JPS5846158B2 - How to store solid chlorine agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for safely preserving solid chlorine agents that tend to generate decomposed gases such as chlorine gas and nitrogen chloride gas during storage.

Conventionally, solid chlorine agents include trivalent hydrogenated incyanuric acid, bicyclic hydrogenated incyanuric acid, anhydrides, hydrates, or mixtures thereof of sodium salts or potassium salts of dicyclic hydrogenated incyanuric acid, or mixtures thereof. Compositions are known in which auxiliary agents are further blended into powdered, powdered,
It is widely used as a disinfectant, disinfectant, bleach, etc. in various fields in the form of granules, granules, or tablets.

However, after these solid chlorine agents are produced in factories, it takes commercial routes such as land and sea routes, for example, 1 to 2 years, before they are put into practical use at the site of use. After that, the contents are transported, transported, and stored in airtight packaging containers made of materials such as paper, plastic, and metal. As a result, various undesirable, and in some cases dangerous, accidents have occurred.

For example, the ink markings written on the outer surface of the packaging container may become unclear or erased, or in severe cases, the material of the container may be corroded or damage may occur due to increased internal pressure.

In addition, the decomposed gas not only causes discomfort to workers when the package is opened and put into use, but is also harmful to the human body, and there has been a strong desire in the technical field to solve these problems.

Therefore, considerable research has been conducted to investigate the causes of these accidents and to find countermeasures.For example, in order to suppress the generation of decomposition gas from the solid chlorine agent mentioned above, it is necessary to reduce the moisture content in the product. There are several other proposals, such as that it is effective or that it is effective to completely block out moisture from the outside air during storage, but none of them are satisfactory.

For example, manufacturing completely anhydrous products is almost impossible in industrial production, and even if metal is used as a material for packaging containers that can be completely isolated from the outside air, the inside of the product gradually deteriorates during long-term storage. Accumulation of sealed decomposition gas may cause corrosion of the vessel wall or deformation or damage of the vessel due to increased pressure.

There are also proposals to form solid chlorine agents into granules or tablets in order to reduce the specific surface area, but this is not an effective method for long-term storage.

Furthermore, there have been proposals to coat the surface of the solid chlorine agent with a film of an inert substance, such as paraffin wax or polyvinyl alcohol, but this is not as effective as the above, and moreover, when used for pool disinfection, oil must be added to the pool water. If it is supplied, it becomes S and is not preferred.

Furthermore, another proposal is to add and mix an ordinary desiccant, such as potash alum, into a solid chlorine agent, but the effect is not sufficient and in some cases may promote the generation of decomposed gas. Yes, it's not good.

Another proposal is to add and mix a stabilizer, such as limonene, to the solid chlorine agent in order to suppress its decomposition, but this method is also insufficiently effective and, on the contrary, promotes the generation of decomposed gas. Or even yellow coloration may occur.

Still another proposal is to store solid chlorine in a paperboard container whose inner wall is coated with an alkali metal silicate, or in a container containing solid chlorine, as described in U.S. Pat. No. 3,061,549. Along with solid chlorine agents, mixtures of MnO2 and CuO, activated alumina, zeolite, clay, pennite, activated montmorillonite, silver phosphate, silver nitrate, mercury nitrate, alkali metal hydroxide, alkali metal carbonate, alkali There is also a known storage method that encloses a small package containing a harmful gas converting agent such as an earth metal oxide in a polyethylene perforated bag, but the container made of paperboard coated with an alkali metal silicate does not last long. Not only does it deteriorate over time and cannot withstand long-term storage, but it also cannot sufficiently suppress the decomposition of the solid chlorine agent, making it impossible to store the solid chlorine agent unchanged for a long period of time.

In addition, another aspect of the above-mentioned U.S. patent, a storage method in which a polyethylene bag containing a small package containing a harmful gas converting agent is enclosed in a container, also prevents accidents due to breakage of the bag during transport or transportation of the container. For example, contact and mixing of the solid chlorine agent and the above-mentioned harmful gas converting agent are likely to occur in the container, and if the power deteriorates, the decomposition of the solid chlorine agent may be accelerated, or the solid chlorine agent may remain unaltered, high-purity product. cannot be stored for a long period of time, and there are still difficulties in implementation.

The present inventors intended to solve the problems in the above-mentioned prior art, and as a result of detailed experimental research, we found that Cab, MgO
, Fed, Na3PO4, etc. were found to be extremely excellent absorbents for the decomposed gas of solid chlorine agents, and compositions obtained by melt-kneading these metal compounds into plastics such as polyethylene and polypropylene were developed. The composition must also exhibit an extremely excellent absorption effect against the decomposition gas of the solid chlorine agent, and the films, sheets, etc. obtained from the composition must be strong and durable, and have material suitability as a storage container. They found this and completed the present invention.

An object of the present invention is to provide a container for a solid chlorine agent containing anhydrous, hydrated, or a mixture thereof of trisubstituted incyanuric acid, disubstituted incyanuric acid, sodium salt or potassium salt of disubstituted incyanuric acid. When stored sealed inside,
By strongly absorbing and fixing the gas generated by decomposition without promoting the generation of decomposition gas, there is no damage or breakage to the container surface or substrate, and no harmful gases, odors, etc. are generated when the container is opened. It is an object of the present invention to provide a simple and safe method for preserving the solid chlorine agent, which does not allow it to evaporate.

Still another object of the present invention is to stably store the solid chlorine agent in a container without deteriorating the performance of the solid chlorine agent, causing deterioration, coloring, etc., and without containing undesirable accompanying materials even in practical use. The purpose is to provide a method for storing information.

The method for preserving the solid chlorine agent (in accordance with the present invention) is to preserve the solid chlorine agent by storing the anhydride, hydrate, or the sodium salt or potassium salt of trisubstituted isocyanuric acid, dichlorinated isocyanuric acid, dichlorinated incyanuric acid, or the like. into a container made of a composition in which one or more metal compounds selected from the group consisting of trisodium phosphate, calcium or magnesium oxides, and ferrous oxide are finely dispersed in plastic. It is characterized by being stored under sealed conditions.

In a particularly preferred embodiment of the present invention, in the above preservation method, the plastic is an ethylene polymer or copolymer, a propylene polymer or copolymer, a vinyl chloride polymer or copolymer, or a mixture thereof. In some cases.

The solid chlorine agent to which the method of the present invention is applied includes trisubstituted incyanuric acid, disubstituted incyanuric acid, anhydride of sodium salt or potassium salt of disubstituted isocyanuric acid, and disubstituted incyanuric acid. It is a solid drug in the form of powder, granules, or tablets containing as an active ingredient a monohydrate of a sodium salt or potassium salt of an acid, a dihydrate of a sodium salt of dibasic incyanuric acid, or a mixture thereof.

These solid chlorine agents are usually difficult to obtain completely anhydrous as industrial products, and even in closed containers, they generate decomposed gases such as chlorine and nitrogen chloride due to the small amount of water they contain, or they can be used in plastic bags or paper bags. It tends to generate decomposition gas in containers with some air permeability, such as drums.

Furthermore, these solid chlorine agents often contain various components depending on the intended use.

Examples of the metal compound used in the method of the present invention include trisodium phosphate, calcium oxide, magnesium oxide, ferrous oxide, or mixtures thereof.

Plastics used in the present invention include polyethylene, copolymers of ethylene and propylene, butene, vinyl acetate, etc., polyolefin resins such as polypropylene or mixtures thereof, polyvinyl chloride, vinyl chloride and ethylene, propylene, vinyl acetate, etc. Other examples include polyvinyl chloride resins such as copolymers with copolymerizable monomers.

The composition in which the metal compound is finely dispersed in the plastic used in the present invention is obtained by kneading the metal compound in powder or granular form with the plastic while the plastic is melted. Examples of containers made from this composition include various storage containers such as bags, bottles, and boxes made from the above composition.

Since the composition exhibits heat-sealing properties, the container can be easily made into a sealed body by heat-sealing.

The above-mentioned composition used in the present invention usually preferably contains about 10 to 60% of the above-mentioned metal compound. Optional additives such as processing aids,
It may contain fillers, stabilizers, etc.

Further, the above-mentioned kneading can be easily carried out by using a mixing roll, a screw extruder, or the like.

Containers made of the above-mentioned composition used in the present invention can be made by ordinary plastic molding methods, for example, bags can be made into films or sheets by an inflation method, T-die method, etc., and then can be made into bags. can be made by blow molding, and boxes can be made by injection molding.

Their shape and size are not particularly limited, and can be arbitrary depending on the purpose of use, ease of handling, etc.

When storing the solid chlorine agent in the container, in order to prevent outside air from entering, after the solid chlorine agent is placed in the container, the container is immediately sealed and the container is stored as is.

If the strength of the above-mentioned container is insufficient for transportation, transport, handling, etc., the solid chlorine agent package can be made into a complete package by placing the contents in a stronger ordinary outer container. .

Thus, when using the method of the present invention, no deterioration or coloring of the solid chlorine agent to be stored occurs during its storage.

The metal compound significantly exhibits the above-mentioned specific effects,
For example, the object of the present invention cannot be achieved by activated carbon, activated clay, sodium chloride, sodium sulfate, calcium butoxide, aluminum hydroxide, ferric oxide, sodium acid phosphate, and the like.

According to the method of the invention, the metal compound used is
Usually, an amount within a few percent of the solid chlorine agent to be stored is sufficient.

The appropriate amount to be used may vary slightly depending on the material of the container in which the solid chlorine agent is sealed, the storage temperature, the storage period, etc., but for example, when using a metal container as the outer container, one Bags containing about % of metal compounds,
Enclosing a solid chlorine agent in a bottle or box is sufficient, and when the bottle or box is opened after being stored at room temperature for 30 days, the operator will hardly notice any odor of decomposed gas.

According to the present invention, when storing a solid chlorine agent, the container uniformly surrounds the solid chlorine agent from the outside, so the container does not deteriorate at all, and the enclosed solid chlorine agent does not change in quality. , it can be safely stored for a long period of 1 to 2 years.

Hereinafter, the explanation will be given with reference examples, comparative examples, and examples.
The technical scope of the present invention is not limited thereto.

Reference example 1 A particle size of 0.00 cm was placed in a three-necked glass container with an internal volume of 200 m1.
Granular trichloroisocyanuric acid 20 with 25~L4mm, moisture content 0.13%, available chlorine content 90.7%
f, the 10th port is sealed with a rubber stopper, the 20th and 30th ports are closed with valve material glass stoppers, and the outside temperature is 3.
It was stored stationary in a constant temperature room at 5°C for 30 days.

Next, a dry nitrogen gas conduit is connected to the 20th pipe, and the 3rd pipe is connected to the 20th pipe.
0 is connected to a conduit leading to 80 ml of 1% orthotolidine hydrochloride aqueous solution, both valves are opened, dry nitrogen gas is introduced from No. 20, and exhausted from No. 30, and decomposition occurs by conducting it into the above orthotolidine solution. The entire amount of the gas was captured in the orthotolidine solution, and the degree of discoloration of the solution was measured by observing the absorbance of yellow light with a wavelength of 440 mμ using a spectrophotometer.

The scale value observed on the photometer is proportional to the amount of chlorine gas or nitrogen chloride gas captured in the orthotolidine solution, so the amount of decomposition gas generated is indicated by the magnitude of the scale value observed on the photometer. Ru.

In the above experiment, the amount of decomposed gas generated immediately after 30 days was set to 100 on the scale.

Separately, an experiment similar to the above was conducted, and the 30th valve was kept closed and the cracked gas was not passed through the orthotolidine solution.
Upon opening the package, a strong chlorine odor was detected.

In the same manner as above, the amount of decomposed gas generated when the storage period was 3 days and 10 days was measured, and the value on the scale was 32.
and 62.

Reference example 2 Film thickness 0.12mm, length and width 160mm x 220
After connecting a dry nitrogen conduit and a tube connected to the tolizine solution near the top opening of a polyvinyl chloride bag of 100 mm in diameter, 20Of trichloroisocyanuric acid, the same as that used in Reference Example 1, was added from the open end. was placed in the container, sealed by heat fusion method, and left standing in a room at 35° C. and 60% relative humidity for 30 days.

Next, in the same manner as in Reference Example 1, the amount of generated decomposition gas trapped in the orthotolidine solution is measured, and the value is set to 100.

Examples 1 to 5 Plastic films A, B listed in Table 1.

The amount of decomposed gas generated was measured in the same manner as in Reference Example 2 except that bags C, D, and E were used, and the results shown in Table 1 were obtained.

The results in the same table show that the method of the present invention is extremely superior.

Comparative Examples 1 to 4 Four parcels containing granular Cab, MgO, FeO, and Na3PO4 each in a 4-g perforated polyvinyl chloride bag, film thickness 0.12 mm, length and width 160mm and 220mm. Four high-density polyethylene bags and trichloroisocyanuric acid were prepared, and the polyethylene bags were filled with 20 oz of trichloroisocyanuric acid and one of the above packets, sealed by heat sealing, and then further sealed. Place in a kraft cardboard box with a thickness of 3 mm and a length and width between 180 mm and 250 mm, and seal it at 35°C relative temperature 60%.
The properties of the metal compounds, the degree of discoloration of the oil-based printing ink markings on the outer surface of the polyethylene bag, and the degree of deterioration of the cardboard were observed. The results were obtained.

The results in Table 2 show that when storing solid chlorine agents in plastic bags for a particularly long period of time, the method of locally causing metal compounds to exist inside the bag is still insufficient. .

Examples 6-10 Plastic films A of Table 1 (Examples 1-5),
The degree of change in the film material of the bags after one year of storage in the same manner as Comparative Examples 1 to 4 except that bags B, C, D, and E were used.
When the degree of decolorization of the oil-based printing ink mark written on the outer surface of the bag and the degree of deterioration of the cardboard were observed, the results shown in Table 3 were obtained.

Claims (1)

[Scope of Claims] 1. A solid chlorine agent containing an anhydride, a hydrate, or a mixture thereof of a sodium salt or potassium salt of trisubstituted incyanuric acid, disubstituted isocyanuric acid, or dicyclic incyanuric acid. is sealed in a container consisting of a composition in which one or more metal compounds selected from the group consisting of trisodium phosphate, calcium or magnesium oxide, and ferrous oxide are finely dispersed in plastic. A method for preserving the solid chlorine agent, which comprises preserving the solid chlorine agent. 2. The solid chlorine agent according to claim 1, wherein the plastic is an ethylene polymer or copolymer, a propylene polymer or copolymer, a vinyl chloride polymer or copolymer, or a mixture thereof. How to save.