JP5281420B2 - Liquid detergent composition for hard surfaces - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for a hard surface, which has excellent detergency against oil stain etc., and exhibits excellent germicidal effect. <P>SOLUTION: The liquid detergent composition for a hard surface comprises (a) 0.01-5 mass% of one or more selected from a nonionic surfactant and an amphoteric surfactant, (b) a germicidal cationic surfactant of a quaternary ammonium salt type containing one or two 6-16C hydrocarbon groups, (c) a polymer compound obtained by graft polymerizing a monoethylenically unsaturated monomer consisting essentially of acrylic acid and/or methacrylic acid onto a backbone chain of a polyether compound represented by general formula (c1): Y-O(CH<SB>2</SB>CH<SB>2</SB>O)<SB>n</SB>H (wherein Y is a hydrogen atom, methyl, phenyl or benzyl; and n is an average addition molar number and a number of 2-200) and water. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a liquid cleaning composition for hard surfaces.

  In general, cleaning agents for hard surfaces have compositions suitable for each of them in order to remove different stains to be treated, such as bathrooms, kitchens and floors. For example, kitchen cleaners used around kitchens such as ovens, ovens, walls and floors around the range, and exhaust fans are used to remove oil stains that have been altered by the action of heat, sunlight, oxygen in the air, etc. A cleaning agent containing an activator, a solvent, an alkali agent and the like is used. Also, as bathroom cleaners used in bathrooms such as bathtubs, bathroom walls and floors, metal soaps, especially detergents containing detergents, metal ion sequestering agents, etc., are used to remove dirt from fatty acid calcium salts. The agent is used.

  Further, due to the recent increase in hygiene awareness and cleanliness, the sterilization action by using a cleaning agent is strongly desired. Although the cleaning agent originally has the effect of physically washing and removing the bacteria, there is a limit to removing the bacteria attached to the uneven surface such as fine scratches on the surface only with physical force. Therefore, it is preferable to add a disinfectant to the cleaning agent. In this case, the most effective compound as a disinfectant is a cationic surfactant. Cationic surfactants are widely used in the hygiene field and the like because of their broad antibacterial spectrum and rapid action. However, when the cationic surfactant is used in combination with a surfactant other than the cationic surfactant, which is a cleaning component, various disadvantages occur. For example, when combined with an anionic surfactant, the bactericidal efficacy of the cationic surfactant is deactivated. For this reason, many nonionic surfactants must be used as a co-surfactant, which changes the foam quality. On the other hand, in combination with a nonionic surfactant or an amphoteric surfactant, the bactericidal efficacy of the cationic surfactant is often retained, but the foaming power is impaired by the influence of the cationic surfactant. Therefore, in order to compensate for this, the total amount of the surfactant is increased, which not only causes economic inconvenience but also results in a decrease in the bactericidal efficacy of the composition.

  On the other hand, a technique of blending an anionic polymer into a hard surface cleaning composition is also known. Patent Document 1 discloses a composition containing a nonionic surfactant and a water-soluble anionic polymer. Patent Document 1 states that polymers derived from polyacrylic acid, polymethacrylic acid, polymaleic anhydride, and copolymers thereof have a good influence on the cleaning performance of nonionic surfactants. According to the description in Patent Document 1, by adding a certain polymer to a general alkaline hard surface cleaning composition, the first cleaning effect when the composition is first used on the surface, or the improvement of the surface. It is known to be able to obtain one of the second cleaning effects that facilitates repeated cleaning if the soiling is prevented or cannot be prevented. Patent Document 2 discloses a composition containing a nonionic surfactant, a water-soluble anionic polymer, and a cationic surfactant. In Patent Document 2, it is said that the presence of a cationic surfactant can increase the pH of a nonionic surfactant and a polymer-containing product without losing the benefits of the polymer (Patent Document 2-5). Page 19-21).

JP-T 8-510276 JP 2001-514663 A

  As described in the above-mentioned patent documents, common polymers such as polymers derived from acrylic acid, methacrylic acid, maleic anhydride and copolymers thereof, and copolymers of the above carboxylic acid monomers with ethylene, styrene, and methyl vinyl ether. When carboxylic acid is used in combination with a bactericidal cationic surfactant and a nonionic surfactant, the effect of preventing re-adhesion and easy cleaning can be exhibited. However, the sterilization performance is insufficient in the above composition, and particularly when the amount of the polymer is more than a certain amount with respect to the amount of the cationic surfactant, the sterilization when the concentration of the cationic surfactant is low. Performance will be lower than without the polymer.

  It is an object of the present invention to provide a liquid detergent composition for hard surfaces having antifouling prevention property and easy washing property and having excellent bactericidal performance even when the cationic surfactant concentration is low. And

  As a result of intensive studies by the present inventors on the above-mentioned problems, a specific structure obtained by graft polymerization of an unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid with a specific polyether compound as a backbone chain It was found that by using this polymer compound, an excellent bactericidal effect was exhibited even when the concentration of the cationic surfactant having bactericidal properties was low.

The present invention comprises (a) one or more surfactants selected from nonionic surfactants and amphoteric surfactants (hereinafter referred to as component (a)) 0.01 to 5% by mass, (b) carbon number 6 Quaternary ammonium salt type cationic surfactant having 1 or 2 hydrocarbon groups of ˜16 (hereinafter referred to as component (b)) 0.001 to 2% by mass, (c) the following general A polymer compound obtained by graft polymerization of a monoethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid to the backbone of the polyether compound represented by the formula (c1) [hereinafter referred to as component (c) ], And a liquid detergent composition for hard surfaces containing water.
_{Y-O (CH 2 CH 2} O) n H (c1)
(In the formula, Y is a hydrogen atom, methyl group, phenyl group or benzyl group, n is the average number of moles added, and is a number from 2 to 200.)

  Moreover, this invention consists of the liquid cleaning composition for hard surfaces of the said invention, or the sterilization washing | cleaning liquid with the density | concentration of 0.0001-0.01 mass% (b) prepared from this composition on a hard surface. The present invention relates to a method for sterilizing and cleaning hard surfaces to be applied.

  The liquid detergent composition for hard surfaces of the present invention not only has a high bactericidal effect, but also has an excellent detergency. Even when the liquid detergent composition for hard surfaces of the present invention is used in a state where the concentration of the cationic surfactant is low, the cleaning performance is good, and the bactericidal performance is higher than when a conventional anionic polymer is used. Will also improve dramatically. Although the liquid detergent composition for hard surfaces of this invention can be applied to various hard surfaces, since it is especially suitable for the hard surface around a kitchen, it is suitable as a liquid detergent composition for kitchens.

  The liquid detergent composition for hard surface of this invention contains 1 or more types of surfactant chosen from a nonionic surfactant and an amphoteric surfactant as (a) component.

  Although it does not specifically limit as nonionic surfactant, Polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl or alkenyl ether, polyoxybutylene alkyl or alkenyl ether, alkylene oxide addition alkyl group or alkenyl One or more selected from a group-containing nonionic surfactant mixture, sucrose fatty acid ester, aliphatic alkanolamide, fatty acid glycerin monoester, amine oxide, ethylene oxide condensed surfactant and alkyl (poly) glycoside Is preferred. Specific examples of such nonionic surfactants include the following (1) to (11).

(1) Polyoxyethylene alkyl or alkenyl ether, wherein the average carbon number of the alkyl group or alkenyl group is 10 to 20, and the average number of added moles of ethylene oxide (hereinafter referred to as EO) is 1 to 30 mol. some stuff.

(2) Polyoxyethylene alkylphenyl ether, wherein the alkyl group has an average carbon number of 6 to 12 and the average number of moles of ethylene oxide added is 1 to 25 mol.

(3) Polyoxypropylene alkyl or alkenyl ether, wherein the alkyl group or alkenyl group has an average carbon number of 10 to 20, and the number of added moles of propylene oxide (hereinafter referred to as PO) is 1 to 20 mol on average. some stuff.

(4) Polyoxybutylene alkyl or alkenyl ether, wherein the alkyl group or alkenyl group has an average carbon number of 10 to 20, and the number of moles of butylene oxide added is 1 to 20 mol on average.

(5) having an alkyl group or an alkenyl group, ethylene oxide and propylene oxide (EO / PO molar ratio: 0.1 / 9.9 to 9.9 / 0.1) or ethylene oxide and butylene oxide (EO / PO) (Molar ratio: 0.1 / 9.9 to 9.9 / 0.1) is added, and the average carbon number of the alkyl group or alkenyl group is 10 to 20, The average number of moles of alkylene oxide added per molecule is 1 to 30 moles.

(6) A higher fatty acid alkanolamide represented by the following general formula (a1-1) or an alkylene oxide adduct thereof.

(In the formula, R ^1a represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ^2a and R ^3a represent the same or different hydrogen atoms or CH ₃ , p represents a number of 1 to 3, q represents 0 to 0, Indicates the number of 3.)

(7) Sucrose fatty acid ester whose fatty acid part has an average carbon number of 10-20.

(8) Fatty acid glycerin monoester, wherein the fatty acid moiety has an average carbon number of 10-20.

(9) Amine oxide. For example, the alkyl or alkenylamine oxide which has a C1-C24 linear or branched alkyl group or alkenyl group can be mentioned. More preferable amine oxides include alkylamine oxides represented by the following general formula (a1-2).

(Wherein R ^4a represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, R ^5a and R ^6a represent the same or different alkyl groups having 1 to 3 carbon atoms, and D represents —NHC (═O) —. A group or —C (═O) NH— group, E represents an alkylene group having 1 to 5 carbon atoms, and m and n represent m = 0 and n = 0 or m = 1 and n = 1.)
In the general formula (a1-2), R ^4a is an alkyl group or alkenyl group having 8 to 24 carbon atoms, preferably an alkyl group having 12 to 18 carbon atoms, and more preferably an alkyl group having 12 to 14 carbon atoms. Further, an alkyl group having 12 carbon atoms is more preferable. R ^5a and R ^6a are each an alkyl group having 1 to 3 carbon atoms, and a methyl group having 1 carbon atom is particularly preferable.

(10) A nonionic surfactant having a trade name of “Pluronic” (Asahi Denka Co., Ltd.) obtained by condensing ethylene oxide and propylene oxide.

(11) Alkyl (poly) glycoside. For example, alkyl (poly) glycoside represented by the following general formula (a1-3).
R ^7a (OR ^8a ) _x G _y (a1-3)
(Wherein R ^7a represents a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group, R ^8a represents an alkylene group having 2 to 4 carbon atoms, and G represents carbon. (The residue derived from the reducing sugar which has number 5-6 is shown, x (average value) shows 0-5, y (average value) shows 1-5.)

  The average value of x in the formula is 0 to 5, but the water solubility and crystallinity of the cleaning composition can be adjusted by changing this value. That is, the larger the value of x, the higher the water solubility and the lower the crystallinity. The value of x is preferably 0 to 2, particularly preferably 0.

  In the formula, when y is an average value larger than 1, that is, when a sugar chain of two or more sugars is used as a hydrophilic group, the binding mode of the sugar chain is 1-2, 1-3, 1-4, 1- It is possible to include any mixture having six bonds, as well as α-, β-pyranoside bonds or furanoside bonds and mixed modes of these. Moreover, the average value of y in general formula (a1-3) is 1-5, Preferably it is 1-1.5, More preferably, it is 1.1-1.4. In addition, the measured value of y is based on the proton NMR method.

R ^7a in the formula is preferably an alkyl group having 10 to 14 carbon atoms from the viewpoint of solubility and detergency. R ^8a is preferably an alkylene group having 2 to 3 carbon atoms from the viewpoint of water solubility.

  The structure of G in the formula is determined by the raw material of monosaccharide or disaccharide or more, but as the raw material of G, in the case of monosaccharide, glucose, fructose, galactose, xylose, mannose, lyxose, arabinose and a mixture thereof, etc. Examples of the disaccharide or more include maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, tulanose, raffinose, gentianose, merezitose, and a mixture thereof. Among these, preferable raw materials are glucose and fructose for monosaccharides and maltose and sucrose for disaccharides or more from the viewpoint of availability and cost. Among these, glucose is particularly preferable from the viewpoint of easy availability.

  Furthermore, the following general formula (a1-4)

(In the formula, R ^9a represents an alkyl group or alkenyl group having 6 to 24 carbon atoms.)

1 mol adduct of pentaerythritol and isostearyl glycidyl ether, 1 mol adduct of sorbitol and isostearyl glycidyl ether, 1 mol adduct of mannitol and 2-octyldodecyl glycidyl ether, methyl glucoside 1 mol adduct of isostearyl glycidyl ether, 1 mol adduct of diglycerinisostearyl glycidyl ether, phytantriol, etc., and at least 1 long-chain branched alkyl group or alkenyl group and at least 3 Nonionic surfactants having a hydroxyl group can be mentioned.

  Among these nonionic surfactants, nonionic surfactants selected from amine oxides and alkyl (poly) glycosides are preferable, and amine oxides are more preferable.

  Although it does not specifically limit as an amphoteric surfactant, In this invention, it selects from the betaine represented by the following general formula (a2-1), (a2-2), (a2-3) and (a2-4). 1 type or 2 or more types can be mentioned.

(In the formula, R ^10a represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ^11a and R ^12a are the same or different and may be substituted with a hydroxyl group. R ^13a represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, Y represents a hydrogen atom or a hydroxyl group, and r, s, and t each represent a number of 1 to 3. U represents a number of 1 to 5, v represents a number of 1 or more, and w and x represent numbers satisfying 0 ≦ w + x ≦ 4.)

In general formula (a2-1), R ^10a is preferably a saturated alkyl group having 8 to 18 carbon atoms in terms of detergency, and particularly preferably a saturated alkyl group having 10 to 16 carbon atoms. For the same reason, R ^11a and R ^12a are each preferably a methyl group, an ethyl group or a hydroxyethyl group, and r is preferably 1.

In general formula (a2-2), R ^10a is preferably a saturated alkyl group having 8 to 18 carbon atoms in terms of detergency, and particularly preferably a saturated alkyl group having 10 to 16 carbon atoms. For the same reason, R ^11a and R ^12a are each preferably a methyl group, an ethyl group or a hydroxyethyl group, s is preferably 1, and t is preferably 1.

In general formulas (a2-3) and (a2-4), R ^13a is preferably a saturated alkyl group having 9 to 15 carbon atoms in terms of detergency. For the same reason, R ^11a and R ^12a are each preferably a methyl group, an ethyl group or a hydroxyethyl group, u is preferably 2 or 3, v is preferably 1, w is preferably 1, and x is preferably 1. Specific examples thereof include alkylamidopropyl-N, N-dimethylacetic acid betaine, alkylamidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, alkylamidopropyl-N, N-dimethyl-propylsulfobetaine, and the like. Can be mentioned. Among these, in terms of detergency and foaming power, lauric acid amidopropyl-N, N-dimethylacetic acid betaine, myristic acid amidopropyl-N, N-dimethylacetic acid betaine, cocamidoamidopropyl-N, N-dimethyl Preferred are betaine acetate, lauryl hydroxysulfo betaine, amidopropyl laurate-N, N-dimethyl-2-hydroxypropyl betaine, and the like.

  (A) As a component, a nonionic surfactant is preferable among the above-mentioned thing from the point of detergency. Moreover, it is preferable that an amine oxide is included as (a) component, and it is preferable that the ratio of an amine oxide is 95-20 mass% in (a) component, and also it is 90-50 mass%. For example, if an amine oxide is used in excess and an alkyl (poly) glycoside is used in combination, a sufficient effect can be obtained even if the total amount of the component (a) is reduced. When amine oxide and alkyl (poly) glycoside are used in combination, the mass ratio of amine oxide / alkyl (poly) glycoside is preferably 95/5 to 20/80, more preferably 95/5 to 50/50. The content of the component (a) is 0.01 to 5 in the hard surface liquid detergent composition of the present invention, considering sufficient detergency and considering easy removal of the cleaning component by rinsing after use. % By mass, preferably 0.1 to 5% by mass, particularly preferably 0.2 to 5% by mass.

  The liquid detergent composition for hard surfaces of the present invention is a quaternary having one or two hydrocarbon groups having 6 to 16 carbon atoms (for example, alkyl group, alkenyl group, hydroxyalkyl group) as component (b). A cationic surfactant having an antibacterial property of ammonium salt type is contained.

  Examples of the component (b) include a cationic surfactant selected from a compound represented by the following general formula (b1) and a compound represented by the general formula (b2), and an alkylpyridinium salt. A cationic surfactant selected from the compound represented by the formula (1) and the compound represented by the general formula (2) is preferable.

Wherein R ^1b and R ^2b are the same or different and each represents a long chain alkyl group, a long chain alkenyl group or a long chain hydroxyalkyl group having 8 to 16 carbon atoms and 16 to 26 carbon atoms in total, R ^3b and R ^4b is the same or different and represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less, and Z ⁻ represents a halogen atom or a sulfonic acid having 1 to 5 carbon atoms. Indicates an anion residue of ester or sulfate.)

(Wherein R ^5b is a hydrocarbon group having 8 to 16 carbon atoms or

In indicates a group represented by, Z ^- is as defined above. )

  (B) Content of a component is 0.001-2 mass% in the liquid cleaning composition for hard surfaces of this invention, 0.001-1.5 mass%, Furthermore, 0.01-1 mass% is preferable.

  Moreover, in this invention, mass ratio of (a) component and (b) component is 0.1-500 in (a) component / (b) component from a viewpoint of detergency, Furthermore, 1-100, Furthermore 1- 50 and even more preferably 5-50.

The liquid detergent composition for hard surfaces of the present invention is a monoethylene mainly composed of acrylic acid and / or methacrylic acid in the backbone of the polyether compound represented by the following general formula (c1) as component (c). A high molecular compound obtained by graft polymerization of a polymerizable unsaturated monomer.
_{Y-O (CH 2 CH 2} O) n H (c1)
(In the formula, Y is a hydrogen atom, methyl group, phenyl group or benzyl group, n is the average number of moles added, and is a number from 2 to 200.)

  In general formula (c1), Y is preferably a phenyl group, and n is preferably 5 to 100, more preferably 10 to 50, from the viewpoint of achieving the effects of the present invention.

  The component (c) is obtained by adding other unsaturated carboxylic acids to those in which acrylic acid and / or methacrylic acid are essential, and graft polymerization to the polyether compound of the general formula (c1). That is, (c) component contains acrylic acid and / or methacrylic acid as a monoethylenically unsaturated monomer. Examples of monoethylenically unsaturated monomers that can be used in addition to acrylic acid and / or methacrylic acid include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, and maleic anhydride. A known radical initiator can be used as the polymerization initiator. As the component (c), a mass ratio (monoethylenic unsaturated monomer) containing a monoethylenically unsaturated monomer containing acrylic acid and / or methacrylic acid to the polyether compound of the general formula (c1) which is a backbone is used. (Mass ratio of saturated monomer / polyether compound) is preferably obtained by reacting at a ratio of at least 1/4, and the upper limit is not particularly limited, but is preferably 4/4 or less, more preferably 3 / 4 or less. As a specific method for producing the component (c), a monoethylenically unsaturated monomer is used while stirring the polyether compound of the general formula (c1) at 90 ° C. or higher, preferably 100 to 200 ° C. under a nitrogen stream. The acid type (c) component of the present invention can be obtained by dropping the body and the initiator separately and slowly. In the case of making a salt, it can be easily obtained by neutralizing with an alkali agent such as sodium hydroxide after cooling. Also, like an anionic surfactant, it is added to the composition as it is in the acid form. You may neutralize in.

  The weight average molecular weight of the polymer compound as the component (c) is preferably 2,000 to 200,000, more preferably 5,000 to 100,000, from the viewpoint of achieving the effects of the present invention. More preferably, it is 8,000-50,000. This weight average molecular weight is measured by a gel permeation chromatography method (hereinafter referred to as “GPC”).

  (C) 0.01-10 mass% is preferable in the liquid detergent composition for hard surfaces of this invention, as for content of a component, Furthermore, 0.02-8 mass%, Furthermore, 0.05-5 mass% is further. preferable.

  In the present invention, the mass ratio of the component (b) and the component (c) is 0.01 to 10 and preferably 0.02 to (b) component / (c) component from the viewpoint of detergency and bactericidal efficacy. 2, more preferably in the range of 0.02 to 0.5.

  The liquid detergent composition for hard surfaces of the present invention has a particularly remarkable effect of achieving both detergency and bactericidal efficacy. The reason why such a remarkable effect is manifested is not clear, but is thought to be based on the following mechanism. The component (a) and the component (b) are considered to form mixed micelles, but the strength of the ionic repulsion of the hydrophilic group portion in the component (b) and the benzyl group bonded to nitrogen of the hydrophilic group portion It is considered that the micelle structure tends to become sparse due to the size of steric hindrance due to the lower alkyl group, which is thought to bring about a decrease in detergency. However, when the component (c) which is a polyanion is added, the ionic repulsion between the components (b) is weakened, so that the micelle structure becomes dense, the emulsification dispersibility increases, and the detergency is improved. Conceivable. Here, the component (c) is different in structure from general polyacrylic acid or acrylic acid-maleic acid copolymer, and has a polyether compound backbone. The presence of this backbone chain allows the interaction between the carboxylic acid moiety of component (c) and the cationic moiety of component (b) to be maintained moderately without becoming too strong. It can be maintained.

  In addition, since the component (c) is a kind of polycarboxylic acid, it has the effect of preventing re-adhesion and easy cleaning as described in the above-mentioned prior art regarding general polyacrylic acid and the like. It is thought to be possible. The component (c) contributes to the improvement of the detergency as expected, but the effect gives a more favorable result as compared with general polyacrylic acid or the like. The reason for this is not clear, but the backbone of component (c) interacts with surfactant micelles (mixed micelles of component (a) and component (b)), making it effective against hard surfaces and dirt. (A) component, (b) component surfactant and (c) component may be collected.

  The liquid detergent composition for hard surfaces of the present invention can contain alkanolamine as the component (d). Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine, and monoethanolamine is preferable from the viewpoint of detergency.

  The content of the component (d) is preferably 0.01 to 30% by mass, more preferably 0.05 to 30% by mass in the hard surface liquid detergent composition of the present invention in order to impart sufficient detergency. %, More preferably 0.1 to 20% by mass, most preferably 0.3 to 10% by mass.

  In the liquid detergent composition for hard surface of the present invention, a surfactant other than the component (a) can be blended as the component (e). As the component (e), one or more compounds listed as “component (b)” in JP-A No. 11-189796 are used which do not correspond to the component (a) of the present invention. Can do. However, in the liquid detergent composition for hard surfaces of the present invention, the content of an anionic surfactant having 8 or more carbon atoms is 1% by mass or less, and further 0.5% by mass from the viewpoint of bactericidal efficacy and cleaning performance. The following is preferable. In addition, the total amount of (a) component and (e) component is 0.1-5 mass% in the liquid cleaning composition for hard surfaces of this invention, Furthermore, 0.2-3 mass% is preferable. The total amount does not include the amount of component (b).

  In the liquid detergent composition for hard surface of the present invention, a builder component can be blended as the component (f). As a builder component, the following 1 type (s) or 2 or more types can be used.

  (1) Alkali metal salts or alkanolamine salts of phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and phytic acid.

  (2) Ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid Alkali metal salts or alkanolamine salts of phosphonic acids such as ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid.

  (3) Alkali metal salts or alkanolamine salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid.

  (4) Alkali metal salts or alkanolamine salts of amino acids such as aspartic acid, glutamic acid and glycine.

  (5) of aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid Alkali metal salt or alkanolamine salt.

  (6) Alkali metals of organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid Salt or alkanolamine salt.

  (7) An alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A.

  (8) Aminopoly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt, polyethylenepolyaminepoly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt.

  Among these, hydroxycarboxylic acids such as citric acid and malic acid, condensed phosphoric acids such as pyrophosphoric acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid and hydroxyethylethylenediaminetriacetic acid, or salts thereof are preferable. The salt form is preferably a sodium salt, potassium salt, ammonium salt or alkanolamine salt.

  The content of the component (f) in the composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.2 to 1% by mass from the viewpoint of detergency. It is.

  In addition to the above components, the liquid detergent composition for hard surface of the present invention may contain other components in a range that does not impair the object of the present invention. For example, ethanol, propanol, glycerin, ethylene glycol, propylene glycol, propylene glycol methyl ether, diethylene glycol butyl ether, alkyl monoglyceryl ether having 3 to 8 carbon atoms in the alkyl group, polyoxyethylene (n = 1 to 5) phenyl ether ( Or a solvent such as benzyl ether), an antioxidant such as BHT, a fungicide / antibacterial agent, and a preservative. In the liquid detergent composition for hard surfaces of the present invention, polyacrylic acid and its salt, a copolymer of olefin and maleic anhydride and its salt as other optional components, paragraph 0035 of JP-A-7-292398. A dispersant for organic pigments such as carboxylic acid polymers and sulfonic acid polymers described in ˜0038 can be blended.

  In the hard surface liquid detergent composition of the present invention, water is blended together with the above components. The blending amount of water is an amount adjusted to be 100% by mass in total. That is, the balance of the composition is water. Further, the pH at 25 ° C. of the liquid detergent composition for hard surface of the present invention is preferably pH 8 or more, more preferably pH 10 or more, and preferably pH 14 or less, in order to obtain high detergency. The pH is preferably 13 or less. The pH is measured using a pH meter D-52S and a pH electrode 6367-10D manufactured by Horiba, Ltd.

  The liquid detergent composition for hard surfaces of the present invention can be used as a container-containing detergent filled in a container. It is preferable to fill a transparent or translucent container from an aesthetic point of view. A container may be manufactured from 1 or more types chosen from polyethylene, a polyethylene terephthalate, and a polypropylene, for example. In the present invention, the term “transparent or translucent” means that the light transmittance at 660 nm is 10% or more. In the present invention, from the viewpoint of emphasizing the transparency of the container, the light transmittance is 30% or more. The container of 60% or more is more preferable. The light transmittance can be determined from the light transmittance at a wavelength of 660 nm using a UV-2500PC type measuring instrument manufactured by Shimadzu Corporation. The transparent or translucent container should just be a transparent or semi-transparent container part of a liquid cleaning composition, and another part may consist of a member which is not transparent or translucent.

  The present invention relates to a liquid detergent composition for a hard surface. Here, the “hard surface” maintains a certain shape regardless of whether it is planar or three-dimensional. The degree of hardness is not limited as long as it can be washed. This hard surface includes fixed objects such as floors, stairs and walls made of plastic, rubber, metal, tile, brick, concrete, cement, glass, wood, etc., as well as various instruments, instruments, tools, furniture, List all things that people touch, such as tableware.

  Therefore, the liquid detergent composition for hard surfaces of the present invention includes a detergent for kitchens, a detergent for bathrooms, a detergent for floors, a detergent for dishes, a detergent for fully automatic washing machine washing tubs, and a washing for drain pipes. Although it can be applied as a cleaning agent for small items in kitchens and bathrooms, it can be particularly preferably applied as a cleaning agent for kitchens.

  The liquid detergent composition for hard surfaces of the present invention can obtain an excellent bactericidal effect even when the concentration of the component (b) is low, for example, 0.0001 to 0.01% by mass. The composition in which the content of the component (b) is in this range can be used as it is, and the composition in which the content of the component (b) is larger than this range can be diluted with water. Therefore, according to the present invention, a sterilizing cleaning liquid comprising the liquid cleaning composition for hard surface of the present invention or having the concentration (b) prepared from the composition of 0.0001 to 0.01% by mass is applied to the hard surface. A method for sterilizing and cleaning a hard surface is provided.

Examples 1-5, Comparative Examples 1-3
Using each component shown in Table 1, liquid detergent compositions for hard surfaces of Examples and Comparative Examples were obtained. pH (25 degreeC) was adjusted with 6N-sodium hydroxide aqueous solution or 6N-hydrochloric acid as needed. Each test of cleaning performance and bactericidal efficacy was performed by using the liquid cleaning composition for each hard surface according to the following method. The results are shown in Table 1.

(Cleaning performance)
The composition was diluted with ion-exchanged water so that the concentration of the component (b) was 0.001% by mass, and the cleaning performance was evaluated. A model contamination board was prepared by applying 0.01 g of rapeseed oil as uniformly as possible to a polypropylene board (70 mm × 20 mm). About 0.5 g of the diluted liquid detergent composition was dropped onto a model contamination plate fixed horizontally, and the washing liquid was thoroughly blended with absorbent cotton, and then rinsed with running water. This operation was performed on 10 model-contaminated plates, and evaluation was performed according to the following criteria based on the number of plates that felt a feeling of being null on the surface due to residual oil.
4: No more than 2 boards with a feeling of null 3: 3-4 boards with a feeling of null 2: 5-6 boards with a feeling of null 1: More than 7 boards with a feeling of null

(Bactericidal efficacy)
(B) The composition was diluted with ion-exchanged water so that the concentration of the component was 0.001% by mass, and the bactericidal efficacy against Escherichia coli and Staphylococcus aureus was examined. As a specific method, the test was conducted in accordance with the “Detergent activity test method for residential detergents and soap (revised on July 31, 2007)” established by the Japan Soap and Detergent Association, a detergent and soap fair trade council. The following criteria were established and evaluated according to the value of the sterilization activity.
4: Disinfection activity 3.0 or more 3: Disinfection activity 2.5 or more and less than 3.0 2: Disinfection activity 2.0 or more and less than 2.5 1: Disinfection activity less than 2.0

* 1 Anhitoal 20N, Kao Corporation * 2 Mydoll 12, Kao Corporation * 3 Anhitoal 20AB, Kao Corporation * 4 Sanisole C, Kao Corporation * 5 Kotamin D10E, Kao Corporation * 6 The following synthesis Polymer compound synthesized by the method of Example <Synthesis Example>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 100 parts by mass of phenoxypolyethylene glycol having an average molecular weight of 1500 and 5 parts by mass of maleic acid, and heated to dissolve under a nitrogen stream. The temperature was raised to 150 ° C. with stirring. Next, while maintaining the temperature at 150 to 151 ° C., 30 parts by mass of acrylic acid and 4.5 parts by mass of di-t-butyl peroxide are separately dropped continuously over 1 hour, and then the stirring is continued for 40 minutes. It was. After cooling, 135 parts by mass of pure water was added to obtain polymer compound 1.
* 7 Aqualic DL-100, manufactured by Nippon Shokubai Co., Ltd. (average molecular weight 5000)
* 8 A 6N-sodium hydroxide aqueous solution or 6N-hydrochloric acid, and an appropriate amount is an amount for achieving pH in the table.

Claims (6)

(A) 0.01 to 5% by mass of one or more surfactants selected from nonionic surfactants and amphoteric surfactants, and (b) one or two hydrocarbon groups having 6 to 16 carbon atoms. 0.001 to 2% by mass of a quaternary ammonium salt-type bactericidal cationic surfactant, (c) Acrylic acid and / or methacrylic acid in the backbone of the polyether compound represented by the following general formula (c1) A liquid detergent composition for hard surfaces, comprising a polymer compound obtained by graft polymerization of a monoethylenically unsaturated monomer mainly composed of an acid and water.
_{Y-O (CH 2 CH 2} O) n H (c1)
(In the formula, Y is a hydrogen atom, methyl group, phenyl group or benzyl group, n is the average number of moles added, and is a number from 2 to 200.)   The liquid detergent composition for hard surfaces according to claim 1, wherein (a) is at least one selected from amine oxides and alkyl (poly) glycosides. The liquid for hard surfaces according to claim 1 or 2, wherein (b) is a cationic surfactant selected from a compound represented by the following general formula (b1) and a compound represented by the general formula (b2). Cleaning composition.

Wherein R ^1b and R ^2b are the same or different and each represents a long chain alkyl group, a long chain alkenyl group or a long chain hydroxyalkyl group having 8 to 16 carbon atoms and 16 to 26 carbon atoms in total, R ^3b and R ^4b is the same or different and represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less, and Z ⁻ represents a halogen atom or a sulfonic acid having 1 to 5 carbon atoms. Indicates an anion residue of ester or sulfate.)

(Wherein R ^5b is a hydrocarbon group having 8 to 16 carbon atoms or

In indicates a group represented by, Z ^- is as defined above. )   The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein a mass ratio of (a) / (b) is 0.1 to 500.   The liquid detergent composition for hard surfaces according to any one of claims 1 to 4, wherein a mass ratio of (b) / (c) is 0.01 to 5.   A hard bactericidal cleaning solution having a concentration of 0.0001 to 0.01% by mass comprising the liquid detergent composition for hard surface according to any one of claims 1 to 5 and the concentration of (b) prepared from the composition is hard. A method for sterilizing and cleaning hard surfaces applied to surfaces.