WO2023219016A1 - 酸素吸収材、及び物品を保存する方法 - Google Patents

酸素吸収材、及び物品を保存する方法 Download PDF

Info

Publication number
WO2023219016A1
WO2023219016A1 PCT/JP2023/016897 JP2023016897W WO2023219016A1 WO 2023219016 A1 WO2023219016 A1 WO 2023219016A1 JP 2023016897 W JP2023016897 W JP 2023016897W WO 2023219016 A1 WO2023219016 A1 WO 2023219016A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
oxygen
oxygen absorbing
absorbing material
layer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2023/016897
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
菜穂子 小林
和起 河野
一樹 野平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to US18/862,739 priority Critical patent/US20250281901A1/en
Priority to KR1020247036989A priority patent/KR20250009969A/ko
Priority to CN202380038634.3A priority patent/CN119156286A/zh
Priority to JP2024520412A priority patent/JPWO2023219016A1/ja
Priority to EP23803494.6A priority patent/EP4523911A4/en
Publication of WO2023219016A1 publication Critical patent/WO2023219016A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/708—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23B2/712—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23B2/717—Oxygen absorbent
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
    • A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/18—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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B5/00—Packaging individual articles in containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, jars
    • B65B5/04—Packaging single articles
    • 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
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • B65D81/267—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants the absorber being in sheet form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2255/205—Metallic 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
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • 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
    • 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
    • B32B2307/74—Oxygen absorber
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to oxygen absorbing materials and methods for preserving articles.
  • a preservation technique using an oxygen absorber is known as one of the preservation techniques for foods, medicines, etc. Specifically, the technology suppresses oxidative deterioration, discoloration, etc. of the stored object by storing an oxygen absorber inside a sealed package together with the stored object and creating an oxygen-free condition inside the sealed package. It is.
  • Inorganic materials include those using metal powder such as iron, sulfite, bisulfite, and dithionite; organic materials include L-ascorbic acid, erythorbic acid and their salts, and sugars such as glucose. Examples include those using reducing polyhydric alcohols such as , catechol, and pyrogallol.
  • Oxygen absorbing resin compositions containing improved oxygen absorbers are also known.
  • Patent Document 1 describes at least one member selected from the group consisting of iron, cobalt, nickel, and copper as an oxygen-absorbing resin composition that has oxygen-absorbing ability even in an atmosphere with no or almost no moisture.
  • An oxygen absorbent containing a metal obtained by subjecting an alloy containing a transition metal of Disclosed is an oxygen-absorbing resin composition comprising the following: and having a water content of a predetermined value or less.
  • Patent Document 2 discloses that an oxygen containing iron powder or a reducing organic compound, an alkaline compound, and water is placed in a packaging bag constructed by heat-pressing the peripheral edges of sheets made by laminating predetermined packaging materials.
  • the oxygen absorber which is made by enclosing an absorbent composition and whose stiffness value of the heat-sealed part formed at the periphery of the packaging bag by thermal adhesion is within a predetermined range, is unlikely to fall off or damage the food during the packaging process. , and is disclosed to exhibit excellent food preservation effects.
  • the oxygen absorbents used in Patent Documents 1 and 2 both contain metal powder such as iron powder or a reducing organic compound.
  • metal powder such as iron powder or a reducing organic compound.
  • a new material as an oxygen absorber, it can be easily formed into a film without any operations such as kneading the oxygen absorber into the film, and it can be used for storage of water-containing products or high-quality materials.
  • Oxygen-absorbing materials suitable for storing articles in humid environments are being considered.
  • An object of the present invention is to provide an oxygen absorbing material suitable for preserving water-containing articles or preserving articles in a high humidity environment, and a method for preserving articles using the oxygen absorbing material.
  • the present inventors have discovered that the above-mentioned problems can be solved by providing an oxygen absorbing material with a specific structure that includes a base material, an inorganic layer, and a cured product layer of a predetermined epoxy resin composition. That is, the present invention relates to the following. [1] It has a base material (I), an inorganic layer (II), and a cured product layer (III) of an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent including an amine-based curing agent. , an oxygen absorbing material in which the inorganic layer (II) and the cured material layer (III) are adjacent to each other.
  • the article is housed in a packaging material encapsulating the oxygen absorbing material.
  • the article is housed in a packaging material having at least a portion of the oxygen absorbing material, and the packaging material has an oxygen permeability of 1 cc/(m 2 ⁇ day ⁇ atm) or less.
  • an oxygen absorbing material particularly suitable for storing water-containing articles or storing articles in a high humidity environment, and a method for preserving articles using the oxygen absorbing material.
  • (a) is an external photograph of the cut mochi used in Example 24, Comparative Example 2, and Comparative Example 3 before storage.
  • (b) is Example 24, (c) is Comparative Example 2, and (d) is Comparative Example 3, which were housed in a bag-shaped packaging material, and the packaging material was placed in an environment of 40°C and 90% relative humidity. This is a photograph of the appearance of cut mochi after being stored for two months.
  • (a) is an external photograph of the cheese cod used in Example 25, Comparative Example 4, and Comparative Example 5 before storage.
  • (b) is Example 25,
  • (c) is Comparative Example 4, and (d) is Comparative Example 5, which were housed in a bag-shaped packaging material, and the packaging material was placed in an environment of 40°C and 90% relative humidity. This is a photograph of the appearance of cheese cod after being stored for two months.
  • the oxygen absorbing material of the present invention includes a base material (I), an inorganic layer (II), and a cured product layer (III) of an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent containing an amine-based curing agent. ), and the inorganic layer (II) and the cured material layer (III) are adjacent to each other.
  • the oxygen absorbing material of the present invention has oxygen absorbing properties and is particularly suitable for preserving water-containing articles.
  • the oxygen absorbing material of the present invention achieves the above effects is not clear, but it is thought to be as follows. It is thought that the cured layer (III) of a predetermined epoxy resin composition, which the oxygen absorbing material of the present invention has, is oxidized by contacting with the inorganic layer (II) and develops oxygen absorbing properties. It is thought that oxidation of the inorganic layer (II) also progresses under the influence of the adjacent cured material layer (III). Furthermore, since the inorganic layer (II) and the cured material layer (III) have not only oxygen absorbing properties but also gas barrier properties, the packaging material using the oxygen absorbing material of the present invention is suitable for storing articles that are susceptible to oxidative deterioration.
  • the present inventors have found that the oxygen absorption property of the cured material layer (III) due to contact with the inorganic layer (II) is triggered by moisture. Therefore, the oxygen absorbing material of the present invention is suitable for storing water-containing articles or storing articles in a high humidity environment.
  • the layer structure of the oxygen absorbing material of the present invention is not particularly limited as long as it has at least one layer of the base material (I), the inorganic layer (II), and the cured material layer (III). However, from the viewpoint of exhibiting oxygen absorption performance, it is necessary that the inorganic layer (II) and the cured material layer (III) are adjacent to each other. From the viewpoint of expressing oxygen absorption performance and from the viewpoint of protecting the inorganic layer (II), the layer structure of the oxygen absorbing material preferably includes the base material (I), the inorganic layer (II), and the cured material layer ( III) in this order, and the inorganic layer (II) and the cured material layer (III) are adjacent to each other.
  • the oxygen absorbing material preferably has two or more base materials (I), including the base material (IA), the inorganic layer (II), and the cured material layer (III). ), and the base material (IB) in this order.
  • the base material (I) used in the oxygen absorbing material of the present invention is preferably a plastic film from the viewpoint of improving oxygen absorbency and bending resistance.
  • the plastic film used as the substrate (I) include polyolefin films such as low density polyethylene, high density polyethylene, linear low density polyethylene, and polypropylene; polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.
  • the base material (I) is a film selected from the group consisting of a polyolefin film, a polyester film, a polyamide film, and a polyimide film, from the viewpoint of oxygen absorption, bending resistance, strength, and heat resistance.
  • a film selected from the group consisting of a polyolefin film and a polyester film is more preferred, and a polypropylene film or a polyethylene terephthalate (PET) film is even more preferred.
  • PET polyethylene terephthalate
  • the above film may be an unstretched film or may be uniaxially or biaxially stretched.
  • the base material (IA) and the base material (IB) may be made of the same type of resin, or may be made of different types of resin.
  • the base material (IA) and the base material (IB) are preferably made of the same type of resin, and the base material (IA) and the base material (IB) are More preferably, it is a polypropylene film.
  • the thickness of the base material (I) can be appropriately selected depending on the application and is not particularly limited, but from the viewpoint of gas barrier properties and strength, it is preferably 5 to 300 ⁇ m, more preferably 5 to 100 ⁇ m, and even more preferably 10 ⁇ m. ⁇ 60 ⁇ m.
  • the above thickness is the thickness per sheet of the base material (I).
  • the inorganic layer (II) used in the oxygen absorbing material of the present invention may be made of metal foil or formed by a vapor deposition method. From the viewpoint of improving oxygen absorption, the inorganic layer (II) is preferably an inorganic vapor deposited layer formed by a vapor deposition method.
  • the inorganic substance constituting the inorganic layer (II) is preferably an inorganic substance capable of forming an inorganic vapor deposition layer, such as silicon, aluminum, magnesium, calcium, zinc, tin, nickel, titanium, zirconium, carbon, or any of these.
  • the inorganic layer (II) is a silicon oxide (silica) vapor deposited layer, an aluminum vapor deposited layer, or an aluminum oxide vapor deposited layer.
  • An (alumina) vapor-deposited layer is preferable, and from the viewpoint of improving oxygen absorption, an aluminum vapor-deposited layer is more preferable.
  • the thickness of the inorganic layer (II) is preferably 5 nm or more from the viewpoint of improving oxygen absorption and gas barrier properties.
  • the thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and when the inorganic layer (II) is an inorganic vapor-deposited layer, it is preferably 100 nm or less, more preferably 50 nm or less. be.
  • the above thickness is the thickness per layer of the inorganic layer (II).
  • the method for forming the inorganic layer (II) is not particularly limited, but examples of the vapor deposition method include physical vapor deposition methods such as vacuum evaporation method, sputtering method, and ion plating method, plasma chemical vapor deposition method, and thermochemical vapor deposition method. Known vapor deposition methods such as phase epitaxy and chemical vapor deposition such as photochemical vapor deposition may be used.
  • the inorganic layer (II) can be formed, for example, on the base material (I) or on the cured material layer (III).
  • the cured product layer (III) used in the oxygen absorbing material of the present invention is a layer made of a cured product of an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent including an amine-based curing agent. Each component contained in the epoxy resin composition will be explained below.
  • Epoxy resin used in the epoxy resin composition may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, or heterocyclic compounds. When considering the development of high oxygen absorption and gas barrier properties, epoxy resins containing an aromatic ring or alicyclic structure in the molecule are preferred. Specific examples of the epoxy resin include epoxy resins having a glycidylamino group derived from metaxylylene diamine, epoxy resins having a glycidylamino group derived from paraxylylene diamine, and 1,3-bis(aminomethyl).
  • epoxy resins having glycidyloxy groups derived from resorcinol At least one selected from the group consisting of epoxy resins having glycidyloxy groups derived from resorcinol and epoxy resins having glycidyloxy groups derived from resorcinol.
  • the above epoxy resins can be used alone or in combination of two or more.
  • epoxy resins include epoxy resins with glycidylamino groups derived from metaxylylene diamine, and epoxy resins with glycidylamino groups derived from paraxylylene diamine.
  • the "main component” here means that other components may be included without departing from the spirit of the present invention, and is preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the whole. , more preferably 90 to 100% by mass.
  • the epoxy resin curing agent used in the epoxy resin composition contains an amine curing agent from the viewpoint of improving oxygen absorption and gas barrier properties.
  • the amine curing agent polyamines conventionally used as epoxy resin curing agents or modified products thereof can be used.
  • the amine curing agent is preferably a modified polyamine, and more preferably contains a reaction product of the following components (A) and (B).
  • the component (A) is preferably metaxylylene diamine from the viewpoint of improving oxygen absorption and gas barrier properties.
  • the component (B) is at least one selected from the group consisting of unsaturated carboxylic acids represented by the general formula (1) and derivatives thereof.
  • R 1 in the general formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; It is more preferably a hydrogen atom or a methyl group, even more preferably a hydrogen atom.
  • R 2 in the general formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; It is more preferably a group, even more preferably a hydrogen atom or a methyl group, even more preferably a hydrogen atom.
  • Examples of the derivative of the unsaturated carboxylic acid represented by the general formula (1) include esters, amides, acid anhydrides, and acid chlorides of the unsaturated carboxylic acid.
  • the ester of unsaturated carboxylic acid is preferably an alkyl ester, and from the viewpoint of obtaining good reactivity, the alkyl carbon number is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2.
  • Examples of the unsaturated carboxylic acid represented by the general formula (1) and its derivatives include acrylic acid, methacrylic acid, ⁇ -ethyl acrylic acid, ⁇ -propylacrylic acid, ⁇ -isopropylacrylic acid, and ⁇ -n-butylacrylic acid.
  • Acid ⁇ -t-butylacrylic acid, ⁇ -pentylacrylic acid, ⁇ -phenylacrylic acid, ⁇ -benzylacrylic acid, crotonic acid, 2-pentenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-methyl-2-hexenoic acid, 5-methyl-2-hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 4-phenyl-2-butenoic acid, cinnamic acid, o-methyl cinnamon Examples thereof include acids, unsaturated carboxylic acids such as m-methylcinnamic acid, p-methylcinnamic acid, and 2-octenoic acid, and esters, amides, acid anhydrides, and acid chlorides thereof.
  • the component (B) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and derivatives thereof; , crotonic acid, and alkyl esters thereof; more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof; and at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof. is even more preferred, and methyl acrylate is even more preferred.
  • the reaction between the component (A) and the component (B) is carried out at a temperature of 0 to 100°C, more preferably 0 to 70°C.
  • Components (A) and (B) are mixed together under conditions of 100 to 300°C, preferably 130 to 250°C to carry out a Michael addition reaction and an amide group forming reaction by dehydration, dealcoholization, and deamination.
  • the inside of the reaction apparatus may be subjected to reduced pressure treatment at the final stage of the reaction, if necessary.
  • it can also be diluted using a non-reactive solvent if necessary.
  • catalysts such as phosphorous esters may be added as dehydrating agents and dealcoholizing agents.
  • an acid anhydride or acid chloride of an unsaturated carboxylic acid is used as the component (B)
  • Michael addition reaction and amide It is carried out by carrying out a group forming reaction.
  • the inside of the reaction apparatus may be subjected to reduced pressure treatment at the final stage of the reaction, if necessary.
  • it can also be diluted using a non-reactive solvent if necessary.
  • tertiary amines such as pyridine, picoline, lutidine, and trialkylamine can also be added.
  • the epoxy which is the reaction product of component (A) and component (B) The cured material layer (III) formed using a resin curing agent has oxygen absorption properties, gas barrier properties, and good adhesive properties.
  • the reaction molar ratio of the component (B) to the component (A) [(B)/(A)] is preferably in the range of 0.3 to 1.0. If the reaction molar ratio is 0.3 or more, a sufficient amount of amide groups will be generated in the epoxy resin curing agent, and high levels of gas barrier properties and adhesive properties will be exhibited. On the other hand, if the above reaction molar ratio is within the range of 1.0 or less, the amount of amino groups necessary for reaction with the epoxy groups in the epoxy resin is sufficient, and the epoxy resin has excellent heat resistance and solubility in organic solvents and water. It is also excellent. From the viewpoint of oxygen absorption and gas barrier properties of the obtained cured product layer (III), the reaction molar ratio of the component (B) to the component (A) [(B)/(A)] is 0.6 to 1. A range of 0 is more preferable.
  • the above-mentioned amine curing agent is a reaction product of the above-mentioned (A) component and (B) component, and at least one compound selected from the group consisting of the following (C) component, (D) component, and (E) component. It may be a thing.
  • C At least one member selected from the group consisting of monovalent carboxylic acids and derivatives thereof represented by R 3 -COOH (R 3 is a hydrogen atom, an alkyl having 1 to 7 carbon atoms which may have a hydroxyl group) group or an aryl group having 6 to 12 carbon atoms.)
  • R 3 is a hydrogen atom, an alkyl having 1 to 7 carbon atoms which may have a hydroxyl group) group or an aryl group having 6 to 12 carbon atoms.
  • D Cyclic carbonate
  • E Monoepoxy compound having 2 to 20 carbon atoms
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a hydroxyl group, or an aryl group having 6 to 12 carbon atoms, and R 3 preferably represents an alkyl group having 1 to 3 carbon atoms or phenyl. It is the basis.
  • Examples of the monovalent carboxylic acid derivative represented by R 3 -COOH include esters, amides, acid anhydrides, and acid chlorides of the carboxylic acid.
  • the ester of the carboxylic acid is preferably an alkyl ester, and the alkyl carbon number is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2.
  • the component (C) include monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, and benzoic acid, and derivatives thereof.
  • the component (C) may be used alone or in combination of two or more.
  • the cyclic carbonate which is the component (D), is used as necessary from the viewpoint of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving workability.
  • a cyclic carbonate having a six-membered ring or less is preferable.
  • Examples include 1,3-dioxan-2-one.
  • at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and glycerin carbonate is preferred.
  • the monoepoxy compound which is the component (E) is a monoepoxy compound having 2 to 20 carbon atoms, and from the viewpoint of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving workability, it may be added as necessary. used. From the viewpoint of gas barrier properties, a monoepoxy compound having 2 to 10 carbon atoms is preferable, and a compound represented by the following formula (2) is more preferable.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or R 5 -O-CH 2 -, and R 5 represents a phenyl group or a benzyl group.
  • Examples of the monoepoxy compound represented by the formula (2) include ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, phenyl glycidyl ether, and benzyl glycidyl ether.
  • the component (E) may be used alone or in combination of two or more.
  • any one selected from the group consisting of the above-mentioned (C) component, (D) component, and (E) component may be used alone, or two or more types may be used in combination.
  • the amine curing agent may be a reaction product obtained by reacting with other components as long as the effects of the present invention are not impaired.
  • the other components include aromatic dicarboxylic acids or derivatives thereof.
  • the amount of the "other components" used is preferably 30% by mass or less, more preferably 10% by mass or less, and 5% by mass or less of the total amount of the reaction components constituting the amine curing agent. % or less is more preferable.
  • the reaction product of the (A) component and (B) component and at least one compound selected from the group consisting of the (C) component, (D) component, and (E) component is the (C) component. It is obtained by using at least one compound selected from the group consisting of component (D) and component (E) in combination with component (B) and reacting with component (A), which is a polyamine compound.
  • component (A) which is a polyamine compound.
  • the components (B) to (E) may be added in any order and reacted with the component (A), or the components (B) to (E) may be mixed to react with the component (A). It may also be reacted with other components.
  • the reaction between the component (A) and the component (C) can be carried out under the same conditions as the reaction between the component (A) and the component (B).
  • the above component (C) the above (B) component and (C) component may be mixed and reacted with the above (A) component, or the above (A) component and (B) component are first mixed. You may react the said (C) component after reacting.
  • the (D) component and/or (E) component the (A) component and (B) component are first reacted, and then the (D) component and/or (E) component is reacted. It is preferable to react with the component.
  • the reaction between the component (A) and the component (D) and/or the component (E) is carried out by mixing the component (A) with the component (D) and/or the component (E) at a temperature of 25 to 200°C.
  • the addition reaction is carried out under conditions of 30 to 180°C, preferably 40 to 170°C.
  • a catalyst such as sodium methoxide, sodium ethoxide, potassium t-butoxide, etc. can be used if necessary.
  • the component (D) and/or the component (E) may be melted or diluted with a non-reactive solvent as necessary.
  • the amine curing agent is a reaction product of the (A) component and (B) component, and at least one compound selected from the group consisting of the (C) component, (D) component, and (E) component. Even when is preferably in the range of 0.6 to 1.0.
  • the reaction molar ratio of the component (C), component (D), and component (E) to the component (A) [ ⁇ (C)+(D)+(E) ⁇ /(A)] is 0 It is preferably in the range of .05 to 3.1, more preferably in the range of 0.07 to 2.5, and even more preferably in the range of 0.1 to 2.0.
  • reaction molar ratio of the components (B) to (E) to the component (A) [ ⁇ (B)+(C)+(D)+ (E) ⁇ /(A)] is preferably in the range of 0.35 to 2.5, more preferably in the range of 0.35 to 2.0.
  • the amine curing agent which is a reaction product of the above-mentioned (A) component and (B) component, contains only the above-mentioned (A) component and (B) component from the viewpoint of improving oxygen absorption property, gas barrier property, and adhesion.
  • a reaction product obtained by reacting is preferable, and a reaction product obtained by reacting only metaxylylene diamine and an acrylic acid alkyl ester is more preferable.
  • the content of the reaction product of the component (A) and component (B) in the amine curing agent is preferably 50% by mass or more, from the viewpoint of improving oxygen absorption, gas barrier properties, and adhesion. It is more preferably 70% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more and 100% by mass or less.
  • the epoxy resin curing agent used in the present invention may contain curing agent components other than the amine curing agent, but from the viewpoint of improving oxygen absorption and gas barrier properties, the content of the amine curing agent is preferably high. preferable.
  • the content of the amine curing agent in the epoxy resin curing agent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, from the viewpoint of improving oxygen absorption and gas barrier properties. More preferably, it is 90% by mass or more and 100% by mass or less.
  • the blending ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition may be within the standard blending range when producing an epoxy resin reactant by generally reacting the epoxy resin and the epoxy resin curing agent.
  • the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is 0.2 to 12.0.
  • the range is within the range.
  • (number of active hydrogens in epoxy resin curing agent/number of epoxy groups in epoxy resin) is more preferably 0.2 to 10.0, even more preferably is 0.2 to 8.0, even more preferably 0.5 to 6.0, even more preferably more than 1.0 and 5.0 or less, even more preferably 1.1 to 5.0, even more preferably The range is from 2.0 to 5.0, more preferably from 3.0 to 5.0, even more preferably from 3.5 to 5.0.
  • the epoxy resin composition may further contain a coupling agent from the viewpoint of improving the adhesion of the obtained cured product layer (III) to the inorganic layer (II).
  • a coupling agent examples include silane coupling agents, titanate coupling agents, aluminate coupling agents, and the like, with silane coupling agents being preferred.
  • the silane coupling agent examples include a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth)acrylic group, and a mercapto group. Examples include silane coupling agents having the following.
  • a silane coupling agent having an amino group and a silane coupling agent having an epoxy group are selected from the viewpoint of improving the adhesion of the obtained cured product layer (III) to the inorganic layer (II). At least one type is preferred.
  • the content of the coupling agent in the epoxy resin composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of the epoxy resin curing agent. be.
  • the epoxy resin composition may optionally include a thermosetting resin, a wetting agent, a tackifier, an antifoaming agent, a curing accelerator, an antirust additive, a pigment, and an oxygen scavenger to the extent that the effects of the present invention are not impaired.
  • Additives such as agents may be added.
  • the total content of the additives in the epoxy resin composition is preferably 20.0 parts by mass or less, more preferably is 0.001 to 15.0 parts by mass.
  • the total content of the epoxy resin and the epoxy resin curing agent in the solid content of the epoxy resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably is 80% by mass or more, more preferably 85% by mass or more, and 100% by mass or less.
  • Solid content of the epoxy resin composition means the components in the epoxy resin composition excluding water and organic solvent.
  • the epoxy resin composition may contain an organic solvent, and the organic solvent is preferably a non-reactive solvent.
  • the organic solvent is preferably a non-reactive solvent.
  • Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxyethanol,
  • protic polar solvents such as 2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol
  • one or more of ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, etc. may be used. I can do it.
  • at least one selected from the group consisting of methanol, ethanol, and ethyl acetate is preferred.
  • the epoxy resin composition preferably has a low lubricant content from the viewpoint of the obtained cured product layer (III) exhibiting higher adhesiveness.
  • the content of the lubricant in the epoxy resin composition is preferably less than 10 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the total amount of epoxy resin and epoxy resin curing agent in the epoxy resin composition. less than 2 parts by weight, even more preferably less than 1 part by weight, even more preferably less than 0.1 parts by weight, even more preferably less than 0.01 parts by weight, even more preferably 0. Part by mass.
  • the above-mentioned lubricant includes, in addition to components conventionally known as lubricants, unsaturated fatty acid amides having 14 to 24 carbon atoms, such as erucic acid amide and oleic acid amide.
  • the epoxy resin composition preferably has a low content of fillers such as organic or inorganic powder, organic or inorganic fibers, etc., from the viewpoint that the obtained cured material layer (III) exhibits higher adhesiveness.
  • the content of the filler in the epoxy resin composition is preferably less than 10 parts by mass, more preferably less than 100 parts by mass of the total amount of epoxy resin and epoxy resin curing agent in the epoxy resin composition. Less than 5 parts by weight, more preferably less than 2 parts by weight, even more preferably less than 1 part by weight, even more preferably less than 0.1 parts by weight, even more preferably less than 0.01 parts by weight, even more preferably It is 0 parts by mass.
  • the epoxy resin composition can be prepared, for example, by blending predetermined amounts of an epoxy resin, an epoxy resin curing agent, and additives and solvents used as necessary, and then stirring and mixing using known methods and equipment. .
  • the thickness of the cured material layer (III) is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, even more preferably 1.5 ⁇ m, from the viewpoint of improving oxygen absorption and gas barrier properties. That's all. Further, from the viewpoint of improving adhesiveness, the thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 5 ⁇ m or less. The above thickness is the thickness per layer of the cured material layer (III).
  • the oxygen absorbing material of the present invention has arbitrary layers such as an adhesive layer, a primer layer, an ink layer, and a surface protection layer in addition to the base material (I), the inorganic layer (II), and the cured material layer (III). It's okay. However, the inorganic layer (II) and the cured material layer (III) must be adjacent to each other, and no arbitrary layer is included between the inorganic layer (II) and the cured material layer (III).
  • the oxygen absorbing material of the present invention exhibits oxygen absorbing properties through the inorganic layer (II) and the cured material layer (III), so it does not have any oxygen absorbing layers other than the inorganic layer (II) and the cured material layer (III). It is preferable.
  • the oxygen absorbing layer include a polyamide resin layer containing a polyamide resin and a transition metal. Transition metals refer to elements in Groups 3 to 11 of the periodic table, and are compounds that improve oxygen absorption performance by being included in the polyamide resin layer, generally in the form of inorganic acid salts, organic acid salts, or complex salts. It is. Such transition metals include cobalt, copper, cerium, manganese, iron, chromium and nickel.
  • the total content of transition metals in the oxygen absorbing material of the present invention is preferably less than 5 ppm, more preferably less than 3 ppm, even more preferably less than 1 ppm, even more preferably 0. It is less than 1 ppm.
  • the total thickness of the oxygen absorbing material varies depending on the layer structure, but from the viewpoint of improving oxygen absorption and gas barrier properties, it is preferably 6 to 600 ⁇ m, more preferably 10 to 500 ⁇ m, even more preferably 20 to 300 ⁇ m, and even more preferably It is 20 to 200 ⁇ m.
  • the method for producing the oxygen absorbing material of the present invention is not particularly limited, and any known method can be used.
  • a method for manufacturing an oxygen absorbing material in which a base material (I), an inorganic layer (II), and a cured material layer (III) are laminated in this order the inorganic layer (II) is formed on one side of the base material (I).
  • the epoxy resin composition may be applied onto the inorganic layer (II) to a desired thickness, and then the epoxy resin composition may be cured to form a cured layer (III).
  • the cured material layer (III) may be formed on the inorganic layer (II) using a film in which the inorganic layer (II) is previously formed on the base material (I).
  • a method for manufacturing an oxygen absorbing material in which a base material (IA), an inorganic layer (II), a cured material layer (III), and a base material (IB) are laminated in this order an inorganic layer is formed on one side of the base material (IA).
  • Application methods for applying the epoxy resin composition include, for example, bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coating, die coating, slot die coating, vacuum die coating, Examples include dip coating, spin coating, roll coating, spray coating, and brush coating. Among these, bar coating, roll coating, and spray coating are preferred, and industrially, gravure coating, reverse gravure coating, microgravure coating, and microreverse gravure coating are preferred.
  • a step of volatilizing the solvent drying step
  • the conditions in the drying step can be selected as appropriate, and for example, the drying temperature can be 60 to 180° C. and the drying time can be 5 to 180 seconds.
  • the epoxy resin composition is cured to form a cured material layer (III).
  • the curing temperature can be selected, for example, from 10 to 140°C, preferably from 10 to 80°C.
  • the curing time can be selected, for example, in the range of 0.5 to 200 hours, preferably in the range of 2 to 100 hours.
  • the oxygen absorbing material of the present invention has oxygen absorbing properties and excellent gas barrier properties.
  • the oxygen permeability of the oxygen absorbing material at 23° C. and 60% relative humidity varies depending on the barrier properties of the base material (I) and inorganic layer (II) used, but is preferably 1 cc ( m2 ⁇ day ⁇ atm ) or less, more preferably 0.8 cc/(m 2 ⁇ day atm) or less, still more preferably 0.6 cc/(m 2 ⁇ day atm) or less, even more preferably 0.3 cc/(m 2 ⁇ day atm) or less ⁇ ATM) or less.
  • the oxygen permeability of the oxygen absorbing material can be measured by the method described in Examples.
  • the shape of the oxygen absorbing material of the present invention can be appropriately selected depending on the form of use, and can be, for example, sheet-shaped or bag-shaped.
  • Examples of ways to use the oxygen absorbing material include a method in which a film-shaped oxygen absorbing material is sealed inside a packaging material such as a container or a packaging bag; a method in which the oxygen absorbing material is used as a packaging material; and the like.
  • a method of preserving an article according to the present invention is a method of preserving an article using the oxygen absorbing material, and the method includes any one or more of the following embodiments (1) or (2).
  • the article is housed in a packaging material encapsulating the oxygen absorbing material.
  • the article is housed in a packaging material having at least a portion of the oxygen absorbing material, and the packaging material has an oxygen permeability of 1 cc/(m 2 ⁇ day ⁇ atm) or less. Since the oxygen-absorbing material has oxygen-absorbing properties, the article preservation method of the present invention (hereinafter also simply referred to as the "method of the present invention") effectively suppresses oxidative deterioration of the article to be preserved. can do.
  • the article is housed in a packaging material encapsulating the oxygen absorbing material.
  • the shape of the oxygen absorbing material used in the above aspect (1) may be any shape as long as it can be enclosed within the packaging material, and preferably a sheet shape.
  • the oxygen absorbing material may be attached within the packaging material, or may be enclosed within the packaging material while being housed in a packaging bag.
  • the form of the packaging material used in the above aspect (1) can be selected as appropriate depending on the article to be stored or preserved.
  • packaging film for example, packaging film; packaging containers such as packaging bags and bottles; and lids of packaging containers. materials, sealing materials, etc.
  • Specific examples of packaging films or packaging bags include three-sided sealed flat bags, standing pouches, gusset packaging bags, pillow packaging bags, and bags consisting of a main chamber and a sub-chamber, with an easily peelable wall between the main chamber and the sub-chamber. Examples include multi-compartment pouches, shrink film packaging, etc.
  • the thickness and capacity of the packaging material are not particularly limited either, and can be appropriately selected depending on the article to be stored.
  • the material of the packaging material used in the above aspect (1) is not particularly limited, it is preferably a packaging material having gas barrier properties.
  • the packaging material is a packaging bag
  • examples thereof include a packaging bag made of aluminum, a packaging bag using a plastic base material having a transparent vapor deposition layer, and the like.
  • the article is housed in a packaging material having at least a portion of the oxygen absorbing material, and the packaging material has an oxygen permeability of 1 cc/(m 2 ⁇ day ⁇ atm) or less.
  • the packaging material is preferably a packaging material made of the oxygen absorbing material.
  • the oxygen permeability of the packaging material used in the above aspect (2) is a value measured by the method described in Examples at 23° C.
  • the form of the packaging material used in the above aspect (2) is preferably a packaging film or a packaging bag from the viewpoint of having at least a part of the oxygen absorbing material, and a specific example thereof is in the aspect (1) above. Same as described.
  • the thickness and capacity of the packaging material are not particularly limited either, and can be appropriately selected depending on the article to be stored.
  • the method of the present invention may include the aspects (1) and (2) above.
  • the article preferably contains water.
  • the water activity (Aw) of the food is preferably 0.75 or more, more preferably is 0.80 or more, more preferably 0.85 or more, even more preferably 0.90 or more, even more preferably 0.95 or more.
  • the temperature inside the packaging material containing the article is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 25°C or higher, from the viewpoint of increasing the oxygen absorbing property of the oxygen absorbing material. Yes, and usually below 80°C.
  • the packaging material containing the article is stored in an environment that is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 25°C or higher, and usually 80°C or lower.
  • the relative humidity within the packaging material containing the article is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more, from the viewpoint of increasing the oxygen absorption ability of the oxygen absorbing material. and is less than 100%.
  • the packaging material containing the article is stored in an environment where the relative humidity is preferably 85% or higher, more preferably 90% or higher, even more preferably 95% or higher, and 100% or lower.
  • the present invention further includes a base material (I), an inorganic layer (II), and a cured product layer (III) of an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent containing an amine-based curing agent.
  • a base material (I), an inorganic layer (II), and a cured product layer (III) of an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent containing an amine-based curing agent is provided.
  • the details and preferred embodiments of the base material (I), the inorganic layer (II), the cured material layer (III), and the laminate are the same as those described for the oxygen absorbing material.
  • ⁇ Thickness of cured material layer> The measurement was performed using a multilayer film thickness measuring device (“DC-8200” manufactured by Gunze Co., Ltd.).
  • ⁇ Oxygen absorption amount (cc/g)> The film-like oxygen absorbing material obtained in each example was cut to prepare four rectangular test pieces of 5 cm x 15 cm. This was placed in an aluminum bag of approximately 21 cm x 15 cm, and then 200 cc of air was sealed in the bag, the humidity was adjusted so that the inside of the bag reached the humidity listed in the table, and then the bag was sealed. After storing the aluminum bag for a specified period of time at the temperature listed in the table, the oxygen concentration inside the bag was measured using a zirconia oxygen concentration measuring device (“LC-750F” manufactured by Toray Engineering Co., Ltd.), and one piece of oxygen absorbing material was measured. The amount of oxygen absorbed per unit was calculated.
  • LC-750F zirconia oxygen concentration measuring device
  • Production Example 1 (Preparation of epoxy resin curing agent solution A) A reaction vessel was charged with 1 mol of metaxylylene diamine (MXDA). The temperature was raised to 60° C. under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165° C. while distilling off the generated methanol, and the temperature was maintained at 165° C. for 2.5 hours to obtain an amine curing agent.
  • MXDA metaxylylene diamine
  • TTRAD-X an epoxy resin having a glycidylamino group derived from metaxylylene diamine
  • Production Example 3 (Preparation of epoxy resin composition B)
  • the blending amount of methanol as a diluting solvent was 1.98 g
  • the blending amount of epoxy resin curing agent solution A obtained in Production Example 1 was 3.64 g
  • Epoxy resin composition B was prepared in the same manner as in Production Example 2 except for the above.
  • Production example 4 (preparation of epoxy resin composition C)
  • the blending amount of methanol as a diluting solvent was 1.56 g
  • the blending amount of epoxy resin curing agent solution A obtained in Production Example 1 was 4.83 g
  • Epoxy resin composition C was prepared in the same manner as in Production Example 2 except for the above.
  • Production Example 5 (Preparation of epoxy resin composition D)
  • the blending amount of methanol as a diluting solvent was 3.62 g
  • the blending amount of ethyl acetate was 4.30 g
  • the blending amount of epoxy resin curing agent solution A obtained in Production Example 1 was 1.93 g
  • meth The blending amount of epoxy resin having a glycidylamino group derived from xylylene diamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd.) was 0.14 g (number of active hydrogens in epoxy resin curing agent/number of active hydrogens in epoxy resin).
  • Epoxy resin composition D was prepared in the same manner as in Production Example 2, except that the number of epoxy groups was changed to 5.0).
  • Production Example 6 (Preparation of epoxy resin composition E)
  • the blending amount of methanol, which is a diluting solvent was changed to 2.47 g
  • the blending amount of epoxy resin curing agent solution A obtained in Production Example 1 was changed to 2.20 g.
  • the epoxy resin having a glycidylamino group (“TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
  • a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A (“jER828” manufactured by Mitsubishi Chemical Corporation) was used.
  • Production Example 7 (Preparation of epoxy resin composition F)
  • the blending amount of methanol, which is a diluting solvent was changed to 2.40 g
  • the blending amount of epoxy resin curing agent solution A obtained in Production Example 1 was changed to 2.40 g.
  • an epoxy resin having a glycidylamino group (“TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
  • an epoxy resin having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Epoxy resin composition F was prepared.
  • Example 1 (Preparation and evaluation of oxygen absorbing material) On the aluminum vapor-deposited surface of an aluminum vapor-deposited CPP ("Chemilite SF-1" manufactured by Nakai Kogyo Co., Ltd., thickness 25 ⁇ m) in which aluminum was vapor-deposited on one side of an unstretched polypropylene (CPP) film, the film obtained in Production Example 2 was applied.
  • the epoxy resin composition A was coated with bar coater No. 8 was used for coating.
  • the epoxy resin composition was dried by heating at 80° C. for 10 seconds (thickness after drying: 3 ⁇ m).
  • a biaxially oriented polypropylene (OPP) film (“FOR” manufactured by Futamura Chemical Co., Ltd., thickness 20 ⁇ m) was laminated with a nip roll, heated at 40°C for 2 days, and the layer structure shown in Table 1 was applied.
  • An oxygen absorbing material having the following properties was obtained. Using this oxygen absorbing material, the amount of oxygen absorbed was measured by the method described above. In the measurement of the amount of oxygen absorption, the humidity inside the aluminum bag was controlled by enclosing hydrated absorbent cotton inside the bag. The results are shown in Table 1.
  • “A/E” means the number of active hydrogens in the epoxy resin curing agent/the number of epoxy groups in the epoxy resin.
  • Example 1 an oxygen absorbing material was prepared in the same manner as in Example 1, except that the epoxy resin composition was changed to one listed in Table 1, and the amount of oxygen absorbed was measured using the method described above. The results are shown in Table 1.
  • Comparative example 1 an oxygen absorbing material was produced by the following method using a urethane adhesive instead of the epoxy resin composition A.
  • the urethane adhesive used was prepared by adding 0.8 g of CAT-RT37-0.8K, a curing agent, and 38.7 g of ethyl acetate, a solvent, to 17 g of TM-569 as a base agent, and stirring well.
  • the above urethane adhesive was applied to the aluminum vapor deposited surface of the aluminum vapor deposited CPP using bar coater No. 12 and dried at 80° C. for 10 seconds to form an adhesive layer (thickness after drying: 3 ⁇ m).
  • the OPP film having a thickness of 20 ⁇ m was laminated thereon using nip rolls and heated at 40° C. for 2 days to obtain an oxygen absorbing material having the layer structure shown in Table 1.
  • the amount of oxygen absorbed was measured in the same manner as described above.
  • the humidity inside the aluminum bag was controlled by enclosing hydrated absorbent cotton inside the bag. The results are shown in Table 1.
  • the oxygen absorbing material of the present invention has better oxygen absorbing properties than the oxygen absorbing material of the comparative example. Further, from a comparison of Examples 1 to 3, in the epoxy resin composition used for the cured material layer, the number of active hydrogens in the epoxy resin curing agent/the number of epoxy groups in the epoxy resin is in the range of 1.2 to 5.0. In this case, it can be seen that the amount of oxygen absorbed increased even more.
  • Example 5 The epoxy resin obtained in Production Example 2 was applied to the aluminum-deposited side of a polyethylene terephthalate (PET) film with aluminum vapor-deposited on one side (ML-PET manufactured by Mitsui Chemicals Tohcello Co., Ltd., thickness 12 ⁇ m).
  • Composition A was coated with bar coater No. 8 was used for coating.
  • the epoxy resin composition was dried by heating at 80° C. for 10 seconds (thickness after drying: 3 ⁇ m).
  • an unstretched polypropylene (CPP) film ("P1146" manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) was laminated with a nip roll and heated at 40°C for 2 days to form the layer structure shown in Table 2.
  • Example 6 an oxygen absorbing material was produced in the same manner as in Example 5, except that epoxy resin composition C obtained in Production Example 4 was used instead of epoxy resin composition A, and The amount of oxygen absorbed was measured. The results are shown in Table 2.
  • Example 7 In Example 5, aluminum vapor-deposited OPP ("ML-OP102" manufactured by Mitsui Chemicals Tohcello Co., Ltd., thickness 12 ⁇ m), in which aluminum was vapor-deposited on one side of a stretched polypropylene (OPP) film, was used instead of aluminum vapor-deposited PET. Except for the above, an oxygen absorbing material was produced in the same manner as in Example 5, and the amount of oxygen absorbed was measured using the method described above. The results are shown in Table 2.
  • Example 8 In Example 6, an oxygen absorbing material was produced in the same manner as in Example 6, except that the aluminum-deposited OPP was used instead of the aluminum-deposited PET, and the amount of oxygen absorbed was measured by the method described above. The results are shown in Table 2.
  • Example 9 The epoxy resin obtained in Production Example 2 was applied to the alumina-deposited surface of alumina-deposited PET (“Barrierox 1011HG” manufactured by Toray Film Processing Co., Ltd., thickness 12 ⁇ m), in which alumina was deposited on one side of a polyethylene terephthalate (PET) film.
  • Composition A was coated with bar coater No. 8 was used for coating.
  • the epoxy resin composition was dried by heating at 80° C. for 10 seconds (thickness after drying: 3 ⁇ m).
  • an unstretched polypropylene (CPP) film ("P1146" manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) was laminated with a nip roll and heated at 40°C for 2 days to form the layer structure shown in Table 3.
  • An oxygen absorbing material was obtained. Using this oxygen absorbing material, the amount of oxygen absorbed was measured by the method described above. In the measurement of the amount of oxygen absorption, the humidity inside the aluminum bag was controlled by enclosing hydrated absorbent cotton inside the bag. The results are shown in Table 3.
  • Example 10 an oxygen absorbing material was produced in the same manner as in Example 9, except that epoxy resin composition C obtained in Production Example 4 was used in place of epoxy resin composition A, and The amount of oxygen absorbed was measured. The results are shown in Table 3.
  • Example 11 silica vapor-deposited PET ("Tech Barrier TCBL" manufactured by Mitsubishi Chemical Holdings Group, thickness 12 ⁇ m), in which silica was vapor-deposited on one side of a polyethylene terephthalate (PET) film, was used instead of alumina vapor-deposited PET.
  • PET polyethylene terephthalate
  • Example 12 an oxygen absorbing material was produced in the same manner as in Example 10, except that the silica-deposited PET was used instead of the alumina-deposited PET, and the amount of oxygen absorbed was measured by the method described above. The results are shown in Table 3.
  • Table 2 shows an example in which the types of base materials (IA) and (IB) constituting the oxygen absorbing material were changed
  • Table 3 shows an example in which the type of the inorganic layer (II) constituting the oxygen absorbing material was changed.
  • Table 2 shows that among the combinations of base materials (IA) and (IB), the configurations of Examples 1 and 3 increased the amount of oxygen absorption the most.
  • the inorganic layer (II) was an aluminum vapor-deposited layer, the amount of oxygen absorbed increased compared to the cases where the alumina vapor-deposited layer and the silica vapor-deposited layer were used.
  • Example 13 In Example 1, the amount of oxygen absorbed was measured in the same manner as in Example 1, except that the storage temperature of the oxygen absorbing material was changed to 23°C. The results are shown in Table 4.
  • Example 14 In Example 3, the amount of oxygen absorbed was measured in the same manner as in Example 3, except that the storage temperature of the oxygen absorbing material was changed to 23°C. The results are shown in Table 4.
  • Example 15-20 Oxygen absorption was carried out in the same manner as in Example 3, except that the oxygen absorbing material prepared in Example 3 was used and the humidity inside the aluminum bag was adjusted to the humidity listed in Table 5 using water and glycerin. The amount was measured. The results are shown in Table 5.
  • Example 21 shows an example in which aluminum foil was used as the inorganic layer (II).
  • a polyethylene terephthalate film (thickness 12 ⁇ m)
  • bar coater No. 12 was coated with bar coater No. 12 and dried at 80° C. for 10 seconds to form an adhesive layer (thickness after drying: 3 ⁇ m).
  • an aluminum foil with a thickness of 7 ⁇ m was bonded using nip rolls.
  • the epoxy resin composition C obtained in Production Example 4 was applied to the aluminum foil surface using a bar coater No. 8 and dried by heating at 80° C. for 10 seconds (thickness after drying: 3 ⁇ m).
  • an unstretched polypropylene (CPP) film ("P1146" manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) was laminated with a nip roll and heated at 40°C for 2 days to form the layer structure shown in Table 6.
  • An oxygen absorbing material was obtained. Using the oxygen absorbing material, the amount of oxygen absorbed was measured by the method described above. The results are shown in Table 6.
  • Example 3 an oxygen absorbing material was prepared in the same manner as in Example 3, except that the epoxy resin composition shown in Table 7 was used, and the amount of oxygen absorbed was measured by the method described above. The results are shown in Table 7.
  • Example 24 (preservation method)
  • OPP biaxially oriented polypropylene
  • white ink (Bellcolor R115" manufactured by Sakata Inx Co., Ltd.) using a diluting solvent (“FOR” manufactured by Sakata Inx Co., Ltd.). 2 times diluted with "L solvent”) was applied to bar coater No. 8 and dried by heating at 80° C. for 10 seconds (thickness after drying: about 0.5 ⁇ m) to form a colored layer.
  • gravure ink for back printing (“Bell Flora R Medium” manufactured by Sakata Inx Co., Ltd.
  • Epoxy resin composition C obtained in Production Example 4 was applied onto the medium layer using bar coater No. 8 and dried by heating at 80° C. for 10 seconds (thickness after drying: 3 ⁇ m).
  • CPP Aluminum vapor-deposited CPP ("Chemilite SF-1" manufactured by Nakai Kogyo Co., Ltd., 25 ⁇ m thick) in which aluminum was vapor-deposited on the coated surface of the epoxy resin composition and on one side of an unstretched polypropylene (CPP) film.
  • the vapor-deposited surfaces are overlapped and bonded together using nip rolls, and heated at 40°C for 2 days to form CPP film (base material (IA))/aluminum vapor-deposited layer (II)/cured material layer (III)/medium layer/colored layer.
  • An oxygen absorbing material having a structure in which /OPP films (base material (IB)) were sequentially laminated was obtained.
  • the above oxygen absorbing material was made into a bag with the base material (IA) side facing inside to produce a bag-shaped packaging material.
  • the oxygen permeability of the oxygen absorbing material constituting the packaging material was 0.09 cc/(m 2 ⁇ day ⁇ atm).
  • the oxygen permeability was measured by the method described below. Kirimochi (Fig. 1(a), water activity Aw: 0.99) was placed in a bag-shaped packaging material and sealed, and the packaging material was stored for 2 months in an environment of 40 ° C. and 90% relative humidity. did.
  • the initial amount of oxygen in the packaging material was 10 cc, and the initial oxygen concentration in the packaging material was 20.8%. After storage for 2 months, visual observation of the appearance of the cut rice cakes revealed no change in appearance ( Figure 1(b)).
  • the oxygen permeability was measured using an oxygen permeability measuring device ("OX-TRAN2/21" manufactured by Modern Control) under conditions of 23° C. and 60% relative humidity.
  • Example 24 the epoxy resin composition C obtained in Production Example 4 was replaced with the urethane adhesive (17 g of TM-569 as the main ingredient, 0.8 g of CAT-RT37-0.8K as a curing agent, and a solvent). Kirimochi was stored in the same manner as in Example 24, except that 38.7 g of ethyl acetate was added thereto and stirred thoroughly.
  • the oxygen permeability of the oxygen absorbing material constituting the packaging material was 2.7 cc/(m 2 ⁇ day ⁇ atm). After storage for 2 months, the appearance of the cut rice cakes was visually observed and mold growth was observed ( Figure 1(c)).
  • Comparative example 3 The urethane adhesive was applied to one side of aluminum foil (thickness: 7 ⁇ m) using bar coater No. 12 and dried at 80° C. for 10 seconds to form an adhesive layer (thickness after drying: 3 ⁇ m).
  • a PET film (“E5100" manufactured by Toyobo Co., Ltd., thickness 12 ⁇ m) was laminated with a nip roll, and heated at 40°C for 2 days to form the aluminum foil (II) / urethane adhesive layer / PET film.
  • a laminate film having a structure in which the layers were laminated in order was obtained. Thereafter, the urethane adhesive was applied to the aluminum foil surface of the laminate film using a bar coater No.
  • an unstretched polypropylene (CPP) film (P1146 manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m) was laminated using nip rolls, heated at 40°C for 2 days, and CPP/urethane adhesive layer/aluminum foil A laminate having a structure in which (II)/urethane adhesive layer/PET film were laminated in this order was obtained.
  • the laminate was made into a bag with the aluminum foil (II) side facing inside to produce a bag-shaped packaging material.
  • the oxygen permeability of the laminate constituting the packaging material was 0.01 cc/(m 2 ⁇ day ⁇ atm) or less.
  • a cut rice cake (FIG. 1(a)) was housed in a bag-shaped packaging material and sealed, and the packaging material was stored for two months in an environment of 40° C. and 90% relative humidity in the same manner as in Example 24.
  • the initial amount of oxygen in the packaging material was 10 cc, and the initial oxygen concentration in the packaging material was 20.8%.
  • Figure 1(d) After storage for 2 months, the appearance of the cut rice cakes was visually observed, and mold growth was observed (Figure 1(d)).
  • mold grew on the cut rice cakes that were the contents, even though a packaging material with high oxygen barrier properties was used. This is thought to be because the packaging material used did not exhibit oxygen absorbing properties, and the contents deteriorated due to residual oxygen in the packaging material.
  • Example 25 In Example 24, the preservability was evaluated in the same manner as in Example 24, except that the item housed in the packaging material was changed to cheese cod (Figure 2 (a), water activity Aw: 0.99). Ta. After storage for 2 months, visual observation of the appearance of the cheese cod revealed no change in appearance (FIG. 2(b)).
  • Comparative example 4 In Comparative Example 2, preservability evaluation was performed in the same manner as in Comparative Example 2, except that the article housed in the packaging material was changed to cheese cod. After storage for 2 months, the appearance of the cheese cod was visually observed, and mold growth was observed (FIG. 2(c)).
  • Comparative example 5 In Comparative Example 3, preservability evaluation was performed in the same manner as in Comparative Example 3, except that the article housed in the packaging material was changed to cheese cod. After storage for 2 months, the appearance of the cheese cod was visually observed, and mold growth was observed (FIG. 2(d)).
  • an oxygen absorbing material particularly suitable for storing water-containing articles or storing articles in a high humidity environment, and a method for preserving articles using the oxygen absorbing material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Nutrition Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/016897 2022-05-11 2023-04-28 酸素吸収材、及び物品を保存する方法 Ceased WO2023219016A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US18/862,739 US20250281901A1 (en) 2022-05-11 2023-04-28 Oxygen absorbent material and method for storing article
KR1020247036989A KR20250009969A (ko) 2022-05-11 2023-04-28 산소흡수재, 및 물품을 보존하는 방법
CN202380038634.3A CN119156286A (zh) 2022-05-11 2023-04-28 氧吸收材料和保存物品的方法
JP2024520412A JPWO2023219016A1 (https=) 2022-05-11 2023-04-28
EP23803494.6A EP4523911A4 (en) 2022-05-11 2023-04-28 OXYGEN ABSORBING MATERIAL AND METHOD FOR PRESERVING ARTICLE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022078084 2022-05-11
JP2022-078084 2022-05-11

Publications (1)

Publication Number Publication Date
WO2023219016A1 true WO2023219016A1 (ja) 2023-11-16

Family

ID=88730484

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/016897 Ceased WO2023219016A1 (ja) 2022-05-11 2023-04-28 酸素吸収材、及び物品を保存する方法

Country Status (7)

Country Link
US (1) US20250281901A1 (https=)
EP (1) EP4523911A4 (https=)
JP (1) JPWO2023219016A1 (https=)
KR (1) KR20250009969A (https=)
CN (1) CN119156286A (https=)
TW (1) TW202406748A (https=)
WO (1) WO2023219016A1 (https=)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003128022A (ja) * 2001-10-25 2003-05-08 Mitsubishi Gas Chem Co Inc 物品の保存方法
JP2003205583A (ja) * 2002-01-11 2003-07-22 Mitsubishi Gas Chem Co Inc 脱酸素性多層フィルム
JP2010012769A (ja) * 2008-06-03 2010-01-21 Mitsubishi Gas Chemical Co Inc 耐屈曲性ラミネートフィルム
JP2012075716A (ja) * 2010-10-01 2012-04-19 Fujifilm Corp 輸液バックおよび外装用フィルム
JP2015007148A (ja) 2013-06-24 2015-01-15 三菱瓦斯化学株式会社 酸素吸収性樹脂組成物
JP2015085545A (ja) * 2013-10-28 2015-05-07 凸版印刷株式会社 ガスバリア性積層フィルム
JP2016097596A (ja) * 2014-11-21 2016-05-30 三菱瓦斯化学株式会社 ガスバリア性コートフィルム
JP2016140810A (ja) 2015-01-30 2016-08-08 上野製薬株式会社 酸素吸収剤
JP2020082437A (ja) * 2018-11-20 2020-06-04 凸版印刷株式会社 積層体、包装体及び包装物品
WO2021029171A1 (ja) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 ガスバリア性包装材

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5636638B2 (ja) * 2009-06-11 2014-12-10 三菱瓦斯化学株式会社 アミン系エポキシ樹脂硬化剤およびエポキシ樹脂組成物
JP6912012B2 (ja) * 2019-08-14 2021-07-28 三菱瓦斯化学株式会社 エポキシ樹脂組成物、ガスバリア性フィルム及び積層体
JP7775713B2 (ja) * 2020-02-04 2025-11-26 三菱瓦斯化学株式会社 エポキシ樹脂組成物、ガスバリア性積層体、レトルト食品用包装材、防臭用又は保香用包装材、熱収縮性ラベル及びその製造方法、熱収縮ラベル及びこれを有するボトル

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003128022A (ja) * 2001-10-25 2003-05-08 Mitsubishi Gas Chem Co Inc 物品の保存方法
JP2003205583A (ja) * 2002-01-11 2003-07-22 Mitsubishi Gas Chem Co Inc 脱酸素性多層フィルム
JP2010012769A (ja) * 2008-06-03 2010-01-21 Mitsubishi Gas Chemical Co Inc 耐屈曲性ラミネートフィルム
JP2012075716A (ja) * 2010-10-01 2012-04-19 Fujifilm Corp 輸液バックおよび外装用フィルム
JP2015007148A (ja) 2013-06-24 2015-01-15 三菱瓦斯化学株式会社 酸素吸収性樹脂組成物
JP2015085545A (ja) * 2013-10-28 2015-05-07 凸版印刷株式会社 ガスバリア性積層フィルム
JP2016097596A (ja) * 2014-11-21 2016-05-30 三菱瓦斯化学株式会社 ガスバリア性コートフィルム
JP2016140810A (ja) 2015-01-30 2016-08-08 上野製薬株式会社 酸素吸収剤
JP2020082437A (ja) * 2018-11-20 2020-06-04 凸版印刷株式会社 積層体、包装体及び包装物品
WO2021029171A1 (ja) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 ガスバリア性包装材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4523911A4

Also Published As

Publication number Publication date
CN119156286A (zh) 2024-12-17
US20250281901A1 (en) 2025-09-11
KR20250009969A (ko) 2025-01-20
EP4523911A1 (en) 2025-03-19
JPWO2023219016A1 (https=) 2023-11-16
EP4523911A4 (en) 2025-09-03
TW202406748A (zh) 2024-02-16

Similar Documents

Publication Publication Date Title
JP6241674B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物、及びガスバリア性接着剤、並びにガスバリア性積層体
JP6137502B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物、及びガスバリア性接着剤、並びにガスバリア性積層体
CN101679611B (zh) 胺类环氧树脂固化剂、含有该固化剂的气体阻隔性环氧树脂组合物、涂料和层压用粘合剂
JP5776685B2 (ja) エポキシ樹脂硬化剤、エポキシ樹脂組成物及びラミネート用接着剤
TWI507440B (zh) 環氧樹脂硬化劑、環氧樹脂組成物及疊合用接著劑
JP5109877B2 (ja) 耐屈曲性ラミネートフィルム
EP1270206B1 (en) Oxygen-absorbing multi-layer film
TWI902749B (zh) 環氧樹脂組成物、氣體阻隔性疊層體、殺菌食品用包裝材、防臭用或保香用包裝材、熱收縮性標籤及其製造方法、熱收縮標籤及有此標籤之瓶
JP5320924B2 (ja) ガスバリア性積層体
WO2023219016A1 (ja) 酸素吸収材、及び物品を保存する方法
JP5640770B2 (ja) エポキシ樹脂硬化剤の製造方法
TWI902927B (zh) 環氧樹脂組成物、氣體阻隔性疊層體以及包裝材
JP5195122B2 (ja) ガスバリア性容器
JP5051030B2 (ja) ガスバリア性積層体
JP4003041B2 (ja) 脱酸素性多層フィルム
JP4867574B2 (ja) ガスバリアフィルム及びその製造方法
JP4899807B2 (ja) 香辛料含有食品の保存方法
JP5584999B2 (ja) ガスバリアコートフィルム及びその製造方法
JP2006280335A (ja) 酢含有物品の保存方法
JP2006280334A (ja) 醤油含有物品の保存方法
HK1141042B (en) Amine epoxy resin curing agent, gas barrier epoxy resin composition comprising the curing agent, coating agent, and adhesive agent for laminate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23803494

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024520412

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 18862739

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 202380038634.3

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2023803494

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023803494

Country of ref document: EP

Effective date: 20241211

WWP Wipo information: published in national office

Ref document number: 18862739

Country of ref document: US