WO2019142923A1 - Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci - Google Patents

Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci Download PDF

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Publication number
WO2019142923A1
WO2019142923A1 PCT/JP2019/001539 JP2019001539W WO2019142923A1 WO 2019142923 A1 WO2019142923 A1 WO 2019142923A1 JP 2019001539 W JP2019001539 W JP 2019001539W WO 2019142923 A1 WO2019142923 A1 WO 2019142923A1
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WIPO (PCT)
Prior art keywords
covering layer
layer
gas barrier
barrier laminate
coating
Prior art date
Application number
PCT/JP2019/001539
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English (en)
Japanese (ja)
Inventor
岡村　賢吾
美季 福上
Original Assignee
凸版印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018119837A external-priority patent/JP7196431B2/ja
Priority claimed from JP2019005916A external-priority patent/JP7172627B2/ja
Priority claimed from JP2019006095A external-priority patent/JP7271960B2/ja
Priority claimed from JP2019006093A external-priority patent/JP2020114636A/ja
Application filed by 凸版印刷株式会社 filed Critical 凸版印刷株式会社
Priority to CN201980008369.8A priority Critical patent/CN111601711B/zh
Priority to EP19741638.1A priority patent/EP3741560B1/fr
Publication of WO2019142923A1 publication Critical patent/WO2019142923A1/fr
Priority to US16/922,140 priority patent/US11766695B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present disclosure relates to a gas barrier laminate and a package comprising the same.
  • Patent Document 1 discloses a gas barrier laminate including a layer including a neutralized product of a polymer in which at least a part of the -COO- group contained in a functional group is neutralized with a divalent or higher metal ion (polyvalent metal ion) Is disclosed.
  • Such a gas barrier laminate is used, for example, in a package for pressure heating sterilization (retort treatment). Thereby, even after retort treatment is performed on the package, the oxygen barrier property of the package is secured.
  • the oxygen barrier property is an oxygen permeation preventing property.
  • the contents of the retort-treated product contain elemental sulfur
  • a compound derived from elemental sulfur may be generated, and an unpleasant odor (retort odor) resulting therefrom may be generated in the package. Therefore, it is conceivable that the compound that is the cause of retort odor is absorbed by the gas barrier laminate.
  • the oxygen barrier property tends to deteriorate.
  • An object of one aspect of the present disclosure is to provide a gas barrier laminate capable of achieving both suppression of retort odor and oxygen barrier properties, and a package including the same.
  • a gas barrier laminate according to one aspect of the present disclosure includes a resin base, a first covering layer containing a carboxylic acid-based polymer, and a second covering layer containing a polyvalent metal compound and a resin, and the resin base ,
  • the first covering layer and the second covering layer are laminated in this order, and the ratio of the thickness of the second covering layer to the thickness of the first covering layer is 1.0 or more and 4.0 or less
  • the second covering layer satisfies at least one of the following conditions 1 to 3.
  • the haze of the second covering layer is 8% or less.
  • the surface roughness Ra of the second covering layer is 1/2 or less of the thickness of the second covering layer.
  • the number per unit area of concave portions having a diameter of 1.5 ⁇ m or more on the surface of the second covering layer opposite to the first covering layer side is 2 pieces / 0.01 mm 2 or less.
  • This gas barrier laminate comprises a second coating layer containing a polyvalent metal compound.
  • heat treatment such as retort treatment or boiling treatment is performed on the package using the gas barrier laminate, hydrogen sulfide generated from the content containing sulfur element chemically reacts with the polyvalent metal compound of the second covering layer .
  • hydrogen sulfide is captured by the gas barrier laminate, so that retort odor can be suppressed.
  • the polyvalent metal ion generated from the polyvalent metal compound in the second coating layer also reacts with the carboxylic acid-based polymer in the first coating layer by heat treatment, and the carboxylic acid-based polymers are ionically crosslinked via the polyvalent metal ion Cross-linked structure is formed.
  • the oxygen barrier properties of the first covering layer can be improved, and the gas barrier laminate can exhibit excellent oxygen barrier properties by the first covering layer.
  • the ratio of the thickness of the second covering layer to the thickness of the first covering layer is 1.0 or more and 4.0 or less, and the second covering layer satisfies at least one of the conditions 1 to 3
  • the second covering layer satisfies at least one of the conditions 1 to 3
  • the thickness of the second covering layer is, for example, 0.10 ⁇ m or more and 0.50 ⁇ m or less.
  • the second covering layer can contain a sufficient amount of the polyvalent metal compound.
  • the fall of the flexibility of a 2nd coating layer can be suppressed favorably.
  • the polyvalent metal compound is zinc oxide, and the content of zinc oxide may be 65% by mass or more and 85% by mass or less based on the mass of the second covering layer. In this case, it is possible to provide a gas barrier laminate in which suppression of retort odor and oxygen barrier properties are achieved at a higher level while exhibiting light transparency.
  • the gas barrier laminate may further include an inorganic deposited layer containing an inorganic oxide between the resin base and the first covering layer.
  • the oxygen barrier property of the gas barrier laminate can be further improved by the synergistic effect of the first covering layer and the inorganic vapor deposition layer.
  • the gas barrier laminate may further include an underlayer containing a urethane-based compound, between the resin base and the inorganic deposition layer. In this case, peeling between the resin base and the inorganic deposition layer can be further suppressed.
  • the gas barrier laminate may be used in a package to which retort treatment or boiling treatment is applied. According to the above-mentioned gas barrier laminate, it is possible to form a package which can achieve both suppression of retort odor and oxygen barrier properties at a high level even when retort treatment or boiling treatment is performed.
  • a gas barrier laminate according to another aspect of the present disclosure includes a film base made of a plastic material (corresponding to the “resin base” in the above embodiment) and a covering layer provided thereon, and the covering layer is At least one silicon-containing compound selected from the group consisting of a polycarboxylic acid polymer, a silane coupling agent represented by the general formula R 1 Si (OR 2 ) 3 , a hydrolyzate thereof, and a condensate thereof And a polyvalent metal compound having a UV absorbance of 0.3 or more and 0.7 or less, which is a value obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at a wavelength of 350 nm measured by absorption photometry And a ratio of the weight of the polycarboxylic acid polymer to the weight of the silicon-containing compound in the first coating layer is 99.5 / 0.5 to 80.0 / 20.
  • the mass of the silicon-containing compound is a mass in terms of a silane coupling agent
  • R 1 in the general formula is an organic group containing a glycidyloxy group or an amino group
  • R 2 is an alkyl group
  • three R 2 s may be identical to or different from each other.
  • the gas barrier laminate according to the other aspect described above may be provided with an adhesive layer (corresponding to the "underlayer” in the above embodiment) and an inorganic vapor deposition layer made of an inorganic oxide, between the film substrate and the coating layer.
  • the synergetic effect of the first covering layer and the inorganic vapor deposition layer can further improve the oxygen barrier property of the gas barrier laminate, and can further suppress the peeling between the film substrate and the inorganic vapor deposition layer.
  • the gas barrier laminate according to the other aspect described above comprises a modification treated layer on a film substrate, an inorganic deposition layer made of inorganic oxide on the modification treatment layer, and a coating layer on the inorganic deposition layer. It may be By the presence of the modified layer between the film substrate and the inorganic vapor deposition layer, peeling between the film substrate and the inorganic vapor deposition layer can be further suppressed.
  • Another aspect of the present disclosure is a package provided with the gas barrier laminate.
  • hydrogen sulfide generated from the contents is absorbed by the gas barrier laminate.
  • retort odor can be suppressed.
  • the gas barrier laminate can suppress the decrease in the oxygen barrier properties due to the heat treatment, the package can exhibit excellent oxygen barrier properties.
  • FIG. 1 is a schematic cross-sectional view showing a first embodiment of the gas barrier laminate according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing a recess that may be present in the second covering layer of the gas barrier laminate shown in FIG.
  • FIG. 3 is a schematic plan view of the package.
  • FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG. 5 (a) to 5 (d) are schematic cross-sectional views for explaining changes in the gas barrier laminate at the time of performing retort treatment.
  • 6 (a) and 6 (b) are schematic cross-sectional views for explaining the change of the package at the time of performing the retort process.
  • FIG. 1 is a schematic cross-sectional view showing a first embodiment of the gas barrier laminate according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing a recess that may be present in the second covering layer of the gas barrier laminate shown in FIG.
  • FIG. 3 is a
  • FIG. 7 is a schematic cross-sectional view showing a modification of the first embodiment shown in FIG.
  • FIG. 8 is a schematic view showing an example of an aspect in which the film surface is RIE-treated by the planar plasma processing apparatus.
  • FIG. 9 is a schematic view showing an example of an aspect in which the film surface is RIE-treated by the hollow anode type plasma processing apparatus.
  • FIG. 10 is a schematic cross-sectional view showing a second embodiment of the gas barrier laminate according to the present disclosure.
  • FIG. 11 is a schematic cross-sectional view showing a modification of the second embodiment shown in FIG.
  • FIG. 12 is a SEM image of the surface of the second covering layer in the gas barrier laminate obtained in Example 1.
  • FIG. 13 is a SEM image of the surface of the second covering layer in the gas barrier laminate obtained in Comparative Example 1.
  • FIG. 1 is a schematic cross-sectional view of the gas barrier laminate according to the first embodiment.
  • the gas barrier laminate 10A shown in FIG. 1 is a film that exhibits gas barrier properties such as at least oxygen and water vapor.
  • the gas barrier laminate 10A exhibits, for example, at least one of flexibility and light transmission.
  • the gas barrier laminate 10A is a film which has heat resistance and can be used for a package to which pressure heating sterilization treatment (retort treatment) or boiling treatment is applied.
  • the gas barrier laminate 10A may have the required properties (for example, light shielding property, water resistance, temperature and humidity resistance, mechanical strength, printability, decoration ease, etc.) in addition to the gas barrier properties and heat resistance.
  • Retort treatment is, for example, wet heat sterilization treatment prescribed by the Food Sanitation Law, and is performed at 100 ° C. or higher.
  • Boiling treatment is sterilization treatment to hot water the object and is performed at less than 100 ° C.
  • the gas barrier laminate 10 A includes a resin base 1, an underlayer 2 (anchor coat), an inorganic deposition layer 3, a first covering layer 5 a (main coat), and a second covering layer 5 b (top coat).
  • the underlayer 2, the inorganic vapor deposition layer 3, the first covering layer 5a and the second covering layer 5b have a laminated structure in which they are arranged in this order.
  • the resin substrate 1 is a resin film (plastic film) to be a support.
  • the resin substrate 1 includes, for example, polyolefin polymers and acid-modified products thereof; polyester polymers; polyamide polymers; polyether polymers; halogen polymers; acrylic polymers; poiimide polymers; It is a film containing at least one of epoxy polymers.
  • the resin base material 1 may be a copolymer of monomers constituting the above-mentioned polymer.
  • the resin base material 1 may contain natural polymer compounds, such as a cellulose acetate, for example.
  • the resin substrate 1 may be a stretched film or a non-stretched film.
  • the thickness of the resin substrate 1 may be, for example, 5 ⁇ m to 10 mm, 5 ⁇ m to 800 ⁇ m, or 5 ⁇ m to 500 ⁇ m.
  • the resin base material 1 has a first surface 1a in contact with the underlayer 2 and a second surface 1b located on the opposite side of the first surface 1a in the thickness direction. From the viewpoint of adhesion to the underlayer 2, the first surface 1a may be subjected to surface treatment.
  • the surface treatment is, for example, corona treatment, flame treatment, plasma treatment or the like.
  • a barrier film such as a barrier film, an inorganic vapor deposition film, or a metal foil may be provided on the second surface 1 b.
  • the barrier film exhibits, for example, a function to inhibit the liquid and air from passing through the resin base 1, and a function to inhibit light from transmitting through the resin base 1.
  • barrier film examples include films composed of polyvinylidene chloride (PVDC), ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polyvinyl alcohol (PVA) or the like.
  • PVDC polyvinylidene chloride
  • EVOH ethylene vinyl alcohol copolymer
  • PAN polyacrylonitrile
  • PVA polyvinyl alcohol
  • an inorganic vapor deposition film is a film in which aluminum, alumina, or silica etc. were vapor-deposited with respect to the resin film.
  • the underlayer 2 is a layer that contributes to the improvement of the adhesion between the resin substrate 1 and the inorganic vapor deposition layer 3 and contains a urethane compound.
  • the thickness of the underlayer 2 is, for example, 0.01 ⁇ m or more and 2 ⁇ m or less.
  • the thickness of the underlayer 2 may be 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the thickness of the underlayer 2 is 0.01 ⁇ m or more, the characteristics of the underlayer 2 are exhibited well.
  • the thickness of the base layer 2 is 2 ⁇ m or less, the decrease in flexibility of the gas barrier laminate 10A can be favorably suppressed. Thereby, when the gas barrier laminate 10A is bent, generation of a crack in the underlayer 2 can be prevented.
  • the underlayer 2 is formed, for example, by applying a liquid (anchor coat liquid) containing an organosilane or organic metal compound, a polyol compound, an isocyanate compound or the like described later to the first surface 1 a of the resin substrate 1.
  • the solvent of the anchor coating solution is, for example, a polar solvent.
  • the anchor coat liquid is applied to the first surface 1a by a known method such as offset printing, gravure printing, roll coating, and doctor blade method.
  • the underlayer 2 contains, for example, a reaction product of an organosilane or an organic metal compound, a polyol compound, and an isocyanate compound. That is, the base layer 2 can also be said to be a urethane-based adhesive layer.
  • the organosilane is, for example, a trifunctional organosilane or a hydrolyzate of the trifunctional organosilane.
  • the metal element contained in the organometallic compound is, for example, Al, Ti, Zr or the like.
  • the organometallic compound is, for example, a metal alkoxide or a hydrolyzate of the metal alkoxide.
  • each of the organosilane hydrolyzate and the metal alkoxide hydrolyzate may have at least one hydroxyl group.
  • the polyol compound may be a polymer compound.
  • the polyol compound may be an acrylic polyol from the viewpoint of transparency.
  • the isocyanate compound mainly functions as a crosslinking agent or a curing agent.
  • the isocyanate compound may be a monomer or a polymer.
  • the inorganic vapor deposition layer 3 is a layer that exhibits, for example, a gas barrier property (water barrier property) to water vapor, and is located on the underlayer 2.
  • the inorganic vapor deposition layer 3 contains an inorganic oxide.
  • the inorganic oxide include aluminum oxide, silicon oxide, magnesium oxide and tin oxide.
  • the inorganic oxide may be selected from the group consisting of aluminum oxide, silicon oxide, and magnesium oxide from the viewpoint of transparency and water barrier properties of the inorganic vapor deposition layer 3.
  • the thickness of the inorganic vapor deposition layer 3 is, for example, 5 nm or more and 100 nm or less, and may be 10 nm or more and 50 nm or less.
  • the inorganic vapor deposition layer 3 When the thickness of the inorganic vapor deposition layer 3 is 5 nm or more, the water barrier property to water vapor is exhibited well. When the thickness of the inorganic vapor deposition layer 3 is 100 nm or less, the decrease in flexibility of the gas barrier laminate 10A can be favorably suppressed. Thereby, when the gas barrier laminate 10A is bent, generation of a crack in the inorganic vapor deposition layer 3 can be prevented.
  • the inorganic vapor deposition layer 3 may also contain multiple types of inorganic oxides.
  • the inorganic vapor deposition layer 3 is a vapor deposition layer formed by, for example, physical vapor deposition or chemical vapor deposition.
  • the physical vapor deposition method is, for example, a vacuum deposition method, a sputtering method, an ion plating method or the like.
  • a plasma assist method, an ion beam assist method, or the like may be performed.
  • oxygen gas or the like may be supplied into the production chamber when the inorganic vapor deposition layer 3 is formed.
  • the first covering layer 5 a is, for example, a layer showing a gas barrier property (oxygen barrier property) to oxygen, and is located on the inorganic vapor deposition layer 3.
  • the first covering layer 5a contains a carboxylic acid-based polymer.
  • the thickness of the first covering layer 5a is, for example, 0.01 ⁇ m to 5 ⁇ m, and may be 0.02 ⁇ m to 3 ⁇ m or 0.04 ⁇ m to 1.2 ⁇ m. When the thickness of the first covering layer 5a is 0.01 ⁇ m or more, the oxygen barrier property is exhibited well. When the thickness of the first covering layer 5a is 5 ⁇ m or less, the decrease in flexibility of the gas barrier laminate 10A can be favorably suppressed.
  • the thickness of the first covering layer 5a can be adjusted so that the ratio of the thickness of the second covering layer 5b to the thickness of the first covering layer 5a, which will be described later, is within a predetermined range.
  • the first covering layer 5 a is formed, for example, by applying a coating liquid containing at least a carboxylic acid-based polymer on the inorganic vapor deposition layer 3.
  • the coating solution is applied onto the inorganic vapor deposition layer 3 in the same manner as the above-described base layer.
  • the solvent of the coating solution may contain water and / or an organic solvent.
  • the carboxylic acid-based polymer contained in the first covering layer 5a is, for example, an ethylenically unsaturated carboxylic acid polymer; a copolymer of an ethylenically unsaturated carboxylic acid monomer and another ethylenically unsaturated monomer; alginic acid, carboxymethyl cellulose And acid polysaccharides having a carboxy group in the molecule, such as pectin.
  • Ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid.
  • Ethylenically unsaturated monomers include, for example, saturated carboxylic acid vinyl ester monomers (ethylene, propylene, vinyl acetate etc.), alkyl acrylate monomers, alkyl methacrylate monomers, alkyl itaconate monomers, vinyl chloride, vinylidene chloride, styrene, Acrylamide, acrylonitrile and the like.
  • the first covering layer 5a may contain plural types of carboxylic acid-based polymers.
  • the carboxylic acid polymer may be a polymer of a monomer having two or more carboxy groups.
  • the carboxylic acid-based polymer is at least one polymerizable unit selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid and crotonic acid. It may be a polymer containing structural units derived from the body. In this case, the proportion of the structural unit in the polymer may be 80 mol% or more, or 90 mol% or more.
  • the number average molecular weight of the carboxylic acid-based polymer is, for example, 2,000 or more and 10,000,000 or less.
  • the number average molecular weight of the carboxylic acid based polymer may be 5,000 or more and 1,000,000 or less.
  • the first covering layer 5a exhibits sufficient water resistance.
  • the number average molecular weight of the carboxylic acid-based polymer is 10,000,000 or less, the first covering layer 5a can be easily formed.
  • the number average molecular weight of carboxylic acid type polymer is a number average molecular weight of polystyrene conversion calculated
  • the first covering layer 5a is at least one selected from the group consisting of a silane coupling agent, a hydrolyzate thereof and a condensate thereof. And a silicon-containing compound of In addition, in this case, the heat resistance, water resistance, and the like of the first covering layer 5a can be improved.
  • the silane coupling agent is, for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane or the like.
  • the hydrolyzate of the silane coupling agent is one in which at least one of the alkyl groups bonded to oxygen of the coupling agent is substituted with a hydroxyl group.
  • the condensate of the silane coupling agent is, for example, one having a Si-O-Si bond (siloxane bond) by condensation of Si-OH of hydrolyzate of 2 molecules.
  • the mass ratio of the carboxylic acid-based polymer to the silicon-containing compound is, for example, 99.5 / 0.5 to 80/20.
  • a gas barrier laminate 10A exhibiting excellent abuse resistance is obtained.
  • the thickness of the first covering layer 5a tends to be uniform, and the first covering layer 5a can exhibit good acid resistance.
  • Some of the carboxy groups contained in the carboxylic acid-based polymer may be previously neutralized with a basic compound.
  • the oxygen barrier property of the first covering layer 5a can be further improved.
  • the heat resistance of the first covering layer 5a can also be improved.
  • the basic compound include polyvalent metal compounds, monovalent metal compounds, ammonia and the like.
  • the polyvalent metal compound is, for example, the same as the polyvalent metal compound (described in detail later) contained in the second covering layer 5b.
  • the basic compound which is a polyvalent metal compound is, for example, zinc oxide, calcium carbonate, sodium carbonate and the like.
  • the basic compound which is a monovalent metal compound is, for example, sodium hydroxide, potassium hydroxide or the like.
  • the first covering layer 5a contains at least a cation constituting a basic compound.
  • the cation is a polyvalent metal ion diffused from the second covering layer 5 b to the first covering layer 5 a.
  • ionic crosslinking is formed by polyvalent metal ions and carboxy groups.
  • the first covering layer 5a has a crosslinked structure in which carboxylic acid polymers are crosslinked via polyvalent metal ions.
  • the 1st coating layer 5a can exhibit the outstanding oxygen barrier property.
  • the oxygen permeability of the gas barrier laminate 10A is less than or equal to 0.1 cc / m 2 ⁇ day ⁇ atm.
  • the first covering layer 5a may contain various additives.
  • the additive is, for example, a plasticizer, a resin, a dispersant, a surfactant, a softener, a stabilizer, an antiblocking agent, a film forming agent, an adhesive, an oxygen absorbent, and the like.
  • the second covering layer 5b has a function of, for example, supplying a polyvalent metal ion to the first covering layer 5a to form a crosslinked structure of a carboxylic acid-based polymer in the first covering layer 5a and improving the oxygen barrier property. And a layer having a function of absorbing hydrogen sulfide which causes retort odor.
  • the second covering layer 5b is located on the first covering layer 5a and contains a polyvalent metal compound and a resin.
  • the thickness of the second covering layer 5b may be, for example, 0.10 ⁇ m or more and 0.50 ⁇ m or less, and may be 0.19 ⁇ m or more and 0.42 ⁇ m or less.
  • the second covering layer 5b can contain a sufficient amount of the polyvalent metal compound, and heat treatment such as retort treatment or boiling treatment produces oxygen. It can fully suppress that barrier property falls.
  • the thickness of the second covering layer 5 b is 0.50 ⁇ m or less, the decrease in flexibility of the second covering layer 5 b can be favorably suppressed.
  • the thickness of the second covering layer 5b can be adjusted such that the ratio of the thickness of the second covering layer 5b to the thickness of the first covering layer 5a described later is within a predetermined range.
  • the second covering layer 5b is formed, for example, by applying a coating liquid containing a polyvalent metal compound and a resin on the first covering layer 5a.
  • the coating solution is applied onto the first covering layer 5a in the same manner as the above-mentioned base layer.
  • the ratio of the thickness of the second covering layer 5b to the thickness of the first covering layer 5a is 1.0 or more. 0 or less, and may be 1.1 or more and 3.0 or less.
  • the said ratio is less than 1.0, coexistence with retort smell suppression and oxygen barrier property will become difficult.
  • the said ratio is more than 4.0, 2nd coating layer 5b will become thick too much, and coating property will worsen.
  • the polyvalent metal compound contained in the second covering layer 5 b is, for example, a single substance of polyvalent metal, an oxide, a hydroxide, a carbonate, an organic acid salt (for example, an acetate), an inorganic acid salt or the like.
  • the polyvalent metal compound may be an ammonium complex or secondary to quaternary amine complex of a polyvalent metal oxide, or a carbonate or organic acid salt thereof.
  • Examples of the polyvalent metal of the polyvalent metal compound contained in the second covering layer 5b include alkaline earth metals, transition metals, aluminum and the like.
  • the alkaline earth metals are, for example, beryllium, magnesium, calcium.
  • the transition metal is, for example, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc or the like.
  • the polyvalent metal compound may be an oxide, hydroxide, chloride, carbonate or acetate of an alkaline earth metal, cobalt, nickel, copper, zinc or aluminum.
  • the polyvalent metal compound may be an ammonium complex of copper or zinc.
  • the polyvalent metal compound may be zinc oxide, aluminum oxide, calcium hydroxide, calcium carbonate, zinc acetate or calcium acetate.
  • the polyvalent metal compound may be zinc oxide or calcium carbonate.
  • the polyvalent metal compound is zinc oxide.
  • the content of the polyvalent metal compound is, for example, 65% by mass or more and 85% by mass or less based on the mass of the second covering layer 5b.
  • the content is 65% by mass or more
  • the hydrogen sulfide is favorably captured in the second covering layer 5b.
  • diffusion of the hydrogen sulfide (sulfur ion) to the first covering layer 5a is favorably suppressed.
  • at least a part of polyvalent metal ions is diffused to the first covering layer 5a.
  • the oxygen barrier property of the 1st coating layer 5a can be exhibited favorably. Therefore, when the said content rate is 65 mass% or more, gas-barrier laminated body 10A compatible with suppression of retort odor, and oxygen barrier property may be formed.
  • the said content rate is 85 mass% or less, drop-off
  • omission from the 2nd coating layer 5b of a polyvalent metal compound can be suppressed.
  • the polyvalent metal compound is zinc oxide, the light transmittance of the second covering layer 5b can be secured by the content being 85 mass% or less.
  • the resin contained in the second covering layer 5b is, for example, an alkyd resin, a melamine resin, an acrylic resin, a urethane resin, a polyester resin, a phenol resin, an amino resin, a fluorine resin, an epoxy resin, an isocyanate resin or the like.
  • the coating liquid for forming the second covering layer 5b may contain a dispersing agent (for example, an anionic surfactant, a nonionic surfactant) or the like.
  • the coating solution may further contain a softener, a stabilizer, a film forming agent, a thickener and the like.
  • the second covering layer 5b satisfies at least one of the following conditions 1 to 3.
  • the haze of the second covering layer 5b is 8% or less.
  • the surface roughness Ra of the second covering layer 5b is 1/2 or less of the thickness of the second covering layer 5b.
  • the number per unit area of concave portions having a diameter of 1.5 ⁇ m or more on the surface of the second covering layer 5b opposite to the first covering layer 5a is 2 pieces / 0.01 mm 2 or less.
  • Condition 1 specifies that the haze of the second covering layer 5b is 8% or less. When the haze is 8% or less, good oxygen barrier properties can be exhibited. From this point of view, the haze may be 6% or less or 4% or less.
  • Condition 2 specifies that the surface roughness Ra of the second covering layer 5b is equal to or less than half the thickness of the second covering layer 5b.
  • surface roughness Ra is below 1/2 of the thickness of the 2nd coating layer 5b, favorable oxygen barrier property can be expressed.
  • the surface roughness Ra of the second covering layer 5b may be 1/3 or less of the thickness of the second covering layer 5b, or may be 1/4 or less.
  • the surface roughness Ra of the second covering layer 5 b can be less than 0.1 ⁇ m, and may be 0.075 ⁇ m or less.
  • the lower limit of the surface roughness Ra of the second covering layer 5b is the thickness of the second covering layer 5b from the viewpoint that the second covering layer 5b may contain a certain amount or more (for example, 65 mass% or more) of the polyvalent metal compound. Can be 1/20 of the height or 0.01 .mu.m.
  • Condition 3 is that the number per unit area of concave portions having a diameter of 1.5 ⁇ m or more on the surface of the second covering layer 5b opposite to the first covering layer 5a side is 2 pieces / 0.01 mm 2 or less It is specified.
  • FIG. 2 is a schematic cross-sectional view of the second covering layer 5b, and in the surface 5f of the second covering layer 5b opposite to the first covering layer 5a, a recess 5d having a diameter X of 1.5 ⁇ m or more. Shows a formed state.
  • the oxygen barrier property of the gas barrier laminate 10 A is sufficiently reduced by heat treatment such as retort treatment or boiling treatment. It can be suppressed.
  • the number per unit area of the recess 5 d exceeds 2 pieces / 0.01 mm 2
  • the surface 5 f of the second covering layer 5 b becomes rough and uneven, and heat treatment is applied in the state of the package containing the contents. At this time, hydrogen sulfide generated from the contents easily passes through the second covering layer 5b to reach the first covering layer 5a.
  • the number per unit area of the concave portions 5d is more preferably 1 piece / 0.01 mm 2 or less, 0 piece / 0.01 mm Most preferably, it is 2 .
  • the number of recesses 5 d per unit area is measured by the following method. First, the surface 5f of the second covering layer 5b is observed by a scanning electron microscope (SEM), and a magnified image of a 0.1 mm ⁇ 0.1 mm field of view is taken. Count the number. Thus, the number (unit: number / 0.01 mm 2 ) per unit area of the recess 5 d having a diameter of 1.5 ⁇ m or more is obtained.
  • the planar shape of the recess 5d viewed from the direction perpendicular to the surface 5f of the second covering layer 5b may not be circular, and may be elliptical, polygonal, irregular, or two or more of these shapes. It may be a combined shape. When the planar shape of the recess 5 d is not circular, the diameter X of the recess 5 d means the maximum diameter in the shape.
  • the recess having a diameter of less than 1.5 ⁇ m on the surface 5f of the second covering layer 5b has a small influence on the oxygen barrier property, and the number thereof is not particularly limited.
  • the number per unit area of concave portions having a diameter of 1.0 ⁇ m or more on the surface 5f of the second covering layer 5b is two. 0.01 mm 2 or less, one /0.01Mm 2 or less, or is preferably zero /0.01mm 2.
  • the depth (maximum depth) Y of the recess 5 d having a diameter of 1.5 ⁇ m or more is not particularly limited, but is, for example, 50% or more of the thickness of the second covering layer 5 b.
  • the recess 5 d having such a depth has a great influence on the oxygen barrier property.
  • the number per unit area of recesses (diameter is not limited) having a depth of 50% or more of the thickness of the second covering layer 5b is 2 pieces / 0.01 mm 2 or less Is preferable, 1 / 0.01 mm 2 or less is more preferable, and 0 / 0.01 mm 2 is most preferable.
  • the oxygen barrier property of the gas barrier laminate 10A is more sufficiently reduced by heat treatment such as retort treatment or boiling treatment if the number per unit area of the recess having the depth is 2 pieces / 0.01 mm 2 or less. Can be suppressed.
  • the depth of the recess can be measured by, for example, a scanning probe microscope (SPM).
  • SPM scanning probe microscope
  • the method of forming the second covering layer 5b is adjusted Methods are included.
  • the coating solution containing the constituent components of the second covering layer 5b described above is coated on the surface of the first covering layer 5a by the gravure printing method.
  • Method is preferred. More specifically, it is preferable to use a cylinder whose surface is ceramic-coated as a cylinder (plate cylinder) used for gravure printing.
  • the ceramic-coated cylinder is excellent in wettability to the coating liquid, is easy to attach the coating liquid uniformly to the cylinder surface, and is easy to uniformly transfer the coating liquid to the first coating layer 5a. Therefore, the second covering layer 5b satisfying at least one of the conditions 1 to 3 can be easily formed.
  • the second covering layer 5b is formed thicker, for example, the haze and the surface roughness Ra become larger due to the nonuniformity of the thickness or the component, or the recess 5d is easily formed on the surface 5f.
  • the condition of the second covering layer 5 b is sufficiently thick, for example, within the range of 0.1 ⁇ m to 0.5 ⁇ m. It is possible to stably form the second covering layer 5b which satisfies at least one of 1 to 3.
  • the second covering layer 5b may satisfy two of the conditions 1 to 3, and may satisfy three.
  • FIG. 3 is a schematic plan view of the package.
  • FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG.
  • the package 40 is composed of a package 30 and contents 42 contained in the package 30.
  • the package 30 is a sheet (packaging film) 20 formed into a bag shape.
  • the sheet 20 includes a gas barrier laminate 10A, an adhesive layer 21 located on the second covering layer 5b, and a sealant layer 22 located on the adhesive layer 21.
  • the adhesion layer 21 is a layer for adhering the gas barrier laminate 10A and the sealant layer 22.
  • the sealant layer 22 is a layer for fusing a part of the sheets 20 stacked so that the sealant layers 22 face each other.
  • the adhesive layer 21 contains, for example, linear low density polyethylene (LLDPE), polyurethane, polypropylene, an ethylene-unsaturated ester copolymer resin, or a polyester copolymer resin.
  • the sealant layer 22 is a resin layer to be the inner surface of the package 30, and is, for example, an unstretched polypropylene film (CPP film).
  • the thickness of the adhesive layer 21 is, for example, 1 ⁇ m to 5 ⁇ m, and the thickness of the sealant layer is, for example, 10 ⁇ m to 100 ⁇ m.
  • the adhesive layer 21 is formed, for example, by being applied on the second covering layer 5b.
  • the sealant layer 22 is formed, for example, by applying on the adhesive layer 21.
  • the package 30 is formed into a bag shape by heat-sealing an end portion after folding the sheet 20 in two.
  • the outer surface 30 a of the package 30 is made of the resin base 1, and the inner surface 30 b of the package 30 is made of the sealant layer 22. From the outside to the inside of the package 30, the resin base 1, the base layer 2, the inorganic deposited layer 3, the first covering layer 5a, the second covering layer 5b, the adhesive layer 21 and the sealant layer 22 are laminated in this order ing.
  • the package 30 has a main body portion 30c in which the contents 42 are accommodated, a fusion spliced portion 30d positioned at an edge of the main body portion 30c, and a bent portion 30e in which the sheet 20 is bent.
  • the main body portion 30c is a region Rc shown in FIG. 4, and the fusion bonded portion 30d is a region Rd shown in FIG.
  • Contents 42 include, for example, liquid L and solid S.
  • the liquid L is, for example, water, oil, soft drink, alcoholic drink, organic solvent and the like.
  • the solid S is meats, beans and the like containing sulfur-containing amino acids. Sulfur-containing amino acids are, for example, methionine and cysteine.
  • Cysteine is, for example, L-cysteine (2-amino-3-sulfanyl propionic acid: HSCH 2 CH (NH 2 ) COOH) and is represented by the following formula (1).
  • the fusion bonded portion 30d is a portion where a part of the sheet 20 and the other part are heated and compressed. As a result, in the fusion-bonded portion 30d, the resins of the opposing sealant layer 22 melt and mix and thermally fuse.
  • the package 40 may be one that has been subjected to retort processing or boiling processing. Thereby, since the said crosslinked structure is formed in the 1st coating layer 5a, and the formed crosslinked structure remains without being destroyed, the oxygen barrier property by the gas barrier laminate 10A is exhibited favorably.
  • FIGS. 5 (a) to 5 (d) are schematic views for explaining the change of the gas barrier laminate at the time of performing the retort treatment.
  • 6 (a) and 6 (b) are schematic diagrams for explaining the change of the package at the time of execution of retort processing.
  • this retort process it was assumed that each of the gas barrier laminate 10A and the package 40 was heated by steam at 125 ° C. for 30 minutes. The resin base 1 side of the gas barrier laminate 10A was exposed to water vapor. Further, in FIG.
  • R-COOH refers to the carboxylic acid-based polymer
  • R-COO - indicates a carboxylic acid polymer in which the hydrogen ions are released from the carboxy group
  • MO x represents a polyvalent metal compound
  • M y + represents a polyvalent metal ion
  • R-COO-M-OOC-R represents a crosslinked structure of a carboxylic acid-based polymer through a polyvalent metal ion Indicates
  • the oxygen barrier property in the first covering layer 5a is improved by the chemical reaction between the carboxylic acid-based polymer and the polyvalent metal compound during retort treatment.
  • the polyvalent metal compound remaining in the second covering layer 5b exhibits a retort odor absorbing action. Therefore, by performing, for example, retort treatment on the gas barrier laminate 10A, the gas barrier laminate 10A exhibits a retort odor suppression action and good oxygen barrier properties.
  • Hydrogen sulfide passes through the sealant layer 22 and the adhesive layer 21 and enters the gas barrier laminate 10A from the second covering layer 5b side.
  • the hydrogen sulfide which has entered the second covering layer 5b chemically reacts with the polyvalent metal compound contained in the second covering layer 5b.
  • polyvalent metal sulfide is generated in the second covering layer 5b, and hydrogen sulfide is trapped in the second covering layer 5b. Therefore, according to the package 40 using the gas barrier laminate 10A, retort odor can be suppressed.
  • the ratio of the thickness of the second covering layer 5b to the thickness of the first covering layer 5a is 1.0 or more and 4.0 or less, and the second covering layer 5b has the conditions 1 to 3 Meet at least one.
  • the invading hydrogen sulfide may reach the first covering layer 5a, most of the hydrogen sulfide is captured by the second covering layer 5b, so that the sulfur element is contained in the first covering layer 5a after the retort treatment.
  • the rate can be very low (e.g., below 1.0 atm%). Thereby, it can suppress that the said crosslinked structure in the 1st coating layer 5a is destroyed by a sulfur ion. Therefore, even when hydrogen sulfide is generated from the contents 42, the oxygen barrier property of the gas barrier laminate 10A is sufficiently exhibited.
  • the thickness of the second covering layer 5 b is 0.10 ⁇ m or more and 0.50 ⁇ m or less. Therefore, the second covering layer 5b can contain a sufficient amount of polyvalent metal compound. Moreover, the flexible fall of the 2nd coating layer 5b can be suppressed favorably.
  • the polyvalent metal compound is zinc oxide, and the content of zinc oxide is 65% by mass or more and 85% by mass or less based on the mass of the second covering layer 5b. For this reason, it is possible to provide the gas barrier laminate 10A capable of achieving both suppression of retort odor and oxygen barrier properties while exhibiting light transparency.
  • the first covering layer 5a after the retort treatment, has a crosslinked structure in which carboxylic acid polymers are crosslinked via polyvalent metal ions. For this reason, the oxygen barrier property by the 1st coating layer 5a is exhibited favorably.
  • the gas barrier laminate 10A is provided between the resin substrate 1 and the inorganic vapor deposition layer 3 and includes the underlayer 2 containing a urethane compound. For this reason, peeling of the resin base material 1 and the inorganic vapor deposition layer 3 is suppressed.
  • the contents include, but are not limited to, both liquid and solid.
  • the contents may contain only liquid or solid.
  • the liquid contains a sulfur-containing amino acid.
  • the package 30 may contain liquid, semi-solid or gel-like contents. That is, the package 30 may contain a substance that can exert surface tension, such as a liquid.
  • Specific examples of the contents include food such as water, oil, drink, yogurt, jelly, curry, curry, pudding, syrup, jam, mousse, rice cake or soup, medicine, cosmetics, chemicals and the like.
  • the package 30 may contain, for example, sterile hygiene products, medical products, solid food products and the like.
  • the gas barrier laminate 10A includes the underlayer 2, but is not limited thereto. That is, the gas barrier laminate may not include the underlayer 2. Further, in the gas barrier laminate, a modified layer formed by subjecting the first surface 1 a of the resin substrate 1 to reactive ion etching (hereinafter also referred to as “RIE”) instead of the underlayer 2 is performed. You may have.
  • the modification treatment layer refers to a portion in which the vicinity of the surface of the resin substrate 1 is in the form of being reformed into a layer by the RIE treatment.
  • a gas barrier laminate 10B shown in FIG. 7 includes a modified layer 1R between the resin base 1 and the inorganic vapor deposition layer 3.
  • Plasma is used for the RIE process.
  • the chemical effect of imparting a functional group to the surface of the resin substrate 1 can be obtained by radicals or ions generated in the plasma.
  • a physical effect of increasing surface roughness can also be obtained. Therefore, the adhesion between the resin base material 1 and the inorganic vapor deposition layer 3 is improved by the modified treatment layer in which the above-mentioned chemical effect and the above-mentioned physical effect are expressed by the RIE process, and even under high temperature and high humidity environment. Peeling between the resin substrate 1 and the inorganic vapor deposition layer 3 is less likely to occur.
  • the heat resistance of the entire gas barrier laminate is improved, and the occurrence of delamination between the resin substrate 1 and the inorganic vapor deposition layer 3 or the gas barrier when heat treatment such as boiling treatment, retort treatment, heating cooking, etc. is performed. Deterioration of the sex is suppressed.
  • the RIE process to the resin base material 1 can be implemented using a well-known thing as a RIE type plasma processing apparatus.
  • a plasma processing apparatus a winding-type in-line plasma processing apparatus is preferable.
  • a take-up type in-line plasma processing apparatus a planar type plasma processing apparatus, a hollow anode type plasma processing apparatus, or the like can be used.
  • a planar plasma processing apparatus 50A shown in FIG. 8 includes an electrode (cathode) 51 and a cylindrical processing roll 52 for holding the resin substrate 1 in a vacuum chamber, and the electrode 51 is disposed inside the processing roll 52. It is done.
  • the gas of the method of performing RIE processing is introduced to the outside of the processing roll 52 and a voltage is applied to the electrode 51 while conveying the resin base 1 along the processing roll 52, plasma is generated outside the processing roll 52, The radicals in the plasma are attracted to the processing roll side which is the counter electrode, and act on the surface of the resin substrate 1.
  • the resin base 1 is disposed on the side of the electrode 51 which is a cathode, a high self bias is obtained on the resin base 1, and ions I in the plasma are on the resin base 1 side by this high self bias. Is attracted to the surface of the resin base material 1 and a sputtering action (physical action) is exerted to carry out the RIE treatment.
  • plasma treatment is performed by an apparatus in which the electrode 51 for applying a voltage is disposed outside the treatment roll 52, the resin base 1 is disposed on the anode side. In this case, a high self bias can not be obtained, and only radicals act on the resin substrate 1.
  • the action of the radical is only a chemical reaction, and the adhesion between the resin substrate 1 and the inorganic vapor deposition layer 3 can not be sufficiently improved only by the chemical reaction.
  • the hollow anode type plasma processing apparatus 50B shown in FIG. 9 holds the electrode (anode) 51 and the resin substrate 1 in a vacuum chamber, and matches the impedance with the processing roll 52 functioning as the counter electrode (cathode) of the electrode 51. And a gas introduction nozzle 55, and shielding plates 57 disposed at both ends of the electrode 51.
  • the electrode 51 is in the form of a box having an opening on the processing roll 52 side.
  • a gas introduction nozzle 55 is disposed above the electrode 51 so that a gas for performing the RIE process can be introduced into the gap between the electrode 51 and the shield plate 57 and the processing roll 52.
  • the matching box 56 is disposed on the back of the electrode 51 and connected to the electrode 51.
  • the shielding plate 57 has a phase shape along the outer periphery of the processing roll 52, and is disposed outside the processing roll 52 so as to face the processing roll 52.
  • the area (Sa) of the electrode 51 is larger than the area (Sc) of the treated surface of the resin base material 1 serving as the counter electrode, that is, the size of the opening of the electrode (A) Sa> Sc).
  • Gas is introduced into the gap between the electrode 51 and the shielding plate 57 of the hollow anode type plasma processing apparatus 50B and the processing roll 52, and the electrode from the matching box 56 is conveyed while the resin base 1 is transported along the processing roll 52.
  • a voltage is applied to 51, plasma is generated inside the box-shaped electrode 51, and radicals in the plasma are attracted to the side of the processing roll 52, which is the counter electrode, and act on the surface of the resin substrate 1.
  • Sa> Sc a high self bias is generated on the resin base 1, and ions I in the plasma are attracted to the resin base 1 by the high self bias, and the surface of the resin base 1 is obtained.
  • the sputtering action (physical action) works on the surface, and the RIE process is performed.
  • the hollow anode type plasma processing apparatus may further be a magnetic assist holo-anode type plasma processing apparatus in which a magnet is incorporated in a box-shaped electrode to form a self-recording electrode.
  • the magnetic field generated from the magnetic electrode can further enhance the plasma confinement effect and obtain high ion current density with large self-bias. This makes it possible to perform stronger and stable RIE processing at high speed.
  • argon, oxygen, nitrogen, and hydrogen can be used as gas species for performing the RIE process. These gases may be used alone or in combination of two or more.
  • two or more plasma processing apparatuses do not have to use the same one.
  • the resin base material 1 can be treated with a planar type plasma treatment apparatus, and then the treatment can be performed continuously using a hollow anode type plasma treatment apparatus.
  • the contact bonding layer 21 is in contact with the 2nd coating layer 5b, it is not restricted to this.
  • an intermediate layer may be provided between the adhesive layer 21 and the second cover layer 5b.
  • a print layer may be provided on the second covering layer 5b.
  • the print layer contains, for example, a paint for indicating characters, figures and the like, and a transparent resin.
  • the first coating layer 5a has a crosslinked structure of the carboxylic acid-based polymer through polyvalent metal ions, but the present invention is not limited thereto.
  • the first covering layer 5a may have the above-described crosslinked structure before retort treatment is performed. In this case, even if retort treatment is not performed, the gas barrier laminate exhibits excellent oxygen barrier properties.
  • a gas barrier laminate 10C according to a second embodiment shown in FIG. 10 is formed by sequentially laminating an adhesion layer 2A, an inorganic vapor deposition layer 3 and a covering layer 6 on a plastic substrate 1A (film substrate).
  • the adhesion layer 2A and the inorganic vapor deposition layer 3 are not essential, and layers having other functions may be laminated as needed.
  • functional layers such as a surface protective layer, a sealant layer, and a picture layer may be laminated. These functional layers may be a single layer or a combination of multiple layers.
  • FIG. 11 is a modification of the gas barrier laminate 10C according to the second embodiment shown in FIG.
  • a gas barrier laminate 10D shown in FIG. 11 is a reformed layer 1R, an inorganic vapor deposition layer 3 and a covering layer 6 formed by reactive ion etching (hereinafter also referred to as "RIE") treatment on a plastic substrate 1A.
  • RIE reactive ion etching
  • the RIE process may be performed using the above-described planar type plasma processing apparatus 50A and / or the hollow anode type plasma processing apparatus 50B (see FIGS. 8 and 9).
  • layers having other functions may be stacked as necessary.
  • functional layers such as a surface protective layer, a sealant layer, and a picture layer may be laminated. These functional layers may be a single layer or a combination of multiple layers.
  • the plastic base material 1A may be subjected to various pretreatments such as corona treatment and flame treatment on the laminated surface without impairing the barrier performance.
  • the plastic substrate 1A is not particularly limited, and any known material may be used as long as it is transparent and maintains its form even at a heating temperature of 200 ° C. or higher.
  • polyester-based films polyethylene terephthalate, polyethylene naphthalate etc.
  • polyamide-based films nylon-6, nylon-66 etc.
  • polystyrene-based films polyvinyl chloride-based films
  • polyimide-based films polycarbonate-based films
  • a film having a low thermal shrinkage is preferred.
  • the thickness of the film is not particularly limited. Depending on the application, those of about 6 ⁇ m to 200 ⁇ m can be used.
  • the plastic base material 1A may be provided with various pretreatments such as corona treatment, plasma treatment, and flame treatment, and coat layers such as an easy adhesion layer on the laminated surface without impairing the barrier performance.
  • the adhesion layer 2A is provided on the plastic substrate 1A, and the adhesion performance between the plastic substrate 1A and the inorganic vapor deposition layer 3 is improved, and the surface is smoothed to make the inorganic vapor deposition layer in the next step uniform without defects.
  • the object is to obtain two effects of forming a film and further assisting a minute barrier defect of a deposited film to express high barrier performance.
  • non-aqueous resin for example, a silane coupling agent, organic titanate, polyacryl, polyester, polyurethane, polycarbonate, polyurea, polyamide, polyolefin emulsion, polyimide, melamine, A phenol etc. are mentioned. It is more preferable that an organic polymer having at least one or more of a urethane bond and a urea bond is included, in consideration of the heat resistance water resistance of the adhesive layer.
  • polyols such as acrylic and methacrylic polyols and isocyanate compounds having an isocyanate group, or amine resins having an amino group, an epoxy group and a glycidyl group It may be one having a urethane bond formed by reacting an epoxy compound etc., or one having a urea bond by reaction of an isocyanate compound with a solvent such as water or ethyl acetate, or an amine resin having an amino group.
  • the adhesion layer of the non-aqueous resin is more preferably a composite of an acrylic polyol, a polyester polyol, an isocyanate compound, a silane coupling agent and the like.
  • An acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and another monomer, which has a hydroxyl group at an end. And the isocyanate group of the isocyanate compound to be added later.
  • Polyester polyols are terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, Acid raw materials such as hexahydrophthalic acid and reactive derivatives thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, Inner end of polyester resin obtained by known method from alcohol raw materials such as neopentyl glycol, bishydroxyethyl terephthalate, trimethylolmethane, trimethylolpropane, glycerin and pentaerythritol Those having 2 or more hydroxyl groups, are those which react with the is
  • An isocyanate compound is added to enhance adhesion to a substrate or an inorganic oxide by a urethane bond formed by reaction with an acrylic polyol and a polyester polyol, and mainly acts as a crosslinking agent or a curing agent.
  • monomers such as aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI) and hexylene diisocyanate (HMDI); These polymers and derivatives are used, and they may be used alone or as a mixture.
  • silane coupling agent a silane coupling agent containing any organic functional group
  • silane coupling agents such as methoxysilane, glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane or their hydrolysates
  • methoxysilane glycidoxypropyltrimethoxysilane
  • ⁇ -methacryloxypropyltrimethoxysilane ⁇ -methacryloxypropylmethyldimethoxysilane or their hydrolysates
  • the cast method used normally, the dipping method, the roll coating method, the gravure coating method, the screen printing method, the reverse coating method, the spray coating method, the kit coating method, the die coating method, the metal ring bar coating It is possible to use conventionally known methods such as a chamber doctor combined coating method and a curtain coating method.
  • the inorganic vapor deposition layer 3 uses aluminum oxide (AlOx), silicon oxide (SiOx), magnesium fluoride (MgF 2 ), magnesium oxide (MgO) or indium-tin oxide (ITO) as a material having high barrier properties.
  • AlOx aluminum oxide
  • SiOx silicon oxide
  • MgF 2 magnesium fluoride
  • MgO magnesium oxide
  • ITO indium-tin oxide
  • Aluminum oxide or silicon oxide which is an inorganic oxide is preferable in terms of material cost, barrier performance and transparency.
  • the thickness of the inorganic vapor deposition layer 3 is less than 10 nm, there is a problem in the continuity of the thin film, and if it exceeds 300 nm, curling and cracking easily occur, which adversely affects the barrier performance and reduces flexibility. Is from 20 nm to 200 nm. The thickness may be set as appropriate depending on the application.
  • the inorganic vapor deposition layer 3 can be deposited by vacuum deposition means. It is preferable from the viewpoint of barrier performance and film uniformity.
  • the film forming means there are known methods such as a vacuum vapor deposition method, a sputtering method, a chemical vapor deposition method (CVD method), and the vacuum vapor deposition method is preferable because the film forming speed is high and the productivity is high.
  • film forming means by electron beam heating is effective because it is easy to control the film forming speed by the irradiation area, electron beam current, etc. and temperature rise / drop to the deposition material can be performed in a short time. is there.
  • the covering layer 6 includes the following first covering layer 6 a and a second covering layer 6 b containing a polyvalent metal compound.
  • the first coating layer 6a comprises a polycarboxylic acid-based polymer (A1) (hereinafter referred to as "component (A1)”), a silane coupling agent represented by the following general formula (1), a hydrolyzate thereof, and condensation thereof. And a weight ratio of 99.5: 0.5 to 80.0: 20.0 with at least one silicon-containing compound (A2) (hereinafter referred to as “component (A2)”) selected from the group consisting of The mass of the component (A2) is the mass in terms of the silane coupling agent.
  • R 1 Si (OR 2 ) 3 (1) In Formula (1), R 1 is a glycidyloxy group or an organic group containing an amino group, R 2 is an alkyl group, and three R 2 s may be the same or different. ]
  • the first covering layer 6a When most of the carboxy groups of the component (A1) in the first covering layer 6a do not form ionic crosslinks, the first covering layer 6a is flexible. Therefore, when abuse such as stretching is applied, the first covering layer 6a is less likely to have a defect. Therefore, when the gas barrier laminate is subjected to at least one treatment selected from the group consisting of retort treatment, boiling treatment and humidity control treatment after the abuse, the gas barrier property is unlikely to be deteriorated. In addition, when the second covering layer 6b is provided together with the first covering layer 6a, the first covering layer 6a is subjected to at least one process selected from the group consisting of retort treatment, boiling treatment and humidity control treatment.
  • Component (A1) and the polyvalent metal compound contained in the second coating layer 6b react, and the carboxy group of the component (A1) forms an ionic crosslink with the polyvalent metal ion, resulting in excellent gas barrier properties. It can be set as the gas barrier laminate which it has.
  • the polycarboxylic acid-based polymer of the component (A1) is a polymer having two or more carboxy groups in the molecule.
  • the component (A1) include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid, carboxymethylcellulose, pectin And acid polysaccharides having a carboxyl group in the molecule.
  • the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • Examples of the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid include, for example, saturated carboxylic acid vinyl esters such as ethylene, propylene and vinyl acetate, alkyl acrylates, alkyl methacrylates, alkyl itaconate And vinyl chloride, vinylidene chloride, styrene, acrylamide, acrylonitrile and the like. These polycarboxylic acid polymers may be used alone or in combination of two or more.
  • a polymer containing a structural unit derived from a polymerizable monomer is preferable, and a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid
  • the proportion of a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid is preferably 80 mol% or more. And 90 mol% or more is more preferable (however, the total of all structural units constituting the polymer is 100 mol%).
  • the polymer may be a homopolymer or a copolymer.
  • the other structural unit may be, for example, an ethylenically unsaturated singlet copolymerizable with the above-mentioned ethylenically unsaturated carboxylic acid.
  • Constituent units derived from mer and the like can be mentioned.
  • the number average molecular weight of the component (A1) is preferably in the range of 2,000 to 10,000,000, and more preferably 5,000 to 1,000,000. If the number average molecular weight is less than 2,000, the resulting gas barrier laminate can not achieve sufficient water resistance, and the gas barrier properties and transparency may be deteriorated by water, or whitening may occur. On the other hand, when the number average molecular weight exceeds 10,000,000, when forming the layer (A) by coating, the viscosity may be increased and the coatability may be impaired.
  • part of the carboxy groups may be previously neutralized with a basic compound. Water resistance and heat resistance can be further improved by neutralizing in advance a part of the carboxy group of the component (A1).
  • the basic compound is preferably at least one basic compound selected from the group consisting of polyvalent metal compounds, monovalent metal compounds and ammonia.
  • the polyvalent metal compound include the same as the polyvalent metal compounds mentioned in the description of the second covering layer 6b.
  • Examples of the basic compound which is a polyvalent metal compound include zinc oxide, calcium carbonate, sodium carbonate and the like. Can be mentioned.
  • Examples of the basic compound which is a monovalent metal compound include sodium hydroxide and potassium hydroxide.
  • the coating It is preferable that it is 30 mol% or less from a viewpoint of the coating property of a liquid (a), or coating liquid stability, and it is more preferable that it is 25 mol% or less.
  • the component (A1) one type may be used alone, or two or more types may be mixed and used.
  • the component (A2) is a group comprising a silane coupling agent represented by the following general formula (1) (hereinafter sometimes referred to as "silane coupling agent (1)”), its hydrolyzate and condensates thereof And at least one silicon-containing compound selected from The component (A2) improves the adhesion between the inorganic vapor deposition layer 3 and the first covering layer 6a even in a small amount, and improves the heat resistance, water resistance and the like.
  • R 1 Si (OR 2 ) 3 (1) [In Formula (1), R 1 is a glycidyloxy group or an organic group containing an amino group, R 2 is an alkyl group, and three R 2 s may be the same or different. ]
  • Examples of the organic group in R 1 in the general formula (1) include a glycidyloxyalkyl group, an aminoalkyl group and the like.
  • the alkyl group for R 2 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
  • Specific examples of the silane coupling agent (1) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane. It can be mentioned. Among these, ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -aminopropyltrimethoxysilane are preferable.
  • the component (A2) may be the silane coupling agent (1) itself, may be a hydrolyzate obtained by hydrolyzing the silane coupling agent (1), or may be a condensate thereof.
  • the hydrolyzate one in which at least one of the three OR 2 in the general formula (1) is OH is mentioned.
  • the condensate include those in which Si—OH of at least two molecules of hydrolyzate is condensed to form a Si—O—Si bond.
  • what the hydrolyzate of the silane coupling agent condensed may be described as a hydrolysis condensation product.
  • the component (A2) for example, those obtained by performing a hydrolysis and condensation reaction of the silane coupling agent (1) using a sol-gel method can be used.
  • the silane coupling agent (1) is easily hydrolyzed and the condensation reaction easily occurs in the presence of an acid or alkali, so only the silane coupling agent (1), its hydrolyzate alone, or It is rare that these condensates exist alone. That is, the component (A2) usually contains the silane coupling agent (1), its hydrolyzate, and a condensate thereof.
  • hydrolyzate includes partially hydrolyzate and completely hydrolyzate.
  • the component (A2) preferably contains at least a hydrolytic condensate.
  • the silane coupling agent (1) may be directly mixed with the liquid containing the above-mentioned component (A1) and water, and the silane coupling agent (1) may be mixed with water.
  • the hydrolysis and the subsequent condensation reaction may be carried out to obtain a hydrolytic condensate prior to mixing with the polycarboxylic acid polymer.
  • the first covering layer 6a contains the component (A1) and the component (A2) in a mass ratio of 99.5: 0.5 to 80.0: 20.0.
  • the mass of (A2) component is a mass of said silane coupling agent (1) conversion. That is, as described above, the component (A2) usually contains the silane coupling agent (1), the hydrolyzate thereof, and the condensate thereof, but the mass of the component (A2) is the silane coupling agent ( It is the value converted into 1), that is, the preparation amount of the silane coupling agent (1).
  • the gas barrier laminate which is excellent in abuse resistance can be obtained as this mass ratio is the above-mentioned range.
  • the 1st coating layer 6a can be made into a uniform layer without phase separation by containing (A2) component in the said range.
  • the presence of the component (A2) makes the gas barrier laminate resistant to an acid.
  • R 1 is an organic group containing a glycidyloxy group ( ⁇ -glycidoxypropyltrimethoxysilane or ⁇ -glycidoxypropyltriethoxysilane) as the silane coupling agent (1)
  • the mass ratio of the component (A1) to the component (A2) is preferably 99.5: 0.5 to 90.0: 10.0, and 99.0: 1.0 to 95.0: 5. It is particularly preferred that it is 0.
  • component (A1) and The mass ratio to the component (A2) is preferably 99.0: 1.0 to 80.0: 20.0, and 95.0: 5.0 to 80.0: 20.0. Particularly preferred.
  • the first coating layer 6a may contain various additives.
  • a plasticizer a resin, a dispersant, a surfactant, a softener, a stabilizer, an antiblocking agent, a film forming agent, an adhesive, an oxygen absorbent and the like can be mentioned.
  • a plasticizer it is possible to select and use suitably from well-known plasticizers.
  • plasticizer for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol
  • polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene oxide, sorbitol, mannitol, dulcitol, erythritol, glycerin, lactic acid, fatty acid, starch, phthalic ester and the like can be exemplified.
  • polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, glycerin and starch are preferable from the viewpoint of stretchability and gas barrier property.
  • the additive contains a compound having two or more hydroxyl groups such as polyvinyl alcohol, the hydroxyl group of the compound and a part of the carboxy group of the component (A1) may form an ester bond.
  • the mass ratio of the component (A1) to the additive ((A1) component: additive) is usually 70:30 to 99.9: 0.1. In the range of 80:20 to 98: 2.
  • the thickness of the first covering layer 6a is preferably in the range of 0.01 to 5 ⁇ m, more preferably in the range of 0.02 to 3 ⁇ m, and still more preferably in the range of 0.04 to 1 from the viewpoint of gas barrier properties. It is in the range of 2 ⁇ m.
  • the preferable thickness of the sum total of the layer (A) in a coating layer is the same as the above.
  • the first covering layer 6a can usually be formed by a coating method. Specifically, it can be formed by drying a coating film composed of a coating liquid (a) containing the (A1) component and the (A2) component. As the (A1) component and the (A2) component contained in the coating liquid (a), the same as those described above can be used.
  • the coating solution (a) has a mass ratio of 99.5: 0.5 to 80.0: 20.0 between the components (A1) and (A2) (however, the mass of the component (A2) is the silane) It is preferable to contain by coupling agent (1) conversion mass. The preferred reason is the same as above.
  • R 1 is an organic group containing a glycidyloxy group ( ⁇ -glycidoxypropyltrimethoxysilane or ⁇ -glycidoxypropyltriethoxysilane) as the silane coupling agent (1)
  • the mass ratio of the component A1 to the component (A2) is preferably 99.5: 0.5 to 90.0: 10.0, and 99.0: 1.0 to 95.0: 5.0. Is particularly preferred.
  • component (A1) and The mass ratio to the component (A2) is preferably 99.0: 1.0 to 80.0: 20.0, and 95.0: 5.0 to 80.0: 20.0. Particularly preferred.
  • the mass ratio of the component (A1) to the component (A2) contained in the coating solution (a) and the component (A1) in the layer (A) formed using the coating solution (a) is the same as that of the component (A2), but is different, for example, when the component (A1) and the additive react, or when the component (A1) and the component (A2) react, etc. There is.
  • the coating liquid (a) may contain the additive described above, in addition to the components (A1) and (A2), as necessary.
  • the preferable range of the mass ratio of the component (A1) to the additive is the same as described above.
  • the coating liquid (a) can be prepared by mixing the (A1) component, the (A2) component, and the additive optionally contained with a solvent.
  • the solvent used for the coating liquid (a) is not particularly limited as long as it can dissolve the components (A1) and (A2), but usually, the hydrolysis reaction of the silane coupling agent (1) is carried out Water, a mixed solvent of water and an organic solvent, and the like are preferable. Water is most preferable in terms of the solubility of the component (A1) and the cost.
  • organic solvent such as alcohol is preferable in terms of improving the solubility of the silane coupling agent (1) and the coating property of the coating liquid (a).
  • organic solvent at least one organic solvent selected from the group consisting of alcohols having 1 to 5 carbon atoms and ketones having 3 to 5 carbon atoms is preferably used. Specific examples of such organic solvents include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone and the like.
  • a mixed solvent of water and an organic solvent the above-mentioned mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and an alcohol having 1 to 5 carbon atoms is more preferable.
  • a mixed solvent water is present in an amount of 20 to 95% by mass, and an organic solvent is present in an amount of 80 to 5% by mass (provided that the total of water and the organic solvent is 100% by mass). preferable.
  • the (solid content) is preferably 0.5 to 50% by mass, more preferably 0.8 to 30% by mass, and particularly preferably 1.0 to 20% by mass, with respect to the total weight of the coating liquid (a).
  • the coating liquid (a) is applied to the surface on which the first coating layer 6a is to be laminated (for example, on the inorganic vapor deposition layer 3) to form a coating film, and the coating film is dried to form the first coating layer 6a.
  • the coating method of the coating liquid (a) is not particularly limited, and can be appropriately selected from known coating methods. For example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method Spray coating method, kit coating method, die coating method, metalling bar coating method, chamber doctor combined coating method, curtain coating method and the like.
  • the coating amount of the coating liquid (a) is set according to the thickness of the first coating layer 6 a to be formed.
  • the first coating layer 6a is formed by removing the solvent of the coating liquid (a) contained in the coating film by drying.
  • the drying method is not particularly limited, and examples thereof include methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Any of these methods may be used alone or two or more may be combined.
  • the first coating layer 6a formed in this manner contains the (A1) component and the (A2) component, and the coating liquid (a) further contains other components such as additives, etc. ,
  • the other ingredients are included.
  • a compound having two or more hydroxyl groups such as polyvinyl alcohol is used as an additive for the coating solution (a)
  • the hydroxyl group of the compound and the carboxy group of the component (A1) during the above drying, aging treatment, heat treatment, etc. May react with a portion of to form an ester bond.
  • the second covering layer 6b contains a polyvalent metal compound.
  • the polyvalent metal compound is a compound of a polyvalent metal having a metal ion valence of 2 or more.
  • examples of polyvalent metals include alkaline earth metals such as beryllium, magnesium and calcium; transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc and the like; aluminum and silicon.
  • As the polyvalent metal calcium or zinc is particularly preferable from the viewpoint of heat resistance, water resistance, and transparency. That is, as a polyvalent metal compound, a calcium compound or a zinc compound is preferable.
  • polyvalent metal compounds include simple substances of polyvalent metals, oxides, hydroxides, carbonates, organic acid salts (eg, acetates) or inorganic acid salts, ammonium complexes of polyvalent metal oxides or And quaternary amine complexes, or their carbonates or organic acid salts.
  • zinc oxide, aluminum oxide, calcium hydroxide, calcium carbonate, zinc acetate and calcium acetate are preferable, and zinc oxide is particularly preferable.
  • the coating film which consists of a coating liquid (b) containing a polyvalent metal compound
  • a polyvalent metal compound even if the form of a polyvalent metal compound is particulate form, it is non-particulate form
  • it is preferably in the form of particles from the viewpoint of dispersibility, gas barrier property and productivity.
  • the average particle size of such particles is not particularly limited, but from the viewpoint of gas barrier properties and coating suitability, the average particle size is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and 0.1 ⁇ m or less Is particularly preferred.
  • the second covering layer 6b may contain various additives in addition to the polyvalent metal compound, as needed, as long as the effects of the present invention are not impaired.
  • the additive for example, when the layer (B) is formed by drying a coating film made of a coating solution (b) containing a polyvalent metal compound, it is soluble in the solvent used for the coating solution (b) Alternatively, it may contain a dispersible resin, a dispersant soluble or dispersible in the solvent, a surfactant, a softener, a stabilizer, a film forming agent, a thickener and the like. Among the above, it is preferable to contain a resin that is soluble or dispersible in the solvent used for the coating liquid (b).
  • a coating liquid (b) and film forming property improve.
  • resin examples include alkyd resin, melamine resin, acrylic resin, urethane resin, polyester resin, phenol resin, amino resin, fluorine resin, epoxy resin, isocyanate resin and the like.
  • a dispersant that is soluble or dispersible in the solvent used for the coating liquid (b).
  • the dispersant an anionic surfactant or a nonionic surfactant can be used.
  • the surfactant includes (poly) carboxylates, alkyl sulfates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, aromatics Phosphate ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, alkyl allyl sulfate ester salt, polyoxyethylene alkyl phosphate ester, sorbitan alkyl ester, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid Ester, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan alkyl ester, polyoxyethylene alkyl allyl ether, polyoxy Styrene derivatives, polyoxyethylene sorbitol fatty acid esters, polyoxy fatty
  • the mass ratio of the polyvalent metal compound to the additive is 30:70 to 99: 1. It is preferably in the range of 50:50 to 98: 2.
  • the thickness of the second covering layer 6b is preferably in the range of 0.01 to 5 ⁇ m, more preferably in the range of 0.03 to 3 ⁇ m, and still more preferably 0.1 to 1. It is in the range of 2 ⁇ m. Even when the covering layer includes a plurality of second covering layers 6b, the preferable total thickness of the second covering layers 6b in the covering layers is the same as described above.
  • Method of forming second covering layer 6b examples include a coating method, a dipping method, and the like. Among these, the coating method is preferable from the viewpoint of productivity. Hereinafter, the case of forming the second covering layer 6b by the coating method will be described.
  • the formation of the second covering layer 6b by the coating method can be formed by drying a coating film made of the coating liquid (b) containing a polyvalent metal compound.
  • a polyvalent metal compound contained in a coating liquid (b) the thing similar to the above can be used, a calcium compound or a zinc compound is preferable, and a zinc compound is especially preferable.
  • the coating liquid (b) may contain various additives and the like in addition to the polyvalent metal compound, as needed, as long as the effects of the present invention are not impaired.
  • the additive for example, a resin soluble or dispersible in a solvent used for the coating liquid (b), a dispersant soluble or dispersible in the solvent, another surfactant, a softener, a stabilizer, a film A forming agent, a thickener, etc. are mentioned.
  • the coating liquid (b) is mixed with a resin soluble or dispersible in the solvent used for the coating liquid (b) for the purpose of improving the coating property and film forming property of the coating liquid (b). It is preferable to use it.
  • As such resin the thing similar to what was mentioned as various additives which the above-mentioned 2nd coating layer 6b may contain is mentioned.
  • the coating liquid (b) contains an additive, the mass ratio of the polyvalent metal compound to the additive (polyvalent metal compound: additive) is in the range of 30:70 to 99: 1. It is preferable that the ratio be in the range of 50:50 to 98: 2.
  • a solvent used for the coating liquid (b) for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide And toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate and butyl acetate.
  • these solvents may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone and water are preferable from the viewpoint of coatability. Further, from the viewpoint of manufacturability, methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable.
  • the layer (A) formed from a coating liquid (a) is excellent in water resistance, water can be used as a solvent used for a coating liquid (b).
  • the total content of the polyvalent metal compound and the additive in the coating liquid (b) is 1 to 50% by mass based on the total weight of the coating liquid (b) from the viewpoint of coating suitability.
  • the range of 3 to 45% by mass is more preferable, and the range of 5 to 40% by mass is particularly preferable.
  • the coating liquid (b) is applied to the surface (for example, the first covering layer 6a etc.) on which the second covering layer 6b is laminated to form a coating, and the coating is dried to form the second covering layer 6b.
  • the coating method of the coating liquid (b) is not particularly limited, and can be appropriately selected from known coating methods. For example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method Spray coating method, kit coating method, die coating method, metalling bar coating method, chamber doctor combined coating method, curtain coating method and the like.
  • the coating amount of the coating liquid (b) is set according to the thickness of the second coating layer 6 b to be formed.
  • the drying method is not particularly limited, and examples thereof include methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Any of these methods may be used alone or two or more may be combined.
  • the drying temperature is not particularly limited, but in the case of using the above-mentioned water as a solvent or a mixed solvent of water and an organic solvent, the temperature is preferably 50 to 160 ° C. in general. Moreover, it is preferable to carry out the pressure at the time of drying usually under normal pressure or reduced pressure, and from the viewpoint of simplicity of equipment at normal pressure. In the case where the second covering layer 6b formed in this manner contains a polyvalent metal compound and the coating liquid (b) further contains another component such as an additive, the other component is contained. include.
  • Retort treatment is a treatment which pressure-kills microorganisms such as mold, yeast and bacteria in order to preserve food and the like in general.
  • the pasteurization treatment is carried out under conditions of 105 to 140 ° C., 0.15 to 0.30 MPa, for 10 to 120 minutes.
  • steam type using heating steam
  • hot water type using pressurized superheated water, etc.
  • Boiling treatment is a treatment of moist heat sterilization to preserve food and the like.
  • the wet heat sterilization treatment is carried out under the conditions of 60 to 100 ° C. under atmospheric pressure and at a condition of 10 to 120 minutes, although the gas barrier laminate in which the food etc. is packaged is carried out.
  • Boiling treatment is usually carried out using a hot water bath, but there are a batch type which is immersed in a hot water bath at a constant temperature and taken out after a certain time, and a continuous type in which the heat water bath is tunneled and sterilized.
  • the gas barrier laminates 10C and 10D have excellent gas barrier properties and retort odor suppression effects by including the inorganic vapor deposition layer 3 and the covering layer 6.
  • the gas barrier laminates 10C and 10D preferably have an oxygen permeability of 30 cc / m 2 ⁇ day ⁇ MPa or less, more preferably 15 cc / m 2 ⁇ day ⁇ MPa or less, at a temperature of 30 ° C. and a relative humidity of 70% RH. And particularly preferably 1.5 cc / m 2 ⁇ day ⁇ MPa or less.
  • the lower limit is not particularly limited, but is usually 0.01 cc / m 2 ⁇ day ⁇ MPa or more.
  • the gas barrier laminates 10C and 10D have a water vapor permeability at a temperature of 40 ° C. and a relative humidity of 90% RH of usually 5 g / m 2 ⁇ day or less, preferably 5 g / m 2 ⁇ day or less, particularly preferably It is 1 g / m 2 ⁇ day or less.
  • the water vapor transmission rate is preferably as low as possible, and the lower limit thereof is not particularly limited but is usually 0.01 g / m 2 ⁇ day or more.
  • the suppression effect of retort odor can be evaluated by ultraviolet light absorbance.
  • the reason is as follows. That is, when the content is high in sulfur-containing amino acid component, hydrogen sulfide generated at the time of retort treatment penetrates into the gas barrier layer, and hydrogen sulfide reacts with zinc oxide to form zinc sulfide. Zinc oxide inherently forms an ionic crosslink with the carboxy group in the coating layer to exhibit barrier properties, but if zinc sulfide is produced, zinc oxide will be insufficient for that and the barrier properties will deteriorate. It will Therefore, in order not to degrade the gas barrier layer, the amount of zinc oxide is increased, and as a result, the ultraviolet absorbance of the coating layer is increased.
  • the ultraviolet light absorbance is higher, the retort odor can be suppressed and the gas barrier performance can be improved.
  • this not only increases the cost of manufacturing but also reduces the transparency and the appearance performance, so it is not preferable that the ultraviolet light absorbance be too high.
  • the ultraviolet light absorbance is 0.3 or more and 0.7 or less, it has sufficient barrier properties.
  • the ratio of the thickness of the second covering layer 6b to the thickness of the first covering layer 6a may be 1.0 or more and 4.0 or less, or 1.1 or more and 3.0 or less It may be
  • the second covering layer 6b may satisfy at least one of the following conditions 1 to 3, and may satisfy two or three of the following conditions.
  • the haze of the second covering layer 6b is 8% or less.
  • the surface roughness Ra of the second covering layer 6b is 1/2 or less of the thickness of the second covering layer 6b.
  • the number per unit area of concave portions having a diameter of 1.5 ⁇ m or more on the surface of the second covering layer 6b opposite to the first covering layer 6a is 2 pieces / 0.01 mm 2 or less.
  • Example 1 to 3 and Comparative Examples 1 to 3 The preparation method of the anchor coating liquid used by the Example and the comparative example and the coating liquid is shown below.
  • Preparation of anchor coating solution In a diluted solvent (ethyl acetate), 1 part by mass of ⁇ -isocyanatopropyltrimethoxysilane and 5 parts by mass of acrylic polyol were mixed and stirred to obtain a solution. Thereafter, tolylene diisocyanate (TDI) was added to the above solution such that the amount of isocyanate groups was equal to the number of hydroxyl groups of the acrylic polyol. Then, the solution was diluted with ethyl acetate to a concentration of 2% by mass to obtain an anchor coat solution.
  • TDI tolylene diisocyanate
  • a coating solution B was obtained by mixing 100 g of a zinc oxide fine particle water dispersion ("ZE143” manufactured by Sumitomo Osaka Cement Co., Ltd.) and 1 g of a curing agent ("Liofol HAERTER UR 5889-21" manufactured by Henkel).
  • Example 1 (Preparation of gas barrier laminate)
  • the anchor coat solution is dried on the surface of the resin substrate on which a corona treatment has been performed on a biaxially stretched polyethylene terephthalate film ("Lumirror (registered trademark) P60" manufactured by Toray Industries, Inc., thickness 12 ⁇ m, inner corona treatment), after drying
  • the base layer was formed by coating using a bar coater such that the thickness of the layer becomes 0.2 .mu.m and drying at 150.degree. C. for 1 minute.
  • metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced there, aluminum oxide was deposited, and an inorganic deposition layer with a thickness of 20 nm was formed.
  • a coating solution A is applied on the inorganic deposition layer using a bar coater so that the thickness after drying is 0.15 ⁇ m, and then dried at 80 ° C. for 5 minutes, and then 3 ° C. at 50 ° C. After aging for 1 day, heat treatment was further performed at 200 ° C. for 5 minutes to form a first covering layer.
  • the coating solution B is coated on the first coating layer by a gravure printing method using a cylinder (plate cylinder) whose surface is ceramic-coated so that the thickness after drying is 0.25 ⁇ m. Then, it was dried at 90 ° C. for 2 minutes to form a second coated layer.
  • Example 2 A gas barrier laminate and a package were obtained in the same manner as Example 1, except that the thickness of the second covering layer after drying was changed to 0.15 ⁇ m.
  • Example 3 A gas barrier laminate and a package were obtained in the same manner as in Example 1 except that the thickness of the second covering layer after drying was changed to 0.45 ⁇ m.
  • Comparative Example 1 When coating the coating liquid B on the first coating layer, gravure using a cylinder whose surface is plated with Cr so that the thickness after drying (the thickness of the second coating layer) is 1.2 ⁇ m A gas barrier laminate and a packaging film were produced in the same manner as in Example 1 except that the coating was performed by the printing method.
  • Comparative Example 2 A gas barrier laminate and a packaging film were produced in the same manner as in Comparative Example 1 except that the thickness of the second coating layer after drying was changed to 0.07 ⁇ m.
  • Comparative Example 3 An aluminum foil 9 ⁇ m was laminated on a biaxially stretched polyethylene terephthalate film (PET: “Lumirror P60” manufactured by Toray Industries, Inc., 12 ⁇ m thick) by a dry lamination method to obtain a gas barrier laminate (Al foil laminate).
  • PET biaxially stretched polyethylene terephthalate film
  • Al foil laminate a gas barrier laminate
  • ⁇ Surface roughness Ra measurement> The surface roughness Ra of the second covering layer in the gas barrier laminate of each example was measured with a scanning probe microscope (SPM). Specifically, using an apparatus of MFP-3D manufactured by Asylum Research, the measurement was performed at a measurement area of 20 ⁇ m ⁇ 20 ⁇ m and a measurement frequency of 1 Hz. The results are shown in Table 1.
  • the “0.6 mass% cysteine aqueous solution” accommodated in the present example has a higher concentration than the cysteine aqueous solution generated from the actual contents assumed to be accommodated. That is, in the present example, the suppression of retort odor and the confirmation of the oxygen barrier property were performed under more severe conditions than the actual conditions.
  • the obtained package was subjected to retort treatment at 125 ° C. for 30 minutes using a water storage type retort pot.
  • the gas in the package is collected, and the amount of hydrogen sulfide (unit: mass ppm) in the gas is measured by Kitagawa-type gas detector (a gas collector AP-20 and a hydrogen sulfide detector tube manufactured by Komei Rikagaku Kogyo Co., Ltd.) It measured by).
  • Kitagawa-type gas detector a gas collector AP-20 and a hydrogen sulfide detector tube manufactured by Komei Rikagaku Kogyo Co., Ltd.
  • composition for forming adhesion layer Add acrylic polyol and tolysyl isocyanate so that the NCO group is equivalent to the OH group of acrylic polyol, dilute with ethyl acetate so that the total solid content becomes 5 w%, and further add ⁇ - (3, 4 w / w epoxycyclohexyl) trimethoxysilane was added with 5 w% relative to the total solids and mixed to obtain a composition for forming an adhesive layer (coating solution).
  • a reformed layer 1R was formed by RIE using a planar type plasma processing apparatus having the same configuration as that shown in FIG.
  • An argon / oxygen mixed gas was introduced into the electrode portion as a plasma generating gas, and a voltage was applied to the electrode portion using a high frequency power source with a frequency of 13.5 MHz to generate plasma, thereby performing RIE processing.
  • the applied power is 150 W
  • the self bias value is 600 V
  • the plasma density Epd value is 500 W ⁇ sec / m 2 .
  • Coating solution (a) Prepared according to the following procedure. 20 g of a PAA aqueous solution having a number average molecular weight of 200,000 (Aron A-10H, manufactured by Toagosei Co., Ltd., solid content concentration 25 mass%) was dissolved in 58.9 g of distilled water. Thereafter, 0.44 g of aminopropyltrimethoxysilane (APTMS: manufactured by Aldrich) was added, and stirring was performed to obtain a uniform solution, which was used as a coating solution (a).
  • ATMS aminopropyltrimethoxysilane
  • Coating solution (b) Prepared according to the following procedure.
  • a coating solution (b) was obtained by mixing 100 g of a zinc oxide fine particle water dispersion (“ZE143” manufactured by Sumitomo Osaka Cement) and 1 g of a curing agent Liofol HAERTER UR 5889-21 (manufactured by Henkel).
  • ZE143 zinc oxide fine particle water dispersion
  • Liofol HAERTER UR 5889-21 manufactured by Henkel
  • Example 4 Adhesion layer 2A on the corona-treated side of biaxially stretched polyethylene terephthalate film (PET: Toraya, Lumirror (registered trademark) P60, thickness 12 ⁇ m) to a thickness of 0.1 ⁇ m by a gravure coating method using a gravure coating machine
  • PET biaxially stretched polyethylene terephthalate film
  • the metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced therein, and aluminum oxide was deposited to form an inorganic deposition layer 3 with a thickness of 20 nm.
  • the coating solution (a) is applied using a bar coater so that the thickness after drying is 1 ⁇ m, and then dried at 80 ° C.
  • the coating solution (b) has a thickness of 1 ⁇ m after drying, and its UV absorbance is 0.30, which is the absorbance at a wavelength of 350 nm measured by absorptiometry minus the absorbance at a wavelength of 500 nm.
  • the bar coater After coating using a bar coater as a value, it was dried at 90 ° C. for 2 minutes and then aged at 50 ° C. for 3 days to form a second coated layer 6 b.
  • the actual ultraviolet absorbance was measured according to the following measurement method, and was described in Table 2. Moreover, the following other Examples and comparative examples were also measured similarly.
  • an unstretched polypropylene film (CPP: CPP manufactured by Toray Film Co., Ltd., CRP, Trefan NO ZK 207, 60 ⁇ m thickness), a two-component adhesive (Mitsui Chemical A525 /) A52) was used to laminate by a dry lamination method to obtain a laminate film having a configuration of [gas barrier layer / adhesive layer / CPP (60 ⁇ m)].
  • this laminated film was cut into a size of 10 cm ⁇ 10 cm.
  • Two pieces of the cut out film pieces are stacked with the CPP layer facing inside, heat sealed to form a package, in which 150 ml of an L-cysteine aqueous solution having a concentration of 0.3% / L as a sulfur-containing amino acid-containing substance After being filled with Kanto Chemical Co., Ltd. product (using L-cysteine), the package was hermetically sealed by the same heat seal. Then, it retorted at 0.18 MPa and 121 ° C. for 30 minutes using a hot water storage type retort pot.
  • Example 5 The same procedure as in Example 4 is carried out to form a first covering layer 6a, and then a coating liquid (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at 500 nm, is applied using a bar coater with a target value of 0.60, and then dried at 90 ° C. for 2 minutes and aged at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • Comparative Example 4 The same procedure as in Example 4 is carried out to form a first covering layer 6a, and then a coating liquid (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at a wavelength of 100, using a bar coater with a target value of 0.10, and then drying at 90 ° C. for 2 minutes and aging treatment at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • Comparative Example 5 The same procedure as in Example 4 is carried out to form a first covering layer 6a, and then a coating liquid (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at 500 nm, is applied using a bar coater with a target value of 0.20, and then dried at 90 ° C. for 2 minutes and aged at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • Example 6 An RIE treatment was applied to the corona-treated side of a biaxially stretched polyethylene terephthalate film (PET: Lumilar (registered trademark) P60 manufactured by Toray Industries, Inc., thickness 12 ⁇ m) to form a modified layer 1R.
  • PET biaxially stretched polyethylene terephthalate film
  • metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced there, aluminum oxide was deposited, and an inorganic deposition layer 3 having a thickness of 20 nm was formed.
  • the coating solution (a) is applied using a bar coater so that the thickness after drying is 1 ⁇ m, and then dried at 80 ° C.
  • the coating solution (b) has a thickness of 1 ⁇ m after drying, and its UV absorbance is 0.30, which is the absorbance at a wavelength of 350 nm measured by absorptiometry minus the absorbance at a wavelength of 500 nm. After coating using a bar coater as a value, it was dried at 90 ° C. for 2 minutes and then aged at 50 ° C. for 3 days to form a second coated layer 6 b.
  • an unstretched polypropylene film (CPP: CPP manufactured by Toray Film Co., Ltd., Trephan NO ZK 207, 60 ⁇ m thickness), a two-component adhesive (Mitsui Chemical A525 /) A52) was used to laminate by a dry lamination method to obtain a laminate film having a configuration of [gas barrier layer / adhesive layer / CPP (60 ⁇ m)].
  • this laminated film was cut into a size of 10 cm ⁇ 10 cm.
  • Two pieces of the cut out film pieces are stacked with the CPP layer facing inside, heat sealed to form a package, in which 150 ml of an L-cysteine aqueous solution having a concentration of 0.3% / L as a sulfur-containing amino acid-containing substance After being filled with Kanto Chemical Co., Ltd. product (using L-cysteine), the package was hermetically sealed by the same heat seal. Then, it retorted at 0.18 MPa and 121 ° C. for 30 minutes using a hot water storage type retort pot.
  • Example 7 The same procedure as in Example 6 is carried out to form a first covering layer 6a, and a coating solution (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at 500 nm, is applied using a bar coater with a target value of 0.60, and then dried at 90 ° C. for 2 minutes and aged at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • a gas barrier laminate having a configuration of [PET (12 ⁇ m) / modified treated layer 1R / inorganic vapor deposition layer 3 (20 nm) / coating layer 6: first coating layer 6a (1 ⁇ m) / second coating layer 6b (1 ⁇ m)] I got a body. Thereafter, a laminated film is obtained in the same manner as in Example 6, and a package is formed by heat sealing, in which 150 ml of an L-cysteine aqueous solution having a concentration of 0.3% / L (manufactured by Kanto Chemical Co., Ltd., L- After filling with cysteine), it was hermetically packaged by heat sealing as well. Then, it retorted at 0.18 MPa and 121 ° C. for 30 minutes using a hot water storage type retort pot.
  • Comparative Example 6 The same procedure as in Example 6 is carried out to form a first covering layer 6a, and a coating solution (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at a wavelength of 100, using a bar coater with a target value of 0.10, and then drying at 90 ° C. for 2 minutes and aging treatment at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • a gas barrier laminate having a configuration of [PET (12 ⁇ m) / modified treated layer 1R / inorganic vapor deposition layer 3 (20 nm) / coating layer 6: first coating layer 6a (1 ⁇ m) / second coating layer 6b (1 ⁇ m)] I got a body. Thereafter, a laminated film is obtained in the same manner as in Example 6, and a package is formed by heat sealing, in which 150 ml of an L-cysteine aqueous solution having a concentration of 0.3% / L (manufactured by Kanto Chemical Co., Ltd., L- After filling with cysteine), it was hermetically packaged by heat sealing as well. Then, it retorted at 0.18 MPa and 121 ° C. for 30 minutes using a hot water storage type retort pot.
  • Comparative Example 7 The same procedure as in Example 6 is carried out to form a first covering layer 6a, and a coating solution (b) is dried on this layer to a thickness of 1 ⁇ m after drying, and a wavelength of 350 nm measured by absorption photometry.
  • UV absorbance which is obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at 500 nm, is applied using a bar coater with a target value of 0.20, and then dried at 90 ° C. for 2 minutes and aged at 50 ° C. for 3 days
  • the second covering layer 6b was formed.
  • a gas barrier laminate having a configuration of [PET (12 ⁇ m) / modified treated layer 1R / inorganic vapor deposition layer 3 (20 nm) / coating layer 6: first coating layer 6a (1 ⁇ m) / second coating layer 6b (1 ⁇ m)] I got a body. Thereafter, a laminated film is obtained in the same manner as in Example 6, and a package is formed by heat sealing, in which 150 ml of an L-cysteine aqueous solution having a concentration of 0.3% / L (manufactured by Kanto Chemical Co., Ltd., L- After filling with cysteine), it was hermetically packaged by heat sealing as well. Then, it retorted at 0.18 MPa and 121 ° C. for 30 minutes using a hot water storage type retort pot.
  • the measurement range is a wavelength of 300 to 550 nm, and the value obtained by subtracting the absorbance at a wavelength of 500 nm from the absorbance at a wavelength of 350 nm does not include a layer containing a polyvalent metal compound in the same manner (biaxially stretched polyethylene terephthalate
  • the ultraviolet absorbance is defined as the value obtained by subtracting 0.02 of the adhesion layer 2A and the inorganic vapor deposition layer 3 on the film or the measurement value of 0.02 on the biaxially stretched polyethylene terephthalate film and the modification treated layer 1R and the inorganic vapor deposition layer 3).
  • the measurement method is in accordance with JIS K-7126, method B (isostatic pressure), and the measured value is expressed in units [cc / m 2 ⁇ day ⁇ MPa].
  • Method B isostatic pressure
  • the measured value is expressed in units [cc / m 2 ⁇ day ⁇ MPa].
  • [Measuring method of water vapor permeability] The water vapor permeability was measured at a temperature of 40 ° C. and a relative humidity of 90% using a water vapor permeability measuring device (PERMATRAN 3/31 manufactured by Modern Control).
  • the measurement method was in accordance with JIS K-7129, and the measurement value was expressed in the unit [g / m 2 ⁇ day].
  • Adhesion evaluation It evaluated about the package which performed retort treatment. After retorting, the 0.3% / L aqueous L-cysteine solution filled in the package is removed, and the gas barrier laminate dried overnight is subjected to JIS K 6854-3 (T-type peeling). The adhesion was evaluated. In addition, when the package body was cut
  • Retort odor determination of hydrogen sulfide concentration as an alternative evaluation: Evaluation was made on a package subjected to retort treatment. After retorting, the package was opened, and the concentration of hydrogen sulfide in the package was quantified using a Kitagawa-type gas detector (a gas collector "AP-20B" manufactured by Komyura Chemical Industry Co., Ltd. and a hydrogen sulfide detector tube). .
  • Kitagawa-type gas detector a gas collector "AP-20B” manufactured by Komyura Chemical Industry Co., Ltd. and a hydrogen sulfide detector tube.
  • Example 4 the package subjected to retort treatment has sufficient adhesiveness, the concentration of hydrogen sulfide in the package is low, and the oxygen permeability is 1 cc / m 2 ⁇ day ⁇ MPa level, water vapor The permeability is as good as 3 g / m 2 ⁇ day level is obtained, and in Examples 5 to 7 as well, the adhesiveness, the low concentration of hydrogen sulfide, and the low permeability of oxygen and water vapor are similarly obtained. The results were obtained.
  • Comparative Examples 4 to 7 in the state of the gas barrier laminate, both the oxygen permeability and the water vapor permeability are at the same level as in Examples 4 to 7, but the contents containing a large amount of sulfur-containing amino acids
  • an L-cysteine aqueous solution having a concentration of 0.3% / L was used, and retort treatment was performed, whereby the oxygen permeability and the water vapor permeability became high, and the gas barrier properties deteriorated.
  • the concentration of hydrogen sulfide is also high, it indicates that the unpleasant retort odor generated during retort treatment can not be suppressed.
  • the adhesion is insufficient. Therefore, the laminates of Comparative Examples 4 to 7 are not suitable as packaging materials for retort treatment.
  • SYMBOLS 1 Resin base material, 1A ... Plastic base material (film base material), 1R ... Modification process layer, 2 ... Base layer, 2A ... Adhesion layer, 3 ... Inorganic vapor deposition layer, 5a, 6a ...

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

Un stratifié formant barrière contre les gaz selon la présente invention présente une structure qui est pourvue d'un matériau de base en résine, d'une première couche de revêtement qui contient un polymère d'acide carboxylique, et d'une seconde couche de revêtement qui contient un composé métallique polyvalent et une résine, et le matériau de base en résine, la première couche de revêtement et la seconde couche de revêtement étant empilés dans cet ordre. Ce stratifié formant barrière contre les gaz est conçu de telle sorte que : le rapport de l'épaisseur de la seconde couche de revêtement à l'épaisseur de la première couche de revêtement est de 1,0 à 4,0 (inclus); et la seconde couche de revêtement satisfait au moins l'une des conditions 1 à 3 décrites ci-après. (Condition 1) Le trouble de la seconde couche de revêtement est inférieur ou égal à 8 %. (Condition 2) La rugosité de surface Ra de la seconde couche de revêtement représente 1/2 ou moins de l'épaisseur de la seconde couche de revêtement. (Condition 3) Le nombre d'évidements ayant un diamètre de 1,5 µm ou plus par unité de surface dans une surface de la seconde couche de revêtement, ladite surface se trouvant sur le verso de la surface côté première couche de revêtement, est de 2 évidements/0,01 mm2 ou moins.
PCT/JP2019/001539 2018-01-19 2019-01-18 Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci WO2019142923A1 (fr)

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CN201980008369.8A CN111601711B (zh) 2018-01-19 2019-01-18 阻气层叠体以及具备该阻气层叠体的包装材料
EP19741638.1A EP3741560B1 (fr) 2018-01-19 2019-01-18 Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci
US16/922,140 US11766695B2 (en) 2018-01-19 2020-07-07 Gas barrier laminate and packaging material including the same

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JP2018-007295 2018-01-19
JP2018007295 2018-01-19
JP2018-119837 2018-06-25
JP2018119837A JP7196431B2 (ja) 2018-01-19 2018-06-25 ガスバリア積層体および包装体
JP2019-006093 2019-01-17
JP2019-005916 2019-01-17
JP2019005916A JP7172627B2 (ja) 2019-01-17 2019-01-17 ガスバリア積層体及びそれを備える包装体
JP2019-006095 2019-01-17
JP2019006095A JP7271960B2 (ja) 2019-01-17 2019-01-17 ガスバリア積層体及びそれを備える包装体
JP2019006093A JP2020114636A (ja) 2019-01-17 2019-01-17 ガスバリア積層体及びそれを備える包装体

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WO2020149216A1 (fr) * 2019-01-17 2020-07-23 凸版印刷株式会社 Emballage, stratifié formant barrière contre les gaz et corps d'emballage
JP2020114744A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
JP2020114745A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 パッケージ
JP2020196527A (ja) * 2019-06-05 2020-12-10 凸版印刷株式会社 パッケージ
JP2021176296A (ja) * 2020-04-30 2021-11-11 海商株式会社 包装された魚介製品およびその製造方法
CN114728498A (zh) * 2019-11-20 2022-07-08 东洋纺株式会社 层叠薄膜
WO2023074494A1 (fr) * 2021-10-26 2023-05-04 凸版印刷株式会社 Stratifié formant barrière contre les gaz, corps d'emballage et article d'emballage

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JP4365826B2 (ja) 2003-12-03 2009-11-18 株式会社クラレ ガスバリア性積層体および包装体ならびにガスバリア性積層体の製造方法
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WO2020149216A1 (fr) * 2019-01-17 2020-07-23 凸版印刷株式会社 Emballage, stratifié formant barrière contre les gaz et corps d'emballage
JP2020114744A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
JP2020114745A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 パッケージ
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JP2020196527A (ja) * 2019-06-05 2020-12-10 凸版印刷株式会社 パッケージ
CN114728498A (zh) * 2019-11-20 2022-07-08 东洋纺株式会社 层叠薄膜
CN114728498B (zh) * 2019-11-20 2024-01-12 东洋纺株式会社 层叠薄膜
JP2021176296A (ja) * 2020-04-30 2021-11-11 海商株式会社 包装された魚介製品およびその製造方法
JP7241112B2 (ja) 2020-04-30 2023-03-16 海商株式会社 包装された魚介製品およびその製造方法
WO2023074494A1 (fr) * 2021-10-26 2023-05-04 凸版印刷株式会社 Stratifié formant barrière contre les gaz, corps d'emballage et article d'emballage

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