JPS6357030B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a food freshness-preserving agent that has both oxygen absorption ability and carbon dioxide generation ability and is intended to prevent food from deteriorating. In recent years, as a method for preserving the freshness of packaged foods, a method has been implemented in which an oxygen absorber, that is, a substance capable of absorbing oxygen through a redox reaction, is sealed in a packaging container together with the food to prevent the food from deteriorating due to oxygen. ing. However, since this method only absorbs oxygen, although it has the effect of preventing food oxidation and discoloration and suppressing the growth of mold, it cannot be expected to suppress anaerobic bacteria. is difficult to fully satisfy. As a result of studies to solve the above-mentioned drawbacks, the present inventors have found that by imparting carbon dioxide gas generating ability to an oxygen absorbent, more complete freshness of food can be achieved. It has also been found that when an iron-based oxygen absorbent is used as an oxygen absorbent, hydrogen is generated during oxygen absorption, and that there is a possibility of fire and explosion, especially when a large amount of iron-based oxygen absorbent is used. The present inventors have discovered a freshness-preserving agent that is free from the danger of hydrogen generation and has good oxygen absorption ability and carbon dioxide generation ability, and has completed the present invention. The present invention comprises (A) an iron-based substance (hereinafter referred to as component (A)), (B) a halide of an alkali metal or alkaline earth metal (hereinafter referred to as component (B)), (C) carbonate and/or carbonic acid. Hydrogen salt (hereinafter referred to as component (C)), (D) Solid substance that becomes acidic when it interacts with water (hereinafter referred to as (D)
(E) Amino acids with an isoelectric point of 5.0 to 10.0 (hereinafter referred to as (E)
When this is packaged with food or placed in a container, the iron-based material (component (A)) absorbs oxygen in the packaging or container and at the same time , other (B) components, (C) components, and (D) components generate carbon dioxide gas, and this carbon dioxide gas exerts the function of suppressing the proliferation of bacteria (bacteriostatic or antibacterial function). This has an excellent effect on preserving the freshness of the food inside the package or container. Furthermore, carbon dioxide gas has the function of suppressing the life effects of fruits and vegetables and maintaining freshness, and this function can also be utilized in the present invention. Furthermore, the component (E) suppresses the generation of hydrogen, eliminates the dangers caused by hydrogen, and safely provides the above-mentioned oxygen absorption ability and carbon dioxide gas generation ability. The iron-based substance, which is the component (A) of the freshness-preserving agent of the present invention, is a substance that absorbs oxygen by reacting with oxygen in the air and is itself oxidized, and is used as a raw material for iron-based oxygen absorbents. It is widely used,
For example, those mainly containing one or more types selected from the following group can be mentioned. (a) Iron powders such as reduced iron powder, electrolytic iron powder, and atomized iron powder, and partial oxides of the iron powders. (b) For example, ferrous sulfate, ferrous oxide, ferrous hydroxide
A ferrous compound consisting of iron, etc. (c) For example, iron complex oxides such as triiron tetroxide. (d) Iron compounds consisting of, for example, iron carbide, iron sulfide, iron carbonyl, iron silicon, etc. These iron-based substances have the ability to absorb oxygen when used alone, but in the freshness preserving agent of the present invention, they can be used in combination with the other components (B), (C), and (D). When this happens, their interaction significantly increases the oxygen absorption capacity, significantly improving the freshness-keeping effect, and the product after the interaction is harmless. In this regard, for example, (1) oxygen absorbers made of sugars and alkalis, (2) oxygen absorbers made of aromatic polyhydric alcohols such as catechol, resorcinol, and pyrogallol and alkalis, and (3) ascorbic acid and its When an organic oxygen absorber (organic substance and alkali) such as an oxygen absorber consisting of a salt and an alkali is combined with components (B), (C), and (D) in the freshness preserving agent of the present invention and brought into contact. However, as an oxygen absorber, the oxygen absorption capacity decreases or becomes completely absent.
I can not use it. In the present invention, among the iron-based substances as the component (A) exemplified above, the iron powders exemplified in (A) and partial oxides of the iron powders are particularly useful for maintaining the freshness of the present invention. It is preferably used because it exhibits particularly remarkable oxygen absorption ability upon interaction with component (B), component (C), and component (D) of the agent. Further, among the iron powders and partial oxides thereof, fine powders having a particle size of less than 80 mesh are particularly preferably used because they have a high oxygen absorption capacity per unit weight. Alkali metal or alkaline earth metal halides as component (B) of the freshness preserving agent of the present invention are, for example, sodium chloride, potassium chloride, sodium bromide,
Alkali metal halides such as potassium bromide, sodium iodide, potassium iodide, sodium fluoride, potassium fluoride, magnesium chloride, calcium chloride, barium chloride, calcium bromide, magnesium bromide, bromide, etc. It is an alkaline earth metal halide such as barium. These halides can be used either in the form of anhydrous salts or various hydrated salts, and can be used alone or in combination of two or more types. There are no particular limitations on the carbonate and hydrogen carbonate that are component (C) of the freshness-preserving agent of the present invention, and for example,
Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , MgCO ₃ , CaCO ₃ ,
Carbonates and bicarbonates of alkali and alkaline earth metals such as BaCO ₃ , LiHCO ₃ , NaHCO ₃ , KHCO _{3
Hydrogen _ _ _ _ _ _ _} In order to suppress the generation of carbon dioxide as much as possible, carbonates and bicarbonates of alkali and alkaline earth metals are preferable, and among them, bicarbonates are particularly preferably used because they have a high carbon dioxide gas generation efficiency per unit weight. The solid substance that becomes acidic when acting with water, which is component (D) of the freshness preserving agent of the present invention, is the packaging or
A substance that is normally solid and exhibits acidity by chemically and/or physically interacting with water vapor in the atmosphere inside the container, for example, a substance that mainly contains one or more types selected from the following groups: Can be mentioned. For example, benzoic acid, erythorbic acid, caproic acid, glutamic acid, cinnamic acid, succinic acid, salicylic acid, oxalic acid, tartaric acid, sorbic acid, nicotinic acid, lactic acid, fumaric acid, maleic acid, folic acid,
Organic acids such as malic acid and citric acid. For example, inorganic acids such as boric acid. For example, anhydrous acids such as phosphoric anhydride (phosphorus pentoxide) and sulfuric anhydride (sulfur trioxide), which chemically interact (ie, react) with water vapor to produce acids. Among inorganic acid salts or organic acid salts of transition metals,
Something that becomes acidic when it interacts with water (hydrolyzes). Specifically, for example, halogen acid salts, oxyacid salts, and organic acid salts of metals such as iron, cobalt, nickel, copper, zinc, titanium, manganese, aluminum, tin, antimony, lead, and bismuth; For example, iron chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, manganese chloride, aluminum chloride, antimony chloride,
Titanium chloride, aluminum sulfate, iron sulfate, antimony sulfate, tin sulfate, titanium sulfate, manganese sulfate, aluminum nitrate, cobalt nitrate, iron nitrate, copper nitrate, nickel nitrate, nickel perchlorate, iron bromide, copper bromide, odor Examples include nickel oxide, iron iodide, and cobalt acetate. After these substances interact with water, they are hydrolyzed and become acidic. The isoelectric point of component (E) of the freshness preserving agent of the present invention is
There are no particular limitations on the amino acid having a value of 5.0 to 10.0, and any amino acid can be used as long as it has an isoelectric point (pI) within this range. When an amino acid having such a pI value is used, a freshness-preserving agent having very good oxygen absorption ability, carbon dioxide gas generation ability, and hydrogen generation suppression ability can be obtained. In the case of amino acids with a pI value of less than 5.0, the ability to suppress hydrogen generation is insufficient, and in the case of amino acids with a pI value of 10.0 or more, the ability to generate carbon dioxide gas is insufficient. Examples of such amino acids having a pI value of 5.0 to 10.0 include those mainly containing one or more types selected from the following groups. For example, asparagine, aminobutyric acid, alanine, arginine, isoleucine, ornithine, canavanine, glycine, glutamine, sarcosine,
Cysteine, cystine, serine, thyroxine, tyrosine, tryptophan, threonine, norleucine, valine, histidine, hydroxyproline, hydroxylysine, phenylanilan, proline, homoserine, methionine, methylhistidine, lysine, leucine, etc. have pI values of 5.0 or more, 10.0
There are the following amino acids. The freshness-preserving agent of the present invention has the above-mentioned components (A) to (E) as essential components, and if any one component is missing, the effectiveness as a freshness-preserving agent will be reduced. This situation will be explained below using an example in which one component is deleted from each of the five components. If component (A) is missing, no oxygen absorption ability is expressed at all. When component (B) is missing, both the oxygen absorption capacity and the carbon dioxide generation capacity are significantly reduced. If component (C) is missing, the ability to generate carbon dioxide gas will not be expressed at all. If component (D) is missing, the oxygen absorption capacity and carbon dioxide generation capacity will decrease, and especially the carbon dioxide gas that has been emitted into the packaging container will be absorbed again into the freshness-preserving agent, resulting in a long period of time. In terms of the range, carbon dioxide production is substantially reduced. If component (E) is missing, hydrogen will be generated,
There is a risk of explosion or fire when using large amounts of freshness preserving agents as they accumulate when used in packaging containers. The blending ratio of each component in the freshness preserving agent of the present invention is not limited except for component (E), and depends on the type of food, the amount of water evaporation from the food, the required oxygen absorption rate and carbon dioxide generation rate, etc. Generally preferred blending ratios are described below, although they can be varied over a fairly wide range. The carbon dioxide generation efficiency per weight of the freshness preserving agent depends on the blending ratio of components (B) to (D).
Per mol of carbonate and/or hydrogen carbonate of component (C), 0.01 to 3 mol, particularly preferably 0.1 to 2 mol of alkaline earth metal salt of component (B), and 0.1 to 2 mol of the acidic solid substance of component (D). , 0.01 to 4 mol, particularly preferably 0.1
It is preferable to set the blending ratio to 2 moles, and at a blending ratio within this range, the amount of carbon dioxide gas generated per weight of the drug used is high. The balance between the amount of oxygen absorbed and the amount of carbon dioxide gas generated is controlled by the blending ratio of the iron-based material of component (A) and components (B) to (D), and the preferred blending ratio is (A). ) 0.01 to 10 mol of carbonate and/or hydrogen carbonate, which is component (C), per 1 mol of iron-based substance, which is component (C),
In particular, a blending ratio of 0.05 to 5 moles is preferable, and within this range, the amount of oxygen absorbed and the amount of carbon dioxide gas generated are balanced, and a high freshness retention effect can be achieved. The amount of component (E) added varies depending on the blending ratio of components (A) to (D), but is preferably 0.001 to 1 part by weight per 1 part by weight of the total of components (A) to (D). teeth
It is 0.01 to 0.5 parts by weight. If the amount is less than 0.001 part by weight, no effect of suppressing hydrogen generation will be observed, making it difficult to maintain safety. If the amount is more than 1 part by weight, the oxygen absorption capacity and carbon dioxide generation capacity per unit weight of the freshness-preserving agent decrease, resulting in poor practicality. The freshness-preserving agent of the present invention contains the above-mentioned components (A) to (E) as essential components, but in order to improve the miscibility and mutual dispersibility of each component, a poorly water-soluble material is added. Fillers can also be added. Examples of such poorly water-soluble fillers include activated carbon, diatomaceous earth, acid clay, activated clay, silica, perlite, zeolite, alumina, kaolin, talc,
bentonite, calcium silicate, asbestos,
Water-resistant inorganic or organic powders such as magnesia, silica alumina, alkaline earth metal sulfates, carbonates and silicates, silicon nitride, graphite, aluminum hydroxide, iron oxide and cellulose;
Examples include granular materials. The amount of the poorly water-soluble filler added is preferably determined within the range of 0.001 to 10 parts by weight per 1 part by weight of the total of components (A) to (E). If it is less than 0.001 part by weight, there is no effect of improving dispersibility, and if it exceeds 10 parts by weight, the concentration of the active ingredient will be relatively lowered, and the oxygen absorption capacity and carbon dioxide gas generation capacity will be lowered, which is not preferable. Freshness preserving agents react with moisture to exhibit their ability to absorb oxygen and generate carbon dioxide gas, but normally the atmosphere or food contains a considerable amount of moisture, and the moisture that evaporates from it or the moisture in the atmosphere There is no need to add water to the freshness-preserving agent, as it fully demonstrates its ability. It is also a preferred form as it extends the period during which unused freshness preserving agent can be effectively utilized. However, if there is little moisture evaporating from the food or moisture in the atmosphere, and the oxygen absorption rate and carbon dioxide generation rate are slow,
The above slightly water-soluble filler impregnated with water,
By adding it or placing it simultaneously in the package or container, the rate of oxygen absorption and carbon dioxide generation can be increased. The freshness preserving agent of the present invention may be in any form as long as it contains the above components (A) to (E) as essential components. Powder and simply mixed it,
Alternatively, the mixed fine powder may be molded into pellets, beads, rods, blocks, sheets, etc. using a tablet machine, extrusion molding machine, roll molding machine, or the like. During such molding, binders and lubricants commonly used in powder molding can also be used. Such binders include:
For example, starch, carboxymethyl cellulose,
Examples include high molecular weight polymers such as polyvinyl acetate, polyolefin, and polyvinyl alcohol, and examples of lubricants include various stearic acid derivatives. As mentioned above, the freshness preserving agent of the present invention can be used as is in the form of a powder or molded product, or
It can also be used in a bag made of air-permeable packaging material, such as cellophane, various synthetic resin films, and paper. Here, the material, structure, etc. of the packaging material can be changed in various ways as long as it is breathable. In any case, when using a freshness-preserving agent, it is desirable to avoid direct contact with the food to prevent contamination of the target food, and either the freshness-preserving agent or the food, or both, should be covered with a breathable packaging material. It is preferable that the In addition, the freshness preserving agent of the present invention comprises (A) an oxygen absorber as an ingredient, a hydrogen generation inhibitor as an ingredient (E), and (B) an oxygen absorber as an ingredient.
The carbon dioxide generating agent consisting of the components (D) can be molded or packaged separately by the method exemplified above and then used together with the food by being sealed in one package or container. When the freshness preservation agent of the present invention is packaged or sealed in a container with food, it absorbs oxygen in the system and at the same time generates carbon dioxide gas, thereby preventing food from deteriorating due to oxygen and carbonation. It can exhibit the bacteriostatic or antibacterial effect of the gas and the effect of suppressing the biological effects on fruits and vegetables, and can be used safely because the generation of hydrogen is suppressed. The present invention will be explained in more detail by referring to Reference Examples, Comparative Reference Examples, Examples, and Comparative Examples below. Reference Examples 1 to 18 and Comparative Examples 1 to 5 Components (A) to (E) in the amounts shown in Table 1 were thoroughly mixed in a dry nitrogen atmosphere, and then filled into a perforated polyethylene laminate paper bag. , various compositions were manufactured. Subsequently, the paper bag was suspended in a glass bottle having an internal volume of about 1 ml and containing 5 ml of water at the bottom, and then the glass bottle was sealed. In addition, only in Reference Example 18, a dry glass bottle without water coexisting at the bottom was used, and hydrated diatomaceous earth was used as a filler. At room temperature,
After 48 hours, the pressure and composition of the gas in the glass bottle was analyzed to measure the amount of absorbed oxygen, amount of carbon dioxide gas generated, and amount of hydrogen generated, and the results shown in Table 1 were obtained.

【table】

[Table] When component (E) is not added (Comparative Reference Examples 1 and 3), a large amount of hydrogen is generated, and by adding component (E), hydrogen generation is approximately 1/10 to 1/20 suppressed. In the absence of component (A) (Comparative Reference Example 5), carbon dioxide gas generation is observed, but oxygen absorption ability is not observed and it cannot be put to practical use. In the case without component (B) (Comparative Reference Example 2), both oxygen absorption and carbon dioxide generation are extremely poor, and the product is impractical. When there is no component (D) (Comparative Reference Example 4), the amount of carbon dioxide gas generated is small, and it is not practical. Even when there is no moisture in the atmosphere, oxygen absorption and carbon dioxide gas generation performance is observed by adding moisture to the filler (Reference Example 18). Reference example 19 Triiron tetroxide 9.7g, calcium chloride dihydrate 1.5g
The amount of absorbed oxygen, the amount of carbon dioxide gas generated, and the amount of hydrogen generated were measured using a composition consisting of 1.5 g of sodium hydrogen carbonate, 1.5 g of sodium hydrogen carbonate, 1.5 g of succinic acid, and 1.5 g of glycine in the same manner as in Reference Example 1, and the results were as follows. Ta. Oxygen absorption amount 114ml Carbon dioxide gas generation amount 193ml Hydrogen generation amount 0.10ml Example 1 and Comparative Examples 1 to 2 Same composition as Reference Example 2, weight 1/4, and other methods similar to Reference Example 2. A freshness preservation agent packed in a perforated polyethylene paper bag is prepared, and this freshness preservation agent is placed in a polypropylene film (18μ) / ethylene vinyl alcohol copolymer film (15μ) / along with kamaboko (200g) and about 200ml of air.
After being sealed and packaged with a three-layer gas barrier film made of polyethylene film (50 μ), it was stored at room temperature (average temperature 27°C) to prevent changes over time and
The changes in the number of viable bacteria in g were measured, and the results shown in Table 2 were obtained. As a control, a package was packaged in the same manner as above without enclosing a freshness-preserving agent (air-containing packaging, Comparative Example 1), and a package was sealed after replacing with nitrogen gas without enclosing a freshness-preserving agent (comparison). A test for Example 2) was also conducted.

[Table] Example 2 and Comparative Examples 3 to 4 Baumkuchen was sealed and packaged in the same gas barrier film used in Example 1, together with the freshness preserving agent prepared in Reference Example 2 and about 800 ml of air. A storage test was conducted at an average temperature of 27°C. As a control, as in Example 1, tests were also conducted on an air-containing package (Comparative Example 3) and a nitrogen gas purged package (Comparative Example 4). As a result, mold growth was observed after 4 days in the air-containing packaging and 14 days after the nitrogen gas purging packaging, whereas mold growth was observed after 60 days in the packaging containing the freshness-preserving agent prepared in Reference Example 2. However, no mold growth was observed. Furthermore, the hydrogen content was 1% or less. Example 3 and Comparative Example 5 0.5 kg of freshly harvested grapes (Kyoho grapes) were hermetically packaged in a 25μ thick polyethylene sheet together with the perforated polyethylene paper bag freshness preservation agent prepared in Reference Example 2 and about 1 part of air. The average temperature was 26°C). As a control, a test was also conducted on a product packaged in the same manner as above but without the freshness preserving agent (Comparative Example 5). After 3 days and 6 days, the results shown in Table 3 were obtained by a sensory test.

【table】

Claims (1)

[Claims] 1. Consists of the following components, and the amino acid of component (E) is
For 1 part by weight of the total amount of components (A), (B), (C) and (D)
A freshness-preserving agent characterized by containing 0.001 to 1 part by weight. (A) Iron-based substances (B) Halides of alkali metals or alkaline earth metals (C) Carbon salts and/or hydrogen carbonates (D) Solid substances that become acidic when they interact with water (E) Isoelectric points 5.0 to 10.0 amino acids