KR102051789B1 - Cleaning composition and its manufacturing method - Google Patents

Abstract

This invention provides the cleaning composition containing component (A): N-acyl acidic amino acid and / or its salt which have a predetermined structure, and component (B): fatty acid t-butylester which has a predetermined structure. do.

Description

Cleaning composition and its manufacturing method

This invention relates to a cleaning composition and its manufacturing method.

Acylamino acid type surfactant is especially important recently in the point which enables weakly acidic prescription close to pH of hair or skin. For example, Patent Literature 1 discloses a technique for improving malodor, haze, and the like of an acylamino acid surfactant. In addition, Patent Literature 2 discloses a technique for improving the foaming force, usability, and the like of an acylamino acid surfactant.

International Publication No. 00/40546 Brochure International Publication No. 2005/032509 Brochure

Here, in the cleaning composition used for a hair shampoo, body soap, etc., in order to acquire the cleaning effect (the function which absorbs and wraps a dirt with a bubble), and the effect which alleviates the friction of hair and skin, the favorable foam generation of the initial stage is Of course, "bubble lasts long," "bubble soft and firm elasticity", "bubble graininess" is strongly demanded.

However, according to the conventional cleaning composition described in Patent Documents 1 and 2, a product excellent in the quality and foaming power of the acylamino acid surfactant can be obtained, but the durability of the foam and the foaming (elasticity and fineness), etc. It is difficult to get an excellent product.

Then, an object of this invention is to provide the cleaning composition which is excellent in the initial bubble power and excellent in the durability of foam (henceforth "bubble persistence").

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to achieve the said objective, As a result, the cleaning composition containing N-acyl acidic amino acid and / or its salt which have a predetermined structure, and a fatty acid t-butylester which has a predetermined structure is provided. By using, it was found out that the initial bubble power was excellent and the bubble persistence was excellent, and the present invention was completed.

That is, the present invention is as follows.

[One]

The cleaning composition containing following component (A) and following component (B).

Component (A): N-acyl acidic amino acid represented by following General formula (1) and / or following General formula (2), and / or its salt

[Formula 1]

[Formula 2]

(In formula, R <1> represents a C7-C23 alkyl group. M <_1> and M <_2> respectively independently represent a hydrogen atom, an alkali metal or alkaline earth metal, organic or inorganic ammonium, a basic amino acid, or choline. M ₁ and M ₂ may be the same or different.)

Component (B): Fatty acid t-butyl ester represented by following General formula (3)

[Formula 3]

(In formula, R <1> represents a C7-C23 alkyl group.).

[2]

The cleaning composition as described in [1] whose content of the said component (B) is 0.01 mass ppm or more and 1000 mass ppm or less with respect to the mass of the said component (A).

[3]

Further comprising the following component (C),

The cleaning composition as described in [1] or [2] in which content as a free fatty acid of the said component (C) exists in the range of 0.1 mass% or more and 5 mass% or less with respect to the mass of the said component (A).

[Formula 4]

(In formula, R <1> represents a C7-C23 alkyl group. M <_3> represents a hydrogen atom, an alkali metal or alkaline-earth metal, organic or inorganic ammonium, a basic amino acid, or choline.)

[4]

The cleaning composition in any one of [1]-[3] which further contains the following component (D) and / or following component (E).

(D) ： aliphatic amidepropylbetaine and / or alkylbetaine

(E) ： Nonionic Surfactant

[5]

The manufacturing method of the cleaning composition containing the following processes.

1) 1st process which condensates acidic amino acid and fatty acid chloride in 5.0-60 hours in presence of an alkaline compound in the mixed solvent which consists of water and t-butanol substantially, and obtains a reaction liquid.

2) 2nd process which makes the said reaction liquid into pH 1-6 with acid, classifies into organic layer and water layer at the temperature of 35-80 degreeC, and acquires the organic layer containing N-acyl acidic amino acid.

3) The obtained organic layer is mixed with water and / or t-butanol, separated into an organic layer containing an aqueous layer and an N-acyl acidic amino acid at a temperature of 35 to 80 ° C., and an organic layer containing N-acyl acidic amino acid. 3rd process to acquire

4) From the obtained organic layer, neutralize 1/20 or more of the amount of carboxyl groups of the said N-acyl acidic amino acid, and when water temperature is 90 degrees C or less, water is added at the time of distillation, and solid content concentration in an organic layer is carried out. 4th process which keeps the solvent at 5.0-50 mass% with respect to the total amount of the organic layer, and distills off an organic solvent.

[6]

The manufacturing method of the cleaning composition as described in [5] whose time of the said 2nd process is 0.1 to 10 hours.

[7]

The manufacturing method of the cleaning composition as described in [5] or [6] whose time of the said 4th process is 1.0 to 60 hours.

According to the cleaning composition which concerns on this invention, it is excellent in initial bubble power and also excellent in the durability of foam | bubble.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention (henceforth simply a "this embodiment") is demonstrated in detail. This embodiment below is an illustration for demonstrating this invention, and is not intended to limit this invention to the following content. The present invention can be appropriately modified within the scope of the gist of the invention.

[Cleaning agent composition]

The cleaning composition of this embodiment is referred to as the following component (A) (hereinafter, simply referred to as "component (A)" and "(A)"), and following component (B) (hereinafter, simply referred to as "component (B)". , Also called "(B)")

Component (A): N-acyl acidic amino acid represented by following General formula (1) and / or (2), and / or its salt

[Formula 5]

[Formula 6]

In formula (1) and formula (2), R1 represents a C7-C23 alkyl group. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal or alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, or choline. M ₁ and M ₂ may be the same or different.

Component (B): Fatty acid t-butyl ester represented by following General formula (3).

[Component (A): N-acyl acidic amino acid (salt)]

The component (A) of this embodiment is N-acyl acidic amino acid represented by following General formula (1) and / or (2), and / or its salt (henceforth, it is also represented as "N-acyl acidic amino acid (salt)." .) to be.

[Formula 7]

[Formula 8]

In formula (1) and formula (2), R1 represents a C7-C23 alkyl group. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal or alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, or choline, and M ₁ and M ₂ may be the same or different.

Although it does not specifically limit as N-acyl acidic amino acid and / or its salt (henceforth "acyl aspartic acid (salt)" represented by Formula (1)), From a viewpoint of performance and the availability, it is N-lauro Il aspartic acid (R1: C11), N-myristoyl yl aspartic acid (R1: C13), and N-palmitoyl aspartic acid (R1: C15) are preferable. More preferably, they are N-lauroyl aspartic acid and N-myristoyl yl aspartic acid.

Although it does not specifically limit as a salt of acyl aspartate, For example, Metal salts, such as a sodium salt, potassium salt, a lithium salt, magnesium salt, a calcium salt; Ammonium salts, such as an ammonium salt and an alkylammonium salt; Monoethanolamine salt, diethanolamine Amine salts such as salts, triethanolamine salts, aminomethylpropanol salts; basic amino acid salts such as lysine salts and arginine salts, and single substances or mixtures such as choline salts. From the viewpoint of performance and availability, sodium salts, potassium salts, and triethanolamine salts are preferable, and triethanolamine salts are more preferable.

The acyl aspartic acid (salt) represented by Formula (1) may use N-acyl aspartic acid and N-acyl aspartic acid together. In addition, instead of combining salts, N-acyl aspartic acid and a base may be respectively blended to form salts in the formulation formulation.

Although it does not specifically limit as N-acyl acidic amino acid and / or its salt (henceforth "acyl glutamic acid (salt)") represented by Formula (2), N-lauroyl from a viewpoint of a performance and an easy availability. Glutamic acid (R1: 11 carbon atoms), N-myristoylyl glutamic acid (R1: 13 carbon atoms), N-palmitoyl glutamic acid (R1: 15 carbon atoms), and N- palm oil fatty acid acyl glutamic acid (R1: 8-18 carbon atoms) are preferable. Do. More preferably, they are N-lauroyl glutamic acid and N- palm oil fatty acid acyl glutamic acid.

Although it does not specifically limit as a salt of an acyl glutamate, For example, Metal salts, such as a sodium salt, potassium salt, a lithium salt, magnesium salt, a calcium salt; Ammonium salts, such as an ammonium salt and an alkyl ammonium salt; Monoethanolamine salt, diethanolamine salt Amine salts such as triethanolamine salt and aminomethylpropanol salt; basic amino acid salts such as lysine salt and arginine salt, and a single substance or mixture such as choline salt. From the viewpoint of performance and availability, sodium salts, potassium salts, and triethanolamine salts are preferable, and triethanolamine salts are more preferable.

The acyl glutamic acid (salt) represented by Formula (2) may use together N-acyl glutamic acid and N-acyl glutamate. In addition, instead of combining salts, N-acylglutamic acid and a base may be respectively blended to form a salt in the formulation.

Although it does not specifically limit as a component (A), The acyl aspartic acid salt, the acyl aspartic acid potassium salt, the acyl aspartic acid triethanolamine salt, the acyl glutamate salt, the acyl glutamate potassium salt, and the acyl glutamic acid triethanolamine salt are preferable. More preferably, they are acyl aspartic acid triethanolamine salt and acyl glutamic acid triethanolamine salt, More preferably, they are acyl aspartic acid triethanolamine salt.

N-acyl acidic amino acid and / or its salt which is component (A) of this embodiment can be manufactured by the well-known method as described in WO00 / 40546, etc., It is preferable to manufacture by the method mentioned later.

Although content in particular of component (A) is not restrict | limited, It is preferable that they are 0.01 mass% or more and 80 mass% or less with respect to the total amount (100 mass%) of a cleaning composition from a viewpoint of performance and economical efficiency, such as foaming force and foam persistence. . More preferably, they are 0.3 mass% or more and 60 mass% or less, More preferably, they are 1.0 mass% or more and 40 mass% or less.

[Component (B): Fatty acid t-butyl ester]

The component (B) of this embodiment is fatty acid t-butyl ester represented by following General formula (3).

[Formula 9]

In formula (3), R1 represents a C7-C23 alkyl group.

Although it does not restrict | limit especially as fatty acid t-butyl ester represented by Formula (3), From a viewpoint of performance and the availability, capric acid t-butyl ester, decanoic acid t-butyl ester, lauric acid t-butyl ester, and Myristic acid t-butyl ester is preferable. More preferably, it is lauric acid t-butyl ester.

There is no restriction | limiting in the manufacturing method of fatty acid t-butyl ester of Formula (3), What is necessary is just to synthesize | combine using a well-known method. For example, a method of reacting a fatty acid chloride with t-butanol or a condensing agent such as 4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride is used. Although the method of condensing fatty acid and t-butanol is mentioned, the method of using a condensing agent is also preferable because of high yield.

Although content in particular of component (B) is not restrict | limited, It is preferable that they are 0.01 mass ppm or more and 1000 mass ppm or less with respect to the mass of a component (A) from a bubble persistence and economical viewpoint. More preferably, they are 0.5 mass ppm or more and 500 mass ppm or less, More preferably, they are 1.0 mass ppm or more and 400 mass ppm or less. When content is 1000 mass ppm or less, the foam | bubble as a cleaning composition is changed and it gives a foam a soft and firm elasticity more.

[Component (C): fatty acid]

The cleaning composition of this embodiment can further contain the fatty acid or fatty acid salt (it is also only hereafter called "component (C)" and "(C)") represented by following formula (4).

[Formula 10]

(In formula, R <1> represents a C7-C23 alkyl group. M <_3> represents a hydrogen atom, an alkali metal or alkaline-earth metal, organic or inorganic ammonium, a basic amino acid, or choline.)

The component (C) represented by the formula (4) is not particularly limited as long as it is a C1-C23 fatty acid or its salt, but from the viewpoint of performance and availability, lauric acid, laurate, myristic acid, myristic acid salt , Palmitic acid, palmitate, stearic acid, and stearate are preferred. Among them, from the viewpoint of bubble performance, those salts are more preferable.

M ₃ in the formula (4) is not particularly limited as long as it is a hydrogen atom, an alkali metal or an alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, or choline, but an alkali metal and an organic ammonium are preferable in view of the performance of the cleaning composition. Do. Na and K are more preferable, and, as for an alkali metal, ammonium derived from triethanolamine, ammonium derived from diethanolamine, and ammonium derived from ethanolamine are more preferable for organic ammonium.

It is preferable that content as a free fatty acid of component (C) represented by Formula (4) exists in the range of 0.1 mass% or more and 5 mass% or less with respect to the mass of a component (A) from a viewpoint of maintaining the outstanding foamability, More preferably, it exists in the range of 1 mass% or more and 5 mass%. When content exists in such a range, it changes the foam quality as a cleaning composition, gives a foam soft and filled elasticity, and becomes a fine grain foam.

The cleaning composition of this embodiment is referred to as the following component (D) (hereinafter, simply referred to as "component (D)" and "(D)") and / or following component (E) (hereinafter, simply referred to as "component (E) ), And also referred to as "(E)."

Component (D): Aliphatic amidepropylbetaine and / or alkylbetaine

Component (E): Nonionic surfactant.

[Component (D): Betaine

The component (D) of this embodiment is a betaine of fatty acid amide propyl betaine and / or alkyl betaine.

Although it does not specifically limit as fatty acid amide propyl betaine, For example, lauramid propyl betaine, myristamide propyl betaine, stearamide propyl betaine, oleylamide propyl betaine, and cocamide propyl betaine are mentioned. . Among these, lauramid propyl betaine and cocamide propyl betaine are preferable, and lauramid propyl betaine is more preferable.

Although it does not specifically limit as alkylbetaine, For example, lauryl betaine, myristyl betaine, palmity betaine, stearyl betaine, oleyl betaine, and coco betaine are mentioned. Among these, coco betaine and lauryl betaine are preferable, and cocobetain is more preferable.

Although it does not restrict | limit especially as content of a component (D), The mass ratio ((A) / (D)) of the component (D) with respect to a component (A) is 0.1 or more from a foaming force, a thickening effect, and an economical viewpoint. It is preferable that it is 3.0 or less, More preferably, it is 0.2 or more and 2.0 or less.

[Component (E): Nonionic Surfactant]

Component (E) of this embodiment is a nonionic surfactant. Although it does not specifically limit as nonionic surfactant, For example, POE (polyoxyethylene) octyl ether, POE lauryl ether, POE myristyl ether, POE cetyl ether, POE stearyl ether, POE oleyl ether, POE Polyoxyethylene alkyl ethers such as isostearyl ether, POE behenyl ether, and POE octyl (2-ethyl-hexyl) ether; POE POP (polyoxypropylene) butyl ether, POE POE lauryl ether, POE POP cetyl Polyoxyethylene polyoxypropylene glycol types such as ether POE / POP glycol; polyoxyethylene aryl ethers such as POE octylphenyl ether, POE nonylphenyl ether, POE chlorophenyl ether, polyoxyethylene naphthol ether; POE cured castor oil ether, POE castor oil ether; other ethers such as POE lanolin alcohol ether and POE phytosterol; polyjades such as monostearate POE glyceryl and oleic acid POE glyceryl Ethyleneglycerin fatty acid esters; polyoxyethylene sorbitan fatty acid esters such as monolauric acid POE sorbitan, monostearic acid POE sorbitan, tristearic acid POE sorbitan, monoisostearic acid POE sorbitan; hexastearic acid POE sorbitol, And polyoxyethylene sorbitol fatty acid esters such as tetrastearic acid POE sorbitol, tetraoleic acid POE sorbitol, and monolauric acid POE sorbitol.

Moreover, polyethyleneglycol fatty acid ester, such as polyethyleneglycol monolauric acid, polyethyleneglycol monostearic acid, polyethyleneglycol monooleic acid, polyethyleneglycol distearic acid, polyethyleneglycol dioleic acid, polyethyleneglycol diisostearic acid; Ether esters such as esters; glycerin fatty acid esters such as glyceryl monostearate, glyceryl monostearate, glyceryl monostearate, glyceryl monostearate, and glyceryl distearate; diglyceryl monostearate, monooleic acid Glyceryl, Diglyceryl Dioleyl Dioleyl Monoglycerate, Diglyceryl Monostearate, Tetraglyceryl Monostearate, Tetraglyceryl Tristearate, Tetraglyceryl Pentastearate, Hexaglyceryl Monolaurate, Hexamethyl Monohexanoate Glyceryl, di Polyglycerin fatty acid esters, such as stearate decaglyceryl and diisostearate decaglyceryl; sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, mono Sorbitan fatty acid esters such as sorbitan isostearate; ethylene glycol fatty acid esters such as ethylene glycol monolaurate; propylene glycol fatty acid esters such as propylene glycol monostearate and propylene glycol self-emulsifying type.

Pentaerythritol fatty acid esters such as pentaerythritol monostearate and pentaerythritol monooleate; sugar derivatives such as multitolhydroxy fatty acid ethers, alkylated polysaccharides, alkyl (poly) glucosides and sugar esters; α-monoiso Alkyl glyceryl ethers such as stearyl glyceryl ether; organic acid monoglycerides such as acetyl-monogli, monoglyceride lactic acid and monoglyceride citrate; palm oil fatty acid monoethanolamide, lauroyl monoethanolamide, myristoyl monoethanolamide, Fatty acid alkanolamides such as lauroyl diethanolamide, palm oil fatty acid diethanolamide, lauroyl isopropanolamide, myristoyl isopropanolamide, palm oil fatty acid isopropanolamide, POE lauroyl monoethanolamide; POE laurylamine, POE sterol POE alkylamines, such as arylamine; There may be mentioned the reel dimethyl amine oxide, coco dimethyl amine oxide, cocoa dimethylamine mid-propyl amine oxides of the oxide or the like. Among these, fatty acid alkanolamides are preferable, and palm oil fatty acid monoethanolamide, palm oil fatty acid diethanolamide, lauroyl monoethanolamide, lauroyl diethanolamide, and lauroyl isopropanolamide are more preferable.

Although it does not restrict | limit especially as content of component (E), The mass ratio of the component (E) with respect to the sum total of a component (A) and a component (D) from a foaming force, a thickening effect, and an economical viewpoint ((E) / ( It is preferable that (A) + (D))) is 0.1 or more and 1.0 or less, More preferably, it is 0.1 or more and 0.8 or less.

Although pH of the cleaning composition of this embodiment is not specifically limited, It is preferable that it is 4.0-8.0. More preferably, it is 4.5-7.5, More preferably, it is 5.0-7.0.

In addition to the component (A), the cleaning composition of this embodiment can further contain anionic surfactant. Although it does not specifically limit as anionic surfactant, For example, sodium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, lauryl sulfate triethanolamine, etc. Alkyl sulfates and salts thereof; alkyl ether sulfates and salts thereof such as sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, sodium polyoxyethylene oleyl ether sulfate, and polyethanethylene lauryl ether sulfate triethanolamine; Alkyl aryl ether sulfuric acid, such as ethylene octyl phenyl ether sulfate, and its salt; Polyoxyethylene laurate amide ether sodium sulfate, Polyoxyethylene laurate amide ether sulfate triethanolamine, polyoxyethylene myristic amide ether sodium sulfate, polyoxyethylene Oleic acid amide ether sulfur Alkyl amide sulfuric acid, such as sodium acid, polyoxyethylene palm oil fatty acid amide ether sodium sulfate, and oleic acid amide ether sulfate, and its salt; Acyl ester sulfuric acid, such as hardened palm oil fatty acid glycerin sulfate, and its salt; Sodium lauryl sulfonate, sodium myristyl sulfonate, palm oil Alkyl sulfonic acid, such as sodium alkyl sulfonate, and its salt; Alkylbenzene sulfonic acid, such as sodium lineardodecylbenzene sulfonate, and linear dodecylbenzene sulfonate triethanolamine, and its salt; Alkyl naphthalene sulfonic acid and its salt; Formalin, such as the formalin polycondensate of naphthalene sulfonate Condensed sulfonic acids and salts thereof; sulfosuccinic acids and salts thereof such as sodium lauryl disulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, sodium lauryl polyoxyethylenesulfosuccinate, and sodium sodium oleate amide sulfosuccinate; have.

Moreover, alpha-olefinsulfonic acids and its salts, such as sodium dodecene sulfonate, sodium tetradecene sulfonate, potassium dodecene sulfonate, potassium dedecene sulfonate, its salts; (alpha)-sulfolaruic acid methyl ester, (alpha)-sulfomylate acid ester, α-sulfo fatty acid esters and salts thereof such as α-sulfolauric acid (EO) nmethyl ester; palm oil fatty acid acyl-N methyltaurine potassium, lauroyl-Nmethyltaurine sodium, lauroyl-Nmethyltaurine potassium, N such as lauroyl-Nmethyltaurinetriethanolamine, myristoyl-Nmethyltaurine sodium, myristoyl-Nmethyltaurinetriethanolamine, palm oil fatty acid acyl-Nmethyltaurine sodium, palm oil fatty acid acyl-Nmethyltaurinetriethanolamine -Acylmethyl-taurine and its salts; acyl isethionic acid and its salts such as sodium lauroyl isethionate, sodium myristoyl isethionate, and palm oil fatty acid sodium acyl isionate; Acid salts; Alkyl ether, such as sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, potassium polyoxyethylene myristyl phosphate, sodium polyoxyethylene oleyl ether phosphate, and sodium dipolyoxy acetyl oleyl ether phosphate Phosphoric acid and its salts; Alkyl aryl ether phosphoric acid and its salts; Fatty acid amide ether phosphoric acid, such as polyoxyethylene lauryl amide ether sodium phosphate, and its salt are mentioned.

Furthermore, alkyl phosphates and its salts, such as sodium lauryl phosphate, sodium myristyl phosphate, palm oil fatty acid sodium phosphate, potassium myristyl phosphate, lauryl phosphate triethanolamine, and oleyl phosphate diethanolamine; N-lauroyl glutamate, N -Sodium myristoyl glutamate, sodium N- palm oil fatty acid acyl glutamate, potassium N-lauroyl glutamate, potassium N-myristoyl glutamate, potassium N- palm oil fatty acid acyl glutamate, N-lauroyl glutamate triethanolamine, N- Myristoyl glutamic acid triethanolamine, N- palm oil fatty acid acyl glutamic acid triethanolamine, N-lauroyl glycine sodium, N-myristoyl glycine triethanolamine, N-lauroyl-β-alanine potassium, N-lauroyl threonine N-acyl, such as triethanolamine, N-lauroyl sarcosine sodium, N-lauroyl-N-methyl- (beta) -alanine sodium, and N-lauroyl-N-methyl- (beta) -alaninetriethanolamine No acid and its salts; Acyl imino di sodium, such as sodium lauroyl imino diacetic acid, lauroyl imino diacetic acid triethanolamine, palm oil fatty acid sodium acyl imino diacetic acid, lauroyl imino diacetic acid, palm kernel fatty acid sodium imino diacetate Acetic acid and its salts; Sodium polyoxyethylene lauryl ether acetate, Polyoxyethylene myristyl ether acetate, Polyoxyethylene palmityl ether acetate triethanolamine, sodium polyoxyethylene stearyl ether acetate, polyglyceryl lauryl ether acetate, etc. Ether carboxylic acids and salts thereof; acylated peptides such as palm oil fatty acid silk peptides; sodium polyoxyethylene laurate amide ether carboxylate, sodium polyoxyethylene myramide amide ether carboxylate, polyoxyethylene palm oil fatty acid Amide ether Le acid amide ether carboxylic acids and their salts, such as triethanolamine; acyl lactate; alkenyl may be mentioned succinic acid and their salts.

Moreover, the cleaning composition of this embodiment can further contain a cationic surfactant. Although it does not specifically limit as cationic surfactant, For example, lauryl trimethylammonium chloride, myristyl trimethylammonium chloride, palmityl trimethylammonium chloride, stearyl trimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, beryl Monoalkyl quaternary ammonium salts such as heyltrimethylammonium chloride, palm oil alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, palm oil alkyltrimethylammonium bromide, cetyltrimethylammoniummethyl sulfate; dioctyldimethylammonium chloride, dira Dialkyl quaternary ammonium salts such as uryldimethylammonium chloride and distearyldimethylammonium chloride; Lanolin fatty acid aminopropylethyldimethylammoniumethylsulfuric acid, lauroylamino Acylaminoalkyl quaternary ammonium salts such as methylmethyldiethylammoniummethyl sulfate; alkylethenoxy quaternary ammonium salts such as dipalmitylpolyethenoxyethylammonium chloride and distearyl polyethenoxymethylammonium chloride; Alkyl isoquinolinium salts such as uril isoquinolinium chloride; benzalkonium salts such as lauryl dimethylbenzyl ammonium chloride and stearyldimethylbenzyl ammonium chloride; benzyl dimethyl ｛2- [2- (p-1,1,3, Benzethonium salts such as 3, -tetramethylbutylphenoxy) ethoxy] ethyl］ ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; N-cocoyl arginine ethyl ester pyrrolidone carboxylate Acyl basic amino acid alkyl ester salts such as N-laurolysin ethylethyl ester hydrochloride; primary amine salts such as laurylamine hydrochloride; dilaurylamine acetate Alkyl trialkylene glycol ammonium salts such as secondary amine salts; tertiary amine salts; fatty acid amide guanidinium salts; lauryl triethylene glycol ammonium hydrooxide; and the like.

Although content of each surfactant other than the component (A) and component (D) mentioned above is not specifically limited, A component (A) and a component (A) from a viewpoint which exhibits the action and effect of this invention more reliably. And as mass ratio of each surfactant other than a component (D), it is preferable that it is the range of component (A): each surfactant = 1: 1000-300: 1, More preferably, it is the range of 1: 200-100: 1 More preferably, it is the range of 1: 10-10: 1.

The cleaning composition of this embodiment may further contain a cationized polymer in the range which does not inhibit the effect. Although it does not restrict | limit especially as a cationized polymer, For example, chloride O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose (Lion Corporation make, brand name, LeoGuard LP, Union Carbide) Company make, brand name, polymer JR-400, Toho Chemical company make, brand name, Catarina LC-100, LC-200, HC-100, HC-200 others), chloride O- [2-hydroxy-3- (lauryl Dimethyl ammonio) propyl] hydroxyethyl cellulose (Union carbide company make, brand name, polymer LM-200 others), cationized cellulose, such as hydroxyethyl cellulose dimethyl diallyl ammonium chloride, chloride O- [2-hydroxy- Cationized guar gum, dextran chloride hydroxy such as 3- (trimethylammonio) propyl] guar gum (manufactured by Nikko Chemicals Co., Ltd., brand name, JAGA C-13S, Henkel Japan Co., Ltd., brand name, Cosmedia Gua C261 et al.) Propyltrimethylammonium Cationized polysaccharides obtained by cationicating polysaccharides such as cellulose derivatives, natural gums, starches, dextran, and the like, such as cationized dextran such as tere; chloride N- [2-hydroxy-3- (trimethylammonio) propyl] Hydrolysis Casein, Chlorinated N- [2-hydroxy-3- (trimethylammonio) propyl] Hydrolyzed Collagen, Chloride N- [2-hydroxy-3- (trimethylammonio) propyl] Hydrolyzed Silk, Chlorinated N -[2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed keratin, chloride N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein, chloride N- [2-hydroxy Roxy-3- (trimethylammonio) propyl] hydrolysis conchiolin, chloride N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolysis keratin, chloride N- [2-hydroxy-3 -(Stearyldimethylammonio) propyl] hydrolyzed collagen, chloride N- [2-hydroxy-3- (stea) Dimethylammonio) propyl] hydrolyzed silk, chloride N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolysis casein, chloride N- [2-hydroxy-3- (stearyldimethylammoni) O) propyl] hydrolyzed wheat protein, chloride N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolyzed conchiolin, chloride N- [2-hydroxy-3- (lauryldimethylammoni) 5) propyl] hydrolyzed keratin, chloride N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed collagen, chloride N- [2-hydroxy-3- (lauryldimethylammonio) Propyl] hydrolyzed silk, chloride N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed casein, chloride N- [2-hydroxy-3- (lauryldimethylammonio) propyl] Hydrolyzed wheat protein, N- [2-hydroxy-3- (lauryldimethylammonio) propyl chloride] Hydrolyzed conchiolin, N- [2-hydroxy-3- (palm oil) Alkyldimethylammonio) propyl] hydrolyzed soy protein, chloride N- [2-hydroxy-3- (palm oil alkyldimethylammonio) propyl] hydrolyzed casein, chloride N- [2-hydroxy-3- (palm oil alkyl) Dimethylammonio) propyl] hydrolyzed collagen, chloride N- [2-hydroxy-3- (palm oil alkyldimethylammonio) propyl] hydrolyzed silk, chloride N- [2-hydroxy-3- (palm oil alkyldimethylammonium) C) hydrolyzed protein obtained by cationic hydrolysis protein such as propyl] hydrolyzed keratin, N- [2-hydroxy-3- (palm oil alkyldimethylammonio) propyl] hydrolyzed conchiolin; Dimethyldiallyl ammonium acrylamide copolymer (manufactured by Narco Japan, trade name, Mark Coat 550, manufactured by Lion, trade name, Lipoflo MN and others), β-methacryloxyethyltrimethylammonium acrylamide copolymer (example For example, Hakuresu Retin 220), dimethyl diallyl ammonium chloride acrylic acid copolymer, dimethyl diallyl ammonium acrylic acid acrylamide copolymer, vinylpyrrolidone N, N-dimethylaminoethyl methacrylate copolymer Cationic vinyl-based or cationized acrylic-based polymers such as ethyl sulfate and polydimethylmethylene piperidinium (manufactured by Narco Japan, trade name, Mark Coat 100, manufactured by Lion Corporation, trade name, Lipoflo KY, etc.); Copolymer of acid and dimethylaminohydroxypropyldiethylenetriamine (e.g., SANDOZ Co., trade name, Carterine F4), polyethyleneimine (manufactured by Nippon Catalyst Industries, Ltd.) Crude, trade name, Epomy P-100), a condensate of polyamine and polyglycol, dimethyl adipicionate-aminohydroxypropyldiethyltriamine copolymer, aminoethylaminopropylmethylpolysiloxane copolymer, and mixtures thereof Can be mentioned.

In addition, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium described in Japanese cosmetic raw materials collection 2007 (Japan Cosmetics Industry Association, June 28, 2007) -10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-32, polyquaternium-33, polyquaternium-37, polyquaternium-39 , Polyquaternium-43, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-49, Polyquaternium-51, Polyquaternium-52, Polyquaternium-53, Poly Quaternium-55, Polyquaternium-57, Polyquaternium-61, Polyquaternium-64, Polyquaternium-65, Polyquaternium-68, Corohydroxyhydroxytrimonium chloride, Hydroxypropyltrimonium chloride And compounds such as starch and guarhydroxypropyltrimonium chloride.

Among the above, as the cationized polymer, a cationized vinylic and cationized acrylic polymer, a cationized polysaccharide, and a cationized guar gum are preferable, and more preferably, a cationized vinylic and acrylic polymer.

Gemini-type compounds, such as a phosphorylcholine, bispyridinium quaternary ammonium salt, a bichain biscarboxylate, dilauroyl glutamate lysine Na, in the cleaning composition of this embodiment in the range which does not inhibit the effect It may further contain.

In the range which does not impair the effect, the cleaning composition of this embodiment can normally contain the various components used as a cleaning agent or cosmetics suitably according to the objective.

As these components, For example, powder components, such as calcium carbonate, talc, mica, kaolin, titanium dioxide, and zinc dioxide; Jojoba oil, macadamia nut oil, avocado oil, evening primrose oil, mink oil, rapeseed oil, Castor oil, sunflower oil, corn oil, cacao oil, palm oil, rice bran oil, olive oil, almond oil, sesame oil, sunflower oil, soybean oil, camellia oil, apricot seed oil, castor oil, mink oil, cottonseed oil, wax, palm oil, palm kernel oil Natural animal and vegetable fats and oils such as egg yolk oil, lanolin, and squalene; synthetic triglycerides; hydrocarbons such as squalane, liquid paraffin, petrolatum, ceresin, microcrystalline wax, and isoparaffin; carnava wax, paraffin wax, sperm whale, beeswax, cannes Waxes such as delala wax and lanolin; cetanol, stearyl alcohol, lauryl alcohol, cetostearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol Higher alcohols such as kool, hexyldecanol and octyldodecanol; cholesterol and derivatives thereof such as cholesteryl-octyldodecyl-behenyl; isopropyl myristic acid, isopropyl palmitic acid, isopropyl stearic acid, 2 esters such as ethyl glycerol, butyl stearic acid and ethyl linoleate; polar oils such as diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pentaerythritol ether, and polyoxypropylene butyl ether; The oily component described in (Japan Cosmetics Industry Association editing, June 28, 2007) is mentioned.

In addition, methylphenyl polysiloxane, methyl polysiloxane, octamethylcyclo tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, polyoxyethylene methyl polysiloxane Copolymer, polyoxypropylene methyl polysiloxane copolymer, poly (oxyethylene oxypropylene) methyl polysiloxane copolymer, methylhydrogen polysiloxane, tetrahydrotetramethylcyclotetrasiloxane, stearoxymethyl polysiloxane, cetoxymethyl polysiloxane, methyl polysiloxane Emulsion, high polymerization methylpolysiloxane, trimethylsiloxy silicic acid, crosslinking methylpolysiloxane, crosslinking methylphenylpolysiloxane, and the like, amino modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol modified silicone, methacryl modified silicone, mercaptoModified silicone, phenol modified silicone, single-ended reactive silicone, heterofunctional modified silicone, polyether modified silicone, methylstyryl modified silicone, alkyl modified silicone, higher fatty acid ester modified silicone, hydrophilic special modified silicone, higher alkoxy modified silicone, higher fatty acid Silicones including various derivatives such as silicone containing and fluorine-modified silicones; paraaminobenzoic acid and derivatives thereof, homomethyl-7N-acetylalantoranilate, butylmethoxybenzoylmethane, di-paramethoxy cinnamic acid-mono- Paramethoxy cinnamic acid derivatives such as glyceryl 2-ethylhexanoate and octylcinnamate, salicylic acid derivatives such as amyl salicylate, benzophenone derivatives such as 2,4-dihydroxybenzophenone and dimethoxybenzylidene dioxomime Ethyl Hexyl Dazoline Propionate, Liquid Lanolin Acetate, Golden Root Extract Extract, Trianilino-p-Carboethylhexyl When-there may be mentioned UV absorbers such as triazines.

In addition, ascorbic acid and its derivatives, such as arbutin, kojic acid, magnesium ascorbate, glutathione, licorice extract, cloves extract, tea extract, astaxanthin, fecal placenta extract, tocopherol and its derivatives, tranexamic acid and salts thereof , Whitening components such as azulene, γ-hydroxybutyric acid; polyhydric alcohols such as multitol, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycol, sodium pyrrolidone carboxylic acid, lactic acid Organic acids and salts thereof such as soda and sodium citrate, hyaluronic acids and salts thereof such as sodium hyaluronate, hydrolysates of yeast and yeast extracts, fermentation metabolites such as yeast cultures and lactic acid bacteria cultures, and water-soluble proteins such as collagen, elastin, keratin and sericin , Peptides such as collagen hydrolyzate, casein hydrolyzate, silk hydrolyzate, sodium polyaspartate and salts thereof, trehalose, Sugars such as xylobiose, maltose, raffinose, melibiose, sucrose, glucose, vegetable viscous polysaccharides, polysaccharides such as crystalline cellulose, amorphous cellulose, xylan, mannan, galactan, arabinane, arabinoxylan and the like Glycosaminoglycans and salts thereof, such as derivatives, water-soluble chitin, chitosan, pectin, chondroitin sulfate and salts thereof, glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, proline acid, etc. Sugar amino acid compounds such as amino acids and aminocarbonyl reactants, plant extracts such as aloe and maronier, trimethylglycine, urea, uric acid, ammonia, lecithin, lanolin, squalane, squalene, glucosamine, creatinine, DNA, RNA and other nucleic acid-related substances Moisturizers; Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyltrimethylammonium chloride Deether, ethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, starch, soluble starch, carboxymethyl starch, methyl starch, propylene glycol ester of alginic acid, methyl cellulose, gum arabic, xanthan gum, guar gum, locust bean gum, Queen's seed, carrageenan, galactan, pectin, met, dextran, succinoglucan, curdlan, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylic acid ester copolymer, polychlorinated Dimethylmethylene piperidinium, polyacrylic acid ester copolymer, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylic acid, nitrocellulose, polyethylene glycol fatty acid ester, distearic acid polyethylene Polyoxyethylene fatty acid esters, such as glycol, Polyoxyethyl Thickeners, such as polyoxyethylene fatty acid ester methyl glycoside, such as methyl glucoside, such as ethylenediamine tetraacetic acid and its salt, hydroxyethylenediamine triacetic acid and its salt, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphate And metal ion blocking agents such as metaphosphates.

Further, antioxidants such as organic solvents such as ethanol, propylene glycol, 1,3-butylene glycol, butyl hydroxytoluene, tocopherol, phytic acid; citric acid, malic acid, tartaric acid, lactic acid, adipic acid, glutamic acid, aspartic acid Organic acids such as maleic acid; vitamin A and derivatives thereof; vitamin B such as vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and derivatives thereof; ascorbic acid, ascorbic acid sulfate, ascorbic acid Vitamin C, such as acid phosphate ester, vitamin E, such as (alpha) tocopherol, (beta) tocopherol, and (gamma) tocopherol, vitamins, such as vitamin D, vitamin H, and pantothenic acid; nicotinic acid amide, nicotinic acid benzyl, (gamma) -olizanol, allantoin, glyco Tilitinic acid (salt) Glytiletic acid and its derivatives, hinokithiol, musidine, bisabolol, eucalyptol, thymolinositol, saponins (chirayasapo , Azukisaponin, hechimasaponin, etc.) Blood stimulants such as tranexamic acid, pantotelethyl ether, ethynylestradiol, cephalandin, placenta extract, glycoside extract, ceparanthin, vitamin E and derivatives thereof, and gamma-olizanol Topical stimulants such as pepper tin, ginger tin, cantharis tin, nicotinic acid benzyl ester, nutrients such as various vitamins and amino acids, glytilinic acid, glytitinic acid derivatives, allantoin, azulene, aminocaproic acid, hydro Anti-inflammatory agents such as cortisone.

Furthermore, astringents such as zinc oxide, zinc sulfate, allantoinhydroxyaluminum chloride, aluminum chloride, zinc sulfonate carbonate and tannic acid; refreshing agents such as menthol and camphor; antihistamine; tocopherols, BHA, BHT, gallic acid, NDGA, ubi Various drugs such as antioxidants such as quinones; yeasts such as Saccharomyces, filamentous fungi, bacteria, placental placenta, placenta, human umbilical cord, yeast, ucollagen, milk-derived proteins, wheat, soybeans, bovine blood, pig blood, broth, Camomile, cucumber, rice, shea butter, birch, tea, tomato, garlic, hamamaris, rose, loofah, hop, peach, apricot, lemon, kiwi, buckwheat, red pepper, clara, bellflower, lotus flower, sage, Yarrow, Mallow, Cnidium, Bitter, Thyme, Angelica, Backwood, Birch, Horsetail, Scrubber, Maronier, Rock, Arnica, Lily, Wormwood, Peony, Aloe, Aloe Vera, Golden, Yellow Wall, Yellow Flower, Safflower, Cherry Blossom, Root, jujube, dermis, carrot, yulmu rice, Natural extracts obtained by extracting or hydrolyzing from animals and plants, microorganisms such as radish, gardenia, birches, etc. with organic solvents, alcohols, polyhydric alcohols, water, aqueous alcohols, etc .; pigments; flavors; lanolin, cholesterol, saponins, etc. Natural surfactants; polymeric surfactants such as sodium alginate, starch derivatives, tragant gum, and purified water.

Among these, containing the powder component further increases the cleaning power due to the physical frictional effect and tends to adsorb the dirt on the surface of the particles, which is effective.

Moreover, since it contains the effect which solubilizes oily contamination by the solvent effect of an oily component, containing oily component further is suitable for the improvement of washing power. Among the oil-based components, further containing silicones is particularly effective because it gives a fresh texture after use.

Further, further containing a moisturizing agent can suppress the roughness of the skin due to excessive degreasing and tends to contribute to the improvement of the feeling of use.

Moreover, combined use with a metal ion blocking agent and antioxidant is effective in suppressing the change of a product in a long term or severe use conditions, and continuing providing a good usability.

Although the washing | cleaning composition of this embodiment is not specifically limited, It is preferable for cosmetic uses, such as a hair shampoo, a body soap, a face-wash foam, a cleansing oil, a cleansing cream, a cleansing lotion, a cleansing milk, a toothpaste. Moreover, the cleaning composition of this embodiment is a household goods such as kitchen sinks, tableware, baths, tables, desks, furniture, stationery, clothing, ornaments, watches, bags, shoes, such as personal items, copiers, printers, etc. Office supplies, raincoats such as umbrellas and raincoats, bicycles, motorcycles, aircraft, vehicles such as ships, space engineering equipment such as rockets, satellites, medical devices such as MRI and ultrasonic devices, electronic boards, displays, solar cells, lithium ion Electronic materials, such as a battery and an electrode, can be used for various uses, such as electronic devices, such as a television, a telephone, a mobile telephone, a smart phone, and a PC. Although the container of the cleaning composition of this embodiment is not specifically limited, For example, general-purpose containers, such as a tube, a pump bottle, and a cream jar, can be employ | adopted.

[Method for producing detergent composition]

The manufacturing method of the cleaning composition of this embodiment includes the following processes.

(1) A first step of condensation reaction of an acidic amino acid and a fatty acid chloride for 5.0 to 60 hours in the presence of an alkaline compound in a mixed solvent consisting substantially of water and t-butanol (hereinafter referred to as "acylation reaction It is also called "process."

(2) 2nd process which makes the obtained reaction liquid into pH 1-6 with an acid, partitions into an organic layer and an aqueous layer at the temperature of 35-80 degreeC, and acquires the organic layer containing N-acyl acidic amino acid (following, Also called the `` acupuncture process ''.)

(3) The obtained organic layer is mixed with water and / or t-butanol, partitioned into an organic layer containing an aqueous layer and an N-acyl acidic amino acid at a temperature of 35 to 80 ° C, and the N-acyl acidic amino acid from which impurities are removed. 3rd process of acquiring the organic layer to contain (henceforth a "washing process".)

(4) From the obtained organic layer, neutralize 1/20 or more of the amount of carboxyl groups of N-acyl acidic amino acid, and add water in the conditions of 90 degrees C or less of the organic layer, and at the time of distillation, and solid content concentration in an organic layer The 4th process of keeping the organic solvent at 5.0-50 mass% with respect to the total amount (100 mass%) of this organic layer, and distilling off an organic solvent (henceforth a "solvent distillation process.").

[1st process: Acylation reaction process]

The acylation reaction step of the present embodiment is a step of condensation reaction of an acidic amino acid and a fatty acid chloride in the presence of an alkaline compound in a mixed solvent of water and t-butanol, and by the condensation reaction (acylation reaction), (Iii) N-acyl acidic amino acids are produced. Moreover, the reaction liquid obtained by condensation reaction is also called "acylation reaction liquid."

In this embodiment, the time of an acylation reaction process means the time from the time when the trivalent acid of an amino acid, fatty acid chloride, and an alkaline compound began to coexist in a solvent, and to the time when acid was added for the next pickling process. do. When the time of the acylation reaction step is 5.0 hours or more, fatty acid t-butyl ester is substantially produced. Moreover, when the time of an acylation reaction process is 60 hours or less, the fatty acid t-butyl ester produced | generated once is suppressed from decomposing | disassembly, and the obtained cleaning composition contains a fatty acid t-butyl ester substantially. The time of the acylation reaction step is preferably 10 to 40 hours.

In the acylation reaction step, the molar ratio of fatty acid chloride to acidic amino acid is preferably 1.05 or less, more preferably 1.0 or less, and still more preferably 0.98 or less. When the molar ratio of fatty acid halide to acidic amino acid is 1.05 or less, the amount of free fatty acid produced tends to be reduced.

As a composition of the mixed solvent of an acylation reaction process, it is preferable that the capacity ratio (water / t-butanol) of water with respect to t-butanol is the range of 90 / 10-20 / 80, More preferably, it is 85 / 15-50 / 50 range. By being in the range of 90/10 to 20/80, trivalent compounds of acidic amino acids, fatty acid chlorides and alkaline compounds are easily compatible, and the reaction rate can be increased, which is preferable.

Although the injection concentration of the acidic amino acid in an acylation reaction process is not specifically limited, Since the viscosity of a reaction liquid rises with time during reaction, it adjusts to the injection concentration of the grade which can be stirred-mixed at the time of approaching completion | finish of reaction. It is desirable to.

Although the reaction temperature of an acylation reaction process is not specifically limited, From a viewpoint of main reaction promotion and side reaction suppression, it is preferable that it is the range of -10-70 degreeC, More preferably, it is the range of -10-20 degreeC, More preferably Preferably it is -5.0-10 degreeC.

Although it does not restrict | limit especially as an alkaline compound used at an acylation reaction process, For example, inorganic bases, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, are mentioned.

It is preferable to maintain pH in 9-13.5 from a viewpoint of main reaction promotion and side reaction suppression, and, as for pH in an acylation reaction process, it is more preferable to maintain in the range of 10-13.

[The second process: acid pickling process]

In the acid pickling step of the present embodiment, the acylation reaction solution is, for example, pH 1 to 6 with acids such as hydrochloric acid and sulfuric acid (preferably mine), and the organic layer is separated into two layers, an organic layer and an aqueous layer. It is a process to acquire. In the acylation reaction solution, the produced N-acyl acidic amino acid exists in the form of an alkali salt. By adding an acid to this, one part or all part of the carboxyl group in N-acyl acidic amino acid is made into free acid, and it divides into an organic layer and an aqueous layer. Since the dissociation state of a carboxyl group changes by pH at the time of pickling, and the separation state, ie, the mass ratio of an organic layer and an aqueous layer, and the removability of inorganic salts slightly changes, it is preferable to carry out pH 1-3, More preferably, it is pH 1 to 2.5.

It is preferable that the temperature in an acid pickling process is 35-80 degreeC. More preferably, it is 40-70 degreeC. When it is 35 degreeC or more, the time until reaching layer equilibrium can be shortened, and when it reaches an equilibrium, it exists in the tendency which can reduce the amount of residual inorganic salts in an organic layer. Since the boiling point in the normal pressure of the azeotropic composition of water / t-butanol is around 80 ° C., boiling is prevented from occurring at 80 ° C. or lower, and the separation under pressure is unnecessary, which is advantageous in terms of simplification of the apparatus.

The time of an acid pickling process means the settling time in predetermined | prescribed pH and temperature. Although there is no restriction | limiting in stationary time, It is preferable that it is 0.1 to 10 hours from a viewpoint of fully dividing an organic layer and an aqueous layer, and suppressing decomposition of fatty acid t-butyl ester. More preferably, it is 0.2 to 5.0 hours.

[Third process: Water washing process]

The water washing process of this embodiment is a process of making a water-soluble impurity in the organic layer obtained by the acid immersion process shift in water layer by the liquid-liquid extraction method, and reducing it. Specifically, water and / or t-butanol is added to the organic layer after the acid immersion step to adjust the composition of N-acyl acidic amino acid / t-butanol / water, and the liquid extract is a water-soluble impurity in the organic layer, mainly an acylation reaction step and an acid immersion step. Inorganic salts produced in the process are transferred to the water layer.

In a water washing process, water washing temperature becomes like this. Preferably it is 35-80 degreeC, More preferably, it is 40-70 degreeC. By setting the water washing temperature to 35 ° C. or more, the time until reaching the equilibrium equilibrium is not long, and even when the equilibrium is reached, inorganic salts are less likely to remain in the organic layer, regardless of the type of N-acyl acidic amino acid or the concentration in the liquid. It tends to be easy to classify. Moreover, since the boiling point of the azeotropic composition of water / t-butanol is near 80 degreeC, boiling does not occur easily by making water washing temperature 80 degrees C or less, and there exists a tendency for the necessity of using the layering under a pressurization and a special apparatus.

[4th process: solvent distillation removal process]

In the solvent distillation removal process of this embodiment, although distillation operation is performed as N-acyl acidic amino acid salt, it does not specifically limit as a salt, Alkali metal salts, such as sodium, potassium, lithium, alkaline earth metal salts, such as calcium and magnesium And basic amino acid salts such as organic amine salts such as aluminum salts, zinc salts, ammonium salts, monoethanolamine, diethanolamine triethanolamine and triisopropanolamine, and arginine and lysine. In view of the performance and the availability of the cleaning composition, alkali metal salts and triethanolamine salts are preferable. What is necessary is just to add alkali or its aqueous solution, for example, to make N-acyl acidic amino acid into an amine salt or an alkali metal salt. When it is set as N-acyl acidic amino acid salt, it is preferable to add so that 1/20 or more of the carboxyl group content in N-acyl acidic amino acid may become an alkali salt. When the ratio of the alkali salt is 1/20 or more of the carboxyl group content, the effect of alkali addition is sufficiently obtained, and the fluidity of the mixed liquid tends to be preferably improved. It is more preferable to add the ratio of an alkali salt so that it may become 1/10 or more of carboxyl group content, and it is still more preferable to add so that it may become 1/3 or more.

It is preferable that the temperature in a solvent distillation removal process is 90 degrees C or less. By being 90 degrees C or less, the decomposition reaction of N-acyl acidic amino acid or its salt, etc. are suppressed, and there exists a tendency which can maintain product quality favorable. It is more preferable that it is 80 degrees C or less, and it is still more preferable that it is 70 degrees C or less.

In this embodiment, with the time in a solvent distillation removal process, after solvent starts to flow out at a predetermined temperature, t-butanol in a product reaches below a predetermined concentration, and a solvent distillation operation is carried out. It means time to stop. Although solvent distillation removal time in particular is not restrict | limited, It is preferable that it is 1.0 to 60 hours from a viewpoint of suppression of foaming of a cleaning composition, and suppression of decomposition of a fatty acid t-butyl ester. More preferably, it is 5.0 to 40 hours.

In the solvent distillation removal step, since water is also lost together with t-butanol, distillation is performed while adding water. The method of adding water, hot water, or steam intermittently or continuously is mentioned.

In the solvent distillation removal process, the solid content concentration in the liquid at the time of distillation is maintained at 5.0-50 mass% with respect to the total amount (100 mass%) of the liquid by distilling, adding water. When the solid content concentration is 50% by mass or less, high viscosity and solidification of the liquid can be suppressed, and decomposition reaction of N-acyl acidic amino acid or salt thereof can be suppressed due to overheating. When the solid content concentration is 5.0% by mass or more, the concentration of t-butanol can be reduced excessively and the distillation efficiency is lowered, and further concentration may be unnecessary when adjusting to the solid content concentration required as the final product. Do. Solid content concentration becomes like this. More preferably, it is 20-40 mass%, More preferably, it is 25-35 mass%.

In the solvent distillation removal process, it is preferable that t-butanol is removed to the extent that it does not affect the fragrance of a product. From this point of view, the t-butanol content is preferably 0.1 mass ppm or more and 750 mass ppm or less, more preferably 0.1 mass ppm or more and 300 mass ppm or less, further preferably 0.1 mass based on the N-acyl acidic amino acid. It is ppm or more and 150 mass ppm or less.

[Bubble persistence of detergent composition]

By using the cleaning composition of this embodiment, not only the bubble power is excellent, but the bubble which generate | occur | produced is stable for a long time. It is preferable that the cleaning composition of this embodiment maintains 60% or more height from the height of the bubble at the time of bubble generation, and maintains 80% or more height after 5 minutes after foaming on predetermined conditions. More preferred. Such a performance is exhibited by the cleaning composition containing at least a component (A) and a component (B), and the cleaning composition and component (A) component which consist of a component (A), a component (B), and a component (C) ( Cleaner composition consisting of B), component (C), and component (D), component (A), component (B), component (C), and cleaning composition comprising component (E), component (A), component ( It is exhibited in any case of the cleaning composition which consists of B), a component (C), a component (D), and a component (E).

Due to the high bubble persistence, the cleaning composition of the present embodiment further changes the foam quality as the cleaning composition, imparts softness and firmness to the foam, and is in fine grains.

Hereinafter, although an Example is given and a comparative example is given and this embodiment is demonstrated further more concretely, this embodiment is not limited at all by these Examples and a comparative example, unless the summary is exceeded.

<Analysis Method of Fatty Acid t-Butyl Ester (GC / MS Analysis)>

The fatty acid t-butyl ester was analyzed by GC / MS analysis using the following gas chromatograph and mass spectrometer.

Gas Chromatograph (GC)

Device ： Agilent Technology 7890B

Column ： SUPELCO Equity-1 (30 m × 0.25 mmΦ) Film Thickness 0.25 μm

Temperature conditions: 40 ℃ (5 minutes) → 10 ℃ / min → 320 ℃

Flow rate: 1 ml / min

Injection amount ： 1 µl

Injection hole ： 320 ℃ split 1 ： 10

Mass spectrometer (MS)

Device ： Agilent Technology 7000

Ionization ： EI 70 eV

Scan mode: TIC method (m / z = 10 to 800)

Ion source temperature ： 250 ℃

<Bubble power, evaluation method of bubble persistence>

About each cleaning composition shown in the Example and the comparative example, the aqueous solution diluted with water so that solid content might be 0.33 mass% was put into the juicer mixer, it stirred for 30 second, the height of the bubble immediately and after 5 minutes was measured, and immediately after and 5 minutes The height of subsequent bubbles was made into bubble power, respectively. Moreover, the ratio (%) of the height of the bubble after 5 minutes with respect to the height of the bubble immediately after was computed, and bubble persistence was evaluated according to the following references | standards.

◎ ： 80% or more

○: less than 60 to 80%

△ ： 60% or less

<Evaluation Method of Bubble Fineness>

About each cleaning composition shown in the Example and the comparative example, the external appearance of the foam obtained by the Rossmile method of the aqueous solution diluted with water so that solid content might be 0.33 mass% was visually confirmed, and the fineness of the bubble was evaluated according to the following criteria. .

(Double-circle): There are no coarse bubbles, and there are many fine bubbles.

(Circle): Although there are few coarse bubbles, a little coarse bubble mixes with a fine bubble.

(Triangle | delta): Although there are not many coarse bubbles, there are considerable quantities and coarse bubbles mix with fine bubbles.

X: There are many coarse bubbles.

<Evaluation method of elasticity of bubble>

About each cleaning composition shown in the Example and the comparative example, the foam obtained by the Rossmile method was touched by the aqueous solution diluted with water so that solid content might be 0.33 mass%, and the elasticity of foam was evaluated according to the following criteria.

(Double-circle): There is considerable elasticity to foam, and there is sensitivity to foam.

(Circle): Although there is considerable elasticity to foam, there is little sense of being hard to foam.

(Triangle | delta): Although foam is elastic, its elasticity is weak.

X: There is no elasticity in foam.

<Evaluation method of washing power>

1 g of commercially available butter was applied to the dish, and the cleaning composition shown in the examples and the comparative examples was washed with a liquid diluted with water so that the solid content was 0.1 mass%, and then the state of the dish was observed. The cleaning power was evaluated according to the standard.

(Double-circle): Oil of butter did not remain in a dish.

○: Some butter oil remains.

<Analysis Method of Free Fatty Acids (HPLC Analysis)>

The free fatty acid was measured from the peak area area obtained by analysis using the following HPLC.

Detector ： Differential Refractometer (RI)

Separation Tube: A stainless steel tube having an inner diameter of 6 mm and a length of 150 mm was filled with a modification of an octadecylsilyl group on a silica gel having a particle diameter of 5 m and a pore diameter of 12 nm.

Separation tube temperature ： Constant temperature around 40 ℃

Mobile phase ： Methanol / water / dioxane / phosphate = 2000/400/49 / 0.62

Flow rate ： Constant amount around 0.8 ml per minute

More specifically, the free fatty acid (%) was computed from each peak area area of the acylamino acid salt and fatty acid obtained by the analysis using HPLC using the following formula.

Free fatty acid (%) = peak area area of fatty acid / peak area area of acylamino acid salt × 100

<Viscosity>

About each cleaning composition shown in the Example and the comparative example, the viscosity in 25 degreeC was measured using the Brookfield viscometer.

<Synthesis of fatty acid t-butyl ester>

Synthesis Example 1

Synthesis of lauric t-butyl ester

Lauric acid (5.2 g, 0.026 mol), 4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (14.4 g, 0.052 mol) and N-methyl Morpholine (3.2 g, 0.032 mol) was dissolved in t-butanol (228 g) and reacted at 50 degreeC for 20 hours. The reaction solution was analyzed by the above analysis method, and production of lauric acid t-butyl ester was confirmed (yield 73%).

<Synthesis of N-acyl Acid Amino Acid Salts>

[Comparative Example 1]

(Acylation process)

1049 g of 80 mass% t-butanol aqueous solution was added to a mixed solution of 860 g (5.55 mol) of monosodium L-aspartate, 2978 g of pure water and 222 g (5.55 mol) of sodium hydroxide, and this solution was prepared. While maintaining the temperature at 3 ° C, 1210 g (about 5.2 mol) of lauroyl chloride was added dropwise while adjusting the pH to 12 with 25 mass% sodium hydroxide. The time of the acylation process was 2.5 hours.

(Pickling process)

After 1136 g of 80 mass% t-butanol aqueous solution was added, 75% sulfuric acid was added dropwise, the pH of the liquid was adjusted to 2 and the temperature of the liquid was adjusted to 45 ° C., and the mixture was left to stand for 1.0 hour to be partitioned into an organic layer and an aqueous layer. The organic layer was fractionated.

(Washing process)

The organic layer and the same mass of 20 mass% t-butanol aqueous solution were added and stirred with respect to the organic layer separated, and it left still at 45 degreeC for 1 hour, and partitioned into the organic layer and the water layer.

(Solvent distillation step)

Sodium hydroxide was added to the organic layer so that 83% of the carboxyl groups of N-lauroyl-L-aspartic acid in the separated organic layer were in the form of a salt, and pure water was added so that the solid content was 25% by mass. Thereafter, using a spray evaporator, distillation under reduced pressure was carried out at 70 ° C. for 20 hours while pure water was added so as to maintain the solid content at 25% by mass to obtain an aqueous N-lauroyl-L-aspartic acid salt solution ( Yield 98%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

[Examples 1 to 6 and 12]

The lauric acid t-butylester was mixed with the N-lauroyl-L-aspartic acid aqueous solution obtained by the comparative example 1 so that it may become a composition of Table 1, and the cleaning composition was prepared. Moreover, the bubble power and bubble persistence of the obtained detergent composition were shown in Table 1. Since Examples 1-6 contain fatty acid t-butyl ester, it was confirmed at least that the result which was excellent in bubble sustainability was obtained compared with the comparative example 1 which does not contain the said ester.

EXAMPLE 7

(Acylation Process)

To a mixed solution of 1444 g (7.72 mol) of monosodium L-glutamic acid monohydrate, 3070 g of pure water, and 1235 g of 25% aqueous sodium hydroxide solution (7.72 mol of sodium hydroxide), 1647 ml of an 80 mass% t-butanol aqueous solution was added thereto. 1760 g (7.56 mol) of coco chloride was stirred and dripped, adjusting pH to 12 with 25% sodium hydroxide, maintaining solution at 3 degreeC. The time of the acylation process was 6.0 hours.

(Pickling process)

75% sulfuric acid was added dropwise, the pH value of the liquid was adjusted to 2, and the temperature of the liquid was adjusted to 65 ° C. The mixture was left to stand for 1 hour, partitioned into an organic layer and an aqueous layer, and then the organic layer was separated.

(Washing process)

T-butanol and water were added to the organic layer, and the composition was prepared so that the composition was N-cocoyl-L-glutamic acid / t-butanol / water = 33/25/42 mass%, and the organic layer was left standing at 65 ° C for 1.0 hour. And divided into aqueous layer.

(Solvent Distillation Step)

Triethanolamine was added to the organic layer so that 50% of the carboxyl groups of N-cocoyl-L-glutamic acid in the separated organic layer would be in the form of a salt, and pure water was further added so that the solid content was 30% by mass. Then, distillation under reduced pressure was carried out at 70 degreeC for 20 hours, adding pure water so that solid content may be maintained at 30 mass% using the spray evaporator, and the aqueous solution of N-cocoyl-L- glutamic acid triethanolamine salt was obtained (yield) 97%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 8

The aqueous solution containing 30 mass% of N-cocoyl-L-glutamic acid was obtained on the conditions similar to Example 7 except having carried out the time of the acylation process for 30 hours (yield 98%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 9

Except having made the acylation process time 55 hours, the aqueous solution containing 30 mass% of N-cocoyl-L-glutamic acid was obtained on the conditions similar to Example 7 (yield 97%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 10

(Acylation process)

To a mixed solution of 860 g (5.55 mol) of monosodium L-aspartate, 2978 g of pure water, and 222 g (5.55 mol) of sodium hydroxide, 1049 g of an 80 mass% t-butanol aqueous solution was added and the solution was kept at 3 ° C. While adjusting pH to 12 with 25 mass% sodium hydroxide, 1210 g (about 5.2 mol) of lauroyl chlorides were stirred and dripped. The time of the acylation process was 32 hours.

(Pickling process)

After adding 1136 g of 80 mass% t-butanol aqueous solution, 75% sulfuric acid was added dropwise, the pH of the liquid was adjusted to 2 and the temperature of the liquid was adjusted to 45 ° C., and the mixture was allowed to stand for 1.0 hour to be partitioned into an organic layer and an aqueous layer. The organic layer was fractionated.

(Washing process)

The organic layer and the same mass of 20 mass% t-butanol aqueous solution were added and stirred with respect to the separated organic layer, and it left still at 45 degreeC for 1.0 hour, and partitioned into the organic layer and the water layer.

(Solvent distillation step)

Sodium hydroxide was added to the organic layer so that 83% of the carboxyl groups of N-lauroyl-L-aspartic acid in the separated organic layer were in the form of a salt, and pure water was added so that the solid content was 25% by mass. Thereafter, using a spray evaporator, distillation under reduced pressure was carried out at 70 ° C. for 20 hours while pure water was added so as to maintain the solid content at 25% by mass to obtain an aqueous solution of N-lauroyl-L-aspartic acid sodium salt ( Yield 98%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 11

An aqueous solution of N-lauroyl-L-aspartic acid sodium salt was obtained under the same conditions as in Example 10 except that the time of the acid pickling step was 15 hours, and the time of the solvent distillation step was 80 hours. 95%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 12

Aqueous solution of N-lauroyl-L-aspartic acid salt under the same conditions as in Example 10 except that the time of the acidification step of the acylation step was 15 hours, and the time of the solvent distillation step was 80 hours. Was obtained (yield 95%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

EXAMPLE 13

The free fatty acid of lauric acid was added to the composition obtained in Example 12 so that it may become 5 mass%, and the aqueous solution was obtained. Table 1 shows the composition of the aqueous solution (cleaning agent composition).

[Comparative example 2]

Except having made time of the acylation process 2.5 hours, the aqueous solution containing 30 mass% of N-cocoyl-L-glutamic acid was obtained on the conditions similar to Example 7 (yield 96%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

[Comparative Example 3]

Except having made time of the acylation process 68 hours, the aqueous solution containing 30 mass% of N-cocoyl-L-glutamic acid was obtained on the conditions similar to Example 7 (yield 96%). Table 1 shows the composition of the aqueous solution (cleaning agent composition).

Since Examples 10-13 were based on the manufacturing method of this embodiment, the composition containing a fatty acid t-butyl ester and a fatty acid was obtained, and both bubble persistence, the fineness of foam, the elasticity of foam, and the washing power were favorable. On the other hand, Comparative Examples 2 to 3 do not comply with the production method of the present embodiment, and thus a composition containing a fatty acid t-butyl ester cannot be obtained, and there are many free fatty acids, and the foam persistence, the fineness of the foam, the elasticity of the foam, Both the cleaning powers were inferior compared with the thing of Examples 10-13.

[Examples 14-21, Comparative Examples 4-5]

The cleaning composition of the composition of Table 2 was prepared, and bubble persistence and viscosity were evaluated. Since the cleaning composition in Examples 14-21 contains fatty acid t-butyl ester, it was excellent in bubble persistence and became a tendency for a high viscosity. On the other hand, since the cleaning composition in Comparative Examples 4-5 did not contain a fatty acid t-butyl ester, compared with that of Examples 14-21, bubble persistence was inferior and it became a tendency for a viscosity to be low.

The product name and manufacturer corresponding to the component used by (Note 1)-(Note 8) of Table 2 below are shown.

Note 1) Miyoshi Yuji Ahnorex LB-2

Note 2) Miyoshi Holding Co., Ltd. Anho Rex CB-1

Note 3) Shin Nippon Rica Co., Ltd. Rikabion A-100

Note 4) Toho Chemical Industry Co., Ltd. Obazorin BC

Note 5) Kawaken Fine Chemical Co., Ltd. Amisol CME

Note 6) Kawaken Fine Chemical Co., Ltd. Amisol CDE

Note 7) Khao Corporation Aminon C-11S

Note 8) Kawaken Fine Chemical Co., Ltd. Biscopine E2S

This application is based on the JP Patent application (Japanese Patent Application No. 2016-081483) of the Japan Patent Office on April 14, 2016, The content is taken in here as a reference.

Industrial availability

According to the cleaning composition which concerns on this invention, and its manufacturing method, not only the initial bubble power but also the favorable cleaning composition which "good bubbles last long", "soft and dusty resilience of foam", "fineness of foam", etc. are provided. It becomes possible.

Claims (8)

The cleaning composition containing following component (A) and following component (B).
Component (A): N-acyl acidic amino acid represented by following General formula (1) and / or following General formula (2), and / or its salt
[Formula 1]

[Formula 2]

(In formula, R <1> represents a C7-C23 alkyl group. M <_1> and M <_2> respectively independently represent a hydrogen atom, an alkali metal or alkaline earth metal, organic or inorganic ammonium, a basic amino acid, or choline. M ₁ and M ₂ may be the same or different.)
Component (B): Fatty acid t-butyl ester represented by following General formula (3)
[Formula 3]

(In formula, R <1> represents a C7-C23 alkyl group.). The method of claim 1,
Cleaner composition whose content of the said component (B) is 0.01 mass ppm or more and 1000 mass ppm or less with respect to the mass of the said component (A). The method of claim 1,
Further comprising the following component (C),
The cleaning composition in which content as a free fatty acid of the said component (C) exists in the range of 0.1 mass% or more and 5 mass% or less with respect to the mass of the said component (A).
[Formula 4]

(In formula, R <1> represents a C7-C23 alkyl group. M <_3> represents a hydrogen atom, an alkali metal or alkaline-earth metal, organic or inorganic ammonium, a basic amino acid, or choline.) The method of claim 2,
Further comprising the following component (C),
The cleaning composition in which content as a free fatty acid of the said component (C) exists in the range of 0.1 mass% or more and 5 mass% or less with respect to the mass of the said component (A).
[Formula 4]

(In formula, R <1> represents a C7-C23 alkyl group. M <_3> represents a hydrogen atom, an alkali metal or alkaline-earth metal, organic or inorganic ammonium, a basic amino acid, or choline.) The method according to any one of claims 1 to 4,
The cleaning composition further containing the following component (D) and / or following component (E).
(D) ： aliphatic amidepropylbetaine and / or alkylbetaine
(E) ： Nonionic Surfactant The manufacturing method of the cleaning composition containing the following processes.
1) 1st process of condensation reaction of acidic amino acid and fatty acid chloride in the mixed solvent which consists of water and t-butanol in presence of an alkaline compound for 5.0 to 60 hours, and obtaining a reaction liquid
2) 2nd process which makes the said reaction liquid into pH 1-6 with acid, classifies into organic layer and water layer at the temperature of 35-80 degreeC, and acquires the organic layer containing N-acyl acidic amino acid.
3) The obtained organic layer is mixed with water and / or t-butanol, separated into an organic layer containing an aqueous layer and an N-acyl acidic amino acid at a temperature of 35 to 80 ° C., and an organic layer containing N-acyl acidic amino acid. 3rd process to acquire
4) From the obtained organic layer, neutralize 1/20 or more of the amount of carboxyl groups of the said N-acyl acidic amino acid, and when water temperature is 90 degrees C or less, water is added at the time of distillation, and solid content concentration in an organic layer is carried out. 4th process which keeps the solvent at 5.0-50 mass% with respect to the total amount of the organic layer, and distills off an organic solvent. The method of claim 6,
The manufacturing method of the cleaning composition whose time of the said 2nd process is 0.1 to 10 hours. The method according to claim 6 or 7,
The manufacturing method of the cleaning composition whose time of the said 4th process is 1.0 to 60 hours.