KR820000843B1 - Oxygen absorption matter - Google Patents

Abstract

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Description

Oxygen absorption chip that generates carbon dioxide and has high oxygen absorption ability

1 is a characteristic diagram showing the effect of the deoxygenating composition of the present invention,

2 is a characteristic diagram showing the effect of the oxygen absorbing chip of the present invention,

3 is a characteristic diagram showing the relationship between the main crab amount and the oxygen absorption capacity,

4 is a characteristic diagram over time showing the water vaporization prevention action of the film.

The present invention relates to a composition for generating carbon dioxide and having a high oxygen absorption capacity, and a chip for oxygen absorption.

In recent years, for example, the industrial distribution mechanism of the oxygen absorber crab is complicated, and the food itself is diversified regardless of natural foods and processed foods. As a result, various measures to maintain the quality of food have been posted and are now available. For example, there are food additives that are added directly to food, canned foods, retreat pouches, etc., which are placed in containers, and freezing, drying, vacuum packs using packing films, gas flush packs, and the like. .

However, additives, heat, freezing and drying treatments adversely affect the food itself, even if the purpose of food preservation is achieved. Food additives, for example, enter the mouth with food. In addition, heat, freezing, drying treatment, etc. have the disadvantage that the shape, color, flavor, nutrients, etc. of the food itself is damaged. Therefore, in recent years, the gas flush pack using a packaging film attracts attention. Among them, nitrogen gas, carbon dioxide gas or nitrogen gas-carbon gas mixed gas is used, and the purpose is to displace oxygen by putting nitrogen gas in a non-breathable bag with food and to prevent the oxidation and mold of food. . Carbonic acid gas or nitrogen gas-carbonate gas mixed gas has the effect of carrying out the oxygen replacement and suppression of the carbon dioxide gas bacteria and the oxidation inhibitory force, and the effect is large.

However, this also mechanically performs the work in the gas flat shoe, so 100% flushing by gas is difficult, and an average of 2 to 3 oxygen remains, sometimes exceeding 10%. This results in fluctuations in quality, which not only rubs in terms of food safety, but also requires large and heavy equipment. Thus, what was created to solve this problem is called deoxidizer, which is used to deoxidize air in a sealed bag.

The commercially available deoxidizing agents are generally referred to as the trade name ageless (Japanese Mitsubishi Gas, Inc.) using the oxygen absorption process of iron-based (synthetic iron carbide), the trade name ORC (Toyo Kono ring agent), or And organic compound-based trade names Jorrick-A (manufactured by Daisei Hoozai Co., Ltd.). The residual oxygen concentration when using this is extremely excellent, which is 0.1% or less, and deoxygenation is performed in small pieces without using expensive mechanical equipment, and it has been approached until the price can be used by the general public. However, their deoxygenation system also had some problems, first of all, because it absorbs oxygen in the air, the volume occupied by oxygen decreases by 20.9%, so it is easy to become a so-called vacuum state. , Baumkuhen and other foods are deformed. Second, the oxygen absorption rate is different depending on the moisture content (AW) in the airtight bag. The third point is that the iron-based deoxidizer produces iron rust smell and gives a disgust depending on the type of food. The fourth part is to check the presence of foreign substances such as iron by checking the metal detector. Most iron-based carbonic acid reacts with metal detectors, which is why It is extremely difficult haejyeoseo point is subjected to a complicated procedure to be used for.

Zorik-A is a Japanese patent application No. 52-73832 filed by the present applicant and is filed as a thin sheet using organic compounds, unlike iron-based oxygen scavenger, which allows the use of metal detectors. Like a deoxidizer, there is no fear of powder falling off the bag, excellent in safety, no odor like iron rust, no fear of changing the oxygen absorption rate by the water content (AW) in the airtight bag, and the size in the same amount of oxygen absorption. Compared with other, weight and price, it was almost equivalent.

However, what can be said about the general known oxygen deoxidant is that it only absorbs oxygen and produces | generates carbon dioxide gas, and does not have the inhibitory effect on bacteria or mold, or the antioxidant effect of food. Therefore, the gas flushing method has a drawback in that the storage period is short compared to that in which the replacement rate by the mixed gas of carbon dioxide + nitrogen gas is good. In addition, due to the absorption of oxygen, 20.9% of the volume in the airtight bag disappears into a vacuum state, and if it is wrong, there is a drawback of deforming the food shape.

As a result of various experimental studies, the inventors of the present invention do not have any of the above-mentioned drawbacks, and have a completely new deoxidation composition which combines the advantages of using a gas flushed carbon dioxide and the superior oxidizing ability of the deoxidizer. Invented the chip for oxygen absorption.

The oxygen absorbing chip of the present invention (for 400 kPa) has the same dimensions (4 cm x 4 cm x 0.30 cm) and the same occupied volume (2.7 cm 3) compared to the conventionally available product Jorlick-A (for 200 kPa). The weight of the two Jorik-As is about half the price of about 5 yen compared to 8 yen, and is extremely small and light.

The oxygen absorbing chip of the present invention has a deoxygenation capacity (absorption capacity and absorption rate) of at least two times higher than that of the conventional commercial product, Jorrick-A. Occurs. In the oxygen absorbing chip of the present invention, the oxygen concentration in the sealed air of 400 kPa can be made 0.1 to 0.2% in 72 hours and 0.01% or less in 96 hours.

The deoxidized firing composition of the present invention contains a deoxygenated organic compound, an iron compound for producing iron ions in water, for example, a salt of ferrous and / or ferric iron, a solvent, and generates a carbon dioxide gas. At the same time it is characterized by high oxygen absorption-capacity.

The deoxygenated organic compound for use in the present invention is selected from the group consisting of ascorbic acid and its salts, erythrovinic acid and its salts, currychol and resorcin. These are selected and used according to the purpose, among which ascorbic acid and salts thereof, in particular sodium ascorbate, are most suitable in terms of price and availability. The ferrous salts and / or ferric salts are selected from the group consisting of ferrous sulfate, ferrous chloride, ferrous nitrate, mother salts, ferric sulfate, ferric chloride and ferric nitrate. They are used according to the purpose, of which ferrous sulfate is most suitable in terms of safety, availability and price.

The solvent used in the present invention is selected from the group consisting of water and alcohol. Water is particularly suitable because of its wide range of solvent properties and low cost. According to the purpose, alcohol is used for the use in which the alcohol vapor has a bactericidal effect.

The oxygen scavenger composition of the present invention is a liquid composition, which can kill microorganisms such as molds, bacteria, etc. in a closed space such as a warehouse dock, even if left open in a container in the same corner. Evaporated microorganisms can quickly kill microorganisms and are much cheaper and safer than fumigation by clearing gases. In addition, the deoxygenating composition of the present invention is extremely effective when used for the production of gas of the gas flush system.

The oxygen absorbing chip of the present invention is breathable in supporting a deoxygenated organic compound and an iron compound that generates iron ions in water, for example, a salt and a solvent of ferrous and / or ferric iron on a porous object. It is enclosed in a film bag having water permeability and heat sealability, and is characterized in that it has a high coral absorption ability while generating carbon dioxide at a small size and light weight.

The deoxygenated organic compound used in the oxygen absorbing chip of the present invention and the iron compound for producing iron ions in water, for example, the salts of ferrous and / or ferric iron, and the solvent, and the deoxygenated composition Use the same thing as

The porous material used in the oxygen absorbing chip of the present invention is a diatomaceous earth, a fibrous sheet or plate, pulp, zeolite, blast furnace slug, steelmaking slug, coral fragments (not only coral corals but also coral corals), buckwheat husk , Rice bran, rice bran, sorghum dregs, soy dregs, starch, activated carbon, volcanic ash, white mud, volcanic coal, pumice stone, green algae and oil. The film bag containing the deoxygenated base material may be any suitable one as long as it has air permeability and is water permeable and has heat sealability. Conventionally, there was no permeable film except for Tyvek (trade name), which is released from DuPont in the United States. However, Tyvek is not heat sealable and extremely expensive, and coating a small amount of polyolefin so as to have heat sealability such that the air permeability is not lost does not ensure air permeability and does not reliably prevent leaching of water. It became. Therefore, at this point in time, the bag of TK-Z (trade name) film developed, manufactured and marketed by the present applicant is the only film bag suitable for the purpose of the present invention. It is also desirable to have a slight heat seal strength and tear strength so that the child does not tear off the contents with his hands. As such a film bag, only the TK-Z film bag manufactured by the present applicant is suitable at present. The TK-Z film is a resin laminate processed with a nonwoven fabric and is treated to have a small pin hole.

In the present invention, the ratio between the deoxygenated composition and the porous material can be arbitrarily selected according to the degree of the required effect. In view of the efficiency of use, the carbonic acid composition is impregnated into the porous material to the extent that the composition is not exuded from the porous material. It is preferable. This is because the closer to the exuded state, the smaller the contact area of the porous material with air and the slower the reaction rate. However, even if the deoxygenated composition is impregnated into the porous object such that the deoxygenated composition is exuded from the porous material, the TK-Z film produced and sold by the applicant does not leak the exuded deoxygenated composition out of the film bag and the object article. It is extremely safe and hygienic.

The oxygen scavenger base used in the oxygen absorbing chip of the present invention may be any of an oxygen scavenger organic compound and an iron compound that generates iron ions in water, for example, ferrous and / or ferric salts, a solvent and a porous material. Appropriate combinations can be used. Pressing and crimping can be combined suitably in a combination. For example, the fibrous sheet or plate carrying the powder of the deoxygenated organic compound and the aqueous solution-impregnated fibrous sheet or plate of ferrous salt and / or ferric salt are laminated and pressed. Other suitable examples include pressurization or compression by laminating at least one fibrous sheet or plate impregnated with an aqueous solution of a deoxygenated organic compound and ferrous salt and / or ferric salt alone or together with an unimpregnated fibrous sheet or plate. It is.

Oxygen absorption chip of the present invention (development name TR-4) functions as oxygen and generates almost the same capacity of carbon dioxide, so there is no volume change, and in addition to excellent deoxygenation ability, high level of bacterial inhibition and oxidation of carbon dioxide gas When the reaction proceeds and the reaction proceeds, the residual oxygen concentration may be 0.01% or less, and the same size as that of Zoric-A, that is, 4cm × 4cm × 0.3cm, which is equivalent to that of Zoric-A at 0.01%. The oxygen content in the air of 400 kPa is 0.01%, so the deoxidation capacity is remarkably high, and it is small, light weight, cheap, safe and odorless. In addition, the oxygen absorbing chip of the present invention does not react to the metal detector despite the use of iron salts unlike conventional iron-based oxygen scavenger. The reason is not yet clear, but it is probably due to the small amount of iron and the lack of iron ionization. Therefore, even when used for a target article, for example, food, foreign metals in the food can be easily detected. These characteristics are characteristics that were never found in the conventional gas flush method and the deoxidizer method (except Jorrick-A).

The most important aspect of the present invention is to absorb oxygen as the reaction effect between the deoxygenated organic cargo and the iron compound which produces iron ions in water, for example, ferrous salt and / or ferric salt, and the absorption amount is Significantly increased compared with the reaction with alkali, and at the same time, it produces oxygen and almost the same amount of deoxidized gas, there is little volume change, and the inhibitory effect on aerobic bacteria, anaerobic bacteria, and aerobic bacteria is generated by the effect of the generated carbon dioxide gas. It has the effect of preventing the rancidity of oil and fat. The oxygen scavenger having such characteristics is not present in the commercially available oxygen scavenger, and it is difficult to show such an effect even in the gas flushing method.

The following Table 1 shows a comparison between the conventional gas flush method and various deoxygenation methods and TR-4 of the present invention.

[Table 1]

There may be some variation in data values.

In the present invention, the ratio between the deoxygenated organic compound and the iron compound which produces iron ions in water, for example, the ferrous salt and / or the ferric salt, can be arbitrarily selected. The amount of the iron compound that produces iron ions in water to the organic compound may be increased. In the case of using water as the solvent, the amount of the deoxygenated organic compound to water is limited by the amount of the deoxygenated organic compound dissolved in water. However, when the temperature of water is raised, the amount of dissolution increases. For example, 60 parts or more of water is required for 100 parts of ascorbic acid, 80 parts or more of water is required for 100 parts of sodium ascorbate, and 200 parts or more of water is required for 100 parts of sodium erythrobinate. Criteria).

Among the deoxygenated organic compounds, even when hydroquinone, pyrovalent acid, tannic acid, glucose, and the like were reacted with ferrous or ferric salts, the deoxidizing effect as in the case of reacting with an alkali such as sodium hydroxide was not obtained.

A catalyst for promoting the reaction between the deoxygenated organic compound and the iron compound which generates iron ions in water can be added to the deoxygenated composition.

The oxygen absorbing chip of the present invention is different from other known iron-based oxygen scavengers other than Jorrick-A, so that it does not need to replenish moisture in anything else, so that it does not affect the amount of moisture in the airtight space. However, since the iron-based deoxidizer requires water during the reaction process, the reaction rate tends to be largely influenced by the amount of water in the container space.

The invention also relates to a method of manufacturing an oxygen absorbing chip.

The production method of the present invention comprises a deoxygenated organic compound and a deoxygenated base material in combination with a porous material and a composition containing an iron compound, such as ferrous and / or ferric salts and a solvent, produced by iron temperature in water. It is characterized in that it is prepared and heat-sealed while being breathable, having no permeability, and sealing sealant in a film bag.

The deoxygenated composition and the porous material can be combined in any suitable manner to form a deoxygenated base material. In this case, it is not necessary to prepare a deoxygenated composition and then combine it with the porous material, and after the one or two or more of the components of the deoxygenated composition is supported in a solid or liquid phase on the porous material, the remaining constituents of the deoxygenated composition (solid Or a combination thereof, such as liquid phase). What is needed is that the oxygen scavenger composition and the porous object are combined in the oxygen scavenger base, preferably present in a uniform combination throughout.

Therefore, in the combination of the deoxygenated composition and the porous material, for example, after the solution of the deoxygenated organic compound dissolved in the solvent is supported on the porous material, the ferrous salt and / or the ferric salt are added to the porous solution. It is possible to combine by supporting and mixing and sometimes by superimposing or mixing the porous materials again and then compressing them.

Alternatively, the solvent solution of the deoxygenated organic compound with the ferrous salt and / or ferric salt may be combined by supporting the porous material, sometimes overlapping or mixing the porous material, and then compressing the porous material.

Alternatively, the powder of the deoxygenated organic compound may be supported on the porous material and bonded to the porous material impregnated with the solvent solution of ferrous and / or ferric salts, and sometimes combined by overlapping or mixing the porous materials and then compressing them. There is a number.

Pressing or compressing the combined oxygen scavenger composition and the porous material facilitates osmosis of the oxygen scavenger composition into the porous material, while allowing free control of the oxygen scavenger from the porous material. This is also to control the rate of oxygen absorption.

By pressing or pressing, the composition is uniformly dispersed, and even in a very small portion, it is possible to prevent unevenness and to carry it in a waste-free amount, so that the effective use of the deoxygenating composition is possible.

In addition, by pressing or compressing, it is possible to prepare an integral deoxygenated base material, and to simplify the handling and packaging, and to achieve miniaturization and light weight. In addition, by reducing the solvent, the ratio of the deoxygenated organic compound and the iron compound that generates iron ions in water can be increased in size and weight can be achieved while reducing the time in the manufacturing process. The fall of the function of the deoxidation composition by oxygen absorption of can be prevented. Moreover, in order to prevent a fall in function, the method which does not contact oxygen with a deoxygenation composition can be employ | adopted, and it can generally use a sealed system and a non-oxygen gas separator.

In the family register of the manufacturing method of the present invention, the impregnated with an aqueous solution of a deoxygenated compound in a fibrous sheet or plate overlaps with and sometimes does not impregnate an aqueous solution of ferrous and / or ferric salt in the fibrous sheet or plate. After the fibrous sheets or plates are stacked, a plurality of them are laminated and pressed to obtain a deoxygenated base material, which is placed in a film bag having air permeability and heat sealability while being heat-sealed.

In another preferred example of the production process according to the invention, an aqueous solution of a deoxygenated organic compound and ferrous salt and / or ferric salt is superimposed on at least one fibrous sheet or plate and the unimpregnated fibrous sheet or plate Is superposed and a plurality of superposed ones are laminated to obtain a deoxygenated base material, which is placed in a film bag having air permeability and heat sealability while being breathable and heat-sealed.

Another preferred example of the production process according to the invention is a powder of deoxygenated organic compounds which is evenly sprayed onto a fibrous sheet or plate by means of powder spray or other common spraying methods, thereby producing ferrous and / or ferrous salts. The other fibrous sheets or plates impregnated with the aqueous solution were overlapped, and the double-folded one was laminated and compressed to obtain a deoxygenated base material, which was stored in a film bag having air permeability and heat sealability while being breathable. It is a way to seal.

In another preferred example of the production process according to the invention, the ferric salt and / or ferrous salt powder is evenly spread on a fibrous sheet or plate by means of powder spray or other common spraying methods and an aqueous solution of deoxygenated organic compound. The other fibrous sheets or plates impregnated with each other are overlapped, and the double-folded one is compressed in multiple sheets to obtain a deoxygenated substrate, which is put into a film bag having air permeability and heat sealability while being breathable and heat-sealed. The amount of oxygen uptake is determined by the amount of deoxygenated organic compound.

As a method for controlling the reaction rate of the deoxygenation reaction, there are the following methods.

(1) A method of changing the amount of iron compounds that produce iron ions in water to deoxygenated organic compounds. The higher the iron compound, the faster the reaction rate. However, the reaction rate at which the iron compound exceeds about 30% by weight is not gradually increased and slightly delayed.

(2) The method of changing the impregnated weight ratio of the deoxygenated composition to the porous material, the more the porous material and the larger the air contact surface area of the porous material, the faster the reaction rate. In addition, reducing the amount of deoxygenated composition relative to a certain amount of porous material increases the air contact area of the porous material, and speeds up the reaction rate. Therefore, the reaction rate can be selected according to the use of the oxygen absorbing chip.

Although the sealing of a film bag may be performed using an adhesive agent, since this requires a separate material and labor, since cost increases, it is preferable to crimp or hit seal by a tooth press.

Since the deoxygenated organic compound itself is known, the present invention does not have the characteristics of the deoxygenated organic hydrogenation boom itself, and deoxidation having a small and light weight and high deoxygenation ability and carbon dioxide gas generating ability using the deoxygenated organic compound according to the present invention. It is characterized by providing a firing composition and an oxygen absorbing chip. It is well known that the deoxygenated organic compound is markedly enhanced in deoxygenation in the presence of an aqueous solution or a metal such as Cu ions. Therefore, the present invention is not characterized by the aqueous solution in which the deoxygenated organic compound is dissolved. It is distinguished by the fact that an oxygen absorbing chip having high deoxidation capacity and carbon dioxide gas generating capacity at a light weight using an aqueous solution in which an organic compound is dissolved is produced.

As the fibrous sheet or plate, for example, Japanese paper, sunny paper, nonwoven fabric, abrasion cloth, cotton cloth, silk cloth, chemical fiber cloth, or paper can be used.

Impregnation of the solvent solution of a deoxygenation compound can be performed by arbitrary suitable methods of base materials, such as spraying and a coating. Impregnation can be carried out over part or the whole of the fibrous sheet, and it is more preferable to carry out uniformly over the whole.

The impregnation amount is used in an amount to impart a high deoxygenation capacity and a carbon dioxide gas generating ability when an oxygen absorption chip is manufactured according to the method of the present invention.

In the present invention, the oxygen absorption rate can be adjusted by adjusting the impregnation ratio of the main body (deoxygenated organic compound + iron compound + solvent which generates iron ions in water) to the fiber sheet or plate and the air permeability of the film bag. The larger the air permeability of the film bag, the faster the oxygen absorption rate and the slower the rate. The adjustment of air permeability is made by the selection of the size of the pin hole of the film bag. The film bag used for this invention can add or subtract the size of a pinhole so that the problem of exudation to a surface does not arise. Increasing the subject impregnation rate on the fiber sheet slows the oxygen absorption rate. However, when the impregnation rate is extremely high, the oxygen absorption rate is slowed down because the surface area of the fiber is reduced. In this case, the conventional film bag has a problem of exuding to the surface, but in the case of the film bag according to the present invention, no problem of exudation occurs. An effective measure to prevent effusion is to increase the amount of deoxygenated organic compounds in the subject relative to the solvent to increase the subject's viscosity. When this measure is used together with the film bag according to the present invention, it is possible to completely prevent the production of the subject matter from the film bag. This measure speeds up the rate of oxygen absorption.

It is not yet clear why the deoxygenating base of the present invention has a remarkably good deoxygenation capability compared to the conventional product. However, despite or without reason, it is clear that the deoxygenating base of the present invention has remarkably superior deoxygenation ability and carbon dioxide gas generation ability as compared to the conventional products as described below, and one of the reasons is probably to pressurization. It is believed that this is due to the fact that the solvent solution of the oxygen scavenger compound diffuses quickly and uniformly in the fiber sheet and exhibits high oxygen scavenging activity due to the large specific surface area in which the fiber sheet is insulated upon depressurization. It is thought that the ratio of the oxygen scavenger in the oxygen scavenger base is significantly higher than that in the conventional oxygen scavenger as described below. And, for another reason, since alkali is not used in the deoxidizing substrate of the present invention, it is considered that the carbon dioxide gas is not absorbed even if carbon dioxide gas is generated during the reaction process.

The arithmetic absorption chip of the present invention loses its flexibility and is hardened by the absorption of oxygen. This is thought to be due to the formation of some form of crosslinking by oxygen atoms, possibly accompanied by oxygen absorption. This helps to determine the deoxygenation capacity of the oxygen absorbing chip of the present invention.

Conventional oxygen scavengers give no reference to the oxygen scavenging capacity as described above, whether using powders of oxygen scavenging compounds with the exception of Zoric-A, or using aqueous or alkaline aqueous solutions.

The conventional deoxygenation principle is to prepare an alkaline aqueous solution of a deoxygenated compound and adsorb it to a solid adsorbent because the deoxygenated compound is easy to dissolve in the alkaline aqueous solution, or because the alkaline aqueous solution of the deoxygenated compound has high oxygen absorption ability. Since it was necessary to adsorb a large amount of alkaline solution of the deoxygenated compound by using a solid adsorbent, there was a drawback of absorbing oxygen in the air for a long time before encapsulating the film bag.

The present invention uses an extremely small amount of porous material to pressurize and compress the deoxygenated organic compound solvent solution impregnated therewith, so that it can be extremely small in size and thus can be encapsulated in a film bag in a very short time, thereby absorbing almost no oxygen in the air. There is this.

In the pressure crimping process, the non-impregnated fibrous sheet or plate is superimposed on the upper, middle, lower, or upper and lower sides of the impregnated sheet, and this is carried out by one or more pairs of the impregnated sheets. When the non-impregnated sheet is superimposed on or under the impregnated sheet, the loss of the deoxygenated compound and the solvent solution during press compression can be minimized, and the effective deoxygenation surface can be increased.

In the present invention, the following problems exist between the impregnation ratio of the main fiber sheet or the plate and the water permeability and moisture permeability of the film bag surrounding the deoxygenated substrate.

(1) The amount of oxygen absorbed depends on the amount of the main substance. The state which is easy to absorb oxygen means that the deoxygenated effective surface in which the main substance penetrated into the fiber of the fiber sheet or the plate contacts the oxygen is not the surface area of the fiber sheet or the plate. This is done by bringing the fiber to a state nearly equivalent to the total surface area of the fiber. This limits the amount of the subject matter contained in the fibrous sheet or plate to such an extent that the surface area of the fibers therein is not largely lost. In other words, the subject is not simply good, but excessively decreases oxygen absorption. FIG. 1 is a diagram illustrating this relationship. In the diagram, A represents 4 parts of water-resistant filter paper having a size of 2.5 cm × 2.5 cm (total 0.35 g), and sodium ascorbate, FeSO _4, and water is 0.8: 0.16: 0.96. It is used by weight ratio (total amount of 1.92g total) (there is always the surface area of the inner fiber), and this is enclosed in the bag made of TK-Z film, and B is the main amount of 0.92g (inner fiber) Almost does not lose surface area).

The data in the figure show the residual oxygen concentration with respect to the number of days that these ferns were left in 400 kPa of sealed air at a temperature of 25 ° C.

(2) However, in the case where the deoxygenated base material impregnated with the main material is encapsulated in the film bag, the outflow of the main material is a major factor in determining the impregnation ratio.

This is because the general air permeable film has a high water permeability, and therefore the impregnation ratio of the main material is extruded at least on the outer surface of the film bag. For this reason, when a general breathable film bag is used, the amount of the main sheet impregnation to the fiber sheet or the plate or the plate must be reduced, and the amount of the fiber sheet or the plate must be increased to secure a constant oxygen absorption force. Therefore, the subject becomes low density, and it becomes difficult to reduce the size and weight. The film bag having air permeability and no water permeability according to the present invention can increase the impregnation of the subject while preventing the exudation of the subject without such defects. That is, the pressure crimping used in the method of the present invention can freely control the effusion of the subject.

[Reference Example]

Comparative test results on the exudation between TK-Z film and other commercially available drying film

For four sheets of 2.5 cm × 2.5 cm (0.35 g in total), sodium ascorbate, FeSO ₄ and water (weight ratio 1: 0.2: 1.2) were used as the weights shown in the following table as a main subject, and this was a general drying film. , A, B, and TK-Z film were each enclosed in a bag and left in a room at a temperature of 25 ° C. for 10 days. Film A is a plurality of relatively small holes of about 0.5 mm? In the polyethylene film, and film B is a relatively large hole of about 1 mm? In the polyethylene film. As shown in the following table, the film for general desiccant, A, B showed effusion when casting was 0.8g, but TK-Z did not produce effusion even if the main material was 1.6g.

[Reference table]

(3) Since the oxygen absorption reaction process is possible only in the presence of water, the oxygen absorption reaction is stopped when water is lost in the deoxygenated substrate. For this reason, a deoxygenation compound cannot fully exhibit oxygen absorption ability. In terms of preventing evaporation of this water, the TK-Z film is remarkably superior to the desiccant film A, B, which is commercially available as shown in FIG. FIG. 2 shows the test results obtained by impregnating four filter papers (0.32 g in total) of 8 cm by 8 cm with 6.8 kPa of water in each film bag, and maintaining them in a thermostatic chamber having a humidity of 30% and a temperature of 30 ° C.

As described above, the occupant volume of the oxygen scavenger substrate of the invention can be significantly reduced with respect to the high oxygen sorption capacity and the constant oxygen uptake caused by containing a large amount of oxygen scavenger organic compound in the fiber sheet or plate. This is also attributable to the excellent feature of the film bag according to the present invention.

Oxygen absorbing chip of the present invention has the following advantages in addition to the high decarbonization ability, the ability to generate absorbed oxygen and carbon dioxide gas of almost the same capacity, small size, light weight, and low cost.

A) Since the deoxygenated base material is in sheet form, it can be made into a certain shape beforehand. Unlike the filling of the powder, the basis weight and filling of the film bag is accurate, quick, easy, and there is little unevenness and loss, and the working efficiency of automatic filling packing Increase the manufacturing cost. Further, dispersion of the rupture contents of the bag due to the heat seal with the powder adhered to the hit seal face of the film bag is eliminated. In addition, dust is not scattered, contaminated or adhered to the periphery of the automatic filling packing machine and the film bag surface, which is safe and hygienic.

B) It is safe and hygienic because deoxygenated base is not attached to human body and articles during use.

C) Successful use of the deoxygenated compound has been successfully reduced since the efficiency of the deoxygenated compound can be effectively used.

D) There is a limit to the amount of the deoxygenated compound dissolved in water or alcohol solution. According to the present invention, a deoxygenated compound which is easy to be dissolved in an aqueous solution is selected, and this defect is compensated by heating the aqueous solution. It is possible to increase the amount of deoxygenated compound to a high degree.

E) Since the deoxygenation capacity is known by the touch, it can be used any number of times until the deoxygenation capacity is no longer economical.

F) Do not generate heat. Therefore, it is advantageous for the refrigerated product.

G) Easy to transport, package and handle, and inexpensive.

H) The price for the air 400 is about 5 yen or less and the conventional product Jorrick-A is 8 yen for two uses, so it can be used for 100 yen products, for example, for potato chips. The cost burden of the turret is reduced and its use is greatly expanded.

I) As described in (a) above, the contents have good shaping, so the mechanical characteristics on the consumer side are good.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

Example 1

The oxygen uptake when the deoxygenated organic compound terminated the reaction with the ferrous and ferric salts was compared with the maximum oxygen uptake when the alkali was used for the deoxygenated organic compound. 20% FeSO ₄ aqueous solution was used as ferrous salt, and 30% HaOH aqueous solution was used as alkali. The results are shown in Table 2.

[Table 2]

As is apparent from the above Table 2, the use of ferrous salt doubled the oxygen absorption capacity and produced almost the same amount of CO ₂ as the absorbed oxygen as compared with the case of using alkali.

FeCl, Fe (NO ₃ ) ₂ , (NH ₄ ) ₂ , Fe (SO ₄ ) ₂ · 6H ₂ O, Fe ₂ (SO ₄ ) ₃ , FeCl ₃ , Fe (NO ₃ ) _3, etc., have almost the same effect as FeSO ₄ Indicated.

Example 2

The change in reaction rate due to the ratio of the deoxygenated organic compound to ferrous and ferric salts was tested in the case of sodium ascorbate and ferrous sulfate.

What was prepared at each compounding ratio was prepared by adsorbing 0.8 g of diatomaceous earth (silica) at 1.0 g each, and this was put together with 500 kPa of air in a non-breathable bag and tested for the amount of oxygen remaining after several days. The result was as showing in FIG. 3 as an oxygen absorption amount.

In the figure, numerals within o indicate the following compounding ratios.

Sodium ascorbate: FeSO ₄ : H ₂ O = 100: 50: 150 (weight ratio)

② sodium ascorbate: FeSO ₄ : H ₂ O = 100: 20: 120 (〃)

③ sodium ascorbate: FeSO ₄ : H ₂ O = 100: 10: 110 (〃)

④ Sodium ascorbate: FeSO ₄ : H ₂ O = 100: 5: 105 (〃)

⑤ Sodium ascorbate: FeSO ₄ : H ₂ O = 100: 1: 101 (〃)

Example 3

2.5 g of 12 sheets of deoxygenated composition mixed with 100 parts by weight of sodium ascorbate, 20 parts by weight of ferrous sulfate and 120 parts by weight of water, manufactured by Toyoro City, Japan Impregnated with 0.3g, 0.5g, or 0.8g cut to 2.5cm, pressurized it, stored in 4cm × 4cm of TK-Z Film Pe commercially available from the applicant company, and sealed and hydrated A chip was prepared.

The absorbent chip for oxygen was put together with 400 kPa of air in a non-breathable bag and the bag was sealed and the amount of oxygen remaining in the bag after several days was tested. The results were as shown in Table 3 and FIG.

①, ②, and ③ in FIG. 4 indicate that the amount of excitation is 0.3g, 0.5, and 0.8g, respectively.

[Table 3]

As apparent from the above Table 3, when the adsorption amount of the deoxygenating composition to the unit amount of margin was increased, the reaction rate of the deoxygenation reaction was slowed. It is thought that this is because increasing the adsorption amount decreases the porosity of the free space and decreases the area in contact with air. Therefore, the reaction rate can be appropriately determined by selecting the adsorption rate of the oxygen scavenger composition and the porous material according to the intended use of the oxygen absorbing chip.

In addition, when the deoxygenation composition was impregnated into six of the twelve filter papers and bonded to the six unimpregnated filter papers, the result was almost the same as described above.

Example 4

Using the oxygen absorption chip TR-4 of the present invention was tested for glutinous rice cakes the performance for mold was maintained in air at 25 ℃. The results were as shown in the following fourth table.

[Table 4]

Numbers in parentheses represent the percent remaining oxygen concentration after 4 days.

The N ₂ + CO ₂ flush was in the ratio N ₂ : CO ₂ = 7: 3.

After each sample was unable to be decorated, decaying odors and malting were generated.

In the table,-indicates a decorative state, and + indicates that it is not a decorative state.

Example 5

The necessity and practicality of the present invention will be described below by taking a gas flush method for processed food as an example.

The deoxygenating composition or the chip for oxygen absorption of the present invention could be effectively used in place of the gas flush method with respect to the processed food of the gas flush method shown in the following fifth table.

[Table 5]

The fifth table shows the importance of carbon dioxide in the packaging of food.

Example 6

(A) Oxygen absorption chips were prepared by changing the amount of sodium ascorbate with respect to 0.100 g of a 50% aqueous solution of FeSO ₄ . The oxygen absorption capacity was as follows.

(B) From the above results, it was found that according to the production method of the present invention, 0.340 g to 0.350 g of sodium ascorbate is sufficient to absorb oxygen (83.6 kPa) in 400 kPa air.

In addition, the concentration ratio of the solution can be arbitrarily set within the range in which the water-soluble deoxygenated organic compound is dissolved in the aqueous solution. Turned out.

It was also found that the higher the concentration of FeSO ₄ aqueous solution, the faster the oxygen absorption rate.

The ratio of the solvent to the deoxygenated organic compound can be arbitrarily set, but considering the economic feasibility, the range of 10: 1 to 10 was appropriate.

EXAMPLES 7 AND 8

Instead of the sodium ascorbate of Example 6, it was treated in the same manner as in Example 6 using ascorbic acid to obtain almost the same results. The manufacturing price of the chip for oxygen absorption was slightly higher than that in Example 6.

Example 9

A slightly moist silk, wool, cotton, or the like fabric was prepared without the oxygen absorbing chip of the present invention. After about one month each bag was examined. Mold and silk fabric of the control had mold, but no mold at all in the fabric containing the oxygen absorbing chip of the present invention.

Example 10

Conventional SO ₂ gas was used to make the cocoon to kill the silkworm, but this was undesirably staining the cocoon. The oxygen absorbing chip of the present invention was used, that is, it was convenient without staining.

Example 11

A commercially available 35mm camera was placed in a non-breathable bag with a capacity of 400㏄ and stored for one year under sealing. No mold was found in the lens or other parts.

While the present invention has been described with respect to specific examples, the present invention is not limited to these examples, and it is understood that various changes and modifications can be made by those skilled in the art without departing from the widespread settlement and visual field of the present invention. Will be obvious.

Claims (1)

Deoxygenated organic compounds selected from the group consisting of ascorbic acid and salts thereof, erythrovinic acid and salts thereof, catechol and resorcin, ferrous sulfate, ferrous chloride, ferrous nitrate, and mohr's salt ), Ferric sulfate, ferric chloride, and ferric nitrate, selected from the group consisting of ferric oxide, ferric salt and water, which can produce iron ions in water, and a fiber sheet or Oxygen absorption, characterized in that the deoxygenated substrate supported on the plate generates carbon dioxide gas at a small size and light weight encapsulated in a heat sealable film bag which is not breathable and permeable, and has a high oxygen absorption capability. Dragon chip.

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