HK40000835B - Liquid detergent composition for textile products - Google Patents

Description

Liquid detergent composition for fiber products

Technical Field

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

Background Art

Anionic surfactants, particularly alkylbenzene sulfonates, nonionic surfactants containing an oxyalkylene group having 2 to 3 carbon atoms, and olefin sulfonates, particularly internal olefin sulfonates obtained from internal olefins having double bonds internally rather than at the ends of the olefin chain, have been widely used as cleaning ingredients for household and industrial use.

Japanese Patent Application Laid-Open Nos. 2015-28123 and 2014-77126 disclose internal olefin sulfonate compositions containing an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms at a specific ratio, and having a specific ratio of hydroxyl form to olefin form, exhibiting excellent foaming properties. The compositions also describe the use of a solubilizing agent such as propylene glycol.

Japanese Patent Application Laid-Open No. 2003-81935 discloses an internal olefin sulfonate obtained by sulfonating, neutralizing, and hydrolyzing an internal olefin having 8 to 30 carbon atoms and having a double bond at the 2-position of 20 to 95% and a cis/trans ratio of 1/9 to 6/4. Prior art discloses internal olefin sulfonates in which the positional distribution of double bonds is described.

European Patent Publication No. 377261 discloses a detergent composition having excellent cleaning properties and containing an internal olefin sulfonate containing 25% or more of a β-hydroxy form. Specific examples thereof include a liquid detergent containing monopropylene glycol.

Japanese Patent Application Laid-Open No. 2011-32456 describes the use of a water-soluble organic solvent from the viewpoint of improving the stability and solubility of a liquid detergent composition.

Summary of the Invention

The present invention relates to a liquid detergent composition for textile products that has an excellent effect of imparting a good feel to textile products and an excellent cleaning power against stains attached to textile products.

The present invention relates to a liquid detergent composition for textile products, comprising 10% by mass or more and 60% by mass or less of the following component (A), the following component (B), and water.

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th position and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th position and having 17 to 24 carbon atoms is 0.75 to 5.5 (10-1S)/(10-2S).

Component (B): Organic solvent having a hydroxyl group

The present invention relates to a liquid detergent composition for textile products comprising 10% by mass or more and 60% by mass or less of the following component (A1), the following component (B), and water.

Component (A1): an internal olefin sulfonate obtained from an internal olefin having 17 to 24 carbon atoms, wherein the internal olefin is obtained from an olefin having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms (IO-1) and an olefin having a double bond at positions 5 to 17 to 24 carbon atoms (IO-2) in which the mass ratio (IO-1)/(IO-2) is 0.50 to 6.5.

Component (B): Organic solvent having a hydroxyl group

In another aspect, the present invention relates to a liquid detergent composition for textile products comprising 10% by mass or more and 60% by mass or less of the following component (A), the following component (B), and water.

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th positions and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th positions and having 17 to 24 carbon atoms is 0.75 to 5.5, and wherein the internal olefin sulfonate is obtained from an internal olefin having 17 to 24 carbon atoms, and wherein the internal olefin sulfonate (10-1) having a double bond at the 1st to 3rd positions and having 17 to 24 carbon atoms to the internal olefin (10-2) having a double bond at the 5th to 5th positions and having 17 to 24 carbon atoms is 0.50 to 6.5, respectively.

Component (B): Organic solvent having a hydroxyl group

The present invention also relates to a method for producing a liquid detergent composition for textile products, wherein the method comprises mixing the following component (A), the following component (B), and water, wherein the proportion of component (A) in all the mixed components is 10% by mass or more and 60% by mass or less.

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th position and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th position and having 17 to 24 carbon atoms is 0.75 to 5.5 (10-1S)/(10-2S).

Component (B): Organic solvent having a hydroxyl group

According to the present invention, a liquid detergent composition for textile products can be obtained that can maintain the cleaning performance of stains attached to textile products and impart a good texture to the textile products.

DETAILED DESCRIPTION

<Liquid detergent composition for textile products>

The present inventors have discovered that a liquid detergent composition for textile products containing an internal olefin sulfonate having 17 to 24 carbon atoms, water, and an organic solvent having a hydroxyl group, wherein the mass ratio (10-1S) of the internal olefin sulfonate having 17 to 24 carbon atoms and the sulfonic acid group being present at the 2nd to 4th positions to the internal olefin sulfonate having 17 to 24 carbon atoms to the internal olefin sulfonate having 17 to 24 carbon atoms and the sulfonic acid group being present at the 5th to 5th positions, and the internal olefin sulfonate having 17 to 24 carbon atoms (10-2S) is 0.75 to 5.5, has excellent effect of imparting a good feel to textile products and excellent cleaning properties against stains attached to textile products.

Here, the internal olefin sulfonate may be an internal olefin sulfonate obtained from an internal olefin having 17 to 24 carbon atoms, and may be an internal olefin sulfonate obtained from an olefin having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms (IO-1) and an olefin having a double bond at positions 5 to 24 carbon atoms (IO-2) in the internal olefin, wherein the mass ratio (IO-1)/(IO-2) is 0.50 to 6.5.

＜(A)Component＞

The component (A) of the present invention is an internal olefin sulfonate having 17 to 24 carbon atoms. The mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group located at positions 2 to 4 and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group located at positions 5 to 5 and having 17 to 24 carbon atoms is 0.75 to 5.5, as calculated by weight. This component cleans stains attached to fibers. Furthermore, by combining it with the hydroxyl-containing organic solvent (component (B)) described later, the effect of imparting a good feel to fiber products can be enhanced. In particular, even when the liquid detergent composition for fiber products of the present invention is used for cleaning at low temperatures, the effect of imparting a good feel to fibers can be enhanced. Component (A) can be obtained by sulfonating an internal olefin having 17 to 24 carbon atoms. (IO-2S) is preferably an internal olefin sulfonate having a sulfonic acid group at positions 5 to 9 and having 17 to 24 carbon atoms.

The component (A) is an internal olefin sulfonate having 17 to 24 carbon atoms. Furthermore, the component (A) contains an internal olefin sulfonate having 17 to 24 carbon atoms (10-1S) in which the sulfonic acid group is present at positions 2 to 4, and an internal olefin sulfonate having 17 to 24 carbon atoms (10-2S) in which the sulfonic acid group is present at positions 5 to 24, and the mass ratio of (10-1S) to (10-2S) is 0.75 to 5.5.

From the viewpoint of improving the softness of the fiber and improving the cleanability, the mass ratio of the content of (IO-1S) to the content of (IO-2S) in component (A), i.e., (IO-1S)/(IO-2S), is 0.75 or more, more preferably 0.9 or more, further preferably 1.0 or more, further more preferably 1.2 or more, further more preferably 1.4 or more, further more preferably 1.6 or more, further more preferably 2.0 or more, further more preferably 2.4 or more, further more preferably 4.5 or more, and 5.5 or less.

Furthermore, the content of each compound having different positions of the sulfonic acid group in component (A) can be measured using a high performance liquid chromatography mass spectrometer (hereinafter referred to as HPLC-MS). The content of each compound having different positions of the sulfonic acid group in this specification is obtained as the mass ratio of the HPLC-MS peak area of the compound having the sulfonic acid group at each position in all HAS of component (A).

Here, HAS refers to hydroxyalkane sulfonate among compounds produced by sulfonation of internal olefins, that is, a hydroxyl form of internal olefin sulfonate.

In the present invention, the internal olefin sulfonate (IO-1S) in which the sulfonic acid group is present at the 2nd position or higher and the 4th position or lower and the number of carbon atoms is 17 or higher and 24 or lower refers to a sulfonate in which the sulfonic acid group is present at the 2nd position or higher and the 4th position or lower and the number of carbon atoms is 17 or higher and 24 or lower in the HAS body with a carbon number of 17 or higher and 24 or lower.

In addition, the internal olefin sulfonate (IO-2S) in which the sulfonic acid group is present at the 5th position or higher and the number of carbon atoms is 17 or higher and 24 or lower refers to a sulfonate in which the sulfonic acid group is present at the 5th position or higher and the number of carbon atoms is 17 or higher and 24 or lower in the HAS body with a carbon number of 17 or higher and 24 or lower.

The internal olefin sulfonate as component (A) comprises an internal olefin sulfonate (10-1S) in which the sulfonic acid group is present at positions 2 to 4 and has a carbon number of 17 to 24, and an internal olefin sulfonate (10-2S) in which the sulfonic acid group is present at positions 5 to 24 and has a carbon number of 17 to 24. The maximum number of bonding positions of the sulfonic acid group in the internal olefin sulfonate (10-2S) varies depending on the number of carbon atoms.

The mass ratio (10-1S)/(10-2S) of component (A) is based on the final component (A). For example, even if an internal olefin sulfonate is obtained by mixing an internal olefin sulfonate having a mass ratio (10-1S)/(10-2S) outside the above range, it will still be equivalent to the internal olefin sulfonate of component (A) if the mass ratio (10-1S)/(10-2S) in the composition of the internal olefin sulfonate is within the above range.

From the viewpoint of improving the softness of the fiber, the content of (IO-2S) in the component (A) is preferably 60 mass% or less, more preferably 54 mass% or less, further preferably 52 mass% or less, further more preferably 49 mass% or less, further more preferably 45 mass% or less, further more preferably 42 mass% or less, further more preferably 38 mass% or less, further more preferably 33 mass% or less, further more preferably 30 mass% or less, further more preferably 20 mass% or less, and from the viewpoint of ease of production, it is preferably more than 0 mass%, more preferably 5 mass% or more.

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

The component (A) of the present invention can be obtained using as a raw material an internal olefin having 17 to 24 carbon atoms, wherein the mass ratio (IO-1) of the olefin having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms to the olefin having a double bond at positions 5 to 24 carbon atoms is 0.50 to 6.5 (IO-2).

The internal olefin used to obtain component (A) is composed of an olefin (IO-1) having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms, an olefin having a double bond at position 4 and having 17 to 24 carbon atoms, and an olefin (IO-2) having a double bond at positions 5 to 24 carbon atoms. The maximum number of double bond positions in the olefin (IO-2) varies depending on the number of carbon atoms.

From the viewpoint of maintaining the effect of imparting a feel to textile products even when the liquid detergent composition for textile products of the present invention is used for cleaning at low temperatures, the mass ratio (IO-1)/(IO-2) of the olefin having 17 to 24 carbon atoms (IO-1) and having a double bond at the 1st to 3rd positions to the olefin having 17 to 24 carbon atoms (IO-2) (IO-1) is preferably 6.5 or less, more preferably 6.0 or less, even more preferably 5.5 or less, even more preferably 5.0 or less, even more preferably 4.5 or less, even more preferably 4.0 or less, even more preferably 3.5 or less, even more preferably 3.0 or less, even more preferably 2.5 or less, and is preferably 0.50 or more, more preferably 0.60 or more, and even more preferably 0.65 or more.

From the viewpoint of improving the cleanability of stains attached to fiber products, the mass ratio (IO-1)/(IO-2) of the olefin with a double bond present at the 1st position or higher and at the 3rd position or lower among the internal olefins with a carbon number of 17 or higher and 24 or lower (IO-1) to the olefin with a double bond present at the 5th position or higher and at the 24 or lower carbon number (IO-2) is preferably 0.50 or higher, more preferably 0.65 or higher, further preferably 0.70 or higher, further more preferably 0.80 or higher, further more preferably 0.85 or higher, and preferably 6.5 or lower, more preferably 6.0 or lower, and more preferably 5.5 or lower.

In addition, from the viewpoint that the liquid detergent composition for fiber products of the present invention can further clean stains attached to fiber products, (IO-1)/(IO-2) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.65 or more, further more preferably 0.70 or more, further more preferably 0.80 or more, further more preferably 0.85 or more, and preferably 6.5 or less.

Furthermore, the mass ratio (10-1)/(10-2) of the internal olefin used to obtain the component (A) may be based on the final component (A). For example, even an internal olefin sulfonate obtained by mixing an internal olefin sulfonate obtained using as a raw material an olefin having a mass ratio (10-1)/(10-2) outside the above-mentioned range can be equivalent to the internal olefin sulfonate of the component (A) obtained using the specified olefin as a raw material, provided that the mass ratio (10-1)/(10-2) of the olefin equivalent to the raw material olefin is within the above-mentioned range.

From the viewpoint of improving the effect of imparting a feel to fiber products, the number of carbon atoms of the olefin serving as the raw material of component (A) is 17 or more, preferably 18 or more, and 24 or less, preferably 22 or less, more preferably 20 or less, and even more preferably 19 or less.

The internal olefins used as the raw material for component (A) include those containing a trace amount of double bonds at position 1 of the carbon chain, so-called α-olefins (hereinafter also referred to as α-olefins). From the perspective of maintaining the effect of imparting a good feel to textile products even when the liquid detergent composition for textile products is used for cleaning at low temperatures, the α-olefin content in the internal olefins is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less. From the perspective of reducing production costs and improving productivity, it is preferably 0.01% by mass or more.

Sulfonation of internal olefins produces β-sultone in a quantitative manner. A portion of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted to hydroxyalkanesulfonates and olefin sulfonates during the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxyl groups of the resulting hydroxyalkanesulfonates are located within the alkane chain, while the double bonds of the olefin sulfonates are located within the olefin chain. The resulting product is primarily a mixture of these, but some may also contain trace amounts of hydroxyalkanesulfonates with hydroxyl groups at the ends of the carbon chains or olefin sulfonates with double bonds at the ends of the carbon chains.

In this specification, these products and their mixtures are collectively referred to as internal olefin sulfonates (component (A)). Hydroxyalkane sulfonates are referred to as hydroxyl internal olefin sulfonates (HAS), and olefin sulfonates are referred to as olefinic internal olefin sulfonates (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 based on the HPLC-MS peak area of the component (A).

The distribution of double bonds in the olefins in the raw material can be measured, for example, using a gas chromatograph mass spectrometer (hereinafter referred to as GC-MS). Specifically, the components with different carbon chain lengths and double bond positions can be accurately separated using a gas chromatograph (hereinafter referred to as GC), and each component is passed through a mass spectrometer (hereinafter referred to as MS) to identify its double bond position, and the respective ratios are calculated based on the GC peak area. The content of olefins having double bonds at the above-mentioned specific positions uses the value calculated based on the GC peak area. In addition, the positional distribution of double bonds in the case of mixing olefins with different carbon numbers is expressed as the positional distribution of double bonds in olefins with the same carbon number.

In this specification, when a plurality of internal olefin sulfonates obtained from a plurality of raw material olefins having different double bond positions are mixed and used, the double bond position distribution of the raw material olefins of the internal olefin sulfonate is calculated using olefins having the same carbon number.

＜(B) Ingredient＞

Component (B) is an organic solvent having a hydroxyl group and is generally used as a dissolving agent. However, in the present invention, by using component (B) in combination with component (A), the effect of imparting a texture to the fiber product can be enhanced.

From the perspective of enhancing the effect of imparting a good feel to fibers by using it in combination with component (A) of the liquid detergent composition for fiber products of the present invention, component (B) is preferably an organic solvent having a CLogP of -1.5 to 2. In the present invention, CLogP is calculated using ChemProperty in Chem Bio Draw Ultra ver. 14.0 from Perkin Elmer. A larger ClogP value indicates higher hydrophobicity.

From the viewpoint of improving the effect of imparting a feel to textile products even when the liquid detergent composition for textile products of the present invention is used for cleaning at low temperatures, component (B) is an organic solvent having a hydroxyl group, and its CLogP is preferably -1.4 or greater, more preferably -1.2 or greater, even more preferably -1 or greater, even more preferably -0.8 or greater, even more preferably -0.5 or greater, even more preferably -0.1 or greater, even more preferably 0 or greater, even more preferably 0.2 or greater, even more preferably 0.4 or greater, even more preferably 0.6 or greater, and preferably 2 or less, more preferably 1.8 or less, even more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less.

From the viewpoint of improving the effect of imparting a feel to textile products even when the liquid detergent composition for textile products of the present invention is directly applied to and cleaned with the textile products, the component (B) is an organic solvent having a hydroxyl group, and its CLogP is preferably -1.4 or greater, more preferably -1.2 or greater, even more preferably -1 or greater, even more preferably -0.8 or greater, even more preferably -0.5 or greater, even more preferably -0.1 or greater, even more preferably 0 or greater, even more preferably 0.2 or greater, even more preferably 0.4 or greater, even more preferably 0.6 or greater, and preferably 2 or less, more preferably 1.8 or less, even more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less.

From the viewpoint of further enhancing the effect of the component (A) in imparting a texture to the textile product, the component (B) is preferably one or more organic solvents selected from the following components (B1) to (B4).

Component (B1): Monohydric alcohol having 2 to 6 carbon atoms

Component (B2): Alcohol having 2 to 12 carbon atoms and being divalent to dodecavalent

Component (B3): an organic solvent having a hydrocarbon group, an ether group, and a hydroxyl group having 1 to 8 carbon atoms (the hydrocarbon group does not include an aromatic group)

Component (B4): an organic solvent having an aromatic group, an ether group, and a hydroxyl group that may be partially substituted

Specific examples of components (B1) to (B4) are shown below. The numbers in parentheses are calculated values (CLogP) of each component using ChemProperty of Chem Bio Draw Ultra ver. 14.0 manufactured by PerkinElmer.

Examples of the monohydric alcohol having 2 to 6 carbon atoms as the component (B1) include ethanol (-0.24), 1-propanol (0.29), 2-propanol (0.07), and phenol (1.48).

Examples of the alcohol having a carbon number of 2 to 12 and a valence of 2 to 12 as component (B2) include ethylene glycol (-1.4), propylene glycol (-1.1), butanediol (-0.73), hexanediol (-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).

Examples of the organic solvent having a hydrocarbon group, an ether group, and a hydroxyl group having 1 to 8 carbon atoms as the component (B3) include 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-methyl Oxy-2-propanol (-0.30), 1-ethoxy-2-propanol (0.09), 1-methyl glyceryl ether (-1.43), 2-methyl glyceryl ether (-0.73), 1,3-dimethyl glyceryl ether (-0.67), 1-ethyl glyceryl ether (-1.04), 1,3-diethyl glyceryl ether (0.11), triethyl glyceryl ether (0.83), 1-pentyl glyceryl ether (0.54), 2-pentyl glyceryl ether (1.25), 1-octyl glyceryl ether (2.1), 2-ethylhexyl glyceryl ether (2.0).

Examples of the organic solvent having partially substituted aromatic groups, ether groups, and hydroxyl groups as component (B4) include: 2-phenoxyethanol (1.2), diethylene glycol monophenyl ether (1.25), triethylene glycol monophenyl ether (1.08), polyethylene glycol monophenyl ether having an average molecular weight of about 480 (cannot be calculated), 2-benzyloxyethanol (1.1), and diethylene glycol monobenzyl ether (0.96).

The component (B) is preferably an organic solvent having a hydroxyl group selected from the component (B3) and the component (B4) described above, and has a ClogP of 0.6 to 1.5.

From the viewpoint that the liquid detergent for fiber products of the present invention can improve the softness of fiber products even when it is directly and locally attached to fiber products, the content of the organic solvent selected from the above-mentioned components (B3) and (B4) and having a ClogP of 0.6 to 1.5 is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 100% by mass or less in the total component (B).

Water

The liquid detergent composition for textile products of the present invention contains water. For example, water may be contained to maintain the composition in a liquid state at a temperature of 4°C to 40°C. Deionized water (sometimes also referred to as ion-exchanged water) or water to which sodium hypochlorite has been added at a concentration of 1 mg/kg to 5 mg/kg relative to ion-exchanged water may be used. Tap water may also be used.

Fiber

The fiber constituting the fiber product cleaned by the liquid detergent composition for fiber products of the present invention can be any of hydrophobic fiber and hydrophilic fiber. As hydrophobic fiber, for example, can be exemplified: protein fiber (milk protein casein fiber, Promix etc.), polyamide fiber (nylon etc.), polyester fiber (polyester etc.), polyacrylonitrile fiber (acrylic acid etc.), polyvinyl alcohol fiber (vinylon (vinylon) etc.), polyvinyl chloride fiber (polyvinyl chloride etc.), polyvinylidene chloride fiber (vinylidene etc.), polyolefin fiber (polyethylene, polypropylene etc.), polyurethane fiber (polyurethane etc.), polyvinyl chloride/polyvinyl alcohol copolymer fiber (Polychlal etc.), polyalkylene parahydroxybenzoate fiber (benzoate etc.), polyvinyl fluoride fiber (polytetrafluoroethylene etc.), glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, rock fiber (rock fiber), slag fiber (slag fiber), metal fiber (gold wire, silver wire, steel fiber) etc. Examples of hydrophilic fibers include: hair fibers (cotton, cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), coconut fibers, rush, wheat straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca hair, vicuna, angora rabbit hair, etc.), silk fibers (domestic silk, wild silk), feathers, cellulose fibers (rayon, high wet modulus viscose fiber (polynosic), cupra fiber, acetate fiber, etc.), etc.

The fibers are preferably fibers comprising cotton fibers.

＜Fiber products＞

In the present invention, fiber product refers to the fabric, braid, nonwoven fabric and the like using the above-mentioned hydrophobic fiber or hydrophilic fiber and the products such as singlet, T-shirt, Y-shirt, blouse, casual pants, hat, handkerchief, towel, knitwear, socks, underwear, tights obtained using it. From the viewpoint of the improvement effect of the feel of the fiber after cleaning by the fiber product liquid detergent composition of the present invention more easily and practically feel, fiber product is preferably a fiber product comprising cotton fiber. From the viewpoint that the softness of the fiber is further improved, the content of the cotton fiber in the fiber product is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further more preferably 20% by mass or more, further more preferably 100% by mass or more.

＜Composition, etc.＞

From the viewpoint of further improving the cleaning performance of the liquid detergent composition for fiber products per unit mass when cleaning fibers, the content of component (A) in the liquid detergent composition for fiber products of the present invention is 10% by mass or more, preferably 11% by mass or more, and more preferably 12% by mass or more. From the viewpoint of further imparting a better feel to fiber products even when the liquid detergent composition for fiber products of the present invention is used for cleaning at low temperatures, the content is 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

The content of the component (A) contained in the liquid detergent composition for textile products is a value calculated based on the conversion of counter ions into sodium ions, that is, the content is converted into sodium salt.

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

From the viewpoint of further improving the effect of imparting the feel to textile products, the content of component (B) in the liquid detergent composition for textile products of the present invention is preferably 4% by mass or more, more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less.

From the viewpoint of further improving the effect of imparting the feel to textile products, the mass ratio of the content of component (A) to the content of component (B) in the liquid detergent composition for textile products of the present invention, i.e., the content of component (B) / the content of component (A), is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.25 or more, and is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and even more preferably 0.7 or less.

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

＜Feel＞

The hand feel in the present invention refers to the feeling of softness, fluffiness, smoothness, etc. when the fiber product is touched by the skin of the hand.

＜Optional ingredients＞

The liquid detergent composition for textile products of the present invention may contain a surfactant other than component (A) as component (C) within the range that does not impair the effects of the present invention. Component (C) includes one or more surfactants selected from anionic surfactants other than component (A) and nonionic surfactants.

As the component (C), one or more anionic surfactants selected from the group consisting of the following components (c1), (c2), (c3), and (c4) can be mentioned.

(c1) ingredient: alkyl or alkenyl sulfate

(c2) component: polyoxyalkylene alkyl ether sulfate or polyoxyalkylene alkenyl ether sulfate

Component (c3): Anionic surfactant having a sulfonate group (excluding component (A))

(c4) ingredient: fatty acid or its salt

More specifically, component (c1) includes one or more anionic surfactants selected from alkyl sulfates having an alkyl group with 10 to 18 carbon atoms and alkenyl sulfates having an alkenyl group with 10 to 18 carbon atoms. From the viewpoint of improving cleaning properties, component (c1) is preferably one or more anionic surfactants selected from alkyl sulfates having an alkyl group with 12 to 14 carbon atoms, and more preferably one or more anionic surfactants selected from sodium alkyl sulfates having an alkyl group with 12 to 14 carbon atoms.

More specifically, component (c2) includes one or more anionic surfactants selected from polyoxyalkylene alkyl ether sulfates having an alkyl group with 10 to 18 carbon atoms and an average number of alkylene oxide added moles of 1 to 3, and polyoxyalkylene alkenyl ether sulfates having an alkenyl group with 10 to 18 carbon atoms and an average number of alkylene oxide added moles of 1 to 3. From the viewpoint of improving cleaning properties, component (c2) is preferably a polyoxyethylene alkyl ether sulfate having an average number of ethylene oxide added moles of 1 to 2.2, more preferably a polyoxyethylene alkyl ether sulfate having an alkyl group with 12 to 14 carbon atoms and an average number of ethylene oxide added moles of 1 to 2.2, and further preferably a sodium salt of these.

The anionic surfactant having a sulfonate group as the component (c3) refers to an anionic surfactant having a sulfonate group as a hydrophilic group (but excluding the component (A)).

More specifically, component (c3) includes one or more anionic surfactants selected from the group consisting of alkylbenzenesulfonates having an alkyl group of 10 to 18 carbon atoms, alkenylbenzenesulfonates having an alkenyl group of 10 to 18 carbon atoms, alkanesulfonates having an alkyl group of 10 to 18 carbon atoms, α-olefinsulfonates having an α-olefin moiety of 10 to 18 carbon atoms, α-sulfofatty acid salts having a fatty acid moiety of 10 to 18 carbon atoms, α-sulfofatty acid lower alkyl ester salts having a fatty acid moiety of 10 to 18 carbon atoms and an ester moiety of 1 to 5 carbon atoms, and internal olefinsulfonates having a carbon number of 12 to 16 carbon atoms. From the viewpoint of improving cleaning properties, component (c3) is preferably an alkylbenzenesulfonate having an alkyl group of 11 to 14 carbon atoms, and more preferably sodium alkylbenzenesulfonate having an alkyl group of 11 to 14 carbon atoms.

Examples of the fatty acid or salt thereof of the component (c4) include fatty acids or salts thereof having a carbon number of 10 or more and 20 or less. From the viewpoint of further enhancing the fiber softening effect of the component (A), the component (c4) has a carbon number of 10 or more, preferably 12 or more, more preferably 14 or more, and a carbon number of 20 or less, preferably 18 or less.

The salt of the anionic surfactant as the component (c1) to the component (c4) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and even more preferably a sodium salt.

Moreover, as another (C)component, the nonionic surfactant which has a hydroxyl group or a polyoxyalkylene group is mentioned as a (c5)component.

In addition, the liquid detergent composition for textile products of the present invention may further 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 dispersant such as polyacrylic acid, polymaleic acid, and carboxymethyl cellulose

(d2) 0.01% by mass or more and 10% by mass or less of a bleaching agent such as hydrogen peroxide, sodium percarbonate, or sodium perborate

(d3) 0.01% by mass to 10% by mass of tetraacetylethylenediamine, bleach activators represented by general formulas (I-2) to (I-7) of Japanese Patent Application Laid-Open No. 6-316700, and the like

(d4) 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more, and 2% by mass or less, preferably 1% by mass or less of one or more enzymes selected from cellulase, amylase, pectinase, protease, and lipase, preferably one or more enzymes selected from amylase and protease

(d5) 0.001% by mass or more and 1% by mass or less of a fluorescent dye, for example, a fluorescent dye commercially available as Tinopal CBS (trade name, manufactured by Ciba Speciality Chemicals Inc.) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.)

(d6) 0.01% by mass or more and 2% by mass or less of an antioxidant such as butylated hydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite

(d7) Appropriate amounts of pigments, fragrances, antimicrobial preservatives, silicones and other defoaming agents.

The pH value of the liquid detergent composition for textile products 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, and even more preferably 8 or lower. The pH value is measured according to the pH measurement method described below.

<pH Measurement Method>

Connect the combined electrode for pH measurement (glass slip-on type manufactured by HORIBA) to a pH meter (pH/ion meter F-23 manufactured by HORIBA) and turn on the power. Use a saturated potassium chloride aqueous solution (3.33 mol/L) as the internal liquid of the pH electrode. Next, fill a 100 mL beaker with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) and immerse them in a thermostatic bath at 25°C for 30 minutes. Immerse the pH electrode in the standard solution adjusted to a constant temperature for 3 minutes, and perform calibration operations in the order of pH 6.86 → pH 9.18 → pH 4.01. Adjust the sample to be measured to 25°C, immerse the electrode of the above-mentioned pH meter in the sample, and measure the pH value after 1 minute.

The present invention provides a method for cleaning a fiber product using a cleaning solution containing a liquid detergent composition for fiber products of the present invention and water to clean the fiber product. The cleaning method can appropriately apply the matters described in the liquid detergent composition for fiber products of the present invention. The content of the (A) component in the above-mentioned cleaning solution is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1% by mass or less, more preferably 0.8% by mass or less. In addition, the content of the (B) component in the above-mentioned cleaning solution 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 0.5% by mass or less.

The water used in the cleaning method of the fiber products of the present invention is preferably water with hardness. From the viewpoint of further improving the effect of imparting the feel of the fiber products, the hardness of the water is preferably 1°dH or more, more preferably 2°dH or more, further preferably 3.5°dH or more, further more preferably 5°dH or more, further more preferably 7°dH or more, and preferably 20°dH or less, more preferably 18°dH or less, further preferably 15°dH or less. Here, the German hardness (°dH) in this specification refers to the hardness expressed as 1 mg/L (ppm) = about 0.056°dH (1°dH = 17.8ppm) when the concentration of calcium and magnesium in water is converted to CaCO ₃ .

The concentrations of calcium and magnesium for obtaining the German hardness can be determined by a chelate titration method using disodium ethylenediaminetetraacetic acid.

The specific method for measuring the German hardness of water in this specification is shown below.

<German Method for Measuring Water Hardness>

[Reagents]

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 Dojin Chemical Laboratories Co., Ltd.)

Ammonia buffer solution for hardness measurement (a solution prepared by dissolving 67.5 g of ammonium chloride in 570 ml of 28 w/v% ammonia water and adjusting the total volume to 1000 ml with ion-exchanged water)

[Determination of hardness]

(1) Use a full-volume pipette to collect 20 ml of water, which will serve as a sample, into a conical beaker.

(2) Add 2 ml of ammonia buffer for hardness measurement.

(3) Add 0.5 ml of Universal BT indicator. Verify that the solution is purple-red.

(4) While thoroughly shaking the conical beaker to mix, add 0.01 mol/l EDTA·2Na solution dropwise from the burette. The point when the sample water changes color to blue is regarded as the endpoint of the titration.

(5) The total hardness is calculated according to the following calculation formula.

Hardness (°dH) = T × 0.01 × F × 56.0774 × 100/A

T: titration of 0.01 mol/l EDTA·2Na solution (mL)

A: Sample volume (20 mL, the volume of water used as the sample)

F: coefficient 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 higher and 20° dH or lower.

In the fiber product cleaning method of the present invention, the bath ratio value represented by the ratio of the mass (kg) of the fiber product to the amount (liter) of the cleaning liquid, that is, the amount (liter) of the cleaning liquid/the mass (kg) of the fiber product (this ratio will sometimes be referred to as the bath ratio hereinafter) is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, further more preferably 5 or more, and preferably 100 or less.

In the cleaning method of the fiber products of the present invention, from the viewpoint of further improving the effect of imparting the feel of the fiber products, the time for cleaning the fiber products is preferably more than 1 minute, more preferably more than 2 minutes, further preferably more than 3 minutes, and preferably less than 12 hours, more preferably less than 8 hours, further preferably less than 6 hours, further more preferably less than 3 hours, further more preferably less than 1 hour.

The fiber product cleaning method of the present invention is also suitable for a rotary cleaning method. A rotary cleaning method refers to a cleaning method in which a fiber product that is not fixed to a rotating machine is rotated around a rotating axis together with a cleaning liquid. The rotary cleaning method can be implemented using a rotary washing machine. Specific examples of rotary washing machines include drum-type washing machines, pulsator-type washing machines, and agitator-type washing machines. These rotary washing machines can each use a commercially available washing machine for household use. Drum-type washing machines have rapidly become popular in recent years because they can further reduce the amount of water used for a single wash. Drum-type washing machines can particularly reduce the amount of water used during cleaning.

<Method for producing liquid detergent composition for textile products>

The present invention provides a method for producing a liquid detergent composition for textile products, wherein the method comprises mixing the following component (A), the following component (B), and water, wherein the proportion of component (A) in the total mixed components is 10% by mass or more and 60% by mass or less.

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th position and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th position and having 17 to 24 carbon atoms is 0.75 to 5.5 (10-1S)/(10-2S).

Component (B): Organic solvent having a hydroxyl group

Preferred embodiments of components (A) and (B) in this production method are the same as those of the liquid detergent composition for textile products of the present invention. Furthermore, the matters described in the liquid detergent composition for textile products of the present invention can be appropriately applied to this production method. The contents in the above composition can be replaced by the ratio of all the mixed components.

The present invention also provides a method for producing a liquid detergent composition for textile products, comprising mixing the following component (A1), the following component (B), and water, wherein the proportion of component (A1) in all the mixed components is 10% by mass or more and 60% by mass or less.

Component (A1): an internal olefin sulfonate obtained from an internal olefin having 17 to 24 carbon atoms, wherein the internal olefin is obtained from an olefin having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms (IO-1) and an olefin having a double bond at positions 5 to 17 to 24 carbon atoms (IO-2) in which the mass ratio (IO-1)/(IO-2) is 0.50 to 6.5.

Component (B): Organic solvent having a hydroxyl group

Component (A1) in this production method may also be equivalent to component (A). In this case, preferred embodiments of components (A) and (B) are the same as those of the liquid detergent composition for fiber products of the present invention. In addition, the matters described in the liquid detergent composition for fiber products of the present invention may be appropriately applied to this production method. The content in the above composition may be replaced by the ratio of all the mixed components.

<Embodiments of the present invention>

Hereinafter, embodiments of the present invention will be described. To these embodiments, the matters described in the liquid detergent composition for textile products and the method for producing the liquid detergent composition for textile products of the present invention can be appropriately applied.

<1> A liquid detergent composition for textile products, comprising 10% by mass or more and 60% by mass or less of the following component (A), the following component (B), and water.

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th position and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th position and having 17 to 24 carbon atoms is 0.75 to 5.5 (10-1S/10-2S).

Component (B): an organic solvent having a hydroxyl group.

<2> The liquid detergent composition for textile products according to <1>, wherein (IO-2S) is an internal olefin sulfonate having a sulfonic acid group at positions 5 to 9 and having 17 to 24 carbon atoms.

<3> The liquid detergent composition for fiber products according to <1> or <2>, wherein the mass ratio of the content of (IO-1S) to the content of (IO-2S) in component (A), i.e., (IO-1S)/(IO-2S), is 0.75 or more, preferably 0.9 or more, more preferably 1.0 or more, further preferably 1.2 or more, further more preferably 1.4 or more, further more preferably 1.6 or more, further more preferably 2.0 or more, further more preferably 2.4 or more, further more preferably 4.5 or more, and is 5.5 or less.

<4> The liquid detergent composition for fiber products according to any one of <1> to <3>, wherein the content of (IO-2S) in component (A) is preferably 60% by mass or less, more preferably 54% by mass or less, further preferably 52% by mass or less, further more preferably 49% by mass or less, further more preferably 45% by mass or less, further more preferably 42% by mass or less, further more preferably 38% by mass or less, further more preferably 33% by mass or less, further more preferably 30% by mass or less, further more preferably 20% by mass or less, and preferably exceeds 0% by mass, more preferably 5% by mass or more.

<5> The liquid detergent composition for textile products according to any one of <1> to <4>, wherein the ratio of the component (A) in the total anionic surfactants contained in the liquid detergent composition for textile products is 60% by mass or more and 100% by mass or less.

<6> The liquid detergent composition for textile products according to any one of <1> to <5>, wherein the proportion of component (A) in all anionic surfactants contained in the liquid detergent composition for textile products is 70% by mass or more, further 80% by mass or more, further 90% by mass or more, and is 100% by mass or less.

<7> The liquid detergent composition for fiber products according to any one of <1> to <6>, wherein the content of component (B) is preferably 4% by mass or more, more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, and even more preferably 25% by mass or less.

<8> The liquid detergent composition for fiber products according to any one of <1> to <7>, wherein the mass ratio of the content of component (A) to the content of component (B), i.e., the content of component (B)/the content of component (A), is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.25 or more, and is preferably 1 or less, more preferably 0.9 or less, further preferably 0.8 or less, and further more preferably 0.7 or less.

<9> The liquid detergent composition for textile products according to any one of <1> to <8>, wherein the component (B) is one or more selected from the following components (B1) to (B4),

Component (B1): a monohydric alcohol having 2 to 6 carbon atoms;

Component (B2): an alcohol having 2 to 12 carbon atoms and being divalent to dodecavalent;

Component (B3): an organic solvent having a hydrocarbon group, an ether group, and a hydroxyl group having 1 to 8 carbon atoms (the hydrocarbon group does not include an aromatic group);

Component (B4): an organic solvent having an aromatic group which may be partially substituted, an ether group, and a hydroxyl group.

<10> The liquid detergent composition for textile products according to any one of <1> to <9>, wherein the ClogP of the component (B) is -1.5 or more and 2 or less.

<11> The liquid detergent composition for fiber products according to any one of <1> to <10>, wherein component (B) is an organic solvent having a hydroxyl group, wherein CLogP is preferably -1.4 or greater, more preferably -1.2 or greater, further preferably -1 or greater, further more preferably -0.8 or greater, further more preferably -0.5 or greater, further more preferably -0.1 or greater, further more preferably 0 or greater, further more preferably 0.2 or greater, further more preferably 0.4 or greater, further more preferably 0.6 or greater, and preferably 2 or less, more preferably 1.8 or less, further preferably 1.7 or less, further more preferably 1.6 or less, further more preferably 1.5 or less.

<12> The liquid detergent composition for fiber products according to any one of <9> to <11>, wherein the content of the organic solvent selected from the above-mentioned component (B3) and component (B4) and having the above-mentioned ClogP of 0.6 to 1.5 is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 100% by mass or less in the total component (B).

<13> The liquid detergent composition for fiber products according to any one of <1> to <12>, wherein the water content 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.

<14> A method for producing a liquid detergent composition for textile products, comprising mixing the following component (A), the following component (B), and water, wherein the proportion of component (A) in the total mixed components is 10% by mass or more and 60% by mass or less,

Component (A): an internal olefin sulfonate having 17 to 24 carbon atoms, wherein the mass ratio of the internal olefin sulfonate (10-1S) having a sulfonic acid group at the 2nd to 4th position and having 17 to 24 carbon atoms to the internal olefin sulfonate (10-2S) having a sulfonic acid group at the 5th to 5th position and having 17 to 24 carbon atoms is 0.75 to 5.5 (10-1S/10-2S).

Component (B): an organic solvent having a hydroxyl group.

<15> A method for producing a liquid detergent composition for textile products, comprising mixing the following component (A1), the following component (B), and water, wherein the proportion of component (A1) in the total mixed components is 10% by mass or more and 60% by mass or less,

Component (A1): an internal olefin sulfonate obtained from an internal olefin having 17 to 24 carbon atoms, wherein the internal olefin is obtained from an olefin having a double bond at positions 1 to 3 and having 17 to 24 carbon atoms (IO-1) and an olefin having a double bond at positions 5 to 17 and having 24 carbon atoms (IO-2) at a mass ratio (IO-1)/(IO-2) of 0.50 to 6.5 as a raw material;

Component (B): an organic solvent having a hydroxyl group.

<16> The method for producing a liquid detergent composition for fiber products according to <15>, wherein the mass ratio (IO-1)/(IO-2) of the olefin having a double bond at the 1st position or higher and at the 3rd position or lower among the internal olefins having a carbon number of 17 to 24 (IO-1) to the olefin having a double bond at the 5th position or higher and at the 17th to 24th carbon number (IO-2) is preferably 6.5 or lower, more preferably 6.0 or lower, further preferably 5.5 or lower, further more preferably 5.0 or lower, further more preferably 4.5 or lower, further more preferably 4.0 or lower, further more preferably 3.5 or lower, further more preferably 3.0 or lower, further more preferably 2.5 or lower, and preferably 0.50 or higher, more preferably 0.60 or higher, further preferably 0.65 or higher.

<17> A method for cleaning a fiber product, comprising cleaning the fiber product with a cleaning liquid containing the liquid cleaning composition for fiber products according to any one of <1> to <13> and water.

<18> The method for cleaning a fiber product according to <17>, wherein the content of component (A) in the cleaning liquid is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less.

<19> The method for cleaning fiber products as described in <17> or <18>, wherein the content of component (B) in the above-mentioned cleaning liquid is preferably 0.001 mass% or more, more preferably 0.002 mass% or more, and preferably 0.8 mass% or less, more preferably 0.5 mass% or less.

Example

[Preparation of component (A)]

(1) Synthesis of Internal Olefins A to C (Production Examples A to C)

Internal olefins A to C serving as raw materials for the component (A) and the component (A') (comparative component for the component A) were synthesized as follows.

In a flask equipped with a stirrer, 7000 g (25.9 mol) of 1-octadecanol (product name: Kalcol 8098, manufactured by Kao Corporation) and 700 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst (10% by mass relative to the starting alcohol) were added. The mixture was stirred at 280°C while nitrogen was passed through the system (7000 mL/min) for varying reaction times according to Preparation Examples A to C. The resulting crude internal olefin was transferred to a distillation flask and distilled at 148-158°C/0.5 mmHg to obtain internal olefins A to C having 18 carbon atoms and an olefin purity of 100%. The double bond distribution of the resulting internal olefins is shown in Table 1.

(2) Internal olefin D with 16 carbon atoms

As the internal olefin D having 16 carbon atoms, an internal olefin obtained by the method described in Production Example C of JP-A-2014-76988 was used. The double bond distribution of the internal olefin D is shown in Table 1.

[Table 1]

The double bond distribution of internal olefins is measured by gas chromatography (GC). Specifically, dimethyl disulfide is reacted with an internal olefin to form a disulfide derivative, and the components are then separated by GC. The double bond distribution of the internal olefin is determined based on the peak areas of each component. Furthermore, for olefins with 18 carbon atoms, it is structurally indistinguishable between internal olefins with a double bond at the 8th position and those with a double bond at the 9th position. In the case of sulfonation, for convenience, the amount of internal olefins with a double bond at the 8th position is divided by 2 and shown in the columns for the 8th and 9th positions. Similarly, for olefins with 16 carbon atoms, the amount of internal olefins with a double bond at the 7th position is divided by 2 and shown in the columns for the 7th and 8th positions for convenience.

The apparatus and analytical conditions used for the measurement are as follows: GC apparatus "HP6890" (manufactured by HEWLETTPACKARD), column "Ultra-Alloy-1HT capillary column" (30 m × 250 μm × 0.15 μm, manufactured by Frontier Laboratories Ltd.), detector (hydrogen flame ionization detector (FID)), injection temperature 300°C, detector temperature 350°C, He flow rate 4.6 mL/min

(3) Synthesis of (a-1), (a-4), (a'-1) and (a'-2)

A thin-film sulfonation reactor with an external jacket was used, and cooling water at 20°C was passed through the external jacket of the reactor to cause the internal olefins A to D to react with sulfur trioxide gas for sulfonation. The molar ratio of SO ₃ / internal olefin during the sulfonation reaction was set to 1.09. The obtained sulfonated product was added to an alkaline aqueous solution prepared with sodium hydroxide in an amount 1.5 times the theoretical acid value, and neutralized at 30°C for 1 hour while stirring. The neutralized product was hydrolyzed by heating it at 160°C in an autoclave for 1 hour to obtain the crude product of each sodium internal olefin sulfonate. 300 g of the crude product was transferred to a separatory funnel, and after adding 300 mL of ethanol, 300 mL of petroleum ether was added each time to extract and remove oil-soluble impurities. At this time, the inorganic compound (main component was Glauber's salt) precipitated to the oil-water interface due to the addition of ethanol was also separated and removed from the aqueous phase by the oil-water separation operation. This extraction and removal operation was performed three times. The aqueous phase was evaporated to dryness to obtain the following sodium internal olefin sulfonates. Here, the internal olefin sulfonate obtained using internal olefin A as a raw material is designated as (a-1), the internal olefin sulfonate obtained using internal olefin B as a raw material is designated as (a-4), the internal olefin sulfonate obtained using internal olefin C as a raw material is designated as (a'-1), and the internal olefin sulfonate obtained using internal olefin D as a raw material is designated as (a'-2).

The content ratio of the internal olefin sulfonate salts with sulfonic acid groups bonded thereto is measured using high-performance liquid chromatography/mass spectrometry (HPLC-MS). Specifically, the hydroxyl groups with sulfonic acid groups bonded thereto are separated by high-performance liquid chromatography (HPLC) and then passed through a mass spectrometer (MS) for identification. The resulting peak areas are used to determine the respective ratios. In this specification, the respective ratios determined based on the peak areas are calculated as mass ratios.

The apparatus and conditions used for the measurement are as follows: HPLC apparatus "LC-20ASXR" (manufactured by Shimadzu Corporation), column "ODS Hypersil (registered trademark)" (4.6×250 mm, particle size: 3 μm, Thermo Fisher Scientific Corporation), sample preparation (1000-fold dilution with methanol), eluent A (water supplemented with 10 mM ammonium acetate), eluent B (methacrylonitrile/water = 95/5 (v/v) solution supplemented with 10 mM ammonium acetate), gradient (0 minute (A/B = 60/40) → 15.1 to 20 minutes (30/70) → 20.1 to 30 minutes (60/40), MS apparatus "LCMS-2020" (manufactured by Shimadzu Corporation), ESI detection (negative ion detection m/z: 349.15 ((A) component or (A') component with 18 carbon atoms), 321.10 ((A') component with 16 carbon atoms)), column temperature (40°C), flow rate (0.5 mL/min), injection volume (5 μL)

Table 2 shows the positional distribution of carbon atoms to which the sulfonic acid groups of (a-1), (a-4), (a′-1), and (a′-2) were bonded.

[Table 2]

(4) Preparation of other (A) components

(a-1) and (a-4) were mixed to prepare (a-2) and (a-3). Separately, (a-4) and (a'-1) were mixed to prepare (a-5) to (a-9).

Table 3 shows the double bond distribution of the internal olefins used as the raw materials for the obtained (a-1) to (a-9), (a′-1), and (a′-2).

Table 4 shows the positional distribution of carbon atoms to which the sulfonic acid groups of (a-1) to (a-9), (a′-1), and (a′-2) were bonded.

A portion of the internal olefin sulfonic acid sodium salt is shown below.

(a-1): Internal olefin sulfonic acid sodium salt obtained from internal olefin A

The mass ratio of the hydroxyl form (sodium hydroxyalkane sulfonate) to the olefin form (sodium olefin sulfonate) in the sodium internal olefin sulfonate was 82/18.

(a-4): Internal olefin sulfonic acid sodium salt obtained from internal olefin B

The mass ratio of the hydroxyl form (sodium hydroxyalkane sulfonate) to the olefin form (sodium olefin sulfonate) in the sodium internal olefin sulfonate was 83/17.

(a'-1): internal olefin sulfonic acid sodium salt obtained from internal olefin C

The mass ratio of the hydroxyl form (sodium hydroxyalkane sulfonate) to the olefin form (sodium olefin sulfonate) in the sodium internal olefin sulfonate was 83/17.

(a'-2): internal olefin sulfonic acid sodium salt obtained from internal olefin D

The mass ratio of the hydroxyl form (sodium hydroxyalkane sulfonate) to the olefin form (sodium olefin sulfonate) in the sodium internal olefin sulfonate was 84/16.

[Table 3]

[Table 4]

＜Ingredients＞

[(A)Component]

Select from Table 4 to use.

[(A') component] (comparative component of component A)

(a'-1) and (a'-2) in Table 4 were used.

[(B) ingredient]

Component (b-1): phenoxyethanol (ClogP = 1.2) [the organic solvent of the above-mentioned component (B4)]

Component (b-2): diethylene glycol monobutyl ether (ClogP = 0.67) [the organic solvent of the above-mentioned component (B3)]

Component (b-3): ethanol (ClogP = -0.24) [the organic solvent of the above-mentioned component (B1)]

Component (b-4): Propylene glycol (ClogP = -1.1) [the organic solvent for the above-mentioned component (B2)]

Component (b-5): Glycerin (ClogP = -1.5) [the organic solvent for the above-mentioned component (B2)]

Component (b-6): dipropylene glycol monoethyl ether (ClogP = 0.23) [the organic solvent of the above-mentioned component (B3)]

[water]

Ion exchange water

<Preparation of Liquid Detergent Composition for Textile Products>

The liquid detergent compositions for textile products shown in Tables 5 to 7 were prepared using the above-mentioned ingredients, and the following items were evaluated. The results are shown in Tables 5 to 7.

Specifically, the liquid detergent compositions for fiber products shown in Tables 5 to 7 were prepared as follows. A 5 cm long Teflon (registered trademark) stirrer piece was placed in a 200 mL glass beaker and the weight was measured. Next, 80 g of 20°C ion-exchanged water, component (A) or component (A'), and component (B) were added, and the top surface of the beaker was sealed with Saran Wrap (registered trademark).

The beaker containing the contents was placed in a 60°C water bath placed on a magnetic stirrer and stirred at 100 r/min for 30 minutes while the water temperature in the water bath was within the temperature range of 60±2°C. The water in the water bath was then replaced with 5°C tap water, and the mixture was cooled until the temperature of the composition in the beaker reached 20°C. The Saran Wrap (registered trademark) was then removed, and ion-exchanged water was added to bring the mass of the contents to 100 g. The mixture was stirred again at 100 r/min for 30 seconds to obtain the liquid detergent compositions for textile products described in Tables 5 to 7.

<Evaluation method for flexibility>

(1) Evaluation of pretreatment of fiber products

1.7 kg of cotton knitwear (manufactured by Seisen Co., Ltd., pure cotton knitwear, unmercerized (unmercerized), 100% cotton) was washed a total of two times in advance using a standard process in a fully automatic washing machine (NA-F702P manufactured by National) (when cleaning, 4.7 g of Emulgen 108 (manufactured by Kao Corporation), 47 L of water, washing for 9 minutes, rinsing twice, and dehydrating for 3 minutes), and then washed a total of three times with water alone (47 L of water, washing for 9 minutes, rinsing twice, and dehydrating for 3 minutes), and dried for 24 hours in an environment of 23°C and 45% RH.

(2) Evaluation of cleaning of fiber products

(2-1) Method (1)

A National electric drum washing machine (model "N-BK2") was filled with 6.0 L of tap water (3.5° dH) adjusted to 5°C. Four cotton knitwear pieces (approximately 140 g) pretreated by the above method were then added. The liquid detergent composition for textile products listed in Tables 5 and 6 was then added to a bath concentration of 200 mg/kg of component (A) and the fabrics were cleaned for 10 minutes. After cleaning, the fabrics were dehydrated for 1 minute using a Hitachi double-deck washing machine (model "PS-H35L"). Next, 6.0 L of the aforementioned 5°C tap water was added to the drum washing machine. A cotton towel, dehydrated in the Hitachi double-deck washing machine, was further added and rinsed for 3 minutes. The fabrics were then dehydrated for 1 minute using the same double-deck washing machine and then dried for 12 hours under conditions of 20°C and 43% RH.

(2-2) Method (2)

6.0 L of tap water (3.5° dH) adjusted to 5°C was poured into a National electric drum washing machine (model "N-BK2"). Separately, the liquid detergent composition for fiber products described in Table 7 was sprinkled onto four pieces of cotton knitwear (approximately 140 g) pretreated by the above method so that the bath concentration of component (A) was 200 mg/kg. The cotton knitwear to which the liquid detergent composition for fiber products described in Table 7 had adhered was placed in the above washing machine and cleaned for 10 minutes. After cleaning, the cotton knitwear was dehydrated for 1 minute using a Hitachi double-layer washing machine (model "PS-H35L"). Next, 6.0 L of the above-mentioned 5°C tap water was poured into the drum washing machine, and a cotton towel dehydrated in the Hitachi double-layer washing machine was further placed and rinsed for 3 minutes. The cotton knitwear was then dehydrated for 1 minute using the same double-layer washing machine, and then dried for 12 hours under conditions of 20°C and 43% RH.

(3) Evaluation of softness

Six panelists, evaluating the softness of the dried cotton knitted fabric based on the feel of the fiber, rated the softness according to the following criteria. The average score was calculated by rounding to three significant figures. For example, if the rating was between 2 and 3, a score of 2.5 was assigned.

-1 ... not softer than the cotton knitted fabric treated with the composition of Comparative Example 1.

0 ... As soft as cotton knitwear treated with the composition of Reference 1.

1 ... slightly softer than the cotton knitted fabric treated with the composition of Reference 1.

2 ... Softer than cotton knitwear treated with the composition of Reference 1.

3 ... Equally soft as the cotton knitted fabric treated with the composition of Reference 2.

Furthermore, with respect to Table 5, the composition of Comparative Example 3 was used as benchmark 1, and the composition of Example 1 was used as benchmark 2 for evaluation. With respect to Table 6, the composition of Comparative Example 3 was used as benchmark 1, and the composition of Example 8 was used as benchmark 2 for evaluation. With respect to Table 7, the composition of Comparative Example 3 was used as benchmark 1, and the composition of Example 15 was used as benchmark 2 for evaluation. Furthermore, the average score obtained was standardized by taking 3 points (the score of benchmark 2) under the above-mentioned judgment criteria as a relative value of 10 points. When the standardized value is less than 0 points (benchmark 1), it is set to "-1". The results are shown in Tables 5, 6, and 7.

＜Evaluation method of cleanliness＞

(1) Preparation of model sebum-artificially contaminated cloth

A model sebum artificially soiled cloth was prepared by applying a model sebum artificially soiled liquid of the following composition to the cloth. The model sebum artificially soiled cloth was applied by printing the artificially soiled liquid onto the cloth using a gravure roll coater. The process of applying the model sebum artificially soiled liquid to the cloth to produce the model sebum artificially soiled cloth was performed at a gravure roll unit capacity of 58 ^cm³ / ^m² , a coating speed of 1.0 m/min, a drying temperature of 100°C, and a drying time of 1 minute. Cotton 2003 (manufactured by Gutou Shoten) was used as the cloth.

*Composition of the model sebum artificial contamination solution: 0.4% by mass of lauric acid, 3.1% by mass of myristic acid, 2.3% by mass of pentadecanoic acid, 6.2% by mass of palmitic acid, 0.4% by mass of heptadecanoic acid, 1.6% by mass of stearic acid, 7.8% by mass of oleic acid, 13.0% by mass of triolein, 2.2% by mass of n-hexadecyl palmitate, 6.5% by mass of squalene, 1.9% by mass of protein lecithin liquid crystal, 8.1% by mass of Kanuma red clay, 0.01% by mass of carbon black, the remainder being water (total 100% by mass)

(2) Evaluation of cleaning power

Five pieces of the model sebum artificially contaminated cloth (6 cm × 6 cm) prepared above were cleaned at 85 rpm for 10 minutes using a Terg-O-Tometer (Ueshima, MS-8212). The cleaning conditions were that tap water (3.5° dH, 20°C) was injected in such a way that the concentration of the liquid detergent composition for fiber products described in Table 5 became 0.033% by mass, and the cleaning was performed at a water temperature of 20°C. After cleaning, rinse with tap water (20°C) for 3 minutes. The cleaning rate (%) was determined by the following method, and the average value of the five pieces was obtained. The results are shown in Table 5. The reflectance at 550 nm of the original cloth before contamination and before and after cleaning was measured using a colorimeter (manufactured by Nippon Denshoku Co., Ltd., Z-300A).

Cleaning rate (%) = 100 × [(reflectivity after cleaning - reflectivity before cleaning) / (reflectivity of original cloth - reflectivity before cleaning)]

[Table 5]

(1) Mass ratio of (IO-1)/(IO-2) in raw olefins

(2) Mass ratio of (10-1S)/(10-2S) in internal olefin sulfonate

[Table 6]

[Table 7]

Claims (30)

1. A liquid cleaning agent composition for fiber products, wherein, Contains 10% to 60% by mass of the following ingredient (A), the following ingredient (B), and water. (A) Composition: Inner olefin sulfonate, which is an inner olefin sulfonate with 18 carbon atoms, and the mass ratio of an inner olefin sulfonate with 18 carbon atoms in which the sulfonic acid group exists at the 2nd position and the 4th position to an inner olefin sulfonate with 18 carbon atoms in which the sulfonic acid group exists at the 5th position and the sulfonic acid group exists at the 5th position to the 18 ... (B) Component: Organic solvent with hydroxyl groups. 2. The liquid cleaning agent composition for fiber products as described in claim 1, wherein, (IO-2S) is an 18-carbon sulfonate of an inner olefin with a sulfonic acid group located at positions 5 and 9. 3. The liquid cleaning agent composition for fiber products as described in claim 1, wherein, (A) In the component, the mass ratio of the content of (IO-1S) to the content of (IO-2S) is 0.9 or more and 4.8 or less. 4. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, (A) The content of (IO-2S) in the component is less than 60% by mass and more than 0% by mass. 5. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, (A) The content of (IO-2S) in the component is less than 54% by mass and more than 5% by mass. 6. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, The proportion of component (A) in all anionic surfactants contained in the liquid cleaning agent composition for fiber products is 60% by mass or more and 100% by mass or less. 7. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, The proportion of component (A) in all anionic surfactants contained in the liquid cleaning agent composition for fiber products is more than 90% by mass and less than 100% by mass. 8. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, The content of component (A) in the liquid cleaning agent composition for fiber products is 11% by mass or more and 50% by mass or less. 9. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, The content of component (A) in the liquid cleaning agent composition for fiber products is 12% by mass or more and 40% by mass or less. 10. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, (B) The content of component is 4% by mass or more and 35% by mass or less. 11. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, (B) The content of component (B) is more than 5% by mass and less than 30% by mass. 12. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, As the mass ratio of the content of component (A) to the content of component (B), the content of component (B) / the content of component (A) is 0.1 or more and 1 or less. 13. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, As the mass ratio of the content of component (A) to the content of component (B), the content of component (B) / the content of component (A) is 0.1 or more and 0.8 or less. 14. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, As the mass ratio of the content of component (A) to the content of component (B), the content of component (B) / the content of component (A) is 0.2 or more and 0.7 or less. 15. The liquid cleaning agent composition for fiber products according to any one of claims 1 to 3, wherein, (B) Component is selected from one or more of the following components (B1) to (B4). (B1) Composition: Monohydric alcohols with 2 or more but less than 6 carbon atoms; (B2) Composition: Alcohols with 2 or more but less than 12 carbon atoms and with more than two but less than twelve carbon atoms; (B3) Components: Organic solvents having hydrocarbon groups, ether groups and hydroxyl groups with 1 or more and 8 or fewer carbon atoms, wherein the hydrocarbon groups do not include aromatic groups; (B4) Ingredients: Organic solvents having partially substituted or unsubstituted aromatic groups, ether groups and hydroxyl groups. 16. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, (B) The ClogP of component is greater than -1.5 and less than 2. 17. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, (B) is an organic solvent with hydroxyl groups and a ClogP of -1.2 or higher and less than 1.6. 18. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, (B) The component is an organic solvent with hydroxyl groups and a ClogP of 0 or more and 1.5 or less. 19. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, In all components (B), the proportion of an organic solvent selected from components (B3) and (B4) with a ClogP of 0.6 or more and 1.5 or less is 40% by mass or more and 100% by mass or less. 20. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, In all components (B), the proportion of an organic solvent selected from components (B3) and (B4) with a ClogP of 0.6 or more and 1.5 or less is 60% by mass or more and 100% by mass or less. 21. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, The monohydric alcohols with 2 or more but less than 6 carbon atoms that are components of (B1) are compounds selected from ethanol, 1-propanol, and 2-propanol. 22. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, The alcohols that are components of (B2) and have 2 or more but less than 12 carbon atoms and are binary or more but less than 12 are compounds selected from ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and glycerol. 23. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, The organic solvent having a hydrocarbon group, ether group, and hydroxyl group having 1 or more and 8 or fewer carbon atoms as component (B3) is a compound selected from diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3-diethylglycerol ether, triethylglycerol ether, 1-pentylglycerol ether, 2-pentylglycerol ether, 1-octylglycerol ether, and 2-ethylhexylglycerol ether, wherein the hydrocarbon group does not include aromatic groups. 24. The liquid cleaning agent composition for fiber products as claimed in claim 15, wherein, The organic solvent having partially substituted or unsubstituted aromatic groups, ether groups and hydroxyl groups as component (B4) is a compound selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, 2-benzyloxyethanol and diethylene glycol monobenzyl ether. 25. The liquid cleaning agent composition for fiber products as claimed in claim 1, wherein, The water content is 10% by mass or more and 80% by mass or less. 26. A method for manufacturing a liquid detergent composition for fiber products, wherein, The method for manufacturing the liquid detergent composition for fiber products is to mix the following component (A), the following component (B), and water, wherein the proportion of component (A) in the total mixture is 10% by mass or more and 60% by mass or less. (A) Composition: Inner olefin sulfonate, which is an inner olefin sulfonate with 18 carbon atoms, and the mass ratio of an inner olefin sulfonate with 18 carbon atoms in which the sulfonic acid group exists at the 2nd position and the 4th position to an inner olefin sulfonate with 18 carbon atoms in which the sulfonic acid group exists at the 5th position and the sulfonic acid group exists at the 5th position to the 18 ... (B) Component: Organic solvent with hydroxyl groups. 27. A method for cleaning fiber products, wherein, Cleaning of fiber products using a cleaning solution containing the liquid cleaning agent composition for fiber products according to any one of claims 1 to 25 and water. 28. The cleaning method for fiber articles as described in claim 27, wherein, The content of component (A) in the cleaning solution is more than 0.005% by mass and less than 1.0% by mass. 29. The cleaning method for fiber articles as described in claim 27 or 28, wherein, The content of component (B) in the cleaning solution is more than 0.001% by mass and less than 0.8% by mass. 30. The cleaning method for fiber articles as described in claim 27 or 28, wherein, The content of component (B) in the cleaning solution is more than 0.002% by mass and less than 0.5% by mass.