Food-preserving agent and method for preserving food with the food-preserving agent

Abstract: A food-preserving agent comprising an oxygen absorbent and a compound represented by the following structural formula (I): , wherein n is an integer of 2 to 4 and X is H or CH₃, can remove generated acetaldehyde effective, thereby preserving food without any fear of disagreeable odor for a long duration.

Description: BACKGROUND OF THE INVENTION This invention relates to a food-preserving agent and a method for preserving food with the food-preserving agent, and more particularly to a food-preserving agent capable of removing acetaldehyde and a method for preserving food with the said food-preserving agent. Heretofore, methods for preserving food in sealed packages, based on a vacuum treatment or replacement with an anaerobic gas such as a nitrogen gas, etc. have been developed. More recently, methods for preserving food in sealed packages, based on filling of an oxygen absorbent, ethanol vapors, or a transpirating agent, or a combination thereof have been proposed. Particularly, methods for preserving food in sealed packages based on simultaneous use of an oxygen absorbent and ethanol vapors or a transpirating agent have been regarded as one of ideal methods for preserving food, because the former is effective for the control of aerobic bacteria and the latter is effective for the control of anaerobic bacteria. However, it has been found that these methods have a problem, that is, generation of acetaldehyde by contact of ethanol vapors or liquid with an oxygen absorbent and the resulting oxidation of ethanol. Furthermore, it has been found that the generation of acetaldehyde is not only due to the simultaneous use of the oxygen absorbent and ethanol, but also due to food itself, as disclosed in Japanese Patent Application Kokai (Laid-open) No. 62-40273. The generated acetaldehyde itself is a substance causing a disagreeable odor, and its toxicity also is a problem. Practical steps for removing the generated acetaldehyde rapidly have been required to develop and thus extensively investigated. As a result, the following substances have been so far proposed to remove the acetaldehyde, in Japanese Patent Application Kokai No. 61-285973 and 62-40273 et al. (1) Ammonium salts such as ammonia alum, ammonium sulfate, etc. (2) Urea (3) Amino acids such as lysin, arginine, glycine, glutamine, etc. (4) Proteins such as albumen, casein, gluten, etc. (5) Peptides such as peptones, gelatin, etc. (6) Inorganic alkali metal salts such as sodium hydroxide, etc. (7) Sulfites such as sodium sulfite, etc. (8) Bisulfites such as sodium bisulfite, etc. (9) Thiosulfates such as sodium thiosulfate, etc. (10) Sulfates such as sodium sulfate, etc. (11) Aromatic aminosulfonic acids, their alkali metal salts and alkaline earth metal salts such as sulfanilic acid, sodium sulfanilate, etc. (12) Weakly basic ion exchange resins The substances (1) and (2) are preferable with respect to the safety and cost, but have a problem in the ability to remove acetaldehyde. The substances (3) to (5) alone have also a problem in the ability to remove acetaldehyde, and must be used actually together with a toxic alkaline substance, as disclosed, for example, in Japanese Patent Application Kokai (Laid-open) No. 62-40273, and also have such a problem that they are disagreeable odor sources by themselves. The substances (6) to (11) are highly toxic by themselves and also have such a problem that they are disagreeable odor sources. The substance (12) is high in the cost and also has such a problem as an amine odor. SUMMARY OF THE INVENTION An object of the present invention is to provide a food-preserving agent which comprises an oxygen absorbent and a substance that is low in the cost, high in the safety, free from a disagreeable odor and high in the ability to remove acetaldehyde by itself, and a food-preserving agent which comprises the oxygen absorbent, the substance that is high in the ability to remove acetaldehyde, and an ethanol-containing substance, and a method for preserving food with the food-preserving agent. As a result of investigating substances that are low in the cost, high in the safety, free of disagreeable odor and high in the ability to remove acetaldehyde without impairing the ability of an oxygen absorbent to absorb oxygen, the present inventors have found that a compound represented by the following structural formula (I) can meet the requirements. wherein n is an integer of 2 to 4, and X is H or CH₃. The first aspect of the present invention provides a food-reserving agent, which comprises an oxygen absorbent and a compound represented by the foregoing structural formula (I) as a substance capable of removing acetaldehyde. The second aspect of the present invention provides a food-preserving agent, which comprises an ethanol-containing substance, an oxygen absorbent and a compound represented by the foregoing structural formula (I) as a substance capable of removing acetaldehyde. The third aspect of the present invention provides a method for preserving food, which provides a food and a food-preserving agent comprising an oxygen absorbent and a compound represented by the foregoing structural formula (I) as a substance capable of removing acetaldehyde in a sealed package. The fourth aspect of the present invention provides a method for preserving food, which provides a food and a food-preserving agent comprising an ethanol-containing substance, an oxygen absorbent and a compound represented by the foregoing structural formula (I) as a substance capable of removing acetaldehyde in a food-containing sealed package. DETAILED DESCRIPTION OF THE INVENTION Ethanol-containing substance for use in the present invention is not particularly limited, so long as it can contain ethanol, and includes, for example, ethanol-containing carriers such as activated carbon, silicon dioxide, diatomaceous earth, clay, celite, pearlite, zeolite, paper, cloth, cotton, etc. Such an ethanol content of the ethanol-containing substance that the concentration of transpirated ethanol in the sealed package can satisfy the preservation of the food in the sealed package is enough, but also depends on the kind and the amount of food to be preserved. Usually, one part by weight of ethanol is contained in 100 parts by weight of a carrier. Oxygen absorbent for use in the present invention is not particularly limited, so long as it can remove oxygen from air by oxidation reaction, adsorption, absorption, etc., and includes, for example, iron powder, ascorbic acid and erythorbic acid or their salts; unsaturated fatty acids and their salts or esters; catechol; and gallic acid and its salts or esters. Acetaldehyde to be removed according to the present invention is not limited only to the acetaldehyde generated by contact of coexisting ethanol vapors or liquid with an oxygen absorbent and the resulting oxidation of ethanol, but also includes acetaldehyde generated by other factors. For example, acetaldehyde generated from food itself is included. Substance capable of removing acetaldehyde for use in the present invention is a cyclic urea derivative represented by the following structural formula (I): wherein n is an integer of 2 to 4 and X is H or CH₃. The compound represented by the foregoing structural formula (I) includes, for example, 5-membered 2-imidazolidone and 4-methyl-2-imidazolidone, 6-membered 2-oxy-hexahydropyrimidine and 7-membered 2-oxy-1,3-diazepane. A procedure for mixing an ethanol-containing substance, an oxygen absorbent and a substance capable of removing acetaldehyde is not particularly limited, so long as it can conduct uniform mixing. The substance capable of removing acetaldehyde may be mixed in a powdery state, or dissolved in a solvent such as water or ethanol, followed by impregnation of a carrier with the solution and mixing with other component. At least one part by weight, preferably at least 2 parts by weight, of the substance capable of removing acetaldehyde is mixed with 100 parts by weight of a mixture of the ethanol-containing substance and the oxygen absorbent. In the present invention, a food-preserving agent comprising an ethanol-containing substance, an oxygen absorbent and a substance capable of removing acetaldehyde is encased in a small bag of gas-permeable package material which can freely permeate a gas such as oxygen, ethanol or acetaldehyde, and used. The food-preserving agent encased in the small bag is used together with food for the preservation of food contained in a non-gas permeable, sealed package. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below, referring to Examples. Example 1 100 parts by weight of iron powder, 2 parts by weight of calcium chloride and 0.5 parts by weight of activated carbon were mixed together in a mortar to prepare an oxygen absorbent. 133 parts by weight of zeolite was impregnated with 65 parts by weight of 99.5% ethanol to prepare an ethanol-containing substance. 2-imidazolidone and 2-oxy-1,3-diazepane were used as substances capable of removing acetaldehyde. At first, 1.0 g of the oxygen absorbent, 0.9 of the ethanol-containing substance and 0.1 g of powder of the substance capable of removing acetaldehyde were weighed out, encased in a perforated small bag with dimensions of 45 x 40 mm, made from Japanese paper lined with polyethylene, heat sealed and gently shaked for mixing to prepare a food-preserving agent. Then, defatted cotton containing 10 ml of water and the thus prepared food-preserving agent were placed together with 250 ml of air in a so said KON package made from a non-gas permeable lamination film of vinylidene chloride-coated nylon/polyethylene and immediately heat sealed. The KON package was left standing at 25°C, and ethanol vapors, residual oxygen and acetaldehyde were quantitatively analyzed by gas chromatograph day by day. Beside the foregoing samples, samples containing urea and urea derivatives such as N-methylurea, 1,3-dimethylurea, 1,1-dimethylurea, tetramethylurea, ethylurea, 1,3-diethylurea, 1,1-diethylurea, tetraethylurea and n-butylurea as substances capable of removing acetaldehyde, respectively, in place of 2-imidazolidone and 2-oxy-1,3-diagepane were prepared for comparison in the same manner as above. Furthermore, a sample containing lysine hydrochloride alone as an example of amino acid as a substance capable of removing acetaldehyde, and another sample containing lysine hydrochloride and sodium carbonate were prepared for comparison in the same manner as above. Still furthermore, a sample containing amberlite IRA-45 as an example of weakly basic ion exchange resin as a substance capable of removing acetaldehyde was prepared in the same manner as above. All of these samples were tested. The samples are summarized in Table 1 together with the amounts of the respective samples used, and the results are shown in Table 2, where AcH stands for acetaldehyde and EtOH for ethanol. Sample No. Substance capable of removing acetaldehyde Amount 1 2-imidazolidone 0.1g 2 2-oxy-1,3-diazepane 0.1g 3 Urea 0.1g 4 N-methylurea 0.1g 5 1,3-dimethylurea 0.1g 6 1,1-dimethylurea 0.1g 7 Tetramethylurea 0.1g 8 Ethylurea 0.1g 9 1,3-diethylurea 0.1g 10 1,1-diethylurea 0.1g 11 Tetraethylurea 0.1g 12 n-butylurea 0.1g 13 Lysine hydrochloride 0.1g 14 Lysine hydrochloride/sodium carbonate 0.1g/0.1g 15 Ambelite IRA-45 0.1g 16 None As is obvious from Table 2, the substances capable of removing acetaldehyde according to the present invention have a remarkable effect, as compared with the conventional substances. Example 2 Samples each containing 0.025 g, 0.05 g, 0.10 g, 0.20 g of 2-imidazolidone as a substance capable of removing acetaldehyde were prepared as food-preserving agents in the same manner as in Example 1. Furthermore, the thus prepared food-preserving agents were placed in individual KON bags each together with defatted cotton containing 10 ml of water and 250 ml of air in the same manner as in Example 1, and ethanol vapors, residual oxygen and acetaldehyde were quantitatively analyzed by gas chromatograph day by day. Amounts of 2-imidazolidone in the respective samples are shown in Table 3 and the results in Table 4. Sample No. Amount of 2-imidazolidone (g) Ratio of oxygen absorbent ethanol-containing substance/2-imidazolidone (by weight) 16 0.0 100/0 17 0.025 100/ 1.3 18 0.050 100/ 2.6 1 0.100 100/ 5.2 19 0.200 100/10.4 Sample No. Analysis at the time after: O₂ AcH EtOH 16 1st day <0.1% 667 ppm 3524 ppm 2nd day <0.1% 652 ppm 3647 ppm 3rd day <0.1% 680 ppm 3324 ppm 17 1st day <0.1% 109 ppm 3154 ppm 2nd day <0.1% 115 ppm 3230 ppm 3rd day <0.1% 105 ppm 3189 ppm 18 1st day <0.1% 17 ppm 3214 ppm 2nd day <0.1% 22 ppm 3365 ppm 3rd day <0.1% 24 ppm 3188 ppm 1 1st day <0.1% 5 ppm 3318 ppm 2nd day <0.1% 2 ppm 3433 ppm 3rd day <0.1% 0 ppm 3000 ppm 19 1st day <0.1% 0 ppm 3127 ppm 2nd day <0.1% 0 ppm 3333 ppm 3rd day <0.1% 0 ppm 3232 ppm As is obvious from Table 4, at least one part by weight of 2-imidazolidone as a substance capable of removing acetaldehyde per 100 parts by weight of the total of the oxygen absorbent and the ethanol-containing substance has a considerable effect on acetaldehyde removal, and it is practically preferable to use at least 2 parts by weight of 2-imidazolidone. Example 3 23 parts by weight of 2-oxy-1,3-diazepane as a substance capable of removing acetaldehyde was dissolved in 65 parts by weight of ethanol, and 135 parts by weight of zeolite was impregnated with the resulting solution. Then, from 1 g of the thus impregnated zeolite and 1 g of the oxygen absorbent of Example 1 was prepared a food-preserving agent in the same manner as in Example 1. Then, the thus prepared food-preserving agent, defatted cotton containing 10 ml of water and 250 ml of air were filled in a KON bag in the same manner as in Example 1, and ethanol vapors, residual oxygen and acetaldehyde were quantitatively analyzed by gas chromatograph day by day. The results are shown in Table 5 together with the results of Sample No. 2. Sample No. Analysis at the time after: O₂ AcH EtOH 20 1st day <0.1% 18 ppm 3328 ppm 2nd day <0.1% 14 ppm 3169 ppm 3rd day <0.1% 8 ppm 3243 ppm 2 1st day <0.1% 20 ppm 3420 ppm 2nd day <0.1% 15 ppm 3380 ppm 3rd day <0.1% 8 ppm 3100 ppm As is obvious from Table 5, 2-oxy-1,3-diazepane as a substance capable of removing the generated acetaldehyde has the same effect on the acetaldehyde removal, irrespective of use of it as powder or as a solution in ethanol. Example 4 From 0.1 g of 2-imidazolidone as a substance capable of removing acetaldehyde and 1.9 g of the oxygen absorbent of Example 1 was prepared a food-preserving agent in the same manner as in Example 1. For comparison, a food-preserving agent containing no 2-imidazolidone was also prepared. The thus prepared food-preserving agents were placed into the respective KON bags each together with 100 g of a sponge cake containing 1.9 g of ethanol and 2.5 g of water, and 250 ml of air, and ethanol vapors, residual oxygen and acetaldehyde were qualitatively analyzed by gas chromatograph after the first day, the third day and the fifth day. The compositions of the sample are given in Table 6 and the results are shown in Table 7. Sample No. Composition of food-preserving agent 21 (2-imidazolidone/oxygen absorbent) = 0.1/1.9 by weight 22 Only oxygen absorbent Sample No. Analysis at the time after: O₂ AcH EtOH 21 1st day <0.1% 2 ppm 8953 ppm 3rd day <0.1% 0 ppm 9537 ppm 5th day <0.1% 0 ppm 9656 ppm 22 1st day <0.1% 320 ppm 8888 ppm 3rd day <0.1% 380 ppm 9675 ppm 5th day <0.1% 362 ppm 9163 ppm As is obvious from Table 7, vapors of the ethanol added to the food as antiseptics were brought into contact with the oxygen absorbent to generate acetaldehyde, giving off a disagreeable odor. A toxicity would be a problem from the hygienic viewpoint in the case of the food-preserving agent containing no 2-imidazolidone, i.e. containing only the oxygen absorbent. In the case of the food-preserving agent containing 2-imidazolidone, on the other hand, the generated acetaldehyde was removed, and no disagreeable odor was given off. Food preservation with a very high safety could be obtained. Example 5 A food-preserving agent containing 2-oxy-1,3-diazepane as a substance capable of removing acetaldehyde and a food-preserving agent containing no such substance were prepared in the same manner as in Example 4. Then, the thus prepared food-preserving agents were placed into the respective KON bags each together with 100 g of commercially available Hampen (light, puffy cake made of ground fish) in place of the sponge cake of Example 4, and air in the same manner as in Example 4. Residual oxygen and actaldehyde were quantitatively analyzed after the first day, the third day and the fifth day. Compositions of the samples are shown in Table 8 and the results in Table 9. Sample No. Composition of food-preserving agent 23 (2-oxy-1,3-diazepane/oxygen absorbent) = 0.1/1.9 by weight 24 Only oxygen absorbent Sample No. Analysis at the time after: O₂ AcH 23 1st day <0.1% 0 ppm 3rd day <0.1% 0 ppm 5th day <0.1% 0 ppm 24 1st day <0.1% 150 ppm 3rd day <0.1% 179 ppm 5th day <0.1% 162 ppm As is obvious from Table 9, when acetaldehyde was generated from the food itself such as Hampen (light, puffy cake made of ground fish), acetaldehyde existed at a considerably high concentration for a long duration in the case of the food-preserving agent containing no such a substance capable of removing acetaldehyde, and served not only as a disagreeable odor source, but also a toxicity was a problem from the hygienic view point though its transfer into the food. In the case of the food-preserving agent containing 2-oxy-1,3-diazepane, on the other hand, the generated acetaldehyde was removed and no disagreeable odor was given off. Thus, food preservation with a very high safety could be obtained. Example 6 A food-preserving agent comprising the oxygen absorbent, the ethanol-containing substance and 2-imidazoidone as a substance capable of removing acetaldehyde was prepared in the same manner as in Example 1. Then, the thus prepared food-preserving agent was placed in a KON bag together with 200 g (4 pieces) of commercially available cut rice cakes containing no ethanol in place of the ethanol-containing sponge cake of Example 4 and air in the same manner as in Example 4, and ethanol vapors, residual oxygen and acetaldehyde were quantitatively analyzed by gas chromatography after the first day, the third day and the fifth day. In order to determine the transfer of acetaldehyde into the food, the cut rice cakes each after the above-mentioned days were placed in a heat-resistance bottle having a capacity of 1 ℓ, tightly plugged, heated at 100°C and subjected to gas analysis. The results are shown in Table 10. Sample No. Analysis at the time after: O₂ AcH AcH in food EtOH 25 1st day <0.1% 0 ppm 0 ppm 2604 ppm 3rd day <0.1% 0 ppm 0 ppm 2620 ppm 5th day <0.1% 0 ppm 0 ppm 2888 ppm As is obvious from Table 10, the food-preserving agent containing both 2-imidazolidone and ethanol could remove acetaldehyde immediately. Thus, use of the food-preserving agent of the present invention could prevent a disagreeable odor due to acetaldehyde and also could prevent transfer of acetaldehyde having a safety problem into the food. That is, food preservation with a very high safety could be obtained. The food-preserving agent of the present invention can remove acetaldehyde generated from the simultaneous use of an oxygen absorbent and ethanol or from food itself very effectively at a low cost and without giving off a disagreeable odor at all, and thus can serve to preserve food with a very high safety without any fear of disagreeable odor.

Claims: A food-preserving agent, which comprises an oxygen absorbent and a compound represented by the following structural formula (I): wherein n is an integer of 2 to 4 and X is H or CH₃. A food-preserving agent according to claim 1, which comprises an ethanol-containing substance, an oxygen absorbent and a compound represented by the following structural formula (I): wherein n is an integer of 2 to 4 and X is H or CH₃. A method for preserving food, which provides a food and a food-preserving agent comprising an oxygen absorbent and a compound represented by the following structural formula (I): , wherein n is an integer of 2 to 4 and X is H or CH₃, into a sealed package. A method for preserving food according to claim 3, which provides a food and a food-preserving agent comprising an ethanol-containing substance, an oxygen absorbent and a compound represented by the following structural formula (I): wherein n is an integer of 2 to 4 and X is H or CH₃, into a sealed package.

Inventors: HOSOMI AKIRA MITSUBISHI GAS CH, NAKAYAMA FUTOSHI MITSUBISHI GA, SUGIHARA YASUO MITSUBISHI GAS, WAKABAYASHI HIDECHIKA MITSUBIS, HOSOMI, AKIRA, MITSUBISHI GAS CHEM. CO., INC., NAKAYAMA, FUTOSHI, MITSUBISHI GAS CHEMICAL CO.,INC, SUGIHARA, YASUO, MITSUBISHI GAS CHEM. CO., INC., WAKABAYASHI, HIDECHIKA, MITSUBISHI GAS CHEM.CO.INC
Applicants: MITSUBISHI GAS CHEMICAL CO, MITSUBISHI GAS CHEMICAL COMPANY, INC.
Application year: 1992
Main classification: A23L3
IPC codes: A23L3, B01J20