JP6884445B1 - Atmospheric conditioner and manufacturing method of atmosphere adjuster - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an atmosphere adjusting agent and an atmosphere which are highly reactive, can suppress a decrease in atmosphere adjusting ability in a manufacturing process without using expensive manufacturing equipment, and can satisfactorily adjust the atmosphere for culturing. Provided is a method for producing a modifier. SOLUTION: In order to solve the above problems, a mixture containing a main agent, an alkaline agent, water, a carrier and activated carbon, the main agent being erythorbic acids, and a mixture composed of components other than the main agent, and a solid material. The main agent in the state is mixed, and the total amount of water contained in the atmosphere adjusting agent is more than 200 parts by mass with respect to 100 parts by mass of the main agent, and the activated carbon has the total amount of water contained in the atmosphere adjusting agent. 40% by mass or more and 95% by mass or less of the above is contained as impregnated water, and the activated carbon component excluding the impregnated water impregnated in the activated carbon is contained in an atmosphere of 100 parts by mass or more with respect to 100 parts by mass of the main agent. Use as a regulator. [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, 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 Patent Documents 1 to 3, a wide contact area between ascorbic acid and oxygen is secured by impregnating granular activated carbon having a large specific surface area with an aqueous solution of ascorbic acid having a high concentration close to the saturation concentration, and in the initial stage of the reaction. It is said that the amount of carbon dioxide generated 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. Further, in order to adjust the microaerophile culture atmosphere, it is necessary to adjust the oxygen concentration in the atmosphere below the atmosphere (for example, 5% by volume to 12% by volume), while adjusting the carbon dioxide gas concentration above the atmosphere. Therefore, it is necessary to control so as not to absorb oxygen in the atmosphere too much while quickly absorbing oxygen in the atmosphere. Further, if the carbon dioxide concentration in the atmosphere becomes too high, the carbon dioxide gas dissolves in the medium and the pH changes. Therefore, it is necessary to adjust the carbon dioxide gas concentration to a predetermined range (for example, 5% by volume to 10% by volume). is there.

Therefore, the subject of the present invention is that it is highly reactive and can suppress a decrease in the atmosphere adjusting ability in the manufacturing process without using expensive manufacturing equipment or the like, and is a suitable atmosphere for adjusting the culture atmosphere. It is an object of the present invention to provide a method for producing an adjusting agent and an atmosphere adjusting agent.

In order to solve the above problems, the atmosphere conditioner according to the present invention is an atmosphere conditioner containing erythorbic acid as a main agent, potassium carbonate, water, a carrier, and activated carbon.
The activated carbon contains a mixture of constituents other than the main agent and the main agent in a solid state, and the total water content of the atmosphere adjusting agent is more than 200 parts by mass with respect to 100 parts by mass of the main agent. , 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent is contained as impregnated water, and the activated carbon component excluding the impregnated water is contained in 100 parts by mass or more with respect to 100 parts by mass of the main agent. It is characterized by that.

In the atmosphere adjusting agent according to the present invention, the solubility of the main agent in water is a (g / 100g-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 determined. When b (g), it is preferable to satisfy the following relational expression (1).
1.0 <x / ((a / 100) x b) <5.0 ... (1)

In the atmosphere adjusting agent according to the present invention, the activated carbon is preferably a hydrous activated carbon having a particle size of less than 0.1 mm, which contains 40% by mass or more of the total water content contained in the atmosphere adjusting agent as the impregnated water.

In the atmosphere adjusting agent according to the present invention, the amount of impregnated water 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, the amount of supported water supported on the carrier is preferably 5 parts by mass or more and less than 200 parts by mass 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 potassium carbonate is contained in an amount of more than 150 parts by mass 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 100 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 the atmosphere adjusting agent according to the present invention, the amount of potassium carbonate is preferably 125 parts by mass or more and less than 160 parts by mass with respect to 100 parts by mass of the ferrous sulfate heptahydrate.

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 erythorbic acid as a main agent, potassium carbonate, water, a carrier, and activated carbon. The step of obtaining a mixture consisting of the potassium carbonate, the water, the carrier, and the constituent components other than the main agent containing the activated carbon without including the step of dissolving the erythorbic acids in the water, and the main agent in the mixture. Water-containing activated carbon in which 40% by mass or more and 95% by mass or less of the total water content contained in the atmosphere adjusting agent is contained as impregnated water in the activated carbon when the mixture is obtained. At that time, 100 parts by mass or more of the activated carbon component excluding the impregnated water was used with respect to 100 parts by mass of the main agent, and the total amount of water contained in the atmosphere adjusting agent was used with respect to 100 parts by mass of the main agent. Is characterized in that the blending amount of the water is determined so that the amount of water is more than 200 parts by weight.

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).
1.0 <x / ((a / 100) x b) <5.0 ... (1)

According to the present invention, it is highly reactive, and it is possible to suppress a decrease in the atmosphere adjusting ability in the manufacturing process without using expensive manufacturing equipment or the like, and it is possible to satisfactorily adjust the atmosphere for culturing. A method for producing an agent and an atmosphere adjusting agent can be provided.

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, potassium carbonate, water, a carrier, and activated carbon, and the main agent is erythorbic acid, a mixture consisting of constituents other than the main agent, and a solid. It is characterized by containing the main agent of the state.

The atmosphere modifier uses the oxidation reaction of erythorbic acids (a type of ascorbic acid), which is the main ingredient, to absorb oxygen in the atmosphere and release carbon dioxide, thereby increasing the oxygen concentration and carbon dioxide concentration in the culture atmosphere. adjust. Here, the oxidation reaction of the main agent 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 in which a mixture composed of components other than the main agent and a main agent in a solid state are mixed is adopted. adopt. Since the conventional atmosphere adjusting agent requires a step of adjusting the aqueous solution of the main agent at the time of manufacturing, if the contact between the aqueous solution of the main agent and oxygen is not suppressed by keeping the manufacturing process in a nitrogen atmosphere, the oxidation reaction of the main agent proceeds and the atmosphere Adjustability may decrease. Further, if a high concentration aqueous solution close to the saturated concentration is not prepared when preparing the aqueous solution of the main agent, the amount of the main agent blended in the atmosphere adjusting agent decreases, and it becomes difficult to obtain a highly reactive atmosphere adjusting agent. ..

On the other hand, a form in which a mixture composed of components other than the main agent and the main agent in a solid state are mixed is adopted. That is, in the atmosphere adjusting agent according to the present invention, by containing the main agent as a solid instead of dissolving the main agent in water, the main agent is contained with respect to the water content even when the solubility of the main agent in water is not so high. The content can be increased. 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 the main agent. Can be done. 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 the main agent (erythorbic 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, potassium carbonate, water, a carrier, and activated carbon. Further, it is preferable that the content of each component is in the range described later with respect to the main agent in order to adjust the atmosphere for microaerobic culture. Hereinafter, each component will be described including the reaction catalyst.

(1) Main agent Ascorbic acids have been conventionally used as the main agent of an atmosphere adjusting agent. Examples of ascorbic acids include L-ascorbic acid, erythorbic acid (D-isoascorbic acid) which is a stereoisomer thereof, and salts or hydrates thereof. 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.

a) Solubility In the atmosphere conditioner according to the present invention, erythorbic acid, which is not too soluble in water as the main agent among the ascorbic acids listed above and exhibits appropriate solubility, is used as the main agent. 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. For example, among the ascorbic acids listed above, the solubility of sodium L-ascorbic acid in water is 62 (g / 100 g-H ₂ O) (25 ° C.), and the solubility in water is high. When an aqueous solution of a main agent in which the main agent is dissolved in water is supported / impregnated on a carrier as in a conventional atmosphere adjusting agent, it is better to use a highly soluble substance such as sodium ascorbate as the main agent. It is considered that a higher concentration aqueous solution of the main agent can be supported on the carrier, which is preferable for 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. Furthermore, 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. Therefore, 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, from these viewpoints, in the present invention, erythorbic acid having an appropriate solubility in water is used as the main agent. However, the appropriate solubility in water means that in the present invention, it is 45 (g / 100 g-H ₂ O) (25 ° C) or less and 1 (g / 100 g-H ₂ O) (25 ° C) or more. .. For example, the solubility of erythorbic acid is 40 (g / 100 g-H ₂ O) (25 ° C), and the solubility of sodium erythorbate is 16 (g / 100 g-H ₂ O) (25 ° C). As described above, the solubility of erythorbic acids in water is appropriate, and it is preferable to use erythorbic acid salt or erythorbic acid as a main agent. Further, even when two or more kinds of erythorbic acids are used as the main agent, it is preferable that the solubility of each 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. Therefore, among the erythorbics, it is more preferable to use erythorbic acid salt, which has a solubility in water within the above range, as the 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.

b) Blending amount In addition, 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). Then, it is preferable to mix the main agent so as to satisfy the following relational expression (1).
1.0 <x / ((a / 100) x b) <5.0 ... (1)

By determining the blending amount (and total water content) 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 the main agent can be efficiently promoted, and the reactivity is reactive. A high atmosphere conditioner can be obtained. Here, in order to obtain an atmosphere modifier having higher reactivity, it is preferable that the value of the above formula (1) is large. Therefore, the lower limit of the above formula (1) is more preferably 1.2, further preferably 1.5, and even more preferably 1.7.

On the other hand, in order to adjust the atmosphere for microaerobic culture, it is necessary to maintain the oxygen concentration in the range of 5% by volume to 12% by volume as described above while rapidly reducing the oxygen concentration in the atmosphere. Therefore, it is necessary to control so as not to absorb too much oxygen in the atmosphere while maintaining high reactivity. Therefore, by setting the upper limit of the above formula (1) to less than 5.0, the oxygen concentration and carbon dioxide concentration in the atmosphere are quickly adjusted to the concentrations suitable for microaerobic culture, and the concentrations are maintained. It will be easier to do. From this point of view, the upper limit value is more preferably 4.0, further preferably 3.5, and even more preferably 3.0.

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. Further, by appropriately adjusting the volume of the atmosphere to be adjusted, the amount of the atmosphere adjusting agent, and the like, it is possible to adjust the atmosphere suitable for microaerobic culture even if the upper limit value is larger than 5.0. When two or more kinds of erythorbic acids are used as the main agent, the limit amount at which the mixture of the main agent in which each erythorbic acid is mixed at a predetermined mixing ratio is soluble in 100 ml of water (25 ° C.) is defined. The predetermined mixing ratio means the mixing ratio of two or more kinds of erythorbic 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) Potassium carbonate As described above, the oxidation reaction of the main agent is carried out under basic conditions. Potassium carbonate is an alkaline agent for adjusting the reaction field to basic conditions, and is an essential component of the atmosphere conditioner according to the present invention. Conventionally, sodium carbonate, calcium carbonate and the like have also been used as this kind of alkaline agent. However, by using potassium carbonate as the alkaline agent, powder characteristics (fluidity, apparent density, etc.) are better and higher oxygen absorption capacity can be obtained as compared with the case where other alkaline agents are used. Further, by appropriately adjusting the amount of potassium carbonate added, the reaction rate of the oxidation reaction of the main agent can be increased, and the amount of carbon dioxide generated can be easily controlled. In particular, if potassium carbonate is added in excess of a predetermined amount, it becomes possible to suppress the amount of carbon dioxide released. Therefore, it is easy to adjust the oxygen concentration and carbon dioxide concentration to be suitable for the culture atmosphere. From this point of view, it is preferable to use potassium carbonate as the alkaline agent.

When the above erythorbic acid salt is used as the main agent, it is preferable to use potassium carbonate as the alkaline agent from the following points. 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 the main agent, and a highly reactive atmosphere adjusting agent can be obtained. 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, the main agent is decomposed by the alkaline agent when these are mixed, or the oxidation reaction of the main agent proceeds excessively, so that the atmosphere is adjusted. The oxygen absorption capacity of the main agent may decrease or its fluidity may decrease before the agent is manufactured. Based on 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, as the alkaline agent, the main agent is decomposed or oxidized during the manufacturing process. It is possible to prevent the reaction from proceeding and to maintain good fluidity of the atmosphere conditioner.

In the atmosphere adjusting agent according to the present invention, potassium carbonate is preferably contained in an amount of more than 150 parts by mass with respect to 100 parts by mass of the main agent. When adjusting the atmosphere for microaerobic culture, the oxygen concentration in the atmosphere should be about 5% by volume to 12% by volume, and the carbon dioxide concentration should be about 5% by volume to 10% by volume, although it depends on the microorganisms to be cultured. Is preferable. In general, alkali metal carbonates such as sodium carbonate have the ability to generate carbon dioxide. In the oxidation reaction of the main agent, the amount of oxygen absorbed (mol) and the amount of carbon dioxide released (mol) are theoretically the same. Therefore, when an alkali metal carbonate is blended in the atmosphere modifier, more carbon dioxide than the amount of oxygen absorbed (mol) can be released into the atmosphere. On the other hand, potassium carbonate has extremely high solubility in water as described above. Therefore, if a larger amount than the amount generally blended as an alkaline agent, such as an amount exceeding 150 parts by mass, is blended with respect to 100 parts by mass of the main agent, carbon dioxide in the atmosphere and excess potassium carbonate and water in the atmosphere adjusting agent are mixed. It reacts and carbon dioxide is absorbed. By such a mechanism, by blending more potassium carbonate than usual, the carbon dioxide concentration in the atmosphere is adjusted so as not to become too high, and the desired oxygen concentration and carbon dioxide concentration suitable for the atmosphere for microaerobic culture are adjusted. It becomes easy to adjust to. Increasing the amount of potassium carbonate blended with respect to 100 parts by mass of the main agent increases the effect of suppressing the amount of carbon dioxide released. From the viewpoint of adjusting the carbon dioxide concentration to an atmosphere for microaerobic culture, it is more preferable that the concentration is 150 parts by mass or more with respect to 100 parts by mass of the main agent. The upper limit is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less with respect to 100 parts by mass of the main agent. By appropriately adjusting the blending amount of potassium carbonate within such a range, it becomes possible to quickly adjust the oxygen concentration and carbon dioxide concentration suitable for the microorganism to be cultured and the like.

The amount of potassium carbonate is preferably 125 parts by mass or more and less than 160 parts by mass with respect to 100 parts by mass of ferrous sulfate heptahydrate as a reaction catalyst, which will be described later. By blending potassium carbonate in the above range with ferrous sulfate hydrate, carbon dioxide released into the atmosphere can be released into the atmosphere while promoting the oxidation reaction of the main agent with ferrous sulfate heptahydrate. It becomes easy to adjust the carbon dioxide concentration to be suitable for the atmosphere for microaerobic culture.

(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. The present invention is characterized in that, when the main agent is 100 parts by mass, the total amount of water contained in the atmosphere adjusting agent is more than 200 parts by mass. The initial oxygen absorption rate is fast, and the oxygen concentration is suitable for the atmosphere for microaerobic culture (in order to obtain a highly reactive atmosphere conditioner, the total water content is 220 parts by mass or more with respect to 100 parts by mass of the main agent. It is more preferably 235 parts by mass or more, and the total water content is preferably 500 parts by mass or less and 450 parts by mass or less with respect to 100 parts by mass of the main agent. More preferably, it is 400 parts by mass or less.

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 200 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. From this point of view, the content of the supported water is more preferably less than 150 parts by mass, more preferably less than 100 parts by mass, and even more preferably less than 80 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 lower limit of the content of the supported water is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass or more with respect to 100 parts by mass of the main agent as described above. Is more preferable.

On the other hand, the impregnated water is preferably 150 parts by mass or more and 300 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 adjusting agent according to the present invention preferably contains a reaction catalyst for accelerating the oxidation reaction of the main agent. 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 100 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 100 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 450 parts by mass or less, and further preferably 400 parts by mass or less. In particular, when adjusting the atmosphere for microaerobic culture, the content of the carrier is preferably in the range of 200 parts by mass to 400 parts by mass, and is in the range of 230 parts by mass to 350 parts by mass. Is even more preferable.

(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. Further, the upper limit of the water content is not particularly specified, and the maximum amount of water that the activated carbon component can hold is the upper limit. Therefore, the upper limit is approximately 95 parts by mass or less with respect to 100 parts by mass of hydrous activated carbon, and may be 90 parts by mass or less or 85 parts by mass or less depending on the activated carbon component.

On the other hand, the atmosphere adjusting agent contains 100 parts by mass or more of the activated carbon component obtained by removing the impregnated water from the hydrous activated carbon with respect to 100 parts by mass of the main agent. As described above, the atmosphere adjusting agent according to the present invention has a total water content of more than 200 parts by mass with respect to 100 parts by mass of the main agent. If all the water is supported on the carrier, it is necessary to increase the blending amount of the carrier in order to prevent excess water that was not supported on the carrier from being present in the atmosphere conditioner in a free state. is there. Here, the free state means a state in which water exists without being supported on a carrier or activated carbon. The present invention is characterized in that the main agent is contained in a solid state. If free water is present in the atmosphere conditioner, the main agent may dissolve in the free water in the manufacturing process. In that case, if the atmosphere adjusting agent is manufactured in the atmosphere, the oxidation reaction of the main agent proceeds, and the atmospheric super performance of the product may be deteriorated. On the other hand, 100 parts by mass or more of the activated carbon component is blended with 100 parts by mass of the main agent, and 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. By setting the activated carbon, the activated carbon is impregnated with the water required for the oxidation reaction of the main agent while preventing the existence of water in a free state in the manufacturing process, thereby obtaining a highly reactive atmosphere conditioner. Can be done.

The blending amount of the activated carbon component can be appropriately adjusted according to the amount of the main agent and the oxygen concentration and carbon dioxide concentration required for the culture atmosphere. When adjusting the atmosphere for microaerobic culture, the upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 180 parts by mass or less.

Further, the amount of impregnated water is more preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 70% by mass or more of the total amount of water contained in the atmosphere adjusting agent. Further, the upper limit value may be 90% by mass or less, or 85% by mass or less.

Further, by impregnating activated carbon having a small particle size with respect to the main agent in advance with water, a state in which a plurality of activated carbons are attached to the surface of the main agent particles, and an aqueous solution in which the main agent is dissolved in water is used as a carrier. Even without impregnation, 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.

Furthermore, in the atmosphere modifier is preferably 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, 0.50 cm ³ / It is more preferably g or more. 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.

In the above, the atmosphere adjusting agent suitable for adjusting the atmosphere for microaerobic culture has been mainly described, but ascorbic acids as the main agent regardless of the culture atmosphere (including erythorbic acids and other various ascorbic acids listed above). In an atmosphere adjusting agent containing potassium carbonate, water, a hydrous activated carbon containing a predetermined amount of impregnated water, and a carrier made of a porous substance other than activated carbon, the total amount of water contained in the atmosphere adjusting agent as activated carbon. Using a hydrous activated carbon containing 40% by mass or more and 95% by mass or less of the above as impregnated water, the micropore volume of the t-prot method is 0.3 cm ³ / g or more as the hydrous activated carbon, and the mode pore diameter (measurement) by the mercury intrusion method. By using an activated carbon component having a range of 0.04 to 9.0 μm) of 0.050 μm or more, the water required for the oxidation reaction of the main agent can be efficiently supplied from the hydrous activated carbon, and the reactivity is high, and the manufacturing process. It is possible to obtain an atmosphere adjusting agent with less deterioration of the atmosphere adjusting ability. In this case, if the main agent is a solid, it is possible to add a large amount of the main agent in comparison with the water content while suppressing deterioration of the atmosphere adjusting ability in the manufacturing process as described above. The amount (mass) of the atmosphere adjusting agent required for adjusting the desired oxygen absorption amount and carbon dioxide release amount can be easily adjusted. The upper limit of the mode pore diameter (measurement range 0.04 to 9.0 μm) by the mercury intrusion method is not particularly specified, but can be, for example, 0.100 μm or less.

(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 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 or less with respect to the total amount of the constituent components. , Water is 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), reaction catalyst is 20% by mass or less, and a carrier is used. It is preferable that it contains 15% by mass or more and 25% by mass or less, and 5% by mass or more and 15% by mass or less of activated charcoal (however, only the activated carbon component). By containing these components in such a content ratio, the reactivity is high, and the atmosphere can be quickly adjusted to the desired oxygen concentration and carbon dioxide concentration.

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.

For 100 parts by mass (3.0 g) of sodium erythorsorbate (main agent) having an average volume particle size of 266.6 μm, 66.7 parts by mass (2.0 g) of water (added water) and seven ferrous sulfate water. 200.0 parts by mass (6.0 g) of Japanese product (reaction catalyst), 433.3 parts by mass (13.0 g) of hydrous activated charcoal (water content 60% by mass), 300.0 parts by mass of potassium carbonate (alkaline agent) Using 333.3 parts by mass (10.0 g) of (9.0 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. The hydrous activated carbon contains water for an activated carbon component having an average pore diameter of 4.22 nm, a BET specific surface area of 1474 m ² / g, an average volume particle diameter of about 10 μm, and a total pore volume of 1.56 cm ^{3 / g.} Hydrous activated carbon (SA1000W60) manufactured by Futamura Chemical Co., Ltd., which was previously impregnated with water so that the ratio was 60% by mass, was used. Further, when the total amount of the main agent is 100 parts by mass, the hydrous activated carbon contains 173.3 parts by mass (5.2 g) of activated carbon component and 260.0 parts by mass (7.8 g) of impregnated water (see Table 1). ). At this time, the value of the above formula (1) is 1.94 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). Table 3 shows various physical characteristics of activated carbon.

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 in which the mixture composed of the components other than the main agent and the main agent in the solid state are mixed, and this is used as an outer dimension 80 mm × 130 mm. The air-permeable packaging material bag of No. 1 was filled with 17 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 paper / warif with a Wangken-type air permeability (air permeability resistance) of 45 to 60 seconds was used.

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, 173.0 parts by mass (10.9 g) of the activated carbon is prepared with respect to 100 parts by mass (6.3 g) of the main agent, and 325.4 parts by mass (added water) of water (added water) is prepared with respect to 100 parts by mass of the main agent. 20.5g) Prepared. Regarding other components, 331.7 parts by mass (20.9 g) of zeolite and 298.4 parts by mass (18.8 g) of potassium carbonate so as to have substantially the same amount as in Example 1 with respect to 100 parts by mass of the main agent. ), 200.0 parts by mass (12.6 g) of ferrous sulfate heptahydrate was weighed. 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 1.94 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, 346.0 parts by mass (21.8 g) of the hydrous activated carbon was used with respect to 100 parts by mass (6.3 g) of the main agent, and 152.4 parts by mass (9) of water (added water) was used with respect to 100 parts by mass of the main agent. .6g) The atmosphere adjusting agent of Example 3 was produced in the same manner as in Example 1 except that it was used, and the atmosphere adjusting agent 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 173.0 parts by mass of the activated carbon component and 173.0 parts by mass of impregnated water. Regarding other components, 331.7 parts by mass (20.9 g) of zeolite and 298.4 parts by mass (18. 8 g), ferrous sulfate heptahydrate was weighed in an amount of 200.0 parts by mass (12.6 g). In Example 3, the value of the above formula (1) is 1.94 with respect to the blending amount of the main agent (see Table 2).

In Example 4, 250.0 parts by mass (10.0 g) of zeolite, 250.0 parts by mass (10.0 g) of potassium carbonate, and water (added water) were added to 100 parts by mass (4.0 g) of the main agent. Except that 50.0 parts by mass (2.0 g), hydrous activated charcoal was weighed 325.0 parts by mass (13.0 g), and ferrous sulfate heptahydrate was weighed 150.0 parts by mass (6.0 g). , The atmosphere adjusting agent of Example 4 was produced in the same manner as in Example 1, and the atmosphere adjusting agent package of this Example was obtained using this. When the total amount of the main agent is 100 parts by mass, Example 4 contains 130.0 parts by mass of the activated carbon component and 195.0 parts by mass of impregnated water. Further, in Example 4, the value of the above formula (1) is 2.53 with respect to the blending amount of the main agent (see Table 2).

In Example 5, the atmosphere conditioner of Example 5 was used in the same manner as in Example 4, except that 225.0 parts by mass (9.0 g) of potassium carbonate was used with respect to 100 parts by mass (4.0 g) of the main agent. Was produced, and the air conditioner package of this example was obtained using this. 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 2.47 with respect to the blending amount of the main agent (see Table 2).

In Example 6, the atmosphere conditioner of Example 6 was used in the same manner as in Example 4, except that 200.0 parts by mass (8.0 g) of potassium carbonate was used with respect to 100 parts by mass (4.0 g) of the main agent. Was produced, and the air conditioner package of this example was obtained using this. 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 2.58 with respect to the blending amount of the main agent (see Table 2).

In Example 7, the atmosphere adjusting agent of Example 7 was used in the same manner as in Example 4, except that 175.0 parts by mass (7.0 g) of potassium carbonate was used with respect to 100 parts by mass (4.0 g) of the main agent. Was produced, and the air conditioner package of this example was obtained using this. 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 7, the value of the above formula (1) is 2.52 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 the main component, whereas in Example 8, sodium erythorbate having an average volume particle size of 532.5 μm was used. The atmosphere conditioner package of Example 8 was produced in the same manner as in Example 1, and the atmosphere conditioner package of this example was obtained using this. In Example 8, the value of the above formula (1) is 1.94 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 1 except that sodium erythorbate having an average volume particle size of 60.0 μm was used, and this was used to prepare the atmosphere conditioner of this Example. An atmosphere conditioner package was obtained. In Example 8, the value of the above formula (1) is 1.94 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 that of 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, using the activated carbon, each component was weighed in the same manner as in Example 2. Then, in the atmosphere, 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. In Comparative Example 1, the value of the above formula (1) is 1.94 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 4, 5 and 6. However, in Table 4, the oxygen concentration was "○" when it was 5% by volume or more and 12% by volume or less after 60 minutes, and "△" when it was more than 12% by volume and 18% by volume or less, 18 volumes. When it was more than%, it was marked as "x". The carbon dioxide concentration was "○" when it was 5% by volume or more and 10% by volume or less after 60 minutes, 0.1% by volume or more and less than 5% by volume, and more than 10% by volume and 15% by volume or less. In the case of "Δ", when it was less than 0.1% by volume and more than 15% by volume, it was evaluated as "x".

2. Evaluation Results (1) Manufacturability In Examples 1 to 9, 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) Type of activated carbon and amount of impregnated water Next, the types of activated carbon will be considered in comparison with Examples 1 to 3. In Examples 1 to 3, each 100 parts by mass of the main agent contains 173.3 parts by mass of the activated carbon component (see Table 1). Further, the total water content of the atmosphere adjusting agent of Example 1 is 326.7 parts by mass with respect to 100 parts by mass of the main agent, and 325.4 parts by mass in Examples 2 and 3, and the total water content is omitted. It is the same. However, when the atmosphere adjusting agent of Example 1 was used, the oxygen concentration in the atmosphere after 60 minutes was 9.7% by volume (see Table 5), and the carbon dioxide concentration was 6.6% by volume (see Table 5). (See Table 6), it was confirmed that it has an extremely good atmosphere adjusting ability in adjusting the atmosphere for microaerobic culture as shown in Table 4. On the other hand, when the atmosphere adjusting agent of Example 2 was used, the oxygen concentration in the atmosphere after 60 minutes was 13.6% by volume, and the carbon dioxide concentration was 4.7% by volume. When the atmosphere adjusting agent of Example 3 was used, the oxygen concentration in the atmosphere after 60 minutes was 13.3% by volume, and the carbon dioxide concentration was 3.8% by volume. All of them have sufficient atmosphere adjusting ability for adjusting the atmosphere for microaerobic culture, but the results show that the oxygen absorption rate and the carbon dioxide release rate are slightly inferior to those of Example 1. It is considered that such a difference occurs because the activated carbon types used in Examples 1 to 3 are different, and as a result, the amount of added water is different even if the total water content is the same. In Example 1, powdered hydrous activated charcoal (“A” (see Table 3)) having a water content of 60% by mass was used, and 66.7 parts by mass of added water was used with respect to 100 parts by mass of the main agent. It is considered that the water was supported on the carrier as the supporting water. In Example 2, granular activated carbon (“B”) having a water content of 0% by mass in a dry state is mixed with added water in an amount corresponding to the total water content in advance. In Example 3, a hydrous activated carbon (“C”) having a water content of 50% by mass was used, and 152.4 parts by mass (about 2.3 times the amount of water added in Example 1) was added to 100 parts by mass of the main agent. Is used. As described above, when the first to third examples are compared, when the other conditions are almost the same, the difference in the atmosphere adjusting ability is different due to the difference between the ratio of the impregnated water impregnated in the activated carbon and the ratio of the added water. It is recognized that it has occurred. Further, when the total water content is the same, in Examples 1 to 3, the higher the ratio of the impregnated water, the higher the reactivity, and the oxygen concentration and the carbon dioxide concentration suitable for the microaerobic culture atmosphere more quickly. It was confirmed that an adjustable atmosphere conditioner could be obtained. In Table 1, the ratio of the impregnated water to the total water content of the atmosphere adjusting agent of Example 2 is shown as 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 added water corresponding to the total water content with the activated carbon in advance, water is well absorbed in 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 examples. Although it is inferior to that of Example 1, it is equivalent to that of Example 3 or slightly higher than that of Example 2, and it is considered that better results were obtained in Example 2 with respect to the emission rate of carbon dioxide.

(2) Potassium carbonate blending amount Next, the blending amount of potassium carbonate with respect to 100 parts by mass of the main agent will be considered in comparison with Examples 4 to 7. In these examples, the amount of potassium carbonate blended with respect to 100 parts by mass of the main agent differs in the range of 175.0 parts by mass to 250.0 parts by mass, but the blending amounts of the other components are the same. When the amount of potassium carbonate compounded with respect to 100 parts by mass of the main agent differs within the above range, as shown in Tables 5 and 6, the larger the amount of potassium carbonate compounded, the slower the oxygen absorption rate and the carbon dioxide release rate. It was found that the smaller the amount of potassium carbonate blended, the faster the oxygen absorption rate and the carbon dioxide release rate tended to be. However, when Example 6 and Example 7 were compared, the amount of potassium carbonate blended in Example 6 was larger, but the oxygen absorption rate was faster. Further, when comparing Examples 4 to 7, the atmosphere adjusting agents of Examples 5 and 6 are good in adjusting the oxygen concentration and the carbon dioxide concentration suitable for the atmosphere for microaerobic culture more quickly. It was confirmed that. Further, from these results, the blending amount of potassium carbonate is appropriately adjusted so as to be an amount that can be adjusted to a desired concentration within a desired time according to the oxygen concentration and carbon dioxide concentration required for the atmosphere to be adjusted. It was also confirmed that this is preferable.

(3) Main agent particle size Next, the main agent particle size will be considered in comparison with Examples 1, 8 and 9. In Example 1, sodium erythorbate having an average volume particle size of 266.6 μm was used as the main component, whereas in Example 8, the average volume particle size was 532.5 μm, and in Example 9, the average volume particle size was 60.0 μm. The main ingredient was sodium erythorbate. The reactivity of Example 8 was lower than that of Example 1, and the reactivity of Example 9 was slightly improved as compared with Example 1. In Example 1, Example 8 and Example 9, hydrous activated carbon having an average volume particle size of about 10 μm is blended in 433.3 parts by mass with respect to 100 parts by mass of the main agent. On the other hand, when the amount of the main agent is the same, the total surface area of the main agent decreases as the particle size of the main agent increases. That is, finely divided hydrous activated carbon having a particle size of about 1/4 to 1/45 is blended with respect to the main agent at a rate four times or more that of the main agent. In this case, in Example 8 in which the particle size of the main agent is larger than that of Example 1, it is difficult to supply water by the hydrous activated carbon to the inside of the main agent particles, and the surface area of the main agent that contributes to the oxygen absorption reaction is small. Therefore, it is considered that the reactivity has decreased. On the other hand, in Example 9, the particle size of the main agent is smaller than that of Example 1, the reactivity is slightly higher than that of Example 1, and when the particle size of the activated carbon is smaller than the particle size of the main agent, the particle size of the main agent is smaller. It is considered that the contact area with the hydrous activated carbon is increased, and a more reactive atmosphere conditioner can be obtained.

According to the present invention, it is highly reactive, and it is possible to suppress a decrease in the atmosphere adjusting ability in the manufacturing process without using expensive manufacturing equipment or the like, and it is possible to satisfactorily adjust the atmosphere for culturing. A method for producing an agent and an atmosphere adjusting agent is provided.

Claims (9)

An atmosphere conditioner containing a main agent , potassium carbonate, water, a carrier, and activated carbon.
It contains a mixture of constituents other than the main agent and the main agent in a solid state.
The total amount of water contained in the atmosphere adjusting agent is more than 200 parts by mass with respect to 100 parts by mass of the main agent.
The activated carbon contains 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, and the activated carbon component excluding the impregnated water is 100% by mass with respect to 100 parts by mass of the main agent. unrealized or more parts,
The main agent is an atmosphere conditioner characterized by being 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 The atmosphere adjusting agent according to claim 1, which satisfies the relational expression (1) of.
1.0 <x / ((a / 100) x b) <5.0 ... (1) The atmosphere adjusting agent according to claim 2, wherein the amount of impregnated water 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 any one of claims 1 to 3, wherein the amount of supported water supported on the carrier is 5 parts by mass or more and less than 200 parts by mass 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 potassium carbonate is contained in an amount of more than 150 parts by mass with respect to 100 parts by mass of the main agent. The atmosphere adjustment according to any one of claims 1 to 5, wherein ferrous sulfate heptahydrate is contained in a range of 100 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. The atmosphere adjusting agent according to claim 6, wherein the amount of potassium carbonate is 125 parts by mass or more and less than 160 parts by mass with respect to 100 parts by mass of the ferrous sulfate heptahydrate. A method for producing an atmosphere conditioner containing a main agent , potassium carbonate, water, a carrier, and activated carbon.
It does not include the step of dissolving the main agent in the water.
A step of obtaining a mixture consisting of components other than the main agent containing the potassium carbonate, the water, the carrier, and the activated carbon.
The step of adding the main agent to the mixture in a solid state, and
It includes,
The main agent is one or more selected from L-ascorbic acid, erythorbic acid, and salts or hydrates thereof.
When obtaining the mixture, a hydrous activated carbon in which the activated carbon contains 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 is used, and at that time, the impregnated water is removed. The activated carbon component is used in an amount of 100 parts by mass or more with respect to 100 parts by mass of the main agent, and the total water content of the atmosphere adjusting agent is more than 200 parts by mass with respect to 100 parts by mass of the main agent. A method for producing an atmosphere adjusting agent, which comprises determining the blending amount. 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 The method for producing an atmosphere adjusting agent according to claim 8, wherein the blending amounts of the main agent and the water are determined so as to satisfy the relational expression (1).
1.0 <x / ((a / 100) x b) <5.0 ... (1)