JP3515800B2 - Polyoxyethylene fatty acid amide sulfate ester type surfactant, method for producing the surfactant, and detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyoxyethylene fatty acid amide sulfate ester salt having excellent foaming power / detergency, less irritation to skin and hair, and excellent solubility, and a detergent containing the same. It relates to a composition.

[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, a polyoxy alcohol prepared by adding ethylene oxide to fatty acid monoethanolamide, converting the ethylene oxide addition reaction product into a sulfuric acid ester, and neutralizing the product Ethylene fatty acid amide sulfate ester salts have come into use.

However, although the polyoxyethylene fatty acid amide sulfate ester salt obtained by this method is excellent in terms of skin irritation and the like as described above, it contains a water-insoluble compound and contains an insoluble substance. Those with a large amount were at room temperature, and those with a relatively small amount were turbid when cold, which reduced the commercial value. 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 sulfuric acid ester salt 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 the skin and hair, and excellent solubility, the drawback of the conventional polyoxyethylene fatty acid amide sulfate ester salt is that ethylene oxide It was discovered that it is derived from an amide ester that is a by-product during the addition reaction. That is, the polyoxyethylene fatty acid amide sulfuric acid ester salt is produced by adding ethylene oxide to fatty acid monoethanolamide and then converting it into a sulfuric acid ester.
As shown in 1, the disproportionation reaction occurs, and the amide ester (a) and the trialkanolamine (b) are by-produced in the polyoxyethylene fatty acid amide.

[0007]

[Chemical 11]

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 sulfuric acid esterification to obtain a polyoxyethylene fatty acid amide sulfuric acid ester salt, the amide ester does not react with the sulfuric acid esterifying agent and is in the form as it is. , Was mixed in the product polyoxyethylene fatty acid amide sulfate ester salt.

Since the amide ester has a high melting point and is almost insoluble in water, its presence in a large amount causes turbidity and precipitation in the product polyoxyethylene fatty acid amide sulfate ester salt, which lowers the commercial value. Was there. Furthermore, since the amide ester has low foaming power and detergency, the performance originally possessed by the polyoxyethylene fatty acid amide sulfuric acid ester salt is deteriorated.

[0012] Therefore, the present inventors have paid attention to whether the drawbacks of the conventional polyoxyethylene fatty acid amide sulfate ester salt can be eliminated by removing the amide ester by-produced from the polyoxyethylene fatty acid amide sulfate ester salt. As a result of further research, it was obtained by adding ethylene oxide to fatty acid monoethanolamide,
It was found 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. The inventors have found that the polyoxyethylene fatty acid amide sulfuric acid ester salt obtained by chlorinating oxyethylene fatty acid amide with a sulfuric acid ester does not contain an amide ester and can solve the above-mentioned problems, and completed the present invention. That is, the present invention provides (1) the general formula (1)

[0013]

[Chemical 12]

(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)

[0015]

[Chemical 13]

(Wherein RCO and n are the same as defined above, M is an alkali metal atom, an alkaline earth metal atom,
Represents a cationic residue of an ammonium group, an alkanolamine, or a basic amino acid, and v
Represents an integer equal to the valence of the atom or group represented by M)).

(2) The following general formula (3)

[0018]

[Chemical 14]

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 represented by the general formula: (4)

[0020]

[Chemical 15]

(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.

[0022]

[Chemical 16]

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)

[0024]

[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 obtain the general formula (4) and the general formula (6).

[0026]

[Chemical 18]

After the polyoxyethylene fatty acid amide represented by the formula (wherein RCO and m are the same as defined above) is transferred, a sulfuric acid esterifying agent is reacted, and the reaction product is treated with an alkali metal hydroxide. Substance, an alkaline earth metal hydroxide, ammonia, an alkanolamine, or a basic amino acid is used as a neutralizing agent to neutralize the content of the amide ester represented by the general formula (1). General formula (2) of 1.5 wt% or less

[0028]

[Chemical 19]

(In the formula, RCO, n and m are as defined above. M is an alkali metal atom contained in the neutralizing agent,
An alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid, and v represents an integer equal to the valence of the atom or group represented by M). A method for producing a polyoxyethylene fatty acid amide sulfate ester type surfactant.

(3) General formula (1)

[0031]

[Chemical 20]

(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 general formula (2), in which the content of the amide ester represented by the above integer is 1.5 wt% or less.

[0033]

[Chemical 21]

(Wherein RCO and n are the same as defined above, M is an alkali metal atom, an alkaline earth metal atom,
Represents a cationic residue of an ammonium group, an alkanolamine, or a basic amino acid, and v
Represents an integer equal to the valence of the atom or group represented by M)), and a detergent composition containing a polyoxyethylene fatty acid amide sulfate ester type surfactant.

The gist of the invention is as follows.

The polyoxyethylene fatty acid amide sulfate 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 sulfate ester salt type surfactant of the general formula (2). A polyoxyethylene fatty acid amide sulfuric acid ester salt type surfactant having an amide ester content of more than 1.5 wt% has reduced foaming power, detergency, skin irritation, or cold resistance. Not preferable.

The acyl group (RCO) constituting the fatty acid monoethanolamide represented by the general formula (1), which is a raw material of the polyoxyethylene fatty acid amide sulfate ester type surfactant of the present invention, has 6 to 6 carbon atoms. 22 straight or branched chain saturated or unsaturated fatty acid residues, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
Examples thereof include residues of fatty acids such as oleic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, and hardened tallow fatty acid.

In the present invention, m and n in the general formulas (1), (4) and (6) are integers of 1 or more representing a repeating unit of an oxyethylene group, but considering the addition reaction of ethylene oxide, , 1 to 100 is preferable, and 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.
In order to produce a polyoxyethylene fatty acid amide sulfate ester salt of 5 wt% or less, the following may be carried out.

(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
The amide ester contained in the polyoxyethylene fatty acid amide is reacted with 0.8 to 10 times mol of the alkanolamine of the general formula (5).

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 addition of 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 usually 2
It is achieved by stirring at 0-150 ° C for 10 minutes to 12 hours.

The amount of the alkanolamine to be 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, and the excess alkanolamine remains in the product, which not only requires an extra sulfating agent in the subsequent sulfate ester chlorination step. However, the performance of the product polyoxyethylene fatty acid amide sulfate ester salt is deteriorated, and it may cause 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.

If 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 reaction is completed.
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 sulfate ester salt of the final product is usually small, and it does not affect the performance and stability of the product. No removal operation is required as it does not.

(Sulfuric acid ester chlorination step of polyoxyethylene fatty acid amide) This step may be in accordance with the conventional method for producing a polyoxyethylene fatty acid amide sulfuric acid ester salt, for example, polyoxyethylene fatty acid of the general formula (4). After reacting the sulfuric acid ester chlorinating agent with the amide,
It may be neutralized with a neutralizing agent.

Examples of the sulfuric acid esterifying agent used in this step include chlorosulfonic acid, concentrated sulfuric acid, anhydrous sulfuric acid, sulfamic acid and the like.

As the neutralizing agent, a hydroxide of an alkali metal (eg sodium, potassium etc.), a hydroxide of an alkaline earth metal (eg magnesium etc.), ammonia, an alkanolamine (eg triethanolamine), or , Basic amino acids (eg, lysine, arginine, etc.) can be used.

In the present invention, the content of the amide ester in the polyoxyethylene fatty acid amide sulfate ester type surfactant can be measured by the following method. That is, the polyoxyethylene fatty acid amide sulfate ester type surfactant is sufficiently extracted with a solvent such as ethyl acetate. Next, after washing with saturated saline, it is dried over anhydrous sodium sulfate, magnesium sulfate, etc., and the organic layer is concentrated under reduced pressure and dried to give an amide ester. The content of amide ester in the polyoxyethylene fatty acid amide sulfate ester type surfactant can be obtained from the following formula.

[0052]

[Equation 1]

Here, the anion active ingredient is, for example, JI.
SK3362 (1990), Quantification of bound sulfuric acid of total anionic surfactant described in (4.1.1), back titration method (method A)
According to the method, the bound sulfuric acid (as SO ₃ ) in the polyoxyethylene fatty acid amide sulfate ester type surfactant is measured, and it can be calculated by the following formula from the obtained bound sulfuric acid amount.

[0054]

[Equation 2]

In addition to the amide ester, the amide ester obtained by the extraction may contain unreacted polyoxyethylene fatty acid amide that has not been salified as a sulfate ester. In that case, HPLC or ¹ H-
It is necessary to measure the true amide ester content in the extract by NMR and replace that value with the weight of the amide ester obtained by the extraction of the formula shown in Eq.

The content of amide ester in the polyoxyethylene fatty acid amide sulfate ester type surfactant is 1.
When the content is 0% or less, the presence or absence of amide ester can be easily confirmed by TLC analysis. That is, TLC analysis using a silica gel plate (developing solution: chloroform / methanol / ammonia = 100/35/8, detection: phosphomolybdic acid ethanol solution) showed that the amide ester was Rf0.
Since 91 spots are shown, the presence / absence of amide ester can be determined by the presence / absence of spots.

Typical examples of the polyoxyethylene fatty acid amide sulfate ester salt represented by the general formula (2) obtained by the present invention include polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate, polyoxyethylene ( 6) coconut oil fatty acid amide sulfate, polyoxyethylene (11) coconut oil fatty acid amide sulfate ammonium, polyoxyethylene (4) sodium lauric acid amide sulfate, polyoxyethylene (6) myristic acid amide sulfate triethanolamine, polyoxyethylene (11) stearic acid amide sulfuric lysine salt, and polyoxyethylene (21) oleamide magnesium sulfate and the like.

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

A third aspect of the present invention relates to a detergent composition containing a polyoxyethylene fatty acid amide sulfate ester salt having an amide ester content of 1.5 wt% or less, and more specifically, an amide ester. The present invention relates to a detergent composition comprising a polyoxyethylene fatty acid amide sulfate ester salt substantially free of and an anionic surfactant and / or an amphoteric surfactant.

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

In the detergent composition of the third invention, the content of polyoxyethylene fatty acid amide sulfate ester salt having an amide ester content of 1.5 wt% or less is 0.05.
If it is less than 10% by weight, the effect is not sufficient, and if it exceeds 40% by weight, the effect is not increased, which is not preferable.

The polyoxyethylene fatty acid amide sulfate ester salt having an amide ester content of 1.5 wt% or less, which is obtained by the present invention, exhibits surface activity by itself.
By combining with other anionic surfactant and / or amphoteric surfactant, its performance can be further improved. Replacing the components of the cleaning agent containing a polyoxyethylene fatty acid amide sulfuric acid ester salt containing an amide ester, which has been conventionally used, with the polyoxyethylene fatty acid amide sulfuric acid ester salt obtained in the present invention, The detergency is improved, the turbidity is not seen, and the solubility and cold resistance are improved.

As the anionic surfactant used in the detergent composition of the present invention, fatty acid soaps such as sodium laurate and triethanolamine laurate, alkylbenzene sulfonates, α-olefin sulfonates, sodium lauryl sulfate, Lauryl sulfate such as triethanolamine lauryl sulfate, triethanol monododecyl phosphate, sodium polyoxyethylene dodecyl ether phosphate, phosphate ester such as di- (polyoxyethylene (6) coconut oil fatty acid amide) -sodium phosphate , Sodium cocoylmethyl taurine, sodium lauroyl methyl taurine, etc., acyl isethionates such as sodium lauroyl isethionate, disodium lauryl sulfosuccinate, POE (1-4) Ruhokohaku lauryl disodium polyoxyethylene (6) Lauric acid amide sulfosuccinate disodium, sulfosuccinic acid type surfactants such as amide sulfosuccinate disodium oleate,
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 sulfate ester type surfactant having an amide ester content of 1.5 wt% or less, an anionic surfactant and / or an amphoteric surfactant. The compounding ratio 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 sulfate ester salt having an amide ester content of 1.5 wt% or less and the anionic surfactant and / or the amphoteric surfactant is out of the above range, the foaming power / detergency is sufficient. If the total content of each component is less than 0.1% by weight, the effect is not sufficient.

Further, in the detergent composition of the present invention, the following additional components can be used if necessary. As the additional component, for example, coconut oil fatty acid diethanolamide,
Fatty acid diethanolamide such as lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, fatty acid monoethanolamide such as lauric acid monoethanolamide, coconut oil fatty acid diglycolamide, fatty acid diglycolamide such as lauric acid diglycolamide,
Fatty acid isopropanolamide such as lauric acid isopropanolamide, fatty acid ester, alkylamine oxide such as lauryldimethylamine oxide, P
OE higher alcohol ether, POE alkyl phenyl ether, nonionic surfactant such as alkyl glucoside such as decyl glucoside, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride,
Mention may be made of quaternary ammonium salt type cationic surfactants such as distearyldimethylammonium chloride, cationized polymers and cationized guar gum.

The following additional components can also be used as required. 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, and fragrances and pigments. Such.

When the detergent of the present invention is used as a shampoo, the shape is generally liquid or paste (gel), and the appearance is generally 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 use is optional, but typical examples thereof include detergents such as kitchen detergents, hard surface cleaners, facial cleansers, cleansing foams, shampoos and body shampoos.

[0070]

Function: The amide ester content of the present invention is 1.5w.
The reason why the polyoxyethylene fatty acid amide sulfate ester 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 surfactant of the present invention is used. This is because the amide ester undergoes a rearrangement reaction as described below during the production of the agent.

That is, when the amide ester by-produced in the ethylene oxide addition reaction to the fatty acid monoethanolamide is reacted with an alkanolamine, the acyl group on the ester group side of the amide ester becomes A reaction occurs that transfers to the amino group of the alkanolamine.

[0072]

[Chemical 20]

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 production method of 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. It can be used effectively.

Further, even if only the amide ester is removed from the polyoxyethylene fatty acid amide sulfate ester salt containing the amide ester obtained by the conventional production method by extraction with a solvent such as ethyl acetate, the present invention It is possible to obtain a polyoxyethylene fatty acid amide sulfate ester salt having an amide ester content of 1.5 wt% or less. Since the amide ester has almost no solubility in water, the amide ester and the polyoxyethylene fatty acid amide sulfate ester salt can be separated relatively easily 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 described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0078]

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 8
9g was added and reacted in an autoclave at 150 ° C for 1 hour to give polyoxyethylene (3) lauric acid amide 33.
3 g was obtained.

¹ H-NMR analysis for measuring the amide ester content of this product was carried out. That is, the methylene group of -CH ₂ -OCO-R of the amide ester is characteristically observed as a triplet at δ 4.2 ppm when TMS is used as an internal standard, so it is easily distinguished from other signals. To be done. Integral value of CH ₃ group at δ 0.88 ppm and δ 4.2 p
The amide ester content can be easily calculated from the integrated value of the pm 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, —C H 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.

[0083]

[Equation 3]

Comparative Example 1 333 g of polyoxyethylene (3) lauric acid amide containing amide ester obtained in Production Example 1 was heated to 40 ° C. to uniformly dissolve the amide ester, and the solution was dissolved in a nitrogen stream under
Chlorosulfonic acid (119 g) was added dropwise to form a sulfuric acid ester. After removing the hydrogen chloride generated at this time under reduced pressure,
The reaction product was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxyethylene (3) sodium lauric acid amide sulfate (anionic active ingredient: 26%). The NMR measurement results are shown below.

¹ H-NMR (250 MHz, D ₂ O) δ 0.88 ppm (t, 3H, CH ₃ —) δ 1.24 ppm (br, 16H, — CH ₂ —) δ 1.55 ppm (m, 2H, — CH ₂ -CH ₂ -CON
H-) δ 2.20 ppm (t, 2H, -CH ₂ -CONH-) δ 3.34 ppm (t, 2H, -CONH- CH _2- ) δ 3.62 to 3.85 ppm (m, 8H, -OCH ₂ C)
H ₂ O-) δ 4.14 ppm (m, 2H, -OCH ₂ CH ₂ O-SO
₃ Na) amide ester has low solubility in heavy water, so TL
The presence or absence of amide ester was examined by C analysis (silica gel, developing solution: chloroform / methanol / aqueous ammonia = 100/35/8). As a result, an amide ester spot was observed at Rf 0.91.

Then, 100 g of the obtained sodium polyoxyethylene (3) lauric acid amide sulfate was extracted three 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. 2.8 g of ester crystals were obtained. This corresponded to 10.8% by weight based on the pure sodium polyoxyethylene fatty acid amide sulfate. This is a sulfate ester chloride of polyoxyethylene (3) lauric acid amide,
The content of the amide ester in the polyoxyethylene fatty acid amide was the same as the content (10.8% by weight) assumed that the amide ester remained unreacted. It was found that the amide sulfate ester salt remained as it was.

Production Example 2 To 120 g of coconut oil fatty acid methyl obtained by methyl esterifying coconut oil fatty acid (C ₆ -C ₂₂ ) by a conventional method, 31 g of monoethanolamine and 0.3 g of sodium methoxide were added, and methanol was distilled off under reduced pressure. Heat and stir while leaving (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 80 ° C. for 24 hours to obtain polyoxyethylene (3) coconut oil fatty acid amide. ¹ H-NMR analysis of this product (250 MH
z, CDCl ₃ ) and found to contain 2.5 mol% of amide ester.

Comparative Example 2 178 g of polyoxyethylene (3) coconut oil fatty acid amide containing amide ester obtained in Production Example 2 was added at 40 ° C.
The solution was heated to a uniform temperature to dissolve it uniformly, and 60 g of chlorosulfonic acid was added dropwise to the solution under a nitrogen stream to form a sulfuric acid ester. Hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate (anionic active ingredient: 26%). .

100 g of the polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate thus obtained was extracted three 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. 0.78 g of ester crystals were obtained. This corresponded to 3.0% by weight of pure polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate. This was almost the same as the content (3.0% by weight) of sulphate esterification of polyoxyethylene coconut oil fatty acid amide, assuming that the amide ester remained unreacted.

Reference Example 1 In the ethylene addition reaction of Production Example 1, by changing the temperature of the ethylene oxide addition reaction, the influence on the time required for the ethylene oxide addition reaction and the amide ester content in polyoxyethylene lauric acid amide was examined. Examined. The results are shown in Table 1.

[0091]

[Table 1]

From these results, it can be seen that the higher the EO 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 lauric acid monoethanolamide, which is a raw material for ethylene oxide addition, is 78 ° C, it is difficult to add ethylene oxide at a temperature lower than 90 ° 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 333 g of polyoxyethylene (3) 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 did not recognize absorption at 1730 cm ⁻¹ derived from amide ester. The obtained polyoxyethylene (3) lauric acid amide containing no amide ester was a white solid (yield 337 g). The amine value was 5.

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) The amide ester-free polyoxyethylene (3) lauric acid amide 337 g thus obtained was treated at 40 ° C.
The solution was heated to 0 ° C. to dissolve it uniformly, and 119 g of chlorosulfonic acid was added dropwise to this solution under a nitrogen stream to form a sulfuric acid ester. The hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with an aqueous sodium hydroxide solution to synthesize sodium polyoxyethylene (3) lauric acid amide sulfate (anionic active ingredient: 26%). That NM
The R measurement result is shown.

¹ H-NMR (250 MHz, D ₂ O) δ 0.88 ppm (t, 3H, CH ₃ —) δ 1.24 ppm (br, 16H, — CH ₂ —) δ 1.55 ppm (m, 2H, — CH ₂ -CH ₂ -CON
H-) δ 2.20 ppm (t, 2H, -CH ₂ -CONH-) δ 3.34 ppm (t, 2H, -CONH- CH _2- ) δ 3.62 to 3.85 ppm (m, 8H, -OCH ₂ C)
H ₂ O-) δ 4.14 ppm (m, 2H, -OCH ₂ CH ₂ O-SO
₃ Na) TLC analysis showed no amide ester spots.

100 g of the obtained sodium polyoxyethylene fatty acid amide sulfate 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. However, no amide ester was obtained. .

Example 2 178 g of polyoxyethylene (3) coconut oil fatty acid amide containing amide ester obtained in Production Example 2 was added to 1.8 g of monoethanolamine (0.03 mol, 1.2 eq).
(vs amide ester) was added, and the mixture was heated and stirred at 50 ° C. for 1 hour to decompose the amide ester. ^{According to 1} H-NMR analysis and IR analysis, no amide ester remained in the obtained polyoxyethylene (3) coconut oil fatty acid amide.

The amide ester-free polyoxyethylene (3) coconut oil fatty acid amide 13 thus obtained was obtained.
9 g was heated to 40 ° C. to be uniformly dissolved, and 60 g of chlorosulfonic acid was added dropwise to this solution under a nitrogen stream to form a sulfuric acid ester. Hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate (anionic active ingredient: 26
%).

No spots of amide ester were observed in the TLC analysis. Also, the obtained polyoxyethylene (3) coconut oil fatty acid sodium amide sulfate 100 g
Was extracted three 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, but no amide ester was obtained.

Example 3 333 g of polyoxyethylene (3) lauric acid amide obtained in Production Example 1 was added to 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 (3) lauric acid amide.

The amide ester-free polyoxyethylene (3) lauric acid amide 354 thus obtained
g was heated to 40 ° C. to be uniformly dissolved, and 81 g of sulfuric acid anhydride was added to this solution under a nitrogen stream to form a sulfuric acid ester. The reaction product was neutralized with an aqueous solution of triethanolamine to synthesize sodium polyoxyethylene (3) lauric acid amide sulfate (anionic active ingredient: 26%). T
As a result of LC analysis and extraction with ethyl acetate, the obtained polyoxyethylene (3) fatty acid amide triethanolamine sulfate contained no amide ester.

Example 4 To 299 g of methyl stearate, 61 g of monoethanolamine amine and 0.5 g of sodium methoxide were added, and the resulting methanol was stirred under heating under reduced pressure while 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. The thus-obtained 791 g of polyoxyethylene (11) stearic acid amide containing no amide ester was heated to 40 ° C. to be uniformly dissolved, and in this solution, chlorosulfonic acid 11
9 g was added dropwise to form a sulfuric acid ester. The hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with aqueous ammonia to synthesize polyoxyethylene (11) ammonium stearate amide sulfate (anionic active ingredient: 26%). As a result of TLC analysis and extraction with ethyl acetate, the obtained ammonium polyoxyethylene stearate amide sulfate contained no amide ester.

Example 5 108 g of polyoxyethylene (3) lauric acid amide containing an amide ester, which is the intermediate shown in Preparation 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 (3) lauric acid amide. As a result of HPLC analysis, sodium polylaurate was found to be 4% in this polyoxyethylene (3) laurate amide.
It was contained by weight%.

The amide ester-free polyoxyethylene (3) lauric acid amide 334 thus obtained was obtained.
g was heated to 40 ° C. and uniformly dissolved, and 119 g of chlorosulfonic acid was added dropwise to this solution under a nitrogen stream to form a sulfuric acid ester. The hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxyethylene (3) lauric acid amide sulfate sodium salt (anionic active ingredient: 26
%).

When the obtained sodium polyoxyethylene (3) lauric acid amide sulfate was extracted with ethyl acetate, no amide ester was contained. But HPLC
According to the analysis, it contained 1% by weight of sodium laurate.

Example 6 Polyoxyethylene (3) lauric acid sodium amide sulfate containing amide ester obtained in Comparative Example 1 100
g was extracted 3 times with 100 ml of ethyl acetate. The remaining aqueous layer was topped off under reduced pressure. NMR analysis (250 MHz,
D ₂ O) and the results of TLC analysis, the amide ester was observed.

Examples 7 to 17 and Comparative Examples 3 to 7 In Examples 7 to 17 and Comparative Examples 3 to 7, cleaning agents having the compositions shown in Table 2 were prepared. The obtained product 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 standard was 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 △: 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) to obtain 10 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 a sample concentration of 20% by weight was placed in a test tube and stored in a refrigerator at -5 ° C for 7 days to examine cold resistance depending on whether turbidity was observed. .

◯: Transparent and no turbidity Δ: Transparent at room temperature, but white turbid after storage at -5 ° C. for 7 days ×: Turbidity at room temperature 4) Protein denaturation rate test Using aqueous gel filtration high performance liquid chromatography, ovalbumin 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.

[0115]

[Equation 4]

The evaluation standard was set as follows.

Ovalbumin denaturation rate of less than 30% ○ Ovalbumin denaturation rate of 30 to 59% △ Ovalbumin denaturation rate of 60 to 79% × Ovalbumin denaturation rate of 80% or more 4) Comparative target products The comparative products in Table 2 are , commercially available polyoxyethylene fatty acid amide sulfuric acid ester salt surfactants (trade name "San'amido C-3]: manufactured by NOF Corporation, polyoxyethylene (3) coconut oil fatty acid _{(C 12 / C 14 = 75} / 25) Sodium monoethanolamide sulphate) was used and the amide ester content of this product was measured to be 2.0 wt.
%Met. The test results are shown in Table 2.

[0118]

[Table 2]

As is clear from the results shown in Table 2, of Examples 7 to 17 in which the polyoxyethylene fatty acid amide sulfate ester type surfactant of the present invention having an amide ester content of 1.5 wt% or less was blended. The cleansing agent was excellent in foaming power and detergency, was low in skin buildup property, and was also excellent in cold resistance. On the other hand, the conventional amide ester content is 1.5 wt.
% Or more of the polyoxyethylene fatty acid amide sulfate ester type surfactants, the cleaning agents of Comparative Examples 4 to 7 were inferior in any of foaming power, cleaning power, skin irritation and cold resistance. .

[0120]

EXPERIMENTAL EXAMPLE 1 Polyoxyethylene (3) coconut oil containing no amide ester, obtained in Example 2, and fatty acid sodium amide sulfate (26%) were added to N, O-dicocoyl polyoxyethylene (3) coconut oil. After adding a predetermined amount of fatty acid amide (addition amount to polyoxyethylene (3) coconut oil fatty acid amide sodium sulfate pure content), once at 70 ° C
The mixture was heated to 0.degree. C. to dissolve the amide ester and then slowly cooled to check whether turbidity appeared. The results are shown in Table 3.
It was shown to. The evaluation criteria were set as follows. 〇… Transparent and no turbidity △… Transparent at room temperature, but white turbidity after storage at −5 ° C. for 7 days ×… Muddy at room temperature

[0121]

[Table 3]

As is clear from the results shown in Table 3, when the content of the amide ester exceeds 3% by weight, turbidity is observed even at room temperature, and when it is 2 to 3% by weight, turbidity is observed when it is cold. Was inferior. However, l. When it is 5% by weight or less, no turbidity is observed even when cooled,
It was excellent in cold resistance.

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 4 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.

[0126]                       Ingredient weight%         Example 2 compound 10.0         N-2-hydroxyethyl-N-2-coconut oil fatty acid               Amidoethylglycine (30%) 15.0         N-coconut oil fatty acid acyl-L-glutamic acid               Monotriethanolamine (25%) 5.0         Lauroyl methyl taurine sodium (30%) 5.0         Lauric acid diethanolamide 2.0         Coconut oil fatty acid monoethanolamide 1.5         Sodium hyaluronate 0.5         Amount to make caustic soda pH 6.0         Methylparaben 0.1         Fragrance suitable amount         Remaining water The test results are shown in Table 4.

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

[0128]                       Ingredient weight%         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         Distearic acid ethylene glycol ester 2.0         Monoammonium glycyrrhizinate 0.2         Methylparaben 0.1         Amount to adjust citric acid pH to 6.5         Remaining water The test results are shown in Table 4.

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

[0130]                   Ingredient weight%         Compound of Example 3 15.0         Lauric acid monoethanolamide 3.0         2-Palm oil alkyl-N-carboxymethyl-N-               Hydroxyethyl imidazolinium betaine               (30%) 10.0         Piroctone olamine 0.7         Sodium hyaluronate 0.1         Methylparaben 0.1         EDTA 0.1         Citric acid pH = 7         Remaining water The test results are shown in Table 4.

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

[0132]                       Ingredient weight%         Compound of Example 1 5.0         Example 2 compound 10.0         Coconut oil fatty acid amide propyl dimethylamino               Betaine acetate (30%) 20.0         Carboxymethyl chitin 0.1         Methylparaben 0.1         EDTA 0.1         Citric acid pH = 7         Remaining water The test results are shown in Table 4.

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

[0134]                   Ingredient weight%         Compound of Example 1 8.0%         Lauric acid monoethanolamide 2.0         Lauroylmethyl-β-alanine sodium               (30%) 20.0         Stearyl trimethyl ammonium chloride 2.0         Cetyl octoate 0.5         Methylparaben 0.1         EDTA 0.1         Citric acid pH = 7         Remaining water The test results are shown in Table 4.

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

[0136]                   Ingredient weight%         2-alkyl-N-carboxymethyl-N-hydroxy               Ethylimidazolinium betaine (30%) 20.0         Example 2 compound 10.0         Lauric acid diethanolamide 3.0         Lauric acid triethanolamine 7.0         Methylparaben 0.1         EDTA 0.1         Remaining water The test results are shown in Table 4.

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 4 shows the test results.

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

[0140]                   Ingredient weight%         Decyl glucoside (1.7) 5.0         Compound of Example 1 5.0         Cocoyl isethionate sodium 5.0         Lauric acid diethanolamide 3.0         Polyoxyethylene (2) lauric acid monoethanol               Amide 3.0         Methylparaben 0.1         EDTA 0.1         Remaining water The test results are shown in Table 4.

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

[0142]                   Ingredient weight%         Polyoxyethylene (3) lauryl               Sodium ether sulfate 15.0         Compound of Example 4 11.0         Monosodium monolauryl phosphate 4.0         Lauric acid diethanolamide 3.0         Methylparaben 0.1         EDTA 0.1         Remaining water The test results are shown in Table 4.

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

[0144]                   Ingredient weight%         Polyoxyethylene (5) lauric acid monoethanol               Disodium Amidosulfosuccinate (30%) 15.0         Compound of Example 4 11.0         Lauryl dimethylamine oxide 4.0         Ethanol 2.0         Remaining water The test results are shown in Table 4.

[0145]

[Table 4]

As is clear from the results shown in Table 4, the cleaning of Examples 18 to 28 in which the polyoxyethylene fatty acid amide sulfate ester type surfactant having the amide ester content of the present invention of 1.5 wt% or less was blended. The agent was excellent in foaming power, detergency, low in skin irritation, and excellent in cold resistance.

[0147]

According to the present invention, excellent foaming power / cleaning power,
Moreover, it is possible to obtain a polyoxyethylene fatty acid amide sulfuric acid ester salt type surfactant which is less irritating to the skin and hair and which is excellent in cold resistance, and a detergent composition containing the same.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-5-339596 (JP, A) JP-A-3-215410 (JP, A) JP-A-2-222493 (JP, A) JP-A-2- 235999 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B01F 17/00-17/56

Claims (4)

(57) [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, and M represents 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. , V represents an integer equal to the valence of the atom or group represented by M), and is a polyoxyethylene fatty acid amide sulfate ester type surfactant. 2. The following general formula (3): (In the formula, RCO represents a straight chain or branched chain saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms), ethylene oxide is added to the fatty acid monoethanolamide, and 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). (In the formula, RCO and m are the same as defined above), the polyoxyethylene fatty acid amide is transferred to the polyoxyethylene fatty acid amide, a sulfuric esterification agent is reacted, and the reaction product is
An amide ester represented by the above general formula (1), characterized by being neutralized with a neutralizing agent comprising an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonia, an alkanolamine, or a basic amino acid. Content rate of
General formula (2) below 1.5 wt% (In the formula, RCO and n are as defined above. M is an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cation of a basic amino acid contained in the neutralizing agent. Represents a sex residue,
v represents an integer equal to the valence of the atom or group represented by M), and a method for producing a polyoxyethylene fatty acid amide sulfate ester 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) with t% or less: (In the formula, RCO and n are the same as defined above, and M represents 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. , V represents an integer equal to the valence of the atom or group represented by M), and a detergent composition comprising a polyoxyethylene fatty acid amide sulfate ester type surfactant. 4. The polyoxyethylene fatty acid amide sulfate ester type surfactant represented by the general formula (2), wherein the content of the amide ester represented by the general formula (1) is 1.5 wt% or less. And anionic surfactant and /
Alternatively, a detergent composition containing an amphoteric surfactant.