JP2800178B2 - Food preservation composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composition for preserving food, and more particularly to a composition for preserving food for protecting food from spoilage and deterioration.

(Prior art and its problems) In order to prevent spoilage and deterioration of various foods including agricultural products, marine products, livestock products and their processed foods, various mixed-type preservatives have been used conventionally. Dispersion, impregnation,
It can exert its effect by mixing it with food by means such as kneading, so that the original purpose of preservation etc. can be sufficiently achieved, but it is taken into the human body orally and adverse effects on the human body are also considered. Not desirable.

Therefore, non-mixed food preservatives that exhibit preservative action without being mixed with food and are therefore not orally taken up by the human body have been developed. A deoxidizer in which an oxidizing agent such as salt is added to the powder, an ethanol vapor generator in which ethanol is supported on a porous powder, and a combination of an oxygen absorber and an ethanol vapor generator have been proposed. I have.

However, the method using an oxygen scavenger has a drawback that the food hardens to deteriorate the flavor or discolor. Although the method using an ethanol vapor generator improves the above-mentioned drawbacks of the oxygen scavenger, it has a drawback in that foods having a very high water activity must be used in a large amount. Further, in the method in which the oxygen scavenger and the ethanol vapor generator are used in combination, there is a problem that when the generated ethanol itself enters the oxygen scavenger, it is changed to acetaldehyde, and an odor is generated. In addition, these unmixed preservatives do not come into direct contact with food, so they have only a minor adverse effect on food, but their effects are not sufficient compared to mixed preservatives, and therefore, they are compared to achieve a certain effect. It is necessary to use a large amount, and when used in a large amount, there is a disadvantage that the above-mentioned adverse effects increase. At present, it is desired to develop a non-additive food preservative having a high effect in a small amount.

(Technical Problems to be Solved by the Invention) In view of the present situation, an object of the present invention is to solve the above problems and to provide a non-mixed food preservation composition having a higher effect with a small amount. And

(Constitution of the Invention) The present invention provides an ethanol vapor generator; a deoxidizer comprising a metal powder and an oxidation accelerator for the metal powder; and a polymer comprising vinylamine as an essential component and having a vinylamine content of at least 25 mol%. Is a composition for preserving food, characterized by containing as an essential component.

 Hereinafter, the present invention will be described in detail.

As the ethanol vapor generator used in the food preservation composition of the present invention, ethanol is adsorbed on porous particles such as silica, alumina, activated carbon, diatomaceous earth, clay, talc, zeolite, starch, dextrin, and cellulose powder. Or absorbed; ethanol, paper, cotton,
Foam impregnated; ethanol microencapsulated (JP-A-60-99337); air such as a compound having an ethoxy group bonded to a metal atom such as silicon, titanium and tin; Any compound can be arbitrarily selected from compounds capable of producing and releasing ethanol by reacting with water in the water or water evaporating from food or the like (Japanese Patent Application Laid-Open No. Sho 59-16811).

As the oxygen scavenger used in the food preservation composition of the present invention, conventionally known oxygen scavengers can be used, and those obtained by adding an oxidation promoter of the metal powder to the metal powder are preferable. Various kinds of metal powder are used, and iron powder is preferably used.
Almost all metal salts are effective as the oxidation promoter, but alkali metal or alkaline earth metal halides, particularly sodium chloride, potassium chloride, magnesium chloride and the like are most preferred.

The polymer used in the food preservation composition of the present invention contains vinylamine as an essential component and has a vinylamine content of 25 mol% or more. The vinylamine-based polymer functions to capture toxic acetaldehyde generated when the ethanol vapor generator and the oxygen scavenger are used in combination. Preferred polymers include polyvinylamine, a copolymer of vinylamine and vinylformamide, a copolymer of vinylamine and vinylacetamide,
Copolymer of vinylamine and vinyl alcohol, copolymer of vinylamine and styrene, copolymer of vinylamine and vinyl chloride, copolymer of vinylamine and acrylamide, copolymer of vinylamine and acrylic acid or methacrylic acid And a copolymer of vinylamine and acrylate or methacrylate, and a copolymer of vinylamine and acrylonitrile.

It is necessary that the content of vinylamine in the polymer is 25 mol% or more. If the content is less than 25 mol%, the ability to capture acetaldehyde will decrease. Further, the molecular weight of the polymer is preferably 500 or more.

The polymer itself may be used in the form of powder or granules, but it is adsorbed on a carrier such as silica, alumina, activated carbon, zeolite, diatomaceous earth, pulp powder, paper, cloth, and used as a polymer adsorbent. Is also good.

In the present invention, the ethanol vapor generator, the oxygen scavenger, and the vinylamine-based polymer are separately filled and sealed in a gas-permeable container, for example, a paper pouch or a paper pouch laminated with porous polyethylene or the like. Then, it is preferable to put these together with the food in a food storage container or storage bag. These three components may be encapsulated by combining any two of them, or all components may be encapsulated in the same pouch.

Further, together with the above three components, these three components and other additives that do not adversely affect the food may be added. These additives include organic acids, carbon dioxide generators, flavoring agents and the like.

The food preservation composition of the present invention is used for preventing spoilage and deterioration of various foods including agricultural products, marine products, livestock products and processed foods thereof, and in particular, bread, western confectionery, Japanese confectionery,
It is preferably used for delicacies, rice cakes, ham, kamaboko, bamboo rings and the like.

(Examples) Next, after describing a production example of the vinylamine-based polymer used in the present invention as a reference example, specific examples of the food preservation composition of the present invention will be described as examples.

Reference Example 1 N-vinylformamide (10 g) was dissolved by adding water (40 g).
10% aqueous solution of 2,2'-azobisamidinopropane hydrochloride
0.5 g was added, and polymerization was carried out at 60 ° C. for 4 hours after purging with nitrogen.

To an aqueous solution of the obtained polymer, 22 g of 35% hydrochloric acid was added, and 80
C. After 1 hour, 4 hours and 72 hours, 18 g of each reaction mixture was collected and precipitated in methanol, then filtered and dried under reduced pressure to obtain 2.5 g, 2.2 g and 2.3 g of a white powdery polymer, respectively. I got The degree of hydrolysis measured by the colloid titration method was 32 mol%, 70 mol%, and 100 mol%, respectively.

Next, each polymer was dissolved in water, 10 ml of 5N-NaOH was added to dehydrochlorinate, and immediately dialyzed against water using hollow fiber for 5 days. This solution was concentrated to 10% of each polymer.
% Aqueous solution was prepared. Hydrolysis degree is 32mol%, 7 respectively
0 mol% and 100 mol% of the polymer are respectively represented by P (VAm / VFA
m) -1, P (VAm / VFAm) -2, PVAm. These have the following structures, respectively.

(Note) P (VAm / VFAm) means a copolymer of vinylamine (VAm) and vinylformamide (VFAm).

 PVAm means a polymer of vinylamine (VAm).

REFERENCE EXAMPLE 2 Isopropanol (40 g) was added to and dissolved in N-vinylacetamide (10 g), and azobisisobutyronitrile (0.1 g) was added. After purging with nitrogen, polymerization was carried out at 60 ° C. for 4 hours. After completion of the polymerization, the resultant was precipitated in acetone to obtain 9.5 g of a white powdery polymer. Dissolve 2.5 g of this powder in 10 ml of water, add 6 g of 35% HCl,
The mixture was hydrolyzed by reacting at 4 ° C. for 4 hours, precipitated in acetone, filtered and dried under reduced pressure. The degree of hydrolysis measured by the colloid titration method was 60 mol%.

Dissolve 2 g of the polymer thus obtained in water, 5N-NaOH7m
Then, the mixture was treated in the same manner as in Reference Example 1 to obtain a 10% aqueous solution of the polymer. This polymer has the following structure, and is abbreviated as P (VAm / VAAm).

(Note) P (VAm / VAAm) means a copolymer of vinylamine (VAm) and vinylacetamide (VAAm).

Reference Example 3 Isopropanol (60 g) was added to and dissolved in 8.5 g of N-vinylacetamide and 8.5 g of vinyl acetate, and 0.17 g of azobisisobutyronitrile was added. After nitrogen replacement, polymerization was carried out at 60 ° C. for 5 hours. After the completion of the polymerization, the resultant was precipitated in acetone to obtain 15 g of a white powdery polymer. 4g of this powder is 16g of isopropanol
And reacted at 80 ° C. for 32 hours, precipitated in acetone, filtered and dried under reduced pressure. The vinylamine content in the copolymer measured by the colloid titration method is
52 mol%.

3 g of this polymer was dissolved in water, 20 ml of 5N-NaOH was added to remove hydrochloric acid, left for 3 hours, and dialyzed with hollow fiber in the same manner as in Reference Example 1 to obtain a 10% aqueous solution of the polymer. This polymer has the following structure, and is abbreviated as P (VAm / VAl).

(Note) P (VAm / VAl) means a copolymer of vinylamine (VAm) and vinyl alcohol (VAl).

Example 1 3 g of a 10% aqueous solution of PVAm obtained in Reference Example 1 was added to 5 g of porous silicon dioxide (Adsolider 101 manufactured by Freund Corporation) with good stirring, and dried at 105 ° C. for 5 hours to obtain a powdery polymer carrier. I got Hereinafter, a polymer carrier having PVAm supported on silicon dioxide is referred to as AS.

Other polymer obtained in Reference Examples 1, 2, and 3, P (VAm / VFAm)
-1, P (VAm / VFAm) -2, P (VAm / VAAm), P (VAm /
VAl) was similarly adsorbed on silicon dioxide to prepare another polymer support. Further, activated carbon and zeolite were used in place of silicon dioxide as a carrier, and PVAm was carried thereon in the same manner to prepare another polymer carrier. These are collectively shown in Table 1.

Next, 20 g of ethanol was gradually added to 20 g of porous powdery silicon dioxide (Adsolider 101 manufactured by Freund Corporation) with stirring to obtain a powdery ethanol vapor generator in which ethanol was supported on silicon dioxide. The ethanol vapor generator, the oxygen scavenger composed of iron powder and sodium chloride, and the polymer carrier described in Table 1 were uniformly mixed in the proportions shown in Table 2, and laminated with perforated polyethylene on rayon Japanese paper. And heat-sealed. Next, the heat-sealed sachet containing the above composition was placed in a bag (capacity: 500 ml) made of a laminated film of nylon and polyethylene together with 50 g of kamaboko and sealed. Next, it was stored at 25 ° C., and a test was conducted on the state of generation of mold and rot and the generation of odor.

As a comparative example, one without using a polymer carrier,
Using polyallylamine (abbreviated as PAA) and polyethyleneimine (abbreviated as PEI) as polymers, these were adsorbed on silicon dioxide in the same manner as in Example 1 and tested under the same conditions. The results are collectively shown in Table 2.

Example 2 An ethanol vapor generator (identical to that used in Example 1), a deoxidizer composed of iron powder and chloride, and a polymer carrier prepared in Example 1 were uniformly mixed at a ratio shown in Table 3. And heat sealed in a sachet made of laminated perforated polyethylene on rayon Japanese paper. Then, heat-sealed pouches containing the above composition are castella-coated.
Bag made of laminated film of nylon and polyethylene coated with polyvinylidene chloride with 500g (volume 1.0
) And sealed. Next, these were stored at 25 ° C. and tested for mold generation, spoilage and odor.

As comparative experimental examples, those without the polymer support and those supported on silicon dioxide using polyallylamine (PAA) as the polymer were tested under the same conditions. The results are collectively shown in Table 3.

Example 3 10 g of ethanol was gradually added to 20 g of porous aluminum silicate with stirring to obtain a powdery ethanol vapor generator.
The ethanol vapor generator, the oxygen scavenger composed of iron powder and chloride, and the polymer carrier prepared in Example 1 were uniformly mixed at a predetermined ratio shown in Table 4, and perforated polyethylene was added to rayon Japanese paper. It was placed in a small bag made of laminated material and heat sealed. Next, the heat-sealed sachet containing the above composition was put together with 200 g of cut rice cake in a bag (volume 1) made of a laminated film of nylon and polyethylene coated with polyvinylidene chloride and sealed. Next, these were stored at 25 ° C. and tested for the state of mold generation, rot, and odor. The results are collectively shown in Table 4.

As is clear from the above examples, in a non-mixed type food preservation composition comprising a combination of an ethanol vapor generator and an oxygen scavenger, the use of a vinylamine-based polymer causes a high effect with a small amount of use. It is possible. In other words, if you use the same amount as the comparative product,
The antifungal effect can be increased by 50 to 100%, and a high effect can be maintained even if the amount used is reduced.

(Effects of the Invention) As described in detail above, the food preservation composition of the present invention can provide a high antiseptic and antifungal effect with a small amount of use. Therefore, the oxygen scavenger in the food preservation composition improves the flavor of the food. It is possible to minimize problems such as damage or discoloration and a fatal problem as a food preservative such as a malodor of acetaldehyde generated by the reaction of the ethanol generated from the ethanol vapor generator with the oxygen scavenger. In addition, the size and weight of the non-additive food preservative can be reduced.

Claims (1)

(57) [Claims] 1. An ethanol vapor generator; a deoxidizing agent comprising a metal powder and an oxidation promoter for the metal powder; and a polymer having vinylamine as an essential component and having a vinylamine content of 25 mol% or more as an essential component. A composition for preserving food, comprising: