JP2022100664A - Detergent composition for dishwashers - Google Patents

Abstract

To provide a detergent composition for a dishwasher that is less prone to foaming in a washing tank, has great power of washing off composite stains containing protein and lipids, and can reduce odors in the washing tank of the dishwasher after washing.SOLUTION: A detergent composition for dishwashers contains (a) a sulfosuccinic acid branched alkyl ester having a branched alkyl group, which is a C9-11 branched alkyl group, and (b) an inorganic alkali agent.SELECTED DRAWING: None

Description

The present invention relates to a dishwasher detergent composition.

Examples of stains adhering to tableware include oil stains, starch stains such as rice grains, protein stains such as eggs, and pigment stains such as tea. Among these, oil stains and proteins are stains that are difficult to remove, and there is a problem that oil stains reattach to dishes when washed with a dishwasher. In order to enhance the detergency against oil stains, for example, various types and formulations of surfactants, which are active ingredients for cleaning, have been conventionally proposed. Patent Document 1 discloses a technique of an automatic dishwashing detergent containing an anionic surfactant such as dialkylsulfosuccinic acid. Further, Patent Document 2 discloses a technique of using dialkylsulfosuccinic acid having a specific structure as a dishwashing detergent.

In addition to oil stains, the cleaning power of protein stains, especially protein / lipid complex stains such as egg stains, is important as a cleaning agent for dishwashers, and for that purpose, alkali such as sodium carbonate is used as the main cleaning component. Often used. Patent Document 3 discloses a technique of a dishwashing agent for immersion cleaning containing sodium carbonate and dialkyl sulfosuccinic acid.

Japanese Unexamined Patent Publication No. 2019-182904 JP-A-2017-214554 Japanese Unexamined Patent Publication No. 2-151698

When a surfactant is added to a cleaning agent containing alkali as the main cleaning component for the purpose of strengthening oil stains, foam is generated in the washing machine of the dishwasher, and due to the foaming, the expected proteins and lipids are generated. It may be difficult to obtain detergency against complex stains, or the dishwasher itself may stop operating. Further, there is a problem that an odor tends to remain in the washing chamber of the dishwasher after washing.
INDUSTRIAL APPLICABILITY The present invention is a detergent composition for a dishwasher, which has less foaming in the washing chamber, is excellent in detergency of complex stains containing proteins and lipids, and can suppress odor in the washing chamber of the dishwasher after washing. I will provide a.

The present invention comprises (a) a sulfosuccinic acid branched alkyl ester in which the branched alkyl group has 9 or more and 11 or less carbon atoms [hereinafter referred to as (a) component], and (b) an inorganic alkaline agent [hereinafter (b) component. ] Containing a detergent composition for a dishwasher.

According to the present invention, a detergent for a dishwasher that has less foaming in the washing chamber, has excellent detergency for complex stains containing proteins and lipids, and can suppress odor in the washing chamber of the dishwasher after washing. The composition is provided. Further, the detergent composition for a dishwasher of the present invention has an effect of suppressing reattachment of oil stains when washing in a dishwasher, and therefore has excellent cleaning power for oil stains.

The details of the mechanism of action of the present invention are unknown, but the present inventors consider as follows. The component (a) of the present invention is a surfactant having less foaming and having a high oil stain detergency at a low concentration. On the other hand, it is known that an alkaline agent is effective for cleaning lipid / protein stains, but since lipid / protein stains are hydrophobic, contact with a water-soluble inorganic alkaline agent is unlikely to occur. The component (a) can efficiently contact the lipid / protein stain with the inorganic alkaline agent which is the component (b), and as a result, the detergency of the lipid / protein stain can be improved. In addition, the odorous components in the washing cabinet are often caused by lipid / protein-derived components, and by improving the cleaning effect of the component (a) and the inorganic alkaline agent, an excellent deodorizing effect can be obtained. I believe.

<Dishwasher detergent composition>
The component (a) is a sulfosuccinic acid branched alkyl ester in which the branched alkyl group is a branched alkyl group having 9 or more and 11 or less carbon atoms.

Examples of the component (a) include those in which the ester is a monoester and those in which the ester is a diester. Preferably, it is a sulfosuccinic acid branched alkyl diester in which the branched alkyl group is a branched alkyl group having 9 or more carbon atoms and 11 or less carbon atoms.

The branched alkyl group of the component (a) is preferably a branched alkyl group having a main chain having 6 or 7 carbon atoms and a side chain having 1 or more carbon atoms and having a total of 3 carbon atoms in the side chains.
The branched alkyl group of the component (a) is preferably a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.

Examples of the component (a) include sulfosuccinic acid branched alkyl esters represented by the following general formula (a1).

[In the formula, R ^1a and R ^2a are independently branched alkyl groups having 9 or more and 11 or less carbon atoms. A ¹ and A ² are independently alkylene groups having 2 or more and 4 or less carbon atoms, and x and y are average addition moles and are independently 0 or more and 6 or less. M ¹ is a hydrogen atom or a cation. ]

Further, as the component (a), a sulfosuccinic acid branched alkyl ester represented by the following general formula (a1-1) can be mentioned. This compound is a compound having x = 0 and y = 0 according to the general formula (a1).

[In the formula, R ^1a and R ^2a are independently branched alkyl groups having 9 or more and 11 or less carbon atoms. M ¹ is a hydrogen atom or a cation. ]

The following description can be applied to each of the general formula (a1) and the general formula (a1-1).
The carbon atoms of R ^1a and R ^2a may be the same or different.
In the present invention, the hydrocarbon residue obtained by removing the hydroxyl group from the secondary alcohol is included in the chain branched hydrocarbon group.

In the present invention, among the chain-type branched hydrocarbon groups of R ^1a and R ^2a , the hydrocarbon chain having the largest number of carbon atoms counted from the carbon atom bonded to the oxygen atom is used as the main chain, and the hydrocarbon chain is branched from the main chain. The bonded hydrocarbon chain is used as a side chain.
When two or more main chains are considered, that is, when there are two or more hydrocarbon chains having the largest number of carbon atoms (hereinafter, also referred to as the longest hydrocarbon chain), the main chains are determined in the following order.
1. 1. The one with the larger number of carbon atoms in the side chain branched from the longest hydrocarbon chain is the main chain.
2. 2. Next, when the number of carbon atoms of the side chain branched from the longest hydrocarbon chain is the same, the one having a large number of side chains branched from the longest hydrocarbon chain is used as the main chain.
3. 3. Next, when the number of side chains branched from the longest hydrocarbon chain is the same, the one having the side chain on the carbon atom closer to the oxygen atom is the main chain, counting from the carbon atom bonded to the oxygen atom. do.
4. Next, when the positions of the carbon atoms having the side chain closest to the oxygen atom are the same, the one having the largest number of carbon atoms in the side chain closest to the oxygen atom is used as the main chain.
When two or more longest hydrocarbon chains have the same symmetrical structure, either of them may be used as the main chain.

In each of the branched alkyl groups of R ^1a and R ^2a , the total number of carbon atoms constituting the side chain may be the same or different, and is preferably 3 from the viewpoint of detergency and foam suppression of solid fat and the like. be.
In the present invention, the total number of carbon atoms constituting the side chain is the total number of carbon atoms of all side chains other than the main chain in one branched alkyl group, and if there are a plurality of side chains, all of them. It is the total number of carbon atoms in the side chain.

The number of side chains of R ^1a and R ^2a may be the same or different, and may be 1 or more, preferably 3 or less, and more preferably 2 or less from the viewpoint of detergency and foam-suppressing property of solid fat and the like. be.
In the present invention, the number of side chains is the number of side chains branching from the main chain, and the number of side chains does not change even if the side chains further have side chains branching from the side chain. .. However, from the viewpoint of detergency and foam-suppressing property of solid fat and the like, the side chain may further have a side chain branched from the side chain.

The number of branched carbons of R ^1a and R ^2a may be the same or different, and is 1 or more, preferably 3 or less, and more preferably 2 or less from the viewpoint of detergency and foam-suppressing property of solid fat and the like. Is.
In the present invention, the number of branched carbons is the total number of tertiary carbon atoms and quaternary carbon atoms in the chain branched hydrocarbon group.

In a preferred embodiment of R ^1a and R ^2a , the total carbon number of the chain-type branched hydrocarbon groups of R ^1a and R ^2a is independently 9 or more and 11 or less, further 9 or 10, and the number of carbon atoms in the main chain. However, the number of carbon atoms constituting the side chain is independently 1 or more and 3 or less, and the number of side chains is 1 independently.

The specific branched alkyl groups of R ^1a and R ^2a may be the same or different, respectively, and a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group is preferable.

In the general formula (a1), A ¹ and A ² are independently alkylene groups having 2 or more carbon atoms and 4 or less carbon atoms, preferably 3 or less carbon atoms.
In the general formula (a1), x and y are the average number of added moles, and are independently 0 or more and 6 or less, preferably 4 or less, respectively, from the viewpoint of detergency and foam-suppressing property of solid fat and the like. It is more preferably 2 or less, and even more preferably 0.
Further, x + y is preferably 0 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, still more preferably 0, from the viewpoint of detergency and foam-suppressing property of solid fat and the like. ..

In the general formula (a1), M ¹ is a hydrogen ion, an inorganic cation such as a sodium ion, an ammonium ion, a potassium ion, or a magnesium ion, a monoethanolammonium ion, a diethanolammonium ion, a triethanolammonium ion, or a morpholinium ion. It is an organic cation such as, preferably an inorganic cation selected from sodium ion, ammonium ion, potassium ion and magnesium ion.

In the general formula (a1), the method for preparing a compound having the same R1a and ^R2a is not particularly limited, but for example, the method described in US Pat. No. ^2,028,091 is referred to. As a method for preparing an asymmetric compound having different R1a and ^R2a , for example, it can be produced with reference to Japanese Patent Application Laid-Open No. ^58-24555 . As a raw material for the component (a), an alcohol having a predetermined carbon number to which an alkylene oxide is added can also be used.
Suitable alcohols used in the production of component (a) of the present invention include
(1) Primary alcohols typified by 3,5,5-trimethylhexane-1-ol, 2-propylheptane-1-ol, etc.
(2) Secondary alcohols typified by 5-nonanol, 2,6-dimethyl-4-heptanol and the like can be mentioned.

The cleaning agent composition for a dishwasher of the present invention contains the component (a) from the viewpoint of detergency, for example, 0.01% by mass or more, further 0.05% by mass or more, and from the viewpoint of detergency and deodorant property. Further, 0.1% by mass or more, further 0.2% by mass or more, further 0.3% by mass or more, and from the viewpoint of detergency and foaming property, for example, 10.0% by mass or less, further 5.0% by mass. Hereinafter, it can be further contained in an amount of 2.0% by mass or less, further 1.0% by mass or less, and further 0.8% by mass or less.
In the present invention, the description (mass%, etc.) regarding the amount of the component (a) is the mass of the compound converted to sodium salt, for example, the mass when M ¹ in the general formula (a1) is assumed to be sodium. It shall be based on.

The component (b) is an inorganic alkaline agent.
As the component (b), an inorganic alkali metal salt is preferable, and one selected from sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide or Two or more compounds are more preferred. As the component (b), a compound selected from sodium carbonate and potassium carbonate is more preferable.

The cleaning agent composition for a dishwasher of the present invention contains, for example, 3% by mass or more, further 4% by mass or more, and further 5% by mass of the component (b) from the viewpoint of improving the detergency of complex stains containing proteins and lipids. % Or more, further 8% by mass or more, further 10% by mass or more, further 15% by mass or more, and for example, 50% by mass or less, further 40% by mass or less, further 35% by mass or less.

The detergent composition for a dishwasher of the present invention has (a) the content of the component and (b) the content of the component from the viewpoint of the detergency of oil stains and the detergency of complex stains containing proteins and lipids. (B) / (a) is preferably 5 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 15 or more, and preferably 1000 or less, more preferably 500 or less. , More preferably 200 or less, still more preferably 100 or less.
Further, the detergent composition for a dishwasher of the present invention is a mass ratio of the content of the component (a) to the content of the component (b) from the viewpoint of the deodorizing effect (b) / (a). However, it is preferably 500 or less, more preferably 300 or less, still more preferably 200 or less, still more preferably 100 or less.

The detergent composition for a dishwasher of the present invention can contain a metal sequestering agent as the component (c).
The components (c) include citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamate diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, and 1,3-propanediamine triacetic acid. , 1,3-Diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid, triethylenetetraaminehexacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid. Carous acid or a salt thereof, tripolyphosphate or a salt thereof can be used.
As the component (c), citric acid, malic acid, ethylenediamine tetraacetic acid, methylglycine diacetic acid, glutamate diacetic acid, tripolyphosphate, and one or more selected from these salts are preferable, citric acid, trisodium citrate, and the like. When the detergent composition for a dishwasher of the present invention, in which one or more selected from diacetic acid glutamate and salts thereof is more preferable, contains the component (c), the composition may contain the component (c), for example. , 2% by mass or more, further 5% by mass or more, further 10% by mass or more, and 30% by mass or less, further 25% by mass or less, further 20% by mass or less can be contained.

The detergent composition for a dishwasher of the present invention can contain an inorganic peroxide as a component (d).
Examples of the component (d) include sodium percarbonate, perborate (monohydrate or tetrahydrate), percarbonate, persulfate, persilicate and the like.
As the component (d), one or more inorganic peroxides selected from sodium perborate, sodium persulfate, and sodium perborate are more preferable, and the detergent composition for a dishwasher of the present invention is the component (d). In the case of containing, the composition contains (d) component (d) in an amount of 5% by mass or more, further 10% by mass or more, further 15% by mass or more, and 40% by mass or less, further 35% by mass or less, and further 30% by mass or less. can do.
When the detergent composition for a dishwasher of the present invention contains the component (d), the composition contains the component (c) in an amount of, for example, 5% by mass or more, further 10% by mass or more, and further 20% by mass or more. And, it can be contained in an amount of 40% by mass or less, further 35% by mass or less, and further 30% by mass or less.

The detergent composition for dishwashers of the present invention further optionally includes a solvent, a hydrotropic agent, a dispersant, a pH adjuster, a thickener, a viscosity regulator, a fragrance, a colorant, an antioxidant, and an antiseptic. It can contain components such as an agent, a defoaming agent, a bleaching agent (other than the component (d)), a bleaching activator, a rust preventive agent, a powder property improver, and an enzyme.

The detergent composition for a dishwasher of the present invention is preferably a solid composition such as powder, granules, and granules.

From the viewpoint of detergency, the dishwasher detergent composition of the present invention has a pH of a 0.2 mass% water diluted solution at 25 ° C., preferably 8 or more, more preferably 8.5 or more. It is more preferably 9 or more, preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less. The pH can be measured by the glass electrode method.

In the present invention, a method of preparing a washing liquid by diluting the detergent composition for a dishwasher of the present invention with water, for example, 10 times or more and less than 10000 times, and further 50 times or more and less than 5000 times, and using it for washing is preferable. Is.

The detergent composition for a dishwasher of the present invention is used for washing dishes with a dishwasher. Examples of tableware include items used for storing food such as plates, bowls and cups, and items used for separating food such as chopsticks, forks, knives and spoons. In the present invention, the tableware is, in addition to these items, foods such as tappers, storage containers such as bottles, kitchenware such as kitchen utensils, cutting plates, pots, frying pans, and grilled fish, food processors, and cooking appliances such as mixers. May include articles and parts thereof that are in contact with the dishwasher and can be washed in a dishwasher. Examples of the material of tableware include plastic (including silicone resin), metal, pottery, wood, and combinations thereof. The detergent composition for a dishwasher of the present invention is suitably used for washing dishes having a hydrophobic surface, for example, plastic dishes. Cleaning using the detergent composition of the present invention is similar to cleaning with a normal dishwasher.

The components of Tables 2 to 4 were blended with the basic composition of Table 1 to prepare a detergent composition for a dishwasher of Tables 2 to 4. The detergent composition for a dishwasher was used in an automatic dishwasher, and the detergency, the odor in the washing chamber, and the foaming were evaluated by the following methods. The results are shown in the table. In the table, (b) / (a) is shown with the component (a') as the component (a).

(1) Detergency of oil stains Four polypropylene dishes were installed in an automatic dishwasher (NP-45VS6S, manufactured by Panasonic). Two of the dishes were contaminated dishes coated with 3 g of compound stains of lard / salad oil = 1/1 (mass ratio), and the remaining two were uncontaminated dishes.
6.0 g of the dishwasher detergent composition shown in the table was added, and washing was performed in a standard course. A total of four panelists touched all the dishes after washing and gave evaluation points to each dish according to the following criteria. The average value of each example was calculated from the evaluation points obtained from all the panelists and shown in the table.
The total concentration of the components (a) and (b) in the cleaning solution (cleaning solution formed by diluting the cleaning agent composition with water) applied to tableware is such that the amount of the composition added is 6.0 g. In the case, it was 2000 ppm (the same applies to other evaluations).
* Evaluation criteria for detergency (feeling evaluation) 4: Dirt has been removed, and it feels crispy and comfortable to the touch.
3: The squeaky feel is weak, but the dirt is removed.
2: Most of the dirt has been cleaned, but if you rub it with your finger, it will become streaky.
1: It becomes slimy to the touch.
0: You can visually see that oil remains.
It should be noted that the nulling of the dish after washing is caused by the reattachment of oil stains, and in this evaluation method, the squeaky feel means that the reattachment was suppressed.

(2) Detergency of complex stains containing proteins and lipids Four ceramic dishes were installed in an automatic dishwasher (NP-45VS6S, manufactured by Panasonic). Two of the dishes are contaminated dishes with 10 g of denatured egg stains and 5 g of compound stains of lard / salad oil = 1/1 (mass ratio) per dish, and the remaining two are uncontaminated. It was a plate.
6.0 g of the dishwasher detergent composition shown in the table was added, and washing was performed in a standard course. A total of 4 panelists visually observed all the dishes after washing, and the average value of each example was calculated from the evaluation points obtained from all the evaluation point panelists for each dish according to the following criteria, and is shown in the table.
* Evaluation criteria for detergency (visual evaluation) of compound stains 4: All stains are removed and it is good.
It is slightly inferior to 3: 4 points, but it is almost down.
2: There is some dirt left to notice.
1: Dirt has not been removed.
In addition, each panelist touched the dish after cleaning and evaluated the texture by the same evaluation criteria as the cleaning property of oil stains in (1), and the average value is shown in the table.

(3) Smell in the washing cabinet (deodorant effect)
In an automatic dishwasher (NP-45VS6S, manufactured by Panasonic), (i) put 3.5g of mixed stains of curry and rice on one pottery dish, and (ii) remove the stains of the sauce in oil. 2 pieces of 2g on a pottery plate, (iii) 3 pieces of natto stains on a pottery bowl with 1.3g, and (iv) 5g of sauce stains on a pottery plate. I set two pieces of pottery. The amount of the detergent composition for the dishwasher shown in the table was 6.0 g, and the washing was started under the standard course and 30 minutes of drying. After washing, the odor in the washing cabinet of the automatic dishwasher was confirmed by 4 panelists immediately after washing and 30 minutes after washing, respectively, and evaluation points were given according to the following criteria, and the average value is shown in the table. Indicated.
* Criteria for deodorant effect 4 points: The unpleasant odor has disappeared.
3 points: Slightly odorous but not unpleasant.
2 points: It has a slightly unpleasant odor.
1 point: It has an unpleasant odor.

(4) Evaluation of foaming A standard course of cleaning conditions using an automatic dishwasher (NP-TR3, manufactured by Panasonic) using 12.0 g (equivalent to twice the standard usage amount) of the dishwasher cleaning agent composition shown in the table. Cleaning was started at. The operation started from the mist to wash, and 12 minutes later, the operation was stopped, and the state of bubbles in the washing chamber was confirmed. After that, one panelist confirmed the remaining foam after the first drainage and displayed it as a score based on the evaluation standard.
* Evaluation criteria for foaming 4 points: Less foaming and less foam residue after drainage.
3 points: There is some foaming or foam residue, but it is at a level that is not a problem.
2 points: The operation does not stop, but the foaming is such that the rotation of the nozzle slows down.
1 point: Operation stops.

The components in Table 1 are as follows.
Maleic acid copolymer: Copolymer of maleic acid / acrylic acid copolymer (30/70 molar ratio), weight average molecular weight 21000, Poiz-520 (manufactured by Kao Corporation)
-Polypropylene glycol: Weight average molecular weight 3000, average condensation degree about 50 (diol type, Wako Pure Chemical Industries, Ltd.)

* 1: Since the operation of the washing machine stopped, the dishes were taken out from the washing machine and evaluated at the stage when the washing machine stopped.
* 2: The deodorizing effect could not be evaluated because the operation of the washing machine stopped.

The detergent composition for a dishwasher shown in Table 4 is also excellent in deodorizing effect immediately after washing and 30 minutes after washing evaluated by the method (3) above, for example.

The components in Tables 2 to 4 are as follows.
-A-1: Sodium sulfosuccinate di (2-propylheptyl) ester (a compound in which R1a and R2a in the general formula (a1-1) are ² - ^propylheptyl groups and M is sodium, respectively).
-A-2: Sodium sulfosuccinate di (3,5,5-trimethylhexyl) ester (R ^1a and R ^2a in the general formula (a1-1) are 3,5,5-trimethylhexyl groups, respectively, and M is sodium. Compound)
-A'-1: Sodium di (2-ethylhexyl) sulfosuccinate-a'-2: Linear alkyl (10 to 14 carbon atoms) Sodium benzenesulfonate solution (LAS) (The table shows the amount in terms of effective component. rice field.)

A dishwasher detergent composition prepared by blending the components (a) and (b) with the basic composition Examples 1 to 3 in Table 5 in place of the basic composition in Table 1 also has the effect of the present invention. Obtainable.

The components in Table 5 are the same as those in Table 1, and the methylglycine diacetic acid 3Na is as follows.
-Methylglycine diacetate 3Na: Product name "Trilon M Compact" (manufactured by BASF)

Claims (7)

(A) Containing a sulfosuccinic acid branched alkyl ester in which the branched alkyl group has 9 or more and 11 or less carbon atoms [hereinafter referred to as (a) component] and (b) an inorganic alkaline agent [hereinafter referred to as (b) component]. Detergent composition for dishwashers. (A) The branched alkyl group of the component is a branched alkyl group having a main chain having 6 or 7 carbon atoms and a side chain having 1 or more carbon atoms and having a total number of carbon atoms in the side chains of 3 or 4. The cleaning agent composition for a dishwasher according to the description. The cleaning agent composition for a dishwasher according to claim 1 or 2, wherein the branched alkyl group of the component (a) is a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group. The item according to any one of claims 1 to 3, wherein (b) / (a), which is the mass ratio of the content of the component (a) to the content of the component (b), is 5 or more and 1000 or less. Detergent composition for dishwashers. (B) The detergent composition for a dishwasher according to any one of claims 1 to 4, wherein the component is an alkali carbonate metal salt. The detergent composition for a dishwasher according to any one of claims 1 to 5, further comprising a metal sequestering agent as a component (c). The detergent composition for a dishwasher according to any one of claims 1 to 6, further comprising an inorganic peroxide as a component (d).