JPH057773A - Oxygen absorber - Google Patents

Abstract

(57) [Summary] [Purpose] To reduce the size of oxygen absorbers mainly composed of ascorbic acid, and to enable them to be manufactured at low cost. [Composition] The oxygen scavenger is composed of ascorbic acid, an inorganic alkaline substance, a deliquescent substance, a ferrous salt and a dispersant, and is added to the total amount of ascorbic acid, an inorganic alkaline substance, a deliquescent substance and a ferrous salt. At least 3 ascorbic acid
5% by weight and at least one of an inorganic alkaline substance, a deliquescent substance and a ferrous salt is a compound having water of crystallization, which comprises ascorbic acid, an inorganic alkaline substance, a deliquescent substance and a ferrous salt. At least 20% by weight of the water of crystallization is contained in total. As the inorganic alkaline substance, an alkali metal hydroxide and / or an alkali metal carbonate can be used, and an alkali metal hydrogen carbonate may be added.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an oxygen scavenger for absorbing oxygen and generating carbon dioxide gas to prevent deterioration of the quality of foods and the like due to oxygen, and to prevent the growth of microorganisms and mold. Regarding

[0002]

2. Description of the Related Art The typical deterioration of the quality of foods is discoloration of foods, rancidity of oils and fats contained in foods, or reproduction of aerobic bacteria and molds. Oxygen is involved in the deterioration of food quality. Therefore, it has been conventionally practiced to block food from oxygen. For example, foods have been vacuum-packed, nitrogen gas displacement-packed, or air-tightly packed, and at that time, an oxygen absorber is enclosed therein.

As such an oxygen scavenger, one mainly composed of iron powder is generally used, but in the case of foods, a metal detector is used to investigate whether metallic foreign matter is mixed in the package. In such a case, the conventional iron powder-based one would be detected by the metal detector, so an oxygen scavenger mainly composed of ascorbic acid not detected by the metal detector has been proposed. (Japanese Patent Publication No. 58-29069).

[0004]

However, the oxygen scavenger mainly containing ascorbic acid has a problem that the oxygen absorption rate is slower than that mainly containing iron powder. Therefore, not only ascorbic acid, which is the main component, but also other components must be used in a large amount, which results in a problem that the whole becomes heavy and bulky, and the manufacturing cost becomes high. Especially, in the recent trend of diversification and upsizing of food, it is said that each food such as rice cracker, chocolate candy, petit cake, etc. is hermetically packaged and several of them are put together in a large packaging bag. With the widespread adoption of various food packaging forms, it has also become possible to encapsulate an oxygen scavenger in each of the small packages containing such rice crackers. However, the conventional oxygen scavenger mainly containing ascorbic acid has a problem that it cannot be used for such a small package in terms of size and cost.

The present invention is intended to solve the problems of the prior art as described above, and it is an object of the present invention to reduce the size of an oxygen scavenger mainly containing ascorbic acid so that it can be produced at low cost. .

[0006]

The above objects have been achieved by the present invention described below. That is, the present invention, ascorbic acid, an inorganic alkaline substance, a deliquescent substance, a deoxidizer consisting of a ferrous salt and a dispersant, ascorbic acid, an inorganic alkaline substance, a deliquescent substance and a ferrous salt to the total A compound containing at least 35% by weight of the ascorbic acid, and at least one of an inorganic alkaline substance, a deliquescent substance and a ferrous salt having water of crystallization, which is ascorbic acid, an inorganic alkaline substance, a deliquescent substance. And an oxygen scavenger containing at least 20% by weight of the water of crystallization with respect to the total amount of ferrous salts.

In the oxygen scavenger of the present invention, the oxygen absorption rate and the reaction rate are increased by increasing the content ratio of ascorbic acid, and the content ratio of water of crystallization in the components of the oxygen scavenger is
The oxygen absorbing rate is accelerated by at least 20% by weight in the oxygen scavenger excluding the dispersant, and the oxygen scavenger itself is miniaturized by incorporating each component in the necessary minimum amount.

In the present invention, ascorbic acid is a component that absorbs oxygen, and decomposes with the progress of the oxygen absorption reaction to generate carbon dioxide gas. This carbon dioxide also protects the food from bacteria, mold, insects and the like that cannot grow in a high-concentration carbon dioxide atmosphere, and thus effectively functions to preserve the food. Further, it is possible to compensate for the decrease in gas in the packaging bag due to the absorption of oxygen and prevent the packaging bag from being compressed.
As such ascorbic acid, for example, L-ascorbic acid, D-iso-ascorbic acid or their sodium salts can be used. The particle size of ascorbic acid is preferably 100 mesh pass.

Regarding the blending ratio of ascorbic acid,
If it is too small, the oxygen absorption reaction yield will decrease, and if it is too high, an increase in manufacturing cost cannot be avoided, which is not preferable. Therefore, the content of ascorbic acid in the oxygen scavenger excluding the dispersant is at least 35% by weight, preferably 40 to 50% by weight.

The inorganic alkaline substance used in the present invention brings the pH of the oxygen scavenger to the alkaline side in order to start and maintain the oxygen absorption reaction of ascorbic acid.
Examples of such inorganic alkaline substances include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, or sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and the like. Examples thereof include alkali metal or alkaline earth metal carbonates or hydrated salts thereof. In particular, it is preferable to use calcium hydroxide and sodium carbonate decahydrate together in order to sufficiently absorb oxygen in the hermetically sealed package.

The blending ratio of these inorganic alkaline substances depends on the type of alkaline substance used and the like. For example, when only calcium hydroxide is used,
2 to 15% by weight based on the total amount of ascorbic acid, inorganic alkaline substance, deliquescent substance and ferrous salt in the oxygen absorber,
It is preferably 4 to 8% by weight. Further, when calcium hydroxide and sodium carbonate decahydrate are used in combination, calcium hydroxide is contained in an amount of 2 to 15% by weight, preferably ascorbic acid, an inorganic alkaline substance, a deliquescent substance and a ferrous salt. Is 4 to 8% by weight, and sodium carbonate decahydrate is 10 to 50% by weight, preferably 20 to 30% by weight.

Further, as an inorganic alkaline substance, an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate may be added in addition to the above components. This is because calcium hydroxide has an action of absorbing carbon dioxide gas generated from ascorbic acid, so that carbon dioxide gas can be further generated by adding an alkali metal hydrogencarbonate, thereby improving the quality of food. In addition to preventing deterioration of the food, the reduction of the amount of gas inside the packaging bag due to the absorption of oxygen prevents the food from being compressed due to the packaging bag being crushed. The blending ratio of such a hydrogen carbonate depends on the kind of the carbonate used and the like, but when sodium hydrogen carbonate is used as a preferred carbonate compound, ascorbic acid in the oxygen scavenger, an inorganic alkaline substance, It is 5 to 30% by weight, preferably 8 to 20% by weight, based on the total amount of the deliquescent substance and the ferrous salt.

The particle size of the inorganic alkaline substance is about 60.
Those having a pass of -100 mesh are preferable.

The deliquescent substance used in the present invention absorbs water inside the packaging bag in which the oxygen absorber of the present invention is enclosed,
The purpose is to protect foods and the like contained in the packaging bag from moisture, and to take in water for starting the oxygen absorption reaction in the present invention into the oxygen scavenger. Examples of such deliquescent substances that can be used include aluminum chloride, zinc chloride, calcium chloride, iron chloride, sodium hydrogen sulfate, ferric sulfate, bittern, and crude salt. Also, these hydrous salts such as calcium chloride dihydrate can be used. Further, the particle size of the deliquescent substance is preferably 100 mesh pass. The mixing ratio of such deliquescent substance depends on the type of deliquescent substance used,
When calcium chloride dihydrate is used as a preferable deliquescent substance, ascorbic acid, an inorganic alkaline substance,
It is 2 to 10% by weight, preferably 3 to 7% by weight, based on the total amount of the deliquescent substance and the ferrous salt.

The ferrous salt used in the present invention functions as an oxygen absorption reaction catalyst, and ferrous sulfate, ferrous chloride, ferrous hydroxide, or a hydrous salt thereof can be used. Further, the particle size of the ferrous salt is preferably 60 mesh pass.

The mixing ratio of such ferrous iron salt is
Depending on the type of ferrous salt used, etc., when ferrous sulfate heptahydrate is used as the preferred ferrous salt, ascorbic acid as an oxygen scavenger, inorganic alkaline substance, deliquescent substance and It is 5 to 20% by weight, preferably 8 to 13% by weight, based on the total amount of ferrous salts.

In the present invention, at least one of the above-mentioned inorganic alkaline substance, deliquescent substance and ferrous salt is a compound having water of crystallization, and ascorbic acid as an oxygen scavenger, inorganic alkaline substance, deliquescent substance and It is necessary that the amount of water of crystallization is at least 20% by weight, preferably 25 to 30% by weight, based on the total amount of ferrous salts. If it is lower than this range, the oxygen absorption reaction rate is too slow. Conversely, if it is too high, the oxygen absorber itself becomes sticky and its fluidity decreases, and as a result, the oxygen absorber consists of a breathable material. This is because workability at the time of filling the package is reduced. Further, since the oxygen scavenger of the present invention contains the water necessary for the oxygen absorption reaction as the crystal water in the above-mentioned amount, the oxygen absorption reaction proceeds by contact with oxygen even if water is not supplied from the outside. Therefore, the oxygen scavenger of the present invention can be applied to foods having low water activity, such as dried foods such as rice crackers and beans.

The dispersant used in the present invention uniformly disperses the above-mentioned components, ensures air permeability, provides a place for reaction, and further improves filling work characteristics. As such a dispersant, powdered activated carbon having a water content of 10 to 50%, preferably about 30% is preferable. When activated carbon is used, it is also black in color, so that there is an advantage that the entire mixed state can be easily observed.

The blending ratio of such a dispersant is 10 to 30% by weight, preferably 12 based on the total amount of the oxygen scavenger.
To 20% by weight.

If desired, the oxygen scavenger of the present invention may further contain a binder such as crystalline cellulose in order to form the oxygen scavenger into granules. As a result, in the mixing step for producing the oxygen absorber, part of the water of crystallization in the oxygen absorber is released, and moisture can be uniformly applied to the entire oxygen absorber during mixing. Therefore, it is possible to produce a granular oxygen scavenger with very little variation in performance,
In addition, the handleability of the oxygen scavenger is improved, and high-speed filling work into a package made of a gas permeable material becomes possible. The compounding ratio of the binder varies depending on the kind of the binder used and the like, but when crystalline cellulose is used, it is 1 to 1 with respect to the whole oxygen absorber.
It is 0% by weight, preferably 1 to 5% by weight. After granulation, it is preferable to sprinkle the silicon dioxide fine powder with the granular oxygen scavenger of the present invention. As a result, the field of the reaction is surely ensured, and as a result, the oxygen scavenger exhibits reproducible oxygen absorption performance.

The oxygen scavenger of the present invention is prepared by mixing ascorbic acid, an inorganic alkaline substance, a deliquescent substance, a ferrous salt, a dispersant and, if necessary, a binder as described above according to a conventional method. be able to. For example, these components can be mechanically mixed under a nitrogen gas atmosphere, and if necessary, a granulator can be used to obtain granules of a desired size.

The oxygen absorber of the present invention can maintain its performance by being sealed. Therefore, as a product form of the present invention, the oxygen scavenger of the present invention is filled in a breathable bag-like packaging material and then sealed with an airtight packaging material that blocks oxygen and humidity, and is opened at the time of use. You can do it.

As the packaging material for filling the oxygen scavenger of the present invention, for example, a laminated material having a film having heat sealability, breathability and water resistance on the inner surface and a breathable sheet material on the outer surface is used. You can

As the material for the outer surface, paper, non-woven fabric or the like can be used, and the outer surface may be coated with a silicone-based or fluorine-based water repellent or oil repellent.

As a material for the inner surface, a perforated film such as a perforated polyethylene film or a microporous film can be preferably used. Such a microporous film has a Gurley air permeability of 0.01
It is possible to use a material that does not allow water to pass therethrough at atmospheric pressure at ˜1000 seconds / ml and allows water vapor to pass therethrough. In addition, a mixed paper (having heat sealability, air permeability, water resistance, mechanical strength, etc.) in which fibers of thermoplastic resin such as polyethylene are mixed, non-woven fabric having heat sealability, heat seal varnish It is also possible to use a non-woven fabric coated with, a water-resistant processed paper coated with heat seal varnish, and the like.

The airtight packaging material is generally a metal foil such as an aluminum foil or a laminate including a resin layer having excellent gas barrier properties such as polyvinylidene chloride or a saponified product of ethylene-vinyl acetate copolymer. Airtight materials can be used.

[0027]

The oxygen scavenger of the present invention enhances the oxygen absorption reaction yield by increasing the content ratio of ascorbic acid, and increases the oxygen absorption rate by increasing the content ratio of crystal water in the contained components to at least 20% by weight. It is possible to reduce the size of the oxygen scavenger itself by advancing it and adding the respective components in the required minimum amounts.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 and Comparative Example 1 Components A and B shown in Table 1 below were mixed using a V blender under a nitrogen gas atmosphere, and further granulated using an extrusion granulator, and further 4 parts were mixed. The particles were sprinkled with silicon dioxide (Microcomputer F, manufactured by Tomita Pharmaceutical Co., Ltd.) to obtain the oxygen scavenger of the present invention having a particle diameter of 1 to 2 mm. Similarly, a conventional oxygen absorber was obtained as Comparative Example 1. In the component B, activated carbon was used as a dispersant and crystalline cellulose was used as a binder.

[0029]

[Table 1] Example 1 Comparative example 1     Ingredient A (parts by weight)   L-sodium ascorbate 20 25   NaHCO_Three                                4 25   Na_TwoCO_Three・ 10H_Two0 15 25   CaCl_Two・ 2H_TwoO 2 8.3   Ca (OH)_Two                              Two two   FeSO_Four・ 7H_TwoO 5 4.1     Component B (parts by weight)   Activated carbon (Carboraffin, manufactured by Takeda Pharmaceutical Co., Ltd.) 10 16.7Crystalline cellulose (Avicel, manufactured by Asahi Kasei) 34 Of L-ascorbic acid in the component A of the oxygen scavenger of Example 1
The ratio is about 41.6% by weight, and the water of crystallization in the component A is
Was about 25.4% by weight. On the other hand, in Comparative Example 1
The ratio of L-ascorbic acid in the component A of the oxygen absorber is about 2
8% by weight, and the ratio of crystal water in the component A is about 2
It was 1.9% by weight.

20 g of the oxygen scavenger of the present invention and 36 g of the oxygen scavenger for comparison were mixed with polyethylene-blended paper (50 g
/ M ² ) packaging material (110 mm × 130 mm)
Were filled separately. And a sealed container (volume 2500
(ml) was sealed with air, and the oxygen concentration in the container was measured at room temperature with a zirconia oxygen analyzer over time. As a result, both of them absorbed oxygen in the container almost completely in 36 hours. The carbon dioxide concentration at that time was about 20%.

From this, it was found that the oxygen scavenger of the present invention can be used in an amount about half that of the conventional oxygen absorber in order to obtain almost the same oxygen absorption performance as the conventional oxygen absorber.

[0032]

According to the present invention, the oxygen scavenger mainly containing ascorbic acid can be miniaturized and manufactured at low cost.
Further, since the oxygen absorber of the present invention has a high oxygen absorption rate, it can absorb oxygen in a shorter time than the conventional example,
Further, it is also useful for preservation of food at low temperature.

Claims (4)

[Claims] 1. Ascorbic acid, an inorganic alkaline substance,
An oxygen absorber comprising a deliquescent substance, a ferrous salt and a dispersant, wherein the ascorbic acid is contained in an amount of at least 35% by weight based on the total amount of ascorbic acid, an inorganic alkaline substance, a deliquescent substance and a ferrous salt dispersant. And a compound in which at least one of the inorganic alkaline substance, the deliquescent substance and the ferrous salt has water of crystallization, and the amount of ascorbic acid, the inorganic alkaline substance, the deliquescent substance and the ferrous salt dispersant is An oxygen scavenger containing at least 20% by weight of water of crystallization. 2. The inorganic alkaline substance is an alkali metal hydroxide and / or an alkali metal carbonate.
The described oxygen scavenger. 3. The oxygen scavenger according to claim 2, further comprising an alkali metal hydrogen carbonate. 4. The oxygen scavenger according to claim 1, 2 or 3, further comprising a binder.