JPH08337560A - Mixture of polyoxypropylene fatty acid alkanolamide compound, its production and chemical agent containing the same mixture - Google Patents

Abstract

PURPOSE: To obtain a mixture of a polyoxypropylene fatty acid alkanolamide compound excellent in thickening properties, foam increasing properties, foaming stability, emulsification dispersibility, cleanability, etc. CONSTITUTION: A fatty acid alkyl ester of formula I (R is a 7-21C hydrocarbon; R<1> is a 1-3C alkyl) is amidated with an alkanolamine of the formula N2 N-(CH2 CH2 O)p -H ((p) is 1 or 2) in the presence of a base catalyst (e.g. sodium methoxide) at 50-150 deg.C to give a reaction mixture containing a fatty acid alkanolamide of formula II. Ethylene oxide is added to the compound of formula II contained in the reaction mixture to give a reaction mixture containing a polyoxyethylene fatty acid alkanolamide of formula II (EO is oxyethylene; m is an integer of >=0). Propylene oxide is added to the compound of formula III containing in the reaction mixture to give the objective substance of formula IV (PO is a 3C oxyalkyelne; n is an integer of >=0).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention includes a mixture of polyoxypropylene fatty acid alkanolamide compounds (including polyoxypropylene polyoxyethylene fatty acid alkanolamide compounds), a process for industrially easy production thereof and a mixture of the compounds. It relates to various chemical agents. The chemical agent is a thickener, a foaming agent, a foam stabilizer,
Emulsifiers, dispersants, solubilizers, cosmetics with good emulsification stability and excellent usability, and stable in a wide pH range, foaming power / detergency / foaming stability / thickening / low temperature stability It also includes a cleansing composition that is excellent in dryness and has no irritation to the skin and hair.

[0002]

2. Description of the Related Art In general, detergents such as shampoos and body shampoos tend to be required to exhibit rich foaming and excellent detergency. Therefore, a foaming agent that acts as a foaming stabilizer is added to the surfactant that is the main base. In addition, since many of the surfactant components used as the main base have a relatively low viscosity, it is common to add a thickener to adjust the viscosity of the product so that it can be easily handled, depending on the application. Has been done.

Conventionally, as thickeners, foaming agents, and foam stabilizers, such as fatty acid monoethanolamide, fatty acid diglycolamide, and fatty acid diethanolamide, there is little irritation to the skin and hair. The fatty acid alkanolamides were the preferred choice. However, fatty acid monoethanolamide and fatty acid diglycolamide
Although it is extremely excellent in thickening action, it has a drawback in that it has a high melting point and therefore has poor solubility when it is blended in detergents and cosmetics. In particular, fatty acid monoethanolamide causes turbidity and dullness when it is contained in a large amount or when it is stored at a low temperature. Therefore, its use amount, product form, and use are limited. In addition, fatty acid monoethanolamide has a slight ocular mucous membrane irritating property, and has a drawback that when it is put in a shampoo composition or the like, it becomes irritating to the eyes.

Since fatty acid diethanolamide has a lower melting point than fatty acid monoethanolamide, it is excellent in handleability and solubility during compounding. Further, its thickening property is inferior to that of fatty acid monoethanolamide, but it is easy to adjust to an appropriate viscosity, and due to this advantage, it has been favorably used in shampoos and body shampoos. However, compared to fatty acid monoethanolamides, fatty acid diethanolamide is more susceptible to hydrolysis of the amide group, and thus the stability of the compound itself is poor, and the stability is particularly poor in the relatively high pH region of pH 9 or higher. Therefore, it is unsuitable for compounding into a high pH system.

In general, as the foaming agent, long-chain alkyldimethylamine oxide is used in addition to the above fatty acid alkanolamide, which has skin irritation and strongly reduces the recent hypoallergenicity. Considering the demanding tendency, its practical use is being shunned. As other thickeners, foaming agents, and foam stabilizers, for example, fatty acid esters, alkylamine oxides, cellulose derivatives, acrylic acid polymers, polyethylene glycols, higher alcohols, etc. are used. However, they have drawbacks that they are easily decomposed in a certain pH range, have an irritating property, or are expensive.

In order to improve the foaming stability, polyoxyethylene (2 to
10) Fatty acid monoethanolamide and the like are also widely used. However, although these have excellent foaming stability,
There is a drawback that the thickening and foaming properties are not sufficient. Further, polyoxyethylene (2 to 10) fatty acid monoethanolamide produces a small amount of toxic dioxane by polymerization of ethylene oxide itself during the production process, that is, when ethylene oxide is added to fatty acid monoethanolamide. I have a problem. Therefore, after the addition of ethylene oxide, a step of removing dioxane from the reaction mixture is required, which is a drawback that the manufacturing process becomes complicated.

Generally, in cosmetics such as cream,
In order to uniformly emulsify, disperse or solubilize the blended components, higher alcohols, fatty acid esters and the like are used. However, depending on the blending composition, the stability of the emulsion or dispersion is poor and it may separate during long-term storage. Further, there is a drawback that the usability is not sufficiently satisfactory.

Further, as a general emulsifier, fatty acid soap, fatty acid glyceride, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether,
And polyoxyethylene polyoxypropylene block polymers are used. However, the emulsifying power of these conventional emulsifiers is not sufficiently satisfactory. In particular, since an emulsifier containing an ester group is susceptible to hydrolysis, there is a problem that as a result, the emulsion system collapses during long-term storage and a phenomenon such as oil-off occurs.

Further, generally, as the dispersant, an anionic surfactant having a sulfate group or a sulfonic acid group,
Various metal soaps such as stearic acid soap, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, and sorbitan fatty acid ester are used. However, the dispersibility of these conventional dispersants has not been sufficiently satisfactory.

Further, as the solubilizer, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil,
Polyoxyethylene hydrogenated castor oil, sucrose fatty acid monoester, etc. are used. However, these conventional solubilizers are not sufficiently satisfactory in solubilizing power, and particularly when an ester-based solubilizer is used, the solubilized substance may be liberated over time. .

Under the above circumstances, a thickener, a foaming agent, and a foaming stabilizer which are excellent in solubility, handling property, stability and non-irritating property are required. Was there. There has also been a demand for an emulsifier, a dispersant, and a solubilizer that are stable over time. Further, it has been desired to develop a method for producing them industrially easily and safely. Furthermore, cosmetics with good emulsion stability and excellent feeling of use, and excellent foaming power, detergency, foaming stability and thickening, stable in a wide pH range, easy to handle and soluble There has been a demand for a detergent composition which has good properties, is excellent in low temperature stability at the time of compounding, and has no irritation to skin, hair and eye mucous membranes.

Regarding polyoxyalkylene fatty acid alkanolamides, JP-A-53-54208, 54-
15911, 59-210999, 60-4909
9, No. 60-96695, 63-189499, 6
3-196667, JP-A-2-151692, 2-
Although disclosed in Japanese Patent No. 504165 and the like, there is no description about the addition of propylene oxide to a fatty acid alkanolamide.

Further, JP-A-61-161625 and 61-2
27830, 61-227832, 61-2462
96, 62-57491, and 62-20920.
No. 0 and the like describe alkylene oxide adducts of fatty acid alkanolamides, but all are block or random adducts of ethylene oxide and propylene oxide, and the total number of moles added is 1
It is as large as 3 times the mole or more, and its application is only used as a non-aqueous solid dispersant or a non-aqueous detergent.

JP-A-61-114727 describes polyoxypropylene (20) coconut oil fatty acid monoethanolamide. This compound adds propylene oxide in an amount 20 times that of coconut oil fatty acid monoethanolamide. However, the number of moles of propylene oxide added is as large as 20, and its use is described only for a non-aqueous solid dispersant.

[0015]

DISCLOSURE OF THE INVENTION The present invention is a specific useful for chemical agents such as thickeners, foaming agents, foam stabilizers, emulsifiers, dispersants, solubilizers, cosmetics and detergents. Mixture of polyoxypropylene fatty acid alkanolamide compounds, industrially easy production method thereof, and thickener, foaming agent, foam stabilizer, emulsifier, dispersant containing the specific polyoxypropylene fatty acid alkanolamide compound mixture ,
Solubilizer, cosmetics with good emulsion stability and excellent feeling of use, excellent foaming power / detergency / foaming stability / viscosity increase, wide range of pH
To provide a detergent composition that is stable in the area, easy to handle, has good solubility, has good low-temperature stability when blended, has little irritation to skin, hair, and eye mucous membranes and is excellent in safety. To do.

[0016]

Means for Solving the Problems The present inventors have taken advantage of the characteristics of fatty acid alkanolamides, which are typical thickeners, and have instability at high pH, poor handling properties, and low temperature stability during low temperature compounding. To improve problems such as
As a result of diligent research, a mixture of polyoxypropylene fatty acid alkanolamide and polyoxypropylene polyoxyethylene fatty acid alkanolamide (hereinafter referred to as polyoxypropylene fatty acid alkanolamide compound) having a specific number of moles of addition has an excellent increase. It has viscosity, foaming property, foaming stability, and its low melting point makes it easy to handle, and stable in a wide pH range, and also to the skin and hair,
It has very little irritation to the eye mucous membrane, and if it is used, it improves the foaming power / cleansing power / foaming stability / viscosity, has excellent low-temperature stability during compounding, and has little irritation to the skin or hair and is safe. It has been found that a detergent composition having excellent properties can be obtained. More surprisingly, the specific polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is also excellent in emulsifying power, dispersing power and solubilizing power, and when it is used in cosmetics, the emulsion stability is improved. Then
We found that it is excellent in usability. The present invention has been completed based on the above findings.

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

[Chemical 6] (In the formula (1), R is a linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group having 7 to 21 carbon atoms, EO represents an oxyethylene group, and PO represents an oxy group having 3 carbon atoms. Represents an alkylene group, p is 1 or 2, m is 0 or an integer of 1 or more, and n is an integer of 0 or 1 or more)
A mixture of two or more compounds represented by
Is a positive number of 0 or less than 1, and the average value of n is a positive number of 0.3 to 10.

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

[Chemical 7] (In the formula (2), R is the same as above, and R ¹ has ¹ carbon atom.
Represents an alkyl group of ~ 3. ) A fatty acid alkyl ester represented by the following general formula (3):

Embedded image (In the formula (3), p is the same as above.) And reacted with an alkanolamine in the presence of a base catalyst to give the following general formula (4):

[Chemical 9] (In the formula (4), R and p are respectively the same as above.) A reaction mixture containing a fatty acid alkanolamide is prepared, and the reaction mixture is contained in the reaction mixture without purification. The compound of the general formula (4) is subjected to an addition reaction with 0 to 1 times the molar amount of ethylene oxide to give a compound of the following general formula (5):

[Chemical 10] (In the formula (5), R, p and m are the same as described above.) A reaction mixture containing a polyoxyethylene fatty acid alkanolamide compound represented by the formula (5) was prepared, and the reaction mixture was purified without purification. The compound of the general formula (5) contained in this reaction mixture had a molar amount of 0.
It is characterized in that an addition reaction of 3 to 10 times the molar amount of propylene oxide is carried out.

The thickener of the present invention is characterized by containing a mixture of the polyoxypropylene fatty acid alkanolamide compound of the above formula (1).

The foam increasing agent of the present invention is characterized by containing the polyoxypropylene fatty acid alkanolamide compound mixture of the above formula (1).

The foam stabilizer of the present invention is characterized by containing the mixture of polyoxypropylene fatty acid alkanolamide compounds of the above formula (1).

The emulsifier of the present invention contains the polyoxypropylene fatty acid alkanolamide compound mixture of the above formula (1).

The dispersant of the present invention is characterized by containing the polyoxypropylene fatty acid alkanolamide compound mixture of the above formula (1).

The solubilizer of the present invention is characterized by containing a mixture of the polyoxypropylene fatty acid alkanolamide compound of the above formula (1).

The cosmetic of the present invention is characterized by containing the polyoxypropylene fatty acid alkanolamide compound mixture of the above formula (1).

The detergent of the present invention is characterized by containing the polyoxypropylene fatty acid alkanolamide compound mixture of the above formula (1).

The detergent composition of the present invention comprises a mixture of the polyoxypropylene fatty acid alkanolamide compound of the above formula (1), an anionic surfactant, a cationic surfactant,
It is characterized by containing at least one selected from an amphoteric surfactant and a nonionic surfactant.

[0028]

The polyoxypropylene fatty acid alkanolamide compound mixture contained in the mixture of the present invention will be described in detail below. In the following compound names, the number in parentheses is the number of moles of propylene oxide subjected to the addition reaction with respect to 1 mole of the fatty acid alkanolamide. (1) Polyoxypropylene (0.3) lauric acid monoethanolamide, polyoxypropylene (1) lauric acid monoethanolamide, polyoxypropylene (2) lauric acid monoethanolamide, polyoxypropylene (5) lauric acid monoethanolamide Ethanolamide, polyoxypropylene (10) lauric acid monoethanolamide, polyoxypropylene (1.5) capric acid monoethanolamide, polyoxypropylene (1.5) decanoic acid monoethanolamide, polyoxypropylene (1.5 ) Myristic acid monoethanolamide, polyoxypropylene (1.5) palmitic acid monoethanolamide, polyoxypropylene (1.5) stearic acid monoethanolamide, polyoxypropylene (1.
5) Isostearic acid monoethanolamide, polyoxypropylene (1.5) oleic acid monoethanolamide, polyoxypropylene (1.5) linoleic acid monoethanolamide, polyoxypropylene (1.5) linolenic acid monoethanolamide, Polyoxypropylene (1.5) -2-octyldecanoic acid monoethanolamide, polyoxypropylene (1.5) -2-heptylundecanoic acid monoethanolamide, polyoxypropylene (1.5) coconut oil fatty acid monoethanolamide , Polyoxypropylene (1.5) tallow fatty acid monoethanolamide, and polyoxypropylene (1.5) palm kernel oil fatty acid monoethanolamide, such as polyoxypropylene (1.5) fatty acid monoethanolamide,

(2) Polyoxypropylene (0.3) lauric acid diglycolamide, polyoxypropylene (1) lauric acid diglycolamide, polyoxypropylene (2) lauric acid diglycolamide, polyoxypropylene (5) Lauric acid diglycolamide, polyoxypropylene (10) lauric acid diglycolamide, polyoxypropylene (1.5) capric acid diglycolamide, polyoxypropylene (1.5) decanoic acid diglycolamide, polyoxypropylene ( 1.
5) myristic acid diglycolamide, polyoxypropylene (1.5) palmitic acid diglycolamide, polyoxypropylene (1.5) stearic acid diglycolamide, polyoxypropylene (1.5) isostearic acid diglycolamide, Polyoxypropylene (1.5) oleic acid diglycolamide, polyoxypropylene (1.5) linoleic acid diglycolamide,
Polyoxypropylene (1.5) linolenic acid diglycolamide, polyoxypropylene (1.5) -2-octyldecanoic acid diglycolamide, polyoxypropylene (1.5) -2-heptylundecanoic acid diglycolamide, Polyoxypropylene (1.5) Coconut oil fatty acid diglycolamide, Polyoxypropylene (1.5)
Polyoxypropylene (1.5) fatty acid diglycol amides such as tallow fatty acid diglycol amide and polyoxypropylene (1.5) palm kernel oil fatty acid diglycol amide.

The polyoxypropylene polyoxyethylene fatty acid alkanolamide compound of the present invention is exemplified below. 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 (0.5) lauric acid monoethanolamide, polyoxypropylene (1) polyoxyethylene (1) lauric acid monoethanolamide, polyoxypropylene (2) poly Oxyethylene (1) lauric acid monoethanolamide, polyoxypropylene (5) polyoxyethylene (0.1) lauric acid monoethanolamide, polyoxypropylene (10) polyoxyethylene (0.
3) lauric acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) capric acid monoethanolamide, polyoxypropylene (1.
5) Polyoxyethylene (1) decanoic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) myristic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1)
Palmitic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) stearic acid monoethanolamide, polyoxypropylene (1.
5) Polyoxyethylene (1) isostearic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) oleic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) linoleic acid Monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) linolenic acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) -2-octyldecanoic acid monoethanolamide, polyoxy Propylene (1.5) Polyoxyethylene (1) -2-heptylundecanoic acid monoethanolamide, polyoxypropylene (1.5) Polyoxyethylene (1) coconut oil fatty acid monoethanolamide, polyoxypropylene (1.5 )
Polyoxypropylene (1) tallow fatty acid monoethanolamide, polyoxypropylene (1.5) polyoxyethylene (1) palm kernel oil fatty acid monoethanolamide and other polyoxypropylene polyoxyethylene fatty acid monoethanolamide, and

(4) polyoxypropylene (0.3) polyoxyethylene (0.5) lauric acid diglycolamide, polyoxypropylene (1) polyoxyethylene (1) lauric acid diglycolamide, polyoxypropylene ( 2) polyoxyethylene (1) lauric acid diglycolamide, polyoxypropylene (5) polyoxyethylene (0.1) lauric acid diglycolamide,
Polyoxypropylene (10) polyoxyethylene (0.3) lauric acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) capric acid diglycolamide, polyoxypropylene (1.
5) Polyoxyethylene (1) decanoic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) myristic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) palmitic acid Diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) stearic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) isostearic acid diglycolamide, polyoxypropylene (1. 5) Polyoxyethylene (1) oleic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) linoleic acid diglycolamide, polyoxypropylene (1.
5) Polyoxyethylene (1) linolenic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) -2-octyldecanoic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene ( 1) -2-heptylundecanoic acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) coconut oil fatty acid diglycolamide, polyoxypropylene (1.5) polyoxyethylene (1) tallow fatty acid di Glycolamide, polyoxypropylene (1.
5) Polyoxyethylene (1) Polyoxypropylene polyoxyethylene fatty acid diglycolamide such as palm kernel oil fatty acid diglycolamide.

Among the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention, comparing the polyoxypropylene fatty acid monoethanolamide compound mixture with the polyoxypropylene fatty acid diglycolamide compound mixture, the fatty acid acyl groups are the same and When the average number of moles of added oxide is the same, the polyoxypropylene fatty acid monoethanolamide compound mixture is superior in terms of thickening property, foaming property, emulsifying property, solubilizing property, but foaming stability, From the viewpoint of dispersibility, the polyoxypropylene fatty acid diglycolamide compound mixture is superior. In addition, the polyoxypropylene fatty acid diglycolamide compound mixture has a low melting point, and thus is excellent in solubility, handling property, and cold resistance. The same applies to the relationship between the polyoxypropylene polyoxyethylene fatty acid diglycolamide compound mixture and the polyoxypropylene polyoxyethylene fatty acid diglycolamide compound mixture. In the compound of the general formula (1), when p is 3 or more, that is, 3 or more glycol groups (CH ₂ CH ₂ ) such as polyoxypropylene (polyoxyethylene) fatty acid tri-, tetra- or pentaglycolamide compound. With O groups), the thickening, foaming and foaming stability of these compounds decreases sharply with increasing number of glycol groups (p).

The polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is prepared from ethylene oxide (E
The average value of the number m of added moles of O) is 0 or a positive number of 1 or less. If the average number of added moles exceeds 1, the resulting compound mixture will have insufficient thickening property and foaming property. In order to obtain a particularly thickening agent, it is preferable that the average number of moles of ethylene oxide added be 0.5 or less. Among them, the number of average addition moles of ethylene oxide is 0, that is, one in which no ethylene oxide is added. Are better. When the ethylene oxide addition mole number is larger than 1, the average addition mole number of ethylene oxide is 1 or less (0
However, it has a lower melting point, so it is more excellent in terms of solubility, handling, and cold resistance, but it is inferior in viscosity increasing, foam increasing, solubilizing, etc. There is.

The addition mole number n of propylene oxide in the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is 0 or an integer of 1 or more, and its average value, that is, the average addition mole number is 0.3 to 10. If the average number of added moles is less than 0.3, the melting point becomes excessively high, resulting in poor handleability and poor solubility. However, when it exceeds 10, the thickening property, the foaming property, the foaming stability, the emulsifying property, the dispersibility and the solubilizing property are drastically lowered. Within the average addition mole number range of propylene oxide of 0.3 to 10, the smaller the average addition mole number is, the better the thickening property, the foam increasing property, the emulsifying property and the solubilizing property. The number is preferably 0.3-2. On the other hand, regarding foaming stability and dispersibility, the larger the number of added moles, the better. Specifically, the average number of added moles is 2 to 1
It is preferably 0.

Polyoxyethylene fatty acid alkanolamide is a compound having a structure similar to that of polyoxypropylene fatty acid alkanolamide or polyoxypropylene polyoxyethylene fatty acid alkanolamide contained in the compound mixture of the present invention. Comparing this compound with the compound mixture of the present invention, the compound mixture of the present invention is more excellent in thickening and foaming properties, has a lower dioxane content, and a detergent composition containing the same has a better cleaning property. Show power.

The method for producing the polyoxypropylene fatty acid alkanolamide compound mixture represented by the general formula (1) will be described in detail below.

The polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is produced by adding propylene oxide to the fatty acid alkanolamide. Further, the polyoxypropylene polyoxyethylene fatty acid alkanolamide compound mixture of the present invention, after adding ethylene oxide to the fatty acid alkanolamide,
Further, it is produced by adding propylene oxide.

Here, as the fatty acid alkanolamide, fatty acid monoethanolamide or fatty acid diglycolamide is used. Specific examples of the fatty acid monoethanolamide include capric acid monoethanolamide, decanoic acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid. Monoethanolamide, oleic acid monoethanolamide, linoleic acid monoethanolamide, linolenic acid monoethanolamide, 2-octyldecanoic acid monoethanolamide,
2-heptyl undecanoic acid monoethanolamide, coconut oil fatty acid monoethanolamide, tallow fatty acid monoethanolamide, palm kernel oil fatty acid monoethanolamide and the like can be mentioned. These fatty acid monoethanolamides may be used alone or as a mixture of two or more kinds.

As the fatty acid diglycolamide,
Capric acid diglycolamide, decanoic acid diglycolamide, lauric acid diglycolamide, myristic acid diglycolamide, palmitic acid diglycolamide, stearic acid diglycolamide, isostearic acid diglycolamide, oleic acid diglycolamide, linoleic acid Diglycolamide, linolenic acid diglycolamide, 2-octyldecanoic acid diglycolamide, 2-heptylundecanoic acid diglycolamide, coconut oil fatty acid diglycolamide, tallow fatty acid diglycolamide, palm kernel oil fatty acid diglycolamide, etc. Used. These fatty acid diglycolamides alone,
Alternatively, they are used as a mixture of two or more kinds. Further, it may be a mixture of one or more fatty acid monoethanolamide and one or more fatty acid diglycolamide.

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

The method for adding propylene oxide to the fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide is not particularly limited. For example, Lewis acid catalyst such as boron trifluoride, sodium hydroxide, potassium hydroxide, sodium methoxide,
Propylene oxide can be reacted with the alkanolamide compound in the presence of a base catalyst such as sodium ethoxide. This reaction requires the presence of either catalyst, and with highly purified fatty acid alkanolamides the addition reaction either 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. If the temperature is lower than 80 ° C., the reaction is slow, and if the temperature is higher than 180 ° C., the coloring becomes remarkable, which is not preferable. Therefore, in order to prevent or suppress coloring, it is effective to replace the air in the reactor with an inert gas in advance. As a method of charging propylene oxide, (a) charging before heating,
Any method may be used, such as (b) heating to the reaction temperature and then press-fitting in a liquid state, or (c) heating to the reaction temperature and then blowing in a gas state. However, since heat is generated during the addition reaction, temperature control may be difficult with the method (a). Therefore, when manufacturing in large quantities, it is preferable to adopt the method (b) or (c), which allows easy temperature control.

After completion of the propylene oxide addition reaction, the obtained reaction mixture containing polyoxypropylene fatty acid alkanolamide and polyoxypropylene polyoxyethylene fatty acid alkanolamide can be used as it is in the next step without purification. In general, polyoxyethylene fatty acid alkanolamides such as fatty acid alkanolamides to which ethylene oxide is added contain a small amount of toxic dioxane,
Although the step of removing this dioxane is required, in the method for producing the compound mixture of the present invention, since ethylene oxide is not used or the amount thereof is small even when used, the amount of dioxane produced is extremely small. It does not require the step of removing dioxane from the reaction mixture except in special cases. However, when it is necessary to avoid the presence of a small amount of dioxane or a small amount of dissolved propylene oxide, dioxane and dissolved propylene oxide can be easily removed by lightly reducing the pressure of the reaction mixture.

When it is necessary to avoid the remaining catalyst used, the following treatment may be performed. That is, when a Lewis acid is used as a catalyst, the amount of the catalyst used in the reaction mixture is quenched by adding 1 to 100 times the amount of water, and then the Lewis acid is removed under reduced pressure. When a base catalyst is used, it may be neutralized with a mineral acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid. However, when the inorganic salt or organic salt formed at that time is also repelled, it can be easily removed by a method such as filtration.

In the propylene oxide addition reaction, a solvent may be used as long as it does not inhibit the reaction. Examples of the solvent that can be used include hydrocarbon solvents such as hexane, benzene, toluene, and xylene, halogen solvents such as chloroform and dichloroethane, and ether solvents such as tetrahydrofuran, diisopropyl ether, and dibutyl ether. be able to. When these solvents are used, it is necessary to remove the solvent by distilling it off under reduced pressure after the completion of the propylene oxide addition reaction.

To obtain the fatty acid alkanolamide,
(1) a method of dehydration-condensing a fatty acid and an alkanolamine, (2) a method of reacting a fatty acid halide with an alkanolamine, and (3) a method of reacting a lower alcohol ester of a fatty acid with a lower alcohol while removing the lower alcohol from the alkanolamine, etc. Can be used. The method (1) has a drawback that it is difficult to complete the reaction, some unreacted raw materials remain, and the reaction temperature must be higher than that of the other methods, resulting in remarkable coloring. In the above method (2), since hydrogen chloride is generated, a reagent and a device for trapping the hydrogen chloride are required, and the problem of corrosion of the device and the fatty acid halide are relatively expensive. Hard to say.

In order to obtain the polyoxypropylene fatty acid alkanolamide or polyoxypropylene polyoxyethylene fatty acid alkanolamide of the present invention, the method (3) above in which the obtained fatty acid alkanolamide has a high purity is preferable. A base catalyst is used in the reaction (3). As described above, it is necessary to use a catalyst for the ethylene oxide or propylene oxide addition in the next step. However, when the fatty acid alkanolamide is produced by the method (3), the base catalyst is ethylene oxide and propylene oxide addition reaction. Since it is also effective as a catalyst, it is not necessary to add a catalyst essential for this addition reaction at the stage of adding ethylene oxide or propylene oxide, so this method is a very efficient method.

The most efficient method for producing the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is, for example, as follows. That is, a fatty acid alkanolamide is prepared by heating a reaction system containing a fatty acid lower alkyl ester, monoethanolamine or diglycolamine, and a base catalyst to carry out a condensation reaction while distilling off the generated lower alkanol. next,
This fatty acid alkanolamide is subjected to a propylene oxide addition reaction or ethylene oxide addition reaction, and then a propylene oxide addition reaction.
An example of one embodiment of this reaction is as follows.

[Chemical 11]

The fatty acid lower alkyl ester represented by the general formula (2) used in the present invention is, for example, capric acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, 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, isopropyl ester and the like.

The alkanolamine represented by the general formula (3) used in the present invention is either monoethanolamine or diglycolamine. The molar ratio (3) / (2) between the alkanolamine represented by the general formula (3) and the fatty acid alkyl ester represented by the general formula (2) is
It is preferably 0.8: 1 to 1.2: 1.
More preferably, it is 0: 1 to 1.1: 1.

Examples of the base catalyst used in 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 suitable, and a reaction time of up to 12 hours is sufficient. Since the lower alcohol produced by the amidation reaction is distilled off, it is preferable to control the pressure within the range of 0.1 to 760 mmHg.
Is more preferable. However, at this time, it is desirable to set the pressure 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 obtained fatty acid alkanolamide reaction mixture containing a 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 carried out by the above method. However, in general, many fatty acid alkanolamides and polyoxyethylene (0 to 1) fatty acid alkanolamides solidify when cooled, so that the temperature of the reaction solution is adjusted to a desired propylene oxide addition temperature, and the propylene oxide is liquid or Gaseous method,
That is, the above-mentioned methods (2) to (3) are efficient.

After the addition of propylene oxide, if the base catalyst used as the reaction catalyst becomes problematic, the reaction mixture is neutralized with an acidic substance such as hydrochloric acid, sulfuric acid, acetic acid, sulfurous acid or sulfurous acid gas to form the reaction mixture. The salt may be removed by filtration. In addition, when a small amount of unreacted propylene oxide dissolved in the reaction solution is to be repelled after the addition of propylene oxide, the residual propylene oxide can be easily removed by lightly reducing the pressure inside the reaction vessel.

The polyoxypropylene fatty acid alkanolamide compound mixture represented by the general formula (1) of the present invention has surface-active ability by itself. However, when this is used alone, the foaming power and the cleaning power are not always sufficient. However, by combining this with other surfactants, the performance of the other surfactants can be enhanced. Performances that can be enhanced by blending the compound mixture of the present invention include thickening (thickening agent), foaming power (foaming agent), and foam stabilizing property (foaming stabilizer) for long-lasting foaming. .

The polyoxypropylene fatty acid alkanolamide compound mixture represented by the general formula (1) of the present invention not only has excellent properties as a thickener, a foaming agent and a foaming stabilizer, but also on the skin. It is characterized by less irritation to hair, hair and eye mucous membranes, excellent handling and solubility properties, and being difficult to hydrolyze even in a wide range of pH. Therefore, as compared with conventional thickeners composed of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides, foaming agents, and foam stabilizers, thickeners composed of the compound mixture of the present invention, foaming agents, And the foam stabilizers can be applied to a wider range of fields and various product forms. Furthermore, the compound mixture of the present invention is also excellent in emulsifying power, dispersing power, and solubilizing power, and because of its good solubility and hardly decomposing property, cosmetics, detergents, fibers, foods, agricultural chemicals, coatings, It can be used as an excellent emulsifier, dispersant, and solubilizer in various fields such as molecules.

General formula (1) used in the cosmetics of the present invention
Although the content of the polyoxypropylene fatty acid alkanolamide compound mixture represented by is not particularly limited,
The amount is preferably 1 to 20% by weight, more preferably 1 to 5% by weight. If the content in the cosmetic is less than 0.1% by weight, the effect may be insufficient, and it is 2
If it exceeds 0% by weight, the emulsion stability of the obtained cosmetic composition may be deteriorated and the stickiness during use may be excessively strong.

The cosmetics of the present invention include cetyl alcohol,
Higher alcohols such as stearyl alcohol and behenyl alcohol, higher alcohol ethers such as cetyl alcohol polyglycol ether, higher fatty acids such as stearic acid, higher fatty acid salts such as triethanolamine stearate, and glyceryl stearate, and isopropyl palmitate such as isopropyl palmitate. Fatty acid esters and the like can be added.

In the cosmetic of the present invention, if necessary, polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, lanolins, polyacrylic acid polymers, hyaluronic acid, carboxymethyl chitin. , Elastin, chondroitin sulfate,
Water-soluble polymer substances such as dermatanic acid, fibronectin, and ceramides, cell activating agents such as aloe extract, and placenta extract, allantoin, and anti-inflammatory agents such as glycyrrhizinate, edetate, citric acid, malic acid, And chelating agents such as gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2,4,4′-trichloro-2 ′
-Hydroxydiphenyl ether, 3,4,4'-trichlorocarbanilide, benzalkonium chloride, hinokitiol, and preservatives such as resorcin, bactericides, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and ascorbic acid Antioxidant, oxybenzone, 4-tert-butyl-
An ultraviolet absorber such as 4′-methoxybenzoylmethane and 2-ethylhexylparadimethylaminobenzoate, a silicone compound such as amino-modified silicone and polyether-modified silicone, a fragrance, and a dye can be appropriately blended.

The state of the cosmetic of the present invention is not limited, and may be any state such as solution, emulsion, powder dispersion, water-oil two-layer liquid. In order to produce the cosmetic of the present invention, the required components may be blended and mixed by a blending method generally used by those skilled in the art.

The application of the cosmetic of the present invention is also optional, but typical examples are skin cosmetics such as lotion, emulsion, cream, pack, cleansing, beauty essence, foundation, and rinse, hair. Treatment, hair conditioner, hair brushing agent,
Hair cosmetics such as hair nicks, permanent wave agents, hair depigmenting agents, and hair dyes, makeup soaps, and bath agents are included.

The content of the polyoxypropylene fatty acid alkanolamide compound mixture represented by the general formula (1) contained in the detergent composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, More preferably,
It is 1 to 5% by weight. Content in the cleaning composition is 0.1
If it is less than 20% by weight, the effect may be insufficient.
The thickening property may decrease, and the stickiness during use may become excessively strong.

As the anionic surfactant to be added to the detergent composition of the present invention, sodium laurate and fatty acid soaps such as triethanolamine laurate,
Alkylbenzene sulfonate, α-olefin sulfonate, sodium lauryl sulfate, lauryl sulfate such as triethanolamine lauryl sulfate, polyoxyethylene (3) ether sulfate such as sodium lauryl ether sulfate, polyoxyethylene (3) coconut Amide ether sulfate, such as oil fatty acid sodium amide sulfate,
Triethanolamine monododecyl phosphate, and phosphoric acid esters such as sodium polyoxyethylene dodecyl ether phosphate, acyl methyl taurine salts such as sodium cocoyl methyl taurine and sodium lauroyl methyl taurine, and acyl isethionates such as sodium lauroyl isethionate A sulfosuccinic acid type surfactant such as disodium lauryl sulfosuccinate, disodium lauryl sulfosuccinate, POE (1-4) disodium lauryl sulfonate, and polyoxyethylene (5) disodium lauric acid monoethanolamide sulfosuccinate, an alkyl ether carboxylate, Cocoyl sarcosine sodium, lauroyl sarcosine sodium, myristoyl sarcosine sodium, lauroyl sarcosine potassium, and lauroyl sarcosine N-acyl sarcosine salts such as triethanolamine, cocoyl-N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine sodium, myristoyl-N-methyl-β-alanine sodium, palmitoyl-N-methyl- N-acyl-β-alanine salts such as β-alanine sodium, stearoyl-N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine potassium, and lauroyl-N-methyl-β-alanine triethanolamine. N-, such as sodium N-lauroyl aspartate, triethanolamine N-lauroyl aspartate, and sodium N-myristoyl aspartate.
Acyl aspartates and amidocarboxylic acid type surfactants such as N-acyl glutamate such as sodium N-lauroyl glutamate, triethanolamine N-lauroyl glutamate, sodium N-cocoyl glutamate, and triethanol amine N-cocoyl glutamate. And so on.

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. Can be mentioned.

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 amphoteric surfactants such as-(2-hydroxyethyl) lauric acid amide] ethyl} glycine and N- {2- [N- (2-hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, alkyl sulfobetaines Examples of the amphoteric surfactants include 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, and fatty acid diglycolamides such as lauric acid diglycolamide, fatty acid isopropanolamides such as lauric acid isopropanolamide, polyoxyethylene (2) lauric acid monoethanolamide, And polyoxyethylene (5) coconut oil fatty acid monoethanolamide and other polyoxyethylene fatty acid monoethanolamide, fatty acid ester, and lauryldimethylamine oxide Kill amine oxide, POE higher alcohol ether, POE alkylphenyl ethers, and the like nonionic surfactants such as alkyl glucosides, such as decyl glucoside and the like.

The amount of the anionic surfactant, cationic surfactant, amphoteric surfactant and / or nonionic surfactant used in the detergent composition of the present invention can be appropriately set depending on the purpose of use. However, 1 to 99% by weight is generally suitable for the total weight of the detergent.

The detergent composition of the present invention may contain the following additional components, if desired. That is, as additional components, for example, cationized polymers, cationized guar gum, glycerin, propylene glycol, 1,3-butylene glycol, and polyhydric alcohols such as sorbitol, methylpolysiloxane, and silicols such as oxyalkylene-modified organopolysiloxane. ,
Anti-dandruff agents such as zinc pyrithione and piroctone olamine, hyaluronic acid, collagen, elastin chondroitin sulfate, dermatanic acid, fibronectin, ceramides, chitin, and water-soluble polymer substances such as chitosan, aloe extract, and placenta extract Cell activating agents, allantoin, and anti-inflammatory agents such as glycyrrhizinate, chelating agents such as edetate, pyrophosphate, hexametaphosphate, citric acid, malic acid, and gluconic acid, benzoate, salicylate, sorbin Acid salt, dehydroacetate, paraoxybenzoate, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether,
Preservatives such as 3,4,4'-trichlorocarbanito, benzalkonium chloride, hinokitiol, and resorcin, bactericides, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and ascorbic acid, fragrances In addition, pigments and the like can be mentioned.

The state of the detergent composition of the present invention is not limited and may be any state such as liquid, paste, gel, powder and solid. 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 mixed by a compounding method generally used by those skilled in the art.

The application of the detergent composition of the present invention is also optional, but typical examples include detergents such as kitchen detergents, hard surface detergents, face cleansers, cleansing foams, shampoos, body shampoos, and solid detergents. Is mentioned.

The reason why the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention exhibits high stability in a wide range of pH can be explained as follows. That is, fatty acid diethanolamide is susceptible to hydrolysis at high pH because it is a tertiary amide. Since the polyoxypropylene fatty acid alkanolamide compound contained in the mixture of the present invention has a secondary amide group,
It is quite stable against acids and alkalis and less susceptible to hydrolysis than tertiary amides.

Among the polyoxypropylene fatty acid alkanolamide compound mixtures of the present invention, those having an average added mole number of propylene oxide of 2 or less have particularly excellent properties in thickening and foaming properties. It is considered that the addition reaction mechanism of propylene oxide to fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide is characteristic. The primary addition reaction to the hydroxyl group of propylene oxide proceeds relatively easily. At this time, depending on the position of the methyl group, the resulting PO adduct is represented by the following reaction formula and gives two kinds of compounds (a) and (b).

[0073]

[Chemical 12]

The production ratio of these two compounds is (a) when a base catalyst such as sodium methoxide is used.
(B) ≈85: 15, which gives an overwhelmingly large amount of the secondary alcohol compound (a). The reason for this is clear. That is, 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, when nucleophilically attacking propylene oxide, propylene oxide is This is because, as shown below, it is more likely to react with the oxirane ring carbon having less steric hindrance by the methyl group.

[0075]

[Chemical 13]

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).

[0077]

Embedded image

Other products are the following compounds (ii) to (i
v).

[Chemical 15]

When the number of moles of propylene oxide added is small due to the propylene oxide addition reaction as described above, the addition reaction proceeds relatively sequentially, and therefore, the oxidization of the fatty acid alkanolamide or the polyoxyethylene fatty acid alkanolamide is carried out. The distribution of the number of propylene groups is quite narrow. However, this does not apply when the average number of added moles of propylene oxide is large.

On the other hand, the distribution of the number of oxyethylene groups of the polyoxyethylene fatty acid alkanolamide obtained by adding ethylene oxide to the fatty acid alkanolamide is broad. The reason for this is that in the case of ethylene oxide addition, since the products are all primary alcohol compounds, there is no distinction between ethylene oxide-free ones and ethylene oxide-added ones or more, and the addition in the next step It lies in the fact that the reaction proceeds. The polyoxypropylene (2) lauric acid monoethanolamide mixture and the polyoxypropylene (2) lauric acid diglycolamide mixture of the present invention and, as a comparative mixture, polyoxyethylene (2) lauric acid monoethanolamide mixture and polyoxyethylene (2) The distribution state of oxyalkylene groups in the lauric acid diglycolamide mixture is shown in FIG.

When the number of oxypropylene groups or oxyethylene groups is large, the melting point of the obtained compound is lowered and the handling property is improved, but the thickening property thereof is drastically lowered. When 2 mol of ethylene oxide is subjected to the addition reaction, polyoxyethylene fatty acid alkanolamide having 3 or more oxyethylene groups is produced at a total content of 31 to 34% by weight. Further, a compound having 0 oxyethylene groups, that is, a compound to which ethylene oxide is not added, is also present in a proportion of 13 to 15% by weight. Therefore, even when 2 mol of ethylene oxide is subjected to the addition reaction, actually, those having 2 oxyethylene groups account for only 30 to 36% by weight of the whole product. On the other hand, when propylene oxide is added, the content of the polyoxypropylene fatty acid alkanolamide having 3 or more oxypropylene groups is as small as 17 to 19% by weight, and the content of the compound having 1 or 0 oxypropylene groups is contained. The proportion is also small.

In recent years, in studies on ethylene oxide adducts of higher alcohols, ethylene oxide is added by using a special catalyst, or ethylene oxide is added by a usual method, and then the number of added moles other than the intended product is produced. Narrow range ethoxylate (NRE) is a higher alcohol ethoxylate whose oxyethylene group distribution range has been narrowed by cutting it with a method such as distillation.
It is reported that this has improved performance such as thickening and less irritation compared to the conventional one showing a broad distribution.

Among the polyoxypropylene fatty acid alkanolamide compound mixtures of the present invention, those having an average added mole number of propylene oxide of 2 or less are considered to be a kind of narrow range isomer. By replacing ethylene oxide with propylene oxide without using a special catalyst or purification method such as distillation, the narrow range conversion which was never obtained by the method of adding ethylene oxide by the usual method was used. It is thought that it was achieved.

However, various effects recognized in the present invention are as follows.
It cannot be explained only by narrowing, but it is presumed that it is expressed by the influence of the terminal hydroxypropyl group and many other factors.

As described above, the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention further improves the performance of fatty acid diethanolamide and further eliminates the drawbacks thereof. In particular, the physical properties such as melting point and solubility are similar to the fatty acid diethanolamide conventionally used in the blended products such as cosmetics and detergent compositions, and thus, the polyoxypropylene fatty acid of the present invention is used instead. With the alkanolamide compound mixture,
Effects such as thickening, foaming power, detergency, foaming stability, and emulsion stability can be expected. Furthermore, since the compound mixture of the present invention has strong resistance to hydrolysis, it can be used also in a compound having a high pH, which has heretofore been unable to use fatty acid diethanolamide. It is less likely to limit the range of use compared to.

In the conventional fatty acid diethanolamide, when an optimum one for the compounding system is selected,
Only allowed to change the composition of fatty acids,
In the compound mixture of the present invention, not only the fatty acid composition but also the type of alkanolamide group, the number of moles of ethylene oxide added, and the number of moles of propylene oxide added can be changed. Therefore, there are many performance expression variables to satisfy a wide variety of demands, such as when importance is attached to thickening, when high foaming stability is required, or when sufficient emulsion stability is required. It is more likely to be added to.

[0087]

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 mixture) To 214 g of methyl laurate, monoethanolamine 6 was added.
2 g and sodium methoxide 1 g were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 90 ° C., 1 hour) to prepare 244 g of lauric acid monoethanolamide. 244 g of this lauric acid monoethanolamide and 58 g of propylene oxide (1
Was mixed in an autoclave and stirred at 120 ° C. for 3 hours to synthesize a polyoxypropylene (1) lauric acid monoethanolamide mixture. Yield: 302g.

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, 147
^{0,1378,1128,1052cm -1 1 H-NMR (Bruker} AC-250, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
_{4.1ppm (m, 7H, -CH 2} CH 2 OCH 2 CHO
-), 6.09ppm (br, 1H, NH)

GLC analysis: A 20 mg sample of trimethylsilyl (TMS) was injected into GLC. GLC conditions Carrier: Helium Flow rate: 30 ml / min Column: CHROMPACK OV1701 25m × 0.32mm ID, film thickness 0.2μ Initial temperature: 230 ° C Heating rate: 5 ° C / min Final temperature: 300 ° C Inlet temperature: 280 ° C Detection Instrument: FID Table 1 shows the retention time and composition of the GLC analysis.

[0091]

[Table 1]

Example 2 (polyoxypropylene (1) la
Preparation of diglycolamide uric acid mixture) 214 g of methyl laurate and 10 parts of diglycolamine
6 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 120 ° C., 1 hour) to prepare 290 g of lauric acid diglycolamide. 290 g of this lauric acid diglycolamide and 58 g of propylene oxide (1 mol) were charged into an autoclave and stirred at 120 ° C. for 3 hours to synthesize a polyoxypropylene (1) lauric acid diglycolamide mixture.

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 , 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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 11H, - ( CH 2 CH 2 O) 2 -C
_{H 2 CHO -), 6.09ppm (} br, 1H, NH)

GLC analysis: same as described in Example 1. Table 2 shows the analysis results (holding time and composition).

[Table 2]

Examples 3-8 and Comparative Examples 1-2 (polio)
Xypropylene lauric acid monoethanolamide mixture
Preparation of) monoethanolamine 6 to 214 g of methyl laurate
2 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. 244 g of this lauric acid monoethanolamide was placed in an autoclave and heated to 90 ° C. with stirring, and the amount of propylene oxide shown in Table 3 was press-fitted from the propylene oxide introducer into the autoclave.
The mixture was stirred at 0 ° C. for 3 hours to synthesize polyoxypropylene lauric acid monoethanolamide mixtures having various average addition mole numbers.

Table 3 shows various physical properties and compositions.

[Table 3]

Examples 9-14 and Comparative Examples 3-4 (poly
Oxypropylene lauric acid diglycolamide mixture
Preparation of 228 g of ethyl laurate and 10 parts of diglycolamine
6 g and 2 g of sodium methoxide were added, and by-product ethanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to prepare 288 g of lauric acid diglycolamide. This was placed in an autoclave and heated to 90 ° C. with stirring, to which the amount of propylene oxide shown in Table 4 was pressure-injected from a propylene oxide introducer and stirred at 100 ° C. for 3 hours to give various average addition mole numbers. A polyoxypropylene lauric acid diglycolamide mixture was synthesized.

Table 4 shows various physical properties and compositions.

[Table 4]

Comparative Example 5 (Polyoxypropylene (1)
Preparation of Triglycolamide Uric Acid Mixture) To 214 g of methyl laurate, triglycolamine 1
50 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20
mmHg, 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 (1 time molar amount) of propylene oxide in a gaseous state was blown into the autoclave, and the mixture was stirred at 100 ° C. for 6 hours to polyoxypropylene (1) lauric acid. A triglycolamide mixture was synthesized.

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, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 15H, - ( CH 2 CH 2 O) 3 CH
₂ CHO-), 6.09ppm (br, 1H, NH)

Example 15 (Polyoxypropylene (2)
Polyoxyethylene (1) monoethanol laurate
Preparation of amide mixture) Monoethanolamine 6 was added to 214 g of methyl laurate.
2 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to prepare 244 g of lauric acid monoethanolamide. This was placed in an autoclave, heated to 90 ° C. and stirred, while ethylene oxide (44 g, 1 time molar amount) was blown into the autoclave in a gaseous state.
The reaction was carried out at 20 ° C for 2 hours. The polyoxyethylene (1) lauric acid monoethanolamide mixture-containing reaction product thus obtained was charged with 288 g of propylene oxide and subsequently 116 g (2 times the molar amount) of propylene oxide from a propylene oxide introducer and stirred at 100 ° C. for 3 hours. Then, a polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide mixture was synthesized. When the amount of dioxane contained in this mixture was quantified, it was 5 ppm
Met. Therefore, it could be used as it is without any special dedioxane treatment.

The physical properties of the product are 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, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 14H, - ( CH 2 CH 2 O) 2 -
(CH ₂ CHO) ₂ −), 6.09 ppm (br, 1H,
NH)

Example 16 (Polyoxypropylene (2)
Polyoxyethylene (1) diglycolamine laurate
Preparation of de-mixture) 214 g of methyl laurate and 10 parts of diglycolamine
6 g and 1 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to prepare 288 g of lauric acid diglycolamide. This was put in an autoclave, heated to 90 ° C. and stirred, while 44 g (1 times molar amount) of ethylene oxide was blown into the autoclave in a gaseous state.
The reaction was carried out at 0 ° C for 2 hours. To 332 g of the polyoxyethylene (1) lauric acid diglycolamide mixture-containing reaction mixture thus obtained, 116 g of propylene oxide (2 times the molar amount) was continuously introduced from a propylene oxide introducer, and the mixture was stirred at 100 ° C. for 3 hours. A polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide mixture was synthesized. When the amount of dioxane contained in this mixture was quantified, it was 4 ppm. After adding 4.5 g of water to this and stirring for 30 minutes, it was subjected to dedioxane treatment under reduced pressure (20 mmHg, 1
The dioxane content of the resulting treatment mixture was <1 ppm.

The physical properties of this mixture 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, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 18H, - ( CH 2 CH 2 O) 3 -
(CH ₂ CHO) ₂ −), 6.09 ppm (br, 1H,
NH)

Comparative Example 6 (polyoxypropylene (2)
Lioxyethylene (2) monoethanolamine laurate
Preparation of a mixture) To 214 g of methyl laurate, monoethanolamine 6
2 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. This was placed in an autoclave, heated to 90 ° C. and stirred, and 88 g (2 times the molar amount) of ethylene oxide was blown into this in a gaseous state, and 120
The reaction was performed at 0 ° C for 2 hours. Polyoxyethylene (2) lauric acid monoethanolamide mixture 3 thus obtained
To the reaction mixture containing 32 g, 116 g of propylene oxide (2 times the molar amount) was injected under pressure from a propylene oxide introducer, and the mixture was stirred at 100 ° C. for 3 hours to polyoxypropylene (2) polyoxyethylene (2) lauric acid monoethanol. An amide mixture was synthesized. The amount of dioxane contained in this mixture was determined to be 25 ppm.

The physical properties of this mixture were as follows. Melting point: -5 ° C or lower Hydroxyl value: 126 Amine value: 10.3 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, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 18H, - ( CH 2 CH 2 O) 3 -
(CH ₂ CHO) ₂ −), 6.09 ppm (br, 1H,
NH)

Comparative Example 7 (polyoxypropylene (2)
Lioxyethylene (2) lauric acid diglycolamide
Preparation of mixture) 214 g of methyl laurate and 10 parts of diglycolamine
6 g and 1 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to obtain 288 g of lauric acid diglycolamide. This was put in an autoclave, heated to 90 ° C. and stirred, while 88 g of ethylene oxide (2 times the molar amount) was blown into this in a gaseous state, and 120 ° C.
And reacted for 2 hours. Polyoxyethylene (2) lauric acid diglycolamide mixture 376 thus obtained
Following this, 116 g of propylene oxide (2 times the molar amount) was introduced under pressure from a propylene oxide introducer to obtain 100 g.
The mixture was stirred at 0 ° C. for 3 hours to synthesize a polyoxypropylene (2) polyoxyethylene (2) lauric acid diglycolamide mixture. When the amount of dioxane contained in this mixture was quantified, it was 25 ppm. After adding 4.5 g of water and stirring for 30 minutes, dedioxane was removed under reduced pressure (20 mmHg, 100 ° C., 1 hour), and the dioxane content was less than 1 ppm.

The physical properties of this mixture are as follows. Melting point: -5 ° C or lower Hydroxyl value: 114 Amine value: 12.5 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, CDCl
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
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 22H, - ( CH 2 CH 2 O) 4 -
(CH ₂ CHO) ₂ −), 6.09 ppm (br, 1H,
NH)

[0109]Example 17 (polyoxypropylene (2)
Preparation of lauric acid monoethanolamide mixture) Purified monoethanol laurate in an autoclave
Amide 243g and BF ₃・ Contain 2.4g of ether complex
Further, 116 g of propylene oxide (2 times mole)
(Amount) was added and reacted at 150 ° C. for 1 hour. End of reaction
After adding water to quench, desolvation is performed under reduced pressure.
Polyoxypropylene (2) monoethanoic acid laurate
360 g of the amide mixture were obtained.

Table 5 shows the distribution of the number of oxypropylene groups by GLC analysis.

[Table 5]

As shown in Table 5, the distribution of the number of oxypropylene groups was slightly narrower than that of the products prepared by using the base catalyst in the examples.

Example 18 (Polyoxypropylene (2)
Preparation of lauric acid diglycolamide mixture) Put 243 g of purified lauric acid diglycolamide and 2.4 g of BF ₃ · ether complex into an autoclave, and further add 116 g of propylene oxide (2 times the molar amount), and 150 ° C. Reacted 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 obtain 360 g of a polyoxypropylene (2) lauric acid monoethanolamide mixture. Table 6 shows the number distribution of oxypropylene groups by GLC analysis.

[0113]

[Table 6] As shown in Table 6, the distribution of the number of oxypropylene groups was slightly narrower than that of the product prepared using the base catalyst of Example 12.

Comparative Example 8 (Polyoxyethylene (2) Lau
Preparation of phosphoric acid monoethanolamide mixture) Monoethanolamine 6 was added to 214 g of methyl laurate.
2 g and 0.5 g of sodium methoxide were added, and the mixture was heated under reduced pressure while distilling off by-produced methanol (10
At 0 ° C., 20 mmHg, 1 hour), 243 g of lauric acid monoethanolamide was obtained. After heating this to 120 ° C., 88 g (2 times the molar amount) of ethylene oxide was gasified and blown in. After the addition, the mixture was further heated at 120 ° C. for 1 hour to obtain 331 g of a polyoxyethylene (2) lauric acid monoethanolamide mixture. 1,4 in this mixture
-It contained 50 ppm of dioxane.

10 mg of this mixture was taken, trimethylsilylated and subjected to GLC analysis. The results are shown in Table 7.

[Table 7]

As shown in Table 7, as compared with the oxypropylene group number distribution in the polyoxypropylene (2) lauric acid monoethanolamide mixture of Example 6, the ethylene oxide adduct mixture of Comparative Example 8 was The number of oxypropylene groups was broadly distributed. In particular, comparing the residual amounts of the unreacted raw materials, the product obtained by adding twice the molar amount of propylene oxide contained no unreacted raw material, while the product obtained by adding the double molar amount of ethylene oxide was used. 10 for the comparative mixture
% Of unreacted raw material remained.

Comparative Example 9 (Polyoxyethylene (2) Lau
Preparation of phosphoric acid diglycolamide mixture) 214 g of methyl laurate and 10 parts of diglycolamine
6 g and 0.5 g of sodium methoxide were added, and the mixture was heated under reduced pressure while distilling off by-produced methanol (10
At 0 ° C., 20 mmHg, 1 hour), 287 g of lauric acid diglycolamide was obtained. After heating this to 120 ° C., 88 g (2 times the molar amount) of ethylene oxide was gasified and blown in. After the addition, the mixture was further heated at 120 ° C. for 1 hour to obtain 375 g of a polyoxyethylene (2) lauric acid diglycolamide mixture. 1,4-
It contained 30 ppm of dioxane. Since the allowable concentration of dioxane is said to be 25 ppm, it was necessary to subject this product to dedioxane treatment. After adding 3.7 g of water to remove dioxane and stirring for 30 minutes, 100 ° C.
The solvent was removed under reduced pressure at 0 mmHg for 1 hour to remove dioxane.

10 mg of this product was taken, subjected to trimethylsilylation, and then analyzed by GLC. Table 8 shows the results.

[Table 8]

As shown in Table 8, in Example 1 above.
As compared with the oxypropylene group number distribution of the polyoxypropylene (2) lauric acid diglycolamide mixture of No. 2, in the ethylene oxide adduct mixture of Comparative Example 9, the number of ethylene oxide groups was broadly distributed. In particular, comparing the residual amounts of the unreacted raw materials, it was found that the unreacted raw materials were not contained in the mixture to which the propylene oxide double molar amount was added, whereas this Comparative Example 9
In the mixture to which a double molar amount of ethylene oxide was added, 10% or more of unreacted raw material remained.

Comparative Example 10 (Polyoxypropylene (1)
Preparation of lauric acid monoethanolamide mixture) To 200 g of lauric acid, 62 g of monoethanolamine was added, and the mixture was heated and stirred at 180 ° C for 12 hours under a nitrogen stream.
The reaction was carried out while distilling off the water produced at this time, but the amount of distilled water was 80% of the theoretical amount. As a result of GLC analysis, the content of lauric acid monoethanolamide in the reaction product was 75%. To this reaction product, 58 g (1 time molar amount) of propylene oxide was added, and an addition reaction was carried out at 120 ° C. for 1 hour in an autoclave. As a result of GLC analysis, the product was almost composed of a propylene oxide adduct of monoethanolamine, and the content of the target substance was 12%. The obtained reaction product had a blackish brown color and had an unpleasant odor.

Example 19 (Polyoxypropylene (1)
Preparation of lauric acid diglycolamide mixture) 106 g of diglycolamine and 1000 g of chloroform
111 g of triethylamine was added to this solution, and the mixture was cooled to 10 ° C. To this, 219 g of lauric acid chloride was added dropwise while keeping the reaction temperature at 20 ° C. After the completion of dropping, the mixture was stirred at 30 ° C. for 1 hour. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration. The filtrate was washed 3 times with 500 ml of 1N hydrochloric acid, then 3 times with 500 ml of saturated aqueous sodium hydrogen carbonate, and finally with saturated aqueous sodium sulfate solution. The product was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain 272 g of lauric acid diglycolamide (yield 95%) as a white solid.

Lauric acid diglycolamide 2 obtained
72 g, 61 g of propylene oxide (1 molar amount), and 0.5 g of sodium methoxide were placed in an autoclave, and the mixture was heated and stirred at 130 ° C. for 2 hours to add propylene oxide. The yield of the obtained polyoxypropylene (1) lauric acid diglycolamide mixture was 333 g (yield 95%). The results of various analyzes were the same as those obtained by the method of Example 2 except that the hydroxyl value was 172 and the amine value was 11.0.

As described above, the production method using a fatty acid halide such as lauric acid chloride as a starting material requires a reaction solvent such as chloroform or water, and an alkali or a base for trapping hydrochloric acid produced by the reaction. And
Further, a step of removing salts such as triethylamine hydrochloride and sodium chloride produced by trapping hydrochloric acid (specifically, steps such as filtration and washing with water) is required. Therefore, the yield is slightly lowered. Further, in the step of removing the salt, the base catalyst necessary for the addition of propylene oxide in the next step is also removed from the system, and therefore the base catalyst must be added again at the stage of adding propylene oxide. In addition, the corrosion of the equipment due to hydrochloric acid or salt generated in the acylation reaction is also a big problem. As described above, the method of producing a fatty acid halide is complicated in operation, requires an auxiliary material, and has a problem of corrosion. Therefore, as an industrial production method, the method of the present invention described in Example 2 is used. It is far inferior to the manufacturing method.

Comparative Example 11 (Polyoxypropylene (1)
Preparation of lauric acid monoethanolamide mixture) To 214 g of methyl laurate, monoethanolamine 6
2 g and 2 g of sodium methoxide were added, and by-product methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. The amine value of this product is 6.
It was 2. This was dissolved in 3000 ml of xylene, washed twice with 800 ml of 2 wt% hydrochloric acid water, and then saturated saline solution 80
The extract was washed 3 times with 0 ml and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, recrystallized from THF-toluene to purify lauric acid monoethanolamide 195.
g was obtained (80% yield). The amine value of this product is 0.01
Met. This was placed in an autoclave, and 46 g of propylene oxide (1 times the molar amount) was added to obtain 150
The mixture was stirred at ℃ for 6 hours, but no reaction occurred and only raw materials were recovered.

Melting point measurement The melting point was measured according to the Japanese Pharmacopoeia B-414 melting point measuring method (first method). For compounds that are liquid at room temperature or that are difficult to fill in capillaries, refer to Japanese Pharmacopoeia B-
The melting point was defined as the freezing point measured according to the 116 Freezing Point Measurement Method. Table 9 below shows the melting points of the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture and the polyoxypropylene fatty acid alkanolamide of the present invention and, for reference, the melting points of the fatty acid alkanolamide and the fatty acid diethanolamide which are propylene oxide addition raw materials.

[0126]

[Table 9]

As shown in Table 9, the reaction product to which propylene oxide was added had a melting point considerably lower than that of the fatty acid alkanolamide before addition. Among the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide mixtures of the present invention, those having a large number of moles of propylene oxide added were liquid at room temperature.
This melting point value was lower than the melting point of the corresponding fatty acid diethanolamide. Generally, when preparing a blended product, a liquid compound is easier to handle than a solid or powdery compound. However, even if it is a solid or a powder, if it is easily dissolved by heating, it may be melted once and then added to the compounded product.
If the temperature exceeds 0 ° C, even if you try to dissolve it in a heated water bath,
It does not melt easily and is inconvenient to handle. In that respect, the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide mixture of the present invention has a low melting point, and therefore, it can be made into a liquid by only slightly heating, and as a result, the handling property at the time of compounding is extremely improved. It was

27 g of isopropanol and 71 g of purified water were added to 2 g of the hydrolysis test sample to dissolve it, and then citric acid or caustic soda was added to adjust the pH to a predetermined value, and this solution was stored at 50 ° C. for 1 month. During that time, the pH was measured every week, and if it seemed to change, it was adjusted to the original pH value with citric acid or caustic soda. One month later, the content of lauric acid produced by hydrolysis in the sample solution was measured by GLC (absolute calibration curve method). From this lauric acid content, the hydrolysis rate was calculated by the following formula. Hydrolysis rate (%) = (lauric acid content × 200.3) /
(Number of moles of charged sample) × 100 Test results are shown in Table 10.

[0129]

[Table 10]

As shown in Table 10, lauric acid diethanolamide was found to be susceptible to hydrolysis. In particular, it was confirmed that decomposition was easily performed at pH 3 or lower or 9 or higher. On the other hand, the polyoxypropylene fatty acid monoethanolamide mixture of the present invention showed a low hydrolysis rate in a wide pH range, like lauric acid monoethanolamide. Therefore, it was revealed that the polyoxypropylene fatty acid monoethanolamide mixture of the present invention is stable in a wide range of pH, and therefore, there is less restriction on pH when it is attempted to blend it.

Ocular Mucosal Irritation Test To a Japanese white rabbit female (14 weeks old), 0.1 ml of a 10% sample solution or suspension was dropped on the lower right eyelid sac, and the upper and lower eyelids were aligned for about 5 seconds and well contacted. , Left as it is. The other side (left eye) served as an untreated control. Judgment is administration 1,
Drai after 3,6 hours and after 1,2,3,4,7 days
It was performed according to the criteria of the ze method. Based on the maximum value of the average stimulation value and the duration of the score, the safety evaluation criteria are KAY
It was performed based on the eye irritation evaluation criteria of & CALANDRA. The evaluation has the following eight levels. 1: No irritation 2: Practically no irritation 3: Minimal irritation 4: Mild irritation 5: Moderate irritation 6: Strong irritation 7: Extremely irritation 8: Maximum irritation The test results are shown in Table 11.

[0132]

[Table 11]

As shown in Table 11, it was confirmed that the polyoxypropylene (polyoxyethylene) fatty acid monoethanolamide mixture of the present invention had substantially no ocular mucosal irritation. On the other hand, slight irritation was observed in the compounds having an average number of moles of propylene oxide added outside the scope of the present invention. In addition, slight stimulation was also observed with fatty acid monoethanolamide. In addition, slight irritation was observed with polyoxyethylene fatty acid monoethanolamide. From the above results, it was confirmed that the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide mixture used in the present invention is a compound that can be safely used in detergents such as shampoos and cosmetics such as rinses.

Examples 20 to 26 and Comparative Examples 12 to 20 In each of Examples 20 to 26 and Comparative Examples 12 to 20, polyoxypropylene fatty acid monoethanolamide, polyoxypropylene fatty acid diglycolamide,
Polyoxypropylene polyoxyethylene fatty acid monoethanolamide, polyoxypropylene polyoxyethylene fatty acid diglycolamide and commercially available fatty acid alkanolamide were used to prepare compositions having the compounding compositions shown in Tables 12 and 13. The obtained composition was subjected to a thickening test, a foaming force test and a foaming stability test. Each test was performed by the following method.

1) Thickening test 7.5 ml of a sample was put in a small amount of a sample adapter and placed at 25 ° C.
After the temperature was kept at, the viscosity was measured with a B-type viscometer (B8M manufactured by Tokyo Keiki Co., Ltd.). 2) Foaming power test The detergent was diluted with distilled water so that the pure content of the active agent 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 200 mm or more ○: Good foaming, foaming power of 180 mm or more, less than 200 mm △ ... Normal foaming, foaming power of 150 mm or more, less than 180 mm × ... Poor foaming, foaming power of 150 mm Less than

3) Foaming Stability Test When conducting the loss-miles foaming force test described above, the foaming force immediately after charging and the foaming force after 5 minutes were measured to obtain the foam damping rate. Attenuation rate (%) = (FH ₀ −FH ₅ ) / (FH ₀ ) × 10
However, in the above formula, FH ₀ : foaming power immediately after charging FH ₅ : foaming power after 5 minutes Evaluation criteria were set as follows. ∘: Foaming stability is extremely good, damping rate is less than 10% ◯: Foaming stability is good, damping rate is 10 to 20% △: Foaming stability is normal, damping rate is 21 to 50% × ... Foaming stability Table 12 and Table 13 show the test results, which are poor in properties and have an attenuation rate of 50% or more.

[0137]

[Table 12]

[0138]

[Table 13]

As is clear from the results shown in Tables 12 and 13, the composition containing the fatty acid alkanolamide derivative has a higher viscosity than that of the polyoxyethylene lauryl ether sulfate Na alone. It was confirmed that the amide derivative also has a thickening property. However, the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is
It is suitable because it has an appropriate viscosity. Also,
Polyoxyethylene lauryl ether sulfate Na
The foaming power is higher when the fatty acid alkanolamide derivative is contained than when it is alone, but when the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is contained, other fatty acid alkanolamides are contained. The rate of increase in foaming power was larger than that of the above. A similar tendency was observed for foam stability.
From the above results, the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention is a thickener, a foaming agent,
It was confirmed to have excellent properties as a foam stabilizer.

Of the results shown in Tables 12 and 13, when the average added molar amount of propylene oxide was fixed to 1 times the molar amount, the relationship between the number of oxyethylene groups in the molecule of the resulting mixture and the change in viscosity increase was shown in FIG. Shows the graph. From FIG. 2, the change in viscosity when the number of oxyethylene groups is changed can be read.

As is apparent from FIG. 2, those having an oxyethylene group number (p) of less than 1, that is, lauric acid isopropanolamide have too high a viscosity and are difficult to use. Further, when the number of oxyethylene groups (p) exceeds 2, the viscosity sharply decreases. In contrast, the oxyethylene group number (p) used in the present invention is 1, that is, the monoethanolamide compound mixture, and the oxyethylene group number (p) is 2, that is, the diglycol amide compound, has an appropriate viscosity. Was confirmed.

Similarly, among the results in Tables 12 and 13, when the number of oxyethylene groups (p) in the compound molecule was fixed at 1, the average number of moles of propylene oxide added and the viscosity increase of the resulting compound mixture were measured. The relationship is shown in FIG. From FIG. 3, it is possible to read the change in viscosity when the average added mole number of propylene oxide is changed.

As is clear from FIG. 3, propylene oxide and the ones having an average addition mole number of less than 0.3 have a sharply increased viscosity and are difficult to use as a cleaning agent. On the other hand, the average number of added moles of the present invention (0.3 to
It can be seen that the propylene oxide addition compound mixture having 10) has an appropriate viscosity. However, since the viscosity tends to decrease as the average added mole number of propylene oxide is increased, it is preferable that the average added mole number of propylene oxide is 2 or less particularly when used in a detergent such as shampoo.

Examples 27 to 30 and Comparative Examples 21 to 28 Polyoxypropylene fatty acid monoethanolamide mixture, polyoxypropylene fatty acid diglycolamide mixture, polyoxypropylene polyoxyethylene fatty acid monoethanolamide mixture, poly The emulsifying power of oxypropylene polyoxyethylene fatty acid diglycolamide mixture and commercially available fatty acid alkanolamides were measured. The emulsification test was performed by the following method.

Dissolve an amount of the sample shown in Table 14 in distilled water,
The pH was adjusted to 7 with citric acid or caustic soda, and this was used as a sample solution. 10 ml of this sample solution and olive oil 2
g and 30 ml were put into a test tube with a ground stopper, shaken vigorously 50 times, and allowed to stand. After 30 minutes, the state inside the test tube was observed. "Insoluble" when the sample is not dissolved in distilled water, "Emulsified" when the sample is dissolved in distilled water and does not separate into an aqueous layer and an emulsified layer (including oil layer) and is emulsified When was dissolved in distilled water and separated into an aqueous layer and an emulsified layer, the thickness of the emulsified layer was measured in mm, and this was taken as the emulsifying power. The test results are shown in Table 14.

[0146]

[Table 14]

As is clear from the results shown in Table 14, when the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention were used, even when they were completely emulsified or separated. The emulsified layer was thick. This means that the emulsifying power of the compound mixture is excellent. Therefore, it was confirmed that the compound mixture of the present invention is useful as an emulsifier. On the other hand, as shown in Comparative Examples 21 to 27, other fatty acid alkanolamides and polyoxypropylene fatty acid alkanolamide compound mixtures outside the scope of the present invention have no water solubility in the sample itself, or have water solubility. The thickness of the emulsified layer was thin and the emulsifying power was not sufficient.

Examples 31 to 34 and Comparative Examples 29 to 36 Polyoxypropylene fatty acid monoethanolamide mixture (Example 8), polyoxypropylene fatty acid diglycolamide mixture (Example 14) and polyoxypropylene shown in Table 15. The dispersion power in oil was measured for the polyoxyethylene fatty acid monoethanolamide mixture, the polyoxypropylene polyoxyethylene fatty acid diglycolamide mixture and the commercially available fatty acid alkanolamides. The dispersion test was performed by the following method.

As inorganic powder, 100 g of alumina powder having an average particle diameter of 1 μ and titanium oxide powder 10 having an average particle diameter of 0.8 μ
The inorganic powder was mixed with 0 g, and the inorganic powder was mixed with 500 g of light oil in which the amount of the dispersant shown in Table 15 was dissolved with respect to the weight of the inorganic powder, and the dispersibility was tested. In this test, the test sample was placed in a 2 liter beaker, stirred for 1 minute at 120 rpm using a 4-blade impeller, and then allowed to stand for 1 minute to remove the residual state of alumina powder and titanium oxide powder at the bottom of the beaker. Observe and, if all of the powder was dispersed in oil, and most of the powder was dispersed in oil, but remained slightly at the bottom, further vigorously stir at 4000 rpm for 5 minutes using a homogenizer. A 500 ml graduated cylinder was allowed to stand for 1 day, and then a glass rod having a diameter of 5 mm and a weight of 50 g was dropped into the dispersion through a guide provided on the top of the cylinder to observe the precipitation state. The dispersion stability was evaluated according to the following two grades. ○: The rod reached the bottom of the cylinder. B: The rod stopped without reaching the bottom of the cylinder, and a consolidation layer was generated. X: Dispersion did not occur at the initial stirring. The test results are shown in Table 15.

[0150]

[Table 15]

As is clear from Table 15, the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention have excellent dispersibility in oil and are useful as dispersants in oil. It is a thing.

Examples 35-38 and Comparative Examples 37-44 Polyoxypropylene fatty acid monoethanolamide mixture of the present invention (Example 8), polyoxypropylene fatty acid diglycolamide mixture (Example 14), polyoxypropylene polyoxy. Lime soap dispersancy was measured for ethylene fatty acid monoethanolamide mixture, polyoxypropylene polyoxyethylene fatty acid diglycolamide mixture and commercially available fatty acid alkanolamide mixture. This dispersion test was conducted by the following method.

The method of Borghetti et al. (J. Am.
il Chem. Soc., 27 , 88 (1950)). A 0.5 wt% aqueous solution of sodium oleate was placed in a 50 ml test tube with a stopper, and then 5 ml of a 0.25 wt% aqueous solution of the sample to be tested.
0.8824 g of CaCl ₂ .2H ₂ O and M
0.8132 g of gCl ₂ .6H ₂ O was added to 10 ml of hard water prepared by dissolving in 1 liter of distilled water, and the whole was added to 30 ml.
Distilled water was added to make up to ml. The mixed solution was repeatedly inverted 20 times, and then the test tube was allowed to stand in a thermostat at 25 ° C for 30 seconds to observe the condition of the particles of lime soap, and 0.25 wt. % Sample aqueous solution was added. From the added amount Aml of the sample aqueous solution at that time, the lime soap dispersive power (LSDP) was calculated by the following formula. LSDP (%) = (Aml × 0.0025) /0.025
The results of the × 100 test are shown in Table 16.

[0154]

[Table 16]

As is apparent from Table 16, it was confirmed that the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention were excellent in lime soap dispersibility. Therefore, the compound mixture of the present invention is useful as a dispersant in water. The results also show that the detergent containing the mixture of the present invention has excellent hard water resistance.

Examples 39 to 42 and Comparative Examples 45 to 52 Polyoxypropylene fatty acid monoethanolamide mixture of the present invention (Example 1), polyoxypropylene fatty acid diglycolamide mixture (Example 2), polyoxypropylene polyoxy Solubilizing power was measured for ethylene fatty acid monoethanolamide mixture (Example 15), polyoxypropylene polyoxyethylene fatty acid diglycolamide mixture (Example 16) and commercially available fatty acid alkanolamides. The solubilization test was performed by the following method.

Sample solutions having the compositions shown in Table 17 were prepared. Put 20 ml of this sample solution into a test tube with 30 ml stopper,
The temperature was adjusted to 20 ° C. in a constant temperature bath. Toluene was added dropwise to the sample solution with a microsyringe while shaking the test tube vigorously, and the amount of toluene (μ
1) is used to indicate the solubilization limit amount of the test solution. The test results are shown in Table 17.

[0158]

[Table 17]

As is clear from the results shown in Table 17, the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention had a high solubilization amount. This means that the compound mixture of the present invention is
It shows that the solubilizing power is superior to other fatty acid alkanolamides, polyoxypropylene fatty acid alkanolamides outside the scope of the present invention, or polyoxypropylene polyoxyethylene fatty acid alkanolamides.

Examples 43 to 46 and Comparative Examples 58 to 60 In Examples 43 to 46 and Comparative Examples 53 to 60, hand creams having the compositions shown in Table 18 were prepared.
The obtained cosmetics were subjected to the following emulsion stability test and sensory test.

These tests were conducted by the following methods. 1) Emulsion stability test After heating component A and component B separately to 75 ° C., component B
Ingredient A was added to. At this time, it was emulsified by vigorous stirring using a 4-blade impeller. The emulsion was cooled to room temperature while continuing stirring, and then stored at room temperature for 1 month to examine the emulsified state. The evaluation criteria were set as follows. ⊙: Completely emulsified ∘: Partially separated part is observed △: Partially separated ×: Completely separated

2) Sensory test The sensory test was performed by 10 professional panelists actually using it, and the feeling after use. The evaluation criteria were set as follows. ⊚: Answered by 8 people or more ○: Answered by 6-7 people △: Answered by 4-5 people ×: Answered by 3 people or less Table 18 shows the test results.

[0163]

[Table 18]

As is apparent from Table 18, the cream containing the polyoxypropylene fatty acid alkanolamide mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention was excellent in emulsion stability. Also, the usability was excellent. On the other hand, a cream containing a fatty acid alkanolamide or the like or a polyoxypropylene fatty acid alkanolamide outside the scope of the present invention was inferior in emulsion stability and usability.

Examples 47 to 52 and Comparative Examples 61 to 70 In Examples 47 to 52 and Comparative Examples 61 to 70, cleaning agents having the compositions shown in Table 19 were prepared. The obtained product was subjected to a foaming power test, a detergency test, a foaming stability test, a thickening test, a cold resistance test and a protein denaturation test.

These tests were conducted by the following methods. 1) Foaming power test Same as the method described in Example 20. 2) Detergency test Sudan III 0.1% was added to beef tallow as an indicator, 5 g of it was applied to a porcelain dish (diameter 25 cm), and this beef tallow application dish was soaked in 30 g of a 10 wt% washing solution. The washing power was defined as the number of dishes that were washed by rubbing with a sponge and washed until the tallow could no longer be washed from the dishes.

3) Foaming stability test Same as the method described in Example 20. 4) Thickening test The viscosity was measured by the same method as that described in Example 20, and it was examined whether there was thickening. The evaluation criteria were set as follows. ◎: Remarkable thickening effect ○: Thickening effect ×: No thickening effect observed

5) Cold Resistance Test A sample was put in a test tube and stored in a freezer at −5 ° C. for 7 days to examine whether or not turbidity was observed. The evaluation criteria were set as follows. ◎ ... No turbidity after storage at -5 ° C for 7 days ◯ ... Transparency at room temperature, but slight turbidity at -5 ° C, storage for 7 days △ ... Cloudy at room temperature × ... Crystal precipitation

6) Protein Denaturation Rate Test The ovalbumin denaturation rate when the sample was added to the ovalbumin pH7 buffer solution at a sample concentration of 1% using aqueous gel filtration high performance liquid chromatography was 220%.
It measured using the absorption peak of nm. Denaturation rate (%) = (H _o −H _s ) / H _o × 100 H _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 less than 10% ◯: Ovalbumin denaturation rate 10-29% △: Ovalbumin denaturation rate 30-59% ×: Ovalbumin denaturation rate 60% or more

The test results are shown in Table 19.

[Table 19]

As is clear from the results in Table 19, Examples 47 to 5 containing the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention.
The cleaning agent of No. 2 was excellent in foaming power, cleaning power and foaming stability, had an appropriate thickening property, was excellent in cold resistance, and had low irritation. On the other hand, it contained a polyoxypropylene fatty acid alkanolamide mixture outside the range used in the present invention, a polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture outside the scope of the present invention, a fatty acid alkanolamide and a polyoxyethylene fatty acid monoethanolamide. The cleaning agents of Comparative Examples 61 to 70 were inferior in any of foaming power, cleaning power, foaming stability, thickening property, cold resistance and irritation.

Examples 53-60 and Comparative Examples 71-78 In Examples 53-60 and Comparative Examples 71-78, cleaning agents having the compositions shown in Table 20 were prepared. The obtained product was subjected to a foaming power test, a detergency test, a foaming stability test, a thickening test, a cold resistance test and a protein denaturation test.

The test results are shown in Table 20.

[Table 20]

As is clear from the results of Table 20, the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention, an anionic surfactant,
The cleaning agents of Examples 53 to 60, which consist of at least one selected from an amphoteric surfactant, a cationic surfactant and a nonionic surfactant, are excellent in foaming power, cleaning power and foaming stability and are suitable. It had thickening properties, excellent cold resistance, and low irritation. On the other hand, a polyoxypropylene fatty acid alkanolamide mixture outside the scope of the present invention,
Polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture, fatty acid alkanolamide and polyoxyethylene fatty acid monoethanolamide, and at least one selected from anionic surfactant, amphoteric surfactant, cationic surfactant and nonionic surfactant The cleaning agents of Comparative Examples 71 to 78 consisting of and were inferior in any of foaming power, cleaning power, foaming stability, viscosity increasing, cold resistance, and irritation.

Examples 61 to 75 and Comparative Examples 79 to 93 In Examples 61 to 75 and Comparative Examples 79 to 93, cleaning agents having the compositions shown in Table 21 and Table 22 were prepared. The obtained product was subjected to a foaming power test, a detergency test, a foaming stability test, a thickening test, a cold resistance test and a protein denaturation test.

The test results are shown in Tables 21 and 22.

[Table 21]

[0177]

[Table 22]

As is clear from the results shown in Tables 21 and 22, the detergent using the polyoxypropylene fatty acid alkanolamide mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention contained fatty acid diethanolamide. Compared with conventional detergents, the foaming power, cleaning power, foaming stability, and thickening property were excellent, although the cold resistance and the protein denaturation rate were similar. Therefore, in a compounded product using a conventional fatty acid diethanolamide, a more excellent cleaning can be achieved by using the polyoxypropylene fatty acid alkanolamide mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention instead of the fatty acid diethanolamide. It was confirmed that it could be used as an agent.

Further, the cleaning composition of Example 75 showed almost no decrease in pH as compared with the cleaning composition of Comparative Example 93 even after being stored at 50 ° C. for one month. In general, the pH is adjusted to around 10 in a compound based on fatty acid soap, so that it is difficult to use fatty acid diethanolamide which is easily hydrolyzed at such a high pH. However, since the polyoxypropylene fatty acid alkanolamide mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention are stable even at the above-mentioned high pH, it was confirmed that blending with fatty acid soap is also possible.

Example 76 A cream having the following composition was prepared by a usual method and subjected to the same emulsification test as in Example 27. As a result, the emulsion stability and usability were excellent. Ingredients wt% Polyethylene glycol monostearate (40EO) 1.0 Polyoxypropylene (2) stearic acid monoethanolamide mixture 1.0 Self-emulsifying glyceryl monostearate 5.0 stearic acid 5.0 Behenyl alcohol 1.0-Liquid paraffin 10.0-Cetyl octanoate 10.0-Ethyl paraoxybenzoate 0.2-Glycerin 5.0-Luffa extract 1.0-Preservative 0.5-Purified water balance

Example 77 A milky lotion having the following composition was prepared by a usual method, and its performance was sensory-evaluated. As a result, a moist feel was exhibited. Ingredients% by weight • Compound mixture of Example 1.0 • Polyoxyethylene sorbitan monostearate (20EO) 1.0 • Polyoxyethylene sorbitate tetraoleate (60EO) 0.5 • Stearic acid 0.5 • Behenyl alcohol 0 .5 ・ Avocado oil 3.0 ・ Glyceryl trioctanoate 5.0 ・ 1,3-butylene glycol 5.0 ・ Xanthan gum 0.1 ・ Disodium edetate 0.2 ・ Preservative 0.1 ・ Purified water balance

Example 78 A milky lotion having the following composition was prepared by a usual method, and its performance was sensory-evaluated. As a result, a moist feel was exhibited. Ingredients wt% -Polyoxyethylene hydrogenated castor oil (60EO) 8.0-Ethanol 15.0-Polyoxypropylene (1) myristic acid diglycolamide mixture 0.5-Behenyl alcohol 1.0-Methyl paraoxybenzoate 0.1・ Glycerin 5.0 ・ Purified water balance

Example 79 A stick-form antiperspirant having the following composition was prepared by a usual method, and its performance was sensory-evaluated. As a result, a good antiperspirant action was shown. Ingredients% by weight • Compound mixture of Example 15 28.5 • POP (3) myristyl ether 15.0 • Propylene glycol 30.0 • Aluminum chlorohydrate propylene glycol complex 20.0 • Perfume 1.0 • Purified water balance

Example 80 An aftershaving lotion having the following composition was prepared by a usual method, and the performance thereof was subjected to a sensory evaluation to find that the tingling sensation after shaving was small. Ingredients wt% -Propylene glycol 51.8-Polyoxypropylene (1) Coconut oil fatty acid monoethanol amide 7.5-POE (75) Lanolin 1.2-Sodium stearate 8.5-Dye 0.1-Perfume oil 3. 0-Alcohol 5.0-POE (20) sorbitan monolaurate 3.0-Purified water balance

Example 81 A bath agent having the following composition was prepared by a usual method, and its performance was sensory evaluated. As a result, a moist feeling on the skin after bathing was shown. Ingredient% by Weight Sodium Sulfate 54.0 Sodium Bicarbonate 10.0 Sodium Carbonate 5.0 Sodium Chloride 30.0 Polyoxypropylene (1) Linoleic Acid Diglycolamide Mixture 1.0

Example 82 A poultice of the following composition was prepared by a usual method, and its performance was sensory-evaluated. As a result, it was found to be excellent in usability. Ingredients wt% -Polyacrylic acid 30.0-Crotamiton 1.0-Sodium polyacrylate 7.0-Aluminum chloride 0.3-Glycerin 20.0-Sorbitan monooleate 1.0-Polyoxypropylene (0.7 ) Oleic acid monoethanol amide 0.7 ・ Titanium oxide 5.0 ・ Purified water balance

Example 83 A creamy foundation having the following composition was prepared by an ordinary method, and the performance thereof was subjected to a sensory evaluation. As a result, it had good elongation during use and an excellent feeling in use. Ingredients wt% -Dimethylpolysiloxane (6cs) 10.0-Methylphenylpolysiloxane 3.0-Octamethylcyclotetrasiloxane 10.0-Polyoxyalkylene-modified silicone 5.0-Compound mixture of Example 8 0.5- Titanium oxide 5.0, sericite 2.0, talc 3.0, red iron oxide 0.4, iron oxide yellow 0.7, iron oxide black 0.1, glycerin 5.0, phosphoramidon 0.25, 6-amino- n-caproic acid 0.5-preservative appropriate amount-fragrance appropriate amount-purified water balance

Example 84 A pack agent having the following composition was prepared by a usual method, and the performance thereof was subjected to a sensory evaluation. As a result, spreadability during application was good and peelability was excellent. Ingredients% by weight • Dipropylene glycol 3.0 • Polyethylene glycol 3.0 • 1,3-Butylene glycol 1.0 • Glycerin 2.0 • Sodium pyrrolidonecarboxylate 1.0 • Lactic acid 0.5 • Sodium lactate 0.5・ Polyvinyl alcohol 12.0 ・ Polyoxypropylene (10) isostearic acid diglycol amide mixture 0.3 ・ Ethanol 3.0 ・ Polyoxyethylene polyoxypropylene decyl tetradecyl ether 0.3 ・ Preservative proper amount ・ Perfume proper amount ・ Refining Remaining water

As is clear from the results of Examples 76 to 84, the skin cosmetics containing the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention were excellent in emulsion stability and feel during or after use.

Example 85 A hair conditioner having the following composition was prepared by a usual method, and the performance thereof was sensory-evaluated. As a result, the hair after use showed a moist feel. Ingredient% by weight- Compound mixture of Example 4 1.0-Polyvinylpyrrolidone 2.0-Hydrolysed collagen peptide 0.2-Ethanol 5.0-Purified water balance

Example 86 A hair brushing agent having the following composition was prepared by an ordinary method, and the performance thereof was subjected to a sensory evaluation to find that it was excellent in combability. Ingredients% by weight -Cocoyl arginine ethyl ester-PCA salt 0.5-Ethanol 5.0-Polyoxypropylene (1.5) Polyoxyethylene (1) Palmitic acid monoethanolamide mixture 0.1-Methylparaben 0.1-Fragrance 0.1 ・ Purified water balance

Example 87 A hair cream having the following composition was prepared by a usual method,
When subjected to the same emulsion stability test as in Example 27, the emulsion stability and the feeling of use were excellent. Ingredients wt% Liquid paraffin 10.0 Squalane 7.0 Jojoba oil 3.0 Solid paraffin 3.0 Polyoxyethylene cetyl ether 1.5 Polyoxypropylene (1) Caprylic acid monoethanolamide mixture 1. 5 ・ Sorbitan sesquioleate 0.8 ・ Preservative 0.3 ・ Purified water balance

Example 88 A hair treatment cream having the following composition was prepared by a usual method and subjected to the same emulsion stability test as in Example 27. As a result, the emulsion stability was good and the hair after use had a moisturizing effect. Give a feeling of use. Ingredients wt% -Avocado oil 5.0-Squalane 7.0-Liquid paraffin 10.0-Stearic acid 3.0-Glycerin monostearate 3.0-Polyoxypropylene (5) Polyoxyethylene (0.5) Palm Nuclear oil fatty acid monoethanolamide mixture 2.0 ・ Lanolin alcohol 5.0 ・ Sodium edetate 0.1 ・ Preservative 0.2 ・ Purified water balance

Example 89 A hair rinse having the following composition was prepared by a usual method, and the performance thereof was subjected to a sensory evaluation. As a result, the fingers passed smoothly and the hair after use had a moist feeling. Ingredients wt% -Cetyl alcohol 3.0-Liquid paraffin 3.0-Cetyl octanoate 8.0-Polyoxypropylene (2) coconut oil fatty acid diglycolamide mixture 2.0-Stearyltrimethylammonium chloride 3.0-Paraoxybenzoic acid Methyl acid 0.1 ・ Purified water balance

Example 90 A blow dry conditioner having the following composition was prepared, and the performance thereof was subjected to a sensory evaluation. As a result, the hair after blow had less damage and showed a moist feel. Ingredients wt% -Quaternized polyvinylpyrrolidone 2.0-Oleyldimethylbenzylammonium chloride 0.6-POE (20) sorbitan monolaurate 0.2-Compound mixture of Example 10 0.3-Ethanol 3.0-Purification Remaining water

Example 91 A first agent for permanent wave having the following composition was prepared, and its performance was sensory-evaluated. As a result, excellent set persistence was shown. In addition, the hair had little damage after use and exhibited excellent moisturizing feeling and gloss. Ingredients wt% Cetyltrimethylammonium chloride 4.0 Polyether-modified silicone 1.5 Ammonium thioglycolate 12.0 Silk fibroin peptide 0.5 Monoethanolamine 0.8 Emulsifier 1.0 Example 17 Compound mixture of 0.3 ・ Lauric acid diethanolamide 0.3 ・ Dipotassium glycyrrhizinate 0.05 ・ EDTA 0.1 ・ Ammonia water pH = 9 amount ・ Purified water balance

As is clear from the results of Examples 85 to 91, the hair cosmetics containing the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention were excellent in emulsion stability. In addition, since the hair is less irritating, the hair after use has an excellent feeling of use.

Example 92 A rinse-inclusive shampoo having the following composition was prepared, and Example 4 was used.
The same foaming power, detergency, foaming stability, viscosity increasing, cold resistance, and protein denaturation rate tests as in Example 7 were performed. Ingredients wt% N-carboxymethyl-N- {2- [2-hydroxyethyl-coconut oil fatty acid amide] ethyl} glycine 20.0-N-cocoyl-L-glutamic acid triethanolamine 5.0-2-coconut oil Alkyl-N-carboxyethyl-N-hydroxy-ethylimidazolinium betaine 10.0-coconut oil fatty acid diethanolamide 1.0-polyoxypropylene (0.5) coconut oil fatty acid monoethanol amide mixture 1.0-stearyl chloride Trimethylammonium 1.5-Cetyl octoate 0.5-Carboxymethyl chitin 0.1-Hyaluronic acid 0.1-Sodium edetate 0.1-Preservative 0.1-Purified water balance Table 23 shows the test results.

Example 93 A conditioning shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients wt% -Polyoxyethylene (3) sodium lauryl sulfate 10.0-Lauroyl-N-methyl-β-alanine sodium 20.0-Polyoxyethylene (3) coconut oil fatty acid monoethanolamide sodium sulfate 2.0-Cation Guar gum 0.3 ・ Lauric acid monoethanolamide 2.0 ・ Compound mixture of Example 12 1.0 ・ Glycerin 3.0 ・ Sodium edetate 0.1 ・ Citric acid pH = 6.5 ・ Purified water The balance test results are shown in Table 23.

[0200]Example 94 A pearly shampoo having the following composition was prepared and used in Example 92:
It was subjected to the same test. Ingredient weight% -N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine 15.0-2-coconut oil alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30%) 10.0-Palm Oil fatty acid amide dimethylpropyl betaine 5.0-Lauroyl-N-methyltaurine sodium 5.0-Polyoxypropylene (0.3) coconut oil fatty acid monoethanol amide mixture 1.0-Palm oil fatty acid diethanolamide 2.0-Palm Oil fatty acid monoethanolamide 1.5 ・ Amount of caustic soda pH = 6 ・ Methylparaben 0.1 ・ Perfume proper amount ・ Purified water balance Table 23 shows the test results.

Example 95 A gel shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients wt% -Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate 25.0-Lauric acid isopropanolamide 8.0-Compound mixture of Example 9 1.0-Carboxymethyl chitin 0.1-Methylparaben 0.1 -EDTA 0.1-Amount of citric acid pH = 7.0-Purified water The balance test results are shown in Table 23.

Example 96 A shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredient Weight% & C _{14-.alpha.-olefin} sulfonate sodium 5.0 - sodium cocoyl isethionate 5.0 lauroyl -N- methyl taurine sodium 5.0-polyoxyalkylene-modified organopolysiloxane (a 20% denaturing polyoxyethylene 20% by weight of the group) 1.0-Compound mixture of Example 7 5.0-Lauric acid monoethanolamide 2.0-Methylparaben 0.1-EDTA 0.1-Purified water Residual test results are shown in Table 23.

Example 97 A shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients% by weight Sodium lauryl sulphate 15.0 POE (3) sodium lauryl ether carboxylate 5.0 Sodium mono (polyoxyethylene (6) lauric acid amide) phosphate 4.0 4.0 Polyoxypropylene (1) poly Oxyethylene (0.2) palmitic acid monoethanolamide mixture 3.0 • Methylparaben 0.1 • EDTA 0.1 • Purified water Residual test results are shown in Table 23.

Example 98 A body shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients wt% 2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30%) 20.0-triethanolamine monododecylphosphate 5.0-polyoxypropylene (1) polyoxyethylene ( 0.8) Myristic acid diglycolamide mixture 3.0-Triethanolamine laurate 7.0-Methylparaben 0.1-EDTA 0.1-Purified water Residual test results are shown in Table 23.

Example 99 A body shampoo having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients wt% -Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 10.0-Polyoxyethylene (5) lauric acid monoethanolamide disodium sulfosuccinate (30%) 5.0-Lauroyl sarcosine Sodium 5.0-Lauryldimethylamine oxide 4.0-Compound mixture of Example 1-Diethanolamine laurate 3.0-Ethanol 2.0-Purified water Residual test results are shown in Table 23.

Example 100 A face wash having the following composition was prepared and subjected to the same tests as in Example 92. Ingredient% by weight N-2-hydroxyethyl-N-2-coconut oil fatty acid amide Ethyl-β-alanine (30%) 60.0 Lauric acid diethanolamide 7.0 ・ 2-Alkyl-N-carboxymethyl-N -Hydroxy-ethylimidazolinium betaine (30%) 5.0-Monylammonium glycyrrhizinate 0.2-Polyoxypropylene (2) diglycol amide isostearate 1.0-Polyoxyethylene (2) lauric acid monoethanolamide 0.5-Allantoin 0.5-Methylparaben 0.1-Amount of citric acid pH = 6.5-Purified water Residual test results are shown in Table 23.

Example 101 A hard surface cleaning agent having the following composition was prepared and subjected to the same test as in Example 92. Ingredients wt% -Polyoxypropylene (1) Coconut oil fatty acid monoethanolamide 3.0-Sodium xylene sulfonate 6.0-Trisodium phosphate 5.0-POP (2) methyl ether 4.0-Pine oil 2. 0-Purified water The balance test results are shown in Table 23.

Example 102 A kitchen detergent having the following composition was prepared and subjected to the same tests as in Example 92. Ingredients% by weight- sodium α-olefin sulfonate 15.0-laurylamide dimethylhydroxypropyl sulfobetaine (30%) 5.0-lauryl glucoside 3.0-POE (2) lauric acid monoethanolamide 2.0-edetic acid Salt 0.1-Polyoxypropylene (1.5) oleic acid monoethanol amide 0.3-Purified water Residual test results are shown in Table 23.

Example 103 An automatic dishwashing detergent of the following composition was prepared and Example 92
The same test was performed. Ingredients wt% Na lauryl benzene sulfonate 20.0 Sodium xylene sulfonate 5.4 Sodium sulfate 1.0 Lauryl alcohol ammonium sulfate 8.35 Polyoxypropylene (0.5) myristic acid monoethanol amide 5.0 -Purified water Table 23 shows the balance test results.

Example 104 An oven cleaner having the following composition was prepared and subjected to the same test as in Example 93. This cleaning agent was particularly effective for removing oil stains that were thermally deteriorated. Ingredients wt% POE (9) sodium nonylphenyl ether sulfate 3.0 POE (9) sodium nonylsulfophenyl ether sulfate 3.0 sodium hydroxide 4.0 polyoxypropylene (1) coconut oil fatty acid diglycolamide 5.0 Purified water The balance test results are shown in Table 23.

[0211]

[Table 23]

As is apparent from the results in Table 23, Examples 92 to 10 containing the polyoxypropylene fatty acid alkanolamide mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture of the present invention.
The cleaning agent of No. 4 was excellent in foaming power, cleaning power, foaming stability, thickening property and cold resistance, and had a low protein denaturation rate.

Example 105 An enzyme-containing detergent having the following composition was prepared, and its performance was sensory-evaluated. As a result, it showed excellent detergency. Ingredients wt% -POE (6) C _10-14 fatty alcohol ether 17.0-alkylbenzenesulfonic acid diethanolamine salt 60.0-polyoxypropylene (1) coconut oil fatty acid monoethanol amide 22.0-Enzyme AP 0.2- Lipase A 0.15 ・ Hard water (100ppm) 0.65

Example 106 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
The sensory evaluation of the performance showed that the skin after use had an excellent refreshing feeling. Ingredients% by weight • Base for soap (beef tallow: coconut = 8: 2) 93.3 • N-lauroyl-L-sodium aspartate 2.0 • Titanium oxide 0.1 • Edetate 0.1 • Example 12 Compound mixture 4.5

Example 107 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
The sensory evaluation of the performance showed that the skin after use had an excellent moist feeling. Ingredients wt% N-lauroyl-L-glutamate monosodium 50.0 N-oleoyl-L-glutamate monosodium 41.0 Myristyl alcohol 8.0 The compound mixture of Example 16 1.0

Example 108 A bubble bath agent having the following composition was prepared, and its performance was sensory-evaluated. As a result, a moist feeling was imparted to the skin after bathing. Ingredient wt% Distearyldimethylammonium chloride 59.0 Palm oil fatty acid amide propyldimethylglycine 16.0 Dimethylmyristylamine oxide 4.0 Polyoxypropylene (0.5) myristic acid monoethanol amide 7.0 Fragrance 1.0 ・ Purified water balance

Example 109 A waterless hand cleaner having the following composition was prepared,
A sensory evaluation of the performance showed a good detergency. Ingredients wt% Deodorized kerosene 20.0 Oleic acid 10.0 Methylcyclohexanol 2.0 Compound mixture of Example 1 4.5 POE (40) Lanolin alcohol 4.0 Hexylene glycol 4.5 Potassium hydroxide 0.2 ・ Triethanolamine 3.2 ・ Perfume proper amount ・ Preservative proper amount ・ Purified water balance

Example 110 A dry cleaning detergent having the following composition was prepared, and its performance was sensory-evaluated. As a result, the cleaning ability was excellent. Ingredients wt% -Alkylbenzene sulfonic acid dibutyl isopropanol amine salt 30.0-Compound mixture of Example 4 15.0 2-Ethylhexyl sulfosuccinate 20.0-Petroleum solvent 35.0

Example 111 A solid deodorant type toilet bowl cleaner used in a water tank having the following composition was prepared, and its performance was sensory evaluated. As a result, excellent cleaning power was exhibited. Ingredients wt% -Polyethylene glycol 11000 47.0-Compound mixture of Example 3 30.0-Dye 3.0-Menthol 10.0-Geraniol 10.0

Example 112 A furniture polish having the following composition was prepared, and its performance was sensory-evaluated. As a result, it showed excellent stain-removing ability on the wall surface of the furniture and gave gloss after use. Ingredients% by weight • Polyoxypropylene (2) myristic acid diglycolamide 3.0 • Stearic acid 1.2 • Mineral seal oil 20.0 • Heavy mineral oil 20.0 • Purified water balance

Example 113 A solid car wash having the following composition was prepared, and its performance was sensory-evaluated. As a result, it showed excellent detergency. Ingredients wt% -coconut oil fatty acid monoethanolamide 53.0-polyethylene glycol 6000 20.0-compound mixture of Example 6.0-stearyltrimethylammonium chloride 8.0-liquid paraffin 5.0-silicone oil 2.0・ Amine-modified silicone oil 2.0

[0222]

EFFECTS OF THE INVENTION The polyoxypropylene fatty acid alkanolamide compound mixture of the present invention has the features of low melting point, good handling property, stability in a wide pH range, and less irritation to the eye mucous membrane. Further, the compound mixture of the present invention, when used in combination with other surfactants, has excellent thickening / foaming / foaming stability, so that it is easy to handle, has excellent low-temperature stability, and has a wide range. It can also be used at a pH of 2 and can be used as a safe thickener / foaming agent / foaming stabilizer with less irritation, and has excellent emulsifying power / dispersing power / solubilizing power. -Can be used as a solubilizer.

Further, in the method for producing a polyoxypropylene fatty acid alkanolamide compound mixture of the present invention, a highly pure polyoxypropylene fatty acid alkanolamide compound mixture can be produced without a purification step between steps or after the final step. I found a thing. According to the method of the present invention, a polyoxypropylene fatty acid alkanolamide compound mixture can be easily produced industrially.

Further, by using the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention, it is possible to obtain a cosmetic composition which is excellent in emulsion stability and at the same time is excellent in usability. Furthermore, the detergent composition containing the polyoxypropylene fatty acid alkanolamide compound mixture of the present invention has less irritation to the skin, hair, and eye mucous membranes, and further has foaming power / detergency / viscosity / foaming stability. It is possible to obtain a detergent composition which can be improved and is easy to prepare due to its low melting point and which is also excellent in low temperature stability.

[Brief description of drawings]

FIG. 1 is a graph showing the distribution of the number of PO groups (n) and the number of EO groups (m) in a compound mixture of the present invention and a comparative compound mixture.

FIG. 2 is a graph showing the relationship between the number of oxyethylene groups (p) and viscosity in the compound mixture of the present invention.

FIG. 3 shows the number of PO groups (n) in the compound mixture of the present invention.
Is a graph showing the relationship between viscosity and viscosity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location A61K 7/40 A61K 7/40 B01F 17/22 B01F 17/22 17/42 17/42 B01J 31 / 02 101 B01J 31/02 101X C07C 231/02 C07C 231/02 231/12 231/12 233/20 9547-4H 233/20 C09K 3/00 103 C09K 3/00 103H 111 111B C11D 1/52 C11D 1/52 // C07B 61/00 300 C07B 61/00 300

Claims (11)

[Claims] 1. The following general formula (1): (In the formula (1), R is a linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group having 7 to 21 carbon atoms, EO represents an oxyethylene group, and PO represents an oxy group having 3 carbon atoms. Represents an alkylene group, p is an integer of 1 or 2, m is an integer of 0 or 1 or more, and n is an integer of 0 or 1 or more), which is a mixture of two or more compounds. A mixture of polyoxypropylene fatty acid alkanolamide compounds, characterized in that the average value of m is 0 or a positive number of 1 or less and the average value of n is a positive number of 0.3 to 10. 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 ~ 3. ) And a fatty acid alkyl ester represented by the following general formula (3): (In the formula (3), p is the same as above.) And reacted with an alkanolamine in the presence of a base catalyst to give the following general formula (4): (In the formula (4), R and p are the same as described above.) A reaction mixture containing a fatty acid alkanolamide represented by the formula (4) was prepared, and the reaction mixture was added to the reaction mixture without purification. The compound represented by the general formula (4) is subjected to an addition reaction with 0 to 1 times the molar amount of ethylene oxide to give a compound represented by the following general formula (5): (In the formula (5), R, p and m are respectively the same as above.) A reaction mixture containing a polyoxyethylene fatty acid alkanolamide was prepared, and the reaction mixture was purified without purification. The compound of the general formula (5) contained in the reaction mixture has a molar amount of 0.3 to 1
The method for producing a polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1, wherein 0-fold mole of propylene oxide is subjected to an addition reaction. 3. A thickener containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 4. A foam booster containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 5. A foam stabilizer containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 6. An emulsifier containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 7. A dispersant containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 8. A solubilizing agent containing the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 9. A cosmetic comprising the mixture of polyoxypropylene fatty acid alkanolamide compounds according to claim 1. 10. A detergent composition comprising the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1. 11. A mixture of the polyoxypropylene fatty acid alkanolamide compound mixture according to claim 1 and at least one selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. A cleaning composition comprising: