JP2018012816A - Bath room detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bath room detergent composition that has excellent detergency and excellent bactericidal power and can inhibit discoloration of metal well.SOLUTION: A bath room detergent composition contains a surfactant (A), an aminocarboxylic acid type chelator (B), water-soluble silver (C), and polyhexamethylene biguanide (D), where a silver concentration is 0.0002-0.02 mass% relative to the bath room detergent composition, and a mass ratio represented by the (C) component/the (D) component is 0.03-4.SELECTED DRAWING: None

Description

  The present invention relates to a bathroom cleaner composition.

It is required to provide sterilizing power to the bathroom cleaning composition because of increasing hygiene awareness of consumers.
For example, Patent Document 1 proposes a bathroom cleaning composition to which sterilizing power is imparted by a combination of an anionic surfactant, a water-soluble solvent, a sequestering agent, and a polyhexamethylene biguanide antibacterial agent. ing.

JP 2011-190376 A

Silver compounds are known as compounds having excellent sterilizing power. When the present inventors tried to mix | blend a silver compound in the composition of patent document 1 instead of a polyhexamethylene biguanide type | system | group antibacterial agent, the cleaning composition for bathrooms was added to the metal product in a bathroom. It has been found that discoloration may occur in the metal product when contacted.
An object of the present invention is to provide a bathroom cleaning composition having good detergency and good sterilizing power and good metal discoloration inhibiting property (hard to cause discoloration of metal).

The present invention has the following aspects.
[1] A bathroom cleaner composition containing a surfactant (A), an aminocarboxylic acid chelating agent (B), water-soluble silver (C), and polyhexamethylene biguanide (D), A bathroom in which the silver concentration is 0.0002 to 0.02% by mass with respect to the bathroom cleaner composition, and the mass ratio represented by the component (C) / the component (D) is 0.03 to 4. Detergent composition.
[2] The bathroom cleaning composition according to [1], wherein the pH at 25 ° C. is 10.1 or more and less than 12.
[3] The bathroom cleaner composition according to [1] or [2], wherein the component (A) includes a non-soap anionic surfactant (a1).

[4] The non-soap anionic surfactant (a1) is an α-olefin sulfonate having an alkyl group having 10 to 20 carbon atoms, a linear alkylbenzene sulfonate having an alkyl group having 10 to 20 carbon atoms, Alkyl sulfate having an alkyl group having 10 to 20 carbon atoms, α-sulfo fatty acid ester salt having an alkyl group derived from fatty acid having 10 to 20 carbon atoms, and polyoxy having an average addition mole number of ethylene oxide of 1 to 10 The bathroom cleaner composition according to [3], comprising at least one selected from the group consisting of ethylene alkyl ether sulfates.
[5] The bathroom cleaning composition according to [4], wherein the non-soap anionic surfactant (a1) includes an α-olefin sulfonate having an alkyl group having 10 to 16 carbon atoms.
[6] The bathroom cleaner composition according to any one of [1] to [5], wherein the component (C) is a silver complex.
[7] The bathroom cleaner according to any one of [1] to [6], wherein the content of the component (D) is 0.005 to 0.05% by mass with respect to the bathroom cleaner composition. Composition.

  ADVANTAGE OF THE INVENTION According to this invention, it has the favorable detergency and the favorable disinfection power, and can provide the detergent composition for bathrooms with the favorable discoloration suppression property (it is hard to produce discoloration) of a metal.

  The bathroom cleaner composition of the present invention (hereinafter also simply referred to as “cleaner composition”) is a liquid composition containing the following components (A) to (D).

<(A) component>
The component (A) is a surfactant. Examples include non-soap anionic surfactant (a1), higher fatty acid salt (a2), amphoteric surfactant (a3), nonionic surfactant (a4), and cationic surfactant (a5).
One surfactant may be used, or two or more surfactants may be used in combination.
The component (A) preferably contains at least a non-soap anionic surfactant (a1).
In the present invention, the non-soap anionic surfactant is an anionic surfactant excluding a higher fatty acid salt, and the higher fatty acid salt is a saturated or unsaturated fatty acid salt having 8 to 24 carbon atoms.

[Non-soap anionic surfactant (a1)]
The non-soap anionic surfactant (a1) is not particularly limited, and examples thereof include linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), polyoxyethylene alkyl ether sulfate (AES), α -Olefin sulfonate (AOS), alkane sulfonate, α-sulfo fatty acid ester salt (α-SF), polyoxyethylene alkyl ether carboxylate and the like. The non-soap anionic surfactant (a1) is particularly excellent in detergency.
The non-soap anionic surfactant (a1) may be used alone or in combination of two or more.

As the linear alkylbenzene sulfonate, an alkyl group having 10 to 20 carbon atoms is preferable, and an alkyl group having 10 to 16 carbon atoms is more preferable.
As the alkyl sulfate, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 10 to 16 carbon atoms in the alkyl group are more preferable.
The polyoxyethylene alkyl ether sulfate is more preferably one having an alkyl group having 10 to 20 carbon atoms and an average added mole number of ethylene oxide of 1 to 10.
As the α-olefin sulfonate, those having an alkyl group having 10 to 20 carbon atoms are preferable, and those having an alkyl group having 10 to 16 carbon atoms are more preferable.
As the alkane sulfonate, an alkyl group having 10 to 20 carbon atoms is preferable, and an alkyl group having 10 to 16 carbon atoms is more preferable.
As the α-sulfo fatty acid ester salt, the alkyl group derived from the fatty acid preferably has 10 to 20 carbon atoms, and more preferably the alkyl group has 10 to 18 carbon atoms.
As the polyoxyethylene alkyl ether carboxylate, one having an alkyl group having 10 to 20 carbon atoms and an average added mole number of ethylene oxide of 1 to 10 is more preferable.

Among these, linear alkylbenzene sulfonate, alkyl sulfate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfate, α-sulfo fatty acid ester salt (α-SF) are preferable, and α-olefin sulfonate. Is more preferable.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Of these, alkali metal salts such as sodium salt and potassium salt are preferred.

The component (A) contains a non-soap anionic surfactant (a1), and the non-soap anionic surfactant (a1) is an α-olefin sulfonate having an alkyl group having 10 to 20 carbon atoms, carbon number 10 A linear alkylbenzene sulfonate having an alkyl group of ˜20, an alkyl sulfate having an alkyl group of 10 to 20 carbon atoms, an α-sulfo fatty acid ester salt having an alkyl group derived from a fatty acid of 10 to 20 carbon atoms, And one or more selected from the group consisting of polyoxyethylene alkyl ether sulfates having an average addition mole number of 1 to 10 of ethylene oxide.
More preferably, the non-soap anionic surfactant (a1) contains an α-olefin sulfonate having an alkyl group having 10 to 16 carbon atoms.

[Higher fatty acid salt (a2)]
The higher fatty acid salt (a2) is a saturated or unsaturated fatty acid salt having 8 to 24 carbon atoms.
For example, potassium salts of higher fatty acids such as C12-C18 saturated and unsaturated fatty acids, coconut oil fatty acids, hardened coconut oil fatty acids, palm oil fatty acids, hardened palm oil fatty acids, beef tallow fatty acids, or hardened beef tallow fatty acids which are mixtures thereof, Fatty acid soap such as sodium salt, triethanolamine salt, or ammonium salt; alkyl ether carboxylate, N-acyl sarcosine salt, or N-acyl glutamate of the higher fatty acid.
More specifically, for example, potassium laurate, potassium myristate, potassium stearate, sodium lauryl ether carboxylate, sodium N-lauroyl sarcosine, sodium N-lauroyl glutamate, N-lauroylmethyl-β-alanine triethanolamine, etc. Can be mentioned.
The fatty acid salt may be blended as it is, or the fatty acid salt and the alkali may be blended separately in the detergent composition and neutralized. The higher fatty acid salt (a2) is particularly excellent in the effect of suppressing foaming during rinsing.

[Amphoteric surfactant (a3)]
The kind of amphoteric surfactant (a3) is not particularly limited, and can be appropriately selected from known amphoteric surfactants. For example, specific examples of amphoteric surfactants include betaine type amphoteric surfactants such as alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone betaine type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, N -Amino acid type amphoteric surfactants such as acyl amino acid salts, N-acyl methyl taurate salts, alkyl amino acid types, and phosphoric acid type amphoteric surfactants.
Among these, betaine-type amphoteric surfactants are preferable, and it is particularly preferable that the amphoteric surfactant (a3) contains lauryldimethylaminoacetic acid betaine.

[Nonionic surfactant (a4)]
Nonionic surfactant (a4) includes polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid polyglycerin ester, fatty acid sucrose ester, fatty acid alkanolamide, alkylamine Examples thereof include oxides and alkylamidoamine oxides.
Among these, polyoxyethylene alkyl ether is preferable, and the nonionic surfactant (a4) particularly preferably includes polyoxyethylene alkyl ether.

[Cationic surfactant (a5)]
Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts, imidazolium salts, and the like. The counter ions of these cationic surfactants are halogen ions, methyl sulfate ions and the like.

The content of the component (A) (hereinafter also referred to as “(A) component total amount”) is preferably 0.1 to 5% by mass, and 1 to 5% by mass with respect to the total mass of the cleaning composition. % Is more preferable. When the total amount of component (A) is not less than the lower limit of the above range, good detergency is easily obtained, and when it is not more than the upper limit, good rinsing properties are easily obtained.
Moreover, 10-100 mass% is preferable with respect to the total amount of (A) component, non-soap-type anionic surfactant (a1) is preferable, 15-90 mass% is more preferable, and 20-85 mass% is further more preferable.
Moreover, it is preferable that 0.1-5 mass% of alpha olefin sulfonates are included with respect to the gross mass of a cleaning composition, 0.2-4 mass% is more preferable, 0.3-4 mass% Is more preferable.

<(B) component>
The component (B) is an aminocarboxylic acid type chelating agent.
As the component (B), methyl glycine diacetate (MGDA), aspartate diacetate (ASDA), isoserine diacetate (ISDA), β-alanine diacetate (ADAA), serine diacetate (SDA), glutamate diacetate (GLDA), Iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), nitrilotriacetic acid (NTA), iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionic acetic acid, Triethylenetetraamine hexaacetic acid (TTHA), ethylene glycol diamine tetraacetic acid, hydroxyethyleneiminodiacetic acid (HIDA), hydroxyethylenediamine triacetic acid (HEDTA), dihydroxyethyl group Syn (DHEG), N-lauroylethylenediaminetriacetic acid, cyclohexane-1,2-diaminetetraacetic acid, diencoric acid, glycol etherdiaminetetraacetic acid (GEDTA), dicarboxymethylglutamic acid (CMGA), (S, S) -ethylenediaminedi Examples thereof include succinic acid (EDDS) and salts thereof.
Among these, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DTPA), or a salt thereof is preferable. Ethylenediaminetetraacetic acid (EDTA) or a salt thereof is particularly preferred.
As the component (B), any one type may be used alone, or two or more types may be combined.

  It is preferable that content of (B) component is 0.2-5 mass% with respect to the total mass of a cleaning composition, and 0.5-3 mass% is more preferable. When the content of the component (B) is not less than the lower limit of the above range, good detergency can be easily obtained, and when it is not more than the upper limit, good metal discoloration suppressing properties can be easily obtained.

<(C) component>
(C) A component is water-soluble silver. The “water-soluble silver” in the present invention contains silver, and when formulated so that the silver concentration with respect to the total mass of the cleaning composition is 0.0002 to 0.02% by mass, the cleaning composition contains It can be dissolved transparently or evenly dispersed. In particular, those that are transparently soluble in the detergent composition are preferred. Silver is silver alone.

As water-soluble silver, (1) a silver complex or (2) a silver carrier is preferable.
(1) Silver complexes include silver and amino acids (histidine, arginine, creatinine, etc.), silver and carboxylic acids (pyruvic acid, glycolic acid, acetic acid, butyric acid, salicylic acid, etc.), silver, carboxylic acid, and amino acid. And a complex of silver and an imidazole derivative.
(2) As a silver carrier, silver salt or silver itself, inorganic phosphates such as zirconium phosphate and calcium phosphate, metal oxides such as silicon oxide, aluminum oxide and boron oxide, zeolites, viscous minerals, silica gel and the like Those supported on a compound may be mentioned.
(1) A silver complex or (2) a silver carrier can be obtained from a commercial product.

From the viewpoint of sterilization power and suppression of metal discoloration, a silver complex is preferable, and a silver complex containing an amino acid such as creatinine is more preferable.
The content of the component (C) in the cleaning composition is such that the concentration of silver derived from the component (C) is 0.0002 to 0.02% by mass with respect to the total mass of the cleaning composition. And the concentration of the silver is preferably 0.0005 to 0.01% by mass, and more preferably 0.001 to 0.005% by mass. When it is at least the lower limit of the above range, good sterilizing power can be easily obtained, and when it is at most the upper limit, good metal discoloration suppressing properties are easily obtained.

<(D) component>
(D) A component is polyhexamethylene biguanide or its acid salt.
Examples of polyhexamethylene biguanide or its acid salt include compounds represented by the following general formula (I).

[Wherein, m is an integer of 2 to 14. HR represents an organic acid or an inorganic acid. n means the number of HR and is an integer of 0 to 5 m. ]
In said formula (I), m is an integer of 2-14, the integer of 10-14 is preferable, the integer of 11-13 is more preferable, and 12 is especially preferable.
In the formula (I), HR represents an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid or acetic acid, more preferably hydrochloric acid.
n is an integer of 0 to 5 m. When n is 0, the compound represented by the formula (I) is polyhexamethylene biguanide. When n is not 0, the compound represented by the formula (I) is a partial or full acid salt of polyhexamethylene biguanide. n is preferably an integer of 1 to 5 m, more preferably an integer of 2 to 3 m, still more preferably an integer of m to 2 m, and particularly preferably m.

In the present invention, the mass ratio represented by component (C) / component (D) (hereinafter also referred to as C / D ratio) is 0.03 to 4, preferably 0.05 to 2, 1 is more preferable. When the C / D ratio is at least the lower limit of the above range, good sterilizing power can be easily obtained, and when the C / D ratio is at most the upper limit, good metal discoloration inhibiting properties can be easily obtained.
The content of the component (D) is preferably 0.005 to 0.05% by mass, more preferably 0.005 to 0.03% by mass with respect to the total mass of the cleaning composition, -0.03 mass% is still more preferable. When the content of the component (D) is at least the lower limit of the above range, good metal discoloration suppressing properties are easily obtained, and when it is at most the upper limit, a good appearance of the cleaning composition is easily obtained. For example, when there is too much content of (D) component, cloudiness will arise in a cleaning composition and transparency may be lost.

<PH>
The cleaning composition of the present invention preferably has a pH at 25 ° C. of 10.1 or more and less than 12. The pH is preferably 10.1 to 11.4, more preferably 10.4 to 11.4.
When the pH is not less than the lower limit within the above range, good detergency can be obtained, and when the pH is not more than the upper limit, good metal discoloration suppression can be obtained.
The pH of the cleaning composition in the present invention is a value measured at 25 ° C. according to JIS Z8802: 2011.

<PH adjuster>
In order to make the cleaning composition of the present invention have the above pH, a pH adjusting agent is blended as necessary.
Although it does not specifically limit as a pH adjuster, Organic acids, such as inorganic acids, such as hydrochloric acid and a sulfuric acid, a citric acid, a succinic acid, malic acid, a fumaric acid, tartaric acid, malonic acid, a maleic acid, p-toluenesulfonic acid, ethylenediaminetetra Examples include acid agents such as acetic acid, sodium hydroxide and potassium hydroxide, ammonia and derivatives thereof, and amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and alkali agents such as sodium carbonate and potassium carbonate.
In particular, an acid selected from hydrochloric acid, sulfuric acid, and citric acid is preferable. Or the alkali agent chosen from sodium hydroxide and potassium hydroxide is preferable.
Any one of the pH adjusting agents may be used alone, or two or more may be used in combination.

<Solvent>
The cleaning composition of the present invention usually contains water as a solvent because it is easy to prepare the cleaning composition and easily dissolves in water upon rinsing. A water-soluble solvent may be contained in addition to water as a solvent. In the present invention, the water-soluble solvent refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
Examples of water-soluble solvents include diethylene glycol monobutyl ether (also known as butyl carbitol), triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, propylene glycol monopropyl ether, A fit etc. are mentioned.
A water-soluble solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the water-soluble solvent is preferably 0.1 to 5.0% by mass and more preferably 1.0 to 3.0% by mass with respect to the total mass of the cleaning composition.
The total content of water and the water-soluble solvent in the cleaning composition is not particularly limited, but is preferably 50 to 99.5% by mass, and 70 to 99% by mass with respect to the total mass of the cleaning composition. More preferably, 75-98 mass% is further more preferable.

<Other optional components>
The cleaning composition of the present invention can contain components that can usually be used in cleaning agents in addition to the above components, if necessary. Examples of such optional components include preservatives, antifungal agents, dyes, antioxidants, thickeners, ultraviolet absorbers, solubilizers, and fragrances.

The cleaning composition of the present invention preferably has a viscosity at 25 ° C. of 1 to 100 mPa · s, and more preferably 1 to 50 mPa · s.
If the viscosity in 25 degreeC is more than the said lower limit, the adhesiveness of the cleaning composition with respect to washing | cleaning objects, such as a bathtub, will improve more. When the viscosity at 25 ° C. is not more than the above upper limit value, the cleaning composition can be easily discharged from a discharge container such as a spray container, and the handleability is improved.
The viscosity at 25 ° C. of the cleaning composition in the present invention is a value measured using a B-type viscometer (manufactured by TOKIMEC) after adjusting the sample to 25 ° C. (an example of measurement conditions: rotor No. 1, the rotation number is 60 rpm, and the viscosity after 10 rotations is measured).

  The cleaning composition of the present invention is produced by a conventionally known production method. For example, the method of adding the said (A)-(D) component to a solvent, adding a pH adjuster and another arbitrary component as needed, and mixing this is mentioned.

  The cleaning composition of the present invention can be used, for example, by impregnating a cleaning tool such as a sponge with the cleaning composition, and rubbing a cleaning target such as a bathroom wall surface, a bathtub surface, or other bathroom accessories with a sponge or the like. Examples of usage include washing, use of cleaning composition in a discharge container, application of an appropriate amount of the cleaning composition from the discharge container to the object to be cleaned, and scrubbing with a sponge. .

Examples of the discharge container for storing the cleaning composition of the present invention include a spray container and a squeeze container. However, a spray container is preferable because it is excellent in applicability to an 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 manually operated or electrically operated.
As an aerosol spray container, what is described in Unexamined-Japanese-Patent No. 9-3441, Unexamined-Japanese-Patent No. 9-58765 etc. is mentioned, for example. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, or 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, JP-A-10-76196, and the like.
As an example of a dispenser spray container, the thing as described in Unexamined-Japanese-Patent No. 9-256272 etc. is mentioned, for example.
Examples of the pressure accumulation type trigger spray container include those described in JP2013-154276A.
Among these, a pressure accumulation type trigger spray container is preferable because the spray properties and spray pattern are good and good coating properties are obtained.

  As described above, the cleaning composition of the present invention contains the surfactant (A) and the aminocarboxylic acid type chelating agent (B), and contains water-soluble silver (C) so that the silver has a specific concentration. In addition, since it contains polyhexamethylene biguanide (D) so as to have a predetermined C / D ratio, it has a good detergency and a good sterilizing power, and is excellent in metal discoloration suppression.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The composition of the cleaning composition of each example is shown in Tables 1-5.
The raw materials used in this example are as follows.

<(A) component>
[Non-soap anionic surfactant (a1)]
(A1-1): C14-α sodium olefin sulfonate, manufactured by Lion Corporation, trade name “Lipolane LJ441”. “C” in “C14” means the number of carbon atoms, and the same applies hereinafter.
(A1-2): Lauryl sulfate, Lion Corporation, trade name “Sunnol LM-1130”.
(A1-3): C12-18α sulfo fatty acid methyl ester salt, manufactured by Lion Corporation, trade name “MIZULAN FL-80”.
(A1-4): Polyoxyethylene alkyl (C12-14) ether sulfate [average added mole number of ethylene oxide 2], manufactured by Shin Nippon Rika Co., Ltd., trade name “Sinoline SPE-1250”.
(A1-5): Long-chain alkyl (C10-16) sodium alkylbenzenesulfonate, manufactured by Lion Corporation, trade name “Lypon PS230”.

[Higher fatty acid salt (a2)]
(A2-1): Palm oil fatty acid potassium, manufactured by Lion Chemical Co., Ltd., trade name “coconut oil fatty acid potassium”.
(A2-2): Potassium myristate, manufactured by NOF Corporation, trade name “NONSAR MK-1”.
[Amphoteric surfactant (a3)]
(A3-1): Lauryldimethylaminoacetic acid betaine, manufactured by Sanyo Chemical Industries, Ltd., trade name “Levon LD-36”.
[Nonionic surfactant (a4)]
(A4-1): Polyoxyethylene alkyl (C-12, 14) ether, Lion Corporation, trade name “Leox CL-70”.

<(B) component>
(B-1): Disodium ethylenediaminetetraacetate (EDTA2Na), manufactured by Akzo Nobel, trade name “Disorbin NA2”.
(B-2): Hydroxyethylenediaminetriacetic acid (HEDTA), manufactured by Kyrest Co., Ltd., trade name “Kyrest HA”.
(B-3): Dihydroxyethylglycine (DHEG), manufactured by Kyrest Co., Ltd., trade name “Kyrest GA”.
(B-4): Hydroxyethyleneiminodiacetic acid (HIDA), manufactured by Kyrest Co., Ltd., trade name “Kyrest EA”.
(B-5): Diethylenetriaminepentaacetic acid (DTPA), manufactured by Kyrest Co., Ltd., trade name “Kyrest PA”.

<(C) component>
(C-1): Silver complex, manufactured by J Chemical Co., Ltd., trade name “CF01”, silver concentration 2.5%. Complex of silver, carboxylic acid and creatinine.
(C-2): Silver carrier, manufactured by Koa Glass Co., Ltd., trade name “Million Guard PG601”, silver concentration 3.1%.
(C-3): Silver carrier, JGC Catalysts & Chemicals Co., Ltd., trade name “Atom Ball UA”, silver concentration 0.1%.

<(D) component>
(D-1): Polyhexamethylene biguanide hydrochloride, manufactured by Arch Chemical Japan, trade name “Proxel IB”.
<Other ingredients>
pH adjusting agent: 1N sodium hydroxide, 1N hydrochloric acid (manufactured by Kanto Chemical Co., Inc.).
<Solvent>
Water-soluble solvent: diethylene glycol monobutyl ether.
Water: Purified water.

<Examples 1 to 25 and Comparative Examples 1 to 6>
According to the composition shown in Tables 1 to 5, after adding (A) component, (B) component, (C) component, (D) component and water-soluble solvent to water and mixing, pH is expressed with a pH adjuster. The detergent composition was obtained by adjusting to the medium value. In Comparative Example 1, the component (A) was not used, in Comparative Example 2, the component (B) was not used, in Comparative Example 3, the component (C) was not used, and in Comparative Example 4, the component (D) was not used. .
The viscosities at 25 ° C. of the cleaning compositions obtained in Examples 1 to 25 were all in the range of 1 to 3 mPa · s.
In the table, unless otherwise specified, mass% represents pure content.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content “appropriate amount” of the pH adjusting agent is an amount required to bring the pH of the cleaning composition of each example to the value in the table.
In the table, the water content “balance” means the balance added so that the total amount (mass%) of all the ingredients contained in the cleaning composition is 100 mass%.

<Evaluation method>
About the cleaning composition of each example, the cleaning power, disinfection power, and the metal discoloration inhibitory property were evaluated as follows. The evaluation results are shown in Tables 1-5.
[Evaluation of cleaning power]
Three adult men bathed three times each on the inner wall surface of a tub in a general household (bath once a day and repeated for three days, during which time only the bath water was replaced and the tub was not washed), and dirt was adhered.
Without removing the hot water in the bathtub, the hot water was immediately removed after spraying the cleaning composition so that the entire water surface was covered with foam. After leaving hot water for 60 seconds, it was rinsed with tap water (15 ° C.). After thoroughly drying, apply a residual protein detection solution (trade name “New Ultester P”, manufactured by Albose) to the entire inner wall of the bathtub, leave it for 60 seconds, and rinse with tap water (15 ° C.). did.
As a control example, without washing the inner wall surface of the bathtub to which dirt was adhered in the same manner, after removing hot water and drying it sufficiently, the residual protein detection solution was applied and allowed to stand for 60 seconds, and then rinsed with tap water. .
The colored state of the inner wall surface of the bathtub was visually observed and scored according to the following criteria. The evaluation was performed by five people, and the average value of the scores of the five people was used as the evaluation result. Three or more points were accepted.
[Evaluation criteria for cleaning power]
5 points: A level at which coloring is not discriminated even if eyes are closed.
4 points: A level where you can see the color when you look closely.
3 points: Although it was thinner than the control example, it is a level where it can be seen that it is colored.
2 points: Slightly thinner than the control example, but at a level where it is clearly colored.
1 point: The same coloring level as the control example.

[Evaluation of sterilizing power]
(1) Preparation of Control Sample A 0.05 mass% aqueous solution of polyoxyethylene sorbitan monooleate (trade name “Tween 80”, manufactured by Tokyo Chemical Industry Co., Ltd.) was autoclaved and used as a control sample.
(2) Preparation of bacterial solution for test S. aureus and Escherichia coli were mixed with TSA (Triple Soy Agar) medium (Dif
co), and cultured in advance at 37 ° C. for 18 to 20 hours. Next, this bacterium is inoculated into TSA medium, pre-cultured at 37 ° C. for 18 to 20 hours, and then prepared to be 106 CFU / mL using a sterilized 1 / 2NB (Nutrient Broth) medium (manufactured by Difco). did.
(3) Preparation of inactivating agent 30 g of a mixture of polypeptone, lecithin, and polysorbate (LP diluted solution Daigo (trade name), manufactured by Nippon Pharmaceutical Co., Ltd.) was dissolved in 1 L of purified water by heating and autoclaved.
(4) Sterilization of test tube Dry heat sterilization was performed at 180 ° C. for 1 hour.
(5) Bactericidal power measurement To a sterilized test tube, 1 mL of a test bacterial solution stored for 1 month in an environment at 50 ° C. is added, followed by an evaluation sample (cleaning composition obtained in each example) or a control. 9 mL of the sample was added, and allowed to stand after stirring. After standing for 10 minutes, 1 mL was collected by stirring and added to a sterilized test tube containing 9 mL of an inactivating agent, and the mixture was stirred as Test Solution-1.
Test solution-1 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 value obtained by subtracting the Log bacterium value of the evaluation sample from the Log bacterium value of the control sample was defined as the sterilization activity value, and the determination was made according to the following criteria. ◎ and ○ were accepted.
[Evaluation criteria for sterilizing power]
A: Bactericidal activity value is 2.0 or more.
○: The sterilization activity value is 1.5 or more and less than 2.0.
(Triangle | delta): Bactericidal activity value is 1.2 or more and less than 1.5.
X: Bactericidal activity value is less than 1.2.

[Evaluation of metal discoloration suppression]
The cleaning composition obtained in each example was dropped on a copper, brass, and aluminum substrate by 2 to 3 drops, wiped with a wet cloth after 24 hours, visually observed for the degree of discoloration, and evaluated according to the following criteria: did. The evaluation was performed by five people, and the average value of the scores of the five people was used as the evaluation result.
[Evaluation criteria for metal discoloration inhibition]
4 points: A level at which discoloration cannot be discerned even if eyes are closed.
3 points: If you look closely, you can see that it is discolored, but you are not worried.
2 points: A level that is worrisome when you notice that the color has changed.
1 point: A level that clearly shows discoloration.

From the results shown in Tables 1 to 5, it was confirmed that the cleaning compositions of Examples 1 to 25 to which the present invention was applied were excellent in detergency and excellent in sterilizing power and metal discoloration suppression.
On the other hand, Comparative Example 1 that does not contain the component (A) and Comparative Example 2 that does not contain the component (B) had insufficient detergency compared to the examples.
The comparative example 3 which does not contain the component (C) and the comparative example 5 which contains the component (C) and the component (D) whose C / D ratio value is smaller than the range of the present invention have insufficient sterilizing power. .
Comparative Example 4 containing no component (D) and Comparative Example 6 containing a component (C) and a component (D) whose C / D ratio value is larger than the range of the present invention are insufficient in discoloration suppression of metal. there were.

Claims (3)

A detergent composition for bathroom containing a surfactant (A), an aminocarboxylic acid type chelating agent (B), water-soluble silver (C), and polyhexamethylene biguanide (D),
Silver concentration is 0.0002-0.02 mass% with respect to the said bathroom cleaner composition,
The bathroom cleaning composition whose mass ratio represented by said (C) component / said (D) component is 0.03-4.   The bathroom cleaning composition according to claim 1, wherein the pH at 25 ° C is 10.1 or more and less than 12.   The bathroom cleaning composition according to claim 1 or 2, wherein the component (A) contains a non-soap anionic surfactant (a1).