JP7149840B2 - Toilet liquid detergent composition - Google Patents

Description

The present invention relates to a liquid toilet cleaning composition.

Liquid detergent compositions used in toilets are required to have not only a cleaning effect but also an effect of deodorizing or deodorizing excrement odors. Such bad odors may be caused by bacteria and the like, and a liquid toilet cleaning composition is required to have a sterilizing effect or an antibacterial effect.

For example, Patent Document 1 proposes a toilet liquid detergent composition containing N-lauroylaminopropyl-N,N-dimethylamine oxide and didecyldimethylammonium chloride.
According to the invention of Patent Literature 1, improvement in detergency and sterilization power is achieved.

JP 2010-162321 A

However, liquid toilet detergent compositions are required to have further improved detergency. In addition, simply increasing the content of the cleaning component (surfactant, etc.) in order to enhance the detergency will increase the effectiveness of the liquid toilet cleaning composition on objects to be cleaned other than the toilet bowl (e.g., toilet seat, floor, etc.). When a cleaning method of applying and wiping off (wiping cleaning) is performed, traces of wiping remain on the object to be cleaned, and the surface of the object to be cleaned tends to be sticky (poor wiping properties).

Accordingly, an object of the present invention is to provide a liquid toilet detergent composition that is superior in detergency and sterilization power and has good wiping properties.

The present invention has the following aspects.
[1] Component (A): one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and semipolar surfactants, and component (B): represented by the following formula (b1) component (C): a cationic surfactant having one or two alkyl groups having 8 to 18 carbon atoms; component (D): water; amount is 0.5 to 5% by mass based on the total mass, the content of the component (B) is 0.2 to 4.5% by mass based on the total mass, and the component (A) A liquid detergent composition for toilets, wherein the mass ratio represented by /(component (B) + component (C)) is 0.5 to 15.

[In the formula (b1), X is an oxygen atom or a CH ₂ O group, R ¹ is an alkylene group having 2 or 3 carbon atoms, and m represents the average number of repetitions of (R ¹ O) 1 ∼6, and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[2] The liquid toilet cleaning composition according to [1], which has a viscosity of 50 mPa·s or less at 25°C.
[3] The liquid toilet detergent composition according to [1] or [2], wherein the mass ratio represented by component (B)/component (C) is 1 to 35.
[4] The toilet liquid detergent composition according to any one of [1] to [3], which does not substantially contain an anionic surfactant.
[5] The component (A) contains the component (a1): an amphoteric surfactant, and the content of the component (a1) is 50% by mass or more relative to the total mass of the surfactant. The liquid toilet cleaning composition according to any one of [1] to [4].
[6] The total amount of the component (B) and the component (C) is 0.21 to 5% by mass with respect to the total mass, [1] to [5]. Liquid toilet cleaning composition.
[7] Any of [1] to [6], wherein the total amount of the component (A), the component (B), and the component (C) is 0.75 to 7% by mass relative to the total mass. or the toilet liquid detergent composition according to claim 1.

ADVANTAGE OF THE INVENTION According to the toilet liquid detergent composition of the present invention, the detergency and the sterilizing power are excellent, and the wiping property can be improved.

<<Liquid detergent composition for toilet>>
The liquid detergent composition for toilets of the present invention (hereinafter also simply referred to as "liquid detergent") contains components (A) to (D).

<(A) Component>
Component (A) is one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and semipolar surfactants. A liquid detergent can improve detergency and wiping property by containing (A) component.
Component (A) includes an amphoteric surfactant (hereinafter also referred to as "(a1) component") and a nonionic surfactant (hereinafter also referred to as "(a2) component"), which are commonly used in liquid detergents. , semipolar surfactants (hereinafter also referred to as "(a3) component"), and the like.
Among these, as the component (A), the components (a1) and (a2) are preferable, and the component (a1) is more preferable. By using the component (a1) together with the component (B) and the component (C), detergency and wiping properties can be improved. In addition, the liquid detergent is likely to enhance the sterilization power by using the component (a1) together with the component (B) and the component (C).
From the viewpoint of enhancing the sterilizing power, it is preferable that the liquid detergent does not substantially contain an anionic surfactant. "Containing substantially no anionic surfactant" means that the content of the anionic surfactant is 0.2% by mass or less with respect to the total mass of the liquid detergent.

(Component (a1))
The (a1) component is an amphoteric surfactant. The component (a1) is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants. Among these, betaine-based amphoteric surfactants are preferred.
Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, and imidazolinium betaine. amphoteric surfactants, phosphobetaine amphoteric surfactants, aminopropionic acid amphoteric surfactants, and the like.
As the component (a1), a carbobetaine-based amphoteric surfactant and an amidobetaine-based amphoteric surfactant are preferable, and an amidobetaine-based amphoteric surfactant is more preferable.

(1) Carbobetaine-based amphoteric surfactants include, for example, betaine laurate dimethylaminoacetate, betaine myristyldimethylaminoacetate, betaine stearyldimethylaminoacetate, and the like.
(2) Amphoteric surfactants based on amidobetaine include, for example, coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauramidopropyl betaine, isostearamidopropyl betaine, and the like.
(3) Examples of sulfobetaine-based amphoteric surfactants include, for example, coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryldimethylaminohydroxysulfobetaine, laurylhydroxysulfobetaine, coconut oil fatty acid dimethylsulfopropylbetaine, laurylsulfobetaine, stearylsulfo betaine, myristylsulfobetaine and the like.
(4) Examples of imidazolinium betaine amphoteric surfactants include coconut oil alkyl-N-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2- Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like can be mentioned.
(5) Phosphobetaine-based amphoteric surfactants include, for example, lauryl hydroxyphosphobetaine.
(6) Examples of aminopropionic acid-based amphoteric surfactants include sodium laurylaminodipropionate and triethanolamine laurylaminodipropionate.
(7) Examples of amino acid-based amphoteric surfactants include laurylamino fatty acid salts, stearylamino fatty acid salts, and myristylamino fatty acid salts.

As the component (a1), among those mentioned above, lauramidopropyl betaine, lauryldimethylamino betaine, and stearyldimethylamino betaine are preferable. Lauramidopropyl betaine and lauryldimethylaminoacetic acid betaine are more preferable as the component (a1) from the viewpoint of facilitating the wiping off.
Examples of counter ions of the salt include alkali metal ions, ammonium ions, ions of alkanolamine salts, and the like. Among these, alkali metal ions are preferred, and sodium ions and potassium ions are more preferred.

(a1) Component is commercially available. Examples of commercially available component (a1) include lauramidopropyl betaine “Enagicol (registered trademark) L-30B (manufactured by Ipposha Yushi Kogyo Co., Ltd.)” and coconut oil fatty acid amidopropyl betaine. "CAB-30 (manufactured by Ipposha Yushi Kogyo Co., Ltd.)", "TEGO BETAIN CK-OK (manufactured by Degussa)" which is a coconut oil fatty acid amidopropyl betaine, "Ampholex" which is a palm kernel oil fatty acid amidopropyl betaine (registered trademark) PB-1 (manufactured by Miyoshi Oil Co., Ltd.)”, “Levon (registered trademark) LD-36 (manufactured by Sanyo Chemical Industries Co., Ltd.)” which is betaine lauryldimethylaminoacetate and “Ovazoline (registered trademark)” LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)”, and “Amphitol (registered trademark) 86B (manufactured by Kao Corporation)” which is betaine stearyldimethylaminoacetate.

The content of component (a1) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass, relative to the total mass of the surfactant.

((a2) component)
The (a2) component is a nonionic surfactant. Examples of the component (a2) include the following compounds (1) to (8).
(1) an alkylene oxide having 2 to 4 carbon atoms, or an average of 3 to 30 moles of ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl ether having an added linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(2) an alkylene oxide having 2 to 4 carbon atoms, or an average of 3 to 30 moles of ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl (or alkenyl) phenyl ether having an added linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(3) C1-2 alkyl ester of long-chain fatty acid with 10-20 carbon atoms, either alkylene oxide with 2-4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/ 9.9-9.9/0.1) added on average 3-30 moles of fatty acid alkyl ester alkoxylate.
(4) A sorbitan ester of a long-chain fatty acid with 10 to 20 carbon atoms, either an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9). .9/0.1) added with an average of 3 to 30 moles of polyoxyalkylene sorbitan fatty acid ester.
(5) A long-chain fatty acid with 10 to 20 carbon atoms, either an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) added with an average of 3 to 30 moles of polyoxyalkylene fatty acid ester.
(6) Add either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) to hydrogenated castor oil. A polyoxyalkylene hydrogenated castor oil with an average addition of 3 to 30 moles.
(7) Esters of long-chain fatty acids having 10 to 20 carbon atoms and glycerin (glycerin fatty acid esters).
(8) Linear or branched alkyl polyglycosides having 10 to 20 carbon atoms.

(a2) WHEREIN: A primary alcohol and a secondary alcohol are mentioned as an aliphatic alcohol used. Moreover, the alkyl group may have a branched chain.
Among the above, as the component (a2), a branched-chain alkyl group having 12 to 18 carbon atoms, an alkylene oxide having 2 carbon atoms, and a polyoxyalkylene alkyl ether having 5 to 9 moles of alkylene oxide are preferred. Component (a2) is more preferably an alkyl polyglucoside having 12 to 16 carbon atoms.

(Component (a3))
Component (a3) is a semi-polar surfactant (amine oxide surfactant). Component (a3) includes, for example, alkylamine oxides such as dodecyldimethylamine oxide (AX), myristyldimethylamine oxide and coconutalkyldimethylamine oxide; amidoamines such as coconut oil fatty acid amidopropylamine oxide and lauramidopropylamine oxide; oxide and the like. Among these, dodecyldimethylamine oxide (AX) is preferable as the component (a3).

The content of component (A) is 0.5 to 5% by mass, preferably 0.8 to 4% by mass, more preferably 1.0 to 2.5% by mass, relative to the total mass of the liquid detergent. preferable. (A) It is easy to improve the detergency of a liquid detergent as content of a component is more than the said lower limit. (A) It is easy to raise the wiping off property of a liquid detergent as content of a component is below the said upper limit.
(A) Component may be used individually by 1 type, and may use 2 or more types together.

<(B) Component>
The component (B) is a compound represented by the following formula (b1). Component (B) is a so-called aromatic glycol ether.

In formula (b1), X is an oxygen atom or a CH ₂ O group, R ¹ is an alkylene group having 2 or 3 carbon atoms, and m represents the average repeating number of (R ¹ O) 1 to 6, and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In formula (b1), X is preferably an oxygen atom. R ¹ is preferably an alkylene group having 2 carbon atoms, that is, an ethylene group. m is preferably 1 to 3, more preferably 1. R ² is preferably a hydrogen atom.

Component (B) includes, for example, monoethylene glycol monophenyl ether, triethylene glycol monophenyl ether, monopropylene glycol monophenyl ether, tripropylene glycol monophenyl ether, and the like. Among them, monoethylene glycol monophenyl ether is preferable as the component (B) from the viewpoint of easily increasing detergency.

The content of component (B) is preferably 0.2 to 4.5% by mass, more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent. (B) It is easy to improve the detergency of a liquid detergent as content of a component is more than the said lower limit. (B) It is easy to raise the wiping off property of a liquid detergent as content of a component is below the said upper limit.
(B) component may be used individually by 1 type, and may use 2 or more types together.

<(C) Component>
Component (C) is a cationic surfactant having one or two alkyl groups of 8 to 18 carbon atoms. Component (C) is a so-called mono-long chain alkyl cationic surfactant or di-long chain alkyl cationic surfactant.
As component (C), conventionally known cationic surfactants can be used, and examples thereof include quaternary ammonium salts, guanidine salts, amidoamine type surfactants, and the like.

(1) Examples of quaternary ammonium salts include dodecyltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and the like. is mentioned.
(2) Guanidine salts include, for example, lauramidobutylguanidine acetate, myristate amidebutylguanidine acetate, and acetate amidebutylguanidine palmitate.
(3) Amidoamine-type surfactants include, for example, stearic acid dimethylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminoethylamide, stearic acid di Propylaminopropylamide, palmitate dimethylaminoethylamide, palmitate dimethylaminopropylamide, myristate dimethylaminoethylamide, myristate dimethylaminopropylamide and the like.

As the component (C), a quaternary ammonium salt is preferable among the above from the viewpoint of excellent sterilizing power. Among quaternary ammonium salts, dodecyltrimethylammonium chloride and stearyltrimethylammonium chloride are particularly preferred as component (C).

The content of component (C) is preferably 0.01 to 3% by mass, more preferably 0.03 to 1% by mass, and more preferably 0.05 to 0.6% by mass, relative to the total mass of the liquid detergent. More preferred. (C) It is easy to raise the disinfection power of a liquid detergent as content of a component is more than the said lower limit. (C) It is easy to raise the detergency of a liquid detergent as content of a component is below the said upper limit more.
(C) component may be used individually by 1 type, and may use 2 or more types together.

The mass ratio represented by (A) component/((B) component + (C) component) (hereinafter also referred to as “A/(B+C) ratio”) is 0.5 to 15, and 0.7 ~14 is preferred, and 0.8-12 is more preferred. When the A/(B+C) ratio is at least the above lower limit, the wiping properties of the liquid detergent are likely to be enhanced. When the A/(B+C) ratio is equal to or less than the above upper limit value, the wiping property of the liquid cleaning agent is likely to be enhanced, and the sterilization power of the liquid cleaning agent is likely to be enhanced.

The mass ratio represented by component (B)/component (C) (hereinafter also referred to as “B/C ratio”) is preferably 1-35, more preferably 3-25. When the B/C ratio is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the B/C ratio is equal to or less than the above upper limit, it is easy to increase the wiping property of the liquid detergent.

The total amount of components (B) and (C) (total amount of BC) is preferably 0.21 to 5% by mass, more preferably 0.25 to 3.2% by mass, relative to the total mass of the liquid detergent. More preferably, 0.5 to 2.1% by mass is even more preferable. When the total amount of BC is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the total amount of BC is equal to or less than the above upper limit, it is easy to enhance the wiping property of the liquid detergent.

The total amount of components (A), (B) and (C) (ABC total amount) is preferably 0.75 to 7% by mass, preferably 1 to 6% by mass, based on the total mass of the liquid detergent. is more preferred, and 2 to 4% by mass is even more preferred. When the ABC total amount is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the ABC total amount is equal to or less than the above upper limit, it is easy to improve the wiping property of the liquid detergent.

<(D) Component>
(D) A component is water. Component (D) is not particularly limited, and purified water or tap water may be used.
The content of component (D) is preferably 80 to 95% by mass, more preferably 88 to 94% by mass, relative to the total mass of the liquid detergent. (D) When the content of the component is at least the above lower limit, the wiping properties of the liquid detergent are likely to be enhanced. (D) It is easy to raise the detergency of a liquid detergent as content of a component is below the said upper limit.

<Optional component>
The liquid cleansing agent of the present invention can contain, if necessary, components that can be normally used in liquid cleansing agents for toilets, in addition to the above components. Such optional ingredients include, for example, bactericidal agents (except for component (C)), preservatives, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (however, , (excluding component (B).), fragrances, pH adjusters, and the like.

Examples of pH adjusters include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and ammonia. Among these, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferable, and sulfuric acid and potassium hydroxide are more preferable, from the viewpoint of easy adjustment of pH.
One of the pH adjusters may be used alone, or two or more of them may be used in combination.

When the liquid detergent contains optional components, the content of the optional components is preferably 0.3 to 19.2% by mass relative to the total mass of the liquid detergent.

In addition, the total amount of the components constituting the liquid detergent of the present invention does not exceed 100% by mass.

≪Method for producing liquid detergent≫
A liquid detergent is manufactured by a conventionally well-known manufacturing method. For example, the above components (A) to (C) are added to component (D), which is a solvent, optional components are added as necessary, and the mixture is mixed.

The pH of the liquid detergent at 25°C is preferably 5-9, more preferably 6-8. When the pH is within the above numerical range, the usability of the liquid detergent is likely to be improved.
The pH can be adjusted by adding an appropriate amount of pH adjuster.
The pH used herein is a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) at 25°C.

The viscosity of the liquid detergent at 25° C. is preferably 50 mPa·s or less, more preferably 30 mPa·s or less, and even more preferably 10 mPa·s or less. When the viscosity at 25°C is equal to or less than the above upper limit, the wiping property of the liquid detergent is likely to be improved. Although the lower limit of the viscosity at 25°C is not particularly limited, it is substantially 0.8 mPa·s.
The viscosity of the liquid detergent can be adjusted by adjusting the content of component (D), adding a thickener, and the like.
Viscosity in the present specification is measured at 25° C. using a Brookfield viscometer, rotor No. 1. A value measured 60 seconds after the start of rotation of the rotor at a rotor speed of 60 rpm.

≪How to use the liquid detergent≫
As a method of using the liquid detergent, for example, the liquid detergent is stored in a discharge container, an appropriate amount of the liquid detergent is applied to the toilet bowl from this discharge container, and after a certain period of time has passed, it is rinsed with a flush or the like. ” is used.
Further, as another usage method, there is a usage method of applying an appropriate amount of liquid detergent to the toilet bowl and rubbing it with a cleaning brush for "scrubbing".
Alternatively, there is a usage method in which a liquid detergent is applied to the toilet seat or the floor of the toilet and wiped off with a cloth or paper for "wiping off".

A spray container, a squeeze container, or the like can be used as a discharge container for containing the liquid cleaning agent. Among them, a spray container is preferable as the discharge container for containing the liquid detergent because of its excellent applicability to the object to be cleaned.
Spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressure accumulation type), dispenser spray containers, and the like. These containers may be manually operated or electrically operated. Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as the propellant. These propellants may be used alone or in combination of two or more.
Examples of trigger spray containers include those described in JP-A-9-268473 and JP-A-10-76196.
Examples of dispenser spray containers include those described in, for example, JP-A-9-256272.
Examples of the pressure accumulation type trigger spray container include those described in JP-A-2013-154276.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.
Raw materials and measurement/evaluation methods used in Examples and Comparative Examples are as follows.

≪Raw materials used≫
<(A) Component>
A-1: Lauramidopropyl Betaine, “Enagicol (registered trademark) L-30B” manufactured by Lion Corporation.
A-2: Betaine lauryldimethylaminoacetate, "Lebon (registered trademark) LD-36" manufactured by Sanyo Chemical Industries, Ltd.
A-3: Betaine stearyldimethylaminoacetate, "Amphitol (registered trademark) 86B" manufactured by Kao Corporation.
A-4: 12-16 alkyl polyglucoside (APG), "PLANTACARE 1200up" manufactured by Cognis.
A-5: AX, n-dodecyldimethylamine oxide, Lion Specialty Chemicals Co., Ltd. "Cadenax (registered trademark) DM12D-W".

<(B) Component>
B-1: Ethylene glycol monophenyl ether (phenoxyethanol), "Phenyl glycol" manufactured by Nippon Nyukazai Co., Ltd.
B-2: Diethylene glycol monophenyl ether, "Phenyl glycol (2 mol)" manufactured by Nippon Nyukazai Co., Ltd.
B-3: Hexaethylene glycol monophenyl ether, "Phenyl glycol (5.5 mol)" manufactured by Nippon Nyukazai Co., Ltd.
<Component (B'): Comparative product of component (B)>
B'-1: Diethylene glycol monobutyl ether, Nippon Nyukazai Co., Ltd. "butyl diglycol".

<(C) Component>
C-1: dodecyltrimethylammonium chloride, "Lipocard (registered trademark) 12-37W" manufactured by Lion Specialty Chemicals Co., Ltd.;
C-2: Stearyltrimethylammonium chloride, Lion Specialty Chemicals Co., Ltd., "Lipocard (registered trademark) T-833".
C-3: Lauramidobutylguanidine acetate, "C12A4G" manufactured by Lion Corporation.
C-4: Dimethylaminopropylamide stearate, "Catinal (registered trademark) MPAS" manufactured by Toho Chemical Industry Co., Ltd.
<Component (C'): Comparative product of component (C)>
C′-1: benzalkonium chloride (alkyldimethylbenzylammonium chloride having 7 carbon atoms in the alkyl group), “Benzalkonium chloride solution” manufactured by Kankasu Chemical Industry Co., Ltd.;

<(D) Component>
D-1: Water (purified water), "purified water" manufactured by Kanto Kagaku Co., Ltd.

<Optional component>
PVA: polyvinyl alcohol (PVA), "PVA-217" manufactured by Kuraray Co., Ltd.;
Xanthan gum: xanthan gum, "Monat Gum (registered trademark) DA" manufactured by DSP Gokyo Food & Chemical Co., Ltd.;
Ethanol: Ethanol, "Synthetic 95" manufactured by Nippon Alcohol Sales Co., Ltd.
Perfume: Perfume composition A described in JP-A-2003-183697.
pH adjuster: sulfuric acid, "sulfuric acid" manufactured by Kanto Chemical Co., Ltd., potassium hydroxide, "liquid caustic potash" manufactured by AGC Corporation.

[Examples 1 to 43, Comparative Examples 1 to 8]
≪Manufacturing liquid detergent≫
500 g of the liquid detergent of each example was prepared by the following procedure.
According to the formulations in Tables 1 to 6, components (A) to (C) and optional components are mixed with component (D), and if necessary, a pH adjuster (sulfuric acid or potassium hydroxide) is newly added to pH 7. 0, component (D) was added until the amount reached 500 g to obtain the liquid detergent of each example.
In the table, the unit of "composition" is "% by mass" and indicates the amount in terms of pure content. In the table, "-" indicates that the component is not included. In the table, "Balance" of component (D) indicates the amount required to make the total mass of the liquid detergent 100% by mass (500 g). In the table, the blending amount of the pH adjuster, "appropriate amount", indicates the amount required to adjust the pH of the liquid detergent to 7.0. Examples 24 and 25 are reference examples.

<Measurement of viscosity>
The liquid detergent of each example was adjusted to 25° C. and measured using a Brookfield viscometer (manufactured by TOKIMEC). 1. At a rotor rotation speed of 60 rpm, the value after 60 seconds from the start of rotation of the rotor was measured as the viscosity. The measured viscosity was evaluated based on the following evaluation criteria. The results are shown in Tables 1-6.
"Evaluation criteria"
◎◎: Viscosity is 10 mPa·s or less.
A: Viscosity is more than 10 mPa·s and 30 mPa·s or less.
○: Viscosity is more than 30 mPa·s and 50 mPa·s or less.
(triangle|delta): Viscosity is more than 50 mPa*s and 100 mPa*s or less.
x: Viscosity exceeds 100 mPa·s.

<Evaluation of sterilization power>
The disinfecting power of the liquid detergent of each example was evaluated as follows.
(1) Preparation of Control Sample A 0.05% by mass aqueous solution of polyoxyethylene sorbitan monooleate (trade name “Tween80”, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was sterilized with high pressure steam and used as a control sample.
(2) Preparation of Test Bacterial Solution Staphylococcus aureus and Escherichia coli were inoculated into TSA (Triptic Soy Agar) medium (manufactured by Difco) and precultured at 37° C. for 18 to 20 hours. Next, this bacterium was inoculated into TSA medium, precultured at 37° C. for 18 to 20 hours, and then adjusted to 10 6 CFU/mL using sterilized 1/2NB (Nutrient Broth) medium (manufactured by Difco). did.
(3) Preparation of inactivating agent A mixture of polypeptone, lecithin, and polysorbate (LP diluent Daigo (trade name), manufactured by Nihon Pharmaceutical Co., Ltd.) was heated and dissolved in 1 L of purified water and sterilized with high pressure steam. Using.
(4) Sterilization of test tube Dry heat sterilization was performed at 180°C for 1 hour.
(5) Measurement of sterilization power 1 mL of the test bacterial solution stored in a 50 ° C. environment for 1 month was added to a sterilized test tube, followed by an evaluation sample (liquid detergent obtained in each example) or a control sample. was added, and the mixture was left standing after stirring. After standing still for 10 minutes, 1 mL was collected from the mixture by stirring, added to a sterilized test tube containing 9 mL of an inactivating agent, and stirred to obtain test liquid (i).
The test liquid (i) was applied to the TSA medium by the pour culture method, and after culturing at 37° C. for 40 hours, the number of bacteria was determined. The Log bacterium number obtained by subtracting the Log bacterium number of the evaluation sample from the Log bacterium number of the control sample was taken as the bactericidal activity value, and the bactericidal power was evaluated based on the following evaluation criteria. ⊚, ⊚, and ∘ were regarded as acceptable. The results are shown in Tables 1-6.
"Evaluation criteria"
◎◎: The sterilization activity value is 2.5 or more.
A: The sterilization activity value is 2.0 or more and less than 2.5.
○: The sterilization activity value is 1.5 or more and less than 2.0.
x: The sterilization activity value is less than 1.5.

<Evaluation of wiping property>
100 μL of each liquid detergent was placed on a slide glass and lightly wiped with eight-folded toilet paper. After drying, the remaining wiping marks were visually observed, and the wiping property was evaluated based on the following evaluation criteria. ⊚, ⊚, and ∘ were regarded as acceptable. The results are shown in Tables 1-6.
"Evaluation criteria"
⊚: Absolutely no wiping marks remain, and no stickiness is felt at all.
⊚: A very slight fine linear wiping mark remains, but it is not sticky and does not bother me.
◯: Slightly fine linear wiping marks remain, but stickiness is not noticeable.
Δ: Wiping traces are partially left, and stickiness is also felt.
x: Wiping marks remain on the entire surface, and stickiness is also felt.

<Evaluation of detergency>
100 μL of urine from 5 adult males was placed on a ceramic plate of 25 mm×100 mm, left at room temperature (25° C.) for 24 hours, and dried. After drying, the ceramic plate was immersed in 20 mL of the liquid detergent of each example for 30 seconds in a 50 mL vial and then taken out. After the ceramic plate was taken out and washed twice with water, five expert panelists visually evaluated the degree of remaining dirt based on the following evaluation criteria. The average value of the evaluation results of the expert panelists was obtained, and 3 to 5 points were regarded as passing. The results are shown in Tables 1-6.
"Evaluation criteria"
5 points: The dirt is completely removed.
4 points: Almost all stains are removed.
3 points: About half of the dirt is removed.
2 points: Slightly soiled.
1 point: The dirt is not removed at all.

As shown in Tables 1 to 5, in Examples 1 to 43 to which the present invention is applied, the evaluation of the sterilization power is "◎◎" or "◎", and the evaluation of the wiping property is "◎◎" or "◎". Or "○", and the evaluation of detergency was 3 to 5 points.
On the other hand, as shown in Table 6, in Comparative Example 1, in which the content of component (A) is outside the scope of the present invention, the evaluation of wiping property was "Δ" and the evaluation of detergency was 2 points. . Comparative Example 2, in which the content of the component (A) was outside the scope of the present invention, was evaluated as "Fair" in the wiping property.
Comparative Example 3, in which the content of component (B) was outside the scope of the present invention, was evaluated as 2 points for detergency. Comparative Example 4, in which the content of the component (B) was outside the scope of the present invention, was evaluated as "Poor" in the wiping property. In Comparative Example 5, in which the component (B) was used as a comparative product, the evaluation of the wiping property was “Δ”.
Comparative Example 6, in which the component (C) was used as a comparative product, received an evaluation of 2 points for detergency.
Comparative Example 7, in which the A/(B+C) ratio was outside the scope of the present invention, was evaluated as "Δ" in terms of wiping properties. In Comparative Example 8, in which the A/(B+C) ratio was outside the range of the present invention, the evaluation of sterilization power was "x" and the evaluation of wiping property was "Δ".

From these results, it was confirmed that the liquid detergent to which the present invention is applied is superior in detergency and sterilization power, and has good wiping properties.

Claims (4)

(A) component: one or more amphoteric surfactants selected from carbobetaine-based amphoteric surfactants and amidobetaine-based amphoteric surfactants ;
(B) component: a compound represented by the following formula (b1);
(C) component: one or more cationic surfactants selected from dodecyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauramidobutylguanidine acetate and dimethylaminopropylamide stearate ;
(D) component: water and
contains a
The content of the component (A) is 0.5 to 5% by mass with respect to the total mass,
The content of the component (B) is 0.2 to 4.5% by mass with respect to the total mass,
A toilet liquid detergent composition, wherein the mass ratio represented by component (A)/(component (B)+component (C)) is 0.5 to 15.

[In the formula (b1), X is an oxygen atom or a CH ₂ O group, R ¹ is an alkylene group having 2 or 3 carbon atoms, and m represents the average number of repetitions of (R ¹ O) 1 ∼6, and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] The liquid toilet cleaning composition according to claim 1, wherein the viscosity at 25°C is 50 mPa·s or less. The liquid toilet detergent composition according to claim 1 or 2, wherein the mass ratio represented by component (B)/component (C) is 1 to 35. The liquid toilet cleaning composition according to any one of claims 1 to 3, which does not substantially contain an anionic surfactant.