JP2943156B2 - Oxygen scavenger - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an oxygen scavenger. More specifically, the present invention relates to a novel oxygen absorber containing glycerin as a main component.

In this specification, the term "deoxidizer" is mainly used to mean "a composition having an oxygen-absorbing effect" (an oxygen absorber composition). Oxygen package).

[Conventional technology]

As a preservation technique for foods and the like, there is a technique using an oxygen scavenger, and the food etc. and an oxygen scavenger are placed in a gas-barrier sealed bag or sealed container (hereinafter, sometimes simply referred to as a sealed container or container). It is used to prevent the oxidation of foods and the growth and growth of bacteria and molds, etc., by making the sealed system substantially oxygen-free, and is used for storage of a wide variety of foods and the like.

Conventionally, as the oxygen scavenger, iron oxide as a main agent has been used because of its oxygen absorbing ability, ease of handling, safety, cost, and the like.

By the way, in the case of packaged food, for example, after the food is sealed in a packaging bag, it is applied to a metal detector in order to check for contamination.

However, since the oxygen absorber containing iron powder as a main component is naturally detected by the metal detector, the metal detector cannot be applied to packaged food and the like in which the oxygen absorber is enclosed.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION In view of the above-described problems of the related art, it is an object of the present invention to prevent oxygen from being detected even when a deoxidizer is applied to a metal detector.

[Means for solving the problem]

Means for solving the above problem is that the oxygen scavenger is a composition comprising glycerin and an alkaline substance.

As an embodiment of the solving means, there may be mentioned a deoxygenating agent comprising the above-mentioned glycerin and an alkaline substance, and a composition obtained by mixing other components as needed with this deoxidizing agent. (2) a deoxidizer composed of glycerin, an alkaline substance and water; (3) a deoxidant composed of glycerin, an alkaline substance and a transition metal compound (excluding dithionite); ) A deoxidizer consisting of glycerin, an alkaline substance, a transition metal compound (excluding dithionite) and water, (5) a deoxidizer consisting of glycerin, an alkaline substance and a water-insoluble solid, (6) glycerin, An oxygen absorber consisting of an alkaline substance, a poorly water-soluble solid and water, (7) glycerin, an alkaline substance, a transition metal compound (8) glycerin, an alkaline substance, a transition metal compound (however, excluding dithionite), a deoxidizer composed of a poorly water-soluble solid and water. Can be

In the above solution, glycerin may be a commercially available one, and may contain impurities such as water.

Further, the alkaline substance is a substance which exhibits alkalinity by acting on or dissolving in water, such as an alkali metal or alkaline earth metal hydroxide, carbonate, hydrogen carbonate, tertiary phosphate, Secondary phosphates and the like are preferable, and alkali metal and alkaline earth metal hydroxides are particularly preferable. Specifically, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, trisodium phosphate, dibasic sodium phosphate, potassium hydroxide, potassium carbonate,
Preferred are potassium hydrogen carbonate, potassium triphosphate, dipotassium phosphate, calcium hydroxide, magnesium hydroxide and the like. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like are particularly preferable. The alkaline substance can be used alone or in combination of two or more. The mixing amount of the alkaline substance with respect to glycerin is preferably at least 10 times, more preferably 30 to 1,000 parts, per 100 parts of glycerin (parts by weight, hereinafter the same). If the mixing amount of the alkaline substance is less than the above range, it is not preferable because the oxygen absorption amount as the composition is small, and if the mixing amount of the alkaline substance is more than the above range, the oxygen absorption amount per unit weight is small. It is necessary to increase the size of the packaging material for packaging the composition, which causes inadequacy in loading the food package, and is also undesirable in appearance.

Transition metal compounds (excluding dithionite) include transition metal halides, sulfates, nitrates, phosphates, carbonates, organic acid salts, oxides, hydroxides, and other double salts. , A chelate compound and the like, and a compound which generates a metal ion in the presence of water is preferable. As the transition metal, iron, cobalt, nickel, copper, zinc, manganese or the like is used. Copper, iron, manganese or the like is preferable, and iron is most preferable in consideration of safety. Specific examples of the most preferred transition metal compound (excluding dithionite) include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous hydroxide, and ferrous hydroxide. Inorganic or organic iron compounds such as ferrous iron, iron citrate, ferrous tartrate and ferric tartrate can be mentioned. These transition metal compounds may be added alone or in combination of two or more, if necessary, and serve as a catalyst for the composition of the present invention, and the amount thereof is preferably at least 1 part based on 100 parts of glycerol, Particularly preferred is 5 parts or more.

A poorly water-soluble solid is a solid substance that is insoluble or hardly soluble in water, and specifically, for example, activated carbon, zeolite,
Perlite, diatomaceous earth, activated clay, silica, kaolin, talc, benite, activated alumina, gypsum, silica alumina, calcium silicate, magnesium oxide, graphite, carbon black, aluminum hydroxide, iron oxide, etc. Can be The hardly water-soluble solid is used alone or in combination of two or more as necessary. By blending the poorly water-soluble solid, it is possible to increase the oxygen absorption rate or oxygen absorption amount and to simplify the handling of the composition.
Further, the contact area of the liquid component in the composition with oxygen can be increased by blending the hardly water-soluble solid. The amount of the hardly water-soluble solid is appropriately selected in relation to other components, and is not particularly limited, but is preferably 0.1 to 10,000 parts, more preferably 1 to 1,000 parts, per 100 parts of glycerin.

When water is not added in the above-mentioned solution, the water necessary for the reaction is supplied by water that evaporates from the preservation material such as food. When water is added to the oxygen scavenger composition, the oxygen absorption reaction proceeds without depending on water from food or the like, so that the progress of the oxygen absorption reaction can be adjusted by the amount of water added. The amount of water to be added in this case is not particularly limited, but is preferably adjusted to 70% by weight or less of the whole composition, more preferably 50% by weight or less. If the amount of water added is greater than the above range, the composition becomes a paste, and the area of contact of the composition with oxygen is undesirably reduced.

In the present invention, the mixing method of each component described above is not particularly limited. When the components are a liquid and a powder, any method may be used as long as each component can be uniformly mixed. A method of impregnating the liquid with the liquid after adding the liquid to the granular material and so on may be employed. Each of the above components is usually contained in a breathable packaging material to form a package. As the packaging method, for example, after mixing the respective components, the components can be wrapped in a small bag sealed by a packing machine with a heat seal at a peripheral portion of a breathable packaging material to obtain an oxygen absorber package.

The package of the oxygen scavenger can be provided for preservation of foods and the like by a method of containing and sealing in a non-breathable packaging material with the foods or a hermetic container together with the foods.

[Action]

The oxygen absorber of the present invention is applied to foods with relatively high water content when water is not added to the composition, and the type that absorbs moisture evaporating from food into the composition to absorb oxygen is used. Can be. Glycerin has an extremely strong hygroscopic property, and thus performs a good deoxygenating function in an atmosphere having a high water vapor acidity. In this case, there is an advantage that the handleability until sealing with the food is good. In addition, if water is added to the composition, it can be used as a deoxidizing agent that deoxidizes regardless of the water content of the food.

〔Example〕

Examples 1 to 8 Oxygen absorbers shown in Table 1 were mixed and then stored in a small bag (50 mm long, 80 mm wide) made of a packaging material laminated with paper and perforated polyethylene. It was a package.
This oxygen absorber package was put together with 1,000 ml of air into a bag in which polyvinylidene chloride-coated stretched nylon and polyethylene were laminated, sealed, and allowed to stand at 25 ° C. Six days later, the oxygen concentration in the bag was measured, and the amount of oxygen absorbed was determined, as shown in Table 1.

In Examples 1, 3, 5, and 7, absorbent cotton impregnated with water was sealed together, and the operation was performed under a relative humidity of 100%.

Example 9 Glycerin 2 g, calcium hydroxide 2 g, ferrous chloride 0.4
g, 1.2 g of silica powder, 0.4 g of activated carbon and 1.2 g of water were mixed and used as an oxygen scavenger.

Two days later, when the oxygen concentration in the bag was measured, the oxygen concentration was
It was less than 0.1%. The amount of oxygen absorbed at this time was 206 ml.

Example 10 2 g of glycerin, 3.4 g of calcium hydroxide, manganese chloride
The same operation as in Example 1 was carried out except that 0.6 g, 2.6 g of silica powder and 2 g of water were mixed and used as an oxygen scavenger.

Two days later, when the oxygen concentration in the bag was measured, the oxygen concentration was
It was less than 0.1%. The amount of oxygen absorbed at this time was 206 ml.

Example 11 glycerin 2 g, calcium hydroxide 3.4 g, copper sulfate 0.6 g,
The same operation as in Example 1 was carried out except that 2.6 g of activated carbon and 3.4 g of water were mixed and used as an oxygen scavenger.

Two days later, when the oxygen concentration in the bag was measured, the oxygen concentration was
It was less than 0.1%. The amount of oxygen absorbed at this time was 206 ml.

Example 12 After 400 adults of black elephant were bred in 1 kg of brown rice for 1 week, the adults were removed. Divide the remaining brown rice into 40g each,
The following samples were provided.

40 g of brown rice as a sample and the oxygen scavenger package of Example 9 were placed in a bag formed by laminating polyvinylidene chloride-coated stretched nylon and polyethylene, and sealed so that the air amount in the bag was 1,000 ml. Ten identical samples were prepared and stored in a constant temperature room at 20 ° C. After storage for 20 days, the container was opened and left as it was in a room at 25 ° C., and the number of black elephants emerging from the sample brown rice was recorded.

The same test as above was carried out except that the oxygen scavenger package was not enclosed in the bag as a control. In this case, the number of black elephants that emerged was set to 100%.

 The results are shown in Table 2.

Example 13 Ten buns of 15 g and the oxygen absorber package of Example 11 were placed in a bag formed by laminating polyvinylidene chloride coated stretched nylon and polyethylene so that the air amount in the bag was 1,000 ml. Stored tightly at 20 ° C. One week later, the oxygen concentration and carbon dioxide concentration in the bag were measured, and the properties of the bun were observed.

The same test as described above was conducted except that the oxygen scavenger package was not enclosed in a bag as a control.

 The results are shown in Table 3.

[Effects of the Invention] Since the oxygen scavenger of the present invention does not use iron powder, it does not detect even if it is put on a metal detector after sealing with food, so that it is possible to inspect for contamination of food. Furthermore, since glycerin is used as a main ingredient, the safety of components is high, and no toxic gas is emitted during the reaction.

The oxygen scavenger of the present invention can be used not only for preservation of foods (antifungal, prevention of decay by bacteria, prevention of insects, prevention of oxidative deterioration, retention of flavor and freshness, prevention of fading, etc.) Clothing, fur, medical equipment / instruments, precision equipment / equipment / parts, electronic equipment / equipment, electronic materials / parts, preservation of articles such as antiques, fungicide, prevention of microbial contamination such as bacteria, insect control, oxidation prevention It can be applied to a wide range of articles to be stored, such as fading prevention and rust prevention.

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Claims (12)

(57) [Claims] An oxygen scavenger comprising glycerin and an alkaline substance. 2. An oxygen scavenger comprising glycerin, an alkaline substance and water. 3. An oxygen scavenger comprising glycerin, an alkaline substance and a transition metal compound (excluding dithionite). 4. An oxygen scavenger comprising glycerin, an alkaline substance, a transition metal compound (excluding dithionite) and water. 5. An oxygen scavenger comprising glycerin, an alkaline substance and a hardly water-soluble solid. 6. An oxygen scavenger comprising glycerin, an alkaline substance, a hardly water-soluble solid and water. 7. An oxygen scavenger comprising glycerin, an alkaline substance, a transition metal compound (excluding dithionite) and a hardly water-soluble solid. 8. An oxygen scavenger comprising glycerin, an alkaline substance, a transition metal compound (excluding dithionite), a poorly water-soluble solid, and water. 9. The method according to claim 1, wherein the alkaline substance is a hydroxide, carbonate, hydrogencarbonate, tertiary phosphate or secondary phosphate of an alkali metal or alkaline earth metal. Oxygen agent. 10. The transition metal compound (excluding dithionite) is a halide, sulfate, nitrate, phosphate, carbonate, organic acid salt or hydroxide of iron, copper or manganese. The oxygen scavenger according to claim 3, 4, 7, or 8. 11. An oxygen-absorbing agent package containing the oxygen-absorbing agent according to claim 1 in a small bag made of a breathable packaging material. 12. A food package comprising the oxygen scavenger package according to claim 11 and food in an airtight container made of a non-breathable packaging material.