JP6653751B2 - Detergent composition and method for producing the same - Google Patents

Description

  The present invention relates to a detergent composition and a method for producing the same.

  Acylamino acid-based surfactants have recently received particular attention since they enable a weakly acidic formulation close to the pH of hair and skin. For example, Patent Literature 1 discloses a technique for improving the odor, turbidity, and the like of an acylamino acid-based surfactant. Patent Literature 2 discloses a technique for improving the foaming power, feeling of use, and the like of an acylamino acid-based surfactant.

WO 00/40546 pamphlet WO 2005/032509 pamphlet

  Here, in the detergent composition used for hair shampoo, body soap, etc., the initial bubbling is good in order to obtain a cleaning effect (a function of absorbing dirt with foam and wrapping it around) and an effect of reducing friction between hair and skin. Needless to say, there is a strong demand for “long-lasting foam”, “thin elasticity of foam”, and “fineness of foam texture”.

  However, according to the conventional detergent compositions as described in Patent Documents 1 and 2, products excellent in the quality and foaming power of acylamino acid-based surfactants can be obtained, but the sustainability of foaming can be obtained. It is difficult to obtain a product excellent in foam quality and foam quality (elasticity and fineness).

  Therefore, an object of the present invention is to provide a detergent composition that has excellent initial foaming power and excellent foaming persistence (hereinafter, also referred to as “foaming persistence”).

  The present inventors have made intensive studies to achieve the above object, and as a result, have found that a washing containing an N-acyl acidic amino acid having a predetermined structure and / or a salt thereof, and a fatty acid t-butyl ester having a predetermined structure. By using the agent composition, it was found that the initial foaming power was excellent and the foaming sustainability was excellent, and the present invention was completed.

（式中、Ｒ１は、炭素数７〜２３のアルキル基を示す。Ｍ_１、及びＭ_２は、各々独立に、水素原子、アルカリ金属若しくはアルカリ土類金属、有機若しくは無機アンモニウム、塩基性アミノ酸、又はコリンを示す。Ｍ_１、及びＭ_２は、同じであっても、異なっていてもよい。）
成分（Ｂ）：下記一般式（３）で表される脂肪酸ｔ−ブチルエステル

（式中、Ｒ１は、炭素数７〜２３のアルキル基を示す。）。
［２］
前記成分（Ｂ）の含有量が、前記成分（Ａ）の質量に対して、０．０１質量ｐｐｍ以上１０００質量ｐｐｍ以下である、［１］に記載の洗浄剤組成物。
［３］
下記成分（Ｃ）をさらに含み、
前記成分（Ｃ）の遊離脂肪酸としての含有量が、前記成分（Ａ）の質量に対して、０．１質量％以上５質量％以下の範囲にある、［１］又は［２］に記載の洗浄剤組成物。

（式中、Ｒ１は、炭素数７〜２３のアルキル基を示す。Ｍ_３は、水素原子、アルカリ金属若しくはアルカリ土類金属、有機若しくは無機アンモニウム、塩基性アミノ酸、又はコリンを示す。）
［４］
下記成分（Ｄ）、及び／又は下記成分（Ｅ）をさらに含有する、［１］〜［３］のいずれかに記載の洗浄剤組成物。
（Ｄ）：脂肪族アミドプロピルベタイン及び／又はアルキルベタイン
（Ｅ）：ノニオン系界面活性剤
［５］
以下の工程を含む、洗浄剤組成物の製造方法。
１）実質的に水とｔ−ブタノールとからなる混合溶媒中、アルカリ性化合物の存在下で５．０〜６０時間、酸性アミノ酸と脂肪酸クロライドとを縮合反応し、反応液を得る第一工程
２）得られた前記反応液を、酸でｐＨ１〜６とし、３５〜８０℃の温度において有機層と水層とに分層し、Ｎ−アシル酸性アミノ酸を含む有機層を取得する第二工程
３）取得した前記有機層を、水及び／又はｔ−ブタノールと混合し、３５〜８０℃の温度において水層とＮ−アシル酸性アミノ酸を含む有機層とに分層し、Ｎ−アシル酸性アミノ酸を含む有機層を取得する第三工程
４）取得した前記有機層から、前記Ｎ−アシル酸性アミノ酸のカルボキシル基量の１／２０以上を中和し、有機層の温度が９０℃以下の条件で、かつ、蒸留時において水を添加し有機層中の固形分濃度を該有機層の総量に対して５．０〜５０質量％に維持して、有機溶媒を留去する第四工程
［６］
前記第二工程の時間が、０．１〜１０時間である、［５］に記載の洗浄剤組成物の製造方法。
［７］
前記第四工程の時間が、１．０〜６０時間である、［５］又は［６］に記載の洗浄剤組成物の製造方法。That is, the present invention is as follows.
[1]
A cleaning composition comprising the following component (A) and the following component (B).
Component (A): N-acyl acidic amino acid represented by the following general formula (1) and / or the following general formula (2) and / or a salt thereof

(Wherein, R ₁ represents an alkyl group having 7 to 23 carbon atoms. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal or an alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, or .M _1, and M ₂ indicating the choline can be the same or different.)
Component (B): fatty acid t-butyl ester represented by the following general formula (3)

(In the formula, R1 represents an alkyl group having 7 to 23 carbon atoms.)
[2]
The cleaning composition according to [1], wherein the content of the component (B) is 0.01 mass ppm or more and 1000 mass ppm or less based on the mass of the component (A).
[3]
It further contains the following component (C),
The content according to [1] or [2], wherein the content of the component (C) as a free fatty acid is in the range of 0.1% by mass or more and 5% by mass or less based on the mass of the component (A). Detergent composition.

(Wherein, R1 is .M ₃ represents an alkyl group having 7 to 23 carbon atoms is a hydrogen atom, an alkali metal or alkaline earth metal, an organic or inorganic ammonium, basic amino acid, or choline.)
[4]
The cleaning composition according to any one of [1] to [3], further comprising the following component (D) and / or the following component (E).
(D): aliphatic amidopropyl betaine and / or alkyl betaine (E): nonionic surfactant [5]
A method for producing a cleaning composition, comprising the following steps.
1) First step of subjecting acidic amino acid and fatty acid chloride to a condensation reaction in a mixed solvent consisting essentially of water and t-butanol in the presence of an alkaline compound for 5.0 to 60 hours to obtain a reaction solution 2) The second step of obtaining the organic layer containing the N-acyl acidic amino acid by adjusting the pH of the obtained reaction solution to 1 to 6 with an acid and separating the organic layer and the aqueous layer at a temperature of 35 to 80 ° C. 3) The obtained organic layer is mixed with water and / or t-butanol, separated into a water layer and an organic layer containing an N-acyl acidic amino acid at a temperature of 35 to 80 ° C., and containing an N-acyl acidic amino acid. Third step of obtaining an organic layer 4) From the obtained organic layer, neutralize at least 1/20 of the amount of carboxyl groups of the N-acyl acidic amino acid, at a temperature of the organic layer of 90 ° C. or lower, and Water added during distillation Maintained at 5.0 to 50 wt% solids concentration in the layer to the total amount of the organic layer, a fourth step of distilling off the organic solvent [6]
The method for producing a cleaning composition according to [5], wherein the time of the second step is 0.1 to 10 hours.
[7]
The method for producing a cleaning composition according to [5] or [6], wherein the time of the fourth step is 1.0 to 60 hours.

  ADVANTAGE OF THE INVENTION According to the cleaning composition which concerns on this invention, it is excellent in the initial foaming power and the persistence of foaming.

  Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the invention.

式（１）及び式（２）中、Ｒ１は、炭素数７〜２３のアルキル基を示す。Ｍ_１、及びＭ_２は、各々独立に、水素原子、アルカリ金属若しくはアルカリ土類金属、有機若しくは無機アンモニウム、塩基性アミノ酸、又はコリンを示す。Ｍ_１、及びＭ_２は、同じであっても、異なっていてもよい。
成分（Ｂ）：下記一般式（３）で表される脂肪酸ｔ−ブチルエステル。(Detergent composition)
The cleaning composition of the present embodiment includes the following component (A) (hereinafter, also simply referred to as “component (A)” and “(A)”) and the following component (B) (hereinafter, simply referred to as “component (B)”. ) ", Also referred to as" (B) ").
Component (A): N-acyl acidic amino acid represented by the following general formula (1) and / or (2) and / or a salt thereof

In the formulas (1) and (2), R1 represents an alkyl group having 7 to 23 carbon atoms. 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): a fatty acid t-butyl ester represented by the following general formula (3).

式（１）及び式（２）中、Ｒ１は、炭素数７〜２３のアルキル基を示す。Ｍ_１、及びＭ_２は、各々独立に、水素原子、アルカリ金属若しくはアルカリ土類金属、有機若しくは無機アンモニウム、塩基性アミノ酸、又はコリンを示し、Ｍ_１、及びＭ_２は、同じであっても、異なっていてもよい。[Component (A): N-acyl acidic amino acid (salt)]
The component (A) of the present embodiment refers to an N-acyl acidic amino acid represented by the following general formula (1) and / or (2) and / or a salt thereof (hereinafter collectively referred to as “N-acyl acidic amino acid (salt) ) ").

In the formulas (1) and (2), R1 represents an alkyl group having 7 to 23 carbon atoms. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal or an alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, or choline, and even if M ₁ and M ₂ are the same, , May be different.

  The N-acyl acidic amino acid represented by the formula (1) and / or a salt thereof (hereinafter, also referred to as “acyl aspartic acid (salt)”) is not particularly limited, but from the viewpoint of performance and availability. N-lauroyl aspartic acid (R1: carbon number 11), N-myristoyl aspartic acid (R1: carbon number 13), and N-palmitoyl aspartic acid (R1: carbon number 15) are preferred. More preferred are N-lauroyl aspartic acid and N-myristoyl yl aspartic acid.

  The salt of the acyl aspartate is not particularly limited, and examples thereof include metal salts such as sodium salt, potassium salt, lithium salt, magnesium salt, and calcium salt; ammonium salts such as ammonium salt and alkyl ammonium salt; monoethanolamine salt , Diethanolamine salts, triethanolamine salts, aminomethylpropanol salts and the like; basic amino acid salts such as lysine salts and arginine salts; From the viewpoints 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 the formula (1) may be used in combination with N-acyl aspartic acid and N-acyl aspartate. Further, instead of compounding the salt, N-acyl aspartic acid and a base may be compounded respectively to form a salt in the compounding formula.

  The N-acyl acidic amino acid represented by the formula (2) and / or a salt thereof (hereinafter also referred to as “acyl glutamic acid (salt)”) is not particularly limited, but from the viewpoint of performance and availability, -Lauroylglutamic acid (R1: carbon number 11), N-myristoylylglutamic acid (R1: carbon number 13), N-palmitoylglutamic acid (R1: carbon number 15), and N-coconut fatty acid acylglutamic acid (R1: carbon number 8) To 18) are preferable. More preferred are N-lauroyl glutamic acid and N-coconut fatty acid acylglutamic acid.

  The salt of the acylglutamate is not particularly limited, and examples thereof include metal salts such as sodium salt, potassium salt, lithium salt, magnesium salt and calcium salt; ammonium salts such as ammonium salt and alkylammonium salt; monoethanolamine salt; Examples thereof include amine salts such as diethanolamine salt, triethanolamine salt and aminomethylpropanol salt; basic amino acid salts such as lysine salt and arginine salt; and single or mixture of choline salts. From the viewpoints of performance and availability, sodium salts, potassium salts, and triethanolamine salts are preferable, and triethanolamine salts are more preferable.

  The acylglutamic acid (salt) represented by the formula (2) may be used in combination with N-acylglutamic acid and N-acylglutamate. Further, instead of compounding the salt, N-acylglutamic acid and a base may be compounded respectively to form a salt in the compounding formula.

  The component (A) is not particularly limited, but includes sodium acylaspartate, potassium potassium acylaspartate, triethanolamine acylaspartate, sodium sodium acylglutamate, potassium potassium acylglutamate, and triethanolamine acylglutamate. preferable. More preferred are acylaspartic acid triethanolamine salts and acylglutamic acid triethanolamine salts, and even more preferred are acylaspartic acid triethanolamine salts.

  The N-acyl acidic amino acid and / or a salt thereof, which is the component (A) of the present embodiment, can be produced by a known method described in WO00 / 40546 and the like, and is preferably produced by a method described below. .

  The content of the component (A) is not particularly limited. It is preferable that the content be from 01% by mass to 80% by mass. It is more preferably from 0.3% by mass to 60% by mass, and further preferably from 1.0% by mass to 40% by mass.

式（３）中、Ｒ１は、炭素数７〜２３のアルキル基を示す。[Component (B): fatty acid t-butyl ester]
The component (B) of the present embodiment is a fatty acid t-butyl ester represented by the following general formula (3).

In the formula (3), R1 represents an alkyl group having 7 to 23 carbon atoms.

  The fatty acid t-butyl ester represented by the formula (3) is not particularly limited, but from the viewpoint of performance and availability, t-butyl caprate, t-butyl decanoate, and t-butyl laurate are used. And t-butyl myristate are preferred. More preferably, t-butyl laurate is used.

  The method for producing the fatty acid t-butyl ester of the formula (3) is not limited, and may be synthesized using a known method. For example, a method of reacting a fatty acid chloride with t-butanol, or a method using a condensing agent such as 4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride to react with the fatty acid A method of condensing with t-butanol may be mentioned, but a method using a condensing agent is preferable because of high yield.

  The content of the component (B) is not particularly limited, but may be 0.01 mass ppm or more and 1000 mass ppm or less based on the mass of the component (A) from the viewpoint of foaming sustainability and economy. preferable. More preferably, it is 0.5 to 500 ppm by mass, and still more preferably 1.0 to 400 ppm by mass. When the content is 1000 ppm by mass or less, the foam quality of the detergent composition is changed, and the foam has more elasticity.

（式中、Ｒ１は、炭素数７〜２３のアルキル基を示す。Ｍ_３は、水素原子、アルカリ金属若しくはアルカリ土類金属、有機若しくは無機アンモニウム、塩基性アミノ酸、又はコリンを示す。）[Component (C): fatty acid]
The cleaning composition of the present embodiment can further include a fatty acid or a fatty acid salt represented by the following formula (4) (hereinafter, also simply referred to as “component (C)” or “(C)”).

(Wherein, R1 is .M ₃ represents an alkyl group having 7 to 23 carbon atoms is a hydrogen atom, an alkali metal or alkaline earth metal, an organic or inorganic ammonium, basic amino acid, or choline.)

  The component (C) represented by the formula (4) is not particularly limited as long as it is a fatty acid having 1 to 23 carbon atoms or a salt thereof, but from the viewpoint of performance and availability, lauric acid, laurate, myristic acid , Myristate, palmitic acid, palmitate, stearic acid, and stearates are preferred. Among them, those which are salts thereof are more preferable from the viewpoint of foaming performance.

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 from the viewpoint of each performance of the cleaning composition. , Alkali metals and organic ammoniums are preferred. The alkali metal is more preferably Na and K, and the organic ammonium is more preferably ammonium derived from triethanolamine, ammonium derived from diethanolamine, and ammonium derived from ethanolamine.

  The content of the component (C) represented by the formula (4) as a free fatty acid is from 0.1% by mass to 5% by mass with respect to the mass of the component (A) from the viewpoint of maintaining excellent foamability. %, More preferably in the range of 1% by mass to 5% by mass. When the content is in such a range, the foam quality as the detergent composition is changed, the foam is given more elasticity, and the foam becomes finer in texture.

The cleaning composition of the present embodiment includes the following component (D) (hereinafter, also simply referred to as “component (D)” or “(D)”) and / or the following component (E) (hereinafter, simply referred to as “component”). (E) ", also referred to as" (E) ").
Component (D): aliphatic amidopropyl betaine and / or alkyl betaine Component (E): nonionic surfactant.

[Component (D): betaines]
The component (D) of the present embodiment is betaines of fatty acid amide propyl betaine and / or alkyl betaine.

  Examples of the fatty acid amide propyl betaine include, but are not particularly limited to, lauramidopropyl betaine, myristamidopropyl betaine, stearamidopropyl betaine, oleylamidopropyl betaine, and cocamidopropyl betaine. Of these, lauramidopropyl betaine and cocamidopropyl betaine are preferred, and lauramidopropyl betaine is more preferred.

  Examples of the alkyl betaine include, but are not particularly limited to, lauryl betaine, myristyl betaine, palmityl betaine, stearyl betaine, oleyl betaine, and coco betaine. Among them, cocobetaine and laurylbetaine are preferred, and cocobetaine is more preferred.

  The content of the component (D) is not particularly limited, but from the viewpoint of foaming power, thickening effect, and economy, the mass ratio of the component (D) to the component (A) ((A) / (D) ) Is preferably from 0.1 to 3.0, more preferably from 0.2 to 2.0.

[Component (E): Nonionic surfactant]
The component (E) of the present embodiment is a nonionic surfactant. The nonionic surfactant is not particularly limited. For example, POE (polyoxyethylene) octyl ether, POE lauryl ether, POE myristyl ether, POE cetyl ether, POE stearyl ether, POE oleyl ether, POE isostearyl ether, POE Polyoxyethylene alkyl ether such as behenyl ether and POE octyl (2-ethyl-hexyl) ether; polyoxy such as POE • POP (polyoxypropylene) butyl ether, POE • POE lauryl ether, POE • POP cetyl ether POE • POP glycol Ethylene polyoxypropylene glycol type; POE octyl phenyl ether, POE nonyl phenyl ether, POE chlorophenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as naphthol ether; POE hardened castor oil ether; POE castor oil ether; other ethers such as POE lanolin alcohol ether and POE phytosterol; polyoxyethylene glycerin fatty acids such as POE glyceryl monostearate and POE glyceryl oleate Esters: Polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monolaurate, POE sorbitan monostearate, POE sorbitan tristearate, POE sorbitan monoisostearate; POE sorbitol hexastearate, POE sorbitol tetrastearate, POE sorbitol tetraoleate Sorbitol fats, such as POE and sorbitol monolaurate Ester, and the like.

  Also, polyethylene glycol fatty acid esters such as polyethylene glycol monolauric acid, polyethylene glycol monostearic acid, polyethylene glycol monooleic acid, polyethylene glycol distearic acid, polyethylene glycol dioleic acid, and polyethylene glycol diisostearic acid; and ethers such as polyethylene glycol lanolin fatty acid esters. Ester type; glyceryl fatty acid ester such as glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monohydroxystearate, glyceryl distearate; diglyceryl monostearate, diglyceryl monooleate, diglyceryl dioleate, monoisostearin Diglyceryl acid, tetraglyceryl monostearate, triglyceride Polyglycerol fatty acid esters such as tetraglyceryl thearate, tetraglyceryl pentastearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl distearate, decaglyceryl diisostearate; sorbitan monolaurate, sorbitan monostearate, monooleic acid Sorbitan fatty acid esters such as sorbitan, sorbitan trioleate, sorbitan tristearate and sorbitan monoisostearate; ethylene glycol fatty acid esters such as ethylene glycol monolaurate; propylene such as propylene glycol monostearate and self-emulsifying propylene glycol monostearate Glycol fatty acid esters.

  Furthermore, pentaerythritol fatty acid esters such as pentaerythritol monostearate and pentaerythritol monooleate; sugar derivatives such as maltitol hydroxy fatty acid ether, alkylated polysaccharide, alkyl (poly) glucoside and sugar ester; α-monoisostearyl glyceryl ether Alkyl glyceryl ethers such as acetyl monoglycol, lactic acid monoglyceride, citric acid monoglyceride, etc .; organic acid monoglycerides; coconut oil fatty acid monoethanolamide, lauroyl monoethanolamide, myristoyl monoethanolamide, lauroyl diethanolamide, coconut oil fatty acid diethanolamide, lauroyl Isopropanolamide, myristoyl isopropanolamide, coconut oil fatty acid isopropanolamide, POE Uronium yl monoethanolamide fatty acid alkanolamides, such as; POE lauryl amine, POE alkylamines such as POE stearyl amine; lauryl dimethyl amine oxide, coco dimethyl amine oxide, and amine oxides such as cocoamidopropyl dimethylamine oxide. Among them, fatty acid alkanolamides are preferable, and coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, lauroyl monoethanolamide, lauroyl diethanolamide, and lauroyl isopropanolamide are more preferable.

  Although the content of the component (E) is not particularly limited, the mass ratio of the component (E) to the sum of the components (A) and (D) ( (E) / ((A) + (D))) is preferably from 0.1 to 1.0, more preferably from 0.1 to 0.8.

  The pH of the cleaning composition of the present embodiment is not particularly limited, but is preferably 4.0 to 8.0. More preferably, it is 4.5 to 7.5, and still more preferably, it is 5.0 to 7.0.

  The cleaning composition of this embodiment can further contain an anionic surfactant in addition to the component (A). Examples of the anionic surfactant include, but are not particularly limited to, for example, sodium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, triethanolamine lauryl sulfate, and the like. Alkyl sulfuric acid and its salt; Alkyl ether sulfuric acid such as sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, sodium polyoxyethylene oleyl ether sulfate and triethanolamine polyoxyethylene lauryl ether; Alkyl aryl ether sulfuric acid such as sodium oxyethylene octyl phenyl ether sulfate and salts thereof; polyoxyethylene lauric acid amide Sodium sulfate, polyoxyethylene lauric amide ether triethanolamine sulfate, polyoxyethylene myristic acid amide ether sodium sulfate, polyoxyethylene oleic acid amide ether sodium sulfate, polyoxyethylene coconut oil fatty acid amide ether sodium sulfate, oleic acid amide Alkyl amide sulfuric acid such as sodium ether sulfate and salts thereof; acyl ester sulfuric acid such as hydrogenated coconut oil fatty acid sodium glycerin sulfate and salts thereof; alkyl sulfonic acid such as sodium lauryl sulfonate, sodium myristyl sulfonate and coconut oil sodium alkyl sulfonate; Its salts; alkylbenzene sulfones such as sodium linear dodecylbenzenesulfonate and triethanolamine linear dodecylbenzenesulfonate And a salt thereof; alkylnaphthalenesulfonic acid and a salt thereof; a formalin condensed sulfonic acid such as a formalin polycondensate of a naphthalenesulfonic acid salt and a salt thereof; disodium lauryl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, and polyoxyethylene Sulfosuccinic acids such as lauryl sulfosuccinate disodium and disodium amide amide sulfosuccinate, and salts thereof.

  Α-olefinsulfonic acids such as sodium dodecenesulfonate, sodium tetradecenesulfonate, potassium dodecenesulfonate and potassium detradecenesulfonate and salts thereof; α-sulfourauric acid methyl ester, α-sulfomyristic acid Α-sulfofatty acid esters such as methyl ester and α-sulforauric acid (EO) n methyl ester and salts thereof; coconut fatty acid acyl-N-methyltaurine potassium, lauroyl-N-methyltaurine sodium, lauroyl-N-methyltaurine potassium, lauroyl -N-methyltaurine triethanolamine, myristoyl-N-methyltaurine sodium, myristoyl-N-methyltaurine triethanolamine, coconut fatty acid acyl-sodium N-methyltaurine, coconut fatty acid acyl-N-methyl N-acylmethyl-taurine such as taurine triethanelamine and salts thereof; acylisethioic acids and salts thereof such as sodium lauroylisethionate, sodium myristoylisethionate and coconut oil fatty acid sodium acylisethionate; alkylsulfoacetates; polyoxyethylene Alkyl ether phosphoric acids such as sodium lauryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, potassium polyoxyethylene myristyl phosphate, sodium polyoxyethylene oleyl ether phosphate, sodium dipolyoxyethylene oleyl ether phosphate, and salts thereof Alkyl aryl ether phosphoric acid and salts thereof; fatty acid amide ether phosphoric acid such as sodium polyoxyethylene lauryl amide ether phosphate and salts thereof. It is.

  Further, alkyl phosphoric acids such as sodium lauryl phosphate, sodium myristyl phosphate, sodium coconut fatty acid phosphate, potassium myristyl phosphate, triethanolamine lauryl phosphate, diethanolamine oleyl phosphate, and salts thereof; sodium N-lauroylglutamate; -Sodium myristoyl glutamate, sodium N-coconut fatty acid acylglutamate, potassium N-lauroylglutamate, potassium N-myristoylglutamate, potassium N-coconut fatty acid acylglutamate, triethanolamine N-lauroylglutamate, triethanolamine N-myristoylglutamate , N-coconut fatty acid acylglutamate triethanelamine, N-lauroylglycine sodium, N-myristoylglycol Triethanolamine, potassium N-lauroyl-β-alanine, N-lauroylthreonine triethanolamine, sodium N-lauroyl sarcosine, sodium N-lauroyl-N-methyl-β-alanine, N-lauroyl-N-methyl-β-alanine N-acyl amino acids such as alanine triethanolamine and salts thereof; sodium lauroyl iminodiacetate, triethanolamine lauroyl iminodiacetate, coconut oil fatty acid acyl iminodidiacetate, disodium lauroyl iminodidiacetate, sodium palm kernel fatty acid iminodiacetic acid, etc. Acyl iminodiacetic acid and its salts; sodium polyoxyethylene lauryl ether acetate, potassium polyoxyethylene myristyl ether acetate, triethano polyoxyethylene palmityl ether acetate Ether carboxylic acids and salts thereof, such as ruamine, sodium polyoxyethylene stearyl ether acetate and sodium polyglyceryl lauryl ether; acylated peptides such as coconut oil fatty acid silk peptide; sodium polyoxyethylene lauric acid amide ether carboxylate; polyoxyethylene myristine Amide ether carboxylic acids such as sodium acid amide ether carboxylate, polyoxyethylene coconut oil fatty acid amide ether carboxylic acid triethanolamine and the like; acyl lactate; alkenyl succinic acid and the salt thereof.

  Moreover, the cleaning composition of this embodiment can further contain a cationic surfactant. The cationic surfactant is not particularly limited, for example, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, Monoalkyl quaternary ammonium salts such as coconut oil alkyltrimethylammonium chloride, tallowalkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methylsulfate; dioctyldimethylammonium chloride, dilauryldi Dialkyl quaternary ammonium salts such as tillammonium chloride and distearyldimethylammonium chloride; acylaminoalkyl quaternary ammonium salts such as lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate and lauroylaminoethylmethyldiethylammonium methyl sulfate; dipalmityl Alkylethenoxy quaternary ammonium salts such as polyethenoxyethylammonium chloride and distearylpolyethenoxymethylammonium chloride; alkylisoquinolinium salts such as laurylisoquinolinium chloride; lauryldimethylbenzylammonium chloride, stearyldimethylbenzyl Benzalkonium salts such as ammonium chloride; benzyldimethyl {2- [2- (p-1,1,3,3, -tetra) Benzethonium salts such as ethylmethylammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; N-cocoylarginine ethyl ester pyrrolidone carboxylate; N-lauroyl lysine ethyl ethyl ester hydrochloride Acyl basic amino acid alkyl ester salts such as laurylamine hydrochloride; secondary amine salts such as dilaurylamine acetate; tertiary amine salts; fatty acid amide guanidinium salts; Examples thereof include alkyltrialkylene glycol ammonium salts such as ethylene glycol ammonium hydroxide.

  The content of each surfactant other than the above-mentioned components (A) and (D) is not particularly limited, but from the viewpoint of more reliably exerting the action and effect of the present invention, the components (A) and (A) ) And each surfactant other than the component (D) is preferably in the range of component (A): each surfactant = 1: 1000 to 300: 1, more preferably 1: 200 to 100. : 1, more preferably 1:10 to 10: 1.

  The cleaning composition of the present embodiment may further contain a cationized polymer as long as the effect is not impaired. Examples of the cationized polymer include, but are not particularly limited to, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (manufactured by Lion, trade name, Leogard LP, manufactured by Union Carbide, Trade name, polymer JR-400, manufactured by Toho Chemical Co., Ltd., trade name, Catinal LC-100, LC-200, HC-100, HC-200, etc.), O- [2-hydroxy-3- (lauryldimethylammonio) chloride ) Propyl] hydroxyethylcellulose (manufactured by Union Carbide Co., Ltd., trade name, polymer LM-200, etc.), cationized cellulose such as hydroxyethylcellulose dimethyldiallylammonium chloride, etc., O- [2-hydroxy-3- (trimethylammonio) chloride ) Propyl] guar gum (Nikko Chemi) Such as cationized guar gum such as Luz, trade name, Jaguar C-13S, Henkel Japan, trade name, Cosmedia Guar C261, etc., and cationized dextran such as dextran chloride hydroxypropyltrimethylammonium ether. Cationized polysaccharides obtained by cationizing polysaccharides such as cellulose derivatives, natural gums, starch and dextran; N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed casein; 2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed collagen, N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed silk, N- [2-hydroxy-3- (trimethyl) chloride Ammonio) propyl] hydrolyzed keratin, N chloride [2-Hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein, N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed conchiolin, N- [2-hydroxy-3 chloride] -(Stearyldimethylammonio) propyl] hydrolyzed keratin, N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolyzed collagen, N- [2-hydroxy-3- (stearyldimethylammonio) chloride ) Propyl] hydrolyzed silk, N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolyzed casein, N- [2-hydroxy-3- (stearyldimethylammonio) propyl] hydrolyzed wheat Protein, N- [2-hydroxy-3- (stearyldimethyi chloride) Luammonio) propyl] hydrolyzed conchiolin, N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed keratin, N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed Collagen, N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed silk, N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed casein, N- [ 2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed wheat protein, N- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydrolyzed conchiolin, N- [2-hydroxy-chloride 3- (coconut oil alkyldimethylammonio) propyl] hydrolysis Bean protein, N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed casein, N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] chloride Hydrolyzed collagen, N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed silk, N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] chloride A cationized hydrolyzed protein obtained by cationizing a hydrolyzed protein such as hydrolyzed keratin, N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed conchiolin, or the like; Dimethyl diallyl ammonium chloride / acrylamide copolymer (manufactured by Narco Japan, trade name, Marcoat 550, LA ON Corporation, trade name, Lipoflow MN, etc.), β-methacryloxyethyltrimethylammonium / acrylamide copolymer (for example, Retin 220 manufactured by Hercules), dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acryl Acid / acrylamide copolymer, vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, polydimethyldimethylmethylenepiperidinium chloride (Nalco Japan, trade name, Marcoat 100, Lion Corporation, trade name) Cationized vinyl polymers or cationized acrylic polymers such as lipoflow KY, etc .; and copolymers of adipionic acid and dimethylaminohydroxypropyldiethylenetriamine (for example, trade name, Cartereti, manufactured by Sandoz Co.) F4), polyethyleneimine (Nippon Shokubai Kogyo Co., Ltd., trade name, Epomiri P-100), condensate of polyamine and polyglycol, dimethyl adipionate-aminohydroxypropyl diethyltriamine copolymer, aminoethylaminopropyl methylpoly Examples include siloxane copolymers and mixtures thereof.

  Also, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium described in Japan Cosmetic Ingredient Collection 2007 (edited by Japan Cosmetic Industry Association, June 28, 2007) -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, polyquaternium-55, polyquaternium-57, polyquaternium-61, polyquater Um -64, polyquaternium -65, polyquaternium -68, fenugreek hydroxypropyltrimonium chloride, chloride Hidorokishipuropirutorimoniumu starch, compounds such as guar hydroxypropyltrimonium chloride may be mentioned.

  Among the above, the cationized polymer is preferably a cationized vinyl-based or cationized acrylic-based polymer, a cationized polysaccharide, or a cationized guar gum, and more preferably a cationized vinyl-based or acrylic polymer.

  The cleaning composition of the present embodiment further contains a gemini-type compound such as a phosphorylcholine, a bispyridinium quaternary ammonium salt, a double-chain biscarboxylate, or lysine Na dilauroylglutamate as long as the effect is not impaired. You may.

  The cleaning composition of the present embodiment can appropriately contain various components usually used as a cleaning agent or a cosmetic according to the purpose, as long as the effects are not impaired.

  As these components, for example, powder components such as calcium carbonate, talc, mica, kaolin, titanium dioxide, zinc dioxide; jojoba oil, macadamia nut oil, avocado oil, evening primrose oil, mink oil, rapeseed oil, castor oil, sunflower oil , Corn oil, cacao oil, coconut oil, rice bran oil, olive oil, almond oil, sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, mink oil, cottonseed oil, mocro, palm oil, palm kernel oil, egg yolk Natural animal and vegetable fats and oils such as oil, lanolin and squalene; synthetic triglycerides; hydrocarbons such as squalane, liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin; carnauba wax, paraffin wax, whale wax, beeswax, candelilla wax, lanolin Waxes and the like; Higher alcohols such as tanol, stearyl alcohol, lauryl alcohol, cetostearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol; cholesterol such as cholesteryl-octyldodecyl-behenyl; Esters such as myristic acid, isopropyl palmitic acid, isopropyl stearic acid, glycerol 2-ethylhexanoate, butyl stearic acid, and ethyl linoleate; diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pentaerythritol ether, and polyoxypropylene butyl ether Polar oil; Japan Cosmetic Ingredients Collection 2007 (Japan Cosmetic Industry Association) Edit, include the oil component according to June 28, 2007).

  In addition, methylphenylpolysiloxane, methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, polyoxyethylene. Methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer, poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, methylhydrogenpolysiloxane, tetrahydrotetramethylcyclotetrasiloxane, stearoxymethylpoly Siloxane, ethoxymethylpolysiloxane, methylpolysiloxane emulsion, highly polymerized methylpolysiloxane, trimethylsiloxysilicic acid, frame Methyl-polysiloxane, cross-linked methylphenylpolysiloxane, etc., as well as amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, one-terminal reactive silicone, Various derivatives such as heterofunctional group 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 containing silicone and fluorine modified silicone. Silicones including: para-aminobenzoic acid and derivatives thereof, homomethyl-7N-acetylalantranilanilate, butylmethoxybenzoylmethane, -Paramethoxycinnamic acid-paramethoxycinnamic acid derivatives such as glyceryl mono-2-ethylhexanoate and octylcinnamate; salicylic acid derivatives such as amyl salicylate; benzophenone derivatives such as 2,4-dihydroxybenzophenone; dimethoxybenzylidene dioxo UV absorbers such as imidazoline ethylhexyl propionate, liquid lanolin acetate, Scutellaria root extract, and trianilino-p-carboethylhexyloxy-triazine.

  Further, arbutin, kojic acid, ascorbic acid and its derivatives such as magnesium phosphate ascorbate, glutathione, licorice extract, clove extract, tea extract, astaxanthin, beef placenta extract, tocopherol and its derivatives, tranexamic acid and its salts, azulene And whitening ingredients such as γ-hydroxybutyric acid; polyhydric alcohols such as maltitol, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol and glycol; organic acids such as sodium pyrrolidone carboxylate, sodium lactate and sodium citrate. Acids and salts thereof, hyaluronic acid and salts thereof such as sodium hyaluronate, hydrolysates of yeast and yeast extract, yeast culture solutions, fermentation metabolites such as lactic acid bacteria culture solutions, and water-soluble proteins such as collagen, elastin, keratin, and sericin. , Collagen hydrolyzate, casein hydrolyzate, silk hydrolyzate, peptides such as sodium polyaspartate and salts thereof, trehalose, xylobiose, maltose, raffinose, melibiose, sucrose, glucose, vegetable mucopolysaccharide and the like. Polysaccharides such as saccharides, crystalline cellulose, non-crystalline cellulose, xylan, mannan, galactan, arabinan, arabinoxylan and derivatives thereof, water-soluble chitin, chitosan, pectin, glycosaminoglycans such as chondroitin sulfate and salts thereof and salts thereof. Amino acids such as glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine and prophosphoric acid, sugar amino acid compounds such as aminocarbonyl reactants, plant extracts such as aloe and maronier, and trimethyl Glycine, urea, uric acid, ammonia, lecithin, lanolin, squalane, squalene, glucosamine, creatinine, humectants such as nucleic acid-related substances such as DNA and RNA; carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride ether, ethylcellulose, hydroxypropyl Cellulose, methyl hydroxypropyl cellulose, starch, soluble starch, carboxymethyl starch, methyl starch, propylene glycol alginate, methyl cellulose, gum arabic, xanthan gum, guar gum, locust bingham, quince seed, carrageenan, galactan, pectin, mannan, dextran, sac Shinoglucan, curdlan, gelatin, casein, albu , Collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polydimethyldimethylmethylenepiperidinium chloride, polyacrylate copolymer, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether Thickening of polyoxyethylene fatty acid esters such as carboxyvinyl polymer, polyacrylic acid, nitrocellulose, polyethylene glycol fatty acid ester, polyethylene glycol distearate, and polyoxyethylene fatty acid ester methyl glycoside such as polyoxyethylene dioleic acid methyl glucoside Agents: ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyacrylic acid Acid salts, and sequestering agents such as metaphosphoric acid salts.

  Furthermore, organic solvents such as ethanol, propylene glycol and 1,3-butylene glycol; antioxidants such as butylhydroxytoluene, tocopherol and phytic acid; citric acid, malic acid, tartaric acid, lactic acid, adipic acid, glutamic acid, asparagine Organic acids such as acid and maleic acid; Vitamin A and its derivatives; Vitamin B6 such as vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives; ascorbic acid, ascorbic acid sulfate, and ascorbic acid Vitamin C such as acid phosphate ester, vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, vitamin D such as vitamin H, pantothenic acid; nicotinamide, benzyl nicotinate, γ-oryzanol Allantoin, glycyrrhizic acid (salt) glycyrrhetinic acid and derivatives thereof, hinokitiol, mucidin, bisabolol, eucalyptol, thymol inositol, saponins (e.g., quilayasaponin, azusaponin, hetimasaponin) tranexamic acid, pantoterethyl ether, ethinyl estradiol, Blood circulation enhancers such as cephalandin, placenta extract, assembly extract, cepharanthin, vitamin E and its derivatives, gamma-oryzanol; local stimulants such as pepper tincture, shoal tincture, canthari tincture, nicotinic acid benzyl ester, various vitamins and amino acids Nutrients, glycyrrhetinic acid, glycyrrhizic acid derivatives, anti-inflammatory agents such as allantoin, azulene, aminocaproic acid and hydrocortisone.

  Further, astringents such as zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc sulfocarbonate, tannic acid; cooling agents such as menthol, camphor; antihistamines; tocopherols, BHA, BHT, gallic acid, NDGA, ubiquinone Various drugs such as antioxidants such as Saccharomyces; yeast, filamentous fungi, bacteria, bovine placenta, human placenta, human umbilical cord, yeast, bovine collagen, milk-derived protein, wheat, soybean, bovine blood, swine blood, cockscomb, Chamomile, cucumber, rice, shea butter, birch, tea, tomato, garlic, hamamelis, rose, loofah, hop, peach, apricot, lemon, kiwi, dokudami, capsicum, clara, sagebrush, kohone, sage, sawtooth grass, mallow, Senkyu, assembly, thyme, touki, spruce Birch, horsetail, loofah, marronnier, saxifrage, arnica, lily, mugwort, peonies, aloe, aloe vera, ougon, oakaku, kouka, safflower, sanshin, shikon, taisou, chimp, carrot, yokinin, adlay, gardenia, sawara, etc.・ Natural extract obtained by extracting or hydrolyzing microorganisms and a part thereof with organic solvents, alcohols, polyhydric alcohols, water, aqueous alcohols, etc .; pigments; fragrances; natural surfactants such as lanolin, cholesterol, saponin; alginic acid Polymer surface activity such as sodium, starch derivative, tragacanth rubber; purified water.

  Among them, the addition of a powder component is effective because it increases the detergency by the physical friction effect and tends to adsorb dirt on the particle surface.

  Further, since the oily component further contains an effect of solubilizing oily stains due to the solvent effect of the oily component, it is suitable for improving detergency. It is particularly effective to further include silicones among the oily components to give a refreshing feel after use.

  Furthermore, when the humectant is further contained, it is possible to suppress the roughening of the skin due to excessive degreasing, and tends to contribute to the improvement in use feeling.

  Further, the combined use with a sequestering agent or an antioxidant is effective in suppressing a change in a product under a long-term or severe use condition and continuing to provide a good feeling of use.

  Although not particularly limited, the cleaning composition of the present embodiment is suitable for cosmetic applications such as hair shampoo, body soap, facial cleansing foam, cleansing oil, cleansing cream, cleansing lotion, cleansing milk, and toothpaste. Further, the detergent composition of the present embodiment is a kitchen sink, tableware, a bath, a table, a desk, furniture, daily necessities such as stationery, clothing, ornaments, watches, bags, personal items such as shoes, copying machines, Office supplies such as printers, rain gear such as umbrellas, wings, etc., vehicles such as bicycles, motorcycles, aircraft, ships, etc., space engineering equipment such as rockets and satellites, medical equipment such as MRI and ultrasonic devices, electronic boards, displays, It can be used for various purposes such as electronic materials such as solar cells, lithium ion batteries, and electrodes, and electronic devices such as televisions, telephones, mobile phones, smartphones, and personal computers. The container of the cleaning composition of the present embodiment is not particularly limited, and for example, a general-purpose container such as a tube, a pump-type bottle, and a cream jar can be employed.

(Production method of detergent composition)
The method for producing the cleaning composition of the present embodiment includes the following steps.
(1) The first step of performing a condensation reaction between an acidic amino acid and a fatty acid chloride in a mixed solvent substantially consisting of water and t-butanol in the presence of an alkaline compound for 5.0 to 60 hours to obtain a reaction solution ( Hereinafter, it is also referred to as “acylation reaction step”.)
(2) A second step in which the obtained reaction solution is adjusted to pH 1 to 6 with an acid and separated into an organic layer and an aqueous layer at a temperature of 35 to 80 ° C to obtain an organic layer containing an N-acyl acidic amino acid. (Hereinafter, also referred to as “acid precipitation step”)
(3) The obtained organic layer was mixed with water and / or t-butanol, separated into a water layer and an organic layer containing an N-acyl acidic amino acid at a temperature of 35 to 80 ° C. to remove impurities. Third step of obtaining an organic layer containing an N-acyl acidic amino acid (hereinafter, also referred to as "water washing step")
(4) The obtained organic layer is neutralized with at least 1/20 of the amount of carboxyl groups of the N-acyl acidic amino acid, and the organic layer is heated under the condition that the temperature of the organic layer is 90 ° C. or lower and water is added during distillation. The fourth step of distilling off the organic solvent while maintaining the solid content concentration in the layer at 5.0 to 50% by mass with respect to the total amount (100% by mass) of the organic layer (hereinafter referred to as "solvent distilling step") Also called.)

[First step: acylation reaction step]
The acylation reaction step of the present embodiment is a step of performing a condensation reaction between an acidic amino acid and a fatty acid chloride in a mixed solvent of water and t-butanol in the presence of an alkaline compound. As a result, a crude N-acyl acidic amino acid is produced. Further, the reaction solution obtained by the condensation reaction is also referred to as “acylation reaction solution”.

  In the present embodiment, the time of the acylation reaction step is defined as the time when the acidic amino acid, the fatty acid chloride, and the alkaline compound start to coexist in the solvent, and the acid is added for the next acid precipitation step. It means the time until you start to do it. By making the time of the acylation reaction step 5.0 hours or more, the fatty acid t-butyl ester is substantially produced. In addition, since the time of the acylation reaction step is 60 hours or less, the decomposition of the fatty acid t-butyl ester once generated is suppressed, and the obtained detergent composition substantially converts the fatty acid t-butyl ester. Including. 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 even more preferably 0.98 or less. When the molar ratio of the fatty acid halide to the acidic amino acid is 1.05 or less, the amount of free fatty acid produced tends to be easily reduced.

  As the composition of the mixed solvent in the acylation reaction step, the volume ratio of water to t-butanol (water / t-butanol) is preferably in the range of 90/10 to 20/80, and more preferably 85/15. ５０50/50. When the ratio is in the range of 90/10 to 20/80, the acidic amino acid, the fatty acid chloride, and the alkaline compound are easily compatible with each other, and the reaction rate can be increased.

  The charge concentration of the acidic amino acid in the acylation reaction step is not particularly limited, but since the viscosity of the reaction solution increases with time during the reaction, the charge concentration is adjusted to such an extent that stirring and mixing can be performed at a point near the end of the reaction. Is preferred.

  The reaction temperature of the acylation reaction step is not particularly limited, but is preferably in the range of -10 to 70C, more preferably in the range of -10 to 20C, from the viewpoint of accelerating the main reaction and suppressing the side reaction. Preferably it is in the range of -5.0 to 10C.

  The alkaline compound used in the acylation reaction step is not particularly limited, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide.

  From the viewpoint of accelerating the main reaction and suppressing the side reaction, the pH in the acylation reaction step is preferably maintained at 9 to 13.5, more preferably 10 to 13.

[Second step: acid precipitation step]
In the acid precipitation step of the present embodiment, the acylation reaction solution is adjusted to pH 1 to 6 with an acid (preferably mineral acid) such as hydrochloric acid or sulfuric acid, and separated into two layers, an organic layer and an aqueous layer. This is a step of obtaining an organic layer. In the acylation reaction solution, the produced N-acyl acidic amino acid exists in the form of an alkali salt. By adding an acid thereto, part or all of the carboxyl group in the N-acyl acidic amino acid is converted into a free acid, whereby the organic layer and the aqueous layer are separated. Depending on the pH during the acid precipitation, the dissociation state of the carboxyl group changes, and the separation state, that is, the mass ratio between the organic layer and the aqueous layer and the removability of the inorganic salts slightly change. More preferably, the pH is from 1 to 2.5.

  The temperature in the acid precipitation step is preferably from 35 to 80 ° C. More preferably, it is 40 to 70 ° C. When the temperature is 35 ° C. or higher, the time until the separation reaches equilibrium can be shortened, and the remaining amount of the inorganic salt in the organic layer tends to be reduced when the equilibrium is reached. Since the boiling point of the azeotropic composition of water / t-butanol at normal pressure is around 80 ° C., boiling at 80 ° C. or less is prevented, so that separation under pressure is not required and the apparatus is simplified. This is advantageous in terms of conversion.

  The time of the acid precipitation step means a standing time at a predetermined pH and temperature. The standing time is not limited, but is preferably 0.1 to 10 hours from the viewpoint of sufficiently separating the organic layer and the aqueous layer and suppressing the decomposition of the fatty acid t-butyl ester. More preferably, it is 0.2 to 5.0 hours.

[Third step: washing step]
The water washing step of the present embodiment is a step in which water-soluble impurities in the organic layer obtained in the acid precipitation step are transferred into the water layer by a liquid-liquid extraction method to reduce the amount. Specifically, water and / or t-butanol are added to the organic layer after the acid precipitation step to adjust the composition of the N-acyl acidic amino acid / t-butanol / water, and the aqueous solution in the organic layer is extracted by liquid-liquid extraction. The acidic impurities, mainly the inorganic salts generated in the acylation reaction step and the acid precipitation step, are transferred into the aqueous layer.

  In the water washing step, the water washing temperature is preferably 35 to 80 ° C, more preferably 40 to 70 ° C. By setting the water washing temperature to 35 ° C. or higher, the time until the separation reaches equilibrium does not increase, and even when the equilibrium is reached, the inorganic salt hardly remains in the organic layer. Separation tends to be easy regardless of the middle concentration. In addition, since the boiling point of the azeotropic composition of water / t-butanol is around 80 ° C., by setting the washing temperature to 80 ° C. or less, boiling hardly occurs, and it is necessary to use a layer under pressure and a special device. Tends to be small.

[Fourth Step: Solvent Evaporation Step]
In the solvent distillation step of the present embodiment, the distillation operation is performed as an N-acyl acidic amino acid salt, but the salt is not particularly limited, and an alkali metal salt such as sodium, potassium, and lithium, calcium, Examples thereof include alkaline earth metal salts such as magnesium, aluminum salts, zinc salts, ammonium salts, organic amine salts such as monoethanolamine, diethanolamine / triethanolamine and triisopropanolamine, and basic amino acid salts such as arginine and lysine. From the viewpoints of performance and availability of the detergent composition, alkali metal salts and triethanolamine salts are preferred. To convert the N-acyl acidic amino acid into an amine salt or an alkali metal salt, for example, an alkali or an aqueous solution thereof may be added. When forming an N-acyl acidic amino acid salt, it is preferable to add the salt so that at least 1/20 of the carboxyl group content in the N-acyl acidic amino acid becomes 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 solution tends to be suitably improved. The ratio of the alkali salt is more preferably added so as to be at least 1/10 of the carboxyl group content, and further preferably so as to be at least 1/3.

  The temperature in the solvent distillation step is preferably 90 ° C. or lower. When the temperature is 90 ° C. or lower, the decomposition reaction of the N-acyl acidic amino acid or a salt thereof is suppressed, and the product quality tends to be kept good. The temperature is more preferably 80 ° C or lower, and further preferably 70 ° C or lower.

  In the present embodiment, the time in the solvent distillation step refers to the time from when the solvent starts to be distilled at a predetermined temperature, when t-butanol in the product reaches a predetermined concentration or less, and when the solvent distillation operation is stopped. means. The solvent distillation time is not particularly limited, but is preferably 1.0 to 60 hours from the viewpoint of suppressing foaming of the detergent composition and suppressing decomposition of the fatty acid t-butyl ester. More preferably, it is 5.0 to 40 hours.

  In the solvent distillation step, water is lost together with t-butanol, so distillation is performed while adding water. Examples of the method include intermittent or continuous addition of water, hot water, or steam.

  In the solvent distillation step, the solid concentration in the liquid at the time of distillation is maintained at 5.0 to 50% by mass with respect to the total amount (100% by mass) of the solution by performing distillation while adding water. I do. When the solid content concentration is 50% by mass or less, it is possible to suppress the viscosity and solidification of the liquid, and to suppress the occurrence of a decomposition reaction of the N-acyl acidic amino acid or a salt thereof due to overheating. When the solid concentration is 5.0% by mass or more, the concentration of t-butanol can be prevented from excessively decreasing and the distillation efficiency can be prevented from decreasing. This is preferable because concentration may not be required. The solid content concentration is more preferably 20 to 40% by mass, and still more preferably 25 to 35% by mass.

  In the solvent distillation step, t-butanol is preferably removed to such an extent that the t-butanol does not affect the scent of the product. From this viewpoint, 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 with respect to the N-acyl acidic amino acid. And more preferably 0.1 to 150 ppm by mass.

(Foaming persistence of the detergent composition)
By using the cleaning composition of the present embodiment, not only the foaming power is excellent, but also the generated foam is stable for a long time. The cleaning composition of the present embodiment preferably maintains a height of 60% or more from the height of foam at the time of foaming, and 5% after foaming under predetermined conditions, and 80% or more. Is more preferably maintained. Such performance is exhibited by a detergent composition containing at least the component (A) and the component (B), and a detergent composition comprising the component (A), the component (B), and the component (C). (A) Detergent composition comprising component (B), component (C) and component (D), detergent composition comprising component (A), component (B), component (C) and component (E) The present invention is exerted in any of the detergent compositions composed of a product, component (A), component (B), component (C), component (D), and component (E).

  The cleaning composition of the present embodiment has a high foaming sustainability, which further changes the foam quality of the cleaning composition, imparts a firm elasticity to the foam, and provides fine foam. It is in.

  Hereinafter, the present embodiment will be described more specifically with reference to specific examples and comparative examples.However, the present embodiment is not limited by these examples and comparative examples unless it exceeds the gist thereof. Absent.

<Analytical method for fatty acid t-butyl ester (GC / MS analysis)>
Fatty acid t-butyl ester was analyzed by GC / MS analysis using the following gas chromatograph and mass spectrometer.
・ Gas chromatograph (GC)
Apparatus: Agilent Technology 7890B
Column: SUPELCO Equity-1 (30 m × 0.25 mmΦ) Film thickness 0.25 μm
Temperature conditions: 40 ° C (5 min) → 10 ° C / min → 320 ° C
Flow rate: 1 mL / min
Injection volume: 1 μL
Inlet: 320 ° C Split 1:10
・ Mass spectrometer (MS)
Apparatus: Agilent Technology 7000
Ionization: EI 70 eV
Scan mode: TIC method (m / z = 10-800)
Ion source temperature: 250 ° C

<Evaluation method of foaming power and foaming sustainability>
For each of the detergent compositions shown in Examples and Comparative Examples, an aqueous solution diluted with water so as to have a solid content of 0.33% by mass was put into a juicer mixer and stirred for 30 seconds. The height was measured, and the foaming height immediately after and 5 minutes later was defined as the foaming power. Further, the ratio (%) of the height of foaming after 5 minutes to the height of foaming immediately after was calculated, and the foaming sustainability was evaluated according to the following criteria.
◎: 80% or more ○: 60 to less than 80% △: 60% or less

<Evaluation method of foam fineness>
For each of the detergent compositions shown in Examples and Comparative Examples, an aqueous solution diluted with water such that the solid content was 0.33% by mass was visually observed for the appearance of foam obtained by the Rossmile method. The fineness of the foam was evaluated according to criteria.
A: There are no coarse bubbles and there are many fine bubbles.
：: There are few coarse bubbles, but slightly coarse bubbles are mixed with fine bubbles.
Δ: There are not many coarse bubbles but a considerable amount, and coarse bubbles are mixed with fine bubbles.
×: Many coarse bubbles.

<Evaluation method of foam elasticity>
For each of the detergent compositions shown in Examples and Comparative Examples, an aqueous solution diluted with water so as to have a solid content of 0.33% by mass was touched with a foam obtained by the Rossmile method, and foamed according to the following criteria. Was evaluated for its elasticity.
：: The foam has considerable elasticity, and the foam also has a sense of dust.
：: The foam has considerable elasticity, but the foam has little dustiness.
Δ: The foam has elasticity, but the elasticity is weak.
×: The foam has no elasticity.

<Evaluation method for detergency>
A dish was coated with 1 g of commercially available butter, and each of the detergent compositions shown in Examples and Comparative Examples was washed using a solution diluted with water so that the solid content was 0.1% by mass. The condition of the dish was observed, and the detergency was evaluated according to the following criteria.
A: Butter oil does not remain on the plate.
：: Butter oil remains slightly.

<Analysis of free fatty acids (HPLC analysis)>
The free fatty acids were measured from the peak area obtained by the following analysis using 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 silica gel having a particle size of 5 μm and a pore size of 12 nm modified with an octadecylsilyl group.
Separation tube temperature: constant temperature around 40 ° C. Mobile phase: methanol / water / dioxane / phosphoric acid = 2000/400/49 / 0.62
Flow rate: A certain amount around 0.8 mL per minute

More specifically, free fatty acids (%) were calculated from the respective peak area areas of acyl amino acid salts and fatty acids obtained by analysis using HPLC, using the following formula.
Free fatty acid (%) = peak area of fatty acid / area of peak area of acyl amino acid salt × 100

<Viscosity>
For each of the detergent compositions shown in the examples and comparative examples, the viscosity at 25 ° C. was measured using a B-type viscometer.

<Synthesis of fatty acid t-butyl ester>
[Synthesis Example 1] Synthesis of t-butyl laurate laurate (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-methylmorpholine (3.2 g, 0.032 mol) were dissolved in t-butanol (228 g) and reacted at 50 ° C. for 20 hours. The reaction solution was analyzed by the above-mentioned analysis method, and formation of t-butyl laurate was confirmed (yield 73%).

<Synthesis of N-acyl acidic amino acid salt>
[Comparative Example 1]
(Acylation step)
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% by mass aqueous t-butanol solution was added, and the solution was maintained at 3 ° C. While adjusting the pH to 12 with 25% by mass sodium hydroxide, 1210 g (about 5.2 mol) of lauroyl chloride was added dropwise with stirring. The duration of the acylation step was 2.5 hours.

(Acid precipitation process)
After adding 1136 g of an 80% by mass aqueous solution of t-butanol, 75% sulfuric acid was added dropwise to adjust the pH of the solution to 2 and the temperature of the solution to 45 ° C., and allowed to stand for 1.0 hour to form an organic layer. After separating into a water tank, the organic layer was separated.

(Washing process)
A 20% by mass aqueous solution of t-butanol having the same mass as the organic layer was added to the separated organic layer, stirred, and allowed to stand at 45 ° C. for 1 hour to separate the organic layer and the aqueous layer.

(Solvent distilling step)
Sodium hydroxide is added to the organic layer so that 83% of the carboxyl groups of N-lauroyl-L-aspartic acid in the separated organic layer are in the form of a salt, and the solid content is adjusted to 25% by mass. To which pure water was added. Thereafter, vacuum distillation was performed at 70 ° C. for 20 hours using a spray evaporator while adding pure water so as to maintain the solid content at 25% by mass, to obtain an aqueous solution of sodium N-lauroyl-L-aspartate. (98% yield). Table 1 shows the composition of the aqueous solution (detergent composition).

[Examples 1 to 6 and 12]
To the aqueous solution of N-lauroyl-L-aspartic acid obtained in Comparative Example 1, t-butyl laurate was mixed so as to have the composition shown in Table 1, to prepare a detergent composition. In addition, Table 1 shows the foaming power and foaming sustainability of the obtained detergent composition. Since Examples 1 to 6 contained a fatty acid t-butyl ester, it was at least confirmed that a result having excellent foaming sustainability was obtained as compared with Comparative Example 1 not containing the ester.

[Example 7]
(Acylation step)
To a mixed solution of 1444 g (7.72 mol) of monosodium L-glutamate monohydrate, 3070 g of pure water, and 1235 g (7.72 mol of sodium hydroxide) of a 25% aqueous sodium hydroxide solution, 1647 mL of an 80% by mass t-butanol aqueous solution was added. While maintaining this solution at 3 ° C., 1760 g (7.56 mol) of cocoyl chloride was added dropwise with stirring while adjusting the pH to 12 with 25% sodium hydroxide. The duration of the acylation step was 6.0 hours.

(Acid precipitation process)
The pH value of the solution was adjusted to 2 by adding 75% sulfuric acid, and the temperature of the solution was adjusted to 65 ° C .. The solution was allowed to stand for 1 hour to separate an organic layer and an aqueous layer, and then the organic layer was separated. .

(Washing process)
T-Butanol and water are added to the separated organic layer to prepare a composition of N-cocoyl-L-glutamic acid / t-butanol / water = 33/25/42% by mass. The mixture was allowed to stand for 0 hour to separate into an organic layer and an aqueous layer.

(Solvent distilling step)
Triethanolamine is added to the organic layer so that 50% of the carboxyl group of N-cocoyl-L-glutamic acid in the separated organic layer is in the form of a salt, and the solid content is further adjusted to 30% by mass. Pure water was added. Thereafter, using a spray evaporator, vacuum distillation was performed at 70 ° C. for 20 hours while adding pure water so as to maintain the solid content at 30% by mass, and N-cocoyl-L-glutamic acid triethanolamine aqueous solution was added. (97% yield). Table 1 shows the composition of the aqueous solution (detergent composition).

Example 8
An aqueous solution containing 30% by mass of N-cocoyl-L-glutamic acid was obtained under the same conditions as in Example 7 except that the time of the acylation step was changed to 30 hours (yield 98%). Table 1 shows the composition of the aqueous solution (detergent composition).

[Example 9]
An aqueous solution containing 30% by mass of N-cocoyl-L-glutamic acid was obtained under the same conditions as in Example 7 except that the time for the acylation step was 55 hours (yield 97%). Table 1 shows the composition of the aqueous solution (detergent composition).

[Example 10]
(Acylation step)
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% by mass aqueous t-butanol solution was added, and the solution was maintained at 3 ° C. While adjusting the pH to 12 with 25% by mass sodium hydroxide, 1210 g (about 5.2 mol) of lauroyl chloride was added dropwise with stirring. The duration of the acylation step was 32 hours.

(Acid precipitation process)
After adding 1136 g of an 80% by mass aqueous solution of t-butanol, 75% sulfuric acid was added dropwise to adjust the pH of the solution to 2 and the temperature of the solution to 45 ° C., and allowed to stand for 1.0 hour to form an organic layer. After separating into a water tank, the organic layer was separated.

(Washing process)
To the separated organic layer, a 20% by mass aqueous solution of t-butanol having the same mass as the organic layer was added, stirred, and allowed to stand at 45 ° C. for 1.0 hour to separate the organic layer and the aqueous layer.

(Solvent distilling step)
Sodium hydroxide is added to the organic layer so that 83% of the carboxyl groups of N-lauroyl-L-aspartic acid in the separated organic layer are in the form of a salt, and the solid content is adjusted to 25% by mass. To which pure water was added. Thereafter, vacuum distillation was performed at 70 ° C. for 20 hours using a spray evaporator while adding pure water so as to maintain the solid content at 25% by mass, to obtain an aqueous solution of sodium N-lauroyl-L-aspartate. (98% yield). Table 1 shows the composition of the aqueous solution (detergent composition).

[Example 11]
An aqueous solution of sodium N-lauroyl-L-aspartate was obtained under the same conditions as in Example 10 except that the time for the acid precipitation step was 15 hours and the time for the solvent distillation step was 80 hours (yield). 95%). Table 1 shows the composition of the aqueous solution (detergent composition).

[Example 12]
An aqueous solution of sodium N-lauroyl-L-aspartate was obtained under the same conditions as in Example 10 except that the time for the acid precipitation step in the acylation step was set to 15 hours and the time for the solvent distillation step was set to 80 hours. (95% yield). Table 1 shows the composition of the aqueous solution (detergent composition).

Example 13
An aqueous solution was obtained by adding the free fatty acid of lauric acid to the composition obtained in Example 12 so as to be 5% by mass. Table 1 shows the composition of the aqueous solution (detergent composition).

[Comparative Example 2]
An aqueous solution containing 30% by mass of N-cocoyl-L-glutamic acid was obtained under the same conditions as in Example 7 except that the time of the acylation step was changed to 2.5 hours (yield: 96%). Table 1 shows the composition of the aqueous solution (detergent composition).

[Comparative Example 3]
An aqueous solution containing 30% by mass of N-cocoyl-L-glutamic acid was obtained under the same conditions as in Example 7 except that the time of the acylation step was changed to 68 hours (96% yield). Table 1 shows the composition of the aqueous solution (detergent composition).

  Since Examples 10 to 13 follow the production method of the present embodiment, a composition containing fatty acid t-butyl ester or fatty acid is obtained, and the foaming sustainability, the fineness of the foam, the elasticity of the foam, and the cleaning power are improved. All were good. On the other hand, Comparative Examples 2 and 3 do not follow the production method of the present embodiment, so that a composition containing fatty acid t-butyl ester cannot be obtained, the amount of free fatty acids is large, foaming persistence, fineness of foam, Both of the elasticity and the detergency were inferior to those of Examples 10 to 13.

[Examples 14 to 21, Comparative Examples 4 and 5]
A cleaning composition having the composition shown in Table 2 was prepared, and the foaming durability and viscosity were evaluated. Since the cleaning compositions in Examples 14 to 21 contained the fatty acid t-butyl ester, the cleaning compositions were excellent in foaming durability and tended to have high viscosity. On the other hand, since the cleaning compositions in Comparative Examples 4 and 5 did not contain the fatty acid t-butyl ester, the foaming sustainability was inferior and the viscosity tended to be lower than those of Examples 14 to 21.

The product names and manufacturers corresponding to the components used in Table 2 (Note 1) to (Note 8) are shown below.
Note 1) Miyoshi Oil & Fat Co., Ltd. Anhorex LB-2
Note 2) Miyoshi Oil & Fat Co., Ltd. Amphorex CB-1
Note 3) Rikabion A-100, Shin Nippon Rika Co., Ltd.
Note 4) Obazoline BC by Toho Chemical Industry Co., Ltd.
Note 5) Kawaken Fine Chemical Co., Ltd. Amizole CME
Note 6) Kawaken Fine Chemical Co., Ltd. Amizole CDE
Note 7) Kao Corporation Aminone C-11S
Note 8) VISCO FINE E2S, Kawaken Fine Chemical Co., Ltd.

  This application is based on a Japanese patent application filed with the Japan Patent Office on April 14, 2016 (Japanese Patent Application No. 2016-084833), the contents of which are incorporated herein by reference.

  According to the detergent composition and the method for producing the same according to the present invention, in addition to the initial foaming power, “the foaming lasts longer”, “the foam elasticity”, and “the fineness of the foam texture”. And the like can provide a good cleaning composition.

Claims (4)

A cleaning composition comprising the following component (A) and the following component (B).
Component (A): N-acyl acidic amino acid represented by the following general formula (1) and / or the following general formula (2) and / or a salt thereof

(Wherein, R ₁ represents an alkyl group having 7 to 23 carbon atoms. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal or an alkaline earth metal, an organic or inorganic ammonium, a basic amino acid, Or M ₁ and M ₂ may be the same or different.)
Component (B): fatty acid t-butyl ester represented by the following general formula (3)

(In the formula, R1 represents an alkyl group having 7 to 23 carbon atoms.)   The cleaning composition according to claim 1, wherein the content of the component (B) is 0.01 mass ppm or more and 1000 mass ppm or less based on the mass of the component (A). It further contains the following component (C),
The cleaning agent according to claim 1, wherein the content of the component (C) as a free fatty acid is in the range of 0.1% by mass or more and 5% by mass or less based on the mass of the component (A). Composition.

(Wherein, R1 is .M ₃ represents an alkyl group having 7 to 23 carbon atoms is a hydrogen atom, an alkali metal or alkaline earth metal, an organic or inorganic ammonium, basic amino acid, or choline.) The cleaning composition according to any one of claims 1 to 3, further comprising the following component (D) and / or the following component (E).
(D): aliphatic amidopropyl betaine and / or alkyl betaine (E): nonionic surfactant