JP5634762B2 - Liquid detergent composition for automatic dishwashers - Google Patents

Description

    The present invention relates to a liquid detergent composition for an automatic dishwasher.

  As described in Patent Documents 1 and 2, it is known to add a metal chelating agent such as glutamic acid diacetic acid and its salt to an automatic dishwasher cleaning agent. Furthermore, as described in Patent Document 2, a liquid detergent for an automatic dishwasher containing a metal chelating agent is used in combination with a polycarboxylic acid type polymer compound such as an acrylic acid / maleic acid copolymer as a polymer dispersant. This is preferable for the purpose of improving detergency.

  On the other hand, a liquid detergent for an automatic dishwasher is not preferred because it has a low viscosity, and when used in a washing machine having an automatic inlet for the detergent, all or one of the detergents is used in the pre-washing process. Since the part leaks, there is a problem that the original cleaning performance cannot be obtained. In order to solve this problem, Patent Document 3 discloses that the liquid detergent composition is thickened using a polyacrylic acid thickener and is appropriately yielded so that the detergent composition stays at the automatic detergent inlet. A technique for assigning a value is disclosed.

JP 2008-127490 A JP 2006-152287 A JP 2008-163292 A

  However, when a polyacrylic acid thickener is blended, it contains an aminocarboxylic acid type chelating agent such as glutamic acid diacetic acid, a polymer type chelating agent or dispersing agent such as an acrylic acid / maleic acid copolymer or a salt thereof. When the amount is large, the salt strength increases, so that the solubilized / emulsified state of the nonionic surfactant having a role as a detergent component becomes unstable, and there is an important problem that separation occurs during storage. Therefore, a technique for stably thickening a liquid detergent composition for an automatic dishwasher containing a large amount of a chelating agent is desired.

  Accordingly, an object of the present invention is to provide a liquid detergent for an automatic dishwasher that contains a large amount of a chelating agent, does not cause separation of a nonionic surfactant or the like during storage, and has high detergency against tea astringent stains It is to provide a composition.

  The present invention comprises (a) a chelating agent (excluding (c) and (d)) [hereinafter referred to as component (a)] 15 to 30% by mass, (b) a nonionic surfactant [hereinafter referred to as (b) Component)], (c) copolymer of acrylic acid and (meth) acrylic acid alkyl ester or salt thereof (hereinafter referred to as component (c)), (d) crosslinked polyacrylic acid or salt thereof (hereinafter referred to as component (d)) In addition, the total content of (c) and (d) is 0.7 to 3.5% by mass, and the mass ratio of (c) / (d) is 0.01 to 1. And a liquid detergent composition for an automatic dishwasher.

  According to the present invention, a liquid detergent composition for an automatic dishwasher that contains a large amount of a chelating agent, does not cause separation of a nonionic surfactant or the like during storage, and has high detergency against tea astringent stains. Is provided.

<(A) component>
The component (a) of the present invention is a compound having a metal ion chelating ability, and includes a low molecular chelating agent having a small molecular weight and a high molecular chelating agent having a high molecular weight excluding the components (c) and (d). .

  As the low molecular chelating agent, a water-soluble organic acid having a molecular weight of 40 to 400, preferably 200 to 400, more preferably 200 to 380, or a salt thereof can be blended. In particular, a polyvalent carboxylic acid having 2 or more, preferably 2 to 6 carboxylic acid groups in the molecule, or a salt thereof is preferable.

  Specifically, carboxylic acid selected from gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid and fumaric acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, serine An aminocarboxylic acid selected from diacetic acid and aspartic acid diacetic acid, a phosphonic acid selected from hydroxyethanediphosphonic acid and aminotrimethylenephosphonic acid, and salts thereof such as alkali metal salts, alkaline earth metal salts or amine salts; Particularly preferred are citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid and their alkali metal or alkanolamine salts.

  The polymer chelating agent is preferably a compound having a weight average molecular weight of 1,000 to 100,000. As the polymer chelating agent, it is preferable to use a polymer compound containing a monomer structural unit having a carboxylic acid group excluding the component (c) and the component (d), and particularly derived from an acrylic acid monomer and / or a maleic acid monomer. Those having a monomer constituent unit are preferable, and polyacrylic acid, a copolymer of acrylic acid and maleic acid, isobutylene or a copolymer of diisobutylene and maleic acid are particularly preferable in terms of washing performance. The polymeric chelating agent may be an alkali metal salt or an alkanolamine salt. The salt of the polymer chelating agent may be either one using a salt-type compound as a monomer, neutralized after polymerization, or a combination of both. The weight average molecular weight of the component (b) polymer chelating agent can be determined by using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent and using polyethylene glycol as a standard substance by gel permeation chromatography. .

  When a copolymer of acrylic acid and maleic acid or a salt thereof is used as the polymer chelating agent, the molar ratio of acrylic acid / maleic acid is preferably 0.1 to 9, more preferably 0.2 to 4, and still more preferably 1. .5-4.

  The liquid detergent composition for automatic dishwashers of this invention contains (a) component 15-30 mass%, Preferably it is 15-27 mass%, More preferably, 17-25 mass% is contained.

  The content of the low molecular chelating agent, in particular, the low molecular chelating agent having the molecular weight in the composition is preferably 5 to 25% by mass, more preferably 7 to 20% by mass, and particularly preferably 7 to 15% by mass. .

  The content of the polymer chelating agent, particularly the polymer chelating agent having the molecular weight, is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, and still more preferably 5 to 12% by mass. .

  In the present invention, as the component (a), it is preferable to use a low-molecular chelating agent, particularly a high-molecular chelating agent of the molecular weight, and a high-molecular chelating agent, particularly the high-molecular chelating agent of the molecular weight. And the mass ratio of the low-molecular chelating agent / polymer chelating agent is preferably 0.3 to 3, more preferably 0.5 to 2, and particularly preferably 0.6 to 2 . Furthermore, it is preferable to contain (a1) aminocarboxylic acid or a salt thereof as a low-molecular chelating agent and (a2) a copolymer of acrylic acid and maleic acid or a salt thereof as a high-molecular chelating agent. The mass ratio is also preferably within the above range.

<(B) component>
The component (b) used in the present invention is a nonionic surfactant from the viewpoint of storage stability and cleaning performance, and specifically, a polyoxyalkylene type nonionic surfactant (polyoxyethylene monoalkyl or monooxygen). Alkenyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene monoalkyl or monoalkenyl ether, polyoxybutylene monoalkyl or monoalkenyl ether, alkylene oxide-added monoalkyl group or monoalkenyl group-containing nonionic surfactant mixture, etc.) Sucrose fatty acid ester, aliphatic alkanolamide, fatty acid glycerin monoester, amine oxide, and glycoside nonionic surfactant (alkyl glycoside, etc.). Specific examples of such nonionic surfactants include the following (1) to (11).

(1) Polyoxyalkylene monoalkyl or monoalkenyl ether type nonionic surfactant, in particular, the alkyl group or alkenyl group has an average carbon number of 8 to 20, and the average added mole number of alkylene oxide is more than 0 to 110. In addition, the average number of moles of ethylene oxide added is 1 to 30 moles. Preferred compounds include polyoxyalkylene monoalkyl or monoalkenyl ether type non-ion represented by the following general formula (b1), and polyoxyethylene monoalkyl or monoalkenyl represented by the following general formula (b1-1). Mention may be made of ethers.
R ¹¹ [(OC ₂ H ₄ ) _l / (OC ₃ H ₆ ) _m ] OH (b1)
[Wherein R ¹¹ is a hydrocarbon group having 8 to 18 carbon atoms, l and m are average added mole numbers, l is a number from 0 to 10, and m is a number from 0 to 100, l and m are not 0 at the same time. “/” Indicates that the oxyethylene group and the oxypropylene group may be added randomly or in a block regardless of the order. ]
_{^{R 11 '(OC 2 H 4}} ) m O H (b1-1)
[Wherein, R ^{11 ′} is an alkyl group or alkenyl group having 8 to 18 carbon atoms, m is an average added mole number, and is a number of 1 to 6. ]

(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 monoalkyl or monoalkenyl ether, wherein the alkyl group or alkenyl group has an average carbon number of 8 to 20 and the average number of propylene oxide addition moles of 1 to 20 mol.

(4) Polyoxybutylene monoalkyl or monoalkenyl ether, wherein the alkyl group or alkenyl group has an average carbon number of 8 to 20 and an average number of moles of butylene oxide addition of 1 to 20 mol.

(5) Having an alkyl group or alkenyl group only at one end, ethylene oxide and propylene oxide (molar ratio of ethylene oxide / propylene oxide is 0.01 to 99) or ethylene oxide and butylene oxide (of ethylene oxide / propylene oxide) A nonionic surfactant mixture obtained by adding a molar ratio of 0.01 to 99), wherein the average number of carbon atoms of the alkyl group or alkenyl group is 8 to 20, and the number of moles of alkylene oxide added per molecule Is an average of 1 to 30 moles.

(6) A higher fatty acid alkanolamide represented by the following general formula (b2) or an alkylene oxide adduct thereof.

[Wherein R ²¹ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ²² and R ²³ are the same or different and are a hydrogen atom or a methyl group, p is a number of 1 to 3, and q is 0 It is a 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 (b3).

[Wherein R ³¹ is a hydrocarbon group having 6 to 24 carbon atoms, R ³² and R ³³ may be the same or different, and a hydrocarbon group having 1 to 3 carbon atoms, D is —COO—, — CONH—, a group selected from —O—, E is a divalent hydrocarbon group having 1 to 5 carbon atoms, a and b are a = 0 and b = 0, or a = 1 and b = 1. ]

(10) A glycoside nonionic surfactant. For example, a compound represented by the following general formula (b4).
R ⁴¹ (OR ⁴² ) _x G _y (b4)
[Wherein, R ⁴¹ represents a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, preferably an alkyl group, and R ⁴² represents an alkylene group having 2 to 4 carbon atoms. G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x (average value) is 0-5, and y (average value) is 1-5. ]

The value of x in the general formula (b4) is preferably 0 to 2, particularly preferably 0. Moreover, the average value of y in general formula (b4) 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. Preferred raw materials are glucose and fructose for monosaccharides, and maltose and sucrose for disaccharides and higher in view of their availability and cost. R ⁴¹ is preferably a linear or branched alkyl group having 8 to 18 carbon atoms in total.

(11) A linear or branched alkyl glyceryl ether having 5 to 20 carbon atoms.

  Among these nonionic surfactants, (1), (5), (6), (9), (10) and (11) are preferred, and (1), (5), (9), (10 ) And (11) are preferable, and (1) and (10) are more preferable. Therefore, the component (b) of the present invention is preferably at least one selected from polyoxyethylene monoalkyl or monoalkenyl ether and alkyl glycoside.

The component (b) preferably contains the polyoxyethylene alkyl or alkenyl ether represented by the general formula (b1-1). In this invention, it is preferable that carbon number of R11 ^' in general formula (b1-1) is 8-14, and 12-12 carbon atoms are especially preferable at the point of low-foam property and detergency. Moreover, the alkyl group or alkenyl group of R ^{11 ′} in formula (b1-1) is particularly preferably derived from a secondary alcohol. Moreover, as for the average addition mole number m of the ethylene oxide of general formula (b1-1), 2-4 are preferable. In the nonionic surfactant of the general formula (b1) and (b1-1), the remaining unreacted alcohol is preferably 2% by mass or less.

  In the liquid detergent composition for an automatic dishwasher of the present invention, the component (b) is preferably 0.01 to 3% by mass, more preferably 0.1 to 2.8 from the viewpoint of storage stability and cleaning performance. It is contained by mass%, more preferably 0.5-2.8 mass%, still more preferably 1.5-2.5 mass%.

<(C) component>
The liquid detergent composition for an automatic dishwasher of the present invention contains a copolymer of acrylic acid and (meth) acrylic acid alkyl ester or a salt thereof as component (c). Examples of the salt of the copolymer include sodium salt, potassium salt, alkanolamine salt, ammonium salt and the like, and any of those using a salt type compound as a monomer or neutralized after copolymerization may be used. It may be used in combination. (Meth) acrylic acid means acrylic acid and / or methacrylic acid. In addition, the component (c) is a polymer chelate of the component (a) in that the viscosity measured by a Brookfield viscometer at 20 ° C. in a 0.2 mass% aqueous solution adjusted to pH 7.0 exceeds 50 mPa · s. Distinguished from agents.

  (C) As for the (meth) acrylic-acid alkylester which comprises a component, the alkyl group which comprises ester has 8-30 carbon atoms, Furthermore, 10-30, Especially 10-22 are preferable. The component (c) may contain a structural unit derived from an alkylene oxide having 2 to 4 carbon atoms (hereinafter referred to as AO), and examples of AO include ethylene oxide and propylene oxide, preferably ethylene oxide. Can do. The average added mole number of AO is preferably 5-20.

  Moreover, (meth) acrylic-acid alkylester 0.2-10 is preferable with respect to acrylic acid 100 by molar ratio, and, as for the ratio of the monomer of (c) component, 0.5-5 are especially preferable, and AO origin When a structural unit is introduced, it is preferable to use 0.2 to 10 of an AO adduct of (meth) acrylic acid alkyl ester and / or an acrylic acid AO adduct with respect to 100 of acrylic acid.

  The (c) copolymer of acrylic acid and (meth) acrylic acid alkyl ester or a salt thereof contains an aqueous solution containing 0.2% by mass of the component (c) and adjusted to pH 7.0 with sodium hydroxide at 20 ° C. The viscosity measured with a Brookfield viscometer (rotor No. 4, rotation speed: 12 r / m) is preferably 500 mPa · s or more, more preferably 1000 to 70,000 mPa · s, still more preferably 1500 to 40,000 mPa · s.

  Component (c) is one in which the constituent monomers are acrylic acid or a salt thereof and alkyl methacrylate, and further contains only acrylic acid or a salt thereof and alkyl methacrylate as a substantial constituent monomer. Preferably, a cross-linked acrylic acid / methacrylic acid alkyl ester obtained by using a compound having at least two ethylenically unsaturated groups as a cross-linking agent with respect to 100 parts by weight of acrylic acid. Copolymers are preferred.

  As the component (c), for example, commercially available products such as Carbopol ETD2020 manufactured by Noveon Inc., Akpek HV501ER, and Akpek HV701EDR manufactured by Sumitomo Seika Co., Ltd. can be used. These can also use 2 or more types together.

<(D) component>
The liquid detergent composition for an automatic dishwasher of the present invention contains crosslinked polyacrylic acid or a salt thereof as the component (d). Examples of the salt include sodium salt, potassium salt, alkanolamine salt, ammonium salt and the like, and any of those using a salt-type compound as a monomer or neutralized after polymerization may be used together. It may be. In addition, the component (d) is a polymer chelate of the component (a) in that a 0.2 mass% aqueous solution adjusted to pH 7.0 has a viscosity measured with a Brookfield viscometer at 20 ° C. exceeds 50 mPa · s. Distinguished from agents.

  The component (d) is a cross-linked polysiloxane obtained by using, as a cross-linking agent, a compound having at least two ethylenically unsaturated groups of 0.01 to 3 parts by mass with respect to 100 parts by mass of acrylic acid. Acrylic acid or its salt is mentioned.

  As the compound having at least two ethylenically unsaturated groups, for example, at least one of pentaerythritol tetraallyl ether, tetraallyloxyethane, triallyl phosphate, and polyallyl saccharose is preferable. It is preferable that a crosslinking agent is 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts of acrylic acid.

  As the cross-linked polyacrylic acid or a salt thereof as component (d), for example, commercially available products such as Carbopol 980 and Carbopol 981 manufactured by Noveon Inc., Akpec HV501E and HV505E manufactured by Sumitomo Seika Co., Ltd. are used. be able to. These can also use 2 or more types together.

  The cross-linked polyacrylic acid or salt thereof as component (d) contains 0.2 mass% of component (d) and an aqueous solution adjusted to pH 7.0 with sodium hydroxide at 20 ° C. at a Brookfield viscometer ( Rotor No. 4, having a viscosity measured at a rotational speed of 12 r / m) is preferably 500 mPa · s or more, more preferably 1,000 to 70,000 mPa · s, and still more preferably 1,500 to 40 , 000 mPa · s.

  It is preferable that (c) component and (d) component exist in a cleaning composition as a salt with the below-mentioned pH adjuster.

  The total content of the component (c) and the component (d) in the composition is 0.7 to 3.5% by mass, preferably 0.9 to 2.5% by mass from the viewpoints of thickening and storage stability. %, More preferably 1-2% by mass.

  The mass ratio of (c) / (d) is 0.01 to 1 from the viewpoints of thickening and storage stability, preferably 0.05 to 0.8, more preferably 0.1 to 0.00. 6.

  In the liquid detergent composition for an automatic dishwasher of the present invention, the total of component (c) and component (d) is preferably 0.7 to 3.5% by mass, more preferably 0.9 to 2.5. It is contained by mass%, more preferably 1-2% by mass.

  Moreover, in the liquid detergent composition for automatic dishwashers of this invention, mass ratio with (a) component and the sum total of (c) component and (d) component is [(c) + (d)] / In (a), it is preferably 0.01 to 1, more preferably 0.01 to 0.5, and further preferably 0.02 to 0.2 from the viewpoint of thickening and storage stability.

<Other ingredients>
In the composition of the present invention, it is preferable from the viewpoint of the cleaning effect that a polypropylene glycol (hereinafter referred to as component (e)) having a weight average molecular weight of 600 to 20,000, preferably 2,000 to 10,000 is blended. It is preferable that the polypropylene glycol is blended in the composition in an amount of 0.1 to 10% by mass, further 0.5 to 5% by mass, particularly 1 to 5% by mass. The weight average molecular weight of polypropylene glycol can be determined using a light scattering method, and can be measured by a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.).

  When polypropylene glycol is used as the solvent, in order to uniformly disperse it in the composition, as component (b), at least one selected from the above (1), (5), (9) and (10) is used. It is preferable to use it. From the viewpoints of dispersion stability and low foamability, the mass ratio of component (e) / component (b) is preferably 0.1 to 9, more preferably 0.2 to 2.5, and still more preferably 0.4. ~ 1.5.

  The liquid detergent composition for an automatic dishwasher of the present invention preferably contains an enzyme as the component (f) for the purpose of further enhancing the cleaning effect.

  Specific examples include cellulase, protease, lipase, amylase, esterase, pectinase, lactase, and peroxidase, and protease and amylase are particularly preferable.

  Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, esperase, evalase, cannase, ovozyme (Novozymes Japan K.K.), Excellase, properase, Perfect OX, and Perfect L (Genencor Kyowa). .

  Examples of commercially available enzymes that can be used as amylase include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry Co., Ltd.), Plaster HP A, Plaster OxAm (Genencor Kyowa). it can.

  In the present invention, it is preferable to use protease and amylase in combination, and the mass ratio of amylase / protease as the amount of enzyme protein is preferably 0.01 to 15, more preferably 0.02 to 9, and particularly preferably 0.2 to 9. 4.

  The amount of component (f) in the composition is preferably 0.005 to 3% by mass, more preferably 0.01 to 2.5% by mass, and still more preferably 0.03 to 2% by mass as the amount of enzyme protein. %.

  When the component (f) is added to the liquid detergent composition for an automatic dishwasher of the present invention, it is preferable to contain a water-soluble calcium salt [hereinafter referred to as the component (g)] as an enzyme stabilizer. As the water-soluble calcium salt, calcium chloride is preferable. (G) Content of a component becomes like this. Preferably it is 0.01-1 mass% in a composition, More preferably, it is 0.02-0.5 mass%, More preferably, it is 0.05-0.3 mass%.

  The liquid detergent composition for an automatic dishwasher of the present invention has at least one solvent selected from ethylene glycol, propylene glycol, glycerin and sorbitol (hereinafter referred to as component (h)) for the purpose of further improving stability. Is preferably blended. As the component (h), propylene glycol and / or glycerin is preferable, and the content in the composition is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 2 to 5% by mass. .

  The liquid detergent composition for an automatic dishwasher according to the present invention contains the above-mentioned components (a) to (d), as well as optional (e) to (h) components. A liquid composition dissolved in, emulsified and dispersed in, preferably in the form of an aqueous solution. The water used is preferably ion-exchanged water or distilled water from which a small amount of metal has been removed, and hypochlorous dissolved in 0.1 to 10 ppm of chlorine. It is also suitable to use chloric acid sterilized water.

  The pH at 25 ° C. (JIS-Z-8802: 1984 “pH measurement method”) of the liquid detergent composition for an automatic dishwasher of the present invention is 6 to 9, preferably 7 to 8 from the viewpoint of storage stability. It is. In order to obtain such a pH, a pH adjusting agent can be used. Specifically, an inorganic alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and an organic alkaline agent selected from amine compounds. Can be mentioned. As the amine compound, amine compounds represented by the following general formulas (I) to (IV) are suitable. An appropriate amount of the pH adjuster is appropriately added to adjust the pH of the liquid detergent composition of the present invention.

(In the formula, R ¹ , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ , R ¹² , R ¹³ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms. R ² , R ³ , R ⁵ , R ⁷ , R ⁹ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.)

  Examples of the compound represented by the general formula (I) include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol and the like.

  Examples of the compound represented by the general formula (II) include N- (β-aminoethyl) ethanolamine.

Examples of the compound represented by the general formula (III) include diethylenetriamine.
Examples of the compound represented by the general formula (IV) include morpholine and N-ethylmorpholine.

  Among these, from the viewpoint of storage stability and cost of the cleaning composition, hydroxides such as potassium hydroxide and sodium hydroxide are preferable as the inorganic alkaline agent, and monoethanolamine is preferable as the organic alkaline agent.

  The liquid detergent composition for an automatic dishwasher of the present invention preferably has a viscosity at 20 ° C. of 500 to 5,000 mPa · s, more preferably 800 to 4,000 mPa · s, and still more preferably 1000 to 3000 mPa · s. It is s and such a viscosity can be suitably adjusted with the kind and content of (c) component. The viscosity is measured using a Brookfield viscometer (when the viscosity is 4,000 mPa · s or less, rotor No. 3, the rotation speed is 30 r / m, the viscosity exceeds 4,000 mPa · s, and is 20,000 mPa · s or less. In this case, the rotor No. 4 is used with a rotation speed of 30 r / m.

  Moreover, the liquid detergent composition for automatic dishwashers of this invention adds (a) component to water, for example so that the sum total of (a) component may be 15 mass% or more, and described above pH adjuster. After adjusting the pH at 25 ° C. to 5 or less, it is preferable to add and disperse the component (c) and the component (d). The pH can be adjusted by a part of the component (a).

  Moreover, as a stirrer used when producing the detergent composition for an automatic dishwasher of the present invention, a stirrer that can be mixed under high shear conditions is preferable from the viewpoint of blending stability. Ajihomomica, Primix Co., Ltd. K. Homomixer, T.W. K. Homo disperse is preferred, and the continuous type is T.I. K. Pipeline homomixer, T.W. K. A homomic line mill or the like is preferable.

  Moreover, the liquid detergent composition for an automatic dishwasher of the present invention is preferably an emulsion, and in particular, the average particle diameter (median diameter) of the emulsified particles of the composition is less than 10 μm, and more preferably less than 5 μm. Preferably there is. In addition, the average particle diameter (median diameter) of the emulsified particles of the composition is a value measured with a particle size distribution meter (HORIBA LA-950V2, Horiba, Ltd.) using ion-exchanged water as a dispersion medium.

  With the compounding compositions shown in Tables 1 and 2, a liquid detergent composition for an automatic dishwasher was prepared and evaluated as follows. The compositions other than Comparative Example 5 were all emulsions having an average particle size of the emulsified particles of less than 10 μm at the time of preparation.

<Brown tea stain cleaning performance>
* Used washing machine Using an automatic dishwasher (model NP-P45M1PS) manufactured by Matsushita Electric Industrial Co., Ltd., speedily put the following tableware (contaminated hot water) and the liquid detergent composition for the automatic dishwasher shown in Table 1 or 2 I drove on the course.
Contaminated hot water: 3 (prepared by the following method)
Water used: 3.2 ° dH water Detergent composition added amount: 6 g

* Preparation and evaluation method of contaminated hot water cups After 3 packs of black tea (Nitto black tea) in 1 liter of hot water (3.2 ° dH hard water) for 10 minutes, the black tea is made of melamine (upper diameter: approx. 95 mm, height: approx. 50 g) was poured into the mixture, discarded after 60 minutes, and further naturally dried for one day and night. After the washing, the adhesion state of the 3 tea astringents was observed on a panel of men and women in their 30s (2 each), and evaluated according to the following criteria. 2 shows.
4: There is no tea astringent 3: There is a little tea astringent, but there is no problem in use 2: A level where tea astringent remains and needs to be washed again 1: A level where tea astringency is hardly removed

<Storage stability>
200 g of the liquid detergent composition shown in Tables 1 and 2 is put in a transparent container made of PET, stored at 50 ° C. for 30 days, and the appearance of the composition after storage is observed. In Tables 1 and 2, the results were evaluated as “◯” when the level was not problematic in use, and “X” when the level was separated.

  * 1 In Comparative Example 5, since the total amount of the component (c) and the component (d) could not be blended due to thickening, the viscosity measurement and subsequent evaluation were not performed.

In addition, the components (part) in the table are as follows.
<(A) component>
Acrylic acid / maleic acid copolymer salt: weight average molecular weight of about 30,000, acrylic acid / maleic acid molar ratio = 2.3, sodium salt

<(B) component>
Nonionic surfactant 1: polyoxyethylene alkyl ether obtained by adding an average of 3 moles of oxyethylene groups to a secondary higher alcohol having 12 to 14 carbon atoms in the alkyl group [in the general formula (b1-1), R ^{11 ′} is a secondary alkyl group having 12 to 14 carbon atoms, and m is a nonionic surfactant having 3)
Nonionic surfactant 2: polyoxyethylene alkyl ether obtained by adding an average of 4 mol of oxyethylene groups to a linear primary higher alcohol having 12 carbon atoms in the alkyl group [in the general formula (b1-1), R ^{11 ′} is a linear primary alkyl group having 12 carbon atoms, and m is a nonionic surfactant having 4)
And non-ionic surfactants 3: carbon atoms in the alkyl group is 12, a linear primary alkyl groups R ⁴¹ of the average glucose degree of condensation alkylglycosides 1.3 [formula (b4) in 12 carbons , G is a glucose residue, x is 0, and y is 1.3 alkylpolyglycoside]

<(C) component>
Copolymer of cross-linked acrylic acid / alkyl methacrylate: ACPEC HV701EDR [Cross-linked acrylic acid / alkyl methacrylate (carbon number: 10-30) copolymer, manufactured by Sumitomo Seika Co., Ltd.] (viscosity at 20 ° C .: the above-mentioned ACPEC HV701EDR An aqueous solution containing 0.2% by mass and adjusted to pH 7.0 with sodium hydroxide had a viscosity of 13,000 mPa measured at 20 ° C. using a Brookfield viscometer <rotor No. 4, rotation speed 12 r / m>.・ S)

<(D) component>
-Cross-linked polyacrylic acid: ACPEC HV501E [Cross-linked polyacrylic acid, manufactured by Sumitomo Seika Co., Ltd.] (Viscosity at 20 ° C: 0.2% by mass of the ACPEC HV501E, pH 7.0 with sodium hydroxide The adjusted aqueous solution was measured at 20 ° C. with a Brookfield viscometer <rotor No. 4, rotation speed 12 r / m> (viscosity of 4,000 mPa · s)

Hydroxyethyl cellulose: HEC Daicel SE900 (Daicel Chemical Industries, Ltd.) (Viscosity at 20 ° C .: An aqueous solution containing 1% by mass of SE900 at 20 ° C. Brookfield viscometer <rotor No. 4, rotation speed 12 r / m > Viscosity measured at> 5,000 mPa · s)
<(E) component>
Polypropylene glycol: weight average molecular weight of about 3,000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
<Component (f)>
・ Α-Amylase: Termamyl Ultra 300L (Novozymes Japan Ltd.)
・ Protease: Everase 16L (Novozymes Japan K.K.)

Claims (5)

(A) Chelating agent (excluding (c) and (d)) 15 to 30% by mass, (b) nonionic surfactant, (c) copolymer of acrylic acid and (meth) acrylic acid alkyl ester or salt thereof , (D) crosslinked polyacrylic acid or a salt thereof, and water, the total content of (c) and (d) is 1 to 2.5 % by mass, and the mass ratio of (c) / (d) The liquid detergent composition for automatic dishwashers whose is 0.01-1.   The liquid detergent composition for automatic dishwashers of Claim 1 whose viscosity in 20 degreeC is 500-5,000 mPa * s.   The liquid detergent composition for automatic dishwashers according to claim 1 or 2, wherein the mass ratio of [(c) + (d)] / (a) is 0.01-1.   The automatic dishwasher according to any one of claims 1 to 3, comprising (a) (a1) an aminocarboxylic acid or a salt thereof, and (a2) a copolymer of acrylic acid and maleic acid or a salt thereof. Liquid detergent composition.   The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the pH at 25 ° C is 6 to 9.