JP2019182970A - Liquid detergent for fiber product - Google Patents

Abstract

To provide a liquid detergent for fiber product effectively preventing quality reduction of the fiber product.SOLUTION: There is provided a liquid detergent for fiber product containing (A) a nonionic surfactant containing (A1) a compound represented by the general formula (a1), and (B) alkylamide amine, and further containing one or more kind selected from (C) higher fatty acid, (D) a defoaming silicone selected from oil type, oil compound type, emulsion type, and self-emulsifiable type, (E) specific aliphatic acid ester, and (F) specific propylene oxide addition product, having a mass ratio (A1)/(B) of 4 to 20. R-O-(RO)-H (a1). In the formula (a1), Rrepresents a C12 to 16 alkyl group, Rrepresents a C2 to 4 alkylene group and n is 3 to 10.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent for textile products.

Textile products such as clothing rub against each other during washing and wearing, producing pills. In particular, a knitted product made of wool or chemical fiber is liable to be deteriorated by washing or wearing. Such deterioration in quality is a big problem for so-called fashionable clothes.
In order to solve such problems, a cleaning agent has been proposed that specifically prevents degradation of the quality of the textile product when worn (Patent Document 1).

Japanese Patent Laying-Open No. 2015-127369

However, although the conventional technique can prevent the deterioration of quality when worn, it has not been sufficient to prevent the deterioration of quality due to washing.
Then, an object of this invention is to provide the liquid cleaning agent for textiles which can prevent the quality degradation of textiles more favorably.

Ｘ−ＣＯＯ−Ｙ ・・・（ｅ）

式（ａ１）中、Ｒ^２１は分岐鎖を有する炭素数１２〜１６のアルキル基、又は炭素数１２〜１６の直鎖アルキル基を示し、Ｒ^２１が前記直鎖アルキル基の場合、酸素原子は、前記直鎖アルキル基中の２級炭素原子に結合する。Ｒ^２２は炭素数２〜４のアルキレン基を表す。また、ｎはＲ^２２Ｏの平均繰り返し数を示し３〜１０である。
式（ｂ）中、Ｒ^１０は、炭素数９〜２３の直鎖もしくは分岐鎖の炭化水素基である。Ｒ^１１は、炭素数１〜４の直鎖又は分岐鎖のアルキレン基である。Ｒ^１２及びＲ^１３は、それぞれ独立に炭素数１〜４の直鎖もしくは分岐鎖のアルキル基、炭素数１〜４の直鎖もしくは分岐鎖のヒドロキシアルキル基、又はオキシエチレン基の平均繰り返し数が１〜２５の（ポリ）オキシエチレン基である。
式（ｅ）中、Ｘは、炭素数５〜２１の分岐鎖状アルキル基、又は炭素数５〜２１の直鎖状アルキル基である。Ｘが直鎖状アルキル基である場合、式（ｅ）中のカルボニル基の炭素原子に結合する炭素原子は第２級炭素原子である。Ｙは、炭素数３〜１６のアルキル基、又は−（Ｒ^３１Ｏ）_ｍ１−Ｒ^３２である。Ｒ^３１は、炭素数２〜４のアルキレン基である。ｍはＲ^３１Ｏの平均繰り返し数を示し１〜５である。Ｒ^３２は、炭素数１〜１６のアルキル基、フェニル基又はベンジル基である。
式（ｆ１）中、Ｒ^１は炭素数１〜８の炭化水素基を示し、ＰＯはオキシプロピレン基を示し、ｎ１はＰＯの平均繰り返し数を示し１０〜３５０である。
式（ｆ２）中、ＰＯはオキシプロピレン基を示し、ｎ２、ｎ３はそれぞれ独立にＰＯの平均繰り返し数を示し、ｎ２、ｎ３の合計は１０〜３５０である。
式（ｆ３）中、ＰＯはオキシプロピレン基を示し、ｎ４、ｎ５、ｎ６はそれぞれ独立にＰＯの平均繰り返し数を示し、ｎ４、ｎ５、ｎ６の合計は１０〜３５０である。 The present invention has the following aspects.
[1] (A) Nonionic surfactant other than the propylene oxide adduct of alcohol represented by any one of the following general formulas (f1) to (f3), which is a compound represented by the following general formula (a1) A nonionic surfactant containing (A1);
(B) contains an alkylamidoamine represented by the following general formula (b), and
(C) Higher fatty acid, (D) Antifoam silicone selected from oil type, oil compound type, emulsion type, self-emulsifying type, (E) fatty acid ester represented by the following general formula (e), and (F) Containing one or more selected from propylene oxide adducts of alcohol represented by any of the following general formulas (f1) to (f3),
The liquid detergent for textiles whose ratio (A1) / (B) of the mass of said (A1) to the mass of said (B) is 4-20.
_{^{R 21 -O- (R 22 O)}} n -H ··· (a1)

X-COO-Y (e)

In the formula (a1), R ²¹ represents a branched alkyl group having 12 to 16 carbon atoms or a linear alkyl group having 12 to 16 carbon atoms, and when R ²¹ is the linear alkyl group, the oxygen atom is To a secondary carbon atom in the linear alkyl group. R ²² represents an alkylene group having 2 to 4 carbon atoms. Moreover, n shows the average repeating number of R < ²² > O, and is 3-10.
In formula (b), R ¹⁰ is a linear or branched hydrocarbon group having 9 to 23 carbon atoms. R ¹¹ is a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently an average repeating number of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or an oxyethylene group. 1 to 25 (poly) oxyethylene groups.
In formula (e), X is a C5-C21 branched alkyl group or a C5-C21 linear alkyl group. When X is a linear alkyl group, the carbon atom bonded to the carbon atom of the carbonyl group in formula (e) is a secondary carbon atom. Y is an alkyl group having 3 to 16 carbon atoms, or ^{- _{(R 31 O) m1 -R 32}} . R ³¹ is an alkylene group having 2 to 4 carbon atoms. m shows the average repeating number of R < ³¹ > O, and is 1-5. R ³² is an alkyl group having 1 to 16 carbon atoms, a phenyl group, or a benzyl group.
In formula (f1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, PO represents an oxypropylene group, and n1 represents an average number of repetitions of PO and is 10 to 350.
In formula (f2), PO represents an oxypropylene group, n2 and n3 each independently represents the average number of repetitions of PO, and the total of n2 and n3 is 10 to 350.
In formula (f3), PO represents an oxypropylene group, n4, n5 and n6 each independently represents the average number of repetitions of PO, and the total of n4, n5 and n6 is 10 to 350.

[2] The liquid detergent for textiles according to [1], wherein the total content of (C), (D), (E), and (F) is 0.0001 to 10% by mass.
[3] The ratio (A1) / (A) of the mass of the (A1) to the mass of the (A) is 0.001 to 0.8, for the textile product according to [1] or [2] Liquid cleaning agent.

[4] After the fiber product is stirred and dehydrated in the cleaning liquid containing the liquid cleaning agent according to [1] to [3], the fiber product is stirred in rinsing water that does not contain the liquid cleaning agent, and then dehydrated. A method of washing textile products, which is performed only once.
[5] When the ratio of the mass of the cleaning liquid to the mass of the textile product when stirring the textile product in the cleaning liquid containing the liquid detergent is 15 to 30, and when the textile product is stirred in the rinsing water The method for washing a textile product according to [4], wherein a ratio of a mass of the rinsing water to a mass of the textile product is 15 to 30.

  According to the liquid detergent for textiles of the present invention, generation of pills due to rubbing during washing can be suppressed. Further, since the foam is good and the rinsing can be performed only once, rubbing due to washing can be reduced to the minimum. Therefore, it is possible to better prevent the deterioration of the quality of the textile product.

[Liquid cleaning agent]
The liquid detergent for textiles of the present invention (hereinafter sometimes simply referred to as a liquid detergent) contains (A) a nonionic surfactant containing a specific compound (A1) and (B) a specific alkylamidoamine. And (C) a higher fatty acid, (D) a specific antifoam silicone, (E) a specific fatty acid ester, and (F) one or more selected from propylene oxides of a specific alcohol.
Hereinafter, (A) a specific nonionic surfactant (A) component, a specific compound (A1) (A1) component, (B) a specific alkylamidoamine (B) component, (C) a higher fatty acid (C) component, (D) a specific antifoam silicone (D) component, (E) a specific fatty acid ester (E) component, and (F) a propylene oxide of a specific alcohol (F) Sometimes referred to as a component.

<(A) component>
The component (A) is a nonionic surfactant other than the component (F) described later. The component (A) includes a compound (A1) represented by the following general formula (a1). The component (A) functions as a cleaning component that removes dirt from the textile product. Moreover, by including (A1) component, (B) component becomes easy to osmose | permeate textiles, and it becomes easy to improve pill preventing property.
R ²¹ —O— (R ²² O) _n —H (a1)

In the formula (a1), R ²¹ represents a branched alkyl group having 12 to 16 carbon atoms or a linear alkyl group having 12 to 16 carbon atoms, and when R ²¹ is the linear alkyl group, the oxygen atom is To a secondary carbon atom in the linear alkyl group. R ²² represents an alkylene group having 2 to 4 carbon atoms. Moreover, n is 3-10 with the average repeating number of R < ²² > O.

In formula (a1), R ²¹ is preferably a linear alkyl group having 12 to 16 carbon atoms, and more preferably a linear alkyl group having 12 to 14 carbon atoms.
Examples of R ²² O include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, from the viewpoint of liquid stability, an oxyethylene group or an oxypropylene group is preferable, and only the oxyethylene group or oxyethylene It is more preferable that it is both a group and an oxypropylene group. When it is both an oxyethylene group and an oxypropylene group, the oxyethylene group and the oxypropylene group may be random or may be a block.
n is a number of 3 to 10 in terms of the average number of repetitions of R ²² O, preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3.

(A1) As a component, you may use a commercial item. Commercially available products include, for example, Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (the numbers after C13 and C indicate the carbon number of alcohol. The same applies hereinafter), Neodol (registered trademark) manufactured by Shell. (Mixture of C12 and C13), Sasol (registered trademark) 23 (mixture of C12 and C13) manufactured by Sasol, and EXXAL (registered trademark) 13 (C13), etc. With addition of ethylene oxide;
A C13 alcohol obtained by subjecting an alkene having 12 carbon atoms obtained by trimerization of butene to the oxo method to which 3 or 5 moles or 7 moles of ethylene oxide is added (Lutensol®) TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF);
A product obtained by adding 9 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (Lutensol XP90, manufactured by BASF);
7 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (Lutensol XL70, manufactured by BASF);
A product obtained by adding 6 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (Lutensol XA60, manufactured by BASF);
What added 3 or 5 or 7 or 9 mol of ethylene oxide to C12-14 secondary alcohol (Softanol (registered trademark) 30, Softanol 50, Softanol 70, Softanol 90, manufactured by Nippon Shokubai Co., Ltd.) Etc.

From the viewpoint of easy penetration into the fiber, as the component (A1), R ²¹ is a linear alkyl group having 12 to 14 carbon atoms, and the oxygen atom is bonded to the secondary carbon atom in R ^21. And n is preferably 3. Among these, those in which R ²² O is an oxyethylene group are preferable.
A commercial product in which R ²¹ is a linear alkyl group having 12 to 14 carbon atoms, the oxygen atom is bonded to the secondary carbon atom in R ²¹ , R ²² O is an oxyethylene group, and n is 3. As such, SOFTANOL 30 may be mentioned.
(A1) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (A) other than the component (A1) and the component (F) (hereinafter sometimes referred to as the component (A2)) is not particularly limited as long as it has the effect of the present invention.
For example, fatty acid alkyl ester, higher alcohol (alcohol having 8 to 22 carbon atoms), alkylphenol, higher fatty acid (fatty acid having 8 to 22 carbon atoms), higher fatty acid alkyl ester (ester having a fatty acid residue having 8 to 22 carbon atoms) Or alkylene oxide adducts such as higher amines (amines having an alkyl group having 8 to 22 carbon atoms), polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide additions thereof Body, polyhydric alcohol fatty acid ether, alkyl amine oxide, alkenyl amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glucoside, etc. And the like.

Of these, polyoxyalkylene type nonionic surfactants (hereinafter, also referred to as “component (a2)”) other than the component (A1) represented by the following general formula (a2) are preferable.
_{^{R 71 -J- (EO) p (}} PO) q -R 72 ··· (a2)

In formula (a2), R ⁷¹ represents a hydrocarbon group having 8 to 22 carbon atoms, and R ⁷² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
J represents a functional group such as —O—, —COO—, and —CONH—.
EO represents an oxyethylene group, and PO represents an oxypropylene group.
p is a number of 3 to 20 representing the average number of repetitions of EO (that is, the average number of moles of ethylene oxide added).
q is a number from 0 to 6 that represents the average number of repetitions of PO (that is, the average number of moles of propylene oxide added).

However, when J is —O—, the sum of p and q is 3 to 10, and R ⁷² is a hydrogen atom, R ⁷¹ is not a branched alkyl group having 12 to 16 carbon atoms.
Moreover, J is -O-, and the sum of p and q is 3 to ^10, a ^{R 72} is a hydrogen atom, and, when J is bound to the secondary carbon atom in ^{R 71, R 71} is , It is not a linear alkyl group having 12 to 16 carbon atoms.

R ⁷¹ has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. If carbon number is in the said range, the cleaning power of a liquid cleaning agent will increase more.
^R71 may or may not have an unsaturated bond.
R ⁷¹ is preferably an alkyl group or an alkenyl group.
R ⁷¹ may be linear or branched.
Examples of R ⁷¹ include hydrocarbon groups derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

R ⁷² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
When R ⁷² is an alkyl group, R ⁷² preferably has 1 to 3 carbon atoms.
When R ⁷² is an alkenyl group, R ⁷² preferably has 2 to 3 carbon atoms.

In formula (a2), when J is —O—, the component (A2) is an alkyl ether type nonionic surfactant.
When J is —O—, from the viewpoint of improving detergency, R ⁷¹ is a linear alkyl group having 10 to 20 carbon atoms, a branched alkyl group having 10 to 20 carbon atoms, or 10 to 20 carbon atoms. A linear alkenyl group or a branched alkenyl group having 10 to 20 carbon atoms, a linear alkyl group having 10 to 18 carbon atoms or a branched alkyl group having 10 to 18 carbon atoms, or A linear alkenyl group having 10 to 18 carbon atoms or a branched alkenyl group having 10 to 18 carbon atoms is more preferable. When J is —O—, R ⁷² is preferably a hydrogen atom.

In formula (a2), when J is —COO—, the component (A2) is a fatty acid ester type nonionic surfactant.
When J is —COO—, from the viewpoint of improving detergency, R ⁷¹ is a linear alkyl group having 9 to 21 carbon atoms, a branched alkyl group having 9 to 21 carbon atoms, or 9 to 9 carbon atoms. A linear alkenyl group having 21 or a branched alkenyl group having 9 to 21 carbon atoms is preferable, a linear alkyl group having 11 to 17 carbon atoms or a branched alkyl group having 11 to 17 carbon atoms, Alternatively, a linear alkenyl group having 11 to 17 carbon atoms or a branched alkenyl group having 11 to 17 carbon atoms is more preferable. When J is —COO—, R ⁷² is preferably an alkyl group having 1 to 3 carbon atoms.

p is a number of 3 to 20, and a number of 5 to 18 is preferable. If p is less than or equal to the above upper limit, the HLB value will not be too high, and the cleaning power will not easily decrease. If p is more than the said lower limit, the odor derived from the raw material of (d1) component itself is hard to generate | occur | produce.
q is a number from 0 to 6, and a number from 01 to 3 is preferable. If q is less than or equal to the above upper limit value, storage stability under high temperature conditions is unlikely to decrease.
"-(EO) _p (PO) _q- " may be a random chain in which EO and PO are mixed and may be a block chain arranged in a block shape.

In the component (A2), the distribution of the number of repetitions of EO or PO is not particularly limited as long as it has the effect of the present invention. In the component (A2), the distribution of the number of repetitions of EO or PO is likely to vary depending on the reaction method in producing the component (A2).
The distribution of the number of repetitions of EO or PO is determined by using ethylene oxide or propylene oxide as a raw material (primary or secondary higher alcohol, higher fatty acid, When added to higher fatty acid amides or the like, the distribution tends to be relatively wide.

For the distribution of the number of repetitions of EO or PO, ethylene oxide or propylene oxide can be selected from, for example, Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn described in JP-B-615038. ^When a specific alkoxylation catalyst such as magnesium oxide to which metal ions such as ²⁺ are added is added to the raw material, the distribution tends to be relatively narrow.

(A2) As a component, you may use a commercial item. As a commercial item, for example, 12 mol equivalent or 15 mol equivalent ethylene oxide was added to linear natural alcohol such as CO-1214 or CO-1270 (trade name) manufactured by Procter & Gamble Co. thing;
12-carbon equivalent or 15-mol equivalent ethylene oxide added to C13 alcohol obtained by subjecting alkene having 12 carbon atoms obtained by trimerization of butene to oxo method (Lutensol (registered trademark) TO12, Lutensol) TO15 etc., manufactured by BASF);
What added 12 mol equivalent or 15 mol equivalent ethylene oxide to C12-14 secondary alcohol (Softanol (registered trademark) 120, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.);
What added 15 mol of ethylene oxide (polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)) to the palm fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst It is done.

Among these, from the viewpoint of rinsing properties, anti-pilling properties (acceleration of adsorption of the component (B)), and detergency, the linear natural alcohol (for example, CO-1270) manufactured by Procter & Gamble, An average of 12 moles of ethylene oxide added, and an average of 10 moles of ethylene oxide added to a linear natural alcohol (for example, CO-1270) manufactured by Procter & Gamble Co .;
Polyoxyalkylene alkyl ether in which an average of 9 moles of ethylene oxide, an average of 2 moles of propylene oxide, and an average of 9 moles of ethylene oxide are added to C12-14 linear primary alcohol in this order;
In formula (a2), a compound in which R ⁷¹ is a linear alkyl group having 12 to 14 carbon atoms, R ⁷² is a hydrogen atom, J is —O—, and p = 2 and q = 18 is preferable. .
These components may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the entire component (A) in the liquid detergent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass with respect to the total mass of the liquid detergent.
When the content of the entire component (A) in the cleaning liquid is equal to or more than the preferable lower limit value, the cleaning power and the effect of penetrating and adsorbing the component (B) on the fiber product tend to be high.
Further, when the content of the entire component (A) in the cleaning liquid is equal to or less than the preferable upper limit value, it becomes easy to obtain a cleaning liquid with better rinsing properties.
The total content of the component (A) in the cleaning liquid obtained by dissolving the liquid cleaning agent in water is preferably 50 to 1000 ppm by mass, more preferably 70 to 800 ppm by mass with respect to the total mass of the cleaning liquid. More preferably, the content is 100 to 600 ppm by mass.
When the content of the entire component (A) in the cleaning liquid is equal to or more than the preferable lower limit value, the cleaning power and the effect of penetrating and adsorbing the component (B) on the fiber product tend to be high.
Further, when the content of the entire component (A) in the cleaning liquid is equal to or less than the preferable upper limit value, it becomes easy to obtain a cleaning liquid with better rinsing properties.

The content of the component (A1) in the liquid detergent is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the total mass of the liquid detergent, It is more preferable that it is 10 mass%, and 1-3 mass% is especially preferable.
When the content of the component (A1) in the liquid detergent is equal to or more than the preferred lower limit, when this is dissolved in water, it tends to be a cleaning liquid having a high detergency and an effect of penetrating and adsorbing the component (B) on the fiber product.
Moreover, when the content of the component (A1) in the liquid cleaning agent is equal to or less than the preferable upper limit value, when this is dissolved in water, it becomes easy to obtain a cleaning solution having better rinsing properties.

The content of the component (A1) in the cleaning liquid obtained by dissolving the liquid cleaning agent in water is preferably 10 to 500 ppm by mass, more preferably 20 to 400 ppm by mass, with respect to the total mass of the cleaning liquid. More preferably, it is 30-350 mass ppm.
When the content of the component (A1) in the cleaning liquid is equal to or more than the preferable lower limit, the cleaning power and the effect of penetrating and adsorbing the component (B) on the fiber product are likely to be high.
In addition, when the content of the component (A1) in the cleaning liquid is equal to or less than the preferable upper limit value, the cleaning liquid is more likely to have better rinsing properties.

The content of the component (A2) in the liquid detergent is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, and more preferably 10 to 25 mass% with respect to the total mass of the liquid detergent. % Is more preferable, and 15 to 25% by mass is particularly preferable.
When the content of the component (A2) in the liquid cleaning agent is equal to or more than the preferable lower limit value, when this is dissolved in water, a cleaning liquid with high cleaning performance tends to be obtained.
Moreover, when the content of the component (A2) in the liquid cleaning agent is equal to or less than the preferable upper limit value, when this is dissolved in water, a cleaning liquid excellent in rinsing properties is likely to be obtained.

The content of the component (A2) in the cleaning liquid obtained by dissolving the liquid cleaning agent in water is preferably 10 to 1000 ppm by mass, more preferably 50 to 600 ppm by mass, based on the total mass of the cleaning liquid. More preferably, it is 70-400 mass ppm.
When the content of the component (A2) in the cleaning liquid is not less than the preferable lower limit value, the cleaning performance tends to be high.
In addition, when the content of the component (A2) in the cleaning liquid is equal to or less than the preferable upper limit value, the cleaning liquid is more likely to have better rinsing properties.

(A) The ratio (A1) / (A) of the mass of the component (A1) to the mass of the entire component is preferably 0.001 to 0.8, more preferably 0.01 to 0.7, and 0.05 to 0. .6 is more preferable, and 0.05 to 0.2 is particularly preferable.
When (A1) / (A) is at least the preferred lower limit, the penetration adsorption effect of the component (B) on the fiber product tends to increase.
Moreover, since (A1) / (A) is below the preferable upper limit, the stability of the cleaning agent can be improved, so that separation and solidification hardly occur.

<(B) component>
The component (B) is an alkylamidoamine represented by the following general formula (b). The component (B) penetrates into the fiber product and exhibits the effect of preventing pills.

In formula (b), R ¹⁰ is a linear or branched hydrocarbon group having 9 to 23 carbon atoms. The number of carbon atoms in R ¹⁰ is preferably 15 to 21. If it is in the said range, it will be excellent in the effect which reduces the friction in the washing | cleaning liquid of textiles, and suppresses generation | occurrence | production of a pill.
R ¹⁰ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
R ¹¹ is a linear or branched alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ¹¹ is 2-3 are preferable. If it is in the said range, it will be excellent in the effect which reduces the friction in the washing | cleaning liquid of textiles, and suppresses generation | occurrence | production of a pill.
R ¹² and R ¹³ are each independently an average repeating number of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or an oxyethylene group. 1 to 25 (poly) oxyethylene groups.
R ¹² and R ¹³ are preferably a methyl group or an ethyl group.

Examples of the component (B) include lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide. Long chain aliphatic amidodialkyl tertiary amines;
Aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine;
Tertiary amines such as palmitic acid diethanolaminopropylamide and stearic acid diethanolaminopropylamide are listed.
Of these, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide are preferable.

The component (B) may be present in the form of a salt in the liquid cleaning agent or in a cleaning solution obtained by dissolving the liquid cleaning agent in water.
(B) As a salt of a component, the acid salt etc. which neutralized (B) component with the acid are mentioned. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. These acids may be used singly or in combination of two or more.

Among the components (B), an aliphatic amidoalkyl tertiary amine such as a long-chain aliphatic amidodialkyl tertiary amine can be produced, for example, by the following method.
Fatty acid or fatty acid derivative (fatty acid lower alkyl ester, animal fat or vegetable oil or the like) is condensed with dialkyl (or alkanol) aminoalkylamine, and then unreacted dialkyl (or alkanol) aminoalkylamine is reduced in pressure. Alternatively, an aliphatic amidoalkyl tertiary amine can be produced by distilling off by nitrogen blowing.

  Here, as the fatty acid or fatty acid derivative, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, beef tallow fatty acid, palm kernel Examples include oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, castor oil fatty acids, olive oil fatty acids and other vegetable or animal oil fatty acids, and methyl esters, ethyl esters, glycerides, etc., among them palmitic acid, stearic acid, oleic acid, Behenic acid and the like are preferable. These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

  Examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is preferable.

Examples of commercially available products of component (B) include lipomin APA168-65E (manufactured by Lion Specialty Chemicals, Inc., dimethylaminopropylamide stearate).
(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The content of the component (B) in the liquid detergent (in the case of a salt, the content as an alkylamidoamine. The same applies hereinafter) is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent. 0.05 to 10% by mass is more preferable, and 0.1 to 5% by mass is even more preferable.
When the content of the component (B) in the liquid cleaning agent is equal to or more than the preferable lower limit value, when this is dissolved in water, it tends to be a cleaning solution having a high anti-pilling effect.
Moreover, when the content of the component (B) in the liquid cleaning agent is equal to or less than the preferable upper limit value, when this is dissolved in water, it becomes easy to obtain a cleaning liquid with better rinsing properties.

The content of the component (B) in the cleaning liquid obtained by dissolving the liquid cleaning agent in water is preferably 0.01 to 100 ppm by mass, and 0.1 to 80 ppm by mass with respect to the total mass of the cleaning liquid. Is more preferable, and it is further more preferable that it is 1-50 ppm.
When the content of the component (B) in the cleaning liquid is equal to or more than a preferable lower limit value, the effect of preventing pilling tends to be high.
Further, when the content of the component (B) in the cleaning liquid is equal to or less than the preferable upper limit value, it becomes easy to obtain a cleaning liquid with more excellent rinsing properties.

The ratio (A1) / (B) of the mass of the component (A1) to the mass of the component (B) is 4-20. (A1) / (B) is preferably from 5 to 15, and more preferably from 5 to 10.
When (A1) / (B) is 4 or more, the pill preventing effect can be enhanced.
Moreover, when (A1) / (B) is 20 or less, the stability of the cleaning agent can be improved, and separation and solidification hardly occur.

<(C) component>
Component (C) is a higher fatty acid. Component (C) forms a complex with component (B) and contributes to improving the slipperiness of clothing. In addition, it combines with metal ions in tap water and exhibits a bubble breaking effect.
10-20 are preferable and, as for carbon number of the hydrocarbon group of a higher fatty acid, 12-18 are more preferable. As component (C), caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, behenic acid and other single fatty acids, coconut oil fatty acid, beef tallow fatty acid, etc. Of mixed fatty acids.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
As a combination, a combination of a fatty acid having 12 carbon atoms in a hydrocarbon group and a fatty acid having 14 to 18 carbon atoms in a hydrocarbon group is preferable, and the number of carbon atoms in a fatty acid having 12 carbon atoms and two or more hydrocarbon groups. Are more preferred in combination with 14-18 fatty acids.
The ratio of the fatty acid having 14 to 18 carbon atoms to the mass of the fatty acid having 12 to 18 carbon atoms, [fatty acid having 14 to 18 carbon atoms] / [fatty acid having 12 carbon atoms] is preferably 0.03 or more and 10 or less. 0.05 or more and 0.8 or less are preferable, and 0.06 or more and 0.5 or less are more preferable.

The component (C) may be present in the form of a salt in the liquid cleaning agent or in a cleaning solution obtained by dissolving the liquid cleaning agent in water.
Examples of the salt form of component (C) include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolammonium and diethanolammonium.
As commercially available products of component (C) or salts thereof, coconut fatty acid sodium ((coconut fatty acid) manufactured by NOF Corporation) is neutralized with sodium hydroxide which is a pH adjuster, C16 soap ((palmitic acid) Sodium) manufactured by Kanto Chemical Co., Ltd.).

The content of the component (C) in the liquid detergent (in the case of a salt, the content as a higher fatty acid. The same applies hereinafter) is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent. 0.05 to 10% by mass, more preferably 0.08 to 5% by mass, and particularly preferably 0.1 to 1.5% by mass.
When the content of the component (C) in the liquid detergent is equal to or more than the preferable lower limit, when this is dissolved in water, it becomes easy to obtain a cleaning liquid having a high effect of preventing pilling and excellent rinsing properties.
Moreover, when the content of the component (C) in the liquid cleaning agent is not more than the preferable upper limit value, when this is dissolved in water, it becomes easy to obtain a cleaning liquid having an excellent anti-pilling effect.

The content of the component (C) in the cleaning liquid in which the liquid cleaning agent is dissolved in water is preferably 0.01 to 1000 ppm by mass, and preferably 0.1 to 500 ppm by mass with respect to the total mass of the cleaning liquid. Is more preferable, and it is further more preferable that it is 1-100 mass ppm.
When the content of the component (C) in the cleaning liquid is equal to or more than the preferable lower limit, the effect of preventing pilling is high and excellent rinsing properties are easily obtained.
Moreover, when the content of the component (C) in the cleaning liquid is equal to or less than the preferable upper limit value, the effect of preventing pilling is excellent.

<(D) component>
Component (D) is an antifoam silicone selected from an oil type, an oil compound type, an emulsion type, and a self-emulsifying type. (D) component adsorb | sucks to clothing together by the hydrophobic interaction with (B) component, and contributes to the improvement of the slipperiness of clothing. Moreover, since it has a defoaming property, it contributes to the improvement of foam breakage.

The oil-type antifoaming silicone is an antifoaming agent composed of 100% unmodified silicone oil and containing no silica. SH200 (Toray Dow Corning Co., Ltd.) is mentioned as a commercial item.
The oil compound type antifoaming silicone is an antifoaming agent in which water-insoluble particles such as fine powder silica are blended with silicone oil. Commercially available products include 8590 Additive (Toray Dow Corning Co., Ltd.), AF-8014 Antifoam (Toray Dow Corning Co., Ltd.), AC-8066 Antifoam (Toray Dow Corning Co., Ltd.), ACP-3073 Antifoam ( Toray Dow Corning Co., Ltd.), KS-66 (Shin-Etsu Chemical Co., Ltd.) and the like.

The solution-type antifoam silicone is an antifoamer obtained by dissolving silicone oil in a solvent such as isoparaffin. KS-602A (Shin-Etsu Chemical Co., Ltd.) etc. are mentioned as a commercial item.
Emulsion type antifoaming silicone is an antifoaming agent obtained by emulsifying a silicone oil compound with a nonionic activator. Commercially available products include FS Antiform 93 (Toray Dow Corning Co., Ltd.), KM-73 (Shin-Etsu Chemical Co., Ltd.), KM-7750 (Shin-Etsu Chemical Co., Ltd.), and KM-7752 (Shin-Etsu Chemical Co., Ltd.). Etc.
The self-emulsifying type antifoaming silicone is an antifoaming agent composed of a hydrophilic modified silicone oil and an oil compound. Examples of commercially available products include KS-537 (Shin-Etsu Chemical Co., Ltd.).

The reason why the component (D) exhibits the defoaming property is that the surface tension of the silicone oil is small, and therefore the defoaming property is exhibited. In addition, when water-insoluble particles are blended as in the oil compound type, it is considered that water-insoluble particles carried to the foam surface by silicone oil physically break the bubbles.
The solution type, emulsion type, and self-emulsification type are obtained by adding an emulsifier or the like to silicone oil in order to improve dispersibility during use.

The content of the component (D) in the liquid cleaning agent is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass with respect to the total mass of the liquid cleaning agent, More preferably, it is 0.001-2 mass%, and 0.005-1 mass% is especially preferable.
When the content of the component (D) in the liquid detergent is equal to or more than the preferable lower limit, when this is dissolved in water, it becomes easy to obtain a cleaning liquid that has a high anti-pilling effect and good rinsing properties.
Moreover, when content of (D) component in a liquid cleaning agent is below a preferable upper limit, when this is melt | dissolved in water, it will become easy to become a cleaning liquid with a high pill preventing effect.

The content of the component (D) in the cleaning liquid in which the liquid cleaning agent is dissolved in water is preferably 0.001 to 500 ppm by mass, and 0.01 to 100 ppm by mass with respect to the total mass of the cleaning liquid. Is more preferable, and it is still more preferable that it is 0.05-50 mass ppm.
When the content of the component (D) in the cleaning liquid is equal to or more than the preferable lower limit value, it becomes easy to obtain a cleaning liquid that has a high anti-pilling effect and good rinsing properties.
Moreover, when content of (D) component in a washing | cleaning liquid is below a preferable upper limit, it becomes easy to become a washing | cleaning liquid with the more excellent pill preventing effect.

<(E) component>
The component (E) is a fatty acid ester represented by the following general formula (e). The component (E) is adsorbed to the clothing together by the hydrophobic interaction with the component (B), and contributes to improving the slipperiness of the clothing. In addition, it exhibits a bubble breaking effect due to its hydrophobicity.
X-COO-Y (e)
In formula, X is a C5-C21 branched alkyl group or a C5-C21 linear alkyl group. When X is a linear alkyl group, the carbon atom bonded to the carbon atom of the carbonyl group in formula (e) is a secondary carbon atom. Y is an alkyl group having 3 to 16 carbon atoms, or ^{- _{(R 31 O) m1 -R 32}} . R ³¹ is an alkylene group having 2 to 4 carbon atoms. m shows the average repeating number of R < ³¹ > O, and is 1-5. R ³² is an alkyl group having 1 to 16 carbon atoms, a phenyl group, or a benzyl group.

In the formula (e), X is a branched alkyl group having 5 to 21 carbon atoms or a linear alkyl group having 5 to 21 carbon atoms, preferably a branched alkyl group having 5 to 21 carbon atoms. It is.
The carbon number of the branched or straight chain alkyl group in X is preferably 5 to 13 carbon atoms, more preferably 6 to 11 carbon atoms, and further preferably 6 to 10 carbon atoms. If the number of carbon atoms is less than the preferred lower limit, it may be difficult to obtain a pill preventing effect and an antifoaming effect. When the carbon number exceeds the preferable upper limit, the hydrophobicity becomes too strong, and the dispersibility in the cleaning liquid may be impaired.

When X is a linear alkyl group, the carbon atom bonded to the carbon atom of the carbonyl group in formula (e) is a secondary carbon atom.
When X is a branched alkyl group, the number of branched side chains is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. When the number of side chains is within the above range, a sufficient anti-pilling effect and antifoaming property are exhibited.

In the formula (e), Y is an alkyl group having 3 to 16 carbon atoms, or ^{- _{(R 31 O) m -R 32}} .
When Y is an alkyl group: The alkyl group in Y preferably has 6 to 10 carbon atoms. If the carbon number is at least the preferred lower limit, it is easy to obtain a pill preventing effect and an antifoaming effect. If the number of carbon atoms is less than or equal to the preferred upper limit value, the hydrophobicity does not become too strong, so that it is easy to obtain good dispersibility in the cleaning liquid.
Y may be a linear alkyl group or a branched alkyl group, and among them, a branched alkyl group is preferable. If Y is a branched alkyl group, the effect of preventing pilling and the antifoaming property can be further enhanced.
When Y is a branched chain, the number of side chains is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. When the number of side chains is within the above range, a sufficient anti-pilling effect and antifoaming property are exhibited.

Preferable Y includes, for example, isotridecyl group, ethylhexyl group, hexyldecyl group, isobutyl group, and isopropyl group. Among them, ethylhexyl group is preferred from the viewpoints of anti-pilling effect and antifoaming property, and dispersibility in a cleaning solution. Is more preferable.
When Y is an alkyl group, the branched or linear alkyl group in X preferably has 5 to 13 carbon atoms, more preferably 6 to 11 carbon atoms, still more preferably 7 to 10 carbon atoms, and 7 to 9 carbon atoms. Is particularly preferred. When the carbon number of X is within the above range, the balance between hydrophilicity and hydrophobicity becomes better, and the effect of preventing pilling and defoaming can be further enhanced.

When Y is — (R ³¹ O) _m —R ³² : R ³¹ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, more preferably 3 carbon atoms. An alkylene group. If carbon number is in the said range, the balance of hydrophilic property and hydrophobicity will become favorable, and a pill preventing effect and antifoaming property will be improved.
m shows the average repeating number of R < ³¹ > O, and is 1-5. m is preferably 2 to 5, and more preferably 3. When m is at least the preferred lower limit, the hydrophobicity does not become too strong, and good liquid stability when used as a liquid detergent is easily obtained. If m is less than or equal to the preferred upper limit, the hydrophilicity does not become too strong, and it is easy to obtain a pill preventing effect and an antifoaming effect.

R ³² is an alkyl group having 1 to 16 carbon atoms, a phenyl group or a benzyl group, and among them, an alkyl group having 1 to 16 carbon atoms is preferable. If R ³² is an alkyl ^group, the carbon number of ^{R 32} is 1 to 12, more preferably 1 to 6, 1 (i.e., methyl group) is more preferred. When the carbon number of R ³² is within the above range, the dispersibility in the cleaning liquid becomes better.
When Y is — (R ³¹ O) _m —R ³² , the branched or linear alkyl group in X preferably has 5 to 13 carbon atoms, more preferably 7 to 11 carbon atoms, 9 is more preferable. When the carbon number of X is within the above range, the balance between hydrophilicity and hydrophobicity becomes better, and the effect of preventing pilling and defoaming can be further enhanced.

The component (E) can be produced by a conventionally known method.
For example, in the formula (e), the method for producing the component (E) in which Y is an alkyl group includes a method by transesterification between fats and oils and a monohydric alcohol, and a method by transesterification between waste cooking oil and a monohydric alcohol. And a method of esterifying a fatty acid with a monohydric alcohol, a method by transesterification of a fatty acid alkyl ester and a monohydric alcohol, and the like.
(E) Carbon number of the fatty acid residue which comprises a component cuts a carbon fraction by distilling (E) component, for example, or two types of carbon fraction of the fatty-acid alkylester which has desired carbon number It can adjust by using the raw material mix | blended above.

  (E) Although it does not specifically limit as fats and oils used for the manufacturing method of a component, Vegetable oil or animal oil is preferable and vegetable oil is more preferable. Examples of vegetable oils include rapeseed oil, sunflower oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, corn oil, coconut oil, palm oil, palm kernel oil, and the like. Absent. Among these, palm kernel oil and coconut oil are preferred because of the high content of fatty acids having 6 to 14 carbon atoms. Examples of animal oils include beef tallow, pork tallow, and fish oil, but are not particularly limited thereto.

  (E) Although it does not specifically limit as alcohol used for the manufacturing method of component, Linear natural alcohols, such as CO-1214 or CO-1270 by Procter & Gamble Co., Diadol (made by Mitsubishi Chemical Corporation) (Registered Trademark) (C13, the number after C indicates the carbon number of alcohol. The same applies hereinafter), Neodol (registered trademark) manufactured by Shell (mixture of C12 and C13), Safo (registered by Sasol) Trademark) 23 (mixture of C12 and C13) and the like are preferable.

  Examples of the component (E) include 2-ethylbutyl 2-ethylbutanoate, 2-ethylhexyl 2-ethylbutanoate, 2-ethyloctyl 2-ethylbutanoate, 2-ethyldecyl 2-ethylbutanoate, 2-ethyldodecyl 2-ethylbutanoate. 2-ethylbutyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, 2-ethyloctyl 2-ethylhexanoate, 2-ethyldecyl 2-ethylhexanoate, 2-ethyldodecyl 2-ethylhexanoate, 2- 2-ethylbutyl ethyloctanoate, 2-ethylhexyl 2-ethyloctanoate, 2-ethyloctyl 2-ethyloctanoate, 2-ethyldecyl 2-ethyloctanoate, 2-ethyldodecyl 2-ethyloctanoate, 2-ethyldecanoic acid 2 -Ethylbutyl, 2-ethyldecanoic acid Ruhexyl, 2-ethyloctyl 2-ethyldecanoate, 2-ethyldecyl 2-ethyldecanoate, 2-ethyldodecyl 2-ethyldecanoate, 2-ethylbutyl 2-ethyldodecanoate, 2-ethylhexyl 2-ethyldodecanoate, 2-ethyldodecane 2-ethyloctyl acid, 2-ethyldecyl 2-ethyldodecanoate, 2-ethyldodecyl 2-ethyldodecanoate, 2-ethylbutyl 2-ethyltetradecanoate, 2-ethylhexyl 2-ethyltetradecanoate, 2-ethyltetradecanoic acid 2- Ethyloctyl, 2-ethyltetradecanoate 2-ethyldecyl, 2-ethyltetradecanoate 2-ethyldodecyl, 2-ethylpentadecanoate 2-ethylbutyl, 2-ethylpentadecanoate 2-ethylhexyl, 2-ethylpentadecanoate 2-ethyloctyl 2-ethylpentadecanoate 2-ethyldecyl, 2-ethylpentadecanoate 2-ethyldodecyl, 2-ethylhexadecanoate 2-ethylbutyl, 2-ethylhexadecanoate 2-ethylhexyl, 2-ethylhexadecanoate 2-ethyloctyl, 2-ethyl Monoester oils such as 2-ethyldecyl hexadecanoate, 2-ethyldodecyl 2-ethylhexadecanoate, isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate; Examples include acid neopentyl glycol.

Among these, since the defoaming effect is more easily obtained, 2-ethylbutyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, 2-ethyloctyl 2-ethylhexanoate, 2-ethylhexanoic acid 2- One or more compounds selected from the group consisting of ethyl decyl and 2-ethyl dodecyl 2-ethylhexanoate are preferred, and among these, 2-ethylhexyl 2-ethylhexanoate is particularly preferred.
(E) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The content of the component (E) in the liquid detergent is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass with respect to the total mass of the liquid detergent, It is more preferable that it is 0.08-5 mass%, and 0.1-1.5 mass% is especially preferable.
When the content of the component (E) in the liquid detergent is equal to or more than the preferred lower limit, when this is dissolved in water, it becomes easy to obtain a cleaning liquid that has a high anti-pilling effect and good rinsing properties.
Moreover, when the content of the component (E) in the liquid cleaning agent is equal to or less than the preferable upper limit value, when this is dissolved in water, it tends to be a cleaning liquid having a high anti-pilling effect.

The content of the component (E) in the cleaning liquid in which the liquid cleaning agent is dissolved in water is preferably 0.01 to 100 ppm by mass, and preferably 0.1 to 80 ppm by mass with respect to the total mass of the cleaning liquid. Is more preferable, and it is further more preferable that it is 1-50 mass%.
When the content of the component (E) in the cleaning liquid is equal to or higher than the preferable lower limit, the cleaning liquid is likely to have a high anti-pilling effect and good rinsing properties.
Moreover, when the content of the component (E) in the cleaning liquid is equal to or less than the preferable upper limit value, it becomes easy to obtain a cleaning liquid with a more excellent pill preventing effect.

<(F) component>
Component (F) is a propylene oxide adduct of alcohol represented by any one of general formulas (f1) to (f3). The component (F) is adsorbed to the clothing together by the hydrophobic interaction with the component (B), and contributes to improving the slipperiness of the clothing. In addition, it exhibits a bubble breaking effect due to its hydrophobicity.

  Component (F) is a monoalcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol; diol such as ethanediol, triol such as glycerin, tetraol such as erythritol, hexaol such as sorbitol, etc. A polyhydric alcohol obtained by adding propylene oxide.

In formula (f1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, PO represents an oxypropylene group, and n1 represents an average number of repetitions of PO and is 10 to 350.
In formula (f2), PO represents an oxypropylene group, n2 and n3 each independently represents the average number of repetitions of PO, and the total of n2 and n3 is 10 to 350.
In formula (f3), PO represents an oxypropylene group, n4, n5 and n6 each independently represents the average number of repetitions of PO, and the total of n4, n5 and n6 is 10 to 350.

In formula (f1), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms. Preferably it is C1-C3.
Examples of R ¹ include an alkyl group and an alkylene group.
Examples of R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group.
N1 to n6 in the formulas (f1) to (f3) are each preferably 10 to 50, and more preferably 15 to 40.

The weight average molecular weight of the component (F) is preferably 2500 to 5500, and more preferably 3000 to 5000.
If it is more than the said lower limit, it becomes easy to improve a pill preventing effect more. If it is below the said upper limit, rinse property will become easy to improve more.
In the present specification, the weight average molecular weight is determined from a molecular weight distribution obtained by GPC (gel permeation chromatography) using polypropylene glycol (weight average molecular weight: 800, 1,200, 2,000, 4,000) as a standard.
The component (F) may be one type or two or more types.

In the case of the compound represented by the formula (f1), the component (F) can be produced by a method in which propylene oxide is addition-polymerized to an alcohol (R ¹ —OH). In the case of the compound represented by the formula (f2), it can be produced by a method in which propylene oxide is added to ethylene glycol. In the case of the compound represented by the formula (f3), it can be produced by a method of subjecting glycerin to addition polymerization of propylene oxide.
By adjusting the supply amount of propylene oxide to be subjected to addition polymerization, a propylene oxide adduct having a desired weight average molecular weight can be produced.

The content of the component (F) in the liquid detergent is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass with respect to the total mass of the liquid detergent, It is more preferable that it is 0.08-5 mass%, and 0.1-1.5 mass% is especially preferable.
When the content of the component (F) in the liquid detergent is equal to or more than the preferable lower limit, when this is dissolved in water, it becomes easy to obtain a cleaning liquid that has a high anti-pilling effect and good rinsing properties.
In addition, when the content of the component (F) in the liquid detergent is equal to or less than the preferable upper limit value, when this is dissolved in water, it tends to be a cleaning liquid having a high anti-pilling effect.

The content of the component (F) in the cleaning liquid obtained by dissolving the liquid cleaning agent in water is preferably 0.01 to 100 ppm by mass, and preferably 0.1 to 80 ppm by mass with respect to the total mass of the cleaning liquid. Is more preferable, and it is further more preferable that it is 1-50 mass ppm.
When the content of the component (F) in the cleaning liquid is equal to or more than the preferable lower limit value, the cleaning liquid is likely to have a high anti-pilling effect and good rinsing properties.
Moreover, when the content of the component (F) in the cleaning liquid is equal to or less than the preferable upper limit value, the cleaning liquid is more excellent in the effect of preventing pilling.

  Among the components (C), (D), (E), and (F), two or more types can be used in combination. When using 2 or more types together, the combined use of (C) component and (D) component, (C) component and (E) component, (C) component and (F) component is preferable, (C) component and (D) The combined use of the components is particularly preferable in terms of enhancing the pill preventing effect and rinsing properties. When the component (C) and the component (D) are used in combination, the mass ratio (D) / (C) of the component (D) to the component (C) is preferably 0.001 to 10, more preferably 0.005 to 5. Preferably, 0.01-1 is especially preferable.

The total content of (C), (D), (E), and (F) in the liquid detergent is preferably 0.0001 to 10% by mass with respect to the total mass of the liquid detergent. 0.001 to 5% by mass is more preferable, 0.01 to 3% by mass is further preferable, and 0.5 to 2% by mass is particularly preferable.
When the sum of the contents of (C), (D), (E), and (F) is equal to or more than the preferable lower limit value, the effect of preventing pilling is high and rinsing properties can be improved. When the sum of the contents of (C), (D), (E), and (F) is equal to or less than the preferable upper limit value, it can be uniformly dispersed in the cleaning agent.

The total content of (C), (D), (E), and (F) in the cleaning liquid in which the liquid cleaning agent is dissolved in water is 0.001 to 500 ppm by mass with respect to the total mass of the cleaning liquid. It is preferably 0.01 to 100 ppm by mass, more preferably 0.05 to 50 ppm by mass.
When the sum of the contents of (C), (D), (E), and (F) is equal to or more than the preferable lower limit value, the effect of preventing pilling is high and rinsing properties can be improved. When the sum of the contents of (C), (D), (E), and (F) is equal to or less than the preferable upper limit value, it can be uniformly dispersed in the cleaning agent.

<Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of handling during production, solubility in water when used, and the like.

<Optional component>
The liquid detergent of the present invention may contain an optional component as long as it does not impair the effects of the present invention.
Examples of the optional component include components usually used in liquid detergents. Examples include cationic surfactants other than component (B), anionic surfactants other than component (C), amphoteric surfactants, and solvents other than water. , Chelating agent, enzyme, hydrotrope agent, soil release agent, anti-contamination agent, detergency builder, stabilizer, alkali agent, texture improver, preservative, fluorescent agent, dye transfer inhibitor, pearl agent, antioxidant Examples of agents, antibacterial agents, and coloring agents include general-purpose dyes or pigments, emulsifying agents, fragrances, insoluble particles, pH adjusters, and natural products.

(solvent)
Examples of solvents other than water that can be used in the liquid detergent of the present invention include, for example, monohydric alcohols having 2 to 4 carbon atoms, polyhydric glycols, and glycol ether solvents represented by the following formula (g1), It is a solvent selected from the group consisting of the solvent represented by (g2).
R ^41- (OR ⁴² ) _m2 OH (g1)
In the formula (g1), R ⁴¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁴² represents an alkylene group having 2 to 4 carbon atoms, m represents an average number of repetitions of OR ⁴² , and 1 to 5 It is.
CH ₃ OCR ³³ (CH ₃ ) CHR ³⁴ CHR ³⁵ OR ³⁶ (g2)
In the formula, R ^{33 to} R ³⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁶ is a hydrogen atom or an acetyl group.

Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyvalent glycol include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether solvent represented by the formula (g1) include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and the like. .

  Examples of the solvent represented by the formula (g2) include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, and 3-methoxy-2. -Methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1-propylbutanol, 3 -Methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl acetate, 3-methoxy-2 -Ethylbutyl acetate, 3-methoxy-2-propylbutyla Tate, 3-methoxy-1-methyl-butyl acetate, 3-methoxy-1-ethyl butyl acetate, 3-methoxy-1-propyl-butyl acetate and the like.

Among these, ethanol, propylene glycol, diethylene glycol monobutyl ether, and 3-methoxy-3-methylbutanol are preferable from the viewpoint of fluidity as an inhibitor, mild odor, and availability of raw materials.
These components may be used individually by 1 type, and may be used in combination of 2 or more type.

As for content of the whole solvent containing water, 40-90 mass% is preferable with respect to the total mass of a liquid detergent. When the content is less than or equal to the above upper limit value, the amount of the cleaning agent used for washing can be reduced. When the content is at least the lower limit, it is easy to impart fluidity and liquid stability as a liquid detergent.
As for content of solvents other than water, 1-25 mass% is preferable with respect to the total mass of a liquid detergent. Raw material cost can be reduced as content is below the said upper limit. When the content is at least the lower limit, it is easy to impart fluidity and liquid stability as a liquid detergent.
The ratio of the mass of the solvent other than water to the mass of the entire solvent including water is preferably 0.01 to 0.5. When this mass ratio is at least the lower limit value, fluidity and liquid stability as a liquid detergent can be easily imparted. Raw material cost can be reduced as this mass ratio is below the upper limit.

(Cationic surfactant)
Examples of the cationic surfactant other than the component (B) that can be used in the liquid detergent of the present invention include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, and alkylpyridinium salt cationic surfactants. Is mentioned.

(Anionic surfactant)
The liquid cleaning agent of the present invention exhibits excellent cleaning power by using an anionic surfactant other than the component (C) (hereinafter also referred to as component (H)). The component (H) is also considered to form a complex with the component (B) in the cleaning liquid and enhance the adsorption of the component (B) to the fiber product.

As the component (H), linear alkylbenzene sulfonic acid; α-olefin sulfonic acid; linear or branched alkyl sulfate ester; alkyl ether sulfate ester or alkenyl ether sulfate ester; alkane sulfonic acid having an alkyl group; α-sulfo Examples include fatty acid esters.
The component (H) may be present in the form of a salt in the liquid cleaning agent or in a cleaning solution obtained by dissolving the liquid cleaning agent in water.
Examples of the salt form of component (H) include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

As the linear alkylbenzene sulfonic acid, those having 8 to 16 carbon atoms in the linear alkyl group are preferable, and those having 10 to 14 carbon atoms are more preferable.
As alpha-olefin sulfonic acid, a C10-C20 thing is preferable.
As the alkyl sulfate, those having 10 to 20 carbon atoms in the alkyl group are preferable.
The alkyl ether sulfate ester or alkenyl ether sulfate ester has a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. An average of 1 to 5 moles of polyoxyethylene alkyl ether sulfate, which may be an oxypropylene group, is preferred.
As the alkanesulfonic acid, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 14 to 17 are more preferable. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are more preferable.
As the α-sulfo fatty acid ester, fatty acid residues having 10 to 20 carbon atoms are preferable.

Among these (H) components, at least one selected from linear alkylbenzene sulfonic acid, alkane sulfonic acid, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonic acid is preferable.
In particular, linear alkylbenzene sulfonic acid is most preferable from the viewpoint of easy formation of a complex with the component (B) and improved low-temperature stability.

As the component (H), other anionic surfactants other than those described above may be used. Examples of the other anionic surfactants include carboxylic acid type anionic surfactants such as alkyl ether carboxylic acid, polyoxyalkylene ether carboxylic acid, alkyl (or alkenyl) amide ether carboxylic acid, and acylamino carboxylic acid; And phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester, polyoxyalkylene alkyl phosphoric acid ester, polyoxyalkylene alkyl phenyl phosphoric acid ester, and glycerin fatty acid ester monophosphoric acid ester.
These components (H) may be used alone or in combination of two or more.

The content of the component (H) in the liquid detergent (in the case of a salt, the content as an acid or the like; the same applies hereinafter) is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent. 1-10 mass% is more preferable, and 1-5 mass% is further more preferable.
If content of (H) component is more than the said lower limit, detergency will be raised more and it will be easy to accelerate | stimulate adsorption | suction of (B) component. If it is below the upper limit, good rinsing properties can be easily obtained.
In the cleaning agent, the ratio (B) / (H) of the mass of the component (B) to the mass of the component (H) is preferably 0.1 to 3, and more preferably 0.6 to 2. When (B) / (H) is within the above range, the effect of preventing pills is enhanced. This is presumably because the component (B) and the component (H) form a complex and are easily adsorbed by the fiber product.

In addition, the stability of the liquid preparation may be deteriorated by blending the component (C) in the liquid detergent containing the component (B), but the stability is improved by blending the component (H). Become. The ratio (C) / (H) of the mass of the component (C) to the mass of the component (H) is preferably 0.01 to 10, preferably 0.05 to 8, and more preferably 0.1 to 5.
When (C) / (H) is within the above range, the stability is further improved. Specifically, as the component (H) whose stability is improved in combination with the component (C), linear alkylbenzene sulfonic acid is most preferable.

(Amphoteric surfactant)
The amphoteric surfactant that can be used in the liquid detergent of the present invention may be any amphoteric surfactant conventionally used in liquid detergents for clothing and the like, for example, alkylbetaine type, alkylamide betaine Examples thereof include amphoteric surfactants such as type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, and phosphoric acid type.
These amphoteric surfactants may be used singly or in appropriate combination of two or more.

(Chelating agent)
Examples of the chelating agent that functions as a metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid.
When the liquid cleaning agent of this invention contains a chelating agent, 0.1-20 mass% is preferable with respect to the total mass of a liquid cleaning agent.

(Hydrotrope agent)
Examples of the hydrotrope (hereinafter sometimes referred to as component (I)) include para-toluenesulfonic acid or a salt thereof, cumenesulfonic acid or a salt thereof, benzoate, phenoxyethanol, urea, and the like.
When the liquid detergent of the present invention contains a hydrotrope, the content of the hydrotrope is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent.
Although the stability of a liquid formulation may deteriorate by mix | blending (C) component in the cleaning agent containing (B) component, stability becomes favorable by mix | blending (I) component. The ratio (C) / (I) of the mass of the component (C) to the mass of the component (I) is preferably from 0.01 to 10, preferably from 0.1 to 8, and more preferably from 1 to 5. When (C) / (I) is within the above range, the stability is further improved. Phenoxyethanol and cumene sulfonate are more preferred as component (I) that improves stability in combination with component (C).

(Recontamination inhibitor)
The anti-staining agent is at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one repeating unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. And water-soluble polymers having units.
Specifically, the product name “TexCare SRN-100” (manufactured by Clariant, weight average molecular weight 2000 to 3000), the product name “TexCare SRN-300” (manufactured by Clariant, weight average molecular weight 7000), and the product name “Repel- “O-Tex Crystal” (manufactured by Rhodia), trade name “Repel-O-Tex QC” (manufactured by Rhodia) and the like.

Among these, TexCare SRN-100 is preferable because it is highly soluble in water and excellent in storage stability. Moreover, it is preferable to use the brand name TexCare SRN-170 (manufactured by Clariant), which is commercially available as a 70% aqueous solution of the TexCare SRN-100, from the viewpoint of excellent handleability.
Other anti-staining agents include alkylene oxide adducts of polyalkyleneimines and alkylene oxide adducts of polyalkyleneamines. Specifically, a trade name “Sokalan HP20” (manufactured by BASF) and the like can be mentioned.
When the liquid detergent of the present invention contains a recontamination inhibitor, the content of the recontamination inhibitor is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.

(Alkaline agent)
Examples of the alkali agent include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

(Texture improver)
In order to improve the texture after drying, a silicone oil having a modifying group may be blended. Examples thereof include polyether-modified silicone, amino polyether-modified silicone, amide polyether-modified silicone, alkyl polyether-modified silicone, and the like. By blending the silicone oil having a modifying group, the friction of the textile product in the bath is reduced, and the effect of preventing pills is increased.

  Examples of commercially available products include “CF1188N”, “BY16-878”, “BY16-891”, “BY16-893”, “FV2090-01”, “SILSTLE104”, “SF8417” manufactured by Toray Dow Corning Co., Ltd. , “SF8418”, “BY16-837”, “BY16-906”, “FZ-2203”, “FZ-3789”, etc., “KF-877”, “KF-889”, “KF-889” manufactured by Shin-Etsu Chemical Co., Ltd. "W-22Soft (registered trademark) CTA", "WetSoft AE200", "WetSoft NE810", "WetSoft NE820", "WetSoft WP201" manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and the like.

(Preservative)
Examples of the preservative include “Caisson CG” (trade name) manufactured by Dow Chemical Company, “Acciside MBS” (trade name) manufactured by Sor Japan, “NIPACIDE BIT 20” (trade name) manufactured by Clariant, and the like. .

(Antioxidant)
Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite and the like.
When the liquid detergent of this invention contains antioxidant, 0.01-2 mass% is preferable with respect to the gross mass of a liquid detergent.

(Coloring agent)
Examples of the colorant include Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Red No. 106, Yellow No. 203, and Turquoise P-GR (all products Name) and other general-purpose dyes and pigments.
When the liquid detergent of the present invention contains a colorant, the content of the colorant is preferably 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.

(Fragrance)
As a fragrance | flavor, the fragrance | flavor component etc. which are described in Unexamined-Japanese-Patent No. 2002-146399 are mentioned, for example.
When the liquid detergent of this invention contains a fragrance | flavor, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent.

(PH adjuster)
The liquid detergent of the present invention preferably has a pH of 4 to 10 at 25 ° C, more preferably 4 to 9, and still more preferably 4 to 8. When the pH is in such a range, the storage stability of the liquid detergent can be maintained well.
The pH of the liquid detergent can be adjusted by adding a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable.
In the present specification, pH means a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) with a measurement target at 25 ° C.

(Extracts such as natural products)
Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Ginger, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plants such as St. John's Wort.
When the liquid detergent of the present invention contains an extract such as a natural product, the content of the extract such as a natural product is preferably 0 to 0.5% by mass with respect to the total mass of the liquid detergent.
These components may be used individually by 1 type, and may be used in combination of 2 or more type.

[How to wash]
The method for washing textile products of the present invention (hereinafter also simply referred to as “washing method”) is a method of washing using the liquid detergent of the present invention. Since the liquid cleaning agent of the present invention is excellent in rinsing properties, the number of times of rinsing is only one in the washing method of the present invention.
That is, in the washing method of the present invention, the fiber product is stirred and dehydrated in the cleaning liquid containing the liquid detergent of the present invention, and then the fiber product is stirred and dehydrated in rinsing water not containing the liquid detergent. This is a method for washing textile products that is performed only once.

  In the washing method of the present invention, in the case of a fully automatic washing machine (including a drum type and a vertical type), it is preferable to use a course having a weak water flow compared to a standard course, an automatic course, and the like. For example, a course named a house cleaning course, a fashionable wear course, a dry course, a soft course, a delicate course, a home cleaning course, or the like is selected depending on the model. The rinsing method for these courses includes water rinsing, irrigation rinsing, shower rinsing, etc., all of which are set once.

The amount of cleaning agent used is preferably 30 to 40 g per 1.5 kg of clothing for a drum-type washing machine, and 30 to 40 g for 30 L of water at the time of washing for a vertical washing machine. If it is below the upper limit, rinsing properties are good, and if it is above the lower limit, it is good for preventing pilling and cleaning power.
The amount of clothes put into one washing is preferably 1.5 kg or less per 10 kg capacity of the washing machine if it is a drum type washing machine, and is preferably 3.5 kg or less per 10 kg capacity of the washing machine if it is a vertical washing machine. .
If the amount of water can be selected manually, the bath ratio (bath ratio = amount of water L during washing / kg of clothing) is 15 or more for a drum-type washing machine, or a vertical washing machine. 30 or more is preferable. If it is more than a lower limit, the friction between clothes can be prevented and adsorption | suction of B component can be improved.

The water used for washing is preferably 1 to 5 ° DH hard water. Detergency is high if the hardness is below the upper limit, and rinsing properties are good if the hardness is above the lower limit. The water temperature is preferably 10 to 30 ° C. If the water temperature is lower than the upper limit, the effect of preventing pilling is high, and if the water temperature is higher than the lower limit, the cleaning power and rinsing properties are excellent.
The washing time is preferably 5 to 15 minutes. If it is below the upper limit, the effect of preventing pills is high, and if it is above the lower limit, the cleaning power is excellent. If rinsing is possible, such as water rinsing, shower rinsing, and rinsing, washing with water is preferable from the viewpoint of rinsing properties. The dehydration time is preferably 1 to 6 minutes, and if it is not more than the upper limit value, the effect of preventing pilling is high, and if it is not less than the lower limit value, water drainage is good.

  The preferable setting conditions in a specific washing machine are as follows. The amount of water during washing in the fully automatic washing machine was measured using a liquid flow meter “LW20-PTN” (manufactured by Horiba, Ltd.).

In the case of a fully automatic drum type washing machine NA-VX7600L (Panasonic, manufactured in 2015, 10 kg capacity), it is a house cleaning course (washing 13 minutes, water rinsing 1 time, dehydration 2 minutes setting). With this setting, the amount of water when washing with a total of 1.5 kg of clothes is 24 L, and the amount of water when rinsing is 32 L.
In the case of a fully automatic drum-type washing machine TW-4000VFL (S) (TOSHIBA, manufactured in 2008, 9 kg capacity), a dry course (7 minutes for washing, one rinsing with water and 5 minutes for dehydration) is set. With this setting, the amount of water at the time of washing when a total of 1.5 kg of clothes is put is 26 L, and the amount of water at the time of rinsing is 27 L.
In the case of a fully automatic vertical washing machine NA-FW80S1 (Panasonic, manufactured in 2014, 8 kg capacity), a dry course is set (15 minutes for washing, 1 rinse, 1 minute for dehydration). With this setting, the amount of water when washing when a total of 1.5 kg of clothes is put in is 57 L, and the amount of water when rinsing is 52 L.
In the case of a fully automatic vertical washing machine AW-8V2 (TOSHIBA, manufactured in 2014, 8 kg capacity), a dry course (6 minutes for washing, 1 rinse with water, 6 minutes for dehydration) is set. With this setting, when a total of 1.5 kg of clothing is put in, the amount of water at the time of washing is 73 L, and the amount of water at the time of rinsing is 70 L.
In the case of a fully automatic vertical washing machine BW-D10XTV (HITACHI, manufactured in 2014, 10 kg capacity), a dry course (9 minutes for washing, one rinsing with water, 1 minute for dehydration) is set. With this setting, the amount of water when washing when a total of 1.5 kg of clothing is put in is 49 L, and the amount of water when rinsing is 47 L.

Examples of the textile product to be subjected to the washing method of the present invention include clothing, cloths, bedding, and curtains.
The material of the fiber product is not particularly limited, and may be any of natural fibers such as wool, cotton, silk and hemp, and chemical fibers such as polyester, acrylic, nylon, rayon and polyamide.

  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]
<(A) component>
(A-11) Lutensol TO- 7 ( trade name, manufactured by _BASF), alkyl group of _{C 13 H 27 O (CH 2} CH 2 O) 7 H, carbon atoms ^{R 21} is a branched chain ^{13, R 22} O Is ethylene oxide and n is 7.
(A-12) Softanol 30 (trade name, manufactured by Nippon Shokubai Co., Ltd.), R ²¹ is a linear alkyl group having 12 to 14 carbon atoms, and the oxygen atom is a secondary carbon atom in R ^21. A compound which is bonded and R ²² O is an oxyethylene group.
(A-13) Softanol EP5035 (trade name, manufactured by BASF), R ²¹ is a branched alkyl group having 12 to 14 carbon atoms, R ²² O is ethylene oxide, and n is 3.5.

<(B) component>
(B-1) Lipomin APA168-65E (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.), a mixture of the mass of stearic acid dimethylaminopropylamide and the mass of palmitic acid dimethylaminopropylamide = 7/3. Stearic acid dimethylaminopropylamide is a compound in which R ¹⁰ is a linear alkyl group having 17 carbon atoms, R ¹¹ is a linear alkylene group having 3 carbon atoms, and R ¹² and R ¹³ are alkyl groups having 1 carbon atom. Palmitic acid dimethylaminopropylamide is a compound in which R ¹⁰ is a linear alkyl group having 15 carbon atoms, R ¹¹ is a linear alkylene group having 3 carbon atoms, and R ¹² and R ¹³ are alkyl groups having 1 carbon atom. is there.

<(C) component>
(C-1) Zushi fatty acid (trade name, manufactured by NOF Corporation).
(C-2) C16 soap (trade name, manufactured by Kanto Chemical Co., Inc.), sodium palmitate.

<(D) component>
(D-1) SH200 (trade name, manufactured by Toray Dow Corning).
(D-2) 8590 Additive (trade name, manufactured by Toray Dow Corning).
(D-3) AF-8014 Antiform (trade name, manufactured by Toray Dow Corning).
(D-4) AC-8066 Antiform (trade name, manufactured by Toray Dow Corning).
(D-5) ACP-3073 Antiform (trade name, manufactured by Toray Dow Corning).
(D-6) FS Antiform 93 (trade name, manufactured by Toray Dow Corning).
(DX) KM-91P (Shin-Etsu Chemical Co., Ltd.), a powder type antifoaming silicone that does not correspond to the component (D).

<(E) component>
(E-1) 2-ethylhexyl 2-ethylhexanoate (synthesized by the following synthesis method). X is a compound having a branched alkyl group having 7 carbon atoms, and Y is a compound having a branched alkyl group having 8 carbon atoms.

(Synthesis method of E-1)
A 5 L four-necked flask was charged with 1700 g of 2-ethylhexanoic acid, 1425 g of 2-ethylhexanol, and 17 g of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.) as a catalyst, and was purged with nitrogen. Then, while flowing nitrogen at a flow rate of 1 mL / second, the liquid temperature was raised to 140 ° C. to carry out an esterification reaction, and water produced by the reaction was removed by distillation. After removing water, the temperature was raised to 200 ° C. while gradually reducing the pressure to 0.6 kPa to obtain a crude product. Next, 21.5 g of Hyflo Supercell (trade name, manufactured by Nacalai Tesque Co., Ltd.) (1.5 parts by mass with respect to 100 parts by mass of the crude product) as a filter aid is added to 1500 g of the crude product and stirred for 10 minutes. And uniformly dispersed. Then, pressure filtration was performed at 80 ° C. to obtain 2-ethylhexyl 2-ethylhexanoate.

<(F) component>
(F-1) Actol T-4000 (trade name, manufactured by Mitsui Chemicals, Inc.) polyoxypropylene glyceryl ether, mass average molecular weight 4000, compound represented by the formula (f3).
(F-2) Actol T-3000 (trade name, manufactured by Mitsui Chemicals) polyoxypropylene glyceryl ether, mass average molecular weight 3000, compound represented by the formula (f3).
(F-3) Actol T-5000 (trade name, manufactured by Mitsui Chemicals, Inc.) polyoxypropylene glyceryl ether, mass average molecular weight 5000, compound represented by the formula (f3).

<(A2) component>
(A-21) A product obtained by adding an average of 12 moles of ethylene oxide to linear natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble Co.).
(A-22) An average of 10 moles of ethylene oxide added to a linear natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble Co.).
(A-23) Polyoxyalkylene alkyl ether in which an average of 9 mol of ethylene oxide, an average of 2 mol of propylene oxide, and an average of 9 mol of ethylene oxide are added in this order to a linear primary alcohol having 12 to 14 carbon atoms . In General Formula (a2), R ⁷¹ is a linear alkyl group having 12 to 14 carbon atoms, R ⁷² is a hydrogen atom, J is 0, p = 2, and q = 18.

<(H) component>
(H-1) Lipon LH-200 (trade name, LAS manufactured by Lion Corporation), linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms, average molecular weight 322.

<(I) component>
(I-1) Sodium benzoate (trade name, manufactured by Toagosei Co., Ltd.), sodium benzoate.
(I-2) 2-phenoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.).
(I-3) Teikatox N5040 (trade name, manufactured by Teika Co., Ltd.), sodium cumene sulfonate.
(I-4) An aqueous paratoluenesulfonic acid solution (manufactured by Meitomo Sangyo Co., Ltd.).

<Solvent>
(Ethanol) Specific alcohol 95 degree synthesis (trade name, manufactured by Nippon Alcohol Sales Co., Ltd.).
(PG) Propylene glycol (manufactured by BASF).
(BC) Butyl diglycol (trade name, manufactured by Nippon Emulsifier Co., Ltd.), butyl carbitol.
(Water) Ion exchange water.

<Other optional components>
(POE-modified silicone) CF1188N (trade name, manufactured by Toray Dow Corning Co., Ltd.), polyether-modified silicone, and texture improver.
(Amino POE modified silicone) FZ-3789 (trade name, manufactured by Toray Dow Corning Co., Ltd.), amino polyether modified silicone, texture improver.
(SR agent) TexCare SRN-170C (trade name, manufactured by Clariant Japan KK), soil release agent.
(Citric acid) Liquid citric acid (trade name, Lion Specialty Chemicals Co., Ltd.), chelating agent.
(Fragrance) Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
(BHT) SUMILZER BHT-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.), dibutylhydroxytoluene, antioxidant.
(Dye) Kayanol Milling (trade name, manufactured by Nippon Kayaku Co., Ltd.), Acid Red 138.
(BIT) NIPACIDE BIT 20 (trade name, manufactured by Clariant Japan KK), 1,2-benzoisothiazolin-3-one, preservative.
(MBS) ACTICIDE MBS (trade name, manufactured by THOR GmbH), 2-methyl-4-isothiazolin-3-one / 1,2-benzisothiazolin-3-one, preservative.
(NaOH) Sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), alkaline agent.
(MEA) Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.), alkali agent.

[Evaluation methods]
<Evaluation of hairball prevention>
40g of each liquid washing was put into a fully automatic electric washing machine (Panasonic (NA-VX7600L)), and a commercial knit (UNIQLO "Extra Fine Merino V Neck Sweater (Long Sleeve)" (100% hair)) 7 pieces of commercially available shirts (“BV GOLD round neck short sleeve shirt” (100% cotton) manufactured by Fujibow apparel) were added so that the total amount of clothing would be 1.5 kg.

Using 3 ° DH hard water at 15 ° C., washing was carried out in a house cleaning course (10 minutes for washing, 1 rinse with water, 3 minutes for dehydration). After washing, the knit was laid flat and dried overnight in a place not exposed to direct sunlight. After repeating this washing and drying three times, the knit after drying was compared visually with the reference fabric, and the average score was calculated by assigning points according to the following criteria.
In addition, the reference | standard cloth was produced as follows.
Judgment was accepted when the score was 2 or more (◎, ○, △) (◎: average score 4 or more, ○: average score 3 or more and less than 4 points, Δ: average score 2 or more and less than 3 points) , X: less than 2 average points).

(Standard fabric manufacturing method)
The new knit (UNIQLO “Extra Fine Merino V-Neck Sweater (Long Sleeve)” (100% wool) was cut into two pieces each having a diameter of 140 mm, and the Martindale abrasion tester (James H. Heal & Co. Ltd. The upper part (test piece holder) and the lower part (pilling table) of “Max-Martindale 909” (Halifax, England) were set. The abrasion method was based on J method (modified Martindale method) of JIS L1076, and the number of abrasions was 0, 50, 100, 300, and 500, and reference fabrics having different five levels of pill generation were produced.

(Evaluation criteria)
1 point: Equivalent to a reference cloth worn 500 times by a Martindale abrasion tester.
2 points: Equivalent to a reference cloth worn 300 times by a Martindale abrasion tester.
3 points: Equivalent to a reference fabric worn 100 times by a Martindale abrasion tester.
4 points: Equivalent to the reference fabric worn 50 times by the Martindale abrasion tester.
5 points: Equivalent to the reference fabric that was worn 0 times by the Martindale abrasion tester.

<Rinseability evaluation>
40 g of each liquid detergent composition is put into a fully automatic electric washing machine (manufactured by Panasonic (NA-VX7600L)), and a commercially available knit ("Extra Fine Merino V Neck Sweater (Long Sleeve)" manufactured by UNIQLO (hair 100) %)), And seven commercially available shirts (“BV GOLD round neck short sleeve shirt” (100% cotton) manufactured by Fujibow apparel) were added so that the total amount of clothing would be 1.5 kg.
Then, using 3 ° DH hard water at 15 ° C., washing was performed in a house cleaning course (washing for 10 minutes, water injection once, dehydration for 3 minutes setting). This operation was repeated 5 times continuously using the same knit. When dehydrating, the window of the washing machine had bubble residue, and whether the washing machine automatically extended the number of times of rinsing due to insufficient rinsing was evaluated according to the following evaluation criteria (◎ and ○ were accepted).

(Judgment)
(Double-circle): There is no foam residue at the time of spin-drying | dehydration, and automatic rinsing does not occur.
○: There is no foam residue at the time of dehydration, and rinsing automatic extension occurs.
Δ: Foam remains during dehydration, and rinsing does not automatically extend.
X: There is a foam residue at the time of dehydration, and automatic rinsing occurs.

<Stability evaluation>
The cleaning composition was taken in a cylindrical glass bottle, closed, and stored in a thermostatic bath at −5 ° C. for 1 month. The appearance after storage was visually observed, storage stability was evaluated based on the following criteria, and those with ◎, ○, and Δ were accepted.
A: Uniform, free of suspended matter and sediment, and fluid.
○: Although there is no suspended matter or sediment, it is slightly cloudy. There is fluidity.
Δ: There are suspended matter and sediment. There is fluidity.
X: There is no suspended matter or sediment. There is no fluidity.

(Examples 1 to 23, Comparative Examples 1 to 4)
The liquid detergent of each example was prepared with the formulation shown in Tables 1-4.
In addition, the compounding quantity in a table | surface is a pure part conversion value. Moreover, the component whose compounding quantity is not described in the table | surface is not mix | blended. Further, “appropriate amount” in the table means “amount in which the pH is in the range of 6-8”.
The results of evaluating the anti-pilling property, rinsing property and stability of the liquid cleaning agent of each example are shown in the table.

As shown in Tables 1 to 4, Examples 1 to 23 were good in preventing pills, rinsing properties and stability. On the other hand, Comparative Example 1 which does not contain the component (A1) and does not contain any of the components (C), (D), (E) and (F) is inferior in preventing pilling and rinsing. It was. Moreover, the comparative example 2 which does not contain any component of (C), (D), (E), (F) was inferior to pill preventing property and rinsing property, and the comparative example 3 was inferior to rinsing property. In addition, Comparative Example 4 which does not contain any of the components (C), (D), (E) and (F) and contains an antifoaming silicone which does not fall under the component (D) is inferior in stability. It was.
From the above results, by applying the present invention, it is possible to suppress the generation of pills due to rubbing during washing, the foam is good and the rinsing can be performed only once. It was confirmed that it could be reduced to the minimum.

Claims (5)

(A) Nonionic surfactant other than the propylene oxide adduct of alcohol represented by any one of the following general formulas (f1) to (f3), which is a compound (A1) represented by the following general formula (a1) A nonionic surfactant containing,
(B) contains an alkylamidoamine represented by the following general formula (b), and
(C) Higher fatty acid, (D) Antifoam silicone selected from oil type, oil compound type, emulsion type, self-emulsifying type, (E) fatty acid ester represented by the following general formula (e), and (F) Containing one or more selected from propylene oxide adducts of alcohol represented by any of the following general formulas (f1) to (f3),
The liquid detergent for textiles whose ratio (A1) / (B) of the mass of said (A1) to the mass of said (B) is 4-20.
_{^{R 21 -O- (R 22 O)}} n -H ··· (a1)

X-COO-Y (e)

In the formula (a1), R ²¹ represents a branched alkyl group having 12 to 16 carbon atoms or a linear alkyl group having 12 to 16 carbon atoms, and when R ²¹ is the linear alkyl group, the oxygen atom is To a secondary carbon atom in the linear alkyl group. R ²² represents an alkylene group having 2 to 4 carbon atoms. Moreover, n shows the average repeating number of R < ²² > O, and is 3-10.
In formula (b), R ¹⁰ is a linear or branched hydrocarbon group having 9 to 23 carbon atoms. R ¹¹ is a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently an average repeating number of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or an oxyethylene group. 1 to 25 (poly) oxyethylene groups.
In formula (e), X is a C5-C21 branched alkyl group or a C5-C21 linear alkyl group. When X is a linear alkyl group, the carbon atom bonded to the carbon atom of the carbonyl group in formula (e) is a secondary carbon atom. Y is an alkyl group having 3 to 16 carbon atoms, or ^{- _{(R 31 O) m1 -R 32}} . R ³¹ is an alkylene group having 2 to 4 carbon atoms. m shows the average repeating number of R < ³¹ > O, and is 1-5. R ³² is an alkyl group having 1 to 16 carbon atoms, a phenyl group, or a benzyl group.
In formula (f1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, PO represents an oxypropylene group, and n1 represents an average number of repetitions of PO and is 10 to 350.
In formula (f2), PO represents an oxypropylene group, n2 and n3 each independently represents the average number of repetitions of PO, and the total of n2 and n3 is 10 to 350.
In formula (f3), PO represents an oxypropylene group, n4, n5 and n6 each independently represents the average number of repetitions of PO, and the total of n4, n5 and n6 is 10 to 350.   The liquid detergent for textiles according to claim 1, wherein the total content of (C), (D), (E), and (F) is 0.0001 to 10% by mass.   The liquid detergent for textiles according to claim 1 or 2, wherein a ratio (A1) / (A) of the mass of (A1) to the mass of (A) is 0.001 to 0.8.   After stirring and dehydrating a textile product in the cleaning liquid containing the liquid detergent according to any one of claims 1 to 3, the textile product is stirred in rinsing water not containing the liquid detergent, and then dehydrated. A method of washing textile products, which is performed only once.   The ratio of the mass of the cleaning liquid to the mass of the textile product when stirring the textile product in the cleaning liquid containing the liquid detergent is 15 to 30, and the fiber when the textile product is stirred in the rinsing water The method for washing a textile product according to claim 4, wherein a ratio of the mass of the rinsing water to the mass of the product is 15 to 30.