Liquid detergent composition for textile products

Abstract

In washing machines with automatic detergent dispensing, the liquid detergent composition filled in the tank is more likely to have its liquid stability compromised. This invention was made in view of these circumstances, and aims to improve the liquid stability of a liquid detergent composition for textile products while maintaining excellent cleaning power. [Solution] (A) Component: R 1 -O-[(EO) s (PO) t The product comprises a nonionic surfactant represented by ]-H, (B) component: at least one selected from alkoxylated polyalkyleneimines and alkoxylated polyalkyleneamines, and (C) component: water.

Description

[Technical Field]

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

[0002] Liquid detergent compositions for textile products such as clothing contain surfactants. These liquid detergent compositions are required to exhibit cleaning effectiveness with a small amount of use. Concentrated liquid detergent compositions are one example of such compositions.

[0003] Concentrated liquid detergent compositions contain a high concentration of surfactants, resulting in a low water content. Therefore, while concentrated liquid detergent compositions offer excellent cleaning power, they suffer from poor liquid stability. For example, under high-temperature conditions (e.g., above 40°C), they tend to change color or decrease in volume (low high-temperature stability). Conversely, under low-temperature conditions (e.g., below 5°C), they tend to precipitate or gel (low low-temperature stability). To address these problems, a liquid detergent composition has been proposed containing two specific nonionic surfactants, a non-soap-based anionic surfactant, and water in specific proportions (Patent Document 1). According to the invention described in Patent Document 1, improvements in cleaning power, low-temperature stability, and high-temperature stability are achieved. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-177870 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Incidentally, there are washing machines that automatically dispense liquid detergent compositions (automatic detergent dispensing washing machines). In automatic detergent dispensing washing machines, the liquid detergent composition is contained in a tank inside the washing machine. The detergent tank is generally not sealed and is exposed to the heat generated by the washing machine. As a result, the liquid detergent composition filled in the tank is more likely to lose its liquid stability. Therefore, the present invention aims to provide a liquid detergent composition for textile products that has excellent cleaning power and superior liquid stability. [Means for solving the problem]

[0006] The present invention has the following aspects. <1> (A) Components: A nonionic surfactant represented by the following formula (a1), R 1 -O-[(EO) s (PO) t ]-H ···(a1) (In 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 a block manner. However, R 1 In R 1 (This is 50% or more of the total mass.) (B) Component: At least one selected from alkoxylated polyalkyleneimines and alkoxylated polyalkyleneamines, (C) Ingredients: Water and, A liquid detergent composition for textile products containing [the specified ingredient]. <2> Furthermore, component (D): contains a miscible organic solvent. <1> A liquid detergent composition for textile products as described above. <3> The content of component (A) is 5 to 45% by mass relative to the total mass of the liquid detergent composition for textile products. <1> or <2> A liquid detergent composition for textile products as described above. <4> The content of the component (B) is 0.5 to 5% by mass based on the total mass of the liquid detergent composition for textile products, and the liquid detergent composition for textile products according to any one of <1> to <3>. <5> The content of the component (C) is 50 to 80% by mass based on the total mass of the liquid detergent composition for textile products, and the liquid detergent composition for textile products according to any one of <1> to <4>.

Effect of the Invention

[0007] According to the liquid detergent composition for textile products of the present invention, it has excellent detergency and is even more excellent in liquid stability.

Mode for Carrying Out the Invention

[0008] (Liquid Detergent Composition for Textile Products) The liquid detergent composition for textile products of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") contains components (A) to (C).

[0009] <Component (A)> The component (A) is a nonionic surfactant represented by the following formula (a1). R 1 -O-[(EO) s / (PO)t]-H ···(a1) (In the 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 repeat number of EO, PO is an oxypropylene group, and t is a number from 1 to 5 indicating the average repeat number of PO. EO and PO may be randomly added or block-added. However, in R 1 , a hydrocarbon group having 14 carbon atoms is 50% by mass or more of the total mass of R 1 .)

[0010] In the formula (a1), the number of carbon atoms of R 1 is 12 to 18, and 12 to 14 are preferred.

[0011] In the component (A), R1 The proportion of C14 hydrocarbon groups to the total mass of hydrocarbon groups is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 100% by mass. When the proportion of C14 hydrocarbon groups is above the lower limit mentioned above, the cleaning power can be further enhanced. Surfactants using natural oil raw materials typically have lipophilic groups with 12 to 14 carbon atoms. However, the hydrophobicity of hydrocarbon groups with 14 carbon atoms is higher than that of hydrocarbon groups with 12 carbon atoms, resulting in a decrease in critical micelle concentration (CMC). Therefore, R 1 Reducing the proportion of C12 hydrocarbon groups in the solution lowers the CMC (critical micelle concentration), thereby improving cleaning power at low concentrations. 1 Reducing the proportion of C16 hydrocarbon groups in the liquid detergent composition can further improve its low-temperature stability.

[0012] R 1 The distribution of carbon atoms in this material is measured by gas chromatography-mass spectrometry (GC-MS).

[0013] In formula (a1), s is between 12 and 25, preferably between 14 and 20, more preferably between 14 and 18, and even more preferably between 14 and 16. When s is within the above range, the sebum stain removal power is good. When s is below the above upper limit, the removal power against sebum stains increases.

[0014] In formula (a1), t is between 1 and 5, with 1 to 3 being more preferred. When t is above the lower limit, the low-temperature stability of the detergent composition can be further enhanced. When t is below the upper limit, the cleaning power at low concentrations can be further enhanced.

[0015] In formula (a1), EO represents an oxyethylene group and PO represents an oxypropylene group. EO and PO may be added randomly or in a block manner, with random addition and PO-terminated block addition being preferred. Random addition can further enhance the low-temperature stability of the detergent composition. PO-terminated block addition can further enhance rinsability during washing. One method for arranging EO and PO randomly is to introduce ethylene oxide and propylene oxide simultaneously. Methods for arranging EO and PO in a block-like manner include introducing ethylene oxide followed by propylene oxide, introducing propylene oxide followed by ethylene oxide, introducing ethylene oxide followed by propylene oxide, and then introducing ethylene oxide again. The aforementioned component (A) may be a single type or a combination of two or more types.

[0016] (A) The content of component (A) is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass, based on the total mass of the liquid detergent composition. If the content of component (A) is above the lower limit, the cleaning power can be further enhanced. If the content of component (A) is below the upper limit, the viscosity of the liquid detergent composition is reduced, and the low-temperature stability can be further enhanced.

[0017] <(B) component> Component (B) is at least one selected from alkoxylated polyalkyleneimine (component (b1)) and alkoxylated polyalkyleneamine (component (b2)). By containing component (B), the liquid detergent composition can enhance its cleaning power, improve liquid stability, and suppress weight loss during storage.

[0018] Component (b1) is an alkylene oxide adduct of a polyalkylene imine. Component (b1) can be represented, for example, by the following formula (II). NH 2 -R 21 -(NA-R 21 ) n -NH2···(II) In formula (II), R 21 Each of these is an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another branched polyamine chain, and n is a number of 1 or more. However, not all of A are hydrogen atoms. R 21R is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. 21 The alkylene group having 2 to 4 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. Polyalkyleneimines are obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms by conventional methods. Examples of alkyleneimines having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. As the polyalkylene imine, polyethyleneimine (PEI) and polypropyleneimine are preferred, with PEI being more preferred. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms in its structure. The weight-average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, even more preferably 400 to 1000, and particularly preferably 500 to 800. The weight-average molecular weight of component (b1) was determined by gel permeation chromatography (GPC) using polyethylene glycol as the standard substance. The polyalkylene imine is preferably one that has 5 to 30 active hydrogen atoms per molecule, more preferably one that has 7 to 25, and even more preferably one that has 10 to 20. (b1) Component is obtained by adding an alkylene oxide to a polyalkylene imine. Examples of this method include adding an alkylene oxide such as ethylene oxide to the starting material, a polyalkylene imine, at 100-180°C in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate. Examples of alkylene oxides include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred. (b1) Examples of components include ethylene oxide adducts of polyalkyleneimines, propylene oxide adducts of polyalkyleneimines, and ethylene oxide-propylene oxide adducts of polyalkyleneimines. The ethylene oxide-propylene oxide adducts of polyalkyleneimines are obtained by adding ethylene oxide and propylene oxide to polyalkyleneimines, and the order of addition of ethylene oxide and propylene oxide to the polyalkyleneimine, as well as the form of addition (block-like, random), are arbitrary. (b1) The component is preferably an ethylene oxide adduct of polyalkyleneimine or an ethylene oxide-propylene oxide adduct of polyalkyleneimine, and more preferably an ethylene oxide adduct of polyalkyleneimine. (b1) The component is preferably one in which an average of 5 to 40 alkylene oxides are added to one active hydrogen atom of the raw material polyalkyleneimine, and preferably one in which an average of 10 to 30 alkylene oxides are added. That is, it is preferably one in which an average of 5 to 40 moles of alkylene oxides are added to one mole of active hydrogen of the raw material polyalkyleneimine, and preferably one in which an average of 10 to 30 moles of alkylene oxides are added. (b1) The weight-average molecular weight of component is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 5,000 to 30,000, and particularly preferably 10,000 to 20,000. (b1) Examples of components include the compound shown in formula (II-a).

[0019] [ka]

[0020] In formula (II-a), R 32 Each of these is an alkylene group having 2 to 6 carbon atoms, and each of these is a number of 1 or more. R 32 The alkylene group having 2 or 3 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. m is (R 32 This is the average number of repetitions of O), and each is independently preferably 5 to 40, and more preferably 10 to 30. (b1) The components may be synthetic or commercially available. Examples of commercially available products include the "Sokalan HP20" manufactured by BASF.

[0021] (b2) Component is an alkylene oxide adduct of a polyalkyleneamine. Polyalkyleneamines are represented by the following formula (III).

[0022] NH2(R 31 NH) l H ···(III) In formula (III), R 31 is an alkylene group having 2 to 6 carbon atoms, and l is a number greater than or equal to 1.

[0023] R 31 R is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. 31 The alkylene group having 2 to 4 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. Polyethyleneamines are preferred as polyalkyleneamines. Examples of polyethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. These polyethyleneamines can be obtained by known production methods, for example, by reacting ammonia with ethylene dichloride.

[0024] The weight-average molecular weight of the polyalkyleneamine is preferably 60 to 1800, more preferably 60 to 1000, and even more preferably 60 to 800. The polyalkyleneamine is preferably one that has 6 to 30 active hydrogen atoms in one molecule, and more preferably one that has 7 to 20 active hydrogen atoms.

[0025] Component (b2) is obtained by adding an alkylene oxide to a polyalkyleneamine. This reaction can be carried out in the same manner as for component (b1). Examples of alkylene oxides include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred. (b2) Examples of components include ethylene oxide adducts of polyalkyleneamines, propylene oxide adducts of polyalkyleneamines, and ethylene oxide-propylene oxide adducts of polyalkyleneamines. (b2) The component is preferably an ethylene oxide adduct of polyalkyleneamine or an ethylene oxide-propylene oxide adduct of polyalkyleneamine, and more preferably an ethylene oxide adduct of polyalkyleneamine. (b2) The component is preferably one in which an average of 5 to 40 alkylene oxides are added to one active hydrogen atom of the raw material polyalkyleneamine, and preferably one in which an average of 10 to 30 alkylene oxides are added. That is, it is preferably one in which an average of 5 to 40 moles of alkylene oxides are added to one mole of active hydrogen of the raw material polyalkyleneamine, and preferably one in which an average of 10 to 30 moles of alkylene oxides are added.

[0026] (b2) The weight-average molecular weight of component is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 5,000 to 30,000, and particularly preferably 10,000 to 20,000.

[0027] (B) Component (b1) is preferred. Among the components of (b1), the ethylene oxide adduct of polyethyleneimine (ethoxylated polyethyleneimine) is preferred.

[0028] (B) The content of component (B) is preferably 0.5 to 5% by mass, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 2% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is above the lower limit, the cleaning power can be further enhanced and weight loss can be further suppressed. If the content of component (B) is below the upper limit, the low-temperature stability can be further enhanced.

[0029] The ratio of the content of component (B) to the content of component (A), expressed as the mass ratio of component (B) / component (A) (B / A ratio), is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, and even more preferably 0.05 to 0.1. If the B / A ratio is above the lower limit, the moisture retention capacity is increased, and weight loss during storage can be further suppressed. If the B / A ratio is below the upper limit, the cleaning power can be further increased.

[0030] <(C) component> Component (C) is water. The liquid detergent composition can be made more dispersible in water by including component (C). (C) Examples of components include purified water, ion-exchanged water, distilled water, pure water, tap water, well water, etc.

[0031] The content of component (C) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and particularly preferably 60 to 70% by mass, based on the total mass of the liquid detergent composition. If the content of component (C) is above the lower limit, the viscosity of the liquid detergent composition can be reduced and the low-temperature stability can be further improved. If the content of component (C) is below the upper limit, the evaporation of component (C) can be suppressed and weight loss during storage can be further reduced.

[0032] <(D) component> The liquid detergent composition may contain component (D) (a water-miscible organic solvent). By containing component (D), the liquid detergent composition can further suppress weight loss and improve low-temperature stability.

[0033] (D) Examples of components include ethanol, 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 with an average number of repeating oxyethylene groups of 4 to 8.

[0034] From the viewpoint of versatility and volatility, ethanol, ethylene glycol, propylene glycol, glycerin, polyethylene glycol, 3-methoxy-3-methylbutanol, and phenoxyethanol are preferred as component (D), and propylene glycol, glycerin, polyethylene glycol, and 3-methoxy-3-methylbutanol are more preferred. These (D) components may be a single type or a combination of two or more types.

[0035] The content of component (D) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total mass of the liquid detergent composition. If the content of component (D) is above the lower limit, the proportion of water in the liquid detergent composition can be reduced, thereby suppressing evaporation and further reducing weight loss. In addition, if the content of component (D) is above the lower limit, the low-temperature stability of the liquid detergent composition can be further improved. If the content of component (D) is below the upper limit, the amount of other components can be sufficiently ensured.

[0036] <Optional ingredients> The liquid detergent composition may contain other components (optional components) besides components (A) to (D). Optional ingredients include surfactants other than component (A) (optional surfactants), antibacterial agents, organic acids, viscosity reducers, solubilizers, alkalizing agents, metal ion scavengers, antioxidants, preservatives, enzymes (protease, lipase, cellulase, etc.), enzyme stabilizers, texture enhancers, alkali builders (alkanolamine, etc.), hydrotropes, fluorescent agents, fluorescent whitening agents, color transfer inhibitors, re-soiling inhibitors, pearlescent agents, soil release agents, fragrances, colorants, emulsifiers, extracts of natural products, pH adjusters, etc. These optional ingredients may be used individually or in combination of two or more. Furthermore, the sum of components (A) to (D) and the above optional components shall not exceed 100% by mass.

[0037] ≪Optional surfactants≫ Examples of optional surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants other than component (A). These optional surfactants may be used individually or in combination of two or more types. When a liquid detergent composition contains an optional surfactant, an anionic surfactant is preferred as the optional surfactant. The inclusion of an anionic surfactant enhances the re-soiling prevention performance.

[0038] Examples of nonionic surfactants other than component (A) include polyoxyethylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl)amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like.

[0039] Examples of anionic surfactants include non-soap-based anionic surfactants, higher fatty acids, or their salts. Examples of non-soap-based anionic surfactants include linear alkylbenzene sulfonic acid or its salts; α-olefin sulfonates; linear or branched alkyl sulfate ester salts; alkyl ether sulfate ester salts or alkenyl ether sulfate ester salts; alkane sulfonates having alkyl groups; and α-sulfo fatty acid ester salts.

[0040] Linear alkylbenzene sulfonic acid or its salt is preferably one in which the linear alkyl group has 8 to 16 carbon atoms, and more preferably one in which the linear alkyl group has 10 to 14 carbon atoms. As for α-olefin sulfonates, those with 10 to 20 carbon atoms are preferred. Alkyl sulfate esters with 10 to 20 carbon atoms are preferred. Preferably, the alkyl ether sulfate or alkenyl ether sulfate has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, to which an average of 1 to 10 moles of ethylene oxide is added (i.e., polyoxyethylene alkyl ether sulfate or polyoxyethylene alkenyl ether sulfate). The alkanesulfonate has 10 to 20 carbon atoms, preferably 14 to 17, and secondary alkanesulfonates are particularly preferred. As the α-sulfo fatty acid ester salt, those with 10 to 20 carbon atoms are preferred.

[0041] Examples of salts of non-soap-based anionic surfactants include alkali metal salts such as sodium salts and potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, alkanolamine salts such as 2-amino-2-methylpropanol salt and 2-amino-2-methylpropanediol.

[0042] Examples of higher fatty acids and their salts (so-called soaps) include fatty acids with 8 to 22 carbon atoms (higher fatty acids) or their salts (higher fatty acid salts). Examples of higher fatty acids include salts of 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, as well as mixed fatty acids such as coconut oil fatty acids and beef tallow fatty acids. Examples of salts of these higher fatty acids include alkali metal salts such as sodium salts and potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, alkanolamine salts such as 2-amino-2-methylpropanol salt and 2-amino-2-methylpropanediol, and basic amino acid salts such as lysine and arginine.

[0043] Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts; long-chain aliphatic amide alkyl tertiary amines or salts thereof such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, laurate dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearate dimethylaminopropylamide, behenate dimethylaminopropylamide, and oleate dimethylaminopropylamide; and palmitate diethanolaminopropylamide, stearate diethanolaminopropylamide, and the like.

[0044] Examples of amphoteric surfactants include alkylbetaine type, alkylamidebetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphate-type amphoteric surfactants. These optional surfactants may be used individually or in combination of two or more. They may be used individually or in combination of two or more.

[0045] (A) The total amount of component and optional surfactant (total surfactant amount) is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, relative to the total mass of the liquid detergent composition. The content of component (A) relative to the total mass of the total amount of surfactants is preferably 50% by mass or more, more preferably 60% by mass or more, and may be 100% by mass.

[0046] ≪Metal ion scavenger≫ Examples of metal ion scavenging agents include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid. The content of the metal ion scavenging agent is preferably, for example, 0.1 to 20% by mass relative to the total mass of the liquid detergent composition.

[0047] Antioxidants Examples of antioxidants include butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite. The antioxidant content is preferably, for example, 0.01 to 2% by mass relative to the total mass of the liquid detergent composition.

[0048] <<Preservatives>> Examples of preservatives include "Caisson CG" (product name) from Dow Chemical, "Acticide MBS" (product name) from Soe Japan, and "NIPACIDE BIT 20" (product name) from Clariant. The preservative content is preferably, for example, 0.001 to 1% by mass relative to the total mass of the liquid detergent composition.

[0049] <Coloring agents> Examples of colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names). These colorants may be used individually or in combination of two or more. The colorant content is preferably 0.00005 to 0.005% by mass relative to the total mass of the liquid detergent composition.

[0050] Emulsifying agent Examples of emulsifying agents include polystyrene emulsion and polyvinyl acetate emulsion, typically emulsions with a solid content of 30-50% by mass. Specifically, examples include polystyrene emulsion (manufactured by Saiden Chemical Co., Ltd., product name Saibinol RPX-196 PE-3, solid content 40% by mass). These emulsifying agents may be used individually or in combination of two or more. The emulsifying agent content is preferably 0.01-0.5% by mass relative to the total mass of the liquid detergent composition.

[0051] ≪Fragrance≫ Examples of fragrances include the fragrance components described in Japanese Patent Publication No. 2002-146399. These fragrances may be used individually or in combination of two or more. The fragrance content is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent composition.

[0052] ≪Extract≫ Extracts of natural products include Japanese pagoda tree, bearberry, echinacea, golden flower, phellodendron, coptis japonica, allspice, oregano, Japanese pagoda tree, chamomile, honeysuckle, Sophora flavescens, schizonepeta, jasmine, bay laurel, magnolia, burdock, comfrey, jasmine, burnet, peony, ginger, tall goldenrod, elderberry, sage, mistletoe, Atractylodes macrocephala, thyme, Anemarrhena asphodeloides, clove, Satsuma mandarin, tea tree, and barbecue. Examples of plants include Lee, Houttuynia cordata, Nandina domestica, Frankincense, Armillaria japonica, White sedge, Saposhnikovia divaricata, Watercress, Hops, Rosehip, Mountain grape, Purple sedge, European mint, Belamcanda chinensis, Japanese perilla, Eucalyptus, Lavender, Rose, Rosemary, Balan, Japanese cedar, Gilead balsam, White cinquefoil, Kochia cypress, Willow, Gentian, Sweetgum, Adenophora triphylla, Japanese water chestnut, Japanese knotweed, Licorice, and St. John's wort. The extract content is preferably, for example, 0 to 0.5% by mass relative to the total mass of the liquid detergent composition.

[0053] ≪Insoluble particles≫ Insoluble particles are particles that exist as solids in a liquid detergent composition without dissolving. Examples of insoluble particles include capsule particles, beads or pearlescent agents to impart a specific product aesthetic, bentonite, and carboxymethylcellulose (CMC). The insoluble particles may be used individually or in combination of two or more types. Capsule particles contain an active ingredient enclosed within a capsule wall formed from a polymer compound. Capsule particles can be manufactured by known methods, such as interfacial polymerization and in-situ polymerization. Examples of polymer compounds that form the capsule wall include synthetic polymers such as polyacrylic acid-based, polyvinyl-based, polymethacrylic acid-based, melamine-based, and urethane-based polymers. These may be used individually or in combination of two or more types. Examples of active ingredients include fragrance components and sunscreen components (UV absorbers, UV scatterers, etc.).

[0054] pH adjuster Examples of pH adjusting agents include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; sodium carbonate; and acidulants such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. Among these, alkanolamines, sodium hydroxide, potassium hydroxide, and sodium carbonate are preferred. pH adjusters may be used individually or in combination of two or more types.

[0055] (Physical properties) pH The pH of the liquid detergent composition at 25°C is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 8. Skin irritation can be reduced if the pH is within the above preferred range. The pH is measured using a pH meter (for example, using the "HM-30G" product name manufactured by Toa DKK Co., Ltd.).

[0056] ≪Viscosity≫ The viscosity of the liquid detergent composition at 25°C is preferably 10 to 1,000 mPa·s, and more preferably 10 to 500 mPa·s. A viscosity within this range ensures good handling. Viscosity was measured using a Brookfield viscometer (Type B viscometer) with the rotor speed set to 60 rpm, after 60 seconds.

[0057] (Method for producing liquid detergent composition) Liquid detergent compositions can be manufactured according to conventionally known manufacturing methods. For example, a liquid detergent composition can be manufactured by dissolving components (A), (B), (C), (D), and optionally any other components in a portion of water, adjusting the pH with a pH adjuster as needed, and then adding the remaining water.

[0058] (How to use) Methods of using the liquid detergent composition of the present invention (i.e., methods for washing textile products) include, for example, putting the liquid detergent composition into the detergent dispenser of a washing machine and then starting the washing machine; adding the liquid detergent composition to the water together with the items to be washed during washing; immersing the items to be washed in a cleaning solution prepared by dissolving the liquid detergent composition in water beforehand; and applying the liquid detergent composition directly to the items to be washed, leaving it for, for example, 3 minutes to 24 hours, and then performing a normal wash.

[0059] Furthermore, it is preferable to use a washing machine equipped with an automatic detergent dispenser (a washing machine with automatic detergent dispensing). The automatic detergent dispenser is a device that automatically dispenses liquid detergent composition from a tank containing the composition into the washing tub via a filter at the bottom of the tank to remove debris and through a dispensing pipe. A measuring device such as a syringe pump is provided in the middle of the dispensing pipe, allowing a fixed amount, set according to the amount of laundry, to be transferred from the tank to the washing tub. Using an automatic detergent dispenser not only eliminates the hassle of measuring, but also prevents liquid detergent from getting on your hands or spilling and staining the washing machine or surrounding area during the measuring process.

[0060] Furthermore, it is preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. Using an automatic dispenser is also preferable because it allows for accurate measurement of even small amounts of liquid cleaning agent composition, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse. Some automatic dispensers utilize infrared sensors or similar technologies to dispense liquids automatically without requiring the user to touch any switches. Using such an automatic dispenser allows users to measure out liquid detergent compositions simply by holding a container in one hand, significantly reducing the burden on the user.

[0061] When using an automatic dispenser, it is also preferable to receive the liquid detergent composition dispensed into a flexible container and then place that flexible container directly into the washing machine. This ensures that the entire amount of the dispensed liquid detergent composition is reliably dissolved in the washing solution. Examples of materials for flexible containers that can be directly put into a washing machine include silicone resin, polyvinyl chloride, elastomer, flexible polyester, flexible polypropylene, and polyurethane.

[0062] Examples of items to be washed include clothing, dishcloths, towels, sheets, curtains, and other textile products. The material of the textile products is not particularly limited and may be any of the following: natural fibers such as cotton, silk, and wool, or synthetic fibers such as polyester and polyamide.

[0063] When a liquid detergent composition is dissolved in water to make a cleaning solution, it is preferable to dilute it, for example, 5 to 6,000 times (by volume). The water ratio per item being washed (mass of washing solution / mass of items being washed) is preferably 5 or higher for drum-type washing machines and preferably 10 or higher for top-loading washing machines. [Examples]

[0064] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0065] (Raw materials used) <(A) component> • A-1 (AEP nonionic): Manufactured by Sanyo Chemical Industries, Ltd., product name "Emulmin CS-100W". A compound obtained by randomly adding 15 moles of ethylene oxide and 1.7 moles of propylene oxide to an alcohol having a linear alkyl group with 14 carbon atoms. A-2(C14 15EO3PO): A PO-terminated compound obtained by adding 15 moles of ethylene oxide to an alcohol having a linear alkyl group with 14 carbon atoms, followed by the addition of 3 moles of propylene oxide. A-3(C14 20EO3PO): A PO-terminated compound obtained by adding 20 moles of ethylene oxide to an alcohol having a linear alkyl group with 14 carbon atoms, followed by the addition of 3 moles of propylene oxide.

[0066] <Optional surfactants> · A'-1(C124 15EO3PO): A PO-terminated compound produced by adding 15 moles of ethylene oxide to 1 mole of a primary alcohol (mass ratio of C12 alcohol to C14 alcohol = 7 / 3), followed by the addition of 3 moles of propylene oxide. Manufactured by Lion Chemical Co., Ltd. A'-2(C14 15EO): A compound obtained by adding 15 moles of ethylene oxide to 1 mole of a primary alcohol (100% C14 alcohol). A'-3 (LMAO): A primary alcohol (mass ratio of C12 alcohol to C14 alcohol = 7 / 3) to which 15 moles of ethylene oxide are added. LMAO-90 (trade name), manufactured by Lion Corporation. A'-4(LAS): Linear alkylbenzene sulfonic acid, Lypon LH-200 (trade name), 10-14 carbon atoms, average molecular weight 322, manufactured by Lion Specialty Chemicals. · A'-5(AES(1EO)): Polyoxyalkylene alkyl ether sulfate. A mixture of polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene myristyl ether sodium sulfate, with an average number of EO added moles of 1.

[0067] <(B) component> • B-1 (HP20): Ethylene oxide adduct of polyethyleneimine, BASF, trade name: Sokalan HP20. In formula (II-a), R 32 A compound in which is ethylene and m is 20.

[0068] <(C) component> ·Purified water.

[0069] <(D) component> D-1: Solfit (trade name), 3-methoxy-3-methylbutanol, manufactured by Kuraray Co., Ltd. D-2: PEG, polyethylene glycol, mass-average molecular weight 1000, manufactured by Junsei Chemical Co., Ltd. D-3: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd.

[0070] <Common ingredients> • Coconut fatty acid: Coconut fatty acid (PKO) TC (product name), manufactured by NOF Corporation... 1% by mass. • Fragrance: Fragrance composition A described in Tables 11-18 of Japanese Patent Publication No. 2002-146399... 1% by mass. • Enzyme: Coronase Evity48L (product name), manufactured by Novozymes, Inc. ... 1% by mass. • Dichrosan: TINOSAN HP100 (product name), manufactured by BASF... 1% by mass. • Citric acid: Liquid citric acid (product name), manufactured by Ipposha Oil & Fat Industry Co., Ltd. ... 0.1% by mass. Sodium benzoate: Sodium benzoate, 35% aqueous solution (product name), manufactured by Lion Specialty Chemicals, Inc. ... 1% by mass. • Sodium hydroxide: Sodium hydroxide (product name), manufactured by Toagosei Co., Ltd. ... 0.4% by mass.

[0071] (Evaluation method) <Cleaning power> The soiled cloth was made by impregnating oil-based cloth (unstained cloth) with artificial stains (manufactured by the Japan Laundry Science Association), and then cutting it into 5cm x 5cm pieces. A Terg-O-tometer (manufactured by UNITED STATES TESTING) was used as the cleaning test device. As the cleaning solution, a liquid cleaning agent composition was added to 900 mL of water (25°C, 3°DH) to a concentration of 200 ppm and stirred for 30 seconds. The cleaning solution, 10 of the aforementioned soiled cloths, and the cleaned knitted cloth were placed in a cleaning test machine, and the cloths were washed for 10 minutes at 120 rpm and 25°C, with a bath ratio of 20:1. Afterwards, they were transferred to a twin-tub washing machine (Mitsubishi Electric, product name "CW-C30A1-H1"), spun dry for 1 minute, rinsed in 30L of water (25°C, 3°DH) for 3 minutes, and air-dried. The reflectance of unstained cloth and soiled cloth before and after washing was measured using a colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700"), and the washing rate (%) was calculated using the following formula (s1).

[0072] Cleaning rate (%) = (K / S of soiled cloth before cleaning - K / S of soiled cloth after cleaning) / (K / S of soiled cloth before cleaning - K / S of unsoiled cloth) × 100 ... (s1) [In formula (s1), K / S=(1-R / 100) 2 (2R / 100). R is reflectance (%).

[0073] ≪Judgment criteria≫ ◎: The average cleaning rate is 60% or higher. ○: The average cleaning rate is between 50% and 60%. △: The average cleaning rate is between 40% and 50%. ×: The average cleaning rate is less than 40%.

[0074] <Weight remaining rate> Each example was filled with 20g of the liquid cleaning agent in a transparent glass bottle (wide-mouth standard bottle, PS-NO.6), and left undisturbed in an open system in a constant temperature bath at 40°C and 20% RH for two weeks. The weight of the contents of the glass bottle after standing (W1) and the weight of the contents of the glass bottle before standing in a constant temperature bath at 40°C and 20% RH (W0) were measured, and the weight retention rate (%) was calculated using the following formula (s2). A higher retention rate indicates that the weight loss has been suppressed.

[0075] Weight remaining rate (%)=W1 / W0×100...(s2)

[0076] ≪Judgment criteria≫ ◎: Weight retention rate is 85% or higher. ○: Weight retention rate is 80% or more but less than 85%. △: Weight retention rate is 75% or more but less than 80%. ×: Weight retention rate is less than 75%.

[0077] <Low temperature stability> 85 mL of the liquid detergent composition was filled into a glass bottle (wide-mouth standard bottle PS-NO.11), sealed with the lid, and stored undisturbed in a constant temperature bath set to -5°C for 4 weeks. The appearance of the liquid detergent composition was visually observed, and its low-temperature stability was evaluated according to the following evaluation criteria.

[0078] ≪Evaluation Criteria≫ ◎: The liquid remains uniformly clear for more than 4 weeks from the start of storage. ○: The liquid is uniform and transparent for more than 3 weeks but less than 4 weeks from the start of storage. △: The liquid remains uniform and transparent for more than two weeks but less than three weeks from the start of storage. ×: The liquid will no longer be a uniform, clear liquid within two weeks of the start of storage.

[0079] (Examples 1-14, Comparative Examples 1-3) Each component was mixed according to the composition shown in Tables 1 and 2. Sodium hydroxide was added to achieve the pH shown in the table at 25°C, and then purified water was added to bring the total volume to 100% by mass to obtain the liquid detergent composition for each example. A "-" in the table indicates that the ingredient is not included. The content of each ingredient is shown as the amount equivalent to its pure content (enzymes and fragrances are shown as content in their natural form).

[0080] [Table 1]

[0081] [Table 2]

[0082] As shown in Tables 1-2, Examples 1-14 to which the present invention was applied showed a cleaning efficiency of "△" to "◎", a weight retention rate of "◎" or "○", and low-temperature stability of "◎" or "○". From the results of Examples 1-6 and 14, it was found that a higher average number of repeats of EO in component (A) resulted in a higher weight retention rate. The results from Examples 7-8 showed that the higher the total amount of surfactant, the greater the cleaning power. The results from Examples 9-10 showed that a higher content of component (B) resulted in increased cleaning power. From the results of Examples 1, 11-12, the higher the boiling point of component (D), the higher the weight retention rate. The results from Examples 1 and 13 showed that as the content of component (D) increased, the weight retention rate also increased. R 1 In R 1 Comparative Example 1, which contained less than 50% of the total mass, had a cleaning power of "△". Comparative Example 2, which used a nonionic surfactant that does not contain PO, showed a low-temperature stability rating of "△". Comparative Example 3, which lacked component (B), had a cleaning power of "△" and a weight retention rate of "×". From the results above, it was confirmed that by applying the present invention, it is possible to improve liquid stability while maintaining excellent cleaning power.

Claims

1. (A) Components: A nonionic surfactant represented by the following formula (a1), 2 １ --[(5O) ｓ / (O) ｔ ・・・(11) (In 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 a block manner. However, R １ In this case, a hydrocarbon group with 14 carbon atoms is R １ (This is 50% or more of the total mass.) (B) Component: At least one selected from alkoxylated polyalkyleneimines and alkoxylated polyalkyleneamines, (C) Ingredients: Water and A liquid detergent composition for textile products containing [the specified ingredient].

2. Furthermore, the liquid detergent composition for textile products according to claim 1, further comprising component (D): a miscible organic solvent.

3. The liquid detergent composition for textile products according to claim 1 or 2, wherein the content of component (A) is 5 to 45% by mass relative to the total mass of the liquid detergent composition for textile products.

4. The liquid detergent composition for textile products according to claim 1 or 2, wherein the content of component (B) is 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition for textile products.

5. The liquid detergent composition for textile products according to claim 1 or 2, wherein the content of component (C) is 50 to 80% by mass with respect to the total mass of the liquid detergent composition for textile products.

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