Liquid dishwasher detergent composition

Abstract

To provide a liquid detergent composition for dishwashers which is excellent in staining-prevention properties and filter clogging prevention properties.SOLUTION: A liquid detergent composition for dishwashers includes a component (A): at least one selected from the group consisting of sulfurous acid, sulfurous acid salt, hydrogen sulfite, and hydrogen sulfite salt, a component (B): at least one selected from the group consisting of cyclic monoterpene alcohol and non-cyclic monoterpene alcohol, a component (C): an acidic polysaccharide, and a component (D): anion surfactant. A mass ratio represented by the component (A) / the component (B) is 0.00005 to 200. A mass ratio represented by the component (C) / the component (B) is 0.01 to 1000.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid dishwasher detergent composition. [Background technology]

[0002] Known liquid detergent compositions for dishwashers include those containing an anionic surfactant and an acidic polysaccharide (Patent Document 1), those containing a surfactant and a cyclic terpene or an acyclic terpene (Patent Document 2), and those containing a surfactant, a carbonate or bicarbonate, and a sulfite or bicarbonate (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-10190 [Patent Document 2] Japanese Patent Application Publication No. 2019-218515 [Patent Document 3] Patent Publication No. 2021-91838 Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, objects to be cleaned, such as tableware, may become discolored when stains that easily discolor (colored stains) such as curry, tomato juice, meat sauce, etc. are attached to the objects to be cleaned. Therefore, a detergent composition is required to have the ability to prevent the objects to be cleaned from being discolored by colored stains (stain prevention property). However, conventional liquid detergent compositions for dishwashers do not necessarily have sufficient stain-preventing properties.

[0005] Furthermore, from the viewpoints of storage stability and usability, it is desirable for liquid detergent compositions to have a certain degree of viscosity, and a thickener such as an acidic polysaccharide may be blended in the composition, as described in Patent Document 1. Furthermore, a fragrance may also be blended in the composition to impart a fragrance. In recent years, dishwashers equipped with an automatic detergent dispensing function have come into practical use. Typically, a filter is attached to the detergent tank that contains the liquid detergent composition to prevent foreign matter from entering the dishwasher. However, when a liquid detergent composition containing a thickener or a fragrance is filled into a detergent tank, the thickener may aggregate in the detergent tank or the fragrance may accumulate, causing filter clogging. Conventional liquid detergent compositions for dishwashers do not necessarily have sufficient filter clogging prevention properties.

[0006] An object of the present invention is to provide a liquid detergent composition for dishwashers that is excellent in preventing discoloration and filter clogging. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] Component (A): at least one selected from the group consisting of sulfurous acid, sulfite salts, hydrogen sulfite, and hydrogen sulfite salts; (B) component: at least one selected from the group consisting of cyclic monoterpene alcohols and acyclic monoterpene alcohols; (C) component: acidic polysaccharides, (D) component: anionic surfactant; Contains the mass ratio of the component (A) to the component (B) is 0.00005 to 200; A liquid detergent composition for dishwashers, wherein the mass ratio of the component (C) to the component (B) is 0.01 to 1,000. [2] The liquid dishwasher detergent composition according to [1], further comprising component (E): a chelating agent having a molecular weight of 800 or less. [3] The liquid dishwasher detergent composition according to [1] or [2] above, further comprising component (F): at least one selected from the group consisting of carbonic acid, carbonates, hydrogen carbonates, and hydrogen carbonates. [4] The liquid dishwasher detergent composition according to any one of [1] to [3] above, wherein the component (C) contains xanthan gum. [5] The liquid dishwasher detergent composition according to any one of [1] to [4] above, wherein the component (D) comprises at least one selected from the group consisting of monoalkyl sulfosuccinic acids and monoalkyl sulfosuccinate salts. [6] The liquid dishwasher detergent composition according to any one of [1] to [5], wherein the component (B) comprises at least one selected from the group consisting of linalool, borneol, l-menthol, nerol, geraniol, dihydromyrcenol, 3,7-dimethyl-3-octanol, and citronellol. [Effects of the Invention]

[0008] According to the present invention, a liquid detergent composition for dishwashers that is excellent in preventing discoloration and filter clogging can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. The liquid dishwasher detergent composition of the present invention (hereinafter also simply referred to as "liquid detergent composition") is a composition containing the following components (A), (B), (C), and (D). The liquid detergent composition preferably further contains at least one of the following components (E) and (F). The liquid detergent composition may also contain water. The liquid detergent composition may also contain other components (optional components) other than the components (A), (B), (C), (D), (E), (F), and water, as needed.

[0010] <Component (A)> The component (A) is at least one selected from the group consisting of sulfurous acid, sulfites, hydrogen sulfites, and hydrogen sulfites. When the liquid detergent composition contains the component (A), the coloring prevention properties are improved. In the present invention, "stain prevention property" refers to the ability to prevent staining of objects to be washed, such as tableware, caused by stains (stains) that are easily stained, such as curry, tomato juice, meat sauce, tomato ketchup, tea stains, and coffee.

[0011] Sulfite is a compound of sulfite ions (SO3 2- Examples of sulfites include alkali metal salts of sulfite such as sodium sulfite and potassium sulfite; alkaline earth metal salts of sulfite such as calcium sulfite, magnesium sulfite and barium sulfite; and ammonium sulfite. Bisulfite is a hydrogen sulfite ion (HSO3 - Examples of bisulfites include alkali metal bisulfites such as sodium bisulfite and potassium bisulfite; alkaline earth metal bisulfites such as calcium bisulfite and magnesium bisulfite; and ammonium bisulfite. Of these, sulfites and hydrogen sulfites are preferred as component (A), and from the viewpoint of further improving the coloration prevention properties, sulfites are more preferred, and sodium sulfite is even more preferred. The component (A) may be used alone or in combination of two or more.

[0012] The content of component (A) is preferably 0.00005 to 0.2% by mass, more preferably 0.0005 to 0.05% by mass, based on the total mass of the liquid detergent composition. When the content of component (A) is within the above range, the coloring prevention property is further improved. In particular, when the content of component (A) is equal to or less than the above upper limit, the filter clogging prevention property is further improved.

[0013] <(B) component> Component (B) is at least one selected from the group consisting of cyclic monoterpene alcohols and acyclic monoterpene alcohols. When the liquid detergent composition contains component (B), the ability to prevent filter clogging is improved.

[0014] Examples of cyclic monoterpene alcohols include borneol, 1-menthol, terpinen-4-ol, and α-terpineol. Examples of the acyclic monoterpene alcohols include linalool, nerol, geraniol, dihydromyrcenol, 3,7-dimethyl-3-octanol, citronellol, and lavandulol.

[0015] The ClogP value of component (B) is preferably 5.00 or less, more preferably 4.00 or less, even more preferably 3.70 or less, and particularly preferably 3.40 or less. There is no particular lower limit for the ClogP value of component (B), but it is preferably, for example, 1.00 or more. When the ClogP value of component (B) is equal to or less than the upper limit above, the filter clogging prevention property is further improved.

[0016] The "ClogP value" refers to the 1-octanol / water partition coefficient (P), which represents the ratio of equilibrium concentrations of a chemical substance in 1-octanol and water, expressed in the form of logarithm logP to the base 10. The ClogP value can be determined by the f-value method (hydrophobic fragment constant method) by decomposing the chemical structure of a compound into its constituent elements and integrating the hydrophobic fragment constant f-values ​​of each fragment (see, for example, Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).

[0017] As component (B), from the viewpoint of further improving the anti-clogging properties of the filter, linalool, borneol, l-menthol, nerol, geraniol, dihydromyrcenol, 3,7-dimethyl-3-octanol, and citronellol are preferred, linalool, borneol, l-menthol, nerol, geraniol, and dihydromyrcenol are more preferred, and linalool, borneol, and l-menthol are even more preferred. The component (B) may be used alone or in combination of two or more.

[0018] The content of component (B) is preferably 0.001 to 1 mass %, more preferably 0.01 to 0.5 mass %, based on the total mass of the liquid detergent composition. When the content of component (B) is within the above range, the anti-clogging properties of the filter are further improved.

[0019] The mass ratio of component (A) to component (B) (hereinafter also referred to as "A / B ratio") is 0.00005 to 200, preferably 0.0001 to 100, more preferably 0.001 to 10, and even more preferably 0.01 to 5. When the A / B ratio is within the above range, the coloring prevention property and the filter clogging prevention property are further improved.

[0020] <(C) component> Component (C) is an acidic polysaccharide. When the liquid detergent composition contains the component (C), the anti-clogging properties of the filter are improved. The term "acidic polysaccharide" refers to a saccharide that is composed of two or more monosaccharides and has an acidic functional group that can form a salt with an inorganic cation when dissolved in water. Preferably, the polysaccharide is a water-soluble polymer that dissolves in water, and is a thickening polysaccharide that exhibits viscosity or gelation, particularly in the acidic pH range.

[0021] The monosaccharides that serve as the constituent units of acidic polysaccharides are not particularly limited, but examples include neutral sugars such as glucose, galactose (D- and L-forms), xylose, mannose, rhamnose, fucose, and arabinose; uronic acids such as guluronic acid, iduronic acid, mannuronic acid, glucuronic acid, and galacturonic acid; and amino sugars such as glucosamine and galactosamine. The acidic functional group is not particularly limited, but examples thereof include -COOH (carboxy group), -SO3H (sulfo group), -OSO3H, and -CH2OSO3H. Examples of acidic polysaccharides include xanthan gum, gellan gum, carrageenan, pectin, soybean polysaccharides, alginic acid, gum arabic, karaya gum, tragacanth gum, hyaluronic acid, agaropectin, porphyran, fucoidan (sulfated fucan), and ascophyllan. Among these, xanthan gum and gellan gum are preferred as component (C), with xanthan gum being more preferred, from the viewpoint of further improving the anti-clogging properties of the filter. The component (C) may be used alone or in combination of two or more.

[0022] The content of component (C) is preferably 0.01 to 1 mass %, more preferably 0.05 to 0.75 mass %, based on the total mass of the liquid detergent composition. When the content of component (C) is within the above range, the anti-clogging properties of the filter are further improved.

[0023] The mass ratio of component (C) to component (B) (hereinafter also referred to as "C / B ratio") is 0.01 to 1000, preferably 0.05 to 200, and more preferably 0.1 to 100. When the C / B ratio is within the above range, the anti-clogging properties of the filter are further improved.

[0024] <(D) component> Component (D) is an anionic surfactant. By including the component (D), the liquid detergent composition exhibits excellent detergency and also improves the coloration prevention properties.

[0025] Examples of anionic surfactants include soaps and non-soap anionic surfactants. The component (D) may be used alone or in combination of two or more.

[0026] Examples of soap include higher fatty acids and salts thereof. Examples of higher fatty acids include single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid, and salts thereof; and mixed fatty acids such as coconut fatty acid and beef tallow fatty acid. Examples of salt forms of higher fatty acids include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.). Among these, lauric acid, myristic acid, palmitic acid, coconut fatty acid, or salts thereof are preferred as soap. The soap may be used alone or in combination of two or more kinds.

[0027] Examples of non-soap anionic surfactants include sulfonic acids or salts thereof, sulfates or salts thereof, carboxylic acids or salts thereof, and phosphates or salts thereof. Examples of sulfonic acids or salts thereof include alkylbenzenesulfonic acids or salts thereof (LAS), alkylsulfuric acids or salts thereof, alkanesulfonic acids or salts thereof, α-olefinsulfonic acids or salts thereof, α-sulfofatty acids or salts thereof, α-sulfofatty acids alkyl esters or salts thereof, monoalkylsulfosuccinic acids or salts thereof, and dialkylsulfosuccinic acids or salts thereof. Examples of sulfate esters or salts thereof include alkyl sulfate esters or salts thereof (AS), alkenyl sulfate esters or salts thereof, polyoxyalkylene alkyl ether sulfate esters or salts thereof, and polyoxyalkylene alkenyl ether sulfate esters or salts thereof. Examples of the carboxylic acid or salt thereof include alkyl ether carboxylic acid or salt thereof, amide ether carboxylic acid or salt thereof, sulfosuccinic acid or salt thereof, and amino acid-based anionic surfactants. Examples of the phosphate ester or its type include alkyl phosphate ester or its salt, and alkyl ether phosphate ester or its salt. Examples of salt forms of non-soap anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The non-soap anionic surfactants may be used alone or in combination of two or more.

[0028] Among these, non-soap anionic surfactants are preferred as component (D). From the viewpoint of increasing compatibility with component (B), which in turn makes it less likely that component (C) will be hindered from retaining water molecules, makes component (C) less likely to condense, and makes it easier to prevent filter clogging, the non-soap anionic surfactant preferably has an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms. The alkyl group and alkenyl group may be linear or branched. Furthermore, from the viewpoint of further improving the coloration prevention properties, the non-soap anionic surfactant is preferably a sulfonic acid or a salt thereof, or a sulfate ester or a salt thereof, more preferably a monoalkyl sulfosuccinic acid or a salt thereof, an alkylbenzenesulfonic acid or a salt thereof, or an alkyl sulfate ester or a salt thereof, still more preferably a monoalkyl sulfosuccinic acid or a salt thereof, an alkylbenzenesulfonic acid or a salt thereof, or an alkyl sulfate ester having an alkyl group of 10 to 12 carbon atoms or a salt thereof, particularly preferably a monoalkyl sulfosuccinic acid or a salt thereof, an alkylbenzenesulfonic acid or a salt thereof, or an alkyl sulfate ester having an alkyl group of 10 carbon atoms or a salt thereof, and most preferably a monoalkyl sulfosuccinic acid or a salt thereof.

[0029] The monoalkylsulfosuccinic acid or a salt thereof is preferably a compound represented by the following general formula (1).

[0030] [ka]

[0031] In formula (1), R 1represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms; AO represents an oxyalkylene group; n represents the average number of repetitions of AO and is an integer of 0 to 10; and Ma and Mb each independently represent a counter ion.

[0032] R 1 is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. R 1 The number of carbon atoms is 8 to 18, preferably 12 to 16, and more preferably 12 to 14. R 1 As the alkyl group, a linear or branched alkyl group having 12 to 16 carbon atoms is preferable, a linear or branched alkyl group having 12 to 14 carbon atoms is more preferable, and a linear alkyl group having 12 to 14 carbon atoms is even more preferable.

[0033] AO is an oxyalkylene group. Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group, etc. Among these, an oxyethylene group is preferred. n represents the average number of repeats (number of moles added) of AO and is an integer of 0 to 10. From the viewpoints of detergency against protein stains, low foaming properties, performance in inhibiting cloudy stains on glass tableware, and performance in preventing odor adhesion, n is preferably 1 to 8, and more preferably 4 to 8.

[0034] Ma and Mb are each independently a counter ion. Examples of counter ions include hydrogen ions and ions capable of forming water-soluble salts. Among these, ions capable of forming water-soluble salts are preferred. Examples of ions that can form water-soluble salts include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; and protonated ethanolamine. Ma and Mb are each independently preferably an alkali metal ion or an alkaline earth metal ion, more preferably a sodium ion or a magnesium ion, and even more preferably a sodium ion. Ma and Mb may be the same type of counter ion or different types of counter ions, but are preferably the same type of counter ion. If Ma is a divalent or higher counter ion, the number of Ma bound to -SO3 is 1 / 2. For example, if Ma is a magnesium ion, the number of Ma is 1 / 2. When Mb is a divalent or higher valent counter ion, Mb is considered to be bonded to -O at a number obtained by multiplying Mb by 1 / valency.

[0035] The compound represented by general formula (1) includes, for example, disodium monolauryl sulfosuccinate when n is 0. When n is 1 or more, it includes, for example, polyoxyethylene monoalkyl sulfosuccinate. Examples of polyoxyethylene monoalkyl sulfosuccinates include polyoxyethylene (1) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (2) monolauryl disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (carbon number 12 to 14) sulfosuccinate 2 triethanolamine, polyoxyethylene (3) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (3) monolauryl disodium sulfosuccinate, polyoxyethylene (3) monolauryl magnesium sulfosuccinate, and polyoxyethylene (3) monococonut oil fatty acid (carbon number 8 to 18) ) disodium sulfosuccinate, polyoxyethylene (5) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (5) monococonut oil fatty acid (carbon number 8 to 18) disodium sulfosuccinate, polyoxyethylene (5) monolauryl sulfosuccinate diethanolamide, polyoxyethylene (5) lauryl sulfosuccinate magnesium, polyoxyethylene (5) monococonut oil fatty acid (carbon number 8 to 18) disodium sulfosuccinate, polyoxyethylene (5) lauroylethanolamide sulfosuccinate disodium, polyoxyethylene (7) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (7) magnesium monolauryl sulfosuccinate. The number in parentheses after polyoxyethylene indicates the average number of repeating oxyethylene groups.

[0036] The content of component (D) is preferably 0.5 to 5 mass %, more preferably 1 to 3 mass %, based on the total mass of the liquid detergent composition. When the content of component (D) is equal to or greater than the lower limit, the coloration prevention property is further improved. When the content of component (D) is equal to or less than the upper limit, the coloration prevention property is maintained well while the filter clogging prevention property is further improved.

[0037] <(E) component> Component (E) is a chelating agent having a molecular weight of 800 or less. When the liquid detergent composition contains the component (E), the coloring prevention property and the filter clogging prevention property are further improved.

[0038] The molecular weight of the chelating agent is not more than 800, preferably from 100 to 800, and more preferably from 150 to 500. When the molecular weight of the chelating agent is not more than the above upper limit, the cleaning power against protein stains, the ability to inhibit cloudy stains on glass tableware, and the ability to prevent odor adhesion are improved.

[0039] Examples of chelating agents having a molecular weight of 800 or less include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminedisuccinic acid, L-aspartic acid-N,N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol ether diaminetetraacetic 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, and salts thereof. As the salt constituting the chelating agent, alkali metal salts are preferred, and sodium salts and potassium salts are more preferred, from the viewpoint of further improving the cleaning power against protein stains, the ability to inhibit clouding of glass tableware, and the ability to prevent odor adhesion. Among these, from the viewpoint of further improving the coloration prevention property and the filter clogging prevention property, citric acid, ethylenediaminetetraacetic acid, L-glutamic acid diacetic acid, methylglycine diacetic acid, or a salt thereof is preferred as component (E), and citric acid or a salt thereof is more preferred. The component (E) may be used alone or in combination of two or more.

[0040] The content of component (E) is preferably 5 to 20 mass %, more preferably 7 to 15 mass %, based on the total mass of the liquid detergent composition. When the content of component (E) is equal to or greater than the above-mentioned lower limit, the coloring prevention property is further improved. When the content of component (E) is equal to or less than the above-mentioned upper limit, the filter clogging prevention property is further improved.

[0041] <(F) Component> The component (F) is at least one selected from the group consisting of carbonic acid, carbonates, hydrogen carbonates, and hydrogen carbonates. When the liquid detergent composition contains the component (F), the coloring prevention property and the filter clogging prevention property are further improved.

[0042] Carbonates are carbonate ions (CO3 2- Examples of carbonates include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate, magnesium carbonate and barium carbonate; and ammonium carbonate. Bicarbonate is a compound of hydrogen carbonate ions (HCO3 - Examples of hydrogen carbonates include alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate; and ammonium hydrogen carbonate. Among these, carbonates and bicarbonates are preferred as component (F), and from the viewpoint of further improving the prevention of coloration and the prevention of filter clogging, alkali metal carbonates and alkali metal bicarbonates are more preferred, with alkali metal bicarbonates being even more preferred. The component (F) may be used alone or in combination of two or more.

[0043] The content of component (F) is preferably 0.1 to 5 mass%, more preferably 0.3 to 3 mass%, based on the total mass of the liquid detergent composition. When the content of component (F) is equal to or greater than the above-mentioned lower limit, the coloring prevention property is further improved. When the content of component (F) is equal to or less than the above-mentioned upper limit, the filter clogging prevention property is further improved.

[0044] <Water> As the water, purified water, ion-exchanged water, distilled water, tap water, etc. can be used. The water may be used alone or in combination of two or more kinds.

[0045] <Optional ingredients> Optional components include water-miscible organic solvents, surfactants other than component (D) (hereinafter also referred to as "other surfactants"), pH adjusters, hydrotropes, dispersants, thickeners other than component (C) (hereinafter also referred to as "other thickeners"), viscosity modifiers, chelating agents other than component (E) (hereinafter also referred to as "other chelating agents"), solubilizers, antioxidants, preservatives, disinfectants, bleaches, bleach activators, oil absorbents, antifoaming agents, dish protectants, colorants, enzymes, and fragrances other than component (B) (hereinafter also referred to as "other fragrances"). The optional components may be used alone or in combination of two or more.

[0046] A water-miscible organic solvent is an organic solvent that dissolves 50 g or more in 1 L of water at 25°C. Examples of water-miscible organic solvents include monohydric alcohols having 2 to 4 carbon atoms, such as ethanol, 1-propanol, 2-propanol, and 1-butanol; polyhydric alcohols having 2 to 4 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, and glycerin; and glycol ethers, such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. The water-miscible organic solvents may be used alone or in combination of two or more.

[0047] Examples of other surfactants include nonionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. The other surfactants may be used singly or in combination of two or more.

[0048] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters such as sorbitan fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl polyglycosides, and glycerin fatty acid esters. The nonionic surfactants may be used alone or in combination of two or more.

[0049] Examples of cationic surfactants include myristate dimethylaminoethylamide, myristate diethylaminoethylamide, myristate dipropylaminoethylamide, myristate dimethylaminopropylamide, myristate diethylaminopropylamide, myristate dipropylaminopropylamide, palmitate dimethylaminoethylamide, palmitate diethylaminoethylamide, palmitate dipropylaminoethylamide, palmitate dimethylaminopropylamide, palmitate diethylaminopropylamide, palmitate dipropylaminopropylamide, stearic acid dimethylaminoethylamide, stearic acid diethylaminoethylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminopropylamide, arachidic acid dimethylaminoethylamide, arachidic acid diethylaminoethylamide, arachidic acid dipropylaminoethylamide, arachidic acid dimethylaminopropylamide, arachidic acid dimethylaminopropylamide, arachidic acid and alkylamidoamines such as arachidic acid diethylaminopropylamide, arachidic acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dipropylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenic acid dipropylaminopropylamide, myristic acid dimethylaminoethylmethylamide, palmitic acid dimethylaminoethylmethylamide, stearic acid dimethylaminoethylmethylamide, arachidic acid dimethylaminoethylmethylamide, behenic acid dimethylaminoethylmethylamide, myristic acid dimethylaminopropylmethylamide, palmitic acid dimethylaminopropylmethylamide, stearic acid dimethylaminopropylmethylamide, arachidic acid dimethylaminopropylmethylamide, behenic acid dimethylaminopropylmethylamide, myristate propyltrimethylammonium salt, palmitic acid propyltrimethylammonium salt, and stearic acid propyltrimethylammonium salt. Examples of salt forms of cationic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The cationic surfactants may be used alone or in combination of two or more.

[0050] Examples of amphoteric surfactants include carboxylate-type, sulfate-type, sulfonate-type, phosphate-type, etc. Among these, carboxylate-type amphoteric surfactants are preferred. Examples of carboxylate-type amphoteric surfactants include betaine-type amphoteric surfactants such as lauryl dimethyl aminoacetic acid betaine, coconut alkyl dimethyl aminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl dimethyl aminoacetic acid betaine, and coconut alkyl amidopropyl dimethyl aminoacetic acid betaine. The amphoteric surfactants may be used alone or in combination of two or more.

[0051] Examples of semi-polar surfactants include alkyldimethylamine oxide-type semi-polar surfactants such as lauryl dimethylamine oxide, coconut alkyl dimethylamine oxide, lauryl diethylamine oxide, and n-dodecyl dimethylamine oxide; and alkanoylamido alkyl dimethylamine oxide-type semi-polar surfactants such as lauric acid amidopropyl amine oxide. Among these, alkyldimethylamine oxide-type semi-polar surfactants are preferred. The semi-polar surfactants may be used singly or in combination of two or more.

[0052] Examples of pH adjusters include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; 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 oxalic acid. The pH adjusters may be used alone or in combination of two or more. The amount of pH adjuster added may be appropriately determined so as to adjust the liquid detergent composition to a predetermined pH.

[0053] <Physical properties> (pH) The pH of the liquid detergent composition at 25°C is preferably 5 to 10.5, more preferably 6 to 9, and even more preferably 7 to 8. When the pH of the liquid detergent composition is equal to or higher than the above lower limit, the detergency is enhanced. When the pH of the liquid detergent composition is equal to or lower than the above upper limit, deterioration of the objects to be washed, such as tableware, and clouding of glass tableware are less likely to occur. The pH of the liquid detergent composition can be adjusted, if necessary, by adding a pH adjuster. The pH of the liquid detergent composition at 25°C is a value measured by a method in accordance with "pH measurement method" of JIS Z 8802:2011.

[0054] (viscosity) The viscosity of the liquid detergent composition at 25°C is preferably from 10 to 2000 mPa·s, more preferably from 100 to 1000 mPa·s. The viscosity of the liquid detergent composition at 25°C is a value measured in accordance with Viscosity Measurement Method 2, General Test Method, of the Quasi-drug Ingredients Standards 2006. Specifically, the value is measured using a Vismetron viscometer with rotors No. 2 to No. 4, at a rotation speed of 6 rpm, for 120 seconds.

[0055] <Manufacturing method> The method for producing the liquid detergent composition is not particularly limited, and the liquid detergent composition can be produced in accordance with a conventional method. For example, the liquid detergent composition can be produced by mixing the above-mentioned components (A), (B), (C), and (D), a portion of water, and, if necessary, one or more optional components other than components (E), (F), and a pH adjuster, adjusting the pH to a predetermined value using a pH adjuster if necessary, and then mixing the remaining water.

[0056] <How to use> The liquid detergent composition of the present invention can be used in a dishwasher, and may be used depending on the type of dishwasher and the degree of soiling of the objects to be washed, such as dishes. An example of a method for cleaning objects to be cleaned in a dishwasher using the liquid detergent composition of the present invention is a method that includes both a washing step and a rinsing step. Examples of washing methods include a step of washing objects while heating the washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30°C) into the dishwasher to a predetermined washing temperature (the temperature of the washing liquid circulating during washing) (hereinafter referred to as the "washing step"), a step of rinsing the washed objects with tap water at room temperature (hereinafter referred to as the "rinsing (1) step"), and a step of further rinsing the objects after the rinsing (1) step while heating the tap water from 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. In a typical standard wash cycle, the wash temperature is about 55 to 65°C and the temperature rise rate is about 2 to 3°C / min. In a low-temperature wash cycle, the wash temperature is about 35 to 45°C and the temperature rise rate is about 1°C / min. The liquid detergent composition of the present invention has excellent detergency against oily stains even in low-temperature wash cycles, and exhibits excellent detergency even at a wash temperature of 35°C, for example. In either course, the amount of liquid detergent composition used at one time is preferably 2 to 9 g per approximately 3 liters of tap water in the case of a liquid detergent.

[0057] Furthermore, the objects to be cleaned may be washed using a dishwasher equipped with an automatic detergent dispensing function (automatic detergent dispensing dishwasher), which has recently become practical. The automatic detergent dispensing function is a device that automatically dispenses the liquid detergent composition from a detergent tank containing the liquid detergent composition into the dishwasher chamber through a filter for preventing foreign matter from entering the detergent tank, a dispensing pipe, etc., which are attached to the detergent tank. The liquid detergent composition of the present invention has excellent anti-clogging properties for filters, and is therefore suitable as a detergent for dishwashers equipped with an automatic detergent dispensing function.

[0058] <Action and effect> The liquid detergent composition of the present invention contains components (A), (B), (C), and (D), and since the A / B ratio and C / B ratio are within the above ranges, it has excellent anti-coloring properties and anti-clogging properties for filters. [Example]

[0059] The present invention will be described in more detail below by showing examples, but the present invention is not limited to the following description.

[0060] "Raw materials used" The following compounds were used as component (A). A-1: Sodium sulfite (Fujifilm Wako Pure Chemical Industries, Ltd., reagent).

[0061] The following compounds were used as component (B). B-1: Linalool (Fujifilm Wako Pure Chemical Industries, first-grade reagent, ClogP value = 3.38). B-2: Borneol (Tokyo Chemical Industry Co., Ltd., reagent, ClogP value = 2.86). B-3: l-Menthol (Tokyo Chemical Industry Co., Ltd., reagent, ClogP value = 3.38). B-4: Nerol (Tokyo Chemical Industry Co., Ltd., reagent, ClogP value = 3.47). B-5: Geraniol (Fujifilm Wako Pure Chemical Industries, Ltd., first-grade reagent, ClogP value = 3.47). B-6: Dihydromyrcenol (Fujifilm Wako Pure Chemical Industries, Ltd., reagent, ClogP value = 3.47). B-7: 3,7-dimethyl-3-octanol (Tokyo Chemical Industry Co., Ltd., reagent, ClogP value = 3.52). B-8: Citronellol (Tokyo Chemical Industry Co., Ltd., reagent, ClogP value = 3.56).

[0062] The following compounds were used as component (C). C-1: Xanthan gum (manufactured by Sansho Co., Ltd., product name "KELZAN T"). C-2: Gellan gum (manufactured by Sansho Co., Ltd., product name "KELCO-CRETE DG").

[0063] The compound shown below was used as component (D). D-1: Sodium monoalkyl sulfosuccinate (disodium polyoxyethylene monoalkyl (carbon number 12-14) sulfosuccinate, manufactured by Toho Chemical Industry Co., Ltd., trade name "Kohacool L-400"). D-2: LAS (sodium linear alkyl (carbon number 12-14) benzenesulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon LS-250"). D-3: C10 AS (sodium linear alkyl (carbon number 10) sulfate, manufactured by Fluorochem Ltd., trade name "n-Decyl sodium sulfate"). D-4: C12 AS (sodium linear alkyl (carbon number 12) sulfate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Sunol LM-1130").

[0064] The compound shown below was used as component (E). E-1: Sodium citrate (manufactured by Fuso Chemical Co., Ltd., trade name "trisodium citrate"). E-2: EDTA-Na (disodium ethylenediaminetetraacetic acid, Tokyo Chemical Industry Co., Ltd., reagent). E-3: GLDA (manufactured by Cherest Co., Ltd., trade name "L-glutamic acid diacetate tetrasodium salt"). E-4: MGDA (manufactured by BASF, trade name "trisodium methylglycine diacetate").

[0065] The compound shown below was used as component (F). F-1: Sodium bicarbonate (Fujifilm Wako Pure Chemical Industries, Ltd., reagent). F-2: Potassium bicarbonate (Fujifilm Wako Pure Chemical Industries, Ltd., reagent). F-3: Sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd., reagent). F-4: Potassium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd., reagent).

[0066] As optional components, the compounds shown below were used. Propylene glycol: Fujifilm Wako Pure Chemical Industries, Ltd., Reagent. Fragrance composition: A mixture of the formulation shown in Table 1. pH adjuster: Sodium hydroxide (AGC Corporation, 48% sodium hydroxide). pH adjuster: Potassium hydroxide (AGC Corporation, 48% potassium hydroxide). pH adjuster: sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0067] [Table 1]

[0068] "Examples 1 to 53, Comparative Examples 1 to 8" <Preparation of Liquid Detergent Composition> According to the formulations in Tables 2 to 10, 0.8 kg of each liquid detergent composition was prepared by dissolving optional components other than components (A), (B), (C), (D), (E), (F), and the pH adjuster, as well as the pH adjuster, in water as a solvent. Specifically, water was added to a 1-L beaker (12 cm diameter) so that the total amount of water accounted for 40% by mass of the entire composition. A HEIDON FBL1200 Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) stirrer was equipped with a four-blade paddle with a diameter of 7.5 cm, a width of 1.5 cm, and an angle of 45°. Then, component (C) and optional component propylene glycol were added while mixing, while stirring at 400 to 900 rpm to prevent the contents from scattering. Next, components (D) and (E) were added, and a pH adjuster (sodium hydroxide, potassium hydroxide, or sulfuric acid) was added to adjust the pH to around 7. Then, component (F) was added, and another pH adjuster was added to adjust the pH to 7.5. After cooling to room temperature, components (A), (B), and the fragrance composition were added while stirring at a rotation speed of 650 rpm. After the addition was completed, the mixture was stirred for 5 minutes, and the remaining water was added so that the total composition was 100% by mass. The mixture was then stirred at a rotation speed of 650 rpm with the stirrer for 1 minute to obtain a liquid detergent composition. The pH (25°C) of the liquid detergent composition was measured using a glass electrode pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G") after adjusting the liquid detergent composition to 25°C in accordance with JIS Z 8802:2011 "pH measurement method." The resulting liquid detergent compositions were evaluated for their anti-coloring properties and anti-clogging properties by the following methods. The results are shown in Tables 2 to 10.

[0069] <Evaluation of coloring prevention properties> (The dirt used for evaluation) A commercially available pasta sauce (manufactured by Nisshin Seifun Welna Co., Ltd., product name "Ma Ma Meat Sauce") was used as the stain. 30 g of meat sauce was placed on a plastic plate (100 mm radius, 25 mm height) to uniformly contaminate the surface of the plate, and then the meat sauce was removed with a spoon and allowed to adhere to the plastic plate. A total of six contaminated plates were prepared in this way.

[0070] (dishwasher) A dishwasher (manufactured by Panasonic Corporation, model name "NP-45MD8") was used as the dishwasher. In the evaluation of staining prevention, the washing process was carried out by operating the dishwasher on the standard course set in the dishwasher. The details of the standard course are shown below. <<Standard Course>> After adding 8 g of the liquid detergent composition (per 3 L of tap water) to the dishwasher, tap water at approximately 5°C is introduced into the dishwasher to prepare a cleaning solution, which is heated to 40°C at a rate of 2-3°C / min while washing for 20 minutes, and then the cleaning solution is drained. Fresh tap water is then introduced, and rinsing (2 minutes per rinse) and draining are repeated three times. After draining, fresh tap water is introduced, and rinsing (final rinse) is performed once for 20 minutes while the temperature is raised to 70°C at a rate of 2-3°C / min. After draining, the dishes are dried by circulating warm air.

[0071] (Evaluation method) Six contaminated dishes were loaded into the dishwasher in the designated locations according to the instructions, and 8 g of the liquid detergent composition was added. The washed plastic dishes were then re-contaminated with meat sauce and then washed again. This process of contamination and washing was repeated 30 times, and the plastic dishes after the 30th wash were visually observed and evaluated for staining resistance based on the following evaluation criteria.

[0072] (Evaluation criteria) A: No stains or discoloration can be seen on the entire plate. B: Slight staining (1cm 2 (less than) is permitted. C: Partial stain (1cm 2 (above) will be awarded one point. D: Partial stain (1cm 2 Two points above are accepted. E: Partial stain (1cm 2 Three or more of the above are clearly visible, or there is faint discoloration on the entire plate. F: Partial stain (1cm 2 or more) are found, or the entire surface of the plate is heavily stained, making it uncomfortable to reuse.

[0073] <Evaluation of clogging prevention> (Evaluation method) The anti-clogging properties of the liquid detergent composition were evaluated using a test sieve, which was designed to resemble a filter installed in the detergent tank of an automatic detergent-dispensing dishwasher. Specifically, 0.8 kg of the liquid detergent composition was passed through a 30-mesh filter (inner diameter 75 mm, depth 20 mm, manufactured by Tokyo Screen Co., Ltd.) 10 times. The amount of residue on the filter was then visually observed, and the anti-clogging properties were evaluated based on the following evaluation criteria.

[0074] (Evaluation criteria) A: No residue is found at all. B: A small amount of residue is observed. C: Residue is clearly visible, but no clogging or changes in filtration time are observed. D: Residue is clearly visible, filtration time is long, and clogging is observed.

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] [Table 5]

[0079] [Table 6]

[0080] [Table 7]

[0081] [Table 8]

[0082] [Table 9]

[0083] [Table 10]

[0084] In Tables 2 to 10, the amount (mass%) of each component is the ratio to the total mass of the liquid detergent composition, and unless otherwise specified, is shown as a pure content. The amount of water "balanced" means that water is added so that the total amount (mass%) of all components contained in the liquid detergent composition is 100 mass%. The amount of pH adjuster "appropriate amount" is the amount required to adjust the liquid detergent composition to the desired pH. Furthermore, a blank column for the amount means that the component is not added (amount 0 mass%). In addition, the "A / B ratio" in Tables 2 to 10 is the mass ratio expressed as (A) component / (B component). The "C / B ratio" is the mass ratio expressed as (C) component / (B component). In Tables 2 to 10, the C / B ratios are rounded to two decimal places.

[0085] As is clear from Tables 2 to 9, the liquid detergent compositions of the examples were excellent in preventing coloration and filter clogging. On the other hand, as is clear from Table 10, the liquid detergent composition of Comparative Example 1, which did not contain component (A), was poor in coloration prevention properties. The liquid detergent composition of Comparative Example 2, which did not contain component (B), was poor in preventing clogging of the filter. The liquid detergent composition of Comparative Example 3, which did not contain component (C), was inferior in preventing clogging of the filter. The liquid detergent composition of Comparative Example 4, which did not contain component (D), was poor in coloration prevention properties. A / B ratio is 600 or 6.67 x 10 -6 The liquid detergent compositions of Comparative Examples 5 and 6 were inferior in the ability to prevent coloring and filter clogging. The liquid detergent compositions of Comparative Examples 7 and 8, in which the C / B ratio was 2400.00 or 0.00, were inferior in the ability to prevent clogging of the filter.

Claims

1. Component (A): at least one selected from the group consisting of sulfurous acid, sulfite salts, hydrogen sulfite salts, and hydrogen sulfite salts; (B) component: at least one selected from the group consisting of cyclic monoterpene alcohols and acyclic monoterpene alcohols; (C) component: acidic polysaccharide; Component (D): an anionic surfactant; Contains the mass ratio of the component (A) to the component (B) is 0.00005 to 200; A liquid detergent composition for dishwashers, wherein the mass ratio of the component (C) to the component (B) is 0.01 to 1000.

2. 2. The liquid dishwasher detergent composition according to claim 1, further comprising component (E): a chelating agent having a molecular weight of 800 or less.

3. 3. The liquid dishwasher detergent composition according to claim 1, further comprising: (F) component: at least one selected from the group consisting of carbonic acid, carbonates, hydrogen carbonates, and hydrogen carbonates.

4. The liquid dishwasher detergent composition according to claim 1 or 2, wherein the component (C) comprises xanthan gum.

5. 3. The liquid dishwasher detergent composition according to claim 1, wherein the component (D) comprises at least one selected from the group consisting of monoalkyl sulfosuccinic acids and monoalkyl sulfosuccinate salts.

6. The liquid dishwasher detergent composition according to claim 1 or 2, wherein the component (B) comprises at least one selected from the group consisting of linalool, borneol, 1-menthol, nerol, geraniol, dihydromyrcenol, 3,7-dimethyl-3-octanol, and citronellol.

Images