JPH07197078A - Polyoxyethylene fatty acid amide sulfosuccinic acid ester type surfactant, its production and detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject surfactant excelling in foaming power and detergency, lowly irritable to the skin or the hair and excelling in low- temperature properties. CONSTITUTION:This surfactant is a polyoxyethylene fatty acid amide sulfosuccinic acid salt type surfactant represented by formula II (wherein one of X<1> and X<2> is hydrogen, the other is an SO3M<2> group; and M<1> and M<2>, which are the same or different from each other, are each hydrogen, a cationic residue of an alkali metal, an alkaline earth metal atom, an ammonium group or an alkanolamine originated in the sulfonating agent or a cationic residue of a basic amino acid) and having a content of an amide ester represented by formula I (wherein RCO is a 6-22 C linear or branched saturated or unsaturated fatty acid residue; and (n) is integer of 1 or greater).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant excellent in foaming power / detergency, less irritating to skin and hair, and excellent in solubility, and the same. The present invention relates to a detergent composition containing

[0002]

2. Description of the Related Art Conventionally, anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates and α-olefin sulfonates have been widely used as surfactants for detergents. . However, all of these anionic surfactants have skin irritation to some extent, but when they are continuously used, they have a problem of roughening the skin.

In recent years, for the purpose of improving skin irritation, polyoxyethylene fatty acid amide sulfosuccinate salt type obtained by addition reaction of fatty acid monoethanolamide with ethylene oxide and chlorination of the ethylene oxide addition reaction product Surfactants have come into use.

However, the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant obtained by this method contains a compound which is insoluble in water, although it is excellent in terms of skin irritation and the like. When the content of the insoluble matter is high, the turbidity occurs at room temperature even when the content of the insoluble matter is relatively low, and the commercial value is lowered. Further, it cannot be said that the foaming power and the cleaning power are sufficient, and they are not satisfactory.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
It is intended to provide a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant having excellent detergency, less irritation to the skin and hair, and excellent solubility, and a detergent composition containing the same. .

[0006]

[Means for Solving the Problems] The present inventors
As a result of repeated studies to obtain a detergent composition having excellent detergency, less irritation to skin and hair, and excellent solubility, the conventional polyoxyethylene fatty acid amide sulfosuccinate salt type surfactant has It has been discovered that the defect is derived from an amide ester that is a by-product during the ethylene oxide addition reaction.

That is, the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant is manufactured through a step of adding ethylene oxide to fatty acid monoethanolamide. Causing a disproportionation reaction such that the amide ester (a) is present in the polyoxyethylene fatty acid amide.
And trialkanolamine (b) are by-produced.

[0008]

[Chemical 13]

This disproportionation reaction is remarkable when ethylene oxide is added at a temperature of 150 ° C. or higher. If the ethylene oxide addition temperature is lowered, the disproportionation reaction can be suppressed, but if the ethylene oxide addition temperature is lowered, the ethylene oxide addition reaction takes time. Further, when the fatty acid monoethanolamide as a raw material has a high melting point, it is not possible to add ethylene oxide at a temperature equal to or lower than the melting point because a heterogeneous reaction occurs.

Therefore, as long as ethylene oxide is added to the fatty acid monoethanolamide, it is unavoidable that this disproportionation reaction occurs and the amide ester by-produced in the polyoxyethylene fatty acid amide is mixed. It was

When this polyoxyethylene fatty acid amide containing an amide ester is subjected to sulfosuccinic acid esterification to obtain a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt, the amide ester does not react with the sulfosuccinic acid esterifying agent. As it was, it was mixed in the product polyoxyethylene fatty acid amide sulfosuccinate salt.

Since this amide ester has a high melting point, when it is present in a large amount, it causes turbidity or precipitation in the product polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant. In addition, since amide ester has almost no polarity and is poorly water-soluble, it is not sufficiently compatible with other surfactants, and turbidity due to amide ester may occur even in the formulation of detergents, which makes the product valuable. Had lowered. Furthermore, since the amide ester has low foaming power and detergency, the performance originally possessed by the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant has been deteriorated.

Therefore, the inventors of the present invention removed the amide ester by-produced from the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant to remove the conventional polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant. Focusing on the possibility that the drawbacks of amide can be eliminated, the results of our research have shown that by adding alkanolamine to polyoxyethylene fatty acid amide containing amide ester, the amide ester can be rapidly transferred and decomposed into polyoxyethylene fatty acid amide. It was found that a polyoxyethylene fatty acid amide containing no amide ester thus obtained was salinized with a sulfosuccinic acid ester to obtain a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant. Including It found that can solve Orazu above problems, and have completed the present invention.

That is, the present invention provides (1) general formula (1)

[0015]

[Chemical 14]

(In the formula, RCO is a linear or branched saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and n is 1
The content of the amide ester represented by the above integer is 1.5 wt% or less, the general formula (2)

[0017]

[Chemical 15]

(In the formula, RCO and n are as defined above. X
Any one of ¹ and X ² represents a hydrogen atom, and the other one is-
Represents a SO ₃ M ² group, and M ¹ and M ² are the same or independently of each other, hydrogen or an alkali metal atom, an alkaline earth metal atom, an ammonium group or a cationic residue of an alkanolamine contained in the sulfonating agent. Or represents a cationic residue of a basic amino acid), a polyoxyethylene fatty acid amide sulfosuccinate-type surfactant.

(2) The following general formula (3)

[0020]

[Chemical 16]

Ethylene oxide is added to the fatty acid monoethanolamide represented by the formula (wherein RCO represents a linear or branched, saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms) to give a compound of the general formula (4)

[0022]

[Chemical 16]

(Wherein RCO is as defined above, n is 1
A polyoxyethylene fatty acid amide represented by the above formula is produced, and the general formula (1) contained in the polyoxyethylene fatty acid amide.

[0024]

[Chemical 17]

0.8 to 0.8 with respect to the amide ester represented by the formula (wherein RCO and n are the same as defined above).
10-fold molar general formula (5)

[0026]

[Chemical 17]

An alkanolamine represented by the formula (wherein m represents an integer of 1 or more) is reacted with the amide ester of the general formula (1) to give the general formula (4) and the general formula (6).

[0028]

[Chemical 18]

After the transfer to the polyoxyethylene fatty acid amide represented by the formula (wherein RCO and m are the same as defined above), maleic anhydride is reacted to give a compound of the general formula (7)

[0030]

[Chemical 19]

A mono (polyoxyethylene fatty acid amide) maleic acid ester represented by the formula (wherein RCO and n are the same as defined above) is prepared, and alkali metal, alkaline earth metal, ammonia, alkanolamine and Acid containing a sulfite selected from at least one basic amino acid and / or a neutralizing agent selected from at least one alkali metal hydroxide, alkaline earth metal hydroxide, ammonia, alkanolamine and basic amino acid. A general formula (1), characterized in that a sulfonating agent comprising at least one selected from sulfite and / or acidic sulfite is reacted.

[0032]

[Chemical 20]

(Wherein RCO and n are the same as defined above), the content of the amide ester represented by the general formula (2) is 1.5 wt% or less.

[0034]

[Chemical 21]

(In the formula, RCO and n are as defined above. X
Any one of ¹ and X ² represents a hydrogen atom, and the other one is-
Represents a SO ₃ M ² group, and M ¹ and M ² are the same or independently of each other, hydrogen or an alkali metal atom, an alkaline earth metal atom, an ammonium group or a cationic residue of an alkanolamine contained in the sulfonating agent. Or represents a cationic residue of a basic amino acid), a process for producing a polyoxyethylene fatty acid amide sulfosuccinate-type surfactant.

(3) General formula (1)

[0037]

[Chemical formula 22]

(In the formula, RCO is a linear or branched saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and n is 1
The content of the amide ester represented by the above integer) is 1.5 wt% or less, and the general formula (2)

[0039]

[Chemical formula 23]

(In the formula, RCO and n are as defined above. X
Any one of ¹ and X ² represents a hydrogen atom, and the other one is-
Represents a SO ₃ M ² group, and M ¹ and M ² are the same or independently of each other, hydrogen or an alkali metal atom, an alkaline earth metal atom, an ammonium group or a cationic residue of an alkanolamine contained in the sulfonating agent. Or a polyoxyethylene fatty acid amide sulfosuccinate type surfactant represented by the formula (1) or a cationic residue of a basic amino acid).

(4) In the above item (3), the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type interface represented by the general formula (2), in which the content of the amide ester of the general formula (1) is 1.5 wt% or less. A detergent composition comprising an active agent and an anionic surfactant and / or an amphoteric surfactant.

The main points are as follows.

The polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant of the present invention is characterized in that the amide ester content is 1.5 wt% or less. The content of the amide ester of the general formula (1) means the content of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant of the general formula (2). The amide ester content is
A polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant exceeding 1.5 wt% is not preferable because one of foaming power, detergency, skin irritation and cold resistance is lowered.

The acyl group (RCO) constituting the fatty acid monoethanolamide represented by the general formula (3), which is a raw material of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant of the present invention, has 6 carbon atoms. 22 linear or branched saturated or unsaturated fatty acid residues, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, coconut oil fatty acid, Palm oil fatty acids,
Residues of fatty acids such as palm kernel oil fatty acid and hardened beef tallow fatty acid may be mentioned.

In the present invention, the general formulas (1), (2),
M and n in (4), (6) and (7) are integers of 1 or more representing a repeating unit of an oxyethylene group, but in consideration of the addition reaction of ethylene oxide, 1 to
The range of 100 is preferable, and the range of 1 to 21 is more preferable.

Examples of the polyoxyethylene fatty acid amide represented by the general formula (4) of the present invention include polyoxyethylene (3) coconut oil fatty acid amide, polyoxyethylene (6) coconut oil fatty acid amide, and polyoxyethylene ( 11) Coconut oil fatty acid amide, polyoxyethylene (2) lauric acid amide, polyoxyethylene (3) lauric acid amide, polyoxyethylene (4) lauric acid amide, polyoxyethylene (6) lauric acid amide,
Examples thereof include polyoxyethylene (11) lauric acid amide, polyoxyethylene (6) myristic acid amide, polyoxyethylene (11) stearic acid amide, and polyoxyethylene (21) oleic acid amide.

The amide ester content of the present invention is 1.
The production of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant of 5 wt% or less may be carried out as follows.

(Production Step of Polyoxyethylene Fatty Acid Amide) This step may be in accordance with the conventional method for producing polyoxyethylene fatty acid amide. For example, fatty acid monoethanolamide of the general formula (3) may be added with sodium methoxide. Ethylene oxide may be added at 80 to 200 ° C. in the presence of a base catalyst such as sodium ethoxide, and sodium hydroxide.

(Amide ester decomposition step) This step is
0.8 to 10 times mol of the general formula (5) with respect to the amide ester contained in the polyoxyethylene fatty acid amide
React with the alkanolamine of.

Examples of the alkanolamine of the general formula (5) used in the present invention include monoethanolamine, diglycolamine, triglycolamine, polyglycolamine and the like.

The method of the rearrangement reaction after adding the alkanolamine is not particularly limited, but the reaction temperature is preferably the melting point of the polyoxyethylene fatty acid amide or higher. This transfer reaction proceeds relatively easily, and is usually achieved by stirring at 20 to 150 ° C. for 10 minutes to 12 hours.

The amount of alkanolamine added is 0.8 to 10 times the molar amount of the amide ester in the polyoxyethylene fatty acid amide at the time when the ethylene oxide addition is completed. When the amount is less than 0.8 times, the total amount of amide ester cannot be converted into polyoxyethylene fatty acid amide and remains. Even if the amount exceeds 10 times the molar amount, the effect does not change, an excess amount of alkanolamine remains in the product, and maleic anhydride is simply required in the next maleic acid esterification step. In addition, the performance of the product polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant is deteriorated and it causes coloring over time, which is not preferable.

In this step, the transfer reaction can be promoted by adding a trace amount of base in addition to the alkanolamine. However, when ethylene oxide is added to the fatty acid monoethanolamide, a base catalyst is usually used, so it is not necessary to add a base catalyst.

When it is desired that the excess amount of the alkanolamine added in the transfer reaction remains, it is possible to remove the alkanolamine under reduced pressure after the completion of the reaction.
However, this case is limited to the case of using a low-boiling alkanolamine such as monoethanolamine or diglycolamine. However, if the amount of alkanolamine added is within the specified range, the amount of alkanolamine remaining in the polyoxyethylene fatty acid amide sulfosuccinate ester salt of the final product is usually small, which may affect the performance and stability of the product. No removal operation is required.

(Maleic Acid Esterification Step) This step may be in accordance with the conventional method for producing a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt. For example, in the polyoxyethylene fatty acid amide of the general formula (4),
0.9-1.4 times the molar amount of maleic anhydride 20-120
The reaction may be performed at 30 ° C. for 30 minutes to 6 hours.

(Sulfonation Step) This step may be in accordance with the conventional method for producing a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt, and may be a mono (polyoxyethylene fatty acid amide) maleic acid ester of the general formula (7). It may be reacted with a sulfonating agent.

As sulfonating agents, sulfite and /
Alternatively, an acidic sulfite and / or an acidic sulfite containing a neutralizing agent is used. For example, as the sulfite,
Sodium sulfite, potassium sulfite, magnesium sulfite, ammonium sulfite, triethanol sulfite and the like, examples of the acid sulfite, sodium acid sulfite, potassium acid sulfite and the like, as the neutralizing agent, an alkali metal (for example, sodium, Potassium etc.)
Hydroxide, alkaline earth metal (eg, magnesium) hydroxide, ammonia, alkanolamine (eg, triethanolamine), or basic amino acid (eg, lysine, arginine).

The sulfonating agent is preferably used in at least an equimolar amount or more, particularly in a 1.03 to 1.2-fold molar excess with respect to maleic anhydride.

The sulfonation reaction is carried out in the presence of water for 20 to 10
It is preferable to react at a temperature of 0 ° C. for 30 minutes to 5 hours,
An appropriate amount of water is 60 to 80% by weight based on the charged weight. A typical example of the polyoxyethylene fatty acid amide sulfosuccinate salt type surfactant represented by the general formula (2) obtained by the present invention is given below. , Polyoxyethylene (3) coconut oil fatty acid amide diammonium sulfosuccinate, polyoxyethylene (6) coconut oil fatty acid amide dipotassium sulfosuccinate, polyoxyethylene (1
1) Coconut oil fatty acid amide sodium sulfosuccinate triethanolamine, polyoxyethylene (6) lauric acid amide disodium sulfosuccinate, polyoxyethylene (6) myristic acid amide sodium ammonium sulfosuccinate, polyoxyethylene (11) stearic acid amide Examples thereof include sulfosuccinic acid dilysine salt and polyoxyethylene (21) oleic acid amide magnesium sulfosuccinate.

The amide ester content was 1.5 w.
As a method of producing a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant having a concentration of t% or less, a polyoxyethylene sulfosuccinic acid amide is treated by treating with low concentration alkaline water to hydrolyze only the ester group of the amide ester And a method of decomposing it into fatty acid soap, and a method of extracting amide ester from polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant containing amide ester.

A third aspect of the present invention relates to a detergent composition containing a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant having an amide ester content of 1.5 wt% or less. Specifically, a cleaning characterized by containing a polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant having an amide ester content of 1.5 wt% or less, and an anionic surfactant and / or an amphoteric surfactant. The present invention relates to an agent composition.

The content of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant having an amide ester content of not more than 1.5 wt% used in the detergent composition of the third invention in the detergent composition is , 0.05 ~
It is 40% by weight, more preferably 0.1 to 30% by weight.

When the content of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant having an amide ester content of 1.5 wt% or less in the detergent composition of the second invention is less than 0.05% by weight. However, the effect is not sufficient, and addition of more than 40% by weight is not preferable because the effect is not increased.

The polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant having an amide ester content of 1.5 wt% or less, which is obtained by the present invention, exhibits surface activity by itself, but other anionic interfaces By combining with an active agent and / or an amphoteric surfactant, its performance can be further improved. The component of the detergent containing a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant containing an amide ester which has been conventionally used is the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type interface obtained in the present invention. When replaced with an activator, the foaming power / detergency is improved, turbidity is not seen, and solubility and cold resistance are improved.

Examples of anionic surfactants used in the detergent composition of the present invention include fatty acid soaps such as sodium laurate and triethanolamine laurate, alkylbenzene sulfonates, α-olefin sulfonates, sodium lauryl sulfate, Lauryl sulfate triethanolamine and other lauryl sulfates, polyoxyethylene (3) sodium lauryl ether sulfate and other ether sulfates, polyoxyethylene (3) coconut oil fatty acid amide amide sulfate and other amide ether sulfates, monododecyl phosphate trioxide Phosphate esters such as ethanol, sodium polyoxyethylene dodecyl ether phosphate, di- (polyoxyethylene (6) coconut oil fatty acid amide) -sodium phosphate, cocoyl methyl taurine sodium, lauroyl methyl Acylmethyltaurine salts such as Gaulin sodium acyl isethionates such as sodium lauroyl isethionate, sodium lauryl sulfosuccinate, disodium POE (1 to 4) sodium lauryl sulfosuccinate disodium, sulfosuccinic acid type surfactants such as,
Alkyl ether carboxylates, cellulose derivatives such as carboxymethyl cellulose, N-acyl sarcosine salts such as cocoyl sarcosine sodium, lauroyl sarcosine sodium, myristoyl sarcosine sodium, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine, cocoyl-N-methyl-β.
-Sodium alanine, lauroyl-N-methyl-β-
Alanine sodium, myristoyl-N-methyl-β-
Alanine sodium, palmitoyl-N-methyl-β-
Alanine sodium, stearoyl-N-methyl-β-
N-acyl-β-alanine salts such as sodium alanine, lauroyl-N-methyl-β-alanine potassium, lauroyl-N-methyl-β-alanine triethanolamine, sodium N-lauroyl aspartate, N-
Lauroyl aspartic acid triethanolamine, N-
N-acyl aspartates such as sodium myristoyl aspartate, sodium N-lauroyl glutamate, triethanolamine N-lauroyl glutamate, sodium N-cocoyl glutamate, N-acyl glutamate such as triethanolamine N-cocoyl glutamate, N- 2-hydroxyethyl-N-2
-Lauric acid amidoethylglycine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amidoethylglycine, N-2-hydroxyethyl-N-2-lauric acid amidoethyl-β-alanine, N-2-hydroxyethyl -N-2-coconut oil fatty acid amide ethyl-β-alanine,
N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) lauric acid amido] ethyl} glycine,
N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, N- {2- [N- (2-hydroxyethyl) lauric acid amide] ethyl} glycine , N- {2- [N- (2
Examples include amide carboxylic acid type surfactants such as -hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine.

Examples of the amphoteric surfactant used in the detergent composition of the present invention include alkyl betaine type amphoteric surfactants such as lauryl betaine, amido betaine type amphoteric surfactants such as lauroyl amidopropyl betaine, and 2-alkyl- Imidazoline-type amphoteric surfactants such as N-carboxymethylimidazolinium betaine and 2-alkyl-N-carboxyethylimidazolinium betaine, alkylsulfobetaine-type amphoteric surfactants, coconut oil fatty acid amide dimethylhydroxypropylsulfobetaine, etc. Amidosulfobetaine type amphoteric surfactants and the like can be used.

In the detergent composition of the present invention, a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant and an anionic surfactant and / or an amphoteric surfactant having an amide ester content of 1.5 wt% or less. The compounding ratio with is preferably 20: 1 to 1:20, and the total content of each component is preferably 0.1% or more. If the compounding ratio of the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant having an amide ester content of 1.5 wt% or less and the anionic surfactant and / or amphoteric surfactant is outside the above range, the foaming power is obtained.・
The detergency is not sufficient and the total content of each component is 0.1
If it is less than wt%, the effect is not sufficient. Further, in the detergent composition of the present invention, the following additional components can be used if necessary. Examples of the additional component include fatty acid diethanolamide such as coconut oil fatty acid diethanolamide and lauric acid diethanolamide, fatty acid monoethanolamide such as coconut oil fatty acid monoethanolamide and lauric acid monoethanolamide, coconut oil fatty acid diglycolamide and lauric acid. Fatty acid diglycolamide such as diglycolamide, fatty acid isopropanolamide such as lauric acid isopropanolamide, fatty acid ester, alkylamine oxide such as lauryldimethylamine oxide, POE higher alcohol ether, POE alkylphenyl ether, alkylglucoside such as decylglucoside, etc. Nonionic surfactants, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, disterate Quaternary ammonium salt cationic surfactants such as Lil dimethyl ammonium, cationized polymers and cationic guar gum and the like.

The following additional components can also be used if necessary. Examples of these additional components include polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, silicones such as methylpolysiloxane and oxyalkylene-modified organopolysiloxane, zinc pyrithione and piroctone olamine. Antidandruff agents, hyaluronic acid, collagen, elastin chondroitin sulfate, dermatanic acid, water-soluble polymer substances such as fibronectin, ceramides, chitin, chitosan, cell activating agents such as aloe extract, placenta extract, allantoin, glycyrrhizinate, etc. Anti-inflammatory agent, edetate, pyrophosphate, hexametaphosphate, citric acid, malic acid, chelating agent such as gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2 4,4'-trichloro-2'-hydroxy-diphenyl ether, 3,
Preservatives such as 4,4'-trichlorocarbanito, benzalkonium chloride, hinokitiol and resorcin, bactericides, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate and ascorbic acid, fragrances and pigments Can be mentioned.

When the detergent of the present invention is used as a shampoo, it is generally in the form of liquid or paste (gel), and its appearance is transparent, pearl, or emulsion, but is not limited thereto. Not something. In order to produce the detergent of the present invention, a compounding method generally used by those skilled in the art may be used.

The application is optional, but typical examples thereof include detergents such as kitchen detergents, hard surface cleaners, facial cleansers, cleansing foams, shampoos and body shampoos.

[0071]

Function: The amide ester content of the present invention is 1.5w.
The reason why the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant of t% or less is excellent in foaming power / cleansing power, less irritating to skin and hair, and excellent in solubility is that the interface of the present invention is used. This is because the amide ester undergoes a rearrangement reaction as described below during the production of the activator.

That is, when the amide ester by-produced in the ethylene oxide addition reaction is reacted with an alkanolamine, the acyl group on the ester group side of the amide ester becomes an amino group of the alkanolamine as shown in the reaction formula. A transfer reaction occurs.

[0073]

[Chemical formula 24]

By this transfer reaction, the amide ester is almost quantitatively converted into polyoxyethylene fatty acid amide.

If only the amide ester is decomposed, it is possible to hydrolyze only the ester group of the amide ester by treating with a low-concentration alkaline water to decompose it into polyoxyethylene fatty acid amide and fatty acid soap. is there. However, this method produces a small amount of irritating fatty acid soap. Further, the total amount of amide ester by-produced by the addition of ethylene oxide is not converted into polyoxyethylene fatty acid amide, which is not efficient.

According to the present invention, an excess fatty acid soap is not formed and the by-produced amide ester can be directly converted into a polyoxyethylene fatty acid amide again. Therefore, the by-product amide ester can be effectively used. it can.

Further, from the polyoxyethylene fatty acid amide sulfosuccinate ester type surfactant containing an amide ester obtained by the conventional production method, only the amide ester is removed by extraction with a solvent such as ethyl acetate. Even in this case, it is possible to obtain the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt-type surfactant having an amide ester content of 1.5 wt% or less according to the present invention. Since the amide ester has almost no solubility in water, it is possible to relatively easily separate the amide ester and the polyoxyethylene fatty acid amide sulfosuccinate salt type surfactant by using an extraction solvent such as ethyl acetate. However, this method must use a flammable or volatile solvent, requires an extra step of extraction, and requires topping after extraction, which is not suitable for an industrial production method.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[0079]

The present invention will be described in more detail with reference to the following examples.

Production Example 1 Monoethanolamine 61 was added to 214 g of methyl laurate.
g and 0.5 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while stirring with heating (20 m
mHg, 90 ° C., 1 hour), and 244 g of lauric acid monoethanolamide was obtained. To this, ethylene oxide 2
After adding 20 g, the mixture was reacted in an autoclave at 150 ° C. for 1 hour to give polyoxyethylene (6) lauric acid amide 4
64 g was obtained.

¹ H-NMR analysis was performed to determine the amide ester content of this product. That is, when the TMS is used as the internal standard, the methylene group of -CH2-OCO-R of the amide ester is characteristically observed as a triplet at δ 4.2 ppm, so it is easily distinguished from other signals. It Integral value of CH3 group at δ 0.88 ppm and δ 4.2
The amide ester content can be easily calculated from the integrated value of the ppm signal. Moreover, although it can be analyzed by IR analysis, it is not suitable for quantification. However, it is suitable for making a judgment as to whether or not an amide ester is present. That is, the presence or absence of the amide ester can be determined by the presence or absence of absorption of C═O stretching of the ester group of the amide ester at 1730 cm ⁻¹ .

The results of ¹ H-NMR analysis and the amide ester content are shown below.

¹ H-NMR (250 MHz, CDCl ₃ ,
Internal standard TMS) The signal of δ 0.88 ppm (t, CH ₃ ) is set to 3H, and each signal is integrated δ 4.22 ppm (t, 0.13H, —CH ₂ —OCO).
-C ₁₁ H ₂₃₎ amide ester content: 7 Amide ester content from the integral value of the mole% NMR signals were found by the following formula.

[0084]

[Equation 1]

Comparative Example 1 464 g of polyoxyethylene (6) lauric acid amide containing amide ester obtained in Production Example 1 was heated to 40 ° C. to uniformly dissolve it, and 100 g of maleic anhydride was added to this solution. In addition, the mixture was heated and stirred under a nitrogen stream at 65 ° C. for 1 hour to form a maleic acid ester. To the obtained mono (polyoxyethylene (6) lauric acid maleate) was added dropwise a 15 wt% sodium sulfite aqueous solution prepared by dissolving 138.6 g of anhydrous sodium sulfite in 786 g of purified water at 20 ° C over 10 minutes, and then at 60 ° C. The mixture was stirred for 4 hours and sulfonated to synthesize polyoxyethylene (6) lauric acid amide disodium sulfosuccinate (anionic active ingredient:
30%). This was cloudy at room temperature.

TLC analysis (silica gel, developing solution: chloroform / methanol / aqueous ammonia = 100/35 /
The presence or absence of amide ester was examined in 8). As a result, Rf
A spot of amide ester was observed at 0.91.

Then, the obtained polyoxyethylene (6)
Lauric acid amide disodium sulfosuccinate 100 g
Was extracted 3 times with 100 ml of ethyl acetate, the ethyl acetate layer was washed with water, dried over magnesium sulfate, and then the solvent was removed to obtain 2.1 g of an amide ester crystal. This corresponds to 6.9% by weight of polyoxyethylene (6) lauric acid amide disodium sulfosuccinate, which is sulfosuccinic acid salt of polyoxyethylene (6) lauric acid amide. Was assumed to remain unreacted (6.9%).
It was found that the amide ester in the polyoxyethylene fatty acid amide did not undergo sulfosuccinate ester salification and remained in the product polyoxyethylene fatty acid amide sulfosuccinate salt as it was.

Production Example 2 31 g of monoethanolamine and 0.3 g of sodium methoxide were added to 119 g of coconut oil fatty acid methyl obtained by methyl esterifying coconut oil fatty acid (C6 to C22) by a conventional method, and methanol was distilled off under reduced pressure. While heating and stirring (2
(0 mmHg, 100 ° C., 2 hours), coconut oil fatty acid monoethanolamide was synthesized. To this, 44 g of ethylene oxide was added and reacted in an autoclave at 130 ° C. for 2 hours to obtain polyoxyethylene (3) coconut oil fatty acid amide. 1H-NMR analysis (250MH
z, CDCl3) was carried out and the amide ester content was calculated to find that it contained 5.0 mol% of amide ester.

Comparative Example 2 To 135 g of polyoxyethylene (3) coconut oil fatty acid amide containing amide ester obtained in Production Example 50 was added 50 g of maleic anhydride, and the mixture was stirred at 50 ° C. for 2 hours to form a maleic acid ester. . To the obtained mono (polyoxyethylene (3) coconut oil fatty acid amide) maleate, 117 g of magnesium sulfite hexahydrate was dissolved in purified water 18
A weight% magnesium sulfite aqueous solution was added dropwise at 20 ° C. over 10 minutes, and then heated and stirred at 60 ° C. for 5 hours to be sulfonated to synthesize polyoxyethylene (3) coconut oil fatty acid amide magnesium sulfosuccinate (anionic active ingredient: 26%) 100 g of the obtained polyoxyethylene (3) coconut oil fatty acid amide magnesium sulfosuccinate was added to ethyl acetate 10%.
The mixture was extracted 3 times with 0 ml, the ethyl acetate layer was washed with water, dried over magnesium sulfate, and then the solvent was removed to obtain 1.3 g of amide ester crystals. This corresponded to 5.0% by weight of pure polyoxyethylene (3) coconut oil fatty acid amide magnesium sulfosuccinate. This was almost the same as the content (5.1% by weight) of polyoxyethylene (3) coconut oil fatty acid amide, which was assumed to remain without being reacted in the sulfosuccinic acid esterification.

Reference Example 1 In the ethylene addition reaction of Production Example 2, the time required for the ethylene oxide addition reaction and the amide ester content in the polyoxyethylene (3) coconut oil fatty acid amide were changed by changing the temperature of the ethylene oxide addition reaction. Was investigated. The results are shown in Table 1.

[0091]

[Table 1]

From these results, it can be seen that the higher the ethylene oxide addition temperature, the shorter the ethylene oxide addition reaction time, but the higher the amide ester content. It is also found that even if the reaction temperature is lowered, a small amount of amide ester is produced. Since the melting point of coconut oil fatty acid monoethanolamide, which is a raw material for ethylene oxide addition, is 70 ° C, it is substantially difficult to add ethylene oxide at a temperature lower than 80 ° C. Therefore, it is understood that the formation of amide ester is unavoidable as long as the ethylene oxide addition reaction is carried out.

Example 1 To 464 g of polyoxyethylene (6) lauric acid amide containing amide ester obtained in Production Example 1, 4.3 g (0.07 mol, 1.0 eq) of monoethanolamine was added.
(vs amide ester) was added, and the mixture was heated and stirred at 80 ° C. for 1 hour to carry out a amide ester transfer reaction. In the ¹ H-NMR analysis after the reaction, a signal at δ 4.22 ppm was not observed, so that the amide ester was completely disappeared. In addition, no signal derived from monoethanolamine was observed. In addition, IR analysis also showed that absorption at 1730 cm -1 derived from the amide ester was not recognized. The obtained polyoxyethylene (6) lauric acid amide containing no amide ester was a white solid (yield 468 g). The amine value of this product was 5.
The results of ¹ H-NMR and IR analysis are shown below.

¹ H-NMR analysis (250 MHz, CDC
l _3, internal standard TMS) δ0.88ppm (t, 3H, CH 3) δ1.26ppm (br, 16H, - CH 2 -) δ1.62ppm (m, 2H, - CH 2 -CH 2 -CO
-) δ1.89ppm (br, 1H, - OH) δ2.18ppm (t, 2H, - CH 2 -CONH-) δ3.47ppm (q, 2H, - CH 2 -NHCO-) δ3.66ppm (m, 10H _{, -O CH 2 CH 2 O-)} δ6.07ppm (br, 1H, - NH -) IR analysis (KBr tablet) 3284cm ^-1 (NH stretch, OH stretch) 1634 cm ^-1 (amide I) 1564 cm ^-1 (amide II) 1138 cm ^-1 (C-O-C expansion and contraction) 468 g of polyoxyethylene (6) lauric acid amide containing no amide ester obtained in this manner was added at 40 ° C.
The solution was heated to 0 ° C. to uniformly dissolve it, and 100 g of maleic anhydride was added to the solution under a nitrogen stream and stirred at 50 ° C. for 1 hour to form a maleic acid ester. Of the resulting mono (polyoxyethylene (6) lauric acid amide) maleate
The result of ¹ H-NMR analysis was as follows.

¹ H-NMR analysis (250 MHz, CDC
l _3, internal standard TMS) δ0.88ppm (t, 3H, CH 3) δ1.26ppm (br, 16H, - CH 2 -) δ1.62ppm (m, 2H, - CH 2 -CH 2 -CO
-) Δ 2.20 ppm (m, 2H, -CH ₂ -CONH-) δ 3.4 to 3.8 ppm (m, 22H, -NH- ( CH
_{2 CH 2 O) 5 - CH} 2 CH 2 O-) δ4.37ppm (m, 2H, -OCH 2 CH 2 O-CO
−) Δ 6.15 to 6.40 ppm (m, 2H, − CH═CH
−) To this, 138.6 g of anhydrous sodium sulfite was added to purified water 7
A 15 wt% sodium sulfite aqueous solution dissolved in 86 g was added dropwise at 20 ° C. over 10 minutes, and then the mixture was heated and stirred at 60 ° C. for 1 hour to be sulfonated to give polyoxyethylene (6).
Disodium lauric acid amide sulfosuccinate was synthesized (anionic active ingredient: 26%). No turbidity was observed in this object. The result of the NMR analysis is shown.

[0096]¹ H-NMR(250MHz, D₂O) δ 0.88 ppm (t, 3H,CH ₃ −) Δ1.29 ppm (br, 16H, −CH ₂ −) Δ1.61 ppm (m, 2H, −CH ₂ -CH₂-CON
H−) δ 2.27 ppm (t, 2H, −CH ₂ -CONH-) [delta] 2.82-3.18 ppm (m, 2H, -OCO-C
H ₂ -CHSO₃Na (CO₂Na), -OCO-CH
(SO₃Na)-CH ₂ -CO₂Na) δ 3.41 ppm (t, 2H, -NH-CH ₂ CH ₂ O
−) Δ3.63 to 3.86 ppm (m, 2H, —NHCH₂
CH ₂ O- (CH ₂ CH ₂ O)_Four−CH ₂ CH₂OCO-) delta 3.95 to 4.05 ppm (m, 1H, -OCO-C
H₂−CHSO₃Na (CO₂Na), -OCO-CH
(SO₃Na) -CH₂-CO₂Na) δ 4.30 ppm (m, 2H, -OCH₂ CH ₂ O-CO
−) TLC analysis showed spots of amide ester
There wasn't.

100 g of the obtained polyoxyethylene (6) lauric acid amide disodium sulfosuccinate was extracted 3 times with 100 ml of ethyl acetate, the ethyl acetate layer was washed with water and dried over magnesium sulfate, and the solvent was removed. No ester was obtained.

Example 2 178 g of polyoxyethylene (3) coconut oil fatty acid amide containing amide ester obtained in Preparation Example 2 was added to 3.7 g of monoethanolamine (0.06 mol, 1.2 eq).
(vs amide ester) was added, and the mixture was heated and stirred at 50 ° C. for 2 hours to decompose the amide ester. Polyoxyethylene (3) obtained by ¹ H-NMR analysis and IR analysis
No amide ester remained in the coconut oil fatty acid amide. 139 g of amide ester-free polyoxyethylene (3) coconut oil fatty acid amide thus obtained
To this, 50 g of maleic anhydride was added, and the mixture was heated and stirred at 60 ° C. for 1 hour to form a maleic ester.

To the obtained mono (polyoxyethylene (3) coconut oil fatty acid amide) maleate, 69 g of anhydrous sodium sulfite was dissolved in 393 g of purified water.
A weight% sodium sulfite aqueous solution was added dropwise at 20 ° C. over 10 minutes, and then heated and stirred at 60 ° C. for 3 hours to be sulfonated to synthesize polyoxyethylene (3) coconut oil fatty acid amide disodium succinate (anion effective). Ingredient: 26%). No turbidity was observed in this product.

By TLC analysis, no spot of amide ester was observed. Further, 100 g of the obtained polyoxyethylene (3) coconut oil fatty acid amide disodium sulfosuccinate was extracted 3 times with 100 ml of ethyl acetate, the ethyl acetate layer was washed with water, dried over magnesium sulfate, and then the solvent was removed. No ester was obtained.

Example 3 To 464 g of the polyoxyethylene (6) lauric acid amide obtained in Comparative Example 1, triglycolamine (2- [2
-(2-aminoethoxy) -ethoxy] -ethanol)
21 g (0.14 mol, 2 eq vs amide ester) was added, and the mixture was heated and stirred at 50 ° C. for 2 hours to decompose the amide ester. ^{From 1} H-NMR analysis and IR analysis,
No amide ester remained in the obtained polyoxyethylene (6) lauric acid amide.

The amide ester-free polyoxyethylene (6) lauric acid amide 485 thus obtained was obtained.
g at 40 ° C. to dissolve uniformly, and to this solution, under a nitrogen stream, 100 g of maleic anhydride was added,
The mixture was stirred at 0 ° C for 2 hours to form a maleic acid ester. Obtained mono (polyoxyethylene (6) lauric acid amide)
Maleate with sodium bisulfite (SO ₂ : 61%)
An aqueous solution prepared by dissolving 118 g and triethanolamine (168 g) in purified water (786 g) was added dropwise at 20 ° C. over 10 minutes, and then the mixture was heated and stirred at 60 ° C. for 3 hours to sulfonate and neutralize the polyoxyethylene (6). Lauric acid amide sodium triethanolamine sulfosuccinate was synthesized (anionic active ingredient: 26%). No turbidity was observed in this object.

As a result of TLC analysis and ethyl acetate extraction,
No amide ester was contained in the obtained polyoxyethylene (6) lauric acid amide sulfosuccinic acid triethanolamine.

Example 4 61 g of monoethanolamine amine and 0.5 g of sodium methoxide were added to 299 g of methyl stearate, and the resulting methanol was distilled off under reduced pressure while stirring under heating (20 mmHg, 110 ° C., 1 hour) to prepare stearin. 328 g of acid monoethanolamide was obtained. To this, 441 g of ethylene oxide was added, and 1 was added in the autoclave.
The reaction was carried out at 50 ° C for 1 hour to obtain 769 g of polyoxyethylene (11) stearic acid amide. ^{According to 1} H-NMR analysis, the amide ester content of this product was 10.4 mol%.

22 g (0.21 mo) of diglycolamine (2- (2-aminoethoxy) -ethanol) was added to the obtained polyoxyethylene (11) stearic acid amide.
1, 2 eq vs. amide ester) was added and the mixture was heated with stirring at 50 ° C. for 2 hours to decompose the amide ester. ¹ H-
From the NMR analysis and IR analysis, no amide ester remained in the obtained polyoxyethylene (11) stearic acid amide. 101 g of maleic anhydride was added to 791 g of polyoxyethylene (11) stearic acid amide containing no amide ester thus obtained,
The mixture was heated and stirred at 70 ° C. for 30 minutes to form a maleic acid ester. The obtained mono (polyoxyethylene (11) stearic acid amide) maleate was added to sodium bisulfite (S
O2: 61%) (118 g) was dissolved in purified water (738 g) to prepare a 14 wt% sodium hydrogen sulfite aqueous solution at 20 ° C.
After dripping over 0 minutes, the mixture was heated and stirred at 90 ° C. for 5 hours for sulfonation, and then ammonia water (28%) 6
After adding 7 g and neutralizing, polyoxyethylene (11) stearic acid amide sodium ammonium sulfosuccinate was synthesized (anionic active ingredient: 26%). No turbidity was observed in this product.

As a result of TLC analysis and extraction with ethyl acetate,
The obtained polyoxyethylene (11) stearic acid amide sodium ammonium sulfosuccinate contained no amide ester.

Example 5 463 g of polyoxyethylene (6) lauric acid amide containing an amide ester, which is the intermediate shown in Comparative Example 1.
500 ml of a 1% by weight sodium hydroxide aqueous solution was added thereto, and the mixture was heated with stirring at 50 ° C. for 3 hours to hydrolyze the amide ester. Then, water was removed under reduced pressure to obtain amide ester-free polyoxyethylene (6) lauric acid amide. From the HPLC analysis, sodium polylaurate was found to be present in this polyoxyethylene (6) laurate amide.
It was contained by weight%.

The amide ester-free polyoxyethylene (6) lauric acid amide 468 thus obtained was obtained.
100 g of maleic anhydride was added to g, and the mixture was heated and stirred at 63 ° C. for 1 hour to form a maleic acid ester. To the obtained mono (polyoxyethylene (6) lauric acid amide) maleate, 138.6 g of anhydrous sodium sulfite was added to purified water 7
15% sodium sulfite aqueous solution dissolved in 86 g,
After dropping at 20 ° C over 10 minutes, the above compound was sulfonated by heating and stirring at 60 ° C for 2 hours to synthesize polyoxyethylene (6) lauric acid amide disodium sulfosuccinate (anionic active ingredient: 27%). .

When the obtained polyoxyethylene (6) lauric acid amide disodium sulfosuccinate was extracted with ethyl acetate, no amide ester was contained. However, 1% by weight of sodium laurate was contained by HPLC analysis.

Example 6 100 g of polyoxyethylene (6) lauric acid amide disodium sulfosuccinate containing amide ester obtained in Comparative Example 1 was extracted 3 times with 100 ml of ethyl acetate. The remaining aqueous layer was topped off under reduced pressure. As a result of NMR analysis (250 MHz, D ₂ O) and TLC analysis, amide ester was not recognized.

Examples 7 to 17 and Comparative Examples 3 to 6 The polyoxyethylene fatty acid amide sulfosuccinate ester type surfactants obtained in Examples 1 and 2 and Comparative Example 1 were blended as shown in Table 2. To prepare a cleaning agent. The obtained detergent was subjected to the following foaming power, detergency test, cold resistance test and protein denaturation test.

These test methods were carried out by the following methods.

1) Foaming Power Test The cleaning agent was diluted with distilled water so that the active agent pure content was 0.2%, and the foaming power was measured according to the method described in JIS K3362.

The evaluation criteria were set as follows.

∘: Very good foaming, foaming power of 200 mm or more ○: Good foaming, foaming power of 170 mm or more, 200 mm
Less than Δ: Foaming is normal, foaming power is 130 mm or more, 170 mm
Less than × ... Poor foaming, foaming power less than 130 mm 2) Detergency test 0.1% Sudan III as an indicator was added to beef tallow, and 5% of this was applied to a porcelain dish (diameter 25 cm). The washing power was determined by scrubbing with a sponge soaked with 30% by weight of a washing solution, and the number of dishes washed until no more beef tallow was washed from the dishes.

3) Cold resistance test A sample prepared to have a sample concentration of 20% by weight was put in a test tube and stored in a refrigerator at -5 ° C for 7 days to examine whether or not turbidity was observed, thereby determining cold resistance. .

◯: Transparent and no turbidity Δ: Transparent at room temperature, but cloudy when stored at −5 ° C. for 7 days ×: Turbidity at room temperature 4) Protein denaturation rate test Using ovalbumin using aqueous gel filtration high performance liquid chromatography. When the sample was added to the pH7 buffer solution so that the sample concentration was 1%, the ovalbumin denaturation rate was 220%.
It measured using the absorption peak of nm.

[0118]

[Equation 2]

The evaluation criteria were set as follows.

Ovalbumin denaturation rate less than 30% Ovalbumin denaturation rate 30 to 59% ΔOvalbumin denaturation rate 60 to 79% × Ovalbumin denaturation rate 80% or more The test results are shown in Table 2.

As is clear from the results shown in Table 2, the cleaning agents of Examples 7 to 17 containing the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant of the present invention containing substantially no amide ester were prepared. It had excellent foaming power, detergency, low skin irritation, and excellent compatibility. on the other hand,
The cleaning agents of Comparative Examples 6 to 11 in which the conventional polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant containing amide ester was blended were slightly inferior in foaming power, detergency, skin irritation and compatibility. Was there.

[0122] Example 18 A conditioning shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Compound of Example 1 10.0 Lauroylmethyl-β-alanine sodium (30%) 20.0 Cationized guar gum ^{* 1} 0.3 Lauric acid diethanolamide 2.0 Glycerin 3.0 Carboxymethyl chitin 0.2 EDTA 0.1 Adjust citric acid pH to 6.5 Water balance [Note] * 1: MEYHALL, trademark: JAGUAR
Table 3 shows the C-120 test results.

Example 19 A pearly shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Compound of Example 2 10.0 N-2-hydroxyethyl-N-2-coconut oil fatty acid amidoethylglycine (30%) 20.0 N-coconut oil fatty acid acyl-L-glutamic acid monotri Ethanolamine (25%) 5.0 Lauroylmethyltaurine sodium (30%) 5.0 Lauric acid diethanolamide 2.0 Coconut oil fatty acid monoethanolamide 1.5 Sodium hyaluronate 0.5 Citric acid pH to 6.0 Amount Methylparaben 0.1 Perfume Appropriate amount Water balance Table 3 shows the test results.

Example 20 A face cleanser having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% N-2-hydroxyethyl-N-2-coconut oil fatty acid Amidoethyl-β-alanine (30%) 10.0 Compound of Example 2 20.0 Lauric acid diethanolamide 7.0 Ethylene distearate Glycol ester 2.0 Monoammonium glycyrrhizinate 0.2 Methylparaben 0.1 Citric acid Adjusted to pH 6.5 Water balance Table 3 shows the test results.

Example 21 A transparent antidandruff shampoo having the following composition was prepared, and Example 1 was used.
The same test was performed.

Ingredients wt% Compound of Example 3 15.0 Lauric acid monoethanolamide 5.0 2-Coconut oil Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (30%) 10.0 Pirocton Olamine 0.7 Sodium hyaluronate 0.1 Methylparaben 0.1 EDTA 0.1 Citric acid pH = 7 Water balance Table 3 shows the test results.

Example 22 A gel shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Compound of Example 1 5.0 Compound of Example 2 10.0 Coconut oil fatty acid amidopropyldimethylamino betaine acetate (30%) 20.0 Carboxymethyl chitin 0.1 Methylparaben 0.1 EDTA 0 Amount of citric acid pH = 7 Water balance test results are shown in Table 3.

Example 23 A rinse-inclusive shampoo having the following composition was prepared, and Example 1 was used.
The same test was performed.

Ingredients wt% Compound of Example 1 8.0% Lauric acid monoethanolamide 2.0 Lauroylmethyl-β-alanine sodium (30%) 20.0 Stearyltrimethylammonium chloride 2.0 Cetyl octanoate 0.5 Methylparaben 0.1 EDTA 0.1 Citric acid pH = 7 Amount of residual water test results are shown in Table 3.

Example 24 A body shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients% by weight 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (30%) 20.0 Compound of Example 2 10.0 Lauric acid diethanolamide 3.0 Lauric acid triethanolamine 7.0 Methylparaben 0.1 EDTA 0.1 Water balance Table 3 shows the test results.

Example 25 A shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Compound of Example 1 10.0 C _14- α Sodium olefinsulfonate 5.0 Oxyalkylene-modified organopolysiloxane (20% modification: 20% by weight of polyoxyethylene groups) 1.0 Diethanolamine laurate Do 5.0 Lauric acid monoethanolamide 2.0 Methylparaben 0.1 EDTA 0.1 Water balance Table 3 shows the test results.

Example 26 A shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Decyl glucoside (1.7) 5.0 Compound of Example 1 5.0 Sodium cocoyl isethionate 5.0 Lauric acid diethanolamide 3.0 Polyoxyethylene (2) lauric acid monoethanol amide 3.0 Methylparaben 0.1 EDTA 0.1 Water balance Table 3 shows the test results.

Example 27 A shampoo having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients wt% Polyoxyethylene (3) lauryl sodium ether sulphate 15.0 Compound of Example 4 11.0 Sodium monolauryl phosphate 4.0 Lauric acid diethanolamide 3.0 Methylparaben 0.1 EDTA 0.1 Table 3 shows the water balance test results.

Example 28 A kitchen detergent having the following composition was prepared and subjected to the same test as in Example 1.

Ingredients% by Weight Polyoxyethylene (3) lauric acid monoethanol sodium amide sulphate (30%) 10.0 Polyoxyethylene (3) lauryl ether disodium sulfosuccinate (30%) 5.0 Compound of example 4 11.0 Lauryl dimethylamine oxide 4.0 Ethanol 2.0 Water balance Table 3 shows the test results.

[0144]

[Table 3]

As is clear from the results shown in Table 3, the composition of Examples 18 to 28 containing the polyoxyethylene fatty acid amide sulfosuccinic acid ester salt-type surfactant of the present invention having an amide ester content of 1.5 wt% or less. The cleansing agent was excellent in foaming power, detergency, low skin irritation and excellent compatibility.

[0146]

According to the present invention, a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant having an amide ester content of 1.5 wt% or less is excellent in foaming power and detergency, and moreover, to the skin and hair. It is possible to obtain a detergent composition having less irritation and excellent solubility.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): (Wherein RCO is a linear or branched saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and n is an integer of 1 or more), and the content of the amide ester is 1.5 w.
General formula (2), characterized in that it is t% or less. (In the formula, RCO and n are the same as defined above. ^One of X ¹ and X ² represents a hydrogen atom, the other represents a —SO ₃ M ² group, and M ¹ and M ² represent Identical or independent of each other,
Representing an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid contained in hydrogen or a sulfonating agent), a polyoxyethylene fatty acid amide sulfosuccinic acid Acid salt type surfactant. 2. The following general formula (3): (In the formula, RCO represents a linear or branched saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms.) Ethylene oxide is added to the fatty acid monoethanolamide to give a compound represented by the general formula (4): [Chemical 4] (Wherein RCO is the same as defined above, n is an integer of 1 or more), and polyoxyethylene fatty acid amide represented by the general formula (1) ] (In the formula, RCO and n are the same as defined above), 0.8 to 10-fold mol of the general formula (5): (Wherein, m is an integer of 1 or more) is reacted to react the amide ester of the general formula (1) with the general formula (4) and the general formula (6). (Wherein RCO and m are the same as defined above), the polyoxyethylene fatty acid amide is converted to maleic anhydride, and then the compound represented by the general formula (7) A mono (polyoxyethylene fatty acid amide) maleic acid ester represented by the formula (wherein RCO and n are the same as defined above) is prepared, and an alkali metal, an alkaline earth metal, ammonia, an alkanolamine and a basic amino acid are added thereto. And / or an acidic sulfite containing a neutralizing agent selected from at least one of alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, alkanolamines and basic amino acids, and And / or reacting with a sulfonating agent comprising at least one selected from acidic sulfites, represented by the general formula (1): (Wherein RCO and n are the same as defined above), the content of the amide ester represented by the general formula (2) is 1.5 wt% or less. (In the formula, RCO and n are the same as defined above. ^One of X ¹ and X ² represents a hydrogen atom, the other represents a —SO ₃ M ² group, and M ¹ and M ² represent Identical or independent of each other,
Representing an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid contained in hydrogen or a sulfonating agent), a polyoxyethylene fatty acid amide sulfosuccinic acid Method for producing acid salt type surfactant. 3. A compound represented by the general formula (1): (Wherein RCO is a linear or branched saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and n is an integer of 1 or more), and the content of the amide ester is 1.5 w.
General formula (2) of t% or less (In the formula, RCO and n are the same as defined above. ^One of X ¹ and X ² represents a hydrogen atom, the other represents a —SO ₃ M ² group, and M ¹ and M ² represent Identical or independent of each other,
Representing an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid contained in hydrogen or a sulfonating agent), a polyoxyethylene fatty acid amide sulfosuccinic acid A detergent composition comprising an acid salt type surfactant. 4. The general formula (2) according to claim 3, wherein the content of the amide ester of the general formula (1) is 1.5 wt% or less.
And a polyoxyethylene fatty acid amide sulfosuccinic acid ester salt type surfactant represented by and an anionic surfactant and / or an amphoteric surfactant.