Liquid detergent composition for fibrous products

Abstract

To provide a liquid detergent composition for fibrous products having enhanced liquid stability and reduced foaming.SOLUTION: A liquid detergent composition for fibrous products comprises, in specific proportions: (A) a non-soap anionic surfactant including at least one selected from α-olefin sulfonic acid and a salt thereof, internal olefin sulfonic acid and a salt thereof, and alkylsulfosuccinic acid and a salt thereof; (B) a specific nonionic surfactant; (C) a water-miscible organic solvent having a boiling point of 120°C or higher; and (D) water.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid detergent composition for textile products.

Background Art

[0002] In a washing machine with an automatic detergent dispensing function, a liquid detergent composition for textile products (hereinafter sometimes simply referred to as "liquid detergent composition") is stored in a non-sealed dedicated tank inside the washing machine. The stored liquid detergent composition is automatically metered and introduced into the washing tub at each washing, for example, by setting the usage amount per 30 L of water.

[0003] As the liquid detergent composition, there is a concentrated liquid detergent composition containing a surfactant at a high concentration. The concentrated liquid detergent composition exhibits detergency with a small usage amount. For example, Patent Document 1 proposes a liquid detergent composition containing a specific anionic surfactant, a nonionic surfactant, a specific organic solvent, and an enzyme.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Incidentally, in a washing machine with a detergent automatic dosing function, it is necessary to clean (tank cleaning) the tank for automatic dosing and the supply path about once every few months. At this time, the tank is taken out, the inside of the tank is cleaned, and then warm water is put into the tank to clean the supply flow path of the liquid detergent composition. The tank has a foreign matter filtration filter. There are problems that the area around the foreign matter filtration filter is easily exposed to air and the liquid detergent composition easily adheres, and the liquid detergent composition located inside the foreign matter filtration filter is difficult to dissolve. Also, when tap water directly hits the foreign matter filtration filter during tank cleaning, foaming is promoted. If foaming persists during tank cleaning, there is a problem that it is impossible to determine the end of tank cleaning. These problems may become prominent when using a conventional concentrated liquid detergent composition. Also, as described above, in a washing machine with a detergent automatic dosing device, the liquid detergent composition is stored in a dedicated tank inside the washing machine. In a washing machine with a detergent automatic dosing device, the usage mode of the liquid detergent composition is different from that of the conventionally used liquid detergent composition in a bottle, such as being heated when the drying function of the washing machine is used. The liquid detergent composition in the tank may have the solvent volatilize and the viscosity increase in a high-temperature environment such as being heated. When the viscosity of the liquid detergent composition increases, problems such as inappropriate metering may occur. Alternatively, at low temperatures, the liquid detergent composition in the tank may lose its fluidity due to separation or the like. When the fluidity of the liquid detergent composition is lost, problems such as inappropriate metering may occur. Therefore, the liquid detergent composition is required to have better liquid stability. The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid detergent composition for textile products that is excellent in liquid stability and can suppress foaming.

Means for Solving the Problems

[0006] The present invention has the following aspects. <1> (A) Component: A non-soap anionic surfactant containing at least one essential anionic surfactant selected from α-olefin sulfonic acid and its salts, internal olefin sulfonic acid and its salts, and alkyl sulfosuccinic acid and its salts, (B) Component: A nonionic surfactant containing at least one selected from the nonionic surfactant (b1) represented by the following formula (b1), the nonionic surfactant (b2) represented by the following formula (b2), and the nonionic surfactant (b3) represented by the following formula (b3), R 11 -O-[(EO) h / (A 11 O) j -(EO) k -R 12 ···(b1) [In the formula (b1), R 11 is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a primary carbon atom, R 12 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, h is a number from 3 to 25 indicating the average number of EO repetitions, A 11 O is at least one of an oxypropylene group and an oxybutylene group, j is a number from 0.1 to 10 indicating the average number of A 11 O repetitions, and k is a number from 0 to 20 indicating the average number of EO repetitions.] R 21 -O-[(EO) p / (A 21 O) q -(EO) r -R 22 ···(b2) [In the formula (b2), R 21 is a branched hydrocarbon group having 8 to 22 carbon atoms, R 22 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 indicating the average number of EO repetitions, A 12 O is at least one of an oxypropylene group and an oxybutylene group, q is a number from 0.1 to 10 indicating the average number of A 21is a number from 0 to 10 indicating the average number of repetitions of O, and r is a number from 0 to 20 indicating the average number of repetitions of EO. R 31 -O-[(EO) s / (A 31 O) t -(EO) u -R 32 ···(b3) [In the formula (b3), R 31 is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a secondary carbon atom. R 32 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, s is a number from 3 to 25 indicating the average number of repetitions of EO, and A 31 O is at least one of an oxypropylene group and an oxybutylene group, t is a number from 0 to 10 indicating the average number of repetitions of A 31 O, and u is a number from 0 to 20 indicating the average number of repetitions of EO. (Component (C): A water-miscible organic solvent having a boiling point of 120 °C or higher, and (Component (D): Water, and A liquid detergent composition for textile products containing The content of the essential anionic surfactant is less than 10% by mass based on the total mass of the liquid detergent composition for textile products. The content of the component (D) is 30% by mass or less based on the total mass of the liquid detergent composition for textile products. The ratio of the content of the component (A) to the content of the component (B), and the mass ratio represented by (A) component / (B) component is less than 1. The total of the mass of the component (A) and the mass of the component (B) is 50% by mass or more based on the total mass of the liquid detergent composition for textile products. The ratio of the mass of the component (C) to the mass of the component (D), and the mass ratio represented by (C) component / (D) component is 1.2 or less. A liquid detergent composition for textile products. <2> The component (B) is at least one specific nonionic surfactant selected from the component (b1) in which the total of h and k in the formula (b1) is 12 or more, the component (b2) in which the total of p and r in the formula (b2) is 12 or more, and the component (b3) in which the total of s and u in the formula (b3) is 12 or more. The liquid detergent composition for textile products according to <1>. <3> The content of the specific nonionic surfactant is 20% by mass or more based on the total mass of the liquid detergent composition for textile products. The liquid detergent composition for textile products according to <2>. <4> The component (C) contains at least one selected from phenoxyethanol, diethylene glycol monobutyl ether, propylene glycol, and polyethylene glycol. The liquid detergent composition for textile products according to any one of <1> to <3>.

Advantages of the Invention

[0007] According to the liquid detergent composition for textile products of the present invention, it has excellent liquid stability and can suppress foaming.

Embodiments 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") is a composition containing components (A) to (D).

[0009] <Component (A)> The component (A) is a non-soap anionic surfactant containing at least one essential anionic surfactant selected from α-olefin sulfonic acid and its salts (AOS, hereinafter sometimes referred to as "(a1) component"), internal olefin sulfonic acid and its salts (IOS, hereinafter sometimes referred to as "(a2) component"), and alkyl sulfosuccinic acid and its salts (hereinafter sometimes referred to as "(a3) component"). By including the component (A), the liquid stability (low-temperature stability) at low temperatures (for example, 0°C or lower) of the liquid detergent composition can be enhanced. The "non-soap anionic surfactant" is an anionic surfactant excluding higher fatty acids or their salts (so-called soaps). Higher fatty acids are typically fatty acids having 8 to 22 carbon atoms.

[0010] Examples of the component (a1) include AOS having 8 to 24 carbon atoms. Examples of the salt of the component (a1) include alkali metal salts, alkaline earth metal salts, alkanolamine salts and the like. Examples of the alkali metal salts include sodium salts, potassium salts and the like. Examples of the alkaline earth metal salts include calcium salts, magnesium salts and the like. Examples of the amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts and the like.

[0011] The component (a2) is a compound obtained by sulfonating an olefin in which a double bond is present inside the 2-position. Examples of the component (a2) include IOS having 8 to 24 carbon atoms. The salt of the component (a2) is the same as the salt of the component (a1).

[0012] Examples of the component (a3) include compounds having an alkyl group having 5 to 18 carbon atoms. The salt of the component (a3) is the same as the salt of the component (a1).

[0013] The essential anionic surfactant may be any one of them alone or a combination of two or more of them.

[0014] ≪Other non-soap anionic surfactants≫ The component (A) may contain a non-soap anionic surfactant (optional anionic surfactant) other than the essential anionic surfactant. Examples of optional anionic surfactants include linear alkylbenzene sulfonic acids having 8 to 22 carbon atoms or salts thereof (LAS), linear or branched alkyl sulfates having 10 to 24 carbon atoms or salts thereof (AS), polyoxyalkylene alkyl (or alkenyl) ether sulfates or salts thereof (AES, APS, AEPS), alkane sulfonic acids or salts thereof, α-sulfofatty acid esters having 10 to 18 carbon atoms or salts thereof, hydroxyalkane sulfonic acids or salts thereof (HAS), alkyl ether carboxylic acids or salts thereof, polyoxyalkylene ether carboxylic acids or salts thereof, alkylamide ether carboxylic acids or salts thereof, alkenylamide ether carboxylic acids or salts thereof, carboxylic acid type anionic surfactants such as acylaminocarboxylic acids or salts thereof; phosphate ester type anionic surfactants such as alkyl phosphate esters or salts thereof, polyoxyalkylene alkyl phosphate esters or salts thereof, polyoxyalkylene alkyl phenyl phosphate esters or salts thereof, glycerin fatty acid ester monophosphate esters or salts thereof, and the like. Salts of these optional anionic surfactants are the same as those of component (a1). These optional anionic surfactants may be used alone or in combination of two or more.

[0015] As the optional anionic surfactant, LAS, AS, AES, APS, and AEPS are preferred. From the viewpoint of sebum detergency, AS, AES, APS, and AEPS are more preferred. From the viewpoint of foam suppression, AEPS is even more preferred. As the optional anionic surfactant, from the viewpoint of foam suppression, it preferably has a branched alkyl group, EO, and PO in its structure. From the viewpoint of sebum detergency, it is more preferred to have either EO or PO, and even more preferred to have both EO and PO. By containing EO, the evaporation of water in a high-temperature environment can be better suppressed (excellent high-temperature stability). By containing PO, the effect of foam suppression can be enhanced more during automatic dosing tank cleaning.

[0016] AES, APS, and AEPS are represented by the following formula (a11) (component (a11)). R1 -O-[(EO) m / (PO) n -SO3 - M + ···(a11) [(In the formula (a11), R 1 is 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. M + is a counter cation.]

[0017] (In the formula (a11), R 1 has 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 14 carbon atoms.) R 1 is preferably a linear alkyl group having 10 to 20 carbon atoms, more preferably a linear alkyl group having 12 to 14 carbon atoms. Examples of the linear alkyl group having 12 to 14 carbon atoms include a dodecyl group, a tridecyl group, and a tetradecyl group.)

[0018] m is 0.1 or more, preferably 0.1 to 5, more preferably 0.1 to 3, still more preferably 0.5 to 3, particularly preferably 1 to 3.) n is 0 to 6, preferably 0 to 3, more preferably 0.5 to 2.) m + n is 0.1 or more, preferably 0.5 to 10, more preferably 1 to 5.)

[0019] When n is not 0, that is, when the component (a11) has EO and PO, there is no particular limitation on the distribution (arrangement order) of EO and PO in [(EO) m / (PO) n . These may be arranged in a block form or in a random form. Also, EO may be bonded to "R 1 -O-", or PO may be bonded to "R 1 -O-". As a method of arranging EO and PO in a block form, for example, there are a method of introducing propylene oxide after introducing ethylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, a method of introducing propylene oxide after introducing ethylene oxide, and further introducing ethylene oxide, etc. The (a11) component preferably has any one of EO, PO, and BO, more preferably has EO and PO or EO and BO, and even more preferably has EO and PO. Since EO has high hydrophilicity and interacts with water in the liquid detergent composition, the high-temperature stability can be further enhanced. Since PO distorts the structure of the nonionic surfactant, foaming during automatic dosing tank cleaning can be better prevented. M + Examples include Na + , K + , H + and the like.

[0020] As the (a11) component, from the viewpoint of sebum detergency, R 1 is a linear or branched alkyl group having 10 to 20 carbon atoms or a linear or branched alkenyl group having 10 to 20 carbon atoms, and those in which m + n is 1 to 5 are preferred. The above-mentioned optional anionic surfactant may be used alone or in combination of two or more.

[0021] ≪Content of component (A)≫ The content of the (A) component is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass with respect to the total mass of the liquid detergent composition. When the content of the (A) component is at least the above lower limit value, the low-temperature stability can be further enhanced. When the content of the (A) component is at most the above upper limit value, foaming can be more suppressed (the foaming suppression effect can be further enhanced).

[0022] The content of the essential anionic surfactant (essential A amount) is less than 10% by mass, preferably 0.05% to less than 10% by mass, more preferably 0.1% to 9% by mass, still more preferably 1% to 9% by mass, and particularly preferably 1% to 5% by mass, based on the total mass of the liquid detergent composition. When the essential A amount is at least the above lower limit value, the low-temperature stability can be further enhanced. When the essential A amount is at most the above upper limit value, the foaming inhibitory effect can be further enhanced.

[0023] The mass ratio of the essential A amount to the total mass of component (A) (essential A / A ratio) is preferably 0.01 to 0.8, more preferably 0.01 to 0.5, still more preferably 0.01 to 0.3, and particularly preferably 0.01 or more and less than 0.2. When the essential A / A ratio is at least the above lower limit value, the low-temperature stability can be further enhanced. When the essential A / A ratio is at most the above upper limit value, the foaming inhibitory effect can be further enhanced.

[0024] <Component (B)> Component (B) is a nonionic surfactant containing at least one selected from nonionic surfactant (b1) ((b1) component), nonionic surfactant (b2) ((b2) component), and nonionic surfactant (b3) ((b3) component). By containing component (B), the liquid detergent composition enhances the low-temperature stability and the foaming inhibitory effect.

[0025] ≪Component (b1)≫ Component (b1) is nonionic surfactant (b1) represented by the following (b1) formula.

[0026] R 11 -O-[(EO) h / (A 11 O) j -(EO) k -R 12 ···(b1) [In the (b1) formula, R 11 is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a primary carbon atom, R 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, h is a number from 3 to 25 indicating the average number of repeating units of EO, A 11 O is at least one of an oxypropylene group and an oxybutylene group, and j is a number from 0.1 to 10 indicating the average number of repeating units of A 11 O, and k is a number from 0 to 20 indicating the average number of repeating units of EO.]

[0027] R 11 is a linear hydrocarbon group having 8 to 22 carbon atoms, which is a so-called primary hydrocarbon group. R 11 may be a saturated hydrocarbon or an unsaturated hydrocarbon, and a saturated hydrocarbon is preferred. R 11 has 8 to 22 carbon atoms, preferably 10 to 18, more preferably 12 to 18. (b1) In the formula, the carbon atom of R 11 bonded to -O- is a primary carbon atom. In the formula (b1), -O- is bonded to the carbon atom located at the end of the straight chain among the carbon atoms constituting R 11 .

[0028] R 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. R 12 When it is an alkyl group, it has 1 to 6 carbon atoms, preferably 1 to 3. R 12 When it is an alkenyl group, it has 2 to 6 carbon atoms, preferably 2 to 3. R 12 is particularly preferably a hydrogen atom.

[0029] h is from 3 to 25, preferably from 5 to 25, more preferably from 12 to 25, still more preferably from 12 to 23, and particularly preferably from 15 to 23. j is from 0.1 to 10, preferably from 0.5 to 6, more preferably from 2 to 6. When j is at least the lower limit value of the above range, the foaming suppression effect can be enhanced more. When j is at most the upper limit value of the above range, the low-temperature stability can be enhanced more. k is from 0 to 20, preferably from 0 to 15, more preferably from 0 to 10. The sum (h + k) of h and k is preferably from 3 to 30, more preferably from 5 to 25, still more preferably from 12 to 25, particularly preferably from 12 to 23, and most preferably from 15 to 23. When h + k is at least the above lower limit value, the high-temperature stability can be further enhanced.

[0030] [(EO) h / (A 11 O) j There is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO, and BO. These may be arranged in a block pattern or in a random pattern. Also, EO may be bonded to “R 11 -O-”, and PO or BO may be bonded to “R 11 -O-”. Component (b1) preferably has EO and PO, or EO and BO, and more preferably has EO and PO. Since EO has high hydrophilicity and interacts with water in the liquid detergent composition, it can prevent the evaporation of water and further enhance the high-temperature stability. Since PO distorts the structure of the nonionic surfactant, it can further enhance the foam suppression effect.

[0031] Examples of commercially available products of component (b1) include Emulgen LS-110, Emulgen MS-110 manufactured by Kao Corporation, Pluronic (registered trademark) PE 6800, Pluronic (registered trademark) RPE 1740 manufactured by BASF Corporation, etc.

[0032] ≪Component (b2)≫ Component (b2) is a nonionic surfactant (b2) represented by the following formula (b2).

[0033] R 21 -O-[(EO) p / (A 21 O) q -(EO) r -R 22 ···(b2) [In formula (b2), R 21 is a branched hydrocarbon group having 8 to 22 carbon atoms, R22 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 indicating the average number of repeating units of EO, and A 12 O is at least one of an oxypropylene group and an oxybutylene group, q is a number from 0 to 10 indicating the average number of repeating units of A 21 O, and r is a number from 0 to 20 indicating the average number of repeating units of EO.]

[0034] R 21 is a branched hydrocarbon group having 8 to 22 carbon atoms. R 21 may be a saturated hydrocarbon or an unsaturated hydrocarbon, and a saturated hydrocarbon is preferred. R 21 has 8 to 22 carbon atoms, preferably 10 to 18, and more preferably 12 to 18. The carbon atom of R bonded to -O- 21 may be a primary carbon atom or a secondary carbon atom. When the carbon atom of R bonded to -O- 21 is a primary carbon atom, -O- is bonded to the carbon atom located at the end of the straight chain among the carbon atoms constituting R. When the carbon atom of R bonded to -O- 21 is a secondary carbon atom, -O- is bonded to the carbon atom located other than the end of the straight chain among the carbon atoms constituting R. 21 21 22 22

[0035] R 22 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. R 22 When R is an alkyl group, the number of carbon atoms is 1 to 6, preferably 1 to 3. R 22 When R is an alkenyl group, the number of carbon atoms is 2 to 6, preferably 2 to 3. R 22 is particularly preferably a hydrogen atom.

[0036] p is from 3 to 25, preferably from 5 to 18, more preferably from 5 to 15, even more preferably from 5 to 10, and particularly preferably from 5 to 8. q ranges from 0 to 10, preferably from 0 to 6, more preferably from 0 to 3. When p is greater than or equal to the lower limit of the above range, the foaming suppression effect can be enhanced more. When p is less than or equal to the upper limit of the above range, the low-temperature stability can be enhanced more. r ranges from 0 to 20, preferably from 0 to 15, more preferably from 0 to 10. The sum of p and r (p + q) is preferably from 3 to 30, more preferably from 5 to 25, still more preferably from 5 to 20, particularly preferably from 5 to 15, very preferably from 5 to 10, and most preferably from 5 to 8. When p + r is greater than or equal to the lower limit of the above range, the high-temperature stability can be enhanced more. When p + r is less than or equal to the upper limit of the above range, the low-temperature stability can be enhanced more.

[0037] When q is not 0, that is, when the (b2) component has EO and PO, EO and BO, or EO, PO, and BO, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO, and BO in [(EO) p / (A 21 O) q . These may be arranged in a block shape or in a random shape. Also, EO may be bonded to "R 21 -O-", or PO or BO may be bonded to "R 21 -O-". The (b2) component preferably has EO and PO, or EO and BO, and more preferably has EO and PO. Since EO has high hydrophilicity and interacts with water in the liquid detergent composition, the high-temperature stability can be enhanced more.

[0038] Examples of commercially available products of the (b2) component include, for example, those obtained by adding 3 to 10 mol equivalents of ethylene oxide to alcohols such as DiaDole (registered trademark) manufactured by Mitsubishi Chemical Corporation (the number after C13 and C indicates the carbon number of the alcohol. The same applies hereinafter), Neodol (registered trademark) manufactured by Shell (a mixture of C12 and C13), Safol (registered trademark) 23 (a mixture of C12 and C13) manufactured by Sasol, and EXXAL (registered trademark) 13 (C13); Alcohols with 13 carbon atoms obtained by subjecting an alkene with 12 carbon atoms, which is obtained by trimerizing butene, to the oxo process, and having 3, 5, or 7 molar equivalents of ethylene oxide added thereto (Lutensol® TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF); Alcohols with 13 carbon atoms obtained by subjecting an alkene with 12 carbon atoms, which is obtained by trimerizing butene, to the oxo process, and having 12 or 15 molar equivalents of ethylene oxide added thereto (Lutensol® TO12, Lutensol TO15, etc., manufactured by BASF); Alcohols with 10 carbon atoms obtained by subjecting pentanol to the Garbett reaction and having 9 molar equivalents of ethylene oxide added thereto (Lutensol XP90, manufactured by BASF); Alcohols with 10 carbon atoms obtained by subjecting pentanol to the Garbett reaction and having 7 molar equivalents of ethylene oxide added thereto (Lutensol XL70, manufactured by BASF); Alcohols with 10 carbon atoms obtained by subjecting pentanol to the Garbett reaction and having 6 molar equivalents of ethylene oxide added thereto (Lutensol XA60, manufactured by BASF), etc. can be mentioned. Among these, products such as Sasol's product name Safol23 (branching ratio: 50% by mass) (obtained by subjecting olefins obtained from coal gasification to the oxo process to obtain alcohols and then further hydrogenating), and Shell Chemicals' product name Neodol23 (branching ratio: 20% by mass) (produced from n-olefins by the improved oxo process and rectified), when it is a "mixture" of a compound in which the hydrocarbon group of R in the (a2) formula is a branched chain and a compound in which the hydrocarbon group of R in the (a1) formula is a straight chain, the one with a branched chain is defined as the (a2) component, and the one with a straight chain is defined separately as the (a1) component. The "branching ratio" indicates the ratio (% by mass) of the higher alcohol with a branched chain to the total higher alcohol. 21 For a compound in which the hydrocarbon group of R in the (a2) formula is a branched chain and a compound in which the hydrocarbon group of R in the (a1) formula is a straight chain, in the case of a "mixture", the one with a branched chain is defined as the (a2) component, and the one with a straight chain is defined separately as the (a1) component. The "branching ratio" indicates the ratio (% by mass) of the higher alcohol with a branched chain to the total higher alcohol. 11 ≪Component (b3)≫

[0039] The (b3) component is a nonionic surfactant (b3) represented by the following (b3) formula. The (b3) component is a nonionic surfactant (b3) represented by the following (b3) formula.

[0040] R 31 -O-[(EO) s / (A 31 O) t -(EO) u -R 32 ···(b3) [(In the formula (b3), R 31 is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a secondary carbon atom, and R 32 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, s is a number from 3 to 25 indicating the average number of EO repetitions, A 31 O is at least one of an oxypropylene group and an oxybutylene group, and t is a number from 0 to 10 indicating the average number of repetitions of A 31 O, and u is a number from 0 to 20 indicating the average number of repetitions of EO.)]

[0041] R 31 is a linear hydrocarbon group having 8 to 22 carbon atoms. R 31 may be a saturated hydrocarbon or an unsaturated hydrocarbon, and a saturated hydrocarbon is preferred. R 31 has 8 to 22 carbon atoms, preferably 10 to 18, more preferably 12 to 18. The carbon atom of R 31 bonded to -O- is a secondary carbon atom. In the formula (b3), -O- is bonded to a carbon atom located other than the terminal of the straight chain among the carbon atoms constituting R 31 .

[0042] R 32 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. R 32 When R is an alkyl group, it has 1 to 6 carbon atoms, preferably 1 to 3. R 32 When R is an alkenyl group, it has 2 to 6 carbon atoms, preferably 2 to 3. R 32 is particularly preferably a hydrogen atom.

[0043] s is from 3 to 25, preferably from 5 to 25, more preferably from 7 to 20, still more preferably from 7 to 18, particularly preferably from 9 to 18, and most preferably from 11 to 18. t is from 0 to 10, preferably from 0 to 6, and more preferably from 2 to 6. When t is at least the lower limit of the above range, the foaming suppression effect can be further enhanced. When t is at most the upper limit of the above range, the low-temperature stability can be further enhanced. u is from 0 to 20, preferably from 0 to 15, and more preferably from 0 to 10. The total of s and u (s + u) is preferably from 3 to 30, more preferably from 5 to 25, still more preferably from 5 to 20, particularly preferably from 7 to 20, very preferably from 9 to 18, and most preferably from 11 to 18. When s + u is at least the lower limit of the above range, the high-temperature stability can be further enhanced. When s + u is at most the upper limit of the above range, the low-temperature stability can be further enhanced.

[0044] When t is not 0, that is, when the (b3) component has EO and PO, EO and BO, or EO, PO, and BO, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO, and BO in [(EO) s / (A 31 O) t . These may be arranged in a block shape or in a random shape. Further, EO may be bonded to "R 31 -O-", or PO or BO may be bonded to "R 31 -O-". When t is not 0, the (b3) component preferably has EO and PO, or EO and BO, and more preferably has EO and PO. Since EO has high hydrophilicity and interacts with water in the liquid detergent composition, the high-temperature stability can be further enhanced.

[0045] Examples of commercially available products of the (b3) component include, for example, Softanol (registered trademark) 120 manufactured by Nippon Shokubai Co., Ltd.

[0046] The (b1) component, the (b2) component, and the (b3) component may be any one of them alone or in combination of two or more.

[0047] <<Other nonionic surfactants>> The component (B) may contain a nonionic surfactant other than the components (b1), (b2), and (b3) (optional nonionic surfactant). Examples of the optional nonionic surfactant include alkylene oxide adducts such as alkylphenols and amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, 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. These optional nonionic surfactants may be used alone or in combination of two or more.

[0048] <<Content of component (B)>> The content of the component (B) is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, and even more preferably 35 to 45% by mass based on the total mass of the liquid detergent composition. When the content of the component (B) is at least the above lower limit value, the high-temperature stability can be further enhanced. When the content of the component (B) is at most the above upper limit value, the low-temperature stability can be further enhanced.

[0049] The content of the components (b1), (b2), and (b3) (collectively sometimes referred to as "specific nonionic surfactants") having an average number of repeating oxyethylene groups of 12 or more is preferably 20 to 50% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass based on the total mass of the liquid detergent composition. When the content of the specific nonionic surfactant is at least the above lower limit value, the high-temperature stability can be further enhanced and the foam suppression effect can be further enhanced. When the content of the specific nonionic surfactant is at most the above upper limit value, the low-temperature stability can be further enhanced. The specific nonionic surfactant is a nonionic surfactant with h + k in the formula (b1) being 12 or more if it is the component (b1). Similarly, if it is the component (b2), it is a nonionic surfactant with p + r in the formula (b2) being 12 or more. Similarly, if it is the component (b3), it is a nonionic surfactant with s + u in the formula (b3) being 12 or more.

[0050] The total mass of the components (b1), (b2), and (b3) is defined as the essential B amount. The essential B amount is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 40% by mass based on the total mass of the liquid detergent composition. When the essential B amount is at least the above lower limit value, the high-temperature stability can be further enhanced. When the essential B amount is at most the above upper limit value, the low-temperature stability can be further enhanced and the foaming suppression effect can be further enhanced.

[0051] The mass ratio of the essential B amount to the total mass of the component (B) (essential B / B ratio) is preferably 0.3 to 1.0, more preferably 0.5 to 1.0. When the essential B / B ratio is at least the above lower limit value, the foaming suppression effect can be further enhanced. When the essential B / B ratio is at most the above upper limit value, the low-temperature stability can be further enhanced.

[0052] The lower limit value of the total mass of the component (A) and the component (B) (AB amount) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more based on the total mass of the liquid detergent composition. The upper limit value of the AB amount is preferably 65% by mass or less, more preferably 60% by mass or less based on the total mass of the liquid detergent composition. The AB amount is preferably 30 to 65% by mass, more preferably 40 to 60% by mass, and even more preferably 50 to 60% by mass based on the total mass of the liquid detergent composition. When the AB amount is at least the lower limit value of the above range, the high-temperature stability can be further enhanced. When the AB amount is at most the upper limit value, the foaming suppression effect can be further enhanced and the low-temperature stability can be further enhanced.

[0053] The ratio of the content of component (A) to the content of component (B), which is represented by the mass ratio (A / B ratio) of component (A) / component (B), is less than 1, preferably from 0.1 to less than 1, more preferably from 0.3 to less than 1, and even more preferably from 0.4 to 0.8. When the A / B ratio is at least the above lower limit value, the low-temperature stability can be further enhanced. When the A / B ratio is at most the above upper limit value, the high-temperature stability can be further enhanced, and the foam-suppressing effect can be further enhanced.

[0054] <Component (C)> Component (C) is a water-miscible organic solvent having a boiling point of 120°C or higher. By containing component (C), the high-temperature stability of the liquid detergent composition can be further enhanced.

[0055] "Water-miscible" means the property of dissolving 25 g or more in 1 L of water at 25°C. That is, component (C) is an organic solvent that dissolves 25 g or more in 1 L of water at 25°C.

[0056] The boiling point of component (C) is 120°C or higher, preferably from 120 to 400°C, more preferably from 150 to 350°C, and even more preferably from 180 to 300°C. When the boiling point of the water-miscible organic solvent is within the above range, the high-temperature stability can be enhanced. It should be noted that the boiling point of component (C) is the normal boiling point (NBP) at 1 atmosphere (1013 hPa).

[0057] As the water-miscible organic solvent, there is no particular limitation as long as it has a boiling point of 120°C or higher and is water-miscible. For example, 3-methoxy-3-methyl-1-butanol (boiling point 174°C), ethylene glycol (boiling point 197°C), diethylene glycol (boiling point 244°C), butylene glycol (boiling point 207°C), hexylene glycol (boiling point 197°C), glycerin (boiling point 290°C), sorbitol (boiling point 296°C), diglycerin (boiling point 214°C), triethylene glycol (boiling point 285°C), polyethylene glycol 400 (boiling point 250°C), propylene glycol (boiling point 188°C), dipropylene glycol (boiling point 232°C), tripropylene glycol (boiling point 273°C), ethylene glycol monoethyl ether (boiling point 135°C), ethylene glycol monobutyl ether (boiling point 171°C), diethylene glycol monomethyl ether (boiling point 194°C), diethylene glycol monoethyl ether (boiling point 202°C), diethylene glycol monoisopropyl ether (boiling point 207°C), diethylene glycol monobutyl ether (boiling point 230°C), diethylene glycol monoisobutyl ether (boiling point 160°C), triethylene glycol monomethyl ether (boiling point 122°C), triethylene glycol monobutyl ether (boiling point 276°C), triethylene glycol monoisobutyl ether (boiling point 160°C), tetraethylene glycol monomethyl ether (boiling point 158°C), propylene glycol monoethyl ether (boiling point 133°C), dipropylene glycol monobutyl ether (boiling point 227°C), tripropylene glycol monobutyl ether (boiling point 276°C), diethylene glycol diethyl ether (boiling point 188°C), phenoxyethanol (boiling point 247°C), etc. may be mentioned. Among these, from the viewpoints of low-temperature stability, high-temperature stability, and mildness of odor, it is preferable to contain one or more of phenoxyethanol, diethylene glycol monobutyl ether, propylene glycol, and polyethylene glycol, and it is more preferable to combine two or more of them. As a combination of water-miscible organic solvents, it is preferably to contain diethylene glycol monobutyl ether. It is more preferable to combine diethylene glycol monobutyl ether with propylene glycol, phenoxyethanol, and polyethylene glycol, and it is even more preferable to combine diethylene glycol monobutyl ether with propylene glycol. By containing diethylene glycol monobutyl ether, the low-temperature stability is improved, and by containing propylene glycol, phenoxyethanol, and polyethylene glycol, the water evaporation during high-temperature storage is prevented.

[0058] ≪Content of Component (C)≫ (C) The content of the component is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, even more preferably 3 to 18% by mass, and particularly preferably 3 to 13% by mass based on the total mass of the liquid detergent composition. When the content of component (C) is at least the above lower limit value, the high-temperature stability can be further enhanced, and the low-temperature stability can be further enhanced. When the content of component (C) is at most the above upper limit value, the high-temperature stability can be further enhanced.

[0059] When component (C) contains diethylene glycol monobutyl ether (DEGBE), the mass ratio of DEGBE to the content of component (C) excluding DEGBE (DEGBE / other C ratio) is preferably 1 or more, more preferably 1 to 10, and even more preferably 1 to 5. When the DEGBE / other C ratio is at least the above lower limit value, the low-temperature stability can be further enhanced. When the DEGBE / other C ratio is at most the above upper limit value, the high-temperature stability can be further enhanced.

[0060] <Component (D)> (D) The component is water. By containing component (D), the liquid detergent composition can be quickly dispersed in water.

[0061] ≪Content of Component (D)≫ The content of component (D) is 30% by mass or less, preferably 28% by mass or less, and more preferably 25% by mass or less, based on the total mass of the liquid detergent composition. Also, the content of component (D) is preferably 8% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, based on the total mass of the liquid detergent composition. When the content of component (D) is below the above upper limit value, the high-temperature stability can be enhanced. Also, when the content of component (D) is above the above lower limit value, the low-temperature stability can be further enhanced. Note that the above lower limit value and the above upper limit value can be combined as appropriate. For example, the content of component (D) may be 8 to 30% by mass, 10 to 28% by mass, or 15 to 25% by mass, based on the total mass of the liquid detergent composition.

[0062] In the liquid detergent composition, the mass ratio of component (C) to component (D), represented by (C) component / (D) component (C / D ratio), is preferably 1.2 or less, more preferably 0.1 to 1.0, further preferably 0.1 to 0.7, and particularly preferably 0.3 to 0.7. When the C / D ratio is above the above lower limit value, the high-temperature stability is enhanced and the low-temperature stability can be enhanced. When the C / D ratio is below the above upper limit value, the high-temperature stability and the low-temperature stability are enhanced, and the appearance is excellent under high-temperature and low-temperature environments.

[0063] <Optional component> The liquid detergent composition may contain other components (optional components) other than component (A), component (B), component (C), and component (D) within a range that does not impair the effects of the present invention. Examples of the optional component include components commonly used in liquid detergent compositions. Examples of the optional component include, for example, surfactants other than component (A) and component (B) (optional surfactants), organic solvents other than component (C), chelating agents, detergency builders, stabilizers, alkali agents (e.g., alkanolamines such as monoethanolamine, diethanolamine, triethanolamine), metal ion scavengers, softening agents such as silicone, preservatives, fluorescent agents, anti-migration agents, pearlescent agents, antioxidants, antibacterial agents, general-purpose dyes or pigments as colorants, emulsifying agents, fragrances, pH adjusters, etc. In the liquid detergent composition, the total amount of components (A) to (D) and optional components does not exceed 100% by mass.

[0064] ≪Optional surfactant≫ Examples of the optional surfactant include cationic surfactants, amphoteric surfactants, semi-polar surfactants, and the like.

[0065] ≪Soap≫ The liquid detergent composition may contain a higher fatty acid or a salt thereof (soap). The "higher fatty acid" is a fatty acid having 8 to 22 carbon atoms. Although the higher fatty acid or a salt thereof is in the category of anionic surfactants, it has a different action from the non-soap anionic surfactant of component (A), functions as an antifoaming agent, and contributes to the improvement of rinsability. When the rinsability is improved, the number of rinsing processes and the time during automatic dosing tank cleaning can be reduced.

[0066] As the higher fatty acid, a linear monocarboxylic acid having 8 to 18 carbon atoms is preferable. Examples of the linear monocarboxylic acid having 8 to 18 carbon atoms include compounds represented by the formula (e1). R 9 -COOH ···(e1) In the formula (e1), R 9 is an aliphatic hydrocarbon group having 7 to 17 carbon atoms.

[0067] In the formula (e1), the aliphatic hydrocarbon group of R 9 may be linear or branched, and a linear or branched alkyl group, or a linear or branched alkenyl group is preferable. The number of carbon atoms of R 9 is 7 to 17, and 11 to 17 is preferable. When the number of carbon atoms of R 9 is not less than the above lower limit value, the antifoaming effect can be enhanced. When the number of carbon atoms of R 9 is not more than the above upper limit value, the solubility in water is further increased.

[0068] Examples of the salt form in higher fatty acids include alkali metal salts, alkaline earth metal salts, amine salts, or ammonium salts. Examples of alkali metal salts include sodium salts or potassium salts. Examples of alkaline earth metal salts include calcium salts or magnesium salts. Examples of amine salts include alkanolamine salts (such as monoethanolamine salts, diethanolamine salts, or triethanolamine salts).

[0069] The content of the higher fatty acid or its salt is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less based on the total mass of the liquid detergent composition. When the total content of the higher fatty acid or its salt is within the above range, the defoaming property is further enhanced.

[0070] ≪Enzyme≫ The liquid detergent composition may further contain an enzyme. Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, pectinase, nuclease, etc. The enzyme may be used alone or in combination of two or more. These enzymes are generally commercially available as preparations containing the enzyme (enzyme preparations). When preparing the liquid detergent composition, they are usually formulated in the form of enzyme preparations.

[0071] As the protease, a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease, is preferred. Examples of protease-containing preparations (protease preparations) include, for example, those with 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, Progress Uno101L, which are available from Novozymes; and those with the trade names Purafect L, Purafect OX, Properase L, etc., which are available from Genencor.

[0072] Examples of amylase-containing preparations (amylase preparations) include, for example, those with the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify Prime, which are available from Novozymes; those with the trade name Maxamyl, which is available from Genencor; those with the trade name Pullulanase Amano, which is available from Amano Enzyme; and those with the trade name DB-250, which is available from Seikagaku Corporation.

[0073] Examples of lipase-containing preparations (lipase preparations) include, for example, those with the trade names Lipex 100L, Lipolase 100L, etc., which are available from Novozymes.

[0074] Examples of cellulase-containing preparations (cellulase preparations) include, for example, those with the trade names Carezyme 4500L, Carezyme Premium 4500L, Endolase 5000L, Celluclean 4500T, etc., which are available from Novozymes.

[0075] Examples of the preparation containing mannanase (mannanase preparation) include those with the trade names Mannaway 4.0L and Mannaway 200L available from Novozymes.

[0076] Examples of the preparation containing pectinase (pectinase preparation) include Pectawash, Pectaway, and XPect available from Novozymes. Examples of the preparation containing nuclease (nuclease preparation) include Pristine 100L available from Novozymes, Cyronase Cold-Active Nuclease available from Takara Bio, and Benzonase available from Millipore. These enzyme preparations may be used alone or in combination of two or more.

[0077] ≪Hydrotrope≫ The liquid detergent composition may further contain a hydrotrope. A hydrotrope is a compound that has a relatively low molecular weight, has a hydrophilic group and a hydrophobic group in the molecule, and is formulated to prevent changes in viscosity (mainly a viscosity-reducing effect) and crystal precipitation at low or high temperatures. Examples of the hydrophilic group include a hydroxyl group (-OH), an ester group (-COO-), a carboxyl group (-COOH), an ether group (-O-), a sulfo group (-SO3H), etc. Examples of the hydrotrope include p-toluenesulfonic acid, cumenesulfonic acid, benzoic acid and its salts, etc. Among them, cumenesulfonic acid is preferred. The hydrotrope may be used alone or in combination of two or more. The content of the hydrotrope is preferably 0 to 10% by mass, more preferably 4 to 8% by mass, based on the total mass of the liquid detergent composition. When the total content of the hydrotrope is within the above range, the viscosity of the liquid detergent composition decreases, and the discharge stability from the automatic dosing tank is improved. Also, precipitation of enzymes, etc. during storage at high temperatures can be suppressed.

[0078] ≪pH adjuster≫ Examples of the pH adjuster include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine, sodium hydroxide, potassium hydroxide, sulfuric acid, and the like. The pH adjuster may be used alone or in combination of two or more.

[0079] (Method for producing a liquid detergent composition) The liquid detergent composition of the present embodiment can be produced according to a method for producing a conventionally known liquid detergent composition. For example, after adding and mixing each component except the pH adjuster to a part of water, adding the pH adjuster as necessary to adjust the pH, and then adding the remaining part of water to make the total amount 100% by mass. The obtained liquid detergent composition is preferably stored in a container such as a bottle container, a squeeze container, or a pouch container to obtain a containerized liquid detergent product.

[0080] As one aspect of the container of the containerized liquid detergent product, a plastic container including a plastic container body and a plastic cap can be used. The container body has a mouth part, and the cap is configured to be detachably attached to the mouth part. The material of the container body is preferably a synthetic resin having transparency or translucency, such as a polyethylene resin, a polypropylene resin, or a polyethylene terephthalate (PET). Examples of the molding method of the container body include a biaxial stretch blow molding method. The cap is preferably a cap having a measuring cylinder part capable of measuring the liquid detergent (hereinafter also referred to as a measuring cap). The material of the cap is preferably a synthetic resin having transparency or translucency, such as a polyethylene resin, a polypropylene resin, or a polyethylene terephthalate (PET). Examples of the molding method of the cap include an injection molding method. The shape of the measuring cap can be a known shape. For example, as described in JP-A-2020-200095, it can have a shape including a measuring cylinder part extending in the axial direction and a tongue-like part provided at a part of the circumferential direction centered on the axis at the tip of the measuring cylinder part in the axial direction and protruding in the axial direction.

[0081] Usage method As a usage method (i.e., a washing method) of the liquid detergent composition, for example, a method of putting the liquid detergent composition into the inlet of the liquid detergent composition of the washing machine and then operating the washing machine, a method of putting the liquid detergent composition into water together with the object to be washed during washing, a method of immersing the object to be washed in a cleaning liquid prepared by previously dissolving the liquid detergent composition in water, a method of directly applying the liquid detergent composition to the object to be washed and leaving it for, for example, 3 minutes to 24 hours, and then performing normal washing, etc. can be mentioned.

[0082] Moreover, it is most preferable to use a washing machine equipped with a detergent automatic dosing function that has been put into practical use in recent years. The detergent automatic dosing function is a function of automatically dosing the detergent from the tank storing the detergent to the washing tub via the dosing pipe. A metering means such as a syringe pump is provided in the middle of the dosing pipe, and a fixed amount set according to the amount of the laundry, etc. can be transferred from the tank to the washing tub.

[0083] By using the detergent automatic dosing function, not only can the labor of metering be saved, but also it is possible to avoid the situation where the liquid detergent composition adheres to the hands or spills during metering and stains the washing machine and its surroundings. Moreover, since the liquid detergent composition of the present embodiment is a concentrated type, the usage amount per washing may be very small, around 10 mL. Such a small amount of the liquid detergent composition is difficult to accurately measure with a cap or the like, and it is easy for the liquid amount to be insufficient or excessive. By using the detergent automatic dosing function, even a small amount of the liquid detergent composition can be accurately measured, so it is preferable because it can exhibit sufficient detergency and avoid waste due to overuse.

[0084] It is also preferable to use an automatic dispenser that can automatically discharge a predetermined amount of liquid. When using an automatic dispenser, even a small amount of the liquid detergent composition can be accurately measured, so it is easy to exhibit sufficient detergency and avoid waste due to overuse, which is preferable. Among automatic dispensers, there are also commercially available ones that use an infrared sensor or the like to automatically discharge without touching a switch or the like. By using such an automatic dispenser, it is possible to measure the liquid detergent composition simply by inserting a container held in one hand, and the effect of reducing the burden on the user is great.

[0085] When using an automatic dispenser, it is also preferable to receive the liquid detergent composition discharged into a flexible container and directly put the flexible container into the washing machine. Thereby, the entire amount of the discharged liquid detergent composition can be surely dissolved in the cleaning liquid. Examples of the material of the flexible container that can be directly put into the washing machine include, for example, silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, and the like.

[0086] Examples of the objects to be washed include, for example, textile products such as clothing (apparel), dishcloths, towels, sheets, curtains, etc. The material of the textile product is not particularly limited, and it may be any of natural fibers such as cotton, silk, and wool, and chemical fibers such as polyester and polyamide. When the liquid detergent composition is dissolved in water and used, it is preferably diluted, for example, 5 to 10,000 times (volume basis), and more preferably diluted 100 to 6,000 times. The bath ratio (mass of cleaning liquid during washing / mass of object to be washed), which is the amount of water per mass of the object to be washed, is preferably 5 or more for a drum-type washing machine and 10 or more for a vertical-type washing machine. The amount of the liquid detergent composition used in the washing process is preferably such that the ratio of the mass of the object to be washed (fabric amount) / mass of the liquid detergent composition is 10 to 1,000, more preferably 10 to 800, and even more preferably 100 to 800. The liquid detergent composition is suitable as a liquid detergent composition for textile products.

[0087] The liquid detergent composition of this embodiment contains component (A) and component (B) as surfactants, and contains component (C), thereby being excellent in detergency, high-temperature stability, and low-temperature stability. In addition, it is a concentrated liquid detergent composition with a water content of 30% by mass or less, and can exhibit detergency with a small amount of use.

[0088] In a washing machine equipped with a detergent automatic dosing function, the temperature inside the tank that houses the detergent also tends to rise during clothes drying. Also, since the detergent is sucked and transferred from the tank by a syringe pump or the like, the tank for the detergent is not completely sealed. As shown in the examples described later, when the liquid detergent is stored in the tank of a washing machine equipped with a detergent automatic dosing function, the weight tends to decrease. Since the liquid detergent composition of this embodiment is excellent in high-temperature stability, it is suitable as a liquid detergent for automatic detergent dosing because it is used in the tank of a washing machine equipped with a detergent automatic dosing function. In addition, since it is a concentrated liquid detergent that can exhibit high detergency with a small amount of use, it is also suitable as a liquid detergent for automatic detergent dosing in terms of the number of times of washing that can be performed with the capacity of the tank of the washing machine. Therefore, the liquid detergent composition of the present invention is particularly suitable for use in washing machines with an automatic detergent dosing function.

Examples

[0089] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0090] (Raw materials used) <Component (A)> · a1: AOS, sodium α-olefin sulfonate, manufactured by Lion Corporation, trade name "Lipolan LB-840" (corresponding to component a1). · a2-1: C16 IOS, sodium salt of internal olefin sulfonic acid having 16 carbon atoms (corresponding to component (a2)). The mass ratio of olefin form (sodium olefin sulfonate) / hydroxy form (sodium hydroxyalkane sulfonate) is 15 / 85. The mass ratio of the positional distribution of sulfonic acid groups in the HAS form was as follows: position 1 / position 2 / position 3 / position 4 / position 5 / positions 6 - 8 = 1.5 / 24.1 / 19.9 / 24.6 / 14.1 / 15.8. Also, (IO-1S) / (IO-2S) = 2.3 (mass ratio).

[0091] ≪Measurement method≫ The positional distribution of sulfonic acid groups in the HAS form and the mass ratio of the olefin form to the hydroxy form (HAS form) contained in each internal olefin sulfonate were measured by a high-performance liquid chromatography mass spectrometer. Note that for internal olefin sulfonates with double bonds at the 6th position or higher, the peaks overlapped and they could not be clearly fractionated. The equipment and analysis conditions used for the measurement are as follows. 〔Measuring equipment〕 LC device: "LC-20ASXR" (manufactured by Shimadzu Corporation). LC-MS device: "LCMS-2020" (manufactured by Shimadzu Corporation). Column: ODS Hypersil (length: 250 mm, inner diameter: 4.6 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific). Detector: ESI(-), m / z = 349.15 (C18), 321.10 (C16), 293.05 (C14). 〔Solvent〕 Solvent A: 10 mM ammonium acetate aqueous solution. Solvent B: Acetonitrile / water = 95 / 5 solution added with 10 mM ammonium acetate. 〔Elution conditions〕 Gradient: Solvent A 60% Solvent B 40% (0 - 15 minutes) → Solvent A 30% Solvent B 70% (15.1 - 20 minutes) → Solvent A 60% Solvent B 40% (20.1 - 30 minutes). Flow rate: 0.5 ml / min. Column temperature: 40 °C. Injection volume: 5 μL.

[0092] ·a2-2: Sodium salt of internal olefin sulfonic acid with 18 carbon atoms, corresponding to the (a2) component. The mass ratio of olefin form (sodium olefin sulfonate) / hydroxy form (sodium hydroxyalkane sulfonate) was 16 / 84. The mass ratio of the positional distribution of sulfonic acid groups in the HAS form was as follows. 1st / 2nd / 3rd / 4th / 5th / 6 - 9th = 1.5 / 22.1 / 17.2 / 21.8 / 13.5 / 23.9. Also, (IO - 1S) / (IO - 2S) = 1.6 (mass ratio). ·a3: Alkyl sulfosuccinate, sodium dioctyl sulfosuccinate, Sunmorin OT - 70 (manufactured by Sanyo Chemical Industries), corresponding to the (a3) component.

[0093] ≪Optional anionic surfactant≫ ·a4 - 1: AEPS(2EO, 2PO), the alkyl group is derived from lauryl alcohol, the average added molar number of propyleneoxy groups is 2 moles, and the average added molar number of ethyleneoxy groups is 2 moles. Sodium salt of (polyoxypropylene) polyoxyethylene lauryl ether sulfate. ·a4 - 2: APS(0.6PO): A compound obtained by adding 0.6 moles of propylene oxide to 1 mole of natural alcohol with an alkyl chain of C8:C10:C12 = 5:5:90 (mass ratio, the number following C means the number of carbon atoms), then sulfating it with sulfur trioxide and neutralizing it with an aqueous sodium hydroxide solution (neutralized until the pH of a 10% dilution with water reaches 11). ·a4 - 3: AES(1EO), polyoxyethylene alkyl ether sulfate (manufactured by Lion Corporation). A compound obtained by adding 1 mole equivalent of ethylene oxide to natural alcohol (product name "CO - 1270" manufactured by P&G). ·a4 - 4: LAS, sodium linear alkylbenzene sulfonate (manufactured by Lion Corporation, product name "Lipon LH - 200").

[0094] <(B) component> ·b1-1: Linear AE (9EO, 2PO, 9EO), polyoxyalkylene lauryl ether (a compound obtained by adding an average of 9 moles of ethylene oxide, then an average of 2 moles of propylene oxide, and then an average of 9 moles of ethylene oxide to 1 mole of lauryl alcohol. In the (b1) formula, R 11 = lauryl group, h = 9, j = 2, k = 9, AO = oxypropylene group, R 12 = hydrogen atom). Corresponds to the (b1) component. ·b1-2: Linear AE (20EO, 6PO), polyoxyalkylene lauryl ether (a compound obtained by adding an average of 20 moles of ethylene oxide and then an average of 6 moles of propylene oxide to 1 mole of lauryl alcohol. In the (b1) formula, R 11 = lauryl group, h = 20, j = 6, k = 0, A 11 O = oxypropylene group, R 12 = hydrogen atom). Corresponds to the (b1) component. ·b1-3: Linear AE (15EO, 2PO), polyoxyalkylene lauryl ether (a compound obtained by adding an average of 15 moles of ethylene oxide and then an average of 2 moles of propylene oxide to 1 mole of lauryl alcohol. In the (b1) formula, R 11 = lauryl group, h = 15, j = 2, k = 0, A 21 O = oxypropylene group, R 12 = hydrogen atom). Corresponds to the (b1) component. ·b2-1: Branched AE (14EO, PO), Lutensol XL140, manufactured by BASF. In the (b2) formula, R 21 = 2-propylheptyl group, p + r = 14, q > 0, AO = oxypropylene group, R 22 = hydrogen atom). Corresponds to the (b2) component. ·b3-1: Secondary linear AE (12EO), Softanol 120, manufactured by Nippon Shokubai. In the (b3) formula, R 31 = secondary alkyl group having 12 to 14 carbon atoms, s = 12, t = 0, u = 0, A 31 O = oxypropylene group, R 32 = hydrogen atom). Corresponds to the (b3) component. ·b4-1: LMAO, polyoxyethylene alkyl ether (prepared by adding 15 moles of ethylene oxide to 1 mole of primary alcohol (mass ratio of C12 alcohol / C14 alcohol = 7 / 3)). In formula (b1), R 11 is an alkyl group with 12 carbon atoms (C12) and an alkyl group with 14 carbon atoms (C14) (mass ratio C12:C14 = 70:30), and the carbon atom of R 11 bonded to -O- is a primary carbon atom, h = 15, j = 0, k = 0, R 12 is a hydrogen atom), trade name "LMAO-90", manufactured by Lion Corporation, corresponding to an optional nonionic surfactant.

[0095] <(C) component> ·c-1: DEGBE, diethylene glycol monobutyl ether, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ·c-2: PPG, propylene glycol, manufactured by The Dow Chemical Company. ·c-3: 2-PE, 2-phenoxyethanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ·c-4: PEG, polyethylene glycol 1000, trade name "PEG#1000-L60", manufactured by Lion Corporation.

[0096] <(C’) component> ·c’-1: Ethanol.

[0097] <(D) component> · Water: Ion-exchanged water.

[0098] <Optional component> · Coconut fatty acid: Trade name "Coconut Fatty Acid", manufactured by NOF Corporation. · CSA: Cumene sulfonate, manufactured by Wako Pure Chemical Industries, Ltd. · Dichlorosan: 4,4’-dichloro-2-hydroxydiphenyl ether, trade name "TINOSAN HP100", manufactured by BASF SE. · Protease: Trade name "Progress Uno", manufactured by Novozymes Japan K.K. · Amylase: Trade name "Amplify Prime", manufactured by Novozymes Japan K.K. · Nuclease: Cyronase Cold-Active Nuclease (manufactured by Takara Bio Inc., product code 2670A, an endonuclease derived from Shewanella sp. expressed in recombinant Escherichia coli). · BHT: Dibutylhydroxytoluene, trade name "SUMILZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd. · Fragrance: The fragrance composition described in [Table 1] of JP 2021-113271. · Dye: Green No. 202, manufactured by Kisuika Kasei Co., Ltd. · MEA: Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd.

[0099] (Evaluation method) <High-temperature stability> According to the description in the table, the liquid detergent compositions of each example were put into the storage containers described in the table and subjected to the evaluation of high-temperature stability. In the case of storage container A, a transparent glass bottle (wide-mouth standard bottle, PS-NO.6) was filled with 20 mL of the liquid detergent composition of each example, and it was left standing in a constant-temperature bath at 40 °C for 7 days with the lid open for storage. In the case of storage container B, an automatic detergent tank (part number BD-SX110CL-002, capacity: about 1000 mL, non-sealed container) attached to a drum-type washing machine (BD-SX110E) manufactured by Hitachi was filled with 400 mL of the liquid detergent composition of each example, and it was left standing in a constant-temperature bath at 40 °C for 14 days with the lid closed for storage. The weight loss rate (%) before and after storage was calculated, and the appearance of the liquid detergent composition in the container after storage was visually observed and evaluated according to the following evaluation criteria.

[0100] ≪Evaluation criteria≫ ◎: The weight loss rate is 0% or more and less than 10%. 〇: The weight loss rate is 10% or more and less than 20%. △: The weight loss rate is 20% or more and less than 30%. ×: The weight loss rate is 30% or more, or precipitates are observed in the liquid detergent composition in the container.

[0101] <Low-temperature stability> A 20 mL portion 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 capped and sealed. It was then left standing in a constant temperature bath at -5°C for 7 days for storage. After storage, the appearance of the liquid detergent composition in the glass bottle was visually observed, and the low-temperature stability was evaluated according to the following evaluation criteria.

[0102] ≪Evaluation Criteria≫ ◎: The liquid detergent composition in the glass bottle is transparent, no precipitate substances are observed, and the fluidity of the liquid is high. 〇: Turbidity is observed in the liquid detergent composition in the glass bottle, but the liquid has fluidity. △: The liquid detergent composition in the glass bottle is transparent, no precipitate substances are observed, but the fluidity of the liquid is low. ×: Turbidity is observed in the liquid detergent composition in the glass bottle, and the liquid has no fluidity.

[0103] <Foam Suppression Effect> Water with a hardness of 3°DH was added to the liquid detergent composition of each example to prepare a sample aqueous solution with a concentration of 300 ppm (mass basis). 20 mL of the sample aqueous solution was placed in a transparent Eppendorf tube (flat-bottomed colorimetric tube with a common stopper, capacity 100 mL), and the Eppendorf tube was stoppered. The stoppered Eppendorf tube was shaken 20 times at a speed of 2 reciprocations per second, and the foam height immediately after that was measured and evaluated according to the following criteria. [Evaluation Criteria] ◎: Foam height is 0 mL or more and less than 5 mL. 〇: Foam height is 5 mL or more and less than 10 mL. △: Foam height is 10 mL or more and less than 15 mL. ×: Foam height is 15 mL or more.

[0104] (Examples 1 to 21, Comparative Examples 1 to 8) According to the compositions shown in Tables 1 to 5, components (A) to (D) and optional components were added to water and mixed to prepare the liquid detergents of each example. Note that the compounding amounts in the tables are values in terms of pure components. Also, components not listed with compounding amounts in the tables are not compounded. The "appropriate amount" of MEA indicates the amount necessary and sufficient to adjust the pH of the liquid detergent composition to 7.5. The amount of water is the calculated amount assuming the amount of monoethanolamine is zero, and the actual amount of water is the amount at which the total amount (mass %) of all the compounding components including monoethanolamine becomes 100 mass %. For the liquid detergent compositions of each example, the high-temperature stability, low-temperature stability, and foaming suppression effect were evaluated, and the results are shown in the table.

[0105]

Table 1

[0106]

Table 2

[0107]

Table 3

[0108]

Table 4

[0109]

Table 5

[0110]

Table 6

[0111] As shown in Tables 1 to 5, in Examples 1 to 21, the high-temperature stability was “○” or “◎”, the low-temperature stability was “○” or “◎”, and the foaming suppression effect was “○” or “◎”. In Comparative Example 1 which does not contain any of the components (a1) to (a3), and Comparative Example 6 in which the content of component (D) is 30.6 mass %, the low-temperature stability was “×”. In Comparative Example 2 in which the amount of Essential A was 12 mass %, the foaming suppression effect was “×”. Comparative Example 3 containing component (C’) instead of component (C), and Comparative Example 7 with a content of component (C) of 19% by mass had a high-temperature stability of “×”. Comparative Example 4 with a content of component (B) of 35% by mass had a low-temperature stability and a foam-suppressing effect of “△”. Comparative Example 5 with a content of component (D) of 32.6% by mass and an AB amount of 43.0% by mass, and Comparative Example 8 with an A / B ratio of 1.2 had a low-temperature stability of “△”. From the above results, it was confirmed that by applying the present invention, the liquid stability can be enhanced and foaming can be suppressed.

Claims

1. Component (A): A non-soap anionic surfactant containing at least one essential anionic surfactant selected from α-olefin sulfonic acid and its salts, internal olefin sulfonic acid and its salts, and alkyl sulfosuccinic acid and its salts, Component (B): A nonionic surfactant containing at least one selected from the nonionic surfactant (b1) represented by the following formula (b1), the nonionic surfactant (b2) represented by the following formula (b2), and the nonionic surfactant (b3) represented by the following formula (b3), R １１ -O-[(EO) ｈ / (AO) １１ O) ｊ -(EO) ｋ -R １２ ・・・(b1) [In the formula (b1), R １１ is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a primary carbon atom, R １２ 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, h is a number from 3 to 25 indicating the average number of repeating units of EO, AO １１ O is at least one of an oxypropylene group and an oxybutylene group, j is a number from 0.1 to 10 indicating the average number of repeating units of AO １１ O, and k is a number from 0 to 20 indicating the average number of repeating units of EO.] R ２１ -O-[(EO) ｐ / (AO) ２１ O) ｑ -(EO) ｒ -R ２２ ・・・(b2) [In the formula (b2), R ２１ is a branched hydrocarbon group having 8 to 22 carbon atoms, R ２２ 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 indicating the average number of repeating units of EO, AO １２ O is at least one of an oxypropylene group and an oxybutylene group, q is a number from 0 to 20 indicating the average number of repeating units of AO ２１The number from 0 to 10 indicating the average number of repetitions of O, and r is the number from 0 to 20 indicating the average number of repetitions of EO. R ３１ -O-[(EO) ｓ / (A ３１ O) ｔ ]-(EO) ｕ -R ３２ ・・・(b3) [In the formula (b3), R ３１ is a linear hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom bonded to -O- is a secondary carbon atom, R ３２ 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, s is a number from 3 to 25 indicating the average number of repetitions of EO, A ３１ O is at least one of an oxypropylene group and an oxybutylene group, t is a number from 0 to 10 indicating the average number of repetitions of A ３１ O, and u is a number from 0 to 20 indicating the average number of repetitions of EO. Component (C): A water-miscible organic solvent having a boiling point of 120 ° C or higher, and Component (D): Water, and A liquid detergent composition for textile products containing The content of the essential anionic surfactant is less than 10% by mass based on the total mass of the liquid detergent composition for textile products, The content of the component (D) is 30% by mass or less based on the total mass of the liquid detergent composition for textile products, The ratio of the content of the component (A) to the content of the component (B), and the mass ratio represented by (A) component / (B) component is less than 1, The total of the mass of the component (A) and the mass of the component (B) is 50% by mass or more based on the total mass of the liquid detergent composition for textile products, The ratio of the mass of the component (C) to the mass of the component (D), and the mass ratio represented by (C) component / (D) component is 1.2 or less, A liquid detergent composition for textile products.

2. The component (B) of the liquid detergent composition for textile products according to claim 1 contains at least one specific nonionic surfactant selected from the component (b1) in which the total of h and k in the formula (b1) is 12 or more, the component (b2) in which the total of p and r in the formula (b2) is 12 or more, and the component (b3) in which the total of s and u in the formula (b3) is 12 or more.

3. The content of the specific nonionic surfactant is 20% by mass or more based on the total mass of the liquid detergent composition for textile products, according to the liquid detergent composition for textile products described in claim 2.

4. The component (C) of the liquid detergent composition for textile products according to claim 1 contains at least one selected from phenoxyethanol, diethylene glycol monobutyl ether, propylene glycol, and polyethylene glycol.

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