JP6914507B2 - Manufacturing method of organic oxygen scavenger - Google Patents

Description

The present invention relates to a method for producing an organic oxygen scavenger, and more particularly to a method for producing a carbon dioxide gas generating type organic oxygen scavenger which is not detected by a metal detector and has high safety.

In the distribution process, in order to prevent oxidation of foods and the like, foods and the like are enclosed in a packaging container (including a packaging bag) together with an oxygen scavenger. By using an oxygen scavenger, it becomes possible to absorb oxygen in the packaging container and store foods and the like in an oxygen-free atmosphere. For this reason, in the food industry and the like, oxygen scavengers are widely used in order to prevent quality deterioration due to oxidation of foods and the like and to distribute foods and the like in good condition for a long period of time.

The oxygen scavenger includes an iron-based oxygen scavenger whose main component is iron powder and an organic-based oxygen scavenger whose main component is an organic oxidizable substance. Conventionally, iron-based oxygen scavengers have been widely used because they are inexpensive and have a stable oxygen absorbing ability. However, in recent years, the demand for organic oxygen scavengers that are not detected by the metal detector is increasing because the metal detector may perform a metal foreign matter contamination inspection in the distribution process of foods and the like.

As such an organic oxygen scavenger, for example, an oxygen scavenger containing ascorbic acid as a main component is known (see, for example, Patent Document 1). The oxygen scavenger containing ascorbic acid as the main component contains an alkaline agent, a reaction catalyst, water and the like, and reacts ascorbic acid with oxygen in the atmosphere to remove oxygen in the atmosphere. This is called a deoxygenation reaction. Since a carbonate or the like is used as an alkaline agent in such an oxygen scavenger, carbon dioxide gas is released into the atmosphere. That is, since the so-called vacuum phenomenon of the packaging container does not occur, it is suitable as an oxygen scavenger to be used together with soft foods and the like.

Japanese Unexamined Patent Publication No. 2003-10627

However, an oxygen scavenger containing ascorbic acid as a main component has a lower oxygen absorbing capacity than an iron-based oxygen scavenger, and an organic oxygen scavenger having a higher oxygen absorbing capacity is required. Further, in the oxygen scavenger containing ascorbic acid as the main component, carbon dioxide gas is generated as the deoxygenation reaction progresses. When carbon dioxide gas is generated, the packaging bag or the like filled with the oxygen scavenger swells, and when the internal pressure thereof becomes high, the packaging bag or the like may burst. Therefore, it is not preferable that the amount of carbon dioxide generated exceeds the amount of oxygen absorbed in the atmosphere by the oxygen scavenger (hereinafter referred to as "oxygen absorption amount").

The subject of the present invention is a carbon dioxide gas generating type organic oxygen scavenger, which has a good oxygen absorbing ability and the amount of carbon dioxide generated is about the same as the amount of oxygen absorbed. And its manufacturing method.

To solve the above SL problem, a method of manufacturing an organic-based oxygen absorber according to the present invention comprises a main agent, an alkali agent, and water, and the reaction catalyst, an organic consisting of granules comprising a carrier removal A method for producing an organic oxygen scavenger for producing an oxygen agent, wherein elisorbate is used as the main agent, potassium carbonate is used as the alkaline agent, and a first mixed component containing the main agent is used. The reaction catalyst and the second mixed component containing water are mixed, and the third mixed component containing the alkaline agent is mixed with the mixture to granulate, and the first mixed component is formed. Is characterized by including the above-mentioned carrier.

In the method for producing an organic oxygen scavenger according to the present invention, the third mixed component may contain the carrier, and the carrier may be blended into the first mixed component and the third mixed component, respectively. preferable.

In the method for producing an organic oxygen scavenger according to the present invention, the first mixed component preferably contains a tannin compound. Further, it is more preferable that the third mixed component contains hydrous activated carbon.

According to the organic oxygen scavenger according to the present invention, it is a carbon dioxide gas generating type organic oxygen scavenger, has a sufficient oxygen absorbing ability, and the amount of carbon dioxide generated is about the same as the amount of oxygen absorbed. An organic oxygen scavenger can be provided and can be produced.

Hereinafter, preferred embodiments of the organic oxygen scavenger according to the present invention will be described.

1. 1. Organic oxygen scavenger The organic oxygen scavenger according to the present invention is an organic oxygen scavenger composed of a main agent, an alkaline agent, water, a reaction catalyst, and a granulated product containing a carrier, and serves as the main agent. , Erythorbic acid salt is used, and potassium carbonate is used as an alkaline agent.

According to the organic oxygen scavenger according to the present invention, by using elisorbate as a main agent and potassium carbonate as an alkaline agent, it is a carbon dioxide gas generating type organic oxygen scavenger and has sufficient oxygen. It has an absorptive capacity, and the amount of carbon dioxide (carbon dioxide) generated can be made to be about the same as the amount of oxygen removed from the atmosphere (hereinafter, referred to as "oxygen absorption amount"). In the present invention, the "oxygen absorption capacity" is evaluated based on the oxygen absorption rate and the oxygen absorption amount, and the high oxygen absorption capacity means that the oxygen absorption rate is high and the oxygen absorption amount is large. means. The evaluation method will be described later, but a high oxygen absorption rate means that the oxygen concentration after 24 hours is 1.0% or less, and a large oxygen absorption amount means that the oxygen absorption amount after 168 hours is 1.0% or less. It means that it is 200 mL or more. Further, "the amount of carbon dioxide generated is about the same as the amount of oxygen absorbed" means that the amount of carbon dioxide generated is 105% or less of the amount of oxygen gas absorbed, and the amount of carbon dioxide generated is the amount of oxygen gas absorbed. It means that it is 75% or more of. When the amount of carbon dioxide generated exceeds 105% of the amount of oxygen gas absorbed, the packaging bag or the like swells, and when it is less than 75%, the packaging bag contracts and a vacuum phenomenon occurs. The amount of carbon dioxide generated is preferably 100% or less, preferably 80% or more, and more preferably 85% or more of the oxygen gas absorption amount. Within this range, it is preferable that the difference between the amount of carbon dioxide generated and the amount of oxygen gas absorbed is small.

The organic oxygen scavenger according to the present invention preferably contains a tannin compound and a hydrous activated carbon in addition to the above-mentioned main agent, alkaline agent, water, reaction catalyst and carrier. Hereinafter, the constituent components of the organic oxygen scavenger will be described in the order of main agent, water, alkaline agent, reaction catalyst, tannin compound, and hydrous activated carbon.

(1) Main agent In the organic oxygen scavenger according to the present invention, erythorbic acid salt is used as the main agent. In the present invention, the main agent means the component having the highest content among the components contributing to the deoxygenation reaction in the organic oxygen scavenger. Erythorbic acid salt means an alkali metal salt of erythorbic acid and the like, and sodium erythorbate can be particularly preferably used in the present invention. Since sodium erythorbate is easily available and inexpensive as compared with ascorbic acid, the organic oxygen scavenger can be produced at a lower cost than when ascorbic acid is used as a main agent. Further, since sodium erythorbate is a compound that is also used as a food additive, it is highly safe when used as a main ingredient of an organic oxygen scavenger used together with oral products such as foods.

Further, erythorbic acid salt is an easily oxidizing compound and reacts well with oxygen in the atmosphere in the presence of an alkaline agent and water to remove oxygen in the atmosphere. Along with this deoxygenation reaction of erythorbic acid salt, carbon dioxide gas equivalent to the amount of oxygen absorbed is released into the atmosphere. Therefore, although it is a carbon dioxide gas generating type oxygen scavenger that does not cause a vacuum phenomenon, carbon dioxide gas is not released into the atmosphere in excess of the oxygen absorption amount as in the case of using ascorbic acid as a main agent. It is possible to prevent the internal pressure of a bag or the like from being increased in a package filled with an organic oxygen scavenger. When ascorbic acid is used as the main agent, the amount of carbon dioxide generated exceeds 110% of the amount of oxygen absorbed. Further, when ascorbic acid salt is used in the organic oxygen scavenger according to the present invention, the oxygen absorbing ability is poor and it is not practically usable.

(2) Alkaline agent In the organic deoxygen agent according to the present invention, the alkaline agent is an essential component for advancing the deoxygenation reaction. The present invention is characterized in that potassium carbonate is used as the alkaline agent. The deoxygenation reaction of an organic oxygen scavenger is carried out under basic conditions using water (liquid phase) as a reaction field. Therefore, conventionally, as an alkaline agent, alkali metals such as potassium carbonate, sodium carbonate and calcium carbonate, or carbonates of alkaline earth metals have been used. However, as a result of diligent research by the present inventors, when erythorbic acid salt is used as the main agent, by using potassium carbonate, the powder characteristics (fluidity, appearance) are compared with the case where other alkaline agents are used. It has been found that an organic oxygen scavenger having good density, etc.), high oxygen absorption capacity, and a small amount of carbon dioxide gas generated can be obtained. The reason is not clear, but it is presumed as follows, for example.

Erythorbic acid salt has low solubility in water. For example, sodium erythorbate has a solubility in water of 16 g / 100 g (25 ° C.), and sodium erythorbate is a poorly soluble compound in water. On the other hand, the solubility of potassium carbonate in water is as high as 113.5 g / 100 g (25 ° C.), and it is an easily soluble compound. As described above, the deoxygenation reaction with the oxygen scavenger is carried out under basic conditions using water (liquid phase) as a reaction field. Here, 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 favorable reaction field for the above-mentioned deoxygenation reaction, and it becomes difficult to proceed with the deoxygenation reaction by the main agent. , Oxygen absorption capacity decreases. 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 hydrolyzed by the alkaline agent when these are mixed, or the deoxygenation reaction by the main agent proceeds excessively. It is not preferable because the oxygen absorption capacity of the main agent decreases and the fluidity of the granulated product decreases before the oxygen agent is produced.

In the present invention, by using erythorbic acid salt having low solubility in water as the main agent and potassium carbonate having high solubility in water as the alkaline agent, the main agent is hydrolyzed or deoxygenation reaction occurs during the manufacturing process. It is possible to prevent excessive progress, and it is possible to maintain good fluidity of the granulated product. In particular, when the organic oxygen scavenger is produced by the method described later, it prevents a decrease in oxygen absorption capacity during the production process, has good production efficiency, and has high oxygen absorption capacity when used as a product. An organic oxygen scavenger can be obtained.

In the organic oxygen scavenger according to the present invention, potassium carbonate as an alkaline agent is preferably contained in an amount of 15 parts by mass or more and 40 parts by mass or less, preferably 20 parts by mass or more, with respect to 100 parts by mass of erythorbic acid as the main agent. It is more preferable that it is contained in an amount of 35 parts by mass or less.

(3) Water Water is an essential component in the organic oxygen scavenger according to the present invention. Water provides a reaction field by acclimatizing the constituent components constituting the organic oxygen scavenger, and when the main agent is 100 parts by mass, the water contains 10 parts by mass or more and 100 parts by mass or less. preferable. In particular, from the viewpoint of maintaining the fluidity of the granulated product, the water content when the main agent is 100 parts by mass is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less. .. If the water content is high, it becomes difficult for the carrier described later to retain water and the like, which is not preferable. On the other hand, in order to allow the deoxygenation reaction to proceed satisfactorily, the water content is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 25 parts by mass or more. ..

(4) Reaction catalyst The organic oxygen scavenger according to the present invention contains a reaction catalyst for promoting a deoxygenation reaction with erythorbic acid salt. As the reaction catalyst, for example, an organic metal 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, and manganese, or a compound salt, or It is preferable to use an inorganic catalyst such as these hydrates. An organic oxygen scavenger having a high oxygen absorbing ability can be obtained by the configuration including a reaction catalyst.

When the organic oxygen scavenger contains a tannin compound described later, iron hydrochloride, nitrate, sulfate, double salt, etc., or hydrates thereof, that is, an iron catalyst should be used. Is preferable. The iron catalyst easily forms a complex with the tannin compound. Probably because of this, it is possible to obtain an organic oxygen scavenger having high oxygen absorption capacity and better fluidity of the granulated product. In order to obtain such an effect, it is particularly preferable to use ferrous sulfate hydrate among the iron catalysts.

In the organic oxygen scavenger 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 added to 100 parts by mass of the main agent erythorbic acid salt. It is preferable to contain 3 parts by mass or more and 20 parts by mass or less. If the content of the reaction catalyst is less than 3 parts by mass, the effect of promoting the deoxygenation reaction is low, which is not preferable. In promoting the deoxygenation reaction, the content of the reaction catalyst is more preferably 5 parts by mass or more, and further preferably 7 parts by mass or more. On the other hand, when the content of the reaction catalyst exceeds 20 parts by mass, it becomes difficult to dissolve the reaction catalyst in water unless the content of water is increased more than the amount described later. If the water content is increased above the amount described below, it becomes difficult to granulate. On the other hand, if the water content is within an appropriate range that allows granulation, the entire amount of the reaction catalyst cannot be dissolved in water. Therefore, the surplus reaction catalyst is mixed with other components in the powder state, and the effect of promoting the deoxygenation reaction is saturated. From this point of view, the content of the reaction catalyst is more preferably 16 parts by mass or less, and further preferably 14 parts by mass or less.

(5) Carrier The organic oxygen scavenger according to the present invention contains a carrier capable of carrying water because it contains water as a constituent component. By including the carrier, the constituent components of the organic oxygen scavenger can be granulated and handled as a powder. As the carrier, a porous substance such as wet silica, activated carbon, zeolite, vermiculite, and montmorillonite can be used. One or more of these porous substances can be used alone or in combination.

In particular, in the organic oxygen scavenger according to the present invention, it is preferable to use wet silica as a carrier. Wet silica refers to synthetic silica produced by a wet manufacturing method such as a sedimentation method or a gel method. Dry silica produced by the vapor phase method or the like does not have pores inside the particles, whereas wet silica has pores inside the particles. By using silica having such pores, the constituent components of the organic oxygen scavenger can be retained in the pores. Further, by using wet silica as a carrier, a granulation effect can be obtained, powdering when the organic oxygen scavenger is filled in the packaging bag by a filling packaging machine or the like is suppressed, and the fluidity is improved. Further, since the constituent components of the organic oxygen scavenger containing water can be retained in the pores of the wet silica, even when the organic oxygen scavenger is sealed in the packaging material, the surface of the packaging material is covered. It is possible to suppress so-called "exudation", in which the color looks dark as if water has exuded.

In the organic oxygen scavenger, it is preferable to use wet silica having an average pore diameter of 300 Å or more and 600 Å or less in order to obtain the above-mentioned effects. When the average pore diameter exceeds 600 Å, the apparent density of the granulated product becomes small, so that the powdering is likely to occur and the fluidity is also lowered. Therefore, it is not preferable because the production efficiency is lowered. From this point of view, the average pore diameter is more preferably 550 Å or less, and even more preferably 500 Å or less. On the other hand, when the average pore diameter is less than 300 Å, it becomes difficult to sufficiently retain the constituent components of the organic oxygen scavenger in the pores of the wet silica. Therefore, it is necessary to increase the content of wet silica in the organic oxygen scavenger as compared with the components involved in the deoxygenation reaction of the organic oxygen scavenger such as the main agent, alkaline agent, reaction catalyst, and water. be. In that case, the main agent and oxygen in the atmosphere cannot be efficiently brought into contact with each other, and the amount of oxygen absorbed per unit mass of the organic oxygen scavenger decreases, which is not preferable. From this point of view, the average pore diameter is more preferably 350 Å or more, and further preferably 400 Å or more. The "average pore diameter" refers to the volume average of the values measured by the mercury intrusion method.

The average particle size of the wet silica is preferably 50 μm or more and 200 μm or less, and more preferably 80 μm or more and 180 μm or less. Assuming that the average pore diameter is within the above preferable range, if the average particle size of the wet silica is less than 50 μm, the specific gravity of the wet silica becomes smaller than that in the case where the average particle size is 50 μm or more. Therefore, the apparent density of the granulated product is reduced, and for the same reason as described above, the production efficiency is lowered, which is not preferable. On the other hand, assuming that the average pore diameter is within the above preferable range, if the average particle size exceeds 200 μm, the specific gravity becomes larger as compared with the case where the average particle size is 200 μm or less. Therefore, the apparent density of the granulated product is increased, and the production efficiency is improved. However, the pore volume per unit mass of wet silica is reduced. Therefore, it is necessary to increase the content of wet silica in the organic oxygen scavenger as compared with the components involved in the deoxygenation reaction of the organic oxygen scavenger such as the main agent, alkaline agent, reaction catalyst, and water. be. In that case, it is not preferable because the amount of oxygen absorbed per unit mass of the organic oxygen scavenger is reduced. The "average particle size" refers to the volume average of the values measured by the laser diffraction / scattering method.

In the organic oxygen scavenger according to the present invention, the content of the carrier is preferably 30 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of erythorbic acid salt as the main agent. If the content of the carrier is less than 30 parts by mass, the water required for the deoxygenation reaction cannot be sufficiently supported, and an organic oxygen scavenger having high oxygen absorption capacity can be obtained and as a powder of granulated material. It becomes difficult to maintain the characteristics of. From these viewpoints, the content of the carrier is more preferably 35 parts by mass or more, and further preferably 40 parts by mass or more. On the other hand, when the content of the carrier exceeds 60 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 organic oxygen scavenger is reduced, which is not preferable. From these viewpoints, the content of the carrier is more preferably 55 parts by mass or less, and further preferably 50 parts by mass or less.

(6) Tannin Compound In the organic oxygen scavenger according to the present invention, it is preferable that the granulated product contains a tannin compound in addition to the main agent, alkaline agent, water, reaction catalyst and carrier. Oxygen absorption capacity is improved by using a tannin compound together with a main agent, an alkaline agent, water, a reaction catalyst and a carrier. In addition, the apparent density and specific gravity of the granulated product are increased, and the granulation effect is improved.

The tannin compound is a composite compound (polyphenol compound) in which two or more benzene rings containing one or more phenolic hydroxyl groups are contained in the chemical structural formula. The tannin compound may be any of those produced by chemical synthesis and those extracted from the fruits, leaves and flowers of plants, bark and the like. Examples of the tannin compound extracted from the plant include those extracted from quebracho, wattle (mimosa), chestnut lumber, myrobalan, gambir, hemlock, oak and the like. From the viewpoints of easy availability, low cost, high safety, and high granulation effect, it is particularly preferable to use condensed tannin or hydrolyzed tannin, which is a tannin compound extracted from a plant.

Here, the condensed tannin is a polymer of a compound having a flavanol skeleton, and its structure is diverse and complicated. There are hundreds or more types of condensed tannins, and any of the condensed tannins may be used in the present invention.

Hydrolyzed tannins form ester bonds with aromatic compounds such as gallic acid and ellagic acid, and their structures are diverse and complex. There are hundreds or more types of hydrolyzed tannins, and any of the hydrolyzed tannins may be used in the present invention.

Here, the tannin compound itself is also an easily oxidizing compound that is easily oxidized by oxygen in the air. For this reason, as described above, the oxygen absorption capacity is improved by the configuration containing the tannin compound as compared with the case where the tannin compound is not contained. As will be described later in the examples, when potassium carbonate is used as the alkaline agent, the oxygen absorption capacity is improved by adding the tannin compound.

When the organic oxygen scavenger according to the present invention is configured to contain a tannin compound, it is preferable that the tannin compound is contained in an amount of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of erythorbic acid salt as the main agent. .. In order to obtain the granulation effect, the tannin compound is more preferably 1.0 part by mass or more, and further preferably 2.0 part by mass or more with respect to 100 parts by mass of the main agent. Further, from the viewpoint that it becomes easier to knead each component satisfactorily, the tannin compound is more preferably contained in an amount of 8 parts by mass or less, more preferably 6 parts by mass or less, based on 100 parts by mass of the main agent.

(7) Hydrous Activated Carbon Further, the organic oxygen scavenger according to the present invention may contain hydrous activated carbon as a component thereof in addition to the carrier. In the present invention, hydrous activated carbon means activated carbon containing water in advance. As mentioned above, water is an essential component in advancing the deoxygenation reaction. However, when the content of water as a liquid increases, it becomes difficult to granulate the organic oxygen scavenger. Further, if the content of water as a liquid increases, the deoxygenation reaction of the main agent may proceed in the manufacturing process of the organic oxygen scavenger. By impregnating the granulated product with water as the hydrous activated carbon, the water required for the deoxygenation reaction can be obtained from the hydrous activated carbon when the organic oxygen scavenger is used.

Here, the water content of the hydrous activated carbon is preferably 30% by mass to 65% by mass. The volume average particle size of the hydrous activated carbon is preferably 5 μm to 15 μm. In the organic oxygen scavenger according to the present invention, when the granulated product contains hydrous activated carbon, the content of hydrous activated carbon is 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the main agent. Is preferable.

(8) Content ratio of each component Next, the content ratio of each component to the total amount of the components of the organic oxygen scavenger will be described. First, with respect to the total amount of the constituent components of the organic deoxidizer according to the present invention, the main agent is 40% by mass or more and 50% by mass or less, the alkaline agent is 10% by mass or more and 15% by mass or less, and the water is 15% by mass or more and 20% by mass. % Or less, the reaction catalyst is preferably contained in an amount of 3% by mass or more and 6% by mass or less, and the carrier is preferably contained in an amount of 17% by mass or more and 22% by mass or less. By containing these essential components in such a content ratio, it is a carbon dioxide gas generating type organic oxygen scavenger, has high oxygen absorbing ability, and the amount of carbon dioxide generated is the same as the amount of oxygen absorbed. An organic oxygen scavenger can be obtained.

Here, when the organic deoxidizer contains a tannin compound, the content of the tannin compound with respect to the total amount of the constituent components of the organic deoxidizer is preferably 0.1% by mass or more and 10% by mass or less. It is more preferably 0.5% by mass or more and 6% by mass or less, and further preferably 1% by mass or more and 3% by mass or less.

When the organic oxygen scavenger contains hydrous activated carbon, the content of the hydrous activated carbon with respect to the total amount of the constituent components of the organic oxygen scavenger is preferably 0.1% by mass or more and 10% by mass or less, and is 0. More preferably, it is 5.5% by mass or more and 6% by mass or less.

2. Method for Producing Organic Oxygen Scavenger Next, a method for producing the organic oxygen scavenger according to the present invention will be described. In the method for producing an organic oxygen scavenger according to the present invention, erythorbic acid salt is used as a main agent, potassium carbonate is used as an alkaline agent, and a first mixed component containing the main agent, a reaction catalyst, and water are contained. The second mixed component is mixed, and the third mixed component containing an alkaline agent is mixed with the mixture to granulate, and the first mixed component is characterized by containing the above-mentioned carrier. By adopting this method, the organic oxygen scavenger according to the present invention described above can be produced.

Here, in the first mixed component, it is preferable that the main agent and the carrier are mixed in advance. Further, it is preferable that the second mixed component is prepared as a reaction catalyst solution by mixing the reaction catalyst and water in advance. As mentioned above, erythorbic acid salt used as a main agent has low solubility in water. The deoxygenation reaction with the main agent is carried out in the presence of an alkaline agent and water. By mixing the first mixed component and the second mixed component in a state where each component is mixed in advance, the water content required for the deoxygenation reaction of the main agent is retained in the carrier contained in the first mixed component. And the two can be mixed well. On the other hand, since the first mixed component and the second mixed component do not contain an alkaline agent, the deoxygenation reaction by the main agent does not proceed even if both are mixed. Therefore, the first mixed component and the second mixed component can be mixed in the atmosphere.

Here, by mixing the tannin compound with the first mixed component in the above-mentioned range, it becomes possible to suppress the powdering of the first mixture by the granulation effect of the tannin compound, and the first mixed component. And the second mixed component can be sufficiently mixed. By mixing the first mixed component and the second mixed component well and sufficiently retaining the second mixed component on a carrier such as wet silica, it is easy to obtain a granulated product having a high apparent density. Therefore, an organic oxygen scavenger having a high oxygen absorbing ability can be obtained.

Then, the third mixed component containing the alkaline agent is mixed with the mixture obtained by mixing the first mixed component and the second mixed component. The third mixed component does not contain water. Therefore, the third mixed component is mixed as a powder with respect to the mixture of the first mixed component and the second mixed component. As described above, the water contained in the second mixed component is retained by the carrier contained in the first mixed component. Therefore, even if the third mixed component is mixed with the mixture of both in the atmosphere, the main agent is hydrolyzed or the deoxygenation reaction proceeds excessively before the granulated product is produced. Can be prevented. From these facts, it is possible to suppress a decrease in the oxygen absorption capacity of the main agent until the oxygen scavenger is produced.

In the method for producing an organic oxygen scavenger according to the present invention, it is more preferable that the third mixed component contains a carrier, and the carrier is blended with the first mixed component and the third mixed component, respectively. By blending a carrier into each of the first mixed component and the third mixed component, an organic oxygen scavenger having better oxygen absorption capacity as compared with the case where the carrier is blended only in the first mixed component. Is obtained.

When the organic oxygen scavenger contains hydrous activated carbon, the hydrous activated carbon is preferably contained in the third mixed component. By including the hydrous activated carbon in the third mixed component, the water content for dissolving the alkaline agent can be provided by the hydrous activated carbon.

When the third mixed component contains not only an alkaline agent but also a component other than the alkaline agent (support, water-containing activator), a mixture of the first mixed component and the second mixed component in a state in which these are mixed in advance. Or each component may be sequentially added to the mixture of the first mixed component and the second mixed component without premixing each component constituting the third mixed component.

Here, since the main agent, alkaline agent, water, reaction catalyst, carrier, tannin compound, and hydrous activated carbon are as described above, the description thereof will be omitted here. The content of each component with respect to 100 parts by mass of the main agent and the content ratio of each component with respect to the total amount of the components of the organic oxygen scavenger are as described above, and description thereof will be omitted here.

Regarding the carrier, the entire amount of the carrier contained in the organic oxygen scavenger may be blended with the first mixed component, but as described above, the carrier is mixed with the first mixed component and the third mixed component. It is preferable to distribute the oxygen scavenger to an organic oxygen scavenger having better oxygen absorption capacity. From this point of view, the content of the carrier contained in the first mixed component is preferably 70% by mass or less, and preferably 60% by mass or less, of the total amount of the carrier contained in the organic oxygen scavenger. More preferably, it is 50% by mass or less. The content of the carrier contained in the first mixed component is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.

The granulated product granulated by mixing the first mixed component to the third mixed component as described above is filled and packaged in a breathable packaging material. 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 these 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. The organic oxygen scavenger package as a product can be obtained by filling the breathable packaging material with the organic oxygen scavenger in a predetermined amount and closing the opening.

When obtaining an organic oxygen scavenger package as described above, the apparent density of the granulated material as a raw material has a great influence on the good production efficiency.

The apparent density of the granulated product shall be measured as follows in accordance with JIS Z 2504: 2012. The sample (granulation powder) is closed in the opening of the funnel having an orifice diameter of 5 mm, the sample is put into the funnel, the sample is dropped into a 25 cc stainless cup, and the weight of the sample packed in the 25 cc cup is divided by the stainless cup volume. The obtained value is used as the apparent density of the sample.

When the apparent density is ^{less than 0.55 g / cm 3} , powdering is likely to occur during filling and packaging, and the fluidity is also lowered. Therefore, from the viewpoint of production efficiency, the apparent density of the granulated product ^{is preferably 0.55 g / cm 3} or more. Further, in the organic oxygen scavenger, the lower the apparent density of the granulated product, the larger the size of the organic oxygen scavenger as a product with respect to the amount of oxygen that can be absorbed per unit. In that case, the usability of the product is poor and the cost increases. Therefore, from the viewpoint of ease of use and cost of the product, it is preferable that the apparent density of the granulated product is within the above range.

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.

Sodium erythorbinate (main agent) 18 g, water 6.5 g, ferrous sulfate hydrate (reaction catalyst) 1.8 g, wet silica (supporter) 7.5 g, alkaline agent (potassium carbonate) 4.5 g, hydrous activated carbon Using 0.5 g (water content 60% by mass), the organic oxygen scavenger according to the present invention was produced as follows. Wet silica with an average pore diameter of 448 Å, a specific surface area of 201 m ² / g, an average particle diameter of 150 μm, a pore volume of 2.41 mL / g, and an oil absorption of 250 mL / g (wet silica manufactured by Oriental Silica Corporation). (Tokuseal PR)) was used.

First, the total amount of the main agent and a part of the wet silica (40% by mass of the total amount of the wet silica) were mixed to obtain a first mixed component. Moreover, the total amount of water and the total amount of ferrous sulfate hydrate were mixed to obtain a second mixed component. Further, the remaining wet silica, the total amount of the alkaline agent, and the total amount of the hydrous activated carbon were used as the third mixed component.

In the atmosphere, the first mixed component and the second mixed component were mixed (kneaded) to obtain a mixture composed of the first mixed component and the second mixed component. Next, the third mixed component was mixed (kneaded) with the mixture to obtain a granulated product. The apparent density of the obtained granulated product was 0.612 g / cm ³ . An organic oxygen scavenger made of this granulated product is filled in a breathable packaging material bag (seal width 5 mm) having an outer size of 65 mm × 55 mm sealed on three sides in a predetermined amount (2.8 g), and the opening is heat-laminated. It was sealed and sealed to form an organic oxygen scavenger package. Further, as the breathable packaging material, a material having a four-layer laminated structure of perforated (polyester / polyethylene) / paper / perforated polyethylene and having a galley type air permeability of 6000 to 10000 seconds / 100 ml was used.

In Example 2, a granulated product was obtained in the same manner as in Example 1 except that 0.5 g of the condensed tannin compound was added when the first mixed component was obtained. The apparent density of the granulated product was 0.611 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 3, 1.0 g of the hydrolyzed tannin compound was added when the first mixed component was obtained, and the content of ferrous sulfate hydrate was 2.0 g when the second mixed component was obtained. A granulated product was obtained in the same manner as in Example 1 except that the content of potassium carbonate as an alkaline agent was 6.0 g when the third mixed component was obtained. The apparent density of the granulated product was 0.622 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 4, 0.5 g of the condensed tannin compound was added when the first mixed component was obtained, and the content of ferrous sulfate hydrate was 2.0 g when the second mixed component was obtained. , A granulated product was obtained in the same manner as in Example 1 except that the content of potassium carbonate as an alkaline agent was 6.0 g when the third mixed component was obtained and the following was used as the wet silica. .. The apparent density of the granulated product was 0.605 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 4, the wet silica has an average pore diameter of 482 Å, a specific surface area of 191 m ² / g, an average particle diameter of 100 μm, a pore volume of 2.18 mL / g, and an oil absorption of 280 mL / g (Oriental silica). Wet silica (Tokuseal NR) manufactured by Corporation was used.

In Example 5, 0.5 g of the condensed tannin compound was added when the first mixed component was obtained, and the content of ferrous sulfate hydrate was 1.7 g when the second mixed component was obtained. , A granulated product was obtained in the same manner as in Example 1 except that the content of potassium carbonate as an alkaline agent was 6.0 g when the third mixed component was obtained. The apparent density of the granulated product was 0.614 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 6, granulation was carried out in the same manner as in Example 1 except that the content of sodium erythorbate as a main ingredient was 16 g and 0.5 g of a condensed tannin compound was added when the first mixed component was obtained. I got something. The apparent density of the granulated product was 0.612 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 7, when the second mixed component was obtained, the content of ferrous sulfate hydrate was 2 g, the content of potassium carbonate as an alkaline agent was 6.0 g, and the condensed tannin compound 0. Granules were obtained in the same manner as in Example 1 except that 5 g was added. The apparent density of the granulated product was 0.630 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 8, 0.5 g of the condensed tannin compound was added when the first mixed component was obtained, and the content of ferrous sulfate hydrate was 2.0 g when the second mixed component was obtained. , A granulated product was obtained in the same manner as in Example 1 except that the content of potassium carbonate as an alkaline agent was 6.0 g when the third mixed component was obtained and the following was used as the wet silica. .. The apparent density of the granulated product was 0.530 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package. The granulated product of Example 8 was produced in the same manner as the granulated product of Example 4, except that the types of wet silica were different.

In Example 8, the wet silica has an average pore diameter of 690 Å, a specific surface area of 262 m ² / g, an average particle diameter of 12.3 μm, a pore volume of 2.43 mL / g, and an oil absorption of 230 mL / g ( Wet silica (Fine X12) manufactured by Oriental Silica Corporation was used.

In Example 9, the same procedure as in Example 7 was carried out except that the entire amount of wet silica was used when obtaining the first mixed component and no wet silica was added when obtaining the third mixed component. Obtained a granulated product. The apparent density of the granulated product was 0.592 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 10, except that the first mixed component and the second mixed component were mixed in a nitrogen atmosphere to obtain the above mixture, and the third mixed component was mixed with the mixture in a nitrogen atmosphere. Obtained a granulated product in the same manner as in Example 7. The apparent density of the granulated product was 0.585 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

In Example 11, a granulated product was obtained in the same manner as in Example 2 except that when the first mixed component was obtained, the total amount of wet silica was 60% by mass. The apparent density of the granulated product was 0.662 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

Comparative example

[Comparative Example 1]
In Comparative Example 1, granulated products were obtained in the same manner as in Example 1 except that the same amount (4.5 g) of sodium carbonate was used instead of potassium carbonate as the alkaline agent. The apparent density of the granulated product was 0.513 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

[Comparative Example 2]
In Comparative Example 2, granules were obtained in the same manner as in Example 1 except that the same amount (4.5 g) of calcium carbonate was used instead of potassium carbonate as the alkaline agent. The apparent density of the granulated product was 0.444 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

[Comparative Example 3]
In Comparative Example 3, granulated products were obtained in the same manner as in Example 2 except that the same amount (4.5 g) of sodium carbonate was used instead of potassium carbonate as the alkaline agent. The apparent density of the granulated product was 0.549 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

[Comparative Example 4]
In Comparative Example 4, granulated products were obtained in the same manner as in Example 2 except that the same amount (4.5 g) of calcium carbonate was used instead of potassium carbonate as the alkaline agent. The apparent density of the granulated product was 0.512 g / cm ³ . Then, in the same manner as in Example 1, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

[Comparative Example 5]
In Comparative Example 5, granulated products were obtained in the same manner as in Example 11 except that sodium ascorbate was used instead of sodium erythorbate as the main agent. The apparent density of the granulated product was 0.570 g / cm ³ . Then, in the same manner as in Example 11, the granulated product was filled in a predetermined amount of a breathable packaging material bag to produce an organic oxygen scavenger package.

<evaluation>
Using each organic oxygen scavenger package produced in each Example and each Comparative Example, the oxygen absorption capacity and the amount of carbon dioxide gas generated by the organic oxygen scavenger according to the present invention were evaluated. The evaluation methods and evaluation results are as follows. Further, Tables 1 and 2 show the content of each component with respect to 100 parts by mass of the main agent in each Example and each Comparative Example, the content ratio of each component with respect to the total amount of the components of the organic oxygen scavenger, and the apparent density. , Oxygen absorption capacity, carbon dioxide gas generation amount, etc.

1. 1. Evaluation method The oxygen absorption capacity and carbon dioxide gas generation amount of each organic oxygen scavenger were evaluated as follows.
(1) Oxygen absorption rate and carbon dioxide gas generation rate This organic oxygen scavenger package was placed in a gas barrier bag (220 x 180 mm) of polyvinylidene chloride coat / polyethylene laminate film, filled with 500 ml of air, and sealed. A plurality of sealed bags were prepared.

In order to evaluate the oxygen absorption rate and carbon dioxide gas generation rate of the obtained organic oxygen scavenger package at room temperature, each sealed bag was held at 25 ° C., and the oxygen concentration (% by volume) in each bag after 24 hours. And the carbon dioxide concentration (% by volume) was measured using Check Mate 3 manufactured by PBI Dansensol. The results are shown in Tables 1 and 2 in the column displaying "after 24 hours".

(2) Oxygen absorption amount and carbon dioxide gas generation amount In order to measure the oxygen absorption amount per package of each organic oxygen scavenger package, 1500 ml of air is filled in each organic oxygen scavenger package in the same manner as described above. A sealed bag was prepared and kept at 25 ° C., and the amount of oxygen absorbed and the amount of carbon dioxide generated after 168 hours were measured. The results are shown in Tables 1 and 2 in the column displaying "after 168 hours".

2. Evaluation Results (1) Oxygen Absorption Rate, Oxygen Absorption Amount and Carbonate Gas Generation Rate, Carbonation Gas Generation Amount The organic oxygen scavengers made of the granules produced in Examples 1 to 11 are Comparative Examples 1 to Comparative Examples. Compared with the organic oxygen scavenger made of the granulated product prepared in No. 5, the oxygen absorption rate and the amount of oxygen absorption are high, and it has a practically sufficient oxygen absorption capacity.

Further, the organic oxygen scavengers of Examples 1 to 11 and Comparative Examples 1 to 4 all contain sodium erythorsorbate as a main component, and the amount of carbon dioxide generated after 168 hours is the amount of oxygen absorbed after 168 hours. The amount of the organic oxygen scavenger package and the sealed bag in which the organic oxygen scavenger package is enclosed is excessive due to the generated carbon dioxide gas while preventing the so-called vacuum phenomenon from occurring. It did not swell.

On the other hand, Comparative Example 5 is the same as Example 11 except that the main agent is sodium ascorbate. In Comparative Example 5, the amount of carbon dioxide generated after 168 hours was almost the same as the amount of oxygen absorbed after 168 hours as in Example 11, but the oxygen absorption rate was slow and the amount of oxygen absorbed was low, so that it was practically used. It does not endure.

(2) Types of Alkaline Agents Example 1 is compared with Comparative Examples 1 and 2. The organic oxygen scavengers of Example 1, Comparative Example 1 and Comparative Example 2 differ in the type of alkaline agent. In Example 1, potassium carbonate is used as the alkaline agent, whereas sodium carbonate is used in Comparative Example 1 and calcium carbonate is used in Comparative Example 2. The organic oxygen scavenger of Comparative Example 1 has the same deoxidizing rate as that of Example 1, but the amount of oxygen absorbed is 80 mL or more less than that of Example 1, and the oxygen absorbing capacity is lower than that of Example 1. The organic oxygen scavenger of Comparative Example 2 has a lower deoxidizing rate and an oxygen absorbing capacity than that of Example 1.

(3) Presence or absence of tannin compound and type of tannin compound Example 1, Comparative Example 1 and Comparative Example 2 are compared with Example 2, Comparative Example 3 and Comparative Example 4. Example 2 and Comparative Example 3 and Comparative Example 4 differ in the presence or absence of the tannin compound from Example 1, Comparative Example 1 and Comparative Example 2, respectively. It can be confirmed that the organic oxygen scavenger of Example 2 is a scavenger having higher oxygen absorption capacity than that of Example 1. Further, as compared with Example 2, it can be confirmed that Comparative Example 3 and Comparative Example 4 have low oxygen absorption capacity.

Here, in Examples 1 and 2 in which potassium carbonate was used as the alkaline agent, it was confirmed that the oxygen absorption capacity was significantly improved by adding the tannin compound. However, when Comparative Example 1 and Comparative Example 3 using other alkaline agents (sodium carbonate, calcium carbonate) are compared with Comparative Example 2 and Comparative Example 4, the tannin compound is added by adding the tannin compound. It was confirmed that the oxygen absorption capacity was reduced as compared with the case where there was no case, unlike the case of the example.

Further, in Example 2, a condensed tannin compound was used, and in Example 3, a hydrolyzed tannin compound was used. Both have the same oxygen absorption capacity, but it is confirmed that the oxygen absorption capacity is somewhat higher when the condensed tannin compound is used.

(4) Types of Carriers Example 2, Example 4, and Example 8 are compared. In these examples, wet silica having different physical properties is used as a carrier. In Examples 2 and 4, etc., wet silica having an average particle size of 100 μm or 150 μm is used, whereas in Example 8, an extremely small wet silica having an average particle size of 12.3 μm is used. The average pore diameter is also 690 Å, which is larger than 600 Å. The organic oxygen scavenger of Example 8 has a good oxygen absorbing ability. However, when the breathable packaging material is filled, powdering occurs and the fluidity is poor, which is not preferable in terms of production efficiency.

(5) Manufacturing method Example 5 and Example 9 are compared. In Example 9, the entire amount of the carrier is blended with the first mixed component, and the granulated product is prepared by mixing the third mixed component with the mixture of the first mixed component and the second mixed component. is doing. On the other hand, in Example 5, the carrier is blended with the first and third mixed components, respectively, and the third mixed component is mixed with the mixture of the first mixed component and the second mixed component. We are making granules. It was confirmed that an organic oxygen scavenger having high oxygen absorption capacity could be obtained in both cases, but as in Example 5, the carrier was used rather than the entire amount of the carrier being added to the first mixed component. It was confirmed that when each of the first and third mixed components was blended, the apparent density of the granulated product was higher, and an organic oxygen scavenger having good powder properties could be obtained from the viewpoint of production efficiency.

Finally, Example 5 and Example 10 are compared. In Example 5, the granulated product was prepared in the atmosphere, whereas in Example 10, the granulated product was prepared in the nitrogen atmosphere. Even if the content of each component and the method for producing the granulated product are the same, by producing the granulated product in the atmosphere, the powder has a higher oxygen absorption capacity and a higher apparent density of the granulated product. It was confirmed that an organic oxygen scavenger with good properties can be obtained.

According to the present invention, it is a carbon dioxide gas generating type organic oxygen scavenger, which has a good oxygen absorbing ability and the amount of carbon dioxide generated is about the same as the amount of oxygen absorbed. And a method for producing the same.

Claims (5)

A main agent, and an alkali agent, a water, a reaction catalyst, a method of manufacturing an organic-based oxygen scavenger for the production of organic oxygen scavenger consisting of granules containing a carrier,
Erythorbic acid salt was used as the main agent.
Potassium carbonate was used as the alkaline agent.
The first mixed component containing the main agent and the second mixed component containing the reaction catalyst and water are mixed, and the third mixed component containing the alkaline agent is mixed with the mixture to prepare the mixture. To be grained
The first mixed component comprises the carrier.
A method for producing an organic oxygen scavenger. The method for producing an organic oxygen scavenger according to claim 1 , wherein the third mixed component contains the carrier, and the carrier is blended with the first mixed component and the third mixed component, respectively. The method for producing an organic oxygen scavenger according to claim 1 or 2 , wherein the first mixed component contains a tannin compound. The third mixture component is organic method for producing oxygen scavenger as claimed in any one of claims 3, including a water-containing activated charcoal. In the air, a manufacturing method of an organic oxygen absorber according to any one of claims 1 to 4, wherein the third mixture component is mixed from the first mixture component.