JP2596598B2 - Method for producing edible oxygen scavenger - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an edible oxygen absorber for deoxidizing and preserving food.

(Prior art)

Conventionally, as a method for improving the preservability of food by utilizing the deoxygenating ability of coexisting glucose, glucose oxidase / catalase preparation and water, as described in U.S. Pat.No. 2,758,932, glucose oxidase A method of enclosing an aqueous solution containing a catalase preparation and glucose in a bag made of a film material having water resistance such as polyethylene, and storing it airtightly with food,
As described in JP-A-49-86285, after an aqueous solution containing glucose oxidase / catalase and glucose is absorbed into a porous material such as a crosslinked polymer material,
There has been a method in which this is sealed in a bag made of a water-resistant film material having air permeability, and when used, the sealed oxygen absorbent bag is stored in an airtight container together with food. However, in the former method, since the air permeability of the bag made of the film material is used, the bag made of the film material is forced to be very thin. There is a flaw that stains the prepared food. In addition, the latter method has a drawback in that a porous material having a large specific volume is used as a carrier, so that an extra packaging material is required and a special material is required as a carrier. In both cases, if the oxygen absorbent itself comes into direct contact with the preserved food, it poses a problem in food hygiene.

Therefore, as a solution to the above disadvantage, Japanese Patent Laid-Open No.
There is a technique according to 83266. The oxygen scavenger according to this technology is a water-in-oil type of glucose, a glucose oxidase / catalase preparation and an aqueous phase as an inhibitor of crystallization of glucose, and an oil phase composed of an edible oil and fat and an emulsifier which are solid at ordinary temperature. This is an edible coating material in an elsion state.

[Problems to be solved by the invention]

However, in the edible coating material disclosed in the above-mentioned JP-A-57-83266, since fats and oils are used as a material, applicable foods include fats and oils such as peanuts, hazelnuts or chocolate, and can be coated. Limited to solid foods. In addition, the reaction for absorbing oxygen is carried out in the aqueous phase, but in the coating material, the aqueous phase is surrounded by the oil phase, so that it is not easy for oxygen to dissolve into the aqueous phase, and the oxygen absorption rate is low. Is significantly limited. Furthermore, the weight ratio of the aqueous phase to the entire coating material is 50%.
The amount of oxygen absorbed per unit weight is extremely small because it is appropriate or less, and a large amount of coating material is required for better deoxygenation.

The present invention has been completed in view of the above points, is edible, can be brought into direct contact with food, and has a good function retention that does not reduce the deoxygenation ability before use. An object of the present invention is to provide an oxygen scavenger having a sufficient oxygen absorbing power.

[Means for solving the problem]

As a result of repeated studies to achieve the above object, the present inventors have obtained the following findings and completed the present invention.

Glucose oxidase oxidizes glucose and produces gluconic acid and hydrogen peroxide (C ₆ H ₁₂ O ₆ + H ₂ O +
O ₂ → C ₆ H ₁₂ O ₇ + H ₂ O ₂ ), and tacalase reacts to decompose the hydrogen peroxide generated by this reaction (2H ₂ O ₂
→ O ₂ + 2H ₂ O) is catalyzed.

That is, the reaction of (2C ₆ H ₁₂ O ₆ + O ₂ → 2C ₆ H ₁₂ O ₇ ) proceeds, and the effect of oxygen absorption, that is, the effect of deoxygenation in the outside world can be obtained by utilizing this reaction.

On the other hand, since the reaction catalyzed by glucose oxidase is a reaction requiring water, the reaction can be stopped by drying. Furthermore, in the case of drying, freeze-drying can be employed to prevent enzyme inactivation due to heating. Thus, the freeze-dried product obtained by the treatment becomes an oxygen scavenger that can maintain the oxygen absorbing power without stopping the reaction unless it absorbs moisture.
Accordingly, the gist of the present invention is to provide an edible oxygen scavenger characterized in that glucose and glucose oxidase / catalase are supported on a carrier having water absorbency and water retention together with water, and then the carrier is freeze-dried. It is a manufacturing method of.

 Hereinafter, the present invention will be described in detail.

First, an edible carrier is used as the carrier having water absorbency and water retention in the present invention, and usually, cellulose powder, starch or an appropriate mixture thereof is used.
As the cellulose powder, a powder of 200 mesh or less is usually used to make the oxygen scavenger porous. In addition, as the starch, raw starch such as potato, corn, rice, wheat or the like or a processed starch thereof (alpha starch, dextrin, soluble starch, etc.) can be used. By using starch, sedimentation of contents such as oxygen preparations in an aqueous solution before freeze-drying can be prevented, and the oxygen absorber after drying can be prevented from becoming non-uniform, and can be prevented from being out of shape. When using a mixture of starch and cellulose powder as the carrier, in order to improve the water retention, 1 to starch.
It is preferable to use three times the weight of cellulose powder.

As the glucose used in the present invention, commercially available glucose can be generally used, and the amount added to the oxygen scavenger is determined according to the amount of oxygen to be absorbed when the oxygen scavenger is used. However, when the glucose content in the dry weight of the oxygen scavenger exceeds 50% by weight, it takes time to freeze-dry the aqueous solution, and further, when the oxygen scavenger is stored in a dry state, the oxygen scavenger is not used during storage. It becomes easy to absorb moisture, which causes a decrease in deoxygenation ability. Therefore, it is preferable that the glucose content does not exceed 50% by weight.

Glucose oxidase / catalase can be generally used in the form of a commercial preparation. Its titer is 30 ° C, oxygen 1.
Assuming that the unit absorbs 0 × 10 ⁻³ ml, the amount of the enzyme added to the oxygen scavenger is 1 unit of the air in the sealed package.
If deoxygenated within 30 days, 30 ml per 40 ml of air in the package
Effective deoxygenation can be performed by setting the amount to about 0 to 1000 units. More preferably, about 600 units is particularly effective from the viewpoints of deoxygenation ability and economy. That is, if the content of glucose oxidase / catalase is less than 300 units, the deoxygenating ability may not be sufficiently exhibited. Further, even if the content is added so as to be more than 1000 units, the residual oxygen amount cannot be remarkably reduced, so that it is economical to set the content to 1000 units or less. In addition, it is needless to say that individual glucose oxidase and catalase can be mixed and prepared in consideration of the respective titers.

In the method of the present invention, glucose and glucose oxidase / catalase are made into an aqueous solution together with a carrier having water absorbing and water retaining properties. Mixing when making the aqueous solution,
In order to prevent the deoxidation reaction of the oxygen scavenger from proceeding as much as possible by mixing, it is preferable to perform the reaction at a temperature lower than normal temperature and quickly. Alternatively, the aqueous solution can be obtained by mixing a previously prepared aqueous solution of glucose oxidase / catalase with an aqueous solution obtained by mixing glucose and a carrier.

The amount of water used in the aqueous solution is desirably 15 to 25 times the weight of the carrier, and if the amount used is less than 15 times the weight, the oxygen scavenger to be a product is subjected to the following freeze-drying treatment. Are not easily porous, and a material having a sufficient water retention ability cannot be obtained. On the other hand, if the weight is more than 25 times the weight, a large amount of time and high cost are required for freeze-drying in the next step, which is not preferable in terms of production efficiency and economy.

Next, the aqueous solution is frozen as quickly as possible to stop the oxygen absorption reaction by glucose oxidase / catalase in the aqueous solution, and then dried by a vacuum drying method to maintain the oxygen activity.
The freeze-drying treatment can be performed by a usual method. When the water content of the freeze-dried product is 3% or less, the oxygen scavenger according to the present invention can be obtained.

Furthermore, in the present invention, glucose oxidase
As a result of the oxygen absorption reaction catalyzed by catalase, glucose is oxidized to produce gluconic acid,
pH drops. Therefore, it is preferable to add a buffer in advance when preparing an aqueous solution of glucose, glucose oxidase / catalase, and a carrier in order to prevent the enzyme from being deactivated due to a decrease in pH. As the buffer, sodium citrate, sodium carbonate, sodium phosphate, or the like can be used, and the buffer is added so that the pH when the oxygen scavenger is used is 5.0 to 8.0. In this range, the deoxygenation ability tends to increase at a higher pH, so that the reaction system is preferably set in a neutral to alkaline range. However,
If the pH exceeds 8.0, the stability of the enzyme activity may be adversely affected, and the taste of the food to be deoxygenated may be adversely affected.

(Operation)

Foods can be deoxygenated and stored using the oxygen scavenger according to the present invention. That is, the oxygen absorber according to the present invention starts the enzyme absorption reaction catalyzed by glucose oxidase / catalase by absorbing water,
Immediately before the food is sealed and stored in the air-impermeable packaging material, the oxygen absorber according to the present invention absorbs water and is added to the contained food,
Or, when the food itself is a highly water-containing food, the oxygen absorber according to the present invention is directly attached to the food while being dried, and then deoxygenated in the package by sealing, and the food is stored for a long time. be able to. The amount of water absorbed when the oxygen absorber is used is usually practically 2 to 4 times the weight of the carrier. As the shape of the oxygen absorber, a pellet, a stick, a sheet, a granule, or the like is appropriately employed depending on the type or shape of the food to be stored.
The oxygen scavenger according to the present invention can be used for deoxidizing and preserving various foods, and has a wide versatility. However, it is preferable that the food to be preserved is a water-containing food. Also, when water is absorbed by the oxygen absorber at the start of use, several percent of alcohol (edible)
When added together with water, alcohol is vaporized and the oxygen concentration in the package is relatively reduced, which is effective for more complete deoxygenation storage.

〔Example〕

After mixing 20.4 g of cellulose powder, 20.4 g of potato starch, 47.4 g of glucose, 4.7 g of trisodium citrate, and 700 ml of water, the mixture is gradually heated. The heating is performed while mixing well until the starch is completely gelatinized to obtain a first solution. An aqueous solution (355 units / ml of enzyme activity) of a glucose oxidase / catalase preparation prepared in advance is mixed with the first solution to obtain a second solution. At this time, the first solution prepared in advance is kept at a temperature of 40 ° C. or less in order to prevent inactivation of the enzyme. Once the second solution has been thoroughly mixed, it is placed in a molding container and immediately frozen. The frozen second solution is dried at a vacuum of 0.5 Torr at 60 ° C. for about 24 hours,
As a%, 91 g of the oxygen scavenger of the present invention was obtained.

[Test Example I]

FIG. 1 shows the oxygen absorber 422m obtained according to the above embodiment.
The time-dependent change in the oxygen concentration in the container when 0.5 ml of water was added to g (dry weight) and deoxidation was performed in a sealed container having a capacity of 40 ml is shown. The container used for the test used an air-impermeable syringe, and the reaction was performed at 30 ° C.

From FIG. 1, when 0.5 ml of water is added to 422 mg (dry weight) of the oxygen scavenger according to the present invention, oxygen is almost completely removed from 40 ml (30 ° C.) of air for about 8 hours. I understand.

(Test Example II)

FIG. 2 shows the case where the oxygen absorber of the above embodiment absorbing 2% ethyl alcohol was added (deoxygenation zone), the case where no oxygen absorber was added (control zone), and the case where the oxygen absorber was used. The results of a rice cake preservation test are shown for the case where only 2% ethyl alcohol was added in the same amount as the deoxygenated zone without adding (alcohol zone).

In this preservation test, 30 g of commercially available raw mochi was used, and each of the raw mochi was used as a 160 ml capacity air-impermeable pouch (PET 12 μm).
/ AL9μ / ON15μ / HDPE60μ) and stored at 30 ° C. In the oxygen-absorbing zone, an oxygen absorber made by absorbing 1.5 ml of 2% ethyl alcohol into 1.2 g (dry weight) of the oxygen absorber,
Only 1.5 ml of 2% ethyl alcohol in the alcohol area,
Each was enclosed in a pouch with rice cake.

FIG. 2 shows the results of a sensory test on the oxygen concentration in the pouch, the degree of mold generation on the rice cake surface, and the odor 1 to 4 weeks after the sealed storage in the pouch.

FIG. 2 clearly shows that the oxygen scavenger according to the present invention has the effect of removing oxygen in the pouch, preventing the growth of mold and extending the shelf life of the rice cake.

(Effect)

As described above, the oxygen absorber according to the present invention has a versatile, warm, porous structure that can be directly added to food because the carrier and other raw materials are all edible, Because it can contain a relatively large amount of water,
It is a good oxygen absorber with a high oxygen absorption rate and a large amount of absorbed oxygen. Furthermore, as long as it is dry, the oxygen scavenging ability is stopped and the oxygen scavenging ability is not reduced, so that the function is excellent and the storage stability of the oxygen scavenger itself is also excellent.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing the deoxidizing effect of one embodiment of the oxygen scavenger of the present invention, and FIG. 2 is a preservation test of rice cake by one embodiment of the oxygen scavenger of the present invention. FIG.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masahiro Yamazaki 4-1-1, Nishinakajima, Yodogawa-ku, Osaka-shi, Osaka

Claims (1)

(57) [Claims] 1. Glucose and glucose oxidase.
A method for producing an edible oxygen scavenger, comprising: supporting catalase together with water on a carrier having water absorbency and water retention, and then freeze-drying the carrier.