JP5503445B2 - Organic oxygen scavenger manufacturing apparatus and organic oxygen scavenger manufacturing method - Google Patents

Description

  The present invention relates to an organic oxygen absorber that removes oxygen from the atmosphere by absorbing oxygen, and more specifically, an organic oxygen absorber manufacturing apparatus and an organic oxygen absorber that can maintain manufacturing efficiency throughout the year. It relates to the manufacturing method.

  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 is possible to absorb oxygen in the packaging container and store foods and the like in an oxygen-free atmosphere. For this reason, quality deterioration by oxidation etc. of food etc. can be prevented and food etc. can be distributed in a good state over a long period of time. As an oxygen scavenger, an iron oxygen scavenger mainly composed of iron powder and an organic oxygen scavenger material mainly composed of an organic easily oxidizable substance are known. Conventionally, iron-based oxygen scavengers have been widely used because they are inexpensive and have a stable oxygen absorption capacity.

  However, in recent years, metal detectors have been used in the process of distributing food, etc., and metal detectors have been inspected by metal detectors, and foods that are heated in their packaging containers in a microwave oven have been distributed. There is an increasing demand for organic oxygen scavengers that can be heated in a microwave oven without being detected. Therefore, the present applicant has proposed, for example, organic oxygen scavengers shown in Patent Documents 1 and 2.

  By the way, in the manufacturing process of an oxygen scavenger, an operation of filling a packaging material with a deoxidizing material as a raw material is performed. In this filling operation, for example, an automatic filling device as described in Patent Document 3 is used. The automatic filling device described in Patent Document 3 includes a measuring turntable that is rotatably provided, a hopper that supplies a deoxidizing material to the measuring turntable, and a plurality of measuring masses embedded in the measuring turntable. Yes. The hopper supplies deoxidized material to the approximate center of the surface of the weighing turntable. On the other hand, the weighing mass is concentrically embedded in the vicinity of the outer periphery of the surface of the weighing turntable. The deoxidizing material supplied from the hopper moves from the approximate center of the board surface to the outer peripheral side due to the centrifugal force accompanying the rotating operation of the weighing turntable. In the process, a deoxidizing material is put into the measuring mass. The shutter provided at the lower portion of the weighing mass opens in order from the weighing mass after the weighing is completed, and a predetermined amount of deoxidizing material is filled in the packaging material disposed below the weighing mass.

Japanese Patent Laid-Open No. 2007-76962 JP 2007-268326 A JP 2007-168831 A

  However, in the case of an organic deoxidizing material, when the atmospheric humidity increases, the organic deoxidizing material adheres to the inner wall surface of the weighing mass, and the metering cannot be performed correctly, resulting in a variation in filling amount. there were. For this reason, when an organic deoxidizing material adheres to the weighing mass, it is necessary to temporarily stop the filling operation of the organic deoxidizing material and perform a cleaning operation of the weighing mass, etc. It was the cause of the efficiency drop.

  Here, it is considered that the organic deoxidation material adheres to the weighing mass because the moisture content of the organic deoxidation material increases. For example, the present applicant has proposed an organic oxygen scavenger based on a hydroxyl-reactive type easily oxidizable organic substance in which the hydroxyl group contributes to the oxidation reaction. Since the hydroxyl group is a hydrophilic group, an organic deoxidation material mainly composed of a hydroxyl-oxidized easily oxidizable organic substance has a higher hygroscopicity than an iron-based deoxidation material. Further, the hydroxyl-oxidized easily oxidizable organic substance reacts with oxygen in the atmosphere to generate water. For this reason, when the atmospheric humidity increases, the moisture content of the organic deoxidizing material increases due to the moisture absorption of the organic deoxidizing material or the progress of the oxidation reaction. As a result, it is considered that the fluidity of the organic deoxidation material is reduced and adheres to the weighing mass.

  Therefore, in order not to be affected by the humidity change of the external atmosphere accompanying the changing seasons, it is conceivable to configure the surroundings of the weighing turntable in a closed system and keep the atmospheric humidity in the measurement turntable below a certain level. . However, since it is necessary to supply raw materials to the weighing turntable and a weighing mass having a lower opening is provided, the inside of the weighing turntable communicates with the external atmosphere. It is difficult to have a completely sealed structure around the measurement turntable including the portion communicating with the external atmosphere, while preventing the measurement turntable from rotating. In addition, regardless of whether organic deoxidizing material is attached to the weighing mass, the weighing turntable and the weighing mass require regular cleaning. It is thought that it falls.

  As described above, an object of the present invention is to provide an organic deoxidizing material manufacturing apparatus and an organic deoxidizing material manufacturing method capable of maintaining the manufacturing efficiency of an organic oxygen scavenger throughout the year with a simple configuration. With the goal.

  Accordingly, the inventors of the present invention have intensively studied to achieve the above object, and as a result, have come up with the following apparatus for producing an organic oxygen scavenger and a method for producing an organic deoxidizing material.

  An apparatus for producing an organic oxygen scavenger according to the present invention includes a measuring turntable to which an organic deoxidizing material is supplied, and a plurality of measuring masses to which the organic deoxidizing material is charged by a rotating operation of the measuring turntable. And a shutter that freely closes and opens the lower opening of the weighing mass, opens the shutter, and fills the packaging material disposed below the weighing mass with the weighed organic deoxidation material, In an organic oxygen scavenger manufacturing apparatus that manufactures an organic oxygen scavenger, the metering rotation is performed so that the average value when the oxygen concentration in the metering turntable is measured every minute is 3.25 vol% or less. Nitrogen supply means for supplying nitrogen into the panel is provided.

  In the apparatus for producing an organic oxygen scavenger according to the present invention, the nitrogen supply means performs the measurement so that the average value when the oxygen concentration in the measurement rotating disk is measured every minute is 1.5 vol% or less. Nitrogen is preferably supplied into the rotating disk.

In the apparatus for producing an organic oxygen scavenger according to the present invention, the nitrogen supply amount of the nitrogen supply means is 1.0 L / min to 2 per 1 L of the filling atmosphere volume (S) represented by the following formula (1). .4 L / min is preferable.
S = S _t −S _o (1)
However, in the above formula (1), S _t represents the total void volume (L) in the metering turntable, S _o is representative of the volume (L) occupied by organic deoxidizer within the metering turntable Yes.

  In the apparatus for producing an organic oxygen scavenger according to the present invention, it is preferable that the organic deoxidation material is mainly composed of an easily oxidizable organic substance having a hydroxyl group.

  In the apparatus for producing an organic oxygen scavenger according to the present invention, when the organic deoxidation material contains 100 parts by weight of the easily oxidizable organic substance as a main agent, it contains 10 parts by weight to 200 parts by weight of water as an auxiliary agent. It is preferable.

  The method for producing an organic oxygen absorber according to the present invention is an organic oxygen absorber for producing an organic oxygen absorber by filling a packaging material with a predetermined amount of an organic oxygen absorber using an automatic filling device. The automatic filling device includes a weighing turntable to which an organic deoxidation material is supplied, and a plurality of weighing masses to which the organic deoxidation material is charged by a rotation operation of the measurement turntable. And a shutter that freely opens and closes the lower opening of the weighing mass, while supplying nitrogen into the weighing turntable so that the oxygen concentration in the weighing turntable is 3.25 vol% or less, The organic deoxygenating agent is manufactured by opening the shutter and filling the measured organic deoxidation material in the packaging material disposed below the weighing mass.

  According to the present invention, the organic deoxidizing material is supplied by the measuring mass while supplying nitrogen into the measuring turntable so that the oxygen concentration in the measuring turntable is 3.25 vol% or less by the nitrogen supply means. By weighing, the humidity in the weighing turntable can be lowered and the oxidation reaction of the organic deoxidizing material can be prevented. This prevents the moisture content of the organic deoxidizing material from increasing, maintains the fluidity of the organic deoxidizing material, and prevents the organic deoxidizing material from adhering to the inner wall surface of the measuring mass. Can do. In addition, according to the above configuration, the configuration around the weighing turntable is not a sealed structure, but nitrogen is supplied to reduce the oxygen concentration in the weighing turntable, so the conventional apparatus configuration is greatly changed. Therefore, the production efficiency of the organic oxygen scavenger can be maintained throughout the year with a simple configuration.

It is a side view which shows typically the structure of the automatic filling apparatus as a manufacturing apparatus of the organic type oxygen absorber which concerns on this invention. However, the measuring turntable, the cover member, and the weathering member are shown in cross section. It is a perspective view which shows a measurement rotary disk and a measurement mass. It is a figure which shows the variation in the filling amount of the organic type oxygen absorber manufactured in Example 1- Example 3 and a comparative example.

  Hereinafter, embodiments of an organic oxygen scavenger manufacturing apparatus and an organic oxygen scavenger manufacturing method according to the present invention will be described. The organic oxygen absorber according to the present invention is obtained by packaging an organic deoxidizing material as a content with a packaging material. In the present embodiment, an automatic filling apparatus 100 shown in FIG. 1 will be described as an example of an organic oxygen scavenger manufacturing apparatus. An automatic filling device 100 shown in FIG. 1 is used for measuring a predetermined amount of an organic deoxidizing material and continuously packaging it in a packaging material. In the automatic filling device 100, the organic deoxidizing material is weighed in the rotation operation of the weighing turntable 20 using the weighing turntable 20 in which the weighing mass 10 (see FIG. 2) is embedded. When the packaging material is filled with an organic deoxidizing material, a method is employed in which a shutter that closes the lower opening of the weighing mass 10 is opened and dropped into the packaging material disposed below the weighing mass 10. The organic deoxidation material according to the present invention is prepared so as to maintain practical fluidity at the time of filling.

  However, as the humidity of the external atmosphere increases, the fluidity of the organic deoxidizing material decreases due to reasons such as moisture absorption. Specifically, when the relative humidity of the external atmosphere exceeds approximately 65%, the organic deoxidizing material adheres to the inner wall surface of the weighing mass 10 and the filling amount varies. In the present invention, when the packaging material is filled with the organic deoxidizing material, nitrogen is supplied so that the oxygen concentration of the filling atmosphere of the organic deoxidizing material is 3.25 vol% or less using the nitrogen supply means. Thus, the fluidity of the organic deoxidizing material can be maintained regardless of changes in the external atmosphere, and the production efficiency of the organic oxygen scavenger can be maintained throughout the year. Hereinafter, in the present embodiment, after describing the organic oxygen scavenger according to the present invention, the configuration of the automatic filling apparatus 100 shown in FIG. 1 will be described, and the nitrogen supply means will be described.

1. Organic oxygen scavenger 1-1 Organic deoxidation material First, the organic deoxidation material according to the present invention will be described. The organic deoxidation material according to the present invention appropriately contains, as well as a main component composed of an easily oxidizable organic substance, subcomponents required when the main component performs an oxidation reaction with oxygen in the atmosphere.

<Main agent>
Easily oxidizable organic substance: In the present invention, an easily oxidizable organic substance refers to an organic substance that readily undergoes an oxidation reaction with oxygen in the atmosphere, and is the main component of the organic deoxidation material according to the present invention. Examples of easily oxidizable organic substances include, for example, hydroxylated oxidizable organic substances having a hydroxyl group involved in an oxidation reaction with oxygen in the atmosphere, unsaturated fats and oils, unsaturated fatty acids, unsaturated polymers, and the like. A double bond oxidation type easily oxidizable organic substance in which a double bond is involved in an oxidation reaction with oxygen in the atmosphere can be mentioned. In the present invention, either a hydroxyl-oxidized easily oxidizable organic substance or a double-bond oxidized easily oxidizable organic substance may be used. In the following, a hydroxyl-oxidized easily oxidizable organic substance is taken as an example. I will give you a description.

  Specifically, as a hydroxyl-oxidized easily oxidizable organic substance, a compound compound (hereinafter referred to as polyphenol compound) containing two or more benzene rings containing one or more phenolic hydroxyl groups such as tannin or tannic acid in the chemical structural formula And polyhydric alcohol compounds such as ascorbic acid, glycerin and glycol, and monocyclic polyhydric phenol compounds such as catechol, hydroquinone and gallic acid. Among these, polyphenol compounds can be preferably used.

  The polyphenol compound is contained as a component of plant fruits, leaves, flowers, bark and the like. Specific examples of the polyphenol compound include tannin or tannic acid, catechin, quercetin, flavone, flavanone, flavonol, isoflavone, anthocyanin and the like as main components. As the polyphenol compound used in the present invention, either one produced by chemical synthesis or one extracted from a plant may be used. Moreover, as a polyphenol compound extracted from a plant, either a crude polyphenol compound containing impurities or a purified polyphenol compound from which impurities have been removed may be used. Examples of polyphenol compounds extracted from plants include condensed tannins extracted from quebracho and wattle (mimosa), hydrolyzed tannins extracted from chestnuts (chestnut astringents), tea catechins (teaflavin and epigallo) Examples thereof include a mixture of catechin gallate and the like, epigallocatechin gallate simple extract), cocoon polyphenol (anthocyanin), apple polyphenol (catechin and quercetin and the like), and the like. By using such a polyphenol compound, it is possible to obtain an organic deoxidation material that is inexpensive, highly safe, and has a desired deoxygenation performance.

  Among these polyphenol compounds, those containing at least one selected from tannin, tannic acid, catechin, quercetin, flavone, flavanone, flavonol, isoflavone, and anthocyanin are preferable. Among these, tannin or tannic acid, in particular, condensed tannin or tannic acid as the main component is the main agent because it is easily available, inexpensive, and exhibits sufficient oxygen absorption ability as the main agent. It is preferable to use as. Condensed tannins are difficult to change in the chemical structure of the main skeleton in response to changes in the atmospheric environment such as pH change, and at the same time, functional groups involved in the deoxygenation reaction are retained, so deoxygenation is independent of environmental changes. It is preferably used in terms of maintaining ability.

<Adjunct>
The organic deoxidation material according to the present invention contains water, an alkali agent, and other optional components added as an auxiliary agent together with the above-mentioned main agent. Water is added to act with the main agent and the alkaline agent or to dissolve the main agent and the alkaline agent and provide a field for the oxidation reaction of the main agent. The alkaline agent is a substance that acts or dissolves in water and exhibits alkalinity, and becomes an essential substance when the easily oxidizable organic substance as the main agent advances an oxidation reaction with oxygen in the atmosphere. Each will be described below.

Water: In the organic deoxidation material according to the present invention, when the main agent is 100 parts by weight, it is preferable to contain 10 parts by weight to 200 parts by weight of water. When the main agent is 100 parts by weight, by setting the water to 200 parts by weight or less, the practical fluidity when filling the packaging material with the mixture can be maintained. On the other hand, when the content of water is less than 10 parts by weight when the main agent is 100 parts by weight, each composition constituting the organic deoxidation material such as the main agent and the alkali agent is difficult to mix and the deoxygenation ability is lowered. . In addition, an appropriate amount of water is required to exhibit an appropriate deoxygenation capacity. Since the organic deoxidation material according to the present invention is used after being packaged in a breathable packaging material, if the water content of the organic deoxidation material is insufficient, the water content of the stored product is reduced. It is also possible to carry out the oxidation reaction by absorption. However, even in consideration of this point, when the water content is less than 10 parts by weight with respect to 100 parts by weight of the main agent, the amount of water required for the deoxygenation reaction is insufficient and it is difficult to absorb the water from the stored product. When it is, it becomes difficult to exhibit a desired deoxygenation capability. However, when the organic deoxidation material is used together with a stored product having a low water content, when the main agent is 100 parts by weight, it is preferable to contain 100 parts by weight or more of water. This is because by containing 100 parts by weight or more of water with respect to 100 parts by weight of the main agent, appropriate deoxygenation ability can be exhibited even when moisture cannot be absorbed from the stored product.

Alkaline agent: In the present invention, calcium hydroxide is used as the alkali agent. Compared with other alkaline agents that have been used in conventional organic deoxidizing materials, calcium hydroxide is less likely to cause a reaction such as hydrolysis on the oxidizable organic substance that is the main agent. It is also considered that calcium hydroxide can be stabilized at a pH suitable for the oxidation reaction of easily oxidizable organic substances by interaction with water. For this reason, by using calcium hydroxide as an alkaline agent, the functional group (hydroxyl group) related to deoxidation of the main agent can be stably maintained, and when the oxygen concentration in the atmosphere increases, the main agent and the atmosphere The oxidation reaction with the oxygen in the inside can be rapidly advanced. However, the pH range suitable for the oxidation reaction of the easily oxidizable organic substance is generally in the range of pH 9 to pH 12.

Here, the average particle diameter D ₅₀ of calcium hydroxide is preferably 0.5 μm to ₂₀₀ μm, more preferably 1 μm to 80 μm, and most preferably 2 μm to 60 μm. By using calcium hydroxide having such powder characteristics, an excellent deoxygenation capacity and deoxygenation rate can be realized. At the same time, in the production of the organic deoxidation material according to the present invention, it is possible to make it easy to become familiar with other compositions by kneading. That is, when the average particle diameter D _{50 of} calcium hydroxide is less than 0.5 μm, blocking occurs when the organic deoxidation raw material (main agent, auxiliary agent) is kneaded and powder flowability is reduced. . As a result, there are problems such as unevenness in the kneading state of the organic deoxidation raw material and adhesion of calcium hydroxide to the mixing container. Further, if the average particle size of the calcium hydroxide D ₅₀ is less than 0.5 [mu] m, easily dust calcium hydroxide whirled up, powder bite in the sealing portion when enclosed the organic deoxidizing material to wrapping material The seal may be incomplete. For this reason, defective products such as the appearance of the organic oxygen scavenger package as a product may be damaged, or powder leakage may occur from the seal portion. On the other hand, if the average particle diameter D ₅₀ of calcium hydroxide exceeds 200 [mu] m, the specific surface area of calcium hydroxide is reduced, since the reaction rate in the oxidation reaction of the deoxidizer is undesirably reduced.

Here, in this invention, it is preferable to use together calcium carbonate with the above-mentioned calcium hydroxide as an alkaline agent. When calcium hydroxide fine powder is used as the alkali agent, the specific surface area of calcium hydroxide is increased, and the reaction rate of the deoxygenation reaction (oxidation reaction) of the main agent is considered to be improved. However, as described above, the smaller the average particle diameter D ₅₀ of the calcium hydroxide, apt powder whirled up, the problem is likely to occur in kneading properties and fluidity with other compositions. Therefore, in the organic deoxidation material according to the present invention, it is preferable to use calcium carbonate together with calcium hydroxide as the alkaline agent. Calcium carbonate is an alkaline agent that is poorly soluble in water, has a large specific gravity, and when used as an alkaline agent together with calcium hydroxide, an effect of suppressing calcium hydroxide powdering can be obtained. In addition, it is considered that calcium carbonate carries the main agent and also functions as a carrier that provides a reaction field. Therefore, in the present invention, by using calcium carbonate together with calcium hydroxide as an alkaline agent, even when using fine calcium hydroxide suitable for promoting deoxygenation reaction, suppressing powdering during kneading, and Calcium carbonate carries the main agent and plays a role as an alkali agent. As a result, conventionally, there is no need to separately use a carrier such as silicon dioxide, and the amount of the alkali agent in the entire organic deoxidation material can be increased, so when compared with the case where a carrier such as silicon dioxide is used, Deoxygenation ability can be improved.

  When calcium carbonate is used in combination as the alkaline agent, it is preferable to use 5 to 50 parts by weight of calcium carbonate with respect to 100 parts by weight of calcium hydroxide. When the content of calcium carbonate is less than 5 parts by weight, when mixing the raw material components of the organic deoxidizing material, powdering occurs and fluidity is reduced. Not suitable for acid materials. On the other hand, calcium carbonate is a weak alkali agent, and when only calcium carbonate is used as an alkali agent for a deoxidizing material, the deoxidizing capacity of the deoxidizing material becomes insufficient. For this reason, when the content of calcium carbonate exceeds 50 parts by weight with respect to 100 parts by weight of calcium hydroxide, the content ratio of calcium carbonate in the alkaline agent increases, and the amount of deoxygenated per unit weight of the deoxidizing material is reduced. Since it decreases, it is not preferable.

  However, when calcium carbonate is not used together with calcium hydroxide, silicon dioxide, aluminum silicate, alumina, activated alumina, aluminum hydroxide, calcium silicate, diatomaceous earth, pearlite, zeolite, activated clay, etc. may be used as a support. it can.

Other subcomponents: In addition, as a subcomponent of the organic deoxidation material according to the present invention, a catalyst for increasing the oxidation reaction rate of the main agent may be included. As the catalyst, either an inorganic catalyst or an organic catalyst can be used. As an inorganic catalyst, for example, transition metal salts such as iron, nickel, copper and manganese, transition metal salts such as nitrate or sulfate, alkali metal salts such as sodium chloride, alkaline earth metal salts such as calcium chloride, etc. Can be mentioned. Further, as the organic catalyst, for example, an organic catalyst such as naphthohydroquinone, phloroglycine, t-butylcatechol, t-butylhydroquinone, 5-methylresorcin and the like can be used. Moreover, the organic deoxidation raw material which concerns on this invention is good also as a structure which contains activated carbon further as a subcomponent. By adding activated carbon as a composition, a low molecular weight substance generated after the oxidation reaction of the main agent can be captured and volatilization of the low molecular weight substance can be prevented.

Organic deoxidizer particle size: Average particle diameter D ₅₀ of the organic oxygen material according to the present invention, it depends on the average particle diameter D ₅₀ of the calcium hydroxide used as an alkaline agent. As the average particle diameter D ₅₀ of the calcium hydroxide used as the alkaline agent is small, the average particle diameter D ₅₀ of the organic deoxidizer produced also becomes smaller. With calcium hydroxide having an average particle diameter D ₅₀ in the range described above, by kneading the base resin, and other auxiliary agents, the particle size of the finally produced organic deoxidizer is a 500μm or less Yes, preferably 400 μm or less, most preferably 300 μm or less. However, it is set as the value measured using the scanning electron microscope (JSM-6060A) by JEOL Co., Ltd. for the measurement of the said particle size. The organic deoxidation material according to the present invention is thus fine particles and also has a high water content as an auxiliary agent. However, by using the automatic filling device 100 described later, an organic oxygen scavenger is manufactured by the method according to the present invention, and thus the packing material is continuously filled in the state of fine particles without going through the granulation step. It is possible.

1-2 Packaging Material The organic deoxidation material described above is packaged and used with a breathable packaging material. Because organic oxygen scavengers react with oxygen in the atmosphere and absorb oxygen in the atmosphere, if they are not packaged with a breathable packaging material, they cannot exhibit their oxygen scavenging ability. is there.

  The packaging material is preferably made of a material having moisture resistance and oil repellency in consideration of the usage mode of the organic oxygen scavenger. Since organic oxygen scavengers are enclosed in packaging containers together with stored products such as foods that contain moisture and oil, if moisture or oil that has been leached from foods etc. touches organic deoxidation materials via the packaging material This is because the oxygen absorption capacity of the organic deoxidizing material may be reduced. Furthermore, considering the manufacturing process of the organic oxygen scavenger, the packaging material is preferably heat-sealing because it is heat-sealed to form a bag as will be described later.

Composite film: As the packaging material according to the present invention, any material may be used as long as it has the above-mentioned properties. In the present invention, a composite film obtained by laminating an outer layer material and an inner layer material by lamination, or A composite film obtained by laminating an outer layer material and an inner layer material and further laminating an outermost layer film on the outer layer material side can be suitably used. By using such a composite film, the materials required for the outer layer material and the inner layer material are appropriately selected, and if necessary, the outer layer film is further laminated on the outer side of the outer layer material, thereby requiring the above-mentioned packaging material. That is, air permeability, moisture resistance and oil repellency, and heat sealability can be satisfied. For example, as the outermost layer film, a perforated resin film in which a plurality of fine through holes are provided in a thermoplastic resin film can be used. Specifically, a perforated polyester film, a perforated polyethylene film, a perforated polypropylene film, or the like can be used. The outer layer material is paper, woven fabric, non-woven fabric, etc., which can be bonded to the inner layer material, or laminated with the inner layer material and the outermost layer film, and has air permeability even after bonding. It is preferable that it is comprised. Specifically, kraft paper, oil repellent paper, water repellent paper and the like can be used as the paper, and examples of the woven fabric and non-woven fabric include woven fabric and non-woven fabric made of polyester, polyamide and the like. Further, as the inner layer material, it is preferable to use a material capable of heat-sealing the inner layer materials by heat sealing. Specifically, a material made of polyethylene such as low density polyethylene and linear low density polyethylene is preferably used. it can.

2. Automatic filling device 100 (Organic oxygen absorber production device)
Next, the automatic filling apparatus 100 of this Embodiment is demonstrated. As shown in FIG. 1, the automatic filling device 100 of the present embodiment includes a hopper 30 that stores an organic deoxidation material as a raw material, and a weighing turntable 20 that is supplied with the organic deoxidation material from the hopper 30. And a plurality of weighing masses 10 (see FIG. 2) into which the organic deoxidation material is charged by the rotating operation of the weighing turntable 20. However, in FIG. 1, the weighing turntable 20 shows a cross section thereof.

  The automatic filling apparatus 100 also includes a shutter (not shown) that closes the lower opening of the weighing mass 10 so as to be freely opened and closed. The shutter opens and closes when the weighing mass 10 rotates to a pre-positioned raw material filling position. An opening / closing mechanism is provided. A filling chute 40 is provided below the measuring turntable 20 to guide the organic deoxidized material falling from the measuring hole 11 to the packaging material at the raw material charging position. Moreover, as a packaging material, what has the heat seal property formed in the elongate sheet form is used. Further, the automatic filling device 100 is provided with a heat seal portion so that the packaging material formed in the long sheet shape is folded in two along the longitudinal direction with the crease down, and perpendicular to the crease at a predetermined interval. A continuous bag body having an upper opening serving as an enclosure port is formed, and a bag-making conveyance unit (not shown) for continuously supplying the packaging material below the filling chute 40 in this state is provided. Hereinafter, each component will be described.

Hopper 30: The hopper 30 is a storage container that stores an organic deoxidation material as a raw material. The hopper 30 has a raw material inlet 31 at the top and a raw material outlet 32 at the bottom. The raw material discharge port 32 is disposed close to the surface 21 of the weighing turntable 20. The organic deoxidation material accommodated in the hopper 30 falls by its own weight and is supplied to the approximate center of the surface 21 of the weighing turntable 20 through the material discharge port 32. However, the hopper 30 is supported by the hopper support member 60 so that the raw material discharge port 32 is positioned substantially at the center of the weighing turntable 20.

Weighing turntable 20: As shown in FIG. 2, the weighing turntable 20 has a substantially disk shape as viewed from above and receives a raw material discharged from the hopper 30, and is supported so as to be horizontally rotatable. A plurality of through-holes 22 penetrating in the thickness direction are provided concentrically on the outer peripheral side of the measuring turntable 20 on the surface 21 of the measuring turntable 20, and the measuring mass 10 is detachable in each of the through-holes 22. Buried. An outer peripheral wall 23 is provided upright at the outer peripheral end of the surface 21 of the weighing turntable 20 so that the organic deoxidizing material is not scattered outside the measurement turntable 20 by centrifugal force. .

Cover member 50: Further, as shown in FIG. 1, the circumference of the weighing turntable 20 is covered with a cover member 50. The cover member 50 is also shown in cross section in FIG. The cover member 50 has an upper surface portion 51 that covers the upper portion of the weighing turntable 20 and an outer peripheral portion 52 that covers the outer peripheral surface of the outer peripheral wall 23 of the measurement turntable 20. A substantially circular opening is formed in the approximate center of the upper surface portion 51, and the lower portion of the hopper 30 described above is inserted. The cover member 50 is supported by the hopper support member 60. At this time, a gap is provided between the upper surface portion 51 of the cover member 50 and the upper end of the outer peripheral wall 23 of the weighing turntable 20 so as not to hinder the rotation operation of the measurement turntable 20. Further, a gap is also provided between the outer peripheral portion 52 of the cover member 50 and the outer peripheral wall 23 of the measuring turntable 20. Thus, the cover member 50 is fixed to the hopper support member 60 in a state where the cover member 50 and the weighing turntable 20 are separated from each other. By covering the periphery (upper part and outer periphery) of the weighing turntable 20 with the cover member 50, the organic deoxidizing material in the measurement turntable 20 is scattered outside beyond the outer peripheral wall 23 of the measurement turntable 20. Can be prevented.

  Further, the cover member 50 is configured to be divided into two or three in consideration of maintainability when cleaning the weighing turntable 20 or the weighing mass 10 or the like. That is, the cover member 50 having the above shape is configured by combining two or three divided members having a part of the upper surface part 51 and a part of the outer peripheral part 52. Then, the cover member 50 covers the weighing turntable 20 and the outer periphery of the hopper 30 on the raw material discharge port 32 side, and is fixed to the hopper support member 60, and then the outer periphery of the hopper 30 and the upper surface portion of the cover member 50. Between the opening formed in the approximate center of 51, it is lined using a lined member 70. In this way, the outer periphery of the hopper 30 inserted on the board surface 21 side of the weighing turntable 20 is conspicuous with the outer periphery on the raw material discharge port 32 side through the opening formed in the approximate center of the upper surface portion 51 of the cover member 50. Accordingly, it is possible to prevent the organic deoxidizing material from being scattered from the cover portion to the outside of the cover member 50.

  The weathering member 70 may be configured to fill a gap between the outer periphery of the hopper 30 and the cover member 50 using, for example, a sealant, caulking, or the like. However, in consideration of removing the cover member 50 during maintenance, a commercially available weather tape, an adhesive tape such as a craft tape, a gum tape, or the like can be suitably used as the weather member 70. By using these adhesive tapes, after attaching the cover member 50, it is possible to easily mark the part, and when removing the cover member 50, the weathering member 70 can be easily removed.

  In addition, a temperature sensor, a humidity sensor, and an oxygen concentration sensor (all not shown) are attached to the back surface side of the upper surface portion 51 of the cover member 50, that is, the side facing the inner side of the weighing turntable 20, and these Using the sensor, the temperature, humidity, and oxygen concentration in the weighing turntable 20 can be measured at any time.

Weighing mass 10: As shown in FIG. 2, the weighing mass 10 has the same thickness as the board surface 21 of the weighing rotating board 20, and has a measuring hole 11 penetrating in the thickness direction of the board surface 21. That is, the weighing mass 10 is formed in a ring shape. The outer diameter of the weighing mass 10 is substantially equal to the diameter of the through hole 22 formed in the weighing turntable 20 and is detachably embedded in each through hole 22. The capacity that can be measured by the measuring mass 10 is determined by the hole diameter of the measuring hole 11 and the thickness of the measuring mass 10. A plurality of measuring masses 10 having different hole diameters of the measuring holes 11 are prepared, and can be replaced with a measuring mass 10 having an appropriate hole diameter as appropriate according to the filling amount of the organic deoxidation material. However, when producing an organic oxygen scavenger, since products with the same filling amount are usually produced continuously, each through hole 22 of the measuring turntable 20 has the same diameter as the measuring hole 11. Are buried.

Shutter: The shutter closes the lower opening of the measuring hole 11 formed in the measuring mass 10 so as to be freely opened and closed. The shutter is provided on the back side of the surface 21 of the weighing turntable 20 for each through hole 22 and functions as a lower lid of the weighing mass 10 embedded in the through hole 22. Then, when the weighing mass 10 moves to a predetermined raw material filling position with the rotation of the weighing turntable 20, the shutter is opened, and the organic deoxidation material in the weighing mass 10 falls due to its own weight. The packaging material is filled through the filling chute 40. At this raw material filling position, a shutter opening / closing mechanism (not shown) is provided that opens the shutter only while the weighing mass 10 passes through the raw material filling position.

Filling Chute 40: As shown in FIG. 1, the filling chute 40 is formed in a funnel shape, and is provided at the raw material filling position. Under the filling chute 40, a bag inlet for the bag transported by the bag making transport unit described above is disposed. The organic deoxidizing material dropped from the weighing mass 10 is filled into the bag body through the filling chute 40.

Mass cutting plate: Further, a mass cutting plate (not shown) is provided on the surface 21 of the weighing rotating plate 20 to cut the weighing mass 10 when the weighing mass 10 passes below. Yes. In the present embodiment, since the weighing mass 10 is embedded in the board surface 21 of the weighing turntable 20, the plate end face of the mass cutting plate is arranged so as to be in contact with or close to the board surface 21. The organic deoxidizing material supplied to the approximate center of the board surface 21 is thrown into the weighing mass 10 embedded in the board surface 21 by centrifugal force as the weighing turntable 20 rotates. Then, by passing below the mass cutting plate, the measuring mass 10 is cut, and the measuring mass 10 into which a predetermined amount of the organic deoxidizing material is charged moves toward the raw material filling position. The mass cutting plate cuts the weighing mass 10 and partitions the panel surface 21 into the weighing side and the filling side so that the organic deoxidizing material does not move to the weighing mass 10 side that has passed through the mass cutting plate. It also functions as a partition plate.

Bag making and conveying section: The bag making and conveying section described above folds a long sheet-like packaging material into two along the longitudinal direction so that the crease is sideways, and at regular intervals so as to be orthogonal to the crease. A continuous bag body is formed by heat-sealing, and the packaging material is continuously conveyed so that the upper opening as the sealing port is located below the filling sheet. Note that after the bag body is filled with a predetermined amount of the organic deoxidizing material, the upper opening of the bag body is heat-sealed by a top seal device (not shown). As a result, an organic oxygen scavenger is produced in which an organic deoxidizing material is sealed in a bag formed of a packaging material.

3. Nitrogen supply means configuration: Next, the nitrogen supply means will be described. The nitrogen supply means supplies nitrogen into the weighing turntable 20, and connects, for example, a nitrogen cylinder storing nitrogen or a nitrogen generator, and the nitrogen cylinder or nitrogen generator and the inside of the measurement turntable 20. A nitrogen supply tube 81, a nitrogen cylinder or a nitrogen generator, and a flow rate adjusting valve provided at a connection portion between the nitrogen supply tube 81 and the like are configured. The nitrogen supply tube 81 is inserted through the insertion hole 53 formed in the cover member 50. And the nitrogen supply amount supplied in the measurement turntable 20 can be adjusted by adjusting the valve opening degree of a flow regulating valve.

  Here, as the organic deoxidation material according to the present invention, an organic deoxidation material mainly composed of the hydroxyl-oxidized easily oxidizable organic material can be suitably used. In this case, the organic deoxidation material is prepared so as to contain 10 parts by weight to 200 parts by weight of water as an auxiliary agent when containing 100 parts by weight of the easily oxidizable organic substance as the main agent. This means that, as described above, it is possible to maintain practical fluidity when filling the packaging material with the organic deoxidizing material by setting it to 200 parts by weight or less of water, and to contain 10 parts by weight or more of water. In order to make it easy to mix each composition and to exhibit an appropriate deoxygenation ability.

  However, a hydroxyl-oxidized easily oxidizable organic substance has a hydroxyl group, which is a hydrophilic group, and therefore has high hygroscopicity. For this reason, when the atmospheric humidity in the measuring turntable 20 increases, it is conceivable that the easily oxidizable organic material absorbs moisture, and the moisture content of the organic deoxidizing material increases by the moisture content absorbed. Further, water is added as an auxiliary agent in order to provide a reaction field for the main agent to perform a deoxygenation reaction and to exert an appropriate deoxygenation capability. For this reason, when the content of water increases due to moisture absorption, it is considered that the deoxygenation ability of the oxidation reaction of the easily oxidizable organic substance is improved. When the easily oxidizable organic substance reacts with oxygen in the atmosphere, water is by-produced by the reaction between the hydroxyl group and oxygen. Accordingly, when the external atmosphere around the measuring turntable 20 becomes humid, the hydroxyl-oxidized easily oxidizable organic substance absorbs moisture or the oxidation reaction proceeds, so that the water content of the organic deoxidizing material becomes the moisture during preparation. It is considered that the fluidity of the organic deoxidizing material is lowered due to the increase in amount. However, in the present invention, when the external atmosphere is humid, when the relative humidity is about 65% or more and / or when nitrogen is not supplied into the measuring turntable 20, the inner wall surface of the measuring mass 10 is organic. Humidity to the extent that system deoxidation material begins to adhere.

  Therefore, when the surrounding external atmosphere in the measuring turntable 20 becomes humid and the organic deoxidizing material adheres to the inner wall surface of the measuring mass 10, the measuring turntable is turned on by the nitrogen supply means. Nitrogen is preferably supplied so that the oxygen concentration in 20 falls within the following range. By supplying nitrogen so that the oxygen concentration is in the following range, the fluidity of the organic deoxidizing material can be maintained. Thereby, even when the external atmosphere is humid, the organic deoxidizing material is prevented from adhering to the inner wall surface of the measuring mass 10, the variation in the filling amount with respect to the packaging material is prevented, and the production efficiency is maintained throughout the year. be able to.

Here, when the oxygen concentration in the measuring turntable 20 is measured every minute by the nitrogen supply means, nitrogen is supplied so that the average value is 3.25 vol% or less. It is preferable to do. Although the oxygen concentration in the atmosphere is about 20.8 vol%, the above effect can be obtained by supplying nitrogen into the measuring turntable 20 to reduce the oxygen concentration to 3.25 vol% or less. Even when nitrogen is supplied into the measuring turntable 20 by the nitrogen supply means, if the average value when the oxygen concentration is measured every minute after the start of nitrogen supply exceeds 3.25 vol%, the external atmosphere Is humid, it tends to be difficult to maintain the fluidity of the organic deoxidizing material, and adhesion to the weighing mass 10 can be seen. For this reason, the production efficiency of the organic oxygen scavenger varies according to the change in the external atmosphere.

  At this time, it is more preferable to supply nitrogen so that the average value of the oxygen concentration measured every minute after supplying nitrogen into the measuring turntable 20 is 1.5 vol% or less. More preferably, nitrogen is supplied so as to be 0.0 vol% or less. If the average oxygen concentration measured every minute after the oxygen concentration in the measuring turntable 20 starts supplying nitrogen is 1.5 vol% or less, the humidity in the measuring turntable 20 can be reduced. In addition, the reaction between the organic deoxidizing material and the oxygen in the atmosphere during the filling operation can be extremely effectively reduced. For this reason, the oxygen scavenging ability of the organic oxygen scavenger obtained as the final product is increased. As the oxygen concentration in the measuring turntable 20 decreases, the deoxygenation ability tends to increase. Therefore, it is more preferable to supply nitrogen into the measurement turntable 20 by the nitrogen supply means so that the oxygen concentration in the measurement turntable 20 is 1.0 vol% or less.

Average concentration reaching time: It is preferable to supply nitrogen by the nitrogen supplying means so that the oxygen concentration of the weighing turntable 20 reaches the above range within a predetermined average concentration reaching time after the supply of nitrogen is started. . Specifically, the average concentration arrival time is preferably within 5 minutes, more preferably within 3 minutes, and even more preferably within 2 minutes. As described above, the cover member 50 is disposed away from the outer peripheral wall 23 so as not to hinder the rotation operation of the weighing turntable 20, and the cover member 50 is provided with the weighing mass 10 embedded in the board surface 21 of the measurement turntable 20. The lower opening is opened at the raw material filling position. Thus, since the inside of the measurement turntable 20 communicates with the external atmosphere, the oxygen concentration in the measurement turntable 20 before supplying nitrogen is about 20.8%, which is equal to the external atmosphere. When the supply of nitrogen is started, oxygen in the measuring turntable 20 is replaced with nitrogen, and the oxygen concentration in the measuring turntable 20 gradually decreases. Therefore, the shorter the time from the start of the supply of nitrogen until the average value of the oxygen concentration reaches the above-mentioned range, the oxygen concentration in the measuring turntable 20 is quickly reduced, and the humidity in the measuring turntable 20 is increased. Can be quickly reduced. As a result, it is possible to prevent a decrease in fluidity of the organic deoxidation material even immediately after the start of nitrogen supply, thereby reducing variations in the filling amount of the organic oxygen absorber produced immediately after the start of nitrogen supply. it can. Here, when the time until the average value of the oxygen concentration in the measuring turntable 20 is within the above range exceeds 5 minutes, the moisture content increases due to the moisture absorption of the organic deoxidizing material or the progress of the oxidation reaction. As a result, the fluidity of the organic deoxidizing material is lowered, so that the organic deoxidizing material adheres to the inner wall surface of the measuring mass 10. On the other hand, if the average value of the oxygen concentration until 5 minutes elapses is within the above range, the practical fluidity of the organic deoxidizing material can be maintained even if the external atmosphere is humid. Further, it is possible to prevent the organic deoxidation material from adhering to the inner wall surface of the weighing mass 10 and to prevent variation in the filling amount. In order to prevent the fluidity of the organic deoxidizing material from decreasing at an earlier stage, it is better that the average concentration time is shorter. Therefore, the average concentration arrival time is more preferably within 3 minutes, and even more preferably within 2 minutes. When actually manufacturing an organic oxygen absorber using the automatic filling apparatus 100 shown in FIG. 1, the organic oxygen absorber is charged at a rate of 40 to 100 per minute. Since 100 to 200 organic oxygen absorbers are packaged and shipped in one bag, they are manufactured at a rate of 1 to 5 minutes per bag. Therefore, by reducing the oxygen concentration of the metering turntable 20 within the above-mentioned range, even when an organic oxygen scavenger is produced immediately after the start of nitrogen supply, the variation in the filling amount is reduced, and the production yield is reduced. Can be improved.

Variation in oxygen concentration: Further, when the oxygen concentration is measured every minute, it is preferable that the variation in the measured value is small. Specifically, after the average value of the oxygen concentration falls within the above range, the difference in the oxygen concentration value measured every minute is preferably within 1.0 vol%, and within 0.3 vol% It is more preferable that it is 0.1 vol% or less. By maintaining the fluctuation of the oxygen concentration in the measuring turntable 20 within the above-mentioned range, the progress of the oxidation reaction of the organic deoxidation material is prevented, and an organic deoxygenating agent having a more homogeneous deoxygenation capacity is continuously added. Can be manufactured in large quantities. When the difference between the values before and after the measured value of oxygen concentration measured every minute exceeds 1.0 vol%, the variation of oxygen concentration in the measuring turntable 20 becomes large, and a homogeneous product is continuously manufactured. May be difficult.

Nitrogen supply amount: Here, the nitrogen supply means has a nitrogen supply amount of 1.0 L / min to 2.4 L per 1 L of filling atmosphere volume (S) represented by the following formula (1) in the measuring turntable 20. / Min is preferable.
(Formula) S = S _t −S _o (1)
However, the filling atmosphere volume (S) represented by the following formula (1) is the volume S occupied by the organic deoxidation material in the measuring turntable 20 with the total space volume in the measuring turntable 20 being S _t (L). _{When o} (L), it means the volume represented by

In the present embodiment, the “total space volume on the weighing turntable 20” means “the volume of the space partitioned by the face 21 of the measurement turntable 20, the outer peripheral wall 23, and the top surface portion of the cover member 50. ". And when not covering the circumference | surroundings of the measurement turntable 20 with the cover member 50, it points out "the volume of the space partitioned off by the board surface 21 and the outer peripheral wall 23 of the measurement turntable 20," and the top surface part is set to the measurement turntable 20 itself. When the cover member 50 that covers is integrally attached, “the volume of the space partitioned by the board surface 21, the outer peripheral wall 23, and the top surface part of the measuring turntable 20” is indicated. On the other hand, the volume occupied by the organic deoxidizing material (S _o ) refers to the volume occupied by the organic deoxidizing material in the measuring turntable 20.

  When the nitrogen supply amount is less than 1.0 L / min per 1 L of the filling atmosphere volume (S) of the measuring turntable 20 expressed by the above formula (1), the oxygen in the measurement turntable 20 measured every minute The average value of the concentration cannot be in the above range, and the practical fluidity of the organic deoxidizing material cannot be maintained. Further, when the nitrogen supply amount exceeds 2.5 L / min, the rate at which nitrogen flows into the weighing turntable 20 becomes too fast, and air flows from the gap between the weighing turntable 20 and the cover member 50, and the weighing is performed. On the contrary, the oxygen concentration in the turntable 20 may increase and a desired effect may not be obtained. From this point of view, the nitrogen supply amount is more preferably 1.8 L / min or less, and further preferably 1.5 L / min or less per 1 L of the above-mentioned filled atmosphere volume (S). However, the relationship between the oxygen concentration in the metering turntable 20 and the nitrogen supply amount depends on the size and shape of the metering turntable 20, the volume occupied by the organic deoxidizing material in the metering turntable 20, the metering turntable 20 and the cover member. Since it varies depending on the size and shape of the gap with respect to 50, it is not strictly limited to the above range, and it is preferable to appropriately supply the amount according to the embodiment.

For example, to give a specific example, the inner diameter of the measuring turntable 20 is 350 mm (outer diameter 354 mm), the height of the measuring turntable 20 is 80 mm, and from the surface 21 of the measuring turntable 20 to the upper surface portion 51 of the cover member 50. When the height of is 90 mm, the total space volume (S _t ) in the weighing turntable 20 is obtained by the following equation (2).
S _t = π × (350/2) ² × 90 = 8.7 (L) (2)

When the organic deoxidizing material occupies up to half the height of the outer peripheral wall 23 in the measuring turntable 20, the volume (S _o ) occupied by the organic deoxidizing material in the measuring turntable 20 is expressed by the following formula ( 3).
S _o = π × (350/2) ² × (80 × 1/2) = 3.8 (L) (3)

At this time, the filling atmosphere volume (S) in the measuring turntable 20 (including the top surface portion formed by the cover member 50) is a value obtained from the above formula (1) by the above formulas (2) and (3). It can be obtained by substituting.
S = 8.7-3.8 = 4.9 (L)

  The filling atmosphere volume (S) obtained as described above is 4.9 L, the inner diameter of the upper surface portion 51 of the cover member 50 is 358 mm, the upper end of the outer wall of the measuring turntable 20 and the upper surface portion 51 of the cover member 50. When there is a gap of 10 mm between the first and the second, the amount of nitrogen supplied into the measuring turntable 20 is preferably 4.9 L / min to 12.3 L / min. At this time, the nitrogen supply amount is more preferably 6.4 L / min to 8.8 L / min, and further preferably 6.9 L / min to 7.4 L / min.

  By the way, when supplying nitrogen gas into the inside of the measurement turntable 20, a plurality of nitrogen supply points may be provided. By supplying nitrogen gas into the measuring turntable 20 from a plurality of locations, it becomes easy to make the oxygen concentration or nitrogen concentration in the measuring turntable 20 uniform. In this case, for example, regardless of the humidity of the external atmosphere, nitrogen is always supplied from one location at a constant amount or at a constant rate, and from other locations, the supply amount or supply of nitrogen is changed according to the humidity change of the external atmosphere. It is also a preferable aspect to change the speed. The organic deoxidation material according to the present invention performs a deoxygenation reaction that reacts with oxygen in the atmosphere and absorbs oxygen in the atmosphere. Therefore, it is preferable to fill the organic deoxidizing material in a nitrogen-substituted atmosphere regardless of the humidity of the external atmosphere. In this case, when the relative humidity of the external atmosphere is 65% or less, it is sufficient to supply nitrogen so that the oxygen concentration in the measuring turntable 20 is 6.0 vol% or less, more preferably 5.2 vol% or less. When the relative humidity of the external atmosphere exceeds 65% and the organic deoxidizing material adheres to the inner wall surface of the measuring mass 10, the oxygen concentration in the measuring turntable 20 is as described above. Nitrogen may be supplied from another location so that it becomes 3.25 vol% or less.

  For example, the filling atmosphere volume (S) represented by the above formula (1) exemplified as a specific example is 4.9 L, and a 10 mm gap is provided between the upper end of the outer peripheral wall 23 and the upper surface portion 51 of the cover member 50. In some cases, the oxygen concentration in the measuring turntable 20 can be reduced to about 5.1% by constantly supplying nitrogen at a rate of 2 L / min from one location regardless of the humidity change in the external atmosphere. And the oxygen concentration in the measuring turntable 20 measured every minute by supplying nitrogen in the range of 2.9 L / min to 10.31 L / min according to the humidity of the external atmosphere from the other location. The average value can be adjusted to about 0.9 vol% to 3.25 vol% within 5 minutes. At this time, it is more preferable to supply nitrogen into the measuring turntable 20 in the range of 4.4 L / min to 10.3 L / min, and supply in the range of 4.9 L / min to 5.4 L / min. It is more preferable.

  However, from the viewpoint of preventing reaction of the organic deoxidation material with atmospheric oxygen during the filling operation, it is preferable to supply nitrogen gas into the hopper 30 as well. In this case, for example, a plurality of nitrogen supply holes for supplying nitrogen into the hopper 30 are formed, and a nitrogen supply tube 81 connected from a nitrogen cylinder or a nitrogen generator is inserted into the nitrogen supply hole. can do.

  Further, as described above, the adjustment of the valve opening degree of the flow rate adjustment valve provided in the nitrogen supply means may be performed manually or by automatic control. In any case, the nitrogen supply amount may be increased or decreased according to the oxygen concentration in the measuring turntable 20 output from the oxygen concentration sensor attached to the upper surface portion 51 of the cover member 50. By conducting an experiment or the like in advance, the correlation between the nitrogen supply amount and the oxygen concentration in the measuring turntable 20 is checked, and the oxygen concentration in the measuring turntable 20 is constant so as to become a predetermined concentration. It is good also as a structure which supplies nitrogen with nitrogen supply amount. Furthermore, an external atmospheric humidity measuring means for measuring the humidity of the external atmosphere is provided, and when the humidity measured by the external atmospheric humidity measuring means is equal to or higher than a predetermined humidity, the nitrogen supply means starts supplying nitrogen. It is good also as a structure which provides the control means to control. Further, the control means is connected to an oxygen concentration sensor and / or humidity sensor, and based on the oxygen concentration detection signal and / or humidity detection signal input from these sensors, the valve of the flow rate adjustment valve provided in the nitrogen supply means It is good also as a structure which adjusts an opening degree.

  As described above, when the organic deoxidizing material is filled into the bag body by using the automatic filling apparatus 100 to produce the organic oxygen scavenger, the nitrogen supply means is used when the external atmosphere is humid. Thus, by supplying nitrogen so that the average value when the oxygen concentration in the measuring turntable 20 is measured every minute is 3.25 vol% or less, the organic deoxidation is performed regardless of the change in the external atmosphere. The practical fluidity of the material can be maintained and the production efficiency of the organic oxygen scavenger can be maintained throughout the year. Further, as described above, the nitrogen supply means is configured to form the insertion hole 53 in the cover member 50 that covers the circumference of the weighing turntable 20 and supply nitrogen through the insertion hole 53 through the nitrogen supply tube 81. Therefore, the oxygen concentration in the weighing turntable 20 can be within the above-described range with a simple configuration without greatly changing the conventional configuration of the automatic filling device 100.

  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.

<Adjustment of organic deoxidation material>
First, 11 g of condensed tannin (kebracho extracted tannin) as a main ingredient and 11 g of water were mixed. To this mixture, 0.14 g of t-butylcatechol was added as a reaction catalyst and mixed. Subsequently, calcium hydroxide (average particle diameter D ₅₀ = 4.7 μm) and 13.0 g of calcium carbonate were added to the mixture in this order as an alkaline agent and kneaded. Thereafter, 2.0 g of activated carbon was added, and further kneaded and then aged to obtain an organic deoxidation material (organic deoxidation material). That is, it was set as the structure which contains 100 weight part of water with respect to 100 weight part of organic easily oxidizable substances as a main ingredient. At this time, the particle size of the obtained organic deoxidation material was 385 μm or less. However, it is set as the value measured using the scanning electron microscope (JSM-6060A) by JEOL Co., Ltd. for the measurement of the said particle size.

<Packaging material>
As a packaging material for packaging the organic deoxidized material prepared as described above, an outermost layer film made of a perforated polyester film having a thickness of 12 μm, an outer layer material made of 50 g / m ² of water-resistant and oil-resistant paper, and a thickness of 25 μm. A composite film was used in which the inner layer material made of the perforated polyester was made into a three-layer laminate by heat lamination.

<Manufacture of organic oxygen scavenger>
The organic deoxidation material prepared as described above was continuously filled into 200 bags formed of the above-described packaging material using the automatic filling device 100 shown in FIG. 1, and the variation in the filling amount was examined. . The inner diameter of the weighing turntable 20 of the automatic filling device 100 used at this time was 350 mm. Further, the height of the outer peripheral wall 23 of the measuring turntable 20 (height from the board surface 21) was 80 mm. Furthermore, the inner diameter of the upper surface portion 51 of the cover member 50 that covers the circumference of the measuring turntable 20 is 358 mm, and the upper surface portion 51 is disposed 10 mm away from the upper end of the outer peripheral wall 23. Further, the gap between the opening formed in the center of the cover member 50 and the outer periphery of the hopper 30 was stretched using a gummed tape. The organic deoxidizing material was supplied into the measuring turntable 20 from the surface 21 to a height of about 40 mm.

Therefore, the total space volume (S _t ) in the weighing turntable 20 surrounded by the board surface 21 and the outer peripheral wall 23 of the weighing turntable 20 and the upper surface portion 51 of the cover member 50 is 8.7 L. The volume (S _o ) occupied by the organic deoxidation material is 3.8 L, and when these are substituted into the above equation (1), the filling atmosphere volume (S) in the measuring turntable 20 is 8.7 L-3. It was 8L = 4.9L.

Nitrogen supply amount: At this time, a nitrogen supply tube 81 connected to a nitrogen cylinder (liquefied nitrogen manufactured by Taiyo Nissan Corp.) via a flow rate adjustment valve is measured via an insertion hole 53 formed in the upper surface portion 51 of the cover member 50. It was inserted into the inside of the turntable 20. Then, nitrogen was supplied into the measuring turntable 20 through the nitrogen supply tube 81 at a rate of 5 L / min. That is, the supply amount of nitrogen was set to 1.0 L / min with respect to 1 L of the filling atmosphere volume (S) in the measuring turntable 20. However, in Example 1, nitrogen was supplied into the inside of the weighing turntable 20 from two places. The nitrogen supply rate at one location was 2 L / min, and the nitrogen supply rate from the other location was 3 L / min. At this time, when the oxygen concentration in the measuring turntable 20 was measured every minute, the average value of the oxygen concentration from the start of nitrogen supply until 5 minutes passed was 3.2 vol%. In the following, “the nitrogen supply amount per 1 L of the filling atmosphere volume (S) in the measuring turntable 20” is referred to as “the nitrogen supply amount per unit”, and “the actual nitrogen supply amount in the measurement turntable 20”. This is referred to as the total nitrogen supply.

  As described above, the organic deoxidizing material was filled into the bag formed of the packaging material at a filling rate of 70 pieces per minute while supplying nitrogen into the measuring turntable 20. At this time, the measuring mass 10 having the measuring holes 11 that can be filled with 0.9 g of organic deoxidizing material for each bag was used. And the weight of the organic deoxidation material with which the inside of the bag body was filled one by one was measured, and the variation in filling amount was investigated. Further, the obtained organic oxygen scavenger was left indoors at room temperature, and the amount of oxygen absorbed was measured after 1 day and after 4 days, respectively.

  In Example 2, except that the total nitrogen supply amount was increased from 5 L / min to 7 L / min, the amount of filling was set to 0.9 g in 201 bags by the same method as Example 1, and the organic system was used. Filled with deoxidized material. At this time, the nitrogen supply amount per unit is about 1.4 L / min. Further, similarly to Example 1, nitrogen is supplied from two locations into the measuring turntable 20, the nitrogen supply amount at one location is set to 2 L / min, and the nitrogen supply rate from the other location is increased to 5 L / min. did. At this time, when the oxygen concentration was measured every minute, the average value of the oxygen concentration from the start of the supply of nitrogen to the lapse of 5 minutes was 0.9 vol%. For the organic oxygen scavenger obtained in Example 2, as in Example 1, the weight of the organic oxygen scavenging material filled in each bag was measured, and the variation in the filling amount was examined, and the oxygen absorption amount Was measured.

  In Example 3, except that the total nitrogen supply amount was increased from 5 L / min to 12 L / min, 200 bags were filled in an organic system by the same method as in Example 1 so that the filling amount became 0.9 g. Filled with deoxidized material. At this time, the supply amount of nitrogen per unit is about 2.4 L / min. Similarly to Example 1, nitrogen was supplied into the inside of the weighing turntable 20 from two places. The amount of nitrogen supplied from one location was 2 L / min, and the amount of nitrogen supplied from the other location was increased from 3 L / min to 10 L / min. Further, when the oxygen concentration was measured every minute, the average value of the oxygen concentration after the start of the supply of nitrogen until 5 minutes was 1.3 vol%. For the organic oxygen scavenger obtained in Example 3, as in Example 1, the weight of the organic deoxidation material filled in each bag was measured, and the variation in the filling amount was examined and the oxygen absorption amount was also measured. Was measured.

Comparative example

  As a comparative example, the total amount of nitrogen supplied was 2 L / min, and 200 bags were filled in the same amount as in Example 1 except that nitrogen was supplied only from one place in the measuring turntable 20. The organic deoxidizing material was filled so as to be 9 g. At this time, the nitrogen supply amount per unit is about 0.4 L / min. Further, when the oxygen concentration was measured every minute, the average value of the oxygen concentration from the start of the supply of nitrogen to the lapse of 5 minutes was 5.1 vol%.

[Evaluation]
1. First, Table 1 shows the average values of oxygen concentration, humidity, and temperature in the measuring turntable 20 in each of Examples 1 to 3 and Comparative Example 1. Moreover, the average value of oxygen concentration, humidity, and temperature in the external atmosphere at this time is shown. However, each average value shown in Table 1 is a value from the start of the supply of nitrogen into the measuring turntable 20 until 5 minutes have passed.

  As shown in Table 1, in the comparative example in which the total nitrogen supply amount to the measuring turntable 20 was 2 L / min, the average value of the oxygen concentration during 5 minutes after the start of the nitrogen supply was 5.1 vol%. Met. On the other hand, in Examples 1 to 3, the total nitrogen supply amount to the measuring turntable 20 is 3 L / min, 5 L / min, and 10 L / min higher than the comparative example, respectively, and the average of the oxygen concentration The values were 3.2 vol%, 0.9 vol%, and 1.3 vol%, respectively. From the results, the unit nitrogen supply rate is 1.0 L / min, 1.4 L / min, 2.4 L / min, and 1.0 L / min or more, thereby measuring the inside of the measuring turntable 20 measured every minute. It can be seen that the average value of the oxygen concentration of the sample was 3.2 vol% or less. Moreover, compared with Example 2, Example 3 with much nitrogen supply amount has increased the average value of the said oxygen concentration from 0.9 vol% to 1.3 vol%. Therefore, it can be seen that simply increasing the nitrogen supply amount does not cause the oxygen concentration in the metering turntable 20 to decrease linearly. The measuring turntable 20 is not completely sealed, and a gap is provided between the cover member 50 and the outer peripheral wall 23 of the measuring turntable 20. For this reason, when the nitrogen supply amount is increased, it is considered that the oxygen concentration increases conversely even if the external atmosphere flows into the measuring turntable 20 due to a so-called entrainment phenomenon and the nitrogen supply amount is increased.

  Table 1 shows an average value of the relative humidity in the measuring turntable 20 and an average value of the relative humidity in the external atmosphere. Here, in Comparative Example 1, the relative humidity in the external atmosphere is 76%, while the relative humidity in the weighing turntable 20 is 83%. This is because the organic deoxidation material supplied into the weighing turntable 20 contains water as an auxiliary agent, so that the relative humidity in the measurement turntable 20 is externally affected by the influence of moisture released from the organic deoxidation material. It is considered that the relative humidity in the atmosphere increases. Similarly, in Example 1, the relative humidity in the measuring turntable 20 is 83%, and the relative humidity in the external atmosphere is 79%. Therefore, the organic deoxidizing material is supplied into the measuring turntable 20. This shows that the relative humidity in the weighing turntable 20 increases. On the other hand, regarding Example 2, the relative humidity in the measuring turntable 20 is 69%, and the relative humidity in the external atmosphere at this time is 77%. Further, regarding Example 3, the relative humidity in the weighing turntable 20 is 68%, and the relative humidity in the external atmosphere at this time is 79%. Therefore, it can be seen that setting the total nitrogen supply amount to 5 L / min and the unit nitrogen supply amount to 1.4 L / min or more has the effect of reducing the relative humidity in the weighing turntable 20.

2. Changes in Oxygen Concentration Next, Table 2 shows changes in the oxygen concentration in the measuring turntable 20 in each of Examples 1 to 3 and Comparative Example 1.

  In each of Examples 1 to 3, the average value of the oxygen concentration in the measuring turntable 20 is reduced to 3.25 vol% or less within 2 minutes. In Examples 2 and 3, the average value of the oxygen concentration in the measuring turntable 20 is reduced to 1.5 vol% or less within 2 minutes. Further, in Example 2, the average value of the oxygen concentration in the measuring turntable 20 is reduced to within 1.0% within 3 minutes. On the other hand, in the comparative example, the measured value of the oxygen concentration when 4 minutes passed was 1.8 vol%, but the average value of the oxygen concentration in the measuring turntable 20 within 3. 5 minutes was 3.25 vol% or less. There was no reduction.

  Moreover, in the comparative example 1, the measured value of oxygen concentration is fluctuate | varied greatly every minute in the range of 6.7 vol%-1.8 vol% every minute. On the other hand, in Example 1, the measured value of the oxygen concentration fluctuates in the range of 0.1 vol% to 2.4 vol% every minute, and the fluctuation range is smaller than that of the comparative example. In Example 2, the fluctuation value per minute of the measured value of the oxygen concentration is within 0.3 vol%, and the same applies to Example 3. In Example 2, after 2 minutes, the oxygen concentration shows a substantially constant value, the fluctuation range is within 0.1 vol%, and the oxygen concentration in the measuring turntable 20 is kept substantially constant. Is done. From this, it can be seen that, in comparison with the comparative example, Examples 1 to 3 can reduce the average value of the oxygen concentration quickly, and the fluctuation of the oxygen concentration is small. Further, even if the nitrogen supply amount is increased, the fluctuation range of the oxygen concentration does not decrease linearly, but the fluctuation range of the oxygen concentration is smaller in Example 2 where the nitrogen supply amount is smaller than that in Example 3. It turns out that it becomes small. Also from this fact, when supplying nitrogen into the measuring turntable 20, in order to reduce the oxygen concentration in the measuring turntable 20 and to keep the oxygen concentration in the measuring turntable 20 stable, nitrogen supply It can be seen that it is not necessary to simply increase the amount.

3. Next, the average value of the filling amount of the organic oxygen scavenger in each bag of the organic oxygen scavenger manufactured in Table 3 is shown in Table 3. FIG. 3 shows a variation of the filling amount of the organic deoxidizing material in each bag in a graph.

  As shown in Table 3, the average value of the filling amount of the organic oxygen scavenger produced in Example 1 and Example 3 was 0.9 g, and the filling amount of the organic oxygen scavenger produced in Example 2 was The average value of was 0.89 g. From the result, by setting the oxygen concentration to 3.25 vol% or less within 5 minutes from the start of the supply of nitrogen to the weighing turntable 20, the target filling amount for each bag is reduced. It can be seen that the same amount of organic deoxidation material can be filled. On the other hand, the average value of the filling amount of the organic oxygen scavenger produced in the comparative example was 0.81 g, and there was a large variation as shown in FIG. Considering that the smallest filling amount was 0.62 g and the largest filling amount was 0.9 g, the fluidity of the organic deoxidation material is maintained under the production conditions of the comparative example. It can be seen that the organic deoxidizing material adhered to the inner wall surface of the measuring mass 10, and the organic deoxidizing material could not be accurately measured by the measuring mass 10. Moreover, since the average value of the filling amount is 0.81 g and the number of bags having the filling amounts of 0.72 g and 0.79 g is the largest, the filling amount of the organic deoxidizing material is small overall. There is a high possibility that the desired deoxygenation ability cannot be exhibited.

4). Next, Table 4 shows changes in the amount of oxygen absorbed when the organic oxygen scavengers obtained in Examples 1 to 3 and Comparative Example are left indoors. However, the oxygen absorption amount indicates the oxygen absorption amount (ml) per gram of the organic deoxidation material. In addition, the organic oxygen scavengers obtained in Examples 1 to 3 and the comparative example were each left in the room for 3 bags, and the oxygen absorption amount was determined from the respective weight changes after 1 day and after 4 days. It was.

  As shown in Table 4, when the organic oxygen absorber produced in Examples 1 to 3 was left in the room, the organic oxygen absorber produced in Example 1 was the organic oxygen absorber produced in Comparative Example. The amount of oxygen absorbed was the same as that of the oxygen agent. On the other hand, the organic oxygen absorber produced in Example 2 and Example 3 showed a larger oxygen absorption amount than the comparative example. From this result, in order to reduce the variation in the filling amount, the nitrogen supply amount is set to 1.0 L / min or more per 1 L of the filling atmosphere volume (S), and the oxygen concentration in the measuring turntable 20 is 3.25 vol%. Although it is effective to make the following, in order to produce an organic oxygen scavenger with higher deoxygenation capacity, it is better to increase the nitrogen supply amount per liter of the filled atmosphere volume (S). I understand.

  The apparatus for producing an organic oxygen scavenger according to the present invention allows nitrogen to be added to the measuring turntable so that the average value when the oxygen concentration in the measuring turntable is measured every minute is 3.25 vol% or less. Nitrogen supply means for supplying is provided, and the fluidity of the organic deoxidation material can be maintained, and this can be suitably used when producing an organic oxygen scavenger. In addition to the production of the organic deoxidation material, the organic oxygen scavenger production apparatus according to the present invention is a material that absorbs moisture and decreases its fluidity when the humidity in the atmosphere increases, It can also be suitably used as a fluid filling device used for filling a material whose fluidity changes due to a change in atmospheric humidity, such as a material that reacts with oxygen to produce water. Similarly, the method for producing an organic oxygen absorber according to the present invention is not limited to the production of an organic oxygen absorber, but also water that reacts with oxygen in the atmosphere or a material whose fluidity decreases due to moisture absorption. The present invention can be suitably applied to a filling operation for a material to be generated.

Claims (6)

A weighing turntable to which an organic deoxidation material is supplied, a plurality of weighing masses to which the organic deoxidation material is introduced by the rotation operation of the weighing turntable, and a shutter for closing and opening a lower opening of the measurement mass And opening the shutter at a predetermined raw material filling position, and filling the measured organic deoxidation material into the packaging material disposed below the weighing mass to produce an organic oxygen scavenger In the production equipment for organic oxygen scavengers,
Nitrogen supply means for supplying nitrogen into the measuring turntable is provided so that the average value when the oxygen concentration in the measuring turntable is measured every minute is 3.25 vol% or less. Equipment for producing organic oxygen scavengers.   The said nitrogen supply means supplies nitrogen in the said measurement turntable so that the average value when measuring the oxygen concentration in the said measurement turntable every minute may be 1.5 vol% or less. Organic oxygen scavenger production equipment. The nitrogen supply amount by the nitrogen supply means is 1.0 L / min to 2.4 L / min per 1 L of the filling atmosphere volume (S) represented by the following formula (1). The manufacturing apparatus of the organic type deoxidation raw material of description.
S = S _t −S _o (1)
However, in the above formula (1), S _t represents the total void volume (L) in the metering turntable, S _o is representative of the volume (L) occupied by organic deoxidizer within the metering turntable Yes.   4. The apparatus for producing an organic oxygen scavenger according to claim 1, wherein the organic deoxidizing material is mainly composed of an easily oxidizable organic substance having a hydroxyl group. 5.   The said organic deoxidation raw material contains 10 weight part-200 weight part of water as an auxiliary agent, when the said easily oxidizable organic substance is included as 100 parts by weight as a main ingredient, The manufacture of the organic deoxidizer of Claim 4 apparatus. A method for producing an organic oxygen scavenger for producing an organic oxygen scavenger by filling a packaging material with a predetermined amount of an organic oxygen scavenging material using an automatic filling device,
The automatic filling device includes a measuring turntable to which an organic deoxidizing material is supplied, a plurality of measuring masses to which the organic deoxidizing material is charged by a rotating operation of the measuring turntable, and a lower opening of the measuring mass. With a shutter that can be opened and closed freely,
While supplying nitrogen into the measuring turntable so that the oxygen concentration in the measuring turntable is 3.25 vol% or less, the shutter is opened and the packaging material arranged below the measuring mass is weighed. Filling an organic deoxidation material prepared to produce an organic oxygen scavenger,
A method for producing an organic oxygen scavenger characterized by the following.

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