JP5098447B2 - Method for producing gas barrier laminate and gas barrier laminate - Google Patents

Description

  The present invention is susceptible to deterioration due to the influence of oxygen and the like, and is processed under high-temperature hot water conditions such as packaging materials for precision metal parts such as foods, beverages, medicines, pharmaceuticals, and electronic parts, boil, retort sterilization, etc. The present invention relates to a method for producing a gas barrier laminate (for example, a film or a sheet) and a gas barrier laminate obtained.

  Conventionally, a polymer containing a highly hydrophilic high hydrogen bonding group in a molecule represented by poly (meth) acrylic acid or polyvinyl alcohol has been used as a gas barrier polymer. However, films made of these polymers have very excellent gas barrier properties such as oxygen under dry conditions, while they have gas barrier properties such as oxygen due to their hydrophilicity under high humidity conditions. There was a problem that the gas barrier laminate had poor resistance to humidity and hot water.

  In order to solve these problems, in International Publication No. WO03 / 091317 (Patent Document 1), a polycarboxylic acid polymer layer and a polyvalent metal compound-containing layer are laminated adjacent to each other on a support. It is disclosed that a polyvalent metal salt of a polycarboxylic acid polymer is obtained by the reaction, and that the gas barrier laminate obtained in this way has a high oxygen gas barrier property even under high humidity conditions. ing.

  On the other hand, as a method for forming a gas barrier layer without an adjacent structure of a polycarboxylic acid polymer layer and a polyvalent metal compound-containing layer as contained in the gas barrier film of Patent Document 1, hydrolysis is performed on a substrate. A layer of a composition containing a hydrolytic condensate of a functional metal compound and a polycarboxylic acid polymer is formed, and this composition layer is immersed in a polyvalent metal ion solution to produce a gas barrier laminate. A method has also been proposed (Patent Document 2). The obtained gas barrier layer has a sea-island microstructure having a sea layer mainly composed of a neutralized product of a polycarboxylic acid polymer and an island phase mainly composed of a hydrolysis condensate of a hydrolyzable metal compound. It is characterized.

  On the other hand, the applicant of the present invention is a polymerization containing an α, β-unsaturated carboxylic acid monomer and a dissolved or dispersed polyvalent metal ion in an amount that neutralizes 10 to 90% of the carboxyl group. The manufacturing method (patent document 3) of the gas-barrier laminated body which apply | coated the property composition on the base material and formed gas barrier property by superposing | polymerizing is developed. Thereby, it does not include the adjacent structure of the polycarboxylic acid-based polymer layer and the polyvalent metal compound-containing layer as included in the gas barrier film of Patent Document 1, and the gas barrier property described in Patent Document 2 above. The present inventors have succeeded in producing a simple gas barrier laminate that does not require ionization treatment by immersion of a polycarboxylic acid polymer layer with a polyvalent metal compound as in film production.

However, there are severe requirements for gas barrier laminates used as packaging materials, etc., for example, withstanding high-temperature hot water treatment such as boiling and retort sterilization, and for packaging materials during the packaging process or during transportation of packaged products. There is a need for further improvements such as the formation of a gas barrier layer with good adhesion to a substrate that can withstand external forces applied.
WO03 / 091317A1 WO2005 / 053954A1 publication WO 2006/059773 A1

  Therefore, the main object of the present invention is to produce a gas barrier layered product having a gas barrier layer which is essentially a single layer and exhibits good gas barrier properties, and further improved in characteristics, without going through a complicated dipping process. Another object of the present invention is to provide a method for producing a rational gas barrier laminate.

Therefore, the main object of the present invention is to produce a gas barrier layered product having a gas barrier layer which is essentially a single layer and exhibits good gas barrier properties, and further improved in characteristics, without going through a complicated dipping process. Another object of the present invention is to provide a method for producing a rational gas barrier laminate.
The method for producing a gas barrier laminate of the present invention has been developed to achieve the above-described object, and more specifically includes the following steps 1 to 3;
Step 1: α, β-unsaturated carboxylic acid monomer (A), polyvalent metal ion (B) and halogen in an amount to neutralize 10 to 90% of the α, β-unsaturated carboxylic acid monomer A polymerizable composition comprising at least one hydrolyzable metal compound (C) containing a metal atom to which at least one characteristic group selected from an atom and an alkoxy group is bonded (provided that a crosslinking agent having a group that reacts with a carboxyl group ) forming a coating film excluding) those containing by coating on the substrate (1),
Step 2: Polymerizing the coating film of the polymerizable composition to form a polymer layer containing an inorganic substance derived from the hydrolyzable metal compound (C) and an ion-crosslinked polycarboxylic acid polymer, and Step 3 : A step of heat-treating the polymer layer formed in Step 2 at a temperature of 50 to 400 ° C. to form a gas barrier layer containing an inorganic substance and an ion-crosslinked polycarboxylic acid polymer.

One feature of the gas barrier laminate of the present invention thus formed is that the gas barrier layer is homogeneous (that is, does not have the sea-island microstructure as found in the gas barrier layer of Patent Document 2). Generally, at 30 ° C. and 80% RH, it has excellent gas barrier properties represented by a low oxygen permeability of 10 cc / m ² · day · atm or less.

  Hereinafter, the manufacturing method of the gas barrier laminate of the present invention will be sequentially described according to the steps 1 to 3.

<< Step 1: Formation of polymerizable coating film >>
In the method of the present invention, first, an α, β-unsaturated carboxylic acid monomer (A) and a polyvalent metal ion in an amount that neutralizes 10 to 90% of the α, β-unsaturated carboxylic acid monomer. A polymerizable composition containing (B) and at least one hydrolyzable metal compound (C) containing a metal atom to which at least one characteristic group selected from a halogen atom and an alkoxy group is bonded is coated on the substrate (1). To form a coating film.

(Α, β-unsaturated carboxylic acid monomer (A))
As the α, β-unsaturated carboxylic acid monomer (A), acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, senecioic acid, tiglic acid, sorbic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid And mesaconic acid or their anhydrides are preferred, and acrylic acid and methacrylic acid are more preferred. Acrylic acid is particularly preferable in terms of gas barrier properties and cost. Monomers other than (meth) acrylic acid such as itaconic acid, citraconic acid and maleic acid are preferably used in combination with acrylic acid or methacrylic acid as a minor component of less than 50% by weight. The α, β-unsaturated carboxylic acid monomers can be used alone or in combination of two or more.

  These α, β-unsaturated carboxylic acid monomers (A) are solids in the finally obtained polymerizable composition (all components except water alone or a mixed solvent of water and a compatible organic solvent). Is used in an amount such that the ratio of 15 to 95% by weight.

(Polyvalent metal ion (B))
The polyvalent metal ion (B) is a polyvalent metal ion derived from the polyvalent metal compound (B ′). As the polyvalent metal compound, generally used is a compound that generates polyvalent metal ions by ion dissociation in water. The polyvalent metal compound (B ′) is a single polyvalent metal atom or a polyvalent metal compound that gives a metal ion having a valence of 2 or more.

  Specific examples of the polyvalent metal constituting the polyvalent metal compound (B ′) include metals of Group 2A of the periodic table such as beryllium, magnesium and calcium; titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, A transition metal such as zinc; aluminum can be mentioned, but is not limited thereto. Among these, zinc, calcium, copper, magnesium, aluminum, and iron are preferable. That is, as the polyvalent metal ion (B), at least one of divalent and trivalent metal ions is preferably used. The α, β-unsaturated carboxylic acid metal salt has different solubility in water depending on the type of metal, but zinc and calcium are particularly preferable as the metal species from the viewpoint of solubility.

  Specific examples of the polyvalent metal compound include, but are not limited to, oxides, hydroxides, carbonates, organic acid salts, and inorganic acid salts of polyvalent metals. Examples of organic acid salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, α, β-monoethylenically unsaturated Examples include, but are not limited to, carboxylates. Examples of the α, β-monoethylenically unsaturated carboxylate include zinc diacrylate, calcium diacrylate, magnesium diacrylate, copper diacrylate, and aluminum acrylate.

  Examples of inorganic acid salts include, but are not limited to, chlorides, sulfates, and nitrates.

  If an acid-derived component remains in the gas barrier layer, the barrier property tends to be impaired. In this sense, the polyvalent metal compound is preferably an oxide or hydroxide of a polyvalent metal, and particularly preferably zinc oxide, magnesium oxide, or calcium hydroxide.

  These polyvalent metal compounds can be used alone or in combination of two or more.

  The polyvalent metal ion (B) resulting from these polyvalent metal compounds is 10 to 90 (mol)%, preferably 15 to 87%, more preferably of the α, β-unsaturated carboxylic acid monomer (A). Is used in an amount to neutralize 20-85%. The lower limit of the degree of neutralization can be increased to 25%, 30% or 40%. When the degree of neutralization is low, the gas barrier property of the resulting gas barrier laminate tends to be reduced, but this tendency is alleviated by increasing the amount of the hydrolyzable metal compound (C) added. On the other hand, when the degree of neutralization becomes too high, the solubility of metal ions decreases, and a uniform polymerizable composition cannot be obtained, or the produced film is whitened. The amount of polyvalent metal ions and the degree of neutralization are preferably adjusted in consideration of the type of α, β-unsaturated carboxylic acid monomer used, the type and valence of the polyvalent metal compound, and the like.

  The polymerizable composition used in the present invention can contain monovalent metal ions such as sodium and potassium as long as the uniformity as the coating liquid is not impaired. When a monovalent metal ion is contained, it is used in an amount that neutralizes 2 to 20 mol%, preferably 5 to 15 mol% of the α, β-unsaturated carboxylic acid monomer (A). It is preferable in terms of gas barrier properties.

(Hydrolyzable metal compound (C))
The hydrolyzable metal compound (C) as the third component contained in the polymerizable composition contains a metal atom to which at least one characteristic group selected from a halogen atom and an alkoxy group is bonded. It is represented by chemical formula (I).

[Chemical formula 2]
_{^{M 1 (OR 1) n R}} 2 m-n-t-s X 1 t Z 1 s ... (I)
[In the chemical formula (I), ^{M 1} is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Te, W or Nb Represents. M ¹ is preferably Si, Al, Ti or Zr, and particularly preferably Si. In the chemical formula (I), R ¹ is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or a t-butyl group, preferably a methyl group or an ethyl group. It is a group. R ² is an organic group such as an alkyl group, an aralkyl group, an aryl group, or an alkenyl group, and is preferably an alkyl group similar to R ¹ . In the chemical formula (I), X ¹ represents a halogen atom. Examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. In chemical formula (I), Z ¹ represents an organic group substituted with a functional group. Here, examples of the functional group include an epoxy group, a (meth) acryloxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, and a carbodiimide group. ) An acryloxy group, an amino group, an isocyanate group, a ureido group or a halogen atom is preferred, and at least one selected from an epoxy group, a (meth) acryloxy group, an amino group and an isocyanate group is particularly preferred. It is also preferred that the functional group has reactivity with the carboxyl group. Examples of the organic group substituted with such a functional group include those similar to R ² . In the chemical formula (I), m is equal to the valence of the metal element M ¹ . In chemical formula (I), n represents 0 to m, t represents 0 to m, and s represents an integer of 0 or 1. However, 1 ≦ n + t and n + t + s ≦ m.

In the hydrolyzable metal compound (C), in the formula (I), n and t are each 0 to (m−1) (where 1 ≦ n + t ≦ (m−1), preferably n + t = (M-1)) (that is, in addition to a halogen atom and / or an alkoxy group, at least ^one of R ² and Z ¹ is included), and n + t = m (that is, a halogen atom) And / or a compound (C2) containing only an alkoxy group), and a combination of each of them is preferable. In the compound (C1) and the compound (C2), M ¹ , R ¹ and X ¹ may be the same or different.

  Specific examples of the compound (C1) include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropyltrichlorosilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrichlorosilane. , Chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloropropyltrichlorosilane, bromopropyltrimethoxysilane, γ-bromopropyltriethoxysilane, γ-bromopropyltrichlorosilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane , Mercaptopropyltrichlorosilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, isocyanate Topropyltrichlorosilane, ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, ureidopropyltrichlorosilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Examples include silane, (meth) acryloxypropyltrimethoxysilane, vinyltrichlorosilane, methyltriisopropoxytitanium, methyldiisopropoxyaluminum, and the like. Preferred compounds (C1) include vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, aminopropyl Examples include trimethoxysilane and aminopropyltriethoxysilane.

  Specific examples of the compound (C2) include silicon alkoxides such as tetramethoxysilane, tetraethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; tetra Halogenated silanes such as chlorosilane and tetrabromosilane; alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium; titanium halides such as tetrachlorotitanium; trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum , Alkoxy aluminum compounds such as tributoxy aluminum and diethoxy aluminum chloride; tetraethoxy zirconium, tetraiso Alkoxyzirconium compounds such Ropo alkoxy zirconium, and the like.

  In the polymerizable composition used in step 1 of the present invention, the weight fraction of compound (C) contained in the total solid content (= compound (C) / [α, β-unsaturated carboxylic acid monomer) (A) + polyvalent metal ion (B) + compound (C)] × 100) is used in a proportion of 1 to 80% by weight, preferably 2 to 70% by weight. If it is less than 1% by weight, the addition efficiency of the compound (C) is poor, and if it exceeds 80% by weight, the polymerization efficiency of the α, β-unsaturated carboxylic acid (A) and the flexibility of the resulting polymer film may be impaired. There is. Comparing the properties of the compounds (C1) and (C2), the compound (C1) tends to slightly lower the gas barrier property, and the compound (C2) tends to lower the flexibility of the resulting polymer film. . Therefore, when the weight fraction of the compound (C) becomes 70% by weight or more and the influence becomes large, the molar ratio of (C1) / (C2) is 0.05 or more, more preferably 0.1 or more. Most preferably, it is preferably 0.25 or more.

  In the polymerizable composition used in Step 1 of the present invention, at least part of the compound (C) is hydrolyzed, and a partial hydrolyzate, a complete hydrolyzate and a (part) of the complete hydrolyzate. Condensate is included in a mixed state. The hydrolysis of the compound (C) is generally performed by adding the compound (C) to water before or after the addition of the α, β-unsaturated carboxylic acid monomer (A) or the polyvalent metal compound (B ′). Although it occurs automatically in the process of adding and mixing in the product, if necessary, the humidity may be adjusted after polymerization of the composition coating film (step 2) to promote hydrolysis.

  In the polymerizable composition used in Step 1, in addition to the hydrolyzable metal compound (C), a hydrogen bonding functional group selected from a hydroxyl group, an amino group, a carbonyl group, an amide group, and a carboxyl group is further added in the molecule. It is also preferable to include at least one hydrogen bonding substance (D). This is because such a substance (D) can be expected to further improve the gas barrier properties of the resulting polymer film through the protection of the compound (C) and the suppression of the polycondensation reaction after hydrolysis. Specific examples of such a hydrogen bonding substance (D) include polyvinyl alcohol, glycerin, polyacrylamide, chitosan, gelatin, polyethylene glycol and the like. Among them, polyvinyl alcohol is preferably used. In the polymerizable composition, the hydrogen bonding substance (D) is a total amount of 100 parts by weight of α, β-unsaturated carboxylic acid monomer (A) + polyvalent metal compound ion (B) + compound (C). The ratio is preferably 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight. If it is less than 0.5 part by weight, the addition efficiency is poor, and if it exceeds 50 parts by weight, the polymerization efficiency of the α, β-unsaturated carboxylic acid (A) may be impaired.

  The polymerizable composition used in the present invention uses water as a main solvent or dispersion medium, but does not inhibit uniform dissolution or dispersion of each component and does not inhibit the polymerization reaction, and a small amount of water and A compatible organic solvent may be added. Examples of the organic solvent compatible with water include alcohols, and the addition of alcohols is preferable in terms of enhancing the solubility of the hydrolyzable metal compound (C). Furthermore, a small amount of acid may be added to promote hydrolysis of the hydrolyzable metal compound (C).

(Other ingredients)
The polymerizable composition of the present invention can contain a polymerization initiator as necessary. As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator are representative. A photopolymerization initiator and a thermal polymerization initiator may be used in combination. Thermal polymerization initiators also include azo compounds and peroxides that are activated by irradiation with ionizing radiation.

  When irradiating the wet coating film with ultraviolet rays, it is preferable to contain a photopolymerization initiator in the polymerizable composition. Photoinitiators are sometimes simply referred to as photoinitiators or sensitizers. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler ketones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, thioxanthones, and mixtures of two or more thereof.

  When these photopolymerization initiators are added to the polymerizable composition, they are usually added to the polymerizable composition in a proportion of 0.001 to 10% by weight, preferably 0.01 to 5% by weight. The photopolymerization initiator is not necessarily added, but when polymerization is performed by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator in order to increase the polymerization efficiency.

  When performing thermal polymerization by heating a wet coating film, it is preferable to use a thermal polymerization initiator that is thermally dissociated to exhibit a function as an initiator. Examples of the thermal polymerization initiator include persulfate, azo polymerization initiator, and peroxide. When a thermal polymerization initiator is used, it is usually added to the polymerizable composition in a proportion of 0.001 to 10% by weight, preferably 0.01 to 5% by weight.

  In the polymerizable composition of the present invention, a thickener, an inorganic layered compound, a dispersant, a surfactant, a softening agent, a heat stabilizer, an antioxidant, an oxygen absorbent, a colorant, an anti-reflective agent, if necessary. A blocking agent, a polyfunctional monomer, etc. can be contained.

  The polymerizable composition used in the present invention can be obtained by stirring and mixing each of the above components by a conventional method, but the solid content concentration in the composition (water and an organic solvent compatible with water to be added as necessary) The concentration of all components excluding) is adjusted in the range of 15 to 95% by weight, preferably 20 to 94% by weight, more preferably 25 to 93% by weight.

  Subsequently, the polymeric composition obtained above is apply | coated on a base material (1), and a coating film is formed.

  Although it does not specifically limit as a base material (1), Paper, a plastic or rubber film (a sheet | seat is included), or these composites are used preferably. The substrate is generally used in the form of a film or a sheet, but may be a molded body having a three-dimensional shape such as a plastic container, a tube, or a tire if desired.

  As a base material (1), the unstretched film or stretched film which consists of plastics is preferable. The type of plastic composing the base plastic film is not particularly limited. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin Olefin polymers such as, and acid-modified products thereof; polyvinyl acetate, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol such as polyvinyl alcohol, and modified products thereof; polyethylene terephthalate Polyesters such as polybutylene terephthalate and polyethylene naphthalate; Aliphatic polyesters such as polyε-caprolactone, polyhydroxybutyrate and polyhydroxyvalerate; Nylon 6, nylon 66, nylon 12, nylon Polyamides such as 6/66 copolymer, nylon 6/12 copolymer, metaxylene adipamide / nylon 6 copolymer; polyethers such as polyethylene glycol, polyethersulfone, polyphenylene sulfide, polyphenylene oxide; poly Halogenated polymers such as vinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride; acrylic polymers such as polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, and polyacrylonitrile; polyimide resins; Other resins such as alkyd resin, melamine resin, acrylic resin, nitrified cotton, urethane resin, unsaturated polyester resin, phenol resin, amino resin, fluororesin, and epoxy resin used for paints; cellulose, starch, plastic Examples thereof include natural polymer compounds such as lulan, chitin, chitosan, glucomannan, agarose, and gelatin; and mixtures thereof.

If necessary, the plastic film can be subjected to pretreatment such as etching, corona discharge, plasma treatment, electron beam irradiation, or an adhesive can be applied in advance. As a base material, the surface of a plastic film is made of an inorganic material such as silicon oxide, aluminum oxide, aluminum or silicon nitride; a thin film such as a metal compound formed by vapor deposition, sputtering or ion plating. it can. The surface of the plastic film used as the substrate may be printed. The plastic film may be a multilayer film made of a plurality of plastic films or a laminated film with other materials such as paper. Furthermore, the plastic film may be an oxygen-absorbing resin composition film having oxygen-absorbing ability, or an oxygen-absorbing multilayer film of the film and another plastic film.

  In order to apply the polymerizable composition on a substrate, use any coating method such as spraying, dipping, coating using a coater, printing using a printing machine, etc. on one or both sides of the substrate. Can do. When coating using a coater or printing machine, for example, gravure coaters such as direct gravure method, reverse gravure method, kiss reverse gravure method, offset gravure method; reverse roll coater, micro gravure coater, air knife coater, dip coater, Various systems such as a bar coater, comma coater, and die coater can be employed.

The thickness of the wet polymerizable composition film formed is such that the thickness of the polymer film (gas barrier layer) produced through the following step 2 is usually 0.001 μm to 1 mm, preferably 0.01 to 100 μm. It is preferable to adjust so that it may become the range of 0.04-10 micrometers preferably. The coating amount of the polymerizable composition, depending on the solids concentration is preferably 0.01 to 1000 g / ^{m 2,} preferably from 0.1 to 100 g / ^{m 2,} more preferably 80 g / ^{m 2} .

<< Step 2: Formation of polymer layer >>
The coating film of the polymerizable composition formed on the substrate (1) in the above step 1 was polymerized to contain an inorganic substance derived from the compound (C) and crosslinked with the polyvalent metal ion (B). A polymer layer containing a polycarboxylic acid polymer (polymer of α, β-unsaturated carboxylic acid monomer (A)) is formed.

  For this purpose, the water content of the coating film of the polymerizable composition applied and formed on the substrate (1) may be once dried, but it is preferably ionized to the coating film that has been kept wet without being dried. The α, β-unsaturated carboxylic acid monomer (A) is polymerized by treatment with radiation, heating, or both.

  In this way, the α, β-unsaturated carboxylic acid monomer (A) is polymerized by irradiation with ionizing radiation and / or heat treatment of the wet coating film formed from the polymerizable composition, and the A carboxylic acid polymer is formed. At the same time, the produced polycarboxylic acid-based polymer is ionically cross-linked by the polyvalent metal ion (B) to form a cured coating film, which is derived from the hydrolyzable metal compound (C) in the cured coating film. Minerals are taken up.

  As the ionizing radiation, ultraviolet rays, electron beams (beta rays), gamma rays and alpha rays are preferable, and ultraviolet rays and electron beams are more preferable. In order to irradiate ionizing radiation, an apparatus that generates each radiation source is used. In order to irradiate an electron beam, an accelerated electron beam extracted from an electron beam accelerator of 20 to 2000 kV is usually used. The irradiation dose of the accelerated electron beam is usually 1 to 300 kGy, preferably 5 to 200 kGy. The penetration depth of the electron beam into the irradiated object varies depending on the acceleration voltage. The higher the acceleration voltage, the deeper the electron beam penetrates. When an electron beam is used, the adhesiveness between a base material and a coating film can be improved by a graft reaction of an α, β-unsaturated carboxylic acid monomer to a base material such as a plastic film.

To irradiate ultraviolet rays, using UV irradiation devices such as germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, electrodeless lamps, Irradiate light including a wavelength region of 200 to 400 nm. The lamp output of the UV irradiation apparatus is usually selected from the range of 30 to 300 W / cm as the input wattage per 1 cm of emission length. The light emission length is usually selected from the range of 40 to 2500 mm. When the UV irradiation dose is 100 mJ / cm ² or more, the α, β-unsaturated carboxylic acid is rapidly polymerized, and thus the conveyance speed and the lamp output are not particularly limited.

  In order to form the polymer layer by heating the wet coating film, the wet coating film is usually heated to a temperature of 50 to 250 ° C, preferably 60 to 220 ° C, more preferably 70 to 200 ° C. Examples of the heating means include a method of heating the coating film using a heater, and a method of passing the coating film through a heating furnace whose temperature is controlled. The heating time is usually 1 to 120 minutes, preferably 3 to 60 minutes, more preferably 5 to 30 minutes. It is preferable from the viewpoint of gas barrier properties of the cured coating that the heating time is lengthened as the heating temperature is low and the heating time is shortened as the heating temperature is high.

  Ionizing radiation can be directly applied to the wet coating, but if it is desired to remove the polymerization inhibition effect due to oxygen, the irradiation and / or heat treatment of ionizing radiation is performed using nitrogen gas, carbon dioxide gas, or noble gas. It is preferable to carry out in inert gas atmosphere. In order to maintain the wet state of the coating film and remove the effect of inhibiting polymerization due to oxygen at the same time, the surface of the wet coating film formed on the substrate (1) (support) is transferred to another substrate (2) ( It is also preferable to coat with a coating material. Examples of other base materials used as the covering material include, but are not limited to, a light transmissive plastic film, a glass plate, paper, and an aluminum foil. When the polymerization is carried out by irradiation with ionizing radiation, it is sufficient that only one of the base materials (1) and (2) located on the side irradiated with ionizing radiation is transparent to ionizing radiation. When an electron beam is used as the ionizing radiation, the type of the substrate on the ionizing radiation transmitting side is not limited.

  In the production method of the present invention, a coating film of the polymerizable composition is formed on a substrate (1) such as a plastic or rubber film or paper (step 1), and the surface of the coating film is preferably immediately applied to another substrate. It is preferable to carry out the continuous treatment (step 2) by coating with the material (2) and transporting it to the ionizing radiation irradiation device and / or the heating device while keeping the wet state of the coating film. The conveyance speed can be appropriately set in consideration of the necessary dose and the amount of heat during irradiation with ionizing radiation and / or heat treatment.

<< Step 3: Formation of Gas Barrier Layer >>
In the production method of the present invention, the polymer layer formed in the above step 2 (polymerization step) is then heat-treated at 50 to 400 ° C. This heat treatment removes moisture in the cured coating film (polymer layer), improves the oxygen gas barrier property, promotes the hydrolysis polycondensation reaction of the hydrolyzable metal compound (C), and hydrolyses and condenses. In order to remove the residual organic component in the material and improve the gas barrier property of the gas barrier layer to be formed, it is carried out to change it into a preferable inorganic material. The heat treatment temperature is preferably 70 to 350 ° C, more preferably 90 to 300 ° C. This heat treatment is more effective when the polymerization (step 2) proceeds mainly by irradiation with ionizing radiation, and is generally carried out for 1 second to 72 hours, preferably 5 seconds to 2 hours. In the case of thermal polymerization, it can be appropriately shortened. The heat treatment can also be performed after the substrate (1) and / or the substrate (2) is peeled off. The thickness of the gas barrier monk formed by the method of the present invention is usually 0.001 μm to 1 mm, preferably 0.01 to 100 μm, more preferably 0.04 to 10 μm from the viewpoint of the barrier property. It is preferable to adjust.

The gas barrier laminate obtained through the above steps or the gas barrier film obtained by peeling the substrate (1) and / or substrate (2) therefrom has excellent oxygen gas barrier properties, and has a temperature of 30 ° C. and a relative humidity of 80. % Oxygen permeability measured under high humidity conditions is usually 10 cc / m ² · day · atm or less, preferably 5 cc / m ² · day · atm or less, more preferably 3 cc / m ² · day · atm or less, Particularly preferably, it is 1 cc / m ² · day · atm or less. The lower limit of the oxygen permeability is usually about 0.0001 cc / m ² · day · atm, and in many cases about 0.001 cc / m ² · day · atm.

(Use)
The gas barrier laminate obtained by the method of the present invention and the gas barrier film obtained by peeling the substrate therefrom can be used as a gas barrier packaging material, a packaging material for heat sterilization, or a film for a vacuum heat insulating material. . The gas barrier film of the present invention is particularly suitable as a packaging material for foods, beverages, medicines, pharmaceuticals, electronic parts, precision metal parts and the like that are easily altered by oxygen.

  Specific examples of the shape of the package to be formed include a flat pouch, a standing pouch, a pouch with a nozzle, a pillow bag, a gusset bag, and a shell-type packaging bag.

  Specific examples of the shape of the packaging container to be formed include bottles, trays, cups, tubes, tires, and the like. The gas barrier film of the present invention can also be used for applications such as packaging container lids and mouth seals. As a method for forming a packaging bag or packaging container, various methods employed in the technical field such as a heat fusion method can be employed.

[Example]
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

<Oxygen permeability>
The oxygen permeability described in the present specification is based on a measurement value obtained by the following measurement method.

That is, the oxygen permeability of the film was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 80% using an oxygen permeability tester “Oxtran 2/20” manufactured by Modern Control. The measurement method was performed according to ASTM D 3985-81 (corresponding to JIS K 7126 method B). The unit of the measured value is cc / m ² · day · atm. The oxygen volume (cc value) indicates a value in STP (that is, standard conditions (0 ° C., 1 atm)).

  The measurement of the oxygen permeability of the laminate was performed in the state of the laminate, but since the oxygen permeability of the film or paper used as the substrate is sufficiently large, the measured value is substantially equal to the oxygen permeability of the gas barrier layer. It can be evaluated that they match.

<Base material>
In the following examples and comparative examples, plastic films used as substrates are as follows.

(1) PET # 12: polyethylene terephthalate film, “Lumirror P60” manufactured by Toray Industries, Inc., thickness 12 μm;
(2) PET # 50: polyethylene terephthalate film, “Lumirror S10” manufactured by Toray Industries, Inc., thickness 50 μm;
(3) ONy # 15: biaxially stretched 6 nylon film, “EMBLEM ONBC” manufactured by Unitika Ltd., thickness 15 μm, single-sided corona treated product (4) OPP # 20: biaxially stretched polypropylene film, manufactured by Toray Industries, Inc. “Torphan BO”, thickness 20 μm, single-sided corona-treated product (5) PI # 25: polyimide film, “Kapton 100EN” manufactured by Toray DuPont Co., Ltd., thickness 25 μm, single-sided corona-treated product (6) Art paper: Basis weight 100 g / m ² (thickness 120 μm) (Art paper is a paper material whose surface is smoothed by an inorganic material such as kaolin, a resin, or a mixture thereof.)
(7) Ethylene propylene (EPT) rubber sheet, “EPT508Z” manufactured by Kureha Elastomer Co., Ltd., thickness 1 mm
(8) Al vapor-deposited PET (# 12): Aluminum vapor-deposited biaxially stretched PET, thickness 12 μm, manufactured by Tosero Co., Ltd., “TL-PET H # 12”

[Preparation of polymerizable composition (coating liquid)]
(Coating fluid S-1)
A mixture of 2.2 parts by weight of vinyltrimethoxysilane (VTMS, manufactured by Aldrich) and 8.7 parts by weight of tetramethoxysilane (TMOS, manufactured by Shin-Etsu Silicone) was used as a water source and 0 as a hydrolysis catalyst. .1N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 2.4 parts by weight, and a hydrolysis and polycondensation reaction was performed in a nitrogen atmosphere at room temperature for 10 minutes. 17.4 parts by weight of zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 26.0 parts by weight of distilled water and 43.4 parts by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) are added to the obtained sol. The liquid mixture obtained by adding in order under stirring was added and mixed to obtain a coating liquid S-1 having a composition as shown in Table 1. The appearance of the obtained coating liquid S-1 was colorless and transparent.

(Coating fluid S-2)
To a mixture of 2.2 parts by weight of γ-glycidoxypropyltrimethoxysilane (GPTMS, manufactured by Shin-Etsu Silicone) and 19.7 parts by weight of tetraethoxysilane (TEOS, manufactured by Aldrich), 3N 0.1N hydrochloric acid was added. .7 parts by weight was added and stirred at room temperature for 15 minutes to conduct hydrolysis and polycondensation reaction. 17.5 parts by weight of calcium carbonate (manufactured by Wako Pure Chemical Industries), 21.9 parts by weight of distilled water, and 35.0 parts by weight of acrylic acid are sequentially added to the obtained sol under stirring in this order. The mixed liquid was added and mixed to obtain a coating liquid S-2 having a composition as shown in Table 1. The appearance of the obtained coating liquid S-2 was colorless and transparent.

(Coating fluid S-3)
To a mixture of 4.9 parts by weight of methacryloxypropyltrimethoxysilane (MPTMS, manufactured by Aldrich) and 3.3 parts by weight of tetramethoxysilane, 1.3 parts by weight of 0.1N hydrochloric acid was added, and the temperature was 10 ° C. under a nitrogen atmosphere. The mixture was stirred for 1 hour to conduct hydrolysis and polycondensation reaction. 16.8 parts by weight of zinc carbonate (manufactured by Wako Pure Chemical Industries) and 16.8 parts by weight of distilled water, 48.8 parts by weight of acrylic acid, and benzophenone (manufactured by Wako Pure Chemical Industries) 0 with respect to the obtained sol .6 parts by weight and 8.1 parts by weight of glycerin (manufactured by Wako Pure Chemical Industries, Ltd.) in this order were added in order under stirring and mixed to obtain a composition as shown in Table 1. Coating liquid S-3 was obtained. The appearance of the obtained coating liquid S-3 was colorless and transparent.

(Coating fluid S-4)
A mixture of 36.4 parts by weight of aminopropyltrimethoxysilane (APTMS, Aldrich) and 4.0 parts by weight of tetramethoxysilane was mixed with 6.5 parts by weight of 0.1N hydrochloric acid at 0 ° C. for 30 minutes. Decomposition and polycondensation reactions were performed. To the obtained sol, 2.4 parts by weight of zinc oxide, 10.1 parts by weight of distilled water, and 40.5 parts by weight of acrylic acid were added in this order under stirring in this order, and a mixed solution was added and mixed. Thus, a coating liquid S-4 having a composition as shown in Table 1 was obtained. The appearance of the obtained coating liquid S-4 was colorless and transparent.

(Coating fluid S-5)
To a mixture of 0.02 part by weight of γ-glycidoxypropyltrimethoxysilane and 3.1 parts by weight of tetramethoxysilane, 0.7 part by weight of 0.1N hydrochloric acid is stirred for 30 minutes at room temperature, A condensation reaction was performed. To the obtained sol, 11.3 parts by weight of magnesium oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 38.8 parts by weight of distilled water, and 46.8 parts by weight of acrylic acid were sequentially added in this order with stirring. The obtained mixed liquid was added and mixed to obtain a coating liquid S-5 having a composition as shown in Table 1. The appearance of the obtained coating liquid S-5 was colorless and transparent.

(Coating fluid S-6)
To a mixture of 35 parts by weight of aminopropyltrimethoxysilane and 15 parts by weight of tetraethoxysilane, 7.9 parts by weight of 0.1N hydrochloric acid was added and stirred at 0 ° C. for 10 minutes to conduct hydrolysis and polycondensation reaction. . 5 parts by weight of zinc oxide, 8 parts by weight of distilled water, 17 parts by weight of acrylic acid and 48 parts by weight of a 5 wt% aqueous solution of polyvinyl alcohol (Poval (trademark registration 110) manufactured by Kuraray Co., Ltd.) prepared in advance are obtained. Were added in order in this order under agitation and mixed to obtain a coating liquid S-6 having a composition as shown in Table 1. The appearance of the obtained coating liquid S-6 was colorless and transparent.

(Coating fluid S-7)
To a mixture of 5.8 parts by weight of aminopropyltrimethoxysilane and 5.8 parts by weight of tetramethoxysilane, add 2.3 parts by weight of 0.1N hydrochloric acid, stir at 0 ° C. for 30 minutes, hydrolysis and polycondensation. Reaction was performed. To the obtained sol, 17.3 parts by weight of zinc oxide, 25.9 parts by weight of distilled water, and 43.1 parts by weight of acrylic acid were sequentially added in this order with stirring, and the mixed solution obtained was added and mixed. The coating liquid S-7 having the composition as shown in Table 1 was obtained. The appearance of the obtained coating liquid S-7 was colorless and transparent.

(Coating fluid S-8)
To a mixture of 1.0 part by weight of vinyltrimethoxysilane and 8.7 parts by weight of tetraethoxysilane, add 1.8 parts by weight of 0.1N hydrochloric acid, and stir at room temperature for 30 minutes in a nitrogen atmosphere. A condensation reaction was performed. To the obtained sol, 13.8 parts by weight of zinc oxide, 25.8 parts by weight of distilled water, and 49.0 parts by weight of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were sequentially added in this order with stirring. The obtained mixed liquid was added and mixed to obtain a coating liquid S-8 having a composition as shown in Table 1. The appearance of the obtained coating liquid S-8 was colorless and transparent.

(Coating fluid S-9)
To a mixture of 13.6 parts by weight of methacryloxypropyltrimethoxysilane and 1.5 parts by weight of tetramethoxysilane, 1.9 parts by weight of 0.1N hydrochloric acid is added and stirred for 30 minutes at room temperature in a nitrogen atmosphere. Decomposition and polycondensation reactions were performed. Calcium carbonate 12.1 parts by weight and distilled water 22.6 parts by weight, maleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 40.8 parts by weight, polyacrylamide (molecular weight 10,000) 50 wt% aqueous solution (with respect to the obtained sol) Aldrich's 15.1 parts by weight were added in order in this order under stirring, and the resulting mixed liquid was added and mixed to obtain a coating liquid S-8 having the composition shown in Table 1. The appearance of the obtained coating liquid S-8 was colorless and transparent.

(Coating fluid S-51)
To a mixture of 15.6 parts by weight of γ-glycidoxypropyltrimethoxysilane and 62.3 parts by weight of tetramethoxysilane was added 17.1 parts by weight of 0.1N hydrochloric acid, and the mixture was stirred at room temperature for 15 minutes. A polycondensation reaction was performed. With respect to the obtained sol, 16.8 parts by weight of polyacrylic acid (PAA) Aron A-10H (registered trademark) (number average molecular weight 20000, 25% by weight aqueous solution) manufactured by Toa Gosei Co., Ltd. and 0.8% of zinc oxide The liquid mixture obtained by adding weight parts in this order in order under stirring was added and mixed to obtain a coating liquid S-51 having a composition as shown in Table 1. The appearance of the obtained coating solution was colorless and transparent.

(Coating fluid S-52)
Hydrolysis and polycondensation reaction by adding 11.9 parts by weight of 0.1N hydrochloric acid to a mixture of 70.5 parts by weight of methacryloxypropyltrimethoxysilane and 17.6 parts by weight of tetramethoxysilane and stirring for 30 minutes at room temperature The coating liquid S-52 having the composition shown in Table 1 was obtained. The appearance of the obtained coating solution was colorless and transparent.

Example 1
The thickness after film-forming on the polyethylene terephthalate (PET # 50) using the desktop coater ("K303PR00FER" manufactured by RK Print-Coat Instruments) immediately after preparation of the coating liquid (S-1) prepared above. Was 1 μm. After coating, the nylon film (ONy # 15) is immediately covered with a nylon film (ONy # 15), and the layer structure of “base material (PET # 50) / coating liquid S-1 coating film / base material (ONy # 15)” A multilayer structure with Next, from the top of the solution ONy substrate, using an EB irradiation apparatus of a tray transfer conveyor type (“CB250 / 15 / 180L”, EB apparatus manufactured by Iwasaki Electric Co., Ltd.), an acceleration voltage of 100 kV, a transfer speed of 10 m / min, and an irradiation dose of 50 kGy. An electron beam (EB) was irradiated under the conditions, and a polymerization treatment was performed.

  The obtained multilayer structure was dried in a gear oven at 100 ° C. for 1 hour and then heat-treated at 200 ° C. for 30 minutes, and the resulting laminate having an inorganic-containing ion-crosslinked polycarboxylic acid polymer layer at 30 ° C. and 80% RH. The oxygen permeability was measured.

(Example 2)
The coating liquid (S-2) prepared above was coated on a polyimide film substrate so that the thickness after film formation would be 1 μm using a desktop coater immediately after the preparation. A multilayer structure having a layer configuration of “25 / Coating fluid S-2 coating film” was obtained. Next, using the above-mentioned EB irradiation apparatus, an electron beam (EB) was irradiated and polymerized under the conditions of an acceleration voltage of 100 kV, a conveyance speed of 10 m / min, and an irradiation dose of 100 kGy. Furthermore, after drying at 100 ° C. for 1 hour in a gear oven, heat treatment was performed at 300 ° C. for 2 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the laminate having the inorganic substance-containing ion-crosslinked polycarboxylic acid polymer layer was measured. did.

(Example 3)
The coating liquid (S-3) prepared above was coated on a PET (50 #) substrate so that the thickness after film formation was 2 μm using a desktop coater immediately after preparation. Immediately after coating, the aluminum vapor-deposited PET film (# 12) is covered so that the vapor-deposited surface and the coated surface are in contact with each other, and the layer configuration of “base PET # 50 / coating solution S-3 coating / Al vapor-deposited PET” A multilayer structure with Next, the obtained multilayer structure was subjected to thermal polymerization treatment at 70 ° C. for 12 hours in a gear oven, and further heat-treated at 210 ° C. for 1 hour. The oxygen permeability in 30 degreeC80% RH of the laminated body which has a layer of the obtained inorganic substance containing ion bridge | crosslinking polycarboxylic acid type polymer was measured.

Example 4
After preparing the coating liquid (S-4) prepared above, it was quickly coated on a PET (12 #) substrate so that the thickness after film formation was 2 μm using a desktop coater. Immediately after coating, a nylon film (ONy # 15) was applied to the surface of the coating film to obtain a multilayer structure having a layer structure of “base material PET # 12 / coating liquid S-4 / base material ONy # 15”. . Next, polymerization treatment was performed by irradiating an electron beam (EB) from above the substrate ONy under the conditions of an acceleration voltage of 100 kV, a conveyance speed of 10 m / min, and an irradiation dose of 100 kGy using the EB irradiation apparatus described above. Further, after drying in a gear oven at 100 ° C. for 1 hour, heat treatment at 200 ° C. for 30 minutes, and measuring the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate having an inorganic substance-containing ion-crosslinked polycarboxylic acid polymer layer. did.

(Example 5)
After the coating liquid (S-5) prepared above was prepared, it was quickly coated on an art paper (# 120) substrate using a desktop coater so that the thickness after film formation was 1 μm. Immediately after coating, a nylon film (ONy # 15) was covered on the surface of the coating film to obtain a multilayer structure having a layer configuration of “base art paper / coating liquid S-5 / base ONy # 15”. Next, using a UV irradiation device ("COMPACT UV CONVEYORCSOT-40", manufactured by GS YUASA Co., Ltd.) from above the substrate ONy, the lamp output is 120 W / cm, the conveyance speed is 2 m / min, and the lamp height is 24 cm. Ultraviolet rays (UV) were irradiated to carry out the polymerization treatment. Further, heat treatment was performed in a gear oven at 100 ° C. for 24 hours, and the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate having the inorganic-containing ion-crosslinked polycarboxylic acid polymer layer was measured.

(Example 6)
Coating solution S-6 prepared above is coated on an ethylene propylene rubber sheet (EPT rubber sheet, thickness 1 mm) substrate using a tabletop coater immediately after preparation so that the thickness after film formation is 2 μm. did. Immediately after coating, a nylon film (ONy # 15) was placed on the surface of the coating film to obtain a multilayer structure having a layer structure of “base material EPT rubber sheet / coating liquid S-6 / base material ONy # 15”. . Next, polymerization treatment was performed by irradiating an electron beam (EB) from above the substrate ONy under the conditions of an acceleration voltage of 100 kV, a conveyance speed of 10 m / min, and an irradiation dose of 50 kGy using the EB irradiation apparatus described above.

  Furthermore, after drying at 100 ° C. for 1 hour in a gear oven, heat treatment was performed at 200 ° C. for 10 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the laminate having the inorganic substance-containing ion-crosslinked polycarboxylic acid polymer layer was measured. did.

(Example 7)
The coating liquid S-7 prepared above was coated on a nylon film (ONy # 15) substrate using a desktop coater immediately after preparation so that the thickness after film formation was 2 μm. Immediately after coating, a PET film (PET # 12) was placed on the surface of the coating film to obtain a multilayer structure having a layer structure of “base material ONy # 15 / coating liquid S-7 / base material PET # 12”. . Next, polymerization treatment was performed by irradiating an electron beam (EB) on the base material PET under the conditions of an acceleration voltage of 100 kV, a conveyance speed of 10 m / min, and an irradiation dose of 100 kGy using the EB irradiation apparatus described above.

  Furthermore, after drying at 100 ° C. for 1 hour in a gear oven, heat treatment was performed at 200 ° C. for 30 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate having an inorganic substance-containing ion-crosslinked polycarboxylic acid polymer layer was measured. did.

(Example 8)
After preparing the coating liquid (S-8) prepared above, it was quickly coated on a PET (# 12) substrate using a desktop coater so that the thickness after film formation was 2 μm. Immediately after coating, a nylon film (ONy # 15) was placed on the coating surface to obtain a multilayer structure having a layer structure of “base material PET # 12 / coating liquid S-8 / base material ONy # 15”. .

  Next, polymerization treatment was performed by irradiating ultraviolet rays (UV) from above the substrate ONy under the conditions of a lamp output of 120 W / cm, a conveyance speed of 2 m / min, and a lamp height of 24 cm using the above-described UV irradiation apparatus. Furthermore, after drying at 100 ° C. for 30 minutes in a gear oven, heat treatment was performed at 150 ° C. for 5 hours, and the oxygen permeability at 30 ° C. and 80% RH of the laminate having the inorganic substance-containing ion-crosslinked polycarboxylic acid polymer layer was measured. did.

Example 9
After preparing the coating liquid (S-9) prepared above, it was quickly coated on a PET (# 12) substrate using a tabletop coater so that the thickness after film formation was 2 μm. A multi-layer structure having a layer structure of “base material PET # 12 / coating liquid S-8 / base material OPP # 20” which is obtained by covering a coating film surface with a biaxially stretched polypropylene film (OPP # 20) immediately after coating. Got. Next, polymerization treatment was performed by irradiating an electron beam (EB) from above the base material OPP under the conditions of an acceleration voltage of 150 kV, a conveyance speed of 10 m / min, and an irradiation dose of 100 kGy using the EB irradiation apparatus described above. Further, heat treatment was performed in a gear oven at 100 ° C. for 24 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate having the inorganic-containing ion-crosslinked polycarboxylic acid polymer layer was measured.

(Comparative Example 51)
The coating liquid (S-1) prepared above was coated on a PET (# 12) substrate using a desktop coater immediately after the preparation so that the thickness after film formation was 2 μm. Immediately after coating, a nylon film (ONy # 15) was placed on the surface of the coating film to obtain a multilayer structure having a layer structure of “base material PET # 12 / coating liquid S-1 / base material ONy # 15”. . Subsequently, after leaving to stand at room temperature and drying, heat treatment was performed at 200 ° C. for 30 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate was measured.

(Comparative Example 52)
A laminate was prepared in the same manner as in Comparative Example 51 except that the coating liquid S-51 was used instead of the coating liquid S-1, and the oxygen permeability at 30 ° C. and 80% RH was measured.

(Comparative Example 53)
The coating liquid (S-52) prepared above was coated on a PET (# 12) substrate using a desktop coater immediately after preparation so that the thickness after film formation was 2 μm. Immediately after coating, a nylon film (ONy # 15) was applied to the surface of the coating film to obtain a multilayer structure having a layer structure of “base material PET # 12 / coating liquid S-52 / base material ONy # 15”. . Next, an electron beam (EB) was irradiated from above the substrate ONy using the above-described EB irradiation apparatus under the conditions of an acceleration voltage of 100 kV, a conveyance speed of 10 m / min, and an irradiation dose of 100 kGy.

  Furthermore, after drying at 100 ° C. for 1 hour in a gear oven, heat treatment was performed at 200 ° C. for 30 minutes, and the oxygen permeability at 30 ° C. and 80% RH of the obtained laminate was measured.

The summary of the above Examples and Comparative Examples is summarized in Table 2 below.

  According to Table 2 above, it can be seen that gas barrier laminates having low oxygen permeability (excellent gas barrier properties) were obtained by the examples of the present invention.

  As described above, according to the present invention, a gas barrier layer that exhibits a good gas barrier property with a single layer without passing through a complicated dipping process by a simple process combination of preparation / application / polymerization / heat treatment of the polymerizable composition. A gas barrier laminate is formed.

Claims (15)

A method for producing a gas barrier laminate comprising the following steps 1 to 3;
Step 1: α, β-unsaturated carboxylic acid monomer (A), polyvalent metal ion (B) and halogen in an amount to neutralize 10 to 90% of the α, β-unsaturated carboxylic acid monomer A polymerizable composition comprising at least one hydrolyzable metal compound (C) containing a metal atom to which at least one characteristic group selected from an atom and an alkoxy group is bonded (provided that a crosslinking agent having a group that reacts with a carboxyl group ) the excluding) those containing, by coating on the substrate (1) forming a coating film,
Step 2: Polymerizing the coating film of the polymerizable composition to form a polymer layer containing an inorganic substance derived from the hydrolyzable metal compound (C) and an ion-crosslinked polycarboxylic acid polymer, and Step 3 : A step of heat-treating the polymer layer formed in Step 2 at a temperature of 50 to 400 ° C. to form a gas barrier layer containing an inorganic substance and an ion-crosslinked polycarboxylic acid polymer. α, β-unsaturated carboxylic acid monomer (A) is acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, senecioic acid, tiglic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, The production method according to claim 1, which is at least one unsaturated carboxylic acid compound selected from the group consisting of mesaconic acid and acid anhydrides thereof. The production method according to claim 1 or 2, wherein the polyvalent metal ion (B) is at least one polyvalent metal ion selected from the group consisting of divalent metal ions and trivalent metal ions. The production method according to any one of claims 1 to 3, wherein the hydrolyzable metal compound (C) contains at least one compound represented by the following chemical formula (I).
[Chemical 1]
_{^{M 1 (OR 1) n R}} 2 m-n-t-s X 1 t Z 1 s ... (I)
[In the chemical formula (I), ^{M 1} is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Te, W or Nb Represents. R ¹ represents an alkyl group, R ² represents an organic group selected from an alkyl group, an aralkyl group, an aryl group or an alkenyl group, and Z ¹ represents an organic group having a functional group. X ¹ represents a halogen atom. m is equal to the valence of M ¹ . n represents 0 to m, t represents 0 to m, and s represents an integer of 0 or 1. However, 1 ≦ n + t and n + t + s ≦ m. ] Compound (C) is at least one compound (C1) in which n and t are 0 to (m−1) (where 1 ≦ n + t ≦ m−1) in formula (I), and n + t = m The production method according to claim 4, comprising at least one compound (C2). In the compound (C), Z ¹ in the formula (I) is an organic group having at least one functional group selected from an epoxy group, a (meth) acryloxy group, an amino group, a hydroxyl group, and an isocyanate group. The manufacturing method of Claim 4 or 5. The process according to any one of claims 4-6 wherein the metallic element M ¹ is silicon atom. In the polymerizable monomer composition in the step 1, the weight fraction of the compound (C) contained in the total solid content “compound (C) / [α, β-unsaturated carboxylic acid monomer (A) +” The production method according to claim 1, wherein the polyvalent metal ion (B) + compound (C)] × 100 ”is 1 to 80%. 9. The polymerizable composition according to claim 1, further comprising a substance containing at least one hydrogen bonding functional group selected from a hydroxyl group, an amino group, a carbonyl group, an amide group, and a carboxyl group in the molecule. The manufacturing method as described in. The manufacturing method according to any one of claims 1 to 9, wherein the polymerizable composition further contains a photopolymerization initiator, a thermal polymerization initiator, or both. Step 1 includes compound (C), partial hydrolyzate of compound (C), complete hydrolyzate of compound (C), partial hydrolysis condensate of compound (C), and compound (C). A solution (S) containing at least one metal element-containing compound selected from a condensed part of a complete hydrolyzate, the α, β-unsaturated carboxylic acid monomer (A), and a polyvalent metal ion (B) The method according to any one of claims 1 to 10, which is a step of applying the composition on the substrate (1) after preparing the composition. The production method according to any one of claims 1 to 11, wherein the polymerization treatment of the polymerizable composition in the step 2 is treatment by irradiation with ionizing radiation, heating or both of the coating film. In step 1, after forming a coating film on the substrate (1), a step of coating the surface of the coating film with another or similar substrate (2) is arranged, and then in step 2, the substrate ( The manufacturing method according to claim 12, wherein the coating film between 1) and the substrate (2) is subjected to treatment with irradiation of ionizing radiation and / or heating. The manufacturing method according to claim 12 or 13, wherein the ionizing radiation in the step 2 is ultraviolet rays, electron beams, gamma rays, or α rays. The production method according to claim 12 or 13, wherein the polymerization treatment by heating in the step 2 is a heat treatment in which heating is performed at a temperature of 50 to 250 ° C for 1 to 120 minutes .