JP2008212838A - Oxygen absorbent - Google Patents
Oxygen absorbent Download PDFInfo
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- JP2008212838A JP2008212838A JP2007054256A JP2007054256A JP2008212838A JP 2008212838 A JP2008212838 A JP 2008212838A JP 2007054256 A JP2007054256 A JP 2007054256A JP 2007054256 A JP2007054256 A JP 2007054256A JP 2008212838 A JP2008212838 A JP 2008212838A
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- Prior art keywords
- oxygen absorbent
- oxygen
- stainless steel
- weight
- organic compound
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000001301 oxygen Substances 0.000 title claims abstract description 80
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 80
- 239000002250 absorbent Substances 0.000 title claims abstract description 59
- 230000002745 absorbent Effects 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 22
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 20
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000010935 stainless steel Substances 0.000 claims abstract description 15
- 238000007689 inspection Methods 0.000 claims abstract description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000013305 food Nutrition 0.000 abstract description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal salts Chemical class 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 4
- 238000011179 visual inspection Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 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
- 238000009826 distribution Methods 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
本発明は、密封包装内又は密封容器内に食品と共に封入して用いる酸素吸収剤に関する。 The present invention relates to an oxygen absorbent that is used in a sealed package or a sealed container together with food.
食品分野では、食品の保存性改善や酸化等による変質防止を目的として、従来から酸素吸収剤が利用されている。食品分野で利用されている酸素吸収剤には、鉄を主剤とする無機系のものと還元性有機化合物を主剤とする有機系のものが知られ、食品の種類や目的に応じてこれらの酸素吸収剤が使い分けられている。 In the food field, oxygen absorbers are conventionally used for the purpose of improving the storage stability of foods and preventing deterioration due to oxidation or the like. Oxygen absorbers used in the food field are known to be inorganic based on iron and organic based on reducing organic compounds. These oxygen absorbers are used depending on the type and purpose of the food. Absorbents are used properly.
鉄を主剤とする酸素吸収剤は、酸素吸収速度は速いものの、錆の発生による食品汚染や酸素吸収に伴い包装内の容積が減少するため、食品の形状を壊し易いという問題があった。これに対し還元性有機化合物を主剤とする酸素吸収剤は、錆の発生が無く、酸素吸収に伴い炭酸ガスを発生するため、包装内の容積が一定に保たれ、食品の形状を壊すことが無い。そのため還元性有機化合物を主剤とする酸素吸収剤は、特にスポンジケーキ等の形状が崩れ易い食品での利用が拡大している。酸素吸収剤は食品工場で食品と共に包装袋等に投入されるが、実際に投入されたか、その在否を確認する必要がある。酸素吸収剤の在否は目視ないし金属探知機による検査によって確認しているが、目視検査は多大な労力を要すると共に検査もれが避けられず、また不透明な包装材料を使用した場合には検査が不可能であるため、金属探知機による検査が主流となっている。しかしながら、金属探知機を利用した検査が可能なのは鉄を主剤とする酸素吸収剤だけであり、還元性有機化合物を主剤とする酸素吸収剤には適用できないため、還元性有機化合物を主剤とする酸素吸収剤の検査は目視に頼らざる得なかった。 Although the oxygen absorbent mainly composed of iron has a high oxygen absorption rate, there is a problem that the shape of the food is easily broken because the volume in the package is reduced due to food contamination and oxygen absorption due to the generation of rust. On the other hand, oxygen absorbers based on reducible organic compounds do not generate rust and generate carbon dioxide gas due to oxygen absorption, so the volume in the package is kept constant and the shape of the food can be destroyed. No. For this reason, the use of oxygen absorbents mainly composed of reducing organic compounds in foods, such as sponge cakes, whose shape tends to collapse is expanding. The oxygen absorbent is put into a packaging bag or the like together with food at a food factory, and it is necessary to check whether it is actually put in or not. The presence or absence of oxygen absorbers is confirmed by visual inspection or inspection with a metal detector, but visual inspection requires a lot of labor and is inevitable, and inspection is not possible when opaque packaging materials are used. This is impossible, so metal detectors are the mainstream. However, inspection using a metal detector is possible only for oxygen absorbers based on iron, and not applicable to oxygen absorbers based on reducing organic compounds. The inspection of the absorbent had to rely on visual inspection.
そのため還元性有機化合物を主剤とする酸素吸収剤においても目視に頼らない効率的な検査手段が望まれていた。 For this reason, there has been a demand for an efficient inspection means that does not rely on visual inspection even in an oxygen absorbent mainly composed of a reducing organic compound.
本発明は、還元性有機化合物を主剤とする酸素吸収剤が有する、錆の発生が無いという特徴を維持しつつ、食品工場等で異物検査のために使用されている金属探知機を用いてその在否を確認することが可能な酸素吸収剤を提供することを目的とする。 The present invention uses a metal detector that is used for foreign matter inspection in food factories, etc. while maintaining the characteristics that the oxygen absorbent mainly composed of a reducing organic compound has no rust. An object is to provide an oxygen absorbent capable of confirming the presence or absence.
本発明者らは、鋭意検討の結果、還元性有機化合物を主剤とする組成物にステンレス粉末を配合することにより、錆等により食品を汚染することが無く、且つ金属探知機により酸素吸収剤投入の有無を確認できることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have blended stainless steel powder with a composition containing a reducible organic compound as a main ingredient, so that food is not contaminated by rust and the like, and an oxygen absorber is charged by a metal detector. The present inventors have found that the presence or absence of this can be confirmed, and have completed the present invention.
すなわち本発明は、還元性有機化合物を主剤とする酸素吸収剤組成物およびステンレス粉末を通気性の袋に充填してなる、酸素吸収剤に関する。 That is, the present invention relates to an oxygen absorbent composition formed by filling a breathable bag with an oxygen absorbent composition mainly composed of a reducing organic compound and stainless powder.
本発明の酸素吸収剤に配合するステンレス粉末としてはフェライト系ステンレス、マルテンサイト系ステンレス、オーステナイト系ステンレス、析出硬化系ステンレスが挙げられる。その中でもフェライト系ステンレス、マルテンサイト系ステンレスが好ましく、耐酸化性能、入手のし易さおよびコストの点でフェライト系ステンレスがより好ましい。これらステンレス粉末は２種以上を併用してもよい。 Examples of the stainless powder blended in the oxygen absorbent of the present invention include ferritic stainless steel, martensitic stainless steel, austenitic stainless steel, and precipitation hardening stainless steel. Among them, ferritic stainless steel and martensitic stainless steel are preferable, and ferritic stainless steel is more preferable in terms of oxidation resistance, availability, and cost. Two or more of these stainless steel powders may be used in combination.
ステンレス粉末の割合は酸素吸収剤内剤、即ち酸素吸収剤組成物とステンレス粉末の合計量の３〜１０重量％が好ましく、５〜８重量％がさらに好ましい。ステンレス粉末の割合が３重量％未満の場合、金属探知機の感度を高感度に設定する必要があり、ノイズによる判定ミスが起こり易くなる。また、ステンレス粉末の割合が１０重量％を超えると酸素吸収剤本来の目的である酸素吸収能が低下する場合がある。 The ratio of the stainless steel powder is preferably 3 to 10% by weight, more preferably 5 to 8% by weight, based on the total amount of the oxygen absorbent internal agent, that is, the oxygen absorbent composition and the stainless powder. When the ratio of the stainless steel powder is less than 3% by weight, it is necessary to set the sensitivity of the metal detector to high sensitivity, and a determination error due to noise is likely to occur. On the other hand, if the ratio of the stainless steel powder exceeds 10% by weight, the oxygen absorption ability, which is the original purpose of the oxygen absorbent, may be lowered.
ステンレス粉末の粒子径は特に限定なく、偏析が生じず、酸素吸収剤内剤を小袋に分ける際に個体差があまり大きくならないよう十分な流動性を有し、また粉末の飛散が激しくないものであれば問題なく用いることができる。例えば粒子径６３μｍ以下の粒子を９５重量％以上含有し、且つ粒子径４４μｍ未満の粒子を５０〜８０重量％含有するものを用いればよい。粒子径６３μｍ以下の粒子を９８重量％以上含有し、且つ粒子径４４μｍ未満の粒子を５５〜７５重量％含有するものがさらに好ましく用いられる。あまり粒子径が小さいと、粉末の飛散が激しくなり小袋の封止部分に付着することによりシール不良が発生しやすくなる傾向にある。 The particle size of the stainless steel powder is not particularly limited, segregation does not occur, it has sufficient fluidity so that individual differences do not become too large when dividing the oxygen absorbent internal agent into sachets, and powder scattering is not severe. It can be used without any problems. For example, what contains 95% by weight or more of particles having a particle diameter of 63 μm or less and 50 to 80% by weight of particles having a particle diameter of less than 44 μm may be used. More preferably, particles containing 98% by weight or more of particles having a particle diameter of 63 μm or less and 55 to 75% by weight of particles having a particle diameter of less than 44 μm are used. If the particle size is too small, the powder will scatter more and will tend to adhere to the sealed portion of the sachet, which will likely cause a sealing failure.
なお、本明細書および請求の範囲において、「酸素吸収剤組成物」は酸素吸収剤の内剤として配合されるステンレス粉末以外の成分であって、従来より酸素吸収剤として知られている組成物を言うものとする。本発明の酸素吸収剤に配合される還元性有機化合物を主剤とする酸素吸収剤組成物としては、食品等の保存に用いられることが知られているアスコルビン酸、グリセリン、カテコール等を主剤として含む酸素吸収剤組成物がいずれも好適に用いられ、特に限定されない。例えば特許第２７０１９９９号公報、特開２００３−１０６２７号公報、特許第２９４３１５６号公報、特公平０３−２１２１４号公報に記載のものが例示される。 In the present specification and claims, the “oxygen absorbent composition” is a component other than stainless powder blended as an internal agent of an oxygen absorbent, and has been conventionally known as an oxygen absorbent. Shall be said. The oxygen absorbent composition mainly composed of the reducing organic compound blended in the oxygen absorbent of the present invention contains ascorbic acid, glycerin, catechol and the like, which are known to be used for the preservation of foods, as a main ingredient. Any oxygen absorbent composition is suitably used and is not particularly limited. Examples thereof include those described in Japanese Patent No. 2701999, Japanese Patent Application Laid-Open No. 2003-10627, Japanese Patent No. 2943156, and Japanese Patent Publication No. 03-21214.
主剤となる還元性有機化合物としては、アスコルビン酸、グリセリン、カテコール等が挙げられ、その中でもアスコルビン酸が好ましい。アスコルビン酸は、Ｌ−アスコルビン酸の他、Ｄ−iso−アスコルビン酸(エリソルビン酸)を用いることができる。Ｌ−アスコルビン酸とＤ−iso−アスコルビン酸は併用してもよい。また、アスコルビン酸は未中和物も使用できるが、適当なアルカリ、例えばアルカリ金属、アルカリ土類金属等で完全に、あるいは部分的に中和されていてもよい。特に好ましい塩はナトリウム、カリウム、カルシウム等である。 Examples of the reducing organic compound as the main agent include ascorbic acid, glycerin, catechol and the like, and among them, ascorbic acid is preferable. As for ascorbic acid, D-iso-ascorbic acid (erythorbic acid) can be used in addition to L-ascorbic acid. L-ascorbic acid and D-iso-ascorbic acid may be used in combination. Ascorbic acid can also be used as an unneutralized product, but it may be completely or partially neutralized with an appropriate alkali such as an alkali metal or alkaline earth metal. Particularly preferred salts are sodium, potassium, calcium and the like.
還元性有機化合物は、酸素吸収剤組成物全量の１０〜６０重量％、特に１５〜５０重量％が好ましい。還元性有機化合物の割合が１０重量％未満の場合には酸素吸収剤全体量が過大となり、６０重量％を超える場合には、その分他の成分の配合量を減少させることとなるため、全体のバランスが崩れ、酸素吸収速度が低下する傾向がある。 The reducing organic compound is preferably 10 to 60% by weight, particularly preferably 15 to 50% by weight, based on the total amount of the oxygen absorbent composition. When the ratio of the reducing organic compound is less than 10% by weight, the total amount of the oxygen absorbent is excessive, and when it exceeds 60% by weight, the blending amount of other components is reduced accordingly. The balance of oxygen tends to be lost, and the oxygen absorption rate tends to decrease.
本発明に用いられる酸素吸収剤組成物は、主剤となる還元性有機化合物以外にアルカリ性化合物、反応促進物、シリカおよび水を含有するものであるのが好ましい。 The oxygen absorbent composition used in the present invention preferably contains an alkaline compound, a reaction accelerator, silica and water in addition to the reducing organic compound as the main agent.
アルカリ性化合物としては、アルカリ金属またはアルカリ土類金属、アルミニウム等の水酸化物、炭酸塩、炭酸水素塩、有機酸、例えば酢酸、乳酸、クエン酸、りんご酸、オキザロ酢酸等のアルカリ金属塩等が例示される。その中でも、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸塩、炭酸水素塩が安全性の点で好ましい。これら炭酸塩、炭酸水素塩は２種以上を併用してもよい。 Alkali compounds include alkali metals or alkaline earth metals, hydroxides such as aluminum, carbonates, hydrogen carbonates, organic acids such as alkali metal salts such as acetic acid, lactic acid, citric acid, malic acid, oxaloacetic acid, etc. Illustrated. Among these, carbonates and bicarbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate are preferable from the viewpoint of safety. Two or more of these carbonates and bicarbonates may be used in combination.
アルカリ性化合物の割合は、酸素吸収剤組成物全量の１〜６０重量％が好ましく、５〜５０重量％がより好ましい。アルカリ性化合物の割合が１重量％未満の場合、あるいは６０重量％を超える場合には酸素吸収能が十分に発揮されない場合がある。 The proportion of the alkaline compound is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, based on the total amount of the oxygen absorbent composition. When the ratio of the alkaline compound is less than 1% by weight or exceeds 60% by weight, the oxygen absorbing ability may not be sufficiently exhibited.
反応促進物としては、還元性有機化合物の酸素吸収剤としての作用を発現するための触媒として作用するものを意味する。このような反応促進物としては活性炭、鉄、銅、亜鉛、すずなどの遷移金属またはその塩などが用いられるが、その作用の発現性及び安全性から特に活性炭あるいは鉄を含む化合物（以下、鉄化合物という）が好ましい。鉄化合物としては第一鉄塩、第二鉄塩いずれであってもよく、あるいは有機酸との鉄塩であってもよい。具体的には硫酸塩、塩酸塩、クエン酸塩、シュウ酸塩等、特に水溶性の鉄化合物が好ましい。特に好ましい鉄化合物としては、硫酸第一鉄、塩化第一鉄、硫酸第二鉄、塩化第二鉄等が例示される。 The reaction accelerator means a substance that acts as a catalyst for expressing the action of the reducing organic compound as an oxygen absorbent. As such a reaction accelerator, activated carbon, transition metals such as iron, copper, zinc, tin, or salts thereof are used, and activated carbon or a compound containing iron in particular (hereinafter referred to as iron Compound). The iron compound may be either a ferrous salt or a ferric salt, or may be an iron salt with an organic acid. Specifically, water-soluble iron compounds such as sulfates, hydrochlorides, citrates and oxalates are particularly preferable. Particularly preferred iron compounds include ferrous sulfate, ferrous chloride, ferric sulfate, ferric chloride and the like.
反応促進物の割合は還元性有機化合物１００重量部に対し１〜２００重量部が好ましく、５〜１００重量部がより好ましい。反応促進物の量が１重量部より少ない場合あるいは２００重量部より多い場合には、酸素吸収能が十分に発揮されない場合がある。 The proportion of the reaction accelerator is preferably 1 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the reducing organic compound. When the amount of the reaction accelerator is less than 1 part by weight or more than 200 parts by weight, the oxygen absorption capacity may not be sufficiently exhibited.
シリカとしては、ケイ酸ナトリウムの酸による分解等の液相法、ハロゲン化ケイ素の水熱分解等の気相法のいずれの方法で製造されたものでも使用することができる。シリカの粒径は１０００μｍ以下のものが好ましく、５００μｍ以下のものが特に好ましい。
シリカの割合は、酸素吸収剤組成物全量の５〜５０重量％が好ましく、１０〜３０重量％がより好ましい。５重量％より少ないと流動性が低下し、５０重量％より多いと飛散性が増大する。
As silica, those produced by either a liquid phase method such as decomposition of sodium silicate with an acid or a gas phase method such as hydrothermal decomposition of silicon halide can be used. The particle size of silica is preferably 1000 μm or less, and particularly preferably 500 μm or less.
The proportion of silica is preferably 5 to 50% by weight, more preferably 10 to 30% by weight of the total amount of the oxygen absorbent composition. If it is less than 5% by weight, the fluidity is lowered, and if it is more than 50% by weight, the scattering property is increased.
本発明の酸素吸収剤において、酸素吸収作用を発現させるためには水が必要となるが、この水はどのような形で存在していてもよい。水の添加方法としては、例えば、水を直接添加する方法、バーミキュライト、ゼオライト等の保水材に吸着ないし含浸させた形で添加する方法、他の成分中の結晶水として添加する方法等が挙げられる。あるいは、対象食品から蒸散される水蒸気として存在させてもよい。好ましい適用としては、酸素吸収速度あるいは適応食品の広範さから、水を何らかの方法で別途添加するのがよい。この場合の水の割合は酸素吸収剤組成物全量の５〜５０重量％が好ましく、１０〜３５重量％がより好ましい。水の量が５重量％より少ないと酸素吸収能力が低下する傾向があり、飛散性も増大する。５０重量％より多い場合には流動性が悪化する傾向にある。 In the oxygen absorbent of the present invention, water is required to develop the oxygen absorbing action, but this water may be present in any form. Examples of the method of adding water include a method of adding water directly, a method of adding in a form adsorbed or impregnated in a water retention material such as vermiculite and zeolite, a method of adding as crystal water in other components, and the like. . Or you may make it exist as water vapor | steam transpired from object food. As a preferred application, water is preferably added separately by some method because of the oxygen absorption rate or the wide range of applicable foods. In this case, the proportion of water is preferably 5 to 50% by weight, more preferably 10 to 35% by weight of the total amount of the oxygen absorbent composition. If the amount of water is less than 5% by weight, the oxygen absorption capacity tends to decrease and the scattering property also increases. When it is more than 50% by weight, the fluidity tends to deteriorate.
本発明の酸素吸収剤は上記成分を混合した酸素吸収剤組成物とステンレス粉末を混合し、適当量を通気性の袋に充填することによって製造される。通気性の袋としては、従来より酸素吸収剤に用いられているものであればいずれも特に制限なく用いることができる。その材質としては、プラスチック、紙、不織布等が例示されるが、その中でもプラスチック包材が耐油性の点で好ましい。 The oxygen absorbent of the present invention is produced by mixing an oxygen absorbent composition in which the above components are mixed with stainless steel powder and filling an appropriate amount in a breathable bag. Any breathable bag can be used without particular limitation as long as it has been conventionally used for oxygen absorbers. Examples of the material include plastic, paper, and non-woven fabric. Among them, a plastic packaging material is preferable from the viewpoint of oil resistance.
本発明の酸素吸収剤は、有機系酸素吸収剤の特徴を維持しつつ、金属探知機を用いて効率的に在否を確認することができる。従って、本発明の酸素吸収剤を封入した製品について酸素吸収剤を封入したことの確認検査を金属探知器を用いて行う、検品法もまた、本発明に含まれる。 The presence or absence of the oxygen absorbent of the present invention can be efficiently confirmed using a metal detector while maintaining the characteristics of the organic oxygen absorbent. Accordingly, the present invention also includes an inspection method in which a metal detector is used to perform a verification test for sealing an oxygen absorbent for a product in which the oxygen absorbent of the present invention is sealed.
以下、実施例により本発明を更に説明する。
実施例１および比較例１〜２
（金属探知機検出試験）
方法：
表１に示す組成の内剤を十分に混合した後、紙製の小袋（４ｃｍ×６ｃｍ）に１．２ｇずつ封入して酸素吸収剤各１００個を製造した。製造した酸素吸収剤を塩化ビニリデンコートナイロン／ポリエチレン製の袋にスポンジケーキと共に１個ずつ密封し、金属探知機（大和製衡株式会社製、ＭＡ-３１１７）に通して検出数をカウントした。尚、使用したステンレス粉末の粒度分布は表２に示した。
The following examples further illustrate the present invention.
Example 1 and Comparative Examples 1-2
(Metal detector detection test)
Method:
After thoroughly mixing the internal preparations having the compositions shown in Table 1, 1.2 g each was enclosed in a paper sachet (4 cm × 6 cm) to produce 100 oxygen absorbers. The produced oxygen absorbents were sealed one by one with a sponge cake in a bag made of vinylidene chloride coated nylon / polyethylene, and passed through a metal detector (manufactured by Yamato Seisaku Co., Ltd., MA-3117) to count the number of detections. The particle size distribution of the used stainless steel powder is shown in Table 2.
結果：
ステンレス粉末を使用した本発明の酸素吸収剤および鉄粉を主剤とする比較例１の酸素吸収剤は全て金属探知機に検出された。結果を表３に示す。
result:
All of the oxygen absorbent of the present invention using stainless steel powder and the oxygen absorbent of Comparative Example 1 mainly composed of iron powder were detected by a metal detector. The results are shown in Table 3.
（食品保存試験）
方法：
金属探知機検出試験で製造した食品包装体を２５℃、２４時間保存した後、食品形状の変化を評価した。
(Food preservation test)
Method:
The food package manufactured by the metal detector detection test was stored at 25 ° C. for 24 hours, and then the change in food shape was evaluated.
結果：
実施例１および比較例２の酸素吸収剤を使用したスポンジケーキは形状に変化は見られなかったが、比較例１のものは包装内部の圧力低下により食品が圧迫され、潰れていた。また、比較例１の酸素吸収剤には錆の発生が見られたが、実施例１では錆は発生しなかった。結果を表３に示す。
Sponge cakes using the oxygen absorbents of Example 1 and Comparative Example 2 did not change in shape, but those of Comparative Example 1 were crushed because the food was pressed by the pressure drop inside the package. Moreover, although generation | occurrence | production of rust was seen in the oxygen absorbent of the comparative example 1, in Example 1, rust did not generate | occur | produce. The results are shown in Table 3.
（細菌検査）
方法：
金属探知器試験で使用した実施例１および比較例１〜２の酸素吸収剤と同一の酸素吸収剤を塩化ビニリデンコートナイロン／ポリエチレン製の袋に饅頭と共に１個ずつ密封し、これを２５℃の恒温器内で保存した。初発及び３０日後に饅頭の一部を採取し、細菌検査を行った。細菌検査は１サンプルより２０ｇを採取し、１０倍量の滅菌済生理食塩水を添加した後破砕処理を行って得た液を検査原液として行った。なお、酸素吸収剤を含有しない試験区をコントロールとした。
(Bacteria test)
Method:
The same oxygen absorbent as that used in Example 1 and Comparative Examples 1 and 2 used in the metal detector test was sealed in a vinylidene chloride-coated nylon / polyethylene bag one by one with a pier, and this was sealed at 25 ° C. Stored in a thermostat. A portion of the wharf was collected after the first onset and 30 days later and tested for bacteria. Bacteria test was performed using 20 g from one sample, adding 10 times the amount of sterilized physiological saline, and then crushing it as a test stock solution. In addition, the test group containing no oxygen absorbent was used as a control.
結果：
いずれの酸素吸収剤を用いた場合も３０日後の菌数に大きな差は見られず、ステンレス粉末を含有した酸素吸収剤を用いることにより、食品の保存性が低下することは無かった。結果を表４に示す。
result:
When any oxygen absorbent was used, there was no significant difference in the number of bacteria after 30 days, and the use of an oxygen absorbent containing stainless steel powder did not reduce the food storage stability. The results are shown in Table 4.
Claims (7)
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| KR101526654B1 (en) * | 2013-03-05 | 2015-06-09 | 주식회사 립멘 | Organic Oxygen Absorbent using the Porous Carrier and Method of Preparing Thereof |
| JP2017030813A (en) * | 2015-08-03 | 2017-02-09 | 三菱瓦斯化学株式会社 | Deoxidation agent package, and presence confirmation method of the same |
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| JPH0381098A (en) * | 1989-08-24 | 1991-04-05 | Kobe Steel Ltd | Manufacture of complex member |
| JPH07187238A (en) * | 1993-12-28 | 1995-07-25 | Freunt Ind Co Ltd | Packing material, pressure-sensitive adhesive tape, bag for food keeping agent, and method for detecting the agent |
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| JP2017030813A (en) * | 2015-08-03 | 2017-02-09 | 三菱瓦斯化学株式会社 | Deoxidation agent package, and presence confirmation method of the same |
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