JP7130533B2 - Cleaning composition for flush toilet - Google Patents

Description

The present invention provides a cleansing toilet for flushing toilets with excellent foaming properties by containing a specific cationic surfactant, a polyoxyethylene alkyl ether type nonionic surfactant, a fatty acid alkanolamide and an alcohol having 2 to 6 carbon atoms. Regarding the composition.

Cleaning agents used in flush toilets include so-called on-tank ones that are used by placing them in the hand wash section of the water storage tank of the flush toilet, and those that are attached to the rim of the toilet bowl of the flush toilet. Further, various forms are known, such as one arranged in a water storage tank of a flush toilet. Among them, on-tank ones are widely used because they are easy to install and replace.
This on-tank cleaning agent is used with a solid or liquid cleaning composition loaded in a chemical supply container. By flushing water from the flush toilet, the water that flows out from the hand washing unit flows into the on-tank chemical supply container, and the water with the cleaning agent eluted is stored in the water storage tank, or in the water storage tank. The cleansing composition is dripped naturally and then flushed to discharge from the water storage tank into the toilet bowl. In addition, the user can obtain a high sense of use by generating abundant foam inside the toilet bowl during flushing.
On the other hand, in the toilet bowl, in addition to stains such as feces, urinary stones, scale, and the like, stains derived from microorganisms such as blackheads are generated. In order to suppress such stains derived from microorganisms, it is effective to incorporate an antibacterial agent into the cleaning agent, and a general cationic surfactant is widely used as the antibacterial agent. Certain cationic surfactants such as quaternary ammonium salts are excellent in antibacterial action, and can be applied to cleaning agents for flush toilets (for example, Patent Document 1) or used in combination with nonionic surfactants. It has been proposed to use it as a device (for example, Patent Document 2). However, when some cationic surfactants are used in combination with a substance that induces an ion exchange reaction, the interaction not only impairs the antibacterial action, but also causes the formation of insoluble matter, resulting in foaming that is satisfactory to the user. The problem was that I didn't get it.

JP 2006-321884 A JP 2001-329294 A

When the toilet bowl is flushed, rich foaming occurs inside the toilet bowl, so that the user can get a high feeling of use. However, cleaning compositions containing cationic surfactants such as quaternary ammonium salts, which are excellent in antibacterial action, have problems with foaming properties. Therefore, several cleaning agents with improved foaming properties have been proposed. However, it is difficult to say that sufficient foaming properties are obtained to satisfy many users, and further improvements have been desired.
Accordingly, an object of the present invention is to provide a cleaning composition for flush toilets, which is superior in both antibacterial action and foaming property to conventional cleaning agents.

As a result of intensive research to solve the above problems, the present inventors have found a specific cationic surfactant, a polyoxyethylene alkyl ether type nonionic surfactant, a fatty acid alkanolamide and a By containing alcohol, it is possible to obtain a cleaning agent with significantly improved foaming properties compared to cleaning agents containing conventional cationic surfactants, and furthermore, it is excellent in the sustainability of this foam. The inventors have found that and completed the present invention.
Among the cationic surfactants with antibacterial action in conventional detergents, by adopting those that form counterions with the anion ions of organic acids, excellent antibacterial action is maintained and high foaming is achieved. It was found for the first time that the properties and foam retention are excellent, and the above problems were solved.

［式中、Ｒ_１は炭素数８～１８のアルキル基であり、Ｒ_２は炭素数１～１８のアルキル基、ベンジル基または炭素数１～１０のアルキル鎖を有するアルキルフェニルジエトキシ基の何れかであり、Ｒ_３は炭素数１～４のアルキル基または－（ＣＨ_２ＣＨ_２Ｏ）_ｎ－Ｈ基（式中、ｎは０～５何れかの整数を表す。）の何れかであり、Ｒ_４は炭素数１～４のアルキル基である。Ｒ_１とＲ_２は同一であっても異なっていてもよく、Ｒ_３とＲ_４は同一であっても異なっていてもよい。Ａ^－は有機酸のアニオンイオンである。］
成分（ｂ）：下記一般式（２）で表されるＨＬＢが１０以上のノニオン系界面活性剤

［式中、Ｒ_５は炭素数９～２０のアルキル基であり、ｍは任意の整数である。］
成分（ｃ）：脂肪酸アルカノールアミド
成分（ｄ）：炭素数２～６のアルコール
２．オンタンク用に用いられる１．に記載の水洗トイレ用洗浄組成物。
３．１．または２．に記載の水洗トイレ用洗浄組成物を、貯水タンク上蓋に設置する容器に収納して適用することを特徴とする、水洗トイレ用洗浄組成物の使用方法。 Specifically, the gist of the present invention is as follows.
1. A cleaning composition for a flush toilet, comprising the following components (a), (b), (c) and (d).
Component (a): a cationic surfactant represented by the following general formula (1)

[In the formula, R ₁ is an alkyl group having 8 to 18 carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyldiethoxy group having an alkyl chain having 1 to 10 carbon atoms. and R ₃ is either an alkyl group having 1 to 4 carbon atoms or a —(CH ₂ CH ₂ O) _n —H group (wherein n represents an integer of 0 to 5) , R ₄ is an alkyl group having 1 to 4 carbon atoms. R ₁ and R ₂ may be the same or different, and R ₃ and R ₄ may be the same or different. A ⁻ is an anion of an organic acid. ]
Component (b): A nonionic surfactant represented by the following general formula (2) and having an HLB of 10 or more

[In the formula, R ₅ is an alkyl group having 9 to 20 carbon atoms, and m is an arbitrary integer. ]
Component (c): Fatty acid alkanolamide Component (d): Alcohol having 2 to 6 carbon atoms2. Used for on-tank 1. 2. The cleaning composition for flush toilets according to .
3.1. or 2. 2. A method for using a flush toilet cleaning composition, characterized in that the flush toilet cleaning composition according to 1. is housed in a container to be installed on the upper lid of a water storage tank and applied.

The flush toilet cleaning composition of the present invention comprises a cationic surfactant that forms a counterion with an anion of an organic acid, a polyoxyethylene alkyl ether type nonionic surfactant that is a specific HLB, and a fatty acid alkanolamide. and an alcohol having 2 to 6 carbon atoms, the foaming property is remarkably improved, and further, a cleaning agent excellent in the persistence of the foam can be obtained. Moreover, since the cleaning composition for flush toilets of the present invention contains a specific cationic surfactant having an antibacterial action, it is possible to obtain excellent antibacterial properties in addition to excellent foaming properties.
As a result, the cleaning composition for flush toilets of the present invention can remove microbial-derived black stains adhering to flush toilets and various other types of stains with long-term stable detergency. In particular, the flush toilet cleansing composition of the present invention produces abundant foam inside the toilet bowl when flushing the toilet, so that the user can obtain a high feeling of use. In addition, the flush toilet cleaning composition of the present invention is useful because it can be suitably used as an on-tank cleaning agent.

［式中、Ｒ_１は炭素数８～１８のアルキル基であり、Ｒ_２は炭素数１～１８のアルキル基、ベンジル基または炭素数１～１０のアルキル鎖を有するアルキルフェニルジエトキシ基の何れかであり、Ｒ_３は炭素数１～４のアルキル基または－（ＣＨ_２ＣＨ_２Ｏ）_ｎ－Ｈ基（式中、ｎは０～５何れかの整数を表す。）の何れかであり、Ｒ_４は炭素数１～４のアルキル基である。Ｒ_１とＲ_２は同一であっても異なっていてもよく、Ｒ_３とＲ_４は同一であっても異なっていてもよい。Ａ^－は有機酸のアニオンイオンである。］ Hereinafter, the flush toilet cleaning composition of the present invention will be described in detail.
<Component (a)>
The flush toilet cleaning composition of the present invention contains a cationic surfactant represented by the following general formula (1) as component (a).

[In the formula, R ₁ is an alkyl group having 8 to 18 carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyldiethoxy group having an alkyl chain having 1 to 10 carbon atoms. and R ₃ is either an alkyl group having 1 to 4 carbon atoms or a —(CH ₂ CH ₂ O) _n —H group (wherein n represents an integer of 0 to 5) , R ₄ is an alkyl group having 1 to 4 carbon atoms. R ₁ and R ₂ may be the same or different, and R ₃ and R ₄ may be the same or different. A ⁻ is an anion of an organic acid. ]

The cationic surfactant represented by the general formula (1) functions as a component having antibacterial and bactericidal action in the flush toilet cleaning composition of the present invention, and the present general formula (2). By combining the component (b) of the invention, the fatty acid alkanolamide of the component (c), and the alcohol having 2 to 6 carbon atoms (d), the foaming property is remarkably improved, and the foam persistence is improved. It is possible to obtain a cleaning composition excellent in
In the above general formula (1), R ₁ is an alkyl group having 8 to 18 carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyl group having an alkyl chain having 1 to 10 carbon atoms. any ethoxy group, R ₁ and R ₂ may be the same or different, and R ₂ is an alkyl group having 1 to 4 carbon atoms or 8 to 18 carbon atoms, a benzyl group, a carbon An alkylphenyldiethoxy group having an alkyl chain of 8 to 10 numbers is preferable, an alkyl group having 8 to 18 carbon atoms, a benzyl group, and an alkylphenyldiethoxy group having an alkyl chain of 8 carbon atoms are more preferable, and 18 alkyl groups are particularly preferred. R ₃ is either a C 1-4 alkyl group or a —(CH ₂ CH ₂ O) _n —H group, R ₄ is a C 1-4 alkyl group, and R ₃ and R ₄ may be the same or different, and R ₄ is preferably a methyl group or a --(CH ₂ CH ₂ O) _n --H group. A ⁻ is an anion of an organic acid. Examples of anions of organic acids include carboxylate ions such as propionate ion and adipate ion, sulfate ions such as methosulfate ion and ethosulfate ion, phosphate ions such as cetylphosphate ion, carbonate ion, Examples include sulfonate ions, among which carboxylate ions and sulfate ions are preferred. In order to obtain excellent foaming properties, it is extremely important that the counter ion of component (a) of the flush toilet cleaning composition of the present invention is not a halogen but an organic acid.
With such a component (a) cationic surfactant, it is possible to obtain an excellent improvement in foamability and an effect of maintaining it.

Specific examples of cationic surfactants represented by the general formula (1) include: dilauryldimethylammonium, dimyristyldimethylammonium, dicetyldimethylammonium, distearyldimethylammonium, benzalkonium and the like. Among these, as the component (a) of the present invention, didecyldimethylammonium methosulfate, didecyldimethylammonium ethosulfate, didecyldimethylammonium propionate, didecyldimethylammonium adipate, didecylmonomethylpolyoxyethylammonium methoxide Sulfate, didecylmonomethylpolyoxyethylammonium ethosulfate, didecylmonomethylpolyoxyethylammonium propionate, didecylmonomethylpolyoxyethylammonium adipate are preferred, didecyldimethylammonium methosulfate, didecyldimethylammonium ethosulfate, didecyl Dimethylammonium propionate, didecyldimethylammonium adipate, didecylmonomethylpolyoxyethylammonium propionate are particularly preferred.

In the flush toilet cleaning composition of the present invention, the amount of the cationic surfactant (a) to be blended is not particularly limited, but is preferably in the range of 1.0 to 50.0% by weight, and 3.0 to 30.0% by weight. A range of 0% by weight is more preferred, and a range of 5.0 to 25.0% by weight is particularly preferred.
In addition, the concentration of the component (a) cationic surfactant when used is, for example, when used as an on-tank liquid detergent, the liquid detergent drips naturally into the tank or when it is flushed, the inside of the container When the liquid detergent is eluted, the liquid detergent accumulates in the tank together with the water. It means the concentration in the tank at this time, and the concentration is in the range of 0.1 to 25.0 ppm. It is preferable to design

［式中、Ｒ_５は炭素数９～２０のアルキル基であり、ｍは任意の整数である。］ <Component (b)>
The flush toilet cleaning composition of the present invention contains, as component (b), a nonionic surfactant having an HLB of 10 or more represented by the following general formula (2).

[In the formula, R ₅ is an alkyl group having 9 to 20 carbon atoms, and m is an arbitrary integer. ]

In the general formula (2), R ₅ represents a linear or branched (isotype) alkyl group having 9 to 20 carbon atoms. The nonionic surfactant represented by the general formula (2) may be a single compound or a mixture as long as R ₅ has 9 to 20 carbon atoms.
The nonionic surfactant of the component (b) of the present invention has an HLB (Hydrophile-Lipophile Balance) of 10 or more, preferably in the range of 10 or more and 18 or less. A nonionic surfactant having an HLB of less than 10 as the component (b) of the present invention cannot improve foamability or maintain foamability.
Here, in the nonionic surfactant represented by the general formula (2), it is known that the number of added moles of ethylene oxide (EO) and HLB are generally correlated. Changing the number of moles can be done by methods well known in the art. In addition, the HLB value can be calculated by several methods well known in the art, and was calculated by the Griffin method in the present invention. In the nonionic surfactant represented by the general formula (2), m is an arbitrary integer, but when R ₅ is linear, m is preferably an integer of 5 to 50, Integers from 6 to 30 are particularly preferred.

Commercially available nonionic surfactants can be used as the component (b) of the present invention. Commercially available products include, for example, Fine Surf D-1307 (POE (7) decyl ether, HLB: 13.2, manufactured by Aoki Yushi Kogyo Co., Ltd.), Safety Cut LI-3062 (POE (7) alkyl (C9- 11) Ether, HLB: 12.8, manufactured by Aoki Oil Industry Co., Ltd.), Safetycut LI-3085 (POE (8) alkyl (C9-11) ether, HLB: 13.9, manufactured by Aoki Oil Industry Co., Ltd.), etc. is mentioned. Here, for example, when POE (7) alkyl (C9-11) ether is explained, "POE" is polyoxyethylene, (7) is m in the general formula (2), alkyl (C9-11) means an alkyl mixture of 9 to 11 carbon atoms. These component (b) nonionic surfactants can be used alone or in combination of two or more.
In the flush toilet cleaning composition of the present invention, the nonionic surfactant content of component (b) is preferably more than 5.0% by weight to enhance detergency. In particular, when the cleaning composition for flush toilets of the present invention is used as an on-tank cleaning agent, it is preferable because a high-concentration formulation is possible.
In the flush toilet cleaning composition of the present invention, the component (b) nonionic surfactant can be appropriately blended within the range of more than 5.0% by weight and not more than 45% by weight, depending on the purpose. .

<Component (c)>
The flush toilet cleaning composition of the present invention contains a fatty acid alkanolamide as component (c). Specific examples of fatty acid alkanolamides include lauric acid diethanolamide, lauric myristate diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, fatty acid (8 to 18 carbon atoms) methylethanolamide, coconut oil fatty acid diethanolamide, Palm kernel fatty acid diethanolamide, modified coconut fatty acid diethanolamide, coconut fatty acid monoethanolamide, stearic acid monoethanolamide, lauric acid monoisopropanolamide, coconut fatty acid N-methylethanolamide. Among them, fatty acid (8 to 18 carbon atoms) methylethanolamide, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, and coconut oil fatty acid N-methylethanolamide are preferred.
Conventionally, fatty acid alkanolamides have been known to have the effect of enhancing the foaming properties of anionic surfactants, and have therefore been used in combination with detergents. , does not contain anionic surfactants. In the present invention, by blending a cationic surfactant that forms a counterion with an anion of an organic acid and a polyoxyethylene alkyl ether type nonionic surfactant with a fatty acid alkanolamide, rich foaming can be achieved. The present inventors have found that it is possible to achieve the present invention. This was first clarified by the present inventors through various experiments described later, and is an extremely excellent finding.
In the present invention, the amount of fatty acid alkanolamide as component (c) is preferably 0.1% by weight or more and 20% by weight or less, more preferably 0.3% by weight or more and 15% by weight or less, in the composition. .5% by weight or more and 10% by weight or less is particularly preferred.

<Component (d)>
The flush toilet cleaning composition of the present invention contains an alcohol having 2 to 6 carbon atoms as component (d), including monohydric alcohols, dihydric alcohols and trihydric alcohols. Component (d) includes ethanol, 1-propanol, isopropanol, 1-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, propylene glycol monomethyl ether, propylene glycol-n-propyl ether, diethylene glycol monomethyl ether. , In addition to hexanediol, 2-methoxyethanol, 2-methoxypropanol, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, etc. are preferred, and component (d) is one or two. More can be used.
In the present invention, the amount of the alcohol having 2 to 6 carbon atoms as the component (d) is preferably 0.1% by weight or more and 20% by weight or less in the composition, and 0.5% by weight or more and 15% by weight or less. More preferably, 1% by weight or more and 10% by weight or less is particularly preferable.

The flush toilet cleaning composition of the present invention can be obtained by a known production method using a known formulation aid.
<Other components (formulation aids)>
The flush toilet cleaning composition of the present invention may optionally contain surfactants, fragrances, pigments, viscosity modifiers, etc. other than components (a) to (c) as long as the effects of the present invention are not impaired. good too.

<Other surfactants>
The flush toilet cleaning composition of the present invention may contain surfactants other than components (a) to (c). Examples of surfactants that may be contained in the flush toilet cleaning composition of the present invention include nonionic surfactants such as amine oxides, amidoamine oxides, POE alkylamines, glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose. Fatty acid esters, polyoxyalkylene alkyl ethers other than component (b), alkyl polyglucosides, etc. Cationic surfactants include quaternary ammonium salts other than component (a), benzalkonium salts, benzethonium salts, pyridinium salts, Examples include imidazolinium salts and biguanide compounds, and amphoteric surfactants include alkylcarboxybetaine, alkylsulfobetaine and the like. Moreover, the amount of the optional surfactant in the flush toilet cleaning composition is preferably, for example, 0 to 10% by weight. The flush toilet cleaning composition of the present invention preferably does not contain an anionic surfactant.

<Perfume>
Fragrances include, for example, essential oils extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, camphor; limonene, linalool, linalool acetate, borneol, citral, citronellal, menthol, cineol and other natural fragrances and synthetic fragrances. In addition, plant extracts such as Japanese cypress and tea can also be used as deodorizing fragrances. These perfumes are preferably blended in an amount of 0.5 to 25% by weight, more preferably 1 to 20% by weight, in the flush toilet cleaning composition.

<Pigment>
As the dye, water-soluble legal dyes are preferable, for example, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 2, Green No. 3, Red No. 201, Red No. 205, Red No. 213, Red No. 214, Red No. 219, Red No. 227, Red No. 230 (1), Red 230 No. (2), Red No. 231, Red No. 232, Orange No. 207, Yellow No. 202 (2), Yellow No. 203, Green No. 205, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Red No. 401, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403 (1), Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402, Purple 401 No. 401 black, and the like. Also, two or more of these dyes may be used in combination to give various colors. These pigments are preferably added in an amount of 0.01 to 5% by weight in the cleaning composition for flush toilets.

The flush toilet cleaning composition of the present invention may further contain a chelating agent, a specific gravity adjuster, an ultraviolet inhibitor, an antioxidant and the like. Furthermore, if necessary, it may contain an insect repellent component, an insecticidal component, a repellent component, a bactericidal component (antibacterial component), and the like.
The content of other components (formulation aids) in the flush toilet cleaning composition of the present invention is arbitrary and not particularly limited as long as the present invention can be achieved.

The cleaning composition for flush toilets of the present invention is used for cleaning flush toilets, and is particularly suitably used as a cleaning composition for on-tank flush toilets.
An example of the use of the flush toilet cleaning composition of the present invention for cleaning and removing stains from a toilet bowl is as follows. ), or the flush toilet cleaning composition of the present invention may be placed on the rim of the toilet bowl. As a result, in the case of an on-tank type, when flush water is re-stored in the tank after flushing the toilet, a predetermined amount of the flush toilet cleaning composition of the present invention is eluted or released into the flush water. Alternatively, the cleaning composition is dripped naturally, and the cleaning composition for a flush toilet of the present invention can be brought into contact with the soiled toilet bowl during cleaning (during flushing) of the toilet bowl. Here, the flush toilet means a toilet configured so that water is stored in a tank as flush water, and the flush water stored in the tank is flushed into the toilet bowl to clean the toilet bowl. .

Hereinafter, the cleaning composition for flush toilets of the present invention will be described in more detail based on test examples and the like, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight" unless otherwise specified.

<Foamability Evaluation 1>
The following evaluation test was conducted to confirm the effect of each of the components (a) to (c) of the present invention on the foamability of the flush toilet cleaning composition of the present invention.
(1) Preparation of Test Specimen Flush toilet cleaning compositions (Examples 1 to 6, Comparative Examples 1 to 5) was diluted with water to a concentration of 0.025% by weight, and this was used as a test specimen.
(2) Foaming property evaluation method Put 200 mL of the test sample in a 400 mL separatory funnel (the inner diameter of the tip of the leg is about 3 mm), put 50 mL in a 500 mL graduated cylinder, and place it 30 cm from the liquid surface in the graduated cylinder. The tip of the separatory funnel was placed at a height, and 200 mL of the test sample was dropped in about 15 seconds (range of 14 to 16 seconds). Measure the amount of foam (mL) formed on the liquid surface in the graduated cylinder immediately after dropping the entire amount of the test sample in the separating funnel and 3 minutes later. Amount of foam after minute (mL)”. Also, the foam retention rate (%) was calculated by the following formula.
"Calculation formula for foam retention rate"
Foam residual rate (%) = “foam volume after 3 minutes (mL)” ÷ “initial foam volume (mL)” × 100
Table 1 shows the "initial foam volume (mL)", "foam volume after 3 minutes (mL)", and "foam retention rate (%)" for each cleaning composition.
As the cleaning composition for flush toilets of the present invention, it was determined that a composition having an "initial foam volume (mL)" of 100 or more and a "foam retention rate (%)" of 80% or more was practical.

The following materials were used for the composition components used in the "foamability evaluation 1".
Didecyldimethylammonium methosulfate: Lion Specialty Chemicals Co., Ltd. Didecyldimethylammonium ethosulfate Didecylmonomethylpolyoxyethylammonium propionate: Lonza Japan Co., Ltd. Cetyltrimethylammonium methosulfate: Lion Specialty Chemicals Co., Ltd. Made by Didecyldimethylammonium Adipate: Made by Sanyo Chemical Industries, Ltd.
POE (7) alkyl (C9-11) ether: "Safety Cut LI-3062" HLB 12.8 manufactured by Aoki Oil Industry Co., Ltd.
Fatty acid (C8-C18) methyl ethanolamide: manufactured by Kao Corporation
3-Methoxy-3-methyl-1-butanol: "Solfit Fine Grade" manufactured by Kuraray Co., Ltd.
Polyvinylpyrrolidone: "PVP K-90" manufactured by Nippon Shokubai Co., Ltd.
Dioctyldimethylammonium chloride: manufactured by Lonza Japan Co., Ltd. Didecyldimethylammonium chloride: manufactured by Lonza Japan Co., Ltd. Distearyldimethylammonium chloride: manufactured by NOF Corporation
POE (3) lauryl ether: "Brownon EL-1503P" HLB8.3 manufactured by Aoki Oil Industry Co., Ltd.

As is clear from Table 1, all of the flush toilet cleaning compositions of Examples 1 to 6, which are specific examples of the present invention, have an initial foam volume of 100 mL or more and a foam retention rate of 80% or more, which is above the practical level. It was found to be a cleaning composition that has excellent foaming properties and excellent foam sustainability. In particular, the cleaning composition of Example 2 had an initial foam volume of 120 mL and a foam retention rate of about 94%.
On the other hand, the cleaning composition of Comparative Example 1, which does not contain the component (c) of the present invention, has a low initial foam volume and a low foam retention rate, and in particular exhibits an HLB different from that of the component (b) of the present invention. It was found that the cleaning composition of Comparative Example 5 containing a nonionic surfactant had extremely low initial foam volume and foam retention rate.
Surprisingly, the cleaning compositions of Comparative Examples 2 to 4 containing a cationic surfactant different from the component (a) of the present invention, in which "A ⁻ " in the general formula (1) is a chloride anion. Compared to the cleaning composition of Example 1, both the initial foam volume and the foam retention rate were greatly reduced, and it was also clear that the cleaning composition was not excellent in foamability.
Accordingly, in the flush toilet cleaning composition of the present invention, a component (a) that forms a counter ion with an anion of an organic acid is selected from among known cationic surfactants having an antibacterial action. It was found that a cleaning composition having high foaming properties and excellent foam retention can be obtained. This is a particularly remarkable effect that the present inventor confirmed for the first time through experiments.

<Foamability Evaluation 2>
In order to confirm the influence of the component (c) of the present invention on the foamability of the flush toilet cleaning composition of the present invention, the following test was conducted.
(1) Preparation of Test Specimen Flush toilet cleaning composition (Examples 1, 7, Comparative Example 6, 7) was diluted with water to a concentration of 0.025% by weight, and this was used as a test sample.
(2) Evaluation method of foamability A test was performed in the same manner as in "Evaluation of foamability 1" above, and the "initial foam volume (mL)" and the "foam volume after 3 minutes (mL)" were measured, The foam retention rate (%) was calculated by the above formula. Table 2 shows the "initial foam volume (mL)", "foam volume after 3 minutes (mL)", and "foam residual rate (%)" for each cleaning composition.

In "Foamability Evaluation 2", the composition components used in addition to "Foamability Evaluation 1" are as follows.
Coconut oil fatty acid diethanolamide: PPG-24 Glycereth-24 manufactured by Matsumoto Yushi Seiyaku Co., Ltd. PPG75-PEG300 Hexylene glycol manufactured by Sanyo Chemical Industries Co., Ltd.

As is clear from Table 2, the flush toilet cleaning compositions of Examples 1 and 7, which are specific examples of the present invention, had an initial foam volume and a foam It was found that both the residual ratio was at a practical level or higher, and the cleaning composition had excellent foamability and excellent foam sustainability.
On the other hand, the cleaning compositions of Comparative Examples 6 and 7, which contain nonionic surfactants, which are considered to be involved in foaming properties in the same way as fatty acid alkanolamides, instead of the component (c) of the present invention, have an initial foaming rate of It was found that the amount, especially the foam retention rate, was low, and it was not practical.
From this evaluation test, it was found that the cleaning composition for flush toilets of the present invention has high foaming property by including fatty acid alkanolamide as an essential component among nonionic surfactants that are considered to be involved in foaming property. It was found that a cleaning composition with excellent foam retention can be obtained.

<Foamability Evaluation 3>
In order to confirm the influence of the component (b) of the present invention on the foamability of the flush toilet cleaning composition of the present invention, the following test was conducted.
(1) Preparation of Test Specimens Cleansing compositions for flush toilets (Examples 1, 8 to 16, Comparative Example 5) was diluted with water to a concentration of 0.025% by weight, and this was used as a test specimen.
(2) Evaluation method of foamability A test was performed in the same manner as in "Evaluation of foamability 1" above, and the "initial foam volume (mL)" and the "foam volume after 3 minutes (mL)" were measured, The foam retention rate (%) was calculated by the above formula. Table 3 shows the "initial foam volume (mL)", the "foam volume after 3 minutes (mL)", and the "residual foam rate (%)" of each cleaning composition.

In "Foamability Evaluation 3", the composition components used in addition to "Foamability Evaluation 1" are as follows.
POE (10) cetyl ether: "Brownon CH-310L" HLB 12.9 manufactured by Aoki Oil Industry Co., Ltd.
POE (7) decyl ether: "Fine Surf D-1307" HLB13.2 manufactured by Aoki Oil Industry Co., Ltd.
POE (9) Lauryl ether: Kao Corporation "Emulgen 109P" HLB13.4
POE (30) lauryl ether: "Brownon EL-1530" HLB17.4 manufactured by Aoki Oil Industry Co., Ltd.

As is clear from Table 3, the cleaning compositions for flush toilets of Examples 1 and 8 to 16, which are specific examples of the present invention, differed in the type of nonionic surfactant as component (b). When the HLB is 10 or more, both the initial foam volume and the foam retention rate are at or above the practical level, and it has become clear that the cleaning composition has excellent foaming properties and excellent foam sustainability.
On the other hand, as described above, the cleaning composition of Comparative Example 5 containing a nonionic surfactant with an HLB of less than 10 was found to have extremely low initial foam volume and foam residual rate.
Moreover, it was confirmed that, as in Example 16, even when polyvinylpyrrolidone was not contained, a cleaning composition having excellent foaming properties and foam persistence could be obtained.
According to this evaluation test, the cleaning composition for flush toilets of the present invention is excellent in high foaming property and foam retention by using a polyoxyethylene alkyl ether type nonionic surfactant having an HLB of 10 or more as an essential component. It became clear that it can be used as a cleaning composition.

<Foamability Evaluation 4>
In order to confirm the influence of the component (d) of the present invention on the foamability of the flush toilet cleaning composition of the present invention, the following test was conducted.
(1) Preparation of Test Specimens Cleansing compositions for flush toilets (Examples 1, 17 to 19, Comparative Example 8) was diluted with water to a concentration of 0.025% by weight, and this was used as a test sample.
(2) Evaluation method of foamability A test was performed in the same manner as in "Evaluation of foamability 1" above, and the "initial foam volume (mL)" and the "foam volume after 3 minutes (mL)" were measured, The foam retention rate (%) was calculated by the above formula. Table 4 shows the "initial foam volume (mL)", "foam volume after 3 minutes (mL)", and "foam residual rate (%)" for each cleaning composition.

As is clear from Table 4, in the flush toilet cleaning compositions of Examples 1 and 17 to 19, which are specific examples of the present invention, the blending amount and type of the component (d) alcohol having 2 to 6 carbon atoms were changed. However, both the initial foam amount and the foam retention rate were above the practical level, and it was found that the cleaning composition was excellent in foaming properties and excellent in foam sustainability.
On the other hand, the cleaning composition of Comparative Example 8, which did not contain the component (d) of the present invention, had a low initial foam volume, particularly a low foam retention rate, and was found to be unpractical. According to this evaluation test, the cleaning composition for flush toilets of the present invention can be made into a cleaning composition with high foaming property and excellent foam retention by including the component (d) alcohol having 2 to 6 carbon atoms as an essential component. became clear.

The flush toilet cleaning composition of the present invention comprises a cationic surfactant that forms a counterion with an anion of an organic acid, a polyoxyethylene alkyl ether type nonionic surfactant that is a specific HLB, and a fatty acid alkanolamide. and an alcohol having 2 to 6 carbon atoms, the foaming property is remarkably improved, and further, a cleaning agent excellent in the persistence of the foam can be obtained. Moreover, since the flush toilet cleaning composition of the present invention contains a specific cationic surfactant having an antibacterial action, it is possible to obtain excellent antibacterial properties in addition to excellent foaming properties. , suitable as an on-tank cleaning agent.

Claims (3)

A cleaning composition for a flush toilet, comprising the following components (a), (b), (c) and (d).
Component (a): a cationic surfactant represented by the following general formula (1)

[In the formula, R ₁ is an alkyl group having 8 to 18 carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyldiethoxy group having an alkyl chain having 1 to 10 carbon atoms. and R ₃ is either an alkyl group having 1 to 4 carbon atoms or a -(CH ₂ CH ₂ O)nH group (wherein n represents an integer of 0 to 5). , R ₄ is an alkyl group having 1 to 4 carbon atoms. R ₁ and R ₂ may be the same or different, and R ₃ and R ₄ may be the same or different. A ⁻ is an anion of an organic acid. ]
Component (b): A nonionic surfactant represented by the following general formula (2) and having an HLB of 10 or more

[In the formula, R ₅ is an alkyl group having 9 to 20 carbon atoms, and m is an arbitrary integer. ]
Component (c): Fatty acid alkanolamide Component (d): Alcohol having 2 to 6 carbon atoms (excluding glycerol) The flush toilet cleaning composition according to claim 1, which is used for on-tank. 3. A method for using a flush toilet cleaning composition, comprising storing the flush toilet cleaning composition according to claim 1 or 2 in a container to be installed on the upper lid of a water storage tank.