JPH0132829B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a preservation method that suppresses as much as possible the generation of gases such as chlorine and nitrogen chloride due to decomposition of chlorinated isocyanuric acid or its salt. Chlorinated isocyanuric acid or its salts that are generally used in practical use include trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, anhydrous and monohydrate of sodium or potassium dichlorinated isocyanurate. , a dihydrate of dichlorinated sodium isocyanurate, and the like. These are hereinafter collectively referred to as chlorinated isocyanuric acids. These chlorinated isocyanuric acids are generally put into practical use in powder form or in the form of granules, granules, or tablets. Furthermore, a dried product with a moisture content of 1% or less is usually used. These chlorinated isocyanuric acids are widely used as disinfectants, disinfectants, bleaches, etc. in various fields. Furthermore, if chlorinated isocyanuric acids are left exposed to the atmosphere, they will decompose and generate harmful gases such as chlorine and nitrogen chloride. For this reason,
After manufacture, until they are put into practical use, they are generally stored and transported in airtight containers made of paper, plastic, metal, or the like. However, when stored and transported for a long period of time, a considerable amount of decomposition gas is generated even in these closed containers, causing various undesirable and even dangerous events. There is. Various methods have been proposed to suppress decomposition by adding additives to chlorinated isocyanuric acids, but the effects may not be sufficient or the additives may have an unfavorable effect on the practical use of chlorinated isocyanuric acids. ing. In addition, JP-A No. 55-98274 discloses that chlorinated isocyanuric acids are mixed with one or more metal compounds selected from the group consisting of calcium or magnesium oxides and ferrous oxides in plastics. A method has been proposed in which the dispersed composition is stored in a sealed bag or container. This method is certainly effective in suppressing the decomposition of chlorinated isocyanuric acids. However, the effects vary significantly depending on the type of additive proposed, and are less effective for long-term storage. That is, the surfaces of bags and containers tend to absorb moisture, and in the case of films, they become wrinkled and wavy, reducing the deodorizing effect.
Furthermore, moisture absorption on the surface of the container makes storage difficult, and ink markings on the surface become unclear. Furthermore,
Plastic films or sheets into which the additives generated are mixed have poor heat-sealing properties, low strength, and are prone to tearing at the corners. The method of the present invention has an excellent effect of suppressing the decomposition of chlorinated isocyanuric acids, and even when kept for more than 10 months up to about 3 years, the decomposition of chlorinated isocyanuric acids is minimal, causing damage to containers and printing ink. No deterioration occurs, and the container used has good heat sealing properties.
To provide a method for preserving chlorinated isocyanuric acids having high strength and no hygroscopicity. In the method for preserving chlorinated isocyanuric acids according to the present invention, 10 to 10 parts by weight of one or more metal oxides selected from the group consisting of calcium oxide, magnesium oxide, and boron oxide are added to 100 parts by weight of the synthetic resin. This method is characterized by storing the product under seal in a container made of a multilayer structure in which synthetic resin layers containing no metal oxide are laminated on both the inner and outer surfaces of a synthetic resin layer containing 200 parts by weight. In a preferred embodiment of the method of the present invention, the synthetic resin is a polymer or copolymer of ethylene, propylene, vinyl chloride or vinylidene chloride, or a mixture thereof. In another preferred embodiment of the method of the present invention, the thickness of the metal resin layer mixed with the metal oxide is 20 to 200μ, and the thickness of the synthetic resin layer not mixed with the metal oxide is 10 to 200μ. be. In yet another preferred embodiment of the method of the present invention, the weight of the metal oxide in the synthetic resin layer mixed with the metal oxide is 0.1 to 10% based on the weight of the chlorinated isocyanuric acids to be stored. It is. The method of the present invention will be explained in more detail below. In the method of the present invention, synthetic resin layers that do not contain metal oxides are laminated on both the inner and outer surfaces of the synthetic resin layer that contains metal oxides. . In the method of the present invention, the metal oxide mixed into the synthetic resin of the middle layer is one or more metal oxides selected from the group consisting of calcium oxide, magnesium oxide, and boron oxide. Metal oxides other than those mentioned above, such as the metal oxides and oxide salts other than those listed in JP-A-55-98274, are significantly inferior in effectiveness to the above-mentioned metal oxides. The above metal oxide is mixed into the synthetic resin as a finely divided anhydride. It is desirable that the size of the fine powder is smaller than the thickness of the middle layer. The amount mixed into the synthetic resin is suitably in the range of 10 to 200 parts by weight per 100 parts by weight of the synthetic resin. If the amount is less than 10 parts by weight, it is difficult to obtain the effects of the method of the present invention. However, although the method of the present invention can be effective if the container capacity is made small relative to the container surface area, it is not economical in this case. Moreover, if it exceeds 200 parts by weight, molding becomes difficult. Furthermore, the amount of metal oxide mixed in the middle layer must also be taken into consideration based on the weight of the chlorinated isocyanuric acids stored in the container. Since these metal oxides play a major role in suppressing the decomposition of chlorinated isocyanuric acids, the weight of the metal oxides in the middle layer used in the container is based on the weight of the chlorinated isocyanuric acid stored in the container. 0.1 of the weight of acids
% or more. Furthermore, even if the concentration is increased to 10%, the decomposition inhibiting effect remains the same. The method of mixing the above metal oxides into synthetic resin is as follows:
It is carried out in the same way as the method for adding general processing aids, fillers, stabilizers, etc. That is, it is mixed in by methods such as adding it during melt-kneading of synthetic resins or adding it during kneading with a screw extruder. The synthetic resin used in the method of the present invention includes:
Any material that can be formed into a sheet or film may be used. Among these, polymers or copolymers of ethylene, propylene, vinyl chloride or vinylidene chloride, or mixtures thereof are preferred. In the method of the present invention, the middle layer and the inner and outer layers are laminated to form a triple structure, and the triple structure forms a container. The triple structure may be created by any conventional method. For example, 3
The layers are coextruded to form a blown film, which is then heat-sealed to form a bag. In addition, a bottle is made from a three-layer coextruded parison by blow molding. In addition, a method of laminating and adhering calender sheets is also used. The thickness of the middle layer and the inner and outer layers as a three-layer structure is preferably in the range of 40 to 600 μm from the viewpoint of strength and practical use. However, in the case of storage for a relatively short period of time, the thickness may be thinner than the above-mentioned lower limit thickness, and when it is desired to use a large container, it may be thicker than the above-mentioned upper limit thickness. Further, it is effective to make the thickness of the inner and outer layers each 10 μm or more. Therefore, the thickness of the middle layer is 20 to 200μ, and the thickness of each of the inner and outer layers is 10μ.
~200μ is preferred. The method of the present invention is configured as described above. In an embodiment, from the viewpoint of ease of storage and transportation and strength, a plurality of three-layered packages are generally housed in an outer container made of stronger cardboard or the like. 3
The layered structure container may be used in duplicate, and a plurality of the packages may be placed in a more durable outer container. Actually, the outer layer is 100μ, the middle layer is 250μ, the inner layer is 50μ, and the total thickness is 400μ.
Then, chlorinated isocyanuric acids are stored in a blow bottle with a capacity of 1 (polyethylene is used as the synthetic resin) and sealed with a polyethylene cap.
600 bottles were made, stored and transported, and good results were obtained. Furthermore, when a relatively large amount of chlorinated isocyanuric acids is desired to be stored in a fiber drum, the fiber drum may be lined with the three-layer structure used in the method of the present invention. When the fiber drum is sufficiently airtight, the three-layer structure used in the present invention may be used as a lid. Furthermore, the container used in the method of the present invention may be housed in a cardboard box and used as a large bag (outer bag) into which a plurality of containers containing chlorinated cyanuric acids or a mixed product are placed. Since the method of the present invention is configured and carried out as described above, it can produce many excellent effects as described below. That is, chlorinated isocyanuric acids can be stored for a long period of time, such as 10 months or more, approximately 3 years, while suppressing their decomposition. Therefore, when the container is opened, there is almost no odor of decomposed gas such as chlorine or nitrogen chloride, and the container will not be damaged or the printing ink will change in quality. Furthermore, since both sides of the container are made of synthetic resin layers that do not contain metal oxides, they have good heat sealability and do not absorb moisture. Furthermore, this container has great strength. Therefore, the method of the present invention has extremely great practical value. Next, examples of the method of the present invention will be described. In the examples, several types of chlorinated isocyanuric acids were stored and sealed in three-layer plastic film bags made of various metal oxides, and after being stored under certain conditions, the condition was evaluated by visual observation and sensory testing. . In addition, as a comparative example, when a plastic film containing no metal oxides was used for the container,
When a single-layer plastic film containing a metal oxide is used as proposed in Publication No. 98274, and a two-layer structure in which a plastic film not containing a metal oxide is laminated only on the outside of a plastic film containing a metal oxide. A storage test using a body film was conducted in the same manner as in Examples. Specifications, conditions, etc. for each material, test, evaluation, etc. are as follows. (1) Test chlorinated isocyanuric acids (1) Trichloroisocyanuric acid granules (TCCA
It is abbreviated as ) Moisture 0.19%, particle size 0.24-1.4mm, available chlorine content 90.4%. (2) Dichloroisocyanuric acid granules (abbreviated as DCCA) Moisture 0.21%, particle size 0.24-1.4 mm, available chlorine content 71.7%. (3) Sodium dichloroisocyanurate anhydrate granules (abbreviated as DCC-Na) Moisture 0.96%, particle size 0.24-1.4 mm, available chlorine content 60.4%. (2) Metal oxide Calcium oxide (CaO), magnesium oxide (MgO), and boron oxide (B ₂ O ₃ ) were all used, and fine powders that passed through a 300 mesh sieve (0.046 mm or less) were used. (3) Synthetic resins, containers, and packaging methods The synthetic resins used were a 1:1 mixture of high-density and low-density polyethylene (PE), polypropylene (PP), and polyvinylidene chloride (PViC). For the layer in which the metal oxide is mixed, this is kneaded and melted with a synthetic resin, and made into a single-layer or multi-layer inflation film with a thickness of 120μ or 180μ by single-layer, double-layer or triple-layer coextrusion, cutting, 280mm (length) x 220mm (width) bag (inner bag) by heat fusion
After printing the product name, design, directions for use, etc. on the container surface using chlorine-resistant printing ink, 1 kg of chlorinated isocyanuric acid was added to each container, and the containers were sealed by heat sealing. (4) Preservation method: 15 bags of the packaging obtained in the previous (3), length x width.
After putting it in a single-layer plastic bag (outer bag or large bag) with a size of 850 x 400 mm and a thickness of 100μ, and sealing it, it is further placed into a bag with a length x width x height of 395 x 350 x 175 mm and a thickness of 3.
I put it in a mm craft cardboard box and sealed it with glue. (5) Storage conditions Stored in a warehouse for 10 months including summer. (6) Evaluation items and evaluation methods (1) Degree of deterioration (fading) of printing ink Changes in the printed ink (pigment) and changes in sharpness were visually observed and evaluated according to the degree of decolorization as shown below. For example, ultramarine blue deteriorates as follows: dark blue → blue → light blue → gray → disappear. ◎ No change at all 〇 Slightly bleached △ Significantly bleached × Very markedly bleached (2) Embrittlement of cardboard The embrittlement of the outside and inside of the box due to operator's finger pressure was evaluated in the following 5 grades by sensory test and visual observation. ◎ No change on the outside and inside 〇 Slight embrittlement on the inside □ Significant embrittlement on the inside △ Significant embrittlement on the inside, slight embrittlement on the outside It was evaluated on a five-point scale. ◎ No chlorine odor at all 〇 Faint chlorine odor □ Weak chlorine odor △ Fairly strong chlorine odor × Extremely strong chlorine odor Specifications and conditions in Examples and Comparative Examples are shown in Table 1, and evaluation results are shown in Table 2.

【table】

【table】

[Table] As is clear from Tables 1 and 2, in the examples using the method of the present invention, there was almost no deterioration of the printing ink or embrittlement of the cardboard, and there was only a slight chlorine odor when the package was opened. be. On the other hand, the evaluation values of comparative examples that did not use the method of the present invention were significantly inferior. In particular, evaluations of Nos. 10 to 15 using single-layer plastic films that do not contain metal oxides such as CaO are poor. No. 13 is relatively good because the sample
This is because DCC-Na is relatively difficult to decompose. Comparative example No. corresponding to the embodiment of the invention of JP-A No. 55-98274.
Nos. 1 to 7 are better than Nos. 10 to 15, but not sufficient. Comparative Examples Nos. 8 and 9 correspond to the three-layer structure of the present invention with the inner layer removed, and although they are superior to other comparative examples, they are not as good as the examples. Those with only outer and middle layers tend to absorb moisture and are difficult to preserve. In addition, moisture absorption causes warping, reducing the deodorizing effect.

Claims (1)

[Claims] 1. 100 parts by weight of one or more metal oxides selected from the group consisting of calcium oxide, magnesium oxide, and boron oxide per 100 parts by weight of synthetic resin.
~200 parts by weight of the synthetic resin layer on both the inside and outside sides.
A method for preserving chlorinated isocyanuric acid or a salt thereof, which comprises storing the chlorinated isocyanuric acid or its salt in a container made of a multilayer structure in which synthetic resin layers not containing the metal oxide are laminated. 2. The method for preserving chlorinated isocyanuric acid or a salt thereof according to claim 1, wherein the synthetic resin is a polymer or copolymer of ethylene, propylene, vinyl chloride, vinylidene chloride, or a mixture thereof. 3. Claim 1 or 2, wherein the thickness of the synthetic resin layer mixed with the metal oxide is 20 to 200 μm, and the thickness of the synthetic resin layer not mixed with the metal oxide is 10 to 200 μm. A method for preserving chlorinated isocyanuric acid or its salt. 4. Claim 3, wherein the weight of the metal oxide in the synthetic resin layer mixed with the metal oxide is 0.1 to 10% based on the weight of the chlorinated isocyanuric acid or its salt to be stored. A method for preserving chlorinated isocyanuric acid or its salt.