WO2024190713A1 - 脱酸素剤包装体、並びに脱酸素剤用通気性包装材及びその製造方法 - Google Patents

脱酸素剤包装体、並びに脱酸素剤用通気性包装材及びその製造方法 Download PDF

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Publication number
WO2024190713A1
WO2024190713A1 PCT/JP2024/009213 JP2024009213W WO2024190713A1 WO 2024190713 A1 WO2024190713 A1 WO 2024190713A1 JP 2024009213 W JP2024009213 W JP 2024009213W WO 2024190713 A1 WO2024190713 A1 WO 2024190713A1
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WIPO (PCT)
Prior art keywords
layer
packaging material
oxygen absorber
breathable packaging
nonwoven fabric
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
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PCT/JP2024/009213
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English (en)
French (fr)
Japanese (ja)
Inventor
大揮 佐藤
理紗 渡辺
朋央 増山
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 KR1020257029699A priority Critical patent/KR20250161546A/ko
Priority to EP24770819.1A priority patent/EP4682080A1/en
Priority to JP2025506831A priority patent/JPWO2024190713A1/ja
Priority to CN202480017233.4A priority patent/CN120752186A/zh
Publication of WO2024190713A1 publication Critical patent/WO2024190713A1/ja
Priority to IL323116A priority patent/IL323116A/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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an oxygen absorber package, a breathable packaging material for oxygen absorbers, and a method for producing the same.
  • oxygen absorbers are used to remove oxygen from the sealed containers in which these items are stored, in order to prevent oxidative deterioration and enable long-term storage.
  • Oxygen absorbers are used in a variety of ways depending on the purpose and manner of use. For example, oxygen absorbers in powder or tablet form are packaged in packaging material to form small pouches into oxygen absorber packages. If this oxygen absorber package is placed inside a sealed container in which food or other items are stored, the oxygen absorber inside the oxygen absorber package will remove the oxygen from within the sealed container, preventing the food or other items from deteriorating due to oxidation.
  • the packaging materials used for such oxygen absorbers include sheets of resin, paper, or nonwoven fabric, as well as laminates of these.
  • packaging materials that have laminated layers of resin, paper, or nonwoven fabric include packaging materials in which a resin layer with pre-formed ventilation holes is laminated with a layer of paper or nonwoven fabric. By using a resin layer with pre-formed ventilation holes, ventilation with the outside is ensured, allowing the oxygen absorber to effectively exert its oxygen absorbing performance.
  • oxygen absorbers are used for various foods, and when an oxygen absorber package is used for foods that contain a lot of oil, if the packaging material does not have oil resistance or the oil resistance of the packaging material is insufficient, the oil will seep into the packaging material, causing a decrease in breathability and resulting in a decrease in oxygen scavenging performance. In addition, the seeped oil may cause the oxygen absorber to deteriorate and the appearance of the oxygen absorber package to be damaged.
  • greaseproof paper coated with or impregnated with a fluorine-containing greaseproofing agent hereinafter also referred to as "fluorine-based greaseproof paper" has been widely used as the packaging material.
  • a water- and oil-resistant agent composition suitable for use in packaging materials for oxygen absorbers contains a perfluoroalkyl compound (hereinafter, abbreviated as "PFAS"). Since PFAS is persistent and highly bioaccumulative, there has been a movement to restrict its use worldwide, particularly in Europe and the United States, in recent years. For this reason, there is a demand for defluorination of packaging materials for oxygen absorbers as well.
  • PFAS perfluoroalkyl compound
  • the inventors' research has revealed that when non-fluorine-containing greaseproof paper or nonwoven fabric is used instead of fluorine-based greaseproof paper, there are problems with oil resistance and oxygen scavenging performance.
  • the present invention aims to provide an oxygen absorber package that can be defluorinated and exhibits excellent oil resistance and oxygen absorbing performance, as well as a breathable packaging material for oxygen absorbers and a method for producing the same.
  • An oxygen absorber package comprising an oxygen absorber and a breathable packaging material containing the oxygen absorber, the breathable packaging material has a configuration including, in this order, an outer layer having no through-holes, a base layer and a welding layer, an intermediate layer including a nonwoven fabric, and an inner layer having through-holes,
  • the breathable packaging material does not contain fluorine,
  • the melting point of the resin constituting the nonwoven fabric is 50° C. or more higher than the melting point of the resin constituting the welding layer or the melting point of the resin constituting the inner layer,
  • the oxygen absorber package, wherein the nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.
  • the breathable packaging material is formed into a bag shape by heat-sealing edges of the breathable packaging material with the inner layer facing inward,
  • a breathable packaging material for an oxygen absorber comprising an outer layer having no through-holes, a base layer and a welding layer in this order, an intermediate layer including a nonwoven fabric, and an inner layer having through-holes, in this order,
  • the breathable packaging material for oxygen absorbers does not contain fluorine
  • the melting point of the resin constituting the nonwoven fabric is 50° C. or more higher than the higher of the melting point of the resin constituting the welding layer and the melting point of the resin constituting the inner layer
  • the breathable packaging material for an oxygen absorber wherein the nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.
  • the inner layer is placed on the inside, and the edges are heat-sealed to form a bag shape,
  • the breathable packaging material for an oxygen absorber according to the above-mentioned [8], wherein the width perpendicular to the longitudinal direction of the heat-sealed portion is 0.3 mm or more and 15 mm or less.
  • the present invention provides an oxygen absorber package that can be used for defluorination and has excellent oil resistance and oxygen absorbing properties, as well as a breathable packaging material for oxygen absorbers and a method for producing the same.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of an oxygen absorber package according to the present embodiment.
  • FIG. 2 is a schematic view of one embodiment of the oxygen absorber package according to the present embodiment shown in FIG. 1, observed from the X direction.
  • the oxygen absorber package the breathable packaging material for an oxygen absorber, and the method for producing the same according to the present invention will be described in detail below.
  • the term “A to B” in relation to numerical values means “A or more and B or less” (when A ⁇ B) or "A or less and B or more” (when A>B).
  • a combination of preferred embodiments is a more preferred embodiment.
  • "(meth)acrylate”, “(meth)acrylic”, “(meth)acrylic acid”, etc. mean acrylate and/or methacrylate, acrylic and/or methacrylic, acrylic acid and/or methacrylic acid, etc., respectively.
  • the oxygen absorber package of the present invention comprises an oxygen absorber and a breathable packaging material containing the oxygen absorber, the breathable packaging material having a configuration including, in this order, an outer layer having no through holes and including a base material layer and a welding layer, an intermediate layer including a nonwoven fabric, and an inner layer having through holes, the breathable packaging material does not contain fluorine, the melting point of a resin constituting the nonwoven fabric is 50° C. or more higher than the melting point of a resin constituting the welding layer or the melting point of a resin constituting the inner layer, whichever is higher, and the nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the oxygen absorber package of the present invention.
  • the oxygen absorber package 100 includes an oxygen absorber 30 and a breathable packaging material 10 containing the oxygen absorber 30.
  • the breathable packaging material 10 includes, in this order, an outer layer 11 having no through-holes and including a base layer 11a and a welding layer 11b, an intermediate layer 13 including a nonwoven fabric, and an inner layer 15 having a through-hole H.
  • the breathable packaging material 10 does not contain fluorine
  • the melting point of the resin constituting the nonwoven fabric is 50°C or more higher than the melting point of the resin constituting the welding layer 11b or the melting point of the resin constituting the inner layer 15, whichever is higher
  • the thickness t of the nonwoven fabric is 0.20 mm or more and 0.42 mm or less.
  • the oxygen absorber package 100 of the present invention has the above-mentioned configuration, and is therefore compatible with defluorination, and can also exhibit excellent oil resistance and oxygen absorbing performance.
  • the reason why the oxygen absorber package of the present invention exhibits the above-mentioned effects is not clear, but one possible reason is as follows.
  • breathable packaging materials used in oxygen absorber packages have a structure that includes an outer layer, an intermediate layer, and an inner layer, in that order.
  • Conventional breathable packaging materials generally have an outer layer that is perforated to provide breathability. This causes oil to seep in through the perforations in the outer layer, but by using fluorine-based greaseproof paper, which has excellent oil resistance and breathability, as the intermediate layer, the seepage of oil into the inner layer is suppressed.
  • non-fluorine-based greaseproof paper when used as an intermediate layer of a breathable packaging material, although it can prevent oil from penetrating, there is a problem that the breathability of the breathable packaging material 10 is reduced and the oxygen absorbing performance is deteriorated.
  • fluorine-free greaseproof paper and nonwoven fabrics that have the same breathability as fluorine-based greaseproof paper have inferior oil resistance compared to fluorine-based greaseproof paper. Although they can ensure sufficient breathability as breathable packaging materials, they can have the problem of oil seepage, and the permeated oil can deteriorate the oxygen absorbing agent, resulting in a decrease in oxygen absorbing performance.
  • containing no fluorine means that it does not contain fluorine as a component that is intentionally blended and contained. Therefore, this does not apply to cases where fluorine is unintentionally contained.
  • unintentionally contained fluorine include fluorine as an unavoidable impurity that is mixed in in small amounts during the manufacturing process, cleaning process, etc.
  • the content of unintentionally contained fluorine is, for example, less than 100 ppm.
  • oxygen absorbers containing iron powder as the main component are preferred from the viewpoint of oxygen absorption performance. Furthermore, in the case of oxygen absorbers containing iron powder as the main component, if oil soaks into the breathable packaging material, the soaked oil may react with the iron powder in the oxygen absorber, generating a peculiar odor. In order to suppress the generation of such odor, the breathable packaging material that encases the iron-based oxygen absorber is required to have good breathability as well as high oil resistance. Therefore, the breathable packaging material used in the present invention is preferably used when the oxygen absorber contains iron powder as the main component, since it has good breathability and can exhibit particularly excellent oil resistance. As an oxygen absorber containing iron powder as the main component, an iron-based self-reacting oxygen absorber containing iron powder, metal halide, carrier, and water is preferred.
  • the melting point of the resin constituting the base layer 11a is preferably higher than that of the resin constituting the inner layer 15, and the greater the temperature difference between these melting points, the more preferable.
  • the melting point of the resin constituting the base material layer 11a is preferably 200 to 300°C, more preferably 220 to 280°C, and even more preferably 235 to 270°C.
  • the melting point of the resin constituting the welding layer 11b is preferably 85 to 125°C, more preferably 90 to 120°C, and even more preferably 95 to 115°C, from the viewpoint of ensuring good adhesion to the base layer 11a and the intermediate layer 13.
  • the melting point can be measured by the method described in the Examples, and the value given in the catalogue may be used.
  • the welding layer 11b preferably contains a material having heat sealability.
  • the material having heat sealability include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene- ⁇ -olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, acid-modified polyolefin resin obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fum
  • the thickness of the welding layer 11b is not particularly limited, but from the viewpoint of ensuring good adhesion with the base layer 11a and the intermediate layer 13, it is preferably 0.5 to 25 ⁇ m, more preferably 1 to 20 ⁇ m, and even more preferably 10 to 20 ⁇ m.
  • the thickness can be measured by the method described in the examples, and the catalog value may be used.
  • the surface of the outer layer 11 facing the base layer 11a can be printed or drawn by gravure printing or the like.
  • the intermediate layer 13 is a layer containing a nonwoven fabric, and is preferably a layer consisting of only a nonwoven fabric. Such an intermediate layer 13 imparts a certain degree of durability and breathability to the breathable packaging material 10, and at the same time, plays a role in preventing leakage of the oxygen absorber 30 contained in the oxygen absorber package 100.
  • the nonwoven fabric constituting the intermediate layer 13 is a nonwoven fabric made of resin, the melting point of the resin constituting the nonwoven fabric is 50°C or more higher than the higher of the melting point of the resin constituting the welding layer 11b or the melting point of the resin constituting the inner layer 15, and the thickness t of the nonwoven fabric is 0.20 mm or more and 0.42 mm or less.
  • the breathable packaging material 10 exhibits excellent breathability.
  • the nonwoven fabric used in the present invention has a melting point of the resin that constitutes the nonwoven fabric that is at least 50°C higher than the higher of the melting point of the resin that constitutes the welding layer 11b or the melting point of the resin that constitutes the inner layer 15, and the thickness t of the nonwoven fabric is 0.20 mm or more and 0.42 mm or less. This ensures breathability from the cross section 13e of the middle layer 13 at the edge portion 10E of the breathable packaging material 10.
  • the oxygen absorber package 100 shown in Figure 1 comprises an oxygen absorber 30 and a breathable packaging material 10 that contains the oxygen absorber 30. Furthermore, the oxygen absorber package 100 shown in Figure 1 is formed into a bag shape by heat welding (heat sealing) the edges 10E of the breathable packaging material 10 with the inner layer 15 on the inside. In Figure 1, the dashed arrow F indicates the flow of gas corresponding to ventilation.
  • the intermediate layer 13 of the breathable packaging material 10 contains a nonwoven fabric with excellent breathability, which enables ventilation (gas flow F) from the cross section 13e of the intermediate layer 13 at the edge portion 10E of the breathable packaging material 10 through the through hole H of the inner layer 15, thereby ensuring breathability to the inside of the breathable packaging material 10.
  • gas flow F gas flow
  • the resin constituting the nonwoven fabric does not melt and clog the mesh of the nonwoven fabric due to welding during lamination in the manufacturing process of the breathable packaging material 10 or heat welding when forming the breathable packaging material 10 into a bag shape, and the good breathability characteristic of nonwoven fabric can be maintained.
  • the thickness t of the nonwoven fabric 0.20 mm to 0.42 mm, a sufficient area is secured for the cross section 13e of the intermediate layer 13 at the edge portion 10E of the breathable packaging material 10, and no lamination defects (interlayer peeling) occur, so that a breathable packaging material with good breathability can be obtained.
  • the resin constituting the nonwoven fabric is not particularly limited, but examples thereof include thermoplastic resins such as polypropylene, polyamide, and polyester. More specifically, examples thereof include nylon (Ny)-based nonwoven fabrics (such as the "Eltas (registered trademark) series” manufactured by Asahi Kasei Corporation), polyethylene terephthalate (PET)-based nonwoven fabrics (such as the "Eltas (registered trademark) series” manufactured by Asahi Kasei Corporation), and TYVEK (registered trademark, manufactured by Asahi DuPont Flashspan Products Co., Ltd.).
  • the nonwoven fabric preferably contains one or more types selected from the group consisting of polyamide and polyester, more preferably one or more types selected from the group consisting of polyamide and polyester, and even more preferably polyester.
  • the melting point of the resin constituting the nonwoven fabric is 50° C. or more higher than the melting point of the resin constituting the welding layer 11b or the melting point of the resin constituting the inner layer 15, whichever is higher, preferably 70° C. or more higher, more preferably 90° C. or more higher, even more preferably 100° C. or more higher, and even more preferably 110° C. or more higher.
  • the temperature difference between the melting point of the resin constituting the nonwoven fabric and the higher melting point of the resin constituting the welding layer 11b or the melting point of the resin constituting the inner layer 15 is not particularly limited, and may be, for example, 215° C. or less, or 200° C. or less.
  • the melting point of the resin constituting the nonwoven fabric is preferably 150°C or higher and 300°C or lower, more preferably 200°C or higher and 300°C or lower, even more preferably 200°C or higher and 270°C or lower, and even more preferably 230°C or higher and 270°C or lower.
  • the melting point can be measured by the method described in the Examples, and the value given in the catalogue may be used.
  • the basis weight of the nonwoven fabric is not particularly limited, but is preferably 20 to 120 g/m 2 , more preferably 35 to 95 g/m 2 , and even more preferably 40 to 70 g/m 2. By setting the basis weight of the nonwoven fabric within the above range, sufficient durability and breathability can be obtained.
  • the basis weight can be measured in accordance with JIS P 8124:2011 "Paper and paperboard -- Method of measurement of basis weight," but catalog values may also be used.
  • the thickness of the nonwoven fabric is 0.20 mm or more, preferably 0.22 mm or more, more preferably 0.25 mm or more, from the viewpoint of good breathability, and is 0.42 mm or less, preferably 0.39 mm or less, more preferably 0.35 mm or less, particularly from the viewpoint of weldability between the intermediate layer 13 and the inner layer 15.
  • the thickness is 0.20 mm or more and 0.42 mm or less, preferably 0.22 mm or more and 0.39 mm or less, more preferably 0.25 mm or more and 0.35 mm or less.
  • the thickness can be measured by the method described in the examples, and the catalog value may be used.
  • the breathability of the nonwoven fabric is not particularly limited, and for example, the air resistance in accordance with JIS P8117:2009 is, for example, 100 seconds or less, preferably 50 seconds or less, and more preferably 10 seconds or less.
  • the air resistance can be measured by the method described in the Examples, and catalog values may be used.
  • the intermediate layer 13 may contain components other than those constituting the nonwoven fabric, as long as the effects of the present invention are not hindered.
  • Other components that can be used in the intermediate layer 13 are not particularly limited as long as they do not contain fluorine, and examples of such components include sizing agents (anti-bleeding agents), water-resistant agents, water-repellent agents, paper strength agents, and dyes. It is preferable that the intermediate layer 13 is composed only of nonwoven fabric.
  • the inner layer 15 is a layer located on the inner surface side of the breathable packaging material 10. Such an inner layer 15 has through holes H.
  • the inner layer 15 has through holes H, which allows ventilation from the outside to the inside of the breathable packaging material 10.
  • the inner layer 15 preferably contains a thermoplastic resin.
  • a thermoplastic resin There are no particular limitations on the type of thermoplastic resin, and a suitable type can be selected depending on the intended use and the desired physical properties. One type may be used alone, or two or more types may be used in combination.
  • the resin constituting the inner layer 15 examples include olefin-based resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer resins, ethylene-(meth)acrylate copolymer resins, etc.
  • olefin-based resins are preferred, polyethylene and polypropylene are more preferred, and linear low-density polyethylene, high-density polyethylene, and unstretched polypropylene are even more preferred.
  • the inner layer 15 preferably comprises linear low density polyethylene, and more preferably is linear low density polyethylene.
  • the melting point of the resin constituting the inner layer 15 is preferably 80°C or higher, more preferably 95°C or higher, and even more preferably 110°C or higher. By setting it within the above range, when sealing the breathable packaging material 10, the resin constituting the inner layer 15 does not melt even if heat sealing is performed, and as a result, the oxygen absorber can be securely sealed without powder leakage.
  • the melting point of the resin constituting the inner layer 15 is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. By setting it within the above range, sufficient sealing can be achieved in a short time without setting the heat sealing temperature to a very high temperature.
  • the melting point of the resin constituting the inner layer 15 is preferably 80 to 200°C, more preferably 95 to 180°C, and even more preferably 110 to 150°C.
  • the melting point can be measured by the method described in the Examples, and the value given in the catalogue may be used.
  • the inner layer 15 may further contain other components in addition to the thermoplastic resin.
  • Other components that can be used in the inner layer 15 are not particularly limited as long as they do not contain fluorine, but examples include additives such as stabilizers, lubricants, antistatic agents, anti-fogging agents, fillers, colorants, plasticizers, and nucleating agents.
  • the thickness of the inner layer 15 is not particularly limited, but is preferably 0.5 to 80 ⁇ m, more preferably 1 to 60 ⁇ m, even more preferably 10 to 50 ⁇ m, and even more preferably 20 to 50 ⁇ m. By setting the thickness of the inner layer 15 within the above range, sufficient adhesive strength can be obtained with short-time heat sealing. The thickness can be measured by the method described in the examples, and the catalog value may be used.
  • the inner layer 15 has a through hole H.
  • the through hole H is a hole that penetrates from one surface of the inner layer 15 to the other surface.
  • the diameter or density of the through holes H can be adjusted as appropriate so that the desired breathability (air permeability) is obtained for the breathable packaging material 10 as a whole.
  • the diameter or density can be adjusted by its shape, penetration direction, arrangement, number, etc.
  • the diameter or density can be adjusted by the perforation conditions such as the irradiation voltage, current, irradiation time, irradiation direction, etc.
  • the shape of the through hole H is not particularly limited, and examples of the cross section include a circle, a triangle, a square, an ellipse, etc., and the vertical section is preferably a cone, pyramid, etc. tapered from the inner layer 15 side toward the intermediate layer 13 side, or from the intermediate layer 13 side toward the inner layer 15 side.
  • the diameter of the through hole H is not particularly limited, and the diameter ⁇ 1 of the through hole H on the surface of the inner layer 15 that is not in contact with the intermediate layer 13 and the diameter ⁇ 2 of the through hole H on the surface of the inner layer 15 that is in contact with the intermediate layer 13 may be the same or different.
  • the diameters ⁇ 1 and ⁇ 2 of the through hole H can be measured by the method described in the Examples, and are taken as the dimension (long diameter) of the longest part of the opening diameter.
  • the diameters ⁇ 1 and ⁇ 2 of the through holes H may be adjusted as appropriate according to the breathability required for the breathable packaging material 10, for example, 100 to 2500 ⁇ m, preferably 200 to 2000 ⁇ m, more preferably 400 to 1000 ⁇ m, and even more preferably 600 to 1000 ⁇ m.
  • the breathability can be improved while preventing the oxygen absorber 30 inside from leaking out when the oxygen absorber package 100 is made.
  • the method for obtaining the inner layer 15 having the through holes H is not particularly limited, and the inner layer 15 having the through holes H can be formed by subjecting the resin sheet or film constituting the inner layer 15 to a hole opening treatment by a known method.
  • the hole opening treatment method include a method using a needle, a method using a blade, a method using electron beam irradiation, a method using a laser, and the like.
  • the method of opening holes using needles is preferred from the viewpoint of easy control of the size and position of the openings, and the method of opening holes through a cylindrical jig with needles attached to the side (hereinafter also referred to as a "needle roll") is more preferred from the viewpoint of continuously producing a breathable packaging material 10 with a stable density and shape of the openings.
  • the needle diameter of the needle roll is preferably 0.1 to 2.0 mm, more preferably 0.3 to 1.0 mm, and even more preferably 0.5 to 0.7 mm.
  • the needle pattern can be appropriately adjusted in consideration of the air permeability, etc.
  • the temperature of the needle roll can be opened at room temperature, but the opening process can be more stably performed by heating the needle roll within a range not exceeding the melting point of the resin used in the inner layer 15.
  • the processing direction of the hole opening process may be formed so as to penetrate the inner layer 15 from the surface on the side not in contact with the intermediate layer 13, or may be formed so as to penetrate the inner layer 15 from the surface on the side in contact with the intermediate layer 13.
  • the shape of the vertical cross section of the through holes H changes, and the air permeability, etc. can be adjusted.
  • the diameter of the through hole H can be appropriately controlled by the tool used for the hole opening process, the formation direction, etc. Specifically, when a tapered cone-shaped needle is used, if the diameter of the through hole H on the surface of the inner layer 15 that is not in contact with the intermediate layer 13 is taken as diameter ⁇ 1 and the diameter of the through hole H on the surface of the inner layer 15 that is in contact with the intermediate layer 13 is taken as diameter ⁇ 2, (1) when the through hole H is formed so as to penetrate the inner layer 15 from the surface on the side not in contact with the intermediate layer 13, the relationship ⁇ 1> ⁇ 2 is satisfied, and (2) when the through hole H is formed so as to penetrate the inner layer 15 from the surface on the side in contact with the intermediate layer 13, the relationship ⁇ 1 ⁇ 2 is satisfied.
  • the breathable packaging material 10 used in the present invention is for housing the oxygen absorber 30, and is not particularly limited as long as it has a shape capable of housing the oxygen absorber 30, but is preferably in the form of a bag.
  • the bag-shaped breathable packaging material include one formed by bonding two sheets of breathable packaging material 10 with the inner layer 15 on the inside to form a bag, one formed by bonding one sheet of breathable packaging material 10 and one sheet of non-breathable packaging material with the inner layer 15 on the inside to form a bag, and one formed by folding one sheet of breathable packaging material with the inner layer 15 on the inside and bonding the edges together excluding the folded portion to form a bag.
  • the method for bonding the breathable packaging material 10 is not particularly limited, and can be a known method, such as dry lamination or heat sealing.
  • the method for bonding the breathable packaging material 10 is heat sealing
  • the welding temperature during heat sealing is preferably lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer 13. By using the above welding temperature, it is possible to prevent the resin constituting the nonwoven fabric from melting and clogging the pores, and it is possible to maintain good breathability of the breathable packaging material 10.
  • the breathable packaging material 10 when the breathable packaging material 10 is rectangular, examples of the material include two sheets of breathable packaging material 10 stacked together and heat-sealed at the four sides to form a bag, one sheet of breathable packaging material 10 stacked together with one sheet of non-breathable packaging material and heat-sealed at the four sides to form a bag, and one sheet of breathable packaging material 10 folded and heat-sealed at three sides excluding the folded part to form a bag.
  • the breathable packaging material 10 may be made into a cylindrical shape and both ends and the body of the cylindrical body may be heat-sealed to form a bag.
  • the width perpendicular to the length direction of the heat-welded portion is preferably 0.3 mm to 15 mm, more preferably 3 mm to 10 mm.
  • the oxygen absorber can be well retained inside the breathable packaging material.
  • the "length direction of the heat-sealed portion" refers to a continuous direction along the edge of the breathable packaging material. Note that the edge does not necessarily have to be straight and may be curved.
  • FIG 2 is a schematic diagram of the oxygen absorber package 100 of the present invention shown in Figure 1, viewed from the X direction.
  • region S the portion where the edges 10E are heat-sealed together with the inner layer 15 facing inward is shown as region S.
  • L1 and L2 the length direction of the heat-sealed portion S is shown as continuous directions L1 and L2 along the edges 10E of the breathable packaging material 10, and the widths perpendicular to the length directions L1 and L2 of the heat-sealed portion are shown as widths w1 and w2.
  • the method for producing the breathable packaging material 10 of the present invention is not necessarily limited, but preferably includes a step of laminating and welding the outer layer 11 including the base material layer 11a and the welding layer 11b in this order, the intermediate layer 13, and the inner layer 15 in a configuration including the aforementioned base material layer 11a and the welding layer 11b in this order, and the welding step is carried out at a temperature lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer 13.
  • the details of each layer are as described above.
  • the breathable packaging material 10 produced by this manufacturing method exhibits good breathability because the resin that makes up the nonwoven fabric of the middle layer 13 does not melt during the process of stacking and welding the various layers, and the nonwoven fabric does not become clogged.
  • the procedure for laminating and welding the outer layer 11, intermediate layer 13, and inner layer 15 in this order is not limited, so long as the layers are laminated to form the layer configuration.
  • the inner layer 15 and the intermediate layer 13 may be laminated and welded in advance to form a composite layer, and then the outer layer 11 may be laminated and welded on the intermediate layer 13 side of the composite layer, or (2) the outer layer 11 and the intermediate layer 13 may be laminated and welded in advance to form a composite layer, and then the inner layer 15 may be laminated and welded on the intermediate layer 13 side of the composite layer, or (3) the three layers may be laminated and welded at the same time.
  • the procedure (1) above is preferable from the viewpoint of being able to check the state of the openings in the inner layer 15 while working.
  • the method for laminating and welding each layer is not particularly limited, and any known method such as thermal lamination can be used.
  • the welding can be performed in a manner that does not cause the layers to peel off, and may be partial welding or full welding, but full welding is preferable from the viewpoint of ensuring good adhesion.
  • the welding temperature may be any temperature lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer 13, and may be appropriately selected taking into consideration the melting point of the resin constituting the inner layer 15 and the melting point of the resin constituting the welding layer 11b of the outer layer 11. From the viewpoint of obtaining good adhesion, it is preferable that the welding temperature is higher than the higher of the melting point of the resin constituting the inner layer 15 and the melting point of the resin constituting the welding layer 11b of the outer layer 11. Specifically, the welding temperature is preferably 150°C or higher and 280°C or lower, more preferably 170°C or higher and 230°C or lower, and even more preferably 170°C or higher and lower than 230°C.
  • the method for producing the oxygen absorber package 100 of the present invention is not particularly limited, and a suitable method can be adopted as appropriate, taking into consideration the purpose of use, environment, etc.
  • the oxygen absorber package 100 of the present invention has excellent oil resistance and oxygen absorbing performance because it contains the breathable packaging material 10 of the present invention. Therefore, it is particularly suitable for use in preserving objects that contain a relatively large amount of oil.
  • the oxygen absorber package 100 of the present invention it is preferable to use a package that includes the oxygen absorber package 100, an item to be preserved, and a gas barrier container that contains them.
  • preserved items include baked goods such as madeleines and financiers, and sweets such as chocolate confectionery; dairy products such as cheese and butter; meats such as beef, pork, and chicken; processed meat products such as salami, sausage, and ham; dried foods such as powdered soup, powdered seasonings such as dashi stock, powdered coffee, powdered milk for infants, and powdered diet foods; chemicals such as pesticides and insecticides; medicines; cosmetics; pet food; and a variety of other items.
  • baked goods such as madeleines and financiers, and sweets such as chocolate confectionery
  • dairy products such as cheese and butter
  • meats such as beef, pork, and chicken
  • processed meat products such as salami, sausage, and ham
  • dried foods such as powdered soup, powdered seasonings such as dashi stock, powdered coffee, powdered milk for infants, and powdered diet foods
  • chemicals such as pesticides and insecticides
  • medicines such as pesticides and insecticides
  • cosmetics such
  • the present invention is particularly suitable for foods containing lipids in an amount of 1% by mass or more and 50% by mass or less.
  • Such foods are not only susceptible to deterioration by oxygen, but also susceptible to problems such as oil seeping into the oxygen absorber package.
  • an oxygen absorber package containing the breathable packaging material of the present invention it is possible to effectively suppress the penetration of oil into the oxygen absorber in particular.
  • such foods include chocolate confectionery containing 1% to 50% by mass of lipids, and meat (e.g., beef) containing 1% to 50% by mass of lipids.
  • the oxygen absorber package of the present invention is particularly useful when stored at room temperature (e.g., 25° C.), and in the case of meat, the oxygen absorber package of the present invention is particularly useful when stored under refrigerated conditions (e.g., 5° C. to 10° C.).
  • Comparative Example 10 delamination occurred during the manufacturing process, and a breathable packaging material having the specified structure was not obtained, so no oxygen absorber package was produced. Therefore, for Comparative Example 10, a portion of the breathable packaging material in which delamination occurred and good interlayer adhesion was selected, the cut surface was observed, and the thickness of the intermediate layer was measured. In addition, when the intermediate layer is a nonwoven fabric, the nonwoven fabric is embossed, and therefore the thickness varies greatly depending on the observation point.
  • the melting point was measured in accordance with JIS K 7121-1987 using a differential scanning calorimeter ("DSC-60" manufactured by Shimadzu Corporation) under a nitrogen atmosphere.
  • the basis weight is the weight per 1 m2 of nonwoven fabric or greaseproof paper, and the value listed in the catalog was used.
  • Air permeability resistance The air permeability resistance was measured using an Oken type air permeability tester (manufactured by Asahi Seiko Co., Ltd., model EG02) in accordance with JIS P8117:2009. The measurement was performed in a mode in which the median value of the measurable range was 2000. The measurement was performed 10 times for the same nonwoven fabric or greaseproof paper.
  • Outer layer Two-layer non-porous film: Prepared in the following manner. A polyethylene terephthalate film (thickness 12 ⁇ m, melting point 255° C.; hereinafter referred to as “PET film”) was laminated as a base layer and a low-density polyethylene (thickness 15 ⁇ m, melting point 105° C.; hereinafter referred to as “PE”) was laminated as a welding layer, and extrusion laminated to obtain a two-layer non-porous film.
  • PET film polyethylene terephthalate film
  • PE low-density polyethylene
  • the non-perforated film was perforated using a needle roll (needle pattern 10.0 mm x 10.0 mm, needle diameter 0.6 mm) from the surface of the PET film through to the PE to form external ventilation holes, thereby obtaining a two-layered perforated film.
  • Fluorine-based greaseproof paper greaseproof paper with a fluorine-containing greaseproofing agent applied to the surface, basis weight 50 g/m 2 , air resistance 6 to 9 seconds (average 7 seconds)
  • Non-fluorine-based grease-resistant paper grease-resistant paper impregnated with a starch-based grease-resistant agent, basis weight 35 g/m 2 , air resistance 340 to 1700 seconds (average 765 seconds)
  • Inner layer Prepared by the following method.
  • a linear low density polyethylene film (thickness 40 ⁇ m, melting point 123° C.; hereinafter referred to as “LLDPE40”) was perforated using a needle roll (perforation rate 5.7 places/cm 2 , needle diameter 0.6 mm, needle pattern 5.0 mm ⁇ 5.0 mm) to obtain an inner layer.
  • Oxygen absorbers Powdered iron-based self-reacting oxygen absorbers, including iron powder, calcium chloride, sodium chloride, water-impregnated diatomaceous earth, and activated carbon.
  • the protective PET film on the intermediate layer side was peeled off, and a two-layer non-porous film was laminated on the intermediate layer as an outer layer with the PE side facing the intermediate layer, and the entire surface was heat-laminated to obtain a packaging multilayer film (breathable packaging material).
  • the thermal lamination was performed by placing a protective PET film (same as above) on the outer layer again, and pressing an iron (same as above) heated to a surface temperature of 185° C. against the protective PET film on the outer layer side for 5 seconds. After welding, all of the protective PET films were removed.
  • the obtained breathable packaging material had a layer structure of outer layer (two-layer non-porous film: base layer (PET film)/welding layer (PE))/middle layer (PET nonwoven fabric 1)/inner layer (LLDPE40, diameter ⁇ 1 of through hole H: 860 ⁇ m).
  • the diameter ⁇ 1 of the through hole H was measured by the following method. First, a seal check liquid (Ageless Seal Check Liquid manufactured by Mitsubishi Gas Chemical Co., Ltd.) was sprayed onto one surface of the inner layer of the breathable packaging material having the above-mentioned layer structure, and then the seal check liquid remaining on the surface of the inner layer was thoroughly wiped off with a paper wiper (Kimwipe), and only the portion exposed through the through hole H of the intermediate layer (the opening portion) was dyed. The dyed openings were randomly selected and observed using a digital microscope (same as above) to measure the dimension (long diameter) of the longest part of the opening diameter. The measured values of the six randomly selected openings were averaged to obtain the diameter ⁇ 1 of the through hole H.
  • a seal check liquid (Ageless Seal Check Liquid manufactured by Mitsubishi Gas Chemical Co., Ltd.) was sprayed onto one surface of the inner layer of the breathable packaging material having the above-mentioned layer structure, and then the seal check liquid remaining
  • Example 2 to 4 breathable packaging materials and oxygen absorber packages were produced in the same manner as in Example 1, except that the intermediate layer was changed to that shown in Table 1.
  • Comparative Examples 1 to 4 the breathable packaging material and the oxygen absorber package were prepared in the same manner as in Example 1, except that the outer layer was changed to a two-layer perforated film and the middle layer was changed to that shown in Table 1.
  • Comparative Examples 5 to 9 breathable packaging materials and oxygen absorber packages were produced in the same manner as in Example 1, except that the intermediate layer was changed to that shown in Table 1.
  • Comparative Example 10 Comparative Example 10
  • the intermediate layer was changed to that shown in Table 1, but under the same conditions as in Example 1, the intermediate layer and the inner layer could not be well welded together, and the layers easily peeled off (interlayer peeling), and it was not possible to prepare a breathable packaging material having a predetermined layer structure. Therefore, it was not possible to prepare an oxygen absorber package.
  • the melting point of the resin constituting the nonwoven fabric of the middle layer is 50°C higher than the melting point of the resin constituting the welding layer or the melting point of the resin constituting the inner layer, whichever is higher, and the thickness of the nonwoven fabric is 0.20 mm to 0.42 mm, can withstand defluorination and exhibit excellent oil resistance and oxygen absorbing performance (Examples 1 to 4).
  • the oxygen absorber package and breathable packaging material for oxygen absorbers according to the present invention can be used for a wide range of purposes, regardless of the object, such as food, medicine, etc.
  • Oxygen absorber package 10 Breathable packaging material 10E: Edge of breathable packaging material 11: Outer layer 11a: Base material layer 11b: Welded layer 13: Intermediate layer 13e: Cross section of intermediate layer 15: Inner layer H: Through hole 30: Oxygen absorber F: Gas flow t: Thickness of nonwoven fabric w: Width of heat-sealed portion X: Viewing direction in FIG. 2 L1 and L2: Continuous direction along edge 10E of breathable packaging material 10 w1 and w2: Width perpendicular to length directions L1 and L2 of heat-sealed portion S: Heat-sealed portion

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Food Science & Technology (AREA)
  • Packages (AREA)
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PCT/JP2024/009213 2023-03-14 2024-03-11 脱酸素剤包装体、並びに脱酸素剤用通気性包装材及びその製造方法 Ceased WO2024190713A1 (ja)

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KR1020257029699A KR20250161546A (ko) 2023-03-14 2024-03-11 탈산소제 포장체, 및 탈산소제용 통기성 포장재 및 그 제조 방법
EP24770819.1A EP4682080A1 (en) 2023-03-14 2024-03-11 Oxygen scavenger package, air-permeable packaging material for oxygen scavenger, and method for producing same
JP2025506831A JPWO2024190713A1 (https=) 2023-03-14 2024-03-11
CN202480017233.4A CN120752186A (zh) 2023-03-14 2024-03-11 脱氧剂包装体、以及脱氧剂用透气性包装材料及其制造方法
IL323116A IL323116A (en) 2023-03-14 2025-09-02 Oxygen absorber package, air-permeable packaging material for oxygen absorbers, and methods for producing the same

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JP2023-039303 2023-03-14

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JPS60240664A (ja) * 1984-05-15 1985-11-29 三菱瓦斯化学株式会社 包装材料
JPH03229610A (ja) * 1990-02-01 1991-10-11 Ooe Kagaku Kogyo Kk 吸着剤封入袋
JPH06329178A (ja) * 1993-05-19 1994-11-29 Toagosei Chem Ind Co Ltd 酸素吸収剤包装体
JP2002113828A (ja) * 2000-08-03 2002-04-16 Idemitsu Petrochem Co Ltd 包装用積層材料および包装体
JP2004345700A (ja) * 2003-05-23 2004-12-09 Shin Nippon Alc Kogyo Kk 通気性包材
JP2009035689A (ja) 2007-08-03 2009-02-19 Asahi Glass Co Ltd 撥水耐油剤組成物、撥水耐油紙およびその製造方法
JP2010235131A (ja) * 2009-03-30 2010-10-21 Asahi Kasei Fibers Corp 通気性成形体
JP2019162834A (ja) * 2018-03-20 2019-09-26 Ｊｘｔｇエネルギー株式会社 通気性包装材料、包装体及びその製造方法
CN214190801U (zh) * 2020-09-27 2021-09-14 沈庆鑫 一种改良脱氧剂包装袋

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Publication number Priority date Publication date Assignee Title
JPS60240664A (ja) * 1984-05-15 1985-11-29 三菱瓦斯化学株式会社 包装材料
JPH03229610A (ja) * 1990-02-01 1991-10-11 Ooe Kagaku Kogyo Kk 吸着剤封入袋
JPH06329178A (ja) * 1993-05-19 1994-11-29 Toagosei Chem Ind Co Ltd 酸素吸収剤包装体
JP2002113828A (ja) * 2000-08-03 2002-04-16 Idemitsu Petrochem Co Ltd 包装用積層材料および包装体
JP2004345700A (ja) * 2003-05-23 2004-12-09 Shin Nippon Alc Kogyo Kk 通気性包材
JP2009035689A (ja) 2007-08-03 2009-02-19 Asahi Glass Co Ltd 撥水耐油剤組成物、撥水耐油紙およびその製造方法
JP2010235131A (ja) * 2009-03-30 2010-10-21 Asahi Kasei Fibers Corp 通気性成形体
JP2019162834A (ja) * 2018-03-20 2019-09-26 Ｊｘｔｇエネルギー株式会社 通気性包装材料、包装体及びその製造方法
CN214190801U (zh) * 2020-09-27 2021-09-14 沈庆鑫 一种改良脱氧剂包装袋

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Title
See also references of EP4682080A1

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CN120752186A (zh) 2025-10-03
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KR20250161546A (ko) 2025-11-17

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