JP7285770B2 - dishwashing detergent - Google Patents

Description

The present invention relates to dishwashing detergents.

2. Description of the Related Art Washing of dishes and the like is usually performed while scrubbing the dishes and the like with a sponge to which a dishwashing agent is added.
By the way, when washing colored oil stains such as curry and meat sauce, solid fat containing pigment tends to remain on the sponge. In particular, solid fat on plastic containers such as lunch boxes tends to remain on sponges. In such a case, in addition to washing the tableware, etc., it takes time and effort to wash the sponge. Therefore, dishwashing detergents are required to sufficiently remove oil stains and to prevent solid fat from remaining on sponges after dishwashing.

As a cleaning agent capable of sufficiently cleaning highly denatured oil stains, Patent Document 1 discloses a cleaning composition for hard surfaces containing a specific acetal derivative, a surfactant, a builder and water.
In addition, Patent Document 2 discloses a detergent composition containing a specific 1,3-dioxolane-2-one derivative as a detergent that exerts excellent detergency against various stains.

JP-A-8-3590 JP-A-2001-49293

However, the cleaning method using the cleaning composition described in Patent Document 1 and Patent Document 2 involves immersing a soiled article in the undiluted solution of the cleaning composition, or dripping the undiluted solution of the cleaning composition onto the stain. This is a method of washing dirt by rubbing it with a sponge, like washing dishes. put away.
An object of the present invention is to provide a dishwashing detergent that hardly leaves stains on a sponge in a washing method in which it is used after being diluted with water when washing dishes.

The present invention has the following aspects.
[1] (A) component: an anionic surfactant,
(B) component: a compound represented by the following general formula (B-1);
(C) component: an amine oxide surfactant represented by the following general formula (C-1);
(D) component: containing a monohydric alcohol having 2 to 4 carbon atoms,
The content of the component (C) is 1.0% by mass or more, and the content of the component (D) is 0.1 to 1.5% by mass, relative to the total mass of the dishwashing detergent,
The mass ratio represented by the (A) component/the (C) component is 0.5 to 2.0,
A dishwashing detergent, wherein the mass ratio represented by component (B)/component (D) is 1.5 to 15.

In general formula (B-1), R ² is a linear or branched alkyl group having 1 to 14 carbon atoms, a linear or branched alkenyl group having 1 to 14 carbon atoms, or a linear chain having 1 to 14 carbon atoms. or a branched hydroxyalkyl group or hydrogen, and R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched alkenyl group having 1 to 5 carbon atoms. is a group or hydrogen.

In general formula (C-1), R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, and B is -CONH-, -NHCO-, - is COO-, -OCO- or -O-, and r is a number of 0 or 1;

[2] The dishwashing detergent of [1], wherein the mass ratio of component (A)/component (B) is from 1.0 to 5.0.
[3] The dishwashing detergent according to [1] or [2], wherein the mass ratio of component (A)/component (D) is 5.0 to 17.
[4] The mass ratio represented by (the (A) component + the (C) component)/(the (B) component + the (D) component) is 1.5 to 6.0 [1] The dishwashing detergent according to any one of ~[3].
[5] Component (A) is a polyoxyalkylene alkyl ether sulfate ester or its salt, a linear alkylbenzene sulfonic acid or its salt, an alkyl group-containing alkanesulfonic acid or its salt, an α-olefin sulfonate, or an internal olefin. The dishwashing detergent of any one of [1] to [4], containing one or more selected from sulfonates.
[6] The dishwashing detergent according to any one of [1] to [5], wherein the total amount of surfactant is 10 to 30% by mass relative to the total mass of the dishwashing detergent.
[7] Any one of [1] to [6], wherein the mass ratio represented by the total amount of surfactant / (above component (B) + component (D)) is 1.5 to 6.0 Dishwasher.
[8] Any one of [1] to [7], wherein the total content of the component (A) and the component (B) is 10 to 30% by mass relative to the total mass of the dishwashing detergent. dishwashing detergent.

According to the present invention, it is possible to provide a dishwashing detergent that does not easily leave stains on a sponge in a washing method in which it is used after being diluted with water when washing dishes.

FIG. 1(a) is a photograph showing an example of an evaluation of "I" in the evaluation of residual dirt on a sponge, and FIG. 1(b) is a photograph showing an example of an evaluation of "II". FIG. 1(c) is a photograph showing an example when the evaluation is "III".

The present invention will be described in detail below.
The dishwashing detergent of the present invention is a composition containing the following components (A), (B), (C) and (D). The dishwashing detergent may further contain optional components other than the (A) component, (B) component, (C) component and (D) component as needed.

<(A) Component>
(A) Component is an anionic surfactant.
The anionic surfactant may be any anionic surfactant conventionally used in liquid detergents for dishwashing and the like. salts thereof, polyoxyalkylene alkyl ether sulfate esters or salts thereof, polyoxyalkylene alkenyl ether sulfate esters or salts thereof, alkanesulfonic acids having alkyl groups or salts thereof, α-sulfo fatty acid esters or salts thereof, alkyl sulfosuccinates or salts thereof, α-olefin sulfonates, internal olefin sulfonates, and the like;
Salt forms of the anionic surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; alkanolamine salts such as monoethanolammonium, diethanolammonium and triethanolamine. .
The (A) component is preferably a non-soap anionic surfactant from the viewpoint of increasing detergency.

As the straight-chain alkylbenzenesulfonic acid or its salt, a straight-chain alkylbenzenesulfonic acid having a straight-chain alkyl group having 8 to 16 carbon atoms or a salt thereof is preferable, and a straight-chain alkylbenzenesulfonic acid having a straight-chain alkyl group having 10-14 carbon atoms. or salts thereof are particularly preferred.
As the linear or branched alkyl sulfate or its salt, an alkyl sulfate having 10 to 20 carbon atoms or its salt is preferable.

Examples of polyoxyalkylene alkyl ether sulfate esters or salts thereof include compounds represented by the following general formula (A-1).
R ¹ -O-[(PO) _p /(EO) _q ]-SO ₃ ^- 1/X M ⁺ (A-1)
(In general formula (A-1), R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is a primary carbon atom. PO represents an oxypropylene group, EO represents an oxyethylene group, p represents the average number of repetitions of PO, a number satisfying 0 ≤ p < 1, q represents the average number of repetitions of EO, 0 < q A number that satisfies ≦4, M ⁺ is a cation other than a hydrogen ion, and X is the valence of M ⁺ .)

In general formula (A-1), R ¹ has 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms. R ¹ is preferably an alkyl group derived from a fats and oils raw material from the standpoints of detergency and environment. Suitable oil and fat raw materials include palm kernel oil, coconut oil, and the like.

The average repeating number of PO (that is, the average number of added moles of propylene oxide) is 0 or more and less than 1, preferably 0.
The average repeating number of EO (that is, the average number of added moles of ethylene oxide) is more than 0 and 4 or less, preferably 1-3.
When p is greater than 0, in (PO) _p /(EO) _q , EO and PO may be added randomly or in blocks, regardless of the arrangement state.

In general formula (A-1), M ⁺ is a cation other than a hydrogen ion and has a valence of X. M ⁺ includes those capable of forming water-soluble salts, such as alkali metals, alkaline earth metals, ammonium or alkanolamines.
Alkali metals include sodium, potassium and the like.
Alkaline earth metals include calcium, magnesium and the like.
Alkanolamine includes monoethanolamine, diethanolamine, triethanolamine and the like.

Examples of compounds represented by the general formula (A-1) include polyoxyethylene (1) linear alkyl (C12) ether sulfate sodium salt and polyoxyethylene (2) linear alkyl (C12) ether sulfate sodium salt. salt, polyoxyethylene (4) linear alkyl (C12) ether sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) ether sulfate sodium salt, polyoxy Ethylene (1) linear alkyl (C12/14 = 75/25; derived from natural fat) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12/14 = 75/25; derived from natural fat) ether sulfate Ester sodium salt, polyoxyethylene (4) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) ether sulfate ester sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear chain Alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate ester sodium salt and the like.

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 oils and fats" means a mixture of a straight-chain alkyl group with 12 carbon atoms and a straight-chain alkyl group with 14 carbon atoms (mixing ratio: mass ratio 75/25), which means that it is a linear alkyl group derived from natural fats and oils.

The polyoxyalkylene alkenyl ether sulfate ester or salt thereof has a linear or branched alkenyl group having 8 to 18 carbon atoms, and has an average of 1 to 10 mol of an oxyethylene group (EO) added, and an average Those to which 0 to 6 moles of oxypropylene group (PO) are added (ie, polyoxyethylene (propylene) alkenyl ether sulfate) are preferred.
Alkanesulfonic acids having an alkyl group or salts thereof include alkanesulfonic acids having 10 to 20 carbon atoms or salts thereof, preferably alkanesulfonic acids having 14 to 17 carbon atoms or salts thereof, and secondary alkanesulfonic acids. or salts thereof are particularly preferred.
As α-sulfo fatty acid esters or salts thereof, α-sulfo fatty acid ester salts having 10 to 20 carbon atoms are preferred.
As the α-olefin sulfonate, an α-olefin sulfonate having 10 to 20 carbon atoms is preferable. The α-olefin sulfonate is a surfactant obtained by sulfonating an olefin having a carbon-carbon double bond at the α-position, neutralizing it with an alkali such as sodium hydroxide, and hydrolyzing it.
As the internal olefin sulfonate, an internal olefin sulfonate having 8 to 24 carbon atoms is preferable, and examples thereof include the internal olefin sulfonate described in JP-A-2003-81935. Internal olefin sulfonate is a surfactant obtained by sulfonating an olefin with a carbon-carbon double bond at the 2nd or higher position (internal), neutralizing it with an alkali such as sodium hydroxide, and hydrolyzing it. be.

These anionic surfactants are readily available on the market. Moreover, you may use what was synthesize|combined by the well-known method.
Among these, from the viewpoint that the effects of the present invention are particularly easy to obtain, the component (A) includes polyoxyalkylene alkyl ether sulfate esters or salts thereof, linear alkylbenzene sulfonic acids or salts thereof, and alkanesulfonic acids having an alkyl group. or salts thereof, α-olefin sulfonates, and internal olefin sulfonates are preferred, and polyoxyalkylene alkyl ether sulfate esters or salts thereof, linear alkylbenzene sulfonic acids or salts thereof, alkanesulfonic acids having alkyl groups or salts thereof More preferably, polyoxyethylene (1) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) ether sulfate ester sodium salt, linear alkyl (C12) benzenesulfonate, alkanesulfonate having an alkyl group is more preferred. In particular, it is preferable to combine polyoxyethylene (1) linear alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate sodium salt and linear alkyl (C12) benzenesulfonate.
Component (A) may be used singly or in combination of two or more.

<(B) Component>
Component (B) is a compound represented by the following general formula (B-1) (hereinafter also referred to as a “dioxolane compound”).

In general formula (B-1), R ² is a linear or branched alkyl group having 1 to 14 carbon atoms, a linear or branched alkenyl group having 1 to 14 carbon atoms, or a linear chain having 1 to 14 carbon atoms. or a branched hydroxyalkyl group or hydrogen, and R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched alkenyl group having 1 to 5 carbon atoms. is a group or hydrogen.

In general formula (B-1), R ² is preferably a linear or branched hydroxyalkyl group having 1 to 14 carbon atoms, more preferably a linear primary hydroxyalkyl group having 1 to 14 carbon atoms. A linear primary hydroxyalkyl group having 1 to 7 carbon atoms is more preferred, and a linear primary hydroxyalkyl group having 1 to 3 carbon atoms is particularly preferred.
In general formula (B-1), each of R ³ and R ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyl group having 1 to 4 carbon atoms. groups are more preferred.

Component (B) includes, for example, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4- Methanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, 2,2-dimethyl-1,3-dioxolane-4-ethanol, 2,2-dimethyl-1,3-dioxolane-4- Propanol, 2,2-dimethyl-1,3-dioxolane-4-butanol, 2,2-dimethyl-1,3-dioxolane-4-pentanol, 2,2-dimethyl-1,3-dioxolane-4-hexanol , 2,2-dimethyl-1,3-dioxolane-4-heptanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-propanol, 2-isobutyl-2-methyl-1,3-dioxolane-4 -butanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-pentanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-hexanol, 2-isobutyl-2-methyl-1, 3-dioxolane-4-heptanol and the like.
Among these, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol and 2,2-dimethyl-1,3-dioxolane-4-methanol are preferred from the viewpoint that the effects of the present invention are particularly easily obtained. preferable.
(B) component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

<(C) Component>
Component (C) is an amine oxide surfactant represented by the following general formula (C-1).

In general formula (C-1), R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, and B is -CONH-, -NHCO-, - is COO-, -OCO- or -O-, and r is a number of 0 or 1;

In general formula (C-1), R ⁵ has 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms. R ⁵ is preferably a linear or branched alkyl group having 8 to 18 carbon atoms.
In general formula (C-1), each of R ⁶ and R ⁷ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and more preferably both R ⁶ and R ⁷ are a methyl group. preferable.
In general formula (C-1), B is preferably -CONH-.
In general formula (C-1), r is a number of 0 or 1, preferably 0.

Specific examples of component (C) include alkyldimethylamine oxides such as lauryldimethylamine oxide (n-dodecyldimethylamine oxide), palm alkyldimethylamine oxide, and lauryldiethylamine oxide; alkanoylamides such as lauramidopropyldimethylamine oxide; Alkyldimethylamine oxide and the like can be mentioned. Among these, alkyldimethylamine oxide is preferable, and lauryldimethylamine oxide is more preferable because of its excellent detergency against oil stains.
Component (C) may be used singly or in combination of two or more.

<(D) Component>
Component (D) is a monohydric alcohol having 2 to 4 carbon atoms.
Component (D) includes, for example, ethanol, n-propanol, isopropanol, normal butanol, secondary butanol, and tertiary butanol. Among these, ethanol is preferable from the viewpoint of being particularly excellent in the effect of suppressing solid fat from remaining on the sponge.
Component (D) may be used alone or in combination of two or more.

<Optional component>
The dishwashing detergent may contain optional components other than the components described above, if necessary, as long as the effects of the present invention are not impaired.
Examples of optional components include components used in detergent compositions for washing dishes, kitchens, hard surfaces, clothes, etc. Specific examples include solvents, components other than components (A) and (C). surfactants (other surfactants), hydrotropic agents other than component (D), preservatives, inorganic builders, pH adjusters, bleaching components, metal trapping components, radical trapping agents, fragrances, enzymes, pigments, etc. mentioned.

Water is preferred as the solvent. Using water as a solvent facilitates preparation of the dishwashing detergent. In addition, better solubility in water is obtained when using dishwashing detergents.
As water, ion-exchanged water, distilled water, tap water, or the like can be used.

Other surfactants include nonionic surfactants, cationic surfactants, amphoteric surfactants and the like.
Examples of nonionic surfactants (excluding component (C)) include polyoxyalkylene alkyl ethers and alkyl polyglycosides. Nonionic surfactants may be used singly or in combination of two or more.
Cationic surfactants include, for example, didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyldihydroxyethylammonium chloride, ditallowalkyldimethylammonium chloride, di(stearoyloxy ethyl)dimethylammonium chloride, di(oleoyloxyethyl)dimethylammonium chloride, di(palmitoyloxyethyl)dimethylammonium methosulfate, di(stearoyloxyisopropyl)dimethylammonium chloride, di(oleoyloxyisopropyl)dimethylammonium chloride, di (oleoyloxybutyl)dimethylammonium chloride, di(stearoyloxyethyl)methylhydroxyethylammonium methosulfate, tri(stearoyloxyethyl)methylmethosulfate and the like. The "beef tallow alkyl" group has 14 to 18 carbon atoms. Cationic surfactants may be used singly or in combination of two or more.
Amphoteric surfactants (excluding component (C)) include, for example, carboxylate type (also referred to as betaine type), sulfate type, sulfonate type, and phosphate type. can be used. Among these, the carboxylate type is preferred.
Specific examples of carboxylate-type amphoteric surfactants include betaine lauryldimethylaminoacetate, betaine coconut alkyldimethylaminoacetate, betaine coconut fatty acid amidopropyl betaine, betaine lauramidopropyldimethylaminoacetate, and betaine coconut alkylamidopropyldimethylamino acetate. and betaine acetate. Amphoteric surfactants may be used singly or in combination of two or more.

By including a hydrotrope agent other than the component (D) in the dishwashing detergent, mainly the storage stability (particularly low-temperature stability) of the dishwashing detergent is improved, making it easier to stably ensure a transparent appearance. .
Examples of hydrotropic agents (excluding component (D)) include toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, cumenesulfonate, benzoic acid, and benzoate. Toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, and cumenesulfonate may be any of the o-, m-, and p-isomers. body is preferred. Preferred hydrotropic agents are p-toluenesulfonic acid, p-toluenesulfonate, benzoic acid, and benzoates.
One type of hydrotrope agent may be used alone, or two or more types may be used in appropriate combination.

By including a preservative in the dishwashing detergent, even if microorganisms or the like are mixed in the dishwashing detergent, the growth of bacteria can be suppressed.
Examples of antiseptics include isothiazoline compounds, and specific examples include benzisothiazolinone (1,2-benzisothiazolin-3-one), methylisothiazolinone (2-methyl-4-isothiazolin-3- on), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, and the like. Among these, 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred.
The preservatives may be used singly or in combination of two or more.

Examples of inorganic builders include magnesium sulfate, sodium sulfate, zinc sulfate and zinc oxide. Among these, zinc oxide and zinc sulfate are preferable because zinc salts have the effect of improving the sterilizing power.
An inorganic builder may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

Examples of pH adjusters include inorganic alkaline agents and organic alkaline agents.
Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Among these, hydroxides such as sodium hydroxide and potassium hydroxide are preferable because they tend to improve the storage stability of dishwashing detergents.
Examples of organic alkaline agents include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, N - Amine compounds such as ethylmorpholine. Among these, monoethanolamine is preferred because it tends to improve the storage stability of the dishwashing detergent.
When the pH of the dishwashing detergent is too high, inorganic acids such as hydrochloric acid, sulfuric acid and sulfamic acid; and acids such as carboxylic acids such as acetic acid and citric acid may be used as pH adjusters.

Examples of enzymes include protease, amylase, cellulase, pectinase, mannanase, catalase, and the like.
Enzymes are generally commercially available as formulations containing enzymes (enzyme formulations). When preparing dishwashing detergents, enzymes are usually incorporated in the form of enzyme preparations.
The protease is preferably a protease having serine, histidine, and aspartic acid in its molecule, such as serine protease.
Examples of protease-containing preparations (protease preparations) include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, and Alcalase 2.5L available from Novozymes. Alcalase Ultra 2. 5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Coronase Evity 48L, Progress Uno 101L; available from Genencor under the trade names Purafect L, Purafect OX, Prop erase L and the like.
Amylase-containing preparations (amylase preparations) include, for example, Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L and Amplify Prime available from Novozymes; xamyl; Amano Enzyme Pullulanase Amano (trade name) available from Seikagaku Corporation; DB-250 (trade name) available from Seikagaku Corporation;
When the dishwashing detergent contains at least one of protease and amylase, it is preferable to use catalase together for the purpose of enhancing its stability. Thereby, residual hydrogen peroxide derived from the component (C) can be decomposed.

<Content>
The content of component (A) is preferably 30% by mass or less, more preferably 5.0 to 30% by mass, and even more preferably 7.0 to 20% by mass, relative to the total mass of the dishwashing detergent. If the content of component (A) is within the above range, the effect of suppressing solid fat from remaining on the sponge can be easily obtained.

The content of component (B) is preferably 0.15 to 22.5% by mass, more preferably 2.5 to 10% by mass, more preferably 2.5 to 7.0% by mass, relative to the total mass of the dishwashing detergent. % is more preferred, and 4.0 to 6.0% by mass is particularly preferred. If the content of component (B) is within the above range, dirt such as solid fat is prevented from remaining on the sponge.

The total content of components (A) and (B) is preferably 10 to 30% by mass relative to the total mass of the dishwashing detergent. When the total content of components (A) and (B) is within the above range, the effect of suppressing solid fat from remaining on the sponge is likely to be obtained.

The content of component (C) is 1.0% by mass or more, preferably 2.0 to 15% by mass, more preferably 6.0 to 12% by mass, relative to the total mass of the dishwashing detergent. When the content of component (C) is within the above range, dirt such as solid fat is prevented from remaining on the sponge.

The content of component (D) is 0.1 to 1.5% by mass, preferably 0.6 to 1.2% by mass, relative to the total mass of the dishwashing detergent. When the content of component (D) is within the above range, dirt such as solid fat is prevented from remaining on the sponge.
Component (D) is thought to improve the solubility of solid fats through a synergistic effect with component (B). Difficult to dissolve solid fat. In addition to the adsorption of the component (B) on the solid fat, the adsorption of the component (D) improves the solubility of the solid fat and suppresses its residue on the sponge. Therefore, if the content of the component (D) is less than the above lower limit, the amount of the component (D) is small, and the component (D) cannot be sufficiently adsorbed to the solid fat, making it difficult to improve the solubility of the solid fat. It is thought that fat tends to remain on the sponge. If the content of the component (D) exceeds the above upper limit, the adsorption of the component (B) to the solid fat is hindered by the component (D), the solubility of the solid fat is difficult to improve, and the solid fat remains on the sponge. It is thought that it becomes easier.

The total content of all surfactants contained in the dishwashing detergent (hereinafter also referred to as "total amount of surfactants") is preferably 10 to 30% by mass relative to the total mass of the dishwashing detergent. , 15 to 25 mass % is more preferable. If the total amount of the surfactant is at least the above lower limit, it becomes easier to obtain the effect of suppressing solid fat from remaining on the sponge while exhibiting high detergency. If the total amount of the surfactant is not more than the above upper limit, the surfactant can suppress the incorporation of the components (B) and (D) into the micelles, so the solid fats of the components (B) and (D) can be suppressed. Adsorption to is less likely to be inhibited. Therefore, it becomes easy to obtain the effect of improving the solubility of the solid fat by the (B) component and the (D) component.

When the dishwashing detergent contains water, the water content is preferably 85% by mass or less, more preferably 40 to 85% by mass, and even more preferably 45 to 80% by mass, relative to the total mass of the dishwashing detergent. . If the water content is at least the above lower limit, gelation is suppressed, and the uniformity of the liquid can be further improved. If the content of water is equal to or less than the above upper limit, the content of each component can be ensured, the viscosity does not become too low, and the composition is easier to use.

When the dishwashing detergent contains a hydrotrope agent other than the component (D), the content of the hydrotrope agent other than the component (D) is 2.0 to 30% by mass with respect to the total mass of the dishwashing detergent. Preferably, 3.0 to 10% by mass is more preferable. As long as the content of the hydrotrope agent is within the above range, the effects of the hydrotrope agent can be sufficiently obtained without interfering with the effects of the present invention.

When the dishwashing detergent contains a preservative, the content of the preservative is preferably 0.0002 to 0.01% by mass (2 to 100 ppm by mass) relative to the total mass of the dishwashing detergent, and is 0.0005. ~0.004% by mass (5 to 40 ppm by mass) is more preferred. If the content of the preservative is within the above range, the effects of the preservative can be sufficiently obtained without interfering with the effects of the present invention.

When the dishwashing detergent contains an inorganic builder, the content of the inorganic builder is preferably 0.05 to 5% by mass relative to the total mass of the dishwashing detergent.
In addition, the sum total of content of all the components contained in the detergent for tableware shall be 100 mass %.

<mass ratio>
The mass ratio represented by (A) component / (C) component (hereinafter also referred to as “A / C ratio”) is 0.5 to 2.0, preferably 0.5 to 1.5, and 0 .9 to 1.4 are more preferred. If the A/C ratio is within the above range, dirt such as solid fat is suppressed from remaining on the sponge.

The mass ratio represented by component (B)/component (D) (hereinafter also referred to as “B/D ratio”) is 1.5 to 15, preferably 2.0 to 8.0, and 3.0. ~6.0 is more preferred. If the B/D ratio is within the above range, dirt such as solid fat is suppressed from remaining on the sponge.
If the B / D ratio is less than the above lower limit, the component (D) is excessive relative to the component (B), the adsorption of the component (B) to the solid fat is hindered by the component (D), and the solid fat It is thought that the solubility is difficult to improve, and the solid fat tends to remain in the sponge. If the B/D ratio exceeds the above upper limit, the component (B) is excessive relative to the component (D), and the component (D) cannot be sufficiently adsorbed to the solid fat, making it difficult to improve the solubility of the solid fat. , it is thought that the solid fat tends to remain on the sponge.

The mass ratio represented by (A) component/(B) component (hereinafter also referred to as "A/B ratio") is preferably 1.0 to 5.0, more preferably 1.4 to 4.0, 2.0 to 3.0 is more preferable. If the A/B ratio is within the above range, the effect of suppressing the solid fat from remaining on the sponge is likely to be obtained.

The mass ratio represented by component (A)/component (D) (hereinafter also referred to as “A/D ratio”) is preferably 5.0-17, more preferably 8.0-14. If the A/D ratio is within the above range, the effect of suppressing the solid fat from remaining on the sponge is likely to be obtained.

The mass ratio represented by ((A) component + (C) component) / ((B) component + (D) component) (hereinafter also referred to as “(A + C) / (B + D) ratio”) is 1.5. ~6.0 is preferable, and 2.0 to 5.0 is more preferable. When the (A+C)/(B+D) ratio is within the above range, the effect of suppressing the solid fat from remaining on the sponge is likely to be obtained.

The mass ratio represented by the total amount of surfactant/((B) component + (D) component) (hereinafter also referred to as "total amount of surfactant/(B+D) ratio") is 1.5 to 6.0. is preferred, and 2.0 to 5.0 is more preferred. If the total amount of surfactant/(B+D) ratio is within the above range, the effect of suppressing the solid fat from remaining on the sponge is likely to be obtained.

<Manufacturing method>
The dishwashing detergent is prepared by, for example, adding the above-described components (A), (B), (C) and (D), and optionally optional components other than the solvent and the pH adjuster to the solvent. It can be produced by mixing and, if necessary, adjusting the pH to an arbitrary value using a pH adjuster.

<pH>
The pH of the dishwashing detergent at 25°C is preferably 6-8. If the pH of the dishwashing detergent at 25°C is within the above range, the hydrolysis of the component (B) can be suppressed, and the penetration detergency increases.
In the present invention, the pH (25°C) of the dishwashing detergent indicates a value measured by a method conforming to JIS Z 8802:1984 "pH measurement method".
The pH of the dishwashing detergent may be adjusted using the pH adjuster described above.

<How to use>
The method of using the dishwashing detergent, that is, the method of washing dishes is described below.
Methods for washing dishes include a method in which an arbitrary amount of dishwashing detergent is attached to a cleaning tool, and the cleaning tool is used to scrub the object to be cleaned (scrubbing operation); the dishwashing detergent is dispersed in water. (immersion operation) method (immersion method) in which the object to be washed is immersed in the washing liquid for an arbitrary time (immersion time). In the immersion operation, if necessary, the object to be cleaned may be scrubbed with a cleaning tool in the cleaning liquid.
After the scrubbing operation or the immersion operation, the object to be washed is rinsed with rinsing water to wash away the dishwashing detergent adhering to the object to be washed (rinsing operation). The washed tableware is obtained through the rinsing operation.
Objects to be washed include tableware such as plates, chopsticks, and spoons. Also, objects to be cleaned may be kitchen utensils such as cooking utensils such as pots, knives, and cutting boards. In the present invention, tableware and cooking utensils are generally referred to as "tableware."

<Effect>
In the dishwashing detergent of the present invention described above, since the component (A) and the components (B), (C) and (D) in specific amounts are contained in a specific ratio, high detergency can be achieved. While exhibiting the above, stains are less likely to remain on the sponge in a washing method in which the sponge is used after being diluted with water for washing dishes.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, unless otherwise specified, the compounding amount of the components used in each example is a pure content conversion value.

"Raw materials used"
(A) The compound shown below was used as a component.
A-1: sodium polyoxyethylene alkyl ether sulfate (AES), in the above general formula (A-1), R ¹ = linear alkyl group having 12 to 14 carbon atoms, p = 0, q = 1, M ⁺ = sodium, synthesized by the synthesis method below.
A-2: Sodium alkylbenzene sulfonate (LAS) having 10 to 14 carbon atoms, trade name "Taika Power L121" manufactured by Tayka Co., Ltd., neutralized with sodium hydroxide.
A-3: Sodium secondary alkanesulfonate (SAS) having 14 to 17 carbon atoms (manufactured by Clariant Japan Co., Ltd., trade name "HOSTAPUR SAS 30A").
A-4: Sodium α-olefin sulfonate (AOS) having 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Liporan LB-440”).
A-5: Inner olefin sulfonate synthesized by the method described in Example 4 of JP-A-2003-81935 (the total ratio of carbon-carbon double bonds present at the 2-position is 86%, cis The isomer/trans isomer ratio is 49/51, contains 6.3% by mass of paraffin components, has 16 or less carbon atoms: 1% by mass, 14% by mass of 17 carbon atoms, 35% by mass of 18 carbon atoms, and 19 carbon atoms Sodium internal olefin sulfonate ( IOS)).

(Synthesis method of A-1)
In a 4 L autoclave, 400 g of P&G's product name "CO1270 alcohol (C12/C14 = 75%/25%, mass ratio)" as raw material alcohol and 0.8 g of potassium hydroxide as a reaction catalyst were charged, and the autoclave was After purging the inside with nitrogen, the temperature was raised while 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. The average number of added moles of ethylene oxide in the obtained polyoxyalkylene ether was 1.
Next, 237 g of ethylene oxide of the polyoxyalkylene ether thus obtained was placed in a 500 mL flask equipped with a stirrer and purged with nitrogen. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid.
Next, A-1 was obtained by neutralizing the resulting polyoxyethylene alkyl ether sulfuric acid with an aqueous sodium hydroxide solution.

(B) The compound shown below was used as a component.
· B-1: 2,2-dimethyl-1,3-dioxolane-4-methanol, in the above general formula (B-1), R ² = hydroxymethyl group, R ³ = methyl group, R ⁴ = methyl group ( Rhodia Poliamida e Especialidades Ltd., trade name "Augeo Clean Multi").
B-2: 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, in the above general formula (B-1), R ² = hydroxymethyl group, R ³ = isobutyl group, R ⁴ = methyl Group (manufactured by Rhodia Poliamida e Especialidades Ltd., trade name "Augeo Clean Plus").

As the component (C), the compounds shown below were used.
C-1: lauryl dimethylamine oxide (AX), in the above general formula (C-1), R ⁵ = linear alkyl group having 12 carbon atoms, R ⁶ = methyl group, R ⁷ = methyl group, r = 0 (manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Cadenax DM12D-W”).
C-2: lauramidopropyl dimethylamine oxide (APAX), in the above general formula (C-1), R ⁵ = linear alkyl group having 11 carbon atoms, R ⁶ = methyl group, R ⁷ = methyl group, B = -CONH-, R ⁸ = propyl group, r = 1 (manufactured by Clariant Japan Co., Ltd., trade name "GENAMINOX AP").

The compounds shown below were used as the component (D) or its substitute (component (D')).
· D-1: Ethanol (manufactured by Kanto Chemical Co., Ltd.).
· D'-1: butyl carbitol (manufactured by Nippon Nyukazai Co., Ltd.).
- D'-2: Propylene glycol (manufactured by Dow Chemical Company, trade name "propylene glycol").

The compounds shown below were used as optional components.
· pTS-H: p-toluenesulfonic acid (manufactured by Kanto Kagaku Co., Ltd.).
- Sodium benzoate: Sodium benzoate (manufactured by Kanto Kagaku Co., Ltd.).
MIT: 2-methyl-4-isothiazolin-3-one (manufactured by Rohm and Haas Japan Co., Ltd., trade name "Neoron M-10").
· BIT: 1,2-benzisothiazolin-3-one (manufactured by Arch Chemicals, trade name "PROXEL XL2").
- Citric acid: (manufactured by Fuso Chemical Co., Ltd., trade name "citric acid (anhydrous)").
- Zinc oxide: (manufactured by Mitsui Kinzoku Mining Co., Ltd.).
- Sulfamic acid: (manufactured by Fuso Chemical Industry Co., Ltd.).
Perfume: A 1:1 (mass ratio) mixture of the perfume composition A and the perfume composition B described in Tables 1 to 6 of Japanese Patent Application No. 2017-085282.

"Examples 1 to 25, Comparative Examples 1 to 11"
<Preparation of dishwashing detergent>
1000 g of dishwashing detergents having formulations shown in Tables 1 to 7 were prepared by the following procedure.
Put the (A) component, (B) component, (D) component or (D') component, pTS-H, Na benzoate, and citric acid in a 1 L beaker, and stir with a magnetic stirrer (manufactured by Fine). , trade name “F-606N”). Subsequently, component (C) and the remaining optional components (excluding water) are added and sufficiently stirred, and if necessary, a pH adjuster (water After adding an appropriate amount of sodium oxide, sulfuric acid), water (ion-exchanged water) was added so that the total amount was 100% by mass, and the mixture was stirred well to obtain a dishwashing detergent. Zinc oxide and sulfamic acid were added after mixing and dissolving both components in an appropriate amount of water in advance.
Adjust the temperature of the dishwashing detergent to 25 ° C., use a glass electrode pH meter (manufactured by Toa DKK Co., Ltd., trade name "HM-30G"), and immerse the glass electrode directly in the dishwashing detergent for 1 minute. The pH indicated after the passage of time was measured. The measurement method was performed in accordance with JIS Z 8802:1984 "pH measurement method". The results are shown in Tables 1-7.
For each example of the dishwashing detergent obtained, the amount of dirt remaining on the sponge was evaluated as follows. The results are shown in Tables 1-7.

<Evaluation>
(Evaluation of dirt remaining on sponge)
Sudan IV (manufactured by Kanto Chemical Co., Ltd.) 1 g of beef tallow (Fuji Film Wako Pure Chemical Industries, Ltd.) colored to a concentration of 1% by weight is placed in a plastic container (12 cm long × 17 cm wide × 5 cm high) (Iwasaki Industry Co., Ltd.) Company product, product name “Neo Keeper”) was uniformly applied to the entire inner surface of the product to make a dirt model. Next, take 38g of tap water and 2g of dishwashing detergent on a dishwashing sponge (manufactured by 3M Japan Co., Ltd., trade name "Scotch Bright") measuring 11cm long x 7cm wide x 3cm high, and knead it by hand 10 times. , the bottom of the dirt model was rubbed 10 times, the side was rubbed 10 times, and the four corners were rubbed 5 times each. After that, the sponge surface was thoroughly rinsed with tap water at about 25° C., and the surface of the sponge was visually observed, and the residual dirt on the sponge (residue of colored beef tallow) was evaluated according to the following evaluation criteria. For example, when the sponge surface is shown in FIG. 1(a), it is judged to be "I", when shown in FIG. ” and judge.
I: The area of remaining soil is 5% or less of the surface area of the sponge.
II: The area of remaining soil is more than 5% and 10% or less of the surface area of the sponge.
III: The area of remaining soil is more than 10% and 40% or less of the surface area of the sponge.
IV: The area remaining soiled is more than 40% of the surface area of the sponge.

In Tables 1 to 7, "balance" is the amount of water (% by mass) required to make the total dishwashing detergent 100% by mass. Ingredients whose blending amounts are not listed in the table are not blended.
Moreover, "A/C ratio" is a mass ratio represented by (A) component/(C) component. "B/D ratio" is a mass ratio represented by component (B)/component (D). "B/D'ratio" is the mass ratio represented by component (B)/component (D'). "A/B ratio" is a mass ratio represented by component (A)/component (B). "A/D ratio" is a mass ratio represented by component (A)/component (D). "A/D'ratio" is the mass ratio represented by (A) component/(D') component. The "(A+C)/(B+D) ratio" is a mass ratio represented by ((A) component + (C) component)/((B) component + (D) component). The "(A+C)/(B+D') ratio" is a mass ratio represented by ((A) component + (C) component)/((B) component + (D') component). The "total amount of surfactant/(B+D) ratio" is the mass ratio represented by the total amount of surfactant/(component (B)+component (D)). The "total amount of surfactant/(B+D') ratio" is the mass ratio represented by the total amount of surfactant/((B) component + (D') component). "A+B" is the total content of the components (A) and (B) in 100% by mass of the dishwashing detergent. In addition, each mass ratio was obtained by rounding off to the second decimal place. The total amount of surfactant and the total content of components (A) and (B) were obtained by rounding off to the first decimal place.

As is clear from Tables 1 to 5, the dishwashing detergents of each example did not easily leave stains on the sponge when used after being diluted with water for dishwashing.
On the other hand, as is clear from Tables 6 and 7, the dishwashing detergents of Comparative Examples 1 to 3, which did not contain any of the components (A), (B) and (C), left stains on the sponge. It was easy.
The dishwashing detergents of Comparative Examples 4 and 9, in which the content of the component (D) was less than 0.1% by mass or more than 1.5% by mass, tended to leave stains on the sponge.
The dishwashing detergents of Comparative Examples 5 and 6 having an A/C ratio of less than 0.5 or more than 2.0 tended to leave stains on the sponge.
The dishwashing detergents of Comparative Examples 7 and 8 with a B/D ratio of less than 1.5 or more than 15 tended to leave stains on the sponge.
The dishwashing detergents of Comparative Examples 10 and 11, in which the component (D') was used instead of the component (D), tended to leave stains on the sponge.

Claims (5)

(A) component: an anionic surfactant;
(B) component: a compound represented by the following general formula (B-1);
(C) component: an amine oxide surfactant represented by the following general formula (C-1);
(D) component: containing a monohydric alcohol having 2 to 4 carbon atoms,
The content of the component (C) is 1.0% by mass or more, and the content of the component (D) is 0.1 to 1.5% by mass, relative to the total mass of the dishwashing detergent,
The mass ratio represented by the (A) component/the (C) component is 0.5 to 2.0,
A dishwashing detergent, wherein the mass ratio represented by component (B)/component (D) is 1.5 to 15.

(In the general formula (B-1), R ² is a linear or branched alkyl group having 1 to 14 carbon atoms, a linear or branched alkenyl group having 1 to 14 carbon atoms, a straight chain having 1 to 14 carbon atoms, a chain or branched hydroxyalkyl group or hydrogen, and R ³ and R ⁴ are each independently a straight or branched chain alkyl group having 1 to 5 carbon atoms, a straight or branched chain alkyl group having 1 to 5 carbon atoms, an alkenyl group or hydrogen.)

(In general formula (C-1), R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, B is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and r is a number of 0 or 1.) 2. The dishwashing detergent according to claim 1, wherein the mass ratio represented by component (A)/component (B) is 1.0 to 5.0. 3. The dishwashing detergent according to claim 1, wherein the mass ratio represented by component (A)/component (D) is 5.0 to 17. Claims 1 to 3, wherein the mass ratio represented by (the (A) component + the (C) component)/(the (B) component + the (D) component) is 1.5 to 6.0. A dishwashing detergent according to any one of the preceding claims. The component (A) is a polyoxyalkylene alkyl ether sulfate ester or its salt, a linear alkylbenzene sulfonic acid or its salt, an alkyl group-containing alkanesulfonic acid or its salt, an α-olefin sulfonate, or an internal olefin sulfonate. The dishwashing detergent according to any one of claims 1 to 4, comprising one or more selected from

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