JP6872411B2 - Liquid detergent for dishwasher - Google Patents

Description

The present invention relates to a dishwasher detergent.

For washing with a dishwasher, a special detergent (dishwasher detergent) is generally used. If there is a lot of foaming in the dishwasher cleaning agent, the overflow phenomenon that bubbles overflow during the operation of the dishwasher and the air biting phenomenon that sufficient injection force cannot be obtained due to the bubbles getting entangled in the circulating water, etc. Since it may occur, it is required to have low foaming property (less foaming).

As for dishwashers, models with a lower washing temperature than before have become widespread from the viewpoint of energy saving and the like. For example, in addition to the standard course (normal mode) in which hot water of about 55 to 65 ° C circulates, models equipped with a power saving mode such as the "low temperature course" in which hot water whose water temperature is about 10 ° C lower than this circulates are launched. ing. When the cleaning temperature is low, the cleaning power tends to decrease, and oil stains tend to remain, and the cleaning power against oil stains tends to be insufficient.

In the examples of Patent Document 1, secondary sodium alkanesulfonate, linear alkylbenzene sulfonate, or C12, 13 are used as detergents for dishwashers that have low foaming properties and can be used in a power saving mode (cleaning liquid 40 ° C.). Compositions comprising polyoxyethylene alkyl ether sulfate and certain alkylamide amines have been described.

Japanese Unexamined Patent Publication No. 2015-010186

However, in recent years, there has been a demand for further lowering of the cleaning temperature. In addition, since the amount of dirt brought into the dishwasher tends to increase, the performance of the conventional dishwasher detergent is not always sufficient.
Specifically, in the past, before washing dishes with a dishwasher, pre-washing was performed to remove foodstuffs and stains adhering to the dishes to some extent, but recently there has been a remarkable tendency not to perform this pre-washing. The amount of dirt brought into the dishwasher is increasing. As the amount of dirt increases, recontamination is likely to occur. Especially when cleaning tableware with a hydrophobic surface such as polypropylene tableware, recontamination by oil is likely to occur. As a result, oil stains are attached to the tableware after cleaning, and the cleaning power against oil stains becomes insufficient.
An object of the present invention is to provide a dishwasher detergent having low foaming properties and excellent detergency against oil stains even in low temperature washing.

The present invention has the following aspects.
[1] Component (A): An anionic surfactant containing an α-sulfofatty acid alkyl ester salt (a1) represented by the following general formula (I), and component (B): represented by the general formula (II). Contains compounds,
A dishwasher detergent having a mass ratio of 0.1 to 10 represented by component (B) / component (A).
R ^11- CH (SO ₃ M) -COOR ¹² ... (I)
[In formula (I), R ¹¹ is an alkyl group having 14 to 16 carbon atoms, R ¹² is an alkyl group having 1 to 2 carbon atoms, and M is a counter ion. ]

[In formula (II), R ¹ represents a linear or branched chain alkyl or alkenyl group having 13 to 21 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. R ³ represents an alkylene group having 1 to 4 carbon atoms. R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively, and may be the same or different from each other. ]
[2] The component (B) is represented by the general formula (II), R ¹ is a linear alkyl group having 13 to 21 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The dishwasher cleaning agent according to [1], which is one or more selected from the group consisting of compounds in which R ³ is an alkylene group having 1 to 4 carbon atoms and R ⁴ and R ^{5 are alkyl groups having 1 to 4 carbon atoms.} ..
[3] The component (a1) is a compound (a1-C16) having 14 carbon atoms ^{in R 11 in} the general formula (I) and 16 carbon atoms ^{in R 11 in the general formula (I).} The dishwasher detergent according to [1] or [2], which comprises the compound (a1-C18) and has a mass ratio of (a1-C16): (a1-C18) of 30:70 to 90:10.

[4] Containing the component (A), the component (B), and a solvent,
The content of the component (A) is 0.1 to 5% by mass.
The dishwasher detergent according to any one of [1] to [3], which further contains an alkyl polyglycoside (C) having a branched alkyl group and one or both of an aromatic sulfonic acid or a salt thereof (D). ..
[5] The dishwasher detergent according to [4], wherein the mass ratio represented by [(C) component + (D) component] / (A) component is 2 to 30.
[6] For the dishwasher of [4] or [5], which contains the component (C) and the component (D) and has a mass ratio represented by the component (C) / component (D) of 0.03 to 29. Washing soap.
[7] The dishwasher detergent according to any one of [1] to [6], wherein the component (C) is 2-ethylhexyl polyglycoside and the component (D) is cumene sulfonate.

[8] The component (A), the component (B), the component (C), the component (D), and the solvent are contained.
The component (A) is an α-sulfofatty acid alkyl ester salt (a1) represented by the general formula (I).
The component (C) is a 2-ethylhexyl polyglycoside, and the component (D) is a cumene sulfonate.
The content of the component (A) is 0.2 to 1.2% by mass, and the content is 0.2 to 1.2% by mass.
The mass ratio represented by the component (B) / component (A) is 0.3 to 3.0.
The mass ratio represented by the [(C) component + (D) component] / (A) component is 5.0 to 15.0.
The dishwasher detergent according to any one of [1] to [7], wherein the mass ratio represented by the component (C) / component (D) is 0.5 to 1.0.

The dishwasher detergent of the present invention has low foaming properties and is excellent in detergency against oil stains even in low temperature washing.

The dishwasher detergent of the present invention (hereinafter, may be simply referred to as a detergent) is a composition containing the component (A) and the component (B). It may be a powder or a liquid containing a solvent. When it is a liquid, it is preferable to further contain one or both of the component (C) and the component (D), and it is more preferable to contain both the component (C) and the component (D).

<Ingredient (A)>
The component (A) is an anionic surfactant and contains the component (a1). The component (a1) and an anionic surfactant other than the component (a1) (hereinafter, referred to as the component (a2)) may be used in combination.
[(A1) component]
The component (a1) is an α-sulfofatty acid alkyl ester salt (α-SF salt) represented by the following general formula (I). The component (a1) may be used alone or in combination of two or more.
When the cleaning agent contains the component (a1), excellent cleaning power against oil stains can be obtained. For example, even when tableware having a hydrophobic surface is washed in a low temperature course, good cleaning power against oil stains can be obtained.

R ^11- CH (SO ₃ M) -COOR ¹² ... (I)
In formula (I), R ¹¹ is an alkyl group having 14 to 16 carbon atoms. The alkyl group may be linear or branched. Even if the ^{number of carbon atoms of R 11} is less than 14 or more than 16, the detergency against oil stains becomes insufficient.
When two or more kinds of the components (a1) are used, ^{the carbon numbers of R 11} may be the same or different from each other.

In formula (I), R ¹² is an alkyl group having 1 to 2 carbon atoms. When R ¹¹ has 1 to 2 carbon atoms, it has excellent detergency against oil stains. R ¹² is preferably a methyl group.
When two or more kinds of the components (a1) are used, ^{the carbon numbers of R 12} may be the same or different from each other.

In formula (I), M is a counterion. M may be any as long as the component (a1) can form a water-soluble salt. For example, alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and magnesium ion, ammonium ion, and the like. Examples thereof include protonated ethanolamine, and among them, alkali metal ions are preferable, and sodium ions are more preferable.

Particularly from the viewpoint of excellent detergency for oil stains at low temperatures washing, (a1) component, a compound the carbon number of ^{R 11} in the formula (I) is 14 and (a1-C16), ^{R 11} in the formula (I) It is preferably a mixture containing the compound (a1-C18) having 16 carbon atoms. In this case, the mass ratio of (a1-C16): (a1-C18) is preferably 30:70 to 90:10, more preferably 60:40 to 90:10.
Examples of (a1-C16) include α-sulfopalmitate methyl ester salt and α-sulfopalmitate ethyl ester salt.
Examples of (a1-C18) include α-sulfostearic acid methyl ester salt and α-sulfostearic acid ethyl ester salt.
As a mixture of different compounds the carbon number of R ^11, alpha-Suruhoyashi oil fatty acid methyl ester salts, alpha-Suruhoyashi oil fatty acid ethyl ester salts and the like.
Of these, a mixture of α-sulfopalmitic acid methyl ester salt and α-sulfostearic acid methyl ester salt is preferable.

[(A2) component]
The component (a2) is an anionic surfactant other than the component (a1). For example, sulfonate type, sulfate ester type, carboxylate type, and phosphate ester salt type anionic surfactants can be mentioned.
Examples of the sulfonate type include α-sulfo fatty acid alkyl ester salt, alkane sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene sulfate, α-olefin sulfonate, alkyl sulfosuccinate, and dialkyl sulfosuccinic acid. Examples include salt.
Examples of the sulfate ester salt type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, and polyoxyalkylene alkenyl ether sulfate ester salts.
Examples of the carboxylate type include alkyl ether carboxylate, amide ether carboxylate, sulfosuccinate, amino acid-based anionic surfactant and the like.
Examples of the phosphoric acid ester salt type include alkyl phosphate ester salts and alkyl ether phosphoric acid ester salts.

Examples of the salt constituting the component (a2) include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium) and diethanolamine salt (diethanolammonium). ), Alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like.

The component (a2) preferably has an alkyl group having 8 to 18 carbon atoms or has an alkenyl group having 8 to 18 carbon atoms, and more preferably has an alkyl group having 8 to 18 carbon atoms. .. The alkyl group or the alkenyl group may be linear or branched.

Among the above, as the component (a2), a sulfonate type and a sulfate ester salt type are preferable because they have good detergency against oil stains and can easily secure low foaming properties.
Among them, α-sulfomystic acid methyl ester sodium, α-sulfolauric acid methyl ester sodium, secondary alkane (14 to 17 carbon atoms) sodium sulfonate, linear alkyl (16 to 17 carbon atoms) are excellent in detergency against oil stains. 10 to 14 carbon atoms) Sodium benzene sulfonate, α-olefin (12 to 18 carbon atoms) sodium sulfonate, sodium lauryl sulfate, polyoxyethylene (1 to 3 mol on average), polyoxyethylene (1 to 3 mol) Alkyl (12-14 carbon atoms) ether sulfate sodium, α-sulfomyristic acid methyl ester sodium, α-sulfolauric acid methyl ester sodium, secondary alkane (14-17 carbon atoms) sodium sulfonate, and linear alkyl More preferably one or more selected from the group consisting of sodium benzenesulfonate (10 to 14 carbon atoms).

The content of the component (A) with respect to the cleaning agent is preferably 0.1% by mass or more from the viewpoint of detergency, and preferably 10% by mass or less from the viewpoint of low foaming property.
When the cleaning agent is a liquid, the content of the component (A) with respect to the cleaning agent is more preferably 0.1 to 5% by mass, further preferably 0.2 to 3% by mass from the viewpoint of stability during low-temperature storage. ..
The content of the component (a1) with respect to the component (A) is preferably 50% by mass or more, more preferably 70% by mass or less, and particularly preferably 100% by mass from the viewpoint of detergency against oil stains.

<Ingredient (B)>
The component (B) is a compound represented by the general formula (II). The component (B) may be one kind or two or more kinds in combination.

In formula (II), R ¹ is a linear or branched-chain alkyl group having 13 to 21 carbon atoms or a linear or branched-chain alkenyl group having 13 to 21 carbon atoms. Of these, R ¹ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms.
The number of carbon atoms of the alkyl group and alkenyl group for R ¹ are each a 13 to 21, since the anti-foaming effect is enhanced more, preferably carbon atoms 15 to 21, more preferably a carbon number 15 to 19 is there.

In formula (II), R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. The number of hydroxy groups in the hydroxyalkyl group in R ^{2 may be one or two or more.} Among them, as R ² , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.

In formula (II), R ³ is an alkylene group having 1 to 4 carbon atoms. The carbon number of R ³ is preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3.
In formula (II), R ⁴ and R ⁵ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively. R ⁴ and R ⁵ may be the same or different from each other.
The ^{number of carbon atoms of the alkyl group in R 4} and R ⁵ is 1 to 4, respectively, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. Among them, R ⁴ and R ⁵ are preferably alkyl groups having 1 to 4 carbon atoms, respectively, and are preferably the same as each other.

Specifically, as the component (B)
Myristic acid dimethylaminoethylamide (R ² = hydrogen atom, R ³ = ethylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Myristic acid diethylaminoethylamide,
Myristic acid dipropylaminoethylamide,
Myristic acid dimethylaminopropylamide,
Myristic acid diethylaminopropylamide,
Myristic acid dipropylaminopropylamide,
Palmitic acid dimethylaminoethylamide (R ² = hydrogen atom, R ³ = ethylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Palmitic acid diethylaminoethylamide,
Dipropylaminoethyl palmitate,
Palmitic acid dimethylaminopropylamide,
Palmitic acid diethylaminopropylamide,
Dipropylaminopropyl palmitate,
Dimethylaminoethylamide stearate (R ² = hydrogen atom, R ³ = ethylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Diethylaminoethylamide stearate,
Dipropylaminoethyl amide stearate,
Dimethylaminopropyl amide stearate,
Diethylaminopropyl amide stearate,
Dipropylaminopropyl amide stearate,
Behenic acid dimethylaminoethylamide (R ² = hydrogen atom, R ³ = ethylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Behenic acid diethylaminoethylamide,
Behenic acid dipropylaminoethylamide,
Behenic acid dimethylaminopropylamide,
Behenic acid diethylaminopropylamide,
Behenic acid dipropylaminopropylamide,
Dimethylaminoethylmethylamide myristate (R ² = methyl group, R ³ = ethylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Palmitic acid dimethylaminoethylmethylamide,
Dimethylaminoethylmethylamide stearate,
Behenic acid dimethylaminoethylmethylamide,
Myristic acid dimethylaminopropylmethylamide (R ² = methyl group, R ³ = propylene group, R ⁴ = methyl group, R ⁵ = methyl group),
Palmitic acid dimethylaminopropylmethylamide,
Dimethylaminopropylmethylamide stearate,
Behenic acid dimethylaminopropylmethylamide can be mentioned.

The component (B) is represented by the general formula (II), where R ¹ is a linear alkyl group having 13 to 21 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is carbon. One or more selected from the group consisting of compounds consisting of an alkylene group having a number of 1 to ⁴ and an alkyl group having R 4 and R ⁵ having 1 to 4 carbon atoms is preferable, and myristic acid dimethylaminopropylamide and palmitate dimethylaminopropylamide are preferable. , Dimethylaminopropylamide stearate, and dimethylaminopropylamide behenate, one or more selected from the group.

The content of the component (B) with respect to the cleaning agent is preferably 0.01% by mass or more from the viewpoint of low foaming property, and is preferably 10% by mass or less from the viewpoint of low foaming property and detergency against oil stains. preferable.
When the cleaning agent is a liquid, the content of the component (B) with respect to the cleaning agent is more preferably 0.1 to 5% by mass, further preferably 0.2 to 3% by mass from the viewpoint of stability during low-temperature storage. ..

In the present invention, the "mass ratio represented by the component (B) / component (A) (hereinafter, also referred to as (B) / (A))" refers to the mass of the component (A) in the cleaning agent. (B) Represents the ratio of the content mass of the component.
The mass ratio represented by the component (B) / component (A) is 0.1 to 10, preferably 0.2 to 5, and more preferably 0.3 to 3.
When the component (B) / component (A) is at least the lower limit of the above range, the foam suppressing effect of the component (B) is likely to be exhibited. When it is not more than the upper limit of the above range, the detergency against oil stains is enhanced.

<Ingredient (C)>
The component (C) is an alkyl polyglycoside having a branched alkyl group. The component (C) contributes to the low temperature stability of the liquid detergent, among other nonionic surfactants. The component (C) may be used alone or in combination of two or more.
Examples of the component (C) include compounds represented by the following general formula (III).
R ²¹ (OR ²² ) _x G _y … (III)
In the formula (III), R ²¹ is a branched-chain alkyl group having 8 to 18 carbon atoms, and a branched-chain alkyl group having 8 to 10 carbon atoms is preferable.
R ²² is an alkylene group having 2 to 4 carbon atoms, and G is a residue derived from a reducing sugar.
x is the average number of repetitions of (OR ²² ), which is a number from 0 to 5, preferably a number from 0 to 2, and more preferably 0.
y is the average degree of condensation of sugars, which is a number of 1 to 5, preferably a number of 1 to 3, more preferably 1 to 2, and even more preferably 1 to 1.5.

As G, residues derived from reducing sugars of monosaccharides, disaccharides or trisaccharides or more are preferable.
Examples of the reducing sugar of the monosaccharide include glucose, galactose, xylose, mannose, lyxose, arabinose, fructose or a mixture thereof.
Examples of the reducing sugars of disaccharides or trisaccharides or more include maltose, xylobiose, isomaltose, cellobiose, gentibios, lactose, sucrose, nigerose, turanose, raffinose, gentianose or a mixture thereof.
Among these, as G, one or more selected from the group consisting of residues derived from glucose, fructose, maltose, and sucrose is preferable, and residues derived from glucose are more preferable.
Examples of commercially available products of the component (C) include LG Household & Health Care trade name: Milcoside 435N, Seppic trade name: Simulsol AS48 and the like.

<Ingredient (D)>
The component (D) is an aromatic sulfonic acid or a salt thereof. The component (D) contributes to the low temperature stability of the liquid detergent. The component (D) may be used alone or in combination of two or more.
As the component (D), various aromatic sulfonic acids and / or salts thereof can be used. For example, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid and / or a salt thereof and the like can be mentioned.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
Of these, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid and / or a salt thereof are preferable, and cumene sulfonic acid and / or a salt thereof is particularly preferable from the viewpoint of low temperature stability.

When the cleaning agent contains the component (C) and / or the component (D), the mass ratio represented by the component [(C) component + (D) component] / (A) component (hereinafter, [(C) + (D) )] / (Also referred to as (A)) is preferably 2 to 40, more preferably 5 to 15, and even more preferably 6 to 12. Within this range, both low foaming property during washing and storage stability at low temperature are likely to be compatible.
When the cleaning agent contains the component (C) and the component (D), the mass ratio represented by the component (C) / component (D) (hereinafter, also referred to as (C) / (D)) is 0.03 to 29. It is preferably 0.03 to 15, more preferably 0.2 to 5, and particularly preferably 0.5 to 1. Within this range, the storage stability at low temperature is more excellent due to the synergistic effect of the component (C) and the component (D).

The content of the component (C) with respect to the cleaning agent is preferably 0.05 to 10% by mass, more preferably 0.1 to 3% by mass, still more preferably 0.1 to 1% by mass. When the content of the component (C) is not less than the lower limit value in the above range, the low temperature stability is more excellent, and when it is not more than the upper limit value, the low foam property is excellent.
The content of the component (D) with respect to the cleaning agent is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and even more preferably 1 to 5% by mass. When the content of the component (D) is at least the lower limit of the above range, the low temperature stability is improved. On the other hand, even if the content exceeds the upper limit, further improvement in low temperature stability cannot be expected. Further, if the content of the component (D) is too large, the low temperature stability is lowered.
The total content of the component (C) and the component (D) with respect to the cleaning agent is preferably 1 to 15% by mass, more preferably 2 to 5% by mass. Within this range, it is easy to achieve both storage stability at low temperature and low foaming property during washing.

<Arbitrary ingredient>
The cleaning agent of the present invention may contain arbitrary components other than the components (A) to (D) as long as the effects of the present invention are not impaired. Optional ingredients can include ingredients known in detergents for washing dishes.
For example, chelating agents, bleaching agents, bleaching activators, alkaline builders, enzymes (eg amylase, protease), plant extracts, fragrances, oil absorbers, defoamers, tableware protectants, thickeners, colorants, preservatives. , Step agents and the like can be used.

Chelating agents are roughly classified into polyacrylic acid-based high molecular weight chelating agents and organic acid-based low molecular weight chelating agents. Specific examples of the polymer chelating agent include poly (meth) acrylic acid or a salt thereof, (meth) acrylic acid-maleic acid copolymer or a salt thereof, and an ethylene-maleic acid copolymer or a salt thereof. Acrylic acid / maleic acid copolymers are particularly preferable, and those having a copolymerization ratio (molar ratio) of 75/25 to 50/50 and a mass average molecular weight of 10,000 to 100,000 are preferable. Moreover, as a salt, a sodium salt, a potassium salt and the like can be mentioned. In addition, one or more high molecular weight polycarboxylic acids (salts) to be used can be used alone or in combination.
Specific examples of the low molecular weight chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), β-alanine diacetic acid (EDETA) or ethylenediaminediamine disuccinic acid (EDDS), L-asparaginic acid-N, N-2. Acetic acid (ASDA), dihydroxyethylethylenediaminetetraacetic acid (DHEDDA), hydroxyethyliminodiacetic acid (HIMDA), Na citrate, K citrate, hydroxyethylethylenediaminetriacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GEDTA), L − Glutamate diacetate tetrasodium (CMGA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA), diethylenetriaminetetraacetic acid (DTPA), triethylenetetraminehexacetic acid (TTHA), dihydroxyethylglycine (DHEG), 3- Hydroxy-2,2'-iminodiacetic acid tetrasodium (HIDS), serine diacetic acid (SDA), asparagine diacetic acid, methylglycine diacetic acid (MGDA), hydroxyethanephosphonic acid (HEDP), aminotrieethylenephosphonic acid (NTMP) , Tripolyphosphoric acid (STPP), etc., but from the viewpoint of achieving both cloudy detergency and tea astringent detergency, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), β-alanine diacetic acid (EDETA) or ethylenediaminediaminediamine are available. Succinic acid (EDDS), L-asparaginic acid-N, N-diacetic acid (ASDA), dihydroxyethylethylenediaminediamine diacetic acid (DHEDDA), hydroxyethyliminodiacetic acid (HIMDA), Na citrate, hydroxyethylethylenediaminetriacetic acid (HEDTA) ), Glyylenediaminetetraacetic acid (GEDTA), L-glutamate tetraacetic acid diacetate (CMGA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA), diethylenetriaminetetraacetic acid (DTPA), triethylenetetraminehexacetic acid ( TTHA), dihydroxyethylglycine (DHEG), 3-hydroxy-2,2'-imilotriacetic acid tetrasodium (HIDS), serine diacetic acid (SDA), asparagine diacetic acid, methyl glycine diacetic acid (MGDA) are preferable.
Further, Na citrate, K citrate, tetrasodium L-glutamate diacetate (CMGA), methylglycine diacetic acid (MGDA), and diethylenetriamine pentaacetic acid (DTPA) are more preferable as those exhibiting higher detergency.

(Manufacturing method of cleaning agent)
The cleaning agent of the present invention is not particularly limited, and a conventionally known production method can be used.
As a method for producing a liquid cleaning agent, a solvent, a component (A), a component (B), a component (C) and / or a component (D), and if necessary, an arbitrary component are mixed. Is prepared by

Water is preferable as the solvent, and a water-miscible organic solvent may be used in addition to water.
The "water-miscible organic solvent" refers to an organic solvent that dissolves in 1 L of ion-exchanged water at 25 ° C. in an amount of 50 g or more. The water-miscible organic solvent may be any one that becomes a uniform solution when mixed with water, and among them, monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycols. Examples include ether.

The pH (25 ° C.) of the liquid detergent is preferably 5 or more from the viewpoint of corrosiveness to the dishwasher, preferably 8 or less from the viewpoint of low foaming property, and more preferably 6 to 8.
In the present invention, the pH (25 ° C.) of the dishwasher detergent indicates a value measured by a method based on JIS Z 8802: 1984 "pH measurement method".
For adjusting the pH of the dishwasher detergent of the present invention, for example, a known pH adjusting agent such as an inorganic alkaline agent, an organic alkaline agent, or an inorganic acid is used.
When the cleaning agent is a solid, the pH of the aqueous solution at the operating temperature is preferably 5 to 11, and more preferably 6 to 10.

(How to use cleaning agent)
The detergent of the present invention may be used according to the model of the dishwasher and the degree of stain on the dishes and the like.
Examples of the method of washing the object to be washed by the dishwasher using the detergent include a method having both washing and rinsing steps.
As a washing method, for example, the washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30 ° C.) into the dishwasher chamber is raised to a predetermined washing temperature (the temperature of the washing liquid circulated during washing). A process of cleaning the object to be cleaned while warming (hereinafter referred to as "cleaning process"), a process of rinsing the object to be cleaned after cleaning with tap water at room temperature (hereinafter referred to as "rinsing (1) process"), and While raising the temperature of tap water at room temperature from 70 to 75 ° C. at 2 to 3 ° C./min, the cleaning object after the rinsing (1) step is further rinsed (hereinafter referred to as "rinsing (2) step"). ) Is mentioned. The cleaning time in the cleaning step is preferably 10 to 40 minutes.
In the case of a general standard course, the cleaning temperature in the cleaning step is about 55 to 65 ° C., and the heating rate is about 2 to 3 ° C./min. In the low temperature course, for example, the cleaning temperature is about 35 to 45 ° C. and the heating rate is about 1 ° C./min. The cleaning agent of the present invention has excellent detergency against oil stains even in low-temperature cleaning, and for example, exhibits excellent detergency even when the cleaning temperature is 35 ° C.
In any course, the amount of the cleaning agent used at one time is preferably 3 to 9 g with respect to about 3 liters of tap water in the case of a liquid cleaning agent.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
Tables 1 to 7 show the composition of the cleaning agents of each example.
The unit of the blending amount in the table is "mass%", and all the components indicate the net conversion amount.
"Appropriate amount" indicates the amount of the pH adjuster added so that the pH of the cleaning agent is 7.0.
"Balance" means that water is blended so that the total blending amount (mass%) of all the blended components contained in the cleaning agent of each example is 100% by mass.
The components shown in the table will be described below.

<Ingredient (A)>
[(A1) component]
A mixture of a1-1 (α-SF salt): sodium α-sulfo fatty acid methyl ester ((a1-C16): (a1-C18) with a mass ratio of 80:20, purity 90%, manufactured by Lion Ecochemicals, Inc. Name: MIZULA F FL-80).
a1-2 (α-SF salt): Sodium α-sulfostearate methyl ester obtained in Synthesis Example 1.
a1-3 (α-SF salt): Sodium α-sulfopalmic acid methyl ester obtained in Synthesis Example 2.

[Component (a2): Component (A) other than component (a1)]
a2-1 (α-SF salt): Sodium α-sulfomyristic acid methyl ester obtained in Synthesis Example 3.
-A2-2 (α-SF salt): Sodium α-sulfolauric acid methyl ester obtained in Synthesis Example 4.
-A2-3 (SAS): Secondary alkane (carbon number 14 to 17) sodium sulfonate (manufactured by Clariant Japan Co., Ltd., trade name: HOSTAPUR SAS 30A).
-A2-4 (LAS): Sodium linear alkyl benzene sulfonic acid (10 to 14 carbon atoms) (straight chain alkyl benzene sulfonic acid (manufactured by TAYCA Corporation, trade name: TAYCA Power L121) neutralized with NaOH).
-A2-5 (AES): Polyoxyethylene (average 3 mol) alkyl (12 to 14 carbon atoms) ether sulfate ester salt (manufactured by Lion Corporation, trade name: Sannol LMT-1430).
-A2-6 (AOS): α-olefin (14 carbon atoms) sodium sulfonate (manufactured by Lion Corporation, trade name: Liporan LJ-441).
-A2-7 (soap): Sodium lauric acid (lauric acid (manufactured by NOF CORPORATION, trade name: NAA-122) neutralized with sodium hydroxide).

<Ingredient (B)>
B-1: Methylaminopropylamide obtained in Synthesis Example 5 (R ¹ = linear alkyl group having 13 carbon ^{atoms, R 2} = hydrogen atom, R ³ = propylene group in the general formula (II)) (CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group).
B-2: C18 dimethylaminopropylamide (manufactured by Toho Kagaku Co., Ltd., trade name "catinal MPAS"); R ¹ in general formula (II) = a molecule having a linear alkyl group having 15 carbon atoms (C16 (C16 ( Palmitate dimethylaminopropylamide)) and R ¹ = a molecule that is a linear alkyl group with 17 carbon atoms (C18 (dimethylaminopropylamide stearate)) in terms of mass ratio of C16: C18 = 3: 7 Mixture of. R ² = hydrogen atom, R ³ = propylene group ((CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group.
B-3: Bechenic acid dimethylaminopropylamide obtained in Synthesis Example 6 (R ¹ = linear alkyl group having 21 carbon ^{atoms, R 2} = hydrogen atom, R ³ = propylene group in general formula (II)) (CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group.

<Ingredient (C)>
C-1: 2-ethylhexyl glucoside (manufactured by LG Household & Health Care, trade name: Milcoside 435N).
<(C') component: Alkyl polyglycoside having no branched alkyl group>
C'-1: C8-10 linear alkyl glucoside (manufactured by BASF, trade name: Glucopon215UP).
C'-2: Caprylyl glycoside (manufactured by LG Household & Health Care, trade name: Milcoside 430N).

<Ingredient (D)>
D-1: Sodium cumene sulfonate (manufactured by TAYCA, trade name: TAYCA TOX N5040).
D-2: Potassium cumene sulfonic acid (cumene sulfonic acid (manufactured by Teika Co., Ltd., trade name: Teika Power 500) was neutralized with potassium hydroxide and used).
D-3: Sodium p-toluenesulfonate (manufactured by Kanto Chemical Co., Inc., reagent first grade).
D-4: Sodium benzenesulfonate (manufactured by Kanto Chemical Co., Inc.).

<Arbitrary ingredient>
pH adjuster: 1N sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.) or 1N sulfate (manufactured by Kanto Chemical Co., Inc.).
Amylase: Made by Novozymes Japan, Product name: Termamil Ultra 300L.
Protease: Made by Novozymes Japan, trade name: Sabinase 16XL.
Na citrate: Sodium citrate, manufactured by Fuso Chemical Industry Co., Ltd.
Water: Ion-exchanged water.

[Synthesis Example 1]
1 kg (3.3 mol) of stearic acid methyl ester (“Pastel M-18” manufactured by Lion Specialty Chemicals Co., Ltd.) was placed in a reactor having a capacity of 3 L, and anhydrous sulfuric acid (“Nisso Sulfone” manufactured by Nisso Metallochemical Co., Ltd. ”) 323 g (4 mol) was heated and gasified, and sulfonated by pouring it through a nitrogen flow in an open system. The reaction temperature was 80 ° C., and the supply rate of anhydrous sulfuric acid was 10 g / min. Then, the aging reaction was carried out at 80 ° C. for 30 minutes to obtain an α-sulfofatty acid methyl ester.
20% by mass (290 g) of methanol (manufactured by Kanto Chemical Co., Inc.) with respect to the obtained α-sulfofatty acid methyl ester, and 2% by mass (35% by mass) of hydrogen peroxide in terms of pure content (35% by mass H ₂ O ₂ ). After adding 83 g) as (manufactured by Kanto Chemical Co., Inc.), esterification and bleaching were carried out by reacting at 80 ° C. for 60 minutes.
The obtained bleaching acid was adjusted to pH 7.0 with an aqueous sodium hydroxide solution, and the reaction solvent was distilled off under reduced pressure. Since it foams on the way, isopropanol was added and water was distilled off while azeotropically boiling. The residue was dissolved in a mixture of ethanol / water = 9/1 (volume ratio) by heating at 60 ° C., and the insoluble matter was removed by filtration. The filtrate was cooled to 5 ° C. and recrystallized, and then the precipitate was filtered off and dried in vacuum to obtain sodium α-sulfostearate methyl ester.

[Synthesis Example 2]
In Synthesis Example 1, 1 kg (3.7 mol) of palmitic acid methyl ester (“Pastel M-16” manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of stearic acid methyl ester, and the amount of anhydrous sulfuric acid used was 359 g (4.5 mol). ) Was obtained in the same manner as in Synthesis Example 1 to obtain α-sulfopalmitic acid methyl ester sodium.

[Synthesis Example 3]
In Synthesis Example 1, 1 kg (4.1 mol) of methyl myristic acid (“Pastel M-14” manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of the stearic acid methyl ester, and the amount of anhydrous sulfuric acid used was 398 g (5.0 mol). Synthetic was carried out in the same manner as in Synthesis Example 1 except that it was changed to α-sulfomyristic acid methyl ester sodium.

[Synthesis Example 4]
In Synthesis Example 1, 1 kg (4.6 mol) of methyl laurate (“Pastel M-12” manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of the stearic acid methyl ester, and the amount of anhydrous sulfuric acid used was 449 g (5.6 mol). Synthetic was carried out in the same manner as in Synthesis Example 1 except that it was changed to α-sulfolauric acid methyl ester sodium.

[Synthesis Example 5]
In a 4-necked flask with a capacity of 3 L, 907.0 g (3.97 mol) of methyl myristate (molecular weight 228.4) and 121.6 g (1.19 mol) of dimethylaminopropylamine (DMAPA, molecular weight 102.2) were added. Was charged, and the inside of the reaction vessel was replaced with nitrogen under reduced pressure twice, and then the temperature was raised to 185 ° C. After aging for 1.5 hours with the reaction starting at 180 ° C., 405.7 g (3.97 mol) of DMAPA (molecular weight 102.2) was added dropwise over 4 hours.
After completion of the dropping, aging was carried out for 7 hours, then the temperature was raised to 195 ° C., and excess DMAPA was removed under reduced pressure (treatment for 1 hour after reaching 2.4 kPa) to obtain 1183 g of myristic acid (C14) dimethylaminopropylamide. Obtained.

[Synthesis Example 6]
Behenic acid (C22) dimethylaminopropylamide was obtained in the same manner as in Synthesis Example 5 except that methyl behenate was used instead of methyl myristate in Synthesis Example 5.

<Examples and comparative examples>
According to the compositions shown in Tables 1 to 7, 0.8 kg of the cleaning agent (liquid) of each example was prepared as follows. Ingredients whose blending amount is not listed in the table are not blended.
First, sodium citrate (arbitrary component) was dissolved in water in a 1 L beaker to prepare an aqueous solution of sodium citrate (0.4 kg) in an amount (0.4 kg) that was 50% by mass of the total detergent. When sodium citrate was not blended, an amount (0.4 kg) of water corresponding to 50% by mass of the total detergent was placed in a 1 L beaker.
Separately, in a 1 L capacity beaker, water adjusted to 75 ° C., (A) component, (B) component, (C) component (or (C') component), and (D) component are mixed and these are mixed. The surfactant solution was prepared so that the total amount was 40% by mass (0.32 kg) of the total amount of the cleaning agent.
Next, the aqueous sodium citrate solution (or water) prepared above was heated to 75 ° C., and the entire amount of the surfactant solution adjusted to 75 ° C. was added while stirring at 6000 rpm of an azihomo mixer, and then for 30 seconds. The mixture was stirred to obtain a mixed solution.
After cooling this mixed solution to 25 ° C., the pH of the cleaning agent (25 ° C.) was adjusted to 7.0 using 1N sodium hydroxide or 1N sulfuric acid as a pH adjuster. Next, enzymes (amylase, protease) were added and stirred, and the remaining water was added and stirred so that the total amount of the detergent was 100% by mass (0.8 kg) to obtain a liquid detergent.
The pH (25 ° C.) value was measured by measuring a liquid cleaning agent adjusted to 25 ° C. using a glass electrode type pH meter (HM-30G, manufactured by DKK-TOA CORPORATION).

For the cleaning agents of each example, the low foaming property, the detergency against oil stains in low temperature cleaning, and the low temperature stability of the liquid were evaluated by the following methods. The results are shown in the table.
<Evaluation method>
[Low foaming]
The amount of detergent used in the table is put into an automatic dishwasher (manufactured by Panasonic, model: NP40SX-2, amount of water used in the washing process is about 3 L), and standard using water at room temperature (5 ° C). I drove on the course. The door was opened at the same time as the operation was stopped 1 minute after the start of cleaning, and the height of bubbles (mm) on the water surface in the refrigerator was measured on a scale 15 seconds later. The bubble height was measured at any three points, and the average value was calculated. The foam height is preferably 10 mm or less in terms of the operational suitability of the automatic dishwasher.

[Cleaning power against oil stains (low temperature course)]
Automatic dishwashing of polypropylene lunch box (length 110 mm, width 170 mm, height 35 mm) contaminated with 6 g of mixed oil of beef fat / lard / butter / salad oil = 3/3/3/1 and 6 g of retort curry (Bon Curry Gold 21 dry) It was loaded into a dryer (manufactured by National Co., Ltd., model: NP-45MD6S), and washed in a low-temperature course (cleaning temperature 35 ° C., cleaning time about 40 minutes) with the amount of cleaning agent used in the table. .. The finished condition of a total of 10 surfaces, 5 inner surfaces and 5 outer surfaces of the bento box after cleaning, was sensory-evaluated based on the following criteria. 3 points or more is preferable.
(Criteria for scoring)
6 points: Oil stains on all 10 sides of the lunch box have been completely removed.
5 points: Oil stains on the 8th to 9th sides of the lunch box have been completely removed, and when the remaining sides are carefully observed, very slight adhesion is observed, but it is a level that does not need to be rewashed.
4 points: Oil stains on the 6th to 7th sides of the lunch box have been completely removed, and when the remaining sides are carefully observed, very slight adhesion is observed, but it is a level that does not need to be rewashed.
3 points: Oil stains on 5 or less sides of the lunch box have been completely removed, and when the remaining sides are carefully observed, very slight adhesion is observed, but it is a level that does not need to be rewashed.
2 points: Oil stains remain thinly on one or more sides of the lunch box and need to be rewashed.
1 point: Oil remains sticky on one or more sides of the lunch box and needs to be rewashed.

[Low temperature stability]
50 mL of the cleaning agent of each example was placed in a colorless and transparent glass sample bottle (PS11 standard bottle), and the lid was closed and sealed to prepare an evaluation sample. The evaluation samples were allowed to stand in a constant temperature bath at 10 ° C., 5 ° C., 0 ° C., and −5 ° C., respectively, and stored for 1 week.
The appearance of the liquid after storage was visually observed, and it was judged that there was a change when at least one of solidification or precipitate was formed. The low temperature stability of the cleaning agent was evaluated based on the following criteria.
(Evaluation criteria)
A: No change at storage temperature -5 ° C.
B: There is a change at the storage temperature of -5 ° C, and there is no change at 0 ° C.
C: There is a change at the storage temperature of 0 ° C, and there is no change at 5 ° C.
D: There is a change at the storage temperature of 5 ° C, and there is no change at 10 ° C.
E: There is a change at the storage temperature of 10 ° C.

As shown in the results of Tables 1 to 7, the cleaning agents of Examples 1 to 64 are excellent in low foaming property, have many oil stains, have a low cleaning temperature of 35 ° C., and are prone to recontamination with oil. Excellent detergency against oil stains was obtained even under the harsh conditions of polypropylene tableware. Further, in Examples 1 to 4, 6, 7, 9, 10, 12 to 25, 27 to 62 containing one or both of the component (C) and the component (D), the low temperature stability of the liquid was good. there were.
Comparative Examples 3 to 9 containing no component (A) and Comparative Example 2 in which the mass ratio of the component (B) / component (A) exceeds 10 have good low foaming properties, but are used for cleaning against oil stains in low temperature cleaning. The power was insufficient. Moreover, the low temperature stability was insufficient in spite of containing the component (C) and the component (D).
In Comparative Example 1 in which the mass ratio of the component (B) / component (A) was less than 0.1, the detergency against oil stains in low-temperature cleaning was good, but the low foaming property was insufficient.
In Examples 63 and 64 in which the component (C') was used instead of the component (C), the low foaming property and the detergency were good, but the low temperature stability was insufficient.

Claims (6)

Component (A): An anionic surfactant containing an α-sulfofatty acid alkyl ester salt (a1) represented by the following general formula (I) .
Component (B): Contains a compound represented by the general formula (II) and a solvent .
Component (B) / (A) weight ratio expressed by components Ri 0.1-10 der,
The content of the component (A) is 0.1 to 5% by mass.
Furthermore branched one or you containing both, machine dishwashing liquid detergent of the alkyl polyglycosides (C), and an aromatic sulfonic acid or a salt thereof (D) having an alkyl group.
R ^11- CH (SO ₃ M) -COOR ¹² ... (I)
[In formula (I), R ¹¹ is an alkyl group having 14 to 16 carbon atoms, R ¹² is an alkyl group having 1 to 2 carbon atoms, and M is a counter ion. ]

[In formula (II), R ¹ represents a linear or branched chain alkyl or alkenyl group having 13 to 21 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. R ³ represents an alkylene group having 1 to 4 carbon atoms. R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively, and may be the same or different from each other. ] The component (B) is represented by the general formula (II), where R ¹ is a linear alkyl group having 13 to 21 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is. The liquid cleaning agent for a dishwasher according to claim 1, wherein the liquid cleaning agent for a dishwasher according to claim 1, wherein the alkylene group having 1 to 4 carbon atoms and R ⁴ and R ⁵ are one or more selected from the group consisting of compounds which are alkyl groups having 1 to 4 carbon atoms. .. The component (a1) is a compound (a1-C16) having 14 carbon atoms ^{in R 11} in the general formula (I) and a compound (a1) having 16 carbon atoms ^{in R 11 in the general formula (I).} The liquid detergent for a dishwasher according to claim 1 or 2, which comprises −C18) and has a mass ratio of (a1-C16): (a1-C18) of 30:70 to 90:10. The liquid detergent for a dishwasher according to any one of claims 1 to 3, wherein the mass ratio represented by [component (C) + component (D)] / component (A) is 2 to 30. The dishwasher according to any one of claims 1 to 4, which contains the component (C) and the component (D) and has a mass ratio of the component (C) / component (D) of 0.03 to 29. Liquid cleaning agent for machines. The liquid detergent for a dishwasher according to any one of claims 1 to 5, wherein the component (C) is a 2-ethylhexyl polyglycoside and the component (D) is a cumene sulfonate.