JPH0967333A - Polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture, its production and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject mixture consisting of specific compounds expressed by a specific formula, having excellent frothing power, detergent power and pH stability, giving extremely low stimulation to the skin and the hair and refreshing feeling to the body and suitable as a surfactant, etc. SOLUTION: The objective mixture is composed of two or more kinds of compounds of formula [R is a 7-12C (un)saturated hydrocarbon group; EO is oxyethylene group; PO is oxypropylene group; (x) is 1 or 2; (y) and (z) are each 0 or >=1; M<1> is an alkali metal, an alkaline earth metal, ammonium, a cationic residue of an alkanolamine or a cationic residue of a basic amino acid; (m) is an integer equal to the valence number of the M<1> atom or group] provided that (y') (the average of (y)) is 0 or a positive number of <=1 and (z') (the average of (z)) is a positive number of 0.3-20.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a mixture of polyoxypropylene fatty acid alkanolamide sulfate ester compounds (including polyoxypropylene fatty acid alkanolamide sulfate ester salt and polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt). The present invention relates to an industrially easy manufacturing method thereof and a detergent composition containing the compound mixture.

More specifically, the present invention is excellent in foaming power and detergency, has a large amount of foam, is creamy, and has no feeling of slimyness or squeaking during rinsing and is excellent in usability. In addition, polyoxypropylene fatty acid alkanolamide sulfate ester compound (polyoxypropylene fatty acid alkanolamide sulfate ester compound and polyoxypropylene fatty acid alkanolamide sulfate ester salt compound The present invention relates to an oxypropylene polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt compound (hereinafter the same), a method for industrially producing it efficiently and with excellent stability, and a detergent composition containing the same. is there.

[0003]

2. Description of the Related Art Generally, anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates and α-olefin sulfonates are widely used as detergents for cleaning. However, all of these anionic surfactants have skin irritation to varying degrees, but when used continuously for a long period of time, they have the problem of roughening the skin or hair.

In recent years, as a cleansing agent for improving skin irritation, it is produced by adding ethylene oxide to fatty acid monoethanolamide, converting the ethylene oxide addition reaction product into a sulfuric acid ester, and neutralizing the product. Anionic activators are known. The composition produced by the above method has the following general formula (6):

[Chemical 6] (In the formula (6), R and EO are the same as above, n is an integer of 1 or more, and m and M ¹ are the same as above.).

Since the polyoxyethylene fatty acid monoethanolamide sulfate ester salt of the above general formula (6) is easily hydrolyzed and has low chemical stability, when it is used as a detergent, the viscosity and pH decrease with time. It had a defect such as occurrence of. This drawback has, as a result, led to a deterioration in the quality stability of products containing the polyoxyethylene fatty acid monoethanolamide sulfate salt.

The cause of the low stability of the compound of formula (6) is
It is considered to be in the fatty acid monoethanolamide sulfate ester salt contained in the detergent. Therefore,
In order to reduce the content of the fatty acid monoethanolamide sulfate ester salt present in the polyoxyethylene fatty acid monoethanolamide sulfate salt-containing composition, the number of moles of ethylene oxide added is increased in the polyoxyethylene fatty acid monoethanolamide synthesis process. The method of doing is taken. Specifically, when the ethylene oxide addition mole number is 4 or more (n ≧ 4), the content of the fatty acid monoethanolamide remaining in the product mixture in the obtained polyoxyethylene fatty acid monoethanolamide is almost 0%. As a result, the stability of the resulting detergent composition over time is also improved. However, if the number of added moles of ethylene oxide is increased in this way,
The resulting cleaning composition has a problem that the foaming power and the cleaning power are lowered, and the feeling of sliminess increases and the usability deteriorates. Therefore, it has been strongly desired to solve the above problems.

[0007]

DISCLOSURE OF THE INVENTION The present invention is excellent in foaming power / detergency, rich in foam amount and creamy, and excellent in feeling of use without slimy feeling or tingling sensation during rinsing, and on skin and A polyoxypropylene fatty acid alkanolamide sulfate ester compound mixture having less irritation to hair and having high product stability, and a method for producing the same,
And a detergent composition containing the same.

[0008]

[Means for Solving the Problems] The present inventors
A detergent with high detergency, abundant foam volume and creamy, an excellent feeling of use with no slimy feeling or tingling sensation during rinsing, low irritation to skin and hair, and high product stability. As a result of earnest research to obtain a composition, a fatty acid monoethanolamide, a fatty acid diglycolamide, a polyoxyethylene fatty acid monoethanolamide, or a polyoxyethylene fatty acid diglycolamide of a sulfuric acid ester salt compound of a propylene oxide adduct was found. Found to be effective in solving the above problems,
The present invention has been completed.

In the present invention, the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound includes polyoxypropylene fatty acid alkanolamide sulfate ester salt and polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt.
The present invention also includes a method for producing a polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture and a detergent composition containing the same.

That is, the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention has the following general formula (1):

[Chemical 7] (In the formula (1), R represents a linear or branched saturated hydrocarbon or unsaturated hydrocarbon group having 7 to 21 carbon atoms, E
O represents an oxyethylene group, PO represents an oxypropylene group, x represents an integer of 1 to 2, y, and z
Are each independently an integer from 0 to 1 or more.
M ¹ 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, and m
Represents an integer equal to the valence of the atom or group represented by M ¹ . ) A mixture of two or more compounds represented by the formula (1), wherein the average value y'of y in this compound mixture is 0.
Or a positive number less than or equal to 1 and an average value z of z is 0.3
It is characterized by being a positive number of -20.

The method for producing the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the above formula (1) according to the present invention is represented by the following general formula (2):

Embedded image (In the formula (2), R is the same as above, and R ¹ has ¹ carbon atom.
Represents an alkyl group of 1 to 3. ) A fatty acid alkyl ester represented by the following general formula (3):

Embedded image (In the formula (3), x is the same as the above.) The alkanolamine represented by the formula (3) is reacted in the presence of a base catalyst, and the following general formula (4) produced by this reaction:

Embedded image (In the formula (4), R and x are the same as above.) A reaction mixture containing a fatty acid alkanolamide was prepared, and the reaction mixture was added to the reaction mixture without purification. The following general formula (5) produced by this addition reaction by adding 0 to 1 times the molar amount of ethylene oxide to the compound of the general formula (4)

Embedded image (In the formula (5), R, x, EO and y are the same as defined above.) A reaction mixture containing a polyoxyethylene fatty acid alkanolamide compound is prepared, and the reaction mixture is not purified. In addition, the compound of the general formula (5) contained in the reaction mixture is subjected to an addition reaction with 0.3 to 20 times the molar amount of propylene oxide, and the addition reaction product is converted into a sulfuric acid ester salt. It is a feature.

The detergent composition of the present invention is a detergent composition containing a mixture of the polyoxypropylene fatty acid alkanolamide sulfate ester compound of the above formula (1).

The detergent composition of the present invention comprises a mixture of polyoxypropylene fatty acid alkanolamide sulfate ester salt of the above formula (1), an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. It is preferable to contain at least one selected from

The detergent composition according to the present invention comprises the polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture (A) represented by the above formula (1) and N-
Acyl amino acid and its salt (Ba), amidocarboxylic acid type surfactant (Bb), and amphoteric surfactant (B
It is preferable that it contains at least one surfactant (B) selected from c).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the polyoxypropylene fatty acid monoethanolamide sulfate ester salt contained in the compound mixture of the present invention are shown in the following [1] and [2].
It is as follows. In the compound names below, the number in parentheses is the number of moles of propylene oxide that has been subjected to the addition reaction with respect to 1 mole of the fatty acid alkanolamide.

[1] Polyoxypropylene (0.3) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (1) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (1.5) lauric acid monoethanolamide sulfate Sodium, polyoxypropylene (2) sodium lauric acid monoethanolamide sulphate, polyoxypropylene (2) potassium lauric acid monoethanolamide sulphate, polyoxypropylene (2) magnesium lauric acid monoethanolamide sulphate, polyoxypropylene (2) Lauric acid monoethanolamide ammonium sulfate, polyoxypropylene (2) lauric acid monoethanolamide triethanolamine sulfate, polyoxypropylene (2) lauric acid monoethanolamine Desulfate lysine salt, polyoxypropylene (5) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (10) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (20) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (1.5) Capric acid monoethanolamide sodium sulfate, polyoxypropylene (2) Decanoic acid monoethanolamide sodium sulfate,
Polyoxypropylene (3) Myristic acid monoethanolamide sodium sulfate, Polyoxypropylene (5)
Sodium palmitate monoethanolamide sulfate, polyoxypropylene (10) Sodium stearic acid monoethanolamide sulfate, polyoxypropylene (2
0) Isostearic acid monoethanolamide sulfate, polyoxypropylene (3) oleic acid monoethanolamide sulfate, polyoxypropylene (2) linoleic acid monoethanolamide sulfate, polyoxypropylene (2) linolenic acid monoethanolamide sulfate Sodium, polyoxypropylene (5) -2-heptyl undecanoic acid sodium monoethanolamide sulfate, polyoxypropylene (1) coconut oil fatty acid sodium monoethanolamide sulfate, polyoxypropylene (0.3) tallow fatty acid monoethanolamide sodium sulfate , And polyoxypropylene (2)
Palm kernel oil fatty acid monoethanolamide sodium sulfate.

[2] Polyoxypropylene (0.3) sodium diglycolamide laurate sulfate, polyoxypropylene (1) sodium diglycolamide laurate sulfate, polyoxypropylene (1.5) diglycolamide laurate sulfate Sodium, polyoxypropylene (2) sodium lauric acid diglycolamide sulfate, polyoxypropylene (2) potassium lauric acid diglycolamide sulfate, polyoxypropylene (2)
Lauric acid diglycolamide magnesium sulfate, polyoxypropylene (2) lauric acid diglycolamide ammonium sulfate, polyoxypropylene (2) lauric acid diglycolamide sulfate triethanolamine, polyoxypropylene (2) lauric acid diglycolamide sulfate lysine Salt, polyoxypropylene (5) sodium diglycolamide laurate sulfate, polyoxypropylene (10) sodium diglycolamide laurate sulfate, polyoxypropylene (20) sodium diglycolamide laurate sulfate, polyoxypropylene (1. 5) Capric acid sodium diglycolamide sulfate, polyoxypropylene decane (2) sodium acid diglycolamide sulfate, polyoxypropylene (3) diglycerate myristate Sodium amide amide sulfate, polyoxypropylene (5) sodium diglycol amide sulfate palmitate, polyoxypropylene (10) sodium diglycol amide sulfate stearate, polyoxypropylene (20) sodium diglycol amide isostearate sodium polyoxypropylene ( 3) Sodium oleic acid diglycolamide sulfate, polyoxypropylene (2) sodium linoleic acid diglycolamide sulfate, polyoxypropylene (2) sodium diglycolamide linolenic acid, polyoxypropylene (5) -2-heptylundecanoic acid Sodium Diglycolamide Sulfate, Polyoxypropylene (1) Coconut Oil Fatty Acid Sodium Diglycolamide Sulfate, Polyoxypropylene (0.3) Tallow Fatty Acid Diglyce Ruamido sodium sulfate and polyoxypropylene (2) palm kernel oil fatty acid diglycol amides sodium sulfate.

The polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt contained in the compound mixture of the present invention is exemplified in the following [3] and [4].
The number in parentheses in the following compound names represents the number of moles of propylene oxide and ethylene oxide that have been subjected to the addition reaction with respect to 1 mole of the fatty acid alkanolamide.

[3] polyoxypropylene (0.3) polyoxyethylene (1) sodium lauric acid monoethanolamide sulphate, polyoxypropylene (1) polyoxyethylene (0.2) sodium lauric acid monoethanolamide sulphate, Polyoxypropylene (1) Polyoxyethylene (0.5) Sodium lauric acid monoethanolamide sulfate, Polyoxypropylene (1) Polyoxyethylene (1) Sodium lauric acid monoethanolamide sulfate, Polyoxypropylene (1.5) Polyoxyethylene (1) lauric acid monoethanolamide sodium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide sodium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauri Acid monoethanolamide potassium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide magnesium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide ammonium sulfate, polyoxypropylene ( 2) Polyoxyethylene (1) lauric acid monoethanolamide triethanolamine sulfate, polyoxypropylene (2) Polyoxyethylene (1) lauric acid monoethanolamide sulfate lysine salt, polyoxypropylene (5) polyoxyethylene (1 ) Sodium lauric acid monoethanolamide sulfate, polyoxypropylene (10) polyoxyethylene (1) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (20) polyoxy Tylene (1) sodium lauric acid monoethanolamide sulfate, polyoxypropylene (1.5) polyoxyethylene (1) sodium capric acid monoethanolamide sulfate, polyoxypropylene (2) polyoxyethylene (1) monoethanol decanoate Sodium amidosulfate,
Polyoxypropylene (3) Polyoxyethylene (1)
Myristic acid sodium monoethanolamide sulfate, polyoxypropylene (5) polyoxyethylene (1) sodium palmitic acid monoethanolamide sulfate, polyoxypropylene (10) polyoxyethylene (1) sodium stearate monoethanolamide sulfate, polyoxy Propylene (20) Polyoxyethylene (1) Isostearic acid monoethanolamide sodium sulfate,
Polyoxypropylene (3) Polyoxyethylene (1)
Oleic acid monoethanolamide sodium sulfate, polyoxypropylene (2) polyoxyethylene (1) linoleic acid sodium monoethanolamide sulfate, polyoxypropylene (2) polyoxyethylene (1) linolenic acid monoethanolamide sodium sulfate, polyoxy Propylene (5) Polyoxyethylene (1) -2-heptyl undecanoic acid monoethanolamide sodium sulfate,
Polyoxypropylene (1) Polyoxyethylene (1)
Coconut oil fatty acid monoethanolamide sodium sulfate, polyoxypropylene (0.3) polyoxyethylene (1) tallow fatty acid monoethanolamide sodium sulfate, and polyoxypropylene (2) polyoxyethylene (1) palm kernel oil fatty acid monoethanol Sodium amidosulfate.

[4] Polyoxypropylene (0.3) polyoxyethylene (1) sodium lauric acid diglycolamide sulfate, polyoxypropylene (1) polyoxyethylene (0.2) sodium diglycolamide lauric acid sulfate, Polyoxypropylene (1) Polyoxyethylene (0.5) Sodium lauric acid diglycolamide sulfate, Polyoxypropylene (1) Polyoxyethylene (1) Sodium lauric acid diglycolamide sulfate, Polyoxypropylene (1.5) Polyoxyethylene (1) sodium lauric acid diglycolamide sulfate, polyoxypropylene (2) polyoxyethylene (1) sodium diglycolamide lauric acid,
Polyoxypropylene (2) Polyoxyethylene (1)
Lauric acid diglycolamide potassium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide magnesium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide ammonium sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide triethanolamine sulfate, polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide sulfate lysine salt, polyoxypropylene (5) polyoxyethylene ( 1) Sodium lauric acid diglycolamide sulfate, polyoxypropylene (1
0) Polyoxyethylene (1) sodium lauric acid diglycolamide sulfate, polyoxypropylene (20)
Polyoxyethylene (1) lauric acid diglycolamide sodium sulfate, polyoxypropylene (1.5) polyoxyethylene (1) capric acid sodium diglycolamide sulfate, polyoxypropylene (2) polyoxyethylene (1) decanoic acid Sodium diglycolamide sulfate, polyoxypropylene (3) polyoxyethylene (1) sodium myristate diglycolamide sulfate, polyoxypropylene (5) polyoxyethylene (1) sodium diglycolamide palmitate, polyoxypropylene ( 10) Polyoxyethylene (1) sodium stearate diglycolamide sulfate, polyoxypropylene (20) Polyoxyethylene (1) sodium isostearate diglycolamide sulfate, polyoxypropyi Down (3) polyoxyethylene (1) diglycol amides sodium sulfate oleate,
Polyoxypropylene (2) Polyoxyethylene (1)
Sodium linoleic acid diglycolamide sulfate, polyoxypropylene (2) polyoxyethylene (1) sodium linolenic acid diglycolamide sulfate, polyoxypropylene (5) polyoxyethylene (1) -2-heptylundecanoic acid diglycolamide sulfate Sodium, polyoxypropylene (1) polyoxyethylene (1) coconut oil fatty acid diglycolamide sodium sulfate, polyoxypropylene (0.3) polyoxyethylene (1) tallow fatty acid diglycolamide sodium sulfate, and polyoxypropylene ( 2) Polyoxyethylene (1) Palm kernel oil fatty acid diglycolamide sodium sulfate.

The alkanolamide group constituting the polyoxypropylene fatty acid alkanolamide compound of the present invention means a monoethanolamide group or a diglycolamide group. That is, x = 1 or 2 in the formula (1). When the alkanolamide group has a long oxyethylene group chain like the triglycolamide group (that is, x ≧ 3), the polyoxypropylene fatty acid alkanolamide sulfate compound mixture obtained by sulfating it is used. At the same time, it has a drawback in that a strong tingling sensation appears, and the foaming power and cleaning power decrease.

The average value y'of the number of moles y of ethylene oxide (EO) added in the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention is y '.
Is a positive number of 0 or 1 or less. When the average value y ′ of the number of added moles y exceeds 1, the foaming power and detergency of the resulting polyoxypropylene fatty acid alkanolamide sulfate compound mixture become insufficient, and a slippery feeling appears at the time of use.
The creamy feeling of the foam becomes poor. In order to obtain those having excellent foaming power and detergency, it is preferable that the average value y ′ of the ethylene oxide addition mole number y is 0 or 0.5 or less, and among them, the ethylene oxide addition mole number y is particularly preferable.
The average value y'of 0, that is, the product to which ethylene oxide is not added is superior to the product to which ethylene oxide is added in foaming power and detergency. On the other hand, in terms of stability, when compared with the product without addition of ethylene oxide and the product with addition of ethylene oxide, the product with addition is superior.

The addition mole number z of propylene oxide in the polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture of the present invention is an integer of 0 or 1 or more, and its average value z ', that is, the average mole number is 0.3. ~ 20. This average added mole number z'is 0.3
If it is less than 1, the stability is poor and the water solubility is low. In some cases, crystals may precipitate during low temperature storage. When the average value z'exceeds 20, the foaming power and the detergency are deteriorated, and the refreshing feeling after the washing is lost and a slippery feeling appears. Within the range of 0.3 to 20 of the average added mole number z'of propylene oxide, the smaller the average added mole number z'of the foaming power, the detergency, and the refreshing feeling, the more specifically, the average. It is preferable that the number of added moles z'is 0.3 to 3. On the other hand, for stability, the larger the number of added moles z ', the better, and specifically, the average number of added moles z'is preferably 3 to 20.

The counter cation M ¹ of the product of the present invention includes alkali metal atoms such as sodium and potassium, alkaline earth metal atoms such as magnesium and calcium,
Ammonium groups, cationic residues of alkanolamines such as triethanolamine, and cationic residues of basic amino acids such as lysine and arginine are used.

Hereinafter, a method for producing a mixture containing the polyoxypropylene fatty acid alkanolamide sulfate ester salt represented by the general formula (1) and the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt will be described in detail.

The polyoxypropylene fatty acid alkanolamide sulfate compound mixture of the present invention is produced by sulfuric acid esterification of a polyoxypropylene fatty acid alkanolamide mixture obtained by adding propylene oxide to a fatty acid alkanolamide. The polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt mixture of the present invention is a polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture obtained by adding ethylene oxide to a fatty acid alkanolamide by a conventional method and then adding propylene oxide. After that, it is produced by sulphating a sulfuric ester.

The conditions for the addition reaction of ethylene oxide to the fatty acid alkanolamide are not particularly limited,
For example, reacting a fatty acid alkanolamide with ethylene oxide in the presence of a Lewis acid catalyst such as boron trifluoride or titanium chloride, or a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. Achieved by
This addition reaction requires the presence of the catalyst as described above, and the non-catalyzed addition reaction of ethylene oxide to the highly purified fatty acid alkanolamide by acid treatment or the like does not proceed or becomes very slow.

The method of adding propylene oxide to the fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide is not particularly limited, but a Lewis acid catalyst such as boron trifluoride or titanium chloride, or sodium hydroxide or potassium hydroxide. It is achieved by reacting propylene oxide in the presence of a base catalyst such as sodium methoxide, sodium methoxide, or sodium ethoxide. This addition reaction requires the presence of any of the above catalysts and the uncatalyzed addition reaction of propylene oxide to highly purified fatty acid alkanolamides does not proceed or is very slow.

The temperature of the propylene oxide addition reaction is
It may be higher than the melting point of the fatty acid alkanolamide or the polyoxyethylene fatty acid alkanolamide,
80-180 degreeC is preferable. When the addition reaction temperature is lower than 80 ° C., the reaction is slow, and when it is higher than 180 ° C., the coloring is remarkable, which is not preferable. In order to prevent or suppress such coloring, it is effective to replace the air in the reactor with an inert gas in advance. As a method of charging propylene oxide,
Any method such as (a) charging before heating, (b) heating to the reaction temperature and then press-fitting in a liquid state, (c) heating to the reaction temperature and then blowing in a gas state may be used. However, since this addition reaction is exothermic, the temperature control may become difficult if the method (a) is adopted. Therefore, in mass production, it is preferable to employ the methods (b) to (c), which are easy to control the temperature.

After the completion of the propylene oxide addition reaction, the obtained polyoxypropylene fatty acid alkanolamide and / or polyoxypropylene polyoxyethylene fatty acid alkanolamide-containing reaction mixture is directly subjected to the sulfuric acid esterification reaction in the next step without purification. Be served.

In the propylene oxide addition reaction, a solvent may be used as long as it does not hinder the reaction. Examples of the solvent that can be used at this time include hydrocarbon solvents such as hexane, benzene, toluene, and xylene,
Halogen-based solvents such as chloroform and dichloroethane,
And tetrahydrofuran, diisopropyl ether,
And ether solvents such as dibutyl ether.

To prepare the sulfate ester salts of the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture, the polyoxypropylene fatty acid alkanolamide compound mixture is reacted with a sulfate esterifying agent. Is converted to a sulfuric acid ester, and the reaction product is neutralized with a neutralizing agent.

As the sulfuric acid esterifying agent, for example, chlorosulfonic acid, concentrated sulfuric acid, sulfuric acid anhydride, sulfamic acid and the like can be used. Further, as the neutralizing agent, a hydroxide of an alcal metal (for example, sodium, potassium, etc.),
Hydroxides or oxides of alcal earth metals (eg magnesium, calcium etc.), ammonia, alkanolamines (eg triethanolamine) or basic amino acids (eg lysine, arginine etc.) can be used. When sulfamic acid is used as the sulfuric acid esterifying agent, the sulfuric acid esterification product is an ammonium salt, and therefore neutralization is not necessary.

In the method of the present invention, to obtain a fatty acid alkanolamide compound, (1) a method of dehydrating and condensing a fatty acid and an alkanolamine, (2) a method of reacting a fatty acid halide with an alkanolamine, and (3) a base catalyst In the presence, a method of producing a lower alcohol ester of fatty acid and an alkanolamine as a by-product, a method of reacting while removing the lower alcohol, and the like can be used.

In the above method (1), it is difficult to complete the reaction, some unreacted raw materials remain, and the reaction temperature must be higher than that in other methods. It has a serious drawback. The above method (2) requires a reagent and a device for trapping hydrogen chloride, which is generated, and also has a problem of corrosion of the device and fatty acid halide is relatively expensive, and thus is an industrially excellent method. It is hard to say.

In order to obtain the polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture of the present invention, the above method (3) is preferable because the fatty acid alkanolamide used can be produced in high purity. A basic catalyst is used in the reaction (3). As described above, it is necessary to use a catalyst for the addition of ethylene oxide or propylene oxide in the next step. However, when the fatty acid alkanolamide is prepared by the method (3), the base catalyst is used for the addition reaction of ethylene oxide and propylene oxide. Since it is also effective as a catalyst, if the method (3) is adopted, it is not necessary to add a catalyst essential for the addition reaction at the stage of adding ethylene oxide or propylene oxide. Therefore, this method is a very efficient method. is there.

An example of the most efficient method for producing the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention is as follows.
That is, a fatty acid alkanolamide is prepared by heating a reaction system containing a fatty acid lower alcohol ester, monoethanolamine or diglycolamine, and a base catalyst to carry out a condensation reaction while distilling off the generated lower alcohol. Next, this fatty acid alkanolamide is subjected to an addition reaction of propylene oxide or ethylene oxide, and then an addition reaction of propylene oxide. Then, this product is further reacted with a sulfuric acid esterifying agent and then neutralized with a neutralizing agent. An example of this reaction is as follows.

[0038]

[Chemical 12]

Examples of the fatty acid alkyl ester represented by the general formula (2) used in the method of the present invention include capric acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid and linoleic acid. , Linolenic acid, coconut oil fatty acid, beef tallow fatty acid, and palm kernel oil fatty acid such as methyl ester, ethyl ester, propyl ester, and isopropyl ester.

The alkanolamine represented by the general formula (3) used in the method of the present invention is monoethanolamine,
Either diglycolamine (x = 1 or 2). An alkanolamine represented by the general formula (3):
The molar ratio [(3) / (2)] to the fatty acid alkyl ester represented by the general formula (2) is preferably 0.8 to 1.2, more preferably 1.0 to 1.1.

Examples of the base catalyst used in the method of the present invention include metal alkoxides such as sodium methoxide and sodium ethoxide, and metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount used is preferably 0.01 to 5 mol% and more preferably 0.5 to 2 mol% with respect to the fatty acid alkyl ester represented by the general formula (2).

The temperature of the amidation reaction is 50 to 150 ° C.
Is preferable, and a reaction time of 12 hours or less is sufficient. Since the lower alcohol produced by the amidation reaction is distilled off, the pressure in the reaction system should be 0.1 to 760 mm.
It is preferable to control in the range of Hg, 10 to 5
The range of 0 mmHg is more preferable. However, at this time, it is desirable to set the reaction conditions while checking the relationship with the temperature so that the reaction temperature does not exceed the boiling points of the fatty acid lower alkyl ester and the alkanolamine.

Since this amidation reaction proceeds almost quantitatively, the fatty acid alkanolamide-containing reaction mixture containing the base catalyst can be directly subjected to the next ethylene oxide or propylene oxide addition reaction without purification. The addition reaction of ethylene oxide or propylene oxide may be performed by the method described above. However, in general, many fatty acid alkanolamides and polyoxyethylene (0 to 1) fatty acid alkanolamides solidify when cooled. It is effective to charge propylene oxide in a liquid or gas form by the method (1) or (3). The reaction of sulfuric acid esterification may be performed by the method described above.

The polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture represented by the general formula (1) of the present invention is useful as a component of a detergent, and this is preferably used in a detergent. It is added at a content rate of 05 to 40% by weight, more preferably 0.1 to 30% by weight.

The polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture represented by the general formula (1) of the present invention has a sufficient surface activity even by itself. However, when it is used alone, the detergency is not always sufficient. However, surprisingly, it can be combined with other surfactants to enhance the performance of itself and the other surfactants. Further, it has a strong effect of alleviating the irritation of other surfactants. As other surfactants to be combined with the compound mixture of the general formula (I) of the present invention, any of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used. It may be selected from these according to the above and combined.

Examples of the anionic surfactant used in the detergent composition of the present invention include fatty acid soaps such as sodium laurate and triethanolamine laurate, and organic sulfones such as alkylbenzene sulfonates and α-olefin sulfonates. Acid salt, sodium lauryl sulfate, lauryl sulfate such as triethanolamine lauryl sulfate, ether sulfate such as polyoxyethylene (3) sodium lauryl ether sulfate, polyoxyethylene (3) coconut oil fatty acid amide ether sulfate such as sodium amide sulfate Salts, triethanolamine monododecyl phosphate, phosphoric acid esters such as sodium polyoxyethylene dodecyl ether phosphate, acylmethyl tau such as sodium cocoyl methyl taurine, sodium lauroyl methyl taurine Down salts, acyl isethionates, such as sodium lauroyl isethionate, sodium lauryl sulfosuccinate, disodium, POE (1 to 4) lauryl disodium sulfosuccinate, polyoxyethylene (5)
Sulfosuccinic acid type surfactants such as lauric acid monoethanolamide disodium sulfosuccinate, alkyl ether carboxylates, cocoyl sarcosine sodium,
N-acyl sarcosine salts such as sodium lauroyl sarcosine, sodium myristoyl sarcosine, potassium lauroyl sarcosine, triethanolamine, sodium cocoyl-N-methyl-β-alanine, sodium lauroyl-N-methyl-β-alanine, myristoyl-N -Methyl-β-alanine sodium, palmitoyl-N-methyl-β-alanine sodium, stearoyl-N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine potassium, lauroyl-N-methyl-β-alanine N-acyl-β-alanine salts such as triethanolamine, N-
N-acyl aspartates such as sodium lauroyl aspartate, triethanolamine N-lauroyl aspartate, sodium N-myristoyl aspartate, sodium N-lauroyl glutamate, N
-Lauroyl glutamic acid triethanolamine, N-
Examples thereof include amidecarboxylic acid type surfactants such as N-acylglutamates such as sodium cocoyl glutamate and triethanolamine N-cocoyl glutamate.

Examples of the cationic surfactant used in the detergent composition of the present invention include quaternary ammonium salt type cationic surfactants such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and distearyl dimethyl ammonium chloride. To be

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, N-2-hydroxyethyl-N-2-lauric acid amidoethylglycine, N- 2-hydroxyethyl-N-
2-coconut oil fatty acid amide ethylglycine, N-2-hydroxyethyl-N-2-lauric acid amide ethyl-β-
Alanine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethyl-β-alanine, N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) lauric acid amide] ethyl} glycine, N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine, N- {2- [N
Amidoamine type amphoteric surfactants such as-(2-hydroxyethyl) lauric acid amide] ethyl} glycine and N- {2- [N- (2-hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, alkylsulfobetaine type Examples thereof include amphoteric surfactants and amide sulfobetaine-type amphoteric surfactants such as coconut oil fatty acid amide dimethylhydroxypropyl sulfobetaine.

Examples of the nonionic surfactant used in the detergent composition of the present invention include coconut oil fatty acid diethanolamide and fatty acid diethanolamide such as lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, and lauric acid monoethanol. Fatty acid monoethanolamides such as amides, coconut oil fatty acid diglycolamides, fatty acid diglycolamides such as lauric acid diglycolamide, fatty acid isopropanolamides such as lauric acid isopropanolamide, polyoxyethylene (2) lauric acid monoethanolamide, and Polyoxyethylene (5) Polyoxyethylene fatty acid monoethanolamide such as coconut oil fatty acid monoethanolamide, fatty acid ester, alkyl such as lauryldimethylamine oxide Min oxide, POE higher alcohol ether, POE alkylphenyl ethers, and the like nonionic surfactants such as alkyl glucosides, such as decyl glucoside and the like.

As a preferred example of the detergent composition of the present invention, a component (A) consisting of a mixture of one or more polyoxypropylene fatty acid alkanolamide sulfate ester salt compounds represented by the general formula (1) and an N-acyl amino acid And salts thereof (acyl amino acid type surfactants) (B
Those containing at least one surfactant (B) selected from a), an amidocarboxylic acid type surfactant (Bb), and an amphoteric surfactant (Bc) have excellent foaming power and detergency. It is especially excellent, has a creamy foam quality, does not feel slimy or tingling during rinsing, has an excellent feeling of use, and has minimal irritation to the skin and hair. It is suitable as a composition.

The above-mentioned component (Ba) of the detergent composition of the present invention
Examples of the N-acyl amino acid type surfactant and the amidocarboxylic acid type surfactant used as and (Bb) include the following general formula (8):

Embedded image (However, in the formula (8), R ² represents a linear or branched saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, and R ³ represents an N-acyl amino acid type surfactant ( Ba)
In the formula (a) to (d) below, and in the amidocarboxylic acid type surfactant (Bb), a member selected from the groups (e) to (h) below. And M ² is a hydrogen atom, an alcal metal atom,
It represents an alcal earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid, and m represents an integer equal to the valence of M ² . ) Is mentioned.

In the N-acyl amino acid type surfactant compound (Ba) of the general formula (8), as the compound in which R ³ represents the group of the formula (a), cocoyl sarcosine sodium, lauroyl sarcosine sodium and myristoyl sarcosine sodium are exemplified. , Lauroyl sarcosine potassium,
Lauroyl sarcosine triethanolamine and the like can be mentioned.

In the compound (Ba) of the formula (8), R ³
A compound of formula (b) is cocoyl-N-
Methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine sodium, myristoyl-N-methyl-β-alanine sodium, palmitoyl-N-methyl-β-alanine sodium, stearoyl-N-methyl-β-alanine sodium , Lauroyl-N-methyl-β-alanine potassium, lauroyl-N-methyl-
β-alanine triethanolamine and the like can be mentioned.

In the compound (Ba) of the formula (8), R ³
Examples of the compound represented by the formula (c) include triethanolamine N-lauroyl aspartate and sodium N-myristoyl aspartate.

In the compound (Ba) of the formula (8), R ³
Examples of the compound represented by the formula (d) include sodium N-lauroylglutamate, triethanolamine N-lauroylglutamate, sodium N-cocoylglutamate, and triethanolamine N-cocoylglutamate.

In the amidecarboxylic acid type surfactant compound (Bb) of the formula (8), the compound in which R ³ represents the group of the formula (e) is N-2-hydroxyethyl-N-2-lauric acid amide. Examples thereof include ethylglycine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine, and the like.

In the compound (Bb) of the formula (8), R ³
Examples of the compound represented by the formula (f) include N-2-hydroxyethyl-N-2-lauric acid amidoethyl-β-alanine, and N-2-hydroxyethyl-N-2-coconut oil fatty acid amidoethyl-β. -Alanine and the like.

In the compound (Bb) of the formula (8), R ³
Is a compound of the formula (g), N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl)
Lauric acid amide] ethyl} glycine, N-carboxymethyl-N- {2- [N ′-(2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine and the like can be mentioned.

In the compound (Bb) of the formula (8), R ³
A compound represented by formula (h) includes N- {2- [N
Examples include-(2-hydroxyethyl) lauric acid amide] ethyl} glycine, and N- {2- [N- (2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine.

In the detergent composition of the present invention, the component (A) comprising the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt compound mixture represented by the formula (1) and the N-acyl amino acid salt (B
a), an amidocarboxylic acid type surfactant (Bb), and a surfactant component (B) consisting of at least one of an amphoteric surfactant (Bc), in a blending weight ratio (solid content) (A) /
(B) is preferably 9: 1 to 1: 9, and
The total content of the component (A) and the component (B) in this composition is preferably 0.1% by weight or more, and 0.1% by weight or more.
It is more preferably about 30% by weight. When the compounding ratio of the component (A) and the component (B) is out of the above range, the obtained detergent has a slimy feel or an insufficient refreshing feel, and the component (A) and the component If the total content with (B) is less than 0.1% by weight, the effect is not sufficient.

If desired, the detergent composition of the present invention may contain water-soluble polymers such as cationized polymer and cationized guar gum. In addition, the detergent composition of the present invention contains, if necessary, polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, and silicones such as methylpolysiloxane and oxyalkylene-modified organopolysiloxane. , Zinc pyrithione, antidandruff agent such as piroctone olamine, hyaluronic acid, collagen, elastin chondroitin sulfate, dermatanic acid, water-soluble polymer substances such as fibronectin, ceramides, chitin, chitosan, aloe extract, placenta extract and other cells Activator, allantoin, anti-inflammatory agent such as glycyrrhizinate, edetate, pyrophosphate, hexametaphosphate,
Chelating agents such as citric acid, malic acid, gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 3, 4,4 '
-Trichlorocarbanito, benzalkonium chloride, hinokitiol, resorcin and other preservatives, fungicides, dibutylhydroxytoluene, butylhydroxyanisole,
Antioxidants such as propyl gallate and ascorbic acid,
Fragrances and pigments can be appropriately added.

The state and shape of the detergent composition of the present invention are not limited, and any state and shape such as liquid, paste, gel, powder and solid may be used. The appearance is generally transparent, pearly, or emulsified, but is not limited to this. In order to produce the detergent composition of the present invention, the required components may be blended and mixed by an appropriate method and device.

The detergent composition of the present invention may be used for any purpose, but typically, it is a detergent such as kitchen detergent, hard surface detergent, face wash, cleansing foam, shampoo, body shampoo and solid detergent. Is mentioned.

The excellent characteristics of the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture represented by the general formula (1) of the present invention are that the propylene oxide group is added to the fatty acid alkanolamide group by an addition reaction. It is considered to be derived. The first-order addition reaction of propylene oxide with respect to the hydroxyl group of fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide proceeds relatively easily. The reaction at this time is shown by the following reaction formula, and the PO adduct produced gives two kinds of compounds (a) and (b) different from each other depending on the position of the methyl group of propylene oxide.

[0065]

Embedded image

The production ratio of these two compounds (a) and (b) is (a) :( b) ≈85: 15 when a base catalyst such as sodium methoxide is used, which is overwhelmingly large. To give the secondary alcohol compound (a). The reason for this is clear. That is, when the alkoxide of the fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide produced by the reaction of the fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide and the base catalyst reacts by nucleophilically attacking propylene oxide, This is because the oxide easily reacts with the oxirane ring carbon having less steric hindrance by the methyl group as shown below.

[0067]

Embedded image

Next, consider the step of adding another molecule of propylene oxide to the compounds (a) and (b). The reaction rate is faster in the case of adding to the compound (b) than in the case of the compound (a), but as for the ratio of the products, many of them still add to the compound (a), and the products are the same as in the first step. Contains a large amount of secondary alcohol compounds. As a result, the main product is the following compound (i).

Embedded image Other products are the following compounds (ii) to (iv).

Embedded image

In the addition reaction of propylene oxide as described above, when the addition mole number of propylene oxide is small, the addition reaction proceeds relatively sequentially, and therefore the fatty acid alkanolamide or the polyoxyethylene fatty acid alkanolamide is added. The distribution of the number of oxypropylene groups is quite narrow. However, this is not the case when the added mole number of propylene oxide is large.

On the other hand, the polyoxyethylene fatty acid alkanolamide obtained by adding ethylene oxide to the fatty acid alkanolamide has a wide distribution of the number of oxyethylene groups. The reason is that, in the case of addition of ethylene oxide, since the products are all primary alcohol compounds, there is a difference in reactivity between those without addition of ethylene oxide and those with addition of 1 mol or more. It is due to the fact that the addition reaction of the next stage proceeds. For example, FIG. 1 shows distribution states of oxypropylene groups and oxyethylene groups in a polyoxypropylene (2) lauric acid monoethanolamide mixture used in the present invention and a polyoxyethylene (2) lauric acid monoethanolamide mixture for comparison. Shown in.

It should be noted here that when alkylene oxide is added to lauric acid monoethanolamide in an amount of twice its molar amount, the number of oxyalkylene groups contained in the reaction mixture is 0, that is, the addition reaction. It is the residual content of the compound that did not undergo the treatment. That is, in the reaction mixture when ethylene oxide was added, the unreacted material to which ethylene oxide was not added remained at a high content rate of 13% by weight, whereas when propylene oxide was added, the unreacted material was not exist. The difference in the content ratio of the unreacted substances does not change even if these propylene oxide adducts are salified with sulfuric acid ester. That is, 13% by weight of lauric acid monoethanolamide sulphate ester salt remains in the polyoxyethylene (2) lauric acid monoethanolamide sulphate ester salt-containing mixture obtained by adding 2-fold molar amount of ethylene oxide. . It is known that the sulfuric acid ester salt of fatty acid alkanolamide unreacted with alkylene oxide greatly affects the stability of the main product polyoxyalkylene fatty acid monoethanolamide sulfuric acid ester salt compound. That is, the fatty acid alkanolamide sulfate ester salt is a compound that is easily decomposed with time, and a blended product containing this often shows an increase in viscosity and a decrease in pH with time.

On the other hand, the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture according to the present invention has a small content of the fatty acid alkanolamide sulfate ester salt, which is the causative agent of the instability, and therefore has stability over time. improves.

Regarding the foaming power and the refreshing feeling of use, it is generally said that it is better that the number of moles of alkylene oxide added is smaller, and it is desired that the oxyalkylene group is as short as possible. In the case of the polyoxyethylene fatty acid alkanolamide sulfate ester salt, as described above, the number of moles of ethylene oxide added must be 3 times or more moles in order to have an acceptable stability over time. . When the amount is less than 3 times the molar amount, the performance is excellent, but the decomposition gradually occurs.
Not suitable for long-term storage. However, the propylene oxide-added product of the present invention does not affect stability even if it is stored for a long period of time as long as it is a 1.5-fold or more molar propylene oxide adduct. Thus, in the case of adding propylene oxide according to the present invention,
Since a compound having a short number of oxypropylene groups can be synthesized without impairing the stability of the obtained compound mixture, there is an advantage that the foaming power and the like can be enhanced.

In recent years, in studies on ethylene oxide adducts of higher alcohols, higher alcohol ethoxylates having a narrowed EO distribution are called "narrow range", and narrow range polyoxyethylene alkyl ether sulfuric acid ester salts obtained by sulfuric acid esterification thereof are It has been reported that the cleaning performance is higher and the irritation is less than that of the conventional one having a broad distribution. The polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt mixture of the product of the present invention are considered to be a kind of narrow range. That is, the present invention was achieved by replacing the narrow range conversion, which was obtained only by adding conventional ethylene oxide, with propylene oxide. However, the above-mentioned various effects observed in the compound mixture of the present invention cannot be explained only by the narrow range effect, and are achieved by the influence of the sulfate group of the terminal hydroxypropyl group and many other factors. However, its mechanism of action has not been sufficiently clarified.

As described above, the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention further improves the characteristic performance of the polyoxyethylene fatty acid alkanolamide sulfate ester salt, and further eliminates the drawbacks thereof. It was done. In addition, the physical properties such as compatibility of the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention with other surfactants and additives are similar to those of the corresponding polyoxyethylene compound, and By using the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture of the present invention in place of the polyoxyethylene fatty acid alkanolamide sulfate ester salt that has been used as a component of a detergent composition, etc. Further effects can be expected in enhancement and improvement in stability over time.

[0076]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Polyoxypropylene (1)
Preparation of Uric Acid Monoethanolamide Sodium Sulfate) Monoethanolamine 62 was added to 214 g of methyl laurate.
g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. This was placed in an autoclave, 58 g (1 mol) of propylene oxide was further added, and the mixture was stirred at 120 ° C. for 3 hours to obtain 302 g of polyoxypropylene (1) lauric acid monoethanolamide.

The physical properties were as follows. Melting point: 36 ° C. Hydroxyl value: 191 Amine value: 6.0 IR analysis (Hitachi 270-30, KBr tablets): 329
2,3092, 2916, 2848, 1642, 156
^{4,1470,1378,1124,1052cm -1 1 H-NMR (Bruker} AC-250, CDC
l ₃ , TMS internal standard): δ 0.88 ppm (t, 3H,-
_{CH 3), 1.14ppm (m,} 3H, -CH (CH 3)
-O-), 1.26ppm (br, 16H, -CH
₂ −), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CO
NH -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 7H, -CH 2 CH 2 OCH
₂ CHO-), 5.86 ppm (br, 1H, NH),

GLC analysis: A sample obtained by converting 20 mg of the sample into TMS was injected into GLC. GLC conditions Carrier: Helium Flow rate: 30 ml / min Column: CHROMPACK OV1701 25 m × 0.32 mm ID, film thickness 0.2 μ Initial temperature: 230 ° C. Temperature rising rate: 5 ° C./min Final temperature: 300 ° C. Inlet temperature: 280 ° C. Detection Instrument: Table 1 shows the results of FID GLC analysis.

[0080]

[Table 1]

The reaction mixture containing polyoxypropylene (1) lauric acid monoethanolamide obtained was heated to 65 ° C.
The mixture was heated to a uniform temperature to melt it, and 119 g of chlorosulfonic acid was added dropwise to this melt under a nitrogen stream to polyoxypropylene (1) lauric acid monoethanolamide as a sulfuric ester. After removing hydrogen chloride generated at this time under reduced pressure, the reaction product was neutralized with sodium hydroxide to synthesize a polyoxypropylene (1) sodium lauric acid monoethanolamide sulfate mixture (anionic active ingredient: 26 %).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (m, 19H, -CH 2} -, - CH
_{(CH 3) -O -),} 1.60ppm (t, 2H, - CH
_{2 CH 2 CONH -), 2.18ppm} (t, 2H, - C
_{H 2 CONH -), 3.3~3.8ppm (} m, 7H, -
_{CH 2 CH 2 OCH 2 CHOSO 3} Na-).

Examples 2-5 and Comparative Examples 1-2 (polio)
Xypropylene lauric acid monoethanolamide sulfate
Preparation of Thorium) In each of Examples 2 to 5 and Comparative Examples 1 and 2, 62 g of monoethanolamine and 2 g of sodium methoxide were added to 214 g of methyl laurate, and the resulting methanol was distilled off under reduced pressure with heating and stirring (20 mmHg. , 14
(0 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. Put this in an autoclave and keep it at 90 ℃
While heating and stirring, the amount of propylene oxide shown in Table 2 was injected under pressure from a propylene oxide introducer, and the reaction system was stirred at 100 ° C. for 3 hours to polyoxypropylene lauric acid monoethanolamide mixture ( A mixture of compounds having different propylene oxide addition mole numbers was synthesized. Table 2 shows various physical properties and compositions.

[0084]

[Table 2]

1 mol of the obtained reaction product containing polyoxypropylene lauric acid monoethanolamide having various mol numbers of propylene oxide added was heated to 65 ° C. to be uniformly melted, and the melt was subjected to a nitrogen stream. Then, 119 g of chlorosulfonic acid was added dropwise to form a sulfuric acid ester.
Hydrogen chloride generated at this time was removed under reduced pressure, and the obtained reaction product was neutralized with sodium hydroxide to give polyoxypropylene lauric acid monoethanolamide sulfate sodium salt having various propylene oxide addition mole numbers. Table 3 shows the names of the compounds obtained in each Example and Comparative Example in which a mixture was synthesized (anionic active ingredient: 26%).

[0086]

[Table 3]

Example 6 (polyoxypropylene (1) la
Preparation of sodium diglycolamide urinate ) 214 g of methyl laurate and 106 of diglycolamine
g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(150 ° C., 1 hour) to obtain 290 g of lauric acid diglycolamide. Put this in the autoclave and 90
58 g (1 time mole) of gaseous propylene oxide was blown into this while heating and stirring at 100 ° C., and 100 ° C.
After stirring for 6 hours, 346 g of a polyoxypropylene (1) lauric acid diglycolamide mixture was synthesized.

The physical properties were as follows. Melting point: 30 ° C. Hydroxyl value: 170 Amine value: 10.7 IR analysis (Hitachi 270-30, KBr tablet): 330
4,3084,2920,2852,1648,155
6,1466,1376,1286,1128cm ^{-1 1} H
-NMR (Bruker AC-250, CDCl 3, T
MS internal standard): δ 0.88 ppm (t, 3H, -C)
_{H 3), 1.14ppm (d,} 3H, -CH (CH 3) -
O -), 1.26ppm (br, 16H, -CH 2 -),
1.62ppm (t, 2H, - CH 2 CH 2 CONH
−), 2.18 ppm (t, 2H, − CH ₂ CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 11H, - (CH 2 CH 2)
₂ OCH ₂ CHO-), 6.09 ppm (br, 1H, N
H)

GLC analysis: same as the method described in Example 1.
Table 4 shows the obtained analysis results.

[Table 4]

The obtained polyoxypropylene lauric acid diglycolamide mixture was heated to 65 ° C. to be uniformly melted, and 119 g of chlorosulfonic acid was added dropwise to the melt under a nitrogen stream to give polyoxypropylene lauric acid. The diglycol amide was sulfated. The hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with sodium hydroxide to synthesize a polyoxypropylene lauric acid diglycolamide sodium sulfate mixture (anionic active ingredient: 26%).

¹ H-NMR (Bruker AC-25
0, D ₂ O): δ 0.88 ppm (t, 3H, -C
_{H 3), 1.11~1.43ppm (m,} 19H, -CH
_{2 -, - CH (CH 3} ) -O -), 1.60ppm (t,
_{2H, - CH 2 CH 2 CONH} -), 2.18ppm
_{(T, 2H, - CH 2} CONH -), 3.3~3.8pp
m (m, 11H, - ( CH 2 CH 2 O) 2 -CH 2 CH
OSO ₃ Na-),

Examples 7-10 and Comparative Examples 3-4 (poly
Oxypropylene lauric acid diglycolamide sulfate
Preparation of Thorium) In each of Examples 7 to 10 and Comparative Examples 3 to 4, 214 g of methyl laurate and 106 g of diglycolamine were added.
And 1 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(40 ° C., 0.5 hour) to obtain 288 g of lauric acid diglycolamide. Put this in the autoclave and
While heating to 0 ° C. and stirring, the propylene oxide of the addition amount shown in Table 4 was pressure-inserted from the propylene oxide introducer, and the mixture was stirred at 100 ° C. for 3 hours and various addition mole numbers of polyoxypropylene lauric acid diester were added. A mixture of glycolamides was synthesized.

The physical properties and composition are shown in Table 5.

[Table 5]

1 mol of the obtained polyoxypropylene lauric acid monoethanolamide reaction product was heated to 65 ° C. to be melted uniformly, and 119 g of chlorosulfonic acid was added dropwise to the melt under a nitrogen stream to obtain a sulfuric ester. Turned into
The hydrogen chloride generated at this time was removed under reduced pressure, and the reaction product was neutralized with sodium hydroxide to synthesize a mixture of polyoxypropylene lauric acid diglycolamide sulfate sodium salt with various addition mole numbers (anion. Active ingredient: 26%).

Table 6 shows the names.

[Table 6]

Example 11 (Polyoxypropylene (2)
Polyoxyethylene (1) monoethanol laurate
Preparation of triethanolamine midsulfate ) Monoethanolamine 63 was added to 214 g of methyl laurate.
g and 0.5 g of sodium methoxide were added, and the produced methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 100 ° C., 1 hour) to obtain 243 g of lauric acid monoethanolamide. Put this in an autoclave and stir with heating at 90 ° C while stirring with ethylene oxide 44
g was injected in a gaseous state and reacted at 110 ° C. for 2 hours to prepare a polyoxyethylene (1) lauric acid monoethanolamide mixture. To this, 116 g (2 times mole) of propylene oxide was press-fitted and stirred at 130 ° C. for 4 hours to obtain polyoxypropylene (2) polyoxyethylene (1).
A lauric acid monoethanolamide mixture was synthesized.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 140 Amine value: 5.6 IR analysis (Hitachi 270-30, KBr tablet): 331
2,3080, 2924, 2852, 1650, 155
6,1466,1376,1352,1286,111
^{4cm -1 1 H-NMR (Bruker} AC-250, CDC
l ₃ , TMS internal standard): δ 0.88 ppm (t, 3H,-
_{CH 3), 1.14ppm (br,} 6H, -CH (C
_{H 3) -O -), 1.26ppm} (br, 16H, -CH
₂ −), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CO
NH -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 14H, - (CH 2 CH 2)
₂ O (CH ₂ CHO) ₂ −), 6.09 ppm (br, 1
H, NH)

The above mixture was heated to 40 ° C. to be uniformly melted, and the melt was mixed with chlorosulfonic acid 120 in a nitrogen stream.
g to form a sulfate ester, and then neutralized with an aqueous solution of triethanolamine to give polyoxypropylene (2)
A polyoxyethylene (1) lauric acid monoethanolamide sulfate triethanolamine salt mixture was synthesized (anionic active ingredient: 30%).

Example 12 (Polyoxypropylene (2)
Polyoxyethylene (1) diglycolamine laurate
Preparation of triethanolamine dodecyl sulfate) Diglycolamine 106 was added to 214 g of methyl laurate.
g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(100 ° C., 1 hour) to obtain 290 g of lauric acid diglycolamide. Put this in the autoclave and 90
The mixture was heated and stirred at 0 ° C., 44 g of ethylene oxide was injected under pressure in a gaseous state, and the mixture was reacted at 100 ° C. for 2 hours to prepare a polyoxyethylene (1) lauric acid diglycolamide mixture. 116 g (2 times mole) of propylene oxide was pressed into this and stirred at 130 ° C. for 4 hours to synthesize a polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide mixture.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 125 Amine value: 7.6 IR analysis (Hitachi 270-30, KBr tablet): 331
0,3080,2920,2852,1650,155
6,1466,1376,1350,1288,111
^{4cm -1 1 H-NMR (Bruker} AC-250, CDC
l ₃ , TMS internal standard): δ 0.88 ppm (t, 3H,-
_{CH 3), 1.14ppm (d,} 6H, -CH (CH 3)
-O-), 1.26ppm (br, 16H, -CH
₂ −), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CO
NH -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 18H, - (CH 2 CH
₂ O) _3- (CH ₂ CHO) _3- ), 6.09 ppm (b
r, 1H, NH)

This was heated to 40 ° C. and uniformly melted,
To this melt, 118 g of chlorosulfonic acid was added dropwise under a nitrogen stream to form a sulfuric acid ester, which was then neutralized with an aqueous triethanolamine solution to give polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide trisulfate. An ethanolamine salt mixture was synthesized (anionic active ingredient: 30%).

Comparative Example 5 (Polyoxypropylene (1)
Preparation of sodium triglycolamide urinate sulfate) 214 g of methyl laurate and 15 parts of triglycolamine
0 g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmH
g, 150 ° C., 1 hour) to obtain 333 g of lauric acid triglycolamide. This was placed in an autoclave and heated and stirred at 90 ° C., 58 g of gaseous propylene oxide was blown into this, and the mixture was stirred at 100 ° C. for 6 hours to synthesize a polyoxypropylene (1) lauric acid triglycolamide mixture. did.

The physical properties were as follows. Melting point: 24 ° C. Hydroxyl value: 144 Amine value: 2.7 IR analysis (Hitachi 270-30, KBr tablets): 330
4,3084,2920,2852,1648,155
^{6,1466,1376,1286,1128cm -1 1 H-NMR (Bruker} AC-250, CDC
l ₃ , TMS internal standard): δ 0.88 ppm (t, 3H,-
_{CH 3), 1.14ppm (d,} 3H, -CH (CH 3)
-O-), 1.26ppm (br, 16H, -CH
₂ −), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CO
NH -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 15H, - (CH 2 CH
₂ O) ₃ --CH ₂ CHO--), 6.09 ppm (br, 1
H, NH)

This was heated to 40 ° C. to uniformly melt,
120 g of chlorosulfonic acid was added dropwise to this melt under a nitrogen stream to form a sulfuric acid ester, which was then neutralized with an aqueous sodium hydroxide solution to synthesize a polyoxypropylene (1) lauric acid triglycolamide sulfate triethanolamine salt mixture. (Anion active ingredient: 30%).

Comparative Example 6 (polyoxypropylene (1)
Lioxyethylene (2) monoethanolamine laurate
Preparation of sodium dosulfate ) Monoethanolamine 62 was added to 214 g of methyl laurate.
g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(150 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. This was subjected to an addition reaction with a 2-fold molar amount of ethylene oxide (130 ° C., 2 hours) to obtain 332 g of polyoxyethylene (2) lauric acid monoethanolamide mixture. This was further subjected to an addition reaction of 58 g (1 mol) of propylene oxide (140 ° C., 1 hour) to synthesize a polyoxypropylene (1) polyoxyethylene (2) lauric acid monoethanolamide mixture.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 150 Amine value: 9.7 IR analysis (Hitachi 270-30, KBr tablet): 331
2,3080, 2924, 2852, 1650, 154
8, 1466, 1376, 1352, 1286, 111
^{4cm -1 1 H-NMR (Bruker} AC-250, CDC
l ₃ , TMS internal standard): δ 0.88 ppm (t, 3H,-
_{CH 3), 1.14ppm (d,} 3H, -CH (CH 3)
-O-), 1.26ppm (br, 16H, -CH
₂ −), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CO
NH -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68ppm (br, 1H , -OH) 3.2~4.1ppm (m, 15H, - (CH 2 CH
₂ O) ₃ --CH ₂ CHO--), 6.09 ppm (br, 1
H, NH)

This is heated to 40 ° C. to be uniformly melted,
120 g of chlorosulfonic acid was added dropwise to this melt under a nitrogen stream to form a sulfuric acid ester, which was then neutralized with an aqueous sodium hydroxide solution to give polyoxypropylene (1) polyoxyethylene (2) lauric acid monoethanolamide trisulfate. An ethanolamine salt mixture was synthesized (anionic active ingredient: 30%).

Example 13 (Polyoxypropylene (2)
Preparation of sodium lauric acid monoethanolamide sulfate
And lauric acid monoethanolamide 243g purified to Ltd.) autoclave, placed BF3 · etherate 2.4 g, further adding propylene oxide 116 g, 1
The reaction was carried out at 50 ° C for 1 hour. After completion of the reaction, water was added to quench the reaction, and then the solvent was removed under reduced pressure to give a polyoxypropylene (2) lauric acid monoethanolamide mixture 36.
0 g was obtained. Table 7 shows the oxypropylene group number distribution by GLC analysis.

[0109]

[Table 7]

From Table 7, it can be seen that the distribution of the number of oxypropylene groups is slightly narrower than that of the product reacted with the base catalyst of Example 3. The obtained polyoxypropylene (2) lauric acid monoethanolamide was salified with a sulfuric ester by the method described in Example 3 to synthesize polyoxypropylene (2) lauric acid monoethanolamide sodium sulfate (anionic active ingredient: 26 %).

Comparative Example 7 (Polyoxypropylene (1)
Preparation of uric acid monoethanolamide) 62 g of monoethanolamine was added to 200 g of lauric acid, and the mixture was heated with stirring at 180 ° C for 12 hours under a nitrogen stream. During that time, the reaction was carried out while distilling off the water produced. The distilled water content was 80% of the theoretical amount. As a result of GLC analysis, the content of lauric acid monoethanolamide in the reaction product was 75.
%Met. 58 g of propylene oxide was added thereto, and an addition reaction was carried out at 120 ° C. for 1 hour in an autoclave. As a result of GLC analysis, the reaction product was almost composed of a propylene oxide adduct of monoethanolamine, and the content of the target product was only 12%.
Further, the obtained product had a blackish brown color. No subsequent sulfation was performed.

Comparative Example 8 (Polyoxypropylene (1)
Preparation of uric acid monoethanolamide) Monoethanolamine 62 was added to 214 g of methyl laurate.
g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. The amine value of this product was 6.2. This was dissolved in 3000 ml of xylene and washed twice with 800 ml of 2% by weight hydrochloric acid water. Then, saturated saline solution 800
After washing with ml three times, it was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, recrystallized from THF-toluene to purify lauric acid monoethanolamide 194.
g was obtained (80% yield). The amine value of this product is 0.01
Met. This was put in an autoclave, and 46 g (1 mol) of propylene oxide was added, and the mixture was heated to 150 ° C.
After stirring for 6 hours, no reaction occurred and only the raw material was recovered.

Comparative Example 9 (Polyoxyethylene (2) Lau
Preparation of phosphoric acid monoethanolamide sodium sulfate 243 g of lauric acid monoethanolamide and 0.5 g of sodium hydroxide were placed in an autoclave and heated to 90 ° C. to melt. Ethylene oxide 88
g was injected under pressure and reacted at 110 ° C. for 2 hours to obtain polyoxyethylene (2) lauric acid monoethanolamide.
The oxyethylene group distribution of this product is shown in Table 8.

[0114]

[Table 8]

The above amide compound was heated to 40 ° C. and melted, and then 119 g of chlorosulfonic acid was added dropwise to form a sulfuric acid ester, which was then neutralized with an aqueous sodium hydroxide solution to give polyoxyethylene (2) laurin. A sodium acid monoethanolamide sulfate mixture was obtained (active anion ingredient: 26%).

Examples 14 to 25 and Comparative Examples 10 to 17 In Examples 14 to 25 and Comparative Examples 10 to 17, the compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 and 9 and commercially available poly were used. Using oxyethylene (3) sodium lauryl ether sulfate, a cleaning composition having the composition shown in Table 9 was prepared. The obtained product was subjected to the following foaming power, detergency test, pH stability, skin irritation test, sensory 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 0.25%, 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 220 mm or more ○: Good foaming, foaming power of 200 mm or more, less than 220 mm △: Normal foaming, foaming power of 170 mm or more, less than 200 mm × ... Poor foaming, foaming power of 170 mm Less than

2) Detergency test 0.1% SudanIII as an indicator was added to beef tallow,
Apply this 5% to a magnetic dish (25 cm diameter),
The detergency was indicated by the number of dishes that had been washed by scrubbing with a sponge soaked with 30 g of a 10% by weight washing solution until the beef tallow could no longer be washed from the dishes.

3) pH stability test A 2% washing solution adjusted to pH 7.0 was placed in a constant temperature bath at 50 ° C, and the pH after 30 days was measured.

4) Skin Irritation (Rough Hand) Test Immerse the hand in the 1% washing solution for 30 minutes a day to the wrist, and 3
After repeating for one day, the condition of the skin was determined on the following day based on the following criteria, and the average score of 20 testers was obtained. 3 points: Hands were not rough 2 points: Hands were slightly rough 1 point: Roughness Evaluation criteria were set as follows. …: Average point 2.1 to 3.0 ○: Average point 1.1 to 2.0 ×: Average point 0 to 1.0

5) Sensory (smoothness) test Ten panelists aged 20 to 40 were made to have a bath sponge containing 5 ml of the sample, and the hands and forearms were washed three times with warm water at about 40 ° C. The sensation during use during rinsing was evaluated according to the following criteria, and then the average value of sensation during use when naturally dried was determined. 4 points: No slimy feeling at all, refreshing 3 points: Almost no slimy feeling, refreshing 2 points… Slightly slimy feeling, light refreshing 1 point… Clearly remaining slimy feeling, refreshing The criteria for evaluation are set as follows. A: Average score 3.1 to 4.0 A: Average score 2.1 to 3.0 B: Average score 1.1 to 2.0 X: Average score 0 to 1.0

6) Protein denaturation test Using an aqueous gel filtration high performance liquid chromatography, the ovalbumin denaturation rate when the sample was added to an ovalbumin pH7 buffer solution so that the sample concentration was 1% was 220 nm.
It was calculated from the following formula using the absorption peak of Denaturation rate (%) = [(H 2 _O −H _S ) / H 2 _O ] × 100 H 2 _O : 220 nm absorption peak height of ovalbumin H _S : 22 when the sample was added to the ovalbumin buffer solution
The standard for evaluating the height of the 0 nm absorption peak was set as follows. ◎ ... Ovalbumin denaturation rate is less than 10% ◯ ... Ovalbumin denaturation rate is 10 to less than 29% △ ... Ovalbumin denaturation rate is 30 to less than 49% × ... Ovalbumin denaturation rate is 50% or more

The test results are shown in Table 9.

[Table 9]

As is clear from the results shown in Table 9, the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide sulfuric acid ester salt mixture of the present invention is excellent in foaming power, detergency and pH stability, and causes no skin irritation. There was little property and protein denaturation, and the usability was refreshing. On the other hand, in the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt and the polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt outside the scope of the present invention, foaming power, detergency, pH stability, skin irritation, In terms of refreshing feeling and protein denaturation,
It was inferior to the product of the present invention.

[0125] In each of Examples 26 to 33 and Comparative Examples 18 to 25 Examples 26 to 33 and Comparative Examples 18 to 25 were prepared detergent composition shown in Table 10. The product obtained is subjected to a foaming power test, a detergency test, a pH stability test,
It was subjected to skin irritation test, sensory test and protein denaturation test. These test methods were the same as in Example 14.

The test results are shown in Table 10.

[Table 10]

As is clear from the results in Table 10, the polyoxypropylene fatty acid alkanolamide sulfate ester salt mixture or polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt mixture of the present invention, an anionic surfactant and a cationic surfactant were used. Example 2 consisting of an amphoteric surfactant or a nonionic surfactant
The cleaning agents of 6 to 33 are more excellent in foaming power and cleaning power than in the case where the polyoxypropylene fatty acid alkanolamide sulfate ester salt and the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester salt are not contained (Comparative Example), It was confirmed that skin irritation and protein denaturation were low.

[0128] In each of Examples 34-43 and Comparative Examples 26-45 Examples 34-43 and Comparative Examples 26-45 were prepared detergent composition shown in Table 11 and Table 12. The product obtained is tested for foaming power, detergency, and pH.
It was subjected to stability test, skin irritation test, sensory test and protein denaturation test. These test methods were the same as in Example 14. The test results are shown in Tables 11 and 12.

[0129]

[Table 11]

[0130]

[Table 12]

As is clear from the results shown in Tables 11 and 12, the polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfuric acid ester salt mixture of the present invention and N-acyl amino acid, amide The detergent composition comprising a combination of a carboxylic acid type surfactant or an amphoteric surfactant was particularly excellent in foaming power and detergency, and had a very refreshing feeling. In addition, it was found to be suitable for shampoos and body shampoos because it is less irritating. However, the comparative examples were inferior to those of the present invention in any of the above characteristics.

Example 44 A rinse-incorporating shampoo having the following composition was prepared, and Example 1 was used.
It used for the same test as 4. Component weight% N-carboxymethyl-N- {2- [2-hydroxyethyl-coconut oil fatty acid amide] ethyl} glycine (30%) 20.0 N-cocoyl-L-glutamic acid triethanolamine (30% ) 5.0-2-coconut oil alkyl-N-carboxyethyl-N-hydroxy-ethylimidazolinium betaine (30%) 10.0-polyoxypropylene (2) coconut oil fatty acid monoethanolamide sulfate triethanolamine salt Mixture 5.0 • Coconut oil fatty acid diethanolamide 1.0 • Stearyl trimethyl ammonium chloride 1.5 • Cetyl octanoate 0.5 • Carboxymethyl chitin 0.1 • Hyaluronic acid 0.1 • Sodium edetate 0.1 • Preservative Agent 0.1-Purified water The balance test results are shown in Table 13.

Example 45 A conditioning shampoo having the following composition was prepared and subjected to the same test as in Example 14. Component wt% Polyoxyethylene (3) sodium lauryl sulphate 10.0-Lauroyl-N-methyl-β-alanine sodium (30%) 20.0-Polyoxyethylene (3) coconut oil fatty acid monoethanolamide sodium sulphate (30%) 2.0-Polyoxypropylene (1) myristic acid monoethanolamide magnesium sulfate mixture 2.0-caronated guar gum 0.3-lauric acid monoethanolamide 2.0-glycerin 3.0-edetic acid Sodium 0.1-Amount of citric acid pH = 6.5-Purified water Balance Table 13 shows the test results.

[0134]Example 46 A pearly shampoo having the following composition was prepared and used in Example 14
It was subjected to the same test. Component weight% -N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine 15.0-2-coconut oil alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine (30%) 10.0-Palm Oil fatty acid amide propyl dimethyl betaine 5.0 Lauroyl-N-methyl taurine sodium 5.0 Polyoxypropylene (3) palmitic acid diglycolamide ammonium sulfate salt mixture 5.0 Palm oil fatty acid diethanolamide 2.0 Palm oil Fatty acid monoethanolamide 1.5 ・ Amount to be caustic soda pH = 6.5 ・ Methylparaben 0.1 ・ Perfume proper amount ・ Purified water balance Table 13 shows the test results.

Example 47 A gel shampoo having the following composition was prepared and subjected to the same test as in Example 14. Component weight% Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 20.0 Polyoxypropylene (5) polyoxyethylene (0.5) Isostearic acid monoethanolamide sulfate potassium salt mixture 5 0.0-Lauric acid isopropanolamide 8.0-Carboxymethyl chitin 0.1-Methylparaben 0.1-EDTA 0.1-Citric acid pH = 7.0 Amount-Purified water balance Table 13 shows the test results.

Example 48 A shampoo having the following composition was prepared and subjected to the same test as in Example 14. Component % by weight -C14-α olefin sulfonate 5.0-Sodium cocoyl isethionate 5.0-Lauroyl-N-methyl taurine sodium 5.0-Polyoxypropylene (10) Polyoxyethylene (0.2) Oleic acid diglycolamide sulfate lysine salt mixture 5.0 ・ Oxyalkylene-modified organopolysiloxane (20% modification: 20% by weight of polyoxyethylene group) 1.0 ・ Lauric acid monoethanolamide 2.0 ・ Methylparaben 0.1 ・EDTA 0.1 • Purified water The balance test results are shown in Table 13.

Example 49 A shampoo having the following composition was prepared and subjected to the same tests as in Example 14. Ingredient wt% sodium lauryl sulfate 15.0 polyoxypropylene (20) palm kernel oil fatty acid monoethanol amide sulfate sodium salt mixture 5.0 POE (3) sodium lauryl ether carboxylate 5.0 mono (polyoxy Ethylene (6) lauric acid amide) Sodium phosphate 4.0 • Methylparaben 0.1 • EDTA 0.1 • Purified water Residual test results are shown in Table 13.

Example 50 A body shampoo having the following composition was prepared and subjected to the same test as in Example 14. Component weight% 2-lauryl-N-carboxymethyl-N-hydroxy ethylimidazolinium betaine (30%) 20.0 Polyoxypropylene (5) Polyoxyethylene (0.8) Tallow fatty acid diglycolamide sulfate Triethanolamine salt mixture 5.0 • Triethanolamine monododecylphosphate 5.0 • Triethanolamine laurate 7.0 • Methylparaben 0.1 • EDTA 0.1 • Purified water Residual test results are shown in Table 13.

Example 51 A body shampoo having the following composition was prepared and subjected to the same test as in Example 14. Component weight% Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 10.0 Polyoxypropylene (1) polyoxyethylene (1) lauric acid diglycolamide sulfate sodium salt mixture 10.0 -Polyoxyethylene (5) lauric acid monoethanolamide disodium sulfosuccinate (30%) 5.0-lauroyl sarcosine sodium 5.0-lauryl dimethylamine oxide 4.0-lauric acid diethanolamide 3.0-ethanol 2. 0-Purified water The balance test results are shown in Table 13.

Example 52 A face wash having the following composition was prepared and subjected to the same test as in Example 14. Component wt% N-2-hydroxyethyl-N-2-coconut oil fatty acid amide Ethyl-β-alanine (30%) 60.0 Polyoxypropylene (0.5) coconut oil fatty acid monoethanol amide ammonium sulfate mixture 10.0-Lauric acid diethanolamide 7.0-2-Alkyl-N-carboxymethyl-N-hydroxy-ethylimidazolinium betaine (30%) 5.0-Monylammonium glycyrrhizinate 0.2-Polyoxyethylene ( 2) Lauric acid monoethanolamide 0.5 ・ Allantoin 0.5 ・ Methylparaben 0.1 ・ Citric acid pH = 6.5 ・ Purified water balance Table 13 shows the test results.

Example 53 A coin surface cleaning agent having the following composition was prepared and subjected to the same test as in Example 14. Component % by weight- Sodium xylene sulfonate 6.0-Polyoxypropylene (20) Polyoxyethylene (1) Myristic acid monoethanolamide sulfate sodium salt mixture 5.0-Trisodium phosphate 5.0-POP (2) Methyl ether 4.0, pine oil 2.0, purified water balance Table 13 shows the test results.

Example 54 A kitchen detergent having the following composition was prepared and subjected to the same test as in Example 14. Component wt% -sodium α-olefin sulfonate 15.0-laurylamide dimethyl hydroxypropyl sulfobetaine (30%) 5.0-polyoxypropylene (3) lauric acid myristic acid (75:25) monoethanolamide magnesium sulfate Salt mixture 5.0-Lauryl glucoside 3.0-POE (2) lauric acid monoethanolamide 2.0-Edetate 0.1-Purified water balance Table 13 shows the test results.

Example 55 An automatic dishwashing detergent having the following composition was prepared, and Example 14 was prepared.
The same test was performed. Component wt% Sodium lauryl benzene sulfonate 20.0 Polyoxypropylene (2) stearic acid monoethanolamide Sulfate sodium salt mixture 6.0 Sodium xylene sulfonate 5.4 Sodium sulfate 1.0 Lauryl alcohol ammonium sulfate 8.35 ・ Purified water The balance test results are shown in Table 13.

Example 56 An oven cleaner having the following composition was prepared and subjected to the same tests as in Example 14. It was effective in removing oil stains that were thermally altered. Component wt% POE (9) sodium nonylphenyl ether sulfate 3.0 POE (9) sodium nonylsulfophenyl ether sulfate 3.0 polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide sulfate Sodium salt mixture 2.0-Sodium hydroxide 4.0-Polyoxypropylene (1) coconut oil fatty acid diglycolamide 5.0-Purified water balance Table 13 shows the test results.

[0145]

[Table 13]

As is clear from the results of Table 13, the cleaning agents of Examples 44 to 56 containing the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide sulfate ester salt mixture of the present invention have a foaming power, a cleaning power, It also had excellent pH stability and had little skin irritation and protein denaturation.
The sensory test showed a refreshing feel.

Example 57 An enzyme-containing cleaning composition having the following composition was prepared and its performance was evaluated. As a result, excellent cleaning power was exhibited. Component % by weight • POE (6) C _10-14 fatty alcohol ether 17.0 • Alkylbenzene sulfonic acid diethanolamine salt 60.0 • Polyoxypropylene (2) coconut oil fatty acid monoethanolamide sulfate diethanolamine salt mixture 5.0 • Palm Oil fatty acid monoethanolamide 22.0 Enzyme AP 0.2 Lipase A 0.15 Hard water (100 ppm) 0.65

Example 58 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
When its performance was evaluated, the skin after use showed an excellent refreshing feeling. Component weight%・ Soap substrate (beef tallow: coconut = 8: 2) 92.3 ・ N-lauroyl-L-sodium aspartate 2.0 ・ Polyoxypropylene (2) tallow fatty acid monoethanolamide sulfate triethanolamine salt Mixture 1.0 Titanium oxide 0.1 Edetate 0.1 Lauric acid diethanolamide 4.5

Example 59 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
When its performance was evaluated, the skin after use showed an excellent moist feeling. Component wt% N-lauroyl-L-glutamate monosodium 50.0 N-oleyl-L-glutamate monosodium 41.0 Myristyl alcohol 7.0 Polyoxypropylene (1) oleic acid diglycolamide 1. 0 Magnesium sulfate mixture ・ Lauric acid diethanolamide 1.0

Example 60 A bubble bath agent having the following composition was prepared and its performance was evaluated. As a result, a moist feel to the skin after bathing was given. Component weight% Distearyldimethylammonium chloride 59.0 Coconut oil fatty acid amide propyldimethylglycine 16.0 Polyoxypropylene (20) Polyoxyethylene (1) Coconut oil fatty acid diglycolamide sulfate lysine salt mixture 1.0・ Dimethylmyristylamine oxide 4.0 ・ Palm oil fatty acid diethanolamide 7.0 ・ Fragrance 1.0 ・ Purified water balance

[0151]

The polyoxypropylene fatty acid alkanolamide sulfate ester mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide sulfate ester mixture of the formula (1) of the present invention have foaming power, detergency and pH stability. It is an excellent surfactant that is extremely excellent in skin irritation, has very little irritation to the skin and hair, and has a refreshing feeling of use. In addition, the cleaning agent containing this has high foaming power and cleaning power,
Conventional alkyl ether sulfate ester salts and polyoxyethylene alkyl ether sulfates have almost no pH drop, and also reduce the irritation to the skin and hair by other surfactants, and have a refreshing feel with less numbness. As compared with a detergent containing an ester salt or polyoxyethylene fatty acid monoethanolamide, a detergent having a safer and excellent performance can be obtained. Further, a detergent comprising the compound mixture of the present invention and at least one selected from N-acyl amino acid salts, amide carboxylates, and amphoteric surfactants is further excellent in foaming power and detergency and has less irritation. Since the foam quality is creamy, it is suitable for use in shampoos and body shampoos. In addition, the method of the present invention enables efficient and industrially easy production of a polyoxypropylene fatty acid alkanolamide sulfate ester mixture and a polyoxypropylene fatty acid alkanolamide sulfate ester mixture.

[Brief description of drawings]

FIG. 1 is a graph showing the number distribution of oxypropylene groups and oxyethylene groups in polyoxypropylene (2) lauric acid monoethanolamide and polyoxyethylene (2) lauric acid monoethanolamide.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C11D 1/83 1:10 3:34 3:33)

Claims (5)

[Claims] 1. The following general formula (1): (In the formula (1), R represents a linear or branched saturated hydrocarbon or unsaturated hydrocarbon group having 7 to 21 carbon atoms, E
O represents an oxyethylene group, PO represents an oxypropylene group, x represents an integer of 1 to 2, y, and z
Each independently represents an integer of 0 to 1 or more,
M ¹ 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, and m is a valence of the atom or group represented by M ^1. Represents an integer equal to. ), A mixture of two or more kinds of compounds, wherein the average value y'of y in the mixture of compounds is a positive number of 0 or 1 and the average value z'of z is 0.3 to 2
A polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture, which is a positive number of 0. 2. The following general formula (2): (In the formula (2), R is the same as above, and R ¹ has ¹ carbon atom.
Represents an alkyl group of 1 to 3. ) And a fatty acid alkyl ester represented by the following general formula (3): (In the formula (3), x is the same as the above.) The alkanolamine represented by the formula (3) is reacted in the presence of a base catalyst, and the following general formula (4) produced by this reaction: (In the formula (4), R and x are the same as described above.) A reaction mixture containing a fatty acid alkanolamide is prepared, and the reaction mixture is contained in the reaction mixture without purification. The following general formula (5) produced by this addition reaction is carried out by adding 0 to 1 times the molar amount of ethylene oxide to the compound of the general formula (4): (In the formula (5), R, x, EO and y are the same as defined above.) A reaction mixture containing a polyoxyethylene fatty acid alkanolamide compound is prepared, and the reaction mixture is not purified. In addition, the compound of the general formula (5) contained in the reaction mixture is subjected to an addition reaction with 0.3 to 20 times mol of propylene oxide, and the addition reaction product is sulphated. The method for producing a polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture according to claim 1. 3. A detergent composition containing the polyoxypropylene fatty acid alkanolamide sulfuric acid ester salt compound mixture according to claim 1. 4. A mixture of the polyoxypropylene fatty acid alkanolamide sulfate ester salt compound according to claim 1 and at least one selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. A cleaning composition containing one of the above. 5. The polyoxypropylene fatty acid alkanolamide sulfate ester salt compound mixture (A) according to claim 1, an N-acyl amino acid and a salt thereof (B).
a), an amidocarboxylic acid type surfactant (Bb), and a surfactant (B) comprising at least one selected from an amphoteric surfactant (Bc), and a detergent composition comprising the same. .