Liquid detergent composition for dishwashers

Abstract

To provide a liquid detergent composition for dishwasher, which, even when stored for a long period of time, hardly generates problems of reattachment of stains removed and water spots formed on a surface of tableware and the like and which can suppress deterioration of a scent.SOLUTION: There is provided a liquid detergent composition for dishwasher, comprising (A) Component: an anionic surfactant, (B) component: one or more kinds selected from (B1) component which is phenylboronic acid or a derivative thereof and (B2) component which is isothiazolinone or a derivative thereof, and (C) component: a chelating agent, and (D) component: an enzyme including amylase, where a content of the (A) component relative to total mass of the liquid detergent composition for dishwasher is 0.1 to 10 mass% and a content of the (B) component relative to the total mass of the liquid detergent composition for dishwasher is 0.0001 to 0.016 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a liquid detergent composition for dishwashers. [Background technology]

[0002] In recent years, dishwashers have become widespread not only in kitchens of hotels, restaurants, and school lunch centers, but also in ordinary households, for washing dishes, cooking utensils, and other items to be washed. Generally, special detergents (dishwasher detergent compositions) are used for washing dishes in dishwashers.

[0003] Liquid detergent compositions used for dishwashers require high cleaning power against complex stains, such as a mixture of oil and starch. Therefore, enzymes such as protease and amylase are often added to improve cleaning power. It is known that the storage stability of proteases, among the enzymes incorporated into liquid detergent compositions, can be improved by incorporating phenylboronic acid or its derivatives (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-222882 [Patent Document 2] Special Publication No. 2014-523474 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, the liquid detergent compositions for dishwashers described in Patent Documents 1 and 2 were prone to problems such as the re-adhesion of removed dirt and the formation of water spots on the surface of dishes when stored for extended periods. In addition, the fragrance sometimes deteriorated, resulting in the development of an unpleasant odor. In view of the above circumstances, the present invention aims to provide a liquid detergent composition for dishwashers that, even when stored for a long period of time, is less likely to cause problems such as the re-adhesion of removed dirt or the formation of water spots on the surface of tableware, and also suppresses deterioration of fragrance. [Means for solving the problem]

[0006] To achieve the above objectives, the present invention employs the following configuration. [1](A)Component:Anionic surfactant, (B) Component: One or more selected from Component (B1), which is phenylboronic acid or a derivative thereof represented by the following formula (b1), and Component (B2), which is isothiazolinone or a derivative thereof represented by the following formula (b2) or the following formula (b3), (C) Ingredients: Chelating agent and, (D) Components: A liquid dishwasher detergent composition containing an enzyme including amylase,

[0007] [ka]

[0008] (However, in equation (b1), R 1 ~R 3 (These are selected from a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a chlorine atom, a fluorine atom, -OH, -SCH3, -NH2, and -C(=O)H, and may be the same or different from each other.)

[0009] [ka]

[0010] (However, in equation (b3), R 4 R is one of the hydrogen atoms and a hydrocarbon group having 1 to 8 carbon atoms, 5 R is one of the following selected from a hydrogen atom, -CH3, a chlorine atom, a bromine atom, and -NH2, 6is any one selected from a hydrogen atom, -CH3, a chlorine atom, and -CH2NH2, and R 4 ~R 6 may be the same as each other. ) The content of the component (A) is 0.1 to 10% by mass with respect to the total mass of the liquid detergent composition for dishwashers, and the content of the component (B) is 0.0001 to 0.016% by mass with respect to the total mass of the liquid detergent composition for dishwashers. A liquid detergent composition for dishwashers.

[0011] [2] The content of the component (C) is 10 to 20% by mass with respect to the total mass of the liquid detergent composition for dishwashers. The liquid detergent composition for dishwashers according to [1]. [3] The ratio [(C) / (A)] of the mass of the component (C) to the mass of the component (A) is 1 to 200. The liquid detergent composition for dishwashers according to [1] or [2]. [4] The ratio [(A) / (B)] of the mass of the component (A) to the mass of the component (B) is 10 to 100,000. The liquid detergent composition for dishwashers according to any one of [1] to [3]. [5] The component (A) is one or more anionic surfactants selected from sulfonic acids or their salts and sulfuric esters or their salts. The liquid detergent composition for dishwashers according to any one of [1] to [4]. [6] The pH is 7 to 9. The liquid detergent composition for dishwashers according to any one of [1] to [5]. [Effects of the Invention]

[0012] The liquid detergent composition for dishwashers of the present invention is less likely to cause reattachment of removed dirt or problems with water droplet marks (water spots) formed on the surface of dishes and the like even when stored for a long time, and can also suppress the deterioration of the fragrance. [Embodiments for Carrying Out the Invention]

[0013] The liquid detergent composition for dishwashers of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") is a liquid detergent composition containing components (A), (B), (C), and (D) described below. The following descriptions of constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments.

[0014] In this specification, numerical ranges represented using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. (A) The content of component is given in the form of salt. The content of components (B) and (C) is given as the content in the form of acid. That is, for components (B) and (C) when they form a salt, the content is given as an acid equivalent based on the molecular weight when the cations are replaced with protons. (D) The content of component is the content as an enzyme preparation.

[0015] <(A) component> Component (A) is an anionic surfactant. Component (A) may be used alone, or two or more may be used in appropriate combinations.

[0016] Component (A) is preferably an anionic surfactant (excluding higher fatty acids or their salts) having an alkyl group with 8 to 18 carbon atoms or an alkenyl group with 8 to 18 carbon atoms. C8 to 18 alkyl groups are particularly preferred. The higher fatty acids or their salts are so-called soaps. The alkyl group or alkenyl group may be linear or branched. (A) Examples of components include sulfonic acids, sulfate esters, carboxylic acids, phosphate esters, and salts thereof.

[0017] Examples of sulfonic acids or their salts include alkylbenzene sulfonic acid, alkyl sulfuric acid, polyoxyalkylene sulfuric acid, alkane sulfonic acid, α-olefin sulfonic acid, α-sulfo fatty acid, α-sulfo fatty acid alkyl ester, alkyl sulfosuccinic acid, dialkyl sulfosuccinic acid, and salts thereof.

[0018] Examples of sulfate esters or their salts include alkyl sulfate esters, alkenyl sulfate esters, polyoxyalkylene alkyl ether sulfate esters, polyoxyalkylene alkenyl ether sulfate esters, and salts thereof. Examples of carboxylic acids or their salts include alkyl ether carboxylic acids, amide ether carboxylic acids, sulfosuccinic acid, and their salts, as well as amino acid-based anionic surfactants. Examples of phosphate esters or their salts include alkyl phosphate esters, alkyl ether phosphate esters, and salts thereof.

[0019] Examples of component (A) in salt form include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; alkanolamine salts such as monoethanolamine salt (monoethanolammonium), diethanolamine salt (diethanolammonium), and triethanolamine salt (triethanolammonium); and ammonium salts.

[0020] Among the above, as component (A), sulfonic acid or its salts, sulfate ester salts or their salts are preferred, and sulfonic acid or its salts are particularly preferred, because they have good cleaning power against oil stains and are easy to ensure low foaming. Among sulfonic acids or their salts, one or more selected from the group consisting of alkanesulfonic acid, alkylbenzenesulfonic acid, dialkylsulfosuccinic acid, monoalkylsulfosuccinic acid, and their salts are preferred because they have particularly high cleaning power against oil stains. Alkanesulfonic acid or its salt, alkylbenzenesulfonic acid or its salt are more preferred, alkanesulfonic acid or its salt, linear alkylbenzenesulfonic acid or its salt are particularly preferred, and alkanesulfonic acid or its salt is especially preferred.

[0021] Examples of alkanesulfonic acids or their salts include alkanesulfonic acids having 10 to 20 carbon atoms or their salts, with alkanesulfonic acids having 14 to 17 carbon atoms or their salts being preferred, and secondary alkanesulfonic acids (SAS) having 14 to 17 carbon atoms or their salts being particularly preferred. Examples of SAS salts include sodium salts.

[0022] Linear alkylbenzenesulfonic acid or its salts are preferably linear alkylbenzenesulfonic acid or its salts having 8 to 16 carbon atoms in the linear alkyl group, and linear alkylbenzenesulfonic acid (LAS) or its salts having 10 to 14 carbon atoms in the linear alkyl group are particularly preferred. Examples of LAS salts include sodium salts and potassium salts. As monoalkyl sulfosuccinic acid or its salt, sodium monoalkyl sulfosuccinate having 10 to 18 carbon atoms is preferred.

[0023] In the liquid detergent composition, the content of component (A) is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the liquid detergent composition. (A) When the content of component is within the above range, an effect of preventing the re-adhesion of fine particles is obtained. (A) When the content of component is below the above upper limit, an effect of preventing deterioration of the fragrance is obtained.

[0024] <(B) component> Component (B) is one or more selected from the components (B1) and (B2) listed below. (Component (B) may be used alone or in appropriate combination of two or more thereof.)

[0025] [Component (B1)] (Component (B1) is phenylboronic acid represented by the following formula (b1) or its derivative.) (Component (B1) may be used alone or in appropriate combination of two or more thereof.)

[0026] [Chemical formula]

[0027] However, in formula (b1), R 1 ~R 3 is any one selected from a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a chlorine atom, a fluorine atom, -OH, -SCH3, -NH2, and -C(=O)H, and they may be the same or different from each other.) R 1 ~R 3 When R

[0028] ~R 1 ~R 3 is a hydrocarbon group having 1 to 3 carbon atoms, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be either linear or branched.)[[ID=3,9]]

[0029] Specific examples of component (B1) include phenylboronic acid, 4-formylphenylboronic acid (4FPBA), 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 4-isopropylphenylboronic acid, 3-chlorophenylboronic acid, 3-fluorophenylboronic acid, 3-hydroxyphenylboronic acid, 4-hydroxyphenylboronic acid, 4-(methylthio)phenylboronic acid, 4-vinylphenylboronic acid, 3-aminophenylboronic acid.) In particular, from the viewpoint of preventing the re-adhesion of fine particles during long-term use, preventing the formation of water spots, and preventing deterioration of the fragrance, 4-formylphenylboronic acid (4FPBA), 2-methylphenylboronic acid, 4-(methylthio)phenylboronic acid, and phenylboronic acid are preferred, with 4-formylphenylboronic acid (4FPBA) being especially preferred.

[0030] [(B2) component] Component (B2) is isothiazolinone or a derivative thereof represented by the following formula (b2) or formula (b3). (B2) Component may be used alone or in combination of two or more as appropriate.

[0031] [ka]

[0032] However, in equation (b3), R 4 R is one of the hydrogen atoms and a hydrocarbon group having 1 to 8 carbon atoms, 5 R is one of the following selected from a hydrogen atom, -CH3, a chlorine atom, a bromine atom, and -NH2, 6 R is one of the following: hydrogen atom, -CH3, chlorine atom, and -CH2NH2. 4 ~R 6 These may be identical to each other.

[0033] The component (B2) represented by the above formula (b2) is 1,2-benzoisothiazole-3-one (BIT). Specific examples of component (B2) represented by formula (b3) include methylisothiazolinone (MIT), chloromethylisothiazolinone (CMIT), octylisothiazolinone (OIT), and dichlorooctylisothiazolinone (DCOIT). The component (B2) is preferably 1,2-benzoisothiazol-3-one (BIT) or methylisothiazolinone (MIT), with 1,2-benzoisothiazol-3-one (BIT) being particularly preferred.

[0034] In the liquid detergent composition, the content of component (B) is 0.0001 to 0.016% by mass, preferably 0.005 to 0.014% by mass, and more preferably 0.0075 to 0.012% by mass, relative to the total mass of the liquid detergent composition. (B) When the content of component (B) is above the lower limit, an effect of preventing the re-adhesion of fine particles and preventing the formation of water spots can be obtained. (B) When the content of component (B) is within the above range, an effect of preventing deterioration of the fragrance can be obtained.

[0035] <(C) component> Component (C) is a chelating agent. Component (C) may be used alone or in combination of two or more as appropriate. (C) As component, any of the common chelating agents used in dishwasher detergents can be used, and either low molecular weight chelating agents with a molecular weight of 800 or less or high molecular weight chelating agents with a molecular weight of 1000 or more may be used.

[0036] Examples of low molecular weight chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N,N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamic acid diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2'-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphate, or salts thereof.

[0037] For polymer chelating agents, those with a weight-average molecular weight of 1000 or more are preferred. Examples of polymer chelating agents include polyacrylic acid or its salts, polymethacrylic acid or its salts, acrylic acid-maleic acid copolymer or its salts, methacrylic acid-maleic acid copolymer or its salts, ethylene-maleic acid copolymer or its salts, etc. Among these, acrylic acid-maleic acid copolymer or its salts are preferred as polymer chelating agents. The copolymerization ratio (molar ratio) of acrylic acid and maleic acid is preferably acrylic acid / maleic acid = 75 / 25 to 50 / 50, and the preferred weight-average molecular weight is 10,000 to 100,000. The weight-average molecular weight for polymer chelating agents is the value measured by gel permeation chromatography using sodium polyacrylate as the standard substance.

[0038] As the salt constituting the chelating agent, alkali metal salts are preferred, with sodium salts and potassium salts being more preferred. Among these, citric acid or its salts are particularly preferred from the viewpoint of preventing water spot formation and preventing deterioration of aroma.

[0039] In the liquid detergent composition, the content of component (C) is preferably 10 to 20% by mass, and more preferably 10 to 15% by mass, relative to the total mass of the liquid detergent composition. (C) When the content of component C is above the lower limit above, the water spot formation prevention effect is enhanced. (C) When the content of component C is below the upper limit above, the fragrance deterioration prevention effect is enhanced. <(D) component> Component (D) is an enzyme. Component (D) may be used alone or in combination of two or more as appropriate. Component (D) contains at least amylase. The enzymes other than amylase are not particularly limited, and any of the common enzymes used in liquid detergent compositions for dishwashers can be used. Examples include protease, lipase, cellulase, glucanase, etc. Component (D) may consist of amylase alone, but from the viewpoint of comprehensive stain removal, it is preferable to use other enzymes, especially proteases, in combination.

[0040] In the liquid detergent composition, the content of component (D) is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.1 to 1% by mass, based on the total mass of the liquid detergent composition. (D) When the content of component (D) is above the lower limit, the effect of preventing re-adhesion of fine particles and the effect of preventing water spot formation are enhanced. (D) When the content of component (D) is below the upper limit, the effect of preventing deterioration of fragrance is enhanced.

[0041] The ratio of the mass of component (C) to the mass of component (A) [(C) / (A)] is preferably 1 to 200, and more preferably 20 to 30. When the ratio [(C) / (A)] is above the lower limit, the effect of preventing deterioration of the aroma is enhanced. When the ratio [(C) / (A)] is below the upper limit, the effect of preventing the re-adhesion of fine particles is enhanced.

[0042] The ratio of the mass of component (A) to the mass of component (B) [(A) / (B)] is preferably 10 to 100,000, more preferably 20 to 1,000, and even more preferably 40 to 100. When the ratio [(A) / (B)] is above the lower limit, the effect of preventing the re-adhesion of fine particles is enhanced. When the ratio [(A) / (B)] is below the upper limit, the effect of preventing deterioration of the aroma is enhanced.

[0043] <medium> The liquid detergent composition of the present invention contains water as a medium. The water content in the liquid detergent composition is preferably 60 to 99% by mass, and more preferably 70 to 95% by mass, based on the total mass of the liquid detergent composition. When the water content is within the above range, the liquid detergent composition is easier to prepare.

[0044] <Optional ingredients> The liquid detergent composition of the present invention may contain any component commonly found in detergents for washing dishes, as long as it does not contradict the purpose of the present invention. For example, other substances commonly used in dishwasher detergent compositions, such as surfactants other than component (A), carbonates, defoamers, thickeners, plant extracts, oil absorbents, dish protectants, colorants, hydrotropes, antioxidants, pH adjusters, fragrances, and bleaches, may be used.

[0045] [Other surfactants] Other surfactants include amideamine-type surfactants such as dimethylaminopropyl stearate. If other surfactants are included, the content of the other surfactants in the liquid detergent composition is preferably 0.1 to 5% by mass, and more preferably 0.1 to 2% by mass, based on the total mass of the liquid detergent composition.

[0046] [Carbonates, etc.] Examples of carbonates include carbonic acid, carbonates, bicarbonates, and bicarbonate salts. Carbonates are carbonate ions (CO3 2- This refers to all compounds containing carbonate. Examples of carbonates include alkali metal salts of carbonate such as sodium carbonate and potassium carbonate; alkaline earth metal salts of carbonate such as calcium carbonate, magnesium carbonate, and barium carbonate; and ammonium carbonate. Bicarbonates are composed of bicarbonate ions (HCO3). - This refers to all compounds containing ). Examples of bicarbonates include alkali metal salts of bicarbonate such as sodium bicarbonate and potassium bicarbonate; alkaline earth metal salts of bicarbonate such as calcium bicarbonate and magnesium bicarbonate; and ammonium bicarbonate. If carbonates or the like are included, their content is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass, relative to the total mass of the liquid detergent composition.

[0047] [Antifoaming agent] The type of defoaming agent is not particularly limited, and any of the common defoaming agents used in liquid detergent compositions for dishwashers can be used. A silicone-based defoaming agent is preferred.

[0048] The silicone-based defoaming agent is not particularly limited and can be an oil type, compound type, self-emulsifying compound type, or powder type. Examples include dispersions or emulsions of polyorganosiloxane oil or resin such as polydimethylsiloxane, and combinations of polyorganosiloxane, which is chemically adsorbed or melted onto silica, and silica particles. For example, FS Antifoam 1266 (manufactured by Dow Chemical) and FS Antifoam 93 (manufactured by Dow Chemical) are preferred.

[0049] The defoaming agent may be used alone, or two or more types may be used in appropriate combinations. If an antifoaming agent is included, its content is preferably 0.01 to 2% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the liquid detergent composition. If the antifoaming agent content is above the lower limit, it is easier to improve the low-foaming properties. If the antifoaming agent content is below the upper limit, it is easier to improve the storage stability.

[0050] [Thickener] Examples of thickening agents include water-soluble polymers such as pectin, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid esters, acrylic acid polymers, methacrylic acid polymers, xanthan gum, guar gum, gelatin, sodium alginate, acacia gum, and starch; and water-swellable clay minerals such as smectite. Smectite can be either natural or synthetic.

[0051] The thickening agent may be used alone, or two or more types may be used in appropriate combinations. If a thickening agent is included, its content is preferably 0.1 to 20% by mass relative to the total mass of the liquid detergent composition. When the content of the thickening agent is within this range, it can adequately exhibit performance in preventing deterioration and alteration of the fragrance.

[0052] [Hydrotrope] Examples of hydrotropes include polyols, aromatic carboxylic acids, or aromatic sulfonic acids. For example, ethylene glycol, propylene glycol, sodium cumenesulfonate, potassium cumenesulfonate, ammonium cumenesulfonate, sodium xylenesulfonate, potassium xylenesulfonate, ammonium xylenesulfonate, sodium toluenesulfonate, potassium toluenesulfonate, ammonium toluenesulfonate, and sodium benzoate.

[0053] Hydrotropes may be used individually or in combination of two or more types as appropriate. If a hydrotrope is included, its content is preferably 1 to 10% by mass relative to the total mass of the liquid detergent composition.

[0054] [pH adjuster] Examples of pH adjusting agents include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine; inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as acetic acid and oxalic acid. From the standpoint of storage stability and cost of the liquid detergent composition, potassium hydroxide and sodium hydroxide are preferred among inorganic bases, and potassium hydroxide is particularly preferred from the viewpoint of storage stability and liquid fluidity. Among organic bases, monoethanolamine is preferred. pH adjusting agents may be used individually or in appropriate combinations of two or more types.

[0055] <ph> The pH (at 25°C) of the liquid detergent composition is preferably 5 to 11, and more preferably 7 to 9. If the pH of the liquid detergent composition is above the lower limit, it becomes easier to enhance its cleaning power against complex stains. If the pH of the liquid detergent composition is below the upper limit, it becomes easier to prevent deterioration or alteration of the fragrance. In this specification, the pH (25°C) of the liquid detergent composition is the value measured by a method conforming to JIS Z 8802:2011 "Method for measuring pH".

[0056] <Viscosity> The viscosity of the liquid detergent composition at 25°C is preferably 10 to 2000 mPa·s, and more preferably 100 to 1000 mPa·s. In this specification, the viscosity of the liquid detergent composition at 25°C is the value measured by a method conforming to the viscosity measurement method No. 2 of the general test methods of the Quasi-drug Raw Materials Standards 2006. Specifically, it is the value measured using a bismetron viscometer under the conditions of rotor No. 2 to No. 4, rotation speed: 6 rpm, and 120 seconds.

[0057] <Manufacturing method> Liquid detergent compositions can be manufactured in accordance with conventionally known methods for manufacturing liquid detergent compositions. For example, components (A) and (C), along with optional components as needed, are dissolved in a portion of water, the pH is adjusted to around 7 with a pH adjuster as needed, then components (B) and (D), along with optional components as needed, the pH is further adjusted with a pH adjuster as needed, and finally the remaining water is added to prepare the composition.

[0058] <How to use> The liquid detergent composition can be used in dishwashers and should be used according to the model of the dishwasher and the degree of soiling of the dishes. A method for cleaning objects using a dishwasher detergent composition in a dishwasher includes a method that includes both washing and rinsing steps.

[0059] As a washing method, for example, there is a method that includes the steps of: washing the objects to be washed while raising the temperature of a washing solution prepared by introducing tap water at room temperature (preferably around 5 to 30°C) into the dishwasher chamber to a predetermined washing temperature (temperature of the washing solution circulating during washing) (hereinafter referred to as the "washing step"); rinsing the washed objects with tap water at room temperature after washing (hereinafter referred to as the "rinsing (1) step"); and further rinsing the objects after the rinsing (1) step while raising the temperature of tap water at room temperature to preferably 70 to 75°C at a rate of 2 to 3°C / minute (hereinafter referred to as the "rinsing (2) step"). The washing time in the washing step is preferably 10 to 40 minutes.

[0060] In a typical standard cycle, the washing temperature during the washing process is around 55-65°C, and the heating rate is around 2-3°C / minute. In a low-temperature cycle, for example, the washing temperature is around 35-45°C, and the heating rate is around 1°C / minute. In all courses, the amount of dishwasher detergent composition used per wash is preferably 2 to 9 g per approximately 3 liters of tap water.

[0061] <Effects and Effects> The liquid detergent composition described above is less likely to cause problems such as the re-adhesion of removed dirt or the formation of water spots on the surface of tableware, even when stored for a long period of time, and it also suppresses deterioration of the fragrance. If starch stains remain on tableware, their stickiness makes it easier for fine particles to adhere and for water spots to form. On the other hand, by combining components (A) to (D) within an appropriate range in this invention, starch stains can be thoroughly cleaned, and the above problem can be solved.

[0062] <Container-packaged liquid dishwasher detergent product> By housing the liquid detergent composition in a container, it can be made into a liquid detergent article for dishwashers in a container. The container is manufactured using, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, or synthetic resins that are mixtures thereof as raw material resins, by blow molding or injection molding these raw material resins. The shape of the container is not particularly limited and may be a round bottle, a square bottle, or a pouch. [Examples]

[0063] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials used in this embodiment are as shown in the <Raw Materials Used> section below.

[0064] <Raw materials used> [(A) component] A-1: LAS, linear alkyl (12-14 carbon atoms) sodium benzenesulfonate (product name: Lypon LS-250, Lion Specialty Chemicals Co., Ltd.). A-2: SAS, sodium secondary alkanesulfonate (product name: HOSTAPUR SAS 30AJ, Clariant Japan Co., Ltd.). A-3: Sodium monoalkyl sulfosuccinate, disodium polyoxyethylene monoalkyl (12-14 carbon atoms) sulfosuccinate (product name: Kohacool L-400, Toho Chemical Co., Ltd.). A-4: C12AS, linear alkyl (12 carbon atoms) sulfate sodium (product name: Sanol LM-1130, Lion Specialty Chemicals Co., Ltd.). A-5: AES, polyoxyethylene (1) alkyl (12 carbon atoms) ether sulfate sodium (product name: Sanol LMT-1430, Lion Specialty Chemicals Co., Ltd.).

[0065] [(B) Component] B-1: 4FPBA, 4-formylphenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-2: 2-Methylphenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-3: 4-(methylthio)phenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-4: 3-Chlorophenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-5: 3-Hydroxyphenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-6: 3-aminophenylboronic acid (Kanto Chemical Co., Ltd., reagent). B-7: Phenylboronic acid (Tokyo Chemical Industries, Ltd., reagent). B-8: BIT, 1,2-benzoisothiazole-3-one (Tokyo Chemical Industries, Ltd., reagent). B-9: MIT, Methylisothiazolinone (Kanto Chemical Co., Ltd., Reagent).

[0066] [(C) component] C-1: Citric acid (product name: Purified citric acid (anhydrous), Fuso Chemical Industries Co., Ltd.). C-2: MA, maleic acid / acrylic acid copolymer sodium salt (product name: Aquaric TL400, molar ratio of acrylic acid / maleic acid = 60 / 40, weight-average molecular weight 50000). C-3: MGDA, trisodium methylglycinediacetate (trade name: Trilon M Compactate, BASF). C-4: GLDA, tetrasodium glutamate diacetate (product name: Kirest CMG-40, Kirest Co., Ltd.). C-5: EDTA, ethylenediaminetetraacetic acid (Tokyo Chemical Industries, Ltd., reagent).

[0067] [(D1) component] D-1: Amylase (product name: Achieve alpha 100L, Novozymes). D-2: Protease (product name: Savinase Ultra 16XL, Novozymes).

[0068] [Hydrotrope] • Propylene glycol (Fujifilm Wako Pure Chemical Corporation, reagent). • Sodium benzoate (Fujifilm Wako Pure Chemical Corporation, reagent). • Stabilizer: Calcium chloride (Fujifilm Wako Pure Chemical Corporation, reagent) • Thickening agent: Xanthan gum (product name KELZAN T, Kelco)

[0069] [pH adjuster] Sodium hydroxide (48% sodium hydroxide, AGC Inc.). Sulfuric acid (Kanto Chemical Co., Ltd., reagent).

[0070] <Examples 1-47, Comparative Examples 1-9> According to the proportions (in mass%) shown in Tables 1-7, components (A), (B), (C), and (D), along with other components, were dissolved in water as the medium, and the pH was adjusted with a pH adjuster to prepare 0.8 kg of each example of the liquid detergent composition. Of Examples 1 to 47, Examples 1 to 14 and 17 to 47 are reference examples.

[0071] Specifically, water was added to a 1L beaker (12cm in diameter) in an amount equivalent to approximately 60% by mass of the entire liquid detergent composition. This beaker was equipped with a HEIDON FBL1200 Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.) agitator with a four-blade paddle that is 7.5 cm in diameter, 1.5 cm wide, and angled at 45 degrees. Then, while stirring at a rotation speed of 400-900 rpm to prevent the contents from splashing, xanthan gum was added to the water in an amount equal to 0.3% by mass of the total liquid detergent composition and stirred. After that, components (A) and (C) were mixed and dissolved, and a pH adjuster (sodium hydroxide or sulfuric acid) was added to adjust the pH to around 7.

[0072] Next, propylene glycol and sodium benzoate were added in amounts equal to 5.0% by mass of the total liquid detergent composition, and calcium chloride was added in amounts equal to 0.3% by mass of the total liquid detergent composition, while stirring with the stirrer at a rotation speed of 650 rpm. After cooling to room temperature, the pH was adjusted to 7.0 with a pH adjuster (sodium hydroxide or sulfuric acid), and components (B) and (D) were added. After the addition was complete, the mixture was stirred for 5 minutes, and the remaining water was added so that the total liquid detergent composition was 100% by mass. The mixture was then stirred with the stirrer at a rotation speed of 650 rpm for 1 minute to obtain the liquid detergent compositions of each example. The pH (25°C) was measured using a glass electrode pH meter (HM-30G, manufactured by Toa DKK Co., Ltd.) on a liquid detergent composition adjusted to 25°C.

[0073] <Evaluation Method> [Preparation of contaminated serving dishes] Six large ceramic plates (115mm radius, 25mm height) were used to create a mixture of contaminated food as follows: 30g of a mixture of 200g of instant curry, one large egg, and 150g of rice was placed on each plate. After uniformly contaminating the plate surface, the mixture was discarded. However, about 10 grains of rice were left on each plate, crushed with a spoon, and stuck to the plate surface. For the retort curry, we used Bon Curry Gold Spicy, manufactured by Otsuka Foods. For the rice, we used a type of locally distributed rice equivalent to Koshihikari, with the rice-to-water ratio being the standard for a rice cooker, and the rice was used within 12 hours of cooking.

[0074] [Long term storage] Assuming long-term storage indoors during the summer, 40g of each example's liquid detergent composition was placed in a 50mL glass bottle, sealed, and stored at 35°C for one month to obtain the long-term stored liquid detergent compositions for each example.

[0075] [Prevention of re-adhesion of fine particles] Six contaminated large plates prepared as described above, three uncontaminated teacups (65mm in diameter, 80mm in height, 35mm in inner diameter of the base, 6mm in depth), and three uncontaminated glasses (60mm in diameter, 110mm in height) were placed in a dishwasher (manufactured by Panasonic Corporation, model NP-45MD8S) in the designated area according to the instruction manual of the automatic dishwasher. 8g of the long-term stored liquid detergent composition for each example was added, and the dishwasher was washed and dried using the standard course. The contents of the standard course are shown below.

[0076] Standard course: After adding the liquid detergent composition to the dishwasher, 3 liters of tap water at approximately 5°C are introduced into the machine to prepare the detergent solution. The dishwasher is then heated to 40°C at a rate of 2-3°C / min for 20 minutes, and the detergent solution is drained. Next, fresh tap water is introduced, and the rinsing (2 minutes / rinse) and draining cycle is repeated three times. After draining, fresh tap water is introduced, and one final rinse (20 minutes) is performed while the temperature is heated to 70°C at a rate of 2-3°C / min. After draining, the dishes are dried by circulating warm air.

[0077] After drying, three teacups and three glasses were removed from the dishwasher and visually inspected. The performance in preventing the re-adhesion of particulate matter was evaluated based on the following evaluation criteria. For each sample, the standard cleaning and drying process described above, followed by visual inspection, was performed three times. The average score from the three tests is shown in Tables 1-7. An average score of 3 points or higher was considered a passing grade.

[0078] (Evaluation Criteria) 6 points: No re-adhesion of fine particles was observed on any of the teacups or glasses. 5 points: One or fewer teacups and glasses in total showed signs of re-adhesion of fine particles. 4 points: A total of 2 or fewer teacups and glasses showed signs of re-adhesion of fine particles. 3 points: A total of 3 or fewer teacups and glasses were found to have re-adhesion of fine particles. 2 points: A total of 4 or fewer teacups and glasses were found to have re-adhesion of fine particles. 1 point: A total of 5 or more teacups and glasses showing signs of re-adhesion of fine particles.

[0079] [Prevents water spot formation] Six contaminated large plates prepared as described above and six uncontaminated glasses (60 mm in diameter, 110 mm in height) were placed in a dishwasher (manufactured by Panasonic Corporation, model NP-45MD8S) in the designated area according to the instruction manual of the automatic dishwasher. 8 g of the long-term stored liquid detergent composition for each example was added, and the dishwasher was washed and dried using the standard course.

[0080] After drying, six glasses were visually inspected after being removed from the dishwasher, and the total number of water spots formed on the six glasses was determined. The water spot prevention performance was then evaluated based on the following evaluation criteria. (Note: 1-100 mm) 2 Each white inversion was counted as a single water spot, and if multiple water spots overlapped, they were counted as a single water spot. For each sample, the standard cleaning and drying process described above, followed by visual inspection, was performed three times. The average score from the three tests is shown in Tables 1-7. An average score of 3 points or higher was considered a passing grade.

[0081] (Evaluation Criteria) 6 points: The total number of water spots is 5 or less. 5 points: The total number of water spots is between 6 and 10. 4 points: The total number of water spots is between 11 and 20. 3 points: The total number of water spots is between 21 and 30. 2 points: The total number of water spots is 31-40. 1 point: The total number of water spots is 41 or more.

[0082] [Odor suppression] 50g of the liquid detergent composition immediately after preparation was placed in a 50mL glass bottle, sealed, and stored at 35°C for one month. The bottle was then cooled to 25°C, and a sensory evaluation was conducted by three odor specialists on a panel, based on the evaluation criteria below. The liquid detergent composition immediately after preparation was used as the reference sample. Tables 1-7 show the average score given by three odor specialists for each case. An average score of 2 points or higher was considered a passing grade.

[0083] (Evaluation Criteria) 5 points: No change in aroma was detected at all, and its distinctive characteristics remained unchanged. 4 points: I noticed a slight change in the aroma, but the distinctive characteristics remain unchanged. 3 points: I noticed a slight change in the aroma and a minor shift in its characteristics, but it doesn't affect its usability. Points 2: I noticed a change in the aroma and a shift in its characteristics, but it was not unpleasant. 1 point: The fragrance has clearly changed, its distinctive characteristics have been altered, and it is unpleasant.

[0084] [Table 1]

[0085] [Table 2]

[0086] [Table 3]

[0087] [Table 4]

[0088] [Table 5]

[0089] [Table 6]

[0090] [Table 7]

[0091] As shown in Tables 1-6, Examples 1-47 all demonstrated excellent effects in preventing the re-adhesion of fine particles, preventing water spot formation, and suppressing unpleasant odors. In contrast, as shown in Table 7, Comparative Examples 1 to 9 were inferior in at least one evaluation item.< / ph>

Claims

1. (A) Ingredients: Anionic surfactant, (B) Component: One or more selected from component (B2), which is isothiazolinone or a derivative thereof represented by the following formula (b2) or formula (b3), (C) Ingredients: Chelating agent and (D) Component: A liquid dishwasher detergent composition containing an enzyme including amylase, 【Chemistry 1】 (However, in formula (b3), R ４ is either a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ５ is either a hydrogen atom, -CH ３ , a chlorine atom, a bromine atom, or -NH ２ , and R ６ is either a hydrogen atom, -CH ３ , a chlorine atom, or -CH ２ NH ２ , and R ４ to R ６ may be the same as each other.) A liquid dishwasher detergent composition in which the content of component (A) is 0.1 to 10% by mass relative to the total mass of the liquid dishwasher detergent composition, the content of component (B) is 0.0001 to 0.016% by mass relative to the total mass of the liquid dishwasher detergent composition, and the ratio of the mass of component (A) to the mass of component (B) [(A) / (B)] is 10 to 100,000.

2. The dishwasher liquid detergent composition according to claim 1, wherein the content of component (C) is 10 to 20% by mass relative to the total mass of the dishwasher liquid detergent composition.

3. The liquid detergent composition for dishwashers according to claim 1 or 2, wherein the ratio of the mass of component (C) to the mass of component (A) [(C) / (A)] is 1 to 200.

4. The liquid detergent composition for dishwashers according to claim 1 or 2, wherein component (A) is one or more anionic surfactants selected from sulfonic acid or a salt thereof, and sulfate ester or a salt thereof.

5. A liquid detergent composition for dishwashers according to claim 1 or 2, wherein the pH is 7 to 9.

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