JP2008163292A - Thickened liquid detergent composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition having good detergency and high viscosity. <P>SOLUTION: This thickened liquid detergent composition comprises an alkali agent containing one or more selected from among an amine compound, potassium hydroxide and potassium carbonate, a polyacrylic acid thickener and water, wherein the pH at 25°C is 8.0-11.0, the content of sodium ions is ≤1 mass%, and the content of a surface active agent is ≤10 mass%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thickened liquid detergent composition and a method for producing the same.

  In recent years, automatic dishwashers have rapidly spread, and washing machines that reduce the amount of washing water used from the viewpoint of energy saving and resource saving and increase the amount of tableware to be washed at one time have become mainstream. is occupying. However, if washing is performed using a powder detergent while the tableware is excessively packed in such a washing machine, there may be a problem that the powder detergent remains undissolved in the tableware or a gap in the cabinet.

As a countermeasure, it has been proposed to use a highly soluble liquid detergent. Patent Document 1 discloses a technique that applies a nonionic surfactant, an enzyme, and an alkanolamine, and Patent Document 2 discloses a technique related to an emulsifying detergent that applies a nonionic surfactant, a builder, and a polyacrylic acid thickener. However, Patent Document 3 discloses a technique for applying an alkanolamine, an alkali compound, and a water-soluble polymer chelate-forming agent. Patent Document 4 discloses a boron compound, a polyhydroxy compound, calcium ion, water, an enzyme, and a polyacrylic acid-based polymer. A technique for applying a sticky agent is disclosed.
Japanese Patent Laid-Open No. 3-126798 JP-A-6-80998 JP 2000-256700 A JP 2004-525219 A

  As described above, Patent Documents 1 and 3 disclose that a liquid detergent composition is blended with a nonionic surfactant or an alkanolamine. However, when a low-viscosity liquid detergent composition is used, all or part of the detergent leaks out in the pre-washing process when used in a washing machine having an automatic detergent inlet, so that the original cleaning performance cannot be obtained. There was a problem.

  On the other hand, in order to solve this problem, in Patent Documents 2 and 4, it is necessary to thicken a liquid detergent composition using a polyacrylic acid thickener and to leave the detergent composition at an automatic detergent inlet. A technique for providing an appropriate yield value is disclosed. However, a liquid detergent composition containing a polyacrylic acid-based thickener exhibits good thickening and yield values in weakly acidic to neutral conditions, but rapidly increases when the pH is increased by adding a large amount of alkaline agent. Since the viscosity decreased, there was a problem in cleaning performance.

  Patent Documents 1 to 4 do not describe a problem relating to the viscosity of the alkaline agent and the liquid detergent composition necessary for enhancing the cleaning performance.

  An object of the present invention is to provide a liquid cleaning composition that exhibits good cleaning performance and has a high viscosity, and a method for producing the same.

  This invention contains the alkali agent containing 1 or more types chosen from an amine compound, potassium hydroxide, and potassium carbonate, the polyacrylic acid type | system | group thickener, and water, and pH in 25 degreeC is 8.0-11. The present invention relates to a thickened liquid detergent composition having a surfactant content of 10% by mass or less.

  Moreover, this invention is a manufacturing method of the thickened liquid cleaning composition in any one of Claims 1-5, Comprising: pH at 25 degreeC is adjusted to 8.0-11.0, and sodium ion It is related with the manufacturing method of the liquid detergent composition made to thicken by adjusting content of 1 to 1 mass% or less.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition which has the outstanding washing | cleaning performance and was thickened in the system with low surfactant density | concentration, especially suitable as an object for automatic dishwashers is provided.

<Alkaline agent>
The alkaline agent used in the present invention contains one or more selected from amine compounds, potassium hydroxide and potassium carbonate.

When an amine compound is used as the alkali agent, amine compounds represented by the following general formulas (1) to (4) are suitable.

(Wherein R ¹ , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ , R ¹² , R ¹³ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 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 (1) include monoethanolamine, diethanolamine, N-methylpropanol, and 2-amino-2-methyl-1-propanol.
Examples of the compound represented by the general formula (2) include N- (β-aminoethyl) ethanolamine.
Examples of the compound represented by the general formula (3) include diethylenetriamine.
Examples of the compound represented by the general formula (4) include morpholine and N-ethylmorpholine.

  Among these, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol and morpholine are preferable, and monoethanolamine is particularly preferable.

  In the present invention, sodium compounds such as sodium hydroxide, sodium carbonate, and sodium silicate can also be used as the alkali agent. In that case, the content of sodium ions in the liquid detergent composition is 1% by mass or less, The amount is preferably 0.8% by mass or less, particularly preferably 0.5% by mass or less. In addition, sodium ion concentration is a density | concentration including what is brought in from an anionic surfactant and a chelating agent other than an alkali agent, for example. In the present invention, sodium ions are not only dissociated but also all sodium in dissociation equilibrium.

  The blending amount of the alkaline agent in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 3 to 10% by mass from the viewpoint of cleaning performance.

  In the present invention, it is preferable to use an amine compound, particularly monoethanolamine, and at least one selected from potassium hydroxide and potassium carbonate as the alkali agent. From the viewpoint of cleaning performance and thickening in a high pH range, the ratio of monoethanolamine to one or more potassium compounds selected from potassium hydroxide and potassium carbonate, that is, monoethanolamine / (potassium hydroxide + potassium carbonate) The mass ratio is preferably 95/5 to 20/80, more preferably 90/10 to 30/70, and particularly preferably 80/20 to 40/60.

<Polyacrylic acid thickener>
In this invention, a polyacrylic acid type | system | group thickener is contained as a thickener. The polyacrylic acid thickener is (meth) acrylic acid [meaning methacrylic acid or acrylic acid. ], A 0.2% by mass aqueous solution adjusted to pH 7.0 with sodium hydroxide at 20 ° C., and a Brookfield viscometer (viscosity is 4000 mPa · s). In the following cases, the rotor No. 3, the rotation speed 30r / m, the viscosity exceeds 4000mPa · s, and in the case of 20,000mPa · s or less, the rotor No. 4, the rotation speed 30r / m, the viscosity 20,000mPa · s. Is higher than 500 mPa · s, preferably 1000 to 70,000 mPa · s, more preferably 1500 to 40,000 mPa · s. It is a molecular compound.

  Polyacrylic acid thickeners include cross-linked (meth) acrylic acid polymers [hereinafter referred to as (i)], copolymers of (meth) acrylic acid and (meth) acrylic acid esters [hereinafter (ii) Or more] selected from the group consisting of: These thickeners are preferably present in the liquid detergent composition as a salt with an alkaline agent. In addition, (i) is one kind of carboxyvinyl polymer.

  (i) The crosslinked (meth) acrylic acid polymer is preferably an acidic polymer compound having a carboxyl group, and is a polymer in which the main constituent monomer is acrylic acid, and has a molar ratio of 0 to 100 acrylic acid as a crosslinking agent. .1 (meth) acrylic acid esters (those that are esterified with 2 or more substitutions with polyols), and those that are usually used in cosmetics and pharmaceutical external preparations can be used without limitation. it can. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, polyethylene glycol, polypropylene glycol, polyglycerin, and other various sugars. In particular, a crosslinked acrylic acid homopolymer in (i) is most preferred.

  Such a crosslinked (meth) acrylic acid polymer comprises (meth) acrylic acid and, if necessary, other polymerizable monomers, and (meth) acrylic acid or other vinyl carboxylic acid compound. You may manufacture from the monomer esterified by substitution or more.

  For (i), for example, commercially available products such as Carbopol 980 and Carbopol 981, manufactured by Noveon Inc., and ACPEC HV501, HV501E, and HV505E manufactured by Sumitomo Seika Co., Ltd. can be used. These can also use 2 or more types together.

  (I) The average molecular weight of the crosslinked (meth) acrylic acid polymer is preferably 500,000 to 10,000,000, and it is particularly preferable to use a polymer having a weight average molecular weight of 500,000 to 2,000,000.

  Next, a copolymer of (ii) (meth) acrylic acid and (meth) acrylic acid ester will be described. In the copolymer, the hydrocarbon group constituting the ester of the structural unit (meth) acrylic acid ester (which means acrylic acid ester or methacrylic acid ester) is preferably an alkyl group, and the carbon number thereof is 8 to 30. Furthermore, 10-30, especially 10-22 are preferable.

  Moreover, the copolymer of (ii) may contain the structural unit derived from a C2-C4 alkylene oxide (henceforth AO), As ethylene oxide, propylene oxide, ethylene oxide, and propylene as AO A combination of oxides may be used. Preferably, ethylene oxide can be used. The average added mole number of AO is preferably 5-20.

  Moreover, the ratio of the monomer structural unit from the (meth) acrylic acid ester in the copolymer of (ii) is 0.2-10 of (meth) acrylic acid ester with respect to (meth) acrylic acid 100 by molar ratio. Is preferable, and 0.5 to 5 is particularly preferable. When a structural unit derived from AO is introduced, an AO adduct of (meth) acrylic acid ester and / or a (meth) acrylic acid AO adduct in molar ratio ( It is preferable to use 0 to 10 with respect to 100 of (meth) acrylic acid.

  The specific monomer molar ratio is 0.2 to 10 moles of methacrylic acid ester, preferably 0.5 to 5 moles per 100 moles of acrylic acid, and an AO adduct of (meth) acrylic acid ester and / or Or (meth) acrylic acid AO adduct 0-10 mol, Preferably it is 0.5-5 mol.

  In addition, the copolymer of (ii) (meth) acrylic acid and (meth) acrylic acid ester shall include the thing which esterified thru | or added AO after (meth) acrylic acid polymer later.

  Examples of the copolymer (ii) of (meth) acrylic acid and (meth) acrylic acid ester include commercially available products such as Carbopol ETD2020 manufactured by Noveon Inc. and Akpec HV501ER manufactured by Sumitomo Seika Co., Ltd. Product can be used. These can also use 2 or more types together.

  The content of the polyacrylic acid thickener in the composition is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 4% by mass, particularly preferably from the viewpoint of thickening and usability. It is 0.7-2.5 mass%.

  The polyacrylic acid thickener (i) or (ii) is preferably present in the cleaning composition as a salt with the alkali agent.

<Enzyme>
In the present invention, it is preferable to add an enzyme, and 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, everase, cannase, esperase, ovozyme (Novozymes Japan Co., Ltd.), plafect, propelase, and plafect OX (Genencore International).

  Examples of commercially available enzymes that can be used as amylases include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry Co., Ltd.), Plaster ST, Plaster OxAm (Genencor International). 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 1/99 to 94/6, more preferably 2/98 to 90/10, particularly preferably. 20/80 to 80/20.

  In the present invention, these enzymes are preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.03 to 0.3% by mass as enzyme protein in the composition. It is preferable to mix. An enzyme having a high stability in the liquid detergent is more preferably used.

  When an enzyme is blended in the present invention, an enzyme stabilizer is preferably blended in order to suppress enzyme deactivation in a neutral to weak alkaline aqueous solution containing an alkali agent.

  As the enzyme stabilizer, boric acid or one or more selected from boron compounds capable of forming boric acid, ethylene glycol, propylene glycol, glycerin, sorbitol, and water-soluble calcium salts are preferably blended.

  In the present invention, the enzyme stabilizer is preferably added in an amount of 0.001 to 50% by mass, more preferably 0.01 to 40% by mass, particularly preferably 1 to 40% by mass, and propylene glycol and / or glycerin and water. It is preferable to use a calcium salt together.

  The balance of the present invention is water. It is preferable to use ion exchange water. The composition of the present invention may be composed of only the above components, but in order to further improve the cleaning performance, a surfactant, a solvent, a low molecular chelating agent, a high molecular chelating agent can be blended, and others , Pigments, fragrances, antifoaming agents and ethanol can also be blended.

<Surfactant>
As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be blended. In particular, a nonionic surfactant can be blended from the viewpoint of cleaning performance. preferable.

  Nonionic surfactants include polyoxyethylene monoalkyl or monoalkenyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene monoalkyl or monoalkenyl ether, polyoxybutylene monoalkyl or monoalkenyl ether, alkylene oxide addition Among monoalkyl or monoalkenyl group-containing nonionic surfactant mixtures, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants and alkyl glycosides One or more selected from are preferred. More specific examples of such nonionic surfactants include the following (1) to (11).

  (1) Polyoxyethylene monoalkyl or monoalkenyl ethers, wherein the alkyl group or alkenyl group has an average carbon number of 10 to 20 and the average number of moles of ethylene oxide added is 1 to 30 mol.

  (2) Polyoxyethylene alkylphenyl ethers having an alkyl group having an average carbon number of 6 to 12 and an ethylene oxide addition mole number of 1 to 25 mol on average.

  (3) Polyoxypropylene monoalkyl or monoalkenyl ethers, wherein the alkyl group or alkenyl group has an average carbon number of 10 to 20, and the average number of propylene oxide additions is 1 to 20 mol.

  (4) Polyoxybutylene monoalkyl or monoalkenyl ethers, 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 only at one end, ethylene oxide and propylene oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.1) or ethylene oxide and butylene oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.1) ) Is a nonionic surfactant mixture in which the alkyl group or alkenyl group has an average carbon number of 10 to 20, and the average number of moles of alkylene oxide added per molecule is 1 to 30 moles. some stuff.

  (6) Higher fatty acid alkanolamides represented by the following general formula (A) or alkylene oxide adducts 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 H 2 or CH ₃ , p is a number of 1 to 3, q is 0 to 0 Is a number of 3.]

  (7) Sucrose fatty acid esters whose fatty acid moiety has an average carbon number of 10 to 20.

  (8) Fatty acid glycerin monoesters having an average number of carbon atoms in the fatty acid portion of 10 to 20.

  (9) Amine oxides. 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 (B).

In the general formula (6), R ²⁴ 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 ²⁵ and R ²⁶ are each an alkyl group having 1 to 3 carbon atoms, and a methyl group having 1 carbon atom is particularly preferable.

  (10) Alkyl polysaccharides. For example, an alkyl polysaccharide represented by the following general formula (C).

R ²⁷ (OR ²⁸ ) _x G _y (C)
[Wherein R ²⁷ represents a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ²⁸ represents an alkylene group having 2 to 4 carbon atoms, and G represents carbon. It is a residue derived from a reducing sugar having a number 5-6. x (average value) is 0-5, and y (average value) is 1-5. ]
A preferable value of x in the general formula (C) is 0 to 2, particularly preferably 0.

Moreover, the average value of y in the general formula (C) is 1 to 5, preferably 1 to 1.5, and more preferably 1.1 to 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.

  (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 preferable, and (1), (5), (9) and (11 ) Is particularly preferred.

  In this invention, the compounding quantity of surfactant is 10 mass% or less, it is not necessary to contain, and it is preferable that 0.005-10 mass% is mix | blended in a composition from the point of washing | cleaning performance, and more. Preferably it is 0.05-5 mass%.

<Solvent>
In the composition of the present invention, it is preferable that a polypropylene glycol having a weight average molecular weight of 600 to 20000, preferably 2000 to 10,000 is blended as a solvent in terms of cleaning effect and low foaming property. Polypropylene glycol is preferably blended in the composition in an amount of preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 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, it is preferable to use a surfactant in order to uniformly disperse it in the composition, and in particular, nonionic surfactants, especially (1), (5), (9) and ( It is preferable to use one or more selected from 10). From the viewpoint of dispersion stability and low foaming property, the mass ratio of polypropylene glycol / nonionic surfactant is preferably 90/10 to 10/90, more preferably 70/30 to 20/80, and particularly 60/40 to Preferably it is 30/70.

<Chelating agent>
In the present invention, the low molecular chelating agent is a water-soluble organic acid having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, or a salt thereof. In particular, it is preferable to blend a polyvalent carboxylic acid having 2 or more, preferably 2 to 6 carboxylic acid groups or a salt thereof in the molecule.

Specifically, carboxylic acid selected from formic acid, acetic acid, 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 Preferred are aminocarboxylic acids selected from diacetic acid, serine diacetic acid and aspartic acid diacetic acid, phosphonic acids selected from hydroxyethanediphosphonic acid and aminotrimethylenephosphonic acid, and alkali metals, alkaline earth metals or amine salts thereof. In particular, citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid and alkali metal salts or alkanolamine salts thereof are preferable.
In this invention, when mix | blending a chelating agent as a salt, as above-mentioned, it is necessary to restrict | limit the sodium ion density | concentration in a composition to below a specific density | concentration. It is only necessary to obtain a chelate agent other than a sodium salt, but if this is not possible, the chelate agent may be blended as an acid and neutralized in the system by blending an amine compound, potassium carbonate or potassium hydroxide. .
In the present invention, the chelating agent is counted as an acid form, and is preferably contained in the composition in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, particularly 1 to 10% by mass. .

  In the present invention, a polymer chelating agent can be blended. The polymer chelating agent is a non-polyacrylic acid thickener as described above, and a 0.2 mass% aqueous solution adjusted to pH 7.0 is prepared at 20 ° C. using a Brookfield viscometer (rotor No. 1, A compound having a viscosity of 50 mPa · s or less measured at a rotational speed of 60 r / m). The high-molecular chelating agent is different from the low-molecular chelating agent in that it is a compound having a weight average molecular weight of 1000 to 100,000. As the polymer chelating agent, it is preferable to use a polymer compound containing a monomer constituent unit having a carboxylic acid group, particularly those having a monomer constituent unit derived from an acrylic acid-based monomer and / or a maleic acid-based monomer. Acrylic acid, a copolymer of acrylic acid and maleic acid, and a copolymer of isobutylene or diisobutylene and maleic acid are preferred in terms of cleaning performance. The polymer chelating agent may be a salt, but the sodium ion concentration is limited, so the blending of sodium salt is limited. The polymer chelating agent is preferably added to the composition in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly 1 to 10% by mass.

  When a copolymer of acrylic acid and maleic acid is used as the polymer chelating agent, the molar ratio of acrylic acid / maleic acid is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 50 / A polymer compound of 50 to 80/20 is preferred.

  As with the low-molecular chelating agent, the high-molecular chelating agent is limited in sodium ions in the composition, and therefore, care should be taken when blended as a salt. However, some polymer chelating agents in acid form have poor solubility in water, so they can be formulated as potassium salts or amine compound salts, or as partially neutralized sodium salts in consideration of sodium restrictions. After dissolving, the composition may be prepared by blending potassium hydroxide or potassium carbonate.

  In the present invention, it is preferable to use a low-molecular chelating agent and a high-molecular chelating agent in combination as the chelating agent. , Preferably 0.1 to 3, more preferably 0.2 to 3, particularly preferably 0.3 to 2.

  In the present invention, citric acid is used as the low molecular chelating agent, and the weight average molecular weight as the high molecular chelating agent is 1,000 to 50,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 100. It is preferable to use a copolymer of acrylic acid and maleic acid, preferably 10,000 to 100,000. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.

<PH>
The liquid detergent composition of the present invention is obtained by adding a balanced amount of water to the components selected from the above-mentioned components in addition to the alkali agent and the polyacrylic acid-based thickener. From the viewpoint of irritation to eyes and skin and thickening, the pH at 25 ° C. is 8.0 to 11.0, preferably 9.0 to 11.0, particularly 9.5 to 10.8. . The pH is preferably adjusted with an aqueous potassium hydroxide solution. The pH is measured according to 7.2 (measurement method) of JIS Z 8802.

<Content of sodium ion>
The liquid detergent composition of the present invention has a sodium ion content of 1% by mass or less, preferably 0.8% by mass or less, particularly preferably 0.5% by mass or less, from the viewpoint of thickening.
<Viscosity>
The liquid detergent composition of the present invention is a Brookfield viscometer (rotor No. 3 when the viscosity is 4000 mPa · s or less, rotor 30 rpm when the viscosity exceeds 4000 mPa · s at 20 ° C. No. 4 and a viscosity measured at a rotation speed of 30 r / m) is preferably 500 mPa · s or more, more preferably 1000 to 8000 mPa · s, and particularly preferably 1500 to 4000 mPa · s. By setting the viscosity within the above range, when used as a cleaning agent for an automatic dishwasher having a detergent automatic inlet, the detergent does not leak out in the pre-washing process, and the usability is improved.

  The liquid detergent composition of the present invention is particularly suitable as a detergent for an automatic dishwasher. Examples of preferred embodiments of the present invention are shown below. In addition, it adjusts so that content of a sodium ion may be 1 mass% or less by selecting a raw material component.

<Alkaline agent>
1 to 7% by mass of an amine compound selected from monoethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol and 1 to 5% by mass of potassium hydroxide are blended.

<Polyacrylic acid thickener>
The polyacrylic acid-based thickener is a polymer having a molecular weight of 500,000 to 2,000,000 and the main constituent monomer is acrylic acid. ) 0.5-4 mass% of carboxy vinyl polymer containing acrylic acid ester is blended.
<Enzymes and enzyme stabilizers>
An enzyme mix | blends amylase and protease and the protein amount in a composition is 0.01-0.5 mass% in total. As an enzyme stabilizer, 0.01 to 40% by mass of one or more selected from ethylene glycol, propylene glycol and glycerin and 0.01 to 2% by mass of a water-soluble calcium salt are blended.

<Surfactant>
As the surfactant, polyoxyethylene monoalkyl or monoalkenyl ether, polyoxypropylene monoalkyl or monoalkenyl ether, having an alkyl group or alkenyl group only at one end, ethylene oxide and propylene oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.1) or a nonionic surfactant mixture in which ethylene oxide and butylene oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.1) are added, and the average carbon number of the alkyl group or alkenyl group is A nonionic surfactant selected from 10 to 20 and having an average number of moles of added alkylene oxide per molecule of 1 to 30 moles is blended in an amount of 0.05 to 5% by mass.

<Solvent>
As a solvent, 0-5 mass% of polypropylene glycol having a weight average molecular weight of 2000-4000 is blended.

<Chelating agent>
As a low molecular chelating agent, citric acid is 1 to 10% by mass, and as a polymer chelating agent, a copolymer of acrylic acid and maleic acid having a weight average molecular weight of 1,000 to 100,000 is 1 to 10% by mass. The ratio of the copolymer of citric acid / acrylic acid and maleic acid is blended at a mass ratio of 0.1 to 3

  A balanced amount of water is added to adjust the pH at 25 ° C. to preferably 9.0 to 11.0, and the viscosity measured by the above method at 20 ° C. to 1000 to 8000 mPa · s.

<Method for producing liquid detergent composition>
In the production method of the present invention, after the polyacrylic acid thickener and further other components to be blended as necessary are dissolved in water, the above-mentioned predetermined pH is obtained using an alkali agent (preferably potassium hydroxide). It is obtained by increasing the viscosity by adjusting. The content of sodium ions is adjusted to the predetermined value or less by selecting the raw material to be used.

<Leakage from automatic detergent inlet>
Washing machine used: Sanyo Electric Co., Ltd. automatic dishwasher (model DW-SA1) is used, and the liquid detergent composition shown in Table 1 is placed in the detergent automatic inlet, the lid is closed, and operation is performed on a standard course. did. This washing machine is of a type in which a pre-washing process of about 4 minutes is performed after the start of operation and then drained, and then water is newly poured, an automatic detergent inlet is opened, and a normal washing process is performed. .

With this model, after 4 minutes from the start of operation, the door of the cleaning machine was opened, the lid of the automatic detergent inlet was opened, and whether or not the cleaning composition remained was evaluated according to the following criteria. The results are shown in Table 1.
A: 90% or more of the cleaning composition remains.
○: 70% or more of the cleaning composition remains.
Δ: 50% or more of the cleaning composition remains.
X: Only 30% or less of the cleaning composition remains.

<Denatured protein stain cleaning performance>
Washing machine used: An automatic dishwasher (model NP-60SS6) manufactured by Matsushita Electric Industrial Co., Ltd. was used, and the following tableware and the detergent composition shown in Table 1 were put in and operated on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of the type that is dried after being warmed).
Contaminated dishes: 4 (prepared by the following method)
Water used: 3.5 g DH water detergent composition added amount: 6 g

<Preparation and evaluation method of contaminated dishes>
2 g of egg yolk was applied as uniformly as possible to a magnetic dish having a diameter of 23 cm, and the one denatured at 90 ° C. for 1 hour was used for washing. Measure the weight of the dish before contamination (M ₁ ), the weight of the dish before washing (M ₂ ), the weight of the dish before and after washing (M ₃ ), and calculate the washing rate by the following formula. The average value of the cleaning rate is shown in Table 1.
Washing rate (%) = (M ₂ −M ₃ ) / (M ₂ −M ₁ ) × 100

<Dispersion stability>
Put 200g of the detergent composition shown in Table 1 in a plastic transparent container (Family Fresh Container manufactured by Kao Corporation), store in a 50 ° C thermostatic bath for one week, observe the composition after storage, and change from before storage The case where there was no separation was evaluated as “◯”, and the case where separation was observed was evaluated as “×”.

(note)
1) Monoethanolamine 2) 2-Amino-2-methyl-1-propanol 3) ACPEC 501 (manufactured by Sumitomo Seika Co., Ltd.) (viscosity at 20 ° C., pH 7 and 0.2% is 7000 mPa · s) Stuff)
4) HEC Daicel SE850 (manufactured by Daicel Chemical Industries, Ltd.) (with a viscosity of 10 mPa · s at 20 ° C., pH 7 and 0.2%)
5) A polyoxyethylene alkyl ether obtained by adding an average of 3 moles of an oxyethylene group to a secondary higher alcohol having 12 alkyl atoms.
6) Polyoxyethylene alkyl ether obtained by adding an average of 4 moles of oxyethylene groups to a linear higher alcohol having 12 carbon atoms in the alkyl group.
7) 2-Ethylhexyl monoglyceryl ether 8) Weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
9) Sokaran CP45 (BASF) (number of moles of acrylic acid / number of moles of maleic acid = 70/30, weight average molecular weight 70,000, 20 ° C., pH 7 and 0.2%) Viscosity under the conditions of 3 mPa · s)
10) Duramil 300L (Novozymes Japan Co., Ltd.)
11) Everase 16L (Novozymes Japan K.K.)
12) Glycerin 13) Calcium chloride

Claims (5)

  Contains an alkali agent containing at least one selected from amine compounds, potassium hydroxide and potassium carbonate, a polyacrylic acid thickener and water, and has a pH of 8.0 to 11.0 at 25 ° C., sodium A thickened liquid detergent composition having an ion content of 1% by mass or less and a surfactant content of 10% by mass or less.   The thickened liquid detergent composition according to claim 1, wherein the viscosity at 20 ° C is 500 mPa · s or more.   The thickened liquid detergent composition according to claim 1 or 2, wherein the alkaline agent is a combination of an amine compound and one or more selected from potassium hydroxide and potassium carbonate.   The alkaline agent is a combination of monoethanolamine and one or more selected from potassium hydroxide and potassium carbonate, and the mass ratio of monoethanolamine / (potassium hydroxide + potassium carbonate) is 95/5 to 20/80. The thickened liquid detergent composition according to claim 3. It is a manufacturing method of the thickened liquid cleaning composition in any one of Claims 1-4, Comprising: The pH in 25 degreeC is adjusted to 8.0-11.0, and content of sodium ion is 1 The manufacturing method of the liquid detergent composition made to thicken by adjusting to mass% or less.