JP7292183B2 - Hard surface cleaner composition - Google Patents

Description

The present invention relates to hard surface cleaner compositions.

In general, fatty acids contained in soaps and body shampoos and tap water adhere to hard surfaces such as plastics, tiles, stainless steel, ceramics, and glass used for bathtubs, floors, walls, and utensils in bathrooms. A mixture of organic matter such as fatty acid metal salts (soap scum) formed by binding calcium in water, nitrogen-containing compounds such as proteins, free fatty acids, glycerides, fatty acid metal salts (soap scum), etc., and inorganic substances such as mud. There is a hot water scale stain.

BACKGROUND ART Conventionally, various detergent compositions have been proposed for removing stains in bathrooms. Patent Document 1 discloses a bathroom liquid detergent composition containing a surfactant including a non-soap anionic surfactant, a glycol solvent, and an aminocarboxylic acid-type chelating agent, and having a pH of more than 10 and less than 12. It is

Due to the growing awareness of hygiene among consumers, a cleaning agent composition for bathrooms is required to have a sterilizing power. Patent Literature 2 discloses a bathroom detergent composition imparted with sterilizing power by a combination of an anionic surfactant, a water-soluble solvent, a chelating agent, and a polyhexamethylene biguanide-based antibacterial agent.
Patent Documents 3 to 5 disclose a composition containing polylysine and an inorganic compound supporting silver (silver nanocolloid) as a disinfectant.

JP 2016-124965 A JP 2011-190376 A JP 2006-151907 A Japanese Patent Application Laid-Open No. 2006-151908 Japanese Patent Application Laid-Open No. 2007-332130

However, in bathroom detergent compositions containing anionic surfactants to improve detergency and foaming during use, cationic polymers and inorganic disinfectants are used in combination to impart disinfecting power. Then, due to the formation of a complex with an anionic surfactant, etc., there is a problem that the sterilizing power is lowered especially after high-temperature storage. In addition, there is a problem that weakly alkaline to alkaline solutions are less effective against Staphylococcus aureus on many hard surfaces.

An object of the present invention is to provide a hard surface detergent composition which is excellent in detergency, sterilization power and liquid color stability.

The present invention has the following aspects.
[1] (A) component: an anionic surfactant,
(B) component: at least one selected from the group consisting of silver compounds, polyhexamethylene biguanides and salts thereof, and (C) component: at least one selected from the group consisting of basic polyamino acids and salts thereof. death,
(Silver element + polyhexamethylene biguanide + salt thereof in component (B))/component (C) has a mass ratio of 0.025 to 3.0,
A hard surface cleaning composition having a pH of 9 to 12 at 25°C.
[2] Silver in which the component (B) is complexed with at least one selected from the group consisting of polymers, amino acids, and monovalent to divalent carboxylic acids having a total of 3 to 8 carbon atoms (excluding amino acids). , polyhexamethylene biguanide and salts thereof. The hard surface cleaning composition of [1] above.
[3] Component (D): The hard surface cleaning composition of [1] or [2] above, which further contains a chelating agent.
[4] The hard surface cleaning composition of [3], wherein the component (D) contains at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salts and citric acid or its salts.
[5] The component (B) contains a silver compound,
The hard surface cleaning composition according to any one of [1] to [4], further comprising (E) component: an aromatic water-soluble solvent.
[6] The component (B) contains a silver compound,
The hard surface cleaning composition according to any one of the above [1] to [5], further comprising component (F): a nonionic surfactant.
[7] The above [1] to [1] to [1], wherein the component (B) contains a silver compound, and the mass ratio represented by silver element in the component (B)/component (C) is 0.1 to 1 6].
[8] Component (B) contains polyhexamethylene biguanide or a salt thereof, and the mass ratio represented by (polyhexamethylene biguanide in component (B) + salt thereof)/component (C) is 0.00. 5 to 3.0, the hard surface cleaning composition according to any one of the above [1] to [7].

The hard surface detergent composition of the present invention is excellent in detergency, sterilization power and liquid color stability.

The hard surface cleaning composition of the present invention contains components (A), (B) and (C).
The hard surface cleaning composition of the present invention is typically a liquid composition containing water.
The hard surface cleaning composition of the present invention preferably further contains at least one component selected from component (D), component (E) and component (F).
The hard surface cleaning composition of the present invention may, if necessary, further contain components other than components (A) to (F) within a range that does not impair the effects of the present invention.

<(A) Component>
(A) Component is an anionic surfactant.
Component (A) is used to exhibit effective detergency against sebum stains, protein stains, and the like adhering to hard surfaces.
Component (A) includes alkyl (C10-C14) benzenesulfonates, alkane (C10-C20) sulfonates, alkyl sulfates (C10-C20), alkyl sulfates (C10-C20) polyoxyethylene salts, α - olefin (C10-C16) sulfonates, alkyl (C10-C20) phenoxyphenyl disulfonates, fatty acid (C10-C20) salts, α-sulfo fatty acid (C10-C18) salts, ether carboxylic acids (C10-C20) salt, alkyl (C10-C20) phosphate, alkyl (C10-C20) polyoxyethylene phosphate, dialkyl (C8-C20) sulfosuccinate ester salt, alkyl (C10-C20) sulfosuccinate, alkenyl (C10- C20) succinates, N-acyl (C10-C20) amino acid salts, N-acyl (C10-C20) methyltaurate salts, and the like. "C" means the number of carbon atoms, and so on. These anionic surfactants can be used singly or in combination of two or more.
Among these, at least one selected from the group consisting of alkylbenzenesulfonates and α-olefinsulfonates is preferred from the standpoint of detergency.
Examples of salts include alkali metal salts such as sodium salts and potassium salts, and alkanolamine salts such as monoethanolamine salts and diethanolamine salts. Among them, alkali metal salts such as sodium salts and potassium salts are preferred.

<(B) Component>
Component (B) is at least one selected from the group consisting of silver compounds, polyhexamethylene biguanides and salts thereof.
Among components (B), silver compounds include, for example, the following components (B1), (B2) and (B3).

The (B1) component is silver complexed with a polymer (hereinafter sometimes referred to as (b11) component).
The content of silver element in component (B1) is, for example, 0.1 to 60% by mass, alternatively 0.5 to 15% by mass, alternatively 20 to 100,000 ppm, or at least 20 ppm, alternatively 20-4,000 ppm, alternatively 20-1,500 ppm, alternatively 30-75 ppm, alternatively at least 50 ppm.

The polymer of component (B1) is selected from the group consisting of unit A represented by the following formula (1), unit B represented by the following formula (2), and unit C represented by the following formula (3). (However, the ratio of the unit B is 99.5% by mass or less with respect to the total mass of the polymer.).

wherein X is selected from unsaturated or aromatic heterocycles having at least one heteroatom selected from the group consisting of N, O and S;
n is 0 or 1,
R ¹ is selected from H, CH ₃ and CO ₂ R ⁴ , R ⁴ is selected from H, CH ₃ , C ₂ H ₅ and C3-C24 alkyl groups;
^{R2 is} selected from H, _CH3 , _C2H5 , a phenyl group, _CH2CO2R5 , and _CO2R5 ^, _wherein ^R5 is _H , _a glycidyl group, ( _CH2CHR11O ) ^m H, (CH ₂ CHR ¹¹ O) _m —COCH ₂ COCH ₃ , and CH ₂ CH(OH)CH ₂ Q, R ¹¹ is selected from H, CH ₃ and a phenyl group, m is 1 is an integer of ~20, Q is selected from OH, SO _Z , and X, and Z is selected from H, Na, K, and _NH , provided that said polymer contains said unit B and said unit C is not included, R ² is -CH ₂ CO ₂ R ⁵ or -CO ₂ R ⁵ , R ⁵ is CH ₂ CH(OH)CH ₂ Q, Q is X,
R ³ is selected from H, CH ₃ , phenyl group, sulfonated phenyl group, phenol group, acetate group, hydroxy group, fragment OR ¹ , --CO ₂ R ¹² and --CONR ⁶ R ⁷ and R ¹² is selected from H, CH ₃ , C ₂ H ₅ , and C3-C24 alkyl groups, and R ⁶ and R ⁷ are each independently H, CH ₃ , C ₂ H ₅ , C(CH ₃ ) ₂ CH ₂ SO ₃ Z, and a C3-C8 alkyl group;
R ⁸ and R ⁹ are each independently selected from H, CH ₃ , C ₂ H ₅ , and C3-C24 linear or branched alkyl groups;
R ¹⁰ is a C1-C8 alkylene group, a C2-C8 alkenylene group, a C6-C10 unsaturated acyclic group, a C6-C10 cyclic group, a C6-C10 aromatic group, an oxy C2-C4 alkylene group, and a poly (oxy C2-C4 alkylene) _b groups, where b is an integer of 2-20;

In the specification and claims, "alkyl" includes straight-chain, branched-chain and cyclic alkyl groups. "Alkenyl" includes straight and branched chain alkenyl groups.
The unsaturated or aromatic heterocycle includes, for example, a 5- to 7-membered heterocycle having an unsaturated bond; an aromatic heterocycle having at least one heteroatom selected from the group consisting of N, O and S isomers of such heterocycles and combinations thereof are included. Additionally, suitable heterocycles include, for example, 5- to 7-membered heterocycles fused together to form larger 9- to 14-membered heterocycles having at least one N, O or S atom. ring; can include isomers of such heterocycles and combinations thereof.

The polymer of component (B1) may contain a heterocyclic ring-containing polymer.
Heterocycles include imidazole, thiophene, pyrrole, oxazole, thiazole and their respective isomers (e.g. thiazol-4-yl, thiazol-3-yl and thiazol-2-yl), tetrazole, pyridine, pyridazine, pyrimidine , pyrazines, azoles, indazoles, triazoles and their respective isomers (eg 1,2,3-triazole and 1,2,4-triazole), and imidazole 1,2,3-triazole-1,2,4- Combinations thereof such as triazole, benzotriazole, methylbenzotriazole, benzothiazole, methylbenzothiazole, benzimidazole and methylbenzimidazole are included.

Heterocycle-containing polymers include, for example, polymers containing units derived from heterocycle-containing monomers. Examples of heterocyclic ring-containing monomers include vinylimidazole and vinylpyridine.
The heterocycle-containing polymer may contain units derived from non-heterocycle-containing monomers in addition to units derived from heterocycle-containing monomers.

The polymer of component (B1) typically contains units derived from a cross-linking agent.
The proportion of units derived from the cross-linking agent is preferably 0.5 to 60% by mass, more preferably 2 to 10% by mass, and even more preferably 5 to 8% by mass, relative to the total mass of the polymer.
Cross-linking agents may be those commonly used, such as di-, tri-, tetra- and higher polyfunctional ethylenically unsaturated monomers. divinylnaphthalene; divinylxylene; ethylene glycol diacrylate; trimethylolpropane triacrylate; diethylene glycol divinyl ether; Glycol Dimethacrylate (“EGDMA”); Diethylene Glycol Dimethacrylate (“DEGDMA”); Propylene Glycol Dimethacrylate; Propylene Glycol Diacrylate; Trimethylolpropane Trimethacrylate (“TMPTMA”); 1,3-butylene glycol diacrylate; 1,3-butylene glycol dimethacrylate; 1,4-butanediol diacrylate; diethylene glycol diacrylate; diethylene glycol dimethacrylate; 1,6-hexanediol dimethacrylate; tripropylene glycol diacrylate; triethylene glycol dimethacrylate; tetraethylene glycol diacrylate; polyethylene glycol 200 diacrylate; bisphenol A diacrylate; ethoxylated bisphenol A dimethacrylate; polyethylene glycol 600 dimethacrylate; poly(butanediol) diacrylate; pentaerythritol triacrylate; divinylsilane; trivinylsilane; dimethyldivinylsilane; divinylmethylsilane; methyltrivinylsilane; diphenyldivinylsilane; divinylphenylsilane; trivinylphenylsilane; dimethylvinyldisiloxane; poly(methylvinylsiloxane); poly(vinylhydrosiloxane); poly(phenylvinylsiloxane) and mixtures of two or more thereof.

The (B1) component polymer is typically particulate.
The average particle size of the polymer is preferably 1 to 200 nm, more preferably 1 to 50 nm, and even more preferably less than 10 nm. The average particle size is the number average particle size measured by a light scattering method.
The molecular weight of the polymer is, for example, 500-5000.

(B1) As the component, SILVADUR (registered trademark) 900 Antimicrobial, SILVADUR (registered trademark) 930 Antimicrobial, and SILVADUR (registered trademark) 930FLEX Antimicrobial provided by Dow Chemical Japan; Commercially available products such as Lurol (registered trademark) Ag-1500 provided by Co., Ltd.; and Brian BG-1 (registered trademark) provided by Matsumoto Yushi Pharmaceutical Co., Ltd. can be used. SILVADUR 930 Antimicrobial is a silver complexed with a polymer having less than 10% by weight of units derived from a crosslinker, containing vinylimidazole as heterocyclic ring-containing monomer and having an average particle size of less than 10 nm.
(B1) component can be used individually by 1 type or in combination of 2 or more types.

The component (B2) is selected from the group consisting of an amino acid (component (b21)), a monovalent to divalent carboxylic acid having 3 to 8 total carbon atoms (component (b22)), and an imidazole derivative (component (b23)). Silver complexed with at least one compound.
Component (B2) includes complexes of silver and amino acids (histidine, arginine, creatinine, etc.), complexes of silver and carboxylic acids (pyruvic acid, glycolic acid, acetic acid, butyric acid, salicylic acid, etc.), and silver, carboxylic acids and amino acids. and complexes of silver and imidazole derivatives (imidazoline, etc.). These (B2) components can be used individually by 1 type or in combination of 2 or more types. As component (B2), commercially available products such as J-Chemical CF-01 (complex of creatinine, fumaric acid and silver) can be used.
Among these, silver complexed with at least one selected from components (b21) and (b22) is preferred as the component (B2).

Component (B3) is silver oxide, chloride, nitrate, sulfate or silver itself supported on a particulate carrier.
Specific examples of carriers include phosphates (zirconium phosphate, calcium phosphate, etc.), metal oxides (silicon oxide, aluminum oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, etc.), inorganic compounds (zeolites, clay minerals, etc.). , silica gel, etc.). These carriers can be used singly or in combination of two or more. As the carrier, a metal oxide is preferable from the viewpoint of supporting strength.
As the component (B3), colloidal alumina silica supported with silver oxide is preferable.
The average particle size of component (B3) is preferably 1 to 500 nm, more preferably 1 to 100 nm. The average particle size is the number average particle size measured by a light scattering method. If the average particle size is 500 nm or less, the dispersed state of the particles will be stable, and if it is 100 nm or less, the dispersed state of the particles will be more stable. In addition, the smaller the average particle size, the easier the contact between the bacteria and the dispersed particles, and the more advantageous the sterilizing power.
As the component (B3), commercially available products such as ``ATOMY BALL-S'', ``ATOMY BALL-L'' and ``ATOMY BALL-UA'' manufactured by Catalysts & Chemicals Co., Ltd. can be used.
(B3) component can be used individually by 1 type or in combination of 2 or more types.
As the silver compound, the components (B1) and (B2) are preferred, and silver complexed with at least one selected from the group consisting of the components (b11), (b21) and (b22) is preferred.

Among the components (B), polyhexamethylene biguanide and salts thereof (hereinafter also referred to as "component (B4)") include, for example, compounds represented by the following formula (4).

In the formula, y is an integer of 2-14, preferably an integer of 10-14, more preferably an integer of 11-13, particularly preferably 12.
HR is an organic or inorganic acid, preferably hydrochloric acid, gluconic acid or acetic acid, particularly preferably hydrochloric acid.
x represents the number of HR and is an integer of 0 to 5y, preferably an integer of 1 to 5y, more preferably an integer of 2 to 3y, still more preferably an integer of y to 2y, particularly preferably y.
(B4) A commercial item can be used as a component. An example of a commercially available product is Proxel IB (registered trademark) manufactured by Lonza Japan Co., Ltd., which is poly(hexamethylenebiguanide) hydrochloride in which x and y in the formula (4) are 12 and HR is hydrochloric acid. is mentioned.

(B) component can be used individually by 1 type or in combination of 2 or more types.
Component (B) is preferably at least one selected from the group consisting of component (B1), component (B2) and component (B4) from the viewpoint of sterilizing power and liquid color stability, component (b11), Silver complexed with at least one selected from the group consisting of components (b21) and (b22) is more preferred, and component (B1) is even more preferred. The silver complexed with at least one selected from the group consisting of the components (b21) and (b22) is preferably a complex of the component (b21) and silver, a complex of the component (b22) and silver, and creatinine. and silver complexes, and fumaric acid and silver complexes are more preferable. It is particularly preferred to include both creatinine and silver complexes and fumaric acid and silver complexes.

<(C) Component>
Component (C) is at least one selected from the group consisting of basic polyamino acids and salts thereof.
A basic polyamino acid is one that has an amino group or the like in a side chain or a structural unit, exhibits basicity when dissolved in an aqueous solution, and exhibits cationic properties in an acidic environment.
Monomers (amino acids) constituting basic polyamino acids include lysine, histidine, arginine and the like.
As the basic polyamino acid, polylysine is preferable from the viewpoint of antibacterial effect. Polylysine is a polymer of the essential amino acid L-lysine. Examples of polylysine include α-polylysine and ε-polylysine, with ε-polylysine being preferred.
ε-Polylysine is a linear chain of L-lysines. As ε-polylysine, one represented by the following formula (5) is preferable.

式中、ｚは２５～３５の整数である。

In the formula, z is an integer of 25-35.

ε-Polylysine may be obtained by any known method. For example, Streptomyces alplus subspecies lysinopolymerus described in Patent No. 1245361 is mixed with 5% by mass of glycerin, 0.5% by mass of yeast extract, 1% by mass of ammonium sulfate, and 0.08% by mass of dipotassium hydrogen phosphate. , Potassium dihydrogen phosphate 0.136% by mass, magnesium sulfate heptahydrate 0.05% by mass, zinc sulfate heptahydrate 0.004% by mass, iron sulfate heptahydrate 0.03% by mass ε-polylysine obtained by culturing in a medium adjusted to pH 6.8 and separating and collecting from the resulting culture can be used. In addition, ε-polylysine can be easily synthesized using a solid-phase method or the like commonly used for peptide synthesis, and can also be synthesized using a commercially available peptide synthesizer or the like. Furthermore, ε-polylysine can be mass-produced in microbial cells, plant cells, and animal cells using a genetic engineering technique using a gene encoding the amino acid sequence of a lysine peptide. The crude synthetic peptide obtained here is further purified by means commonly used for purification of proteins and peptides, such as gel filtration, normal-phase, reverse-phase HPLC (high-performance liquid chromatography), and ion-exchange column purification. Is possible.

The number average molecular weight of component (C) is preferably 500 to 100,000, more preferably 1,000 to 50,000, even more preferably 2,000 to 20,000.
The number average molecular weight of component (C) is a value converted to standard polystyrene measured by gel permeation chromatography.
(C) A commercial item can be used as a component. Examples of commercially available products include polylysine (number average molecular weight: about 4000, 25% aqueous solution) manufactured by Chisso Co., Ltd., which is ε-polylysine.
(C) Component can be used individually by 1 type or in combination of 2 or more types.

<(D) Component>
(D) Component is a chelating agent.
Component (D) exerts excellent detergency against fatty acid metal salts, sebum and protein stains adhering to hard surfaces such as bathtubs, and also exerts a sterilizing effect against microorganisms.
As the component (D), those commonly used can be used, and examples thereof include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, phosphoric acids and the like. Organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, hydroxycarboxylic acids (glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxy methyl tartaric acid, citric acid, malic acid, gluconic acid, etc.). Aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, triethylenetetrahexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, and hydroxyethylimino. diacetic acid, cyclohexane-1,2-diaminetetraacetic acid, and the like. Phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and derivatives thereof, 1-hydroxyethane-1,1,2 -triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylene phosphonic acid and the like. Phosphonocarboxylic acids include 2-nosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid and the like. Phosphoric acids include condensed phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, and phytic acid. These chelating agents can be used in the form of acids, and can also be used with basic substances such as salts with alkali metals such as potassium and sodium, salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. It is also possible to use it in the form of a salt with These chelating agents can be used singly or in combination of two or more.
As component (D), ethylenediaminetetraacetic acid or a salt thereof is preferable from the viewpoint of detergency. Citric acid or a salt thereof is preferred from the viewpoint of sterilizing power, and ethylenediaminetetraacetic acid or a salt thereof, citric acid or a salt thereof is more preferably used in combination from the viewpoints of detergency and sterilizing power.
is preferred.

<(E) Component>
Component (E) is an aromatic water-soluble solvent. A water-soluble solvent refers to a solvent that dissolves 3 g or more in 1 L of deionized water at 25°C. Component (E) is preferably an aromatic ether of (poly)alkylene glycol having an alkylene glycol unit with 2 to 3 carbon atoms. When the component (B) contains a silver compound, precipitation of silver during high-temperature storage can be suppressed. Specific examples of component (E) include ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of 200 to 1000, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether. benzyl ether and the like. Among these, aromatic ethers having an ethylene glycol unit having 2 carbon atoms are preferred, aromatic ethers having a phenyl group are more preferred, and diethylene glycol monophenyl ether is even more preferred. These aromatic ethers can be used singly or in combination of two or more.

<(F) Component>
(F) Component is a nonionic surfactant. Used to improve high temperature stability. Component (F) includes higher alcohols, alkylphenols, polyoxyalkylene-type nonionic surfactants obtained by adding alkylene oxides to higher fatty acids or higher amines, polyoxyethylene-polyoxypropylene block copolymers, fatty acid alkanolamides, and polyhydric alcohols. Fatty acid esters or their alkylene oxide adducts, fatty acid polyglycerol esters, sugar fatty acid esters, alkyl (or alkenyl) amine oxides, amidoamine oxides, hydrogenated castor oil alkylene oxide adducts, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, alkyl polyglycosides, glyceryl ethers, and the like. Among these, a polyoxyalkylene type nonionic surfactant obtained by adding alkylene oxide to a higher alcohol is preferable.
Alkylene oxides include ethylene oxide and propylene oxide, with ethylene oxide being preferred. The average number of added moles of the alkylene oxide is preferably 3-15, more preferably 5-10, and particularly preferably 6-8.
The number of carbon atoms in the alkyl group of the higher alcohol is preferably 8-20, more preferably 10-15.
Among them, oxoalcohol ethoxylate, Guerbet alcohol ethoxylate and natural alcohol ethoxylate are preferable, and oxoalcohol ethoxylate and Guerbet alcohol ethoxylate are more preferable.
The oxoalcohol ethoxylate preferably has an alkyl group of 10 to 15 carbon atoms and an average number of moles of ethylene oxide added of 6 to 15. Specifically, the LutensolTO series of BASF is preferable.
The Guerbet alcohol ethoxylate preferably has 10 carbon atoms in the alkyl group and 6 to 15 average moles of ethylene oxide. Specifically, the Lutensol XP series of BASF is preferable.
The natural alcohol ethoxylate preferably has an alkyl group of 12 to 14 carbon atoms and an average number of moles of ethylene oxide added of 6 to 15.
(F) Component can be used individually by 1 type or in combination of 2 or more types.
Component (F) is preferably used in combination with component (E) from the viewpoint of high-temperature stability.

<Other ingredients>
Other components include, for example, cationic surfactants, amphoteric surfactants, fragrances, pH adjusters, water-soluble solvents (excluding component (E)), pigments, dyes, thickeners, viscosity adjusters, surface modifiers, Stabilizers, antioxidants, ultraviolet absorbers, solubilizers and the like can be mentioned. These optional components are not particularly limited as long as they are commonly used in detergents.

Cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts, imidazolinium salts and the like. Counterions (anions) of these cationic surfactants include halogen ions.

Examples of amphoteric surfactants include alkylbetaine-type, alkylamidobetaine-type, imidazoline-type, alkylaminosulfone-type, alkylaminocarboxylic acid-type, alkylamidocarboxylic acid-type, amideaminoacid-type, and phosphoric acid-type amphoteric surfactants. be done. Among them, the alkylaminocarboxylic acid type is preferable from the viewpoint of detergency.

The perfume is not particularly limited, but examples include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, and aliphatic Ethers, ethers such as aromatic ethers, oxides such as aliphatic oxides and terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, aliphatic Ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids , Hydrogenated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones, lactones such as aromatic lactones, aliphatic esters, Esters such as furan-based carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene-based carboxylic acid esters, aromatic carboxylic acid esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, Various synthetic flavors and natural flavors from plants are included, such as nitrogen-containing compounds such as indole. These fragrances can be used singly or in combination of two or more, and are usually used in combination of two or more.

The pH adjuster is not particularly limited, but may be selected from inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, and p-toluenesulfonic acid. acid agents, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc. It is preferable to use an alkaline agent selected from hydrochloric acid, sulfuric acid, citric acid It is more preferable to use an acid agent selected from and an alkali agent selected from sodium hydroxide and potassium hydroxide. These pH adjusters can be used singly or in combination of two or more.

<Content of each component>
In the hard surface cleaning composition, the content of component (A) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total mass of the hard surface cleaning composition. % is more preferred. If the content of component (A) is at least the lower limit of the above range, the detergency will be better, and if it is at most the upper limit of the above range, the disinfecting power will be better.

The content of component (B) is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.05% by mass, more preferably 0.001%, based on the total mass of the hard surface cleaning composition. ~0.01% by mass is more preferred. If the content of the component (B) is at least the lower limit of the range, the sterilizing power is more excellent, and if it is the upper limit of the range or less, the liquid color stability is more excellent, and the liquid color turns yellow during storage. is less likely to occur.
When the component (B) contains a silver compound, the content of the silver compound indicates the amount converted to elemental silver.

The mass ratio represented by (elemental silver in component (B) + polyhexamethylene biguanide + salt thereof)/component (C) (hereinafter also referred to as "B/C ratio") is 0.025 to 3.0. 0, preferably 0.075 to 0.3. If the B/C ratio is at least the lower limit of the above range, good sterilizing power can be obtained even after the hard surface cleaning composition is stored at high temperatures. If the B/C ratio is equal to or less than the upper limit of the above range, good liquid color stability can be obtained.

The total amount of components (B) and (C) is preferably 0.005 to 0.03% by mass, more preferably 0.01 to 0.02% by mass, relative to the total mass of the hard surface cleaning composition. preferable.

When the component (B) contains a silver compound, the content of the silver compound is the mass ratio represented by silver element in the component (B)/component (C) (hereinafter also referred to as "Ag/C ratio"). is preferably 0.1 to 1, more preferably 0.2 to 0.6. If the Ag/C ratio is equal to or higher than the lower limit of the above range, the sterilization performance will be more excellent. If the B/C ratio is equal to or less than the upper limit of the above range, liquid color stability is more excellent.

When component (B) contains polyhexamethylene biguanide or a salt thereof, the mass ratio represented by (polyhexamethylene biguanide in component (B) + salt thereof)/component (C) is 0.5 to 3.0. 0 is preferred, and 1.0 to 2.0 is more preferred. If the mass ratio is at least the above lower limit, it is easy to obtain good sterilization power even after the hard surface cleaning composition is stored at high temperatures. If the mass ratio is equal to or less than the above upper limit, it is easy to obtain good liquid color stability.

When the component (B) contains the component (B1), the content of the component (B1) is preferably at least 0.001% by mass in terms of silver element concentration with respect to the total mass of the hard surface cleaning composition. . The upper limit of the content of component (B1) (in terms of silver element concentration) is, for example, 0.005% by mass.
When the component (B) contains the component (B2), the content of the component (B2) is preferably 0.0005% by mass or more in terms of silver element concentration with respect to the total mass of the hard surface cleaning composition. . The upper limit of the content of component (B2) (in terms of silver element concentration) is, for example, 0.02% by mass.
When the component (B) contains the component (B3), the content of the component (B3) is preferably 0.001% by mass or more in terms of silver element concentration with respect to the total mass of the hard surface cleaning composition. . The upper limit of the content of component (B3) (in terms of silver element concentration) is, for example, 0.01% by mass.

(B) When the component contains the (B4) component, the content of the (B4) component is the mass ratio represented by the (B4) component/(C) component in the (B) component (hereinafter, “B4/C ratio”) is preferably 0.5 to 10, more preferably 1 to 5. If the B4/C ratio is at least the lower limit of the above range, the sterilization performance will be more excellent. If the B4/C ratio is equal to or less than the upper limit of the above range, the sterilization performance will be more excellent.

The content of component (C) is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.1% by mass, and more preferably 0.01% by mass, relative to the total mass of the hard surface cleaning composition. ~0.05% by mass is more preferred. If the content of component (C) is at least the lower limit of the above range, the sterilizing power is superior, and if it is at most the upper limit of the above range, deterioration of aroma after high-temperature storage can be suppressed.

The content of component (D) is preferably 0.1 to 10.0 parts by mass, more preferably 0.1 to 5.0 mass %, and 1.5 parts by mass, based on the total mass of the hard surface cleaning composition. ~3.0% by mass is more preferred. (D) If the content of the component is within the above range, the detergency and sterilization power will be more excellent.

The content of component (E) is preferably 0.01 to 10% by mass, more preferably 0.1 to 1.0% by mass, still more preferably 0.01 to 1.0% by mass, based on the total mass of the hard surface cleaning composition. 25 to 0.75% by mass. (E) When the content of the component is within the above range, high-temperature stability and sterilization performance are more excellent.

The content of component (F) is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and still more preferably the total mass of the hard surface cleaning agent. It is 0.25 to 0.5% by mass. When the content of component (F) is within the above range, high-temperature stability and sterilization performance are more excellent.

The pH of the hard surface cleaning composition at 25°C is 9-12, preferably 10-12. When the pH is at least the lower limit of the above range, the detergency for hard surfaces is excellent. When the pH is equal to or lower than the upper limit of the above range, the detergency for hard surfaces is excellent.
The pH of the hard surface cleaning composition is a value measured at 25°C according to JIS Z8802:2011.

The hard surface cleaning composition of the present invention comprises (A) component, (B) component, (C) component, water, optionally (D) component, (E) component, (F) component and other components. can be prepared by mixing and adjusting the pH as necessary.
The pH of the hard surface cleaning composition can be adjusted with a pH adjuster or the like.

The hard surface cleaning composition of the present invention described above contains components (A), (B), and (C), and has a B/C ratio of 0.025 to 3.0. Since it has a pH of 9 to 12 at 25°C, it is excellent in detergency, sterilization power and liquid color stability.

Examples of hard surface materials to which the hard surface cleaning composition of the present invention is applied include plastics, tiles, stainless steel, ceramics, and glass. Specific examples of hard surfaces include bathroom tubs, bathroom floors, walls and fixtures, faucets and faucets, tub lids, bathroom doors, mirrors, drains, and the like.
The hard surface cleaning composition of the present invention has a high detergency against sebum and protein stains adhering to the floor and walls in a bathtub and bathroom, and has a high sterilization performance against Staphylococcus aureus. It is suitable for use.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" in the examples indicates pure "% by mass". The raw materials used in this example are as follows.

<(A) Component>
A-1: AOS, sodium C14-α olefin sulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Liporan LJ441".
A-2: LAS, linear alkyl (C12-14) sodium benzenesulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon PS-230".
A-3: AES, polyoxyethylene (2) sodium lauryl sulfate. Manufactured by Shin Nippon Rika Co., Ltd., trade name "Sinoline SPE-1250". "(2)" in the above "polyoxyethylene (2)" means the average number of repeating oxyethylene groups.
A-4: SDS, lauryl sulfate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Sunol LM-1130".

<(B) Component>
B-1: Silver complexed with a polymer, trade name "SILVADUR 930 Antimicrobial" manufactured by Dow Chemical Japan Co., Ltd. (elemental silver concentration: 0.1%).
B-2: Silver complexed with carboxylic acid and creatinine, trade name “CF-01” manufactured by J Chemical Co., Ltd. (elemental silver concentration: 2.5%).
B-3: Nanocolloid in which silver oxide is supported on colloidal alumina silica, trade name "ATOMYBALL UA" (silver element concentration ^* 0.0686%) manufactured by Catalysts and Chemicals.
B-4: Polyhexamethylene biguanide hydrochloride, trade name "Proxel IB" manufactured by Lonza Japan Co., Ltd.

*Method of measuring elemental silver concentration:
A stock solution of component (B) containing silver (ATOMYBALL UA, etc.) was diluted with nitric acid (reagent special grade, Wako Pure Chemical Industries) and distilled water to give a 0.1 M nitric acid aqueous solution to prepare a measurement sample. On the other hand, a silver ion standard solution (1000 ppm solution, Wako Pure Chemical Industries, Ltd.) was diluted to 0.1 M nitric acid aqueous solution in the same manner as the measurement sample to prepare standard solutions of 1 ppm and 0.01 ppm. Then, the silver concentrations of the measurement sample and the standard sample are measured using an inductively coupled plasma atomic emission spectrometer (“Optima 5300DV” manufactured by Perkin Elmer), and the emission intensity of the obtained measurement sample is calibrated using a standard solution. A quantitative value was obtained by converting to a silver element concentration by linear method.

<(C) Component>
C-1: Polylysine, trade name "polylysine" manufactured by JNC Corporation.

<(D) Component>
D-1: Disodium ethylenediaminetetraacetate (EDTA2Na), trade name "Disolvin NA2" manufactured by Akzo Nobel Co., Ltd.
D-2: Citric acid, manufactured by Fuso Chemical Industries, Ltd., trade name “purified citric acid (anhydrous)”.

<(E) Component>
E-1: Diethylene glycol monophenyl ether, trade name "Phenyldiglycol" manufactured by Nippon Nyukazai Co., Ltd.
E-2: Ethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., trade name "Phenyl glycol".

<(F) Component>
F-1: Oxoalcohol (C13, 100% branched) ethoxylate [average number of added moles of ethylene oxide: 7], trade name “Lutensol TO-7” manufactured by BASF.

<Optional component>
pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid, manufactured by Kanto Kagaku Co., Ltd.
Water-soluble solvent: diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd., product "butyl diglycol".
Dye A: Direct Blue 86, manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumilight Supra Turquise Blue G conc".
Pigment B: Fast Green FCF, manufactured by Kisumi Kasei Co., Ltd., trade name "Green No. 3".
Perfume: Perfume compositions (perfume A and perfume B) shown in Table 1 were used.

<Examples 1 to 25, Comparative Examples 1 to 6>
According to the compositions shown in Tables 2, 3, and 4, the components (A) to (F) were added to water and mixed, and the pH was adjusted to the value shown in the table with a pH adjuster, and optional components were added. to obtain a hard surface cleaning composition of each example.
In the table, when there is a blank compounding component, that compounding component is not blended. In the table, the "appropriate amount" of the pH adjuster is the amount required to adjust the pH of the hard surface cleaning composition of each example to the value shown in the table. In the table, the water content "balance" means the balance added so that the total amount of all ingredients contained in the hard surface cleaning composition is 100%.
The cleaning power, disinfecting power, liquid color stability, and high-temperature stability of the hard surface cleaning composition of each example were evaluated as follows. The results are shown in Tables 2, 3 and 4.

(Evaluation of detergency)
After fixing a glass fiber reinforced plastic (FRP) test piece (2 cm x 10 cm) to the inner wall surface of a bathtub in a general household, three adult males each bathed three times (one bath a day for three days, During this time, only the bath water was changed, and the bathtub was used without being washed), and the test piece was stained (bath scale stain).
After sufficiently drying the soiled test piece, the hard surface cleaning composition of each example was dripped onto the test piece so that the entire surface of the test piece was wet, left to stand for 30 seconds, and then tap water (15 °C). The test pieces were sufficiently dried, and the state of removal of stains from the surfaces of the five test pieces was evaluated by visual inspection and finger touch according to the following evaluation criteria for detergency. In the following evaluation criteria, ⊚ and ◯ were regarded as acceptable.
[Evaluation criteria for detergency]
⊚: Stain removal is very good [out of five test pieces, no stains are visually observed on all five test pieces, and the entire surface of the five test pieces is smooth to the touch].
○: Good stain removal [Out of the 5 test pieces, no stains were visually observed in one or more test pieces, and a smooth finger touch was obtained on the entire surface of the test piece. At least one test piece feels rough to the touch].
△: Stain hardly removed [Out of the 5 test pieces, 5 were visually observed to be soiled, and all 5 were felt to be rough to the touch. less than before washing].
×: No dirt removed [out of 5 test pieces, 5 were visually observed to be dirty, all 5 were rough to the touch, and the visual dirt and rough touch were not washed off. same as before].

(Evaluation of sterilization power)
(1) Preparation of control sample:
A control sample was prepared by autoclaving a 0.05% aqueous solution of polyoxyethylene sorbitan monooleate (Tween 80, manufactured by Tokyo Chemical Industry Co., Ltd.).
(2) Preparation of test bacterial solution:
Staphylococcus aureus was inoculated into TSA (Triptic Soy Agar) medium (manufactured by Difco) and pre-cultured 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). bottom.
(3) Preparation of inactivating agent:
30 g of a mixture of polypeptone, lecithin, and polysorbate (LP diluent Daigo (trade name), manufactured by Nihon Pharmaceutical Co., Ltd.) was dissolved in 1 L of purified water under heating and sterilized with high pressure steam to prepare an inactivator.
(4) Sterilization of test tubes:
The test tube was subjected to dry heat sterilization at 180° C. for 1 hour.
(5) Sterilization power measurement:
An evaluation sample (hard surface cleaning composition of each example) and a control sample were stored in an environment at 50°C for one month.
To a sterilized test tube, 1 mL of the test bacterial solution was added, followed by 9 mL of an evaluation sample or a control sample that had been stored in an environment of 50° C. for 1 month, and left to stand 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 solution-1. Test solution-1 was applied to TSA medium by the pour culture method, cultured at 37° C. for 40 hours, and 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 defined as the sterilization activity value, and was judged according to the following criteria. In the following evaluation criteria, ⊚, ⊙ and ◯ were regarded as passed.
[Evaluation criteria for sterilization power]
◎◎: The sterilization activity value is 3.0 or more.
A: The sterilization activity value is 2.5 or more and less than 3.0.
○: The sterilization activity value is 2.0 or more and less than 2.5.
Δ: The sterilization activity value is 1.5 or more and less than 2.0.
x: The sterilization activity value is less than 1.5.

(Evaluation of liquid color stability)
Pouch bags for plastic whose inner material is polyethylene (PE) are filled with the hard surface cleaning composition of each example, and these pouch bags are placed outdoors (details: 5th floor of Lion Co., Ltd. in Hirai, Edogawa-ku, Tokyo). After storing on the roof of the building for 1 week (approximately 4 MJ as UV dose) and 1 month (approximately 15 MJ as UV dose), the content liquid was transferred to a colorless and transparent glass bottle and visually evaluated according to the following criteria. In the following evaluation criteria, ⊚, ⊙ and ◯ were regarded as passed.
[Evaluation Criteria for Liquid Color Stability]
⊙⊚: Almost no liquid discoloration was observed after 1 week or 1 month.
A: Almost no liquid discoloration was observed after 1 week, and slight liquid discoloration was observed after 1 month.
Good: Slight discoloration of the liquid after 1 week, and slight discoloration of the liquid after 1 month.
Δ: Slight liquid discoloration was observed after 1 week, and obvious liquid discoloration was observed after 1 month.
x: Obvious discoloration of liquid after 1 week.

(Evaluation of high temperature stability)
A 50 mL glass bottle ("SV-50A" by Nichiden Rika Glass Co., Ltd.) was filled with 50 g of the hard surface cleaning composition of each example, covered, and then stored in a constant temperature room at 40°C for 4 months. After 2 months, 3 months, and 4 months, the state of the cleaning composition for hard surfaces was visually evaluated, and ⊚, ⊚ and ◯ were evaluated as acceptable according to the following evaluation criteria.
[Evaluation Criteria for High Temperature Stability]
⊚: No precipitate was observed even after 4 months.
A: No precipitate was observed after 3 months, and a precipitate was observed after 4 months.
◯: No precipitate was observed after 2 months, and a precipitate was observed after 3 months.
Δ: No precipitate was observed after 1 month, and precipitate was observed after 2 months.
x: Precipitates were observed after 1 month.

The hard surface detergent compositions of Examples 1 to 25 were excellent in hard surface detergency, sterilization power, and liquid color stability.
Examples 17 to 25 containing a silver compound as the (B) component and containing at least one of the (E) component and the (F) component had high-temperature stability of "◯" to "◎◎".
The hard surface cleaning composition of Comparative Example 1, which did not contain component (A), was inferior in cleaning power for hard surfaces.
The hard surface cleaning compositions of Comparative Examples 2 and 3, which did not contain component (B) or component (C), were inferior in disinfecting power.
The hard surface cleaning composition of Comparative Example 4 with a B/C ratio of less than 0.025 was inferior in disinfecting power.
The hard surface cleaning composition of Comparative Example 5 with a B/C ratio of more than 3.0 was inferior in liquid color stability.
The hard surface cleaning composition of Comparative Example 6 having a pH of less than 9 was inferior in hard surface detergency.

Claims (6)

(A) component: an anionic surfactant,
(B) component: at least one selected from the group consisting of silver compounds, polyhexamethylene biguanides and salts thereof, and (C) component: at least one selected from the group consisting of basic polyamino acids and salts thereof. death,
(Silver element + polyhexamethylene biguanide + salt thereof in component (B))/component (C) has a mass ratio of 0.025 to 3.0,
A hard surface cleaning composition having a pH of 9 to 12 at 25°C. The component (B) is silver complexed with at least one selected from the group consisting of polymers, amino acids, monovalent to divalent carboxylic acids with 3 to 8 total carbon atoms (excluding amino acids), polyhexa The hard surface cleaning composition according to claim 1, which is at least one selected from the group consisting of methylene biguanide and salts thereof. (D) Component: The hard surface cleaning composition according to claim 1 or 2, further comprising a chelating agent. 4. The hard surface cleaning composition according to claim 3, wherein the component (D) contains at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salts and citric acid or its salts. The component (B) contains a silver compound,
5. The hard surface cleaning composition according to any one of claims 1 to 4, further comprising component (E): an aromatic water-soluble solvent. The component (B) contains a silver compound,
6. The hard surface cleaning composition according to any one of claims 1 to 5, further comprising component (F): a nonionic surfactant.