JPH05112387A - Sealed package of iodine and iodine containing compound - Google Patents

Abstract

PURPOSE:To enable handling of a package without housing it in a fiber drum by a method wherein iodine or, iodine containing compound or goods containing it is package and sealed with a specific film material such as polyvinylidene chloride. CONSTITUTION:As packaging material for packaging sealingly corrosive and stimulating iodine, iodine compound or goods containing it (referred as goods hereinafter), film material is used which comprises polyvinylidene chloride or vinylidene chloride-vinyl chloride copolymer having a prescribed thickness. In order to improve gas barrier, on an outer surface of the above-mentioned thermoplastic polymer, metal film prominent in corrosion-proofness against iodine such as tantalum, titanium, Ni-Cr alloy (Hastelloy C) is steamed or adhered. This permission prevented and sealed package can be handled safely without housing it in a fiber drum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hermetically sealed package which is hermetically sealed and packaged with a thermoplastic polymer material so as to prevent permeation of highly corrosive or irritating iodine or iodine compounds.

[0002]

2. Description of the Related Art Iodine has a strong corrosive property, and penetrates a film of a resin which is generally used, and has an adverse effect such as corroding a substance outside thereof.

Further, among iodine-containing compounds, substances having a strong reducing property are easily oxidized or reduced by an oxidizing agent such as oxygen, and substances having a strong oxidizing property are easily oxidized or reduced by various reducing agents to generate free iodine. Further, iodine-containing complexes, molecular compounds, adsorbents and the like also generate iodine due to physical effects such as thermal alteration and chemical effects such as decomposition. However, as described above, iodine has a problem that it diffuses and permeates through the conventional resin film and corrodes external substances. On the other hand, there is an example in which iodine is simply packed in a bag such as Saran, but it is used for the corrosion-resistant packaging by utilizing the chemical resistance of Saran against corrosive iodine. It does not teach anything about preventing the permeation of iodine gas through the film.

Therefore, it has been conventionally practiced to line the inside of a container of such a corrosive substance with a resin that is chemically stable to the corrosive substance. It sometimes corroded the body metal. To solve this problem, for example, as described in Japanese Patent Publication No. 40-26310, a gap is formed between the metal peripheral wall of the container main body and the inner resin lining layer wall, and an inert gas is continuously introduced into this gap. A technique is known in which the corrosive substances that are discharged and then diffused through the resin lining layer are expelled out of the system together with the gas.

[0005]

However, it is troublesome to form a container having such a gap and having a gas introduction means and a discharge means, and it is inevitably a large-scale container. Since a gas source (cylinder) and the like must be provided inevitably, it is difficult to make the container easy to carry. Further, it is difficult to make a small-sized container and mass-produce the container because there is a limitation that each container must be equipped with a gas introduction means, a gas source (cylinder) and the like.

[0006] By the way, many studies have been conducted on the diffusion and permeation of gases and vapors into polymer solids because of their academic and practical interest. And the process of gas permeation through the solid polymer membrane involves the condensation and dissolution of gas on one side of the membrane,
It is known that adsorption and the like occur, and then the gas diffuses in the solid and is vaporized and desorbed on the other side of the membrane. However, gas permeability to polymer solids has been tested with water vapor, oxygen, nitrogen, etc., and some organic compounds have been tested, but halogen gas has not been fully tested. The reality was that there was none.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made, as a result of various studies on the permeability (difficulty, speed, etc.) of a polymer solid membrane, particularly iodine gas, and as a result, a certain chlorine-containing thermoplastic polymer was obtained. Based on this finding, it was found that the polymer can be used as a polymer solid membrane to extremely effectively prevent the permeation of iodine gas, and therefore the polymer can be used to achieve the permeation prevention by packaging and sealing iodine. Invented the invention.

That is, according to the present invention, iodine, an iodine-containing compound or an article containing them is wrapped with a film material made of polyvinylidene chloride or a vinylidene chloride-vinyl chloride copolymer having a predetermined thickness and sealed, and iodine is obtained. The present invention provides a sealed package for preventing permeation of an iodine-containing compound or an article containing the same, which package can be handled without being stored in a fiber drum.

In the present invention, in order to improve the gas barrier property, a metal film may be deposited or adhered on the outer surface of the thermoplastic polymer. There is no particular limitation on the type of metal used at this time. That is, when iodine permeates a polymer material, corrosion resistance to iodine is required, but in the case of the above-mentioned thermoplastic polymer, since permeation of iodine hardly occurs, it is necessary to select a metal having corrosion resistance to iodine. There is no. However, from the viewpoint of corrosion resistance to iodine, tantalum, titanium, Ni—Cr alloy (Hastelloy C) and the like are particularly excellent.

The packaging material used in the present invention has little or no permeation of iodine, which is a condition required for packaging materials of iodine and iodine-containing compounds. Permeation of other gases, especially oxygen, hydrogen and water vapor, is low. It is satisfied that the deterioration of the packaging material due to iodine is small, or that the deterioration does not occur. These are polymers having a substituted ethylene skeleton containing chlorine as described above, such as those having a substituted ethylene skeleton, those that are difficult to adsorb the packaging iodine in the polymer skeleton, those that have high crystallinity, etc. preferable.

Next, iodine-containing compounds to which the present invention can be applied include iodine methyl represented by the formula R ¹ I (R ¹ is an alkyl group), ethyl iodide, propyl iodide, isopropyl iodide, butyl iodide, Methylene iodide represented by the formula R ² I ₂ (R ² is a divalent aliphatic hydrocarbon group) such as amyl iodide, hexyl iodide, heptyl iodide, octyl iodide, cetyl iodide and octadecyl iodide. , Ethylidene iodide, ethylene iodide, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, etc., and the formula R ³ I ₃ (R ³ is a trivalent aliphatic hydrocarbon group) Iodoform represented by, iodoacetylene, diiodoacetylene, which is an iodide of an unsaturated hydrocarbon,
Propargyl iodide, vinyl iodide, 1.2-diiodoethylene, isopropenyl iodide, allyl iodide, etc.
Alicyclic hydrocarbon iodides such as cyclopentyl iodide and cyclohexyl iodide, aromatic hydrocarbon iodides such as iodobenzene, benzyl iodide, xylylene iodide, diiodobenzene and iodotoluene Iodides such as 2-iodoethyl alcohol, γ and β-iodoisopropyl alcohol that are iodides, iodoacetaldehyde that is iodide of aldehydes, iodoacetones that are iodides of ketones, iodideacetones such as diiodoacetone, etc. Iodoacetic acid, acetyl iodide, iodobenzoic acid, benzoyl iodide, etc. which are substituted aromatic iodides, iodophenol, 3.5-diiodosalicylic acid, iodoalfionic acid, iodophthalein, triphenylmethyl iodide , Erythrosine, etc. N-methylpyridinium iodide, which is an alkylpyridinium iodide, such as β-iodoethylamine, which is an iodide of amine, and melamine iodide, which is a hydroiodide salt of various amines, such as ethylenediamine dihydroiodide and melamine hydroiodide. , N-ethylpyridinium iodide, N-n-propylpyridinium iodide, N-isopropylpyridinium iodide, N-n-butylpyridinium iodide, and the like, and complexes of these alkylpyridinium iodides and iodine, and complexes of iodine and various compounds with pyrene. -Iodine, perylene-iodine, phenothiazine-iodine, N-methylphenothiazine-iodine, N-ethylphenothiazine-iodine, benzidine-iodine, phenoxazine-iodine, polyvinylpyrrolidone-iodine, interface Sex agent - iodine (iodophor), polyvinyl alcohol - iodine, beta-cyclodextrin - iodine, starch - iodine, proteins - such as iodine, wherein R ¹ IO ₂
An iodooxy compound represented by (R ¹ has the same meaning as described above), a formula R ¹ IO (R ¹ has the same meaning as described above)
An iodoso compound represented by the formula [R ¹ IR ¹ ] ⁺ I
(R ¹ has the same meaning as described above), a quaternary ammonium salt represented by R ⁴ R ⁵ R ⁶ R ⁷ N ⁺ I (where R ^{4 to} R ⁷ are alkyl groups), etc. There is.

Further, as the iodine-containing compound to which the present invention can be applied, the following inorganic compounds can be mentioned in addition to the above-mentioned organic compounds. For example, in a compound containing iodine as a cation, ICIO ₄ , I (CIO ₄ )
₃ , ICN, ISCN, I (SCN) _3, etc., and iodine oxides such as I ₂ O, I ₂ O ₃ , I ₂ O ₅ , I ₂ O ₇ , and IO.
₄ and corresponding acids HIO, HIO ₂ , HIO
₃ , HIO _4, etc., periodic acid H ₅ IO ₄ , and iodine iodides ICI, ICI ₃ , IBr, IF ₅ , I
Examples thereof include F _{7 and the} like, hydroiodic acid (HI) and the like.

These iodine and iodine-containing compounds are
In addition to being packaged by itself, it is also packaged together with other metal parts in the object to be packaged. Therefore, in the packaging method of the present invention, in addition to the case where the packaging materials are brought into close contact with each other after the articles to be packaged are accommodated inside, the packaging material can be brought into close contact with the metal component.

The term "packaging and sealing" as used in the present invention means that a specific material specified in the present invention is used in a predetermined thickness so as to prevent iodine and the like from permeating out of the system. Not only packaging but also the method of hermetically storing in a container. The thickness of the film material is sufficient to prevent the permeation of iodine gas and is appropriately determined according to the application, but it is needless to say that the thicker it is, the more complete gas barrier property is.

[0015]

EFFECTS OF THE INVENTION According to the present invention, there is an excellent effect that iodine having strong corrosiveness and irritancy or a compound containing it can be completely sealed. Further, according to the present invention,
The packaging material is not deteriorated by iodine.
Such application fields of the present invention are wide, and particularly preferable examples thereof include reagents, medicines, bactericides, batteries (lithium-iodine batteries) containing iodine and iodine-containing compounds that are easily unstable or deteriorated in the atmosphere. There is packaging such as battery contents containing iodine).

[0016]

【Example】

Next, the present invention will be described in more detail based on examples. Example 1 As test iodine-containing compounds, I ₃ ^■ a 1.0 mol /
Liter aqueous solution containing, crystals of iodine, complexes and polyvinylpyrrolidone consisting of N-n-butyl-pyridinium iodide and I ₂ Metropolitan - using iodine complex. As packaging material, 0.05 mm thick polyvinylidene chloride (film I), vinylidene chloride-vinyl chloride copolymer (film
The film of II) was used. For comparison, a polyethylene film (Film III) was also subjected to the same test.

First, an iodine adsorption test was conducted as follows. Put the iodine-containing sample and the film sample in a closed glass container and set them at a predetermined temperature (30 ° C, 40 ° C or 50 ° C).
The film sample was taken out, washed and dried, and the weight change was measured. The results are shown in Table 1. From the results in this table, it is understood that the films I and II of the present invention have a far smaller iodine adsorption amount than the film III.

[0018]

[Table 1]

Then, a permeability test was conducted. This is 2
A film sandwiched between two glass containers was used. An iodine-containing sample was placed in one container and an iodine detection solution (starch aqueous solution) was placed in the other container.
C., 40.degree. C. or 50.degree. C.), and the time until the color reaction of the iodine detection solution occurs was measured. The results are shown in Table 2. From the results in this table, the films I and II are film II.
It can be seen that the permeability of iodine is lower than that of I.

[0020]

[Table 2]

Comparative Example Chlorine gas as a halogen-containing substance for testing instead of iodine,
A permeability test was conducted in the same manner as in Example 1 except that bromine gas was used. The three types of films used in Example 1 were used as the packaging material.

In this test, one container was filled with chlorine gas or bromine gas, and the other container was filled with a liquid containing KI and starch. The permeated chlorine or bromine is Cl ₂ (or Br ₂ ) + 2Kl → 2KCl (or KB
r) + I ₂ produces iodine, which is detected by starch and turns purple. The time required for the color reaction to occur was measured, and the results are shown in Table 3.

[0023]

[Table 3]

From the results in the above table, it is understood that the permeation of chlorine gas and bromine gas is significantly faster than that of iodine. Therefore, the packaging material using the above material is most suitable for iodine, and cannot be used as a packaging material for sealing other halogen such as chlorine and bromine.

Example 2 A sample was prepared by fusing an aluminum foil having a thickness of 0.05 mm to the same film as that used in Example 1, and the same adsorption test and permeability test as in Example 1 were conducted. As a result, the amount of iodine adsorbed was about 15% lower than in the case of Example 1, and there was no particular problem, with only a sample in which peeling between the foil and the film was likely to be observed. Then, for the permeability test, all samples did not permeate after 240 days.

Claims (2)

[Claims] 1. Iodine, an iodine-containing compound obtained by wrapping iodine, an iodine-containing compound or an article containing them, with a film material made of polyvinylidene chloride or a vinylidene chloride-vinyl chloride copolymer having a predetermined thickness and hermetically sealed. A sealed package for preventing permeation of articles containing them, wherein the package can be handled without being housed in a fiber drum. 2. The package according to claim 1, wherein the film material made of the thermoplastic polymer has a metal film formed on the outer surface.