JPH10264279A - One side absorptive deoxidation multilayered body and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To preclude a deoxidation component from being projected, and widen the selectivity of material of a barrier layer by providing a shielding layer having a resin layer of a non- porous thin film and a protection layer in which a resin composition having a grain water- insoluble filler dispersed therein is made being porous minutely, on the absorptive surface side of a deoxidation layer employing a minutely porous deoxidation resin layer. SOLUTION: On one surface of a resin composition layer 3 with deoxidizing component dispersed, one or more layers are laminated in which a thermoplastic resin layer 2 having oxygen permeability, and a resin composition layer 1 with a dispersed grain insoluble filler are bonded respectively, and a thermoplastic resin layer 5 is laminated on the other surface of the layer 3. The base material of a resin laminated body comprising each adjacent layer being heat-welded each other is oriented and, on the oriented base material layer 5 surface, a barrier layer 4 is laminated, and then, each provided on one surface of a deoxidizing layer comprising the layer 3 made being porous continuously minutely is a non-porous oxygen permeable layer having at least the layer 1 made being thinned and an oxygen permeable layer comprising the layer 2 made being porous continuously minutely, followed by providing the barrier layer 4 laminated on the oriented cushion layer having the layer oriented, on the other surface of the layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a single-sided absorption-type oxygen-absorbing multilayer film or sheet having an oxygen absorbing function and a method for producing the same. In more detail, a nonporous thin film oxygen-permeable layer and a microporous oxygen-permeable layer are provided on the absorption surface of the microporous deoxygenation layer formed simultaneously by stretching the resin laminate of the base material, Also, the present invention relates to a film- or sheet-shaped single-sided absorption deoxidized multilayer body having excellent deoxidation performance and having water and oil resistance by disposing a barrier layer on the other surface of the deoxidized layer, 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 accidental 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.

[0003] An oxygen-absorbing composition in which a particulate or powdery oxygen-absorbing component is dispersed and fixed using a thermoplastic resin as a matrix component is used for such an oxygen-absorbing material. Oxygen absorbers, especially iron powder-based oxygen absorbers with excellent deoxidation performance are often used, but it is not preferable that the oxygen absorber itself comes into direct contact with food or other packaged objects, and It is known that a deoxidized layer made of a deoxidized resin composition is provided and this is covered with a gas-permeable shielding layer to form a deoxidized multilayer body. In general, the deoxidized multilayer body has a multilayer structure in which one surface is covered with a gas-permeable material and the other surface is covered with a gas barrier material as an oxygen absorbing surface. 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 in which the deoxidizing component is blended is relatively low, so that the deoxidizing resin layer itself does not have high deoxidizing performance. This is because the oxygen permeability of the resin shielding layer that covers the absorption surface of the layer is low. 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 elution of the deoxidized component, the shielding layer of the deoxidized layer is preferably a non-porous resin layer. However, if this resin layer is thick, oxygen permeability is not 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. When the thickness of the film of the momentum shielding layer is increased, the air permeability is impaired, and as a result, the deoxygenation rate must be low.

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 It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a microporous oxygen-absorbing resin layer having excellent oxygen-absorbing performance as an oxygen-absorbing layer. Equipped with a non-porous thin film oxygen permeable layer as an isolation layer on the side, the deoxygenated component does not protrude to the surface, and even when used for liquid substances, there is no contamination due to the elution of the deoxygenated component for safety and health. There is no problem, and it is possible to use various materials for the barrier layer, it is easy to manufacture and process, and it is a single-sided absorption type deoxygenated multilayer body in the form of a film or sheet excellent in deoxidation performance and excellent in water resistance and oil resistance. It is to provide a manufacturing method thereof.

[0011]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a microporous oxygen-absorbing resin excellent in oxygen-absorbing performance as the oxygen-absorbing layer of the oxygen-absorbing multilayer body. Using a layer, on the absorption surface side of this deoxidizing layer, a resin layer of a non-porous thin film and a layer obtained by dispersing a finely porous resin composition in which a particulate poorly water-soluble filler is dispersed as a protective layer are laminated. By providing a shielding layer having a configuration as described above, a film having an excellent deoxygenation rate, no deoxygenation component protruding to the surface, and no danger of elution of the deoxygenation component even when used for a liquid substance. It has been found that a deoxygenated multilayer body in the shape of a sheet or a sheet can be obtained. In the production of the deoxidized multilayer body, a layer of a thermoplastic resin having oxygen permeability and a layer of a resin composition in which a particulate poorly water-soluble filler is dispersed on the absorption surface side of the layer of the resin composition in which the deoxidized component is dispersed By stretching the resin laminate obtained by combining and laminating, a shielding layer that combines a continuous microporous oxygen-permeable layer and a continuous microporous oxygen-permeable layer on a continuous microporous deoxygenation layer is formed at once I found what I could do. At the same time, a resin layer (buffer layer) is provided in advance on the other surface on the absorption surface side of the resin laminate, and is stretched to laminate a barrier layer on the surface of the buffer layer. It has been found that a single-sided absorption deoxidized multilayer body in the form of a film or sheet can be easily produced.

That is, the present invention relates to a film-shaped or sheet-shaped oxygen-absorbing multilayer body having an oxygen-permeable layer on one side of a deoxygenation layer and a barrier layer on the other side, and a resin in which an oxygen-absorbing component is dispersed. A resin composition in which at least an oxygen-permeable layer C made of a nonporous thin-film thermoplastic resin and a granular poorly water-soluble filler are dispersed on one surface of a deoxidized layer A in which the composition is continuously microporous. A microporous oxygen-permeable layer B, and a buffer layer E made of a thermoplastic resin on the other surface of the layer A, and a buffer of a laminate formed by heat-sealing the adjacent layers. Provided is a single-sided absorption deoxidized multilayer body characterized in that a barrier layer (D) is laminated on a layer (E) side.
Hereinafter, the “single-sided absorption-type oxygen-absorbing multilayer body” may be referred to as a “oxygen-absorbing multilayer body” or “multilayer body”.

Here, the deoxidized multilayer body of the present invention includes a deoxidized layer A in which a resin composition in which a deoxidized component is dispersed is made microporous, and iron powder is used as a main component of the deoxidized component. Is preferred.

On the absorption surface side of the oxygen-absorbing layer A, a resin composition in which an oxygen-permeable layer C made of a nonporous thin-film thermoplastic resin and a particulate water-insoluble filler are dispersed is made microporous. The oxygen permeable layer B is formed by combining at least one layer with each other to form a shielding layer (oxygen permeable layer). The oxygen permeability of the oxygen permeable layer C is 1 × 10
^{-11 to} 6 × 10 ^-9 [cm ³ / cm ² · sec · Pa] is preferable.

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 oxygen-absorbing multilayer body according to the present invention is a one-side absorption oxygen absorber, and the shielding layer formed on the absorption surface side of the oxygen-absorbing layer A preferably has a simple structure. A
, An oxygen permeable layer B and an oxygen permeable layer C are stacked in this order, or a deoxygenation layer A in which an oxygen permeable layer C and an oxygen permeable layer B are stacked in that order.

The present invention also relates to a method for producing the above-mentioned single-sided absorption-type oxygen-absorbing multilayer body, wherein the oxygen-permeable thermoplastic resin is provided on one surface of a layer a of a resin composition in which an oxygen-absorbing component is dispersed. The layer c and the layer b of the resin composition in which the particulate poorly water-soluble filler is dispersed are respectively combined in one or more layers, and a layer e of a thermoplastic resin is laminated on the other surface of the layer a. The base material of the resin laminate obtained by heat-sealing the respective layers to each other is stretched, and then the barrier layer D is laminated on the layer e surface of the stretched base material, so that the layer a is continuously microporous. A layer of oxygen-permeable layer C in which at least layer c is made thinner and oxygen-permeable layer B in which layer b is made continuous and microporous on one surface of the oxygen-absorbing layer A comprising A filter having a barrier layer D laminated on a buffer layer E formed by stretching a layer e on the other side of A To provide a method of manufacturing a side absorption type oxygen multilayered body for producing a beam-like or sheet-like oxygen multilayered body.

Here, in the production method of the present invention,
It is preferable to stretch the base material of the resin laminate in the uniaxial direction or the biaxial direction by 2 to 20 times in terms of area. The stretching of the resin laminate of the substrate may be any of uniaxial stretching, biaxial simultaneous stretching, and biaxial sequential stretching.

In the present invention, by laminating a barrier layer D via a buffer layer E on the other surface of the oxygen-absorbing layer A of the stretched resin laminate, a material having excellent oxygen barrier properties or a composite material can be obtained. Various materials can be laminated by appropriately selecting a method such as adhesion, fusion, extrusion coating, vapor deposition or the like according to the material or configuration. If, for example, an adhesive is applied to the oxygen-absorbing layer A formed by direct stretching without the intervention of the buffer layer E, the adhesive will permeate the microporous layer formed in the oxygen-absorbing layer A, Further, if a resin layer having a high softening point is to be thermally fused, the microporous layer will be damaged, and the above-mentioned known method cannot be adopted. However, according to the present invention, it is possible to form the barrier layer D by laminating through the buffer layer E even if the material cannot be laminated and stretched in advance as a barrier layer on the resin laminate. .

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION FIG. 1 shows a non-porous layer C / porous layer B / oxygen-absorbing layer A.
/ Buffer layer E / adhesive layer F / barrier layer D. Here, the configuration of the absorption surface in FIG. 1 and the non-porous layer C / porous layer B / deoxygenation layer A may be replaced with a porous layer B / non-porous layer C / deoxygenation layer A. Here, the oxygen permeable layer C is referred to as a non-porous layer C, and the oxygen permeable layer B is referred to as a porous layer B. Further, an adhesive layer F is provided between the buffer layer E and the barrier layer D.

The deoxidized multilayer body of the present invention can be used in various forms for a part or all of a packaging bag or a packaging container, with the absorbent surface inside, as a packaging material having a deoxidizing performance. For example, FIG. 2 shows an example in which the oxygen absorber 10 is used as a top seal film of a packaging container 20, and FIG. 3 shows an example in which the oxygen absorber 10 is used on one side of a packaging bag. Here, the item to be packaged is not limited to a solid, but may include a liquid, or both a solid and a liquid.

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.

In the case of the pressure difference p (the pressure difference is constant) between both surfaces of the membrane having the area A and the time t required to pass the gas having the volume V, the gas permeability (P / X, P The transmission coefficient, X is the thickness of the film) is expressed by the following equation. P / X =
V / (A ・ p ・ t)

In a finite system for deoxidation using a deoxygenated multilayer body handled here, since the pressure of oxygen decreases with deoxidation, considering that the pressure difference decreases, the oxygen concentration is reduced. 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, when the oxygen permeability required for the non-porous oxygen permeable layer C of the deoxidized multilayer body according to the present invention is calculated from the above gas permeability equation, p _a = 1.013 × 10 ⁵ Pa
In (normal ^{_{pressure), V a /A=0.1 ~5cm 3 /}} cm 2 ( in the amount of air present in the packaged articles side per unit surface area of the absorbing surface side of the oxygen multilayered body, deoxygenated object of the present invention The system is almost included in this range), the time required for deoxidation t = 0.5 to 5d
When _{ay, V a / (A ·} t) = 0.02~10cm 3 / cm 2 ·
day, and eventually P / X = 1.1 × 10 ^-11 to 5.7 × 10 ^-9
[Cm ³ / cm ² · sec · Pa].

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.

There is no particular limitation on the case where the same resin as this layer C is used as the matrix component of the other oxygen-desorbing layer A or the oxygen-permeable layer B. The affinity between the resin and the resin constituting 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 for a case where the nonporous oxygen-permeable layer C is formed using polypropylene, which is a typical nonpolar 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 nonporous oxygen-permeable layer C is determined by the required performance of the object to be deoxidized 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 granular water-insoluble fillers are dispersed in a thermoplastic resin is made continuous and 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, a filler such as an oxide having a low risk of burning is desirable.

Suitable examples of the inorganic filler used in the oxygen-permeable layer B include silica, diatomaceous earth, talc, titania, and barium sulfate. 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 for the thermoplastic resin used for the oxygen-permeable layer B, the oxygen permeability of the resin itself is not so serious because it is 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 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.

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 particulate water-insoluble 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 determined to protect and reinforce the oxygen permeable layer C from external force, prevent damage to the layer C by deoxygenated particles (for example, breakage by large iron powder), Is necessary, and the thickness is preferably at least the maximum particle diameter of the deoxidizing component. 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-described 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 located between the oxygen-absorbing layer A and the oxygen-permeable layer B, the continuous microporous oxygen-permeable layer B containing a poorly water-soluble filler is supplied from outside. Acts to protect the oxygen permeable layer C of the non-porous thin film against the force of the layer B. When the layer C is on the content side of the layer B, the layer B acts to reinforce the layer C from behind. In any case, in the deoxidized multilayer body of the present invention, the oxygen-permeable layer B functions as a protective layer for 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 oxygen-absorbing layer A is made of a layer of an oxygen-absorbing resin composition obtained by dispersing an oxygen-absorbing component in a thermoplastic resin and has been 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, those obtained by adding iron powder and various salts, particularly a metal halide, particularly those obtained by coating the surface of iron powder with a metal halide are preferred.

The size of the particles of the deoxidizing component such as iron powder is as follows:
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 in the case of the oxygen-permeable layer B, which is made microporous, the thermoplastic resin used for the oxygen-absorbing layer A also has the oxygen permeability of the resin itself because it becomes microporous. There is no particular limitation as long as it can easily mix and disperse the deoxidizing component such as iron powder, and the selection of the resin is similar to 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 10 to 10% by volume in order to similarly make the porous material microporous.
It is selected in the range of 60% by volume, more preferably 20 to 40% by volume. 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.

The deoxidized layer A also has a microporous volume fraction of 0.1 or more and an upper limit of 0.9 or less, preferably 0.5 or less, like the oxygen-permeable layer B. The air permeability in the oxygen-absorbing layer A is ensured by the continuous microporous structure formed in the resin composition in which the particulate oxygen-absorbing component is dispersed, and oxygen can easily reach the oxygen-absorbing component in the layer.

First, the thickness of the deoxidizing layer A is substantially determined by the total amount of oxygen absorbed. 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.
Three times the basics. 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.

As the thermoplastic resin used for the buffer layer E,
There is no particular limitation as long as it can be heat-fused to the resin of the oxygen-absorbing layer A and can be integrally stretched as the resin laminate.
Compatible with the deoxygenation layer A, selected in consideration of processability,
Usually, polyolefin resins such as polyethylene and polypropylene are used. The thickness of the buffer layer E is 10 to 50.
0 μm, more preferably 20 to 200 μm.

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; Low oxygen permeable resins such as alcohol copolymers may be mentioned. 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 the resin can be used substantially as a barrier layer by increasing the thickness. Further, as a material constituting 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 metal or metal oxide,
It may be a composite film using a deposited film of silicon oxide or the like. The barrier layer D is laminated on the buffer layer E after stretching the resin laminate of the stretching substrate, and an adhesive layer can be provided between the buffer layer E and the barrier layer D.

The oxygen-depleted multilayer body of the present invention is suitable for use as a packaging material in a system containing a large amount of 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.

When various films are used for, for example, food packaging containers, there are generally standards to be satisfied for the amount of dissolution. 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 determined for each resin type, and as an example of a higher specified value,
There are 240 ppm of polystyrene and 150 ppm of polyethylene and polypropylene (30 ppm when used in applications exceeding 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 type may be selected in accordance with 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,
Since the measurement is performed only on the side in contact with the object to be deoxidized, the oxygen absorption surface of the deoxidized multilayer body is the measurement site.

The deoxidized multilayer body of the present invention can be used in various forms as a film-shaped or sheet-shaped deoxidized packaging material, for example, for 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, a resin laminate of a stretching base material is produced in advance, and then a plurality of resin layers of the resin laminate are simultaneously 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.

For the production of a resin laminate of a substrate on which a plurality of resin layers are laminated, it is possible to use ordinary methods such as co-extrusion, extrusion coating and extrusion lamination.
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 stretching of the resin laminate of the base material may be performed 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.

The oxygen-absorbing multilayer body of the present invention is of a one-side absorption type, and a barrier layer D is laminated on the other side of the absorption surface of the oxygen-absorbing layer A via a buffer layer E. The barrier layer D is a heat laminate,
Adhesion or fusion is performed by a known method such as dry lamination or extrusion coating to obtain a final multilayer structure.

[0056]

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 Deoxygenation Performance (Measurement of Deoxygenation Time and Total Oxygen Absorption) A sample having a predetermined area (area: 300 cm ² , dimensions: 15 cm × 20 cm) treated with an end face and water for humidification were included. Absorbent cotton and 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) Evaluation of Elution of Deoxygenated Component (Iron Ion) Sample (area: 300 cm) subjected to the end face 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 determined to be 3 ppm from a taste test using an aqueous solution of ferric chloride 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: An oxygen-absorbed sample (dimensions: 2) having an end face treated at the opening (opening area 200 cm ² ) of a test container containing 400 cm ³ of n-heptane (special reagent grade).
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 method is described in the “Standards for Foods, Additives, etc.” (No. 370 of the Ministry of Health and Welfare, No. 370 of 1959).
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, the 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. Next, using a twin-screw extruder, the granular deoxygenated component and a predetermined resin are kneaded at a predetermined mixing ratio, extruded from a strand die, cooled, and then cut with a pelletizer to obtain resin composition pellets. The material for the oxygen layer A was used.

As a poorly water-soluble filler for the oxygen-permeable layer (porous layer) B, synthetic silica (Tatsumori Co., Ltd., trade name;
CRYSTALITE VXS2, average particle size 5 μm)
The synthetic silica and the predetermined resin were kneaded with a screw extruder at a mixing ratio of 50:50 (weight ratio) to obtain a pellet of a resin composition, which was used as a material of the porous layer B. When diatomaceous earth (RADIOLITE F, Showa Chemical Industry Co., Ltd., average particle size 7 μm) is used as the poorly water-soluble filler, diatomaceous earth 4
A mixture having a mixing ratio of 0 wt% and a resin of 60 wt% was used. However, in the following examples, the former was used unless otherwise specified.

(1) Polypropylene (FX4D): Mitsubishi Chemical
Co., Ltd. has a brand name of polypropylene,
Is a copolymer containing a small amount of other α-olefin,
Rate 6.0g / 10min, melting point 140 ℃, 25 ℃
Oxygen permeability coefficient of 1.4 × 10 ^-13[cm^Three・ Cm / cm^Two・
sec Pa]. (2) Linear low-density polyethylene (ULTZEX 2520F): three
Well Petrochemical Industry Co., Ltd.
There is a copolymer containing some other α-olefins.
Body, melt flow rate 2.3g / 10min, melting point 118
C., oxygen transmission coefficient at 25 ° C. 3.0 × 10^-13[cm^Three
・ Cm / cm^Two-Sec-Pa]. (3) 4-methyl-1-pentene copolymer (TPX MX002
 ): Mitsui Petrochemical Industry Co., Ltd., melt flow rate 22
g / 10min (260 ° C), melting point 235 ° C, acid at 25 ° C
Elemental transmission coefficient 2.4 × 10^-12[cm^Three・ Cm / cm^Two・ Sec ・
Pa]. (4) Ethylene-propylene copolymer (TAFMER S-4030
 ): Mitsui Petrochemical Industry Co., Ltd., mol fraction of ethylene component
Is about 0.5, melt flow rate 0.2g / 10min (19
0 ° C), oxygen transmission coefficient alone is unknown, polypropylene
(FX4D) Oxygen permeation of mixture with 50wt% at 25 ℃
Coefficient 3.0 × 10^-13[cm^Three・ Cm / cm^Two-Sec-Pa]. (5) Ethylene-propylene copolymer (TAFMER P-0680
 ): Mitsui Petrochemical Industry Co., Ltd., mol fraction of ethylene component
Is about 0.75, melt flow rate 0.4g / 10min (1
90 ° C.), oxygen permeability coefficient at 25 ° C. 1.4 × 10^-12
[cm^Three・ Cm / cm^Two・ Sec ・ Pa], linear low density polyethylene
At 25 ° C of a mixture with 30 wt% of ren (ULTZEX 2520F)
Permeation coefficient 8.2 × 10^-13[cm^Three・ Cm / cm^Two・
sec Pa]. (6) Hydrogenated styrene-butadiene copolymer and polyp
Mixture with propylene (DYNARON H4800N): Nippon Synthetic Rubber
Co., Ltd., polypropylene fraction 30wt%, melt flow
16 g / 10 min (230 ° C). (7) Ethylene-vinyl acetate copolymer (LV360): Mitsubishi
Chemical Co., Ltd., vinyl acetate fraction 10wt%, melt flow
9.0g / 10min, melting point 95 ° C. (8) Adhesive polyolefin (ADMER NF300): Mitsui Ishi
Oil Chemical Industry Co., Ltd., melt flow rate 1.3g / 10mi
n (190 ° C), melting point 120 ° C. (9) Adhesive polyolefin (ADMER NF550): Mitsuiishi
Oil Chemical Industry Co., Ltd., melt flow rate 6.2g / 10mi
n (190 ° C), melting point 120 ° C. (10) Nylon MXD (MX-NYLON 6007): Mitsubishi Gas
Chemical Co., Ltd., melt flow rate 2.0g / 10min, melting
Point 240 ° C. (11) ethylene-vinyl alcohol copolymer (EVAL E
P-E105): Kuraray Co., Ltd., mole fraction of ethylene component 0.
44, melt flow rate 5.5g / 10min (190 ° C)
 Mp 165 ° C. (12) As an oxygen barrier film, a 15 μm thick
Iron film (SUPERNYL, Mitsubishi Chemical Corporation), or
Nylon and polypropylene laminated film (SUPERNYL
Include a thin adhesive layer between the nylon and polypropylene layers
Using a total thickness of 65 μm, Mitsubishi Chemical Corporation)
Adhesive for dry lamination (Toyo Morton (
AD-585 and CAT-10) were used.

Example 1 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin component for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, a layer of 100 μm for the non-porous layer C / a layer of 150 μm for the porous layer B / a deoxygenation layer A Four layers were laminated by co-extrusion with the structure and the thickness of the layer 150 μm / the buffer layer E 300 μm. This four-layer product was simultaneously biaxially stretched at a temperature of 130 ° C. and three times longer by three times longer. The outline of the thickness of each layer after stretching is as follows: nonporous layer C 10 μm / porous layer B 55 μm /
Deoxygenation layer A was 60 μm / buffer layer E was 35 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to corona discharge treatment with a discharge energy of 3.6 kJ / m ² (60 W / m ² / min in a conventional unit), and then the nylon film is subjected to dry laminating adhesive. (Thickness after drying is about 10 μm), and a deoxygenation film having a six-layer structure of nonporous layer C / porous layer B / deoxygenation layer A / buffer layer E / adhesion layer F / barrier layer D did. Deoxygenation time is 2.0 days, iron elution is 0.06 pp after 20 days
m, the elution amount of n-heptane from the non-porous layer C side is 1 cm
0.08 mg per ² .

Example 2 A mixture of 70% by weight of an ethylene-propylene copolymer (TAFMER P-0680) and 30% by weight of a linear low-density polyethylene (ULTZEX 2520F) as a resin component for the non-porous layer C, a porous layer B and the oxygen-absorbing layer A, using a linear low-density polyethylene (same as above) as the resin component and the buffer layer E using a linear low-density polyethylene (same as the resin component).
40 μm per layer / 100 μm per layer of the porous layer B / 100 μm per layer of the deoxidizing layer A / layer 200 pertaining to the buffer layer E
Four layers were laminated by co-extrusion with a thickness of μm and each thickness. This four-layer product was uniaxially stretched at a temperature of 100 ° C. and a length of 4 times. The outline of the thickness of each layer after stretching is as follows: Non-porous layer C 10 μm
/ Porous layer B 40 μm / deoxygenation layer A 40 μm / buffer layer E
It was 50 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). Non-porous layer C / porous layer B / deoxygenation layer A / buffer layer E / adhesive layer F / barrier layer D
Was obtained. The deoxidation time was 1.
7 days, iron elution was 0.09 ppm after 20 days, non-porous layer C
Elution amount from the side to the n- heptane 1 cm ² per 0.0
2 mg.

Example 3 As a resin component for the non-porous layer C and the buffer layer E, 4-methyl-1-pentene copolymer (TPX MX002), porous layer B
And 4-methyl-1- as a resin component for the deoxidation layer A
Using a pentene copolymer (same as above), a layer 40 μm for the non-porous layer C / a layer 100 μm for the porous layer B / a deoxygenation layer A
And a layer having a thickness of 200 μm per 100 μm per buffer layer E, and four layers were laminated by co-extrusion. The four-layered product was uniaxially stretched at a temperature of 130 ° C. and a length of 4 times. The outline of the thickness of each layer after stretching is as follows.
m / the layer relating to the porous layer B / 40 μm / the layer relating to the oxygen scavenging layer A / 80 μm / the layer relating to the buffer layer E = 25 μm. This 4
The surface of the buffer layer E of the layer-stretched product is subjected to a corona discharge treatment with a discharge energy of 1.8 kJ / m ² , and then a nylon film is adhered with an adhesive for dry lamination (about 10 μm in thickness after drying). Porous layer C / porous layer B / porous deoxygenated layer A
/ A buffer layer E / adhesive layer F / barrier layer D. Deoxygenation time 0.7 days, iron elution 2
After 0 day, the concentration was 0.12 ppm, and the amount of elution from the nonporous layer C side into n-heptane was 0.30 mg / cm ² .

Example 4 A mixture of a hydrogenated styrene-butadiene copolymer and polypropylene (DYNARO
NH4800N), polypropylene (FX4D) as a resin component for the porous layer B and the deoxygenation layer A, and polypropylene (same as above) as a resin component for the buffer layer E, and a layer for the nonporous layer C of 100 μm / porous. Layer 150 μm according to the porous layer B / 150 μm layer according to the deoxidizing layer A / layer 300 according to the buffer layer E
Four layers were laminated by co-extrusion with a thickness of μm and each thickness. This four-layer product is heated at 130 ° C, 3x3 x 3x2
Axial simultaneous stretching was performed. The outline of the thickness of each layer after stretching is as follows: non-porous layer C 10 μm / porous layer B 55 μm / deoxygenation layer A 60 μm
m / buffer layer E was 35 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). Non-porous layer C / porous layer B / deoxygenation layer A / buffer layer E / adhesive layer F
/ Oxygen barrier film having a six-layer structure of barrier layer D. Deoxygenation time is 1.3 days, iron elution is 0.08 ppm after 20 days
The elution amount of n-heptane from the non-porous layer C side was 1 cm.
0.60 mg per ² .

Example 5 A mixture of 70% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 30% by weight of polypropylene (FX4D) as the resin component for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, a layer of 100 μm for the non-porous layer C / a layer of 150 μm for the porous layer B / a deoxygenation layer A Four layers were laminated by co-extrusion with the structure and the thickness of the layer 150 μm / the buffer layer E 300 μm. The four-layer product was uniaxially stretched at a temperature of 130 ° C. and a length of 6 times. The outline of the thickness of each layer after stretching is as follows: non-porous layer C 17 μm / porous layer B 70 μm / deoxygenation layer A8
0 μm / buffer layer E was 50 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). ,
The oxygen-absorbing film had a six-layer structure of a nonporous layer C / porous layer B / oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D.
Deoxygenation time is 2.1 days, iron elution is 0.09 after 20 days.
ppm, elution amount of n-heptane from the non-porous layer C side is 1
0.45 mg per cm ² .

Example 6 A mixture of 70% by weight of ethylene-propylene copolymer (TAFMER S-4030) and 30% by weight of polypropylene (FX4D) as a resin component for the non-porous layer C, a porous layer B and a deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, a layer of 100 μm for the non-porous layer C / a layer of 150 μm for the porous layer B / a deoxygenation layer A Four layers were laminated by co-extrusion with the structure and the thickness of the layer 150 μm / the buffer layer E 300 μm. The four-layered product was simultaneously biaxially stretched at a temperature of 130 ° C. and 4 × 4 × 4. The thickness of each layer after stretching was as follows: non-porous layer C 7 μm / porous layer B 30 μm / deoxygenation layer A 35 μm / buffer layer E 20 μm. This 4
The surface of the buffer layer E of the layer-stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is adhered with an adhesive for dry lamination (about 10 μm in thickness after drying). An oxygen-absorbing film having a six-layer structure of porous layer C / porous layer B / oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D was used. The deoxygenation time was 1.3 days, the elution of iron was 0.08 ppm after 20 days, and the elution amount of n-heptane from the nonporous layer C side was 0.24 mg / cm ² .

Example 7 Ethylene-vinyl acetate copolymer (LV360) was used as the resin component for the nonporous layer C, and linear low-density polyethylene (ULTZEX 252) was used as the resin component for the porous layer B and the oxygen-absorbing layer A.
0F), a linear low-density polyethylene (same as above) was used as the resin component for the buffer layer E, and E40 μm for the nonporous layer C.
Four layers were laminated by co-extrusion, with the respective configurations and thicknesses: 100 μm for the porous layer B / 100 μm for the oxygen-absorbing layer A / 200 μm for the buffer layer E. The four-layered product was uniaxially stretched at a temperature of 80 ° C. and a length of 4 times. The outline of the thickness of each layer after stretching is as follows: non-porous layer C 10 μm / porous layer B 40 μm
m / deoxygenation layer A 40 μm / buffer layer E 50 μm.
The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then the nylon film is dried with an adhesive for dry lamination (about 10 μm in thickness after drying).
m), and the non-porous layer C / porous layer B / deoxygenation layer A
/ A buffer layer E / adhesive layer F / barrier layer D. Deoxidation time is 1.4 days, iron elution is 2
It was 0.07 ppm after 0 days, and the amount of elution from the nonporous layer C side into n-heptane was 0.01 mg / cm ² .

Example 8 A mixture of 70% by weight of ethylene-propylene copolymer (TAFMER S-4030) and 30% by weight of polypropylene (FX4D) as a resin component for the non-porous layer C, diatomaceous earth as a poorly water-soluble filler, and porous Using polypropylene (same as above) as the resin component for the layer B and the oxygen-absorbing layer A and polypropylene (same as the same) as the resin component for the buffer layer E, the layer of the nonporous layer C 100 μm / the layer of the porous layer B 150 μm / layer relating to the deoxygenation layer A 150 μm / layer relating to the buffer layer E 300 μm,
With the above structure and each thickness, four layers were laminated by co-extrusion.
This four-layer product was simultaneously biaxially stretched at a temperature of 130 ° C. and three times longer by three times longer. The outline of the thickness of each layer after stretching is as follows.
0 μm / porous layer B 55 μm / deoxygenation layer A 60 μm / buffer layer E 35 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). , Non-porous layer C
/ Porous layer B / porous deoxygenated layer A / buffer layer E / adhesive layer F
/ Oxygen barrier film having a six-layer structure of barrier layer D. Deoxygenation time is 1.2 days, iron elution is 0.08 ppm after 20 days
And the amount of elution from the non-porous layer CC side to n-heptane is 1 c
0.34 mg per m ² .

Example 9 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin components for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, a layer of 100 μm for the non-porous layer C / a layer of 150 μm for the porous layer B / a deoxygenation layer A Four layers were laminated by co-extrusion with the structure and the thickness of the layer 150 μm / the buffer layer E 800 μm. This four-layer product was simultaneously biaxially stretched at a temperature of 130 ° C. and three times longer by three times longer. The outline of the thickness of each layer after stretching is as follows: nonporous layer C 10 μm / porous layer B 55 μm /
Deoxygenation layer A was 60 μm / buffer layer E was 90 μm. On the buffer layer E side of the four-layer stretched product, a laminated film of nylon and polypropylene (the polypropylene side is in contact with the buffer layer E) is laminated by heat fusion to form a nonporous layer C / porous layer B
/ Deoxygenation layer A / Buffer layer E / Fused layer (polypropylene) /
A six-layer oxygen-absorbing film composed of a barrier layer D (nylon) was obtained. However, the heating in the heat fusion was performed only from the nylon layer side, and the temperature and the heating time were set to minimize the non-porosity of the deoxidized layer A and the porous layer B due to heat. The deoxygenation time was 2.3 days, the elution of iron was 0.06 ppm after 20 days, and the elution amount of n-heptane from the nonporous layer C side was 0.08 mg per 1 cm ² .

Example 10 Linear low-density polyethylene (ULTZEX 2520F) as the resin component for the nonporous layer C and the buffer layer E, and linear low-density polyethylene for the porous layer B and the deoxygenation layer A Using polyethylene (same as above), layer 40 μm for non-porous layer C / layer 100 μm for porous layer B / layer 100 for oxygen-absorbing layer A
Four layers were laminated by co-extrusion at a thickness of 800 μm and a thickness of μm / buffer layer E. The four-layer product was uniaxially stretched at a temperature of 100 ° C. and a length of 4 times. The outline of the thickness of each layer after stretching is as follows: non-porous layer C 10 μm / porous layer B 40 μm
/ Deoxygenation layer A 40 μm / buffer layer E 200 μmm.
A layer of adhesive polyolefin (ADMER NF550) having a thickness of 15 μm and a thickness of 20 μm were provided on the buffer layer E side of the four-layer stretched product.
Ethylene-vinyl alcohol copolymer (EVAL EP-E10
The layers of 5) are simultaneously laminated by co-extrusion lamination to form a nonporous layer CC / porous layer B / deoxygenation layer A / buffer layer E / adhesive resin layer (ADMER) / barrier layer D (EVAL). 6 of
A deoxidized film having a layer structure was obtained. However, the co-extrusion lamination was performed at a molten resin temperature and a laminating speed that minimized nonporous formation of the deoxidized layer A and the porous layer B due to heat. The deoxygenation time was 2.8 days, the elution of iron was 0.07 ppm after 20 days, and the amount of elution from the nonporous layer C into n-heptane was less than 0.01 mg / cm ² .

Example 11 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as a resin component for the nonporous layer C, a porous layer B and a deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, the layer 150 μm according to the porous layer B / the layer 100 μm according to the non-porous layer C / the deoxygenation layer A Four layers were laminated by co-extrusion with the structure and the thickness of the layer 150 μm / the buffer layer E 300 μm. This four-layer product was simultaneously biaxially stretched at a temperature of 130 ° C. and three times longer by three times longer. The outline of the thickness of each layer after stretching is as follows: porous layer B 55 μm / porous layer C 10 μm /
Deoxygenation layer A was 60 μm / buffer layer E was 35 μm. The surface of the buffer layer E of the four-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then the nylon film is subjected to dry laminating adhesive (thickness after drying is about 10 μm).
To form an oxygen-absorbing film having a six-layer structure of porous layer B / non-porous layer C / oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D. The deoxygenation time was 2.1 days, the elution of iron was 0.15 ppm after 20 days, and the elution amount of n-heptane on the porous layer B side was 0.10 mg / cm ² .

COMPARATIVE EXAMPLE 1 Polypropylene (FX4D) was used as the resin component for the porous layer B and the deoxygenation layer A, and polypropylene (same as above) was used as the resin component for the buffer layer E.
.mu.m / 150 .mu.m of the layer relating to the deoxidizing layer A / 300 .mu.m of the layer relating to the buffer layer E.
The layers were stacked. The three-layered product was simultaneously biaxially stretched at a temperature of 130 ° C. at a length of 3 × 3. The approximate thickness of each layer after stretching was: porous layer B 55 μm / deoxygenation layer A 60 μm / buffer layer E 35 μm. The surface of the buffer layer E of the three-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). , Porous layer B /
An oxygen-absorbing film having a five-layer structure of porous oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D was used. Deoxidation time is 0.6
After 2 days, the elution of iron is 2 ppm (20% if immersed in ethanol for several tens of seconds before immersion in aqueous hydrochloric acid.
The amount eluted from the barrier layer D side into n-heptane was less than 0.01 mg / cm ² .

Comparative Example 2 A mixture of 50% by weight of ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin component for the non-porous layer C, Using polypropylene (same as above) and polypropylene (same as above) as a resin component for the buffer layer E, a structure of 100 μm for the nonporous layer C / 150 μm for the oxygen-absorbing layer A / 300 μm for the buffer layer E And three layers were laminated by coextrusion at each thickness. The three-layer product is heated to a temperature of 130.
The film was biaxially stretched at a temperature of 3 times the length and 3 times the width. The outline of the thickness of each layer after stretching is as follows: nonporous layer C10 μm / deoxygenation layer A60
μm / buffer layer E was 35 μm. The surface of the buffer layer E of the three-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). The oxygen-absorbing film had a five-layer structure of nonporous layer C / oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D. The deoxygenation time was 1.9 days, the elution of iron was 1.1 ppm after 20 days, and the elution amount of n-heptane from the nonporous layer C side was 0.1 ppm / cm ² .
09 mg. When observed with an optical microscope, a slight amount of iron powder penetrating the nonporous layer C was confirmed.

Comparative Example 3 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin components for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as the resin component according to (1) and polypropylene (same as above) as the resin component according to the buffer layer E, a layer 25 μm for the non-porous layer C / a layer 20 μm for the porous layer B / a deoxygenation layer A Four layers were laminated by co-extrusion with the configuration and the thickness of the layer 150 μm / the buffer layer E 200 μm. The surface of the unstretched four-layer buffer layer E is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then the nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). And the non-porous layer C /
An oxygen-absorbing film having a six-layer structure of porous layer B / oxygen-absorbing layer A / buffer layer E / adhesive layer F / barrier layer D was used. The deoxygenation time was 40 days, the elution of iron was 0.03 ppm after 20 days, and the amount of elution from the nonporous layer C side to n-heptane was 0.1 per cm ² .
It was 12 mg.

COMPARATIVE EXAMPLE 4 Polypropylene (FX4D) was used as the resin component for the porous layer B and the deoxidizing layer A, and polypropylene (same as above) was used as the resin component for the buffer layer E.
Three layers were laminated by co-extrusion, each having a structure of m / 150 μm of the layer for deoxidizing layer A / 300 μm of the layer for the buffer layer E. This three-layer product is heated at 130 ° C, 3 times vertically and 3 times horizontally.
The film was biaxially stretched at the same time. The outline of the thickness of each layer after stretching is
Porous layer B 55 μm / deoxygenation layer A 60 μm / buffer layer E3
It was 5 μm. The surface of the buffer layer E of the three-layer stretched product is subjected to a corona discharge treatment with a discharge energy of 3.6 kJ / m ² , and then a nylon film is bonded with an adhesive for dry lamination (about 10 μm in thickness after drying). , A porous layer B / porous deoxygenated layer A / buffer layer E / adhesive layer F / barrier layer D. Further, on the porous layer B side of the five-layer product, 50 wt% of ethylene-propylene copolymer (TAFMER S-4030) was added.
% And polypropylene (FX4D) 50 wt%, an attempt was made to add a 10 μm thick non-porous layer by extrusion coating. Possibly due to lack of heat of the molten resin and slight unevenness of the porous layer B part,
At μm, fusion was not possible and lamination was impossible.

Comparative Example 5 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin component for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as a resin component according to the present invention, the thickness and the thickness of the layer of the non-porous layer C 100 μm / the porous layer B 150 μm / the oxygen absorbing layer A 150 μm Three layers were laminated by extrusion. This 3
The layered product was simultaneously biaxially stretched at a temperature of 130 ° C. and 3 times length × 3 times width. The outline of the thickness of each layer after stretching is as follows: Non-porous layer C 10 μm
/ Porous layer B 55 μm / porous deoxygenation layer A 60 μm. On the oxygen-absorbing layer A side of the three-layer stretched product, a nylon film is coated with an adhesive for dry lamination (with a thickness of about 50 after drying).
μm) to form an oxygen-absorbing film having a five-layer structure of nonporous layer C / porous layer B / oxygen-absorbing layer A / adhesive layer F / barrier layer D (the lamination strength of the barrier layer is sufficiently high. T). The deoxygenation time was 10 days. It is considered that a part or all of the pores of the porous oxygen-absorbing layer A and the porous layer B were filled with the adhesive. The elution of iron was 0.06 ppm after 20 days, and the elution amount of n-heptane from the nonporous layer C side was 0.08 mg / cm ² .

Comparative Example 6 Ethylene-propylene was used as the resin component for the nonporous layer C.
50% by weight of copolymer (TAFMER S-4030) and polypropylene
(FX4D) Mixture with 50wt%, porous layer B and deoxygenation layer
Using polypropylene (same as above) as the resin component for A
And the layer of the nonporous layer C 100 μm / the layer of the porous layer B
Configuration of layer 150 μm / layer 150 μm related to deoxidation layer A
And three layers were laminated by coextrusion at each thickness. This 3
The layered product is biaxially stretched at 130 ° C, 3x3x3x
Was. The outline of the thickness of each layer after stretching is as follows: Non-porous layer C 10 μm
/ Porous layer B 55 μm / deoxygenation layer A 60 μm.
On the oxygen-absorbing layer A side of this three-layer stretched product, nylon and polypropylene
Pyrene laminated film (Polypropylene side for oxygen scavenging layer A)
Are in contact with each other) by heat sealing to form a non-porous layer C / porous
Layer B / deoxygenation layer A / fusion layer (polypropylene) / burr
Oxygen layer D (nylon)
Was. However, heating in heat fusion is performed from the nylon layer side.
Only to make the deoxygenation layer A and the porous layer B nonporous by heat.
And the heating time were minimized. Deoxygenation time
It was 15 days. Of pores between the deoxidizing layer A and the porous layer B,
Some or all are considered to be nonporous due to heat
You. Elution of iron was 0.06 ppm after 20 days, non-porous layer C side
Elution amount into n-heptane from ^Two0.08 per
mg.

Comparative Example 7 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin components for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as a resin component according to the present invention, the thickness and the thickness of the layer of the non-porous layer C 100 μm / the porous layer B 150 μm / the oxygen absorbing layer A 150 μm Three layers were laminated by extrusion. This 3
The layered product was simultaneously biaxially stretched at a temperature of 130 ° C. and 3 times length × 3 times width. The outline of the thickness of each layer after stretching is as follows: Non-porous layer C 10 μm
/ Porous layer B 55 μm / deoxygenation layer A 60 μm.
A 15 μm-thick adhesive polyolefin (ADMER NF550) layer and a 20 μm-thick ethylene-vinyl alcohol copolymer (EVAL EP-E105)
Are simultaneously laminated by co-extrusion lamination to form a five-layer structure comprising a nonporous layer C / porous layer B / deoxygenation layer A / adhesive resin layer (ADMER) / barrier layer D (EVAL). An oxygen film was used. However, the co-extrusion lamination was performed at a molten resin temperature and a laminating speed that minimized nonporous formation of the deoxidized layer A and the porous layer B due to heat. The deoxidation time was 12 days. It is considered that some or all of the pores in the deoxidized layer A and the porous layer B were made nonporous by heat. Elution of iron is 0.07 ppm after 20 days, non-porous layer C
Elution amount from the side to the n- heptane 1 cm ² per 0.0
It was less than 1 mg.

Comparative Example 8 A mixture of 50% by weight of an ethylene-propylene copolymer (TAFMER S-4030) and 50% by weight of polypropylene (FX4D) as the resin components for the non-porous layer C, the porous layer B and the deoxidized layer A Using polypropylene (same as above) as a resin component according to the present invention, the thickness and the thickness of the layer of the non-porous layer C 100 μm / the porous layer B 150 μm / the oxygen absorbing layer A 150 μm Three layers were laminated by extrusion. This 3
The layered product was simultaneously biaxially stretched at a temperature of 130 ° C. and 3 times length × 3 times width. The outline of the thickness of each layer after stretching is as follows: Non-porous layer C 10 μm
/ Porous layer B 55 μm / porous deoxygenation layer A 60 μm. A nylon film is adhered to the porous deoxygenated layer A side of the three-layer stretched product with a dry laminating adhesive (about 10 μm in thickness after drying) to form a nonporous layer C / porous layer B / deoxygenated layer. An attempt was made to provide a deoxidized film having a five-layer structure of layer A / adhesive layer / barrier layer D. When the surface on which the adhesive is applied is on the oxygen-absorbing layer A side, the adhesive is significantly absorbed by the oxygen-absorbing layer A, and when the surface on which the adhesive is applied is on the nylon film side, the adhesive layer and the oxygen-absorbing layer A Shortage of contact area of
In each case, the barrier layer D was easily peeled off. Therefore, it was found that the provision of the above-described buffer layer E was suitable for improving the adhesion between the deoxidizing layer A and the barrier layer D.

[0084]

EFFECT OF THE INVENTION The film- or sheet-shaped deoxidized multilayer body of the present invention has a novel deoxygenation property which has an excellent deoxidation rate, has a property of preventing the elution and contamination of deoxidized components, and is excellent as a packaging material. 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 the drawings]

FIG. 1 is a cross-sectional view of a layer configuration example of a one-sided absorption type deoxidized multilayer body of the present invention.

FIG. 2 is a cross-sectional view of a packaging container using the film-shaped single-sided absorption type deoxidized multilayer body of the present invention as a top seal film.

FIG. 3 is a cross-sectional view of a packaging bag using the film-shaped single-sided absorption-type deoxidized multilayer body of the present invention on one side.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Non-porous oxygen-permeable layer C 2 Porous oxygen-permeable layer B 3 Porous deoxygenation layer A 4 Barrier layer D 5 Buffer layer E 6 Adhesion layer F (adhesive, resin for adhesion, etc.) 10 One side Absorption type film-shaped deoxidizing multilayer body 30 Contents (solid, liquid, solid and liquid, etc.) 40 Container body with barrier property 50 General barrier film or barrier bag without deoxidizing function

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Chiharu Nishizawa 6-1-1-1 Shinjuku, Katsushika-ku, Tokyo Tokyo Metropolitan Research Institute of Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Noriyuki Kimura 6-1-1 Shinjuku, Katsushika-ku, Tokyo No.1 Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory

Claims (8)

[Claims] 1. An oxygen-permeable layer is provided on one side of a deoxygenation layer,
In a film-shaped or sheet-shaped oxygen-absorbing multilayer body provided with a barrier layer on the other surface, at least one non-porous surface of the oxygen-absorbing layer A in which a resin composition in which an oxygen-absorbing component is dispersed is continuously made microporous. Oxygen permeable layer C made of thin film thermoplastic resin
And an oxygen-permeable layer B in which a resin composition in which granular poorly water-soluble fillers are dispersed is continuously made microporous, and a buffer layer E made of a thermoplastic resin is provided on the other surface of the layer A. A barrier layer D is laminated on the surface of the buffer layer E of a laminate obtained by heat-sealing each of the adjacent layers, the single-sided absorption-type deoxidized multilayer body. 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. The deoxidized oxygen absorber according to claim 1, wherein an oxygen permeable layer C and an oxygen permeable layer B are laminated on one surface of the deoxygenated layer A in this order from the deoxygenated layer A. 6. The deoxidized oxygen absorber according to claim 1, wherein an oxygen-permeable layer B and an oxygen-permeable layer C are laminated on the entire surface of the oxygen-absorbing layer A in this order. 7. A layer c of a thermoplastic resin having oxygen permeability on one surface of a layer a of a resin composition in which a deoxygenating component is dispersed, and a layer b of a resin composition in which a particulate poorly water-soluble filler is dispersed. Are laminated in combination with one or more layers, and a layer e of a thermoplastic resin is laminated on the other surface of the layer a, and the base material of the resin laminate obtained by heat-sealing the adjacent layers to each other is stretched; Next, a barrier layer D is laminated on the layer e surface of the stretched base material, and a non-porous layer obtained by thinning at least the layer c on one surface of the oxygen-absorbing layer A in which the layer a is continuously microporous. A barrier formed by laminating a buffer layer E in which a layer e is stretched on the other surface of the layer A, comprising an oxygen permeable layer C and an oxygen permeable layer B in which the layer b is made continuous and microporous. Method for producing single-sided absorption deoxidized multilayer body for producing film-shaped or sheet-shaped deoxidized multilayer body provided with layer D Law. 8. The method according to claim 8, wherein the base material of the resin laminate is uniaxially or
The production method according to claim 9, wherein the film is stretched 2 to 20 times in an axial direction in terms of area.