JP3033154B2 - How to store solid chlorine agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a safe preservation method for a solid chlorine agent which easily generates a decomposition gas such as a chlorine gas, a nitrogen chloride gas and a chlorine oxide gas during the preservation.

[Prior art] Conventionally, as a solid chlorine agent, trichloroisocyanuric acid, dichloroisocyanuric acid, alkali metal salts of dichloroisocyanuric acid, highly bleached powder, or sodium chlorite, etc. Compositions and the like are known. These are widely used in various fields as fungicides, disinfectants, bleaches and the like in the form of powder, granules, granules or tablets. However, since these solid chlorine agents are produced in factories and used for a number of days before they are put to practical use at the site of use, for example, as long as one to two years pass,
Usually once produced, transported in a sealed packaging container made of paper, plastic, metal, etc.,
During transport, storage, etc., various undesired problems have occurred due to the decomposition gas generated from the solid chlorine agent enclosed therein, and in some cases, dangerous accidents have occurred. For example, when used for disinfection of pools, septic tanks, etc., usually the product name and date of manufacture are indicated, and the product packaged in a plastic film with instructions for use and handling precautions is packed in several bags. In many cases, cardboard or the like, which is convenient for transportation, is filled.However, the strength of corrugated cardboard or fiber drums decreases significantly after production at a factory and before the solid chlorine agent is used. In cans, for example, on iron drums, rust is noticeable,
Brown iron chloride drips from the lid, which can significantly impair the image of the product. In addition, the above-mentioned decomposition gas not only causes discomfort during opening and practical use, but also is harmful to the human body, and it has been strongly desired in the art to solve these problems.

Therefore, research on the causes of these accidents and research on countermeasures has been carried out considerably.For example, in order to suppress the generation of decomposition gas from the solid chlorine agent, it is effective to reduce the moisture content in the product. In addition to the theory that it is effective to completely block the outside moisture during storage, there are some proposals, but none of them are satisfactory. There is also a proposal that the solid chlorine agent is in the form of granules or tablets in order to reduce the specific surface area, but this is not an effective method for long-term storage. Furthermore, there is a proposal to coat the surface of the solid chlorine agent with an inert substance, for example, a film of paraffin or polyvinyl alcohol, but the effect is not sufficient as described above, and in the case of polyvinyl alcohol, moisture is rather absorbed and decomposition gas is increased. In addition, when used for pool sterilization, oil is supplied to the pool water, which is not preferable.

Some proposals have conventionally been made as a solution to such a problem.

For example, in U.S. Pat.No. 4,334,160, calcium oxide, sodium phosphate, ferrous oxide, magnesium oxide,
Activated carbon, activated clay, zeolite, compounds such as sodium sulfate are put in a porous bag with air permeability, and a method of stably storing by enclosing with a solid chlorine agent has been proposed. Sufficient berries cannot be obtained, the generation of chlorine, nitrogen chloride and chlorine oxide gas from the solid chlorine agent is not sufficiently suppressed, and the decomposition of available chlorine is also large.

Further, a method of using a plastic in which oxides of trisodium phosphate, calcium or magnesium are finely dispersed in a plastic as a plastic container for storage (Japanese Patent Publication No. 58-46158), melamine, ammeline ammelide, etc. A method has been proposed in which a finely dispersed plastic is used as a storage container (Japanese Patent Publication No. 59-40180). These methods are good at low temperatures, but have a high temperature and a humidity of 70%.
If this is the case, there are some problems.

Furthermore, Japanese Patent Application Laid-Open No. 58-128382 proposes a method of suppressing the generation of chlorine gas using a specific synthetic zeolite (main component is aluminosilicate), but a remarkable effect is not necessarily obtained. Also, Japanese Patent Application Laid-Open No. 61-145169 proposes to use a preservative comprising a combination of a specific alumina and activated carbon.However, since activated carbon is used, it is not possible to use it in contact with a solid chlorine agent. It is not possible to use the preservative in a gas-permeable container, and when used in a cardboard box or the like, there is a disadvantage that the space is reduced accordingly.

[Problems to be solved by the invention]

In order to eliminate the above-mentioned problems, that is, to eliminate the occurrence of damage, breakage, etc. on the surface of a container such as a cardboard as a packaging material for a solid chlorine agent and a substrate, the present inventors have proposed a plastic film surrounding the solid chlorine agent as water. By using a special packaging material that does not allow gas to pass through, such as chlorine, nitrogen chloride, and chlorine oxide, it does not cause damage or breakage to the container surface such as corrugated cardboard or the substrate, and can be used to simplify the use of solid chlorine agents. Considering that it can be preserved, using various films as a packaging agent for solid chlorine agent,
After leaving the product for a certain period of time under high temperature and humidity, extracting the contents, and examining the measurement and evaluation of cardboard strength and fiber drum strength, polyvinyl alcohol and ethylene / vinyl alcohol copolymer with excellent oxygen gas barrier properties were examined. It has been found that a multilayer film having an intermediate layer has excellent effects, and has completed the present invention.

[Means for solving the problem]

That is, the present invention relates to a method for storing a solid chlorine agent, which comprises using a film of a multilayer polymer having an intermediate layer of an ethylene / vinyl alcohol copolymer or polyvinyl alcohol in a film bag for packaging the solid chlorine agent.

Examples of the solid chlorine agent of the present invention include trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, alkali metal salts of dichlorinated isocyanuric acid, highly bleached powder, and sodium chlorite. Examples of the alkali metal salt of dichlorinated isocyanuric acid include anhydrous and hydrated sodium salts and potassium salts produced industrially.

The multilayer polymer film having an intermediate layer of ethylene / vinyl alcohol copolymer (EVOH) or polyvinyl alcohol (PVOH) used in the present invention has excellent oxygen barrier properties and is used as a bag and a wrap for food packaging. And are readily available. The multilayer polymer film has the inner and outer layers adhered to each other with an adhesive polyolefin resin such as polyethylene, polypropylene, and ethylene vinyl acetate. As the film for the inner and outer layers, at least one film selected from polyolefins such as polyethylene and polypropylene, polyesters, polyamides and the like is used.

It is known that the above-mentioned solid chlorine agent easily generates a decomposition gas under high temperature and high humidity. For example, as a solid chlorine agent, trichlorinated cyanuric acid with an effective chlorine content of 89.0%
Five 15g tablets were placed in a 500cc sealed flask, and the initial humidity was 40 ° C and 50% humidity. The amount of decomposition gas generated after 24 hours was 2mg, but the initial temperature was 40 ° C and 70% humidity. And 24
After hours, it increased to 4 mg. Five tablets were placed in the following three types of film bags (size: 10 cm x 10 cm) and heat-sealed. Each of them was placed in a 500 cc sealed flask, and left at an initial humidity of 40 ° C and 70% humidity. The generation of cracked gas was measured.

Multilayer film (manufactured by Nippon Matai Co., Ltd., trade name: VARIEST E type) with a low-density polyethylene EVOH as an intermediate layer and an inner and outer layer of low-density polyethylene (100 μm) having a thickness of 100 μm, and a polyvinylidene fluoride intermediate layer (3 μm) A multilayer film sandwiched between polypropylene 25 µm and linear low-density polyethylene 25 µm (trade name: Alphan KOP, manufactured by Honshu Paper Co., Ltd.) As a result, the decomposition gas in the low-density polyethylene bag after standing for 24 hours is 1.5 mg, and the polyvinylidene fluoride is In the multilayer film as the intermediate layer, blisters were observed in the bag at 0.4 mg in 3 days after leaving the decomposition gas for 24 hours, and polyvinylidene chloride and peeling of the exterior were observed. However, in the case of the multilayer film having an intermediate layer of EVOH used in the present invention, it was zero even after 30 days, and was only 0.003 mg after 60 days.

It is known that the above-mentioned multilayer film having EVOH and polyvinylidene fluoride as inner layers has a low oxygen permeability and a low moisture permeability. However, surprisingly, a multilayer film having polyvinylidene fluoride as an inner layer has a large amount of decomposition gas generated and permeated by a solid chlorine agent. It is considered that the reason for this is that, due to the hydrogen bond with the OH group of vinyl alcohol in the intermediate layer, the initially permeated moisture is retained in the intermediate layer, and the external moisture cannot enter from the intermediate layer. On the other hand, when the intermediate layer was polyvinylidene fluoride, there was no OH group and there was nothing to cause strong hydrogen bonding, so water was not retained, and because it entered the interior, it reacted with the solid chlorine agent and generated decomposition gas. I think that the.

In the method for storing a solid chlorine agent of the present invention, the solid chlorine agent may be packaged only in the above-mentioned multilayer film, but the solid chlorine agent is packaged in a conventionally used film,
The exterior may be packaged with the multilayer film used in the present invention, or a solid chlorine agent may be packaged with the multilayer film of the present invention, and the exterior may be packaged with a film conventionally used.

A film of a multilayer polymer having an intermediate layer of an ethylene / vinyl alcohol copolymer or polyvinyl alcohol used in the present invention, which is packaged with a solid chlorine agent, placed in a cardboard box, and stored for a long period of time. Since no more decomposition gas is generated, there is an excellent effect that there is no deterioration of the corrugated cardboard which has been a problem in the past.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 A multilayer film bag (thickness gauge) in which 12 μm of an ethylene / vinyl alcohol copolymer was used as an intermediate layer, and the inner and outer layers were made of low-density polyethylene 30 μm, and the intermediate layer and the inner and outer layers were bonded with a commonly used adhesive polyolefin resin. 70μ, manufactured by Nippon Matai Co., Ltd. Variest film E type 20cm
× 15 cm), 300 g of a 15 g tablet of trichlorinated isocyanuric acid was placed therein, heat-sealed, and then stored in a 2 liter glass sealed container at 40 ° C. and 90% humidity. After 24 hours, when the decomposition gas in the closed container that had permeated the film was measured, the concentration in 2 l was 0.5 ppm or less. The concentration in 2 liters was 0.5 ppm or less, even if left under the same conditions for up to three months.

Comparative Example 1 In place of the multilayer film of Example 1, a commercially available low-density polyethylene bag (20 cm × 15 cm) having a thickness of 100 μm was used.
When stored under the same conditions as in Example 1, after 24 hours, the decomposition gas in the closed container that had passed through the film was measured.
The concentration in 2 l became 26000 ppm. It can be seen that the generation of decomposition gas is much larger than in Example 1.

Comparative Example 3 Instead of the multilayer film of Example 1, a multilayer film (53 μm in thickness, manufactured by Honshu Paper Company, trade name: Alphan KOP) was used as a polyvinylidene fluoride intermediate layer (3 μm) sandwiched between polypropylene 25 μm and linear low density polyethylene 25 μm. When stored under the same conditions as in Example 1, when the decomposition gas in the sealed container that had passed through the film was measured 24 hours later, the concentration in 2 l was 160 ppm,
In three days, blisters were seen in the bag, and polyvinylidene chloride and peeling of the outer layer were seen.

Example 2 1000 tablets (15 kg) of 15 g tablets of trichlorinated isocyanuric acid
Was placed in a high-density polyethylene small bag 50 having a thickness of 100 μm, and each tablet was heat-sealed. Next, 50 polyethylene bags were used as the bag (50 cm × 80 cm) of the intermediate layer 12 μm used in Example 1 and a film of 70 μm in total.
cm) and the upper part was squeezed with a polyethylene-coated wire. The cardboard is a commonly used outer dimension of 410 × 360 × 200 mm, front liner white B220, AB flute, and has a body frame. After storing the entire cardboard in a constant temperature and humidity of 40 ° C. and a humidity of 75% for 4 months, the contents were taken out, and the strength of the cardboard by a full compression test was 550 kg. The total compressive strength of the new cardboard was 750 kg.

Comparative Example 4 1000 tablets (15 kg) of 15 g tablets of trichlorinated isocyanuric acid
Were placed in a high-density polyethylene small bag 50 having a thickness of 100 μm, and each bag was heat-sealed. Next, 50 polyethylene bags were used in Comparative Example 1 for 100 bags.
μm in a commercially available low-density polyethylene bag (50 cm × 80 cm), the upper part is squeezed with a polyethylene-coated wire in the same manner as in Example 2, placed in a cardboard box, and the entire cardboard is placed in a constant temperature and humidity room at 40 ° C. and 75% humidity. After storage for 4 months, the contents were taken out, and the strength of the cardboard was determined by a total compression test. The strength was 80 kg, and the cardboard was significantly deteriorated until it was easily crushed by hand.

Comparative Example 5 1000 tablets (15 kg) of 15 g tablets of trichlorinated isocyanuric acid
Was placed in a high-density polyethylene small bag 50 having a thickness of 100 μm, and each tablet was heat-sealed. Next, 50 polyethylene bags were used as the polyvinylidene fluoride intermediate layer (3 μm) used in Comparative Example 3 and polypropylene was used.
Put in a multilayer film bag (50 cm × 80 cm) sandwiched between 25 μm and linear low-density polyethylene 25 μm, squeeze the upper part with a polyethylene-coated wire as in Example 2, put in cardboard, put the whole cardboard at 40 ° C., humidity 75
% For 4 months, the contents were taken out, and the strength of the corrugated cardboard was measured by a full compression test. The strength was 390 kg, which was 70% that of Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 251/36 B32B 27/30 B65D 81/00 B65D 85/84 B65D 85/82 C01B 11/06 C01B 11 / 10 CA (STN)

Claims (2)

(57) [Claims] 1. A method for storing a solid chlorine agent, comprising using a film of a multilayer polymer having an intermediate layer of an ethylene / vinyl alcohol copolymer or polyvinyl alcohol in a film bag for packaging the solid chlorine agent. 2. The method for preserving a solid chlorine agent according to claim 1, wherein the inner and outer layers of the multi-layer film are at least one film selected from polyolefin, polyester and polyamide.