JP5393067B2 - Solid cleaning agent for flush toilet tank - Google Patents

Description

  The present invention relates to a solid cleaning agent for flush toilets containing a predetermined amount of metal ion-carrying zeolite.

  Cleaning agents for flush toilets are mainly used for on-tank cleaning agents installed in the hand-washing part at the top of the water storage tank together with the storage container, and for in-tank cleaning used by immersing in the water storage tank. There are two types of agents. Among these, the cleaning agent for on-tank has advantages in use such as easy installation, the remaining amount of cleaning agent can be easily confirmed, and a fragrance effect can be imparted by blending of fragrances. It is in circulation.

An on-tank cleaning agent is required to have both excellent cleaning characteristics and elution characteristics as its basic performance. The former characteristic, that is, the cleaning characteristic is a characteristic that imparts an excellent cleaning action to water flushed in the toilet bowl, and is indispensable as a cleaning agent. In addition, the latter characteristic, that is, the elution characteristic, is a characteristic that a desired amount of a cleaning component is stably eluted by a short contact with water for cleaning even if there is a difference in temperature, and is affected by temperature. It is essential for providing a stable cleaning effect throughout the year. Such characteristics are essential for cleaning agents for flush toilet tanks. That is, it is desirable that the elution characteristics of the cleaning agent for the flush toilet tank are not easily affected by the difference in temperature, and the elution rate is required to be stable or constant throughout the year. Conventionally, various prescriptions have been examined and developed as flushing toilet-on-tank cleaning agents by paying attention to the above-described cleaning characteristics and elution characteristics (see, for example, Patent Document 1).
JP 2000-273383 A

  From the background as described above, the present invention is not easily affected by the water temperature, and since the difference in the number of hot water and cold water is small, solid washing for flush toilet on tank having stable elution characteristics regardless of the season or region The main purpose is to provide an agent.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, by mixing a predetermined amount of metal ion-carrying zeolite into a toilet solid detergent, the difference in elution rate depending on the water temperature (that is, the number of possessions) It was found that the difference can be reduced. Further, the present inventors have found that a more stable elution characteristic can be imparted by blending a builder such as an organic acid salt and an inorganic acid salt in addition to the metal ion-carrying zeolite. The present invention has been completed by making further improvements based on such findings.

That is, this invention is the solid washing | cleaning agent for flush toilet on tank hung up below:
Item 1. A solid detergent for flush toilet tank, containing 0.5 to 20% by weight of metal ion supported zeolite.
Item 2. Item 2. The solid cleaning agent for flush toilets according to Item 1, further comprising at least one builder of either an organic acid salt or an inorganic acid salt.
Item 3. Item 3. The solid cleaning agent for flush toilet tank according to Item 2, wherein the builder is an inorganic acid salt.
Item 4. Item 4. The solid detergent for flush toilet tank according to Item 2 or 3, wherein the builder is any one of sulfate and carbonate.
Item 5. Item 5. The solid cleaning agent for flush toilets according to any one of Items 2 to 4, wherein the builder contains at least sodium sulfate.
Item 6. Item 6. The solid cleaning agent for flush toilets according to any one of Items 2 to 5, wherein the blending ratio of the builder is 15 to 60% by weight.
Item 7. Item 7. The solid detergent for flush toilet tank according to any one of Items 1 to 6, wherein the metal ions supported on the metal ion-supported zeolite include at least one of silver ions and zinc ions.
Item 8. Item 8. The solid detergent for flush toilet on-tank according to any one of Items 2 to 7, wherein the mixing ratio of the metal ion-carrying zeolite and the builder is 0.01 to 420 parts by weight with respect to 1 part by weight of the metal ion-carrying zeolite. .
Item 9. Item 10. A solid cleaning agent for flush toilets according to any one of Items 1 to 8, further comprising a surfactant.
Item 10. Item 10. The solid detergent for flush toilet tank according to Item 9, wherein the surfactant contains at least one of an anionic surfactant and a nonionic surfactant.
Item 11. Item 11. The solid detergent for flush toilet tank according to any one of Items 1 to 10, which is a kneaded molded product.
Item 12. A method for producing a solid detergent for flush toilet on-tank containing metal ion-supported zeolite, comprising a step of kneading and molding a raw material containing metal ion-supported zeolite.
Item 13. Use of a solid composition for a flush toilet on-tank containing 0.5 to 20% by weight of a metal ion-supported zeolite for the production of a flush toilet toilet tank cleaner.

  ADVANTAGE OF THE INVENTION According to this invention, the solid washing | cleaning agent for flush toilet on tanks with a small difference in the frequency | count of warm water and cold water and a stable elution rate can be obtained. Therefore, the solid detergent for flush toilet on-tank of the present invention is not easily affected by the difference in temperature and temperature depending on the season and region, and can maintain a certain dissolution property throughout the year.

  Moreover, the manufacturing method of the solid detergent for toilets of this invention is shape | molded by solid form by kneading | mixing shaping | molding. The solid cleaning agent thus obtained has an appropriate hardness that can be easily controlled by water pressure when used as an on-tank cleaning agent while maintaining a solid shape.

  Such a solid cleaning agent of the present invention, for example, in the case of a total amount of about 25 g of the solid cleaning agent, has a holding frequency of about 400 to 600 times at a water temperature of 25 ° C. and about 500 to 800 times at a water temperature of 5 ° C., The difference in the number of times due to the difference in water temperature (for example, 25 ° C. and 5 ° C.) can be reduced to about 300 times or less, preferably about 200 times or less.

<Solid detergent for flush toilet tank>
The solid detergent for flush toilet tank of the present invention contains a predetermined amount of metal ion-carrying zeolite. Further, the solid cleaning agent of the present invention is a cleaning agent for an on-tank of a flush toilet (that is, a detergent that is used by being installed in a hand-washing portion of a flush toilet, and is installed in a water supply channel in the flush toilet. Used as a cleaning agent). When the solid cleaning agent of the present invention is used as a cleaning agent for a flush toilet tank, the solid cleaning agent may be used as it is installed in a hand-washing part of a flush toilet, but is usually in a state of being contained in a container. Used in the hand-washing part of a flush toilet. Hereinafter, each component of the solid cleaning agent for flush toilet on tank of the present invention will be described.

(i) Metal ion-supported zeolite The metal ion-supported zeolite used in the present invention is one in which metal ions are supported on zeolite (zeolite: aluminosilicate) by an ion exchange reaction.

  As the zeolite, various zeolites such as natural zeolite (sometimes referred to as zeolite), artificial zeolite such as A-type zeolite, Y-type zeolite, P-type zeolite, and X-type zeolite can be used.

  The metal ions supported on the zeolite include at least one of silver ions, zinc ions, magnesium ions, tin ions, iron ions, nickel ions, platinum ions, gold ions, sodium ions, calcium ions, potassium ions, and copper ions. Preferably, it is a silver ion, a zinc ion, and more preferably a silver ion.

  The zeolite may carry one type of metal ion selected from these metal ions, but it can also carry two or more types of metal ions. In addition, in the present invention, the metal ion-supported zeolite may be used alone, or two or more metal ion-supported zeolites may be used in combination.

  The metal ions are supported on the metal ion-supported zeolite in a ratio of usually about 0.01 to 20% by weight, preferably about 0.1 to 15% by weight, more preferably about 1 to 10% by weight as metal ions. Yes. For example, when the metal ion is silver ion, it is preferably in the range of about 0.1 to 15% by weight as silver ion. Moreover, when a metal ion is a zinc ion, it is about 0.1-20 weight% as a zinc ion, Preferably it is the range of about 0.1-10 weight%.

  Moreover, when using in combination of 2 or more types of metal ion carrying | support zeolite, it does not specifically limit as a content rate of each metal ion in the metal ion carrying | support zeolite total amount, It can set suitably. For example, when a silver ion-supported zeolite and a zinc ion-supported zeolite are used in combination as the metal ion-supported zeolite, the ratio in terms of the weight of metal ions is about 0.005 to 100 parts by weight of zinc ions with respect to 1 part by weight of silver ions. The amount is preferably about 0.05 to 80 parts by weight, more preferably about 0.5 to 20 parts by weight. Accordingly, when two or more kinds of metal ion-carrying zeolites are used in combination, the blending amount can be appropriately set with reference to the content ratio of each metal ion.

  In the solid detergent of the present invention, the blending ratio of the metal ion-supported zeolite may be appropriately set according to the type and blending ratio of other blending components, but as an example, the total amount of the solid detergent The proportion of the metal ion-supported zeolite is 0.5 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 2 to 10% by weight.

  In addition, the zeolite as described above can also be obtained commercially. Table 1 below shows an example of physical properties of trade name: Zeomic, product number: AJ10N, Sinanen Zeomic Co., Ltd. as a zeolite that supports both commercially available silver ions and zinc ions.

  In addition, as other products, trade name: Zeomic, manufactured by Sinanen Zeomic Co., Ltd., product number: AG10N (M is Ag in the composition shown in Table 1); product name: Zeomic, product number: ZA10N (in the composition shown in Table 1) M is Zn), and the physical properties (property, true specific gravity, bulk specific gravity, average particle diameter, pH) of these zeolites are equivalent to those of AJ10N described in Table 1 above.

  By blending a predetermined amount of the metal ion-carrying zeolite, it is possible to obtain a solid detergent for flush toilet on-tank with a small variation in elution characteristics depending on the water temperature.

(ii) Surfactant The solid detergent of the present invention usually contains a surfactant together with the above metal ion-carrying zeolite in order to impart cleaning properties. As the surfactant used in the present invention, a conventionally known surfactant can be used and is not particularly limited. Examples of the cationic surfactant include alkyl (C ₆ -C ₂₀ ) trimethylammonium salt, dialkyl (C ₆ -C ₂₀₎ dimethyl ammonium salts, and alkyl (C _{6 ~C 20)} quaternary ammonium salts of dimethyl benzyl ammonium salts, alkyl (C _{6 ~C 20)} amine salts, alkyl (C _{6 ~C 20)} amine Examples thereof include ethylene oxide adducts and alkylpyridinium, and dimethylbenzylammonium salt is preferred.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, alkyl sarcosine salt, alkyl sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene alkyl ether sulfate. Ester salt, alkyl sulfoacetate, α-glycerin monoalkyl ether-α′-sulfonate, α-sulfo fatty acid salt, α-acyl-α′-sulfonyl diglyceride salt, N-acylmethyl taurine salt, fatty acid isopropanolamide sulfate Examples thereof include ester salts, sodium N-acyl glutamate, and potassium salts and lithium salts thereof, preferably alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, alkyl Rukoshin salts, alkyl sulfate salts, polyoxyalkylene alkyl ether sulfate, alkyl sulfo acetates, more preferably α- sodium olefin sulfonate, sodium lauroyl sarcosinate, sodium lauryl sulfoacetate.

  Nonionic surfactants include, for example, higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid alkanolamide ethylenes. Oxide adducts, fat and oil ethylene oxide adducts, polyoxyalkylene alkyl ethers, polyoxyalkylene block copolymers (ethylene oxide / propylene oxide block copolymers, ethylene oxide / propylene oxide / butylene oxide copolymers) , Fatty acid ester of glycerol, fatty acid ester of pentaerythritol, aliphatic ester of sorbitol, fatty acid ester of sorbitan Examples include fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, hydroxyalkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines, preferably higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohols. A fatty acid ester ethylene oxide adduct and a polyoxyalkylene block copolymer, more preferably a polyoxyalkylene block copolymer.

  Although the said surfactant may be used individually by 1 type, it can also be used in combination of 2 or more type. Preferably, at least one surfactant selected from the anionic surfactants and nonionic surfactants is used.

  The amount of the surfactant is not particularly limited as long as it is an amount that imparts good cleaning properties to the solid detergent of the present invention and does not impair the effects of the present invention, but is usually about 10 to 80% by weight, The amount is preferably about 20 to 60% by weight, more preferably about 30 to 50% by weight.

  Usually, by blending the above surfactant, the solid detergent for flush toilet on-tank tends to be unstable in elution characteristics, but the solid detergent of the present invention has the above-mentioned (i) metal ion-carrying zeolite and By blending the following (iii) builder, stable elution characteristics can be imparted. In particular, when a polyoxyalkylene block polymer is used as a surfactant, the elution characteristics tend to be unstable due to temperature differences. By combining sodium sulfate, the elution characteristics can be kept more stable regardless of whether it is hot water or cold water.

(iii) Builder By adding a builder to the solid detergent for flush toilet tank of the present invention, more stable elution characteristics can be imparted. The builder used in the present invention is selected from organic acid salts and inorganic acid salts. The organic acid salt used in the present invention is not particularly limited as long as a desired effect can be obtained. For example, citric acid, malic acid, succinic acid, maleic acid, fumaric acid, gluconic acid, adipic acid, lactic acid, tartaric acid, Examples include alkali metal salts such as glycolic acid and ascorbic acid, and an alkali metal salt of citric acid is preferable.

  The inorganic acid salt is not particularly limited as long as the desired effect is obtained. Specifically, alkali metal chloride, carbonate, hydrogen carbonate, sulfate, phosphate, borate, silica Examples of the acid salt include carbonates and sulfates. Examples of such inorganic acid salts include sodium sulfate, potassium sulfate, sodium chloride, sodium carbonate, sodium hydrogen carbonate, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, borax and the like, preferably an alkali metal Sulfates and alkali metal carbonates, more preferably sodium sulfate.

  Among the above builders, sodium sulfate can be mentioned as a more remarkable effect of the present invention. Although the said organic acid salt and inorganic acid salt can also be used individually by 1 type, you may use it in combination of 2 or more type.

  When a builder is added to the solid detergent of the present invention, the total amount is about 1 to 83.5% by weight, preferably about 15 to 60% by weight, more preferably about 20 to 60% by weight, and further preferably 30 to 50% by weight. %.

  By blending a builder in an amount of 15% by weight or more, the difference in the number of times between hot water and cold water can be reduced, and in particular, good shape retention can be imparted when producing a solid detergent by kneading and molding. As a result, a solid cleaning agent that is sufficiently suitable for practical use and production can be obtained.

  The blending ratio of the builder and the metal ion-carrying zeolite can be appropriately set as long as the above blending ratio is satisfied. For example, the builder is about 0.01 to 420 parts by weight, preferably 0.1 to 400 parts by weight with respect to 1 part by weight of the metal ion-carrying zeolite. About 1 part by weight, more preferably about 0.5 to 200 parts by weight, and still more preferably about 1 to 100 parts by weight.

  When using sodium sulfate or sodium carbonate as a builder, the above blending ratio is satisfied, and sodium sulfate or sodium carbonate is about 0.5 to 400 parts by weight, preferably 1 to 1 part by weight of metal ion-carrying zeolite. About 200 parts by weight, more preferably about 1 to 100 parts by weight, still more preferably about 1.25 to 100 parts by weight, and particularly preferably about 1.25 to 89 parts by weight.

  Preferred embodiments of the present invention include sodium sulfate as a builder, silver ion-supported zeolite or zinc ion-supported zeolite as a metal ion-supported zeolite, a mixture of these metal ion-supported zeolites, or a zeolite that supports both silver ions and zinc ions. Is used. The blending amount of each component can be appropriately set based on the blending ratio.

(iv) Other components The solid cleaning agent of the present invention is blended with a known coloring agent for the purpose of coloring water that is flushed to the toilet bowl during use (water that is washed to wash the toilet bowl after use). can do. The colorant used in the present invention is not particularly limited. For example, Blue No. 1, Blue No. 2, Blue No. 3, Blue No. 205, Yellow No. 3, Yellow No. 4, Yellow No. 202 (1), yellow Examples include No. 203, Red No. 105, Red No. 106, Red No. 2, and Red No. 3.

  The blending amount of the colorant can be appropriately set according to the color tone, and is, for example, about 0.5 to 30% by weight, preferably about 1 to 20% by weight, more preferably based on the total amount of the solid detergent of the present invention. Is about 1 to 15% by weight.

  Further, in addition to the above components, a pigment can be blended for the purpose of coloring the solid detergent of the present invention. As a pigment mix | blended with the solid cleaning agent of this invention, either an organic pigment or an inorganic pigment may be sufficient. Further, the white pigment or the colored pigment is not questioned, and may be appropriately selected according to the color tone to be applied to the solid detergent. Specific examples of inorganic pigments include titanium oxide, talc, calcium carbonate, zinc oxide, zinc sulfide, barium sulfate, calcium sulfate and its hydrate, iron oxide, cadmium sulfide, lead chromate, zinc chromate, carbon black, etc. Is exemplified. As organic pigments, red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 220, red 221, orange 203, orange 204 No., Yellow 205, Red 404, Red 405, Yellow 401, Blue 404 and the like, but are not limited thereto.

  When a pigment is blended in the solid detergent of the present invention, the blending ratio is, for example, 0.05 to 2% by weight, preferably 0.05 to 1.5% by weight of the pigment with respect to the total amount of the solid detergent. % By weight, more preferably 0.1 to 1% by weight.

  In addition to the above components, the solid cleaning agent of the present invention may further include builders, enzymes, bactericides, chelating agents, fragrances, deodorants, emulsifying and solubilizing agents for oily components, and bulking agents as necessary. Further, additives such as a solubility adjusting agent, a bleaching agent, a water repellent, a hydrophilic agent, a filler, a pH adjusting agent, a thickener, a moldability improving agent, a lubricant, and a buffering agent can be contained in an appropriate amount.

  As the builder used in the present invention, compounds used in the technical field other than those described above can be used. Specifically, polyalkylene oxide, polyethylene glycol, sodium carboxymethylcellulose, sodium hydroxypropylmethylcellulose, polyvinylpyrrolidone And polyester polyol, polyethylene glycol distearate, glucose, sucrose, fructose, lactose, carrageenan, gellan gum, guar gum, tamarind gum, xanthan gum, locust bean gum, sorbitol, starch, higher alcohol and the like.

  Specific examples of the enzyme used in the present invention include protease, lipase, amylase, cellulase, xylanase, and mannase.

  Specific examples of the bactericides used in the present invention include quaternary ammonium salts such as alkylbenzyldimethylammonium salts and didecyldimethylammonium salts, heterocyclic compounds such as cetylpyridinium salts and benzoisothiazolines, silver oxide, Examples include silver-containing water-soluble glass, silver compounds such as zeolite supporting silver, and other metal compounds.

  Specific examples of the chelating agent used in the present invention include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexa Examples include acetic acid and salts thereof.

<Method for producing solid detergent for flush toilet on tank>
The solid cleaning agent of the present invention is produced by mixing a predetermined amount of the above-described blending components and molding the mixture into a predetermined shape. The solid detergent of the present invention is desirably molded so as to be about 10 to 40 g, preferably about 20 to 30 g per molded product from the viewpoint of ease of use, aesthetics, and the like.

  The solid detergent of the present invention can be produced by a method generally used in the field of solid detergent, and is not particularly limited. For example, a kneaded product obtained by mixing a predetermined amount of the above-described blending components is subjected to various molding processes. To obtain a molded product. As the molding process, for example, the kneaded tableting molding method in which the obtained kneaded product is molded by pressing or tableting; the above-described blended components are extruded while kneading with a kneader, and extruded to the discharge part of the kneader. Examples thereof include a kneading extrusion molding method in which a kneaded product is cut with a cutting machine and molded. When subjected to the molding treatment, a binder, a lubricant, and the like can be blended as necessary.

  The solid detergent of the present invention is preferably a kneaded molded product. The solid detergent obtained by kneading and molding has a disintegration characteristic suitable as a solid detergent for a flush toilet tank while having a hardness necessary for maintaining a solid shape.

  In order to satisfy these characteristics, the solid detergent of the present invention desirably has a hardness of usually 200 g or more, preferably 400 g or more, more preferably 600 g or more. The hardness here refers to a rheometer (SUN RHEO METER CR-500DX; manufactured by San Kagaku Co., Ltd.) 24 hours after the preparation of the solid cleaning agent, a specimen temperature of 25 ° C., a needle diameter of a pressure-sensitive axis (adapter) of 3 mmφ, a needle This is the load (g) applied to the pressure sensitive shaft when the pressure sensitive shaft is pushed into the specimen to 4.5 mm at an input speed of 60 mm / min.

In order to obtain the solid detergent of the present invention having the hardness, for example, when tableting is performed, the tableting pressure can be appropriately set based on the hardness, but is usually in the range of about 100 to 1000 kgf / cm ^2. Is suitably used, and it is sufficient to use about 100 kgf / cm ² or more if the shape of the cleaning agent is adjusted.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples. Unless otherwise specified, the unit of each component in the composition is% by weight.

1. Manufacture of solid detergent for flush toilet on tank Solid detergent for flush toilet on tank having the composition shown in Tables 3 and 4 below (Examples 1-8 and Comparative Examples 1-5, cylindrical shape with a diameter of 30 mm, 25 g per piece ) Was prepared. Specifically, among the blended components, a predetermined amount of the powder component is stirred for about 10 seconds at about 3000 rpm with a Henschel mixer (manufactured by Mitsui Miike Kogyo Co., Ltd.), and then the remaining blended components (liquid components) are mixed. A predetermined amount was added and stirred again for about 10 seconds. 1 kg of the obtained mixture was kneaded into a columnar shape having a diameter of about 20 mm at a speed of 96 rpm with a kneader (S1-KRC kneader, manufactured by Kurimoto Tekko Co., Ltd.). The obtained cylindrical kneaded product is taken out in units of 25 g, and tableted into a cylindrical shape with a diameter of 30 mm at a tableting pressure of 100 kgf / cm ^{2 using} a hydraulic tableting machine (manufactured by Riken Seiki Co., Ltd.). A solid detergent for tanks was produced.

2. Performance evaluation of solid detergent for flush toilet tank (1)
The following evaluation test was performed using the obtained solid detergent for flush toilet on tank as a solid detergent for flush toilet on tank.

[Elution rate evaluation test]
The solid cleaning agent for the flush toilet on-tank is housed in an on-tank fragrance cleaner container ("Kobayashi Pharmaceutical Co., Ltd." Bluelet scented bouquet fragrance "main body container: flower-shaped container). Amount of water stored: 10 liters, TOTO S721B manufactured by TOTO EQUIPMENT CO., LTD. The temperature of the inflow water from the toilet tank hand wash section to the low tank is maintained at 25 ° C. or 5 ° C., the flow rate of the inflow water is adjusted to 50 mL / second, and the tank full time (the toilet water flow is “large” After 4 seconds of flushing with the lever, adjust the time until the storage of water in the tank is completed to 60 seconds (as a result, the total amount of water flowing from the toilet tank hand washing section per flush is 3L.) Set the “Large” lever of the water flow to automatically flash for 4 seconds at a rate of once every hour, and set the number of flushes until the solid detergent for the flush toilet on tank runs out. Measured. Here, the temperature of the inflowing water of 25 ° C. assumes the use conditions in summer, and the temperature of the inflow water of 5 ° C. assumes the use conditions in winter.

  From the measured number of flushes, the elution rate was evaluated according to the criteria shown in Table 2 below. In this test, it is assumed that if the number of flashes is 350 times or more, it can normally withstand use for about one month.

  In this test example, 2 to 4 points of the above evaluation criteria were not easily affected by the water temperature, and were used as solid detergents having a certain dissolution property. In the above evaluation criteria, the two points are at a level that causes no practical problems as a solid cleaning agent.

3. Evaluation results The results obtained are shown in Tables 3 and 4 below. In Tables 3 and 4 below, Zeomic AJ10N is a zeolite carrying both silver ions and zinc ions.

  From the results shown in Tables 3 and 4, it was shown that when no metal ion-carrying zeolite was blended (Comparative Examples 1 to 3), the above criteria were not satisfied and certain elution characteristics could not be maintained. On the other hand, when the blending amount of the metal ion-carrying zeolite is 0.5 to 20% by weight and the blending ratio of sodium sulfate when the metal ion-carrying zeolite is 1 part by weight is 1.25 to 89 parts by weight, The difference in the number of cold water (5 ° C.) and warm water (25 ° C.) was about 40 to 250 times, indicating that good elution characteristics were maintained (Examples 1 to 8).

  Furthermore, when the blending amount of the metal ion-carrying zeolite is 0.5 to 10% by weight and the blending ratio of sodium sulfate when the metal ion-carrying zeolite is 1 part by weight is 3.5 to 89 parts by weight, The difference in the number of cold water (5 ° C.) and warm water (25 ° C.) was about 40 to 180 times, indicating that the remarkably superior elution characteristics were maintained (Examples 1 to 4 and 6). And 7).

  From the above, it has been shown that the flushing toilet-on-tank solid cleaning agent of the present invention can reduce the difference in the number of flushes depending on the water temperature.

4). Performance evaluation of solid detergent for flush toilet tank (2)
The above “1. Examples 9 to 11 were prepared according to the description of "Manufacture of solid detergent for flush toilet on tank", and the obtained solid detergent for flush toilet on tank was used as a solid detergent for flush toilet on tank. 2. The dissolution rate was evaluated according to the evaluation test method described in “Performance Evaluation of Solid Cleaning Agent for Flush Toilet Tank”. The results are shown in Table 5 below. In Table 5 below, Zeomic AJ10N is a zeolite that supports both silver ions and zinc ions, Zeomic AG10N is a zeolite that supports only silver ions, and Zeomic ZA10N is a zeolite that supports only zinc ions. .

  From the results shown in Table 5 above, the solid detergent (Example 9) using zeolite supporting only silver ions also exhibits the same elution performance as zeolite supporting both silver ions and zinc ions. It has been shown.

  Moreover, about the solid cleaning agent (Example 10) using the zeolite which carry | supports only a zinc ion, the result inferior to Example 3 or Example 9 was shown a little. However, the elution performance of Example 10 has no problem at a practical level, and it has been shown that a solid detergent capable of sufficiently exhibiting the effects of the present invention can be obtained even when zinc ion-carrying zeolite is used.

  Further, when comparing the results of Example 3 using sodium sulfate as a builder and Example 11 using sodium carbonate as a builder, it is more flushing with water temperature when sodium sulfate is added than when sodium carbonate is added as a builder. It has been shown that the difference in the number of times can be reduced, and the effects of the present invention can be exhibited more remarkably.

Claims (12)

A solid detergent for flush toilet tank, containing 0.5 to 20% by weight of metal ion supported zeolite. Furthermore, the solid washing | cleaning agent for flush toilet on tanks of Claim 1 containing at least 1 sort (s) of either organic acid salt or inorganic acid salt. The solid cleaning agent for flush toilet on tank according to claim 2, wherein the builder is an inorganic acid salt. 4. The solid cleaning agent for flush toilet tank according to claim 2, wherein the builder is any one of sulfate and carbonate. The solid cleaner for flush toilet on tank according to any one of claims 2 to 4, wherein the builder contains at least sodium sulfate. The solid cleaning agent for flush toilet on tanks according to any one of claims 2 to 5, wherein a blending ratio of the builder is 15 to 60% by weight. The solid washing | cleaning agent for flush toilets in any one of Claims 1-6 in which the metal ion carry | supported by the said metal ion carrying | support zeolite contains at least any one of a silver ion and a zinc ion. 8. The solid washing for flush toilet on tank according to claim 2, wherein the mixing ratio of the metal ion-carrying zeolite and the builder is 0.01 to 420 parts by weight with respect to 1 part by weight of the metal ion-carrying zeolite. Agent. Furthermore, the solid washing | cleaning agent for flush toilet on tanks in any one of Claims 1-8 containing surfactant. The solid cleaning agent for flush toilets according to claim 9, wherein the surfactant includes at least one of an anionic surfactant and a nonionic surfactant. The solid washing | cleaning agent for flush toilet on tanks in any one of Claims 1-10 which is a kneaded molding. A water-washed toilet-on-tank solid cleaning agent containing metal ion-supported zeolite, comprising a step of kneading and molding a raw material containing metal ion-supported zeolite so that the final concentration of metal ion-supported zeolite is 0.5 to 20% by weight . Production method.