WO2023243625A1 - ガスバリア性積層体、包装フィルム、包装容器及び包装製品 - Google Patents

ガスバリア性積層体、包装フィルム、包装容器及び包装製品 Download PDF

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Publication number
WO2023243625A1
WO2023243625A1 PCT/JP2023/021855 JP2023021855W WO2023243625A1 WO 2023243625 A1 WO2023243625 A1 WO 2023243625A1 JP 2023021855 W JP2023021855 W JP 2023021855W WO 2023243625 A1 WO2023243625 A1 WO 2023243625A1
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Prior art keywords
gas barrier
layer
barrier laminate
coating layer
barrier coating
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Ceased
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PCT/JP2023/021855
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English (en)
French (fr)
Japanese (ja)
Inventor
美季 福上
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Toppan Holdings Inc
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Toppan Holdings Inc
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Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to CN202380044385.9A priority Critical patent/CN119300977A/zh
Priority to JP2024528873A priority patent/JPWO2023243625A1/ja
Priority to EP23823915.6A priority patent/EP4541580A4/en
Publication of WO2023243625A1 publication Critical patent/WO2023243625A1/ja
Priority to US18/977,080 priority patent/US20250100262A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present disclosure relates to a gas barrier laminate, a packaging film, a packaging container, and a packaging product.
  • packaging containers such as packaging bags used for packaging foods, pharmaceuticals, etc.
  • water vapor, oxygen, and other contents are denatured to prevent deterioration and decay of the contents and to maintain their functions and properties.
  • Gas barrier properties are required to block the entry of harmful gases. Therefore, gas barrier laminates have conventionally been used in these packaging bags.
  • a gas barrier laminate generally includes a base layer, a vapor deposited layer, and a gas barrier coating layer in this order.
  • Patent Document 1 includes a base material layer containing a polyolefin, a metal oxide layer, and a gas barrier coating layer in this order, and the gas barrier coating layer is composed of silicon atoms in silicon alkoxide or its hydrolyzate.
  • the content ratio a/b of the content (a parts by mass) and the water-soluble polymer content (b parts by mass) is 3/97 or more and 45/55 or less in mass ratio.
  • Gas barrier laminates have been disclosed that have excellent gas barrier properties after being tested and subjected to abuse tests.
  • a sealant layer is generally attached to the gas barrier coating layer. Further, after the packaging bag is filled with contents and sealed, it is sometimes subjected to high temperature sterilization treatment at 121° C. or higher (hereinafter referred to as "high retort treatment").
  • high retort treatment high temperature sterilization treatment at 121° C. or higher
  • the gas barrier laminate described in Patent Document 1 has room for improvement in terms of gas barrier properties after high retort treatment and lamination strength with the sealant layer.
  • the present disclosure has been made in view of the above problems, and provides a gas barrier laminate, a packaging film, and a gas barrier laminate having excellent gas barrier properties and excellent adhesion with a sealant layer even after high-retort treatment.
  • the purpose is to provide packaging containers and packaging products.
  • the present disclosure includes a base material layer containing a thermoplastic resin, a vapor deposition layer, and a gas barrier coating layer in this order, and performs X-ray photoelectron spectroscopy on the surface of the gas barrier coating layer.
  • the ratio of silicon atoms to carbon atoms Si/C
  • the narrow spectrum of the Si2p orbital is 100 to 100.
  • a gas barrier laminate in which the half width of a peak appearing in a binding energy region of 107 eV is 1.85 eV or less.
  • the gas barrier laminate of the present disclosure has excellent gas barrier properties and excellent adhesion with the sealant layer even after high retort treatment.
  • the gas barrier laminate further includes an anchor coat layer between the base layer and the vapor deposition layer.
  • the surface smoothness of the anchor coat layer is improved more than the surface smoothness of the base material layer. Therefore, it is possible to make the thickness of the vapor deposited layer uniform, and the gas barrier properties of the gas barrier laminate can be further improved.
  • the gas barrier coating layer is made of a cured product of a composition containing a water-soluble polymer, a first silicon compound, and a second silicon compound, and the first silicon compound is as follows:
  • the second silicon compound contains at least one of a silicon alkoxide represented by the general formula (1) and a hydrolyzate thereof, and the second silicon compound contains at least one of a silicon alkoxide represented by the following general formula (2) and a hydrolyzate thereof. may be included.
  • OR 1 represents a hydrolyzable group.
  • R2Si ( OR3 ) 3 represents a hydrolyzable group.
  • n represents an integer of 1 or more.
  • the thickness of the gas barrier coating layer is preferably 100 nm or more and 700 nm or less. In this case, compared to the case where the thickness of the gas barrier coating layer is less than 100 nm, the gas barrier properties of the gas barrier laminate can be further improved even after high retort treatment. Moreover, compared to a case where the thickness of the gas barrier coating layer exceeds 700 nm, the gas barrier laminate is less likely to curl, and is easier to use as a gas barrier laminate for a packaging film included in a packaging bag.
  • the water-soluble polymer of the gas barrier coating layer may be a polyvinyl alcohol resin or a modified product thereof. In this case, this composition can impart superior gas barrier properties to the gas barrier laminate by curing. Further, even when cured, this composition can impart superior flexibility to the gas barrier laminate, and can further improve gas barrier properties after abuse.
  • the vapor deposition layer may contain at least one selected from aluminum oxide and silicon oxide.
  • the vapor deposition layer since both SiO x and AlO x have excellent water vapor barrier properties, the water vapor barrier properties of the gas barrier laminate can be improved. .
  • the present disclosure is a packaging film including the gas barrier laminate and a sealant layer. Since this packaging film includes the above-mentioned gas barrier laminate, it has excellent gas barrier properties even after high-retort treatment, and the gap between the sealant layer and the gas barrier coating layer in the gas barrier laminate constituting the packaging film is Peeling can be suppressed.
  • the present disclosure is a packaging container provided with the above-mentioned packaging film. Since this packaging container is equipped with the above-mentioned packaging film, it has excellent gas barrier properties even after high-retort treatment, and prevents peeling between the sealant layer and the gas barrier coating layer in the gas barrier laminate that constitutes the packaging film. Can be suppressed.
  • the present disclosure is a packaging product including the packaging container described above and contents filled in the packaging container.
  • This packaging product includes the above-mentioned packaging container, and the packaging container has excellent gas barrier properties even after high-retort treatment, and the packaging film includes a gas barrier coating layer and a sealant layer included in the gas barrier laminate. Since it is possible to suppress peeling between the two, deterioration in the quality of the contents due to oxygen contamination can be suppressed for a long period of time.
  • a gas barrier laminate, a packaging film, a packaging container, and a packaging product are provided that have excellent gas barrier properties and excellent adhesion with a sealant layer even after high retort treatment. .
  • FIG. 1 is a cross-sectional view showing an embodiment of a gas barrier laminate of the present disclosure.
  • FIG. 1 is a cross-sectional view showing an embodiment of the packaging film of the present disclosure.
  • FIG. 1 is a side view illustrating an embodiment of the packaged product of the present disclosure.
  • FIG. 1 is a cross-sectional view showing an embodiment of the gas barrier laminate of the present disclosure.
  • a gas barrier laminate 10 shown in FIG. 1 includes a base layer 1 containing a thermoplastic resin, a vapor deposition layer 3, and a gas barrier coating layer 4 in this order.
  • the ratio of silicon atoms to carbon atoms (Si/C) measured by X-ray photoelectron spectroscopy (XPS) is 0.25 to 0.90, and the Si2p orbital is The half-width of the peak appearing in the binding energy region of 100 to 107 eV in the narrow spectrum (hereinafter simply referred to as "Si2p orbital peak half-width") is 1.85 eV or less.
  • the gas barrier laminate 10 may have an anchor coat layer 2 as an intermediate layer between the base layer 1 and the vapor deposited layer 3.
  • This gas barrier laminate 10 has excellent gas barrier properties even after high retort treatment, and has excellent adhesion between the gas barrier coating layer 4 and the sealant layer.
  • the base layer 1 is a layer that serves as a support for the gas barrier coating layer 4, and contains a thermoplastic resin.
  • thermoplastic resins include polyolefin resins, polyester resins, polyamide resins, polyether resins, acrylic resins, and natural polymer compounds (cellulose acetate, etc.). These may be used alone or in a mixture of two or more.
  • the thickness of the base material layer 1 is not particularly limited, but may be, for example, 0.1 mm or less. Among these, the thickness of the base material layer 1 may be 40 ⁇ m or less, 35 ⁇ m or less, or 30 ⁇ m or less. When the thickness of the base material layer 1 is 40 ⁇ m or less, the flexibility of the gas barrier laminate 10 improves more than when the thickness of the base material layer 1 exceeds 40 ⁇ m, and the flexibility of the gas barrier laminate 10 after abuse improves. Oxygen gas barrier properties can be further improved. However, from the viewpoint of improving strength, the thickness of the base layer 1 is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more.
  • the material constituting the anchor coat layer 2 is not particularly limited as long as it can improve the adhesion between the base layer 1 and the vapor deposited layer 3; Contains a reaction product of a silane or organometallic compound, a polyol compound, and an isocyanate compound. That is, the anchor coat layer 2 can also be said to be a urethane adhesive layer.
  • the organosilane is, for example, a trifunctional organosilane or a hydrolyzate of a trifunctional organosilane.
  • the organometallic compound is, for example, a metal alkoxide or a hydrolyzate of a metal alkoxide. Examples of the metal elements contained in the organometallic compound include Al, Ti, and Zr.
  • the metal constituting the metal or metal oxide examples include at least one metal selected from the group consisting of Si, Al, Mg, Sn, Ti, and In.
  • the metal oxide is preferably at least one selected from the group consisting of silicon oxide (SiO x ) and aluminum oxide (AlO x ). Since both SiO x and AlO x have excellent water vapor barrier properties, the water vapor barrier properties of the gas barrier laminate 10 can be improved. Among these, SiO x is preferable as the metal oxide. In this case, the gas barrier laminate 10 can have better water vapor barrier properties.
  • the vapor deposition layer 3 may be composed of a single layer or a plurality of layers.
  • the thickness of the vapor deposition layer 3 is not particularly limited, it is preferably 5 nm or more. In this case, the gas barrier properties of the gas barrier laminate 10 are more improved than when the thickness of the vapor deposited layer 3 is less than 5 nm.
  • the thickness of the vapor deposited layer 3 is more preferably 8 nm or more, particularly preferably 10 nm or more. Moreover, it is preferable that the thickness of the vapor deposition layer 3 is 80 nm or less.
  • the flexibility of the gas barrier laminate 10 is further improved compared to the case where the thickness of the vapor deposited layer 3 exceeds 80 nm, and the gas barrier properties of the gas barrier laminate 10 after abuse can be further improved. Further, the gas barrier properties of the gas barrier laminate 10 after high retort treatment can be further improved.
  • the thickness of the vapor deposited layer 3 may be 70 nm or less, or may be 60 nm or less.
  • the gas barrier coating layer 4 is a layer that covers the vapor deposited layer 3 and has gas barrier properties, and is composed of a cured product of a composition for forming a gas barrier coating layer.
  • Si/C silicon atoms to carbon atoms
  • XPS X-ray photoelectron spectroscopy
  • the degree of polymerization of the water-soluble polymer is not particularly limited, but from the viewpoint of improving the gas barrier properties of the gas barrier laminate 10, it is preferably 300 or more.
  • the degree of polymerization of the water-soluble polymer is preferably 450 to 2,400.
  • the content of water-soluble polymer in the solid content is not particularly limited, but is preferably 25% by mass or more. In this case, by curing, the gas barrier properties of the gas barrier laminate 10 can be further improved even after high retort treatment.
  • the content of the water-soluble polymer in the solid content is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more.
  • the content of the water-soluble polymer in the solid content is 30% by mass or more, the gas barrier laminate becomes more difficult to form due to curing than when the content of the water-soluble polymer in the solid content is less than 30% by mass.
  • gas barrier properties can be further improved even after high retort treatment.
  • the content of water-soluble polymer in the solid content may be less than 100% by mass, but is preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass or less. is particularly preferred.
  • the content of the water-soluble polymer in the solid content is 80% by mass or less, the gas barrier laminate after high retort treatment is lower than when the content of the water-soluble polymer in the solid content exceeds 80% by mass.
  • the adhesion between the gas barrier coating layer 4 of the body 10 and the sealant layer can be further improved.
  • the first silicon compound includes at least one of a silicon alkoxide and a hydrolyzate thereof.
  • the silicon alkoxide described above is preferably represented by the following general formula (1).
  • OR 1 represents a hydrolyzable group.
  • R 1 include an alkyl group and -C 2 H 4 OCH 3 .
  • the alkyl group include a methyl group and an ethyl group. Among these, ethyl group is preferred.
  • TEOS tetraethoxysilane
  • the content of the first silicon compound in the solid content is not particularly limited, but is preferably 25% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. In this case, compared to the case where the content of the first silicon compound in the solid content is less than 25% by mass, the gas barrier properties of the gas barrier laminate 10 can be further improved by curing even after high retort treatment. can.
  • the monovalent organic group represented by R 2 includes a monovalent organic group containing a vinyl group, an epoxy group, a mercapto group, an amino group, or an isocyanate group.
  • a monovalent organic group containing a vinyl group, an epoxy group, a mercapto group, an amino group, or an isocyanate group.
  • an isocyanate group is preferable. In this case, it becomes possible for the composition to have better hot water resistance by curing, and it becomes possible to impart greater laminate strength to the gas barrier laminate 10 even after high retort treatment.
  • R 3 examples include an alkyl group and -C 2 H 4 OCH 3 .
  • the alkyl group examples include a methyl group and an ethyl group. Among these, methyl group is preferred. In this case, hydrolysis takes place quickly.
  • R 3 may be the same as or different from R 2 . Further, R 3 may be the same or different from each other.
  • n represents an integer of 1 or more.
  • the silane coupling agent represents a monomer, whereas when n is 2 or more, the silane coupling agent represents a multimer.
  • n is 3.
  • the hot water resistance of the gas barrier coating layer 4 can be further improved, and it becomes possible to impart greater laminate strength to the gas barrier laminate 10 even after high retort treatment.
  • Examples of the second silicon compound (silane coupling agent) include silane coupling agents having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Silane coupling agents with epoxy groups such as propyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silane coupling agents with mercapto groups such as silane; silane coupling agents with amino groups such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane, 1,3, Examples include silane coupling agents having an isocyanate group such as 5-tris(3-methoxysilylpropyl
  • the content of the second silicon compound in the solid content is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, particularly preferably 7% by mass or more. In this case, greater laminate strength can be imparted to the gas barrier laminate 10 by curing than in the case where the content of the second silicon compound in the solid content is less than 3% by mass even after high retort treatment. Can be done.
  • the content of the second silicon compound in the solid content is preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 12% by mass or less. In this case, the content of the water-soluble polymer and the first silicon compound in the gas barrier coating layer 4 is relatively higher than when the content of the second silicon compound in the solid content exceeds 20% by mass. Therefore, good gas barrier properties can be maintained.
  • the first silicon compound is a silicon alkoxide represented by the general formula (1) and its hydrolyzate.
  • the mass of the first silicon compound is converted to the mass of SiO2
  • the second silicon compound contains at least one of a silicon alkoxide represented by the general formula (2) and a hydrolyzate thereof, , the mass of the second silicon compound is converted into the mass of (R 2 Si(OH) 3 ) n to perform the calculation.
  • the solid content may further contain known additives such as a dispersant, a stabilizer, a viscosity modifier, and a coloring agent, as necessary, within a range that does not impair the gas barrier properties of the gas barrier coating layer 4.
  • Total content of components in solid content The total content of the water-soluble polymer, the first silicon compound, and the second silicon compound (silane coupling agent) in the solid content is not particularly limited, but is usually 95% by mass or more, preferably 97% by mass or more. It is at least 100% by mass.
  • Aqueous media include water, hydrophilic organic solvents, or mixtures thereof.
  • hydrophilic organic solvents include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; carbitols; nitrites such as acetonitrile. . These can be used alone or in combination of two or more.
  • the aqueous medium is preferably an aqueous medium consisting only of water or an aqueous medium containing water as a main component.
  • the content of water in the aqueous medium is preferably 70% by mass or more, more preferably 80% by mass or more.
  • the thickness of the gas barrier coating layer 4 is more preferably 150 nm or more, and particularly preferably 200 nm or more.
  • the thickness of the gas barrier coating layer 4 is preferably 700 nm or less. Compared to the case where the gas barrier coating layer 4 has a thickness of more than 700 nm, the gas barrier laminate 10 is less likely to curl and can be easily used as a gas barrier laminate for a packaging film included in a packaging bag.
  • the thickness of the gas barrier coating layer 4 is more preferably 500 nm or less, particularly preferably 400 nm or less.
  • the base material layer 1 is prepared.
  • the vapor deposition layer 3 can be formed, for example, by a vacuum film forming method.
  • the vacuum film forming method include physical vapor deposition and chemical vapor deposition.
  • the physical vapor deposition method include a vacuum deposition method, a sputter deposition method, an ion plating method, and the like.
  • a vacuum evaporation method is particularly preferably used.
  • the vacuum deposition method include a resistance heating vacuum deposition method, an EB (Electron Beam) heating vacuum deposition method, and an induction heating vacuum deposition method.
  • the chemical vapor deposition method include thermal CVD, plasma CVD, and photoCVD.
  • the gas barrier coating layer 4 has a silicon atom to carbon atom ratio (Si/C) when performing elemental quantitative analysis on the surface of the gas barrier coating layer 4 by X-ray photoelectron spectroscopy. is 0.25 to 0.90, and the peak half width of the narrow spectrum of the Si2p orbit appearing at 100 to 107 eV is 1.85 eV or less.
  • Curing can be performed, for example, by heating.
  • the gas barrier coating layer 4 can be cured by adjusting the mass ratio of PVA, TEOS, and SC agent, and setting the heating temperature to, for example, 65 to 130°C and the heating time to 5 seconds to 2 minutes. good.
  • FIG. 2 the same components as in FIG. 1 are denoted by the same reference numerals, and redundant explanation will be omitted.
  • FIG. 2 is a cross-sectional view showing an embodiment of the packaging film of the present disclosure.
  • the packaging film 20 includes a gas barrier laminate 10 and a sealant layer 21 that is laminated on the gas barrier laminate 10. It is arranged on the gas barrier coating layer 4 side of layer 1.
  • the gas barrier coating layer 4 and the sealant layer 21 may be bonded together by an adhesive layer 22, or the gas barrier coating layer 4 and the sealant layer 21 may be bonded together directly. May be glued
  • sealant layer 21 examples of the material for the sealant layer 21 include thermoplastic resins such as polyolefin resins and polyester resins, but polyolefin resins are generally used. Specifically, polyolefin resins include low density polyethylene resin (LDPE), medium density polyethylene resin (MDPE), linear low density polyethylene resin (LLDPE), ethylene-vinyl acetate copolymer (EVA), and ethylene- ⁇ .
  • LDPE low density polyethylene resin
  • MDPE medium density polyethylene resin
  • LLDPE linear low density polyethylene resin
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- ⁇ ethylene- ⁇ .
  • Olefin copolymers ethylene resins such as ethylene-(meth)acrylic acid copolymers, homopolypropylene (PP), propylene-ethylene random copolymers, propylene-ethylene block copolymers, propylene- ⁇ -olefin copolymers
  • Polypropylene resins such as, or mixtures thereof can be used.
  • the material of the sealant layer 21 can be appropriately selected from the above-mentioned thermoplastic resins depending on the intended use and temperature conditions such as boiling treatment and high retort treatment. From this point of view, polyolefin resin is preferable. Further, when the base layer 1 contains a polyester resin, the material of the sealant layer 21 is preferably a polyester resin from the viewpoint of recyclability.
  • This packaging product 40 includes a packaging container 30, which has excellent gas barrier properties even after high retort treatment, and which has a gas barrier coating layer 4 included in the gas barrier laminate in the packaging film 20. Since peeling between the sealant layer 21 and the sealant layer 21 can be suppressed, deterioration in the quality of the contents C due to the mixing of oxygen can be suppressed for a long period of time.
  • the gist of the present disclosure is as follows.
  • a base material layer containing a thermoplastic resin, a vapor deposition layer, and a gas barrier coating layer are provided in this order, When performing elemental quantitative analysis on the surface of the gas barrier coating layer by X-ray photoelectron spectroscopy, the ratio of silicon atoms to carbon atoms (Si/C) is 0.25 to 0. 90, and the peak half width of the narrow spectrum of the Si2p orbit appearing at 100 to 107 eV is 1.85 eV or less.
  • the gas barrier laminate thus obtained was subjected to narrow analysis under the following measurement conditions using the following measuring equipment to obtain narrow spectra of O1s, N1s, C1s, and Si2p orbitals on the surface of the gas barrier coating layer. . Then, for each element of O, N, C, and Si, using relative sensitivity coefficients of 2.28 eV for O1s, 1.61 eV for N1s, 1.00 eV for C1s, and 0.9 eV for Si2p, the respective peak areas were calculated. , elemental quantitative values (atomic %) were determined, and Si/C was calculated using the obtained elemental quantitative values. The results are shown in Table 1.
  • ⁇ Measuring equipment> JEOL Ltd., JPS-9030 type photoelectron spectrometer ⁇ Measurement conditions> (Spectrum acquisition conditions) Incident X-ray: MgK ⁇ (h ⁇ 1253.6eV) X-ray output: 100W (10kV/10mA) Measurement area: Circular area with a diameter of 6 mm Photoelectron capture angle: 90° (Measurement condition) Dwell Time: 100ms Measurement step: 0.2eV Pass energy: 10eV Total number of times: 5 times
  • an AC2 layer forming composition is used as an anchor coat layer forming composition, an AC2 layer is formed so that the film thickness is 1500 nm, and a coating liquid is prepared.
  • a gas barrier coating layer the mass ratio (mass%) of PVA, TEOS (SiO 2 equivalent value) and SC agent ((R 2 Si (OH) 3 ) n equivalent value) in the solid content is shown in Table 1.
  • a gas barrier laminate was produced in the same manner as in Example 1 except that the values shown were used.
  • Example 10 Instead of forming an anchor coat layer as an intermediate layer on the base layer, the surface layer of the base layer is modified by reactive ion etching (RIE) to form the intermediate layer.
  • RIE reactive ion etching
  • PVA TEOS
  • TEOS SiO 2 equivalent value
  • SC agent ((R 2 Si(OH) 3 ) n equivalent in the solid content)
  • a gas barrier laminate was produced in the same manner as in Example 1, except that the mass ratio (mass %) of the sample was set to the values shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/021855 2022-06-15 2023-06-13 ガスバリア性積層体、包装フィルム、包装容器及び包装製品 Ceased WO2023243625A1 (ja)

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JP2024528873A JPWO2023243625A1 (https=) 2022-06-15 2023-06-13
EP23823915.6A EP4541580A4 (en) 2022-06-15 2023-06-13 GAS BARRIER LAMINATE, PACKAGING FILM, PACKAGING CONTAINER AND PACKAGED PRODUCT
US18/977,080 US20250100262A1 (en) 2022-06-15 2024-12-11 Gas-barrier laminate, packaging film, packaging container, and packaged product

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