JPH11169016A - Package of oxygen-generating agent and transportation of live fish - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a package of an oxygen generating agent having simple structure, enabling easy and safe operation, stably generating oxygen over a long period and effective for preventing the lowering of activity or the death of living fish during transportation by packaging a solid peroxide, etc., with a specific moisture-permeable material. SOLUTION: This package can be produced by packaging a solid peroxide consisting of one or more materials selected from adduct of sodium carbonate and hydrogen peroxide, sodium perborate monohydrate and sodium perborate tetrahydrate and activated carbon having a median particle diameter of 25-5,000 μm with a moisture-permeable material such as a microporous membrane made of a plastic sheet having a cup moisture permeability (40 deg.C, 90% RH) of >=20 g/m<2> /24 hr and free from the penetration of water under normal pressure. The weight ratio of the solid peroxide to the activated carbon is 100/(0.01-100) and the packaged oxygen-generation agent is preferably sealed in a vessel for the transportation of live fish.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxygen generating agent package and a method for transporting live fish using the oxygen generating agent package.

[0002]

2. Description of the Related Art In many cases, edible live fish such as carp and eel and ornamental fish such as goldfish are transported by placing water and live fish in a polyethylene bag, injecting oxygen into a corrugated cardboard, placing it on a truck or aircraft, and placing it on a truck or aircraft. . However, since oxygen in the system is consumed by respiration of live fish, transporting the fish for more than 24 hours is usually difficult, and dead fish may occur even within 24 hours.

On the other hand, hydrogen peroxide or a hydrogen peroxide adduct is brought into contact with a hydrogen peroxide decomposing catalyst in water to decompose hydrogen peroxide to generate oxygen.
Techniques for combinations with various catalysts are known (for example, JP-A-60-122703). However, simply contacting hydrogen peroxide or the like with a catalyst in water is too rapid for the generation of oxygen. It is not suitable for applications requiring stable generation.

[0004] As an oxygen generating material for use in transporting live fish, etc., an aqueous solution of peroxide and a decomposer wrapped in a multi-layered package (Japanese Patent Application Laid-Open No. 1-103902) are known. Coated with a water-permeable sheet containing an activated carbon layer (JP-A-5-306104), and packaged with a composition of a hydrogen peroxide addition compound and a solidifying agent (JP-A-7-289114). ), But the conditions are such that the composition components do not elute into water at the time of use, the operation is simple, oxygen is generated stably for a long time, the production cost is low, and the storage stability is excellent. Until now, everything has been met.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its object is to provide:
An object of the present invention is to generate oxygen stably with a simple structure, simple operation, safe and stable for a long time, and to prevent the vitality of live fish during plastic transportation from being reduced and to prevent evil.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in an oxygen generating agent package in which a peroxide and activated carbon are wrapped with a water-resistant moisture-permeable material, activated carbon is used. It has been found that the oxygen generation rate and the storage stability can be controlled by adjusting the particle size of, and the present invention has been completed. That is, the present invention is a solid peroxide and a median particle diameter of the activated carbon 25～5000Myuemu, cup HoToru humidity (40 ℃, 90% RH) is 20g / m ^2/2
The present invention relates to an oxygen generator package that is packaged with a moisture-permeable material that is 4 hours or more and does not allow water to pass through at normal pressure.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The solid peroxide of the present invention includes:
Sodium hydrogen carbonate adduct, sodium perborate monohydrate, sodium perborate tetrahydrate, calcium peroxide, barium peroxide, persulfate with sodium carbonate and hydrogen peroxide added at a molar ratio of 2: 3 In addition to inorganic peroxides such as potassium and potassium hydrogen persulfate, organic peroxides can be used. Among them, sodium hydrogencarbonate adduct, sodium perborate monohydrate and sodium perborate tetrahydrate are preferable in terms of storage stability and the like. Also,
One of these may be used alone, or two or more of them may be used.

[0008] In particular, commercial grades of sodium carbonate hydrogen peroxide adducts include various grades in which stability or the like is changed by adding or coating various salts and the like, and any of them can be used. . In addition, since the amount of generated oxygen or the rate of generated oxygen changes depending on the grade used, it can be used properly depending on the target duration of oxygen generation.

There is no particular limitation on the type of activated carbon of the present invention.
Representative commercial products include plant-based activated carbon using coconut shell or wood as a raw material, and mineral-based activated carbon using coal, pitch, or the like as a raw material. In addition, a catalytically activated carbon (CENTAUR, manufactured by Toyo Calgon Co., Ltd.) with an increased hydrogen peroxide decomposition efficiency can be used. Further, one of these may be used alone, or two or more thereof may be used.

The median particle size of the present invention is defined by JIS-K147.
The particle size distribution is obtained by the method of 4, and a cumulative particle size diagram is created, and the sieve opening when the sieve passing percentage of the diagram is 50% is referred to. The median particle size of the activated carbon used in the present invention is 2
It is 5 to 5000 μm, preferably 45 to 1000 μm. For example, a commercially available product having a limited particle size may be used, or a product obtained by crushing commercially available granular activated carbon and sieving the same may be used. When the median particle diameter is less than 25 μm, not only may the oxygen generation rate be too high to obtain a predetermined oxygen generation duration, but also it becomes difficult to uniformly mix peroxide and activated carbon. . Median particle size is 50
When it is larger than 00 μm, oxygen generation hardly occurs. In addition, depending on the stability of the solid peroxide, the peroxide decomposition ability of the activated carbon, the moisture permeability of the packaging material, the weight ratio of the solid peroxide to the activated carbon, the intended oxygen generation rate, etc. The preferred range will vary.

In the oxygen generator package of the present invention, if the particle size of the activated carbon is relatively small, the initial oxygen generation rate is high, but the oxygen generation rate tends to decrease with time. When the particle size of the activated carbon is relatively large, the initial oxygen generation rate is low, but the oxygen generation rate tends to increase over time. Further, by selecting an intermediate particle size between the two, the oxygen generation rate can be made substantially constant from the initial stage to the final stage.

The optimum weight ratio between the solid peroxide and the activated carbon depends on the type of the solid peroxide, the particle size of the activated carbon, the type of the packaging material, the intended duration of oxygen generation, and the like.
It is preferably in the range of 00: 0.01 to 100: 100. In general, as the ratio of activated carbon increases, the oxygen generation rate increases, and above a certain ratio, the oxygen generation rate does not change.

[0013] The packaging material of the present invention has a cup method moisture permeability (4
0 ℃, 90% RH) is 20g / m ² / 24hr or more, preferably 20~100000g / m ² / 24hr, a moisture-permeable material which is impervious to water and atmospheric pressure. Cup method moisture permeability (40 ° C, 90% RH) is JIS-Z0208
Is the water vapor permeability measured by In addition, a non-breathable film may be used in combination as a part of the packaging material.

When the ratio of the area of the moisture-permeable material in the entire packaging area increases, the amount of water vapor permeated into the packaging material increases, and the oxygen generation rate increases. Further, even when a moisture-permeable material having a high moisture permeability is used, the oxygen generation rate is increased. Therefore,
It is preferable to select the ratio of the moisture-permeable material and the type of the moisture-permeable material so as to obtain an appropriate oxygen generation rate. For the portion where the moisture-permeable material is not used, for example, a non-moisture-permeable water-resistant material such as a plastic multilayer stretched film obtained by dry laminating a polyethylene film and polyethylene terephthalate or a molded container can be used. Specific examples of the moisture-permeable material include a microporous film made of a plastic sheet having micropores and a nonwoven fabric made of a plastic sheet having micropores.

In order to produce a microporous membrane which can be used as the moisture permeable material of the present invention, for example, a synthetic resin film exemplified by polyethylene, polypropylene, polyfluoroethylene resin or the like is subjected to cold stretching and contains foreign matter. Stretching the film, extracting foreign matter from the film containing foreign matter,
A method of extracting the foreign material from the film containing the foreign material and then stretching the film, or a method of irradiating the film with an electron beam, or the like is employed.

Commercially available microporous membranes suitable for use in the present invention include, for example, Duragard (Celanese, USA) and FP-2 (Asahi Kasei Corporation)
NOP (Nippon Petrochemical Co., Ltd.), Nitoflon N
TF (manufactured by Nitto Electric Industry Co., Ltd.), NF sheet (manufactured by Tokuyama Soda Co., Ltd.), Cellpore NW11 (Sekisui Chemical Co., Ltd.)
And polyflon paper (manufactured by Daikin Industries, Ltd.).

The maximum pore diameter of the opening of the nonwoven fabric which can be used as the moisture permeable material of the present invention is preferably 2 μm or less. As the nonwoven fabric, for example, various types of plastic fibers exemplified by polyethylene, polypropylene, polyfluoroethylene, polyester, nylon, or the like, which are bonded by heat, pressure, an adhesive, or the like can be used. It is preferable that long fibers are joined together by pressure.

Commercially available nonwoven fabrics suitably used in the present invention include, for example, Tyvek (manufactured by DuPont, USA), IEL, Spunpond (manufactured by Asahi Kasei Kogyo Co., Ltd.), and Axter (manufactured by Toray Industries, Inc.) Manufactured).

The above-mentioned plastic microporous membrane or nonwoven fabric may be laminated with another material for the purpose of improving the heat sealing property and reinforcing the strength. As the laminated material for improving the heat sealing property, a film made of a plastic having a softening point lower than the softening point of a microporous membrane or a nonwoven fabric and having perforated holes (hereinafter, referred to as a perforated sheet) is preferable. Examples thereof include materials such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), and polyethylene ionomer. When a perforated sheet is used, the perforated sheet may be heat-sealed to the microporous film or nonwoven fabric in advance, or the laminated material and the microporous film or nonwoven fabric are separately prepared and the peripheral portion is heat-sealed. Just do it. In addition, it is preferable that the perforated sheet is disposed so as to come inside the package.

The reinforcing material is preferably made by knitting a band of synthetic fiber made of polyethylene. Usually, a band having a width of 10 mm or less is knitted in a lattice and a vertical band and a horizontal band are heat-sealed. Things are used. Specifically, for example,
Nisseki Warif (manufactured by Nippon Petrochemical Industry Co., Ltd.) is preferably used. The reinforcing material is preferably heat-sealed between the microporous membrane or nonwoven fabric and the perforated sheet, and is arranged in order of the microporous membrane or nonwoven fabric, the reinforcing material, and the perforated sheet from the outside of the package. Is preferred.

The shape and manufacturing method of the package of the present invention are not particularly limited. For example, a package can be manufactured by sandwiching solid peroxide and activated carbon on both sides with a packaging material, and heat-sealing the four sides of the packaging material. In this case,
It is preferable to heat seal between the moisture permeable materials, or to heat seal between the moisture permeable material and the non-moisture permeable waterproof material.

The oxygen generator package of the present invention generates oxygen by contact with water or steam. Even if the package is brought into contact with liquid water, water does not penetrate into the package, but water vapor in equilibrium with the liquid water passes through the moisture-permeable material and comes into contact with the oxygen generating agent. Occurs.

When the oxygen generator package of the present invention is used for transport and storage of live fish and shellfish, it is better to make the system using the oxygen generator package a closed system or a system close to a closed system. This is preferable because the gas 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. By adopting such a method, for example, 3 days to 5 days
Oxygen can be continuously generated in the system during the day to allow live fish and shellfish to grow.

If the oxygen-generating agent package of the present invention is left in the air, water vapor in the air may enter the package and the peroxide may be decomposed little by little. Therefore,
The oxygen generating agent package of the present invention is preferably sealed and stored with a moisture-impermeable water-resistant material, or stored in the presence of a desiccant such as silica gel. In particular, when emphasis is placed on storage stability, it is preferable to use an oxygen generator package having a relatively large activated carbon particle size.

[0025]

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 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 and activated carbon having a median particle size of 150 to 300 μm (granulated activated carbon Kuraray Coal PW manufactured by Kuraray Chemical Co., Ltd.
Filled with 0.4g, 120mm long
X An oxygen generating agent package heat sealed on all four sides to obtain a width of 85 mm and a seal width of 10 mm was obtained. One obtained oxygen generating agent package was floated on water (1 L) in a glass sealed container (total internal volume about 2 L) connected to a wet gas meter.
The cumulative amount of oxygen gas generated from the time of charging was 0.6 L up to 24 hours, 3.0 L up to 72 hours, and 3.5 L up to 120 hours.

Example 2 Example 1 was repeated except that activated carbon having a median particle size of 75 to 150 μm was used instead of activated carbon having a median particle size of 150 to 300 μm.
The same was done. The cumulative amount of oxygen gas generated from the time of charging was 0.9 L until 24 hours, and 3.L until 72 hours.
It was 3.5 L until 2 L and 120 hours later.

Example 3 The procedure of Example 1 was repeated, except that activated carbon having a median particle size of 45 to 75 μm was used instead of activated carbon having a median particle size of 150 to 300 μm. The cumulative amount of oxygen gas generated since the preparation was
1.7 L up to 24 hours later, 3.4 L up to 72 hours later
L, 3.5 L until 120 hours later.

Example 4 Instead of activated carbon having a median particle size of 150 to 300 μm (granular activated carbon Kuraray Coal PW manufactured by Kuraray Chemical Co., Ltd.), a median particle size of 300 to 600 μm was used.
Activated carbon (granular CENTAU manufactured by Toyo Calgon Co., Ltd.)
R was pulverized and sieved), except that R was used. The cumulative amount of oxygen gas generated from the time of charging was 0.3 L up to 24 hours later, 2.8 L up to 72 hours later, and 3.5 L up to 120 hours later.

Example 5 Instead of two 160 μm-thick polyethylene nonwoven fabrics,
The procedure was performed in the same manner as in Example 1 except that one nonwoven fabric made of polyethylene having a thickness of 160 μm and one laminated film obtained by dry laminating a polyethylene film having no holes and a polyethylene terephthalate film were used. The cumulative amount of oxygen gas generated from the charging time was 0.6 L up to 24 hours, 2.6 L up to 72 hours, and 3.5 L up to 120 hours.

Example 6 Instead of two 160 μm-thick polyethylene nonwoven fabrics,
50 μm thick polypropylene microporous membrane (Duragard, Celanese, USA) / polyethylene reinforcement (Nisseki Warif, Nippon Petrochemical Industries, Ltd.)
One packaging material formed by heat-sealing three layers of polyethylene film having small holes with a diameter of 0.3 mm at mm intervals, and a thickness 4 having small holes of system 0.2 mm at intervals of 1 mm each on the left, right, top and bottom.
The procedure was performed in the same manner as in Example 1 except that one laminated packaging material in which a 0 μm EVA film and a 150 μm thick microporous film (Cerpore, manufactured by Sekisui Chemical Co., Ltd.) were laminated was used. However, heat sealing was performed so that the perforated sheet layer was located inside the package. The cumulative amount of oxygen gas generated since the preparation was
0.5L until 24 hours, 2.2 after 72 hours
L, 3.5 L until 120 hours later.

Example 7 40 g of sodium hydrogen carbonate adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a median particle size of 150 to 300 μm
40 g of sodium hydrogencarbonate adduct (SPC-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) instead of 0.4 g of activated carbon
Example 1 was repeated except that 0.8 g of activated carbon having a particle size of 45 to 75 µm was used. The cumulative amount of oxygen gas generated from the time of charging was 0.9 L up to 24 hours later, 2.1 L up to 72 hours later, and 3.3 L up to 120 hours later.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no powdered activated carbon was used. The cumulative amount of oxygen gas generated from the preparation was 0.0 L until 24 hours, 0.1 L until 72 hours, and 120 L.
It was 0.3 L until after the time.

Comparative Example 2 The procedure of Example 1 was repeated, except that activated carbon having a median particle size of 5,000 μm or more was used instead of activated carbon having a median particle size of 150 μm to 300 μm. Even after 120 hours from the charging, the amount of generated oxygen gas was 0.1 L.

Comparative Example 3 Instead of two 160 μm-thick polyethylene nonwoven fabrics,
The procedure was performed in the same manner as in Example 1 except that two laminated films obtained by dry laminating a polyethylene film having no holes and a polyethylene terephthalate film were used.
Even after 120 hours from the charging, no oxygen gas was generated.

Comparative Example 4 Instead of 40 g of sodium hydrogencarbonate adduct, 10
The operation was performed in the same manner as in Example 1 except that 40 g of a 30% aqueous hydrogen peroxide solution was used. After 2.5 L of oxygen gas was generated in 30 minutes from the charging, no oxygen gas was generated at all.

Example 8 In a polyethylene bag, 70 goldfish (total weight 650)
g), 3 L of water and 3 pieces of the oxygen generating agent package prepared by the method of Example 1, and after blowing about 5 L of oxygen gas, the mouth of the bag was tied with a rubber band and left at 25 ° C. for 48 hours. At the time of the lapse, all the fish had survived, and at the time of the lapse of 72 hours, 55 goldfish had survived.

Comparative Example 5 When the same procedure as in Example 8 was carried out except that the oxygen generator package was not inserted, all the goldfish had died after 48 hours.

[0039]

According to the present invention, the survival rate of live fish and shellfish during transportation and storage can be increased. In addition, it can be suitably used as an oxygen generating material in an emergency such as at the time of oxygen deficiency or harmful gas generation, or as a material for maintaining freshness of plants.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Chiharu Nishizawa 2-4-16-1 Hinagahigashi, Yokkaichi-shi, Mie Pref.

Claims (6)

[Claims] 1. A solid peroxide having a median particle size of 25 to 50.
Activated carbon of 00 μm and a cup method moisture permeability (40 ° C., 90
% RH) is packaged by moisture-permeable material which is impervious to water and and atmospheric pressure at 20g / m ² / 24hr or more oxygen generating agent package. 2. The oxygen generator package according to claim 1, wherein the moisture-permeable material is a microporous film made of a plastic sheet. 3. The oxygen generator package according to claim 1, wherein the moisture-permeable material is a nonwoven fabric made of a plastic sheet having fine pores. 4. The oxygen generation according to claim 1, wherein the solid peroxide is at least one selected from sodium hydrogen carbonate adduct, sodium perborate monohydrate and sodium perborate tetrahydrate. Agent package. 5. The weight ratio of solid peroxide to activated carbon is 10
The oxygen generator package according to claim 1, wherein the ratio is 0: 0.01 to 100: 100. 6. A method for transporting live fish, comprising enclosing the package of claim 1 in a transporter.