JP2018188785A - Fiber product washing method and liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a washing method capable of improving cleaning performance of dirt which is difficult to remove by a conventional method. SOLUTION: A liquid cleaning agent 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 is used as a fiber. A fiber containing a water-miscible organic solvent (C2) having an SP value of 12 or more, preferably the liquid cleaning agent is applied to stains of the product, left to stand for 30 minutes or more, and then brought into contact with water for washing treatment. How to wash the product. [Selection diagram] None

Description

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

In order to improve the washing performance against dirt that is difficult to remove by ordinary washing, a method of performing ordinary washing after applying a liquid detergent to the dirt portion of an object to be washed and leaving it to stand is known.
However, when the liquid cleaning agent is applied to the object to be cleaned and left to stand, moisture and solvent in the liquid cleaning agent are evaporated, and the liquid cleaning agent is concentrated on the object to be cleaned. As a result, when the article to be washed comes into contact with water during washing, the liquid detergent may gel, and sufficient cleaning power may not be exhibited. For this reason, the standing time from applying the liquid cleaning agent to the object to be washed until washing is usually about 5 minutes.
For example, Patent Documents 1 and 2 describe examples in which a liquid detergent is applied to meat sauce stains, left for 5 minutes, and then washed in water.

Japanese Patent Laying-Open No. 2015-193859 Japanese Patent Laying-Open No. 2015-25062

However, the conventional method has insufficient cleaning performance against stubborn stains such as ink stains such as oil-based pens and ballpoint pens.
An object of this invention is to provide the washing method which can improve the washing | cleaning performance of the stain | pollution | contamination which was hard to remove by the conventional method, and a liquid cleaning agent.

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

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

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

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

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

<(A) component>
The component (A) is a nonionic surfactant.
As a nonionic surfactant, the nonionic surfactant currently used for the liquid cleaning agent for textiles can be used. (A) A component may be 1 type and may use 2 or more types together.
A compound represented by the following general formula (I) (hereinafter also referred to as compound (I)) is preferable in that it is difficult to gel when a liquid detergent is applied to a textile product and left for a long time.
In addition, a compound represented by the following general formula (II) (hereinafter also referred to as compound (II)) is preferable in terms of excellent detergency such as ink stains and sebum stains.

_{^{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 and is a number from 0 to 6, u represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, PO is 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 the formula (II), R ³ is a hydrocarbon group having 7 to 22 carbon atoms, v represents an average number of repetitions of EO, 3 to 20, and w represents an average number of repetitions of PO. Is a number of -6, x represents the average number of repetitions of EO, is a number of 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 branched primary hydrocarbon group and a linear secondary hydrocarbon group. Good.
In the general formula (II), when R ³ is a linear hydrocarbon group, v + x is preferably 3-20, more preferably 5-18, still more preferably 6-18, and particularly preferably 11-18. 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 branched primary hydrocarbon group and a linear secondary hydrocarbon group, v + x is particularly preferably from 3 to 8, and w is 0. Is preferred.

The compound (I) is preferably a polyoxyethylene fatty acid alkyl ester, in particular, R ¹ in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ² is a methyl group, and s = 15, t = 0 and u = 0 are more preferred (hereinafter sometimes referred to as MEE).
A polyoxyethylene fatty acid alkyl ester, particularly MEE, is a nonionic surfactant having a weak molecular orientation and an unstable micelle in an aqueous solution system. For this reason, polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and it is presumed that the solubility in water can be improved even if one kind alone is blended in a large amount in a liquid detergent. . Accordingly, it can be considered that when the liquid detergent containing polyoxyethylene fatty acid alkyl ester comes into contact with water, it is quickly dispersed to form a washing liquid. In addition, the concentration of polyoxyethylene fatty acid alkyl ester in the cleaning liquid becomes uniform quickly, and the cleaning liquid and the object to be cleaned (textile products) can be brought into contact with each other from the initial stage of cleaning. As a result, high cleaning power is demonstrated. It is considered possible.

As the compound (I), among the polyoxyethylene fatty acid alkyl esters, those having a narrow ratio indicating a distribution ratio of compounds having different numbers of added moles of ethylene oxide are preferably 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less. As for a narrow rate, 20-60 mass% is more preferable. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at low temperatures may be lowered, and therefore the narrow ratio is more preferably 25 to 40% by mass.
The narrow rate of polyoxyalkylene type nonionic surfactants such as polyoxyethylene fatty acid alkyl esters is a value determined by the following mathematical formula (S).

In the formula (S), S _max represents the number of added moles of alkylene oxide (value of s + t in the formula (I)) in the alkylene oxide adduct most frequently present in the polyoxyalkylene type nonionic surfactant.
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (% by mass) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the whole component represented by formula (S).
The narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.

The production method of the polyoxyethylene fatty acid alkyl ester is not particularly limited. For example, a method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP, A 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⁺⁾ that have been surface-modified with a metal hydroxide or the like. , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a mixed metal oxide catalyst such as magnesium oxide, a hydrotalcite calcined catalyst whose surface is modified with a metal hydroxide and / or a metal alkoxide, etc. Is mentioned.
In the surface modification of the composite metal oxide catalyst, the ratio of the metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the composite metal oxide. It is more preferable to set it as -5 mass parts.
The production method of the polyoxyethylene fatty acid alkyl ester is not limited to the method described above. For example, the 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 oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like. For example, alkaline earth of carboxylic acid Examples include an alkoxylation catalyst prepared from a mixture of a metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid.

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. Particularly preferred is 25 to 35% by mass. When the content of the component (A) is not less than the lower limit, the cleaning power when applied for a long time is more excellent, and when it is not more than the upper limit, the liquid stability of the liquid detergent is more excellent.
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). More preferably.
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 90 to 100% by mass with respect to the total mass of the component (A). preferable.
When the compound (I) and the compound (II) are used in combination, the content of the compound (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, with respect to the total mass of the liquid detergent. -40 mass% is further more preferable. The content of the compound (II) is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, and further preferably 4 to 6% by mass with respect to the total mass of the liquid detergent.
0.5-60 are preferable, as for mass ratio of content represented by compound (I) / compound (II), 2-10 are more preferable, and 4-8 are more preferable.
When (A) component contains compound (I), it is preferable that the ratio of MEE is 80-100 mass% with respect to the total mass of compound (I), 85-100 mass% is more preferable, 90- 100 mass% is more preferable.

<(B) component>
Component (B) is a higher fatty acid or a salt thereof. “Higher fatty acid” means a fatty acid having 8 to 22 carbon atoms. (B) A component contributes to the improvement of rinse property. When the rinsing property is improved, the number of rinsing processes after the cleaning process 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 [wherein R ¹¹ is an aliphatic hydrocarbon group having 7 to 17 carbon atoms. ] The compound represented by this is mentioned.
In the above formula, the aliphatic hydrocarbon group for R ¹¹ may be linear or branched, linear or branched alkyl group, or linear or branched Alkenyl groups are preferred. The number of carbon atoms in the aliphatic hydrocarbon group for R ¹¹ is 7 to 17, 11 to 17 carbon atoms are preferred. When the carbon number of R ¹¹ is 7 or more, the effect of preventing recontamination is further increased. On the other hand, when the carbon number of R ¹¹ is 17 or less, the solubility of the component (B) in water is further increased.

(B) As a form of the salt in a component, an alkali metal salt, alkaline-earth metal salt, an amine salt, or an ammonium salt is mentioned. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
The component (B) may be a single chain length mixture or a mixture of two or more chain lengths.

When the component (B) is contained in the liquid detergent, the mass ratio of the content represented by the component (A) / component (B) is preferably 1 to 35, more preferably 4 to 35, and 6 to 6 35 is more preferable. When it is less than or equal to the upper limit value, good rinsing properties are easily obtained during a washing process after long-time 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 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 properties are easily obtained during the washing treatment after long-time application. If it is below the upper limit, the stability of the liquid detergent is excellent.
In particular, the component (B) preferably contains a coconut fatty acid or a salt thereof. (B) It is preferable that the sum total ratio of a coconut fatty acid and a coconut fatty acid salt is 60-100 mass% with respect to the total mass of a component, 80-100 mass% is more preferable, 90-100 mass% is further more preferable. .

<(C) component>
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. Furthermore, it is preferable to contain a water-miscible organic solvent (C2) having an SP value of 12 or more.
In the present specification, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
As the SP value, a value defined by regular solution theory introduced by Hildebrand is used. Specifically, the SP value is defined by δ = (ΔH / V−T) 1/2 from the molar evaporation heat ΔH and the molar volume V. In other words, this is a value calculated from the parallel root (cal / cm ³ ) ^{1/2 of the} heat of evaporation required for evaporating a 1 molar volume of liquid.
The SP value of the component (C1) is preferably 7 or more and less than 12, more preferably 8 to 10, and still more preferably 9 to 10.
The SP value of the component (C2) is preferably 12 or more, 22 or less, more preferably 12-18, and still more preferably 12-15.
Examples of the component (C1) include butanol (δ = 11.4), butyl carbitol (δ = 9.9), 3-methoxy-3-methyl-1-butanol (δ = 9.88), ethylene glycol mono Examples include butyl ether (δ = 9.5) and methoxybutyl acetate (δ = 8.9). As the component (C1), one type may be used, or two or more types 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), ethanol (δ = 12.92). As the component (C2), one type may be used, or two or more types 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, and in the range of 4 to 8 The inside is more preferable, and the range of 3 to 5 is more preferable. When two or more components (C1) or (C2) 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. It is preferable that

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 with respect to the total mass of the liquid detergent. When it is at least the lower limit, the detergency when applied for a long time is more excellent. The higher the content of the component (C1), the shorter the application time (the standing time after applying the liquid cleaning agent) necessary for exhibiting excellent cleaning power.
Although the upper limit of content of (C1) component is not specifically limited, From a viewpoint of the odor of a liquid detergent, 10 mass% or less is preferable, 8 mass% or less is more preferable, and 6 mass% or less is further more preferable.
When the liquid cleaning agent contains the component (C2), the content of the component (C2) is preferably 1 to 10% by mass, more preferably 1 to 8% by mass with respect to the total mass of the liquid cleaning agent. 3% by mass is more preferable. When it is at least the lower limit value, the liquid stability of the liquid detergent is excellent. Moreover, the rinse property at the time of the washing process after long-time application | coating is more excellent. It is excellent from a viewpoint of cost that it is below the upper limit.

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 with respect to the total mass of the liquid detergent, and 3 to 15 % By mass is more preferable, and 5 to 10% by mass is more preferable.
0.1-8 are preferable, as for mass ratio represented by (C1) component / (C2) component, 1-6 are more preferable, and 1-4 are more preferable. When it is at least the lower limit value, the liquid stability is more excellent, and when it is at most 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, you may contain 1 or more types chosen from an anionic surfactant (D), a cationic surfactant (E), and an amphoteric surfactant. It is preferable to include at least one selected from an anionic surfactant (D) and a cationic surfactant (E).
40 mass% or more is preferable with respect to the total mass of a liquid detergent, 50 mass% or more is more preferable, 60 mass% or more is further more preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further 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 from the viewpoint of detergency, and when it is not more than the upper limit, the liquid stability is more excellent.

<(D) component>
Component (D) is an anionic surfactant (excluding higher fatty acid salts).
As an anionic surfactant, the anionic surfactant conventionally used for liquid detergents for textiles etc. 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; alkanesulfonic acid having 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 alkenyl amide 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 And salts thereof, phosphate ester type anionic surfactants such as polyoxyalkylene alkylphenyl phosphate or salt thereof, glycerin fatty acid ester monophosphate ester or salt thereof, and the like.
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; alkanolamine salts such as monoethanolammonium and diethanolammonium.
(D) A component may be used individually by 1 type and may use 2 or more types together.

  When the component (D) is contained in the liquid detergent, the content of the component (D) is less than 50% by mass, preferably 1 to 35% by mass, and 3 to 25% with respect to the total mass of the liquid detergent. The mass% is more preferable, and 5 to 20 mass% is more preferable. When it is at least the lower limit value, the cleaning power when applied for a long time is more excellent, and when it is at most the upper limit value, the stability of the liquid cleaning agent is more excellent.

<(E) component>
(E) A component is a cationic surfactant.
Examples of cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, 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 salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like. These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. Among them, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide Particularly preferred is dimethylaminopropylamide oleate or a salt thereof. Mixtures of these are also preferred.
The cationic surfactant can be appropriately selected from known cationic surfactants. For example, cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts can also be used.
(E) A component may be used individually by 1 type and may use 2 or more types together.

  When the component (E) is contained in the liquid detergent, the content of the component (E) is preferably 1 to 10% by mass, more preferably 1 to 7% by mass with respect to the total mass of the liquid detergent. -5 mass% is further 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 most the upper limit value, the stability of the liquid detergent is more excellent.

<Amphoteric surfactant>
As the amphoteric surfactant, amphoteric surfactants conventionally used for liquid detergents for textile products and the like can be used. Examples thereof include amphoteric surfactants such as alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type or phosphoric acid type. An amphoteric surfactant may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

<Water>
The liquid detergent preferably contains water. 5 mass% or more is preferable with respect to the total mass of a liquid detergent, 10 mass% or more is more preferable, and 20 mass% or more is further more preferable.
In addition, the sum total of content of all the components contained in a liquid detergent shall be 100 mass%.

<(F) component>
The liquid detergent preferably contains a propylene oxide adduct (F) (polyoxypropylene glyceryl ether) of a trihydric alcohol. (F) As for the mass mean molecular weight of a component, 1500-6000 are preferable, 2500-5500 are more preferable, 3000-5000 are more preferable. The component (F) contributes to foam suppression. (F) A component may be used individually by 1 type and may use 2 or more types together.
When the component (F) is contained in the liquid detergent, the content of the component (F) is preferably 0.1 to 5% by mass and more preferably 0.5 to 3% by mass with respect to the total mass of the liquid detergent. Preferably, 0.6 to 2% by weight is more preferable.

<Other optional components>
In addition to the above-mentioned 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, hydrotropes (eg, polyethylene glycol, aromatic sulfonic acid or salts thereof), detergency builders, stabilizers, alkali agents (eg, monoethanolamine, diethanolamine, triethanolamine) Etc.), texture improvers such as silicone, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, general-purpose dyes or pigments as colorants, emulsifying agents, perfumes, pH adjustment Agents and the like.

(Chelating agent (metal sequestering agent))
The liquid detergent may contain a chelating agent that can chelate metal ions.
Examples of chelating agents include organic chelating agents. Specifically, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 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, ethylenediaminetetraxymethylenesulfonic acid Or the salt etc. are mentioned. Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetraxymethylenesulfonic acid are more preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable. A chelating agent may be used individually by 1 type, and may use 2 or more types together.

(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.
The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease.
In general, a preparation containing a protease (protease preparation) is commercially available. In preparing the liquid detergent, the protease is usually formulated using this protease preparation.
Examples of protease preparations include, but are not limited to, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Evaluse Ultra 16L, Esperase Ultra 16L, Esperase Ultra L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names Purefect L, Purefect OX, Properase L, etc. available from Genencor.
Examples of the amylase preparation include, for example, trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stayzyme 12L, and Steinzyme Plus 12L available from Genencore; Amano; trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase preparation include trade names Lipex 100L and Lipolase 100L available from Novozymes.
Cellulase preparations include, for example, Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endulase 5000L (trade name, manufactured by Novozymes), Cellclean 4500T (trade name, Novozymes) Etc.).
Examples of mannanase preparations include trade name Mannaway 4L available from Novozymes.
The said enzyme may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
The enzyme content is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent as an enzyme preparation.

The liquid detergent is preferably contained in a container to form a container-containing liquid detergent. All components of the liquid cleaning agent may be stored in a container to form a one-component liquid cleaning agent. The liquid cleaning agent is divided into a plurality of liquids (for example, two liquids) and each stored in a container (for example, two liquids). Type liquid cleaner).
When using a two-component liquid detergent, the first liquid, the second liquid, and the fiber product are applied to the fiber product so that they are 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 amount of liquid detergent used”.

In the case of the two-component type, the mass ratio of the first liquid to the second liquid applied to the textile product is not particularly limited, but is preferably 3: 1 to 1: 3, particularly 1: 1 is preferred.
The content of the component (A) is preferably 2.5 to 80% by mass, more preferably 5 to 70% by mass with respect to each of the total mass of the first liquid and the total mass of the second liquid. 5-60 mass% is further more preferable, and 10-50 mass% is especially preferable. When it is at least the lower limit value, the cleaning power 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 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, the detergency when applied for a long time is more excellent. The higher the content of the component (C1), the shorter the application time (the standing time after applying the liquid cleaning agent) necessary for exhibiting excellent cleaning power. Although the upper limit of content of (C1) component is not specifically limited, From a viewpoint of the odor of a liquid detergent, 10 mass% or less is preferable, 8 mass% or less is more preferable, and 6 mass% or less is further more preferable.

  When the component (C2) is contained in either one or both of the first liquid and the second liquid, the component (C2) with respect to each of the total mass of the first liquid and the total mass of the second liquid The content of is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, and 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. Moreover, the rinse property at the time of the washing process after long-time application | coating is more excellent. It is excellent from a viewpoint of cost that it is below the upper limit.

It is preferable that either one or both of the first liquid and the second liquid further contain 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 with respect to the total mass of the first liquid and the total mass of the second liquid, 0.5-5 mass% is further more preferable. When it is at least the lower limit value, good rinsing properties can be easily obtained during the washing treatment after long-time application, and when it is at most the upper limit value, the stability of the liquid detergent is excellent.

  20-80 mass% is preferable with respect to each of the total mass of a 1st liquid, and the total mass of a 2nd liquid, 20-80 mass% is more preferable, 25-75 mass% is more preferable, 30-70 More preferred is mass%. When it is at least the lower limit value, it is more excellent in terms of detergency, and when it is at most the upper limit value, it is more excellent in liquid stability.

Either one or both of the first liquid and the second liquid may further contain a 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, with respect to the total mass of the first liquid and the total mass of the second liquid, 0.3-2 mass% is further more preferable.

The preferred ranges of the water content relative to the total mass of the first liquid and the water content relative to the total mass of the second liquid are each preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass. 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 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.

<Method for producing liquid detergent>
The one-component liquid detergent is produced by mixing the component (A), the component (C1), and other components to be contained as necessary. Furthermore, it is preferable to store in a container to obtain a liquid detergent contained in the container.
The two-component liquid cleaning agent is a method of mixing components to be contained in each solution, and prepares a first liquid and a second liquid, respectively, and accommodates them in a container to form a container-containing liquid cleaning agent. The container for storing the first liquid and the container for storing the second liquid may be separate or may be integrated.
The container is preferably a container that can directly apply a liquid cleaning agent to the textile product from the discharge port of the container. The container which can be used repeatedly may be sufficient and a disposable container may be sufficient.

<Washing method for textile products>
The washing method of the present invention is a method in which the liquid cleaning agent according to the present invention is applied to the soil of a textile product, left for 30 minutes or more, and then washed with water.
By applying the liquid cleaning agent to the textile product, the soiled portion of the textile product is impregnated with the liquid cleaning agent, and the soiling and the liquid cleaning agent are brought into contact with each other.
When applying a liquid detergent to textiles, it is preferable to contact the dirt with the liquid detergent concentration maintained, so that the liquid detergent can be directly applied to the dirt without immersing the textile in water. Apply. The application amount is set to be equal to or more than the amount that the liquid cleaning agent permeates the entire portion where the dirt adheres.
The standing time after application (hereinafter also referred to as application time) is preferably 30 minutes to 24 hours, and more preferably 12 to 24 hours. Excellent detergency is exhibited by leaving it to stand for 30 minutes or more. The detergency improves as the standing time increases, and reaches a limit in about 24 hours.

The washing treatment method may be any method in which the textile product coated with the liquid detergent is brought into contact with at least water, and dirt and the liquid detergent adhering to the textile product are transferred to the water to be removed. There is no particular limitation. A normal washing process includes a washing process and a rinsing process. The rinsing process is a process for removing the remaining liquid cleaning agent after the cleaning process. After the rinsing treatment, drying or the like is performed to remove moisture from the article to be washed (textile product).
In the cleaning treatment, in a cleaning liquid containing water and a liquid cleaning agent, preferably, an external force is applied to the object to be cleaned to transfer the dirt into the cleaning liquid, followed by dehydration and the like to separate the object to be cleaned from the cleaning liquid. .
In the rinsing process, after the cleaning process is performed, in the rinsing water that does not contain the liquid cleaning agent, preferably, an external force is applied to the object to be cleaned, and the remaining liquid cleaning agent is transferred to the rinsing water, followed by dehydration, etc. To separate the article from the rinse water.
The washing process is usually performed once. The rinsing process may be performed once or repeated twice or more. One rinsing treatment is preferable because it saves the use of rinsing water and shortens the washing time.
The method of applying external force to the object to be washed may be, for example, a method of applying mechanical force by a washing machine, or a method of hand washing such as fir washing, push washing, tapping washing, grabbing washing, pinch washing, or shaking washing.

  Only the water may be brought into contact with the textile product at the start of the washing process (cleaning process), or a cleaning liquid containing water and a liquid cleaning agent may be used. When only water is brought into contact, the liquid cleaning agent applied to the textile product is dispersed in water to form a cleaning liquid. When the cleaning liquid containing water and the liquid cleaning agent is brought into contact, 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 increases.

The article to be washed in the laundry process may include not only the textile product to which the liquid detergent is applied, but also other textile products to which the liquid detergent is not applied.
The amount of the liquid cleaning agent used in the cleaning treatment is preferably such that the ratio of the total mass (cloth amount) of the object to be cleaned / the total mass of the liquid cleaning agent is 10 to 500, more preferably 10 to 300, and 10 to 100. Is more preferable. When it is at least the lower limit value, it is excellent in rinsing properties when applied for a long time, and when it is not more than the upper limit value, it is excellent in the cleaning power of other textile products to which no liquid detergent is applied.
All of the liquid detergent used in the laundry process may be used to apply the textile product to the soil, a portion may be applied to the textile product soil, and the rest may be added during the laundry process.
The amount of water used in the cleaning treatment is preferably 30 times or more, more preferably 30 to 500 times, and more preferably 30 to 300 times the amount of liquid detergent used in the cleaning treatment. When it is at least the lower limit, the rinsing properties are more excellent. If it is below the upper limit, the cleaning performance is more excellent.

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

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) component>
A-1 (MEE): fatty acid methyl ester ethoxylate (12 to 14 carbon atoms of fatty acid, average addition mole number of EO of 15), in the above general formula (I), R ¹ = alkyl group having 11 carbon atoms and carbon number 13 alkyl groups, R ² = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method. Narrow rate 30%.
A-2 (AE (15)): A product obtained by adding 15 moles of ethylene oxide to natural alcohol. In the general formula (II), R ³ = alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, v = 15, w = 0, x = 0. Synthesized by the following synthesis method.
A-3 (AE (10)): A product obtained by adding 10 moles of ethylene oxide to natural alcohol. In the 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 (mass ratio of 12 alcohols / 14 alcohols = 7/3), 8 moles of ethylene oxide, 2 moles of propylene oxide, 8 moles of ethylene oxide Are added in this order in blocks. In the 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 product obtained by adding 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms. Product name “Softanol 70” manufactured by Nippon Shokubai Co., Ltd. In the general formula (II), R ³ = secondary alkyl group having 12 to 14 carbon atoms, v = 7, w = 0, x = 0.
A-6: An average of 6 moles of ethylene oxide was added to a mixture of C12 primary alcohol (C12OH) and C14 primary alcohol (C14OH) (mass ratio C12OH / C14OH = 75/25). What you did. Product name “Leox CL-60”, manufactured by Lion Corporation. In the 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.

<(B) component>
B-1: Palm fatty acid, manufactured by NOF Corporation, trade name “Zushi 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 Co., Ltd., trade name “Solfit (Fine Grade)”.
C1-2: Butyl carbitol (diethylene glycol monobutyl ether), manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl diglycol”.
<(C2) component>
C2-1: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”.
C3-2: Propylene glycol, manufactured by ADEKA, trade name “propylene glycol”.

<(D) component: anionic surfactant>
D-1: Linear alkyl benzene sulfonic acid (LAS) (manufactured by Lion, trade name “Lypon LH-200”).
D-2: Polyoxyalkylene alkyl ether sulfate ester salt (AES), (mixture of sodium polyoxyethylene lauryl ether sulfate ester and sodium polyoxyethylene myristyl ether sulfate ester, average addition mole number of EO 1).
D-3: Monoethanolamine salt (AEPS) of polyoxyalkylene alkyl ether sulfate. Synthesized by the following synthesis method.
<(E) component: cationic surfactant>
E-1: Dialkyldimethylammonium salt (carbon number of alkyl group: 14), manufactured by Kao Corporation, trade name “Cotamine D2345P”.
<(F) component>
PPG 4000: propylene oxide adduct of trihydric alcohol (polyoxypropylene glyceryl ether, manufactured by Mitsui Chemicals, trade name “Actol T-4000”, mass average molecular weight 4000.
<Water>
-Purified water: manufactured by Kanto Chemical Co., Inc.

<Other optional components>
-Paratoluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
-Sodium lactate: manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.
MGDA: methyl glycine diacetic acid trisodium, manufactured by BASF, trade name “Trilon M Liquid”.
・ Calcium chloride: Product name “Calcium chloride” manufactured by Kanto Chemical Co., Inc.
-Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name "sodium benzoate".
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
-Soil release polymer: manufactured by Clariant Japan, trade name “TexCare SRN-170C”, mass average molecular weight = 2000 to 3000, pH (5 mass% aqueous solution at 20 ° C.) = 4, viscosity (20 ° C.) = 300 mPa · s) . TexCare SRN-170C is a 70% by weight 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: Tsurumi Soda Co., Ltd., trade name "sodium hydroxide".
Alcalase: Protease preparation manufactured by Novozymes, trade name “Alcalase 2.5L”.
-Dye: Product name "Green No. 3", manufactured by Hatake Kasei Co., Ltd.
Citric acid: “Citric anhydride” manufactured by Fuso Chemical Industry.
Monoethanolamine: Nippon Shokubai Co., Ltd., trade name “monoethanolamine”.
-Sodium bicarbonate: manufactured by Kanto Chemical Co., Ltd., trade name “sodium bicarbonate”.
2H-08: 2-ethylhexyl isooctylate, manufactured by Lion Specialty Chemicals, trade name “2-ethylhexyl isooctylate”.
-Sokalan CP9: copolymer sodium salt of olefin and maleic acid, manufactured by BASF, trade name “Sokalan CP9”.
Blue HP: Dye, manufactured by Milliken, trade name “LIQUIINT Blue 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>
The synthesis was performed according to the synthesis method described in JP-A No. 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 Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. An autoclave was charged with 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 in a 4 L autoclave. The catalyst was reformed inside. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The obtained reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter 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 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, 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 through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. After completion of the addition of ethylene oxide, aging was performed 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 so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and AE (15EO) was 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, a temperature control device and an automatic introduction device, a linear primary alcohol having 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity> 99 %] 640 g and KOH 1.0 g were charged, and dehydration was performed at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, and after heating up to 120 ° C., 199 g of propane-1,2-diyl oxide was charged. Subsequently, after addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide was charged. Subsequently, after 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 for 30 minutes at 80 ° C. and then extracted. The average added mole number of propylene oxide was 1.0, and the average added mole number of ethylene oxide was An alkoxylate with a value of 2.0 was obtained. The resulting alkoxylate was sulfated in a falling film reactor using SO3 gas. The obtained sulfate was neutralized with monoethanolamine to obtain AEPS.

(Examples 1-16)
Examples 1 to 3, 5 to 7, and 9 to 16 are examples, and examples 4 and 8 are comparative examples.
Detergency against ink stains when a liquid detergent is produced with the formulation shown in Tables 1 to 3 and the textile is washed under the conditions shown in the table (application time, “H” in the table is “hour”). And the rinsing property 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 production of the liquid detergent was carried out by adding the components (A) to (F) and other optional components to water according to the formulation shown in the table and mixing them.
In the table, the following values a to f in the liquid cleaning agent of each example are described.
a: mass ratio of component (A) / component (B), b: total content of component (A), c: total content of component (D), d: total content of surfactant, e: Total content of (C1) component and (C2) component, f: Mass ratio of (C1) component / (C2) Note that the unit of content in the table is “mass%” and is converted to a pure content Indicates the amount. A blank in the table means that the component is not blended (the same applies hereinafter).

(Examples 17 to 22)
Examples 17-22 are examples. With the formulation shown in Table 4, a liquid detergent was produced in the same manner as in Example 1, and each container was housed to produce a container-containing detergent. About the obtained container washing | cleaning agent, it carried out similarly to Example 1, and evaluated the cleaning power with respect to ink stain | pollution | contamination, and a rinse property. The results are shown in the table.
The compositions of the liquid detergents of Example 15 and Example 19 are the same.

In Examples 17 and 18, the application container (capacity: 250 g) shown in FIG. 1 was filled with a liquid detergent. In the application 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 denotes a cap. When using the container-containing cleaning agent of this example, the liquid cleaning agent in the container body 2 is impregnated in the sponge head 1 and the sponge head 1 is brought into contact with the textile product, so that the liquid cleaning agent is directly applied to the textile product. To do.
In Example 19, a bag-like container (Japanese Patent No. 4246760, container shown in FIG. 1) was filled with a liquid detergent. When using the container-containing cleaning agent 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 provided in Example 20A with two storage parts of a container (container disclosed in JP2013-184716A, FIG. 4) in which a container for storing two liquids separately is provided and the two liquids are discharged simultaneously. 15 mL of the liquid cleaning agent (first liquid) and 15 mL of the liquid cleaning agent (second liquid) produced in Example 20B were filled. When using the container-containing cleaning agent of this example, the liquid cleaning agents in the two storage portions are simultaneously discharged from the opening formed by bending the lid portion into 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 were placed in the two containers of the same container as Example 20. Each 15 mL was filled.
In Example 24, a liquid detergent was filled in a squeeze container (manufactured by Lion, dish detergent, main body container of Charmy Magica (product name), capacity: 230 ml) equipped with a push-pull cap. When using the container-containing cleaning agent 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 used mass of the liquid detergent is 30 mL. The values of a to f in the total used mass of Examples 20 and 21 are shown in the table.
The values of a to d in the first liquid and the second liquid are as follows.
The mass ratio of a: (A) component / (B) component is 13.43 for Example 20A, 18.59 for Example 20B, 17.50 for Example 21A, and 18.75 for Example 21B.
b: The total of component (A) is 27 mass% for Example 20A, 29 mass% for Example 20B, 35 mass% for Example 21A, and 15 mass% for Example 21B.
c: The total of component (D) is 13 mass% for Example 20A, 14 mass% for Example 20B, 15 mass% for Example 21A, and 15 mass% for 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]
Five pieces of cotton cloth and tet cotton cut into 5 cm × 5 cm were prepared as evaluation cloths. “Tet cotton” refers to a blend of Tetron (registered trademark) and cotton broad (50% polyester / 50% cotton).
The evaluation cloth was coated with an ink of an oil-based pen (manufactured by ZEBRA, trade name “Mackey Extra Fine”) to prepare an ink-stained cloth with oil-based ink stains attached. At this time, oil-based ink was applied to the center of the evaluation cloth so as to form letters with a diameter of 2 cm.
This ink soiled cloth was washed by the following procedure.
Apply 1.0 mL of the liquid cleaning agent of each example to the ink stain cloth so that the oil-based ink stain adhered to the ink stain cloth becomes the center, leave it for a predetermined time, and then wash by the following washing method. The dirt was washed. The application time (standing time) from the application of the liquid detergent to the start of the washing treatment was 5 minutes, 0.5 hours, 12 hours, or 24 hours. The washing process was started when the ink soiled cloth (or evaluation cloth) was in contact with water (hereinafter the same).
Into a fully automatic washing machine (product name: AW-80VC, manufactured by Toshiba), put 34 L of tap water of 15 ° C. and 10 sheets of the ink-stained cloth, and put other items to be washed so that the bath ratio is 20 times. According to the standard course, the operation of sequentially washing 10 minutes, rinsing once, and dehydrating 3 minutes was performed once, and then air-dried. The bath ratio is a ratio (unit: times) represented by cleaning liquid (unit: L) / object to be cleaned (unit: kg).
The color difference meter (product name: SE200 type) made by Nippon Denshoku Co., Ltd. is used for the reflectance (R) of the evaluation cloth without ink stains, the ink dirt cloth before washing, and the ink dirt cloth after washing. The washing rate (%) was calculated by the following formula.
Washing rate (%) = 100 × (K / S of ink dirt cloth before washing−K / S of ink dirt cloth after washing) / (K / S of ink dirt cloth before washing−Evaluation cloth) 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 dirt cloth before washing, or an ink dirt after washing. This is the reflectance (%) of the cloth.
For each of the 10 ink soiled cloths, the cleaning rate (%) was calculated, the average value was obtained, and the coating detergency against ink stains was evaluated based on the following criteria. If the cleaning rate (average value) was 40% or more (evaluation AC), it was determined that the cleaning power was good.
A: The cleaning rate (average value) is 60% or more.
B: The cleaning rate (average value) is 50% or more and less than 60%.
C: The cleaning rate (average value) is 40% or more and less than 50%.
D: The cleaning rate (average value) is less than 40%.

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

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

From the results shown in Tables 1 to 4, Examples 1 to 3, 5 to 7, and 9 to 22 show good detergency against ink stains, and Comparative Examples 4 and 8 have insufficient detergency. It was.
In Examples 1 to 4 shown in Table 1, the composition of the cleaning composition is the same. In Example 4 where the application time was 5 minutes, the detergency of ink stains was insufficient, whereas in Examples 1 to 3 where the application time was 30 minutes, 12 hours and 24 hours, Good detergency was exhibited, and the longer the coating time, the higher the detergency.
From the results of Table 2, in Example 8 not containing the component (C1), the detergency of ink stains was insufficient, while in Examples 5 to 7 containing the component (C1), good against ink stains The detergency was demonstrated, and the higher the content of the component (C1), the higher the detergency. Moreover, the rinsability improved and the usability improved as the content of the component (C1) increased.

Examples 9 to 11 shown in Table 3 are examples in which the content of the component (C2) is changed. From these results, it is understood that the component (C2) contributes to improvement of rinsing properties 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 properties.
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 properties.

1 Sponge head 2 Container body 3 Cap

Claims (5)

  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 is applied to a textile product. A method for washing textile products, in which after 30 minutes of standing, the substrate is washed with water.   The method for washing a textile product according to claim 1, wherein the liquid detergent contains a water-miscible organic solvent (C2) having an SP value of 12 or more.   The textile product according to claim 1 or 2, wherein the liquid detergent contains a compound (B) selected from higher fatty acids and salts thereof, and the mass ratio of (A) component / (B) component is 1 to 35. Washing method.   The method for washing a textile product according to any one of claims 1 to 3, wherein a total content of the surfactant is 40% by mass or more with respect to a total mass of the liquid detergent.   The liquid cleaning agent for application | coating used for the washing | cleaning method of the textiles as described in any one of Claims 1-4.

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