JP2000041527A - Package of oxygen-generating agent.carbon dioxide- absorbing agent and transportation of live fishes or shellfishes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a safe oxygen-generating agent.carbon dioxide-absorbing agent package having a simple structure, capable of being simply treated, and capable of enhancing the survival rates of live fishes or shellfishes on their transportation or storage to reduce the cost of the transportation by placing a drying agent in the oxygen-generating agent pack. SOLUTION: This oxygen-generating agent.carbon dioxide-absorbing agent package is obtained by packaging an oxygen-generating pack and a carbon dioxide-generating pack with a packaging material capable of passing water at atmospheric pressure. Therein, a drying agent is placed in the oxygen-generating pack. The oxygen-generating pack is preferably obtained by packing a solid peroxide, a peroxide decomposition catalyst and the drying agent such as silica gel, activated alumina or zeolite with a moisture-penetrable material having a cup method moisture permeability of >=20 g/m2/24 hr (40 deg.C, 90% RH) and not passing water at atmospheric pressure. The carbon dioxide-absorbing agent pack is preferably obtained by packing an alkaline earth metal hydroxide and the drying agent with a gas-penetrable material having a Gurley air permeability (JIS-P8117) of 0.1-3,000 sec/air/100 ml and not passing water at atmospheric pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen generator / carbon dioxide absorbent package which is effective for use in transporting live fish and shellfish.

[0002]

2. Description of the Related Art Edible live fish and shellfish such as flounder, eel, and shellfish and ornamental fish such as goldfish are transported by placing water and live fish in plastic film bags, injecting oxygen into cardboard boxes, placing them in cardboard boxes, placing them on trucks or aircraft, and carrying them. Often done. Such a so-called plastic transportation is a simple and low-cost method, but since oxygen in the system is consumed and carbon dioxide is generated by respiration of live fish, transportation for 24 hours or more is usually difficult, and within 24 hours. But dead fish may occur. The number of live fish that can be transported in one bag is also limited.

[0003] On the other hand, as an oxygen generating material for use in transporting live fish and the like, an aqueous solution of a peroxide and a decomposing agent are wrapped in a multi-layered package (Japanese Patent Laid-Open No. 1-103902).
Japanese Patent Application Laid-Open No. 5-306104), those obtained by coating a peroxide or the like with a water-permeable sheet containing an activated carbon layer (JP-A-5-306104), and those obtained by packaging a composition of a hydrogen peroxide addition compound and the like and a solidifying agent. JP-A-7-289114) and the like have been proposed. However, those that satisfy all of the conditions such that the composition components do not elute into water at the time of use, the operation is simple, oxygen is stably generated for a long time, the production cost is low, and the storage stability is excellent It was not obtained so far.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and has as its object the simple and simple operation and safe transport of live fish and shellfish for a long time. It is an object of the present invention to provide a package of an oxygen generating agent and a carbon dioxide gas absorbing agent.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that storage stability can be improved by adding a desiccant to an oxygen generator package and a carbon dioxide gas absorbent package. The inventors have found that the present invention is very excellent, and have completed the present invention. That is, the present invention relates to an oxygen generating agent / carbon dioxide absorbing agent package obtained by packaging an oxygen generating agent package and a carbon dioxide gas absorbent package with a packaging material that allows water to pass at normal pressure. The present invention relates to an oxygen-generating agent / carbon dioxide-absorbing agent package characterized by including a desiccant in the body.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The oxygen generator package of the present invention comprises a solid peroxide, a peroxide decomposition catalyst and a desiccant, and a cup method with a moisture permeability (40 ° C., 90% RH) of 20 g / m 2. ² /
A package is used that is wrapped with a moisture-permeable material that is not less than 24 hours and does not allow water to pass at normal pressure.

[0007] Examples of the solid peroxide include sodium hydrogen carbonate adduct to which sodium carbonate and hydrogen peroxide are added at a molar ratio of 2: 3, sodium perborate monohydrate, sodium perborate tetrahydrate. Material, calcium peroxide,
In addition to inorganic peroxides such as barium peroxide, potassium persulfate and potassium hydrogen persulfate, organic peroxides can be used. One of these may be used alone, or two or more of them may be used. As the peroxide decomposition catalyst, one of manganese dioxide, activated carbon and catalase may be used alone, or two or more of them may be used.

[0008] The optimum weight ratio of the solid peroxide to the peroxide decomposition catalyst depends on the combination of the solid peroxide, the peroxide decomposition catalyst and the packaging material, and the desired oxygen generation duration, but is generally about 100: 0. It is preferably in the range of 0.01 to 100: 100. In general, the oxygen generation rate increases as the ratio of the catalyst increases, and the oxygen generation rate does not change above a certain ratio. Further, the solid peroxide and the peroxide decomposition catalyst may be simply mixed, and the mixture may be formed into a tablet or the like.

Although there is no particular limitation on the type of desiccant in the oxygen generating agent package, it is preferable to use at least one selected from silica gel, activated alumina and zeolite in consideration of performance and ease of handling. The optimal weight ratio between the solid peroxide and the desiccant varies depending on the type and moisture content of the solid peroxide and the catalyst, the type of the desiccant, the moisture permeability of the packaging material, and the storage conditions. : 100 is preferable. The presence of a desiccant in the oxygen generator package keeps the water vapor concentration in the package low, increasing the stability of peroxide during storage, and expanding the storage bag to prevent collapse of the package. Can be prevented.

As the moisture-permeable material of the present invention, a microporous film made of a plastic sheet having micropores, a nonwoven fabric made of a plastic sheet having micropores, and the like can be used. Commercially available microporous membranes include, for example, Duragard (Celanese, USA) and FP-2
(Made by Asahi Kasei Corporation), NOP (Nippon Petrochemical Co., Ltd.)
Nitoflon NTF (Nitto Electric Industries, Ltd.), N
F-sheet (manufactured by Tokuyama Soda Co., Ltd.), SELPORE NW11 (manufactured by Sekisui Chemical Co., Ltd.), polyflon paper (manufactured by Daikin Industries, Ltd.) and the like. Commercially available non-woven fabrics having micropores include, for example, Tyvek (manufactured by DuPont, USA), IEL, Spun Pond (Asahi Kasei Corporation)
And Axter (manufactured by Toray Industries, Inc.).

There is no particular limitation on the shape and production method of the oxygen generator package of the present invention. For example, a package can be manufactured by sandwiching an oxygen generating agent between packaging materials and heat sealing four sides of the packaging material. In the case of this method, it is preferable to heat seal between the gas permeable materials, or to heat seal between the gas permeable material and the impermeable water-resistant material.

[0012] As the carbon dioxide gas absorbent package of the present invention,
Alkaline earth metal hydroxide and desiccant are packaged with a gas permeable material that has a Gurley air permeability (JIS-P8117) of 0.1 to 3000 seconds / 100 ml of air and is impermeable to water at normal pressure. Using a carbon dioxide absorbent package. As the alkaline earth metal hydroxide, for example, at least one selected from calcium hydroxide and magnesium hydroxide can be used. As the gas permeable material, the same material as the moisture permeable material of the oxygen generator package can be used, and the production of the package can be performed in the same manner as the oxygen generator.

As the desiccant, the same one as in the oxygen generator package can be used. The presence of the desiccant in the oxygen generating agent package keeps the water vapor concentration in the package low, and enhances the stability of the alkaline earth metal hydroxide during storage.

As the packaging material of the present invention which allows water to pass at normal pressure, it does not allow solid components such as oxygen generators and carbon dioxide absorbents to pass through.
Any material can be used as long as it can transmit water, oxygen, and carbon dioxide, and woven fabric, nonwoven fabric, paper, and the like are used. Above all, it is preferable to use a hydrophobic water-permeable nonwoven fabric from the viewpoint of not impairing the performance of the carbon dioxide gas absorbent. From the viewpoint of productivity, it is preferable to use a material that can be heat-sealed.

The oxygen generator / carbon dioxide absorbent package of the present invention has a cup method moisture permeability (40 ° C., 90% RH) of 20 g.
It is preferably stored in / m ² / outer bag made of moisture-impermeable material of less than 24 hr or. As the moisture-impermeable material, an aluminum foil, an aluminum-deposited film, a silica-deposited film, a polyvinyl alcohol-based film, a barrier nylon-based film, a polyvinylidene chloride coated film, or the like can be used.

It is preferable to use an outer bag made of a moisture-impermeable material as a sealed bag because the invasion of water vapor from the outside is suppressed and the effect of the desiccant in the oxygen generating agent is remarkably exhibited. It is also preferable to make a pinhole in the outer bag in order to avoid expansion of the outer bag when only a part of the peroxide is decomposed to generate oxygen. In this case, a desiccant may be further coexisted in the outer bag in order to absorb a small amount of water that enters from the outside through the pinhole.

When the oxygen generator / carbon dioxide absorbent package of the present invention is used for transport and storage of live fish and shellfish, it is preferable to use a closed system or a system close to the closed system to generate oxygen gas. Is preferred because it is easily dissolved in water. For example, a method of putting live fish and shellfish, water, the oxygen generating agent package of the present invention and, if necessary, oxygen gas into a bag made of polyethylene or the like and tying the mouth of the bag with a rubber band or the like can be adopted.
In addition, the oxygen generator / carbon dioxide absorbent package can be used simply by throwing it into the transport bag, but it can also be used by fixing it to the head space of the transport bag with an adhesive or an adhesive tape. Good.

[0018]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Microporous polypropylene membrane (Duragard, manufactured by Celanese Corporation, USA) having a thickness of 50 μm / reinforcing material made of polyethylene (Nisseki Warif, manufactured by Nippon Petrochemical Industry Co., Ltd.) 40 g of sodium hydrogen peroxide adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) between two packaging materials obtained by heat-sealing three layers of polyethylene film having small holes with a diameter of 0.3 mm. Then, 2.0 g of manganese dioxide (manufactured by Aldrich) and 2.0 g of activated alumina were filled, and an oxygen generating agent package was obtained which was heat-sealed on four sides so as to have a length of 120 mm × width of 85 mm and a seal width of 10 mm.
However, heat sealing was performed so that the perforated sheet layer was located inside the package.

A granular material is placed between one 160 μm-thick polyethylene non-woven fabric (manufactured by DuPont, Tyvek, USA) and one laminated film obtained by dry laminating a polyethylene film having no holes and a polyethylene terephthalate film. Of 40 g of calcium hydroxide, and heat-sealed the four sides so as to have a length of 120 mm × a width of 85 mm and a seal width of 10 mm to obtain a carbon dioxide gas absorbent package. Furthermore, three prepared oxygen generating agent packages and two carbon dioxide gas absorbents were placed between two 90-μm-thick hydrophobic nonwoven fabrics (Melfit, manufactured by Unicell Corporation), which are water-permeable materials. 200mm x 150mm width, seal width 1
An oxygen-generating agent / carbon dioxide absorbent package having four sides heat-sealed so as to be 0 mm was obtained.

The obtained two packages of the oxygen generator / carbon dioxide absorbent are sandwiched between ^two laminated films (a cup method moisture permeability of 1 g / m 2/24 hr) obtained by laminating an aluminum-evaporated polyester film and a polyethylene film. Heat sealed. The sealed outer bag containing the oxygen generator package is
When stored in a thermo-hygrostat at 80 ° C. and a relative humidity of 80% for 2 months, no expansion of the outer bag was observed.

One package of the oxygen-generating agent after storage is sealed in a glass sealed container connected to a wet gas meter (with a total internal volume of about 2).
L) floated on water (1 L). The cumulative amount of oxygen gas generated from the charging time was 1.3 L up to 24 hours later, 2.8 L up to 72 hours later, and 3.4 L up to 120 hours later.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the activated alumina was not filled in the oxygen generator package and the carbon dioxide gas absorbent package. An oxygen generator package was prepared and placed in a sealed outer bag.
The outer bag containing the oxygen generator / carbon dioxide absorbent package
When stored in a thermo-hygrostat at 80 ° C and 80% relative humidity,
The outer bag expanded and burst in two weeks.

Example 2 A 160 μm-thick polyethylene nonwoven fabric (Tyvek,
Sodium hydrogen peroxide adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 40 between two sheets (Dupont, USA)
g, activated carbon having a particle size of 150 μm to 300 μm (granulated activated carbon Kuraray Coal PW manufactured by Kuraray Chemical Co., Ltd., pulverized and sieved) and 4.0 g of silica gel are filled, and are 120 mm long × 85 mm wide and 10 mm wide.
Thus, an oxygen generating agent package having four sides heat-sealed was obtained. Further, a carbon dioxide gas absorbent was obtained in the same manner as in Example 1 except that 4.0 g of silica gel was used instead of 2.0 g of activated alumina.

The obtained four oxygen generating agent packages and two carbon dioxide gas absorbent packaging materials were wrapped with a hydrophobic nonwoven fabric in the same manner as in Example 1 to obtain an oxygen generating agent / carbon dioxide gas absorbent package. Was. The obtained oxygen generating agent, carbon dioxide gas absorbent package two, laminated film laminated with polyvinylidene chloride-coated stretched nylon film and a polyethylene film (cup HoToru humidity 4g / m ² / 24hr) four sides sandwiched between two Heat sealed. 1 of the outer bag containing the oxygen generator package
When pinholes having a diameter of 0.2 mm were formed at two locations and stored in a thermo-hygrostat at 30 ° C. and a relative humidity of 80% for 2 months, the residual ratio of available oxygen in the peroxide was 95%.

One package of the oxygen-generating agent after storage was sealed in a glass sealed container connected to a wet gas meter (total internal volume of about 2).
L) floated on water (1 L). The cumulative amount of oxygen gas generated from the time of charging was 0.5 L up to 24 hours, 2.9 L up to 72 hours, and 3.5 L up to 120 hours.

Comparative Example 2 The procedure of Example 2 was repeated except that the inside of the oxygen generating agent package and the carbon dioxide gas absorbent package were not filled with silica gel. The outer bag containing the oxygen generator package was placed at 30 ° C. and a relative humidity of 8
When stored in a 0% constant temperature / humidity chamber for 2 months, the residual ratio of available oxygen in the peroxide was 74%. The accumulated oxygen gas generation amount was 0.4 L up to 24 hours later, 1.5 L up to 72 hours later, and 2.4 L up to 120 hours later.

Example 3 A catalase solution (Ask Super 25, Mitsubishi Gas Chemical Co., Ltd.) was used in place of 0.4 g of activated carbon and 4.0 g of silica gel.
Oxygen generator package was obtained in the same manner as in Example 2 except that 0.2 g of the synthetic zeolite and 1.0 g of absolutely dried synthetic zeolite were used. Further, a carbon dioxide gas absorbent was obtained in the same manner as in Example 1 except that 1.0 g of completely dried synthetic zeolite was charged instead of 2 g of activated alumina. The effective oxygen residual ratio in the peroxide after storage was 92%. The cumulative amount of generated oxygen gas was 0.9 L up to 24 hours, 2.0 L up to 72 hours, and 2.8 L up to 120 hours.

Comparative Example 3 The same procedure as in Example 3 was carried out except that the synthetic zeolite was not filled in the oxygen generator package and the carbon dioxide gas absorbent package. When the outer bag with the oxygen generator package was stored in a thermo-hygrostat at 30 ° C. and a relative humidity of 80% for 2 months, the residual ratio of available oxygen in the peroxide was 59%. The accumulated oxygen gas generation amount was 0.6 L, 72 L until 24 hours later.
It was 1.2 L until after the hour and 1.5 L until after 120 hours.

Example 4 An oxygen generator / carbon dioxide absorbent package was obtained in the same manner as in Example 2 except that silica gel was not filled in the carbon dioxide absorbent package. The resulting oxygen generating agent package 2 and silica gel 40 g, and the four sides are sandwiched by the laminate film laminated with aluminum-deposited polyester film and a polyethylene film (cup HoToru humidity 1g / m ² / 24hr) heat sealed. A pinhole having a diameter of 0.2 mm was made in one place of the outer package containing the oxygen generator / carbon dioxide absorbent package, and stored in a thermo-hygrostat at 30 ° C. and a relative humidity of 80% for 2 months. The residual ratio of available oxygen in the oxide is 93
%Met.

In a bag made of polyethylene, 150 goldfish (total weight: about 1 kg), 10 L of water, and one preserved oxygen generator / carbon dioxide absorbent package were placed, and about 20 L of oxygen gas was placed.
After blowing, the mouth of the bag was tied with a rubber band and left at 25 ° C. After 72 hours, the oxygen concentration of the headspace gas was 86%, and the carbon dioxide gas concentration was 11%. After 96 hours, the oxygen concentration of the headspace gas was 79%, the carbon dioxide concentration was 14%, and all the goldfish were alive.

Comparative Example 4 An oxygen generator / carbon dioxide absorbent package was prepared in the same manner as in Example 4 except that the oxygen generator package was not filled with silica gel. Two of the obtained oxygen generating agent / carbon dioxide absorbent package and 56 g of silica gel were placed in an outer packaging bag having a pinhole and containing the oxygen generating agent / carbon dioxide absorbent package. Remove the outer bag containing the oxygen generator / carbon dioxide absorbent package
When stored for 2 months in a thermo-hygrostat at 0 ° C. and 80% relative humidity, the residual ratio of available oxygen in the peroxide was 64%.

In a polyethylene bag, put 150 goldfish (total weight: about 1 kg), 10 L of water and one package of the stored oxygen generator / carbon dioxide absorbent, and put about 20 L of oxygen gas.
After blowing, the mouth of the bag was tied with a rubber band and left at 25 ° C. After 72 hours, the oxygen concentration of the headspace gas was 83%, and the carbon dioxide gas concentration was 12%. After 96 hours, the oxygen concentration of the headspace gas was 73%, the carbon dioxide concentration was 15%, and about 10% of the goldfish died.

[0034]

According to the present invention, the survival rate of live fish and shellfish during transportation and storage can be increased. In addition, since the transport time can be extended, plastic transport of live fish to distant areas, which has been impossible until now, becomes possible. Furthermore, since the amount of live fish and shellfish that can be enclosed in the transport bag can be increased, transport costs can be reduced.

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 2B104 BA16 CA09 CE03 EB15 EF03 4G042 BA06 BA44 BB05 BC06 4G066 AA12A AA12B AA16A AA16B AA17A AA17B AA20A AA20B AA22A AA22B AA61A A13BA23 AC13 BA16 AC13 BA23AC13 DA01 DA07 EA20 FA33 FA38 FA40

Claims (7)

[Claims] 1. An oxygen generator / carbon dioxide absorbent package obtained by packaging an oxygen generator package and a carbon dioxide gas absorbent package with a packaging material that allows water to pass at normal pressure. Oxygen generator characterized by adding desiccant to
Carbon dioxide absorbent package. 2. The oxygen generator / carbon dioxide absorbent package according to claim 1, wherein a desiccant is placed in the carbon dioxide gas absorbent package. 3. The oxygen generator package comprises a solid peroxide, a peroxide decomposition catalyst, and a desiccant, which are subjected to cup method water vapor transmission (40%).
° C., and at 90% RH) is 20g / m ² / 24hr or more, and atmospheric pressure is formed by wrapping a breathable material which is impervious to water in claim 1 oxygen generating agent, carbon dioxide gas absorbent package described. 4. A carbon dioxide gas absorbent package comprising an alkaline earth metal hydroxide, a desiccant and a desiccant, having a Gurley air permeability (JIS-P8117) of 0.1 to 3000 seconds / air 1
The oxygen generator / carbon dioxide absorbent package according to claim 1, which is packaged with a gas permeable material which is 00 ml and does not allow water to pass through at normal pressure. 5. The desiccant is silica gel, activated alumina,
2. The method according to claim 1, which is at least one selected from zeolites.
Or the package of oxygen generator / carbon dioxide absorbent according to 2 above. 6. A method for transporting live fish and shellfish, wherein the oxygen generator / carbon dioxide absorbent package according to claim 1 or 2 is enclosed in a transport bag. 7. The oxygen generator / carbon dioxide absorbent package according to claim 1 or 2, wherein the cup method moisture permeability (40 ° C., 90% R) is used.
Oxygen generating agent, carbon dioxide gas absorbent package in which H) is packaged by a packaging material made of moisture-impermeable material of less than 20g / m ² / 24hr.