JP5294161B2 - Moisture resistant oxygen scavenger - Google Patents
Moisture resistant oxygen scavenger Download PDFInfo
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- JP5294161B2 JP5294161B2 JP2012011318A JP2012011318A JP5294161B2 JP 5294161 B2 JP5294161 B2 JP 5294161B2 JP 2012011318 A JP2012011318 A JP 2012011318A JP 2012011318 A JP2012011318 A JP 2012011318A JP 5294161 B2 JP5294161 B2 JP 5294161B2
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- oxygen scavenger
- oxygen
- iron powder
- high humidity
- package
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- 229940123973 Oxygen scavenger Drugs 0.000 title claims abstract description 71
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000005871 repellent Substances 0.000 claims abstract description 16
- 230000002940 repellent Effects 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 15
- 150000005309 metal halides Chemical class 0.000 claims abstract description 15
- 239000005022 packaging material Substances 0.000 claims abstract description 15
- -1 alkali metal salt Chemical class 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 235000013305 food Nutrition 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- 229910001622 calcium bromide Inorganic materials 0.000 description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229940114926 stearate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000021186 dishes Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical group [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical group [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Packages (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Description
本発明は耐湿性を有する脱酸素剤に関する。詳しくは見かけ容積あたりの酸素吸収能力が大きく、高湿度下においても長期間にわたり酸素吸収性能を維持できる改良された脱酸素剤組成物、脱酸素剤包装体及び脱酸素方法に関するものである。 The present invention relates to an oxygen scavenger having moisture resistance. More specifically, the present invention relates to an improved oxygen scavenger composition, oxygen scavenger package, and oxygen scavenging method that have a large oxygen absorbing capacity per apparent volume and can maintain oxygen absorbing performance over a long period of time even under high humidity.
鉄粉の酸化反応を利用した脱酸素剤は、食品などの物品と共にガスバリア性容器に密封収納し容器内の酸素を除去することで、食品などの物品の品質や鮮度を保持するために既に広く利用されている。この市販の脱酸素剤は、水分共存下における鉄粉と酸素との反応を利用したものであり、鉄粉の酸化反応促進のために、通常、塩化ナトリウムや塩化カルシウムなどのハロゲン化金属及び酸素の吸収速度・量の増加および取り扱いの面から無機フィラーが添加された脱酸素剤が特許文献１に開示されている。 An oxygen scavenger using the oxidation reaction of iron powder is already widely used in order to maintain the quality and freshness of food and other items by sealing and storing it in a gas barrier container together with items such as food and removing oxygen in the container. It's being used. This commercially available oxygen scavenger uses a reaction between iron powder and oxygen in the presence of moisture. In order to promote the oxidation reaction of iron powder, metal halides such as sodium chloride and calcium chloride and oxygen are usually used. Patent Document 1 discloses an oxygen scavenger to which an inorganic filler is added from the viewpoint of an increase in the absorption rate / amount of water and handling.
従来、鉄粉とハロゲン化金属及び無機フィラーからなる脱酸素剤を水分含有量が多く水分活性の高い食品に適用した際に、食品中の水分が脱酸素剤包装体中に移行して脱酸素剤表面が水で覆われることで脱酸素反応が停止する問題点があった。この問題を解消するために、シリカ又はゼオライトなどからなる無機フィラーを多量に配合して水分を分散させることで脱酸素能力を保持させる方法が行われている。しかし、無機フィラーを添加することにより能力保持性は改善されるが、酸素吸収量当たりの脱酸素剤組成物の見かけ使用容量が大きくなり、脱酸素剤包装体とした場合の包装材料の寸法が大きくなり、コストアップになるといった問題点があった。 Conventionally, when an oxygen scavenger consisting of iron powder, metal halide and inorganic filler is applied to a food with a high water content and high water activity, the water in the food is transferred into the oxygen scavenger package and deoxygenated. There was a problem that the deoxygenation reaction was stopped by covering the surface of the agent with water. In order to solve this problem, a method of maintaining a deoxygenation capacity by blending a large amount of an inorganic filler made of silica or zeolite and dispersing water is performed. However, the ability retention is improved by adding an inorganic filler, but the apparent use capacity of the oxygen scavenger composition per oxygen absorption amount increases, and the dimensions of the packaging material in the case of an oxygen scavenger package are reduced. There was a problem that it became large and cost increased.
本発明は従来技術における脱酸素剤の上記課題を解決し、脱酸素剤組成物の単位体積あたりの酸素吸収能力が高く、高湿度雰囲気下においても長期間にわたり酸素吸収性能を維持できる脱酸素剤を提供することを目的とする。 The present invention solves the above problems of the deoxidizer in the prior art, higher oxygen absorption capacity per unit volume of the oxygen scavenger composition, deoxygenated that also maintain the oxygen absorbing performance over a long period of time under a high humidity atmosphere The purpose is to provide an agent.
本発明者らは上記問題に鑑み鋭意研究を重ねた結果、撥水剤を添加した脱酸素剤組成物を用いることで高湿度下で使用した場合でも、脱酸素剤包装体中に侵入した水分が脱酸素剤組成物上で水滴状となり脱酸素剤自体を覆うことなく長期間にわたり脱酸素能力を維持できることを見出し、本発明に到達するに至った。 As a result of intensive studies in view of the above problems, the present inventors have found that moisture that has penetrated into the oxygen scavenger package even when used under high humidity by using an oxygen scavenger composition to which a water repellent is added. Has been found to be in the form of water droplets on the oxygen scavenger composition and can maintain the oxygen scavenging ability over a long period of time without covering the oxygen scavenger itself, and has reached the present invention.
本発明は、鉄粉１００重量部、ハロゲン化金属０．０１〜２０重量部及び撥水剤０．０１〜５重量部を添加した脱酸素剤組成物に関する。撥水剤としては、金属石鹸が好ましく、金属石鹸としては脂肪酸のアルカリ金属塩及び脂肪酸のアルカリ土類金属塩が好ましく、特に脂肪酸のアルカリ土類金属塩が好ましい。中でもステアリン酸のアルカリ金属塩及びアルカリ土類金属塩が好ましく、ステアリン酸のアルカリ土類金属塩がより好ましい。
また、本発明は、前記脱酸素剤組成物を、無機フィラーを配合することなく通気性包装材料で包装してなる高湿度用脱酸素剤包装体、及び、この脱酸素剤包装体を使用して、７０〜１００％ＲＨの高湿度下のガスバリア性容器内空間を脱酸素する方法に関する。
The present invention relates to an oxygen scavenger composition to which 100 parts by weight of iron powder, 0.01 to 20 parts by weight of a metal halide and 0.01 to 5 parts by weight of a water repellent are added. As the water repellent, a metal soap is preferable. As the metal soap, an alkali metal salt of a fatty acid and an alkaline earth metal salt of a fatty acid are preferable, and an alkaline earth metal salt of a fatty acid is particularly preferable. Of these, alkali metal salts and alkaline earth metal salts of stearic acid are preferable, and alkaline earth metal salts of stearic acid are more preferable.
In addition, the present invention uses a high-humidity oxygen absorber package formed by packaging the oxygen absorber composition with a breathable packaging material without blending an inorganic filler, and the oxygen absorber package. The present invention relates to a method for deoxygenating a space in a gas barrier container under a high humidity of 70 to 100% RH.
本発明の脱酸素剤組成物は、無機フィラーを添加しなくとも高湿度下における酸素吸収能力を維持することができるので、７０〜１００％ＲＨ、特に飽和又は飽和に近い高湿度雰囲気で使用されても酸素吸収性能を維持する。また、無機フィラーの配合を省略した場合には、脱酸素剤組成物の酸素吸収量当たりの見かけ使用容量が大きくなることもない。 Since the oxygen scavenger composition of the present invention can maintain the oxygen absorption capacity under high humidity without adding an inorganic filler, it is used in a high humidity atmosphere of 70 to 100% RH, particularly saturated or close to saturation. Even oxygen absorption performance is maintained. Further, when the blending of the inorganic filler is omitted , the apparent usage capacity per oxygen absorption amount of the oxygen scavenger composition does not increase.
本発明の脱酸素剤包装体は、高湿度下でも長期間にわたり酸素吸収性能を発揮し、また医薬品、食品などを長期間に亘って保存できる。高湿度状態での酸素吸収性能は無機フィラーを配合しなくても発揮することができる。無機フィラーの配合を省略することにより、同じ酸素吸収量を発揮する脱酸素剤組成物の見かけ容積が従来の脱酸素剤組成物（無機フィラーを配合）の見かけ容積より減少し、コンパクトにでき、その結果、脱酸素剤包装体とした時の包装材料の使用量を削減することができる。 The oxygen scavenger package of the present invention exhibits oxygen absorption performance over a long period of time even under high humidity, and can store medicines, foods, etc. over a long period of time. The oxygen absorption performance in a high humidity state can be exhibited without blending an inorganic filler. By omitting the blending of the inorganic filler, the apparent volume of the oxygen scavenger composition that exhibits the same amount of oxygen absorption is reduced from the apparent volume of the conventional oxygen scavenger composition (blending the inorganic filler), making it compact. As a result, the amount of packaging material used when the oxygen scavenger package is obtained can be reduced.
以下に、本発明の方法について詳細に説明する。
脱酸素剤の主剤となる鉄粉は、酸化されていない鉄が表面に露出したものであれば特に限定されるものではなく、還元鉄粉、電解鉄粉、噴霧鉄粉などが好適に用いられる。その他、鋳鉄などの粉砕物、切削品などを用いることができる。鉄粉は、酸素との接触を良好にするために通常平均粒径１ｍｍ以下、好ましくは５００μｍ以下、より好ましくは１００μｍ以下の鉄粉が用いられる。
ハロゲン化金属は、鉄粉の酸化を助ける酸化促進剤であり、アルカリ金属又はアルカリ土類金属のハロゲン化物が用いられ、塩化ナトリウム、塩化カルシウム、塩化マグネシウム、臭化ナトリウム、臭化カルシウム等が例示される。
鉄粉に対するハロゲン化金属の使用量は鉄粉１００重量部に対し、０．０１〜２０重量部の範囲で使用される。
Hereinafter, the method of the present invention will be described in detail.
The iron powder as the main component of the oxygen scavenger is not particularly limited as long as unoxidized iron is exposed on the surface, and reduced iron powder, electrolytic iron powder, sprayed iron powder, etc. are preferably used. . In addition, pulverized products such as cast iron, cut products, and the like can be used. As the iron powder, an iron powder having an average particle diameter of 1 mm or less, preferably 500 μm or less, more preferably 100 μm or less is used in order to improve contact with oxygen.
Metal halides are oxidation promoters that help oxidize iron powder. Alkali metal or alkaline earth metal halides are used, and examples include sodium chloride, calcium chloride, magnesium chloride, sodium bromide, and calcium bromide. Is done.
The usage-amount of the metal halide with respect to iron powder is used in 0.01-20 weight part with respect to 100 weight part of iron powder.
一般に高湿度下で脱酸素剤包装体を用いた場合、脱酸素剤包装体の通気性包装材料（包材）を通し、脱酸素剤包装体内への水蒸気透過による水分移行が起こり、鉄粉の表面が水分で覆われ酸素吸収能力の低下が起こる。しかし、本発明では、撥水剤を添加することで移行してきた水分が鉄粉表面から弾かれ、水滴状となることなどにより、水分の脱酸素剤表面への広がりが抑えられ脱酸素性能の低下を防ぐことが可能となる。 In general, when an oxygen scavenger package is used under high humidity, moisture transfer occurs due to water vapor permeation into the oxygen scavenger package through the breathable packaging material (packaging material) of the oxygen scavenger package. The surface is covered with moisture and the oxygen absorption capacity is reduced. However, in the present invention, the moisture that has been transferred by adding a water repellent is repelled from the surface of the iron powder and becomes water droplets. It is possible to prevent the decrease.
脱酸素能力保持性を向上させるために加える撥水剤としては、撥水機能を保有する物質であり、特に金属石鹸が好ましい。 The water repellent added to improve the deoxygenation ability retention is a substance having a water repellent function, and metal soap is particularly preferable.
金属石鹸としては、脂肪酸、ロジン酸、ナフテン酸のアルカリ金属塩又はアルカリ土類金属塩が好ましく、特に脂肪酸のアルカリ土類金属塩が好ましい。金属石鹸に用いる脂肪酸としては、酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸及びステアリン酸が例示される。中でもステアリン酸バリウム、ステアリン酸カリウム、ステアリン酸ナトリウム、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸マグネシウムなどのステアリン酸アルカリ金属塩及びステアリン酸アルカリ土類金属塩が好ましい。これらの中で特にステアリン酸カルシウム及びステアリン酸マグネシウムなどのステアリン酸アルカリ土類金属塩は、添加した際の能力保持性能向上効果が大きく、安全性も高く好ましい。また、これらは単体で用いても良いし、複合して用いても良い。 As the metal soap, an alkali metal salt or an alkaline earth metal salt of fatty acid, rosin acid, or naphthenic acid is preferable, and an alkaline earth metal salt of a fatty acid is particularly preferable. Examples of fatty acids used in metal soaps include butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. Of these, alkali metal stearate and alkaline earth metal stearate such as barium stearate, potassium stearate, sodium stearate, calcium stearate, zinc stearate, aluminum stearate and magnesium stearate are preferable. Among these, alkaline earth metal stearates such as calcium stearate and magnesium stearate are particularly preferable because they have a large effect of improving ability retention performance when added and have high safety. These may be used alone or in combination.
撥水剤は、用いる撥水剤、適用される期間、適用される保存物品の保有する水分量により適宜選ばれるが、少なすぎると効果が小さく、鉄粉１００重量部に対して０．０１〜５重量部、好ましくは０．０５〜１重量部添加される。添加量は、添加量が多すぎると鉄粉が脱酸素に必要な水分を有効に利用することが出来なくなり酸素吸収速度が低下するとともにコストアップとなり好ましくない。 The water repellent is appropriately selected depending on the water repellent used, the application period, and the amount of water held by the applied storage article. However, if the amount is too small, the effect is small, and 0.01 to 100 parts by weight of iron powder. 5 parts by weight, preferably 0.05 to 1 part by weight is added. If the addition amount is too large, the iron powder cannot effectively use the water necessary for deoxygenation, and the oxygen absorption rate is lowered and the cost is increased.
以上のように、本発明の脱酸素剤組成物は、主剤の鉄粉と酸化促進剤であるハロゲン化金属及び撥水剤からなる。鉄粉、ハロゲン化金属及び撥水剤は、組成物として通気性包装材料により包装される。例えば、鉄粉、ハロゲン化金属、撥水剤を機械的に混合する方法、鉄粉にハロゲン化金属を付着せしめた後に撥水剤を混合する方法、鉄粉にハロゲン化金属と撥水剤を付着せしめる方法等、結果的に鉄粉、ハロゲン化金属及び撥水剤が充分に混合される方法により製造できる。 As described above, the oxygen scavenger composition of the present invention comprises the main component iron powder, the metal halide as the oxidation accelerator, and the water repellent. The iron powder, metal halide and water repellent are packaged by a breathable packaging material as a composition. For example, a method of mechanically mixing iron powder, metal halide and water repellent, a method of mixing a water repellent after attaching a metal halide to iron powder, and a metal halide and water repellent to iron powder. As a result, it can be produced by a method in which iron powder, metal halide and water repellent are sufficiently mixed.
本発明の脱酸素剤組成物には上記の鉄粉、ハロゲン化金属の他に必要に応じて添加剤を加える事ができる。例えば、臭気防止、粉塵抑制、対マイクロ波耐性、水素発生抑制などを目的とし、シリカ、アルミナ、活性炭、重曹などを適宜混合する事ができる。 In addition to the above iron powder and metal halide, an additive may be added to the oxygen scavenger composition of the present invention as necessary. For example, silica, alumina, activated carbon, sodium bicarbonate, or the like can be appropriately mixed for the purpose of preventing odor, suppressing dust, resistance to microwaves, suppressing hydrogen generation, and the like.
但し、これらの添加剤を添加混合した場合は、酸素吸収可能量当たりの脱酸素剤包装体のサイズが大きくなり、脱酸素剤包装体を構成する通気性包装材料の使用量が増大することになるので、添加量は必要最小限とする。添加剤の総添加量は、鉄粉とハロゲン化金属の合計量１００重量部に対し、０〜３５重量部が好ましく、０〜２５重量部の添加量がより好ましい。 However, when these additives are added and mixed, the size of the oxygen scavenger packaging body per oxygen-absorbable amount increases, and the amount of breathable packaging material constituting the oxygen scavenger packaging body increases. Therefore, the amount added is kept to the minimum necessary. The total amount of additives is preferably 0 to 35 parts by weight, more preferably 0 to 25 parts by weight, based on 100 parts by weight of the total amount of iron powder and metal halide.
高湿度条件で使用する場合、従来の脱酸素剤組成物には、酸素吸収性能の維持のために、シリカ又はアルミナなどの無機フィラーが添加されている。しかし、本発明においては、高湿度条件で使用する場合であっても、酸素吸収性能が維持されるので、シリカ又はアルミナなどの無機フィラーの添加を省略することができ、酸素吸収量当たりの脱酸素剤組成物の見かけ容量を小さくすることができる。 When used under high humidity conditions, an inorganic filler such as silica or alumina is added to the conventional oxygen scavenger composition in order to maintain oxygen absorption performance. However, in the present invention, even when used under high humidity conditions, the oxygen absorption performance is maintained, so the addition of an inorganic filler such as silica or alumina can be omitted, and the desorption per oxygen absorption amount can be omitted. The apparent capacity of the oxygen agent composition can be reduced.
本発明に用いられる脱酸素剤組成物は、通気性包装材料を一部又は全面に使用して充填包装し、脱酸素剤包装体として使用することができる。その際に用いられる通気性包装材料としては、酸素吸収効果を十分に得るためにできるだけ通気性の高い包装材料が望ましい。たとえば、和紙、洋紙、レーヨン紙などの紙類、パルプ、セルロース、合成樹脂からの繊維などの各種繊維類を用いた不織布、プラスチックフィルムまたはその穿孔物など、あるいは炭酸カルシウムなどを添加した後延伸したマイクロポーラスフィルムなど、さらにはこれらから選ばれる２種以上を積層したものなどを挙げることができる。通気性包装材料としては、ポリエチレンからなる不織布、あるいは不織布とマイクロポーラスフィルムとの積層物が好ましい。 The oxygen scavenger composition used in the present invention can be filled and packaged using part or the entire surface of a breathable packaging material and used as an oxygen scavenger package. The breathable packaging material used at that time is desirably a packaging material having as high a breathability as possible in order to obtain a sufficient oxygen absorption effect. For example, non-woven fabrics using various fibers such as Japanese paper, western paper, rayon paper, pulp, cellulose, fibers from synthetic resins, plastic films or perforated materials thereof, or stretching after adding calcium carbonate or the like. Examples thereof include a microporous film, and further a laminate of two or more selected from these. As the breathable packaging material, a nonwoven fabric made of polyethylene or a laminate of a nonwoven fabric and a microporous film is preferable.
本発明の脱酸素剤組成物は、無機フィラーを配合することなく通気性包装材料で包装して高湿度用脱酸素剤包装体とすることができる。かかる脱酸素剤包装体は、７０〜１００％ＲＨ、特に飽和又は飽和に近い高湿度下にあるガスバリア性容器内空間を良好に脱酸素するために使用することができる。 The oxygen scavenger composition of the present invention can be packaged with a breathable packaging material without blending an inorganic filler to form a high-humidity oxygen scavenger package. Such an oxygen scavenger package can be used to satisfactorily deoxygenate a space in a gas barrier container under high humidity of 70 to 100% RH, particularly saturated or nearly saturated.
本発明の脱酸素剤組成物または本発明の脱酸素剤組成物を通気性包装材料により充填包装した脱酸素剤包装体を、保存物品とともにガスバリア性容器に密封して使用することができる。用いるガスバリア性容器の形状、材質は、例えば、金属缶、ガラス瓶、プラスティック容器、袋など、密封可能で実質的にガスバリア性を有していれば制限されない。又、ポリエチレンテレフタレート／アルミ蒸着／ポリエチレン、延伸ポリプロピレン／ポリビニルアルコール／ポリエチレン、ポリ塩化ビニリデンコート延伸ナイロン／ポリエチレンなどの多層シートやフィルム、ナイロン系の共押出し多層シートやフィルムに例示され
る、酸素透過度０．０５〜２０ｍｌ／ｍ2・２４ｈｒ・ａｔｍ（２５℃、５０％ＲＨ）の積層体から成る包装容器、袋が簡便に使用できる。
The oxygen scavenger composition of the present invention or the oxygen scavenger package in which the oxygen scavenger composition of the present invention is filled and packaged with a breathable packaging material can be used by being sealed in a gas barrier container together with a storage article. The shape and material of the gas barrier container to be used are not limited as long as the gas barrier container can be sealed and substantially has gas barrier properties, such as a metal can, a glass bottle, a plastic container, and a bag. Also, oxygen permeability, exemplified by multilayer sheets and films such as polyethylene terephthalate / aluminum deposition / polyethylene, stretched polypropylene / polyvinyl alcohol / polyethylene, polyvinylidene chloride-coated stretched nylon / polyethylene, and nylon coextruded multilayer sheets and films. Packaging containers and bags made of a laminate of 0.05 to 20 ml / m 2 · 24 hr · atm (25 ° C., 50% RH) can be used conveniently.
本発明の脱酸素剤組成物は、７０〜１００％ＲＨの高湿度下でも好適に脱酸素する。特に、本発明の脱酸素剤組成物は、耐湿性の要求される用途に好適に使用される。例えば、餅、米飯、ハム、総菜などの食品の長期保存に好適である。 The oxygen scavenger composition of the present invention suitably deoxygenates even under high humidity of 70 to 100% RH. In particular, the oxygen scavenger composition of the present invention is suitably used for applications requiring moisture resistance. For example, it is suitable for long-term storage of foods such as rice cakes, cooked rice, ham, and prepared dishes.
以下に実施例を挙げ、本発明をより具体的に説明する。但し本発明はこれら実施例に制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
実施例１
塩化カルシウム０．５ｇを水７ｍｌに溶解し、この水溶液を鉄粉（平均粒径５０μｍ）１００ｇに混合しながら加え乾燥させることによって塩化カルシウムが付着した鉄粉を得、これにステアリン酸カルシウム粉末（堺化学工業（株）製、粒径７５μｍ以下の粒子の占有率９９ｗｔ％）を０．２ｇ添加し十分に混合することで脱酸素剤組成物を調製した。得られた脱酸素剤組成物１．８０ｇを、片面にＰＥＴ／ＬＬＤＰＥ／ＥＶＡからなる非通気性積層フィルム、片面にポリエチレン製不織布からなる通気性積層フィルムを用いた通気面が長辺４０ｍｍ×短辺３７ｍｍの長方形小袋に四方シール充填して脱酸素剤包装体とした。
Example 1
0.5 g of calcium chloride is dissolved in 7 ml of water, and this aqueous solution is mixed with 100 g of iron powder (average particle size 50 μm) and dried to obtain iron powder having calcium chloride attached thereto. An oxygen scavenger composition was prepared by adding 0.2 g of Chemical Industry Co., Ltd. product (occupancy ratio of 99 wt% of particles having a particle size of 75 μm or less) and mixing well. 1.80 g of the obtained oxygen scavenger composition was mixed with a non-breathable laminated film made of PET / LLDPE / EVA on one side and a breathable laminated film made of a polyethylene nonwoven fabric on one side with a long side of 40 mm × short A rectangular sachet with a side of 37 mm was filled with a four-sided seal to form an oxygen scavenger package.
この脱酸素剤包装体を用いて、高湿度環境で脱酸素剤への水分移行処理を行い、その後の酸素吸収能力の保持を評価することにより、脱酸素剤の能力保持性を評価した。
水１０ｍｌを含浸した加湿用の含水綿、前記脱酸素剤包装体を１３０ｍｍ×１４０ｍｍのガスバリア袋（ポリ塩化ビニリデンコート延伸ナイロン／ポリエチレンのラミネートフィルム）に入れ、両者を樹脂製のネットで隔離し、５ｍｌの空気とともに密封した。この密封した袋（以下、水分移行処理袋）を３５℃の恒温槽中に５日、７日または９日間保管し、飽和湿度条件下で脱酸素剤に水分移行を起こさせた。密封した水分移行処理袋を開封し、この水分移行処理を行った脱酸素剤包装体を取り出し、酸素濃度２％に調整した酸素と窒素との混合ガス５００ｍｌと共に別のガスバリア袋に密封し、５℃の恒温槽中に放置し、２４時間後のこのガスバリア袋（以下、密封ガスバリア袋）内の酸素濃度を測定し飽和湿度下での水分移行処理前後での酸素吸収能力保持性を評価した。結果を表１に示す。
本発明の脱酸素剤は、高湿度雰囲気に５日間以上放置した後も、いずれも２４時間以内の完全な脱酸素（密封ガスバリア袋内酸素濃度０．０１％以下）を達成し、酸素吸収能力を保持していることが確認された。
また、調製した脱酸素剤組成物表面に少量の水を滴下すると、滴下した水が水滴になることが観察された。
Using this oxygen scavenger package, moisture transfer treatment to the oxygen scavenger was performed in a high humidity environment, and the subsequent retention of oxygen absorbing capacity was evaluated to evaluate the capacity retention of the oxygen scavenger.
Moisturized wet cotton impregnated with 10 ml of water, the oxygen scavenger package is placed in a 130 mm × 140 mm gas barrier bag (polyvinylidene chloride-coated stretched nylon / polyethylene laminate film), and both are separated by a resin net, Sealed with 5 ml of air. This sealed bag (hereinafter referred to as a moisture transfer treatment bag) was stored in a thermostatic bath at 35 ° C. for 5, 7, or 9 days to cause moisture transfer to the oxygen scavenger under saturated humidity conditions. The sealed moisture transfer treatment bag is opened, the oxygen scavenger package subjected to the moisture transfer treatment is taken out, sealed in another gas barrier bag together with 500 ml of a mixed gas of oxygen and nitrogen adjusted to an oxygen concentration of 2%, and 5 The sample was allowed to stand in a thermostat at 0 ° C., and the oxygen concentration in this gas barrier bag (hereinafter referred to as a sealed gas barrier bag) after 24 hours was measured to evaluate the oxygen absorption capacity retention before and after the moisture transfer treatment under saturated humidity. The results are shown in Table 1.
The oxygen scavenger of the present invention achieves complete oxygen scavenging within 24 hours (oxygen concentration within the sealed gas barrier bag is 0.01% or less) even after being left in a high humidity atmosphere for 5 days or more. It was confirmed that
Moreover, when a small amount of water was dropped on the prepared oxygen scavenger composition surface, it was observed that the dropped water became water droplets.
実施例２〜５
実施例１で使用したステアリン酸カルシウムをそれぞれステアリン酸マグネシウム、ステアリン酸バリウム、パルミチン酸カリウム、ラウリン酸ナトリウムに替えた以外は実施例１と同様に脱酸素剤及び脱酸素剤包装体を作製した。作製した脱酸素剤包装体を実施例１と同様の試験を行い、酸素吸収能力保持性の評価を行った。結果を表１に示す。
実施例１と同様に作製した脱酸素剤組成物の表面に少量の水を滴下すると、滴下した水は、何れも水滴となることが観察された。
Examples 2-5
An oxygen scavenger and oxygen scavenger package were prepared in the same manner as in Example 1 except that the calcium stearate used in Example 1 was replaced with magnesium stearate, barium stearate, potassium palmitate and sodium laurate, respectively. The produced oxygen scavenger package was tested in the same manner as in Example 1 to evaluate the oxygen absorption capacity retention. The results are shown in Table 1.
When a small amount of water was dropped on the surface of the oxygen scavenger composition produced in the same manner as in Example 1, it was observed that all of the dropped water became water droplets.
実施例６〜８
実施例１で使用した塩化カルシウムを同量の臭化カルシウムに替え、ステアリン酸カルシウムの添加量を０．０５ｇ、０．５ｇ又は１．０ｇに替えた以外は実施例１と同様に脱酸素剤及び脱酸素剤包装体を作製した。作製した脱酸素剤包装体を実施例１と同様の試験を行い、酸素吸収能力保持性の評価を行った。結果を表１に示す。
実施例１と同様に作製した脱酸素剤組成物の表面に少量の水を滴下すると、滴下した水は、水滴となることが観察された。
Examples 6-8
In the same manner as in Example 1 except that the calcium chloride used in Example 1 was replaced with the same amount of calcium bromide and the addition amount of calcium stearate was changed to 0.05 g, 0.5 g, or 1.0 g, and An oxygen scavenger package was prepared. The produced oxygen scavenger package was tested in the same manner as in Example 1 to evaluate the oxygen absorption capacity retention. The results are shown in Table 1.
When a small amount of water was dropped on the surface of the oxygen scavenger composition produced in the same manner as in Example 1, it was observed that the dropped water became water droplets.
比較例１
実施例１で使用したステアリン酸カルシウムを用いなかった以外は実施例１と同様に脱酸素剤及び脱酸素剤包装体を作製した。作製した脱酸素剤包装体を実施例１と同様の試験を行い、酸素吸収能力保持性の評価を行った。結果を表１に示す。水分移行処理期間が７日以上で酸素吸収能力が低下していた。
実施例１と同様に作製した脱酸素剤組成物の表面に少量の水を滴下すると、滴下した水は、そのまま脱酸素剤組成物の内部に染みて広がっていくことが観察された。
Comparative Example 1
An oxygen scavenger and oxygen scavenger package were prepared in the same manner as in Example 1 except that the calcium stearate used in Example 1 was not used. The produced oxygen scavenger package was tested in the same manner as in Example 1 to evaluate the oxygen absorption capacity retention. The results are shown in Table 1. The oxygen absorption capacity was reduced when the moisture transfer treatment period was 7 days or longer.
When a small amount of water was dropped on the surface of the oxygen scavenger composition produced in the same manner as in Example 1, it was observed that the dripped water permeated into the oxygen scavenger composition as it was and spread.
実施例９
以下の実装試験を行った。
ガスバリア袋（ポリ塩化ビニリデンコート延伸ナイロン／ポリエチレンのラミネートフィルム）２２０ｍｍ×３３０ｍｍに入れた炊飯米１０５０ｇ上に実施例１と同様にして調製した脱酸素剤包装体１包を直接載せ、密封した。この密封容器を２５℃で３０日間保管した後、密封容器内酸素濃度を測定したところ０．１％未満であり、炊飯米の風味は良好であった。脱酸素剤包装体を取り出し調べたところ、錆の発生は認められなかった。脱酸素剤包装体と接触していた炊飯米の部分には、外観上の異常は認められず、ロダンカリ法による試験を行ったが鉄の反応は検出されなかった。
Example 9
The following mounting tests were conducted.
One oxygen scavenger package prepared in the same manner as in Example 1 was directly placed on 1050 g of cooked rice in a gas barrier bag (polyvinylidene chloride-coated stretched nylon / polyethylene laminate film) 220 mm × 330 mm and sealed. After this sealed container was stored at 25 ° C. for 30 days, the oxygen concentration in the sealed container was measured and found to be less than 0.1%, and the flavor of the cooked rice was good. When the oxygen scavenger package was taken out and examined, generation of rust was not observed. No abnormal appearance was observed in the portion of the cooked rice that had been in contact with the oxygen scavenger package, and a test by the Rodankari method was performed, but no iron reaction was detected.
Claims (2)
７０〜１００％ＲＨの高湿度用脱酸素剤包装体。 An oxygen scavenger composition in which 100 parts by weight of iron powder, 0.01 to 20 parts by weight of a metal halide and 0.01 to 5 parts by weight of a metal soap as a water repellent is mixed, is air permeable without blending an inorganic filler . A package of oxygen absorber for high humidity of 70 to 100% RH, which is packaged with a packaging material.
請求項１記載の７０〜１００％ＲＨの高湿度用脱酸素剤包装体。 The metal soap is an alkali metal salt or an alkaline earth metal salt of a fatty acid,
The oxygen-absorbing agent package for high humidity of 70 to 100% RH according to claim 1.
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| JP2012011318A JP5294161B2 (en) | 2012-01-23 | 2012-01-23 | Moisture resistant oxygen scavenger |
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| JP2012011318A JP5294161B2 (en) | 2012-01-23 | 2012-01-23 | Moisture resistant oxygen scavenger |
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| JP2004141275A Division JP4942289B2 (en) | 2004-05-11 | 2004-05-11 | Moisture resistant oxygen scavenger |
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| JP3132015B2 (en) * | 1991-01-10 | 2001-02-05 | 三菱瓦斯化学株式会社 | Oxygen absorbent molded article and method for producing the same |
| JPH05177130A (en) * | 1991-12-26 | 1993-07-20 | Toagosei Chem Ind Co Ltd | Oxygen absorbent |
| JP3212912B2 (en) * | 1997-07-15 | 2001-09-25 | 東亜合成株式会社 | Oxygen absorbent and its manufacturing method |
| JP2001037456A (en) * | 1999-07-27 | 2001-02-13 | Mitsubishi Gas Chem Co Inc | Preservation of product of low moisture content |
| JP2001300306A (en) * | 2000-04-28 | 2001-10-30 | Kureha Chem Ind Co Ltd | Carbon dioxide adsorbent |
| JP2003340274A (en) * | 2002-05-23 | 2003-12-02 | Mitsubishi Gas Chem Co Inc | Improved oxygen scavenger composition |
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