JP7149841B2 - Toilet liquid detergent composition and toilet liquid detergent product - Google Patents

Description

The present invention relates to a liquid toilet cleaner composition and a liquid toilet cleaner product.

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, didecyldimethylammonium chloride, and a specific β-glucuronidase inhibitor. ing.
According to the invention of Patent Document 1, it is intended to suppress the generation of excrement odor.

JP 2010-162321 A

However, liquid toilet detergent compositions are required to have further improved detergency. In addition, in order to enhance detergency and sterilization power, it is required that a sufficient amount of foam be formed (excellent foamability) in the liquid toilet detergent composition discharged from a spray container or the like. It is

Accordingly, an object of the present invention is to provide a toilet liquid detergent composition and a toilet liquid detergent product that are superior in detergency, sterilization power and foamability.

The present invention has the following aspects.
[1] Component (A): one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and semipolar surfactants;
(B) component: a compound represented by the following formula (b1);
(C) component: a quaternary ammonium salt (c1) having one or two alkyl groups having 10 to 14 carbon atoms and a quaternary ammonium salt (c2) having one alkyl group having 16 to 18 carbon atoms;
(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 5% by mass with respect to the total mass,
The content of the component (c1) is 0.05 to 0.8% by mass with respect to the total mass,
The mass ratio represented by the component (c1)/component (c2) is 2 to 15,
A liquid toilet detergent composition having a viscosity of 50 mPa·s or less at 25°C.
R ¹ —O—(R ² O) _m —R ³ (b1)
[In formula (b1), R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, R ² is an alkylene group having 2 or 3 carbon atoms, and m is , (R ² O) is a number from 1 to 6 representing the average number of repetitions. ]
[2] The liquid toilet detergent composition according to [1], wherein the mass ratio represented by component (A)/component (B) is 0.45 to 5.
[3] The liquid toilet cleaning composition according to [1] or [2], which does not substantially contain an anionic surfactant.
[4] 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 [3].
[5] The total amount of the component (A) and the component (B) is 0.7 to 10% by mass relative to the total mass, according to any one of [1] to [4]. Liquid toilet cleaning composition.
[6] The liquid toilet cleaning agent according to any one of [1] to [5], wherein the content of component (C) is 0.05 to 1.2% by mass relative to the total mass. Composition.
[7] A liquid toilet detergent product comprising a discharge container containing the liquid toilet detergent composition according to any one of [1] to [6].

According to the toilet liquid detergent composition of the present invention, it is excellent in detergency, sterilization power and foamability.

<<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. The liquid detergent can improve detergency and foamability by containing the component (A).
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 component (a1) together with component (B) and component (C), detergency and foamability 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).

(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. Lauramidopropylbetaine and lauryldimethylaminoacetic acid betaine are more preferable as the component (a1) from the viewpoint of easily increasing the foamability.
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). However, component (B), which will be described later, is not classified as a nonionic surfactant.
(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 foamability 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 glycol-based solvent.
R ¹ —O—(R ² O) _m —R ³ (b1)

In formula (b1), R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, R ² is an alkylene group having 2 or 3 carbon atoms, and m is It is a number from 1 to 6 representing the average repetition number of (R ² O). m R ² may be the same or different.

In formula (b1), R ¹ is preferably an alkyl group having 2 to 4 carbon atoms or a phenyl group. R ³ is preferably a hydrogen atom. R ² is preferably an alkylene group having 2 carbon atoms, that is, an ethylene group. m is preferably 1 to 3.

Examples of component (B) include ethylene glycol, 1,3-propanediol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, polyoxyethylene (m1 = 2 to 3) polyoxypropylene (m2 = 2 to 3) dimethyl ether (m1 and m2 are the average addition moles, respectively) number), polyoxyethylene (m3=1 to 6), phenyl ether (m3 represents the average added mole number), and the like.
The component (B) can be appropriately selected and used according to desired performance such as detergency against stains, sterilization power, and foamability.
From the viewpoint of excellent detergency and foamability, component (B) is preferably a compound in which R ¹ is a phenyl group (so-called aromatic glycol ether), more preferably monoethylene glycol monophenyl ether.

The content of component (B) is 0.2 to 5% by mass, preferably 0.3 to 4% by mass, more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent. (B) When the content of the component is within the above numerical range, the detergency and foamability of the liquid detergent are likely to be enhanced.
(B) component may be used individually by 1 type, and may use 2 or more types together.

The total amount of components (A) and (B) (AB total amount) is preferably 0.7 to 10% by mass, more preferably 1.1 to 8% by mass, relative to the total mass of the liquid detergent. , 1.5 to 5.5 mass % is more preferable. When the AB total amount is at least the above lower limit, it is easy to increase the detergency of the liquid detergent. It is easy to raise the foamability of a liquid detergent as AB total amount is below the said upper limit.

The mass ratio represented by component (A)/component (B) (hereinafter also referred to as “A/B ratio”) is preferably 0.45-5, more preferably 0.8-4. When the A/B ratio is at least the above lower limit, the detergency of the liquid detergent can be easily increased. If the A/B ratio is equal to or less than the above upper limit, the foamability of the liquid detergent can be easily increased.

<(C) Component>
Component (C) is a quaternary ammonium salt (c1) having one or two alkyl groups having 10 to 14 carbon atoms and a quaternary ammonium salt (c2) having one alkyl group having 16 to 18 carbon atoms. be. Component (C) is a so-called mono-long-chain alkyl quaternary ammonium salt or di-long-chain alkyl quaternary ammonium salt.

((c1) component)
Component (c1) is a quaternary ammonium salt having one or two alkyl groups of 10 to 14 carbon atoms.
Examples of component (c1) include dodecyltrimethylammonium chloride, decyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, and didecyldimethylammonium chloride.
As the component (c1), a quaternary ammonium salt having one alkyl group having 10 to 14 carbon atoms (a so-called mono long-chain alkyl quaternary ammonium salt) is preferable from the viewpoint of excellent sterilizing power, and dodecyltrimethylammonium chloride is preferable. more preferred.

The content of component (c1) is 0.05 to 0.8% by mass, preferably 0.08 to 0.7% by mass, and 0.1 to 0.5% by mass, relative to the total mass of the liquid detergent. % by mass is more preferred. (c1) When the content of the component is at least the above lower limit, the sterilization power of the liquid detergent is likely to be enhanced. (c1) It is easy to raise the cleaning power of a liquid cleaning agent as content of a component is below the said upper limit.
(c1) component may be used individually by 1 type, and may use 2 or more types together.

(Component (c2))
Component (c2) is a quaternary ammonium salt containing one alkyl group having 16 to 18 carbon atoms.
Component (c2) includes, for example, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and the like.
As the component (c2), stearyltrimethylammonium chloride is preferable from the viewpoint of excellent sterilizing power and foamability.

The content of component (c2) is preferably 0.003-0.4% by mass, more preferably 0.005-0.35% by mass, and more preferably 0.007-0. 25% by mass is more preferred. (c2) When the content of the component is at least the above lower limit, the sterilization power of the liquid cleaning agent is likely to be enhanced, and the foamability is likely to be enhanced. (c2) It is easy to raise the detergency of a liquid cleaning agent as content of a component is below the said upper limit more.

The content of component (C) (total amount of C) is preferably 0.05 to 1.2% by mass, more preferably 0.09 to 1.0% by mass, with respect to the total mass of the liquid detergent. 0.10 to 0.8 mass % is 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.

The mass ratio represented by component (c1)/component (c2) (hereinafter also referred to as “c1/c2 ratio”) is 2 to 15, preferably 2.5 to 14, more preferably 3 to 10. , 3.5 to 9 are particularly preferred. When the c1/c2 ratio is at least the above lower limit, the detergency of the liquid detergent can be easily increased. If the c1/c2 ratio is equal to or less than the above upper limit, the foamability of the liquid detergent can be easily increased.

<(D) Component>
(D) A component is water. Component (D) is not particularly limited, and purified water, ion-exchanged 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) It is easy to raise the foamability of a liquid detergent as content of a component is more than the said lower limit. (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. Examples of such optional components include disinfectants (excluding component (C)), preservatives, antifungal agents, and surfactants (excluding components (A) and (C)). , pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (excluding component (B)), fragrances, pH adjusters and the like.
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.

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 sodium 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 50 mPa·s or less, preferably 30 mPa·s or less, and even more preferably 10 mPa·s or less. If the viscosity at 25°C is equal to or less than the above upper limit, the foamability 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".

≪Toilet liquid detergent products≫
The toilet liquid detergent product of the present invention contains the toilet liquid detergent composition of the present invention in a discharge container.
The discharge container used for the toilet liquid detergent product of the present invention may be any container capable of discharging the internal solution (liquid detergent), such as an aerosol type discharge container that discharges with high-pressure gas, a non-aerosol type discharge container, or the like. is mentioned. Among these, the non-aerosol type discharge container is preferable from the viewpoint of usability and influence on the environment.
Examples of non-aerosol-type discharge containers include discharge containers such as spray containers, squeeze containers, and pump-type containers. Among these, a spray container is preferable in terms of usability. Spray containers include, for example, trigger spray containers, dispenser spray containers, and the like. Among them, a trigger spray container is preferable as the spray container from the viewpoint of easily increasing the foamability.
Trigger spray containers include a direct pressure type and an accumulator type. As the trigger spray container, an accumulator type is preferable from the viewpoint of easily increasing the foamability.
Here, an accumulator type trigger spray container is one in which even if the trigger is operated, liquid will not be sprayed from the nozzle until the liquid pressure in the cylinder reaches a predetermined pressure. A container configured to eject a liquid substance when the pressure is increased to a predetermined level or higher. These containers may be manually operated or electrically operated.

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.

The internal solution may be discharged in a form of foam or mist, but from the viewpoint of foamability, the form of foam is preferable.
As a method for discharging the internal solution in the form of foam, there is a method (foamer method) in which the internal solution is mixed with air and discharged in the form of foam.
A foamer-type discharge container usually comprises a container body containing a liquid detergent, and an injection nozzle attached to an opening of the container body for foaming the liquid detergent contained in the container body and discharging it to the outside. I have.
As a mechanism in which the injection nozzle foams the liquid detergent in the container main body, the liquid is introduced from the container main body into the foaming cylinder incorporated at the tip of the injection nozzle, and the liquid is applied to the wall of the foaming cylinder. Examples include those that cause collision to generate turbulence and promote mixing with air, and those that place a barrier or mesh in front of the injection nozzle to form bubbles. Air for generating foam is introduced from outside the container. Conventionally known structures can be applied to the detailed structures of these mechanisms, and are not particularly limited.
Examples of the foamer-type discharge container include those described in JP-A-2005-187601.

[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.
B-4: Ethylene glycol, "Ethylene glycol B" manufactured by Mitsubishi Chemical Corporation.
B-5: Diethylene glycol monobutyl ether, "Butyl diglycol" manufactured by Nippon Nyukazai Co., Ltd.

<(C) Component>
((c1) component)
C1-1: dodecyltrimethylammonium chloride, “Lipocard (registered trademark) 12-37W” manufactured by Lion Specialty Chemicals Co., Ltd.;
C1-2: Didecyldimethylammonium chloride, Lion Specialty Chemicals Co., Ltd. "Lipocard (registered trademark) 210-80E".
(Component (c2))
C2-1: Stearyltrimethylammonium chloride, Lion Specialty Chemicals Co., Ltd., "Lipocard (registered trademark) T-833".
<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 (ion-exchanged water).

<Optional component>
PVA: polyvinyl alcohol (PVA), "PVA-217" manufactured by Kuraray Co., Ltd.;
Xanthan gum: Xanthan gum, "KELZAN" manufactured by Sansho 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, Kanto Kagaku Co., Ltd. "sulfuric acid", potassium hydroxide, AGC Co., Ltd. "liquid caustic potash", sodium hydroxide, AGC Co., Ltd. "liquid caustic sodium".

[Examples 1 to 43, Comparative Examples 1 to 11]
≪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 5, components (A) to (C) and optional components are mixed with component (D), and if necessary, a pH adjuster (sulfuric acid, potassium hydroxide, or sodium hydroxide) is newly added. In addition, the pH was adjusted to 7.0, and the component (D) was added until the amount reached 500 g to obtain a 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. In addition, Examples 30 and 31 are reference examples.

<Evaluation 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. "A", "B" and "C" were regarded as passing. The results are shown in Tables 1-5.
"Evaluation criteria"
A: Viscosity of 10 mPa·s or less.
B: Viscosity of more than 10 mPa·s and 30 mPa·s or less.
C: Viscosity more than 30 mPa·s and 50 mPa·s or less.
D: Viscosity of more than 50 mPa·s and 100 mPa·s or less.
E: Viscosity over 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.) is heated and dissolved in 1 L of purified water (manufactured by Kanto Chemical Co., Ltd.). and sterilized with high pressure steam.
(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. "I", "II" and "III" were regarded as passing. The results are shown in Tables 1-5.
"Evaluation criteria"
I: The sterilization activity value is 2.5 or more.
II: The sterilization activity value is 2.0 or more and less than 2.5.
III: The sterilization activity value is 1.5 or more and less than 2.0.
IV: The sterilization activity value is less than 1.5.

<Evaluation of foamability>
The liquid detergent of each example was contained in a discharge container (“TA-FA” manufactured by Yoshino Kogyosho Co., Ltd., foam trigger spray container pressure accumulation type, 1 stroke (about 0.5 g/stroke)). Using this discharge container, the liquid detergent was discharged in 5 strokes into a 200 mL tall beaker, the height of foam was measured with a ruler, and foamability was evaluated based on the following evaluation criteria. "I", "II" and "III" were regarded as passing. The results are shown in Tables 1-5.
"Evaluation criteria"
I: The foam height is 4.0 cm or more.
II: The foam height is 3.5 cm or more and less than 4.0 cm.
III: The foam height is 3.0 cm or more and less than 3.5 cm.
IV: Foam height less than 3.0 cm.

<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 1-5.
"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 4, in Examples 1 to 43 to which the present invention is applied, the viscosity evaluation is "A", "B" or "C", and the sterilization power evaluation is "I", "II or "III", the evaluation of foaming property was "I", "II" or "III", and the evaluation of detergency was 3 to 5 points.
On the other hand, as shown in Table 5, Comparative Examples 1 and 2, in which the content of component (A) was outside the scope of the present invention, had an evaluation of foamability of "IV".
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 component (B) was outside the scope of the present invention, was evaluated as "IV" in foamability.
Comparative Example 5, in which the c1/c2 ratio was outside the range of the present invention, was evaluated as "IV" in sterilization power and 2 points in detergency. Comparative Example 6, in which the c1/c2 ratio was outside the range of the present invention, was evaluated as "IV" in foamability and 2 points in detergency. Comparative Example 7, in which the c1/c2 ratio was outside the range of the present invention, was evaluated as 2 points for detergency. Comparative Example 8, in which the c1/c2 ratio is outside the scope of the present invention, was evaluated as "IV" in foamability.
Comparative Example 9, which had a viscosity outside the scope of the present invention, had a viscosity evaluation of "D" and a foamability evaluation of "IV". Comparative Example 10, which had a viscosity outside the scope of the present invention, had a viscosity evaluation of "E" and a foamability evaluation of "IV".
Comparative Example 11, in which the component (C) was used as a comparative product, received an evaluation of 2 points for detergency.

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

Claims (4)

(A) component: one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and semipolar surfactants;
(B) component: one or more aromatic glycol ethers selected from ethylene glycol monophenyl ether, diethylene glycol monophenyl ether and hexaethylene glycol monophenyl ether ;
Component (C): Quaternary ammonium salt ( c1 ) and a quaternary ammonium salt (c2) having one alkyl group having 16 to 18 carbon atoms and three methyl groups ,
(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 5% by mass with respect to the total mass,
The content of the component (c1) is 0.05 to 0.8% by mass with respect to the total mass,
The mass ratio represented by the component (c1)/component (c2) is 2 to 15,
A liquid toilet detergent composition having a viscosity of 50 mPa·s or less at 25°C. The liquid toilet detergent composition according to claim 1, wherein the mass ratio represented by component (A)/component (B) is 0.45 to 5. The liquid toilet cleaning composition according to claim 1 or 2, which does not substantially contain an anionic surfactant. A toilet liquid detergent product comprising the toilet liquid detergent composition according to any one of claims 1 to 3 contained in a discharge container.