JPH11100201A - Oxygen generating agent package and method for transporting live fish - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxygen generating agent package which is simple in structure, is easy to operate, is safe, is capable of generating oxygen stably for a long time and prevents the degradation in the activity of live fishes and the death thereof at the time of transporting by packaging a solid peroxide and a peroxide decomposing catalyst with a hygroscopic material which has specific cup method moisture permeability and does not allow the permeation of water under atm. pressure. SOLUTION: The solid peroxides, such as sodium carbonate hydrogen peroxide adduct, sodium perborate monohydrate and sodium perborate tetrahydrate and the peroxide decomposing catalysts, such as hydroxide, oxide, chloride, sulfate, acetate, carbonate and phosphate of various kinds of metals are packaged with the hygroscopic material which has the cup method moisture permeability (40 deg.C, 90% RH) of >=20 g/m<2> /24 hr, more preferably 20 to 100,000 g/m<2> /24 hr and does not allow the permeation of the water under atm. pressure in such a manner that the weight ratio thereof attains 100:0.01 to 100:100, by which the oxygen generating agent package is obtd. The live fishes are transported by encapsulating the oxygen generating agent package, the live fishery products and the water into a plastic transporting bag.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen generating agent package and the transport of live fish plastic 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 agent for use in transporting live fish and the like, an aqueous solution of a peroxide and a decomposing agent 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. There is still nothing to satisfy.

[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 As a result of intensive studies to solve the above problems, the present inventors have found that the rate of oxygen generation can be controlled by adjusting the amount of water vapor brought into contact with a specific oxygen generating agent. They have found that they can do this and have completed the present invention. That is, the present invention relates to a method in which a solid peroxide and a peroxide decomposition catalyst are mixed with each other by a cup method moisture permeability (40 ° C, 90% RH).
There is a 20g / m ² / 24hr or more, it relates to an oxygen generating agent packaging body formed by packing by and breathable material impervious to water 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.

[0009] Peroxide decomposition catalysts include hydroxides, oxides, chlorides, sulfates, acetates, carbonates, phosphates, double salts and oxyacid salts of various metals, as well as alumina, activated carbon, Examples thereof include porous adsorbents such as zeolite and silica gel, enzymes such as catalase, and organic acids such as fumaric acid. Among them, manganese dioxide, activated carbon, and catalase are preferable in consideration of the peroxide decomposition performance, availability, and the like. One of these may be used alone, or two or more of them may be used.

The weight ratio of the solid peroxide to the peroxide decomposition catalyst varies depending on the combination of the solid peroxide, the peroxide decomposition catalyst and the packaging material, and the intended duration of oxygen generation.
The ratio is preferably in the range of 100: 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.

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 package.

When the ratio of the area of the moisture-permeable material to the total 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 non-breathable portion not using a moisture-permeable material, for example, a moisture-permeable moisture-resistant material such as a plastic multilayer stretched film or a molded container obtained by dry laminating a polyethylene film and polyethylene terephthalate 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 cold-drawn 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 suitably used in the present invention include, for example, Juraguard (manufactured by Celanese Corporation, USA), FP-2 (manufactured by Asahi Kasei Corporation), NOP (Nippon Petrochemical Co., Ltd.) )), Nitoflon NTF (Nitto Denki Kogyo), NF Sheet (Tokuyama Soda Co., Ltd.), Cellpore NW11 (Sekisui Chemical Co., Ltd.), Polyflon Paper (Daikin Industries, Ltd.)
Manufactured).

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, Span Pond (manufactured by Asahi Kasei Kogyo), Axter (manufactured by Toray Industries, Inc.) Is mentioned.

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 formed 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.

There is no particular limitation on the shape and manufacturing method of the package of the present invention. For example, a package can be manufactured by sandwiching both sides of a solid peroxide and a peroxide decomposition catalyst with a packaging material and heat sealing four sides of the packaging material. In the case of this method, it is preferable to heat seal between the moisture permeable materials or heat seal with the moisture permeable material and the moisture-impermeable water-resistant 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, it is possible to continuously generate oxygen in the system for 3 to 5 days and to grow live fish and shellfish.

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.

[0021]

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 Polyethylene nonwoven fabric having a thickness of 160 μm (Tyvek,
Sodium hydrogen peroxide adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 40 between two sheets (Dupont, USA)
g, and 0.4 g of powdered activated carbon (Kuraray Coal PW, manufactured by Kuraray Chemical Co., Ltd.), 120 mm long × 85 m wide
m, an oxygen generating agent package having four sides heat-sealed so as to have a seal width of 10 mm. Obtained oxygen generator package 1
Each piece 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 preparation was 1.5 hours after 24 hours.
L, 3.1 L up to 72 hours later, and 3.5 L up to 120 hours later.

Example 2 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 time of charging was 1.1 L up to 24 hours later, 2.4 L up to 72 hours later, and 3.5 L up to 120 hours later.

Example 3 Instead of two 160 μm-thick polyethylene nonwoven fabrics,
50 μm thick microporous polypropylene membrane (Duragard, Celanese, USA) / polyethylene reinforcement (Nisseki Warif, Nippon Petrochemical Industries, Ltd.) / Small 0.3 mm in diameter at 7 mm intervals on each side The procedure was performed in the same manner as in Example 1 except that two packaging materials formed by heat-sealing three layers of a polyethylene film having holes were used. However, heat sealing was performed so that the perforated sheet layer was located inside the package. The cumulative amount of oxygen gas generated from the time of preparation was 0.1 until 24 hours later.
7 L, 2.0 L until after 72 hours, and 3.2 L until after 120 hours.

Example 4 Instead of two 160 μm-thick polyethylene non-woven fabrics as shown in FIG.
40 μm thick EVA film with small holes and thickness 1
50 μm microporous membrane (Cellpore, Sekisui Chemical Co., Ltd.)
1) and a thickness of 160 μm
Example 1 except that one piece of polyethylene nonwoven fabric was used.
The same was done. However, heat sealing was performed so that the EVA layer was located inside the package. The cumulative amount of oxygen gas generated from the time of charging was 1.2 L up to 24 hours later, 2.7 L up to 72 hours later, and 3.5 L up to 120 hours later.

Example 5 Instead of 40 g of sodium hydrogen carbonate adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.), sodium hydrogen carbonate adduct (SPC-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) ) 4
The procedure was performed in the same manner as in Example 1 except that 0 g was used. The cumulative amount of oxygen gas generated from the time of preparation was 0.1 until 24 hours later.
The volume was 1.4 L for 6 L, 72 hours later, and 2.2 L for 120 hours later.

Example 6 Instead of 40 g of sodium carbonate hydrogen peroxide adduct (SPC-G, manufactured by Mitsubishi Gas Chemical Co., Ltd.), sodium perborate monohydrate (15% perbon, manufactured by Mitsubishi Gas Chemical Co., Ltd.) ) 4
The procedure was performed in the same manner as in Example 1 except that 0 g was used. The cumulative amount of oxygen gas generated from the time of preparation was 0.1 until 24 hours later.
4 L, 1.5 L up to 72 hours later, 2.3 L up to 120 hours later.

Example 7 The procedure of Example 1 was repeated except that 0.4 g of activated carbon powder was replaced by 2.0 g of manganese dioxide (a reagent manufactured by Aldrich). The cumulative amount of oxygen gas generated since the preparation was
1.4 L up to 24 hours, 2.9 up to 72 hours
L, 3.4 L until 120 hours later.

Example 8 The procedure of Example 1 was repeated except that 0.2 g of a catalase solution (Ask Super 25, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of 0.4 g of the activated carbon powder. The cumulative amount of oxygen gas generated from the time of preparation was 1.0 L, 72 hours after 24 hours.
It was 2.1 L until after the hour and 2.8 L until after 120 hours. In addition, no hydrogen peroxide was detected in the water.

Comparative Example 1 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 2 Instead of 40 g of sodium hydrogencarbonate adduct, 10 g
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.

Comparative Example 3 The same operation 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.

Example 9 70 goldfish (total weight 650) were placed in a polyethylene bag.
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, a total number of the goldfish had survived, and at the lapse of 72 hours, 54 goldfish had survived.

Comparative Example 4 The same procedure as in Example 9 was carried out except that the oxygen generator package was not inserted, and all the goldfish had died after 48 hours.

[0034]

According to the present invention, the survival rate of live fish and shellfish during transportation and storage of plastic can be increased. Further, it can be suitably used as an oxygen generator in an emergency such as in the case of oxygen deficiency or generation of harmful gas, or as a plant freshness preserving agent.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of an embodiment of an oxygen generating agent package of the present invention.

[Explanation of symbols]

 1: Moisture permeable material 2: Perforated sheet 3: Moisture permeable material 4: Solid peroxide and peroxide decomposition catalyst

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

Claims (7)

[Claims] 1. A solid peroxide and a peroxide decomposition catalyst,
Cup method moisture permeability (40 ° C, 90% RH) is 20 g / m ²
/ Oxygen generator package packaged with a moisture-permeable material that is not less than 24 hours and does not allow water to pass at normal pressure. 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 generator 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. Packaging. 5. The peroxide decomposition catalyst is manganese dioxide,
The oxygen generator package according to claim 1, which is at least one selected from activated carbon and catalase. 6. The weight ratio of the solid peroxide to the peroxide decomposition catalyst is from 100: 0.01 to 100: 100.
The oxygen generator package according to the above. 7. A method for transporting live fish, wherein the oxygen generating agent according to claim 1 is enclosed in a transport bag.