JPH04131072A - Deoxidizing agent - Google Patents

Abstract

PURPOSE:To provide a deoxidizing agent not generating acetaldehyde and capable of being prepared at a low cost by compounding a sugar alcohol, an alkaline substance and a transition metal compound. CONSTITUTION:(A) A sugar alcohol (preferably glycerol), (B) an alkaline substance (preferably calcium hydroxide), (C) a transition metal compound (preferably ferrous chloride) and, if necessary, a polyhydric alcohol, a filler, etc., are received in an air-diffusible packaging material to provide the objective deoxidizing agent for ethanol-containing foods. The components A, B and C are preferably employed in a ratio of 100 pts.wt.: 30-5000 pts.wt: >=5 pts.wt., respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen scavenger. More specifically, the present invention relates to a novel oxygen scavenger whose main components are a sugar alcohol, an alkaline substance, and a transition metal compound.

In this specification, the term "oxygen scavenger" is mainly used to mean a "composition that has an oxygen scavenging effect" (oxygen scavenger composition), but it also refers to a "package of a composition that has an oxygen scavenging effect" (oxygen scavenger composition). It is also sometimes used to mean an oxygen agent package.

[Conventional technology]

Oxygen absorbers are used as a preservation technique for foods, etc.
This is a gas-barrier sealed bag or container (hereinafter referred to as
Sometimes simply called a sealed container or container. ) By placing food, etc. and an oxygen scavenger inside the sealed system to create a substantially oxygen-free condition, it suppresses the oxidation of foods, etc. and the growth and proliferation of bacteria and mold. Used for preservation.

Conventionally, oxygen scavengers based on iron powder have been used for reasons such as their oxygen absorption ability, ease of handling, safety, and cost. Furthermore, recently, oxygen scavengers based on ascorbic acid have been put into practical use.

On the other hand, a preservation method that prevents food spoilage by containing ethyl alcohol in the food itself is also commonly practiced.

Using an oxygen absorber in combination with these ethanol-containing foods is more effective in preventing spoilage.

[Problem to be solved by the invention]

However, when ethanol-containing foods are deoxidized using an oxygen absorber based on iron powder, the ethanol that evaporates from the food reacts with the oxygen absorber components to produce acetaldehyde, which causes an unpleasant odor. was there. As a countermeasure to this problem, a method has been proposed in Jikai 62-40273 to blend a compound with an amino group such as a weakly basic ion exchange resin to absorb and remove acetaldehyde, but this method conversely causes the generation of amine odor. Moreover, the formulations were also expensive and impractical.

Furthermore, oxygen scavengers based on ascorbic acid produce much less acetaldehyde than oxygen scavengers based on iron powder, but the cost of the base ingredient is high.

[Means to solve the problem]

The inventors of the present invention have conducted extensive studies to solve the above problems, and have found that an oxygen scavenger consisting of a sugar alcohol, an alkaline substance, and a transition metal compound is low cost and does not generate acetaldehyde for ethanol-containing foods. The present inventors have discovered that it can be suitably used, and have completed the present invention.

That is, the present invention is an ethanol-containing food oxygen absorber comprising a sugar alcohol, an alkaline substance, and a transition metal compound.

Examples of the sugar alcohol in the present invention include sugar alcohols having 3 to 6 carbon atoms, and more specifically, sugar alcohols having 3 carbon atoms such as glycerin, sugar alcohols having 4 carbon atoms such as Eris IJ), arabitol, Examples include sugar alcohols with 5 carbon atoms such as xylitol and arabitol, and sugar alcohols with 6 carbon atoms such as sorbitol and mannitol. Particularly preferred is glycerin.

Furthermore, in addition to sugar alcohols, 1.2-4'' recalls such as propylene glycol, ethylene glycol, and others can also be used as the main ingredient.

Alkaline substances include substances that exhibit alkalinity by acting with or dissolving in water, such as hydroxides, carbonates, hydrogen carbonates, tertiary phosphates, and tertiary phosphates of alkali metals or alkaline earth metals. Acid salts are preferred, and alkali metal hydroxides are particularly preferred. Specifically, preferred examples include sodium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide. Among these, calcium hydroxide is particularly preferred. The alkaline substances can be used alone or in combination of two or more. The amount of the alkaline substance mixed with the sugar alcohol is preferably 10 parts or more, more preferably 30 to 5,000 parts, per 100 parts (by weight, the same applies hereinafter) of the sugar alcohol. If the amount of the alkaline substance mixed is less than the above range, the amount of oxygen absorbed by the composition will be small, which is undesirable.If the amount of the alkaline substance mixed is more than the above range, the amount of oxygen absorbed per unit weight will be small. It is necessary to increase the size of the packaging material used to package the composition, which causes inconvenience in terms of loading into a food package, and is also unfavorable in terms of appearance.

Examples of the transition metal compound include transition metal halides, sulfates, nitrates, phosphates, carbonates, oxides, hydroxides, organic acid salts, other double salts, and chelate compounds. As the transition metal, iron, cobalt, nickel, copper, zinc, manganese, etc. are used, and preferred are iron, copper, manganese, etc., and particularly preferred is manganese, which has a fast reaction rate.

Preferred specific examples of transition metal compounds include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, cuprous chloride, cupric chloride, cupric sulfate, cupric hydroxide, Copper citrate, copper tartrate, manganese chloride, manganese bromide, manganese acetate,
Examples include manganese hydroxide. These transition metal compounds are added singly or in combination of two or more as necessary, and act as a catalyst for the composition of the present invention, and the amount thereof is preferably 1 part or more per 100 parts of sugar alcohol. Particularly preferred is 5 parts or more.

Further, other components can be added to the composition according to the present invention as necessary.

Polyhydric phenols exhibit a catalytic effect similar to transition metal compounds, and are especially effective when used in combination with transition metal compounds, making it possible to increase the amount of oxygen absorbed per unit amount of the composition.

Specific examples of polyhydric phenols include catechol, resorcinol, hydroquinone, pyrogallol, resorcylic acid,
gallic acid, tannin, tannic acid, protocatechuic acid,
Examples include 3,4-dihydroxyphenylalanine and caffeic acid.

The amount of polyhydric phenols added is preferably 1 part or more and 1000 parts or less per 100 parts of glycerin. If the amount added is small, the effect as a catalyst will be insufficient, and even if 1000 parts or more is added, the glycerin will not contribute to an increase in the amount of oxygen absorbed commensurate with the increase in the amount of the composition, resulting in poor economic efficiency.

Addition of a filler is effective, for example, in improving the fluidity of the granular composition and making it easier to handle, as well as increasing the oxygen absorption rate or amount by increasing the contact area of the liquid component with oxygen.

Specific examples of fillers include activated carbon, zeolite 1 perlite, diatomaceous earth, activated clay, silica, kaolin, talc,
bentonite, activated alumina, gypsum, silica alumina,
Examples include powders or granules such as calcium silicate, magnesium oxide, graphite, carbon black, aluminum hydroxide, iron oxide, and the like.

Although it is not always necessary to add water, it is desirable to adjust the amount appropriately since the addition of water may increase the oxygen absorption rate or the amount of oxygen absorption.

In the present invention, there are no particular restrictions on the method of mixing the above-mentioned components, but if the components are liquid and powder, any method that can uniformly mix each component may be used, and if granules are used as the component, for example, A method may be adopted in which the liquid is impregnated into the granular material and then the powder is added so as to be sprinkled thereon. Each of the above components is usually housed in an air-permeable packaging material to form a package. As for the packaging method, for example, after mixing each component, it can be wrapped in a pouch sealed by heat-sealing the periphery of an air-permeable packaging material using a backing machine to form an oxygen absorber package.

This oxygen absorber package can be used to preserve ethanol-containing food by storing it in a non-breathable packaging material and sealing it together with ethanol-containing food, or by storing it together with ethanol-containing food in an airtight container and sealing it. .

Alternatively, a so-called ethanol generator, which is a filler impregnated with ethanol or an aqueous ethanol solution, can be used in conjunction with food preservation.

〔Example〕

Example 1 Glycerin 0.5g, water 0.4g, manganese chloride 0.2
g, calcium hydroxide (granular) 2g, activated carbon 0.05g
After mixing, the mixture was placed in a small bag (50 mm in length and 80 mm in width) made using a packaging material made of a laminate of paper and perforated polyethylene to form an oxygen absorber package. This oxygen absorber package was placed in a bag made of polyvinylidene chloride coated stretched nylon and polyethylene laminated together with 200 ml of air and 100 g of castella sprayed with 4 g of 50% ethanol, and the bag was sealed and left in an atmosphere at 25°C. Table 1 shows the results of gas chromatograph analysis of the oxygen concentration and acetaldehyde concentration in the system after 5 days.

The oxygen concentration inside the bag is completely deoxidized (below 0.1%),
The concentration of acetaldehyde in the system was also below the analysis lower limit of 30 ppm. Furthermore, after the analysis, the bag was opened and the odor was checked, but no abnormal odor including acetaldehyde odor was observed.

Table 15 days later concentration analysis results in the system Example 2 Glycerin 0.5g, water 0.3g, calcium hydroxide 0
゜5g, copper sulfate 0.1g, activated carbon 0. The same procedure as in Example 1 was carried out except that Ig and 0.3 g of silica powder were mixed to form a composition. The results are shown in Table 2.

The oxygen concentration inside the bag is completely deoxidized (below 0.1%), and the acetaldehyde concentration in the system is 3°ppm, which is the lower limit of analysis.
It was below. Furthermore, after the analysis, the bag was opened and the odor was checked, but no abnormal odor including acetaldehyde odor was observed.

Table 25 days later concentration analysis results in the system Example 3 Glycerin 0.5g, water 0.3g, calcium hydroxide 0
゜5g, ferrous chloride 0. Ig, catechol 0.05g
The same procedure as in Example 1 was carried out except that 0.1 g of activated carbon and 0.3 g of silica powder were mixed to form a composition. The results are shown in Table 3. The oxygen concentration inside the bag was completely deoxidized (less than 0.1%), and the acetaldehyde concentration in the system was 30 pp, which is the lower limit of analysis.
m or less. Furthermore, after the analysis, the bag was opened and the odor was checked, but no abnormal odor including acetaldehyde odor was observed.

Table 3 System concentration analysis results after 5 days Example 4 Sorbitol 1g, water 0.6g, potassium hydroxide 1g1
The same procedure as in Example 1 was carried out except that 0.2 g of cuprous chloride and 1.4 g of activated carbon were mixed to form a composition. The results are shown in Table 4.

The oxygen concentration inside the bag is completely deoxidized (below 0.1%),
The concentration of acetaldehyde in the system was also below the analysis lower limit of 30 ppm. Furthermore, after the analysis, the bag was opened and the odor was checked, but no abnormal odor including acetaldehyde odor was observed.

Table 4 Results of analysis of concentration in the system after 5 days Example 5 Glycerin 0.5g, water 0.4g, manganese chloride 0.2
g.

After mixing 2 g of calcium hydroxide (granular) and 0.05 g of activated carbon, the mixture was placed in a small bag (50 mm in length and 80 mm in width) made from a packaging material laminated with paper and perforated polyethylene. did. In addition, after impregnating 4 g of 50% ethanol with 4 g of silica powder, we made a small bag (vertical 5
0 mm, width 80 mm) and used as an ethanol generator. 200 ml of air and 100 g of castella
Then, put it in a bag made of polyvinylidene-coated stretched nylon and polyethylene, and after sealing it,
It was left in an atmosphere at 5°C. Table 5 shows the results of gas chromatograph analysis of the oxygen concentration and acetaldehyde concentration in the system after 5 days.

The oxygen concentration inside the bag is completely deoxidized (below 0.1%),
The concentration of acetaldehyde in the system was also below the analysis lower limit of 30 ppm. Furthermore, after the analysis, the bag was opened and the odor was checked, but no abnormal odor including acetaldehyde odor was observed.

Table 5 Results of system concentration analysis after 55 days Comparative Example 1 Iron powder 0.5g, saturated saline 0.2g, zeolite 0.5
The procedure was the same as in Example 1 except that g was mixed to prepare a composition. The results are shown in Table 6.

Although the oxygen concentration in the bag was completely deoxygenated (less than 0.1%), the acetaldehyde concentration in the system reached 250 ppm, and when the bag was opened, an acetaldehyde odor was felt.

Table 6 Results of system concentration analysis after 65 days [Effects of the invention] The oxygen absorber of the present invention does not produce acetaldehyde even when ethanol coexists, and can be suitably used for deoxidizing storage of ethanol-containing foods. .

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent attorney: Sadafumi Tebori

Claims (1)

[Scope of Claims] 1) An ethanol-containing oxygen absorber for food comprising a sugar alcohol, an alkaline substance, and a transition metal compound. 2) An oxygen absorber package comprising an ethanol-containing food oxygen absorber containing a sugar alcohol, an alkaline substance, and a transition metal compound housed in an air-permeable packaging material. 3) An oxygen absorber package consisting of an ethanol-containing oxygen absorber for food containing a sugar alcohol, an alkaline substance, and a transition metal compound is housed in a breathable packaging material, and the food is housed in a non-breathable packaging material or an airtight container. A food package that is sealed or hermetically sealed.