WO2008001732A1 - Procédé de déshumidification/désoxygénation et emballage désoxygénant, film qui présente une fonction de désoxygénation et composition de résine désoxygénante, toutes deux présentant une fonction de déshumidification - Google Patents

Procédé de déshumidification/désoxygénation et emballage désoxygénant, film qui présente une fonction de désoxygénation et composition de résine désoxygénante, toutes deux présentant une fonction de déshumidification Download PDF

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Publication number
WO2008001732A1
WO2008001732A1 PCT/JP2007/062730 JP2007062730W WO2008001732A1 WO 2008001732 A1 WO2008001732 A1 WO 2008001732A1 JP 2007062730 W JP2007062730 W JP 2007062730W WO 2008001732 A1 WO2008001732 A1 WO 2008001732A1
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WO
WIPO (PCT)
Prior art keywords
oxygen
dehumidifying function
moisture
oxide
atmosphere
Prior art date
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PCT/JP2007/062730
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English (en)
Japanese (ja)
Inventor
Kazuya Kinoshita
Isamu Yashima
Original Assignee
Mitsui Mining & Smelting Co., Ltd.
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Filing date
Publication date
Application filed by Mitsui Mining & Smelting Co., Ltd. filed Critical Mitsui Mining & Smelting Co., Ltd.
Priority to TW096123036A priority Critical patent/TWI474860B/zh
Publication of WO2008001732A1 publication Critical patent/WO2008001732A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0207—Compounds of Sc, Y or Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • 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.
  • 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.
  • 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.
  • 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).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11 226388
  • the iron-based oxygen scavenger requires water in the deoxygenation reaction.
  • moisture is emitted from the moisture retaining agent, so that the humidity in the sealed bag increases.
  • a dehumidifier 3 such as silica gel is enclosed. There is.
  • 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.
  • 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.
  • 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)
  • Mg magnesium
  • Ca calcium
  • La lanthanum
  • Nb niobium
  • Pr praseodymium
  • Y yttrium
  • 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%.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • FIG. 1 is a graph showing the relationship between the amount of additive element added and the lattice constant.
  • FIG. 2 is a graph showing the relationship between the amount of additive element (Ca) added and the lattice constant.
  • FIG. 3 is a graph showing the relationship between the amount of additive element (Sr) added and the lattice constant.
  • 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 is a graph showing the relationship between the amount of additive element (Pr) added and the lattice constant.
  • FIG. 7 is a graph showing the relationship between the amount of additive element (Y) added and the lattice constant.
  • 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 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 is a graph showing the relationship between the amount of additive and the amount of oxygen absorbed after 96 hours in FIG.
  • 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 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 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 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.
  • 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.
  • cerium oxide as the inorganic oxide, which has a particularly large oxygen absorption capability.
  • 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.
  • cerium oxide reacts with moisture in the atmosphere to cause hydrate (C
  • C The function of removing moisture in the sealed atmosphere is demonstrated by forming eO ⁇ ⁇ ).
  • 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.
  • this specific additive element examples include magnesium (Mg), calcium (Ca), stoichiometric titanium (Sr), barium (Ba), lanthanum (La), niobium (Nb), praseodymium (Pr) or yttrium (Y )) Or a mixture thereof.
  • yttrium (Y), calcium (Ca), and praseodymium (Pr) are particularly preferable because they increase oxygen absorption.
  • the oxygen absorption amount is increased as follows.
  • 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.
  • 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.
  • Figure 1 shows the relationship between the amount of additive elements added and the lattice constant.
  • 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)
  • Fig. 7 shows yttrium (Y).
  • 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.
  • 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).
  • 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.
  • 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).
  • a predetermined pressure for example, 0.5 t / cm 2 or more.
  • 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.
  • 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.
  • the deoxidizer composed of the composite oxide mainly composed of cerium oxide according to the present embodiment has the following actions and effects.
  • 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.
  • 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.
  • 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.
  • 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 can be provided.
  • a deoxygenating functional film 20A having a dehumidifying function may be used.
  • 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.
  • reference numeral 25 indicates oxygen
  • 26 indicates moisture.
  • an outer layer 24 is provided outside the gas barrier layer 22 to protect the gas barrier layer.
  • 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.
  • 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.
  • an anoremi foil, polybutyl alcohol, polyvinyl chloride is used as the gas barrier layer 22 as the gas barrier layer 22.
  • Nylidene-coated stretched nylon (trade name), terephthalic acid-trimethylhexamethylenediamine condensed polymer, 2,2-bis (P-aminocyclohexyl) propane adipic acid copolymer, ethylene-bial alcohol copolymer,
  • 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.
  • 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
  • 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).
  • a sealant layer for example, a polyolefin such as PP or PE.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • various metal foils including aluminum foil, aluminum vapor deposition film, various oxide (silica, titania, zirconia, alumina) vapor deposition film
  • oxide silicon, titania, zirconia, alumina
  • 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.
  • 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
  • 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. .
  • 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.
  • the material constituting the resin layer 41 may be any material that can permeate oxygen and moisture.
  • 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.
  • these resins can be used alone or as a blend.
  • 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.
  • 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.
  • 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.
  • the silica gel alone is lg
  • 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.
  • 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 ⁇ in FIG. 19).
  • the silica gel alone of Comparative Example 1 is a change in moisture in the package (about 7% decrease).
  • 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).
  • the combination of the iron powder type oxygen scavenger, the water retention agent and the silica gel of Comparative Example 3 (indicated by ⁇ in Fig. 19) was confirmed to have a dehumidifying function by silica gel in Comparative Example 2 (mostly No change).
  • the oxygen scavenger having the dehumidifying function of cerium oxide alone of Example 1 exhibits the dehumidifying function (about 16% decrease) over a predetermined time. It was confirmed that
  • 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.
  • the deoxygenating function is exhibited while exhibiting the dehumidifying function. Suitable for storing things.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Gas Separation By Absorption (AREA)
  • Packages (AREA)
  • Wrappers (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Drying Of Gases (AREA)

Abstract

Selon l'invention, un comprimé (10) à conserver est enfermé dans un film (11) à barrière de gaz avec un agent désoxygénant (12) qui présente une fonction de déshumidification. L'agent désoxygénant (12) comprend un composant d'oxyde minéral qui comprend au moins un élément de l'ensemble constitué de l'oxyde de cérium, de l'oxyde de zinc et de l'oxyde de titane et de leurs mélanges, chacun présentant un déficit en oxygène. Cela permet d'absorber et d'enlever l'oxygène de l'atmosphère et d'absorber aussi l'humidité présente dans l'atmosphère. La fonction d'absorption de l'oxygène et de l'humidité peut être améliorée en plaçant du calcium (Ca) ou similaires sous forme d'une solution solide dans le composant d'oxyde minéral.
PCT/JP2007/062730 2006-06-29 2007-06-25 Procédé de déshumidification/désoxygénation et emballage désoxygénant, film qui présente une fonction de désoxygénation et composition de résine désoxygénante, toutes deux présentant une fonction de déshumidification WO2008001732A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW096123036A TWI474860B (zh) 2006-06-29 2007-06-26 A dehumidification / deoxidation method, a deoxidizing package having a dehumidifying function, and a deoxidized film or deoxidizing resin composition

Applications Claiming Priority (4)

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JP2006179857 2006-06-29
JP2006-179857 2006-06-29
JP2006-355376 2006-12-28
JP2006355376 2006-12-28

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008140004A1 (fr) * 2007-05-10 2008-11-20 Mitsui Mining & Smelting Co., Ltd. Agent désoxydant et procédé pour le produire
CN102056660A (zh) * 2008-07-11 2011-05-11 三井金属矿业株式会社 脱氧剂
CN113477044A (zh) * 2021-07-08 2021-10-08 湖北恒维通智能科技有限公司 一种用于金属增材制造的超低氧水含量气氛控制装置

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* Cited by examiner, † Cited by third party
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JPWO2012057161A1 (ja) * 2010-10-26 2014-05-12 三井金属鉱業株式会社 一酸化炭素の製造方法及び製造装置
JP6577848B2 (ja) * 2014-12-26 2019-09-18 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． ガス吸着材、及びこれを用いた真空断熱材

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WO2005009593A1 (fr) * 2003-07-21 2005-02-03 Entegris, Inc. Purification de gaz d'hydrure destinee a l'industrie des semi-conducteurs
JP2005105194A (ja) * 2003-10-01 2005-04-21 Toppan Printing Co Ltd 酸素吸収能を有する樹脂組成物およびそれを用いた積層体、包装体
WO2005070832A1 (fr) * 2004-01-21 2005-08-04 Mitsui Mining & Smelting Co., Ltd. Poudre d'oxydes en solution solide
WO2005088298A1 (fr) * 2004-03-12 2005-09-22 Mitsui Mining & Smelting Co., Ltd. Agent de détection de l'oxygène
JP2006095833A (ja) * 2004-09-29 2006-04-13 Toppan Printing Co Ltd 酸素吸収バリア性積層体及びそれを用いて作製された包装体
JP2006130717A (ja) * 2004-11-04 2006-05-25 Toppan Printing Co Ltd 積層体、およびこれを用いた容器

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JP4454276B2 (ja) * 2003-10-01 2010-04-21 凸版印刷株式会社 酸素吸収能を有する樹脂組成物およびそれを用いた積層体、包装体

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JPH0375202A (ja) * 1989-08-17 1991-03-29 Japan Pionics Co Ltd 水素化物ガスの精製方法
JP2000093734A (ja) * 1997-09-19 2000-04-04 Aeronex Inc 非腐食性ガス流から水を除去するための方法、組成物 およびその装置
JP2000070437A (ja) * 1998-06-04 2000-03-07 Aruze Corp 遊技機
JP2004337840A (ja) * 2003-03-17 2004-12-02 Umicore Ag & Co Kg 酸素吸蔵材料、該酸素吸蔵材料の製造法及び内燃機関の排ガス浄化用触媒
WO2005009593A1 (fr) * 2003-07-21 2005-02-03 Entegris, Inc. Purification de gaz d'hydrure destinee a l'industrie des semi-conducteurs
JP2005105194A (ja) * 2003-10-01 2005-04-21 Toppan Printing Co Ltd 酸素吸収能を有する樹脂組成物およびそれを用いた積層体、包装体
WO2005070832A1 (fr) * 2004-01-21 2005-08-04 Mitsui Mining & Smelting Co., Ltd. Poudre d'oxydes en solution solide
WO2005088298A1 (fr) * 2004-03-12 2005-09-22 Mitsui Mining & Smelting Co., Ltd. Agent de détection de l'oxygène
JP2006095833A (ja) * 2004-09-29 2006-04-13 Toppan Printing Co Ltd 酸素吸収バリア性積層体及びそれを用いて作製された包装体
JP2006130717A (ja) * 2004-11-04 2006-05-25 Toppan Printing Co Ltd 積層体、およびこれを用いた容器

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008140004A1 (fr) * 2007-05-10 2008-11-20 Mitsui Mining & Smelting Co., Ltd. Agent désoxydant et procédé pour le produire
CN102056660A (zh) * 2008-07-11 2011-05-11 三井金属矿业株式会社 脱氧剂
CN113477044A (zh) * 2021-07-08 2021-10-08 湖北恒维通智能科技有限公司 一种用于金属增材制造的超低氧水含量气氛控制装置
CN113477044B (zh) * 2021-07-08 2022-04-22 湖北恒维通智能科技有限公司 一种用于金属增材制造的超低氧水含量气氛控制装置

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TWI474860B (zh) 2015-03-01
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JP2008238170A (ja) 2008-10-09
JP4210310B2 (ja) 2009-01-14

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