JP5253712B2 - Liquid detergent composition for clothing - Google Patents

Description

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

2. Description of the Related Art Conventionally, liquid cleaning compositions for clothing have been required to have high cleaning power against dirt that is difficult to remove, such as mud dirt.
As a conventional liquid cleaning composition for clothing, for example, Patent Document 1 discloses a cleaning composition combining a plurality of types of specific surfactants for the purpose of cleaning stubborn dirt. .
Patent Document 2 discloses a liquid detergent composition for clothing that uses a specific nonionic surfactant for the purpose of satisfying both texture and detergency without feeling of squeak.
Japanese Patent No. 3556806 Japanese Patent No. 2813112

  However, the compositions described in Patent Documents 1 and 2 are not satisfactory in the cleaning effect against mud dirt.

  Therefore, an object of the present invention is to provide a liquid detergent composition for clothing having a good detergency against mud dirt.

［式中、Ｘ、Ｙ、Ｚは、それぞれ独立してＨ、Ｃ_ｎ”Ｈ_{２ｎ”＋１}、または（ＣＨ_３）_２ＣＨ（ｎ”は１〜３の整数である）であり；Ｍは、Ｈ、アルカリ金属原子、アルカリ土類金属原子、ＮＨ_４ ^＋、または、アルカノールアミン類を示す。］
（Ｃ）下記一般式（ＩＩ）で表される化合物及び下記一般式（ＩＩＩ）で表される化合物から選ばれる１種以上の化合物

（式中、Ｒ^１１、Ｒ^１２は、それぞれ独立に、炭素数１〜２０の直鎖または分岐鎖のアルキル基またはアルケニル基、直鎖ヒドロキシアルキル基、トリル基、フェニル基、ベンジル基のいずれかであり；Ｒ^１３は、炭素数８〜２０の直鎖または分岐鎖のアルキル基またはアルケニル基、直鎖ヒドロキシアルキル基、トリル基、フェニル基、ベンジル基のいずれかであり；ＥＯはエチレンオキシド基であり；ａ、ｂはそれぞれ０以上の整数を示し、ａ＋ｂは１０以上であり；Ｘ_１ ⁻は、陰イオンである。）
本発明の衣料用液体洗浄剤組成物は、さらに（Ｄ）１−ヒドロキシエタン−１，１−ジホスホン酸及び／またはその塩を含有することが好ましい。 In order to solve the above-mentioned problems, the present invention proposes a liquid cleaning composition for clothing comprising the following components (A), (B), and (C).
(A) 2-50% by mass of a polyoxyethylene alkyl ether having an alkyl group with 10-20 carbon atoms and an average added mole number of ethylene oxide of 3-26,
(B) a compound represented by the following general formula (I),

Wherein X, Y and Z are each independently H, C _{n ″} H _{2n ″ +1} , or (CH ₃ ) ₂ CH (n ″ is an integer from 1 to 3); H, an alkali metal atom, an alkaline earth metal atom, NH ₄ ⁺ , or an alkanolamine is represented.]
(C) One or more compounds selected from the compound represented by the following general formula (II) and the compound represented by the following general formula (III)

(In the formula, each of R ¹¹ and R ¹² is independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, or a benzyl group. R ¹³ is any one of a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, and a benzyl group; EO is an ethylene oxide group Yes; a and b each represent an integer of 0 or more, a + b is 10 or more; and X ₁ ⁻ is an anion.)
The liquid detergent composition for clothing of the present invention preferably further contains (D) 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof.

  In the present invention, a liquid detergent composition for clothing having good detergency against mud dirt can be provided.

(A) component (A) A component is 2-50 mass% of polyoxyethylene alkyl ethers whose carbon number of an alkyl group is 10-20, and whose average added mole number of ethylene oxide is 3-26.
The carbon number of the alkyl group is preferably 11 or more, more preferably 12 or more, and the upper limit is preferably 18 or less, particularly 15 or less, from the viewpoint of mud dirt cleaning power.
In addition, in 1 mol of component (A), the average added mole number of ethylene oxide is preferably 5 or more, more preferably 8 or more, and the upper limit is preferably 20 or less, more preferably from the viewpoint of mud dirt cleaning power. Is 18 or less.
The component (A) is a nonionic surfactant, and can be obtained by addition reaction of higher oxide with ethylene oxide by a conventional method using an alkali catalyst or the like, or a commercially available product can be used.
Examples of higher alcohols include linear primary alcohols, branched primary alcohols, linear secondary alcohols, and the like.

(A) A component can be used 1 type or in mixture of 2 or more types.
(A) The compounding quantity of a component is 2-50 mass% in the liquid cleaning composition for garments. Preferably it is 10-50 mass%, More preferably, it is 15-45 mass%, Especially preferably, it is the range of 20-40 mass%. When the blending amount of the component (A) is within this range, the detergency of mud dirt is improved. Moreover, the detergency of sebum dirt is improved.

Component (B) The component (B) is a compound represented by the general formula (I).
In the formula, X, Y and Z are each independently H, C _{n ″} H _{2n ″ +1} or (CH ₃ ) ₂ CH (where n ″ is an integer of 1 to 3), preferably CH ₃ It is.
M represents H; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as magnesium or calcium; NH ₄ ⁺ ; or an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine, preferably sodium Monoethanolamine and diethanolamine.

Examples of specific compounds include benzene sulfonic acid, benzene sulfonic acid sodium salt, benzene sulfonic acid potassium salt, benzene sulfonic acid ammonium salt, benzene sulfonic acid magnesium salt, benzene sulfonic acid calcium salt, and benzene sulfonic acid monoethanolamine salt. Benzenesulfonic acid diethanolamine salt, benzenesulfonic acid triethanolamine salt, p-toluenesulfonic acid, p-toluenesulfonic acid sodium salt, p-toluenesulfonic acid potassium salt, p-toluenesulfonic acid ammonium salt, p-toluenesulfonic acid Magnesium salt, p-toluenesulfonic acid calcium salt, p-toluenesulfonic acid monoethanolamine salt, p-toluenesulfonic acid diethanolamine salt, p-toluenesulfonic acid triethanol Min salt, o- or m- or p-xylene sulfonic acid, o- or m- or p-xylene sulfonic acid sodium salt, o- or m- or p-xylene sulfonic acid potassium salt, o- or m- or p Xylenesulfonic acid ammonium salt, o- or m- or p-xylenesulfonic acid magnesium salt, o- or m- or p-xylenesulfonic acid calcium salt, o- or m- or p-xylenesulfonic acid monoethanolamine salt O- or m- or p-xylenesulfonic acid diethanolamine salt, o- or m- or p-xylenesulfonic acid triethanolamine salt, cumenesulfonic acid, cumenesulfonic acid sodium salt, cumenesulfonic acid potassium salt, cumenesulfonic acid Ammonium salt, cumene sulfonic acid Magnesium salts, particulate members sulfonic acid calcium salt, particulate members acid monoethanolamine salt, particulate members acid diethanolamine salt, particulate members acid triethanolamine salt and the like.
Of these, p-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid or monoethanolamine salts thereof are preferable.

(B) A component can be used 1 type or in mixture of 2 or more types.
The blending amount of the component (B) is preferably 1 to 15% by mass, more preferably 3 to 10% by mass, and particularly preferably 3 to 6% by mass in the liquid detergent composition for clothing. It is. When the component (B) is in this range, the detergency of mud dirt is improved. Moreover, since it is excellent in storage stability, it is preferable.

Component (C) The component (C) is one or more compounds selected from a compound represented by the following general formula (II) and a compound represented by the following general formula (III).
In the general formula (II), R ¹¹ and R ¹² are each independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, a phenyl group, or a benzyl group. Indicates either.
More preferably, carbon number of an alkyl group is 10-18. The carbon number of the alkenyl group is particularly preferably 10-18.
In the long-chain hydroxyalkyl group, the alkyl group preferably has 10 to 20 carbon atoms, particularly 10 to 18 carbon atoms. The number of hydroxy groups is 1-3, for example, Preferably it is one.
Particularly preferably, one of R ¹¹ and R ¹² is a combination of a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, and the other is a combination of a methyl group, a tolyl group or a benzyl group.

EO represents an ethylene oxide group. a and b each independently represent an average addition mole number of an ethylene oxide group, and are each independently an integer of 0 or more.
Moreover, a + b is 10 mol or more, Preferably it is 10-50 mol. When a + b is 10 mol or more, the effect of dispersing organic substances in the mud is improved, and the detergency against mud dirt is improved.
X ₁ ⁻ is an anion, a halogen atom ion such as chlorine ion, bromine ion, iodine ion, or the general formula R ⁴ O ₄ ⁻ [wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms (methyl group) , An ethyl group, a propyl group, etc., particularly preferably a methyl group].

Examples of commercially available products include, for example, trade name “Bisnor UP-10” (R ¹¹ : beef tallow-derived alkyl group (carbon number: 14 to 20), R ¹² : benzyl group, a + b = 30, manufactured by Yushi Co., Ltd. , _X ^{1 -:} Cl -) and, Lion Akzo Co., trade name "Ethoquad (Esokato) C / 25" ^{(R 11:} alkyl group derived from coconut oil (having 8 to 18 carbon ^{atoms), R 12:} methyl Group, a + b = 15, X ₁ ⁻ : Cl ⁻ ) and the like.

In the general formula (III), R ¹³ is any one of a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, a phenyl group, and a benzyl group. .
More preferably, carbon number of an alkyl group is 10-18. The carbon number of the alkenyl group is particularly preferably 10-18.
In the long-chain hydroxyalkyl group, the alkyl group preferably has 10 to 20 carbon atoms, particularly 10 to 18 carbon atoms. The number of hydroxy groups is 1-3, for example, Preferably it is one.
R ¹³ is particularly preferably a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms.

EO represents an ethylene oxide group. a and b are average addition mole numbers of ethylene oxide groups, and each independently represents an integer of 0 or more. Moreover, a + b is 10 mol or more, Preferably it is 10-50 mol. When a + b is 10 or more, the effect of dispersing organic substances in the mud is improved, and the detergency against mud dirt is improved.
Examples of commercially available products include a product name “ETHOMEEN C / 25” (R ¹³ : alkyl group derived from coconut oil (carbon number: 8 to 18), a + b = 15), manufactured by Lion Akzo Co., Ltd. Product name “ETHOMEEN SA2Y-103” (R ¹³ : Alkyl group derived from hardened beef tallow (carbon number 14 to 20), a + b = 50), manufactured by Akzo Co., Ltd., trade name “ETHOMEEN (ESOMINE) SAJ-103” (R ¹³ : alkyl group derived from hard beef tallow (carbon number: 12 to 20), a + b = 10) and the like.

(C) component can be used 1 type or in mixture of 2 or more types.
The content of the component (C) is preferably 0.5 to 10% by mass, preferably 0.5 to 5% by mass, in the liquid detergent composition for clothing, from the viewpoint of improving the cleaning effect of mud dirt. . It is preferable to use in this range also from the point of the cleaning effect with respect to sebum dirt.
It should be noted that the content of the component (C) is preferably 10% by mass or less, which facilitates formulation and is preferable.

Component (D) Component (D) is 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof.
By blending the component (D), the effect of the present invention is improved.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt.
Of these, 1-hydroxyethane-1,1-diphosphonic acid is preferred.
(D) component can be used 1 type or in mixture of 2 or more types.
The content of the component (D) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, in the liquid detergent composition for clothing, from the viewpoint of mud dirt cleaning power. By being 0.1 mass% or more, the detergency of mud dirt improves, and when it is 10 mass% or less, (D) component can be mix | blended more stably. Moreover, it is preferable also from the point of the cleaning power improvement of sebum dirt.

Other optional components Nonionic surfactants and anionic surfactants other than the component (A) can be blended in the liquid detergent composition for clothing of the present invention.
The nonionic surfactant has an alkyl group having 8 to 18 carbon atoms, an alkyl polyglucoside having an average addition mole number of 1 to 10 glucose units, an alkyl group having 8 to 18 carbon atoms, and an average of glycerin units. Alkyl glyceryl ether having 1 to 3 addition moles, fatty acid diethanolamide having 10 to 20 carbon atoms, alkyl group having 10 to 18 carbon atoms, methoxypolyoxyethylene alkanoate having an average addition mole number of ethylene oxide of 1 to 30, etc. Is mentioned.
The amount of the nonionic surfactant other than the component (A) is preferably in the range of 0 to 10% by mass in the liquid detergent composition for clothing.

As an anionic surfactant, an alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms, an alkyl sulfate having an alkyl group having 10 to 20 carbon atoms, an alkyl group having 10 to 20 carbon atoms, and ethylene oxide Polyoxyethylene alkyl ether sulfate having an average addition mole number of 1 to 10, α-olefin sulfonate having an alkyl group having 10 to 20 carbon atoms, alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, carbon number Examples include α-sulfo fatty acid methyl ester salts having 10 to 20 alkyl groups, polyoxyethylene alkyl ether carboxylates having 10 to 20 carbon atoms and an average addition mole number of ethylene oxide of 1 to 10. .
The compounding amount of these anionic surfactants is preferably in the range of 0 to 10% by mass in the liquid detergent composition for clothing.

The liquid detergent composition for clothing of the present invention may contain other optional components as necessary.
Specifically, examples of the hydrotrope include glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and alcohols such as ethanol. Among these, polyethylene glycol and ethanol having a mass average molecular weight of 400 to 5000 are preferable.
Examples of the alkali agent include alkanolamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The alkanolamine may be used alone or in combination of two or more.
The blending amount of these hydrotropes and alkali agents is preferably in the range of 0.1 to 10% by mass, more preferably 1 to 5% by mass in the liquid cleaning composition for clothing.

Moreover, the liquid cleaning composition for clothing may contain 0 to 1% by mass of a fatty acid having 8 to 22 carbon atoms as a foam suppressant. Fatty acids having a carbon number in the range of 8 to 22 are preferable, and saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, or oleic acid, linoleic acid, linolenic acid, etc. Any of unsaturated fatty acids may be used. Of these, palmitic acid is most preferred.
Furthermore, for the purpose of preventing recontamination, 0 to 2% by mass of a recontamination inhibitor such as polyvinylpyrrolidone and carboxymethylcellulose, and 0 to 1% by mass of an enzyme such as lipase, cellulase, amylase and protease for the purpose of improving detergency. For the purpose of enzyme stabilization, boric acid, borax, formic acid or salts thereof, calcium salts such as calcium chloride and calcium sulfate 0 to 3% by mass, dimethyl silicone, polyether-modified silicone, amino-modified for the purpose of improving the texture 0-5% by mass of silicone such as silicone, 0-1% by mass of fluorescent agent such as distyryl biphenyl type for the purpose of improving whiteness of white clothing, acid dyes, etc. for the purpose of coloring liquid detergent compositions 0.0001 to 0.001% by mass of the above dye, dibutylhydroxytoluene and the like for the purpose of stabilizing the fragrance Antioxidant 0.0001 mass%, the purpose of antiseptic, antibacterial agents such as caissons CG / ICP may be added 0 to 0.05 wt%. Examples of the fragrance for aroma include a fragrance composition containing a fragrance component, a solvent and a stabilizer described in JP-A No. 2002-146399, and the like in the liquid cleaning composition for clothing of the present invention. 0.01 to 1% by mass can be added.
Furthermore, as a pH adjuster, inorganic acids and inorganic bases such as sulfuric acid, sodium hydroxide, potassium hydroxide and the like can be blended. The pH of the liquid detergent composition for clothing of the present invention includes mud dirt cleaning power, From the viewpoint of maintaining detergency after storage, 7.0 to 11.0 is preferable, and 9.0 to 10.5 is more preferable.

The liquid detergent composition for clothing of the present invention can be prepared based on a conventional method, preferably using water as a solvent.
The usage method is a normal usage method, that is, a method of pouring water together with the laundry at the time of washing, a method of directly applying the liquid cleaning composition for clothing to mud and sebum soil, and a liquid cleaning composition for clothing to water. For example, a method of immersing clothing by dissolving it in Also preferred is a method in which a liquid detergent composition for clothing is applied to the laundry and allowed to stand as appropriate, followed by normal washing using a laundry liquid containing an anionic surfactant.

  Thus, in this invention, the liquid cleaning composition for clothes which has favorable detergency with respect to mud dirt can be provided. Moreover, the liquid detergent composition for clothes of the present invention exhibits a high detergency against sebum stains.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

(Examples 1-16, Comparative Examples 1-6)
The liquid cleaning composition for clothes having the composition shown in Tables 1 to 4 was prepared. In addition, the unit of the compounding quantity shown in the table | surface is the mass%, The water amount was adjusted so that the total amount might be 100 mass%.
That is, the component (A) and polyethylene glycol were stirred and dissolved at 50 ° C. or lower, and then cooled to 40 ° C. or lower. All subsequent steps were performed between room temperature and 40 ° C.
Thereafter, component (B), monoethanolamine, or diethylamine was added and stirred.
Thereafter, 90% of the total mass of purified water (balance) was added, and the fragrance was added and stirred. And after adding (C) component, (D) component other arbitrary components, and the pigment | dye, and stirring, pH was adjusted so that it might become the value shown in the table | surface, and the remaining purified water was added.
The pH was adjusted with a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH of the liquid cleaning composition for clothing to be adjusted was a value shown in the table.

  About the obtained liquid cleaning composition for clothes, it evaluated as follows and the result was shown according to Tables 1-4.

<Description of ingredients shown in the table>
(A) Component A-1: C _n H _{2n + 1} O (EO) ₁₅ H (n = 12/13 mixture (mass ratio 55/45)), a synthetic product produced by the following method (synthesis method of A-1)
Product name Safol 23 alcohol (branch rate 50% ^{* 1} ) 224.4g, 30% NaOH aqueous solution 2.0g was extract | collected in the pressure | voltage resistant reaction container, and the inside of a container was substituted by nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. . After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, and thus obtained.
* 1 Branching rate: The branching rate indicates the ratio of the number of carbon atoms constituting the branched chain to the total number of carbon atoms.

_{A-2: C n H 2n} + 1 CH C m H 2m + 1 O (EO) 9 H (m + n = 11~13),
Nippon Shokubai Co., Ltd. product name Softanol 90, average EO 9 mol adduct of branched chain-containing secondary alcohol)

_{A-3: C n H 2n} + 1 O (EO) 15 H (n = 12/14 mixture (weight ratio 71/29)), synthesized the synthetic product by the following methods.
(Synthesis method of A-3)
P & G C _12-14 alcohol 224.4 g was used and synthesized in the same manner as A-1.

_{A-4: C 13 H 27} O (EO) 5 H ( branched chain-containing, dyad - Le 13, branching ratio ^* 1 50%)
Average EO 5 mol adduct of branched chain-containing higher alcohol of C13 manufactured by Mitsubishi Chemical Corporation

_{A-5: C 13 H 27} O (EO) 7 H (C chain length, branched),
BASF Lutensol TO7

(B) Component B-1: p-toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd. B-2: cumenesulfonic acid: manufactured by Teika Co., Ltd. Trade name “Taikatox 500”
B-3: m-xylenesulfonic acid: Mitsubishi Gas Chemical Co., Ltd. trade name “SXA-60”

(C) Component C-1: Esocate C / 25 (trade name, manufactured by Lion Akzo Co., Ltd .; compound represented by formula (II), wherein R ^{11 is} an alkyl group derived from coconut oil (8 to 8 carbon atoms) 18), R ¹² : methyl group, a + b = 15, X ₁ ⁻ = Cl ⁻ )
C-2: Esomine SA2Y-103 (trade name, manufactured by Lion Akzo Co., Ltd .; compound represented by formula (III), wherein R ^{13 is} an alkyl group derived from cured beef tallow (carbon number 14-20), a + b = 50 )
C-3: Esomine SAJ-103 (trade name, manufactured by Lion Akzo Co., Ltd .; compound represented by formula (III), wherein R ^{13 is} an alkyl group derived from cured beef tallow (carbon number 12 to 20), a + b = 10 )
C-4: Bisnor UP-10 (trade name, manufactured by Otsuka Kogyo Co., Ltd .; compound represented by formula (II), wherein R ^{11 is} an alkyl group derived from beef tallow (14 to 20 carbon atoms), R ¹² : benzyl group, a + b = 30, X ₁ ⁻ = Cl ⁻ )

(D) Component D-1: 1-hydroxyethane-1,1-diphosphonic acid (trade name “BRIQUEST ADPA-A” manufactured by ALBRITE & WILSON)

Optional component Monoethanolamine: Diethanolamine manufactured by Nippon Shokubai Co., Ltd .: LAS-Na manufactured by Nippon Shokubai Co., Ltd .: Linear alkylbenzene sulfonate sodium salt (alkyl group having carbon number 10/12/14) blend)
Palmitic acid: Ethanol manufactured by Nippon Oil & Fats Co., Ltd .: 95 vol% Synthetic ethanol Propylene glycol manufactured by NEDO: PEG # 1000 (mass average molecular weight 1000) Fragrance composition manufactured by Nippon Oil & Fats Co., Ltd .: JP 2002-146399 A Perfume compositions A to D described in Tables 11 to 18 described in Japanese Patent Publication
Dye A: Green 201, Sakai Kasei Co., Ltd. Dye B: Yellow 201, Sakai Kasei Co., Ltd. Dye C: Green No. 3, Sakai Kasei Co., Ltd. Dye D: Kirin Yellow-WG-G CONC, Central Synthetic Chemistry Stearyltrimethylammonium chloride manufactured by Lion Co., Ltd.

《Mud dirt cleaning power evaluation》
15 g of horticultural black soil (manufactured by kyotochiya) was weighed, put into 500 g of tap water, and dispersed with a homogenizer (KINEMATICA Switzerland), trade name Polytron Type PT 10/35) at 80 rpm for about 5 minutes. In the obtained mud dispersion, 15 pieces of cotton knitted fabric cut into 10 cm x 25 cm (Dyeing material, manufactured by Tanigami Shoten Co., Ltd., unsilled with cotton knit) are immersed, and the fabric is thoroughly rubbed by hand. The mud dispersion was uniformly contained throughout. The cloth was taken out and lightly squeezed with a roller. After naturally drying for 1 hour, it was further dried for 1 hour in a thermostatic bath at 105 ° C.
Finally, the surface of the cloth was rubbed with a urethane sponge, and the excess mud particles were removed and used as a model mud soil cloth for evaluation.
Each model mud soil cloth adjusted as described above was divided into five pieces (each 2 × 2 cm ² ), and this was used as an evaluation cloth for the experiment.
The following method was applied as the cleaning method. That is, 0.6 g of the liquid detergent composition for clothing was applied to 5 sheets of soiled cloth, left for 5 minutes, and then 5 sheets of soiled cloth were directly put into a Terg-O-Tometer (cleaning tester). After putting 0.9L of tap water (hardness 3DH) 0.9C and stirring at 120 rpm for 10 minutes, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation) and dehydrated for 1 minute. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

<< Evaluation of sebum dirt cleaning power >>
Ten sheets of sebum soiled cloth (contaminated cloth) prepared by rubbing the sebum dirt on the face against 100th cotton plain weave cloth (uncontaminated cloth) cut to 10 cm square were prepared.
As a washing method, 0.6 g of a liquid detergent composition for clothing was put into a Terg-O-Tometer, stirred for 30 seconds, and then 10 pieces of dirty cloth were put into the Terg-O-Tometer as they were at 15 ° C. After adding 0.9L of tap water (hardness 3DH) and stirring at 120 rpm for 10 minutes, it was transferred to a two-tank washing machine (Mitsubishi Electric Corporation, product number: CW-C30A1-H1) and dehydrated for 1 minute. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

"Evaluation criteria"
The mud dirt cleaning power and sebum dirt cleaning power are measured by using a colorimetric color difference meter (Nippon Denshoku Co., Ltd., trade name: SE2000) to measure the Z value of the raw cloth before and after cleaning. The washing rate was evaluated. The average value of 10 sheets was used for each evaluation.

Washing rate (%) = (Z value after washing−Z value before washing) / (Z value of raw fabric−Z value before washing) × 100

The mud dirt cleaning power was evaluated according to the following criteria.
A: Cleaning rate exceeds 25% B: Cleaning rate 20-25%
C: Cleaning rate less than 20%

The evaluation of the sebum dirt cleaning power was performed according to the following criteria.
A: Cleaning rate exceeds 60% B: Cleaning rate 40-60%
C: Cleaning rate less than 40%

As is apparent from the results shown in Tables 1 to 4, it was confirmed that good detergency was obtained for both mud and sebum soils in the examples according to the present invention.

Claims (2)

Following component (A) contains the component (B), and component (C), the amount of anionic surfactant is 0 to 10 mass%, pH is a 9.0 to 11.0 der Rukoto A liquid detergent composition for clothing.
(A) 15 to 50% by mass of polyoxyethylene alkyl ether having 10 to 15 carbon atoms of the alkyl group and 3 to 26 average addition moles of ethylene oxide,
(B) a compound represented by the following general formula (I),

Wherein X, Y and Z are each independently H, C _{n ″} H _{2n ″ +1} , or (CH ₃ ) ₂ CH (n ″ is an integer from 1 to 3); H, an alkali metal atom, an alkaline earth metal atom, NH ₄ ⁺ , or an alkanolamine is represented.]
(C) One or more compounds selected from a compound represented by the following general formula (II) and a compound represented by the following general formula (III).

(In the formula, each of R ¹¹ and R ¹² is independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, or a benzyl group. R ¹³ is any one of a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, and a benzyl group; EO is an ethylene oxide group Yes; a and b each represent an integer of 0 or more, a + b is 10 or more; and X ₁ ⁻ is an anion.) Furthermore (D) 1-hydroxyethane-1,1-diphosphonic acid and / or laundry liquid detergent composition according to claim 1 salt thereof.