JP7561620B2 - Liquid detergents for textile products and containerized liquid detergent products - Google Patents

Description

The present invention relates to a liquid detergent for textile products and a packaged liquid detergent product.
This application claims priority based on Japanese Patent Application No. 2018-168016, filed on September 7, 2018, the contents of which are incorporated herein by reference.

Liquid detergents can be applied directly to stains on textile products such as clothing, and are therefore likely to be effective in removing stubborn, localized sebum and oil stains.
Patent Document 1 describes an example in which a liquid detergent containing a specific nonionic surfactant (a polyoxyethylene alkyl ether having an average added mole number of oxyethylene groups of 5 to 8) is applied to dark stains caused by sebum, left for 5 minutes, and then washed with a cleaning liquid containing a powder detergent.
Patent Document 2 describes an example in which a liquid detergent containing a specific nonionic surfactant (a polyoxyethylene alkyl ether having an average added mole number of oxyethylene groups of 2 to 50) is applied to black tea stains, and then the stains are washed with water.

JP 2005-132898 A JP 2009-263464 A

However, the methods of Patent Documents 1 and 2 are not necessarily sufficient, and further improvement in cleaning power is required.
In the hope of improving the cleaning power, the inventors extended the time between applying the liquid detergent of Patent Document 1 to the stained area and washing it, but found that the stained area spread more than before washing. Therefore, with conventional liquid detergents, it is necessary to apply the detergent to the stained area and then immediately carry out a cleaning process.
Furthermore, liquid detergents are required to have the stability to maintain their liquid state (liquid stability).

The present invention aims to provide a liquid detergent for textile products and a containerized liquid detergent product that have good liquid stability, excellent cleaning power, and excellent effect of suppressing the spread of dirt when applied to the item to be washed and left to dry (anti-spread of dirt).

The present invention has the following aspects.
[1] The following component (A),
A liquid detergent for textile products comprising the following component (B):
When the component (A) is composed only of the following LAS, the content of the LAS is more than 15% by mass based on the total mass of the liquid detergent for textile products,
The content of the (B) component is 3 to 20% by mass based on the total mass of the liquid detergent for textile products,
The content of the following component (C) is less than 5% by mass based on the total mass of the liquid detergent for textile products,
The content of the following (D) component is less than 10% by mass based on the total mass of the liquid detergent for textile products,
The total mass of surfactants (excluding soap) is 30% by mass or less based on the total mass of the liquid detergent for textile products;
A liquid detergent for textile products, wherein the mass ratio of the component (A) to the component (B) is 0.2 to 5.
Component (A): one or more selected from the group consisting of polyoxyalkylene alkyl ether sulfate or its salt, α-olefin sulfonic acid or its salt (AOS), alkyl sulfate or its salt (AS), linear alkylbenzene sulfonic acid or its salt (LAS), olefin form (IOS) and hydroxy form (HAS) of internal olefin sulfonic acid or its salt, and alkane sulfonic acid or its salt (SAS).
(B) Component: Sugar alcohol.
Component (C): a compound represented by the following general formula (c-1):
(D) Component: Citric acid.
R ² -O-[(EO) _s /(PO) _t ] ^-R3 ...(c-1)
In formula (c-1), ^R2 is a hydrocarbon group having 6 to 22 carbon atoms, ^R3 is a hydrogen atom, an alkyl group, or an alkenyl group, EO is an oxyethylene group, PO is an oxypropylene group, s represents the average number of repetitions of EO and is a number from 3 to 15, and t represents the average number of repetitions of PO and is a number from 0 to 6.
[2] A liquid detergent for textile products, wherein the component (A) is polyoxyalkylene alkyl ether sulfate or a salt thereof, and the mass ratio of the component (A)/the component (B) is 0.2 to 5.
[3] The liquid detergent for fabric products according to [1] or [2], wherein the component (B) is at least one of glycerin and sorbitol.
[4] The liquid detergent for textile products according to any one of [1] to [3], further comprising the following component (E):
(E) Ingredient: Soap.
[5] The liquid detergent for textile products according to [4], wherein the content of the (E) component is 0.1 to 3.0 mass % based on the total mass of the liquid detergent for textile products.
[6] The liquid detergent for textile products according to [5], wherein the content of the (E) component is 0.5 to 1.5 mass% based on the total mass of the liquid detergent for textile products.
[7] The liquid detergent for textile products according to any one of [1] to [6], wherein the content of the (A) component is 4 mass% or more based on the total mass of the liquid detergent for textile products.
[8] The liquid detergent for textile products according to [7], wherein the content of the (A) component is 7 to 25 mass % based on the total mass of the liquid detergent for textile products.
[9] The liquid detergent for textile products according to [8], wherein the content of the (A) component is 10 to 20 mass % based on the total mass of the liquid detergent for textile products.
[10] The liquid detergent for textile products according to any one of [1] to [9], wherein the mass ratio of the (A) component to the (B) component is 0.5 to 3.
[11] The liquid detergent for textile products according to [10], wherein the mass ratio of the (A) component to the (B) component is 0.8 to 2.
[12] The liquid detergent for fabric products according to any one of [1] to [11], wherein the mass ratio of total surfactants to component (C) is 5 or more.
[13] The liquid detergent for textile products according to [12], wherein the mass ratio of total surfactants to component (C) is 15 or more.
[14] The liquid detergent for textile products according to any one of [1] to [13], wherein the component (A) is a compound represented by the following general formula (a-1):
R ¹ -O-[(EO) _k /(PO) _n ] _-SO3 ^- M ⁺ ...(a-1)
In formula (a-1), ^R1 is a linear or branched alkyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, k represents the average number of repetitions of EO and is a number of 0 or more, n represents the average number of repetitions of PO and is a number of 0 to 6, and M ⁺ is a counter cation.
[15] The liquid detergent for fabric products according to [14], wherein R ¹ in the formula (a-1) is a linear alkyl group having 12 or 14 carbon atoms, k is 1, n is 0, and M is sodium.
[16] The liquid detergent for textile products according to any one of [1] to [15], wherein the content of the (C) component is 1 mass% or less based on the total mass of the liquid detergent for textile products.
[17] The liquid detergent for textile products according to [16], which does not contain the component (C).
[18] The liquid detergent for textile products according to any one of [1] to [17], wherein the content of the (D) component is 5 mass% or less based on the total mass of the liquid detergent for textile products.
[19] The liquid detergent for textile products according to [18], wherein the content of the (D) component is 1 mass% or less based on the total mass of the liquid detergent for textile products.
[20] The liquid detergent for textile products according to [19], which does not contain the component (D).
[21] The liquid detergent for textile products according to any one of [1] to [20], wherein the total mass of the surfactant is 5 to 25 mass% based on the total mass of the liquid detergent for textile products.
[22] The liquid detergent for textile products according to any one of [1] to [21], wherein the content of surfactants (other surfactants) other than the component (A) and the component (C) is 10 mass % or less based on the total mass of the liquid detergent for textile products.
[23] The liquid detergent for textile products according to [22], wherein the content of the other surfactant is 1 mass % or less based on the total mass of the liquid detergent for textile products.
[24] The liquid detergent for textile products according to [23], which does not contain any other surfactants.
[25] The liquid detergent for textile products according to any one of [1] to [24], containing 50 to 85 mass% of water based on the total mass of the liquid detergent for textile products.
[26] The liquid detergent for textile products according to any one of [1] to [25], which is used by sprinkling it on textile products.
[27] A container-packed liquid detergent product, in which the liquid detergent for fabrics according to any one of [1] to [26] is packed in a squeeze container.
[28] A method for washing textile products, comprising applying the liquid detergent for textile products according to any one of [1] to [26] to a textile product, leaving the textile product for 30 minutes or more, and then contacting the textile product with water or a cleaning liquid containing fresh detergent to carry out a cleaning treatment.
[29] The method for washing textile products according to [28], further comprising spraying the liquid detergent for textile products onto the textile products to apply the liquid detergent for textile products to the textile products.
[30] The method for washing textile products according to [29], wherein the liquid detergent for textile products contained in a squeeze container is sprayed onto the textile products in a shower-like manner.

According to the present invention, it is possible to provide a liquid detergent for textile products and a containerized liquid detergent product that have good liquid stability, excellent cleaning power, and excellent effectiveness in suppressing the spread of dirt when applied to the item to be washed and left to stand.

The present invention will be described in detail below.
In this specification, the textile product to be washed is also referred to as "item to be washed."

"Liquid cleaning agent"
The liquid detergent for textile products of the present invention (hereinafter also simply referred to as "liquid detergent (α)") is a composition containing the following components (A) and (B). The liquid detergent (α) may optionally further contain one or more of the following components (C), (D), (E) and water.

<Component (A)>
The component (A) is at least one member selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, α-olefin sulfonic acid or a salt thereof (AOS), alkyl sulfate or a salt thereof (AS), linear alkylbenzene sulfonic acid or a salt thereof (LAS), an olefin form (IOS) and a hydroxy form (HAS) of an internal olefin sulfonic acid or a salt thereof, and an alkane sulfonic acid or a salt thereof (SAS).
Of these, polyoxyalkylene alkyl ether sulfate or a salt thereof is preferred as component (A).

Examples of the polyoxyalkylene alkyl ether sulfate include a compound represented by the following general formula (a-1) (hereinafter referred to as "compound (a-1)").
R ¹ -O-[(EO) _k /(PO) _n ] _-SO3 ^- M ⁺ ...(a-1)
In formula (a-1), ^R1 is a linear or branched alkyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, k represents the average number of repetitions of EO and is a number of 0 or more, n represents the average number of repetitions of PO and is a number of 0 to 6, and M ⁺ is a counter cation.
The content of the component (a0) in formula (a-1) where k=0 and n=0 is preferably 35 to 55 mass % relative to the total mass of the component (A).

R ¹ is preferably a linear or branched alkyl group having 10 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 12 to 14 carbon atoms.
k is preferably an integer of 0 to 5, more preferably an integer of 0.1 to 2, even more preferably an integer of 0.5 to 2, and particularly preferably an integer of 0.5 to 1.5.
n is preferably 0 to 3, and more preferably 0.
k+n is preferably a number greater than 0, and more preferably 1 to 5.
When k and n are not 0, that is, when compound (a-1) has both EO and PO, EO and PO may be added in a block form or random form in [(EO) _k /(PO) _n ]. Examples of the method of adding EO and PO in a block form include a method of introducing ethylene oxide and then propylene oxide, and a method of introducing propylene oxide and then ethylene oxide. The molar distribution of ethylene oxide and propylene oxide added is not particularly limited.
Examples of the salts of polyoxyalkylene alkyl ether sulfate include alkali metal salts with sodium, potassium, etc., alkaline earth metal salts with magnesium, etc., and alkanolamine salts with monoethanolamine, diethanolamine, etc.

The AOS preferably has 8 to 24 carbon atoms.
AS preferably has 8 to 20 carbon atoms.
The LAS preferably has an alkyl group having 8 to 18 carbon atoms.
The carbon numbers of IOS and HAS are preferably each 8 to 24.
The SAS preferably has 8 to 20 carbon atoms.
Examples of the salts of α-olefinsulfonic acid, alkyl sulfate ester, linear alkylbenzenesulfonic acid, internal olefinsulfonic acid, and alkanesulfonic acid include alkali metal salts with sodium, potassium, etc., alkaline earth metal salts with magnesium, etc., and alkanolamine salts with monoethanolamine, diethanolamine, etc.

The component (A) may be a commercially available product or may be produced by a known synthesis method. When the component (A) is produced by a known synthesis method, the component (A) can be produced by reacting a polyoxyalkylene alkyl ether with sulfuric anhydride or chlorosulfonic acid.
The component (A) contained in the liquid detergent (α) may be one type or two or more types.

The content of the (A) component is preferably 4% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on the total mass of the liquid detergent (α). The content of the (A) component is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less, based on the total mass of the liquid detergent (α). The content of the (A) component is preferably 4 to 25% by mass, more preferably 5 to 25% by mass, even more preferably 7 to 25% by mass, particularly preferably 10 to 20% by mass, and most preferably 10 to 17% by mass, based on the total mass of the liquid detergent (α). When the content of the (A) component is equal to or greater than the lower limit of the above range, the anti-spreading property of dirt (especially the anti-spreading property of dirt for oily dirt) and the detergency are more excellent. When the content of the (A) component is equal to or less than the upper limit of the above range, the usability and anti-foaming property during cleaning are excellent.
However, when component (A) consists only of LAS, the content of LAS is more than 15 mass% and preferably 20 mass% or more based on the total mass of the liquid detergent (α).The content of LAS is preferably more than 15 mass% and 25 mass% or less based on the total mass of the liquid detergent (α), and more preferably 20 to 25 mass%.

<Component (B)>
Component (B) is a sugar alcohol.
The term "sugar alcohol" refers to a polyhydric alcohol obtained by reducing the aldehyde and ketone groups of a sugar to alcohol groups.
Examples of sugar alcohols include glycerin, diglycerin, polyglycerin, sorbitol, erythritol, xylitol, sorbitol (D-sorbitol), mannitol, maltitol, trehalose, etc. Among these, glycerin and sorbitol are preferred from the viewpoint of further improving the cleaning power.
The component (B) contained in the liquid detergent (α) may be one type or two or more types.

The content of the (B) component is 3% by mass or more, preferably more than 3% by mass, more preferably 4% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, based on the total mass of the liquid detergent (α). The content of the (B) component is 20% by mass or less, preferably 17% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the liquid detergent (α). The content of the (B) component is 3 to 20% by mass, preferably 4 to 20% by mass, more preferably 5 to 20% by mass, even more preferably 7 to 20% by mass, particularly preferably 7 to 17% by mass, and most preferably 10 to 15% by mass, based on the total mass of the liquid detergent (α). If the content of the (B) component is equal to or more than the lower limit of the above range, the cleaning power is improved, and if it is equal to or less than the upper limit, the dirt spread prevention property and usability are excellent.

The mass ratio (A/B ratio) represented by component (A)/component (B) is 0.2 or more, preferably 0.5 or more, and more preferably 0.75 or more. The A/B ratio is 5 or less, preferably 3 or less, and more preferably 2 or less. The A/B ratio is 0.2 to 5, preferably 0.5 to 3, and more preferably 0.75 to 2. When the A/B ratio is equal to or more than the lower limit of the above range, the composition is excellent in preventing the spread of dirt and in detergency, and when the A/B ratio is equal to or less than the upper limit of the above range, the composition is excellent in liquid stability.
In particular, when component (A) is polyoxyalkylene alkyl ether sulfate or a salt thereof, the A/B ratio is 0.2 or more, preferably 0.5 or more, and more preferably 0.75 or more. Also, the A/B ratio is 5 or less, preferably 3 or less, and more preferably 2 or less. The A/B ratio is 0.2 to 5, preferably 0.5 to 3, and more preferably 0.75 to 2. When the A/B ratio is equal to or more than the lower limit of the above range, the stain spread prevention property and detergency are excellent, and when it is equal to or less than the upper limit, the liquid stability is excellent.

<Component (C)>
The component (C) is a compound represented by the following general formula (c-1) (hereinafter referred to as “compound (c-1)”).
R ² -O-[(EO) _s /(PO) _t ] ^-R3 ...(c-1)
In formula (c-1), ^R2 is a hydrocarbon group having 6 to 22 carbon atoms, ^R3 is a hydrogen atom, an alkyl group, or an alkenyl group, EO is an oxyethylene group, PO is an oxypropylene group, s represents the average number of repetitions of EO and is a number from 3 to 15, and t represents the average number of repetitions of PO and is a number from 0 to 6.

The hydrocarbon group represented by ^R2 may be saturated or unsaturated. ^R2 is preferably a linear or branched alkyl or alkenyl group, more preferably an alkyl group.
^R2 preferably has 8 to 22 carbon atoms, more preferably has 10 to 18 carbon atoms, and further preferably has 12 to 16 carbon atoms.
The alkyl group for ^R3 preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
The alkenyl group for ^R3 preferably has 2 to 6 carbon atoms, and more preferably has 2 to 3 carbon atoms.
s is preferably 7 to 15, and more preferably 12 to 15.
t is preferably an integer of 0 to 3, and more preferably an integer of 0 to 1.
s+t is a number greater than 0, and is preferably 5-20.
When t is not 0, that is, when compound (c-1) has both EO and PO, EO and PO may be added in a block fashion or random fashion in [(EO) _s /(PO) _t ].

A smaller content of component (C) is preferred in order to prevent the spread of dirt when the liquid detergent (α) is applied to a textile product and then left to stand.
Specifically, the content of component (C) is preferably less than 5 mass % based on the total mass of the liquid detergent (α).
That is, it is preferable that the liquid detergent (α) does not contain the component (C), or that the content of the component (C) relative to the total mass of the liquid detergent (α) is more than 0 mass% and less than 5 mass%.
The content of the above component (C) is more preferably 1% by mass or less, even more preferably less than 1% by mass, particularly preferably 0.5% by mass or less, and most preferably 0.1% by mass or less.

<Other surfactants>
The liquid detergent (α) may contain one or more other surfactants that do not fall under either of the components (A) and (C).
Examples of the other surfactants include anionic surfactants other than component (A) (excluding component (E) (soap) described below), nonionic surfactants other than component (C), cationic surfactants, amphoteric surfactants, and amine oxide surfactants. These surfactants may be any surfactant known in liquid detergents. The content of the other surfactants is preferably 25% by mass or less based on the total mass of the liquid detergent (α).

Examples of nonionic surfactants other than the component (C) include compounds represented by the following general formula (c-2) (hereinafter referred to as "compound (c-2)").
R ⁴ -O- [(EO) _p / (PO) _q ] - (EO) _r -R ⁵ ... (c-2)
In formula (c-2), R ⁴ is a hydrocarbon group having 6 to 22 carbon atoms, R ⁵ is a hydrogen atom, an alkyl group or an alkenyl group, EO is an oxyethylene group, PO is an oxypropylene group, p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, the sum of p and r is a number of 16 or more, and q is a number of 0 to 10.
When p and q are not 0, that is, when compound (c-2) has both EO and PO, EO and PO may be added in a block fashion or random fashion in [(EO) _p /(PO) _q ].
The content of the compound (c-2) is preferably 25 mass % or less based on the total mass of the liquid detergent (α).

The total mass of the surfactants (excluding component (E) (soap) described below) is 30 mass% or less, preferably 4 to 30 mass%, more preferably 5 to 30 mass%, even more preferably 5 to 25 mass%, and particularly preferably 5 to 20 mass%, based on the total mass of the liquid detergent (α). When the total mass of the surfactants is equal to or more than the lower limit of the above range, the cleaning power and the ability to prevent the spread of dirt are excellent. When the total mass of the surfactants is equal to or less than the upper limit of the above range, the usability and the ability to prevent foaming during cleaning are excellent. In addition, the liquid stability is excellent.
The "total mass of surfactants" refers to the total mass of component (A), component (C), and other surfactants.

The content of the other surfactant is preferably 25% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 1% by mass or less, based on the total mass of the liquid detergent (α). The content of the other surfactant may be zero.
The content of the (A) component is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and very preferably 100% by mass. Also, when the (A) component is polyoxyalkylene alkyl ether sulfuric acid or its salt, the content of the polyoxyalkylene alkyl ether sulfuric acid or its salt is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and very preferably 100% by mass, based on the total mass of the surfactant.
The mass ratio (total surfactant/C ratio) represented by the total surfactant/(C) component is preferably 5 or more, more preferably 10 or more, and even more preferably 15 or more. If it is equal to or more than the lower limit of the above range, the dirt spread prevention property is more excellent. Here, "total surfactant" refers to all surfactants contained in the liquid detergent (α) (excluding the (E) component (soap) described later). The total surfactant/C ratio is preferably 80 or less, more preferably 70 or less, even more preferably 50 or less, and particularly preferably 30 or less.

<Component (D)>
Component (D) is citric acid.
As the citric acid, any citric acid used in general liquid detergents can be used.

The content of the component (D) is less than 10% by mass relative to the total mass of the liquid detergent (α). That is, the liquid detergent (α) may include an embodiment in which the component (D) is not contained, or an embodiment in which the content of the component (D) relative to the total mass of the liquid detergent (α) is more than 0% by mass and less than 10% by mass.
The content of the above component (D) is more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less. When the content of the component (D) is equal to or less than the upper limit of the above range, the liquid stability is excellent.
When the liquid detergent (α) contains the component (D), the content of the component (D) is preferably 0.1 mass% or more, more preferably 0.4 mass% or more. When the content of the component (D) is equal to or more than the lower limit of the above range, the viscosity of the liquid detergent (α) can be easily adjusted to a viscosity that is excellent in usability while maintaining the liquid stability.

<Component (E)>
Component (E) is a soap.
As the soap, any soap used in general liquid detergents can be used, among which higher fatty acids having 10 to 20 carbon atoms and salts thereof are preferred, and higher fatty acids having 12 to 18 carbon atoms and salts thereof are more preferred.
The higher fatty acids constituting the soap may be saturated fatty acids, unsaturated fatty acids, or mixtures of saturated and unsaturated fatty acids. Examples of higher fatty acids include stearic acid, linoleic acid, oleic acid, coconut fatty acid, etc.
Examples of salts of higher fatty acids include alkali metal salts with sodium, potassium, etc., alkaline earth metal salts with magnesium, etc., and alkanolamine salts with monoethanolamine, diethanolamine, etc.

The content of component (E) is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.0% by mass, and even more preferably 0.5 to 1.5% by mass, based on the total mass of the liquid detergent (α). When the content of component (E) is equal to or greater than the lower limit of the above range, the foaming prevention properties during cleaning are excellent, and when the content is equal to or less than the upper limit of the above range, the liquid stability is excellent.

<Water>
The liquid detergent (α) preferably contains water.
The water content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the liquid detergent (α). When the water content is equal to or more than the lower limit of the above range, the liquid detergent (α) is excellent in usability and foaming prevention during cleaning. In addition, the liquid detergent (α) is easily prepared. In addition, the liquid stability is excellent. Furthermore, when the liquid detergent (α) is applied to a textile product, the liquid detergent (α) is easily sprinkled on the textile product.
The content of water is preferably 90 mass % or less, more preferably 85 mass % or less, based on the total mass of the liquid detergent (α).

<Optional ingredients>
The liquid detergent (α) may contain, in addition to the above-mentioned components (A) to (E), other surfactants, and water, any optional components known in the field of liquid detergents.
Examples of the optional components include organic solvents other than the component (B), organic acids other than the component (D), antifoaming agents, metal ion scavengers (chelating agents), enzymes, alkaline agents, pH adjusters, antioxidants, preservatives, antibacterial agents, texture improvers, dye transfer inhibitors, redeposition inhibitors, pearlizing agents, soil release agents, dispersants, hydrotropic agents, fragrances, colorants, emulsifying agents, fluorescent agents, and extracts.

Examples of organic solvents other than component (B) include ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether (butyl carbitol), polyethylene glycol, 3-methoxy-3-methylbutanol, and phenoxyethanol.
The organic solvent other than the component (B) contained in the liquid detergent (α) may be one type or two or more types.
The content of the organic solvent other than the component (B) is preferably 1 to 30% by mass based on the total mass of the liquid detergent (α).

Examples of the antifoaming agent include silicone, propylene oxide adducts of alcohols (excluding component (C) and nonionic surfactants other than component (C)), and fatty acid esters.
Examples of silicones include dimethyl silicone, polyether-modified silicone, amino-modified silicone, etc. The content of silicone is preferably 0.001 to 20% by mass based on the total mass of the liquid detergent (α).
Examples of the propylene oxide adduct of alcohol (excluding component (C) and nonionic surfactants other than component (C)) include those obtained by adding propylene oxide to monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, etc., and those obtained by adding propylene oxide to polyhydric alcohols such as diols such as ethanediol, triols such as glycerin, tetraols such as erythritol, and hexaols such as sorbitol. The content of the propylene oxide adduct of alcohol is preferably 0.1 to 10% by mass based on the total mass of the liquid detergent (α).
Examples of fatty acid esters include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctanoate, 2H08), etc. The content of fatty acid esters is preferably 0.01 to 5% by mass based on the total mass of the liquid detergent (α).

Examples of metal ion capturing agents (chelating agents) include organic phosphonic acids such as lactic acid, ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), hydroxyiminodisuccinic acid (HIDS), diethylenetriaminepentaacetic acid (DTPA), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), etc. Examples of salt forms of chelating agents include sodium, potassium, calcium, magnesium, etc.
The liquid detergent (α) may contain one type of chelating agent or two or more types of chelating agents.
The content of the chelating agent is preferably 0.001 to 10% by mass based on the total mass of the liquid detergent (α).

Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, etc. Here, "enzyme" refers to an enzyme preparation.
Examples of proteases include protease preparations available from Novozymes, such as Medley (registered trademark) Core 210L and Savinase (registered trademark) 16L.
Examples of amylase include amylase preparations available from Novozymes, such as Amplify 12L (registered trademark) and Medley (registered trademark) Core 210L (product name).
Examples of lipase include Lipex (registered trademark) 100L, which is a lipase preparation available from Novozymes.
The liquid detergent (α) may contain one type of enzyme or two or more types of enzymes.
The content of the enzyme is preferably 0.01 to 10% by mass based on the total mass of the liquid detergent (α).

Examples of the antioxidant include BHT (dibutylhydroxytoluene) and BHA (butylhydroxyanisole).
The liquid detergent (α) may contain one type of antioxidant, or two or more types of antioxidants.
The content of the antioxidant is preferably 0.01 to 3 mass % based on the total mass of the liquid detergent (α).

Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan Co., Ltd., and "NIPACIDE BIT 20" (trade name) manufactured by Clariant.
The liquid detergent (α) may contain one type of preservative or two or more types of preservatives.
The content of the preservative is preferably 0.001 to 1% by mass based on the total mass of the liquid detergent (α).

Examples of antibacterial agents include cationic disinfectants such as diclosan, triclosan, and quaternary ammonium salts (benzalkonium chloride).
The liquid detergent (α) may contain one type of antibacterial agent or two or more types of antibacterial agents.
The content of the antibacterial agent is preferably 0.001 to 10% by mass based on the total mass of the liquid detergent (α).

Examples of the soil release agent include a polymer having at least one repeating unit selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and an oxyalkylene unit. Examples of such polymers include those described in International Publication No. 2017/142012. Examples of commercially available SR agents include "TexCare SRN-170" manufactured by Clariant.
Further, as the soil release agent, a polymer (P) such as an alkylene oxide adduct of polyalkyleneamine can be mentioned. Examples of the alkylene oxide adduct of polyalkyleneamine include those described in International Publication No. 2017/142012 and JP-A No. 2017-514967. Examples of the polymer (P) include the product name "Sokalan HP20" manufactured by BASF Corporation.
Further, examples of the soil release agent include the cationic cellulose described in JP 2019-90057 A.
The liquid cleaning agent (α) may contain one type of soil release agent or two or more types of soil release agents.
The content of the soil release agent is preferably 0.1 to 20 mass % based on the total mass of the liquid detergent (α).

Examples of the dispersant include polyacrylic acid and its salts, polymethacrylic acid and its salts, and polymeric polycarboxylic acids and their salts.
The dispersant contained in the liquid detergent (α) may be one type or two or more types.
The content of the dispersant is preferably 0.01 to 5% by mass based on the total mass of the liquid detergent (α).

The fragrance may be a fragrance raw material alone or a fragrance composition comprising a fragrance raw material, a fragrance solvent, a fragrance stabilizer, etc., and any fragrance normally used in liquid detergent compositions may be blended. Capsule fragrances may also be blended.
The liquid detergent (α) may contain one type of fragrance agent or two or more types of fragrance agents.
The content of the fragrance is preferably 0.01 to 5% by mass based on the total mass of the liquid detergent (α).

Examples of colorants include quinone-based dyes, triphenylmethane-based dyes, xanthene-based dyes, quinoline-based dyes, pyrene-based dyes, etc. In this specification, "C.I." is an abbreviation for Color Index.
The structure of each dye is listed in the "Legal Dyes Handbook" (edited by the Japan Cosmetic Industry Council) and the "Dye Handbook" (edited by the Society of Organic Synthesis).
Examples of quinone dyes include C.I. Solvent Blue 63 (C.I. Solvent Blue 63, Blue No. 403), and Milliken Corporation's Liquitint Blue HP, Liquitint Blue BL, and Liquitint Blue MC.
An example of the triphenylmethane dye is Green No. 3 (C.I. 42053).
An example of the quinoline dye is Yellow No. 203 (C.I. Acid Yellow 3).
The colorant contained in the liquid detergent (α) may be one type or two or more types.
The content of the colorant is preferably 0.1 to 100 ppm by mass based on the total mass of the liquid detergent (α).

Examples of the fluorescent agent include biphenyl-type fluorescent agents such as 4,4'-bis(2-sulfostyryl)biphenyl disodium salt, and stilbene-type fluorescent agents such as 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate.
The liquid detergent (α) may contain one type of fluorescent agent or two or more types of fluorescent agents.
The content of the fluorescent agent is preferably 0.01 to 10% by mass based on the total mass of the liquid detergent (α).

Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, etc.), ammonia, etc. Among these, from the viewpoint of liquid stability, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamines are preferred, and sulfuric acid and sodium hydroxide are more preferred.
The liquid detergent (α) may contain one type of pH adjuster or two or more types of pH adjusters.

<pH>
The pH of the liquid detergent (α) at 25° C. is preferably 5 to 9, more preferably 5.5 to 8.5, even more preferably 6 to 8, particularly preferably 6.5 to 8, and most preferably 7 to 8. When the pH of the liquid detergent (α) is within the above range, the liquid stability is excellent. In addition, it is easy to prevent the influence on textile products when the liquid detergent (α) is left to stand after application.
The pH of the liquid detergent (α) can be adjusted, if necessary, by adding a pH adjuster.
In this specification, pH refers to a value measured at 25° C. using a pH meter (product name: HM-30G, manufactured by DKK-TOA Corporation).

<Viscosity>
The viscosity (V ₂₀ ) of the liquid detergent (α) at 20° C. is preferably 5 to 200 mPa·s, more preferably 10 to 100 mPa·s, and even more preferably 15 to 60 mPa·s. When the viscosity (V ₂₀ ) of the liquid detergent (α) is equal to or greater than the lower limit of the above range, the liquid detergent (α) tends to remain on dirt adhering to the textile product when it is sprinkled on the textile product. When the viscosity (V ₂₀ ) of the liquid detergent (α) is equal to or less than the upper limit of the above range, the liquid detergent (α) tends to be sprinkled on the textile product when it is applied to the textile product.
The ratio (V ₅ /V ₂₀ ) of the viscosity (V ₅ ) at 5° C. of the liquid detergent ( _α ) to the viscosity (V 20 ) is preferably 1-4, more preferably 1-3, and even more preferably 1-2.
The viscosity of the liquid detergent (α) can be adjusted, if necessary, by the amount of solvent or hydrotrope (e.g., toluenesulfonic acid, toluenesulfonates, cumenesulfonic acid, cumenesulfonates, benzoic acid, benzoates, etc.) added, pH, etc.
In this specification, the viscosity refers to a value measured at 20°C or 5°C using a Brookfield type viscometer.

<Containerized liquid cleaning agent products>
The liquid detergent (α) is preferably contained in a container and used as a container-packed liquid detergent product.
Examples of the container include a squeeze container, a trigger container, a container with an application surface for directly applying the liquid to the textile product, etc. Among these, a squeeze container is preferred from the viewpoints of being able to apply a large amount at one time, being able to apply the liquid uniformly and quickly even over a wide area, and being able to apply the liquid pinpoint even over a narrow area.
The squeeze container has a container body that is deformed by squeezing (compression), a discharge port for discharging the liquid detergent (α) contained in the container body, and a cap attached to the mouth of the container body, and the container body is deformed by squeezing the body of the container body by hand while tilting or standing upside down, and the liquid detergent (α) is discharged from the discharge port. When the squeezed state of such a squeeze container is released, the deformation of the container body is released, and the liquid detergent (α) remaining in the discharge port is returned to the container body by the bag suction mechanism (suction mechanism) at that time. A known container can be used as the squeeze container, and for example, a known squeeze container disclosed in JP 2002-264958 A can be used.

<Production Method>
The liquid detergent (α) can be produced according to a conventional method for producing a liquid detergent. For example, when producing a liquid detergent (α) containing water, each component except the pH adjuster is added to a part of the water as a dispersion medium and mixed, and then the pH adjuster is added as necessary to adjust the pH, and the remaining water is added to make the total amount 100 mass%, to produce the liquid detergent (α). Furthermore, it is preferable to put it in a container such as a squeeze container to make it into a container-packed liquid detergent product.

The liquid detergent (α) of the present invention contains specific amounts of the above-mentioned components (A) and (B), and the contents of components (C) and (D) in the liquid detergent (α) are specified, so that the liquid stability is good, the cleaning power is excellent, and the ability to prevent the spread of dirt is excellent.

<How to use (washing method)>
In order to obtain a high detergency, the liquid detergent (α) of the present invention is applied as is to the stains on the textile product (item to be washed) without diluting it with water or the like, and then left to stand. This is suitable for a method in which the fabric is treated with a detergent and then washed.
The liquid detergent (α) is applied to the textile product, so that the soiled portion of the textile product is impregnated with the liquid detergent (α) and the soiled portion is brought into contact with the liquid detergent (α).
When applying the liquid detergent (α) to a textile product, it is preferable to contact the liquid detergent (α) with the dirt while maintaining the concentration of the liquid detergent (α). Therefore, the textile product is not immersed in water, and the dirt is removed. A liquid cleaning agent (α) is applied to the surface.

There is no particular limitation on the method of applying the liquid detergent (α) to the textile product. For example, a container-packed liquid detergent product in which the liquid detergent (α) is contained in a squeeze container, trigger container, or the like may be used, and the liquid detergent (α) may be sprinkled on the textile product by separating the nozzle of the container from the textile product (i.e., in a state in which the nozzle and the textile product are not in contact). Alternatively, a container-packed liquid detergent product in which the liquid detergent (α) is contained in a container or the like having a coating surface may be used, and the coating surface of the container may be brought into contact with the textile product to directly apply the liquid detergent (α) to the textile product. From the viewpoint of uniform and rapid application over a wide area, the method of sprinkling the liquid detergent (α) on the textile product is preferred. Among these, the method of sprinkling the liquid detergent (α) contained in a squeeze container on the textile product in a shower-like manner is particularly preferred, from the viewpoint of a large amount of application per time and uniform and rapid application over a wide area. The force of the squeeze may be adjusted according to the area of the soiled portion, and if the soiled portion is wide, the force of the squeeze may be strengthened to sprinkle the liquid detergent (α) in a shower-like manner. If the dirty area is small, reduce the squeeze force and spray the liquid detergent (α) onto the area.

The amount of liquid detergent (α) applied is preferably at least the amount that allows the liquid detergent (α) to penetrate the entire stained area. The amount of liquid detergent (α) applied is preferably at least 100% owf (amount of liquid detergent (α) applied per unit weight of textile product) by fiber weight, more preferably at least 200% owf, and even more preferably at least 300% owf. There is no particular upper limit to the amount of liquid detergent (α) applied, but an amount that is, for example, 1000% owf or less by fiber weight is preferred.

The time period for leaving the liquid detergent (α) after application to the textile product until washing is preferably 30 minutes or more, more preferably 1 hour or more, even more preferably 3 hours or more, and particularly preferably 6 hours or more. By leaving the liquid detergent (α) for 30 minutes or more, the water in the liquid detergent (α) applied to the textile product evaporates, and the liquid detergent (α) is concentrated on the textile product. As a result, the compatibility with dirt is increased, and excellent detergency is exhibited.
The liquid detergent (α) has an advantage that it can be left for a longer time than conventional detergents because of its excellent ability to prevent the spread of dirt. The time may be, for example, 24 hours or more. There is no particular upper limit to the time, but the time is preferably, for example, 168 hours (one week) or less.
The water content in the liquid detergent (α) after standing is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the liquid detergent (α), and may be 0% by mass. The water content in the liquid detergent (α) after standing can be calculated by measuring the weight of the textile product before and after standing and considering the difference (reduction) as the amount of water evaporated.

The environment during standing after application is not particularly limited, but the temperature is preferably 5 to 40° C., more preferably 10 to 35° C., and even more preferably 15 to 30° C. The humidity is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less. The lower limit of the humidity is not particularly limited, but for example, the humidity is preferably 15% or more.
There is no particular restriction on the place where it is left, and it may be placed in any place, such as a washing machine drum, a laundry basket, or a washbasin, but a place that does not trap humidity, such as a laundry basket, is more preferable.

The washing method is not particularly limited as long as it is a method in which the textile product coated with the liquid detergent (α) is brought into contact with water or a washing liquid containing a new detergent (β) to remove dirt and the liquid detergent (α) adhering to the textile product by transferring them into the water. A typical washing process includes a washing process and a rinsing process. The rinsing process is a process for removing the liquid detergent (α) remaining on the textile product after the washing process. After the rinsing process, the textile product is dried or the like to remove moisture.
In the washing treatment, the textile product is placed in a washing liquid containing water or a new detergent (β), preferably by applying an external force to the textile product to transfer the dirt into the washing liquid, and then the textile product is separated from the washing liquid by dehydration or the like.
In the rinsing process, after the cleaning process, an external force is preferably applied to the textile product in rinsing water not containing the liquid detergent (α) and the detergent (β) to transfer the liquid detergent (α) remaining in the textile product into the rinsing water, and then the textile product is separated from the rinsing water by dehydration or the like.
The washing step is usually carried out once. The rinsing step may be carried out once or may be repeated two or more times. If the rinsing step is carried out once, the amount of rinsing water used can be reduced and the washing time can be shortened, which is preferable.
The method of applying an external force to the textile product may be, for example, a method of applying mechanical force using a washing machine, or a method of hand washing such as rubbing, pressing, beating, grabbing, pinching, or shaking.

At the start of the cleaning process, the textile product may be contacted with water alone, or with a cleaning liquid containing water and a new cleaning agent (β). When the textile product is contacted with water alone, the liquid cleaning agent (α) applied to the textile product is dispersed in the water to form a cleaning liquid. When the textile product is contacted with water and a cleaning liquid containing a cleaning agent (β), the liquid cleaning agent (α) applied to the textile product is dispersed in the cleaning liquid, and the concentration of the cleaning agent components in the cleaning liquid increases.
The detergent (β) may be liquid or powder. There is no particular limitation on the detergent (β), and a known detergent for textile products can be used. In addition, the detergent (β) may be a liquid detergent (α) or a commercially available product. In particular, the detergent (β) is preferably a detergent containing polyoxyethylene fatty acid methyl ester (MEE) and polyoxyethylene alkyl ether (AE).
Commercially available products of the detergent (β) include, for example, “TOP NANOX” and “TOP CLEAR LIQUID” manufactured by Lion Corporation; “ATTACK NEO”, “ATTACK ZERO”, and “ATTACK High Penetration Biogel” manufactured by Kao Corporation; “ARIEL ION POWER GEL” and “ARIEL POWER GEL BALL” manufactured by Procter & Gamble Co., Ltd.

The textile products in the washing process may include not only textile products to which the liquid detergent (α) has been applied, but also other textile products to which the liquid detergent (α) has not been applied.
The amount of detergent used in the cleaning treatment is preferably such that the ratio of the total mass of the textile product (mass of fabric) to the total mass of the detergent (total mass of the liquid detergent (α) and the detergent (β)) is 10 to 500, more preferably 10 to 300, and even more preferably 10 to 100. When the ratio of the total mass of the textile product to the total mass of the detergent is equal to or more than the lower limit of the above range, the rinsing property is excellent when applied for a long period of time, and when it is equal to or less than the upper limit of the above range, the cleaning power of other textile products to which the liquid detergent (α) is not applied is superior.
When a liquid detergent (α) is used as the detergent (β), all of the liquid detergent (α) used in the cleaning process may be used to apply to the stains on the textile product, or a portion of the liquid detergent (α) may be applied to the stains on the textile product and the remainder may be added during the cleaning process.
The amount of water used in the cleaning treatment is preferably 50 times or more, more preferably 50 to 1500 times, and even more preferably 50 to 1000 times, the amount of the cleaning agent used in the cleaning treatment (the total mass of the liquid cleaning agent (α) and cleaning agent (β)). When the amount of water used in the cleaning treatment is equal to or more than the lower limit of the above range, the rinsing property is superior, and when the amount of water used in the cleaning treatment is equal to or less than the upper limit of the above range, the cleaning performance is superior.

According to the above-mentioned method for washing textile products, the liquid detergent (α) of the present invention is used, so that even if the liquid detergent (α) is applied to the textile product (item to be washed) and then left for a long period of time (e.g., 30 minutes or more), the spread of dirt can be suppressed and excellent cleaning power can be exhibited.

Examples of textile products include clothing, dishcloths, sheets, curtains, and pillowcases. Among these textile products, clothing and pillowcases are particularly suitable. There are no particular limitations on the material of the textile products, and they may be natural fibers such as cotton, silk, and wool, or chemical fibers such as polyester and polyamide.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.
It should be noted that Example 16 is a reference example.

"Raw materials used"
As the component (A), the compound shown below was used.
A-1: AES. Polyoxyalkylene alkyl ether sulfate (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average number of moles of EO added: 1). In formula (a-1), R ¹ is a linear alkyl group having 12 and 14 carbon atoms, k is 1, n is 0, and M is sodium. The proportion of the compound in which k is 0 and n is 0 (component (a0)) relative to the entirety of A-1 is 43 mass%. Synthesized by the method of Preparation Example 1 below.
A-2: Sodium α-olefin sulfonate (AOS), trade name "Lipolan LB-840", manufactured by Lion Corporation.
A-3: Sodium lauryl sulfate (AS), SDS, trade name "sodium dodecyl sulfate", manufactured by Wako Pure Chemical Industries, Ltd.
A-4: Sodium linear alkylbenzene sulfonate (LAS), trade name "Lipon LS-250", manufactured by Lion Corporation.
A-5: secondary sodium alkane sulfonate (SAS), product name "SAS30", manufactured by Clariant Japan.
A-6: IOS, an inner olefin sulfonate synthesized by the method described in Example 7 of JP-A-2001-247534.

As the component (B), the compound shown below was used.
B-1: Glycerin. Product name: "Glycerin for cosmetics", manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.
B-2: Sorbitol. Product name "Sorbit L-70", manufactured by Mitsubishi Corporation Foodtech Co., Ltd.

As the component (C), the compound shown below was used.
C-1: Polyoxyethylene alkyl ether (a compound represented by formula (c-1), in which R ² is an alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), R ³ is a hydrogen atom, s is 6, and t is 0), trade name "Rheox CL-60", manufactured by Lion Corporation.
C-2: Polyoxyethylene alkyl ether (a compound represented by the formula (c-1), in which R ² is an alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), R ³ is a hydrogen atom, s is 15, and t is 0), trade name "LMAO-90", manufactured by Lion Chemical Co.

As the component (D), the compound shown below was used.
D-1: Citric acid. Product name: "Anhydrous Citric Acid", manufactured by Fuso Chemical Co., Ltd.

As the component (E), the compound shown below was used.
E-1: Coconut fatty acid. Product name: "Coconut fatty acid (PKO) TC", manufactured by NOF Corporation.

As optional components, the compounds shown below were used.
[Common component X] Total 0.7% by mass
・Fragrance: 0.1% by mass.
・2-ethylhexyl isooctyl acid...0.5% by mass.
・Enzyme・・・・・・・・・・・・・・・0.1% by mass.

[Common component Y] Total 11.7% by mass
・Fragrance: 0.1% by mass.
・Enzyme・・・・・・・・・・・・・・・0.1% by mass.
Sodium cumene sulfonate: 1.5% by mass.
Phenoxyethanol: 3.0% by mass.
-AE (10EO2PO10EO)...7.0% by mass.

The common components are as follows:
Fragrance: Fragrance composition A described in Tables 7 to 14 of JP-A No. 2003-268398.
2-Ethylhexyl isooctyl acid: Trade name "2-Ethylhexyl isooctyl acid", manufactured by Lion Specialty Chemicals.
Enzyme: Product name "Medley Core 210L", manufactured by Novozymes.
Sodium cumene sulfonate: Trade name "Teikatox N5040", manufactured by Teika Corporation.
- Phenoxyethanol: Product name "Phenyl Glycol", manufactured by Nippon Nyukazai Co., Ltd.
AE (10EO2PO10EO): A compound in which 10 moles of ethylene oxide, 2 moles of propylene oxide, and 10 moles of ethylene oxide are block-added, in this order, to a natural alcohol (mass ratio of alcohol having 12 carbon atoms/alcohol having 14 carbon atoms=7/3). A compound in which, in formula (c-2), R ⁴ is an alkyl group having 12 carbon atoms (C12) and an alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=70:30), R ⁵ is a hydrogen atom, p is 10, q is 2, and r is 10.

[Other optional ingredients]
PEG: Polyethylene glycol with a weight average molecular weight of 1000. Product name "PEG#1000-L60", manufactured by Lion Corporation.
- pH adjuster: MEA (monoethanolamine (alkaline agent)), product name "monoethanolamine", manufactured by Nippon Shokubai Co., Ltd.

[Preparation Example 1: Synthesis of component (A-1)]
In a 4 L autoclave, 400 g of Procter &Gamble's CO1270 alcohol (a mixture of C12 alcohol and C14 alcohol in a mass ratio of 75/25) was charged as a raw material alcohol, and 0.8 g of potassium hydroxide catalyst was charged as a reaction catalyst, and the inside of the autoclave was replaced with nitrogen, and then the temperature was raised with stirring. Next, 91 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, and an alcohol ethoxylate was obtained by reaction.
Analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard, a detector: a flame ionization detector (FID), and a column: Ultra-1 (manufactured by HP, L25m×φ0.2mm×T0.11μm) showed that the average number of moles of ethylene oxide added in the obtained alcohol ethoxylate was 1.0. In addition, the amount of compounds to which ethylene oxide was not added (those that ultimately became component (a0)) was 43% by mass based on the total amount of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after replacing with nitrogen, 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40° C. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. This was then neutralized with an aqueous sodium hydroxide solution to obtain A-1.

"Examples 1 to 17, Comparative Examples 1 to 7"
Each component was added to water and mixed according to the composition shown in Tables 1 to 4 to prepare a liquid detergent (α) of each example.
The amounts in the table are calculated as pure contents. Components whose amounts are not shown in the table are not included. The "appropriate amount" of pH adjuster content is the amount required to adjust the pH of each liquid composition to 7 at 25°C. The "balance" water content means the remainder added so that the total of all components contained in liquid composition (α) is 100% by mass.
The liquid detergent (α) of each example was evaluated for its ability to prevent dirt from spreading, its cleaning power, and its liquid stability by the following methods. The results are shown in Tables 1 to 4.

"Evaluation Method"
<Evaluation of stain spread prevention ability>
(1) Preparation of oil-stained and soiled cloth A B. V. D. GOLD 100% cotton crew neck short sleeve T-shirt (Tanigashiro Shoten) cut to a size of 5 cm x 5 cm was used as an unsoiled cloth.
For Examples 1 to 11 and Comparative Examples 1 to 7, 0.050 mL of a sebum model soiling oil, which was a mixed oil containing oleic acid, triolein, etc. to which 0.03% by mass of Oil Red had been added, was dropped onto an unsoiled cloth, and the cloth was dried at room temperature for 1 hour to prepare an oil-stained soiled cloth.
For Examples 12 to 17, 0.050 mL of chili oil (manufactured by SB Foods Co., Ltd.) was dropped onto an unsoiled cloth, which was then dried at room temperature for 1 hour to prepare an oil-stained and soiled cloth.

(2) Evaluation of stain spread prevention properties For each of five oil-stained and soiled cloths, 0.3 mL of the liquid detergent (α) to be evaluated was sprinkled on the area where the oil had been dropped using a pipette, and the cloth was left for 12 hours in an environment of 25°C and 60% humidity to prepare a test cloth.
The length of the major axis of the oil stain was measured as the spreading diameter for the oil-stained cloth (control) before the liquid detergent (α) was applied, and the test cloth after the liquid detergent (α) was applied and left for 12 hours. The average value of the spreading diameters for the five oil-stained cloths was calculated, and the spread prevention property of the stain was evaluated according to the following criteria.
If the average spread diameter of the test fabric is A (mm) and the average spread diameter of the control is B (mm), then A-B is the "difference in the average spread diameters." If the "difference in the average spread diameters" is less than 6 mm, it is judged as passing.
(Evaluation Criteria)
I: The difference in the average value of the expansion diameter is less than 3 mm.
II: The difference in the average value of the expansion diameter is 3 mm or more and less than 6 mm.
III: The difference in the average value of the expansion diameter is 6 mm or more.

<Evaluation of cleaning power>
(1) Preparation and cleaning of oil-stained and soiled cloth 0.050 mL of a model soiled oil prepared by diluting beef tallow five-fold with chloroform and adding 0.03% by mass of oil red was dropped onto the above-mentioned unsoiled cloth, and the cloth was air-dried at room temperature for 2 hours to prepare an oil-stained and soiled cloth (before cleaning).
For each of five oil-stained and soiled cloths, 0.3 mL of the liquid detergent (α) to be evaluated was sprinkled onto the oil-dropped area using a pipette, and the cloth was left to stand for 6 hours in an environment of 25°C and 60% humidity to prepare a test cloth.
Next, the five test cloths and a charge cloth (a knitted cloth cut into small pieces, thoroughly washed, rinsed, and dried) were placed in a Terg-O-Tometer (manufactured by UNITED STATES TESTING) containing 900 mL of 15°C tap water and 0.3 g of a commercially available detergent (trade name "TOP NANOX", manufactured by Lion Corporation) and washed for 10 minutes at 120 rpm. The amount of the charge cloth was set so that the bath ratio (mass of the cleaning liquid/total mass of the charge cloth) was 20 times.
Thereafter, five test cloths after washing were taken out, rinsed with running water for three minutes in a two-tub washing machine (product number "CW-C30A1" manufactured by Mitsubishi Electric Corporation), dehydrated for one minute, and then air-dried to obtain oil-stained and soiled cloths after washing.

(2) Evaluation of cleaning power Using a colorimeter (product name "SE2000", manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance of an unsoiled cloth and an oily and soiled cloth before and after cleaning were measured, and the cleaning rate (%) was calculated according to the following formula (ii).
Cleaning rate (%)=(K/S of oily soiled cloth before cleaning−K/S of oily soiled cloth after cleaning)/(K/S of oily soiled cloth before cleaning−K/S of unsoiled cloth)×100 (ii)
[In formula (ii), K/S is (1-R/100) ² /(2R/100), R represents the reflectance (%) of the oil-stained cloth before cleaning, the oil-stained cloth after cleaning, or the unsoiled cloth. K represents the absorption coefficient, S represents the scattering coefficient, and R represents the absolute reflectance.]
The higher the cleaning rate, the stronger the cleaning power.
The average value of the cleaning rate of the five oil-stained and soiled cloths was calculated, and the cleaning power was evaluated according to the following criteria: When the average value of the cleaning rate is 65% or more, it is judged as passing.
(Evaluation Criteria)
I: The average cleaning rate is 75% or more.
II: The average cleaning rate is 65% or more and less than 75%.
III: The average cleaning rate is 55% or more and less than 65%.
IV: The average cleaning rate is less than 55%.

<Evaluation of Liquid Stability>
40 g of the liquid detergent (α) of each example was filled into a transparent glass bottle, which was then sealed with a lid, and stored in each of the thermostatic chambers at 0° C. and 50° C. for 24 hours.
After storage for 24 hours, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent (α) was evaluated according to the following criteria.
(Evaluation Criteria)
I: Colorless, transparent and fluid even after storage at 0°C and 50°C.
II: After storage at least at either 0° C. or 50° C., the occurrence of precipitation or turbidity and solidification of the content liquid were observed.

In Tables 1 to 4, "A/B ratio" is the mass ratio expressed as component (A)/component (B). "Total surfactant/C ratio" is the mass ratio expressed as total surfactant/component (C).

As shown in Tables 1 to 4, Examples 1 to 17 had good detergency and liquid stability, and were excellent in preventing the spread of dirt when the liquid detergent (α) was applied and left for a long period of time.
On the other hand, Comparative Example 1, which did not contain the component (A), was inferior in detergency and in preventing the spread of dirt.
Comparative Example 2, in which component (A) consisted only of LAS and the LAS content was 15% by mass, had poor cleaning power and was also poorer in preventing the spread of dirt than Examples 1 to 17.
The sample in Comparative Example 3, in which the content of component (B) was less than 3 mass %, had poor detergency.
Comparative Example 4, in which the content of component (C) was 5 mass % or more, was inferior in preventing the spread of dirt.
In Comparative Example 5, in which the content of component (D) was 10 mass % or more, the liquid stability was poor.
Comparative Example 6, in which the A/B ratio was less than 0.2, had poor cleaning power and was also poorer in preventing the spread of dirt than Examples 1 to 17.
Comparative Example 7, in which the A/B ratio was greater than 5, had poor liquid stability.

Claims (6)

The following component (A),
A liquid detergent for textile products comprising the following component (B):
When the component (A) is composed only of the following LAS, the content of the LAS is more than 15% by mass based on the total mass of the liquid detergent for textile products,
The content of the (B) component is 3 to 20% by mass based on the total mass of the liquid detergent for textile products,
The content of the following component (C) is less than 5% by mass based on the total mass of the liquid detergent for textile products,
The content of the following (D) component is less than 10% by mass based on the total mass of the liquid detergent for textile products,
The total mass of surfactants (excluding soap) is 30% by mass or less based on the total mass of the liquid detergent for textile products;
A liquid detergent for textile products , wherein the mass ratio of the component (A) to the component (B) is 0.2 to 5.
Component (A): one or more members selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, α-olefin sulfonic acid or a salt thereof (AOS), alkyl sulfate or a salt thereof (AS), linear alkylbenzene sulfonic acid or a salt thereof (LAS) , and alkanesulfonic acid or a salt thereof (SAS).
(B) Component: Sugar alcohol.
Component (C): a compound represented by the following general formula (c-1):
(D) Component: Citric acid.
R ² -O-[(EO) _s /(PO) _t ] ^-R3 ...(c-1)
In formula (c-1), ^R2 is a hydrocarbon group having 6 to 22 carbon atoms, ^R3 is a hydrogen atom, an alkyl group, or an alkenyl group, EO is an oxyethylene group, PO is an oxypropylene group, s represents the average number of repetitions of EO and is a number from 3 to 15, and t represents the average number of repetitions of PO and is a number from 0 to 6. The liquid detergent for textile products according to claim 1, wherein the component (A) is polyoxyalkylene alkyl ether sulfate or a salt thereof, and the mass ratio of the component (A)/the component (B) is 0.2 to 5. The liquid detergent for textile products according to claim 1 or 2, wherein the component (B) is at least one of glycerin and sorbitol. The liquid detergent for textile products according to any one of claims 1 to 3, further comprising the following component (E):
(E) Ingredient: Soap. The liquid detergent for textile products according to any one of claims 1 to 4, which is used by sprinkling it on textile products. A liquid detergent product in a container, in which the liquid detergent for textile products according to any one of claims 1 to 5 is contained in a squeeze container.