Deoxidizer packaging body, air-permeable packaging material for deoxidizer, and method for producing same

Abstract

A deoxidizer packaging body (100) provided with a deoxidizer (30) and an air-permeable packaging material (10) in which the deoxidizer (30) is housed, said air-permeable packaging material (10) having a structure comprising, in this order, an outer layer (11) that does not have a through-hole, an intermediate layer (13) that contains a non-woven fabric, and an inner layer (15) that has a through-hole (H), said outer layer (11) comprising a base material layer (11a) and a welded layer (11b) in this order. The air-permeable packaging material (10) does not contain fluorine, the melting point of the resin constituting the non-woven fabric is 50 DEG C or more higher than the melting point of the resin constituting the fusion layer (11b) or the melting point of the resin constituting the inner layer (15), and the thickness of the non-woven fabric is 0.20-0.42 mm (inclusive).

Description

Technical Field

[0001] The present invention relates to a deoxidizer package, a breathable packaging material for a deoxidizer, and a method for producing the same. Background Art

[0002] For various items such as food, beverages, pharmaceuticals, medical products, cosmetics, metal products, and electronic products that are easily affected by oxygen and deteriorate or deteriorate, deoxidizers are used to remove oxygen from sealed containers to prevent oxidative degradation and enable long-term storage.

[0003] Oxidizers can be used in various ways depending on their intended use and usage. For example, a powdered or tableted deoxidizer can be packaged with packaging material to form a small pouch-shaped deoxidizer package. When this deoxidizer package is placed in a sealed container containing food, the deoxidizer inside the deoxidizer package removes oxygen from the sealed container, thereby preventing oxidative degradation of the food.

[0004] As packaging materials for such deoxidizers, packaging materials made from sheets of resin, paper, or nonwoven fabric, and / or packaging materials formed by laminating these sheets, are used. Examples of packaging materials formed by laminating layers of resin, paper, or nonwoven fabric include those formed by laminating layers of resin with pre-perforated air holes with layers of paper or nonwoven fabric. Using a resin layer with pre-perforated air holes ensures air permeability to the outside, effectively demonstrating the deoxidizer's deoxidation performance.

[0005] Furthermore, deoxidizers are suitable for a variety of foods. However, when deoxidizer packaging is used for foods containing large amounts of oil, if the packaging material is not oil-resistant or has insufficient oil resistance, there is a problem of oil seeping into the packaging material, reducing air permeability and thus degrading deoxidation performance. Furthermore, there is the problem of the infiltrated oil degrading the deoxidizer or impairing the appearance of the deoxidizer packaging.

[0006] In order to solve such problems, oil-resistant paper coated or impregnated with an oil-resistant agent containing fluorine (hereinafter also referred to as "fluorine-based oil-resistant paper") has been widely used as a packaging material in conventional deoxidizer packages.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-35689 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] However, as disclosed in Patent Document 1, water and oil repellent compositions suitable for use as packaging materials for deoxidizers contain perfluoroalkyl compounds (hereinafter referred to as "PFAS"). Due to their poor decomposition and high bioaccumulation potential, there has been a trend in recent years to restrict the use of PFAS worldwide, particularly in Europe and the United States.

[0012] Therefore, defluorination is also required in packaging materials for deoxidizers. However, studies by the present inventors have revealed problems with oil resistance and deoxidation performance when fluorine-free oil-resistant paper or nonwoven fabric is used instead of fluorine-based oil-resistant paper.

[0013] Therefore, an object of the present invention is to provide a deoxidizer package that can cope with defluorination and can exhibit excellent oil resistance and deoxidation performance, as well as a breathable packaging material for a deoxidizer and a method for producing the same.

[0014] Solutions for solving problems

[0015] That is, the gist of the present invention is as follows.

[0016] [1] A deoxidizer package comprising a deoxidizer and a breathable packaging material containing the deoxidizer,

[0017] The air-permeable packaging material has a structure comprising: an outer layer including a base material layer and a welding layer in order and having no through-holes, an intermediate layer including a non-woven fabric, and an inner layer having through-holes.

[0018] The aforementioned breathable packaging material does not contain fluorine,

[0019] The melting point of the resin constituting the nonwoven fabric is 50° C. or higher than the melting point of the resin constituting the fusion bond layer or the melting point of the resin constituting the inner layer, whichever is higher.

[0020] The nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.

[0021] [2] The deoxidizer package according to [1] above, wherein the base layer comprises one or more materials selected from the group consisting of polyethylene terephthalate and biaxially stretched polypropylene.

[0022] [3] The deoxidizer package according to [1] or [2], wherein the welding layer comprises one or more selected from the group consisting of polyethylene and ethylene copolymers.

[0023] [4] The deoxidizer package according to any one of [1] to [3] above, wherein the nonwoven fabric comprises one or more selected from the group consisting of polyamide and polyester.

[0024] [5] The deoxidizer package according to any one of [1] to [4] above, wherein the inner layer comprises linear low-density polyethylene.

[0025] [6] The deoxidizer package according to any one of [1] to [5], wherein the melting point of the resin constituting the nonwoven fabric is 150° C. or higher and 300° C. or lower.

[0026] [7] The deoxidizer package according to any one of [1] to [6] above, wherein the air-permeable packaging material is formed into a bag shape by heat-sealing the edges of the inner layer to the inner side.

[0027] The width of the heat-welded portion perpendicular to the longitudinal direction is 0.3 mm or more and 15 mm or less.

[0028] [8] A breathable packaging material for an oxygen scavenger, comprising: an outer layer including a base material layer and a welding layer in order and having no through-holes; an intermediate layer including a non-woven fabric; and an inner layer having through-holes.

[0029] The aforementioned breathable packaging material for deoxidizer does not contain fluorine.

[0030] The melting point of the resin constituting the nonwoven fabric is 50° C. or 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.

[0031] The nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.

[0032] [9] The air-permeable packaging material for deoxidizer according to [8] above, wherein the inner layer is placed inside and the edges are heat-fused to form a bag shape.

[0033] The width of the heat-welded portion perpendicular to the longitudinal direction is 0.3 mm or more and 15 mm or less.

[0034]

[10] A method for producing a breathable packaging material for a deoxidizer, which is the method for producing a breathable packaging material for a deoxidizer according to [8] or [9] above.

[0035] The manufacturing method includes the steps of stacking and welding to form a structure including, in order, the outer layer, the intermediate layer, and the inner layer, which in order include the base material layer and the welding layer.

[0036] The welding step is performed at a temperature lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer.

[0037] Effects of the Invention

[0038] According to the present invention, there can be provided a deoxidizer package that can cope with defluorination and exhibit excellent oil resistance and deoxidation performance, as well as a breathable packaging material for a deoxidizer and a method for producing the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic cross-sectional view showing one form of the deoxidizer package according to the present embodiment.

[0040] Figure 2 Observed from the X direction Figure 1 Schematic diagram of one form of the deoxidizer package according to this embodiment. DETAILED DESCRIPTION

[0041] Hereinafter, embodiments of the deoxidizer package, the air-permeable packaging material for deoxidizer, and the method for producing the same according to the present invention will be described in detail.

[0042] It should be noted that in this specification, the term "A to B" related to the description of numerical values ​​means "A or more and B or less" (when A < B) or "A or less and B or more" (when A > B). In addition, in the present invention, a combination of preferred aspects is a more preferred aspect.

[0043] Furthermore, in this specification, unless otherwise specified, "(meth)acrylate", "(meth)acryloyl", "(meth)acrylic acid" and the like refer to acrylate and / or methacrylate, acryloyl and / or methacryloyl, acrylic acid and / or methacrylic acid, etc., respectively.

[0044] [Deoxidizer packaging]

[0045] The deoxidizer package of the present invention comprises a deoxidizer and a breathable packaging material containing the deoxidizer.

[0046] The air-permeable packaging material has a structure comprising: an outer layer including a base material layer and a welding layer in order and having no through-holes, an intermediate layer including a non-woven fabric, and an inner layer having through-holes.

[0047] The breathable packaging material does not contain fluorine,

[0048] The melting point of the resin constituting the nonwoven fabric is 50° C. or 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.

[0049] The nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.

[0050] Figure 1This is a schematic cross-sectional view showing one embodiment of the deoxidizer package of the present invention. The deoxidizer package 100 includes a deoxidizer 30 and a breathable packaging material 10 containing the deoxidizer 30. The breathable packaging material 10 has a structure comprising, in order, an outer layer 11 having no through-holes, including a base layer 11a and a welding layer 11b, an intermediate layer 13 comprising a nonwoven fabric, and an inner layer 15 having through-holes H. The breathable packaging material 10 does not contain fluorine. The melting point of the resin constituting the nonwoven fabric is at least 50°C 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 between 0.20 mm and 0.42 mm.

[0051] The deoxidizer package 100 of the present invention has the above structure and can cope with defluorination and exhibit better oil resistance and deoxidation performance. The reason why the deoxidizer package of the present invention exhibits the above effects is not yet clear, but one of the reasons is considered to be as follows.

[0052] Typically, breathable packaging materials used for deoxidizer packaging consist of an outer layer, an intermediate layer, and an inner layer in this order. To impart breathability, conventional breathable packaging materials typically have the outer layer perforated. Although oil can penetrate through the perforations in the outer layer, using fluorine-based oil-resistant paper, which exhibits excellent oil resistance and breathability, as the intermediate layer prevents oil from penetrating into the inner layer.

[0053] On the other hand, in response to the recent trend towards defluorination, the present inventors conducted research on breathable packaging materials that do not use fluorine-based oil-resistant paper as an intermediate layer. As a result, they found that when fluorine-free oil-resistant paper or non-woven fabric is used instead of fluorine-based oil-resistant paper, there is a problem in that it is not possible to achieve both oil resistance and deoxidation performance.

[0054] Specifically, oil-resistant paper that doesn't use a fluorine-based oil-proofing agent (hereinafter also referred to as "non-fluorine-based oil-resistant paper") has lower air permeability than fluorine-based oil-resistant paper. Therefore, when using non-fluorine-based oil-resistant paper as the middle layer of a breathable packaging material, while it can prevent oil intrusion, it also reduces the air permeability of the breathable packaging material 10 and deteriorates its deoxidation performance.

[0055] On the other hand, oil-resistant paper and non-woven fabrics that have air permeability equivalent to that of fluorine-based oil-resistant paper but do not contain fluorine have inferior oil resistance compared to fluorine-based oil-resistant paper. Although they can ensure sufficient air permeability as breathable packaging materials, they have the problem of oil infiltration. There is a case where the infiltrated oil causes the deoxidizer to deteriorate, thereby worsening the deoxidation performance.

[0056] Furthermore, the method of imparting oil resistance by not subjecting the outer layer of the air-permeable packaging material to pore-perforating treatment can prevent oil from entering the interior of the air-permeable packaging material. However, there is a problem in that the air permeability of the air-permeable packaging material is reduced, and the deoxidation performance is deteriorated.

[0057] Therefore, the present inventors have conducted intensive research on the balance between oil resistance and deoxidation performance, and found that Figure 1 As shown, the breathable packaging material 10 has the following structure, which includes, in sequence: an outer layer 11 that does not have through holes, an intermediate layer 13 that includes a specified non-woven fabric, and an inner layer 15 that has through holes H. As a result, the breathable packaging material 10 as a whole can form a fluorine-free structure, thereby ensuring excellent oil resistance and air permeability. As a result, a deoxidizer package body 100 that can cope with defluorination and has excellent oil resistance and deoxidation performance can be obtained.

[0058] Specifically, the breathable packaging material 10 used in the present invention lacks through-holes in its outer layer 11, resulting in excellent oil resistance. Furthermore, by using a fluorine-free nonwoven fabric as the intermediate layer 13, instead of the widely used fluorine-based oil-resistant paper, it is able to cope with defluorination. Furthermore, the intermediate layer 13 comprises a specified nonwoven fabric, and the inner layer 15 has through-holes H. This allows air to flow from a cross section 13e of the intermediate layer 13 at an edge 10E of the breathable packaging material 10 to the through-holes H of the inner layer 15, ensuring sufficient air permeability both inside and outside the breathable packaging material 10.

[0059] It is considered that by using such a gas-permeable packaging material 10 , the deoxidizer package 100 of the present invention can achieve both excellent oil resistance and deoxidation performance.

[0060] It should be noted that, in this specification, "fluorine-free" means that the component intentionally contained does not contain fluorine. Therefore, this does not apply to unintentional fluorine. Examples of unintentional fluorine include small amounts of fluorine that are unavoidably introduced as impurities during the manufacturing process, cleaning process, etc. In the fluorine-free, breathable packaging material 10 used in the present invention, the content of unintentional fluorine is, for example, less than 100 ppm.

[0061] Hereinafter, the structure of the deoxidizer package according to this embodiment will be described in detail.

[0062] <Deoxidizer>

[0063] The deoxidizer 30 used in the present invention is not particularly limited, and known deoxidizers can be used. For example, deoxidizers that use metal powders such as iron powder, reducing inorganic substances such as iron compounds, reducing organic substances such as polyphenols, polyols, ascorbic acid or its salts, metal complexes, or polymer compounds having carbon-carbon double bonds as the main agent for the oxygen absorption reaction can be used. The deoxidizer does not necessarily have to be a single component; for example, a catalyst, water, a metal salt, a carrier, and the like can be combined with metal powders such as iron powder.

[0064] Among them, from the perspective of oxygen absorption performance, deoxidizers containing iron powder as the main component are preferred. Furthermore, in deoxidizers containing iron powder as the main component, when oil penetrates into the breathable packaging material, the infiltrated oil sometimes reacts with the iron powder of the deoxidizer to produce a unique odor. In order to suppress the generation of such odor, the breathable packaging material used to wrap the deoxidizer containing iron as the main component requires good air permeability and high oil resistance. Therefore, the breathable packaging material used in the present invention is suitable for use in cases where the deoxidizer contains iron powder as the main component in terms of having good air permeability and being able to exert particularly excellent oil resistance. As the deoxidizer containing iron powder as the main component, an iron-based self-reactive deoxidizer containing iron powder, a metal halide, a carrier, and water is preferred.

[0065] The form of the deoxidizer 30 is not particularly limited and can be appropriately adopted in consideration of the intended use, environment, etc. The deoxidizer 30 can be, for example, in a powdered form or formed into tablets. When the deoxidizer 30 is in a powdered form, the size and shape of the through-holes H and the particle size of the deoxidizer 30 are preferably adjusted to prevent the deoxidizer 30 powder from penetrating the intermediate layer 13 through the through-holes H of the inner layer 15 and leaking out of the cross section 13e of the intermediate layer 13 at the edge 10E of the air-permeable packaging material 10.

[0066] <Breathable Packaging Materials (Breathable Packaging Materials for Deoxidizers)>

[0067] The breathable packaging material 10 used in the present invention is a breathable packaging material for an oxygen scavenger (hereinafter sometimes referred to as a "breathable packaging material") having the following structure, which includes, in sequence: an outer layer 11 including a base material layer 11a and a welding layer 11b and having no through-holes, an intermediate layer 13 including a non-woven fabric, and an inner layer 15 having through-holes H. The breathable packaging material 10 does not contain fluorine, the melting point of the resin constituting the aforementioned non-woven fabric is 50°C or higher than the melting point of the resin constituting the aforementioned welding layer 11b or the melting point of the resin constituting the aforementioned inner layer 15, whichever is higher, and the thickness t of the aforementioned non-woven fabric is not less than 0.20 mm and not more than 0.42 mm.

[0068] Hereinafter, each layer of the air-permeable packaging material 10 of this embodiment and its components will be described in detail.

[0069] (Outer layer)

[0070] The outer layer 11 is a layer located on the outer surface side of the air-permeable packaging material 10. The outer layer 11 includes a base material layer 11a and a welding layer 11b in this order, and does not have through holes.

[0071] Since the outer layer 11 does not have through holes, it is possible to effectively suppress the intrusion of oil from the outside into the inner side of the air-permeable packaging material 10 .

[0072] The outer layer 11 only needs to include a base material layer 11 a and a fusion bonding layer 11 b in contact with the intermediate layer 13 , and may further include other layers as needed. However, the outer layer 11 is preferably a layer consisting of the base material layer 11 a and the fusion bonding layer 11 b .

[0073] The base material layer 11a, the welding layer 11b and other layers preferably contain a thermoplastic resin. The thermoplastic resin is not particularly limited and can be selected appropriately according to the intended use and desired physical properties. One type can be used alone or two or more types can be used in combination.

[0074] The melting point of the resin constituting the base layer 11a is preferably higher than the melting point of the resin constituting the welding layer 11b, and the greater the temperature difference between these melting points, the more preferable. Furthermore, the melting point of the resin constituting the base layer 11a is preferably higher than the melting point of the resin constituting the inner layer 15, and the greater the temperature difference between these melting points, the more preferable.

[0075] From the viewpoint of obtaining sufficient strength and flexibility as the air-permeable packaging material 10 , the melting point of the resin constituting the base layer 11 a is preferably 200 to 300°C, more preferably 220 to 280°C, and even more preferably 235 to 270°C.

[0076] In order to ensure good adhesion to the base material layer 11 a and the intermediate layer 13 , the melting point of the resin constituting the welding layer 11 b is preferably 85 to 125° C., more preferably 90 to 120° C., and even more preferably 95 to 115° C.

[0077] It should be noted that the melting point can be measured by the method described in the Examples, or the catalog value can be used.

[0078] Examples of the base material layer 11a include polyethylene terephthalate, biaxially stretched polypropylene, and biaxially stretched nylon. In particular, the base material layer 11a preferably comprises one or more materials selected from the group consisting of polyethylene terephthalate and biaxially stretched polypropylene, more preferably one or more materials selected from the group consisting of polyethylene terephthalate and biaxially stretched polypropylene, further preferably polyethylene terephthalate or biaxially stretched polypropylene, and even more preferably polyethylene terephthalate.

[0079] It should be noted that the base material layer 11 a may be a single-layer film or a multi-layer film composed of two or more layers of different materials.

[0080] The welding layer 11b preferably comprises a heat-sealable material. Examples of heat-sealable materials include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-α-olefin copolymers polymerized using a metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, polyvinyl acetate resins, poly(meth)acrylic acid resins, and polyvinyl chloride resins. In particular, the welding layer 11b preferably comprises one or more species selected from the group consisting of polyethylene and ethylene copolymers, more preferably one or more species selected from the group consisting of polyethylene and ethylene copolymers, further preferably polyethylene, and even more preferably low-density polyethylene.

[0081] Furthermore, from the perspective of increasing the degree of freedom in heat-sealing conditions (temperature, pressure, time) of the air-permeable packaging material 10, the melting point of the resin constituting the welding layer 11b is preferably lower than the melting point of the resin constituting the inner layer 15, and the greater the temperature difference between these melting points, the more preferred.

[0082] Each layer constituting the outer layer 11 may further contain other components in addition to the thermoplastic resin. Other components that can be used in the outer layer 11 are not particularly limited as long as they do not contain fluorine, and examples thereof include additives such as stabilizers, lubricants, antistatic agents, antifogging agents, fillers, colorants, plasticizers, and nucleating agents.

[0083] The thickness of the outer layer 11 is not particularly limited, but is preferably 1 to 50 μm, more preferably 2 to 40 μm, even more preferably 4 to 35 μm, and even more preferably 8 to 30 μm. By setting the thickness of the outer layer 11 within the above range, a breathable packaging material 10 having sufficient strength can be obtained, while also having the appropriate flexibility required for processing such as bending during the manufacture of the deoxidizer package.

[0084] The thickness of the base material layer 11 a is not particularly limited, but is preferably 0.5 to 25 μm, more preferably 1 to 20 μm, and even more preferably 5 to 15 μm from the viewpoint of obtaining sufficient strength and flexibility as the air-permeable packaging material 10 .

[0085] The thickness of the welding layer 11 b is not particularly limited, but is preferably 0.5 to 25 μm, more preferably 1 to 20 μm, and even more preferably 10 to 20 μm from the viewpoint of ensuring good adhesion with the base layer 11 a and the intermediate layer 13 .

[0086] It should be noted that the thickness can be measured by the method described in the examples, or the catalog value can be used.

[0087] Note that, on the surface of the outer layer 11 on the side of the base material layer 11 a , printing or drawing may be performed by gravure printing or the like as needed.

[0088] (Middle layer)

[0089] The intermediate layer 13 is a layer comprising nonwoven fabric, preferably a layer consisting only of nonwoven fabric. Such an intermediate layer 13 not only imparts a certain degree of durability and air permeability to the breathable packaging material 10, but also prevents leakage of the deoxidizer 30 contained in the deoxidizer package 100.

[0090] The nonwoven fabric constituting the intermediate layer 13 is made of a resin having a melting point that is at least 50°C 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 from 0.20 mm to 0.42 mm. By using such a nonwoven fabric as the intermediate layer 13, the breathable packaging material 10 exhibits excellent air permeability.

[0091] The nonwoven fabric used in the present invention has a resin comprising a melting point that is at least 50°C higher than the melting point of the resin comprising the welding layer 11b or the melting point of the resin comprising the inner layer 15, whichever is higher. The thickness t of the nonwoven fabric is between 0.20 mm and 0.42 mm. This ensures air permeability through the cross-section 13e of the intermediate layer 13 at the edge 10E of the air-permeable packaging material 10.

[0092] first, Figure 1 The deoxidizer package 100 shown includes a deoxidizer 30 and a gas-permeable packaging material 10 that contains the deoxidizer 30. Figure 1 The deoxidizer package 100 shown is formed into a bag shape by heat-sealing the edges 10E of the air-permeable packaging material 10 with the inner layer 15 as the inner side. Figure 1 In FIG. 1 , the dotted arrow F indicates the flow of gas corresponding to ventilation.

[0093] The deoxidizer package 100 of the present invention enables air permeation (gas flow F) from the cross section 13e of the intermediate layer 13 at the edge 10E of the air-permeable packaging material 10 through the through holes H of the inner layer 15 by making the intermediate layer 13 of the air-permeable packaging material 10 include a non-woven fabric with excellent air permeability, thereby ensuring air permeability to the inside of the air-permeable packaging material 10.

[0094] In this case, the melting point of the resin constituting the nonwoven fabric is at least 50°C higher than the melting point of the resin constituting the weld layer 11b or the melting point of the resin constituting the inner layer 15, whichever is higher. This prevents the resin constituting the nonwoven fabric from melting and clogging the mesh of the nonwoven fabric due to welding during lamination or heat fusion during bag-forming during the manufacturing process of the breathable packaging material 10, thereby maintaining the excellent air permeability unique to nonwoven fabrics. Furthermore, it is believed that by setting the thickness t of the nonwoven fabric to be between 0.20 mm and 0.42 mm, a sufficient area for the cross-section 13e serving as the intermediate layer 13 is ensured at the edge 10E of the breathable packaging material 10, and lamination defects (interlayer delamination) are prevented, thereby achieving a breathable packaging material with excellent air permeability.

[0095] The resin constituting the nonwoven fabric is not particularly limited, and examples thereof include thermoplastic resins such as polypropylene, polyamide, and polyester. More specifically, examples thereof include nylon (Ny) nonwoven fabrics (e.g., the "ELTAS (registered trademark) series" manufactured by Asahi Kasei Corporation), polyethylene terephthalate (PET) nonwoven fabrics (e.g., the "ELTAS (registered trademark) series" manufactured by Asahi Kasei Corporation), and TYVEK (registered trademark, manufactured by DuPont-Asahi Flash Spun Products Co., Ltd.). The nonwoven fabric preferably comprises one or more members selected from the group consisting of polyamides and polyesters, more preferably one or more members selected from the group consisting of polyamides and polyesters, and even more preferably polyester.

[0096] The melting point of the resin constituting the nonwoven fabric is at least 50°C 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. This temperature range prevents thermal deformation or clogging of the nonwoven fabric caused by welding during the manufacturing process of the breathable packaging material 10 or by heating during heat sealing of the edge 10E, thereby ensuring good air permeability. The temperature difference between the melting point of the resin constituting the nonwoven fabric and 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, is not particularly limited and may be, for example, 215°C or lower or 200°C or lower.

[0097] Specifically, the melting point of the resin constituting the nonwoven fabric is preferably 150°C to 300°C, more preferably 200°C to 300°C, further preferably 200°C to 270°C, and even more preferably 230°C to 270°C.

[0098] It should be noted that the melting point can be measured by the method described in the Examples, or the catalog value can be used.

[0099] The weight per unit area of ​​the nonwoven fabric is not particularly limited, but is preferably 20 to 120 g / m 2 , more preferably 35~95g / m 2 , more preferably 40~70g / m 2 By setting the basis weight of the nonwoven fabric within the above range, sufficient durability and air permeability can be obtained.

[0100] It should be noted that the measurement of the basis weight may be carried out in accordance with JIS P 8124:2011 “Paper and paperboard—Determination of basis weight”, or a catalog value may be used.

[0101] From the perspective of good air permeability, the thickness of the nonwoven fabric is 0.20 mm or more, preferably 0.22 mm or more, and more preferably 0.25 mm or more. In particular, from the perspective of good weldability between the intermediate layer 13 and the inner layer 15, the thickness is 0.42 mm or less, preferably 0.39 mm or less, and more preferably 0.35 mm or less. Specifically, it is 0.20 mm or more and 0.42 mm or less, preferably 0.22 mm or more and 0.39 mm or less, and more preferably 0.25 mm or more and 0.35 mm or less.

[0102] It should be noted that the thickness can be measured by the method described in the examples, or the catalog value can be used.

[0103] The air permeability of the nonwoven fabric is not particularly limited, but the air permeability resistance according to JIS P8117:2009 is, for example, 100 seconds or less, preferably 50 seconds or less, and more preferably 10 seconds or less.

[0104] It should be noted that the air permeability resistance can be measured by the method described in the examples, or the catalog value can be used.

[0105] The intermediate layer 13 may contain other components besides those constituting the nonwoven fabric, as long as they do not impair the effects of the present invention. Other components that can be used in the intermediate layer 13 are not particularly limited, as long as they do not contain fluorine. Examples include sizing agents (barriers), water-resistant agents, water-repellent agents, paper strengthening agents, and dyes. It should be noted that the intermediate layer 13 is preferably composed solely of nonwoven fabric.

[0106] (Inner layer)

[0107] The inner layer 15 is a layer located on the inner surface side of the air-permeable packaging material 10. The inner layer 15 has through-holes H therein.

[0108] Since the inner layer 15 has the through-holes H, air can pass from the outside to the inside of the air-permeable packaging material 10 .

[0109] The inner layer 15 preferably contains a thermoplastic resin. The thermoplastic resin is not particularly limited, and a suitable type can be appropriately selected according to the intended use and desired physical properties. One type can be used alone, or two or more types can be used in combination.

[0110] Examples of the resin constituting the inner layer 15 include olefin resins such as polyethylene and polypropylene; ethylene-vinyl acetate copolymer resins; and ethylene-(meth)acrylate copolymer resins. Among these, olefin resins are preferred from the viewpoint of adhesiveness, polyethylene and polypropylene are more preferred, and linear (linear) low-density polyethylene, high-density polyethylene, and unstretched polypropylene are even more preferred.

[0111] More specifically, the inner layer 15 preferably includes linear low-density polyethylene, and more preferably linear low-density polyethylene.

[0112] 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, even if heat sealing is performed, the resin constituting the inner layer 15 will not cause the problem of dissolution. As a result, the deoxidizer can be securely enclosed without causing powder leakage. In addition, 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, even if the heat sealing temperature is not set to such a high temperature, it can be fully sealed in a short time. More specifically, the melting point of the resin constituting the inner layer 15 is preferably 80~200°C, more preferably 95~180°C, and even more preferably 110~150°C.

[0113] It should be noted that the melting point can be measured by the method described in the Examples, or the catalog value can be used.

[0114] The inner layer 15 may further include 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. Examples of other components include stabilizers, lubricants, antistatic agents, antifogging agents, fillers, colorants, plasticizers, and nucleating agents.

[0115] The thickness of the inner layer 15 is not particularly limited, but is preferably 0.5 to 80 μm, more preferably 1 to 60 μm, further preferably 10 to 50 μm, and even more preferably 20 to 50 μm. By setting the thickness of the inner layer 15 within the above range, sufficient adhesive strength can be achieved with a short heat seal time.

[0116] It should be noted that the thickness can be measured by the method described in the examples, or the catalog value can be used.

[0117] The inner layer 15 has a through hole H. Here, the through hole H is a hole that penetrates from one surface to the other surface of the inner layer 15 .

[0118] The diameter or opening density of the through-holes H can be appropriately adjusted to achieve the target air permeability (air permeability) of the entire air-permeable packaging material 10. Specifically, when using a cutter or a needle, the diameter or opening density can be adjusted by adjusting the shape, penetration direction, arrangement, number, etc. When using a laser or an electron beam, the perforation conditions can be adjusted by adjusting the irradiation voltage, current, irradiation time, irradiation direction, etc.

[0119] In addition, the shape of the through hole H is not particularly limited. As a cross section, for example, a circle, a triangle, a quadrilateral, a square, an ellipse, etc. can be cited. The longitudinal section is preferably a cone or a pyramid with a tapered tip from the inner layer 15 side toward the middle layer 13 side, or from the middle layer 13 side toward the inner layer 15 side.

[0120] The diameter of the through-hole H is not particularly limited; the diameter φ1 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 φ2 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. It should be noted that the diameters φ1 and φ2 of the through-hole H can be measured by the method described in the Examples and are the dimensions of the longest diameter portion of the opening (the major diameter).

[0121] The diameters φ1 and φ2 of the through-holes H can be appropriately adjusted based on the desired air permeability of the air-permeable packaging material 10, and are, for example, 100 to 2500 μm, preferably 200 to 2000 μm, more preferably 400 to 1000 μm, and even more preferably 600 to 1000 μm. By setting the diameters within these ranges, good air permeability can be achieved, and the deoxidizer 30 located inside the deoxidizer package 100 can be prevented from leaking to the outside.

[0122] 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 a resin sheet or film constituting the inner layer 15 to a pore-forming treatment using a known method. Specific examples of the pore-forming treatment method include a method using a needle, a method using a cutter, a method using electron beam irradiation, and a method using a laser.

[0123] Among these methods, the use of needles for perforation is preferred from the perspective of easily controlling the size and position of the openings. From the perspective of producing a breathable packaging material 10 with a consistent and stable density and shape of the openings, the use of a cylindrical jig with needles attached to its sides (hereinafter referred to as a "needle roller") is more preferred. The diameter of the needles of the needle roller 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. By setting the needle diameter within this preferred range, the shape of the openings is stabilized, making it easier to adjust the air permeability. Furthermore, the needle pattern can be adjusted appropriately based on factors such as air permeability. Furthermore, when using the needle roller, perforation can be performed even at room temperature. However, by heating the needle roller within a range that does not exceed the melting point of the resin used in the inner layer 15, the perforation process can be performed more stably.

[0124] Regarding the direction of the pore opening treatment (the direction in which the through-holes H are formed), the through-holes H may be formed so as to penetrate the inner layer 15 from the surface not in contact with the intermediate layer 13, or may be formed so as to penetrate the inner layer 15 from the surface in contact with the intermediate layer 13. Depending on the formation direction, the shape of the longitudinal cross-section of the through-holes H changes, and it is possible to adjust the air permeability, etc. In particular, from the perspective of surface smoothness, it is preferable to form the through-holes H so as to penetrate the inner layer 15 from the surface not in contact with the intermediate layer 13.

[0125] The diameter of the through hole H can be appropriately controlled by the jig used for the hole-forming process, the forming direction, etc. Specifically, when a needle having a tapered tip is used, the diameter of the through hole H in the surface of the inner layer 15 not in contact with the intermediate layer 13 is set to diameter φ1, and the diameter of the through hole H in the surface of the inner layer 15 in contact with the intermediate layer 13 is set to diameter φ2, (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 of φ1>φ2 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 of φ1<φ2 is satisfied.

[0126] (Shape of breathable packaging material)

[0127] The air-permeable packaging material 10 used in the present invention is a material for housing the deoxidizer 30 . The shape of the air-permeable packaging material 10 is not particularly limited as long as it can house the deoxidizer 30 , but is preferably a bag-shaped material.

[0128] Examples of bag-shaped breathable packaging materials include those formed by laminating two sheets of breathable packaging materials 10 with the inner layer 15 facing inward, those formed by laminating one sheet of breathable packaging material 10 and one sheet of non-breathable packaging material with the inner layer 15 facing inward, and those formed by bending one sheet of breathable packaging material with the inner layer 15 facing inward and laminating the edges excluding the bent portion.

[0129] The method of laminating the air-permeable packaging material 10 is not particularly limited and can be performed by a known method, for example, dry lamination, heat sealing, etc.

[0130] When heat sealing is used to bond the breathable packaging material 10, the fusion temperature during heat sealing is preferably lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer 13. By setting the fusion temperature to this level, the resin constituting the nonwoven fabric can be prevented from melting and clogging the mesh, thereby maintaining good air permeability of the breathable packaging material 10.

[0131] In the case of a quadrilateral air-permeable packaging material 10, examples include a bag-shaped bag formed by overlapping two sheets of air-permeable packaging material 10 and heat-sealing the four sides; a bag-shaped bag formed by overlapping a single sheet of air-permeable packaging material 10 and a single sheet of non-air-permeable packaging material and heat-sealing the four sides; and a bag-shaped bag formed by folding a single sheet of air-permeable packaging material 10 and heat-sealing the three sides excluding the folded portion. Furthermore, the bag-shaped bag may be formed by forming the air-permeable packaging material 10 into a tube and heat-sealing the ends and the main body of the tube.

[0132] Furthermore, when the air-permeable packaging material 10 is formed into a bag shape by heat-sealing the edges 10E with the inner layer 15 positioned inward, the width of the heat-sealed portion perpendicular to the longitudinal direction is preferably from 0.3 mm to 15 mm, more preferably from 3 mm to 10 mm. When the width of the heat-sealed portion perpendicular to the longitudinal direction is within this range, the deoxidizer can be well retained within the air-permeable packaging material.

[0133] In this specification, the "longitudinal direction of the heat-sealed portion" refers to a continuous direction along the edge of the air-permeable packaging material. It should be noted that the edge does not necessarily need to be straight and may also be curved.

[0134] Figure 2 Observed from the X direction Figure 1 Schematic diagram of the deoxidizer package 100 of the present invention is shown. Here, the inner layer 15 is positioned inside, and the portion where the edges 10E are heat-fused together is represented as region S. Furthermore, the longitudinal directions of the heat-fused portion S are represented as directions L1 and L2 along the edges 10E of the air-permeable packaging material 10, and the widths of the heat-fused portion perpendicular to the longitudinal directions L1 and L2 are represented as widths w1 and w2.

[0135] (Method for producing breathable packaging material)

[0136] The manufacturing method of the breathable packaging material 10 of the present invention does not need to be limited, and preferably includes a process of stacking and welding in a manner to form the following structure, which structure includes, in sequence: the outer layer 11 including the above-mentioned base material layer 11a and the above-mentioned welding layer 11b, the above-mentioned intermediate layer 13, and the above-mentioned inner layer 15; the above-mentioned welding process is carried out at a temperature lower than the melting point of the resin of the non-woven fabric constituting the above-mentioned intermediate layer 13.

[0137] It should be noted that the details of each layer are as described above.

[0138] The air-permeable packaging material 10 produced by such a production method does not melt the resin of the nonwoven fabric constituting the intermediate layer 13 during the process of laminating and welding the layers, and the mesh of the nonwoven fabric is not clogged, thereby exhibiting good air permeability.

[0139] The order of stacking and welding the layers in a manner that forms a structure including the outer layer 11, the intermediate layer 13, and the inner layer 15 in this order is not limited as long as the layers are stacked in a manner that forms the layer structure. For example, (1) the inner layer 15 and the intermediate layer 13 can be stacked and welded in advance to form a composite layer, and then the outer layer 11 can be stacked and welded on the intermediate layer 13 side of the composite layer. (2) The outer layer 11 and the intermediate layer 13 can be stacked and welded in advance to form a composite layer, and then the inner layer 15 can be stacked and welded on the intermediate layer 13 side of the composite layer. (3) Three layers can be stacked and welded at the same time. Among them, from the viewpoint of being able to perform the operation while confirming the state of the opening of the inner layer 15, the above step (1) is preferred.

[0140] The method for laminating and welding the layers is not particularly limited, and for example, known methods such as heat lamination can be used. Welding can be performed in a manner such that the layers do not peel off, and can be partial welding or full-surface welding. However, from the perspective of ensuring good adhesion, full-surface welding is preferred.

[0141] The fusion temperature can be any temperature lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer 13 and can be appropriately selected based on the melting points of the resin constituting the inner layer 15 and the resin constituting the fusion layer 11b of the outer layer 11. To achieve good adhesion, the fusion temperature is preferably higher than the higher of the melting points of the resin constituting the inner layer 15 and the resin constituting the fusion layer 11b of the outer layer 11. Specifically, the fusion 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.

[0142] <Method for Manufacturing Deoxidizer Package>

[0143] The method for manufacturing the deoxidizer package 100 of the present invention is not particularly limited, and an appropriate method may be employed in consideration of the intended use, environment, etc. For example, the deoxidizer 30 is preferably packaged so as to contact the inner layer 15 of the breathable packaging material 10. More specifically, the deoxidizer 30 is preferably housed inside the breathable packaging material 10, which is laminated with the inner layer 15 as the inner side, to form a bag, and the opening of the breathable packaging material 10 is sealed.

[0144] <Application of deoxidizer package>

[0145] The oxygen scavenger package 100 of the present invention includes the air-permeable packaging material 10 of the present invention, and thus has excellent oil resistance and deoxidation performance. Therefore, it is particularly suitable for storing objects containing a large amount of oil.

[0146] When the deoxidizer package 100 of the present invention is used, it is preferable to prepare a package including the deoxidizer package 100 , objects to be stored, and a gas barrier container for storing the objects.

[0147] Examples of the items to be stored include baked snacks such as madeleine and financier, and chocolate snacks; dairy products such as cheese and butter; edible meats such as beef, pork, and chicken; processed animal meats such as salami, sausage, and ham; powdered soup bases, powdered seasonings such as soup base (dashi no su), powdered coffee, powdered milk for infants, powdered diet foods, and other dry foods; chemicals such as pesticides and insecticides; pharmaceuticals; cosmetics; pet food; and various other items.

[0148] The present invention is particularly suitable for foods containing 1% to 50% lipids by mass. Besides being susceptible to deterioration due to oxygen, such foods are also susceptible to problems such as oil seeping into the deoxidizer packaging. However, using a deoxidizer packaging comprising the breathable packaging material of the present invention can effectively inhibit oil from permeating into the deoxidizer.

[0149] More specifically, such foods include chocolate confectionery containing 1% to 50% fat by mass, and edible meat (e.g., beef) containing 1% to 50% fat by mass. The oxygen scavenger package of the present invention is particularly useful when the chocolate confectionery is stored at room temperature (e.g., 25° C.), and when the meat is stored under refrigerated conditions (e.g., 5° C. to 10° C.).

[0150] While the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, but includes the concept of the present invention and all aspects encompassed by the claims, and various modifications are possible within the scope of the present invention.

[0151] Example

[0152] Hereinafter, the present embodiment will be described in detail using Examples and Comparative Examples. However, the present embodiment can be modified as appropriate as long as the effects of the present invention are achieved.

[0153] <Measurement>

[0154] Various measurements in Examples and Comparative Examples were performed as follows.

[0155] (thickness)

[0156] The thickness shall be the value listed in the catalog, except for the thickness of the intermediate layer below.

[0157] [Thickness of the middle layer (non-woven fabric)]

[0158] The thickness of the intermediate layer (non-woven fabric) was measured as follows: the air-permeable packaging material of the deoxidizer package was cut at a portion other than the peripheral heat-sealed portion, the thickness of the intermediate layer in the cut surface was observed using a digital microscope ("VHX-5000" manufactured by KEYENCE Co., Ltd.), and the distance between the two points was measured using the attached software.

[0159] It should be noted that in Comparative Example 10, delamination occurred during the manufacturing process, preventing the production of a breathable packaging material having the desired composition. Consequently, the deoxidizer package was not produced. Therefore, for Comparative Example 10, a portion of the breathable packaging material that had delamination and exhibited good interlayer adhesion was selected and observed through the aforementioned cut surface to measure the thickness of the intermediate layer.

[0160] Furthermore, when the intermediate layer is a nonwoven fabric, the embossed nonwoven fabric exhibits significant differences in thickness depending on the observation point. In particular, the difference in thickness is particularly large between the embossed compressed and uncompressed portions. Therefore, in this measurement, an uncompressed portion of the nonwoven fabric is randomly selected from the cross-section, and the thickness of the thickest portion of this uncompressed portion is measured. The thickness values ​​measured at these three randomly selected uncompressed portions are averaged to obtain the thickness t of the nonwoven fabric.

[0161] On the other hand, when the intermediate layer is oil-resistant paper, the thickness does not vary significantly depending on the observation point. Therefore, the thickness of the selected portion is measured by arbitrarily selecting an observation point on the cross-section. The average of the thickness measurements at these three randomly selected points is used as the thickness of the oil-resistant paper.

[0162] (Melting Point)

[0163] The melting point was measured in a nitrogen atmosphere using a differential scanning calorimeter ("DSC-60" manufactured by Shimadzu Corporation) in accordance with JIS K 7121-1987.

[0164] (Weight per unit area)

[0165] The unit area weight is per 1m 2 For the weight of non-woven fabrics or oil-resistant paper, use the value recorded in the catalog.

[0166] (Breathability resistance)

[0167] Air permeability resistance was measured in accordance with JIS P8117:2009 using an Oken air permeability tester (Asahi Seiko Co., Ltd., Model EG02). The measurement was performed with the median value of the measurable range set at 2000. The measurement was repeated 10 times for each nonwoven fabric or oil-resistant paper.

[0168] <Materials>

[0169] Materials and the like used in Examples and Comparative Examples are shown below.

[0170] (1) Outer layer

[0171] · Two-layer non-porous film: produced by the following method.

[0172] A polyethylene terephthalate film (thickness 12 μm, melting point 255°C; hereinafter referred to as "PET film") as a substrate layer and a low-density polyethylene (thickness 15 μm, melting point 105°C; hereinafter referred to as "PE") as a welding layer were stacked and extrusion laminated to obtain a two-layer non-porous film.

[0173] · Two-layer porous film: produced by the following method.

[0174] The non-porous film was perforated using a needle roller (needle pattern 10.0 mm x 10.0 mm, needle diameter 0.6 mm) so as to penetrate from the surface of the PET film to the PE film to form external air holes, thereby obtaining a two-layer perforated film.

[0175] (2) Middle layer

[0176] PET nonwoven fabric 1: Asahi Kasei Corporation "ELTAS (registered trademark) E01040", weight per unit area 40 g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0177] PET nonwoven fabric 2: Asahi Kasei Corporation "ELTAS (registered trademark) E01050", weight per unit area 50 g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0178] PET nonwoven fabric 3: Asahi Kasei Corporation "ELTAS (registered trademark) E01070", weight per unit area 70g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0179] PET nonwoven fabric 4: Asahi Kasei Corporation "ELTAS (registered trademark) E01012", weight per unit area 12 g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0180] PET nonwoven fabric 5: Asahi Kasei Corporation "ELTAS (registered trademark) E01030", weight per unit area 30 g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0181] PET nonwoven fabric 6: Asahi Kasei Corporation's "ELTAS (registered trademark) E01100", weight per unit area 100 g / m 2 , air permeability resistance 0 seconds, melting point 257 ℃

[0182] Ny nonwoven fabric: Asahi Kasei Corporation's "ELTAS (registered trademark) N01050," weight per unit area 50 g / m 2 , air permeability resistance 0 seconds, melting point 215 ℃

[0183] PET-PE nonwoven fabric: "ELEVES (registered trademark) S0503WDO" manufactured by Unitika Ltd., weight per unit area: 50 g / m 2 , air permeability resistance 0 seconds, melting point 127 ℃

[0184] Fluorine-based oil-resistant paper: Oil-resistant paper coated with a fluorine-containing oil-resistant agent on the surface, with a unit weight of 50g / m 2 , Breathability resistance 6~9 seconds (average 7 seconds)

[0185] Non-fluorine oil-resistant paper: Oil-resistant paper impregnated with starch-based oil-resistant agent, with a unit weight of 35g / m 2 , Breathability resistance 340~1700 seconds (average 765 seconds)

[0186] (3) Inner layer: Made in the following way.

[0187] A linear low-density polyethylene film (thickness 40 μm, melting point 123° C.; hereinafter referred to as “LLDPE40”) was subjected to a hole-forming treatment (opening rate 5.7 points / cm) using a needle roller. 2 , needle diameter 0.6 mm, needle pattern 5.0 mm×5.0 mm) to obtain the inner layer.

[0188] (4) Deoxidizer: A powdered iron-based self-reactive deoxidizer containing iron powder, calcium chloride, sodium chloride, diatomaceous earth impregnated with water, and activated carbon.

[0189] (Example 1)

[0190] [1] Production of breathable packaging materials

[0191] First, a PET nonwoven fabric 1 was used as an intermediate layer. The intermediate layer and the inner layer were stacked with the needle-pierced surface of the inner layer facing outward, and heat-laminated and fully fused to obtain a two-layer composite film.

[0192] It should be noted that the thermal lamination process is carried out as follows: the above-mentioned intermediate layer and inner layer are laminated and clamped with two protective PET films (100 μm), and an iron ("NI-CL312-H" manufactured by Panasonic Corporation) heated to a surface temperature of 185°C is pressed on the protective PET film on the intermediate layer side for 3 seconds.

[0193] Next, the protective PET film on the middle layer side is peeled off, and a two-layer non-porous film as an outer layer is arranged and stacked on the middle layer with the PE side and the middle layer side facing each other, and heat lamination is performed and full-surface welding is performed to obtain a packaging material multilayer film (breathable packaging material).

[0194] Note that the heat lamination process was performed by overlaying a protective PET film (same as above) on the outer layer and pressing an iron (same as above) heated to a surface temperature of 185°C against the outer protective PET film for 5 seconds. After welding, the entire protective PET film was removed.

[0195] The obtained breathable packaging material has the following layer structure: outer layer (two-layer non-porous film: base layer (PET film) / welding layer (PE)) / intermediate layer (PET nonwoven fabric 1) / inner layer (LLDPE40, through hole H diameter φ1: 860 μm).

[0196] [Diameter of through hole H φ1]

[0197] The diameter φ1 of the through-hole H is measured by the following method.

[0198] First, a seal check liquid ("AGELESS Seal Check Liquid" manufactured by Mitsubishi Gas Chemical Co., Ltd.) is blown onto one surface of the inner layer of the breathable packaging material having the above-mentioned layer structure. Then, the seal check liquid remaining on the surface of the inner layer is thoroughly wiped off with kimwipes, and only the portion of the middle layer exposed through the through hole H (the opening portion) is dyed.

[0199] The dyed openings are randomly selected and observed using a digital microscope (same as above). The size of the longest opening diameter (long diameter) is measured, and the measured values ​​of the randomly selected six openings are averaged to obtain the diameter φ1 of the through-hole H.

[0200] [2] Production of deoxidizer packaging

[0201] The resulting breathable packaging material was cut into 6 cm x 4 cm pieces, folded in half at the center of the long side with the inner layer facing inward, and heat-sealed with one side open at a 5 mm width to produce a small, breathable packaging material with an outer dimension of 3 cm x 4 cm. After filling this breathable packaging material with 0.7 g of deoxidizer, the open side of the breathable packaging material was heat-sealed with a 5 mm width to obtain a deoxidizer package.

[0202] Heat sealing was performed using a tabletop sealer ("P-300" manufactured by Fuji Impulse Co., Ltd.) with the knob 8 adjusted.

[0203] (Examples 2 to 4)

[0204] In Examples 2 to 4, air-permeable packaging materials and deoxidizer packages were produced by the same method as in Example 1, except that the intermediate layer was changed to the intermediate layer shown in Table 1.

[0205] (Comparative Examples 1 to 4)

[0206] In Comparative Examples 1 to 4, air-permeable packaging materials and oxygen scavenger packages were produced 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 the one shown in Table 1.

[0207] (Comparative Examples 5 to 9)

[0208] In Comparative Examples 5 to 9, air-permeable packaging materials and oxygen scavenger packages were produced by the same method as in Example 1, except that the intermediate layer was changed to the intermediate layer shown in Table 1.

[0209] (Comparative Example 10)

[0210] In Comparative Example 10, the intermediate layer was replaced with the one shown in Table 1. However, under the same conditions as in Example 1, the intermediate layer could not be properly fused to the inner layer, resulting in a state where the layers easily separated (interlayer delamination). Consequently, it was not possible to produce a breathable packaging material having the desired layer structure. Therefore, it was not possible to produce an oxygen scavenger package.

[0211] <Evaluation>

[0212] The following evaluation tests were performed using the deoxidizer packages produced in Examples and Comparative Examples. Note that, for Comparative Example 10, since a deoxidizer package could not be produced, the following evaluation tests were not performed.

[0213] [Contains fluorine]

[0214] Among the materials used above, the only material containing fluorine was fluorine-based oil-resistant paper. Therefore, in this example, the use of fluorine-based oil-resistant paper was evaluated as containing "fluorine," and all other materials were evaluated as containing "no fluorine." The results are shown in Table 1.

[0215] [Evaluation test]

[0216] One oxygen scavenger package was placed in contact with one piece of fruit cake (trade name: "Semple Amoy Wine Fruts Pound Cake") (20 g) and placed in an oxygen barrier bag (size: 150 mm × 200 mm, oxygen permeability: 0.53 mL / m2) along with 100 ml of air. 2 The sealed oxygen barrier bags were then immediately placed in a 25°C constant temperature oven and stored for one week.

[0217] One week later, the oil resistance and deoxidation performance were evaluated by the following methods. The results are shown in Table 1.

[0218] (Oil resistance)

[0219] After one week, the oxygen barrier bag was opened, the deoxidizer package was removed, and the deoxidizer (raw material powder) filled in the deoxidizer package was removed. The presence of oil permeation into the deoxidizer was visually inspected. In this example, if the deoxidizer became wet due to oil permeation and lost its fluidity, it was evaluated as "yes"; otherwise, it was evaluated as "no."

[0220] (Deoxidation performance)

[0221] After one week, a rubber sheet for sampling (25 mm x 25 mm, 2 mm thick) was attached to the unopened oxygen barrier bag. A syringe was inserted through the rubber sheet to sample the gas inside and measure the oxygen concentration.

[0222] The measurement was performed using a gas chromatograph ("GC-2014" manufactured by Shimadzu Corporation). The oxygen concentration was calculated by substituting the measured value into a pre-prepared calibration curve.

[0223] The above measurement was performed three times, and the arithmetic mean of the results was used to evaluate the oxygen concentration within the oxygen barrier bag. A lower oxygen concentration within the oxygen barrier bag indicates better deoxygenation performance of the oxygen scavenger package used. In this example, an oxygen concentration within the oxygen barrier bag of 0.1% or less was considered good.

[0224] [Table 1]

[0225]

[0226] As shown in Table 1, it was confirmed that the deoxidizer package using the following breathable packaging material can cope with defluorination and exhibit excellent oil resistance and deoxidation performance: the outer layer has no through-holes, the melting point of the resin constituting the non-woven fabric of the intermediate layer is 50°C or 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 non-woven fabric is 0.20 mm to 0.42 mm (Examples 1 to 4).

[0227] In contrast, it was confirmed that when the outer layer of the breathable packaging material used had through holes (Comparative Examples 1 to 4), when the outer layer of the breathable packaging material used did not have through holes but the intermediate layer was fluorine-based oil-resistant paper (Comparative Example 5), when it was non-fluorine-based oil-resistant paper (Comparative Example 6), and when it was a non-woven fabric that did not meet the specified conditions (Comparative Examples 7 to 9), it was not possible to cope with defluorination or to achieve both excellent oil resistance and deoxidation performance.

[0228] It was confirmed that when a nonwoven fabric having a thickness exceeding the prescribed thickness was used as the intermediate layer of a breathable packaging material, a breathable packaging material having a prescribed layer structure could not be obtained due to lamination failure (interlayer delamination) (Comparative Example 10).

[0229] Industrial applicability

[0230] The deoxidizer package and the air-permeable packaging material for deoxidizer of the present invention can be used in a wide range of applications, such as food and pharmaceuticals, regardless of the target object.

[0231] Description of Reference Numerals

[0232] 100: deoxidizer packaging

[0233] 10: Breathable packaging materials

[0234] 10E: Edge of breathable packaging material

[0235] 11: Outer layer

[0236] 11a: Base material layer

[0237] 11b: Welding layer

[0238] 13: Middle layer

[0239] 13e: Cross section of the middle layer

[0240] 15: Inner layer

[0241] H: Through hole

[0242] 30: deoxidizer

[0243] F: Gas flow

[0244] t: thickness of non-woven fabric

[0245] w: Width of the heat-welded portion

[0246] X: Observation Figure 2 Direction

[0247] L1 and L2: Continuous direction along the edge 10E of the air-permeable packaging material 10

[0248] w1 and w2: Width of the heat-welded portion perpendicular to the longitudinal directions L1 and L2

[0249] S: Heat-welded part

Claims

1. A deoxidizer package comprising a deoxidizer and a breathable packaging material containing the deoxidizer. The breathable packaging material has the following structure, which comprises: The outer layer having no through-holes and including a base material layer and a fusion bonding layer, the middle layer including a non-woven fabric, and the inner layer having through-holes are sequentially included. The breathable packaging material does not contain fluorine, The melting point of the resin constituting the nonwoven fabric is 50° C. or 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. The nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.

2. The deoxidizer package according to claim 1, wherein The base layer includes one or more materials selected from the group consisting of polyethylene terephthalate and biaxially stretched polypropylene.

3. The deoxidizer package according to claim 1 or 2, wherein The welding layer includes one or more types selected from the group consisting of polyethylene and ethylene copolymers.

4. The deoxidizer package according to any one of claims 1 to 3, wherein The nonwoven fabric includes one or more selected from the group consisting of polyamide and polyester.

5. The deoxidizer package according to any one of claims 1 to 4, wherein The inner layer comprises linear low-density polyethylene.

6. The deoxidizer package according to any one of claims 1 to 5, wherein The melting point of the resin constituting the nonwoven fabric is 150° C. or higher and 300° C. or lower.

7. The deoxidizer package according to any one of claims 1 to 6, wherein The air-permeable packaging material is formed into a bag shape by heat-sealing the edges of the inner layer. The width of the heat-welded portion perpendicular to the longitudinal direction is 0.3 mm or more and 15 mm or less.

8. A breathable packaging material for a deoxidizer, having the following structure, which comprises: The outer layer having no through-holes and including a base material layer and a fusion bonding layer, the middle layer including a non-woven fabric, and the inner layer having through-holes are sequentially included. The breathable packaging material for the deoxidizer does not contain fluorine. The melting point of the resin constituting the nonwoven fabric is 50° C. or 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. The nonwoven fabric has a thickness of 0.20 mm or more and 0.42 mm or less.

9. The air-permeable packaging material for deoxidizer according to claim 8, wherein the inner layer is positioned inside and the edges are heat-fused to form a bag shape. The width of the heat-welded portion perpendicular to the longitudinal direction is 0.3 mm or more and 15 mm or less.

10. A method for producing a breathable packaging material for a deoxidizer, which is the method for producing a breathable packaging material for a deoxidizer according to claim 8 or 9. The manufacturing method includes the steps of stacking and welding to form the following structure, which sequentially includes: The outer layer, the intermediate layer, and the inner layer sequentially comprising the base material layer and the welding layer, The welding step is performed at a temperature lower than the melting point of the resin constituting the nonwoven fabric of the intermediate layer.

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