JP7692860B2 - Toilet bowl cleaner - Google Patents

Description

The present invention relates to a toilet bowl cleaner utilizing chlorine dioxide. More specifically, the present invention relates to
The present invention relates to a toilet cleaner that can be suitably used in an embodiment in which it is placed on the bowl side of a toilet lid.

In homes and commercial facilities, keeping toilets in a hygienic state is important not only for maintaining the health of residents and users, but also for living comfortably and with a good mood. Cleaning is necessary to keep toilets in a hygienic state, but even if the toilet is cleaned regularly, feces will inevitably adhere to the toilet and blackening will occur around the water. For this reason, in addition to regular cleaning, scrubbing is also required when dirt occurs, which is time-consuming. To reduce this time-consuming process, toilet cleaners have traditionally been placed in the hand washing area, water tank, rim, bowl, etc. of the toilet, and the toilet cleaner is diluted in flush water and then run into the bowl to prevent or remove dirt and blackening that adheres to the bowl.

However, conventional toilet cleaners that do not require scrubbing are insufficient in removing stains such as feces and blackheads (stain removal effect) and in preventing the adhesion of such stains (stain prevention effect), so they do not have a sufficiently high cleaning action, and further improvements are required. Furthermore, since all of these toilet cleaners are used by diluting them with flush water, the cleaning action is limited to the part of the bowl through which the flush water passes, and improvements are required.

In light of this background of conventional technology, there is a need for the development of a toilet cleaner that has excellent cleaning action against feces and black stains, and can exert an anti-fouling effect without scrubbing, even in areas of the toilet bowl where flush water does not pass.

On the other hand, chlorine dioxide has antibacterial, antifungal, deodorizing, and virus-removing properties, and is known to be usable for cleaning indoor spaces (e.g., Patent Documents 1 and 2), but it is not known to have stain-removing or antifouling properties. Toilet cleaners are required to have stain-removing and antifouling properties, but these properties are not known for chlorine dioxide, and no toilet cleaners containing chlorine dioxide have been reported.

JP 2007-217239 A Japanese Patent Application Publication No. 11-278808

The object of the present invention is to provide a toilet cleaner that has high stain removal and anti-fouling effects and provides an excellent cleaning effect. Another object of the present invention is to provide a toilet cleaner that, in addition to having high stain removal and anti-fouling effects and excellent cleaning effects, can easily clean the bowl of a toilet without diluting it with flush water, and can provide an excellent anti-fouling effect even in the bowl of a toilet where flush water does not pass.

The inventors conducted extensive research to solve the above problems and found that chlorine dioxide has excellent stain-removing and stain-preventing properties and can be used as a cleaning component in toilet cleaners. Furthermore, the inventors found that when a composition that releases chlorine dioxide is placed on the bowl side of a toilet lid and the lid is closed, the gaseous chlorine dioxide released from the composition spreads throughout the entire surface of the bowl, the rim (including the back side), and the inside of the rim (water-passing area), providing an anti-staining effect to these areas. The present invention was completed based on these findings and through further research.

That is, the present invention provides the following aspects.
Item 1. A toilet bowl cleaner comprising a composition that releases chlorine dioxide.
Item 2. Used to flush a toilet bowl having an openable toilet lid,
Item 2. The toilet cleaner according to item 1, which is placed on the bowl side of the toilet lid of the toilet, on the surface of the bowl of the toilet, or on the rim part at the upper end of the bowl of the toilet.
Item 3. The toilet cleaner according to Item 2, which is used by being placed on the bowl side of the toilet lid of the toilet.
Item 4. The toilet bowl cleaner according to any one of Items 1 to 3, wherein the composition contains a chlorine dioxide generating source.
Item 5. The toilet bowl cleaner according to Item 4, wherein the source of chlorine dioxide generation is a hydrochlorite and an acid.
Item 6. The toilet bowl cleaner according to any one of Items 1 to 5, which is used as a toilet bowl stain remover.
Item 7. The toilet bowl cleaner according to any one of Items 1 to 5, which is used as an antifouling agent for a toilet bowl.
Item 8. A method for cleaning a toilet, comprising cleaning a toilet using the toilet cleaner according to any one of items 1 to 7.

The toilet cleaner of the present invention has the effect of removing stains such as feces, blackening, and the substances that cause these (stain removal effect), as well as the effect of preventing the adhesion of these stains (stain prevention effect), and can exert an excellent cleaning action.

In addition, in a preferred embodiment of the toilet cleaner of the present invention, gaseous chlorine dioxide can be released and spread throughout the entire surface of the bowl of the toilet, the rim (including the back surface), and even the inside of the rim (water-passing area), so that an excellent anti-fouling effect can be imparted even to parts of the bowl that do not come into contact with flush water or that are difficult to contact with. Furthermore, because chlorine dioxide is heavier than air and highly soluble in water, it can impart an excellent anti-fouling effect to parts that are imparted with anti-fouling effects by conventional toilet cleaners, such as the puddle parts of the bowl.

FIG. 1 is a schematic diagram showing an embodiment in which the toilet cleaner of the present invention is applied to the bowl side of the toilet lid of a toilet (when the toilet lid is open). FIG. 1 is a schematic diagram showing an embodiment in which the toilet cleaner of the present invention is applied to the bowl side of a toilet lid (when the toilet lid is closed).

The toilet cleaner of the present invention is characterized by comprising a composition that releases chlorine dioxide (hereinafter referred to as a "chlorine dioxide-releasing composition"). The toilet cleaner of the present invention is described in detail below.

Chlorine Dioxide Releasing Compositions The chlorine dioxide releasing compositions used in the present invention are designed to release chlorine dioxide in a gaseous or dissolved state.

The chlorine dioxide-releasing composition used in the present invention is not particularly limited in composition as long as it can release chlorine dioxide, and may contain chlorine dioxide itself (hereinafter referred to as the "composition of the first embodiment"), or may contain a chlorine dioxide generating source and generate chlorine dioxide continuously (hereinafter referred to as the "composition of the second embodiment"). The composition of the second embodiment is suitable as the chlorine dioxide-releasing composition used in the present invention because it has excellent sustained chlorine dioxide releasing properties and can be used for a long period of time. The composition of the first embodiment and the composition of the second embodiment will be described below.

[Composition of the first embodiment]
The composition of the first embodiment is specifically an aqueous solution containing chlorine dioxide. The aqueous solution containing chlorine dioxide can be obtained, for example, by bubbling chlorine dioxide gas into water to prepare an aqueous solution containing chlorine dioxide.

The content of chlorine dioxide in the composition of the first embodiment may be appropriately set to an effective amount that can exert a cleaning action (stain removal effect and stain prevention effect) depending on the mode of chlorine dioxide release, the installation site of the toilet cleaner of the present invention, etc., and may be, for example, 10 ppm to 10,000 ppm, preferably 50 to 6,000 ppm.

As the composition of the first embodiment, the aqueous solution containing chlorine dioxide may be used as it is in liquid form, or may be formed into a gel using a gelling agent. The type of gelling agent used to form the gel is as described below in the section "Composition of the second embodiment."

[Composition of the second embodiment]
The composition of the second embodiment may be any composition that contains a chlorine dioxide generating source and is designed to generate chlorine dioxide, and its composition, production method, etc. are publicly known in Patent Documents 1 and 2, etc.

Specific examples of sources of chlorine dioxide used in the composition of the second embodiment include chlorite and acid. Chlorite can react with acid in the presence of water to generate chlorine dioxide.

The type of chlorite used as one component of the chlorine dioxide generation source is not particularly limited, but examples include alkali metal salts of chloric acid such as lithium chlorite, sodium chlorite, and potassium chlorite; and alkaline earth metal salts of chloric acid such as calcium chlorite, magnesium chlorite, and barium chlorite. These chlorites may be used alone or in combination of two or more.

The content of chlorite in the composition of the second embodiment is determined by the shape of the composition of the second embodiment,
This may be appropriately set depending on the manner in which chlorine dioxide is released, the installation location, etc., but for example, 0.
The content is 1 to 30% by weight, preferably 1 to 10% by weight.

The type of acid used as one of the components of the chlorine dioxide generation source is not particularly limited, as long as it is an acidic acid when dissolved in water and can generate chlorine dioxide from chlorite in the presence of water. Examples of the acid include phosphoric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite, potassium pyrosulfite, sodium acid hexametaphosphate, potassium acid hexametaphosphate, sodium acid pyrophosphate, potassium acid pyrophosphate, and sulfur. Examples of the acids include solid acids such as sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, glutamic acid, aspartic acid, glycolic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, salicylic acid, gallic acid, tropic acid, ascorbic acid, and gluconic acid; and liquid acids such as hydrochloric acid and sulfuric acid. These acids may be used alone or in combination of two or more.

The content of the acid in the composition of the second embodiment may be set appropriately depending on the shape of the composition of the second embodiment, the manner in which chlorine dioxide is released, the installation site, etc., but it is desirable that the content be equal to or greater than the minimum amount required to react with the total amount of chlorite, specifically 0.01 to 15% by weight, preferably 1 to 10% by weight.

The composition of the second embodiment does not necessarily need to contain water, because chlorite and acid can be reacted to generate chlorine dioxide by absorbing water vapor in the air or by using flash water in the embodiment in which the composition is diluted with flash water and used. However, from the viewpoint of efficiently generating chlorine dioxide, it is desirable for the composition of the second embodiment to contain water.

When water is contained in the composition of the second embodiment, the content of water may be appropriately set depending on the shape of the composition of the second embodiment, and may be, for example, 30 to 99.69% by weight, preferably 70 to 97% by weight.

When the composition of the second embodiment contains water, the composition of the second embodiment may be in the form of an aqueous solution, or the composition of the second embodiment may be in the form of a gel and water may be retained in the gel, or a water-retaining base that retains water may be included.

When forming a gel and retaining moisture in the gel, the type of gelling agent used for gelation is not particularly limited, but examples include brown algae-, green algae- or red algae-derived ingredients such as alginic acid, agar, carrageenan, and fucoidan; polysaccharides such as byakki extract, pectin, locust bean gum, and aloe polysaccharide; gums such as xanthan gum, tragacanth gum, and guar gum; cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose; synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, and acrylic acid/methacrylic acid copolymer; polyglutamic acid and its derivatives; sugar compounds mainly composed of glucosyltrehalose and hydrolyzed hydrogenated starch; and various water-absorbing resins such as starch-based, cellulose-based, and synthetic polymer-based.

When a gelling agent is contained in the composition of the second embodiment, the content is not particularly limited, but may be, for example, 0.2 to 25% by weight, preferably 1 to 10% by weight.

When a moisture-retaining base that retains moisture is included, the type of moisture-retaining base to be used is not particularly limited, as long as it has the property of being able to retain water, but examples include porous substances such as diatomaceous earth, zeolite, kaolin, perlite, bentonite, and charcoal. These moisture-retaining bases may be used alone or in combination of two or more.

When the composition of the second embodiment contains a moisture-retaining base, the content is not particularly limited, but may be, for example, 0.2 to 25% by weight, preferably 1 to 10% by weight.

When the composition of the second embodiment contains a moisture-retaining base that retains moisture, it may further contain a deliquescent solid agent as necessary. When moisture is retained in the moisture-retaining base, the water content in the composition of the second embodiment becomes relatively low, and the rate of chlorine dioxide generation may be slowed down, but by further containing a deliquescent solid agent, it becomes possible to promote the generation of chlorine dioxide. There are no particular limitations on the type of deliquescent solid agent, and examples include aluminum chloride, calcium chloride, magnesium chloride, potassium monohydrogen phosphate, and glycerin. These deliquescent solid agents may be used alone or in combination of two or more.

When the composition of the second embodiment contains a deliquescent solid agent, the content is not particularly limited, but may be, for example, 0.1 to 30% by weight, preferably 1 to 20% by weight.

Furthermore, when the composition of the second embodiment contains water, the water in the composition of the second embodiment may contain chlorine dioxide dissolved therein. By thus containing dissolved chlorine dioxide in the chlorine dioxide generating composition, it becomes possible to release chlorine dioxide more efficiently.

When the composition of the second embodiment contains dissolved chlorine dioxide, the content of chlorine dioxide may be set appropriately depending on the content of water, etc., and may be, for example, 10 ppm to 10,000 ppm, preferably 50 to 6,000 ppm.

The shape of the composition of the second embodiment may be appropriately set depending on the composition. For example, when water is not blended, or when a moisture-retaining base that retains moisture is included, examples of the shape include tablet, powder, granule, etc. When water is blended in a form other than blending a moisture-retaining base that retains moisture, examples of the shape include liquid, gel, paste, etc.

[Amount of chlorine dioxide released from chlorine dioxide-releasing composition]
The amount of chlorine dioxide released from the chlorine dioxide-releasing composition may be controlled by appropriately adjusting the composition of the composition depending on the manner in which chlorine dioxide is released, the installation site, and the like.

For example, when gaseous chlorine dioxide is to be released, it is desirable to set the chlorine dioxide gas concentration in the internal space of the toilet bowl (the space formed by the toilet lid and the bowl portion, etc.) formed when the toilet lid is closed for 12 hours to 0.01 ppm or more, preferably 0.01 to 100 ppm, more preferably 0.02 to 10 ppm, and particularly preferably 0.1 to 1 ppm. By controlling the chlorine dioxide gas concentration in the internal space of the toilet bowl formed when the toilet lid is closed to be within the above range, it is possible to impart even more excellent dirt removal and anti-fouling effects. The concentration of chlorine dioxide gas generated can be controlled by appropriately adjusting the content of chlorine dioxide contained in the chlorine dioxide-releasing composition and/or the composition and content of the chlorine dioxide generating source.

Other ingredients that can be included in the chlorine dioxide-releasing composition
The chlorine dioxide-releasing composition used in the present invention may contain, in addition to the above-mentioned components, fragrances, surfactants, solvents other than water, enzymes, bactericides, chelating agents, colorants, pigments, deodorants, emulsifiers, solubilizers, extenders, solubility regulators, bleaching agents, water repellents, hydrophilic agents, fillers, pH regulators, buffers, antifoaming agents, excipients, etc. The contents of these components may be appropriately set depending on the shape of the chlorine dioxide-releasing composition, the types of components used, etc.

Usage The toilet cleaner of the present invention has an excellent cleaning effect, due to the action of chlorine dioxide, which not only removes stains such as feces, but also prevents the adhesion of feces and stains that cause blackening. Therefore, the toilet cleaner of the present invention can be used as a toilet stain remover and can also be used as a toilet stain-proofing agent.

The toilet cleaner of the present invention may be used for cleaning a toilet in a form in which gaseous chlorine dioxide is released from the chlorine dioxide-releasing composition, or in a form in which dissolved chlorine dioxide is released from the chlorine dioxide-releasing composition. In a form in which gaseous chlorine dioxide is released, the specific gravity of gaseous chlorine dioxide is higher than that of air, and the released chlorine dioxide can be spread over the entire surface of the bowl portion, making it possible to impart a stain removal effect and a stain prevention effect even to areas that do not come into contact with flush water, which is particularly suitable for the toilet cleaner of the present invention.

Hereinafter, the form that releases gaseous chlorine dioxide will be referred to as "air-type toilet cleaner," and the form that releases dissolved chlorine dioxide will be referred to as "dissolved-type toilet cleaner," and the manner of use for each will be explained.

[Air-type toilet bowl cleaner]
In the case of an air-type toilet cleaner, the chlorine dioxide-releasing composition is attached to the wall surface of the internal space of the toilet bowl formed when the toilet lid is closed, such as the surface of the toilet lid on the bowl side, the surface of the bowl, the rim, etc. The chlorine dioxide-releasing composition installed in such a location releases gaseous chlorine dioxide into the space formed by the toilet lid and the bowl, etc. of the toilet bowl when the toilet lid is closed, and spreads chlorine dioxide over the entire surface of the bowl, the rim (including the back surface), and the inside of the rim (water passing part), thereby imparting a dirt removal effect and a dirt prevention effect even to areas that do not come into contact with flush water.

Air-type toilet cleaners can be used on Western-style toilets, Japanese-style toilets, toilets for easily converting Japanese-style toilets into Western-style toilets, toilets with toilet seats attached, portable toilets, etc., but are preferably used on Western-style toilets.

In the case of a Japanese-style toilet, the toilet lid corresponds to the toilet cover, and the bowl corresponds to the toilet container. The rim of the toilet serves to place the toilet seat at the top end of the bowl in a Western-style toilet, and is located close to the floor on which the toilet is placed in a Japanese-style toilet. The rim of a Western-style toilet usually has a water passage (water passage) inside for guiding flush water.

When installing an air-type toilet cleaner in the bowl or rim, the installation location is:
The portion may be a portion that comes into contact with flush water, or a portion that does not come into contact with flush water.

In the case of air-type toilet cleaners, in order to enhance the effect of spreading chlorine dioxide over the entire surface of the bowl of the toilet, it is desirable to attach the chlorine dioxide-releasing composition to the bowl side of the toilet lid. Figures 1 and 2 show schematic diagrams of an embodiment in which a chlorine dioxide-releasing composition 1 is installed on the bowl 3 side of a toilet lid 2 of a Western-style toilet. In Figure 1, the toilet lid 2 of the Western-style toilet is in an open state, and in Figure 2, the toilet lid 2 of the Western-style toilet is in a closed state. For the sake of convenience, the flow path of flush water from the water storage tank to the bowl is omitted in Figures 1 and 2.

Air-type toilet cleaners are stored in containers and placed in a designated area for use.
When the air-type toilet bowl cleaner is in the form of a sticky gel, the air-type toilet bowl cleaner may be adsorbed directly onto the installation site without being placed in a container.

The container used for the air-type toilet cleaner may be capable of releasing gaseous chlorine dioxide to the outside of the container while retaining the chlorine dioxide-releasing composition. Specifically, a container having a storage section for storing the chlorine dioxide-releasing composition and a release section for releasing gaseous chlorine dioxide generated from the chlorine dioxide-releasing composition to the outside of the container may be used. The container may be provided with a fixing section, such as an adhesive, a suction cup, or a member for engaging with the rim section, for fixing the container to the toilet lid or rim section of the toilet.

One embodiment of a container used for an air-type toilet cleaner is a container having a storage section that stores a chlorine dioxide-releasing composition and a release section that is made of a permeable film through which chlorine dioxide can pass (chlorine dioxide-permeable film).

The chlorine dioxide permeable film used as the release section may be a so-called fragrance permeable film, which is disclosed in WO 98/23304, JP 6-219479 A, U.S. Patent No. 5,518,790, and the like, and is publicly known. The material constituting the chlorine dioxide permeable film is not particularly limited, and examples thereof include polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene ethyl acrylate, paper, and mixtures thereof. Among these, linear low density polyethylene (LLDPE) is preferable. The chlorine dioxide permeable film used as the release section may be a single layer film made of one material, or a multilayer film in which two or more layers made of the same or different materials are laminated.

The container having a release part made of a chlorine dioxide permeable film may be made of only a chlorine dioxide permeable film, or may be made of a combination of a chlorine dioxide permeable film and a chlorine dioxide impermeable material. In the present invention, the chlorine dioxide impermeable material refers to a material that does not allow not only the chlorine dioxide releasing composition but also chlorine dioxide to pass through. As such a chlorine dioxide impermeable material, various types of materials are known, including, for example, glass, polyvinylidene chloride, polyethylene terephthalate, ethylene vinyl acetate copolymer, aluminum, etc., and these can be appropriately selected and used.
The chlorine dioxide impermeable member can take various forms, such as a film, a sheet, a bag, a container, etc., as long as it can be combined with the chlorine dioxide permeable film to form a container capable of enclosing the chlorine dioxide-releasing composition.

A container having a release section made of a chlorine dioxide permeable film may be directly provided with a fixing section such as an adhesive or a suction cup for fixing to a toilet lid or the like, or the container may be supported on a removable support, and the support may be provided with a fixing section for fixing to a toilet lid, rim, or the like.

A container having a release section made of a chlorine dioxide-permeable film can be used with any shape of chlorine dioxide-releasing composition, but is particularly suitable for use as a container for storing a liquid or gel-like chlorine dioxide-releasing composition.

In addition, when the chlorine dioxide-releasing composition is in a shape-retaining form (gel, tablet, granule, powder, etc.), a container having a release section made of nonwoven fabric may be used. The container having a release section made of nonwoven fabric may be formed into a container shape (bag shape) using only nonwoven fabric, or may be formed by combining nonwoven fabric with a chlorine dioxide impermeable member. The material and shape of the chlorine dioxide impermeable member are as described above.

A container having a release section made of nonwoven fabric may be directly provided with a fixing section such as an adhesive or a suction cup for fixing to a toilet lid, rim, etc., or the container may be supported on a removable support, and the support may be provided with a fixing section for fixing to a toilet lid, rim, etc.

Furthermore, when the chlorine dioxide-releasing composition is in a shape that retains its shape (such as a gel, tablet, granule, or powder), a container may be used that has a storage section that can maintain the chlorine dioxide-releasing composition in a fixed state and an opening (releasing section) for releasing gaseous chlorine dioxide generated from the chlorine dioxide-releasing composition to the outside of the container.

[Dissolved toilet bowl cleaner]
In the case of a dissolved-type toilet bowl cleaner, the chlorine dioxide-releasing composition may be installed and used so as to come into contact with flush water of the toilet bowl and release chlorine dioxide in a dissolved state into the flush water. That is, in the case of a dissolved-type toilet bowl cleaner, it may be used in the form of an on-tank cleaner for flush toilets, an in-tank cleaner for flush toilets, a rim cleaner for flush toilets, a cleaner attached to the surface of a toilet bowl, etc.

An on-tank cleaning agent for flush toilets is a cleaning agent that is placed on top of the hand washing section of a flush toilet. When the container in which the cleaning agent is stored comes into contact with flush water supplied to the hand washing section, the cleaning agent flows out of the container, and the flush water with the cleaning agent dissolved in it is released into the toilet bowl, thereby cleaning the toilet bowl.

A flush toilet in-tank cleaner is a cleaner that is placed in the water tank of a flush toilet and used; when it comes into contact with flush water in the water tank, the cleaner dissolves, and when flushed, the flush water with the cleaner dissolved in it is released into the toilet bowl, thereby cleaning the toilet bowl. When used as an in-tank cleaner for flush toilets, the toilet bowl cleaner of the present invention is preferably in solid form.

A cleaning agent for the rim of a flush toilet is attached to the rim of a flush toilet, and when the flush water released into the toilet bowl comes into contact with a container containing the cleaning agent, the cleaning agent flows out of the container, and the flush water with the cleaning agent dissolved in it is released into the toilet bowl, thereby cleaning the toilet bowl.

A cleaning agent used by adhering to the surface of a toilet is a cleaning agent that is installed in a state of being attached to the surface of the toilet, and when it comes into contact with the flush water released into the toilet during flushing, the cleaning agent dissolves into the flush water, thereby cleaning the toilet. When used as a cleaning agent by adhering to the surface of a toilet, the toilet cleaning agent of the present invention is preferably in a gel form in order to provide adhesion to the toilet surface.

When the toilet cleaner of the present invention is used as an on-tank cleaner or rim cleaner for a flush toilet, the container for storing the toilet cleaner needs only to have a storage section for storing the toilet cleaner and a discharge hole for discharging the toilet cleaner out of the container, and the toilet cleaner in the storage section can be discharged out of the container via the discharge hole when the container comes into contact with water. Conventional containers for on-tank cleaners or rim cleaners for flush toilets can be used.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these.

Test Example 1: Evaluation of fecal removal effect A gel-type detergent having the composition shown in Table 1 was prepared, and the following test was carried out using a mixture of salad oil and carbon black as model fecal dirt in a salad oil:carbon black mass ratio of 100:2.

30g of each gel-type detergent was placed in a container having a storage section and an opening communicating from the storage section to the outside of the container. 3g of model dirt was applied to the bowl section of a toilet bowl with an openable toilet lid [TOTO water tank (model number: S721) and TOTO toilet bowl (model number: C720)] so as to cover an area of approximately 200cm2. Next, each gel-type detergent placed in a container was attached to the bowl section side of the toilet bowl lid, and the toilet bowl was left for 12 hours with the toilet lid closed. After that, 100ml of air was sucked from the space inside the toilet bowl (the space formed by the toilet lid and the bowl section, etc.) with a syringe, and a chlorine dioxide gas detector tube (No. 23M (measurement range 0.1-10ppm) or No. 23L (measurement range 0.025-1.2ppm) (both manufactured by Gastec Corporation)) was inserted to measure the chlorine dioxide gas concentration. After leaving the container for 12 hours, about 13 L of water was flushed out, and the amount of remaining model dirt was visually determined, and the dirt removal effect was evaluated according to the following criteria.
<Criteria for judging dirt removal effect>
⊚: The remaining rate of model dirt is less than 5%.
◯: The remaining rate of model dirt is 5% or more and less than 20%.
Δ: The remaining rate of model dirt is 20% or more and less than 50%.
×: The remaining rate of model dirt is 50% or more.

The results are shown in Table 1. As a result, it was confirmed that by placing a gel-type cleaning agent containing a chlorine dioxide source on the toilet lid, chlorine dioxide gas can be released into the space inside the toilet, and this has the effect of removing dirt from the toilet bowl.

Test Example 2: Evaluation of feces and blackhead removal effect and antifouling effect (field test)
The following field test was carried out using the gel detergent prepared in Test Example 1. Each gel detergent contained in a container was attached to the bowl side of the toilet lid of a household toilet for a four-person family.
The container used was the same as in Test Example 1. The toilet bowl was not cleaned for 7 days,
A household toilet was used. When the toilet was not in use, the toilet lid was kept closed. A household toilet for a four-person family is usually used 15 to 25 times per day. After 7 days of use, the toilet was visually inspected for the presence or absence of fecal stains and black spots, and the effect of removing fecal stains and black spots was evaluated according to the following criteria.
<Criteria for judging dirt removal effect>
⊚: No fecal stains or black spots were observed at all.
○: Fecal stains or black spots are slightly observed.
Δ: Fecal stains or black spots are slightly observed.
×: Significant fecal stains or black spots are observed.

The results are shown in Table 2. As a result, it was confirmed that by placing a gel-type cleaning agent containing a chlorine dioxide source on the toilet cover, the adhesion of fecal stains and black stains was sufficiently suppressed even when the toilet was used for seven days without cleaning, and that the release of chlorine dioxide gas into the space inside the toilet bowl provided excellent stain removal and anti-soiling effects.

Test Example 3: Evaluation of the effect of preventing blackening Gel-type cleaners having the compositions shown in Table 3 were prepared, and 10 g of each gel-type cleaner was used to evaluate the effect of preventing blackening. A potato dextrose agar medium was prepared in a plastic petri dish having a diameter of 8.7 cm, and 100 μl of a bacterial solution containing Cladosporium halotolerans (NBRC111839) (causing bacteria of blackening) adjusted to a concentration of 1×10 ⁸ cells/ml was applied. Next, the petri dish with the bacteria applied (with the lid open) and the gel-type cleaner contained in the container were placed in a plastic case with a lid (volume 25 cm×15 cm×10 cm), the plastic case was sealed, and the container was left at 22.5° C. for 5 days. The container used was the same as in the case of Test Example 1. Thereafter, the growth state of the bacteria on the plastic petri dish was visually confirmed, and the effect of preventing blackening was evaluated according to the following criteria. After the test was completed (after leaving the container stationary for 5 days), 100 ml of air was drawn into the container through a gap created by slightly opening the container lid, and the syringe was connected to a chlorine dioxide gas detector similar to that in Test Example 1 to measure the chlorine dioxide gas concentration.
<Criteria for determining effectiveness in preventing dark spots>
○: No bacterial colonies were observed on the petri dish.
Δ: The number of bacterial colonies observed in the petri dish was 10 or less.
×: The number of bacterial colonies observed in the petri dish was 11 or more and 100 or less.
XX: Numerous bacterial colonies were observed in the petri dish.

The results are shown in Table 3. As a result, it was confirmed that the proliferation of bacteria that cause blackening can be effectively suppressed by releasing chlorine dioxide gas using a gel-type cleaning agent that contains a chlorine dioxide source.

1 Chlorine dioxide releasing composition 2 Toilet cover 3 Bowl 4 Water

Claims (7)

comprising a composition that releases chlorine dioxide,
The composition is in a gel or paste form, and is attached to a portion of a wall surface of an internal space of a toilet bowl formed when the toilet lid is closed, which does not come into contact with flush water, and is used as a toilet bowl stain remover in such a manner that gaseous chlorine dioxide is released into the internal space so as to reach a concentration of 0.1 ppm or more in 12 hours ;
The composition is used by being contained in a container having a storage portion and a release portion made of a permeable film through which chlorine dioxide can pass . Used to flush a toilet bowl having an openable toilet lid,
2. The toilet bowl cleaner of claim 1, which is applied to the bowl side of the toilet lid, the surface of the bowl of the toilet, or the rim of the toilet. The toilet cleaner according to claim 2, which is used by being placed on the bowl side of the toilet lid of the toilet. The toilet bowl cleaner according to any one of claims 1 to 3, wherein the composition contains a source of chlorine dioxide. The toilet bowl cleaner according to claim 4, wherein the source of chlorine dioxide is a chlorite and an acid. The toilet bowl cleaner according to any one of claims 1 to 5, which is used as a toilet bowl stain remover and toilet bowl stain-proofing agent. A method for cleaning a toilet, comprising cleaning a toilet using the toilet cleaner according to any one of claims 1 to 6.