JPH0443694B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxygen scavenger with excellent reaction activity with atmospheric oxygen (oxygen scavenging activity).

It has been known that metallic iron, iron alloys, and iron compounds (hereinafter referred to as iron components) such as metallic iron, iron carbide, silicon iron, and iron carbonate react with atmospheric oxygen in the presence of moisture. Various oxygen scavengers using this principle have been proposed. However, since such iron components react slowly with oxygen in the air, they are generally used in combination with various electrolytes as auxiliaries, but in this case, the deoxidation reaction rate varies depending on the type of electrolyte. metal halides generally exhibit the best deoxidation reaction activity.

The present inventors have developed an oxygen scavenger consisting of a combination of such an iron component and an electrolyte as an auxiliary agent.
After conducting various studies on the types of electrolytes used as auxiliary agents and their effect on promoting the deoxidation reaction, it was surprisingly discovered that porous materials adsorbed with chlorine dioxide have an excellent effect on promoting the deoxidation reaction.
The present invention has now been completed.

That is, according to the present invention, there is provided an oxygen scavenger characterized by comprising an iron component having oxygen scavenging activity and an auxiliary component formed by adsorbing chlorine dioxide onto a porous material.

In addition to metallic iron, the iron component used in the present invention includes iron alloys such as iron carbide and iron silicon, and iron compounds such as iron carbonate and iron acetate. All of these react with atmospheric oxygen in the presence of a water bulge. In this case, it is advantageous to use the iron component in the form of fine powder with a small particle size, and the amount of iron component passing through 150 meshes is 50
It is advantageous to use a fine powder of at least 80% by weight, preferably at least 80% by weight.

The auxiliary component used in the present invention is chlorine dioxide adsorbed onto a porous material. In this case, the adsorption treatment of chlorine dioxide can be carried out by adding and mixing chlorine dioxide in the form of an aqueous solution to the filler, or, of course, it is also possible to directly add chlorine dioxide itself. Various porous substances are employed as the porous substance, such as zeolite, sepiolite, loess, kaolin, diatomaceous earth, talc, bentonite, perlite, white clay, activated carbon,
Examples include porous materials such as silica, alumina, magnesia, and silica gel. This porous material is used in the form of powder or granules, and its particle size is not particularly limited, but generally those with an average particle size in the range of 50 to 200 mesh are employed. Even more advantageously,
As this porous substance, it is preferable to use two types, coarse powder and fine powder, in combination. In this case, as the fine powder porous material, one whose passing through the 100 to 150 mesh is 50% by weight or more, preferably in the range of 80 to 100% by weight, is applied, and as the coarse powder porous material, 100 to 150 mesh is used.
A material having a mesh passing amount of 50% by weight or less, preferably a 50 mesh passing amount of 50% by weight or less is used, and in some cases, particles having a particle size of about 2 to 5 mm can also be used. In addition, in order to produce an auxiliary component by using a combination of fine powder and coarse powder of the porous substance described above, first, the coarse powder porous substance is made to contain an aqueous solution of chlorine dioxide, and then this is mixed with fine powder. Mix porous materials. In this case, the fine powder component and the coarse powder component are preferably manufactured from the same raw material, but they may be manufactured from different raw materials. For example, the fine powder component may be zeolite,
Activated carbon can be used as the coarse powder component, and vice versa.

The amount of the aqueous solution of chlorine dioxide added to the coarse powder component is based on the mixture of the fine powder component and the coarse powder component, and the total water content is below its saturated water absorption, usually 20 to 90% of the saturated water absorption. Preferably 30-60%
It is better to make it so that As the total water content in the mixture increases, the flowability of the mixture becomes correspondingly poorer, resulting in poorer compatibility with filling machines. Furthermore, when the moisture content approaches the saturated water absorption capacity of the porous material, wetting occurs on the powder surface, which naturally causes the powders to adhere to each other. This is not preferable because the surface becomes wet with adhering water, which significantly inhibits the oxygen scavenging activity of the iron component. The mixing ratio of the fine powder component and the coarse powder component is 10 to 80% by volume, preferably 30 to 60% by volume of the fine powder component.
and coarse powder component 90-20% by weight, preferably 70-40%
It is capacity %. A porous material made of a mixture of fine powder and coarse powder and containing chlorine dioxide has good fluidity and excellent compatibility with filling machines, and is also excellent as a reaction auxiliary component for iron components. shows.

In the present invention, the amount of chlorine dioxide added to the filler is not particularly limited, but is generally 0.01 to 10 g, preferably 0.1 g to 100 cm ³ of the porous material.
A small amount of ~5g is sufficient. In addition, when a chlorine dioxide aqueous solution is contained in a filler, other auxiliary components can be added to this aqueous solution as necessary, for example, other electrolytes such as metal halide compounds can be added, and dry Glycerin, polyethylene glycol, etc. can be added as an inhibitor, and furthermore, ethanol, ethylene glycol, etc. can be added as an antifreeze agent. The amount of porous material containing chlorine dioxide used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 1 part by weight of the metal component.

In the present invention, it has been found that when a porous material adsorbing chlorine dioxide is used as an auxiliary additive component, a very advantageous oxygen scavenger can be obtained.
In other words, an oxygen absorber that combines a porous material that has adsorbed chlorine dioxide and an iron component has the property of releasing chlorine dioxide gas, which has sterilizing power, in the presence of moisture, so it is not a sterilizing agent. It can be used as a powerful oxygen scavenger. In the case of oxygen scavengers, they can effectively suppress the growth of aerobic bacteria such as mold because they can reduce the oxygen concentration within the food packaging to 1% or less. It showed no effect on the proliferation of. On the other hand, since chlorine dioxide exhibits excellent sterilizing power against anaerobic bacteria, it can effectively suppress the growth of anaerobic bacteria within the packaging system. Moreover, this chlorine dioxide has sterilizing power against not only anaerobic bacteria but also aerobic bacteria.
Therefore, the oxygen scavenger of the present invention can be said to be an epoch-making product that has both oxygen scavenging and sterilizing functions, and its significance in the food field is extremely great.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Iron component: As the iron component, reduced iron powder with a 150 mesh passing amount of 65% by weight and a 200 mesh passing amount of 50% by weight was used.

(2) Auxiliary component: An aqueous solution of chlorine dioxide with a concentration of 0.8% by weight is mixed with a porous material (sepiolite) (particle diameter: approximately 0.5~
1 mm, moisture 8% by weight) per 100 parts by weight, 20
They were added in parts by weight and mixed uniformly to obtain a porous material on which chlorine dioxide was adsorbed. This porous material containing chlorine dioxide had excellent fluidity with no adhering water observed on its surface.

(3) Oxygen scavenger reactivity test 1.5 g of the above iron powder was filled into medicine wrapping paper (manufactured by Kepron Co., Ltd., medicine wrapping paper for Kepron No. 1), then 4 g of the porous substance containing chlorine dioxide was filled, and the opening was closed. It was sealed to produce an oxygen absorber filling bag.

This oxygen absorber-filled bag was placed in a container (plastic bag) with a space volume of approximately 720 c.c., and the entirety was sealed, and the oxygen concentration in the sealed space was measured at predetermined time intervals. As a result, the oxygen concentration was 14% in 6 hours and 14% in 24 hours.
4.5%, and 0.1% at 48 hours.

Example 2 10 g of an aqueous solution containing 0.8% by weight of chlorine dioxide and 5% by weight of common salt was added to and mixed with 50 g of granular zeolite. Put 4g of this mixture and 1.5g of iron powder into a medicine bag,
An oxygen scavenger filling bag A was prepared by sealing the opening.
Place this oxygen absorber filling bag A into a piece of rice cake (approximately 40g).
It was placed in a plastic container with an internal volume of approximately 720 c.c., and the whole was sealed.

On the other hand, for comparison, 10 g of a 6% aqueous solution of sodium chloride was added to and mixed with 50 g of zeolite granules. Put 4g of the mixture and 1.5g of iron powder into a paper bag,
An oxygen scavenger filling bag B was prepared by sealing the opening.
This deoxidizer-filled bag B was placed in a plastic container B together with 40 g of waxy slices in exactly the same manner as the oxygen agent-filled bag A, and the whole was sealed.

Next, after 36 hours had passed, the oxygen concentration in each container was measured, and the oxygen concentration in both containers A and B was 0.1% or less. That is, it was confirmed that it was completely deoxidized.

Next, one pinhole was made with a needle in the containers A and B, and the containers were left at room temperature to observe the growth of mold on the surface of the sticky rice cakes. the result,
The rice cakes in Container B for comparison showed mold growth after 4 days, and after 7 days, the entire surface was covered with blue mold. On the other hand, no mold growth was observed on the rice cakes held in the container A according to the present invention even after one month had passed.

Note that the oxygen concentration in containers A and B did not drop below 10% due to the pinholes being drilled, and the oxygen concentration in both containers after 3 days was approximately 11%. .

From the above results, it is considered that the mold prevention in Container A observed in this case is clearly due to the action of a trace amount of chlorine dioxide released from the filler used as an auxiliary component.

Claims (1)

[Claims] 1. An oxygen scavenger consisting of an iron component with oxygen scavenging activity and a porous material that has adsorbed chlorine dioxide.