JP2009073947A - Dishwashing detergent composition for washing before machine-washing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dishwashing detergent composition for washing before machine-washing, which has high detergency and high washing sustention even if diluted to low concentration when washing tableware with an automatic dishwasher, particularly an automatic dishwasher for business use, and which is excellent also in low-temperature stability and high-temperature stability. <P>SOLUTION: The dishwashing detergent composition for washing before machine-washing contains (a) a potassium salt of an alkylbenzenesulfonic acid having a 10-15C alkyl group, (b) a sulfate type surfactant having an 8-16C alkyl group, (c) a surfactant selected from amine oxide type surfactants represented by general formula (1) and betaine type surfactants represented by general formula (2), (d) an alkyl glycoside type surfactant represented by general formula (3): R<SP>10</SP>-(OR<SP>11</SP>)<SB>c</SB>G<SB>d</SB>, and (e) magnesium sulfate and/or magnesium chloride, in a specific ratio each. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a detergent composition suitable for pre-washing machine washing such as an automatic dishwashing machine in dish washing.

  Conventionally, automatic dishwashers are often used for cleaning dishes in various commercial facilities and general households.In particular, dishwashers for business use consume a large amount of dishes at a time compared to household ones. Since cleaning is sometimes performed and the cleaning time is extremely short, before performing mechanical cleaning, it is performed by placing dishes in a sink or the like filled with a cleaning solution diluted with a cleaning agent. Cleaning before such mechanical cleaning is an important factor for the washing of dishes. Patent Document 1 discloses a commercial automatic dishwasher having a preliminary cleaning process.

  Alkyl benzene sulfonate (LAS) -based cleaning agents are mainly used as pre-cleaning agents because of their excellent cost performance and high detergency, but they are highly degreased and cause rough hands. On the other hand, the sulfate type surfactant type has a defect inferior in detergency although it is less rough. Patent Document 2 discloses a pre-cleaning agent composition containing a nonionic surfactant and an enzyme as surfactants by blending a carboxylic acid with sulfate or hydrochloride.

As a method for improving the low temperature stability of a liquid detergent composition containing a high concentration of an ionic surfactant and a chelating agent, Patent Document 3 describes the formulation of a hydrotrope agent and sodium ions (Na ⁺ ) and The molar ratio of potassium ions (K ⁺ ) is limited and blended in the composition.
JP-T 9-509073 JP 2004-196901 A JP 2007-023210 A

  In such pre-washing in mechanical washing, when performing a washing method of washing dishes etc. in a washing water bath in which a cleaning agent is added to water (hot water) stretched on the sink, since the washing liquid is thin, the number of sheets that can be processed is It is limited and the cleaning solution must be replaced frequently. In addition, as a method of reducing the number of times the cleaning liquid is replaced, it is conceivable to increase the concentration of the cleaning agent. However, foaming due to the residual detergent adversely affects the subsequent machine cleaning, and the running cost is further burdened on the environment.

  In other words, in washing water for pre-washing by machine washing, even if the concentration of the cleaning agent is low, it is excellent in cleaning sustainability (meaning that the number of dishes that can be processed etc. increases), and the washing up is good. There is a strong demand for dishwashing agents for machine washing. However, the technique of Patent Document 2 is inferior in cleaning power and washing up.

  In addition, when an inorganic substance such as an inorganic sodium salt is added to a composition containing a surfactant at a high concentration, there is a concern about stability at low temperatures (precipitation of an inorganic salt or the like).

  On the other hand, liquid detergents containing alkanolamines may be colored by storage at high temperatures, and the solution is also desired.

  The object of the present invention is to have a high washing power and a high washing durability even when diluted to a low concentration when washing dishes with an automatic dishwashing machine, in particular, a commercial automatic dishwashing machine, and It is an object of the present invention to provide a dishwashing composition for washing before machine washing which is excellent in low temperature stability and high temperature stability.

  In the present invention, (a) a potassium salt of alkylbenzenesulfonic acid having an alkyl group having 10 to 15 carbon atoms (hereinafter referred to as component (a)) is 1 to 10% by mass, and (b) an alkyl group having 8 to 16 carbon atoms. 10 to 30% by mass of a sulfate ester type surfactant (hereinafter referred to as component (b)), (c) an amine oxide type surfactant represented by the following general formula (1) and the following general formula (2) 1 to 15% by mass of a surfactant selected from betaine surfactants represented below (hereinafter referred to as component (c)), (d) an alkyl glycoside surfactant represented by the following general formula (3) , (D) component] 10-20% by mass, (e) magnesium sulfate and / or magnesium chloride (hereinafter referred to as (e) component) containing 0.1-5% by mass in terms of anhydrous, (c) component / (B) component mass ratio is Is from 0.067 to 0.50, mechanical treatment before washing dishwashing detergent composition.

[Wherein, R ¹ is an alkyl group or alkenyl group having 8 to 16 carbon atoms, R ² is an alkylene group having 1 to 5 carbon atoms, and R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. Or it is a hydroxyalkyl group. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and a is a number of 0 or 1. ]

[Wherein, R ⁵ is an alkyl or alkenyl group having 9 to 23 carbon atoms, R ⁶ is an alkylene group having 1 to ⁶ carbon atoms, and R ⁷ and R ⁸ are each an alkyl group having 1 to 3 carbon atoms. Or it is a hydroxyalkyl group and R < ⁹ > is a C1-C5 alkylene group which may be substituted by a hydroxy group. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and b is a number of 0 or 1. D is a group selected from —COO ⁻ , —SO ₃ ⁻ , and —OSO ₃ ^— . ]
R ¹⁰ − (OR ¹¹ ) _c G _d (3)
[Wherein R ¹⁰ is an alkyl group having 8 to 16 carbon atoms, R ¹¹ is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, c is an average value of 0 to 6, and d is It is a number with an average value of 1-10. ]

  Moreover, this invention relates to the washing | cleaning method which performs this washing | cleaning using a dishwasher, after prewashing a to-be-washed object in the washing water bath containing the dishwashing agent composition for machine washing before the said this invention.

  Since a commercial cleaning machine is continuous and has a very short cleaning time of 40 to 50 seconds, it is preferable to perform pre-cleaning. The composition of the present invention is used for pre-cleaning when such a commercial cleaning machine is used. It is effective as a cleaning agent.

  The dishwashing composition for machine washing before washing according to the present invention maintains high cleaning power even when the diluted cleaning agent concentration is dilute, and improves cleaning durability. This reduces the labor, running costs and the environment. Furthermore, there is no influence on the machine cleaning process by the residual detergent. For this reason, it is particularly suitable as a dishwashing composition for washing before machine washing used in a lean washing method. In addition, since storage stability at low temperatures is excellent, problems such as crystal precipitation are remarkably reduced. Furthermore, since it is excellent in high temperature stability, the coloring problem at the time of high temperature storage is also eliminated.

<(A) component>
The component (a) is an alkylbenzenesulfonic acid potassium salt having an alkyl group having 10 to 15 carbon atoms, and the content in the composition is 1 to 10% by mass, preferably 2 to 5% by mass, more preferably 4 to 4%. 5% by mass. When the content is within the above range, sufficient detergency can be exhibited, and an effect is manifested particularly in detergency when the concentration of the composition is low.

In this invention, coloring of the liquid at the time of a high temperature storage can be suppressed by using alkylbenzenesulfonic acid potassium salt as (a) component. The content of the component (a) is preferably 5% by mass or less in the composition from the viewpoint of low temperature stability, and is preferably 2% by mass or more, and more preferably 4% by mass or more in consideration of detergency. However, since sodium ions (Na ⁺ ) brought into the composition from the component (b) and other components also affect the low temperature stability, total sodium ions (Na ⁺ ) and total potassium ions ( The molar ratio of K ⁺ ) is preferably Na ⁺ / K ⁺ = 2.5-10. The upper limit of the molar ratio is preferably 8 or less, and the lower limit is preferably 4.5 or more. Sodium ion and potassium ion concentrations can be determined by the atomic absorption method.

  (A) A component may be obtained by neutralizing with an alkaline agent such as potassium hydroxide or potassium carbonate in the composition by blending in an acid form.

<(B) component>
The component (b) of the present invention is a sulfate ester type surfactant having an alkyl group having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms. As the component (b), an alkyl group having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and an average added mole number of 1.5 to 4, preferably 1.6 to 4 mol, particularly preferably 2 to 3 are used. And polyoxyethylene alkyl ether sulfate ester salt having a molar oxyethylene group (hereinafter referred to as component (b1)). The alkyl group of the component (b1) is preferably one containing a branched chain from the viewpoint of the cleaning effect, and the mass ratio of the polyoxyalkylene branched chain alkyl ether sulfate salt in the total polyoxyalkylene alkyl ether sulfate salt is 20 to 70. It is preferable from the point of the washing | cleaning effect that it is mass% and also 20-60% mass%. Such a component (b1) can be produced using an alcohol obtained by hydroformylating a linear 1-alkene as a raw material. Here, hydroformylation is a method in which an alcohol is obtained by adding carbon monoxide to a linear 1-alkene using a carbonyl complex such as iron, cobalt, or nickel as a catalyst, and a linear alkyl group and a methyl branched chain. An alcohol containing an alkyl group is obtained. The polyoxyalkylene alkyl ether sulfate salt of the component (b1) is an alkylene oxide that requires ethylene oxide (hereinafter referred to as EO) in addition to such an alcohol, such as EO alone, EO and propylene oxide (hereinafter referred to as EO). (Denoted as PO), etc., preferably EO alone, and further sulfated with sulfur trioxide or chlorosulfonic acid and neutralized with an alkali agent. The average added mole number of alkylene oxide is preferably 1.5 to 4, more preferably 1.6 to 4, and particularly preferably 2 to 3, in order to achieve excellent cleaning performance. As an alkaline agent used for neutralization, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, and magnesium carbonate are preferable, and sodium hydroxide, potassium hydroxide, and magnesium hydroxide are more preferable.

  (B) A component can be mix | blended individually or in combination of 2 or more types. As content in a composition, it is 10-30 mass%, Preferably it is 15-30 mass%, Most preferably, it is 20-30 mass%. Specifically, the sodium salt is preferably 20 to 30% by weight.

<(C) component>
The component (c) is a surfactant selected from the amine oxide type surfactant represented by the general formula (1) and the betaine type surfactant represented by the general formula (2). In general formula (1), R ¹ is preferably an alkyl group or alkylene group having 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms. R ² is preferably an alkylene group having 2 or 3 carbon atoms. a is preferably a number of 1. In general formula (2), R ⁵ is preferably an alkyl or alkenyl group having 9 to 17 carbon atoms, particularly preferably 10 to 16 carbon atoms, and R ⁶ is preferably 1 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms. The alkylene group, b is preferably 0. R ⁷ and R ⁸ are preferably a methyl group, an ethyl group or a hydroxyethyl group, and R ⁹ is preferably an alkylene group having 1 to 3 carbon atoms which may be substituted with a hydroxy group. D is -SO ₃ from the viewpoint of cleaning effect ^- is good.

  (C) A component can be mix | blended individually or in combination of 2 or more types. As content in a composition, it is 1-15 mass%, Preferably it is 1-10 mass%, Most preferably, it is 3-10 mass%.

  The mass ratio of the component (c) to the component (b) is such that the component (c) / component (b) is 0.067 to 0.50, more preferably 0, from the viewpoint of the detergency and stability of the composition. 125 to 0.25.

<(D) component>
The component (d) is an alkyl glycoside surfactant represented by the general formula (3). In the general formula (3), R ¹⁰ is preferably an alkyl group having 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, R ¹¹ is preferably an ethylene group or a propylene group, particularly preferably an ethylene group, and d is preferably an average. A value of 1 to 5, particularly preferably a number of 1 to 2. (D) Content in the composition of a component is 10-20 mass%, Preferably it is 10-15 mass%.

<(E) component>
The component (e) of the present invention is magnesium sulfate and / or magnesium chloride, and a hydrate is preferably used at the time of blending. Examples of the hydrate include magnesium sulfate heptahydrate and magnesium chloride hexahydrate which are stable at room temperature. (E) Content in the composition of a component is 0.1-5 mass% in anhydrous conversion, Preferably it is 0.2-2.5 mass%. When the content is within the above range, sufficient detergency can be exhibited, and the stability of the composition can be enhanced.

In addition, the present liquid detergent composition contains almost no known aromatic hydrotrope such as lower alkyl benzene sulfonate having 1 to 4 alkyl groups having 1 to 4 carbon atoms or cumene sulfonate. Excellent detergency and storage stability can be obtained. Even when the content of the aromatic hydrotrope is 0.5% by mass or less, sufficient stability can be obtained. In addition, when mix | blending with a sodium salt or potassium salt, it is preferable to satisfy | fill the conditions of the said [Na ⁺ ] / [K ⁺ ] (molar ratio).

<Other ingredients>
A solvent, an antibacterial agent, a fragrance, a pigment, a dye, and the like can be added to the dishwashing composition for washing before machine washing of the present invention as long as the problems of the present invention can be solved.

<Dishwashing composition for machine washing before washing>
The dishwashing composition for machine washing before washing according to the present invention is obtained by mixing the above-described components (a) to (e) and other components with water as necessary, and is a transparent liquid at 20 ° C. Are preferred. As the water, ion-exchanged water or distilled water can be used. Further, a small amount of chlorine may be contained for the purpose of sterilizing or sterilizing water.

  The viscosity (20 ° C., measurement method described in Examples) of the dishwashing composition for machine washing before washing of the present invention is preferably 100 (mPa · s) or more, more preferably 200 to 500 (mPa) for handling. S).

  The viscosity as used in the present invention is measured as follows. First, TOKIMEC. The rotor type no. Prepare one equipped with 3 rotors. The sample is filled in a tall beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. A sample adjusted to a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 60 r / m, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the present invention.

  The pH (25 ° C.) of the dishwashing composition for machine pre-washing of the present invention is preferably 6.0 to 8.0 for the stability of the composition. More preferably, it is set to 6.0 to 7.0 in order to express cleaning performance more effectively and to ensure stability. The pH is measured according to JIS Z 8802 7.2 (measurement method).

  As the pH adjuster, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as citric acid, succinic acid, malic acid and lactic acid can be used as the acid agent. Sodium hydroxide, potassium hydroxide, sodium carbonate, Alkanolamines such as potassium carbonate or monoethanolamine, diethanolamine, triethanolamine can be used as the alkali agent. However, it is necessary to use alkanolamine as long as the storage stability is not impaired.

<Washing method>
In the cleaning method of the present invention, the object to be cleaned is pre-washed in a washing water bath containing the above-described dishwashing composition for machine washing at a low concentration, and then machine washing is performed using a dishwasher as the main washing. This is a cleaning method to be performed.

Specific examples of the cleaning method include the following cleaning operations.
(I) After washing the dishes such as dishes and cooking utensils for a suitable time in the washing water bath containing the dishwashing composition for washing before machine washing of the present invention, after washing the dishes in the washing water bath, How to perform machine cleaning.
(II) A method of performing machine washing after washing an object to be washed such as tableware and cooking utensils in a washing water bath containing the dishwashing composition for washing before machine washing according to the present invention without leaving.

  In these cleaning methods, prior to machine cleaning, pre-cleaning is performed by simply rubbing with a sponge or a cloth cloth in a cleaning water bath containing the dishwashing composition for pre-machine cleaning of the present invention. However, it is also possible to use a method in which the machine is removed from the washing water bath and subjected to machine washing as it is without performing an operation such as rubbing. The cleaning method of the present invention is particularly suitable for the pre-cleaning of mechanical cleaning according to (II). In any of the cleaning methods, a flexible absorbent such as a sponge or a cloth product such as a cloth can be used as necessary.

  In the cleaning method (dilute cleaning method) of the present invention, the concentration of the dishwashing composition for machine washing before washing in the washing water bath is preferably 0.005 to 0.5% by mass, and 0.01 to 0.1% by mass. % Is more preferable, and 0.01-0.05 mass% is still more preferable.

Example 1
Using the components shown in Table 1, dishwashing compositions for machine washing before washing were prepared, and the pH, viscosity, detergency, high temperature storage stability, and low temperature storage stability of these compositions were evaluated by the methods described below. . The results are shown in Table 1.

<PH>
The pH is measured using a pH meter F-52 manufactured by HORIBA, Ltd. at 25 ° C. for the dishwashing composition for washing before machine washing (stock solution). The pH was measured by the pH measurement method of “JIS Z 8802 7.2”.

<Viscosity>
TOKIMEC INC. B type viscometer manufactured by BM Prepare one equipped with 3 rotors. The dishwashing composition for washing before machine washing shown in Table 1 is filled in a beaker for viscosity measurement, and the temperature is sufficiently adjusted in a constant temperature water bath at 20 ° C. The beaker containing the composition was set in a viscometer, and the viscosity after 60 seconds was measured at a rotor rotational speed of 60 r / min.

<Detergency>
A plastic wash tub is filled with 10 L of water (temperature: 30 ° C., German hardness: 3.5 ° DH), and a predetermined amount of the dishwashing composition for washing before machine washing (concentration of cleaning composition: 0.04% by mass). Dissolve and stir well. Prepared model soiled dishes (5g of beef tallow / rapeseed oil = 1/1 (mass ratio) applied to a polypropylene dish and allowed to stand at room temperature for 24 hours) are washed in a washing water bath (diluted) In the state immersed in the composition), it is washed with a new sponge (trade name Kikuron manufactured by Kikuron Co., Ltd., flexible absorber of 115 mm × 75 mm × 35 mm). When you no longer feel null, move to the next plate and repeat. During washing and washing water baths in washing bowls, the cleaning power is reduced because dirt accumulates. The end point of the washing was the number of dishes one before the dish that could not be nullified when washed with a sponge.

  Normally, dishes and other dishes are roughly pre-washed before machine washing and then set in a machine washing machine to perform the main washing. In this example, the effect of pre-washing washing and the durability of the washing power are clearly defined. In order to do so, the cleaning power evaluation in the diluted cleaning system, that is, the evaluation before the mechanical cleaning was performed.

<High temperature storage stability>
A 5 L bottle was filled with 5 L of a dishwashing composition for washing before machine washing (stock solution) and stored in a temperature-controlled room adjusted to 50 ° C. for 20 days, and then the appearance of the composition was evaluated. In the evaluation, “◯” indicates that the material is hardly colored, “Δ” indicates that the material is colored but within the allowable range, and “X” indicates that the material is largely colored and is outside the allowable range.

<Low temperature storage stability>
A 5L bottle is filled with about 1/5 (1000 mL) of the pre-machine dishwashing detergent composition (stock solution) and stored in a thermostatic chamber adjusted to 0 ° C. The inner wall surface of the bottle was evenly wetted with the filled composition once a day, and the appearance of the composition after storage for 20 days was evaluated. The results are shown in Table 1.

(Note) The symbols in the table represent the following.
・ LAS-K: neutralized dodecylbenzenesulfonic acid with potassium hydroxide ・ AES: sodium polyoxyethylene alkyl ether sulfate ester [raw alcohol is 1-decene and 1-dodecene 50/50 (mass ratio) It is an alcohol obtained by hydroformylation. After adding an average of 2 moles of EO to this alcohol, it was sulfated with sulfur trioxide and neutralized with sodium hydroxide. The ratio of the total polyoxyethylene branched chain alkyl ether sulfate sodium in the total polyoxyethylene alkyl ether sulfate sodium was 42% by mass. ]
Amphoteric 1 (Note): N-lauroylaminopropyl-N, N-dimethylamine oxide Amphoteric 2 (Note): N-lauryl-NN-dimethyl-N- (2-hydroxy-3-sulfopropyl) ammonium Sulfobetaine / APG: straight chain mixed alkyl having alkyl group composition of 12/14 carbon atoms = 60/40 (mass ratio), alkyl glucoside having an average glucoside condensation degree of 1; LAS-Na: dodecylbenzenesulfonic acid as NaOH -LAS-MEA: neutralized dodecylbenzenesulfonic acid with monoethanolamine-Nonion: polyoxyethylene lauryl ether [EO average addition mole number 4]
Preservative: Proxel BDN [Arch Chemicals Japan Co., Ltd.]
(Note) Both amphoteric 1 and 2 used contained a small amount of sodium chloride.

Claims (3)

(A) 1 to 10% by mass of a potassium salt of alkylbenzenesulfonic acid having an alkyl group having 10 to 15 carbon atoms, (b) 10 to 30% by mass of a sulfate ester type surfactant having an alkyl group having 8 to 16 carbon atoms (C) 1 to 15% by mass of a surfactant selected from an amine oxide type surfactant represented by the following general formula (1) and a betaine type surfactant represented by the following general formula (2), (d 10) -20% by mass of alkylglycoside surfactant represented by the following general formula (3), (e) 0.1-5% by mass of magnesium sulfate and / or magnesium chloride as anhydrous conversion, (c ) Component / (b) The mass ratio of a component is 0.067-0.50.

[Wherein, R ¹ is an alkyl group or alkenyl group having 8 to 16 carbon atoms, R ² is an alkylene group having 1 to 5 carbon atoms, and R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. Or it is a hydroxyalkyl group. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and a is a number of 0 or 1. ]

[Wherein, R ⁵ is an alkyl or alkenyl group having 9 to 23 carbon atoms, R ⁶ is an alkylene group having 1 to ⁶ carbon atoms, and R ⁷ and R ⁸ are each an alkyl group having 1 to 3 carbon atoms. Or it is a hydroxyalkyl group and R < ⁹ > is a C1-C5 alkylene group which may be substituted by a hydroxy group. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and b is a number of 0 or 1. D is a group selected from —COO ⁻ , —SO ₃ ⁻ , and —OSO ₃ ^— . ]
R ¹⁰ − (OR ¹¹ ) _c G _d (3)
[Wherein R ¹⁰ is an alkyl group having 8 to 16 carbon atoms, R ¹¹ is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, c is an average value of 0 to 6, and d is It is a number with an average value of 1-10. ] The dishwashing composition for machine washing pre-washing according to claim 1, wherein the molar ratio of sodium ion (Na ⁺ ) to potassium ion (K ⁺ ) is Na ⁺ / K ⁺ = 2.5-10. A cleaning method for performing main cleaning using a dishwasher after pre-cleaning an object to be cleaned in a cleaning water bath containing the dishwashing composition for machine cleaning before washing according to claim 1 or 2.