TW200927282A - Deoxidizer - Google Patents

Abstract

A deoxidizer characterized by having a trigonal crystal structure and containing any of cerium oxides of the formula Ce2O3-x (x is a numeral of 0 to less than 1). Especially preferably, the cerium oxide is represented by the formula Ce2O3-x (x is a numeral of over 0 to less than 1). The cerium oxide may be loaded with an element capable of increasing the amount of oxygen absorbed by the cerium oxide, such as Ca.Preferably, the cerium oxide is produced by firing an oxygenous cerium salt or a hydrate thereof at 1000 DEG C or above in a reducing atmosphere. Also preferably, the cerium oxide is produced by firing the cerium oxide of the formula CeO2 at 1200 DEG C or above in a reducing atmosphere.

Description

200927282 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an oxygen scavenger containing cerium oxide. Further, the tree uses the oxygen scavenger, the deoxidizing resin composition, and the cavity. Further, the present invention relates to a method for producing the aforementioned cerium oxide. [Prior Art] In recent years, in order to meet the high requirements for food safety and quality maintenance, ❹ ❹ 2 has made the inside of the package for foods in packaged foods anaerobic, and the products are oxidized and deteriorated. Specifically, the de-emulsion which removes the oxygen of the atmosphere and the foodstuff are placed in the inside of the package for food, and the residual oxygen in the inside of the package is removed, so that the slag and the mouth are separated. Also, no... The inside of the package is an anaerobic-food package, and::: into the above-mentioned deoxidizer - the door-to-milk meets the food package, and the inside of the food package is invaded by the inside. The deoxidizer removes it and the like. The oxygen is also used as an oxygen scavenger for removing oxygen in the atmosphere and a material composed of an organic material and a material for the I (four) material. The consideration of these materials is mainly to use an oxygen-based deoxidizer as an oxygen generator such as the following chemical formula (;,). The iron is removed from the atmosphere, and the iron is reacted with a small amount of moisture in the atmosphere, the oxygen in the emulsion, thereby removing oxygen from the atmosphere.冋

Fe+1/2H2〇+3/4〇2~Fe〇〇H (1) Kernel, use the previous iron system $ stomach & In the case of an iron-based oxygen scavenger, the following problems are required: (1) The amount of water required for the reaction with oxygen is small but necessary, so the performance of the dry food 133482.doc 200927282 deoxidizer is preserved: electronic parts and solder powder If the situation of avoiding aquatic products is not enough, it will not be fully utilized. (2) The food packaged with the iron-based deoxidizer +, the incorporation of foreign matter such as metal into the metal is detected in the shape of the metal, the iron powder in the oxygenator will react to the metal detector 'cannot be carried out Easy check. (3) There was a fire caused by rapid microwave heating of a microwave oven or the like.

As an oxygen scavenger of (4) an oxygen scavenger, it has been proposed to have an inorganic oxide, that is, an inorganic compound having an oxygen deficiency (see Patent Documents! to 5). In the same literature, as the inorganic oxide having oxygen deficiency, there are exemplified by dioxins, zinc oxide, and cerium oxide. The inorganic oxide having oxygen deficiency is cerium oxide, which is a fluorite-type crystal structure. These inorganic oxides are advantageously in contact with the oxygen-based oxygen scavengers in the absence of moisture in the reaction with oxygen. However, the oxygen absorption of these inorganic oxides is less than that of iron-based deoxidizers. Patent Document 1: JP-A-2005-104064 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. 2005-105195. Patent Document 3: JP-A-2005-105195 Patent Document 4: JP-A-2005-1051 99 SUMMARY OF THE INVENTION The present invention provides an oxygen scavenger comprising a crystal structure having a trigonal crystal form, and having a Ce2〇3 χ (χ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 2005 2005 C C C C C C C C C C , less than 1) expressed by yttrium oxide. Further, the present invention provides an oxygen scavenger which is 133482.doc 200927282 bag having air permeability resistance: a package in which the aforementioned oxygen scavenger is contained. Further, the present invention provides a deoxidizing agent and a resinous resin composition having oxygen permeability, which comprises the foregoing: a second hair: a deoxidized laminate film provided by the aforementioned wall property "Gas barrier layer" "a barrier layer has a milk barrier that is easily transmitted through the other surface of the deoxidation layer, and is formed by an oxygen-permeable layer that has oxygen permeability. The present invention provides a method for producing an oxidation decoration. The oxidized crystal structure of the octagonal crystal form is represented by a number of 〇3 〇 办 ) ) ) ' ' ' ' ' 该 该 该 该 该 该 该 该 该 该 该 该 该 将 含 含 含 含 含 含 含The step of firing in (10) or more; or the step of cultivating the oxidized bromine represented by Ce 〇 2 in a reducing atmosphere in 12 以上 or more. EMBODIMENT Hereinafter, the present invention will be described based on preferred embodiments thereof. The oxygen scavenger of the present invention contains a cerium oxide having a specific crystal structure as a constituent component. Specifically, the oxidized metal has a crystal structure of a trigonal crystal structure, and has a Ce2〇3.x (x system or more). , less than the number of i) Further, in the following description, in order to distinguish the oxidized metal from the previously known oxidized crystal having a fluorite crystal structure and having oxygen deficiency, it is referred to as a trigonal cerium oxide. It has the crystal structure shown in Fig.!, that is, with & axis length, b-axis length and c-axis length are the same, and the angle between each axis" β and 丫 133482.doc -8 · 200927282

They are all the same and are non-90 degree angles of the 曰μ A degree of crystal structure. It is oxidized with a sapphire crystal structure, and it was made by the ancient "Ten & There is a crystal structure as shown in Fig. 2. As described above, the number 彳矣-4 A 钸 of the trigonal crystal oxidation is represented by Ce2〇h (x system 〇 or more, less than i). In the formula, xg 〇 _ sliding digonal crystal oxidized bromine, having a crystal structure as shown in Fig. 1. The number of the valence A-僧.Λ-shaped two-day type yttrium oxide 钸 钸 买 买 买 买 买 买 买 〇 〇 〇 〇 心 心 心 心 心 心 η η η η η η η η η η η η In the crystal structure, the oxygen is a defect state in a few places in the position. Therefore, the oxygen number of the situation, for the - part decoration, due to the price of the electric compensation type emulsification 钸 铧 ... ... ... ... ... ...... That is, X is. In addition, the trigonal crystal oxidation of the case is a divalent <!汲僧# β π system becomes an abnormal valence state in which a part of the valence valence is valence. The binary crystal yttrium oxide has a higher φ. That is, the more the oxygen deficiency is, the more the oxygen absorption amount is, and if the value is larger, the oxygen absorption amount is higher. ❹ 曰 曰 曰 不易 不易 不易 Λ Λ Λ Λ Λ Λ Λ Λ 曰 曰 不易 曰 曰 曰 曰 曰 曰From this point of view, the X value in 1, the red from Α is preferably greater than 0, small, preferably greater than 〇, and 0.5 Τ'. #,π Reason A * Bu Another, let x upper limit be less than one, X is 1 in the case of yttrium oxide will be the helmet method - ancient a ^ structure, and become the rock pound ^ ^ gentry to maintain the two sides The crystal yield of the 曰 type. When it is a crystal structure of a salt-salt type, it is difficult to achieve a desired oxygen-absorbing Si oxide, and it is contacted with oxygen and absorbed. First, oxygen deficiency is relatively high, and it has been previously known to have a stone structure. With the crystal structure and oxygen-deficient oxygen I7, there is no change in the crystal structure after absorption of milk. 'Formula (10) 2 y is used as 133482.doc 200927282 The y value of oxygen deficiency is only above 〇, less than 〇·5 Changes within the scope. Because of this difference, the trigonal cerium oxide system has a high oxygen absorption amount far exceeding the theoretical limit of cerium oxide having a fluorite-type crystal structure. . The oxygen absorption amount of the ternary crystal cerium oxide can be further increased by adding the element which increases the amount of emulsion absorption to the cerium oxide to form a composite oxide. Adding elements such as a group consisting of magnesium (Mg), calcium (Ca), strontium (Sr) strontium (Ba), strontium (La), strontium (Nb), strontium and barium

Choose at least one of them. Among these elements, at least one selected from the group consisting of (7), 33 (Ca), and 镨 (4) is added, and the amount of oxygen absorption can be remarkably increased, which is particularly suitable. The total addition amount of the elements described above is preferably from 1 to 20 mol% with respect to the ruthenium atom from the viewpoint of stably increasing the oxygen absorption amount of the trigonal iridium oxide. The fluorite 35 cerium oxide previously known has high oxygen ion conductivity, so its activity is very high and the oxygen absorption rate is very fast. Because of the use of fluorite-type oxidizing screen deoxidizer, while waiting for the target product (such as dry food or tablets, etc.): the oxygen is absorbed during the sealing of the packaging bag, thereby reducing the oxygen and oxygen of the oxygen scavenger the amount. In contrast, the trigonal cerium oxide has a feature that the oxygen absorption rate is relatively slow, in addition to the feature of high oxygen absorption. The reason why the oxygen absorption rate is slow is that the deoxidizer of the present invention does not have the oxygen ion-conducting trigonal crystal cerium oxide, and even if the contact is gradually oxidized, it is waiting for the target product - The time of the seal is set to have a degree of freedom.曰 = crystalline oxidized bromine is generally used in a powder state. Depending on the case, the trigonal antimony oxide can also be used in a state in which a molded body such as a molded body is compressed. Further, 133482.doc 200927282 Trigonal crystalline cerium oxide can constitute the deoxidizing agent of the present invention by using itself alone. Alternatively, the trioxane type cerium oxide may be used in combination with other substances to form the oxygen scavenger of the present invention. As other substances, for example, various dehumidifications (four) can be cited. By deuterium (4), a deoxidizing agent having dehumidifying energy can be constructed. In combination with the desiccant (4), the ratio of the total weight of the oxidized decorative material oxidized bromine to the dehumidifying agent is preferably from 5 〇 to 99% by weight, particularly from 6 〇 to 85 % by weight. On the other hand, the proportion of desiccant should be the weight of the curse, especially

It is 15 to 40% by weight. As the dehumidifying agent, any of an inorganic substance and an organic substance can be used. As an inorganic dehumidifying agent, it can be used as a mineral stone such as m-ray phos stone, clinoptilolite, sweater, etc., molecular material synthesis zeolite, bulk soil, montmorillonite and other clay minerals, Shi Xijiao, Oxidation Ming, oxidation mother , hygroscopic salts, etc. As the organic dehumidifying agent, paper poly, paper containing paper, poly-α, β-unsaturated (tetra), poly-α, ρ-unsaturated acid-exchanged ionic cross-linking material, and part of E-wife-acetate copolymer can be used. Completely compounded, partially/completely structured of polyvinyl acetate vinegar, cellulose-based derivatives, poly-sweet oxide derivatives, polyester, polyamine, and the like. Among the above-mentioned desiccant, it is particularly preferable to use minerals from the viewpoints of a large moisture absorption per unit weight, a large moisture absorption force under low humidity, chemical stability, and no toxicity reduction. When the digonal crystal cerium oxide is used in a powder state, the particle diameter may be selected according to the dosage form of the deoxidizing agent of the invention. For example, in the case where the oxygen scavenger of the present invention is contained in a bag-like package having a gas permeation resistance (for example, 1 〇 to touch,), the average particle diameter is obtained from the point of ensuring sufficient specific surface area and ensuring oxygen contact. It should be 〇〇ι ~ι〇〇 (4), especially 133482.doc 200927282 0.0H μπ^. In the case where the epoxy resin of the present invention and the resin composition having oxygen permeability form a film form, the particle diameter of the oxidized crystal is preferably not more than the thickness of the film. From this viewpoint, the average particle diameter of the oxidized decorative material is preferably 0.01 20 μηι, especially 〇〇1 to 1 〇 (4). The average diameter in the present specification is measured by a laser diffraction scattering type particle size distribution measuring apparatus. The deoxidizer of the present invention is an oxygen-removing body by being housed in a bag-like package having an air resistance (for example, air resistance of 1 〇 to 1 〇〇〇〇〇 second). The deoxidized body of the shape is sealed with the packaging material 与, such as a dried food or a lozenge. Examples of the material having air permeability resistance constituting the package include polypropylene, polybutan, polymethylpentene, thermoplastic elastomer, polyethylene terephthalate, and stone retort resin. Dilute-vinyl acetate copolymer, polyisoprene, ultra-low density polyethylene, low-density polyethylene, medium-density polyethylene, propylene-ethylene copolymer, propylene-ethylene random polymer, ethylene· A film made of various thermoplastic resins such as an α-olefin copolymer is subjected to a laminate of a perforator, paper, or nonwoven fabric or a combination thereof. The anti-Φ air permeability here is measured according to JIS Ρ 8117, and indicates the time required for 100 mL of air to completely pass through the area of 〇〇〇 〇〇〇 642 m 2 at a pressure difference of l_23 kPa. The oxygen scavenger of the present invention may be kneaded with a resin having oxygen permeability to constitute a deoxidizing resin composition. The resin composition is used in the form of pellets, for example, as a raw material of various resin molded bodies. Further, the resin composition is used in the form of various resin molded bodies formed in the form of pellets, for example, a film shape 1, or a disk-open state. Regardless of the form of the resin composition, the proportion of the oxygen scavenger in the resin composition is preferably from 1 to 90% by weight, particularly from 2 to 8 % by weight, from the viewpoint of exhibiting a degassing function. . The other party 133482.doc • 2 - 200927282 The ratio of the resin in the resin composition is preferably from 10 to 90% by weight, particularly from 20 to 80, from the viewpoint of maintaining the strength and formability of the resin composition. weight%. ❹ ❹ When the above resin composition is used in the form of a film, the thickness of the film is preferably 00 (four), especially 20 40 μm, depending on the specific use of the film. In the case where the resin composition is in the form of a film, other components which can improve the properties of the resin composition can be added to the resin composition as needed, in addition to the oxygen-removing agent and the oxygen-permeable resin. Examples of the other component include a pigment for coloring the resin composition into a specific color, and a filler for increasing the strength of the resin composition. The film may be used in a single layer state composed of a deoxidizing resin composition as described above. Alternatively, it may be used in a state of having a multilayer structure of an deoxidizing layer composed of the above-described deoxidizing resin composition. In the latter case, the example of the multilayer structure may be exemplified by one side of the deoxidizing layer composed of the above-described deoxidizing resin composition, a gas barrier layer having a gas barrier property, and another side of the deoxidizing layer. An oxygen permeation layer dioxide layer film having oxygen permeability is laminated. The foregoing oxygen-depleting laminate film is used in such a manner that the gas barrier layer is outward (i.e., on the atmospheric side) and the oxygen-permeable layer is inward (i.e., on the side of the atmosphere to be deoxidized). The gas barrier layer 'haves at least oxygen permeability and preferably has barrier properties against moisture. The foregoing deoxidized layered body cavity; one embodiment of the enamel film is shown in FIG. The deoxidized laminate film shown in the figure 1 has a deoxidizing layer 11 composed of the above-described deoxidizing resin composition. It’s time to go to the drawer! The surface of the oxygen layer 1 is provided with a gas barrier layer 12 adjacent to the deoxidizing layer 11. The other side is connected to the other side of the deoxidizing layer, and is provided with an oxygen-permeable layer 13 adjacent to the deoxidizing layer 11 of 133482.doc -13.200927282. Further, the outer side of the gas barrier layer 12 is provided with a protective layer 14 of the gas barrier layer 12 adjacent to the gas barrier layer 12. The material of the gas barrier layer 12 in the deoxidized laminate film 1 shown in FIG. 3 can be coated with a stretched nylon (trade name) or a terephthalic acid using, for example, a foil, a polyethylene glycol, a polyethylene terephthalate. Tris- decyl hexamethylenediamine polycondensate formic acid, 2,2-bis(p-aminocyclohexyl)propane-adipate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, nylon MXD (trade name) ), nylon 6 (trade name), nylon 6,6 (trade name), and the like. The oxygen-permeable layer 13 in the deoxidized laminate film 1 shown in Fig. 3 is a layer which is at least permeable to oxygen. The trioxane type cerium oxide is preferably used in combination with a desiccant. The oxygen permeable layer 13 is preferably a layer which is permeable to oxygen and moisture. As the material of the oxygen-permeable layer 13, for example, non-woven fabric, polyethylene (low density polyethylene, ultra low density polyethylene, etc.), extended polypropylene (PP), polypropylene, ethylene propylene copolymer, ethylene propylene rubber, ethylene can be used. An ethyl acrylate copolymer or the like. As the material of the protective layer 14 in the deoxidized laminate film 1 shown in Fig. 3, for example, polyethylene, polypropylene, polyethylene terephthalate (PET), polyamide or the like can be used. Another embodiment of the deoxidized laminate film is shown in FIG. The laminate film 10' shown in the figure is further laminated on the laminate film shown in Fig. 3 to further increase the thickness of the laminate. Specifically, a buffer layer 15 is provided between the deionized layer and the gas barrier layer 12. Further, a gas barrier layer 16 is provided on the outer side of the gas barrier layer 12, that is, between the gas barrier layer 12 and the protective layer 14. 133482.doc 14 200927282 The deoxidized laminate film 10 shown in Fig. 4, the buffer layer 15 is a layer which buffers the physical impact applied from the outer side of the film 10'. As the material of the buffer layer 15, for example, polyethylene, polypropylene, or the like can be used. ❹

The high-gas barrier layer 16 of the deoxidized laminate film 10 shown in Fig. 4 is a layer having a higher ability to block oxygen permeation than the gas barrier layer 12. As the material of the high gas barrier layer 16, various metal tanks such as aluminum foil, vapor-deposited films of various metals including aluminum, and various types of oxides (diox, titanium dioxide, oxidation, oxidation) can be used. Film and the like. The six-layer structure deoxidized laminate film 1 shown in Fig. 4 enhances the cushioning effect on the physical impact applied from the outside of the film as compared with the deoxidized laminate film 10 shown in Fig. 3. At the same time, the invasion of external gases is more difficult. Therefore, the deoxidized laminate film 1 shown in Fig. 14 has a higher added value than the deoxidized laminate film 10 shown in Fig. 4 . The following is a description of a preferred method for producing a trigonal crystal oxide used in the pure agent of the present invention. As a raw material for producing a trigonal crystal oxide: In the middle, an oxonium salt or a hydrate thereof is used (hereinafter, these are referred to as oxygen-containing salts). The oxonium salt is finally calcined under a reducing atmosphere to obtain a target trigonal cerium oxide. The oxonium salt is a compound of ruthenium (10) composed of an anion containing oxygen paired with the „) ion. As an anion containing oxygen, ions, nitrate ions, sulfate ions, gas oxide ions, etc. can be used. The oxyanion-containing compound can be used in a reducing atmosphere, such as hydrogen, using a ratio of dihexahydrate, octahydrate, etc., (iv), and nitrogen oxide 133482.doc 15 200927282: oxonium salt. In the middle of the burning, it can be transferred to the trigonal crystal yttrium oxide. The manufacturing method is excellent in productivity because the step of the i phase is I. Therefore, the (4) is burned, and the lattice can be controlled by adjusting the strip. The degree of oxygen deficiency in the middle. As a money condition, for example, a material having a desired amount of milk: a trigonal crystal of cerium oxide having a desired amount of milk is obtained. In the case of 1050 t, only fH or more is used.

The calcination can be shortened by raising the calcination temperature. However, if the 'increasing the boiling temperature' is more than 105 (for rc, it is necessary to use a ceramic material such as alumina as the core tube of the furnace for cooking, which is not advantageous because of the use of the core material of the ceramic material. There are difficulties in safety and cost. Conversely, even if it is carried out at a low temperature of 1050 〇 below, the desired trigonal cerium oxide can be obtained, which is the advantage of this manufacturing method. At 1050 C In the following calcination, a stainless steel which is a safe and inexpensive material can be used as the core tube. From the point of performing the low-temperature calcination below 1〇5〇, the specific surface area of the obtained digonal crystal yttrium oxide can be enlarged. It is also advantageous. The larger the specific surface area, the larger the contact area with oxygen, and the higher the oxygen absorption rate. As a specific example of the reducing atmosphere, the hydrogen concentration in the atmosphere is preferably 4% by volume or more. In particular, in the case of a carbon monoxide atmosphere, the concentration of one of the carbon oxides in the atmosphere is preferably 4% by volume or more, especially 80% by volume or more. The concentration of acetylene in the medium is preferably 2 vol. / or more, especially 7 〇 volume 0 /. or more. Adding an element which increases the oxygen absorption amount to the trigonal cerium oxide, and replacing it with solid solution 'will contain The oxonium salt is mixed with a compound of the element (such as oxygen 133482.doc -16-200927282), and the mixture is replaced by the above-mentioned ! ^ reduction peening. Stone type cerium oxide, and then: Oxygen salt temporarily produces a trigonal crystal oxygen cut. To rmrr money step can also get two = (four) lower can be burned. As a burning condition, for example, it can be burned for more than 1 hour in C. The knee will be burned. The obtained fluorite-type cerium oxide is also in the first order. The crystallization of the fluorite-type cerium oxide is obtained. The conditions of the reduction sinter are more stringent than those of the above-mentioned baking method. Specifically, the concentration of hydrogen is preferably 50% by volume or more. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, In the case of more temperate conditions, the reduction is carried out. Trigonal crystal oxide decoration. Konjac The oxygen scavenger of the present invention containing the trigonal crystal cerium oxide obtained by the above methods, such as placing it in an atmosphere, absorbing the atmosphere to make oxygen. Therefore, the deoxidizing agent is Products such as foods are sealed and contained in a packaging bag, so that the oxygen in the packaging bag can be removed, and the freshness of the food can be maintained. The atmosphere described here is such that foods, electronic parts, pharmaceuticals, and the like are stored. The atmosphere of the living environment is high. The reduced pressure state of the package (vacuum packaging, etc.) to the pressurized state (pressure sterilization of the sterilization treatment, shape maintenance of the package, etc.). Regarding the temperature, it ranges from 50C (when frozen) to 18〇. (: (sterilization of food)). In addition, the atmosphere is not necessarily air, and it can also be washed in an inert gas such as nitrogen. 133482.doc 200927282 Washing 'The oxygen concentration is decreased β. In addition, it will contain trigonal cerium oxide. The oxygen scavenger of the present invention is introduced into a liquid such as water or water/glutle solution, and can absorb dissolved oxygen in the liquid. Further, the oxygen scavenger of the present invention containing the trigonal cerium oxide can be contacted with the atmosphere. By reducing the concentration of oxygen in the atmosphere, high-purity nitrogen gas can be obtained. In the case of 豸, high-purity nitrogen gas can be obtained by using the apparatus shown in Fig. 5. The apparatus 20 shown in the figure has a compressor that compresses the atmosphere 21 22. The filter 23, the hollow wire film 24, and the deoxidizing device 28 for removing dust in the atmosphere 21. The hollow wire film 24 is formed by bundling hollow wires separating the nitrogen component and the oxygen component in the compressed air. The deaerator 28 is a device for removing a trace amount of oxygen contained in the nitrogen component separated by the hollow coil 24. The deoxidizing device 28 is filled with the oxygen scavenger of the present invention. Compressed air in, by compression The air pipe is sent to the hollow fiber membrane through a filter 23 such as a pre-filter and a particulate filter that removes foreign matter in the compressed air. Between φ of the compressor 22 and the filter 23, drying of the compressed air may be provided. Drying mechanism such as machine. When the pre-filter is used together with the particulate filter, the pre-filter should remove more than 3 μ of the foreign matter present in the compressed air. The particulate filter should remove 0.01 μ or more of the compressed empty milk. Small foreign matter. Under the particulate filter, it can also be equipped with an activated carbon filter with the ability to remove the odor in compressed air. Hollow wire film 24 is made of polyester or polyolefin, and is made up of thousands of suction tubes. The hollow wires are bundled and bundled, and the compressed air is passed through the inside of the hollow wire to utilize the difference in the speed of the hollow film passing through the various gases, so that the nitrogen in the air has the highest content of 133482.doc 18 200927282. The velocity 77 of the gas passing through the hollow wire membrane is a relatively quick release gas and a relatively slow release gas, and the residual gas is nitrogen. In particular, the hollow wire film is intended to be designed. , Most easily through water vapor 'immediately followed by hydrogen and helium, is then - carbon monoxide, oxygen and finally, the most easily through air and nitrogen, are used as the residual gas of the gas through the hardest in #.

The compressed air passes through the gas pipe and reaches the branching portion 25 by the nitrogen gas remaining through the hollow wire film 24. From the branching portion 25, the two piping systems are divided into two. The piping system has a nitrogen gas. The branching pipe li and the second closing pipe 26 are provided with a nitrogen gas second branch pipe L2. The second opening and closing valve 27, the deaerator 28, and the oxygen ampometer 3 are sequentially placed in the second branch pipe L2. By opening the first opening and closing valve 26, the second opening and closing valve 27 is closed, and nitrogen having a purity of about 95% to < 9% is released from the first branch pipe L1. The second opening and closing valve 27 is opened by closing the closing valve 26', and nitrogen having a purity of about 95% to 99.9% is introduced into the deaerator 28. Then, in the deoxygenation unit 28, in addition to: oxygen, a high purity nitrogen gas of about 99.9% or more is obtained. The purity of the high purity nitrogen gas is monitored by an oxygen concentration meter 30. The present invention is not limited to the foregoing embodiment. For example, the trigonal cerium oxide produced by the above various methods has a weak view of the fluorite-type cerium oxide according to the conditions of the reduction calcination: (4). That is, there is a fluorite-type oxidized (four) amount mixed with a trigonal crystal oxide. However, such a trace amount of #石型钸 is contained in the trigonal form of oxidation as permitted by the present invention.实施 [Embodiment] 133482.doc • 19-200927282 Hereinafter, the present invention will be described in further detail by way of examples. However, the scope of the invention is not limited to the embodiment. [Example 1] 75 g of hydrogencarbonate was dissolved in 5 ml of water to prepare an aqueous solution. While admixing the aqueous solution, 5 〇〇 ml of a cerium nitrate aqueous solution of 〇·1 滴 was dropped to carry out reverse neutralization. The resulting precipitate was washed twice with ion-exchanged water to obtain cesium carbonate octahydrate.

The obtained cesium carbonate octahydrate 8 1 · 5 7 g was mixed with about 3 g of post-acid. The mixture was subjected to a reduction treatment (4 〇〇 SCCM flow under hydrogen 1% by gas). The treatment temperature is l00 (rc, the treatment time is 2 hours. Thus, a crystal structure having a trigonal crystal form is obtained, and the solid solution is used, and the yttrium oxide represented by "~" is determined. The crystal structure is determined by XRD measurement. The oxygen content is determined by oxygen absorption described later. The measurement of the amount is obtained by inverse calculation. The average particle size of the trigonal cerium oxide is 2 (four). The SEM image of the trigonal cerium oxide obtained by the three-party cerium oxide in the cerium oxide is 1 相对. [Example 2] In the same manner as in Example 1, except that the conditions of (8) generation and working hours were used, a crystal structure having a trigonal crystal form was obtained, and a gas cylinder represented by Ce2〇2.7 was obtained. The emulsion has a mean particle diameter of 2 μηη. [Example 3] The compound obtained in Example 1 is obtained by the mixture of the acid yttrium octahydrate and the calcium carbonate, and the mixture is obtained. Heat treatment under the emulsion of solid solution dance (_°C, 1 small brocade. The cerium oxide is reduced and calcined (hydrogen 133482.doc -20- 200927282 400 SCCM flow under 100% gas, window 1200 C, 1 hour) Obtaining a crystal structure having a right two-sided crystal form, 〇 ,

The average particle size of cerium oxide is 2 〇 μιη. Crystal I

[Example 4] Except for the conditions of the original calcination, a ruthenium oxide having a trigonal crystal form (4) 2 and a Ce2〇27 was obtained in the same manner as in Example 3 under the conditions of 1 hour. The average particle diameter of the trigonal crystal oxide: "(4) The sem image of the trigonal cerium oxide transmitted as shown in Fig. 7 [Comparative Example 1] The cerium carbonate obtained in Example 1 was used as a raw material, and it was placed under the atmosphere. The treatment was carried out (6 GG C, 1 hour) to obtain an oxidized decoration. The oxidized decoration was subjected to reduction peening (a flow rate of SCCM and a flow rate of 1GG (rc, H, H) in the hydrogen gas to obtain a crystal structure having a fluorite type. The average particle diameter of the cerium oxide obtained by the oxidation of the composition represented by CeOh66 was 2 μm. [Evaluation 1 (oxygen absorption amount)] 氧 The oxygen absorption amount of the oxidized articles obtained in the examples and the comparative examples was measured. The oxygen absorption amount of the obtained cerium oxide was 45, whereas the oxygen absorption amount of cerium oxide obtained in the comparative example was 34. The results show that the trigonal cerium oxide obtained in each example is compared with In the case of the fluorite-type cerium oxide of the example, the oxygen absorption amount is extremely high. [Evaluation 2 (oxygen absorption rate)] The oxidation (IV) oxygen absorption rate obtained in the examples is as shown in Fig. 8. As a result of the above, it can be seen that the oxidized articles of the examples can absorb oxygen for a long time. 'It is also known by appropriately adjusting the roasting reducing conditions, may be 133482.doc • 21 · 200927282 controlling oxygen absorption rate. [Possibility of industrial use]

As described in detail above, according to the present invention, a novel cerium oxide-based deoxidizing agent having a high oxygen absorption amount far exceeding the theoretical limit of the prior cerium oxide having a fluorite-type crystal structure can be provided. The amount of oxygen absorption can be further increased in the case where a specific element is added to cerium oxide. Further, the oxygen scavenger of the present invention does not react in the metal detector, and the product which is packaged together with the food or the like is easily subjected to the inspection of foreign matter such as metal of the metal detector. Further, the oxygen-removing agent of the present invention does not ignite due to the irradiation of microwaves, so that the product packaged together with food or the like can be safely heated in a microwave oven or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the crystal structure of a trigonal cerium oxide. Fig. 2 is a schematic view showing the crystal structure of fluorite-type cerium oxide. Fig. 3 is a schematic view showing an embodiment of the deoxidized laminate of the present invention.

Fig. 4 is a view showing the mode of the deoxidized laminate film of the present invention. Fig. 5 of another embodiment shows a high-purity mode diagram using the oxygen scavenger of the present invention. < Figure 6 is an SEM image of the trigonal cerium oxide obtained in Example 1. Fig. 7 is a SEM image of the trigonal ^, vaporized enthalpy obtained in Example 4. Figure 8 is a graph showing the speed = obtained by the various embodiments. Oxygen absorption of binary crystal oxidation decoration [Main component symbol description] 133482.doc -22. 200927282 ίο 10' 11 12 13 14 15 16 ❹ 21 22 23 24 25 26 27 28 ❿ 30 L1 ' L2 deoxidized laminate film Oxygen buildup film deoxidation layer gas barrier layer oxygen permeation layer protective layer buffer layer height gas barrier layer atmospheric compressor filter hollow line membrane diverging part first opening and closing valve second opening and closing valve deaerator oxygen concentration meter nitrogen first Bifurcated tube nitrogen second branch tube 133482.doc -23-

Claims (1)

200927282 X. Patent application scope · · An oxygen scavenger, characterized by: a crystal structure of Ce Ο , , , and a two-sided crystal form Ke2〇3-x (x system 0 or more, less than 2. Item! The deoxidizer, which is not the cerium oxide. Less than 1) means that the oxygen is cut. One is greater than. 3. The oxygen scavenger of item 1, wherein an element which increases the oxygen absorption amount of the oxidized layer is added to the cerium oxide. They are more oxidized. 4. The deoxygenated body will form a de-emulsion in a bag-like package of the requested 丨❹ 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容 收容The permeable resin is the deoxidizing agent of claim 1 and the deoxidizing resin composition of claim 5, which has a shape of a pellet, a film, or a disk. , 7·: = laminated film 'based on the deoxidizing resin assembly barrier of claim 5】 One side of the oxygen layer, a gas barrier with a gas barrier layer is deposited on the other side of the deoxidation layer, and the layer has oxygen Permeable oxygen is easily transmitted through the layer. 8. The deoxidized laminate film of item 7 is characterized in that between the deoxidation layer and the gas barrier layer, a layer is accumulated to have a physical impact on the outer side of the gas barrier layer, and The step layer has a high gas barrier layer that has a higher ability to block oxygen permeation than the gas barrier layer. A method for producing an oxidized ruthenium, wherein the ruthenium oxide has a crystal structure of a trigonal crystal form, and is Ce2〇3_x (x system 〇 or more, less than 1). The hydrate is calcined at a temperature above 10 ° C under the original atmosphere of 133482.doc 200927282. 10. A method for producing cerium oxide, wherein the cerium oxide has a crystal structure of a trigonal crystal form and is represented by Ce203-X (x-based 0 or more and less than 1), and the method for producing cerium oxide includes Ce02 The step of calcining the cerium oxide at 1200 ° C or higher in a reducing atmosphere. 133482.doc