JP2013032437A - Detergent composition for toilet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for a toilet, which shows stability in a shape of an adherent material even if the adherent material is applied on the surface of the toilet, and which is excellent in slow solubility to repetitive flashing.SOLUTION: The detergent composition for the toilet comprises: (a) 21-50 mass% of specific polyalkylene glycol; (b) a calcium chloride and/or a magnesium chloride; and (c) water. The mass ratio of (b)/(c) is 0.08 to 0.7.

Description

  The present invention relates to a toilet bowl cleaning composition.

  With regard to flushing toilet bowls, conventionally, there has been known a detergent composition for the purpose of continually washing the toilet bowl and keeping it clean by eluting the detergent active ingredient into the wash water in the tank. It has been. These are known as auto cleaners for toilets. For example, Patent Document 1 describes a cleaning gel composition that is slowly soluble in water and contains carrageenan, a cleaning agent, and a fragrance as a gelling agent. Patent Document 2 describes a cleaning composition containing calcium chloride and a surfactant. The composition absorbs water due to the hygroscopic property of calcium chloride, and the absorbed water dissolves a chemical such as a surfactant and acts on the object as a cleaning agent. Patent Document 3 discloses a nonionic surfactant for maintaining the adhesion to a hard surface of a preparation, an anionic surfactant for foaming, and calcium sulfate for adjusting the specific gravity of the preparation. An input-type solid fragrance cleaning agent containing is described.

  There has also been proposed a type of cleaning agent that is applied directly to a toilet or the like and allows the active ingredient to be released slowly with flash water. In Patent Document 4, a cleaning composition that continues to adhere to a hard surface when discharged from a container and a cleaning component discharged from the container adhere to and solidify on the hard surface, and then gradually dissolves the active ingredient while gradually dissolving with water. A cleaning method for cleaning by releasing is described.

JP-A-57-162799 Japanese Unexamined Patent Publication No. 2002-3388 JP-A-10-140186 JP 2005-187511 A

  As described above, toilets that do not have a tank are increasing in recent years. For such toilets, it is not possible to use a conventional toilet auto cleaner in which the cleaning agent is gradually dissolved in the cleaning water in the tank. Therefore, there is a demand for a composition for a toilet autocleaner that can be applied to a toilet without a tank, and a cleaning method using such a composition. However, Patent Documents 1 to 3 do not describe any adhesion of the cleaning composition to the toilet surface. On the other hand, the composition containing a water dissolution delay component and a cleaning component described in Patent Document 4 can be used by being applied to the toilet surface. However, after application, the composition is left on the toilet surface for a long time after being applied. As a result, crystals are generated due to the volatilization of water, the transparency is lost, and further, insolubilization or collapse occurs, and the performance that should be originally exhibited cannot be exhibited.

  Accordingly, an object of the present invention is to provide a toilet cleaner composition that is stable in the form of deposits and is excellent in gradual dissolution with respect to repeated flashes even after being applied to the surface of a toilet. . Furthermore, the subject of this invention is providing the cleaning composition for toilet bowls which was excellent also in the maintainability of a cleaning power.

The present invention comprises (a) 21 to 50% by mass of a polyalkylene glycol represented by the following general formula (a1) [hereinafter referred to as component (a)], (b) calcium chloride and / or magnesium chloride [hereinafter referred to as (b And (c) water (hereinafter referred to as (c) component), and the mass ratio (b) / (c) between (b) and (c) is 0.08 to 0.7. The present invention relates to a toilet bowl cleaning composition.
^R1a- O-[(PO) _m / (EO) _n ] -H (a1)
[Wherein R ^1a is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, and m and n represent the average number of moles added of PO and EO, respectively. , Each is a number from 0 to 100, and m and n are numbers that do not become 0 at the same time. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]

Moreover, this invention relates to the toilet bowl washing | cleaning method including the process of the following 1-2.
Process 1: The process of apply | coating the cleaning composition for toilets of the said invention to a toilet bowl.
Step 2: Applying water to the composition applied in Step 2 to form a cleaning medium containing (a) and water, and applying the cleaning medium to a toilet bowl.

  ADVANTAGE OF THE INVENTION According to this invention, even after apply | coating to the surface to a toilet bowl, the form of the deposit | attachment is stable and the toilet bowl cleaning composition excellent in the slow solubility with respect to repeated flash | flush is provided. Furthermore, according to this invention, the cleaning composition for toilet bowls excellent also in the maintainability of a cleaning power is provided.

<(A) component>
The toilet bowl cleaning composition of the present invention contains a compound selected from polyalkylene glycols represented by the following general formula (a1) as component (a). The component (a) is a cleaning component, and is also a component that affects the adhesion of the cleaning composition for toilet according to the present invention to the toilet surface, the form stability after adhesion, and the durability of the cleaning power.
^R1a- O-[(PO) _m / (EO) _n ] -H (a1)
[Wherein R ^1a is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, and m and n represent the average number of moles added of PO and EO, respectively. , Each is a number from 0 to 100, and m and n are numbers that do not become 0 at the same time. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]

In general formula (a1), R ^1a is a hydrocarbon group having 8 to 22 carbon atoms. From the viewpoint of adhesion to the toilet bowl surface of the toilet cleaner composition of the present invention, form stability after adhesion, and durability of detergency, R ^1a is a linear or branched alkyl group having 8 to 22 carbon atoms. Alternatively, an alkenyl group is preferable, a linear alkyl group or alkenyl group having 8 to 22 carbon atoms is more preferable, and a linear alkyl group having 8 to 22 carbon atoms is still more preferable. Moreover, from the viewpoints of adhesion to the toilet surface of the toilet bowl cleaning composition of the present invention, form stability after adhesion, and durability of detergency, R ^1a has 8 or more carbon atoms, preferably 12 That's it. From the viewpoint of the cleaning performance of the toilet bowl cleaning composition of the present invention and the form stability after adhering to the toilet bowl, the carbon number of R ^1a is 22 or less, preferably 18 or less, more preferably 14 or less. It is.

Further, (a) component adhesion to the toilet surface of the toilet bowl detergent compositions of the present invention, the form stability after attachment, and in view of sustainability of detergency, in the general formula (a1), R ^1a May be a mixture of compounds having hydrocarbon groups having different carbon numbers.

Moreover, in the toilet bowl cleaning composition of the present invention, the proportion of the compound having 12 to 18 carbon atoms of R ^{1a in} the component (a) is preferably 20 to 100 from the viewpoint of durability of the cleaning power. % By mass, more preferably 40 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 100% by mass.

  Moreover, in general formula (a1), m is a number of 0-100. From the viewpoint of adhesion to the toilet surface, form stability after adhesion, detergency, and durability of detergency, it is preferably 30 or less, more preferably 5 or less, more preferably 1 or less, Even more preferably 0.

  In general formula (a1), n is a number from 0 to 100, and n and m are not 0 at the same time. From the viewpoint of adhesion to the toilet bowl surface and morphological stability after adhesion, n is 0 or more, preferably 10 or more, and more preferably 20 or more. From the viewpoint of detergency and durability of detergency, it is 100 or less, preferably 80 or less, more preferably 70 or less, still more preferably 50 or less, and even more preferably 30 or less.

  The component (a) is preferably a compound wherein m in the general formula (a1) is 0, n is 20 to 80, and further 20 to 30.

<(B) component>
The toilet bowl cleaning composition of the present invention contains calcium chloride and / or magnesium chloride as the component (b). The component (b) is a component that has hygroscopicity or deliquescence and maintains the form stability and transparency of the deposit after application.

  The component (b) is preferably calcium chloride, more preferably calcium chloride anhydride and calcium chloride dihydrate, from the viewpoint of the form stability and transparency of the deposit after application of the toilet bowl cleaner composition, and calcium chloride. Anhydrides are more preferred.

<(C) component>
The toilet bowl cleaning composition of the present invention contains water as the component (c).

<Cleaning composition for toilet bowl>
The toilet bowl cleaning composition of the present invention contains a component (a), a component (b), and a component (c) under specific conditions. In addition to a cleaning effect as an auto cleaner for toilets, Due to the adherence of the cleaning composition to the toilet surface and the excellent form stability after application of the cleaning composition for toilet bowl, the cleaning composition has excellent detergency.

  Although this reason is not certain, since the (a) component and the (c) component form a gel with an appropriate viscosity, the adhesiveness of the toilet cleaner composition to the toilet surface is expressed. Furthermore, by containing the component (b) having hygroscopicity at a specific ratio with respect to the component (c), the volatilization of the component (c) can be prevented, and the excellent form stability and detergency of the adhered composition can be prevented. It is thought that persistence is expressed. At that time, as shown in a comparative example to be described later, even if the compound has a hygroscopic property, a compound not corresponding to the component (b) cannot obtain the effect of the present invention. It is inferred that a unique effect is manifested by a different mechanism of action.

  In the toilet bowl cleaning composition of the present invention, the amount of the component (a) is 21 to 55% by mass. From the viewpoint of gel formation and adhesion to a toilet bowl, it is 21% by mass or more, preferably 25% by mass or more, and more preferably 35% by mass or more. Morphological stability, detergency maintenance, and adhesion From the viewpoint of the subsequent transparency maintaining property, it is 55% by mass or less, preferably 40% by mass or less.

  The toilet bowl cleaning composition of the present invention preferably contains 5% by mass or more, more preferably 6% by mass or more from the viewpoint of the form stability after adhering the component (b), and the form stability after adhering, From the viewpoint of maintaining transparency after adhesion, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. In the present invention, the mass of the component (b) for calculating mass% and mass ratio is the mass in terms of anhydride.

  The toilet bowl cleaning composition of the present invention contains water as the component (c) together with the above components. The water content is an amount that is adjusted so that the total amount of the toilet bowl cleaning composition is 100% by mass. That is, the balance of the toilet bowl cleaning composition is water.

  The mass ratio (b) / (c) of the (b) component and the (c) component of the toilet bowl cleaning composition of the present invention is 0.08 to 0.7. (B) / (c) is 0.08 or more, preferably 0.09 or more from the viewpoint of maintaining the form stability after adhesion and the transparency after adhesion, and maintains transparency after adhesion. From the viewpoint, it is 0.7 or less, preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.2 or less.

  The mass ratio (a) / (c) of the component (a) and the component (c) of the toilet bowl cleaning composition of the present invention is a viewpoint of form stability after adhesion, transparency maintenance property after adhesion, and slow solubility. To preferably 0.3 to 1.5, more preferably 0.3 to 1.0, still more preferably 0.5 to 1.0, and particularly preferably 0.7 to 0.9.

  The toilet bowl cleaning composition of the present invention has a quaternary ammonium salt type bactericidal property having one or two hydrocarbon groups having 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, for the purpose of imparting bactericidal properties. You may mix | blend the cationic surfactant which it has [henceforth (d) component].

  Examples of the cationic surfactant include one or more cationic surfactants selected from a cationic surfactant represented by the following general formula (d1) and a cationic surfactant represented by the general formula (d2). Agents are preferred.

[Wherein R ^1d is a hydrocarbon group having 8 to 18 carbon atoms, or

(In the formula, R ^5d , R ^6d , R ^7d , R ^9d and R ^10d are each independently an alkyl group having 1 to 3 carbon atoms, and R ^8d , R ^11d and R ^12d are each independently having 1 to 3 carbon atoms. R ^2d and R ^3d each independently represents an alkyl group having 1 to 3 carbon atoms, and R ^4d represents an alkylene group having 1 to 3 carbon atoms. Z ⁻ represents an anion group, preferably a halogen ion, an amino acid ion, a fatty acid soap anion residue, a phosphate ester anion residue having a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, phosphone Polycyclic aromatic having acid ester anion residue, sulfonate ester anion residue or sulfate ester anion residue, or styrene sulfonate ion having a polymerization degree of 3 or more, or having a hydrocarbon group as a substituent An anionic oligomer or polymer containing a formalin condensate of a sulfonated compound is shown. ]

[Wherein, R ^13d and R ^14d each independently represents a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group having 6 to 14 carbon atoms and a total carbon number of R ^13d and R ^14d of 16 to 26. R ^15d and R ^16d are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (OR ^17d ) _n —OH (wherein R ^17d is an alkenyl group having 2 to 4 carbon atoms, and n is 1 Represents a number of from 10 to 10.), and Z ⁻ represents the same meaning as described above. ]

In general formula (d1), R ^1d is preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an alkyl group having 8 to 14 carbon atoms, from the viewpoint of bactericidal properties. In general formula (d2), R ^13d and R ^14d are each independently preferably an alkyl group having 8 to 12 carbon atoms. Further, Z ⁻ in the general formulas (d1) and (d2) is preferably a halogen ion.

  The content of the cationic surfactant is preferably 0.1 to 5% by mass and more preferably 1 to 3% by mass in the composition from the viewpoint of bactericidal properties.

  The toilet bowl cleaning composition of the present invention may contain a cleaning component other than the component (a) [hereinafter referred to as component (e)]. As the cleaning component, a surfactant is preferable, and among these, a nonionic surfactant other than the component (a) is preferable.

  Preferred components (e) include (e-1) alkyl glyceryl ether type surfactant (hereinafter referred to as (e-1) component) and (e-2) amphoteric surfactant (hereinafter referred to as (e). -2) component], (e-3) alkanolamide surfactant (hereinafter referred to as component (e-3)) and (e-4) amine oxide surfactant (hereinafter referred to as component (e-4) And the like.

The component (e-1) preferably contains an alkyl glyceryl ether having 6 to 18 carbon atoms in the alkyl group. Specifically, the compound of the following general formula (e1) is suitable.
R ^1e —O— (Gly) _r —H (e1)
[Wherein, R ^1e represents an alkyl group having 6 to 18 carbon atoms, Gly represents a residue obtained by removing two hydrogen atoms from glycerin, r represents an average number of added moles, and represents a number of 1 to 4. . ]

The structure represented by Gly is the structure represented by —CH ₂ CH (OH) CH ₂ — in which the 1-position and 3-position hydroxy groups of glycerol are bonded, or the 1-position and 2-position hydroxy groups of glycerol are bonded. The structure is represented by —CH (CH ₂ OH) CH ₂ —, which varies depending on the catalyst and reaction conditions.

  (E-1) Content of a component is 0.1-10 mass% in a composition, Furthermore, 1-5 mass% is preferable.

  Examples of the component (e-2) include betaine-type surfactants, amino acid-type surfactants, and imidazoline-type surfactants, and any of them may be used as long as it is used in a normal cleaning composition. Examples of such betaine-type surfactants include sulfobetaines such as ralylsulfobetaine, alkylbetaines such as lauryldimethylbetaine, alkylamidopropylbetaines such as coconut fatty acid amidepropylbetaine, and 2-undecyl-1-carboxyl. Examples thereof include imidazolinium betaines such as methyl-1-hydroxyethylimidazolinium betaine and 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine. The content of the component (e-2) is preferably 0.1 to 10% by mass and more preferably 1 to 5% by mass in the composition from the viewpoint of gel stability.

  Examples of the component (e-3) include amidated products of alkanolamines such as monoethanolamine, diethanolamine, and methylmonoethanolamine with fatty acids such as lauric acid and myristic acid. The content of the component (e-3) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass in the composition from the viewpoint of gel stability.

  As the component (e-4), N-alkanoylaminopropyl-N, N-diaminomethyl oxide (lauroyl or myristyroyl as alkanoyl), N-alkyl-N, N-diaminomethyl oxide (lauryl group as alkyl group or Myristyl group). The content of the component (e-4) is preferably 0.1 to 10% by mass and more preferably 1 to 5% by mass in the composition from the viewpoint of gel stability.

  The content of the component (a) in the cleaning composition of the present invention is such that the composition after adhering is gradually dissolved relative to the total content of the components (a), (d), and (e). From a viewpoint, Preferably it is 30-100 mass%, More preferably, it is 50-100 mass%, More preferably, it is 80-100 mass%. This is a ratio obtained by [(a) component content] / [(a) component content + (d) component content + (e) component content] × 100.

  To the toilet bowl cleaning composition of the present invention, a builder component [hereinafter referred to as component (f)] may be blended for the purpose of improving cleaning properties. Examples of the builder component include the following.

(I) Amino acids such as aspartic acid, glutamic acid and glycine, and alkali metal salts or alkanolamine salts thereof.

(Ii) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid, etc. Aminocarboxylic acids and alkali metal salts or alkanolamine salts thereof;

(Iii) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, and other organic acids, and alkali metal salts thereof Or an alkanolamine salt.

  Among these, hydroxycarboxylic acids such as citric acid and malic acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and hydroxyethylethylenediaminetriacetic acid, and salts thereof are preferable. The salt form is preferably a sodium salt, potassium salt, ammonium salt or alkanolamine salt.

  The content of the builder component is preferably 0.1 to 5% by mass, particularly preferably 1 to 3% by mass in the composition from the viewpoint of detergency.

  In the present invention, the combination of the cationic surfactants represented by the general formulas (1) and (2) and the builder components described in the above (i) to (iii) is used in the toilet water seal part. The effect of preventing generated ring dirt is further improved. Therefore, it is preferable to use a combination of a cationic surfactant and a builder component. The mass ratio of the cationic surfactant to the builder component is preferably 0.1 to 10 and more preferably in the range of 0.5 to 2 in terms of the cationic surfactant / builder component. Although the reason for this is not clear, the builder component and the cationic surfactant cause a weak interaction, which causes ring contamination by preventing the cationic surfactant from being adsorbed and stabilized on the toilet surface. It is considered that a bactericidal effect is expressed in the water seal portion.

The toilet bowl cleaning composition of the present invention preferably has a viscosity at 25 ° C. of 10 Pa · s or more from the viewpoint of adhesion to the toilet bowl and morphological stability on the toilet bowl surface. The viscosity of the composition can be measured using, for example, Physica MCR-301 manufactured by Anton Paar, CP50-1 (Series 3275) as a plate, and a shear rate of 0.1 s- ¹ . The viscosity at 25 ° C. is more preferably 10 Pa · s or more and 1,000 Pa · s or less from the viewpoint of adhesion to the toilet bowl and morphological stability on the toilet bowl surface.

  Moreover, it is preferable that the toilet bowl cleaning composition of the present invention is gradually soluble in water. Here, being slowly soluble in water means that a mass of 0.60 to 0.65 g is taken at a position of about 3 cm from a rim in a toilet (C730B manufactured by TOTO), a diameter of 12 to 15 mm, and a thickness of about 5 mm. When the composition is applied in a disk shape and repeatedly flashed at intervals of 2 minutes, it is necessary to flash 6 times or more, preferably 15 times or more until the composition after adhesion completely disappears. In this case, the composition may be applied to a plurality of places in one toilet, preferably two places, and the test may be performed, and an average value of the number of flushes until each composition disappears may be employed. Moreover, since it can be judged that it has sufficient slow solubility if the frequency | count of flush is 100 times or more, the upper limit of the frequency | count of flush can be set to 100 times.

  The pH at 25 ° C. of the toilet bowl cleaning composition of the present invention is preferably 2 to 13, more preferably 3 to 11, and particularly preferably 3 to 7. The pH is measured by diluting the composition with distilled water or the like, for example, until the surfactant concentration becomes 1% by mass, using a Horiba Ltd. pH meter D-52S, pH electrode 6367-10D. Can do.

<How to wash the toilet bowl>
In the toilet bowl cleaning method of the present invention, the cleaning composition of the present invention is applied to a toilet bowl, and water is applied to the applied gel composition to elute the polyoxyalkylene alkyl ether of component (a). To clean the toilet bowl. Specifically, the following steps 1-2 are included.
Process 1: The process of apply | coating the cleaning composition for toilets of the said invention to a toilet bowl.
Step 2: Applying water to the composition applied in Step 2 to form a cleaning medium containing component (a) and water, and applying the cleaning medium to a toilet bowl.

  Examples of the application of the cleaning composition to the toilet in Step 1 include a method of applying using a tool such as a spatula, and a method of applying by filling and extruding into a syringe-like tool. The application amount of the cleaning composition is preferably 2 to 15 g, more preferably 3 to 10 g per use on the toilet surface. 2 g or more is preferable from the viewpoint of durability of the detergency, and 15 g or less is preferable from the viewpoint of use efficiency of the cleaning composition.

  In step 2, water is applied to the composition applied in step 1 (for example, by bringing running water into contact) to form a cleaning medium containing component (a) and water, and the cleaning medium is applied to the toilet bowl. In step 1, the composition of the present invention having a viscosity of preferably 10 Pa · s or more at 25 ° C. is applied. If the cleaning composition for toilet bowl of the present invention applied in step 1 is washed per flush in a general flush toilet, peeling, excessive dissolution, decrease in viscosity, etc. due to contact with water The cleaning component containing the component (a) is released by contact with the water staying at the application site, and the toilet bowl is cleaned. That is, the cleaning is performed when the cleaning medium containing the component (a) and water comes into contact with the toilet. (A) The washing | cleaning medium containing a component and water can contain the water-soluble component from a gel suitably. The cleaning composition of the present invention may be a toilet cleaning medium composition, a toilet cleaning composition, or a toilet autocleaner composition.

  In this invention, it is preferable to apply | coat a cleaning composition to the rim | limb part (edge back part) of a seat-type flush toilet (what is called a Western-style toilet bowl). Usually, a seat-type flush toilet is provided with a supply port for washing water for cleaning the inner wall surface of the bowl of the toilet body, and in many cases, a water discharge port is provided on the back of the periphery of the toilet. In this invention, it is preferable to apply | coat the cleaning composition of this invention downstream of the flow path of the wash water discharged | emitted from a seat-type flush toilet in process 1, and to form a gel.

<Example 1 and Comparative Example 1>
Using the components shown in Tables 1 and 2, toilet bowl cleaning compositions of Examples and Comparative Examples were obtained. Each toilet bowl cleaning composition was applied and tested for the form stability, transparency maintenance, and gradual solubility of the composition after application and adhesion by the following methods.

In addition, about the composition in which the following symbols were described in the various evaluation column in a table | surface, evaluation could not be performed for each reason.
(Note 1) The blended composition did not become a gel and did not adhere to the toilet surface. Alternatively, the blended composition flowed immediately after application on the petri dish surface.
(Note 2) Precipitation occurred in the blended composition and could not be applied.
(Note 3) The blended composition was separated and could not be evaluated.

(Morphological stability)
In the center of the glass petri dish, 0.5 g of the composition was weighed and applied in a mountain shape (diameter 14 mm, height 10 mm). This petri dish is inclined by 30 ° and left in a room at 20 ° C. and 70% RH. The form of the composition after 7 days was evaluated according to the following evaluation criteria.
4; height of the composition after 7 days is 8 mm or more 3; height of the composition after 7 days is 3 mm or more and less than 8 mm 2; height of the composition after 7 days is 1 mm or more and less than 3 mm 1; composition after 7 days Less than 1mm in height

(Transparency maintenance)
Next, in the form stability test, the appearance of the composition remaining in the first applied part was observed after 7 days and evaluated according to the following evaluation criteria. About the composition moved from the first applied part at the time point after 7 days, the compounded composition that could not be applied due to further precipitation (the above Note 2), and the composition that could not be separated and evaluated (the above Note 3) Did not evaluate.
3; The attached composition is transparent (the composition has no non-uniform turbidity and transmits light) 2; A part of the attached composition is cloudy 1; The whole composition is cloudy

(Slow solubility)
Take a mass of 0.60-0.65g in two places on the right side (3cm from the rim) 5cm from the point on the 3cm water seal side from the center rim in the front center in the toilet (C730B made by TOTO), The composition was applied in a disk shape having a diameter of 12 to 15 mm and a thickness of about 5 mm, and flashing was repeated. The interval between flushes was 2 minutes, and flushing was continued until the deposits were completely removed, and the number of times was used as a measure of slow dissolution. However, the upper limit of the flash was 100 times. When flushing is performed under these conditions, those that require flushing 6 times or more, preferably 15 times or more, until the composition after adhesion completely disappears, have slow solubility. Tables 1 and 2 show the average value of the number of flashes at two locations.

(Viscosity of composition)
Physica MCR-301 manufactured by Anton Paar, CP50-1 (Series 3275) was used as a plate, and the shear rate was 0.1 s ⁻¹ . As a result, the viscosities at 25 ° C. of the compositions of the examples were all in the range of 10 Pa · s to 1,000 Pa · s.

The components in the table are as follows. P is the average number of moles added.
* 1 Sanisole C (manufactured by Kao Corporation)
* 2 Emanon 3199RV (Kao Corporation)

  From the results of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2, if the content of component (a) is within a predetermined range, the blended composition becomes a uniform gel. On the other hand, when the content of the component (a) is less than the range of the present invention (Comparative Example 1-1), the composition does not become a gel, and it remains on the toilet surface even when the composition is applied. I found out I couldn't. Moreover, when there is more content of (a) component than the range of this invention (comparative example 1-2), it will be in the non-uniform | heterogenous state which a part of compounding component isolate | separated and cannot be used as an auto cleaner for toilets. I understood.

  From the results of Examples 1-4 to 1-6 and Comparative Examples 1-3 to 1-5, when the mass ratio (b) / (c) is smaller than the range of the present invention (Comparative Examples 1-3, 1- 4) is inferior in form stability and transparency maintenance of the composition after application and adhesion, and when it is large (Comparative Example 1-5), a part of the composition is precipitated and cannot be used as a toilet auto cleaner. I understood that.

  From the results of Comparative Examples 1-6 to 1-14, when the component (b) is not used, or even when a hygroscopic compound other than the component (b) is used instead of the component (b), the toilet auto cleaner It was found that the composition could not be used as Further, as in Comparative Example 1-14, even when sodium chloride capable of supplying chlorine ions and magnesium sulfate capable of supplying magnesium ions are used in combination, the effect of the present invention cannot be obtained. ) It was found that it was significant to use the compound of the component.

<Example 2 and Comparative Example 2>
Using the toilet bowl cleaning composition obtained in Example 1, the following methods evaluated the antifouling property and the antifouling property as an index of cleaning performance.

(Stain adhesion prevention and dirt removal)
(1) Pretreatment The composition is applied to a disk shape having a diameter of 12 to 15 mm and a thickness of about 5 mm at a location of about 3 cm from a rim in a toilet (C730B made by TOTO), and three compositions. Then, flush once and treat the inside of the toilet bowl with the dissolved composition.
(2) Test (2-1) Test 1st time After pre-treatment, oleic acid colored with 0.6% by mass of Sudan II was placed in front of the toilet water seal part (front) at about 10 cm (approx. A total of 0.1 g) was dropped, and it was confirmed whether or not the colored oleic acid remained visually in the dropping part. The state at this time was evaluated as antifouling adhesion, and evaluated according to the following five levels. Next, flushing was performed once, and the soil removability was evaluated based on whether or not the dropped oleic acid remained above the water seal portion. Evaluation was performed in the following five stages.

(2-2) Second test to fifth test After the first test, the second to fifth tests were continuously performed without performing pretreatment. That is, oleic acid colored with 0.6% by mass of Sudan II was dropped at about 10 cm in front of the toilet seal (front) and at approximately four locations (total 0.1 g), and oleic acid remained in the dripping part. Was confirmed visually. The state at this time was evaluated for the second time for anti-stain adhesion, and then flushed once to evaluate the soil removability (second time) of whether or not the dropped oleic acid remained above the water seal. did. This operation was repeated, and the evaluation of stain adhesion prevention and stain removal was evaluated up to a total of five times. The antifouling property and the dirt removal performance were evaluated each time. The results are shown in Table 3.

(Evaluation criteria for dirt adhesion prevention)
5: There is no adhesion at the dropping part (0 places)
4; Adhering to the dropping part 1; 3; Adhering to the dropping part 2; 2; Adhering to the dropping part 3; 1; Adhering to the dropping part 4

(Evaluation criteria for dirt removal)
5: Residual oleic acid cannot be confirmed at any of the four locations.
4; Partial residue of oleic acid is observed only in one of the four locations 3; Partial residual of oleic acid is observed in two to four of the four locations 2; 1-3 of the four locations Oleic acid remains in almost the same state as the dropped part 1; oleic acid remains in almost the same state as the dropped part in all four places

  As a result of the stain adhesion prevention test and the stain removal property test, it was found that the composition of the present invention has excellent stain adhesion prevention property and stain removal property.

  According to the present invention, after applying to the surface of a toilet bowl, the form of the deposit is stable, and the toilet bowl cleaning composition having excellent gradual solubility against repeated flashes and the composition are used. A toilet bowl cleaning method is provided.

Claims (6)

(A) 21 to 50% by mass of polyalkylene glycol represented by the following general formula (a1), (b) calcium chloride and / or magnesium chloride, and (c) water, (b) and (c) The toilet bowl cleaning composition whose mass ratio (b) / (c) is 0.08-0.7.
^R1a- O-[(PO) _m / (EO) _n ] -H (a1)
[Wherein R ^1a is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, and m and n represent the average number of moles added of PO and EO, respectively. , Each is a number from 0 to 100, and m and n are numbers that do not become 0 at the same time. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]   The toilet bowl cleaning composition according to claim 1, which has a viscosity at 25 ° C of 10 Pa · s or more.   The toilet cleaner composition according to claim 1 or 2, wherein the mass ratio (a) / (c) of (a) to (c) is 0.3 to 1.5.   The toilet bowl cleaning composition according to any one of claims 1 to 3, which contains 5 to 25 mass% of (b).   The toilet cleaner composition according to any one of claims 1 to 4, wherein (a) is a compound wherein m in the general formula (a1) is 0 and n is 20 to 80. A toilet cleaning method comprising the following steps 1-2.
Process 1: The process of apply | coating the toilet bowl cleaning composition of any one of Claims 1-5 to a toilet bowl.
Step 2: Applying water to the composition applied in Step 2 to form a cleaning medium containing (a) and water, and applying the cleaning medium to a toilet bowl.