JP6884444B1 - Atmospheric conditioner and manufacturing method of atmosphere adjuster - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an atmosphere adjusting agent and a method for producing an atmosphere adjusting agent, which are highly reactive and can suppress a decrease in atmosphere adjusting ability in a manufacturing process without using expensive manufacturing equipment or the like. To provide. SOLUTION: In order to solve the above problems, a main agent, an alkaline agent, water, a carrier and activated carbon are contained, the main agent is ascorbic acids, and the alkaline agent, water, a carrier and activated carbon are used. The atmosphere-adjusting agent is characterized by containing a mixture of constituent components other than the main agent containing and, and a main agent in a solid state, and the amount of the main agent is set to a predetermined value according to the solubility of the main agent in water. Further, when the atmosphere adjusting agent is produced, the step of dissolving the ascorbic acids in water is not included. [Selection diagram] None

Description

The present invention relates to an atmosphere adjusting agent and a method for producing the same, and more particularly to an atmosphere adjusting agent having high reactivity and capable of suppressing deterioration in a manufacturing process and a method for producing the same.

Various organisms exist in the natural world, and among them, there are anaerobic microorganisms that grow in an atmosphere where oxygen does not exist, and microaerobic microorganisms that grow in an atmosphere where oxygen is lower than the atmospheric atmosphere. When culturing these microorganisms in a research institution or the like, it is necessary to control the concentration of oxygen, carbon dioxide, etc. in the growing atmosphere to a concentration suitable for culturing. Also, when culturing cells in the field of biotechnology, the oxygen and carbon dioxide concentrations in the culture atmosphere must be adjusted as necessary. As a simple method for adjusting the atmosphere in such a case, an atmosphere adjusting agent that reacts ascorbic acids with oxygen in the atmosphere to remove oxygen in the atmosphere and at the same time releases carbon dioxide gas is used. (See Patent Document 1, Patent Document 2 and Patent Document 3).

In these atmosphere modifiers, an aqueous solution of ascorbic acid is prepared and impregnated with activated carbon which is a porous carrier, so that the water required for the oxidation reaction of ascorbic acid is supplied from the aqueous solution of ascorbic acid, and the ascorbic acid and the ascorbic acid are supplied. It is supposed that the ascorbic acid is brought into contact with oxygen to promote the oxidation reaction of ascorbic acids.

By the way, conventionally, even in oxygen scavengers used for storing foods and the like, it has been practiced to maintain the storage atmosphere of foods and the like in an oxygen-free state by utilizing the oxidation reaction of ascorbic acids. However, as compared with such conventional oxygen scavengers, the atmosphere conditioner used for culturing bacteria and cells must adjust the culture atmosphere to a desired oxygen concentration and concentration in a much shorter time. In particular, in order to adjust the anaerobic culture atmosphere, it is necessary to rapidly absorb oxygen in the atmosphere. Therefore, in Patent Documents 1 to 3, by impregnating an aqueous solution of ascorbic acid having a high concentration close to the saturation concentration into granular activated carbon having a large specific surface area, a wide contact area between ascorbic acid and oxygen is secured and the reaction is carried out. It is said that the amount of carbon dioxide generated in the initial stage is large and the desired culture atmosphere can be adjusted in a short time.

Japanese Patent No. 5682831 Japanese Patent No. 5714790 Japanese Patent No. 6593564

However, since the atmosphere adjusting agents disclosed in Patent Documents 1 to 3 have high reactivity at the initial stage, when the aqueous solution of ascorbic acids comes into contact with oxygen during the manufacturing process, the oxidation reaction proceeds and the atmosphere adjusting ability deteriorates. It ends up. To prevent this, large-scale manufacturing equipment is required to keep each manufacturing process in a nitrogen atmosphere.

Therefore, the subject of the present invention is to provide an atmosphere adjusting agent and a method for producing an atmosphere adjusting agent, which are highly reactive and can suppress a decrease in the atmosphere adjusting ability in the manufacturing process without using expensive manufacturing equipment or the like. To do.

In order to solve the above problems, the atmosphere adjusting agent according to the present invention is an atmosphere adjusting agent containing a main agent, an alkaline agent, water, a carrier, and activated carbon, and the main agent is ascorbic acid. When the solubility of the main agent in water is a (g / 100 g-H ₂ O) (25 ° C.), the amount of the main agent contained in the atmosphere adjusting agent is x (g), and the total water content is b (g), the following It is characterized by satisfying the relational expression (1) of the above, and containing a mixture composed of components other than the main agent containing the alkaline agent, the water, the carrier and the activated carbon, and the main agent in a solid state.
1.3 <x / ((a / 100) x b) ≤ 25.0 ... (1)

In the atmosphere adjusting agent according to the present invention, the activated carbon is a hydrous activated carbon having an average volume particle size of less than 0.1 mm containing 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent as impregnated water. It is preferable to have.

In the atmosphere adjusting agent according to the present invention, the water content of the hydrous activated carbon is preferably 45 parts by mass or more with respect to 100 parts by mass of the hydrous activated carbon.

In the atmosphere adjusting agent according to the present invention, it is preferable that the activated carbon component obtained by removing the impregnated water from the hydrous activated carbon is contained in an amount of 125 parts by mass or less with respect to 100 parts by mass of the main agent.

In the atmosphere adjusting agent according to the present invention, it is preferable that the micropore volume of the activated carbon by the t-plot method is 0.3 cm ^{3 / g or more.}

In the atmosphere adjusting agent according to the present invention, it is preferable that the mode pore diameter (measurement range 0.04 to 9.0 μm) of the activated carbon by the mercury injection method is 0.050 μm or more.

In the atmosphere adjusting agent according to the present invention, it is preferable that the total amount of water contained in the atmosphere adjusting agent is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the main agent.

In the atmosphere adjusting agent according to the present invention, it is preferable that potassium carbonate is contained in an amount of 35 parts by mass or more and 150 parts by mass or less as the alkaline agent with respect to 100 parts by mass of the main agent.

In the atmosphere adjusting agent according to the present invention, it is preferable that ferrous sulfate heptahydrate is contained in a range of 30 parts by mass or more and 250 parts by mass or less as a reaction catalyst with respect to 100 parts by mass of the main agent.

In order to solve the above problems, the method for producing an atmosphere adjusting agent according to the present invention is a method for producing an atmosphere adjusting agent containing a main agent, an alkaline agent, water, a carrier, and activated carbon. Is an ascorbic acid, and does not include a step of dissolving the main agent in the water, and a step of obtaining a mixture consisting of the alkali agent, the water, the carrier, and the constituent components other than the main agent containing the activated carbon. It is characterized by comprising a step of adding the main agent in a solid state to the mixture.

In the method for manufacturing the atmosphere adjusting agent according to the present invention, the solubility in water of the main agent _{a (g / 100g-H 2} O) (25 ℃), the main agent amount contained in the atmosphere modifier x (g), total When the water content is b (g), it is preferable to determine the blending amounts of the main agent and the water so as to satisfy the following relational expression (1).
1.3 <x / ((a / 100) x b) ≤ 25.0 ... (1)

In the method for producing an atmosphere adjusting agent according to the present invention, the activated carbon is preliminarily impregnated with 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent, and the activated carbon containing the impregnated water is impregnated. It is preferable to obtain the mixture using.

According to the present invention, there is provided an atmosphere adjusting agent and a method for producing an atmosphere adjusting agent, which are highly reactive and can suppress a decrease in atmosphere adjusting ability in a manufacturing process without using expensive manufacturing equipment or the like. Can be done.

Hereinafter, preferred embodiments of the atmosphere conditioner according to the present invention will be described.

1. 1. Atmosphere adjuster The atmosphere adjuster according to the present invention contains a main agent, an alkaline agent, water, a carrier, and activated carbon, the main agent is ascorbic acid, and the solubility of the main agent in water is a (g / 100 g-). H 2 _O) (25 ° C.), when the base resin amount contained in the atmosphere adjusting agent was x (g), the total water content b (g), satisfies the following relational formula (1), configurations other than the base resin It is characterized by containing a mixture of components and a main agent in a solid state.
1.3 <x / ((a / 100) x b) ≤ 25.0 ... (1)

The atmosphere adjusting agent adjusts the oxygen concentration and the carbon dioxide concentration in the culture atmosphere by absorbing oxygen in the atmosphere and releasing carbon dioxide by utilizing the oxidation reaction of ascorbic acids as the main agent. The oxidation reaction of ascorbic acids is carried out under basic conditions using water (liquid phase) as a reaction field. Therefore, water is an essential constituent. In the conventional atmosphere adjusting agent, a form in which a carrier is impregnated with an aqueous solution as an aqueous solution is adopted, whereas in the present invention, a form containing a mixture composed of components other than the main agent and a main agent in a solid state is adopted. Since the conventional atmosphere adjusting agent requires a step of adjusting the aqueous solution of ascorbic acid at the time of production, the oxidation reaction of ascorbic acid proceeds unless the contact between the aqueous solution of ascorbic acid and oxygen is suppressed by keeping the manufacturing process in a nitrogen atmosphere. However, the ability to adjust the atmosphere may decrease. Further, when preparing an aqueous solution of ascorbic acids, if a high concentration aqueous solution close to the saturation concentration is not prepared, the amount of the main agent compounded in the atmosphere adjusting agent decreases, and it becomes difficult to obtain a highly reactive atmosphere adjusting agent. Become.

On the other hand, in the present invention, the main agent is blended so as to satisfy the above formula (1), and a form containing a mixture composed of components other than the main agent and the main agent in a solid state is adopted. That is, in the atmosphere adjusting agent according to the present invention, the main agent content is increased with respect to the water content by containing the main agent in an amount exceeding the solubility as a solid, instead of dissolving the main agent in water. Can be done. Further, as described later, in the atmosphere adjusting agent, for example, activated carbon is impregnated with water in advance, and when the atmosphere adjusting agent is used, the impregnated water is used to promote the oxidation reaction of ascorbic acids. be able to. From these things, a highly reactive atmosphere conditioner can be obtained. On the other hand, the atmosphere adjusting agent can eliminate the step of adjusting the aqueous solution of ascorbic acid at the time of production. That is, since the main agent can be handled in a solid (powder) state even during manufacturing, even if the atmosphere adjusting agent is manufactured in the atmosphere, the oxidation reaction of the main agent does not proceed, and the atmosphere adjusting ability in the manufacturing process is improved. The decrease can be suppressed. Therefore, the atmosphere adjusting agent can be manufactured with a simple manufacturing facility without a large-scale and expensive manufacturing facility for maintaining the manufacturing process in a nitrogen atmosphere. Hereinafter, each component of the atmosphere adjusting agent will be described in detail in order. The atmosphere adjusting agent may contain a reaction catalyst in addition to the main agent, alkaline agent, water, carrier, and activated carbon. Therefore, the reaction catalyst will also be described below.

(1) Main agent As the ascorbic acid as the main agent, L-ascorbic acid, erythorbic acid (D-isoascorbic acid) which is a stereoisomer thereof, and salts or hydrates thereof can be used. For example, examples of L-ascorbic acid salt include sodium L-ascorbic acid, potassium L-ascorbic acid, calcium L-ascorbic acid, and the like. Examples of the erythorbic acid salt include sodium erythorbate, potassium erythorbate, calcium erythorbate and the like. One or more of these can be used as the main agent.

In particular, in the atmosphere adjusting agent according to the present invention, it is preferable that the main agent is not too soluble in water and exhibits an appropriate solubility. For example, sodium L-ascorbic acid has a solubility in water of 62 (g / 100 g-H ₂ O) (25 ° C.) and is highly soluble in water. When an aqueous solution of ascorbic acid is supported / impregnated in a carrier like a conventional atmosphere conditioner, it is better to use a highly soluble ascorbic acid such as sodium ascorbic acid as the main agent to achieve a higher concentration of ascorbic acid. An aqueous solution of acids can be supported on the carrier, which is preferable in obtaining a highly reactive atmosphere conditioner. On the other hand, in the present invention, since the main agent is contained in a solid state, a desired amount of the main agent can be contained even if the solubility in water is not as high as that of ascorbic acid salt. Obtainable. Further, when the same amount of the main agent is used, the amount of the carrier compounded can be reduced as compared with the conventional case, so that the weight of the whole can be reduced and the material cost can be reduced. Further, if the solubility in water becomes too high, the main agent may absorb moisture in the manufacturing process and the oxidation reaction may proceed. On the other hand, when it shows almost no solubility in water, it may be difficult to obtain a highly reactive atmosphere conditioner. Therefore, as described above, it is preferable that the base material has an appropriate solubility in water.

Here, the solubility of the main agent in water is expressed by the solubility of the main agent in water. However, the solubility generally refers to the limit amount at which a certain solute dissolves in a certain amount of solvent, and here, it represents the solubility in 100 g (100 ml) of water at 25 ° C. At this time, the solubility of the main agent in water _{is preferably 45 (g / 100 g-H 2} O) (25 ° C.) or less and 1 (g / 100 g-H ₂ O) (25 ° C.) or more. Ascorbic acids having a solubility within such a range include erythorbic acid (solubility: 40 g / 100 g-H ₂ O), ascorbic acid (solubility: 33 (g / 100 g-H ₂ O) (25 ° C.), erythorbic acid salt. (For example, the solubility of sodium erythorbate: 16 (g / 100 g-H ₂ O) (25 ° C.) can be mentioned, and it is preferable to use these as the main agent. However, even when two or more types of main agents are used, respectively. It is preferable that the solubility of is within the above range.

Further, the solubility of the main agent in water _{is more preferably 40 (g / 100 g-H 2} O) (25 ° C.) or less and 5 (g / 100 g-H ₂ O) (25 ° C.) or more, more preferably 30 (g / g / g /. 100 g-H ₂ O) (25 ° C) or less 8 (g / 100 g-H ₂ O) (25 ° C) or more is more preferable, and 20 (g / 100 g-H ₂ O) (25 ° C) or less 10 ( It is more preferably g / 100 g−H ₂ O) (25 ° C.) or higher. More specifically, it is more preferable to use erythorbic acid salt, which has a solubility in water within the above range, as a main agent. Since erythorbic acid salt is easily available and inexpensive as compared with ascorbic acid and ascorbic acid salt, the atmosphere adjusting agent can be produced at a lower cost than when these are used as a main agent.

Further, the blending amount of the main agent shall satisfy the above formula (1). By determining the blending amount of the main agent so as to satisfy the above formula (1) according to the solubility of the main agent in water, the oxidation reaction of ascorbic acids can be efficiently promoted, and a highly reactive atmosphere adjusting agent can be obtained. Obtainable.

Here, in order to obtain an atmosphere modifier having higher reactivity, the lower limit of the above formula (1) is more preferably 1.5. In particular, in order to adjust the atmosphere for anaerobic culture, it is necessary to absorb oxygen in the atmosphere more quickly than when adjusting the atmosphere for microaerobic culture. The oxygen absorption rate varies depending on the total amount of water in the atmosphere adjuster and the amount of impregnated water impregnated in activated carbon, but the lower limit is more preferably 2.0 in order to adjust the atmosphere for anaerobic culture. It is more preferably 0.0. Further, if the upper limit of the above formula (1) becomes too large, the amount of the main agent becomes too large with respect to the solubility of the main agent in water and the total water content. In this case, the oxygen absorption rate decreases, and the effect of increasing the amount of the main agent diminishes. From this point of view, the upper limit of the above formula (1) is preferably 20.0, more preferably 18.0, and even more preferably 15.0. When these preferable values are adopted in the above formula (1), the inequality sign with the equal sign may be replaced with the inequality sign with the equal sign for the lower limit value, or the inequality sign with the equal sign may be replaced with the inequality sign for the upper limit value. .. When two or more kinds of ascorbic acids are used as the main agent, the limit amount at which the mixture of the main agent in which each ascorbic acid is mixed at a predetermined mixing ratio dissolves in 100 ml of water (25 ° C.) is defined. The predetermined mixing ratio means the mixing ratio of two or more kinds of ascorbic acids as the main agent.

Further, the average volume particle size of the main agent is preferably 20 μm or more and 600 μm or less, and is preferably larger than the average volume particle size of the activated carbon as described later. The "average volume particle size" of the main agent was calculated from the product of the weight frequency and the median value of the particles existing between the meshes after sorting the particles for each mesh by the sieving method. It was set as a value.

(2) Alkaline agent As described above, since the oxidation reaction of ascorbic acids is carried out under basic conditions, the alkaline agent is an essential component of the atmosphere adjusting agent according to the present invention. In the present invention, for example, an alkali metal carbonate can be preferably used as the alkaline agent. By using an alkali metal carbonate, the amount of carbon dioxide released into the atmosphere due to the oxidation reaction of ascorbic acids can be adjusted. As the alkali metal carbonate, potassium carbonate, sodium carbonate, calcium carbonate and the like can be preferably used.

Here, when erythorbic acid salt is used as the main agent as described above, it is particularly preferable to use potassium carbonate as the alkaline agent. The solubility of potassium carbonate in water is 113.5 (g / 100 g-H ₂ O) (25 ° C.), and the solubility in water is extremely high. On the other hand, the solubility of erythorbic acid salt in water is as described above, and the solubility in water is lower than that of potassium carbonate. When a compound having low solubility in water is used for both the main agent and the alkaline agent, it becomes difficult to adjust a preferable reaction field for rapidly advancing the oxidation reaction of ascorbic acids, and a highly reactive atmosphere adjusting agent is obtained. It becomes difficult. On the other hand, when a compound having high solubility in water is used for both the main agent and the alkaline agent, ascorbic acids are decomposed by the alkaline agent when these are mixed, and the oxidation reaction of the ascorbic acids proceeds excessively. The oxygen absorption capacity of the main agent may decrease or its fluidity may decrease before the atmosphere adjusting agent is produced.

From these facts, by using erythorbic acid salt, which has relatively low solubility in water, as the main agent and potassium carbonate, which has extremely high solubility in water, the main agent is decomposed and the oxidation reaction proceeds during the manufacturing process. It is possible to prevent this from occurring, and it is possible to maintain good fluidity of the atmosphere adjusting agent.

Even when the main agent is other than erythorbic acid salt, when potassium carbonate is used as the alkaline agent, the powder characteristics (fluidity, apparent density, etc.) are better than when other alkaline agents are used. High oxygen absorption capacity can be obtained. Further, by appropriately adjusting the amount of potassium carbonate added, it becomes easy to control the amount of carbon dioxide generated, and the oxygen concentration of the atmosphere adjusting agent according to the use such as for anaerobic culture and microaerobic culture. And it becomes easy to adjust to the carbon dioxide concentration. On the other hand, from the above viewpoint, when ascorbic acid salt having high solubility in water is used as the main agent, it is also preferable to use sodium carbonate or calcium carbonate having low solubility in water as the alkaline agent as compared with ascorbic acid salt.

In the atmosphere adjusting agent according to the present invention, the alkaline agent is preferably contained in an amount of 10 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the main agent, and is used for anaerobic culture, microaerobic culture and the like as described above. Therefore, it is preferable to appropriately adjust the content of the alkaline agent according to the type of the main agent.

For example, when erythorbic acid salt is used as the main agent and potassium carbonate is used as the alkaline agent, when adjusting the atmosphere for anaerobic culture, potassium carbonate is contained in an amount of 35 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of erythorbic acid salt. Is preferable. In order to more quickly adjust the atmosphere for anaerobic culture, it is more preferable that potassium carbonate is contained in an amount of 40 parts by mass or more, and more preferably more than 40 parts by mass, based on 100 parts by mass of erythorbic acid salt. Similarly, it is more preferable to contain 130 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 90 parts by mass or less with respect to 100 parts by mass of erythorbic acid salt.

(3) Water Water is an indispensable component for acclimatizing components other than the main agent constituting the atmosphere adjusting agent and providing a place for the oxidation reaction of the main agent. In the present invention, when the main agent is 100 parts by mass, the total amount of water contained in the atmosphere adjusting agent is preferably 20 parts by mass or more and 150 parts by mass or less. In order to obtain a highly reactive atmosphere conditioner, the total water content is more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the main agent. Is more preferable. Further, the total water content is preferably 140 parts by mass or less, and more preferably 120 parts by mass or less with respect to 100 parts by mass of the main agent.

In the atmosphere adjusting agent according to the present invention, it is preferable that water is supported (impregnated) on each of the carrier and the activated carbon. That is, the total water content is the amount of water supported on the carrier (hereinafter referred to as "supported water") and the amount of water supported (impregnated) on the activated carbon (hereinafter referred to as "impregnated water"). It is the total value with the quantity. Then, it is preferable that the activated carbon is impregnated with 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent as impregnated water. In order to obtain a highly reactive atmosphere conditioner, it is preferable that 45% by mass or more, more preferably 55% by mass or more of the total water content is impregnated with activated carbon as impregnated water. Further, it is preferable that 5% by mass or more and 60% by mass or less of the total water content contained in the atmosphere adjusting agent is supported on the carrier.

Further, in the atmosphere adjusting agent, the amount of supported water is preferably 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the main agent. In the present invention, water added as a liquid when producing an atmosphere adjusting agent (hereinafter referred to as "added water") is mainly supported on a carrier, and a hydrous activated carbon containing impregnated water in advance is used in addition to the added water. Is preferable. That is, it is preferable that the amount of supported water and the amount of added water are substantially the same. In this case, the amount of added water is preferably such that the amount of water that can be supported by the carrier is not exceeded. When the amount of added water increases beyond the amount of water that can be supported by the carrier, it becomes difficult for the carrier to support the entire amount, and excess water added to the supported water is present in the atmosphere conditioner. become. The atmosphere adjusting agent is characterized by containing the main agent in a solid state. However, if excess water added to the supported water is present in the atmosphere adjusting agent, the carrier cannot retain water and the fluidity deteriorates, or it becomes difficult to maintain the main agent in a solid state. .. Further, in the manufacturing process of the atmosphere adjusting agent, the main agent may come into contact with the added water or absorb moisture, and the oxidation reaction of the main agent may proceed. Therefore, when the content of the carrier is increased so that all the added water is supported on the carrier, it is necessary to increase the content of the carrier as compared with the constituent components that contribute to the oxidation reaction of the main agent. In that case, it becomes difficult to efficiently proceed with the oxidation reaction of the main agent, and it becomes difficult to obtain a highly reactive atmosphere adjusting agent. Therefore, the content of the supported water is more preferably less than 80 parts by mass, more preferably less than 50 parts by mass, and even more preferably less than 40 parts by mass with respect to 100 parts by mass of the main agent. Further, if the amount of supported water is too small, it becomes difficult to dissolve components other than the main agent such as an alkaline agent in the supported water and support the carrier as an aqueous solution. From this point of view, the content of the supported water is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more with respect to 100 parts by mass of the main agent.

On the other hand, the impregnated water is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the main agent. Oxidation of the main agent by adding 40% by mass or more and 95% by mass or less of the total water content of the atmosphere adjusting agent to the activated carbon as impregnated water and adding water to the main agent so that the impregnated water is within the above range. A sufficient amount of water required for the reaction can be secured. Furthermore, when an aqueous solution in which the main agent is dissolved in water is supported (impregnated) on a carrier or activated carbon, the concentration of the main agent or alkaline agent decreases as the amount of water increases, and a highly reactive atmosphere conditioner is obtained. It becomes difficult. On the other hand, according to the present invention, by impregnating fine powdered activated carbon with water, it is possible to provide water necessary for the oxidation reaction of the main agent without adjusting the main agent or alkaline agent to the state of an aqueous solution. it can.

(4) Reaction catalyst The atmosphere conditioner according to the present invention preferably contains a reaction catalyst for promoting the oxidation reaction of ascorbic acids. As the reaction catalyst, for example, an organic metal-based catalyst such as iron citrate or iron phthalocyanine can be used, but a hydrochloride, nitrate, sulfate, or compound salt of a transition metal such as iron, nickel, copper, or manganese, or a compound salt, or It is preferable to use an inorganic catalyst such as these hydrates. An atmosphere conditioner having a high oxygen absorbing ability can be obtained by the configuration including the reaction catalyst. In particular, in the atmosphere conditioner, it is preferable to use ferrous sulfate heptahydrate as a reaction catalyst.

In the atmosphere adjusting agent according to the present invention, the content of the reaction catalyst can be appropriately adjusted according to the type of the reaction catalyst and the like, but the reaction catalyst is 30 parts by mass or more and 250 parts by mass with respect to 100 parts by mass of the main agent. It is preferable to include the following. When the content of the reaction catalyst is less than 30 parts by mass, it becomes difficult to quickly adjust the culture atmosphere to the desired oxygen concentration and carbon dioxide concentration. As will be described later, the atmosphere modifier is basically mixed with other components in a solid (powder) state without being dissolved in water, even for the reaction catalyst. Even if a part of the reaction catalyst may dissolve in the supported water, for example, the surplus reaction catalyst will be mixed with other components in the form of powder. Even in such a state, the powdered activated carbon is impregnated with, for example, a saturated amount of water as impregnated water and contained in the atmosphere adjusting agent as the hydrous activated carbon, so that the impregnated water is used for the reaction field. Can be obtained and the reaction catalyst can function.

(5) Carrier The atmosphere conditioner according to the present invention includes a carrier capable of supporting water. By including the carrier, the constituent components of the atmosphere conditioner can be granulated and handled as a powder. As the carrier, a porous substance such as zeolite, wet silica, vermiculite, or montmorillonite can be used. One or more of these porous substances can be used alone or in combination.

The average volume particle size of the carrier is preferably 0.01 mm or more and 3 mm or less, more preferably 0.1 m or more and 2 mm or less, and further preferably 0.2 m or more and 1.2 mm or less.

In the atmosphere adjusting agent according to the present invention, the content of the carrier is preferably 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the main agent. If the content of the carrier is less than 50 parts by mass, it is not possible to sufficiently support water and the like required for the deoxygenation reaction, and a highly reactive atmosphere conditioner can be obtained and the characteristics of the granulated material as a powder can be obtained. It becomes difficult to maintain. From these viewpoints, the content of the carrier is more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more. On the other hand, when the content of the carrier exceeds 500 parts by mass, the content of the carrier with respect to the main agent is large, and the main agent and oxygen in the atmosphere cannot be efficiently brought into contact with each other. Therefore, the amount of oxygen absorbed per unit mass of the atmosphere adjusting agent is reduced, which is not preferable. From these viewpoints, the content of the carrier is more preferably 350 parts by mass or less, and further preferably 200 parts by mass or less. In particular, when adjusting the atmosphere for anaerobic culture, it is preferable that the content of the carrier is 200 parts by mass or less in order to obtain a highly reactive atmosphere adjusting agent.

(6) Hydrous activated carbon The atmosphere conditioner according to the present invention contains activated carbon in addition to the above-mentioned carrier. Here, the activated carbon is preferably a powdered activated carbon having an average volume particle size of less than 0.2 mm, more preferably less than 0.1 mm. Further, it is preferable that the activated carbon has a smaller average volume particle size than the main agent. Further, it is preferable that the average volume particle size is smaller than that of the above-mentioned carrier. In particular, the average volume particle size is preferably 5 μm or more and 15 μm or less.

Activated carbon is also a porous substance and can be impregnated with water. As described above, the activated carbon is preferably a hydrous activated carbon that contains a predetermined amount of water as impregnated water in advance. Here, pre-containing a predetermined amount of water as impregnated water means that the pores of the activated carbon are already impregnated with a predetermined amount of water before the activated carbon is mixed with other constituent components. To do.

The water content of the hydrous activated carbon, that is, the ratio of the impregnated water in the hydrous activated carbon is preferably 45 parts by mass or more, more preferably 50 parts by mass or more, and 55 parts by mass or more with respect to 100 parts by mass of the hydrous activated carbon. It is more preferable to have 57 parts by mass or more.

On the other hand, the amount of the activated carbon component obtained by removing the impregnated water from the hydrous activated carbon is preferably 125 parts by mass or less, more preferably 100 parts by mass or less, and 70 parts by mass or less with respect to 100 parts by mass of the main agent. It is even more preferably 55 parts by mass or less, and even more preferably 45 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more.

By impregnating activated carbon with a small particle size with respect to the main agent in advance, a state in which a plurality of activated carbons are attached to the surface of the main agent particles is obtained, and the support is impregnated with an aqueous solution in which the main agent is dissolved in water. At least, when the atmosphere adjusting agent is used, water can be efficiently supplied to the main agent to quickly adjust the oxygen concentration and the carbon dioxide concentration in the atmosphere.

It is preferable that t-Plot method micropore volume of activated carbon is 0.30 cm ³ / g or more, more preferably 0.40 cm ³ / g or more, it is 0.50 cm ³ / g or more More preferred. The t-Plot method micropore volume can be measured using, for example, BELSORP-miniII manufactured by Microtrac Bell, Inc. after performing pretreatment by vacuum degassing at 130 ° C. for 8 hours. Specifically, the adsorption / desorption isotherm with nitrogen was measured using a constant volume method, and the analysis was performed by Harkins-Jura-BEL. The above value can be obtained by calculating using the t reference curve.

The porous substance containing activated carbon has a large number of pores, and the pores are divided into macropores, mesopores, micropores and the like according to the pore size. The total pore volume represents the volume of all pores regardless of the pore diameter. The pore diameter decreases in the order of macro hole, meso hole, and micro hole. In the atmosphere adjusting agent according to the present invention, no particular correlation was observed between the value of the total pore volume and the high reactivity (oxygen absorption rate, carbon dioxide release rate, etc.). On the other hand, a correlation was observed between the micropore volume and the high reactivity, and the larger the micropore volume, the better the reactivity. Although the reason has not been clarified, it is speculated that the water impregnated in the micropores strongly contributes to the progress of the oxidation reaction of the main agent in the atmosphere adjusting agent containing the main agent in a solid state. Further, the micropores are more likely to absorb water due to the capillary phenomenon than the macropores and mesopores having a large pore diameter, and when the total pore volumes are the same, the larger the micropore volume, the easier it is to obtain activated carbon having a high water content. it is conceivable that. As will be described in Examples described later, a correlation is also observed between the high water content and the high reactivity of the activated carbon. From these facts, it is considered that the larger the micropore volume, the more efficiently the oxidation reaction of the main agent can proceed, and the more highly reactive atmosphere adjusting agent can be obtained.

Further, it is preferable that the mode pore diameter (measurement range 0.04 to 9.0 μm) of the activated carbon by the mercury injection method is 0.050 μm or more. The mode pore diameter (measurement range 0.04 to 9.0 μm) is, for example, a pore diameter of 0.04 μm to 9.0 μm under measurement conditions in a high pressure range of 20 to 5000 psi using a mercury press-fit porosimeter PoreMaster 33GT manufactured by AntonioPaar. It can be obtained by measuring the range of and analyzing it with the attached software.

As described above, in the atmosphere adjusting agent according to the present invention, a highly reactive atmosphere adjusting agent can be obtained when the composition contains activated carbon having a large micropore volume. Further, in the atmosphere adjusting agent according to the present invention, a correlation is observed between the size of the mode pore diameter and the high reactivity, and it is more reactive when activated carbon having a large mode pore diameter is used. An atmosphere modifier can be obtained. The reason for this has not been clarified, but it is inferred as follows. When the mode pore diameter was measured with the measurement range of 0.006 μm to 9.0 μm, no correlation was observed between the mode pore diameter and the high reactivity. On the other hand, a correlation was observed in the above measurement range. From this, the micropores having the mode pore diameter within the above range have a relatively large pore diameter among the micropores, and absorb water well due to the capillary phenomenon. On the other hand, if the pore diameter of the micropores becomes too small, it becomes difficult for water to enter the pores due to the capillary phenomenon, and the action due to surface adsorption becomes greater than the water absorption action due to the capillary phenomenon. In that case, even if the activated carbon is immersed in water, it becomes difficult to absorb water into the pores, and water molecules adsorbed in the pores become difficult to be released to the outside due to hydrogen bonds generated between the pore walls. .. Therefore, by making the micropores having a relatively large mode pore diameter, the amount of water impregnated in the activated carbon can be increased, and the water is released well during the oxidation reaction of the main agent, so that the reactivity is high. It is speculated that it will be easier to obtain an atmosphere conditioner.

(7) Content ratio of each component Next, the content ratio of each component to the total amount of the component of the atmosphere conditioner will be described. However, the total amount of the constituent components includes the main agent, alkaline agent, water, carrier, and activated carbon, and when the atmosphere adjusting agent contains other components such as a reaction catalyst, all the other components are included.

When the atmosphere adjusting agent according to the present invention is used as an atmosphere adjusting agent for anaerobic culture, the main agent is 10% by mass or more and 35% by mass or less, the alkaline agent is 10% by mass or more and 15% by mass or less, and water is used with respect to the total amount of the constituent components. 10% by mass or more and 25% by mass or less (of which, supporting water is 3% by mass or more and 25% by mass or less, impregnated water is 0% by mass or more and 20% by mass or less), the reaction catalyst is 15% by mass or less, and the carrier is 15% by mass. % Or more and 25% by mass or less, and preferably contains 4% by mass or more and 15% by mass or less of activated charcoal (however, only the activated charcoal component). By containing these components in such a content ratio, a highly reactive atmosphere conditioner for anaerobic culture can be obtained.

On the other hand, when the atmosphere adjusting agent according to the present invention is used as an atmosphere adjusting agent for microaerobic culture, the main agent is 5% by mass or more and 10% by mass or less and the alkaline agent is 15% by mass or more and 25% by mass with respect to the total amount of the constituent components. % Or less, water 20% by mass or more and 25% by mass or less (of which, supporting water is 3% by mass or more and 25% by mass or less, impregnated water is 0% by mass or more and 20% by mass or less), and the reaction catalyst is 20% by mass or less. It is preferable that the body is contained in an amount of 15% by mass or more and 25% by mass or less, and activated charcoal (however, only the activated carbon component) is contained in an amount of 5% by mass or more and 15% by mass or less. By containing these components in such a content ratio, a highly reactive atmosphere conditioner for microaerobic culture can be obtained.

2. Method for producing an atmosphere adjusting agent Next, an example of a method for producing an atmosphere adjusting agent according to the present invention will be described. The method for producing an atmosphere adjusting agent according to the present invention does not include a step of dissolving the main agent in water, but includes a step of obtaining a mixture consisting of constituent components other than the main agent including an alkaline agent, water, a carrier and activated charcoal, and a main agent in the mixture. Including the step of adding. At that time, for example, as described below, a step of preparing a raw material and a step of mixing components other than the main agent (carrier, alkaline agent, water, activated carbon (hydrous activated carbon), reaction catalyst) in a predetermined order. And are preferably included. Hereinafter, each step will be described in order, but the method for producing the atmosphere adjusting agent according to the present invention is not limited to the method described below, and does not include the step of dissolving the main agent in water, and the alkaline agent, water, and the like. It can be appropriately changed as long as it includes a step of obtaining a mixture consisting of constituent components other than the main agent containing the carrier and the active charcoal, and a step of adding the main agent to the mixture.

(1) Step of preparing raw materials Prepare the main agent, alkaline agent, carrier, water, and activated carbon in predetermined amounts. In addition, a reaction catalyst is prepared as needed. Since each of these constituent components is as described above, description thereof will be omitted here. However, it is preferable to prepare water as the added water by the amount of the supported water to be supported on the carrier. As for activated carbon, it is preferable to prepare the above-mentioned hydrous activated carbon containing a predetermined amount of impregnated water in advance. When preparing a predetermined amount of hydrous activated carbon, a commercially available hydrous activated carbon having a water content of the above ratio may be prepared so that the activated carbon component is a predetermined amount, or a predetermined amount of activated carbon in a dry state is prepared. Water may be impregnated in advance so that the water content becomes the above ratio with respect to the activated carbon. Further, the impregnated water impregnated in the activated charcoal and the supported water carried on the carrier are prepared as added water (water), and the activated charcoal and the total amount of the added water are mixed before mixing the carrier and the added water. The activated charcoal may be impregnated with water of impregnated water in advance. In the following, a case where hydrous activated carbon is used and only the amount of supported water is prepared as added water will be described as an example.

(2) Step of mixing components other than the main agent in a predetermined order After preparing a predetermined amount of each raw material, the components other than the main agent are mixed. At that time, it is preferable to mix the hydrous activated carbon after supporting the added water on the carrier. Furthermore, it is preferable to prepare a mixture composed of components other than the main ingredient while mixing each component in the order of a) to d) below.

a) A predetermined amount of the carrier and a predetermined amount of the alkaline agent are mixed.
b) Add water is mixed with the mixture of a) above.
c) Hydrous activated carbon is mixed with the mixture of b) above.
d) The reaction catalyst is mixed with the mixture of the above c).

However, in each of the above mixing steps, the components are mixed until they are sufficiently compatible with each other. For example, when potassium carbonate is used as the alkaline agent, the carrier and the alkaline agent are sufficiently mixed in the mixing step of a), and then the added water is added and mixed in the mixing step of b) to add water. Potassium carbonate dissolves and is supported on the carrier. In that state, the carrier carrying the water in which the alkaline agent is dissolved and the hydrous activated carbon are mixed by the mixing step of c), and the reaction catalyst is mixed by d). Since the main agent is not added in a) to d), each of the mixing steps of a) to d) can be performed in the atmosphere, and the respective constituent components can be sufficiently mixed.

(3) Step of adding the main agent in a solid state to the mixture composed of the constituent components other than the main agent For example, the main agent is added to the mixture composed of all the constituent components other than the main agent obtained through the mixing steps of a) to d) above. By adding in the state of, the atmosphere adjusting agent according to the present invention can be obtained. In this way, water is supported on the carrier or impregnated with hydrous activated carbon as impregnated water before the step of adding the main agent to the mixture composed of the constituent components other than the main agent. It is possible to prevent direct contact between the main agent and water. Therefore, the progress of the oxidation reaction of the main agent can be suppressed in the step as well, so that the step can be performed in the atmosphere. Further, by using a hydrous activated carbon obtained by impregnating the activated carbon with water in advance, a granulation effect can be obtained, and even if the activated carbon is a fine powder, the constituent components other than the main agent can be favorably contained while suppressing powdering and the like. The mixed mixture can be obtained as a granulated product. Then, even when the main agent is added to this mixture in a solid state, the mixture and the main agent can be mixed well. Further, as described above, by adjusting the blending amount of the main agent to satisfy the formula (1), a highly reactive atmosphere adjusting agent can be obtained.

(4) Filling Step The step of adding the main agent in a solid state to the mixture composed of the constituent components other than the main agent can be performed in the step of filling and packaging the atmosphere adjusting agent in the breathable packaging material. For example, by filling the breathable packaging material with a predetermined amount of the mixture and a predetermined amount of the main agent, the above step can be performed while filling the breathable packaging material with a predetermined amount of the atmosphere adjusting agent. .. In this way, when the breathable packaging material is filled and packaged, the mixture and the main agent are mixed due to an impact generated when the mixture is put into the breathable packaging material. Further, the breathable packaging material may be filled in advance with a mixture of a mixture composed of components other than the main agent and the main agent.

Here, the breathable packaging material may be any sheet-like or film-like packaging material having oxygen permeability, and has appropriate breathability such as a perforated resin film, paper, or non-woven fabric. Any of those having the above can be used. In particular, a packaging material having heat sealability in addition to breathability is preferable. For example, with a laminate in which a perforated (polyester / polyethylene) film, paper, and a perforated polyethylene film are laminated in this order, or with paper or a non-woven fabric. , A laminate obtained by laminating a perforated polyethylene film or the like is preferable. In addition, polyethylene non-woven fabric and the like can also be used. By filling the breathable packaging material with the above-mentioned atmosphere adjusting agent in a predetermined amount and closing the opening, an atmosphere adjusting agent package as a product can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

22.2 parts by mass (3.0 g) of water (added water) and seven waters of ferrous sulfate with respect to 100 parts by mass (13.5 g) of sodium elisorbate (main agent) having an average volume particle size of 266.6 μm. 37.0 parts by mass (5.0 g) of Japanese product (reaction catalyst), 96.3 parts by mass (13.0 g) of hydrous activated charcoal (water content 60% by mass), 44.4 parts by mass of potassium carbonate (alkaline agent) Using 74.1 parts by mass (10.0 g) of (6.0 g) and zeolite (support), the atmosphere conditioner according to the present invention was produced as follows. The numerical values shown in parentheses indicate the values actually weighed for each component. Further, as the hydrous activated carbon, a hydrous activated carbon (SA1000W60) manufactured by Futamura Chemical Co., Ltd., which was previously impregnated with water so that the water content was 60% by mass with respect to the activated carbon component, was used. Further, when the total amount of the main agent is 100 parts by mass, the hydrous activated carbon contains 38.5 parts by mass (5.2 g) of activated carbon component and 57.8 parts by mass (7.8 g) of impregnated water (see Table 1). ). At this time, the value of the above formula (1) is 7.80 with respect to the blending amount of the main agent (see Table 2). Further, the hydrous activated carbon used in Example 1 is designated as activated carbon "A" (see Table 3). The average volume grain size of the activated carbon is about 10 μm, and other physical properties such as the micropore volume of the t-plot method, the mode pore diameter by the mercury intrusion method, and the like are shown in Table 3.

In the air, the total amount of zeolite and the total amount of potassium carbonate were mixed, and after these were sufficiently mixed, the total amount of water (added water) was added. Then, the whole amount of hydrous activated carbon was added and mixed, ferrous sulfate heptahydrate was added, and the mixture was further mixed. In this way, a mixture in which all the components other than the main ingredient were sufficiently mixed was obtained. Then, the total amount of the main agent is added to the total amount of the mixture composed of all the components other than the main agent to obtain an atmosphere adjusting agent containing the mixture composed of the components other than the main agent and the main agent in a solid state, which has an outer dimension of 80 mm × 260 mm. A breathable packaging material bag was filled with 24 g each to prepare an atmosphere-adjusting agent package of this example. As the breathable packaging material, a three-layer laminated structure of paper / perforated polyethylene / warif with a Wangken-type air permeability (air permeability resistance) of 45 to 60 seconds was used. More specifically, the breathable packaging material bag is provided with heat-sealing portions having a sealing width of 5 mm on each of the three sides and the center position in the longitudinal direction, whereby two filling portions having an outer dimension of 80 mm × 130 mm are formed. Each of these two filling portions is filled with 12 g of an atmosphere adjusting agent to form one package of the atmosphere adjusting agent.

In Example 2, the same activated carbon component as in Example 1, but in a dry state activated carbon containing no impregnated water (activated carbon (SA1000) manufactured by Futamura Chemical Co., Ltd.) (activated carbon "B") (see Tables 1 and 3). Was used. Then, 38.6 parts by mass (9.3 g) of the activated carbon is prepared with respect to 100 parts by mass (24.1 g) of the main agent, and 79.7 parts by mass (added water) of water (added water) is prepared with respect to 100 parts by mass of the main agent. 19.2g) Prepared. Regarding other components, 73.9 parts by mass (17.8 g) of zeolite and 44.4 parts by mass (10.7 g) of potassium carbonate were added so that the blending amount was substantially the same as in Example 1 with respect to 100 parts by mass of the main agent. ), Ferrous sulfate heptahydrate was weighed in 36.9 parts by mass (8.9 g). Then, by adding the total amount of water to the total amount of activated carbon, a mixture of activated carbon and water was prepared, and after mixing the total amount of zeolite and the total amount of potassium carbonate, the mixture of activated carbon and water was added. The atmosphere conditioner package of Example 2 was produced in the same manner as in Example 1, and the atmosphere conditioner package of this example was obtained using this. In the mixture of activated carbon and water, a part of water was impregnated with activated carbon, but the whole amount could not be impregnated with activated carbon. Further, in Example 2, the value of the above formula (1) is 7.81 with respect to the blending amount of the main agent (see Table 2).

In Example 3, a hydrous activated carbon (activated carbon "C") having the same activated carbon component as in Example 1 but having a moisture content of 50% by mass (hydrous activated carbon (SA1000W50) manufactured by Futamura Chemical Co., Ltd.) was used (Tables 1 and Table). 3). Then, 76.8 parts by mass (18.5 g) of the hydrous activated carbon was used with respect to 100 parts by mass (24.1 g) of the main agent, and 41.5 parts by mass (10) parts of water (added water) was added to 100 parts by mass of the main agent. .0 g) The atmosphere conditioner package of Example 3 was produced in the same manner as in Example 2 except that it was used, and the atmosphere conditioner package of this example was obtained using this. When the total amount of the main agent is 100 parts by mass, the hydrous activated carbon contains 38.4 parts by mass of the activated carbon component and 38.4 parts by mass of impregnated water. Regarding other components, 73.9 parts by mass (17.8 g) of zeolite and 44.4 parts by mass (10.) of potassium carbonate were added so that the blending amount was the same as in Example 2 with respect to 100 parts by mass of the main agent. 7 g), ferrous sulfate heptahydrate was weighed in 36.9 parts by mass (8.9 g). In Example 3, the value of the above formula (1) is 7.80 with respect to the blending amount of the main agent (see Table 2).

In Example 4, hydrous activated carbon (moisture content 60% by mass) was used in the same manner as in Example 1 except that 81.5 parts by mass (11.0 g) was used with respect to 100 parts by mass (13.5 g) of the main agent. The atmosphere conditioner package of Example 4 was produced, and the atmosphere conditioner package of this example was obtained using the same. When the total amount of the main agent is 100 parts by mass, Example 4 contains 32.6 parts by mass of the activated carbon component and 48.9 parts by mass of impregnated water. Further, the other components were weighed so as to have the same blending amount as in Example 1 with respect to 100 parts by mass of the main agent. In Example 4, the value of the above formula (1) is 8.82 with respect to the blending amount of the main agent (see Table 2).

In Example 5, a hydrous activated carbon (moisture content of 60% by mass) was used in the same manner as in Example 1 except that 59.3 parts by mass (8.0 g) was used with respect to 100 parts by mass (13.5 g) of the main agent. The atmosphere conditioner package of Example 5 was produced, and the atmosphere conditioner package of this example was obtained using the same. When the total amount of the main agent is 100 parts by mass, Example 5 contains 23.7 parts by mass of the activated carbon component and 35.6 parts by mass of impregnated water. Further, the other components were weighed so as to have the same blending amount as in Example 1 with respect to 100 parts by mass of the main agent. In Example 5, the value of the above formula (1) is 10.80 with respect to the blending amount of the main agent (see Table 2).

In Example 6, a hydrous activated carbon (moisture content of 60% by mass) was used in the same manner as in Example 1 except that 37.0 parts by mass (5.0 g) was used with respect to 100 parts by mass (13.5 g) of the main agent. The atmosphere conditioner package of Example 6 was produced, and the atmosphere conditioner package of this example was obtained using the same. When the total amount of the main agent is 100 parts by mass, Example 6 contains 14.8 parts by mass of the activated carbon component and 22.2 parts by mass of impregnated water. Further, the other components were weighed so as to have the same blending amount as in Example 1 with respect to 100 parts by mass of the main agent. In Example 6, the value of the above formula (1) is 14.01 with respect to the blending amount of the main agent (see Table 2).

In Example 1, 13.5 g of the main agent, 3.0 g of added water, and 5.0 g of ferrous sulfate heptahydrate were used, whereas in Example 7, 11.0 g of the main agent was used (about 11.0 g of Example 1). 81%), 2.0 g of added water and 6.0 g of ferrous sulfate heptahydrate were used, but the atmosphere conditioner of Example 7 was produced in the same manner as in Example 1 and used. The air conditioner package of this example was obtained. Although the amount of the main agent in Example 7 is different from that in Example 1, since the amount of the added water and the amounts of the components other than ferrous sulfate heptahydrate used are the same, other than the added water with respect to 100 parts by mass of the main agent. The blending amount of each component of is larger than that of Example 1 (see Table 1). The same applies to Examples 8 and 9. Further, in Example 7, the value of the above formula (1) is 7.02 with respect to the blending amount of the main agent (see Table 2).

In Example 8, an atmosphere adjusting agent of Example 8 was produced in the same manner as in Example 7 except that 7.0 g of the main agent was used (about 52% of Example 1), and this Example was used. Atmosphere modifier packaging was obtained. In Example 8, the value of the above formula (1) is 4.44 with respect to the blending amount of the main agent (see Table 2).

In Example 9, the atmosphere conditioner of Example 9 was produced in the same manner as in Example 7 except that 5.0 g of the main agent was used (about 37% of Example 1), and this Example was used. Atmosphere modifier packaging was obtained. In Example 9, the value of the above formula (1) is 3.24 with respect to the blending amount of the main agent (see Table 2).

In Example 1, sodium erythorbate having an average volume particle size of 266.6 μm was used as a main component, whereas in Example 10, sodium erythorbate having an average volume particle size of 532.5 μm was used. Further, the amount of the main agent was 10.0 g (about 74% of Example 1), 100.0 parts by mass (10.0 g) of zeolite and 60.0 parts by mass (6. 0 g), hydrous activated charcoal (moisture content 60% by mass) was weighed in 130.0 parts by mass (13.0 g), and ferrous sulfate heptahydrate was weighed in 60.0 parts by mass (6.0 g). Except for these points, the atmosphere conditioner package of Example 10 was produced in the same manner as in Example 1, and the atmosphere conditioner package of this example was obtained using this. In Example 10, the value of the above formula (1) is 5.79 with respect to the blending amount of the main agent (see Table 2).

In Example 11, the atmosphere conditioner of Example 11 was produced in the same manner as in Example 10 except that sodium erythorbate having an average volume particle size of 45.0 μm was used as the main agent, and this embodiment was used. An example atmosphere conditioner package was obtained. In Example 11, the value of the above formula (1) is 5.79 with respect to the blending amount of the main agent (see Table 2).

Comparative example

[Comparative Example 1]
In Comparative Example 1, an activated carbon having the same activated carbon component as in Example 1 but not containing impregnated water (activated carbon (SA1000) manufactured by Futamura Chemical Co., Ltd.) (activated carbon "B") was used. The activated carbon is the same as the activated carbon used in Example 2. Then, 38.6 parts by mass (9.3 g) of the activated carbon is prepared with respect to 100 parts by mass (24.1 g) of the main agent, and 79.7 parts by mass (added water) of water (added water) is prepared with respect to 100 parts by mass of the main agent. 19.2g) Prepared. Regarding other components, 44.4 parts by mass (10.7 g) of potassium carbonate and 36. 9 parts by mass (8.9 g) and zeolite (support) were weighed 73.9 parts by mass (17.8 g).

In the air, the total amount of the main agent and the total amount of water were mixed to obtain a mixed solution in which the main agent was dissolved in water to the dissolution limit. After adding and mixing the total amount of potassium carbonate and the total amount of ferrous sulfate heptahydrate to this mixed solution, the total amount of zeolite and the total amount of activated carbon were added and mixed to obtain a mixture of all raw materials. The resulting mixture became stone-like, difficult to fill in a breathable packaging bag, and could not be used as an atmosphere conditioner. Therefore, in Comparative Example 1, the value of the above formula (1) was not obtained with respect to the blending amount of the main agent (see Table 2).

[Comparative Example 2]
In Comparative Example 2, an activated carbon "D" of a type different from that of Example 1 was used. Specifically, the activated carbon contains impregnated water having an average pore diameter of 1.70 nm, a BET specific surface area of 1021 m ² / g, a particle size of 30 mesh to 150 mesh, and a total pore volume of 0.43 cm ^{3 / g.} Activated carbon in a non-dry state (activated carbon manufactured by Ajinomoto Fine-Techno Co., Ltd. (Y-30 / 150) was used, and 96.3 parts by volume of the activated carbon was used with respect to 100 parts by mass of the main agent. The atmosphere adjusting agent of Comparative Example 2 was produced in the same manner as in Example 1, and the atmosphere adjusting agent package of this example was obtained using the same. In Comparative Example 2, the blending amount of the main agent was expressed in the above formula (1). The value is 27.97 (see Table 2).

[Comparative Example 3]
In Comparative Example 3, an activated carbon "E" of a type different from that of Example 1 and Comparative Example 2 was used. Specifically, the activated carbon does not contain impregnated water having an average pore diameter of 3.67 nm, a BET specific surface area of 710 m ² / g, an average volume particle size of about 100 μm, and a total pore volume of 0.65 cm ^{3 / g.} Activated carbon in a dry state (activated carbon (AZO) manufactured by Norit Co., Ltd.) was used. Then, an atmosphere adjusting agent of Comparative Example 3 was produced in the same manner as in Example 1 except that 96.3 parts by mass of the activated carbon was used with respect to 100 parts by mass of the main agent, and this was used in the present Example. An atmosphere conditioner package was obtained. In Comparative Example 3, the value of the above formula (1) is 27.97 with respect to the blending amount of the main agent (see Table 2).

Table 1 shows the production conditions such as the blending amount of each component in the above-produced Examples and Comparative Examples. In Table 1, the blending amount (ratio) of each component is shown in "parts by mass" when the blending amount of the main agent used in producing each atmosphere adjusting agent is 100 parts by mass. Further, Table 2 shows the total amount (g) of the atmosphere adjusting agent to be filled in one package of the atmosphere adjusting agent, the amount of the main agent, the amount of components other than the main agent, the total amount of water, and the value of the above formula (1).

Further, in Table 3, for the activated carbon used in each Example and Comparative Example, the type, form, water content, total pore volume, average pore diameter, BET specific surface area, t-prot method micropore volume, mercury intrusion method Pore volume (0.04 to 9.0 μm), mercury intrusion mode Pore diameter (0.04 to 9.0 μm), mercury intrusion pore volume (0.006 to 9.0 μm), mercury intrusion mode The pore diameter (0.006 to 9.0 μm) is shown. The total pore volume and the like of the activated carbon shown in Table 3 were measured as follows.

(1) Total pore volume, average pore diameter, BET specific surface area, t-prot method These are measured by the measurement conditions shown in (i) below and analyzed by the analysis method shown in (ii) below. The measured value was obtained.

(I) Measurement conditions Measuring device: BELSORP-miniII manufactured by Microtrack Bell Co., Ltd.
Pretreatment: Vacuum deaeration at 130 ° C for 8 hours Measurement method: Measurement of adsorption / desorption isotherm with nitrogen using the constant volume method Adsorption temperature: 77K
Adsorbent: Nitrogen Saturated vapor pressure: Measured Equilibrium waiting time: 500 Sec
Adsorbent cross-sectional area: 0.162 nm ²

(Ii) Analysis method-Total pore volume The total pore volume was calculated by the following formula from the adsorption amount of the relative pressure (P / P0) of the adsorption isotherm of 0.99.
_{V P = V / 22414 × M} g / ρ g
V _P: the total pore volume of up to relative pressure (0.99), V: adsorption amount M _g of the relative pressure (0.99): The molecular weight of the adsorbate _{(N 2) (28.013),} ρ g: adsorption Quality (N ₂ ) density (0.808)
22414: Volume of gas per mole

-Average pore diameter The value calculated based on the following formula from the total pore volume value and the surface area value calculated by the BET method was taken as the average pore diameter.
D = 4V / A x 1000
D: Pore diameter (nm), V: Total pore volume, A: Specific surface area

-BET specific surface area The value was measured using the above measuring device based on the BET method.

-T-Plot method analysis method Based on the t-Plot method, Harkins-Jura-BEL. The micropore volume was calculated using the t-reference curve.

(2) Mercury press-fitting method Pore volume and mode Pore diameter For these, the measurement device shown below is used, and the measurement results obtained under the measurement conditions shown below are analyzed using the software attached to the measurement device below. The value was set.
Measuring device: Mercury press-fit porosimeter manufactured by AntonioPaar PoreMaster33GT
Measurement conditions: High pressure range 20 to 5000 psi (pore diameter 0.04 μm to 9.0 μm)
High pressure range 20-33000 psi (pore diameter 0.006 μm to 9.0 μm)

<Evaluation>
The oxygen absorption capacity and the amount of carbon dioxide generated by the atmosphere conditioner according to the present invention were evaluated using the atmosphere conditioner packages produced in each Example and each Comparative Example. The evaluation methods and evaluation results are as follows.

1. 1. Evaluation method The oxygen absorption capacity and carbon dioxide gas generation amount of each atmosphere conditioner were evaluated as follows.
This atmosphere adjusting agent package was placed in a gas barrier bag (260 × 350 mm) of polyvinylidene chloride coat / polyethylene laminate film, and 2500 ml of air was filled to prepare a plurality of sealed bags.

In order to evaluate the oxygen absorption rate and carbon dioxide gas generation rate of the obtained atmosphere adjuster package at room temperature, each sealed bag is held at 25 ° C., and the oxygen concentration (% by volume) in each bag is maintained every 10 minutes. And the carbon dioxide concentration (% by volume) was measured using Check Mate 3 manufactured by PBI Dansensol. The results are shown in Tables 5 and 6.

2. Evaluation Results (1) Manufacturability In Examples 1 to 11, after obtaining a mixture consisting of components other than the main agent in the air, the mixture and the main agent in a solid state are filled in a container and packaging material bag in the air. By doing so, an atmosphere conditioner was manufactured. On the other hand, in Comparative Example 1, an atmosphere adjusting agent was produced by mixing the main agent and water in the atmosphere and then sequentially mixing each component. In Example 2 and Comparative Example 1, the atmosphere conditioner is produced under the same conditions except that the mixing order of each component is different.

In Comparative Example 1, as described above, the mixture composed of all the constituents including the main agent became stone-like, and it was difficult to fill the breathable packaging material bag, so that it could not be used as an atmosphere adjusting agent. In Comparative Example 1, water and the main agent are first mixed, and an alkaline agent is added to a saturated aqueous solution in which the main agent is dissolved (however, the main agent exceeds the dissolution limit), so that the main agent is erythorbine. It is probable that the conditions required for the oxidation reaction of sodium acid acid were met, the oxidation reaction of the main agent proceeded, and the mixture consisting of all the components including the main agent became stone-like. On the other hand, unlike each of the above examples, the step of dissolving the main agent in water was not included, and after obtaining a mixture other than the main agent, the main agent in a solid state was added to the mixture to produce the mixture in the atmosphere. It was confirmed that it was possible to suppress the progress of the oxidation reaction of the main agent and that the atmosphere conditioner could be satisfactorily produced.

(2) Types of activated carbon Next, the types of activated carbon will be considered in comparison with Example 1, Comparative Example 2 and Comparative Example 3. In Example 1, 96.3 parts by mass of powdered hydrous activated carbon (“A” (see Table 3)) having a water content of 60% by mass is used with respect to 100 parts by mass of the main agent. On the other hand, in Comparative Example 2 and Comparative Example 3, 96.3 parts by mass of granular activated carbon (“D”) or powdered activated carbon (“E”) having a water content of 0% by mass in a dry state was used. There is. The blending amount of activated carbon with respect to 100 parts by mass of the main agent is the same, but as shown in Table 1, the blending amount of the activated carbon component and the total water content in the atmosphere adjusting agent containing the impregnated water are different. In Example 1, the amount of activated carbon component with respect to 100 parts by mass of the main agent was 38.5 parts by mass, whereas in Comparative Example 2 and Comparative Example 3, the amount of activated carbon component with respect to 100 parts by mass of the main agent was 96.3 parts by mass. is there. Further, in Example 1, the total water content (including added water and impregnated water) in the atmosphere adjusting agent is 80.0 parts by mass, whereas in Comparative Example 2 and Comparative Example 3, 22.2 parts by mass. Is. As a result, the value of the above formula (1) is 7.80 in Example 1, whereas it is 27.97 in Comparative Example 2 and Comparative Example 3. In the atmosphere adjusting agents of Comparative Example 2 and Comparative Example 3, the amount of the main agent mixed with respect to the total water content was large, and as shown in Tables 4 to 6, the atmosphere adjusting ability was significantly different from that of the atmosphere adjusting agent of Example 1. occured. Specifically, in the atmosphere adjusting agent of Example 1, it took 70 minutes for the oxygen concentration in the sealed bag to become 0.1% or less, whereas the atmosphere adjusting agent of Comparative Example 2 took 70 minutes. It took 48 hours, and the atmosphere conditioner of Comparative Example 3 took 216 hours. Further, as shown in Tables 5 and 6, the oxygen concentration in the atmosphere can be reduced to 1% or less before the elapse of 40 minutes, and the carbon dioxide concentration in the atmosphere can be increased to nearly 20%. It was confirmed that the atmosphere can be quickly adjusted to be suitable for anaerobic culture. On the other hand, the atmosphere modifiers of Comparative Example 2 and Comparative Example 3 did not show such high reactivity. Therefore, when the same amount of activated carbon is used for the main agent, by using the hydrous activated carbon impregnated with water in advance, an amount of water suitable for rapidly advancing the oxidation reaction of the main agent can be added without increasing the amount of added water. It was confirmed that the atmosphere adjusting agent can be easily contained and a highly reactive atmosphere adjusting agent can be obtained.

(3) Moisture content of activated carbon and ratio of impregnated water in total water content Next, by comparing Example 1, Example 2 and Example 3, the water content of activated carbon and the ratio of impregnated water in total water content are considered. To do. Examples 2 and 3 each have the same activated carbon component as that of Example 1, and use activated carbon having a different water content. In the atmosphere adjusting agents of Examples 1, 2 and 3, the amount of the activated carbon component and the total amount of water to be blended with respect to 100 parts by mass of the main agent are the same, and the blending amounts of the other components are also the same. In Example 1, since the hydrous activated carbon having a water content of 60% by mass is used, the ratio of the impregnated water to the total water content is 72.2% by mass. On the other hand, in Example 2, since activated carbon having a water content of 0% by mass is used, Table 1 shows that the ratio of impregnated water to the total water content is 0% by mass. However, the activated carbon used in Example 2 has the same activated carbon component as in Example 1, and has the same values in the t-plot method micropore volume and the mode pore diameter (measurement range 0.04 to 9.0 μm). .. Therefore, by mixing the total amount of the added water with the activated carbon in advance, water is absorbed well into the pores of the activated carbon, and the ratio of the impregnated water in the total water content and the water content in the activated carbon are inferior to those in Example 1. It is presumed that the water content was about 55% and the proportion of impregnated water was about 60% by mass, which was higher than that of Example 3. In Example 3, a hydrous activated carbon having a water content of 50% by mass is used, and 41.5 parts by mass of added water is used with respect to 100 parts by mass of the main agent. Therefore, the ratio of the impregnated water to the total water content is 48.1% by mass. %. Due to such a difference in the ratio of the impregnated water to the total water content, the atmosphere adjusting ability differs as shown in Tables 4 to 6, and the atmosphere adjusting agent of Example 1 shows a high atmosphere adjusting ability. Therefore, it was confirmed that the atmosphere adjusting ability was slightly lowered in Examples 2 and 3 in which the ratio of the impregnated water to the total water content was low. However, in the atmosphere adjusting agent of Example 2, the time required to reduce the oxygen concentration in the atmosphere to 0.1% or less is 5 hours, and the activated carbon is impregnated with a predetermined amount of water in advance. It was confirmed that a relatively high atmosphere adjustment ability can be obtained. Further, also for the atmosphere adjusting agent of Example 3, the time required to reduce the oxygen concentration in the atmosphere to 0.1% or less is 13 hours, which is compared with the atmosphere adjusting agents of Comparative Example 2 and Comparative Example 3. It is also confirmed that high atmosphere adjustment ability can be realized.

(4) Blending amount of hydrous activated charcoal and ratio of impregnated water in total water content Next, comparing Examples 1 and 4 to 6, the blending amount of hydrous activated charcoal and the total water content with respect to 100 parts by mass of the main agent Consider the proportion of impregnated water. In these examples, the blending amount of the hydrous activated carbon with respect to 100 parts by mass of the main agent is different, and as a result, the total water content and the impregnated water amount in the atmosphere adjusting agent and the ratio of the impregnated water in the total water content are different. The blending amount of the components of is the same. The amount of the hydrous activated carbon compounded in Example 1 was 96.3 parts by mass, whereas in Example 4 it was 81.5 parts by mass, in Example 5 it was 59.3 parts by mass, and in Example 6 it was 37.0 parts by mass. It is a part (see Table 1). As shown in Tables 4 to 6, the time required for the atmosphere adjusting agent of Example 4 to reduce the oxygen concentration in the atmosphere to 0.1% or less is 90 minutes, which is longer than that of Example 1. However, it was confirmed that it had high reactivity. In Examples 1 and 4 to 6, the time required to reduce the oxygen concentration in the atmosphere to 0.1% or less increased as the blending amount of the impregnated activated carbon with respect to 100 parts by mass of the main agent decreased. However, in Examples 4 to 6, the oxygen concentration in the atmosphere can be reduced to 0.1% or less within 7 hours, and it is recognized that the atmosphere can be adjusted in a practically good manner. Further, referring to Tables 5 and 6, by adjusting the blending amount of the hydrous activated carbon so that the ratio of the impregnated water in the total water content is 60% by mass or more, the reactivity is higher and the oxygen concentration in the atmosphere. And it is recognized that an atmosphere adjusting agent capable of rapidly adjusting the carbon dioxide concentration to the atmosphere for anaerobic culture can be obtained.

(5) Main agent compounding amount Next, the compounding amount of the main agent or the compounding amount of other components with respect to the main agent will be considered by comparing Examples 1 and 7 to 9. Examples 1 and 7 to 9 use different amounts of the main agent, which are 13.5 g, 11.0 g, 7.0 g, and 5.0 g, respectively, but the amounts of other components used are omitted. It is the same. Therefore, the blending amount of the other components with respect to 100 parts by mass of the main agent is relatively large in Examples 7 to 9 as compared with Example 1 except for the amount of added water in Example 7. With reference to Table 4, when the amounts of other components used are the same in Example 1 and Examples 7 to 9, the oxygen concentration in the atmosphere is reduced to 0.1% or less as the amount of the main agent compounded decreases. The time required to do this has increased. However, in Examples 7 and 8, the oxygen concentration in the atmosphere can be reduced to 0.1% or less within 3 hours, and it is recognized that the atmosphere can be adjusted in a practically good manner. On the other hand, in Example 9 in which the amount of the main agent blended was about 37% with respect to Example 1, it took 20 hours to reduce the oxygen concentration in the atmosphere to 0.1% or less. However, at least the amount of the main agent is at least as compared with Comparative Example 2 and Comparative Example 3, and an atmosphere adjusting agent having a high reactivity is obtained, and by using the hydrous activated carbon, an atmosphere adjusting agent having a high atmosphere adjusting ability can be obtained. It is also confirmed that it can be done.

(6) Main agent particle size Next, the main agent particle size will be considered by comparing Example 1, Example 10, and Example 11. In Example 1, sodium erythorbate having an average volume particle size of 266.6 μm was used as the main component, whereas in Example 10, the average volume particle size was 532.5 μm, and in Example 11, the average volume particle size was 45.0 μm. The main ingredient was sodium erythorbate. Further, although the blending amount of the other components is different from that of Example 1, when the other conditions are the same as those of Example 1, the larger the particle size of the main agent, the slightly lower the reactivity, and the particle size of the main agent becomes larger. It was confirmed that the smaller the value, the better the reactivity. In the above example, hydrous activated carbon having an average volume particle size of about 10 μm is used. By using a fine powdered hydrous activated carbon having a particle size of about 1/4 to 1/55 with respect to the main agent, a large number of hydrous activated carbons are present around the main agent particles in the atmosphere adjusting agent, and water required for the oxidation reaction of the main agent. Can be satisfactorily supplied from hydrous activated carbon. It is considered that if the particle size of the main agent becomes smaller, the contact area with the hydrous activated carbon increases, and a more reactive atmosphere adjusting agent can be obtained.

(7) Equation (1)
Next, the value of equation (1) will be considered. The atmosphere regulator of Example 1 and the atmosphere regulators of Comparative Example 2 and Comparative Example 3 are as described above. Comparing Examples 1 to 11, the type of activated charcoal, the water content of the activated charcoal and the ratio of impregnated water in the total water content, the blended amount of the hydrous activated charcoal and the impregnated water ratio in the total water content, the main agent blending amount, and the main agent granules Although the reactivity of the atmosphere adjusting agent changes depending on the diameter, it is considered that a highly reactive atmosphere adjusting agent can be obtained although there is a difference in each case. Further, comparing each example, in order to adjust the anaerobic culture atmosphere more quickly, the value of the formula (1) is preferably 5 or more and 10 or less, and at that time, the ratio of the impregnated water to the total water content. Was confirmed to be preferably 65% by mass or more and 95% by mass or less. However, as a result of separate confirmation by the present inventors, when adjusting the atmosphere for microaerobic culture, even if the value of the formula (1) is about 1.5, it takes about 1 hour for microaerobic culture. The oxygen concentration and carbon dioxide concentration can be adjusted to suit the atmosphere, and the value of the formula (1) can be appropriately determined according to the required reaction rate and the oxygen concentration and carbon dioxide concentration to be adjusted. It can be said that it is preferable.

(8) Physical characteristics of activated carbon Table 3 shows the physical characteristics of the activated carbon used in each Example and Comparative Example. Activated carbon A~ charcoal E is the total pore volume is 0.43cm ³ /g~1.56cm ³ / g, an average pore diameter in the range of 1.7Nm～4.2Nm. As described above, in the examples using activated carbon A to activated carbon C, an atmosphere modifier having higher reactivity than in Comparative Examples 2 and 3 using activated carbon D and activated carbon E was obtained. As described in the column of the embodiment, in the atmosphere adjusting agent according to the present invention, the correlation between the value of the total pore volume and the high reactivity (oxygen absorption rate, carbon dioxide release rate, etc.) is No particular recognition was made. However, a correlation was observed between the micropore volume by the t-prot method and the high reactivity, and it is better to use activated carbon A, activated carbon B and activated carbon C, which have larger micropore volumes than activated carbon D and activated carbon E. The oxidation reaction of the above can proceed efficiently, and a highly reactive atmosphere conditioner was obtained. In addition, the mode pore diameter (measurement range 0.04 to 9.0 μm) by the mercury intrusion method showed a value of 0.050 μm or more for activated carbon A, activated carbon B, and activated carbon C, whereas it was 0. It showed a small value of 03644 μm. On the other hand, the mode pore diameter (measurement range 0.006 to 9.0 μm) by the mercury intrusion method is 0.00549 μm for activated carbon A, activated carbon B and activated carbon C, whereas activated carbon D is 0.01201 μm, which is twice as large. Despite the larger value, the reactivity was inferior to that of the activated carbons A to C, and the activated carbon E was the same value as 0.00549 μm, but the reactivity was the worst. Therefore, as described above, a correlation was observed between the size of the mode pore diameter (measurement range 0.04 to 9.0 μm) and the high reactivity, and the mode pore diameter (measurement range 0.04 to 9.0 μm) was observed. It is considered that a highly reactive atmosphere conditioner can be obtained by using a large activated carbon (9.0 μm).

According to the present invention, there is provided an atmosphere adjusting agent and a method for producing an atmosphere adjusting agent, which are highly reactive and can suppress a decrease in atmosphere adjusting ability in a manufacturing process without using expensive manufacturing equipment or the like. Can be done.

Claims (12)

An atmosphere conditioner containing a main agent, an alkaline agent, water, a carrier, and activated carbon.
The main agent is one or more selected from L-ascorbic acid, erythorbic acid, and salts or hydrates thereof.
When the solubility of the main agent in water is a (g / 100 g-H ₂ O) (25 ° C.), the amount of the main agent contained in the atmosphere adjusting agent is x (g), and the total water content is b (g), the following Satisfy the relational expression (1) of
An atmosphere conditioner comprising the mixture of the alkaline agent, the water, the carrier, and components other than the main agent containing the activated carbon, and the main agent in a solid state.
1.3 <x / ((a / 100) x b) ≤ 25.0 ... (1) The atmosphere adjustment according to claim 1, wherein the activated carbon is a hydrous activated carbon having an average volume particle size of less than 0.1 mm containing 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent as impregnated water. Agent. The atmosphere adjusting agent according to claim 2, wherein the amount of impregnated water of the hydrous activated carbon is 45 parts by mass or more with respect to 100 parts by mass of the hydrous activated carbon. The atmosphere adjusting agent according to claim 2 or 3, wherein the activated carbon component obtained by removing the impregnated water from the hydrous activated carbon is contained in an amount of 125 parts by mass or less with respect to 100 parts by mass of the main agent. The atmosphere adjusting agent according to any one of claims 1 to 4, wherein the activated carbon has a micropore volume of 0.3 cm ^{3 / g or more by the t-plot method.} The atmosphere adjusting agent according to any one of claims 1 to 5, wherein the mode pore diameter (measurement range 0.04 to 9.0 μm) of the activated carbon by the mercury injection method is 0.050 μm or more. The atmosphere adjusting agent according to any one of claims 1 to 6, wherein the total amount of water contained in the atmosphere adjusting agent is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the main agent. The atmosphere adjusting agent according to any one of claims 1 to 7, which contains 35 parts by mass or more and 150 parts by mass or less of potassium carbonate as the alkaline agent with respect to 100 parts by mass of the main agent. The atmosphere adjustment according to any one of claims 1 to 8, wherein ferrous sulfate heptahydrate is contained in a range of 30 parts by mass or more and 250 parts by mass or less as a reaction catalyst with respect to 100 parts by mass of the main agent. Agent. A method for producing an atmosphere adjusting agent according to any one of claims 1 to 9, wherein the atmosphere adjusting agent is produced.
When the solubility of the main agent in water is a (g / 100 g-H ₂ O) (25 ° C.), the amount of the main agent contained in the atmosphere adjusting agent is x (g), and the total water content is b (g), the following A method for producing an atmosphere adjusting agent, which comprises determining the blending amounts of the main agent and the water so as to satisfy the relational expression (1) of.
1.3 <x / ((a / 100) x b) ≤ 25.0 ... (1) A step of obtaining a mixture consisting of components other than the main agent containing the alkaline agent, the water, the carrier, and the activated carbon.
The step of adding the main agent to the mixture in a solid state, and
The method for producing an atmosphere adjusting agent according to claim 10 . Claim 10 or claim that the activated carbon is pre-impregnated with 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent, and the activated carbon containing the impregnated water is used to obtain the mixture. Item 10. The method for producing an atmosphere adjusting agent according to Item 11.