JP2007224199A - Liquid detergent composition for clothes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothes, having excellent rinsability. <P>SOLUTION: The liquid detergent composition for the clothes contains the following components (A), (B) and (C): (A) an ethylene oxide adduct represented by general formula (I) (wherein, R<SP>1</SP>is a 7-21C linear or branched alkyl group or alkenyl group; R<SP>2</SP>is a 1-3C alkyl group; and n is an average number of added moles of ethylene oxide), and having ≥55 mass% narrow rate exhibiting the proportion of distribution of ethylene oxide adducts having different number of added mols of ethylene oxide; (B) a semipolar surfactant and/or an ampholytic surfactant; and (C) a chelating agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  Conventionally, nonionic surfactants and combinations of nonionic surfactants and anionic surfactants have been used as liquid cleaning compositions for clothing.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, alkyl glycoside and the like are generally used.
In recent years, a detergent composition in which a fatty acid polyoxyalkylene alkyl ether, which is an ester-type nonionic surfactant, is used as a cleaning component has been proposed.

As a detergent composition using a fatty acid polyoxyalkylene alkyl ether, for example, an alkoxylated carboxylic acid ester (fatty acid polyoxyalkylene alkyl ether) is used to reduce the viscosity of an aqueous surfactant system (formulation). Have been proposed (see Patent Document 1).
Also, a liquid detergent composition containing a hydrophilic organic compound such as low-molecular glycols or polyoxyalkylene ether and an enzyme, which prevents the formation of a film due to gelation of the liquid surface of the detergent composition (Patent Document) 2), liquid detergent compositions containing an anionic surfactant and a hydrotrope (see Patent Document 3), and the like.
In addition, an anionic surfactant is used in combination, and a detergent composition having excellent detergency and foaming power (see Patent Document 4) and polyoxyalkyleneamine are used in combination, and even a small amount of surfactant (low concentration) is high. A liquid detergent composition for clothing that does not cause yellowing while having cleaning performance (see Patent Document 5) has been proposed.
JP 2002-526599 A Japanese Patent Laid-Open No. 2000-192099 JP-A-5-202381 JP 2000-144179 A JP 2005-171195 A

On the other hand, a liquid detergent composition for clothing is conventionally required to have a high detergency. Furthermore, in recent years, it has been required to have good rinsing properties such as quick blowout of bubbles.
However, the cleaning compositions described in Patent Documents 1 to 5 are not satisfactory in rinsing properties.
Accordingly, an object of the present invention is to provide a liquid detergent composition for clothing having excellent rinsing properties.

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) An ethylene oxide adduct represented by the following general formula (I), wherein the ethylene oxide adduct has a narrow ratio of 55% by mass or more indicating a distribution ratio of ethylene oxide adducts having different moles of addition of ethylene oxide. body,
(B) a semipolar surfactant and / or an amphoteric surfactant,
(C) Chelating agent.

［式中、Ｒ^１は炭素数７〜２１の直鎖状もしくは分岐鎖状のアルキル基またはアルケニル基であり；Ｒ^２は炭素数１〜３のアルキル基であり；ｎはエチレンオキサイドの平均付加モル数を示し、５〜３０である。］

[Wherein R ¹ is a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; n is an average addition of ethylene oxide] The number of moles is shown and is 5-30. ]

  In the liquid detergent composition for clothes of the present invention, the component (C) preferably contains 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof.

  Here, in the present specification and claims, the “narrow ratio indicating the distribution ratio of ethylene oxide adducts having different numbers of added moles of ethylene oxide” refers to those represented by the following formula (S). .

［式中、ｎ_ｍａｘは全体のエチレンオキサイド付加体中に最も多く存在するエチレンオキサイド付加体のエチレンオキサイドの付加モル数を示す。ｉはエチレンオキサイドの付加モル数を示す。Ｙｉは全体のエチレンオキサイド付加体中に存在するエチレンオキサイドの付加モル数がｉであるエチレンオキサイド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most present in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an added mole number of ethylene oxide present in the entire ethylene oxide adduct. ]

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothes excellent in the rinse property can be provided.

The liquid detergent composition for clothing according to the present invention comprises (A) an ethylene oxide adduct represented by the above general formula (I), and the proportion of the distribution of ethylene oxide adducts having different addition moles of ethylene oxide. It contains an ethylene oxide adduct having a narrow ratio of 55% by mass or more, (B) a semipolar surfactant and / or an amphoteric surfactant, and (C) a chelating agent.
Hereinafter, each component will be described in detail.

(A) component In this invention, (A) component is the ethylene oxide adduct represented by the said general formula (I), Comprising: The distribution ratio of the ethylene oxide adduct from which the addition mole number of ethylene oxide differs is shown. An ethylene oxide adduct having a narrow rate of 55% by mass or more.
The narrow rate is preferably 65% by mass or more. The higher the narrow ratio, the better. However, the upper limit is substantially 80% by mass or less. When the narrow rate is 55% by mass or more, rinsing properties are improved.

The narrow rate can be controlled by, for example, the method for producing the component (A).
(A) Although it does not restrict | limit especially as a manufacturing method of a component, As a suitable method, ethylene oxide is addition-polymerized to fatty-acid alkylester, for example using the surface-modified composite metal oxide catalyst. The method (refer the said patent document 4) is mentioned.
As a preferable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Tl ³⁺ , surface-modified with a metal hydroxide or the like are used. Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide, and a hydrotalcite fired product whose surface is modified with a metal hydroxide and / or metal alkoxide Such as a catalyst.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

In the general formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms.
In R ¹ , the number of carbon atoms of the alkyl group and alkenyl group is preferably 9 to 17 from the viewpoint of improving the detergency against sebum dirt and mud dirt.
R ² is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
n shows the average addition mole number of ethylene oxide, and is 5-30. Preferably, it is 7 to 20 from the viewpoint of improving detergency against sebum stains, mud stains, etc., and liquid stability (for example, stability over time at low temperature) of the liquid detergent composition for clothing.
The component (A) used in the present invention has a high narrow ratio. In addition, the component (A) has no hydrophilic group at the end of the molecule (end-capped type) and has a highly polar carbonyl group in the molecule.
From these, it is speculated that the component (A) has a weak molecular orientation in an aqueous solution system and that micelles are unstable nonionic surfactants, and are considered to contribute to the improvement of rinsing properties. .

(A) A component can be used 1 type or in mixture of 2 or more types.
(A) Content of a component is preferably 10-50 mass% in the liquid cleaning composition for garments, More preferably, it is 20-40 mass%. When the content of the component (A) is within this range, good rinsing properties can be obtained. Moreover, the detergency with respect to sebum dirt, mud dirt, etc. and the liquid stability (especially stability with time at low temperature) of the liquid detergent composition for clothing are improved. Furthermore, rinsing properties are further improved by being below the upper limit of the range.

(B) component In this invention, (B) component is a semipolar surfactant and / or an amphoteric surfactant.
Examples of the semipolar surfactant include amine oxide surfactants represented by the following general formula (II).

[Wherein, R ³ has 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, and more preferably a linear or branched alkyl group or alkenyl group having 10 to 14 carbon atoms; R ⁴ , R ⁵ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group. R ⁶ is an alkylene group having 1 to 4 carbon atoms; X is a group selected from —CO—NH—, —NHCO—, —COO—, —OCO— and —O—; n ′ is 0 or 1 It is. ]

  Specific examples include alkyl dimethylamine oxide and alkylamidopropyl dimethylamine oxide. Among these, alkyldimethylamine oxide is preferable from the viewpoint of improving detergency against mud dirt and the like, and n-dodecyldimethylamine oxide is particularly preferable. For example, n-dodecyldimethylamine oxide is commercially available from Lion Akzo Co., Ltd.

Examples of amphoteric surfactants include N-alkyl or alkenyl amino acids or salts thereof, and betaines.
In the N-alkyl or alkenyl amino acid, an alkyl group or an alkenyl group is bonded to a nitrogen atom, and one or two “—R—COOH” (wherein R represents a divalent hydrocarbon group, preferably an alkylene A group having a structure in which a group represented by 1 to 2 carbon atoms is bonded. In a compound in which one “—R—COOH” is bonded, a hydrogen atom is further bonded to the nitrogen atom.
One “—R—COOH” is called a mono form, and two are called a di form. In the component (C), any of these mono and di forms can be used.
In the N-alkyl or alkenyl amino acid, the alkyl group or alkenyl group preferably has 10 to 20 carbon atoms, and these may be linear or branched.
The salt is preferably an alkali metal salt such as sodium or potassium, and is preferably a sodium salt.
Preferred examples of the N-alkyl or alkenyl amino acid or salt thereof include alkyl or alkenylaminopropionic acid or a salt thereof, and laurylaminopropionic acid or a sodium salt thereof is more preferred.
Examples of commercially available products include Naurylaminopropionic acid Na (manufactured by Yushi Kogyo Co., Ltd.). This is a 90% by mass: 10% by mass mixture of mono and di.

Examples of betaines include alkyl betaines, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazolinium betaines, phosphobetaines, and the like. Specifically, fatty acid amidopropyl betaine such as lauric acid amidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, lauryldimethylbetaine, etc. And alkyldimethylbetaine.
Examples of commercially available products include lauric acid amidopropyl betaine (trade name “Softazoline LPB”; manufactured by Kawaken Fine Chemical Co., Ltd.), lauryl dimethyl betaine (trade name “Amphithol 24B”; manufactured by Kao Corporation), and the like.
Of these, alkylbetaines, amidebetaines, and sulfobetaines are preferable, and amidepropylbetaine laurate and lauryldimethylbetaine are particularly preferable.

As the component (B), N-alkyl or alkenyl amino acids or salts thereof, alkyl betaines, amide betaines, and sulfobetaines are particularly preferable.
(B) A component can be used 1 type or in mixture of 2 or more types.
The content of the component (B) is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass in the liquid detergent composition for clothing, from the viewpoint of improving the detergency against mud dirt and the like. %. Moreover, the cleaning power with respect to sebum dirt improves also in this range. Furthermore, if it is below the upper limit of the range, the rinsing time is shortened and the rinsing properties are improved.

In the liquid cleaning composition for clothing of the present invention, the component (A) and the component (B) are used in combination as main cleaning components. Since the component (A) and the component (B) have little residue (adsorption amount) on the object to be washed, the concentration of the component (A) and the component (B) in the rinsing liquid at the rinsing stage in the washing operation is Expected to be lower.
In addition, the component (A) is presumed that micelles formed at a low concentration are unstable from the molecular structure. Therefore, it is considered that the component (A) has low foam stability, and thereby, good rinsing properties are exhibited in a combined system with the component (B).
From the above reasons, it is presumed that the combined use of the component (A) and the component (B) greatly contributes to the improvement of the rinsing properties of the liquid detergent composition for clothing of the present invention.

(C) component In this invention, (C) component is a chelating agent.
Chelating agents are those that mainly capture polyvalent metal ions contained in tap water or dirt, and have the action of capturing polyvalent metal ions when dissolved in water. If there is no particular limitation, for example, inorganic polyphosphate compounds such as tripolyphosphate; phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, ethane-1,1-diphosphonic acid or their salts; Hydroxycarboxylic acids such as acid, malic acid or salts thereof; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid or salts thereof are preferably used.
Among them, phosphonic acid chelating agents and carboxylic acid chelating agents are preferable as organic chelating agents, ethylenediaminetetraacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, citric acid or salts thereof are more preferable, and 1-hydroxyethane. -1,1-diphosphonic acid and / or its salts are particularly preferred.
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.
As component (C), 1-hydroxyethane-1,1-diphosphonic acid is most preferable.
(C) component can be used 1 type or in mixture of 2 or more types.
The content of the component (C) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, in the liquid detergent composition for clothing. By being more than the lower limit of this range, the cleaning power especially against mud dirt is improved. On the other hand, component (C) can be blended more stably by being below the upper limit.

Other optional components In addition to the components (A) to (C), other optional components can be blended in the liquid cleaning composition for clothing of the present invention as necessary.
Specific examples include one or more selected from benzenesulfonic acid, alkylbenzenesulfonic acid, benzenesulfonate, and alkylbenzenesulfonate.
In the alkylbenzene sulfonic acid and the alkylbenzene sulfonate, the number of alkyl groups (substituents) is preferably 1 to 3, more preferably 1 to 2. The alkyl group preferably has 1 to 3 carbon atoms, more preferably a methyl group or an isopropyl group, and still more preferably a methyl group.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt. Can be mentioned. Of these, sodium salts, monoethalamine salts, and diethanolamine salts are preferred.
Among them, preferable examples include compounds represented by the following general formula (III).

［式中、Ｘ”、Ｙ”、Ｚ”は、それぞれ独立して水素原子、Ｃ_ｎ”Ｈ_{２ｎ”＋１}（ｎ”は１〜３の整数である。）または（ＣＨ_３）_２ＣＨであり；Ｍは、水素原子、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。］

[Wherein, X ″, Y ″ and Z ″ each independently represent a hydrogen atom, C _{n ″} H _{2n ″ +1} (n ″ is an integer of 1 to 3) or (CH ₃ ) ₂ CH. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, NH ₄ ⁺ or an alkanolamine. ]

In the general formula (III), X ″, Y ″, and Z ″ each independently represent a hydrogen atom, C _{n ″} H _{2n ″ +1} (n ″ is an integer of 1 to 3) or (CH ₃ ). ₂ CH, preferably CH ₃ , (CH ₃ ) ₂ CH, and more preferably CH ₃ .
M represents a hydrogen atom; 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, monoethalamine 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, and p-toluenesulfonic acid, cumenesulfonic acid, and m-xylenesulfonic acid are more preferable.
These can be used alone or in combination.
These contents are preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and particularly preferably 2 to 6% by mass in the liquid detergent composition for clothing. If it exists in this range, mud will disperse | distribute more finely and the cleaning power with respect to mud dirt will improve. Moreover, the production | generation suppression effect of the film | membrane formed when this liquid detergent composition for clothes gelatinizes on the surface of the liquid detergent composition for clothes is also improved.

Moreover, the liquid detergent composition for clothes which concerns on this invention may contain a hydrotrope agent and an alkaline agent.
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 weight average molecular weight of 400 to 5000 (preferably about 1000) are preferable.
Examples of the alkali agent include alkanolamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like, and monoethanolamine is preferable. One or more alkanolamines may be used in combination.
The content of these hydrotrope agent and alkali agent is preferably 1 to 15% by mass in the liquid cleaning composition for clothing, respectively.

Moreover, the liquid cleaning composition for clothes which concerns on this invention may contain 0-15 mass% of C8-C22 fatty acid and / or its salt as a foam suppressor.
The fatty acid preferably has 8 to 22 carbon atoms, for example, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid Any of these may be used. Of these, palmitic acid is most preferred.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; ammonium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt.

Furthermore, the liquid detergent composition for clothing according to the present invention comprises 0 to 2% by mass of a recontamination inhibitor such as polyvinylpyrrolidone or carboxymethylcellulose for the purpose of preventing recontamination; a lipase or cellulase for the purpose of improving detergency. 0 to 1% by mass of enzymes such as amylase and protease; 0 to 3% by mass of calcium salts such as boric acid, borax, formic acid or salts thereof, calcium chloride and calcium sulfate for the purpose of enzyme stabilization; 0 to 5% by weight of silicone such as dimethyl silicone, polyether-modified silicone, amino-modified silicone; 0 to 1% of fluorescent whitening agent such as distyrylbiphenyl type for the purpose of improving whiteness of white clothing %; 0.0001 to 0.001% by mass of a pigment such as an acid dye for the purpose of coloring a liquid detergent composition; For the purpose of, for example, 0.0001 to 0.5% by mass of an antioxidant such as dibutylhydroxytoluene; 0 to 0.05% by mass of an antibacterial agent such as caisson CG (trade name) for the purpose of antiseptic properties can do.
Examples of the fragrance for aroma include a fragrance composition described in JP-A-2002-146399, a fragrance composition containing a solvent and a stabilizer, and the like in the liquid detergent composition for clothing of the present invention. 0.01-1 mass% can be mix | blended with this.

Furthermore, inorganic acids and inorganic bases such as sulfuric acid, sodium hydroxide, and potassium hydroxide can be blended as a pH adjuster.
The pH of the liquid cleaning composition for clothing of the present invention is preferably pH 4.0 to 10.0, more preferably pH 4.0 to 8.0, from the viewpoint of improving the temporal stability of the liquid cleaning composition for clothing. Adjust to.

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 the liquid detergent composition for clothing of the present invention (the product of the present invention) into the water together with the laundry at the time of washing, and the product of the present invention for mud and sebum soil. Examples thereof include a direct coating method, a method in which the product of the present invention is preliminarily dissolved in water, and clothes are immersed. Also preferred is a method in which the product of the present invention is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution.

According to the present invention, by containing the component (A), the component (B), and the component (C), it is possible to provide a liquid detergent composition for clothing excellent in rinsing properties.
Moreover, the liquid detergent composition for clothes of this invention is excellent also in the detergency with respect to mud dirt.
In addition, since the component (A) used in the present invention is excellent in liquid stability (especially stability at low temperatures), it is a general-purpose surfactant generally used in the preparation of liquid detergent compositions for clothing. The amount of hydrotrope added can be reduced compared to the case where the agent is used. Thereby, the liquid cleaning composition for clothing containing the component (A) is economically advantageous and has a low environmental load.
The component (A) used in the present invention is obtained from a plant-derived raw material. Accordingly, the present invention, such as the reduction of CO _2, it is possible to provide an environment load is low for clothing liquid detergent composition.
Moreover, the liquid detergent composition for clothes of this invention has the mildness with respect to skin, such as this clothing, when the clothes etc. which were washed with this liquid detergent composition for clothing are worn, for example.

  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 1-14, Comparative Example 1)
Liquid detergent compositions for clothing having the compositions shown in Tables 1 to 3 were prepared as follows.
In addition, the unit of the compounding quantity in a table | surface is the mass%, and adjusted the water quantity so that the total amount might be 100 mass%.
First, 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, p-toluenesulfonic acid, cumenesulfonic acid or m-xylenesulfonic acid and monoethanolamine or diethanolamine were added and stirred.
Thereafter, 90% by mass of the total mass of purified water (balance) was added, and the fragrance was added and stirred.
Furthermore, after adding (B) component, (C) component other arbitrary components, and stirring, pH was adjusted and the remaining purified water was added and the liquid cleaning composition for garments was prepared.
The pH was adjusted by appropriately adding a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH of the liquid detergent composition for clothes at 7.0 was 7.0.

  About the obtained liquid cleaning composition for clothing, it evaluated by the method and evaluation criteria shown below, and the result was written together in Tables 1-3.

≪Description of ingredients shown in the table≫
(A) Component A-1: C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₉ OCH ₃ , narrow ratio 70% by mass, synthetic product.
A-2: C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ , narrow ratio 65% by mass, synthetic product.
_{A-3: C 17 H 33} CO (OC 2 H 4) 15 OCH 3, narrow of 65 wt%, the composition.
A-1, A-2 and A-3 are synthetic products produced according to the synthesis method described in JP-A No. 2000-144179 (A-1 is described in JP-A No. 2000-144179). (A-2 corresponds to the sample D described in the publication, and A-3 corresponds to the sample F described in the publication).

A-4 (comparative product): C _n H _{2n + 1} O (EO) ₁₅ H (a mixture of a compound in which n is 12 and a compound in which n is 14 (mixing ratio is 71:29 by mass ratio)), Synthetic product.
(Synthesis method of A-4)
224.4 g of C _12/14 alcohol (branch rate ^{* 10} mass%) manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. 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% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining A-4. It was.
* 1 Branching rate: The branching rate refers to the ratio of the number of moles of alcohol having a branched alkyl group to the number of moles of alcohol in the raw material alcohol.

(B) Component B-1: Naurylaminopropionic acid, manufactured by Otsuka Kogyo Co., Ltd.
B-2: Amidopropyl betaine laurate, manufactured by Kawaken Fine Chemicals Co., Ltd., trade name “SOFTAZOLINE LPB”.
B-3: Lauryl dimethyl betaine, manufactured by Kao Corporation, trade name “Amphitor 24B”.

(C) Component C-1: 1-hydroxyethane-1,1-diphosphonic acid, manufactured by ALBRITE & WILSON, trade name “BRIQUEST ADPA-A”.
C-2: Trisodium citrate dihydrate, manufactured by Miles (USA).
C-3: Edetic acid (ethylenediaminetetraacetic acid) tetrasodium tetrahydrate, manufactured by Akzo Nobel.

Optional component p-toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd.
Cumene sulfonic acid: manufactured by Teika Co., Ltd., trade name “Taikatox 500”.
m-Xylenesulfonic acid: Mitsubishi Gas Chemical Co., Ltd., trade name “SXA-60”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Diethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Palmitic acid: manufactured by Nippon Oil & Fats Co., Ltd.
Ethanol: Product name “95 vol% synthetic ethanol” manufactured by NEDO.
Polyethylene glycol: Product name “PEG # 1000” (weight average molecular weight 1000) manufactured by NOF Corporation.
Fragrance compositions A and C: Fragrance compositions described in Tables 11 to 18 of JP-A-2002-146399.
Dye A: Product name “Green 201”, manufactured by Sakai Kasei Co., Ltd.
Dye B: Product name “Yellow 203” manufactured by Sakai Kasei Co., Ltd.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.

≪Rinse evaluation≫
0.6 g of each liquid detergent composition for clothing was dissolved in 900 ml of water to obtain a sample solution, and the foaming property at 25 ° C. was measured. The measurement was performed using a Ross-Miles test apparatus in accordance with the measurement method of JIS K3362.
The foaming property was calculated by the following formula and evaluated based on the following criteria.
Bubble breakability (%) = (bubble height 5 minutes after completion of dropping) / (bubble height immediately after completion of dropping) × 100
Evaluation standard of bubble breakage ◎: Less than 50%.
A: 50% or more and less than 70%
Δ: 70% or more and less than 90%.
X: 90% or more.

≪Evaluation of cleaning power against mud dirt≫
15 g of horticultural black soil (manufactured by Kyotochiya) was weighed, put into 500 g of tap water, and dispersed with a homogenizer (manufactured by KINEMATICA Swiss, trade name: Polytron Type PT 10/35) at 80 rpm for about 5 minutes.
In the obtained mud dispersion, 15 cotton knitted fabrics cut to 10 cm × 25 cm (dyed test material, cotton knit unsilled by Tanigami Shoten Co., Ltd.) (hereinafter referred to as “raw fabric”) are immersed. The cloth was thoroughly rubbed by hand, and the mud dispersion was uniformly contained throughout the cloth. Then, 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 prepared above was divided into 5 sheets (2 × 2 cm ² each), and this was used as an evaluation cloth (dirt 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 is applied to 5 sheets of soiled cloth, left for 5 minutes, and then 5 sheets of soiled cloth are directly put into a Terg-O-Tometer (cleaning tester). After putting 0.9 L of tap water (hardness 3DH) at 120 rpm and stirring for 10 minutes, it was transferred to a two-tank washing machine (manufactured by 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.

The detergency against mud stains was measured using a colorimetric color difference meter (trade name: SE2000, manufactured by Nippon Denshoku Co., Ltd.), using the following formula: It was calculated as a washing rate.
For the evaluation, an average value of five evaluation cloths for each liquid cleaning composition for clothing was used.

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

Evaluation of the detergency against mud soil was evaluated based on the following criteria.
A: The cleaning rate exceeds 25%.
B: The washing rate is 20 to 25%.
C: The cleaning rate is 15 to less than 20%.
D: The cleaning rate is less than 15%.

As is clear from the results shown in Tables 1 to 3, it was confirmed that all of the examples according to the present invention were excellent in rinsing properties.
In addition, it was confirmed that the examples were also excellent in cleaning power against mud dirt.
On the other hand, the comparative example had poor rinsability.

Claims (2)

A liquid detergent composition for clothing comprising the following component (A), component (B) and component (C).
(A) The following general formula (I)

[Wherein R ¹ is a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; n is an average addition of ethylene oxide] The number of moles is shown and is 5-30. ]
An ethylene oxide adduct represented by the formula (1), wherein the ethylene oxide adduct has a narrow ratio of 55% by mass or more, indicating the proportion of distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide added,
(B) a semipolar surfactant and / or an amphoteric surfactant,
(C) Chelating agent. The liquid cleaning composition for clothing according to claim 1, wherein the component (C) contains 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof.