JP5448381B2 - Iodine rapid release material and method for producing the same - Google Patents

Description

The present invention relates to an iodine release material having a high iodine release rate when contacted with water and a method for producing the same, and in particular, iodine is adsorbed to a polyvinyl acetal porous material by a loose bond and is very short in water. The present invention relates to an iodine rapid release material and a method for producing the same.

Iodine is hardly soluble in water and is a solid crystal at room temperature, but has sublimation properties. Moreover, since iodine has a strong bactericidal action, it is widely used as a wound disinfectant or a mouthwash. Usually, iodine is dissolved in ethanol and used as an iodine tincture containing potassium iodide as an additive, or it is combined with polyvinylpyrrolidone to increase the iodine concentration in the aqueous solution and at the same time stabilize the popidone iodine solution. . These chemical solutions have been used historically and are widely used for medical use and general household use, respectively. These chemical solutions generally contain a high concentration of iodine. However, the bactericidal action of iodine is largely due to free iodine, and free iodine has a large bactericidal power even at low concentrations.

In the aqueous solution, the released iodine is iodide ion (I ⁻ ), diatomic iodine (I ₂ ), triiodide ion (I ₃ ⁻ ), pentaiodide ion (I ₅ ⁻ ), hypoiodous acid (HIO). ), Hypoiodite ion (IO ⁻ ), and iodate ion (IO ³⁻ ). Among these, diatomic iodine (I ₂ ) is considered to have the highest bactericidal activity, and this is generally called free iodine. However, since this free iodine is hardly soluble in water as described above, it is difficult to stably dissolve in water when it volatilizes outside the system or crystallizes and precipitates. For this reason, it was necessary to increase the solubility with potassium iodide or polyvinylpyrrolidone.

On the other hand, instead of supplying iodine in a solution state as described above, methods have been proposed in which iodine is adsorbed on a synthetic resin or the like and distributed, and iodine water is prepared and used when necessary (Patent Documents 1 and 2). ). In this method, 100 to 600% by weight of iodine is adsorbed on an ethylene-vinyl alcohol-based resin or ABS (acrylonitrile-butadiene-styrene) resin, and iodine that is stable for a long time by iodine released continuously from the iodine adsorbing resin. It is to provide a solution. However, this method is not suitable for a state where it can be used in a short time because the release rate of iodine is relatively slow. In particular, when it is used for conventional wound disinfection, it is impossible to predict when it will be necessary, and thus it has been difficult to satisfy urgent demands.

Further, a composition in which acetalized polyvinyl alcohol and iodine are combined (Patent Document 3) has been proposed. As described in the lower left column on page 5, the iodine is assumed to be released slowly. And is not intended for rapid iodine release materials. An antimicrobial material (Patent Document 4) in which iodine is adsorbed on polyethylene, polypropylene, copolyester or the like has also been proposed, but release in units of time is being examined as described in page 15 of the publication. This is not intended to release iodine in a very short time. Furthermore, an ion-exchange resin and a substance that absorbs iodine (Patent Document 5) have been proposed. This is to sterilize blood, blood fractions, and other protein-containing solutions by passing through the column, By flowing a small amount of a protein-containing solution through a column packed with a packing adsorbed with iodine, an attempt is made to disinfect by increasing the contact area between the solution and the packing. In this method, it is completely impossible to obtain a large amount of iodine water, and it is not shown how much iodine is released. Furthermore, elemental iodine-containing substances such as iodinated agarose (Patent Document 6) have also been proposed. However, a mixture of polymer particles capable of slowly releasing iodine and polymer particles capable of adsorbing iodine is liquid. And a method for removing excess iodine simultaneously with sterilization, which uses polyvinyl acetal for capturing iodine.
JP-A-9-67216 Japanese Patent Laid-Open No. 10-165960 Japanese Patent Laid-Open No. 2-29962 Japanese National Patent Publication No. 9-509876 Special Table 2000-514045 Special table 2003-512136 gazette

The present invention has been made as a result of studying a new application as a problem that has not been considered at all in the above-described prior art, and its object is that when the iodine release rate is high and when contacted with water, It is to provide an iodine rapid release material that can prepare iodine water that can be used for disinfection in a very short time, and further improve the storage stability after production, and a method for producing the same.

As a result of intensive studies to achieve the above object, the present inventors impregnated a specific wetting agent before adsorbing iodine on a polyvinyl acetal porous material having a specific degree of acetalization or iodine adsorption treatment. The obtained iodine release material is made into water by impregnating with a wetting agent later, or by adjusting the volume ratio of solid iodine to the space at the time of iodine adsorption treatment to an appropriate binding force between iodine and the polymer. It has been found that iodine water can be obtained in a very short time by bringing it into contact with the present invention, leading to the present invention.

That is, the present invention relates to (a) a polyvinyl acetal porous material having an acetalization degree of 55 to 80 mol%, and a group consisting of 1 to 50% by weight of glycerin, ethylene glycol, and polyethylene glycol with respect to the porous material. (B) impregnating one or more selected wetting agents; (b) sealing 10 to 400% by weight of solid iodine with respect to the porous body together with the impregnated porous body in a container; and c) a step of heating the interior of the container at 30 to 100 ° C. to adsorb iodine, and a method for producing an iodine rapid release material. Thus, when the porous body is impregnated with the wetting agent, not only the adsorption efficiency of iodine is excellent, but it is also possible to adsorb in a state where iodine can be rapidly released.

After the step (c), (d) 1 to 100% by weight of a porous material after adsorption of iodine is further impregnated with one or more wetting agents selected from the group consisting of glycerin, ethylene glycol, and polyethylene glycol. You may add the process to make. This is because the storage stability of the rapid iodine release material is further improved by re-impregnating the wetting agent after the iodine adsorption treatment.

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Furthermore, in the step (b) , the present invention is sealed in the container at a volume ratio of solid matter (total volume of porous body and solid iodine): air layer of 10:90 to 65:35, The present invention relates to a method for producing a rapid iodine release material characterized in that iodine is adsorbed to the porous body in a short time by heating the inside at 30 to 100 ° C. to vaporize iodine. By adsorbing iodine at a specific volume ratio in the reaction vessel, the porous body and iodine can be brought into an appropriate binding force, and the later-described release of iodine can be performed rapidly.

According to the volume ratio, solid iodine is once vaporized and then adsorbed to the porous body. Therefore, if the vaporizable volume is too large , the solid iodine is not adsorbed to the porous body and exists in a gaseous state, and if it is too small, the amount vaporized. Therefore, the adsorption rate tends to be slow, and it is desirable to treat at an appropriate ratio.

The iodine rapid release material of the present invention thus obtained has a feature that the iodine release rate is preferably 0.07 to 3 mg / sec. Here, the iodine release rate in the present invention means that 0.5 g of the iodine rapid release material is put into a 100 ml vial (inner diameter: about 35 mm, height: about 120 mm), 100 ml of water is added at room temperature, and the bottle is sealed. The iodine rapid release material is taken out immediately after being allowed to stand for 2 seconds, and defined as a value obtained by measuring the iodine concentration released within 10 seconds from the start of contact.

According to the method for producing an iodine release material of the present invention, iodine rapid release capable of preparing a concentration of iodine water that can be used for disinfection within a very short time, specifically within 30 seconds, more preferably within 10 seconds. The material is manufactured. In the production, it is a simple production method and does not require special machinery and equipment, and the cost is low. Moreover, the rapid release material of iodine obtained by the present invention is stable in the dry state, and can be handled with bare hands as it is, suppressing the sublimation rate of iodine, and is excellent in safety.

Another feature is that the stability of the storage period can be further improved by applying a wetting agent treatment to the release material after adsorbing iodine. And since iodine water necessary for disinfection can be obtained immediately by contact with the rapid iodine release material and water, it not only fully performs its function in emergency, disaster, etc., but also for nursing facilities and home use It is suitable to be always available.

Hereinafter, the present invention will be specifically described.
In the production of the iodine rapid release material of the present invention, a polyvinyl acetal porous material is used as a substrate for adsorbing iodine. This is because the porous body increases the contact area with water and improves the release efficiency of adsorbed iodine. The porosity of the porous body is preferably 50 to 95%, particularly preferably 60 to 93%. If the porosity is lower than the above range, it is difficult to obtain the desired rapid release of iodine. If the porosity is above the above range, the mechanical strength of the porous body may be lowered. The pore diameter is 40 to 1000 μm, preferably 50 to 800 μm. When the pore diameter is less than the above, water permeability when contacted with water is deteriorated, it may be difficult to obtain a desired iodine release rate, and when the pore diameter is larger than the above, The mechanical strength of the material may decrease.

The polyvinyl acetal porous material has an acetalization degree of 50 to 90 mol%, preferably 55 to 80 mol%. This is because if it exceeds 90 mol%, the amount of iodine adsorbed is insufficient, and if it is lower than 50 mol%, the water resistance is poor. Polyvinyl acetal is obtained by a condensation reaction of polyvinyl acetaldehyde with polyvinyl alcohol, but formaldehyde, butyraldehyde, or the like can also be used. When formaldehyde is used, it is known that the glass transition temperature becomes high and the heat resistance is excellent. Further, when butyraldehyde is used, since it has excellent solubility in a solvent, a product having a high degree of acetalization can be obtained, but the heat resistance becomes poor. In addition, as a polyvinyl acetal type porous body, the bell eater D series or Berglin made from Aion Co., Ltd. can be used, for example.

The polyvinyl acetal porous material is processed into an appropriate shape. For example, any form is possible as long as it can be processed, such as a sheet shape, a rod shape, and a spherical shape. After the following steps (such as the step of adsorbing iodine), the desired shape can be obtained. However, it is better to work in an appropriate shape in advance than actual treatment after adsorbing a large amount of iodine. It is because it can adsorb | suck uniformly on the surface of each discharge | release material to be used. One of the preferred forms is a sheet-like piece, for example, 10 × 10 mm square and a thickness of 2 to 5 mm.

As one method for producing the rapid iodine release material of the present invention, there is a method in which iodine is adsorbed after impregnating the polyvinyl acetal porous material with a wetting agent (step (a)). Specific examples of the wetting agent in this case include glycerin, ethylene glycol, polyethylene glycol, ethylene oxide / propylene oxide block copolymer, alkyl polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty acid polyoxyethylene sorbitan ester, fatty acid poly A group consisting of oxyethylene sorbitol ester, polyoxyethylene hydrogenated castor oil, fatty acid sorbitan ester, fatty acid polyglycerin ester and fatty acid sucrose ester can be mentioned. These may be used alone or in combination of two or more.

When the polyvinyl acetal porous material contains the wetting agent, the working range for producing the rapid release material for iodine according to the present invention is remarkably widened and the production is facilitated, and the stability against heat during storage is remarkably improved. The reason for this is not yet clear, but it may be because the wetting agent has an effect of suppressing the excessive binding of iodine and the polyvinyl acetal porous material.

The wetting agent impregnation method is, for example, a method in which the wetting agent is brought into direct contact with the surface of the porous body and compressed, a method in which the porous body is squeezed and sucked in an aqueous wetting agent solution, or dried. The wetting agent can also be sucked with a nonwoven fabric or the like. In addition, excess wetting agent may be removed by centrifuging the porous body after impregnation. The wetting agent in the step (a) is 1 to 50% by weight, preferably 5 to 30% by weight, based on the polyvinyl acetal porous body. When the content is less than 1% by weight, it is difficult to uniformly coat the surface of the porous body, so that it is difficult to obtain the effect of impregnation (fast release of iodine when contacted with water). Further, even if it exceeds 50% by weight, there is little effect and it is economically disadvantageous.

Among the wetting agents, preferred are glycerin, ethylene glycol and polyethylene glycol (polyethylene glycol having a molecular weight of 2 to 3.5 million can be used, and preferably has a molecular weight of 200 to 3000). It is glycerin, and these exhibit excellent effects in terms of economy, operability, iodine release, storage stability, and the like. Moreover, these are substances that are released with iodine, leached into the resulting iodine water, and are highly safe even if used for disinfection of wounds. It may have an effect of stabilizing iodine by forming a complex with iodine in iodine water.

After impregnating the polyvinyl acetal porous body with the wetting agent as described above, this is sealed in a container together with solid iodine (step (b)). At this time, solid iodine is 10 to 400% by weight with respect to the porous body. Since the total amount of solid iodine is basically vaporized in a sealed container and adsorbed to the porous body, the amount of adsorption is inevitably determined by adjusting the amount of sealing, so it is desirable. What is necessary is just to add the quantity. Of course, it is possible to terminate the reaction before the total amount of added solid iodine is vaporized, but the total amount is allowed to react if the remaining solid iodine is separated or the problem of iodine vapor in the gas phase is taken into consideration. Is desirable. Thus, the greatest feature of the present invention is that no unnecessary components are produced after the reaction. Usually, in the process of producing a compound, a purification process, a separation process, etc. are often required due to some impurities, by-products, unreacted raw materials, etc., but in the production method of the present invention, Since it can manufacture without providing such a separate process, manufacturing cost can be significantly reduced. If the adsorption amount of iodine to the polyvinyl acetal porous material is less than 10% by weight, the iodine release rate when contacted with water becomes insufficient, and if it exceeds 400% by weight, the heating time for achieving the iodine adsorption amount is insufficient. It takes a long time. A preferable iodine adsorption amount is 30 to 300% by weight, and a particularly preferable iodine adsorption amount is 30 to 200% by weight.

After sealing in a container in this way, the whole container is put into a heatable machine such as a dryer, and iodine is vaporized by heating at 30 to 100 ° C., preferably 50 to 90 ° C. (step (c)). As temperature conditions at this time, for example, when solid iodine is added in an amount of 50 to 100% by weight, the temperature is 90 ° C. for 1 to 2 hours, 80 ° C. for 5 to 10 hours, and 60 ° C. for about 6 to 24 hours. However, there is no problem even if it is heated for a longer time. However, it is desirable to select the minimum necessary temperature and time to directly affect manufacturing costs. If the set temperature is too high, the polyvinyl acetal porous material may be deteriorated. Therefore, a temperature exceeding 100 ° C. is not suitable, and if it is lower than 30 ° C., vaporization of iodine is very slow. This is not preferable because it takes a long time.

Although the iodine rapid release material obtained by the above can be used as a product as it is, it can be impregnated with a wetting agent again (step (d)). The wetting agent used at this time is the same as that used in step (a). Specifically, glycerin, ethylene glycol, polyethylene glycol, ethylene oxide / propylene oxide block copolymer, alkyl polyoxyethylene Examples include a group consisting of ether, fatty acid polyoxyethylene ester, fatty acid polyoxyethylene sorbitan ester, fatty acid polyoxyethylene sorbitol ester, polyoxyethylene hydrogenated castor oil, fatty acid sorbitan ester, fatty acid polyglycerin ester, and fatty acid sucrose ester. In the step (d), 1 to 100% by weight of a wetting agent can be allowed to act on the porous body after iodine adsorption. This concentration is higher than that in the step (a), but since the heating step (c) is performed after the step (a), the vapor pressure of the wetting agent at that time is taken into consideration. The wetting agents used in step (a) and step (d) may be the same or different. Also, the wetting agent at this time can be used alone or in admixture of two or more.

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The wetting agent such as glycerin can be used as it is to impregnate the porous polyvinyl acetal, but it is preferably mixed with water and used in the form of an aqueous solution. When the case of glycerol is illustrated, it is preferable to use it as a 10 to 90 weight% aqueous solution of glycerol. Particularly preferred is a 30 to 70% by weight aqueous solution.

As an impregnation method in the step (d) or (C ′), a polyvinyl acetal porous material chip adsorbed with iodine may be attached to the wetting agent with tweezers, and then the excess wetting agent may be sucked with a nonwoven fabric or the like. After immersing the polyvinyl acetal porous material adsorbing iodine in a wetting agent liquid, the excess wetting agent may be removed by a centrifugal separator. Another effective method is to attach a wetting agent liquid to the surface of the porous polyvinyl acetal chip, and then rub the chip onto a smooth surface such as a petri dish using tweezers to infiltrate the wetting agent into the porous body. It is.

The effect of impregnating the porous material after adsorbing iodine with the wetting agent (addition of step (d) or step (c ′)) further improves the long-term storage stability of the iodine rapid release material. In addition to maintaining the function of rapidly releasing the desired iodine even if the storage temperature becomes too high. In addition, the release rate of iodine is also faster than the release material produced by the steps (a) to (c).

The iodine rapid release material thus obtained is characterized in that the release of iodine when brought into contact with water is extremely fast compared to the prior art. In particular, in the present invention, the iodine release rate is defined as follows. That is, 0.5 g of iodine rapid release material was placed in a 100 ml vial (inner diameter: about 35 mm, height: about 120 mm), 100 ml of water was added at room temperature, sealed, and allowed to stand for 10 seconds, and then immediately released with iodine. It is defined as a value obtained by taking out the material and measuring the iodine concentration released within 10 seconds from the start of contact. The iodine rapid release material of the present invention has an iodine release rate of 0.07 to 3 mg / sec. When it is desired to obtain a large amount of iodine water or to obtain high concentration iodine water, the ratio of water to be brought into contact with the iodine rapid release material may be appropriately adjusted. In addition, the iodine release rate in the present invention was determined by simply immersing the iodine rapid release material in water for the method of contact with water in consideration of variation due to measurement conditions, but in actual usage, it was immersed. It is also possible to release iodine faster by shaking and stirring the whole in the state. The contact time with water is usually about 3 to 20 seconds, but the contact time may be further increased when the iodine concentration is particularly desired to be increased or when the volume of water is large.

There is also a method of adsorbing iodine without adding a wetting agent. The points to be noted in that case will be described below. First of all, the porous body and iodine are sealed in the container, but the volume ratio of the solid (the combined porous body and solid iodine) and the air portion (solid: It is characteristic that air) is 10:90 to 65:35. It is because the iodine which vaporized by setting it as such a ratio will be adsorb | sucked to a porous body rapidly. This ratio is particularly preferably 15:85 to 55:45. If the ratio of solids is lower than 10, it is economically disadvantageous in production. On the other hand, if the ratio of solids is more than 65, the adsorption of iodine becomes slow and at the same time becomes non-uniform and a good product cannot be obtained. It is of course possible to apply this ratio to a production method (specifically, step (b) or step (a ′)) in which the wetting agent is used. When the above-mentioned wetting agent is used, it is possible to rapidly adjust the iodine without having to strictly control various conditions in the process of adsorbing iodine, for example, the volume ratio and the heat history described below, as compared with the case where the wetting agent is not used. Since a release material is obtained, it can be said that it is advantageous for quality control.

The second point to note in the case of a production method that does not use a wetting agent is that it is necessary to strictly control the temperature and time at which solid iodine is vaporized and adsorbed on the porous body. Specifically, when 50 to 100% by weight of iodine is adsorbed to the porous body, the total heating time is 6 to 24 hours at 60 ° C, 4 to 12 hours at 70 ° C, and 5 to 10 hours at 80 ° C. At 90 ° C., it is 1 to 2 hours. This heating time refers to the case of continuous heating, but it goes without saying that if the temperature is lowered during that time, the heat treatment takes longer time, whereas if the temperature is raised, the heat treatment takes shorter time. Even if it is adsorbed over the heating time, iodine is not immediately released, but the bond strength between iodine and the porous body increases in proportion to the excess time, and the iodine release rate decreases. It becomes difficult to obtain a desired iodine rapid release material (iodine release rate of 0.07 to 3 mg / sec). In addition, as a method which does not fail in temperature control, it can also carry out by the method of mixing by the ratio of the iodine to adsorb | suck and ending heating when the added solid iodine becomes invisible.

By the way, as a conventional technique of adsorbing iodine to a polymer other than polyvinyl acetal, for example, when iodine is adsorbed to an ABS resin, when the heating time is prolonged, iodine diffuses from the surface of the resin to the inside, and thus iodine is gradually released. It can be used as a material. On the other hand, in the case of a polyvinyl acetal porous material, when the heating time is prolonged, not only the initial iodine release when contacted with water is remarkably delayed, but also the sustained release with time is remarkably lowered. The reason for this is not clear, but in the case of polyvinyl acetal, it is not because the distribution of iodine changes, but it is considered that the binding state with iodine changes and it becomes difficult to release iodine. On the other hand, in the case of ABS resin, when iodine is adsorbed on the surface, the iodine release rate when it comes into contact with water is strong even though it is difficult to handle with bare hands when the iodine is strongly sublimated in the dry state. It is extremely slow compared to the polyvinyl acetal porous material produced by the method of the present invention. On the other hand, the polyvinyl acetal based porous material is characterized by the fact that, as described above, by proper management of the heating process, there is little sublimation of iodine in the dry state, and the iodine release rate when contacted with water is extremely fast. .

Further, in the case of ABS resin, for example, when 100% by weight of iodine is adsorbed using molding pellets, after heating for 10 hours at 70 ° C. to adsorb iodine, no additional heat treatment is performed. And, the sublimation property of iodine from the pellet is remarkable, and it is difficult to handle with bare hands. Moreover, the iodine release rate of the ABS resin pellets by the above method is on the order of 3 mg / hour according to the method defined in the present invention. In addition, when the pellets were heat treated at 100 ° C. for 24 hours and handled with bare hands, the iodine release rate was on the order of 4 mg / day, and the iodine release was incomparable with the polyvinyl acetal porous material of the present invention. The speed is slow. Therefore, the present invention is not suitable for use in preparing a disinfectant solution that can rapidly release iodine and cope with an emergency.

In the production method in which the wetting agent of the present invention is impregnated, the amount of solid iodine mixed with the polyvinyl acetal porous material is preferably set to an amount to be adsorbed. It is also possible to adjust the amount to be adsorbed by adding solid iodine above the expected amount and taking out the porous material with solid iodine remaining after a suitable time, but solid iodine is sublimable This is because the sublimated iodine may be sucked during the operation of taking out the porous body after adsorption, and care is required in the work environment.

The rapid release material of iodine obtained by the above production method has a black appearance, but since the amount of iodine that sublimes is small like solid iodine, the skin is not soiled even if handled with bare hands in a short time. Therefore, handling is easier and safer than solid iodine. Moreover, iodine can be released very quickly when it comes into contact with water, and iodine water can be easily produced. The iodine release rate of the release material is 0.07 to 3 mg / sec as described above, and since it does not become overconcentrated in terms of the solubility of iodine in water, iodine water with an appropriate concentration can be obtained. It is done.

In order to prepare iodine water from the iodine rapid release material of the present invention, the following method is used as a specific example. The polyvinyl acetal porous material is cut into a sheet having a suitable size, for example, a thickness of 4 to 5 mm, to 10 × 10 mm, and an iodine rapid release material is produced by any one of the above production methods. About 1 to 10 release materials are placed in a 100 ml glass vial, tap water is added to the glass, and the mixture is shaken for several seconds to several tens of seconds. With this alone, iodine water having an iodine concentration of 30 to 300 ppm can be obtained from tap water. Since free iodine has a high bactericidal effect, this iodine water exhibits a sufficient disinfecting effect against various bacteria, fungi and viruses. After the obtained iodine water is used up, it can be refilled with tap water and manufactured in the same manner, and can be re-prepared by repeating several times to several tens of times. Therefore, it is extremely useful for emergency disinfection at the time of a disaster or for simple disinfection in hospitals and other facilities.

Further, as a method for preparing iodine water using the iodine rapid release material of the present invention, for example, a container having a capacity of about 120 ml having a cap with a detachable nozzle can be used. By using the nozzle, the iodine water in the container can be accurately sprayed to the target site, and it is possible to use it more conveniently. As the container, it is also possible to use a container in which the internal pressure of the container is increased by a pump or the like for injection. In any case, the iodine rapid release material of the present invention and water are brought into contact with each other, so that iodine water having a concentration capable of being disinfected in a few seconds to several tens of seconds can be obtained. It can be used for the preparation of In addition, when the iodine rapid release material of the present invention is brought into contact with 1 to 2 liters of water, a large amount of iodine water having a concentration that can be used for disinfection in several minutes to several tens of minutes can be prepared. Such iodine water is useful for disinfecting fingers and instruments in elderly facilities.

The production method of the present invention will be described below with specific examples.
(Reference Example 1)
A 4 mm thick polyvinyl acetal sponge (Brand Eater F (D), manufactured by Aion Co., Ltd.) was cut into a size of 10 × 10 mm, and 10.1 g (160 cut pieces) of iodine (flakes) (Nippon Natural Gas Co., Ltd.) was mixed in a glass vial with a capacity of 400 ml and sealed. Here, the volume ratio of solid: air was 40:60. This was heated in a 90 ° C. oven for 1.5 hours with occasional shaking of the container. At this time, solid iodine disappeared in appearance. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 50% by weight. The sponge on which iodine was adsorbed was not easily soiled even when touched by hand, and was easy to handle. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Comparative Example 1)
The sponge obtained by adsorbing 50 wt% iodine obtained in Reference Example 1 was further heated in an oven at 90 ° C. for 3 hours. There was no change in the adsorption amount of iodine from the weight measurement of the sponge after the reaction. However, the iodine release rate of the obtained iodine release material was 0.03 mg / sec.

(Reference Example 2)
Mixing Put the same polyvinyl acetal sponge 10.1g iodine 10.3g Reference Example 1 in the same vial, tightly sealed (where solid: volume ratio of air was 42:58), Reference Example Heated for 5 hours at 80 ° C. with occasional shaking as in 1 . At this time, solid iodine disappeared visually. From the measurement of the weight of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 100% by weight. The sponge on which iodine was adsorbed was not easily soiled even when touched by hand, and was easy to handle. The iodine rapid release material obtained had an iodine release rate of 0.45 mg / sec.

(Reference Example 3)
The same polyvinyl acetal sponge 10.4 g as in Reference Example 1 and 2.7 g of iodine were placed in the same vial, mixed and sealed (where the solid: air volume ratio was 39:61), 80 Heated for 1 hour with occasional shaking at ° C. At this time, it was confirmed by visual observation that solid iodine substantially disappeared. From the weight measurement of the polyvinyl acetal sponge after the reaction, the iodine adsorption amount was 25% by weight. The iodine rapid release material obtained had an iodine release rate of 0.2 mg / sec.

(Comparative Example 2)
The sponge obtained by adsorbing 25 wt% iodine obtained in Reference Example 3 was further heated in an oven at 80 ° C. for 3 hours. There was no change in the adsorption amount of iodine from the weight measurement of the sponge after the reaction. However, the iodine release rate of the obtained iodine release material was 0.04 mg / sec.

(Reference Example 4)
Mixing Put the same polyvinyl acetal sponge 10.1g iodine 3.2g Reference Example 1 in the same vial, tightly sealed (where solid: volume ratio of air was 39:61), Reference Example In the same manner as in No. 1 , the mixture was heated at 65 ° C. with occasional shaking for 3 hours, heated to 80 ° C. and heated for 1 hour. At this time, solid iodine disappeared visually. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 30% by weight. The sponge on which iodine was adsorbed was not easily soiled even when touched by hand, and was easy to handle. The iodine rapid release material obtained had an iodine release rate of 0.25 mg / sec.

(Comparative Example 3)
The sponge obtained by adsorbing 30 wt% iodine obtained in Reference Example 4 was further heated in an oven at 80 ° C. for 4 hours. There was no change in the adsorption amount of iodine from the weight measurement of the sponge after the reaction. However, the iodine release rate of the obtained iodine release material was 0.04 mg / sec.

8 pieces of sponge pieces adsorbed with iodine obtained in Reference Examples 1 to 4 and Comparative Examples 1 to 3 were placed in a 100 ml vial, poured with 80 ml of tap water, and capped. The container was grasped and shaken for 10 seconds, the content liquid was transferred to another container, 80 ml of tap water was again poured into the vial with the sponge left, the same was shaken, and the content liquid was further transferred to another container. . Table 1 shows the results of repeating such a cycle five times and measuring the iodine concentration of each solution.

From the results in Table 1, in the sponges adsorbed with iodine obtained in Reference Examples 1 to 4 , iodine water having a concentration sufficient for disinfection was obtained in the first to fifth iodine water production. The iodine water concentrations obtained in Examples 1 to 3 were all insufficient for disinfection. Moreover, although the iodine density | concentration after immersing the sponge which adsorb | sucked the iodine obtained in Comparative Examples 1-3 for 1 hour and 5 hours was measured, it has hardly raised, From this, in Comparative Examples 1-3 The low release of iodine is not caused by the distribution of iodine adsorbed in the polyvinyl acetal sponge, but is presumed to be due to the difference in the binding state between the polyvinyl acetal and iodine.

Example 1
A 4 mm thick polyvinyl acetal sponge (trade name: Beleater F (D), manufactured by Aion Co., Ltd.) was cut into a size of 10 × 10 mm. This 10.1 g (160 pieces) was dipped in a mixture of 10 parts of polyethylene glycol 1000 (reagent grade 1 manufactured by Wako Pure Chemical Industries, Ltd.) and 10 parts of water for 30 minutes, and then well-squeezed and dried at 60 ° C. did. Due to the increase in weight, the content of polyethylene glycol 1000 was 13.8% by weight. The polyvinyl acetal sponge 11.7g of polyethylene glycol 1000 and the like iodine 5.3g Reference Example 1 were mixed were are in the same vial as in Reference Example 1 (where solid: volume ratio of the air 37: 63) and heated in an oven at 60 ° C. with occasional shaking for 5 hours, then heated to 80 ° C. and heated for 2 hours. At this time, solid iodine disappeared in appearance. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 50% by weight. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Reference Example 5)
Iodine was adsorbed in the same manner as in Example 1 except that polyethylene glycol 1000 was not impregnated. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 50% by weight. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Example 2)
The sponge obtained by adsorbing 50% by weight of iodine obtained in Example 1 was further heated at 80 ° C. for 24 hours. There was no change in the weight of the sponge, and therefore there was no change in the amount of iodine adsorbed. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Comparative Example 4)
The sponge adsorbed with 50% by weight of iodine obtained in Reference Example 5 was further heated at 80 ° C. for 24 hours. There was no change in the weight of the sponge, and therefore there was no change in the amount of iodine adsorbed. However, the iodine release rate of the obtained iodine release material was 0.04 mg / sec.

Eight small pieces of sponge adsorbed with iodine obtained in Examples 1 and 2, Reference Example 5 and Comparative Example 4 were placed in a 100 ml vial, poured with 80 ml of tap water, and capped. The container was grasped and shaken for 10 seconds, the content liquid was transferred to another container, 80 ml of tap water was again poured into the vial with the sponge left, the same was shaken, and the content liquid was further transferred to another container. . Table 2 shows the results of repeating such a cycle five times and measuring the iodine concentration of each solution.

About Example 1 , the iodine water suitable for disinfection was obtained 5 times. In Example 2, the heating time was extended, but the obtained iodine water had the same results as in Example 1 . On the other hand, Comparative Example 4 is a case where ethylene glycol 1000 is not contained, but it can be seen that the iodine concentration of the obtained iodine water is considerably lowered by extending the heating time.

(Example 3)
The same polyvinyl acetal sponge as in Reference Example 1 was cut into a size of 10 × 10 mm. This 10.1 g (160 pieces) was immersed in a mixed solution of 10 parts of ethylene glycol (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 10 parts of water for 30 minutes, and then well-squeezed and dried at 60 ° C. Due to the increase in weight, the ethylene glycol content was 13.9% by weight. The ethylene glycol and polyvinyl acetal sponge 11.5g containing the same iodine 5.3g Reference Example 1 were mixed were are in the same vial as in Reference Example 1, 5 with shaking occasionally vessel in 60 ° C. oven Heated for a period of time, then heated to 80 ° C. and heated for 2 hours. At this time, solid iodine disappeared in appearance. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 50% by weight. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

Example 4
The sponge adsorbed with 50% by weight of iodine obtained in Example 3 was further heated at 80 ° C. for 24 hours. There was no change in the weight of the sponge, and therefore there was no change in the amount of iodine adsorbed. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Example 5)
The same polyvinyl acetal sponge as in Reference Example 1 was cut into a size of 10 × 10 mm. This 10.1 g (160 pieces) was immersed in a mixed solution of 10 parts of glycerin (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 10 parts of water for 30 minutes, and then well-squeezed and dried at 60 ° C. Due to the increase in weight, the glycerin content was 12.8% by weight. Similar iodine 5.3g polyvinyl acetal sponge 11.6g containing the glycerin and the Reference Example 1 were mixed were are in the same vial as in Reference Example 1, 5 hour with shaking occasionally vessel in 60 ° C. oven Then, heated to 80 ° C. and heated for 2 hours. At this time, solid iodine disappeared in appearance. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 50% by weight. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

(Example 6)
The sponge obtained by adsorbing 50% by weight of iodine obtained in Example 5 was further heated at 80 ° C. for 24 hours. There was no change in the weight of the sponge, and therefore there was no change in the amount of iodine adsorbed. The iodine rapid release material obtained had an iodine release rate of 0.35 mg / sec.

Eight small pieces of sponge adsorbed with iodine obtained in Examples 3 to 6 were placed in a 100 ml vial, poured with 80 ml of tap water, and capped. The container was grasped and shaken for 10 seconds, the content liquid was transferred to another container, 80 ml of tap water was again poured into the vial with the sponge left, the same was shaken, and the content liquid was further transferred to another container. . Table 3 shows the results of repeating such a cycle five times and measuring the iodine concentration of each solution.

The sponge containing the wetting agent of the present invention ( Examples 3 to 6 ) can release iodine in a short time even if the heating time is treated for a long time. In practice, the shorter the heat treatment, the lower the cost, so it will not heat up unnecessarily for a long time, but even if the temperature control is a little appropriate, the resulting rapid iodine release material has the desired function. It can be seen that it is possible to fully demonstrate. Further, since it is difficult to deteriorate even if it is temporarily exposed to high temperature during storage, it is advantageous for long-term storage.

(Example 7)
Placed in the same vial as in Example 5 with polyvinyl acetal sponge 11.4g containing glycerol 12.8% by weight of the same (cutting pieces 150) and (Reference Example 1 The same iodine 10.5g Reference Example 1 The mixture was heated in an oven at 70 ° C. for 10 hours with occasional shaking, then heated to 80 ° C. and heated for 5 hours, and the amount of iodine adsorbed was determined from the weight measurement of the polyvinyl acetal sponge after the reaction. The iodine release rate of the obtained iodine rapid release material was 0.45 mg / sec.

(Example 8)
Put the same iodine 15.9g polyvinyl acetal sponge 11.4g containing 12.8 wt% same glycerol as in Example 5 and (or cut pieces 150) as in Reference Example 1 in the same vial as in Reference Example 1 Mix and heat in an 80 ° C. oven for 20 hours with occasional shaking of the container. From the measurement of the weight of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 149.6% by weight with respect to the sponge. The iodine rapid release material obtained had an iodine release rate of 0.6 mg / sec.

Example 9
Put the same iodine 21.2g polyvinyl acetal sponge 11.4g containing 12.8 wt% same glycerol as in Example 5 and (or cut pieces 150) as in Reference Example 1 in the same vial as in Reference Example 1 Mix and heat in an 80 ° C. oven for 10 hours with occasional shaking, then at 60 ° C. for 4 days. From the weight measurement of the polyvinyl acetal sponge after the reaction, the iodine adsorption amount was found to be 198.9% by weight with respect to the sponge. The iodine rapid release material obtained had an iodine release rate of 0.7 mg / sec.

In the case of the sponge obtained by adsorbing iodine obtained in Example 7 , four small pieces, and in the case of the sponge obtained in Examples 8 and 9 , two small pieces were put into a 100 ml vial, and 80 ml of tap water was poured. , Covered. The container was grasped and shaken for 10 seconds, the content liquid was transferred to another container, 80 ml of tap water was again poured into the vial with the sponge left, the same was shaken, and the content liquid was further transferred to another container. . Table 4 shows the results of repeating such a cycle five times and measuring the iodine concentration of each solution.

It can be seen that iodine of a sufficient concentration for disinfection is released in a very short time from any iodine rapid release material.

(Example 10)
11.5 g of polyvinyl acetal sponge containing 12.8% by weight of glycerin as in Reference Example 1 and 30.8 g of iodine are mixed in the same vial, and sometimes at 60 ° C. using the same apparatus as in Reference Example 1. Heated with shaking for 35 hours. At this time, solid iodine disappeared visually. From the weight measurement of the polyvinyl acetal sponge after the reaction, it was found that the iodine adsorption amount was 306% by weight (vs. polyvinyl acetal). The sponge on which iodine was adsorbed was not easily soiled even when touched by hand, and was easy to handle. The iodine rapid release material obtained had an iodine release rate of 0.82 mg / sec.

(Reference Example 6)
The same polyvinyl acetal sponge (10.2 g) (160 pieces) and iodine (15.3 g) as in Reference Example 1 were mixed in a vial with a capacity of 400 ml and sealed (here, the volume ratio of solid: air was 43: 57). This was placed in an oven at 60 ° C. and heated for 25 hours with occasional shaking. The iodine disappeared completely in appearance. The iodine adsorption calculated from the weight increase was 147% by weight (vs. polyvinyl acetal). Next, a 70% by weight aqueous solution of glycerin (glycerin as in Example 5 ) was prepared and placed in a beaker. A part of the cut piece adsorbing iodine was pinched with tweezers and immersed in an aqueous glycerin solution, and the excess glycerin solution was wiped with a nonwoven fabric (step (c ′)). The adhesion amount of glycerin calculated from the increase in weight was 15.8% by weight (decided piece after iodine adsorption). Prepare two unsealed cut pieces not impregnated with glycerin (Comparative Example 5) and cut pieces impregnated with glycerin ( (Reference Example 6) ) and sealed in 20 ml glass vials. Each one was placed in an oven at 40 ° C. and each one was stored at room temperature. The iodine release rate was measured after 8 months. The results are shown in Table 5.

From the results shown in Table 5, for those not impregnated with glycerin, the iodine release rate was significantly reduced when stored at 40 ° C. for 8 months compared to room temperature storage.

(Example 11)
As in Example 5 , 10.3 g of polyvinyl acetal sponge containing 12.8% by weight of glycerin (145 pieces of cutting pieces) and 15.5 g of iodine were put in a 400 ml vial and sealed and mixed. This was placed in an oven at 60 ° C. and heated for 25 hours with occasional shaking. The iodine disappeared completely in appearance. The iodine adsorption calculated from the weight increase was 162.5% by weight (vs. polyvinyl acetal). Next, a 50% by weight aqueous solution of glycerin was prepared and placed in a petri dish. A part of the cut piece adsorbing iodine was pinched with tweezers to attach glycerin, then rubbed on the bottom of an empty petri dish to allow glycerin to penetrate into the sponge, and the excess glycerin liquid was wiped with a nonwoven fabric ( Step (d)). The adhesion amount of glycerin calculated from the increase in weight was 12.6% by weight (the cut piece after adsorption to iodine). Prepare 20 pieces of each of the cut pieces that have been subjected to step (d) in a 20 ml vial and the cut pieces that have been finished up to the iodine adsorption process, and seal each two pieces in an oven at 40 ° C. Each one was stored at room temperature. The iodine release rate was measured after 8 months. The results are shown in Table 6.

The results in Table 6 indicate that those subjected to step (d) have a higher original iodine release rate than those not subjected to the step, and are highly stable against long-term storage at high temperatures. It was done. It can also be seen that compared with Comparative Example 5 in which no glycerin is impregnated, the decrease in iodine release rate is much less when the glycerin is impregnated before the iodine adsorption reaction.

Using the cut pieces prepared in the same manner as in Example 11 , two sealed pieces (with or without the step (d)) were prepared, each containing 5 cut pieces in a vial, and each one piece was prepared. Were placed in an oven at 60 ° C., and each one was stored at room temperature. The release rate of iodine was measured after 2 months, and the results are shown in Table 7.

From the results in Table 7, it was shown that those subjected to step (d) were more stable against long-term storage at high temperatures than those not subjected to the step (d). Therefore, it can be seen that the rapid release material for iodine is highly effective in maintaining the function even when stored at high temperature by impregnating with a wetting agent after adsorption of iodine.

With the production method of the present invention, iodine can be stably fixed and high concentration iodine water can be obtained in a short time when brought into contact with water. In addition, it is possible to provide an iodine rapid release material that is suitable for regular use as a nursing facility or home.

Claims (4)

(A) One or more kinds selected from the group consisting of 1 to 50% by weight of glycerin, ethylene glycol, and polyethylene glycol in a polyvinyl acetal porous body having an acetalization degree of 55 to 80 mol% (B) a step of sealing 10 to 400% by weight of solid iodine with respect to the porous body together with the porous body after the impregnation, and (c) 30 inside the container. A process for heating iodine at 100 ° C. to adsorb iodine, and a method for producing an iodine rapid release material. (D) After the step (c), the porous body after iodine adsorption is further impregnated with 1 to 100% by weight of one or more wetting agents selected from the group consisting of glycerin, ethylene glycol and polyethylene glycol. The manufacturing method according to claim 1, further comprising the step of:   In the step (b), the solid volume (the total volume of the porous body and solid iodine): the volume ratio of the air layer is 10:90 to 65:35, and the container is hermetically sealed. Or the manufacturing method of 2. The iodine rapid release material of the iodine rapid release material obtained by the manufacturing method in any one of Claims 1 thru | or 3 is 0.07-3 mg / sec.
(Iodine release rate: 0.5 g of iodine rapid release material was placed in a 100 ml vial (inner diameter: about 35 mm, height: about 120 mm), 100 ml of water was added at room temperature, sealed, and allowed to stand for 10 seconds. This is defined as the value obtained by taking out the iodine rapid release material and measuring the iodine concentration released within 10 seconds from the start of contact.)