JPH0321214B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and improved oxygen scavenger with excellent oxygen scavenging effects. Factors that affect food quality include oxygen, light,
Various factors can be considered, such as heat, microorganisms, and moisture. Among these factors, oxygen present in food packaging containers in particular can cause rancidity of food, growth of aerobic microorganisms,
It has long been well known that light, heat, etc. promote oxidation and deterioration of the resident components of foods, and that they are a major cause of deterioration in the quality of foods. Today, various methods are being considered to maintain the quality of food. For example, methods using food additives; ultraviolet irradiation methods; heat sterilization methods using infrared rays, high frequencies, and microwaves; radiation treatment methods such as X-rays, beta rays, and alpha rays; gas sterilization methods using ozone, ethylene oxide, propylene oxide, etc. Methods using bacteriostatic effects such as gas displacement packaging using carbon dioxide gas, nitrogen gas, etc. and vacuum packaging; Methods using aseptic filling such as aseptic packaging and bolt packaging; Methods using freezing, refrigeration, filtration, washing, etc. ing. Many of these quality preservation methods are
This is done to prevent direct oxidative deterioration caused by oxygen within the food packaging system, or to suppress the growth of aerobic microorganisms that cause deterioration in food quality. However, among these methods, quality preservation methods that use food additives, such as antioxidants, synthetic preservatives, synthetic sterilizers, etc., require the addition of drugs directly or indirectly to the food. Considering today's thinking, which is based on safety, such a method cannot be said to be desirable. On the other hand, a method of preserving the quality of foods by using an oxygen scavenger that itself has an oxygen absorbing effect has been attracting attention in recent years. According to this method, the oxygen scavenging function can be fully demonstrated simply by allowing the food and the oxygen scavenger to coexist in a separated state within the food packaging system, making it an ideal method for maintaining food quality and preserving food. It can be said that. Various oxygen scavengers of this type have been proposed in the past, and some of them have been put into practical use. For example, fruits and vegetables can be grown by removing oxygen from the atmosphere using an oxygen scavenger consisting of a mixture of hydrosulfite, calcium hydroxide, sodium bicarbonate, and activated carbon, with water added as necessary. A method for preserving freshness has been proposed. In addition, what has been put into practical use is a mixture of reduced iron powder, metal halides such as sodium chloride and copper chloride, and water-insoluble fillers such as activated carbon and zeolite, and further water or sodium sulfite crystals and sodium carbonate crystals. Oxygen scavengers obtained by mixing water-donating compounds such as In addition, various oxygen scavengers have been proposed, including those using glycose oxidase, those using palladium and hydrogen, those using polyphenol oxidase, and those using asconbic acid. Among the above-mentioned oxygen scavengers, those that use hydrosulfide have the disadvantage of generating toxic sulfur dioxide gas due to decomposition of the components, while oxygen scavengers that are made of a mixture whose main component is reduced iron powder The presence of moisture is essential for the reaction between iron and oxygen, but the presence of moisture causes each component in the mixture to react, resulting in a decrease in oxygen absorption capacity. Also, when using a metal detector to detect metal fragments that should not be included in food, if you use an oxygen absorber containing iron, the oxygen absorber itself will react to the metal detector. There is also the disadvantage of storing it away. On the other hand, as an oxygen scavenger proposed by the same applicant as the present application, there is one containing catechol and activated carbon (Japanese Patent Application Laid-Open No. 55-54034). This oxygen absorber is
The present invention overcomes the drawbacks of conventional oxygen scavengers as described above, is safe, does not react to metal detectors, and has effective oxygen absorbing ability. However, as a result of further research on the above-mentioned oxygen scavenger containing catechol and activated carbon, the present inventors have found that it is possible to further blend an alkaline compound therein, and furthermore, to combine both an alkaline compound and a water or water-donating compound. It was found that the oxygen absorption capacity was increased by adding . However, what the inventors had not anticipated was that when a compound that can simultaneously function as both an alkaline compound and a water-donating compound was combined with catechol and activated carbon, the alkaline compound and the separate water-donating compound The present invention was completed based on the discovery that the oxygen absorption capacity is increased compared to when a donor compound is blended. That is, the present invention is an oxygen scavenger characterized by containing catechol, activated carbon, and a compound that can simultaneously function as both an alkaline compound and a moisture-donating compound. Catechol used in the present invention is also called pyrocatechin and has the following structural formula: In the oxygen scavenger of the present invention, the oxygen scavenging effect is expressed by the reaction of the above-mentioned catechol molecules with oxygen, but the details of the reaction mechanism have not been clarified. The activated carbon used in the present invention may be any of various mineral and vegetable activated carbons, such as coal-based activated carbon, coke-based activated carbon, petroleum pit activated carbon, coconut shell-based activated carbon, sawdust-based activated carbon, and pulp waste liquid-based activated carbon. can. However, in experiments conducted by the present inventors, mineral-based activated carbon had a superior deoxidizing effect compared to vegetable-based activated carbon, and among mineral-based activated carbon, coal-based activated carbon was superior. These activated carbons are 30~
A particle size of 150 mesh can be preferably used.
The blending amount of activated carbon is 1 to 1 part by weight of catechol.
2 parts by weight is preferred. The "compound capable of simultaneously fulfilling the functions of both an alkaline compound and a water-donating compound" used in the present invention is a compound whose aqueous solution obtained by dissolving it in water exhibits alkalinity and has water of crystallization. Examples of such compounds include compounds that are salts of weak acids and strong bases and contain water of crystallization. Specifically, _{Na2CO3 ・ 10H2O} , _Na2CO3・_{7H2O ,}
Na ₂ CO ₃・2H ₂ O, K ₂ CO ₃・2H ₂ O, K ₂ CO ₃・
3H ₂ O and the like can be preferably used, and it is desirable to use these in the form of fine powder. The amount of such a compound that has the functions of both an alkaline compound and a water-donating compound can be selected appropriately taking into account the type of compound and the required amount of oxygen removal, but generally, 1 weight of catechol is used. A range of about 0.5 to 3 parts by weight per part is desirable. In producing the oxygen scavenger of the present invention, the components may be simply mixed and then filled into a bag made of a suitable breathable film in, for example, an oxygen-free atmosphere or an atmosphere substituted with _N2 . Mixing of each component can be carried out using _an appropriate method, for example, activated carbon and Na ₂ CO ₃ . It can be done in a simple way.
Alternatively, a predetermined amount of each component may be mixed at once, and then a predetermined amount of this mixture may be filled into a bag.
Furthermore, if necessary, the mixture of each component can be molded and granulated using a tablet machine, extrusion molding machine, roll molding machine, etc. As mentioned above, the oxygen scavenger according to the present invention includes an oxygen scavenger made of a mixture of catechol and activated carbon, an oxygen scavenger containing an alkaline compound, and a oxygen scavenger containing an alkaline compound and a moisture donor. Compared to those containing sexual compounds,
An even better deoxidizing effect can be obtained. According to the experiments conducted by the present inventors, if the oxygen scavenging efficacy of a mixture of catechol and activated carbon is 1, the oxygen scavenger composed of catechol + activated carbon + alkaline compound is calculated per a certain amount of catechol weight. The oxygen scavenging effect was 1.2 to 1.5 times higher, and the oxygen scavenger consisting of catechol + activated carbon + alkaline compound + water donor compound was 1.5 to 2.0 times more effective. _On the other hand, in the oxygen scavenger of the present invention, when Na ₂ CO ₃ . was gotten. Such oxygen scavenging efficacy is about 1.5 times as high as the oxygen scavenging efficacy per weight of iron of conventional oxygen scavengers whose main component is iron. As can be seen from the above explanation, the oxygen scavenger of the present invention is a mixture of catechol and activated carbon, which contains a compound that can simultaneously function as both an alkaline compound and a moisture-donating compound in addition to catechol and activated carbon. It is possible to obtain an even better oxygen scavenging effect compared to oxygen scavengers made of the above, or oxygen scavengers with an alkaline compound added thereto, or even oxygen scavengers with an alkaline compound and a moisture-donating compound added thereto. . Furthermore, since there is no decrease in oxygen absorption ability as seen with conventional oxygen scavengers whose main component is iron, quality safety can be guaranteed, and furthermore, it can be used with metal detectors. The oxygen scavenger of the present invention is not only applicable to foods, but also to prevent insects and mildew on clothing, and to prevent rust on metal products.
It can be widely applied to prevent various unfavorable effects brought about by the presence of oxygen, such as preventing deterioration of chemical products and prevention of deterioration and decrease in efficacy of medicines. The present invention will be further explained below with reference to Examples. Example 1 The ingredients shown in Test Nos. 3 to 12 in Table 1 were mixed, each mixture was separately placed in a gas barrier film bag and sealed, and the amount of oxygen absorbed in the bag at 28°C was determined. was measured over time. Test Nos. 1 and 2 in Table 1 are tests for catechol and activated carbon alone, respectively, in a manner similar to the above.
The results of each test are shown in Table 1. As can be seen from Table 1, the oxygen scavengers of the present invention (Test Nos. 10 and 11) have superior oxygen scavenging efficacy compared to the others. In particular, the oxygen scavenger of the present invention has a remarkable deoxidizing effect even when compared to the one containing an alkaline compound and water (Test No. 6) or the one containing an alkaline compound and a water-donating compound (Test No. 8). Oxygen efficacy was observed.

【table】

[Table] Example 2 The mixture having the composition shown in Test No. 10 of Example 1 was
The oxygen absorber of the present invention was prepared by filling it into a composite film bag having an appropriate air permeability. For comparison, only activated carbon corresponding to Test No. 2 of Example 1,
Further, the mixtures having the compositions shown in No. 4 and No. 6 were respectively filled into the same composite film bags as above. Next, add these oxygen absorbers to 100g of sweet chestnuts and 500g of air.
Each bag was sealed in a gas-barrier film bag along with cc and stored at 28°C for 3 months to observe the growth of mold on the surface of the sweet chestnuts. The results are shown in Table 2.

[Table] Significant occurrence.
・The decrease in oxygen concentration after 30 days in Test No. 2 is due to the growth of mold.
As can be seen from Table 2, in Test Nos. 4, 6, and 10, no mold growth was observed on the surface of sweet chestnuts until 3 months of storage, but especially in Test No. 4 using the oxygen scavenger of the present invention. In .10, the oxygen concentration decreased to 0.00% on the first day of storage, showing particularly excellent oxygen scavenging efficacy. Furthermore, in Test No. 2 (activated carbon only), mold growth was observed from around 2 weeks, and changes in the color and gloss of the sweet chestnut surface were observed.

Claims (1)

[Claims] 1. An oxygen scavenger characterized by containing catechol, activated carbon, and a compound that can simultaneously function as both an alkaline compound and a moisture-donating compound.