JP2016011342A - Detergent composition for tableware - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for tableware excellent in detergency and foaming property, and capable of preventing food material odor from remaining on a sponge by daily tableware washing.SOLUTION: The detergent composition for tableware contains (A) component: at least one kind selected from a semipolar surfactant, an ampholytic surfactant and a cationic surfactant, (B) component: a surfactant other than the (A) component, (C) component: an alcohol component containing monovalent alcohol having branched hydrocarbon group and (D) component: at least one kind selected from zinc, copper, manganese, nickel, cobalt and iron, and has a mass ratio represented by the (A) component/the (C) component of 4.1 to 20.

Description

  The present invention relates to a dishwashing detergent composition.

  In recent years, sponges for washing dishes have been diversified. For example, as a sponge with better foam than conventional urethane sponge, it is covered with an acrylic or polyester net, covered with a polypropylene or polyethylene terephthalate pile, and an acrylic non-woven fabric. Sponge etc. are used.

  However, while such a sponge has better foam retention, a part of the food is easily held inside the sponge, and the odor of the food (odor derived from fish and other foods) may be transferred to the sponge. In particular, when the sponge is covered with a pile, hydrophobic stains tend to remain on the pile material, and the odor of food tends to remain on the sponge.

Sponge odor prevention methods include impregnating a sponge with a certain amount of dishwashing detergent composition and allowing it to stand overnight (about 18 hours) to prevent the growth of bacteria. Deodorization method to deodorize by soaking in.
As a dishwashing detergent composition having a sterilizing power, a liquid detergent composition in which a nonionic surfactant, an amphoteric surfactant and a biguanide antibacterial agent are combined is known (see Patent Document 1). .

JP 2012-197335 A

In the case of the conventional sterilization method or deodorization method, it takes time and effort to prevent the smell of the sponge. Therefore, it is required that the smell of the sponge can be prevented together by performing a simpler method such as daily dishwashing.
However, it is known that dishwashing detergent compositions used for dishwashing, etc. have sterilizing power in addition to the basic detergency and foaming ability, but only by performing daily dishwashing It was not possible to prevent the odor from remaining on the sponge.

  The present invention has been made in view of the above circumstances, and provides a dishwashing detergent composition that is excellent in detergency and foaming properties, and that can prevent food odor from remaining on the sponge by performing daily dishwashing. With the goal.

The present invention has the following aspects.
[1] (A) component: at least one selected from a semipolar surfactant, an amphoteric surfactant, and a cationic surfactant; (B) component: a surfactant other than the component (A); (C) component: an alcohol component containing a monohydric alcohol having a branched hydrocarbon group, and (D) component: at least one selected from zinc, copper, manganese, nickel, cobalt, and iron The cleaning composition for tableware whose mass ratio represented by (A) component / (C) component is 4.1-20.
[2] Component (E): It further contains a sequestering agent, and the mass ratio represented by (C) component / (metal ion in (D) component + (E) component) is 1.6 to 10. The cleaning composition for tableware as described in [1].
[3] The detergent composition for tableware according to [2], wherein the component (E) is an aminocarboxylic acid type sequestering agent.

  The dishwashing detergent composition of the present invention has excellent detergency and foaming ability, and can prevent food odor from remaining on the sponge by performing daily dishwashing.

Hereinafter, the present invention will be described in detail.
The dishwashing detergent composition of the present invention is a liquid detergent and contains the following components (A), (B), (C), and (D). Moreover, it is preferable that the cleaning composition for tableware further contains (E) component.
In the following specification, the ability to prevent food odor from remaining on the sponge is sometimes referred to as “deodorization”.

<(A) component>
The component (A) is at least one selected from a semipolar surfactant, an amphoteric surfactant, and a cationic surfactant. When the detergent composition for tableware contains the component (A), it exhibits high detergency (especially detergency against oil stains) and excellent foamability due to interaction with the component (B) described later. Moreover, by using together with (C) component and (D) component which are mentioned later, it can prevent that a foodstuff odor remains in sponge by daily dishwashing.

Examples of the amphoteric surfactant include a carboxylate type, a sulfate ester type, a sulfonate type, and a phosphate ester salt type, and any of these can be used.
Specific examples of the carboxylate type amphoteric surfactant include lauryl dimethylaminoacetic acid betaine, coconut alkyldimethylaminoacetic acid betaine, coconut oil fatty acid amidepropylbetaine, lauric acid amidepropyldimethylaminoacetic acid betaine, coconut alkylamidopropyldimethylamino Examples include betaine-type amphoteric surfactants such as betaine acetate and laurylpropylaminoacetic acid betaine.
These amphoteric surfactants may be used alone or in combination of two or more.

It does not specifically limit as a cationic surfactant, A well-known thing can be used.
Specifically, didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyl dihydroxyethylammonium chloride, di-tallow alkyldimethylammonium chloride, di (stearoyloxyethyl) dimethyl Ammonium chloride, di (oleoyloxyethyl) dimethylammonium chloride, di (palmitoyloxyethyl) dimethylammonium methosulfate, di (stearoyloxyisopropyl) dimethylammonium chloride, di (oleoyloxyisopropyl) dimethylammonium chloride, di (oleoyl) Oxybutyl) dimethylammonium chloride Di (stearoyl oxy ethyl) methyl-hydroxyethyl ammonium methosulfate, tri (stearoyl oxyethyl) methyl methosulfate, stearyl trimethyl ammonium chloride. The “beef tallow alkyl” group has 14 to 18 carbon atoms.

  In the present invention, the semipolar surfactant is an amine oxide type surfactant. Examples of amine oxide surfactants include alkylamine oxide and alkanoylamide alkylamine oxide.

As the component (A), a semipolar surfactant is preferably used, and a semipolar surfactant represented by the following general formula (1) is more preferably used as the semipolar surfactant.
R ^1- (D) _p -N (-R ² ) (-R ³ ) → O (1)

In formula (1), R ¹ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ² and R ³ each independently represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and D represents —C (═O) (— NH—R ⁴ ) — is represented, R ⁴ represents an alkylene group having 1 to ⁴ carbon atoms, and p is an integer of 0 to 1.

In Formula (1), R ¹ represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms. Among these, R ¹ is preferably an alkyl group having 8 to 18 carbon atoms. The alkyl group and alkenyl group in R ¹ may be linear or branched.
The number of carbon atoms in the alkyl group and alkenyl group for R ¹ is 8 to 18, 10 to 14 is preferred.

R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. The number of hydroxy groups in the hydroxyalkyl group in R ² and R ³ may be one or two or more. Among these, R ² and R ³ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. More preferably, R ² and R ³ are both methyl groups. The alkyl group and hydroxyalkyl group in R ² and R ³ may be linear or branched.

D represents —C═O (—NH—R ⁴ ) —, and R ⁴ represents an alkylene group having 1 to ⁴ carbon atoms.
p is an integer of 0 to 1, and 0 is preferable.

Specific examples of the semipolar surfactant represented by the formula (1) include lauryl dimethylamine oxide (n-dodecyldimethylamine oxide), coconut alkyldimethylamine oxide, lauryl diethylamine oxide, lauric acid amidopropyl dimethylamine oxide, and the like. Is mentioned.
Of these, lauryl dimethylamine oxide is preferred because it can easily provide detergency against oil stains and a deodorizing effect.
These semipolar surfactants may be used alone or in combination of two or more.

  5-20 mass% is preferable and, as for content of (A) component in 100 mass% of cleaning compositions for tableware, 6-10 mass% is more preferable. If content of (A) component is more than the said lower limit, the detergency with respect to oil dirt and foaming property will increase more. On the other hand, if content of (A) component is below the said upper limit, it can suppress that the viscosity of the detergent composition for tableware rises too much, and can maintain a cleaning power and foamability favorably.

<(B) component>
The component (B) is a surfactant other than the component (A). When the cleaning composition for tableware contains the component (B), it exhibits high detergency (especially detergency against oil stains) and excellent foamability due to the interaction with the component (A). Moreover, by using together with (C) component and (D) component which are mentioned later, it can prevent that a foodstuff odor remains in sponge by daily dishwashing.
Examples of the component (B) include anionic surfactants and nonionic surfactants.

(Anionic surfactant)
Examples of the anionic surfactant include linear alkyl benzene sulfonate, α-olefin sulfonate, linear or branched alkyl sulfate ester, alkyl ether sulfate ester or alkenyl ether sulfate ester, and an alkyl group. Examples include alkane sulfonates and α-sulfo fatty acid ester salts.
Examples of these salts include alkali metal salts such as sodium and potassium; alkanolamine salts such as monoethanolamine and diethanolamine.

As the anionic surfactant, an anionic surfactant represented by the following general formula (2) is preferable.
_{^{R 5 -O- (PO) m -}} (EO) n -SO 3 - M + ... (2)

In formula (2), R ⁵ represents a linear alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is a primary carbon atom. PO is an oxypropylene group, EO is an oxyethylene group, m is the average number of repetitions of PO, n is the average number of repetitions of EO, and 0 ≦ m <1 and 0 <n ≦ 4. M ⁺ is a cation other than hydrogen ions.

In formula (2), R ⁵ represents a linear alkyl group having 8 to 18 carbon atoms. The number of carbon atoms of the alkyl group in R ⁵ is preferably 10 to 14, 12 to 14 is more preferable. R ⁵ is preferably an alkyl group derived from a fat and oil raw material in terms of detergency and environment. Suitable fats and oils include palm kernel oil, coconut oil and the like.

PO is an oxypropylene group, m represents the average number of repeating POs (average number of moles added), and 0 ≦ m <1.
EO is an oxyethylene group, n represents the average number of EO repeats (average number of moles added), and 0 <n ≦ 4.
When both EO and PO are present, the arrangement state thereof does not matter.

M ⁺ is, for example, an ion of alkali metal, alkaline earth metal, ammonium or alkanolamine, and may be any one that can form a water-soluble salt. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

Specific examples of the anionic surfactant represented by the formula (2) include polyoxyethylene (1) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) ether sulfate. Sodium salt, polyoxyethylene (4) linear alkyl (C12) ether sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (1) Linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt, polyoxyethylene (2) Linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt , Polyoxyethylene (4) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Ether sodium sulfate, polyoxypropylene (0.4) polyoxyethylene (1.5) a linear alkyl; and (C12 / 14 = 75/25 derived from a natural fat) ether sulfate sodium salt and the like.
Among them, polyoxyethylene (1) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt is preferable because it can easily obtain detergency against oil stains and a deodorizing effect.

Here, for example, “polyoxyethylene (1)” means that the average number of repeating oxyethylene groups is 1 (the average number of added moles of ethylene oxide is 1).
“C12 / 14 = 75/25; derived from natural fats and oils” means a mixture of a compound having a linear alkyl group having 12 carbon atoms and a compound having a linear alkyl group having 14 carbon atoms (mixing ratio: by mass ratio). 75/25) and a linear alkyl group derived from natural fats and oils.
These anionic surfactants may be used alone or in combination of two or more.

(Nonionic surfactant)
It does not specifically limit as a nonionic surfactant, A well-known thing can be used.
Specifically, R ⁶ —O— (R ⁷ O) _q —H (where R ⁶ is a linear or branched hydrocarbon group having 10 to 18 carbon atoms; R ⁷ is a carbon atom having 1 to 3 carbon atoms) A hydrogen group, preferably an alkylene group; q is an average number of R ⁷ O repeats, and is a number of 1 to 20, preferably 5 to 15.) , Alkyl glycosides, sorbitan fatty acid esters and the like. Among them, R ⁶ is a linear or branched alkyl group having 10 to 18 carbon atoms, R ⁷ is an alkylene group having 2 to 3 carbon atoms, and q is 5 to 20, a polyoxyalkylene addition type nonionic interface An activator (polyoxyalkylene alkyl ether) is preferred.

  3-25 mass% is preferable and, as for content of (B) component in 100 mass% of cleaning compositions for tableware, 5-20 mass% is more preferable. If content of (B) component is more than the said lower limit, the detergency with respect to oil dirt and foaming property will increase more. On the other hand, if content of (B) component is below the said upper limit, it can suppress that the viscosity of the detergent composition for tableware raises too much, and can maintain a cleaning power and foamability favorably.

<(C) component>
The component (C) is an alcohol component containing a monohydric alcohol having a branched hydrocarbon group. The effect that the cleaning composition for tableware contains the component (C) increases the detergency by interaction with the component (A) and the component (D) described later, and prevents the odor of food ingredients from remaining on the sponge. Demonstrate.

8-24 are preferable and, as for carbon number of the hydrocarbon group in the monohydric alcohol which has a branched hydrocarbon group, 10-16 are more preferable. Such a monohydric alcohol may be a primary alcohol, a secondary alcohol, or a tertiary alcohol as long as it has a branched hydrocarbon group, but a primary alcohol is preferred.
Further, from the viewpoint of enhancing the detergency and preventing the odor of food ingredients from remaining on the sponge, it is preferably a monohydric alcohol and a branched gerbet alcohol having a hydrocarbon group having 8 to 24 carbon atoms. A branched gerbet alcohol having 10 to 16 carbon atoms is more preferable.
Preferable examples of the monohydric alcohol having a branched hydrocarbon group include, for example, 2-ethyl-1-hexanol, 2-propyl-1-heptanol, 2-butyl-1-octanol, 2-butyl-1-decanol, 2 Primary alcohols such as hexyl-1-octanol, 2-hexyl-1-decanol, 2-hexyl-1-dodecanol, 2-octyl-1-dodecanol, 2-decyl-1-tetradecanol; Secondary alcohols such as 2-heptanol are exemplified. Among these, primary alcohols 2-butyl-1-octanol, 2-butyl-1-decanol, 2-hexyl-1-octanol, and 2-hexyl-1-decanol are preferable.
These monohydric alcohols having a branched hydrocarbon group may be used alone or in combination of two or more.

(C) The ratio of the monohydric alcohol having a branched hydrocarbon group in 100% by mass of the component is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and 100% by mass. Is particularly preferred.
The component (C) is a monovalent having a branched hydrocarbon group in terms of the effect of preventing interaction with the component (A) and the component (B) or detergency and preventing the odor of food from remaining on the sponge. It is preferable to use at least 20% by mass of alcohol in the component (C).

The component (C) may contain an alcohol other than the monohydric alcohol having a branched hydrocarbon group (other alcohol).
Examples of other alcohols include monovalent primary alcohols having a straight chain hydrocarbon group having 8 or more carbon atoms. Specific examples include decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol and the like.

As a commercial item of (C) component, for example, Safol 23 (manufactured by Sasol, C12 / C13 = 50% / 50%, mass ratio, branching rate 50%), Diador 13 (manufactured by Mitsubishi Chemical Corporation, C13: 100) %, Branching rate 50%), neodol 23 (manufactured by Shell, C12 / C13 = 40% / 60%, mass ratio, branching rate 20%), etc. Mixed primary alcohol with a monohydric alcohol having a hydrocarbon group; Isophor 12 (manufactured by Sasol, C12: 100%, branching rate 100%), Isophor 14T (manufactured by Sasol, C12 / 14/16 = 20 % / 50% / 30%, mass ratio, branching rate 100%), isophor 16 (manufactured by Sasol, C16: 100%, branching rate 100%), isophor 20 (manufactured by Sasol, C20: 10) 0%, branching rate 100%), etc.
Here, “C12” is a monohydric alcohol having a branched or straight chain alkyl group having 12 carbon atoms, and “C13” is a monohydric alcohol having a branched or straight chain alkyl group having 13 carbon atoms. That is. Further, the “branch rate” is a ratio (mass%) of a monohydric alcohol having a branched hydrocarbon group in the alcohol.

  0.6-3 mass% is preferable and, as for content of (C) component in 100 mass% of cleaning compositions for tableware, 1-2 mass% is more preferable. If content of (C) component is more than the said lower limit, a deodorizing effect will increase more. On the other hand, if content of (C) component is below the said upper limit, it can suppress that the viscosity of a detergent composition for tableware raises excessively, or a uniformity falls, Detergency and foamability Can be maintained well.

  The mass ratio represented by the component (A) / component (C) (hereinafter sometimes referred to as “(A) / (C) mass ratio”) is 4.1 to 20, and 4.2. To 10 is preferred. When the mass ratio (A) / (C) is within the above range, the effect of the component (D) described later is sufficiently exhibited, and the deodorizing effect is enhanced. In particular, if the (A) / (C) mass ratio is not less than the above lower limit value, the deodorizing effect is improved. Moreover, it can suppress that the viscosity of the detergent composition for tableware rises excessively, and a handleability becomes favorable. On the other hand, if (A) / (C) mass ratio is below the said upper limit, the deodorizing effect, especially the deodorizing effect with respect to the amine odor of fish will increase.

  Further, the total content of the component (A) and the component (C) in 100% by mass of the dishwashing detergent composition (hereinafter sometimes referred to as “(A) + (C) content”) is 5. 0.5-21 mass% is preferable, and 6.5-11 mass% is more preferable. When the (A) + (C) content is within the above range, the deodorizing effect is further enhanced.

<(D) component>
The component (D) is at least one selected from zinc, copper, manganese, nickel, cobalt, and iron. An excellent deodorizing effect is exhibited when the detergent composition for tableware contains the component (D).

  (D) As a component, zinc, copper, and manganese are preferable, zinc and copper are more preferable, and zinc is still more preferable. By using these components (D), the deodorizing effect can be further enhanced.

  (D) component may be mix | blended as various metal compounds, and may be mix | blended as a complex with (E) component mentioned later. However, it is preferable to mix | blend (D) component as a metal compound from viewpoints, such as the beauty | look of a cleaning composition for tableware, and production efficiency.

  The metal compound only needs to be soluble in water. Examples of the salt forming the metal compound include inorganic salts such as nitrates, sulfates, chlorides, perchloric acid peroxides, ammonium chloride salts, and cyanides; acetates , Organic salts such as gluconate, tartrate and glycine.

The zinc compound is not particularly limited as long as it releases zinc ions in water. For example, zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, Examples include zinc tartrate and zinc perchlorate. Among these, zinc sulfate, zinc chloride, and gluconate are preferable, and zinc sulfate is more preferable in terms of handling property, cost, raw material supply property, and the like.
The copper compound is not particularly limited as long as it releases copper ions in water. For example, copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper ammonium chloride, copper gluconate, Examples include copper tartrate and copper perchlorate. Among these, copper sulfate, copper chloride, and copper gluconate are preferable and copper sulfate is more preferable in terms of handleability, cost, raw material supply property, and the like.
The manganese compound is not particularly limited as long as it releases manganese ions in water, and examples thereof include manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, and manganese acetylacetonate. Among these, manganese sulfate and manganese chloride are preferable in terms of handleability, cost, raw material supply property, and the like.

  The content of the component (D) in 100% by mass of the detergent composition for tableware is determined in the range of 0.001 to 2% by mass, for example, depending on the type of the component (D). If content of (D) component is more than the said lower limit, a deodorizing effect will increase more. On the other hand, if content of (D) component is below the said upper limit, it can suppress that (D) component isolate | separates from the detergent composition for tableware, and can maintain a deodorizing effect favorably.

For example, when using zinc as the component (D), the content of zinc in 100% by mass of the dishwashing detergent composition is preferably 0.002 to 2% by mass, more preferably 0.02 to 1% by mass, 0.05-0.5 mass% is further more preferable. If the zinc content is not less than the above lower limit, the deodorizing effect is further enhanced, but even if the content exceeds the upper limit, the deodorizing effect may not be further improved.
Or when using copper as (D) component, 0.001-0.5 mass% is preferable, and, as for content of copper in 100 mass% of detergent compositions for tableware, 0.01-0.3 mass% Is more preferable, and 0.02-0.15 mass% is further more preferable. If the copper content is equal to or higher than the lower limit, the deodorizing effect is increased. However, even if the content exceeds the upper limit, the deodorizing effect may not be further improved.
Or when using manganese as (D) component, 0.001-0.5 mass% is preferable, and, as for content of manganese in 100 mass% of cleaning compositions for dishes, 0.01-0.3 mass% Is more preferable, and 0.02-0.15 mass% is further more preferable. If the manganese content is not less than the lower limit, the deodorizing effect is enhanced. However, even if the manganese content exceeds the upper limit, the deodorizing effect may not be further improved.

  In addition, when mix | blending (D) component as a complex with (E) component mentioned later, a complex can be manufactured with the manufacturing method of the complex as described in international publication 09/078459, for example.

<(E) component>
(E) A component is a sequestering agent. When the detergent composition for tableware contains (E) component, the deodorizing effect becomes easier to exhibit by interaction with (C) component and (D) component.

  As the component (E), an aminocarboxylic acid type sequestering agent is preferable. Specifically, nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, Examples include aminocarboxylates such as iminodisuccinate; hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine. Among them, an aminocarboxylic acid type sequestering agent having two or more carboxy groups in the molecule is preferable, and a compound represented by the following general formula (3) or the following general formula (4) is more preferable. .

In Formula (3), X ^{1 to} X ⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or a cationic ammonium, R ⁸ represents a hydrogen atom or a hydroxy group, and s is 0 or 1 Represents an integer.

In Formula (4), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom, and X ^{5 to} X ⁷ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or Represents cationic ammonium, and t represents an integer of 0 to 5.

In the formula ⁽³⁾ as the alkali metal in the X 1 to X ^4, sodium, potassium and the like. Examples of the alkaline earth metal include calcium and magnesium. When at least one of X ^{1 to} X ⁴ is an alkaline earth metal, it corresponds to 1/2 atom. For example, when ^{X 1} is a calcium, -COOX ¹ is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
Among these, X ^{1 to} X ⁴ are preferably alkali metals.
X ^{1 to} X ⁴ in the formula (3) may be the same or different.

R ⁸ in formula (3) may be either a hydrogen atom or a hydroxy group.
As for s in Formula (3), 1 is preferable.

  Examples of the compound represented by the formula (3) include iminodisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, and salts thereof. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is more preferable.

In formula (4), the alkali metal, alkaline earth metal, and cationic ammonium in X ^{5 to} X ⁷ are the same as the alkali metal, alkaline earth metal, and cationic ammonium in X ^{1 to} X ⁴ , respectively. Is mentioned. X ^{5 to} X ⁷ are preferably alkali metals.
X ^{5 to} X ⁷ in the formula (4) may be the same or different from each other.

The alkyl group in A of Formula (4) may be linear or branched. 1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxy group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, and a hydrogen atom, and is preferably a hydrogen atom.
As for t in Formula (4), the integer of 0-2 is preferable and 1 is more preferable.

  Examples of the compound represented by the formula (4) include nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, hydroxyethyliminodiacetic acid, Examples include salts. Among these, nitrilotriacetic acid, methyl glycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid or a salt thereof is preferable, and methyl glycine diacetic acid or a salt thereof is more preferable. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is preferable.

  Examples of the component (E) other than the aminocarboxylic acid type sequestering agent include citric acid, glycolic acid, lactic acid, tartaric acid, malic acid, maleic acid, gluconic acid, and alkali metal salts or alkanolamine salts thereof. Can be mentioned.

These (E) components may be used individually by 1 type, and may use 2 or more types together.
0.1-3 mass% is preferable and, as for content of (E) component in 100 mass% of cleaning compositions for tableware, 0.3-1 mass% is more preferable. If content of (E) component is more than the said lower limit, a deodorizing effect will increase more. On the other hand, if content of (E) component is below the said upper limit, it can suppress that complex formation with (D) component becomes strong too much, and can maintain a deodorizing effect favorably.

  Moreover, the mass ratio (hereinafter referred to as “(C) / ((D) + (E)) mass ratio” expressed by (C) component / (metal ion in (D) component + (E) component)). Is preferably 1.6 to 10, more preferably 2 to 8. If the (C) / ((D) + (E)) mass ratio is within the above range, the deodorizing effect is further enhanced.

  In addition, the mass ratio represented by the metal ions in the component (E) / component (D) (hereinafter sometimes referred to as “(E) / ((D) mass ratio”)) is preferably 1 to 50, The deodorizing effect is further enhanced if the mass ratio (E) / ((D) is within the above range.

<Optional component>
The dishwashing detergent composition of the present invention usually contains water as a solvent.
Moreover, the detergent composition for tableware of this invention is the range normally used for detergents for dishwashing etc. as needed in the range which does not impair the effect of this invention besides (A)-(E) component. The additive may be further contained.
Examples of additives include hydrotropes, chelating agents (excluding the component (E)), pH adjusters, enzymes, viscosity adjusters, thickeners, surface modifiers, antioxidants, ultraviolet absorbers. , Solubilizers, polymer compounds, preservatives, antibacterial agents, dispersants and the like.

(Hydrotrope agent)
Examples of the hydrotrope include monovalent primary alcohols having a straight chain hydrocarbon group having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, glyceryl ethers having 4 to 10 carbon atoms, and paratoluene sulfone. Examples include acids, p-toluene sulfonate, cumene sulfonic acid, cumene sulfonate, benzoic acid, benzoate and the like.
Examples of the monovalent primary alcohol having a linear hydrocarbon group having 2 to 4 carbon atoms include ethanol, n-propanol, and n-butanol.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glyceryl ether having 4 to 10 carbon atoms include hexyl glyceryl ether.

Among these, ethanol and p-toluenesulfonate are preferable in that they are excellent in the dissolution effect and usability of the components (A) to (E) in the dishwashing detergent composition.
These hydrotropes may be used alone or in combination of two or more.
1-30 mass% is preferable and, as for content of the hydrotrope agent in 100 mass% of cleaning compositions for tableware, 5-20 mass% is more preferable.

<Manufacturing method>
It does not restrict | limit especially as a manufacturing method of the cleaning composition for tableware. For example, it is manufactured by mixing the components (A) to (D), water as a solvent, and the component (E) and optional components as necessary.

The pH (25 ° C.) of the cleaning composition for tableware is preferably 6 to 8 in that the cleaning power is enhanced.
In this invention, pH (25 degreeC) of the cleaning composition for tableware shows the value measured by the method based on JISZ8802: 1984 "pH measuring method".
In order to adjust the pH of the cleaning composition for tableware, a pH adjusting agent such as an inorganic alkaline agent or an organic alkaline agent is preferably used. Examples of the inorganic alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, and among them, the storage stability of the dishwashing detergent composition is likely to improve, so sodium hydroxide, potassium hydroxide Etc. are preferred. Examples of the organic alkali agent include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N- (β-aminoethyl) ethanolamine, diethylenetriamine, morpholine, N- Examples thereof include amine compounds such as ethylmorpholine. Among them, monoethanolamine is preferable because the storage stability of the dishwashing detergent composition is easily improved. In addition, when pH is too high, it adjusts, for example using inorganic acids, such as hydrochloric acid and a sulfuric acid; Acids, such as carboxylic acids, such as an acetic acid and a citric acid.

<How to use>
The method for using the dishwashing detergent composition of the present invention is not particularly limited, and is generally applied to a dishwashing composition by directly applying the dishwashing detergent composition to a sponge containing water and foaming. A method is mentioned.

<Effect>
According to the dishwashing detergent composition of the present invention described above, the detergency and foamability are excellent due to the interaction between the component (A) and the component (B). In addition, food odor can be prevented from remaining on the sponge by the interaction of the components (A) to (D).
The reason why the detergent composition for tableware of the present invention is excellent in the deodorizing effect is not clear, but is presumed as follows.
By containing (A) component and (C) component by a specific ratio, the detergent composition for tableware has moderate viscosity, and the sustainability of foam improves. As a result, bubbles are likely to stay in the sponge, the effect of the component (D) is sufficiently exhibited, and the deodorizing effect is considered to be enhanced.

In particular, if the cleaning composition for tableware contains the component (E), the deodorizing effect is more easily exhibited. The reason for this is estimated as follows.
The dish cleaning composition contains the component (E), so that the component (D) in the dish cleaning composition contains the component (E) and a complex (hereinafter sometimes referred to as “metal complex”). It becomes easy to form and (D) component can exist stably in a system. In the vicinity of the (D) component of this metal complex, it is considered that the water coordinated with the (E) component or the (D) component serving as a ligand is easily replaced with another substance. For this reason, in a metal complex, a positively charged odor is substituted with the component (D) and combined with the (E) component in the metal complex, and a negatively charged odor is replaced with water or the (E) component. Thus, it is considered to be combined with the component (D) in the metal complex. In this way, the metal complex is presumed to better capture the odor component, and it can be considered that the food odor remains on the sponge more effectively.
Moreover, it is thought that the metal complex inactivates the microorganisms adhering to the sponge and suppresses the growth of the microorganisms, and as a result, the food odor is also reduced.
Furthermore, the effect that the odor component is captured by the metal complex is continuously exhibited. Therefore, it is considered that the growth of bacteria and the generation of odor can be suppressed for a long time.

  As described above, with the dishwashing detergent composition of the present invention, a certain amount of the dishwashing detergent composition is impregnated into the sponge and left to stand overnight (about 18 hours), or the sponge is soaked in the bleaching agent. You can prevent the smell of sponges by washing the dishes every day, even if you don't need them.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used.
(A-1): n-dodecyldimethylamine oxide (AX) (manufactured by Lion Akzo, “Aromox DM12D-W (C)”, semipolar surfactant)
(A-2): Amidopropyldimethylamine oxide (APAX) laurate (manufactured by Clariant Japan, “GENAMINOX AP”, semipolar surfactant)
-(A-3): laurylpropylaminoacetic acid betaine (manufactured by Lion Corporation, “Enazicol L-30B”, amphoteric surfactant)
-(A-4): Stearyltrimethylammonium chloride (manufactured by Lion Corporation, “Arcard T-800”, cationic surfactant)

As the component (B), the following compounds were used.
(B-1): Sodium polyoxyethylene alkyl ether sulfate (AES) (R ⁵ in the general formula (2) = C12 and C14 linear alkyl group (C12 / C14 = 75% / 25%, (Mass ratio), m = 0, n = 1, M ⁺ = sodium)
(B-2): Polyoxyethylene alkyl ether sodium sulfate (AES) (R ⁵ in the general formula (2) = C12 and C14 linear alkyl group (C12 / C14 = 75% / 25%, (Mass ratio), m = 0, n = 4, M ⁺ = sodium)
(B-3): Sodium polyoxyalkylene alkyl ether sulfate (AES) (R ⁵ in the general formula (2) = C12 and C14 linear alkyl group (C12 / C14 = 75% / 25%, (Mass ratio), m = 0.4, n = 1.5, M ⁺ = sodium)
(B-4): polyoxyethylene (9) lauryl ether (manufactured by Lion Corporation, “Leox LC-90”)

Synthesis method of (B-1):
A 4L autoclave was charged with 400 g of P & G brand name CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio) as raw material alcohol and 0.8 g of a potassium hydroxide catalyst as a reaction catalyst, and nitrogen was added to the autoclave. The temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain polyoxyethylene alkyl ether. The average addition mole number (average repetition number) of ethylene oxide of the obtained polyoxyethylene alkyl ether was 1.
Next, 237 g of the obtained polyoxyethylene alkyl ether was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, this was neutralized with an aqueous sodium hydroxide solution to obtain sodium polyoxyethylene alkyl ether sulfate (B-1).

Synthesis method of (B-2):
A method similar to the synthesis of (B-1) was used. However, 364 g of ethylene oxide was introduced to obtain a compound having an average addition mole number (average number of repetitions) of ethylene oxide of polyoxyethylene alkyl ether of 4 and reacted with 96 g of liquid sulfuric anhydride (sulfane) to obtain polyoxyethylene alkyl ether Sulfuric acid was obtained. Subsequently, this was neutralized with an aqueous sodium hydroxide solution to obtain sodium polyoxyethylene alkyl ether sulfate (B-2).

Synthesis method of (B-3):
A method similar to the synthesis of (B-1) was used. However, in (B-1), when only ethylene oxide was introduced, in (B-3), after 48 g of propylene oxide was introduced and reacted, 136 g of ethylene oxide was subsequently introduced, and propylene oxide of polyoxyalkylene alkyl ether was introduced. A compound having an average addition mole number (average repetition number) of 0.4 and an average addition mole number (average repetition number) of ethylene oxide of 1.5 was obtained, and 96 g of liquid sulfuric anhydride (sulfane) was reacted to obtain polyoxy An alkylene alkyl ether sulfuric acid was obtained. Next, this was neutralized with an aqueous sodium hydroxide solution to obtain sodium polyoxyalkylene alkyl ether sulfate (B-3).

As the component (C) and the substitute for the component (C) (component (C ′)), the following compounds were used.
(C-1): 2-butyl-1-octanol (manufactured by Sasol, “Isophor 12”)
(C-2): A mixture of 2-butyl-1-octanol, 2-butyldecanol, and 2-hexyl-1-octanol (manufactured by Sasol, “Isophor 14T”)
(C-3): a mixture of a monohydric alcohol having an alkyl group having 12 carbon atoms and a monohydric alcohol having an alkyl group having 13 carbon atoms (manufactured by Shell, “Neodol 23”, C12 / C13 = 40% / 60%, mass ratio, branching rate 20%)
(C-4): 2-ethyl-1-hexanol (manufactured by Yoneyama Pharmaceutical Co., Ltd.)
(C-5): 2-octyl-1-dodecanol (manufactured by Sasol, “Isophor 20”)
-(C'-1): Dodecyl alcohol (made by Yoneyama Pharmaceutical Co., Ltd.)

As the component (D), the following compounds were used.
-(D-1): Zinc sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.)
-(D-2): Copper sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.)
-(D-3): Manganese sulfate monohydrate (manufactured by Kanto Chemical Co., Inc.)

As the component (E), the following compounds were used.
(E-1): Trisodium methylglycine diacetate (MGDA) (manufactured by BASF, “Trilon M Compactate”)
(E-2): Trisodium nitrilotriacetate (NTA) (manufactured by BASF, “Trilon A92R”)
(E-3): sodium citrate triacid dihydrate (manufactured by Showa Chemical Co., Ltd.)

The following compounds were used as optional components.
・ Ethanol (hydrotrope agent): manufactured by Kanto Chemical Co., Ltd. ・ p-TS (hydrotrope agent): p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.)
・ Water: Distilled water

"Example 1"
<Preparation of detergent composition for tableware>
1000 g of a dishwashing detergent composition having the composition shown in Table 1 was prepared by the following procedure.
The component (A) and ethanol were placed in a 1 L beaker and sufficiently stirred with a magnetic stirrer (Fine, “F-606N”). Subsequently, the component (B), the component (C), the component (D), the component (E), and an optional component other than water are added, and after mixing, the pH at 25 ° C. becomes 7.5. After adding an appropriate amount of a pH adjuster (sodium hydroxide) as necessary, distilled water was added so that the total amount was 100% by mass, and the mixture was further stirred to obtain a dishwashing detergent composition. .
The pH of the dishwashing detergent composition (25 ° C.) was adjusted to 25 ° C. using a glass electrode type pH meter (“HM-30G” manufactured by Toa DKK Corporation) The electrode was directly immersed in the dishwashing detergent composition, and the pH indicated after 1 minute was measured. The measuring method was performed according to JIS Z 8802: 1984 “pH measuring method”.

The following evaluation was performed about the obtained cleaning composition for tableware. The results are shown in Table 1.
In addition, the unit of the compounding quantity in Table 1 is mass%, and shows the pure amount conversion amount. Further, the balance amount of water is water whose blending amount is adjusted so that the total amount (overall amount) of the dish detergent composition as the final product is 100% by mass.

<Evaluation of cleaning power>
Sudan IV (manufactured by Kanto Chemical Co., Ltd.) 2 g of beef tallow (manufactured by Wako Pure Chemical Industries, Ltd.) colored so as to have a concentration of 0.5% by mass is a sealed plastic container 10 cm long x 15 cm wide x 5 cm high (Iwasaki Kogyo Co., Ltd., “Neokeeper”) was applied uniformly on the entire inner surface to make a dirt model.
Take 13.8cm in length × 6.0cm in width and 3.5cm in height for a dishwashing sponge (manufactured by Sumitomo 3M Co., Ltd., “Scotch Bright Foamed Yutaka Net Sponge”) with 38g of tap water and 2g of a detergent composition for dishwashing. After squeezing 10 times by hand, the bottom surface inside the sealed container was rubbed 10 times, the side surface 1 time, and the four corners 5 times, and then rinsed with tap water. The inside of the sealed container after rinsing was visually observed, and the cleaning power was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The stain residue of the colored beef tallow is not visually recognized, and there is no null due to the beef tallow residue.
(Double-circle): The stain | pollution | contamination remainder of colored beef tallow is not recognized visually, but there is a slight null with the beef tallow residue.
◯: Slightly residual dirt of colored beef tallow is visually observed, and there is a null due to beef tallow residue.
(Triangle | delta): The stain | pollution | contamination residue of colored beef tallow is recognized visually, and there exists a null with the beef tallow residue.
X: The stain residue of the colored beef tallow is considerably large visually.

<Evaluation of foaming property>
Take 13.8cm in length × 6.0cm in width and 3.5cm in height for a dishwashing sponge (manufactured by Sumitomo 3M Co., Ltd., “Scotch Bright Foamed Yutaka Net Sponge”) with 38g of tap water and 2g of a detergent composition for dishwashing. 10 times by hand and whipped. The foam quality (foam feel) of the foam generated on the dishwashing sponge at this time was visually observed, and foamability was evaluated based on the following evaluation criteria.
A: The texture is very fine, viscous creamy foam, and hardly drops from the sponge.
○: The texture is fine and creamy, and it is difficult to sag from the sponge.
Δ: A fine but fine creamy foam that tends to sag slightly from the sponge.
X: The texture is rough and watery foam spills from the sponge.

<Deodorization evaluation>
(Deodorization evaluation 1: Fish-derived odor)
The saury was dropped into three pieces, the body part was pureed with a food processor, 2 g was spread on a plastic cutting board, and this was used as a test cutting board. Take 13.8cm in length × 6.0cm in width and 3.5cm in height for a dishwashing sponge (manufactured by Sumitomo 3M Co., Ltd., “Scotch Bright Foamed Yutaka Net Sponge”). After squeezing and foaming by hand 5 times, the test cutting board was washed. The odor of the sponge after rinsing with tap water was sensoryly evaluated according to the following five evaluation criteria. The evaluation was performed by calculating an average value of five professional panelists.
5 points: No odor residue.
4 points: I feel a very weak smell, but I can't tell what it is.
3 points: Slightly smell of fish.
2 points: The fish smells clearly.
1 point: Feels the smell of fish intensely.

(Deodorization evaluation 2: Oil + cabbage-derived odor)
2 g of a mixture of cabbage pureed and mixed oil (butter / lard / beef tallow / olive oil dissolved in 3/3/2/1) at a mass ratio of 1: 1 are placed on a plate. This was used as a test dish. Take 13.8cm x 6.0cm x 3.5cm height of a dishwashing sponge (Sumitomo 3M Co., Ltd., "Scotch Bright Foamed Yutaka Net Sponge") and take 38g of tap water and 3g of a dishwashing detergent composition. After foaming by hand 5 times, 5 test dishes were washed successively. The washed sponge was put in a plastic bag with a chuck and sealed, and then left at 35 ° C. After 8 hours, the odor of the sponge was sensoryly evaluated according to the following five-level evaluation criteria. The evaluation was performed by calculating an average value of five professional panelists. In addition, “Snow Brand Hokkaido Butter” manufactured by Snow Brand Megmilk Co., Ltd. is used as butter, Wako Pure Chemical Industries Co., Ltd. is used as beef tallow, and “OLIVE OIL EXTRA VIRGIN” manufactured by Ajinomoto Co. is used as olive oil. Using.
5 points: No odor residue.
4 points: I feel a very weak smell, but I can't tell what it is.
3 points: Slightly smell of ingredients.
2 points: The smell of ingredients is clearly felt.
1 point: The smell of food is felt intensely.

"Examples 2-31, Comparative Examples 1-7"
Except having changed the compounding quantity of each component as shown in Tables 1-4, the detergent composition for tableware of each example was prepared like Example 1, and various evaluation was performed. The results are shown in Tables 1-4.

In Tables 1 to 4, “(A) + (C) content” is the total content (% by mass) of component (A) and component (C) in 100% by mass of the dishwashing detergent composition. is there. The “(E) / (D) mass ratio” is a ratio (mass ratio) between the content of the (E) component and the content of the metal ion in the (D) component. “(A) / (C) Mass ratio” is a ratio (mass ratio) between the content of the component (A) and the content of the component (C). The “(C) / ((D) + (E)) mass ratio” is the ratio (mass of the content of the (C) component and the sum of the content of the metal ion and the (E) component in the (D) component. Ratio).
For Comparative Example 7, “(A) + (C) content”, “(A) / (C) mass ratio”, and “(C) / ((D) + (E)) mass ratio” In determining the value, the content of the component (C ′) was used instead of the content of the component (C).

  As is apparent from Tables 1 to 3, the dishwashing detergent composition obtained in each example was excellent in cleaning power against oil stains, foaming properties, and deodorizing effect. From these results, it was shown that the dishwashing composition of the present invention can prevent the odor of food ingredients from remaining on the sponge by performing daily dishwashing.

On the other hand, as apparent from Table 4, the dishwashing detergent composition of Comparative Example 1 having a mass ratio represented by (A) component / (C) component of 2.5 is a deodorant for fish-derived odors. It was inferior in effect. Moreover, it was inferior to foaming property.
(A) The detergent composition for tableware of the comparative example 2 whose mass ratio represented by a component / (C) component is 27.7 is with respect to foodstuff smell (a fish-derived odor, and oil + cabbage-derived odor). It was inferior in the deodorizing effect.
(A) The cleaning composition for tableware of the comparative example 3 which does not contain a component was inferior in the deodorizing effect with respect to foodstuff odor. Moreover, it was inferior to the cleaning power.
The detergent composition for tableware of the comparative example 4 which does not contain (B) component was inferior in the deodorizing effect with respect to foodstuff odor. Moreover, it was inferior also in the detergency and foaming property.
The dishwashing detergent composition of Comparative Example 5 containing no component (C) was inferior in the deodorizing effect on the food odor.
The detergent composition for tableware of the comparative example 6 which does not contain (D) component was inferior in the deodorizing effect with respect to foodstuff odor.
The detergent composition for tableware of the comparative example 7 which used dodecyl alcohol instead of (C) component was inferior in the deodorizing effect with respect to foodstuff odor.

Claims (3)

(A) component: at least one selected from a semipolar surfactant, an amphoteric surfactant, and a cationic surfactant;
(B) component: surfactant other than (A) component,
(C) component: an alcohol component containing a monohydric alcohol having a branched hydrocarbon group;
(D) component: containing at least one selected from zinc, copper, manganese, nickel, cobalt, and iron,
The detergent composition for tableware whose mass ratio represented by (A) component / (C) component is 4.1-20.   (E) component: It further contains a metal ion sequestering agent, and the mass ratio represented by (C) component / (metal ion in (D) component + (E) component) is 1.6 to 10. Item 2. A cleaning composition for tableware according to Item 1.   (E) The cleaning composition for tableware of Claim 2 whose component is an aminocarboxylic acid type sequestering agent.