JP2007161805A - Liquid detergent composition for clothes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothes which has good detergency for dirt and in which a film formed by gelation of the liquid detergent composition cannot be easily produced on the surface of the liquid detergent composition. <P>SOLUTION: The liquid detergent composition for clothes comprises (A) a non-soap anionic surfactant, (B) an amphoteric surfactant and/or a polyoxyethylene derivative of a primary amine, (C) 1-hydroxyethane-1,1-diphosphonic acid and/or a salt thereof, and (D) one or more selected from the group consisting of benzenesulfonic acid, an alkylbenzenesulfonic acid, a benzenesulfonate, and an alkylbenzenesulfonate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

In recent years, liquid detergent compositions for clothing have been used more frequently than powder detergent compositions because they do not cause powdering and are easily soluble in water filled in the washing machine tub. .
In the future, it is expected that the rate of increase in the use of the liquid detergent composition will rapidly increase with the spread of the fully automatic washing machine having an automatic charging system for the washing machine in the washing machine tank.

On the other hand, a liquid detergent composition for clothing is conventionally required to have a high detergency.
On the other hand, for example, Patent Document 1 discloses a liquid detergent composition in which a metal ion scavenger is blended in order to remove metal ions in water that serve as a washing inhibition factor.
Patent Document 2 discloses a liquid laundry detergent composition in which components such as a specific zwitterionic polymer, a polyamine dispersant, and a surfactant are combined to improve detergency against mud dirt, which is stubborn dirt. Is disclosed.

In addition, in a liquid detergent composition for clothing, the liquid detergent composition gels on the surface of the liquid detergent composition in a container with an open lid, an automatic loading port of a fully automatic washing machine, or the like. There exists a problem that the film | membrane formed by this is easy to produce | generate. This is particularly noticeable in so-called concentrated liquid cleaning compositions for clothing having a high surfactant content.
For the above problem, for example, a nonionic surfactant, a liquid detergent composition for clothing containing a compound having potassium in the molecule (see Patent Document 3), and two types of nonions with different average added mole numbers of ethylene oxide A liquid detergent composition (see Patent Document 4) containing a surfactant and polyethylene glycol has been proposed.
Japanese Patent Laid-Open No. 2004-220961 Special table 2003-524065 gazette JP 2000-282088 A Japanese Patent Laid-Open No. 2001-3100

However, in the compositions described in Patent Documents 1 and 2, the cleaning effect on mud soil is not satisfactory, and further improvement is desired.
Moreover, in the composition of patent document 3, 4, the production | generation of the membrane | film | coat formed when this liquid detergent composition gelatinizes on the surface of a liquid detergent composition is not fully suppressed. However, further improvement is desired.
Furthermore, recently, with the widespread use of fully automatic washing machines having a laundry reservation timer, it has been strongly demanded to suppress the formation of a film formed by the gelation.

  Therefore, in the present invention, it has a good detergency against mud stains, and on the surface of the liquid detergent composition, a film formed by the gelation of the liquid detergent composition is hardly generated. It is an object of the present invention to provide a liquid cleaning composition for clothing.

In order to solve the above-mentioned problems, the present invention proposes a liquid detergent composition for clothing comprising the following components (A), (B), (C) and (D): To do.
(A) a non-soap anionic surfactant,
(B) an amphoteric surfactant and / or a compound represented by the following general formula (I):
(C) 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof,
(D) One or more types selected from benzenesulfonic acid, alkylbenzenesulfonic acid, benzenesulfonate, and alkylbenzenesulfonate.

［式中、Ｒ^１３は炭素数８〜２０の直鎖もしくは分岐鎖状のアルキル基またはアルケニル基、長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８以上である。］

[Wherein, 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; EO is an ethylene oxide group; A and b each represent an integer of 0 or more, and a + b is 8 or more. ]

Moreover, it is preferable that the liquid cleaning composition for clothes of this invention contains (E) nonionic surfactant further.
Moreover, the liquid detergent composition for clothes of this invention is 35 / 65-90 / 10 in the mixing ratio of said (A) non-soap anionic surfactant and said (E) nonionic surfactant by mass ratio. It is preferable that

  According to the present invention, clothing having a good detergency against mud stains and hardly forming a film formed by gelation of the liquid detergent composition on the surface of the liquid detergent composition. A liquid detergent composition can be provided.

The liquid detergent composition for clothing of the present invention comprises (A) a non-soap anionic surfactant, (B) an amphoteric surfactant and / or a compound represented by the general formula (I), and (C) 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof and (D) one or more selected from benzenesulfonic acid, alkylbenzenesulfonic acid, benzenesulfonate and alkylbenzenesulfonate .
Preferably, the liquid detergent composition for clothes of the present invention further contains (E) a nonionic surfactant.
Hereinafter, each component will be described in detail.

(A) component (A) A component is a non-soap anionic surfactant. The non-soap system improves the cleaning power against mud dirt. Moreover, the production | generation suppression effect of the membrane | film | coat formed when this liquid cleaning composition for garments gelatinizes on the surface of the liquid cleaning composition for garments improves.
Among these, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, alkane sulfonate, linear alkylbenzene sulfonate, and polyoxyethylene alkyl ether sulfate are preferable.
As an alpha olefin sulfonate, carbon number of an alkyl group becomes like this. Preferably it is 14-18, More preferably, it is 14.
As alpha-sulfo fatty acid methyl ester salt, carbon number of a fatty acid becomes like this. Preferably it is 8-18, More preferably, it is 12-16.
The alkane sulfonate is preferably a secondary alkane sulfonate. Carbon number of an alkyl group becomes like this. Preferably it is 10-21, More preferably, it is 10-14.
As linear alkylbenzene sulfonate, carbon number of an alkyl group becomes like this. Preferably it is 8-16, More preferably, it is 10-14.
As polyoxyethylene alkyl ether sulfate, carbon number of an alkyl group becomes like this. Preferably it is 10-20, More preferably, it is 10-16. Moreover, the average addition mole number of ethylene oxide becomes like this. Preferably it is 0.5-8.
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, sodium salts are preferred.

(A) A component can be used 1 type or in mixture of 2 or more types.
The content of the component (A) is preferably 11 to 60% by mass, more preferably 15 to 45% by mass, and further preferably 15 to 40% by mass in the liquid detergent composition for clothing. If it is in this range, the cleaning power against mud dirt is improved. 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. Furthermore, the foaming is improved, a suitable amount of foam is obtained, and a visual effect such as a cleaning feeling that the cleaning power is felt high is obtained.

Component (B) The component (B) is an amphoteric surfactant and / or a compound represented by the general formula (I).
Examples of amphoteric surfactants include N-alkyl or alkenyl amino acids or salts thereof, betaines, and the like.
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 group, particularly preferably having 1 to 2 carbon atoms.). 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 (B), 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 a sodium salt or a potassium salt, and more preferably a sodium salt.
As the N-alkyl or alkenyl amino acid or a salt thereof, alkyl or alkenylaminopropionic acid or a salt thereof is preferable, and laurylaminopropionic acid or a sodium salt thereof is more preferable.
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. Of these, alkylbetaines, amide betaines, and sulfobetaines are preferable, and amidepropyl betaine laurate and lauryldimethylbetaine are particularly preferable.
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.

In the compound represented by the general formula (I), R ¹³ is 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, a benzyl group. One of them.
The number of carbon atoms of the alkyl group is more preferably 10-18. The number of carbon atoms 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 preferably 10 to 18 carbon atoms. The number of hydroxy groups is preferably 1 to 3, and more preferably 1.
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 number of ethylene oxide group, and each independently represents an integer of 0 or more.
Moreover, a + b is 8 or more, Preferably it is 8-60. When a + b is 8 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 : palm oil-derived alkyl group (8 to 18 carbon atoms), a + b = 15) manufactured by Lion Akzo Co., Ltd .; Product name “ETHOMEEN SA2Y-103” (R ¹³ : Alkyl group carbon number 16-18, a + b = 50) manufactured by Akzo Co., Ltd .; Product name “ETHOMEEN” manufactured by Lion Akzo Co., Ltd. SAJ-103 "(R < ¹³ >: Alkyl group derived from cured beef tallow (carbon number 12-20), a + b = 10) and the like.

The component (B) is preferably an N-alkyl or alkenyl amino acid or a salt thereof, alkylbetaine, amidebetaine, sulfobetaine, or a compound represented by the above general formula (I), preferably sodium laurylaminopropionate, lauric acid More preferred are amidopropyl betaine, lauryl dimethyl betaine, and trade name “ETHOMEEN (ESOMINE) SA2Y-103”.
(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 and more preferably 0.5 to 5% by mass in the liquid cleaning composition for clothing. By being 0.5 mass% or more, the cleaning power against mud dirt is improved. On the other hand, when it is 10% by mass or less, the rinsing time can be further shortened.

Component (C) The component (C) is 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof.
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 the component (C), 1-hydroxyethane-1,1-diphosphonic acid is particularly 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, from the viewpoint of detergency against mud dirt. is there. By being 0.1 mass% or more, the cleaning power against mud dirt is improved. On the other hand, by being 10 mass% or less, (C) component can be mix | blended more stably.

(D) Component (D) A component is 1 or more types chosen from a benzenesulfonic acid, an alkylbenzenesulfonic acid, a benzenesulfonate, and an alkylbenzenesulfonate.
In the alkyl benzene sulfonic acid and the alkyl benzene sulfonate, the number of alkyl groups 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.

  Especially, the compound represented by the following general formula (II) is mentioned as a suitable thing of (D) component.

［式中、Ｘ、Ｙ、Ｚは、それぞれ独立してＨ、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、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。］

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

In the general formula (II), X, Y, and Z are each independently H, C _{n ″} H _{2n ″ +1} (where n ″ is an integer of 1 to 3) or (CH ₃ ) ₂ CH And preferably CH ₃ , (CH ₃ ) ₂ CH, and more preferably CH ₃ .
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, 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.

(D) component can be used 1 type or in mixture of 2 or more types.
The content of the component (D) is 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. When the component (D) is in this range, the mud is more finely dispersed and the detergency against mud dirt is improved. 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.

(E) component It is preferable that the liquid cleaning composition for clothes of this invention contains (E) nonionic surfactant further. (E) By containing a component, the cleaning power with respect to mud dirt improves.
Nonionic surfactants include, for example, polyoxyethylene alkyl ethers having an alkyl group having 10 to 20 carbon atoms and an average added mole number of ethylene oxide of 3 to 26, an alkyl group having 8 to 18 carbon atoms, and a glucose unit. An alkyl polyglucoside having an average addition mole number of 1 to 10, an alkyl group having 8 to 18 carbon atoms, an alkyl glyceryl ether having an average addition mole number of 1 to 3 glycerol units, a fatty acid diethanolamide having 10 to 20 carbon atoms, Examples thereof include methoxypolyoxyethylene alkanoates having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 1 to 30. Among these, polyoxyethylene alkyl ethers having an alkyl group with 10 to 20 carbon atoms and an average added mole number of ethylene oxide of 3 to 26 are preferable.

The carbon number of the alkyl group in the polyoxyethylene alkyl ether is preferably 11 or less, more preferably 12 or more, and the upper limit is preferably 18 or less, more preferably from the viewpoint of detergency against mud dirt. 15 or less.
In addition, the average added mole number of ethylene oxide is preferably 5 or more, more preferably 8 or more, and the upper limit value is preferably 20 in 1 mole of the polyoxyethylene alkyl ether from the viewpoint of mud dirt detergency. Below, more preferably 18 or less.
The polyoxyethylene alkyl ether can be obtained by subjecting a higher alcohol to addition reaction of ethylene oxide by a conventional method using an alkali catalyst or the like, or a commercially available product can be used. As higher alcohols, linear primary alcohols, branched primary alcohols, linear secondary alcohols and the like are preferably used.

  The content of the component (E) is preferably 0 to 25% by mass in the liquid cleaning composition for clothing. When the upper limit of the range is 25% by mass or less, the liquid stability (the surface of the liquid detergent composition for clothing does not cause gelation of the liquid detergent composition for clothing, and the stable state is achieved. Characteristics that can be maintained).

  In the liquid detergent composition for clothing of the present invention, the mixing ratio of the (A) non-soap anionic surfactant and the (E) nonionic surfactant is 35/65 to 90/10 in mass ratio. It is preferable that it is, and it is more preferable that it is 55 / 45-85 / 15. When the mixing ratio of the component (A) in this range is 35 or more, the liquid stability is improved. On the other hand, when the mixing ratio of the component (A) is 90 or less, the cleaning power against mud dirt is improved.

Other optional components 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 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 detergent composition for clothes may contain 0-15 mass% of C8-C22 fatty acid and / or its salt as a foam suppressant.
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 salts or alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt.

  Further, for the purpose of preventing recontamination, 0 to 2% by mass of a recontamination inhibitor such as polyvinylpyrrolidone and carboxymethylcellulose; 0 to 1% by mass of an enzyme such as lipase, cellulase, amylase and protease for the purpose of improving detergency. ; 0-3 mass% of calcium salts such as boric acid, borax, formic acid or salts thereof, calcium chloride, calcium sulfate for the purpose of enzyme stabilization; dimethyl silicone, polyether-modified silicone, amino for the purpose of improving the texture; 0 to 5% by mass of silicone such as modified silicone; 0 to 1% by mass of fluorescent agent such as distyrylbiphenyl type for the purpose of improving whiteness of white clothing; acidic dye for the purpose of coloring liquid detergent composition 0.0001 to 0.001% by mass of a pigment such as dibutylhydroxytoluene for the purpose of stabilizing aroma 0.0001 wt% of an antioxidant; the purpose of antiseptic, antibacterial agents such as caissons CG (trade name) may be blended with 0 to 0.05% by weight, and the like.

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 detergent composition for clothing of the present invention is preferably 7.0 to 11.0 from the viewpoint of cleaning power against mud stains and maintenance of cleaning power after storage, and 9.0 to 10.5. It is more preferable that

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.

As described above, according to the present invention, a film formed by gelation of the liquid detergent composition is formed on the surface of the liquid detergent composition, which has good detergency against mud dirt. It is possible to provide a liquid detergent composition for clothing that is difficult to wear.
The liquid detergent composition for clothes of the present invention is suitable for use in a fully automatic washing machine having an automatic charging system of a washing agent into a washing machine tub, a fully automatic washing machine having a laundry reservation timer, and the like. Is.

  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 1-6, Comparative Examples 1-5)
Liquid detergent compositions for clothing having the compositions shown in Tables 1 and 2 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) (both the components (A) and (E) in Examples 3 to 6) 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 (D) and monoethanolamine (both monoethanolamine and diethanolamine in Examples 4, 6 and 5) were added and stirred.
Thereafter, 90% 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 clothing was obtained.
The pH was adjusted by adding a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. of the prepared liquid detergent composition for clothing would be the values shown in Tables 1 and 2. .

  The obtained liquid cleaning composition for clothing was evaluated by the following methods and evaluation criteria, and the results are shown in Tables 1 and 2.

≪Description of ingredients shown in the table≫
(A) Component A-1: α-olefin sulfonic acid Na, manufactured by Lion Corporation (carbon number 14).
A-2: Sodium salt of α-sulfohexadecyl fatty acid methyl ester, manufactured by Lion Corporation.
A-3: Sodium salt of α-sulfo fatty acid methyl ester, manufactured by Lion Corporation (carbon number of fatty acid: 14 to 16).
A-4: Secondary alkane sulfonic acid Na, manufactured by Clariant Japan Co., Ltd. (carbon number 14-18).
A-5: Linear alkylbenzene sulfonate Na, manufactured by Lion Corporation (alkyl group having 10 to 14 carbon atoms).
A-6: Polyoxyethylene alkyl ether sulfate Na, manufactured by Lion Corporation (alkyl group having 12 to 14 carbon atoms, average addition mole number of ethylene oxide of 3).

(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 “
Softazolin LPB ".
B-3: Lauryldimethylbetaine, manufactured by Kao Corporation, trade name “Amphitor 24B”.
B-4: Compound represented by the above general formula (I), manufactured by Lion Akzo Co., Ltd., trade name “ETHOMEEN SA2Y-103” (R ¹³ : alkyl group having 16 to 18 carbon atoms, a + b = 50).

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

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

(E) Component E-1: polyoxyethylene alkyl ether (mixture of carbon number of alkyl group: 12/13 (branch ratio ^{* 1} 50%, mass ratio 55/45), average number of added moles of ethylene oxide: 15), A synthetic product manufactured by the following method.
(Synthesis method of E-1)
Product name “Safol 23 alcohol” (branch rate ^{* 1} 50%) 224.4 g, manufactured by Sasol
2.0 g of 30% NaOH aqueous solution was collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid 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 then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, and E-1 was obtained.
* 1 Branching ratio: The ratio of the number of carbon atoms constituting the branched chain to the total number of carbon atoms.

E-2: Polyoxyethylene alkyl ether (a mixture of alkyl groups having a carbon number of 12/14 (mass ratio 71/29), average number of moles of ethylene oxide added: 15), a synthetic product produced by the following method.
(Method for synthesizing E-2)
It was synthesized in the same manner as E-1 using 224.4 g of C12-14 alcohol manufactured by P & G.

E-3: 9 mole average addition mole number of ethylene oxide of branched chain-containing secondary alcohol, Nippon Shokubai Co., Ltd., trade name “Softanol 90”.

Optional component alkylamidopropyldimethylamine-1 (mixture of alkyl groups having 8/10 carbon atoms (mass ratio 6/4)), synthetic product.
Alkylamidopropyldimethylamine-2 (carbon number of alkyl group: 18), synthetic product.
The above two types of alkylamidopropyldimethylamine were synthesized by the method described in JP-A-2005-187502.

Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd.
Diethanolamine, manufactured by Nippon Shokubai Co., Ltd.
Palmitic acid, manufactured by NOF Corporation.
Ethanol (95 vol% synthetic ethanol), manufactured by NEDO.
Polyethylene glycol, manufactured by NOF Corporation, trade name “PEG # 1000” (weight average molecular weight 1000).
Propylene glycol, manufactured by Showa Denko K.K.
Fragrance composition: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
Dye A: Green 201, manufactured by Sakai Kasei Co., Ltd.
Dye B: Yellow 201, manufactured by Sakai Kasei Co., Ltd.

≪Evaluation of cleaning power against mud dirt≫
10 g of horticultural black soil (manufactured by Kyotochiya) was weighed and poured into 500 g of tap water, and dispersed with a homogenizer (manufactured by 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 made by Tanigami Shoten Co., Ltd., cotton knit unsilled) are immersed, and the cloth is thoroughly rubbed by hand. The mud dispersion was uniformly contained throughout. 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: The washing rate was evaluated.
The evaluation used the average value in five evaluation cloths, respectively.

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 dirt was performed according to the following criteria.
A: The cleaning rate exceeds 30%.
B: The washing rate is 25 to 30%.
C: The cleaning rate is 20 to less than 25%.
D: The cleaning rate is less than 20%.

≪Evaluation of film formation suppression≫
Weigh out 5g of the liquid detergent composition for clothing shown in Tables 1 and 2 in a petri dish with a diameter of 5 cm and leave it in a constant temperature room at 25 ° C and 45% humidity for 48 hours with the top of the petri dish open. The state of the surface of the liquid detergent composition was visually observed and evaluated based on the following criteria.
A: Almost no change.
○: Slight film formation is observed, but there is no practical problem.
Δ: A film is clearly observed on the surface.
X: A film is formed on the surface and loses fluidity.

As is apparent from the results shown in Tables 1 and 2, in the examples according to the present invention, the liquid detergent has a good detergency against mud dirt and the surface of the liquid detergent composition. It was confirmed that a film formed by the gelation of the composition was difficult to generate.

Claims (3)

A liquid detergent composition for clothing comprising the following component (A), component (B), component (C) and component (D).
(A) a non-soap anionic surfactant,
(B) an amphoteric surfactant and / or a compound represented by the following general formula (I):
(C) 1-hydroxyethane-1,1-diphosphonic acid and / or a salt thereof,
(D) One or more types selected from benzenesulfonic acid, alkylbenzenesulfonic acid, benzenesulfonate, and alkylbenzenesulfonate.

[Wherein, 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; EO is an ethylene oxide group; A and b each represent an integer of 0 or more, and a + b is 8 or more. ]   The liquid detergent composition for clothing according to claim 1, further comprising (E) a nonionic surfactant. The liquid detergent composition for clothes according to claim 2, wherein a mixing ratio of the (A) non-soap anionic surfactant and the (E) nonionic surfactant is 35/65 to 90/10 in mass ratio. object.