Gas barrier coating composition and gas barrier laminate

Abstract

The present invention relates to a gas barrier coating composition comprising a metal oxide and a phosphoric acid compound. A polyvalent metal carboxylate soluble in phosphoric acid is added to the metal oxide and the phosphoric acid compound to provide a coating composition and a gas barrier laminate having the gas barrier coating film (gas barrier layer). The coating composition can form a gas barrier coating film having excellent oxygen barrier properties, water vapor barrier properties, and transparency without volatilizing an inorganic acid.

Description

Technical Field

[0001] The present invention relates to a gas barrier coating composition comprising a metal oxide, a phosphoric acid compound, and a polyvalent metal carboxylate soluble in phosphoric acid. More specifically, the present invention relates to a coating composition that exhibits excellent oxygen and moisture barrier properties and effectively prevents the generation of inorganic acids during coating film formation, and to a gas barrier laminate including the coating film. Background Art

[0002] Conventionally, there is known a gas barrier laminate in which a film composed of metal atoms and phosphorus atoms is formed on a plastic substrate.

[0003] For example, Patent Document 1 below proposes a substantially continuous and substantially non-crystalline gas-impermeable membrane comprising a metal orthophosphate in which the atomic ratio of metal to phosphorus is approximately 2.3 to 0.5, 50% to 100% of the metal atoms are aluminum, 0% to 50% of the metal atoms are selected from tin, titanium, and zirconium, and 0% to approximately 20% of the metal atoms are selected from zinc, chromium, and magnesium.

[0004] However, this gas barrier film still does not meet the requirements of oxygen barrier properties and water vapor barrier properties. In addition, the addition of resin to improve adhesion to the coated substrate is shown, but the effect of adding resin to improve the oxygen and water vapor barrier properties of the coating film is not clear.

[0005] In order to solve such a problem, Patent Document 2 below describes a composite structure comprising a substrate (X) and a layer (Y) laminated on the substrate (X), wherein the layer (Y) contains a reaction product (R) which is a reaction product of at least a metal oxide (A) and a phosphorus compound (B), and the reaction product (R) is a reaction product of at least a metal oxide (A) and a phosphorus compound (B). -1 ~1400cm -1 In the infrared absorption spectrum of the layer (Y) within the range of 1 ) at 1080cm -1 ~1130cm -1 , the metal atoms (M) constituting the metal oxide (A) are aluminum.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Publication No. 57-42032

[0009] Patent Document 2: Japanese Patent No. 4961054 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] The composite structure described in Patent Document 2 satisfies both oxygen barrier properties and water vapor barrier properties. However, since aluminum oxide is used as a raw material, there are concerns about stability against acids and bases contained in the content.

[0012] In order to solve such problems, the present inventors have proposed a gas barrier coating composition comprising a zirconium oxide, a phosphoric acid compound, and an amine compound (Japanese Patent Application No. 2020-55007).

[0013] The aforementioned gas barrier coating composition can form a coating film with both oxygen and water vapor barrier properties. However, it suffers from the following problem: the inorganic acid added to stabilize the zirconium oxide dispersion volatilizes during formation of the gas barrier coating film, adversely affecting equipment and the working environment. To address this issue, the use of zirconium oxide that does not use an inorganic acid as a stabilizer has been considered. However, this also presents the problem of insufficient moisture barrier performance even with the addition of an amine compound.

[0014] Therefore, an object of the present invention is to provide a gas barrier coating composition comprising a metal oxide and a phosphate compound, wherein the coating composition can form a gas barrier coating having superior oxygen barrier properties, water vapor barrier properties, and transparency without volatilizing an inorganic acid, and a gas barrier laminate having the gas barrier coating film (gas barrier layer).

[0015] Technical Solution

[0016] According to the present invention, there is provided a gas barrier coating composition characterized by containing a metal oxide, a phosphoric acid compound, and a carboxylate of a polyvalent metal soluble in phosphoric acid.

[0017] The gas barrier coating composition of the present invention preferably includes the following.

[0018] 1. The polyvalent metal carboxylate is composed of a polyvalent metal ion and an amine compound containing an organic carboxylic acid.

[0019] 2. The polyvalent metal ion is an aluminum ion.

[0020] 3. The amine compound is an amino acid.

[0021] 4. The polyvalent metal carboxylate is aluminum glycinate.

[0022] 5. The metal oxide is zirconium oxide.

[0023] 6. The phosphate compound is at least one of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and cyclic polyphosphoric acid.

[0024] According to the present invention, there is also provided a gas barrier laminate comprising a coating film formed from the above-mentioned gas barrier coating composition on a substrate.

[0025] In the gas barrier laminate of the present invention, the following are preferred.

[0026] 1. The coating film contains at least two metal phosphate compounds, which have an infrared absorption spectrum at 1000 cm -1 ~1130cm -1 The range has infrared absorption becoming the maximum absorption peak.

[0027] 2. The coating film contains at least one metal oxide.

[0028] 3. The coating film has a maximum peak in the range of 400 eV to 405 eV in terms of the bond energy of N obtained by XPS.

[0029] 4. There is an adhesion-promoting coating between the substrate and the coating film.

[0030] 5. The substrate is composed of a 12 μm thick biaxially stretched polyester, and a coating of 1.0 g / m 2 The coating film, when a 50 μm thick unstretched polypropylene film is arranged on the coating film, has an oxygen permeability of 25 cc / m 2 ·day·atm (40℃90%RH) or less, and water vapor transmission rate is 5.5g / m 2 · Days (40℃ 90% RH) or less.

[0031] Effects of the Invention

[0032] The gas barrier coating composition of the present invention utilizes a metal oxide and a phosphoric acid compound, along with a polyvalent metal carboxylate soluble in phosphoric acid, to produce a barrier coating composition with highly dispersed metal oxide particles without requiring a large amount of inorganic acid. As a result, no inorganic acid volatilization occurs during coating film formation, minimizing the impact on equipment and preventing degradation of the working environment. Furthermore, a uniform and dense crosslinked structure based on the metal oxide and phosphoric acid compound is formed, resulting in a coating film exhibiting excellent oxygen and water vapor barrier properties.

[0033] Furthermore, polyvalent metal carboxylates can supplement metal ions by replenishing metal ions, eliminating metal ion deficiencies. Furthermore, the amine compound containing an organic carboxylic acid reacts with the metal ions and phosphoric acid, becoming incorporated into the crosslinked structure and acting as a binder between the metal oxide particles. This results in a coating film with few defects. This, combined with the aforementioned uniform and dense crosslinked structure, can further enhance oxygen and water vapor barrier properties. Consequently, the gas barrier coating composition of the present invention can provide not only gas barrier laminates for non-retort applications, but also gas barrier laminates that can withstand retort sterilization.

[0034] Furthermore, by using zirconium oxide as the metal compound, a coating film can be formed that is stable against acids and bases contained in the contents, thereby exhibiting further excellent oxygen barrier properties and water vapor barrier properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a diagram showing the cross-sectional structure of an example of the gas barrier laminate of the present invention.

[0036] Figure 2 This is a diagram showing the cross-sectional structure of another example of the gas barrier laminate of the present invention. DETAILED DESCRIPTION

[0037] (Gas barrier coating composition)

[0038] The gas barrier coating composition of the present invention is characterized in that it contains a metal oxide, a phosphoric acid compound, and a carboxylate of a polyvalent metal soluble in phosphoric acid.

[0039] As described above, the present invention has found that the inclusion of a metal oxide and a phosphoric acid compound and a carboxylate of a polyvalent metal soluble in phosphoric acid can improve the dispersibility of metal oxide particles and provide excellent oxygen barrier properties and water vapor barrier properties even without the presence of an inorganic acid.

[0040] [Metal oxides]

[0041] The metal oxide used in the gas barrier coating composition of the present invention is preferably an oxide of a divalent or higher-valent metal atom, but is not limited thereto. Examples thereof include oxides of magnesium, calcium, iron, zinc, aluminum, silicon, titanium, zirconium, and the like. Among them, zirconium oxide is preferably used.

[0042] Zirconium oxide contains Zr and O as component elements. Amorphous zirconium oxide primarily contains zirconium hydroxide (Zr(OH)4) and / or zirconium oxyhydroxide (ZrO(OH)2), while crystalline zirconium oxide primarily contains hydrated zirconium oxide (ZrO2·xH2O) and / or zirconium oxide (ZrO2). The term "primary component" refers to a component present at a ratio of 50% or greater. The crystallinity of zirconium oxide and zirconium oxide coated with a gas barrier film can be evaluated by identifying characteristic X-ray peaks of crystalline zirconium using a conventionally known X-ray diffraction apparatus.

[0043] In the present invention, the zirconium oxide may be either crystalline or amorphous (zirconium oxide).

[0044] Generally, zirconium oxide is used in the form of a sol containing zirconium oxide particles as a dispersant and an inorganic acid such as nitric acid as a stabilizer. In the present invention, as described above, in order to prevent the volatilization of the acid during coating film formation due to the presence of an inorganic acid, it is preferred to use the following zirconium oxide sol instead of nitric acid and other inorganic acids, wherein the zirconium oxide sol uses a carbonate, ammonium carbonate salt, an organic dispersant, etc.

[0045] Furthermore, by incorporating an amine compound such as aluminum glycinate described later as a polyvalent metal carboxylate soluble in phosphoric acid, a uniform, dense, and defect-free coating film can be formed. Therefore, even when crystalline zirconium oxide is used, both oxygen barrier properties and moisture barrier properties equivalent to those achieved when amorphous zirconium having a large number of hydroxyl groups used for the phosphorylation reaction is used can be achieved.

[0046] Furthermore, the average particle size (D50) of the primary particles of zirconium oxide is ideally 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less. This allows for the formation of a uniform coating film with excellent transparency. It should be noted that the average particle size (D50) is the volume average particle size measured by laser diffraction / scattering, and D50 represents the 50th percentile value in the volume-based particle size distribution. Using such fine-particle zirconium oxide as a raw material can achieve excellent transparency.

[0047] [Phosphate compounds]

[0048] Examples of the phosphoric acid compounds used in the present invention include orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and their derivatives. Specific examples of polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid formed by condensing four or more phosphoric acids. Examples of derivatives of the aforementioned compounds include orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, their salts, (partial) ester compounds, halides (such as chlorides), and dehydrates (such as phosphorus pentoxide). Examples of phosphonic acid derivatives also include compounds in which the hydrogen atom directly bonded to the phosphorus atom of phosphonic acid (HP(=O)(OH)2) is substituted with an alkyl group optionally having various functional groups (for example, nitrilotris(methylenephosphonic acid) and N,N,N',N'-ethylenediaminetetra(methylenephosphonic acid)), their salts, (partial) ester compounds, halides, and dehydrates. Furthermore, organic polymers containing phosphorus atoms, such as phosphorylated starch, may also be used. These phosphoric acid compounds may be used alone or in combination of two or more.

[0049] In the present invention, it is particularly preferred to use at least one of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and cyclic polyphosphoric acid.

[0050] [Polyvalent metal carboxylates]

[0051] The polyvalent metal carboxylates soluble in phosphoric acid used in the present invention are preferably those composed of polyvalent metal ions and an amine compound containing an organic carboxylic acid. The polyvalent metal ions dissolved in the phosphoric acid-soluble polyvalent metal carboxylates supplement the metal ion deficiency in the binder between the particles in the crosslinked structure of the metal oxide and phosphoric acid, further improving oxygen barrier properties and water vapor barrier properties.

[0052] As the polyvalent metal ion in the carboxylate of a polyvalent metal, there is no particular limitation as long as a polyvalent metal ion that can crosslink a carboxyl group can be provided. As the polyvalent metal ion, examples include: alkaline earth metals (magnesium Mg, calcium Ca, strontium Sr, barium Ba, etc.), periodic table 8 group metals (iron Fe, ruthenium Ru, etc.), periodic table 11 group metals (copper Cu, etc.), periodic table 12 group metals (zinc Zn, etc.), periodic table 13 group metals (aluminum Al, etc.), particularly preferably divalent to trivalent, preferably aluminum ion. In addition, the above-mentioned metal ions can be used alone or in combination of two or more.

[0053] Examples of the amine compound containing an organic carboxylic acid that can form a polyvalent metal carboxylate with a polyvalent metal ion include amino acid compounds having an amino group and a carboxyl group.

[0054] Examples of amino acid compounds include α-amino acids such as glycine, alanine, serine, tryptophan, arginine, glutamic acid, and aspartic acid; β-amino acids such as β-alanine; γ-amino acids such as γ-aminobutyric acid; and amino acid polymers. More than one of these may be used in combination, and glycine and aspartic acid are particularly preferably used.

[0055] In the present invention, aluminum glycinate can be particularly preferably used as the polyvalent metal carboxylate.

[0056] [Preparation of composition]

[0057] The gas barrier coating composition of the present invention may be either an aqueous or solvent-based composition as long as it contains the above-mentioned metal oxide, phosphoric acid compound, and polyvalent metal carboxylate, but is preferably an aqueous composition.

[0058] Ideally, a sol containing metal oxide fine particles as a dispersoid is used as the metal oxide in the gas barrier coating composition. As described above, in the present invention, a sol containing metal oxide fine particles as a dispersoid is preferably used that does not contain an inorganic acid as a stabilizer.

[0059] Furthermore, for similar reasons, it is desirable that the gas barrier coating composition of the present invention not use a volatile and corrosive inorganic acid such as nitric acid, hydrochloric acid, or acetic acid as a deflocculant. Such an inorganic acid is used to improve the dispersibility of the metal oxide fine particles and to produce a dispersion having excellent transparency and viscosity stability.

[0060] Next, the phosphoric acid compound, the polyvalent metal carboxylate, and the metal zirconium oxide are mixed in a solvent capable of dissolving the phosphoric acid compound and the polyvalent metal carboxylate.

[0061] As such an aqueous medium, conventionally known aqueous media such as distilled water, ion-exchanged water, and pure water can be used. Similar to conventional aqueous compositions, organic solvents such as alcohols, polyols, and their derivatives, and ketones can be included. When such a co-solvent is used, the content can be 1% to 90% by weight relative to the resin component in the aqueous composition. By including the solvent within this range, film-forming performance is improved. As such an organic solvent, amphiphilic organic solvents are preferred. Examples include methanol, ethanol, isopropyl alcohol, n-butanol, methyl ethyl ketone, butyl cellosolve, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, acetone, and methyl ethyl ketone.

[0062] Furthermore, in the present invention, a conventional dispersion treatment can be performed during the preparation of the coating material for forming the gas barrier laminate. Known dispersion treatment methods include pulverization of fine particles by cavitation using an ultrasonic homogenizer, mechanical dispersion using a disperser using a rotary blade, and dispersion using a grinder using glass or zirconia beads. In the present invention, these coating material microdispersion treatments can be preferably used.

[0063] In the gas barrier coating composition of the present invention, the phosphoric acid compound and the polyvalent metal carboxylate may be added within a range that does not impair the oxygen barrier property and the water vapor barrier property.

[0064] The phosphate compound is preferably blended so that the net intensity ratio P(P-kα) / M(M-kα) of the metal oxide or polyvalent metal carboxylate to the phosphate compound as measured by fluorescent X-rays is in the range of 0.5 to 20. When zirconium oxide is used as the metal oxide, it is preferably blended so that the net intensity ratio P(P-kα) / Zr(Zr-kα) of the zirconium oxide to the phosphate compound as measured by fluorescent X-rays is in the range of 1.0 to 8.0. It is particularly preferably blended so that the net intensity ratio P(P-kα) / Zr(Zr-kα) of the zirconium oxide to the phosphate compound as measured by fluorescent X-rays is in the range of 2.0 to 7.0. Furthermore, when an aluminum salt is used as a carboxylate of a polyvalent metal, it is preferably blended so that the net intensity ratio P(P-kα) / Al(Al-kα) of the aluminum salt to the phosphate compound obtained by fluorescent X-ray measurement is in the range of 0.1 to 12.0, and particularly preferably blended so that the net intensity ratio P(P-kα) / Al(Al-kα) of the aluminum salt to the phosphate compound obtained by fluorescent X-ray measurement is in the range of 3.0 to 8.0.

[0065] Furthermore, the amount of polyvalent metal carboxylates added to gas barrier coating compositions varies depending on the type of polyvalent metal carboxylates used and cannot be generally specified. However, it is preferably added in an amount of 1 to 300 parts by mass, and particularly preferably in an amount of 5 to 50 parts by mass, relative to 100 parts by mass of the metal oxide. If the amount added is less than the above range, the effects obtained by adding the polyvalent metal carboxylates will not be fully achieved compared to those within the above range. Even if the amount added is greater than the above range, not only will no further effects be achieved, but the barrier structure of the coating film may be defective compared to that within the above range.

[0066] The gas barrier coating composition may contain, in addition to the above-mentioned components, a crosslinking agent, a metal complex, a polymer compound, a filler, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, and the like.

[0067] (Gas barrier coating)

[0068] The gas barrier coating film formed by the gas barrier coating composition of the present invention comprises the metal oxide, the phosphoric acid compound, and the polyvalent metal carboxylate. Specifically, phosphate ester bonds are formed, and the metal oxide and the phosphoric acid compound are cross-linked, thereby forming a dense cross-linked structure. Furthermore, the amine compound containing an organic carboxylic acid in the polyvalent metal carboxylate reacts with the metal ions and phosphoric acid to form an ammonium salt compound, which is incorporated into the cross-linked structure, or forms a polyamide formed by condensation of the amine compounds, thereby forming a composite structure.

[0069] Therefore, the coating film comprising the gas barrier coating composition of the present invention has the following characteristics: the FT-IR spectrum of the coating film alone is 800 cm -1 ~1400cm -1 In the infrared absorption spectrum within the range of 1000cm -1 ~1130cm -1 The infrared absorption peak is the maximum in the range of 1650cm and has the following characteristics: the maximum peak is in the range of nitrogen (N) bond energy (400eV to 405eV) obtained by X-ray photoelectron spectroscopy (XPS) of the gas barrier coating monomer. -1 The infrared absorption wavelength confirms the formation.

[0070] Furthermore, in a coating film formed from the gas barrier coating composition of the present invention, the net intensity ratio P(P-kα) / M(M-kα) of the metal oxide or polyvalent metal carboxylate to the phosphoric acid compound, as measured by fluorescent X-rays, is 0.5 to 20. When the metal oxide is zirconium oxide, it is preferably in the range of 1.0 to 8.0, particularly preferably 2.0 to 7.0. When the polyvalent metal carboxylate is an aluminum salt, it is preferably in the range of 0.1 to 12.0, particularly preferably 3.0 to 8.0. By maintaining the net intensity ratio P(P-kα) / M(M-kα) within this range, the phosphoric acid compound reacts efficiently with the hydroxyl groups of the metal oxide in the coating film, preventing excess or deficiency. This allows for the formation of a uniform and dense coating film, resulting in excellent oxygen barrier properties and water vapor barrier properties. Specifically, if the net intensity ratio measured by fluorescent X-rays is below the above range, the amount of phosphate compound is insufficient, resulting in insufficient bonding between the metal atom particles and an increase in the amount of hydroxyl groups on the surfaces of the metal atom particles, which may reduce oxygen barrier properties and water vapor barrier properties. On the other hand, if the net intensity ratio measured by fluorescent X-rays is above the above range, the amount of phosphate compound is excessive, which increases the amount of hydroxyl groups derived from phosphate groups and may further reduce oxygen barrier properties and water vapor barrier properties.

[0071] (Gas Barrier Laminate)

[0072] The gas barrier laminate of the present invention is a laminate having a gas barrier layer formed of the gas barrier coating film on at least one surface of a substrate. Figure 1 As shown, a gas barrier layer 3 is formed on a substrate 1 via an anchor coating layer 2 (described later). The anchor coating layer 2 is a coating film that has excellent adhesion to the plastic substrate 1. By forming the gas barrier layer on this coating film, the interlayer adhesion between the gas barrier layer and the plastic substrate is significantly improved, effectively preventing the gas barrier layer from peeling from the substrate even when retorting.

[0073] Furthermore, in the gas barrier laminate of the present invention, if Figure 2 As shown, it is preferable that a moisture-resistant resin layer 4 made of a thermoplastic resin such as an unstretched polypropylene resin film is formed on the gas barrier layer 3 .

[0074] The gas barrier layer of the gas barrier laminate of the present invention has sufficient gas barrier properties, especially oxygen barrier properties and water vapor barrier properties. The gas barrier laminate comprises a 12 μm thick substrate film made of biaxially stretched polyester and a coating amount of 1.0 g / m 2 When the gas barrier film (gas barrier layer) is formed by the above-mentioned gas barrier film (gas barrier layer) and the unstretched polypropylene film with a thickness of 50 μm, it has the following excellent oxygen barrier properties and boiling resistance: the oxygen permeability (according to JIS K-7126) is 25cc / m 2 ·day·atm (40℃90%RH) or less, and water vapor transmission rate is 5.5g / m 2 · Days (40℃ 90% RH) or less.

[0075] Furthermore, the gas barrier laminate having the above-described structure has excellent transparency with a total light transmittance of 85% or more and a haze of 30% or less.

[0076] [Base material]

[0077] As the substrate of the gas barrier laminate, conventionally known substrates composed of resins such as thermoplastic resins and thermosetting resins, fibers such as paper and non-woven fabrics can be used, but preferably, films, sheets, or packaging materials in the form of bottles, cups, trays, cans, etc. made from thermoplastic resins that can be thermoformed by methods such as extrusion molding, injection molding, blow molding, stretch blow molding or pressure molding can be listed.

[0078] Examples of the thermoplastic resin constituting the substrate include olefin copolymers such as low-, medium- or high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-1-butene copolymers, ionomers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, and polyethylene naphthalate; polyamides such as nylon 6, nylon 6,6, nylon 6,10, and meta-xylylenediamine adipamide; styrene copolymers such as polystyrene, styrene-butadiene block copolymers, styrene-acrylonitrile copolymers, and styrene-butadiene-acrylonitrile copolymers (ABS resin); vinyl chloride copolymers such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers; acrylic copolymers such as polymethyl methacrylate and methyl methacrylate / ethyl acrylate copolymers; and polycarbonate.

[0079] In the present invention, a sheet made of polyethylene terephthalate, polybutylene terephthalate, or polypropylene can be particularly preferably used.

[0080] These thermoplastic resins may be used alone or as a blend of two or more, or different resins may be present as a laminate. Furthermore, the plastic substrate may be a single layer or a laminate of two or more layers, such as obtained by simultaneous melt extrusion or other lamination processes.

[0081] If desired, one or more additives such as pigments, antioxidants, antistatic agents, ultraviolet absorbers, and lubricants may be added to the melt-moldable thermoplastic resin in an amount ranging from 0.001 to 5.0 parts by weight based on 100 parts by weight of the resin.

[0082] Furthermore, for example, in order to reinforce the container, one or more of a fiber reinforcement material such as glass fiber, aromatic polyamide fiber, carbon fiber, pulp, cotton / cotton linter, or a powder reinforcement material such as carbon black or white carbon black, or a sheet reinforcement material such as glass flakes or aluminum flakes may be added in an amount of 2 to 150 parts by mass relative to 100 parts by mass of the thermoplastic resin. Furthermore, for the purpose of bulking, one or more of heavy or soft calcium carbonate, mica, talc, kaolin, gypsum, clay, barium sulfate, alumina powder, silica powder, magnesium carbonate, etc. may be added in an amount of 5 to 100 parts by mass relative to 100 parts by mass of the thermoplastic resin according to a formulation known per se.

[0083] Furthermore, for the purpose of improving gas barrier properties, 5 to 100 parts by mass of flaky inorganic fine powder, such as water-swellable mica or clay, may be added based on a known formulation to 100 parts by mass of the thermoplastic resin.

[0084] Similarly, for the purpose of improving the gas barrier properties, a thin film layer of an inorganic material such as silicon oxide or aluminum oxide may be formed on a plastic substrate physically or chemically using a vapor deposition method.

[0085] Furthermore, the substrate can ultimately be a film, sheet, or molded article such as a container, or the coating can be pre-applied to a preform used to form a container. Examples of such preforms include: bottomed or bottomless cylindrical parisons for biaxial stretch blow molding; tubes for plastic container molding; sheets for vacuum molding, pressure molding, and plug-assist molding; and films for heat-sealing lids and bag making.

[0086] [Adhesion-promoting coating]

[0087] As an adhesion-enhancing coating formed on the surface of the substrate as needed, an adhesion-enhancing coating used in a gas barrier laminate can be used, preferably an adhesion-enhancing coating composed of a previously known polyurethane resin composed of a hydroxyl-containing compound as a main agent of an acrylic resin, polyol, etc. and an isocyanate curing agent, or an adhesion-enhancing coating further compounded with a silane coupling agent.

[0088] <Polyurethane resin>

[0089] As the polyurethane resin constituting the anchor coating layer, a known polyurethane resin conventionally used for an anchor coating layer can be used, which contains a hydroxyl-containing compound and an isocyanate compound as a main component of an acrylic resin, a polyol, or the like.

[0090] In the present invention, it is desirable to use a polyurethane resin having a glass transition temperature (Tg) of 80°C or higher, particularly a polyurethane resin in the range of 80°C to 120°C. If the glass transition temperature is below this range, the heat resistance of the anchor coating layer deteriorates compared to that within this range. Furthermore, during drying of the gas barrier layer, the gas barrier coating shrinks due to heating, potentially causing cracks in the gas barrier layer and reducing barrier properties.

[0091] As the acrylic resin, there can be used conventionally known polymers and copolymers synthesized by solution polymerization or suspension polymerization using a radical initiator or the like.

[0092] The glass transition temperature of the acrylic resin is preferably -50°C to 100°C, more preferably 40°C to 100°C. Furthermore, the number average molecular weight of the acrylic resin is preferably 500,000 to 100,000, more preferably 500,000 to 80,000. Furthermore, the hydroxyl value of the acrylic resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 80 mgKOH / g to 180 mgKOH / g.

[0093] The monomers for forming the copolymer are not particularly limited, and copolymers prepared by combining methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-hydroxyethyl methacrylate, t-butyl acrylate, and the like as needed can be used.

[0094] Examples of the polyol include diol, polyester polyol, polyether polyol, acrylic polyol, and urethane-modified products thereof. In particular, acrylic polyol and diol are preferably used.

[0095] The glass transition temperature of the polyester polyol is preferably -50° C. to 100° C., more preferably -20° C. to 80° C. The number average molecular weight of these polyester polyols is preferably 500,000 to 100,000, more preferably 500,000 to 80,000.

[0096] Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, and 1,6-hexanediol.

[0097] As the isocyanate component serving as a curing agent for the polyurethane resin, aromatic diisocyanate, aromatic aliphatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, etc. can be used.

[0098] Examples of the aromatic diisocyanate include toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof) (TDI); phenylene diisocyanate (m- or p-phenylene diisocyanate or a mixture thereof); 4,4'-diphenyl diisocyanate; 1,5-naphthalene diisocyanate (NDI); diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI); 4,4'-xylene diisocyanate (TODI), and 4,4'-diphenyl ether diisocyanate.

[0099] Examples of the aromatic aliphatic diisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), and ω,ω′-diisocyanate-1,4-diethylbenzene.

[0100] Examples of the alicyclic diisocyanate include 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate)) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis(isocyanatemethyl)cyclohexane (1,3- or 1,4-bis(isocyanatemethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), and the like.

[0101] Examples of the aliphatic diisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate caffeic acid methyl ester.

[0102] The polyisocyanate component may include polyfunctional polyisocyanate compounds such as isocyanurate, biuret, and allophanate derived from the above-mentioned polyisocyanate monomers, or polyfunctional polyisocyanate compounds containing terminal isocyanate groups obtained by reaction with trifunctional or higher polyol compounds such as trimethylolpropane and glycerol.

[0103] The polyisocyanate component preferably has a glass transition temperature (Tg) of 50° C. or higher and a number average molecular weight (Mn) of 400 or higher, and particularly preferably has a glass transition temperature (Tg) of 60° C. or higher and a number average molecular weight (Mn) of 500 or higher.

[0104] In the present invention, xylylene diisocyanate is also preferably used among the above-mentioned isocyanate components.

[0105] <Silane coupling agent>

[0106] As the silane coupling agent used in the anchor coating, an epoxysilane-based coupling agent can be preferably used.

[0107] As such epoxysilane coupling agents, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. can be used.

[0108] Examples of the silane coupling agent include tetramethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane, and these can be used as needed.

[0109] Furthermore, for the purpose of improving hot water-resistant adhesive strength, the silane coupling agent used may be one that has been subjected to hydrolysis or condensation reaction as needed.

[0110] [Anchor Coat Forming Composition]

[0111] In the present invention, the composition for forming an anchor coating layer preferably contains the aforementioned polyurethane resin, or further contains a silane coupling agent. Furthermore, the anchor coating layer composition may be either aqueous or solvent-based. From the perspective of the working environment, an aqueous composition is preferably used, and the polyurethane resin used is preferably a water-soluble or water-dispersible polyurethane.

[0112] In the anchor coat-forming composition, the epoxy silane compound is preferably contained in an amount of 1 to 80 parts by mass relative to 100 parts by mass (solid content) of the polyurethane resin. If the epoxy silane compound is less than the above range, the crack resistance during drying cannot be satisfied compared to the case within the above range. On the other hand, even if the epoxy silane compound is more than the above range, it is difficult to further improve the adhesion and crack resistance, and the economic efficiency is also deteriorated.

[0113] Furthermore, the aqueous medium may contain the same conventionally known aqueous medium as used in the gas barrier layer-forming composition, and organic solvents such as alcohols, polyols, and derivatives thereof.

[0114] In addition to the above-mentioned components, the composition for forming the adhesion coating may also contain known curing accelerators, fillers, softeners, anti-aging agents, stabilizers, adhesion promoters, leveling agents, defoaming agents, plasticizers, inorganic fillers, tackifying resins, fibers, colorants such as pigments, and agents for extending the usable time.

[0115] (Method for producing gas barrier laminate)

[0116] In the method for producing the gas barrier laminate of the present invention, the gas barrier coating composition of the present invention may be directly applied to at least one surface of the substrate. However, it is preferred to apply the anchor coating layer-forming composition before applying the gas barrier coating composition.

[0117] The amount of the anchor coating composition to be applied is determined by the content of the polyurethane resin and the silane coupling agent in the composition and cannot be generally specified. However, it is preferably 0.05 g / m2 based on the solid content weight of the coating film. 2 ~1.00g / m 2 It is preferably applied in a manner within the range of 0.10 g / m2, particularly preferably in a manner within the range of 0.10 g / m2 in terms of the solid content weight of the coating film. 2 ~0.50g / m 2 If the amount of the anchor coating applied is less than the above range, the anchor coating may not be fixed to the substrate compared to the case within the above range. On the other hand, if the amount of the anchor coating applied is more than the above range, the economic efficiency becomes worse.

[0118] The anchor coat-forming composition applied to the substrate depends on its composition and coating amount, but the solvent in the composition is removed by drying at a temperature of 80°C to 150°C for 1 to 60 seconds. This allows for economical formation of the anchor coat even when the substrate is made of a low-melting-point plastic such as polypropylene.

[0119] Next, a gas barrier coating composition is applied onto the anchor coat-forming composition from which the solvent has been removed and which is in a dry state. The amount of the gas barrier coating composition applied depends on the content of the metal oxide, phosphate compound, and polyvalent metal carboxylate in the composition and cannot be generally specified. However, it is preferably 0.05 g / m² based on the solid content weight of the coating film. 2 ~3.0g / m 2 It is preferably applied in a manner within the range of 0.1 g / m2, and particularly preferably in a manner such that the solid content weight of the coating film becomes 0.1 g / m2. 2 ~1.0g / m 2 If the coating amount is less than the above range, sufficient barrier properties cannot be obtained. On the other hand, even if the coating amount is more than the above range, it is only economical and has no special advantages.

[0120] Next, the gas barrier coating composition is heated at a temperature of 80°C to 220°C, particularly 140°C to 220°C, for 1 second to 10 minutes, depending on the composition and coating amount of the metal oxide, phosphate compound, and polyvalent metal carboxylate used in the composition. This reduces the difference in shrinkage between the gas barrier layer and the anchor coating layer caused by heating, improving the crack resistance of the gas barrier layer. Furthermore, the interlayer adhesion between the gas barrier layer and the anchor coating layer is significantly improved, preventing the gas barrier layer from peeling from the substrate even after retort sterilization.

[0121] The anchor coating layer-forming composition and the gas barrier coating composition can be applied, dried, or heat-treated by conventionally known methods.

[0122] The coating method is not limited thereto, and for example, coating can be performed by spraying, dipping, or using a bar coater, a roll coater, a gravure coater, or the like.

[0123] Furthermore, the drying or heat treatment can be performed by oven drying (heating), infrared heating, high-frequency heating, or the like.

[0124] Example

[0125] The present invention is further described by the following examples, but the present invention is not limited by the following examples. It should be noted that various measurement methods and evaluation methods in the examples and comparative examples are as follows.

[0126] (Example 1)

[0127] Zirconium oxide sol (ZSL-00120B, manufactured by Daiichi Kinzoku Chemical Industry Co., Ltd. (crystalline zirconium oxide, tetragonal system, carbonate dispersion stabilizer, solid content (ZrO2 equivalent) = 20%)) was used as the main agent of the gas barrier coating composition. First, the zirconium oxide sol was diluted by adding water and isopropyl alcohol. Next, water as an additive solution, 50 phr of phosphoric acid (75% by Wako Pure Chemical Industries, Ltd.) calculated as the non-volatile content of phosphoric acid, and 29 phr of aluminum glycinate (Tokyo Chemical Industry Co., Ltd.), a polyvalent metal carboxylate, were mixed relative to 100 phr of the zirconium oxide sol solid content (ZrO2 equivalent) to prepare a liquid. Finally, the additive solution was added to the diluted zirconium oxide sol solution and stirred for a predetermined time. This resulted in a gas barrier coating composition with a coating solid content of 12% and a water / isopropyl alcohol ratio of 80 / 20.

[0128] (Method for preparing gas barrier laminate sample)

[0129] The gas barrier coating composition prepared was used to prepare a sample of a gas barrier laminate in the following manner: A 12 μm thick biaxially stretched polyester film (Lumirror P60 manufactured by Toray Film Processing Co., Ltd.) was coated using a bar coater at a coating weight of 1.3 g / m 2 The gas barrier coating composition was applied in a manner of , and heated and dried at 220° C. for 10 minutes in a box oven to obtain a sample of a gas barrier laminate.

[0130] (Method for Preparing Laminated Body Samples for Gas Barrier Property Evaluation)

[0131] As for the laminate sample for evaluating gas barrier properties, a laminate for evaluating gas barrier properties was prepared as follows: a bar coater was used to coat the surface of the gas barrier laminate coated with the gas barrier coating composition at a coating amount of 4.0 g / m 2 A urethane adhesive (TAKENATE A-315 / TAKENATE A-50, manufactured by Mitsui Chemicals, Inc.) was applied and dried using a dryer, and then laminated onto a 50 μm thick unstretched polypropylene film (Torayfan ZK401, manufactured by Toray Film Manufacturing Co., Ltd.).

[0132] (Example 2)

[0133] As an anchor coat, 3-glycidoxytrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 phr of a water-dispersible polyurethane resin (TAKELAC WPB341, solid content = 30%, Tg = 115°C, manufactured by Mitsui Chemicals, Inc.) to give 30 phr, and the mixture was further diluted with pure water to give a solid content of 8.0%, followed by stirring to obtain an anchor coat coating composition A. The coating composition was applied using a bar coater at a coating amount of 0.20 g / m 2 The obtained adhesion coating composition A was applied in a manner of 100° C. and dried at 140° C. for 1 minute.

[0134] Furthermore, the coating amount was 2.0 g / m 2 A gas barrier layer was formed on the anchor coating layer in the same manner as in Example 1 except for the above, thereby obtaining a gas barrier laminate and a laminate for evaluating gas barrier properties.

[0135] (Example 3)

[0136] As an anchor coat, a polyisocyanate curing agent (TAKENATE D-110N, solid content = 75%, TPI adduct type of meta-xylylenediisocyanate) was added to 100 phr of an acrylic resin (Acrynal TZ#9515, Tg = 83°C, solid hydroxyl value = 180 mgKOH / g, manufactured by Toei Chemicals Co., Ltd.) to give 40 phr. The mixture was further diluted with 2-butanone / ethyl acetate = 70 / 30 to give a solid content of 4.0%, and stirred to obtain an anchor coat coating composition B. The coating was applied using a bar coater at a coating amount of 0.25 g / m 2 The obtained anchor coating composition B was applied in a manner of , and a drying heat treatment was performed at 140° C. for 1 minute.

[0137] Furthermore, the coating amount was 1.9 g / m 2 A gas barrier layer was formed on the anchor coating layer in the same manner as in Example 1 except for the above, thereby obtaining a gas barrier laminate and a laminate for evaluating gas barrier properties.

[0138] (Example 4)

[0139] In Example 2, the coating amount was 2.1 g / m 2 A gas barrier laminate and a laminate for evaluating gas barrier properties were obtained by the same method as in Example 2, except for the above. Two sheets of the obtained laminate for evaluating gas barrier properties were placed opposite each other and heat-sealed to form a three-way sealed bag (130 cm × 170 cm) with a seal width of 5 mm. The resulting bag was filled with 200 g of pure water and heat-sterilized at 121°C for 30 minutes in a retort apparatus. Samples were then cut out to obtain retorted laminates for evaluating gas barrier properties.

[0140] (Comparative Example 1)

[0141] In Example 1, the coating amount was set to 1.1 g / m2 in the same manner except that the phosphoric acid content in the gas barrier coating composition was set to 51 phr and aluminum glycinate was not added. 2 A gas barrier laminate and a laminate for evaluating gas barrier properties were obtained in the same manner as in Example 1 except for the above.

[0142] (Comparative Example 2)

[0143] In Example 1, the polyvalent metal carboxylate of the gas barrier coating composition was replaced with 48 phr of glycine instead of aluminum glycinate, and the coating amount was set to 1.1 g / m 2 A gas barrier laminate and a laminate for evaluating gas barrier properties were obtained in the same manner as in Example 1 except for the above.

[0144] (Reference Example 1)

[0145] In Example 1, as the metal oxide, zirconium oxide sol (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., ZSL-00120A, crystalline zirconium oxide, tetragonal system, dispersion stabilizer is nitric acid, solid content = 30%) was used. The addition amount of phosphoric acid was set to 54 phr, and the film thickness of the coating film was set to 1.0 g / m 2 , and except for this, a gas barrier laminate and a laminate for gas barrier evaluation were obtained by the same method as in Example 1.

[0146] (Reference Example 2)

[0147] In Example 1, the gas barrier coating composition was not applied, and a 12-μm-thick biaxially stretched polyester film (manufactured by TorayFilm Processing Co., Ltd., Lumirror P60) was used as the base material. Except for this, a laminate for gas barrier evaluation was obtained by the same method as in Example 1.

[0148] (Evaluation Method)

[0149] Using the following evaluation methods, as shown in Table 2, the evaluation results of the gas barrier laminate and the laminate for gas barrier evaluation were obtained.

[0150] [Oxygen Transmission Rate]

[0151] Each laminate for gas barrier evaluation obtained in the examples, comparative examples, and reference examples was measured using an oxygen transmission rate measuring device (OX-TRAN 2 / 21 manufactured by Modern Control). The measurement conditions were set to a temperature of 40°C and a relative humidity of 90%. <X

[0152] [Water Vapor Transmission Rate]

[0153] Each laminate for gas barrier evaluation obtained in the examples, comparative examples, and reference examples was measured using a water vapor transmission rate measuring device (PERMATRAN-W 3 / 31 manufactured by Modern Control). The measurement conditions were set to a temperature of 40°C and a relative humidity of 90%.

[0154] [Infrared Absorption Spectrum]

[0155] Regarding each gas barrier laminate obtained in the examples and comparative examples, the infrared absorption spectrum of the gas barrier coating film coated on the polyester base material was measured using a Fourier transform infrared spectrophotometer (FT / IR-6600 manufactured by JASCO Corporation). When the spectrum of the plastic film used as the base material interfered, it was corrected by subtracting it by the difference spectrum.

[0156] <Measurement Conditions of FT-IR Device>

[0157] Equipment used: FT / IR-6600 manufactured by JASCO.

[0158] Measurement conditions: ATR method (Ge prism).

[0159] Detector: MCT.

[0160] Attachment: Thunder Dome.

[0161] Wavelength range: 800cm -1 ~

[0162] 1400cm -1 .

[0163] Membrane measurement surface: barrier coating surface.

[0164] [Fluorescent X-ray Evaluation]

[0165] As a method for evaluating the elements contained in the gas barrier layered products obtained in the Examples and Comparative Examples, phosphorus and zirconium were quantified using a commercially available fluorescent X-ray analyzer. The net intensities obtained in the measurements for each gas barrier layered product were defined as P / Zr and P / Al for P, Zr, and Al, respectively. The ratios of the metal elements in the coatings were calculated for evaluation. Regarding Al, a score of 0 was assigned to any Al detected as a coating component using fluorescent X-ray analysis.

[0166] <Measurement conditions of fluorescent X-ray analyzer)

[0167] Equipment used: Rigaku Electron ZSX100e.

[0168] Measurement conditions: Measurement targets: Zr-Kα ray, P-Kα ray, Al-Kα ray.

[0169] Measuring diameter: 10mm.

[0170] Measurement X-ray: Rh (4.0 kW) 50 kV 72 mA (2θ = 0 to 90).

[0171] Film measurement surface: Measured by irradiating X-rays from the barrier coating surface.

[0172] [X-ray photoelectron spectroscopy]

[0173] As a method for evaluating the chemical bonding state of the elements contained in each gas barrier laminate obtained in the Examples and Comparative Examples, the constituent elements of the sample and their electronic states can be analyzed by irradiating the sample surface with X-rays and measuring the energy of the generated photoelectrons. Nitrogen and zirconium were analyzed using a commercially available X-ray photoelectron spectrometer. 5 / 2The peak position was set to 185.0 to analyze the bond energy of the elements obtained in the measurement of each gas-barrier laminate, and the bonding state of nitrogen elements in the coating film was evaluated. Zr3d used in peak correction 5 / 2 The numerical value referred to the literature J. inorg. nucl. Chem. Vol. 43, No. 12, pp. 3329-3334, 1981.

[0174] <Measurement Conditions of X-ray Photoelectron Spectrometer>

[0175] Equipment used: K-ALPHA manufactured by Thermo Fisher SCIENTIFIC.

[0176] Measurement conditions: Measured elements Zr3d, N1s.

[0177] Peak correction: Zr3d 5 / 2 : 185.0.

[0178] Type of X-ray: Al monochromator.

[0179] Pass Energy: 150.0 eV.

[0180] Measurement diameter: 400 μm.

[0181] Film measurement surface: Gas-barrier coating film surface.

[0182] The various measurement and evaluation results of the above-mentioned examples, comparative examples and reference examples are shown in Table 1 and Table 2.

[0183] [Table 1]

[0184]

[0185]

[0186] [Table 2]

[0187]

[0188] [Abbreviations in the Table]

[0189] ZSL-00120B: Crystalline zirconium oxide (carbonate type).

[0190] ZSL-00120A: Crystalline zirconium oxide (nitrate type).

[0191] P-Kα / Zr-Kα: Refers to the content ratio of phosphorus element (P) to zirconium element (Zr) derived from the phosphoric acid compound in the coating film.

[0192] P-Kα / Al-Kα: refers to the content ratio of phosphorus (P) derived from the phosphate compound to aluminum (Al) in the coating film.

[0193] Fluorescence X-ray evaluation: The maximum wavelength of the infrared absorption spectrum will be observed at 1000 cm -1 ~1130cm -1 phosphate, and samples in which at least aluminum and zirconium polyvalent metal elements were detected by fluorescent X-ray measurement were set as ○.

[0194] In Table 2, "ND" means "not detected" and "-" means not determined.

[0195] Industrial applicability

[0196] The gas barrier coating composition of the present invention can form a coating film having excellent oxygen barrier properties and water vapor barrier properties, and can be preferably used as a transparent high-barrier packaging material.

[0197] Description of Reference Numerals

[0198] 1: substrate;

[0199] 2: Adhesion-enhancing coating;

[0200] 3: Gas barrier layer (gas barrier film);

[0201] 4: Moisture-resistant resin layer.

Claims

1. A gas barrier coating composition, characterized in that Contains: metal oxides, phosphoric acid compounds, and polyvalent metal carboxylates soluble in phosphoric acid. The metal oxide is zirconium oxide, the polyvalent metal carboxylate is aluminum glycinate, The net intensity ratio P(P-kα) / Zr(Zr-kα) of the zirconium oxide and the phosphate compound obtained by fluorescent X-ray measurement is in the range of 1.0 to 8.0, and the net intensity ratio P(P-kα) / Al(Al-kα) of the aluminum glycinate and the phosphate compound obtained by fluorescent X-ray measurement is in the range of 0.1 to 12.

0.

2. The gas barrier coating composition according to claim 1, wherein The phosphate compound is at least one of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and cyclic polyphosphoric acid.

3. A gas barrier laminate, characterized in that: A coating film formed from the gas barrier coating composition according to claim 1 or 2 is provided on a substrate.

4. The gas barrier laminate according to claim 3, wherein The coating film has an infrared absorption spectrum at 1000 cm -1 ~1130cm -1 The range has infrared absorption becoming the maximum absorption peak. The gas barrier laminate according to claim 3 or 4, wherein The coating film contains a metal oxide. The gas barrier laminate according to claim 3 , wherein The coating film has a maximum peak in the range of 400 eV to 405 eV in the bond energy of N obtained by XPS.

7. The gas barrier laminate according to claim 3, wherein The coating film contains a polyamide condensate.

8. The gas barrier laminate according to claim 3, wherein The coating film contains a carboxylate of a polyvalent metal.

9. The gas barrier laminate according to claim 3, wherein An adhesion-promoting coating is provided between the substrate and the coating film.

10. The gas barrier laminate according to claim 3, wherein The substrate is composed of a biaxially stretched polyester with a thickness of 12 μm, and a coating amount of 1.0 g / m 2 The coating film, when a 50 μm thick unstretched polypropylene film is arranged on the coating film, has an oxygen permeability of 25 cc / m at 40°C and 90% RH. 2 ·day·atm or less, and the water vapor transmission rate is 5.5g / m at 40℃90%RH 2 · Days or less.

Images