WO2007032435A1

WO2007032435A1 - Liquid detergent composition for clothes

Info

Publication number: WO2007032435A1
Application number: PCT/JP2006/318260
Authority: WO
Inventors: Izumi Onuki; Toshihiko Tachikawa; Megumu Ono; Takahiro Okamoto; Tetsuya Katagi
Original assignee: Lion Corporation
Priority date: 2005-09-16
Filing date: 2006-09-14
Publication date: 2007-03-22
Also published as: JP2007077352A; KR20080045144A; JP4896475B2; KR101240698B1

Abstract

Disclosed is a liquid detergent composition for clothes characterized by containing (A) polyoxyethylene alkyl ether, (B) a compound represented by the general formula (I) below, (C) a semipolar surface active agent, an amphoteric surface active agent or a compound represented by the general formula (II) or (III) below, and (D) 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof. (I) (In the formula (I), X, Y and Z respectively represent a hydrogen atom, CnH2n+1 or (CH3)2CH (wherein n is an integer of 1-3); and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, NH4+ or an alkanolamine.) (II) (III) (In the formulae (II) and (III), R11, R12 and R13 respectively represent an alkyl group, an alkenyl group, a straight chain hydroxyalkyl group, a tolyl group, a phenyl group or a benzyl group; EO represents an ethylene oxide group; a and b respectively represent a number not less than 0 and a + b is not less than 10; and X- represents an anion.)

Description

Specification

Liquid detergent composition for clothing

Technical field

[0001] The present invention relates to a liquid detergent composition for clothing.

This application is filed on September 16, 2005. This application was filed in Japanese Patent Application No. 2005-269972. This claim is based on priority, and its contents are incorporated herein by reference.

Background art

[0002] Conventionally, liquid detergent compositions for clothing have been required to remove mud stains and the like!

As a conventional liquid detergent composition for clothing, for example, Patent Documents 1 and 2 mainly include one or more surfactants selected from amine oxides and amphoteric surfactants for the purpose of cleaning dark stains. An acidic laundry pretreatment composition and an acidic coating detergent composition, which are various components, are disclosed.

Patent Document 3 is intended for cleaning dark stains, and includes one or more surfactants selected from amine oxides and amphoteric surfactants, and organic acids and inorganic acids of pKa2.0 to 6.8. A laundry pre-treatment composition containing the same is disclosed.

Patent Document 4 describes a liquid detergent composition for clothing containing a specific amphoteric surfactant and a nonionic surfactant.

Patent Document 5 describes a pretreatment agent for mud soil comprising an acidic composition containing a compound having a phosphonic acid group! Speak.

[0003] Patent Document 6 discloses a cleaning composition combining a plurality of types of specific surfactants for the purpose of cleaning stubborn dirt! Speak.

Patent Document 7 discloses a liquid detergent composition for clothing that uses a specific non-ionic surfactant for the purpose of satisfying both a texture and a detergency with a squeaky feeling! Speak. In Patent Document 8, a polyoxyethylene alkyl ether having an alkyl group of 10 to 20 carbon atoms and an average added mole number of ethylene oxide of 8 to 26 (hereinafter, this component is referred to as “specific nonionic surfactant”). ), And Z or the alkyl group has carbon atoms Contains polyoxyethylene alkyl ether sulfate with a force of 10 to 20 and an average number of moles of ethylene oxide of 1 to 5, and 1-hydroxyethane 1,1-diphosphonic acid or A composition containing the salt is disclosed.

[0004] Patent Document 1: Japanese Patent Laid-Open No. 2000-109889

Patent Document 2: JP 2000-109893 A

Patent Document 3: Japanese Unexamined Patent Publication No. 2000-109890

Patent Document 4: Japanese Patent Laid-Open No. 08 157870

Patent Document 5: Japanese Patent Laid-Open No. 3-26797

Patent Document 6: Japanese Patent No. 3556806

Patent Document 7: Japanese Patent No. 2813112

Patent Document 8: Japanese Patent Laid-Open No. 2004-210961

Disclosure of the invention

Problems to be solved by the invention

[0005] However, in the compositions described in Patent Documents 1 and 2, the main component is only the amphoteric surfactant, so that the cleaning effect on mud soil is not satisfactory.

In addition, the composition described in Patent Document 3 may not have a sufficient mud dirt cleaning effect.

Even though the compositions described in Patent Documents 4 to 8, the cleaning effect against mud dirt is not satisfactory.

[0006] Accordingly, an object of the present invention is to provide a liquid detergent composition for clothing having good detergency against mud dirt and sebum dirt.

Means for solving the problem

[0007] The present invention, (A) polyoxyethylene alkyl ethers from 2 to 50 mass carbon number of the hydrophobic groups is the average number of added moles force ^ to 26 Echirenokishido at 10~20 ^_0/0; (B) The following general formula (I):

(In the formula, X, Y and Ζ are each independently a hydrogen atom, C 又は or (CH) CH (where η is η 2η + 1 3 2

Μ represents a hydrogen atom, an alkaline metal atom, an alkaline earth metal atom, ΝΗ ^4+, or an anoreno-norenoamine)

(C) a semipolar surfactant, an amphoteric surfactant, and the following general formula (II) or (III): NO (EO) _a H

₊ Ζ —— (Π)

R ¹²ヽ (EO) _b H

_R , ₃ N)

\ (EO) _b H

(In the formula, ¹ and R ¹² are each independently a linear or branched alkyl group or a alkenyl group having 1 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, a benzyl group, R ¹³ represents any one of a linear or branched alkyl group or a alkenyl group having 8 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, or a benzyl group. EO represents an ethylene oxide group, a and b are each 0 or more, a + b is 10 or more, and (in other words, represents an anion). A liquid detergent composition for clothing, comprising: at least one selected compound; and (D) l-hydroxyethane-1,1-diphosphonic acid or a salt thereof.

The liquid detergent composition for clothing can further contain (E) monoethanolamine.

The invention's effect

In the present invention, a liquid detergent composition for clothing having good detergency against mud dirt can be provided. BEST MODE FOR CARRYING OUT THE INVENTION

[0009] Component (A)

(A) component is a polyoxyethylene alkyl ether from 2 to 50 mass ^_0/0 of the average Tsukeka卩mole number 3-26 of Echirenokishido is at 10 to 20 carbon atoms in the hydrophobic groups (alkyl group). The lower limit of the number of carbon atoms in 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 terms of mud soil detergency, the average number of added moles of ethylene oxide is preferably 5 or more, more preferably 8 or more, and the upper limit is preferably 20 or less in 1 mol of component (A). More preferably, it is 18 or less.

Component (A) is a non-ionic surfactant, which can be obtained by addition reaction of ethylene oxide with a higher alcohol by a conventional method using an alkali catalyst or the like, or using a commercially available product. I'll do it.

Examples of higher alcohols include linear primary alcohols, branched primary alcohols, linear secondary alcohols, and the like.

[0010] The component (A) can be used alone or in combination of two or more.

The amount of component (A) is 2 to 50% by mass in the liquid detergent composition for clothing. Preferably rather it is 10 to 50 mass%, more preferably from 15 to 45 weight ^_0/0, particularly preferably in the range of 20 to 40 wt%. (A) Ingredient strength of component If it is within this range, the detergency of mud dirt is improved. In addition, the detergency of the sebum stain and the liquid stability (characteristics that do not cause gelling or the like and can maintain a stable state) are improved.

[0011] Component (B)

Component (B) is a compound represented by general formula (I).

In the formula, X, Υ and Z are each independently H, C H or (CH) CH (where n is 1 to

n 2n + l 3 2

Is an integer of 3, and preferably CH.

Three

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. Of these, sodium, monotamine, and diethanolamine are preferable. [0012] Specific examples of the compound include benzene sulfonic acid, sodium benzene sulfonate, potassium benzene sulfonate, ammonium benzene sulfonate, magnesium benzene sulfonate, calcium benzene sulfonate, 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, magnesium p-toluenesulfonate, calcium p-toluenesulfonate, monoethanolamine p-toluenesulfonate, diethanolamine p-toluenesulfonate, triethanolamine p-toluenesulfonate 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 sulphonate potassium salt, o or m or p-xylene sulphonate ammonium -Um salt, o or m—or p xylene sulfonic acid magnesium salt, o or m or p xylene sulfonic acid calcium salt, o or m—or p xylene sulfonic acid monoethanolamine salt, o or m or p xylene sulfonic acid Ethanolamine salt, o- or m- or p-xylenesulfonic acid triethanolamine salt, cumenesulfonic acid, cumenesulfonic acid sodium salt, cumenesulfonic acid potassium salt, cumenesulfonic acid ammonium salt, cumenesulfonic acid magnesium Salt, cumium sulfonate calcium Salt, cumenesulfonic acid monoethanolamine salt, cumenesulfonic acid diethanolamine salt, cumenesulfonic acid triethanolamine salt, and the like. Of these, P-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid or their monoethanolamine salts are preferred!

[0013] Component (B) may be used alone or in combination of two or more.

The blending amount of 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 a range. When the component (B) is within this range, the detergency of mud dirt is improved. Further, it is preferable because of excellent storage stability.

[0014] Component (C)

Component (C) is a semipolar surfactant, amphoteric surfactant, general formula (Π):

And the general formula (ΠΙ): '(E0) _a H

R 13 N

(E0) _b group is a group force that also has a compound power represented by at least one compound selected.

[0015] Examples of the semipolar surfactant include amine oxide surfactants represented by the following general formula (IV).

[0016] [Chemical 2]

R '-(A—R „--N → 0 (IV)

R

(In the formula, R ¹ is a linear or branched alkyl group or a alkenyl group having 8 to 18, preferably 8 to 16, and more preferably 10 to 14 carbon atoms; ² and R ³ are each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, and A is —CO—NH—, —NHCO— , —COO—, —OCO—, or —O—power is also a group selected, and n ′ is 0 or 1.)

[0018] Specific examples include alkyldimethylamine oxide, alkylamidopropyldimethylaminooxide, and the like, and preferably n-dodecyldimethylamine, where alkyldimethylamine oxide is desirable for the detergency of the detergency. Oxide is preferred. n-dodecyldimethylamine oxide is commercially available, for example, from Lionaxo Corporation.

[0019] Examples of amphoteric surfactants include N-alkyl or alkyl amino acids or salts thereof, and betaines.

An N-alkyl or alkylamino acid has an alkyl group or an alkyl group bonded to a nitrogen atom, and one or two “one R—COOH” (where R is a divalent hydrocarbon). Group, preferably an alkylene group, particularly preferably having 1 to 2 carbon atoms). “One R—a compound with one COOHJ bonded! /, In which a hydrogen atom is bonded to a nitrogen atom.

“—R—COOH” is one thing and two things are di. In the component (C), any of these mono and di forms can be used.

In the N-alkyl or alkaryl amino acid, the alkyl group and the alkenyl group preferably have 10 to 20 carbon atoms, and these may be linear or branched. The salt is preferably a sodium salt that is preferably an alkali metal salt such as sodium or potassium.

Preferable examples include alkyl or alk-laminopropionic acid or a salt thereof, and laurylaminopropionic acid or a sodium salt thereof is more preferable.

Examples of commercially available products include Naurylaminopropionic acid Na (manufactured by Hokata Oil and Fat Co., Ltd.). This is a 90% by weight: 10% by weight mixture of mono and di.

[0020] Examples of betaines include alkyl betaines, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazole betaines, phosphobetaines, and the like. Specific examples include amidepropyl betaine laurate. Examples include fatty acid amidopropyl betaine, 2-alkyl N carboxymethyl N hydroxyethyl imidazolium betaine, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, and alkyldimethylbedine such as lauryldimethylbedine.

Commercially available products include amidopropyl betaine laurate (trade name “Softazoline LPB”; manufactured by Kawaken Fine Chemicals Co., Ltd.), lauryl dimethyl betaine (trade name “Amphitol 24B”; manufactured by Kao Co., Ltd.), and the like. .

Of these, alkylbedine, amidebedine, and sulfobedine are preferred. Amidopropylbetaine and lauryldimethylbetaine are particularly preferred.

Among the amphoteric surfactants, N-alkyl or alkaryl amino acids or salts thereof, alkylbedines, amidebedines, and sulfobedines are particularly preferable.

[0021] In the general formula (R), R ¹¹ and R ¹² are each independently a linear or branched alkyl or alkyl group having 1 to 20 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, Hue It represents either a nyl group or a benzyl group.

The number of carbon atoms of the alkyl group is more preferably 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, for example, 1 to 3, and preferably 1.

Particularly preferably, ^one of R ¹ and R ^{12 is} a combination of a straight-chain or branched alkyl group or alkyl group having 10 to 18 carbon atoms, the other is a acetyl group, a tolyl group or a benzyl group.

[0022] EO represents an ethylene oxide group. a and b each independently represent an average number of moles of addition of the ethylene oxide group, and each independently represents 0 or more.

A + b is 10 mol or more, preferably 10 to 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— is an anion, such as a halogen atom ion such as chlorine ion, bromine ion, iodine ion, or the general formula R ⁵ SO— (where R ⁵ is an alkyl group having 1 to 3 carbon atoms (methyl group, Yetil

Four

Group, propyl group, etc., particularly preferably a methyl group).

[0023] Examples of commercially available products include, for example, trade name “Bisnol UP-10” manufactured by Otsuka Oil Co., Ltd. (1 ^ ¹¹ : alkyl group derived from beef tallow (carbon number 14-20), 1 ^ ¹² : benzyl. group, a + b = 30, X ": CD and Lion 'Akuzo Co., trade name" Ethoquad ^{^{(Esokado) C / 25J (R 1 1}} : alkyl groups derived from coconut oil (carbon number 8-18), R ¹² : methyl group, a + b = 15, X_: Cl_) and the like.

In the general formula (ΠΙ), R ¹³ represents a linear or branched alkyl group or a alkenyl group having 8 to 20 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, a phenol. Group or benzyl group.

The number of carbon atoms of the alkyl group is more preferably 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, for example, 1 to 3, and preferably one.

R ¹³ is particularly preferably a linear or branched alkyl group or a alkenyl group having 10 to 18 carbon atoms.

[0025] EO represents an ethylene oxide group. a and b are the average number of moles of ethylene oxide groups, and each independently represents 0 or more. A + b is 10 mol or more, preferably 10 to 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.

As commercially available products, for example lion 'Akuzo Co., Ltd., trade name "ETHOMEEN (Esomin) CZ25" (R ^13: alkyl group derived from coconut oil (carbon number 8~ 18), a + b = 15), Lion' Product name “ETHOMEEN SA2Y—103” (R ¹³ : Alkyl group derived from hardened beef tallow (carbon number 14-20), a + b = 50), Lion AXO Co., Ltd. Product name “ET HOMEEN SAJ-103” (R ¹³ : Alkyl group derived from hardened beef tallow (carbon number 12 to 20), a + b = 10), and the like.

[0026] The component (C) can be used alone or in combination.

The content of the component (C) 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 of mud soil. . In this range, the detergency against sebum dirt is also improved.

By setting the amount to 10% by mass or less, the rinsing time is shortened, and preparation becomes easier, which is more preferable.

[0027] Component (D)

Component (D) is 1-hydroxyethane-1,1-diphosphonic acid and Z 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.

Of these, 1 hydroxyethane 1, 1-diphosphonic acid is preferred.

Component (D) can be used alone or in combination.

The content of the component (D) is, from the viewpoint of mud dirt cleaning power, in the liquid detergent composition for clothing, Preferably it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%. When the content is 0.1% by mass or more, the detergency of mud soil is improved, and when the content is 10% by mass or less, the component (D) can be blended more stably. It is also preferable in terms of improving the detergency of sebum dirt.

[0028] Component (E)

Component (E) is monoethanolamine.

The blending amount of monoethanolamine is 0.1 to 20% by mass, preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass in the liquid detergent composition for clothing. Within this range, the sebum dirt and mud dirt cleaning power is improved. In addition, it becomes easy to adjust to the preferred pH range described later, and the storage stability is improved. It has excellent stability and can prevent precipitation.

Examples of monoethanolamine are commercially available from Nippon Shokubai Co., Ltd. and Mitsui Chemicals.

[0029] Other optional ingredients

In the liquid detergent composition for clothing of the present invention, a non-ionic surfactant or a cationic surfactant other than the component (A) can be blended.

The non-ionic surfactant has an alkyl group having 8 to 18 carbon atoms, an alkyl polydarcoside having an average number of moles of 1 to 10 glucose glucose, and an alkyl group having 8 to 18 carbon atoms. The glycerin unit has an average number of moles of alkyl glyceryl ether having 1 to 3 carbon atoms, a fatty acid diethanolamide having 10 to 20 carbon atoms, an alkyl group having 10 to 18 carbon atoms, and an average mole number of ethylene oxide. Examples thereof include methoxypolyoxyethylene alkanoates having a number of 1 to 30.

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.

[0030] Examples of the ionic surfactant include alkylbenzene sulfonates having an alkyl group having 8 to 16 carbon atoms, alkyl sulfates having an alkyl group having 10 to 20 carbon atoms, and alkyl having 10 to 20 carbon atoms. Polyoxyethylene having an average number of moles of ethylene oxide of 1 to 10 Ethylene alkyl ether sulfate, a-olefin sulfonate having an alkyl group having 10 to 20 carbon atoms, alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, α- having an alkyl group having 10 to 20 carbon atoms Examples thereof include sulfo fatty acid methyl ester salts, polyoxyethylene alkyl ether carboxylates having an alkyl group having 10 to 20 carbon atoms and an average number of moles of ethylene oxide of 1 to 10.

The amount of these key-on surfactants is preferably in the range of 0 to 10% by mass in the liquid detergent composition for clothing.

[0031] The liquid cleaning 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, triethanolamine and the like, and the alkanolamine may be used alone or in combination of two or more.

The blending amount of these hydrotropes and alkaline agents is preferably 0.1 to L0 mass%, more preferably 1 to 5 mass% in the liquid detergent composition for clothing.

[0032] 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 preferably saturated fatty acids such as cabrylic acid, strong puric acid, lauric acid, myristic acid, palmitic acid and stearic acid, or oleic acid and linoleic acid. Any of unsaturated fatty acids such as linolenic acid may be used. Of these, palmitic acid is most preferred.

Furthermore, for the purpose of preventing recontamination, 0-2% by mass of a recontamination inhibitor such as polybulurpyrrolidone and carboxymethylcellulose, and for the purpose of improving detergency, enzymes such as lipase, cellulase, amylase and protease are used. ~ 1% by mass, for the purpose of enzyme stabilization, 0-3% by mass of calcium salts such as fluoric acid, borax, formic acid or salts thereof, calcium chloride / calcium sulfate, dimethyl silicone, poly Ether-modified Recone, 0-5 weight silicone, such as Amino-modified silicone ^_0/0, the purpose of whiteness improvement in white garments, Jisuchirirubifue - a fluorescent agent Le type such as 0 to 1 mass%, the clothing the liquid detergent composition coloring purposes, a dye such as acid dye 0.0001 to 0.001 mass%, the purpose incense air stabilization, the Sani spoon inhibitor such as dibutylhydroxytoluene 0.5 0001-0. 5 mass ⁰ / _0, for the purpose of antiseptic, antibacterial agents such as caissons CGZICP 0~0. 05 mass ^_0/0, a higher fatty acid or a polyether-modified silicone defoaming purposes, 0-5 weight silicone, such as Amino-modified silicone down % Can be blended. Examples of the fragrance for aroma include a fragrance composition containing a fragrance component, a solvent and a stabilizer described in JP-A-2002-146399, and the liquid detergent composition for clothing of the present invention. In the product, 0.01 to 1 mass% can be blended.

Furthermore, as a pH adjuster, inorganic acids and inorganic bases such as sulfuric acid, sodium hydroxide, potassium hydroxide and the like can be blended. 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 amount of component (E) can be set so that the pH falls within this range.

[0033] 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 the liquid cleaning composition for clothing is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a laundry liquid containing a cation surfactant.

[0034] As described above, in the present invention, a liquid detergent composition for clothing having good detergency against mud dirt can be provided. In addition, the liquid detergent composition for clothing of the present invention exhibits a high detergency even against sebum dirt.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified. [0036] (Examples 1 to 49, Comparative Example 1 to LO)

A liquid detergent composition for clothing having the composition shown in the table was prepared as follows. The unit of the blending amount in the table is mass%, and the amount of water was adjusted so that the total amount would be 100 mass%. Cooled to below 40 ° C. All subsequent steps were performed between room temperature and 40 ° C. Thereafter, the component (B) and the component (E) or diethanolamine were added and stirred. Thereafter, 90% of the mass of purified water (norrance) was added, and a fragrance was added and stirred. Furthermore, after adding (C) component, (D) component, other arbitrary components, and the pigment | dye, 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 adjusted liquid detergent composition for clothing would be the value shown in the table. . And it evaluated by the following method and evaluation criteria, and the result was shown according to the table.

[0037] << Description of ingredients shown in the table >>

(A) component

A—1: C H 2 O (EO) H (n = 12Zl3 mixture (mass ratio 55Z45)), (Synthesis below n 2n + l 15

Synthetic products obtained by the law).

Synthesis method of A-1

Product name 3 & 123 alcohol made by Sasol (branch rate * ¹ 50%) 224.4 g, 30% NaOH aqueous solution 2. Og was collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen.

Next, dehydration was performed at a temperature of 100 ° C and a pressure of 2. OkPa or less for 30 minutes, and then 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 acid / ethylene, after aging at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes, unreacted acid / ethylene was distilled off at a temperature of 180 ° C and a pressure of 6. OkPa or less for 10 minutes. . Next, after cooling the temperature to below 100 ° C, the pH of the 1% aqueous solution of the reactants will be about 7. Similarly, 70% p toluenesulfonic acid was added and neutralized to obtain A-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.

[0038] A-2: C H CH C H O (EO) H (m + n = ll to 13),

n 2n + l m 2m + l 9

Nippon Shokubai Co., Ltd. product name Softanol 90 (average EO (ethylene oxide) 9 mol adduct of secondary alcohol containing branched chain))).

[0039] A—3: CH 2 O (EO) H (n = 12/14 mixture (mass ratio 71/29)), (synthesis method n 2n + l 15

Synthetic products obtained by the law).

Synthesis method of A-3

It was synthesized in the same way as A-1 using 224.4 g of P & Gi ^ C alcohol.

12-14

[0040] A-4: C H O (EO) H (Branched chain content, Dyadol 13, branching rate "50%) (Mitsubishi

13 27 5

Gaku Co., Ltd. C 13 branched chain-containing higher alcohol average E05 mol adduct).

A-5: C H O (EO) H (C chain length, branched type), (BASF, product name: Lutenzol TO

13 27 7

7).

[0041] Component (B)

B-l: p-toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd.

B— 2: Cumenesulfonic acid: Tika Co., Ltd. Trade name “Tikatotus 500”

B—3: m-xylenesulfonic acid: product name “SXA-60” manufactured by Mitsubishi Gas Chemical Company, Inc.

[0042] Component (C)

C-1: Laurylaminopropionic acid Na: Made by Otsuka Oil Industry Co., Ltd.

C—2: Amidopropyl betaine laurate: Kawaken Fine Chemical Co., Ltd. Product name “SOFTA ZOLINE: LPB”

C-3: n-dodecyldimethylamine oxide: manufactured by Lionakuzo Co., Ltd.

C— 4: Lauryldimethylbetaine: product name “Amphitor 24B” manufactured by Kao Corporation

C-5: Esocad CZ25 (trade name, manufactured by Lionakuzo Co., Ltd .; compound represented by general formula (Π), where R ^{11 is} an alkyl group derived from coconut oil (carbon number 8 to 18), R ¹² : Methyl group, a + b = 15,

X "= C1")

C 6: Esomine SA2Y—103 (trade name, manufactured by Lionakuzo Co., Ltd .; compound represented by general formula (III), where R ^{13 is} an alkyl group derived from hardened beef tallow (carbon number 14-20), a + b = 50) C-7: Esomin SAJ - 103 (trade name, Raionakuzo Co., represented by reduction compounds with formula (III), where R ^13: hardened tallow-derived alkyl group (12 to 20 carbon atoms), a + b = 10) C-8: Bisnole UP—10 (trade name, manufactured by Yushi Kogyo Co., Ltd .; compound represented by general formula (Π), where R ¹¹ : alkyl group derived from beef tallow (carbon number 14 -20), R ¹² : benzyl group, a + b = 30, X = Cr)

[0043] Component (D)

D— 1: 1—Hydroxyethane 1, 1—Diphosphonic acid: ALBRITE & WILSON Product name “BRIQUEST ADPA— A”

[0044] Component (E)

E-1: Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.

[0045] Optional ingredients

Diethanolamine: Made by Nippon Shokubai Co., Ltd.

Sodium carbonate: Asahi Glass Co., Ltd. Trade name “Soda Ash”

Sodium hydroxide: Pure chemical reagent

LAS— Na: Lion Corporation

Linear alkyl benzene sulfonate sodium (alkyl group carbon number carbon number 10Z1

2Z 14 mixture)

Palmitic acid: manufactured by Nippon Oil & Fats Co., Ltd.

Ethanol: 95vol% synthetic ethanol NEDO made

Polyethylene glycol: PEG # 1000 (mass average molecular weight 1000) Perfume composition manufactured by Nippon Oil & Fats Co., Ltd .: Perfume compositions A to D described in Tables 11 to 18 described in JP-A-2002-146399

Dye A: Green 201, manufactured by Hagi Kasei Co., Ltd.

Dye B: Yellow 201, manufactured by Hagi Kasei Co., Ltd.

Dye C: Green No. 3, manufactured by Hagi Kasei Co., Ltd.

Dye D: Kirin Yellow—WG—G CONC, manufactured by Chuo Synthetic Chemical Co., Ltd.

Stearyl trimethylammo chloride -Lum: manufactured by Lionakuzo Co., Ltd.

[0046] Storage stability evaluation and criteria The liquid detergent composition for clothing, lOOmL, was stored and sealed in a glass bottle with a screw cap of lOOmL and stored in a thermostatic chamber at 50 ° C for 1 month. Storage stability was evaluated based on the following criteria by visually comparing the liquid detergent composition for clothing after storage and immediately after blending.

A: No change from immediately after compounding.

B: Crystals are precipitated in the blend.

[0047] Mud dirt cleaning power evaluation

Horticultural black soil (kyotochiya) 15g was weighed and put into 500g of tap water, and dispersed for 5 minutes at 8 Orpm with homogenizer 1 (trade name Polytron Type PT 10/35) manufactured by KINEMATICA ^ Iss. I let you. In the resulting mud dispersion, 15 pieces of cotton knitted fabric cut into 10cm x 25cm (dyeing material made by Tanigami Shoten Co., Ltd., unstained cotton knit) is immersed, and the cloth 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 excess mud particles were removed as a model mud soil cloth for evaluation. did.

Each model mud soil cloth adjusted as described above was divided into 5 pieces (2 × ² cm ² each), and this was used as an evaluation cloth for the experiment.

The following method was applied as the cleaning method. In other words, apply 0.6g of liquid detergent composition for clothing per 5 sheets of dirt cloth, leave it for 5 minutes, and then put 5 sheets of dirt cloth as it is into Terg-O-Tomete r (cleaning test machine) 25 ° C tap water (hardness 3DH) 0.9L was added and stirred for 10 minutes at 120rpm, then transferred to a two-tank washing machine (Mitsubishi Electric Corp., product number: CW—C30A1—HI) and dehydrated for 1 minute. did. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

[0048] << Evaluation of Detergency of Sebum Dirt >>

Ten sheets of sebum soiled cloth (contaminated cloth) prepared by rubbing the sebum dirt on the face on 100th cotton plain weave cloth (uncontaminated cloth) cut into 10 cm square were prepared.

As a cleaning method, 0.6 g of the liquid detergent composition for clothing was put into Terg—O—Tometer, stirred for 30 seconds, and then 10 pieces of dirt cloth were put into Terg—O—Tometer as they were. 5 ° C tap water (hardness 3DH) 0.9L is added, stirred at 120rpm for 10 minutes, then washed in two tanks Machine (Mitsubishi Electric Corp., product number: CW-C30A1-HI) and dehydrated for 1 minute. afterwards,

It was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

[0049] << Evaluation criteria for cleaning power >>

Mud dirt cleaning power and sebum dirt cleaning power

The Z value was measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd .: trade name SE2000) and evaluated as a cleaning rate of the following formula. The average value of 10 sheets was used for each evaluation.

[0050] Cleaning rate (%) = (Z value after cleaning—z value before cleaning) Z (z value of raw fabric—Z value before cleaning) X 10

0

[0051] 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%

[0052] 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%

[0053] [Table 1]

Example 1 2 3 4 5 6

A-1 30 30 30 33 30

W 3 乂 J

A-2 30

B-1 3.5 4 3.5 5

(B) Component B-2 3.5

B-3 3.5

C-1 2 2 3 2 2

Shiso So J

C-2 2

Component (D) D-1 0.5 0.5 0.5 0.5 1.0 0.5

(E) Component E-1 3.0 4.0 3.0 3.0

Jieta

Nord 1.0 1.0 Amine

Arrangement / Noremi

0.1 0.1 0.1 0.1 0.1 α-Tinic acid

Narita

1 2 1 2 1 1 min Knoll

Poljec

Lengli 2 3 2 2 2 2 Optional Call

Ingredients

Fragrance composition A B C D A C Fragrance

0.2 0.2 0.1 0.2 0.1 0.1

Dye A 0.0006 0.0003 0.0002 0.0006 Dye B 0.0001 0.0003 0.0002 0.0002 Sodium hydroxide

Thorium appropriate amount appropriate amount or sulfuric acid

Purified Water Balance Balance / Lance Knock Balance Balance / Lance ρΗ 10.0 10.4 10.0 10.0 9.5 10.0 Sebum Dirt Detergency AAAABB Mud Dirt Detergency AAAABA

Example 7 8 9 10 11 12

A-3 30 30 30 25 25

(A) component

A-4 20 5

B-1 3.5 3.5 3.5 3.5 5.5 5.5

(B) Component B-2

B-3

C-1 5 2 2

(C) component

C-3 2 3 4

Component (D) D-1 0.5 0.5 0.5 0.5 0.5 0.5

(E) Component E-1 5.0 5.0 5.0 3.0 3.0 Diethanol 2.0

Ammin

Palmitic acid 0.1 0.1 0.1 0.1 0.1 0.1

Ethanol 1 1 1 1 5 1 min Polyethylene

2 2 2 2 5 2 Glycol

Fragrance composition A B C D A C

Perfume compounding amount 0.2 0.2 0.1 0.2 0.1 0.1 Dye A 0.0006 0.0006 0.0006 0.0006 0.0006 Dye B 0.0001 0.0001 0.0001 0.0001 0.0001 Dye C 0.0002 Sodium hydroxide Appropriate amount

Purified water Balanced balance Lance no Lansperance / Lance pH 10.5 10.5 10.5 10.0 9.5 10.0 Sebum dirt cleaning power AAABBA Mud dirt cleaning power AAAABA

Example 13 14 15 16

A-1 30 22.5 15 29

(A) component

A-5 7.5 15

B-1 3.5 3.5 3.5 3.5

(B) Component B-2

B-3

C-1 2 2 2

C-4 2

(C) component

C-5

C-6

(D) Component D-1 0.5 0.5 0.5 0.5 (E) Component E-1 3.0 1.0 3.0 3.0

□ LAS-Na 1 component Palmitic acid 0.1 0.1 0.1 0.1 min Ethanol 1 1 1 1 Polyethylene

2 2 2 2 Glycol

Fragrance composition A B C D Fragrance content 0.2 0.2 0.1 0.2 Dye A 0.0006 0.0006 0.0006 Dye B 0.0001 0.0001 0.0001 Dye!) 0.0002 Sodium hydroxide

Um or sulfuric acid

Purified water Balance balance / Lance no pH Lance 10.0 10.0 10.0 10.0 Sebum dirt cleaning power AABA Mud dirt cleaning power ABA ^A

Comparative Example 1 2 3 4 5 6

A-1 30 30 30 1

(Α) Ingredient

A-2

B-l 3.5

(Β) Component B-2

B-3 3.5

C-l 2 2

(C) component

C-3 10 10

(D) Component D-l 1 3.0

(Ε) Component E-l

Arrangement

1.0 1.0

α

Ammin

Completion

Noremic acid 0.1 0.1 0.1

Min

Ethanol 1 2 1

Polyethylene

2 3 2

Tt sound ΛΛ Dalicall

1 ±, Seiso J

Fragrance composition A B C

Perfume content 0.2 0.2 0.1

Dye C 0.0002 0.0003 0.0006

Sodium hydroxide Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount

Purified water PALANCE NOLANCE / LANCE BALANCE NOLANCE NOLANCE ρΗ 9.5 9.5 9.5 6.5 6.0 1.5 Sebum dirt cleaning power BBBCCC Mud dirt cleaning power CCCBCB

Examples 17 18 19 20 21

A-1 30 30 30 30

(Α) Ingredient

Α-2 30

B-1 3.5 3.5 3.5

(Β) Ingredient Β-2 3.5

Β-3 3.5

(C) Component C-5 2 2 2 4 3

Component (D) D-1 0.5 0.5 0.5 0.5 0.5 distribution

(Ii) Component E-1 3.0 2.5 3.0 2.5 3.0 Palmitic acid 0.1 0.1 0.1 0.1 Composition

Ethanol 1 2 1 1 1 min Polyethylene

2 3 2 2 2 Dalicall

Optional ingredients Fragrance composition A B C A C

Perfume content 0.2 0.2 0.1 0.1 0.1 Dye A 0.0006 0.0003 0.0002 0.0006

Dye B 0.0001 0.0003 0.0002 Purified water Balance balance

ΡΗ 10.0 9.5 10.0 9.5 10.0 Sebum dirt cleaning power AAAAA Mud dirt cleaning power ABABA

Example 22 23 24 25 26 27

A-3 30 30 30 30 25

(A) component

A-4 20 5

B-1 3.5 3.5 3.5 3.5 3.5 3.5

(B) Component B-2

B-3

C-6 2 2 2

(C) Component C-7 3 2

C-8 2

(D) component D-1 0.5 0.5 0.5 0.5 1.0 0.5

(E) Component E-1 2.0 3.0 3.0 3.0 2.5 3.0 Component Remitic acid 0.1 0.1 0.1 0.1 0.1 0.1 min Ethanol 1 1 1 1 5 1 Polyethylene

2 2 2 2 5 2 Glycol

Fragrance composition A B C D A C Optional ingredients

Perfume content 0.2 0.2 0.1 0.2 0.1 0.1 Dye A 0.0006 0.0006 0.0006 0.0006 0.0006 Dye B 0.0001 0.0001 0.0001 0.0001 0.0001 Dye C 0.0002 Purified water / Lancezo Lance Balance Nolance / Lance Nolance pH 9.0 10.0 10.0 10.0 9.5 10.0 Sebum dirt cleaning power AAAABA Mud dirt cleaning power BAAAAA

Example 28 29 30 31

A-1 30 22.5 15 29

(Α) Ingredient

Α-5 7.5 15

B-1 3.5 3.5 3.5 3.5

(Β) Ingredient Β-2

Β-3

C-5 2 2 2

(C) component

C-6 2

(D) Component D-1 0.5 0.5 0.5 0.5 (V) Component E-1 3.0 2.5 3.0 3.0 α LAS-Na 1 Component Palmitic acid 0.1 0.1 0.1 0.1 min Ethanol 1 1 1 1 Polyethylene

2 2 2 2 Glycol

Optional ingredients Fragrance composition ABCD Fragrance content 0.2 0.2 0.1 0.2 Dye A 0.0006 0.0006 0.0006 Dye B 0.0001 0.0001 0.0001 Dye C 0.0002 Purified water Nolance / Lance balance balance Η 10.0 9.5 10.0 10.0 Sebum dirt cleaning power AABA Mud dirt cleaning power ABAA

Comparative Example 7 8 9 10

A-1 30 30 30 30

(A) component

A-2

B-1 3.5 3.5

(B) Component B-2

B-3 3.5

(0 component C- 5 2

(D) Component D-1 0.5

(E) Component E-1 2.5 2.5 2.5 3.0

Chloride

□

Trimechinole 2 Comic Ammonium

Minute Palmitic acid 0.1 0.1 0.1 0.1 Ethanol 1 2 1 1 Optional polyethylene

2 3 2 2 Glycol

Fragrance composition A B C A Fragrance content 0.2 0.2 0.1 0.2 Dye C 0.0002 0.0003 0.0006 0.0002 Purified water Balance balance balance pH 9.5 9.5 9.5 10.0 Sebum dirt cleaning power B B B A Mud dirt cleaning power C C C C

[0061] [Table 9]

Example 32 33 34 35 36 37

A- 1 30 30 30 33 30

(Α) Ingredient

Α-2 30

(Ii) Component B-1 3.0 4.0 3.0 3.0 4.0 3.5

C-1 2 1.5 3

(C) Component C-2 2 3

C-5 2

Component (D) D-1 0.5 0.5 0.5 0.5 1 0.5

(Ii) Component E-1 3.0 4.0 3.0 3.5 2.5 3.5 π

Panolemitic acid 0.1 0.1 0.1 0.1 0.1

Ethanol 1 2 1 2 1 1 min Polyethylene

2 3 2 2 2 2 Glycol

Optional ingredients Fragrance composition A B C D A C Blending amount of fragrance 0.2 0.2 0.1 0.2 0.1 0.1 Dye A 0.0006 0.0003 0.0002 0.0006 Dye B 0.0001 0.0003 0.0002 0.0002 Purified water Palansperance Balance balance / lance

ΡΗ 10.0 10.5 10.0 10.5 9.5 10.0 Storage stability A A A A A A Sebum dirt cleaning power A A A A A A Mud dirt cleaning power A A A A B A

[0063] [Table 11]

[0064] As apparent from the results shown in Table 1-L I, it was confirmed that in the examples according to the present invention, good detergency was obtained for both mud soil and sebum soil. Further, when the component (E) was further contained, it was confirmed that the composition was excellent in storage stability.

Industrial applicability

[0065] According to the present invention, it is possible to provide a liquid detergent composition for clothing having good detergency against mud dirt.

Claims

The scope of the claims

(A) Average number of moles of added Echirenokishido number 10 to 20 carbon atoms in the hydrophobic group is 3 polyoxyethylene alkyl ethers from 2 to 50 mass ^_0/0;

(B) The following general formula (I):

A compound represented by:

(C) Semipolar surfactant, amphoteric surfactant, and the following general formula (II) or (III):

Me E. ) _a H

(Μ)

R ¹³ —— Ν

\ (EO) _b H

(In the formula, ¹ and R ¹² are each independently a linear or branched alkyl group or a alkenyl group having 1 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, a benzyl group, R ¹³ represents any one of a linear or branched alkyl group or a alkenyl group having 8 to 20 carbon atoms, a linear hydroxyalkyl group, a tolyl group, a phenyl group, or a benzyl group. EO represents an ethylene oxide group, a and b each represents 0 or more, a + b represents 10 or more, and represents an anion)

At least one compound selected from the group consisting of:

(D) 1-hydroxyethane-1, 1 diphosphonic acid or a salt thereof;

A liquid detergent composition for clothing, comprising: The liquid detergent composition for clothing according to claim 1, further comprising (E) monoethanolamine.