TW201406947A - Dish detergent composition - Google Patents

Abstract

Provided are: a dish detergent composition which has excellent washing performance against stains that are dried complexes of lipids and proteins and are firmly adhered onto the surfaces of dishes; and a method for washing dishes using the dish detergent composition. A dish detergent composition comprising (A) a compound represented by general formula (1), (B) an ester-type nonionic surfactant produced from a fatty acid having 16 to 18 carbon atoms and an alcohol and (C) an alkaline agent, wherein the content of the component (A) is 0.1 to 50 mass%, the content of the component (B) is 0.1 to 15 mass% and the content of the component (C) is 5 to 80 mass%. (In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms; and M1, M2 and M3 independently represent an atom or a group selected from a hydrogen atom, an alkali metal atom, an ammonium group, an alkanolammonium group and an alkylammonium group.)

Description

Tableware detergent composition

The present invention relates to a dishwashing detergent composition useful as a detergent composition for an automatic dishwashing machine, and a cleaning method for a tableware using the same, which exhibits a high cleaning power for a firmly fixed stain.

Stains that are complexed with lipids and proteins, such as semi-cooked egg yolks, are firmly fixed to the tableware after drying, so that it is difficult to clean by an automatic tableware cleaner. Therefore, when the automatic dishwashing machine is used to clean such stains, the following pretreatment is required, that is, the tableware is immersed in water in advance, or gently hand-washed, etc., which is time consuming and labor intensive.

Therefore, the industry is expected to develop a cleaning agent for an automatic tableware cleaning machine which can remove stains without performing the above-mentioned time-consuming and labor-intensive pretreatment.

In recent years, from the viewpoint of environmental awareness, in the detergent for automatic dishwashing machine, a large amount of organic chelating agent having good biodegradability has been formulated. Examples of the organic chelating agent include glycine-N,N-diacetic acid derivatives (hereinafter also referred to as "GDA"). The GDA is an excellent cleaning base which is biodegradable and has a high chelation property. For the above reasons, GDA has been attracting attention as a material for reducing the amount of use of the surfactant (see Patent Document 1).

Patent Document 2 describes a detergent preparation containing a mixture of a polycarboxylic acid salt modified to be hydrophobic and a polycarboxylate modified to be hydrophilic, a complexing agent, and a low foaming nonionic property. Surfactants, bleaches, builders, enzymes, and the like. Further, in the cited document 2, GDA as a kind of a blocking agent is described.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-540375

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-500878

The present invention relates to a dishwashing detergent composition comprising a compound (A) represented by the following formula (1), an ester type nonionic surfactant having a carbon number of 16 to 18 and an alcohol (B) And the alkali agent (C), wherein the content of the component (A) is 0.1 to 50% by mass, the content of the component (B) is 0.1 to 15% by mass, and the content of the component (C) is 5 to 80% by mass. %,

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, an alkanolammonium, and an alkylammonium).

The cleaning agent described in Patent Document 2 is intended to suppress the formation of water spots, and the cleaning power of the stains complexed with lipids and proteins has not been studied. Further, Patent Document 2 describes only GDA as a kind of a blocking agent, and the relationship between GDA and cleanability and the amount of blending thereof have not been sufficiently studied.

The present invention provides a dishwashing detergent composition which exhibits excellent cleaning performance against stains (hereinafter, also referred to as "composite stains") which are composited with a lipid and a protein and firmly adhered to the surface of the tableware, and used The cleaning method of the tableware.

That is, the gist of the present invention is as follows.

[1] A dishwashing detergent composition containing a compound represented by the following formula (1) (A) an ester type nonionic surfactant (B) having a carbon number of 16 to 18 and an alcohol, and an alkali agent (C), and the content of the component (A) is 0.1 to 50% by mass, The content of the component (B) is 0.1 to 15% by mass, and the content of the component (C) is 5 to 80% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

[2] A method of cleaning a tableware, wherein the cleaning water having a concentration of the cleaning agent composition of the tableware of 0.02 to 0.4% by mass is brought into contact with the object to be cleaned attached to the tableware.

[3] A method for cleaning tableware, which comprises a compound (A) represented by the following formula (1), an ester type nonionic surfactant having a carbon number of 16 to 18 and an alcohol (B) And the tableware detergent composition of the alkali agent (C) is in contact with the tableware, and the content of the component (A) in the total of the components (A), (B) and (C) is 0.1 to 60% by mass, The content of the component (B) is 0.1 to 40% by mass, and the content of the component (C) is 5 to 99.8% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

According to the present invention, it is possible to provide a dishwashing detergent which exhibits excellent cleaning performance by stains which are compounded with a lipid and a protein and which are firmly fixed to the surface of the dishware. Cleaning methods for objects and utensils using them.

[Tableware detergent composition]

The dishwashing detergent composition of the present invention contains the compound (A) represented by the above formula (1), an ester type nonionic surfactant (B) having a carbon number of 16 to 18 and an alcohol, and a base. (C), wherein the content of the component (A) is 0.1 to 50% by mass, the content of the component (B) is 0.1 to 15% by mass, and the content of the component (C) is 5 to 80% by mass. It also shows excellent cleaning properties for composite stains. Further, the dishwashing detergent composition may be in any form of powder, granules, or solution.

<(A) component>

The component (A) is a compound represented by the following formula (1).

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

The hydrocarbon group represented by R in the above formula (1) is preferably an alkyl group or an alkenyl group. In the present invention, the alkyl group has a carbon number of from 1 to 12, preferably from 1 to 6, more preferably from 1 to 3. Further, the number of carbon atoms of the alkenyl group is 2 to 12, preferably 2 to 6, more preferably 2 to 3. When the carbon number is within the above range, the biodegradability and cleaning power of the obtained dishwashing detergent composition become good.

Specific examples of the preferred alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Among them, a methyl group is preferred. The term "various" as used herein refers to various isomers including positive, second, third, and different.

Further, specific examples of the preferred alkenyl group include a vinyl group, an allyl group, a 2-butenyl group, and a 2-methyl-2-propenyl group.

M ¹ , M ² and M ³ in the above formula (1) may each independently represent a hydrogen atom, an alkali metal such as sodium or potassium, or ammonium, an alkanolammonium or an alkylammonium. Among these, from the viewpoint of availability and cost reduction, a hydrogen atom or an alkali metal is preferred, and sodium is particularly preferred.

In the present invention, as the compound represented by the above formula (1), trisodium methylglycine diacetate is preferred.

The component (A) may be either a liquid or a solid. However, from the viewpoint of efficiently producing a dishwashing detergent composition and handling properties, it is preferably a solid.

The component (A) is contained in the dishwashing detergent composition in an amount of 0.1 to 50% by mass. When the content of the component (A) is 0.1% by mass or more, the effect as an organic chelating agent can be sufficiently exhibited, and if it is 50% by mass or less, the dishwashing detergent composition can be produced at low cost.

The content of the component (A) in the dishwashing detergent composition is preferably 1% by mass or more, more preferably from the viewpoint of sufficiently obtaining the effect of the organic chelating agent and the cost-effective production. It is 5% by mass or more, more preferably 10% by mass or more, further preferably 13% by mass or more, and more preferably 45% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. Further, it is more preferably 20% by mass or less. Specifically, it is preferably 1 to 45% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass, still more preferably 13 to 20% by mass.

<(B) component>

As the component (B), an ester type nonionic surfactant having a carbon number of 16 to 18 and an alcohol is used, and for example, a fatty acid alkyl ester selected from the group consisting of an alkyl group and an alkyl group is preferably an alkyl group. Poly or monooxyalkylene fatty acid esters, glycosylated poly or monoglyceride fatty acid esters, sorbitan fatty acid esters, sorbitan At least a part or two or more of a polyoxyethylene sorbitan fatty acid ester and a sugar fatty acid ester which are ethylated by an oxy group.

Specifically, it is preferably selected from the group consisting of glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and sucrose fatty acids. One or two or more kinds of esters.

More specifically, it is preferably selected from the group consisting of glyceryl palmitate, glycerin pearl photoacid ester, glyceryl stearate, glyceryl oleate, palm kernel oil, fatty acid monoglyceride, sorbitan monopalmitate, Sorbitol monobead photoacid ester, sorbitan monostearate, sorbitan monooleate, polyethylene glycol monopalmitate, polyethylene glycol monobead photoacrylate, polyethylene Glycol monostearate, polyethylene glycol monooleate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monobead photoate, polyoxyethylene sorbitan One or more of stearate, sucrose monopalmitate, sucrose monobehenate, sucrose monostearate, and sucrose monooleate.

Among these, glycerin fatty acid esters and sorbitan fatty acid esters are preferred, and glyceryl monostearate, glycerol monooleate, sorbitan monopalmitate, sorbitan are more preferred. Monostearate, sorbitan monooleate, and palm kernel oil constitute a fatty acid monoglyceride.

The component (B) is contained in the dishwashing detergent composition in an amount of 0.1 to 15% by mass. When the content of the component (B) is 0.1% by mass or more, the cleaning performance of the composite stain is improved, and when it is 15% by mass or less, the dishwashing detergent composition can be produced at low cost.

In view of the above, the content of the component (B) in the dishwashing detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and still more preferably 4%. The mass% or more is preferably 14% by mass or less, more preferably 13% by mass or less, further preferably 12% by mass or less, and still more preferably 11% by mass or less.

The content of the component (B) in the dishwashing detergent composition is preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably from the viewpoint of producing the dishwashing detergent composition at a lower cost. It is 8 mass% or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less.

<(C) component>

As the alkali agent, an alkali metal carbonate, an alkali metal ruthenate, an amine compound or the like can be used.

The alkali metal carbonate is preferably one or more selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. Further, an anhydrous salt of sodium carbonate which is well known as soda ash can also be used.

As the alkali metal ruthenate, a crystalline layered sodium citrate (manufactured by Tokuyama Siltech Co., Ltd., trade name "Purifeed") or the like can be used. Further, an amorphous one can also be used. Further, alkali metal silicate is also effective as an antioxidant for tableware.

As the amine compound, an alkanolamine can be mentioned. In the present invention, a primary alkanolamine is particularly preferred, and specific examples thereof include monoethanolamine. Among these alkaline agents, alkali metal carbonates are preferred.

The alkaline agent can be used in the form of powder or granules. The granules can be used by appropriately adjusting the particle diameter or the bulk specific gravity by granulation treatment or the like.

The component (C) is contained in the dishwashing detergent composition in an amount of 5 to 80% by mass. When the content of the component (C) is 5% by mass or more, the cleaning performance of the composite stain is improved, and when it is 80% by mass or less, the handleability of the detergent composition is improved.

In view of the above, the content of the component (C) in the dishwashing detergent composition is preferably 10% by mass or more, more preferably 13% by mass or more, still more preferably 15% by mass or more, and still more preferably 18% by mass. The mass% or more is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, and still more preferably 45% by mass or less.

The content of the component (C) in the dishwashing detergent composition is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30, from the viewpoint of further improving the cleaning performance of the composite stain. The mass% or more is more preferably 35% by mass or more, and still more preferably 40% by mass or more.

The total content of the component (A), the component (B) and the component (C) in the above-mentioned dishwashing detergent composition is preferably 30% by mass or more, and more preferably 35, from the viewpoint of obtaining excellent cleaning performance. The mass% or more is more preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less.

The total content of the component (A), the component (B), and the component (C) is preferably 45% by mass or more, more preferably 50% by mass or more, and still more preferably from the viewpoint of obtaining more excellent cleaning performance. 55 mass% or more, and more preferably 60 mass% or more.

The mass ratio of the component (A) to the component (B) in the above-mentioned dishwashing detergent composition [(A)/(B)] is preferably 1.0 or more from the viewpoint of the cleaning performance of the composite stain. It is preferably 1.5 or more, and more preferably 2.0 or more, and is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 6.0 or less from the viewpoint of the cleaning performance of the oil stain.

The mass ratio [(A)/(B)] is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less from the viewpoint of further improving the cleaning performance of the oil stain.

Further, the mass ratio of the component (B) to the component (C) [(B)/(C)] is preferably 0.01 or more, and more preferably 0.05 or more, from the viewpoint of the cleaning performance of the composite stain. Furthermore, it is preferably 0.08 or more, and from the viewpoint of the cleaning performance of the oil stain, it is preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.8 or less.

The mass ratio [(B)/(C)] is preferably 0.6 or less, more preferably 0.4 or less, further preferably 0.2 or less, and still more preferably 0.15 or less, from the viewpoint of further improving the cleaning performance of the oil stain. More preferably, it is 0.1 or less.

<(D) component>

In the present invention, from the viewpoint of improving the cleaning performance of the dishwashing detergent composition, it is preferred to use the copolymer (D) comprising a carboxylic acid derived from a carbon number of 3 to 6 having a reactive unsaturated group. The structural unit of the salt thereof (d-1) and the structural unit derived from the olefin (d-2) having 2 to 12 carbon atoms.

The carboxylic acid having a carbon number of 3 to 6 having a reactive unsaturated group or a salt thereof (hereinafter also referred to as a component (d-1)) is preferably selected from the group consisting of maleic acid and maleic anhydride. One or two or more of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, and the like may be these acid anhydrides. The component (d-1) may be any of a monocarboxylic acid and a dicarboxylic acid, but from the viewpoint of improving cleanability, a dicarboxylic acid is preferred.

The olefin having 2 to 12 carbon atoms (hereinafter also referred to as the component (d-2)) is preferably one selected from the group consisting of ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene. 2 or more types. The carbon number of the olefin is more preferably 4 to 12, still more preferably 6 to 10.

Among these, a copolymer obtained by combining maleic acid and diisobutylene or a salt thereof is preferred.

The (d-1) component in the component (D) is preferably 0.1 or more, more preferably 0.2 or more, based on the molar ratio [(d-1) component/(d-2) component] of the component (d-2). Further, it is preferably 0.3 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less.

The constituent monomers other than the components (d-1) and (d-2) above may be selected from the group consisting of acrylamide, methacrylamide, tert-butyl acrylamide, vinyl acetate, styrene, and nails. Hydroxyethyl acrylate, methyl methacrylate, butyl acrylate, stearyl methacrylate, styrene sulfonic acid and its salts, acrylamide-2-methylpropane sulfonic acid and its salts, 2-(A One or more of the acryloyloxy) ethanesulfonic acid and a salt thereof.

The total content of the component (d-1) and the component (d-2) in the component (D) is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, and preferably 100 mol. %the following. That is, the copolymer (D) in the present invention is preferably a copolymer consisting essentially only of the component (d-1) and the component (d-2). Further, the component (D) may be a salt, and examples thereof include a sodium salt, a potassium salt, and an ammonium salt.

The weight average molecular weight of the component (D) is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, and more preferably 50,000 or less, still more preferably 30,000 or less, and further Preferably, the amount is 20,000 or less, and more preferably 15,000 or less.

In addition, the weight average molecular weight of the component (D) in the present specification is a value obtained by using gel permeation chromatography using polystyrene as a standard substance. In the gel permeation chromatography, a solution of 60 mmol/L of phosphoric acid and 50 mmol/L of lithium bromide in dimethylformamide can be used as a developing solvent to connect two TSKgel α-Ms as a column.

When the average particle diameter of the component (D) is 10 μm or more, the blocking effect is suppressed. When the content is 500 μm or less, the solubility is improved. Therefore, the content is preferably 10 to 500 μm, more preferably 30 to 400 μm, and further preferably 50~300μm.

The average particle size was measured using a standard sieve of JIS K 8801 (mesh 2000 to 45 μm), and after vibrating for 5 minutes, the median diameter was calculated based on the weight fraction depending on the size of the sieve.

More specifically, a 12-segment sieve having a mesh of 45 μm, 63 μm, 90 μm, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm was used. The trays are sequentially stacked from the smaller mesh screen. 100 g of the particles were placed from the uppermost 2000 μm sieve, covered, and mounted on a Rotap Vibrating Screen (manufactured by HEIKO Co., Ltd., pp 156 times/min, vibration: 290 times/min). After vibrating for 5 minutes, the mass of the particles remaining on each of the sieves and the tray was measured, and the mass ratio (%) of the particles on each sieve was calculated. The value is plotted on the logarithmic probability paper {the horizontal axis is the mesh (particle diameter) of the sieve, and the vertical axis is the mass ratio}, and the line connecting the points is drawn, and the particle diameter corresponding to the mass ratio of 50% by mass is drawn. Set to the average particle size.

The component (D) is preferably contained in the dishwashing detergent composition in an amount of from 1 to 30% by mass. When the content of the component (D) is at least 1% by mass, the cleanliness of the composite stain is improved. When the content is 30% by mass or less, the solubility of the component (D) in water is improved, so that it is excellent in cleaning performance.

The content of the component (D) in the dishwashing detergent composition is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4, from the viewpoint of improving the cleaning performance and the solubility in water. The mass% or more is more preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and still more preferably 12% by mass or less. Specifically, it is preferably 2 to 25% by mass, more preferably 3 to 20% by mass, still more preferably 4 to 15% by mass, still more preferably 5 to 12% by mass.

The mass ratio of the component (A) to the component (D) in the above-mentioned dishwashing detergent composition [(A)/(D)] is preferably 0.5 or more from the viewpoint of improving the cleaning performance of the composite stain. More preferably, it is 1.1 or more, and further preferably 1.3 or more, and from the viewpoint of improving oil re-adhesion performance, it is preferably 5.0 or less, more preferably 4.4 or less, still more preferably 3.9 or less.

The mass ratio [(B)/(D)] of the component (B) to the component (D) is preferably 0.01 to 5.0. When the mass ratio [(B)/(D)] is 0.01 or more, the cleaning performance against oil stains is improved, and when it is 5.0 or less, the oil re-adhesion performance is improved.

The mass ratio [(B)/(D)] is 0.01 or more, preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.25 or more, further preferably 0.4 or more, and 5.0 or less, preferably 2.0. Hereinafter, it is more preferably 1.7 or less, further preferably 1.3 or less, and still more preferably 1.0 or less. Specifically, it is from 0.01 to 5.0, preferably from 0.05 to 2.0, more preferably from 0.08 to 1.7, still more preferably from 0.25 to 1.3, still more preferably from 0.4 to 1.0.

The total content of the component (A), the component (B), and the component (D) in the dishwashing detergent composition is preferably 10% by mass or more, and more preferably 17 or less, in view of the excellent cleaning performance. The mass% or more is more preferably 28% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

The pH of the 0.1% by mass aqueous solution of the above-mentioned dishwashing detergent composition at 25 ° C is preferably 9 to 13. When the pH of the aqueous solution is 9 or more, the cleaning power is increased, and when the pH is 13 or less, the damage of the tableware can be suppressed, and the workability is improved. From the above viewpoints, the pH of the 0.1% by mass aqueous solution at 25 ° C is preferably 9.5 or more, more preferably 10 or more, further preferably 10.5 or more, and preferably 11.4 or less, more preferably 11.3 or less, and further It is preferably 11.2 or less.

<Other ingredients>

In the dishwashing detergent composition, other components which are usually used for the detergent can also be formulated. For example, an enzyme, a builder, a metal ion blocking agent other than the component (A), a surfactant other than the component (B), a bleach, a bleach activator, an oil absorbing powder, an extender or a diluent Enzyme stabilizers such as calcium salts or formic acid, perfumes, pH adjusters, antibacterial/mold inhibitors, and pigments.

(enzyme)

The dishwashing detergent composition of the present invention preferably contains an enzyme. The enzyme is preferably one or more selected from the group consisting of a protease, an amylase, a lipase, a cellulase, an esterase, and a peroxidase, and a granulated product which is a commercially available product can be used. The above enzymes may be appropriately selected in consideration of storage stability of other components and the like. Among these, an amylase which acts on gelatinized starch which is difficult to remove with other surfactants is preferably expected. Further, protease is also preferred because the protease exerts a remarkable effect on a modified protein which is difficult to remove by using a surfactant or the like.

The content of the enzyme in the dishwashing detergent composition is preferably 0.2 to 20% by mass, more preferably 0.4 to 14% by mass, still more preferably 0.4 to 10% by mass.

(metal ion blocker)

As the metal ion blocking agent other than the component (A), citric acid, malic acid, tartaric acid, succinic acid, L-glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, or the like can be used. Nitrotriacetic acid, 1,3-propanediaminetriacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid And a polycarboxylic acid such as triethylenetetraamine hexaacetic acid, dihydroxyethylglycine, or hydroxyethylethylenediamine dicarboxymethylglutamic acid or a salt thereof. Among these, citric acid, succinic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, hydroxyethylethylenediamine dicarboxymethylglutamic acid, and the alkali metal salts thereof are preferred. Further, a phosphate such as sodium tripolyphosphate can also be used.

(surfactant)

Examples of the surfactant include a nonionic surfactant other than the component (B), an anionic surfactant, an amphoteric surfactant, and a cationic surfactant.

(bleach)

The bleaching agent is preferably an organic peracid such as magnesium monoperoxyphthalate or a salt thereof, an alkali metal perborate (monohydrate or tetrahydrate), percarbonate or persulfate. The ceric acid salt is one or more of the peroxides which generate hydrogen peroxide in the aqueous solution. Among these, inorganic peroxides such as sodium persulfate, sodium percarbonate, and sodium perborate are more preferred.

(bleach activator)

In the present invention, a bleach activator which is usually formulated as a cleaning agent for an automatic dishwashing machine can be blended as a cleaning auxiliary component for further improving the cleaning power.

The bleach activator is used in combination with the above bleaching agent and is a substance which reacts with hydrogen peroxide released from the bleaching agent to form an organic peracid having a higher redox potential. Specifically, it is preferably selected from tetraethylenesulfonylethylenediamine (TAED), tetraethylenemethylidenediamine (TAMD), alkylnonoxybenzenecarboxylic acid or a salt thereof, or an alkoxybenzene. The sulfonate, for example, one or more of n-decyl or isodecyloxybenzenesulfonate (normal or iso-NOBS).

(oil-absorbing powder)

As the oil absorbing powder, amorphous ceria, dextrin, or the like can be used.

As a commercially available product of the amorphous ceria, Tokusil NR, Tokusil NP (manufactured by Oriental Silicas Corporation), Florite (manufactured by Tomita Pharmaceutical Co., Ltd.), TIXOLEX 25 (manufactured by Kofran Chemical Co., Ltd.), and Sylopure (Fuji Silysia ( Share) manufacturing) and so on.

Examples of the dextrin include those obtained by hydrolyzing starch derived from various cereals using an acid or an amylase. Various decomposition products exist depending on the degree or structure of hydrolysis. For example, starch dextrin (soluble starch), red dextrin, colorless dextrin, maltodextrin, cyclodextrin, etc. are mentioned. Among them, the DE value (starch decomposition rate = glucose equivalent mass / total solid matter component mass × 100) is preferably 0.1 to 10, more preferably 0.1 to 5. Further, it is preferred that the DE value is preferably from 0.1 to 3 from the viewpoint of alkali resistance even if it is rapidly dissolved in cold water or warm water.

Among the above oil-absorbing powders, amorphous ceria is preferred. The oil absorbing powder may be used singly or in combination of two or more.

(extender, thinner)

Examples of the extender or diluent include sulfates such as sodium sulfate and magnesium sulfate. If a bulking agent or diluent is formulated, it can be dispersed to an appropriate concentration by diluting the components. It is also effective for maintaining the stability of each component in an amount suitable for use. As the sodium sulfate, a commercial product such as "A6 Glauber's salt" manufactured by Shikoku Chemicals Co., Ltd. can be used. The Glauber's salt which can be used in the present invention is preferably 90% by mass or more based on the total particle diameter of 20 μm or less from the viewpoint of solubility.

Further, the total content of the extender and the diluent in the detergent composition for tableware is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and still more preferably 3 mass% or more, and preferably 50 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, further preferably 10 mass% or less, and still more preferably 5% by mass or less. When the total content of the extender and the diluent is 0.01% by mass or more, the stability of each component can be improved, and if it is 50% by mass or less, a detergent composition which can be easily handled can be obtained.

(antifoaming agent)

In order to suppress foaming, the above-mentioned dishwashing detergent composition preferably contains an antifoaming agent.

As the antifoaming agent, a polyfluorene defoaming agent can be mentioned. As the form of the polyoxygen antifoaming agent, any of an oil type, a composite type, a powder type, and an emulsion type can be used.

The content of the polyfluorene defoaming agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less. When it is at least the lower limit value, effective defoaming performance can be obtained, and if it is at most the upper limit value, the defoaming performance can be exhibited while maintaining the cleaning performance.

<Form of dishwashing detergent composition>

The dishwashing detergent composition may also be used in the form of a powdered detergent, or may be dissolved in water, an organic solvent or the like and used in the form of a solution-like detergent, and may also be granulated into granules. As a cleaning agent.

Examples of the solvent which can be used in the case of a detergent in the form of a solution include water, ethanol, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, and isoprene. Alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutyl Alcohol, phenoxyethanol, phenethylene glycol, phenoxyisopropanol, butyl diethylene glycol (diethylene glycol monobutyl ether), di-n-butyl diethylene glycol, benzyl alcohol, and the like. When the solution is used in the form of a solution, the amount of the solvent in the detergent composition of the dish is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably from the viewpoint of stabilizing the properties of the solution. It is 10% by mass or more. Moreover, the amount of the solvent in the dishwashing detergent composition is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20%, from the viewpoint of inexpensively producing the dishwashing detergent composition. %the following.

As a mixing method, a Henschel mixer (NIPPON COKE & ENGINEERING), a high-speed mixer (manufactured by FUKAE POWTEC), a cone mixer (manufactured by Hosokawa Micron), and a belt type are used. A well-known mixer such as a mixer (manufactured by Tetsuo Co., Ltd.), a V-type blender (manufactured by DALTON Co., Ltd.), or a table kneading machine (manufactured by the company) is particularly preferable. To use a conical mixer that does not apply shear forces when agitating. Further, part or all of the above components may be mixed and then co-granulated by a granulator.

Examples of the granulation method include an extrusion granulation method, a rotary granulation method, a crush granulation method, a fluidized bed granulation method, a spray granulation method, and a crush granulation method. Among these, the extrusion granulation method and the rotary granulation method are more preferred.

Examples of the extrusion granulator include a biaxial granulator, a wet extrusion granulator, a pan granulator (manufactured by DALTON Co., Ltd.), and a basket granulator (manufactured by Kikusui Seisakusho Co., Ltd.). A known extrusion granulator such as a horizontal extrusion type spiral extrusion granulator (manufactured by Okawara Seisakusho Co., Ltd.) described in Japanese Patent Laid-Open No. Hei 10-192688.

(adhesive)

In the case where the above-mentioned dishwashing detergent composition is granulated, a nonionic surfactant or a polymer binder may be used in order to increase the physical strength of the granulated material.

As the nonionic surfactant, in addition to the component (B), (B) can be suitably used. Other than the others.

The polymer is preferably polypropylene glycol, polyethylene glycol, polyoxyethylene alkyl ether or polyoxyethylene phenol ether. More preferably, it is polyethylene glycol or polypropylene glycol.

As the binder, one type of the above compounds may be used alone or two or more types may be used in combination. Further, from the viewpoint of improving the defoaming property in the case where the granulated product is used as the powder detergent composition, polypropylene glycol can also be used as the antifoaming agent.

When the granulated product contains polypropylene glycol, the content thereof is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, even more preferably from 3 to 12% by mass, based on the granule.

When the granulated product contains polyethylene glycol, the content thereof is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, even more preferably from 3 to 10% by mass, based on the granule.

Ease of manufacture it is, and the viewpoint of enhancing the solubility, the bulk specific gravity of the powder used in the form of the detergent is preferably 0.7 ~ 0.9g / cm ^3, more preferably 0.75 ~ 0.85g / cm ^3.

The dishwashing detergent composition of the present invention has higher cleaning performance than the conventional dishwashing detergent composition, and thus can be used in a reduced amount. Moreover, since the amount of use can be reduced, the size of the container can be reduced, and the amount of use of the packaging material can be reduced.

Further, the dishwashing detergent composition of the present invention is suitable for a detergent composition for an automatic dishwashing machine.

[Cleaning method of tableware]

In the cleaning method of the tableware of the present invention, the cleaning water having a concentration of the cleaning agent composition of the tableware of 0.02 to 0.4% by mass is brought into contact with the object to be cleaned attached to the tableware. The total concentration of the above components (A), (B) and (C) in the above clean water is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, and still more preferably 0.09%. The mass% or more is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, and still more preferably 0.12% by mass or less. When the concentration is at least the lower limit value, the cleaning power is increased, and if it is at most the upper limit value, it is not only excellent in cost but also small in capacity, and can be made into a cleaning agent which is easy to handle.

Moreover, the cleaning method of the tableware of the present invention is an ester type nonionic surfactant (B) containing a compound (A) represented by the following formula (1), a fatty acid having a carbon number of 16 to 18, and an alcohol, And the tableware detergent composition of the alkali agent (C) is in contact with the tableware, and the content of the component (A) in the total of the components (A), (B) and (C) is 0.1 to 60% by mass, The content of the component (B) is 0.1 to 40% by mass, and the content of the component (C) is 5 to 99.8% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

When the content of the component (A) is at least the following lower limit, the effect as an organic chelating agent can be sufficiently obtained, and if it is at most the following lower limit, the cost can be suppressed and efficiently produced. The content of the component (A) in the total of the components A), (B) and (C) is 0.1% by mass or more, preferably 5% by mass or more, more preferably 12% by mass or more, and still more preferably 15% by mass. % or more is 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 25% by mass or less.

When the content of the component (B) is at least the lower limit value, the cleaning performance of the composite stain is improved, and if it is at most the lower limit value described below, it can be produced at low cost. Therefore, the above (A) and (B) and The content of the component (B) in the total of the components (C) is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and 40%. The mass% or less is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 17% by mass or less, and still more preferably 8% by mass or less.

When the content of the component (C) is at least the lower limit value, the cleaning performance of the composite stain is improved, and if it is at most the following lower limit, the handleability of the detergent composition is improved. The content of the component (C) in the total of the components (A), (B) and (C) is 5% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35 mass% or more, more preferably 50 mass% or more, and 99.8% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 79% by mass or less, and still more preferably 78% by mass or less.

In the above embodiment, the present invention discloses the following dishwashing detergent composition and tableware cleaning method.

[1] A dishwashing detergent composition comprising a compound (A) represented by the following formula (1), an ester type nonionic surfactant having a carbon number of 16 to 18 and an alcohol (B) And the alkali agent (C), wherein the content of the component (A) is 0.1 to 50% by mass, the content of the component (B) is 0.1 to 15% by mass, and the content of the component (C) is 5 to 80% by mass. .

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, an alkanolammonium, and an alkylammonium).

[2] The dishwashing detergent composition according to [1], wherein the hydrocarbon group represented by R in the above formula (1) is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and various butyl groups. One or two or more of various pentyl groups and various hexyl groups.

[3] The dishwashing detergent composition according to [1] or [2], wherein the hydrocarbon group represented by R in the above formula (1) is selected from the group consisting of a vinyl group, an allyl group, a 2-butenyl group, and One or two or more of 2-methyl-2-propenyl groups.

[4] The dishwashing detergent composition according to any one of [1] to [3] wherein, in the above formula (1), M ¹ , M ² and M ³ are each independently selected from a hydrogen atom and a sodium. One of an alkali metal such as potassium, ammonium, an alkanolammonium or an alkylammonium, more preferably sodium.

[5] The dishwashing detergent composition according to any one of [1] to [4] wherein the component A is trisodium methylglycine diacetate.

[6] The dishwashing detergent composition according to any one of [1] to [5] wherein the content of the component (A) in the detergent composition of the tableware is preferably 1% by mass or more, more preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 13 mass% or more, and more preferably 45 mass% or less, more preferably 30 mass% or less, further preferably 25% by mass or less, and further More preferably, it is 20 mass% or less.

[7] The dishwashing detergent composition according to any one of [1] to [6] wherein the component (B) is a fatty acid alkyl ester selected from the group consisting of an alkylene group and an ethylenic group. Or at least a poly(ethylene)alkylene fatty acid ester, a glycosylated poly or monoglyceride fatty acid ester, a sorbitan fatty acid ester, or a sorbitan One or two or more of a polyoxyethylene sorbitan fatty acid ester and a sugar fatty acid ester which are partially ethylated by an oxygen group.

[8] The dishwashing detergent composition according to any one of [1] to [7] wherein the content of the component (B) in the dishwashing detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and more preferably 14% by mass or less, more preferably 13% by mass or less, still more preferably 12% by mass or less, and further preferably It is more preferably 11% by mass or less, further preferably 10% by mass or less, further 9% by mass or less, further 8% by mass or less, further 6% by mass or less, and further 5% by mass or less.

[9] The dishwashing detergent composition according to any one of [1] to [8] wherein the component (C) is one selected from the group consisting of an alkali metal carbonate, an alkali metal silicate, and an amine compound. Or two or more.

[10] The dishwashing detergent composition according to any one of [1] to [9] wherein the content of the component (C) in the dishwashing detergent composition is preferably 10% by mass or more, more preferably 13% by mass or more, further preferably 15% by mass or more, more preferably 18% by mass or more, further 20% by mass or more, further 25% by mass or more, further 30% by mass or more, and further 35 The mass% or more is further 40% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, and still more preferably 45% by mass or less.

[11] The dishwashing detergent composition according to any one of [1] to [10] wherein the total content of the component (A), the component (B) and the component (C) is 30 to 80% by mass.

[12] The dishwashing detergent composition according to any one of [1] to [11] wherein the total content of the component (A), the component (B), and the component (C) is preferably 30% by mass or more. It is more preferably 35 mass% or more, further preferably 40 mass% or more, further 45 mass% or more, further 50 mass% or more, further 55 mass% or more, further 60 mass% or more, and preferably 80. The mass% or less is more preferably 75% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

[13] The dishwashing detergent composition according to any one of [1] to [12] wherein the mass ratio of the component (A) to the component (B) in the dishwashing detergent composition is [(A) / (B)] is preferably 1.0 or more, more preferably 1.5 or more, still more preferably 2.0 or more, and is preferably 10.0 or less, more preferably 8.0 or less, further preferably 6.0 or less, and further 5.0 or less. It is 4.0 or less, and further 3.0 or less.

[14] The dishwashing detergent composition according to any one of [1] to [13] wherein the mass ratio of the component (B) to the component (C) is preferably [(B)/(C)]. It is 0.01 or more, more preferably 0.05 or more, still more preferably 0.08 or more, and is preferably 1.2 or less, more preferably 1.0 or less, further preferably 0.8 or less, further preferably 0.6 or less, further 0.4 or less, and further 0.2. Hereinafter, it is further 0.15 or less, and further 0.1 or less.

[15] The dishwashing detergent composition according to any one of [1] to [14] wherein the 0.1% by mass aqueous solution of the above-mentioned dishwashing detergent composition has a pH of 9 to 13 at 25 °C.

[16] The dishwashing detergent composition according to any one of [1] to [15] wherein the pH of the 0.1% by mass aqueous solution of the above-mentioned dishwashing detergent composition is preferably 9.5 or more at 25 ° C, more It is preferably 10 or more, more preferably 10.5 or more, and is preferably 11.4 or less, more preferably 11.3 or less, still more preferably 11.2 or less.

[17] The dishwashing detergent composition according to any one of [1] to [16] which further contains an enzyme.

[18] The dishwashing detergent composition according to any one of [1] to [17] wherein the enzyme is one selected from the group consisting of a protease, an amylase, a lipase, a cellulase, an esterase, and a peroxidase. Kind or more than two.

[19] The dishwashing detergent composition according to any one of [1] to [18] further comprising a carboxylic acid having a carbon number of 3 to 6 derived from a reactive unsaturated group or a salt thereof (d- 1) a copolymer (D) of a structural unit and a structural unit derived from an olefin (d-2) having 2 to 12 carbon atoms, and the content of the component (D) is 1 to 30% by mass.

[20] The dishwashing detergent composition according to any one of [1] to [19] which is used in an automatic tableware cleaning machine.

[21] A method of cleaning a tableware, wherein the cleaning agent composition according to any one of [1] to [20] has a concentration of 0.02 to 0.4% by mass of clean water and is attached to the tableware to be cleaned. Contact with matter.

[22] The method for cleaning a tableware according to [21], wherein a total concentration of the components (A), (B) and (C) in the clean water is preferably 0.02% by mass or more, more preferably 0.05% by mass or more. Further, it is preferably 0.07% by mass or more, more preferably 0.09% by mass or more, and is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass. Hereinafter, it is more preferably 0.12% by mass or less.

[23] A method for cleaning a dish comprising an ester-type nonionic surfactant (B) comprising a compound (A) represented by the following formula (1), a fatty acid having a carbon number of 16 to 18, and an alcohol; And the tableware detergent composition of the alkali agent (C) is in contact with the tableware, and the content of the component (A) in the total of the components (A), (B) and (C) is 0.1% by mass or more. It is preferably 5% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, and preferably 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and further preferably The content of the component (B) is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and 40% by mass or less. The content of the component (C) is preferably 5% by mass or less, more preferably 20% by mass or less, more preferably 20% by mass or less, still more preferably 17% by mass or less, still more preferably 8% by mass or less, and the content of the component (C) is 5% by mass or more. It is preferably 25 mass% or more, more preferably 30 mass% or more, further preferably 35 mass% or more, further preferably 50 mass% or more, and 99.8% by mass or less, preferably 85 mass% or less, more preferably It is 80% by mass or less, more preferably 79% by mass or less, and still more preferably 78% by mass or less.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

[24] The use of the dishwashing detergent composition according to any one of [1] to [19], which is used as a dishwashing detergent.

[25] The use of the dishwashing detergent composition according to any one of [1] to [19], which is used as a cleaning agent for an automatic tableware cleaning machine.

[26] The use of the dishwashing detergent composition according to any one of [1] to [19], which is used as a dishwashing detergent, and which is obtained according to any one of [1] to [19] The cleaning water having a concentration of the cleaning agent composition of 0.02 to 0.4% by mass is in contact with the object to be cleaned attached to the tableware.

[27] The use of the dishwashing detergent composition according to any one of [1] to [19], which is used as a dishwashing detergent, and (A), (B) and (C) in clean water The total content of the components is 0.02% by mass or more, preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.09% by mass or more, and 0.4% by mass or less, preferably 0.3% by mass or less. More preferably, it is 0.2 mass% or less, further preferably 0.15 mass% or less, and most preferably 0.12%. The clean water of the mass% or less is in contact with the object to be cleaned attached to the tableware.

Example 1

The detergent composition for an automatic dishwashing machine of Example 1 was prepared in the following order (1) to (3).

(1) The component (A), sodium sulfate, (C) component, Purifeed pellet, succinic acid, or polyethylene glycol are mixed.

(2) A mixture of the polypropylene glycol, the fragrance, and the component (B) is added to the mixture obtained in (1) and mixed.

(3) The mixture obtained in (2) is further added with sodium percarbonate, tetraethyleneethylenediamine, α-amylase, protease, and mixed to prepare a detergent composition for an automatic tableware cleaner.

Examples 2 to 13 and Comparative Examples 1 to 6

A detergent composition for an automatic dishwashing machine was prepared in the same manner as in Example 1 except that the ratios shown in Tables 1 and 2 were used. Further, only the ester or the alkyl compound added in Comparative Examples 1 to 6 was mixed in the step (2) instead of the component (B) to prepare a second mixture.

<Evaluation of cleanliness>

‧Test tableware production

(1) Breaking 5 eggs, removing the protein and separating to obtain the egg yolk.

(2) The above egg yolk was added to a screw cap sample bottle (No. 8), and heated in a water bath at 73 to 75 ° C for 10 minutes.

(3) The screw cap sample bottle was taken out from the water bath, and allowed to stand at room temperature for 1 hour, and the semi-cooked egg yolk was placed on the tea filter net for screen filtration.

Further, the so-called screen filtration refers to an operation of crushing the food material by a net having a small mesh.

(4) After filtering the semi-cooked egg yolk with a sieve, fully stir it, and take 3g for the obtained one. It was uniformly applied to ceramic tableware with a brush (9-inch soup plate (diameter 233 mm × 24 mm, Putian Store Co., Ltd.) for white jade business.

(5) The semi-cooked egg yolk coated on the ceramic tableware was dried at room temperature for a day and night to prepare test dishes.

In addition, as the tea filter net, a "clean tea filter net 72 mm" manufactured by SUN-CORPORATION (material: 18-8 stainless steel, caliber: 72 mm, mesh diameter: 0.6 mm) was used.

‧ cleaning test

The cleaning agent composition for the automatic dishwashing machine prepared in the above-mentioned Examples and Comparative Examples was put into a dish cleaning and drying machine (Panasonic), model "NP-" so that the concentration in the cleaning liquid at the time of cleaning became 0.1% by mass. In the detergent tank of P45M2PS" (built-in), it is cleaned in a fast process. Further, on the right end of the place where the tableware is placed on the right side of the basket under the tableware cleaning and drying machine, the stained surface of the stained ceramic tableware is erected toward the inner side. Two ceramic dishes that are not stained are placed next to each other.

‧ Evaluation method

The amount of the semi-cooked dried egg yolk remaining on the surface of the test dish was evaluated by visual inspection at 6 levels of 0 to 5. The results are shown in Tables 1 and 2.

(judgment basis)

5: Completely clean.

4: Although some stains remain, they are almost clean (within the allowable range).

3: Although most of it is clean, there are stains left. Or the stain remains on the whole lighter (outside the allowable range).

2: Slightly clean, but most of the stain remains.

1: Almost unclean.

0: Not clean at all.

<pH value determination>

Using a pH meter (manufactured by Horiba, Ltd., model "F-52", pH electrode 6367-10D), The pH at 25 ° C was measured in accordance with JIS Z-8802:1984. As the measurement solution, the detergent composition prepared by the above method was diluted to 0.1% by mass by using deionized water.

The details of the compounds described in the table are as follows. Further, the unit of the content described in the table is % by mass, and the value of the concentration of the active ingredient is not considered.

*1: Made by BASF Japan, "Trilon M Powder"

(Methylglycine diacetate trisodium), active ingredient 87% by mass

*2: Kao (stock) manufacturing, "EXCEL VS-95", active ingredient 100% by mass

*3: Kao (stock) manufacturing, "EXCEL 200", active ingredient 85 mass%

(glyceryl stearate / oleic acid glyceride weight ratio: 71/29)

*4: Kao (stock) manufacturing, "RHEODOL SP-S10V"

Active ingredient 100% by mass

*5: Kao (stock) manufacturing, "EMANON 3199V"

Active ingredient 100% by mass

*6: Kao (stock) manufacturing, "RHEODOL TW-S106"

Active ingredient 97.3% by mass

*7: Manufacturing of Mitsui Chemicals Co., Ltd.

"Ryoto Sugar Ester P-1570"

Active ingredient 100% by mass

*8: 100% by mass of active ingredient of Wako Pure Chemical Industries Co., Ltd.

*9: Japanese catalyst (shares), "monoethanolamine"

Active ingredient 100% by mass

*10: Wako Pure Chemical Industry Co., Ltd. manufactures, reagents special grade

*11: Made by Nippon Peroxide, model "KCPZ"

Sodium percarbonate coated on the surface with sodium metaborate

It contains 5% by mass of sodium carbonate and 1% by mass of sodium citrate.

*12: Made by Tokyo Chemical Industry Co., Ltd.

*13: manufactured by Tokuyama Siltech Co., Ltd., "Purifeed Granules"

*14: Made by Novozymes Japan, "Duramyl 120T"

*15: Made by Novozymes Japan

"Savinase 18T"

*16: Wako Pure Chemical Industries Co., Ltd. manufactures, special reagents

*17: Kao (stock) manufacturing, polyethylene glycol

(quantitative average molecular weight = 8,500)

*18: Asahi Glass Co., Ltd., "PREMINOL S4011"

(quantitative average molecular weight = 10,000)

*19: Kao (stock) manufacturing

Further, the addition molar number of ethylene oxide (EO) in the "polyoxyethylene (6) alkyl ether" in Tables 1 and 2 was 6.

As is clear from Tables 1 and 2, the dishwashing detergent composition of the present invention exhibits excellent cleaning properties against the composite stain.

Example 14

The detergent composition for an automatic dishwashing machine of Example 14 was prepared in the following order (1) to (4).

(1) The component (A), sodium sulfate, sodium carbonate, sodium citrate, succinic acid, or polyethylene glycol were mixed in a 30 L conical mixer (rotation: 110 r/min, revolution: 4 r/min).

(2) Polypropylene glycol and a fragrance are mixed in the mixture obtained in (1).

(3) The mixture obtained in (2) is mixed with sodium carbonate, tetraethyleneethylenediamine, α-amylase, and protease.

(4) Preparing a 10% by mass aqueous solution of the component (D) (a salt of a copolymer of diisobutylene and maleic acid) and a 10% by mass ethanol solution of the component (B), respectively, and the solution (3) The mixture obtained in the mixture is mixed to prepare a detergent composition for an automatic tableware cleaner.

Examples 15 to 27 and Comparative Examples 7 to 9

A detergent composition for an automatic dishwashing machine was prepared in the same manner as in Example 14 except that the ratios are shown in Tables 3 and 4.

<Evaluation of cleanliness>

‧Test tableware production

Test tableware was prepared in the following order.

(1) Break 5 eggs, use egg yolk separator to remove protein and separate to obtain egg yolk.

(2) The above egg yolk was added to a screw cap sample bottle (No. 8), and heated in a water bath at 73 to 75 ° C for 10 minutes.

(3) The screw cap sample bottle was taken out from the water bath, and allowed to stand at 25 ° C for 1 hour, and the semi-cooked egg yolk was placed on the tea strain net for screen filtration.

Further, the so-called screen filtration refers to an operation of crushing the food material by a net having a small mesh.

(4) Filter the semi-cooked egg yolk with a sieve, and mix and mix the lower part of the self-filtering tea net, then take 3g and apply it evenly to the pottery tableware with a brush (white oyster soup with 9-inch soup plate (diameter 233mm×24mm) ), Putian Store Co., Ltd.).

(5) The semi-cooked egg yolk coated on the ceramic tableware was dried at 25 ° C for a day and night to prepare test dishes.

In addition, as the tea filter net, a "clean tea filter net 72 mm" manufactured by SUN-CORPORATION (material: 18-8 stainless steel, caliber: 72 mm, mesh diameter: 0.6 mm) was used.

<pH value determination>

The pH value at 25 ° C was measured in accordance with JIS Z-8802:1984 using a pH meter (manufactured by Horiba, Ltd., model "F-52", pH electrode 6367-10D). As the measurement solution, the detergent composition prepared by the above method was diluted to 0.1% by mass by using deionized water.

‧ cleaning test

The cleaning agent composition for the automatic dishwashing machine prepared in the above-mentioned examples and the comparative examples was put into a dish cleaning and drying machine (Panasonic), model "NP-TR3" (desktop) so that the concentration in the cleaning liquid became 0.1% by mass. )) in the detergent tank (use of tap water: 3L). Further, the above concentration is the total concentration of each component described in Table 1, and the concentration of water and ethanol used for dissolving the component (B) and the component (D) is not calculated as the concentration of the detergent composition for the automatic dish cleaner. Further, regarding ethanol, the same amounts were used in the examples and comparative examples, respectively.

In the place where the tableware is placed on the right side of the basket under the tableware cleaning and drying machine, three test pieces are erected every one erected groove of the tableware, and cleaned in a rapid process. Furthermore, The surface on which the stain of the test tableware adhered was erected toward the inner side. In the three test dishes, two test dishes at both ends were evaluated.

‧ Evaluation method

The amount of dry, semi-cooked egg yolk remaining on the surface of the test dish was evaluated by visual inspection on a scale of 0 to 5. The evaluation was performed by evaluation by 5 people and calculation of the average value. In other words, the five evaluators evaluated the two test dishes described above, and calculated the average value, thereby performing evaluation.

The results are shown in Tables 3 and 4.

(judgment basis)

5: Completely clean.

4: Although some stains remain, they are almost clean (within the allowable range).

3: Although most of it is clean, there are stains left. Or the stain remains on the whole lighter (outside the allowable range).

2: Slightly clean, but most of the stain remains.

1: Almost unclean.

0: Not clean at all.

Further, the detergent composition for an automatic dishwashing machine having more than 3, preferably 4 or more, in the above-described criterion has sufficient cleaning performance as a detergent composition for an automatic dishwashing machine.

The details of the compounds described in the table are as follows. Further, the unit of the content described in the table is % by mass, and the value of the concentration of the active ingredient is not considered.

*1a: Made by BASF Japan, "Trilon M Powder"

(Methylglycine diacetate trisodium), active ingredient 87% by mass

*2a: Kao (stock) manufacturing, "EXCEL VS-95", active ingredient 100% by mass

*3a: Kao (share) manufacturing, "EXCEL P-40", active ingredient 100% by mass

*4a: Kao (stock) manufacturing, "RHEODOL MO-60", active ingredient 90% by mass

*5a: Kao (stock) manufacturing, "EMASOL P-10V", active ingredient 100% by mass

*6a: Kao (stock) manufacturing, "EMASOL S-10V", 100% by mass of active ingredient

*7a: Kao (stock) manufacturing, "EMASOL O-10V", active ingredient 100% by mass

*8a: manufactured by Rohm and Hass Japan

"Acusol 460ND"

Weight average molecular weight = 10,000, average particle diameter = 134 μm,

Active ingredient 92% by mass maleic acid / diisobutylene = 1.0 (mole ratio)

*9a: Manufacturing of Wako Pure Chemical Industries Co., Ltd.

*10a: Manufacturing of Wako Pure Chemical Industries Co., Ltd.

*11a: Made by Nippon Peroxide, model "KCPZ"

Sodium percarbonate coated on the surface with sodium metaborate

It contains 5% by mass of sodium carbonate and 1% by mass of sodium citrate.

*12a: Manufacturing of Tokyo Chemical Industry Co., Ltd.

*13a: manufactured by Tokuyama Siltech Co., Ltd., "Purifeed Granules"

*14a: manufactured by Novozymes Japan, "Duramyl 120T"

*15a: Made by Novozymes Japan, "Savinase 18T"

*16a: Wako Pure Chemical Industries Co., Ltd.

*17a: Kao (stock) manufacturing, "K-PEG6000LA"

Number average molecular weight = 8,500

*18a: manufactured by Asahi Glass Co., Ltd., "PREMINOL S4011",

Number average molecular weight = 10,000

Hereinafter, a formulation example showing an embodiment of the detergent composition for an automatic tableware cleaning machine of the present invention will be described.

[table 5]

*19a: Manufactured by Oriental Silicas Corporation

"Tokusil NP"

*20a: Made by Novozymes Japan

"Stainzyme Plus Evity 12T"

*21a: Made by Dow Corning Toray

"FS Antifoam F-16"

As is apparent from the results of Tables 3 and 4, the detergent composition for an automatic dishwashing machine of the present invention exhibits excellent cleaning performance against stains which are compounded with a lipid and a protein and dried and firmly fixed to the tableware. Moreover, as is clear from Table 3, the detergent composition for the dish cleaner can also be used in a powdery or granular state.

Claims (16)

A dishwashing detergent composition comprising a compound (A) represented by the following formula (1), an ester type nonionic surfactant (B) having a carbon number of 16 to 18 and an alcohol, and a base The content of the component (A) is 0.1 to 50% by mass, the content of the component (B) is 0.1 to 15% by mass, and the content of the component (C) is 5 to 80% by mass, (In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, an alkanolammonium, and an alkylammonium). The dishwashing detergent composition of claim 1, wherein the component (A) is trisodium methylglycine diacetate. The dishwashing detergent composition according to claim 1 or 2, wherein the content of the component (A) in the dishwashing detergent composition is from 1 to 45% by mass. The dishwashing detergent composition according to claim 1 or 2, wherein the component (B) is a fatty acid alkyl ester selected from the group consisting of an alkylene group, an ethyloxy group, an ethyloxy group, and an oxy extension group. Agglomerated at least a portion of a propylated poly or monooxyalkylene fatty acid ester, a glycosylated poly or monoglyceride fatty acid ester, a sorbitan fatty acid ester, or a sorbitan by an ethoxyethyl group One or more of oxyethylene sorbitan fatty acid ester and sugar fatty acid ester. The dishwashing detergent composition according to claim 1 or 2, wherein the component (B) in the dishwashing detergent composition is contained in an amount of from 1 to 14% by mass. The dishwashing detergent composition according to claim 1 or 2, wherein the component (C) is selected from a base One or more of a metal carbonate, an alkali metal citrate, and an amine compound. The dishwashing detergent composition according to claim 1 or 2, wherein the component (C) in the dishwashing detergent composition is contained in an amount of 10 to 70% by mass. The dishwashing detergent composition according to claim 1 or 2, wherein the total content of the component (A), the component (B) and the component (C) is 30 to 80% by mass. The dishwashing detergent composition according to claim 1 or 2, wherein the mass ratio of the component (A) to the component (B) in the detergent composition of the tableware is 1.0 to 10.0. . The dishwashing detergent composition according to claim 1 or 2, wherein a mass ratio [(B)/(C)] of the component (B) to the component (C) is 0.01 to 1.2. A dishwashing detergent composition according to claim 1 or 2, which further comprises an enzyme. The dishwashing detergent composition according to claim 1 or 2, which further comprises a structural unit derived from a carboxylic acid having a carbon number of 3 to 6 having a reactive unsaturated group or a salt thereof (d-1) The copolymer (D) of the structural unit of the olefin (d-2) having 2 to 12 carbon atoms, and the content of the component (D) is 1 to 30% by mass. The dishwashing detergent composition according to claim 1 or 2, wherein the 0.1% by mass aqueous solution of the dishwashing detergent composition has a pH of 9 to 13 at 25 °C. A dishwashing detergent composition according to claim 1 or 2, which is used in an automatic tableware cleaning machine. A cleaning method of the tableware, wherein the cleaning water having a concentration of the cleaning agent composition of the dishware according to any one of claims 1 to 14 is 0.02 to 0.4% by mass in contact with the object to be cleaned attached to the tableware. A method for cleaning a tableware comprising a compound (A) represented by the following formula (1), an ester type nonionic surfactant (B) having a carbon number of 16 to 18 and an alcohol, and a base The dishwashing detergent composition of the agent (C) is in contact with the tableware, and the content of the component (A) in the total of the components (A), (B) and (C) is 0.1 to 60% by mass, and the above (B) The content of the component is 0.1 to 40% by mass, and the content of the component (C) is 5 to 99.8 mass%. (In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, an alkanolammonium, and an alkylammonium).