JP7432566B2 - Liquid detergent composition for dishwashers - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to liquid detergent compositions for dishwashers.

Examples of stains that adhere to tableware include oil stains, egg stains, starch stains from rice grains, and pigment stains from tea, etc. Among these, eggs are a complex stain made of fat and protein. This stain is particularly difficult to remove. Furthermore, in recent years, with the spread of automatic dishwashers and dryers, many detergent compositions for dishwashers have been proposed. Detergents for automatic dishwashers are required to have several characteristics that are different from various types of detergents for hand washing and kitchen use. It must have the cleaning power to separate from tableware using mechanical force. Therefore, in order to improve the detergency against this complex stain, proposals have been made to incorporate various compounds as active ingredients, such as specific nonionic surfactants, enzymes, bleaching agents, and chelating agents.

Patent Document 1 discloses a detergent composition for dishwashers that uses a Guerbet type anionic surfactant and a specific polyoxypropylene in combination and has excellent cleaning power for complex stains. Patent Document 2 discloses a composition for dishwashers that uses an alkyl sulfate salt and a specific polyoxyalkylene alkyl ether sulfate together, and further combines a bleach and a builder to enhance performance.
Patent Document 3 discloses a liquid detergent composition that has excellent detergency and foaming power by combining a sulfosuccinic acid alkyl ester salt, another anionic surfactant, and a polyoxyalkylene amine. Patent Document 4 discloses that by using a combination of a sulfosuccinic acid alkyl ester with a specific structure and an alkyl sulfate, the product produces rich foaming and long-lasting foam during washing, while the foam instantly disappears during rinsing, allowing the rinsing process to be completed with just a small amount of water. Disclosed is a dishwashing composition.

Japanese Patent Application Publication No. 11-61177 Japanese Patent Application Publication No. 2005-239809 Japanese Patent Application Publication No. 2018-184495 Japanese Patent Application Publication No. 2013-100462

However, the compositions described in Patent Documents 1 and 2 are powder compositions that exhibit high cleaning power only when the cleaning pH is alkaline from 9 to 12, and are effective against complex stains in the neutral range. No one has yet been found that exhibits sufficient detergency. In addition, in the case of liquid detergent compositions, the use of bleach and enzymes may be limited from the perspective of storage stability, and liquid detergent compositions have sufficient detergency against complex stains in the neutral range. is required.
In addition, the technologies described in Patent Documents 3 and 4 relate to specific foam properties that enable high cleaning power and both foaming and defoaming properties in hand-washing dishwashing detergents through the use of sulfosuccinic acid alkyl esters. It is a technique and does not suggest any superior effect on complex stains.

In the technical field of liquid detergents for dishwashers, there have been cases where sufficient cleaning power has not been achieved when complex stains of oil and protein adhere strongly to tableware. The inventors analyzed the cause of this in detail and found that as the complex stains dry over time, the proteins form a strong structure together with fats and oils, and these structures solidify (increase in melting point) due to aggregation of these structures. It was found that as the process progressed, the cleaning base could no longer be effectively approached. Therefore, it was necessary to develop a cleaning technology that destroys this strong composite stain structure and detaches it from dishes under the neutral pH range, which is the general cleaning condition for liquid detergents for household dishwashers. .

The present invention provides a liquid detergent composition for dishwashers that has superior detergency against complex stains containing proteins and fats and oils. The object of the present invention is to provide a liquid detergent composition for dishwashers that has excellent detergency against complex stains containing proteins and fats and oils, particularly in the neutral range.

The present invention comprises (a) a sulfosuccinic acid branched alkyl ester having a branched alkyl group having 9 to 12 carbon atoms [hereinafter referred to as component (a)], (b) a hydrocarbon group having 10 to 14 carbon atoms, and a sulfuric acid ester The present invention relates to a liquid detergent composition for dishwashers, which contains a base or a sulfonic acid group, an anionic surfactant [excluding component (a)] [hereinafter referred to as component (b)], and water.

According to the present invention, it is possible to provide a liquid detergent composition for dishwashers that has superior detergency against complex stains containing proteins and fats and oils.

Although the mechanism by which the liquid detergent composition for dishwashers of the present invention improves the detergency against complex stains containing proteins and fats and oils is not clear, it is presumed as follows.
It is thought that complex dirt containing proteins forms a strong structure together with fats and oils. It is thought that a film with a protein backbone is formed on the surface of this structure, and that the protein denatures when it is dried or heated, thereby hindering the action of the cleaning base on protein complex stains. It will be done. Therefore, by using component (a) and component (b) together, component (b) acts on the protein-based membrane and promotes the action of component (a) on complex stains containing proteins. However, it is thought that the cleaning effect on this complex stain is exhibited. Note that the liquid detergent composition for dishwashers of the present invention is not limited to this mechanism of action. Further, in the present invention, the detergency includes not only cleaning of dirt adhering to tableware but also good finish after rinsing.

<Liquid detergent composition for dishwashers>
The liquid detergent composition for dishwashers of the present invention comprises (a) a sulfosuccinic acid branched alkyl ester having a branched alkyl group having from 9 to 12 carbon atoms [hereinafter referred to as component (a)], (b) from 10 to 12 carbon atoms. Contains an anionic surfactant having 14 or less hydrocarbon groups and a sulfate ester base or a sulfonic acid base [excluding component (a)] [hereinafter referred to as component (b)], and water.

<(a) component>
Component (a) is a sulfosuccinic acid branched alkyl ester having a branched alkyl group having 9 to 12 carbon atoms.

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

The branched alkyl group of component (a) preferably 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 2 or more and 4 or less.
The branched alkyl group of component (a) is a branched alkyl group selected from a 2-propylheptyl group, a 4-methyl-2-propylhexyl group, a 5-methyl-2-propylhexyl group, and a 3,5,5-trimethylhexyl group. is preferred, and a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group is more preferred.

As the component (a), a sulfosuccinic acid branched alkyl ester represented by the following general formula (a1) can be mentioned.

[In the formula, R ^1a and R ^2a are each independently a branched alkyl group having 9 or more and 12 or less carbon atoms. A ¹ and A ² are each independently an alkylene group having 2 or more and 4 or less carbon atoms, and x and y are the average number of added moles and are each independently 0 or more and 6 or less. M ¹ is a hydrogen atom or a cation. ]

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

[In the formula, R ^1a and R ^2a are each independently a branched alkyl group having 9 or more and 12 or less carbon atoms. M ¹ is a hydrogen atom or a cation. ]

The following explanation can be applied to each of general formula (a1) and general formula (a1-1).
The carbon numbers of R ^1a and R ^2a may be the same or different.
In the present invention, a hydrocarbon residue obtained by removing a hydroxyl group from a 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 the main chain, and the hydrocarbon chain branched from the main chain is The bonded hydrocarbon chains are called side chains.
When there are two or more main chains, 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 chains are determined in the following order.
1. The side chain branching from the longest hydrocarbon chain with a larger number of carbon atoms is considered the main chain.
2. Next, when the number of carbon atoms in the side chains branching from the longest hydrocarbon chain is the same, the one with the larger number of side chains branching from the longest hydrocarbon chain is defined as the main chain.
3. Next, if the number of side chains branching from the longest hydrocarbon chain is the same, the one with the side chain on the carbon atom closer to the oxygen atom, counting from the carbon atom bonded to the oxygen atom, is the main chain. do.
4. Next, when the positions of the carbon atoms having side chains closest to the oxygen atom are the same, the main chain is the one with the largest number of carbon atoms in the side chain closest to the oxygen atom.
In addition, when two or more longest hydrocarbon chains have the same symmetrical structure, either one 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 chains may be the same or different, and is preferably 3 from the viewpoint of detergency.
In the present invention, the total number of carbon atoms constituting side chains is the total number of carbon atoms in all side chains other than the main chain in one branched alkyl group, and if there are multiple side chains, the total number of carbon atoms in all side chains other than the main chain is the total number of carbon atoms in one branched alkyl group. 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 from the viewpoint of detergency, is 1 or more, preferably 3 or less, and more preferably 2 or less.
In the present invention, the number of side chains is the number of side chains branching from the main chain, and even if the side chain has a side chain further branching from the main chain, the number of side chains does not change. . However, from the viewpoint of detergency, the side chain may further have a side chain branching from the side chain.

The number of branched carbon atoms in R ^1a and R ^2a may be the same or different, and from the viewpoint of detergency, is 1 or more, preferably 3 or less, and even more preferably 2 or less.
In the present invention, the number of branched carbon atoms is the total number of tertiary carbon atoms and quaternary carbon atoms in the chain branched hydrocarbon group.

A preferred embodiment of R ^1a and R ^2a is such that the total number of carbon atoms in the chain branched hydrocarbon group of R ^1a and R ^2a is 9 or more and 11 or less, furthermore 9 or 10, and the number of carbon atoms in the main chain is are each independently 6 or 7, the number of carbon atoms constituting the side chain is 1 or more and 3 or less, and the number of side chains is each independently 1.

The branched alkyl groups of R ^1a and R ^2a may be the same or different, and specifically include a 2-propylheptyl group, a 4-methyl-2-propylhexyl group, a 5-methyl-2-propylhexyl group, and a 3-methyl-2-propylhexyl group. , 5,5-trimethylhexyl group.

In general formula (a1), A ¹ and A ² are each independently an alkylene group 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 moles added, and from the viewpoint of detergency, each independently is 0 or more and 6 or less, preferably 4 or less, more preferably 2 or less, More preferably, it is 0.
Further, from the viewpoint of detergency, x+y is preferably 0 or more, and preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, and even more preferably 0.

In the general formula (a1), ^M1 is a hydrogen ion, an inorganic cation such as a sodium ion, an ammonium ion, a potassium ion, a magnesium ion, a monoethanol ammonium ion, a diethanol ammonium ion, a triethanol ammonium ion, a morpholinium ion. and preferably inorganic cations selected from sodium ions, ammonium ions, potassium ions, and magnesium ions.

The method for preparing a compound in which R ^1a and R ^2a are the same in general formula (a1) is not particularly limited, but for example, the method described in U.S. Patent No. 2,028,091 can be referred to. Furthermore, as a method for preparing an asymmetric compound in which R ^1a and R ^2a are different, for example, it can be produced with reference to JP-A-58-24555. As a raw material for component (a), an alcohol having a predetermined number of carbon atoms to which 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 such as 3,5,5-trimethylhexan-1-ol and 2-propylheptan-1-ol, (2) 5-nonanol and 2,6-dimethyl-4-heptanol Examples include secondary alcohols such as .

<(b) component>
Component (b) of the present invention is an anionic surfactant [excluding component (a)] having a hydrocarbon group having 10 to 14 carbon atoms and a sulfuric acid ester base or a sulfonic acid group.
Component (b) is one or more anionic surfactants selected from alkyl sulfate salts having an alkyl group having 10 to 14 carbon atoms and alkanesulfonates having an alkane moiety of 10 to 14 carbon atoms. It may be.
The hydrocarbon group of component (b) may be an alkyl group or an alkenyl group, with an alkyl group being preferred. The number of carbon atoms in the hydrocarbon group of component (b) is 10 or more and 14 or less, preferably 12 or less. The hydrocarbon group of component (b) is preferably one or more selected from a decyl group, a dodecyl group, and a tetradecyl group, and more preferably one selected from a decyl group and a dodecyl group.

Specifically, component (b) includes decyl sulfate ester salt, dodecyl sulfate ester salt, tetradecyl sulfate ester salt, decane sulfonate, dodecane sulfonate, and tetradecane sulfonate; among these, decyl sulfate ester Salt, dodecyl sulfate salt, decane sulfonate, and dodecane sulfonate are preferred, and decyl sulfate salt is more preferred.
Further, the counter ion may be either an inorganic alkali ion or an organic alkali ion, but from the viewpoint of versatility, sodium ion, potassium ion, and ethanolamine ion are preferable.

Further, the liquid detergent composition for dishwashers of the present invention optionally includes an anion having (X) a hydrocarbon group having 9 or less carbon atoms or 15 or more carbon atoms, and a sulfuric acid ester base or a sulfonic acid group. It may also contain a surfactant [hereinafter referred to as component (X)].
In the liquid detergent composition for dishwashers of the present invention, the ratio of the content of component (b) to the total content of components (b) and (X) is preferably from the viewpoint of cleaning properties for protein complex stains. is 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less.
In the liquid detergent composition for dishwashers of the present invention, the ratio of the content of component (b) having a hydrocarbon group having 10 to 12 carbon atoms to the total content of component (b) and component (X). is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass or less, from the viewpoint of cleaning properties of protein composite stains.

<Composition and other components of the liquid detergent composition for dishwashers of the present invention>
The liquid detergent composition for dishwashers of the present invention preferably contains component (a) in an amount of 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.01% by mass or more, from the viewpoint of detergency. It can be contained at least 1% by mass, and from the viewpoint of storage stability, preferably at most 5% by mass, more preferably at most 3% by mass, even more preferably at most 2% by mass, even more preferably at most 1% by mass. .
In the present invention, the description regarding the amount of component (a) (mass%, etc.) 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. shall be based on.

The liquid detergent composition for dishwashers of the present invention contains component (b), from the viewpoint of cleaning performance, preferably at least 1% by mass, more preferably at least 2% by mass, even more preferably at least 3% by mass, and From the viewpoint of suppressing foaming, the content is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less.
In the present invention, descriptions regarding the amount of component (b) (mass %, etc.) are based on the mass of the compound converted to sodium salt.

In the liquid detergent composition for dishwashers of the present invention, the mass ratio (a)/(b) of the content of component (a) and the content of component (b) is determined from the viewpoint of oil stain cleaning performance. It is preferably at least 0.01, more preferably at least 0.05, even more preferably at least 0.1, and from the viewpoint of cleaning properties for protein complex stains, it is preferably at most 5, more preferably at most 1.

The liquid detergent composition for dishwashers of the present invention can contain (c) a chelating agent [hereinafter referred to as component (c)].
Ingredients (c) include citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid. , 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid. Carboxylic acid or its salt, tripolyphosphoric acid or its salt can be used. Examples of the salt of component (c) include alkali metal salts such as sodium salt and potassium salt.
Component (c) is preferably one or more selected from citric acid, malic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, tripolyphosphoric acid, and salts thereof, including citric acid, trisodium citrate, One or more selected from glutamic acid diacetic acid and salts thereof are more preferable from the viewpoint of cleaning properties for protein complex stains.

When the liquid detergent composition for dishwashers of the present invention contains component (c), the composition contains component (c) in an amount of, for example, 2% by mass or more, further 5% by mass or more, further 10% by mass. In addition, the content can be 30% by mass or less, further 25% by mass or less, further 20% by mass or less.

The dishwasher liquid detergent composition of the present invention can include a suds suppressor. Examples of the foam suppressing agent include silicone, high molecular compounds such as polypropylene glycol, and hydrophobic silica particles. The foam suppressor may be, for example, an oil compound containing silicone oil and hydrophobic silica fine powder. Further, the foam suppressor may be selected from compounds that function as oil agents or solvents, and the compound may be a high molecular compound or a low molecular compound. The foam suppressor is preferably a polymer compound, and more preferably polypropylene glycol.
The weight average molecular weight of the polypropylene glycol is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more from the viewpoint of foam suppression, and preferably 10 or more from the viewpoint of formulation stability. ,000 or less, more preferably 8,000 or less, still more preferably 5,000 or less. Here, the weight average molecular weight of polypropylene glycol is calculated based on the measurement of the hydroxyl value (mgKOH/g). Specifically, the weight average molecular weight of component (b) can be calculated as (m×1000×56/OHV). Here, m is the number of hydroxyl groups in polypropylene glycol, and when the polypropylene glycol is a diol type, m is 2, and when the polypropylene glycol is a triol type, m is 3. Moreover, OHV (mgKOH/g) is a hydroxyl value measured according to JISK 0070.

The liquid detergent composition for dishwashers of the present invention contains a surfactant other than the component (a) and the component (b) [hereinafter referred to as "other surfactant"]. ].
Examples of other surfactants include amphoteric surfactants and nonionic surfactants.

As other surfactants, one or more nonionic surfactants selected from alkyl glycosides, alkyl glyceryl ethers, and polyoxyalkylene alkyl ethers are preferred.
In the alkyl glycoside, the number of carbon atoms in the alkyl group is preferably 8 or more, and preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
In the alkyl glyceryl ether, the number of carbon atoms in the alkyl group is preferably 8 or more, and preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
In the polyoxyalkylene alkyl ether, the number of carbon atoms in the alkyl group is preferably 8 or more, and preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less, and an oxyalkylene group, more preferably an oxyethylene group. The average number of moles added is preferably 3 or more, and preferably 20 or less, more preferably 10 or less. The other surfactant is preferably a nonionic surfactant in which the alkyl group is derived from a secondary alcohol. For example, an oxyethylene group is added to the secondary alcohol in an average number of moles of 1 or more and 10 or less. Polyoxyalkylene alkyl ethers are preferred. Component (c) is preferably foam-inhibiting.

The liquid detergent composition for dishwashers of the present invention preferably contains 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.05% by mass or more of other surfactants from the viewpoint of detergency. It can be contained in an amount of .3% by mass or more, and from the viewpoint of foam suppression, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.0% by mass or less.

The ratio of the total content of components (a) and (b) in the total surfactant contained in the liquid detergent composition for dishwashers of the present invention is preferably 20% by mass or more, more preferably 50% by mass. % or more, more preferably 60% by mass or more, and 100% by mass or less, further 90% by mass or less, and even more preferably 80% by mass or less.

When the liquid detergent composition for dishwashers of the present invention contains anionic surfactants other than the components (a) and (b), all the components contained in the liquid detergent composition for dishwashers of the present invention contain In the anionic surfactant, the ratio of the total content of components (a) and (b) is preferably 50% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less. The ratio of the total content of component (a) and component (b) in all anionic surfactants may be 100% by mass.

The liquid dishwashing detergent composition of the present invention optionally includes a sequestering agent, a pigment, a fragrance, an enzyme, a bleaching agent, a surface modifier, a disinfectant, an antioxidant, an antifoaming agent, a preservative, It may also contain optional components such as stabilizers, hydrotropes, pH adjusters, solvents, and thickeners.

The liquid detergent composition for dishwashers of the present invention contains water. Water may be the remainder after removing component (a), component (b), component (c), and other optional components.

The pH at 25°C of the liquid detergent composition for dishwashers of the present invention is preferably 5 or more, more preferably 5.5 or more, still more preferably 6 or more from the viewpoint of cleaning performance, and from the viewpoint of operational safety. From this point of view, it is preferably 11 or less, more preferably 10 or less, and even more preferably 8 or less. Note that pH can be measured by a glass electrode method (the following pHs can also be measured by a similar method).

The liquid detergent composition for dishwashers of the present invention can be used as a cleaning liquid diluted with water (hereinafter referred to as the cleaning liquid of the present invention) at the time of use. The cleaning liquid of the present invention may be a mixture containing the liquid detergent composition for dishwashers of the present invention and water.

The concentration (diluted concentration) of the dishwasher detergent composition of the present invention in use is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably The content is 0.1% by mass or more, and from the viewpoint of foaming, preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less.

The concentration of component (a) when using the dishwasher detergent composition of the present invention is preferably 1 ppm or more, more preferably 2 ppm or more, and even more preferably 5 ppm or more, from the viewpoint of detergency. From the same viewpoint, the content is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 30 ppm or less.

From the viewpoint of detergency, the concentration of component (b) when using the liquid detergent composition for dishwashers of the present invention is preferably 10 ppm or more, more preferably 20 ppm or more, and even more preferably 50 ppm or more. , from the same point of view, preferably 1,000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less.

The liquid detergent composition for dishwashers of the present invention can be used as a cleaning solution diluted appropriately with water etc., and the liquid detergent composition for dishwashers of the present invention can be diluted at 25°C. From the viewpoint of detergency, the pH in Preferably it is 8 or less.
For example, the pH at 25° C. of a mixture containing 0.2% by mass of the liquid detergent composition for dishwashers of the present invention and water is preferably 5.5 or higher, more preferably 6 or higher, from the viewpoint of detergency. , and preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.
The liquid detergent composition for dishwashers of the present invention can effectively remove complex protein stains that have been difficult to remove in the above pH range.

<How to wash dishes>
The liquid detergent composition for dishwashers of the present invention can be used for dishwashers, furthermore automatic dishwashers, and is further suitably used for cleaning with commercial dishwashers. Note that tableware includes cooking utensils, cleaning utensils, and the like.
When cleaning with a dishwasher, or even a commercial dishwasher, the liquid detergent composition for dishwashers of the present invention is used as a cleaning liquid mixed with water. In this case, a certain amount of the composition is optionally transferred into the dishwasher by means of a feeding device, and a proper concentration of the cleaning liquid is maintained.

The present invention provides a cleaning liquid obtained by diluting the liquid detergent composition for dishwashers of the present invention with water, and a cleaning method for cleaning dishes in a dishwasher using the cleaning liquid. This cleaning method includes the steps of preparing a cleaning liquid by diluting the liquid detergent composition for dishwashers of the present invention with water, and washing dishes using the cleaning liquid in a dishwasher. may be included.
In the step of preparing this cleaning liquid, the concentrations of the liquid detergent composition for dishwashers of the present invention, component (a) and component (b) of the present invention in the cleaning liquid are adjusted to the above-mentioned liquid cleaning composition for dishwashers of the present invention. The agent composition is diluted to the concentration at which it will be used. Further, the pH range of the cleaning liquid at 25°C is the same as the preferred pH range at 25°C of the cleaning liquid obtained by diluting the liquid detergent composition for dishwashers of the present invention.

The cleaning temperature of the cleaning liquid is preferably 30°C or higher, more preferably 40°C or higher, from the viewpoint of productivity and cleaning performance, and preferably 80°C or lower, more preferably 70°C or lower, from the viewpoint of cleaning performance. It is.
After the dishes are washed, they are usually washed with water, hot water or hot water, preferably at 40°C or above, more preferably at 60°C or above, in the same dishwasher or even in an automatic dishwasher. Rinsing is performed with hot water of 80° C. or lower for 5 minutes or more and 40 minutes or less.
In a dishwasher, the cleaning liquid is usually circulated by a pump and used repeatedly.

The dishwasher liquid detergent composition of the present invention is used for washing dishes in a dishwasher. Examples of tableware include items used to store food, such as plates, bowls, and cups, and items used to serve food, such as chopsticks, forks, knives, and spoons. In the present invention, tableware includes, in addition to these items, foods such as storage containers such as Tupperware and bottles, cooking utensils such as kitchen knives, cutting boards, pots, frying pans, and fish grills, and cooking appliances such as food processors and mixers. This may include items that come in contact with the items or their parts, and items that can be washed in a dishwasher. Materials for tableware include plastic (including silicone resin, etc.), metal, ceramic, wood, and combinations thereof. The liquid detergent composition for dishwashers of the present invention is suitably used for cleaning tableware having a hydrophobic surface, for example, plastic tableware. Cleaning using the liquid detergent composition for dishwashers of the present invention is similar to cleaning with a normal dishwasher.

In Example 1 and Comparative Example 1, liquid detergent compositions for dishwashers containing the following components (a), (b), and (c) in the proportions shown in Table 1 were prepared, and protein/lipid complexes were prepared. The cleaning performance against dirt and oil stains was evaluated.

<(a) component>
・Sodium di-(2-propylheptyl)sulfosuccinate (manufactured by Kao Corporation)
・Sodium di-(3,5,5-trimethylhexyl)sulfosuccinate (manufactured by Kao Corporation)
<(a') component>
・Sodium di-(2-ethylhexyl)sulfosuccinate: Sanmorin OT-70 (manufactured by Sanyo Chemical Industries, Ltd.)
<(b) component>
・Alkyl (carbon number 10) sodium sulfate: Sodium decyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Alkyl (carbon number 12) sodium sulfate: Sodium dodecyl sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Sodium alkane (carbon number 10) sulfonate: Sodium 1-decane sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)
・Sodium alkane (carbon number 12) sulfonate: Sodium 1-dodecane sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)
<(b') component>
・Alkyl (carbon number 16) sodium sulfate ester: Sodium hexadecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
・Polyoxyethylene alkyl ether (average number of added moles of EO 5, number of carbon atoms in alkyl group 12-14), Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.)
<(c) component>
・Citric acid: Anhydrous citric acid (manufactured by Wako Pure Chemical Industries, Ltd.)
<Other ingredients>
・Polypropylene glycol: Polypropylene glycol (weight average molecular weight 3000) (manufactured by Wako Pure Chemical Industries, Ltd.)
·water

<Evaluation of cleaning performance>
(1) Cleaning performance for protein/lipid complex stains Apply 4 g of soft-boiled egg yolk heated to 70°C to a ceramic dish with a diameter of 20 cm and a center diameter of 15 cm, and dry for one day to remove the contaminated dish with protein/lipid complex stains. Created. Two contaminated dishes were placed in a dishwasher (manufactured by Panasonic, model number: NP-45MS8S), and a clean dish was placed inside the contaminated dish. 6g of the liquid detergent composition for a dishwasher shown in Table 1 was added, and washing was performed in a standard course. Three panelists observed the dishes after washing and gave evaluation scores based on the following criteria. Table 1 shows the average evaluation score rounded to the first decimal place.
In addition, the concentration of component (a) in the cleaning liquid applied to tableware (the cleaning liquid formed by diluting the liquid detergent composition for dishwashers with water) is 10 ppm when the amount of the composition added is 6 g. there were.
*Evaluation criterion 4 for cleaning performance of protein/lipid complex stains: Initial stains are completely cleaned.
3: Almost all cleaning was completed with less than 20% of the initial dirt remaining.
2: 20% or more and 50% or less of the initial adhesion remained, and the cleaning was generally completed.
1: More than 50% of the initial adhesion remained and could hardly be cleaned.
0: More than 75% of the initial adhesion remains and cannot be cleaned at all.

(2) Oil stain cleaning performance Four polypropylene plates were installed in the dishwasher. Two of the plates were contaminated with 3g of a composite stain of lard/rapeseed oil = 1/1 (mass ratio) applied to each plate, and the remaining two were uncontaminated plates.
6g of the liquid detergent composition for a dishwasher shown in Table 1 was added, and washing was performed in a standard course. A total of three panelists touched the dishes after washing and gave evaluation scores based on the following criteria. Table 1 shows the average evaluation score rounded to the first decimal place.
In addition, the concentration of component (a) in the cleaning liquid applied to tableware (the cleaning liquid formed by diluting the liquid detergent composition for dishwashers with water) is 10 ppm when the amount of the composition added is 6 g. there were.
*Evaluation criterion 4 for oil stain cleaning performance: Dirt has been removed and it feels squeaky and pleasant to the touch.
3: Dirt has been removed, but there is no squeaky feel to the touch.
2: Most of the dirt appears to have been cleaned, but when you rub it with your finger, streaks appear.
1: You can see that oil remains.

<Method for measuring pH>
The pH at 25° C. of a diluted solution (composition concentration: 0.2% by mass) containing the dishwasher liquid detergent composition of each Example and Comparative Example was measured by a glass electrode method. The results are shown in Table 1.

Claims (6)

(a) Sulfosuccinic acid branched alkyl ester having a branched alkyl group having 9 to 12 carbon atoms [hereinafter referred to as component (a)]; (b) a hydrocarbon group having 10 to 14 carbon atoms and a sulfuric acid ester base or sulfonic acid A liquid detergent composition for dishwashers, comprising a base, an anionic surfactant [excluding component (a)] [hereinafter referred to as component (b)], and water. The liquid detergent composition for dishwashers according to claim 1, which contains component (a) in an amount of 0.01% by mass or more and 5% by mass or less. The dishwasher liquid according to claim 1 or 2, wherein the branched alkyl group of component (a) is one or more branched alkyl groups selected from 2-propylheptyl group and 3,5,5-trimethylhexyl group. Cleaning composition. The liquid detergent composition for dishwashers according to any one of claims 1 to 3, wherein the hydrocarbon group of component (b) is selected from a decyl group and a dodecyl group. (c) The liquid detergent composition for a dishwasher according to any one of claims 1 to 4, which contains a chelating agent [hereinafter referred to as component (c)]. The dishwasher according to any one of claims 1 to 5, wherein the pH of the mixture containing 0.2% by mass of the liquid detergent composition for dishwashers and water at 25°C is 5.5 or more and 10 or less. Machine liquid cleaning composition.