JP7430526B2 - liquid detergent composition - Google Patents

Description

FIELD OF THE INVENTION This invention relates to liquid detergent compositions.

In recent years, the performance that consumers are looking for in liquid detergents for textile products has diversified, and they are demanding not only good cleaning performance, but also something that does not impair the performance of the product after washing. Specifically, it is required not only to provide flexibility to textile products, but also to not impair their fragrance retention performance.

Conventionally, anionic surfactants, especially alkylbenzene sulfonates, olefin sulfonates, and furthermore, internal olefin sulfonates obtained from internal olefins having a double bond inside the olefin chain rather than at the end, and having 2 carbon atoms. Nonionic surfactants containing ~3 oxyalkylene groups are widely used as household and industrial cleaning ingredients.

Patent Documents 1 to 3 describe internal olefin sulfonates having a specific number of carbon atoms and cleaning compositions containing the same. Patent Documents 1 and 2 describe that it has excellent foaming properties and foam quality when washing hair. Patent Document 3 describes that fibers can be made soft by using them in combination with a specific nonionic surfactant. Patent Document 4 describes that texture such as flexibility can be imparted to textile products by using a predetermined internal olefin sulfonate in a predetermined washing method. Patent Document 5 describes that the water absorbency of textile products can be maintained by using a predetermined internal olefin sulfonate in a predetermined washing method. Patent Document 6 discloses the use of a certain internal olefin sulfonate as a modifier for making textile products soft. Further, Patent Document 7 describes a cleaning composition containing a specific anionic surfactant or nonionic surfactant and fragrance microcapsules.

JP2014-077126A Japanese Patent Application Publication No. 2014-076988 Japanese Patent Application Publication No. 2017-214567 JP2017-214678A JP2018-104880A Japanese Patent Application Publication No. 2018-66102 Japanese Patent Application Publication No. 2016-204508

As mentioned above, it is known that the combination of a specific surfactant and fragrance microcapsules provides excellent fragrance persistence. Detergents using internal olefin sulfonates as surfactants are known to give textile products a soft texture. Detergents designed to not only clean textile products but also add flexibility to them not only add flexibility to textile products, but also improve the longevity of fragrances and make clothing more comfortable. It is hoped that

The present invention provides a liquid detergent composition that has excellent flexibility and fragrance persistence for textile products.

The present inventors conducted intensive research on detergents for textile products using specific internal olefin sulfonates, and found a detergent composition having excellent flexibility and fragrance retention, and provide the present invention. reached.

That is, the present invention provides (A) internal olefin sulfonate [hereinafter referred to as component (A)] from 1% by mass to 50% by mass, and (B) microcapsules encapsulating a fragrance composition [hereinafter referred to as component (B)]. A liquid detergent composition containing 0.01% by mass or more and 2% by mass or less of (C) hydroxyl group-containing organic solvent [hereinafter referred to as component (C)], 3% by mass or more and 30% by mass or less of (C), and water. Regarding.

According to the present invention, it is possible to obtain a liquid detergent composition that can impart flexibility to textile products and has excellent fragrance persistence.

<(A) component>
Component (A) of the present invention is an internal olefin sulfonate. The internal olefin sulfonate of component (A) may be an internal olefin sulfonate having 16 to 24 carbon atoms. After repeated studies on internal olefin sulfonates, we found that internal olefin sulfonates inhibit the formation of hydrogen bonds between fibers of textile products that occur during the dehydration and drying processes, and as a result, the It was thought that this would suppress the hard, stiff feel of textile products after drying and give them flexibility.
The present inventors also found that the effect becomes more pronounced as the proportion of the internal olefin sulfonate having 18 carbon atoms [component (A1)] in component (A) increases. Therefore, the proportion of component (A1) in component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less, and 100% by mass or more. It may be mass %.
The internal olefin sulfonate having carbon atoms other than 18 preferably has carbon atoms of 12 or more, more preferably 14 or more, even more preferably 16 or more, and preferably 24 or less, more preferably 22 or less, and even more. Preferably it is an internal olefin sulfonate of 20 or less.
The number of carbon atoms in component (A) and component (A1) represents the number of carbon atoms in the internal olefin to which the sulfonate is covalently bonded.
In the present invention, by using a predetermined amount of the component (A1) as the component (A), excellent flexibility and fragrance persistence for textile products can be achieved.
The liquid detergent composition of the present invention preferably contains, as component (A), an internal olefin sulfonate having 12 or more carbon atoms, and further preferably 16 or more and 24 or less carbon atoms. Contains an internal olefin sulfonate in which the proportion of component (A1) is 80% by mass or more.
In the present invention, the content of component (A) and component (A) is the amount in terms of sodium salt unless otherwise specified. That is, the mass % and mass ratio of the component (A) and the component (A1) are calculated based on the amount in terms of sodium. Furthermore, the descriptions given below regarding component (A) can also be applied to component (A1).

Component (A), the internal olefin sulfonate, contains 80% by mass or more, preferably 90% by mass or more, more preferably 90% by mass or more, and more preferably It is a sulfonate obtained by sulfonating, neutralizing, and hydrolyzing an internal olefin containing 95% by mass or more.

Such internal olefins include those containing a trace amount of so-called alpha olefins (hereinafter also referred to as α-olefins) in which the double bond is present at the 1st position of the carbon chain. Furthermore, when internal olefins are sulfonated, β-sultones are produced quantitatively, and some of the β-sultones are converted into γ-sultones and olefin sulfonic acids, which are further converted into hydroxyl in the neutralization/hydrolysis process. Converted to alkanesulfonates and olefinsulfonates (eg, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the resulting hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. In addition, the obtained products are mainly mixtures of these, and some of them include hydroxyalkanesulfonates having a hydroxyl group at the end of the carbon chain, or olefins having a double bond at the end of the carbon chain. May contain trace amounts of sulfonates.
In this specification, each of these products and mixtures thereof are collectively referred to as internal olefin sulfonate (component (A)). Furthermore, hydroxyalkanesulfonate is referred to as a hydroxy form of internal olefin sulfonate (hereinafter also referred to as HAS form), and olefin sulfonate is referred to as olefin form of internal olefin sulfonate (hereinafter also referred to as IOS form).
The mass ratio of the HAS form and the IOS form of the compound in component (A) can be measured using a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). Specifically, the mass ratio can be determined from the HPLC-MS peak area of component (A).

Salts of internal olefin sulfonates include alkali metal salts, alkaline earth metal (1/2 atom) salts, ammonium salts, and organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanol ammonium salts having 2 or more and 6 or less carbon atoms, which will be described later. Organic ammonium salts also include salts of amines. From the viewpoint of versatility, the salt of the internal olefin sulfonate is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

As is clear from the above production method, the sulfonic acid group of the internal olefin sulfonate of component (A) exists inside the carbon chain, that is, the olefin chain or the alkane chain, and is partially present in the internal olefin sulfonate. A trace amount of sulfonic acid groups may also be present at the end of the carbon chain.

The content of the internal olefin sulfonate in which the sulfonic acid group is present at the 5th or higher positions, preferably at the 5th or higher and 9th positions in the component (A) is preferably 5% by mass from the viewpoint of improving the flexibility of the fibers. The above is more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 45% by mass or less. It is not more than 40% by mass, more preferably not more than 40% by mass.

The content of an internal olefin sulfonate [hereinafter sometimes referred to as (IO-1S)] in which a sulfonic acid group is present at the 2nd to 4th position in the component (A), Preferably, (IO-1S)/(IO-2S) is the mass ratio to the content of internal olefin sulfonate [hereinafter sometimes referred to as (IO-2S)] present at the 5th to 9th positions. , from the viewpoint of improving fiber flexibility, is preferably 0.5 or more, more preferably 0.75 or more, even more preferably 0.8 or more, even more preferably 1.0 or more, and preferably 10 or less. , more preferably 6 or less, still more preferably 5.5 or less, even more preferably 4 or less. The mass ratio of (IO-1S)/(IO-2S) in component (A1) is also preferably within this range.

The content of each compound having a different sulfonic acid group position in component (A) can be measured by HPLC-MS. In this specification, the content of each compound having a sulfonic acid group at a different position is determined as a mass ratio based on the HPLC-MS peak area of the compound having a sulfonic acid group at each position in all HAS forms of component (A). shall be.

The content of the olefin sulfonate in which the sulfonic acid group is present in the 1-position in the component (A) is such that it provides good flexibility to the fibers even when the temperature of the water used for washing is low, from 0°C to 15°C. From the viewpoint of imparting properties, the content of component (A) is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and production cost. From the viewpoint of reducing the amount of carbon dioxide and improving productivity, the content is preferably 0.01% by mass or more.
The position of the sulfonic acid group in these compounds is in the olefin or alkane chain.

The internal olefin sulfonate can be a mixture of a hydroxy form and an olefin form. The mass ratio (olefin/hydroxy) of the content of the olefin of the internal olefin sulfonate and the content of the hydroxy of the internal olefin sulfonate in component (A) is 0/100 or more, and more preferably 5/ It can be 95 or more, and 50/50 or less, further 40/60 or less, further 30/70 or less, and further 25/75 or less.

The mass ratio between the content of the hydroxyl form of the internal olefin sulfonate in the component (A) and the content of the olefin form of the internal olefin sulfonate in the component (A) is calculated using a high performance liquid chromatography mass spectrometer (HPLC). -MS) according to the method described in the Examples.

Component (A) can be produced, for example, by sulfonating, neutralizing, and hydrolyzing an internal olefin containing a predetermined amount of an internal olefin having 18 carbon atoms, preferably an internal olefin having 18 carbon atoms, as a raw material. . The sulfonation reaction can be carried out by reacting 1.0 to 1.2 moles of sulfur trioxide gas with respect to 1 mole of internal olefin. The reaction temperature can be 20 to 40°C.
Neutralization is carried out by reacting with an aqueous alkali solution of sodium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1.0 to 1.5 times the theoretical value of the sulfonic acid group by mole. The hydrolysis reaction may be carried out at 90 to 200°C for 30 minutes to 3 hours in the presence of water. These reactions can be performed sequentially. Further, after the reaction is completed, it can be purified by extraction, washing, etc.

In addition, in producing the internal olefin sulfonate (A), sulfonation, neutralization, and hydrolysis may be performed using a raw material internal olefin mainly containing an internal olefin having 18 carbon atoms. The raw material internal olefin consisting of the raw material internal olefin can be treated by sulfonation, neutralization, and hydrolysis, and if necessary, multiple types of internal olefin sulfonates having different numbers of carbon atoms prepared in advance can be mixed. good.

In the present invention, the internal olefin refers to an olefin having a double bond inside the olefin chain, as described above. The internal olefin used in component (A) may be used alone with only 18 carbon atoms, or two or more olefins with carbon atoms other than 18 may be used in combination.

When the raw internal olefin is sulfonated, neutralized, and hydrolyzed to obtain the internal olefin sulfonate of component (A) containing a specific amount of component (A1), the double bond in the raw internal olefin is at the 2-position. The total content of internal olefins present is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, even more preferably 25% by mass or more, from the viewpoint of improving the flexibility of the fiber. , still more preferably 30% by mass or more, even more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 60% by mass or less.

The total content of olefins in which a double bond is present in the first position, so-called alpha olefins, in raw internal olefins provides good flexibility to fibers even when the water used for washing is at a low temperature of 0°C to 15°C. From the viewpoint of imparting properties, the content is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and reduces production costs and improves productivity. From this viewpoint, it is preferably 0.01% by mass or more.

The content of the olefin in which the double bond is present at the 6th position or higher in the raw internal olefin is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, from the viewpoint of solution stability. , even more preferably 35% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably It is 10% by mass or less. Note that the maximum value of the double bond position in the raw material internal olefin varies depending on the number of carbon atoms.

The distribution of double bonds in the raw internal olefin can be measured, for example, using a gas chromatograph mass spectrometer (hereinafter abbreviated as GC-MS). Specifically, components with different carbon chain lengths and double bond positions are accurately separated using a gas chromatograph analyzer (hereinafter abbreviated as GC), and each component is subjected to a mass spectrometer (hereinafter abbreviated as MS). The double bond positions can be identified, and the respective ratios can be determined from the GC peak area.

<(B) component>
Component (B) of the present invention is a microcapsule containing a fragrance composition, and when used in combination with component (A), it is possible to enhance fragrance persistence during long-term storage. The present inventors have discovered that the internal olefin sulfonate of component (A) has the effect of softening textile products even during the dehydration process, so that there is less entanglement of laundry items, and the microcapsules of component (B) It is believed that this will reduce the crushing of microcapsules and make it easier for microcapsules to remain inside the textile product.

Component (B) of the present invention is a fragrance microcapsule. A fragrance microcapsule is one in which a fragrance composition is encapsulated. For example, a microcapsule in which a resin is used for the outer shell (wall material) and a fragrance composition is encapsulated by a known method can be mentioned.

The method for preparing perfume microcapsules is not particularly limited, and any known microencapsulation method can be employed. Specifically, chemical production methods (interfacial polymerization method, in situ polymerization method, orifice method), physicochemical methods (coacervation method), mechanical/physical methods (air suspension coating method, spray drying method, high-speed airflow impact method), etc. Examples of the outer shell of perfume microcapsules include various polymeric compounds such as polyurethane, polyamide, melamine resin, urea resin, alginate, gelatin, gum arabic, and starch, as well as inorganic compounds such as silica.

More specifically, regarding the method for manufacturing the fragrance microcapsules of the present invention, see "Make + Use Microcapsules" (Masumi Koishi et al., Industrial Research Association, published in 2005), JP-A No. 2008-63575, JP-A No. 2006 Methods described in Japanese Patent Application Laid-open No. 249326, Japanese Patent Application Publication No. 2006-518790, Japanese Patent Application Laid-Open No. 11-216354, Japanese Patent Application Laid-Open No. 5-222672, etc. can be employed.

A preferred method for producing perfume microcapsules is to obtain an emulsion by dispersing an emulsifier such as an ethylene-maleic anhydride copolymer, a perfume, and any diluent or solvent in water, and then add melamine-formaldehyde to this emulsion. A method of obtaining a slurry of perfume microcapsules by adding a wall material such as a resin and stirring is exemplified. In addition, after preparing a wall material/emulsifier mixture by mixing in advance a monomer that will become the resin forming the wall material and an emulsifier such as isobutylene-maleic anhydride copolymer or acrylic acid-acrylamide copolymer in water. Another method includes emulsifying this wall material/emulsifier mixture with a fragrance and any diluent or solvent, and adding formaldehyde to this emulsion and stirring to obtain a slurry of fragrance microcapsules.

As the fragrance used in the fragrance microcapsules, the fragrance compositions described in JP-A No. 2006-249326, WO 2007/038570, and JP-A 2007-314693 can be used.

The fragrance contained in the capsule of component (B) of the present invention [hereinafter referred to as fragrance (B1)] is a fragrance compound having a logP value of 2.0 or more and 6.0 or less [hereinafter referred to as fragrance compound (b1)]. ] Contains 90% by mass or more. The fragrance (B1) is usually a composition containing a plurality of fragrance compounds including the fragrance compound (b1). The fragrance (B1) preferably contains 95% by mass or more of the fragrance compound (b). In addition, from the viewpoint of ease of manufacturing capsules, the fragrance compound (B1) has a logP value of 2.0 or more, preferably 2.3 or more, more preferably 2.5 or more, and 6.0 or less, and 5 .5 or less, more preferably 5.0 or less.

As the fragrance compound (b1), octanal (3.0), nonanal (3.0), decanal (4.0), lyral (2.2), lyreal (3.9), hexylcinnamic aldehyde (4.9) ), amyl cinnamic aldehyde (4.3), p,t-butylhydrocinnamic aldehyde (3.6), dimethyltetrahydrobenzaldehyde (2.9), hexyl acetate (4.9), tricyclodecenyl acetate (2.4), citronellyl acetate (4.2), geranyl acetate (3.7), linalyl acetate (3.5), terpinyl acetate (3.6), o,t-butylcyclohexyl acetate (4.1) , p,t-butylcyclohexyl acetate (4.1), allylcyclohexyl propionate (2.9), tricyclodecenyl propionate (3.9), allyl caproate (3.2), amyl salicylate (4) .6), hexyl salicylate (5.1), benzyl salicylate (4.2), cyclohexyl salicylate (4.5), cis-3-hexenyl salicylate (4.6), methyl dihydrojasmonate (2.4), α-ionone (3.7), β-ionone (3.7), γ-methylionone (4.0), α-damascone (3.6), β-damascone (3.6), δ-damascone (3 .6), γ-nonalactone (2.8), γ-decalactone (3.3), γ-undecalactone (3.8), Neroline Yarayara (3.2), cyclamenaldehyde (3.5), limonene ( 4.4), Tetrahydrolinalool (3.5), Terpineol (2.6), Geraniol (2.4), Citronellol (3.3), Linalool (2.6), Tetrahydrolinalool (3.5), Eugenol (3.0), dihydromircenol (3.0), phenylhexanol (3.5), methyl anthranilate (2.0), methyl β-naphthyl ketone, (2.8), isoE super ( 4.7), Cedryl methyl ether (5.1), Sandal Mysore Core (manufactured by Kao Corporation) (3.9), Javanol (manufactured by Givaudan) (4.7), Ambroxan (5.3) , 1,8-cineole (2.9), geranylnitrile (3.9), citronellylnitrile (4.4), 11-oxa-16-hexadecanolide (Musk R-1, manufactured by Givaudan) (4.5) , ethylene brasylate (4.6), ethylene dodecanedioate (4.1), and cashmeran (4.0). In addition, as fragrances with a logP value higher than 6.0, cyclopentadecanolide (6.3), cyclohexadecanolide (6.8), and ambrettolide (6.4) are also included in capsules. preferred as Here, the numbers in parentheses are logP values.

In the present invention, the logP value is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol/water partition coefficient P is a distribution equilibrium when a trace amount of a compound is dissolved as a solute in a two-liquid phase solvent of 1-octanol and water, and is the ratio of the equilibrium concentrations of the compound in each solvent. It is common to express them in the form of their logarithm logP to the base 10. The logP values of many compounds have been reported, and many values can be referenced in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS) and the like. If there is no actually measured logP value, it can be calculated using a program such as "CLOGP" available from Daylight CIS. This program outputs the actually measured logP value, if any, as well as the value of "calculated logP (ClogP)" calculated by Hansch and Leo's fragment approach.

The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bonds (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds., p.295, Pergamon Press, 1990). This ClogP value can be used in place of the actually measured logP value when selecting a compound. In the present invention, if there is an actual measured value of logP, it is used, and if there is no measured value, the ClogP value calculated by the program CLOGP v4.01 is used.

In addition to the fragrance (B1), the microcapsules of component (B) may also contain a diluent, a solvent, and a solidifying agent. Examples of the diluent or solvent include ethylene glycol, propylene glycol, dipropylene glycol, and glycerin. Mention may be made of fatty alcohols, fatty acids, lower alcohols of fatty acids or glycerin esters.

The primary average particle diameter of the microcapsules of component (B) is preferably 1 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, and further preferably 20 μm or less. The average particle diameter of the microcapsules of the present invention is the median diameter determined by a laser diffraction/scattering particle size distribution analyzer LA-910 manufactured by HORIBA. Note that component (B) may be partially aggregated to the extent that storage stability is not impaired.

<(C) component>
Component (C) is an organic solvent having a hydroxyl group. Organic solvents are generally used as solubilizers. However, in the present invention, fragrance persistence can be improved by using component (C) in combination with component (A) and (B).

From the viewpoint of increasing fragrance persistence when used in combination with components (A) and (B) of the liquid detergent composition of the present invention, component (C) is an organic solvent with a CLogP of -1.5 or more and 2 or less. It is preferable that there be. In the present invention, CLogP is Perkin Elmer's ChemBioDraw Ultra ver. A calculated value calculated using ChemProperty of 14.0 is used. Note that the larger the value of ClogP, the higher the hydrophobicity.

Component (C) preferably has a CLogP of -1.0 from the viewpoint of improving the effect of imparting texture and fragrance persistence to textile products even when the liquid detergent composition of the present invention is used for washing at low temperatures. 4 or more, more preferably -1.2 or more, even more preferably -1 or more, even more preferably -0.8 or more, even more preferably -0.5 or more, even more preferably -0.1 or more, and more More preferably 0 or more, even more preferably 0.2 or more, even more preferably 0.4 or more, even more preferably 0.6 or more, and preferably 2 or less, more preferably 1.8 or less, even more preferably is an organic solvent having a hydroxyl group of 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less.

Component (C) preferably has a CLogP of - 1.4 or more, more preferably -1.2 or more, even more preferably -1 or more, even 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, even more preferably 0.4 or more, even more preferably 0.6 or more, and preferably 2 or less, more preferably 1.8 or less, It is an organic solvent having a hydroxyl group, more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less.

The (C) component is the following (C1) to (C4) components because the combination of the (A) component and the (B) component can further enhance the effect of imparting flexibility and fragrance persistence to textile products. One or more organic solvents selected from are preferred.
(C1) Component: Monohydric alcohol having 2 to 6 carbon atoms (C2) Component: Alcohol having 2 to 12 carbon atoms and 2 to 12 valences (C3) Component: Carbonized carbon having 1 to 8 carbon atoms Organic solvents containing hydrogen groups, ether groups, and hydroxyl groups (however, hydrocarbon groups exclude aromatic groups)
(C4) Component: Organic solvent having an aromatic group, an ether group, and a hydroxyl group that may be partially substituted

Specific examples of components (C1) to (C4) are shown below. The numbers in parentheses refer to Perkin Elmer's Chem Bio DrawUltra ver. This is the calculated value (CLogP) of each component calculated using ChemProperty of 14.0.

Examples of the monohydric alcohol having 2 to 6 carbon atoms, which is the component (C1), include ethanol (-0.24), 1-propanol (0.29), 2-propanol (0.07), phenol (1 .48).

Examples of the alcohol having a carbon number of 2 or more and 12 or less and a valence of 2 or more and 12 or less, which is the component (C2), include 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), 3-methyl-1,3-butanediol (-0.56), 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, which is the component (C3), 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-methoxy-2-propanol (-0.30), 1-ethoxy-2-propanol (0.09) ), 3-methoxy-3-methyl-1-butanol (0.18), 1-methylglycerin ether (-1.43), 2-methylglycerin ether (-0.73), 1,3-dimethylglycerin ether (-0.67), 1-ethylglycerin ether (-1.04), 1,3-diethylglycerin ether (0.11), triethylglycerin ether (0.83), 1-pentylglycerin ether (0.54) ), 2-pentyl glyceryl ether (1.25), 1-octyl glyceryl ether (2.1), and 2-ethylhexyl glyceryl ether (2.0).

Examples of the organic solvent having an aromatic group, an ether group, and a hydroxyl group which may be partially substituted, which is the component (C4), include 2-phenoxyethanol (1.2), diethylene glycol monophenyl ether (1.25), Examples include triethylene glycol monophenyl ether (1.08), polyethylene glycol monophenyl ether with an average molecular weight of about 480 (cannot be calculated), 2-benzyloxyethanol (1.1), and diethylene glycol monobenzyl ether (0.96). .

Component (C) is an organic solvent having a hydroxyl group selected from the above-mentioned components (C3) and (C4), and preferably has a ClogP of 0.6 or more and 1.5 or less.

The liquid detergent composition of the present invention improves the flexibility of textile products even if it is locally attached to textile products, and provides the above-mentioned (C3) and (C4) components. The content of the organic solvent selected from the above and having a ClogP of 0.6 or more and 1.5 or less is preferably 40% by mass or more, more preferably 50% by mass of all component (C). The content is more preferably 60% by mass or more, and preferably 100% by mass or less.

<Composition>
The content of component (A) in the liquid detergent composition of the present invention is preferably 1% by mass or more, more preferably 5% by mass, from the viewpoint of improving the flexibility of textile products and the fragrance persistence of component (B). Above, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. It is.

The content of component (B) in the liquid detergent composition of the present invention is 0.01% by mass or more, preferably 0.02% by mass or more, and more preferably 0.01% by mass or more, preferably 0.02% by mass or more, from the viewpoint of improving fragrance persistence during long-term storage. .05% by mass or more, more preferably 0.1% by mass or more, and 2% by mass or less, preferably 1.5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass. It is as follows.

The content of component (C) in the liquid detergent composition of the present invention is 3% by mass or more, preferably 4% by mass or more, from the viewpoint of increasing the flexibility of component (A) and the fragrance persistence of component (B). , more preferably 5% by mass or more, still more preferably 6% by mass or more, and 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less. .

The mass ratio (A)/(B) of the content of component (A) and the content of component (B) in the liquid detergent composition of the present invention increases the fragrance persistence of component (B) during long-term storage. From this point of view, it is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 100 or less, more preferably 80 or less, still more preferably 50 or less.

The mass ratio (A)/(C) between the content of component (A) and the content of component (C) in the liquid detergent composition of the present invention is determined from the viewpoint of improving the flexibility and fragrance persistence of component (A). , preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

<Water>
The remainder of the liquid detergent composition of the present invention is water. The water used is generally the water used for liquid detergents, but deionized water (sometimes also called ion-exchanged water) or sodium hypochlorite is added to the ion-exchanged water at a concentration of 1 mg/kg or more and 5 mg/kg or less. Added water can be used. You can also use tap water. The content of water is preferably 4% by mass or more, more preferably 5% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less.

<Optional ingredients, pH, etc.>

The liquid detergent composition of the present invention contains components (D) to (H) shown below and any other optional components described below that are known to be included in liquid detergents, as long as they do not impede the effects of the present invention. It is preferable to do so.

<(D) component>
The liquid detergent composition of the present invention can contain a compound selected from amines and ammonia as component (D). Component (D) acts as an alkaline agent when incorporated into a liquid detergent, but in the present invention, it may be contained in the composition as a counter ion for anionic compounds such as anionic surfactants and chelating agents. , in which case it also acts as a phase stabilizer.

As the component (D), those selected from the following general formulas (d1) to (d4) can be mentioned.

[In the formula, R ¹¹ , R ¹⁴ , R ¹⁶ , R ¹⁸ , R ²⁰ , R ²² , and R ²³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² , R ¹³ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²¹ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms. ]

Examples of the compound represented by the general formula (d1) include ammonia, monoethanolamine, diethanolamine, triethanolamine, N-methylpropanolamine, 2-amino-2-methyl-1-propanol, and the like. Examples of the compound represented by general formula (d2) include N-(β-aminoethyl)ethanolamine and the like. Examples of the compound represented by the general formula (d3) include diethylenetriamine and the like. Furthermore, examples of the compound represented by the general formula (d4) include morpholine, N-ethylmorpholine, and the like.

Preferred component (D) in the present invention is monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, and ammonia, and among these, monoethanolamine is more preferred from the viewpoint of properties and stability as an alkaline agent. When containing an anionic surfactant, component (D) can be blended as a counterion and contributes to liquid phase stability.

From the viewpoint of detergency and liquid phase stability, the content of component (D) in the liquid detergent composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably is 0.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less.

The mass ratio (A)/(D) of the content of component (A) to the content of component (D) in the liquid detergent composition of the present invention is preferably 1 from the viewpoint of detergency and liquid phase stability. Above, it is more preferably 5 or more, still more preferably 10 or more, and preferably 50 or less, more preferably 40 or less, still more preferably 30 or less.

<(E) component>
The liquid detergent composition of the present invention can contain a nonionic surfactant as component (E). As the nonionic surfactant of component (E), there can be mentioned a nonionic surfactant represented by the following general formula (e1).
R ^1e (CO) _m O-(AO) _n -R ^2e (e1)
[In the formula, R ^1e is an aliphatic hydrocarbon group having 9 to 16 carbon atoms, R ^2e is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, The AO group is one or more groups selected from ethyleneoxy groups and propyleneoxy groups, and n is the average number of added moles, which is a number of 3 or more and 50 or less. ]

In general formula (e1), R ^1e is an aliphatic hydrocarbon group having 9 or more and 16 or less carbon atoms. The number of carbon atoms in Re1 is 9 or more, preferably 10 or more, more preferably 11 or more, in order to make it easier to remove dirt attached to the fibers, and 16 or less, preferably in order to further enhance the softening effect of the fibers. is 15 or less, more preferably 14 or less.

The aliphatic hydrocarbon group for R ^1e is preferably a group selected from an alkyl group and an alkenyl group.
In general formula (e1), m is preferably 0.
In general formula (e1), R ^2e is preferably a hydrogen atom.

In general formula (e1), the AO group is one or more groups selected from ethyleneoxy and propyleneoxy groups. When containing 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. The AO group is preferably a group containing an ethyleneoxy group from the viewpoint of not inhibiting the fiber softening effect of component (A).

In general formula (e1), n is the average number of added moles, and is a number of 3 or more and 50 or less. The larger the number of n, the higher the HLB value, and the smaller the number, the lower the HLB value. From the viewpoint of stably blending component (A), n is 3 or more, preferably 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, and more. More preferably 12 or more, and from the viewpoint of cleaning properties of dirt attached to fibers, 50 or less, preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, even more preferably 26 or less, and more More preferably, it is 24 or less.

More preferable compounds as the nonionic surfactant of component (E) of the present invention have an ethyleneoxy group (hereinafter sometimes referred to as EO group) having an average degree of polymerization (or sometimes referred to as average number of added moles) of 3 or more; preferably 5 or more, and 50 or less, preferably 25 or less, and the average degree of polymerization (or sometimes referred to as average number of added moles) of propyleneoxy groups (hereinafter sometimes referred to as PO groups) is 0 or more and 5 or less, The number is preferably 3 or less, and the EO group and the PO group may be a random bond or a block bond, preferably a block bond, and more preferably, from the viewpoint of stability, EOPOEO or POEO, and the alkyl group is derived from a linear primary or secondary alcohol having 12 to 18 carbon atoms, more preferably 12 or 14, and even more preferably 12 carbon atoms. It is oxyethylene (polyoxypropylene) alkyl ether.

In the liquid detergent composition of the present invention, component (E) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of detergency and liquid phase stability. From the viewpoint of fragrance persistence, the content is preferably 30% by mass, more preferably 25% by mass or less, even more preferably 20% by mass or less.

The mass ratio (A)/(E) of the content of component (A) to the content of component (E) in the liquid detergent composition of the present invention is preferably from the viewpoint of liquid phase stability and fragrance persistence. It is 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

In the liquid detergent composition of the present invention, from the viewpoint of liquid phase stability and fragrance persistence, the proportion of component (A) in the total surfactant is preferably 10% by mass or more, more preferably 15% by mass or more, More preferably 18% by mass or more, preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, but the content of component (A) is large from the viewpoint of flexibility and fragrance. The content is preferably 50% by mass or more, and even more preferably 50% by mass or more.

<(F) component>
The liquid detergent composition of the present invention may contain surfactants other than the components (A) and (E). From the viewpoint of detergency, it is preferable to use an anionic surfactant other than component (A) (hereinafter sometimes referred to as component (F)) in combination.

As the anionic surfactant other than the component (A) which is the component (F), the compound (F1) represented by the following general formula (f1), the compound (F2) represented by the general formula (f2), and the general formula ( Examples include one or more compounds selected from compounds (F3) represented by f3).
R ^1f -O-(PO) _m1 (EO) _n1 -SO ₃ M (f1)
(In formula (f1), R ^1f represents an alkyl group having 8 to 22 carbon atoms, the carbon atom bonded to the oxygen atom is the first carbon atom, PO represents a propyleneoxy group, and EO represents an ethyleneoxy group. EO and PO may be block or random bonds, m1 and n1 are the average number of moles added, m is 0 or more and 5 or less, n is 0 or more and 16 or less, and M is a hydrogen atom. , alkali metal, alkaline earth metal (1/2 atom), ammonium or organic ammonium)
R ^2f -B-SO ₃ M (f2)
(In formula (f2), R ^2f represents an alkyl group having 9 to 21 carbon atoms, B represents a benzene ring, and the carbon atom of R ^2f bonded to the carbon atom of B is a secondary carbon atom, M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium or organic ammonium.The sulfonic acid group is bonded to the para position to ^R2 bonded to B.)
R ^3f -CH(SO ₃ M) COOR ⁴ f (f3)
(In formula (f3), R ^3f represents an alkyl group having 6 to 20 carbon atoms, R ^4f represents an alkyl group having 1 to 6 carbon atoms, and M is a hydrogen atom, an alkali metal, an alkaline earth metal ( 1/2 atom), indicating ammonium or organic ammonium)

In the general formula (f1), R ^1f is an alkyl group having preferably 9 or more carbon atoms, more preferably 10 or more carbon atoms, even more preferably 12 or more carbon atoms, and preferably 18 or less, more preferably 16 or less, and still more preferably 14 or less carbon atoms. It is the basis. R ^1f is preferably a straight-chain alkyl group.
In general formula (f1), m1 is preferably 4 or less, more preferably 3 or less.
In the general formula (f1), n1 is preferably 0.5 or more, more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, still more preferably 4 or less.
In general formula (f1), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1/2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium may be a salt of the above-mentioned component (D) with an amine. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and even more preferably sodium.

Component (F1) has an alkyl group with carbon atoms of 12 or more and 14 or less, an average number of added moles of propioxy groups of 0 or more and 4 or less, and an average number of added moles of ethyleneoxy groups of 1 or more and 4 or less (polymer oxypropylene) polyoxyethylene alkyl ether sulfate ester sodium salt is preferred. That is, component (F1) is preferably a compound in the general formula (f1), where R ^1f is an alkyl group having 12 or more and 14 or less carbon atoms, m1 is 0 or more and 4 or less, n1 is 1 or more and 4 or less, and M is sodium. .

In general formula (f2), R ^2f is an alkyl group having 9 or more carbon atoms, preferably 10 or more, more preferably 11 or more, and preferably 18 or less, more preferably 16 or less, and still more preferably 14 or less. .
In general formula (f2), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1/2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium salt may be a salt of the aforementioned component (D) with an amine. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and even more preferably sodium.

As component (F2), p-alkylbenzenesulfonate salts in which the alkyl group has 11 to 14 carbon atoms are preferred, and p-alkylbenzenesulfonic acid sodium salts in which the alkyl group has 11 to 14 carbon atoms are more preferred. That is, component (F2) is preferably a compound in general formula (f2), where R ^2f is an alkyl group having 11 or more and 14 or less carbon atoms, and M is sodium.

In general formula (f3), R ^3f is an alkyl group preferably having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less carbon atoms.
In general formula (f3), R ^4f is an alkyl group having 1 or more carbon atoms, preferably 5 or less carbon atoms, and more preferably 4 or less carbon atoms.
In general formula (f3), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1/2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium salt may be a salt of the aforementioned component (D) with an amine. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and even more preferably sodium.

Component (F3) is preferably an α-sulfo fatty acid methyl ester sodium salt in general formula (f3), where R ^3f is an alkyl group having 11 to 14 carbon atoms, and R ^4f is a methyl group.

As component (F) of the present invention, from the viewpoint of increasing the flexibility of component (A), one or more anionic surfactants selected from component (F1) and component (F2) are preferable, and component (F2) One or more anionic surfactants selected from are more preferred.

From the viewpoint of increasing the flexibility of component (A), the content of component (F) in the liquid detergent composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and The content is preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

The mass ratio (A)/(F) between the content of component (A) and the content of component (F) in the liquid detergent composition of the present invention is preferably set from the viewpoint of increasing the flexibility of component (A). It is 0.1 or more, more preferably 1 or more, even more preferably 2 or more, and preferably 50 or less, more preferably 30 or less, and still more preferably 10 or less.

<(G) component>
The liquid detergent composition of the present invention preferably contains, as component (G), a fragrance composition comprising various fragrance compounds that are blended into detergent products. Component (G) is a fragrance composition that is not encapsulated in microcapsules. Examples of the fragrance compound constituting the fragrance composition of component (G) include the fragrance compounds described in JP-A No. 2017-214676.

<Other ingredients>
In addition to the above components, the liquid detergent composition of the present invention may contain the following components (H1) to (H8).
(H1) 0.01% by mass or more and 10% by mass or less of recontamination prevention agents and dispersants such as polyacrylic acid, polymaleic acid, and carboxymethyl cellulose in the composition (H2) Hydrogen peroxide, sodium percarbonate, sodium perborate, etc. A bleaching agent of 0.01% by mass or more and 10% by mass or less (H3) tetraacetylethylenediamine in the composition, bleaching activity represented by general formulas (I-2) to (I-7) of JP-A-6-316700 A bleach activator such as a bleaching agent is added to the composition at least 0.01% by mass and not more than 10% by mass (H4) of one or more enzymes selected from cellulases, amylases, pectinases, proteases and lipases, preferably amylases and proteases. 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and 2% by mass of one or more enzymes contained in the composition. % or less, preferably 1% by mass or less (H5), fluorescent dyes such as commercially available fluorescent dyes such as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) are used in the composition. 0.001% by mass or more and 1% by mass or less (H6) Antioxidants such as butylated hydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite in the composition 0.01% by mass or more and 2% by mass or less (H7) Add appropriate amounts of antifoaming agents such as pigments, antibacterial preservatives, and silicone.
(H8) In order to suppress separation of the fragrance microcapsules of the component (B), hydrogenated castor oil can be used as the component (H8). The content of the component (H8) in the liquid detergent composition of the present invention is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and 0.1% by mass or more, in terms of suppressing the separation of fragrance microcapsules. More preferably, the amount is % by mass or more. The content of component (H8) in the liquid detergent composition of the present invention is preferably 1% by mass or less, more preferably 0.8% by mass or less, and 0.8% by mass or less, from the viewpoint of lowering the viscosity of the liquid detergent composition. More preferably, it is 5% by mass or less.

The pH at 20° C. of the liquid detergent composition of the present invention is preferably 3 or more, more preferably 4 or more, and even more preferably is 5 or more, and preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less. The pH is measured according to the pH measurement method described below.
<pH measurement method>
Connect the composite electrode for pH measurement (glass rubbed sleeve type, manufactured by HORIBA) to a pH meter (PH/Ion Meter F-23, manufactured by HORIBA), and turn on the power. A saturated potassium chloride aqueous solution (3.33 mol/L) is used as the pH electrode internal solution. Next, fill a 100 mL beaker with each of pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), Immerse in a constant temperature bath at ℃ for 30 minutes. The pH measurement electrode is immersed in a 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 is measured after 1 minute.

From the viewpoint of ease of handling, the viscosity of the liquid detergent composition of the present invention at 20° C. is preferably 10 mPa·s or more, more preferably 30 mPa·s or more, even more preferably 50 mPa·s or more, and preferably is 400 mPa·s or less, more preferably 300 mPa·s or less, still more preferably 200 mPa·s or less. These viscosities were measured using a B-type viscometer (VISCOMETER MODEL DVM-B, manufactured by Tokyo Keiki Co., Ltd.) using rotor No. 3 or 4, the rotation speed was 60 r/min, and the measurement time was 60 seconds.

The liquid detergent composition of the present invention is suitable for use in textile products. Furthermore, the liquid detergent composition of the present invention is suitable for cleaning textile products in water containing hard components. The above-mentioned "suitable for washing textile products in water containing a hardness component" means that textile products can be washed in water containing a hardness component by using the liquid detergent composition of the present invention. This means that the product is soft and has a long-lasting fragrance, and that it can be used to clean stains from textiles.

In the water containing hardness components used for washing, the hardness of the water is preferably 1° dH or more, more preferably 2° dH or more on the German hardness scale, from the viewpoint of further improving the effect of imparting flexibility to textile products. , more preferably 3°dH or more, and preferably 20°dH or less, more preferably 18°dH or less, and even more preferably 15°dH or less. Here, the German hardness (°dH) in this specification refers to the concentration of calcium and magnesium in water in terms of CaCO ₃ concentration of 1 mg/L (ppm) = approximately 0.056°dH (1°dH = 17. 8ppm).
The calcium and magnesium concentrations for this German hardness are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.
A specific method for measuring the German hardness of water in this specification is shown below.
<How to measure the 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 solution for hardness measurement (a solution in which 67.5 g of ammonium chloride was dissolved in 570 ml of 28 w/v% ammonia water and the total volume was made up to 1000 ml with ion-exchanged water)
[Measurement of hardness]
(1) Collect 20 ml of water as a sample into a conical beaker using a whole pipette.
(2) Add 2 ml of ammonia buffer for hardness measurement.
(3) Add 0.5 ml of Universal BT indicator. Confirm that the solution is reddish-purple after addition.
(4) While shaking the conical beaker well, add 0.01 mol/l EDTA/2Na solution dropwise from the buret, and the end point of the titration is when the sample water turns blue.
(5) The total hardness is calculated using the following formula.
Hardness (°dH) = T x 0.01 x F x 56.0774 x 100/A
T: Titration amount (mL) of 0.01 mol/l EDTA/2Na solution
A: Sample volume (20 mL, sample water volume)
F: Factor of 0.01mol/l EDTA/2Na solution

<Fiber>
The fibers to be washed with the liquid detergent composition of the present invention may be either hydrophobic fibers or hydrophilic fibers. Examples of hydrophobic fibers include protein fibers (milk protein casein fiber, Promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), and polyvinyl alcohol fibers. Fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride/ Polyvinyl alcohol copolymer fibers (polycleral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fiber, carbon fiber, alumina fiber, silicone carbide fiber, rock Examples include fibers (rock fibers), mineral slag fibers (slag fibers), metal fibers (gold threads, silver threads, steel fibers), and the like. Examples of hydrophilic fibers include seed hair fibers (cotton, ramie, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (manila hemp, sisal, etc.), coconut fibers, Rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuña, angora, etc.), silk fibers (domestic silkworm silk, wild silkworm silk), feathers, cellulose fibers (rayon, polynosic, cupro, acetate, etc.) etc. are exemplified.

<Textile products>
Examples of textile products include fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics using the above-mentioned hydrophobic fibers and hydrophilic fibers, as well as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, and towels obtained using the same. , refers to products such as knitwear, socks, underwear, and tights.

[How to wash textile products]
The present invention provides a method for cleaning textile products, which comprises cleaning textile products with a cleaning solution containing the liquid detergent composition of the present invention and water.
The method of cleaning textile products of the present invention is, for example, a method of cleaning textile products with a cleaning solution containing the liquid detergent composition of the present invention and water, the cleaning method of textile products having a hardness of more than 0° dH. It's a method.
Further, the method for cleaning textile products of the present invention is, for example, a method of cleaning textile products with a cleaning liquid obtained by mixing the liquid detergent composition of the present invention and water, the hardness of the water being 0° dH or less. This is a method of cleaning textile products that goes beyond the basics.
Moreover, the method for washing textile products of the present invention is a method of washing textile products with a cleaning liquid containing the liquid detergent composition of the present invention and water and having a hardness of more than 0° dH.

In these methods of cleaning textile products of the present invention, the hardness of the cleaning liquid is a value calculated using the above-mentioned "Method for measuring German hardness of water." Further, the hardness of the cleaning liquid can be selected from the preferred range of hardness of water containing the hardness component described in the liquid detergent composition of the present invention. The hardness of the cleaning liquid can also be measured in the same manner as the hardness of water. Further, the hardness of the water used in the cleaning method, for example, the water used for preparing the cleaning liquid, the water used for rinsing, etc., can be selected from the preferred range of hardness of water containing the hardness component described in the liquid detergent composition of the present invention. . The hardness of water can also be measured in the same manner as the hardness of water described above.

In the method for cleaning textile products of the present invention, the cleaning liquid is preferably obtained using the liquid detergent composition of the present invention.

The matters described in connection with the liquid detergent composition of the present invention can be appropriately applied to the method of cleaning fibers of the present invention.

The content of component (A) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.003% by mass or more, and preferably 1.0% by mass or more. It is at most 0.5% by mass, more preferably at most 0.1% by mass, even more preferably at most 0.05% by mass, even more preferably at most 0.02% by mass.

The content of component (B) in the cleaning liquid is preferably 0.000005% by mass or more, more preferably 0.00001% by mass or more, even more preferably 0.0001% by mass or more, and preferably 0.004% by mass or more. It is not more than 0.0002% by mass, more preferably not more than 0.0004% by mass.

The content of component (C) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.003% by mass or more, and preferably 1.0% by mass or more. It is at most 0.5% by mass, even more preferably at most 0.1% by mass, even more preferably at most 0.02% by mass.

The cleaning liquid has a mass ratio (A)/(B) of the content of the component (B) and the content of the component (A), which is determined by the cleaning property of stains attached to the textile product per mass of the cleaning liquid and during long-term storage. From the viewpoint of increasing the fragrance persistence of component (B), the number is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 100 or less, more preferably 80 or less, and still more preferably 50. It is as follows.

In addition, the cleaning liquid has a mass ratio (A)/(C) of the content of the (A) component and the content of the (C) component, which improves the flexibility and scent retention of textile products per mass of the liquid detergent composition. From the viewpoint of improving properties, it is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.

The temperature of the cleaning liquid is preferably 0°C or higher, more preferably 3°C or higher, and even more preferably 5°C or higher, from the viewpoint of improving the ability to clean dirt adhering to textile products. The temperature is preferably 40° C. or lower, more preferably 35° C. or lower, from the viewpoint of not removing too much of the oil contained therein and making the textile product softer and with a lasting fragrance.

The pH of the cleaning solution is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving the ability to clean dirt attached to textile products, and from the viewpoint of making textile products softer and with a lasting fragrance. , preferably 10 or less, more preferably 9 or less. The pH of the cleaning liquid can also be measured in the same manner as the pH of the liquid detergent composition. The cleaning liquid may have a pH within the above range at 20°C.

In recent years, washing machines have become larger, and the value of the bath ratio, which is expressed as the ratio of the mass of clothes (kg) to the amount of water (liters) of washing liquid, is expressed as the ratio of the amount of water (liters) of washing liquid / mass of clothes (kg) (hereinafter, this The ratio (sometimes referred to as bath ratio) tends to decrease. If a household washing machine is used and the bath ratio is small, the agitation during washing increases the friction between textile products, which may impair the softness and fragrance persistence of the textile products. The method for washing textile products of the present invention can finish textile products soft and with a lasting fragrance even under washing conditions where the bath ratio is small. The bath ratio is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, from the viewpoint of making the textile product softer and with a lasting fragrance, and from the viewpoint of maintaining detergency. , preferably 45 or less, more preferably 40 or less, still more preferably 30 or less, even more preferably 20 or less.

The method for washing textile products of the present invention can finish textile products with softer properties and improved fragrance persistence even if the washing time is short. The washing time is preferably 1 minute or more, more preferably 2 minutes or more, and more preferably 1 minute or more, more preferably 2 minutes or more, from the viewpoint of making it easier to remove dirt attached to the textile product or making the textile product softer and with a longer lasting fragrance. Preferably, the heating time is 3 minutes or more, and from the viewpoint of making the textile product softer, the heating time is preferably 1 hour or less, more preferably 30 minutes or less, still more preferably 20 minutes or less, and still more preferably 15 minutes or less.

The method of cleaning textile products of the present invention is suitable for a method in which the fibers are immersed in a liquid used for refining while being fed by a roller or the like, and a rotary cleaning method. The rotary cleaning method refers to a cleaning method in which a textile product that is not fixed to a rotating device rotates together with a cleaning liquid around a rotation axis. The rotary washing method can be carried out with a rotary washing machine. Therefore, in the present invention, it is preferable to wash the textile product using a rotary washing machine in order to make the textile product softer and have a longer lasting fragrance. Specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and an agitator washing machine. As these rotary washing machines, those commercially available for household use can be used.

<Ingredients>
In the Examples and Comparative Examples, the following components were used.
[(A) component]
(a-1): Internal olefin sulfonate sodium salt having 18 carbon atoms The mass ratio of olefin body (sodium olefin sulfonate)/hydroxy body (sodium hydroxyalkanesulfonate) in (a-1) is 16/84. . The mass ratio of the positional distribution of the sulfonic acid groups of the HAS compound in (a-1) is as follows. 1st/2nd/3rd/4th/5th/6th to 9th = 1.5/22.1/17.2/21.8/13.5/23.9. Further, (IO-1S)/(IO-2S)=1.6 (mass ratio).

(a-2): The mass ratio of olefin body (sodium olefin sulfonate)/hydroxy body (sodium hydroxyalkanesulfonate) in internal olefin sulfonate sodium salt having 16 carbon atoms (a-2) is 15/85. . The mass ratio of the positional distribution of the sulfonic acid groups of the HAS compound in (a-2) is as follows. 1st/2nd/3rd/4th/5th/6th to 8th = 1.5/24.1/19.9/24.6/14.1/15.8. Further, (IO-1S)/(IO-2S)=2.3 (mass ratio).

The position distribution of the sulfonic acid group of the HAS form contained in each internal olefin sulfonate and the mass ratio of the olefin form and the hydroxy form (HAS form) were determined using a high performance liquid chromatograph mass spectrometer (hereinafter abbreviated as HPLC-MS). It was measured by Note that the internal olefin sulfonate having a double bond at the 6th position or higher had overlapping peaks and could not be clearly fractionated. The equipment and analysis conditions used for measurement are as follows.
〔measuring equipment〕
LC device: "LC-20ASXR" (manufactured by Shimadzu Corporation)
LC-MS device: "LCMS-2020" (manufactured by Shimadzu Corporation)
Column: ODS Hypersil (length: 250 mm, inner diameter: 4.6 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific) Detector: ESI (-), m/z = 349.15 (C18), 321. 10 (C16), 293.05 (C14)
〔solvent〕
Solvent A: 10mM ammonium acetate aqueous solution Solvent B: Acetonitrile/water = 95/5 solution to which 10mM ammonium acetate was added [Elution conditions]
・Gradient: Solvent A 60% Solvent B 40% (0-15 minutes) → Solvent A 30% Solvent B 70% (15.1-20 minutes) → Solvent A 60% Solvent B 40% (20.1-30 minutes)
・Flow rate: 0.5ml/min
・Column temperature: 40℃
・Injection volume: 5μl

[(B) component]
(b-1): After neutralizing with hydrochloric acid 1.7 g of fragrance microcapsule diisobutylene-maleic anhydride copolymer (Demol EP, solid content 25%, Kao Corporation) produced by the following method, further ionization By diluting with exchanged water, an aqueous solution with a solid content of 3% and a pH of 4.3 was obtained. Next, 36 g of a fragrance composition having the composition shown below was added to 100 g of the diisobutylene-maleic anhydride copolymer aqueous solution, emulsified using a homomixer, and the temperature was raised to 50°C. Next, an aqueous solution containing 12 g of partially methylolated melamine resin (trade name Cymel 385, solid content 80%, manufactured by Cytec Industries Inc.) and 35 g of ion-exchanged water was added dropwise.
This was held at 50°C for 2 hours, further held at 70°C for 1 hour, and further held at 80°C for 3 hours to complete the encapsulation. Thereafter, by cooling, a microcapsule slurry (b-1) with a primary average particle diameter of 7 μm and an effective content of 30% by mass was obtained. In (b-1), the proportion of the fragrance composition having the composition shown below in the microcapsule inclusions (core material) was 80% by mass.
Perfume composition: A perfume composition containing the following perfume ingredients. The numbers in parentheses are parts by mass of each fragrance ingredient when the total of each fragrance ingredient is 1000 parts by weight. Limonene (80), 1,8-cineole (30), γ-undecalactone (50), geraniol (20), terpineol (20), tetrahydrolinalool (50), methyl dihydrojasmonate (120), geranyl acetate ( 55), o,t-butylcyclohexyl acetate (100), tricyclodecenyl propionate (70), Lilial (50), hexyl cinnamic aldehyde (100), α-ionone (80), β-ionone (20) ), γ-methylionone (50), isoE super (60), δ-damascone (2), ambroxane (3), cis-3-hexenyl salicylate (40)

[(C) component]
(c-1): Propylene glycol (c-2): Diethylene glycol monobutyl ether (Wako Pure Chemical Industries, Ltd.)
(c-3): 2-phenoxyethanol (Wako Pure Chemical Industries, Ltd.)

[(D) component]
(d-1): Monoethanolamine

[(E) component]
(e-1): Polyoxyalkylene lauryl ether (per 1 mole of lauryl alcohol, after adding an average of 9 moles of ethyleneoxy groups, adding an average of 2 moles of propyleneoxy groups, and then adding an average of 9 moles of ethyleneoxy groups) molar addition compound, HLB = 14.5, in the general formula (e1), R ^1e : lauryl group, m: 0, AO: ethyleneoxy group and propyleneoxy group, n: 20, R ^2e : hydrogen atom compound)
(e-2): Polyoxyethylene lauryl ether (average number of added moles of oxyethylene group is 10 moles, HLB=14.0, in general formula (e1), R ^1e : lauryl group, m: 0, AO: ethylene Oxy group, n: 10, ^R2e : hydrogen atom compound)

[(F) component]
(f-1): Sodium alkylbenzenesulfonate (alkyl composition: C10/C11/C12/C13 = 11/29/34/26 (mass ratio, the number after C means the number of carbon atoms), mass average carbon number = 17.75)

[(G) component]
(g-1): Flavor composition shown in Table 1

[(H) component]
(h-1): Hydrogenated castor oil

〔water〕
ion exchange water

<Preparation of liquid detergent composition>
A liquid detergent composition shown in Table 2 was prepared using the above-mentioned ingredients, and the following items were evaluated. The results are shown in Table 2. The method for preparing the liquid detergent composition shown in Table 2 was specifically as follows.
A 5 cm long Teflon (registered trademark) stirrer piece was placed in a 200 mL glass beaker and its mass was measured. Next, add 80 g of ion-exchanged water at 20°C, component (C), component (A), component (F), component (D), and component (E) in this order, and then cover the top of the beaker with Saran wrap (registered trademark). The beaker containing the contents was placed in a 60°C water bath set on a magnetic stirrer, and stirred at 100 r/min for 30 minutes while the water temperature in the water bath was within a temperature range of 60±2°C. Thereafter, the pH was adjusted to pH 7 using an alkaline agent (monoethanolamine) or an acid agent (citric acid). Next, the water in the water bath was replaced with tap water at 5°C, and the composition in the beaker was cooled until the temperature of the composition reached 20°C. Next, remove Saran Wrap (registered trademark), add component (G), component (H), and component (B), add ion exchange water so that the mass of the contents becomes 100 g, and repeat at 100 r/min. The mixture was stirred for 30 minutes to obtain the liquid detergent composition shown in Table 2.

<Flexibility evaluation method>
(1) Pretreatment of evaluation fibers (1-1) Pretreatment of cotton knitted fabric 8 pieces of cotton knitted fabric cut in advance to 47cm x 100cm, approximately 1.7kg (manufactured by Shirozome Co., Ltd., cotton knit unsilled) (non-mercerized), 100% cotton) was cumulatively washed twice in the standard cycle of a fully automatic washing machine (NAF702P manufactured by National) (4.7 g of Emulgen 108 (manufactured by Kao Corporation), 47 L of water at the time of washing, After 9 minutes of washing, 2 rinses, and 3 minutes of spin-drying), the product was washed 3 times using only water (47 L of water, 9 minutes of washing, 2 rinses, and 3 minutes of spin-drying) in an environment of 25°C and 45% RH. It was dried for 24 hours. After drying, one piece of cotton knitted fabric was cut into 6 pieces by cutting at 1/3 of the long side and 1/2 of the short side, resulting in a total of 48 test fabrics.

(1-2) Pre-treatment of cotton towel In advance, use a nonionic surfactant (ethylene oxide adduct of lauryl alcohol (average number of added moles: 8)) to prepare a commercially available towel (Hiorie Towel, made in Japan, 100% cotton, Approximately 1.6 kg (34 cm x 86 cm x 12 sheets) was washed through the washing process of Hitachi automatic washing machine NW-6CY 5 times (4.5 g of nonionic surfactant used, standard cycle, 45 L of water, water temperature 20°C, Washing time: 10 minutes, rinsing twice). Thereafter, it was dried for one day under the conditions of 25° C. and 45% RH.

(2) Washing of evaluation fibers Pour 6.5 degrees of city water (3.5°dH, calculated using the water hardness measurement method described above, 20°C) into a National electric bucket washing machine (model number "N-BK2"). 0 L of water was added, 12 g of the liquid detergent composition shown in Table 2 was added, and the mixture was stirred for 1 minute. Thereafter, four pieces of cotton knitted fabric (approximately 140 g) or one cotton towel pretreated in the manner described above were added and washed for 10 minutes. After washing, dehydration was performed for 1 minute using a Hitachi double-layer washing machine (model number "PS-H35L"). Next, 6.0 L of the above-mentioned city water was poured into the above-mentioned bucket washing machine, and the cotton knitted fabric or cotton towels that had been dehydrated in the Hitachi double-layer washing machine were added and rinsed for 3 minutes. Thereafter, similar dehydration treatment was performed for 1 minute using a two-layer washing machine. After performing this rinsing treatment twice in total, it was left to dry under conditions of 25° C. and 45% RH for 12 hours.

(3) Evaluation of flexibility After washing, rinsing, and dehydrating using the liquid detergent composition listed in Table 2 in (2) above, dry the cotton knitted fabric or cotton towel in a room at 20°C and 65% humidity. After being sufficiently dried, the fragrance persistence was evaluated using samples that were left to dry for 24 hours. Six people who are experts in evaluating the texture of fibers gave scores based on the following criteria, and the average score of the six people was calculated. At that time, one evaluator obtained the cotton stockinette score and the cotton towel score for each composition, and the average value thereof was taken as the evaluation score for that composition. The evaluation scores of six people were totaled and the average score was calculated. The results are shown in Table 2. An average score of 0.5 points or more indicates superiority, and an average score of 1 point or more clearly indicates superiority, and higher values are preferable.
-1...The finish is less soft than the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
0: Finished with softness equivalent to that of the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
1...The finished product was slightly softer than the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
2...The finished product was softer than the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
3...The finished product was extremely soft compared to the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.

(4) Evaluation of scent persistence After washing, rinsing, and dehydrating using the liquid detergent composition listed in Table 2 in (2) above, dry cotton stockinette or cotton towels in a room at 20°C and 65% humidity. Persistence of fragrance was evaluated using samples that were dried and left to dry for a total of 48 hours even after being sufficiently dried. The fragrance of the cotton knitted fabric or cotton towel was scored by six experts in this evaluation based on the following criteria, and the average score of the six people was calculated. At that time, one evaluator obtained the cotton stockinette score and the cotton towel score for each composition, and the average value thereof was taken as the evaluation score for that composition. The evaluation scores of six people were totaled and the average score was calculated. The results are shown in Table 2. An average score of 0.5 points or more indicates superiority, and an average score of 1 point or more clearly indicates superiority, and higher values are preferable.
-1...The fragrance was weaker than that of the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
0...The fragrance was equivalent to that of the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1.
1...Compared to the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1, the fragrance was slightly stronger.
2...Compared to the cotton knitted fabric or cotton towel treated with the composition of Comparative Example 1, the scent was stronger.
3...Compared to the cotton stockinette or cotton towel treated with the composition of Comparative Example 1, the scent was very strong.

As shown in Table 2, the liquid detergent composition of the example using component (A) containing a predetermined amount of component (A1) can finish fibers with softness and enhanced fragrance persistence.
Note that the liquid detergent composition of the example can clean stains attached to fibers.

Claims (4)

(A) internal olefin sulfonate [hereinafter referred to as component (A)] from 1% by mass to 50% by mass; (B) microcapsules encapsulating a fragrance composition from 0.01% by mass to 2% by mass; (C) A liquid detergent composition containing 3% by mass or more and 30% by mass or less of an organic solvent having a hydroxyl group [hereinafter referred to as component (C)] and water ,
(C) component is one or more organic solvents selected from the following components (C2) to (C4),
Liquid detergent composition .
(C2) Component: Alcohol with a carbon number of 2 or more and 12 or less and a valence of 2 or more and 12 or less
(C3) Component: Organic solvent containing a hydrocarbon group, an ether group, and a hydroxyl group having 1 to 8 carbon atoms (however, hydrocarbon groups exclude aromatic groups)
(C4) Component: Organic solvent having an aromatic group, an ether group, and a hydroxyl group that may be partially substituted The liquid detergent composition according to claim 1, wherein the proportion of (A1) internal olefin sulfonate having 18 carbon atoms [hereinafter referred to as component (A1)] in component (A) is 80% by mass or more. (A1) Component is an internal olefin sulfonate having 18 carbon atoms (IO-1S) in which a sulfonic acid group is present in the 2nd to 4th position and an internal olefin having 18 carbon atoms in which a sulfonic acid group is present in the 5th or higher position. (IO-1S)/(IO-2S), which is the mass ratio of the content of (IO-1S) and the content of (IO-2S) in the component (A1). 3. The liquid detergent composition according to claim 2, wherein 2S) is 0.5 or more and 10 or less. The liquid detergent composition according to any one of claims 1 to 3, further comprising (D) a compound selected from amines and ammonia from 0.01% by mass to 10% by mass.