JP6979831B2 - How to wash textiles and liquid cleaners - Google Patents

Description

The present invention relates to a method for washing textile products and a liquid detergent used in the washing method.

For stains that are difficult to remove by ordinary washing, a method is known in which a liquid detergent is applied to a soiled portion of an object to be washed and left to stand, and then ordinary washing is performed.
However, when the liquid detergent is applied to the object to be washed and left to stand, the water and the solvent in the liquid detergent evaporate, and the liquid detergent is concentrated on the object to be washed. As a result, when the object to be washed comes into contact with water during washing, the liquid detergent may gel and the sufficient detergency may not be exhibited. Therefore, the leaving time from applying the liquid detergent to the object to be washed until washing is usually about 5 minutes.
For example, Patent Documents 1 and 2 describe an example in which a liquid detergent is applied to a stain on meat sauce, left for 5 minutes, and then washed in water.

Japanese Unexamined Patent Publication No. 2015-193859 Japanese Unexamined Patent Publication No. 2015-25062

However, the conventional method has insufficient cleaning performance for stubborn stains such as ink stains on oil-based pens and ballpoint pens.
An object of the present invention is to provide a washing method and a liquid detergent capable of improving the cleaning performance of stains which are difficult to remove by the conventional method.

The present invention has the following aspects.
[1] A liquid detergent containing a surfactant containing a nonionic surfactant (A) (excluding higher fatty acid salts) and a water-miscible organic solvent (C1) having an SP value of less than 12, as a textile product. A method for washing textile products, which is applied to a cloth, left to stand for 30 minutes or more, and then brought into contact with water for washing.
[2] The method for washing a textile product according to [1], wherein the liquid detergent contains a water-miscible organic solvent (C2) having an SP value of 12 or more.
[3] The liquid detergent contains a compound (B) selected from higher fatty acids and salts thereof, and the mass ratio of the component (A) / the component (B) is 1 to 35, [1] or [2]. How to wash textile products.
[4] The method for washing a textile product according to any one of [1] to [3], wherein the total content of the surfactant is 40% by mass or more with respect to the total mass of the liquid detergent.
[5] A liquid detergent for coating used in the method for washing textile products according to any one of [1] to [4].

[6] The liquid detergent contains the surfactant, the component (C1), and water, and the content of the component (A) is 5 to 80% by mass with respect to the total mass of the liquid detergent. The content of the component (C1) is 1 to 10% by mass, the content of water is 5% by mass or more, and the total content of the surfactant is 40 to 80% by mass, [1. ] How to wash textile products.
[7] The liquid detergent contains the surfactant, the component (C1), a water-miscible organic solvent (C2) having an SP value of 12 or more, and water, with respect to the total mass of the liquid detergent. The content of the component (A) is 5 to 80% by mass, the content of the component (C1) is 1 to 10% by mass, and the content of the component (C2) is 1 to 10% by mass. The method for washing a textile product according to [1], wherein the water content is 5% by mass or more and the total content of the surfactant is 40 to 80% by mass.
[8] The liquid cleaning agent contains the surfactant, the component (C1), a compound (B) selected from a higher fatty acid and a salt thereof, and water, based on the total mass of the liquid cleaning agent. , The content of the component (A) is 5 to 80% by mass, the content of the component (C1) is 1 to 10% by mass, the content of the component (B) is 1 to 10% by mass, and water. The method for washing a textile product according to [1], wherein the content of the above is 5% by mass or more and the total content of the surfactant is 40 to 80% by mass.
[9] The liquid cleaning agent is a compound (B) selected from the surfactant, the component (C1), a water-miscible organic solvent (C2) having an SP value of 12 or more, a higher fatty acid and a salt thereof. The content of the component (A) is 5 to 80% by mass and the content of the component (C1) is 1 to 10% by mass with respect to the total mass of the liquid cleaning agent. C2) The content of the component is 1 to 10% by mass, the content of the component (B) is 1 to 10% by mass, the content of water is 5% by mass or more, and the total content of the surfactant is contained. The method for washing a textile product according to [1], wherein the amount is 40 to 80% by mass.
[10] The method for washing textile products according to [1], wherein the stain is a stain caused by ink, foundation, lipstick, sebum, solid fat, food spill (curry, ketchup, sauce), blood, or yellowing.
[11] The method for washing textile products according to [1], wherein a rinsing treatment is performed once after the washing treatment.

According to the liquid cleaning agent of the present invention, it is possible to improve the cleaning performance of stains that are difficult to remove by the conventional method.
The liquid detergent of the present invention is used in the washing method of the present invention, and can improve the cleaning performance of stains which are difficult to remove by the conventional method.

It is a front view which shows an example of a container.

(Liquid cleaner)
The liquid detergent used in the present invention is a composition containing a surfactant (excluding higher fatty acid salts) and the component (C1). The surfactant contains at least the component (A). The liquid detergent preferably further contains one or both of the component (B) and the component (C2).

<Ingredient (A)>
The component (A) is a nonionic surfactant.
As the nonionic surfactant, the nonionic surfactant used in the liquid detergent for textile products can be used. The component (A) may be one kind or two or more kinds in combination.
A compound represented by the following general formula (I) (hereinafter, also referred to as compound (I)) is preferable because it is difficult to gel when a liquid detergent is applied to a textile product and left for a long time.
Further, a compound represented by the following general formula (II) (hereinafter, also referred to as compound (II)) is preferable in that it is excellent in detergency for ink stains, sebum stains and the like.

R ¹ −C (= O) O − [(EO) _s / (PO) _t ] − (EO) _u −R ² ... (I)
R ^3- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (II)
In formula (I), R ¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, s represents the average number of repetitions of EO, and is a number of 6 to 20. T represents the average number of repetitions of PO, a number from 0 to 6, u represents the average number of repetitions of EO, a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxy. Represents a propylene group. When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be random polymerization or block polymerization.
In formula (II), R ³ is a hydrocarbon group having 7 to 22 carbon atoms, v represents the average number of repetitions of EO, 3 to 20, and w represents the average number of repetitions of PO. The number is ~ 6, x represents the average number of repetitions of EO, the number is 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. When w is 1 or more, in [(EO) _v / (PO) _w ], the oxyethylene group and the oxypropylene group may be random polymerization or block polymerization.
The average number of repetitions can be measured by gas chromatography or the like.

In formula (II), the number of carbon atoms of ^{R 3} is preferably 10 to 22, more preferably from 10 to 20, more preferably 10 to 18.
In the general formula (II), R ³ may be a linear hydrocarbon group, or may be a group selected from a primary hydrocarbon group of a branched chain and a secondary hydrocarbon group of a straight chain. good.
In the general formula (II), when R ³ is a linear hydrocarbon group, v + x is preferably 3 to 20, more preferably 5 to 18, further preferably 6 to 18, and particularly preferably 11 to 18. w is a number from 0 to 6, preferably 0 to 3.
In the general formula (II), when R ³ is a group selected from a primary hydrocarbon group of a branched chain and a secondary hydrocarbon group of a straight chain, v + x is particularly preferably 3 to 8, and w is 0. Is preferable.

As the compound (I), a polyoxyethylene fatty acid alkyl ester is preferable, and in particular, R ¹ in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, and R ² is a methyl group and s. A compound having = 15, t = 0 and u = 0 (hereinafter, may be referred to as MEE) is more preferable.
Polyoxyethylene fatty acid alkyl esters, especially MEE, are nonionic surfactants in which the orientation of molecules is weak and micelles are unstable in an aqueous solution system. Therefore, it is presumed that the polyoxyethylene fatty acid alkyl ester does not cause gelation at a high concentration, and even if a large amount of one type alone is blended in a liquid detergent, its solubility in water can be enhanced. .. Therefore, when a liquid detergent containing a polyoxyethylene fatty acid alkyl ester comes into contact with water, it is considered that the liquid detergent is quickly dispersed to become a cleaning liquid. In addition, the concentration of polyoxyethylene fatty acid alkyl ester in the cleaning liquid quickly becomes uniform, and the cleaning liquid with an appropriate concentration can be brought into contact with the object to be washed (textile products) from the initial stage of cleaning, resulting in high cleaning power. It is thought that it can be done.

Among the polyoxyethylene fatty acid alkyl esters, the compound (I) preferably has a narrow ratio of 20% by mass or more, which indicates the ratio of distribution of compounds having different numbers of moles of ethylene oxide. The upper limit of the narrow ratio is preferably 80% by mass or less. The narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at a low temperature may decrease. Therefore, the narrow ratio is more preferably 25 to 40% by mass.
The narrow ratio of the polyoxyalkylene type nonionic surfactant such as the polyoxyethylene fatty acid alkyl ester is a value obtained by the following formula (S).

In the formula (S), S _max indicates the number of moles of alkylene oxide added (value of s + t in the formula (I)) in the alkylene oxide adduct most abundant in the polyoxyalkylene type nonionic surfactant.
i indicates the number of moles of alkylene oxide added.
Yi indicates the ratio (mass%) of the alkylene oxide adduct in which the number of moles of the alkylene oxide added in the entire component represented by the formula (S) is i.
The narrow ratio can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.

The method for producing the polyoxyethylene fatty acid alkyl ester is not particularly limited, but for example, a method of addition-polymerizing ethylene oxide to the fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (Japanese Patent Laid-Open No. 2000-144179 (No. 2000-144179).
Suitable examples of the surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ^{3+) surface-modified with a metal hydroxide or the like.} , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.), composite metal oxide catalysts such as magnesium oxide, and fired catalysts of hydrotalcite surface-modified with metal hydroxides and / or metal alkoxides, etc. Can be mentioned.
In the surface modification of the composite metal oxide catalyst, the ratio of the metal hydroxide and / or the metal alkoxide to 100 parts by mass of the composite metal oxide is preferably 0.5 to 10 parts by mass. It is more preferable to use ~ 5 parts by mass.
The method for producing the polyoxyethylene fatty acid alkyl ester is not limited to the above-mentioned method. For example, a polyoxyethylene fatty acid alkyl ester can also be produced by a method of adding an alkylene oxide to a fatty acid alkyl ester using an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/0382869, International Publication No. 2012/028435, etc., for example, alkaline earth of carboxylic acid. Examples thereof include an alkoxylation catalyst prepared from a mixture of an alkaline earth metal salt of a metal salt and / or a hydroxycarboxylic acid and sulfuric acid or the like.

The content of the component (A) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 15 to 60% by mass, and 20 to 50% by mass with respect to the total mass of the liquid detergent. It is particularly preferable, and 25 to 35% by mass is most preferable. When the content of the component (A) is not less than the lower limit value, the detergency when applied for a long time is more excellent, and when it is not more than the upper limit value, the liquid stability of the liquid detergent is more excellent.
The component (A) preferably contains one or more selected from the group consisting of compound (I) and compound (II), and contains one or more of compound (I) and one or more of compound (II). Is even more preferable.
The total content of the compound (I) and the compound (II) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass with respect to the total mass of the component (A). preferable.
When compound (I) and compound (II) are used in combination, the content of compound (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and 20 by mass, based on the total mass of the liquid detergent. ~ 40% by mass is more preferable. The content of compound (II) is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, still more preferably 4 to 6% by mass, based on the total mass of the liquid detergent.
The mass ratio of the content represented by the compound (I) / compound (II) is preferably 0.5 to 60, more preferably 2 to 10 and even more preferably 4 to 8.
When the component (A) contains the compound (I), the ratio of MEE to the total mass of the compound (I) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and 90 to 90 to 100%. 100% by mass is more preferable.

<Ingredient (B)>
The component (B) is a higher fatty acid or a salt thereof. The "higher fatty acid" means a fatty acid having 8 to 22 carbon atoms. The component (B) contributes to the improvement of rinseability. When the rinsing property is improved, the number of rinsing treatments after the cleaning treatment can be reduced.
As the higher fatty acid, a chain monocarboxylic acid having 8 to 18 carbon atoms is preferable. Specifically, the general formula: R ^11- COOH [In the formula, R ¹¹ is an aliphatic hydrocarbon group having 7 to 17 carbon atoms. ], Examples thereof include compounds represented by.
In the above formula, ^{the aliphatic hydrocarbon group of R 11} may be linear or branched chain, linear or branched alkyl group, or linear or branched chain. Alkane group is preferred. The aliphatic hydrocarbon group of R ¹¹ has 7 to 17 carbon atoms, preferably 11 to 17 carbon atoms. When the ^{number of carbon atoms of R 11} is 7 or more, the effect of preventing recontamination is further enhanced. On the other hand, when the ^{number of carbon atoms of R 11} is 17 or less, the solubility of the component (B) in water is further enhanced.

Examples of the salt form in the component (B) include alkali metal salts, alkaline earth metal salts, amine salts, ammonium salts and the like. Examples of the alkali metal salt include sodium salt, potassium salt and the like. Examples of the alkaline earth metal salt include calcium salts and magnesium salts. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.
The component (B) may be used alone or in combination of two or more.
Further, the component (B) may be a mixture having a single chain length or a mixture having two or more chain lengths.

When the liquid detergent contains the component (B), the mass ratio of the content represented by the component (A) / the component (B) is preferably 1 to 35, more preferably 4 to 35, and 6 to 6. 35 is more preferred. When it is not more than the upper limit, good rinsing property can be easily obtained during the washing process after long-term application. When it is at least the lower limit, the stability of the liquid detergent is excellent.
The content of the component (B) is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 1 to 5% by mass with respect to the total mass of the liquid detergent. When it is at least the lower limit value, good rinsing property can be easily obtained during the washing process after long-term application. When it is not more than the upper limit, the stability of the liquid detergent is excellent.
In particular, it is preferable that the component (B) contains a coconut fatty acid or a salt thereof. The total ratio of coconut fatty acid and coconut fatty acid salt to the total mass of the component (B) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. ..

<Ingredient (C)>
The component (C) is a water-miscible organic solvent. The liquid detergent contains at least a water-miscible organic solvent (C1) having an SP value of less than 12. Further, it is preferable to contain a water-miscible organic solvent (C2) having an SP value of 12 or more.
As used herein, the water-miscible organic solvent means an organic solvent that dissolves in 1 L of ion-exchanged water at 25 ° C. in an amount of 50 g or more.
As the SP value, the value defined by the regular solution theory introduced by Hildebrand is used. Specifically, the SP value is defined by δ = (ΔH / VT) 1/2 from the molar heat of vaporization ΔH and the molar volume V. That is, it is a value calculated from ^{the parallel root (cal / cm 3} ) ^{1/2 of the} heat of vaporization required for a 1 molar volume of liquid to evaporate.
The SP value of the component (C1) is preferably 7 or more and less than 12, more preferably 8 to 10 and even more preferably 9 to 10.
The SP value of the component (C2) is preferably 12 or more and 22 or less, more preferably 12 to 18, and even more preferably 12 to 15.
Examples of the component (C1) include butanol (δ = 11.4), butyl carbitol (δ = 9.9), 3-methoxy-3-methyl-1-butanol (δ = 9.88), and ethylene glycol mono. Examples thereof include butyl ether (δ = 9.5) and methoxybutyl acetate (δ = 8.9). As the component (C1), one kind may be used, or two or more kinds may be used in combination.
Examples of the component (C2) include glycerin (δ = 21.10), ethylene glycol (δ = 16.30), propylene glycol (δ = 14.80), diethylene glycol (δ = 14.60), and ethanol (δ). = 12.92) and the like. As the component (C2), one kind may be used, or two or more kinds may be used in combination.
When the component (C1) and the component (C2) are used in combination, the difference between the SP value of the component (C1) and the SP value of the component (C2) is preferably in the range of 5 to 10, preferably in the range of 4 to 8. The inside is more preferable, and the range of 3 to 5 is further preferable. When two or more types of the (C1) component or the (C2) component are used, the maximum value and the minimum value of the difference between the SP value of the (C1) component and the SP value of the (C2) component are both within the above range. Is preferable.

The content of the component (C1) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass, and particularly preferably 4% by mass or more, based on the total mass of the liquid detergent. When it is at least the lower limit value, the detergency when applied for a long time is more excellent. The larger the content of the component (C1), the shorter the coating time (time left after applying the liquid detergent) required to exert excellent detergency.
The upper limit of the content of the component (C1) is not particularly limited, but from the viewpoint of the odor of the liquid detergent, 10% by mass or less is preferable, 8% by mass or less is more preferable, and 6% by mass or less is further preferable.
When the liquid detergent contains the component (C2), the content of the component (C2) is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and 1 to 1 to the total mass of the liquid detergent. 3% by mass is more preferable. When it is at least the lower limit value, the liquid stability of the liquid detergent is excellent. In addition, the rinsing property during the washing process after long-term application is more excellent. If it is less than the upper limit, it is excellent from the viewpoint of cost.

When the component (C1) and the component (C2) are used in combination, the total content of the component (C1) and the component (C2) is preferably 2 to 20% by mass, preferably 3 to 15% by mass, based on the total mass of the liquid detergent. The mass% is more preferable, and 5 to 10% by mass is further preferable.
The mass ratio represented by the component (C1) / the component (C2) is preferably 0.1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. When it is at least the lower limit value, the liquid stability is more excellent, and when it is at least the upper limit value, it is excellent from the viewpoint of odor.

The liquid detergent may contain a surfactant other than the component (A). For example, it may contain one or more selected from anionic surfactant (D), cationic surfactant (E), and amphoteric surfactant. It is preferable to contain one or more selected from the anionic surfactant (D) and the cationic surfactant (E).
The total content of the surfactant is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, based on the total mass of the liquid detergent. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less.
When the total content of the surfactant is not less than the lower limit of the above range, it is more excellent in terms of detergency, and when it is not more than the upper limit, it is more excellent in liquid stability.

<(D) component>
The component (D) is an anionic surfactant (excluding higher fatty acid salts).
As the anionic surfactant, an anionic surfactant conventionally used for liquid detergents for textile products and the like can be used. For example, linear alkylbenzene sulfonic acid or salt thereof; α-olefin sulfonic acid or salt thereof; linear or branched alkyl sulfate ester or salt thereof; polyoxyalkylene alkyl ether sulfate ester or salt thereof; polyoxyalkylene alkenyl Ether sulfate ester or salt thereof; Alcan sulfonic acid having an alkyl group or salt thereof; α-sulfo fatty acid ester or salt thereof; Alkyl ether carboxylic acid or salt thereof, Polyoxyalkylene ether carboxylic acid or salt thereof, Alkylamide ether carboxylic acid Or a carboxylic acid type anionic surfactant such as a salt thereof, an alkenylamide ether carboxylic acid or a salt thereof, an acylaminocarboxylic acid or a salt thereof; an alkyl phosphate ester or a salt thereof, a polyoxyalkylene alkyl phosphate ester or a salt thereof, a poly Examples thereof include a phosphate ester type anionic surfactant such as an oxyalkylene alkylphenyl phosphate ester or a salt thereof, a glycerin fatty acid ester monophosphate ester or a salt thereof.
Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolammonium and diethanolammonium.
The component (D) may be used alone or in combination of two or more.

When the liquid detergent contains the component (D), the content of the component (D) is less than 50% by mass, preferably 1 to 35% by mass, preferably 3 to 25, based on the total mass of the liquid detergent. The mass% is more preferable, and 5 to 20% by mass is further preferable. When it is at least the lower limit value, the detergency when applied for a long time is more excellent, and when it is at least the upper limit value, the stability of the liquid detergent is more excellent.

<(E) component>
The component (E) is a cationic surfactant.
Examples of the cationic surfactant include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearate dimethylaminopropylamide, and the like. Long-chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or salts thereof; aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine. Or a salt thereof; examples thereof include palmitate diethanolaminopropylamide and stearate diethanolaminopropylamide. These cationic surfactants may be used alone or in combination of two or more. Among them, capric acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearate dimethylaminopropylamide, behenic acid dimethylaminopropylamide. , Oleic acid dimethylaminopropylamide or a salt thereof is particularly preferable. Mixtures of these are also preferred.
Further, as the cationic surfactant, a known cationic surfactant can be appropriately selected and used. For example, cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, and alkylpyridinium salt can also be used.
The component (E) may be used alone or in combination of two or more.

When the liquid detergent contains the component (E), the content of the component (E) is preferably 1 to 10% by mass, more preferably 1 to 7% by mass, based on the total mass of the liquid detergent. ~ 5% by mass is more preferable. When it is at least the lower limit value, the antibacterial effect when applied for a long time is excellent, and when it is at least the upper limit value, the stability of the liquid detergent is more excellent.

<Amphoteric surfactant>
As the amphoteric surfactant, an amphoteric surfactant conventionally used for liquid detergents for textile products and the like can be used. Examples thereof include amphoteric surfactants such as alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl aminosulfonic acid type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type and phosphoric acid type. The amphoteric tenside may be used alone or in combination of two or more.

<Water>
The liquid detergent preferably contains water. The water content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on the total mass of the liquid detergent.
It is assumed that the total content of all the components contained in the liquid detergent is 100% by mass.

<(F) component>
The liquid detergent preferably contains a propylene oxide adduct (F) (polyoxypropylene glyceryl ether) of a trihydric alcohol. The mass average molecular weight of the component (F) is preferably 1500 to 6000, more preferably 2500 to 5500, and even more preferably 3000 to 5000. The component (F) contributes to foam suppression. The component (F) may be used alone or in combination of two or more.
When the liquid detergent contains the component (F), the content of the component (F) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total mass of the liquid detergent. It is preferable, and 0.6 to 2% by mass is more preferable.

<Other optional ingredients>
In addition to the above components, the liquid detergent may contain components known in the liquid detergent for textile products as long as the effects of the present invention are not impaired.
For example, the following enzymes, the following chelating agents, hydrotropic agents (eg polyethylene glycol, aromatic sulfonic acids or salts thereof, etc.), detergency builders, stabilizers, alkaline agents (eg, monoethanolamine, diethanolamine, triethanolamine, etc.) Alkanolamines, etc.), texture improvers such as silicones, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, general-purpose pigments or pigments as colorants, emulsifying agents, fragrances, pH adjustments, etc. Agents and the like can be mentioned.

(Chelating agent (metal sequestering agent))
The liquid detergent may contain a chelating agent capable of chelating metal ions.
Examples of the chelating agent include organic chelating agents, and specific examples thereof include citric acid, lactic acid, tartrate acid, oxalic acid, malic acid, gluconic acid, nitrilo triacetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, and glycol ether. Diamine tetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraamine hexaacetic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, ethane Organic phosphonic acid derivatives such as hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetraximethylenesulfonic acid. Or those salts and the like. Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetraximethylene sulfonic acid are more preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable. The chelating agent may be used alone or in combination of two or more.

(enzyme)
When the liquid detergent contains an enzyme, the detergency when applied for a long time is further improved.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, cellulase and the like.
As the protease, a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease, is preferable.
Generally, a preparation containing a protease (protease preparation) is commercially available. When preparing a liquid detergent, the protease is usually formulated using this protease preparation.
Examples of the protease preparation include the trade names Subtilise 16L, Subtilisin Ultra 16L, Subtilisin Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, and Esperase AlaseLase8, which can be obtained from Novozymes. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names Purafect L, Purafect OX, Protease L and the like available from Genecore.
As the amylase preparation, for example, trade name Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Steinzyme 12L, Steinzyme Plus 12L, which can be obtained from Novozymes, Inc .; trade name Maxa, which can be obtained from Genecoa, Inc. Amano; The product name DB-250, which can be obtained from Seikagaku Corporation, can be mentioned.
Examples of the lipase preparation include the trade names Lipex 100L and Lipase 100L available from Novozymes.
Examples of the cellulase preparation include Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endolase 5000L (trade name, manufactured by Novozymes), and Cellclean 4500T (trade name, manufactured by Novozymes). (Manufactured by the company) and the like.
Examples of the mannanase preparation include the trade name Mannaway 4L available from Novozymes.
The above-mentioned enzyme may be used alone or in combination of two or more.
The enzyme content is preferably 0.1 to 3% by mass as an enzyme preparation with respect to the total mass of the liquid detergent.

The liquid detergent is preferably contained in a container to be a liquid detergent in a container. All the components of the liquid detergent may be contained in a container to form a one-component liquid detergent, or the liquid detergent may be divided into a plurality of liquids (for example, two liquids) and each contained in the container (for example, two liquids). It may be used as a mold liquid detergent).
When using a two-component liquid detergent, the first liquid, the second liquid, and the textile product are applied to the textile product so as to be in contact with each other. Hereinafter, the total mass of the first liquid and the second liquid applied to the textile product is referred to as "total mass of liquid detergent used".

In the case of the two-component type, the mass ratio of the first liquid to the second liquid to be applied to the textile product is not particularly limited, but 3: 1 to 1: 3 is preferable from the viewpoint of ease of application, and particularly 1: 1. 1 is preferable.
The content of the component (A) is preferably 2.5 to 80% by mass, more preferably 5 to 70% by mass, based on the total mass of the first liquid and the total mass of the second liquid, respectively. 5 to 60% by mass is more preferable, and 10 to 50% by mass is particularly preferable. When it is at least the lower limit value, the detergency when applied for a long time is more excellent, and when it is at least the upper limit value, the liquid stability of the liquid detergent is more excellent.
The content of the component (C1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 1.5% by mass with respect to the total mass of the first liquid and the total mass of the second liquid. % Is more preferable, and 2% by mass or more is particularly preferable. When it is at least the lower limit value, the detergency when applied for a long time is more excellent. The larger the content of the component (C1), the shorter the coating time (time left after applying the liquid detergent) required to exert excellent detergency. The upper limit of the content of the component (C1) is not particularly limited, but from the viewpoint of the odor of the liquid detergent, 10% by mass or less is preferable, 8% by mass or less is more preferable, and 6% by mass or less is further preferable.

When the component (C2) is contained in either or both of the first liquid and the second liquid, the component (C2) is added to each of the total mass of the first liquid and the total mass of the second liquid. The content of the above is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, still more preferably 0.5 to 3% by mass. When it is at least the lower limit value, the liquid stability of the liquid detergent is excellent. In addition, the rinsing property during the washing process after long-term application is more excellent. If it is less than the upper limit, it is excellent from the viewpoint of cost.

It is preferable that either or both of the first liquid and the second liquid further contains the component (B). When both the first liquid and the second liquid contain the component (B), the composition of the component (B) in the first liquid and the composition of the component (B) in the second liquid are the same. May be different.
The content of the component (B) is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total mass of the first liquid and the total mass of the second liquid. 0.5 to 5% by mass is more preferable. When it is at least the lower limit value, good rinsing property can be easily obtained during the washing process after long-term application, and when it is at least the upper limit value, the stability of the liquid detergent is excellent.

The total content of the surfactant is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and 30 to 70 with respect to the total mass of the first liquid and the total mass of the second liquid, respectively. Mass% is more preferred. When it is at least the lower limit value, it is more excellent in terms of detergency, and when it is at least the upper limit value, it is more excellent in liquid stability.

Either or both of the first liquid and the second liquid may further contain the component (F). When both the first liquid and the second liquid contain the component (F), the composition of the component (F) in the first liquid and the composition of the component (F) in the second liquid are the same. May be different.
The content of the component (F) is preferably 0.05 to 5% by mass, more preferably 0.25 to 3% by mass, based on the total mass of the first liquid and the total mass of the second liquid. 0.3 to 2% by mass is more preferable.

The preferable ranges of the water content with respect to the total mass of the first liquid and the water content with respect to the total mass of the second liquid are preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, respectively. The above is more preferable.
In each of the first liquid and the second liquid, the total content of all the components contained in the liquid is assumed to be 100% by mass.

When the enzyme is contained in the liquid detergent, it may be contained in either the first liquid or the second liquid, or may be contained in both.

<Manufacturing method of liquid detergent>
The one-component liquid detergent is produced by mixing the component (A), the component (C1), and other components to be contained, if necessary. Further, it is preferable to store it in a container to prepare a liquid detergent in a container.
The two-component type liquid detergent is prepared by preparing the first liquid and the second liquid, respectively, by a method of mixing the components contained in each liquid, and storing each of them in a container to prepare a liquid detergent in a container. The container for accommodating the first liquid and the container for accommodating the second liquid may be separate or integrated.
The container is preferably a container in which the liquid detergent can be directly applied to the textile product from the discharge port of the container. It may be a container that can be used repeatedly, or it may be a disposable container.

<Washing method for textile products>
The washing method of the present invention is a method in which the above-mentioned liquid detergent according to the present invention is applied to stains on textile products, left for 30 minutes or more, and then brought into contact with water for washing.
By applying the liquid detergent to the textile product, the soiled portion of the textile product is impregnated with the liquid detergent, and the stain and the liquid detergent are brought into contact with each other.
When applying the liquid cleaner to textiles, it is preferable to keep the concentration of the liquid cleaner in contact with the dirt, which is why the liquid cleaner is applied directly to the dirt without immersing the textile in water. Apply. The amount of application should be greater than or equal to the amount at which the liquid detergent permeates the entire area where dirt is attached.
The leaving time after coating (hereinafter, also referred to as coating time) is preferably 30 minutes to 24 hours, more preferably 12 to 24 hours. Excellent detergency is exhibited by leaving it for 30 minutes or more. The detergency improves as the leaving time increases, and reaches a plateau in about 24 hours.

The washing treatment method may be any method as long as the textile product coated with the liquid detergent is brought into contact with at least water to transfer dirt and the liquid detergent adhering to the textile product into water and remove them. Not particularly limited. The usual washing process includes a washing process and a rinsing process. The rinsing treatment is a treatment for removing the residual liquid detergent after the cleaning treatment. After the rinsing treatment, it is dried to remove water from the object to be washed (textile product).
In the cleaning treatment, in a cleaning liquid containing water and a liquid detergent, preferably, an external force is applied to the object to be washed to transfer dirt into the cleaning liquid, and then dehydration or the like is performed to separate the object to be washed from the cleaning liquid. ..
In the rinsing treatment, after the cleaning treatment, an external force is preferably applied to the object to be washed in the rinsing water containing no liquid detergent to transfer the remaining liquid detergent into the rinsing water, and then dehydration or the like. To separate the object to be washed from the rinse water.
The cleaning process is usually performed once. The rinsing process may be performed once or may be repeated twice or more. A single rinse treatment is preferable because it saves the use of rinse water and shortens the washing time.
The method of applying an external force to the object to be washed may be, for example, a method of applying a mechanical force by a washing machine, or a method of hand washing such as scrubbing, pressing, tapping, grasping, pinching, or shaking.

At the start of the washing process (cleaning process), only water may be brought into contact with the textile product, or a cleaning liquid containing water and a liquid detergent may be used. When only water is brought into contact, the liquid detergent applied to the textile product is dispersed in the water to become a cleaning liquid. When the cleaning liquid containing water and the liquid cleaning agent are brought into contact with each other, the liquid cleaning agent applied to the textile product is dispersed in the cleaning liquid, and the concentration of the liquid cleaning agent in the cleaning liquid is increased.

The object to be washed in the washing process may include not only the textile product coated with the liquid detergent but also other textile products not coated with the liquid detergent.
As for the amount of the liquid detergent used in the cleaning treatment, the ratio of the total mass (cloth amount) of the object to be washed / the total mass of the liquid detergent is preferably 10 to 500, more preferably 10 to 300, and 10 to 100. Is even more preferable. When it is at least the lower limit value, it is excellent in rinsing property when applied for a long time, and when it is at least the upper limit value, it is more excellent in detergency of other textile products to which the liquid detergent is not applied.
All of the liquid detergents used in the washing process may be used for application to the stains on the textile products, or some may be applied to the stains on the textile products and the rest may be added during the washing process.
The amount of water used in the cleaning treatment is preferably 30 times or more, preferably 30 to 500 times, more preferably 30 to 300 times the amount of the liquid detergent used in the cleaning treatment. If it is at least the lower limit, the rinsing property is better. If it is less than the upper limit, the cleaning performance is better.

According to the washing method of the present invention, excellent detergency is exhibited by performing a washing treatment after contacting a specific liquid detergent with a stain adhering to a textile product for a long time.
Examples of textile products include clothing, cloths, sheets, curtains and the like. The material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.
The washing method of the present invention is particularly preferably applied to stains that are difficult to remove by conventional washing methods. For example, it is suitable for removing stains caused by ink, foundation, lipstick, sebum, solid fat, food spills (curry, ketchup, sauce), blood, yellowing and the like.

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

(Raw materials used)
<Ingredient (A)>
A-1 (MEE): Fatty acid methyl ester ethoxylate (fatty acid having 12 to 14 carbon atoms, average number of added moles of EO is 15), in the above general formula (I), R ¹ = alkyl group having 11 carbon atoms and carbon number. 13 alkyl groups, R ² = methyl groups, s = 15, t = 0, u = 0. Synthesized by the following synthesis method. Narrow rate 30%.
A-2 (AE (15)): Natural alcohol with 15 mol of ethylene oxide added. In the above general formula (II), R ³ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 15, w = 0, x = 0. Synthesized by the following synthesis method.
A-3 (AE (10)): Natural alcohol with 10 mol of ethylene oxide added. In the above general formula (II), R ³ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 10, w = 0, x = 0. Synthesized by the following synthesis method.
A-4 (EO / PO nonion): Natural alcohol (12 carbons by mass ratio / 14 carbons = 7/3), ethylene oxide equivalent to 8 mol, propylene oxide equivalent to 2 mol, ethylene oxide equivalent to 8 mol Is added in this order as a block. In the above general formula (II), R ³ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, x = 8.
A-5: A secondary alcohol having 12 to 14 carbon atoms to which ethylene oxide equivalent to 7 mol is added. Product name "Softanol 70" manufactured by Nippon Shokubai. In the above general formula (II), R ³ = a secondary alkyl group having 12 to 14 carbon atoms, v = 7, w = 0, x = 0.
A-6: An average of 6 mol of ethylene oxide is added to a mixture (mass ratio C12OH / C14OH = 75/25) of a primary alcohol (C12OH) having 12 carbon atoms and a primary alcohol (C14OH) having 14 carbon atoms. What I did. Product name "Leox CL-60" manufactured by Lion. In the above general formula (II), R ³ = a primary alkyl group having 12 carbon atoms or a primary alkyl group having 14 carbon atoms, v = 6, w = 0, x = 0.

<Ingredient (B)>
B-1: Palm fatty acid, manufactured by NOF Corporation, trade name "palm fatty acid".
B-2: Palmitic acid, manufactured by NOF CORPORATION, trade name "NAA-160".
<(C1) component>
C1-1: 3-Methoxy-3-methyl-1-butanol, manufactured by Kuraray, trade name "Solfit (fine grade)".
C1-2: Butyl carbitol (diethylene glycol monobutyl ether), manufactured by Nippon Embroidery Co., Ltd., trade name "butyl diglycol".
<(C2) component>
C2-1: Ethanol, manufactured by Japan Alcohol Trading Co., Ltd., trade name "Specific alcohol 95 degree synthesis".
C3-2: Propylene glycol, manufactured by ADEKA Corporation, trade name "Propylene glycol".

<Component (D): Anionic surfactant>
D-1: Linear alkylbenzene sulfonic acid (LAS) (manufactured by Lion, trade name "Rypon LH-200").
D-2: Polyoxyalkylene alkyl ether sulfate ester salt (AES), (mixture of polyoxyethylene lauryl ether sulfate ester sodium and polyoxyethylene myristyl ether sulfate ester sodium, average number of moles of EO 1).
D-3: Monoethanolamine salt (AEPS) of polyoxyalkylene alkyl ether sulfate ester. Synthesized by the following synthesis method.
<Component (E): Cationic surfactant>
E-1: Dialkyldimethylammonium salt (alkyl group having 14 carbon atoms), manufactured by Kao Corporation, trade name "Cotamin D2345P".
<(F) component>
-PPG4000: Propylene oxide adduct of trihydric alcohol (polyoxypropylene glyceryl ether, manufactured by Mitsui Chemicals, Inc., trade name "Actcol T-4000", mass average molecular weight 4000.
<Water>
-Purified water: Made by Kanto Chemical Co., Inc.

<Other optional ingredients>
-Paratoluenesulfonic acid: Made by Kyowa Hakko Kogyo Co., Ltd., trade name "PTS acid".
-Sodium lactate: Made by Kanto Chemical Co., Inc., trade name "sodium lactate".
-MGDA: Methylglycine 2 sodium acetate, manufactured by BASF, trade name "Trilon M Liquid".
-Calcium chloride: Made by Kanto Chemical Co., Inc., trade name "calcium chloride".
-Na benzoate: Made by Toagosei Co., Ltd., trade name "sodium benzoate".
Perfume: Perfume composition A according to Tables 11 to 18 of JP-A-2002-146399.
-Soil release polymer: manufactured by Clariant Japan, trade name "TexCare SRN-170C", mass average molecular weight = 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C) = 4, viscosity (20 ° C) = 300 mPa · s) .. TexCare SRN-170C is a 70% by mass aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, mass average molecular weight: 2000 to 3000).
HP-20: Ethylene oxide adduct of polyethyleneimine, manufactured by BASF, trade name "Sokalan HP20".
-Sodium hydroxide: Made by Tsurumi Soda Co., Ltd., trade name "sodium hydroxide".
-Alcalase: Protease preparation manufactured by Novozymes, trade name "Alcalase 2.5L".
-Dye: Made by Ayumi Kaseisha, product name "Green No. 3".
-Citric acid: "Anhydrous citric acid" manufactured by Fuso Chemical Industry.
-Monoethanolamine: Made by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
-Sodium hydrogen carbonate: Made by Kanto Chemical Co., Inc., trade name "sodium hydrogen carbonate".
2H-08: 2-ethylhexyl isooctylate, manufactured by Lion Specialty Chemicals, trade name "2-ethylhexyl isooctylate".
-Sokalan CP9: Sodium salt copolymer of olefin and maleic acid, manufactured by BASF, trade name "Sokalan CP9".
-Blue HP: Dye, manufactured by Milliken, trade name "LIQUITINT Blue HP".
-Yellow No. 203: Dye, manufactured by Chuo Synthetic Chemical Co., Ltd., trade name "Yellow No. 203".
-BIT: 1,2-benzisothiazolin-3-one, manufactured by Clariant Japan, trade name "NIPACIDE BIT 20".

<Synthesis of MEE>
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Composition _{2.5MgO · Al 2 O 3 · zH} 2 O in which alumina hydroxide magnesium (manufactured by Kyowa Chemical Industry Co., Ltd., trade name "Kyoward 300") for 1 hour at 600 ° C., and calcined in a nitrogen atmosphere A fired alumina-magnesium hydroxide (unmodified) catalyst was obtained. 2.2 g of calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged into a 4 L autoclave. The catalyst was modified in the room. Then, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, and the reaction was carried out with stirring.
The obtained reaction solution was cooled to 80 ° C., 159 g of water and 5 g each of activated clay and diatomaceous earth as filtration aids were added and mixed, and then the catalyst was filtered off to obtain MEE.

<Synthesis of AE (15EO)>
224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of a 30 mass% NaOH aqueous solution were charged in a pressure resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Next, after dehydration at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added by a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize the reaction product so that the pH of the 1% by mass aqueous solution became about 7, and AE (15EO) was added. Obtained.

<Synthesis of AE (10EO)>
AE (10EO) was obtained in the same manner as AE (15EO) except that the amount of ethylene oxide (gaseous) used was changed.

<Synthesis of AEPS>
In an autoclave equipped with a stirrer, temperature control device and automatic introduction device, a linear primary alcohol with 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity> 99 %] 640 g and 1.0 g of KOH were charged and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and then 199 g of propane-1,2-diyloxide was charged. Then, after performing an addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide was charged. Then, after performing an addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C. and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then withdrawn. An alkoxylate of 2.0 was obtained. The obtained alkoxylate was sulfated with a descending thin film reactor using SO3 gas. AEPS was obtained by neutralizing the obtained sulfated product with monoethanolamine.

(Examples 1 to 16)
Examples 1 , 3 , 5, 6, 9 , 10, 12 to 16 are Examples, Examples 4 and 8 are Comparative Examples , and Examples 7, 11, 17 and 18 are Reference Examples .
Detergency against ink stains when liquid detergents are manufactured according to the formulations shown in Tables 1 to 3 and the textile products are washed under the conditions shown in the table (application time, "H" in the table is "time"). And rinseability was evaluated by the following method. The usability of the liquid detergent was evaluated by the following method. The results are shown in the table.
The liquid detergent was produced by adding the components (A) to (F) and other optional components to water and mixing them according to the formulation shown in the table.
The table shows the values a to f below for the liquid detergents of each example.
a: mass ratio of (A) component / (B) component, b: total content of (A) component, c: total content of (D) component, d: total content of surfactant, e: Total content of (C1) component and (C2) component, f: (C1) component / mass ratio of (C2) The unit of content in the table is "mass%", converted to pure content. Indicates the amount. Blanks in the table mean that the ingredient is not blended (hereinafter, the same applies).

(Examples 17 to 22)
Examples 17 to 22 are examples. A liquid detergent was produced in the same manner as in Example 1 with the formulations shown in Table 4, and each of them was contained in a container to produce a cleaning agent in a container. With respect to the obtained cleaning agent in a container, the detergency and rinsing property against ink stains were evaluated in the same manner as in Example 1. The results are shown in the table.
The composition of the liquid detergents of Example 15 and Example 19 is the same.

In Examples 17 and 18, the coating container (capacity: 250 g) shown in FIG. 1 was filled with a liquid detergent. In the coating container of this example, the sponge head 1 is attached to the discharge port of the container body 2. Reference numeral 3 in the figure indicates a cap. When using the cleaning agent in a container of this example, the liquid cleaning agent in the container body 2 is impregnated into the sponge head 1 and the sponge head 1 is brought into contact with the textile product to directly apply the liquid cleaning agent to the textile product. do.
In Example 19, a bag-shaped container (Patent No. 4246760, the container shown in FIG. 1) was filled with a liquid detergent. When using the cleaning agent in a container of this example, the liquid cleaning agent is discharged from the opening formed by cutting a part of the bag and applied directly to the textile product.
Example 20 is manufactured in Example 20A by providing an accommodating portion for separately accommodating two liquids, and in two accommodating portions of a container (Japanese Patent Laid-Open No. 2013-184716, the container shown in FIG. 4) in which the two liquids are simultaneously discharged. 15 mL of the liquid detergent (first liquid) and 15 mL of the liquid detergent (second liquid) produced in Example 20B were filled, respectively. When using the cleaning agent in a container of this example, the liquid cleaning agent in the two housing portions is simultaneously discharged from the opening formed by bending the lid portion in a V shape and applied directly to the textile product.
In Example 21, 15 mL of the liquid detergent (first liquid) produced in Example 21A and the liquid detergent (second liquid) produced in Example 21B are placed in two storage portions of the same container as in Example 20. Each was filled with 15 mL.
In Example 24, a squeeze container equipped with a push-pull cap (dishwashing liquid manufactured by Lion, main body container of Charmy Magica (product name), capacity: 230 ml) was filled with a liquid cleaning agent. When using the cleaning agent in a container of this example, the liquid cleaning agent is discharged from the opening of the push-pull cap and applied directly to the textile product.

In Examples 20 and 21, the total mass of the liquid detergent used is 30 mL. The values of a to f in the total mass used in Examples 20 and 21 are shown in the table.
The values of a to d in each of the first liquid and the second liquid are as follows.
a: The mass ratio of the component (A) / the component (B) is 13.43 in Example 20A, 18.59 in Example 20B, 17.50 in Example 21A, and 18.75 in Example 21B.
b: The total of the components (A) is 27% by mass in Example 20A, 29% by mass in Example 20B, 35% by mass in Example 21A, and 15% by mass in Example 21B.
c: The total of the components (D) is 13% by mass in Example 20A, 14% by mass in Example 20B, 15% by mass in Example 21A, and 15% by mass in Example 21B.
d: The total amount of the surfactant is 40% by mass in Example 20A, 43% by mass in Example 20B, 50% by mass in Example 21A, and 30% by mass in Example 21B.

<Evaluation method>
[Ink stain cleaning power]
As evaluation cloths, 5 pieces of cotton cloth and 5 pieces of Tet cotton cut into 5 cm × 5 cm were prepared. "Tet cotton" represents a blend of Tetron® and cotton broadcloth (50% polyester / 50% cotton).
An oil-based pen (manufactured by ZEBRA, trade name "McKee extra-fine") ink was applied to the evaluation cloth to prepare an ink-stained cloth to which oil-based ink stains were attached. At this time, oil-based ink was applied to the center of the evaluation cloth so that the characters had a diameter of 2 cm.
This ink-stained cloth was washed by the following procedure.
1.0 mL of the liquid detergent of each example is applied to the ink-stained cloth so that the oil-based ink stains adhering to the ink-stained cloth become the center, left for a predetermined time, and then washed by the following washing method. Cleaned the dirt. The application time (leaving time) from the application of the liquid detergent to the start of the washing process was 5 minutes, 0.5 hours, 12 hours, or 24 hours. The washing process was started when the ink-stained cloth (or evaluation cloth) came into contact with water (hereinafter, the same applies).
Put 34L of tap water at 15 ° C and 10 sheets of the above ink-stained cloth in a fully automatic washing machine (manufactured by Toshiba, product name: AW-80VC), and put other items to be washed so that the bath ratio is 20 times. According to the standard course, the operation of washing for 10 minutes, rinsing once, and dehydration for 3 minutes was performed once, and then air-dried. The bath ratio is a ratio (unit: times) expressed by a cleaning liquid (unit: L) / object to be washed (unit: kg).
For the evaluation cloth without ink stains, the ink stain cloth before cleaning, and the ink stain cloth after cleaning, the reflectance (R) of each is measured by a color difference meter manufactured by Nippon Denshoku Co., Ltd. (product name: SE200 type). The cleaning rate (%) was calculated by the following formula.
Cleaning rate (%) = 100 × (K / S of ink-stained cloth before cleaning-K / S of ink-stained cloth after cleaning) / (K / S-evaluation cloth of ink-stained cloth before cleaning) K / S) x 100
However, K / S is a value obtained by the formula: (1-R / 100) ² / (2R / 100), and R is an evaluation cloth, an ink stain before cleaning, or an ink stain after cleaning. The reflectance (%) of the cloth.
The cleaning rate (%) was calculated for each of the 10 ink-stained cloths, the average value was calculated, and the coating cleaning ability against ink stains was evaluated based on the following criteria. When the cleaning rate (average value) was 40% or more (evaluations A to C), it was determined that the cleaning power was good.
A: The cleaning rate (average value) is 60% or more.
B: Cleaning rate (average value) is 50% or more and less than 60%.
C: Cleaning rate (average value) is 40% or more and less than 50%.
D: Cleaning rate (average value) is less than 40%.

[Rinseability]
Seven cotton cloths and tet cotton cut into 5 cm × 5 cm were prepared as evaluation cloths.
1.0 mL of the liquid detergent of each example was applied to the evaluation cloth, left for a predetermined time, and then washed by the following washing method. The coating time (leaving time) was 5 minutes, 0.5 hours, 12 hours, or 24 hours.
In a fully automatic drum-type washing machine (manufactured by Toshiba, product name: TW-4000VFL (S)), put 14 evaluation cloths and other items to be washed so that the total mass of the items to be washed is 4 kg. The washing process operation (washing → dehydration → rinsing → dehydration) was performed according to the standard course (one rinse setting), and the amount of water supplied during rinsing was recorded. The amount of water supplied during rinsing is adjusted according to the degree of foaming in the tank. The water used was tap water at 15 ° C.
A liquid detergent was applied to the evaluation cloth after drying in the same manner as described above, and after leaving it for a predetermined time, the washing treatment operation was repeated, and the washing treatment operation was performed a total of 5 times. The average value (average amount of water) of the amount of water supplied at the time of rinsing in the five washing treatment operations was calculated, and the rinsability was evaluated based on the following criteria. The smaller the average amount of water during rinsing, the better the rinsing property.
A: The average amount of water during rinsing is 10L or more and less than 25L.
B: The average amount of water during rinsing is 25L or more and less than 40L.
C: The average amount of water during rinsing is 40L or more and less than 60L.
D: The average amount of water during rinsing is 60L or more.

[Usability]
In the present specification, the usability of the liquid detergent means the usability when the liquid detergent is poured from the bottle to the cap and the liquid detergent in the cap is applied to the textile product.
In order to evaluate usability, a bottle (capacity 200 mL) containing 400 g of a liquid detergent was left in a constant temperature bath at 25 ° C. After 3 hours had passed, the bottle was taken out from the constant temperature bath, the bottle was tilted, and the contents (liquid detergent) were poured into the transparent cap. The ease of pouring the liquid detergent into the cap was evaluated by 10 panelists and scored according to the following criteria. The average score of 10 people is shown in the table.
If the liquid cleaning agent is easy to pour into the cap, the liquid cleaning agent has an appropriate fluidity, and the liquid cleaning agent in the cap can be used when applied to textile products. It is good.
(Evaluation criteria)
1 point: The ease of pouring is very poor.
2 points: Ease of pouring is a little bad.
3 points: Ease of pouring is neither.
4 points: Easy to pour is a little good.
5 points: Very easy to pour.

From the results of Tables 1 to 4, good detergency against ink stains was exhibited in Examples 1 to 3, 5 to 7, 9 to 22, and detergency was insufficient in Examples 4 and 8 as comparative examples. rice field.
Examples 1 to 4 shown in Table 1 have the same composition of the cleaning agent composition. In Example 4 in which the coating time was 5 minutes, the detergency of ink stains was insufficient, whereas in Examples 1 to 3 in which the coating times were 30 minutes, 12 hours, and 24 hours, the cleaning power was insufficient. Good detergency was exhibited, and the longer the application time, the higher the detergency.
From the results in Table 2, in Example 8 containing the component (C1), the detergency of ink stains was insufficient, whereas in Examples 5 to 7 containing the component (C1), the cleaning power was good against ink stains. Detergency was exhibited, and the higher the content of the component (C1), the higher the detergency. Further, the higher the content of the component (C1), the better the rinsing property and the usability.

Examples 9 to 11 shown in Table 3 are examples in which the content of the component (C2) is changed. From these results, it can be seen that the component (C2) contributes to the improvement of rinsability and usability.
Examples 12 to 14 shown in Table 3 are examples in which the content of the component (B) is changed. From these results, it can be seen that the component (B) contributes to the improvement of rinsing property.
Comparing Example 15 shown in Table 3 with Example 2 shown in Table 1, it can be seen that the component (F) contributes to the improvement of detergency and rinsing property.

1 Sponge head 2 Container body 3 Cap

Claims (5)

A surfactant containing a nonionic surfactant (A) and an anionic surfactant (D) (excluding higher fatty acid salts), a water-miscible organic solvent (C1) having an SP value of less than 12, and an SP value of 12 A liquid detergent containing the above water-miscible organic solvent (C2) .
The content of the component (A) is 20 to 50% by mass, the content of the component (D) is 5 to 25% by mass, and the component (C1) is based on the total mass of the liquid detergent. A method for washing textile products, in which a liquid detergent having a content of 2% by mass or more is applied to a textile product, left for 30 minutes or more, and then brought into contact with water for cleaning treatment. The total content of the component (C1) and the component (C2) is 3 to 15% by mass with respect to the total mass of the liquid detergent, and the mass ratio of the component (C1) / component (C2) is 1. 6. The method for washing a textile product according to claim 1. The textile product according to claim 1 or 2, wherein the liquid detergent contains a compound (B) selected from a higher fatty acid and a salt thereof, and the mass ratio of the component (A) / the component (B) is 1 to 35. Washing method. The method for washing a textile product according to any one of claims 1 to 3, wherein the total content of the surfactant is 40% by mass or more with respect to the total mass of the liquid detergent. A liquid detergent for coating used in the method for washing textile products according to any one of claims 1 to 4.

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