JP7630266B2 - Liquid cleaning composition for bathroom - Google Patents

Description

The present invention relates to a liquid cleaning composition for bathrooms.

A wide variety of dirt is present in a bathroom, including limescale, sebum, limescale, mold, etc. Various cleaning compositions have been proposed so far for removing dirt in the bathroom.
For example, Patent Document 1 discloses a hard surface cleaner composition that contains a surfactant including a non-soap anionic surfactant, a glycol solvent, and an aminocarboxylic acid type chelating agent, and has a pH of 10 to 12. This cleaner composition has excellent cleaning power against limescale stains attached to glass fiber reinforced plastic (FRP) surfaces.
Furthermore, Patent Document 2 discloses a composition that contains a glycol solvent and an amine surfactant to enhance the ability to clean sebum adhering to a glass surface.

JP 2016-124965 A JP 2020-105322 A

However, sebum stains are more difficult to remove when they adhere to a highly hydrophobic surface such as a PP (polypropylene) resin than to a highly hydrophilic surface, and therefore, when sebum stains adhere to a bathtub lid or the like made of a PP (polypropylene) resin, it may be difficult to remove the stains using the cleaning compositions of Patent Documents 1 and 2.
In order to improve the cleaning power against sebum stains, it is conceivable to increase the amount of anionic surfactant blended, but if the amount of anionic surfactant blended is too high, the problem of poor rinsing ability arises.
Therefore, an object of the present invention is to provide a liquid cleaning composition for bathrooms that can achieve both improved cleaning power against sebum stains adhering to hydrophobic surfaces such as PP resin and improved rinsing properties.

［一般式（Ｃ１）中、Ａ^１Ｏは炭素数２又は３のオキシアルキレン基であり、ｈはＡ^１Ｏの平均付加モル数を表す１～６の数である。一般式（Ｃ２）中、Ａ^２Ｏは炭素数２又は３のオキシアルキレン基であり、ｊはＡ^２Ｏの平均付加モル数を表す０～６の数である。一般式（Ｃ３）中、Ａ^３Ｏは炭素数２又は３のオキシアルキレン基であり、ｋはＡ^３Ｏの平均付加モル数を表す１～６の数である。］
前記（Ｃ）成分の質量に対する前記（Ｂ）成分の質量の比［（Ｂ）／（Ｃ）］が、０．１～４．０である、浴室用液体洗浄剤組成物。
［２］前記（Ｃ）成分の質量に対する前記（Ａ）成分と前記（Ｂ）成分の合計質量の比［｛（Ａ）＋（Ｂ）｝／（Ｃ）］が、０．８～６である、［１］に記載の浴室用液体洗浄剤組成物。
［３］前記（Ｂ）成分の質量に対する前記（Ａ）成分の質量の比［（Ａ）／（Ｂ）］が、１～２５である、［１］又は［２］に記載の浴室用液体洗浄剤組成物。
［４］さらに、（Ｄ）成分：グリコールエーテル系溶剤を含み、
前記（Ｄ）成分は、下記一般式（Ｄ）で表され、
Ｒ^１Ｏ－（Ａ^４Ｏ）_ｎ－Ｒ^２ ・・・（Ｄ）
［一般式（Ｄ）中、Ｒ^１は炭素数１～８の直鎖状もしくは分岐状のアルキル基であり、Ｒ^２は水素原子、炭素数１～４の直鎖状のアルキル基、又はアセチル基であり、Ａ^４Ｏは炭素数２～４のオキシアルキレン基であり、ｎはＡ^４Ｏの平均付加モル数を表す０．１～２０の数である。］
前記（Ｄ）成分の質量に対する前記（Ｃ）成分の質量の比［（Ｃ）／（Ｄ）］が、０．０５～２．０である、［１］～［３］のいずれか一項に記載の浴室用液体洗浄剤組成物。 In order to achieve the above object, the present invention employs the following configuration.
[1] Component (A): a non-soap anionic surfactant,
(B) component: cationic cellulose,
(C) component: containing an aromatic compound,
The component (C) is represented by any one of the following general formulas (C1) to (C3):

[In general formula (C1), A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, and h is a number from 1 to 6 representing the average number of moles of A ¹ O added. In general formula (C2), A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and j is a number from 0 to 6 representing the average number of moles of A ² O added. In general formula (C3), A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and k is a number from 1 to 6 representing the average number of moles of A ³ O added.]
A bathroom liquid cleaning composition, in which the ratio of the mass of the component (B) to the mass of the component (C) [(B)/(C)] is 0.1 to 4.0.
[2] The bathroom liquid cleaning composition according to [1], wherein the ratio of the total mass of the (A) component and the (B) component to the mass of the (C) component, [{(A)+(B)}/(C)], is 0.8 to 6.
[3] The bathroom liquid cleaning composition according to [1] or [2], wherein the ratio of the mass of the (A) component to the mass of the (B) component [(A)/(B)] is 1 to 25.
[4] Further, the composition contains a component (D): a glycol ether-based solvent,
The component (D) is represented by the following general formula (D):
R ¹ O-(A ⁴ O) _n -R ² ...(D)
[In general formula (D), R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number from 0.1 to 20 representing the average number of moles of A ⁴ O added.]
The bathroom liquid cleaning composition according to any one of [1] to [3], wherein the ratio of the mass of the component (C) to the mass of the component (D) [(C)/(D)] is 0.05 to 2.0.

The bathroom liquid cleaner composition of the present invention provides excellent cleaning power for sebum stains adhering to hydrophobic surfaces such as PP resin without impairing rinsing properties.

The bathroom liquid cleaner composition of the present invention contains the components (A), (B), and (C) described below, and preferably contains the component (D).
The following description of the constituent elements may be based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range including the numerical values before and after "to" as the lower and upper limits. In addition, the content of a component that can be in the form of an acid or a salt is the content in the form of an acid, unless otherwise specified.

<Component (A)>
Component (A) is a non-soap anionic surfactant. A "non-soap anionic surfactant" is an anionic surfactant other than higher fatty acids or salts thereof (so-called soaps). A "higher fatty acid" is a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. In other words, component (A) is an anionic surfactant other than saturated or unsaturated fatty acids having 8 to 24 carbon atoms or salts thereof.
Component (A) is used to provide an effective cleaning power against limescale, sebum stains, and the like that adhere to the inside of the bathroom.

Examples of component (A) include alkylbenzenesulfonates, alkanesulfonates, alkyl sulfates, alkyl polyoxyethylene sulfates, α-olefinsulfonates, internal olefinsulfonic acids or salts thereof in which the carbon-carbon double bond is at the second or higher position (internal), alkylphenoxyphenyl disulfonates, fatty acid salts excluding higher fatty acid salts, α-sulfofatty acid salts, ether carboxylates, alkyl phosphates, alkyl polyoxyethylene phosphates, dialkyl sulfosuccinate salts, alkyl sulfosuccinate salts, alkenyl succinates, N-acyl amino acid salts, and N-acyl methyl taurine salts.

Among these, alkylbenzene sulfonates and α-olefin sulfonates are preferably selected from the viewpoint of excellent cleaning power, with α-olefin sulfonates being particularly preferred. Examples of salts include alkali metal salts such as sodium salts and potassium salts, and alkanolamine salts such as monoethanolamine salts and diethanolamine salts. Of these, alkali metal salts such as sodium salts and potassium salts are preferred.

The component (A) may be used alone or in a suitable combination of two or more types.
The content of component (A) is preferably 0.5 to 5.0 mass% and more preferably 0.5 to 1.5 mass% based on the total mass of the bathroom liquid cleaner composition. A content of 0.5 mass% or more enhances the cleaning power, and a content of 5.0 mass% or less improves the rinsing ability.

<Component (B)>
The component (B) is a cationic cellulose. By including the component (B), the sebum cleansing power and rinsing ability are improved.

Examples of cationic cellulose include cationic cellulose having a structural unit represented by the following general formula (B1) (hereinafter may be referred to as "component (B1)"), cationic cellulose having a structural unit represented by the following general formula (B2) (hereinafter may be referred to as "component (B2)"), cationic cellulose having a structural unit represented by the following general formula (B3) (hereinafter may be referred to as "component (B3)"), and cationic cellulose having a structural unit represented by the following general formula (B4) (hereinafter may be referred to as "component (B4)").
Among these, component (B1) is preferred from the viewpoints of sebum cleansing power and rinsing properties.

In formula (B1), s and t are the average mole numbers of oxyethylene groups added.
The weight average molecular weight of the component (B1) is from 10,000 to several million.
The weight average molecular weight of the component (B2) is from 10,000 to several hundred thousand.

The weight average molecular weight of the component (B3) is from 10,000 to several hundred thousand.
In formula (B4), v and w are the average molar numbers of oxyethylene groups added.
The weight average molecular weight of the component (B4) is from 10,000 to several million.

The degree of cationization of component (B) is preferably 0.4 to 3.0% by mass, and more preferably 1.5 to 2.5% by mass. If the degree of cationization is within the above range, the sebum cleansing power and rinsing ability will be further improved.
The "degree of cationization" herein means the content (mass %) of nitrogen atoms derived from the cationizing agent in the molecules of component (B), i.e., the ratio of the mass of nitrogen atoms to the total mass of component (B).

The degree of cationization of component (B) can be calculated based on the identified chemical structure. When the chemical structure of component (B) is not identified, such as when the ratio of constituent units in component (B) is unknown, the degree of cationization of component (B) is calculated from the nitrogen content determined experimentally. The nitrogen content of component (B) can be measured by the Kjeldahl method, but may be measured by other methods for convenience.

The viscosity of a 2% by mass aqueous solution of component (B) at 25° C. is preferably 50 to 35,000 mPa·s, more preferably 70 to 500 mPa·s, and even more preferably 70 to 200 mPa·s. When the viscosity of a 2% by mass aqueous solution of component (B) is within the above range, the bathroom liquid cleaning composition has excellent water-draining properties when rinsed with running water from a shower or the like and the concentration of the composition becomes low.
The viscosity is a value measured using a Brookfield viscometer for a 2% by mass aqueous solution of component (B) at 25° C. The viscosity measurement conditions are as follows:

Measurement conditions:
[rotor]
The rotor numbers and rotor rotation speeds corresponding to the viscosities to be measured are as follows:
Viscosity less than 500 mPa·s: rotor number 2, rotation speed 60 rpm.
Viscosity of 500 mPa·s or more and less than 2000 mPa·s: rotor number 3, rotation speed 60 rpm.
Viscosity of 2000 mPa·s or more and less than 10000 mPa·s: rotor number 4, rotation speed 60 rpm.
Viscosity of 10,000 mPa·s or more and less than 50,000 mPa·s: rotor number 4, rotation speed 12 rpm.
[Reading the numbers]
60 seconds after the rotor starts spinning.

Specific examples of cationic cellulose include cationic modified hydroxyethyl cellulose such as hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride, which is component (B1), and hydroxyethyl cellulose dimethyl diallyl ammonium chloride polymer, which is component (B2).

Examples of commercially available products of component (B1) include products under the trade name "Leoguard GP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", "Leoguard MGP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", "Leoguard MLP (quaternary nitrogen content 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", "SUPRACARE 212 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co., Ltd.)", "SUPRACARE 240 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co., Ltd.)", "SUPRACARE 241 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Co., Ltd.)", "UCARE Examples of such products include JR125 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Company), trade name "UCARE JR400 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Company), trade name "UCARE LR30M (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Company), trade name "Catinal HC-100 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", trade name "Catinal HC-200 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", trade name "Catinal LC-100 (quaternary nitrogen content 1.0% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", and trade name "Catinal LC-200 (quaternary nitrogen content 1.0% by mass, manufactured by Toho Chemical Industry Co., Ltd.)".

Examples of commercially available products of the component (B4) include products under the trade names "SoftCAT SL-5 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Company)", "SoftCAT SL-60 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Company)", "SoftCAT SL-100 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Company)", "SoftCAT SX-400X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Company)", "SoftCAT SX-1300X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Company)", and "SoftCAT SX-400H (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Company)".
Among these, "SUPRACARE 212" and "UCARE JR125" which are component (B1) are preferred from the viewpoint of water drainage performance.

The component (B) may be used alone or in a suitable combination of two or more types.
The content of component (B) is preferably 0.01 to 1.0 mass%, more preferably 0.1 to 0.4 mass%, and particularly preferably 0.16 to 0.4 mass%, based on the total mass of the bathroom liquid cleaner composition. When the content of component (B) is within the above range, it is easy to achieve both sebum cleansing power and rinsing performance. By making it 0.01 mass% or more, it is easy to obtain sufficient sebum cleansing power. By making it 1.0 mass% or less, it is easy to obtain sufficient rinsing performance.

<Component (C)>
Component (C) is an aromatic compound represented by any one of the following general formulas (C1) to (C3). Component (C) is used to provide an effective cleaning power against sebum stains adhering to the interior of the bathroom.

In general formula (C1), A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, and h is a number from 1 to 6 representing the average number of moles of A ¹ O added. In general formula (C2), A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and j is a number from 0 to 6 representing the average number of moles of A ² O added. In general formula (C3), A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and k is a number from 1 to 6 representing the average number of moles of A ³ O added.
Each of A ¹ O, A ² O, and A ³ O is preferably an oxyethylene group having 2 carbon atoms. Each of h and k is preferably an integer of 1 to 3. j is preferably an integer of 0 to 3.

Specific examples of aromatic compounds represented by (C1) include ethylene oxide adducts (EO adducts) such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and polyoxyethylene glycol monophenyl ether, and propylene oxide adducts (PO adducts) such as propylene glycol monophenyl ether, dipropylene glycol monophenyl ether, and polyoxypropylene glycol monophenyl ether.

Specific examples of the aromatic compound represented by (C2) include benzyl alcohol and ethylene glycol monobenzyl ether.
Specific examples of the aromatic compound represented by (C3) include 2-phenylethyl alcohol.

Among these, EO adducts such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and polyoxyethylene glycol monophenyl ether are preferred, with ethylene glycol monophenyl ether and diethylene glycol monophenyl ether being particularly preferred.

The component (C) may be used alone or in a suitable combination of two or more types.
The content of component (C) is preferably 0.1 to 3.0% by mass, more preferably 0.5 to 2.0% by mass, and particularly preferably 0.8% to 1.5% by mass, based on the total mass of the bathroom liquid cleaner composition. When the content of component (C) is within the above range, it is easy to achieve both sebum cleansing power and rinsing properties. By making it 0.1 mass% or more, it is easy to obtain sufficient sebum cleansing power. By making it 3.0 mass% or less, it is possible to suppress the tendency to choke when filling a spray container and using it.

<Component (D)>
The component (D) is a glycol ether solvent represented by the following general formula (D).
Component (D) is used in combination with component (C) to provide an effective cleaning power against sebum stains adhering to the interior of the bathroom.

R ¹ O-(A ⁴ O) _n -R ² ...(D)
In general formula (D), R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number from 0.1 to 20 that represents the average number of moles of A ⁴ O added.

R ¹ is preferably a linear alkyl group having 1 to 4 carbon atoms, and more preferably a linear alkyl group having 2 to 4 carbon atoms.
^R2 is preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.
A ⁴ O is preferably an oxyalkylene group having 2 to 3 carbon atoms, and more preferably an oxyethylene group having 2 carbon atoms.
n is preferably 1 to 3, and more preferably 2.

Specific examples of the component (D) include ethylene glycol-based ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether; and propylene glycol-based ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
Among these, ethylene glycol ethers are preferred, and diethylene glycol monobutyl ether is more preferred.

The component (D) may be used alone or in a suitable combination of two or more types.
The content of component (D) is preferably 0.1 to 5.0% by mass, and more preferably 1.0 to 2.5% by mass, based on the total mass of the bathroom liquid cleaner composition. By setting the content within this range, better sebum cleansing power and rinsing properties can be obtained.

<Mixing ratio>
In the bathroom liquid cleaner composition of the present invention, the ratio of the mass of component (B) to the mass of component (C) [(B)/(C)] is 0.1 to 4.0, and preferably 0.2 to 1.5.
By setting the ratio [(B)/(C)] to 0.1 to 4.0, good sebum cleansing power and rinsing properties can be obtained.

In the bathroom liquid detergent composition of the present invention, the ratio of the total mass of the (A) component and the (B) component to the mass of the (C) component, [{(A)+(B)}/(C)], is preferably 0.8 to 6, and more preferably 2.0 to 5.0. By having [{(A)+(B)}/(C)] of 0.8 to 6, it becomes easier to obtain good sebum cleansing power and rinsing properties.

In the bathroom liquid cleaner composition of the present invention, the ratio of the mass of component (A) to the mass of component (B) [(A)/(B)] is preferably from 1 to 25, and more preferably from 2.5 to 15. By having [(A)/(B)] from 1 to 25, it becomes easier to obtain good sebum cleansing power and rinsing properties.

When the bathroom liquid cleaner composition of the present invention contains component (D), the ratio of the mass of component (C) to the mass of component (D) [(C)/(D)] is preferably 0.05 to 2.0, and more preferably 0.1 to 0.5. By having [(C)/(D)] of 0.05 to 2.0, it becomes easier to obtain good sebum cleansing power and rinsing properties.

<Optional ingredients>
The bathroom liquid cleaner composition of the present invention may contain, as necessary, components that are usually used in bathroom liquid cleaner compositions, in addition to the above components (A) to (D). Examples of such optional components include water, higher fatty acid salts, water-soluble solvents (excluding components (C) and (D)), bactericides, preservatives, antifungal agents, colorants, antioxidants, thickeners, UV absorbers, metal sequestering agents, solubilizers, emulsifiers, fragrances, pH adjusters, etc.

From the viewpoints of ease of handling and improved rinsing properties, the bathroom liquid cleaner composition preferably contains water as a solvent.
The water content is not particularly limited, but is preferably 50 to 99 mass %, more preferably 70 to 99 mass %, and even more preferably 90 to 99 mass %, relative to the total mass of the bathroom liquid cleaner composition.

The pH adjuster is not particularly limited, but it is preferable to use an alkaline agent selected from inorganic acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof, and it is more preferable to use an acid agent selected from hydrochloric acid and sulfuric acid, or an alkaline agent selected from sodium hydroxide and potassium hydroxide.
The pH adjusters may be used alone or in combination of two or more.

When the bathroom liquid cleaning composition contains optional components other than water, the content of the optional components other than water is preferably 0.1 to 10 mass%, and more preferably 0.1 to 5 mass%, relative to the total mass of the bathroom liquid cleaning composition.
The total amount of the components constituting the bathroom liquid cleaner composition of the present invention is 100% by mass.

<Properties of the composition>
The bathroom liquid cleaner composition of the present invention preferably has a pH at 25° C. of 6 or more, more preferably 9 or more, even more preferably 9.5 to 12, and particularly preferably 10 to 11. By setting the pH in this range, good descaling power is easily obtained.
The pH can be adjusted by adding an appropriate amount of a pH adjuster.
In this specification, the pH is a value measured at 25° C. using a pH meter (product name: HM-30G, manufactured by DKK-TOA Corporation).

The viscosity of the bathroom liquid cleaning composition of the present invention at 25°C is preferably 1 to 100 mPa·s, more preferably 1 to 50 mPa·s. If the viscosity at 25°C is equal to or greater than the above lower limit, the adhesion of the bathroom liquid cleaning composition to the object to be cleaned, such as a bathtub, is improved. If the viscosity at 25°C is equal to or less than the above upper limit, the bathroom liquid cleaning composition is easy to dispense from a dispenser such as a spray container, and handling is improved.

The viscosity of the bathroom liquid cleaner composition can be adjusted by the water content, the addition of a thickener, etc.
The viscosity of the bathroom liquid cleaning composition is measured at 25° C. using a Brookfield viscometer with rotor number 1 at a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

<Method of manufacturing bathroom liquid cleaning composition>
The bathroom liquid cleaner composition is produced by a conventionally known production method, for example, a method in which the above-mentioned components (A) to (D) are added to water as a solvent, and optional components are added as necessary, followed by mixing.

<Method of using the bathroom liquid cleaning composition>
Methods for using the bathroom liquid cleaner composition include, for example, a method in which a cleaning tool such as a sponge is impregnated with the bathroom liquid cleaner composition and the object to be cleaned, such as the wall surfaces of the bathroom, the surface of the bathtub, and other bathroom ancillary facilities, is scrubbed with the sponge or the like, or a method in which the bathroom liquid cleaner composition is stored in a dispensing container, an appropriate amount of the bathroom liquid cleaner composition is applied from this dispensing container to the object to be cleaned, and after a certain period of time has passed, the object is rinsed with a shower or the like, thereby performing a "non-scrubbing" method.
The bathroom liquid cleaner composition of the present invention is particularly suitable for cleaning bathroom accessories made of PP, such as bath covers, bathroom mats (slatted floors), bathroom chairs, soap stands, drain strainers and hair catchers.

Examples of the discharge container for containing the bathroom liquid cleaner composition include spray containers and squeeze containers. Among them, spray containers are preferred as the discharge container for containing the bathroom liquid cleaner composition because they have excellent applicability to the object to be cleaned.

Examples of the spray container include an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, and the like. These containers may be either manual or electric. 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, and the like can be used as a propellant. These propellants may be used alone or in combination of two or more. Examples of the trigger spray container include those described in JP-A-9-268473 and JP-A-10-76196. Examples of the dispenser spray container include those described in JP-A-9-256272. An example of a pressure-accumulation type trigger spray container is described in JP 2013-154276 A.
Among these, trigger spray containers are preferred because they have good spray properties and spray patterns and provide good application properties.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. In the examples, "%" indicates "mass %" of the pure content unless otherwise specified. The composition of the bathroom liquid cleaner composition of each example is shown in Tables 1 to 5. The raw materials used in each example are as follows. The symbols in the tables represent the following:

<Ingredients used>
[Component (A)]
A-1: AOS, sodium C14-α olefin sulfonate, trade name "Lipolan LJ441" manufactured by Lion Specialty Chemicals Co., Ltd. The number after the "C" in "C14" above indicates the number of carbon atoms, and the same applies below.
A-2: LAS, sodium linear alkyl (C12-14) benzenesulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon PS-230".

[Component (B)]
B-1: Cationic cellulose, manufactured by Dow Chemical Japan, trade name "Supracare 212", quaternary nitrogen content 1.9% by mass, viscosity of 2% by mass aqueous solution at 25°C 130 mPa·s).
B-2: Cationic cellulose, manufactured by Toho Chemical Industry Co., Ltd., product name "Catinal LC-100", quaternary nitrogen content 1.0% by mass, viscosity of 2% by mass aqueous solution at 25°C 600 mPa·s).
B-3: Cationic cellulose (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Leoguard GP", quaternary nitrogen content 1.8% by mass, viscosity of 2% by mass aqueous solution at 25° C. 300 mPa·s).

[Component (C)]
C-1: Ethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., trade name "Phenyl Glycol".
C-2: Diethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., trade name "Phenyl Diglycol".
C-3: Polyoxyethylene monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., trade name "Phenyl Glycol 55".
C-4: Benzyl alcohol, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Benzyl Alcohol".
C-5: Ethylene glycol monobenzyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "2-(Benzyloxy)ethanol".

[Component (D)]
D-1: Diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd., trade name "Butyl Diglycol".

[Other ingredients]
Potassium coconut oil fatty acid: manufactured by Lion Specialty Chemicals Co., Ltd., product name "Potassium coconut oil fatty acid."
pH adjuster: 1N sodium hydroxide (Kanto Chemical Co., Ltd.).
Water: Ion-exchanged water.

<Examples 1 to 24, Comparative Examples 1 to 4>
According to the compositions shown in Tables 1 to 5, components (A) to (D) and other components were added to water and mixed, and the pH was adjusted to the value in the table with a pH adjuster to obtain a bathroom liquid cleaning composition of each example. The compositions (components and content (mass %)) of the bathroom liquid cleaning composition of each example obtained are shown in the tables. Unless otherwise specified, mass % indicates pure content. In the tables, if there is a component that is left blank, that component is not included. In the tables, the content of pH adjuster "appropriate amount" is the amount required to adjust the pH of the bathroom liquid cleaning composition of each example to the value in the table. In the tables, the content of water "balance" refers to the remainder added so that the total content (mass %) of all components contained in the bathroom liquid cleaning composition becomes 100 mass %.

<Evaluation method>
The bathroom liquid cleaner compositions of each example were evaluated for sebum detergency and rinsing ability as follows. The results are shown in Tables 1 to 5.

[Evaluation of sebum stain cleaning power]
A dirt liquid was prepared by mixing 30 g of beef tallow (Kanto Chemical Co., Ltd.), 20 g of soybean oil (Kanto Chemical Co., Ltd.), 0.05 g of Sudan IV (Kanto Chemical Co., Ltd.) with 50 mL of chloroform (Kanto Chemical Co., Ltd., special grade). 50 mL of this dirt liquid was placed in a glass bottle, and a 1 x 5 cm PP plate (Test Piece Co., Ltd.) was immersed in it, removed, and dried for at least 1 hour to prepare a dirt plate.

50 mL of the bathroom liquid cleaner composition described in the Examples and Comparative Examples was placed in a 100 mL glass bottle, and the dirty board was immersed in this bathroom liquid cleaner composition for 3 minutes. After that, the dirty board was removed and the state of dirt removal was visually observed and evaluated according to the following evaluation criteria. In the following evaluation criteria, if it is rated as ◯ or higher, the cleaning power for practical epidermal grease stains is good.

Evaluation criteria: Excellent stain removal.
Good: Dirt removal is good.
△: Dirt removal is uneven.
×: Almost no dirt is removed.

[Evaluation of rinsing ability]
The liquid bathroom cleaner composition of each example was filled into a trigger container of a commercially available bathroom cleaner "Ofuro no Look," and sprayed 10 times at equal intervals into the inside of an FRP bathtub (100 x 75 x 65 cm). After that, the entire inside surface of the bathtub was rubbed in a circular motion with a urethane sponge while applying a load of about 10 g/ ^cm2 , and then rinsed with tap water using a shower (water temperature 15°C, flow rate 0.2 L/sec). The time until the foam completely disappeared from the bathtub drain was measured, and the rinsing ability of the liquid bathroom cleaner composition was evaluated according to the following evaluation criteria. In the following evaluation criteria, ◎ and ○ were considered to be acceptable.

Evaluation criteria.
◎: Less than 19 seconds.
○: 20 seconds or more and less than 23 seconds.
△: 23 seconds or more but less than 30 seconds.
×: More than 31 seconds.

As shown in Tables 1 to 4, all of Examples 1 to 24 were excellent in sebum cleansing power and rinsing ability.
In contrast, as shown in Table 5, Comparative Example 1 not containing component (B) and Comparative Example 2 not containing component (C) had insufficient sebum cleansing power.
Moreover, Comparative Examples 3 and 4, in which [(B)/(C)] was outside the range of 0.1 to 4.0, had insufficient sebum cleansing power, and Comparative Example 4 also had insufficient rinsing properties.

Claims (3)

Component (A): a non-soap anionic surfactant;
(B) component: cationic cellulose,
(C) component: containing an aromatic compound,
The component (C) is represented by any one of the following general formulas (C1) to (C3):

[In general formula (C1), A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, and h is a number from 1 to 6 representing the average number of moles of A ¹ O added. In general formula (C2), A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and j is a number from 0 to 6 representing the average number of moles of A ² O added. In general formula (C3), A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and k is a number from 1 to 6 representing the average number of moles of A ³ O added.]
the ratio of the mass of the component (B) to the mass of the component (C) [(B)/(C)] is 0.1 to 4.0;
A bathroom liquid cleaning composition , in which the ratio of the total mass of the component (A) and the component (B) to the mass of the component (C), [{(A)+(B)}/(C)], is 0.8 to 6 . 2. The bathroom liquid cleaning composition according to claim 1 , wherein the ratio of the mass of the component (A) to the mass of the component (B) [(A)/(B)] is 1 to 25. Further, it contains a component (D): a glycol ether-based solvent,
The component (D) is represented by the following general formula (D):
R ¹ O-(A ⁴ O) _n -R ² ...(D)
[In general formula (D), R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number from 0.1 to 20 representing the average number of moles of A ⁴ O added.]
The bathroom liquid cleaning composition according to claim 1 or 2 , wherein the ratio of the mass of the (C) component to the mass of the (D) component [(C)/(D)] is 0.05 to 2.0.