HK1214291B

HK1214291B - Liquid detergent composition for clothing

Info

Publication number: HK1214291B
Application number: HK16102223.7A
Authority: HK
Inventors: 喜多亚矢子; 柳泽友树; 牧昌孝
Original assignee: 花王株式会社
Priority date: 2012-12-28
Filing date: 2013-12-25
Publication date: 2018-08-03

Description

Liquid detergent composition for clothing

Technical Field

The present invention relates to a liquid detergent composition for clothing and a method for cleaning clothing.

Background

In recent years, the global energy problems, the reduction of carbon dioxide emissions, the lack of hydration problems, and the like have been increasing, and environmental awareness has been increasing. From the viewpoint of reduction in the amount of resin in a container, reduction in the cost of transportation fuel, reduction in waste after use, and the like, technologies relating to a high-concentration liquid detergent composition are disclosed. For example, jp 2011-208130 a discloses a liquid detergent composition containing (a) a nonionic surfactant having an average molar number of addition of alkylene oxide groups of 16 to 35, (b) an anionic surfactant having an alkylene oxide group having 3 and/or 4 carbon atoms, and (c) a specific solvent, and having a high concentration of the surfactant. In the examples, as an optional component, a compound obtained by adding ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms in an average amount of 3 moles was used. It is described that the composition is excellent in low-temperature storage stability, solubility in water, and cleaning performance.

Further, anionic surfactants have been known as surfactants to be incorporated in liquid detergent compositions for clothing, and for example, anionic surfactants having an ethyleneoxy group and a propyleneoxy group in the molecule have been used conventionally. Jp 56-5896 a discloses a detergent composition containing a cationic active agent and an anionic active agent containing an ethyleneoxy group and an propyleneoxy group in the molecule, and describes that a polyoxyethylene alkyl or alkenyl ether may be blended therein.

In Japanese Kokai publication 2009-185252, a liquid detergent composition is disclosed in which a linear polyoxyalkylene alkyl ether sulfate and a polyoxyethylene alkyl ether having a low ethylene oxide addition mole number are used in combination under specific conditions.

Jp 2012 a 107102 a discloses a liquid detergent composition containing a specific branched compound, a specific alkyl sulfate having an oxypropylene group and an oxyethylene group, and an amphoteric surfactant and/or a semi-polar surfactant.

Jp 2010-202720 a discloses a liquid detergent composition containing a specific sulfate ester having an oxypropylene group and an oxyethylene group, a surfactant capable of forming a complex ionically with the sulfate ester and having a hydrocarbon group having at least 1 carbon atom number of 8 to 18, an antibacterial metal ion, at least one member selected from the group consisting of a hydrotrope and an organic solvent, and water under specific conditions.

On the other hand, there is a type of a household full-automatic washing machine, more specifically, a household drum full-automatic washing machine, a household pulsator full-automatic washing machine, or a household agitation full-automatic washing machine, which includes a washing program (also referred to as a fast program) capable of shortening a washing time including a cleaning time, a rinsing time, and a dehydrating time, in addition to a standard program. In the procedure of shortening the washing time, reduction of the number of rinsing times or shortening of the time for cleaning the laundry with the detergent composition is carried out. In general, the washing time in the standard program is set to 10 minutes to 15 minutes, and the washing time in the fast program is set to 5 minutes, for example, in some cases. In addition, the user may arbitrarily set the washing time to 5 minutes. The user can shorten the time required for washing by selecting a quick program and can use the time effectively. In addition, the amount of electricity required for washing can be reduced. When a program for shortening the washing time is selected, effects such as reduction in the number of times of rinsing and shortening of the cleaning time can be obtained.

Disclosure of Invention

The present invention relates to a liquid detergent composition for clothing, which is prepared by mixing the following components (a), (b), (c) and water, wherein the total mixing amount of the components (a) and the mixing amount of the components (b) is more than 15 mass% and less than 70 mass% relative to the total mass of all the mixing raw materials, the mass ratio of the mixing amount of the components (a) to the mixing amount of the components (b) is more than 0.5 and less than 7 in terms of the components (b)/the components (a),

(a) the components: a nonionic surfactant represented by the following general formula (1),

R¹O-(EO)_mH (1)

[ in the formula, R¹Represents a hydrocarbon group having 8 to 18 carbon atoms, EO represents an ethyleneoxy group, m represents an average molar number of addition, and m is a number of 1 to 10.]

(b) The components: an anionic surfactant represented by the following general formula (2),

R²O-[(A¹O)_p/(EO)_q]-SO₃M (2)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p and q represent average addition mole numbers, p is a number of 1 to 5, and q is a number of 0 to 10. "/" indicates block bonding in any order (A)¹O)_pRadical and (EO)_qAnd (4) a base. M is a cation.]

(c) The content of the organic solvent having 1 or more hydroxyl groups is 5% by mass or more and 40% by mass or less based on the total mass of all the blending raw materials.

The present invention relates to a liquid detergent composition for clothing, which is prepared by mixing the following components (a), (b), (c) and water, wherein the total mixing amount of the components (a) and the mixing amount of the components (b) is more than 15 mass% and less than 70 mass%, and the mass ratio of the mixing amount of the components (a) and the mixing amount of the components (b) is more than 0.5 and less than 10 in terms of the components (b)/the component (a).

(a) The components: a nonionic surfactant represented by the following general formula (1)

R¹O-(EO)_mH (1)

(b) The components: an anionic surfactant represented by the following general formula (2-1),

R²O-(A¹O)_p-(EO)_q-SO₃M (2-1)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p and q represent average addition mole numbers, p is a number of 0.5 or more and 5 or less, and q is a number of 0 or more and 10 or less. M is a cation.]

(c) An organic solvent having 1 or more hydroxyl groups: the content thereof is 5 to 40% by mass (mass% is relative to the total mass of all the blended raw materials).

The present invention relates to a liquid detergent composition for clothing, which is obtained by blending the following component (a), component (b), component (c) and water, wherein the mass ratio of the blending amount of the component (a) to the blending amount of the component (b) is 0.4 to 10 in terms of the component (b/(a).

R¹O-(EO)_mH (1)

(b) The components: an anionic surfactant represented by the following general formula (2-2),

R²O-(EO)_p-(A¹O)_q-SO₃M (2-2)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p and q represent average addition mole numbers, p is a number of 0.5 or more and 5 or less, and q is a number of 0.5 or more and 5 or less. M is a cation.]

(c) An organic solvent having 1 or more hydroxyl groups in the molecule: the content thereof is 5 to 40 mass% (mass% is relative to the total mass of all the blending raw materials).

The present invention relates to a liquid detergent composition for clothing, which is obtained by blending the following component (a), component (b), component (c) and water, wherein the mass ratio of the blending amount of the component (a) to the blending amount of the component (b) is 0.5 to 5 in terms of the component (b/(a).

R¹O-(EO)_mH (1)

R²O-(A¹O)_p-(EO)_q-SO₃M (2-1)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from the group consisting of an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy groupP and q represent average molar numbers of addition, p is a number of 0.5 to 5 inclusive, and q is a number of 0 to 10 inclusive. M is a cation.]

The present invention also relates to a method for cleaning clothing, wherein the clothing is cleaned for 1 to 7 minutes by using a cleaning liquid containing water and 0.01 to 0.1 mass% of the liquid detergent composition for clothing of the present invention, the temperature of the cleaning liquid being 0 to 35 ℃, and the bath ratio represented by the ratio of the mass of the clothing to the amount (liter) of the cleaning liquid is 3 to 50 inclusive.

Detailed Description

Japanese patent application laid-open publication 2011-208130 does not suggest an improvement in cleaning speed. Japanese patent laid-open No. Sho 56-5896 does not suggest an improvement in cleaning speed.

In the case of performing washing in the rapid procedure as described above, the user expects the same stain removal as in the normal washing procedure even if the cleaning time is short. However, it was found that: if the cleaning time is shortened, the cleaning performance tends to be lowered more than the degree predicted from the shortening of the cleaning time.

The invention provides a liquid detergent composition for clothing, which can show sufficient cleaning power even if the cleaning time is short. Specifically, a liquid detergent composition for clothing is provided which can achieve a cleaning power equivalent to a 10-minute washing time with a 5-minute washing time.

According to the present invention, a liquid detergent composition for clothing can be provided which exhibits sufficient detergency even with a short cleaning time. The liquid detergent composition for clothing of the present invention can achieve a cleaning power equivalent to that of a standard procedure having a sufficient cleaning time even when a rapid procedure is selected. The liquid detergent composition for clothing of the present invention is excellent not only in the speed of cleaning sebum stains but also in the performance of cleaning especially the falling stains which are difficult to remove.

The present inventors have found that by blending the component (a) and the component (b) in a specific blending amount and mass ratio and using the component (c) in combination, a cleaning power equivalent to that of a standard procedure with a sufficient cleaning time can be achieved even when the cleaning time is short. Hereinafter, the present invention will be described in some cases where the meaning of "a cleaning time is short and a cleaning power equal to or higher than that of a standard procedure in which a sufficient cleaning time can be achieved" is expressed as "a cleaning speed is high" or "a cleaning speed can be increased".

< component (a) >

The nonionic surfactant of the component (a) used in the present invention is a compound represented by the following general formula (1).

R¹O-(EO)_mH (1)

(a) In the general formula (1) of component (A), R¹The hydrocarbon group has 8 to 18 carbon atoms, and from the viewpoint of detergency, the hydrocarbon group has preferably 10 or more carbon atoms, more preferably 11 or more carbon atoms, and preferably 16 or less, more preferably 14 or less carbon atoms. As R¹The hydrocarbon group of (3) is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group, from the viewpoint of detergency. From the viewpoint of cleaning power, R¹Preferably a linear or branched hydrocarbon group, more preferably a linear hydrocarbon group. From the viewpoint of detergency, as R¹The linear hydrocarbon group of (1) is preferably a linear primary hydrocarbon group. In addition, from the viewpoint that the cleaning speed can be increased, R¹Preferably selected from branched primaryHydrocarbyl and linear secondary hydrocarbyl. In the general formula (1), R bonded to an oxygen atom¹The carbon atom(s) of (c) may be primary or secondary carbon atoms. R bonded to an oxygen atom in the general formula (1) from the viewpoint of detergency¹The carbon atom (b) is preferably a linear primary hydrocarbon group, and is preferably a secondary carbon atom from the viewpoint of enhancing the cleaning speed. From the viewpoint of cleaning power, R¹A linear primary alkyl group having 10 to 16 carbon atoms is preferable. From the viewpoint that the cleaning speed can be increased, R¹Preferably, the alkyl group is a group selected from a branched primary alkyl group having 10 to 16 carbon atoms and a linear secondary alkyl group having 10 to 16 carbon atoms.

The method for obtaining the compound of the general formula (1) is not particularly limited, and can be obtained by subjecting an alcohol having a hydrocarbon group with a carbon atom number of 8 or more and 18 or less to an addition reaction with ethylene oxide. The average molar number m of addition of ethylene oxide is 1 to 10 inclusive. From the viewpoint of cleaning power of sebum stains, m is 1 or more, preferably 2 or more, more preferably 2.5 or more, and still more preferably 3 or more. Further, from the viewpoint of increasing the cleaning speed and the viewpoint of cleaning power when the liquid cleaning agent is applied directly to the food stain, the cleaning rate is 10 or less, preferably 9 or less, and more preferably 8 or less.

The component (a) is preferably R in the general formula (1) from the viewpoint of detergency¹A nonionic surfactant which is a linear primary or secondary alkyl group having 10 to 14 carbon atoms in number and has an average addition mole number m of 3 to 8.

In addition, it is preferable that the component (a) contains R selected from the group consisting of the compounds represented by the general formula (1) from the viewpoint of enhancing the cleaning speed¹Nonionic surfactant which is a branched primary hydrocarbon group and R in the general formula (1)¹Among nonionic surfactants having a linear secondary hydrocarbon group, the nonionic surfactant (a1) [ hereinafter referred to as component (a 1]]The component (a) of (a). (a1) Component (C) is preferably R in the general formula (1)¹The hydrocarbyl group of (a) is an alkyl group. Therefore, the component (a1) is preferably selected fromR in the general formula (1)¹A nonionic surfactant which is a branched primary alkyl group having 8 or more and 18 or less carbon atoms, and R in the general formula (1)¹Among nonionic surfactants having a linear secondary alkyl group having 8 to 18 carbon atoms. When the component (a1) is used, the proportion of the component (a1) in the component (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

Further, the component (a) is preferably the component (a1) and R in the general formula (1) from the viewpoint of improving the cleaning speed¹A nonionic surfactant (a2) having a linear primary hydrocarbon group [ hereinafter referred to as component (a2) ]]Combinations of (a) and (b). When the component (a1) and the component (a2) are used, the total ratio of the component (a1) to the component (a2) in the component (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of improving the cleaning speed.

The most preferable embodiment of the component (a) is that the component (a) contains the component (a1) and the component (a2), and the blending ratio of the component (a1) to the component (a2) is preferably 0.5 or more, more preferably 0.7 or more, more preferably 0.9 or more, more preferably 1.0 or more in terms of the mass ratio of the component (a 1)/the component (a2), and is preferably 7 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, and more preferably 2 or less from the viewpoint of the cleaning power of the falling dirt adhering to the clothing.

The mass ratio of the component (a 1)/component (a2) is preferably 0.7 to 5, more preferably 0.9 to 3, and even more preferably 1.0 to 2, from the viewpoint of enhancing the cleaning speed and achieving a good cleaning effect against the food stain adhering to the clothing.

< component (b) >

By blending the component (b) with the component (a) in a specific ratio and using the component (c) in a specific amount, a liquid detergent composition for clothing which can improve the cleaning speed can be obtained.

(b) The component (A) is an anionic surfactant represented by the following general formula (2).

R²O-[(A¹O)_p/(EO)_q]-SO₃M (2)

Examples of the component (b) include: an anionic surfactant selected from the group consisting of an anionic surfactant represented by the following general formula (2-1) [ hereinafter referred to as component (b1) ], and an anionic surfactant represented by the following general formula (2-2) [ hereinafter referred to as component (b2) ].

R²O-(A¹O)_p1-(EO)_q1-SO₃M (2-1)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p1 and q1 represent average addition mole numbers, p1 is a number of 1 or more and 5 or less, and q1 is a number of 0 or more and 10 or less. M is a cation.]

R²O-(EO)_q2-(A¹O)_p2-SO₃M (2-2)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from alkylene oxide groups having 3 carbon atoms and alkylene oxide groups having 4 carbon atoms, EO represents an ethyleneoxy group, p2 and q2 represent average addition mole numbers, and p2 is 1 or more and 5 or lessQ2 is a number of 0.5 to 5 inclusive. M is a cation.]

The anionic surfactant of component (b1) used in the present invention is a compound represented by the following general formula (2-1).

R²O-(A¹O)_p1-(EO)_q1-SO₃M (2-1)

(b1) In the general formula (2-1) of component (A), R²A hydrocarbon group having 8 to 22 carbon atoms. From the viewpoint of cleaning power, R²Has 8 or more carbon atoms, preferably 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 16 or less carbon atoms, and even more preferably 14 or less carbon atoms. As R²The hydrocarbon group of (3) is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group, from the viewpoint of detergency. From the viewpoint of detergency or availability of raw materials, R²The alkyl group is preferably a linear hydrocarbon group, more preferably a linear alkyl group, and still more preferably a linear primary alkyl group. R²The alkyl group having 12 to 14 carbon atoms is preferable, the linear alkyl group is more preferable, and the linear primary alkyl group is even more preferable. In the general formula (2-1), R bonded to an oxygen atom in the liquid detergent composition is a group represented by formula (2-1)²The carbon atom(s) of (c) is preferably a primary carbon atom.

As A in the general formula (2-1)¹O is an alkylene oxide group having 3 or 4 carbon atoms, and includes 1 or more groups selected from the group consisting of oxytrimethylene, oxypropane-1, 2-diyl, oxybutane-1, 3-diyl, oxybutane-2, 3-diyl and oxytetramethylene. From the viewpoint of availability, it is preferably selected from oxypropylenesAlk-1, 2-diyl [ also commonly referred to sometimes as propyleneoxy]And oxybutane-1, 2-diyl (also commonly referred to as a butenyloxy group), and more preferably oxypropane-1, 2-diyl.

P1 in the formula (2-1) is A¹The average molar number of O added is a number of 1 to 5. From the viewpoint of detergency against sebum stains, p1 is preferably 1.1 or more, more preferably 1.2 or more, more preferably 1.3 or more, more preferably 1.4 or more, more preferably 1.5 or more, and more preferably 1.8 or more. From the viewpoint of enabling the cleaning speed to be increased, p1 is 5 or less, preferably 4 or less, more preferably 3 or less, more preferably 3.0 or less, more preferably 2.9 or less, more preferably 2.8 or less, more preferably 2.5 or less. From the viewpoint of increasing the cleaning speed, the component (b1) is preferably an anionic surfactant having p1 of 1 or more and 3 or less in the general formula (2-1).

Q1 in the general formula (2-1) is the average number of moles of EO added, and is a number of 0 to 10 from the viewpoint of detergency. From the viewpoint of further increasing the cleaning speed, q1 is preferably a number of 0.5 or more, more preferably 0.8 or more, more preferably 1 or more, more preferably 1.5 or more, more preferably 1.8 or more, more preferably 2 or more. From the viewpoint of detergency, q1 is a number of 10 or less, preferably 8 or less, more preferably 5 or less, and more preferably 3 or less. When q1 is not 0, (A)¹O)_p1And (EO)_q1With (A)¹O)_p1、(EO)_q1Sequence of (A) and R²The O blocks are combined.

In addition, M in the general formula (2-1) is a cation. Preferred examples of M include: hydrogen ions, alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions having 1 to 6 carbon atoms.

As the alkali metal ion, there may be mentioned: sodium ions, potassium ions, lithium ions; examples of the alkaline earth metal ion include: magnesium ions; examples of the alkanolammonium ion having 1 to 6 carbon atoms include: monoethanol ammonium ion, triethanol ammonium ion. Among them, from the viewpoint of detergency, alkali metal ions such as sodium ions and potassium ions or monoethanol ammonium ions are preferable, and monoethanol ammonium ions are more preferable.

The method for producing the anionic surfactant represented by the general formula (2-1) is not particularly limited. For example, an intermediate compound (1) is obtained by adding an alkylene oxide having 3 carbon atoms or 4 carbon atoms, preferably propylene oxide, to 1 mole of an alcohol having a hydrocarbon group having 8 to 22 carbon atoms, preferably a linear aliphatic saturated primary alcohol having 10 to 14 carbon atoms, preferably 1.0 mole or more, more preferably 1.1 mole or more, more preferably 1.2 mole or more, more preferably 1.3 mole or more, more preferably 1.4 mole or more, more preferably 1.5 mole or more, more preferably 1.8 mole or more and 5 mole or less, preferably 4 mole or less, more preferably 3 mole or less, more preferably 3.0 mole or less, more preferably 2.9 mole or less, more preferably 2.8 mole or less, more preferably 2.5 mole or less. Next, ethylene oxide is added to the intermediate compound (1) in an amount of 0 mol or more, preferably 0.5 mol or more, more preferably 0.8 mol or more, more preferably 1 mol or more, more preferably 1.5 mol or more, more preferably 1.8 mol or more, more preferably 2 mol or more, and 10 mol or less, preferably 8 mol or less, more preferably 5 mol or less, more preferably 3 mol or less to obtain an intermediate compound (2). Then, the intermediate compound (2) is sulfated and, if necessary, neutralized, whereby an anionic surfactant represented by the general formula (2-1) can be obtained.

The anionic surfactant of component (b2) used in the present invention is a compound represented by the following general formula (2-2).

R²O-(EO)_q2-(A¹O)_p2-SO₃M (2-2)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group having 3 carbon atoms or an alkylene oxide group having 4 carbon atomsIn the alkylene oxide group, EO represents an ethyleneoxy group, p2 and q2 represent an average addition mole number, p2 is a number of 1 or more and 5 or less, and q2 is a number of 0.5 or more and 5 or less. M is a cation.]

(b2) In the general formula (2-2) of component (A), R²、A¹O, M is the same as the general formula (2-1) of the component (b).

Q2 in the general formula (2-2) represents the average molar number of EO molecules added, and is a number of 0.5 to 5. From the viewpoint of enabling the cleaning speed to be increased, q2 is preferably 0.8 or more, more preferably 1 or more, more preferably 1.5 or more, and still more preferably 1.8 or more. From the viewpoint of cleaning power for sebum stains, q2 is preferably 5 or less, more preferably 4 or less, more preferably 3 or less, and more preferably 2.5 or less.

P2 in the formula (2-2) is A¹The average molar number of O added is a number of 1 to 5. From the viewpoint of increasing the cleaning speed, p2 is a number of 1 or more, preferably 1.5 or more, more preferably 1.8 or more. From the viewpoint of detergency, p2 is a number of 5 or less, preferably 4 or less, more preferably 3 or less, and more preferably 2.5 or less.

The method for producing the anionic surfactant represented by the general formula (2-2) is not particularly limited. For example, ethylene oxide is added to 1 mole of an alcohol having a hydrocarbon group having 8 to 22 carbon atoms, preferably a linear aliphatic saturated primary alcohol having 10 to 14 carbon atoms, in an amount of 0.5 mole or more, preferably 0.8 mole or more, more preferably 1 mole or more, more preferably 1.5 mole or more, more preferably 1.8 mole or more, and 5 mole or less, preferably 4 mole or less, more preferably 3 mole or less, more preferably 2.5 mole or less to obtain an intermediate compound (1'). Next, an intermediate compound (2') is obtained by adding an alkylene oxide having 3 carbon atoms and/or an alkylene oxide having 4 carbon atoms, preferably propylene oxide to the intermediate compound (1') in an amount of 1 mol or more, preferably 1.5 mol or more, more preferably 1.8 mol or more, and 5 mol or less, preferably 4 mol or less, more preferably 3 mol or less, more preferably 2.5 mol or less. Then, the intermediate compound (2') is sulfated and, as the case may be, neutralized, whereby an anionic surfactant represented by the general formula (2-2) can be obtained.

< component (c) >

The liquid detergent composition for clothing of the present invention, which comprises the component (a) and the component (b) in a specific ratio, further comprises the component (c) of an organic solvent having 1 or more hydroxyl groups, from the viewpoint of enhancing the cleaning speed and the cleaning power when the liquid detergent composition is applied directly to a falling stain. Further, the component (c) is preferably an organic solvent having a hydroxyl group and an ether group, from the viewpoint that the cleaning speed can be increased.

As the organic solvent having 1 or more hydroxyl groups, 1 or more compounds represented by the following components (c1) to (c6) can be used.

(c1) The components: a monohydric alcohol having an aliphatic hydrocarbon group having 2 to 6 carbon atoms;

examples thereof include: a monohydric alcohol selected from the group consisting of ethanol, 1-propanol, 2-propanol, and 1-butanol.

(c2) The components: an alcohol having 2 to 6 carbon atoms, which is two or more and six or less carbon atoms [ excluding the (c3) component ];

examples thereof include: a dihydric or trihydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol (2-methyl-2, 4-pentanediol), 1, 5-pentanediol, 1, 6-hexanediol and glycerol.

(c3) The components: a polyalkylene glycol containing an alkylene glycol unit having 2 to 4 carbon atoms;

examples thereof include: diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and polyalkylene glycols selected from polyethylene glycols having a weight average molecular weight of 400 to 4000 and polypropylene glycols having a weight average molecular weight of 400 to 4000.

(c4) The components: a monoalkyl ether of a (mono-or poly-) alkylene glycol having an alkylene glycol unit having 2 or more and 4 or less carbon atoms and an alkyl group having 1 or more and 4 or less carbon atoms;

examples thereof include: a compound selected from the group consisting of diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol and 1-ethoxy-2-propanol.

(c5) The components: an alkyl glyceryl ether having an alkyl group having 1 to 8 carbon atoms;

examples thereof include: an alkyl glycerol ether selected from the group consisting of 1-methyl glycerol ether, 2-methyl glycerol ether, 1, 3-dimethyl glycerol ether, 1-ethyl glycerol ether, 1, 3-diethyl glycerol ether, triethyl glycerol ether, 1-pentyl glycerol ether, 2-pentyl glycerol ether, 1-octyl glycerol ether and 2-ethylhexyl glycerol ether.

(c6) The components: aromatic alkyl ethers of (mono or poly) alkylene glycols having an alkylene glycol unit having 2 or 3 carbon atoms;

examples thereof include: a compound selected from the group consisting of 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

In the above-mentioned component (c4) and component (c6), the term "(mono or poly) alkylene glycol" means a mono-alkylene glycol or a poly-alkylene glycol. The term "polyalkylene glycol" means that an alkylene glycol unit is contained in an amount of 2 or more and 9 or less.

From the viewpoint of improving the cleaning speed, it is preferable to use 1 or more selected from the above-mentioned components (c1) to (c6) as the component (c). From the viewpoint of further improving the cleaning speed, it is preferable to use 1 or more compounds selected from the group consisting of the component (c1), (c2), (c4) and (c6), more preferably 1 or more compounds selected from the group consisting of the component (c2) and the component (c4), and still more specifically, 1 or more compounds selected from the group consisting of ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether. In the present invention, as the component (c), 1 or more organic solvents selected from propylene glycol and diethylene glycol monobutyl ether are preferably used, and diethylene glycol monobutyl ether is more preferably used.

< water >)

The liquid detergent composition for clothing of the present invention contains water so that the liquid detergent composition is in a liquid state at 4 to 40 ℃. As the water, deionized water (also referred to as ion-exchanged water) or water obtained by adding 1mg/kg to 5mg/kg of sodium hypochlorite to ion-exchanged water can be used. In addition, tap water may also be used.

Liquid detergent composition for clothing

The liquid detergent composition for clothing of the present invention is prepared by blending component (a), component (b), component (c), water, and optional components. Hereinafter, the mass% is based on the total mass of all the blending materials unless otherwise specified. Further, the content of each component may be replaced by the content of the composition.

In the liquid detergent composition for clothing of the present invention, the mass ratio of the amount of component (a) to the amount of component (b) is 0.5 to 7 inclusive, in terms of component (b/(a). The mass ratio of component (b)/component (a) is 0.5 or more, preferably 0.7 or more, and more preferably 0.9 or more, from the viewpoint of increasing the cleaning speed. The mass ratio of component (b)/component (a) is preferably 1.0 or more, more preferably 1.1 or more, more preferably 1.2 or more, and more preferably 1.5 or more, from the viewpoint of improving the cleaning performance of the exfoliative stains which are difficult to remove and the cleaning performance of the sebum stains. The mass ratio of component (b)/component (a) is preferably 6 or less, more preferably 5 or less, from the viewpoint that the cleaning speed can be maintained even with a smaller amount of component (c). In addition, the mass ratio of component (b)/component (a) is preferably 5 or less, more preferably 4 or less, more preferably 3 or less, more preferably 2.5 or less, and more preferably 2 or less, from the viewpoint of detergency against food stains. The mass ratio of component (b)/component (a) is preferably 1.8 or less from the viewpoint of improving the cleaning speed and having the cleaning performance of a falling stain which is difficult to remove. The mass ratio or mass% of component (b) is calculated by using the mass of the acid-type compound, i.e., a compound assuming that the counter ion is a hydrogen ion, as the mass of component (b), instead of the mass of the salt.

In the liquid detergent composition for clothing of the present invention, the total amount of the component (a) and the component (b) is 15% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, from the viewpoint of obtaining higher detergency with respect to a certain amount of use and from the viewpoint of reducing the amount of use of the composition per 1 time. The total of the amount of the component (a) and the amount of the component (b) is 70% by mass or less, preferably 65% by mass or less, and more preferably 60% by mass or less, from the viewpoint of improving the cleaning speed.

The amount of the component (c) is 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass or more, from the viewpoint of improving the cleaning speed. The amount of component (c) is 40% by mass or less, preferably 35% by mass or less, and more preferably 25% by mass or less, from the viewpoint of economy and storage stability.

The mass ratio of the amount of component (a) and the amount of component (b) to the amount of component (c) is preferably 0.07 or more, more preferably 0.1 or more, more preferably 0.15 or more, more preferably 0.2 or more, and more preferably 0.25 or more, in terms of component (c)/component (a) + (b), from the viewpoint of improving the cleaning speed. From the viewpoint of economy and storage stability, the mass ratio is preferably 3 or less, more preferably 2 or less, more preferably 1 or less, and more preferably 0.5 or less.

From the viewpoint of improving the cleaning speed of sebum stains and improving the cleaning performance of exfoliative stains, the mass ratio of the amount of component (c) to the amount of component (a) is preferably 0.5 to 2.5 in terms of component (a/(c). The mass ratio of component (a)/component (c) is preferably 0.6 or more, and more preferably 0.8 or more, from the viewpoint of economy. The mass ratio of component (a)/component (c) is preferably 2.4 or less, more preferably 2.2 or less, more preferably 2.0 or less, more preferably 1.8 or less, more preferably 1.6 or less, and more preferably 1.4 or less, from the viewpoint of improving the cleaning speed.

In the liquid detergent composition for clothing of the present invention, the total of the blending amount of the component (a), the blending amount of the component (b), and the blending amount of the component (c) is preferably 40 mass% or more and 90 mass% or less. (a) The total of the amount of component (a), the amount of component (b), and the amount of component (c) is more preferably 50% by mass or more, more preferably 52% by mass or more, and more preferably 55% by mass or more, and more preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 65% by mass or less.

By dispersing rapidly when the composition of the present invention is added to water for cleaning, the cleaning speed can be increased. From this viewpoint, the mixing ratio of water in the composition of the present invention is preferably 5% by mass or more. From the viewpoint of being able to mix the component (a), the component (b), and the component (d) described later at a high concentration, the mixing ratio of water is preferably 30% by mass or less, more preferably 25% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less.

< optional component >

The liquid detergent composition for clothing of the present invention may further contain the following component (d) in order to maintain the cleaning rate of sebum stains and improve the cleaning performance of sebum stains.

(d) The components: a nonionic surfactant represented by the following general formula (3)

R³O-(A²O)_nH (3)

[ in the formula, R³Represents a hydrocarbon group having 8 to 22 carbon atoms, A²O represents an alkylene oxide group having 2 to 5 carbon atoms, and n represents an average number of moles added and is a number of 16 to 35. A. the²O contains an ethyleneoxy group having 16 or more carbon atoms on average and having 2 carbon atoms. Wherein, in A²When all O are vinyloxy groups, n is a number of 18 or more.]

(d) In the general formula (3) of component (A), R³Is a hydrocarbon group having 8 to 22 carbon atoms, and from the viewpoint of cleaning power of sebum stains, the number of carbon atoms is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more, and is preferably 18 or less, and still more preferably 16 or less. From the viewpoint of availability of raw materials, R³Linear hydrocarbon groups are preferred. In addition, as R³The hydrocarbon group of (3) is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R³Preferably a straight chain or branched chain hydrocarbon group, more preferably a straight chain hydrocarbon group. In the general formula (3), R bonded to an oxygen atom³The carbon atom(s) of (c) is preferably a primary carbon atom.

The method for obtaining the compound of the general formula (3) is not particularly limited, and can be obtained by adding an alkylene oxide having 2 to 5 carbon atoms to an alcohol having a hydrocarbon group having 8 to 22 carbon atoms. In addition, in the compounds of the general formula (3), ethylene oxide must be used as the above-mentioned alkylene oxide.

Here, the average molar number n of addition of the alkylene oxide having 2 to 5 carbon atoms is 16 to 35. When n is 16 or more, the component (d) is adsorbed together with the component (a) or the component (b) on sebum stains adhered to clothes, and high cleaning performance can be achieved while maintaining cleaning speed. When n is 35 or less, the cleaning performance is good. n is preferably a number of 17 or more,more preferably 18 or more, and still more preferably more than 18. Further, it is preferably 30 or less, more preferably 25 or less. The compound of the general formula (3) contains, as (a), an alkyleneoxy group having 2 carbon atoms, i.e., an ethyleneoxy group, in an amount of 14 moles or more on average, preferably 15 moles or more on average, more preferably 16 moles or more on average, and still more preferably 18 moles or more²O)_n. Or A can be²O is each a vinyloxy group, and n in this case is 18 or more. A other than EO²O is preferably propyleneoxy (also known as oxypropane-1, 2-diyl). In general, n may be an alkylene oxide having 2 to 5 carbon atoms relative to R in the production of the component (d)³The reaction ratio of the alcohol represented by OH. Further, an alkylene oxide group having 3 to 5 carbon atoms is contained as A²The O compound is more excellent in higher concentration than the case of all the ethyleneoxy groups, and is easy to maintain stability.

In addition, component (d) preferably has a propyleneoxy group as A from the viewpoint of improving the cleaning performance of sebum stains²O, and further the component (d) is preferably a compound represented by the following general formula (3-1).

R³O-[(C₂H₄O)_n1/(A²¹O)_n2]-H (3-1)

[ in the formula, R³Has the same meaning as the general formula (3), A²¹O is an alkylene oxide group having 3 to 5 carbon atoms. n1 and n2 represent average molar numbers of addition, n1 represents a number of 15 to 30 inclusive, and n2 represents a number of 1 to 5 inclusive. "/" denotes C₂H₄O radical and A²¹The O group may be combined in any of random and block. In addition, A²¹O may also be divided into multiple chunks.]

The compound of the general formula (3-1) can be obtained by adding ethylene oxide and an alkylene oxide having 3 to 5 carbon atoms randomly or in blocks to an alcohol having 8 to 22 carbon atoms.

In the general formula (3-1), n1 is an average addition mole number of EO, that is, an ethyleneoxy group, and has a lower limit value of 15 or more, preferably 16 or more, more preferably 18 or more, and an upper limit value of 30 or less, preferably 27 or less, more preferably 24 or less, from the viewpoints of storage stability, solubility, and cleaning performance of sebum stains. n2 is the average number of moles of alkylene oxide groups having 3 to 5 carbon atoms added, and has a lower limit of 1 or more, preferably 2 or more, and an upper limit of 5 or less, preferably 4 or less, more preferably 3 or less, from the viewpoint of cleaning performance of sebum stains. N in the general formula (3) has a relationship of n ═ n1+ n2 with n1 and n2 in the general formula (3-1).

A in the general formula (3-1)²¹O, which is an alkylene oxide having 3 to 5 carbon atoms, is obtained by addition reaction of an alkylene oxide having 3 to 5 carbon atoms. Preferred is an alkylene oxide group having 3 carbon atoms and/or an alkylene oxide group having 4 carbon atoms, and specific examples thereof include: trimethylene oxide, oxypropane-1, 2-diyl, oxybutane-1, 3-diyl, oxybutane-2, 3-diyl, oxytetramethylene. A. the²¹O is preferably an oxypropane-1, 2-diyl group (hereinafter, in the present invention, there is also a case where the oxypropane-1, 2-diyl group is a propyleneoxy group or a PO group).

In the present invention, from the viewpoint of obtaining a liquid detergent composition excellent in low-temperature storage stability, cold water solubility and cleaning performance, it is more preferable to use a compound in which the average addition mole number n1 of ethyleneoxy groups is 15 or more, further 16 or more, further 18 or more, and 27 or less, further 24 or less, further 22 or less, and the average addition mole number n2 of propyleneoxy groups, which is PO, is 1 or more, further 2 or more, and further 4 or less, further 3 or less.

In the general formula (3-1), "/" means C as the component (d) in the present invention₂H₄O group, i.e., ethyleneoxy group (hereinafter, referred to as EO) and A²¹The relation of the O groups may be random or block. In addition, A²¹O may also be divided into multiple chunks.

More specific examples of the structure of the above general formula (3-1) include 1 or more compounds selected from the following general formulae (3-1-1) to (3-1-5).

R³O-(A²¹O)_n2-(C₂H₄O)_n1-H (3-1-1)

R³O-(C₂H₄O)_n1-(A²¹O)_n2-H (3-1-2)

R³O-[(C₂H₄O)_n11·(A²¹O)_n2]-(C₂H₄O)_n12-H (3-1-3)

R³O-(C₂H₄O)_n11-[(A²¹O)_n2·(C₂H₄O)_n12]-H (3-1-4)

R³O-(C₂H₄O)_n11-(A²¹O)_n2-(C₂H₄O)_n12-H (3-1-5)

[ in the formula, R³O、n1、n2、(A²¹O) is as defined above, n11 and n12 are average molar numbers of addition, and n1 is n11+ n 12. "·" indicates random incorporation. In addition, A²¹O may also be divided into multiple blocks.]

The compounds represented by the general formulae (3-1-1) to (3-1-5) can be obtained by considering the alkylene oxide relative to R³OH reaction ratio and reaction sequence.

With respect to R in the general formula (3-1)³R of O-bound to an oxygen atom³Is a linear primary alkyl group, and has superior cleaning power compared with a linear secondary alkyl compound. More preferably R³A compound which is a linear primary alkyl group. At R³In the case of a linear primary alkyl group, from the viewpoint of cleaning properties of sebum stains, 1 or more compounds selected from the group consisting of the above general formulae (3-1-2), (3-1-4) and (3-1-5) are preferred, and among them, more preferred is a compound selected from the group consisting of the general formulae (3-1-5)1 or more of the compounds of (1). Bound to R³The proportion of the compound in which the oxyalkylene group on the-O-is an oxyethylene group is more preferably 75 mol% or more, and still more preferably 80 mol% or more (the upper limit is 100 mol% or less) of the compounds constituting the component (d). Such a compound can be obtained by adding an aliphatic alcohol to ethylene oxide first and then removing the unreacted alcohol, or by adding ethylene oxide first to 6 moles or more, preferably 8 moles or more. For example, n1 of the general formula (3-1-2), or n11 of the general formula (3-1-4) or the general formula (3-1-5) has an average molar number of addition of 6 moles or more, preferably 8 moles or more.

In the production of the compound of the general formula (3-1), A may be²¹An alkylene oxide having 3 to 5 carbon atoms, preferably propylene oxide, based on O, and finally adding only 6 mol or more, preferably 8 mol or more of ethylene oxide. For example, the average molar number of addition represented by n12 in the general formula (3-1-5) is 6 mol or more, preferably 8 mol or more.

When the component (d) is blended, the mass ratio of the total of the blending amount of the component (a) and the blending amount of the component (d) to the blending amount of the component (b) is preferably 0.4 or more, more preferably 0.5 or more, more preferably 0.65 or more, and more preferably 0.75 or more in terms of the component (b)/the component (a) + (d), from the viewpoint of improving the cleaning performance of the falling stains. From the viewpoint of solubility in water, the mass ratio is preferably 3 or less, more preferably 2.5 or less, more preferably 2 or less, and more preferably 1.5 or less.

When the component (d) is blended, the mass ratio of the blending amount of the component (d) to the blending amount of the component (a) is preferably 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, more preferably 0.5 or more, and more preferably 1.0 or more in terms of the component (a)/component (d), from the viewpoint of the cleaning performance of the falling stains. From the viewpoint of the cleaning performance of sebum stains, the mass ratio is preferably 3 or less, more preferably 2.5 or less, more preferably 2 or less, and more preferably 1.5 or less.

When the component (d) is blended, the mass ratio of the blending amount of the component (a) and the blending amount of the component (b) and the blending amount of the component (d) to the blending amount of the component (c) is preferably 0.07 or more, more preferably 0.1 or more, and still more preferably 0.15 or more in terms of the component (c)/the component (a) + (b) + (d) from the viewpoint of enhancing the cleaning speed. From the viewpoint of economy, the mass ratio is preferably 3 or less, more preferably 2 or less, more preferably 1 or less, and more preferably 0.5 or less.

The liquid detergent composition for clothing of the present invention may contain a surfactant other than the components (a), (b) and (d) [ hereinafter referred to as component (e) ].

The component (e) includes an anionic surfactant [ hereinafter referred to as component (e1) ]. As the (e1) component, there can be mentioned: an alkylbenzenesulfonic acid having an aliphatic alkyl group having 8 to 22 carbon atoms, a fatty acid having 8 to 22 carbon atoms, an alkanesulfonic acid having 8 to 20 carbon atoms in an alkane, an alkylsulfuric ester and a polyoxyalkylene alkyl ether sulfuric ester each having an aliphatic alkyl group having 8 to 22 carbon atoms, and salts thereof. The component (e1) is preferably an alkylbenzenesulfonic acid having an aliphatic alkyl group having 12 to 16 carbon atoms, a fatty acid having 12 to 18 carbon atoms, or a salt thereof. Examples of the salt of the component (e) include: alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts having 1 to 6 carbon atoms. The salt is preferably 1 or more selected from sodium salt, potassium salt, monoethanolammonium salt, and triethanolammonium salt.

Further, a cationic surfactant may be blended as the component (e). As the cationic surfactant, a compound which can be a cationic surfactant depending on the pH value in water by being compounded with an amine is also referred to as a cationic surfactant for convenience. Specifically, it is preferably selected from tertiary amine salts having an aliphatic alkyl group having 11 to 22 carbon atoms, for example, alkanoylaminopropyl-N, N-dimethylamine [ alkanoyl means an aliphatic alkanoyl group having 11 to 21 carbon atoms ]; examples of the quaternary ammonium surfactant include 1 or more compounds selected from N-alkyl-N, N-trimethylammonium chloride [ alkyl represents an aliphatic alkyl group having 10 to 18 carbon atoms ], N-alkyl-N, N-dimethyl-N-ethylammonium ethylsulfate [ alkyl represents an aliphatic alkyl group having 10 to 18 carbon atoms ], and N, N-dialkyl-N, N-dimethylammonium chloride [ alkyl represents an aliphatic alkyl group having 8 to 12 carbon atoms ].

In addition, an amphoteric surfactant may be blended as the component (e). Examples of the amphoteric surfactant include sulfobetaines and carbonylbetaines having an alkyl group having 10 to 18 carbon atoms.

(e) The amount of the component (b) is preferably 0.5 to 15 mass%, more preferably 0.5 to 10 mass%, based on the total amount of all the raw materials to be blended in the liquid detergent composition for clothing of the present invention. In addition, regarding the quaternary ammonium salt, the mass other than the counter anion is taken as the mass of the quaternary ammonium salt; the tertiary amine is a structure in which a hydrogen atom is substituted in addition to an organic group in a group bonded to a nitrogen atom. When a cationic surfactant is blended as component (e), it is preferably 5% by mass or less from the viewpoint of cleaning performance of sebum stains. The blending in an amount of 5% by mass or less means that the blending is not performed or the blending is performed in an amount exceeding 0% by mass and 5% by mass or less. Preferably 3% by mass or less, more preferably 1% by mass or less, and more preferably no cationic surfactant is blended.

In the liquid detergent composition for clothing of the present invention, an alkaline agent [ hereinafter referred to as component (f) ] is preferably blended from the viewpoint of detergency. The alkali agent may include, in addition to alkali metal hydroxides, alkali metal carbonates, and the like, alkanolamines in which 1 or more and 3 or less of the groups bonded to the nitrogen atom are alkanol groups having 2 or more and 4 or less carbon atoms, and the remainder are alkyl groups having 1 or more and 4 or less carbon atoms or hydrogen atoms. Among them, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. The alkanol group is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. As the alkanolamine, there may be mentioned: alkanolamines such as 2-aminoethanol, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. In the present invention, the component (f) is preferably an alkanolamine selected from the group consisting of monoethanolamine and triethanolamine, and more preferably monoethanolamine.

The alkaline agent as the component (f) may be used for adjusting the pH of the liquid detergent composition for clothing of the present invention to a specific value.

The liquid detergent composition for clothing of the present invention may contain the component (f) in an amount to give the following pH. Specifically, the content may be 0.01% by mass or more, further 0.5% by mass or more, and 10% by mass or less, further 8% by mass or less. Among these, the alkanolamine as the component (f) is preferably blended at 0.5% by mass or more, more preferably at 1% by mass or more, more preferably at 3% by mass or more, and preferably at 8% by mass or less, more preferably at 7% by mass or less, more preferably at 6% by mass or less. In the present invention, the amount of the alkali agent, particularly the alkanolamine, added to the component (f) is also the amount of the counter ion derived from other components added to the composition, such as the component (a) or the component (b).

In the liquid detergent composition for clothing of the present invention, a chelating agent [ hereinafter referred to as component (g) ] may be added. Specific examples of the chelating agent as the component (g) include: aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and the like, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, malic acid, etc., or salts thereof; 1-hydroxyethylidene-1, 1-diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), alkali metal or lower amine salts thereof, and the like. (g) The amount of the component (b) is 0.1 to 5% by mass, preferably 0.1 to 4% by mass, and more preferably 0.1 to 3% by mass, when the component (b) is an acid type.

The following components (h1) to (h6) may be added to the liquid detergent composition for clothing of the present invention.

(h1) Recontamination preventing agents and dispersants such as polyacrylic acid, polymaleic acid, and carboxymethylcellulose in an amount of 0.01 to 10 mass%;

(h2)0.01 to 10% by mass of a bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate;

(h3)0.01 to 10% by mass of a bleaching activator such as tetraacetylethylenediamine, a bleaching activator represented by general formulae (I-2) to (I-7) of Japanese patent application laid-open No. 6-316700;

(h4) 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.3% by mass or more and 2% by mass or less, preferably 1% by mass or less of 1 or more enzymes selected from the group consisting of cellulase, amylase, pectinase, protease and lipase, preferably 1 or more enzymes selected from the group consisting of amylase and protease. The component (h4) is preferably an enzyme containing amylase from the viewpoint of achieving a higher cleaning speed. From the viewpoint of obtaining higher cleaning performance on a clothing having sebum stains adhering thereto, against stains having eating stains such as meat paste adhering thereto, enzymes containing amylase and protease are preferred.

(h5) A fluorescent dye of 0.001 mass% or more and 1 mass% or less, for example, a fluorescent dye commercially available as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) or Whitex SA (trade name, manufactured by sumitomo chemical corporation);

(h6)0.01 to 2 mass% of an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, or sodium bisulfite;

(h7) appropriate amount of pigment, perfume, antibacterial antiseptic, and defoaming agent such as silicone.

The liquid detergent composition for clothing of the present invention has a pH at 20 ℃ of preferably 6 or more, more preferably 6.5 or more, more preferably 7 or more, and preferably 11 or less, more preferably 9 or less, more preferably 8 or less, from the viewpoint of obtaining excellent cleaning performance. The pH was measured by the method described in item 8.3 of JIS K3362:1998, at the temperature described at 20 ℃. The pH measured by the above method is preferably 6 or more and 9 or less, and more preferably 6.5 or more and 8 or less, from the viewpoint of cleaning performance and ease of handling of the liquid detergent composition for clothing of the present invention.

From the viewpoint of easy handling, the viscosity of the liquid detergent composition for clothing of the present invention at 20 ℃ is preferably 10mPa · s or more, more preferably 50mPa · s or more, and even more preferably 100mPa · s or more, and is preferably 500mPa · s or less, more preferably 400mPa · s or less, and even more preferably 300mPa · s or less. It is preferable that the content is adjusted by the component (c) so as to fall within the above range. In the present invention, the viscosity is measured by a B-type viscometer. The rotor is chosen to be viscosity-matched. The liquid detergent composition or the diluted liquid was set to have a viscosity after 60 seconds from the start of spinning by rotating at a rotation speed of 60 r/min. The measurement temperature (liquid temperature) of the viscosity is selected for each target.

From the viewpoint that the cleaning speed can be increased even if the ratio of the mass (kg) of the cloth to the volume (L) of the cleaning liquid containing the liquid detergent composition for clothes of the present invention, that is, the ratio of [ volume (L) of the cleaning liquid) ]/[ mass (kg) of the cloth) ] is as low as 3 or more and 20 or less, and further 3 or more and 15 or less, the viscosity of the liquid detergent composition for clothes of the present invention at 20 ℃ is preferably 500mPa · s or less, and more preferably 400mPa · s or less.

According to the present invention, there is provided a method for producing a liquid detergent composition for clothing, which comprises mixing the following component (a), component (b), component (c), and water, wherein the component (a) and the component (b) are used in a mass ratio such that the total amount of the component (a) and the component (b) is 15 to 70 mass% based on the total mass of all the blending raw materials, and the component (b)/the component (a) is 0.5 to 7. Among the matters described in the liquid detergent composition for clothing, those that can be used can be suitably used in the production method. The component (d) may be further mixed in the production of the liquid detergent composition for clothing.

(a) The components: a nonionic surfactant represented by the following general formula (1);

R¹O-(EO)_mH (1)

(b) The components: an anionic surfactant represented by the following general formula (2);

R²O-[(A¹O)_p/(EO)_q]-SO₃M (2)

(c) An organic solvent having 1 or more hydroxyl groups: the content thereof is 5 to 40 mass% based on the total mass of all the blending raw materials.

[ method for cleaning clothing Material ]

The present invention provides a method for cleaning clothing, which comprises using a cleaning liquid containing water and 0.01-0.1 mass% of the liquid detergent composition for clothing of the present invention, the temperature of which is 0-35 ℃, and cleaning the clothing for 1-7 minutes under the condition that the bath ratio represented by the ratio of the mass of the clothing to the amount (liter) of the cleaning liquid is 3-50 minutes inclusive.

The cleaning liquid preferably contains the liquid detergent composition for clothing of the present invention in an amount of 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 0.2% by mass or less, more preferably 0.1% by mass or less. The cleaning liquid preferably contains the component (a) and the component (b) in a total amount of 0.006% by mass or more, more preferably 0.01% by mass or more, and preferably 0.08% by mass or less, more preferably 0.07% by mass or less.

As the water for preparing the cleaning liquid, any water may be used. Examples thereof include: tap water, ion exchange water, well water, river water, and the like. The hardness of water suitable for cleaning is 1 ° DH to 10 ° DH in terms of german hardness.

From the viewpoint of improving the cleaning speed, the temperature of the cleaning liquid is preferably 0 ℃ or higher, more preferably 3 ℃ or higher, and still more preferably 5 ℃ or higher. From the viewpoint of not excessively removing the oil agent contained in the fiber itself constituting the clothing and maintaining the texture of the fiber, it is preferably 35 ℃ or lower, more preferably 30 ℃ or lower, more preferably 15 ℃ or lower, and more preferably 10 ℃ or lower. In addition, in winter cleaning, even if the clothing is cleaned at a low temperature where the temperature of the cleaning liquid exceeds 0 ℃ to 10 ℃ or less, and further exceeds 3 ℃ to 8 ℃ or less, the cleaning speed of sebum stains is high, and a cleaning method with excellent cleaning power of falling stains can be performed.

In recent years, washing machines have become larger in size, and the value of the bath ratio represented by the ratio of the mass of the laundry to the amount of water (liter) of the cleaning liquid, that is, the value of the amount of water (liter) of the cleaning liquid/the mass (kg) of the laundry (hereinafter, this ratio is sometimes referred to as the bath ratio) tends to be smaller. When the bath ratio is decreased, it is said that, when the household washing machine is used, mechanical force generated by agitation is hardly transmitted to clothes, and thus, cleaning force is decreased. The method for cleaning clothing of the present invention can increase the cleaning speed even under the cleaning condition with a small bath ratio. From the viewpoint of detergency, the bath ratio is preferably 4 or more, and more preferably 5 or more. In addition, the bath ratio is preferably 45 or less, more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and more preferably 15 or less, from the viewpoint that the effect of improving the cleaning speed can be further obtained.

The phrase "further obtaining the effect of improving the cleaning speed" means that the value of "5 min/10 min cleaning relative value (1) (cleaning speed)" described in "(1-2) evaluation of cleaning speed" shown in the following examples or the value of "5 min/10 min cleaning relative value (2)" described in "(2-2) evaluation of cleaning speed" is closer to 1.

The method for cleaning clothing of the present invention can obtain sufficient cleaning power even if the cleaning time is short. From the viewpoint of cleaning power, the cleaning time is 1 minute or more, preferably 2 minutes or more, and more preferably 3 minutes or more. From the viewpoint of further obtaining the effect of improving the cleaning speed, the cleaning time is 7 minutes or less, preferably 5 minutes or less.

The method for cleaning clothing of the present invention can obtain the effect of the present invention on an object to which a mechanical force is not uniformly applied, such as clothing constituting fibers according to the use of a consumer, compared to a method in which fibers are conveyed by a roller or the like and immersed in a liquid for refining, such as a method for refining fibers. In addition, the cleaning method of the present invention is suitable for a rotary cleaning method. The rotary cleaning method is a cleaning method in which a cloth not fixed to a rotating device is rotated around a rotating shaft together with a cleaning liquid. The rotary cleaning method may be implemented by a rotary washing machine. Therefore, in the present invention, it is preferable to perform the cleaning of the cloth using a rotary washing machine. As the rotary washing machine, specifically, there can be mentioned: a drum-type full-automatic washing machine, a pulsator-type full-automatic washing machine, or a pulsator-type full-automatic washing machine. These rotary washing machines may be used as commercially available washing machines for home use, respectively.

From the viewpoint of more reliably achieving an improvement in cleaning speed and a cleaning power of food stains, a preferred method for cleaning clothing of the present invention is a rotary cleaning method using a rotary washing machine, in which water and clothing used for cleaning, and the liquid detergent composition for clothing of the present invention are stirred in the rotary washing machine. The rotary washing machine is preferably a drum type full-automatic washing machine, a pulsator type full-automatic washing machine, or a pulsator type full-automatic washing machine, more preferably a pulsator type full-automatic washing machine or a pulsator type full-automatic washing machine, and even more preferably a pulsator type full-automatic washing machine. In the method, a cleaning method in which the temperature of the cleaning liquid exceeds 0 ℃, preferably exceeds 3 ℃, more preferably 15 ℃ or less, more preferably 10 ℃ or less, more preferably 15 ℃ or less, in terms of mass of clothing (kg)/volume of the cleaning liquid (liter); in the cleaning method, the time from the start of stirring the water, the cloth, and the detergent composition for cleaning to the start of discharging the cleaning liquid from the washing machine is preferably 1 minute or more, more preferably 2 minutes or more, more preferably 3 minutes or more, more preferably 7 minutes or less, more preferably 6 minutes or less, and more preferably 5 minutes or less.

Therefore, as a method for cleaning clothing of the present invention, the following methods for cleaning clothing can be mentioned: the liquid detergent composition for clothing of the present invention contains water and 0.01 to 0.1 mass% of a cleaning liquid at a temperature of more than 0 ℃, preferably more than 3 ℃ to 15 ℃, preferably 10 ℃ or less, and the liquid detergent composition for clothing of the present invention is used in a rotary washing machine, preferably a drum-type full-automatic washing machine, a pulsator-type full-automatic washing machine or a pulsator-type full-automatic washing machine, more preferably a pulsator-type full-automatic washing machine or a pulsator-type full-automatic washing machine, and more preferably a pulsator-type full-automatic washing machine, under the condition that the bath ratio of the mass of the clothing to the amount (liter) of the cleaning liquid is 5 or more, preferably 10 or more to 20 or less, preferably 15 or less, and the temperature of the cleaning liquid detergent composition for clothing is more than 0 ℃, preferably more than 3 ℃ to 0.1 mass%, and the temperature of the cleaning liquid detergent composition for clothing is more than 0 ℃ and the temperature of, Preferably 6 minutes or less, more preferably 5 minutes or less. These rotary washing machines may be used as home-use commercially available washing machines, respectively.

The present invention further discloses the following liquid detergent composition for clothing and a method for cleaning clothing, in relation to the above embodiment.

< 1 > a liquid detergent composition for clothing, which comprises a component (a), a component (b), a component (c) and water, wherein the total amount of the component (a) and the component (b) is 15 to 70 mass% based on the total mass of all the raw materials to be blended, and the mass ratio of the amount of the component (a) to the amount of the component (b) is 0.5 to 7 inclusive, based on the amount of component (b/(a).

R¹O-(EO)_mH (1)

[ in the formula, R¹Represents a hydrocarbon group having 8 or more, preferably 10 or more, more preferably 11 or more, and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms, EO represents an ethyleneoxy group, m represents an average addition mole number, and m is a number of 1 or more, preferably 2 or more, more preferably 2.5 or more, more preferably 3 or more, and 10 or less, preferably 9 or less, more preferably 8 or less.]

R²O-[(A¹O)_p/(EO)_q]-SO₃M (2)

[ in the formula, R²Represents a hydrocarbon group having 8 or more, preferably 10 or more, more preferably 12 or more carbon atoms, and 22 or less, preferably 16 or less, more preferably 14 or less carbon atoms, A¹O represents an alkylenated oxy group selected from an alkylenated oxy group having 3 carbon atoms and an alkylenated oxy group having 4 carbon atoms, EO represents an ethyleneoxy group, p and q represent average addition mole numbers, p is a number of 1 to 5, and q is a number of 0 to 10. "/" indicates block bonding in any order (A)¹O)_pRadical and (EO)_qAnd (4) a base. M is a cation.]

(c) An organic solvent having 1 or more hydroxyl groups: the content thereof is 5% by mass or more, preferably 10% by mass or more, more preferably 13% by mass or more, and 40% by mass or less, preferably 35% by mass or less, more preferably 25% by mass or less, relative to the total mass of all the blending raw materials.

< 2 > the liquid detergent composition for clothing described in < 1 >, wherein the component (b) is an anionic surfactant selected from the group consisting of anionic surfactants represented by the following general formula (2-1) and anionic surfactants represented by the general formula (2-2).

R²O-(A¹O)_p1-(EO)_q1-SO₃M (2-1)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p1 and q1 represent average addition mole numbers, p1 is a number of 1 to 5, and q1 is a number of 0 to 10. M is a cation.]

R²O-(EO)_q2-(A¹O)_p2-SO₃M (2-2)

[ in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group having 3 carbon atoms or a carbon atomEO represents an ethyleneoxy group, p2 and q2 represent an average addition mole number, p2 is a number of 1 to 5, and q2 is a number of 0.5 to 5, among alkylene oxide groups having a sub-number of 4. M is a cation.]

< 3 > the liquid detergent composition for clothing described in < 2 >, wherein the component (b) is an anionic surfactant represented by the general formula (2-1), and p1 in the general formula (2-1) is preferably an anionic surfactant having a number of 1.1 or more, more preferably 1.2 or more, more preferably 1.3 or more, more preferably 1.4 or more, more preferably 1.5 or more, more preferably 1.8 or more, and preferably 4 or less, more preferably 3 or less, more preferably 3.0 or less, more preferably 2.9 or less, more preferably 2.8 or less, more preferably 2.5 or less.

< 4 > the liquid detergent composition for clothing described in < 2 >, wherein the component (b) is an anionic surfactant represented by the general formula (2-2), and p2 in the general formula (2-2) is preferably an anionic surfactant of a number of 1.5 or more, more preferably 1.8 or more, and preferably 4 or less, more preferably 3 or less, more preferably 2.5 or less.

The liquid detergent composition for clothing described in any of < 5 > such as < 1 > to < 4 >, wherein the total amount of the component (a) and the component (b) is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, and more preferably 60% by mass or less, based on the total mass of all the blended raw materials.

The liquid detergent composition for clothing described in any of < 6 > such as < 1 > to < 5 >, wherein the pH at 20 ℃ is preferably 6 or more, more preferably 6.5 or more, more preferably 7 or more, and preferably 11 or less, more preferably 9 or less, more preferably 8 or less.

The liquid detergent composition for clothing described in any of < 7 > such as < 1 > to < 6 >, wherein the mass ratio of the amount of component (a) to the amount of component (b) is preferably 0.7 or more, more preferably 0.9 or more, more preferably 1.0 or more, more preferably 1.1 or more, more preferably 1.2 or more, more preferably 1.5 or more, and preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, more preferably 2.5 or less, more preferably 2 or less, and more preferably 1.8 or less, in terms of component (b/(a) component).

< 8 > the liquid detergent composition for clothing, which is described in any one of < 1 > to < 7 >, wherein the mass ratio of the amount of component (a) to the amount of component (c) is preferably 0.5 or more, more preferably 0.6 or more, more preferably 0.8 or more, and preferably 2.5 or less, more preferably 2.4 or less, more preferably 2.2 or less, more preferably 2.0 or less, more preferably 1.8 or less, more preferably 1.6 or less, and more preferably 1.4 or less, in terms of component (a/(c) component).

< 9 > the liquid detergent composition for clothing described in any one of < 1 > to < 8 >, wherein in the component (a), R is selected from the group consisting of the above-mentioned R in the general formula (1)¹Nonionic surfactant having branched primary hydrocarbon group and R in the above general formula (1)¹The proportion of the nonionic surfactant (a1) in the nonionic surfactant having a linear secondary hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

The liquid detergent composition for clothing described in any one of < 10 > and < 1 > to < 9 > wherein R selected from the group consisting of the above general formula (1) is compounded¹Nonionic surfactant which is a branched primary hydrocarbon group and R in the above general formula (1)¹Among nonionic surfactants having a linear secondary hydrocarbon group, the nonionic surfactant (a1) [ hereinafter referred to as component (a 1]]And R in the above general formula (1)¹The nonionic surfactant (a2) having a straight-chain primary hydrocarbon group [ hereinafter referred to as component (a2) ]]Is formed as component (a).

< 11 > the liquid detergent composition for clothing described in < 10 >, wherein the component (a) comprises the above-mentioned component (a1) and the above-mentioned component (a2), and the blending ratio of the component (a1) to the component (a2) is preferably 0.5 or more, more preferably 0.7 or more, more preferably 0.9 or more, more preferably 1.0 or more, and preferably 7 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, and more preferably 2 or less in terms of the mass ratio of the component (a 1)/the component (a 2).

The liquid detergent composition for clothing described in < 12 > such as < 10 > or < 11 >, wherein the total ratio of the component (a1) to the component (a2) in the component (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

< 13 > the liquid detergent composition for clothing described in any one of < 10 > to < 12 >, wherein the component (a1) is R in the general formula (1)¹A nonionic surfactant which is a linear secondary hydrocarbon group.

< 14 > the liquid detergent composition for clothing described in any one of < 1 > to < 13 >, wherein the component (c) is at least 1 selected from the group consisting of the following components (c2) and (c 4).

(c2) The components: a dihydric or higher and hexahydric or lower alcohol having 2 to 6 carbon atoms (excluding polyalkylene glycols containing alkylene glycol units having 2 to 4 carbon atoms);

(c4) the components: a monoalkyl ether of a (mono-or poly-) alkylene glycol having an alkylene glycol unit having 2 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms.

< 15 > and < 14 > of the liquid detergent composition for clothing, wherein the compounds (c2) and (c4) are at least 1 kind selected from the following compounds.

(c2) Ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, and glycerin;

(c4) diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol and 1-ethoxy-2-propanol.

The liquid detergent composition for clothing described in any of < 16 > and < 1 > to < 15 > further comprising the following component (d), wherein the mass ratio of the total of the amount of the component (a) and the amount of the component (d) to the amount of the component (b) is 0.4 or more and 3 or less in terms of the component (b)/[ (a) component + (d) component ].

(d) The components: a nonionic surfactant represented by the following general formula (3).

R³O-(A²O)_nH (3)

[ in the formula, R³Represents a hydrocarbon group having 8 to 22 carbon atoms, A²O represents an alkylene oxide group having 2 to 5 carbon atoms, and n represents an average number of moles of addition and is a number of 16 to 35. A. the²O contains an ethyleneoxy group having 16 or more carbon atoms on average and having 2 carbon atoms. Wherein, in A²When all O are vinyloxy groups, n is a number of 18 or more.]

< 17 > the liquid detergent composition for clothing described in < 16 >, wherein the component (d) is a compound represented by the following general formula (3-1).

R³O-[(C₂H₄O)_n1/(A²¹O)_n2]-H (3-1)

[ in the formula, R³A hydrocarbon group having 8 to 22 carbon atoms, A²¹O is an alkylene oxide group having 3 to 5 carbon atoms. n1 and n2 are average addition mole numbers, n1 is a number of 15 to 30 inclusive, n2 is a number of 1 to 5 inclusive, and the total number of n1 and n2 is a number of 16 to 35 inclusive. "/" denotes C₂H₄O radical and A²¹The O groups may be combined in any of random and block. In addition, A²¹O may also be divided into multiple chunks.]

The liquid detergent composition for clothing described in < 18 > such as < 16 > or < 17 > whereinAnd (d) the component (a) is a compound as follows: r in the above general formula (3-1)³Preferably 10 or more, more preferably 12 or more, and more preferably 14 or more, and preferably 18 or less, more preferably 16 or less, a²¹O is an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, more preferably an alkylene oxide copolymer having 3 carbon atoms, n1 is preferably a number of 16 or more, more preferably 18 or more and preferably 27 or less, more preferably 24 or less, n2 is preferably a number of 2 or more, more preferably 4 or less, more preferably 3 or less, the total of n1 and n2 is preferably 17 or more, more preferably 18 or more, more preferably more than 18, and preferably 30 or less, more preferably 25 or less, C₂H₄O radical and A²¹The O groups are preferably bonded in blocks.

< 19 > the liquid detergent composition for clothing described in any one of < 16 > to < 18 >, wherein the component (d) is at least 1 compound selected from the following general formulae (3-1-1) to (3-1-5).

R³O-(A²¹O)_n2-(C₂H₄O)_n1-H (3-1-1)

R³O-(C₂H₄O)_n1-(A²¹O)_n2-H (3-1-2)

R³O-[(C₂H₄O)_n11·(A²¹O)_n2]-(C₂H₄O)_n12-H (3-1-3)

R³O-(C₂H₄O)_n11-[(A²¹O)_n2·(C₂H₄O)_n12]-H (3-1-4)

R³O-(C₂H₄O)_n11-(A²¹O)_n2-(C₂H₄O)_n12H (3-1-5)

[ in the formula, R³Is a hydrocarbon group having 8 to 22 carbon atoms, and is preferably linearPrimary alkyl radical, A²¹O is an alkylene oxide group having 3 to 5 carbon atoms. n1 and n2 are average addition mole numbers, n1 is a number of 15 to 30 inclusive, n2 is a number of 1 to 5 inclusive, and the total number of n1 and n2 is a number of 16 to 35 inclusive. n11 and n12 represent average molar numbers of addition, and n1 is n11+ n 12. "·" indicates random incorporation. In addition, A²¹O may also be divided into multiple blocks.]

< 20 > the liquid detergent composition for clothing described in < 19 >, wherein the component (d) is preferably at least 1 compound selected from the group consisting of the above-mentioned general formulae (3-1-2), (3-1-4) and (3-1-5), more preferably at least 1 compound selected from the above-mentioned general formulae (3-1-5).

The liquid detergent composition for clothing described in any of < 21 > such as < 16 > to < 20 >, wherein the mass ratio of the amount of component (d) to the amount of component (a) blended is preferably 0.2 or more, more preferably 0.3 or more, more preferably 0.4 or more, more preferably 0.5 or more, more preferably 1.0 or more, and preferably 3 or less, more preferably 2.5 or less, more preferably 2 or less, and more preferably 1.5 or less, in terms of component (a/(d) component).

The liquid detergent composition for clothing described in any of < 22 > and < 16 > to < 21 > wherein the mass ratio of the total of the amount of component (a) and the amount of component (d) to the amount of component (b) is preferably 0.4 or more, more preferably 0.5 or more, more preferably 0.65 or more, more preferably 0.75 or more, and preferably 3 or less, more preferably 2.5 or less, more preferably 2 or less, and more preferably 1.5 or less in terms of component (b)/[ (a) component + (d) component ].

The liquid detergent composition for clothing described in any of < 23 > to < 22 > wherein 1 or more enzymes selected from the group consisting of cellulase, amylase, pectinase, protease and lipase, preferably 1 or more enzymes selected from the group consisting of amylase and protease, are blended in an amount of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.3% by mass or more and 2% by mass or less, preferably 1% by mass or less.

The liquid detergent composition for clothing described in any of < 24 > such as < 1 > to < 23 > wherein the cationic surfactant is preferably incorporated in an amount of 5% by mass or less, more preferably 4% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, more preferably 1.5% by mass or less, more preferably 1.0% by mass or less, more preferably 0.5% by mass or less, more preferably no cationic surfactant is incorporated.

< 25 > a method for cleaning clothing, wherein the clothing is cleaned for 1 minute or more, under conditions that the bath ratio represented by the ratio of the mass of the clothing to the amount (liter) of the cleaning liquid is 3 or more, preferably 4 or more, more preferably 5 or more and 50 or less, preferably 40 or less, more preferably 30 or less, more preferably 20 or less, more preferably 15 or less, and more preferably 15 or less, under the condition that the mass (kg) of the clothing is 3 or more, preferably 4 or more, more preferably 5 or more and 50 or less, more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and more preferably 15 or less, by using a cleaning liquid composition for clothing, which contains water and any one of the liquid cleaning liquid compositions for clothing described in any one of 0.01% by mass, preferably 0.02% by mass or more and 0.2% by mass, preferably 0.1% by mass or less, and has a temperature of 0 ℃ or more, more preferably 3 ℃ and 35 ℃ or less, more preferably, Preferably 2 minutes or more, more preferably 3 minutes or more and 7 minutes or less, preferably 5 minutes or less.

< 26 > the method for cleaning clothing as < 25 >, wherein the clothing is cleaned for 3 minutes or more and 7 minutes or less.

< 27 > the method for cleaning clothing, as < 25 > or < 26 >, wherein the bath ratio represented by the ratio of the mass of clothing to the amount (liter) of the cleaning liquid is 5 or more and 20 or less in the amount (liter) of the cleaning liquid/the mass (kg) of clothing.

The method for cleaning clothing described in any of < 28 > to < 25 > to < 27 >, wherein the liquid detergent composition for clothing is contained in the cleaning liquid in an amount of 0.02 mass% or more and 0.1 mass% or less.

The method for cleaning the clothing material of < 29 > such as < 25 > to < 28 > wherein the cleaning of the clothing material is performed using a rotary washing machine.

< 30 > the method for cleaning clothing described in < 29 >, wherein the rotary washing machine is a drum type full-automatic washing machine, a pulsator type full-automatic washing machine or a pulsator type full-automatic washing machine, preferably a pulsator type full-automatic washing machine or a pulsator type full-automatic washing machine, more preferably a pulsator type full-automatic washing machine.

Examples

The following examples are illustrative of the practice of the present invention. The examples are illustrative of the present invention and are not intended to limit the present invention.

To confirm the effect of the present invention, Terg-O-Tometer (Ueshima, MS-8212) was used as a cleaning device. The Terg-O-Tometer (Ueshima, MS-8212) is a device for performing rotary cleaning, and is generally used as a model cleaning device for a drum type full-automatic washing machine for a home-use full-automatic washing machine, a pulsator type full-automatic washing machine for a home-use, or a pulsator type full-automatic washing machine for a home-use. In particular to a model cleaning device which is equivalent to a domestic impeller type full-automatic washing machine or a domestic stirring type full-automatic washing machine.

< examples 1-1 to 1-9 and comparative examples 1-1 to 1-5 >

The components shown in table 1 were mixed to obtain compositions of examples and comparative examples.

A stirring device (Stirr Piece) (made of Teflon (registered trademark)) having a diameter of 60mm was added to a 300ml glass beaker, and the component (a), the component (b) or the component (b'), the component (c) and a necessary amount of 95 mass% water (containing 3mg/kg of sodium hypochlorite) were added so as to give a finished mass of 200g and to be the blending amount shown in Table 1. After the charging, the mixture was stirred at 100 rpm for 20 minutes. Thereafter, the components (d) and (e) were added as necessary, the pH of the composition was adjusted to the pH described in table 1 by the component (f), and the remaining water was used to adjust the final finished mass (200g), to obtain the liquid detergent composition for clothing of table 1. In examples 1 to 9, the following other components were added to the component (d). The pH was measured by the method described in item 8.3 of JIS K3362:1998 (the temperature of the composition at the time of measurement was 20 ℃). The pH values reported in table 1 represent the values obtained by re-measuring the pH of the final finished composition. Using each of the obtained compositions, the following evaluations were performed. The results are shown in table 1. The components in the table are as follows.

(a) Composition (I)

(a-1): a compound having an average of 7 moles of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms [ Softanol 70 (trade name), manufactured by Nippon catalyst Co., Ltd., R in the general formula (1) ]¹A compound having a secondary alkyl group having 12 to 14 carbon atoms and m is 7.]

(a-2): a compound in which ethylene oxide is added in an average amount of 4 moles on the average to a linear primary alcohol having 12 carbon atoms [ R in the general formula (1) ]¹Is a linear primary alkyl group having 12 carbon atoms and m is 4.]

(a-3): a compound in which ethylene oxide is added in an average amount of 6 moles on a linear primary alcohol having 12 carbon atoms [ R in the general formula (1) ]¹Is a linear primary alkyl group having 12 carbon atoms and m is 6.]

(b) Composition (I)

(b-1): the anionic surfactant produced by the following production method (b1) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b1) >)

Linear primary alcohol having 12 carbon atoms [ Kalcol2098, product name, manufactured by Kao corporation, Kalcol 2090 ]2340g and KOH 3.5g were added to an autoclave equipped with a stirring device, a temperature control device, and an automatic introducing device, and dehydrated at 110 ℃ for 30 minutes under 1.3 kPa. After dehydration, the temperature was raised to 120 ℃ by nitrogen substitution, and 1460g of propane oxide-1, 2-diyl (hereinafter referred to as "PO") was added. After addition reaction and aging at 120 ℃ were carried out, the reaction mixture was cooled to 80 ℃ and unreacted PO was removed at 4.0kPa, and then 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average molar number of PO added of 2.0.

Using SO₃Gas, sulfating the obtained alkoxylate by descending the membrane reactor. The obtained sulfate was neutralized with monoethanolamine to obtain polyoxypropylene ether-containing sulfate [ (b-1)]The composition of (1).

The obtained (b-1) is a compound as follows: in the general formula (2-1), R²Is a linear primary alkyl group having 12 carbon atoms, A¹O is propyleneoxy, M is monoethanolammonium, p1 averages 2.0, and q1 is 0. As a result of gas chromatography and NMR analysis, the obtained composition contained 98 mass% of the compound represented by the general formula (2-1).

(b-2): the anionic surfactant produced by the following production method (b2) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b2) >)

Linear primary alcohol having 12 carbon atoms [ Kalcol2098, product name, manufactured by Kao corporation, Kalcol 2090 ]2340g and KOH 3.5g were added to an autoclave equipped with a stirring device, a temperature control device, and an automatic introducing device, and dehydrated at 110 ℃ for 30 minutes under 1.3 kPa. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ℃ and then PO 2190g was added. Addition reaction and aging were carried out at 120 ℃ and then cooled to 80 ℃ to remove unreacted PO at 4.0kPa, and then 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average molar number of PO added of 3.0.

After sulfating the obtained alkoxylate in the same manner as in the production process (b1), a composition containing polyoxypropylene alkyl ether sulfate [ (b-2) ] was obtained.

The obtained (b-2) is a compound as follows: in the general formula (2-1), R²Is a linear primary alkyl group having 12 carbon atoms, A¹O is propyleneoxy, M is monoethanolammonium, p1 averages 3.0, q1 is 0. As a result of gas chromatography and NMR analysis, the obtained composition contained 98 mass% of the compound represented by the general formula (2-1).

(b-3): the anionic surfactant produced by the following production method (b3) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b3) >)

Dehydration of a linear primary alcohol having 12 carbon atoms (trade name, Kalcol2098) was carried out in the same manner as in production method (b 1). After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ℃ and then 730g of PO was added. Addition reaction and aging were carried out at 120 ℃ and the temperature was raised to 145 ℃ to which 1107g of ethylene oxide (hereinafter referred to as "EO") was added. After addition reaction and aging at 145 ℃ and cooling to 80 ℃, unreacted EO was removed at 4.0 kPa. After removing unreacted EO, 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average molar number of PO added of 1.0 and an average molar number of EO added of 2.0.

The obtained alkoxylate was sulfated and then neutralized in the same manner as in production method (b1), to obtain a composition containing an alkyl ether sulfate [ (b-3) ].

As a result of gas chromatography and NMR analysis, (b-3) obtained was a compound as follows: in the general formula (2-1), R²Is a linear primary alkyl group having 12 carbon atoms, A¹O is propyleneoxy, M is monoethanolammonium, p1 averages 1.0, and q1 averages 2.0. As a result of gas chromatography and NMR analysis, the obtained composition contained 80 mass% of the compound represented by the general formula (2-1).

(b-4): the anionic surfactant produced by the following production method (b4) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b4) >)

Dehydration of a linear primary alcohol having 12 and 14 carbon atoms (trade name, Kalcol 2470) was carried out in the same manner as in production method (b 1). After dehydration, nitrogen gas was replaced, the temperature was raised to 120 ℃ and thereafter 1460g of PO was added. After addition reaction and aging at 120 ℃ were carried out, the temperature was raised to 145 ℃ and EO 1107g was added. After addition reaction and aging at 145 ℃ and cooling to 80 ℃, unreacted EO was removed at 4.0 kPa. After removing unreacted EO, 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average PO molar number of 2.0 and an average EO molar number of 2.0.

The obtained alkoxylate was sulfated and then neutralized in the same manner as in production method (b1), to obtain a composition containing an alkyl ether sulfate [ (b-4) ].

As a result of gas chromatography and NMR analysis, (b-4) obtained was a compound as follows: in the general formula (2-1), R²Is a linear primary alkyl group having 12, 14 carbon atoms, A¹O is propyleneoxy, M is monoethanolammonium, p1 averages 2.0, and q1 averages 2.0. As a result of gas chromatography and NMR analysis, the obtained composition contained 80 mass% of the compound represented by the general formula (2-1).

(b') component (a): (b) comparative Compound of Components

(b' -1): in the general formula (2-1), R²Is a straight chain with 12 and 14 carbon atomsPrimary alkyl radical, A¹A compound wherein O is propyleneoxy, M is monoethanolammonium, p1 is 0, and q1 averages 2.0.

(c) Composition (I)

(c-1): diethylene glycol monobutyl ether

(c-2): propylene glycol

(c-3): 1, 6-hexanediol

(d) Composition (I)

(d-1): the oil composition is characterized by being obtained by sequentially adding 9 moles of ethylene oxide, 2 moles of propylene oxide and 9 moles of ethylene oxide to 1 mole of straight-chain primary alcohol having 10-14 carbon atoms and derived from coconut oil in a block manner. [ formula R³O-(EO)_n11-(A²O)_n2-(EO)_n12In H, R³Is a linear alkyl group having 10 to 14 carbon atoms, A²A compound wherein O is an oxypropylene group, n11 is 9 on average, n2 is 2 on average and n12 is 9 on average.]

(e) Composition (I)

(e-1): alkyl benzene sulfonic acid having C10-14 straight-chain alkyl group

(e-2): lunac L-55 (trade name) (coconut fatty acid; manufactured by Kao corporation)

(f) Composition (I)

(f-1): monoethanolamine (containing a counter ion as component (b))

< other ingredients >

Polymer (1): a polymer compound synthesized by the method of synthetic example 1 of paragraph 0020 of Japanese patent application laid-open No. 10-60476.

Fluorescent dye: tinopal CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)

Enzyme (1): everlase 16.0L-EX (trade name) (protease, manufactured by Novozymes corporation) enzyme (2): stainzyme (trade name) (Amylase, manufactured by Novozymes Inc.)

Pigment (1): green number 202

Pigment (2): yellow No. 203

(1) Evaluation of cleaning ability

< preparation of contaminated Fabric for evaluation >

Preparation of model sebum Artificial stained cloth

The artificial contaminated model sebum liquid is adhered to cloth to prepare artificial contaminated model sebum cloth. The adhesion of the model sebum artificial stain to the cloth was performed by printing the artificial stain onto the cloth using a gravure roll coater. Making artificial contaminated model sebum liquid adhered to cloth and making artificial contaminated model sebum cloth with 58cm pit capacity in gravure roller³/m²The coating speed was 1.0m/min, the drying temperature was 100 ℃ and the drying time was 1 min. Cotton 2003 (manufactured by a valley store) was used for the cloth.

Composition of model sebum artificial contaminated liquid: 0.4 mass% of lauric acid, 3.1 mass% of myristic acid, 2.3 mass% of pentadecanoic acid, 6.2 mass% of palmitic acid, 0.4 mass% of heptadecanoic acid, 1.6 mass% of stearic acid, 7.8 mass% of oleic acid, 13.0 mass% of glycerol trioleate, 2.2 mass% of n-hexadecyl palmitate, 6.5 mass% of squalene, 1.9 mass% of protein lecithin liquid crystal, 8.1 mass% of Ceratolein, 0.01 mass% of carbon black, and the balance of water (total 100 mass%)

Preparation of meat paste stained cloth

A commercially available retort Meat paste (Mama Meat Sauce manufactured by Nisshin Foods inc., pot, purchased 7 months 2012) was spread on cotton knit cloth (manufactured by a cereal shop) by 0.15g and evenly spread, dried at room temperature for 12 hours, and the resultant cloth was supplied to the test.

< method for evaluating cleanliness (1) >

(1-1) evaluation of cleaning ability

67. mu.L each of the liquid detergent compositions was directly applied to 5 pieces of meat paste-stained cloth (6 cm. times.6 cm) prepared as described above, left to stand for 5 minutes in this state, and then placed in 1L of tap water and cleaned at 85rpm by using a Terg-O-Tometer (Ueshima, MS-8212). The cleaning conditions were 10 minutes for cleaning, 0.033 mass% for the concentration of the detergent composition during cleaning, 20 ℃ for water temperature, and 20 for bath ratio (adjusted to 6cm × 6cm cloth cut from cotton 2003 (manufactured by a gorge shop)), and after cleaning, rinsing was performed for 3 minutes with tap water (20 ℃).

The reflectance at 550nm before and after the cleaning of the original cloth before the staining and the reflectance before and after the cleaning were measured by a colorimeter (Z-300A manufactured by Nippon Denshoku Co., Ltd.), and the cleaning ratio (%) (the cleaning ratio is an average of the cleaning ratios of 5 blocks) was obtained from the following equation.

Cleaning ratio (%) < 100 × [ (reflectance after cleaning-reflectance before cleaning)/(reflectance of original cloth-reflectance before cleaning) ]

The relative cleaning value (1) was obtained from the following formula based on the cleaning ratio (%) of the composition of comparative examples 1 to 3 (indicated by a numerical value in parentheses in the table). The results are shown in the table.

Relative cleaning value (1) ═ cleaning rate (%) of comparative examples or comparative examples- [ cleaning rate (%) of comparative examples 1 to 3 (reference composition) ]

The higher the value of the relative cleaning value (1), the higher the cleaning power. When the difference from the cleaning value (1) was 3 or more, a significant difference was observed.

(1-2) evaluation of cleaning speed (1)

5 model sebum artificially stained cloths (6 cm. times.6 cm) made as described above were cleaned at 85rpm for 5 minutes or 10 minutes using a Terg-O-Tometer (Ueshima, MS-8212). The cleaning conditions were such that the concentration of the liquid detergent composition was 0.033 mass%, the water temperature was 20 ℃, and the bath ratio was 20 (adjusted so that cotton 2003 (manufactured by gorge shop) was cut into a 6cm × 6cm cloth), and after cleaning, the cloth was rinsed with tap water (20 ℃) for 3 minutes. The cleaning ratio was measured by the method described in (1-1) above, and the average of 5 blocks was determined. From the respective cleaning rates (average values) of 5 minutes and 10 minutes of the cleaning time, a relative cleaning value (1) of 5 minutes/10 minutes was obtained by the following equation. The results are shown in the table. In the table, the cleaning rate (average value) of 5 minutes of the cleaning time in the evaluation (1) of the cleaning speed is also represented as "cleaning rate after 5 minutes (1)".

Relative cleaning value (1) of 5 min/10 min (cleaning speed) — cleaning rate (%) of 5 min cleaning time/cleaning rate (%) of 10 min cleaning time)

[ Table 1]

< examples 1-10 to 1-27, comparative examples 1-6, and 1-7 >

The components shown in table 2 were mixed in the same manner as in example 1-1 and the like to prepare liquid detergent compositions for clothing described in table 2, and the cleaning power and the cleaning speed were evaluated by the following "cleaning evaluation method (2)". The results are shown in table 2.

Comparative examples 1 to 6 are compositions similar to those of example 10 of Japanese patent application laid-open publication No. 2011-208130.

< method for evaluating cleanliness (2) >

(2-1) evaluation of cleaning ability

The evaluation was carried out by the same evaluation method as in the above "(1-1) evaluation of cleaning power" of example 1-1 and the like, except that comparative examples 1-6 were used as references instead of comparative examples 1-3. The evaluation results herein were taken as "relative cleanliness value (2)".

(2-2) evaluation of cleaning speed (2)

5 model sebum artificially stained cloths (6 cm. times.6 cm) made in example 1-1, etc. were cleaned with a Terg-O-Tometer (Ueshima, MS-8212) at 85rpm for 5 minutes or 10 minutes. At this time, the liquid detergent composition and model sebum artificial stain cloth were added to tap water (20 ℃) at the same time and cleaned. The cleaning conditions were that the liquid detergent composition concentration was 0.033 mass%, the water temperature was 20 ℃, and the bath ratio was 20 (adjusted to a cloth obtained by cutting cotton 2003 (manufactured by gorge shop) into 6cm × 6cm), and after cleaning, rinsing was performed for 3 minutes with tap water (20 ℃). The cleaning ratio was measured by the method described in (2-1) above, and the average of 5 blocks was determined. Based on the respective cleaning rates (average values) of 5 minutes and 10 minutes of the cleaning time, a relative cleaning value (2) of 5 minutes/10 minutes was obtained by the following equation. The results are shown in the table. In the table, the cleaning rate (average value) of 5 minutes of the cleaning time in the evaluation (2) of the cleaning speed is also represented as "cleaning rate after 5 minutes (2)".

Relative cleaning value (2) of 5 min/10 min (cleaning speed) — cleaning rate (%) of 5 min cleaning time/cleaning rate (%) of 10 min cleaning time)

*1: also included are the amounts of moieties carried by component (b).

< examples 1-28 to 1-30 and comparative examples 1-8 to 1-10 >

The components shown in table 3 were mixed in the same manner as in example 1-1 and the like to prepare liquid detergent compositions for clothing described in table 3, and the cleaning power was evaluated by the following "cleaning evaluation method (3)". The results are shown in table 3.

< method for evaluating cleanliness (3) >

(3-1) cleaning ratio of sebum stain (%)

In the above "(2-2) evaluation (2)" of cleaning speed of examples 1 to 10 and the like, the cleaning rate (average value) of the cleaning time 5 minutes with the bath ratio set to 12 was measured, and is represented as "cleaning rate after 5 minutes (3)" in the table.

[ Table 3]

1 also includes the amount of the moiety carried by component (b).

Examples 1 to 28 of Table 3 and examples 1 to 1 of Table 1, examples 1 to 29 of Table 3 and examples 1 to 2 of Table 1, or examples 1 to 30 of Table 3 and examples 1 to 3 of Table 1 differ only in bath ratio. The cleaning time 5 minutes was about the same cleaning rate, and good cleaning power was exhibited even when the bath ratio was lowered. On the other hand, when the cleaning rate of 5 minutes was compared between comparative examples 1 to 8 in table 3 and comparative examples 1 to 1 in table 1, and comparative examples 1 to 9 in table 3 and comparative examples 1 to 3 in table 1, or between comparative examples 1 to 10 in table 3 and comparative examples 1 to 5 in table 1, it was found that the cleaning rate was significantly reduced in comparative examples 1 to 8 to 1 to 10 in which cleaning was performed at a bath ratio as low as 12, as compared with the case of cleaning at a bath ratio of 20.

< examples 1-31 to 1-39 >)

Liquid detergent compositions were prepared using various anionic surfactants different in p1 and q1 in the general formula (2-1) as the component (b), and the evaluation of cleaning speed (2) was carried out by the method of the cleaning evaluation method (2) of examples 1 to 10 and the like. The results are shown in table 4. The component (b) used in this example is as follows.

(b-5): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 1.0 and the average molar number q1 of added EO is 1.0. The amount of the acid form added in the table corresponds to the amount of the acid form added in component (b), and monoethanolamine as a counter salt (the total amount used in the production process) is added in total as component (f).

(b-6): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 1.0 and the average molar number q1 of added EO is 3.0. The amount of the acid form added in the table corresponds to the amount of the acid form added in component (b), and monoethanolamine as a counter salt (the total amount used in the production process) is added in total as component (f).

(b-7): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 2.0 and the average molar number q1 of added EO is 1.0. The amount of the acid form added in the table corresponds to the amount of the acid form added in component (b), and monoethanolamine as a counter salt (the total amount used in the production process) is added in total as component (f).

(b-8): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 2.0 and the average molar number q1 of added EO is 3.0. The amount of the acid form added in the table corresponds to the amount of the acid form added in component (b), and monoethanolamine as a counter salt (the total amount used in the production process) is added in total as component (f).

(b-9): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 3.0 and the average molar number q1 of added EO is 1.0. The amount of the acid form added in the table corresponds to the amount of the acid form added in component (b), and monoethanolamine as a counter salt (the total amount used in the production process) is added in total as component (f).

(b-10): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 3.0 and the average molar number q1 of added EO is 2.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-11): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 3.0 and the average molar number q1 of added EO is 3.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

[ Table 4]

1 also includes the amount of the moiety carried by component (b).

< blend examples 1-1 to 1-16 >

Liquid detergent compositions for clothing shown in tables 5 and 6 were prepared by using various anionic surfactants different in p1 and q1 in the general formula (2-1) as the component (b). The component (b) used in this example is as follows. The effects of the present invention are considered to be exhibited in the blending examples 1-1 to 1-16.

(b-12): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 4.0 and the average molar number q1 of added EO is 1.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-13): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 4.0 and the average molar number q1 of added EO is 2.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-14): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 4.0 and the average molar number q1 of added EO is 3.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-15): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 4.0 and the average molar number q1 of added EO is 4.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-16): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 4.0 and the average molar number q1 of added EO is 5.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-17): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 5.0 and the average molar number q1 of added EO is 1.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-18): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 5.0 and the average molar number q1 of added EO is 2.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-19): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 5.0 and the average molar number q1 of added EO is 3.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-20): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 5.0 and the average molar number q1 of added EO is 4.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-21): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 5.0 and the average molar number q1 of added EO is 5.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-22): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 1.0 and the average molar number q1 of added EO is 4.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-23): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 1.0 and the average molar number q1 of added EO is 5.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-24): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 2.0 and the average molar number q1 of added EO is 4.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-25): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) wherein the average molar number p1 of added PO is 2.0 and the average molar number q1 of added EO is 5.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-26): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 3.0 and the average molar number q1 of added EO is 4.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

(b-27): the anionic surfactant produced by the same raw material and the same production method as in the above production method (b4) is a compound of the general formula (2-1) in which the average molar number p1 of added PO is 3.0 and the average molar number q1 of added EO is 5.0. The amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (total amount used in the production process) is added to component (f).

[ Table 5]

[ Table 6]

1 also includes the amount of the moiety carried by component (b).

< examples 2-1 to 2-6 and comparative examples 2-1 to 2-3 >

The components shown in table 7 were mixed to obtain compositions of examples and comparative examples.

A stirring device (made of Teflon (trademark)) having a diameter of 60mm was added to a 300ml glass beaker, and the component (a), the component (b), the component (c), and a necessary amount of 95 mass% water (containing 3mg/kg of sodium hypochlorite) were charged in such a manner that the finished mass was 200g and the blending amount shown in Table 7 was attained. After the charging, the mixture was stirred at 100 rpm for 20 minutes. Thereafter, the components (d) and (e) were added as needed, the pH of the composition was adjusted to the pH described in table 7 by the component (f), and the remaining amount of water was used to adjust the composition to a final finished mass (200g), to obtain the liquid detergent composition for clothing of table 7. In examples 2 to 6, the following other components were added at the time of adding the component (d). The pH was measured by the method described in item 8.3 of JIS K3362:1998 (the temperature of the composition at the time of measurement was 20 ℃). Using each of the obtained compositions, the following evaluations were performed. The components in the table are as follows. The results are shown in Table 7. The components in the table are as follows.

(a) Composition (I)

(a-1): a substance having an average of 7 moles of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms [ Softanol 70 (trade name, manufactured by Nippon catalyst Co., Ltd.) ]

(a-2): a substance having an average of 3 moles of ethylene oxide added to a primary alcohol having 12 carbon atoms [ Emulgen103 (trade name, manufactured by Kao corporation) ]

(a-3): a substance having an average of 5 moles of ethylene oxide added to a primary alcohol having 12 carbon atoms [ Emulgen105 (trade name, manufactured by Kao corporation) ]

(b) Composition (I)

(b 2-1): the anionic surfactant produced by the following production method (b2-1) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b2-1) >)

Linear primary alcohols having 12 and 14 carbon atoms (trade name, Kalcol 2470)1107g derived from natural oils and fats and 3.5g of KOH were added to an autoclave equipped with a stirrer, a temperature controller and an automatic inlet, and the mixture was dehydrated at 110 ℃ and 1.3kPa for 30 minutes.

After dehydration, nitrogen gas was replaced, the temperature was raised to 145 ℃ and 1107g of ethylene oxide (hereinafter referred to as "EO") was added. After addition reaction and aging at 145 ℃ and cooling to 80 ℃, unreacted EO was removed at 4.0 kPa. After removing unreacted EO, the temperature was raised to 120 ℃ and 1460g of propane oxide-1, 2-diyl (hereinafter referred to as "PO") was added. After addition reaction and aging at 120 ℃ were carried out, 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average number of moles of EO added of 2.0 and an average number of moles of PO added of 2.0.

Using SO₃The gas sulfates the alkoxylate obtained by descending the membrane reactor. The obtained sulfate was neutralized with monoethanolamine to obtain a polyoxypropane-1, 2-diyl alkyl ether sulfate salt [ (b2-1)]The composition of (1).

As a result of gas chromatography and NMR analysis, (b2-1) obtained was the following compound: in the general formula (2-2), R²Is a linear primary alkyl group having 12, 14 carbon atoms, A¹O is an allyloxy group, p2 averages 2.0, and q2 averages 2.0.

(b 2-2): an anionic surfactant produced by the following production method (b2-2) [ the amount blended in the table is the amount blended in the acid form corresponding to component (b), and monoethanolamine as a counter salt (the total amount used in the production method) is added up to component (f). ]

< manufacturing method (b2-2) >)

After dehydration, nitrogen substitution was performed, the temperature was raised to 145 ℃ and 554g of EO was added. After addition reaction and aging at 145 ℃ and cooling to 80 ℃, unreacted EO was removed at 4.0 kPa. After removal of unreacted EO, the temperature was raised to 120 ℃ and 1460g of PO was added. After addition reaction and aging at 120 ℃ were carried out, 3.8g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ℃ for 30 minutes and then extracted to obtain an alkoxylate having an average EO addition mole number of 1.0 and an average PO addition mole number of 2.0.

Using SO₃The gas passes through a falling film reactor to sulfate the alkoxylate obtained. The obtained sulfate was neutralized with monoethanolamine to obtain a polyoxypropane-1, 2-diyl alkyl ether sulfate salt [ (b2-2)]The composition of (1).

As a result of gas chromatography and NMR analysis, (b2-2) obtained was a compound represented by the following formula: in the general formula (2-2), R²Is a linear primary alkyl group having 12, 14 carbon atoms, A¹O is an allyloxy group, p2 averages 2.0, and q2 averages 1.0.

(c) Composition (I)

(c-1): diethylene glycol monobutyl ether

(c-2): propylene glycol

(c-3): 1, 6-hexanediol

(d) Composition (I)

(d-1): at 1 mol per time9 moles of ethylene oxide, 2 moles of propylene oxide and 9 moles of ethylene oxide are sequentially added to a linear primary alcohol having 10 to 14 carbon atoms derived from coconut oil in a block manner. [ formula R³O-(EO)_n11-(A²O)_n12-(EO)_n13In H, R³Is a linear alkyl group having 10 to 14 carbon atoms, A²A compound wherein O is oxypropylene, n11 is 9 on average, n12 is 2 on average and n13 is 9 on average, wherein R is³85 mol% or more of the compound of-O-EO and 90 mol% or more of the compound of-EO-H.]

(e) Composition (I)

(e-1): lunac L-55 (trade name) (coconut fatty acid; manufactured by Kao corporation)

(f) Composition (I)

(f-1): monoethanolamine (containing a counter ion as component (b))

< other ingredients >

Pigment (1): green number 202

Pigment (2): yellow No. 203

[1] Evaluation of cleaning ability

< preparation of contaminated Fabric for evaluation >

Preparation of model sebum Artificial stained cloth

A model sebum artificial contaminated liquid composed of the following components was attached to a cloth to prepare a model sebumArtificially polluting cloth. The adhesion of the model sebum artificial stain to the cloth was performed by printing the artificial stain onto the cloth using a gravure roll coater. Making artificial contaminated model sebum liquid adhered to cloth and making artificial contaminated model sebum cloth with 58cm pit capacity in gravure roller³/m²The coating speed was 1.0m/min, the drying temperature was 100 ℃ and the drying time was 1 min. Cotton 2003 (manufactured by a valley store) was used for the cloth.

Preparation of meat paste stained cloth

Commercially available retort meat paste (manufactured by Mama) was spread on a cotton knitted fabric (manufactured by gorge shop) by 0.15g and spread uniformly, dried at room temperature for 12 hours, and the resultant cloth was provided to the test.

< method for evaluating cleanliness >

(1) Evaluation of cleaning ability

67. mu.L each of the liquid detergent compositions for evaluation was directly applied to 5 pieces of meat paste-stained cloth (6 cm. times.6 cm) prepared above, left to stand in this state for 5 minutes, and then placed in 1L of tap water and cleaned at 85rpm by using a Terg-O-Tometer (Ueshima, MS-8212). The cleaning conditions were 10 minutes for cleaning, 0.033 mass% for detergent composition concentration at the time of cleaning, 20 ℃ for water temperature, and 20 for bath ratio (adjusted by cutting cotton 2003 (manufactured by gorge store) into a 6cm × 6cm cloth), and after cleaning, rinsing was performed for 3 minutes with tap water (20 ℃).

The reflectance at 550nm before and after the cleaning of the original cloth before the staining and the reflectance before and after the cleaning were measured by a colorimeter (Z-300A manufactured by Nippon Denshoku Co., Ltd.), and the cleaning ratio (%) was obtained from the following formula (the value in the table is the average value of the cleaning ratios of 5 blocks).

Relative cleaning values were obtained from the following equation based on the cleaning ratio (%) of the composition of comparative example 2-1 (indicated by a numerical value in parentheses in the table). The results are shown in the table.

Relative cleaning value ═ cleaning rate (%) of comparative example or comparative example [ (%) ] -cleaning rate (%) of comparative example 2-1 (reference composition) ]

A higher value of the relative cleaning value indicates a higher cleaning power. When the difference in relative cleanliness values was 3 or more, significant differences were observed.

(2) Evaluation of cleaning speed

5 model sebum artificial stained cloths (6 cm. times.6 cm) made as described above were cleaned with a Terg-O-Tometer (Ueshima, MS-8212) at 85rpm for 5 minutes or 10 minutes. The cleaning conditions were such that the concentration of the liquid detergent composition was 0.033 mass% and the water temperature was 20 ℃, and the liquid detergent composition was rinsed with tap water (20 ℃) for 3 minutes after cleaning. The cleaning ratio was measured by the method described in (1) above, and the average of 5 blocks was determined. From the respective cleaning rates (average values) of 5 minutes and 10 minutes of the cleaning time, a cleaning relative value was obtained by the following formula. The results are shown in the table.

Relative cleaning value (cleaning speed) of 5 min/10 min ═ cleaning rate (%) of 5 min cleaning time/cleaning rate (%) of 10 min cleaning time)

[ Table 7]

Claims

1. A liquid detergent composition for clothing, wherein,

the composition is prepared by mixing the following components (a), (b), (c) and water, wherein the total mixing amount of the component (a) and the mixing amount of the component (b) is 15-70% by mass relative to the total mass of all the mixing raw materials, the mass ratio of the mixing amount of the component (a) to the mixing amount of the component (b) is 0.5-7 in terms of component (b)/component (a),

R¹O-(EO)_mH (1)

in the formula, R¹A hydrocarbon group having 8 to 18 carbon atoms, EO represents an ethyleneoxy group, m represents an average molar number of addition, and m is a number of 1 to 9;

R²O-[(A¹O)_p/(EO)_q]-SO₃M (2)

in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethyleneoxy group, p and q represent average addition mole numbers, p is a number of 1 to 5, and q is a number of 0 to 10; "/" indicates block bonding in any order (A)¹O)_pRadical and (EO)_qA group; m is a cation;

2. The liquid detergent composition for clothing according to claim 1, wherein,

(b) component (b) is an anionic surfactant selected from the group consisting of an anionic surfactant represented by the following general formula (2-1) and an anionic surfactant represented by the following general formula (2-2),

R²O-(A¹O)_p1-(EO)_q1-SO₃M (2-1)

in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethylene oxide group, p1 and q1 represent average addition mole numbers, p1 is a number of 1 to 5, and q1 is a number of 0 to 10; m is a cation, and M is a cation,

R²O-(EO)_q2-(A¹O)_p2-SO₃M (2-2)

in the formula, R²Represents a hydrocarbon group having 8 to 22 carbon atoms, A¹O represents an alkylene oxide group selected from an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, EO represents an ethylene oxide group, p2 and q2 represent average addition mole numbers, p2 is a number of 1 or more and 5 or less, and q2 is a number of 0.5 or more and 5 or less; m is a cation.

3. The liquid detergent composition for clothing according to claim 2, wherein,

(b) the component (B) is an anionic surfactant represented by the following general formula (2-1), and p1 in the general formula (2-1) is a number of 1.1 to 4.

4. The liquid detergent composition for clothing according to claim 2, wherein,

(b) the component (B) is an anionic surfactant represented by the following general formula (2-2), and p2 in the general formula (2-2) is a number of 1.5 to 4.

5. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

(a) the total of the amount of component (a) and the amount of component (b) is 20 to 70 mass% based on the total mass of all the raw materials.

6. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

the pH at 20 ℃ is 6 to 11 inclusive.

7. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

(a) the mass ratio of the amount of component (b) to the amount of component (b) is 0.7 to 6 inclusive, in terms of component (b/(a).

8. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

(a) the mass ratio of the amount of component (a) to the amount of component (c) is 0.5 to 2.5 inclusive, in terms of component (a/(c).

9. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

(a) wherein R is selected from the group consisting of those in the above general formula (1)¹Nonionic surfactant which is a branched primary hydrocarbon group and R in the above general formula (1)¹The proportion of the nonionic surfactant (a1) in the nonionic surfactant having a linear secondary hydrocarbon group is 50% by mass or more.

10. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

(a) wherein R is selected from the group consisting of those in the above general formula (1)¹Nonionic surfactant which is a branched primary hydrocarbon group and R in the above general formula (1)¹The proportion of the nonionic surfactant (a1) in the nonionic surfactant having a linear secondary hydrocarbon group is 90% by mass or more.

11. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

as the component (a), R selected from the group consisting of the above-mentioned general formula (1) is blended¹Nonionic surfactant which is a branched primary hydrocarbon group and R in the above general formula (1)¹The nonionic surfactant (a1) of the nonionic surfactants having a linear secondary hydrocarbon group, and R in the general formula (1)¹A nonionic surfactant (a1) which is a linear primary hydrocarbon group (a2), and the nonionic surfactant (a1) is hereinafter referred to as component (a1), and the nonionic surfactant (a) is hereinafter referred to as component (a)2) Referred to as (a2) component.

12. The liquid detergent composition for clothing according to claim 11, wherein,

(a) the component (b) includes the component (a1) and the component (a2), and the blending ratio of the component (a1) to the component (a2) is 0.5 to 7 in terms of the mass ratio of the component (a 1)/the component (a 2).

13. The liquid detergent composition for clothing according to claim 11, wherein,

(a) the total ratio of the component (a1) and the component (a2) in the component (a) is 50% by mass or more.

14. The liquid detergent composition for clothing according to claim 11, wherein,

the component (a1) is R in the general formula (1)¹A nonionic surfactant which is a linear secondary hydrocarbon group.

15. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

the component (c) is at least 1 selected from the following components (c2) and (c4),

(c2) the components: a dihydric or higher and hexahydric or lower alcohol having 2 or more and 6 or less carbon atoms, and excluding polyalkylene glycols containing alkylene glycol units having 2 or more and 4 or less carbon atoms;

(c4) the components: a monoalkyl ether of a monoalkylene glycol or a monoalkyl ether of a polyalkylene glycol having an alkylene glycol unit having 2 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms.

16. The liquid detergent composition for clothing according to claim 15, wherein,

wherein (c2) and (c4) are each at least 1 selected from the following compounds,

17. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

further contains a component (d) below, wherein the mass ratio of the total of the amount of the component (a) and the amount of the component (d) to the amount of the component (b) is 0.4 to 3 in terms of component (b)/(component (a) + component (d)),

(d) the components: a nonionic surfactant represented by the following general formula (3),

R³O-(A²O)_nH (3)

in the formula, R³Represents a hydrocarbon group having 8 to 22 carbon atoms, A²O represents an alkylene oxide group having 2 to 5 carbon atoms, n represents an average molar number of addition, and is a number of 16 to 35; a. the²O comprises an average of 16 moles or more of a vinyloxy group; wherein, in A²When all O are vinyloxy groups, n is a number of 18 or more.

18. The liquid detergent composition for clothing according to claim 17, wherein,

(d) the component (B) is a compound represented by the following general formula (3-1),

R³O-[(C₂H₄O)_n1/(A²¹O)_n2]-H (3-1)

in the formula, R³A hydrocarbon group having 8 to 22 carbon atoms, A²¹O is an alkylene oxide group having 3 to 5 carbon atoms; n1 and n2 are average addition mole numbers, n1 is a number of 15 to 30 inclusive, n2 is a number of 1 to 5 inclusive, and the total number of n1 and n2 is a number of 16 to 35 inclusive; "/" denotesC₂H₄O radical and A²¹The O groups may be combined in any of random or block form; in addition, A²¹O may also be divided into multiple chunks.

19. The liquid detergent composition for clothing according to claim 17, wherein,

(d) the component (A) is a compound combined by the following steps: r in the above general formula (3-1)³Has 10 to 18 carbon atoms, A²¹O is an alkylene oxide group selected from the group consisting of an alkylene oxide group having 3 carbon atoms and an alkylene oxide group having 4 carbon atoms, n1 is a number of 16 or more and 27 or less, n2 is a number of 2 or more and 4 or less, and the total of n1 and n2 is 17 or more and 30 or less.

20. The liquid detergent composition for clothing according to claim 17, wherein,

(d) the component (A) is at least 1 compound selected from the following general formulas (3-1-1) to (3-1-5),

R³O-(A²¹O)_n2-(C₂H₄O)_n1-H (3-1-1)

R³O-(C₂H₄O)_n1-(A²¹O)_n2-H (3-1-2)

R³O-[(C₂H₄O)_n11·(A²¹O)_n2]-(C₂H₄O)_n12-H (3-1-3)

R³O-(C₂H₄O)_n11-[(A²¹O)_n2·(C₂H₄O)_n12]-H (3-1-4)

R³O-(C₂H₄O)_n11-(A²¹O)_n2-(C₂H₄O)_n12H (3-1-5)

in the formula, R³A hydrocarbon group having 8 to 22 carbon atoms, A²¹O is an alkylene oxide group having 3 to 5 carbon atoms; n1 and n2 represent average molar numbers of addition, n1 represents a number of 15 to 30 inclusive, n2 represents a number of 1 to 5 inclusive,the total number of n1 and n2 is 16 to 35 inclusive; n11 and n12 are average addition mole numbers, and n1 is n11+ n 12; "·" indicates random incorporation; in addition, A²¹O may also be divided into multiple chunks.

21. The liquid detergent composition for clothing according to claim 17, wherein,

R³O-(A²¹O)_n2-(C₂H₄O)_n1-H (3-1-1)

R³O-(C₂H₄O)_n1-(A²¹O)_n2-H (3-1-2)

R³O-[(C₂H₄O)_n11·(A²¹O)_n2]-(C₂H₄O)_n12-H (3-1-3)

R³O-(C₂H₄O)_n11-[(A²¹O)_n2·(C₂H₄O)_n12]-H (3-1-4)

R³O-(C₂H₄O)_n11-(A²¹O)_n2-(C₂H₄O)_n12H (3-1-5)

in the formula, R³Is a linear primary alkyl group having 8 to 22 carbon atoms, A²¹O is an alkylene oxide group having 3 to 5 carbon atoms; n1 and n2 are average addition mole numbers, n1 is a number of 15 to 30 inclusive, n2 is a number of 1 to 5 inclusive, and the total number of n1 and n2 is a number of 16 to 35 inclusive; n11 and n12 are average addition mole numbers, and n1 is n11+ n 12; "·" indicates random incorporation; in addition, A²¹O may also be divided into multiple chunks.

22. The liquid detergent composition for clothing according to claim 20 or 21, wherein,

(d) the component (A) is at least 1 compound selected from the general formulas (3-1-2), (3-1-4) and (3-1-5).

23. The liquid detergent composition for clothing according to claim 17, wherein,

(d) the mass ratio of the amount of component (a) to the amount of component (a) is 0.2 to 3 inclusive, in terms of component (a/(d).

24. The liquid detergent composition for clothing according to claim 17, wherein,

(a) the mass ratio of the total of the amount of component (a) and the amount of component (d) to the amount of component (b) is 0.4 to 3 in terms of component (b)/[ (a) component + (d) component ].

25. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

1 or more enzymes selected from cellulase, amylase, pectinase, protease and lipase are mixed in an amount of 0.01-2 mass%.

26. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

1 or more enzymes selected from amylase and protease are mixed in an amount of 0.01 to 2% by mass.

27. The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein,

the amount of the cationic surfactant is 5% by mass or less.

28. A method for cleaning clothes, wherein,

a cleaning liquid containing water and 0.01 to 0.2 mass% of the liquid detergent composition for clothing, the temperature of which is 0 to 35 ℃, wherein the unit of the amount of the cleaning liquid is liter and the unit of the mass of the clothing is kg, is used for cleaning the clothing for 1 to 7 minutes under the condition that the bath ratio represented by the ratio of the mass of the clothing to the amount of the cleaning liquid is 3 to 50 inclusive, wherein the amount of the cleaning liquid is 3 to 50 inclusive.

29. The cloth cleaning method according to claim 28,

the cloth is cleaned for 3 minutes to 7 minutes.

30. The cloth cleaning method according to claim 28 or 29, wherein,

the bath ratio represented by the ratio of the mass of the clothing to the amount of the cleaning liquid is 5 or more and 20 or less in terms of the amount of the cleaning liquid per unit of liter and the mass of the clothing in terms of kg.

31. The cloth cleaning method according to claim 28 or 29, wherein,

the cleaning liquid contains a liquid detergent composition for clothing in an amount of 0.02 to 0.1 mass%.

32. The cloth cleaning method according to claim 28 or 29, wherein,

the cleaning of the cloth was performed using a rotary washing machine.

33. The cloth cleaning method according to claim 32,

the rotary washing machine is a drum-type full-automatic washing machine, a pulsator full-automatic washing machine or a stirring full-automatic washing machine.