JP2024095193A - Oxygen absorber, manufacturing method thereof, and packaged food - Google Patents

Abstract

【assignment】
To provide an oxygen absorber capable of suppressing deterioration of the appearance of a packaging container caused by shrinkage.
SOLUTION
The oxygen scavenger contains a base agent, an alkaline agent, a reaction catalyst, water, and activated carbon, and has a carbon dioxide generation capacity greater than an oxygen absorption capacity.
[Selection diagram] None

Description

This disclosure relates to oxygen absorbers, methods for producing oxygen absorbers, and packaged foods.

One method for preserving food and other contents for long periods of time is to enclose an oxygen absorber in a packaging container together with the contents. In this method, the food and oxygen absorber are enclosed in a gas-barrier sealed bag or container, and the oxygen in the sealed container is absorbed by the oxygen absorber, keeping the atmosphere inside the sealed container essentially oxygen-free, thereby suppressing quality deterioration due to oxidation and the proliferation of bacteria and microorganisms. There are two main types of oxygen absorbers that are frequently used today: inorganic oxygen absorbers that use iron as a main ingredient, and organic oxygen absorbers that use ascorbic acid and other oxygen-absorbing substances as a main ingredient.

Japanese Patent No. 3541859

The inventors have conducted extensive research and found that some contents contained in packaging containers such as packaging bags have a high carbon dioxide absorption capacity, and when they are contained in the package together with an oxygen scavenger, the amount of air in the packaging bag decreases significantly in conjunction with the oxygen absorption reaction of the oxygen scavenger, causing the packaging bag to shrink. This can lead to a deterioration in the appearance of the package.

The present disclosure has been made in consideration of the above circumstances, and aims to provide an oxygen absorber that can suppress deterioration of the appearance of the packaged body caused by shrinkage of the packaging container. In addition, the present disclosure also aims to provide a method for producing such an oxygen absorber, and a packaged food that contains such an oxygen absorber.

The present disclosure includes the following embodiments.
[1]
The composition includes an organic base material, an alkaline agent, a reaction catalyst, water, and a porous body,
An oxygen scavenger that can generate more carbon dioxide than it can absorb.
[2]
The oxygen scavenger according to [1], which is a granulated product.
[3]
The oxygen scavenger of [1] or [2], wherein the amount of carbon dioxide that can be generated is 0.1% or more greater than the amount of oxygen that can be absorbed.
[4]
The oxygen scavenger according to any one of [1] to [3], wherein the main ingredient contains at least one of ascorbic acid, a stereoisomer of ascorbic acid, and a salt thereof.
[5]
The porous body includes activated carbon,
The oxygen absorbing agent according to any one of [1] to [4], wherein the activated carbon contains 5% or more of the moisture contained in the oxygen absorbing agent.
[6]
The oxygen scavenger according to [5], wherein the content of the activated carbon is 15 to 25 mass% based on the total amount of the oxygen scavenger.
[7]
The oxygen scavenger according to any one of [1] to [6], further comprising a bicarbonate.
[8]
The oxygen scavenger according to any one of [1] to [7], wherein the content of carbonate is 20% by mass or more and the content of calcium hydroxide is 1% by mass or less, based on the total amount of the oxygen scavenger.
[9]
The oxygen scavenger according to any one of [1] to [8], further comprising calcium chloride.
[10]
The oxygen absorbing agent according to any one of [1] to [9], wherein the content of the main agent is 30 mass% or more based on the total amount of the oxygen absorbing agent.
[11]
A method for producing an oxygen scavenger according to any one of [1] to [10],
A manufacturing method comprising a step of mixing raw materials including a base agent, an alkaline agent, a reaction catalyst, water, and a porous body, but not including a drying step.
[12]
A food product, an oxygen absorber according to any one of [1] to [10], and a packaging bag,
the food and the oxygen absorber are sealed in the packaging bag;
A packaged food, wherein the content of the oxygen absorbing agent in the packaging bag is less than 50% by mass of the oxygen absorbing agent's capable of absorbing oxygen and is 0.4 to 0.8% by mass of the amount of air in the packaging bag.

According to the present disclosure, it is possible to provide an oxygen absorber that can suppress deterioration of the appearance of a packaged body caused by shrinkage of the packaging container. In addition, according to the present disclosure, it is also possible to provide a method for producing such an oxygen absorber, and a packaged food that contains such an oxygen absorber.

The oxygen absorber of the present embodiment contains a base agent, an alkaline agent, a reaction catalyst, water, and a porous body, and the amount of carbon dioxide that can be generated is greater than the amount of oxygen that can be absorbed. With such an oxygen absorber, the amount of carbon dioxide generated exceeds the amount of oxygen absorbed, so that even if there is a factor that causes a decrease in the amount of gas in the packaging container, such as the absorption of carbon dioxide by the contents, the packaging container can be prevented from shrinking. Therefore, deterioration of the appearance of the package of the packaged food or the like due to shrinkage of the packaging container can be prevented.
The oxygen absorber of the present embodiment may contain a base material, an alkaline agent, a reaction catalyst, water, and a porous body, and may contain a compound that reacts with oxygen to release carbon dioxide as the base material, and at least one of a carbonate and a hydrogen carbonate as the alkaline agent. With such an oxygen absorber, even if there is a factor that causes a decrease in the amount of gas in the packaging container, such as the absorption of carbon dioxide by the contents, deterioration of the appearance of the packaged body of the packaged food or the like due to the shrinkage of the packaging container can be suppressed.

Here, the oxygen absorption capacity and carbon dioxide generation capacity of the oxygen scavenger are the amounts of oxygen and carbon dioxide that the oxygen scavenger can absorb and generate, and can be expressed in units of, for example, ml/g. The oxygen absorption capacity and carbon dioxide generation capacity of the oxygen scavenger can be measured, for example, by the following method.
(1) A measured amount of oxygen absorber and a specified amount of air are sealed in a bag with oxygen barrier properties.
(2) Leave the container at rest in a 45°C environment for at least 3 days.
(3) Measure the _O2 and _CO2 concentrations inside the barrier bag.
(4) The next day, measure the _O2 and _CO2 concentrations again to confirm that they are unchanged from the previous day.
(5) The amount of oxygen absorbable and the amount of carbon dioxide evolvable are calculated from the _O2 concentration and _CO2 concentration measured in (4) according to the following formula.
_O2 absorbable amount [ml/g] = air volume [ml] × ((20.9 [%] - final _O2 concentration [%]) / 100) / oxygen absorber volume [g]
_CO2 generation capacity [ml/g] = air volume [ml] × (final _CO2 concentration [%]/100)/oxygen absorber volume [g]

For oxygen absorbers, the value of (amount of carbon dioxide that can be generated) - (amount of oxygen that can be absorbed) may be 1 ml/g or more, 2 ml/g or more, or 3 ml/g or more. The value of (amount of carbon dioxide that can be generated) - (amount of oxygen that can be absorbed) may be 25 ml/g or less, or 20 ml/g or less.

For oxygen scavengers, the amount of carbon dioxide that can be generated may be 0.1% or more greater than the amount of oxygen that can be absorbed, 1% or more greater, 3% or more greater, or 5% or more greater.

The oxygen absorption capacity of the oxygen absorber may be 40 ml/g or more, 60 ml/g or more, or 80 ml/g or more. The oxygen absorption capacity of the oxygen absorber may be 150 ml/g or less.

The amount of carbon dioxide that the oxygen absorber can generate may be 40 ml/g or more, 60 ml/g or more, or 80 ml/g or more. The amount of carbon dioxide that the oxygen absorber can generate may be 160 ml/g or less.

The main agent contained in the oxygen scavenger of this embodiment is an organic substance and is an oxygen absorbing substance. Examples of the main agent include compounds that react with oxygen to release carbon dioxide, specifically, ascorbic acid, stereoisomers of ascorbic acid, and salts of ascorbic acid and stereoisomers of ascorbic acid. One or more compounds can be used as the main agent.

The stereoisomer of ascorbic acid may be erythorbic acid. Ascorbic acid and the stereoisomer of ascorbic acid may be L-isomers. The salts of ascorbic acid and the stereoisomer of ascorbic acid may be alkali metal salts or sodium salts. In addition, ascorbic acid, the stereoisomer of ascorbic acid, and the salts thereof may be hydrates.

The content of the main ingredient in the oxygen scavenger may be 15 to 40% by mass, or 20 to 35% by mass, based on the total amount of the oxygen scavenger. The content of the main ingredient in the oxygen scavenger may be 20% by mass or more, 25% by mass or more, or 30% by mass or more, based on the total amount of the oxygen scavenger.

The alkaline agent may be a compound that exhibits alkalinity when dissolved in water to form an aqueous solution, and examples of the alkaline agent include hydroxides, carbonates, bicarbonates, phosphates, and hydrogen phosphates. The alkaline agent may be a salt of an alkali metal or an alkaline earth metal. Specific examples of the alkaline agent include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, radium hydroxide, lithium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate (baking soda), lithium bicarbonate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate. The oxygen scavenger may contain at least one of a carbonate and a bicarbonate. One or more types of alkaline agents may be used.

The content of the alkaline agent in the oxygen scavenger may be 0.5 to 15 mass % relative to the total mass of the oxygen scavenger, 1 to 10 mass %, or 1.5 to 8 mass %.

The alkaline agent may contain a carbonate, an alkali metal carbonate, or sodium carbonate. The carbonate content in the oxygen scavenger may be 25% by mass or more based on the total amount of the oxygen scavenger.

The oxygen scavenger may contain bicarbonate. The bicarbonate may be an alkali metal bicarbonate salt or may be sodium bicarbonate (baking soda). The bicarbonate tends to release carbon dioxide in the oxygen scavenger. The content of the bicarbonate in the oxygen scavenger may be 10 to 30% by mass, or 15 to 25% by mass, based on the total amount of the oxygen scavenger.

The oxygen scavenger preferably contains a compound capable of releasing carbon dioxide. Examples of such compounds include carbonates such as calcium carbonate. The carbonates may be included as an alkaline agent.

The content of alkaline earth metal hydroxide in the oxygen scavenger may be 1 mass % or less, 0.5 mass % or less, or 0.1 mass % or less, based on the total amount of the oxygen scavenger, depending on the content of other components. An example of an alkaline earth metal hydroxide is calcium hydroxide. The oxygen scavenger does not have to contain an alkaline earth metal hydroxide, particularly calcium hydroxide. Since alkaline earth metal hydroxides tend to react with carbon dioxide to form calcium carbonate, when the content of alkaline earth metal hydroxide is within the above range, the adverse effect on the amount of carbon dioxide generated can be sufficiently suppressed.

The reaction catalyst may be a transition metal compound. In the state of the oxygen absorbing composition, the transition metal compound may be dissolved in a liquid agent containing an oxygen absorbing substance. Specific examples of the transition metal element contained in the transition metal compound include iron, cobalt, nickel, copper, zinc, and manganese. The transition metal compound may be, for example, a halide, sulfate, nitrate, phosphate, carbonate, organic acid salt, oxide, hydroxide, or chelate compound of a transition metal. The transition metal compound may be a double salt containing a transition metal element. Examples of the transition metal compound include copper chloride (I), copper chloride (II), copper sulfate (II), copper hydroxide (II), copper oxide (I), copper oxide (II), manganese chloride, manganese nitrate, manganese carbonate, nickel chloride, and iron sulfate (II). The transition metal compound may be an iron compound. One or more types of reaction catalysts may be used.

The content of the reaction catalyst in the oxygen scavenger may be 0.5 to 15 mass%, 1 to 10 mass%, or 1.5 to 8 mass% relative to the total amount of the oxygen scavenger.

Examples of porous bodies include activated carbon, zeolite particles, bentonite particles, activated alumina particles, activated clay, calcium silicate particles, diatomaceous earth, etc. The porous body may contain activated carbon.

The content of the porous body in the oxygen absorber may be 10 to 30% by mass, or 15 to 25% by mass, based on the total amount of the oxygen absorber.

The activated carbon of the porous body may already contain moisture so that the powdered raw material does not fly up during granulation. The activated carbon may already contain 5% or more of the moisture contained in the oxygen scavenger, 8 to 60%, or 10 to 50%.

The amount of activated carbon in the oxygen scavenger may be 10 to 30% by mass, or 15 to 25% by mass, based on the total amount of the oxygen scavenger.

The water contained in the oxygen scavenger may be water of hydration contained in each raw material of the oxygen scavenger, or water that is already contained (impregnated) in the porous body (before mixing). The water content in the oxygen scavenger may be 5 to 25% by mass, or 10 to 20% by mass, based on the total amount of the oxygen scavenger.

The oxygen scavenger may contain calcium chloride to improve granulation. The content of calcium chloride in the oxygen scavenger may be 0.1 to 5% by mass, or 0.5 to 3% by mass, based on the total amount of the oxygen scavenger.

The oxygen scavenger may further contain a binder so that the granules can be easily formed. Specific examples of binders include gum arabic, polyvinyl alcohol, sodium alginate, gelatin, and cellulose. The content of the binder in the oxygen scavenger may be 0.1 to 5% by mass, or 0.5 to 3% by mass, based on the total amount of the oxygen scavenger.

The oxygen scavenger of this embodiment may be in the form of a powder or a granulated product. The granulation method is not particularly limited, and examples thereof include extrusion granulation, stirring granulation, fluidized bed granulation, rolling granulation, and compression granulation. Extrusion granulation can be performed, for example, using a screen with a predetermined number of openings.

The shape of the granules is not particularly limited, but may be, for example, spherical or cylindrical.

The manufacturing method of the oxygen scavenger of this embodiment is not particularly limited, but may be a method including a step of mixing raw materials including a base agent, an alkaline agent, a reaction catalyst, water, a porous body, and other optional components. When the oxygen scavenger is a granulated product, a step of granulating the mixture obtained after the step of mixing the raw materials may be included. In addition, in order to prevent the raw materials from scattering, the manufacturing method of the oxygen scavenger does not need to include a step of drying the raw materials, the mixture, or the oxygen scavenger (drying step).

The oxygen absorber may be used in the form of an oxygen absorber package in which the oxygen absorber is enclosed in a packaging material for the oxygen absorber. The packaging material may be a breathable packaging material.

The oxygen absorber may be used in a state where it is contained in a packaging container such as a packaging bag together with the contents to be contained in the packaging container. The contents include food, infusions, medicines, anaerobic cell culture kits, etc. Infusions may be contained in an infusion bag and then enclosed in the packaging bag.

The packaged food of this embodiment comprises food, the above-mentioned oxygen absorber, and a packaging bag, and the food and the organic oxygen absorber are sealed in the packaging bag. The content of the organic oxygen absorber in the packaging bag may be less than 50% by mass of the oxygen absorption capacity of the organic oxygen absorber, and may be 0.4 to 0.8% by mass of the air volume in the packaging bag. With such an air volume, there tends to be a good balance between the oxygen absorption capacity of the oxygen absorber and the amount of carbon dioxide generated. The packaging bag may be a gas barrier packaging bag.

(Production of oxygen absorbers)
The powder raw material of the oxygen scavenger was mixed uniformly in a sealed state according to the composition in Table 1, and then mixed again while adding water, and the mixture was granulated by an extrusion granulator to obtain a granulated product. Note that the content of water contained in the activated carbon raw material in each example was 45.1% by mass in Example 1, 16.6% by mass in Example 2, 15.7% by mass in Example 3, and 20.7% by mass in Example 4, relative to the total water content contained in the oxygen scavenger.
Main ingredient: Sodium erythorbate 1H ₂ O
_Alkaline agent: _Na2CO3
Activated carbon 1: Carborafine W-30 (water content 30% by mass)
Activated carbon 2: Taiko S-W50 (water content 50% by mass)
Ca(OH) ₂
・Binder: KC Flock (W400G)
Hydrogen carbonate: _{NaHCO3
CaCl2.2H2O ​}
Reaction _catalyst : _FeSO4.7H2O

The oxygen absorption capacity and carbon dioxide generation capacity of the oxygen absorber powder and granules were measured using the above (1) to (5). As Comparative Example 1, an oxygen absorber "Freshness Preservation Agent C Type" manufactured by Toppan Printing Co., Ltd. was used. As Comparative Example 2, an oxygen absorber "Ageless GE Type" (organic carbon dioxide generation type) manufactured by Mitsubishi Gas Chemical Company, Inc. was used. The results are shown in Table 2.

Claims (12)

The composition includes an organic base material, an alkaline agent, a reaction catalyst, water, and a porous body,
An oxygen scavenger that can generate more carbon dioxide than it can absorb. The oxygen scavenger according to claim 1, which is a granulated product. The oxygen absorber according to claim 1 or 2, in which the amount of carbon dioxide that can be generated is 0.1% or more greater than the amount of oxygen that can be absorbed. The oxygen scavenger according to claim 1 or 2, wherein the main ingredient contains at least one of ascorbic acid, a stereoisomer of ascorbic acid, and a salt thereof. The porous body includes activated carbon,
The oxygen scavenger according to claim 1 or 2, wherein the activated carbon contains in advance 5% by mass or more of the moisture contained in the oxygen scavenger. The oxygen absorber according to claim 5, wherein the activated carbon content is 15 to 25 mass% based on the total amount of the oxygen absorber. The oxygen scavenger according to claim 1 or 2, further comprising a hydrogen carbonate salt. The oxygen absorber according to claim 1 or 2, wherein the carbonate content is 20% by mass or more and the calcium hydroxide content is 1% by mass or less, based on the total amount of the oxygen absorber. The oxygen scavenger according to claim 1 or 2, further comprising calcium chloride. The oxygen absorber according to claim 1 or 2, wherein the content of the main agent is 30% by mass or more based on the total amount of the oxygen absorber. A method for producing the oxygen scavenger according to claim 1 or 2, comprising the steps of:
A manufacturing method comprising a step of mixing raw materials including a base agent, an alkaline agent, a reaction catalyst, water, and a porous body, but not including a drying step. A packaging bag comprising a food product, the oxygen absorber according to claim 1 or 2,
the food and the oxygen absorber are sealed in the packaging bag;
A packaged food, wherein the content of the oxygen absorbing agent in the packaging bag is less than 50% by mass of the oxygen absorbing agent's capable of absorbing oxygen and is 0.4 to 0.8% by mass of the amount of air in the packaging bag.