JP6960510B1 - Detergent composition for hard surface and cleaning method for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning agent composition for a hard surface exhibiting excellent detergency and antifouling effects. The present invention contains a cationized polysaccharide as a component (A), an alkaline agent as a component (B), an anionic surfactant as a component (C), and water as a component (D), and (A). Provided is a detergent composition for a hard surface, wherein the value of the mass ratio (A) / (C) of the component and the component (C) is 0.01 or more and 100 or less. [Selection diagram] None

Description

The present invention relates to a cleaning agent composition for a hard surface having excellent detergency and antifouling effect on stains adhering to a hard surface, and a method for cleaning a hard surface using the composition.

Ventilation fans, gas ranges, bath kettles, toilets, tableware, vehicles, buildings, etc. in kitchens in ordinary households are made of hard materials such as metal, plastic, glass, ceramics, and concrete. Various stains adhere to these hard surfaces due to wind and rain, foods, emissions, oils, exhaust gas, etc., but especially at cooking sites, strong oil stains adhere due to baking or long-term use. Various cleaning agents are used to remove such oil stains, but cleaning agents containing various polymers are known because they can be easily removed even if stains adhere after cleaning (antifouling effect). There is.

As a conventional cleaning agent, Cited Document 1 describes a hard surface cleaning agent composition containing an amphoteric polymer containing an acidic group and / or an anionic group and a cationic group and / or an amino group. ing. Reference 2 describes a cleaning agent composition for oil stains containing a (co) polymer containing 30 to 100 mol% of a unit derived from an N, N-diallyl-N, N-dimethylammonium salt monomer. .. Cited Document 3 describes a liquid detergent composition containing cationized cellulose.

Japanese Unexamined Patent Publication No. 2011-219652 Japanese Unexamined Patent Publication No. 2012-193287 Japanese Unexamined Patent Publication No. 2003-155499

However, although the compositions described in Patent Documents 1 and 2 are techniques for forming a hydrophilic film on the surface to prevent reattachment of stains, it is difficult to form a film on a hydrophobic hard surface. The antifouling effect was not fully exhibited.

Patent Document 3 is excellent in drainage property due to the blending of cationized cellulose, but the detergency against seized oil stains is not sufficient and the antifouling effect is not sufficient.

In view of the above circumstances, the present invention is for hard surfaces that exhibit excellent detergency especially against oil stains and further exhibit excellent antifouling effect not only on hydrophilic surfaces but also on hydrophobic surfaces. It is an object of the present invention to provide a cleaning agent composition.

As a result of diligent studies to solve the above problems, the present inventors have conducted diligent studies, and as a result, the (A) component is a cationized polysaccharide, the (B) component is an alkaline agent, the (C) component is an anionic surfactant, and the (D) component. A detergent composition for hard surfaces, which contains water as a base and has a mass ratio (A) / (C) of components (A) to (C) of 0.01 or more and 100 or less, is for conventional hard surfaces. We have found that the problems of the detergent composition can be solved, and have completed the present invention.

That is, the present invention
(1) Cationized polysaccharide as a component (A),
(B) Alkaline agent as an ingredient,
It contains an anionic surfactant as a component (C) and water as a component (D), and the component (B) contains at least one of sodium hydroxide and potassium hydroxide, and the components (A) and (C). the weight ratio of (a) / (C) value is 0.01 or more, 100 Ri der hereinafter pH 13.1 or more at 25 ° C. of the composition, of 14 or less, the cleaning compositions for hard surfaces,
(2) The component (A) is a cationized cellulose, the detergent composition for a hard surface of (1), and the components (3) and (C) are α-olefin sulfonic acid and polyoxyalkylene alkyl ether sulfate. The hard surface detergent composition according to (1) or (2), which contains one or more selected from the group consisting of secondary alkane sulfonic acid and salts thereof.
(4) The hard surface cleaning agent composition according to any one of (1) to (3), which further contains an amphoteric surfactant as the component (E).
(5) The hard surface cleaning agent composition according to any one of (1) to (4), which further contains a nonionic surfactant as the component (F).
(6) The hard surface cleaning agent composition according to any one of (1) to (5), further containing (G) a glycol-based solvent, a glycol ether-based solvent, and a solvent selected from a mixture thereof.
(7) The hard surface cleaning agent composition according to any one of (1) to (6), further containing an aromatic sulfonic acid compound as the component (H).
(8) A detergent composition for a hard surface according to any one of (1) to (7) for cleaning a hard surface of a microwave oven, a sink, a ventilation fan, a countertop or a cooking utensil .
(9) A method for cleaning a hard surface, which comprises spraying the cleaning agent composition for a hard surface according to any one of (1) to (8) onto an object to be cleaned in the form of bubbles using a hand sprayer. (10) The method for cleaning a hard surface according to (9), wherein the hand sprayer is a trigger sprayer or a former player.

The cleaning agent composition for a hard surface of the present invention exhibits excellent detergency against oil stains, and further has an excellent antifouling effect (stains adhere to) not only on hydrophilic surfaces but also on hydrophobic surfaces. The effect of making it easier to drop) is shown.

The present invention contains the above components (A) to (D) as essential components, and the value of the mass ratio (A) / (C) of the components (A) and (C) is 0.01 or more and 100 or less. , A cleaning agent composition for hard surfaces.

<Ingredient (A)>
The component (A) is a cationized polysaccharide. The cationized polysaccharide contributes to the improvement of antifouling property on both the hydrophobic surface and the hydrophilic surface of the detergent composition for hard surface of the present invention.
Examples of the component (A) include water-soluble polysaccharides containing an amino group or an ammonium group in the side chain of the polymer chain of the polysaccharide, or containing a diallyl quaternary ammonium salt as a constituent unit.

Specific examples of the component (A) include cationized cellulose, cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, cationized starch, cationized guar gum, cationized tara gum, cationized phenuglique gum, cationized locust bean gum, and cationized tamarind. And so on. Among these, cationized cellulose, cationized guar gum, and cationized starch are preferable, and cationized cellulose is more preferable.

The cationized polysaccharide of the component (A) contains nitrogen mainly derived from an amino group or an ammonium group, and the nitrogen content thereof is not particularly limited, but is preferably 0.1 to 10.0% by mass. It is preferably 0.5 to 5.0% by mass, further preferably 0.9 to 3.0% by mass, and 1.1% by mass to 2.5% by mass. Most preferred.
Examples of the measurement of the nitrogen content include the Kjeldahl method. As the Kjeldahl method, for example, "Quasi-drug raw material standard 2006 (Yakuji Nippo Co., Ltd.)" general test method 44. It can be measured by decomposing the cationized polysaccharide of the component (A) with sulfuric acid to obtain ammonium sulfate and quantifying the ammonium sulfate with reference to the nitrogen quantification method.

The cationized cellulose used as the component (A) in the present invention is a cellulose obtained by modifying the cellulose with a cationizing agent, but is not particularly limited, and a commercially available known cationized cellulose can be used.
For example, the product name "Leoguard GP (4th grade nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", the product name "Leoguard LP (4th grade nitrogen content 1.0% by mass, Lion)"・ Specialty Chemicals Co., Ltd. ”, product name“ Leoguard MGP (4th grade nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.) ”, Product name“ Leoguard MLP (4th grade nitrogen content) Rate 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd. ”, product name“ SuperCare212 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemicals) ”, product name“ Katinal HC-100 (manufactured by Dow Chemicals Co., Ltd.) ” The quaternary nitrogen content is 1.0 to 2.0% by mass, manufactured by Toho Kagaku Kogyo Co., Ltd.) ”.

The weight average molecular weight of the cationized cellulose used in the present invention is not particularly limited, but is generally 1000 to 5000000, preferably 20000 to 20000, and even more preferably 50000 to 1000000.

Catified guar gum refers to all polysaccharides (guar gum) obtained from the seeds of annual legumes cultivated in Pakistan and India, whose scientific name is Cyamopsis tetragonoloba, modified with a cationizing agent. ..
In the present invention, there is no particular limitation, and a commercially available known cationized guar gum can be used. Examples of commercially available cationized guar gum include Laval gum CG-M series (manufactured by DSP Gokyo Food & Chemicals Co., Ltd.) and trade name "Jaguar C-13S (manufactured by Solvay Co., Ltd.)".
The weight average molecular weight of the cationized guar gum used in the present invention is not particularly limited, but is generally 5000 to 5000000, preferably 1000 to 3000000.

The cationized starch refers to all modified starches obtained by reacting a cationizing agent with starch. In the present invention, a known cationized starch can be used without particular limitation. Examples of commercially available products include the product name "SEMSOMER CI-50 (manufactured by Lubrizol)", the product name "Neotack 40T (manufactured by Nihon Shokuhin Kako)", and the POSIT series (manufactured by Sansho Co., Ltd.).
The weight average molecular weight of the cationized starch used in the present invention is not particularly limited, but is generally 1000 to 5000000, preferably 5000 to 3000000.

The viscosity of the 2% by mass aqueous solution of the component (A) at 25 ° C. is preferably 5 to 5000 mPa · s, more preferably 10 to 3000 mPa · s, and even more preferably 50 to 2500 mPa · s. When the viscosity of the 2% by mass aqueous solution of the component (A) is within the above range, it is more excellent in drainage property at the time of washing at a low concentration. The viscosity is a value measured with a B-type viscometer in a 2% by mass aqueous solution of cationized cellulose at 25 ° C. The viscosity measurement conditions are as follows.
Measurement condition:
[rotor]
The rotor number and rotor rotation speed corresponding to the viscosity of the measurement target are as follows.
-Viscosity is less than 500 mPa · s: Rotor number No. 2. Rotation speed 60 rpm.
-Viscosity of 500 mPa · s or more and less than 2000 mPa · s: Rotor No. 3. Rotation speed 60 rpm.
-Viscosity of 2000 mPa · s or more and less than 10000 mPa · s: Rotor No. 4, rotation speed 60 rpm.
-Viscosity is 10,000 mPa · s or more and less than 50,000 mPa · s: Rotor No. 4, rotation speed 12 rpm.
[Reading numbers]
5 minutes after the start of rotation of the rotor.

The weight average molecular weight of the component (A) of the present invention is a value determined by the gel permeation chromatography (GPC) method.
The equipment and conditions used in the method are as follows.
Column used: Two TSKgel α-M are connected in series.
Free solution: THF (tetrahydrofuran), flow rate: 0.5 mL / min, detector: RI, sample concentration: 0.1% by mass (THF solution), sample volume: 200 μL, column temperature: 40 ° C.

The blending amount of the component (A) is not particularly limited as long as the effect of the present invention is obtained, but is preferably 0.01% by mass or more and 10% by mass or less with respect to the total amount of the hard surface cleaning agent composition of the present invention. , 0.03% by mass or more and 5% by mass or less is more preferable, and 0.05% by mass or more and 2% by mass or less is particularly preferable. If the blending amount of the component (A) is less than 0.01% by mass with respect to the total amount of the hard surface cleaning agent composition of the present invention, the antifouling property may be insufficient, while 10% by mass. If it exceeds%, the storage stability of the composition may deteriorate, and the viscosity of the hard surface detergent composition may become too high, making it difficult to use in a hand sprayer.

<Ingredient (B)>
The hard surface cleaning agent composition of the present invention contains an alkaline agent as the component (B). The alkaline agent improves the detergency of the composition.

As the alkaline agent, a known alkaline agent used in the cleaning composition for a hard surface can be used, and for example, an alkali metal hydroxide compound such as lithium hydroxide, sodium hydroxide, potassium hydroxide; sodium carbonate, Alkali metal carbonates such as potassium carbonate; silicates such as sodium metasilicate, sodium orthosilicate; ammonium compounds such as ammonia, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine; sodium methylate, potassium methylate, etc. Alkali metal methylate can be mentioned.

Among these alkaline agents, it is preferable to use one or more selected from sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and monoisopropanolamine, and sodium hydroxide and water. It is more preferable to use at least one of potassium oxide.

The blending amount of the component (B) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 1% by mass or more and 25% by mass or less with respect to the total amount of the hard surface cleaning agent composition of the present invention. More preferably, it is 5% by mass or more and 20% by mass or less, and particularly preferably 5% by mass or more and 15% by mass or less. If the blending amount of the component (B) is less than 1% by mass with respect to the total amount of the cleaning agent composition for a hard surface of the present invention, the detergency may be insufficient, while it is more than 25% by mass. In that case, the storage stability of the composition may deteriorate.

<Ingredient (C)>
The hard surface cleaning agent composition of the present invention contains an anionic surfactant as the component (C). The anionic surfactant improves the detergency and foamability of the composition.
As the anionic surfactant, a known anionic surfactant used in a cleaning composition for a hard surface can be used, and sulfonic acid and a salt thereof, a sulfate ester and a salt thereof, a carboxylic acid and a salt thereof, and phosphorus can be used. Acid esters can be mentioned.

Examples of sulfonic acid and its salt include alkylbenzene sulfonic acid and its salt, alkyl sulfate and its salt, alkane sulfonic acid and its salt, α-olefin sulfonic acid and its salt, α-sulfo fatty acid and its salt, α-sulfo fatty acid alkyl. Examples thereof include esters and salts thereof, alkylsulfosuccinic acid and salts thereof, dialkylsulfosuccinic acid and salts thereof, and the like.

Examples of the sulfate ester and its salt include an alkyl sulfate ester and a salt thereof, an alkenyl sulfate ester and a salt thereof, a polyoxyalkylene alkyl ether sulfate ester (preferably a polyoxyethylene alkyl ether sulfate ester) and a salt thereof, and a polyoxyalkylene alkenyl ether. Examples thereof include sulfate esters and salts thereof.

Examples of the carboxylic acid and its salt include alkyl ether carboxylic acid and its salt, amide ether carboxylic acid and its salt, sulfosuccinic acid and its salt, amino acid-based anionic surfactant and the like.
Examples of the salt constituting the anionic surfactant include metal salts such as sodium, potassium, magnesium and calcium, and sodium or potassium is preferable, and sodium is more preferable.

The anionic surfactant preferably has an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 12 to 18 carbon atoms. Is more preferable. The alkyl group or the alkenyl group may be linear or branched.

Among the above anionic surfactants, alkane sulfonic acid and its salt, α-olefin sulfonic acid and its salt, and polyoxyalkylene alkyl ether sulfate ester and its salt are preferable, and alkane sulfonic acid and its salt and α-olefin sulfone are preferable. Acids and salts thereof, and polyoxyethylene alkyl ether sulfates and salts thereof are more preferred, polyoxyethylene alkyl ether sulfates and salts thereof and α-olefin sulfonic acids and salts thereof are even more preferred, α-olefin sulfonic acids and salts thereof. The salt is most preferred in terms of foam persistence.

Specific examples of the alkane sulfonic acid and its salt include tetradecane sulfonic acid and its sodium salt, hexadecane sulfonic acid and its sodium salt, and octadecane sulfonic acid and its sodium salt.
Among these, a mixture of secondary sodium alkanesulfonate having 14 or more carbon atoms and 17 or less carbon atoms is preferable.
For example, examples of commercially available products include the product name "HOSTAPUR SAS30 (manufactured by Clariant Japan)", the product name "MERSOLAT H-95 (manufactured by LANXESS)", and "Ramtel PS (manufactured by Kao Corporation)".

As a specific example of the polyoxyalkylene alkyl ether sulfate ester and its salt, a sodium salt having 10 to 18 carbon atoms and an average added molar number of ethylene oxide of 1 to 20 is preferable, and as a commercial product, the trade name "Tikapol NE7030 (Taika Co., Ltd.)" is preferable. ”,“ Emar 20C (manufactured by Kao Corporation) ”and the like.

As the α-olefin sulfonic acid and its salt, a mixture of sodium olefin sulfonic acid having 14 to 16 carbon atoms is preferable, and as a commercially available product, the trade name "HOSTAPUR OS LIQ (manufactured by Clariant Japan)" and the like can be mentioned.

The hard surface cleaning agent composition of the present invention contains water as the component (D). As the water, tap water, softened water, pure water, RO water, ion-exchanged water, and distilled water can be used. As tap water, for example, tap water in Arakawa-ku, Tokyo (pH = 7.6, total alkalinity (converted to calcium carbonate) 40.5 mg / L, German hardness 2.3 ° DH (of which calcium hardness 1. 7 ° DH, magnesium hardness 0.6 ° DH), chloride ion 21.9 mg / L, sodium and its compounds 15 mg / L, nitrate nitrogen and nitrite nitrogen 1.2 mg / L, fluorine and its compounds 0. 1 mg / L, boron and its compounds 0.04 mg / L, total trihalomethane 0.016 mg / L, residual chlorine 0.4 mg / L, organic matter (total organic carbon content) 0.7 mg / L).
The water of (D) of the present invention is the balance with respect to the total amount of the above-mentioned components (A) to (C), or the components (A) to (C), and other components (components (E) to (H)). ) Is the balance of the total amount.

The ratio of the component (A) to the component (C) of the cleaning agent composition for a hard surface of the present invention must have a value of (A) / (C) of 0.01 or more and 100 or less (mass ratio). It is preferably 0.03 or more and 50 or less, and more preferably 0.08 or more and 10 or less. If the value of (A) / (C) is less than 0.01, the antifouling property and the storage stability may be deteriorated. On the other hand, if the value of (A) / (C) exceeds 100, the detergency, foamability and storage stability may deteriorate.
The masses of the components (A) and (C) are the values charged at the time of preparation of the hard surface detergent composition, respectively.

In the hard surface detergent composition of the present invention, in addition to the above components (A) to (D), an amphoteric surfactant as a component (E), a nonionic surfactant as a component (F), and (G) A glycol-based solvent and / or a glycol ether-based solvent can be optionally added as a component, and an aromatic sulfonic acid compound can be optionally added as the component (H).

By using an amphoteric surfactant as the component (E), the detergency and antifouling property of the hard surface detergent composition can be further improved. Known amphoteric surfactants that can be used in the hard surface cleaning composition can be used.

Specific examples of the carboxylic acid type amphoteric surfactant include alkylcarbobetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamide carbobetaine, alkylamide sulfobetaine, alkylamide hydroxysulfobetaine, alkyldimethylbetaine, and alkyldiethyl. Alkyl betaine-type amphoteric surfactants such as betaine, alkylhydroxyethyl betaine, alkylamide propyldimethylaminoacetic acid betaine, alkyldimethylaminoacetic acid betaine, alkyl such as 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine. Imidazolinium betaine type amphoteric surfactant, coconut oil fatty acid amide propyl betaine, palm oil fatty acid amide propyl betaine, laurate amide propyl betaine and ricinoleic acid amide propyl betaine fatty acid amide propyl betaine type amphoteric surfactant, alkylaminoethylglycine, Examples thereof include glycine-type surfactants such as alkyldiaminoethylglycine and dialkyldiaminoethylglycine, and aminopropionic acid-type amphoteric surfactants such as alkylaminopropionate and alkylaminodipropionate.
Among these, alkyl betaine type amphoteric surfactants and aminopropion type amphoteric surfactants are preferable, alkyldimethylaminoacetic acid betaine is preferable as the alkyl betaine type amphoteric surfactants, and aminopropion type amphoteric surfactants are preferable. Alkylaminodipropionate is preferred, and betaine alkyldimethylaminoacetate is more preferred.

Examples of the above alkylaminodipropionate include octylaminodipropionate, decylaminodipropionate, laurylaminodipropionate, myristylaminodipropionate, palmitylaminodipropionate, and oleylaminodi. Examples thereof include propionate, and decylaminodipropionate, laurylaminodipropionate, and myristylaminodipropionate are preferable, and laurylaminodipropionate is more preferable. Moreover, the sodium salt is preferable as a salt.

Examples of the alkyldimethylaminoacetic acid betaine include octyldimethylaminoacetic acid betaine, decyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, oleyldimethylaminoacetic acid betaine, and the like. Betaine aminoacetate, betaine lauryldimethylaminoacetate, betaine myristyldimethylaminoacetate are preferred, and betaine lauryldimethylaminoacetate is more preferred.

The blending amount of the component (E) is not particularly limited as long as the effect of the present invention is obtained, but is preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the hard surface cleaning agent composition of the present invention. , 0.3% by mass or more and 8% by mass or less are more preferable, and 0.5% by mass or more and 5% by mass or less are particularly preferable. If the blending amount of the component (E) is less than 0.1% by mass with respect to the total amount of the cleaning agent composition for a hard surface of the present invention, the cleaning property and the antifouling property may be insufficient, while the cleaning property and the antifouling property may be insufficient. If it exceeds 10% by mass, the storage stability of the composition may deteriorate.

By using the nonionic surfactant of the component (F), the detergency and foamability of the hard surface detergent composition of the present invention can be further improved.
The nonionic surfactant may be, for example, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, or polyoxyethylene polyoxypropylene alkyl ether (the addition form of ethylene oxide and propylene oxide may be random or block. ), Polyethylene glycol propylene oxide adduct, Polyethylene glycol ethylene oxide adduct, Glycerin fatty acid ester or ethylene oxide adduct thereof, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or ethylene oxide thereof. Additives, fatty acid-N-methylmonoethanolamide or ethylene oxide adducts thereof, fatty acid diethanolamide or ethylene oxide adducts thereof, sucrose fatty acid ester, alkyl (poly) glycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, Examples thereof include fatty acid methyl ester ethoxylate and N-long chain alkyldimethylamine oxide. Among these, polyalkylene oxide additives such as polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, and polyoxyethylene polyoxypropylene alkyl ether are preferable because they have a good effect of improving detergency, and the following general formula ( The nonionic surfactant represented by 1) is more preferable:

R ^1- (OC ₂ H ₄ ) _n- OH (1)
(In the formula, R ¹ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and n represents a number of 1 to 20.)

^{R 1} of the general formula (1) represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, preferably a straight chain or a branched chain alkyl group or an alkenyl group, and examples of such a group include a straight chain. Or a branched octyl group, a straight chain or a branched nonyl group, a straight chain or a branched chain decyl group, a straight chain or a branched chain dodecyl group, a straight chain or a branched chain tridecyl group, a straight chain or a branched chain isotridecyl group, a straight chain or a branched chain. Alkyl groups such as chain tetradecyl groups, straight chain or branched chain pentadecyl groups, straight chain or branched chain hexadecyl groups, straight chain or branched chain peptadecyl groups, straight chain or branched chain octadecyl groups; straight chain or branched chain decenyl groups, straight chain Alternatively, an alkenyl group such as a branched chain pentadecenyl group, a straight chain or a branched chain octadecenyl group can be mentioned. Among these, a linear or branched-chain alkyl group having 8 to 14 carbon atoms is preferable, and a secondary alkyl group having 10 to 14 carbon atoms is more preferable because of its excellent detergency and foamability. Further, n is a number of 1 to 20, but a number of 3 to 18 is preferable, and a number of 5 to 18 is more preferable.

As the nonionic surfactant represented by the general formula (1), a commercially available product can be used. For example, the trade name "Softanol 90 (R ¹ : secondary dodecyl group, n = 9: Nippon Catalytic Chemical Industry)" can be used. (Manufactured by Co., Ltd.) ”, product name“ Softanol 120 (R ¹ : secondary dodecyl group, n = 12: manufactured by Nippon Catalytic Chemical Industry Co., Ltd.) ”, Product name“ Softanol 150 (R ¹ : secondary dodecyl group, n = 15: manufactured by Nippon Catalytic Chemical Industry Co., Ltd.) ”, trade name“ Softanol 200 (R ¹ : secondary dodecyl group, n = 20: manufactured by Nippon Catalytic Chemical Industry Co., Ltd.) ”etc. can be used. The above compounds may be combined in combination of two or more.

The amount of the nonionic surfactant as the component (F) is not particularly limited as long as the effect of the present invention is obtained, but is 0.05% by mass or more based on the total amount of the hard surface cleaning agent composition of the present invention. It is preferably 0.1% by mass or more, more preferably 4% by mass or less, and particularly preferably 0.3% by mass or more and 2% by mass or less. If the blending amount of the component (F) is less than 0.05% by mass, improvement in detergency and foamability may not be observed, while if it is more than 5% by mass, the storage stability is adversely affected. there is a possibility.

By using the glycol-based solvent and / or the glycol ether-based solvent which is the component (G), the detergency is further improved.
As the glycol-based solvent and / or the glycol-based solvent which is the component (G) of the present invention, a known solvent which can be blended in the detergent composition for a hard surface can be used.

Examples of the glycol-based solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, isoprene glycol, 1,2-butylene glycol, and 1,3-butylene glycol.

Examples of glycol ether-based solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, tri Ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Examples thereof include glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ethyl ether, and dipropylene glycol methyl ethyl ether. These may be used alone or in combination of two or more.

Among these solvents, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether are preferable from the viewpoint of detergency of the detergent composition for hard surfaces of the present invention.

The blending amount of the solvent of the component (G) is not particularly limited as long as the effect of the present invention is exhibited, but is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the cleaning agent composition for a hard surface of the present invention. It is more preferably 0.5% by mass or more and 12% by mass or less, and particularly preferably 1% by mass or more and 8% by mass or less. If the blending amount of the component (G) is less than 0.1% by mass, improvement in detergency may not be observed, while if more than 15% by mass is added, the storage stability may be adversely affected. There is.

By using the aromatic sulfonic acid compound which is the component (H), the storage stability of the hard surface detergent composition is further improved.
As the aromatic sulfonic acid compound which is the component (H) of the present invention, a known aromatic sulfonic acid compound which can be blended in the cleaning composition for a hard surface can be used.

Examples of the aromatic sulfonic acid compound include methoxybenzene sulfonic acid, methoxybenzene disulfonic acid, dimethoxybenzene sulfonic acid, dimethoxybenzene disulfonic acid, ethoxybenzene sulfonic acid, ethoxybenzene disulfonic acid, diethoxybenzene sulfonic acid, and diethoxybenzene disulfonic acid. , Propoxybenzene sulfonic acid, propoxybenzene disulfonic acid, butoxybenzene sulfonic acid, butoxybenzene disulfonic acid, methyl methoxybenzene sulfonic acid, methyl methoxybenzene disulfonic acid, methoxynaphthalin sulfonic acid, methoxynaphthalin disulfonic acid, dimethoxynaphthalin sulfonic acid, dimethoxynaphthalin Disulfonic acid, methylmethoxynaphthalinsulfonic acid, methylmethoxynaphthalindisulfonic acid, ethoxynaphthalinsulfonic acid, ethoxynaphthalindisulfonic acid, toluenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid and their sodiums and potassium , Lithium, calcium salt and the like. The toluene sulfonic acid and cumene sulfonic acid may be any of the o-form, m-form, and p-form triisomers, respectively. These may be used alone or in combination of two or more.

Among these aromatic sulfonic acid compounds, methoxybenzene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid, and salts thereof are preferable, and cumene sulfonic acid and salts thereof are more preferable.

The blending amount of the aromatic sulfonic acid compound of the component (H) is not particularly limited as long as the effect of the present invention is obtained, but is 0.01% by mass or more based on the total amount of the hard surface cleaning agent composition of the present invention. It is preferably 0.05% by mass or more, more preferably 4% by mass or less, and particularly preferably 0.1% by mass or more and 3% by mass or less. If the blending amount of the component (H) is less than 0.01% by mass, improvement in storage stability may not be observed, and on the other hand, even if more than 4% by mass is added, an effect commensurate with the added amount is obtained. It may not be possible.

<Viscosity>
The hard surface cleaning agent composition of the present invention preferably has a viscosity at 25 ° C. of 200 mPa · s or less, and more preferably 100 mPa · s or less, from the viewpoint of ejection property and foaming property by a hand sprayer. It is preferably 50 mPa · s or less, and more preferably 50 mPa · s or less. Here, the viscosity was determined by the B-type viscometer. The value after stirring for 5 minutes under the conditions of 25 ° C. and a rotation speed of 60 rpm using one rotor was measured.

<pH>
The pH of the detergent composition for a hard surface of the present invention is 9 or more and 14 or less, preferably 10.5 or more and 14 or less, and more preferably 12 or more and 14 or less from the viewpoint of detergency and storage stability. If the pH is less than 9, the detergency may be insufficient.

The detergent composition for a hard surface of the present invention contains components other than the above and other components such as a chelating agent, a builder, a preservative, an enzyme, a pigment, and a fragrance as long as the effects of the present invention are not impaired. Can be done.

Examples of the chelating agent include phosphates such as sodium orthorate, sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate; nitrilotriacetate (NTA), ethylenediamine tetraacetate (EDTA), and hydroxyethylenediamine triacetic acid ( HEDTA), diethylenetriaminopentaacetic acid (DTPA), triethylenetetraamine hexaacetate (TTHA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), methylglycindiacetate (MGDA), glutamate Aminopolyacetic acids such as diacetate (GLDA), aspartic acid diacetate (ASDA), β-alanine diacetate (ADA), serine diacetate (SDA); amino acids such as glycine, alanine, glutamic acid, aspartic acid and , Glucolic acid, lactic acid, citric acid, gluconic acid, tartaric acid, malic acid and other organic acids; polyacrylic acid or its salt, polyfumaric acid or its salt, polymaleic acid or its salt, poly-α-hydroxyacrylic acid or its salt. , Polyacetal acrylic acid or a polymer thereof. These chelating agents are preferably blended in an amount of 0.05 to 10% by mass based on the total amount of the hard surface cleaning agent composition of the present invention.

Examples of the builder include inorganic builders such as sodium sulfate, sodium chloride, and magnesium chloride.

Examples of the preservative include hydantoins, iodo-2-propynylbutylcarbamate, isopropylmethylphenol, hexachlorophene, irgasan, triclosan and the like.

Examples of the enzyme include amylase, protease, lipase, cellulase, glucanase and the like. Examples of the dye include natural dyes, synthetic dyes, and mixtures thereof. In addition, examples of the above-mentioned fragrances include natural fragrances, synthetic fragrances, and blended fragrances thereof.

<How to clean the hard surface>
The method for cleaning a hard surface of the present invention includes contacting a cleaning agent composition for a hard surface containing the above components with a hard surface to which stains (preferably oil stains) are attached.

The hard surface is not particularly limited, but may be either a hydrophobic surface or a hydrophilic surface. Examples include ranges, sinks, ventilators, countertops, cooking utensils, toilet bowls, toilet seats, wash basins, mirrors, bathtubs, tables, chairs, floors, windows and walls.
Examples of the material having a hydrophobic surface include hydrophobic metals such as hydrophobically treated stainless steel, polyvinyl chloride (PVC), ABS resin, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polycarbonate, acrylic resin, and polyurethane. Examples thereof include hydrophobic plastics such as 6-nylon and rubbers such as EPDM, NBR, CR, silicone and urethane. Composite materials such as fiber reinforced plastics (FRP) are also included.
The hydrophobic surface and the hydrophilic surface can be classified by the water contact angle in air. Here, the surface having a water contact angle of 60 ° or more is regarded as a hydrophobic surface, and the surface having a water contact angle of less than 60 ° is regarded as a hydrophilic surface. Divide. The water contact angle of the hard surface in the present invention is a value obtained by the sessile drop method using a contact angle meter (CA-X type) manufactured by Kyowa Interface Science Co., Ltd.

In the method for cleaning a hard surface using the cleaning agent composition for a hard surface of the present invention, the above-mentioned cleaning agent composition for a hard surface can also be used as an undiluted solution, and is 2 to 100 times, preferably 2 to 30 times with water or hot water. It is also possible to prepare and use a cleaning solution diluted twice, more preferably 2 to 10 times. As the water or hot water here, tap water, softened water, pure water, RO water, ion-exchanged water or distilled water, which are the same as the component (D) of the hard surface cleaning agent composition of the present invention, can be used.

The component (A) in the cleaning liquid obtained by diluting the hard surface cleaning agent composition of the present invention is usually 0.0005% by mass or more and 5% by mass or less, preferably 0% by mass, based on the total mass of the cleaning liquid. It is more preferably 0.001% by mass or more and 2% by mass or less, and particularly preferably 0.008% by mass or more and 0.5% by mass or less.
The component (B) in the cleaning liquid obtained by diluting the hard surface cleaning agent composition of the present invention is usually 0.05% by mass or more and 12% by mass or less, preferably 0% by mass, based on the total mass of the cleaning liquid. It is more preferably 1% by mass or more and 10% by mass or less, and particularly preferably 1% by mass or more and 7% by mass or less.
The component (C) in the cleaning liquid obtained by diluting the hard surface cleaning agent composition of the present invention is usually 0.005% by mass or more and 5% by mass or less, preferably 0% by mass, based on the total mass of the cleaning liquid. It is more preferably 0.01% by mass or more and 3% by mass or less, and particularly preferably 0.03% by mass or more and 2% by mass or less.

It is preferable that the hard surface cleaning agent composition of the present invention is filled in a hand sprayer and then sprayed in the form of bubbles so that the dirt on the hard surface of the object to be cleaned is in direct contact with the hard surface cleaning agent composition. ..
It is preferable to spray 0.1 ml to 3 ml, more preferably 0.3 ml to 2.5 ml, and 0.5 ml to 1.5 ml of the hard surface cleaning agent composition of the present invention by one spraying. It is more preferable to do so.

The hard surface cleaning agent composition of the present invention is sprayed directly onto the dirt on the hard surface using a hand sprayer, and then left for a certain period of time, for example, 0 seconds to 600 seconds, preferably 30 seconds to 300 seconds. The hard surface can be cleaned by wiping it off with dirt with a flexible material such as a cloth or sponge, or by rinsing it with water.
The hand sprayer used in the method for cleaning a hard surface of the present invention is not particularly limited, and a known hand sprayer can be used, and a known hand sprayer such as a trigger sprayer or a former player can be used. can.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Each component used in the formulation in Examples and Comparative Examples is shown below. In the following examples and the like, "%" represents mass% unless otherwise specified, and the numerical values of the formulations of Examples and Comparative Examples in the table represent pure mass%. The compounds used in Examples and Comparative Examples are described below.

(A) Component A-1: Cationized cellulose 1 (trade name: Leoguard GP, nitrogen content 1.8% by mass)
, Made by Lion Specialty Chemicals)
A-2: Cationized cellulose 2 (trade name: Leoguard LP, nitrogen content 1.0% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)
A-3: Cationized cellulose 3 (trade name: SupraCare212, nitrogen content 1.9% by mass, manufactured by Dow Chemical Co., Ltd.)
A-4: Cationized cellulose 4 (trade name: Leogard MLP, nitrogen content 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)
A-5: Cationized guar gum (trade name: Labol gum CG-M8M, nitrogen content 2.2-2.8% by mass, manufactured by DSP Gokyo Food & Chemicals Co., Ltd.)
A-6: Cationized starch (trade name: SENSOMER CI-50, nitrogen content 1.8% by mass, manufactured by Lubrizol)

(A) Component comparison component A'-1: Homopolymer of diallyldimethylammonium chloride (weight average molecular weight 75000)

(B) Component B-1: Sodium hydroxide B-2: Potassium hydroxide B-3: Monoethanolamine

(C) Ingredient C-1: Sodium α-olefin sulfonate (trade name: HOSTAPUR OS LIQ, manufactured by Clariant Japan)
C-2: Secondary sodium alkane sulfonate (trade name: HOSTAPUR SAS30, manufactured by Clariant Japan)
C-3: Sodium laurylbenzene sulfonate (trade name: TAYCA Power L121, manufactured by TAYCA)
C-4: Polyoxyethylene (EO3 mol) sodium lauryl ether sulfate (trade name: Emar 20C, manufactured by Kao Corporation)

(D) Component D-1: Ion-exchanged water

(E) Ingredient E-1: Sodium laurylaminodipropionate (trade name: Enagicol DP-30, manufactured by Lion Specialty Chemicals Co., Ltd.)
E-2: 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine (trade name: Energycol CNS, manufactured by Lion Specialty Chemicals Co., Ltd.)
E-3: Sodium lauryldiaminoethylglycine (trade name: Lebon S, manufactured by Sanyo Chemical Industries, Ltd.)
E-4: Betaine lauryldimethylaminoacetic acid (trade name: Anchtor 24B, manufactured by Kao Corporation)

(F) Component F-1: Nonionic surfactant 1 (secondary alcohol with 15 mol of EO added (trade name: Softanol 150, manufactured by Nippon Shokubai Co., Ltd.))
F-2: Nonionic surfactant 2 (secondary alcohol with 9 mol of EO added (trade name: Softanol 90, manufactured by Nippon Shokubai Co., Ltd.))
F-3: Nonionic surfactant 3 (lauryl alcohol with 9 mol of EO added (trade name: Blaunon EL-1509, manufactured by Aoki Oil & Fat Industry Co., Ltd.))

(G) Component G-1: Diethylene glycol monobutyl ether G-2: Triethylene glycol Monobutyl ether G-3: Diethylene glycol

(H) Component H-1: Sodium cumene sulfonate H-2: Sodium toluene sulfonate

In the composition of each example, the water of the component (D) was added to the mixing tank so that the total of the composition was 100% by mass, and then the component (A), the component (B), and the component (C) (necessarily). The components (E), (F), (G), and (H) were mixed in a mixing tank, and the mixture was sufficiently mixed and stirred to prepare the mixture.

Examples 1 to 53, Comparative Examples 1 to 6
The detergent compositions for hard surfaces shown in Tables 1 to 7 were prepared. Detergency, stain resistance, foamability, and storage stability were measured using each hard surface detergent composition. Tables 1 to 6 show the results of Examples 1 to 53, and Table 7 shows the results of Comparative Examples 1 to 6, respectively.

* 1: How to measure pH Connect a composite electrode for pH measurement (made by HORIBA; glass sliding sleeve type) to a pH meter (made by HORIBA; pH / ion meter F-23) and turn on the power. A saturated aqueous potassium chloride solution (3.33 mol / L) was used as the pH electrode internal liquid.
Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 mL beaker, and 25 It was immersed in a constant temperature bath at ° C. for 30 minutes. The electrode for pH measurement was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration operations were performed in the order of pH 6.86 → pH 9.18 → pH 4.01.
Each hard surface detergent composition was filled in a 100 mL beaker and adjusted to 25 ° C. in a constant temperature bath. The pH measuring electrode was immersed in the sample adjusted to a constant temperature for 3 minutes, and the pH of the diluted solution was measured.

* 2: Detergency test Soybean oil was uniformly applied to one side of a stainless steel plate (SUS304, 50 mm × 100 mm) so as to be 0.1 ± 0.01 g, and baked in an oven at 250 ° C. for 120 minutes. The stainless steel plate was leaned vertically, and each hard surface cleaning agent composition was sprayed with a spray gun so as to be sufficiently covered, and contacted for 3 minutes. Then, it was rinsed with running water for 30 seconds and then dried, and the washing rate was calculated by the following formula from the weight change before and after washing, and a washing rate of 85% or more was evaluated as good.
Cleaning rate (%) = {((Stainless steel plate after applying and baking soybean oil)-(Stainless steel plate after cleaning)) / Actual mass of applied soybean oil} x 100

* 3: Antifouling test (hydrophilic surface)
After spraying each hard surface cleaner composition onto one side of a stainless steel plate test piece (SUS304, 75 mm x 150 mm) with a spray gun for 1 minute and rinsing with running water for 30 seconds. It was dried. 2 ml of soybean oil dyed with Sudan III was uniformly applied to the washed surface of the dried test piece with a spatula, then rinsed with running water for 30 seconds, and the surface condition of the dried test piece was evaluated according to the following criteria.
Evaluation criteria ◎: No dirt is found ○: Dirt is less than 10% of the area of the test piece, but dirt can be visually confirmed △: Dirt is attached to 10% to 50% of the area of the test piece × : It was judged that more than 50% of the area of the test piece was dirty, and Δ, ○, and ◎ were judged to be practical.

* 4: Antifouling test (hydrophobic surface)
One side of the test piece (hard PVC, 75 mm x 150 mm) of the resin plate was sprayed with a spray gun to fully cover the cleaning agent composition for each hard surface, contacted for 1 minute, and rinsed with running water for 30 seconds. It was later dried. 2 ml of soybean oil dyed with Sudan III was uniformly applied to the washed surface of the dried test piece with a spatula, then rinsed with running water for 30 seconds, and the surface condition of the dried test piece was evaluated according to the following criteria.
Evaluation criteria ◎: No dirt is found ○: Dirt is less than 10% of the area of the test piece, but dirt can be visually confirmed △: Dirt is attached to 10% to 50% of the area of the test piece × : It was judged that more than 50% of the area of the test piece was dirty, and Δ, ○, and ◎ were judged to be practical.

* 5: Foamability test A 100 mL glass stopper Epton tube was sprayed with a spray gun (T95: Canyon Co., Ltd., about 1 ml per spray) three times for each hard surface cleaning agent composition, and left to stand for 1 minute. The height of bubbles from the cleaning liquid surface was measured and evaluated according to the following criteria.

<Evaluation criteria>
⊚: Foam height is 10 cm or more,
◯: Foam height is 7.5 cm or more and less than 10 cm,
Δ: Bubble height is 5 cm or more, less than 7.5 cm,
X: The height of the bubbles was set to less than 5 cm, and Δ, ◯, and ⊚ were judged to be practical.

* 6: Storage stability test Put each hard surface cleaning agent composition in a closed glass container, leave it in a constant temperature bath at 40 ° C for 6 months, and visually judge the state after 6 months according to the following criteria. evaluated.
Evaluation criteria ○: Stable with no separation or turbidity △: There is no overall separation and some turbidity is observed, but there is no problem in use ×: Separation or turbidity is observed
And, Δ and ○ were judged to be practical.
In addition, Examples 15, 18, 35, 36, 46-49 are reference examples.

Claims (10)

(A) Cationized polysaccharide as a component,
(B) Alkaline agent as an ingredient,
It contains an anionic surfactant as a component (C) and water as a component (D), and the component (B) contains at least one of sodium hydroxide and potassium hydroxide, and the components (A) and (C). the weight ratio of (a) / (C) value is 0.01 or more, 100 Ri der hereinafter pH 13.1 or more at 25 ° C. of the composition, of 14 or less, hard surface detergent composition. The hard surface cleaning agent composition according to claim 1, wherein the component (A) is cationized cellulose. Claim 1 in which the component (C) contains one or more selected from the group consisting of α-olefin sulfonic acid, polyoxyalkylene alkyl ether sulfate ester, secondary alkane sulfonic acid, and salts thereof. Or the hard surface cleaning agent composition according to 2. The hard surface cleaning agent composition according to any one of claims 1 to 3, further comprising an amphoteric surfactant as the component (E). The hard surface cleaning agent composition according to any one of claims 1 to 4, further comprising a nonionic surfactant as the component (F). The hard surface cleaning agent composition according to any one of claims 1 to 5, further comprising a solvent selected from a glycol-based solvent, a glycol ether-based solvent, and a mixture thereof as the component (G). The hard surface cleaning agent composition according to any one of claims 1 to 6, further comprising an aromatic sulfonic acid compound as the component (H). The hard surface cleaning agent composition according to any one of claims 1 to 7, for cleaning the hard surface of a microwave oven, a sink, a ventilation fan, a countertop, or a cooking utensil. A method for cleaning a hard surface, which comprises contacting the hard surface with a hand sprayer in the form of a foam of the detergent composition for a hard surface according to any one of claims 1 to 8. The method for cleaning a hard surface according to claim 9, wherein the hand sprayer is a trigger sprayer or a former player.