JP5329779B2 - Method for producing thickened liquid detergent composition - Google Patents

Description

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

  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 in a washing machine having an automatic detergent inlet, all or part of the detergent leaks in the pre-washing process, and the original cleaning performance cannot be obtained. For this reason, in Patent Documents 2 and 4, the liquid detergent composition is thickened using a polyacrylic acid-based thickener, and an appropriate yield value is set so that the detergent composition stays at the detergent automatic inlet. The technology to grant is disclosed.

  However, as in Patent Documents 2 and 4, the liquid detergent composition blended with a polyacrylic acid thickener exhibits good thickening and yield value with a small addition amount in weakly acidic to neutral, In order to enhance the cleaning performance, if a lot of chelating agents, dispersing agents, and alkali agents are blended to increase the pH, the viscosity is lowered. For this reason, in order to increase the viscosity, it is necessary to increase the amount of addition of the polyacrylic acid thickener itself, but this is technically difficult. There is no description about the technique regarding the manufacturing method of the cleaning composition which mix | blends an agent in high concentration.

  The subject of this invention is providing the manufacturing method of the thickened liquid cleaning composition which can mix | blend polyacrylic acid type | system | group thickener with high concentration.

As a means for solving the problems, the present invention contains a polyacrylic acid-based thickener, a thickened liquid detergent composition having a viscosity at 20 ° C. of 800 mPa · s or more and a pH at 25 ° C. of 8 or more. A method of manufacturing
a) Step of adding an organic acid and / or salt thereof to water so that the concentration thereof is 3% by mass or more and adjusting the pH at 25 ° C. to 5 or less b) Step of adding a polyacrylic acid thickener c ) A step of dispersing the polyacrylic acid thickener added in the previous step d) A step of adding another cleaning component and an alkaline agent for pH adjustment after vacuum defoaming as necessary,
A method for producing a thickened liquid detergent composition is provided.

  According to the production method of the present invention, it is possible to obtain a liquid detergent composition suitable for use in a thickened automatic dishwasher with a good appearance free from the thickening agent.

  The production method of the present invention includes steps a) to d), and a known production process of a cleaning composition can be appropriately added as necessary. Further, in the steps a) to d), two or more steps may be combined into one step, and one step may be divided into two or more steps.

<A) Process>
The step a) is performed such that the concentration of the organic acid and / or salt thereof is 3% by mass or more with respect to water placed in a suitable tank (treatment tank), and the pH at 25 ° C. is 5 or less. It is the process of adjusting to.

  The concentration of the organic acid and / or salt thereof is preferably 5% by mass or more, particularly preferably 8 to 20% by mass. In addition to the organic acid, an inorganic acid may be used. The pH is preferably 4.5 or less, particularly preferably 2 to 4. In the present invention, since the mass of the organic acid salt varies depending on the difference in counter ion, when the concentration is determined, it is converted as the acid type of the organic acid.

  When adding an organic acid and / or salt thereof to water, it is preferable to add the mixture with stirring using a disper or the like.

<B) Process>
Step b) is a step of adding a polyacrylic acid thickener.

  It is preferable to add the polyacrylic acid thickener little by little in a powder state. When adding the thickener, it is preferable to add the water in the tank with stirring using a disper, and in particular, the stirring blade of the stirrer is fixed near the center of the tank containing water and formed during stirring. It is preferable to add a thickener near the center of the vortex.

<C) Process>
Step c) is a step of dispersing the polyacrylic acid thickener added in step b).

  In step c), it is preferable to use a stirrer having a stirring blade during dispersion. Moreover, it is preferable to transfer the content in a tank to the tank suitable for the dispersion process of c) process after completion | finish of b) process. The tank used in the step c) has a circular cross-sectional shape in the width direction, and preferably has a diameter of 2 to 10 times the diameter of the stirring blade.

  When dispersing / dissolving with a stirrer, the peripheral speed of the stirring blade is preferably 10 m / sec or more, more preferably 10.5 m / sec or more, particularly 11 m / sec or more, and the upper limit is preferably 25 m / sec. Hereinafter, it is more preferable to stir at 20 m / sec or less. The stirring time is preferably 3 minutes or longer. The peripheral speed can be obtained from the following equation.

Peripheral speed = π ・ N / 60 ・ D
[Π: Circumferential ratio, N: Number of revolutions of stirring blade (r / m), D: Diameter of stirring blade (m)]

  The stirring blade of the stirrer is preferably a paddle type, a propeller type or the like. As the stirrer, a stirrer that can be dispersed in a shorter time by dispersing the thickener under high shear conditions is preferable. . 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.

  Steps b) and c) may be continuously processed as one step in the same processing tank. For example, after adding a polyacrylic acid thickener, it may be dispersed, or may be dispersed from the start of addition of the polyacrylic thickener, or while adding a polyacrylic thickener. , It may be dispersed from the middle. In addition, when continuously processing as such one process, for example, the size of the tank used when adding the polyacrylic acid thickener is also used when the polyacrylic thickener is dispersed. Try to select a suitable tank.

  c) The mass ratio of the organic acid and / or salt thereof to the polyacrylic acid thickener at the end of the step is that the organic acid salt is converted into an acid form, and then the organic acid / polyacrylic acid thickener = The ratio is preferably 95/5 to 50/50, more preferably 90/10 to 50/50, and particularly preferably 90/10 to 70/30. The above range is preferable because when the polyacrylic acid thickener is blended at a high concentration, the increase in viscosity is suppressed, the stirring efficiency is increased, and the occurrence of lumps is suppressed.

<D) Process>
Step d) is a step of adding other cleaning components and an alkaline agent for pH adjustment after vacuum degassing as necessary.

  The vacuum defoaming is a process of removing bubbles mixed in the thickener dispersing step by lowering the pressure in the tank by reducing the pressure. The preferable pressure in the tank is -40 kPa or less, more preferably -60 kPa or less, and particularly preferably -80 kPa or less.

  The vacuum defoaming treatment can be repeated for one cycle or two or more cycles, with the operation of defoaming under reduced pressure over 1 to 10 minutes, returning to normal pressure, and depressurizing again under one cycle. It is preferable to repeat 3 to 10 cycles with one vacuum defoaming.

  In addition, the dispersion | distribution process of the polyacrylic acid type | system | group thickener of c process and the vacuum defoaming process of d) process can be made parallel. Moreover, the tank (processing tank) used in each process may be the same, and may differ for every process.

  After the steps a) to c) and the vacuum defoaming treatment are completed, the pressure in the tank is returned to normal pressure, and other cleaning components and an alkaline agent for pH adjustment are added. Examples of the other cleaning components include known surfactants, solvents, enzymes, enzyme stabilizers, and fragrances. At this time, after adding a part of the cleaning component (including the surfactant) and the alkali agent, stirring and mixing, vacuum defoaming again, and further adding the remaining cleaning component (including the surfactant) and the alkali agent And can be mixed with stirring. For example, the fragrance is preferably added after completion of the second vacuum defoaming in order to prevent odor deterioration, and the enzyme is preferably added after the second vacuum defoaming is completed in order to maintain the activity.

  For the stirring, it is preferable to use a stirrer having a stirring blade as used in step c). At the time of stirring, it is preferable to set the peripheral speed of the stirring blade to 10 m / sec or less in order to prevent mixing of bubbles due to stirring. More preferably, it is 9.5 m / sec or less, and particularly preferably 9 m / sec or less.

Hereinafter, components used in the method for producing the liquid detergent composition of the present invention will be described.
<Organic acid and / or salt thereof>
The organic acid and / or salt used in the production method of the present invention is a compound that does not exhibit thickening, such as a polyacrylic acid thickener described later, specifically, 0.2 mass adjusted to pH 7.0. % Aqueous solution is a compound having a viscosity of 50 mPa · s or less measured at 20 ° C. with a Brookfield viscometer (rotor No. 1, rotation speed 60 r / m). Such an organic acid or a salt thereof is a water-soluble organic acid or a salt thereof having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, particularly two or more, preferably 2 to 2 in the molecule. It is preferable to blend a polyvalent carboxylic acid having 6 carboxylic acid groups or a salt thereof.

  Examples of those having a molecular weight of 40 to 400 include 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 Aminocarboxylic acids selected from diacetic acid, glutamic acid diacetic acid, serine diacetic acid and aspartic acid diacetic acid, phosphonic acids selected from hydroxyethanediphosphonic acid and aminotrimethylenephosphonic acid, and their alkali metals, alkaline earth metals or Amine salts are preferred, especially citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid and their alkali metal salts, alkaline earth metal salts or alkanolamine salts.

Moreover, in addition to the low molecular weight organic acid and / or salt, a high molecular weight organic acid and / or salt may be added.
As the polymer having a high molecular weight, it is preferable to use a polymer compound containing a monomer structural unit having a carboxylic acid group having a weight average molecular weight of 1,000 to 100,000, particularly an acrylic acid monomer and / or a maleic acid monomer. Those having a monomer constitution unit derived from polyacrylic acid, acrylic acid and maleic acid copolymer, isobutylene or diisobutylene and maleic acid copolymer and their alkali metal salts, alkaline earth metal salts or Alkanolamine salts are preferred in terms of cleaning performance.
The weight average molecular weight can be measured by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance.

  When a copolymer of acrylic acid and maleic acid is used as the high molecular weight organic acid and / or salt, the molar ratio of acrylic acid / maleic acid is 10/90 to 90/10, preferably 20/80 to 80/20, More preferably 50/50 to 80/20.

  In the present invention, as the organic acid and / or salt, it is preferable to use a low molecular weight and a high molecular weight in combination, and the mass ratio of the low molecular weight / high molecular weight is preferably 0.1 to 3 as the acid type. 0.2 to 3 is preferable, and 0.3 to 2 is particularly preferable.

  In the manufacturing method of this invention, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, can be used with an organic acid and / or a salt.

<Polyacrylic acid thickener>
The polyacrylic acid thickener used in the production method of the present invention 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.

  The polyacrylic acid thickener is one or more selected from (i) a crosslinked (meth) acrylic acid polymer and (ii) a copolymer of (meth) acrylic acid and (meth) acrylic acid ester. Can be used. These thickeners are preferably present in the liquid detergent composition as a salt with an alkaline agent.

  (I) Cross-linked (meth) acrylic acid polymer is (meth) acrylic acid homopolymer or copolymer of (meth) acrylic acid and other vinyl carboxylic acid compound with a polyol compound. As described above, the carboxy group is cross-linked by esterification. Regarding the degree of crosslinking, it is preferable that (meth) acrylic acid esterified with a crosslinking agent at a ratio of less than 0.1 with respect to acrylic acid structural unit 100 in a molar ratio. In particular, in (i), a crosslinked product of acrylic acid homopolymer is most preferable.

  (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.

  As such a crosslinked (meth) acrylic acid polymer, those usually used in cosmetics and pharmaceutical external preparations can be used without limitation. For example, Carbopol 980 manufactured by Noveon Inc. Commercial products such as Carbopol 981, Akpec HV501E and HV505E manufactured by Sumitomo Seika Co., Ltd. can be used. These can also use 2 or more types together.

  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.

  The copolymer (ii) may contain a structural unit derived from an alkylene oxide having 2 to 4 carbon atoms (hereinafter referred to as AO). As AO, ethylene oxide, propylene oxide, preferably ethylene oxide is used. Can be mentioned. 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.

The copolymer of (ii) (meth) acrylic acid and (meth) acrylic acid ester may be a product obtained by esterification or AO addition of a (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.

  In the composition obtained by the production method of the present invention, the content of the polyacrylic acid-based thickener is preferably 0.5 to 5% by mass, more preferably 0.7 to 4 in terms of thickening and usability. It is mass%, Most preferably, it is 0.7-2.5 mass%.

<Alkaline agent>
Examples of the alkali agent used in the production method of the present invention include alkanolamine, potassium hydroxide, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, borax, sodium silicate and the like.

When an amine compound is used as the alkali agent, amine compounds represented by the following general formulas (1) to (4) are preferable, and among these, monoethanolamine, diethanolamine, 2-amino-2-methyl-1- Propanol and morpholine are preferred, and monoethanolamine is particularly preferred.

(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).

  In the composition obtained by the production method of the present invention, the content of the alkaline agent is blended in order to obtain a predetermined pH from the viewpoint of cleaning performance, but the specific blending amount is preferably 0.1 to 0.1. 30 mass%, More preferably, it is 1-2 mass%, Most preferably, it is 3-10 mass%.

<Surfactant>
The surfactant used in the production method of the present invention exhibits sufficient water-solubility or water-dispersibility, and particularly when used in an automatic dishwasher, a surfactant that does not generate excessive bubbles is preferable. Specifically, polyoxyethylene monoalkyl or monoalkenyl 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, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants and alkyl glycosides, alkyl glyceryl ethers One or more nonionic surfactants selected from among them are preferred.

（一般式（I）中、
ｍ及びｎは独立して２〜８の整数（好ましくは４〜７の整数）であり、ｍ+ｎは４〜１６の整数（好ましくは８〜１４の整数）であって、ｍ及びｎから構成されるアルキル基の平均炭素数が６〜１６（好ましくは８〜１４）である；
ｋは平均２〜１９（好ましくは平均２〜１０）であり、ｌは平均０〜１０（好ましくは平均０〜３）である；
なお、式中の「／」は、オキシエチレン基及びオキシプロピレン基が、ブロック付加又はランダム付加のいずれでもよいことを意味する。 Among these nonionic surfactants, one or more of primary and secondary alcohol alkoxylate type nonionic surfactants represented by the following general formulas (I) and (II) are preferable.

(In general formula (I),
m and n are each independently an integer of 2 to 8 (preferably an integer of 4 to 7), m + n is an integer of 4 to 16 (preferably an integer of 8 to 14), and m and n The average alkyl number of the alkyl group is 6 to 16 (preferably 8 to 14);
k is an average of 2 to 19 (preferably an average of 2 to 10), and l is an average of 0 to 10 (preferably an average of 0 to 3);
In the formula, “/” means that the oxyethylene group and the oxypropylene group may be either block addition or random addition.

In general formula (II),
R is an alkyl group having an average carbon number of 12 to 20 (preferably an average carbon number of 12 to 14), p is an average of 2 to 15 (preferably an average of 2 to 10), and q is an average of 0 to 10 (preferably Average 0-3).
In addition, “/” in the formula means that the oxyethylene group and the oxypropylene group may be either block addition or random addition).

  The nonionic surfactants represented by the general formulas (I) and (II) are preferably used in combination. In the case of using these in combination, the mass ratio of general formula (I) / general formula (II) is preferably 90/10 to 10/90, more preferably 90, including those contained in the mixture with the fragrance. / 10 to 30/70, more preferably 80/20 to 40/60.

  In the composition obtained by the production method of the present invention, the content of the surfactant is preferably 10% by mass or less, and from the viewpoint of cleaning performance and low foaming property, more preferably 0.005 to 0.005 in the composition. It is preferable that it is 10 mass%, especially 0.05-5 mass%.

<Enzyme>
The composition obtained by the production method of the present invention preferably contains an enzyme, and examples include cellulase, protease, lipase, amylase, esterase, pectinase, lactase, and peroxidase, and protease and amylase are particularly preferable. is there.

  Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, everase, cannase, esperase, ovozyme (Novozymes Japan Co., Ltd.), Pract, Properase, and Plast 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.

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

  As an enzyme stabilizer, boric acid or a boron compound capable of forming boric acid, ethylene glycol, propylene glycol, glycerin, sorbitol, water-soluble calcium salt, sodium nitrite is added. In particular, propylene glycol and / or glycerin and a water-soluble calcium salt are preferably used in combination.

  In the composition obtained by the production method of the present invention, the content of the enzyme stabilizer is preferably 0.001 to 50% by mass, more preferably 0.01 to 45% by mass, and particularly 1 to 45% by mass. .

<Solvent>
In the production method of the present invention, it is preferable to blend polypropylene glycol having a weight average molecular weight of 600 to 20000, preferably 2000 to 10,000 as a solvent from the viewpoint of cleaning effect and low foamability. 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.).

  In the composition obtained by the production method of the present invention, the content of polypropylene glycol is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 3% by mass. It is.

  In the production method of the present invention, sorbitol, a pigment, a fragrance, an antifoaming agent, ethanol and the like can be further blended as necessary.

<Viscosity>
The liquid detergent composition obtained by the production method of the present invention has a Brookfield viscometer at 20 ° C. (when the viscosity is 4000 mPa · s or less, rotor No. 3, rotation speed 30 r / m, viscosity is 4000 mPa · s). In this case, the viscosity measured by the rotor No. 4 and the rotation speed of 30 r / m is 800 mPa · s or more, more preferably 1000 to 8000 mPa · s, and particularly preferably 1500 to 4000 mPa · s. By using the viscosity range, when used as a cleaning agent for an automatic dishwasher, when used for an automatic tableware having an automatic detergent inlet, the detergent does not leak out in the prewashing process, and the usability is improved. .

<PH>
The liquid detergent composition obtained by the production method of the present invention is composed of the above components and a balanced amount of water, but the pH at 25 ° C. is 8 or more from the viewpoint of cleaning performance and irritation to eyes and skin. , 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.

Example 1
a) Process T. of PRIMIX Co., Ltd. K. Water, organic acid (salt of citric acid and acrylic acid / maleic acid copolymer) and calcium chloride were added to the mixing tank equipped with the homodisper at the mass ratio shown in Table 1, and the peripheral speed was 11 m / s. Stir to dissolve. The pH at 25 ° C. was 3.

b) Process The polyacrylic acid type | system | group thickener was added little by little, stirring at a peripheral speed of 11 m / s with a homodisper. After completion of the addition, stirring was continued for 5 minutes at the same peripheral speed, and then the entire amount was transferred to a prime homogenizer tank of Ajihomomica.

c) Process Next, it stirred for 5 minutes with the peripheral speed of 16 m / s of the stirring blade with the azimuthal mixer, and the thickener was disperse | distributed. c) The total concentration of the organic acid at the end of the process was 12.8% by mass, the mass ratio of the organic acid to the polyacrylic acid thickener was 83/17, and the dispersibility of the thickener was good. It was.

d) Step Next, the pressure in the tank was set to -95 kPa, and bubbles mixed in by vacuum defoaming were removed. Subsequently, the pressure in the tank was returned to normal pressure, and glycerin, surfactant-1, surfactant-2, polypropylene glycol, monoethanol while stirring at a peripheral speed of 8.5 m / s with an azimuthomixer. A liquid detergent composition in which amine, potassium hydroxide, α-amylase, and protease are added in this order, and finally, a surfactant-1 and a fragrance previously dissolved in a mass ratio of 80/20 are added to increase the viscosity. I got a thing. The resulting cleaning composition was in a good blending state, the viscosity at 20 ° C. was 2500 mPa · s, and the pH at 25 ° C. was 10.

Comparative Example 1
a) Process T. of PRIMIX Co., Ltd. K. Water, citric acid and calcium chloride were added to the blending tank equipped with the homodisper at a mass ratio shown in Table 1, and dissolved by stirring at a peripheral speed of 11 m / s of the stirring blade. The pH at 25 ° C. was 3.

b) Process The polyacrylic acid type | system | group thickener was added little by little, stirring at a peripheral speed of 11 m / s with a homodisper. After completion of the addition, stirring was continued for 5 minutes at the same peripheral speed, and then the entire amount was transferred to a prime homogenizer tank of Ajihomomica.

c) Process Next, it stirred for 5 minutes with the peripheral speed of 16 m / s of the stirring blade with the azimuthal mixer, and the thickener was disperse | distributed. c) The concentration of citric acid at the end of the process was 3.1% by mass, the mass ratio of citric acid to polyacrylic acid thickener was 48/52, and the dispersibility of the thickener was somewhat poor. It was.

d) Step Next, the pressure in the tank was set to -95 kPa, and bubbles mixed in by vacuum defoaming were removed. Subsequently, the pressure in the tank was returned to normal pressure, and glycerin, surfactant-1, surfactant-2, polypropylene glycol, monoethanolamine while stirring with an azimuthommixer at a peripheral speed of 8.5 m / s. , Potassium hydroxide, α-amylase and protease are added in this order, and finally the surfactant-1 and the fragrance are dissolved in advance at a mass ratio of 80/20, and the liquid detergent composition is thickened. Got. The blending state of the resulting cleaning composition was somewhat poor, and the exact viscosity and pH could not be measured.

Comparative Example 2
a) Process T. of PRIMIX Co., Ltd. K. Water, organic acid (citric acid and acrylic acid / maleic acid copolymer salt), calcium chloride and monoethanolamine were added to the mixing tank equipped with the homodisper in the mass ratio shown in Table 1, and the stirring blade The solution was stirred and dissolved at a peripheral speed of 11 m / s. The pH at 25 ° C. was 5.5.

b) Process The polyacrylic acid type | system | group thickener was added little by little, stirring at a peripheral speed of 11 m / s with a homodisper. After completion of the addition, stirring was continued for 5 minutes at the same peripheral speed, and then the entire amount was transferred to a prime homogenizer tank of Ajihomomica.

c) Step Next, the azihomomoxer was stirred for 5 minutes at a peripheral speed of the stirring blade of 16 m / s to disperse the thickener. c) The total concentration of the organic acid at the end of the process was 12.3% by mass, the mass ratio of the organic acid to the polyacrylic acid thickener was 83/17, and the dispersibility of the thickener was poor. It was.

d) Step Next, the pressure in the tank was set to -95 kPa, and bubbles mixed in by vacuum defoaming were removed. Subsequently, the pressure in the tank was returned to normal pressure, and glycerin, surfactant-1, surfactant-2, polypropylene glycol, monoethanolamine while stirring with an azimuthommixer at a peripheral speed of 8.5 m / s. , Potassium hydroxide, α-amylase and protease are added in this order, and finally the surfactant-1 and the fragrance are dissolved in advance at a mass ratio of 80/20, and the liquid detergent composition is thickened. Got. The blending state of the resulting cleaning composition was poor, and the exact viscosity and pH could not be measured.

Comparative Example 3
a) Process T. of PRIMIX Co., Ltd. K. Water, citric acid and calcium chloride were added to the blending tank equipped with the homodisper at a mass ratio shown in Table 1, and dissolved by stirring at a peripheral speed of 11 m / s of the stirring blade. The pH at 25 ° C. was 3.5.

b) Process The polyacrylic acid type | system | group thickener was added little by little, stirring at a peripheral speed of 11 m / s with a homodisper. After completion of the addition, stirring was continued for 5 minutes at the same peripheral speed, and then the entire amount was transferred to a prime homogenizer tank of Ajihomomica.

c) Step Next, the azihomomoxer was stirred for 5 minutes at a peripheral speed of the stirring blade of 16 m / s to disperse the thickener. c) The concentration of citric acid at the end of the process is 2.4% by mass, the mass ratio of citric acid to polyacrylic acid thickener is 52/48, and the dispersibility of the polyacrylic acid thickener is Somewhat bad.

d) Step Next, the pressure in the tank was set to -95 kPa, and bubbles mixed in by vacuum defoaming were removed. Subsequently, the pressure in the tank was returned to normal pressure, and glycerin, surfactant-1, surfactant-2, polypropylene glycol, monoethanolamine while stirring with an azimuthommixer at a peripheral speed of 8.5 m / s. , Potassium hydroxide, α-amylase and protease are added in this order, and finally the surfactant-1 and the fragrance are dissolved in advance at a mass ratio of 80/20, and the liquid detergent composition is thickened. Got. The blending state of the resulting cleaning composition was somewhat poor, and the exact viscosity and pH could not be measured.

<C) Dispersibility of polyacrylic acid thickener at the end of the process>
○: There is no formation of lumps in the contents in the tank (dispersibility is good).
Δ: Several lumps are formed in the contents in the tank (dispersibility is slightly poor).
X: Numerous lumps are formed in the contents in the tank (dispersibility is poor).

表１中、中間工程での割合は、ａ）工程終了時の各成分の含有割合（質量％）、ｂ）工程終了時の各成分の含有割合（質量％）を示し、ｄ）工程終了時の各成分の割合は、最終的に得られた液状洗浄剤組成物中の各成分の割合を意味する。よって、ａ）工程の組成物中の割合、ｂ）工程の組成物中の割合、ｄ）工程の割合を合計すると、１００質量％となる。 <Formulation state of liquid detergent composition>
○: There is no mixing of lumps in the composition (the blending condition is good).
(Triangle | delta): A little lumps are mixed in in a composition (a mixing | blending state is somewhat bad).
X: A large amount of lumps are mixed in the composition (the blending state is poor).

In Table 1, the ratio in the intermediate process indicates a) the content ratio (mass%) of each component at the end of the process, b) the content ratio (mass%) of each component at the end of the process, and d) at the end of the process. The ratio of each component means the ratio of each component in the finally obtained liquid detergent composition. Therefore, the sum of the proportion in the composition of the step a), the proportion in the composition of the step b), and the proportion of the step d) is 100% by mass.

(note)
1) Socalane CP45 (BASF Corporation) (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)
2) Akpek 501 (manufactured by Sumitomo Seika Co., Ltd.) (with a viscosity of 7000 mPa · s at 20 ° C., pH 7 and 0.2%)
3) 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.
4) A polyoxyethylene alkyl ether obtained by adding an average of 4 moles of an oxyethylene group to a linear higher alcohol having 12 carbon atoms in an alkyl group.
5) Weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
6) Duramil 300L (Novozymes Japan Co., Ltd.)
7) Everase 16L (Novozymes Japan K.K.)
8) A fragrance containing 70% d-limonene

Claims (7)

A method for producing a thickened liquid detergent composition containing a polyacrylic acid-based thickener, having a viscosity at 20 ° C. of 800 mPa · s or more and a pH at 25 ° C. of 8 or more,
a) Step of adding an organic acid and / or a salt thereof to water so that the concentration becomes 3% by mass or more and adjusting the pH at 25 ° C. to 5 or less b) Step of adding a polyacrylic acid thickener c ) A step of dispersing the polyacrylic acid thickener added in the previous step d) A step of adding another cleaning component and an alkaline agent for pH adjustment after vacuum defoaming as necessary,
A method for producing a thickened liquid detergent composition comprising :
The organic acid and / or salt is a compound having a viscosity of 50 mPa · s or less measured at 20 ° C. in a 0.2 mass% aqueous solution adjusted to pH 7.0,
As the organic acid and / or salt thereof, a monomer structural unit having a low molecular weight organic acid and / or salt thereof having a molecular weight of 40 to 400 and a carboxylic acid group having a weight average molecular weight of 1,000 to 100,000. In combination with a high molecular weight organic acid and / or a salt thereof, which is a polymer compound containing
The polyacrylic acid-based thickener is a thickening polymer compound having a viscosity of 500 mPa · s or more measured at 20 ° C. with a 0.2 mass% aqueous solution adjusted to pH 7.0,
A manufacturing method in which steps a) to d) are performed in this order .   c) The mass ratio of the organic acid and / or salt thereof to the polyacrylic acid thickener at the end of the step is organic acid / polyacrylic acid thickener = 95/5 to 50/50. A method for producing a thickened liquid detergent composition as described. The low molecular weight organic acid having a molecular weight of 40 to 400 and / or a salt thereof is formic acid, acetic acid, gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, ethylenediaminetetraacetic acid, From diethylenetriaminepentaacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, serine diacetic acid, aspartic acid diacetic acid, hydroxyethanediphosphonic acid, and aminotrimethylenephosphonic acid, and their alkali metals, alkaline earth metals, or amine salts The manufacturing method of the thickened liquid cleaning composition of Claim 1 or 2 which is 1 or more types chosen. The polymer compound containing a monomer structural unit having a carboxylic acid group having a weight average molecular weight of 1,000 to 100,000 is a copolymer of polyacrylic acid, acrylic acid and maleic acid, isobutylene or diisobutylene and maleic acid. The production of the thickened liquid detergent composition according to any one of claims 1 to 3, which is at least one selected from copolymers and alkali metal salts, alkaline earth metal salts, or alkanolamine salts thereof. Method. The manufacturing method of the thickened liquid cleaning composition in any one of Claims 1-4 whose content of the said polyacrylic acid type | system | group thickener is 0.5-5 mass%. The polyacrylic acid thickener is one or more selected from (i) a crosslinked (meth) acrylic acid polymer, and (ii) a copolymer of (meth) acrylic acid and (meth) acrylic acid ester. The method for producing a thickened liquid detergent composition according to any one of claims 1 to 5. It is a manufacturing method of the cleaning composition for automatic dishwashers, The manufacturing method of the thickened liquid cleaning composition in any one of Claims 1-6 .