WO1998005419A1 - Deoxidizer - Google Patents

Deoxidizer Download PDF

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Publication number
WO1998005419A1
WO1998005419A1 PCT/JP1997/002413 JP9702413W WO9805419A1 WO 1998005419 A1 WO1998005419 A1 WO 1998005419A1 JP 9702413 W JP9702413 W JP 9702413W WO 9805419 A1 WO9805419 A1 WO 9805419A1
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Prior art keywords
glucose
antioxidant
oxygen
carrier
oxygen scavenger
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PCT/JP1997/002413
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French (fr)
Japanese (ja)
Inventor
Seishi Takenawa
Jun Shirai
Mikio Ueda
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Fujisawa Pharmaceutical Co., Ltd.
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Publication of WO1998005419A1 publication Critical patent/WO1998005419A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23L3/3436—Oxygen absorbent

Definitions

  • the conventional methods using glucose and glucose oxidase / catalase enzymes have problems such as slow initial deoxygenation ability, and gradually deactivating the enzyme when stored for a long time, resulting in reduced deoxygenation ability. There was a need for improvement.
  • the present inventors have conducted various studies on the improvement of the initial deoxygenation capacity and the stabilization of the enzyme.As a result, adding an antioxidant to glucose, glucose oxidase As a result of knowing that it can be improved and conducting further research, they have completed the present invention.
  • the present invention provides an oxygen scavenger containing glucose, glucose oxidase, catalase and an antioxidant.
  • glucose oxidase and catalase used in the present invention commercially available ones can be used, respectively. it can.
  • the antioxidant include ascorbic acid, isoascorbic acid, and their alkali metal salts (such as sodium salt and potassium salt). Two or more of these may be used in combination. it can.
  • oxygen scavenger of the present invention a simple mixture of glucose, glucose oxidase, catalase and an antioxidant can be used, but in general, it is possible to use dulose, glucose oxidase, catalase and an antioxidant. It is preferable to use an aqueous solution containing a gelling agent by adding a gelling agent, or a powdered solution obtained by absorbing the aqueous solution into a carrier having a large water retention capacity.
  • preferred examples of the carrier include cellulose, porous resin, activated carbon, silica gel, and the like. Of these, activated carbon is preferred.
  • Preferred examples of the gelling agent include gelatin, agar, and the like.
  • composition ratio of glucose, glucose oxidase, lipase and antioxidant is as follows, taking as an example an oxygen scavenger obtained by absorbing these into a carrier (eg, activated carbon). % By weight in the preparation).
  • a carrier eg, activated carbon
  • Glucose oxidase 0.01-1.0 (with glucose oxidase activity of 50
  • One unit of the enzymatic activity of glucose oxidase is the amount of enzyme that oxidizes 1 / mol of glucose per minute at 35 ° C and pH 5.1 to produce gluconic acid.
  • One unit of catalase enzyme activity is the amount of enzyme that decomposes 1 mol of hydrogen peroxide per minute at 25 ° C and pH 7.0 to produce oxygen and water.
  • glucose oxidase, calatases and antioxidants in a carrier these may be dissolved in water in advance, mixed with a carrier such as activated carbon, and powdered.
  • a carrier such as activated carbon
  • various phosphates, sodium carbonate, sodium hydrogencarbonate, or alkali metal salts of various organic acids, etc. are added to water together with glucose as a pH adjuster. It is preferred to dissolve.
  • An example of a method of using the oxygen scavenger thus adjusted is as follows.
  • a gas-permeable packaging material such as a thin polyethylene film or a thin polystyrene film laminate
  • a low oxygen-permeable packaging material to absorb oxygen in the packaging and deoxygenate.
  • the oxygen absorber of the present invention is formed into a tablet, it can be used by loading it on the back surface of the bottle lid or placing it in the bottom. Further, a sheet obtained by dispersing the oxygen scavenger of the present invention in a nonwoven fabric can be used.
  • Glucose was dissolved to a concentration of 55% in a dihydrogen phosphate solution having a concentration of 2 mol / 1, and 8 g of this solution was weighed. To this, O.lg of a 10% aqueous solution of a glucose oxidase nocatalase enzyme (glucose oxidase activity: 50 units / mg, catalase activity: 150 units) was added and mixed. Separately, powdered activated carbon (3.4 g) was mixed with the prescribed antioxidant in the amount shown in Table 1 in powder form, mixed, and then mixed with the preceding mixture of sugar solution and enzyme solution, followed by uniform mixing. An oxygen agent was prepared.
  • Each oxygen reagent was sealed in an aluminum laminate bag, stored at 40 ° C for 20 days, and then measured for deoxidizing ability.
  • a deoxidizer having a composition to which no antioxidant was added was similarly prepared, and immediately after the preparation and after storage at 40 ° C for 20 days, the deoxygenation ability was measured.
  • the oxygen scavenger was prepared using a mortar cooled to -20 ° C.
  • the oxygen scavenger containing glucose and glucose oxidase, catalase and antioxidant of the present invention has a high initial oxygen scavenging ability, and has a high oxygen scavenging ability without long-term storage. Useful as an oxygen scavenger.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A deoxidizer comprising glucose, a glucose oxidase, a catalase, and an antioxidant.

Description

明 細 書  Specification
脱酸素剤  Oxygen scavenger
背景技術 Background art
近年、 食品等の流通経路が長くなり、 消費者に渡るまでの品質保持の必要性が 増大しているが、 加工食品においては保存料や酸化防止剤の添加、 使用だけでは 充分な効果が得られない場合が多く、 又、 生鲜食品では保存料等の添加物は使用 できないため、 流通設備や包装面からの対応が必要となる状況が増大している。 包装面からの対応としては、 ガスバリヤ一性の高い包材と脱酸素剤を用いて、 包 装内部の酸素を除去する事により、 流通時の品質の劣化を防止する技術が開発さ れ、 普及している。 脱酸素剤には鉄粉、 ァスコルビン酸類、 カテコールなどが用 いられており、 それぞれ使用する目的などによって使い分けられている。  In recent years, the distribution route of foods and other products has become longer, and the necessity of maintaining quality until reaching consumers has increased.However, in processed foods, the addition and use of preservatives and antioxidants alone provide sufficient effects. In many cases, additives such as preservatives cannot be used in raw foods, and the need for distribution facilities and packaging is increasing. As a response from the packaging side, a technology was developed to prevent deterioration in quality during distribution by removing oxygen inside the packaging using a packaging material with high gas barrier properties and an oxygen absorber. are doing. Iron powder, ascorbic acids, catechol, etc. are used as oxygen scavengers, and they are used depending on the purpose of use.
一方、 グルコース、 グルコースォキシダーゼ zカタラーゼ系酵素の酸化反応を 利用した脱酸素剤については、 これらを多孔性の担体に保持させる方法が特開昭 On the other hand, as for the oxygen scavenger utilizing the oxidation reaction of glucose and glucose oxidase z catalase-based enzyme, a method of retaining these on a porous carrier is disclosed in
47— 29545および特開昭 49一 86285に示されているが性能的に問題があり、 実用化 には至っていない。 47-29545 and JP-A-49-86285 show problems in performance and have not been put to practical use.
グルコース、 グルコースォキシダーゼ /カタラーゼ系酵素を用いた従来の方法 では、 初期の脱酸素能が遅いことや、 長時間保存すると徐々に酵素が失活して、 脱酸素能が低下するなどの問題があり、 改良が求められていた。  The conventional methods using glucose and glucose oxidase / catalase enzymes have problems such as slow initial deoxygenation ability, and gradually deactivating the enzyme when stored for a long time, resulting in reduced deoxygenation ability. There was a need for improvement.
本発明者らは、 初期の脱酸素能の向上と酵素の安定化について種々検討した結 果、 グルコース、 グルコースォキシダーゼ //カタラーゼ系酵素に酸化防止剤を添 加することで、 これらの欠点が改善できることを知り、 さらに研究を重ねた結 果、 本発明を完成するに至った。  The present inventors have conducted various studies on the improvement of the initial deoxygenation capacity and the stabilization of the enzyme.As a result, adding an antioxidant to glucose, glucose oxidase As a result of knowing that it can be improved and conducting further research, they have completed the present invention.
発明の開示 Disclosure of the invention
本発明は、 グルコース、 グルコースォキシダーゼ、 カタラーゼおよび酸化防止 剤を含む脱酸素剤を提供するものである。  The present invention provides an oxygen scavenger containing glucose, glucose oxidase, catalase and an antioxidant.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
本発明に用いるグルコースォキシダーゼおよびカタラーゼはそれぞれ、 通常用 いられている市販のものが使用でき、 例えばぺニシリゥム属ゃァスペルギルス属 等の糸状菌を培養して得られる酵素を代表例としてあげることができる。 また、 酸化防止剤の好ましい例としては、 ァスコルビン酸、 イソァスコルビン 酸およびこれらのアル力リ金厲塩 （ナト リウム塩、 力リウム塩等） 等が挙げら れ、 これらは 2種以上併用することもできる。 As the glucose oxidase and catalase used in the present invention, commercially available ones can be used, respectively. it can. Preferable examples of the antioxidant include ascorbic acid, isoascorbic acid, and their alkali metal salts (such as sodium salt and potassium salt). Two or more of these may be used in combination. it can.
本発明の脱酸素剤は、 グルコース、 グルコースォキシダーゼ、 カタラーゼおよ び酸化防止剤を単純に混合したものを使用することができるが、 一般には、 ダル コース、 グルコースォキシダーゼ、 カタラーゼおよび酸化防止剤を含む水溶液を ゲル化剤を添加してゲル化したものを使用するか、 水分保持力の大きい担体に吸 収させて粉末化したものを使用するのが好ましい。  As the oxygen scavenger of the present invention, a simple mixture of glucose, glucose oxidase, catalase and an antioxidant can be used, but in general, it is possible to use dulose, glucose oxidase, catalase and an antioxidant. It is preferable to use an aqueous solution containing a gelling agent by adding a gelling agent, or a powdered solution obtained by absorbing the aqueous solution into a carrier having a large water retention capacity.
ここで、 担体の好ましい例としては、 セルロース、 多孔性樹脂、 活性炭、 シリ 力ゲル等が挙げられるが、 これらのうち活性炭が好適である。 また、 ゲル化剤の 好ましい例としては、 例えばゼラチン、 寒天等が挙げられる。  Here, preferred examples of the carrier include cellulose, porous resin, activated carbon, silica gel, and the like. Of these, activated carbon is preferred. Preferred examples of the gelling agent include gelatin, agar, and the like.
グルコース、 グルコースォキシダーゼ、 力タラ一ゼおよび酸化防止剤の配合割 合は、 これらを担体 （例えば活性炭） に吸収させて得られる脱酸素剤を例にする と、 次のようになる （脱酸素剤中の重量％) 。  The composition ratio of glucose, glucose oxidase, lipase and antioxidant is as follows, taking as an example an oxygen scavenger obtained by absorbing these into a carrier (eg, activated carbon). % By weight in the preparation).
グルコース ： 20— 40  Glucose: 20-40
酸化防止剤 ： 5 - 20  Antioxidant: 5-20
グルコースォキシダーゼ： 0. 01— 1. 0 (グルコースォキシダーゼ活性が 50  Glucose oxidase: 0.01-1.0 (with glucose oxidase activity of 50
ュニッ ト mgとして）  Unit mg)
力タラ一ゼ ： 0. 01— 1. 0 (力タラ一ゼ活性が 150ュニッ トノ mg  Potato: 0.01-1.0 (potency of 150 units / mg)
として）  As)
活性炭 ： 20 - 40  Activated carbon: 20-40
水 ： 20— 40  Water: 20-40
(グルコースォキシダ一ゼの酵素活性 1ユニッ トは、 35°C、 pH5. 1の条件下で 1 分間に 1 / mo lのグルコースを酸化してグルコン酸を生成する酵素量であり、 ま たカタラーゼの酵素活性 1ユニッ トは、 25°C、 pH7. 0の条件下で、 1分間に 1 mo lの過酸化水素を分解して酸素と水を生成する酵素量である。 以下同じ）  (One unit of the enzymatic activity of glucose oxidase is the amount of enzyme that oxidizes 1 / mol of glucose per minute at 35 ° C and pH 5.1 to produce gluconic acid. One unit of catalase enzyme activity is the amount of enzyme that decomposes 1 mol of hydrogen peroxide per minute at 25 ° C and pH 7.0 to produce oxygen and water.
グルコース、 グルコースォキシダ一ゼ、 カラタ一ゼおよび酸化防止剤を担体に 吸収、 保持させる方法としては、 これらをあらかじめ水に溶解して、 例えば活性 炭など担体と混合して粉末化すればよい。 また、 水に溶解する場合、 酵素反応に よりダルコン酸が生成して溶液の pHが低下することを考慮して、 pH調整剤として 各種リン酸塩、 炭酸ナトリウム、 炭酸水素ナトリウムあるいは各種有機酸のアル 力リ金属塩などをグルコースと共に水に溶解することが好ましい。 As a method for absorbing and retaining glucose, glucose oxidase, calatases and antioxidants in a carrier, these may be dissolved in water in advance, mixed with a carrier such as activated carbon, and powdered. When dissolved in water, Considering that dalconic acid is generated and the pH of the solution is lowered, various phosphates, sodium carbonate, sodium hydrogencarbonate, or alkali metal salts of various organic acids, etc., are added to water together with glucose as a pH adjuster. It is preferred to dissolve.
このようにして調整された脱酸素剤の利用方法の例を示せば次の通りである。 すなわち、 使用用途に応じて適宜整形し、 通気性包材例えば薄手のポリエチレン フィルム、 薄手のポリスチレンフィルムをラミネートしたもの等で包装したもの を、 酸素透過性の低い包材で包装した食品の包装中に入れ、 包装中の酸素を吸収 し、 脱酸素する。 また他の例としては、 本発明の脱酸素剤をタブレット化したも ので、 ビンのふたの裏面に装填したり、 底入れして用いることができる。 さらに は、 本発明の脱酸素剤を不織布に分散させてシート状にしたものを用いることが できる。  An example of a method of using the oxygen scavenger thus adjusted is as follows. In other words, during the packaging of foods that are appropriately shaped according to the intended use and packaged with a gas-permeable packaging material, such as a thin polyethylene film or a thin polystyrene film laminate, and then packaged with a low oxygen-permeable packaging material To absorb oxygen in the packaging and deoxygenate. As another example, since the oxygen absorber of the present invention is formed into a tablet, it can be used by loading it on the back surface of the bottle lid or placing it in the bottom. Further, a sheet obtained by dispersing the oxygen scavenger of the present invention in a nonwoven fabric can be used.
次のこの発明を実施例により説明する。  Next, the present invention will be described with reference to examples.
2 mo l / 1 の濃度のリン酸水素二力リゥム溶液にグルコースを 55%濃度になる ように溶かし、 この液 8 gを量り採った。 これにグルコースォキシダーゼノカタ ラーゼ系酵素 （グルコースォキシダーゼ活性： 50ユニット/ mg、 カタラーゼ活性 ： 150ュニッ トノ mg) の 10%水溶液 O. l gを加え混合した。 これとは別に粉末活性 炭 3. 4 gに表 1の量の所定の酸化防止剤を粉末で加えて混合した後先の糖液と酵 素液の混合液を加えて均一に混合して脫酸素剤を調製した。  Glucose was dissolved to a concentration of 55% in a dihydrogen phosphate solution having a concentration of 2 mol / 1, and 8 g of this solution was weighed. To this, O.lg of a 10% aqueous solution of a glucose oxidase nocatalase enzyme (glucose oxidase activity: 50 units / mg, catalase activity: 150 units) was added and mixed. Separately, powdered activated carbon (3.4 g) was mixed with the prescribed antioxidant in the amount shown in Table 1 in powder form, mixed, and then mixed with the preceding mixture of sugar solution and enzyme solution, followed by uniform mixing. An oxygen agent was prepared.
各脫酸素剤はアルミラミネート袋に密封して、 40°Cで 20日間保存した後、 脱酸 素能を測定した。 これとは別に酸化防止剤を加えない組成の脱酸素剤を同様に調 製して、 調製直後および 40°Cで 20日間保存した後、 脱酸素能を測定した。 なお、 脱酸素剤の調製は、 -20°Cに冷却した乳鉢を用いて行った。  Each oxygen reagent was sealed in an aluminum laminate bag, stored at 40 ° C for 20 days, and then measured for deoxidizing ability. Separately, a deoxidizer having a composition to which no antioxidant was added was similarly prepared, and immediately after the preparation and after storage at 40 ° C for 20 days, the deoxygenation ability was measured. The oxygen scavenger was prepared using a mortar cooled to -20 ° C.
(脱酸素能の測定方法）  (Method of measuring deoxygenation capacity)
各脱酸素剤 3 gを量り採り、 250ml容のガラス瓶に入れて密封し、 内部に残存 する酸素比率の経時変化を溶存酸素計 （東亜電波工業社製 DO - 20A型） を用いて 測定した。 表 1 試験区
Figure imgf000006_0001
3 g of each oxygen absorber was weighed out, sealed in a 250 ml glass bottle, and the time-dependent change in the oxygen ratio remaining inside was measured using a dissolved oxygen meter (DO-20A manufactured by Toa Denpa Kogyo Co., Ltd.). Table 1 Test plot
Figure imgf000006_0001
表 2 測定結果Table 2 Measurement results
Figure imgf000006_0002
Figure imgf000006_0002
数値；残存酸素量 （％) 本発明の試験区 （No. 1 〜 5 ) では保存中の脱酸素能の低下が抑えられている - だけでなく、 初期の脫酸素の速度が速くなつていることが分かる。 Numerical value; residual oxygen content (%) In the test plots of the present invention (Nos. 1 to 5), the decrease in the deoxygenation capacity during storage was suppressed-not only, but also the initial oxygen rate increased.
産業上の利用可能性 Industrial applicability
以上のように、 本発明のグルコースおよびグルコースォキシダーゼ、 カタラー ゼおよび酸化防止剤を含む脱酸素剤は、 初期の脱酸素力が高く、 しかも長期保存 中の脱酸素能の低下がない酵素系の脱酸素剤として有用である。  As described above, the oxygen scavenger containing glucose and glucose oxidase, catalase and antioxidant of the present invention has a high initial oxygen scavenging ability, and has a high oxygen scavenging ability without long-term storage. Useful as an oxygen scavenger.

Claims

請求の範囲 The scope of the claims
1 . グルコース、 グルコースォキシダーゼ、 力タラ一ゼおよび酸化防止剤を含む 脱酸素剤。  1. An oxygen scavenger containing glucose, glucose oxidase, glucose, and antioxidants.
2 . 酸化防止剤がァスコルビン酸もしくはそのアル力リ金属塩又はィソァスコル ビン酸もしくはそのアル力リ金属塩である請求の範囲 1の脱酸素剤。  2. The oxygen scavenger according to claim 1, wherein the antioxidant is ascorbic acid or an alkali metal salt thereof or isoascorbic acid or an alkali metal salt thereof.
3 . グルコース、 グルコースォキシダーゼ、 カタラーゼおよび酸化防止剤を担体 に吸収させ、 粉末化して得られる脱酸素剤。  3. An oxygen scavenger obtained by absorbing glucose, glucose oxidase, catalase and an antioxidant into a carrier and pulverizing it.
4 . グルコース、 グルコースォキシダーゼ、 力タラ一ゼおよび酸化防止剤を担体 に吸収させ、 粉末化することを特徴とする脱酸素剤の製造法。  4. A process for producing an oxygen scavenger, which comprises absorbing glucose, glucose oxidase, glucose, and an antioxidant into a carrier and pulverizing the carrier.
5 . 酸化防止剤がァスコルビン酸もしくはそのアル力リ金厲塩又はィソァスコル ビン酸もしくはそのアルカリ金属塩であり、 担体が活性炭である請求の範囲 3の 脫酸素剤。  5. The oxygen reducing agent according to claim 3, wherein the antioxidant is ascorbic acid or its alkali metal salt or isoascorbic acid or its alkali metal salt, and the carrier is activated carbon.
6 . 酸化防止剤がァスコルビン酸もしくはそのアル力リ金厲塩又はィソァスコル ビン酸もしくはそのアル力リ金属塩であり、 担体が活性炭である請求の範囲 4の 脱酸素剤の製造法。  6. The method for producing an oxygen scavenger according to claim 4, wherein the antioxidant is ascorbic acid or its alkali metal salt or isoascorbic acid or its alkali metal salt, and the carrier is activated carbon.
PCT/JP1997/002413 1996-08-06 1997-07-10 Deoxidizer WO1998005419A1 (en)

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WO2005059869A1 (en) * 2003-12-18 2005-06-30 Asahi Kasei Life & Living Corporation Adhesive label
CN116076502A (en) * 2023-03-08 2023-05-09 广西中烟工业有限责任公司 Insecticidal mildew-proof tobacco mellowing composition, and preparation method and application thereof

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