JPH10165960A - Antibacterial composition, its production, antibacterial mixed granular matter using this composition, liquid supply device fitted with microorganism penetration preventing function and iodine-containing solution producing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial compsn. capable of discharging iodine of relativerly high concn. over a long period of time and excellent in handling properties and a method for producing the same. SOLUTION: An ABS resin 4 and solid iodine 5 are sealed in a hermetically closed container 6 to be heated to 55 deg.C or higher. An antibacterial compsn. 14 wherein 70wt.% or more of iodine is added to the resin 4 is obtained by the diffusion of iodine from iodine vapor 5a sublimed from solid iodine 5 to the resin 4 or the direct diffusion of iodine at the contact part with solid iodine 5. At least a part of added iodine is liberated or released in the presence of water to generate antibacterial properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial composition and a method for producing the same, and furthermore, an antibacterial mixed granule using the antibacterial composition, a liquid supply device having a function of preventing intrusion of microorganisms, and an apparatus for producing an iodine-containing solution. About.

[0002]

2. Description of the Related Art Conventionally, hospitals and the like have produced aseptic water using resin beads or fibrous bodies containing iodine (hereinafter referred to as iodine-containing resin bodies), or iodine has been supplied to a faucet portion of a sterile water supply. It has been practiced to arrange a containing resin body to prevent reverse contamination of sterile water due to intrusion of microorganisms from a faucet. Further, an iodine-containing resin body is brought into contact with water, and the iodine contained therein is leached to produce a disinfectant containing a small amount of iodine.

Heretofore, as such an iodine-containing resin body, for example, one obtained by adsorbing 1 to 10% by weight of iodine to ABS (acrylonitrile-butadiene-styrene) resin (Japanese Patent Laid-Open No. 59-193189), acrylic fiber or acrylic fiber Organic polymer, such as polyamide fiber, containing 0.1 to 60% by weight of iodine (JP-B-60-13)
37) Absorbed iodine at 1% by weight or more, desirably at 3% by weight or more on ABS resin granules (JP-A-60-2)
32288), 0.02-0.05 for the organic polymer molded product
A method of performing a heat treatment at 60 ° C. or higher after adsorbing iodine at a concentration of 60% by weight (JP-A-57-51725). Various types have been proposed, such as one that adsorbs iodine on a crosslinked vinylpyrrolidone polymer and is used for purification of organic polymer water (US Pat. No. 3,907,720).

[0004]

In the above-mentioned conventional iodine-containing resin bodies, the amount of iodine added to the total weight of the resin is as small as 60% by weight at the maximum, and is used for preventing reverse contamination of, for example, a faucet for supplying sterile water. When used for, there is a problem that the effect is not persistent. In addition, for a disinfecting solution manufacturing apparatus that needs to release a relatively large amount of iodine for a long period of time, a necessary iodine concentration cannot be essentially obtained,
Alternatively, even if it is obtained, there is a drawback that an economical problem occurs such that the resin body needs to be frequently replaced because the period during which the desired concentration level can be maintained is short. Therefore,
It is conceivable to use solid iodine granules as a source of iodine, but the iodine crystals are brittle and inconvenient to handle, and the finely divided iodine crystals easily mix into sterile water or disinfectant solution There's a problem.

An object of the present invention is to provide an antibacterial composition capable of releasing a relatively high concentration of iodine over a long period of time and also having excellent handleability, a method for producing the same, and the antibacterial composition. It is an object of the present invention to provide an antibacterial mixed granule using the above, an antibacterial mixed granule using the antibacterial composition, a liquid supply device having a function of preventing intrusion of microorganisms, and an apparatus for producing an iodine-containing solution.

[0006]

Means for Solving the Problems and Actions / Effects In order to solve the above-mentioned problems, the antibacterial composition of the present invention comprises an acrylonitrile component and a methacrylonitrile component (hereinafter, referred to as “methacrylonitrile component”).
(When both are collectively referred to as a nitrile component), the resin contains iodine and at least 10% by weight in total, and the iodine content is 70% by weight or more in a weight ratio to the resin. And at least a part of the contained iodine is released or released in the presence of water.

[0007] The present inventors, when using a resin containing 10% by weight or more of the above-mentioned nitrile component as the base of the antibacterial composition, if any appropriate iodine addition conditions are selected, any of the above-mentioned prior art publications. It has been found that a composition containing an extremely high concentration (specifically, 70% by weight or more) of iodine, which is not described, can be obtained. Since the composition has a high content of iodine, it has excellent sustainability of iodine release.For example, when applied to a supply faucet such as sterile water, reverse contamination of sterile water by invading microorganisms from the faucet. The prevention effect can be maintained for a long time,
When used in an apparatus for producing an iodine-containing solution such as a disinfectant, the iodine concentration in the disinfectant can be maintained at a high level for a long time. In addition, despite its extremely high iodine content, for example, it has higher mechanical strength than solid iodine, and is less likely to chip or collapse, so that it is easy to handle. And the problem of being mixed into the disinfectant is less likely to occur.

When the content of the nitrile component in the resin is 1
When the content is less than 0% by weight, the iodine content in the composition is reduced to 70%.
It cannot be increased to more than% by weight. From the viewpoint of increasing the iodine content in the composition, it is more desirable to use a resin containing a nitrile component of 15% by weight or more as the resin.

As the resin, for example, a resin composed entirely of a nitrile component, such as polyacrylonitrile, can be used. However, a resin mainly composed of a copolymer of an acrylonitrile component and a styrene component can be used. By using, the rate of addition reaction of iodine to the resin can be increased, and the maximum achievable iodine addition amount can be increased. Thereby, an antimicrobial composition having a high iodine content and high productivity can be realized.

[0010] As such a copolymer, a copolymer of acrylonitrile and styrene (a so-called AS resin) can be used. A commonly used A
The S resin has an acrylonitrile content of about 20 to 35% by weight and a styrene content of about 70 to 75% by weight. However, in the antibacterial composition of the present invention, the acrylonitrile content is limited to this range. In some cases, for example, by using a resin having a higher acrylonitrile content, the addition reaction rate of iodine or the maximum achievable iodine addition amount can be increased.

Further, in the resin used in the present invention,
More preferably, in a copolymer of an acrylonitrile component and a styrene component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylic rubber, ethylene-propylene copolymer, and chlorinated polyethylene An elastic phase (or rubber component) composed of at least one of the above can be used in which the elastic phase is dispersed by chemical bonding or mixing. Thereby, the amount of iodine added to the resin can be further increased. Of these, acrylonitrile-butadiene-dispersed uniformly in a rubber component such as polybutadiene in an AS resin.
Styrene resins (so-called ABS resins) are particularly excellent in both the iodine addition rate and the maximum achievable iodine addition amount, and can be suitably used in the present invention.

As the ABS resin, those produced by various methods can be used. For example, in order to enhance the compatibility between the AS resin and the polybutadiene rubber, a resin obtained by grafting an AS resin to the surface as a polybutadiene rubber phase is used. What was manufactured using it can be used. In this case, the method of graft bonding or the method of blending the AS resin phase with the polybutadiene rubber phase is not particularly limited.

Generally, commercially available ABS resins have an acrylonitrile component of 20 to 30% by weight, a styrene component of 40 to 70% by weight, and a butadiene component of 10 to 30% by weight.
When the ABS resin having the general composition is used, iodine as much as 200% or more based on the weight of the resin can be easily added, and the composition accompanying the shrinkage of the resin can be easily added. There is an advantage that the physical degradation phenomenon such as the conventional iodine-containing resin composition, such as embrittlement, hardly occurs. In some cases, by further increasing the content of the acrylonitrile component or the butadiene component in the resin, the addition reaction speed of iodine and the maximum achievable iodine addition amount can be further increased. AB
In the S resin, methyl methacrylate, α-methylstyrene, N-
One obtained by further polymerizing one or more monomers such as phenylmaleimide may be used.

In the above resin, if a resin containing a total of 20% by weight or more of an acrylonitrile component and a butadiene component is used, the rate of addition reaction of iodine to the resin and the maximum achievable iodine addition amount can be further increased. Can be. As the resin, more preferably, a resin containing 15% by weight or more of an acrylonitrile component and 10% by weight or more of a butadiene component is preferably used.

Here, it is also possible to use acrylonitrile-chlorinated polyethylene-styrene (ACS) resin using chlorinated polyethylene instead of the butadiene component in the ABS resin. A resin having a structure in which all or a part of a butadiene component is replaced with the above-mentioned chlorinated polyethylene or the various rubber components while mainly containing an acrylonitrile-styrene copolymer is referred to as “ABS resin” or “ABS resin” in a broad sense. It may be called "resin".

In addition, a vinyl chloride-acrylonitrile copolymer resin, a vinylidene chloride-acrylonitrile copolymer resin and the like can also be used. Further, acrylonitrile butadiene rubber (NBR) obtained by copolymerizing acrylonitrile with butadiene may be used. In the case of NBR, the content of acrylonitrile is usually 18 to 50% by weight.
It is about. Further, as the NBR, one containing at least one of divinylbenzene, acrylic acid and methacrylic acid can be used.

Further, the following resins which were originally developed as resins having gas barrier properties can also be used. This is because a copolymer of nitriles such as acrylonitrile or methacrylonitrile as a main component containing 50% by weight or more of the nitriles and styrene or acrylic acid ester, or a copolymer thereof as a continuous phase, butadiene or the like is used. Are dispersed in the continuous phase in the form of a chemical bond or a mixture. As a commercially available product of such a resin, Barex (trade name, Mitsui Toatsu Chemical Co., Ltd.) or Kaneka Panex (trade name, Kanegafuchi Chemical Industry Co., Ltd.) can be used.

The antimicrobial composition as described above specifically forms a resin body of a predetermined shape, and contacts iodine to the resin body by contacting solid iodine and / or iodine vapor. It can be produced by a method including a step of diffusing (an iodine adding step). In this case, the temperature of iodine addition needs to be set to 55 ° C. or higher. When the iodine addition temperature is lower than 55 ° C., the iodine addition rate becomes too low, so that it takes an extremely long time to obtain the expected amount of iodine addition, and in some cases, the intended iodine content cannot be obtained. Cases can also occur. The temperature is more desirably 60 ° C. or higher. On the other hand, if the iodine addition temperature is too high, the resin is softened and fusion or aggregation is likely to occur, which causes problems such as the inability to obtain a composition in the desired form. In this case, the upper limit value of the additional temperature varies depending on the type of the resin, but is preferably adjusted to be generally 120 ° C. or less, more preferably 80 ° C. or less.

According to the above method, an antibacterial composition containing 70% by weight or more of iodine can be produced very easily. As described above, in the prior art, the amount of iodine added to the resin is at most about 60% by weight,
Further iodination was considered to be virtually impossible. However, the present inventors, when appropriately selecting the type of resin and performing iodine addition under the notation conditions, surprisingly, it becomes possible to add iodine far beyond the amount considered to be the limit. As a result, an antibacterial composition having a high iodine content, which has never been conceived in the technical field, has been realized. For example, when the iodine content is 100% by weight or more in terms of a weight ratio with respect to the resin, it becomes possible to dramatically increase the sustainability and release amount of iodine release as compared with a conventional iodine-containing resin body. . Then, for example, when the ABS resin is used as the resin, the weight ratio to the resin is 30 by the above method.
As much as 0-600% by weight of iodine can be easily added. If the iodine content increases to this extent,
For example, the iodine release capacity is almost the same as solid iodine, and since it has much higher mechanical strength and is easier to handle than solid iodine, its value as a high-concentration and long-lived iodine supply source is greatly increased. It is raised to.

The amount of iodine added can be easily adjusted by, for example, appropriately setting the treatment time or treatment temperature of iodine addition, or the amount of iodine mixed with the resin. Specifically, when it is desired to increase the iodine addition amount, the treatment time may be increased or the addition temperature may be increased, and when it is desired to decrease the iodine addition amount, the opposite adjustment may be performed. For example, in the indicated temperature range,
When the amount of added iodine is desired to be 70 to 600% by weight, the processing time can be set in a range of about 8 to 170 hours.

In the iodine adding step, for example, a method of adding iodine by bringing a resin body into contact with solid iodine and directly diffusing iodine from the solid iodine to the resin body can be adopted. In this case, iodine can be diffused into the resin body also from iodine vapor generated from solid iodine. In addition, as solid iodine, usually, flaky crystals can be used,
It is also possible to use powdered iodine with a somewhat lower purity. In addition, iodine can be added by heating the resin body and solid iodine in a state of being sealed in a predetermined space. The solid iodine sealed with the resin body sublimates by heating, and iodine diffuses from the surface of the resin body into the inside through the iodine vapor. Further, when direct contact between solid iodine and the resin body occurs, the above-described direct diffusion of iodine may occur at the contact portion.

The antibacterial composition obtained by adding iodine to a resin body releases iodine when it comes into contact with water, and exhibits excellent antibacterial action mainly due to the oxidizing action of the iodine. Become. Here, the distribution of iodine concentration in the obtained antibacterial composition, since the addition of iodine to the resin body proceeds by diffusion of iodine from the resin surface to the inside, it is likely to be high in the vicinity of the surface layer. Tend. Therefore, when the obtained antibacterial composition is brought into contact with water or the like as it is, the iodine release rate tends to be relatively large in the initial stage and then gradually decreased. In this case, the initial iodine release rate may be excessive depending on the purpose of use of the composition. Then, the iodine concentration distribution in the antibacterial composition can be adjusted (for example, made uniform) by subjecting the resin body after iodine addition to heat treatment at an appropriate temperature.
This makes it possible to adjust the release rate of iodine from the antibacterial composition.

The heat treatment temperature in this case is preferably set in a range of 80 ° C. or higher. If the heat treatment temperature is lower than 80 ° C., the effect of homogenizing the iodine concentration distribution cannot be sufficiently achieved. The heat treatment temperature is more desirably 85 ° C. or more. If the heat treatment temperature is too high, as in the iodine addition step, the resin is softened, and problems such as fusion and aggregation of the composition are likely to occur. In this case, the upper limit value of the additional temperature varies depending on the resin, but is preferably set to about 120 ° C. or less.

The antimicrobial composition can be formed in a granular form (for example, a bead form or a pellet form). This facilitates filling the antibacterial composition into a container, a column, or the like, for example, sterilizing the liquid to be treated by flowing the liquid to the antibacterial composition, or removing iodine from the antibacterial composition. When producing an iodine-containing solution by leaching, the contact efficiency between the liquid and the antibacterial composition can be increased. In this case, the average particle volume is preferably adjusted in the range of, for example, 0.001 to ² cm ³ . If the average particle volume is less than 0.001 cm ³ , the composition may be too finely divided, for example, the resistance during the flow of the liquid may be too large. On the other hand, if it exceeds 2 cm ³ , the contact efficiency between the liquid and the antibacterial composition may not be sufficiently achieved. However, depending on the intended use of the antimicrobial composition,
Average particle volumes outside the above ranges may be possible.

The granular antibacterial composition (hereinafter referred to as “antibacterial composition particles”) has various shapes such as a spherical shape, a spheroidal shape, a columnar shape, a bale shape, a cocoon shape, and an egg shape. Can be formed. For example, in the case of forming as columnar pellets, it can be produced by molding a resin as a raw material into a predetermined pellet shape by known extrusion molding or the like, and adding iodine thereto. On the other hand, by grinding or crushing a lump or pellet composition, an irregularly shaped antibacterial composition can be obtained.

Next, a small piece of an absorbent having liquid absorbability is blended with the above-described antibacterial composition particles at a ratio of 3 to 40% by weight based on the total weight of the antibacterial composition particles. Thereby, the antibacterial mixed granular material of the present invention can be obtained. It is effective to use the antibacterial mixed granules in the following cases, for example. For example, when the granular antibacterial composition is filled in a column or a container and the like, and the iodine-containing liquid is allowed to flow through the column or the container, if the flow of the liquid is stopped for a long time, the iodine-containing liquid remains in the column or the container. In some cases, the leaching of iodine from the composition into the existing liquid may cause a problem that an excessively concentrated iodine solution flows out first when the flow of the liquid is resumed. In such a case, if a small piece of the absorbent is blended, the concentrated iodine solution is retained by the absorbent and hardly flows out at the time of resumption of distribution, so that the above-described problem can be solved. . Also,
When the granular antibacterial composition is packed in a liquid bag or small container and placed near a drain outlet such as a sink or a bath to prevent the generation of offensive odor and sliminess due to the propagation of various bacteria, the antibacterial property If the composition is not always in contact with water, the release of iodine is low and sufficient antimicrobial effects may not be achieved. Therefore, if an absorbent is blended with the antibacterial composition, water is retained in the absorbent and a proper humidity is always given around the composition particles, and thus iodine is always released without excess or shortage,
The antibacterial effect can be enhanced.

When the blending amount of the absorbent is less than 3% of the total weight of the antibacterial composition particles, the effect of retaining the liquid becomes insufficient. On the other hand, when the content exceeds 40% by weight, the volume ratio of the antibacterial composition particles in the antibacterial mixed granules decreases, leading to a reduction in the iodine releasing effect and, consequently, the antibacterial effect.

As the material of the absorbing material, a sponge-like formed material having hydrophilicity, specifically, a sponge having hydrophilicity such as polyvinyl alcohol sponge (hereinafter, referred to as PVA sponge), cellulose sponge, polyurethane sponge, etc. Shape formers can be used. Of these, PV
A sponge is not only excellent in water retention, but also has the property of adsorbing iodine, for example,
As described above, when the flow of the liquid to the antibacterial composition is stopped for a long time, the effect of adsorbing the eluted iodine and preventing the iodine concentration in the surrounding liquid from excessively increasing is also excellent. In this case, it is preferable to use a PVA sponge having a relatively small proportion of formalized hydroxyl groups among its hydroxyl groups, for example, having a degree of formalization of 55 to 55.
It is good to use what is 70%, desirably 57-65%.

On the other hand, in place of the sponge-like material, a small piece of a fiber-like material may be used. Examples of such a fiber-forming product include regenerated cellulose fibers such as viscose rayon and cupra (trade name: Bemberg), cellulose fibers such as cotton fibers and wood pulp fibers, and cellulose acetate fibers and acrylonitrile fibers. And mixtures thereof. In particular, regenerated cellulose fibers are excellent in the effect of absorbing liquid by capillary action. As the small pieces of the fiber-formed product, those formed in a sheet shape by, for example, a dry method, a wet method, a spun bond method, or the like can be used by being cut into small pieces.

In addition, instead of using an antibacterial mixed granule in which a small piece of the above absorbent is blended with a granular antibacterial composition,
For example, the aggregate of the antibacterial composition particles may be wrapped with the sheet of the absorbent material, or contained in a bag made of the absorbent material, or further, in a column or a container, with the layer of the antibacterial composition particles. The same effect can be achieved by laminating an absorbent layer with the liquid in the flowing direction. For example, for a layer of antimicrobial composition particles packed in a column or container, it is possible to arrange a layer of absorbent adjacent at least one side of the liquid inlet and the liquid outlet. it can.

In addition, the resin is supplied to the cavity formed in the mold, and iodine is added to the resin structure molded into a shape corresponding to the cavity, thereby providing the antibacterial property of the present invention. An antimicrobial structure constituted by the composition can also be obtained. According to this, since the resin structure to which iodine is added is formed in advance by molding, a complicated component shape or the like can be easily obtained. For example, an antibacterial component such as a liquid supply tool is used. When constituted by the antibacterial structure of the present invention, there is an advantage that the optimum part shape for effectively extracting the antibacterial action can be freely pursued. The resin structure is manufactured by so-called injection molding, that is, by forming a cavity of the desired shape in a mold and injecting heated and softened resin into the cavity. can do. According to this, a structure having a complicated shape can be manufactured more efficiently. In addition, it is also possible to use a resin structure manufactured by a blow molding method.

In addition, when adding iodine to the resin structure, in order to prevent the addition of iodine to a specific portion of the structure (for example, a portion requiring dimensional accuracy such as a screw portion), A diffusion-blocking coating can be formed on the surface of the structure corresponding to the portion to block or suppress iodine diffusion into the structure. The diffusion blocking coating can be, for example, a resin coating layer, and as a forming method, for example, a method of attaching a resin adhesive tape,
Alternatively, a method in which a resin liquid in which a resin is dissolved or dispersed in a solvent is applied to the surface of the structure to form a resin liquid, or the like, can be exemplified.

Next, a liquid supply device having a function of preventing invasion of microorganisms can be constituted by using the above-mentioned antibacterial composition. The liquid supply device is provided with the antibacterial composition, is disposed near the outlet, and includes an outlet antibacterial portion that comes into contact with a liquid passing from the inlet to the outlet. The outlet antibacterial part releases or releases at least a part of the iodine contained therein in the presence of water, and removes microorganisms that enter the inside from the outlet by the released or released iodine. Or reduce. In such a liquid supply device, microorganisms intruding from the outlet are removed or reduced by the outlet antibacterial portion, so that when the liquid is discharged and supplied through the supply device, the microorganisms intruding from the outlet can be used. Reverse contamination is effectively prevented or suppressed. Further, as described above, the antibacterial composition has an iodine content of 70% by weight relative to the resin.
Since it is as high as% by weight, the above-mentioned effect of preventing reverse contamination is excellent.

The exit antibacterial portion may be an aggregate of the aforementioned antibacterial composition particles contained in the main body. And
The liquid passing from the inlet to the outlet of the main body is brought into contact with the aggregate of the antibacterial small members. According to this structure, the contact area between the liquid and the antibacterial composition is increased, so that the disinfection effect can be further remarkable. Further, the outlet antibacterial portion may be an antibacterial structure disposed separately or integrally with the main body portion.

Specifically, the liquid supply device includes a main body having a liquid inlet and an outlet formed therein, and an attaching portion for attaching the main body to a faucet for supplying the liquid at the inlet. It can also be configured as one. In this case, the liquid supply device can be compactly configured so as to be directly attachable to a faucet or the like. Here, when the exit antibacterial portion is formed of an antibacterial structure in the above-described configuration, the antibacterial portion can be provided integrally with the main body so as to form at least a portion near the outlet on the inner surface of the main body.

Further, the liquid supply tool may be provided with a large number of shower ejection holes as liquid outlets. In this case, the exit antibacterial portion is constituted by an antibacterial structure at least in the vicinity of each shower ejection hole, or is an aggregate of antibacterial composition particles arranged in the shower body.

Further, the liquid supply device may be provided with a disinfecting filter for removing or reducing microorganisms contained in the liquid by filtering the liquid flowing from the inlet. This makes it possible to further reduce the content of microorganisms in the liquid discharged from the outlet,
If used by attaching to the supply port of liquid such as tap water, it is possible to remove or reduce microorganisms from the liquid by filtering with the above sterilization filter, and use a liquid supply device as a kind of microorganism removal device or water purifier Can be used as In this case, a specific substance contained in the liquid is adsorbed while flowing the liquid upstream of the sterilization filter.
It is also possible to provide a suction section for removal. With this adsorbing portion, for example, components that cannot be removed by a sterilization filter, that is, chlorine for disinfecting tap water, other odor components, and the like can be effectively removed or reduced.

On the other hand, an apparatus for producing an iodine-containing solution can be constituted by using the antibacterial composition of the present invention. The device has, for example, a main body in which a liquid inlet and an outlet are formed, and an iodine eluting portion formed of the antibacterial composition or the content thereof and disposed inside the main body, and is provided from the inlet into the main body. When the introduced liquid comes into contact with the iodine elution section, iodine contained in the iodine elution section elutes to become an iodine-containing solution, which is discharged from the outlet. Since the antibacterial composition of the present invention has a high iodine content, only by flowing a liquid to an iodine elution portion composed of the antibacterial composition or the content thereof, a relatively high concentration iodine-containing solution can be obtained. It can be easily manufactured, and its solution can be used, for example, as a disinfectant. In this case, the iodine elution portion can be composed of, for example, an aggregate of the aforementioned antibacterial composition particles, an antibacterial mixed granule, or an antibacterial structure having a predetermined shape.

On the other hand, a liquid as a raw material is stored in a container such as a tank, and an iodine-eluting section is charged and left therein, whereby iodine can be eluted into the liquid to produce an iodine-containing solution. is there. In this case, even if the iodine content in the antibacterial composition is less than 70% by weight, this may be suitably used as a constituent material of the iodine elution portion. For example, when using the obtained iodine-containing solution as a disinfectant, the iodine concentration in the solution is 1 to 100 ppm,
The content is preferably adjusted to 5 to 50 ppm, and the iodine content in the antibacterial composition particles is preferably at least 5% by weight, more preferably at least 10% by weight based on the resin.

For example, in an aqueous disinfectant solution containing iodine, the sublimation of iodine is high. Therefore, if the container containing the solution is not sealed, iodine sublimates and escapes, and the iodine concentration of the solution immediately increases. There is a problem of lowering. However, according to the above-described method in which the iodine eluting portion is put into the raw material liquid and allowed to stand, even if some iodine is sublimated, iodine is newly eluted from the iodine eluting portion. Hateful. If the container is sealed except when the solution is used, and the container is opened only when the solution is used to take out the solution, sublimation of the iodine can be suppressed to a minimum, and the iodine concentration in the solution can be reduced. Can always be maintained at a certain level or higher.

Here, when water or a liquid mainly composed of water is used as the raw material liquid, molecular iodine (I2) is eluted from the iodine elution portion to the water, and even if the concentration is low, a high bactericidal activity is obtained. As a result, even if the iodine concentration in the solution is suppressed to a low level, a necessary and sufficient effect as a disinfectant can be achieved. On the other hand, if a complex-forming organic substance that forms a complex with iodine is added to the raw material liquid and a complex of the iodine eluted from the iodine elution portion and the complex-forming organic substance is formed, iodine in the solution is reduced. It can be stably held, and can prevent iodine from escaping due to sublimation or the like. As such a complex forming organic substance, for example, a surfactant such as polyvinylpyrrolidone, polyvinyl alcohol, cyclodextrin, or poloxamer can be used. In this case, as the resin serving as the base of the antimicrobial composition constituting the iodine eluting portion, if the above-mentioned polyvinylpyrrolidone or polyvinyl alcohol-based resin is used, a part of the resin is eluted together with iodine and the above-mentioned complex is formed. In some cases, a high concentration iodine solution can be obtained.

In addition to the above-mentioned resins which are the bases of the antibacterial composition constituting the iodine-eluting portion, ethylene-vinyl alcohol resins (hereinafter, referred to as ethylene-vinyl alcohol-based resins mainly comprising a copolymer of ethylene and vinyl alcohol) , EVOH resin) can be used. Since the EVOH-based resin can be thermoformed, a complicated shape of the iodine elution portion can be obtained relatively easily. The EVOH-based resin can be entirely composed of a copolymer of ethylene and vinyl alcohol (hereinafter, also simply referred to as a copolymer). In order to adjust the properties, other components may be appropriately added. In this case, it is desirable that the copolymer contains at least 30% by weight. When the content of the copolymer is less than 30% by weight, the thermoformability of the resin may be impaired, or the maximum content of iodine may be reduced, so that sufficient antibacterial action may not be obtained. The copolymer is more desirably contained in an amount of 50% by weight or more. Also, EV
As the copolymer of ethylene and vinyl alcohol contained in the OH-based resin, it is desirable to use a copolymer having an ethylene content of 20 to 50 mol% in the copolymer. If the ethylene content is less than 20 mol%, the thermoformability of the resin will be poor, and if it exceeds 50 mol%, the iodine content will decrease and antibacterial properties may be insufficient.

Commercially available EVOH resins include Soarnol D2908, Soarnol DT2903, Soarnol DC3203, Soarnol E3808, Soarnol ET
3803, Soarnol A4412, Soarnol AT44
03, Soarite M, Soarite G25H, Soarite G40H, Soarite G55H, Soarite S, Soarite G30K, Soarite G50K (all trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EVAL EP-F101,
EVAL EP-H101, EVAL EP-E105, EVAL EP-C110 (all of which are manufactured by Kuraray Co., Ltd., trade names) and the like can be used.

[0044]

Embodiments of the present invention will be described below with reference to the embodiments shown in the drawings. 1 to 9 schematically show various methods for producing the antibacterial composition of the present invention. That is, as shown in FIG. 1A, a thermoplastic resin 1 containing acrylonitrile of 10% by weight or more, preferably 15% by weight or more (hereinafter, represented by an ABS resin in the present embodiment) 1 is used by a pelletizer 2. To form a desired grain shape. In the pelletizer 2, the raw material resin 1 supplied from the hopper 2a to the main body 2b is heated and softened by a heater (not shown), and the screw 2c disposed inside the main body 2b is rotated. The extruded die 2d is extruded from a large number of die holes 2e, and cut into a predetermined length by a rotary cutter (not shown) disposed on the outlet side thereof. It is molded into a (bale-shaped) resin particle (pellet) 4. The volume of the resin particles 4 is adjusted in the range of 0.001 to 0.4 cm ³ . Further, the resin particles 4 may be formed in a spherical shape as shown in FIG. 3C, or may be formed in a spheroidal shape as shown in FIG.

Next, as shown in FIG. 2, the obtained resin particles 4 were sealed in a closed container 6 together with a scaly iodine crystal 5 (or solid iodine powder) and placed outside the container. The resin particles 4 and the iodine crystal 5 are heated by a heater 7 (or in the container or built in the wall of the container). Here, the amount of the iodine crystal body 5 to be enclosed is appropriately selected according to the material and amount of the resin particles 4 and the iodine concentration added per unit weight of the resin particles 4.

Next, as shown in FIGS. 2A and 2B, the resin particles 4 and the iodine crystal 5
Are heated in contact with each other. Then, iodine is diffused and added to the resin particles 4 by directly diffusing iodine from the iodine crystal 5 at the contact portion (iodine adding step). Further, iodine is also diffused into the resin particles 4 from iodine vapor 5a generated by sublimation of the iodine crystal 5. Here, the heating temperature is appropriately selected in the range of 55 to 120 ° C. according to the concentration of iodine to be added to the resin particles 4 and the type of the resin.

In this way, iodine is added to the resin constituting the resin particles 4 to form a granular antibacterial composition (antibacterial composition particles) 14, as shown in FIG. 2 (c). In this case, the resin particles 4 expand due to the addition of iodine, but the shape of the antibacterial composition particles 14 finally obtained largely reflects the shape of the resin particles 4. Here, it is estimated that the iodine concentration distribution inside the grains of the antibacterial composition 14 is as follows. That is, since iodine is added by diffusing from the surface of the molded body toward the inside,
It is considered that a concentrated layer having a relatively high iodine concentration is formed in the surface layer portion, and the iodine concentration gradually decreases toward the inside.

Although it is not impossible to use the antibacterial composition particles in the above-mentioned state as an iodine elution source or the like as it is, for example, when it comes into contact with water or the like, the iodine concentrated in the above-mentioned concentrated layer is once removed. And the release rate may be excessive depending on the purpose of use. Then, heat treatment can be applied to the antibacterial composition particles 14 in order to homogenize it (heat treatment step). That is, as shown in FIG. 3, the antibacterial composition
By heating in a temperature range of 0 to 120 ° C., iodine can be diffused from a high concentration region in the surface layer portion of the antibacterial composition particles 14 to a low concentration region in the inside, and the concentration distribution can be made uniform. Although the furnace 15 is an open-to-atmosphere furnace, an atmosphere furnace or a vacuum furnace can also be used, so that the heat treatment step can be performed in a predetermined gas atmosphere or a vacuum atmosphere.

Next, in the iodine adding step, as shown in FIG. 4, the resin particles 4 and the iodine crystal 5 are sealed in a cylindrical hermetically sealed container 16 and the resultant is rotated in a circumferential direction by a rotating machine 17. It can also be implemented. Here, the heater 7 for heating is built in the wall of the sealed container 16. The amount of the iodine crystal 5 to be sealed is set to a value substantially equal to the amount of iodine to be adsorbed on the resin particles 4, and the entire amount is almost completely consumed by absorption into the resin particles 4. In other words, after the completion of the iodine addition step, the temperature can be raised while maintaining the hermetically sealed state of the container 16, whereby the heat treatment step can be immediately started.

Further, the iodine adding step can be performed in a state where the iodine crystal 5 is not brought into direct contact with the resin particles 4.
That is, as shown in FIG. 5, the resin particles 4 are accommodated in a cylindrical container body 18 formed of a net or the like, and the resin particles 4 are rotated in a circumferential direction by a rotation mechanism 20 including a motor 20 a in a processing chamber 19. The iodine vapor generation source 21 is arranged close to this. The iodine vapor generation source 21 includes a solid iodine accommodating section 22 accommodating the iodine crystal 5, and a heating device 23 for heating the accommodated iodine crystal 5.
The iodine vapor 5a is generated by heating and sublimation of the iodine crystal 5, and the iodine vapor 5a
To add iodine to it. Processing chamber 1
A heater 7 is provided in 9 so that the temperature in the room is maintained at a temperature suitable for adding iodine. In addition, 1
9a is a door for taking in and out the resin particles 4 or the iodine crystal 5 and the like. Here, as shown in FIG.
The resin particles 4 may be formed in a box shape, and the resin particles 4 may be brought into contact with the iodine vapor 5a while vibrating the resin particles 4 together with the container body 18 using the vibrator 24. Thus, the method of contacting only the iodine vapor 5a with the resin particles 4 while avoiding direct contact with solid iodine is particularly effective when it is desired to add iodine to the resin particles 4 as uniformly as possible. In addition,
When the resin particles 4 are brought into contact with the iodine vapor 5a, it is not always necessary to apply rotation or vibration to the resin particles 4.

As shown in FIG. 7, the iodine vapor generating source 21 may be provided outside the processing chamber 19, and the iodine vapor 5a may be introduced into the processing chamber 19 by using the pipe 25. Here, an air blowing mechanism 27 that circulates the iodine vapor 5 a between the iodine vapor generation source 21 and the processing chamber 19 is provided on the pipeline 25. In order to prevent solid iodine from condensing and accumulating on the inner surface of the pipe 25, the pipe 2
The heater 26 can be heated by providing a heater 26 outside (or built in the wall of the conduit 25).

Here, instead of making the resin to which iodine is added into particles, as shown in FIG.
By injecting into a cavity 33 of a desired shape to form a resin structure, and adding iodine thereto by the same method as described above, an antibacterial structure having a shape corresponding to the resin structure is obtained. Can be obtained. Further, when producing a granular antimicrobial composition, as shown in FIG.
For example, the massive antibacterial structure 41 may be pulverized by the pulverizer 40. After the raw resin mass is pulverized by the pulverizer 40, iodine may be added thereto.

Hereinafter, examples of use of the above-described antibacterial structure will be described. FIG. 10 shows an example of the apparatus for producing an iodine-containing liquid of the present invention. The iodine-containing solution producing apparatus 50 is adapted to be used by being attached to a supply faucet of a liquid (for example, water) as a raw material, and has a main body 51 formed in a cylindrical shape and a lower side of an upper main body 52 thereof. A lower body 53 is detachably screwed to the portion from the outside.
A liquid inlet 54 is formed on the upper surface of the upper body 52, and a liquid outlet 55 is formed on the lower surface of the lower body 53. Further, inside the main body 51, a large number of antibacterial composition particles 14 as an iodine supply source are accommodated. The antibacterial composition particles 14 are accommodated in a bag body 60 formed through a liquid by a PVA sponge sheet as an absorbent, and are loaded into the main body 51 together with the bag body 60. Note that the antibacterial composition particles 14 are such that the base resin is an ABS resin, and iodine is added to the resin for 200 to
600% by weight, preferably 250-500% by weight is used.

The liquid outlet 55 is opened at the lower end surface of a lower projecting portion 55a formed so as to project from the lower surface of the lower body 53, and a hose or a tube is required on the outer peripheral surface of the projecting portion 55a. The stopper rib 55b is formed on the outer peripheral surface for connection according to. In addition, the liquid inlet 54 opens on the upper surface of an upper protruding portion 54 a formed to protrude from the upper surface of the upper main body 52. A male screw part 54b is formed on the outer peripheral surface of the upper projecting part 54a, while a faucet mounting part 5 having a female screw part 56a formed inside.
6 is attached to a faucet (not shown) by a screw 57. Then, the male screw portion 54b on the main body 51 side
Is screwed into the female screw portion 56a on the faucet attachment portion 56 side, so that the iodine-containing solution producing apparatus 50 is attached to the faucet.

When the iodine-containing solution producing apparatus 50 is attached to a faucet and a liquid is introduced into the main body 51 from an inlet 54, the iodine is eluted by contact with the antibacterial composition particles 14 to become an iodine-containing liquid. Is discharged from The average volume of the antibacterial composition particles 14, the total amount of the antibacterial composition particles 14 to be filled, and the flow rate of the liquid are, for example, when the obtained iodine-containing liquid is used as an iodine-containing disinfectant, the iodine concentration Is adjusted to be 1 to 50 ppm, preferably 3 to 15 ppm.
Specifically, if the total amount of the antibacterial particles is 10 to 100 g and the supply rate of the liquid is 1 to 3 L / min, the iodine concentration can be adjusted to the above range.

Here, when the circulation of the liquid is stopped for a long time, iodine is eluted from the antibacterial composition particles 14 into the liquid remaining in the main body 51, and the residual liquid having a high iodine concentration is PVA. Absorbent bag 6 made of sponge
And the iodine component is partially P
Since it is adsorbed on the VA sponge, it is possible to avoid the problem that the excessively concentrated iodine solution flows out when the flow of the liquid is resumed. When the concentration of iodine in the obtained solution is to be increased, or when the comfort of using the iodine-containing solution for hand washing or the like is desired to be increased, the temperature of the liquid should be 30 to 4%.
It can be used by heating to about 5 ° C.

As shown in FIG. 10 (b), the antibacterial composition granules 14 are mixed with the antibacterial composition granules 14 by mixing small pieces 61 of an absorbent made of, for example, PVA sponge. May be packed in the bag body 60 and filled in the main body 51. In this case, since the absorption and retention of the residual liquid and the adsorption of iodine also occur on the small pieces 61 of the absorbing material, the above-described effect is further enhanced. In this case, the average volume of the absorbent small pieces 61 is 0.03 to ³ cm ^3, and the blending amount of the absorbent small pieces 61 per 1 g of the antibacterial composition particles 14 is 0.03 to 0.4 g. You. Further, as shown in FIG. 10C, a fibrous aggregate or a sintered body of plastic particles is placed above and below a bag body 60 filled with the antibacterial mixed granular material 62 (or the aggregate of the antibacterial composition particles 14). The filter 63 may be disposed, for example, and an activated carbon layer may be disposed between the bag 63 and the filter 63 disposed on the liquid inlet 54 side.

Further, in the above-mentioned iodine-containing solution producing apparatus 50, if the structure in which the liquid in the main body 51 can quickly flow out from the outlet 55 when the liquid circulation is stopped is adopted, the liquid circulation is stopped for a long time. The problem of an overly concentrated iodine solution flowing out when this is resumed later can likewise be avoided. Specifically, as shown in FIG. 10 (c), a ventilation hole 52a for forming an air communication portion is formed on, for example, the upper surface of the upper main body 52, and this is closed with a stopper 52b while the liquid is flowing. Can be adopted. When the circulation is stopped, the plug 52b is withdrawn to prevent the air from entering the main body 51 through the ventilation hole 52a and the inside of the main body 51 from being decompressed due to the outflow of the liquid. The liquid can be quickly discharged from the nozzle 51.

On the other hand, as shown in FIG.
3 is slightly larger, and the upper body 52 and the lower body 5
A configuration may be adopted in which the edge of the filter 63 is sandwiched between the threaded portion and the filter 3 and the filter 63 is held slightly floated from the bottom surface of the lower body 53. In this case, the liquid outlet 5
The inner opening of the filter 5 is less likely to be closed by the filter 63, and the remaining liquid (particularly, the liquid remaining on the lower side of the floating filter 63) easily flows out from the outlet 55. Further, since the filter 63 is sandwiched between the upper main body 52 and the lower main body 53, the filter 63 also functions as a seal member for preventing liquid leakage from the threaded portions. In this case, if at least one of the upper and lower filters 63 is made of a PVA sponge, the filter 63 simultaneously plays a role of the above-mentioned absorbent and also has an effect of further enhancing the function of preventing the outflow of the liquid having a high iodine concentration. Can be achieved. In addition, from the viewpoint of preventing liquid leakage at the screwing portion, the upper body 52 and the lower body 5 are replaced with the filter 63.
3, a ring-shaped member (for example, P
VA sponge) may be used.

FIG. 11 shows an example in which the main body 51 is formed as a shower faucet. That is, in this configuration, the upper main body 52 and the lower main body 53 are detachable from each other by being screwed together with the male screw part 52a formed on one side and the female screw part 53a formed on the other side. Is combined with An opening 53b is formed on the lower surface side of the lower main body 53, and a shower nozzle member 53d is fitted therein. On the other hand, the upper body 52
A mounting mechanism 56 for mounting the upper main body 52 to the liquid supply passage D such as a hose is provided on the liquid inlet 54 side. The liquid introduced into the main body 51 from the liquid supply passage D comes into contact with the antibacterial mixed granules 62 (or the aggregate of the antibacterial composition particles 14) to become an iodine-containing solution, and is ejected from the shower nozzle hole 53e. It will be. In this case, the iodine content of the antibacterial granular material 14 is suitably 100 to 600% by weight, preferably 200 to 500% by weight based on the resin.

In the above configuration, the antibacterial granular material 1
4 has an iodine content of 70 to 400% by weight (preferably 1
If it is set to be a little lower (00 to 300% by weight), the water can be disinfected by removing or reducing microorganisms by flowing water, for example. In this case, when the water after disinfection is used for drinking, a layer of activated carbon, calcium sulfite or the like may be further circulated to remove dissolved iodine.

Next, FIG. 12 shows an example in which the antibacterial composition of the present invention is used to construct a simple disinfecting unit used in a sink or a bathroom. As shown in FIG. 2B, the sterilization unit 300 includes a container 301 having at least a part of a wall surface formed through a liquid, and an antibacterial mixed granular material 62 accommodated therein. Then, as shown in FIG. 7A, one end of a flexible member 303 such as a thread, a string, or a chain is connected to an attachment portion 302 formed on the container body 301, and the other end side is a sink. It is used by being fixed in the vicinity of a drain port S of a bathroom or a bathroom (for example, a flow-through lid C closing the drain port S). That is, the drain S
The iodine elutes from the antibacterial mixed granular material 62 contained in the container 301 with respect to the moisture existing near the
And the propagation of microorganisms such as various germs around the area is prevented or suppressed. In addition, water is held in the small pieces 61 of the absorbent, so that appropriate moisture is always provided around the antibacterial composition particles 14, and thus iodine can always be released without excess or shortage. In this case, the iodine content of the antibacterial granular material 14 is suitably 100 to 600% by weight, preferably 150 to 500% by weight based on the resin.

The antibacterial mixed granular material 62 is placed in the container 301.
Is used instead of a molded product (an antibacterial structure) of an antibacterial composition, for example, a plate-shaped molded product 305 having a large number of through holes 304 formed in the thickness direction. The member 303 may be fixed near the drain port S. As shown in FIG. 13, a flexible member 303 is attached to a bag body 60 filled with the antibacterial mixed granules 62 (or the antibacterial composition granules 14), for example, into a tea bag shape. It may be configured and fixed to the vicinity of the drain port S.

Further, as shown in FIG. 14, the flow-through lid for closing the drain port S is attached to the antibacterial structure 3 of the composition of the present invention.
It can also be configured as 30. The antibacterial structure 33
Numeral 0 has a disk-shaped bottom 330a, and an outer wall 330b is formed along the outer edge thereof. Also, the bottom 330
An outlet 330c is formed at the center of a, and an inner wall 330d is formed along the inner edge thereof. As shown in FIG. 14A, the antibacterial structure 330 is attached to, for example, the drainage hole S by being fitted into a receiving portion U formed in a stepped surface along the upper portion of the inner edge thereof. You. The drainage W flows into the concave portion 330e formed by the bottom portion 330a, the outer wall portion 330b, and the inner wall portion 330d, and then overflows from the upper edge of the inner wall portion 330d and flows out from the outlet 330c. When the supply of the drainage W is interrupted, the drainage W remains and is retained in the concave portion 330e, and the release of iodine from the antibacterial structure 330 into the drainage W is promoted. Thereby, it is possible to effectively prevent or suppress the propagation of microorganisms and the like around the drain port S.

When the powdery antibacterial composition of the present invention is sprinkled on garbage or the like and used, an effect of suppressing the propagation of various bacteria and generation of offensive odor can be obtained.

The antibacterial structure 3 shown in FIG.
Numeral 10 is configured to have a radial cross-sectional shape by integrating a plurality of plate-like portions 310a on one edge side thereof. As shown in FIG. 2B, for example, such an antibacterial structure 310 is placed in a tank 311 (for example, having a volume of 10 to 2) containing a liquid (for example, water).
0 liter), the liquid L in the tank 311 can be made into an iodine-containing solution by the released iodine. In this case, since the antibacterial structure 310 is formed as an aggregate of the plate portions 310a, the contact area with the liquid L is increased, and the iodine release efficiency is increased. The antibacterial structure 310
Instead, as shown in FIG.
A plate-shaped antibacterial structure 320 having Oa may be used.

As an iodine-containing solution producing device based on a similar principle, a squeeze bottle type container (for example, a washing bottle type) composed of a flexible resin material, or a pump accumulator type or a pump pumping type can be used. It is also possible to adopt a method in which the above-mentioned antibacterial composition particles and a liquid are placed in a container, and iodine is eluted from the antibacterial composition particles into the liquid to obtain an iodine-containing solution. For example, in a squeeze bottle type iodine-containing solution generator 300 shown in FIG. 16, a cylindrical protrusion 302 is integrally provided in a bottle-like liquid container 301 made of a flexible elastic material such as polypropylene. An opening 302a is formed at the tip. A cap member 305 having a liquid outflow nozzle hole 306 formed at the tip thereof is detachably attached to the protruding portion 302 by screwing. As a method of using the same, the cap member 305 is removed, and the liquid container 30 is opened through the opening 302a.
1, a liquid L such as water and a predetermined amount of the antibacterial composition particles 14 are charged, and the cap member 305 is mounted again. As a result, iodine is eluted from the antibacterial composition particles 14 into the liquid L to form an iodine-containing solution. When the iodine-containing solution is used, for example, as a disinfecting solution or the like, by inverting the liquid storage unit 301 and pressing the side surface, the internal pressure in the liquid storage unit 301 rises, and the solution flows out of the liquid outflow nozzle hole 306. Spill out of. The opening 302a of the liquid container 301 is closed by a net 307 (or a filter) for preventing the antibacterial composition particles 14 from leaking out in a state where the flow of the liquid is allowed.

In the above-described iodine-containing solution generator, if the outlet of the container is sealed or can be sealed with the outside air when not in use, the inside of the container can be closed when not in use. This is convenient for preventing iodine from sublimating. For example, in the case of the structure shown in FIG.
A cover member 308 that can open and close the cover 06 can be provided.

In the embodiment shown in FIGS. 15 and 16, the iodine content in the antibacterial composition was 70% by weight.
Even if it is less than this, this may be suitably used as a constituent material of the iodine elution portion. For example, when the obtained iodine-containing solution is used as a disinfectant, the iodine concentration in the solution should be adjusted to 1 to 100 ppm, preferably 5 to 50 ppm, and the iodine content in the antibacterial composition particles Is preferably not less than 5% by weight, more preferably not less than 10% by weight with respect to the resin.

A surfactant such as polyvinylpyrrolidone, polyvinyl alcohol, cyclodextrin, or poloxamer is added to the liquid L as a complex-forming organic substance, and the antibacterial structure 310 or the antibacterial composition particles 14 are added. By forming a complex with iodine eluted from the iodine elution portion and the complex thereof, iodine in the solution can be stably held, and further, escape of iodine due to sublimation or the like can be prevented. In this case, if, for example, a resin mainly composed of polyvinylpyrrolidone or polyvinyl alcohol is used as a resin serving as a base of the antibacterial composition constituting the iodine eluting portion, a part of the resin is eluted with iodine to form the complex. May be done.

The resin serving as the base of the antibacterial composition constituting the iodine eluting portion is the above-mentioned ethylene-vinyl alcohol resin (EVOH resin) mainly composed of a copolymer of ethylene and vinyl alcohol. Can also be used.

FIG. 17 (a) shows an example of a shower faucet fitting (hereinafter, referred to as a shower faucet) as a liquid supply device having a function of preventing microorganisms from entering according to the present invention. That is, in the shower faucet 250, the upper body 2
31 and a lower body portion 232, and the liquid inlet 23
It has a hollow main body 230 whose diameter is reduced on the 6 side. The upper body part 231 and the lower body part 232 are detachably connected to each other by screwing together with a male screw part 231a formed on one side and a female screw part 232a formed on the other side. . An opening 232b is formed on the lower surface side of the lower main body 232 so that the lower main body 23
An antibacterial nozzle member 240 as an outlet antibacterial portion is detachably fitted into the opening 232b from the inside of the container 2,
Locking portion 23 formed along the inner peripheral surface of opening 232b
2c prevents it from falling off. The antibacterial nozzle member 240 is formed in a plate shape as an antibacterial structure as a whole, and a large number of shower nozzle holes 235 are formed through the antibacterial nozzle member 240 in the plate thickness direction. The amount of iodine added to the resin is adjusted in the range of 70 to 200% by weight. On the other hand, a mounting mechanism 237 for mounting the upper main body 231 to the liquid supply path D such as a hose is provided on the liquid inlet 236 side of the upper main body 231.

The shower faucet 250 as described above can be used by attaching it to a faucet 284 for taking out a liquid in a supply line of sterilized water or the like installed in a hospital or the like as shown in FIG. That is, a purification device 2 composed of a reverse osmosis membrane type filtration device or a distillation device.
The raw material water supplied to 81 is sterilized water in which microorganisms are removed or reduced there, and is stored in a tank 282 through a pipe 281a. Then, the stored sterilized water is supplied to each faucet 250 through the pipe 283 and taken out.

Then, as shown in FIG. 17 (a), in the shower faucet 250, the main body 230
The liquid introduced therein is ejected from the shower nozzle hole 235. Here, since the shower nozzle hole 235 is formed in the antibacterial nozzle member 240, intrusion of bacteria and the like into the main body 230 is prevented or suppressed. When the antibacterial effect of the antibacterial nozzle member 240 has been reduced and the life has expired, the lower main body 232 can be removed from the upper main body 231 and replaced with a new one.

Note that, as shown in FIG.
An assembly of the antibacterial composition particles 14 may be accommodated in 30 and the invading bacteria and the like may be removed by the antibacterial composition particles 14. In this case, as the nozzle member, either a member made of an antibacterial composition (240) or a member made of a normal resin having no antibacterial property may be used. In the case of (1), since the microorganisms are removed by both the antibacterial composition particles 14 and the antibacterial nozzle member 240, the effect of preventing the invasion of microorganisms is further enhanced. As shown in FIG. 18, an annular fitting protrusion 24 is provided on the upper surface side of the antibacterial nozzle member 240, for example, along the circumferential direction thereof.
It is also possible to adopt a configuration in which Oa is integrally formed, the fitting projection 240a is press-fitted into the lower main body 232, and this is integrated. In this case, when the life of the antibacterial nozzle member 240 has expired, the lower main body 232 may be replaced with a new one together with the antibacterial nozzle member 240 integrated therewith.

Next, FIG. 20 shows an example of a faucet fixture other than a shower faucet. The faucet attachment 200 has a main body 217 formed in a cylindrical shape, and an upper end of a lower main body 219 is integrally fitted to a lower end of an upper main body 218. Also, the upper end 220 of the upper body 218
Is reduced to form a liquid inlet 220c, and the lower end 221 of the lower body 219 is similarly reduced in diameter to form a liquid outlet 221c. The lower main body 219 is configured as an antibacterial structure, and functions as an exit antibacterial part.

The lower end 221 of the lower body 219 is provided with a retaining rib 221a on the outer peripheral surface thereof for connecting a hose or a tube as required. A male screw portion 220a is formed on the upper end portion 220 of the upper main body 218. The male screw portion 220a is screwed with the female screw portion 222a of the faucet mounting portion 222 so that the two can be integrally assembled. Here, the faucet mounting part 22
0 is attached to a predetermined faucet (not shown) by a screw 224. A cap 221 for closing the liquid outlet 221c when not in use is provided at the lower end 221 of the lower main body 219.
b is detachably mounted. This cap 221b
Can be configured as the antimicrobial structure described above.

As shown in FIG. 21, a sterilization filter 27 made of a porous hollow fiber membrane or the like is provided inside a main body 217.
2 may be arranged to filter the liquid passing from the inlet 220c to the outlet 221c. The sterilization filter 272 is formed by, for example, bending a plurality of porous hollow fiber membranes into a loop (or U-shape) and binding them, and bonding the opening-side end 274 of the same with an adhesive such as a polyurethane resin.
A fixed one can be used.

FIGS. 22 and 23 show another structure of the faucet fitting. For example, in the attachment 200 shown in FIG. 22A, the entire body 217 having a reduced diameter on the liquid outlet 217p side is configured as an antibacterial structure, and a female screw formed on the inner surface of the liquid inlet 217s. In the part 285, this is screwed into the male screw part 286 on the faucet D side, so that the faucet D is detachably mounted. Here, the entire body 217 is not configured as an antibacterial structure, and for example, as shown in FIG.
17q is formed as a separate body, and this is inserted into a recess 2 formed on the inner surface of a main body 217 made of ordinary resin or the like.
17r. On the other hand, in the fixture 200 shown in FIG. 23, the main body 217 is formed of a normal resin, and the outlet 217p thereof is formed to have a size substantially corresponding to the outlet J of the faucet D.
On the other hand, an antibacterial structure 217q of the present invention formed into a honeycomb shape by injection molding is fixed.

[0080]

(Example 1) ABS resin pellets (Diapet AB)
50 g of SPS505 (manufactured by Mitsubishi Rayon Co., Ltd.) and solid iodine (special grade reagent (crystal scaly), Wako Pure Chemical Industries, Ltd.
150g) and a glass wide mouth bottle (volume 250cc)
And sealed. Note that the pellets are cylindrical with a diameter of 2 mm and a length of 3 mm. This was heated to 60 ° C. in an oven while rotating using a rotating machine 17 as shown in FIG. After a lapse of 48 hours in this state, it was visually confirmed from the outside of the transparent bottle, and almost no solid iodine remained. Then, when the heat treatment is continuously performed at 100 ° C. for 24 hours without rotating, the solid iodine completely disappears visually, and the weight of the treated pellet is 199.7 g.
, It was confirmed that almost all of the iodine was absorbed by the resin pellets. 1g of this pellet is 50
When immersed in ml of water (temperature: 20 ° C.) and left for 48 hours, the iodine concentration in the water reached 100 ppm, indicating that the antibacterial composition of the present invention had good iodine elution characteristics. The iodine content is 299.4% by weight based on the resin.

The dimensions of the pellet after iodine absorption expanded to about 2.5 mm in diameter and about 3 mm in length, but the columnar shape was maintained almost as it was, and it was fragile like solid iodine. There was no cracking or chipping when shaking in a bottle.

(Example 2) In the same manner as in Example 1, 10 to 50 g of various amounts of solid iodine per 10 g of ABS resin pellets were put in a bottle, and rotated at 70 ° C while rotating.
Was continued until iodine was completely absorbed, and the amount of iodine added to the resin was calculated from the measurement of the pellet weight after the treatment. FIG. 24 shows the results of plotting the amount of added iodine against the time until iodine was completely absorbed. The amount of iodine added to the resin exceeds 100% by weight in 10 hours,
It can be seen that it has reached nearly 00% by weight.

Example 3 The same ABS resin pellets as used in Example 1 were crushed into small pieces having an average particle size of 1.5 to 2 mm by a predetermined crusher, and 50 g of the crushed pieces were mixed with 75 g of solid iodine. It was put in a bottle and heated at 60 ° C. for 24 hours while rotating as in Example 1. At this time, when visually confirmed from the outside of the transparent bottle, almost no solid iodine remained. Then, when the heat treatment was continued at 90 ° C. for 24 hours without rotating, the solid iodine completely disappeared visually, and it was confirmed that almost all of the iodine was absorbed by the resin pellets (the amount of iodine added to the resin: 150). weight%).

Example 4 5 g of AS resin pellets (Styrac-AS767 (manufactured by Asahi Chemical Industry Co., Ltd.)) and solid iodine (special grade reagent (crystal flakes), Wako Pure Chemical Industries, Ltd.)
5 g) were sealed in a glass wide-mouth bottle (volume: 50 ml). Note that the pellets are cylindrical with a diameter of 2.5 mm and a length of 3.5 mm. This was heated in an oven at 80 ° C. for 24 hours while rotating using a rotating machine 17 as shown in FIG. 4, and then heat treated at 100 ° C. for 8 hours without rotating. Next, after opening this, the resin pellet and the remaining solid iodine were separated using a sieve,
When the weight of the pellet was measured to measure the amount of iodine absorbed, it was 86% by weight based on the weight of the resin. 1 g of the pellet is immersed in 50 ml of water (temperature 20 ° C.)
After standing for 48 hours, the iodine concentration in the water was 70 pp
m, indicating that the antibacterial composition of the present invention has good iodine elution characteristics.

Example 5 50 g of the same ABS resin pellets as used in Example 1 and 75 g of solid iodine were placed in a bottle, and rotated at 60 ° C. while rotating as in Example 1.
After heating for 4 hours, heat treatment was performed at 100 ° C. for 24 hours without rotating. It was confirmed that almost all the solid iodine was absorbed by the resin pellets, and the amount of iodine added to the resin was 150% by weight. 1 g of the pellet after the addition of iodine is poured into 100 cc of water and sealed, and the water is exchanged once a day with a new one once a day in an oven.
When the treatment of heating to 70 ° C. was performed for 70 days, the elution of iodine continued even after 70 days, and the water was exchanged for 2 days.
After 4 hours, the iodine concentration in the water reached 3 ppm.

A cycle in which 8 g of the same pellets are loaded into the main body of a shower faucet as shown in FIG. 17 and hot water of 42 ° C. is continuously supplied at a flow rate of 4 liter / min for 9 hours and then stopped for 15 hours Up to 60 days, and before starting water flow every day, collect 50 cc of water from the faucet,
The iodine concentration was analyzed. For comparison, a similar experiment was performed using pellets in which the amount of iodine added to the resin was 10% by weight. FIG. 25 shows the result. In the case of using the pellets of Examples, elution of about 2.5 ppm of iodine was observed even after 60 days. This concentration is a sufficient value for preventing reverse contamination of the shower faucet due to intrusion of microorganisms. On the other hand, in the case of using the pellet of the comparative example, the elution amount of iodine was less than 1 ppm after 6 days, and it was found that the effect of preventing reverse contamination was lost.

(Example 6) 15 g of pellets having an added amount of iodine of 500% by weight and produced under the conditions of Example 2 were mixed with each other in FIG.
Main body 51 of apparatus for producing iodine-containing solution 50 shown in FIG.
Inside. Then, this was directly connected to a water tap, a cycle in which the tap was opened, water was continuously supplied at a flow rate of 1.5 liter per minute for 9 hours, and then stopped for 15 hours was repeated. The iodine concentration in the effluent was 10 ppm immediately after the start of water flow, 8 ppm at a cumulative water flow of 1000 liters, and 2000 ppm.
It turned out to be 6 ppm in liter, and 1000 to 2000 liter of iodine-containing aqueous solution was obtained. On the other hand, for comparison, a similar experiment was performed using a pellet having an iodine addition amount of 50% by weight. At a cumulative water flow of 500 liters, the iodine concentration was reduced to 4 ppm or less.
At 000 liters, the concentration was 2 ppm or less, which was poor in practicality as an apparatus for producing an iodine-containing aqueous solution.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a method for producing a resin pellet and an example of a pellet shape.

FIG. 2 is an explanatory view showing an example of an iodine adding step of the antibacterial structure of the present invention.

FIG. 3 is an explanatory view of a heat treatment step.

FIG. 4 is an explanatory view showing a first modified example of the iodine adding step.

FIG. 5 is an explanatory view showing a second modified example.

FIG. 6 is an explanatory view showing a third modified example.

FIG. 7 is an explanatory view showing a fourth modified example.

FIG. 8 is a schematic view showing a method for manufacturing a resin structure by injection molding.

FIG. 9 is a schematic view showing a method for producing resin particles by pulverizing a resin structure.

FIG. 10 is a cross-sectional view showing some embodiments of the apparatus for producing an iodine-containing solution of the present invention.

FIG. 11 is a cross-sectional view showing a modification of the iodine-containing solution producing apparatus in which the main body is configured as a shower faucet.

FIG. 12 is an explanatory view showing a simple type sterilization unit using the antibacterial composition of the present invention together with its modified example.

FIG. 13 is a perspective view showing a modification in which the simple disinfecting unit is formed in a tea bag shape.

FIG. 14 is a front sectional view and a perspective view of an antibacterial structure suitable for preventing the propagation of various bacteria in a drain hole.

FIG. 15 is an explanatory diagram showing an antibacterial structure suitable for producing an iodine-containing solution, together with a method of using the same and a modification.

FIG. 16 is a sectional view showing an example of a squeeze bottle type iodine solution generator.

FIG. 17 is a cross-sectional view showing some examples of a shower-type faucet fitting with a microorganism intrusion prevention function.

FIG. 18 is a sectional view showing a modified example thereof.

FIG. 19 is a diagram conceptually showing a supply line of sterilized water.

FIG. 20 is a front sectional view showing an example of a faucet fitting with a microorganism intrusion prevention function.

FIG. 21 is a front sectional view showing a second modified example.

FIG. 22 is a front sectional view and a bottom view showing the third and fourth modified examples.

FIG. 23 is a front sectional view and a bottom view showing a fifth modification.

FIG. 24 is a graph showing experimental results of Example 2.

FIG. 25 is a graph showing experimental results of Example 5.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Resin 4 Resin particle (resin structure) 5 Iodine crystal (solid iodine) 5a Iodine vapor 14 Antibacterial composition particle 50 Iodine-containing solution manufacturing apparatus 60, 61 Absorbent material 62 Antibacterial mixed granular material 200 Faucet fitting (microorganism Liquid supply tool with intrusion prevention function)

Claims (12)

[Claims] 1. A total of 10% by weight of at least one of an acrylonitrile component and a methacrylonitrile component.
It contains the above-mentioned resin and iodine, and the content of iodine is 70% by weight or more relative to the resin, and at least a part of the contained iodine is released or released in the presence of water. An antimicrobial composition characterized in that: 2. The resin according to claim 1, wherein a copolymer of an acrylonitrile component and a styrene component contains polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylic rubber, ethylene-propylene copolymer, and chlorine. The antibacterial composition according to claim 1, wherein the elastic phase composed of at least one of the polyethylene is dispersed by chemical bonding or mixing. 3. The antibacterial composition according to claim 2, wherein the resin contains at least 15% by weight of an acrylonitrile component and at least 10% by weight of a butadiene component. 4. The resin is mainly composed of at least one of an acrylonitrile-butadiene-styrene resin, an acrylonitrile-styrene resin, an acrylonitrile-chlorinated polyethylene-styrene resin, and a vinyl chloride-acrylonitrile copolymer resin. Claim 1
4. The antimicrobial composition according to any one of items 1 to 3. 5. The method according to claim 1, wherein the content of iodine is 100 to 600% by weight based on the weight of the resin.
5. The antibacterial composition according to any one of items 4 to 4. 6. The antibacterial composition according to claim 1, wherein the composition has a granular shape, and the average volume of the particles is 0.001 to 2 cm ^3.
6. The antibacterial composition according to any one of items 1 to 5. 7. The method for producing an antibacterial composition according to claim 1, wherein the resin is brought into contact with solid iodine and / or iodine vapor while being heated to 55 ° C. or higher. And a method for adding an iodine to the resin. 8. The method for producing an antibacterial composition according to claim 1, wherein the resin is brought into contact with solid iodine and / or iodine vapor while being heated to 55 ° C. or higher. The method for producing an antibacterial composition according to claim 7, further comprising: an iodine adding step of adding iodine to the resin; and a heat treatment step of heat treating the resin to which the iodine is added at a temperature of 85 ° C or higher. 9. The particulate antimicrobial composition according to claim 6, wherein a small amount of absorbent having liquid absorbability is 3 to 40% by weight based on the total weight of the particulate antimicrobial particles. Antibacterial mixed granules characterized by being blended in proportions. 10. The antibacterial mixed granule according to claim 9, wherein the small pieces of the absorbent are formed of a sponge-like substance mainly composed of polyvinyl alcohol. 11. An antibacterial composition or a substance thereof according to claim 1, comprising an inlet and an outlet for a liquid, the liquid being disposed near the outlet, and from the inlet to the outlet. An outlet antibacterial portion that comes into contact with the liquid passing therethrough, and microorganisms that enter the inside of the outlet from the outlet are removed or reduced by iodine released or released from the outlet antibacterial portion. A liquid supply device with a function to prevent microbial invasion. 12. A main body having a liquid inlet and an outlet formed therein, and iodine formed of the antibacterial composition or its content according to claim 1 and disposed inside the main body. Having an elution portion, the liquid introduced into the main body from the inlet is brought into contact with the iodine elution portion, iodine contained in the iodine elution portion is eluted into an iodine-containing solution, The iodine-containing solution producing apparatus is discharged from the outlet.