JP6475903B2 - Chlorine sustained release device, method for producing weakly acidic hypochlorous acid water using the same, and simple deodorizing and disinfecting apparatus - Google Patents

Description

  The present invention relates to a chlorine sustained-release device having high safety, excellent sterilization effect and its sustainability, a method for producing hypochlorous acid water using the chlorine sustained-release device, and the chlorine sustained-release It also relates to a simple deodorizing and disinfecting device using tools.

  Chlorine disinfectants are known as aqueous disinfectants that are extremely effective even at low concentrations. For example, it is used for a wide range of sterilization such as drinking water, pool, cooling water, industrial water, sewage, etc. Hypochlorite water, sodium chlorite, sodium hypochlorite etc. are designated as food additives. Therefore, it is used for the purpose of removing microorganisms that adhere to food and cannot be completely washed away.

  Recently, a method of producing hypochlorous acid water by electrolyzing an aqueous solution of a chlorine compound and using it as a disinfectant, disinfectant, and deodorant has come to be widely used. In this case, the pH of the hypochlorous acid water used for disinfection and deodorization is preferably about 3 to 6.5 from the viewpoint of bactericidal effect, safety and corrosivity. For this reason, a method for adjusting the pH of hypochlorous acid water produced by electrolysis has been proposed (Patent Documents 1 and 2). However, these methods require complicated devices and are not suitable for use at home.

  On the other hand, a method of producing a hypochlorous acid water whose pH is adjusted by neutralizing an aqueous sodium hypochlorite solution with hydrochloric acid or the like (Patent Documents 3 to 6) or a method of adjusting the pH by blowing carbon dioxide (Patent Document 7) ) Is done. However, these methods require complicated operations to produce stable and uniform hypochlorous acid water. Moreover, after using hypochlorous acid water, naturally a liquid must be prepared.

  Further, as a device that can be used at home, a method has been proposed in which a solution of a chlorine compound is placed in a small sprayer with a built-in electrode and sprayed with hypochlorous acid water generated by electrolysis during use (Patent Documents 8 to 10). ). This method requires a solution of a chlorine compound, and it is necessary to add a water-soluble organic alkali in order to adjust the pH of hypochlorous acid water.

  Furthermore, it consists of a hydrophobic material containing an acid releasing agent and a diluent and a hydrophilic material containing a chlorite anion, and the hydrophilic material is a composite material that releases chlorine dioxide when the acid releasing agent is hydrolyzed (Patent Document) 11) and those that similarly release chlorine dioxide (Patent Document 12), and the like, but the problem is that the manufacturing process is complicated.

  A solid halogen agent that releases active halogen or a composition containing the solid halogen agent is a sterilizing detergent for drainage (Patent Document 13) that is composed of a material that is not permeable to water but is permeable to moisture. A tool (Patent Document 14) has been proposed in which salts such as calcium chloride and bleaching powder coexist in a container composed of a film having gas permeability at least partially. These tools enable the continuous preparation of hypochlorous acid water by continuous release of chlorine into water. However, the pH of the aqueous solution that has absorbed the released chlorine is not taken into consideration.

Japanese Patent Application Laid-Open No. 2012-196643 JP2013-71103A JP 2011-229833 A JP 2009-29792 A JP 2008-229555 A JP 2006-264996 A JP 2006-320899 A JP 2004-129954 A JP 2004-148109 A JP 2004-130265 A Japanese National Patent Publication No. 10-504841 Japanese National Patent Publication No. 10-504844 Japanese Patent Laid-Open No. 10-212209 JP 2006-167714 A

  The present invention has been made in view of the above-described problems of the prior art, and can easily prepare hypochlorous acid water whose pH is kept from weakly acidic to near neutral from water such as tap water at home. An object of the present invention is to provide a sustained release device for chlorine. Another object of the present invention is to propose a simple deodorizing and disinfecting device that can be used for a long period of time just by replenishing water such as tap water by using the chlorine sustained-release tool as a constituent element. Furthermore, it aims at preventing the contamination by the microorganisms of a water storage part.

  In order to solve the above-mentioned problems, the sustained release tool of the present invention is a tool for storing a chlorine-based disinfectant in a container made of a material that is at least partially gas permeable and that is entirely impermeable to water. And at least a part of the container made of a material having water permeability, and a tool for storing the poorly water-soluble inorganic calcium salt, and used in an aqueous environment.

  The “gas permeability” means that vapors in which water and the like are volatilized permeate other than so-called gases such as oxygen and chlorine. In short, liquid does not permeate, and gas permeates, so that water at normal pressure does not pass through the surface water repellency, such as non-woven fabrics that are widely used in the prior art, but depending on the pressure difference, Excluded are those with large pore sizes that allow liquid to pass through. Therefore, “a material that does not allow water to pass through” is a material that does not allow water to pass even in a state of being pressurized to about 0.5 atm in addition to water at normal temperature and normal pressure.

  The “water permeability” means passing water in a liquid state, and the non-woven fabric is an example. Since the container made of water-permeable material contains inorganic calcium salt that is sparingly soluble in water, it can be left in the water as a tablet without using the container. is there. Moreover, even when using limestone as calcium carbonate, it can be left in water as it is. However, it is preferable to keep it in a water-permeable container and isolate it from the state where the fine inorganic calcium salt released from the tablet is released in water. For this reason, it is desirable to accommodate the container.

  The “in the water environment” includes not only the case of using in water, but also the case of installing the chlorinated disinfectant in a place that is close to water but not in direct contact. On the other hand, it is assumed that the tool for storing the poorly water-soluble inorganic calcium salt is used in water as can be understood from the use of a water-permeable material.

  In the present invention, chlorine gas generated by the decomposition of the chlorine-based disinfectant is released from the inside of the tool to the surrounding environment, thereby maintaining the sterility of water for drinking, or setting the release concentration to a high level for sterilization / disinfection. Can be prepared. Moreover, even when the water in which chlorine is dissolved becomes acidic, the poorly water-soluble inorganic calcium salt is dissolved in the water, and the pH that is inclined to acidity is neutralized to obtain a weakly acidic to neutral aqueous solution. Can do it.

  The chlorinated fungicide is preferably chlorinated isocyanuric acid. Chlorinated isocyanuric acid is a chemically stable solid compound that is easy to handle and can release chlorine without rapid hydrolysis without contact with liquid water. It is because it is excellent.

  It is preferable that the chlorinated isocyanuric acid is trichloroisocyanuric acid and / or dichloroisocyanuric acid. This is because they are highly efficient in reacting with water vapor and releasing chlorine. Moreover, these are because there are many use examples and are being supplied stably industrially. Moreover, it is because it is provided with various dosage forms, such as a powder form, a granular form, and a tablet, according to the intended purpose.

  The poorly water-soluble inorganic calcium salt is preferably at least one selected from calcium carbonate, calcium phosphate, calcium sulfate, calcium fluoride, calcium silicate, and hydroxyapatite. These have long-lasting properties because they react and elute as much as necessary to neutralize the hypochlorous acid water that is poorly soluble in water.

  Further, if the combined chlorine sustained-release device coexists with water in a suitable container, weakly acidic hypochlorous acid water can be obtained. In particular, since a tool containing a chlorine-based disinfectant uses an impermeable container, it is the same whether it is immersed in water or placed in a gaseous environment in contact with water. Therefore, the term “coexistence” means that it is sufficient that the gaseous chlorine released from the tool can be in contact with water as well as being immersed in water.

  Furthermore, in another aspect of the present invention, the combined chlorine sustained-release device, a container that contains water together with the chlorine sustained-release device, and a nozzle that can be moved up and down in an upward biased state from the container opening, A pump mechanism that operates in conjunction with the vertical movement of the nozzle, and by pushing down with a finger a push-down portion that extends radially outward toward the base end side of the nozzle, Provided is a simple deodorizing / sterilizing device in which an internal solution containing chlorine in a container is ejected from the tip of a nozzle by the action. This is for the convenience of the user.

  In another aspect of the present invention, the combined chlorine sustained-release device, a container main body that contains water together with the chlorine sustained-release device, a mounting cylinder fitted to the mouth and neck of the container main body, and the mounting cylinder An upright vertical cylinder, an injection cylinder protruding forward from the upper end of the vertical cylinder, a cylinder protruding forward from an intermediate portion of the vertical cylinder, and slidably fitted in the cylinder; A plunger biased forward, a trigger whose upper rear surface engages with the front end of the plunger and swingably attached to the front of the injection cylinder, and attached to the front end of the injection cylinder A nozzle fitting tube and a nozzle hole are formed, and are rotatably attached to the outer surface of the nozzle fitting tube.A mist-like spray is produced at a predetermined position of the nozzle, and a straight liquid flow is produced at another predetermined position. With a switchable nozzle head By pulling the trigger rearwardly, the inner solution containing chlorine stored in the container body is sucked up, provides a trigger-type deodorant sterilization apparatus ejected through the nozzle hole. This is because spraying is easier to use to disinfect a wide area.

  The deodorizing and sterilizing apparatus of the present invention can be easily configured by combining a commercially available pump container or sprayer and the chlorine release device of the present invention, and supplemented after using tap water or the like as an internal solution. For example, it can be used for a very long time.

  Furthermore, the chlorine sustained release device of the present invention can also be used to prevent microbial contamination of a part where water is constantly stored in an open environment (for example, a faucet at the tip of a water purifier or a shower faucet).

  Since the chlorine sustained release device of the present invention has a simple structure, it is easy to manufacture, and since weakly acidic hypochlorous acid water can be easily prepared from water such as tap water, many articles and the environment can be disinfected safely. Can be deodorized. Furthermore, even if an organic chlorinating agent such as chlorinated isocyanuric acid is used as the chlorinating agent, only the chlorine gas is released from the sustained release device, so the generated hypochlorous acid water does not contain the original chlorinating agent. High safety.

  In addition, the method for producing weakly acidic hypochlorous acid water of the present invention is an extremely simple process of storing the chlorine sustained-release device together with water in a suitable container, so that it can be easily handled in ordinary households. If a pump container or a sprayer is used as the container, it can be used for deodorizing and disinfecting for a long time just by replenishing tap water. I can do it.

FIG. 1 is a diagram showing an example in which the chlorine sustained release device of the present invention is held in a finger spray container. FIG. 2 is a view showing an example in which the chlorine sustained release device of the present invention is held in a trigger type spray container. FIG. 3 is a view showing an example in which the chlorine sustained release device of the present invention is held in a pump container. FIG. 4 is a view showing an example in which the chlorine sustained release device of the present invention is held in a squeeze bottle. FIG. 5 is a view showing an example in which the chlorine sustained release device of the present invention is held in a shower faucet.

  The present invention includes a tool for continuously supplying gaseous chlorine to the water environment (hereinafter also referred to as “chlorine source container”) and a tool for maintaining the surrounding water environment from weakly acidic to near neutral (hereinafter referred to as “chlorine source container”). , Also referred to as “neutralizing agent storage device”). The tools having each function will be described below.

  The material of the container constituting the chlorine source container of the present invention has the property of not allowing water to pass through (water impermeability). Not only water at normal temperature and normal pressure, but also a water-impervious material that does not allow water to pass even if a pressure difference of about 0.5 atm is applied. For example, water at normal pressure does not pass due to surface water repellency, but does not include a material such as a nonwoven fabric that, when pressurized, allows water to pass through due to the large pore diameter. This is because, in such a material, the amount of water that permeates as water vapor is large, accelerates the hydrolysis of the chlorine-based disinfectant and releases excessive chlorine, and makes it difficult to achieve long-term chlorine release. In addition, when water vapor is not allowed to pass through, hydrolysis reaction does not occur, so it is necessary to have water vapor permeability. As a result, the environment inside the chlorine source container of the present invention has an appropriate humidity, and the chlorine-based disinfectant releases chlorine, but maintains a stable state to some extent.

  Since the chlorine source container has gas permeability at a part thereof, the internal pressure does not basically increase excessively. That is, since the chlorine-based disinfectant is not contained in the sealed container, chlorine generated by decomposition is gradually released from the gas permeable portion to the outside environment. If the pressure or chlorine concentration in the space reaches a certain value in an enclosed space, an equilibrium relationship is established that the decomposition of the chlorine-based disinfectant stops, and chlorine is not generated. Continuously releases chlorine. If the outer environment is a sealed space, the chlorine concentration is kept constant by equilibrium with the outer environment.

As the gas-permeable material of the present invention, a gas-permeable non-porous film and a special perforated film can be used. As the non-porous film having gas permeability, a commercially available gas permeable plastic film may be used. It is not necessary to use a film having a particularly high gas permeability, and any film other than a so-called gas barrier film may be used. For example, OPP (biaxially stretched polypropylene film), CPP (unstretched polypropylene film made by T-die casting method), LLDPE (linear low density polyethylene film), high density polyethylene film, polyethylene terephthalate film, nylon film, ethylene -Vinyl acetate copolymer film, polymethylpentene-1 film, polyethylene / polyethylene terephthalate laminate film, polymethylpentene-1 / polyethylene laminate film, etc. are used. On the other hand, gas barrier films such as MXD nylon film, polyvinylidene chloride film and polyacrylonitrile film cannot be used because they do not substantially permeate chlorine.

Since the gas-permeable non-porous film and the special perforated film are also substantially impermeable to water, if this material is used for the entire container, a chlorine source container can be constituted. Among the examples, OPP film, CPP film, LLDPE film, ethylene / vinyl acetate copolymer film and the like are particularly preferable. These are about 1 to 200 [g / m ² · 24 h · 1 atm] (20 ° C., when dried) when expressed in terms of CO ₂ permeability, which is an index of gas permeability. However, it should be noted that the CO ₂ permeability is not necessarily proportional to the permeability of the chlorine gas, and the affinity between the film and the chlorine gas must be taken into consideration, and is only a guide. Since each of the films has a wide range of uses, it has an advantage that it can be obtained very inexpensively and stably.

  The thickness of the gas permeable material used in the present invention is preferably about 5 to 500 μm. Even if the same amount of chlorine-based disinfectant is used, the sustained release amount of chlorine can be increased by reducing the thickness. If it is too thick, it takes time to generate hypochlorous acid water in the initial stage. For example, when using with a bag form, 10-100 micrometers is preferable.

  In the conventional porous film, there are innumerable pores having a pore diameter of about 0.01 to 3 μm (for example, Gore-Tex (registered trademark) manufactured by Japan Gore-Tex Co., Ltd., Espoir (Mitsui Chemicals Co., Ltd.) Registered trademark) and the like. Such a porous film can be used because it allows water vapor to pass therethrough but does not pass water, and is suitable when high chlorine release is required.

  In addition to the non-porous film, a special non-woven fabric can also be used as the gas permeable impermeable material. An example of such a nonwoven fabric is DuPont Tyvek. Tyvek is a heat-bonded sheet in which ultrafine polyethylene fibers are closely intertwined, and has gas permeability and sufficient water impermeability. Tyvek has a higher gas permeability than a non-porous film such as polyethylene, and is therefore advantageously used when high chlorine release is required. For example, when it is necessary to adjust a large amount of hypochlorous acid water, such a material may be used.

Since the release rate of the chlorine gas varies depending on the area of the gas permeable material of the tool containing the chlorine agent, it is desirable to determine the area according to the purpose of use. The suitable area of the gas permeable material varies depending on the gas permeability and thickness of the material. As the gas permeability is higher and the thickness is thinner, the area may be smaller. For example, when a 40 μm thick LLDPE film is used, the ratio (cm ² / g) of the film area (cm ² ) to the chlorine agent (g) in the chlorine source container is preferably 0.5 to 30. When using a trigger spray container or a finger spray container having a capacity of 100 to 500 ml, the ratio is preferably 1 to 8, particularly preferably 1.5 to 5. When the film area is too large, it may be difficult to adjust the concentration of the hypochlorous acid water to be generated. Moreover, when preparing hypochlorous acid water in large quantities, it is preferable to use the said ratio by 5-30. This is because the chlorine concentration tends to increase.

  Examples of the chlorine-based disinfectant used in the present invention include chlorinated isocyanuric acid, bleached powder, advanced bleached powder, chloramine T, chloramine B, hypochlorite, chlorite, and chlorate. Among these, chlorinated isocyanuric acid is preferable in terms of ease of handling and continuous sustained release of chlorine.

  Chlorinated isocyanuric acid is a solid compound that hydrolyzes when released in contact with water to release active chlorine having a strong oxidizing ability and is excellent in stability of active chlorine in water. It is widely used as an active ingredient such as an agent, disinfectant and deodorant. Examples of the chlorinated isocyanuric acid include trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, dihydrate of sodium dichloroisocyanurate and potassium dichloroisocyanurate. Of these, trichloroisocyanuric acid and / or dichloroisocyanuric acid are preferable.

  In addition, bleaching powder and advanced bleaching powder are not enough for sustained release even when used alone, so one or more selected from silica gel, calcium chloride, lithium chloride, ammonium chloride, calcium sulfate, 0.01 times to bleaching powder, etc. It is necessary to coexist at a weight ratio of 100 times.

  The chlorine-based disinfectant is housed in a container made of a material that is at least partially gas permeable and does not allow water to pass through, but in that case, it is preferably a solid. . This is because it is easy to handle and easy to measure. As the solid material, powder, granules, tablets and the like can be appropriately selected. Powdered and granular forms are preferred because the initial chlorine generation amount can be made relatively high. Granules are optimal when handling is considered.

  The container of the neutralizer container used in combination with the chlorine source container is at least partially made of a material having water permeability. Examples of such materials include hydrophilic fibers such as cellulose, rayon, and cotton; hydrophobic fibers such as polypropylene, polyethylene, polyester, and polyamide; and nonwoven fabrics and nets processed from natural fibers such as hemp and wool. .

Any nonwoven fabric may be used as long as it has high water permeability and does not leak the poorly water-soluble inorganic calcium salt. For example, as the characteristics, (1) basis weight: about 10 to 1,000 g / m ² , preferably about ²⁰ to 900 g / m ² (2) air permeability: about 0.1 to 200 cm ³ / cm ² · s, Preferably about 0.2 to 150 cm ³ / cm ² · s (3) Average fiber diameter: 0.5 to 30 μm, preferably about 1 to 10 μm (4) Fabric thickness: about 30 to 5,000 μm, preferably Is about 100 to 2,000 μm. The non-woven fabric is obtained by a conventional method using fibers (a method in which fibers are made into a web and bonded by thermocompression bonding or an adhesive, a needle punch method, a method in which short fibers are made by a paper machine and then thermally bonded). Can be manufactured. As the fibers, composite fibers of polyethylene, polypropylene, and polyester are also preferably used. In addition, when using a limestone with a large particle size by a single item, a nonwoven fabric is unnecessary.

  In the container having the material, a poorly water-soluble inorganic calcium salt is contained, and by immersing this neutralizing agent container in water, the inorganic calcium salt is eluted while being affected by the liquidity of water. is there. Examples of the poorly water-soluble inorganic calcium salt include calcium carbonate, calcium phosphate, calcium sulfate, calcium fluoride, calcium silicate, and hydroxyapatite. Of these, calcium carbonate and calcium phosphate are particularly preferred. This is because the pH of the water in the external environment in which the chlorine released from the chlorine source container is dissolved tends to be acidic, so that the effect of dissolving appropriately and stabilizing from weakly acidic to near neutral is high. Examples of suitable calcium carbonate include pulverized limestone, shells, and corals, and examples of calcium phosphate include hydroxyapatite, tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, and the like. it can.

  The present invention is a sustained-release chlorine device that is used in an aqueous environment by combining the chlorine source container and the neutralizer container, and is characterized in that both are used as a set. The amount of the poorly water-soluble inorganic calcium salt is sufficient if it is sufficient to adjust the pH of the hypochlorous acid produced. The ratio at the time of use of the chlorine agent in the chlorine source container and the poorly water-soluble inorganic calcium salt in the neutralizer container is in the range of 1: 0.02 to 1: 2 by weight, 1: 0.2. A range of ˜1: 0.5 is more preferred. If the amount of the poorly water-soluble inorganic calcium salt is too small, it may be consumed during use and the service life may be shortened.

  On the other hand, there is no particular problem even if the ratio of the poorly water-soluble inorganic calcium salt is larger than the above range. This is because it dissolves in the surrounding water environment according to the chlorine generated from the chlorine source container, so that even if the poorly water-soluble inorganic calcium salt is present excessively, it does not substantially act. Further, if a chlorine source container is additionally used, the remaining poorly water-soluble inorganic calcium salt gradually dissolves. Therefore, the above weight ratio is presented only as a guideline for the initial ratio when a set is sold.

  Next, a method for producing the weakly acidic hypochlorous acid water of the present invention will be briefly described. Put water (tap water, distilled water, membrane filtered water, ion exchange water, etc.) used at home in a storage container with an appropriate capacity, and the chlorine release device of the present invention (chlorine source container + neutralizer storage) In the water, a neutralizer container is disposed, and a chlorine source container is disposed in the water or at a position closest to the water surface. If left as it is for several hours at room temperature, the pH is inclined to acidity due to the diffusion of chlorine into water, the water is neutralized by elution of the poorly water-soluble inorganic calcium salt, and weakly acidic hypochlorous acid water is easy Can be manufactured.

  The ratio (volume: weight) of the volume (L) of water at this time and the weight (g) of the chlorine-based disinfectant in the chlorine source container varies depending on the type of hypochlorous acid water or gas permeable material to be manufactured. However, for example, when it is desired to obtain a product having a chlorine concentration of around 40 ppm using an LLDPE film, the range is 100: 1 to 100: 10, preferably 100: 2 to 100: 6. This ratio is the case where granules are used as a chlorine-based disinfectant, and in the case of tablets, a large amount is required because the surface area is small. On the other hand, in the case of powder, a small amount is sufficient. If the amount of water is relatively larger than the above range, the chlorine concentration tends to decrease, and if the amount of the chlorine-based disinfectant exceeds the above range, the chlorine concentration tends to increase too much.

  The production method of the present invention does not prepare hypochlorous acid water when necessary, but prepares hypochlorous acid water in advance so that it can be used anytime, and maintains the chlorine concentration for a long time. . However, in an emergency, it is also possible to adopt a method in which only the chlorine source container is brought into contact with water first, or the chlorine concentration is increased early by increasing the water temperature, and then the neutralizer container is put into water. it can.

  As a material of the storage container used in the manufacturing method, resins such as glass, high density polyethylene, polypropylene, vinyl chloride, vinylidene chloride, nylon, polyethylene terephthalate, polyacrylonitrile, and the like can be used. Of these, polyethylene and polypropylene are preferred in the sense that they have durability against hypochlorous acid water.

  Moreover, a simple deodorizing and sterilizing apparatus can be obtained using the chlorine sustained release device of the present invention as a constituent element. The apparatus of the present invention preferably employs a conventionally known spray container or sprayer in consideration of convenience during use. Specifically, it is a finger spray container 1 as shown in FIG. 1 and contains water 5 together with a sustained release tool (a tool 2 containing a chlorine-based disinfectant and a tool 3 containing a poorly water-soluble inorganic calcium salt). A container body 8 to be operated, a nozzle 6 standing up and down in an upward biased state from the container body opening, and a pump mechanism (not shown in the figure) that operates in conjunction with the vertical movement of the nozzle. By pushing down the push-down portion 7 extended radially outward toward the base end side of the nozzle with a finger, the internal solution containing chlorine in the container is ejected from the tip of the nozzle by the action of the pump mechanism. Is. Such a container can make the whole size compact, and is convenient for carrying.

  A pistol-type trigger spray container 11 as shown in FIG. 2 can also be used. As a specific configuration, a chlorine sustained-release tool (a tool 12 containing a chlorine-based disinfectant and a tool 13 containing a poorly water-soluble inorganic calcium salt), a container body 18 containing water 15 together with the chlorine sustained-release tool, A mounting cylinder 14 fitted to the neck of the container body, a vertical cylinder 16 standing up from the mounting cylinder, an injection cylinder 17 projecting forward from the upper end of the vertical cylinder, and an intermediate portion of the vertical cylinder A cylinder 19 that protrudes forward from the cylinder, a plunger 20 that is slidably fitted in the cylinder and is urged forward, and an upper rear surface thereof engages with the front end of the plunger, and the injection cylinder A trigger 24 that is swingably attached to the front portion of the nozzle, a nozzle fitting tube 25 that is attached to the front end of the injection tube, and a nozzle hole are formed so as to be rotatable on the outer surface of the nozzle fitting tube. A mist-like jet is installed at a predetermined position of the nozzle. However, in another predetermined position, the straight liquid flow is composed of the switchable nozzle head 26, and by pulling the trigger backward, the internal solution containing chlorine stored in the container body is sucked up, and the nozzle hole Squirting through. The state of the liquid ejected by the rotation of the nozzle head can be changed, so when you want to sterilize intensively, you can use a straight liquid flow, and when you want to sterilize a wide range, you can spray mist-like liquid, depending on the scene it can,

  The chlorine sustained-release tool of the present invention is not limited to the finger spray container or the trigger spray container, but is a chlorine sustained-release tool (a tool 32 containing a chlorine-based disinfectant and a poorly water-soluble inorganic as shown in FIG. 3). A tool 33 for storing calcium salt, a pump container 31 for storing water 35 together with the chlorine sustained-release tool, a chlorine sustained-release tool (tool 42 for storing a chlorine-based disinfectant, and poorly water-soluble inorganic calcium as shown in FIG. 4) By storing the solution together with water using a commercially available container in which the user can refill the inner solution, such as a tool 43) that contains salt, and a squeeze bottle 41 that contains water 45 together with the chlorine release tool. Weakly acidic hypochlorous acid water can be prepared and used for deodorization, sterilization and other purposes.

  Moreover, the chlorine sustained release device of the present invention can be applied to a shower faucet or the like of a water supply device that needs to prevent contamination by bacteria. Or it is a shower head which has an adapter which can be attached to a faucet, and a channel connected to a shower nozzle, and the chlorine sustained release device is located in the channel, and microbial contamination in the channel is prevented. It is also possible to commercialize the product as a set of shower heads.

  For example, a tool 52 for removing a shower cap 55 and containing a chlorine-based disinfectant and a tool 53 for containing a poorly water-soluble inorganic calcium salt are inserted into the shower faucet 51 of FIG. The tool 52 for storing the chlorine-based disinfectant and the tool 53 for storing the poorly water-soluble inorganic calcium salt may be bonded to each other by heat fusion or the like. When the shower cap 55 is tightened and water is passed through, the tools 52 and 53 are lifted, so that the way out of the shower is not affected. When passing water, even if chlorine is released from the chlorine release device, the amount of chlorine relative to the amount of water is negligible.

  When the electromagnetic valve 57 is closed to stop water flow, the water 58 is kept filled from the valve into the faucet. Here, chlorine is released from the chlorine release tool, and the faucet is filled with hypochlorous acid water. Hypochlorous acid water is automatically adjusted to maintain weak acidity by a tool containing a poorly water-soluble inorganic calcium salt. When the water flow is stopped, if microorganisms in the air adhere to the outside of the shower cap 55, the microorganisms may enter the inside through the shower hole 56, and the water inside the faucet may be contaminated. In particular, there is a high risk of contamination. When the sustained release device of the present invention is inserted, the invaded microorganisms are killed by the generated hypochlorous acid water, so that the shower head is always kept in a disinfected state. Next, when water flow is started, hypochlorous acid water flows first, but the pH of the hypochlorous acid water is kept weakly acidic, so there is no concern about metal corrosion.

  The Example which uses the chlorine sustained release tool of this invention below is shown.

Example 1
Example 1
6 g of trichloroisocyanuric acid granules (manufactured by Nankai Chemical Industry Co., Ltd .; STARTRICLON PG) were put into a polyethylene film bag having a size of 25 × 55 mm and a thickness of 40 μm and heat-sealed (chlorine source container). Moreover, 1 g of limestone fine particles (Omi Mining Co., Ltd .; Tankar LG12, particle size 2 to 5 mm) was put into a bag for tea bags (tea pack M manufactured by Subaru Corporation) (neutralizing agent container). Both were placed in a polyethylene bottle with a capacity of 200 mL, sealed with 200 mL of tap water, and placed in a room at 20 to 30 ° C. Table 1 shows the measurement results of the chlorine concentration and pH of the generated hypochlorous acid water.

  As can be seen from the results in Table 1, the sustained-release chlorine device of the present invention has the effect of maintaining the chlorine concentration in the external environment moderately and maintaining the pH in the vicinity of weak acidity.

(Example 2)
7 g of Startryklon PG was put in a polyethylene film bag having a size of 60 × 50 mm and a thickness of 40 μm and heat-sealed (chlorine source container). This bag was placed in a 200 mL polyethylene bottle. Further, Tankar LG12 was put in a bag for a tea bag (neutralizing agent container) and stored in the bottle. 200 mL of tap water was put into the bottle and sealed, and placed in a room at 15 to 22 ° C. Seven days later, the effective chlorine concentration and pH of the liquid in the bottle were measured. After the measurement, the entire liquid was discarded and 200 mL of tap water was newly added. Table 2 shows the results when the amount of Tankar LG12 in the neutralizing agent container is set to each initial value.

  From the results of Table 2, it can be seen that in the system that does not contain Tankar LG12 (sample No. 1), the pH of water is biased to acidity, and it is necessary to pay attention when using it.

(Test Example 1)
Corrosiveness to metals and the like can be considered as a matter to be noted during use. Therefore, the following test was performed and verified.
Test A: Five Zem clips were placed in a 20 mL sample bottle, and the third solution of Example 2 was placed in this, sealed and placed at room temperature for 7 days, and the rust of the clips was examined visually.
Test B: The tissue paper soaked in the third liquid of Example 2 was placed in a petri dish, and five gem clips were placed thereon and placed for 3 days, and then rust was examined visually.

  The results of each test are summarized in Table 3. As is clear from the results shown in Table 3, the hypochlorous acid water obtained by the present invention can be used more safely for metal products and the like.

(Example 3)
In the same manner as in Example 1, a polyethylene film bag containing 7 g of Startryklon PG was prepared. Further, 7 g of powdered calcium carbonate (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was passed through a non-woven bag with water, and both were put together with 200 mL of tap water in a bottle having the same capacity as in Example 1. The chlorine concentration and pH of the solution after 7 days were measured in the same manner as in Example 1, and the results are shown in Table 4. Although it is an expected result, it can be seen from Table 4 that the same effect as in the case of Tankar LG12 can be obtained.

Example 4
10 g of Startryklon PG was put in a polyethylene film bag of size 30 × 70 mm and thickness 40 μm. Moreover, the bag which put 3g Tankar LG12 similarly to Example 1 was created. Both were put together with 500 mL of tap water in a 500 mL trigger spray container (manufactured by Tosei Container Co., Ltd .; NWN-500) to create a simple deodorization / sterilization apparatus. About 30 mL of the solution prepared in this apparatus was used every day, and tap water was replenished every 5 days as the liquid decreased. Table 5 shows the results of measuring the chlorine concentration and pH of the solution every month.

  As can be seen from the results in Table 5, hypochlorous acid water having a stable chlorine concentration and pH can be obtained by the simple deodorizing and sterilizing apparatus of the present invention.

(Example 5)
6 g of Startryklon PG was put in a bag of polyethylene flume having a size of 30 × 40 mm and a thickness of 60 μm. Moreover, the bag which put 3.3g Tankar LG12 similarly to Example 1 was created. Both were put together with 200 mL of tap water into a 200 mL trigger spray container (made by Shinei Kasei Co., Ltd .; Z305) to create a simple deodorization / sterilization apparatus. About 15 mL of the solution prepared in this apparatus was used every day, and tap water was replenished every 5 days as the liquid decreased. Table 6 shows the results of measuring the chlorine concentration and pH of the solution every month. As can be seen from the results in Table 6, a hypochlorous acid water having a stable chlorine concentration and pH can be obtained by manufacturing a simple deodorizing and sterilizing apparatus incorporating the chlorine sustained release device of the present invention according to the capacity. It is done.

(Example 6)
20 g of Startryklon PG was put into a polyethylene film bag having a size of 100 × 130 mm and a thickness of 30 μm and heat-sealed. Moreover, 5 g of Tankar LG12 was put in a bag for a tea bag, and both were put in a 2 L polypropylene bottle. 2 L of tap water was put into the bottle and sealed, and placed in a room at 20 to 25 ° C. Seven days later, the chlorine concentration in the liquid in the bottle was 41 ppm, and the pH was 5.9. 1000 mL of the obtained hypochlorous acid water was subdivided into five trigger type spray containers similar to Example 5 and used for deodorization and sterilization. The 2 L bottle was supplemented with 1000 mL of tap water. When further left standing at room temperature for 3 days, hypochlorous acid water having a chlorine concentration of 40 ppm and a pH of 5.9 was obtained. In this system, even if it is diluted 2 times, it can be seen that it returns to the original chlorine concentration after 3 days.

(Example 7)
In order to measure the falling bacteria, trypsoy agar plate medium (diameter 83 mm) was opened for 30 minutes on the desk (height: 700 mm) in the office. Then, after spraying the whole office using a finger spray as shown in FIG. 1 as a chlorine sustained release tool, the falling bacteria measurement was similarly performed. The finger spray used was heat sealed with 6 g of trichloroisocyanuric acid granules (manufactured by Nankai Chemical Industry Co., Ltd .: STARTRICLON PG) in a polyethylene film bag of size 25 mm × thickness 40 μm (chlorine source container). In addition, 1 g of limestone fine particles (Omi Mining Co., Ltd .: Tankar LG12, particle size 2-5 mm) (neutralizing agent container) is put in a bag for tea bags, and 200 mL of tap water is added at room temperature. What was stored for 4 days was used.

  In addition, after culture | cultivating the culture medium used for falling bacteria measurement in a 30 degreeC thermostat for 48 hours, the number of colonies was counted. As a result, as shown in Table 7, it was confirmed that there was a sterilization effect. Separately, as a result of carrying out the falling bacteria measurement before and after using the chlorine sustained release device in the washroom, the sterilization effect was recognized at any place.

(Example 8)
Three pieces of heat-sealed 5 g Starricron PG in a polyethylene film bag of size 50 × 50 mm and thickness of 40 μm were prepared and stored in three vials each having a capacity of 100 mL. One of the vials (Sample No. 6) contains 2 g of Tankar LG12 in a tea bag bag, and the other (Sample No. 7) contains 2 g of powdered triphosphate. Calcium (manufactured by Nacalai Tesque Co., Ltd.) in tea bags was stored. The remaining one (Sample No. 8) did not contain a neutralizing agent container. Table 8 shows the chlorine concentration and pH of the internal solution after putting 100 mL of tap water into each vial and sealing it and leaving it at room temperature of 25-30 ° C. for 4 days. As shown in the table, it is understood that tricalcium phosphate has the same effect as limestone.

Example 9
A polyethylene bottle having a capacity of 1 L was filled with 5 g of Tankar LG12 in a bag for a tea bag, and 500 mL of tap water was added. Put 20g of Starricron in a polyethylene film bag of size 60x80mm and thickness 30μm (chlorine source container), hang it in the space above the water in the bottle with a string, tighten the cap and seal it It was. After being placed in a room at 23 to 28 ° C. for 2 weeks, the pH and chlorine concentration of the content solution were measured, and the pH was 5.8 and the chlorine concentration was 41 ppm. From this, it was found that the chlorine source container is not necessarily stored in water, but may be configured such that the released chlorine gas is in contact with water.

(Example 10)
10g of Starricron PG was placed in a 60x80mm Tyvek 1073B (thickness 0.19mm, manufactured by DuPont, imported and sold by Asahi DuPont Flashspan Products) and heat-sealed (chlorine source container) . This bag was stored in a 10-liter plastic tank. Further, 10 g of Tancal LG12 was put in a bag for a tea bag (neutralizing agent container) and stored in the tank. The tank was sealed with 10 liters of tap water and placed in a room at 10 to 18 ° C. After 1 month, 1.5 months, and 3 months, the effective chlorine concentration and pH of the liquid in the tank were measured. The results are shown in Table 9.

  As shown in Table 9, it can be seen that a liquid agent having an appropriate effective chlorine concentration can be obtained with the chlorine sustained release device of the present invention even in a large capacity tank.

(Example 11)
Thickness 40μ, size 25 ×, containing 5 g of trichloroisocyanuric acid granules (Starlitron PG manufactured by Nankai Chemical Industry Co., Ltd.) in a shower faucet made of ABS resin equipped with a shower cap that can be attached and detached with the same screw as in FIG. A chlorine release tool consisting of a 50 mm polyethylene film bag and a tea bag bag containing 0.3 g of fine limestone (Tankar LG12, particle size 2-5 mm manufactured by Omi Mining Co., Ltd.) Inserted while wearing. After passing water at 40 ° C., the valve was closed, and after 5 hours, the shower cap was opened and water was collected. The amount of water was 50 ml. When the chlorine concentration and pH of this water were measured, the chlorine concentration was 6.6 ppm and the pH was 6.1. Similarly, the chlorine concentration and pH were measured after 40 hours had passed after the water stoppage, and the chlorine concentration was 22 ppm and the pH was 5.3.

  As a comparative example, measurement was carried out in the same manner as above except that limestone fine particles were not used. After 5 hours, the chlorine concentration was 6.6 ppm and pH 5.3, and after 40 hours, the chlorine concentration was 21 ppm and pH 3.8. there were. As described above, when only a tool that releases chlorine is used, the pH becomes considerably acidic, which may cause skin irritation in the initial stage of use and corrosion of metal parts.

  As described above, the sustained release tool of the present invention is easy to manufacture with a simple combination of a chlorine source container and a neutralizer container. Further, chlorine release is persistent over a long period of time, and an equilibrium state is formed between the inside of the chlorine release device and the surrounding environment, so that the surrounding environment can be maintained with a constant concentration of chlorine. Furthermore, since the pH drop due to the released chlorine is alleviated by the neutralizing agent container, highly safe drinking water can be obtained.

  In addition, since the simple deodorizing and sterilizing apparatus of the present invention can be configured simply by combining a refill bottle with a commercially available liquid spout and a chlorine sustained release device, in addition to daily use, in preparation for an emergency It can also be placed. Furthermore, it is possible to maintain sterility by using the chlorine release device of the present invention in a location where water is accumulated for a relatively long time in an open system such as a shower faucet. It becomes possible.

1 Finger spray container 2, 12, 32, 42, 52 Tool 3, 13, 33, 43, 53 for storing a chlorine-based disinfectant 6 Tool for storing a poorly water-soluble inorganic calcium salt 6 Nozzle 8, 18 Container body 11 Trigger spray Container 26 Nozzle head 31 Pump container 41 Squeeze type bottle 51 Shower faucet

Claims (7)

A tool for containing a chlorine-based disinfectant in a container composed of a material that is at least partially gas permeable and is entirely impermeable to water;
In combination with a tool configured to contain a sparingly water-soluble inorganic calcium salt in a container composed of a material having water permeability at least partially,
The weight ratio of the chlorine-based disinfectant and the poorly water-soluble inorganic calcium salt is in the range of 1: 0.2 to 1: 2.
The two tools are used as a set in a water environment. Wherein a chlorine-based germicide is Ri chlorinated isocyanuric acid der,
When the ratio of the volume of water (L) and the weight (g) of chlorinated isocyanuric acid is used in the range of 100: 1 to 100: 10,
Chlorine concentration in the water, chlorine sustained release ingredients according to claim 1 you, characterized in that it is maintained in the range of 30～92Ppm. The chlorine sustained-release device according to claim 2, wherein the chlorinated isocyanuric acid is trichloroisocyanuric acid and / or dichloroisocyanuric acid. The poorly water-soluble inorganic calcium salts, Ri least 1 Tanedea calcium carbonate, calcium phosphate, calcium fluoride, calcium silicate, hydroxyapatite, selected from,
Claim pH of weakly acidic hypochlorous acid water containing chlorine which is sustained by co chlorine sustained release ingredients and water, characterized in that it is maintained in the range of from 5.3 to 6.1 1 The chlorine sustained release device according to any one of 1 to 3. A weakly acidic second order characterized in that, in a storage container, the chlorine sustained-release device according to any one of claims 1 to 4 and water coexist and the sustained-released chlorine is maintained at a constant concentration for a long time. A method for producing chlorous acid water. The sustained-release chlorine device according to any one of claims 1 to 4,
An adapter that can be attached to the faucet;
A shower head having a flow path communicating with the shower nozzle;
A showerhead sterilization apparatus in which the chlorine sustained release device is placed in the flow path to prevent microbial contamination in the flow path. The sustained-release chlorine device according to any one of claims 1 to 4,
A container body for containing water together with the chlorine sustained release device;
A mounting cylinder fitted to the mouth and neck of the container body;
A vertical cylinder erected from the mounting cylinder;
An injection cylinder projecting forward from the upper end of the vertical cylinder;
A cylinder protruding forward from an intermediate portion of the vertical cylinder;
A plunger slidably fitted in the cylinder and biased forward;
A trigger whose upper rear surface engages with the front end portion of the plunger and is swingably attached to the front portion of the injection cylinder;
A nozzle fitting tube attached to the front end of the injection tube;
The nozzle head is formed with a nozzle hole, and is rotatably attached to the outer surface of the nozzle fitting cylinder. The nozzle head has a mist-like spray at a predetermined position of the nozzle and a straight liquid flow at another predetermined position. Become
The chlorine concentration of the internal solution containing chlorine stored in the container body is maintained at a constant concentration over the entire period of use.
A trigger-type deodorizing and sterilizing device in which an internal solution containing chlorine stored in a container body is sucked up by pulling the trigger backward and ejected through the nozzle hole.

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