JP3425478B2 - Solid compositions for washing toilets containing dyes - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid cleaning composition containing a pigment used in flush toilets. More specifically, the present invention relates to a solid composition for cleaning containing a pigment capable of stably providing a target color tone to the cleaning water from the initial stage of use without depending on the running water temperature of the toilet, and a flush toilet water storage tank. A method of providing a flush toilet flush water with a solid composition for flush toilet wash that can be stored and used in a container installed outside, further without depending on the water temperature by the flush toilet wash solid composition. It is provided.

[0002]

2. Description of the Related Art In a conventional solid composition for flushing toilets, a pigment is blended with a cleaning component and a fragrance as a means for knowing the effective period of the cleaning effect. Since this dye elutes with the surfactant as a cleaning component,
The end point of the cleaning component can be easily confirmed by checking the shade of the color tone of the flush toilet water over time. However,
It is difficult to always provide a stable color tone with the detergent containing this dye, and in particular, the color tone may become dark or light at the initial stage of use.

Therefore, as a method for obtaining a stable color tone, for example, in JP-A-4-253798, a solid detergent for flush toilets containing a mixture of a fast-dissolving dye and a slow-dissolving dye to appropriately adjust the coloring is disclosed. It is shown. Further, in Japanese Examined Patent Publication No. 3-46518, for the purpose of cleaning liquid coloring, which contains a specific coloring agent, the toilet cleaning water is colored, and the colored water after use can be easily decolorized, which is also effective from the viewpoint of environmental hygiene. Compositions are disclosed. On the other hand, Japanese Patent Publication Sho 49-105
In No. 22, a compound obtained by adding 15 moles or more of ethylene oxide to an aliphatic alcohol having 8 or more carbon atoms or a compound obtained by adding 15 moles or more of ethylene oxide to a fatty acid having 8 or more carbon atoms in order to limit the dissolution rate in water, respectively, Cleaning compositions for flush toilets, which are used alone or as a mixture of the two, are shown.

[0004]

In these conventional techniques, as a means for stabilizing the wash water of the flush toilet, the characteristics of the colorant are used, various surfactants are used, Further, the solubility and the like are improved by combining them. However, in these documents, there is no recognition that the shade of the color tone is influenced by the running water temperature of the toilet, that is, it depends on the water temperature, and therefore the relationship between the shade of the color tone and the water temperature dependency is eliminated. Then, there is no suggestion of any means for solving the problem. Then, the present inventors have diligently studied means for solving the above-mentioned problems, and have found a solid composition for flush toilet cleaning capable of solving the above-mentioned problems, and an object thereof is to provide the same. It is a thing.
Another object of the present invention is to provide a method for cleaning a toilet using this solid detergent for flushing toilet.

[0005]

The present invention provides the following (1).
By the means of (7) to (7), the above object is achieved. (1) temperature dependence no, Nin to excellent base in water solubility
Acid or behenic acid and stearic acid ethylene oxalate
A solid composition for flushing toilets containing a pigment, characterized in that a nonionic surfactant which is solid at room temperature and which comprises an id adduct is blended. (2) temperature dependence no, Nin to excellent base in water solubility
Acid or behenic acid and stearic acid ethylene oxalate
A solid composition for washing flush toilets, comprising a colorant, which comprises a nonionic surfactant which is a solid at room temperature and which comprises an id addition product. (3) Behenic acid, or behenic acid and stearic acid, mixed with a monoester type nonionic surfactant consisting of ethylene oxide added in an amount of 50 to 120 mol, depending on the water temperature A solid composition for flushing toilets, which contains a dye capable of obtaining a stable color tone without performing. (4) Behenic acid or a mixture containing stearic acid and behenic acid as a main component, to which ethylene oxide is added, and a monoester type nonionic surfactant having an ethylene oxide addition mole number of 70 to 100 is blended. A solid composition for flush toilet cleaning, comprising a pigment capable of obtaining a stable color tone independently of the water temperature. (5) The above-mentioned (1), wherein the solid composition for flush toilet is formed into two layers, a slow-dissolving dissolution layer and an initial dissolution layer.
~ The solid composition for flush toilet cleaning according to any one of (4). (6) The solid composition for flush toilet cleaning according to any one of (1) to (5) is stored in a container installed outside the flush toilet water storage tank, and used by contacting with running water of the flush toilet. A method of providing stable toilet running water having a stable color tone, which is independent of the water temperature. (7) The composition is stored in a container having a structure in which at least a part of the solid composition for flush toilet cleaning according to any one of (1) to (5) is in contact with water. A cleaning material for flush toilets.

In the present invention, the nonionic surfactant may be one which has no water temperature dependence and is solid at room temperature and which is excellent in water solubility. Particularly, for the purpose of the present invention, the nonionic surfactant does not have water temperature dependence. The monoester type is suitable as the one having the above-mentioned properties, and the fatty acid in the ethylene oxide adduct of the fatty acid is preferably behenic acid (C22, C and numbers). Indicates a carbon number), or a mixture of behenic acid and stearic acid (C18) as a main component, and other fatty acids such as palmitic acid (C16) and arachidic acid (C20) are contained to some extent. It may be a mixture. The two types of fatty acids that are the main constituents shown here do not necessarily have to be composed of a single component, and for example, behenic acid may be that described in a compendial document or the like. More specifically, behenic acid is a cosmetic raw material standard, second edition commentary (Yakuji Nippo (198
According to 4)), mainly behenic acid with a mixture of higher saturated fatty acids (C ₂₂ H ₄₄ O _2: Molecular weight 340.59) consists, in addition, according to contain slightly fatty arachidic acid and lignoceric acid Has been done. Therefore, the fatty acid referred to as behenic acid in the present invention may be within the scope of this description, and other fatty acids are also interpreted according to the descriptions in compendial documents and the like.

In the present invention, ethylene oxide includes ethylene chlorohydrin (HOCH ₂ CH ₂ C
l) obtained by reacting a concentrated alkali with each other, and industrially produced ones that are synthesized by oxidizing ethylene with oxygen, in which the number of added moles of ethylene is 50 to 120, Preferable one is 70 to 100. The number of added moles includes the case where the average number of moles is within the range. When the number of added moles of ethylene is not within the above range, it may not solidify sufficiently, may be easily dissolved, or may cause problems such as insufficient solubility upon contact with water, which is not preferable. In the present invention, the monoester-type nonionic surfactant is obtained by adding ethylene oxide to the above-mentioned fatty acid, and more specifically, an alkali catalyst is used for the fatty acid under pressure and high temperature (180 ° C.>) conditions. It is produced by reacting with ethylene oxide by causing heat generation. By this reaction, a monoester type ethylene oxide adduct is obtained.

In addition to this, it can be obtained by reacting a fatty acid with polyethylene glycol, and is produced by mixing the fatty acid and polyethylene glycol at high temperature. This reaction proceeds at 200 ° C. even without a catalyst, but the reaction can be promoted by adding a catalyst or blowing nitrogen or carbon dioxide gas. At this time, by setting the molar ratio of fatty acid to polyethylene glycol to be 1: 1, it is possible to obtain a composition close to that obtained by directly adding ethylene oxide. As the polyethylene glycol, a general-purpose one composed of a condensation product of ethylene oxide and water may be used, and its average molecular weight is from 2000 to 8000. Here, the average molecular weight of 2000 means that the molecular weight is 1800.
To 2250, and the average molecular weight is 80
00 indicates that the molecular weight is in the range of 8,000 to 10,000.

Examples of the reaction product composition obtained by the above reaction include behenic acid ethylene oxide (5
0-120) mole addition product, ethylene oxide stearate (50-120) mole addition product and the like. The reaction products are all monoester type.
Specifically, polyethylene glycol (4000) stearic acid ester, polyethylene glycol (400)
0) stearic acid / behenic acid ester, polyethylene glycol (6000) behenic acid ester, and the like. For example, a mixture of stearic acid and behenic acid (hereinafter, the mixture is referred to as "stearic acid / behenic acid") can be mentioned. The mixing ratio at this time is 1: 9.
To 9: 1, preferably 4: 6 to 6: 4. However, the term “mixing” as used herein means that two or more kinds of fatty acids are present and is not limited to this range.

More specifically, stearic acid / behenic acid ethylene oxide (50 to 120) mole adduct, polyethylene glycol (2000 to 8000) stearic acid ester, polyethylene glycol (200
0-8000) behenic acid ester, polyethylene glycol (2000-8000) arachidic acid ester,
Examples include polyethylene glycol (2000 to 8000) stearic acid / behenic acid ester and the like. And
The reaction products exemplified above include a reaction product of an ethylene oxide adduct and polyethylene glycol depending on the production method, but in the present invention, the structure and properties are similar or equal, and the names are different depending on the production method. I understand that they are different. In the production method in which a fatty acid and polyethylene glycol are reacted, the reaction time is long, and the reaction product varies from production to production, and it is not stable. It is preferred to use the product.

When the fatty acid is behenic acid or stearic acid / behenic acid, the melting point of the reaction product of the ethylene oxide adduct or polyethylene glycol is higher than that when stearic acid is used. When the composition is formed, it has excellent storage and transportation stability. In order to adjust the solubility of the composition and to stably elute each component in the flush water of the flush toilet, particularly in order to stabilize the color tone, it is necessary to keep the hydrophilicity of the reaction product to an appropriate level. is there. Here, when the fatty acid is stearic acid, the hydrophilicity is high, and therefore the dissolution rate at the time of use tends to increase, while when it is behenic acid or stearic acid / behenic acid, the hydrophilicity is lower than that of stearic acid. Therefore, it is suitable for obtaining an appropriate dissolution rate. The dissolution rate can be adjusted by the number of moles of ethylene oxide added to react with the fatty acid and the molecular weight of polyethylene glycol.
However, there are cases where the above-mentioned number of moles of ethylene oxide added and the molecular weight of polyethylene glycol are out of the range by adjustment, and the reaction product at this time is not suitable for the purpose of the present invention, and behenic acid or stearic acid is used as a fatty acid. It is preferable to use a mixture of behenic acid in an arbitrary ratio.

By blending the above-mentioned monoester type nonionic surfactant with the solid composition for flush toilet, the diluting coloring in the toilet running water which occurs at the initial stage of use is eliminated, and from the first time of use. A stable color tone can be obtained. Specifically, by blending the surfactant, the coloring of the toilet running water by the pigment blended together becomes independent of the water temperature, which makes it stable at low water temperature in winter as at other times. Toilet running water in different colors can be obtained. In the present invention, the monoester type nonionic surfactant is blended in an amount of 3 to 60% by weight, preferably 6 to 30% by weight, based on the total amount of the composition.

Further, as will be described later, when the solid composition is formed into two layers in consideration of solubility, the mixing ratio of the monoester type nonionic surfactant is, for example, an initial dissolution rate. The content in the dissolution layer is 30% by weight, the content in the slow-dissolving dissolution layer is 0% by weight, the total content is 3.6% by weight, and the content in the initial dissolution layer is 100% by weight, slow-dissolving dissolution Content in layer is 50
As the weight%, the total content can be 56% by weight. As another formulation example, the content in the initial dissolution layer is 85% by weight, and the total content is 1
The content may be 0.2% by weight, the content in the initial dissolution layer may be 50% by weight, and the content in the whole may be 6% by weight. Further, various other components such as known dyes, surfactants, and fragrances can be blended in any proportion.

The dye is not particularly limited as long as it is a water-soluble substance or a water-soluble substance which is not deteriorated by air oxidation or the like and is irritating to the eye mucous membrane or the like at the time of use. Of these, at least one kind can be used. For example, Amaranth (Red No. 2), Erythrosin (Red No. 3), New Coccin (Red 102)
No.), Phloxine B (Red No. 104 (1)), Rose Bengal (Red No. 105 (1)), Acid Red (Red No. 106), Tartrazine (Yellow No. 4), Sunset Yellow FCF (Yellow No. 5). ), Brilliant Blue FCF (Blue No. 1), Indigo Carmine (Blue 2)
No.), Fast Green FCF (Green No. 3), Resor Rubin B (Red No. 201), Resor Red (Red No. 20)
5), Rhodamine B (red 213), Rhodamine B
Acetate (Red 214), Brilliant Lake Red (R 219), Fast Acid Magenta (Red 227), Eosin YS (Red 230 (1)), Eosin YSK (Red 230 (2)) ,
Phloxine BK (Red No. 231), Rose Bengal K
(Red 232), orange (daidai 205
No.), erythrosine yellow NA (daidai 207), uranine (yellow 202 (1)), uranin K (yellow 2)
No. 02 (2)), Quinoline Yellow WS (Yellow 203)
No.), pyranine conc (green No. 204), light green SF yellow (green No. 205), patent blue NA (blue No. 202), patent blue CA (blue No. 203), alphazurin FG (blue No. 205), resorcin brown (Brown No. 201), Violamine R (Red 401
No.), Ponceau 3R (Red No. 205), Ponceau R (Red No. 503), Ponceau SX (Red No. 504), Fast Red S (Red No. 506), Orange I (Daidai No. 402), Polar Yellow 5G (Yellow 402). No.), naphthol yellow S (yellow 403 (1)), methanil yellow (yellow 406), fast light yellow 3G (yellow 407), naphthol green B (green 401).
No.), Guinea Green B (Green No. 402), Alizulol Purple (Purple No. 401), Naphthol Blue Black (Black No. 401), and the like.

These dyes can be used alone or in admixture of two or more in order to adjust running water to an arbitrary color tone. The compounding amount is 3 to 5 in the composition.
It is 0% by weight, preferably 5 to 25% by weight. Other surfactants can be used in combination with the above-mentioned nonionic surfactant having no water temperature dependency. The surfactant to be used in combination is not particularly limited as long as it is a commonly used one, and any of anionic surfactants, nonionic surfactants, cationic surfactants, etc. may be used alone or in combination. Can be appropriately selected and used. These surfactants have effects such as cleaning, dispersion, sterilization, antibacterial, etc., and the type and blending amount may be selected depending on which effect is given.

Among the above-mentioned surfactants, anionic surfactants and nonionic surfactants are preferable, and examples of the anionic surfactants include myristic acid, stearic acid, palmitic acid, behenic acid, Salts of higher fatty acids such as isostearic acid and oleic acid such as potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanolamine acid, the above alkali salts of ethercarboxylic acid, salts of N-acylamine acid, N- Acyl sarcon salts, higher alkyl sulfone hydrochloride and the like, and the nonionic surfactants include, for example, polyoxyethylene octyldodecyl alcohol, polyoxyethylene-branched alkyl ethers such as polyoxyethylene-2-decyltetradecyl alcohol, Polyoxy Polyoxyethylene-alkyl ethers such as ethylene-oleyl alcohol ether, polyoxyethylene behenyl alcohol ether, polyoxyethylene stearyl alcohol ether, polyoxyethylene-cetyl alcohol ether, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate Polyoxyethylene-sorbitan monooleate, polyoxyethylene-sorbitan monooleate, polyoxyethylene-sorbitan monoisostearate, polyoxyethylene-sorbitan monolaurate, etc. polyoxyethylene-sorbitan monooleate, glyceryl monostearate , Glycerin fatty acid esters such as glyceryl monomyristate, polyoxyethylene-glyceryl monooleate, Polyoxyethylene-glyceryl monomyristate and other polyoxyethylene-glycerin fatty acid esters, polyoxyethylene-dihydrocholesterol ester, polyoxyethylene-hardened castor oil, polyoxyethylene-hardened castor oil, polyoxyethylene such as isostearate- Hardened castor oil fatty acid ester, polyoxyethylene-nonylphenyl ether, polyoxyethylene-alkylphenyl ether such as polyoxyethylene-octylphenyl ether, ethylene glycol-propylene glycol block polymer, glyceryl isostearyl ether,
Glyceryl ether such as glyceryl myristyl ether, polyoxyethylene-glyceryl isostearyl ether, polyoxyethylene-glyceryl ether such as polyoxyethylene-glyceryl myristyl ether,
Examples thereof include polyglycerin fatty acid esters such as diglyceryl monostearate, decaglyceryl decasterate, decaglyceryl pentane isostearate, decaglyceryl decaisostearate, and diglyceryl diisostearate.

Other surfactants include cationic surfactants such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, dimyristyldimethylammonium methylsulfate, and lauryl. Amino acid type surfactants such as sodium aminopropionate and betaine type surfactants such as lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine Can be mentioned. These surfactants are added in the composition at 30%.
˜95% by weight, preferably 50 to 90% by weight.

Examples of the fragrances include essential oils extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, camphor, and limonene, linalool, linalyl acetate, borneol, citral,
Fragrances such as citronellal, menthol, and cineole can be used alone or in combination. As these fragrances, natural product fragrances, synthetic fragrances and the like can be arbitrarily used, and can be incorporated in the composition in an amount of 1 to 40% by weight, preferably 3 to 30% by weight. Furthermore, an acidic component, a bactericidal agent, an antibacterial agent, a pH adjusting agent, an enzyme, a sequestering agent, and the like can be added together depending on the purpose. As acidic components, iron rust in the toilet bowl and removal of calcium etc. due to excretion and prevention of deposition are confirmed.In addition to organic acids such as oxalic acid, inorganic acids such as sulfamic acid, and acidic salts such as ammonium bifluoride, metallin is further added. Those having a rust preventive action such as acid salts and orthophosphates can be used.

The bactericidal agent and antibacterial agent may be any ones that do not destroy or suppress the above-mentioned dyes, other additives such as surfactants and fragrances, and their effects when incorporated into the composition. In some cases, the above-mentioned surfactant has a bactericidal and antibacterial action, but a water-soluble bactericidal agent and an antibacterial agent may be blended separately, and examples thereof include salicylic acid, siabendazole, and benzoic acid ester. Further, examples of the pH regulator include sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, sodium silicate, sodium tartrate, tartaric acid, sodium citrate, citric acid, acetic acid, sodium acetate, and the like, and examples of the enzyme include protease and lipase. , Amylase, pectinase, cellulase and the like can be added as necessary. In addition to these, specific gravity adjusting agents such as inorganic salts, antifoaming agents such as silicone oil, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA)
A chelating agent or the like can be appropriately blended if necessary.

In the present invention, a method for imparting a desired color tone to running toilet water by using the solid composition for flush toilet using the monoester type nonionic surfactant is as follows. It is preferable to store it in a container to be installed outside. In detail,
It is set in the hand washing part of the upper lid of the flush toilet water storage tank, and every time a fixed amount of water is discharged by the water discharge tap, this water discharge comes into contact with the composition in the storage body and the active ingredient flows out into the water discharge. As long as the container has the container, the composition is filled and stored in a molded container of a suitable metal, plastic, non-woven fabric or the like, and the surface of the composition having a limited area flows in and out through a small hole provided in the container. It is preferred to dissolve in a limited amount of water. As a storage body that meets such a condition, an actual Kaihei 6-8470
The shape disclosed in Japanese Utility Model Publication No. 6-34080 is shown as an example.

When the composition according to the present invention is stored and filled in the above-mentioned container, the following storage is performed so that each component of the composition is efficiently present in the toilet running water. It is preferable to follow the filling method. First, it is divided into an initial dissolution layer that dissolves in contact with running water at the beginning of use and a slow-dissolving dissolution layer that dissolves in contact with running water after the initial dissolution layer is dissolved. The agent is mainly blended, and the slow-dissolving dissolution layer is blended with a surfactant, a fragrance and a dye for imparting effects such as cleaning, dispersion and antibacterial. By filling each of the dissolution layers into two layers in the storage body, the toilet running water can have a stable color tone from the beginning of use, and the water temperature dependency is also eliminated.

Further, the composition of the present invention is not limited to being stored and filled in the above-mentioned container, and can be used by directly putting it in the flush toilet water storage tank. In this case, it is preferable that the monoester type nonionic surfactant is uniformly mixed in the composition. And, the solid composition for flush toilet of the present invention,
Considering durability, storability and stability as a product, the melting point of the composition and various compounds is preferably 45 ° C or higher, more preferably 50 ° C or higher. When the melting point is in the normal temperature range (35 ° C. or lower), the composition may be melted or disintegrated during storage or transfer, and may not be suitable for use, which is not preferable. Behenic acid ethylene oxide adduct or stearic acid /
Behenic acid ethylene oxide adduct has the same detergency as ethylene oxide stearate adduct,
Its melting point is higher than that of the ethylene oxide stearate adduct. They are as seen in Table 1. In Table 1, the melting points ±, +, and ++ are +
The greater the number, the better.

[0023]

[Table 1]

[0024]

EXAMPLES The invention of this application will be described in more detail with reference to examples and comparative examples, but the invention is not limited thereto. Examples, Comparative Examples Each component was heated and melted at a ratio shown in Tables 2 to 4 below at about 60 to 80 ° C., and 3 g as an initial dissolution layer and 22 g as a slowly dissolving layer were formed into a mold having an appropriate shape. It was poured and cooled to solidify to obtain a solid composition for flush toilets having a total weight of 25 g. In the table, the content of each component is% by weight, and
EO is ethylene oxide, PEG is polyethylene glycol, POE is polyoxyethylene, and POP is polyoxypropylene.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

Experimental Examples Using the solid compositions for flush toilets of Examples 1 to 12 and Comparative Examples 1 to 3 shown in Tables 2 to 4, the water temperature dependency of the compositions and the color tone of running water were examined in the following experiments. Measurement and observation were carried out by the method, and the results are shown in Table 2. A container is filled with the solid composition for flush toilet of each of the Examples and Comparative Examples, and the solid composition is stored and stored in a hand washing part (INAX DT873:
INAX). And 5 ° C, 15 ° C and 2
Water at 5 ° C. was made to flow 5 times at intervals of 5 minutes, 3 liters at a time, and the color tone of each running water was measured by measuring the absorbance and visually observing. For the measurement of the absorbance, a value of 629 nm was measured using a V-1000 type spectrophotometer (manufactured by Hitachi, Ltd.). At the same time, the color tone and the difference of each running water were visually confirmed to examine the stability. The measurement results are shown in Table 5.
The evaluation method is as follows. 1 to 5 above
The difference in the measured absorbance values at each water temperature for each running water
The degree of water temperature dependency was evaluated by setting the value to be less than 0.1 ... O, 0.1 to 0.2 ... Δ, greater than 0.2 ... ×. Further, the color tone of each running water was visually observed 1 to 5 times, and the color tone was stable ... ◯, not stable ... ×, and the color tone from the initial use and its stability were evaluated.

[0029]

[Table 5]

[0030]

EFFECTS OF THE INVENTION The flush toilet flushing solid composition according to the present invention provides a stable color tone from the initial use even at running water temperature of the toilet, especially at low water temperature in winter, and gives a stable color tone until the end. Can be provided. Then, it can be used by filling it in a container installed outside the toilet water storage tank or, in some cases, throwing it directly into the water storage tank for use. Since the solid composition for flushing toilets according to the present invention has a higher melting point than the case where the fatty acid is stearic acid alone, even if there is a temperature rise during storage or transportation of the product, deformation or quality It rarely causes a problem that causes deterioration.

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Claims (7)

(57) [Claims] 1. A base material having excellent water solubility, which does not depend on water temperature.
Henic acid, or behenic acid and stearic acid ethylene
A solid composition for flush toilet cleaning, comprising a pigment, which is characterized by being blended with a nonionic surfactant which is solid at room temperature and which comprises an oxide adduct . 2. A base material having excellent water solubility, which does not depend on water temperature.
Henic acid, or behenic acid and stearic acid ethylene
A solid composition for flushing toilets containing a dye, comprising a color stabilizer comprising an oxide adduct and containing a nonionic surfactant that is solid at room temperature. 3. A water temperature, characterized by blending behenic acid, or behenic acid and stearic acid with a monoester type nonionic surfactant which is obtained by adding 50 to 120 moles of ethylene oxide. A solid composition for flushing toilets, which contains a pigment capable of obtaining a stable color tone without depending on 4. A monoester type nonionic surfactant comprising behenic acid or a mixture containing stearic acid and behenic acid as a main component, to which ethylene oxide is added, and the addition mole number of ethylene oxide is 70 to 100. A solid composition for flush toilet cleaning, containing a pigment capable of obtaining a stable color tone independent of the water temperature. 5. The flush toilet flush solid according to any one of claims 1 to 4, wherein the flush toilet flush solid composition is formed in two layers, a slow-dissolving dissolution layer and an initial dissolution layer. Composition. 6. The solid composition for flush toilet cleaning according to any one of claims 1 to 5 is stored in a container installed outside the flush toilet water storage tank and used by contacting with running water of the flush toilet. Characterized by, independent of water temperature,
A method of providing stable color toilet flush water. 7. A container having a structure in which at least a part of the solid composition for flush toilet cleaning according to any one of claims 1 to 5 is in contact with water, and the composition is stored in the container. A cleaning material for flush toilets.