JP2010168429A - Liquid detergent composition for hard surface - 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 exceedingly excellent appearance stability even if prepared by using water containing hardness components. <P>SOLUTION: The liquid detergent composition for a hard surface comprises (a) one or more surfactants selected from a nonionic surfactant and an amphoteric surfactant, (b) a copper phthalocyanine-based pigment, (c) a polymer compound obtained by graft polymerizing a monoethylenic unsaturated monomer consisting essentially of acrylic acid and/or methacrylic acid onto a backbone chain of a specific polyether compound, (d) an alkanolamine 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.

  In addition, for the purpose of improving palatability, the appearance of the cleaning agent may be colored in various liquid colors. At this time, various dyes can be used, but a copper phthalocyanine dye may be used as a dye having high hue stability during storage and giving a vivid hue. For example, in Patent Document 1, a cleaning agent that swells stubborn dirt such as denatured fat and oil stains and can be removed safely, and is easy to use by coloring the liquid, and has excellent storage stability of the dye. Disclosed is a liquid detergent composition in which a water-soluble polymer and a specific phthalocyanine pigment are added at a specific weight ratio to a specific surfactant, a specific solvent, and an alkaline agent-based composition in order to provide an agent composition. is doing.

JP 7-292398 A

  However, in the case of producing a colored composition using a water-soluble polymer specifically described in the text of Patent Document 1, when prepared with water containing calcium ions and magnesium ions as hardness components In particular, when stored at high temperatures, precipitation of pigments and the like may occur, and even when blended with ion-exchanged water or distilled water, it was diluted 2 to 50 times with water containing the above hardness components. When the liquid was stored at a particularly high temperature, precipitation sometimes occurred. In particular, in the cleaning of commercial facilities, from the viewpoint of workability, a large amount of diluted cleaning solution is prepared at a time, and cleaning is performed using small amounts as necessary. When the above-described precipitation occurs in the case of storage, it is necessary to prepare a diluted washing solution again.

  The present invention is a colored hard surface cleaning agent that has excellent detergency against oil stains and the like, and is manufactured with water containing a hardness component or diluted with water containing a hardness component. Therefore, it is an object of the present invention to provide a hard surface liquid detergent composition that does not produce precipitates of pigments or the like even when stored at a high temperature, and has excellent appearance stability.

The present invention includes (a) one or more surfactants selected from nonionic surfactants and amphoteric surfactants (hereinafter referred to as component (a)), (b) copper phthalocyanine dyes (hereinafter referred to as (b) Component)], (c) a polymer obtained by graft polymerization of a monoethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid on the backbone of a polyether compound represented by the following general formula (c1) The present invention relates to a hard surface liquid detergent composition containing a compound (hereinafter referred to as component (c)) 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 of the present invention has excellent detergency against oil stains and the like, and has excellent appearance stability that does not cause precipitation due to the influence of hardness components. That is, the liquid detergent composition for hard surface of the present invention, when manufactured with water containing a hardness component or diluted with water containing a hardness component, precipitates pigments and the like even when stored at high temperatures. It does not generate and has excellent appearance stability. 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.

  In the present invention, the component (a) contains one or more surfactants selected from nonionic surfactants and amphoteric surfactants.

  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, and an alkyl group having 12 to 18 carbon atoms is particularly 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, as for the 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 preferably 0.01 in the liquid detergent composition for hard surface of the present invention in consideration of providing sufficient detergency and considering easy removal of the cleaning component by rinsing after use. -5 mass%, more preferably 0.1-5 mass%, still more preferably 0.2-5 mass%.

  In the present invention, a copper phthalocyanine dye is used as the component (b). Examples of the copper phthalocyanine dye include those represented by the following general formula (b1) and general formula (b2).

C ₃₂ H _(16-n) X _n N ₈ Cu (b1)
(In the formula, n represents an average number of 0 to 4, and X represents a halogen atom.)

[Wherein, R ^{1b to} R ^4b each independently represent a substituent necessary for imparting water solubility to the dye, such as a carboxyl group and a sulfonic acid group, and n1 to n4 are Independently, an integer of 0 to 4 is represented. ]

  In the general formula (b1), examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferable. In the copper phthalocyanine pigment as a blue pigment, the average number of added chlorines for one compound [n in the formula (b1)] is not particularly limited in the present invention, but the number of added chlorine groups is preferably smaller. In particular, 0 to 1 is preferable. Specific examples of the copper phthalocyanine-based blue pigment include Pigment Blue 15 [n = 0 in Formula (b1)], Color Blue (CI) name, and Pigment Blue 15: 1 [Formula (b1) n = 0], Pigment Blue 15: 2 [n = 0 in the formula (VI)], Pigment Blue 15: 3 [n = 0 in the formula (b1)], Pigment Blue 15: 4 [in the formula (b1) N = 0 in the formula (VI) and other dyes such as CAS-RN: 12239-87-1 [n = 1 in the formula (VI)], 147-13-7 [n = 1 in the formula (b1) ] 15975-60-7 [n = 1 in formula (b1)], 35254-77-4 [n = 2 in formula (b1)], 29719-96-8 [n = in formula (b1) 3], 27614-71-7 n = 4 in the formula (b1)], include compounds that have been registered as 16040-69-0 [n = 4 in the formula (VI)]. Among these compounds, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, and Pigment Blue 15: 4 are compounds having an average chlorine addition number n of 0 to 1. Particularly preferred are Pigment Blue 15: 3 and Pigment Blue 15: 4.

  Specific examples of preferable compounds among the compounds represented by the general formula (b2) include Color Index (CI) name, Direct Blue 86, Direct Blue 87, Acid Blue 249, Reactive Blue 15 , Reactive Blue 21, Reactive Blue 25, Reactive Blue 71 and the like, and particularly preferable are Direct Blue 86, Acid Blue 249, Reactive Blue 15, and Reactive Blue 71, and Reactive Blue 71.

  (B) Content of a component is 0.00001-0.05 mass% in the liquid cleaning composition for hard surfaces of this invention, Furthermore, 0.00005-0.02 mass%, Furthermore, 0.0001-0. 01% by mass is preferred.

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. When it is made into 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 while remaining 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 (a) to the component (c) is 0.1 to 30, more preferably 0.5 to 15, more preferably (a) component / (c) component from the viewpoint of detergency. It is preferable that it is 1-10.

  The liquid detergent composition for hard surface of the present invention contains 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 0.01 to 30% by mass in the liquid detergent composition for hard surface of the present invention in order to give sufficient detergency, but preferably 0.05 to 30% by mass. %, More preferably 0.1 to 20% by mass, and most preferably 0.3 to 10% by mass.

  The liquid detergent composition for hard surfaces of the present invention has a quaternary ammonium salt type bactericidal property having one or two hydrocarbon groups having 6 to 16 carbon atoms as component (e) for the purpose of imparting bactericidal properties. You may contain the cationic surfactant which has. However, in this case, at least one compound selected from monocarboxylic acid or a salt thereof containing an aryl group having 10 or less carbon atoms and monosulfonic acid or a salt thereof containing an aryl group having 10 or less carbon atoms as component (f) It is preferable to contain together.

  As the component (e), one or more cationic surfactants selected from a cationic surfactant represented by the following general formula (e1) and a cationic surfactant represented by the general formula (e2) are included. preferable.

Wherein R ^1e and R ^2e are the same or different and each represents a long-chain alkyl group, long-chain alkenyl group or long-chain hydroxyalkyl group having 6 to 14 carbon atoms and 16 to 26 carbon atoms in total, and R ^3e and R ^4e 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 is a halogen atom, an amino acid, a fatty acid, or a carbon atom having 1 to 30 carbon atoms. Anionic residue of a phosphate ester, phosphonate ester, sulfonate ester or sulfate ester having a linear or branched alkyl group or alkenyl group, or a styrene sulfonic acid having a polymerization degree of 3 or more, or a hydrocarbon as a substituent Anionic oligomers or polymers containing formalin condensates of sulfonated polycyclic aromatic compounds Show mer.)

(In the formula, R ^5e is a hydrocarbon group having 8 to 14 carbon atoms, or

Z represents the same meaning as described above. )

In general formula (e1), R ^1e and R ^2e are preferably alkyl groups having 8 to 12 carbon atoms, and R ^3e and R ^4e are preferably alkyl groups having 1 to 3 carbon atoms. In general formula (e2), R ^5e is preferably a hydrocarbon group having 8 to 14 carbon atoms. Further, as Z in the general formulas (e1) and (e2), a halogen atom is particularly preferable.

  Specific examples of suitable component (e) include didecyldimethylammonium chloride, benzalkonium chloride, benzethonium chloride, and the like, particularly those represented by the general formula (d2), such as benzalkonium chloride, benzethonium chloride. Is preferred.

  Further, the component (f) is not particularly limited, and examples thereof include benzoic acid, salicylic acid, benzenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, and alkali metal salts thereof. Among these, preferred compounds are toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and salts thereof. Examples of the salt include alkali metal salts such as sodium and potassium.

  Here, the mass ratio of the (e) component and the (f) component is 0.01 to 10 (e) / (f), more preferably 0.02 to 5, and even more from the viewpoint of appearance stability and bactericidal efficacy. It is preferable that it is 0.03-2.

  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 (g). As the component (g), among compounds listed as “component (b)” in Japanese Patent Application Laid-Open No. 11-189796, one or more compounds not corresponding to the component (a) of the present invention are used. Can do. The total amount of the component (a) and the component (g) is preferably 0.1 to 5% by mass and more preferably 0.2 to 5% by mass in the liquid detergent composition for hard surface of the present invention.

  In the liquid detergent composition for hard surface of the present invention, a builder component can be blended as the component (h). 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 (h) 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 hard surface liquid detergent composition of the present invention, polyacrylic acid and its salt, a copolymer of olefin and maleic anhydride and its salt, and the like, as well 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. In addition, the pH of the liquid detergent composition for hard surface of the present invention at 25 ° C. is preferably pH 8 or higher, more preferably pH 10 or higher, and preferably pH 14 or lower in order to obtain a high detergency. More preferably, the pH is 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 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. 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 combination of component (a), component (b), component (c) and component (d) selected in the present invention includes water used for preparing and diluting the composition containing calcium ions and magnesium ions as hardness components. Even when stored at high temperatures, a hard surface liquid detergent composition that maintains a stable appearance is provided. In the liquid detergent composition for hard surface of the present invention, calcium ions and / or magnesium ions in total are 0.5 mmol / L or more, further 0.7 to 2.5 mmol / L, and further 1.0 to 2.0 mmol. / L concentration. Moreover, in this invention, (a) component, (b) component, (c) component and (d) component, and calcium ion and / or magnesium ion are 0.5 mmol / L or more in total, and also 0.7-2. The manufacturing method of the liquid detergent composition for hard surfaces which has the process of mixing with the water contained by the density | concentration of 1.0-2.0 mmol / L of 0.5 mmol / L and still more is provided. This manufacturing method can be applied to both the manufacturing method of the composition itself (stock solution) and the manufacturing method of the diluted solution of the composition. In the latter case, the liquid detergent composition for hard surface of the present invention containing (a) component, (b) component, (c) component, (d) component and water, and calcium ions and / or magnesium ions in total For dilute hard surfaces having a step of mixing water containing 0.5 mmol / L or more, further 0.7 to 2.5 mmol / L, and further 1.0 to 2.0 mmol / L. It can be implemented as a method for producing a liquid detergent composition.

Examples 1-8, Comparative Examples 1-4
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 appearance stability and cleaning performance was performed by the following method using each liquid detergent composition for hard surfaces. The results are shown in Table 1. In Table 1, in some comparative examples, (a) / (c) mass ratio was shown using the polymer compounds 2 and 3 as the component (c).

(Appearance stability)
The liquid detergent composition is diluted 2 times, 3 times, 5 times, 10 times, 20 times, 40 times and 50 times with water having a calcium ion concentration of 1.78 mmol / L. Prepare a sample in a 100 ml polypropylene container. Each sample (sealed state) is allowed to stand in a room at 40 ° C. for 30 days, and it is checked whether precipitation of pigments or the like occurs in the middle. Appearance stability was evaluated according to the following criteria.
At 4:30 days, no change in appearance was observed in any of the samples.
3: Appearance change was recognized in any sample in 20-29 days.
2: Appearance change was observed in any sample from 10 to 19 days.
1: Appearance changes such as cloudiness and precipitation were observed in any sample within 9 days.

(Cleaning performance)
The cleaning performance was evaluated with a solution obtained by diluting the liquid detergent composition 50 times with water having a calcium ion concentration of 1.78 mmol / L. Rapeseed oil 0.01 g was uniformly applied to a polypropylene plate (70 mm × 20 mm) to prepare a model contaminated plate. 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 that feel a sense of null 3: 3-4 boards that feel a sense of null 2: 5-6 boards that feel a sense of null 1: More than 7 boards that feel a sense of null

* 1 Amhitor 20N, Kao Corporation * 2 Mydoll 12, Kao Corporation * 3 Amhitor 20AB, Kao Corporation * 4 EP-700 BLUE GA: Dainichi Seika Kogyo Co., Ltd. [in general formula (b1) A liquid containing a copper phthalocyanine dye whose n is 0]
* 5 TURQUOISE BLUE SBL CONC: manufactured by Sanyo Dye Co., Ltd. (a liquid containing a copper phthalocyanine dye in which R ^{1b to} R ^4b in the general formula (b2) are sulfonic acid groups and n1 + n2 + n3 + n4 = 2)
* 6 Reactive Blue 71
* 7 Polymer compound synthesized by the method of Synthesis Example below <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.
* 8 Sanizole C: manufactured by Kao Corporation * 9 Aqualic DL-100: manufactured by Nippon Shokubai Co., Ltd. [sodium polyacrylate, average molecular weight 5000]
* 10 Quinnflow 540: manufactured by Nippon Zeon Co., Ltd. [Aqueous solution of sodium salt of pentene-maleic anhydride copolymer]
* 11 6N-sodium hydroxide aqueous solution or 6N-hydrochloric acid, and the appropriate amount is an amount for achieving the pH in the table.

Claims (6)

(A) One or more surfactants selected from nonionic surfactants and amphoteric surfactants, (b) copper phthalocyanine dyes, (c) trunks of polyether compounds 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 acrylic acid and / or methacrylic acid, (d) alkanolamine, and water in the chain.
_{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 detergent composition for hard surfaces according to claim 1 or 2, wherein the mass ratio of (a) / (c) is from 0.01 to 50.   Further, (e) a quaternary ammonium salt type bactericidal surfactant having one or two hydrocarbon groups having 6 to 16 carbon atoms and (f) an aryl group having 10 or less carbon atoms The hard surface according to any one of claims 1 to 3, comprising at least one compound selected from monocarboxylic acid or a salt thereof and monosulfonic acid or a salt thereof containing an aryl group having 10 or less carbon atoms. Liquid detergent composition.   The liquid detergent composition for hard surfaces according to any one of claims 1 to 4, comprising 0.5 mmol / L or more of calcium ions and / or magnesium ions.   The liquid detergent composition for hard surfaces according to claim 4 or 5, wherein the mass ratio of (e) / (f) is 0.01 to 10.