Liquid detergent composition

Abstract

To provide a liquid detergent composition excellent in detergency with a small amount of use.SOLUTION: Nonionic surfactants represented by the following general formula (a1) R1 - O - [(EO) s / (PO) t] - H. (a1) (In the formula (a1), R1 is a hydrocarbyl group having 12 to 18 carbon atoms, EO is an oxyethylene group, s is a number of 12 to 25 indicating the average number of repetitions of EO, PO is an oxypropylene group, and t is a number of 1 to 5 indicating the average number of repetitions of PO. EO and PO may be randomly added or block-added. The hydrocarbons having 14 carbon atoms account for 50% by mass or more of the total amount of R1. A total mass of the component (A) with respect to a total mass of the liquid detergent is 5% by mass or more.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Liquid detergent compositions for textile products such as clothing contain surfactants. Concentrated liquid detergent compositions that can achieve cleaning effects with a small amount of use are desired. Patent Document 1, for example, discloses a concentrated liquid detergent composition for textile products that contains an anionic surfactant and a nonionic surfactant. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2024-64153 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, concentrated liquid detergent compositions contain a high concentration of surfactant, which reduces the proportion of water, which can lead to problems such as gelation, precipitation, etc. Therefore, an object of the present invention is to provide a liquid detergent composition that provides sufficient detergency even when used in a small amount and has good stability. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] Component (A): a nonionic surfactant represented by the following general formula (a1): R 1 -O-[(EO) s / (PO) t ]-H (a1) (In general formula (a1), R 1is a hydrocarbon group having 12 to 18 carbon atoms, EO is an oxyethylene group, s is a number from 12 to 25 indicating the average number of repetitions of EO, PO is an oxypropylene group, and t is a number from 1 to 5 indicating the average number of repetitions of PO. EO and PO may be added randomly or in blocks. However, when the hydrocarbon group having 14 carbon atoms is R 1 It is 50% by mass or more of the total amount.) Component (B): At least one organic solvent selected from 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, diethylene glycol monobutyl ether, polyethylene glycol, 3-methoxy-3-methylbutanol, phenoxyethanol, and polyoxyethylene monophenyl ether having an average repeating number of oxyethylene groups of 4 to 8. Contains A liquid detergent composition, in which the total mass of component (A) is 5 mass% or more relative to the total mass of the liquid detergent. [2] The liquid detergent composition according to [1], further comprising a non-soap anionic surfactant as component (C). [3] The liquid detergent composition according to [1] and [2], further comprising component (D): an enzyme. [4] The liquid detergent composition according to [1], wherein the mass ratio of the component (A) to the component (B) is 1 or more. [5] The liquid detergent composition according to [2], wherein the mass ratio of the component (A) to the component (C) is 5 or more. [6] The liquid detergent composition according to [1], wherein the content of the component (B) is 1 to 20% by mass based on the total mass of the liquid detergent composition. [7] The liquid detergent composition according to [1] further contains a soil release agent. [8] The liquid detergent composition according to [1], which is for use in a washing machine equipped with an automatic detergent dispensing function. [9] A laundry method using the liquid detergent composition according to [1], wherein the amount of the liquid detergent composition used is 3 to 10 g per 30 L of water. [Effects of the Invention]

[0006] An object of the present invention is to provide a liquid detergent composition that has excellent detergency even when used in a small amount. DETAILED DESCRIPTION OF THE INVENTION

[0007] The liquid detergent composition of the present invention is a liquid composition containing component (A) and component (B). <Component (A)> Component (A): a nonionic surfactant represented by the following general formula (a1): R 1 -O-[(EO) s / (PO) t ]-H (a1) (In general formula (a1), R 1 is a hydrocarbon group having 12 to 18 carbon atoms, EO is an oxyethylene group, s is a number from 12 to 25 indicating the average number of repetitions of EO, PO is an oxypropylene group, and t is a number from 1 to 5 indicating the average number of repetitions of PO. EO and PO may be added randomly or in blocks. However, when the hydrocarbon group having 14 carbon atoms is R 1 It is 50% by mass or more of the total amount.) In formula (a1), R 1 is a hydrocarbon group having 12 to 18 carbon atoms, and a hydrocarbon group having 14 carbon atoms is R 1 The hydrocarbon group having 14 carbon atoms is R because of its good detergency. 1 It is preferably 70% by mass of the total amount, more preferably 80% by mass or more, and particularly preferably 100% by mass. R 1 The hydrocarbon group R may be linear or branched. It may or may not have an unsaturated bond. 1 The hydrocarbon group is preferably a straight chain. Surfactants that use natural oils and fats as raw materials usually have lipophilic groups with 12 to 14 carbon atoms, but those with 14 carbon atoms are more hydrophobic than those with 12 carbon atoms, and have a lower critical micelle concentration (CMC). 1 By making it 50% by mass or more of the total amount, it is thought that the CMC of component (A) is lowered, resulting in high detergency even at low concentrations. In addition, a single straight-chain hydrocarbon group with 14 carbon atoms improves detergency even at low concentrations. 1 If the number of carbon atoms in the alkyl group is increased, the low-temperature stability of the liquid detergent composition is deteriorated. The integer s is 12 to 25, preferably 14 to 20, more preferably 14 to 18, and particularly preferably 14 to 16. When s is 12 to 25, the cleansing power for sebum stains is good. When s exceeds 25, hydrophilicity increases and the CMC of component (A) tends to decrease. t is 1 to 5, more preferably 1 to 3. When t is less than 1, the low-temperature stability of the cleansing composition deteriorates, and when t exceeds 5, the cleansing power at low concentrations deteriorates. EO and PO may be added randomly or in blocks, with random addition and terminal block addition of PO being preferred. Methods for randomly arranging EO and PO include, for example, a method of simultaneously introducing ethylene oxide and propylene oxide. Methods for arranging EO and PO in blocks include, for example, a method of introducing ethylene oxide and then propylene oxide, a method of introducing propylene oxide and then ethylene oxide, and a method of introducing ethylene oxide, then propylene oxide, and then ethylene oxide.

[0008] The content of component (A) in the liquid detergent composition is 5% by mass or more, preferably 7 to 60% by mass, more preferably 15 to 50% by mass, and most preferably 25 to 40% by mass. By keeping the content of component (A) within the above range, good detergency can be obtained. When the amount of the liquid detergent composition used is 3 to 10 g per 30 L of water, the content of component (A) relative to the total mass of the liquid detergent composition is preferably 15 to 60 mass%, more preferably 20 to 50 mass%, and particularly preferably 25 to 35 mass%. When the amount of the liquid detergent composition used is 20 to 30 g per 30 L of water, the content of component (A) relative to the total mass of the liquid detergent composition is preferably 5 to 30 mass%, more preferably 5 to 25 mass%, and particularly preferably 8 to 15 mass%. <(B) component> Component (B) is at least one organic solvent selected from 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, diethylene glycol monobutyl ether, polyethylene glycol, 3-methoxy-3-methylbutanol, phenoxyethanol, and polyoxyethylene monophenyl ether having an average repeating number of oxyethylene groups of 4 to 8. Component (B) is preferably ethylene glycol, propylene glycol, glycerin, polyethylene glycol, 3-methoxy-3-methylbutanol, or phenoxyethanol, and more preferably propylene glycol, glycerin, polyethylene glycol, or 3-methoxy-3-methylbutanol. It is preferable to use two or more types of component (B) in combination, and preferred combinations are propylene glycol and glycerin, or polyethylene glycol and 3-methoxy-3-methylbutanol. The content of component (B) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, of the total mass of the liquid detergent composition. When the content of component (B) is within the above range, the liquid detergent composition has good low-temperature stability and good cold water solubility during use. In the liquid detergent composition, the mass ratio of (A) the nonionic surfactant represented by general formula (a1) to (B) the specific organic solvent (hereinafter also referred to as "(A) / (B)") is 1 or more, more preferably 2 to 30, even more preferably 3 to 20, and most preferably 4 to 10. When (A) / (B) is 1 or more, the low-temperature stability of the liquid detergent composition is improved. <(C) component> Component (C) is a non-soap anionic surfactant. The component (C) may be a single surfactant or a combination of two or more surfactants. Examples of anionic surfactants include carboxylic acid-type anionic surfactants such as linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl(alkenyl) ether sulfate ester or its salt (AES), alkyl group-containing alkanesulfonic acid or its salt, α-sulfofatty acid ester or its salt, internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt (HAS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, and acylaminocarboxylic acid or its salt; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, and glycerin fatty acid ester monophosphate ester or its salt.

[0009] Examples of salt forms of 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.).

[0010] These anionic surfactants may be used alone or in combination of two or more. The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (c1).

[0011] R 17 -O-[(EO) m / (PO) n ]-SO3-M + (c1) (In general formula (a4), R 17is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. EO is an oxyethylene group. PO is an oxypropylene group. m is a number of 0.1 or more representing the average number of repetitions of EO. n is a number of 0 to 6 representing the average number of repetitions of PO. [(EO) m / (PO) n ] indicates that there is no restriction on the order of EO and PO, and M + is the countercation.) The AES preferably has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, to which an average of 1 to 5 moles of alkylene oxide is added. The number of carbon atoms in the alkyl or alkenyl group is preferably 10 to 20, more preferably 12 to 14. In particular, a linear alkyl group having 10 to 20 carbon atoms is preferred, and a linear alkyl group having 12 to 14 carbon atoms is more preferred. Specific examples include a dodecyl group, a tridecyl group, and a tetradecyl group. m is preferably from 0.1 to 5, more preferably from 0.1 to 3, further preferably from 0.5 to 2, and particularly preferably from 0.5 to 1.5.

[0012] n is 0 to 6, preferably 0 to 3, and more preferably 0.

[0013] m+n is preferably greater than 0, and more preferably 1 to 5. If n is not 0, that is, if AES has EO and PO [(EO) m / (PO) n In the above, there is no particular limitation on the distribution (arrangement order) of EO and PO, and they may be arranged in a block form or randomly. 17 -O-" or PO may be bonded to "R 17 It may be bonded to "-O-".

[0014] Examples of methods for arranging EO and PO in a block form include a method of introducing ethylene oxide and then propylene oxide, a method of introducing propylene oxide and then ethylene oxide, and a method of introducing ethylene oxide, then propylene oxide, and then ethylene oxide.

[0015] The compound of formula (c1) where m=0 and n=0 is preferably contained in an amount of 35 to 55 mass % relative to the total mass of the compound represented by formula (c1).

[0016] As the anionic surfactant, LAS, AOS, AS and AES are preferred, and among them, from the viewpoint of further enhancing the detergency, LAS and AES are more preferred, and LAS is particularly preferred. The total content of the component (C) is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the liquid detergent composition. The inclusion of component (C) improves odor-removing power. If component (C) is contained in an amount greater than 10% by mass, the detergency at low concentrations will decrease. Furthermore, when an antibacterial agent such as diclosan, which will be described later, is contained, the effect of the antibacterial agent is improved by including component (C). When the liquid detergent composition contains component (C), the mass ratio of (A) nonionic surfactant to (C) anionic surfactant (hereinafter also referred to as "(A) / (C)") is 1 or more, and more preferably 5 or more. <(D) component> Component (D) is an enzyme. Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, pectinase, and nuclease. Proteases are generally commercially available as enzyme-containing preparations (enzyme preparations). When preparing liquid detergents, proteases are usually incorporated in the form of enzyme preparations. The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as a serine protease.

[0017] Examples of preparations containing proteases (protease preparations) include those available from Novozymes under the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Coronase Evity 48L, and Progress Uno101L; and those available from Genencor under the trade names Purafect L, Purafect OX, and Properase L. Examples of preparations containing amylase (amylase preparations) include those available from Novozymes under the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, and Amplify Prime; those available from Genencor under the trade name Maxamyl; those available from Amano Enzyme Inc. under the trade name Pullulanase Amano; and those available from Seikagaku Corporation under the trade name DB-250.

[0018] Examples of preparations containing lipase (lipase preparations) include those available from Novozymes under the trade names Lipex 100L and Lipolase 100L.

[0019] Examples of preparations containing cellulase (cellulase preparations) include those available from Novozymes under the trade names Carezyme 4500L, Carezyme Premium 4500L, Endorase 5000L, and Cellclean 4500T.

[0020] Examples of preparations containing mannanase (mannanase preparations) include those available from Novozymes under the trade names Mannaway 4L and Mannaway 200L.

[0021] Examples of preparations containing pectinase (pectinase preparations) include Pectawash, Pectaway, XPect, and the like available from Novozymes. As a preparation containing a nuclease (nuclease preparation), commercially available products such as Cyronase Cold-Active Nuclease (manufactured by Takara Bio Inc.), Benzonase (manufactured by Millipore), and Pristine 100L (manufactured by Novozymes) can be used. These enzyme preparations may be used alone or in combination of two or more. <Optional ingredients> The liquid detergent may contain components (optional components) other than the components (A), (B), (C) and (D) as long as the effects of the present invention are not impaired.

[0022] Examples of optional components include surfactants other than component (A) and component (C) (optional surfactants), higher fatty acids and salts thereof, organic solvents other than component (B), enzyme stabilizers, hydrotropes, pH adjusters, bleaches, fluorescent brighteners, soil release agents, dispersants, antifoaming agents (excluding component (A) and soap), chelating agents, texture improvers, antibacterial agents, preservatives, antioxidants, fragrances, and pigments.

[0023] The total content of each component in the liquid detergent is 100% by mass. <Optional ingredients> The detergent composition contains one or more fatty acids selected from higher fatty acids (fatty acids having 8 to 22 carbon atoms) and salts thereof (i.e., soaps). By containing higher fatty acids (fatty acids having 8 to 22 carbon atoms) and salts thereof, Improves rinsability.

[0024] The higher fatty acid may be a saturated fatty acid, an unsaturated fatty acid, or a mixture thereof.

[0025] The higher fatty acid preferably has 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms.

[0026] Examples of higher fatty acids include single fatty acids such as stearic acid, linoleic acid, oleic acid, coconut fatty acid, etc., or salts thereof; mixed fatty acids such as coconut fatty acid, beef tallow fatty acid, etc., or salts thereof. These higher fatty acids and salts thereof may be used alone or in combination of two or more. Examples of the salt form of fatty acid include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.).

[0027] The content of the higher fatty acid and its salt is preferably 0.3 to 3 mass %, more preferably 0.5 to 1.5 mass %, based on the total mass of the detergent composition. When the content is equal to or greater than the lower limit, rinsing performance can be further improved. When the content is equal to or less than the upper limit, deterioration of the fragrance of the detergent composition can be effectively suppressed. Examples of optional surfactants include nonionic surfactants other than component (A), cationic surfactants, amphoteric surfactants, and semi-polar surfactants. Examples of optional nonionic surfactants include polyoxyalkylene-type nonionic surfactants other than component (A), 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, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. Examples of polyoxyalkylene nonionic surfactants other than component (A) include compounds represented by the following general formulas (a2) and (a3). R 11 -O-(EO) s -R 12 (a2) (In general formula (a1), R 11 is a hydrocarbon group having 8 to 22 carbon atoms. 12is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. s is a number from 3 to 30 indicating the average number of EO repeats. R 11 may be linear or branched. 11 may be a straight-chain hydrocarbon group, or may be a group selected from a branched-chain primary hydrocarbon group and a straight-chain secondary hydrocarbon group. R 15 -X-[(EO) p / (A 13 O) q ]-(EO) r -R 16 (a3) (In general formula (a3), R 15 is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R 16 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 that indicates the average number of EO repeats. A 13 represents at least one of PO (oxypropylene group) and BO (oxybutylene group); q is a number from 0 to 6 representing the average number of repetitions of A13O; and r is a number from 0 to 20 representing the average number of repetitions of EO. Examples of cationic surfactants include quaternary ammonium salts, etc. Examples of the form of the quaternary ammonium salt include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.).

[0028] Examples of amphoteric surfactants include alkylbetaine type, alkylamidebetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants.

[0029] Examples of the semi-polar surfactant include alkylamine oxide, alkylamidopropyldimethylamine oxide, and the like.

[0030] These optional surfactants may be used alone or in combination of two or more. The total content of (A), (C) and any other surfactants is 5% by mass or more, preferably 7% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and most preferably 25% by mass to 40% by mass, based on the total mass of the liquid detergent composition. When the total amount of surfactants in the liquid detergent composition is 5% by mass or more, the detergency is improved. Examples of organic solvents other than component (B) include organic solvents that have been conventionally used in liquid detergents for clothing, etc. Examples include ethanol, 1-propanol, 1-butanol, sorbitol, and phenoxyisopropanol.

[0031] These organic solvents may be used alone or in combination of two or more.

[0032] The content of organic solvents other than component (B) is preferably 0 to 15 mass %, more preferably 1 to 10 mass %, based on the total mass of the liquid detergent composition. Examples of enzyme stabilizers include boric acid, borax, formic acid or its salts, benzoic acid, lactic acid or its salts, calcium chloride, calcium sulfate, and other calcium salts.

[0033] These enzyme stabilizers may be used alone or in combination of two or more.

[0034] The content of the enzyme stabilizer is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the total mass of the liquid detergent. Examples of hydrotropic agents include paratoluenesulfonic acid or its salts, cumenesulfonic acid or its salts, benzoates, and urea.

[0035] These hydrotropic agents may be used alone or in combination of two or more.

[0036] The content of the hydrotrope agent is preferably 0.01 to 15% by mass relative to the total mass of the liquid detergent. Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), sodium hydroxide, potassium hydroxide, alkanolamines (monoethanolamine, diethanolamine, etc.), ammonia, etc.

[0037] These pH adjusters may be used alone or in combination of two or more. Bleaching agents include hydrogen peroxide.

[0038] The content of the bleaching agent is preferably 0.01 to 10% by mass relative to the total mass of the liquid detergent. Examples of fluorescent brighteners include biphenyl-type fluorescent brighteners such as 4,4'-bis(2-sulfostyryl)biphenyl disodium salt; and stilbene-type fluorescent brighteners such as 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate.

[0039] These fluorescent whitening agents may be used alone or in combination of two or more.

[0040] The content of the fluorescent whitening agent is preferably 0.01 to 10% by mass relative to the total mass of the liquid detergent.

[0041] Examples of soil release agents (SR agents) include polymers having at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene units. Examples of such polymers include those described in International Publication No. 2017 / 142012. Commercially available soil release agents include, for example, Clariant's "TexCare SRN-170" product.

[0042] Further, examples of soil release agents include polymers such as alkylene oxide adducts of polyalkyleneamines.

[0043] Examples of alkylene oxide adducts of polyalkyleneamines include those described in International Publication No. 2017 / 142012 and JP-A No. 2017-514967. Commercially available products include the product name "Sokalan HP20" manufactured by BASF.

[0044] Further, examples of soil release agents include cationized cellulose described in JP 2019-90057 A.

[0045] These soil release agents may be used alone or in combination of two or more.

[0046] The content of the soil release agent is preferably 0.1 to 20% by mass relative to the total mass of the liquid detergent. Adding a soil release agent is preferable from the viewpoint of preventing re-contamination. Examples of dispersants include polyacrylic acid and its salts, polymethacrylic acid and its salts, and polymeric polycarboxylic acids and their salts.

[0047] These dispersants may be used alone or in combination of two or more.

[0048] The content of the dispersant is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent.

[0049] Examples of antifoaming agents include propylene oxide adducts of alcohols (excluding component (A)), fatty acid esters, and the like.

[0050] Examples of propylene oxide adducts of alcohols (excluding component (A)) include those in which propylene oxide is added to monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol; and those in which propylene oxide is added to polyhydric alcohols such as diols such as ethanediol, triols such as glycerin, tetraols such as erythritol, and hexaols such as sorbitol.

[0051] Specific examples of fatty acid esters include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctanoate, 2H08).

[0052] These antifoaming agents may be used alone or in combination of two or more.

[0053] The content of the antifoaming agent is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent.

[0054] Examples of chelating agents include organic phosphonic acids such as ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), hydroxyiminodisuccinic acid (HIDS), diethylenetriaminepentaacetic acid (DTPA), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), and citric acid, or salts thereof.

[0055] Examples of salt forms of the chelating agent include sodium, potassium, calcium, magnesium, and the like.

[0056] These chelating agents may be used alone or in combination of two or more.

[0057] The content of the chelating agent is preferably 0.001 to 10% by mass relative to the total mass of the liquid detergent.

[0058] Examples of the texture improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. These silicones include, for example, oil type, oil compound type, solution type, emulsion type, and self-emulsifying type.

[0059] These texture improvers may be used alone or in combination of two or more.

[0060] The content of the texture improver is preferably 0.1 to 20% by mass relative to the total mass of the liquid detergent.

[0061] Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan Co., Ltd., and "NIPACIDE BIT 20" (trade name) manufactured by Clariant.

[0062] These preservatives may be used alone or in combination of two or more.

[0063] The content of the preservative is preferably 0.001 to 1% by mass relative to the total mass of the liquid detergent. Examples of antioxidants include BHT (dibutylhydroxytoluene) and BHA (butylhydroxyanisole).

[0064] These antioxidants may be used alone or in combination of two or more.

[0065] The content of the antioxidant is preferably 0.01 to 3% by mass relative to the total mass of the liquid detergent. The fragrance may be a fragrance raw material alone or a fragrance composition comprising a fragrance raw material, a fragrance solvent, a fragrance stabilizer, etc. The fragrance may be any fragrance commonly used in liquid detergents. Alternatively, a capsule fragrance may be added to the liquid detergent.

[0066] The content of the fragrance is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent. Examples of dyes include quinone dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, and pyrene dyes. In this specification, the abbreviation "CI" stands for Color Index. The structure of each dye is described in the "Legal Dyes Handbook" (edited by the Japan Cosmetic Industry Council) and the "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry). Examples of quinone dyes include trade names such as CI Solvent Blue 63 (Blue No. 403), Liquitint Blue HP and Liquitint Blue BL manufactured by Milliken. Examples of triphenylmethane dyes include Green No. 3 (CI42053). An example of a quinoline dye is Yellow No. 203 (CI Acid Yellow 3). The content of the dye is preferably 0.1 to 100 ppm by mass relative to the total mass of the liquid detergent. Examples of antibacterial agents include diclosan, triclosan, cationic disinfectants such as quaternary ammonium salts (benzalkonium chloride), zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0067] These antibacterial agents may be used alone or in combination of two or more.

[0068] The content of the antibacterial agent is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and even more preferably 0.1 to 0.5% by mass, relative to the total mass of the liquid detergent. The water is not particularly limited, and can be purified water, distilled water, ion-exchanged water, tap water, etc. One of these may be used alone, or two or more may be used in combination.

[0069] The content of water is preferably 10 to 40 mass %, more preferably 15 to 35 mass %, and even more preferably 20 to 30 mass %, based on the total mass of the liquid detergent composition.

[0070] If the water content is 40 mass % or less, the stability of the liquid detergent composition is improved. <Physical properties> (pH) The pH of the liquid detergent at 25°C is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 8.

[0071] The pH of the liquid detergent can be adjusted by adding a pH adjuster as needed. The pH in this specification is measured at 25°C using a pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G"). (viscosity) The viscosity of the liquid detergent at 25°C is preferably 10 to 2000 mPa·s, more preferably 10 to 100 mPa·s, and even more preferably 10 to 500 mPa·s.

[0072] The viscosity of the liquid detergent was measured using a Brookfield viscometer under the following conditions. <<Measurement conditions>> Rotor: Rotor No. 3 (for values ​​less than 1000 mPa·s) or Rotor No. 4 (for values ​​1000 mPa·s or more). Rotation speed: 60 rpm. Measurement temperature: 25℃. Viscosity reading: 30 seconds after rotor starts rotating. <Manufacturing method> The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced in accordance with a conventional method.

[0073] For example, a liquid detergent can be produced by mixing the above-mentioned components (A), (B), (C), and a portion of component (D), as well as optional components other than the pH adjuster, adjusting the pH to a desired level using a pH adjuster as needed, and then mixing in the remaining component (D). When adjusting the pH to a desired level using a pH adjuster, it is preferable to add component (C) after adjusting the pH.

[0074] <How to use> Methods for using liquid detergents include, for example, putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine, adding the liquid detergent to water together with the items to be washed when washing, immersing the items to be washed in a cleaning solution prepared by dissolving the liquid detergent in water in advance, or applying the liquid detergent directly to the items to be washed and leaving it for, for example, 3 minutes to 24 hours, and then washing as usual. It is also preferable to use a washing machine equipped with an automatic detergent dispensing function, which has recently become practical. This function automatically dispenses detergent from a tank containing the detergent into the washing tub via a dispensing pipe. A measuring device such as a syringe pump is installed in the dispensing pipe, allowing a fixed amount of detergent, set according to the amount of laundry, to be transferred from the tank to the washing tub. Using the automatic detergent dispensing function not only saves you the trouble of measuring the detergent, but also prevents liquid detergent from getting on your hands when measuring it, or from spilling and soiling the washing machine or surrounding area.

[0075] Furthermore, because the liquid detergent of the present invention is concentrated, the amount used per wash may be very small, around 10 mL. Such small amounts of liquid detergent are difficult to accurately measure using a cap or the like, and the amount of liquid is likely to be insufficient or excessive. By using the automatic detergent dispensing function, even small amounts of liquid detergent can be accurately measured, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse, which is preferable. It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. When using an automatic dispenser, it is possible to accurately measure even a small amount of liquid detergent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse.

[0076] Some automatic dispensers on the market use infrared sensors to automatically dispense liquid detergent without touching a switch, etc. By using such an automatic dispenser, the user can measure out the liquid detergent simply by holding the container in one hand, which significantly reduces the burden on the user. When using an automatic dispenser, it is also preferable to receive the dispensed liquid detergent in a soft container and then place the soft container directly into the washing machine, thereby ensuring that the entire amount of dispensed liquid detergent is dissolved in the cleaning liquid.

[0077] Examples of materials for the soft container that can be directly put into the washing machine include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, and the like. Examples of items to be washed include textile products such as clothing, dishcloths, towels, sheets, curtains, etc. The material of the textile products is not particularly limited, and may be any of natural fibers such as cotton, silk, wool, etc., and chemical fibers such as polyester, polyamide, etc.

[0078] When the liquid detergent is used by dissolving it in water, it is preferably diluted, for example, 5 to 5000 times (by volume).

[0079] The liquor ratio, which is the amount of water per amount of clothes (mass of washing liquid / mass of clothes during washing), is preferably 5 or more for drum-type washing machines and 10 or more for vertical washing machines.

[0080] The amount of liquid detergent used in the washing treatment is preferably 10-500, more preferably 10-300, and even more preferably 10-100, in terms of the ratio of the total mass of the items to be washed (cloth mass) / the total mass of the liquid detergent.

[0081] The liquid detergent is suitable as a detergent for textile products. In washing machines with an automatic detergent dispensing function, the temperature inside the tank containing the detergent tends to rise when drying clothes. The liquid detergent of the present invention has excellent high-temperature stability, so it is less likely to form precipitates when stored in the tank of a washing machine with an automatic detergent dispensing function. The liquid detergent of the present invention is less likely to form precipitates when stored not only at high temperatures but also at low temperatures. Therefore, it is possible to prevent the dispensing pipes and syringe pumps of washing machines with an automatic detergent dispensing function from being clogged with precipitates.

[0082] Furthermore, because the liquid detergent of the present invention is less likely to produce precipitates when stored at high or low temperatures, it can prevent the nozzle or dispensing mechanism from becoming clogged with precipitates when used in an automatic dispenser. Therefore, it is possible to install and use a washing machine and automatic dispenser in a place where the temperature fluctuates greatly, such as a balcony. The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0083] The raw materials used and the evaluation methods in the examples and comparative examples are as follows. [Raw materials used] <Component (A)> A-1: AEP non-ionic surfactant [1] (manufactured by Sanyo Chemical Industries, Ltd., product name "Emulmin CS-100W") A-2: AEP nonionic [2] (15EO / 3PO): A PO-terminated compound in which 15 moles of ethylene oxide are added to 1 mole of primary alcohol (100% carbon 14 alcohol), followed by 3 moles of propylene oxide. (Manufactured by Lion Corporation) <(B) component> B-1: Polyethylene glycol (manufactured by Junsei Chemical Co., Ltd., product name "PEG#1000", mass average molecular weight 1000) B-2: Solfit: 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit"). B-3: Glycerin (manufactured by Sakamoto Pharmaceutical Industry Co., Ltd., product name "Glycerin"). B-4: Propylene glycol (manufactured by Chuo Kasei Co., Ltd., product name "Cosmetic Propylene Glycol"). <(C) component> C-1 (LAS): Linear alkylbenzene sulfonic acid with an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals, trade name "Lipon LH-200"). C-2 (AES): Polyoxyalkylene alkyl ether sulfate (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, with an average mole number of EO added of 1). <Optional ingredients> AEP nonionic [3] (15EO / 3PO): A PO-terminated compound in which 15 moles of ethylene oxide are added to 1 mole of primary alcohol (12 carbon atoms / 14 carbon atoms = 7 / 3 by mass), followed by 3 moles of propylene oxide. (Manufactured by Lion Chemical Co.) AE(15EO): Polyoxyethylene alkyl ether (manufactured by Lion Corporation, trade name "LMAO-90"), a compound in which 15 moles of ethylene oxide are added to 1 mole of primary alcohol (mass ratio of C12 alcohol / C14 alcohol = 7 / 3). In formula (a1), R11 is an alkyl group having 12 carbon atoms (C12) and an alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14 = 70:30), R12 is a hydrogen atom, the carbon atom of R11 bonded to -O- is a primary carbon atom, s is 15, t is 0, and u is 0. Coconut fatty acids: Soap (manufactured by NOF Corporation, product name "Coconut Fatty Acids"). Sodium lactate: Enzyme stabilizer (Musashino Chemical Laboratory, product name "Sodium Lactate 60E"). Sodium benzoate: (Lion Specialty Chemicals, trade name "Sodium Benzoate, 35% Aqueous Solution") Paratoluenesulfonic acid: Hydrotrope agent (manufactured by Kyowa Hakko Kirin, trade name "PTS acid"). Sodium hydroxide: pH adjuster (manufactured by Toagosei Co., Ltd., product name "Sodium Hydroxide"). Monoethanolamine: pH adjuster (manufactured by Nippon Shokubai Co., Ltd., product name "Monoethanolamine"). Citric acid: (manufactured by Ipposha Oil & Fat Industries Co., Ltd., product name "Liquid Citric Acid"). Dichlosan (4,4'-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, trade name "TINOSAN HP100"). - Soil Release Polymer 1 (manufactured by BASF, product name "Sokalan HP20"). - Soil Release Polymer 2 (manufactured by Clariant Japan, product name "SRN-170C"). Protease 1 (Novozymes, trade name "Progress Uno100L"). -Protease 2 (manufactured by Novozymes, trade name "Coronase Evity48L"). Amylase (Novozymes, trade name "Amprify Prime 100L"). Mannanase (manufactured by Novozymes, trade name "Mannaway200L"). Pectinase (Novozymes, trade name "XPect1000L"). Cellulase (manufactured by Novozymes, trade name "Carezyme Premium 4500L"). Nuclease (Novozymes, trade name "Pristine 100L"). 1,2-Benzisothiazolin-3-one (manufactured by Clariant Japan, trade name "NIPACIDE BIT20"). Antioxidant: Dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R"). Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399. ·Pigment: Manufactured by Kinmi Kasei Co., Ltd., product name "Green No. 3". Pigment: Brilliant Orange, manufactured by Milliken Japan LLC. Pigment: Made by Milliken Japan LLC, product name "Violet FL". Pigment: Made by Milliken Japan LLC, product name "Violet SH". Pigment: Milliken Japan LLC, product name "SeaGreen CC". Water: Ion-exchanged water. [Storage container] Storage container A: Clear glass bottle (wide-mouth standard bottle, PS-NO.6) Storage container B: Hitachi drum-type washing machine (BD-SX110E) automatic detergent tank (part number BD-SX110CL-002, capacity: approximately 1000 mL, non-sealed container) [Evaluation method] <Cleaning power> Artificially soiled cloth (manufactured by the Laundry Science Association, a general incorporated foundation) was prepared by impregnating unsoiled cloth with artificial soiling, and the resulting cloth was cut into a 5cm x 5cm piece to be used as the soiled cloth.

[0084] The cleaning tester used was a Terg-O-tometer (manufactured by UNITED STATES TESTING).

[0085] The cleaning liquid used was prepared by adding the liquid detergent composition to 900 mL of water (25°C, 5°DH) so that the concentration would be 200 ppm, and stirring for 30 seconds.

[0086] The cleaning solution, 10 of the above soiled fabrics, and the washed knitted fabric were placed in a cleaning tester and washed for 10 minutes at 120 rpm and 25°C with a bath ratio of 20. The fabrics were then transferred to a twin-tub washing machine (Mitsubishi Electric Corporation, product name "CW-C30A1-H1") and dehydrated for 1 minute, then rinsed in 30 L of water (25°C, 5°DH) for 3 minutes and air-dried.

[0087] The reflectance of the unsoiled cloth and the soiled cloth before and after washing was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the cleaning rate (%) was calculated using the following formula (i).

[0088] Cleaning rate (%) = (K / S of soiled cloth before washing - K / S of soiled cloth after washing) / (K / S of soiled cloth before washing - K / S of unsoiled cloth) × 100 (i) [In formula (i), K / S=(1-R / 100) / (2R / 100), where R is the reflectance (%).] The cleaning rates (%) for 10 soiled cloths were calculated and the average value was calculated, and the average cleaning rate (%) was evaluated according to the following evaluation criteria. "Excellent" and "Good" were considered acceptable.

[0089] [Evaluation criteria] ◎: The average cleaning rate is between 80% and 100%.

[0090] Good: The average cleaning rate is between 60% and 80%.

[0091] △: The average cleaning rate is between 40% and 60%.

[0092] ×: The average cleaning rate was 0% or more and less than 40%. <Stability evaluation> In the case of storage container A, 20 mL of the liquid detergent composition of each example was filled into a transparent glass bottle (wide-mouth standard bottle, PS-No. 6), and the bottle was sealed with a lid. In this state, the bottle was left to stand in a thermostatic chamber at 5°C for 7 days.

[0093] In the case of storage container B, 200 mL of the liquid detergent composition of each example was filled into an automatic detergent tank (part number BD-SX110CL-002, capacity: approximately 1000 mL, non-sealed container) attached to a Hitachi drum-type washing machine (BD-SX110E), and the container was left to stand in a constant temperature bath at 5°C for 7 days with the lid closed.

[0094] After storage, in the case of storage container A, the appearance of the liquid detergent composition in the glass bottle was visually observed. In the case of storage container B, various liquid detergent compositions were removed from storage container B and transferred to a transparent glass bottle (wide-mouth standard bottle, PS-No. 6), and then the appearance of the liquid detergent composition was visually observed. For both storage containers A and B, low-temperature stability was evaluated according to the following evaluation criteria. "◎" and "○" were considered to be acceptable.

[0095] [Evaluation criteria] ⊚: The liquid detergent composition in the glass bottle is transparent, with no precipitate or the like observed, and the liquid has high fluidity.

[0096] Good: The liquid detergent composition in the glass bottle was transparent with no precipitate or other visible substances, and the liquid had low fluidity.

[0097] Δ: The liquid detergent composition in the glass bottle was cloudy, but the liquid was fluid.

[0098] ×: The liquid detergent composition in the glass bottle was cloudy and had no fluidity.

[0099]

[0100] [Table 1]

[0101] [Table 2]

Claims

1. Component (A): a nonionic surfactant represented by the following general formula (a1); 2 １ --[(5O) ｓ / (O) ｔ ・・・(11) (In general formula (a1), R １ is a hydrocarbon group having 12 to 18 carbon atoms, EO is an oxyethylene group, s is a number from 12 to 25 indicating the average number of repeats of EO, PO is an oxypropylene group, and t is a number from 1 to 5 indicating the average number of repeats of PO. EO and PO may be added randomly or in blocks. However, when the hydrocarbon group having 14 carbon atoms is R １ It is 50% by mass or more of the total amount.) Component (B): At least one organic solvent selected from 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, diethylene glycol monobutyl ether, polyethylene glycol, 3-methoxy-3-methylbutanol, phenoxyethanol, and polyoxyethylene monophenyl ether having an average repeating number of oxyethylene groups of 4 to 8. Contains A liquid detergent composition in which the total mass of component (A) is 5 mass% or more relative to the total mass of the liquid detergent.

2. The liquid detergent composition according to [1], further comprising a non-soap anionic surfactant as component (C).

3. The liquid detergent composition according to [1] or [2], further comprising a component (D): an enzyme.

4. The liquid detergent composition according to [1], wherein the mass ratio of the component (A) to the component (B) is 1 or more.

5. The liquid detergent composition according to [2], wherein the mass ratio of the component (A) to the component (C) is 5 or more.

6. The liquid detergent composition according to [1], wherein the content of the component (B) is 1 to 20 mass % based on the total mass of the liquid detergent composition.

7. The liquid detergent composition according to [1], further comprising a soil release agent.

8. The liquid detergent composition according to [1], which is for use in a washing machine equipped with an automatic detergent dispensing function.

9. The washing method using the liquid detergent composition according to [1], wherein the amount of the liquid detergent composition used is 3 to 10 g per 30 L of water.

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