TW201139548A - Gas barrier film, and laminate - Google Patents

Abstract

Provided is a gas barrier film which is transparent, and which is suitable for use as a packaging material exhibiting excellent gas barrier properties against oxygen and water vapor. The gas barrier film is configured from a polymer layer having 0.3 to 15 mass% of an acryl amide compound represented by formula (1) and a polyvalent metal salt of an unsaturated carboxylic acid compound. Formula (1) is R1(H)C=C(H)-CO-N(R2)(R3), wherein R1 represents hydrogen or a methyl group, R2 represents hydrogen or C1-4 alkyl groups, R3 represents hydrogen, C1-4 alkyl groups, or a group comprising formula (2), and R2 and R3 may link and form a morpholine ring. Formula (2) is -(R4(R5)(R6))n-Y, wherein n represents an integer between 1 and 5, R4 represents a methylene group or an ethylene group, R5 represents hydrogen or C1-4 alkyl groups, R6 represents C1-4 alkyl groups, and Y represents -OH, -NH2, or -N(CH3)2.

Description

201139548 VI. Description of the Invention: [Technical Fields of the Invention] The permeable system is excellent in adhesion to an inorganic thin film layer or the like, and has gas barrier properties such as oxygen vapor (especially water vapor barrier property). ) Excellent 'is a gas barrier film suitable for packaging materials. [Prior Art] In recent years, for a barrier material such as oxygen or water vapor, such as on a film substrate, such as oxygen cutting, oxidation (four) oxidation reduction, such as vacuum evaporation, sputtering, ion evaporation A transparent gas barrier film formed by a method such as a chemical vapor phase growth method or the like has been attracting attention. In addition, the transparent gas barrier film is generally a film obtained by vapor-depositing an inorganic oxide on a substrate surface composed of a biaxially stretched polyester film excellent in transparency and rigidity, and if the vapor deposition layer is used directly The friction at the time is weak, and when it is used as a film for packaging, when printing and laminating in subsequent processing, and filling of the contents, cracks of inorganic oxide may occur due to friction and stretching, resulting in resistance. The gas is reduced. Proposal: a gas barrier polyglycol alcohol, ethylene vinyl alcohol copolymer, a method of laminating on a biaxially stretched film substrate (for example, Patent Document 丨), or polyvinyl alcohol and poly(methyl) A method of coating a composition of acrylic acid on a biaxially stretched film substrate (for example, Patent Document 2). However, the gas barrier film formed by laminating polyvinyl alcohol has a low oxygen barrier property under high humidity, and the composition of polyephedol and poly(meth)acrylic acid is sufficiently esterified.俾Improve 099145744 3 201139548 The film is blocked, it must be heated for a long time at high temperature, and although it can show oxygen gas barrier properties, it is difficult to say that it is sufficient. On the other hand, the inventors of the present invention have proposed a method for improving gas barrier properties, and it has been proposed to coat a transparent inorganic vapor-deposited film layer with a polyvalent metal salt polymer such as propylene oxide. 3) Although the oxygen barrier gas condition [previous technical literature] is different, it is expected to follow the other layers. [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 32 No. 3287. Patent Document 3: Patent Application No. 2 〇 7_245433 SUMMARY OF INVENTION [Problem to be Solved by the Invention] The object of the present invention is to obtain a gas barrier which is excellent in transparency and water vapor resistance, and is suitable for use in packaging materials. . The gas barrier film provided by the present invention, which is a means for solving the problem, is an unsaturated carboxylic acid containing 0.3 to 15% by mass of the amide compound of the following general formula (1). Multivalent gold polymer layer composition; 099145744 4 201139548

R Η R2

Cssc

H

C·II

N general formula (1)

O [: R is a hydrogen or a methyl group; R2 is a hydrogen or an alkyl group having 1 to 4 carbon atoms; R3 is a group; a group having a gas number of 1 to 4 or a group consisting of the following formula (2); The RR system is connected to the structure of the ring. R5 • General formula (2) - (R4) η - γ R1 [where 'η is an integer from 1 to 5; r4 is a fluorenylene or an ethyl group; ^ is a nitrogen or a carbon number of 1 to 4 A burning group having 1 to 4 carbon atoms; a γ-based collar, -nh2, or -N(CH3)2. (Effect of the Invention) The gas barrier film of the present invention is excellent in adhesion to other layers and is excellent in gas barrier properties such as oxygen and water vapor (especially oxygen gas barrier properties). [Embodiment] <Acrylamide-based compound> The acrylamide-based compound constituting one of the components of the gas barrier film (hereinafter also referred to as "polymer layer") of the present invention is an acrylonitrile represented by the following general formula (1). Amine compounds: 5 099145744 201139548 Η R1 Η

R2

II

General formula (1) 〇R3 [wherein 'R1 is hydrogen or methyl; R2 is hydrogen or carbon number} to 4 alkyl; r3 is hydrogen, carbon number i to 4, or the following The base composed of the formula (7); the R and R-connected structures are formed into a ring. 〕

Rs

General formula (2) R1 [wherein η is an integer of 1 to 5; R4 is a methylene group or an ethyl group; R5 is hydrogen or; ε is an inverse of 1 to 4; R6 is a carbon number! To the base of 4; γ-oH, -ΝΗ2, or -N(CH3)2. Specific examples of the acrylamide-based compound include, for example, N-(2-hydroxyethyl)acrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N,N-monodecylaminopropyl propylamine, N,N-dimercaptopropyl stearylamine, and acrylonitrile porphyrin. <Unsaturated carboxylic acid compound> The unsaturated carboxylic acid compound constituting one of the components of the polyvalent metal salt of the unsaturated carboxylic acid compound of the present invention is, for example, acrylic acid, methacrylic acid, maleic acid, or clothing A carboxylic acid compound having an α,/?-ethylenically unsaturated group such as an acid. 099145744 6 201139548 It is necessary to carry out polymerization in advance, and when polymerization is carried out in advance, the degree of polymerization is set to less than 20 Å, preferably less than 1 。. In addition, when the polymerization is carried out in advance, a polymer obtained by polymerizing a polymer (polymer compound) having a degree of polymerization of 2 Å or more and a polymer obtained by polymerization of a post-valence metal compound may have a gas barrier property under high humidity. Improved care. Further, in the case where the compound is used as the compound, the unsaturated carboxylic acid such as (meth) methacrylate or ethyl (meth) acrylate may be used as long as it does not impair the object of the present invention. The ester compound is subjected to a small amount of copolymerization. In addition, the (mercapto)propenyl group in (meth)acrylic acid, ethyl (meth)acrylate, etc. represents a case where the methacryl group is covered and the case of the acryl group, and the following is also the same. . Among these unsaturated carboxylic acid compounds, the monomer is more likely to form a salt which is completely neutralized by the polyvalent metal compound, and the film obtained by the polymerization of the salt is excellent in gas barrier properties, and thus is preferable. <Multivalent Metal Compound> The polyvalent metal compound constituting one of the components of the polyvalent metal salt of the unsaturated decanoic acid compound of the present invention is as in Groups 2A to 7A, 1B to 3B, and 8 of the periodic table. Metals and metal compounds, such as: magnesium (Mg), dance (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc a divalent or higher metal such as (Zn) or aluminum (A1), an oxide, a hydroxide, a dentate, a carbonate, a phosphate, a phosphite, a hypophosphite, a sulfate or a sulfite of the metal. . Among the metal compounds, preferred are divalent gold compounds of 099145744 7 201139548, more preferably oxidized town, oxidized mother, cerium oxide, zinc oxide, gas oxidized town, hydrogen oxygen, hydrogen hydride, zinc hydroxide, etc. . When the divalent metal compound is used, the film obtained by polymerizing the salt of the above unsaturated carboxylic acid compound is excellent in gas barrier properties under high humidity. At least one of these polyvalent metal compounds may be used, and only two or more kinds may be used. <polyvalent metal salt of unsaturated carboxylic acid compound> The polyvalent metal salt of the unsaturated acid-lowering compound constituting the main component of the gas barrier film of the present invention is an unsaturated carboxylic acid compound having a degree of polymerization of less than 2 Å, and A salt of the above polyvalent metal compound. The polyvalent metal salt of the unsaturated carboxylic acid compound may be one type or a mixture of two or more types. Among the polyvalent metal salts of the unsaturated carboxylic acid compound, the copolymer layer obtained from zinc (mercapto) acrylate is particularly preferred because it has excellent hot water resistance. <Gas barrier film> The gas barrier film of the present invention contains 3 to 15% by mass of the acrylamide compound 〇 (preferably 〇 3 to 10% by mass, more preferably 5 5 to 5% by mass). A film composed of a polymer of a polymetallic salt of the above unsaturated carboxylic acid compound (a total amount of a polyvalent metal salt of a acrylamide compound and an unsaturated carboxylic acid compound is 1% by mass). When the content of the acrylamide-based compound is less than 0.3% by mass, the effect of improving the adhesion of the gas barrier film obtained is low. On the other hand, even if it exceeds 15% by mass, although excellent adhesion is maintained, there is resistance. The tendency to reduce gas. The polymer layer of the present invention is within the scope of not detracting from the object of the present invention, and is still applicable to, for example, decyl (meth) acrylate, ethyl (meth) acrylate, hydrazine, 4 - butanediol. Acrylic acid, diethylene glycol • dipropylene acid @, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, hexanediol • dipropionate, tripropylene glycol • diacrylate An unsaturated acid (di) ester compound such as neopentyl glycol diacrylate; a monomer or a low molecular weight compound such as a vinyl ester compound such as vinyl acetate is copolymerized. Further, the polymer layer of the present invention may be formed by mixing with a vinyl alcohol polymer or a modified vinyl alcohol polymer without departing from the object of the present invention. The modified ethigenate polymer is specifically a part of an OH group such as an ethylene glycol polymer which becomes a matrix, and has an α, /3-ethyl group such as acrylic acid, mercaptoacrylic acid, maleic acid or the like. The unsaturated group carboxylic acid compound or a derivative thereof is reacted to introduce a (meth) acrylate-based (mercapto) acrylate-based modified vinyl alcohol-based polymer. Further, a modified vinyl alcohol-based polymer obtained by a method in which a south molecular reaction is carried out and a reactive functional group is introduced into a side bond of a glycol-based polymer. Specifically, there is a method in which a vinyl ester is polymerized in the presence of a thiol acid, and the obtained polymer is saponified, and a thiol group is introduced only at a molecular terminal, and the thiol group of the vinyl alcohol-based polymer of the matrix is obtained. A part of a 'thiol group-modified vinyl alcohol-based polymer having a thiol group (-SH group). Further, a vinyl alcohol polymer or a vinyl acetate polymer having a carboxyl group or a hydroxyl group may be alkylated using hydrazine such as an organic halodecane, an organic ethoxy decane, and a valerane such as 099145744 9 201139548. a method of adding a post-reformation to a sulphur-burning group, or copolymerizing vinyl acetate with an olefinic unsaturated compound containing a decyl group such as vinyl decane or (meth) acrylamide-alkyl decane. A modified ethylene glycol-based polymer obtained by a method in which a human body is saponified to introduce a decyl group such as a decyl alcohol group or a salt thereof of a hydrolyzate such as an alkoxyalkyl group, a nonyloxyalkyl group or a hydrazine. Specifically, it is a part of the OH group of the ethylene glycol-based condensate such as a matrix, and has a decyl group such as a tridecyloxyalkylene group such as a trimethoxy oxysulfanyl group or a triethoxy oxanyl group. Modification of the vinyl alcohol dimer. Further, it may be a method in which a vinyl alcohol polymer is dispersed in an acetic acid solvent, and a method of adding a diketene thereto, or a vinyl alcohol poly 4 body may be previously dissolved in, for example, dimethylformamidine. a method of adding a croprone to a solvent such as an amine or a dioxane, or a method of directly contacting a vinyl alcohol polymer with a crotonene gas or a liquid valerene, and the like The female alcohol is polyoctabody. Specifically, for example, a modified vinyl alcohol-based polymer such as an ethylene glycol-based modified vinyl alcohol-based polymer having a part of a vinyl alcohol-based polymer of a matrix having an ethylene glycol group. Further, it may contain, for example, an ethylene vinyl alcohol copolymer, a polyvinylpyrrolidone, a polyvinyl ether, a polypropylene decylamine, a polyethylenimine, a starch: a gum arabic, a thiol cellulose, or the like. Polymer; acrylic acid-polymerized oxime, ethylene/acrylic acid copolymer, polyvinyl acetate, ethylene vinegar, acetonitrile copolymer, polyester, polyamine phthalate, etc.; slip agent 曰099145744 201139548 Various additives such as a sliding agent (SliP), an anti-knot, an anti-static (four), an anti-mite, a pigment, a dye, an inorganic or an organic filler, etc., may be contained in order to improve wettability and adhesion to a substrate to be described later. Various surfactants and the like. Among these, 'preferably an acetol polymer, preferably a modified vinyl alcohol polymer' is preferably used in combination with (meth) propylene hydride such as acrylic acid, methyl acrylate or the like. The (meth)acrylic acid-based modified vinyl alcohol-based polymer. The mixing ratio of the propylene-based amine compound, the polyvalent metal salt of the unsaturated m-acid compound, and the vinyl alcohol-based polymer is preferably (10) the guanamine-based compound 〇5 to 15 s%, and the polyvalent unsaturated carboxylic acid compound. 85 to 95% by mass of the metal salt and 1 to 20% by mass of the vinyl alcohol polymer (the total amount of the acrylamide compound, the polyvalent metal salt of the unsaturated carboxylic acid compound, and the vinyl alcohol polymer) is 1〇〇. quality%). The thickness of the polymer layer of the present invention can be determined according to various uses, and is usually 0.01 to 100 / an, preferably 0.05 to 50 / mi, more preferably (U ~ 10 / mi range) < manufacture of gas barrier film In the method for producing a gas barrier film of the present invention, for example, 0.5 to 15% by mass of the acrylamide-based compound, 85 to 95% by mass of the polyvalent metal salt of the unsaturated carboxylic acid compound, and vinyl alcohol-based polymerization can be used. The ratio of 1 to 20% by mass (100% by mass of the propyleneamine compound, the polyvalent metal salt of the unsaturated tickic acid compound, and the ethylene glycol I-incorporated body) is dissolved in a solvent such as water. a method of coating the mixture solution on the surface on which the polymer layer is to be formed; or a solution of the acrylamide compound and a polyvalent metal salt solution of the unsaturated carboxylic acid compound, and then a method in which the amount of the acrylamide compound is /5 to 5 in the form of a mass of A, and is applied to the surface of the polymer layer to be formed, or a acrylamide compound and an unsaturated carboxylic acid; And polyvalent metal compounds After mixing to form an unsaturated carboxylic acid polyvalent metal salt, another component such as a vinyl alcohol polymer is added thereto, and a solution is formed by mixing, and the solution is applied and polymerized. In the unsaturated carboxylic acid compound or a solution thereof, the acrylamide compound and the polyvalent metal compound are added at a ratio of 0.315% by mass based on the acrylamide compound concentration, thereby forming an unsaturated state of the acrylamide-containing compound. A method of coating a solution of a polyvalent metal salt of a phthalic acid compound, adding a vinyl alcohol polymer to the solution, adjusting the entire ratio, and applying the solution. Further, 'in accordance with the layer shape of the polymer layer to be formed, The method of applying the coating is not limited to various known coating methods such as, for example, a method of impregnating a substrate layer in a solution of the mixture or a method of spraying a solution of the mixture onto the surface of a substrate layer. The use of an unsaturated acid-lowering compound in combination with a polyvalent metal compound; in the case of a gluten solution, when the amount of the polyvalent metal compound added is less than that of the unsaturated acid In the case of a laminate having a large content of a free carboxylic acid group, there is a concern that a laminate having a low gas barrier property may be obtained. Further, when the amount of the polyvalent metal compound is added to the carboxyl group of the unsaturated carboxylic acid compound, 1 Chemical equivalents 099145744 12 201139548 In the case where there is an unreacted polyvalent metal compound, there is a concern that the ratio of the polyvalent metal salt of the unsaturated (tetra) compound containing the two olefinic amine-containing compound may be uncontrollable. Therefore, the amount of the polyvalent metal compound added is preferably 1 chemical equivalent with respect to the carboxyl group of the unsaturated carboxylic acid. Further, when an unsaturated tickic acid compound is used, it is mixed with a propylene-based amine compound and a polyvalent metal compound. In the case of a solution, a polyvalent metal salt of an unsaturated tickic acid compound is usually formed during the period in which the (d) (iv) acid compound and the polyvalent metal compound are dissolved in a solvent, but in order to form a polyvalent metal salt, it is preferable to mix 1 More than a minute. Among these methods, a method of adding and mixing a propylene amide compound is added after pre-modulating a polyvalent metal salt of an unsaturated carboxylic acid compound, since the amount of the acrylamide compound can be added at 〇·3 to 15 Any adjustment within the range of mass % is preferred. The solvent used in the mixed solution of the acrylamide compound and the polyvalent metal salt of the unsaturated tickic acid compound may, for example, be a lower alcohol such as water, methanol, ethanol or isopropanol, or a glycerol or a methyl ethyl ketone. The organic solvent or the mixed solvent is preferably water. A method of coating a mixed solution of an acrylamide compound and a polyvalent metal salt of an unsaturated acid compound having a degree of polymerization of less than 20 on a layer on which a polymer layer is to be formed, for example, an air knife coater, Gravure coater, top gravure coater, intaglio gravure coater, reverse gravure and spray nozzle method, top loading reverse coater (top 099145744 13 201139548 feed) Reverse roller coater), bottom feed reverse coater and nozzle feed reverse coater, etc., reverse roll coater, 5 roll coater, knife coater, bar coater, rod Various known coating machines such as a bar reverse coater, a die coater, a multi-layer die coater, a spin coater, and a dip coater, depending on the acrylamide compound and the degree of polymerization a mixed solution of a 2 fluorene unsaturated carboxylic acid compound polyvalent metal salt, dried and polymerized to have a thickness of 0 01 to 10 〇Mm (preferably 〇. 5 to 50 μιη, more preferably 〇.1 to ΐ〇μιη) The method can be appropriately applied in accordance with the specific gravity of the polymer layer. When the acrylamide compound and the polyvalent metal salt of the unsaturated carboxylic acid compound are dissolved, as described above, for example, methyl (meth) acrylate or (曱) may be added without damaging the object of the present invention. Ethyl acrylate, 1,4-butanediol, diacrylate, diethylene glycol diacrylate, tetraethylene glycol, acrylonitrile, polyethylene glycol, dipropionate, Alcohol·diacrylate, propanol-propionate, neopentyl glycol dipropionate, etc., and a monomer or low molecular compound such as a phthalic acid (di)ester compound or a vinyl acetate compound such as vinyl acetate $compound; polyvinyl alcohol, ethylene vinyl alcohol copolymer, polyethylene ratio, bite mesh, polyethylene vinyl, polyacrylamide, polyethylenimine, lake: gum arabic, fluorene fiber A water-soluble polymer such as a glycerin; a polymer of L-acrylic acid, a polyvinyl acetate, a vinyl acetate, a vinyl acetate copolymer, a polystyrene, a polyamine phthalic acid, etc. Wait. In the case of dissolving the compound of the __ system and the metal salt of the money and the ship compound, it is also possible to add, for example, a slip agent, a slip agent, or an anti-wear agent, without damaging the object of the present invention. An agglomerating agent, an antistatic agent, an antifogging agent, a pigment, a dye, an inorganic or organic filler, and various additives may be added in order to improve the m between the substrate and the substrate. Further, the method of forming the gas barrier film may be exemplified by a solution obtained by dissolving (iv) a guanamine compound and a polyvalent metal salt of an unsaturated thief compound, and the solution is not used in combination with the B-based polymer. A method of applying a coating and polymerizing to form a gas barrier, and 2) applying a solution of the ethylene glycol-based polymer and polymerizing to form a gas barrier layer. The order of the above 」ι and "2" can also be changed. Further, a gas barrier film can be formed by sequentially applying and polymerizing a plurality of cold liquids in which the ratio of the vinyl alcohol polymer is different from the zero. When the gas barrier layer of the present invention is directly formed on the inorganic thin film layer such as aluminum vapor film, the gas barrier film adjacent to the inorganic thin film layer is formed into a gas barrier film by using a solution not blended into the vinyl alcohol polymer, and then The solution in which the vinyl alcohol polymer is used in combination is polymerized thereon, whereby the gas barrier film can be formed without directly contacting the layer containing the vinyl alcohol polymer to the inorganic thin film layer. When a solution (coating layer) of a polyvalent metal salt containing an acrylamide compound and an unsaturated phthalic acid compound formed (coated) on the layer on which the polymer layer has been formed is polymerized, various known methods can be used. Specifically, for example, a method of irradiating or heating using an energy ray containing an episode of radiation can be used.菖When the above energy ray is used, it is lifted before the energy ray belonging to the wavelength range of 0-0001 to 800 nm, and the rest is not special.

099145744 lc S 201139548 Restriction The energy ray system may, for example, be a line, a β line, a γ line, a χ line, a visible ray, an ultraviolet ray, an electron beam or the like. Among these energy rays, from the viewpoint of ease of handling, it is preferable that visible light in the wavelength region of 400 to 800 nm, ultraviolet rays in the range of 50 to 4 nm, and 〇〇i to 〇电子2nm range of electron beams. When the energy ray system uses visible light and ultraviolet rays, it is necessary to add a photopolymerization initiator to a mixed solution of the monovalent metal salt of the unsaturated carboxylic acid compound and the polyvalent metal salt. As the photopolymerization initiator, a known product can be used, for example, 2-hydroxy-2-methyl-1-phenyl-propane-indole-ketone (manufactured by Ciba Super Chemical Co., Ltd., trade name DAROCUR® 1173), 1-jing Base-cyclohexyl-phenyl ketone (manufactured by Ciba Super Chemical Co., Ltd., trade name: IRGACURE 184), bis(2,4,6-trimethylphenylhydrazinyl)-phenylphosphine oxide (Ciba Super Chemical Company) , trade name: IRGACURE 819), 1-[4-(2-hydroxyethoxy)-phenyl]_2-trans-based 2_mercapto-1-propan-1-one (Ciba Super Chemical Company) , product name: IRGACURE 2959), a mixture of α-hydroxyketone, decylphosphine oxide, 4-decyldiphenyl ketone and 2,4,6-tridecyldiphenyl hydride (manufactured by Lamberti Super Chemical Co., Ltd., Trade name: ESACURE KT046), ESACURE KT55 (Lamberti Super Chemical), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (manufactured by Lamson Flame Chemical Co., Ltd., trade name: SPEEDCURE TPO), etc. A free radical polymerization initiator which is manufactured/sold by trade name. When the polyvalent metal salt of the unsaturated carboxylic acid compound containing the acrylamide compound is polymerized, the solution may be polymerized in a state containing a solvent such as water to carry out a polymerization of 099145744 16 201139548', or a part thereof may be dried. The polymerization is carried out, and when the solution is applied immediately after the solution is applied, in order to prevent the obtained polymer layer from being whitened, it is preferred to start the polymerization in the presence of a solvent (preferably water) in the case where the metal salt is polymerized. The polymerization was carried out while evaporating the solvent. By using the polymer layer obtained by the above polymerization, the gas barrier performance can be further improved by further performing heat treatment. The heat treatment is preferably carried out in a temperature range of 6 〇 to 35 ° C (preferably 100 to 3 ° C, more preferably ISO to 250 ° C), preferably in an inert gas atmosphere. under. Further, (4) at the time of heat treatment is not particularly limited, and it can be used under pressure, under reduced pressure, and under normal pressure. Further, the heat treatment time is usually from 3 to 90 minutes, preferably from 1 minute to 7 minutes, more preferably from 5 minutes to 6 minutes. In the present month, the polymer layer may be continuously subjected to heat: after temporarily returning to normal temperature, and then the polymer layer is subjected to heat treatment. Pass = system 仏 efficiency touch, (4) continuous steps. The phase step and heat treatment are carried out for the polymer layer to be heat treated. It is further subjected to heat treatment, by dehydration two:: reconfiguring the structure of the film, _ into the stability (four), estimating the partial phase of the cut phase < gas barrier layered body > 1 liter of gas Sex. Further, the gas barrier film of the present invention may further comprise a substrate layer. Beta inorganic film layer, with 099145744

S 201139548 The composition of the barrier laminate of the present invention is, for example, a substrate layer/inorganic film layer/gas barrier film, a substrate layer/undercoat layer/inorganic film layer/gas barrier film, and the like. <Inorganic film layer> The inorganic film layer formed on at least one side of the gas barrier film of the present invention may be, for example, an inorganic compound such as indium, zinc or sulphur dioxide or an oxide thereof, or other inorganic substance. a thin film layer, or a composite such as an oxide, a nitride, a compound, or an oxynitride such as Shixia, Syria, Chin, Wrong, Tin, Zhen, or the like. The method of forming the inorganic thin film layer is a well-known method. For example, a method of forming a film by bribery or chemical vapor deposition (CVD). When the binding reaction is rapidly carried out, the inorganic atom or compound is preferably a chemically active molecular species or atomic species. I Inventively, the inorganic thin film layer of the gas-permeable laminate is preferably an inorganic gasification material, more preferably Si Xi nitride (siN or the like), Shixi oxynitride (9) 0N, or the like. The film formation method of the inorganic thin film layer is not particularly limited, and a vacuum vaporization method, a disordered phase growth method, a physical vapor deposition method, a chemical vapor deposition method (CVD method), a gel-gel method, or the like can be used. . Among them, a film such as a slit method, an ion 1 bond method, a vapor phase evaporation method (CVD), a gas vapor phase forging method (pVD), an electropolymerization method, or the like is used, and a film is introduced under reduced pressure. Thereby, the surface smoothness of the inorganic thin film layer is improved by rapidly reacting the chemically active molecular species such as nitride or oxynitride, and it is predicted that pore formation can be reduced. The thickness of the inorganic thin film layer is usually 0.1 to 0 Å, and preferably 099145744 18 201139548 1 to 500 nm. <Substrate layer> The base material layer used in the gas barrier layered product of the present invention is composed of an organic material such as a thermosetting resin, a thermoplastic resin or paper, and the shape thereof is also exemplified by a sheet or a film. It has the shape of a plate, a cup, a hollow body, and the like. Examples of the thermosetting resin include various known thermosetting resins such as an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea melamine tree, a polyamine phthalate resin, a polyoxin resin, and a polyfluorene resin. Amines, etc. The thermoplastic tree tanning system can be exemplified by various known thermoplastic resins, for example, polyolefin (polyethylene fluorene polypropylene, poly-4-methyl ketone, polybutene, etc.), polyester (poly(p-phenylene terephthalate) Ester, polybutylene terephthalate, polyethylene naphthalate, etc., polydecylamine (nylon-6, nylon-66, poly-m-xylylenediamine, etc.), polyvinyl chloride, Polyimide, ethylene/vinyl acetate copolymer or saponified milk, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionic polymer, gas resin or mixture of materials I The handle base material layer may be a single layer or a laminated film composed of two or more thermoplastic resins in combination with a gas barrier laminate. The resin constituting the base material layer of the present invention is preferably, for example, polypropylene, polyethylene terephthalate, or polyethylene naphthalate, from the viewpoint of excellent transparency, rigidity, and properties. The biaxially stretched film of polyamine is more preferably ethylenediamine (10) polynaphthalene m because it is more excellent in impurities. Further, it may be coated on the surface of the substrate layer such as polyvinylidene chloride, 099145744 201139548 polyvinyl alcohol, ethylene vinyl alcohol copolymer, acrylic resin, urethane resin or the like. Further, in order to improve the adhesion between the surface of the substrate layer and the gas barrier film, surface activation treatment such as corona treatment, flame treatment, plasma treatment, or flame treatment may be applied to the surface. <Undercoat layer> In the gas barrier layered product of the present invention, when the inorganic thin film layer is formed on the base material layer, it is preferred to form an undercoat layer on the surface of the base material layer in advance, preferably forming An undercoat layer of an epoxy (meth) acrylate compound or an amine phthalate acrylate compound. The preferred undercoat layer of the present invention is a layer 0 epoxy (fluorenyl) acrylate system formed by curing an epoxy (meth) acrylate-based compound or an urethane (meth) acrylate-based compound. The compound can be exemplified by, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol s type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, an aliphatic epoxy group. An epoxy compound such as a compound, a compound obtained by reacting with acrylic acid or methacrylic acid, and an acid-modified epoxy (methyl) obtained by further reacting the compound with a slow acid or a dehydrated product thereof Acrylate. The epoxy (meth)acrylic acid S-based compound is a photopolymerization initiator and, if necessary, other photopolymerization or allergic single rider, and (4) is disposed on the surface of the substrate layer. 'Ther is then irradiated with ultraviolet light, etc., and then the cross-linking reaction is used to make the coating of 099145744 20 201139548. The urethane (meth) acrylate type compound is composed of an oligomer composed of a polyol compound and a diisocyanate compound, which is formed by acrylation. The polyamine phthalate oligomer can be obtained from a condensation product of a polyisocyanate and a polyol. Specific examples of the polyisocyanate include, for example, methylene bis(p-phenylene diisocyanate), adduct of hexamethylene diisocyanate/hexanetriol, hexamethylene diisocyanate, and phenylphenyl diisocyanate. , an adduct of phenylphenyl diisocyanate, tridecyl 1,5-diisophthalate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-diphenyl isocyanate dimer, hydrogenated benzodiazepine diisocyanate, ginseng (4-phenylisocyanate) phosphorothioate, etc.; further, specific polyols can be exemplified by polyoxygen A polyether polyol such as tetradecyl glycol; a polyester polyol such as a polyadipate polyol or a polycarbonate polyol; a copolymer of an acrylate and hydroxyethyl methacrylate; and the like. The single system constituting the acrylate can be exemplified by (decyl) decyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (曱) Base) methoxyethyl acrylate, butoxyethyl (meth)acrylate, benzoyl acrylate, and the like. These epoxy (meth) acrylate type compounds and urethane (meth) acrylate type compounds can be used in combination as necessary. Further, the method of carrying out the polymerization is known as various methods, and specifically, a method of performing irradiation or heating by an energy ray containing free radiation.

S 099145744 21 201139548 + When the undercoat layer is formed by hardening, it is more expensive to use such as acetophenone, diphenyl _, stilbene (tetra) benzoyl (tetra), _ fen fen or oxime The material polymerization agent is used, and a photo-sensitizer such as n-butylamine-ethylamine-n-butylphosphine is used as a light sensitizer and mixed. Further, in the present invention, an epoxy (meth) acetoacetate-based compound and an urethane (meth) acrylate-based compound are also used in combination. Further, the specific % oxygen (meth) acetophenone oxime-based compound or the amine phthalic acid sulfonic acid vinegar-based compound is diluted with a (mercapto)acrylic acid monomer. Such a (mercapto)acrylic acid single system can be exemplified by (mercapto) methic acid methyl vinegar, (mercapto) acrylic acid vinegar, (mercapto) butyl acetonate, Acetic acid _2_ ethyl hexanoic acid, (fluorenyl) propylene methoxy ethoxy acetate, (meth) propionic acid butoxyethyl ester, phenyl (meth) acrylate; and polyfunctional monomer Such as: trihydroxymercaptopropane tri(indenyl) acrylate, hexanediol (mercapto) acrylate, tripropylene glycol bis(indenyl) acrylate, diethylene glycol bis(decyl) acrylate, pentaerythritol II (fluorenyl) acrylate, dipentaerythritol hexa(indenyl) acrylate, hydrazine, 6-hexanediol bis(indenyl) acrylate, neopentyl glycol di(meth) acrylate, and the like. Among them, in the case where a urethane (fluorenyl) acrylate-based compound is used as the undercoat layer, the oxygen barrier property of the obtained gas barrier layered product is further improved. The thickness of the undercoat layer of the present invention is usually in the range of 0.01 to 100 g/m2, preferably 0.05 to 50 g/m2, in terms of coating amount. <Manufacturing Method of Gas Barrier Laminate> 099145744 22 201139548 For example, when the gas barrier layered system of the present invention has a substrate layer, in the method for producing the gas barrier film, a layer system in which a gas barrier film is to be formed is used. The above substrate layer can be used. Alternatively, a gas barrier film may be formed in advance and laminated on the substrate layer. <Protective layer> In the gas barrier film or the gas barrier layered product of the present invention, the outermost layer on the gas barrier film side may be provided with a protective layer capable of protecting the gas barrier film. The δ layer is made of a thermosetting resin such as a % oxygen resin, an unsaturated polyester resin, an anthraquinone resin, a urea melamine resin, a polyamine phthalate resin, a polyoxyxylene resin, an amine resin, or a polyimine. , polyolefin (polyethylene, polypropylene, poly 4-methyl-1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, poly Ethylene naphthalate, etc.), polydecylamine (nylon-6, nylon-66, poly-m-decylylenediamine, etc.), polyethylene, polyimine, ethylene, vinyl acetate copolymer Or a layer composed of a saponified product, a polyvinyl alcohol, a polyacrylonitrile, a polycarbonate, a polystyrene, an ionic polymer, or a thermoplastic resin such as a mixture thereof. The protective layer is composed of at least one of the above thermosetting resin or thermoplastic resin, and may be composed of two or more kinds. Further, the protective layer may be a single layer or a plurality of layers of two or more layers. By providing the above protective layer, it is possible to effectively prevent the gas barrier film from being damaged by the external mechanical/chemical action, and to impart a more stable high barrier property. The protective layers may be laminated directly on the gas barrier film, or may be laminated through an anchor c〇at layer composed of an adhesive agent 5 099145744 23 201139548 or the like. The encapsulating layer constituting the anchor layer can be made of the same material as the undercoat layer in addition to the adhesive. The adhesive constituting the tin-solid layer of the present invention can be made, for example, from an organic titanium-based resin, a poly-ethylenimine-based resin, a urethane-based resin, an epoxy resin, or an acrylic tree. a laminating adhesive composed of a resin, a resin containing a thiophene group such as α, a modified lithium resin, a calcined titanate, a polyester polybutadiene, or the like; or a one-component type, a two-component type polyol, a dry lamination adhesive represented by a polyurethane sealant composed of a polyisocyanate, an aqueous urethane ionomer, and a hardener; and such as an acrylic, vinyl acetate, amine An aqueous dry laminating adhesive such as an acid ester or a polyester resin as a main raw material, and a solventless laminating adhesive represented by a polyamine phthalate-based adhesive are treated. Among them, from the viewpoint of excellent water resistance, it is preferred to use a resin composed of a water-soluble or water-dispersible polyurethane s-based resin, a poly-g-type resin, an acrylic resin, or an oxazoline-containing resin. The agent is more preferably an adhesive composed of a polyurethane resin. [Examples] Examples are described below. Physical property values and the like are obtained according to the following evaluation methods. (1) Absorbance ratio (AQ/A): Measurement was carried out in accordance with the above-described recording method. (2) Oxygen permeability [ml/(m2 · day · MPa)]: The stretch film was made of OX-TRAN 2/21 ML manufactured by M〇c〇n Co., Ltd. according to JIS K7126, temperature 2 (TC, humidity 90% RH) (3) Bending test 099145744 24 201139548 The laminated film was overlapped, and the end face was heat-sealed, and the heat-sealed portion was bent, and subjected to boiling treatment at 98 ° C for 30 minutes. After boiling treatment, 'observed the floating state of the bent portion. The evaluation results were evaluated according to "very good", "good", "ordinary", and "bad". (4) Wet peel strength, boiled laminated film According to the wet state, the laminated surface of the barrier film was peeled off from the non-stretched polypropylene film, and after sampling to a width of 15 mm, the peel strength of the 9-inch laminate was measured at a peeling speed of 300 (mm/min). <Production of Solution (S1)> Preparation of 88% by mass of N-(2-hydroxyethyl) acrylamide by acryl (manufactured by Asada Chemical Co., Ltd., a salt of acrylic acid) (manufactured by Xingren Co., Ltd.) 3 mass%, and vinyl alcohol polymer 9% by mass (zinc zinc acrylate, N_(2) a composition comprising _ 乙基 ) 、 、 、 及 及 及 及 及 及 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液25 mass% of photopolymerization initiator hydroxyethoxy phenyl]-2-yl-2-methyl-1-propanone-i-ketone (manufactured by Ciba Super Chemical Co., Ltd., trade name: IRGACURE 2959) And a surfactant (manufactured by Kao Corporation, trade name: EMULGEN 120), according to the solid content ratio of 98.5%, a%, 〇.3%, respectively, to prepare a solution (S1). <Solution (S2) [Production] A photopolymerization initiator [1-[4_(2-hydroxyethoxy)) having a zinc acrylate aqueous solution of 98% by mass based on the solid content ratio and diluted with 2,099,145,744, 25, 2011,395,48% alcohol to 25% by mass. Phenyl]-2-hydroxy-2-methyl-1-propanone (manufactured by Ciba Super Chemical Co., Ltd., trade name: IRGACURE 2959) is 1,9 wt%/0, and a surfactant according to the solid content ratio. (made by Kao Co., Ltd., trade name: EMULGEN 12〇), which was mixed at 0.3% by weight based on the solid content ratio to obtain a zinc acrylate solution (S2) 〇 [Example 1] A zinc oxide solution (S1) of the above-mentioned unsaturated carboxylic acid compound containing N_(2_ethyl) acrylamide on the alumina-deposited polyester film (Mitsui Chemicals TOHCELLO Co., Ltd. t TL-PET H) The coating was carried out by a bar coating method so that the coating amount after drying became 1.2 g/m 2 . Then, it was dried in an oven at 40 C for 15 seconds, and then irradiated onto the entire stretched film so as to have an irradiation light amount of 200 mJ/cm 2 by using an ultraviolet irradiation device to obtain a barrier film having a polymer layer formed on the surface. In the infrared absorption spectrum, the ratio of the absorbance A〇 of vC=〇 of the carboxymethyl group near 1700 cm-i to the absorbance A of the vC=〇 of the carboxylate ion near 1520^11-1 (A〇/A) 0.1. The oxygen permeability of the film was determined to be less than 1 ml/m 2 · day · MPa. Further, a non-stretched polypropylene film (thickness is called and the end face is heat-sealed) is superimposed on the film, and the heat-sealed portion is bent, and the boiling treatment is performed for 981 for 981. The results of the bending test did not reveal the floating phenomenon, which is "very good 099145744 26 201139548 good." In addition, the 'boiled laminated thin crucible in the wet state, the laminated surface of the barrier film, and the non-stretched polypropylene The heat-sealed portion between the films was peeled off, and the width of the sample was taken. After 15 mm, the 9-degree lamination peel strength and the 180-degree lamination peel strength were measured at a peeling speed of 300 mm/min. The 90-degree lamination peel strength was 2.4 N/15 mm. The 180-degree lamination peel strength is 3 7 N/15 mm. The oxygen permeability after the boiled Buddha is 1 ml/m 2 · day · MPa. [Example 2] In Example 1, except N-(2-hydroxyl) The ethyl acetoamine was changed to N,N-didecyl acrylamide (manufactured by Xingren Co., Ltd.), and the rest was carried out in the same manner as in the examples. The oxygen permeability of the film was measured, and the results were Less than lmym2 · day · Mpa β on the 5 hai film weight @ no extended polypropylene film (thickness 7 〇 ^ m), heat the end face In the state where the heat-sealed portion is bent, the boiling treatment is performed for 3 minutes according to 98. The bending test of the film does not show the floating phenomenon, and the system is "good". Further, the boiling layer is laminated. In the wet state, the film is peeled off from the laminated surface of the barrier film and the heat-sealed portion between the non-stretched polypropylene film, and the sample width is 15 mm, and the 9-degree layer is measured according to the peeling density of 300 mm/min. Press peel strength, 180 degree laminate peel strength. 9 twist laminate peel strength is 1.0N/15mm, 180 degree laminate peel strength is 丨〇N/15mm. 099145744 27 201139548 Furthermore, the milk penetration after cooking Linl/ni2 · day · MPa. [Example 3] In Example 1, except for the polyester film which was vapor-deposited alumina (TL-PET H by Mitsui Chemicals TOHCELLO Co., Ltd.), it would not contain ν· A zinc salt solution (S2) of an unsaturated citric acid compound of (2-hydroxyethyl) acrylamide is applied by a bar coating method in a coating amount of 〇4 g/m2 after drying, and an external ray irradiation apparatus is used immediately. Irradiating the entire film as a whole by the amount of light 2 〇〇 mJ/cm 2 and forming a poly A film of the laminated layer was obtained on the film of the combined layer, except that the solution containing the n-(2-hydroxyethyl) acrylamide (S1) was applied, and the oxygen permeability of the film was measured. Fully lml/m2.day.MPa. Overlap the unstretched polypropylene film (thickness 7〇μχη) on the film, heat seal the end face, and bend the heat-sealed portion in a state of 98〇c. Boiling treatment. As a result of the bending test of the film, it was found that the floating phenomenon was "good". In addition, in the wet state, the laminated film of the 'boiled'' is peeled off from the laminated surface of the barrier film and the heat-sealed portion between the non-extended polypropylene film, and the sample width is 15 mm, and is 300 mm/min. The peeling speed was measured at 9 twist laminate peel strength and 180 degree dust peel strength. The 9-degree lamination peel strength is 2 〇N/15 mm or more, and the 180-degree lamination peel strength is 2 〇N/15 mm or more. Further, the oxygen permeability after boiling is 1 ml/m 2 · day · Mpa. 099145744 28 201139548 [Comparative Example] The same procedure was carried out except that N-(2-hydroxyethyl) acrylamide was not used except for the case of Example 1. : & The film was overlaid on a non-stretched polypropylene film (thickness 7 G/mi), and the end face was heat-sealed to a state in which the heat-sealed portion was bent.煮 Boiling treatment for 3 minutes. As a result of the bending test of the film, it was found that the floating phenomenon was "bad". Further, the boiled laminated film is peeled off from the laminated surface of the barrier film and the heat-sealed portion between the non-stretched polypropylene film in a wet state, and the sample width is 15 mm (mm), and then 3 〇〇 The peeling speed of (mm/min) was measured for 9-degree lamination peel strength and 180-degree lamination peel strength. The 9-degree lamination peel strength is 〇.6 (N/15mm), and the 180-degree laminated peel strength is 〇 8 (N/15mm). (Industrial Applicability) The gas barrier film of the present invention and the laminated film using the same are excellent in gas barrier properties under high humidity. This feature can be used for various purposes. It can be suitably used for packaging materials such as dry foods, beverages, boiled • bactericidal foods, health foods, etc., among which high gas barrier properties are required.

Electronic chassis covering materials such as road chassis, 099145744 sorrow 'packages and packaging for medical products and medical appliances 乂 and such as: hard disk, wiring chassis, printing power ±±, ' and such as: liquid crystal display, plasma display

S 29 201139548 Blocking materials for inorganic displays, inorganic/organic EL displays, electronic paper, and other barrier materials for flat-panel displays, and barrier sheets for solar cell backing sheets, and other barrier materials for electronic materials and barrier materials for vacuum insulation materials Packaging materials for industrial products such as ink cartridges, packaging materials for various products, or protective materials for materials such as electronic materials, precision parts, and pharmaceuticals that do not like oxygen penetration and moisture. 099145744 30

Claims (1)

201139548 VII. Patent application range: 1. A gas barrier layer comprising a polymer layer of a polyvalent metal salt of an unsaturated carboxylic acid compound containing 0.3 to 15% by mass of an acrylamide compound represented by the following general formula (1). Composition; cc 2 R Η 3 R / N 1 thief [where 'Rl is hydrogen or methyl; R2 is hydrogen or alkyl having 1 to 4 carbon; R3 is hydrogen, alkyl having 1 to 4 carbon atoms, or a group consisting of the following general formula (2); R2, R3 may be linked to form a porphyrin ring; R5 I - (R4) η - γ General formula (2) ί R1 [wherein η is an integer of 1 to 5 R4 is a methylene group or an ethyl group; a nitrogen group or a carbon number of 1 to 4; R6 is an alkyl group having a carbon number of 4 to 4; an anthracene, -NH2, or _n(CH3)2] . 2. The gas barrier film of claim 1, wherein the acrylamide compound represented by the general formula (1) is from Ν_(2^ethyl)acrylic acid amine, N,N-diethyl 099145744 201139548 acrylamide , acrylonitrile of isopropyl isopropyl acrylamide, N,N-dimethylaminopropyl propyl amide, N,N-dimethyl decylamine, and acryloyl porphyrin Amine compound. 3. The gas barrier film of claim 1, wherein the polyvalent metal compound of the unsaturated carboxylic acid compound and the polyvalent metal salt of at least one selected from the group consisting of Mg, Ca, Ba, Zn and A1 . 4. The gas barrier film of claim 1, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is a salt obtained from a monomer of an unsaturated carboxylic acid or a polymer having a degree of polymerization of less than 2 Å. 5. The gas barrier film of claim 1, wherein the polyvalent metal salt of the unsaturated acid compound is a salt of (meth)acrylic acid. 6. For example, the gas barrier film of the first application of the patent scope, wherein the polymer layer is infrared absorbing light s Jinzhong 'according to the absorbance A of the pC=0 near the 17 〇〇cm_1, and according to the vicinity of 1520 cm-1 The ratio of the absorbance A of the carboxylate ion i; C = 0 (A 〇 / A) is less than 0.25. 7. The gas barrier film according to any one of claims 1 to 6, wherein the protective layer is provided on the surface of the gas barrier film via an anchor coat layer or a pin-free layer. A gas barrier layered product obtained by forming an inorganic thin film layer on at least one side of a polymer layer according to any one of claims 1 to 7. 9. The gas barrier laminate according to the eighth aspect of the invention, wherein the substrate layer is laminated on the other surface of the inorganic thin film layer. 10. The gas barrier laminate according to claim 8, wherein the inorganic thin film layer is passed through an undercoat layer of an epoxy (meth) acrylate compound or an amine phthalate acrylate compound. The laminate is formed on the substrate layer. S 099145744 33 201139548 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: Yi * *»> 5. If there is a chemical formula in this case, please reveal the best Chemical formula showing the characteristics of the invention: Rs I —(R4 ) n — Y General formula (2) I R1 099145744 2 201139548 9w 45 7 4 4 APR 2 2 2011 . VII. Patent application scope: Replacement, 1. Gas barrier film, including the following A polymer layer of a polyvalent metal salt of an unsaturated carboxylic acid compound having a propylene amide compound of the formula (1): 0.3 to 15% by mass; R1; Css Q Η CII ο General formula )1) [wherein 'R is a hydrogen or a fluorenyl group; R2 is a hydrogen or an alkyl group having 1 to 4 carbon atoms; R3 is a hydrogen, an alkyl group having 1 to 4 carbon atoms, or is represented by the following general formula (2) The base of the composition; r2, r3 can be connected to form a imiline ring; R1 I - C RM η - Υ " «General formula (2) 1 R1 [where 'η is an integer from 1 to 5; R4 is an alkylene group or Ethyl group; R5 is hydrogen or an alkyl group having 1 to 4 carbon atoms; R6 is carbon number! An alkyl group of 4; γ-form-11, -NH2, or -N(CH3)2]. 2. The gas barrier film of claim 1, wherein the acrylamide compound represented by the general formula (N) is from N-(2-hydroxyethyl) acrylamide, n, N-diethyl 099145744 31 201139548 rt Selection of acrylamide, N-isopropylacrylamide, N,N-dimercaptopropyl propyl decylamine, hydrazine, hydrazine-dimethyl decylamine, and acrylonitrile porphyrin At least one acrylamide compound. 3. The gas barrier film of the first aspect of the invention, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is at least one selected from the group consisting of Mg, Ca, Ba, Ζη and Α1. 4. The gas barrier film of claim 1, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is a salt obtained from a monomer of an unsaturated carboxylic acid or a polymer having a degree of polymerization of less than 20. 5. The gas barrier film of claim 1, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is a salt of (meth)acrylic acid. 6. The gas barrier film of claim 1, wherein the polymer layer is in the infrared absorption spectrum, according to the absorbance A〇 of the vC=0 of the tick acid group near nOOcm'1, and the carboxylate ion according to the vicinity of 1520 cm_1 The ratio of absorbance A of vC = 0 (A 〇 / A) is less than 0.25. 7. The gas barrier film according to any one of claims 1 to 4, wherein a protective layer is provided on the surface of the gas barrier film via an anchor coat layer or not via an anchor layer. A gas barrier layered product obtained by forming an inorganic thin film layer on at least one side of a polymer layer according to any one of claims 1 to 7. The ninth aspect of the invention is the gas barrier laminate according to the eighth aspect of the invention, wherein the substrate layer is laminated on the other side of the inorganic thin film layer. 10. The gas barrier laminate according to item 8 of the patent application, wherein the inorganic thin film layer is coated with an epoxy (fluorenyl) acrylate compound or a urethane (mercapto) acrylic S compound. The layer is formed by laminating on the substrate layer. Ο 099145744 33