JP2011219645A - Detergent composition for toilet bowl - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for toilet bowls which is easily applied to toilet bowls, and has a durable detergency.SOLUTION: The detergent composition for toilet bowls includes (a) a polyoxyethylene alkyl ether having a 14-22C alkyl group and an average number of moles of ethylene oxide moieties added of 20 to 80, and (b) ethanol, and has a viscosity of 50 to 3,000 mPa s at 25°C.

Description

  The present invention relates to a toilet bowl cleaning method.

  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.

  In addition, as a means that can be applied without being limited to the form of a flush toilet, a method is also known in which a slow-dissolving film is formed on the toilet surface to continuously wash the toilet. For example, Patent Documents 1 and 2 describe a cleaning method in which a component discharged from a container adheres to an arbitrary portion and solidifies, and then is washed by slowly releasing the active component while gradually dissolving with water.

  In addition, a method is also known in which a slow-dissolving gel is attached to the toilet surface, and the cleaning component is gradually released to continuously wash the toilet. For example, Patent Document 3 describes that an agent having a viscosity of 15000 mPa · s or more is directly applied to an object.

JP 2005-187511 A JP 2006-206882 A International Publication No. 02/26925 Pamphlet

  When cleaning a toilet bowl using a composition capable of forming a film that gradually releases the cleaning component, it is easy to apply to the toilet bowl (ease of taking out the cleaning composition from the container, easiness to adhere to the toilet bowl, uniform and It is desired that the cleaning composition is easily applied to a wide range and the cleaning power is excellent in durability.

  However, the composition containing the water dissolution delay component and the cleaning component described in Patent Document 1 is hardly soluble or collapses when the drying process is prolonged, and the slow dissolution characteristics of the components are impaired. Moreover, the composition containing the water dissolution delay component, the chemical | medical agent component, and solvent which are described in patent document 2 has little content of the component which contributes to detergency, and does not have sufficient detergency. In addition, the slow dissolution properties of the components are not sufficient. The composition described in Patent Document 3 has a very high viscosity and is designed to be partially retained by sticking the composition on the toilet surface, so it is suitable for applications that apply uniformly to the toilet surface. Not.

  The subject of this invention is providing the cleaning composition for toilet bowls excellent in the ease of application | coating to a toilet bowl, and the sustainability of the cleaning power.

  The present invention relates to (a) a polyoxyethylene alkyl ether whose alkyl group has 14 to 22 carbon atoms and an ethylene oxide average addition mole number of 20 to 80 (hereinafter referred to as component (a)), and (b) ethanol [ Hereinafter, it is referred to as (b) component], and relates to a toilet bowl cleaning composition having a viscosity at 25 ° C. of 50 to 3000 mPa · s.

Moreover, this invention relates to the toilet bowl washing | cleaning method including the process of following 1-3.
Process 1: The process of apply | coating the cleaning composition for toilets of the said invention to a toilet bowl.
Process 2: The process of volatilizing (b) from the composition apply | coated at the process 1 by leaving it for 1 minute-3 hours after the process 1, and forming a gel with higher viscosity than the composition before application | coating.
Step 3: A step of applying water to the gel formed in Step 2 to produce a washing medium containing (a) and water, and applying the washing medium to a toilet bowl.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for toilet bowls excellent in the ease of application | coating to a toilet bowl and the durability of a cleaning power is provided.

<Cleaning agent composition>

  The viscosity of the cleaning composition of the present invention at 25 ° C. (hereinafter referred to as initial viscosity) is 50 to 3000 mPa · s, preferably 100 to 2500 mPa · s, and more preferably 150 to 2000 mPa · s. It is 50 mP · s or more from the viewpoint of adherence of the cleaning composition to the toilet bowl, and 3000 mP · s or less from the viewpoint of workability such as ease of discharge when the composition is contained in a container.

  The cleaning composition of this invention contains the polyoxyethylene alkyl ether whose carbon number of an alkyl group is 14-22 and whose ethylene oxide average addition mole number is 20-80 as (a) component. The component (a) is a cleaning component and a component that contributes to imparting the initial viscosity and forming a high-viscosity gel after ethanol volatilization. (A) Carbon number of the alkyl group of a component is 14-22, and 16-18 are preferable. It is 14 or more from the viewpoint of adhesion to the toilet and detergency, and is 22 or less from the viewpoint of ease of extracting the composition from the container. Moreover, the ethylene oxide average addition mole number of (a) component is 20-80, 25-70, Furthermore, 30-60 are preferable. It is 20 or more from the viewpoint of detergency, and 80 or less from the viewpoint of adhesion to the toilet. The cleaning composition of the present invention preferably contains 14 to 64% by mass, further 15 to 60% by mass, and more preferably 20 to 50% by mass of the component (a). 14 mass% or more is preferable from a viewpoint of detergency maintenance and the adhesiveness to a toilet bowl, and 64 mass% or less is preferable from a viewpoint of the ease of taking out the composition from a container.

  The cleaning composition of the present invention can contain a cleaning component other than the component (a). As the cleaning component, a surfactant is preferable, and among these, a nonionic surfactant other than the component (a) is preferable. Here, as the nonionic surfactant other than the component (a), a surfactant having a polyoxyethylene (ethylene oxide average added mole number of 1 to 6) chain is preferable, specifically, polyoxyethylene (ethylene oxide). Average addition mole number 1-6) alkenyl (carbon number 8-18) ether, polyoxyethylene (ethylene oxide average addition mole number 1-6) alkyl (carbon number 8-18) phenyl ether, ethylene oxide addition (ethylene oxide average addition) Number of moles 1-6) Alkyl (carbon number 8-18) group or alkenyl (carbon number 8-18) group-containing nonionic surfactant mixture, polyoxyethylene group (ethylene oxide average addition mole number 1-6) Alkyl (8 to 18 carbon atoms) amine oxide, polyoxyethylene group (ethylene oxide It added mole number 1 to 6) containing fatty acid (number 8-18) alkanolamide such as carbon and the like.

  The cleaning composition of the present invention contains ethanol as the component (b). The component (b) is a component that contributes to the provision of the initial viscosity together with the component (a), and is a volatile component, so the viscosity of the composition is increased by volatilizing the component (b) from the composition. Can be made. The cleaning composition of the present invention preferably contains 2 to 30% by mass, and further 3 to 15% by mass of component (b). It is preferably 2% by mass or more from the viewpoint of easy extraction of the composition from the container and a uniform and wide application range, and is preferably 30% by mass or less from the viewpoint of adhesion to the toilet bowl and durability of cleaning power.

  The cleaning composition of the present invention can contain a volatile alcohol other than the component (b). Here, the “volatile component” refers to a substance that has a saturated vapor pressure of 1 kPa or higher at 20 ° C. and volatilizes at 20 ° C. and normal pressure.

  The detergent composition of the present invention has a bactericidal quaternary ammonium salt type having one or two hydrocarbon groups having 6 to 16 carbon atoms, preferably 8 to 14 carbon atoms for the purpose of imparting bactericidal properties. An active surfactant may be added.

  As said cationic surfactant, 1 or more types of cationic surfactant chosen from the cationic surfactant represented by the following general formula (1) and the cationic surfactant represented by General formula (2) Agents are preferred.

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

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms, and R ⁸ , R ¹¹ and R ¹² are each independently having 1 to 3 carbon atoms. R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms, and R ⁴ 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. ]

[In the formula, R ¹³ and R ¹⁴ 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 ¹³ and R ¹⁴ of 16 to 26. R ¹⁵ and R ¹⁶ are independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (OR ¹⁸ ) _n —OH (wherein R ¹⁸ 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 (1), R ¹ 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 detergency. In the general formula (2), R ¹³ and R ¹⁴ are preferably an alkyl group having 8 to 12 carbon atoms independently. Further, as Z ⁻ in the general formulas (1) and (2), a halogen ion is preferable.

  The content of the cationic surfactant is preferably 0.1 to 8% by mass and more preferably 1 to 5% by mass in the composition from the viewpoint of bactericidal properties.

  In the cleaning composition of the present invention, a builder component may be blended for the purpose of improving detergency. 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) Aminocarboxylic acids such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid 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, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, and other organic acids Alkali metal salt or alkanolamine salt.

  Among these, hydroxycarboxylic acids such as citric acid and malic acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid 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 0.2 to 3% by mass in the composition from the viewpoint of detergency.

  In the present invention, by using a combination of the cationic surfactants represented by the above general formulas (1) and (2) and the builder components described in the above (i) to (iii), This improves the effect of preventing ring contamination that occurs on the surface. Therefore, it is preferable to use a combination of a cationic surfactant and a builder component. The weight ratio of the cationic surfactant to the builder component is preferably in the range of 10/1 to 1/10 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, preventing the cationic surfactant from adsorbing and stabilizing on the toilet surface, thereby causing water sealing that causes ring contamination. It is thought that the bactericidal effect is expressed in the part.

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

  The detergent composition of the present invention forms a gel having a viscosity higher than the viscosity of the composition before volatilization due to volatilization of ethanol as component (b). Specifically, the viscosity of the gel formed by volatilization of ethanol as component (b) is preferably 10 Pa · s or more at 25 ° C., more preferably 100 Pa · s or more, and further preferably 1000 Pa · s or more. . The viscosity of the gel is a viscosity of the gel formed after the component (b) is volatilized from the cleaning composition, and can be measured using, for example, TOKIMEC VISCOMETER MODEL BM (manufactured by TOKIMEC INC). Hereinafter, the viscosity of this gel is called “viscosity after volatilization” for convenience. A gel having such a viscosity after volatilization can be formed by sufficiently volatilizing ethanol from the composition, and after the above-described application operation on the toilet surface, the ambient temperature (for example, room temperature) where the toilet is installed is 1 minute to A method of drying for 3 hours is the simplest method. The viscosity after volatilization is preferably 10 Pa · s or more from the viewpoint of the detergency of the gel. The toilet bowl cleaning composition of the present invention was obtained by uniformly applying 10 g to a glass petri dish having an inner diameter of 85 mm and drying it at 40 ° C. and a humidity of 50% for 3 hours. It is preferable to form a gel of 10 Pa · s or more.

  Moreover, it is preferable that the gel formed by volatilization of ethanol which is (b) component is gradually soluble in water. Here, being slowly soluble in water means that 10 g of the composition is uniformly applied to a glass petri dish having an inner diameter of about 85 mm and dried in an environment of 40 ° C. and humidity of 50% for 3 hours. It is a physical property such that when 10 g of 25 ° C. tap water is gently added and left for 1 minute, a part of the component (a) is dissolved in the tap water.

  The composition of the present invention filled in a squeeze container is ejected and applied to the toilet surface, the composition of the present invention filled in a spray container is sprayed and applied to the toilet surface, and the like. By allowing the composition to adhere and allowing the ethanol to evaporate, it is possible to form a gel having the viscosity after volatilization and preferably soluble in water.

  The pH at 25 ° C. of the 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 using a Horiba Ltd. pH meter D-52S and a pH electrode 6367-10D.

<How to wash the toilet bowl>
The toilet bowl cleaning method of the present invention comprises applying the cleaning composition of the present invention to a toilet bowl, volatilizing (b) ethanol from the applied composition, and having a high viscosity and preferably a water-soluble gel. And (a) polyoxyethylene alkyl ether is eluted by applying water to the gel to wash the toilet bowl. Specifically, the following steps 1 to 3 are included.
Process 1: The process of apply | coating the toilet bowl cleaning composition of this invention to a toilet bowl.
Process 2: The process of volatilizing (b) from the composition apply | coated at the process 1 by leaving it for 1 minute-3 hours after the process 1, and forming a gel with higher viscosity than the composition before application | coating.
Step 3: A step of applying water to the gel formed in Step 2 to produce a washing medium containing (a) and water, and applying the washing medium to a toilet bowl.

  The application of the cleaning composition to the toilet bowl in step 1 is a method of discharging the liquid filled in the squeeze container and applying the liquid to the toilet bowl surface, and a method of applying the liquid filled in the spray container to the toilet bowl surface. Etc. The application amount of the cleaning composition is preferably 2 to 50 g, more preferably 5 to 40 g per use on the toilet surface. 2 g or more is preferable from the viewpoint of durability of the detergency, and 50 g or less is preferable from the viewpoint of use efficiency of the cleaning composition.

  Although it does not specifically limit as a squeeze container, Preferably the container as described in Unexamined-Japanese-Patent No. 2009-298426 is mentioned. The container body includes a flexible container body and a pressure regulating member that regulates the pressure deformation of the container body within the container body, and discharges the content liquid by pressing the container body.

Although it does not specifically limit as a spray type container, Preferably the spray container (it is called a trigger type spray container) with which the trigger type sprayer was mounted | worn is mentioned. Examples of the trigger type spray container include a container body containing a liquid detergent composition, and a trigger type liquid ejector attached to the mouth part of the container body, and further, the mouth part of the container body. Is mounted with a trigger sprayer for ejecting a liquid detergent composition, a vertical pipe and a horizontal pipe are formed in the trigger sprayer, and the vertical pipe and the horizontal pipe are formed in the vertical pipe. A spray container (referred to as spray container (I)) in which a valve for blocking communication with the road is provided. The volume of the horizontal line in the spray container (I) is preferably 0.1~0.28cm ^3, volume under the valve of the vertical pipe is preferably 0.06~0.19cm ^3. The spray container (I) is provided with a cylinder at a lower position of the horizontal pipe, and a spin element is mounted at the tip of the horizontal pipe, and a nozzle having a nozzle hole is fitted at the tip of the spin element. It is fixed. The spray container (I) pulls the trigger, discharges the air in the cylinder to the outside, and when the trigger is returned, the liquid detergent composition is sucked up through a vertical pipe immersed in the liquid detergent composition of the container body. By filling the cylinder with liquid and pulling the trigger again, the liquid in the cylinder is pushed out and led to the vertical pipe, and the liquid flow is spun through the horizontal pipe and the spin element, and finally from the nozzle. It is of the type that erupts. As the trigger type spray container, for example, a trigger spray container of “Bath Magiclin Foaming Spray” (Kao Co., Ltd.) washed and dried can be used.

  In step 2, ethanol as the component (b) is volatilized from the composition to form a gel having a higher viscosity than the composition before coating. In step 2, it is preferable to evaporate ethanol as component (b) from the composition to form a viscosity gel of 10 Pa · s or higher at 25 ° C. The gel formed in step 2 is preferably gradually soluble in water. When the coating amount of the composition in step 1 is in the above range, it is usually higher in viscosity than the composition before coating by allowing it to stand at room temperature for several minutes to several hours, specifically for 1 minute to 3 hours. Preferably, a gel that is gradually soluble in water is formed.

  In step 3, water is applied to the gel formed in step 2 (for example, contact with running water, etc.) to produce a cleaning medium containing (a) and water, and the cleaning medium is applied to the toilet bowl. In Step 2, after the gel viscosity reaches 10 Pa · s or higher at 25 ° C., application of water to the gel in Step 3 can be started. If the gel formed from the cleaning composition of the present invention in Step 2 is washed per flush in a general flush toilet, peeling, excessive dissolution, viscosity reduction, 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 washing water discharged | emitted from a seat-type flush toilet in process 1, 2, and to form a gel.

  Using the components shown in Tables 1 and 2, cleaning compositions of Examples and Comparative Examples were obtained. Comparative Example 13 in Table 2 is the composition described in Example 6 of Patent Document 1, and Comparative Example 14 in Table 2 is the composition described in Example 10 of Patent Document 2. pH (25 degreeC) was adjusted with 6N-sodium hydroxide aqueous solution or 6N-hydrochloric acid as needed. Using each of the cleaning compositions, tests for ease of application, cleaning durability, and prevention of ring contamination were conducted by the following methods. Moreover, the initial viscosity of the composition and the viscosity after volatilization were measured by the following methods. The results are shown in Tables 1 and 2.

(Measurement method of viscosity)
The apparatus for measuring the initial viscosity is TOKIMEC INC. A TOKIMEC VISCOMETER MODEL BM manufactured by KK was used. The measurement conditions were 25 ° C. and the rotor was No. 3 was used to set the number of revolutions to 30 rpm, and the measured value one minute after the start of measurement was taken as the initial viscosity.

The viscosity after volatilization was measured using a sample obtained by uniformly applying 10 g of the composition to a glass petri dish having an inner diameter of 85 mm and drying it in an environment of 40 ° C. and 50% humidity for 3 hours. In the composition containing ethanol, ethanol is volatilized under these conditions. The measuring apparatus was Physica MCR-301 manufactured by Anton Paar, and CP50-1 (series 3275) was used as a plate, and measurement was performed at 25 ° C. and a shear rate of 0.1 s ⁻¹ .

(Easy application)
The ease of application when the cleaning composition of Table 1 was applied to the edge back of a Western-style toilet using a 500 ml squeeze container was evaluated. It is defined that the cleaning composition can be discharged simply by grasping the squeeze container, and that the cleaning composition adheres and can be easily applied to the rim of a Western-style toilet. Ten test subjects performed the application work on the toilet toilet rim, and evaluated according to the following evaluation criteria.
1: 0 to 2 persons answered that they could be applied easily.
2: 3-5 responded that they could be applied easily.
3: Six to eight people answered that they could be applied easily.
4: 9-10 responded that they could be applied easily.

(Washing durability)
Using a 500 ml squeeze container, 20 g of the cleaning composition was applied to the edge back of a Western-style toilet and dried at room temperature for 1 hour to form a gel. In the examples, a gel having a viscosity higher than the initial viscosity and gradually soluble in water was formed. 20 μl of model soil (oleic acid: 49.95% by mass, triolein: 49.95% by mass, sudan III: 0.10% by mass) was applied to the toilet surface with a pipette every hour from 9:00 to 17:00 every day. Later, a flash operation was performed. This operation was performed for five consecutive days from Monday to Friday, and the operation was interrupted on Saturday and Sunday. This operation was repeated and evaluated according to the following evaluation criteria.
After 1 to 10 flash operations, there is residual dirt.
2: After 11 to 30 flash operations, there is residual dirt.
3: After 31 to 50 flash operations, dirt remains.
4: No dirt remains after 50 flash operations.

(Ring dirt prevention)
The washing sustainability evaluation method was performed, and the period until ring-shaped dirt was generated on the draft line of the liquid reservoir in the toilet bowl was evaluated according to the following evaluation criteria. Since ring contamination once generated cannot be easily removed by flash operation, the test was terminated when it occurred once.
1: Ring contamination is present after 50 flash operations 2: Ring contamination is not confirmed after 50 flash operations, but ring contamination is confirmed before 70 flash operations 3: 70 operations Ring contamination is not confirmed after the flash operation, and ring contamination is confirmed until the 90th flash operation 4: Ring contamination is not confirmed after the 90th flash operation, and until the 110th flash operation 5: No ring dirt is present after 110 flash operations.

The components in the table are as follows. P is the average number of moles added.
* 1 Cetyl group / stearyl group = 13/87 (mass ratio)
* 2 Sanisole C (manufactured by Kao Corporation)
* 3 HEC Daicel SE-900 (manufactured by Daicel Chemical Industries, Ltd.)
* 4 Coatamine D10E (manufactured by Kao Corporation)

Claims (6)

  (A) a polyoxyethylene alkyl ether having an alkyl group having 14 to 22 carbon atoms and an average number of moles of ethylene oxide added of 20 to 80, and (b) ethanol, and having a viscosity of 50 to 3000 mPa · s at 25 ° C. A toilet bowl cleaning composition.   The toilet bowl cleaning composition according to claim 1, comprising 14 to 64% by mass of (a).   The toilet bowl cleaning composition of Claim 1 or 2 containing 2-30 mass% of (b).   When 10 g is uniformly applied to a glass petri dish having an inner diameter of 85 mm and dried for 3 hours at 40 ° C. and a humidity of 50%, a volatilization of (b) forms a gel having a viscosity at 25 ° C. of 10 Pa · s or more. The cleaning composition for toilet bowl in any one of Claims 1-3. A toilet cleaning method comprising the following steps 1 to 3.
Process 1: The process of apply | coating the toilet bowl cleaning composition in any one of Claims 1-4 to a toilet bowl.
Process 2: The process of volatilizing (b) from the composition apply | coated at the process 1 by leaving it for 1 minute-3 hours after the process 1, and forming a gel with higher viscosity than the composition before application | coating.
Step 3: A step of applying water to the gel formed in Step 2 to produce a washing medium containing (a) and water, and applying the washing medium to a toilet bowl.   The toilet bowl washing method according to claim 5, wherein the viscosity of the gel formed in step 2 is 10 Pa · s or more at 25 ° C.