JPH09234811A - Film-like or sheet-like deoxidizing multilayer body and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent deoxidizing speed by providing a barrier film obtained by combining and layering a resin layer of a non-porous film and a protective layer formed of a finely porous resin composition having a granular water solution retarding filler dispersed therein, on an absorbing face of a finely porous deoxidizing resin layer having excellent deoxidizing performance. SOLUTION: A deoxidizing multilayer body comprises at least a deoxidizing layer 3 formed of a continuously and finely porous resin composition having a deoxidizing component dispersed therein, an oxygen permeating layer 1 formed of a thermoplastic resin of non-porous thin film, and an oxygen permeating layer 2 formed of a continuously and finely porous resin composition having a granular water solution retarding filler dispersed therein. Also, at least on one face of the deoxidizing layer 3, one or more of layers of the oxygen permeating layers 1 and 2 are combined and layered so as to form a barrier layer, wherein adjacent layers are fused with each other so as to form an oxygen absorbing face. When the oxygen permeating layers are to be provided on both faces, a barrier layer 4 is layered on other face of the deoxidizing layer 3 having the oxygen permeating layer on one face.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film-like or sheet-like deoxidizing multilayer body having an oxygen absorbing function and a method for producing the same. Specifically, an oxygen-permeable layer of a non-porous thin film and a microporous oxygen-permeable layer are provided on the absorption surface of the microporous deoxygenation layer formed at the same time by stretching the resin laminate of the base material, The present invention relates to a film-like or sheet-like deoxidizing multilayer body having excellent deoxidizing performance and having water resistance and oil resistance, and a method for producing the same. The deoxidized multilayer body of the present invention is used as a container and a package for accommodating various products which are easily deteriorated under the influence of oxygen represented by food, medicine, metal products, etc. Is done.

[0002]

2. Description of the Related Art For the purpose of preventing deterioration of foods and medicines, metal products, etc. due to oxidation, decay, propagation of mold and bacteria, etc., to remove oxygen in packaging containers and packaging bags containing these products. Oxygen absorbers have been used in the past.
Oxygen absorbers that have been frequently used since their development are in the form of granular or powdered oxygen-absorbing components packed in small bags.
On the other hand, a film-shaped or sheet-shaped oxygen absorber is known as an oxygen absorber that is easier to handle, has a wider application range, and has no problems such as erroneous eating. By using this film or sheet oxygen absorber (hereinafter, simply referred to as “oxygen absorber”) for a container or a bag, the packaging container or the packaging bag itself can have oxygen absorbing performance.

For such a deoxidized body, a deoxidized resin composition in which a granular or powdered deoxidized component is dispersed and fixed using a thermoplastic resin as a matrix component is used, and a known deoxidized component is known. An oxygen scavenger, especially an iron powder-based oxygen scavenger with excellent oxygen scavenging performance, is often used, but it is not preferable that the oxygen scavenger itself is in direct contact with an object to be packaged such as food, and the oxygen scavenger It is known that a deoxidizing layer made of a deoxidizing resin composition is provided and the deoxidizing multilayer body is covered with a breathable shielding layer. Generally, the deoxidized multilayer body is
A multi-layer structure may be used in which one surface is covered with a breathable material as an oxygen absorbing surface and the other surface is covered with a gas barrier material. When a porous ventilation material is used for the shielding layer of the absorbing surface, contamination of the moisture-containing packaged article by the elution of the deoxidized component is often experienced, and the elution of the deoxidized component is likely to occur in the shielding layer. In this respect, a resin layer is preferable, and a laminate in which a layer covering the deoxidation layer is formed of a resin layer is easy and convenient to manufacture and mold.

For example, Japanese Patent Publication No. 62-1824 and Japanese Patent Publication No. 6
For example, a multilayer body in which both surfaces of a deoxygenation layer are covered with a resin layer has been known in 3-2-2648 and the like. However, the deoxidation rate of a conventional deoxidized multilayer in which a deoxidized layer is covered with a resin layer has been extremely low. This is because the oxygen permeability of the polyolefin resin used as the resin to which the deoxidizing component is blended is relatively low, so that the deoxidizing performance of the deoxidizing resin layer itself does not become high, and similarly the deoxidizing property is This is due to the low oxygen permeability of the shielding layer of the resin that coats the layer with the absorbing surface. In other words, this is because the deoxidizing component of the deoxidizing layer is separated between the resin of the matrix component and the resin of the shielding layer.

Japanese Patent Application Laid-Open No. 2-72851 discloses a technique for improving the deoxidizing performance of a deoxidized resin layer itself by stretching a sheet of a resin composition obtained by kneading a deoxidizing component of a main component of iron powder into a thermoplastic resin. A method for forming a deoxygenated layer by making it microporous is described. Japanese Patent Laid-Open No. 2-7
No. 2851 and JP-A-5-162251 disclose a multi-layered body in which a layer of a resin composition containing a deoxidizing component and a layer of a resin composition in which a poorly water-soluble filler is blended with a thermoplastic resin are stretched. A technique is described in which two layers are simultaneously made microporous to form a deoxygenation layer and an isolation layer.

In this case, the two layers made of the resin composition each containing a particulate debris such as a deoxygenating component and a filler are stretched, whereby the interface between the particulate debris and the resin is peeled off to form many pores. The formed pores are mutually connected to form a continuous microporous body as a whole. This significantly improves the oxygen permeability of the resin portion, so that the two layers each have a significantly improved deoxygenation rate and air permeability. Although the microporous body is a porous body, non-polar or low-polarity polymers are used, so that water repellency makes it difficult for water to pass through. As described above, the deoxidized multilayer body in which the continuous microporous oxygen scavenging layer is covered with the continuous microporous shielding layer has a high deoxygenation rate, and can be used for a short period even when the packaged object has a high moisture content. If so, there is no problem of elution and contamination of the deoxygenated component, and it is considered that this is an excellent deoxygenated multilayer.

However, when a relatively low-polarity liquid (for example, when various oils and fats or alcohols are added in addition to water alone) is present in a package such as food, the continuous microporous portion The liquid penetrates into the pores of the deoxygenation, and the deoxygenated component elutes out of the deoxygenated multilayer body through the liquid phase,
There is a problem that the packaged material is contaminated. Further, even in the case of water, if the gas in the pores is dissipated (dissolved in a liquid or the like) over a long period of time, the water penetrates and the deoxygenated component may be eluted similarly. To prevent this, it is possible to apply oil-repellent treatment with a fluorine-based treatment agent, for example, in order to impart oil repellency to the separation layer.However, the treatment agent should be used as much as possible due to the risk of new contamination. Desirably not.

Further, from the viewpoint of preventing the elution of deoxidized components, the shielding layer of the deoxidized layer is preferably a non-porous resin layer, but if this resin layer becomes thick, oxygen permeability will not be sufficient. . For this reason, many examples are known in which a thin plastic layer is used as a shielding layer. For example, Japanese Patent Application Laid-Open No. 5-318675 proposes an oxygen-absorbing multilayer sheet in which a resin film is formed on a deoxidized resin layer which has been rendered microporous by stretching. However, the oxygen-absorbing sheet in which a nonporous thin film is formed directly on the oxygen-absorbing resin layer, the oxygen-absorbing component in the oxygen-absorbing resin, especially iron powder and particles during the production and handling is affected by the thickness of the shielding layer on the sheet surface. However, there is a problem of strength in that the film is protruded into a thin film having a small thickness, and there is still a risk of contamination by a deoxidizing component. Increasing the thickness of the film of the momentum-shielding layer impairs air permeability, resulting in a low deoxidation rate.

For this reason, it is actually not easy to form a deoxidized multilayer body by laminating a nonporous resin thin film having substantially sufficient oxygen permeability on a deoxidized resin layer. In particular, it is almost impossible to commercially produce a thin oxygen-containing multilayer film. For example, even if a film is bonded to a deoxygenated resin layer, there is no adhesive having excellent oxygen permeability, and a non-porous thin film is laminated as a shielding layer by a bonding method to produce a deoxygenated multilayer body. difficult. Also, when attempting to produce a deoxidized multilayer body by a known lamination method such as an extrusion lamination method or a co-extrusion lamination method, since the deoxidized resin layer contains foreign matter such as iron powder, the iron powder breaks the thin film and pinholes are formed. There is a problem in film processing, for example, the occurrence of irregularities or irregularities on the surface of the multilayer body. As described above, even when the deoxidized multilayer body is used as a packaging material, there is no concern about elution and contamination of the deoxygenated component even when used for a liquid substance, and the deoxygenation performance is excellent, and a practical film or sheet is used. The fact is that there is no deoxygenated multilayer body and its manufacturing method.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a microporous deoxygenating resin layer having excellent deoxidizing performance as a deoxidizing layer and an absorbing surface of the deoxidizing layer. With a non-porous thin film oxygen permeable layer as the side isolation layer, the deoxygenated component does not project to the surface, and even when used as a liquid substance, there is no contamination due to the elution of the deoxidized component, which is safe and hygienic. It is an object of the present invention to provide a film-like or sheet-like deoxidizing multilayer body which has no problems, is easy in manufacturing and processing, is excellent in deoxidizing performance, and is excellent in water resistance and oil resistance, and a method for producing the same.

[0011]

Means for Solving the Problems As a result of intensive studies by the present inventors, as a deoxidizing layer of a deoxidizing multilayer body, a microporous deoxygenating resin layer excellent in deoxidizing performance was used. On the absorption surface side of the layer, a shielding layer having a structure in which a resin layer of a non-porous thin film and a layer in which a resin composition in which a granular poorly water-soluble filler is dispersed as a protective layer are made microporous By solving the above problems, the deoxidizing rate is excellent, and the deoxidizing component does not protrude to the surface, and there is no fear of elution of the deoxidizing component even when used as a liquid substance, a film. It has been found that a sheet-shaped or sheet-shaped deoxidized multilayer body can be obtained. Moreover, a resin laminate in which a layer of a thermoplastic resin having oxygen permeability and a layer of a resin composition in which granular poorly water-soluble filler are dispersed are combined and laminated on the absorption surface side of the layer of the resin composition in which the deoxidizing component is dispersed. By stretching the continuous microporous deoxidation layer to form a non-porous thin film oxygen permeable layer and a continuous microporous oxygen permeable layer in a shielding layer at once, the film-like or The present invention has been completed by finding that a sheet-shaped deoxidized multilayer body can be easily produced.

First, according to the present invention, in a film- or sheet-shaped deoxidizing multilayer body in which a plurality of resin layers are laminated on each other to have a deoxidizing function, at least a deoxidizing component is dispersed in the resin composition. The deoxidized layer A obtained by continuously microporous the material, the oxygen permeable layer C made of a non-porous thin film thermoplastic resin, and the resin composition in which granular poorly water-soluble filler is dispersed are continuously microporous. And an oxygen permeable layer B formed by converting the oxygen permeable layer B to at least one surface of the deoxygenation layer A, and the oxygen permeable layer C and the oxygen permeable layer B are laminated in combination of one or more layers, respectively, and adjacent to each other. The oxygen-absorbing surface is formed by heat-sealing each layer to form an oxygen-absorbing surface.

Here, the deoxidizing multilayer body of the present invention comprises a deoxidizing layer A in which a resin composition in which a deoxidizing component is dispersed is made microporous, and as the deoxidizing component, iron powder is used as a main component. Those that do are most preferable.

On the absorption surface side of the deoxidizing layer A, a resin composition in which an oxygen permeable layer C made of a non-porous thin film of a thermoplastic resin and a granular poorly water-soluble filler are dispersed is microporous. An oxygen permeable layer B is formed by combining one or more layers each to form a shielding layer (oxygen permeable layer). The oxygen permeable layer C has an oxygen permeability of 1 × 10 ^{−1 1.}
It is preferably -6 × 10 ^-9 [cm ³ / cm ² · sec · Pa].

Furthermore, when the oxygen-permeable multilayer C of the present invention is immersed in n-heptane on the side where the oxygen-permeable layer C is present, the amount of elution from the oxygen-desorbing multilayer is 0.3 mg / cm ^{2 of} surface area. It is preferable that the content is not more than the above, whereby the deoxidized multilayer body has excellent oil resistance, and when it is used as a packaging material, it is possible to avoid the influence on the article to be packaged.

The deoxidizing multilayer body according to the present invention comprises a deoxidizing layer A.
A non-porous thin film oxygen permeable layer C and the microporous oxygen permeable layer B are combined and laminated on at least one surface of the shielding layer (oxygen permeable layer). When the layer is provided on one side, it is a single-sided absorption type oxygen absorber, and when it is provided on both sides with an oxygen-permeable layer, it is a double-sided absorption type oxygen absorber. In the case of the one-sided absorption type, the barrier layer D is provided on the other surface of the deoxidizing layer A having the oxygen permeable layer on one surface.
Is a laminated multi-layer body. Here, the barrier layer D is
It may be laminated with the deoxidizing layer A via a plurality of layers.

The structure of the shielding layer on the absorbing surface side of the deoxidizing layer A is preferably a simple structure, and the deoxidizing layer A and the oxygen permeable layer B and the oxygen permeable layer C are laminated in this order. Alternatively, the oxygen permeable layer C and the oxygen permeable layer B may be laminated in this order from the deoxidizing layer A.

Further, according to the present invention, at least a deoxidizing component is dispersed in a method for producing a film-like or sheet-like deoxidizing multilayer body in which a plurality of resin layers are laminated on each other so as to have a deoxidizing function. Layer a of the oxygen absorbing resin composition
A layer c of a thermoplastic resin having oxygen permeability and a layer b of a resin composition in which a granular poorly water-soluble filler is dispersed, and the layer c and the layer b are provided on at least one surface of the layer a. Is provided in combination with one or more layers, and each of the adjacent layers is heat-sealed to each other, and a step of stretching the base material of the resin laminate is provided, and the base material of the resin laminate is formed into a thin film by the stretching step. At the same time, while thinning the layer c in a non-porous state to form the oxygen permeable layer C, the layer a is made microporous to make the deoxidized layer A and the layer b microporous to allow oxygen permeation. Provided is a method for producing a deoxidized multilayer body, which comprises simultaneously forming a functional layer B.

Here, in the manufacturing method of the present invention, it is preferable that the base material of the resin laminate is stretched 2 to 20 times in uniaxial direction or biaxial direction in terms of area. The stretching of the resin laminate of the substrate may be any of uniaxial stretching, biaxial simultaneous stretching or biaxial sequential stretching.

In the present invention, the deoxidizing layer A is used as an intermediate layer, and an oxygen permeable layer in which a non-porous thin film oxygen permeable layer C and a microporous oxygen permeable layer B are combined and laminated on one side or both sides. It is possible to produce a single-sided absorption type or double-sided absorption type deoxidized multilayer body having In the case of a one-sided absorption type, a thermoplastic resin in which one or more layers c and b are combined and laminated on one surface of the layer a, and becomes a barrier layer D after stretching on the other surface of the layer a. A single-sided absorption type deoxidized multilayer body can be manufactured by stretching the resin laminated body of the base material on which the above layers are laminated. In this case, the gas barrier layer D may be laminated with the deoxidizing layer A via a plurality of layers. As another method for producing a one-side absorption type deoxidizing multilayer body, the layer c and the layer b are provided on one surface of the layer a.
And (1) and (2) each extend a base material of a resin laminate in which the barrier layer D is formed on the other surface of the deoxidizing layer A formed by microporousizing the layer a of the base material. By laminating, a one-sided absorption type deoxidized multilayer body can be manufactured.

In the case of the double-sided absorption type, the resin laminate is laminated on both surfaces of the layer a by combining one or more layers c and b, and on the other surface of the layer a. A one-sided absorption type deoxidized multilayer body can be manufactured by stretching the resin laminated body of the base material on which the thermoplastic resin layer serving as the barrier layer D is laminated after the stretching.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the single-sided absorption type or double-sided absorption type film-like or sheet-like deoxidizing multilayer body of the present invention are illustrated in the drawings. In addition, here, the oxygen permeable layer C is a non-porous layer C,
The oxygen permeable layer B is paraphrased as the porous layer B. Further, a resin layer (referred to as a buffer layer F) and an adhesive layer E are provided between the deoxidizing layer A and the barrier layer D of the deoxidizing multilayer body, if necessary.

As the one-side absorption type deoxidizing multilayer body, FIG. 1; non-porous layer C / porous layer B / deoxidizing layer A / barrier layer D, FIG. 2; porous layer B / non-porous layer C / Deoxidation layer A / barrier layer D, and FIG. 3; non-porous layer C / porous layer B / deoxidation layer A / buffer layer F / adhesive layer E / barrier layer D are illustrated. In addition, porous layer B / non-porous layer C / porous layer B / deoxidizing layer A / barrier layer D, non-porous layer C / porous layer B / deoxidizing layer A
/ Adhesive layer E / barrier layer D may be used.

As a double-sided absorption type deoxidizing film, FIG. 4; non-porous layer C / porous layer B / deoxidizing layer A / porous layer B
/ The non-porous layer C is illustrated. In addition, porous layer B / nonporous layer C / deoxidized layer A / nonporous layer C / porous layer B, porous layer B / nonporous layer C / porous layer B / deoxidized layer A / It may be porous layer B / non-porous layer C / porous layer B.

The deoxidizing multilayer body of the present invention can be used in various forms as a packaging material having deoxidizing performance for a part or all of a packaging bag or a packaging container. For example, FIG.
This is an example in which the one-sided absorption type oxygen absorber 10 is used for the top seal film of the packaging container 20, and FIG. 6 is an example in which the one-sided absorption type oxygen absorber 10 is used on one side of the packaging bag. Figure 7
Is an example in which the double-sided absorption type oxygen absorber 20 is used as the inner bag of the gas barrier outer bag, and FIG. 8 is an example in which the double-sided absorption type oxygen absorber is housed in the container 50 as a partition. is there. In addition, in the example of FIG. 8, partial molding and heat fusion of the end surface are added to the deoxidized film. Here, the contents are not limited to solids, and may be liquids or both solids and liquids.

Next, each layer constituting the deoxidized multilayer body of the present invention will be described in detail. The oxygen permeability of the non-porous thin film oxygen permeable layer C which plays an important role in the deoxidized multilayer body of the present invention is 1 × 10 ^{-11 to} 6 × 10 ^-9.
[Cm ³ / cm ² · sec · Pa] is desired. The need is understood by the following calculation.

When the pressure difference p on both sides of the membrane having the area A (the pressure difference is constant) and the time t required for permeating a gas having a volume V are defined by the definition, the gas permeability (P / X, P is a gas The permeation coefficient, X is the thickness of the film) is given by the following equation. P / X =
V / (A ・ p ・ t)

In a finite system for deoxidation using the deoxidation multilayer body dealt with here, the oxygen pressure decreases with deoxidation. The change of is not a linear decrease but an almost exponential decrease. Therefore, for example, an oxygen concentration of 20.6
Assuming that the oxygen concentration is reduced from a target system containing air at a volume of 0.1% by volume to an oxygen concentration of 0.1% by volume, the gas permeability in this case is log _e (20.6 / 0.1) = 5 of the value calculated by the above equation.
It should be about twice as much. Furthermore, the volume of air V _a
(V = 0.206 V _a ), air pressure p _a (p = 0.206
From p _a ), the coefficient of 0.206 is canceled out, and the above equation for gas permeability is P / X = 5V _a / (A · p _a · t).

Here, the oxygen permeability required for the non-porous oxygen permeable layer C of the deoxidizing multilayer body according to the present invention is calculated from the above gas permeability formula, p _a = 1.013 × 10 ⁵ Pa
At (normal pressure), V _a /A=0.1 to 5 cm ³ / cm ² (the amount of air present on the side of the object to be packaged per unit surface of the absorbent surface side of the deoxidizing multilayer body, which is the deoxidizing target system according to the present invention) Is included in this range), and assuming that the time required for deoxidation t = 0.5 to 5 days, V _a /(At)=0.02 to 10 cm ³ / cm ² · day
After all, P / X = 1.1 × 10 ^-11 to 5.7 × 10 ^-9 [cm
³ / cm ² · sec · Pa]. When deoxidizing from both sides, the above area may be doubled for one side.

Therefore, the resin and the thickness of the oxygen permeable layer C can be appropriately selected according to the required performance represented by the oxygen permeability P / X. The resin is a non-polar or low-polarity polymer, and its oxygen permeability coefficient P is not particularly limited when the requirement for the oxygen permeability is low. Is 1 × 10 ^-13 [cm ³ · cm / cm ² · sec · Pa] or more, and preferably 1 × 10 ^-12 [cm ³ · cm / cm ² · se]
c · Pa] or higher. In addition, as long as it is nonporous, it may be not only a polymer polymerized from a single monomer species, but also a mixture of various copolymers and resins. Further, the oxygen-permeable layer C may be composed of a plurality of layers as long as the oxygen permeability of the entire layer satisfies the above range.

Specific examples of the resin constituting the oxygen permeable layer C include ethylene, propylene, 1-butene, 4-
There are homopolymers and copolymers of olefins such as methyl-1-pentene, ethylene-vinyl acetate copolymer, polybutadiene, polyisoprene, styrene-butadiene copolymer and hydrogenated products thereof, various silicone resins, and the like. And modified products, grafts, and mixtures thereof.

Further, when the same resin as the layer C is used as the resin serving as the matrix component of the other deoxidizing layer A and the oxygen permeable layer B, there is no particular limitation, but when a different resin is used, The affinity between the resin and the resin forming the layer C is important. That is, when an adhesive is not particularly used for lamination, it is desired that the resin of the layer C and the resin used for the other layers have compatibility with each other. The proof of the “compatibility” here does not need to be thermodynamically strict. For example, if the heat sealing of both can be performed, it may be affirmed.

Here, a trial calculation will be made on the case where the non-porous oxygen permeable layer C is formed by using polypropylene which is a typical non-polar polymer and polymethylpentene having a relatively high oxygen permeability. 1) Polypropylene: oxygen permeability coefficient P = 1.7 × 10
^-13 [cm ³ · cm / cm ² · sec · Pa] (30 ° C) (Polymer
Handbook, 2nd Ed. III-235. J. Brandrup and EHImme
rgut, John Willy & Sons (1975), unit is converted) When thickness X> 10 μm, P / X <1.7 × 10 ⁻¹⁷ [cm
³ / cm ² · sec · Pa].
Typical ^{_{subjects, V a / A = 1cm 3}} / cm 2, t = 1da
In the case of y, the same calculation requires a thickness of X = 3 μm. Although the thickness of the nonporous layer having this thickness is almost at its limit in terms of strength, it can be understood that polypropylene can be used because the layer thickness can be increased in consideration of the required deoxidation time.

2) Polymethylpentene: Oxygen permeability coefficient P
= 2.4 × 10 ^-12 [cm ³ · cm / cm ² · sec · Pa] (25 ° C)
(Polymer Handbook, 2nd Ed. III-235) For a thickness X> 10 μm, P / X <2.4 × 10 ⁻⁹ [cm ³
/ Cm ² · sec · Pa]. In this case, the practical layer since a ^{_{V a / A = 1cm 3 /}} cm 2, t = even for 1day thickness X = 42 .mu.m. As described above, with respect to the oxygen permeability of the nonporous layer for shielding, it is possible to substantially satisfy the required performance by properly selecting an appropriate resin.

The maximum value of the thickness of the non-porous oxygen permeable layer C is determined by the required performance of the deoxidizing target represented by the oxygen permeability and the oxygen permeability coefficient of the resin. However, if it can be manufactured stably so that pinholes do not occur, and if it is certain that pinholes and tears will not occur even in contact with the contents in normal use, it is as thin as possible than the maximum value It is desirable. The thickness of the layer C is required to be at least about 3 .mu.m in production, and generally, the thickness is preferably about 5 to 20 .mu.m.

Next, the oxygen permeable layer B is a layer of a resin composition in which a resin composition in which a granular poorly water-soluble filler is dispersed in a thermoplastic resin is continuously microporous by stretching. The filler used in the layer B is not particularly limited as long as it is an inorganic or organic substance that is insoluble or hardly soluble in water. In particular, when the layer B is located at the outermost layer, it is necessary that the layer B does not elute under these conditions. Further, fillers such as oxides, which have a low risk of burning, are desirable.

Suitable examples of the inorganic filler used in the oxygen permeable layer B include silica, diatomaceous earth, talc, titania, barium sulfate and the like. Suitable examples of the organic filler include a granular resin having a higher melting point than that of the matrix resin, and cellulose powder. The particle size of the filler is not particularly limited as long as it is in a range that is easy to handle, including addition to the resin, but it does not damage other layers and further protects the oxygen-permeable layer C as a continuous porous layer. From
It is desirable that the thickness be smaller than the thickness of the layer C, and it is desirable that the maximum particle size be 10 μm or less.

As the thermoplastic resin used for the oxygen permeable layer B, the oxygen permeability of the resin itself does not matter so much because it is made microporous, and the poorly water-soluble filler can be easily mixed and dispersed. There is no particular limitation as long as it is one.
Rather, good compatibility with the non-porous layer C, ease of stretching,
The selection may be made in consideration of the operating temperature range of the deoxidized multilayer body, and the like, and generally follows the examples of the resin of the nonporous layer C described above.

The addition ratio of the poorly water-soluble filler to the matrix resin is generally 10 to 60% by volume in terms of volume fraction,
More preferably, it is in the range of 20 to 40% by volume. If the addition ratio of the poorly water-soluble filler is too low, it is difficult to make the porous material microporous, and if it is too high, it becomes difficult to form a film or a sheet.

Further, the air permeability of the oxygen permeable layer B is sufficiently ensured by the continuous microporous structure formed in the resin composition in which the granular poorly water-soluble filler is dispersed. This layer B
Is preferably 0.1 or more, and from the viewpoint of the strength of the layer, the upper limit is 0.9 or less, preferably 0.5 or less.

The thickness of the oxygen permeable layer B is to protect or reinforce the oxygen permeable layer C from an external force, and to prevent the layer C from being damaged by deoxidized component particles (eg, broken by a large iron powder). It is necessary to have a thickness such that the maximum particle diameter of the deoxidizing component is at least equal to or larger than the maximum particle diameter. On the other hand, if the thickness is unnecessarily large, the deoxidized multilayer body will be thickened. Therefore, the thickness of the layer B is at most 10 times or less the maximum particle size of the deoxidized component particles. Usually, the range of 20 to 200 μm is preferable.

The above oxygen permeable layer C and oxygen permeable layer B
The two types of layers described above are combined with one or more layers and stacked on the absorption surface side of the deoxidizing layer A to form an oxygen-permeable shielding layer. The position and the number of these two types of oxygen-permeable layers in the multilayer structure are particularly determined if the oxygen-permeable multilayer body is used as a packaging material and between the oxygen-desorbing layer A and the object to be packaged. There is no limitation, and it is appropriately selected according to the use / purpose, productivity, and the like. However, considering that the total number of layers is made as small as possible and that the production is simpler, the oxygen-permeable layer C and the oxygen-permeable layer B are each configured as one layer on the absorption surface side of the oxygen-absorbing layer A. be able to. In this case, the configuration is such that the oxygen-permeable layer C or the oxygen-permeable layer B is located directly on the side of the package, that is, on the outermost layer with respect to the deoxidized layer A.

Here, when the oxygen permeable layer C is between the deoxygenating layer A and the oxygen permeable layer B, the continuous microporous oxygen permeable layer B containing a hardly water-soluble filler is externally applied. Acts to protect the oxygen-permeable layer C of the non-porous thin film against the force of, and when layer C is on the contents side of layer B, layer B acts to reinforce layer C from the back. However, in any case, in the deoxidized multilayer body of the present invention, the oxygen permeable layer B plays a role of a protective layer of the oxygen permeable layer C. Further, the configuration in which the oxygen-permeable layer C is between the deoxidized layer A and the oxygen-permeable layer B is as follows.
During production, the layer C is excellent in that it is hardly damaged due to little deformation in the thickness direction, and is protected from direct impact from the outside after production. On the other hand, the configuration in which the oxygen-permeable layer C is located at the outermost layer is excellent in that even when the oxygen-permeable layer C comes into contact with a low-polarity liquid, there is no penetration of the liquid into the multilayer body. The layer configuration is selected in consideration of these advantages and disadvantages.

The deoxidizing layer A is composed of a layer of a deoxidizing resin composition in which a deoxidizing component is dispersed in a thermoplastic resin, which is made microporous by stretching. Various compositions are known as a deoxidizing component used for the deoxidizing layer A. Among them, metal powders such as iron powder, aluminum powder and silicon powder, inorganic salts such as ferrous salt, and ascorbic acid Alcohols such as salts, catechol and glycerin, and phenols are preferable, and those containing iron powder as a main component are particularly preferable. Further, iron powder and various salts, especially those to which a metal halide is added, and among them, those in which the surface of iron powder is coated with a metal halide are preferable.

The particle size of the deoxidizing component such as iron powder is
As long as the maximum particle size does not exceed the thickness of the deoxidized layer A, there is no particular limitation on the particle size distribution, but finer particles are required in terms of oxidation rate and in that they do not damage other layers (no penetration). desirable. However, if the particles are too fine, careful handling is required due to the danger of dust explosion and the like, and since they are generally expensive, the size of the particles of the deoxidizing component is 10 to 100 μm as an average particle size. Is preferred, and 30 to 50
μm is more preferred.

As for the thermoplastic resin used for the deoxidizing layer A, the oxygen permeability of the resin itself is also microporous, as in the case of the oxygen permeable layer B which is also microporous in this case. There is no particular limitation as long as it is not a serious problem and a deoxidizing component such as iron powder can be easily mixed and dispersed, and the selection of the resin is based on the selection of the resin for the oxygen permeable layer B described above. .

The addition ratio of the deoxidizing component to the thermoplastic resin is in the range of 10 to 10 in terms of volume fraction in order to make the same microporous.
60% by volume, more preferably 20 to 40% by volume is selected. When the addition ratio is expressed in terms of weight fraction, it differs depending on the density of the deoxidizing component. In the case of the deoxidizing component of the iron powder base, the adding ratio is 40 to 90% by weight, more preferably 60 to 85% by weight. Become. In addition, when the amount of iron powder is reduced, continuous microporosity can be similarly obtained by adding another filler.

In the deoxidizing layer A as well as the oxygen permeable layer B, the volume fraction of microporous is 0.1 or more and the upper limit is 0.9 or less, preferably 0.5 or less. The air permeability in the deoxidizing layer A is ensured by the continuous microporous structure formed in the resin composition in which the granular deoxidizing component is dispersed, and oxygen can easily reach the deoxidizing component in the layer.

First, the thickness of the deoxidizing layer A is almost determined by the total amount of absorbed oxygen. That is, the thickness including the minimum amount of the deoxygenated component that can absorb all the oxygen in the target air is the minimum thickness. Usually, in consideration of a slight inflow of oxygen during long-term storage of the contents, to use 2 to 3 times the minimum amount of the deoxidized component, the thickness is 2 to 3 in this minimum case.
Basically 3 times. In addition, when the oxygen scavenging layer is continuously microporous, it immediately participates in oxygen scavenging up to the oxygen scavenging component inside the oxygen scavenging layer as compared with the case where the oxygen scavenging layer is not microporous. Therefore, in particular, the initial absorption rate increases substantially in proportion to the thickness. Therefore, the thickness is determined in consideration of the deoxidation rate. However, on the other hand, since the oxygen transmission of the nonporous oxygen-permeable layer C is rate-determining, the maximum absorption rate is obtained when the transmission rate in the layer C is equal to the absorption rate in the deoxygenation layer A. The thickness of the deoxidizing layer A is appropriately determined in consideration of the above, but is usually preferably 10 to 400 μm.
m, more preferably in the range of 30 to 200 μm.

In the case of the single-sided absorption type, the deoxidizing multilayer body according to the present invention is a multilayer body in which the barrier layer D is laminated on the other side of the absorbing surface of the deoxidizing layer A. Examples of the resin constituting the barrier layer D include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon MXD, chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride, and ethylene-vinyl alcohol copolymer. Examples include low oxygen permeable resins such as coalesced products.
The resin relating to the barrier layer D is not necessarily an oxygen barrier resin, but may be an oxygen permeable resin as long as it can be used substantially as a barrier layer by increasing the thickness. Further, as the material for forming the barrier layer D, in addition to the single-layer film of the low oxygen permeable resin, a composite film of this film, a metal foil such as aluminum, a vapor deposition film of metal or metal oxide, silicon oxide, etc. It may be the composite film used.

In forming the barrier layer D, a resin layer serving as a barrier layer is preliminarily laminated together with other resin layers in accordance with the properties of the constituent materials to form a resin laminate of the stretching base material.
This substrate is stretched to form a barrier layer D, or
A method of laminating the barrier layer D after stretching the resin laminated body of the stretching base material which does not include the resin layer to be the barrier layer can be adopted. Note that another resin layer or an adhesive layer can be provided between the barrier layer D and the deoxidizing layer A in order to stack the barrier layer D.

The deoxygenated multilayer body of the present invention is suitable for use as a packaging material in a system containing various liquids.
It is preferable to have liquid resistance to these liquids. By using a non-polar or low-polarity polymer or a mixture of these polymers as a resin constituting each layer, water, a highly polar solvent such as alcohols, an acid, and an aqueous solution such as an alkali are used. Almost liquid resistance can be provided. However, some non-polar or low-polarity polymers are partially or completely dissolved depending on various oils or low-polarity organic solvents. Therefore, for applications requiring resistance to such various oils and low-polarity organic solvents (hereinafter referred to as oil resistance), it is better to further select a resin type. This selection can be made, for example, by measuring the amount of the resin dissolved in one or more representative solvents, and if the amount of the resin is lower than a predetermined value, the resin can be used for oil-resistant applications.

Regarding the amount of dissolution when various films are used in, for example, food packaging containers, there are generally standards to be met. The standard in Japan is “D” of “Third apparatus and container and packaging” of “Standards for foods and additives” based on the “Food Sanitation Law” (Notification No. 370 of the Ministry of Health and Welfare in 1959).
“2.
Synthetic resin utensils or containers and packaging ". Of these, oil resistance was determined by measuring the amount of evaporation residue in n-heptane (after elution) when the film was immersed at 25 ° C. for 1 hour using 2 cm ³ of n-heptane per 1 cm ² of surface area of the film. (expressed as the ratio of the weight of evaporation residue to the weight of n-heptane). However, the dissolution amount is generally not an equilibrium value due to elution within a finite time. If this amount is below the specified value, it can be used for packaging containers. The specified value is specified for each resin type, and as an example of a higher specified value,
There are 240 ppm of polystyrene, 150 ppm of polyethylene and polypropylene (30 ppm when used in applications above 100 ° C). Using a density of n-heptane of 0.68 g / cm ³ , the surface area of the film was 1 cm 2.
The eluted weight per 240 ppm is about 0.3
Calculated as mg.

As described above, when oil resistance is required for the deoxidized multilayer body, the resin species may be selected according to the above criteria. In general, when the affinity between the resin and the solvent is low, elution occurs only from the vicinity of the surface of the film, but when the affinity is high, the solvent penetrates to the inside of the film layer. Elution also occurs. That is, the amount of elution when the affinity is high is affected not only by the surface area of the film but also by their thickness. Therefore, when measuring the oil resistance of the deoxidized multilayer body, the one having a fixed thickness, that is, the one after complete multilayering is used. Also,
Oxygen absorption surface of the deoxygenation multilayer body (one side with an oxygen permeable layer for one side absorption type, both sides for both sides absorption type) because it is measured only on the side in contact with the deoxygenation target. Is the measurement site.

The deoxidizing multilayer body of the present invention can be used in various forms as a film-shaped or sheet-shaped deoxidizing packaging material, for example, in a part or all of a packaging bag or a packaging container. The packaged material at that time may be a solid, liquid, creamy or slurry-like semi-liquid, or a mixture thereof. Therefore, as a material constituting each layer of the deoxidized multilayer body of the present invention, it is possible to maintain a high deoxygenation rate, prevent elution of deoxygenated components and resins, and cause problems such as new elution. If not, various additives other than the above-described materials can be added. Examples of the additives include pigments and dyes for coloring or hiding, stabilizing components for preventing oxidation and decomposition, antistatic components, moisture absorbing components, deodorizing components, plasticizing components, and flame retarding components. No. Similarly, a printing layer, an easy-opening layer, an easy-peeling layer, and the like can be added as long as the performance of the deoxygenated multilayer body is not adversely affected.

The essential point of the production in the present invention is that a plurality of resin layers are laminated to produce a resin laminate of a base material for stretching in advance, and then a plurality of resin layers of this resin laminate are collectively stretched. It is in. According to this method, the deoxidized layer A and the oxygen-permeable layer B containing the poorly water-soluble filler are each effectively and continuously made microporous, and at the same time, the oxygen-permeable layer C of the nonporous resin layer is stably formed. The oxygen-absorbing layer A, which can be made thinner and has excellent oxygen-absorbing performance, and a nonporous thin-film oxygen-permeable layer C and a microporous oxygen-permeable layer B are laminated on the absorption surface side. It is possible to manufacture a multilayer body including a shielding layer having excellent oxygen permeability. Even if a method of laminating each layer after stretching (including using a ready-made single-layer porous film) is taken, adhesion or fusion is required at the time of lamination, and the microporosity at a sharp angle is caused by the adhesion or fusion. It is impaired and oxygen permeability is lowered, and there is difficulty in adhering or fusing the non-porous thin film.

In the production of the resin laminate of the base material on which a plurality of resin layers are laminated, the usual methods such as coextrusion, extrusion coating and extrusion lamination can be used.
Either technique can provide a multilayer structure consistent with the present invention. In particular, extrusion coating and extrusion lamination, which are sequentially laminated, are preferable, and a once formed smooth film (particularly before stretching, it is thick, so there is no problem in strength)
For example, even if iron powder is used as the deoxidizing component, the other layers are less likely to be affected by the irregularities of the iron powder.

The resin laminate of the substrate may be stretched by any of uniaxial stretching, biaxial simultaneous stretching, and biaxial sequential stretching, as is generally known. The stretching temperature in this case is
The melting temperature of the resin relating to the oxygen-permeable layer C is preferably equal to or lower than the melting temperature, and the stretching ratio is desirably 2 to 20 times in terms of area. Although the thickness of the resin laminate of the base material is reduced by stretching, the change in thickness before and after the stretching is the material constituting each layer,
Since the thickness differs depending on the layer configuration, the stretching ratio, and the like, it is necessary to determine the thickness of each layer to be laminated and the total thickness in advance in consideration of these factors.

As described above, when the deoxidizing multilayer body of the present invention is a single-sided absorption type, it is a multilayer body in which the barrier layer D is laminated on the other side of the absorbing surface of the deoxidizing layer A. The barrier layer D is
The resin layer can be formed by laminating and stretching the resin laminate of the stretching base material, but can also be laminated after stretching the resin laminate of the base material. When the barrier layer D is added later, the layer D can be adhered or fused by a known method such as heat lamination, dry lamination, and extrusion coating to form a final multilayer structure.

[0060]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The common items in the description are as follows. The produced film-shaped or sheet-shaped oxygen-absorbing multilayer body (hereinafter, simply referred to as oxygen-absorbing multilayer body) was evaluated for the oxygen-absorbing performance, the elution of the oxygen-absorbing component, and the oil resistance by the following methods. In the test of the oxygen-absorbing performance, the cross section of the oxygen-absorbing multilayer body of the sample cut into a predetermined size is covered with a synthetic rubber-based adhesive, and the oxygen-absorbing layer may be exposed on the cut surface, which may affect the results. In order to avoid such a situation, the test piece was subjected to an end face treatment. In the dissolution test of the deoxygenated component, the end-treated sample was further subjected to a temperature of 60 ° C. and a relative humidity of 80%.
Was left in the air for about 5 days, and the iron powder in the oxygen-absorbing resin composition was sufficiently oxidized in advance to obtain a measurement sample. Note that this oxidation treatment was performed because iron as a deoxidizing component is easily leached by oxidation.

1) Evaluation of deoxidation performance (measurement of deoxidation time and total oxygen absorption amount) A sample (area: 300 cm ² , size: 15 cm x 20 cm) having a predetermined area subjected to end face treatment and water for humidification were included. Absorbent cotton and a barrier bag made of aluminum foil laminated film (dimensions;
(20 cm × 30 cm), and after filling with a predetermined amount of air, the bag was heat-sealed and sealed. This sealed bag was kept at 25 ° C., and the oxygen concentration in the bag was measured over time using a gas chromatograph (GC-14B, Shimadzu Corporation), and the change in the oxygen concentration was tracked. Normally, the deoxidizing performance is evaluated by the deoxidizing time. When measuring the deoxidizing time, the amount of air to be filled into a sample having an area of 300 cm ² is set to 300 cm ^3, and the oxygen concentration in the bag is 0%. The time required to reach 0.1% by volume was indicated as the deoxygenation time. The measurement of the total oxygen absorption amount is appropriately performed. In this case, the area is 300 cm.
^The amount of air to be filled was set to 1500 cm ³ for the sample No. ^2, and the oxygen absorption amount was calculated from the oxygen concentration at the time when the oxygen concentration in the bag stopped changing, and this was defined as the total oxygen absorption amount.

2) Elution evaluation of deoxidized components (iron ions) Samples (area: 300 cm) subjected to the above-mentioned end surface treatment and oxidation treatment
^2. Dimensions: 15 cm × 20 cm) were placed in a polyethylene container with a lid and placed in a hydrochloric acid aqueous solution (hydrochloric acid concentration: 0.01 N).
It was immersed in 00 cm ³ at 25 ° C., and the iron concentration in the immersion liquid was measured over time using a plasma emission spectrometer (Seiko Electronics Co., Ltd., model name: SPS1200VR). In this case, the hydrochloric acid aqueous solution used was prepared from hydrochloric acid (for atomic absorption analysis) and pure water (conductivity less than 0.07 μS / cm), and the sample had an oxygen-permeable layer B (microporous resin) on the outer surface. In the case of a deoxidized multilayer body having a layer configuration having a layer), the sample was previously immersed in ethanol to reduce the water repellency unless otherwise specified, and then subjected to an immersion test.

The allowable upper limit concentration of iron in this test was set to 3 ppm by the taste test using an aqueous ferric chloride solution as a standard model solution of iron concentration. That is, when the concentration of ferric chloride was gradually increased from 0 ppm using an aqueous ferric chloride solution and the concentration affecting taste was examined, a slight change in taste was observed when the concentration reached about 10 ppm. Therefore, the permissible upper limit concentration of iron was defined as 3 ppm obtained by removing the chlorine content from the ferric chloride concentration of 10 ppm.

3) Evaluation of oil resistance: A deoxidized body sample (dimension: 2; end-face treated) was placed in the opening (opening area 200 cm ² ) of a test container containing 400 cm ³ of n-heptane (special grade reagent).
The absorbent surface of 0 cm × 20 cm, area: 400 cm ² ) was placed on the container side, and the container was sealed with a clamping jig. Then, the container was turned upside down, and n-heptane was brought into contact with the sample. Hold for 1 hour. Subsequently, the n-heptane in contact with the oxygen scavenger sample was evaporated to dryness, the weight of the residue was measured, and the amount of the evaporation residue in the blank test of the same amount of n-heptane was subtracted from this weight. It was divided by the contact area of heptane (200 cm ² ) and expressed as the amount of elution per 2 cm ^{3 of} n-heptane / cm ^{2 of} contact area.

The above-mentioned method is the same as the above-mentioned "Standard of foods, additives, etc." (Ministry of Health and Welfare Notification No. 370 of 1959), "No. 3".
This is a method performed in accordance with “4 Evaporation residue test method” of “B. Test method of utensils or containers and packaging in general” of “Equipment and containers and packaging”, and n-heptane 2 cm ³ calculated from the specified value of polystyrene of 240 ppm. The elution amount per 1 cm ^{2 of} contact area is 0.3 mg as a reference value, and here, oil resistance is judged in comparison with this value. In addition, it can be used for applications that do not require oil resistance, regardless of this evaluation.

Next, common items in the production of the deoxidized multilayer body are as follows. As a deoxidizing component used in the deoxidizing layer A, iron powder (average particle size of about 35 μm, maximum particle size of about 100 μm)
m) is sprayed with a 50% by weight aqueous solution of calcium chloride, dried by heating, and coated on the surface of iron powder with calcium chloride at a ratio of 2 parts by weight per 100 parts by weight of iron powder. Flour) was prepared. Then, using a twin-screw extruder, the granular deoxygenated component and a predetermined resin are kneaded at a mixing ratio of 70:30 (weight ratio), extruded from a strand die, cooled, and then cut with a pelletizer to pellet the resin composition. Got A pellet I of a resin composition containing 70% by weight of calcium chloride-coated iron powder and 30% by weight of various resins was used as a material for the deoxidizing layer A.

As a hardly water-soluble filler for the oxygen permeable layer B, synthetic silica (Tatsumori Co., Ltd., trade name; CRYSTALITE V)
XS2, average particle size 5 μm), and in the same way with a twin-screw extruder,
The synthetic silica and the predetermined resin are mixed at a mixing ratio of 50:50.
The mixture was kneaded (weight ratio) to obtain pellets of the resin composition. A pellet II of a resin composition obtained by mixing 50% by weight of synthetic silica and 50% by weight of various resins was used as a material of the oxygen permeable layer B.

Example 1 In producing a deoxidized multilayer body, the resins used for constituting each layer were as follows. A buffer layer F and an adhesive layer E were provided between the deoxidizing layer A and the barrier layer D of the deoxidizing multilayer body. Resin related to oxygen permeable layer C (non-porous layer);
Ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd .; TAFMER P-0680, molar ratio of ethylene component about 0.75, melt flow rate 0.4 g / 10 min (190
℃), oxygen permeability coefficient at 25 ℃ 1.4 × 10 ^-12 [cm ³
・ Cm / cm ²・ sec ・ Pa]) and linear low-density polyethylene (Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2520F, the trade name is polyethylene, but in reality it is a copolymer containing some α-olefins. , Melt flow rate 2.3g / 10min,
Oxygen transmission coefficient at melting point 118 ℃, 25 ℃ 3.0 × 10
^-13 [cm ³ · cm / cm ² · sec · Pa]) (mixing ratio 70:30 by weight) (oxygen permeability coefficient of mixed resin at 25 ° C 8.2 × 10 ^-13 [cm ³ · cm / cm ²⁾・ Sec ・ Pa]),
Resin related to oxygen permeable layer B (porous layer); same linear low-density polyethylene (Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2
520F), resin for deoxidizing layer A; also linear low-density polyethylene (Mitsui Petrochemical Co., Ltd .; ULTZEX 2520
F), resin for buffer layer F; also linear low-density polyethylene (Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2520F), resin for adhesive layer E; adhesive polyolefin (Mitsui Petrochemical Industry Co., Ltd.); ADMER NF300, melt flow rate 1.
3g / 10min (190 ℃), melting point 120 ℃), barrier layer D
Related resin; Nylon MXD (Mitsubishi Gas Chemical Co., Ltd .; MX
-NYLON 6007, melt flow rate 2.0g / 10min,
Melting point 240 ° C)

Using a coextrusion laminating apparatus, 6 kinds of resin or resin composition for each layer are melted and coextruded to obtain a resin layer for non-porous layer C; 40 μm / filler-containing resin for porous layer B Layer; 100 μm / deoxidizing component-containing resin layer related to deoxidizing layer A; 100 μm / resin layer related to buffer layer F; 1
A resin laminate (thickness: 460 μm) composed of 6 layers of 00 μm / resin layer relating to the adhesive layer E; 20 μm / resin layer relating to the barrier layer D; 100 μm was obtained as a stretching base material. Next, the resin laminate of the above-mentioned substrate is vertically 4 at 100 ° C.
The film was uniaxially stretched at a double magnification to produce a one-side absorption type film-shaped deoxidized multilayer body (thickness: 145 μm). The thickness of each layer of the deoxidized multilayered body after stretching is roughly as follows: non-porous layer C: 10 μm
/ Porous layer B; 40 µm / deoxidation layer A; 40 µm / buffer layer F; 25 µm / adhesive layer E; 5 µm / barrier layer D; 25
μm.

The evaluation results of the single-sided absorption type deoxidized multilayer body were as follows: deoxidation time was 1.7 days, iron elution was 0.09 ppm after 20 days, and non-porous layer C side was changed to n-heptane. The elution amount was 0.02 mg per cm ² .

Example 2 In the resin used for each layer of the deoxidizing multilayer body of Example 1, the resin relating to the non-porous layer C; the ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd .; TAFMER P- 0680)
A resin laminate of a base material for stretching was prepared using the same resin as in Example 1 except for the above. The resulting resin laminate (thickness: 460 μm) was a resin layer related to the non-porous layer C; 4
0 μm / filler-containing resin layer relating to porous layer B; 100
μm / deoxidizing component-containing resin layer related to deoxidizing layer A; 100
μm / resin layer related to buffer layer F; 100 μm / resin layer related to adhesive layer E; 20 μm / resin layer related to barrier layer D; 10
It had a 6-layer structure of 0 μm. Subsequently, the resin laminate as a base material was uniaxially stretched at 100 ° C. at a magnification of 4 times in the longitudinal direction to produce a one-side absorption type film-shaped deoxidized multilayer body (thickness: 145 μm). The thickness of each layer of the deoxidized multilayer body after stretching is roughly,
Non-porous layer C; 10 μm / porous layer B; 40 μm / deoxidation layer A; 40 μm / buffer layer F; 25 μm / adhesive layer E; 5 μ
m 2 / barrier layer D; 25 μm.

The evaluation results of the obtained single-sided absorption type deoxidized multilayer body were as follows: deoxidation time was 1.1 days, and elution of iron was 2
It was 0.13 ppm after 0 days, and the amount eluted from the non-porous layer C side to n-heptane was 0.86 mg per cm ² . In this case, the elution amount from the non-porous layer C was large.

Example 3 The resins used to form each layer of the deoxidized multilayer body were as follows. Here, the adhesive layer E was provided between the deoxidizing layer A and the barrier layer D. Resin relating to non-porous layer C;
A mixture of the ethylene-propylene copolymer (Mitsui Petrochemical Industry Co., Ltd .; TAFMER P-0680) and the linear low-density polyethylene (Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2520F) (weight mixing ratio 70: 30), the resin relating to the porous layer B; the same linear low-density polyethylene (Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2520F), the resin relating to the deoxidizing layer A; the same linear low-density polyethylene (Mitsui Petrochemical) Industry Co., Ltd.
ULTZEX 2520F), resin for adhesive layer E; the adhesive polyolefin (Mitsui Petrochemical Industry Co., Ltd .; ADMER NF300
), Resin for barrier layer D; Nylon MXD (Mitsubishi Gas Chemical Co., Ltd .; MX-NYLON 6007)

By 5 kinds of melt coextrusion, the resin layer relating to the non-porous layer C; 40 μm / the filler-containing resin layer relating to the porous layer B; 100 μm / the deoxidizing component-containing resin layer relating to the deoxidizing layer A; 100 μm / Resin layer related to adhesive layer E: 100 μm
/ Resin layer related to barrier layer D; a resin laminate of 5 layers (thickness: 440 μm) having a constitution of 100 μm was obtained. Subsequently, the resin laminate as the base material was uniaxially stretched at 100 ° C. at a ratio of 4 times the longitudinal direction to obtain a film-type deoxidized multilayer body of one side absorption type (thickness:
0 μm) was produced. The thickness of each layer of the deoxidized multilayer body after stretching is roughly as follows: non-porous layer C; 10 μm / porous layer B 40 μ
m / deoxidation layer A 40 μm / adhesive layer E 25 μm / barrier layer D 25 μm.

The evaluation results of the obtained single-sided absorption type oxygen multilayer bodies were as follows: deoxidation time was 1.7 days, and elution of iron was 2
After 0 days, it was 0.09 ppm, and the amount eluted from the non-porous layer C side to n-heptane was 0.02 mg per cm ² .

Example 4 The resin used to form each layer of the deoxidized multilayer body was as follows.
It was as follows. Resin relating to non-porous layer C; ethylene
Ropylene copolymer (Mitsui Petrochemical Co., Ltd.); TAFMER S
-4030, the mole fraction of ethylene component is about 0.5, melt flow
-Rate 0.2g / 10min (190 ℃)) and polypropylene
(Mitsubishi Chemical Co., Ltd .; FX4D, trade name is polypropylene
There is a copolymer containing some other α-olefins.
Body, melt flow rate 6.0g / 10min, melting point 140
Oxygen permeability coefficient at 25 ℃, 1.4 × 10^-13 [cm^Three・
cm / cm^Two・ Sec ・ Pa]) mixture (weight mixing ratio 50:
50) (oxygen permeability coefficient of mixed resin at 25 ° C. 3.0 ×
Ten^-13 [cm^Three・ Cm / cm ^Two・ Sec ・ Pa]), oxygen permeable layer
Resin related to B; same polypropylene (Mitsubishi Chemical Corporation;
FX4D), resin related to deoxidizing layer A; same polypropylene
(Mitsubishi Chemical Co., Ltd .; FX4D), resin for buffer layer F; same
Ku polypropylene (Mitsubishi Chemical Corporation; FX4D)

By four kinds of melt coextrusion, the resin layer for the non-porous layer C; 100 μm / the filler-containing resin layer for the porous layer B; 150 μm / the deoxidizing component-containing resin layer for the deoxidizing layer A; 150 μm / Resin layer related to buffer layer F; 800μ
A resin laminate (thickness: 1200 μm) having a 4-layer structure of m 2 was obtained. Subsequently, the four-layer resin laminate of the base material was biaxially coaxially stretched at 130 ° C. with a length of 3 times and a width of 3 times to obtain a deoxidized multilayer body (thickness;
215 μm) was prepared. The thickness of each layer of the deoxidized multilayer body after stretching is roughly as follows: non-porous layer C; 10 μm / porous layer B;
55 μm / deoxidation layer A; 60 μm / buffer layer F; 90 μm
Met.

On the buffer layer F side of the deoxygenated multilayer body obtained above, the polypropylene side of the laminated film of nylon and polypropylene was adhered and heat-sealed to obtain a non-porous layer C / porous layer B / deoxidized layer. A single-sided absorption type film-type deoxidized multilayer body having a six-layer structure of layer A / buffer layer F / fusion layer (polypropylene) / barrier layer D (nylon) was produced. In the heat fusion, heating was performed only from the nylon laminated film side, and the heating temperature and time were adjusted so as to minimize the non-pore formation of the porous layer B and the deoxidized layer A due to heat.

The evaluation results of the obtained single-sided absorption type deoxidized multilayer body were as follows: deoxidation time was 2.3 days and iron elution was 2 days.
After 0 day, it was 0.06 ppm, and the amount eluted from the non-porous layer C side to n-heptane was 0.08 mg per cm ² .

Example 5 The linear low-density polyethylene (resin for the non-porous layer C, the porous layer B, the deoxidizing layer A, and the buffer layer F) was used. Mitsui Petrochemical Industry Co., Ltd .; ULTZEX 2520F), by melt coextrusion of 4 layers of 3 types, resin layer related to non-porous layer C: 40 μm / filler-containing resin layer related to porous layer B: 100 μm / Deoxidizing component-containing resin layer related to deoxidizing layer A; 100 μm / buffer layer F
A resin layer having a four-layer structure (thickness: 1040 μm) having a resin layer of 800 μm was obtained. Subsequently, the four-layer resin laminate was uniaxially stretched at 100 ° C. in a length of 4 to prepare a deoxidized multilayer body (thickness: 290 μm). The thickness of each layer of the deoxidized multilayer body after stretching was roughly: non-porous layer C; 10 μm / porous layer B; 40 μm / deoxidized layer A; 40 μm / buffer layer F; 200 μm.

Adhesive polyolefin (Mitsui Petrochemical Co., Ltd .; ADMER NF550, melt flow rate 6.2 g / 10 min (190 ° C.) was used as an adhesive layer E on the buffer layer F side of the deoxidized multilayer body obtained above. ), Melting point 120 ° C.) 15 μ
As a barrier layer D, ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd .; EVAL EP-E105, melt flow rate 5.5 g / 10 min (190 ° C), melting point 16)
5 ° C.) is coextruded to a thickness of 20 μm and laminated to form a non-porous layer C / porous layer B / deoxidizing layer A / buffer layer F / adhesive layer E.
A single-sided absorption type deoxidized multilayer body having a 6-layer structure of a barrier layer D (EVAL) was manufactured.

The evaluation results of the obtained single-sided absorption type deoxidized multilayer body were as follows: deoxidation time was 2.8 days, iron elution was 0.07 ppm after 20 days, and n from the non-porous layer C side was measured. -Elution into heptane was less than 0.01 mg / cm ² .

Example 6 Resin relating to non-porous layer C; ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd .; TAFMER S-4030) and polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) Mixture (mixing ratio by weight 50:50), resin for porous layer B; same polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D), resin for deoxidizing layer A, same polypropylene (Mitsubishi Chemical Co., Ltd .;
FX4D), the resin relating to the buffer layer F; the same polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) is used, respectively, by melt coextrusion of 4 layers of 4 types, the filler-containing resin layer relating to the porous layer B; 150 μm / resin layer related to non-porous layer C; 100
μm / deoxidizing component-containing resin layer related to deoxidizing layer A; 150
A resin layer having a four-layer structure (thickness: 700 μm) of 300 μm / resin layer relating to μm / buffer layer F was obtained. Next, above 4
The layered resin laminate was biaxially coaxially stretched at 130 ° C. with a length of 3 times and a width of 3 times to prepare a deoxidized multilayer body (thickness: 160 μm). The thickness of each layer of the deoxidized multilayer body after stretching is roughly,
Porous layer B 55 μm / non-porous layer C; 10 μm / deoxidized layer A; 60 μm / buffer layer F; 35 μm.

The surface of the deoxidizing multilayer body on the buffer layer F side prepared as described above was subjected to corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then the dry laminate adhesive was applied to this surface to a thickness after drying. To a thickness of 10 μm, and a nylon film is laminated and adhered on this to form a porous layer B / non-porous layer C.
A single-sided absorption type deoxidizing multilayer body having a 6-layer structure of / deoxidizing layer A / buffer layer F / adhesive layer E / barrier layer D (nylon) was produced.

The evaluation results of the obtained single-sided absorption type deoxidized multilayer bodies were as follows: deoxidation time was 2.1 days and iron elution was 2
It was 0.15 ppm after 0 days, and the amount eluted from the non-porous layer C side to n-heptane was 0.10 mg per 1 cm ² .

Example 7 The resins used to form each layer of the deoxidized multilayer body were as follows. Resin related to non-porous layer C; ethylene-propylene copolymer (Mitsui Petrochemical Industry Co., Ltd .; TAFM
ER S-4030) and the polypropylene (Mitsubishi Chemical Co., Ltd.);
FX4D) mixture (weight mixing ratio 50:50), resin relating to porous layer B; same polypropylene (Mitsubishi Chemical Co., Ltd .;
FX4D), resin related to deoxidizing layer A; same polypropylene (Mitsubishi Chemical Corporation; FX4D)

First, a film of the filler-containing resin composition single layer relating to the porous layer B was prepared, and the resin relating to the non-porous layer C was extrusion-coated on this film and laminated to form the non-porous layer C. A film having a two-layer structure of a resin layer (100 μm) / a filler-containing resin layer (150 μm) related to the porous layer B was obtained. The deoxidizing layer A is formed between the two obtained two-layer films.
The deoxidizing component-containing resin composition according to (1) is melt-extruded and laminated, and the resin layer according to the non-porous layer C is 100 μm / the filler-containing resin layer according to the porous layer B is 150 μm / the deoxidizing layer A.
Deoxidizing component-containing resin layer according to the present invention; 150 μm / porous layer B
A resin laminate (thickness: 650 μm) having a five-layer structure of a filler-containing resin layer according to (1), a resin layer related to 150 μm / a non-porous layer C; and 100 μm was prepared.

Next, the five-layer resin laminate of the above-mentioned substrate was placed at 130 ° C.
Was biaxially stretched at a length of 3 times and a width of 3 times to prepare a double-sided absorption type deoxidized multilayer body (thickness: 190 μm). The thickness of each layer of the deoxidized multilayer body after stretching is roughly,
Non-porous layer C; 10 μm / porous layer B; 55 μm / deoxidized layer A; 60 μm / porous layer B; 55 μm / non-porous layer C;
It was 10 μm.

The evaluation results of the obtained bilateral absorption type deoxidized multilayer body were as follows: deoxidation time was 1.0 day, and iron elution was 2 days.
0.13 ppm after 0 days, n from one side of the non-porous layer C side
-The amount eluted into heptane was 0.07 mg / cm ² .

Example 8 The linear low density polyethylene (Mitsui Petrochemical Industry Co., Ltd.) was used for the resin for the non-porous layer C, the resin for the porous B, and the resin for the deoxidizing layer A, respectively. ; ULTZEX 2520
Resin layer of non-porous layer C: 40 μm / filler of porous layer B by melt coextrusion of 5 layers of 3 types using F);
Containing resin layer: 100 μm / deoxidizing component-containing resin layer relating to deoxidizing layer A; 100 μm / filler-containing resin layer relating to porous layer B; 100 μm / resin layer relating to non-porous layer C; 40
A resin laminate (thickness: 380 μm) having a 5-layer structure of μm was obtained.

Subsequently, the five-layer resin laminate of the above-mentioned base material was formed into 10 layers.
The film was uniaxially stretched at a temperature of 4 times at 0 ° C. to prepare a double-sided absorption type deoxidized multilayer film (thickness: 140 μm). The thickness of each layer of the deoxidized multilayer body after stretching is roughly as follows: non-porous layer C; 10 μm / porous layer B 40 μm / deoxidized layer A; 40
μm / porous layer B 40 μm / non-porous layer C: 10 μm.

The evaluation results of the obtained bilateral absorption type deoxidized multilayer body were as follows: deoxidation time was 1.3 days, and iron elution was 2
0.13 ppm after 0 days, n from one side of the non-porous layer C side
-Elution into heptane was less than 0.01 mg / cm ² .

Comparative Example 1 Polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) was used as the resin for the oxygen permeable layer B and the resin for the deoxidizing layer A and the buffer layer F, respectively, by melt coextrusion to obtain a porous film. Filler-containing resin layer relating to the quality layer B; 150 μm / deoxidation layer A
A resin layer having a three-layer structure (thickness: 600 μm) of 150 μm / resin layer related to buffer layer F; 300 μm was obtained. Next, the obtained three-layer resin laminate is simultaneously biaxially stretched at a temperature of 130 ° C. with a length of 3 times and a width of 3 times,
A deoxidized multilayer body (thickness: 150 μm) having no nonporous oxygen permeable layer C was prepared. The thickness of each layer of the deoxidized multilayer body after stretching was roughly: porous layer B; 55 μm / deoxidized layer A; 60 μm / buffer layer F; 35 μm.

The surface of the deoxidizing multilayer body on the buffer layer F side was subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a dry laminating adhesive having a thickness of 10 μm was dried on this surface. And then a nylon film is laminated and adhered onto this to form a one-sided absorption type having a five-layer structure of porous layer B / deoxidizing layer A / buffer layer F / adhesive layer E / barrier layer D (nylon). Was prepared.

The evaluation results of the single-sided absorption type deoxidizing multilayer body without the non-porous oxygen permeable layer C were as follows: deoxidation time was 0.6 days, iron elution was 2 ppm after 20 days, and ethanol was previously prepared. It is 26 ppm when immersed in the porous layer B
Elution amount from the side to the n- heptane 1 cm ² per 0.0
It was less than 1 mg.

Comparative Example 2 Resin relating to non-porous layer C; ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd .; TAFMER S-4030) and polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) Polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) was used for the mixture (weight mixing ratio 50:50), the resin for the deoxidizing layer A and the resin for the buffer layer F, and the non-porous layer C was formed by melt coextrusion. Such a resin layer; 100 μm / a resin layer containing a deoxidizing component related to the deoxidizing layer A; 150 μm / a resin layer related to the buffer layer F;
Three-layer resin laminate of 300 μm (thickness: 550 μm
) Got. Next, the obtained three-layer resin laminate was biaxially simultaneously stretched at 130 ° C. with a length of 3 times and a width of 3 times to prepare a deoxidizing multilayer body (thickness: 105 μm) of a stretching base material. The thickness of each layer of the deoxidized multilayer body after stretching is roughly the same as that of the non-porous layer C; 1
0 μm / deoxidation layer A; 60 μm / buffer layer F; 35 μm. On the buffer layer F side of the above deoxidized multilayer body, Comparative Example 1
Similarly to the above, after the surface treatment, a nylon film is laminated and adhered via a dry laminating adhesive (thickness 10 μm), and a non-porous layer C / deoxidation layer A / buffer layer F / adhesion layer E /
A one-side absorption type deoxidizing multilayer body having a five-layer structure of barrier layer D (nylon) was produced.

The evaluation results of the single-sided absorption type deoxidizing multilayer body without the porous oxygen permeable layer B were as follows: deoxidation time was 1.9 days, iron elution was 1.1 ppm after 20 days, non-porous The amount eluted from the stratum C side to n-heptane was 0.09 mg / cm ² . When the surface of the deoxidized multilayer body on the non-porous layer C side was observed with an optical microscope, a small amount of iron powder penetrating the non-porous layer was observed.

Comparative Example 3 A mixture (weight mixing ratio 50: 5) of the ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd .; TAFMER S-4030) and the polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D).
0), a filler-containing resin composition pellet II using the same polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D), a deoxidizing component-containing resin composition pellet I using the polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D), and The same polypropylene (Mitsubishi Chemical Co., Ltd .; FX4D) was melt-extruded to form a non-porous resin layer; 25 μm / filler-containing resin layer; 20 μm / deoxidizing component-containing resin layer; 150 μm / buffer layer F; 200 μm
A four-layer resin laminate (thickness: 395 μm) was obtained.
Then, the obtained four-layer resin laminate was directly stretched on the surface of the buffer layer F without stretching, as in Comparative Example 1, and after the surface treatment, a nylon film was laminated via an adhesive for dry lamination (thickness: 10 μm). Adhesion was performed to produce a single-sided absorption type oxygen absorbing multilayer body having a six-layer structure of non-porous layer / deoxidizing component-containing resin layer / deoxidizing component-containing resin layer / buffer layer / adhesive layer / barrier layer (nylon).

The evaluation results of the one-side absorption type deoxidized multilayer body obtained above were as follows: deoxidation time was 40 days, iron elution was 0.03 ppm after 20 days, and n-heptane from the non-porous layer side was obtained. The amount eluted into the column was 0.12 mg / cm ² .

Comparative Example 4 The same polypropylene was used as the resin for the porous layer B, the resin for the deoxidizing layer A and the resin for the buffer layer F (Mitsubishi Chemical Co .;
FX4D) by melt coextrusion, the filler-containing resin layer relating to the porous layer B; 150 μm / the deoxidizing component-containing resin layer relating to the deoxidizing layer A; 150 μm / the resin layer relating to the buffer layer F; 300 μm, three layers Structure of resin laminate (thickness: 600
μm) was obtained. Next, the obtained three-layer resin laminate is heated to 130 ° C.
At the same time, the film was simultaneously biaxially stretched 3 times in the longitudinal direction and 3 times in the lateral direction to prepare a deoxidized multilayer body (thickness: 150 μm) as a stretching base material. The thickness of each layer of the multilayer body after stretching is about 55 μm for the porous layer B;
m / deoxidized layer A: 60 μm / buffer layer F: 35 μm. On the surface of the buffer layer F of the above three-layered multilayer body, as in Comparative Example 1, after surface treatment, an adhesive for dry lamination (thickness 10
Nylon films are laminated and adhered to each other to form a porous layer B / deoxidizing layer A / buffer layer F / adhesive layer E / barrier layer D.
(Nylon) has a five-layer structure.

Further, on the side of the porous layer B of the above-mentioned 5-layered multilayer body, the ethylene-propylene copolymer (Mitsui Petrochemical Industry Co., Ltd .; TAFMER S-4030) and the polypropylene (Mitsubishi Chemical Co., Ltd.) ; Mixture with FX4D (weight mixing ratio 5
At 0:50), an attempt was made to additionally form a resin layer C of a non-porous thin film with a thickness of 10 μm by extrusion coating. However, if an attempt is made to heat the porous layer B or the deoxidizing layer A so as not to damage the fine pores, the amount of heat will be insufficient,
Also, the thickness of 10 μm may be due to slight unevenness on the surface of the porous layer B.
In the case of m, fusion could not be performed, and consequently, the resin layer C of a non-porous thin film could not be laminated.

[0102]

INDUSTRIAL APPLICABILITY The film-like or sheet-like deoxidizing multilayer body of the present invention has an excellent deoxidizing rate, has a property of preventing elution and contamination of deoxidizing components, and is a novel deoxidizing material which is excellent as a packaging material. It is the body. Therefore, the deoxidized multilayer body of the present invention is particularly applicable not only to a system with a small amount of liquid components, which was the main application target of the conventional oxygen absorber, but also to a system containing a large amount of various liquid components. It can be used to form containers and packages having the purpose of preventing the oxidation of various products that are easily deteriorated under the influence of oxygen, such as foods, medicines and metal products.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a layer structure example of a one-side absorption type deoxidizing multilayer body (when the nonporous oxygen-permeable layer C is the outermost layer).

FIG. 2 is a cross-sectional view of a layer configuration example of a one-side absorption type deoxidizing multilayer body (in the case where a nonporous oxygen permeable layer C is between a porous oxygen permeable layer B and a deoxidizing layer A).

FIG. 3 is a cross-sectional view of a layer configuration example of a one-side absorption type deoxidizing multilayer body (in the case where a buffer layer F and an adhesive layer E are provided on the barrier layer D side of the deoxidizing layer A).

FIG. 4 is a cross-sectional view of a layer configuration example of a double-sided absorption type deoxidizing multilayer body.

FIG. 5 is a cross-sectional view of a packaging container using a one-side absorption type film-shaped deoxidizing multilayer body as a top seal film.

FIG. 6 is a cross-sectional view of a packaging bag in which a one-sided absorption type deoxidized multilayer film is used on one surface.

FIG. 7 is a cross-sectional view of a packaging bag in which a double-sided absorption type film-shaped deoxidizing multilayer body is used as an inner bag.

FIG. 8 is a sectional view of a packaging bag in which a double-sided absorption type film-shaped deoxidizing multilayer body is used as a partition.

[Explanation of symbols]

1 Non-porous oxygen permeable layer C 2 Porous oxygen permeable layer B 3 Porous deoxidizing layer A 4 Barrier layer D 5 Buffer layer F 6 Adhesive layer E (adhesive, adhesive resin, etc.) 10 One side Absorption-type film deoxidation multilayer body 20 Double-sided absorption-type film deoxidation multilayer body 30 Contents (solid, liquid, solid and liquid, etc.) 40 Barrier container body 50 General barrier film without deoxidation function Or barrier bag

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display area B65D 81/24 B65D 81/24 D // B29K 105: 04 B29L 9:00 (72) Inventor Chiharu Nishizawa Tokyo 6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Research Laboratory, Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Hideyuki Takahashi 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Haruaki Eto 6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Tokyo Factory, Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Noriyuki Kimura 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory

Claims (13)

[Claims] 1. A film-like or sheet-like deoxidizing multilayer body in which a plurality of resin layers are laminated on each other so as to have a deoxidizing function, and at least a resin composition in which a deoxidizing component is dispersed is continuously finely divided. Deoxidized layer A made porous and oxygen permeable layer C made of non-porous thin film thermoplastic resin
And an oxygen permeable layer B obtained by continuously microporous a resin composition in which a granular poorly water-soluble filler is dispersed, and the oxygen permeable layer C and the oxygen permeable layer C on at least one surface of the deoxidation layer A. The oxygen permeable layer B and one or more layers are respectively combined and laminated, and adjacent layers are heat-sealed to each other,
A deoxidized multilayer body having an oxygen absorbing surface. 2. The deoxidized multilayer body according to claim 1, wherein the deoxidized component contains iron powder as a main agent. 3. The oxygen permeable layer C having an oxygen permeability of 1
The deoxidized multilayer body according to claim 1, wherein the density is from 10 ^{-11 to} 6 10 ^-9 [cm ³ / cm ² · sec · Pa]. 4. When the oxygen-permeable layer C of the deoxidized multilayer body is immersed in n-heptane, the amount of elution from the deoxygenated multilayer body is 0.3 mg or less per 1 cm ^{2 of} surface area. Item 2. The deoxidized multilayer body according to Item 1. 5. An oxygen permeable layer C on one surface of the deoxidizing layer A.
And at least one oxygen-permeable layer B are laminated in combination, and the barrier layer D is laminated on the other surface of the deoxidizing layer A, so that oxygen is absorbed from one side of the deoxidizing layer A. The deoxidized multilayer body according to claim 1, configured as described above. 6. An oxygen-permeable layer C and an oxygen-permeable layer B are laminated on both surfaces of the deoxidizing layer A in combination of one or more layers, respectively, and oxygen is absorbed from both sides of the deoxidizing layer A. The deoxidizing multilayer body according to claim 1, which is configured to be 7. The deoxidized oxygen scavenger according to claim 1, wherein an oxygen permeable layer C and an oxygen permeable layer B are laminated in order from the deoxidized layer A on at least one surface of the deoxidized layer A. 8. The deoxidized oxygen scavenger according to claim 1, wherein an oxygen permeable layer B and an oxygen permeable layer C are laminated in order from the deoxidized layer A on at least one surface of the deoxidized layer A. 9. A method for producing a film-like or sheet-like deoxidizing multilayer body in which a plurality of resin layers are laminated on each other so as to have a deoxidizing function, and at least a deoxidizing component is dispersed in the resin composition. Layer a, a layer c of a thermoplastic resin having oxygen permeability, and a layer b of a resin composition in which a granular poorly water-soluble filler is dispersed, and the layer c and the layer a on at least one surface of the layer a. The method includes a step of stretching a base material of a resin laminated body in which at least one layer b is combined and laminated, and adjacent layers are heat-sealed to each other. The material is formed into a thin film and the layer c is thinned in a non-porous state to form the oxygen permeable layer C, while the layer a is continuously microporous to continuously connect the deoxidized layer A and the layer b. Simultaneously forms the oxygen permeable layer B by making it microporous. A method for producing a deoxidized multilayer body, comprising: 10. The method for producing a deoxidized multilayer body according to claim 9, wherein the base material of the resin laminate is stretched in a uniaxial direction or a biaxial direction by 2 to 20 times in area conversion. 11. A base material of the resin laminate is laminated on one surface of the layer a by combining one or more layers of the layer c and the layer b, and is stretched on the other surface of the layer a to form a barrier. The method for producing a deoxidized multilayer body according to claim 9, which is a resin laminate in which thermoplastic resin layers to be the layer D are laminated. 12. The layer c and the layer b are provided on one surface of the layer a.
After stretching the base material of the resin laminated body in which one or more layers are combined and laminated, and further, the layer a of the base material is further stretched.
10. The method for producing a deoxidized multilayer body according to claim 9, wherein the barrier layer D is laminated on the other surface of the deoxidized layer A formed by microporous. 13. A base material of the resin laminate is laminated on both surfaces of the layer a by combining one or more layers c and b, and a barrier is formed on the other surface of the layer a after stretching. The method for producing a deoxidized multilayer body according to claim 9, which is a resin laminate in which thermoplastic resin layers to be the layer D are laminated.