JP2009013325A - Method for producing liquid detergent composition for automatic dishwasher - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a liquid detergent composition for an automatic dishwasher, in which composition perfume is mixed stably but air bubble is not mixed and which composition has an excellent external appearance and is thickened. <P>SOLUTION: The method for producing the liquid detergent composition for the automatic dishwasher, which composition contains a nonionic surfactant, perfume, a thickener and water and has ≥800 mPa s viscosity at 20 °C, comprises: a step (a) of adding the thickener to water; a step (b) of dispersing the thickener in the water by rotating an agitation blade of an agitator at >10 m/sec circumferential speed; a step (c) of defoaming the thickener-dispersed water in vacuum; and a step (d) of adding a mixture, which is obtained by mixing the nonionic surfactant with the perfume by the mass ratio of 90/10 to 50/50, to the defoamed thickener-dispersed water and then mixing the mixture-added thickener-dispersed water by rotating the agitation blade of the agitator at ≥10 m/sec circumferential speed without defoaming in vacuum the mixture-added thickener-dispersed water. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  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 such a washing machine with powder detergent while the tableware is excessively packed, there may be a problem that the powder detergent remains undissolved in the tableware or in the gaps 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, when blending the thickeners described in Patent Documents 2 and 4, it is necessary to disperse with high resilience, so that a large amount of air bubbles are mixed into the cleaning composition during dispersion. When vacuum defoaming is performed to remove bubbles mixed in a large amount, the bubbles can be removed, but there is a problem that the odor deteriorates due to volatilization of a part of the fragrance. Further, such a problem does not occur in a detergent composition having a large amount of surfactant such as a general kitchen detergent or a detergent composition having a low viscosity in which bubbles generated by stirring can be removed at normal pressure.

  Patent Documents 2 and 3 do not describe a technique for blending a fragrance uniformly and stably and preventing air bubbles from being mixed.

  An object of the present invention is to provide a production method capable of obtaining a liquid detergent composition for an automatic dishwasher having a good appearance and capable of stably blending a fragrance and free of bubbles. It is to provide.

As a means for solving the problems, the present invention provides a liquid detergent composition for an automatic dishwasher comprising a nonionic surfactant, a fragrance, a thickener and water and having a viscosity at 20 ° C. of 800 mPa · s or more. A manufacturing method comprising:
a) Step of adding a thickener to water b) Step of dispersing the thickener in water at a peripheral speed of the stirring blade of the stirrer exceeding 10 m / sec c) Step of vacuum defoaming d) Nonionic surfactant and A step of mixing at a peripheral speed of 10 m / sec or less of a stirring blade of a stirrer without adding vacuum, after adding a mixture of a mass ratio of fragrance 90/10 to 50/50,
A method for producing a liquid detergent composition for an automatic dishwashing machine is provided.

  According to the production method of the present invention, it is possible to stably add a fragrance without reducing the odor, and to obtain a liquid detergent composition for an automatic dishwasher having a good appearance and free of bubbles. Can do.

  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>
a) A process is a process of adding a thickener with respect to the water put in the suitable tank (treatment tank). It is preferable to add the 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. In this step, it is preferable to adjust the pH at 25 ° C. to 5 or less with an organic acid or an inorganic acid.

<B) Process>
The step b) is a step of dispersing and dissolving a part or all of the thickener added to the water in the tank.

  In step b), it is preferable to use a stirrer having a stirring blade during dispersion and dissolution. In addition, after the completion of the step a), it is preferable to transfer the contents in the tank to a tank suitable for the dispersion and dissolution treatment in the step b), but in the step a) in advance, suitable for the dispersion and dissolution treatment in the step b). A tank can also be used. The tank used in the step b) preferably has a circular cross-sectional shape in the width direction and 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 set to more than 10 m / sec, preferably 10.5 m / sec or more, more preferably 11 m / sec or more. The upper limit of the peripheral speed of the stirring blade is preferably 25 m / sec or less, more preferably 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, in particular, those capable of dispersing in a shorter time by performing the dispersion of the thickener under high shear conditions are preferable. In a batch system, the azimumixer of Primix Co., Ltd., T.A. 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.

<C) Process>
The vacuum defoaming in step c) is a step of removing bubbles mixed in step b) by lowering the pressure in the tank by reducing the pressure.

  The degree of decompression in the tank is preferably −40 kPa or less, more preferably −60 kPa or less, and particularly preferably −80 kPa or less.

  c) The defoaming treatment in the step 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. In this invention, it is preferable to repeat 3-10 cycles by one vacuum defoaming.

  In the processes of steps a) to c), the steps a) and b) may be performed in parallel, or the steps b) and c) may be performed in parallel. Moreover, the tank (processing tank) used in each process may be the same, and may differ for every process.

<D>Process>
After the steps a) to c), the pressure in the tank is returned to normal pressure, and a nonionic surfactant and a fragrance are added.

  The nonionic surfactant and the fragrance are added in a mass ratio of 90/10 to 50/50, more preferably 90/10 to 60/40, and particularly 85/15 to 70/30. By mixing the nonionic surfactant and the fragrance after mixing in this range, even when stirring at a gentle peripheral speed so that bubbles do not occur, the fragrance should be blended uniformly and stably in the composition. Can do.

In addition, the nonionic surfactant can be added by mixing the whole amount with the fragrance, but only a part of the nonionic surfactant is mixed with the fragrance, and the remainder is not mixed with the fragrance but added separately from the fragrance. Can do. At this time, in the total amount of the nonionic surfactant, the ratio of the mixture added with the fragrance is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. .

  After the fragrance is added, the mixture is stirred without vacuum degassing in order to prevent the fragrance from deteriorating. In order to prevent mixing of bubbles due to stirring, stirring is performed at a peripheral speed of the stirring blade of the stirrer of 10 m / sec or less, preferably 9.5 m / sec or less, particularly 9 m / sec or less, and the lower limit is preferably 3 m. / Sec or more, preferably 5 m / sec.

  In addition to the thickener, the nonionic surfactant and the fragrance component, the liquid detergent composition produced by the production method of the present invention includes other cleaning components (nonionic surfactant not mixed with the fragrance). Included). Other washing components can be added between any two steps a) to d), between any two steps a) to d), or after step d). When other cleaning ingredients other than the perfume are added between step c) and step d) (that is, before step d)), if necessary before the addition of the perfume, a second vacuum defoaming is necessary. You may do.

Hereinafter, components used in the method for producing the liquid detergent composition of the present invention will be described.
<Nonionic surfactant>
The nonionic surfactant used in the production method of the present invention exhibits sufficient water-solubility or water-dispersibility and does not generate excessive foam even when used in an automatic dishwasher, and is added to tap water at 50 ppm. When the dishwasher (NP-C10 manufactured by Matsushita Electric Industrial Co., Ltd.) is operated on a standard course, the number of rotations of the washing nozzle is 65% or more of the number of rotations when operated only with water.

  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 a mixture of monoalkenyl group-containing nonionic surfactants, 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 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, since the blending stability of the fragrance can be further improved, the primary and secondary alcohol alkoxylate type nonions represented by the following general formulas (I) and (II) One or more surfactants are preferred.

(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 nonionic surfactant is preferably 10% by mass or less, more preferably 0.005 to 10 from the viewpoint of cleaning performance and low foamability. It is preferable that it is mass%, especially 0.05-5 mass%.

<Thickener>
Examples of the thickener used in the production method of the present invention include pectin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid ester, polyacrylic acid. Water-soluble polymers such as system thickeners, xanthan gum, guar gum, locust bean gum, gelatin, sodium alginate, gum arabic and starch, and water-swellable clay minerals such as smectite are preferred. The thickener is preferably present in the cleaning composition as a salt with an alkali agent described later.

  Any of natural and synthetic smectites can be used, but those having a glassy content, feldspar, quartz, mica, calcium sulfate, calcium carbonate, manganese carbonate or the like are preferably 5% by mass or less. Preferred smectites include natural or synthetic colloidal silicates such as dioctahedral montmorillonite, beidellite, nontroit and the like, or trioctahedral saponite, hectorite, stevensite and the like. Among them, hectorite is preferable, and examples include Laponite series manufactured by Laporte, Kunipia manufactured by Kunimine Industries, and Smecton manufactured by Corp Chemical.

  Of these, polyacrylic acid thickeners are preferred from the viewpoint of thickening and storage stability. 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.

  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 thickener is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, from the viewpoint of thickening and usability. Especially preferably, it is 0.7-2.5 mass%.

<Fragrance>
The fragrance used in the production method of the present invention preferably contains a terpene hydrocarbon fragrance in an amount of 40% by mass or more, preferably 50% by mass or more, particularly 60% by mass or more.

  The terpene hydrocarbon is an unsaturated hydrocarbon polymerized with isoprene, and an unsaturated hydrocarbon or saturated hydrocarbon (hereinafter referred to as a hydrocarbon terpene compound) having the same skeleton, and further includes a hydroxy group and a ketone group. Further, alcohol compounds having an ester group bonded thereto (hereinafter referred to as alcohol-based terpene compounds), ketone compounds, and ester compounds are also included in the terpene compounds. Also included are isoprene polymerization degrees of two monoterpenes, three sesquiterpenes, and four diterpene compounds.

  Among the terpene hydrocarbons, the terpene hydrocarbon fragrance is preferably a saturated or unsaturated chain or cyclic hydrocarbon monoterpene compound, or a saturated or unsaturated chain or cyclic alcohol monoterpene compound, Specifically, α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene hydrocarbon terpene compound, linalool, geraniol, nerol, citronellol, hydroxycitronellol, tetrahydrolinalool, myrsenol, terpineol, menthol, borneol Alcohol-based terpene compounds that are isopulegol are preferred.

<Alkaline agent>
In the production method of the present invention, an alkaline agent can be blended. Examples of the alkali agent include alkanolamine, potassium hydroxide, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, borax, sodium silicate and the like.

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

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).

  Among these, the compound represented by the general formula (1) is preferable, and specifically, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, and morpholine are preferable, and monoethanolamine is particularly preferable.

<Enzyme>
In the production method of the present invention, it is preferable to mix 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.

  When an enzyme is blended in the production method of 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 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. Is preferred. In particular, it is preferable to use propylene glycol and / or glycerin and a water-soluble calcium salt 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 preferably 1 to 45% by mass. It is.

  The composition of the present invention is a liquid containing water, and it is preferable to use ion-exchanged water. The composition of the present invention may be composed of only the above components, but in order to further improve the cleaning performance, surfactants other than the above-described nonionic surfactants, solvents, low molecular chelating agents, high molecular chelating agents In addition, pigments, antifoaming agents, and ethanol can also be blended.

<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. The weight average molecular weight of polypropylene glycol can be determined using a light scattering method, and can be measured with 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. .

<Chelating agent>
In the production method of the present invention, one or more selected from a low molecular chelating agent and a high molecular chelating agent can be blended as the chelating agent. In addition, the organic acid which has a chelating action can also be used as a pH adjuster.

  As a low molecular chelating agent which can be mix | blended with the manufacturing method of this invention, molecular weight 40-400, Preferably it is 90-360, More preferably, 100-300 water-soluble organic acid or those salts can be mentioned. 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, and particularly citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid. Hydroxyethanediphosphonic acid and their alkali metal or alkanolamine salts are preferred.

  In the composition obtained by the production method of the present invention, the content of the low molecular chelating agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass. .

  As the polymer chelating agent that can be blended by the production method of the present invention, a 0.2 mass% aqueous solution other than the above-mentioned polyacrylic acid thickener and adjusted to pH 7.0 is Brookfield at 20 ° C. It is a compound having a viscosity of 50 mPa · s or less as measured with a type viscometer (rotor No. 1, rotation speed 60 r / m). Specific examples thereof include polymer compounds containing a monomer constituent unit having a carboxylic acid group, and those having a monomer constituent unit derived from an acrylic acid-based monomer and / or a maleic acid-based monomer are particularly preferable, and polyacrylic acid is particularly preferable. 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 since it affects pH, the blending of sodium salt is limited.

  In the composition obtained by the production method of the present invention, the content of the polymer chelating agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass. .

  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 500,000, 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.

  In the composition obtained by the production method of the present invention, the total content when the low molecular chelating agent and the high molecular chelating agent are used in combination is preferably 0.2 to 30% by mass, and more preferably 0.5 to 20% by mass. 0.5 to 15% by mass is particularly preferable.

<PH>
The liquid detergent composition produced in the present invention is obtained by adding a balanced amount of water to the components selected from the above-mentioned components. At this time, the cleaning performance, irritation to eyes and skin, and thickening are obtained. From the above point, the pH at 25 ° C. is preferably 8.0 to 11.0, more preferably 9.0 to 11.0, and particularly preferably 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.

  The liquid detergent composition produced by 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 exceeds 4000 mPa · s) In this case, the viscosity measured by the rotor No. 4 and the rotation speed of 30 r / m is preferably 800 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 an automatic detergent inlet, the cleaning agent does not leak in the pre-washing step, and the usability is improved.

Examples and Comparative Examples a) Step T. of Primics Co., Ltd. K. In a blending tank equipped with a homodisper, ion-exchanged water, citric acid, an acrylic acid / maleic acid copolymer salt and calcium chloride were added at a ratio shown in Table 1, and dissolved at a peripheral speed of 11 m / s. While stirring at the same peripheral speed, the polyacrylic acid thickener was added little by little.
b) Step After the addition of the polyacrylic acid thickener was completed, stirring was continued for 5 minutes at a peripheral speed of 11 m / s, and then the entire amount was transferred to the azimuthomixer tank. Next, the thickener was dispersed by stirring for 5 minutes at a peripheral speed of 16 m / s of Ajihomomica of Primix Co., Ltd.
c) Process Next, the pressure in a tank was set to -95kPa, and the bubble mixed in by vacuum deaeration was removed.
d) Step Subsequently, the pressure in the tank is returned to normal pressure, and glycerin, surfactant-1, surfactant-2, polypropylene glycol, monoethanolamine, at a peripheral speed of 8.5 m / s of the azimuthomixer, Potassium hydroxide, α-amylase, and protease were added in this order, and finally surfactant-1 and a fragrance were dissolved to obtain a thickened liquid detergent composition for an automatic dishwasher. . About each composition, the mixing state of the fragrance | flavor and the mixing state of the bubble were observed with the following method. The results are shown in Table 1.

<Mixed state of fragrance>
The obtained cleaning composition was allowed to stand for 5 minutes in the azimuth mixer, and then the surface condition was visually observed.
○: There is no fragrance floating on the surface of the composition.
(Triangle | delta): There exists a small amount of fragrance | flavor floating on the composition surface.
X: A large amount of fragrance floats on the surface of the composition.

表１中、ａ）工程の含有割合とｄ）工程の含有割合の合計が１００質量％であり、組成物中の各成分の割合を示している。 <Bubble contamination>
In a 100 ml beaker, 100 ml of the composition was poured so as not to contain bubbles, and allowed to stand for 5 minutes.
A: Almost no bubbles are mixed in the composition.
Δ: A small amount of air bubbles is mixed in the composition.
X: A large amount of air bubbles is mixed in the composition.

In Table 1, the sum of the content ratio of the step a) and the content ratio of the step d) is 100% by mass, and indicates the ratio of each component in the composition.

  Example 1 is an example in which Surfactant-1 and perfume were dissolved at a mass ratio of 80/20, and Example 2 was dissolved at a mass ratio of 50/50. In any case, the mixed state of the fragrance was good, and no mixing of bubbles was observed.

  Comparative Example 1 is an example in which Surfactant-1 and perfume are dissolved at a mass ratio of 20/80, and Comparative Example 2 is dissolved at a mass ratio of 0/100. Comparative Example 1 is a state in which the fragrance is slightly floating on the surface of the composition, and Comparative Example 2 has a large amount of fragrance on the surface of the composition, and the mixed state is insufficient.

  Comparative Example 3 is an example in which a fragrance was added and dissolved alone without mixing with Surfactant-1. When the mixture was stirred at the same peripheral speed of 8.5 m / s as in Examples 1 and 2, almost all of the fragrance floated on the composition surface. For this reason, when it manufactured by raising the peripheral speed of the azimuth mixer so that a fragrance | flavor could be wound in the inside of a composition, the mixing state of the fragrance | flavor became favorable, but many air bubbles mixed and the external appearance became bad.

(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 (5)

A method for producing a liquid detergent composition for an automatic dishwasher comprising a nonionic surfactant, a fragrance, a thickener and water and having a viscosity at 20 ° C. of 800 mPa · s or more,
a) Step of adding a thickener to water b) Step of dispersing the thickener in water at a peripheral speed of the stirring blade of the stirrer exceeding 10 m / sec c) Step of vacuum defoaming d) Nonionic surfactant and A step of mixing at a peripheral speed of 10 m / sec or less of a stirring blade of a stirrer without adding vacuum, after adding a mixture of a mass ratio of fragrance 90/10 to 50/50,
A method for producing a liquid detergent composition for an automatic dishwasher. The automatic according to claim 1, wherein the nonionic surfactant is one or more of primary and secondary alcohol alkoxylate type nonionic surfactants represented by the following general formulas (I) and (II). A method for producing a liquid detergent composition for a dishwasher.

(In general formula (I), m and n are each independently an integer of 2 to 8, m + n is an integer of 4 to 16, and the average carbon number of the alkyl group composed of m and n is K is an average number of 2 to 19, and l is an average number of 0 to 10. In the formula, “/” indicates that an oxyethylene group and an oxypropylene group are added in blocks or randomly. It means that any of them may be added.
In general formula (II), R is an alkyl group having an average carbon number of 12 to 20, p is an average of 2 to 15, and q is an average of 0 to 10. In the formula, “/” means that the oxyethylene group and the oxypropylene group may be either block addition or random addition. )   The manufacturing method of the liquid detergent composition for automatic dishwashers of Claim 1 or 2 in which a fragrance | flavor contains 40 mass% or more of terpene hydrocarbon fragrance | flavors.   The terpene hydrocarbon fragrance is selected from α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene, linalool, geraniol, nerol, citronellol, hydroxycitronellol, tetrahydrolinalool, myrsenol, terpineol, menthol, borneol, isopulegol. The method for producing a liquid detergent composition for an automatic dishwasher according to claim 3, wherein the liquid composition is a monoterpene compound.   The manufacturing method of the liquid detergent composition for automatic dishwashers of any one of Claims 1-4 whose thickener is a polyacrylic acid type | system | group thickener.