JP2011219652A - Hard surface detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition which is effective for removing stubborn oil stains, has high anti-redeposition performance, and has a high product stability.SOLUTION: There is provided a hard surface detergent composition containing (A) an amphoteric polymer having both acidic groups and/or anionic groups and cationic groups and/or amino groups, (B) a carboxylic acid type amphoteric surfactant, (C) a nonionic surfactant, (D) an alkali agent, and (E) water, wherein (A)/(B)=1/0.2 to 1/100 (in mass ratio).

Description

  The present invention relates to a hard surface cleaning composition excellent in anti-redeposition property capable of preventing reattachment of dirt after removing stubborn oil stains adhering to a hard surface.

  In general households, kitchen fan, gas range, bath tub, toilet, dishes, vehicles, buildings, etc. are made of hard materials such as metal, plastic, glass, ceramics, concrete. Various stains adhere to these hard surfaces due to wind and rain, foods, emissions, oils, exhaust gases, and the like. Various cleaning agents are used to remove such stains, but in order to prevent the reattachment of stains after cleaning (antifouling effect), cleaning agents containing a polymer in the cleaning agent are known (for example, Patent Documents 1 to 3).

  However, when the amount of the polymer is too large, the product stability of the cleaning agent is deteriorated and aggregation or precipitation occurs, and as a result, the cleaning power may be inferior. On the other hand, if the blending amount of the polymer is reduced below a certain amount in order to increase the product stability of the cleaning agent or maintain the cleaning power, there is a problem that the antifouling effect obtained by the polymer is not sufficiently exhibited. .

  Therefore, the present inventors have invented a hard surface cleaning agent in which a specific amphoteric polymer and a specific amphoteric surfactant are blended in a specific ratio (see Patent Document 4). The cleaning agent according to the present invention has high product stability and high antifouling effect, blackening due to soap scum, yellowing in places called watering facilities such as washstands, toilets and bathrooms, Alternatively, it is effective in removing scales and preventing reattachment of dirt.

JP 2002-146395 A Special table 2003-505535 gazette JP 2008-169361 A Japanese Patent Application No. 2010-022295

In places such as a ventilator or gas range in the kitchen, stubborn oil stains rather than dirt due to soap scum are a problem. The oil stains adhering to the ventilation fan and gas range have undergone reactions such as polymerization due to deterioration, and are very difficult to clean. In addition, it is difficult to completely prevent the adhesion of dirt at such locations where oil stains are adhered, but removal of oil stains, etc., adhered after the antifouling treatment has been carried out. Easy to do. Therefore, a cleaning agent having a more effective cleaning function and antifouling function in a place where stubborn oil stains adhere has been desired.
Therefore, the problem to be solved by the present invention is to provide a cleaning composition that is effective in cleaning stubborn oil stains, has high performance for preventing reattachment of stains, and has high product stability.

  Therefore, the present inventors diligently studied to arrive at the present invention. That is, the present invention comprises (A) an amphoteric polymer containing an acidic group and / or an anionic group and a cationic group and / or an amino group, (B) a carboxylic acid type amphoteric surfactant, and (C) a nonionic interface. For hard surface, comprising activator, (D) alkali agent and (E) water and having a ratio of (A) / (B) = 1 / 0.2 to 1/100 (mass ratio) It is a cleaning composition.

  The effect of the present invention is to provide a cleaning composition that is effective in cleaning stubborn oil stains, has a high performance for preventing reattachment of stains, and has high product stability.

The component (A) of the present invention is an amphoteric polymer containing an acidic group and / or an anionic group and a cationic group and / or an amino group. Examples of the acidic group include groups exhibiting acidity such as a carboxyl group, a sulfo group, and a phosphone group, and examples of the anionic group include ammonium salts, amine salts, and alkali metal salts of the aforementioned acidic groups. On the other hand, examples of the cationic group include quaternary ammonium salts using Cl ⁻ , Br ⁻ , dialkyl sulfate ions, etc. as counter ions. An amino group is a primary amino group such as —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (C ₂ H ₆ ), —N (C ₂ H ₆ ) ₂ , Secondary amino group and tertiary amino group can be mentioned.

  The amphoteric polymer of component (A) is a polymer containing the above acidic group and / or anionic group as essential components in the polymer, and further containing a cationic group or amino group as essential components in the polymer. The amphoteric polymer of component (A) only needs to contain the above-mentioned essential groups, and the production method, the ratio of monomers, raw materials, etc. are not limited, but can be easily produced and have an antifouling effect. Since a high amphoteric polymer can be obtained, the amphoteric polymer obtained by combining and reacting the monomers of the following general formulas (2) to (4) is preferable.

(In the formula, R ^{1 to} R ⁴ are each independently represented by —COOH, —SO ₃ H, —PO ₃ H ₂ , —CO—A—SO ₃ H, —CO—A′—PO ₃ H _2. Or an anionic group comprising an ammonium salt or an alkali metal salt thereof, a hydrogen atom, or a group selected from a hydrocarbon group having 1 to 6 carbon atoms, and A and A ′ each have 1 carbon atom. Represents an alkylene group of ˜3, provided that any one or more of R ^{1 to} R ⁴ must be an acidic group or an anionic group.)

(In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁸ represents an alkylene group having 1 to ⁸ carbon atoms, —COOR ¹² —, —CONHR ¹³ —, —OCOR. ¹⁴ and any one group selected from —R ¹⁵ OCOR ¹⁶ —, R ^{12 to} R ¹⁶ each independently represents an alkylene group having 1 to 6 carbon atoms, and R ⁹ , R ¹⁰ and R ¹¹ are Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R ⁷ represents an alkyl group having 1 to 3 carbon atoms or —R ⁸ —C (R ⁹ ) ═CR ¹⁰ R ¹¹ , and X ⁻ represents Represents an anionic group.)

(In the formula, R ¹⁷ represents an alkyl group having 1 to 3 carbon atoms, R ¹⁹ represents an alkylene group having 1 to 8 carbon atoms, —COOR ²³ —, —CONHR ²⁴ —, —OCOR ²⁵ , and —R ²⁶ OCOR. ²⁷ represents any group selected from-, R ^{23 to} R ²⁷ each independently represents an alkylene group having 1 to 6 carbon atoms, R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, The alkyl group having 1 to 3 carbon atoms is represented, and R ¹⁸ represents an alkyl group having 1 to 3 carbon atoms or —R ¹⁹ —C (R ²⁰ ) ═CR ²¹ R ²² .

Any one or more of R ^{1 to} R ⁴ of the compound represented by the general formula (2) (hereinafter referred to as (a-1)) are —COOH, —SO ₃ H, —PO ₃ H ₂ , — be a _{CO-a-SO 3 H,} -CO-A'-PO 3 acid groups represented by _{H 2,} or ammonium salts of these acidic groups, a lithium salt, sodium salt, anionic groups potassium salt I must. Among R ^{1 to} R ⁴ , those that are not acidic groups or anionic groups are hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, and phenyl group. .

  Specific examples of (a-1) include acrylic acid, methacrylic acid, ethacrylic acid, dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid, and fumaric acid. , Itaconic acid, citraconic acid, mesaconic acid, N-methacryloylalanine, N-acryloylhydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl methacrylate, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid A monomer containing an anionic group obtained by neutralizing these acidic groups with ammonium salt, lithium salt, sodium salt, potassium salt or the like. Among these, since it is excellent in antifouling property, the monomer containing an anionic group is preferable, and acrylate and methacrylate are more preferable.

R ⁵ and R ⁶ of the compound represented by the general formula (3) (hereinafter referred to as (a-2)) represent an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group. , Ethyl group, propyl group, and isopropyl group. R ⁸ represents any one of an alkylene group having 1 to ⁸ carbon atoms, —COOR ¹² —, —CONHR ¹³ —, —OCOR ¹⁴ , and —R ¹⁵ OCOR ¹⁶ —, and the alkylene group having 1 to 8 carbon atoms is For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1 -Methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, etc. are mentioned, and R ^{12 to} R ¹⁶ are each Represents an alkylene group having 1 to 6 carbon atoms, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexene, Len group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2 , 4-dimethylbutylene group, 1,3-dimethylbutylene group and the like. R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group having 1 to 3 carbon atoms include those described above. R ⁷ represents an alkyl group having 1 to 3 carbon atoms or —R ⁸ —C (R ⁹ ) ═CR ¹⁰ R ^11, and examples of the alkyl group having 1 to 3 carbon atoms include those described above. X ⁻ represents an anionic group, and examples of the anionic group include Cl ⁻ , Br ⁻ , dimethyl sulfate ion, and diethyl sulfate ion.

Preferable (a-2) is, for example, acryloylaminoalkyl (C1 to C8) -N, N, N, -trialkyl (C1 to C3) quaternary ammonium salt, methacryloylaminoalkyl (C1 -8) -N, N, N, -trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, N- (ω-alkyl (3 to 10 carbon atoms)) -N, N, N-trialkyl (carbon) (C1-C3) Quaternary ammonium salt, N, N-di (ω-alkyl (C3-C10))-N, N-dialkyl (C1-C3) quaternary ammonium salt. Among these, N, N-di (ω-alkyl (3 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt is more preferable, and N, N-diallyl-N, N-dimethyl quaternary ammonium salt is more preferred. The salt type (X ⁻ type) is preferably Cl ⁻ or dimethyl sulfate ion, and more preferably Cl ⁻ .

R ¹⁷ of the compound represented by the general formula (4) (hereinafter referred to as (a-3)) represents an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group and an ethyl group. , A propyl group, and an isopropyl group. R ¹⁹ is an alkylene group having 1 to 8 carbon ^{atoms, -COOR 23 -, - CONHR 24} -, - OCOR 25, and ^-R 26 OCOR ²⁷ - represents one of, the alkylene group having 1 to 8 carbon atoms, For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1 - methylbutylene group, 2-methyl-butylene group, 3-methyl-butylene, 4-methyl-butylene, 2,4-dimethyl butylene, 1,3-dimethyl butylene group and the ^like, R 23 ^{to R 27} each Represents an alkylene group having 1 to 6 carbon atoms, such as methylene group, ethylene group, propylene group, butylene group, pentylene group, Silene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2 , 4-dimethylbutylene group, 1,3-dimethylbutylene group and the like. R ²⁰ , R ²¹ and R ²² each represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group having 1 to 3 carbon atoms include those described above. R ¹⁸ represents an alkyl group having 1 to 3 carbon atoms or —R ¹⁹ —C (R ²⁰ ) ═CR ²¹ R ^22, and examples of the alkyl group having 1 to 3 carbon atoms include those described above.

  Preferable (a-3) is, for example, acryloylaminoalkyl (C1-8) -N, N, -dialkyl (C1-3) amine, methacryloylaminoalkyl (C1-8) -N, N, -dialkyl (1 to 3 carbon atoms) amine, N- (ω-alkyl (3 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) amine, N, N-di (ω- Alkyl (C3-C10) -N-alkyl (C1-C3) amine is mentioned. Among these, N, N-di (ω-alkyl (3 to 10 carbon atoms) -N-alkyl (1 to 3 carbon atoms) amine is more preferable, and N, N-diallyl-N-methylamine is still more preferable. .

  The above (a-1) and (a-2) are copolymerized, or (a-1) and (a-3) are copolymerized, or (a-1), (a-2) and (a -3) can be copolymerized to obtain the amphoteric polymer of component (A). However, since it is easy to manufacture and has good performance, (a-1) and (a-2) are copolymerized, or Amphoteric polymers obtained by copolymerizing (a-1) and (a-3) are preferred. In obtaining the amphoteric polymer, (a-1), (a-2) and (a-3) may be used alone or in combination of two or more monomers. (A-1) and (a-2) The reaction ratio of (a-1) and (a-3) is not limited, and the reaction may be carried out at an arbitrary ratio. However, since antifouling property is preferable, it is preferable to react at (a-1) / (a-2) = 50/50 to 5/95 (molar ratio), (a-1) / (a-2) = 40/60 to 10/90 (molar ratio) is more preferable for the reaction. Similarly, when (a-3) is used as the monomer, the reaction is preferably carried out at (a-1) / (a-3) = 50/50 to 5/95 (molar ratio), (a-1) / (A-3) = 40/60 to 10/90 (molar ratio) is more preferable. When the proportion of (a-1) exceeds 50 mol% or less than 5 mol%, the antifouling effect of the amphoteric polymer may be lowered. Moreover, since the antifouling effect is high, the amphoteric polymer containing (a-2) is preferable to the amphoteric polymer containing (a-3). When (a-1), (a-2) and (a-3) are copolymerized, (a-1) / (a-2) + (a-3) = 50/50 to 5/95 It is preferable to make it react by (molar ratio), and it is more preferable to make it react by (a-1) / (a-2) + (a-3) = 40 / 60-10 / 90 (molar ratio).

A known polymerization method may be used as the polymerization method for the amphoteric polymer, and radical polymerization is particularly preferable. Specifically, for example, the total amount of monomers to be polymerized is made an aqueous solution of about 20 to 60% by mass, the initiator is added in an amount of 0.1 to 5% by mass with respect to the total amount of monomers, and polymerization is performed at 40 to 80 ° C. for 1 to 30 hours. do it. At this time, the monomer may be added in portions or the initiator may be added in portions. Examples of initiators that can be used include azo initiators such as 2,2′-azobis (2-amidinopropane) dihydrochloride and 2,2′-azobis- (N, N-dimethyleneisobutylamidine) dihydrochloride. Agents, organic peroxides such as hydrogen peroxide and benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, perbenzoic acid, persulfuric acid such as sodium persulfate, potassium persulfate, ammonium persulfate Salts, redox initiators such as hydrogen peroxide-Fe ³⁺ , and other existing radical initiators may be used.

  Depending on the reaction conditions and monomer addition method, the resulting amphoteric polymer is in the form of a block polymer, a random polymer, or a block / random polymer. Any polymerization form may be used, but a random polymer is preferable because the antifouling property is good and the product stability of the finally blended cleaning agent is good. Although the molecular weight of the amphoteric polymer obtained varies depending on the reaction conditions, the weight average molecular weight is preferably 1000 to 3000000, more preferably 10000 to 2000000. If the weight average molecular weight is small, the antifouling effect may not be obtained.If the weight average molecular weight is too large, the viscosity becomes large and handling becomes difficult. It may get worse.

  The component (B) of the present invention is a carboxylic acid type amphoteric surfactant. Carboxylic acid type amphoteric surfactants are those containing a carboxyl group and / or a salt thereof, and an amino group or quaternary ammonium in the molecule, and are generally amino acid type amphoteric surfactants or betaine type amphoteric interfaces. It is called an activator. Examples of such carboxylic acid type amphoteric surfactants include alkylbetaine type amphoteric surfactants such as lauryl dimethyl betaine, lauryl diethyl betaine, stearyl dimethyl betaine, oleyl dimethyl betaine, lauryl dihydroxyethyl betaine; N-coconut fatty acid acyl-N -Carboxymethyl-N-hydroxyethylethylenediamine sodium (2-cocoalkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine), N-coconut fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium, N-tallow Fatty acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium, N-tallow fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenedi Imidazolium betaine-type amphoteric surfactants such as mine sodium; Amidopropyl betaine-type amphoteric surfactants such as amidepropylbetaine laurate, amidopropylbetaine stearate, amidopropylbetaine oleate; sodium laurylaminopropionate, oleylaminopropion Amino acid type amphoteric surfactants such as sodium acid, sodium laurylaminodipropionate, sodium oleylaminodipropionate and the like can be mentioned.

  Among these amphoteric surfactants, an amidopropyl betaine amphoteric surfactant and an amino acid amphoteric surfactant are preferred because they have a large synergistic effect in antifouling properties when blended with the component (A). Amidopropyl betaine More preferred are amphoteric surfactants of the type. In addition, these carboxylic acid type amphoteric surfactants are also involved in detergency, and when added, the detergency against oil stains is improved. When other amphoteric surfactants such as amine oxide type, sulfobetaine type, and phosphobetaine type are used, a good antifouling effect cannot be obtained depending on the material of the object to be cleaned.

  (C) component of this invention is a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether (addition form of ethylene oxide and propylene oxide may be random or block. ), Polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or its ethylene oxide addition , Fatty acid-N-methylmonoethanolamide or its ethylene oxide adduct, fatty acid diethanolamide De or an ethylene oxide adduct, a sucrose fatty acid ester, alkyl (poly) glycerol ether, polyglycerol fatty acid esters, polyethylene glycol fatty acid esters, fatty acid methyl ester ethoxylates, N- long chain alkyl dimethyl amine oxides, and the like. Among these, since the balance between the cleaning effect and the antifouling effect is good, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide A polyalkylene oxide adduct such as an adduct is preferred, and a nonionic surfactant represented by the following general formula (1) is more preferred.

_{R- (OC 2 H 4) n} -OH (1)
(In the formula, R represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n represents a number of 1 to 15)

  R in the general formula (1) represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, such as decyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, Examples thereof include alkyl groups such as peptadecyl group and octadecyl group; alkenyl groups such as decenyl group, pentadecenyl group and octadecenyl group. Among these, an alkyl group having 12 to 16 carbon atoms is preferable because of its large detergency. Moreover, although n is a number of 1-15, the number of 3-12 is preferable and the number of 5-10 is more preferable. The smaller the value of n, the higher the cleaning effect, but the lower the antifouling effect, and the higher the value of n, the higher the antifouling effect, but if the value of n exceeds 15, stubborn oil stains cannot be washed efficiently. There is a case.

  The component (D) of the present invention is an alkaline agent. Specific alkali agents include, for example, strong alkali agents such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium orthosilicate; sodium carbonate, sodium bicarbonate, potassium carbonate, sodium sesquicarbonate, sodium sesquisilicate, mono Examples include weak alkali agents such as ethanolamine, diethanolamine, triethanolamine, and sodium tetraborate. Among these, inexpensive alkali agents such as sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, and triethanolamine are preferable, and sodium hydroxide, potassium hydroxide, and monoethanolamine are more preferable because of high cleaning effect. . In addition, 10 or more are preferable and, as for pH of the cleaning composition for hard surfaces of this invention at the time of mix | blending an alkaline agent, 11 or more are more preferable.

  The ratio of the component (A) and the component (B) in the hard surface cleaning composition of the present invention must be (A) / (B) = 1 / 0.2 to 1/100 (mass ratio). Preferably, (A) / (B) = 1 / 0.5 to 1/50 (mass ratio), more preferably (A) / (B) = 1/1 to 1/20 (mass ratio). The component (A) has an antifouling function, and when the component (B) is added, the antifouling effect is further enhanced by a synergistic effect. However, if there is too little (B) component, the synergistic effect will fall, and if there are too many (B) components, the synergistic effect will fall.

  The detergent composition for hard surface of the present invention is an aqueous solution containing water as the component (E), but if the blending ratio of the component (A) and the component (B) is within the above range, (A) to ( The blending amount of each component of D) is not particularly specified. However, depending on the blending amount of each component, product stability, detergency, and the like may be reduced. Therefore, the blending ratio of each component with respect to the total amount of the cleaning composition is preferably as follows.

  The component (A) is preferably 0.01 to 5% by mass, more preferably 0.03 to 4% by mass, still more preferably 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass with respect to the total amount of the cleaning agent. % Most preferred. If it is less than 0.01% by mass, the antifouling effect may not be obtained, and if it exceeds 5% by mass, the product stability of the cleaning agent may be deteriorated.

  The component (B) is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, still more preferably 0.08 to 5% by mass, and 0.1 to 1% by mass with respect to the total amount of the cleaning agent. % Is most preferred. When it is less than 0.01% by mass, a synergistic effect in antifouling properties with the component (A) may not be obtained. When it exceeds 10% by mass, the synergistic effect with the component (A) is reduced, or the blending amount May not be able to achieve the appropriate effect.

  The component (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, still more preferably 1 to 10% by mass, and most preferably 2 to 8% by mass with respect to the total amount of the cleaning agent. . If it is less than 0.1% by mass, the necessary cleaning power may not be obtained, and if it exceeds 15% by mass, the product stability of the cleaning agent may be deteriorated.

  The component (D) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass, and most preferably 2 to 8% by mass with respect to the total amount of the cleaning agent. . If it is less than 0.1% by mass, the necessary cleaning power may not be obtained, and if it exceeds 20% by mass, the product stability of the cleaning agent may be deteriorated.

  In addition, the water of (E) component is the remainder with respect to the total amount of said (A)-(D) component, or the sum total of (A)-(D) component and other components (the component which can be mix | blended below). The balance with respect to the quantity.

  The hard surface cleaning composition of the present invention is an anionic surfactant, a cationic surfactant, a chelating agent, an organic solvent, a builder, an antiseptic, a dye, a fragrance and the like as long as the effects of the present invention are not impaired. Ingredients can be blended. In actual cleaning, various types of water are used, and water with high hardness may be used. In order to cope with such high hardness water, it is preferable to add a chelating agent capable of maintaining good detergency even in hard water. Moreover, it is preferable to add a cationic surfactant for the purpose of imparting a bactericidal effect. In addition, when compounding a cationic surfactant, an anionic surfactant may be blended together with a cationic surfactant because the product stability may deteriorate and the bactericidal effect may be reduced if an anionic surfactant is blended together. should not be done.

  Examples of the cationic surfactant include alkyl (alkenyl) trimethyl ammonium salt, dialkyl (alkenyl) dimethyl ammonium salt, alkyl (alkenyl) quaternary ammonium salt, mono- or dialkyl (alkenyl) containing ether group, ester group or amide group. ) Quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) amine Examples thereof include salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride. When these cationic surfactants are blended, bactericidal properties can be imparted to the cleaning composition, but the blending amount is preferably 0.01 to 2% by weight, and 0.05 to 1% by weight with respect to the total amount of the cleaning composition. % Is more preferable, and 0.1 to 0.5% by mass is still more preferable. If it is less than 0.01% by mass, the effect as a disinfectant may not be obtained, and if it exceeds 2% by mass, the antifouling effect on the glass or porcelain tile may not be obtained or the product stability may be deteriorated.

  Examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, and phosphate ester salts. , Fatty acid ester sulfate ester salt, glyceride sulfate ester salt, fatty acid ester sulfonate salt, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene Alkyl ether carboxylate, acylated peptide, sulfate ester salt of fatty acid alkanolamide or its alkylene oxide adduct, sulfosuccinate ester, alkylbenzene sulfonate, alkyl naphthalene sulfonate Salt, alkylbenzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyltaurine salt, N-acyl glutamic acid or salt thereof, acyloxyethane sulfonate, alkoxyethane sulfonate, N-acyl -Β-alanine or salt thereof, N-acyl-N-carboxyethyltaurine or salt thereof, N-acyl-N-carboxymethylglycine or salt thereof, acyl lactate, N-acyl sarcosine salt, and alkyl or alkenylaminocarboxy Examples thereof include methyl sulfate. These anionic surfactants are 0.1 to 20% by mass, preferably 0.5 to 15%, based on the total amount of the detergent composition, as a detergent for increasing the detergency when no cationic surfactant is added. It can mix | blend the mass%.

  Examples of chelating agents include phosphates such as sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate; nitrilotriacetate (NTA), ethylenediaminetetraacetate (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA). ), Diethylenetriaminopentaacetate (DTPA), triethylenetetraamine hexaacetate (TTHA), hydroxyethyliminodiacetate (HIDA), dihydroxyethylglycine (DHEG), methylglycine diacetate (MGDA), diglutamate Aminopolyacetates such as acetate (GLDA), aspartate diacetate (ASDA), β-alanine diacetate (ADA), serine diacetate (SDA); amino acids such as glycine, alanine, glutamic acid and aspartic acid , Organic acids such as glycolic acid, lactic acid, citric acid, gluconic acid, tartaric acid, malic acid; polyacrylic acid or its salt, polyfumaric acid or its salt, polymaleic acid or its salt, poly-α-hydroxyacrylic acid or its salt And polymers such as polyacetal acrylic acid or a salt thereof. These chelating agents are preferably blended in an amount of 0.1 to 10% by mass relative to the total amount of the cleaning composition.

  Examples of the organic solvent include ethanol, propanol, 2-propanol, butanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, (mono, di, tri) ethylene glycol (mono, di, tri) propylene Glycol monomethyl ether, , Di, tri) ethylene glycol (mono, di, tri) propylene glycol monoethyl ether, (mono, di, tri) ethylene glycol (mono, di, tri) propylene glycol monopropyl ether, (mono, di, tri) ethylene Examples thereof include lower alcohols and glycol compounds such as glycol (mono, di, tri) propylene glycol monobutyl ether. These organic solvents are preferably blended in an amount of 1 to 10% by mass based on the total amount of the cleaning composition.

  The cleaning composition for a hard surface of the present invention does not select a cleaning part, for example, a range, a sink, a ventilation fan, a cooking table, a cooking device, a toilet, a toilet seat, a wash basin, a mirror, a bathtub, a table, a chair, a floor, a window, and the like. It can be used for cleaning hard surfaces such as walls. Also, the material of these hard surfaces is not limited to any kind, and examples thereof include metals such as stainless steel, copper and iron, porcelain, ceramics, glass, plastics and the like. Dirt that adheres to these hard surfaces is various such as oil stains, water stains, protein stains, inorganic stains, etc., and any stains can be washed and prevented from reattachment. Since the cleaning composition has a high cleaning effect against oil stains and prevention of redeposition, it is highly likely to become dirty with oil, kitchens such as ranges, sinks, ventilation fans, cooking tables and cooking equipment, and walls, floors and windows around the kitchen. It is preferable to use for etc.

  The cleaning composition for hard surface of the present invention may be used by any method as long as it is a known cleaning method, and can be preferably used when it is blended in the above-mentioned preferred blending ratio. Moreover, if it exists in the range of said preferable mixture ratio, you may dilute and use it with water. Examples of the method of use include, for example, a method of spraying the hard surface cleaning composition of the present invention on a hard surface to be cleaned with a spray and then scrubbing with a cloth or sponge, or a method of directly applying the hard surface of the present invention to a cloth or sponge. After the surface cleaning composition is soaked, the dirt is removed by a method such as rubbing the hard surface, and then the detergent and the removed dirt are washed away with water or wiped with a dry cloth or the like.

  Hereinafter, the present invention will be specifically described by way of examples. Three types of test methods including a cleaning test, an antifouling test, and a stability test and the test results are described below.

(Cleaning test)
A soybean plate (10 cm × 5 cm) was uniformly coated on one side so that soybean oil was 0.1 ± 0.01 g, and baked in an oven at 170 ° C. for 30 minutes. This stainless steel plate was completely immersed for 10 minutes at room temperature in a beaker containing the detergent samples described in Tables 1 to 3. The test piece after immersion was taken out from the beaker, washed lightly with running water and then dried, and the washing rate was calculated by the following formula from the change in weight before and after washing.
Cleaning rate (%) = {((stainless plate after applying and baking soybean oil) − (stained stainless plate after washing)) / actual mass of applied soybean oil} × 100

(Anti-fouling test)
Three types of test pieces (15cm x 15cm), each made of stainless steel plate, ceramic tile, and glass plate, each with a sponge fully impregnated with the detergent samples listed in Tables 1 to 3, and one side of the test piece Was washed by reciprocating 5 times, rinsed with running water for 30 seconds and dried. To the cleaned surface of the test piece after drying, 2 ml of soybean oil was uniformly applied with a spatula, then rinsed with running water for 30 seconds and dried. This process of “coating soybean oil → rinsing → drying” was performed twice in total, and the surface state of the test piece after completion was evaluated according to the following index. In the table, the antifouling test 1 is a stainless steel plate, the antifouling test 2 is a ceramic tile, and the antifouling test 3 is a glass plate.
A: No dirt is found.
B: Although the dirt is less than 10% of the area of the test piece, the dirt can be visually confirmed.
C: Dirt adheres to 10% to 50% of the area of the test piece.
D: More than 50% of the area of the test piece is adhered.

(Stability test)
Each composition shown in Table 1 and Table 2 was put in a sealed glass container, left in a constant temperature bath at 40 ° C. for 30 days, and the state after 30 days was visually evaluated according to the following index.
A: Same state as before the stability test (uniform state)
B: Solution is non-uniform C: Solution is completely separated

(Details of each component used for blending)
Nonionic (nonionic) surfactant 1: polyoxyethylene (3) lauryl ether nonionic surfactant 2: polyoxyethylene (5) lauryl ether nonionic surfactant 3: polyoxyethylene (7) lauryl ether nonionic Surfactant 4: Polyoxyethylene (9) lauryl ether nonionic surfactant 5: Polyoxyethylene (13) lauryl ether nonionic surfactant 6: Polyoxyethylene (18) lauryl ether nonionic surfactant 7: Polyoxyethylene (9) octyl ether

Amphoteric surfactant 1: Amidopropyl betaine laurate amphoteric surfactant 2: 2-coconut alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine amphoteric surfactant 3: Sodium laurylaminopropionate amphoteric surfactant 4: Lauryldimethylaminoacetic acid betaine amphoteric surfactant 5: Amidopropyl hydroxysulfobetaine lauric acid amphoteric surfactant 6: Lauryldimethylamine oxide amphoteric surfactant 7: Myristyldimethylamine oxide

Polymer 1: diallyldimethylammonium chloride / acrylic acid (70/30 (molar ratio)) polymer: weight average molecular weight 1200,000
Polymer 2: Diallyldimethylammonium chloride / maleic acid (60/40 (molar ratio)) polymer: weight average molecular weight 1700000
Polymer 3: diallylmonomethylamine / acrylic acid (70/30 (molar ratio)) polymer: weight average molecular weight 800,000
Polymer 4: Diallyldimethylammonium chloride polymer: Weight average molecular weight 40000
Alkaline agent 1: Sodium hydroxide

Alkaline agent 2: Monoethanolamine chelating agent 1: EDTA (ethylenediaminetetraacetic acid)
Cationic surfactant 1: Benzalkonium chloride organic solvent 1: Diethylene glycol monobutyl ether

Claims (6)

  (A) Amphoteric polymer containing acidic group and / or anionic group and cationic group and / or amino group, (B) carboxylic acid type amphoteric surfactant, (C) nonionic surfactant, (D) A hard surface cleaning composition comprising an alkali agent and (E) water and having a ratio of (A) / (B) = 1 / 0.2 to 1/100 (mass ratio).   2. The hard surface cleaning composition according to claim 1, wherein the component (B) is an amidopropyl betaine type or amino acid type amphoteric surfactant.   The said hard surface is a hard surface of a kitchen, The cleaning composition for hard surfaces of Claim 1 or 2 characterized by the above-mentioned. The hard surface cleaning composition according to any one of claims 1 to 3, wherein the component (C) is a nonionic surfactant represented by the following general formula (1).
_{R- (OC 2 H 4) n} -OH (1)
(In the formula, R represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n represents a number of 1 to 15) The component (A) contains a monomer (a-1) containing an acidic group and / or an anionic group represented by the following general formula (2), and a cationic group represented by the general formula (3) The monomer (a-2) or the monomer (a-3) containing the amino group represented by the general formula (4) is converted into (a-1) / (a-2) = 50/50 to 5/95 ( (Molar ratio) or (a-1) / (a-3) = 50/50 to 5/95 (molar ratio). The cleaning composition for hard surfaces according to one item.

(In the formula, R ^{1 to} R ⁴ are each independently represented by —COOH, —SO ₃ H, —PO ₃ H ₂ , —CO—A—SO ₃ H, —CO—A′—PO ₃ H _2. Or an anionic group comprising an ammonium salt or an alkali metal salt thereof, a hydrogen atom, or a group selected from a hydrocarbon group having 1 to 6 carbon atoms, and A and A ′ each have 1 carbon atom. Represents an alkylene group of ˜3, provided that any one or more of R ^{1 to} R ⁴ must be an acidic group or an anionic group.)

(In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁸ represents an alkylene group having 1 to ⁸ carbon atoms, —COOR ¹² —, —CONHR ¹³ —, —OCOR. ¹⁴ and any one group selected from —R ¹⁵ OCOR ¹⁶ —, R ^{12 to} R ¹⁶ each independently represents an alkylene group having 1 to 6 carbon atoms, and R ⁹ , R ¹⁰ and R ¹¹ are Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R ⁷ represents an alkyl group having 1 to 3 carbon atoms or —R ⁸ —C (R ⁹ ) ═CR ¹⁰ R ¹¹ , and X ⁻ represents Represents an anionic group.)

(In the formula, R ¹⁷ represents an alkyl group having 1 to 3 carbon atoms, R ¹⁹ represents an alkylene group having 1 to 8 carbon atoms, —COOR ²³ —, —CONHR ²⁴ —, —OCOR ²⁵ , and —R ²⁶ OCOR. ²⁷ represents any group selected from-, R ^{23 to} R ²⁷ each independently represents an alkylene group having 1 to 6 carbon atoms, R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, The alkyl group having 1 to 3 carbon atoms is represented, and R ¹⁸ represents an alkyl group having 1 to 3 carbon atoms or —R ¹⁹ —C (R ²⁰ ) ═CR ²¹ R ²² .   The component (A) is 0.01 to 5% by mass, the component (B) is 0.01 to 10% by mass, the component (C) is 0.1 to 15% by mass, and the component (D) is 0.1 to 20% by mass. The hard surface cleaning composition according to any one of claims 1 to 5, wherein the hard surface cleaning composition is contained.