JP2005152404A - Gaseous iodine discharge tool, and method and apparatus for preparing iodine-containing solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an iodine gas discharge tool with which a desired iodine-containing liquid can easily and safely be produced, which can be used advantageously for various purposes of disinfection, and in which water and/or an organic solvent and an iodine-adsorbing polymer coexist and the coexisting substances are covered with a gas-permeable pore-less film. <P>SOLUTION: Water and/or the organic solvent coexist with the iodine-adsorbing polymer, thereby adjusting the amount of iodine to be eluted into water outside the iodine gas discharge tool. In the iodine gas discharge tool, water or the organic solvent coexists with the iodine-adsorbing polymer, and these substances are coated with the gas-permeable pore-less film. In the method and apparatus for producing the iodine-containing solution, the polymer and water and/or the organic solvent coexist, and the coexistent substances are coated with the gas-permeable pore-less film to form the iodine gas discharge tool and this tool is then left in a closed system together with water and/or the organic solvent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an iodine gas releasing device in which a polymer compound adsorbing iodine is covered with a gas-permeable non-porous film, an iodine-containing liquid preparation method and an iodine-containing liquid preparation device using the same.

  Iodine is widely used in hospitals and other places because of its strong bactericidal activity and relatively low harm to the human body. Most of them are used in the form of a complex such as povidone iodine, but they can also be adsorbed on a polymer compound or the like, and iodine can be released gradually therefrom (Japanese Patent Laid-Open Nos. 57-51725 and 59-193189). JP-A-60-232288, JP-A-9-67216, JP-A-9-122655, JP-T-9-509876, JP-A-2003-213022).

  Dissolving iodine released from such a polymer compound adsorbing iodine in water can produce bactericidal iodine water, or disinfect the surroundings of the polymer adsorbing iodine. (Japanese Patent Laid-Open No. 10-165960). It is also possible to use iodine gas that is gradually released from the polymer compound adsorbing iodine for disinfection (Japanese Patent Laid-Open No. 2003-213022). However, if the polymer compound adsorbed with iodine is kept in contact with water for a long period of time, the iodine concentration in the water becomes excessive, causing coloring, and unnecessary life wasted on the polymer compound adsorbing iodine by wasting iodine. There is a problem of shortening.

  On the other hand, there is a proposal to control the sublimation of iodine from solid iodine using a porous member or the like (Japanese Patent Publication No. 10-503698). However, there is a problem that solid iodine is dangerous when touched and is extremely difficult to handle due to its high sublimation rate.

JP-A-57-51725 JP 59-193189 A JP-A-60-232288 Japanese Patent Laid-Open No. 9-67216 Japanese Patent Laid-Open No. 9-122655 Special table hei 9-509876 gazette Japanese National Patent Publication No. 10-503698 JP-A-10-165960 Japanese Patent Laid-Open No. 2003-213022

  Here, the present invention has been made in the background of the above-mentioned circumstances, and the problem to be solved thereof is an iodine gas release tool that controls the release of iodine from a polymer compound that has adsorbed iodine. And providing a method for producing an iodine-containing liquid using the same. Another problem to be solved is to provide an iodine-containing liquid preparation apparatus that is simple and easy to use.

  In the present invention, as a result of various investigations to solve the above-mentioned problems, the release of medium-iodine was successfully controlled by coating a polymer compound adsorbing iodine with a gas-permeable non-porous film. Furthermore, by allowing water and / or an organic solvent that interacts with iodine to coexist with the polymer compound that has adsorbed iodine, it succeeded in controlling the iodine gas release rate advantageously, and an iodine-containing liquid using the same is obtained. Got a prospect.

  That is, the first invention is characterized in that water and / or an organic solvent that interacts with iodine coexists in a polymer compound that adsorbs iodine, and this is covered with a gas-permeable nonporous film. The gazette is the gist.

  In the second invention, a polymer compound adsorbing iodine or a polymer compound adsorbing iodine and an organic solvent having an interaction with water and / or iodine is coated with a gas-permeable non-porous film. The gist is a method for producing an iodine-containing liquid by dissolving iodine gas released from an iodine gas release tool in water and / or an organic solvent.

  Furthermore, the third invention is equipped with an iodine gas releasing device in which the polymer compound adsorbing iodine or the polymer and water and / or an organic solvent coexisted with a gas-permeable non-porous film, and can be opened and closed. The gist of the apparatus for producing an iodine-containing liquid preparation incorporated in the apparatus together with water and / or an organic solvent.

  As the polymer compound adsorbed with iodine used in the present invention, a compound obtained by adsorbing iodine to a polymer compound having iodine adsorptivity is used. Examples of iodine adsorbing polymer compounds include ABS resin, AS resin, ethylene / vinyl alcohol copolymer (EVOH resin), ethylene / vinyl acetate copolymer, polyamide, polyacrylonitrile, acrylonitrile / vinyl chloride copolymer, polyurethane resin. Cellulose acetate resin, polyvinyl alcohol, partially formalized polyvinyl alcohol, polyester, polyethylene oxide resin, starch, polyvinylpyrrolidone copolymer (for example, vinylpyrrolidone / methyl methacrylate copolymer) and the like are used. Moreover, even if it is resin with poor iodine adsorption property, it can be used by mixing with said iodine adsorption resin and shape | molding.

  Of the above polymer compounds, ABS resin, AS resin, and ethylene / vinyl alcohol copolymer (EVOH resin) are particularly desirable. In general, commercially available ABS resins are 20 to 30% by weight of acrylonitrile component, 40 to 70% by weight of styrene component, and 10 to 30% by weight of butadiene component, but any of them can be used in the present invention. It is. Commercially available products include, for example, Psycholac ABS (Mitsubishi Rayon Co., Ltd.). As the EVOH resin, one having an ethylene content of 20 to 50 mol% in the copolymer is preferably used. As commercial products, any varieties can be used among Soarnol manufactured by Nippon Synthetic Chemical Co., Ltd. and Eval manufactured by Kuraray Co., Ltd.

  The polymer compound adsorbed with iodine can be used in various forms such as beads, powder, fiber, woven fabric or nonwoven fabric, film or gel. Also, a molded product by thermoforming such as injection molding, extrusion molding, compression molding or the like can be used. A particularly preferred form is beads, and commercially available pellets for injection molding can be used as they are.

  In order to adsorb iodine to an iodine adsorbing polymer compound material (hereinafter abbreviated as a polymer material), a liquid phase method in which the polymer material is immersed in an iodine solution may be used. However, the adsorption amount is increased in the gas phase. This is advantageous because it is easy and waste liquid does not come out. The method for adsorbing iodine to a polymer material is described in detail in JP-A-10-165960. That is, in the vapor phase adsorption of iodine, a polymer material and a predetermined weight of solid iodine to be adsorbed are placed in a sealed container and heated to 50 ° C. or higher, preferably 60 ° C. or higher, so that the total amount of solid iodine is adsorbed to the polymer material. Is done.

  The amount of iodine adsorbed on the polymer material is preferably 5 to 200% by weight. When the polymer material is in the form of beads, the preferred adsorption amount is 30 to 180% by weight (vs. plastic weight).

  After the total amount of solid iodine is adsorbed on the polymer material, the adsorbed iodine can be penetrated further into the polymer material by processing at a temperature higher than the temperature at the time of adsorption. By this heat treatment, it is possible to adjust the release rate of iodine from the polymer material. The heat treatment temperature is preferably 90 to 110 ° C.

  In the present invention, the polymer compound adsorbing iodine is coated with a gas-permeable non-porous film. The gas permeable non-porous film needs to be permeable to iodine gas, but the film permeable to gases such as oxygen and carbon dioxide gas also transmits iodine gas. The material of the film should not be significantly degraded by iodine. As gas permeability, those having low gas permeability such as oriented polypropylene and high density polyethylene are not suitable. Preferred in the present invention are low density polyethylene, linear low density polyethylene (LLDPE), poly-4-methylpentene-1, unstretched polypropylene, ethylene / vinyl acetate copolymer (EVA), ethyl cellulose and the like. A film obtained by combining these gas permeable films by lamination, coextrusion, or the like can also be used. For example, “OT film” (Otsuka Techno Co., Ltd.) in which poly-4-methylpentene-1 and polyethylene are combined can be used. In addition, “Polo Fresh” (Futamura Chemical Industry Co., Ltd.) with improved gas permeability of polypropylene film can be preferably used. As the ethylene / vinyl acetate copolymer film, “Tsulon L, "E series" is preferably used.

  The coating film of the present invention needs to be a nonporous film. Even if the porous film is hydrophobic and does not transmit water, it cannot be used. The porous film has an effect of slightly delaying the release of iodine from the polymer compound adsorbed with iodine, but the effect is insufficient and the object of the present invention cannot be achieved. In addition, the porous film cannot be used for use in a closed system, which will be described later, because the equilibrium of iodine vapor pressure is not established.

  When the oxygen gas permeability of the non-porous film is high, the iodine gas permeability of the iodine gas release tool covered with the film tends to be high. However, oxygen gas permeability and iodine gas permeability do not always coincide completely. For example, 4-methylpentene-1 film has higher oxygen gas permeability than LLDPE, but iodine permeability is comparable. Particularly preferred films in the present invention are low density polyethylene, LLDPE, and ethylene / vinyl acetate copolymer films. In the ethylene / vinyl acetate copolymer film, the iodine gas permeability increases as the vinyl acetate content increases. The iodine gas permeability depends on the thickness of the film, and the thinner the film, the higher the permeability. In the present invention, the preferred thickness is 10 to 180 microns, and particularly preferably 20 to 150 microns.

  In the iodine gas releasing device (hereinafter abbreviated as iodine gas releasing device) in which a polymer compound adsorbing iodine described in JP-A-2003-213022 is coated with a nonporous film, the material of the film used for coating and the film It is possible to adjust iodine gas release by the thickness. However, it has been found that when the iodine gas release tool is used in a closed system, it is difficult to adjust the release of iodine gas depending on the material of the film and / or the thickness of the film. That is, when water and the iodine gas release tool of the present invention are stored in a sealed container, the water dissolves iodine gas released from the iodine gas release tool to become iodine water, but after a certain period of time has passed. When the iodine concentration reaches a certain height, the iodine concentration reaches an equilibrium, and no further increase occurs. The reason for this is not clear, but the main reason is that the iodine saturated vapor pressure in the nonporous film coating by iodine sublimated from the polymer compound adsorbed with iodine and the iodine vapor pressure on the iodine water side are balanced. It is assumed that iodine does not diffuse from the iodine gas releasing device to the water side. This equilibrium concentration does not substantially depend on the material of the film and does not depend on the thickness of the film. When the contact time of the iodine gas release tool and water is short, the iodine vapor pressure does not yet reach equilibrium, so the iodine concentration of iodine water depends on the material and thickness of the film, but after reaching equilibrium, the iodine concentration is reduced. It becomes difficult to adjust by the film. In this case, even if the amount of the polymer compound adsorbing iodine in the nonporous film coating is changed, the equilibrium concentration of iodine does not change. The only means is to change the iodine adsorption state of the polymer compound that has adsorbed iodine and to change the iodine vapor pressure of the polymer compound that has adsorbed iodine, it is possible to change the iodine equilibrium concentration accordingly. .

  The first invention is intended to make it possible to easily adjust the equilibrium iodine concentration in such a closed system. When the polymer compound adsorbing iodine is covered with a gas-permeable non-porous film, The release of iodine from the iodine gas release tool is increased or decreased by causing water and / or an organic solvent that interacts with iodine to coexist with the polymer compound that has adsorbed iodine.

  When water is allowed to coexist with a polymer compound that has adsorbed iodine, the iodine gas released from the iodine gas releasing device increases as compared with the case where water does not coexist. The reason for this is not yet clear, but one reason is that iodine released from the polymer compound that adsorbs iodine dissolves in water, and the vapor pressure of iodine that volatilizes in the coating of the nonporous film from this iodine water. When water does not coexist, it becomes higher than the vapor pressure of iodine sublimated from the polymer compound adsorbed with iodine, so that it is presumed that iodine gas released from the coating of the nonporous film increases.

  On the other hand, when an organic solvent that interacts with iodine or a mixture of water coexists with a polymer compound that has adsorbed iodine, the polymer compound that adsorbs iodine is released from an iodine gas release device that is covered with a nonporous film. It has been found that there is an effect of reducing the iodine gas. Suitable organic solvents that interact with iodine include ethylene glycol, ethanol, isopropanol, polyethylene glycol, diallyl phthalate, and the like. These can also be used by mixing with water. When mixed with water, the water content is preferably 40% by volume or less. If the amount of water is large, the effect of lowering the iodine concentration is lost, and there is no significant difference from the case of the polymer compound adsorbing iodine alone. Among organic solvents that interact with iodine, N-vinylpyrrolidone excessively suppresses the release of iodine, and even in an aqueous solution thereof, the release of iodine is almost zero, so use in the present invention is not preferable. One of the causes of these organic solvents suppressing the release of iodine from iodine gas releasing devices is that these organic solvents dissolve iodine sublimated from the polymer compound that has adsorbed iodine, and the solution by the interaction with the iodine This is thought to reduce the iodine vapor pressure. It should be noted that ethylene glycol is preferable for moderately reducing iodine release from the iodine gas release tool, and polyethylene glycol and ethanol are preferable for significantly reducing iodine release.

  Adjustment of iodine gas release of iodine gas release tool by coexistence of water or an organic solvent that interacts with iodine or a mixture thereof with water is extremely advantageous when the iodine gas release tool is used for disinfection in a closed system. However, adjustment of iodine gas release can be advantageously applied even in an open system. Increasing iodine release from iodine gas releasing devices through the coexistence of water is advantageous for various disinfection systems and the production of iodine water to be described in detail later. This is effective for maintaining a semi-permanently clean surface or environment. The coexistence of water also has an effect that the release of iodine from the iodine gas releasing device does not decrease much even if the amount of the polymer compound adsorbed with iodine is reduced.

  The amount of the organic solvent that interacts with water and / or iodine is preferably just soaked by the polymer compound that has adsorbed iodine, but it can be effective even in a trace amount that adheres to the polymer compound that has adsorbed iodine. Excess water can also be used. When the polymer compound adsorbed with iodine is in the form of beads or pellets, the amount of water and / or the organic solvent having an interaction with iodine is preferably 0.1 to 20 ml with respect to 10 g of the polymer compound adsorbed with iodine. Is 0.5 to 10 milliliters.

  One advantageous application of this system is the prevention of microbial back-contamination of sterile water faucets used for hand-washing in hospital operating rooms, ICUs and the like. In such a sterile water faucet, there is a risk that microorganisms adhering from the faucet side will grow and be mixed into the sterile water when the sterile water apparatus is not used. For this reason, various preventive measures using heat, ultraviolet rays, chemicals and the like have been taken in order to prevent microbial contamination of the faucet. Aseptic water faucets in hospitals usually have shower faucets where warm aseptic water comes out in a shower shape, but there are many fine holes on the surface of the shower faucet, and sterile water is discharged from these holes in a shower shape. . When not in use, the water in the faucet is supported by the surface tension because it has a small hole and is held in the faucet. Therefore, when the iodine gas release tool of the present invention is stored in the faucet, iodine is released into the water in the faucet when the faucet is not used, and the faucet is disinfected. The passage to the sterile water faucet is usually provided with an electromagnetic valve near the faucet and is closed when the faucet is not used. Although there is a small hole on the faucet surface, it is not a complete closed system, but iodine dissolved in water does not volatilize freely into the atmosphere unlike a completely open system. If the faucet is covered with a cap when the faucet is not in use, the system becomes a completely sealed system. When the faucet is used, warm water of about 40 ° C. normally flows. Therefore, iodine released from the iodine gas discharger stored in the faucet is carried away by the 40 ° C. running water. Since the temperature of this flowing water is high, the temperature inside the iodine gas discharger also rises, and therefore the amount of iodine that is wasted away while using the faucet cannot be ignored.

  Here, when the system when the faucet is not used is a closed system, when the time when the faucet is not used is about 20 hours, the iodine concentration of water in the faucet approaches the equilibrium, so the iodine gas releasing device is covered. Even if the thickness of the film is increased to some extent, it does not decrease much compared to the case where it is thin. On the other hand, since the iodine concentration on the running water side is substantially zero when the faucet is used, the amount of iodine removed is almost inversely proportional to the thickness of the coating film. That is, in a system that is closed when the faucet is not used, if the iodine gas release tool is covered with a thick film, the loss of iodine when the faucet is used is reduced, and the iodine concentration in the faucet when the faucet is not used is the thickness of the film. It is possible to keep the same as when it is thin. For example, when an LLDPE film is used as the film, comparing the film with a thickness of 20 microns and the film with a thickness of 60 microns, the iodine concentration in the faucet when the faucet is not used is not much different, and the loss of iodine when the faucet is used is approximately 3 minutes. It can be set to 1. In this case, it is desirable that the system when the faucet is not used be a closed system, but even if it is not a closed system, it is possible to reduce iodine loss when the faucet is used depending on the thickness of the film. In such a system that repeats running and stagnant water, the thickness of the film is preferably 30 to 150 microns, particularly preferably 40 to 100 microns, for the purpose of disinfecting water when stagnant.

  Further, by storing the iodine gas release tool of the present invention in a sealed container free of water, the contents in the container can be sterilized by iodine gas released from the iodine gas release tool. At this time, the iodine concentration can be adjusted by allowing water to coexist with the polymer compound adsorbing iodine.

  When a polymer compound that adsorbs iodine is placed in a tray-like container and the upper surface of the tray is covered with a gas-permeable nonporous film, the film surface is always kept in a state of being sterilized by iodine gas that permeates the film. Also, if you place the items on the film, they will be automatically disinfected. If the upper surface of the tray-like container is a closed system, it is more advantageous for disinfection of the container placed on the film. Here, when water and / or an organic solvent that interacts with iodine coexist in the polymer compound that has adsorbed iodine, the amount of iodine gas released from the gas-permeable non-porous film covering the upper surface of the container is adjusted. be able to. Further, when water is allowed to coexist, the amount of the polymer compound adsorbing iodine used can be reduced.

  Next, iodine water can be easily produced by placing an iodine gas releasing tool in which a polymer compound adsorbing iodine is covered with a gas-permeable non-porous film in a sealed container and putting water in the container.

  Iodine gas is released from the iodine gas release tool housed in the sealed container, and is dissolved in water in the container to become iodine water. Since the container is sealed, the iodine concentration of iodine water reaches an equilibrium after a certain time, and thereafter the concentration becomes substantially unchanged. The equilibrium concentration of iodine water can be adjusted by allowing water and / or an organic solvent having an interaction with iodine to coexist with the polymer compound adsorbing iodine.

  It is desirable that the closed container has an openable / closable port for replenishing water after using iodine water and using it repeatedly. One aspect of the container is a squeeze bottle having a liquid outlet that can be opened and closed in a one-touch manner. This is an elastic plastic container, for example used as a container for kitchen detergents, with a screw-type cap. The cap has a small hole, but is in a sealed state when the cap is pressed. When the cap is pulled, a gap through which the liquid passes is generated, and the liquid is ejected from the small hole of the cap by pushing the container by hand. After use, the cap is sealed by pressing the cap. When the cap of the container is removed and the iodine gas releasing device of the present invention is placed in the container, the container is filled with water and left for 1-2 days, iodine water is produced. The concentration of iodine water reaches equilibrium in a few days, after which the concentration becomes constant. If iodine water is used to replenish water for later use, iodine water is always available. The iodine gas release tool in the container can be used semipermanently. Since there is no change in the concentration of iodine water, it can be stored as it is for several years.

  Another aspect of the container is a pump-type spray bottle. This is used as a container for a detergent marketed as a household detergent or a bathroom detergent. A liquid suction pump is fixed to the cap of the container, and the liquid in the container is sucked up and sprayed from the nozzle by operating the piston of the pump. By operating the nozzle, the container can be sealed with a single touch. Iodine water can be obtained by opening the cap and storing the iodine gas release tool of the present invention in a container, filling the water and keeping the nozzle sealed. Iodine water can be used semi-permanently by opening the cap and supplying water after using iodine water. The concentration of iodine water is constant after equilibration and does not become excessively high.

  Moreover, there exists an air pressurization type spray bottle as another aspect of a container. As shown in FIG. 1, when the inside of the container is manually pressurized by a pump 2 attached to the container main body 1 and the container is opened by pushing the push button 5, the liquid is ejected from the nozzle 4 attached to the container. It is. The screw-type cap 3 at the bottom of the container is removed, and the iodine gas discharge tool of the present invention is stored and filled with water. After using iodine water, water can be replenished from the cap and used semipermanently.

  In the iodine water production apparatus of the present invention, the concentration of iodine water obtained automatically becomes a constant concentration, and there is no fear that the concentration is excessively high. For this reason, it can be safely used even in ordinary households. In many cases, since the equilibrium concentration of iodine is low, it is advantageous to increase the equilibrium iodine concentration by allowing water to coexist with the polymer compound adsorbing iodine.

The iodine water production apparatus of the present invention is useful not only for disinfection in hospitals, nursing homes, food-related facilities, etc., but also for sterilization at home, nursing care, animals, pets, and the like. In addition, the iodine gas release tool and water can be kept in contact with each other for a long time, so that it is useful for disasters.
Hereinafter, in order to clarify the present invention more specifically, some examples of the present invention will be described.

(Experimental example 1)
200 g of pellets for Diapet ABS (variety PS-505) (Mitsubishi Rayon Co., Ltd.) and 260 g of iodine flakes (Japan Natural Gas Co., Ltd.) were placed in a polypropylene bottle, sealed, and sealed at 65 ° C. Iodine was completely adsorbed by heating with occasional shaking in the oven. Then, heat treatment was performed at 80 ° C. for 12 hours and at 105 ° C. for 24 hours. From the weight increase of the pellet, it was found that the pellet adsorbed 130% by weight of iodine with respect to the weight of the ABS resin.

  12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 were put in a small bag of LLV-MTV film (LLDPE, manufactured by Futamura Chemical Co., Ltd.) having different thicknesses and heat sealed. The iodine gas releasing tool was put in a vial having a capacity of 100 ml, and tap water was observed, and the cap was sealed to seal. The sample was left at room temperature without changing water, and the iodine concentration in the water outside the iodine gas releasing device was measured after 1, 4 and 14 days. Here, in group A, only beads were placed in a film sachet, and in group B, 4 ml of water was added to the beads and heat sealed in a coexisting state. The measurement results of iodine concentration are shown in Table 1. By making water coexist with the polymer compound which adsorbed iodine, the density | concentration of the iodine melt | dissolved in the water of the outer side of an iodine adsorption tool became high remarkably. Further, after 4 days, the iodine concentration hardly changed depending on the thickness of the coating film.

12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 are put in a 50 μm-thick LLV-MTV film sachet and heat sealed, and put in a vial with tap water in the same manner as in Example 1 and sealed. The iodine concentration eluted in the outer water was measured without changing the water. Here, 4 ml of ethylene glycol, ethanol, polyethylene glycol 200 and 80 parts by volume of ethanol / 20 parts by volume of organic solvent were allowed to coexist on the beads. For comparison, an experiment using only beads without using an organic solvent was conducted. The results are shown in Table 2. By allowing the organic solvent to coexist with the beads, the concentration of iodine eluted in the water outside the iodine gas releasing tool was significantly reduced.

  The ABS resin beads adsorbed with iodine prepared in Experimental Example 1 were placed in a 50 micron thick LLV-MTV film sachet in the presence of water in the same manner as in Group B of Example 1, and heat sealed. Here, the amount of water coexisting with the beads was 3 ml and 6 ml. Here, in the case of 3 ml, the amount of water was slightly insufficient for the beads to be completely immersed in water, and in the case of 6 ml, the amount of water was sufficient for the beads to be immersed in water. The results of measuring the iodine concentration in the water after 1, 4 and 14 days without changing the water in the same manner as in Example 1 are shown in Table 3. For comparison, the results when water was not coexisted are also shown in Table 3. By allowing water to coexist with the beads, the concentration of iodine eluted in the water outside the iodine gas releasing device was remarkably increased, but the effect of the amount of coexisting water had little difference between 3 ml and 6 ml.

  12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 were each (A) LLV-MTV film (LLDPE, manufactured by Futamura Chemical Co., Ltd.) thickness 40 microns, (B) EVASB-5, thickness 40 A micron, (C) EVASB-10, 40 micron thick (manufactured by Tamapoly Co., Ltd.) pouch was heat sealed, placed in a 100 ml vial, tap water was squeezed, the cap was tightened and sealed. This was left still in 40 degreeC oven. The iodine concentration of water was measured at intervals of 4 days, and the water was updated after the measurement. Table 4 shows iodine concentrations 10 days, 50 days, 100 days, 150 days and 300 days after the start of the immersion experiment. As Comparative Example 1, 12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 packed in a bag for a tee bag were placed in a 100 ml vial and immersed in tap water to measure the iodine concentration. This is also shown in 4. In the case of Comparative Example 1 coated with a nonwoven fabric for a Tae bag that allows iodine gas to pass through without resistance, the elution of iodine into the outside water is extremely high in the initial stage, while the elution of iodine is extremely reduced in the latter stage, and it is used for a long time. Has a problem. On the other hand, when the beads are coated with an LLDPE film or EVA film, iodine can be eluted almost constantly over a long period of time. There was almost no difference in the dissolved iodine concentration depending on the type of film.

  12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 were placed in a sachet of (A) LLV-MTV film, thickness 40 microns, (B) EVASB-5, thickness 40 microns, and the same as in Example 1. The bottle was filled with tap water, sealed and left at room temperature. Without renewing the water, the iodine concentration in the water was measured after 1, 3, 5, 7, and 300 days. Moreover, as Comparative Example 2, the sample put in the bag as in Comparative Example 1 was allowed to stand at room temperature, and the iodine concentration in water was measured in the same manner. The results are shown in Table 5. In Comparative Example 2 in which the beads were coated with the nonwoven fabric for the tay bag, the iodine concentration in the outside water increased with time, and reached an excessive concentration. On the other hand, when the beads are coated with LLDPE and EVA film, a constant value is exhibited after 5 days and does not increase any further. That is, it can be seen that the iodine concentration of water in the container can automatically maintain a constant value. Moreover, the iodine concentration eluted in the outer water was almost the same depending on the material of the film.

  12 g of ABS resin beads adsorbed with iodine prepared in Experimental Example 1 were placed in 30, 60 and 100 micron LLV-MTV film sachets of different thicknesses, heat sealed, and placed in vials to fill tap water. The vial cap was not tightened but left at room temperature. The iodine concentration was measured after 1, 4 and 14 days without changing the water. Here, group A was charged with only beads, and group B was allowed to coexist with 4 ml of water. The measurement results of iodine concentration in water are shown in Table 6. In the case of a closed system (Example 1), it was constant regardless of the thickness of the film, but when the container was not in a closed system as in this example, the iodine concentration in the water outside the iodine gas elution tool Tends to increase as the thickness of the bead-coated film decreases. On the other hand, if water is allowed to coexist in the beads even if it is not a closed system, the iodine concentration in the outside water increases.

  The following experiment was conducted as a model that approximates the amount of iodine that is lost and lost in running water when using sterile water in a sterile water faucet microbial anti-pollution control system. When running water is used, iodine released from the iodine gas release tool is immediately carried away by running water, so the iodine concentration in running water is substantially zero. Therefore, the difference in the vapor pressure of iodine inside and outside the iodine gas elution tool is considered to be larger when water is stagnant. For this reason, it is considered that the amount of iodine released from the iodine gas releasing device is larger than that at the time of stagnation.

  When an aqueous polyvinyl pyrrolidone solution is used as the outer liquid instead of water, polyvinyl pyrrolidone forms a complex with iodine, so the amount of free iodine in the solution is very small. For this reason, the iodine vapor pressure of the solution is considered to be very low. Therefore, if a polyvinylpyrrolidone aqueous solution is used instead of tap water in the same experiment as in Example 1 or 5, it can be considered that the formation of a complex with polyvinylpyrrolidone corresponds to the removal of iodine by running water.

  Accordingly, the relative value of the amount of iodine eluted in the 3% by weight polyvinylpyrrolidone aqueous solution was determined by a colorimetric method (including bound iodine). The measurement was performed 5 days after the iodine gas releasing tool was immersed in the aqueous solution. Comparing the measurement results for LLV-MTV films with a thickness of 30, 60 and 120 microns, if the 120-micron film was used for coating, it was 1.8 for 60 microns and 3.1 for 30 microns. Met. That is, it can be seen that the loss due to the outflow of iodine into the running water is almost inversely proportional to the thickness of the film.

  It was also found that the ethylene / vinyl acetate copolymer film (EVA SB-5 thickness 40 microns) had a relative value of 7.5 and 7.5 times that of a polyethylene 120 micron film.

  Therefore, when the water is stagnant, as is clear in Example 4 or 5, if the system is a closed system, the amount of iodine eluted into the water outside the iodine gas elution tool is within a certain range. Independent of film thickness and material. On the other hand, the amount of iodine that elutes in the running water depends on the material of the covering film, and decreases as the film thickness increases.

  From this, in systems such as prevention of contamination of sterile water faucets, by increasing the thickness of the non-porous film covering the polymer compound adsorbed with iodine, the loss of iodine when using running water is reduced, and When the water is stagnant, sufficient iodine can be eluted to prevent microbial contamination.

FIG. 1 is a longitudinal sectional view showing one embodiment of an air pressure spray bottle used in the iodine-containing liquid preparation production apparatus of the present invention.

Explanation of symbols

1 Container Body 2 Air Pressure Pump 3 Cap 4 Nozzle 5 Push Button

Claims (3)

An iodine gas releasing device characterized in that water and / or an organic solvent coexist in a polymer compound adsorbing iodine and is coated with a gas-permeable non-porous film. A polymer compound adsorbing iodine or the polymer and water and / or an organic solvent coexist, and this is coated with a gas-permeable non-porous film to form an iodine gas release tool, and then water and / or an organic solvent. And a method of preparing an iodine-containing liquid agent by being left in a closed system. An iodine gas releasing device in which a polymer compound adsorbing iodine or the polymer and water and / or an organic solvent coexist and coated with a gas-permeable non-porous film is provided. Or an iodine-containing liquid preparation device built in with an organic solvent.

Images