JP2017110065A - Solid detergent composition for automatic dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid detergent composition for automatic dishwasher excellent in detergency to composite soil of proteins and lipids adhered to tableware and antifoaming properties.SOLUTION: There is provided a solid detergent composition for automatic dishwasher containing (a) an anionic surfactant represented by the following general formula (a1) of 1.5 mass% to 25 mass%, (b) an anionic surfactant represented by the following general formula (b1) of 0 mass% to 2 mass% and (c) a polyvalent aliphatic carboxylic acid or a salt thereof with mass ratio of (a)/(c) of 0.1 to 10. R-O-(PO)-SO-M(a1), where Rrepresents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average addition molar number of PO and the number of 0 to 1.5 and Mrepresents a hydrogen atom or cation. R-O-(PO)-SO-M(b1), where Rrepresents an alkyl group or an alkenyl group having 12 to 14 carbon atoms, PO represents propyleneoxy group, m2 represents the average addition molar number of PO and the number of 0 to 1.5 and Mrepresents a hydrogen atom or cation.SELECTED DRAWING: None

Description

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

Examples of stains attached to tableware include oil stains, starch stains such as rice grains, protein stains such as eggs, and pigment stains such as tea. Among these, the dry stains that are formed by combining lipids and proteins typified by soft-boiled eggs are difficult to remove because they adhere firmly to the dishes and are difficult to remove by washing with an automatic dishwasher. Become. In addition, oil stains are difficult to clean and have the problem of reattaching to tableware.
Patent Document 1 discloses that a nonionic surfactant (A) having a hydrophilic / lipophilic balance (HLB) of 1 to 7.0 is 0.1 to 10% by mass, at least one compound of carbonate and silicate. A detergent composition for an automatic dishwasher containing 5 to 70% by mass of (B), 5 to 20% by mass of percarbonate (C), and having a pH of 9 to 13 in a 0.1% by mass aqueous solution at 25 ° C. Things are disclosed.
Patent Document 2 discloses a cleaning agent containing decyl sulfate and condensed phosphate at a predetermined mass ratio.

JP 2014-1111697 A1 JP 2014-0665812 A

  The present invention provides a solid detergent composition for an automatic dishwasher having excellent detergency (hereinafter also simply referred to as detergency) against protein and lipid composite soil adhering to tableware and foam suppression.

In the present invention, (a) an anionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)] is 1.5% by mass or more and 25% by mass or less, and (b) the following general formula. The anionic surfactant represented by (b1) [hereinafter referred to as component (b)] is 0% by mass to 2% by mass, (c) a polyvalent aliphatic carboxylic acid or a metal salt thereof [hereinafter, (c ) Component]
The mass ratio of (a) component / (c) component is 0.1 or more and 10 or less,
The present invention relates to a solid detergent composition for an automatic dishwasher.
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]
^{_{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[In the formula, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents the average number of moles of PO added, and is a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]

  ADVANTAGE OF THE INVENTION According to this invention, the solid cleaning composition for automatic dishwashers excellent in the detergency with respect to the composite soil of the protein and lipid adhering to tableware, and foam suppression property is provided.

  The present inventors have found that a solid detergent composition for an automatic dishwasher using a combination of the component (a) and the component (c) dramatically improves the detergency against protein and lipid composite soils, Furthermore, since these effects can be obtained even if the content of the component (b) is suppressed, the present inventors have found that the foam suppressing property at the time of washing with an automatic dishwasher is also excellent.

<(A) component>
The component (a) of the present invention is an anionic surfactant represented by the following general formula (a1).
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]

In the general formula (a1), R ¹ is an alkyl group or alkenyl group having 10 carbon atoms from the viewpoint of detergency, and may be linear or branched. R ¹ is preferably a linear alkyl group having 10 carbon atoms.
m1 represents the average number of moles of PO added, and is 0 or more, and from the viewpoint of detergency and foam suppression, it is 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0. .5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less. It is also preferable that m1 is 0.
M ¹ is a hydrogen atom or a cation, and examples of the cation that forms a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Examples of the alkali metal ion include sodium ion, potassium ion, and lithium ion, and examples of the alkanol ammonium ion include monoethanol ammonium ion, diethanol ammonium ion, and triethanol ammonium ion. Among these, sodium ion or potassium ion is preferable.

  Two or more different (a) components may be used.

Incidentally, the compound represented by the general formula (a1) ^is obtained by sulfating the raw material alcohol represented by _{R 1 O- (PO) m1 H} , as long as they do not impair the present ^{invention, R} 1 O -(PO) _m1 H may be used a raw alcohol obtained by slightly adding ethylene oxide.

<(B) component>
The component (b) of the present invention is an anionic surfactant represented by the following general formula (b1).
^{_{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[In the formula, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents the average number of moles of PO added, and is a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]

In the general formula (b1), R ² is an alkyl group or an alkenyl group having 12 to 14 carbon atoms from the viewpoint of detergency and foam suppression, and may be linear or branched. . R ² is preferably a linear alkyl group.
m2 represents the average added mole number of PO and is 0 or more, and from the viewpoint of detergency and foam suppression, 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0. .5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less. It is also preferable that m2 is 0.
M ² is a hydrogen atom or a cation, and examples of the cation that forms a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Examples of the alkali metal ion include sodium ion, potassium ion, and lithium ion, and examples of the alkanol ammonium ion include monoethanol ammonium ion, diethanol ammonium ion, and triethanol ammonium ion. Among these, sodium ion or potassium ion is preferable.

  (B) Two or more different components may be used.

<(C) component>
The component (c) of the present invention is a polyvalent aliphatic carboxylic acid or a metal salt thereof.
Examples of the polyvalent aliphatic carboxylic acid include polyvalent aliphatic carboxylic acids having 3 to 6 carbon atoms or metal salts thereof. These carbon numbers include carbons of carboxylic acid groups.
Examples of the component (c) include one or more polyvalent aliphatic carboxylic acids selected from malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, and metal salts thereof, or metal salts thereof. It is done.
Examples of the metal salt include alkali metal salts such as sodium salt and potassium salt.
The component (c) is preferably at least one polyvalent aliphatic carboxylic acid selected from succinic acid, malic acid, citric acid, and metal salts thereof, or a metal salt thereof, more preferably citric acid or a metal thereof. Salt.

<Composition of a solid detergent composition for an automatic dishwasher>
In the solid detergent composition for an automatic dishwasher of the present invention, the component (a) is 1.5% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of detergency. It is preferably 4% by mass or more, and from the viewpoint of reducing raw material costs and foam suppression, it is 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. . The content of the component (a) is sodium salt equivalent. same as below.

In the solid detergent composition for an automatic dishwasher of the present invention, the component (b) is 0% by mass or more and 2% by mass or less, preferably 1.5% by mass or less, more preferably 1 from the viewpoint of foam suppression. It is contained by mass% or less, more preferably 0.5 mass% or less, still more preferably 0.1 mass% or less, still more preferably substantially 0 mass%, still more preferably 0 mass%.
As the content of the component (b), sodium salt equivalent is used. same as below.

  In the solid detergent composition for an automatic dishwasher of the present invention, the component (c) is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, from the viewpoint of detergency. More preferably, it is 15% by mass or more, and from the same viewpoint, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and still more preferably 30% by mass or less. (C) Acid content is used for content of a component. same as below.

  The solid detergent composition for an automatic dishwasher of the present invention has a mass ratio of (a) component / (c) component, which is a mass ratio of the content of component (a) and the content of component (c). From the viewpoint of detergency, 0.1 or more, preferably 0.15 or more, more preferably 0.2 or more, and from the same viewpoint, 10 or less, preferably 5 or less, more preferably 3 or less, still more preferably Is 2 or less, still more preferably 1 or less, and even more preferably 0.8 or less.

The solid detergent composition for an automatic dishwasher of the present invention preferably further contains (d) an inorganic alkali metal salt [hereinafter referred to as component (d)].
The component (d) is preferably one or more compounds selected from sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sulfate, and potassium sulfate.
In the solid detergent composition for an automatic dishwasher of the present invention, the component (d) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30 from the viewpoint of formulation of the solid detergent. From the viewpoint of detergency, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
Here, the component (d) excludes an alkali metal salt of condensed phosphoric acid described later.

  In the solid detergent composition for an automatic dishwasher of the present invention, the pH of a 0.2 mass% aqueous solution at 20 ° C is preferably 4 or more, more preferably 4.5 or more, and still more preferably from the viewpoint of detergency. 5 or more, more preferably 5.5 or more, and preferably 10 or less, more preferably 9 or less, still more preferably 8 or less, and even more preferably 7 or less, from the viewpoint of suppressing discoloration and foam suppression of aluminum. is there. The aqueous solution is prepared with ion exchange water.

In the solid detergent composition for an automatic dishwasher of the present invention, the content of condensed phosphate is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and preferably Is 0% by mass or more, still more preferably substantially 0% by mass, and still more preferably 0% by mass. In the present invention, even when the content of the condensed phosphate is in such a range, a solid detergent composition for an automatic dishwasher having excellent detergency against protein and lipid composite soil can be obtained. Therefore, it is advantageous for a formulation that suppresses eutrophication.
Here, examples of the condensed phosphate include salts of condensed phosphoric acid selected from pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, and hexametaphosphoric acid. Examples of the counter ion of the condensed phosphate include alkali metals such as sodium and potassium. In this invention, it is preferable that content of the condensed phosphate chosen from metaphosphate and a polyphosphate, and also hexametaphosphate are the said range.

The solid detergent composition for an automatic dishwasher of the present invention may be any powder, tablet, etc., but is preferably a powder detergent composition. The method for producing the powder detergent composition is not particularly limited, and each powder component may be mixed or each powder component may be granulated. For example, extrusion granulation method, compression granulation method, melt granulation method, spray drying granulation method, fluidized bed granulation method, crushing granulation method, stirring granulation method, liquid crystal granulation method, vacuum freeze drying granulation method, Examples thereof include a dry neutralization granulation method, and these production methods may be used singly or in combination.
The bulk density is preferably 200 g / L or more, more preferably 300 g / L or more, more preferably 600 g / L or more, and preferably 1300 g / L or less. The average particle size is preferably 50 μm or more, more preferably 100 μm or more, further preferably 150 μm or more, preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less.

  The solid detergent composition for an automatic dishwasher of the present invention includes a solvent, a hydrotrope agent, a dispersant, a pH adjuster, a thickener, a viscosity adjuster, a fragrance, and a colorant, as long as the object of the present invention is not impaired. Ingredients such as an agent, an antioxidant, an antiseptic, a foam inhibitor, a bleaching agent, and a bleaching activator (those not corresponding to the components (a) to (d)) can be blended.

The solid detergent composition for an automatic dishwasher of the present invention can be used for a dishwasher. Furthermore, it is suitably used for washing with a commercial dishwasher. The tableware includes cooking utensils, cleaning utensils, storage containers, and the like.
When washing with a dishwasher, and further with a commercial dishwasher, the solid detergent composition for an automatic dishwasher of the present invention is used as a washing liquid mixed with water. For example, water or warm water is sprayed with a spray or shower on a composition filled in a dedicated hopper of an automatic dishwasher to prepare a cleaning liquid in which the composition and water are mixed, and the cleaning liquid is used for automatic dishwashing. Supplied inside the machine.

  From the viewpoint of economy, the cleaning liquid prepared from the solid detergent composition for an automatic dishwasher of the present invention is usually preferably prepared while maintaining a constant concentration in a storage tank provided in the automatic cleaning machine.

  According to the present invention, a washing liquid for an automatic washing machine obtained by diluting the solid detergent composition for an automatic dishwashing machine of the present invention with water to 320 times (mass ratio, the same applies hereinafter) to 770 times or less, and the washing liquid are used. A cleaning method for cleaning dishes by an automatic cleaning machine is provided. In this washing method, a step of diluting the solid detergent composition for an automatic dishwasher of the present invention with water to 320 times or more and 770 times or less to prepare a washing liquid for an automatic washing machine, and dish washing using the washing liquid And washing the dishes with an automatic dishwasher. The dilution rate at the time of using the solid detergent composition for an automatic dishwasher of the present invention is preferably 770 times (mass ratio, the same shall apply hereinafter) or less, more preferably 700 times or less, still more preferably 600 times or less, and still more preferably. Is 550 times or less, more preferably 530 times or less, and preferably 320 times or more, more preferably 400 times or more, still more preferably 450 times or more, and further preferably 470 times or more.

  The concentration in the cleaning liquid at the time of using the solid detergent composition for an automatic dishwasher of the present invention is preferably 0.13% by mass or more, more preferably 0.14% by mass or more, from the viewpoints of economy and detergency. More preferably, it is 0.17% by mass or more, more preferably 0.18% by mass or more, further preferably 0.19% by mass or more, and from the same viewpoint, preferably 0.31% by mass or less, more Preferably it is 0.25 mass% or less, More preferably, it is 0.22 mass% or less, More preferably, it is 0.21 mass% or less.

  The washing time is preferably 10 seconds or more, more preferably 20 seconds or more, still more preferably 30 seconds or more from the viewpoint of detergency, and preferably 3 minutes or less from the viewpoint of productivity and economy. More preferably, it is 2 minutes or less, More preferably, it is 1 minute or less.

The cleaning temperature of the cleaning liquid is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of productivity and detergency, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, from the viewpoint of detergency. It is.
After the dishes have been washed, usually immediately in the same dishwasher and further in an automatic dishwasher, water, hot water or hot water, for example, preferably 40 ° C or higher, more preferably 60 ° C or higher, and preferably Rinsing is performed with hot water at 80 ° C. or lower for 5 minutes to 40 minutes.

  In a dishwasher, the cleaning liquid is usually used repeatedly by circulating it with a pump.

  A solid detergent composition for an automatic dishwasher shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. The solid detergent composition for automatic dishwashers in Table 1 was prepared by a conventional method. That is, it was prepared by mixing the powders of component (a), component (b), component (c) and component (d).

<Evaluation method>
(1) Detergency of protein / lipid complex stains Using a yolk separator, melt the egg yolk excluding the egg white, and then add 2 g of yolk to a ceramic dish (23 cm in diameter) so that it becomes a circle with a diameter of 10 cm from the center. And then dried for 1 day to prepare a ceramic platter to which protein / lipid complex soil was adhered. A plurality of earthenware platters with the dirt adhered thereto were prepared. The solid detergent composition for an automatic dishwasher shown in Table 1 was dissolved using tap water (3 ° DH) so as to be a 0.2% by mass aqueous solution to obtain a washing liquid. Using this cleaning solution and two ceramic platters with the above-mentioned dirt attached, cleaning is performed on the standard course of a table-top dishwasher (NP-TR3 manufactured by Panasonic, Inc., cleaning time 19 minutes, cleaning temperature upper limit 56 ° C.). The evaluation was performed according to the following criteria. The average value of the evaluation results of two soiled ceramic platters was determined and shown in the table.
* Criteria for cleaning power 4: Completely cleaned (no dirt left)
3: Almost cleaned (several small yellow spots observed, within tolerance)
2: Slightly dirty (a lot of yellow spots are observed, out of tolerance)
1: Most dirt remains (dirt remains on the surface)

(2) Antifoaming property After putting 6g of the solid detergent composition for automatic dishwashers shown in Table 1 into a tabletop dishwasher (NP-TR3 manufactured by Panasonic Corporation), tap water is used in a standard course. Washing was started and the height of the foam after 20 minutes was measured. The height of the foam was measured based on the drain outlet inside the washing machine. The lower the numerical value, the better the foam height. In this evaluation, the height of the foam is preferably 7 cm or less, more preferably 6 cm or less, still more preferably 5 cm or less, still more preferably 4 cm or less, and even more preferably 3.5 cm or less.

(3) Change in appearance of aluminum during immersion A 0.2% by mass aqueous solution was prepared with ion-exchanged water from a solid detergent composition for an automatic dishwasher shown in Table 1, and an aluminum test piece (Engineering Test Service Co., Ltd.) After 20 mm × 50 mm × 1 mm was immersed for 12 hours (at 25 ° C.), it was rinsed lightly with ion-exchanged water, dried well, and visually evaluated, and evaluated according to the following criteria.
* Judgment criteria for appearance change 4: No change in appearance 3: Although the immersed part is slightly discolored, it is an acceptable level 2: Discoloration is observed in the immersed part 1: It was immersed Noticeable discoloration in the area

The components in the table are as follows. The acid conversion value was used for the content of (c).
Component (a), sodium decyl sulfate: manufactured by Kanto Chemical Co., Inc., in the general formula (a1), a straight-chain alkyl group of ^{R 1} is 10 carbon atoms, m1 is 0, anionic surfactants ^{M 1} is sodium ion Agent

Component (b), sodium dodecyl sulfate: manufactured by Kanto Chemical Co., Inc., in the general formula (b1), a straight-chain alkyl group ^{R 2} is 12 carbon atoms, m2 is 0, anionic surfactants ^{M 2} is sodium ion Agent

(C) Ingredients: Citric acid: manufactured by Kanto Chemical Co., Ltd., reagent grade, citric acid 3Na dihydrate: Trisodium citrate dihydrate, manufactured by Kanto Chemical Co., Ltd., reagent grade

(D) Component / sodium sulfate: manufactured by Kanto Chemical Co., Inc.

It turns out that the Example of this invention is excellent in the balance of a cleaning power and foam suppression property compared with a comparative example.
Among Examples 2-4, it turns out that Example 2 whose mass ratio of (a) component / (c) component is 0.3 is excellent by a detergency. Further, as in Comparative Example 2, when the content of the component (a) is out of the range of the present invention, a good detergency is obtained even if the mass ratio of the component (a) / (c) is 0.3. It turns out that it cannot be obtained.
When Examples 2, 5, 7, and 9 are compared, Examples 2 and 5 in which the content of component (a) is 5% by mass or 7% by mass are more excellent in detergency and are balanced with foam suppression. It turns out that it is excellent.

Claims (4)

(A) An anionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)] is 1.5 mass% or more and 25 mass% or less, and (b) the following general formula (b1). An anionic surfactant [hereinafter referred to as “component (b)”] represented by 0 to 2% by mass, (c) a polyvalent aliphatic carboxylic acid or a metal salt thereof [hereinafter referred to as “component (c)”] Containing
The mass ratio of (a) component / (c) component is 0.1 or more and 10 or less,
Solid detergent composition for automatic dishwashers.
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]
^{_{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[In the formula, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents the average number of moles of PO added, and is a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]   (C) The solid cleaning composition for automatic dishwashers of Claim 1 containing 3 mass% or more and 60 mass% or less of components.   The solid detergent composition for an automatic dishwasher according to claim 1 or 2, further comprising (d) 10% by mass to 95% by mass of an inorganic alkali metal salt.   The solid detergent composition for automatic dishwashers in any one of Claims 1-3 whose pH of 0.2 mass% aqueous solution in 20 degreeC is 4-10.