WO2008001732A1 - Dehumidification/deoxidization method, and deoxidizing package, film having deoxidizing function and deoxidizing resin composition each having dehumidifying function - Google Patents

Abstract

A tablet (10) to be stored is enclosed in a gas-barrier film (11) together with a deoxidizing agent (12) having a dehumidifying function, wherein the deoxidizing agent (12) comprises an inorganic oxide component comprising at least one of cerium oxide, zinc oxide and titanium oxide each having an oxygen defect or a mixture thereof. This enables to absorb and remove oxygen in the atmosphere and also absorb moisture in the atmosphere. The function of absorbing oxygen and moisture can be enhanced by allowing calcium (Ca) or the like to be present in the inorganic oxide component in the form of a solid solution.

Description

 Specification

 Dehumidification, deoxygenation method, deoxygenation package with dehumidification function and deoxygenation functional film or deoxygenation resin composition

 Technical field

 [0001] The present invention relates to a dehumidification method that combines the function of absorbing and removing oxygen in the atmosphere and the function of absorbing and removing moisture. The present invention relates to an oxygen resin composition.

 Background art

 [0002] In recent years, in response to strong demands for food safety and quality maintenance, the oxidative deterioration of food has been suppressed by making the inside of the food packaging body containing the food oxygen-free. ing.

 Specifically, an oxygen scavenger that absorbs and removes oxygen in the atmosphere is placed inside the food packaging body together with the food, and residual oxygen inside the food packaging body is removed to remove the inside of the food packaging body. Anoxic conditions have been achieved. In addition, in an inert gas not containing oxygen, the food is packaged in a food packaging body together with the oxygen scavenger so that oxygen does not enter the food packaging body, and the food A small amount of oxygen that permeates through the package and enters the inside is removed by an oxygen scavenger included.

As described above, oxygen scavengers that remove oxygen in the atmosphere include organic materials and inorganic materials. From the viewpoint of cost, iron, which is an inorganic material, is used. System Oxygen absorbers are mainly used. As shown in the following formula (1), this iron-based oxygen scavenger removes oxygen from the atmosphere by reacting oxygen in the atmosphere with iron together with moisture in the atmosphere. Le, ru (Patent Document 1).

[0004] Fe + 1 / 2H 0 + 3/40 → FeOOH · · · · (1)

 twenty two

 Patent Document 1: Japanese Patent Application Laid-Open No. 11 226388

 Disclosure of the invention

 Problems to be solved by the invention

However, when the conventional iron-based oxygen scavenger as described above is used, There is such a problem.

 [0007] (1) As shown in the above formula (1), the iron-based oxygen scavenger requires water in the deoxygenation reaction. In such an oxygen scavenger, moisture is emitted from the moisture retaining agent, so that the humidity in the sealed bag increases. As a result, for example, as shown in FIG. 22, in order to maintain the dry state of a storage bag, for example, a tablet 2, etc., which is an object to be stored in, for example, a gas barrier film 1, a dehumidifier 3 such as silica gel is enclosed. There is.

 In such a case, in the process of encapsulating the tablet 2 in the gas nore film 1, means for introducing the oxygen scavenger 4 and means for introducing the dehumidifying agent 3 are required. There is a problem.

 On the other hand, if the moisture in the gas barrier film 1 is removed using the dehumidifying agent 3, there is a problem that the water content contributing to the oxidation reaction is lowered and the deoxygenation function is lowered.

[0008] (2) In the case of tablets such as pharmaceuticals and supplements that are extremely reluctant to water, since it is not possible to enclose a water retention agent, it is not possible to promote by moisture as in the above formula (1), There is a problem that the deoxidation function cannot be exhibited well, and as a result, a larger amount of iron powder is required than usual.

 Therefore, in addition to the above-mentioned pharmaceuticals and supplements, the performance of conventional oxygen scavengers cannot be fully exhibited when storing items that are extremely hated of moisture, such as dried foods, electronic parts and solder powder. There is a problem.

 [0009] (3) In addition, when performing an inspection to determine whether or not foreign substances such as metals are mixed in a food packaged with a conventional oxygen scavenger along with an inert gas in the package, an iron-based oxygen absorber There is a problem that a metal detector reacts with the agent and a simple examination cannot be performed.

[0010] (4) There is a problem that it is rapidly heated by a microwave such as a microwave oven and ignites.

In view of such a situation, the emergence of a novel oxygen scavenger that has both a oxygen scavenging function and a dehumidifying function that can sufficiently exhibit the oxygen scavenging function as the oxygen scavenger and can also exhibit the water removing function. Is desired.

In view of the above problems, an object of the present invention is to provide a dehumidification / deoxygenation method, a deoxygenation package having a dehumidification function, a deoxygenation functional film, or a deoxygenation resin composition. Means for solving the problem

 [0013] A first invention of the present invention for solving the above-mentioned problem is the use of an inorganic oxide of any one of cerium oxide, zinc oxide and titanium oxide having oxygen defects, or a mixture thereof. The dehumidification / deoxygenation method is characterized by absorbing and removing oxygen in the atmosphere and absorbing moisture in the atmosphere.

 [0014] A second invention is the same as that of the first invention, in which magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr) or yttrium (Y) The dehumidification / deoxygenation method is characterized in that any one of the above or a mixture thereof is dissolved in the inorganic oxide.

 [0015] A third invention is the dehumidification / deoxygenation method according to the second invention, wherein the total addition amount of the solid solution elements is:! To 20 mol%.

 [0016] The fourth invention comprises an inorganic oxide of any one of cerium oxide, zinc oxide, and titanium oxide having oxygen defects, or a mixture thereof, and absorbs and removes oxygen in the atmosphere, and moisture in the atmosphere. A deoxygenating package comprising a deoxygenating agent having a dehumidifying function that absorbs oxygen and a packaging body containing the deoxidizing agent, wherein the packaging body has oxygen permeability and moisture permeability. A deoxygenated package having a dehumidifying function characterized by having a property.

 [0017] According to a fifth invention, in the fourth invention, magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr) or yttrium (Y) The present invention provides a deoxygenated packaging body having a dehumidifying function characterized in that any one or a mixture of these is dissolved in the inorganic oxide.

 [0018] A sixth invention is the deoxygenated packaging body with a dehumidifying function according to the fifth invention, wherein the total addition amount of the solid solution elements is:! To 20 mol%.

[0019] The seventh invention comprises an inorganic oxide of any one of cerium oxide, zinc oxide and titanium oxide having oxygen defects, or a mixture thereof, and absorbs and removes oxygen in the atmosphere, and also moisture in the atmosphere. Deoxygenation consisting of a deoxidizer with a dehumidifying function that absorbs moisture. [0020] In an eighth aspect based on the seventh aspect, the eighth aspect of the present invention provides a gas barrier layer having gas-releasability provided on one surface of the deoxygenation / moisture absorption layer and the other of the deoxygenation / water absorption layer. A deoxygenating functional film having a dehumidifying function, comprising an oxygen and moisture easily permeable layer provided on a surface and having oxygen and moisture easily permeable layers.

 [0021] A ninth invention is a deoxygenation functional film having a dehumidifying function, characterized in that, in the seventh or eighth invention, an advanced gas barrier layer is provided between the gas barrier layer and the outer layer.

 [0022] A tenth invention is the dehumidifying function according to any one of the seventh to ninth inventions, wherein a buffer layer is provided between the deoxygenated moisture absorbing layer and the gas barrier layer. Deoxygenated functional film with

 [0023] According to an eleventh aspect, in any one of the seventh to tenth aspects, magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr) Or a deoxygenating functional film having a dehumidifying function, wherein any one of yttrium (Y) or a mixture thereof is dissolved in the inorganic oxide.

 [0024] A twelfth invention is the deoxygenation functional film having a dehumidifying function according to the eleventh invention, wherein the total amount of the solid solution element added is 1 to 20 mol%.

 [0025] The thirteenth invention comprises an inorganic oxide of any one of cerium oxide, suboxide 1 ^ or titanium oxide having oxygen defects, or a mixture thereof, and absorbs and removes oxygen in the atmosphere. Provided with a dehumidifying function characterized by dispersing or kneading a deoxygenating agent having a dehumidifying function by absorbing moisture in the atmosphere into a resin having oxygen and moisture easily permeability. It is in a deoxygenated resin composition.

 [0026] In a fourteenth aspect based on the thirteenth aspect, magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr) or yttrium (Y) A deoxygenated resin composition having a dehumidifying function characterized in that any one of these or a mixture thereof is dissolved in the inorganic oxide.

 [0027] A fifteenth aspect of the present invention is the deoxygenated resin composition having a dehumidifying function according to the fourteenth aspect of the present invention, wherein the total amount of the solid solution element added is 1 to 20 mol%.

 The invention's effect

[0028] According to the present invention, a single oxygen scavenger exhibits an oxygen absorbing function and a moisture removing function. Therefore, a conventional dehumidifying agent such as silica gel for removing water can be eliminated.

Brief Description of Drawings

[FIG. 1] FIG. 1 is a graph showing the relationship between the amount of additive element added and the lattice constant.

 [FIG. 2] FIG. 2 is a graph showing the relationship between the amount of additive element (Ca) added and the lattice constant.

 [FIG. 3] FIG. 3 is a graph showing the relationship between the amount of additive element (Sr) added and the lattice constant.

 [FIG. 4] FIG. 4 is a diagram showing the relationship between the amount of additive element (Mg) added and the lattice constant.

 FIG. 5 is a graph showing the relationship between the additive amount of additive element (La) and the lattice constant.

 [FIG. 6] FIG. 6 is a graph showing the relationship between the amount of additive element (Pr) added and the lattice constant.

 [FIG. 7] FIG. 7 is a graph showing the relationship between the amount of additive element (Y) added and the lattice constant.

 [FIG. 8] FIG. 8 is a graph showing the relationship between the elapsed time of oxygen absorption and the amount of absorbed oxygen in the case of additive element (Ca).

 [FIG. 9] FIG. 9 is a graph showing the relationship between the added amount and the oxygen absorption amount after 96 hours in FIG.

FIG. 10 is a graph showing the relationship between the oxygen absorption elapsed time and the oxygen absorption amount in the case of the additive element (Pr).

 [FIG. 11] FIG. 11 is a graph showing the relationship between the amount of additive and the amount of oxygen absorbed after 96 hours in FIG.

 [FIG. 12] FIG. 12 is a graph showing the relationship between the oxygen absorption elapsed time and the oxygen absorption amount in the case of the additive element (Y).

 [FIG. 13] FIG. 13 is a graph showing the relationship between the amount of additive and the amount of oxygen absorbed after 96 hours in FIG.

 FIG. 14 is a schematic view of a package in which a tablet and an oxygen scavenger having a dehumidifying function are sealed in a gas barrier film that is effective in the present embodiment.

 FIG. 15 is a schematic diagram of a deoxygenating functional film having a dehumidifying function.

 FIG. 16 is a schematic diagram of another deoxygenating functional film having a dehumidifying function.

 [FIG. 17] FIG. 17 is a schematic view of a deoxygenation functional package having a dehumidifying function.

 FIG. 18 is a schematic view of a deoxygenating functional resin composition having a dehumidifying function.

FIG. 19 is a graph showing the relationship between elapsed time and humidity change according to the example. FIG. 20 is a graph showing the relationship between the elapsed time and the relative humidity related to the dehumidifying performance of the oxygen scavenger having a dehumidifying function.

 FIG. 21 is a relationship diagram between the elapsed time and the relative humidity related to the initial humidity dependence of the dehumidifying performance of the oxygen scavenger having a dehumidifying function.

 [FIG. 22] FIG. 22 is a schematic view of a package in which a tablet and an oxygen scavenger having a dehumidifying function are sealed in a gas barrier film which is stronger than the conventional example.

 Explanation of symbols

[0030] 10 tablets

 11 Gas barrier film

 12 Oxygen absorber with dehumidifying function

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to the drawings. It should be noted that the present invention is not limited to the embodiments and examples. In addition, constituent elements in the following embodiments and examples include those that can be easily assumed by those skilled in the art or those that are substantially the same.

 [0032] The oxygen scavenger according to the present embodiment absorbs and removes oxygen in the atmosphere and removes water, and its constituent material is one of cerium oxide, titanium oxide, zinc oxide, and the like. Or a mixture thereof.

 Among these, it is preferable to use cerium oxide as the inorganic oxide, which has a particularly large oxygen absorption capability.

[0033] Here, in the following description of the present embodiment, the case where cerium oxide is used as the inorganic oxide will be described below.

 The high-temperature reduction-treated cerium oxide (CeO: where X is a positive number less than 2) having oxygen defects becomes oxygen deficient because oxygen is extracted from the crystal lattice by the reduction treatment, Since it reacts with oxygen as shown in the following formula (2), the effect as an oxygen scavenger is exhibited.

 CeO + ((2-X) / 2) 0 → CeO (2)

 x 2 2

[0034] Although not certain, the cerium oxide reacts with moisture in the atmosphere to cause hydrate (C The function of removing moisture in the sealed atmosphere is demonstrated by forming eO · ηΗ〇).

 Therefore, by using a deoxygenating agent composed of one cerium oxide, a deoxygenating function that has both a deoxidizing function for removing oxygen in a sealed atmosphere and a dehumidifying function for removing moisture in the sealed atmosphere. An agent can be provided.

 [0036] Furthermore, in the present invention, when adjusting the oxide with respect to the cerium oxide having oxygen defects, a specific additive element is added and substituted solid solution is obtained to obtain a composite oxide, and the oxygen absorption amount is increased. Try to increase it significantly.

 Examples of this specific additive element include magnesium (Mg), calcium (Ca), stoichiometric titanium (Sr), barium (Ba), lanthanum (La), niobium (Nb), praseodymium (Pr) or yttrium (Y )) Or a mixture thereof.

 [0037] Of these, yttrium (Y), calcium (Ca), and praseodymium (Pr) are particularly preferable because they increase oxygen absorption.

 These additive elements are added during the production of cerium oxide powder and are dissolved together with cerium oxide to form a composite oxide.

 [0038] By adding this specific additive element, the oxygen absorption amount is increased as follows.

 First, cerium oxide is usually 4 +, but its valence changes to 3 + when reduced at high temperatures. Along with this change in valence, the ionic radius of cerium oxide expands, the crystal lattice itself expands, and the structure becomes unstable. However, the yttrium (Y), calcium (Ca) and brasseodium (Pr) Addition of these lasing forces having an ionic radius smaller than that of expanded 3+ cerium ions can suppress the expansion of the lattice. As a result, more oxygen defects can be retained.

 [0039] The total amount of the additive elements is preferably:! To 20 mol%. This is because if the amount is less than 1 mol%, the amount of the effect of addition is small.

[0040] In general, when an element having no or little change in valence is added to cerium oxide, the effect of increasing the amount of oxygen absorbed is not exhibited, but an element having a specific ion radius such as the additive element described above In the case of (Y, Ca, Pr), the addition of up to about 20 mol% as a total addition amount suppresses the expansion of the cerium oxide fluorite lattice and retains many oxygen defects. As a result, the amount of oxygen absorbed can be increased.

 Here, with reference to FIG. 1, it will be described that a specific additive element forms a composite oxide by solid solution with an inorganic oxide. Figure 1 shows the relationship between the amount of additive elements added and the lattice constant. As shown in Fig. 1, when the additive amount of the additive element increases, the additive element in the oxide dissolves to form a composite oxide, but the lattice constant follows the Begard rule until the solid solution limit. ,, Increase monotonically linearly (may decrease). After exceeding the predetermined inflection point, it exceeds the solid solution limit and is formed as a single oxide.

 FIGS. 2 to 7 show the relationship between the additive amount and the lattice constant for each additive element.

 Fig. 2 shows calcium (Ca), Fig. 3 shows strontium (Sr), Fig. 4 shows magnesium (Mg), Fig. 5 shows lanthanum (La), Fig. 6 shows praseodymium (Pr), and Fig. 7 shows yttrium (Y).

As shown in these drawings, calcium (Ca), strontium (Sr), and magnesium (Mg) are added in an amount of about 20 mol. An inflection point exists at / _o , and lanthanum (La) is about 40 mol. / _o , praseodymium (Pr) was about 50 mol% and yttrium (Y) was about 60 mol%. The results are shown in Table 1. Accordingly, it was confirmed that any element added in an amount of about 1 to 20 mol% was surely in a solid solution state.

[0043] [Table 1]

また、前記無機酸化物に添加される添加元素としては、前記無機酸化物のイオン 半径近傍の元素を添加することが好ましいが、添加により酸素吸収量が増大するも のであれば、これに限定されるものではない。 [0045] さらに、前記添加元素として例えばカルシウム（Ca)を固溶させたものは水分吸収 量を増大することができる。これは、酸化カルシウム（CaO)の結晶の表面近傍の Ca が水分と反応して下記式（3)により多くの水分を吸収するためと考えられる。

Further, as the additive element added to the inorganic oxide, it is preferable to add an element in the vicinity of the ionic radius of the inorganic oxide, but it is limited to this as long as the oxygen absorption amount is increased by the addition. It is not something. [0045] Furthermore, the amount of water absorption can be increased by adding, for example, calcium (Ca) as the additive element. This is presumably because Ca near the surface of the calcium oxide (CaO) crystal reacts with moisture to absorb more moisture according to the following formula (3).

 CaO + H 0 → Ca (OH) (3)

 [0046] In the case of such an oxygen scavenger, for example, a powder of a complex oxide with cerium oxide to which an additive element is added is calcined at a temperature of 1400 ° C or higher (about 1 hour). It can be easily produced by reducing and firing at 1000 ° C for 1 hour in a reducing gas stream such as hydrogen.

[0047] On the other hand, in the case of compacts such as tablets and flakes, a composite oxide powder with cerium oxide to which an additive element is added is applied at a predetermined pressure (for example, 0.5 t / cm ² or more). Can be easily manufactured by sintering at a temperature of 1000 ° C or higher and then reducing and firing in a reducing gas stream such as hydrogen at 1000 ° C for 1 hour. .

 [0048] The oxygen scavenger produced in this way is used by being sealed by a treatment such as laminating with a known oxygen scavenging package such as a porous film that can permeate oxygen sufficiently and sufficiently.

 [0049] In such an oxygen scavenger according to the present embodiment, as shown in the formula (1), by reacting with oxygen in the atmosphere, oxygen is largely absorbed and removed from the atmosphere. be able to.

 Here, the oxygen absorption performance was confirmed using calcium (Ca), praseodymium (Pr) and yttrium (Y) as additive elements. The results are shown in FIG. 8, FIG. 10 and FIG. 12 as a relationship diagram between the elapsed time of oxygen absorption and the amount of absorbed oxygen.

 As shown in Fig. 8, Fig. 10, and Fig. 12, the relationship between elapsed time and oxygen absorption is shown assuming that the addition amount is lmol%, 5mol%, 10mol%, 20mol%, 30mol%, 40mol%, 50mol%, 60mol%. Asked.

 The case of no addition is indicated by a black triangle mark.

[0051] As shown in Fig. 8, Fig. 10 and Fig. 12, as each added amount increased to lmol%, 5mol%, 10mol% and 20mol%, the oxygen absorption amount gradually increased as compared with the case of no addition. It was confirmed that the number would increase. On the other hand, even when added in an amount of 20 mol% or more, the function of increasing oxygen absorption was not exhibited.

[0052] In addition, the relationship between the amount of additive and the amount of oxygen absorbed after 96 hours is shown in FIG. 9, FIG. 11 and FIG.

 As shown in Fig. 9 and Fig. 13, in the case of calcium and yttrium, it was found that the addition amount was 20mo 1%, which became an inflection point, and the additional addition does not contribute to oxygen absorption. In addition, as shown in Fig. 11, in the case of praseodymium, the addition amount is 15 mol. /. It became clear that the addition of more than that did not contribute to oxygen absorption.

 In the case of calcium, it is thought that the oxygen absorption function is inhibited as a result of an increase in the amount of a single oxide other than the solid oxide in the form of a solid solution. In the case of yttrium and brazeodymium, they are well within the solid solution limit, but this is thought to be because the lattice became too small beyond the effect of suppressing the expansion of the lattice.

 [0053] For this reason, the deoxidizer composed of the composite oxide mainly composed of cerium oxide according to the present embodiment has the following actions and effects.

 [0054] (1) Since it can react with oxygen without requiring water at all, it can be used for storage in the case of things that dislike water, such as dry food, electronic parts, solder powder, etc. The

 [0055] (2) Also, since it has a moisture removal function, it is not necessary to separately add a dehumidifying agent as in the prior art to the sealed atmosphere. As a result, for example, as shown in FIG. 14, the oxygen scavenger 12 having a dehumidifying function is provided in the step of enclosing the tablet 10 that is the object to be preserved, for example, the tablet 10 that extremely dislikes moisture, in the gas barrier film 11. It is only necessary to add the dehumidifying agent 3 and the conventional dehumidifying agent 3 can be omitted, and the manufacturing line can be simplified.

 [0056] (3) Moreover, since cerium oxide to which an additive has been added is a non-metal, foreign substances in food can be found using a metal detector that is not detected by a metal detector.

 [0057] (4) Since the resistance to microwaves is also excellent, an oxygen scavenger made of cerium oxide formed by adding an additive element that increases the amount of oxygen absorbed can prevent heating in microwave cooking. it can.

[0058] (5) Furthermore, by adding an additive to cerium oxide, the amount of oxygen absorbed increases. Compared to the case of cerium oxide alone, the oxygen absorption per unit weight can be greatly increased.

 [0059] Thus, according to the present embodiment, a deoxidizing agent having a dehumidifying function that exhibits both a deoxidizing function and a dehumidifying function using cerium oxide, which is an inorganic oxide, and a dehumidifying agent in a sealed atmosphere. A deoxygenation method can be provided.

 Therefore, it is possible to stably preserve pharmaceuticals, supplements, chemicals (eg, pigments, fragrances, fats, enzymes, vitamins, fatty acids) or food materials that are easily oxidized, foods, precision machinery and parts, semiconductor substrates, etc. It becomes possible to do so.

 [0060] Further, as shown in FIG. 15, a deoxygenating functional film 20A having a dehumidifying function may be used.

 As shown in FIG. 15, the deoxygenating functional film 20A is provided on the deoxygen / moisture absorbing layer 21 made of an inorganic oxide such as cerium oxide, and on the outer layer side of the deoxygenating / moisture absorbing layer 21, A gas barrier layer 22 having gas barrier properties and an oxygen and moisture easily permeable layer 23 provided on the inner layer side of the deoxygenated / water absorbing layer 21 and having oxygen and moisture easily permeable are configured. Here, in FIG. 15, reference numeral 25 indicates oxygen, and 26 indicates moisture.

 In FIG. 15, an outer layer 24 is provided outside the gas barrier layer 22 to protect the gas barrier layer.

 In the case of pharmaceuticals or supplements that do not like moisture, the oxygen and moisture permeable layer 23 is on the inner side (that is, the atmosphere side where dehumidification and deoxygenation is desired), and the gas barrier layer 22 is on the outer side (for example, the atmosphere side). As described above, it is packaged, sealed and stably stored by a deoxidation functional film 20A having a dehumidifying function.

 [0061] Here, the deoxygenated / water-absorbing layer 21 includes polypropylene, polybutadiene, polymethylpentene, elastomer, silicon resin ethylene-butyl acetate copolymer, polybutadiene containing inorganic oxide such as cerium oxide. , Polyisoprene, polyethylene (very low density polyethylene, low density polyethylene, medium density polyethylene), propylene-ethylene copolymer, propylene-ethylene random polymer, 'ethylene-ethylene olefin copolymer, etc. However, the present invention is not limited to these examples.

[0062] Here, as the gas barrier layer 22, an anoremi foil, polybutyl alcohol, polyvinyl chloride is used. Nylidene-coated stretched nylon (trade name), terephthalic acid-trimethylhexamethylenediamine condensed polymer, 2,2-bis (P-aminocyclohexyl) propane adipic acid copolymer, ethylene-bial alcohol copolymer, Examples of single-layer or multi-layer materials such as polyvinyl chloride, nylon MXD (trade name), nylon 6 (trade name), nylon 6, 6 (trade name), etc. It is not limited to the above, but it can block any gas and moisture, and preferably any one that blocks oxygen and moisture.

[0063] Further, as the oxygen and moisture easily permeable layer 23, for example, non-woven fabric, polypropylene (PP), polyethylene (ultra low density polyethylene, low density polyethylene, medium density polyethylene), ethylene propylene copolymer, ethylene propylene rubber, Examples of the copolymer may include a single layer or a multilayer such as an ethylene-atalinolenic acid ethynole copolymer, but the present invention is not limited to these, and is capable of permeating gas and moisture, preferably oxygen and Any layer that permeates moisture can be used, for example, a layer made of fibers such as paper.

 The oxygen and moisture easily permeable layer 23 may be used in combination with the function of a sealant layer (for example, a polyolefin such as PP or PE).

[0064] Examples of the outer layer 24 include polyethylene, polypropylene, polyethylene terephthalate (PET), nylon (trade name), and the like, but the present invention is not limited thereto.

 Further, as shown in the deoxygenation functional film 20B in FIG. 16, a buffer layer 27 is provided between the deoxygenation / moisture absorption layer 21 and the gas barrier layer 22, and the film has adhesiveness and buffer properties. You may make it give to.

 Further, an advanced gas barrier layer 28 may be provided between the gas barrier layer 22 and the outer layer 24 to further strengthen the prevention of gas intrusion from the outside.

Here, examples of the buffer layer 27 include resins having a buffering action and an adhesive action, such as polyethylene and polypropylene, but the present invention is not limited thereto.

[0067] Further, as the advanced gas barrier layer 28, for example, various metal foils including aluminum foil, aluminum vapor deposition film, various oxide (silica, titania, zirconia, alumina) vapor deposition film The force which can illustrate etc. This invention is not limited to these.

 [0068] By using a deoxygenation functional film 20B having a dehumidifying function with a six-layer structure as shown in Fig. 16, the buffering action is improved and the prevention of gas intrusion from the outside is strengthened, and the added value is increased. The film can be provided at a high level.

 In addition, as shown in FIG. 17, an oxygen scavenger 30 composed of an inorganic oxide of any one of cerium oxide, zinc oxide, and titanium oxide having oxygen defects, or a mixture thereof, and the oxygen scavenger 30 In addition, a deoxygenated package 32 having a dehumidifying function may be configured from the package 31 having oxygen and moisture permeability.

 The package 31 may be either a single layer or a multilayer, and may be intentionally provided with pinholes to improve oxygen and moisture permeability. .

 Further, as shown in FIG. 18, an oxygen scavenger 40 made of an inorganic oxide of any one of cerium oxide, zinc oxide, and titanium oxide having oxygen defects, or a mixture thereof, is provided in the resin layer 41. The deoxygenated resin composition 42 having a dehumidifying function may be constituted by being dispersed or kneaded.

 [0071] The material constituting the resin layer 41 may be any material that can permeate oxygen and moisture. For example, polyethylene (ultra low density polyethylene, low density polyethylene, medium density polyethylene), polypropylene, propylene Examples include ethylene copolymers, ethylene vinyl acetate copolymers, olefin resins such as blends thereof, styrene resins such as polystyrene, styrene butadiene copolymers, and styrene isoprene copolymers. . Also, these resins can be used alone or as a blend.

 Example

 [0072] An example for confirming the effect of the present invention will be described below, but the present invention is not limited to this example.

[0073] <Raw material adjustment>

While stirring an aqueous solution of ammonium bicarbonate, ammonia, ammonium carbonate and oxalic acid in water, the aqueous cerium nitrate solution was added dropwise for reverse neutralization. Washed with on-exchange water (twice in this example) and filtered. Thereafter, the filtrate was dried (at 300 ° C. for 2 hours) to obtain a powder of acid cerium (CeO) of Example 1 (average particle size: about 0.5

 2

 β m) was obtained (adjustment for cerium oxide alone).

[0074] <Addition of additional elements>

 As Example 2, in the process under the cerium nitrate aqueous droplet for producing the powder of the cerium oxide simple substance, calcium (Ca) was added as an additive element so as to be 10 mol% nitrate.

 [0075] The sintering condition of the molded body of this example was 1100 ° C for 1 hour. Furthermore, the reduction conditions are 100 0. The flow was 400 SCCM with 100% hydrogen gas for 1 hour with C. As the package, an inner bag with many pinholes was used, and the film was packed.

 [0076] The oxygen scavengers of Examples 1 and 2 in the package were sealed with 1.5 g, and the humidity change in the package after a predetermined time was confirmed. In addition, as a comparative example 1, the silica gel alone is lg, as a comparative example 2, the iron powder-based oxygen scavenger that has been commercially available in the past, and as a comparative example 3, the conventional iron powder-based oxygen scavenger and the silica gel are packed in the package. What was enclosed was used. Figure 19 shows the result. Note that the general iron powder type oxygen scavenger used as a comparative example requires a moisture retention agent to keep absorbing oxygen (see formula (1)), and is enclosed.

 [0077] The oxygen scavenger having a dehumidifying function of the cerium oxide simple substance of Example 1 (shown in FIG. 19), and having a dehumidifying function comprising the cerium oxide composite oxide in which calcium in Example 2 is dissolved. Oxygen scavenger (indicated by circles in FIG. 19), silica gel alone of comparative example 1 (indicated by X in FIG. 19), iron powder-based oxygen scavenger and water retention agent in comparative example 2 (black triangle in FIG. 19) This was confirmed by the ability to change the humidity of the combination of the iron powder type oxygen scavenger, the water retention agent and the silica gel of Comparative Example 3 (indicated by Δ in FIG. 19).

 [0078] As shown in FIG. 19, the silica gel alone of Comparative Example 1 (indicated by X in FIG. 19) is a change in moisture in the package (about 7% decrease).

[0079] In addition, the iron powder-based oxygen scavenger and the water retention agent (indicated by black triangles in Fig. 19) of Comparative Example 2 are used to increase the humidity as the amount of moisture from the moisture retention agent increases with time. There was an increase (about 7% increase). [0080] The combination of the iron powder type oxygen scavenger, the water retention agent and the silica gel of Comparative Example 3 (indicated by Δ in Fig. 19) was confirmed to have a dehumidifying function by silica gel in Comparative Example 2 (mostly No change).

 [0081] On the other hand, the oxygen scavenger having the dehumidifying function of cerium oxide alone of Example 1 (indicated by the middle part in FIG. 19) exhibits the dehumidifying function (about 16% decrease) over a predetermined time. It was confirmed that

 [0082] Further, the oxygen scavenger having a dehumidifying function (shown by a circle in FIG. 19) composed of the cerium oxide composite oxide in which calcium of Example 2 is solid-dissolved has a calcium addition effect (about 18%). Decrease) was confirmed.

 [0083] Thus, it was confirmed that the dehumidifying function was manifested by cerium oxide alone (about 23% reduction), compared to the case where silica gel such as a conventional iron powder-based oxygen scavenger was used in combination. In addition, it was confirmed that the composite oxide body made of calcium additive had better dehumidifying performance than cerium alone.

 Next, when cerium oxide alone or calcium was added to cerium oxide at 10 mol%, 20 mol%, and 40 mol%, changes in relative humidity during a predetermined period were confirmed. In the test, when the air volume is 300 ml (oxygen volume 60 ml), “K-Nylon (trade name)” is used as a gas barrier film, and a deoxygenating agent having a dehumidifying and deoxygenating function is enclosed inside, and the test is performed for a predetermined time. The humidity change was measured.

 The results are shown in FIG. As shown in FIG. 20, when calcium was used as an additive element, a decrease in final reached humidity was confirmed by the hygroscopic action of the precipitated calcium oxide even when the solid solution limit exceeded 20 mol%.

[0084] Further, in the above test, when the humidity atmosphere inside the gas barrier film was adjusted to a high level, it was confirmed whether or not the dehumidification performance was dependent on the initial humidity.

 The result is shown in FIG. Even when the initial measurement was 65RH%, 55RH%, 45RH%, and 30RH%, it was found that the relative humidity would be 20RH or less in any case and eventually be around 15RH% in any case. It was confirmed that there was no dependency on the initial humidity.

Industrial applicability As described above, according to the present invention, the deoxygenating function is exhibited while exhibiting the dehumidifying function. Suitable for storing things.

Claims

The scope of the claims  [1] Using an inorganic oxide of cerium oxide, zinc oxide or titanium oxide having oxygen defects, or a mixture thereof, absorbs and removes oxygen in the atmosphere and absorbs moisture in the atmosphere A dehumidification / deoxygenation method characterized by:  [2] In claim 1,  Magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr), yttrium (Y), one or a mixture thereof, the inorganic oxide A dehumidification / deoxygenation method characterized by being dissolved in a solid solution. [3] In claim 2,  A dehumidification / deoxygenation method, wherein the total amount of the solid solution element added is 1 to 20 mol%.  [4] Made of inorganic oxide of cerium oxide, zinc oxide or titanium oxide having oxygen defects, or a mixture of these, absorbs and removes oxygen in the atmosphere and absorbs moisture in the atmosphere An oxygen scavenger having a dehumidifying function and a package containing the oxygen scavenger,  A deoxygenated package having a dehumidifying function, characterized in that the package has oxygen permeability and moisture permeability.  [5] In claim 4,  Magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr), yttrium (Y), one or a mixture thereof, the inorganic oxide Deoxygenated packaging body having a dehumidifying function characterized by being dissolved in [6] In claim 5,  A deoxygenated package having a dehumidifying function, wherein the total addition amount of the solid solution elements is 1 to 20 mol%. [7] Consists of an inorganic oxide of cerium oxide, zinc oxide, or titanium oxide having oxygen defects, or a mixture thereof, and absorbs and removes oxygen in the atmosphere and absorbs moisture in the atmosphere. Deoxygenation / moisture absorbing layer composed of deoxidizer with dehumidifying function A deoxygenating functional film having a dehumidifying function characterized by comprising: [8] In claim 7,  A gas barrier layer provided on one surface of the deoxygenation / moisture absorbing layer and having gas barrier properties;  A deoxygenation function film having a dehumidifying function, comprising an oxygen and moisture easily permeable layer provided on the other surface of the deoxygenated moisture absorbing layer and having oxygen and moisture easily permeable layers .  [9] In claim 7 or 8,  A deoxygenating functional film having a dehumidifying function, wherein an advanced gas barrier layer is provided between a gas noble layer and an outer layer. [10] In any one of claims 7 to 9,  A deoxygenating functional film having a dehumidifying function, wherein a buffer layer is provided between the deoxygenating / moisture absorbing layer and the gas barrier layer. [11] In any one of claims 7 to 10,  Magnesium (Mg), calcium (Ca), strontium (Sr), lanthanum (La), niobium (Nb), praseodymium (Pr), yttrium (Y), one or a mixture thereof, the inorganic oxide A deoxygenating functional film with a dehumidifying function characterized by being dissolved in a solid solution.  [12] In claim 11,  A deoxygenation functional film having a dehumidifying function, wherein a total addition amount of the solid solution elements is 1 to 20 mol%.  [13] It is composed of an inorganic oxide of cerium oxide, zinc oxide or titanium oxide having oxygen defects, or a mixture thereof, and absorbs and removes oxygen in the atmosphere and absorbs moisture in the atmosphere. A deoxygenating resin composition having a dehumidifying function, wherein the deoxidizing agent having a dehumidifying function is dispersed or kneaded in a resin having oxygen and moisture permeability.  [14] In claim 13, Magnesium (Mg), Calcium (Ca), Strontium (Sr), Lanthanum (La), Niobium ( Nb), praseodymium (Pr) or yttrium (Y), one or a mixture thereof, or a mixture thereof, dissolved in the inorganic oxide, and a deoxygenating resin composition having a dehumidifying function .  In claim 14,  A deoxygenated resin composition having a dehumidifying function, wherein a total addition amount of the solid solution elements is 1 to 20 mol%.