WO2023210554A1

WO2023210554A1 - Surfactant composition

Info

Publication number: WO2023210554A1
Application number: PCT/JP2023/016030
Authority: WO
Inventors: 卓司川村
Original assignee: 花王株式会社
Priority date: 2022-04-28
Filing date: 2023-04-24
Publication date: 2023-11-02

Abstract

This surfactant composition contains: (a) 10-30 mass% (exclusive of 10) of a surfactant having a hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (a)); (b) a benzenesulfonic acid in which 1-3 alkyl groups having 1 to 3 carbon atoms may be substituted, or a salt thereof (hereinafter referred to as component (b)); and water, wherein the mass ratio (a)/(b) of the content of component (a) to the content of component (b) is 0.30-2.00.

Description

surfactant composition

The present invention relates to a surfactant composition and a method for controlling foaming properties of the surfactant composition, as well as a detergent composition for a dishwasher and a method for cleaning dishes.

BACKGROUND ART Surfactants are generally used in household cleaning agents and industrial cleaning agents. In addition, in recent years, for the purpose of ease of use and reducing environmental impact, environmentally friendly cleaning agents that have concentrated surfactants to a high concentration to improve ease of use, have compact containers, and reduce the amount of resin have become popular. It will be done.
On the other hand, surfactants have foaming properties as a general property, but for example, in the case of detergents used in automatic dishwashers, there are problems such as foaming causing the machine to stop. In addition, when foaming occurs violently, the rinsing load becomes large and it becomes necessary to use a large amount of water, which may increase the environmental burden. For this reason, a technology that suppresses foaming at the concentration used may be required. In such cases, it is common to use antifoaming agents such as silicone, but cleaning agents that are highly concentrated surfactants and diluted with a large excess of water before use are not effective when diluted. In order to obtain an effective defoaming effect, it is necessary to incorporate the defoaming agent into the concentrated formulation at a relatively high concentration.

Dishwashers are also used to clean dirty dishes, glasses, cooking utensils, and other tableware in the kitchens of homes, restaurants, and coffee shops, and to clean plastic containers for ingredients and products used in food and beverage factories. has been done. The main target stains include food-derived proteins, starches, fats and oils, and these stains are combined and adhere to dishes, glasses, tableware such as cooking utensils, plastic containers, etc. Further, during cooking, these stains may be thermally denatured and become strong stains that may stick.

Usually, washing with a dishwasher is performed in the order of a washing step and a rinsing step. The time required for these steps is very short in terms of process design for commercial use, such as approximately 40 to 180 seconds for the cleaning step and approximately 5 to 20 seconds for the rinsing step. However, in the case of stubborn stains, such a designed time may not be sufficient for cleaning, and it is not uncommon for the cleaning process to take several times the designed time to ensure sufficient cleaning.
It is effective to use a surfactant in combination to quickly clean tough stains made of complex proteins, lipids, and carbohydrates.

JP 2019-151722A discloses a drying finish composition for automatic dishwashers that contains two types of nonionic surfactants, (B) a solubilizer, and (C) water in predetermined amounts. .
In addition, JP 2017-110057 A discloses (a) a predetermined anionic surfactant, (b) a predetermined polymer, (c) an aromatic sulfonic acid, an aromatic carboxylic acid, and salts thereof. Liquid dishwashing detergent compositions containing one or more components as well as water are disclosed.
In addition, JP 2017-119742A describes (A) a surfactant, (B) a chelating agent, (C) a water-soluble solvent, and (D) a compound selected from aromatic sulfonic acids and salts thereof. Disclosed is a dishwasher detergent containing a predetermined amount of (E) water.
Further, JP 2017-110058 A discloses a liquid dishwashing detergent composition containing a specific anionic surfactant and a benzenesulfonic acid type hydrotrope.

Summary of the Invention However, many common antifoaming agents are oil-based compounds such as silicones, and if the antifoaming agent is added at a high concentration to obtain an effective antifoaming effect upon dilution, storage stability will decrease. . For this reason, there is a need for a technique that does not cause problems in storage stability even when a surfactant is blended at a high concentration, and that also provides a high antifoaming effect upon dilution.
The surfactant composition and the foaming control method of the surfactant composition of the present invention are capable of suppressing foaming caused by the surfactant and have excellent storage stability. A method for controlling the foaming properties of active agent compositions is provided.

Furthermore, in the field of detergent compositions for dishwashers, there is a demand for improved detergency against protein stains and lipid stains. On the other hand, for dishwashers, a detergent composition with suppressed foaming properties at the concentration used is desirable.
The dishwasher detergent composition and dishwashing method of the present invention have good cleaning properties for protein stains and lipid stains, can suppress foaming caused by surfactants, and have good storage stability. Provided are an excellent detergent composition for a dishwasher and a method for washing dishes.

The present invention requires (a) more than 10% by mass to 30% by mass of a surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a)], and (b) a surfactant having a hydrocarbon group having 1 to 3 carbon atoms. Contains benzenesulfonic acid or its salt optionally substituted with one or more and three or less alkyl groups [hereinafter referred to as component (b)] and water, the content of component (a) and the content of component (b) The present invention relates to a surfactant composition having a mass ratio (a)/(b) of 0.30 or more and 2.00 or less.

Furthermore, the present invention provides a method for adding component (b) to a surfactant composition containing more than 10% by mass of component (a) and not more than 30% by mass of component (b) and water. The present invention relates to a method for controlling foaming properties of a surfactant composition, in which the mass ratio (a)/(b) of the content is 0.30 or more and 2.00 or less.

In addition, the present invention comprises (c) an anionic surfactant containing the following component (c1) and the following component (c2) [hereinafter referred to as component (c)], the following component (d), and water; The mass ratio (c)/(d) of the content of the component to the content of the component (d) is 1 or more and 20 or less, and the mass ratio (c1) of the content of the component (c1) to the content of the component (c2) The present invention relates to a dishwasher detergent composition in which /(c2) is 0.30 or more and 0.80 or less.
(c1) Component: One or more selected from sulfonic acids having a chain hydrocarbon group having 6 to 16 carbon atoms, sulfuric esters having a chain hydrocarbon group having 6 to 16 carbon atoms, and salts thereof (c2 ) Component: Benzene sulfonic acid or its salt optionally substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms (d) Component: Nonionic having a hydrocarbon group having 6 to 16 carbon atoms surfactant

The present invention also relates to a method of washing dishes, using a dishwasher and washing dishes with a cleaning liquid prepared by diluting the above-mentioned detergent composition for dishwashers with water.

According to the surfactant composition and the foaming control method of the surfactant composition of the present invention, foaming caused by the surfactant can be suppressed, and a surfactant composition with excellent storage stability can be obtained. and a method of controlling foaming properties of a surfactant composition.
Further, according to the dishwasher detergent composition and the dishwashing method of the present invention, the cleaning properties for protein stains and lipid stains are good, and foaming caused by surfactants can be suppressed. A detergent composition for a dishwasher with excellent storage stability and a method for washing dishes are provided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The reason why the surfactant composition of the present invention suppresses foaming caused by surfactants is not necessarily clear, but it is presumed as follows.
By including component (b) in the surfactant composition, the component (b) enters the foam film composed of the surfactant, reducing the stability of the foam film, and as a result, the surfactant It is inferred that foaming caused by component (a) was suppressed when the agent composition was diluted. As a result, even in a surfactant composition containing component (a) at a high concentration, the amount of antifoaming agent conventionally contained for foam suppression can be reduced, and the surfactant composition can be preserved. It is presumed that stability will also be improved.
Furthermore, surfactants having a hydrocarbon group with a carbon number of 8 or more and 18 or less are known to have excellent emulsifying power and high detergency, but even such surfactants can suppress foaming. Therefore, these surfactants can be used in applications where use has been restricted due to foaming properties.
Note that the surfactant composition of the present invention is not limited to the above mechanism of action. Moreover, in the present invention, foaming property may mean that the surfactant composition or a diluted solution of the surfactant composition foams.

In addition, the reason why the detergent composition for dishwashers of the present invention has good cleaning properties for protein stains and lipid stains, suppresses foaming caused by surfactants, and has excellent storage stability is as follows. Although it is not necessarily certain, it is inferred as follows.
When a composition containing only component (c1) is diluted and used for cleaning, a strong foam film is formed, and the foam formed has low foam-breaking properties. On the other hand, when a composition containing components (c1) and (c2) is diluted and washed, a foam film containing a mixture of components (c2) and (c1) is formed. It is presumed that this reduces the packing properties of the foam film and improves the foam-breaking properties of the formed foam.
Therefore, a detergent composition for a dishwasher containing components (c1) and (c2) can suppress foaming caused by components (c1) and (d) when diluting the detergent composition. It is inferred. As a result, even in dishwasher detergent compositions containing components (c1) and (d) at high concentrations, it is possible to reduce the amount of antifoaming agent that was conventionally contained to suppress foaming. It is presumed that the storage stability of the dishwasher detergent composition is also improved.
In addition, a diluted solution containing component (c1) or component (d), which has excellent emulsifying power and high detergency, can be used while suppressing foaming of the diluted solution, so that protein stains and/or stains can be removed in dishwasher applications. It is also presumed that the cleaning performance of oil stains is improved.
Note that the dishwasher detergent composition of the present invention is not limited to the above mechanism of action. In the present invention, low foaming may mean that the detergent composition for a dishwasher or a diluted solution obtained by diluting the detergent composition for a dishwasher with water has low foaming.

<Surfactant composition>
The surfactant composition of the present invention comprises: (a) a surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a)]; (b) an alkyl group having 1 to 3 carbon atoms; Contains benzenesulfonic acid or a salt thereof [hereinafter referred to as component (b)] which may be substituted with 1 or more and 3 or less and water.

<(a) Component>
Component (a) is a surfactant having a hydrocarbon group having 8 to 18 carbon atoms. Component (a) may be a surfactant having a chain hydrocarbon group having 8 to 18 carbon atoms.
Component (a) is (a1) an anionic surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a1)], and (a2) having a hydrocarbon group having 8 to 18 carbon atoms. Nonionic surfactant [hereinafter referred to as component (a2)], (a3) cationic surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a3)], and (a4) carbon number 8 or more One or more surfactants selected from amphoteric surfactants having 18 or less hydrocarbon groups [hereinafter referred to as component (a4)], preferably one or more surfactants selected from components (a1) and (a2). It is a surfactant. The hydrocarbon group 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 (a) is 8 or more, preferably 9 or more, more preferably 10 or more from the viewpoint of detergency, and 18 or less from the viewpoint of composition stability and detergency. Preferably it is 16 or less, more preferably 14 or less.

<(a1) component>
The anionic surfactant as component (a1) includes a linear or branched saturated fatty acid salt having an alkyl group having 8 to 18 carbon atoms, an unsaturated fatty acid salt having an alkenyl group having 8 to 18 carbon atoms, Linear or branched alkyl sulfate salts having 8 to 18 carbon atoms, linear alkylbenzene sulfonates having 8 to 18 carbon atoms, branched alkylbenzene sulfonates having 8 to 18 carbon atoms, 8 to 18 carbon atoms The following linear or branched alkyl sulfonates, alkenyl sulfonates with 8 to 18 carbon atoms, monoalkyl phosphates with 8 to 18 carbon atoms, monoalkenyl phosphates with 8 to 18 carbon atoms , perfluoroalkyl carboxylic acid salts having 8 to 18 carbon atoms, alkylmethyl taurate salts having 8 to 18 carbon atoms, and alkylene oxide adducts thereof.

More specifically, as the component (a1), an anionic surfactant having a hydrocarbon group having 8 or more and 18 or less carbon atoms and a sulfonic acid group or a sulfuric acid ester group can be mentioned. The sulfonic acid group or sulfuric acid ester group may be a salt.

Component (a1) is selected from benzenesulfonic acid and its salt having a hydrocarbon group having 8 to 18 carbon atoms substituting on the benzene ring, and sulfuric acid ester and its salt having a hydrocarbon group having 8 to 18 carbon atoms. One or more selected anionic surfactants may be mentioned.

Examples of benzenesulfonic acids or salts thereof having a hydrocarbon group having 8 or more and 18 or less carbon atoms to be substituted on the benzene ring include alkylbenzenesulfonic acids or salts thereof having a chain alkyl group having 8 or more and 18 or less carbon atoms. The alkyl group has carbon atoms of 8 or more, preferably 9 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 15 or less, from the viewpoint of oil detergency and storage stability as a formulation. , more preferably an alkyl group of 14 or less.

Examples of sulfuric esters or salts thereof having a hydrocarbon group having 8 or more and 18 or less carbon atoms include alkyl sulfuric esters or salts thereof having an alkyl group having 8 or more and 18 or less carbon atoms. From the viewpoint of detergency and storage stability as a preparation, the alkyl group has carbon atoms of 8 or more, preferably 9 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 15 or less, More preferably, it is an alkyl group of 14 or less.

In addition, as components (a1) other than these, α-sulfo fatty acid methyl esters or salts thereof in which the hydrocarbon group of the fatty acid moiety has carbon atoms of 8 or more and 18 or less, preferably 10 or more and 16 or less, carbon atoms of the alkyl group is 8 or more and 18 or less (preferably polyoxyethylene, the average number of added moles is 0.5 or more, preferably 1 or more, and 4 or less, preferably 3 or less) alkyl ether sulfuric acid or its salt, alkyl Alkyl glyceryl sulfonates whose group has 8 to 18 carbon atoms, olefin sulfonic acids or salts thereof whose olefin moiety has 8 to 18 carbon atoms, alkanesulfonic acids whose alkane moieties have 8 to 18 carbon atoms, or Salts thereof, alkylsulfosuccinic acids whose alkyl group has 8 to 18 carbon atoms, or salts thereof, and the like.

Component (a1) salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, and organic amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts. Alkali metal salts are preferred, and sodium salts are more preferred.

Component (a1) is a benzenesulfonic acid or a salt thereof having a hydrocarbon group having 8 or more and 18 carbon atoms to be substituted on the benzene ring, or a salt thereof having 8 or more carbon atoms and 18 carbon atoms, from the viewpoint of oil cleaning properties and storage stability as a preparation. Sulfuric esters or salts thereof having the following hydrocarbon groups, alkylbenzenesulfonic acids or salts thereof having alkyl groups having 8 to 18 carbon atoms, and alkyl sulfuric esters or salts thereof having alkyl groups having 8 to 18 carbon atoms. is preferred. Component (a1) is more preferably an alkyl sulfate having an alkyl group having 8 to 18 carbon atoms or a salt thereof.　

<(a2) component>
Nonionic surfactants as component (a2) include aliphatic alcohol alkylene oxide adducts with 8 to 18 carbon atoms, fatty acid esters of sorbitan alkylene oxide adducts with 8 to 18 carbon atoms, and 8 to 18 carbon atoms. Examples include alkyl glucosides having alkyl groups of 8 to 18 carbon atoms, sucrose fatty acid esters having alkyl groups of 8 to 18 carbon atoms, and alkylamine oxides having alkyl groups of 8 to 18 carbon atoms.

As the component (a2), there can be mentioned a nonionic surfactant represented by the following general formula (a2-1).
R ^1a (CO) _m O-(AO) _n -R ^2a (a2-1)
[In the formula, R ^1a is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R ^2a is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, The AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is the average number of added moles of the AO group, and is a number of 1 to 50. ]

In general formula (a2-1), R ^1a is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. From the viewpoint of oil detergency, the number of carbon atoms in R ^1a is 8 or more, preferably 10 or more, more preferably 11 or more, and from the viewpoint of storage stability as a formulation, 18 or less, preferably 16 or less, more preferably is 15 or less, more preferably 14 or less.
The aliphatic hydrocarbon group for R ^1a is preferably a group selected from an alkyl group and an alkenyl group.
Examples of the aliphatic hydrocarbon group for R ^1a include groups selected from primary alkyl groups and secondary alkyl groups. is preferred. A secondary alkyl group refers to an alkyl group in which the carbon atom of R ^1a bonded to CO or O in R ^1a (CO) _m O- in general formula (a2-1) is a secondary carbon atom. say.
In general formula (a2-1), m is preferably 0.
In general formula (a2-1), R ^2a is preferably a hydrogen atom.

In the general formula (a2-1), the AO group is one or more groups selected from ethyleneoxy and propyleneoxy groups. When the AO group contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be a block type bond or a random type bond. From the viewpoint of oil detergency, the AO group is preferably a group containing an ethyleneoxy group.

In general formula (a2-1), n is the average number of added moles of AO groups, and is a number from 1 to 50. The larger the number of n, the higher the HLB value, and the smaller the number, the lower the HLB value. From the viewpoint of oil detergency, n is 1 or more, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, even more preferably 6 or more, even more preferably 7 or more. And, from the viewpoint of low foaming property and foam breaking property, it is 50 or less, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less.

A more preferable compound as a compound represented by general formula (a2-1) has an ethyleneoxy group (hereinafter sometimes referred to as EO group) having an average degree of polymerization (or sometimes referred to as average number of added moles) of 1 or more, preferably is 3 or more and 25 or less, preferably 20 or less, and the average degree of polymerization (or the average number of added moles) of propyleneoxy groups (hereinafter sometimes referred to as PO groups) is 1 or more, preferably 3 above, and preferably 25 or less, the EO group and the PO group may be a random bond or a block bond, preferably a block bond, and more preferably have oil detergency and low foaming properties. And from the viewpoint of foam breaking properties, the block bonding is in the order of EOPOEO or EOPO with respect to the alkyl ether, and the number of carbon atoms in the alkyl group is 8 or more, more preferably 12 or more, and 18 or less, more It is preferably a polyoxyethylene (polyoxypropylene) alkyl ether derived from 14 or less, more preferably 12, linear primary or secondary alcohols. Component (a2) is more preferably a polyoxyethylene (polyoxypropylene) alkyl ether derived from a secondary alcohol whose alkyl group has carbon atoms of 8 or more, preferably 12 or more, and 18 or less, preferably 14 or less. preferable.

<(a3) component>
The cationic surfactant as component (a3) includes an alkylamine salt having a linear or branched alkyl group having 8 or more and 18 or less carbon atoms, an alkylethylenediamine salt having an alkyl group having 8 or more and 18 or less carbon atoms, carbon Examples include alkyltrimethylammonium salts having an alkyl group of 8 to 18 carbon atoms, dialkyldimethylammonium salts having an alkyl group of 8 to 18 carbon atoms, and the like.

<(a4) component>
The amphoteric surfactant as component (a4) includes alkyl carboxybetaine having an alkyl group having 8 to 18 carbon atoms, alkyl sulfobetaine having an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 18 carbon atoms. Examples include alkylamide amino acid salts having groups.

From the viewpoint of oil detergency, component (a) is preferably one or more compounds selected from component (a1) and component (a2), and is an alkylbenzenesulfonic acid having an alkyl group having 8 to 18 carbon atoms and a salt thereof. , alkyl sulfate esters and salts thereof having an alkyl group having 8 or more and 18 or less carbon atoms, and polyoxyalkylene alkyl ethers having an alkyl group having 8 or more and 18 or less carbon atoms.

<(b) component>
Component (b) is benzenesulfonic acid or a salt thereof which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms. The surfactant composition of the present invention can contain one or more types of component (b).
Component (b) is preferably one or more selected from p-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid, and salts thereof.
Component (b) salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, organic amine salts such as monoethanolamine salts, diethanolamine salts, and triethanolamine salts. and the sodium salt is preferred.

<Composition and other ingredients>
The surfactant composition of the present invention contains component (a) in an amount of more than 10% by mass, preferably 10.5% by mass or more, more preferably 11% by mass or more, still more preferably 12% by mass, from the viewpoint of detergency. The content is more preferably 14% by mass or more, and from the viewpoint of low foaming properties and foam breaking properties, 30% by mass or less, preferably 27% by mass or less, more preferably 25% by mass or less. In addition, in the present invention, in the regulations regarding the mass of component (a), the regulations regarding the mass of component (a1) use values converted to sodium salt. Moreover, it is more preferable that the total content of component (a1) and component (a2) is within the above range.

In the surfactant composition of the present invention, the component (a1) is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, even more preferably 5% by mass or more, from the viewpoint of detergency. The content is at least 6% by mass, more preferably at least 6% by mass, and from the viewpoint of low foaming and foam breaking properties, at most 30% by mass, preferably at most 27% by mass, more preferably at most 25% by mass.

The surfactant composition of the present invention contains component (a2) in an amount of more than 10% by mass, preferably 10.5% by mass or more, more preferably 12% by mass or more, still more preferably 13% by mass, from the viewpoint of detergency. The content is more preferably 14% by mass or more, and from the viewpoint of low foaming properties and foam breaking properties, 30% by mass or less, preferably 27% by mass or less, more preferably 25% by mass or less.

When the surfactant composition of the present invention contains component (a1) and component (a2), the mass ratio (a1)/(a2) of the content of component (a1) and the content of component (a2) is , from the viewpoint of detergency, preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.10 or more, and from the viewpoint of low foaming property and foam breakage property, preferably 50 or less, more It is preferably 40 or less, more preferably 30 or less.

In the surfactant composition of the present invention, component (b) is preferably 3.5% by mass or more, more preferably 5% by mass or more, from the viewpoint of storage stability, low foaming property, and foam breakage property of the preparation. , more preferably 8% by mass or more, and from the viewpoint of performance balance and economy, for example, 60% by mass or less, further 50% by mass or less, further still 40% by mass or less. From the viewpoint of low foaming properties and foam breaking properties, it is preferable that the amount of component (b) contained in the surfactant composition of the present invention is as large as possible. In the present invention, the mass of the component (b) is specified using an acid form conversion value.

In the surfactant composition of the present invention, the mass ratio (a)/(b) of the content of component (a) to the content of component (b) is 0 from the viewpoint of oil detergency and storage stability. .30 or more, preferably 0.50 or more, more preferably 0.70 or more, even more preferably 1.00 or more, and 2.00 or less, preferably 1.00 or more from the viewpoint of low foaming property and foam breaking property. It is 90 or less, more preferably 1.80 or less, even more preferably 1.70 or less. In addition, when the surfactant composition of the present invention contains component (a1) of an anionic surfactant and component (a2) of a nonionic surfactant as component (a), the content of component (a1) and The mass ratio (a1)/(b) of the content of component (b) is preferably 0.30 or more, and preferably 0.80 or less. In the surfactant composition of the present invention, the mass ratio (a1)/(b) may satisfy the above range, and further the mass ratio (a)/(b) may satisfy the above range.

Since the surfactant composition of the present invention can obtain the effects of the present invention over a wide pH range, it can be used at a suitable pH depending on the intended use. The surfactant composition of the present invention has a pH at 25° C. of, for example, 1 or more, further 2 or more, further 3 or more, even 6 or more, and 14 or less, further 13 or less, and even 12 or less. , and further may be 8 or less. This pH is determined by the following measurement method.
<pH measurement method>
A composite electrode for pH measurement (manufactured by Horiba, Ltd., glass Connect the sliding sleeve type). Next, fill a 100 mL beaker with each of pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), Immerse in a constant temperature bath at ℃ for 30 minutes. The pH measurement electrode is immersed in a standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The surfactant composition to be measured is adjusted to 25° C., the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

The surfactant composition of the present invention is not particularly limited; may be 3 or more, further 6 or more, and 14 or less, further 12 or less, and even 8 or less. This pH is determined by the above-mentioned measuring method (however, the surfactant composition is read as a diluted surfactant composition).

The surfactant composition of the present invention may contain water from the viewpoint of storage stability. Examples of water include, but are not limited to, tap water, well water, ion exchange water, distilled water, and the like. Water is preferably used in an amount that accounts for the balance of the composition (an amount that adds up to 100% by weight). The surfactant composition of the present invention contains water in the composition, for example, 5% by mass or more, further 10% by mass or more, further 15% by mass or more, further still 20% by mass or more, further still 25% by mass or more, The content can be 85% by mass or less, further 60% by mass or less. The surfactant composition of the present invention may be a liquid surfactant composition.

Moreover, the surfactant composition of the present invention can also be made into a powder formulation from the viewpoint of suppressing the foaming property of a diluted solution during use. The present invention requires (a) more than 10% by mass to 30% by mass of a surfactant having a hydrocarbon group having 8 to 18 carbon atoms, and (b) 1 to 3 alkyl groups having 1 to 3 carbon atoms. contains benzenesulfonic acid or a salt thereof which may be substituted with less than or equal to 0.00 or less.

The surfactant composition of the present invention includes a solvent, a hydrotrope, a chelating agent, a dispersant, a pH adjuster, a thickener, a viscosity modifier, a fragrance, a coloring agent, and the like, as long as the object of the present invention is not impaired. Components such as foam suppressants and enzymes (excluding those corresponding to components (a) and (b)) can be blended. In addition, the surfactant composition of the present invention can obtain a sufficient foam-inhibiting effect without using a silicone foam-inhibiting agent. The silicone foam inhibitor in the surfactant composition of the present invention is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, even more preferably 0.01% by mass or less, even more preferably substantially Contains no.

The surfactant composition of the present invention is used for suppressing and controlling the foaming property of a surfactant to exert its effects.
For example, the surfactant compositions of the present invention may be cleaning compositions, finishing compositions, descaling compositions.
Specifically, the surfactant composition of the present invention is a hard surface cleaning composition, a cleaning composition for tableware and/or hard surfaces around the kitchen, a dishwashing composition, a dishwasher cleaning composition, etc. It may be a cleaning agent composition for automatic dishwashers, a cleaning agent composition for equipment cleaning, a cleaning agent composition for floors, and furthermore a liquid cleaning agent composition for hard surfaces, tableware and/or kitchen. Liquid cleaning compositions for surrounding hard surfaces, liquid cleaning compositions for tableware, liquid cleaning compositions for dishwashers, liquid cleaning compositions for automatic dishwashers, liquid cleaning compositions for equipment cleaning, floors It may be a liquid cleaning composition for use. These cleaning compositions may be finish compositions or descaling compositions.

Hard items around the kitchen are items used around the kitchen, and specifically include (1) storage areas for food, tableware, and cooking utensils such as refrigerators and cupboards;
(2) food preparation areas such as drains, cooking tables, range hoods, sinks, gas ranges, and microwave ovens; and (3) floors and walls around the storage areas and cooking areas. In the present invention, these are referred to as "hard articles around the kitchen" for convenience.
In addition, as tableware, specifically,
(i) So-called tableware such as plates and bowls;
(ii) Storage containers such as Tupperware and bottles;
(iii) Cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills;
(iv) Parts and appliances that come into contact with food, such as cooking appliances such as food processors and mixers. In the present invention, these are referred to as "tableware" for convenience.

Materials for the hard article include natural resins, synthetic resins (including rubber, urethane, silicone resins, etc.), glass, metals, ceramics, wood, and combinations thereof. The surfactant composition of the present invention can clean these tableware and/or hard articles around the kitchen.

When the surfactant composition of the present invention is used as a detergent composition for a dishwasher, it is possible to incorporate surfactants, which were conventionally limited to be included due to the foaming property of the surfactant. . This increases the degree of freedom in selecting the surfactant to be incorporated into the dishwasher detergent composition, and improves the detergency of the dishwasher detergent composition against oil stains and protein stains.
By increasing the degree of freedom in selecting surfactants to be added to detergent compositions for dishwashers, the detergent composition for dishwashers will have good performance even in the neutral to slightly alkaline range, such as pH 6 or higher and pH 11 or lower. Cleanability can be obtained.

<How to clean hard surfaces>
Hereinafter, one aspect of foaming control in the surfactant composition of the present invention will be explained using an example in which the surfactant composition of the present invention is used for cleaning a hard surface. The active agent composition and the foaming control method of the present invention are not limited to this example.

The present invention provides a method for cleaning a hard surface, which comprises contacting the hard surface with a cleaning liquid prepared by diluting the surfactant composition of the present invention with water (hereinafter referred to as the cleaning liquid of the present invention).
The matters described in connection with the surfactant composition of the present invention can be appropriately applied to the hard surface cleaning method of the present invention. In the surfactant composition used in the hard surface cleaning method of the present invention, component (a), component (b), mass ratio (a)/(b), etc., pH, and specific examples of the target hard surface. and preferred examples are also the same as those for the surfactant composition of the present invention.

The cleaning liquid of the present invention can contain the surfactant composition of the present invention in water, for example, more than 1 times, furthermore, 100 times or more, furthermore, 300 times or more, and up to 10,000 times, furthermore, up to 2,000 times, and even more. It may be prepared by diluting it 1,500 times or less.

From the viewpoint of oil stain cleaning properties and protein stain cleaning properties, the cleaning liquid of the present invention preferably contains component (a) at 0.001% by mass or more, more preferably at least 0.003% by mass, and even more preferably at 0.005% by mass. It can be contained in an amount of at least 0.5% by mass, more preferably at most 0.1% by mass, even more preferably at most 0.05% by mass.

From the viewpoint of low foaming properties and foam breaking properties, the cleaning liquid of the present invention contains component (b) preferably at least 0.0003% by mass, more preferably at least 0.0005% by mass, and even more preferably at least 0.001% by mass. % or more, and preferably 0.06% by mass or less, more preferably 0.04% by mass or less, still more preferably 0.02% by mass or less.

In the present invention, the content ranges of component (a) and component (b) in the cleaning liquid can be set by arbitrarily selecting and combining the above-mentioned values.

The pH of the cleaning liquid of the present invention is preferably 6 or more, more preferably 6.2 or more, still more preferably 6.5 or more, from the viewpoint of reducing the risk of chemical injury and reducing the environmental burden by reducing the pH of wastewater. It is 10.5 or less, more preferably 10.2 or less, even more preferably 10 or less, even more preferably 9 or less.

In the hard surface cleaning method of the present invention, contact between the hard surface and the cleaning liquid of the present invention is preferably carried out using an automatic dishwasher.
Said hard surface is preferably the hard surface of tableware and/or hard articles around the kitchen, more preferably the hard surface of tableware.

In the hard surface cleaning method of the present invention, the cleaning liquid of the present invention is applied to the hard surface for preferably 20 seconds or more, more preferably 30 seconds or more, still more preferably 40 seconds or more, and even more preferably 60 seconds or more, from the viewpoint of cleaning performance. The contact is made for at least 2 seconds, and from the viewpoint of work efficiency, preferably at most 600 seconds, more preferably at most 300 seconds, even more preferably at most 180 seconds, even more preferably at most 100 seconds.

In the hard surface cleaning method of the present invention, the temperature of the cleaning liquid of the present invention is preferably 30°C or higher, more preferably 35°C or higher, still more preferably 40°C or higher, and even more preferably 50°C, from the viewpoint of cleaning performance. The temperature is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower.

In the hard surface cleaning method of the present invention, the flow rate when bringing the cleaning liquid into contact with the hard surface of the tableware, etc. is preferably 5 m/min or more, more preferably 10 m/min or more, and even more preferably is 50 m/min or more, and preferably 2,000 m/min or less, more preferably 1,000 m/min or less, more preferably 500 m/min or less, even more preferably 250 m/min or less, even more preferably 150 m/min. It can be as follows.

After contacting the hard surface with the cleaning liquid of the present invention, it is preferred to rinse the hard surface with water. The temperature of the water rinsing the hard surface is preferably 50°C or higher, more preferably 55°C or higher, even more preferably 60°C or higher, and preferably 80°C or lower.
The rinsing time for the hard surface is preferably 4 seconds or more, more preferably 5 seconds or more, and preferably 10 seconds or less, more preferably 9 seconds or less.
The flow rate of the rinse water is preferably 5 m/min or more, more preferably 10 m/min or more, even more preferably 100 m/min or more, and preferably 2,500 m/min or less, more preferably 2,000 m/min or less, More preferably, it is 1,500 m/min or less.

In the present invention, the automatic dishwasher may be any dishwasher that is generally available on the market, and although it is possible to use a household automatic dishwasher, it is preferably a commercial automatic dishwasher. When cleaning with a commercial dishwasher, the cleaning liquid of the present invention is generally prepared by mixing a concentrated composition of the cleaning liquid of the present invention with water. At this time, a certain amount of the concentrated composition is optionally transferred into the commercial dishwasher by a feeding device to maintain an appropriate concentration of the cleaning liquid. The concentrated composition is supplied by, for example, directly inserting a tube specifically designed for commercial dishwashers into a container made of plastic or the like filled with the composition and sucking it up. The cleaning liquid is then supplied inside the commercial dishwasher.

<Method for controlling foaming properties of surfactant composition>
The present invention includes adding component (b) to a surfactant composition containing more than 10% by mass of component (a) and not more than 30% by mass of component (b), and water. Provided is a method for controlling the foaming properties of a surfactant composition, in which the mass ratio (a)/(b) of the surfactant composition is 0.30 or more and 2.00 or less.
The matters described for the surfactant composition of the present invention can be applied to these methods as appropriate. Preferred embodiments of the composition, for example, specific and preferred examples of component (a) and component (b), content of each component, preferred range of mass ratio (a)/(b), etc. are also included in the surfactant of the present invention. It is the same as the agent composition.
Moreover, the method for controlling the foaming property of the surfactant composition of the present invention may be to suppress the foaming property caused by the surfactant contained in the surfactant composition. That is, the method of controlling the foaming property of a surfactant composition of the present invention may be a method of suppressing the foaming property of the surfactant composition.

In the method for controlling foaming properties of a surfactant composition of the present invention, from the viewpoint of economy and work efficiency, the surfactant composition is preferably 100 times or more, more preferably 200 times or more, and even more preferably is 500 times or more, and from the viewpoint of cleaning properties, preferably 10,000 times or less, more preferably 8,000 times or less, and still more preferably 5,000 times or less. (referred to as a diluted solution) can be used.

From the viewpoint of detergency, the diluted liquid of the present invention contains component (a) preferably at least 0.001% by mass, more preferably at least 0.003% by mass, even more preferably at least 0.005% by mass, and The content is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less.

The diluted liquid of the present invention preferably contains component (b) in an amount of 0.0003% by mass or more, more preferably 0.0005% by mass or more, and still more preferably 0.001% by mass, from the viewpoint of low foaming property and foam breakage property. The content can be at least 0.06% by mass, more preferably at most 0.04% by mass, even more preferably at most 0.02% by mass.

<Cleaning composition for dishwashers>
The dishwasher detergent composition of the present invention comprises (c) an anionic surfactant containing the following component (c1) and the following component (c2) [hereinafter referred to as component (c)], component (d) below, and water. Contains.
(c1) Component: One or more selected from sulfonic acids having a chain hydrocarbon group having 6 to 16 carbon atoms, sulfuric esters having a chain hydrocarbon group having 6 to 16 carbon atoms, and salts thereof (c2 ) Component: Benzene sulfonic acid or its salt optionally substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms (d) Component: Nonionic having a hydrocarbon group having 6 to 16 carbon atoms surfactant

<(c) component>
Component (c) includes component (c1) and component (c2). Component (c) can contain one or more types of component (c1) and one or more types of component (c2).

<(c1) component>
Component (c1) is one or more selected from sulfonic acids having a chain hydrocarbon group having 6 to 16 carbon atoms, sulfuric esters having a chain hydrocarbon group having 6 to 16 carbon atoms, and salts thereof. be.
Component (c1) salts include monovalent metal salts such as sodium salts and potassium salts, divalent metal salts such as magnesium salts, and organic amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts. and the sodium salt is preferred. The same applies to the specific example of component (c1) below.

The sulfonic acid or its salt as component (c1) has a carbon number of 6 or more, preferably 8 or more, more preferably 10 or more from the viewpoint of detergency, and 16 or less from the viewpoint of low foaming property and foam breaking property. , preferably 15 or less, more preferably 14 or less chain hydrocarbon groups, or a salt thereof.
The chain hydrocarbon group is preferably a straight chain or branched hydrocarbon group, more preferably a straight chain or branched alkyl group or alkenyl group, from the viewpoint of detergency, low foaming property and foam breaking property. , more preferably a straight-chain or branched alkyl group, even more preferably a straight-chain alkyl group. The same applies to the sulfonic acid or its salt in the following specific examples.

The sulfonic acid or its salt as the component (c1) is an alkanesulfonic acid or its salt having a hydrocarbon group having 6 or more and 16 or less carbon atoms, or a chain hydrocarbon group (alkyl group or alkenyl group) having 6 or more and 16 or less carbon atoms. α-olefin sulfonic acid or its salt having a hydrocarbon group having 6 to 16 carbon atoms, mono- or dialkyl sulfosuccinic acid having a hydrocarbon group having 6 to 16 carbon atoms or a salt thereof, and these may be used alone or in combination of two or more.

The sulfonic acid or its salt as the component (c1) includes an alkylbenzenesulfonic acid or a salt thereof whose alkyl group has 6 to 16 carbon atoms, an alkenylbenzenesulfonic acid or its salt whose alkenyl group has 6 to 16 carbon atoms, Alkanesulfonic acids or salts thereof in which the alkyl group has 6 to 16 carbon atoms; α-olefin sulfonic acids or salts thereof in which the α-olefin moiety has 6 to 16 carbon atoms; fatty acid moiety has 6 to 16 carbon atoms α-sulfo fatty acids or salts thereof, α-sulfo fatty acid lower alkyl esters or salts thereof in which the fatty acid moiety has 6 or more carbon atoms and 16 or less carbon atoms, and the ester moiety has 1 or more carbon atoms and 5 or less. One type or two or more types may be used.
The sulfonic acid or its salt as the component (c1) may have a benzene ring between the chain hydrocarbon group and the sulfonic acid group, and the alkylbenzene sulfonic acid in which the chain alkyl group has 4 to 16 carbon atoms. or a salt thereof is preferred, and sodium alkylbenzenesulfonate in which the chain alkyl group has 4 to 16 carbon atoms is more preferred.

The sulfuric ester or its salt as the component (c1) has a carbon number of 6 or more, preferably 8 or more, more preferably 10 or more from the viewpoint of detergency, and 16 or less from the viewpoint of low foaming property and foam breaking property. , preferably 15 or less, more preferably 14 or less chain hydrocarbon groups, or a salt thereof.
The chain hydrocarbon group is preferably a straight chain or branched hydrocarbon group, more preferably a straight chain or branched alkyl group or alkenyl group, from the viewpoint of detergency, low foaming property and foam breaking property. , more preferably a straight-chain or branched alkyl group, even more preferably a straight-chain alkyl group. The same applies to the sulfuric esters or salts thereof in the following specific examples.

The sulfuric ester or its salt as the component (c1) is a sulfuric ester having an alkyl group or an alkenyl group having 6 to 16 carbon atoms (alkyl sulfate, alkenyl sulfate, (poly)oxyalkylene alkyl ether sulfate ["poly"] means two or more consecutive oxyalkylene groups], (poly)oxyalkylene alkenyl ether sulfate) and salts thereof, preferably an alkyl sulfate having 6 to 16 carbon atoms. One or more selected from ester salts and (poly)oxyalkylene alkyl ether sulfate salts having an alkyl group having 6 to 16 carbon atoms and an oxyalkylene group having 2 to 3 carbon atoms, more preferably carbon It is an alkyl sulfate ester salt having a number of 6 or more and 16 or less.
The alkyl group or alkenyl group may be linear or branched, and from the viewpoint of detergency, a linear alkyl group or alkenyl group is preferable, and a linear alkyl group is more preferable.

The sulfuric ester or its salt as the component (c1) is preferably one or more selected from the anionic surfactants represented by the following general formula (c1) from the viewpoint of excellent foam suppressing properties and cleaning power for complex stains.
R ^1c -O-(AO) _m1 -SO ₃ -M ₁ (c1)
[In the formula, R ^1c represents an alkyl group or alkenyl group having 6 to 16 carbon atoms, AO represents an ethyleneoxy group or a propyleneoxy group, m1 represents the average number of added moles of AO, and 0 to 1. It is a number less than or equal to 5. M ₁ represents a hydrogen atom or a cation. ]

In the above general formula (c1), R ^1c is an alkyl group or alkenyl group having 6 or more and 16 or less carbon atoms, and may be a straight chain or a branched chain, from the viewpoint of detergency. R ^1c is preferably a linear alkyl group having 6 or more and 16 or less carbon atoms.
m1 indicates the average number of moles of AO added, and is 0 or more, and from the viewpoint of detergency and foam control, 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and even more preferably 0. It is .5 or less, more preferably 0.3 or less, even more preferably 0.1 or less. Further, it is also preferable that m1 is 0.

M ₁ is a hydrogen atom or a cation, and examples of the cation that forms a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Examples of the alkali metal ions include sodium ions, potassium ions, and lithium ions, and examples of the alkanol ammonium ions include monoethanol ammonium ions, diethanol ammonium ions, triethanol ammonium ions, and the like. Among these, sodium ions or potassium ions are preferred.

<(c2) component>
Component (c2) is benzenesulfonic acid or a salt thereof which may be substituted with one to three alkyl groups having 1 to 3 carbon atoms. The dishwasher detergent composition of the present invention can contain one or more types of component (c2).
Component (c2) is preferably one or more selected from p-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid, and salts thereof from the viewpoints of storage stability, low foaming properties, and foam breakage properties.
Component (c2) salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, and organic amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts. and the sodium salt is preferred.

<(d) component>
Component (d) is a nonionic surfactant having a hydrocarbon group having 6 to 16 carbon atoms. Component (d) has a carbon number of 6 or more, preferably 8 or more, more preferably 10 or more from the viewpoint of detergency, and 16 or less, preferably 15 or less, more preferably 14 or less from the viewpoint of storage stability. A nonionic surfactant having a hydrocarbon group, preferably a straight or branched chain hydrocarbon group. Component (d) may contain one or more of the above-mentioned nonionic surfactants.
The nonionic surfactant of component (d) is an aliphatic alcohol alkylene oxide (preferably propylene oxide and/or ethylene oxide) adduct (sometimes referred to as polyoxyalkylene alkyl or alkenyl ether) having 6 to 16 carbon atoms. ), an alkylene oxide, preferably ethylene oxide or propylene oxide, more preferably ethylene oxide may be added, for example, a polyhydric alcohol having 3 to 8 carbon atoms, such as sorbitol, pentaerythritol, glycerin, etc., and a carbon number 6 or more Ester compounds with 16 or less fatty acids (sometimes referred to as polyhydric alcohol fatty acid esters), ethylene oxide or propylene oxide, more preferably monohydric alcohols with 1 to 3 carbon atoms to which ethylene oxide may be added. Examples include esters of fatty acids with 6 to 16 carbon atoms (sometimes referred to as alcohol fatty acid esters), and alkylamine oxides having one straight or branched alkyl group having 8 to 16 carbon atoms.

As component (d), one or more types selected from nonionic surfactants represented by the following general formula (d1) can be mentioned.
R ^1d (CO) _m2 O-(AO) _n -R ^2d (d1)
[In the formula, R ^1d is an aliphatic hydrocarbon group having 6 to 16 carbon atoms, R ^2d is a hydrogen atom or a methyl group, CO is a carbonyl group, m2 is a number of 0 or 1, The AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is the average number of added moles of the AO group, and is a number of 1 to 50. ]

In the general formula (d1), R ^1d is an aliphatic hydrocarbon group having 6 or more and 16 or less carbon atoms. The number of carbon atoms in R ^1d is 6 or more, preferably 8 or more, more preferably 10 or more from the viewpoint of detergency, and 16 or less, preferably 15 or less, more preferably 14 or less from the viewpoint of storage stability. be.
The aliphatic hydrocarbon group for R ^1d is preferably a group selected from an alkyl group and an alkenyl group.
Examples of the aliphatic hydrocarbon group for R ^1d include groups selected from primary alkyl groups and secondary alkyl groups, with secondary alkyl groups being preferred from the viewpoint of low foaming properties and foam breaking properties. The term "secondary alkyl group" refers to an alkyl group in which the carbon atom of R ^1d bonded to CO or O in R ^1d (CO) _m2 O- in general formula (d1) is a secondary carbon atom. The alkyl group is preferably a straight chain. In the present invention, secondary alkyl groups also include those in which the hydrocarbon group itself is a straight chain.
In general formula (d1), m2 is preferably 0.
In general formula (d1), R ^2d is preferably a hydrogen atom.

In the general formula (d1), the AO group is one or more groups selected from ethyleneoxy and propyleneoxy groups. When the AO group contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be a block type bond or a random type bond. From the viewpoint of detergency, the AO group is preferably a group containing an ethyleneoxy group.

In the general formula (d1), n is the average number of added moles of AO groups, and is a number of 1 to 50. The larger the number of n, the higher the HLB value, and the smaller the number, the lower the HLB value. From the viewpoint of oil detergency, n is 1 or more, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, even more preferably 6 or more, even more preferably 7 or more. And, from the viewpoint of low foaming property and foam breaking property, it is 50 or less, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less.

A more preferable compound as a compound represented by general formula (d1) has an ethyleneoxy group (hereinafter sometimes referred to as EO group) having an average degree of polymerization (or sometimes referred to as average number of added moles) of 1 or more, preferably 3. above, and is 25 or less, preferably 20 or less, and the average degree of polymerization (or sometimes referred to as average number of added moles) of propyleneoxy groups (hereinafter also referred to as PO groups) is 1 or more, preferably 3 or more, The number is preferably 25 or less, and the EO group and the PO group may be a random bond or a block bond, preferably a block bond, and more preferably have oil detergency, low foaming property, and foam. From the viewpoint of cuttability, the block bond is in the order of EOPOEO or EOPO with respect to the alkyl ether, and the number of carbon atoms in the alkyl group is 8 or more, more preferably 12 or more, and 16 or less, more preferably Polyoxyethylene (polyoxypropylene) alkyl ethers derived from up to 14, and even more preferably 12, linear primary or secondary alcohols.
Component (d) is more preferably a polyoxyethylene (polyoxypropylene) alkyl ether derived from a secondary alcohol whose alkyl group has carbon atoms of 6 or more, preferably 12 or more, and 16 or less, preferably 14 or less. preferable.

<Composition and other ingredients>
The dishwasher detergent composition of the present invention contains component (c), from the viewpoint of detergency, preferably at least 9% by mass, more preferably at least 10% by mass, even more preferably at least 11% by mass, and even more preferably at least 10% by mass. The content is preferably 12% by mass or more, and from the viewpoint of storage stability, preferably 30% by mass or less, more preferably 28% by mass or less, still more preferably 25% by mass or less. The content of component (c) may be the sum of the content of component (c1) and the content of component (c2). In the present invention, the specification regarding the mass of component (c1) uses a value converted to sodium salt, and the specification regarding the mass of component (c2) uses an acid conversion value.

The detergent composition for dishwashers of the present invention contains component (c1), from the viewpoint of detergency, 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 storage stability, the content is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less.

In the dishwasher detergent composition of the present invention, the component (c2) is preferably 3% by mass or more, more preferably 4% by mass or more, from the viewpoints of low foaming properties, foam breakability, and storage stability. More preferably 5% by mass or more, even more preferably 9% by mass or more, even more preferably 10% by mass or more, and from the economic point of view, preferably 30% by mass or less, more preferably 25% by mass or less, and The content is preferably 20% by mass or less.

In the dishwasher detergent composition of the present invention, the mass ratio (c1)/(c2) of the content of the component (c1) and the content of the component (c2) is determined by the cleaning performance, low foaming property, and foam breakage. From the viewpoint of properties, it is 0.30 or more, preferably 0.35 or more, more preferably 0.40 or more, even more preferably 0.45 or more, even more preferably 0.50 or more, and cleansability and low foaming. From the viewpoint of properties and foam breakability, it is 0.80 or less, preferably 0.75 or less, more preferably 0.70 or less, even more preferably 0.65 or less. From the viewpoint of egg stain cleaning power, the mass ratio (c1)/(c2) is preferably 0.35 or more. In addition, the dishwasher detergent composition of the present invention contains component (d) to improve cleaning performance, but from the viewpoint of low foaming property and foam breakage property, the mass ratio (c1) /(c2) is preferably 0.80 or less. The detergency is more advantageous when a reducing agent, which is the component (f) described later, is used in combination.

The dishwasher detergent composition of the present invention contains component (d) in an amount of preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 6% by mass or more, from the viewpoint of detergency, and From the viewpoint of storage stability, the content is preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 15% by mass or less.

In the dishwasher detergent composition of the present invention, the mass ratio (c)/(d) of the content of component (c) to the content of component (d) is determined by the storage stability, low foaming property, and foaming property. From the viewpoint of breakability, it is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, even more preferably 2 or more, and from the viewpoint of low foaming property and foam breakability, it is 20 or less, preferably 18 Below, it is more preferably 15 or less, still more preferably 10 or less.

The detergent composition for dishwashers of the present invention preferably contains 13% by mass or more, more preferably 15% by mass or more, from the viewpoints of cleanability and economic efficiency, in total of component (c) and component (d). More preferably 18% by mass or more, even more preferably 20% by mass or more, and from the viewpoint of storage stability, low foaming property and foam breaking property, preferably 50% by mass or less, more preferably 45% by mass or less, More preferably, the content is 40% by mass or less. In the dishwasher detergent composition of the present invention, from the viewpoint of oil cleaning tolerance, the total content of the components (c) and (d) in the composition is preferably 15% by mass or more.

The dishwasher detergent composition of the present invention can contain a surfactant other than the component (c) and the component (d).
Surfactants other than component (c) and component (d) include, for example, anionic surfactants [excluding those that fall under component (c)], nonionic surfactants [however, component (d)] ], cationic surfactants, amphoteric surfactants, etc.
In the detergent composition for dishwashers of the present invention, the ratio of the total content of components (c) and (d) to the total content of surfactants contained in the composition ((c) + (d) ) / total surfactant) is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less, from the viewpoint of detergency and storage stability. Furthermore, it may be 95% by mass or less, and even more preferably 90% by mass or less. The detergent composition for dishwashers of the present invention contains 100% by mass of components (c) and (d) as surfactants, that is, the surfactants contained in the detergent composition for dishwashers of the present invention. However, there may be only component (c) and component (d).

<(e) Component>
The dishwasher detergent composition of the present invention can optionally contain (e) a chelating agent.
Component (e) is preferably a chelating agent having a conditional calcium stability constant pK'Ca of 2.6 or more at pH 7.5 and 60° C. from the viewpoint of protein detergency and scale inhibition.
The conditional calcium stability constant pK'Ca of component (e) at pH 7.5 and 60°C is preferably 2.6 or more, more preferably 2.7 or more, and further Preferably it is 3.0 or more, even more preferably 3.2 or more, and from the viewpoint of availability, it is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less.

For the conditional calcium stability constant pK'Ca of component (e) at pH 7.5 and 60°C, a value measured by the following method is used.
Using a calcium ion selective electrode (for example, manufactured by HORIBA), drop 0.2 mL of a 2 g/L calcium chloride solution at 25 °C into 100 mL of distilled water at 60 °C, measure the potential at that time, and evaluate each drop. A first-order approximation formula is calculated by setting the logarithm of the calcium ion concentration in the amount on the horizontal axis and the potential on the vertical axis. Next, add distilled water to component (e) to adjust the concentration to 1 g/L, and adjust the pH to 7.5 with 1N sodium hydroxide and/or 1N hydrochloric acid to prepare a chelating agent solution. . Take out 100 mL of the chelating agent solution, heat it to 60° C., drop 3 mL of 2 g/L calcium chloride solution at 25° C., and measure the potential using a calcium ion selective electrode (for example, manufactured by HORIBA). Substitute the potential at this time into the approximate equation to calculate the uncaptured calcium concentration A (mol/L) in the chelating agent solution, and substitute it into the following equation together with the chelating agent concentration B (mol/L). K'Ca is calculated, and pK'Ca is calculated by taking the logarithm.
K'Ca=(5.4×10 ^-5 -A)/(A×(B-(5.4×10 ^-5 -A)))

Component (e) specifically includes ethylenediaminetetraacetic acid (pK'Ca6.0), hexametaphosphoric acid (pK'Ca5.7), polyacrylic acid (pK'Ca4.2), and acrylic acid-maleic acid copolymer. combination (pK'Ca approximately 4.6 (may vary depending on monomer ratio)), citric acid (pK'Ca 3.4), tripolyphosphoric acid (pK'Ca 3.8), nitrilotriacetic acid (pK'Ca 2. 9), glutamine diacetate (pK'Ca2.7), and salts thereof, and from the viewpoint of protein detergency and scale inhibiting properties, ethylenediaminetetraacetic acid, hexametaphosphoric acid, and polyester are preferred. One or more selected from acrylic acid, acrylic acid-maleic acid copolymer, citric acid, tripolyphosphoric acid, nitrilotriacetic acid, glutamine diacetic acid, and salts thereof, more preferably ethylenediaminetetraacetic acid, hexametaphosphoric acid, and polyester. One or more types selected from acrylic acid, acrylic acid-maleic acid copolymer, citric acid, and salts thereof, more preferably one or more types selected from polyacrylic acid, citric acid, and salts thereof. . Examples of the salt include alkali metal salts such as sodium and potassium salts, ammonium salts, and alkanolamine salts such as monoethanolamine and triethanolamine, and from the viewpoint of easy availability, potassium salts or sodium salts are preferred.

The polyacrylic acid or its salt as component (e) may be a copolymer containing a monomer other than acrylic acid and copolymerizable with acrylic acid (excluding maleic acid). The weight average molecular weight of the component (e), polyacrylic acid or its salt, is 1,000 or more, preferably 2,000 or more, and 20,000 or less, preferably 17, 000 or less. This weight average molecular weight is determined by gel permeation chromatography using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent. Molecular weight standard reagent (manufactured by Aldrich) was used as a standard substance.

The acrylic acid-maleic acid copolymer or its salt as component (e) is a copolymer containing a monomer other than acrylic acid and maleic acid and which is copolymerizable with acrylic acid and/or maleic acid. Good too. The weight average molecular weight of the acrylic acid-maleic acid copolymer or its salt as component (e) is 1,000 or more, preferably 2,000 or more, and preferably 100, 000 or less, more preferably 90,000 or less. This weight average molecular weight is determined by gel permeation chromatography using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent. Molecular weight standard reagent (manufactured by Aldrich) was used as a standard substance.

The dishwasher detergent composition of the present invention contains component (e) preferably at least 0.0001% by mass, more preferably at least 0.0005% by mass, and further Preferably 0.001% by mass or more, even more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass. % or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 6% by mass or more, and from the economic point of view, preferably can be contained in an amount of 40% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less, even more preferably 15% by mass or less, even more preferably 12% by mass or less.

<(f) component>
The dishwasher detergent composition of the present invention may optionally contain (f) a reducing agent having an oxidation-reduction potential of +71 mV or less.
The redox potential of component (f) is, from the viewpoint of protein detergency, at most +71 mV, preferably at most +60 mV, more preferably at most +55 mV, even more preferably at most +50 mV. In addition, the lower the lower limit of the redox potential of component (f), the more effective it can be expected, and although it is not particularly limited, from the viewpoint of availability, it is preferably 0 mV or more, more preferably 3 mV or more. .
For the redox potential of component (f), a value measured by the following method is used. Add distilled water to the component (f) to a concentration of 0.016 mol/L, and add 1 mol/L of hydrochloric acid and/or sodium hydroxide to adjust the pH to 7.5 to prepare a preparation solution. . The temperature of the prepared solution is adjusted to 60° C., and the redox potential is measured using a redox potential meter (for example, an ORP meter (ORP5 Pen ORP meter) manufactured by Sem Corporation).

Specifically, component (f) is one or more selected from sulfite, disulfite, thiosulfate, and iodide salt, and specifically, sodium sulfite (+50 mV), potassium sulfite (+50 mV ), sodium disulfate (+17mV), potassium disulfate (+17mV), potassium iodide (+28mV), sodium iodide (+28mV), sodium thiosulfate (+5mV), and one or more selected from potassium thiosulfate (+5mV) can be mentioned. Component (f) is not particularly limited as long as it has a redox potential of +71 mV or less, but from the viewpoint of protein detergency, it is preferably selected from sodium sulfite, sodium disulfite, potassium iodide, and sodium thiosulfate. More preferably, it is one or more selected from sodium sulfite, sodium disulfite, and sodium thiosulfate. However, the value in parentheses indicates the value of the redox potential.

In the dishwasher detergent composition of the present invention, component (f) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, from the viewpoint of protein detergency. , and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less.

<(g) Component>
The dishwasher detergent composition of the present invention may optionally contain (g) an enzyme.
As component (g), from the viewpoint of finished product quality, one or more enzymes selected from protease, amylase, and lipase are preferred, and protease is more preferred.

Examples of proteases include proteases that can act in neutral or alkaline aqueous solutions. Specific examples of preferred proteases include alkaline proteases described in WO 99/018218, preferably those in which 70% or more of the amino acid sequence shown in SEQ ID NO: 1 or 2 is conserved; Among the alkaline proteases described in JP-A No. 5-25492, preferred examples include alkaline protease K-16 and alkaline protease K-14. In addition, Novozymes products are sold under the trade names Savinase (registered trademark), Cannase (registered trademark), Evalase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark). Proteases produced by Bacillus subtilisins are supplied under the trade names FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark), Prafect (registered trademark), and Prafect prime (registered trademark) manufactured by DuPont. Examples include proteases and mutant types thereof. Among these, there are enzymes in which 80% or more of the amino acid sequence shown by SEQ ID NO: 1 or 2 described in WO 99/018218 is conserved, Sabinase, Evalase, Alcalase, and Progress (Novozymes) manufactured by Novozymes. More preferred are DuPont's Plafect and Plafect Prime. As the protease that can be prepared, for example, KP43 listed in the Examples of JP-A No. 2017-221188 can be used.

Examples of amylase include Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, and Bacillus cereus. , Bacillus macerans ( Bacillusmacerans), Pseudomonas stutzeri, Klebusiella aerogenes, actinomycetes such as Streptomyces griseus, Aspergillus oryzae, Aspergillus niger molds such as illus niger), Seeds of grasses and leguminous plants, digestive glands of animals such as humans and pigs, and those obtained from many organisms can be used. The amylase used in the present invention can be used to transform host cells, etc., which have been transformed with the above-mentioned microorganisms or their mutants, or recombinant vectors having DNA sequences encoding these enzymes or their mutants, into assimilable carbon sources, nitrogen The enzyme can be obtained by inoculating the enzyme into a medium containing essential nutrients and culturing according to a conventional method, and following a general method for collecting and purifying enzymes. The enzyme solution thus obtained can be used as it is, but it can also be purified, crystallized, and made into a powder or liquid preparation by known methods. The amylase used in the present invention is preferably α-amylase. Commercially available amylases that can be used include the trade names Rapidase (manufactured by Gist Brokers), the trade names Termamil, Duramil and Steinzyme (manufactured by Novozymes Japan Co., Ltd.), Amplify (manufactured by Novozymes), and the trade names Plaster ST and Plaster. OxAm (manufactured by Genencore International) can be mentioned.

Preferred lipases include triacylglycerol lipase of EC3.1.1.3, cholesterol esterase of EC3.1.1.13, monoacylglycerol lipase of EC3.1.23, and lipoprotein lipase of EC3.1.1.34. The origin of lipase is not limited, but examples include lipase derived from animals, plants, and microorganisms. Lipases derived from microorganisms include those of the genus Rizopus, Aspergillus, Mucor, Pseudomonas, Geotrichum, Penicillium, Candida, etc. One example is the origin.
The lipases are Lipase A "Amano" 6, Lipase AY "Amano" 30SD, Lipase GS "Amano" 250G, Lipase R "Amano", Lipase DF "Amano" 15, Lipase MER "Amano" (all of these are manufactured by Amano Enzyme Co., Ltd.) ), lipase (manufactured by Nagase Sangyo Co., Ltd.), lipase MY, lipase OF, lipase PL, lipase PLC, lipase QLM, lipase QLC, phospholipase D (manufactured by Meito Sangyo Co., Ltd.), lipoprotein lipase (Oriental Yeast Co., Ltd.) Co., Ltd.), Lipase (manufactured by Toyo Jozo Co., Ltd.), Lipex, Lipolase, Lipase SP-225 (manufactured by Novo), Lipase (manufactured by Gist), Lipase A, Lipase B (manufactured by Sapporo Breweries) Co., Ltd.) can be used.

In the dishwasher detergent composition of the present invention, component (g) is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more as enzyme protein, from the viewpoint of finish quality of washed items. , more preferably 0.0001% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less.
In the present invention, the provisions regarding the mass of component (g) shall be calculated as the amount of enzyme protein.

From the viewpoint of safety, the dishwasher detergent composition of the present invention has a pH at 25° C. of preferably 6 or higher, more preferably 6.2 or higher, even more preferably 6.5 or higher, and preferably 6.5 or higher. It is 11 or less, more preferably 10 or less, even more preferably 9 or less. This pH is determined by the following measurement method.
<pH measurement method>
A pH measurement composite electrode (for example, Horiba, Ltd., pH/Ion Meter F-23) with a saturated potassium chloride aqueous solution (3.33 mol/L) as the pH electrode internal solution Connect the glass sliding sleeve type (manufactured by Seisakusho). Next, fill a 100 mL beaker with each of pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), Immerse in a constant temperature bath at ℃ for 30 minutes. The pH measurement electrode is immersed in a standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The dishwasher detergent composition to be measured is adjusted to 25° C., the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

From the viewpoint of safety, the dishwasher detergent composition of the present invention has a pH at 25° C. of the diluted product diluted with water to a concentration of 0.2% by mass, preferably 6 or more, more preferably 6.5. or more, and preferably 10.5 or less, more preferably 9 or less. This pH is determined by the above-mentioned measurement method (however, the dishwasher detergent composition is read as the diluted dishwasher detergent composition).

The dishwasher detergent composition of the present invention preferably contains water from the viewpoint of stability and workability of the composition. Examples of water include, but are not limited to, tap water, well water, ion exchange water, distilled water, and the like. Water is preferably used in an amount that accounts for the balance of the composition (an amount that adds up to 100% by weight). The detergent composition for a dishwasher of the present invention can contain water, for example, 20% by mass or more, further 24% by mass or more, further 30% by mass or more, and 85% by mass or less.

The detergent composition for a dishwasher of the present invention includes a solvent, a hydrotrope, a dispersant, a pH adjuster, a thickener, a viscosity modifier, a fragrance, a coloring agent, and the like, as long as the object of the present invention is not impaired. Components such as antioxidants, preservatives, foam inhibitors, bleaching agents, and bleach activators (excluding those corresponding to components (c) to (f)) can be blended.

The viscosity at 20° C. of the dishwasher detergent composition of the present invention may be, for example, 1,200 mPa·s or less, and further 1,000 mPa·s or less, from the viewpoint of protein detergency. The lower limit of the viscosity may be 0 mPa·s or more. This viscosity was measured using a B-type viscometer.

In the present invention, tableware is
(i) In addition to so-called tableware such as plates, bowls, cups, chopsticks, knives, forks, and spoons,
(ii) Storage containers such as Tupperware and bottles;
(iii) Cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills;
(iv) Storage or transportation equipment such as racks and containers;
This may include members and equipment that come into contact with foods such as food.

<How to wash dishes>
The present invention provides a method for washing dishes, using a dishwasher and washing dishes with a cleaning liquid prepared by diluting the detergent composition for dishwashers of the present invention with water.
The matters described in connection with the dishwasher detergent composition of the present invention can be appropriately applied to the dishwashing method of the present invention. In the dishwasher detergent composition of the present invention used in the dishwashing method of the present invention, each mass of component (c), component (d), component (e), component (f), and component (g) is The ratio, pH, specific examples and preferred examples of tableware are also the same as those of the dishwasher detergent composition of the present invention.

The cleaning liquid of the present invention contains the detergent composition for dishwashers of the present invention more than 1 times, furthermore, 300 times or more, and less than 5,000 times, furthermore, less than 4,000 times, and furthermore, less than 2,000 times. It may be prepared by diluting it to

The cleaning liquid of the present invention preferably contains component (c), for example, preferably 0.003% by mass or more, more preferably 0.004% by mass or more, and even more preferably is 0.005% by mass or more, even more preferably 0.006% by mass or more, even more preferably 0.007% by mass or more, and from the economic point of view, preferably 30% by mass or less, more preferably 10% by mass. % or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less.

From the viewpoint of cleaning properties, the cleaning liquid of the present invention contains component (c1), for example, preferably 0.003% by mass or more, more preferably 0.004% by mass or more, still more preferably 0.005% by mass or more. More preferably 0.006% by mass or more, even more preferably 0.007% by mass or more, and from the viewpoint of economic efficiency, preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass. The content can be further preferably 0.5% by mass or less, even more preferably 0.1% by mass or less.

The cleaning liquid of the present invention preferably contains component (c2), for example, at least 0.003% by mass, more preferably at least 0.004% by mass, and still more preferably at least 0.00% by mass, from the viewpoint of low foaming properties and defoaming properties. 005% by mass or more, even more preferably 0.006% by mass or more, even more preferably 0.007% by mass or more, and from the viewpoint of economic efficiency, preferably 30% by mass or less, more preferably 10% by mass or less, The content is more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less.

From the viewpoint of cleaning properties, the cleaning liquid of the present invention contains component (d), for example, preferably 0.003% by mass or more, more preferably 0.004% by mass or more, still more preferably 0.005% by mass or more. More preferably 0.006% by mass or more, even more preferably 0.007% by mass or more, and from the viewpoint of economic efficiency, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass. The content can be further preferably 0.5% by mass or less, even more preferably 0.1% by mass or less.

The cleaning liquid of the present invention preferably contains components (c) and (d) in total, for example, preferably 0.005% by mass or more, more preferably 0.00% by mass or more, from the viewpoints of detergency, low foaming properties, and defoaming properties. 007% by mass or more, more preferably 0.008% by mass or more, even more preferably 0.009% by mass or more, even more preferably 0.01% by mass or more, and from an economic standpoint, preferably 50% by mass. The content is more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.1% by mass or less.

The cleaning liquid of the present invention preferably contains component (e) in an amount of, for example, 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.001% by mass, from the viewpoint of protein cleaning properties and scale inhibiting properties. % by mass or more, even more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, and from the economical point of view, preferably 0.2% by mass or less, more preferably 0.15% by mass. % or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less.

From the viewpoint of protein cleaning properties, the cleaning liquid of the present invention contains component (f), for example, preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, still more preferably 0.0008% by mass or more, Even more preferably 0.001% by mass or more, even more preferably 0.003% by mass or more, and from the viewpoint of economic efficiency, preferably 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.001% by mass or more. It can be contained in an amount of 5% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less.

The cleaning liquid of the present invention preferably contains component (g) in an amount of, for example, 0.000001% by mass or more, more preferably 0.000005% by mass or more, and still more preferably 0.00001% by mass, from the viewpoint of finish quality of the cleaning product. Above, even more preferably 0.000015% by mass or more, even more preferably 0.00002% by mass or more, and from the economical point of view, preferably 1% by mass or less, more preferably 0.5% by mass or less, and The content is preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less.

In the present invention, the content ranges of the (c) component, (d) component, (e) component, (f) component, and (g) component in the cleaning liquid are determined by arbitrarily selecting and combining the above-mentioned values. Can be set.

In the tableware cleaning method of the present invention, from the viewpoint of cleaning performance, the cleaning liquid is applied to the tableware for, for example, 20 seconds or more, further 30 seconds or more, further 40 seconds or more, 600 seconds or less, further 300 seconds or less, and further 180 seconds or more. Contact for less than seconds.

In the tableware washing method of the present invention, the temperature of the cleaning liquid can be, for example, 30°C or higher, further 35°C or higher, further 40°C or higher, and 90°C or lower, further 80°C or lower, and further 70°C or lower. .

In the tableware washing method of the present invention, the flow rate when bringing the cleaning liquid into contact with the tableware is preferably 5 m/min or more, more preferably 10 m/min or more, still more preferably 50 m/min or more, from the viewpoint of protein cleaning properties. , and preferably 2,000 m/min or less, more preferably 1,000 m/min or less, and even more preferably 500 m/min or less.

In the tableware washing method of the present invention, it is preferable to rinse the tableware with water after bringing the cleaning liquid into contact with the tableware. The temperature of the water for rinsing tableware is preferably 50°C or higher, more preferably 55°C or higher, even more preferably 60°C or higher, and preferably 80°C or lower.
The rinsing time of the tableware is preferably 4 seconds or more, more preferably 5 seconds or more, and preferably 10 seconds or less, more preferably 9 seconds or less.
The flow rate of the rinse water is preferably 5 m/min or more, more preferably 10 m/min or more, even more preferably 100 m/min or more, and preferably 2,500 m/min or less, more preferably 2,000 m/min or less, More preferably, it is 1,500 m/min or less, even more preferably 250 m/min or less, even more preferably 150 m/min or less.

In the present invention, the dishwasher may be any dishwasher that is generally available on the market, and although it is also possible to use a household automatic dishwasher, a commercial automatic dishwasher is preferable. When cleaning with a commercial automatic dishwasher, the dishwasher detergent composition of the present invention is generally used as a cleaning liquid mixed with water. In this case, a certain amount of the composition is optionally transferred into the interior of the commercial automatic dishwasher by means of a feeding device, and an appropriate concentration of the cleaning liquid is maintained. The detergent composition for dishwashers of the present invention is supplied, for example, by directly inserting a tube specifically designed for commercial automatic dishwashers into a container made of plastic or the like filled with the composition and sucking it up. The cleaning liquid is then supplied to the interior of the commercial automatic dishwasher.

Example <Example 1>
(1) Ingredients The following ingredients were used to prepare the surfactant compositions of Examples and Test Examples listed in Table 1.
<(a) Component>
(a1) Ingredient/C10AS: Sodium decyl sulfate (Emar 3F, manufactured by Kao Corporation)
・C12AS: Sodium dodecyl sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
(a2) component/sec-C12-14EO7PO8.5: polyoxyalkylene (average number of added moles of oxyethylene 7, average number of added moles of oxypropylene 8.5) secondary alkyl (number of carbon atoms 12-14) ether ( Softanol EP7085, manufactured by Nippon Shokubai Co., Ltd.)
<(b) component>
・Para-toluenesulfonic acid (PTS MT-70, manufactured by Meiyu Sangyo Co., Ltd.)
・Meta-xylene sulfonic acid (SXA-60, manufactured by Itochu Chemical Frontier Corporation)
・Cumenesulfonic acid (manufactured by Meiyu Sangyo Co., Ltd.)
<(b') component>
・Silicone antifoaming agent (Antifoam E-20, manufactured by Kao Corporation)

(2) Preparation of surfactant compositions The surfactant compositions shown in Table 1 were prepared and evaluated on the following items.
Components (a) and (b) were mixed in the proportions shown in Table 1, the pH was adjusted to 7 using monoethanolamine and sodium hydroxide, and water was added to prepare a surfactant composition with a total amount of 100 g. . The pH of the surfactant composition is a value measured at 25°C.

(3) Storage stability evaluation method 100 g of the surfactant composition prepared in (2) was added to a transparent standard bottle (mouth inner diameter x body diameter x height: φ31.9 x φ51.5 x 95.5 mm, No. .11, manufactured by AS ONE Co., Ltd.) and allowed to stand at room temperature (25° C.) for one day. Thereafter, the surfactant composition in the standard bottle was visually observed, and the storage stability of the surfactant composition was evaluated based on the following criteria. The results are shown in Table 1.
○: No precipitation or turbidity occurred. ×: Precipitation or turbidity occurred.

(4) Method for evaluating low foaming property and foam breakage property The activator composition was diluted 2,000 times and a cleaning operation was performed. 20 seconds after the start of the washing operation, open the door of the automatic dishwasher and visually check the state of the foam in the cleaning solution in the washing chamber, and check the low foaming property and foam breakage of the surfactant composition based on the following criteria. Gender was evaluated. It can be said that the higher the score, the more suppressed the foaming properties of the surfactant composition.
4: No bubbles at all 3: All bubbles disappear after 5 seconds 2: All bubbles disappear after 10 seconds 1: All bubbles do not disappear even after 10 seconds

<Example 2>
(1) Ingredients The following ingredients were used to prepare the dishwasher detergent compositions of Examples and Test Examples listed in Table 2.
<(c) component>
[(c1) component]
・C10AS: Sodium decyl sulfate (Emar 3F, manufactured by Kao Corporation)
・C10SAS: Alkyl (10 carbon atoms) sulfonic acid sodium salt (sodium 1-decane sulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・LAS: Sodium laurylbenzenesulfonate (Neoperex G-25, manufactured by Kao Corporation)
・C12AS: Sodium dodecyl sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
[(c2) component]
・Para-toluenesulfonic acid (PTS MT-70, manufactured by Meiyu Sangyo Co., Ltd.)
・Meta-xylene sulfonic acid (SXA-60, manufactured by Itochu Chemical Frontier Corporation)
・Cumenesulfonic acid (manufactured by Meiyu Sangyo Co., Ltd.)
<(d) component>
・secC12-14EO7PO8.5: "Softanol EP7085" manufactured by Nippon Shokubai Co., Ltd., a linear secondary alcohol with 12 to 14 carbon atoms, an average of 7 mol of ethylene oxide, and an average of 8.5 mol of propylene oxide, in this order. Added nonionic surfactant <(e) component>
・Citric acid: Citric acid (manufactured by Showa Kako Co., Ltd.), pK'Ca3.4
<(f) component>
・Sodium sulfite: Sodium sulfite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<(g) Component>
・Protease: KP43 protease [prepared by the method described in the Examples of JP-A-2017-221188 (effective content: 2.0% by mass)]
<Other ingredients>
・pH adjuster (MEA): Monoethanolamine (manufactured by Mitsui Chemicals, Inc.)
・Defoaming agent: Antifoam E-20 (manufactured by Kao Corporation)

(2) Preparation of detergent composition for dishwasher The detergent composition for dishwasher shown in Table 2 was prepared and evaluated on the following items.
The components shown in Table 2 were mixed in the proportions shown in Table 2, the pH was adjusted to 6.8 using monoethanolamine (MEA), and water was added to prepare a dishwasher detergent composition with a total amount of 100 g. did. The pH of the dishwasher detergent composition is a value measured at 25°C.

(3) Storage stability evaluation method 100 g of the dishwasher detergent composition prepared in (2) was added to a transparent standard bottle (mouth inner diameter x body diameter x height: φ31.9×φ51.5×95. 5 mm, No. 11, manufactured by As One Co., Ltd.), and allowed to stand at room temperature (25° C.) for 24 hours. Thereafter, the dishwasher detergent composition in the standard bottle was visually observed, and the storage stability of the dishwasher detergent composition was evaluated based on the following criteria. The results are shown in Table 2.
○: No precipitation, turbidity, or separation occurred. ×: Precipitation, turbidity, or separation occurred.

(4) Method for evaluating low foaming properties and foam breaking properties The dishwasher detergent composition prepared in (2) was diluted 2,000 times to obtain a cleaning liquid, and the cleaning liquid was heated to 60°C. Then, a washing operation was performed using an automatic dishwasher (JWE-400TA3, manufactured by Hoshizaki Co., Ltd.). 20 seconds after the start of the washing operation, open the door of the automatic dishwasher and visually check the foam state of the cleaning liquid in the washing tank. And foam breakability was evaluated. It can be said that the higher the score, the more suppressed the foaming properties of the dishwasher detergent composition.
4: No bubbles at all 3: All bubbles disappear after 5 seconds 2: All bubbles disappear after 10 seconds 1: All bubbles do not disappear even after 10 seconds

(5) Evaluation of egg stain cleaning rate Apply 3.0 g of egg yolk evenly with a brush to the bottom surface (180 mm x 100 mm) of a stainless steel vat (external dimensions width 258 mm x depth 177 mm x height 18 mm, bottom internal dimensions 235 mm x 155 mm). I spread it. Then, this stainless steel bat was dried at 30° C. for 30 minutes in a constant temperature bath (FC-612, manufactured by ADVANTEC Co., Ltd.).
Place the stainless steel vat with egg stains on it into the cleaning tank of an automatic dishwasher (JWE-400TA3, manufactured by Hoshizaki Co., Ltd.), and add 2. Washing was performed for 80 seconds using a cleaning solution diluted 0.000 times (dishwasher detergent composition concentration: 0.05% by mass, 60°C), and then rinsed with 2 L of water (80°C). The egg stain cleaning rate was calculated based on the following formula (1). It can be said that the higher the egg stain cleaning rate, the better the egg stain cleaning performance.
Egg stain cleaning rate (mass%) = 100 × [(mass of vat before cleaning) - (mass of vat after cleaning)] / [(mass of vat after egg yolk is attached and dried) - (mass of vat before egg yolk is attached) Weight of bat)〕 (1)

(6) Evaluation of oil cleaning tolerance 3.0 g of salad oil (manufactured by Nisshin Oilio Group Co., Ltd.) was evenly spread on the bottom surface of the stainless steel vat (180 mm x 100 mm) using a brush.
Two bats with salad oil attached and 4.0 g of salad oil were placed in the cleaning tank of an automatic dishwasher (JWE-400TA3, manufactured by Hoshizaki Co., Ltd.), and each dishwasher detergent composition prepared in (2) was prepared. It was washed for 80 seconds using a cleaning solution (60°C) diluted 2,000 times, and then rinsed with 2 L of water (80°C).
Visually check the front and back sides of the vat after cleaning, and if no oil adhesion or oil cloudiness is confirmed on each side, add 0.1 g of the same dishwasher detergent composition into the cleaning tank. Additionally, put two bats with the same salad oil as above and 4.0 g of salad oil into the cleaning tank, wash for 80 seconds with cleaning liquid (60°C), and rinse with 2L of water (80°C) in the same way as above. I did it. This process was repeated until oil adhesion or cloudiness was visually confirmed on the front or back surface of the bat, and the amount of oil added until oil adhesion or cloudiness was confirmed on the vat was measured.
If there is no oil adhesion or cloudiness on either of the two vats, increase the amount of oil to 10g, and if one of the two vats shows oil adhesion or cloudiness, reduce the amount of oil input. The measurement was carried out with a weight of 5 g. The results are shown in Table 2.

Claims

(a) More than 10% by mass and 30% by mass or less of a surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a)]; (b) 1 alkyl group having 1 to 3 carbon atoms; Contains benzenesulfonic acid or a salt thereof which may be substituted with at least 1 and up to 3 [hereinafter referred to as component (b)] and water, and the mass ratio of the content of component (a) to the content of component (b) ( A surfactant composition in which a)/(b) is 0.30 or more and 2.00 or less.
The surfactant composition according to claim 1, wherein component (a) is one or more selected from (a1) anionic surfactants and (a2) nonionic surfactants.
The surfactant composition according to claim 1 or 2, which is a hard surface cleaning composition.
The surfactant composition according to any one of claims 1 to 3, which is a detergent composition for automatic dishwashers.
(a) A surfactant composition containing more than 10% by mass and not more than 30% by mass of a surfactant having a hydrocarbon group having 8 to 18 carbon atoms [hereinafter referred to as component (a)] and water; (b) Benzene sulfonic acid or its salt [hereinafter referred to as component (b)] which may be substituted with one or more and three or less alkyl groups having 1 or more and 3 or less carbon atoms is determined based on the content of component (a) and component (b). A method for controlling the foaming property of a surfactant composition, wherein the mass ratio (a)/(b) of the content is 0.30 or more and 2.00 or less.
The method for controlling the foaming properties of a surfactant composition according to claim 5, wherein the surfactant composition is diluted with water by 100 times or more and 10,000 times or less.
The method for controlling foaming properties of a surfactant composition according to claim 5 or 6, which suppresses foaming properties caused by the surfactant.
(c) An anionic surfactant containing the following (c1) component and the following (c2) component [hereinafter referred to as (c) component], the following (d) component and water, and the content of (c) component and ( d) The mass ratio (c)/(d) of the content of the components is 1 or more and 20 or less, and the mass ratio (c1)/(c2) of the content of the (c1) component and the content of the (c2) component is 0. A detergent composition for a dishwasher having a particle diameter of .30 or more and 0.80 or less.
(c1) Component: One or more selected from sulfonic acids having a chain hydrocarbon group having 6 to 16 carbon atoms, sulfuric esters having a chain hydrocarbon group having 6 to 16 carbon atoms, and salts thereof (c2 ) Component: Benzene sulfonic acid or its salt optionally substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms (d) Component: Nonionic having a hydrocarbon group having 6 to 16 carbon atoms surfactant
The detergent composition for a dishwasher according to claim 8, containing a total of 15% by mass or more and 50% by mass or less of components (c) and (d).
A method for cleaning tableware, which comprises using a dishwasher to wash tableware with a cleaning liquid prepared by diluting the dishwasher detergent composition according to claim 8 or 9 with water.
11. The method for washing tableware according to claim 10, wherein the cleaning liquid is prepared by diluting the dishwasher detergent composition with water to more than 1 to 2,000 times.
The method for cleaning tableware according to claim 10 or 11, wherein the cleaning liquid is brought into contact with the tableware for 20 seconds or more and 600 seconds or less.
The method for washing tableware according to any one of claims 10 to 12, wherein the temperature of the washing liquid is 30° C. or higher and 90° C. or lower.