Dishwasher cleaning composition

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

[Technical field]

[0001] The present invention relates to a detergent composition for dishwashers. [Background technology]

[0002] Examples of stains that adhere 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 protein stains are difficult to remove, and there is a problem that oil stains reattach to tableware when washed in a dishwasher. In order to improve the cleaning power against oil stains, for example, various types and formulations of surfactants that are active ingredients in cleaning have been proposed. Patent Document 1 discloses a technology for an automatic dishwashing detergent containing an anionic surfactant such as dialkyl sulfosuccinic acid. Patent Document 2 discloses a technology for using a dialkyl sulfosuccinic acid with a specific structure in a dishwashing detergent.

[0003] In addition, for dishwashing detergents, the ability to clean protein stains, especially protein-lipid complex stains such as egg stains, is important in addition to oil stains, and for this purpose, alkali such as sodium carbonate is often used as the main cleaning component. Patent Document 3 discloses a technology for a dishwashing detergent for immersion cleaning containing sodium carbonate and dialkyl sulfosuccinic acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-182904 A [Patent Document 2] JP 2017-214554 A [Patent Document 3] Japanese Patent Application Publication No. 2-151698 Summary of the Invention [Problem to be solved by the invention]

[0005] When a detergent containing alkali as the main cleaning component is mixed with a surfactant to enhance the ability to remove oily stains, foam is generated in the washing chamber of the dishwasher, and the foaming can make it difficult to obtain the expected cleaning power against complex stains of protein and lipids, or can even cause the dishwasher to stop operating. In addition, there is a problem that odors tend to remain in the washing chamber of the dishwasher after washing. To provide a detergent composition for dishwashers which generates little foam in the washing chamber, has excellent detergency for complex soiling containing protein and lipid, and can suppress odor in the washing chamber of a dishwasher after washing. [Means for solving the problem]

[0006] The present invention relates to a detergent composition for dishwashers, which contains (a) a branched alkyl sulfosuccinate ester, in which the branched alkyl group has from 9 to 11 carbon atoms [hereinafter referred to as component (a)], and (b) an inorganic alkaline agent [hereinafter referred to as component (b)]. Effect of the Invention

[0007] According to the present invention, there is provided a dishwashing machine detergent composition which produces little foam in the washing chamber, has excellent cleaning power for complex soils containing protein and lipid, and can suppress odor in the washing chamber of a dishwasher after washing. In addition, the dishwashing machine detergent composition of the present invention has an effect of suppressing re-adhesion of oily soils during washing with a dishwashing machine, and therefore has excellent cleaning power for oily soils. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Although the details of the mechanism of action of the present invention are unclear, the present inventors believe as follows. The component (a) of the present invention is a surfactant that foams little and has a high oil stain cleaning power at a low concentration. On the other hand, it is known that alkaline agents are effective for cleaning lipid / protein stains, but lipid / protein stains are hydrophobic and therefore do not easily come into contact with water-soluble inorganic alkaline agents. The component (a) efficiently brings lipid / protein stains into contact with the inorganic alkaline agent (b), thereby improving the cleaning ability of lipid / protein stains. In addition, the odor components in the cleaning chamber are often caused by components derived from lipids / proteins, and it is believed that an excellent deodorizing effect can also be obtained by improving the cleaning effect of the component (a) and the inorganic alkaline agent.

[0009] <Detergent composition for dishwashing machines> The component (a) is a branched alkyl sulfosuccinate ester in which the branched alkyl group has 9 to 11 carbon atoms.

[0010] The component (a) may be a monoester or a diester, and is preferably a branched alkyl sulfosuccinate diester in which the branched alkyl group has 9 to 11 carbon atoms.

[0011] The branched alkyl group of component (a) is preferably a branched alkyl group having a main chain of 6 or 7 carbon atoms and one or more side chains, the total number of carbon atoms in the side chains being 3. 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.

[0012] Examples of the component (a) include branched alkyl sulfosuccinate esters represented by the following general formula (a1).

[0013] [ka]

[0014] [In the formula, R1a , R 2a are each independently a branched alkyl group having 9 to 11 carbon atoms. 1 , A 2 are each independently an alkylene group having 2 to 4 carbon atoms, and x and y are each independently the average number of moles added, and are each independently 0 to 6. 1 is a hydrogen atom or a cation.

[0015] Further, the component (a) may be a branched alkyl sulfosuccinate ester represented by the following general formula (a1-1): This compound is a compound in which x=0 and y=0 in general formula (a1).

[0016] [ka]

[0017] [In the formula, R 1a , R 2a are each independently a branched alkyl group having 9 to 11 carbon atoms. 1 is a hydrogen atom or a cation.

[0018] The following explanation applies to both general formula (a1) and general formula (a1-1). R 1a , R 2a may be the same or different. In the present invention, the branched chain hydrocarbon group includes a hydrocarbon residue obtained by removing a hydroxyl group from a secondary alcohol.

[0019] In the present invention, R 1a , R 2a Among the branched chain hydrocarbon groups, the hydrocarbon chain having the largest number of carbon atoms counted from the carbon atom bonded to the oxygen atom is the main chain, and the hydrocarbon chains branched from the main chain and bonded to the main chain are side chains. When two or more main chains are considered, that is, when there are two or more hydrocarbon chains with the largest number of carbon atoms (hereinafter also referred to as the longest hydrocarbon chain), the main chain is determined in the following order. 1. The side chain branching off from the longest hydrocarbon chain has the larger number of carbon atoms and is considered the main chain. 2. Next, if the number of carbon atoms in the side chains branching off from the longest hydrocarbon chain are the same, the chain with the greater number of side chains branching off from the longest hydrocarbon chain is determined to be the main chain. 3. Next, if the number of side chains branching off from the longest hydrocarbon chain is the same, the one having a side chain on the carbon atom closer to the oxygen atom, counting from the carbon atom bonded to the oxygen atom, is considered to be the main chain. 4. Next, if the positions of the carbon atoms having side chains closest to the oxygen atom are the same, the one with the greater number of carbon atoms in the side chain closest to the oxygen atom is considered to be the main chain. When two or more longest hydrocarbon chains have the same symmetrical structure, either one may be used as the main chain.

[0020] R 1a , R 2a In each of the branched alkyl groups, the total number of carbon atoms constituting the side chains may be the same or different, and is preferably 3 from the viewpoints of detergency for solid grease and the like and foam suppression properties. In the present invention, the total number of carbon atoms constituting the side chains refers to the total number of carbon atoms in all side chains other than the main chain in one branched alkyl group, and when there are multiple side chains, it refers to the total number of carbon atoms in all of those side chains.

[0021] R 1a , R 2a The number of side chains may be the same or different and is 1 or more, preferably 3 or less, more preferably 2 or less, from the viewpoint of detergency for solid oils and the like and foam-suppressing property. In the present invention, the number of side chains refers to the number of side chains branching from the main chain, and the number of side chains does not change even if the side chain has a further side chain branching from the side chain. However, from the viewpoint of cleaning properties for solid grease and foam suppression properties, the side chain may have a further side chain branching from the side chain.

[0022] R 1a , R 2aThe number of branched carbon atoms may be the same or different, and from the viewpoint of detergency for solid grease and the like and foam-suppressing property, is 1 or more, and preferably 3 or less, and further preferably 2 or less. In the present invention, the number of branched carbon atoms means the total number of tertiary carbon atoms and quaternary carbon atoms in the branched chain hydrocarbon group.

[0023] R 1a , R 2a A preferred embodiment of the formula is R 1a , R 2a the total number of carbon atoms in the branched chain hydrocarbon groups is independently 9 or more and 11 or less, further 9 or 10, the number of carbon atoms in the main chain is independently 6 or 7, the number of carbon atoms constituting the side chains is independently 1 or more and 3 or less, and the number of side chains is independently 1.

[0024] R 1a , R 2a Specific branched alkyl groups may be the same or different, and are preferably branched alkyl groups selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.

[0025] In general formula (a1), A 1 , A 2 are each independently an alkylene group having 2 or more carbon atoms and 4 or less, preferably 3 or less, carbon atoms. In general formula (a1), x and y are the average number of moles added, and from the viewpoint of detergency for solid grease and the like and foam-suppressing property, each of them independently is 0 or more and 6 or less, preferably 4 or less, more preferably 2 or less, and even more preferably 0. Furthermore, from the viewpoint of detergency for solid grease and the like and foam suppression properties, x+y is preferably 0 or more and preferably 12 or less, more preferably 6 or less, even more preferably 3 or less, and still more preferably 0.

[0026] In general formula (a1), M 1is a hydrogen ion, an inorganic cation such as a sodium ion, an ammonium ion, a potassium ion, or a magnesium ion, or an organic cation such as a monoethanolammonium ion, a diethanolammonium ion, a triethanolammonium ion, or a morpholinium ion, and is preferably an inorganic cation selected from the group consisting of a sodium ion, an ammonium ion, a potassium ion, and a magnesium ion.

[0027] In general formula (a1), R 1a , R 2a The method for preparing the compound in which R is the same is not particularly limited. For example, the compound can be prepared by referring to the method described in U.S. Pat. No. 2,028,091. 1a , R 2a As a method for preparing an asymmetric compound having different carbon atoms, for example, JP-A-58-24555 can be referred to. As the raw material of component (a), an alkylene oxide added to an alcohol having a predetermined carbon number can also be used. Suitable alcohols for use in the preparation of component (a) of the present invention include: (1) Primary alcohols such as 3,5,5-trimethylhexan-1-ol and 2-propylheptan-1-ol, (2) Secondary alcohols such as 5-nonanol and 2,6-dimethyl-4-heptanol Examples include:

[0028] The dishwasher detergent composition of the present invention may contain component (a) in an amount of, for example, 0.01% by mass or more, and even 0.05% by mass or more from the viewpoint of cleaning power, and in an amount of, for example, 0.1% by mass or more, and even 0.2% by mass or more, and even 0.3% by mass or more from the viewpoints of cleaning power and deodorizing property, and in an amount of, for example, 10.0% by mass or less, and even 5.0% by mass or less, and even 2.0% by mass or less, and even 1.0% by mass or less, and even 0.8% by mass or less from the viewpoints of cleaning power and foaming property. In the present invention, the description of the amount of the component (a) (such as mass %) refers to the mass of the compound converted into a sodium salt, for example, M 1is based on the mass assuming it is sodium.

[0029] Component (b) is an inorganic alkaline agent. As component (b), an inorganic alkali metal salt is preferred, and one or more compounds selected from sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide are more preferred. As component (b), a compound selected from sodium carbonate and potassium carbonate is even more preferred.

[0030] From the viewpoint of improving the cleaning power for complex soils containing protein and lipids, the dishwasher detergent composition of the present invention may contain component (b) in an amount of, for example, 3% by mass or more, further 4% by mass or more, further 5% by mass 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, and further 35% by mass or less.

[0031] In the dishwasher detergent composition of the present invention, from the viewpoint of cleaning power for oil stains and cleaning power for complex stains containing protein and lipids, the mass ratio (b) / (a) of the content of component (a) to the content of component (b) is preferably 5 or more, more preferably 8 or more, even more preferably 10 or more, still more preferably 15 or more, and is preferably 1,000 or less, more preferably 500 or less, more preferably 200 or less, and even more preferably 100 or less. In addition, in terms of deodorizing effect, the dishwasher detergent composition of the present invention has a mass ratio (b) / (a) of the content of component (a) to the content of component (b) of preferably 500 or less, more preferably 300 or less, even more preferably 200 or less, and still more preferably 100 or less.

[0032] The dishwasher detergent composition of the present invention may contain a sequestering agent as component (c). Examples of component (c) that can be used include polycarboxylic acids or salts thereof, such as citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetate, glutamic acid diacetate, hydroxyethyliminodiacetate, ethylenediaminedisuccinic acid, nitrilotriacetic acid, 1,3-propanediaminetriacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid, and tripolyphosphoric acid or a salt thereof. The component (c) is preferably at least one selected from citric acid, malic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, tripolyphosphoric acid, and salts thereof, and more preferably at least one selected from citric acid, trisodium citrate, glutamic acid diacetic acid, and salts thereof. When the dishwasher detergent composition of the present invention contains component (c), the composition may contain component (c) in an amount of, 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, and further 20% by mass or less.

[0033] The detergent composition for dishwashers of the present invention may contain an inorganic peroxide as component (d). Examples of component (d) include sodium percarbonate, perborate (monohydrate or tetrahydrate), percarbonate, persulfate, and persilicate. As the component (d), one or more inorganic peroxides selected from sodium percarbonate, sodium persulfate, and sodium perborate are more preferable. When the dishwasher detergent composition of the present invention contains component (d), the composition may contain 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. When the dishwasher detergent composition of the present invention contains component (d), the composition may contain component (c) in an amount of, for example, 5% by mass or more, further 10% by mass or more, further 20% by mass or more, and 40% by mass or less, further 35% by mass or less, and further 30% by mass or less.

[0034] The dishwasher detergent composition of the present invention may contain, as further optional components, components such as a solvent, a hydrotrope agent, a dispersant, a pH adjuster, a thickener, a viscosity adjuster, a fragrance, a colorant, an antioxidant, a preservative, a foam suppressor, a bleaching agent (other than component (d)), a bleaching activator, a rust inhibitor, a powder property improver, and an enzyme.

[0035] The detergent composition for dishwashers of the present invention is preferably a solid composition such as a powder, granule or particle.

[0036] From the viewpoint of detergency, the dishwasher detergent composition of the present invention has a pH at 25° C. when diluted with water at a concentration of 0.2% by mass of preferably 8 or more, more preferably 8.5 or more, even more preferably 9 or more, and preferably 12 or less, more preferably 11.5 or less, even more preferably 11 or less. The pH can be measured by a glass electrode method.

[0037] In the present invention, a method is preferred in which the dishwasher detergent composition of the present invention is diluted with water, for example, 10 to less than 10,000 times, and further 50 to less than 5,000 times, to prepare a cleaning liquid and use the diluted cleaning liquid for cleaning.

[0038] The detergent composition for dishwashers of the present invention is used for washing tableware with a dishwasher. Examples of tableware include items used for storing food such as plates, bowls, cups, etc., and items used for serving food such as chopsticks, forks, knives, spoons, etc. In the present invention, tableware may mean items that come into contact with food, such as storage containers such as Tupperware and bottles, cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills, and cooking appliances such as food processors and mixers, and parts thereof that can be washed with a dishwasher. Examples of the material of the tableware include plastics (including silicone resins, etc.), metals, pottery, wood, and combinations thereof. The detergent composition for dishwashers of the present invention is suitable for washing tableware having a hydrophobic surface, such as plastic tableware. Washing using the detergent composition of the present invention is similar to washing with a normal dishwasher. EXAMPLES

[0039] The dishwasher detergent compositions shown in Tables 2 to 4 were prepared by mixing the components shown in Tables 2 to 4 with the basic composition shown in Table 1. The dishwasher detergent compositions were used in an automatic dishwasher, and the cleaning performance, odor inside the washing chamber, and foaming were evaluated by the following methods. The results are shown in the tables. In the tables, component (a') is treated as component (a) and (b) / (a) is shown.

[0040] (1) Ability to clean oil stains Four polypropylene dishes were placed in an automatic dishwasher (NP-45VS6S, Panasonic). Two of the dishes were contaminated dishes that had been coated with 3 g of a composite soil of lard and salad oil (1:1 by mass), and the remaining two were uncontaminated dishes. 6.0 g of the dishwasher detergent composition shown in the table was added, and the dishwasher was washed using the standard cycle. A total of four panelists touched all the dishes after washing, and gave each dish an evaluation score according to the following criteria. The average score for each example was calculated from the evaluation scores given by all panelists, and is shown in the table. The total concentration of components (a) and (b) in the cleaning solution applied to the tableware (the cleaning solution formed by diluting the detergent composition with water) was 2000 ppm when the amount of the composition added was 6.0 g (the same was true for other evaluations). *Evaluation criteria for cleaning (hand feel evaluation) 4: The dirt has been removed and it feels squeaky clean and comfortable to the touch. 3: There isn't much of a squeaky feeling, but the dirt is removed. 2: Most of the dirt has been removed, but streaks remain when rubbing with your fingers. 1: It feels slimy when you touch it. 0: You can see that oil remains. The slimy feeling on the dish after washing is caused by the re-adhesion of oily dirt, and in this evaluation method, a squeaky feeling means that re-adhesion has been suppressed.

[0041] (2) Ability to remove complex stains containing proteins and lipids Four ceramic dishes were placed in an automatic dishwasher (NP-45VS6S, Panasonic). Two of the dishes were contaminated dishes that had been stained with 10 g of denatured egg soil and 5 g of a composite soil of lard / salad oil (1 / 1 by mass), and the remaining two were uncontaminated dishes. 6.0 g of the dishwashing detergent composition shown in the table was added, and the dish was washed using the standard cycle. A total of four panelists visually observed all dishes after washing, and rated each dish according to the following criteria. The average score for each example was calculated from the scores given by all panelists, and is shown in the table. *Evaluation criteria for cleaning of complex stains (visual evaluation) 4: All dirt has been removed and the condition is good. It's slightly lower than 3:4, but it's almost a drop. 2: There is noticeable dirt remaining. 1: The dirt is not removed. In addition, each panelist touched the washed dishes and evaluated them by touch using the same evaluation criteria as for the cleaning ability of oily stains in (1), and the average values ​​are shown in the table.

[0042] (3) Odor inside the washing chamber (deodorizing effect) In an automatic dishwasher (NP-45VS6S, Panasonic), (i) two ceramic plates with 3.5g of mixed curry and rice stains, (ii) two ceramic plates with 2g of oil-pickled sardines stains, (iii) three ceramic bowls with 1.3g of natto stains, and (iv) two ceramic plates with 5g of grilled meat sauce stains were set. The amount of dishwasher detergent composition in the table was 6.0g, and the washing conditions were standard course and 30 minutes of drying. After washing, four panelists checked the odor inside the washing chamber of the automatic dishwasher immediately after washing and 30 minutes after washing, and gave evaluation points according to the following criteria, with the average values ​​shown in the table. *Standard for deodorizing effect 4 points: Unpleasant odor has disappeared. 3 points: Slight odor, but not unpleasant. 2 points: Slightly unpleasant odor. 1 point: Unpleasant odor.

[0043] (4) Evaluation of foaming Using 12.0 g (equivalent to twice the standard amount) of the dishwasher detergent composition shown in the table in an automatic dishwasher (NP-TR3, manufactured by Panasonic Corporation), washing was started under standard washing conditions. The operation was stopped 12 minutes after the mist operation changed to washing, and the state of the foam in the washing chamber was confirmed. After that, one panelist checked the remaining foam after the first drainage and displayed it as a score according to the evaluation criteria. *Foaming evaluation criteria 4 points: Little foaming and little foam remaining after draining. 3 points: There is some foaming or residual foam, but it is not a problematic level. 2 points: The machine does not stop operating, but foams so much that the nozzle rotation slows down. 1 point: Operation stops.

[0044] [Table 1]

[0045] The ingredients in Table 1 are as follows: Maleic acid copolymer: Maleic acid / acrylic acid copolymer (30 / 70 molar ratio), weight average molecular weight 21,000, Poiz-520 (Kao Corporation) Polypropylene glycol: Weight average molecular weight 3000, average condensation degree approx. 50 (diol type, Wako Pure Chemical Industries, Ltd.)

[0046] [Table 2]

[0047] [Table 3]

[0048] *1: The washing machine stopped operating, so the dishes were removed from the machine when it stopped and evaluated. *2: The deodorizing effect could not be evaluated because the cleaning machine was stopped.

[0049] [Table 4]

[0050] The dishwasher detergent compositions in Table 4 also have excellent deodorizing effects immediately after washing and 30 minutes after washing, as evaluated by the method (3) above.

[0051] The components in Tables 2 to 4 are as follows. a-1: sodium di(2-propylheptyl) sulfosuccinate (R in general formula (a1-1) 1a , R 2a is a 2-propylheptyl group and M is sodium) a-2: sodium sulfosuccinate di(3,5,5-trimethylhexyl) ester (R in general formula (a1-1) 1a , R 2a is a 3,5,5-trimethylhexyl group and M is sodium) a'-1: Sodium di(2-ethylhexyl) sulfosuccinate a'-2: Linear alkyl (carbon number 10-14) sodium benzenesulfonate solution (LAS) (the amount of active ingredient is shown in the table.)

[0052] The effects of the present invention can also be obtained with dishwasher detergent compositions prepared by blending components (a) and (b) with basic composition examples 1 to 3 of Table 5 instead of the basic composition of Table 1.

[0053] [Table 5]

[0054] The ingredients in Table 5 are the same as those in Table 1, and the trisodium methylglycine diacetate is as follows. Trisodium methylglycine diacetate: Trade name "Trilon M Compactate" (manufactured by BASF)

Claims

1. A dishwashing machine detergent composition comprising: (a) 0.2% by mass or more and 2.0% by mass or less of a branched alkyl sulfosuccinate ester, the branched alkyl group of which has a main chain having 6 or 7 carbon atoms and one or more side chains, and the total number of carbon atoms in the side chains is 3 [hereinafter referred to as component (a)]; and (b) an inorganic alkali agent [hereinafter referred to as component (b)], A detergent composition for dishwashers, in which the mass ratio (b) / (a) of the content of the component (a) to the content of the component (b) is 10 or more and 200 or less, and the detergent composition is used for cleaning after being diluted with water 10 times or more and less than 10,000 times.

2. 2. The dishwasher detergent composition according to claim 1, wherein the branched alkyl group of the component (a) is selected from the group consisting of a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.

3. 3. The dishwashing machine detergent composition according to claim 1, wherein the component (b) is an alkali metal carbonate.

4. The dishwasher detergent composition according to any one of claims 1 to 3, further comprising a metal sequestering agent as component (c).

5. The dishwasher detergent composition according to any one of claims 1 to 4, further comprising an inorganic peroxide as component (d).

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