JPWO2011078167A1 - Gas barrier film and laminate - Google Patents

Abstract

[Problem] To provide a gas barrier film suitable for a packaging material which is transparent and excellent in gas barrier properties such as oxygen and water vapor. [Solution] A gas barrier film comprising a polymer layer of 0.3 to 15% by mass of an acrylamide compound of the following general formula (1) and a polyvalent metal salt of an unsaturated carboxylic acid compound. [However, R1 is hydrogen or a methyl group, R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R3 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group consisting of the following general formula (2): R2 and R3 may be linked to form a morpholine ring. Wherein n is an integer of 1 to 5, R4 is a methylene group or ethylene group, R5 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R6 is an alkyl group having 1 to 4 carbon atoms, Y is , -OH, -NH2, or -N (CH3) 2. ]

Description

  The present invention relates to a gas barrier film that is excellent in adhesiveness with an inorganic thin film layer and the like, has transparency, and is suitable for a packaging material excellent in gas barrier properties such as oxygen and water vapor, particularly water vapor barrier properties.

  In recent years, as a barrier material against oxygen or water vapor, inorganic oxides such as silicon oxide and aluminum oxide have been formed on film substrates by vacuum deposition, sputtering, ion plating, chemical vapor deposition, etc. A transparent gas barrier film is attracting attention. Such a transparent gas barrier film is a film obtained by depositing an inorganic oxide on a base material surface made of a biaxially stretched polyester film that is generally excellent in transparency and rigidity. When used as a packaging film, the inorganic oxide may be cracked by rubbing or stretching during post-processing printing or laminating or filling the contents, and the gas barrier property may be lowered.

  A method of laminating a polyvinyl alcohol having a gas barrier property and an ethylene / vinyl alcohol copolymer on a biaxially stretched film substrate (for example, Patent Document 1) or a biaxial composition of polyvinyl alcohol and poly (meth) acrylic acid A method of coating a stretched film substrate (for example, Patent Document 2) has been proposed. However, the gas barrier film formed by laminating polyvinyl alcohol has a reduced oxygen barrier property under high humidity, and the composition of polyvinyl alcohol and poly (meth) acrylic acid has sufficiently advanced esterification, In order to improve the gas barrier property of the film, it is necessary to heat at a high temperature for a long time. Further, although the oxygen gas barrier property is exhibited, the moisture resistance is not sufficient.

  On the other hand, as a method for improving gas barrier properties, the present inventors have applied a method of coating a polymer of a polyvalent metal salt of an unsaturated carboxylic acid such as zinc acrylate on a transparent inorganic vapor-deposited film layer (for example, Patent Document 3). However, depending on the application, it is desired to improve the adhesion to other layers.

JP 60-157830 A Japanese Patent No. 3203287 JP 2007-245433 A

  An object of the present invention is to obtain a gas barrier film suitable for a packaging material having transparency and excellent gas barrier properties such as oxygen and water vapor, particularly oxygen gas barrier properties.

The present invention provides a gas barrier film comprising a polymer layer of a polyvalent metal salt of an unsaturated carboxylic acid containing 0.3 to 15% by mass of an acrylamide compound represented by the following general formula (1). It is to provide.

[Wherein R ¹ is hydrogen or a methyl group, R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group consisting of the following general formula (2) And R ² and R ³ may be linked to form a morpholine ring. ]

[Where n is an integer of 1 to 5, R ⁴ is a methylene group or ethylene group, R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is an alkyl group having 1 to 4 carbon atoms, or , Y is —OH, —NH ₂ , or —N (CH ₃ ) ₂ . ]

  The gas barrier film of the present invention is excellent in adhesion to other layers, has transparency, and is excellent in gas barrier properties such as oxygen and water vapor, particularly oxygen gas barrier properties.

<Acrylamide compounds>
The acrylamide compound which is one of the components constituting the gas barrier film (hereinafter also referred to as “polymer layer”) of the present invention is an acrylamide compound represented by the following general formula (1).

[Wherein R ¹ is hydrogen or a methyl group, R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group consisting of the following general formula (2) And R ² and R ³ may be linked to form a morpholine ring. ]

[Where n is an integer of 1 to 5, R ⁴ is a methylene group or ethylene group, R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is an alkyl group having 1 to 4 carbon atoms, or , Y is —OH, —NH ₂ , or —N (CH ₃ ) ₂ . ]
Specific examples of these acrylamide compounds include N- (2-hydroxyethyl) acrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, and Examples thereof include acryloylmorpholine.

<Unsaturated carboxylic acid compound>
The unsaturated carboxylic acid compound which is one of the components constituting the polyvalent metal salt of the unsaturated carboxylic acid compound according to the present invention is an α, β-ethylenic acid such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. It is a carboxylic acid compound having an unsaturated group.

  This may be preliminarily polymerized as necessary, and in the case of prepolymerization, the degree of polymerization is preferably less than 20, particularly 10 or less.

  When polymerized in advance, a polymer (polymer compound) having a degree of polymerization of 20 or more is obtained by polymerizing a salt with a polyvalent metal compound described later, and the gas barrier property under high humidity is improved. There is a risk that it will not be.

  In the case where a polymer is used as the unsaturated carboxylic acid compound, a small amount of unsaturated carboxylic acid ester compound such as methyl (meth) acrylate and ethyl (meth) acrylate is used within the range not impairing the object of the present invention. It may be polymerized.

  In addition, the notation of (meth) acryl in (meth) acrylic acid, ethyl (meth) acrylate, etc. indicates that both cases of methacryl and acrylic are included, and so on. .

  Among these unsaturated carboxylic acid compounds, a salt in which a monomer is completely neutralized with a polyvalent metal compound is easy to form, and a film obtained by polymerizing the salt is excellent in gas barrier properties, which is preferable.

<Polyvalent metal compound>
The polyvalent metal compound which is one of the components constituting the polyvalent metal salt of the unsaturated carboxylic acid compound according to the present invention is a metal and metal compound belonging to groups 2A to 7A, 1B to 3B and 8 of the periodic table Specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), bivalent or higher metals such as aluminum (Al), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites of these metals Such as salt. Among these metal compounds, divalent metal compounds are preferable, and magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and the like are more preferable. When these divalent metal compounds are used, the gas barrier property under high humidity of the film obtained by polymerizing the salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination.

<Polyvalent metal salt of unsaturated carboxylic acid compound>
The polyvalent metal salt of an unsaturated carboxylic acid compound as a main component constituting the gas barrier film of the present invention is a salt of an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and the polyvalent metal compound. These polyvalent metal salts of unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds. Among such unsaturated carboxylic acid compound polyvalent metal salts, the copolymer layer from which zinc (meth) acrylate is obtained is particularly excellent in the hot water resistance, and therefore preferred.

<Gas barrier film>
The gas barrier film of the present invention comprises the unsaturated carboxylic acid compound containing 0.3 to 15% by mass, preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass of the acrylamide compound. A film made of a polymer with a polymetal salt (total amount of acrylamide compound and polyvalent metal salt of unsaturated carboxylic acid compound is 100% by mass).

  When the content of the acrylamide compound is less than 0.3% by mass, the effect of improving the adhesiveness of the obtained gas barrier film is small. On the other hand, when the content exceeds 15% by mass, excellent adhesiveness is maintained, but the gas barrier is maintained. Tend to decrease.

  The polymer layer according to the present invention is a methyl (meth) acrylate, ethyl (meth) acrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, tetraethylene as long as the object of the present invention is not impaired. Unsaturated carboxylic acid (di) ester compounds such as glycol diacrylate, polyethylene glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, vinyl ester compounds such as vinyl acetate, etc. These monomers or low molecular weight compounds may be copolymerized.

  Further, the polymer layer according to the present invention may be formed by mixing with a vinyl alcohol polymer or a modified vinyl alcohol polymer as long as the object of the present invention is not impaired.

  Specifically, as the modified vinyl alcohol polymer, a part of the OH group of the vinyl alcohol polymer serving as a substrate is substituted with an α, β-ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid or the like. Examples thereof include (meth) acrylate group-modified vinyl alcohol polymers obtained by reacting with a carboxylic acid compound or a derivative thereof and introducing a (meth) acrylate group.

  Moreover, the modified vinyl alcohol polymer obtained by the method of introduce | transducing a reactive functional group into the side chain of a vinyl alcohol polymer by polymer reaction may be sufficient. Specifically, a vinyl alcohol-based polymer serving as a substrate obtained by polymerizing vinyl esters in the presence of thiolic acid and saponifying the resulting polymer to introduce thiol groups only at the molecular ends. A thiol group-modified vinyl alcohol polymer having a thiol group (—SH group) as a part of the OH group of the coalescence is exemplified.

  Further, a method of adding a silyl group by post-modification using a silylating agent such as organohalogen silane, organoacetoxy silane, organoalkoxy silane to a vinyl alcohol polymer or a vinyl acetate polymer containing a carboxy group or a hydroxyl group, or Copolymers of vinyl acetate and silyl group-containing olefinically unsaturated compounds such as vinyl silane and (meth) acrylamide-alkyl silane are saponified to have alkoxysilyl groups, acyloxysilyl groups or hydrolysates thereof in the molecule. It may be a modified vinyl alcohol polymer obtained by a method of introducing a silyl group such as a silanol group or a salt thereof. Specifically, a silyl group-modified vinyl having a trialkoxysilane group such as a trimethoxysilane group or a triethoxysilane group, a tricarbonyloxysilane group, etc. as part of the OH group of a vinyl alcohol polymer as a substrate. Examples include alcohol polymers.

  Also, a method in which a vinyl alcohol polymer is dispersed in an acetic acid solvent and diketene is added thereto, a vinyl alcohol polymer is previously dissolved in a solvent such as dimethylformamide or dioxane, and the diketene is added thereto. It may be a modified vinyl alcohol polymer obtained by a method of adding, a method of directly contacting a diketene gas or liquid diketene with a vinyl alcohol polymer, and the like. Specifically, a modified vinyl alcohol polymer such as an acetoacetyl group-modified vinyl alcohol polymer having an acetoacetyl group in a part of the OH group of the vinyl alcohol polymer serving as a substrate can be mentioned.

  Furthermore, water-soluble polymers such as ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, gum arabic, and methyl cellulose, acrylate polymer, ethylene / acrylic acid copolymer, High molecular weight compounds such as polyvinyl acetate, ethylene / vinyl acetate copolymer, polyester, polyurethane, etc., lubricant, slip agent, anti-blocking agent, antistatic agent, antifogging agent, pigment, dye, inorganic or organic filling Various additives such as an agent may be included, and various surfactants and the like may be included in order to improve wettability, adhesion, and the like with a base material described later.

  Among these, vinyl alcohol polymers, especially modified vinyl alcohol polymers are preferred, and among them, (meth) acrylate group-modified vinyl alcohol polymers formed by introducing (meth) acrylate groups such as acrylic acid and methacrylic acid. It is more preferable to use together.

  As a mixing ratio of the acrylamide compound, the polyvalent metal salt of the unsaturated carboxylic acid compound, and the vinyl alcohol polymer, the acrylamide compound is 0.5 to 15% by mass, and the polyvalent metal salt of the unsaturated carboxylic acid compound. 85 to 95% by mass, and 1 to 20% by mass of vinyl alcohol polymer (100% by mass in total of acrylamide compound, polyvalent metal salt of unsaturated carboxylic acid compound, and vinyl alcohol polymer) Is preferred.

The thickness of the polymer layer according to the present invention can be determined depending on various uses, but is usually in the range of 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm.
<Method for producing gas barrier film>
As a method for producing a gas barrier film according to the present invention, acrylamide compound 0.5 to 15% by mass, polyvalent metal salt of unsaturated carboxylic acid compound 85 to 95% by mass, and vinyl alcohol polymer 1 to 20 are used. The polymer layer after being dissolved in a solvent such as water at a ratio of mass% (the total of the acrylamide compound, the polyvalent metal salt of the unsaturated carboxylic acid compound, and the vinyl alcohol polymer is 100 mass%). A method of applying a solution of the mixture on the surface on which the acrylamide compound is formed, individually preparing a solution of the acrylamide compound and a solution of the polyvalent metal salt of the unsaturated carboxylic acid compound, and then the amount of the acrylamide compound is 0.5 A method of applying a mixed solution to ˜5% by mass on the surface on which the polymer layer is formed, and an unsaturated carboxylic acid and polyvalent metallization together with an acrylamide compound It is possible to use a method in which a product is mixed to form an unsaturated carboxylic acid polyvalent metal salt, and another component such as a vinyl alcohol polymer is added thereto and a mixed solution is applied and polymerized. it can.

  Further, an unsaturated compound containing an acrylamide compound by adding an acrylamide compound and a polyvalent metal compound to the unsaturated carboxylic acid compound or a solution thereof at a ratio such that the concentration of the acrylamide compound is 0.3 to 15% by mass. A method in which a vinyl alcohol polymer is further added to a solution in which a polyvalent metal salt of a carboxylic acid compound is formed, and the whole ratio is adjusted to be applied can be used.

  Furthermore, depending on the shape of the layer for forming the polymer layer, various known methods such as a method of immersing the base material layer in the solution of the mixture, a method of spraying the solution of the mixture on the surface of the base material layer are not limited to the application method. The coating method can be taken.

  When using a solution in which an unsaturated carboxylic acid compound and a polyvalent metal compound are mixed, if the amount of polyvalent metal compound added is small relative to the unsaturated carboxylic acid, the laminate has a high content of free carboxylic acid groups. As a result, there is a possibility that the laminated body has a low gas barrier property. Moreover, when the addition amount of a polyvalent metal compound exceeds 1 chemical equivalent with respect to the carboxyl group of an unsaturated carboxylic acid compound, an unreacted polyvalent metal compound will exist and the acrylamide type compound formed may be The ratio with the polyvalent metal salt of the unsaturated carboxylic acid compound to be contained may not be controlled. Therefore, it is preferable that the addition amount of a polyvalent metal compound is 1 chemical equivalent with respect to the carboxyl group of unsaturated carboxylic acid.

  In addition, when a solution in which an unsaturated carboxylic acid compound is mixed with an acrylamide compound and a polyvalent metal compound is used, the unsaturated carboxylic acid compound and the polyvalent metal compound are usually unsaturated while being dissolved in the solvent. Although the polyvalent metal salt of a carboxylic acid compound is formed, it is preferable to mix for 1 minute or more in order to ensure the formation of the polyvalent metal salt.

  Among these methods, a method in which a polyvalent metal salt of an unsaturated carboxylic acid compound is prepared in advance and then an acrylamide compound is added and mixed. The addition amount of the acrylamide compound is in the range of 0.3 to 15% by mass. It is preferable because it can be arbitrarily adjusted.

  Solvents used in the mixed solution of the acrylamide compound and the polyvalent metal salt of the unsaturated carboxylic acid compound include water, lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, or a mixture thereof. Although a solvent is mentioned, water is the most preferable.

  As a method of applying a mixed solution of an acrylamide compound and a polyvalent metal salt of an unsaturated carboxylic acid compound having a polymerization degree of less than 20 on the layer for forming the polymer layer, for example, an air knife coater, a direct gravure coater, Gravure offset, arc gravure coater, gravure reverse and jet nozzle type gravure coater, top feed reverse coater, reverse feed coater such as bottom feed reverse coater and nozzle feed reverse coater, 5-roll coater, lip coater, bar coater, bar Using various known coating machines such as reverse coater, die coater, multilayer die coater, spin coater, dip coater and the like, an acrylamide compound and a polyvalent metal salt of an unsaturated carboxylic acid compound having a polymerization degree of less than 20 Appropriately applied according to the specific gravity of the polymer layer so that the thickness after drying and polymerizing the mixed solution is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm. do it.

  When the polyvalent metal salt of the acrylamide compound and the unsaturated carboxylic acid compound is dissolved, as described above, within the range not impairing the object of the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, etc. Monomers such as saturated carboxylic acid (di) ester compounds, vinyl ester compounds such as vinyl acetate, or low molecular weight compounds, polyvinyl alcohol, ethylene / vinyl alcohol copolymers, polyvinyl pyrrolidone, polyvinyl ethyl ester Water-soluble polymers such as tellurium, polyacrylamide, polyethyleneimine, starch, gum arabic, and methylcellulose, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyester, polyurethane High molecular weight compounds such as may be added.

  Further, when dissolving the polyvalent metal salt of the acrylamide compound and the unsaturated carboxylic acid compound, a lubricant, slip agent, anti-blocking agent, antistatic agent, antifogging agent is included within the range not impairing the object of the present invention. Various additives such as pigments, dyes, inorganic or organic fillers may be added, and various surfactants may be added to improve the wettability with the base material layer. Also good.

  In addition, as a method for forming a gas barrier film, 1) as a solution in which a polyvalent metal salt of an acrylamide compound and an unsaturated carboxylic acid compound is dissolved, a solution not using a vinyl alcohol polymer is applied and polymerized. Examples of the method of forming a gas barrier layer after forming a gas barrier film are as follows: 2) applying and polymerizing a solution using a vinyl alcohol polymer together. The order of “1)” and “2)” can be changed.

  Alternatively, a gas barrier film can be formed by sequentially applying and polymerizing a plurality of solutions in which the ratio of the vinyl alcohol-based polymer is gradually different from zero. When the gas barrier layer of the present invention is directly formed on an inorganic thin film layer such as an aluminum vapor deposition film, a gas barrier film is formed using a solution not containing a vinyl alcohol polymer for the gas barrier film in contact with the inorganic thin film layer. Further, by applying and polymerizing a solution using a vinyl alcohol polymer in combination, a gal barrier film can be formed without bringing the layer containing the vinyl alcohol polymer into direct contact with the inorganic thin film layer.

  In order to polymerize a solution (coating layer) containing (coating) an acrylamide-based compound formed on a layer for forming a polymer layer and a polyvalent metal salt of an unsaturated carboxylic acid compound, various known methods, specifically, Examples of the method include irradiation with energy rays containing ionizing radiation or heating.

  When the energy ray is used, it is not particularly limited as long as the wavelength region is an energy ray in the range of 0.0001 to 800 nm. Examples of the energy ray include α rays, β rays, γ rays, X rays, and visible rays. , Ultraviolet rays, electron beams and the like. Among these energy rays, visible light in the wavelength range of 400 to 800 nm, ultraviolet rays in the range of 50 to 400 nm, and electron beams in the range of 0.01 to 0.002 nm are easy to handle and the devices are widespread. Therefore, it is preferable.

  When visible light and ultraviolet light are used as energy rays, it is necessary to add a photopolymerization initiator to a mixed solution of a monovalent metal salt and a polyvalent metal salt of an unsaturated carboxylic acid compound. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals) , 1-Hydroxy-cyclohexyl ruphenyl ketone (Ciba Specialty Chemicals product name; Irgacure 184), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals product) Name; Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) 2959), α-hydroxyketone, acylphosphine. Side, mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name; Essaure KT046 manufactured by Lamberti Chemical Specialty), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6- A radical polymerization initiator manufactured and sold under the trade name of trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO manufactured by Ramson Fire Chemical Co., Ltd.) can be mentioned.

  When polymerizing a polyvalent metal salt of an unsaturated carboxylic acid compound containing an acrylamide compound, the solution may be polymerized in a state of containing a solvent such as water, or may be polymerized after partially drying. However, when the solution is polymerized immediately after coating, the polymerization is started in the coexistence of a solvent, especially water, when the metal salt is polymerized so that the resulting polymer layer is not whitened, and the solvent is evaporated. It is preferable to polymerize.

  The polymer layer obtained by the above polymerization can be further improved in gas barrier performance by further heat treatment.

The heat treatment is preferably performed in a temperature range of 60 to 350 ° C., preferably 100 to 300 ° C., more preferably 150 to 250 ° C. in an inert gas atmosphere. Moreover, the pressure at the time of heat processing is not specifically limited, Any of pressurization, pressure reduction, and normal pressure may be sufficient.
The time for the heat treatment is usually about 30 seconds to 90 minutes, preferably 1 minute to 70 minutes, and more preferably 5 minutes to 60 minutes.

  In the present invention, the polymer layer may be continuously heat-treated, or the polymer layer may be heat-treated after the film is once returned to room temperature. Usually, it is desirable in terms of production efficiency that the process of forming the polymer layer and the process of heat treatment are continued.

The polymer layer subjected to the heat treatment is presumed to have a film structure determined by polymerization. By subjecting this to further heat treatment, it is presumed that the dehydration and the membrane structure become a more stabilized layer by partial rearrangement, and the gas barrier properties are further improved.
<Gas barrier laminate>
The gas barrier film of the present invention may be laminated with an inorganic thin film layer and further a base material layer.

Examples of the structure of the gas barrier laminate of the present invention include substrate layer / inorganic thin film layer / gas barrier film, substrate layer / undercoat layer / inorganic thin film layer / gas barrier film, and the like.
<Inorganic thin film layer>
As the inorganic thin film layer formed on at least one side of the gas barrier film of the present invention, an inorganic compound such as aluminum, zinc or silica or an oxide thereof, and other inorganic thin film layers are used, and silicon, aluminum, titanium, zirconium, Examples thereof include oxides such as tin, magnesium and indium, nitrides, fluorides, and composites thereof such as oxynitrides.

  As a method for forming the inorganic thin film layer, a known method can be used. For example, there is a method of forming a film by sputtering or chemical vapor deposition (CVD).

  In order to perform these bonding reactions quickly, it is desirable that the inorganic atom or compound is a chemically active molecular species or atomic species.

  As the inorganic thin film layer forming the gas barrier laminate of the present invention, inorganic nitride is suitable, and silicon nitride (SiN, etc.) and silicon oxynitride (SiON, etc.) are particularly preferred.

  The method for forming the inorganic thin film layer is not particularly limited, and examples thereof include a vacuum deposition method, a chemical vapor deposition method, a physical vapor deposition method, a chemical vapor deposition method (CVD method), and a sol-gel method. Among these, film formation under reduced pressure such as sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), and plasma CVD is desirable. As a result, the chemically active molecular species containing silicon such as silicon nitride and silicon oxynitride react quickly, improving the surface smoothness of the inorganic thin film layer and reducing the number of holes. It is expected to be.

The thickness of the inorganic thin film layer is usually about 0.1 to 1000 nm, particularly about 1 to 500 nm.
<Base material layer>
The base material layer used in the gas barrier laminate according to the present invention is made of an organic material such as a thermosetting resin, a thermoplastic resin, or paper, and the shape thereof is also a sheet or film, tray, cup, hollow body, etc. The thing which has the shape of can be illustrated.

  Examples of the thermosetting resin include various known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, and polyimides. As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin or These mixtures can be exemplified. The base material layer made of these thermoplastic resins may be a single layer or a laminated film made of two or more kinds of thermoplastic resins depending on the use of the gas barrier laminate.

  Among the resins constituting the base material layer according to the present invention, polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polyamide are preferable because the biaxially stretched film is excellent in transparency, rigidity, and heat resistance, and in particular, polyethylene terephthalate and polyethylene naphthalate. Is preferable because it is more excellent in heat resistance.

  The surface of the base material layer may be coated with polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, acrylic resin, urethane resin, or the like.

Furthermore, in order to improve the adhesion of the surface of the base material layer to the gas barrier film, the surface may be subjected to surface activation treatment such as corona treatment, flame treatment, plasma treatment, flame treatment, etc. .
<Undercoat layer>
In the gas barrier laminate according to the present invention, when the inorganic thin film layer is formed on the base material layer, an undercoat layer, preferably an epoxy (meth) acrylate compound or urethane, is formed on the surface of the base material layer in advance. It is preferable to form an undercoat layer of a (meth) acrylate compound.

  A suitable undercoat layer according to the present invention is a layer formed by curing an epoxy (meth) acrylate compound or a urethane (meth) acrylate compound.

  Epoxy (meth) acrylate compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, aliphatic epoxy compounds, and acrylic compounds and acrylics. Examples include compounds obtained by reacting acid or methacrylic acid, and acid-modified epoxy (meth) acrylates obtained by reacting these compounds with carboxylic acids or anhydrides thereof. These epoxy (meth) acrylate compounds are applied to the surface of the base material layer together with a photopolymerization initiator and, if necessary, other photopolymerization or heat-reactive monomer diluent, and then irradiated with ultraviolet rays. Thus, an undercoat layer is formed by a crosslinking reaction.

  The urethane (meth) acrylate compound is composed of an acrylated oligomer composed of a polyol compound and a diisocyanate compound.

  The polyurethane-based oligomer can be obtained from a condensation product of polyisocyanate and polyol. Specific polyisocyanates include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexane triol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, 1,5- Examples include naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris (4-phenyl isocyanate) thiophosphate, and the like. Typical polyols include polyether polyols such as polyoxytetramethylene glycol, polyadipate polyols, and polycarbonate polyols. What polyester polyols, and the like copolymers of acrylic acid esters and hydroxyethyl methacrylate. As monomers constituting the acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (Meth) acrylate and the like.

  These epoxy (meth) acrylate compounds and urethane (meth) acrylate compounds are used in combination as necessary. Examples of a method for polymerizing these include various known methods, specifically, a method by irradiation with energy rays containing ionizing radiation or heating.

  When the undercoat layer is formed by curing with ultraviolet rays, acetophenones, benzophenones, mifilabenzoylbenzoate, α-amyloxime ester, thioxanthone, etc. are used as photopolymerization initiators, and n-butylamine, triethylamine, triethylamine, It is preferable to use n-butylphosphine or the like as a photosensitizer. In the present invention, the epoxy (meth) acrylate compound and the urethane (meth) acrylate compound are also used in combination.

  In addition, these epoxy (meth) acrylate compounds and urethane (meth) acrylate compounds are diluted with (meth) acrylic monomers. Examples of such (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, and butoxyethyl (meth). Acrylate, phenyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) as multifunctional monomer Examples include acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. It is in.

  In particular, when a urethane (meth) acrylate compound is used as the undercoat layer, the oxygen gas barrier property of the resulting gas barrier laminate is further improved.

The thickness of the undercoat layer concerning this invention is 0.01-100 g / m < ² > normally as a coating amount, Preferably it is the range of 0.05-50 g / m < ² >.
<Method for producing gas barrier laminate>
For example, when the gas barrier laminate according to the present invention has a base layer, the base layer may be used as a layer for forming the gas barrier film in the method for producing a gas barrier film.

In addition, a gas barrier film may be formed in advance and laminated on the base material layer.
<Protective layer>
A protective layer capable of protecting the gas barrier film may be provided on the outermost layer on the gas barrier film side of the gas barrier film or gas barrier laminate according to the present invention.

  As the protective layer, epoxy resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, silicone resin, amino resin, polyimide and other thermosetting resins, polyolefin (polyethylene, polypropylene, poly-4-methyl · 1) -Pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / acetic acid Examples thereof include a layer made of a thermoplastic resin such as a vinyl copolymer or a saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. The protective layer is composed of at least one of the thermosetting resin or thermoplastic resin, and may be a mixture of two or more. Further, the protective layer may be formed of a single layer or a plurality of layers of two or more layers. By providing the protective layer, it is possible to effectively prevent the gas barrier film from being damaged by an external mechanical and chemical action, and to impart more stable and high barrier properties.

  These protective layers may be laminated directly on the gas barrier film, or may be laminated via an anchor coat layer made of an adhesive or the like. As a material constituting the anchor coat layer, a material similar to the undercoat layer can be used in addition to the adhesive. Examples of the adhesive for constituting the anchor coat layer according to the present invention include an organic titanium resin, a polyethyleneimine resin, a urethane resin, an epoxy resin, an acrylic resin, a polyester resin, an oxazoline group-containing resin, and a modification. For laminating adhesives composed of silicone resins and alkyl titanates, polyester-based polybutadiene, etc., or polyurethane-based adhesives consisting of combinations of one- and two-component polyols and polyisocyanates, aqueous urethane ionomers and curing agents, etc. Treated with typical dry laminate adhesives, water-based dry laminate adhesives made mainly of acrylic, vinyl acetate, urethane, polyester resins, etc., and solventless laminate adhesives typified by polyurethane adhesives, etc. You may keep it. Of these, water-soluble or water-dispersible polyurethane resins, polyester resins, acrylic resins, oxazoline group-containing resins, and particularly adhesives made of polyurethane resins are preferably used because of their excellent water resistance.

Examples are described below. Physical property values and the like were determined by the following evaluation methods.
(1) Absorbance ratio (A0 / A): measured by the method described above.
(2) Oxygen permeability [ml / (m ² · day · MPa)]: Using OX-TRAN 2/21 ML manufactured by Mocon, stretched film according to JIS K 7126, temperature 20 ° C., humidity 90% R . H. It measured on condition of this.
(3) Bending test The laminated film was stacked, the end face was heat-sealed, and the boil treatment was performed at 98 ° C for 30 minutes in a state where the heat-sealed portion was bent. The floating state of the bent part after the boil treatment was observed. The evaluation results were evaluated based on “very good”, “good”, “normal”, and “bad”.
(4) Wet peel strength In the wet state, the laminated film was peeled between the laminate surface of the barrier film and the unstretched polypropylene film, sampled to a width of 15 millimeters (mm), and then 300 (mm / min). The 90 ° laminate peel strength and 180 ° laminate peel strength were measured at the peel rate.
<Preparation of solution (S1)>
88% by mass of zinc acrylate (made by Asada Chemical Co., Ltd., zinc salt of acrylic acid), 3% by mass of N- (2-hydroxyethyl) acrylamide (manufactured by Kojin Co., Ltd.), and 9% by mass of vinyl alcohol polymer (acrylic) Using a composition comprising zinc acid, N- (2-hydroxyethyl) acrylamide, and vinyl alcohol polymer as 100 mass%), an aqueous solution thereof (solute concentration: 15 (mass%)) And a photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty) diluted to 25% by mass with methyl alcohol.・ Chemicals brand name; Irgacure 2959)] and surfactant (trade name; Emulgen 120, produced by Kao Corporation) in a solid content ratio of 98.5%, .2%, were mixed so that the 0.3%, to prepare a solution (S1).
<Preparation of solution (S2)>
Photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-diluted aqueous zinc acrylate solution at a solid content ratio of 98.0 mass% and methyl alcohol to 25 mass% Methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by Ciba Specialty Chemicals Co., Ltd.)] in a solid content ratio and a surfactant (trade name: Emulgen 120, manufactured by Kao Corporation) Were mixed at a solid content ratio of 0.3% by weight to prepare a zinc acrylate solution (S2).

[Example 1]
A polyester film (TL-PET H, manufactured by Mitsui Chemicals Tosero Co., Ltd.) on which aluminum oxide is deposited is bar-coated with a solution (S1) of a zinc salt of an unsaturated carboxylic acid compound containing N- (2-hydroxyethyl) acrylamide as described above. Using this method, coating was performed so that the coating amount after drying was 1.2 g / m ² . Next, after drying in an oven at 40 ° C. for 15 seconds, the whole stretched film was irradiated using an ultraviolet irradiation device so that the irradiation light amount was 200 mJ / cm ² , and the barrier film having the polymer layer formed on the surface was obtained. Obtained.

The ratio of the absorbance A, based on the νC = O of carboxylate ions in the vicinity of absorbance A ₀ and 1520 cm ^-1 based on νC = O of the carboxylic acid groups in the vicinity of 1700 cm ^-1 in the infrared absorption spectrum (A ₀ / A) is 0. 1

The oxygen permeability of this film was measured and found to be less than 1 ml / m ² · day · MPa.

  Further, an unstretched polypropylene film (thickness 70 μm) was overlaid on this film, the end face was heat-sealed, and the boil treatment was performed at 98 ° C. for 30 minutes in a state where the heat-sealed portion was bent.

  The result of the bending test of this film was “very good” with no floating.

  Furthermore, after the boiled laminated film is wet, the heat seal part between the laminate surface of the barrier film and the unstretched polypropylene film is peeled off, sampled to a width of 15 mm, and then laminated at a peeling rate of 300 mm / min. Peel strength and 180 degree laminate peel strength were measured. The 90 degree laminate peel strength was 2.4 N / 15 mm, and the 180 degree laminate peel strength was 3.7 N / 15 mm.

Furthermore, the oxygen permeability after boiling was 1 ml / m ² · day · MPa.

[Example 2]
In Example 1, it carried out similarly to the Example except having made N- (2-hydroxyethyl) acrylamide N, N- dimethyl acrylamide (made by Kojin Co., Ltd.).

The oxygen permeability of this film was measured and found to be less than 1 ml / m ² · day · MPa.

  A non-stretched polypropylene film (thickness 70 μm) was overlaid on this film, the end face was heat-sealed, and the boil treatment was performed at 98 ° C. for 30 minutes with the heat-sealed portion bent.

  The result of the bending test of this film was “good” with no floating.

  Furthermore, after the boiled laminated film is wet, the heat seal part between the laminate surface of the barrier film and the unstretched polypropylene film is peeled off, sampled to a width of 15 mm, and then laminated at a peeling rate of 300 mm / min. Peel strength and 180 degree laminate peel strength were measured. The 90 degree laminate peel strength was 1.0 N / 15 mm, and the 180 degree laminate peel strength was 1.0 N / 15 mm.

Furthermore, the oxygen permeability after boiling was 1 ml / m ² · day · MPa.

[Example 3]
In Example 1, a solution of a zinc salt of an unsaturated carboxylic acid compound not containing N- (2-hydroxyethyl) acrylamide (S2) on a polyester film (TL-PET H, manufactured by Mitsui Chemicals, Inc., Cello Co., Ltd.) deposited with aluminum oxide. ) Using a bar coating method so that the coating amount after drying is 0.4 g / m ^2, and immediately irradiating the entire stretched film so that the irradiation light amount is 200 mJ / cm ² using an ultraviolet irradiation device, A laminated film was obtained in the same manner as in Example except that the solution (S1) containing N- (2-hydroxyethyl) acrylamide was applied on the film on which the polymer layer was formed.

The oxygen permeability of this film was measured and found to be less than 1 ml / m ² · day · MPa.

  A non-stretched polypropylene film (thickness 70 μm) was overlaid on this film, the end face was heat-sealed, and the boil treatment was performed at 98 ° C. for 30 minutes with the heat-sealed portion bent.

  The result of the bending test of this film was “good” with no floating.

  Furthermore, after the boiled laminated film is wet, the heat seal part between the laminate surface of the barrier film and the unstretched polypropylene film is peeled off, sampled to a width of 15 mm, and then laminated at a peeling rate of 300 mm / min. The peel strength and 180 degree laminate peel strength were measured. The 90 degree laminate peel strength was 2.0 N / 15 mm or more, and the 180 degree laminate peel strength was 2.0 N / 15 mm or more.

Furthermore, the oxygen permeability after boiling was 1 ml / m ² · day · MPa.

[Comparative example]
In Example 1, it carried out similarly except not using N- (2-hydroxyethyl) acrylamide.

  A non-stretched polypropylene film (thickness 70 μm) was overlaid on this film, the end face was heat-sealed, and the boil treatment was performed at 98 ° C. for 30 minutes with the heat-sealed portion bent.

  As a result of the bending test of this film, floating was observed and it was “defective”.

  Furthermore, after the boiled laminated film is wet, the heat seal part between the laminate surface of the barrier film and the unstretched polypropylene film is peeled off, and after sampling to a width of 15 millimeters (mm), 300 (mm / min) The 90 ° laminate peel strength and 180 ° laminate peel strength were measured at the peel rate. The 90 degree laminate peel strength was 0.6 (N / 15 mm), and the 180 degree laminate peel strength was 0.8 (N / 15 mm).

  The gas barrier film of the present invention and the laminated film using the same are excellent in gas barrier properties under high humidity, and can be used for various applications by taking advantage of such characteristics. Packaging materials such as dried foods, water, boil and retort foods, supplement foods, and food packaging materials that require particularly high gas barrier properties, as well as toiletry products such as shampoos, detergents, bath additives, and fragrances Packaging materials, pharmaceutical products such as powders, granules, tablets, liquid pharmaceuticals including infusion bags, medical applications such as medical device packaging bags and packaging containers, hard disks, wiring boards, printed boards, and other electronic components Packaging materials, liquid crystal displays, plasma displays, inorganic / organic EL displays, barrier materials for flat panel displays such as electronic paper, barrier materials such as back sheets for solar cells, barrier materials for other electronic materials, vacuum heat insulating materials Packaging materials for various products, such as barrier materials for industrial use, packaging materials for industrial products such as ink cartridges, and electronic materials , Precision parts, such as pharmaceuticals, can be suitably used as a protective material of the material dislike transmission and moisture of the oxygen gas.

Claims (10)

A gas barrier film 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).

[Wherein R ¹ is hydrogen or a methyl group, R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group consisting of the following general formula (2) And R ² and R ³ may be linked to form a morpholine ring. ]

[Where n is an integer of 1 to 5, R ⁴ is a methylene group or ethylene group, R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is an alkyl group having 1 to 4 carbon atoms, or , Y is —OH, —NH ₂ , or —N (CH ₃ ) ₂ . ]   The acrylamide compound represented by the general formula (1) is N- (2-hydroxyethyl) acrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethyl. The sub-barrier film according to claim 1, wherein the film is at least one acrylamide compound selected from acrylamide and acryloylmorpholine.   The gas barrier film according to claim 1, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is a polyvalent metal salt with at least one selected from Mg, Ca, Ba, Zn and Al.   The gas barrier film according to 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 polymerization degree of less than 20.   The gas barrier film according to claim 1, 3 or 4, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is a salt of (meth) acrylic acid. The ratio of the absorbance A ₀ based on νC═O of the carboxylic acid group near 1700 cm ⁻¹ and the absorbance A based on νC═O of the carboxylate ion near 1520 cm ⁻¹ in the infrared absorption spectrum (A ₀ / The gas barrier film according to claim 1, wherein A) is less than 0.25.   The gas barrier film according to any one of claims 1 to 6, wherein a protective layer is provided on the surface of the gas barrier film via an anchor coat layer or without an anchor coat layer.   A gas barrier laminate in which an inorganic thin film layer is formed on at least one surface of the polymer layer according to claim 1.   The gas barrier laminate according to claim 8, wherein a base material layer is laminated on the other surface of the inorganic thin film layer.   The gas barrier laminate according to claim 8, wherein the inorganic thin film layer is laminated on the base material layer through an undercoat layer of an epoxy (meth) acrylate compound or a urethane (meth) acrylate compound.