufactured by Kyowa Chemical Industry Co., Ltd.) on the gas barrier coat surface. The aqueous solution was coated with a Mayer bar so as to be 0.9 g / m ² and dried at 100 ° C. for 2 minutes.

  The coated film thus obtained was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Example 9
Compared with Example 8, the base film was changed to a polyethylene terephthalate film (MOS-TH manufactured by Oike Kogyo Co., Ltd., thickness 12 μm) on which SiO _{2 was} deposited. Otherwise in the same manner as in Example 8, a coated film was obtained. The coating agent was applied to the vapor deposition surface. The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Example 10
Compared to Example 8, the coating agent was coated on a corona surface treatment of a polycarbonate film (LEXAN, manufactured by Nippon GE Plastics Co., Ltd., thickness 100 μm) with a Mayer bar so that the coating thickness after drying was about 1 μm. After drying at 100 ° C. for 2 minutes, heat treatment was performed at 220 ° C. for 30 seconds. Thereafter, the iodine compound solution (IV) is applied by a direct gravure method, dried at 100 ° C. for 2 minutes, and then an aqueous dispersion of hydrotalcite (Kyowa Chemical Industry Kyoward, KW-2200) at 50 ° C. And then dipped in 100 ° C. for 2 minutes. Otherwise, it was the same as Example 8.

  The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Example 11
Compared to Example 1, the composition ratio was changed so that the mass ratio of polyvinyl alcohol and ethylene-maleic acid copolymer was 20/80. Other than that, a coating agent and a coated film were obtained in the same procedure as in Example 1. The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Example 12
Compared to Example 1, the composition ratio was changed so that the mass ratio of polyvinyl alcohol and ethylene-maleic acid copolymer was 40/60. Other than that, a coating agent and a coated film were obtained in the same procedure as in Example 1. The obtained film was excellent in gas barrier properties and hot water resistance. Table 1 shows the details of this film.

Comparative Example 1
No iodine compound was applied. Other than that was carried out similarly to Example 1, and obtained the coat film. The obtained film was inferior in gas barrier properties immediately after production. Table 1 shows the details of this film.

Comparative Example 2
The metal compound was not applied. Other than that was carried out similarly to Example 1, and obtained the coat film. The obtained film was inferior in heat-and-moisture resistance and hot water resistance. Table 1 shows the details of this film.

Comparative Example 3
Neither treatment with an iodine compound nor a metal compound was performed. Otherwise in the same manner as in Example 8, a coated film was obtained. The obtained film was inferior in hot water resistance. Table 1 shows the details of this film.

Comparative Example 4
Instead of the ethylene-maleic acid copolymer as the polyvalent carboxylic acid, an acrylic acid-maleic acid copolymer (manufactured by Aldrich) was used. Other than that was carried out similarly to Example 1, and obtained the coat film. The obtained film was inferior in gas barrier property. Table 1 shows the details of this film.

  Each of the films of Examples 1 to 12 has excellent gas barrier performance even under high humidity for a long time, excellent gas barrier performance even under hot water conditions, and gas barrier properties at an initial stage after production. It was also excellent.

In particular, since the film of Example 2 was obtained by adding a layered compound to the coat layer, the effect of improving the gas barrier property was obtained.
As in Examples 1, 3, 4, 5, 8 to 12, excellent gas barrier properties before and after the hot water treatment can be obtained even if the type of base material, the type of metal compound, and the treatment method using iodine compound or metal compound are changed. The film shown was obtained.

  In Example 6, since the component of the protective layer was added to the metal compound, the gas barrier property was excellent accordingly.

  As is clear from the comparison of Examples 1, 7, and 8, even when the combination of the compound (A) and the polyvalent carboxylic acid (B) constituting the coating layer was changed, excellent gas barrier properties were exhibited.

  As in Examples 8, 9, and 10, the type of polyvalent carboxylic acid (B) in the coating layer was changed from ethylene-maleic acid copolymer (b1) to 1,2,3,4-butanetetracarboxylic acid (b2). Even if it changed, it was excellent in gas barrier property and hot water resistance. However, more preferable results were obtained when the ethylene-maleic acid copolymer (b1) was used.

  On the other hand, in Comparative Example 1, when the coating or immersion treatment with the iodine compound (Y) was not performed, the gas barrier property immediately after the production was insufficient because the penetration of the metal compound was slow.

  In Comparative Example 2, coating or dipping treatment with the metal compound (Z) was not performed, and ionic crosslinking could not be performed. Therefore, gas barrier properties were insufficient.

  Since Comparative Example 3 used 1,2,3,4-butanetetracarboxylic acid (b2) having a fast reaction among the polyvalent carboxylic acids (B), the gas barrier properties immediately after the production were good. However, since the coating or immersion treatment with the iodine compound (Y) and the metal compound (Z) is not performed, the gas barrier properties after the wet heat treatment and before and after the hot water treatment are insufficient.

  Since the comparative example 4 used the polyvalent carboxylic acid which does not correspond to the scope of the present invention, the gas barrier property immediately after production is insufficient even when the coating treatment with the iodine compound (Y) or the metal compound (Z) is performed. Met.

Claims (9)

Having a tangified composition (X),
The composition (X) contains a compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C), and the polyvalent carboxylic acid (B) ) Is at least one selected from ethylene-maleic acid copolymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and compound (A) and polyvalent carboxylic acid ( B) has a mass ratio of (A) / (B) = 95/5 to 5/95, and at least a part of compound (A) and polyvalent carboxylic acid (B) is crosslinked,
The tangified composition (X) is subjected to a coating treatment or impregnation treatment using an iodine compound (Y) and then a coating treatment or impregnation treatment using a metal compound (Z). A gas barrier composition structure characterized by comprising:   The gas barrier composition structure according to claim 1, wherein the composition (X) comprises an inorganic layered compound (D). It contains a compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C). The polyvalent carboxylic acid (B) is an ethylene-maleic acid copolymer. It is at least one selected from the polymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and the mass ratio between the compound (A) and the polyvalent carboxylic acid (B) is ( A) / (B) = 95/5 to 5/95, tangifying the composition (X) in which at least a part of the compound (A) and the polyvalent carboxylic acid (B) is crosslinked,
The tangified composition (X) is subjected to a coating treatment or an impregnation treatment using an iodine compound (Y), followed by a coating treatment or an impregnation treatment using a metal compound (Z). A method for producing a gas barrier composition structure.   The method for producing a gas barrier composition structure according to claim 3, wherein the composition (X) contains an inorganic layered compound (D).   A gas barrier film comprising a layer composed of the gas barrier composition structure according to claim 1 or 2 on at least one surface of a thermoplastic resin film.   An inorganic layer is provided between the thermoplastic resin film and the layer composed of the gas barrier composition structure or on the surface side of the layer composed of the gas barrier composition structure. The gas barrier film according to claim 5. It contains a compound (A) having two or more hydroxyl groups in the molecule, a polyvalent carboxylic acid (B), and an alkali compound (C). The polyvalent carboxylic acid (B) is an ethylene-maleic acid copolymer. It is at least one selected from the polymer (b1) and 1,2,3,4-butanetetracarboxylic acid (b2), and the mass ratio of the compound (A) and the polyvalent carboxylic acid (B) is (A ) / (B) = 95/5 to 5/95, and the layer of the composition (X) in which at least a part of the compound (A) and the polyvalent carboxylic acid (B) is crosslinked is thermoplastic. Formed on at least one side of the resin film,
The layer of the composition (X) is subjected to a coating treatment or an impregnation treatment using an iodine compound (Y), followed by a coating treatment or an impregnation treatment using a metal compound (Z). A method for producing a gas barrier film.   8. The method for producing a gas barrier film according to claim 7, wherein the composition (X) contains the inorganic layered compound (D).   The production of a gas barrier film according to claim 7 or 8, wherein an inorganic layer is provided between the thermoplastic resin film and the layer of the composition (X) or on the surface side of the layer of the composition (X). Method.