JP2020105418A - Liquid detergent composition - Google Patents

Abstract

To provide a liquid detergent composition having excellent storage stability at a low temperature.SOLUTION: A liquid detergent composition containing a (A) component shown below, a (B) component shown below, and water, in which the liquid detergent composition contains a potassium ion, and optimally a sodium ion, and a molar ratio in the liquid detergent composition (content of sodium ion)/(content of potassium ion) is 0 or larger and 9 or smaller. (A) component: an internal olefin sulfonate having 14 or larger and 16 or smaller carbons, (B) component: an organic solvent having a hydroxyl group having ClogP of -2 or larger and 2 or smaller.SELECTED DRAWING: None

Description

The present invention relates to a liquid detergent composition and a method for producing a liquid detergent composition.

Conventionally, anionic surfactants, particularly alkylbenzene sulfonates, nonionic surfactants containing an oxyalkylene group having 2 to 3 carbon atoms, olefin sulfonates, especially interiors having double bonds inside rather than at the ends of the olefin chain. Internal olefin sulfonates obtained from olefins as raw materials are widely used as household and industrial cleaning components.

Patent Documents 1 and 2 contain an internal olefin sulfonate having a carbon number of 16 and an internal olefin sulfonate having a carbon number of 18 at a specific ratio, and a hydroxy form/olefin form has a specific ratio. Excellent internal olefin sulfonate compositions are disclosed. It is also described that a solubilizer such as propylene glycol is used.

In Patent Document 3, the total of the ratios in which the double bond exists at the 2-position is 20 to 95%, and the ratio of cis isomer/trans isomer is 1/9 to 6/4, and the inside of 8 to 30 carbon atoms. Disclosed is an internal olefin sulfonate obtained by sulfonation, neutralization and hydrolysis of an olefin. As prior art, internal olefin sulfonates are described in which the distribution of double bond positions is described.

Patent Document 4 discloses a detergent composition having an excellent detergency containing an internal olefin sulfonate containing 25% or more of β-hydroxy form. A specific example describes a liquid laundry detergent containing monopropylene glycol.

Patent Document 5 describes the use of a water-miscible organic solvent from the viewpoint of improving the stability and solubility of the liquid detergent composition.

Patent Document 6 discloses a high concentration containing 55 to 75% by weight of an olefin sulfonate containing 50% by weight or more of an internal olefinsulfonate, 5 to 40% by weight of a predetermined hydrocarbon, and 1 to 40% by weight of water. Surfactant slurries are described.

Patent Document 7 describes a liquid detergent composition for textile products containing an internal olefin sulfonate having a specific hydrophilic group position distribution, an organic solvent having a hydroxyl group, and water.

Non-Patent Document 1 describes that in a straight-chain alkylbenzene sulfonate, the Kraft point is lower when the counter ion is a sodium ion than when the counter ion is a potassium ion. It is well known to those skilled in the art that the lower the Kraft point of a surfactant, the higher the solubility in water.

JP, 2005-28123, A JP, 2014-77126, A JP, 2003-81935, A European Patent Publication No. 377261 JP, 2011-32456, A JP-A-59-27995 JP, 2017-214571, A

A. Moreno, L. Cohen, and JL Berna, "Effects of Structure and Counterion on Physicochemical Properties of Linear Alkylbenzene Sulfonates" (Influence of Structure and Counterions on Physicochemical Properties of Linear Alkylbenzene Sulfonates), The Journal of the American Oil Chemists' Society (JAOCS), American Oil Chemists' Society, 1990, 8 Mon, Vol. 67, No. 8, 547-552

The present invention provides a liquid detergent composition having excellent storage stability at low temperatures, such as less precipitation of solid matter at low temperatures.

The present invention provides a liquid detergent composition containing the following component (A), the following component (B), and water,
The liquid detergent composition contains potassium ions, and optionally sodium ions,
The molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less,
Liquid detergent composition.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2

The present invention also provides a method for producing a liquid detergent composition, which comprises mixing the following component (A), the following component (B) and a component containing water (hereinafter referred to as a mixed component),
The mixed component includes a substance (I) that releases potassium ions in water, and an arbitrary substance (II) that releases sodium ions in water,
Here, the substance (I) may contain the component (A), and the substance (II) may contain the component (A).
The substance (I) and the substance (II) are mixed so that the molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less.
The present invention relates to a method for producing a liquid detergent composition.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2

According to the present invention, a liquid detergent composition having excellent storage stability at low temperatures is provided.
The present invention provides, for example, a liquid detergent composition capable of reducing the degree of precipitation of solid matter at low temperatures. The present invention also provides, for example, a liquid detergent composition in which the hydrated solid has a low melting point.

<Liquid cleaning composition>
In the liquid detergent composition containing the component (A), the component (B), and water, the present inventors have controlled the molar ratio of potassium ion and sodium ion within a specific range, thereby It has been found that the Kraft point can be lowered and the degree of precipitation of solids of the liquid detergent composition can be lowered. As described in Non-Patent Document 1, in the straight-chain alkylbenzene sulfonate, the Kraft point is higher when the counter ion is potassium ion than when it is sodium ion, the solubility in water, and further the stability at low temperature are stable. The sex is considered inferior. However, in the component (A) of the present invention, unlike this behavior, when the counter ion is a potassium ion in the presence of the component (B) of the present invention, the Kraft point of the component (A) becomes low. There was found. The present invention defines the molar ratio of potassium ion and sodium ion of the entire composition in a specific range based on this finding.

<(A) component>
The component (A) of the present invention is an internal olefin sulfonate having a carbon number of 14 or more and 16 or less and has an action of cleaning dirt attached to the fiber. The component (A) can be obtained by sulfonation of an internal olefin having 14 to 16 carbon atoms.

The component (A) includes an internal olefin sulfonate (IO-1S) having a sulfonic acid group at the second to fourth positions and having 14 to 16 carbon atoms, and a carbon number having a sulfonic acid group at the fifth or higher position. It is preferable to contain 14 or more and 16 or less internal olefin sulfonate (IO-2S). The mass ratio of (IO-1S) and (IO-2S) is (IO-1S)/(IO-2S) and is preferably 0.40 or more and 6.0 or less.

(IO-1S)/(IO-2S), which is a mass ratio of the content of (IO-1S) and the content of (IO-2S) in the component (A), is the liquid cleaning of the present invention. Even if the agent composition is exposed to a low temperature environment, from the viewpoint of suppressing precipitation of solid matter, it is preferably 0.40 or more, more preferably 0.50 or more, still more preferably 0.60 or more, and even more preferably 0.80 or more, and from the same viewpoint, preferably 6.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less, still more preferably 3.8 or less, still more preferably 3.5. It is as follows.

In addition, the content of each compound in which the position of the sulfonic acid group is different in the component (A) can be measured by a high performance liquid chromatography mass spectrometer (hereinafter, abbreviated as HPLC-MS). The content of each compound having different sulfonic acid group positions in the present specification is determined as a mass ratio based on the HPLC-MS peak area of the compound having the sulfonic acid group at each position in the total HAS of the component (A). To do.
Here, HAS is a hydroxyalkane sulfonate, that is, a hydroxy form of the internal olefin sulfonate among the compounds produced by sulfonation of the internal olefin sulfonate.
In the present invention, the internal olefin sulfonate having 14 to 16 carbon atoms and having a sulfonic acid group at 2 to 4 positions (IO-1S) means the sulfonic acid in the HAS body having 14 to 16 carbon atoms. It means a sulfonic acid salt having 14 to 16 carbon atoms and having a group at 2 to 4 position.
Further, the internal olefin sulfonate having 14 to 16 carbon atoms and having a sulfonic acid group at 5 or more positions (IO-2S) means that the sulfonic acid group in the HAS body having 14 to 16 carbon atoms is 5 or more positions. Means a sulfonate having 14 to 16 carbon atoms.

The internal olefin sulfonate as the component (A) includes an internal olefin sulfonate (IO-1S) having a sulfonic acid group at the second position to the fourth position and having 14 to 16 carbon atoms, and a sulfonic acid group. Is an internal olefin sulfonate (IO-2S) having 14 or more and 16 or less carbon atoms, which is present at the 5th or higher position. The maximum value of the bond position of the sulfonic acid group in the internal olefin sulfonate (IO-2S) depends on the carbon number.

The mass ratio (IO-1S)/(IO-2S) of the component (A) is based on the finally obtained component (A). For example, even if the internal olefin sulfonate obtained by mixing the internal olefin sulfonate whose mass ratio (IO-1S)/(IO-2S) is outside the above range, in the composition of the internal olefin sulfonate. When the mass ratio (IO-1S)/(IO-2S) is within the above range, it is regarded as the internal olefin sulfonate of the component (A).

Examples of the salt of the internal olefin sulfonate as the component (A) include an alkali metal salt, an alkaline earth metal (1/2 atom) salt, an ammonium salt and an organic ammonium salt. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the organic ammonium salt include alkanol ammonium salts having 1 to 6 carbon atoms.

The component (A) of the present invention is, for example, an internal olefin having 14 or more and 16 or less carbon atoms, and an olefin having 14 or more and 16 or less carbon atoms in which the double bond exists in the first to third positions. The mass ratio of (IO-1) and the olefin (IO-2) having a carbon number of 14 or more and 16 or less in which the double bond exists at the 5-position or more is (IO-1)/(IO-2) and is 0.35 or more. An internal olefin of 6.0 or less can be obtained as a raw material.
The internal olefin for obtaining the component (A) includes an olefin (IO-1) having a carbon number of 14 or more and 16 or less, which has a double bond at the 1-position or more and the 3-position or less, and a double bond at the 4-position. The olefin having 14 to 16 carbon atoms and the olefin (IO-2) having 14 to 16 carbon atoms in which the double bond exists at the 5th or more position. The maximum value of the position of the double bond in the olefin (IO-2) depends on the carbon number.

In the internal olefin having 14 or more and 16 or less carbon atoms, the double bond exists in the 1st or more and 3rd or less positions and the olefin (IO-1) having 14 or more and 16 or less carbons and the number of carbons in which the double bond exists in the 5th or more position The mass ratio (IO-1)/(IO-2) of the olefin (IO-2) of 14 or more and 16 or less can reduce the degree of precipitation of the liquid detergent composition of the present invention during low temperature storage, (B From the viewpoint that the melting point of the hydrated solid in the presence of the component) can be further lowered, it is preferably 6.0 or less, more preferably 5.5 or less, still more preferably 5.0 or less, still more preferably 4.5 or less. , More preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, and from the same viewpoint, preferably 0.40 or more, more preferably 0.5 or more, further preferably Is 0.60 or more, more preferably 0.65 or more.

The mass ratio (IO-1)/(IO-2) of the internal olefin to obtain the component (A) may be based on the finally obtained component (A). For example, even if the internal olefin sulfonate obtained by mixing the internal olefin sulfonate obtained by using an olefin whose mass ratio (IO-1)/(IO-2) is outside the above range, When the mass ratio (IO-1)/(IO-2) in the composition of the olefin corresponding to the olefin is within the above range, it corresponds to the internal olefin sulfonate of the component (A) obtained from the predetermined olefin as a raw material. It can be

The carbon number of the olefin as a raw material of the component (A) is 14 or more and 16 or less from the viewpoint of easily obtaining the effect of reducing the degree of precipitation in the present invention at low temperature storage.

The internal olefin used as the raw material for the component (A) also includes a small amount of so-called alpha olefin (hereinafter also referred to as α-olefin) in which the position of the double bond is at the 1-position of the carbon chain. .. The content of the alpha olefin in the internal olefin is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass from the viewpoint that the degree of precipitation of the liquid detergent composition at low temperature storage can be reduced. % Or less, more preferably 3% by mass or less, and preferably 0.01% by mass or more from the viewpoint of reducing production cost and improving productivity.

When the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of β-sultone is changed to γ-sultone and olefin sulfonic acid, which are further hydroxyalkane sulfone in the neutralization/hydrolysis step. And an olefin sulfonate (eg, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the resulting hydroxyalkane sulfonate is inside the alkane chain and the double bond of the olefin sulfonate is inside the olefin chain. Further, the obtained product is mainly a mixture thereof, and a part thereof is a hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain, or an olefin having a double bond at the end of the carbon chain. A small amount of sulfonate may be contained.
In the present specification, each of these products and the mixture thereof are collectively referred to as an internal olefin sulfonate ((A) component). Further, the hydroxyalkane sulfonate is referred to as a hydroxy form of internal olefin sulfonate (HAS), and the olefin sulfonate is referred to as an olefin form of internal olefin sulfonate (hereinafter, also referred to as IOS).
The mass ratio of the compounds in the component (A) can be measured by HPLC-MS. Specifically, the mass ratio can be determined from the HPLC-MS peak area of the component (A).

The distribution of double bonds in the raw material internal olefin can be measured by, for example, a gas chromatograph mass spectrometer (hereinafter, abbreviated as GC-MS). Specifically, a gas chromatograph analyzer (hereinafter abbreviated as GC) should be used to accurately separate each component with a different carbon chain length and double bond position, and apply each to a mass spectrometer (hereinafter abbreviated as MS). Thus, the double bond position can be identified, and each ratio can be determined from the GC peak area. As the content of the olefin having a double bond at the specific position, the value obtained from the GC peak area is used. When the olefins having different carbon numbers are mixed and used, the position distribution of double bonds is represented by the position distribution of double bonds in the olefins having the same carbon number.

In the present specification, when a plurality of internal olefin sulfonates obtained from a plurality of raw olefins having different double bond positions are mixed and used, two olefins of the raw materials of the internal olefin sulfonate are used. The position distribution of heavy bonds is calculated by using olefins having the same carbon number.

The liquid detergent composition of the present invention is a liquid detergent composition containing the following component (A1), the following component (B), and water,
The liquid detergent composition contains potassium ions, and optionally sodium ions,
The (sodium ion content)/(potassium ion content) mass ratio in the liquid detergent composition is 0 or more and 9 or less,
A liquid detergent composition is included. The matters described for the liquid detergent composition of the present invention can be appropriately applied to this liquid detergent composition.
Component (A1): an internal olefin sulfonate having 14 to 16 carbon atoms, which has a sulfonic acid group at 2 to 4 positions and has 14 to 16 carbon atoms (IO-1S). ) And the internal olefin sulfonate (IO-2S) having 14 or more and 16 or less carbon atoms in which the sulfonic acid group is present at the 5-position or more is 0.40 or more in (IO-1S)/(IO-2S). Internal olefin sulfonate (B) component having a carbon number of 14 or more and 16 or less and 6.0 or less: an organic solvent having a hydroxyl group of ClogP of -2 or more and 2 or less.

<(B) component>
The component (B) is an organic solvent having a hydroxyl group having ClogP of −2 or more and 2 or less. Some of the components (B) are generally used as a solubilizer. Those skilled in the art are searching for an organic solvent having an optimum hydroxyl group depending on the type and content of the surfactant contained in the liquid detergent composition. In the present invention, by adjusting the molar ratio of (content of sodium ions)/(content of potassium ions) in the liquid detergent composition containing the component (A), the degree of precipitation during low temperature storage can be controlled. Can be lowered.

Even if the liquid detergent composition of the present invention is placed in a low temperature environment, the component (B) has a hydroxyl group having a CLogP of −2 or more and 2 or less from the viewpoint of suppressing precipitation of solids in the composition. It is an organic solvent. In the present invention, CLogP is ChemBioDraw Ultra ver. of Perkin Elmer. The calculated value calculated using ChemProperty of 14.0 is used. The larger the value of ClogP, the higher the hydrophobicity.

The component (B) has a CLogP of preferably -1.4 or more, more preferably -1.2 or more, and further preferably from the viewpoint that the liquid detergent composition of the present invention can reduce the degree of precipitation at low temperature storage. Is -1 or more, more preferably -0.8 or more, even more preferably -0.5 or more, even more preferably -0.1 or more, even more preferably 0 or more, even more preferably 0.2 or more. , More preferably 0.4 or more, still more preferably 0.6 or more, and preferably 2 or less, more preferably 1.8 or less, still more preferably 1.7 or less, still more preferably 1.6 or less. , And more preferably an organic solvent having a hydroxyl group of 1.5 or less.

From the viewpoint that the component (B) can significantly lower the melting point of the hydrated solid in the presence of potassium ions than the melting point of the hydrated solid of the component (A) in the presence of sodium ions, CLogP is preferably -1. .4 or more, more preferably -1.2 or more, and from the same viewpoint, preferably 2 or less, more preferably 1.8 or less, still more preferably 1.5 or less, still more preferably 1 or less, still more preferably. Is an organic solvent having a hydroxyl group of 0.8 or less, and more preferably 0.4 or less.

The component (B) is an organic solvent having a hydroxyl group. The component (B) is preferably one or more organic solvents selected from the following components (B1) to (B4) from the viewpoint that the degree of precipitation at low temperature storage can be reduced.
Component (B1): Monovalent alcohol having 2 to 6 carbon atoms (B2) Component: Alcohol having 2 to 12 carbon atoms and divalent to 12 valents (B3) Component: Carbonization having 1 to 8 carbon atoms Organic solvent having hydrogen group, ether group and hydroxyl group (However, hydrocarbon group does not include aromatic group.)
Component (B4): Organic solvent having aromatic group, ether group and hydroxyl group which may be partially substituted. Specific examples of the components (B1) to (B4) are shown below. The numbers in parentheses are ChemBio Draw Ultraver. by Perkin Elmer. It is a calculated value (CLogP) of each component calculated using ChemProperty of 14.0.

As the monohydric alcohol having 2 to 6 carbon atoms, which is the component (B1), for example, ethanol (-0.24), 1-propanol (0.29), 2-propanol (0.07), phenol (1 .48).

As the alcohol having 2 to 12 carbon atoms and 2 to 12 valences, which is the component (B2), for example, ethylene glycol (-1.4), propylene glycol (-1.1), butylene glycol (-0. 73), hexylene glycol (-0.02), diethylene glycol (-1.3), triethylene glycol (-1.5), tetraethylene glycol (-1.66), dipropylene glycol (-0.69). , Tripropylene glycol (-0.55), and glycerin (-1.5).

As the component (B3), an organic solvent having a hydrocarbon group having 1 to 8 carbon atoms, an ether group and a hydroxyl group (provided that the hydrocarbon group excludes an aromatic group), for example, diethylene glycol monomethyl ether (-0. 78), diethylene glycol dimethyl ether (-0.26), triethylene glycol monomethyl ether (-0.96), diethylene glycol monoethyl ether (-0.39), diethylene glycol diethyl ether (0.52), diethylene glycol monobutyl ether (0. 67), dipropylene glycol monomethyl ether (-0.16), dipropylene glycol monoethyl ether (0.23), tripropylene glycol monomethyl ether (-0.03), 1-methoxy-2-propanol (-0. 30), 1-ethoxy-2-propanol (0.09), 1-methyl glycerin ether (-1.43), 2-methyl glycerin ether (-0.73), 1,3-dimethyl glycerin ether (-0). .67), 1-ethylglycerin ether (-1.04), 1,3-diethylglycerin ether (0.11), triethylglycerin ether (0.83), 1-pentylglyceryl ether (0.54), 2 -Pentyl glyceryl ether (1.25), 1-octyl glyceryl ether (2.1), 2-ethylhexyl glyceryl ether (2.0).

As the organic solvent having a partially substituted aromatic group, ether group and hydroxyl group, which is the component (B4), for example, 2-phenoxyethanol (1.2), diethylene glycol monophenyl ether (1.25), Examples include triethylene glycol monophenyl ether (1.08), 2-benzyloxyethanol (1.1), and diethylene glycol monobenzyl ether (0.96).

From the viewpoint that the component (B) can significantly lower the melting point of the hydrated solid in the presence of potassium ions than the melting point of the hydrated solid of the component (A) in the presence of sodium ions, the above-mentioned component (B2), An organic solvent having a hydroxyl group selected from the component (B3) and the component (B4), which is preferably an organic solvent having a hydroxyl group having a ClogP of −1.2 or more and 1.5 or less.
From the viewpoint of being able to significantly lower the melting point of the hydrated solid in the presence of potassium ions than the melting point of the hydrated solid of the component (A) in the presence of sodium ions, the component (B) is more preferably the above-mentioned ( It is preferable to include an organic solvent having a hydroxyl group selected from the component B2).

The liquid detergent composition of the present invention is an organic solvent having a hydroxyl group selected from the above-mentioned (B2) component, (B3) component and (B4) component, from the viewpoint of reducing the degree of precipitation at low temperature storage. The content ratio of the organic solvent having a hydroxyl group of ClogP of 0.6 or more and 1.5 or less is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably, in all components (B). It is 60% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less.

<water>
The liquid detergent composition of the present invention contains water. For example, water can be contained in order to make the composition of the present invention in a liquid state at 4° C. or higher and 40° C. or lower. As the water, deionized water (also referred to as ion-exchanged water) or sodium hypochlorite-added water in an amount of 1 mg/kg or more and 5 mg/kg or less with respect to the ion-exchanged water can be used. Also, tap water can be used.

<Composition, etc.>
The liquid detergent composition of the present invention contains potassium ions and optionally sodium ions, and the molar ratio of (content of sodium ions)/(content of potassium ions) in the liquid detergent composition is 0. The number is 9 or more. The (sodium ion content)/(potassium ion content) molar ratio is preferably 7 or less, more preferably 5 or less, still more preferably 3 or less, even more preferably 2 or less, still more preferably 1 or less. , More preferably 0.8 or less, and preferably 0. When sodium ions are present, the lower limit value is preferably 0.01 or more. In the present invention, the content of sodium ions and the content of potassium ions in the liquid detergent composition shall be calculated based on the amount of ions present in the liquid detergent composition, respectively. ..

Potassium ions and sodium ions are incorporated into the liquid detergent composition of the present invention from the component (A) and other compounds. The content of potassium ion and optional sodium ion in the liquid detergent composition of the present invention is the compounding amount of the compounding ingredients used in the liquid detergent composition, and potassium ion and optional sodium in the compounding ingredient. It can be determined from the content of ions. Further, for example, the amount in the liquid detergent composition can be quantified by a method according to the general rule of ion chromatography of Japanese Industrial Standard, JIS K0127:2013.

The liquid detergent composition of the present invention is more advantageous in the presence of potassium ions than the viewpoint of more easily obtaining the effect of suppressing solid precipitation at low temperatures, or the melting point of the hydrated solid of the component (A) in the presence of sodium ions. From the viewpoint of significantly lowering the melting point of the hydrated solid, 100 g of the composition preferably contains 0.005 mol or more of potassium ions, more preferably 0.01 mol or more, and even more preferably 0.03 mol or more. The content is more preferably 0.04 mol or more, still more preferably 0.05 mol or more, and preferably 0.3 mol or less, more preferably 0.25 mol or less, still more preferably 0.2 mol or less.

The content of the component (A) in the liquid detergent composition of the present invention is preferably 10% by mass or more, more preferably 11% by mass or more, from the viewpoint of more easily obtaining the effect of suppressing solid precipitation at low temperatures. It is preferably 12% by mass or more, and from the same viewpoint, 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.
The content of the component (A) contained in the liquid detergent composition is based on a value calculated by converting to a compound in which counter ions are replaced with hydrogen ions, that is, an acid type compound.

In the present invention, the proportion of the component (A) in the total anionic surfactant contained in the liquid detergent composition is 50% by mass or more, further 60% by mass or more, further 70% by mass or more, further 80% by mass or more, Further, it is preferably 90% by mass or more and 100% by mass or less.

The content of the component (B) in the liquid detergent composition of the present invention is preferably 4% by mass or more, more preferably 5% by mass or more, from the viewpoint of more easily obtaining the effect of suppressing solid precipitation at low temperatures, and , Preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, still more preferably 25% by mass or less.

The liquid detergent composition of the present invention is a mass ratio of the content of the component (A) and the content of the component (B), from the viewpoint of more easily obtaining the effect of suppressing the precipitation of solids at low temperatures, the component (B). Content/component (A) content is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.25 or more, and preferably 1 or less, more preferably 0.9 or less. , More preferably 0.8 or less, still more preferably 0.7 or less.

In the liquid detergent composition of the present invention, the content of water is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less.

<fiber>
The liquid detergent composition of the present invention is preferably a liquid detergent composition for fibers. The fibers constituting the fibers to be washed with the liquid detergent composition of the present invention may be either hydrophobic fibers or hydrophilic fibers. Examples of the hydrophobic fiber include protein fiber (milk protein casein fiber, promix, etc.), polyamide fiber (nylon, etc.), polyester fiber (polyester, etc.), polyacrylonitrile fiber (acrylic, etc.), polyvinyl alcohol fiber. Fibers (such as vinylon), polyvinyl chloride fibers (such as polyvinyl chloride), polyvinylidene chloride fibers (such as vinylidene), polyolefin fibers (such as polyethylene and polypropylene), polyurethane fibers (such as polyurethane), polyvinyl chloride/ Polyvinyl alcohol copolymer fiber (polycleral etc.), polyalkylene paraoxybenzoate fiber (benzoate etc.), polyfluoroethylene fiber (polytetrafluoroethylene etc.), glass fiber, carbon fiber, alumina fiber, silicone carbide fiber, rock Examples thereof include fibers (rock fiber), slag fibers (slug fibers), metal fibers (gold yarn, silver yarn, steel fibers). Examples of hydrophilic fibers include seed hair fibers (cotton, rice noodles, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), vein fibers (manila, sisal, etc.), palm fibers, Igusa, straw, animal hair fiber (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fiber (domestic silk, wild silk), feather, cellulosic fiber (rayon, polynosic, cupra, acetate, etc.) Etc. are illustrated.
The fibers are preferably fibers including cotton fibers.

The present invention is preferably directed to fibers, but its form is not only unprocessed fibers but also woven fabrics using the above-mentioned hydrophobic fibers and hydrophilic fibers, knitted fabrics, non-woven fabrics and the like, and obtained using them. It may be in the form of textile products such as undershirts, T-shirts, shirts, blouses, slacks, hats, handkerchiefs, towels, knits, socks, underwear, tights and the like. The term “fiber” in the present invention may include a fiber product. The fibers are preferably fibers including cotton fibers. The content of the cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further more preferably 20% from the viewpoint of further improving the softness of the fiber. % Or more, more preferably 100% by mass.

<Arbitrary ingredients>
In the liquid detergent composition of the present invention, a surfactant other than the component (A) can be used as the component (C) as long as the effects of the present invention are not impaired. Examples of the component (C) include anionic surfactants other than the component (A), and one or more surfactants selected from nonionic surfactants.

Examples of the component (C) include one or more anionic surfactants selected from the following components (c1), (c2), (c3) and (c4).
Component (c1): Alkyl or alkenyl sulfate ester salt (c2) Component: Polyoxyalkylene alkyl ether sulfate ester salt or polyoxyalkylene alkenyl ether sulfate ester salt (c3) Component: Anionic surfactant having a sulfonate group (however, (Excluding (A) component)
Component (c4): fatty acid or salt thereof

As the component (c1), more specifically, one or more selected from an alkyl sulfate ester salt having an alkyl group having 10 to 18 carbon atoms and an alkenyl sulfate ester salt having an alkenyl group having 10 to 18 carbon atoms. Anionic surfactants of

As the component (c2), more specifically, the alkyl group having 10 to 18 carbon atoms, the alkylene oxide average addition mole number of 1 to 3 or less polyoxyalkylene alkyl sulfate ester salt, and the alkenyl group carbon number One or more anionic surfactants selected from polyoxyalkylene alkenyl ether sulfuric acid ester salts having an alkylene oxide average addition mole number of 1 or more and 3 or less and 10 or more and 18 or less.

The anionic surfactant having a sulfonate group as the component (c3) represents an anionic surfactant having a sulfonate as a hydrophilic group (however, the component (A) is excluded).
As the component (c3), more specifically, an alkylbenzenesulfonate having an alkyl group having 10 to 18 carbon atoms, an alkenyl group having 10 to 18 carbon atoms, and an alkyl group having carbon number Is 10 or more and 18 or less alkane sulfonate, α-sulfo fatty acid salt having 10 or more and 18 or less carbon atoms in the fatty acid moiety, and 10 or more and 18 or less carbon atoms in the fatty acid moiety, and 1 or more carbon atoms in the ester moiety. One or more anionic surfactants selected from α-sulfofatty acid lower alkyl ester salts having 5 or less and internal olefin sulfonates having 12 to 16 carbon atoms can be mentioned.

Examples of the fatty acid or salt thereof as the component (c4) include fatty acids having 10 or more and 20 or less carbon atoms or salts thereof. From the viewpoint of being able to further reduce precipitation at low temperatures, the carbon number of the component (d4) is 10 or more, preferably 12 or more, more preferably 14 or more, and 20 or less, preferably 18 or less.

As the salt of the anionic surfactant which is the component (c1) to the component (c4), an alkali metal salt is preferable, a sodium salt or a potassium salt is more preferable, and a sodium salt is further preferable.

Moreover, as the other component (C), a nonionic surfactant having a hydroxyl group or a polyoxyalkylene group as the component (c5) can be mentioned.
The component (c5) is preferably a nonionic surfactant represented by the following general formula (c5).
^{_{R 1 (CO) m O- (}} AO) n -R 2 (c5)
[In the formula, R ¹ is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R ² is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, and The AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is an average number of moles added and is a number of 3 or more and 50 or less. ]

In general formula (c5), R ¹ is an aliphatic hydrocarbon group having 9 to 16 carbon atoms. From the viewpoint of detergency, the carbon number of R ¹ is preferably 12 or more, more preferably 12.5 or more, still more preferably 13.0 or more, and from the same viewpoint, 16 or less, preferably 15 or less. The aliphatic hydrocarbon group for R ¹ is preferably a group selected from an aliphatic alkyl group and an aliphatic alkenyl group. The carbon number of R ¹ may be the average carbon number.

In general formula (c5), the AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group. When it contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be a block-type bond or a random-type bond. From the viewpoint of detergency, the AO group is preferably a group containing an ethyleneoxy group.

In general formula (c5), n is an average number of moles added and is a number of 3 or more and 50 or less. From the viewpoint of detergency, n is 6 or more, preferably 6.5 or more, more preferably 7 or more, even more preferably 8 or more, even more preferably 9 or more, even more preferably 10 or more, still more preferably 12 From the above, and from the same viewpoint, it is preferably 50 or less, preferably 45 or less, more preferably 40 or less, further preferably 35 or less, even more preferably 26 or less, still more preferably 24 or less.

When the liquid detergent composition of the present invention contains the component (C), the content thereof in the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 8% by mass or less. , And more preferably 6 mass% or less.

In addition, the liquid cleaning composition of the present invention may contain the following components (d1) to (d7).
(D1) 0.01% by mass or more and 10% by mass or less of a redeposition preventing agent and a dispersant such as polyacrylic acid, polymaleic acid and carboxymethylcellulose in the composition (d2) hydrogen peroxide, sodium percarbonate or sodium perborate, etc. 0.01% by mass or more and 10% by mass or less of the bleaching agent in the composition (d3) tetraacetylethylenediamine, the bleaching activity represented by the general formulas (I-2) to (I-7) of JP-A-6-316700. A bleaching activator such as an activator in an amount of 0.01% by mass to 10% by mass in the composition,
(D4) One or more enzymes selected from cellulases, amylases, pectinases, proteases and lipases, preferably one or more enzymes selected from amylases and proteases, in an amount of 0.001 mass% or more, preferably 0.01 Mass% or more, more preferably 0.1 mass% or more, further preferably 0.3 mass% or more, and 2 mass% or less, preferably 1 mass% or less (d5) fluorescent dye, for example, Tinopearl CBS (trade name, Ciba Specialty Chemicals) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) in the composition, 0.001% by mass or more and 1% by mass or less (d6) butylhydroxytoluene, distyrenated cresol, 0.01% by mass or more and 2% by mass or less (d7) of antioxidants such as sodium sulfite and sodium bisulfite in the composition (d7), an appropriate amount of a defoaming agent such as a fragrance, an antibacterial preservative, and silicone.

The pH of the liquid detergent composition of the present invention at 20° C. is preferably 3 or higher, more preferably 4 or higher, and preferably 10 or lower, more preferably 9 or lower, still more preferably 8 or lower. The pH is measured according to the pH measuring method described below.
<Method of measuring pH>
A pH measuring composite electrode (HORIBA glass sliding sleeve type) is connected to a pH meter (HORIBA pH/ion meter F-23), and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol/L) is used as the pH electrode internal liquid. Next, a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) were filled in 100 mL beakers respectively, and 25 Immerse in a constant temperature bath at ℃ for 30 minutes. The pH measuring electrode is immersed in the standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH 6.86→pH 9.18→pH 4.01. The sample to be measured is adjusted to 25° C., the electrode of the pH meter is immersed in the sample, and the pH after 1 minute is measured.

The present invention provides a method for cleaning fibers, which comprises cleaning the fibers with a cleaning liquid containing the liquid detergent composition of the present invention and water. The matters described in the liquid detergent composition of the present invention can be appropriately applied to this cleaning method. The content of the component (A) in the cleaning liquid is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and preferably 1 mass% or less, more preferably 0.8 mass% or less. Is. The content of the component (B) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and preferably 0.6% by mass or less, more preferably 0. It is 5 mass% or less.

Water having hardness is preferable as the water used in the method for cleaning fibers of the present invention. The hardness of water is, in terms of German hardness, preferably 1° dH or more, more preferably 2° dH or more, still more preferably 3.5° dH or more, still more preferably 5° dH. The above is more preferably 7°dH or more, and preferably 20°dH or less, more preferably 18°dH or less, and further preferably 15°dH or less. Here, the German hardness (°dH) in the present specification means the concentration of calcium and magnesium in water in terms of CaCO ₃ conversion concentration of 1 mg/L (ppm)=about 0.056°dH (1°dH=17. 8 ppm).
The calcium and magnesium concentrations for this German hardness are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.
The specific method for measuring the German hardness of water in the present specification is shown below.
<Measuring method of German hardness of water>
〔reagent〕
-0.01 mol/l EDTA-2Na solution: 0.01 mol/l aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH)
・Universal BT indicator (Product name: Universal BT, manufactured by Dojindo Laboratories Co., Ltd.)
-Ammonia buffer for hardness measurement (solution in which 67.5 g of ammonium chloride is dissolved in 570 ml of 28 w/v% ammonia water and the total amount is 1000 ml with ion-exchanged water)
[Measurement of hardness]
(1) Collect 20 ml of sample water into a conical beaker with a whole pipette.
(2) Add 2 ml of ammonia buffer solution for hardness measurement.
(3) Add 0.5 ml of Universal BT indicator. Make sure that the solution after addition is magenta.
(4) While thoroughly shaking the conical beaker, 0.01 mol/l EDTA.2Na solution was added dropwise from the buret, and the time point at which the sample water turned blue was taken as the end point of the titration.
(5) The total hardness is calculated by the following calculation formula.
Hardness (°dH)=T×0.01×F×56.0774×100/A
T: Titration amount of 0.01 mol/l EDTA.2Na solution (mL)
A: Sample volume (20 mL, volume of sample water)
F: Factor of 0.01 mol/l EDTA/2Na solution

The cleaning liquid used in the present invention is preferably a cleaning liquid obtained by mixing the component (A), the component (B), and water having a German hardness of 1° dH or more and 20° dH or less.

In the fiber cleaning method of the present invention, the value of the bath ratio represented by the ratio of the mass of fiber (kg) to the amount of cleaning liquid (liter), that is, the amount of cleaning liquid (liter)/mass of fiber (kg) (hereinafter, This ratio may be used as a bath ratio) is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, and preferably 100 or less.

In the fiber washing method of the present invention, the time for washing the fibers is preferably 1 minute or more, more preferably 2 minutes or more, further preferably 3 minutes or more, and preferably 12 hours or less, more preferably 8 hours or less. , More preferably 6 hours or less, still more preferably 3 hours or less, still more preferably 1 hour or less.

The fiber cleaning method of the present invention is also suitable for a rotary cleaning method. The rotary cleaning method means a cleaning method in which fibers that are not fixed to a rotating device rotate around a rotation axis together with a cleaning liquid. The rotary washing method can be carried out by a rotary washing machine. Specific examples of the rotary washing machine include a drum-type washing machine, a pulsator-type washing machine, and an agitator-type washing machine. As each of these rotary washing machines, a commercially available one for home use can be used. In recent years, drum-type washing machines have rapidly become popular because the amount of water used for one washing can be further reduced. Particularly, the drum-type washing machines can reduce the amount of water used for washing.

<Method for producing liquid detergent composition>
The present invention provides a method for producing a liquid detergent composition, which comprises mixing the following component (A), the following component (B) and a component containing water (hereinafter referred to as a mixed component),
The mixed component includes a substance (I) that releases potassium ions in water, and an arbitrary substance (II) that releases potassium ions in water,
Here, the substance (I) may contain the component (A), and the substance (II) may contain the component (A).
The substance (I) and the substance (II) are mixed so that the molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less.
A method for producing a liquid detergent composition is provided.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2

Preferred embodiments of the component (A) and the component (B) in this production method are the same as those of the liquid detergent composition of the present invention. In addition, the matters described in the liquid detergent composition of the present invention can be appropriately applied to this production method. The content in the composition can be replaced by the ratio in the total components to be mixed. The liquid detergent composition of the present invention can be produced by the method for producing a liquid detergent composition of the present invention.

In the method for producing a liquid detergent composition of the present invention, the mixed component contains a substance (I) that releases potassium ions in water and an arbitrary substance (II) that releases sodium ions in water. The substance (I) and the substance (II) may each contain the component (A). That is, the component (A) may be a part or all of the substance (I). The component (A) may be a part or the whole of the substance (II). Each of the substance (I) and the substance (II) is selected from appropriate substances depending on the use and purpose of the liquid detergent composition. Examples of the substance (I) include alkaline agents such as potassium hydroxide, inorganic potassium salts such as potassium sulfate and potassium chloride, fatty acid potassium having 1 to 18 carbon atoms, and potassium sulfate ester having 1 to 18 carbon atoms. Examples thereof include organic potassium salts having 1 to 18 carbon atoms such as potassium aromatic sulfonate having 1 to 18 carbon atoms. Examples of the substance (II) include alkaline agents such as sodium hydroxide, inorganic sodium salts such as sodium sulfate and sodium chloride, fatty acid sodium having 1 to 18 carbon atoms, sodium sulfate ester having 1 to 18 carbon atoms, Examples thereof include organic sodium salts having 1 to 26 carbon atoms such as sodium aromatic sulfonate having 1 to 26 carbon atoms.

In the method for producing a liquid detergent composition of the present invention, the substance (I) and the substance (II) have a molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition. Mix so as to be 0 or more and 9 or less. The preferable value of this molar ratio is the same as that of the liquid detergent composition of the present invention. Usually, the amounts of potassium ion and sodium ion in the mixed component are known, so the amount of the substance (I) and the substance (II) mixed can be appropriately determined in consideration of the composition of the liquid detergent composition. ..

In the method for producing a liquid detergent composition of the present invention, the ratio of the component (A) in the mixed component is preferably 10% by mass or more, more preferably 11% by mass or more, further preferably 12% by mass or more, and preferably Is 60 mass% or less, more preferably 50 mass% or less, and further preferably 40 mass% or less.

<Melting point lowering agent for hydrated solid>
The present invention is a reducing agent of the melting point of a hydrated solid in a liquid detergent composition, which comprises potassium ions,
The liquid detergent composition contains the following component (A), the following component (B), and water:
It relates to a melting point lowering agent.
Component (A): Internal olefin sulfonate having 14 or more and 16 or less carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 or more and 2 or less (A) component and (B) component in the melting point lowering agent Preferred embodiments of are the same as the liquid detergent composition and the method for producing the same of the present invention, respectively. Further, as the melting point lowering agent, the matters described in the liquid detergent composition and the method for producing the same of the present invention can be appropriately applied.

<Method of lowering melting point of hydrated solid>
The present invention is a method for lowering the melting point of a hydrated solid of a component (A) in a liquid detergent composition containing the following component (A), the following component (B) and water:
The liquid detergent composition contains potassium ion, and optionally sodium ion,
The molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less,
A method for lowering the melting point of a hydrated solid.
Component (A): Internal olefin sulfonate having 14 or more and 16 or less carbon atoms (B) Component: Organic solvent having a hydroxyl group having ClogP of -2 or more and 2 or less (A) component and (B) component in the melting point lowering method Preferred embodiments of are the same as the liquid detergent composition and the method for producing the same of the present invention, respectively. The preferred embodiment of the molar ratio of (content of sodium ion)/(content of potassium ion) is the same as that of the liquid detergent composition and the method for producing the same of the present invention. Further, as the method for lowering the melting point, the manufacturing method of the present invention and the matters described in the manufacturing method can be appropriately applied.

[Production Example of Raw Material for Component (A): Production Example of Internal Olefin A and B Having 16 Carbon]
In a flask equipped with a stirrer, 1-hexadecanol (product name: Calcol 6098, manufactured by Kao Co., Ltd.) 7000 g (28.9 mol), and γ-alumina (STREM Chemicals, Inc.) 700 g (as a raw material alcohol) as a solid acid catalyst. 10% by mass), and the reaction was carried out under stirring at 280° C. while flowing nitrogen (7000 mL/min.) in the system while changing the reaction time for each of the target internal olefins A and B. .. The obtained crude internal olefin was transferred to a distillation flask and distilled at 136-160° C./4.0 mmHg to obtain C16 internal olefins A and B having an olefin purity of 100%. The double bond distribution of the obtained internal olefin is shown.
The double bond distribution (mass %) of the internal olefin A is 1-position/2-position/3-position/4-position/5-position/6-position/7-position/8-position=1.8/40.7/29.3/ It was 15.7/7.3/3.0/1.1/1.1.
The double bond distribution (mass%) of the internal olefin B is 1-position/2-position/3-position/4-position/5-position/6-position/7-position/8-position=0.5/30.1/25.5/ It was 18.9/11.0/7.0/3.5/3.5.

The double bond distribution of the internal olefin was determined by the above method.
In the case of an olefin having 16 carbon atoms, an internal olefin having a double bond at the 7-position and an internal olefin having a double bond at the 8-position are structurally indistinguishable, but are distinguished when sulfonated. For convenience, the values obtained by dividing the amount of the internal olefin having a double bond at the 7-position by 2 are shown in the 7-position and 8-position columns.

[Production Example 1: Production Example of Internal C16 Potassium Olefin Sulfonate]
The internal olefins A and B obtained by the above production example of raw materials are subjected to sulfur trioxide gas using a thin film sulfonation reactor having an outer jacket, and cooling water at 20° C. is passed through the outer jacket of the reactor. Thus, the sulfonation reaction was performed. The SO ₃ /internal olefin molar ratio during the sulfonation reaction was set to 1.09. The obtained sulfonated product was added to an alkaline aqueous solution prepared with 1.5 mol times the theoretical acid value of potassium hydroxide, and neutralized for 1 hour at 30° C. with stirring. The neutralized product was heated in an autoclave at 160° C. for 1 hour for hydrolysis to obtain a C 16 internal potassium olefin sulfonate product. By evaporating this composition to dryness, (a-1) and (a-2), which are internal olefin sulfonates having 16 carbon atoms, were obtained. Here, the internal olefin sulfonate obtained from the internal olefin A as the raw material was designated as (a-1), and the internal olefin sulfonate obtained from the internal olefin B as the raw material was designated as (a-2).
In (a-1), the content rate (mass %) of the internal olefin sulfonate in which the sulfonic acid group is bonded is shown. 1st/2nd/3rd/4th/5-8th = 0.7/32.1/24.2/25.8/17.2. (IO-1S)/(IO-2S)=4.8. In (a-1), the mass of potassium ions was 18.1 g based on 100 g of the acid form of the internal olefin sulfonic acid.
In (a-2), the content rate (mass %) of the internal olefin sulfonate in which the sulfonic acid group is bonded is shown. 1st/2nd/3rd/4th/5-8th=1.5/24.1/19.9/24.6/29.9. (IO-1S)/(IO-2S)=2.3. In (a-2), the mass of potassium ion was 18.1 g based on 100 g of the acid form of the internal olefin sulfonic acid.

[Production Example 2: Production example of internal sodium olefinsulfonate having 16 carbon atoms]
The same operation as in Production Example 1 was performed except that the potassium hydroxide used for neutralizing the sulfonated product in Production Example 1 was replaced with sodium hydroxide. The internal olefin sulfonic acid sodium salt obtained from the internal olefin A was designated as (a-3), and the internal olefin sulfonic acid sodium salt obtained from the internal olefin B was designated as (a-4).
In (a-3), the content rate (mass %) of the internal olefin sulfonate in which the sulfonic acid group is bonded is shown. 1st/2nd/3rd/4th/5-8th = 0.7/32.1/24.2/25.8/17.2. (IO-1S)/(IO-2S)=4.8. In (a-3), the mass of sodium ions was 10.7 g per 100 g of the acid form of the internal olefin sulfonic acid.
In (a-4), the content rate (mass %) of the internal olefin sulfonate in which the sulfonic acid group is bonded is shown. 1st/2nd/3rd/4th/5-8th=1.5/24.1/19.9/24.6/29.9. (IO-1S)/(IO-2S)=2.3. In (a-4), the mass of sodium ions was 10.7 g per 100 g of the acid form of the internal olefin sulfonic acid.

The content ratio of the internal olefin sulfonate having a sulfonic acid group bonded was measured by high performance liquid chromatography/mass spectrometry (HPLC-MS). Specifically, the hydroxy form having a sulfonic acid group bonded thereto was separated by high performance liquid chromatography (HPLC), and each was identified by mass spectrometry (MS). As a result, each ratio was obtained from the HPLC-MS peak area. In the present specification, each ratio obtained from the peak areas was calculated as a mass ratio.
The apparatus and conditions used for the measurement are as follows. HPLC device “LC-20ASXR” (manufactured by Shimadzu Corporation), column “ODS Hypersil (registered trademark)” (4.6×250 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific), sample preparation (methanol) 1000 times), eluent A (10 mM ammonium acetate-added water), eluent B (10 mM ammonium acetate-added methacrylonitrile/water=95/5 (v/v) solution), gradient (0 minutes (A/ B=60/40)→15.1 to 20 minutes (30/70)→20.1 to 30 minutes (60/40), MS device “LCMS-2020” (manufactured by Shimadzu Corporation), ESI detection ( Anion detection m/z: 321.10 (component (A) having 16 carbon atoms), column temperature (40° C.), flow rate (0.5 mL/min), injection volume (5 μL).

The components used in the compositions in the table are shown below.
{(A) component}
(A-1): In the Production Example 1, the potassium salt of an internal olefin sulfonate obtained from the internal olefin A (a-1) is the component (A) and also the substance (I).
(A-2): In the Production Example 1, the potassium salt of an internal olefin sulfonate obtained from the internal olefin B (a-2) is the component (A) and also the substance (I).
(A-3): Internal olefin sulfonic acid sodium salt obtained from internal olefin A in Production Example 2 (a-3) is the component (A) and also the substance (II).
(A-4): In the Production Example 2, the internal olefin sulfonic acid sodium salt (a-4) obtained from the internal olefin B is the component (A) and also the substance (II).
The component (A) is shown in the table by mass% in terms of acid type compound.

{(B) component}
(B-1): Diethylene glycol monobutyl ether (ClogP=0.67)
(B-2): Phenoxyethanol (ClogP=1.2)
(B-3): Propylene glycol (ClogP=-0.96)

{(C) component}
(C-1): Polyoxyalkylene lauryl ether (adding 9 mol of ethyleneoxy groups on average to 1 mol of lauryl alcohol on average, then adding 2 mol of propyleneoxy groups on average, and then adding 9 units of ethyleneoxy groups on average) Molated compound, HLB=14.5, in the general formula (c5), R ¹ : lauryl group, m:0, AO: ethyleneoxy group and propyleneoxy group, n: 20, R ² : compound of hydrogen atom)

{PH adjuster} Monoethanolamine {water}
Deionized water

{Substance (I), Substance (II)}
Among the components, (a-1) and (a-2) correspond to the substance (I). Each of (a-1) and (a-2) releases 18.1 g of potassium ion per 100 g of the acid type compound.
Among the components, (a-3) and (a-4) correspond to the substance (II). (A-3) and (a-4) each release 10.7 g of sodium ion per 100 g of the acid type compound.

<Method for producing liquid detergent composition>
Liquid detergent compositions shown in Tables 1 and 2 were produced using the above-mentioned components, and the following items were evaluated. The results are shown in Tables 1 and 2. The liquid detergent compositions shown in Tables 1 and 2 were specifically manufactured as follows. A Teflon (registered trademark) stirrer piece having a length of 5 cm was placed in a glass beaker having a capacity of 200 mL to measure the mass. Next, 90% by mass of the required amount of the ion-exchanged water at 20° C. and the required amount of the components (A), (B), and (C) are added to make 100 g, and the top of the beaker is added. Was sealed with Saran Wrap (registered trademark). The beaker containing the contents was placed in a 60° C. water bath installed on a magnetic stirrer, and the water in the water bath was stirred at 100 r/min for 30 minutes within a temperature range of 60±2° C. Next, the water in the water bath was replaced with tap water at 5°C, and the composition was cooled in the beaker until the temperature of the composition reached 20°C. Next, the liquid detergent composition was adjusted with monoethanolamine so that the pH at 20° C. was 7.5. The pH was measured with a pH meter using a glass electrode. Next, the Saran Wrap (registered trademark) was removed, ion-exchanged water was added so that the mass of the content was 100 g, and the mixture was stirred again at 100 r/min for 30 seconds, and the liquid detergent composition shown in Tables 1 and 2 was added. I got a thing.

<Measurement method of melting point of hydrated solid>
10 g of the liquid detergent composition shown in Table 1 was put into a No. 4 screw tube (manufactured by AS ONE) and was capped. Next, the screw tube charged with the liquid detergent composition was left in a deep freezer at -30°C for 3 hours, and then left in an ice bath for 2 hours. After that, the temperature was raised at a rate of 12° C./hour, and the state in which the crystal substance in the screw tube was completely melted was visually observed, and the temperature at which the crystal substance was melted was measured. That temperature was taken as the melting point of the hydrated solid.

<Evaluation method of storage stability>
30 g of the composition of Table 2 was added to No. It was put in a standard glass bottle of No. 6, and the height X (cm) from the inner bottom surface of the standard bottle to the liquid surface of the liquid detergent composition was measured. Next, the standard bottle filled with the composition shown in Table 2 was stored in a thermostat at -5°C for 20 days. The standard bottle after 20 days was taken out of the thermostat, and 20 seconds later, the height Y (cm) of the white solid substance precipitated in the contents was measured from the inner bottom surface of the standard bottle. Y/X, which is the ratio of the height X of the liquid detergent composition before storage to the height Y of the precipitated white material after storage at −5° C. for 20 days, was calculated. Further, the degree of turbidity of the liquid after storage at -5°C for 20 days was visually observed. Unless otherwise specified, the liquid was clear.

Claims (7)

A liquid detergent composition containing the following component (A), the following component (B), and water,
The liquid detergent composition contains potassium ions, and optionally sodium ions,
The molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less,
Liquid detergent composition.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2 The liquid detergent composition according to claim 1, wherein the proportion of the component (A) in all the anionic surfactants contained in the liquid detergent composition is 60% by mass or more and 100% by mass or less. The liquid detergent composition according to claim 1 or 2, wherein the component (B) is one or more selected from the following components (B1) to (B4).
Component (B1): Monovalent alcohol having 2 to 6 carbon atoms (B2) Component: Alcohol having 2 to 12 carbon atoms and divalent to 12 valents (B3) Component: Carbonization having 1 to 8 carbon atoms Organic solvent having hydrogen group, ether group and hydroxyl group (However, hydrocarbon group does not include aromatic group.)
Component (B4): Organic solvent having aromatic group, ether group and hydroxyl group, which may be partially substituted As the component (A), an internal olefin sulfonate (IO-1S) having a sulfonic acid group at the second position to the fourth position and having 14 to 16 carbon atoms, and a carbon number having the sulfonic acid group at the fifth position or more. Includes 14 or more and 16 or less internal olefin sulfonate (IO-2S), and the mass ratio of (IO-1S) and (IO-2S) is (IO-1S)/(IO-2S) 0.40 or more. The liquid detergent composition according to any one of claims 1 to 3, which has a content of 6.0 or less. A method for producing a liquid detergent composition, which comprises mixing the following component (A), the following component (B) and a component containing water (hereinafter referred to as a mixed component),
The mixed component includes a substance (I) that releases potassium ions in water, and an arbitrary substance (II) that releases sodium ions in water,
Here, the substance (I) may contain the component (A), and the substance (II) may contain the component (A).
The substance (I) and the substance (II) are mixed so that the molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less.
A method for producing a liquid detergent composition.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2 A melting point lowering agent for a hydrated solid in a liquid detergent composition, which comprises potassium ions,
The liquid detergent composition contains the following component (A), the following component (B), and water:
Melting point lowering agent.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2 A method for lowering the melting point of a hydrated solid of component (A) in a liquid detergent composition containing the following component (A), component (B) and water:
The liquid detergent composition contains potassium ion, and optionally sodium ion,
The molar ratio of (content of sodium ion)/(content of potassium ion) in the liquid detergent composition is 0 or more and 9 or less,
Method of lowering melting point of hydrated solid.
Component (A): Internal olefin sulfonate having 14 to 16 carbon atoms (B) Component: Organic solvent having a hydroxyl group with ClogP of -2 to 2