JPH0987289A - Surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surfactant mixture giving a cleansing agent having high aging stability and excellent frothing power and cleaning power and giving abundant foam and creamy excellent feeling. SOLUTION: This surfactant is a mixture of two or more kinds of compounds of the formula I (R is a 7-21C hydrocarbon group; EO is oxyethylene; PO is oxypropylene; A is RCONH(CH2 CH2 O)x (EO)y (PO)<-> 2 or -OMp ((x) is 1 or 2; (y) and (z) are each ∞0; M is H, an alkali metal, etc.; the average of (y) is 0-5; the average of (z) is 0.3-20). The compound can be produced by reacting a fatty acid alkyl ester of the formula II (R<1> is a 1-3C alkyl) with an alkanolamine of the formula, H2 N-(CH2 CH2 O)x -H to obtain a fatty acid alkanolamide of the formula III, adding ethylene oxide and then propylene oxide to the product to obtain a mixture of two or more kinds of polyoxypropylene fatty acid alkanol amide compounds of the formula IV, reacting the compounds with a phosphorylating agent and finally neutralizing the reaction product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surfactant, a method for producing the same, and a detergent composition using the surfactant. More specifically, it has excellent foaming power and detergency, has a large amount of foam, is creamy, has no feeling of slimyness or squeaks during rinsing, and has excellent usability, and is stable over time. Is good,
Moreover, there is little irritation to the skin and hair, and polyoxypropylene fatty acid alkanolamide phosphate ester (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester or salt thereof) useful as a surfactant or a mixture of salts thereof, The present invention relates to a method for industrially producing it efficiently and with excellent safety, and a detergent composition containing the same.

[0002]

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

In recent years, as a detergent compound for the purpose of reducing skin irritation, a product obtained by adding ethylene oxide to fatty acid monoethanolamide and converting the ethylene oxide addition reaction product into a phosphoric acid ester or a salt thereof has been proposed. Are known. The composition produced by the above method has the following general formula (7):

Embedded image (In the formula (7), R, EO, M and p are the same as above,
A 'is _{RCONHCH 2 CH 2 O (EO)} n group or a -
Represents an OM _p group, and n represents an integer of 1 or more. ).

The polyoxyethylene fatty acid monoethanolamide phosphoric acid ester of the above general formula (7) or its salt is easily hydrolyzed and has a low chemical stability. As a result, the quality stability of the product containing the polyoxyethylene fatty acid monoethanolamide phosphoric acid ester or a salt thereof is deteriorated.

It is considered that one of the causes of the low stability of the product of the compound of formula (7) is due to the fatty acid monoethanolamide phosphate ester or its salt contained in the product. Therefore, in order to reduce the content of the fatty acid monoethanolamide phosphate ester or salt thereof in the reaction product containing polyoxyethylene fatty acid monoethanolamide phosphate ester or salt thereof as a main component,
A method of increasing the number of moles of ethylene oxide used for the addition reaction to the fatty acid monoethanolamide is used. Specifically, if the number of moles n of ethylene oxide to be subjected to the addition reaction is 4 or more with respect to 1 mol of fatty acid monoethanolamide, the content of fatty acid monoethanolamide in the obtained polyoxyethylene fatty acid monoethanolamide Can be almost 0%, and the stability over time is actually improved. However, when the number of moles of ethylene oxide used is increased in this way, the foaming power and detergency of the reaction product obtained will be reduced, and the slimy feeling will increase and the usability will deteriorate. Was there.

The mixture of polyoxypropylene fatty acid alkanolamide phosphates or salts thereof (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphates or salts thereof) of the present invention is a novel article and is therefore to be washed. There is no example used in a drug composition.

[0007]

DISCLOSURE OF THE INVENTION The present invention is excellent in foaming power / detergency, has a large amount of foam and is creamy, and has excellent usability without slimy feeling or tingling sensation at the time of rinsing. A mixture of specific polyoxypropylene fatty acid alkanolamide phosphates or salts thereof (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphates or salts thereof) which is less irritating to hair and is useful as a detergent, its industry The present invention intends to provide an easily and efficiently producing method, and a detergent composition containing a mixture of the specific polyoxypropylene fatty acid alkanolamide phosphate ester or a salt thereof.

[0008]

[Means for Solving the Problems] The present inventors
A detergent with high detergency, abundant foam volume and creamy, an excellent feeling of use with no slimy feeling or tingling sensation during rinsing, low irritation to skin and hair, and high product stability. As a result of intensive studies to obtain a composition, fatty acid monoethanolamide, fatty acid diglycolamide, and polyoxyethylene fatty acid monoethanolamide mixture, and propylene oxide were added to the polyoxyethylene fatty acid diglycolamide mixture, and further, It has been found that a reaction product mixture obtained by salting a phosphoric acid ester is suitable for the above-mentioned applications, and further, a method for producing it efficiently and stably, and a detergent composition containing the mixture obtained by this method. . In particular, a mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester salt compound of the present invention, an N-acyl amino acid (salt), an amidocarboxylic acid type surfactant,
Alternatively, a detergent composition containing an amphoteric surfactant exhibits excellent performance.

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

Embedded image (In the formula (1), R represents a linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group having 7 to 21 carbon atoms, and EO
Represents an oxyethylene group, PO represents an oxypropylene group, A represents _{RCONH (CH 2 CH 2) x} - (EO)
_{represents a y-} (PO) _z -group or a -OM _p group, x represents an integer of 1 or 2, y and z each independently represent 0 or an integer of 1 or more, and M represents a hydrogen atom or an alkali. It represents a metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid, and p represents the reciprocal of the valence of the atom or group represented by M. And a mean value y'of y is 0 or 5
It is the following positive number, and the average value z'of z is 0.3 to 20.
It is characterized by being a positive number.

In the present invention, the compound of the above formula (1) includes a mixture of polyoxypropylene fatty acid alkanolamide phosphate ester salt and a mixture of polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt. Hereinafter, these are collectively referred to as a mixture of polyoxypropylene fatty acid alkanolamide phosphate salt compounds.

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

Embedded image (In formula (2), R is the same as the above, R1 represents a C1-C3 alkyl group.), And the general formula (3):

Embedded image (In the formula (3), x is the same as above) and reacted with an alkanolamine in the presence of a base catalyst to give a compound represented by the general formula (4):

[Chemical 12] (In the formula (4), R and x are the same as above.) A fatty acid alkanolamide represented by The following general formula (5):

Embedded image (In the formula (5), R, x, EO and y are the same as above.)
A reaction product mixture containing a polyoxyethylene fatty acid alkanolamide represented by the formula By adding 0.3 to 20 times the molar amount of propylene oxide, the following general formula (6):

Embedded image (In the formula (6), R, x, EO, y, PO and z are the same as above.) A mixture of two or more polyoxypropylene fatty acid alkanolamide compounds is prepared, and this mixture is converted into a phosphoric ester. React with agents, further alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal oxides, ammonia, alkanolamines,
General formula (1), characterized by neutralizing with a neutralizing agent selected from basic amino acids:

[Chemical 15] (In the formula (1), R, x, y, z, EO, PO, M, p and A are the same as the above), thereby obtaining a mixture of polyoxypropylene fatty acid alkanolamide phosphate ester salt compounds. It is what

Further, the detergent composition of the present invention contains a mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester compound (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt). It is characterized by.

The detergent composition according to the present invention also comprises a mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester compound (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt) and an anion. It is characterized by containing at least one surfactant selected from a surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant.

Furthermore, the detergent composition according to the present invention comprises a mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester salt compounds (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salts). Component (A) and N-
At least one selected from acylamino acids and salts thereof
A component (Ba) consisting of a seed, a component (Bb) consisting of at least one amidocarboxylic acid type surfactant, or a component (Bc) consisting of at least one amphoteric surfactant. It is a thing.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyoxypropylene fatty acid monoethanolamide phosphoric acid ester salt contained in the compound mixture of the present invention is specifically illustrated as follows.
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) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1.5)
Sodium lauric acid monoethanolamide phosphate, polyoxypropylene (2) lauric acid monoethanolamide phosphate, polyoxypropylene (2) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (2) lauric acid monoethanolamide phosphorus Potassium acid, polyoxypropylene (2) lauric acid monoethanolamide magnesium phosphate, polyoxypropylene (2) lauric acid monoethanolamide ammonium phosphate, polyoxypropylene (2) lauric acid monoethanolamide phosphate triethanolamine, Polyoxypropylene (2) lauric acid monoethanolamide phosphoric acid lysine salt, polyoxypropylene (5) lauric acid monoethanolamide sodium phosphate, polyoxypropylene (10 Sodium lauric acid monoethanolamide phosphate, polyoxypropylene (20) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1.5) sodium capric acid monoethanolamide phosphate, polyoxypropylene (2) monodecanoic acid Sodium ethanolamide phosphate, polyoxypropylene (3) sodium myristate monoethanolamide phosphate, polyoxypropylene (5) sodium palmitate monoethanolamide phosphate, polyoxypropylene (10) sodium stearate monoethanolamide phosphate , Polyoxypropylene (20)
Isostearic acid monoethanolamide sodium phosphate, polyoxypropylene (3) oleic acid monoethanolamide sodium phosphate, polyoxypropylene (2) linoleic acid monoethanolamide sodium phosphate, polyoxypropylene (2) linolenic acid monoethanolamide Sodium phosphate, polyoxypropylene (5) -2-heptyl undecanoic acid monoethanolamide sodium phosphate, polyoxypropylene (1) coconut oil fatty acid monoethanolamide sodium phosphate, polyoxypropylene (0.3) tallow fatty acid mono Sodium ethanolamide phosphate, and sodium polyoxypropylene (2) palm kernel oil fatty acid monoethanolamide phosphate.

Specific examples of the polyoxypropylene fatty acid diglycolic acid amide phosphoric acid ester salt contained in the compound mixture of the present invention are as follows. 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.

[2] Polyoxypropylene (0.3) sodium diglycolamide laurate, polyoxypropylene (1) sodium diglycolamide laurate, polyoxypropylene (1.5) diglycol laurate Sodium amidophosphate, polyoxypropylene (2) lauric acid diglycol amide phosphate, polyoxypropylene (2) lauric acid diglycol amide phosphate, polyoxypropylene (2) lauric acid diglycol amide phosphate,
Polyoxypropylene (2) lauric acid diglycol amide magnesium phosphate, polyoxypropylene (2)
Lauric acid diglycol amide ammonium phosphate, polyoxypropylene (2) lauric acid diglycol amide phosphate triethanolamine, polyoxypropylene (2) lauric acid diglycol amide phosphate lysine salt,
Polyoxypropylene (5) sodium diglycolamide laurate phosphate, polyoxypropylene (10)
Sodium lauric acid diglycolamide phosphate, polyoxypropylene (20) Sodium lauric acid diglycolamide phosphate, polyoxypropylene (1.5)
Capric acid diglycolamide sodium phosphate, polyoxypropylene (2) decanoic acid diglycolamide sodium phosphate, polyoxypropylene (3) myristic acid diglycolamide sodium phosphate, polyoxypropylene (5) palmitic acid diglycolamide Sodium phosphate, polyoxypropylene (10) sodium stearate diglycolamide phosphate, polyoxypropylene (20) sodium isostearate diglycolamide phosphate, polyoxypropylene (3) sodium oleate diglycolamide phosphate, poly Oxypropylene (2) sodium diglycolamide linoleate phosphate, polyoxypropylene (2) sodium diglycolamide linolenate phosphate, polyoxypropylene (5) -2 Heptyl undecanoic acid diglycol amides sodium phosphate, polyoxypropylene (1)
Coconut oil fatty acid diglycol amide sodium phosphate, polyoxypropylene (0.3) tallow fatty acid diglycol amide sodium phosphate, and polyoxypropylene (2) palm kernel oil fatty acid diglycol amide sodium phosphate and the like.

Specific examples of the polyoxypropylene polyoxyethylene fatty acid monoethanolamide phosphate ester salt contained in the compound mixture of the present invention are as follows. In the compound names below, the numbers in parentheses are
It is the number of moles of propylene oxide and ethylene oxide that have been subjected to the addition reaction with respect to 1 mole of the fatty acid alkanolamide.

[3] Polyoxypropylene (0.3) polyoxyethylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1) polyoxyethylene (0.2) lauric acid monoethanolamide phosphoric acid Sodium, polyoxypropylene (1) Polyoxyethylene (0.5) Lauric acid monoethanolamide Sodium phosphate, polyoxypropylene (1)
Polyoxyethylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1) polyoxyethylene (5) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1.5)
Polyoxyethylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) lauric acid mono Ethanolamide sodium phosphate, polyoxypropylene (2) polyoxyethylene (1) potassium lauric acid monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) lauric acid monoethanolamide magnesium phosphate, polyoxy Propylene (2) Polyoxyethylene (1) Lauric acid monoethanolamide ammonium phosphate, Polyoxypropylene (2) Polyoxyethylene (1) Laurate monoethanolamide phosphoric acid triethanolamine, Poly Xyloxypropylene (2) Polyoxyethylene (1) Lauric acid monoethanolamide phosphate lysine salt, Polyoxypropylene (5) Polyoxyethylene (1) Lauric acid monoethanolamide sodium phosphate, Polyoxypropylene (10) Polyoxy Ethylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (20) polyoxyethylene (1) sodium lauric acid monoethanolamide phosphate, polyoxypropylene (1.5) polyoxyethylene (1) capric acid Sodium monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) sodium decanoate monoethanolamide phosphate, polyoxypropylene (3) polyoxyethylene (1) monoethanol myristate Sodium phosphonate, polyoxypropylene (5) polyoxyethylene (1) sodium palmitate monoethanolamide phosphate, polyoxypropylene (10) polyoxyethylene (1) sodium stearate monoethanolamide phosphate, polyoxypropylene ( 20) Polyoxyethylene (1) sodium isostearate monoethanolamide phosphate, polyoxypropylene (3) polyoxyethylene (1) sodium oleate monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) Sodium linoleic acid monoethanolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) Sodium linolenic acid monoethanolamide phosphate, polyoxypropylene (5) polyoxyethylene (1) -2-heptyl undecanoic acid monoethanolamide sodium phosphate, polyoxypropylene (1) polyoxyethylene (1) coconut oil fatty acid sodium monoethanolamide phosphate, polyoxypropylene (0.
3) Polyoxyethylene (1) tallow fatty acid monoethanolamide phosphate sodium salt, polyoxypropylene (2) polyoxyethylene (1) palm kernel oil fatty acid monoethanolamide phosphate sodium salt, and the like.

Specific examples of the polyoxypropylene polyoxyethylene fatty acid diglycolic acid amide phosphate ester salt contained in the compound mixture of the present invention are as follows. In the compound names below, the numbers in parentheses are
It is 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.

[4] Polyoxypropylene (0.3) polyoxyethylene (1) sodium lauric acid diglycol amide phosphate, polyoxypropylene (1) polyoxyethylene (0.2) lauric acid diglycol amide phosphoric acid Sodium, polyoxypropylene (1) polyoxyethylene (0.5) sodium lauric acid diglycolamide phosphate, polyoxypropylene (1) polyoxyethylene (1) sodium diglycolamide lauric acid phosphate, polyoxypropylene ( 1) Polyoxyethylene (5) sodium diglycolamide laurate phosphate, polyoxypropylene (1.5) polyoxyethylene (1) sodium diglycolamide laurate phosphate, polyoxypropylene (2) polyoxyethylene ( 1) Lauri Acid diglycol amide phosphoric acid, polyoxypropylene (2) polyoxyethylene (1) sodium lauric acid diglycol amide phosphate, polyoxypropylene (2) polyoxyethylene (1) potassium lauric acid diglycol amide phosphate, poly Oxypropylene (2) Polyoxyethylene (1) Lauric acid diglycolamide magnesium phosphate, Polyoxypropylene (2) Polyoxyethylene (1) Lauric acid diglycolamide ammonium phosphate, Polyoxypropylene (2) Polyoxyethylene (1) lauric acid diglycolamide triethanolamine, polyoxypropylene (2) polyoxyethylene (1) lauric acid diglycolamide phosphoric acid lysine salt, polyoxypropylene (5) polyoxyethylene (1) Uric acid diglycol amide sodium phosphate, polyoxypropylene (10) polyoxyethylene (1) lauric acid diglycol amide sodium phosphate, polyoxypropylene (20) polyoxyethylene (1) lauric acid diglycol amide sodium phosphate , Polyoxypropylene (1.5) polyoxyethylene (1) sodium caprate diglycolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) sodium diglycolamide decanoate, polyoxypropylene (3 )
Polyoxyethylene (1) sodium mycolate diglycolamide phosphate, polyoxypropylene (5) polyoxyethylene (1) sodium palmitate diglycolamide phosphate, polyoxypropylene (10) polyoxyethylene (1) stearic acid Sodium Diglycol Amido Phosphate, Polyoxypropylene (20) Polyoxyethylene (1) Sodium Diglycol Amido Phosphate, Polyoxypropylene (3)
Polyoxyethylene (1) oleic acid diglycolamide sodium phosphate, polyoxypropylene (2) polyoxyethylene (1) linoleic acid sodium diglycolamide phosphate, polyoxypropylene (2) polyoxyethylene (1) linolenic acid Sodium diglycolamide phosphate, polyoxypropylene (5) Polyoxyethylene (1) -2-heptylundecanoic acid Sodium diglycolamide phosphate, polyoxypropylene (1)
Polyoxyethylene (1) coconut oil fatty acid diglycolamide sodium phosphate, polyoxypropylene (0.
3) Polyoxyethylene (1) beef tallow fatty acid diglycol amide phosphate, and polyoxypropylene (2) polyoxyethylene (1) palm kernel oil fatty acid diglycol amide phosphate.

The alkanolamide constituting the polyoxypropylene fatty acid alkanolamide or polyoxypropylene polyoxyethylene fatty acid alkanolamide of the present invention means monoethanolamide or diglycolamide. That is, x in equation (1)
In the case of triglycolamide having an oxyethylene base chain of = 1 or 2 longer than that (that is, x ≧ 3), the product obtained from the product has a strong squeaky feeling and lowers the foaming power and the detergency. It has the drawback.

The ethylene oxide (E) in the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide phosphorus ester salt compound mixture according to the present invention is
The average value y'of the added mole number y of O) is 0-5. If the average added mole number y'exceeds 5, the foaming power and detergency of the resulting product will be poor, and a tingling sensation will appear during use.
Moreover, the creamy feeling of the foam becomes poor. In order to obtain a product having excellent foaming power and detergency, it is preferable that the average number of moles of ethylene oxide added y'is 0.5 or less. Products that do not add ethylene oxide are excellent. On the other hand, regarding the stability, the product with addition of ethylene oxide and the product with addition of ethylene oxide are superior in stability.

In the polyoxypropylene fatty acid alkanolamide phosphate salt compound of the present invention (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate salt), the propylene oxide addition mole number z is 0 or an integer of 1 or more. And the average value (average number of added moles) z'is 0.3 to 20.
When the average added mole number z'is less than 0.3, the resulting product has low chemical stability and low water solubility, and crystals may sometimes be precipitated during storage at low temperature. Further, when the average value z'exceeds 20, the foaming power / cleaning power of the obtained product becomes insufficient, the refreshing feeling after washing is lost, and the feeling of slipperiness appears. Within the range of 0.3 to 20 of the average added mole number z'of propylene oxide, in order to obtain a product having excellent foaming power, detergency and a refreshing feeling, it is preferable that the average added mole number z'is smaller. Specifically, it is preferably 0.3 to 3. On the other hand, for the stability of the product, the larger the average number of moles added, the better,
Specifically, it is preferable that the average added mole number z'is 3 to 20.

As the counter cation M in the compound mixture of the present invention, an alkali metal atom such as sodium and potassium, an alkaline earth metal atom such as magnesium and calcium, an ammonium group, and a cationic residue of an alkanolamine such as triethanolamine. , And cationic residues of basic amino acids such as lysine and arginine are used.

Preparation of a mixture of polyoxypropylene fatty acid alkanolamide phosphate ester phosphate compound represented by the general formula (1) (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester mixture) The method will be described in detail.

The polyoxypropylene fatty acid alkanolamide phosphoric acid ester salt mixture of the present invention is obtained by adding propylene oxide to a fatty acid alkanolamide, converting the polyoxypropylene fatty acid alkanolamide compound mixture into a phosphoric ester, It is obtained by neutralizing accordingly. The polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt compound mixture of the present invention, after adding ethylene oxide to the fatty acid alkanolamide by a conventional method, the obtained polyoxyethylene fatty acid alkanolamide mixture,
Further, propylene oxide is added to prepare a polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture, which is then converted into a phosphoric acid ester, and neutralized if necessary, to obtain the mixture.

The conditions for the reaction of adding ethylene oxide to the fatty acid alkanolamide are not particularly limited,
For example, by reacting a fatty acid alkanolamide with ethylene oxide in the presence of a Lewis acid catalyst such as boron trifluoride or titanium chloride, or a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or sodium ethoxide. To be achieved.
This reaction requires the use of any of the above catalysts, and with highly purified fatty acid alkanolamides the addition reaction does not proceed or is very slow.

The reaction conditions of the method of adding propylene oxide to fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide are not particularly limited, but examples thereof include Lewis acid catalysts such as boron trifluoride and titanium chloride, or sodium hydroxide, In the presence of a base catalyst such as potassium hydroxide, sodium methoxide, or sodium ethoxide, a fatty acid alkanolamide,
Or to polyoxyethylene fatty acid alkanolamide,
This is achieved by reacting propylene oxide. This reaction requires the use of any of the above catalysts, with highly purified fatty acid alkanolamides the addition reaction 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 polyoxyethylene fatty acid alkanolamide used in this reaction, but is preferably 80 to 180 ° C. When the reaction temperature is lower than 80 ° C, the reaction is slow,
If it exceeds 180 ° C., coloring of the obtained product becomes remarkable, which is not preferable. In order to prevent or suppress coloring, it is effective to replace the reaction system with an inert gas in advance. The method for charging propylene oxide may be any of charging before heating, heating at reaction temperature and then pressurizing in liquid form, and heating at reaction temperature and then blowing in gas. However, since heat is generated during the addition reaction, temperature control may be difficult with this method. Therefore, in the case of mass production, it is preferable to use a method whose temperature can be easily controlled.

After the completion of the propylene oxide addition reaction, the obtained polyoxypropylene fatty acid alkanolamide or polyoxypropylene polyoxyethylene fatty acid alkanolamide can be used as it is for the next phosphoric acid ester or its chlorination reaction.

At the time of the propylene oxide addition reaction, a solvent may be used as long as it does not inhibit this reaction. Specific examples of usable solvents include hydrocarbon solvents such as hexane, benzene, toluene and xylene, halogen solvents such as chloroform and dichloroethane, ether solvents such as tetrahydrofuran, diisopropyl ether and dibutyl ether. You can

A mixture of polyoxypropylene fatty acid alkanolamide compounds (including a mixture of polyoxypropylene polyoxyethylene fatty acid alkanolamides) is converted into a phosphoric acid ester, and further a salt thereof is prepared by using a phosphorylating agent and polyoxypropylene. It is obtained by reacting with a fatty acid alkanolamide compound mixture (including polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture) to form a phosphoric acid ester. To obtain the phosphate ester salt, the phosphate ester may be neutralized with a neutralizing agent.

Specific examples of the phosphorylating agent include phosphorus oxychloride, phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid and the like. The reaction method and conditions for the phosphoric acid esterification are not limited, and known methods may be used according to the cognitive conditions. When a phosphoric acid monoester is produced, phosphorus oxychloride is used as a phosphorylating agent, This is used in an amount of 1 to 3 times the molar amount of the polyoxypropylene fatty acid alkanolamide compound mixture (including the polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture), and the reaction temperature is -20 to 50.
C. is preferred. When producing a phosphoric acid diester, diphosphorus pentoxide is used as a phosphorylating agent,
This is 0.2 with respect to the polyoxypropylene fatty acid alkanolamide compound mixture (polyoxypropylene polyoxyethylene fatty acid alkanolamide mixture).
It is preferably used in an amount of 5 to 2 times the molar amount and the reaction temperature is preferably 0 to 80 ° C. In the reaction using diphosphorus pentoxide, a mixture of monoester and diester is often produced.

The phosphoric acid esterification reaction proceeds without solvent, but when the melting point of polyoxypropylene fatty acid alkanolamide or polyoxypropylene polyoxyethylene fatty acid alkanolamide is higher than the reaction temperature, hexane, benzene, toluene, etc. May be carried out in a hydrocarbon-based solvent, an ether-based solvent such as diethyl ether, diisopropyl ether or tetrahydrofuran, or a halogen-based solvent such as chloroform or methylene chloride.

After the phosphoric acid esterification reaction, if phosphoric acid such as orthophosphoric acid or pyrophosphoric acid generated from an excessively used phosphorylating agent remains and causes inconvenience, this is once extracted from the reaction system with a solvent. After that, these phosphoric acids can be easily removed by adding water to the reaction product for liquid separation and washing.

As the neutralizing agent, alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, etc.),
Alkaline earth metal hydroxides (eg magnesium hydroxide), alkaline earth metal oxides (eg magnesium oxide), ammonia, alkanolamines (eg triethanolamine) or basic amino acids (eg Lysine) etc. are used.

In the method of the present invention, to obtain the fatty acid alkanolamide of the formula (3), (1) a method of dehydrating and condensing a fatty acid and an alkanolamine, (2) a method of reacting a fatty acid halide with an alkanolamine, ( 3)
There is a method of reacting a lower alcohol ester of a fatty acid with an alkanolamine in the presence of a base catalyst while removing a lower alcohol produced as a by-product.
The method (1) is not preferable because it is difficult to complete the reaction, some unreacted raw material remains, and adversely affects the reaction in the subsequent steps. Further, since the reaction temperature must be higher than that of other methods, there is a drawback that coloring is remarkable as compared with other methods. In the method (2), hydrogen chloride is generated, so that a reagent or device for trapping it is required. Further, the problem of equipment corrosion and the fatty acid halide are relatively expensive, and it is hard to say that it is an excellent method when it is attempted industrially.

To prepare the polyoxypropylene fatty acid alkanolamide phosphate ester salt compound mixture of the present invention (including the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt mixture), the purity of the obtained fatty acid alkanolamide is used. It is preferable to use the method (3), which has a high value. When the fatty acid alkanolamide is produced by the above method (3), the base catalyst used in this reaction is also effective as a catalyst for the addition reaction of ethylene oxide and propylene oxide. Therefore, at the stage of adding ethylene oxide or propylene oxide, It is very effective as it eliminates the need to add a catalyst essential for this addition reaction.

The most efficient method for producing the polyoxypropylene fatty acid alkanolamide phosphate ester salt compound mixture of the present invention (including polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate salt mixture) is as follows. is there. That is, a raw material mixture consisting of a fatty acid alkyl ester, monoethanolamine or diglycolamine, and a base catalyst is heated to carry out a condensation reaction while distilling off a lower alcohol generated as a by-product to prepare a fatty acid alkanolamide. Next, propylene oxide is added to the reaction product, or ethylene oxide is added, and then a propylene oxide addition reaction is further performed. Then, the obtained compound mixture is reacted with a phosphorylating agent to form a phosphoric acid ester, which is further neutralized with a neutralizing agent to form a phosphoric acid ester salt. An example of one embodiment of this reaction is as follows.

[0042]

Embedded image

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

The alkanolamine represented by the general formula (3) used in the method of the present invention is either monoethanolamine or diglycolamine. The alkanolamine represented by the general formula (3) and the general formula (2)
Molar ratio with fatty acid alkyl ester represented by [(3)
/ (2)] is preferably 0.8 to 1.2,
1.0 to 1.1 is more preferable.

Examples of the base catalyst used in the method of the present invention include metal alkoxides such as sodium methoxide and sodium ethoxide, 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 reaction temperature of the amidation reaction between the compound of formula (2) and the compound of formula (3) is preferably 50 to 150 ° C., and the reaction time of 12 hours or less is sufficient.
Since the lower alcohol, which is a by-product of this amidation reaction, is distilled off, the pressure in the reaction system is 0.1 to 760 mmHg.
Is more preferable, and the range of 10-50 mmHg is more preferable. Generally, it is desirable to set the pressure while considering the relationship between the temperature and the pressure so that the reaction temperature does not exceed the boiling point of the fatty acid alkyl ester (formula (2)) or the alkanolamine (formula (3)).

Since this amidation reaction proceeds almost quantitatively, the obtained fatty acid alkanolamide containing a base catalyst can be directly used for the next ethylene oxide or propylene oxide addition reaction. The addition reaction of ethylene oxide or propylene oxide may be carried out by the method described above, but some fatty acid alkanolamides and polyoxyethylene (0-5) fatty acid alkanolamides solidify when they are cooled. Is maintained at the propylene oxide addition temperature, and propylene oxide is charged into this in a liquid or gas state, that is, the above method (2) or (3) is effective. The phosphoric acid esterification and the reaction to convert it into a salt may be carried out by the method described above.

The mixture of polyoxypropylene fatty acid alkanolamide phosphate ester compounds represented by the general formula (1) of the present invention (including the mixture of polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salts) is When used as one component of a detergent composition, which is useful as an activator, the detergent preferably contains 0.05 to 40% by weight, more preferably 0.1 to 30% by weight. Included in the rate.

The polyoxypropylene fatty acid alkanolamide phosphoric acid ester salt compound mixture (including the mixture of polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphoric acid ester salt) represented by the general formula (1) of the present invention is used alone. However, it has sufficient surfactant activity, but by combining with other surfactants,
Additional effects such as adjusting viscosity and improving foaming stability are observed. Further, the compound mixture of the present invention also has an action of alleviating the irritancy of other surfactants. Other surfactants used in combination with the compound mixture of the present invention are selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.

Examples of the anionic surfactant used in the detergent composition of the present invention include fatty acid soaps such as sodium laurate and triethanolamine laurate, alkylbenzene sulfonates, α-olefin sulfonates, sodium lauryl sulfate. Lauryl sulfate such as triethanolamine lauryl sulfate, ether sulfate such as polyoxyethylene (3) sodium lauryl ether sulfate, amide ether sulfate such as polyoxyethylene (3) coconut oil fatty acid sodium amide sulfate, monododecyl phosphate Triethanolamine, phosphoric acid esters such as sodium polyoxyethylene dodecyl ether phosphate, cocoyl methyl taurine sodium, acyl methyl taurine salts such as sodium lauroyl methyl taurine, lauroyl ise Acyl isethionates, sodium lauryl sulfosuccinate, disodium such as sodium propionic acid,
POE (1-4) disodium lauryl sulphosuccinate, polyoxyethylene (5) lauric acid monoethanolamide sulfosuccinic acid type surfactants such as disodium sulfosuccinate, alkyl ether carboxylates, cocoyl sarcosine sodium, sodium lauroyl sarcosine, N-acyl sarcosine salts such as myristoyl sarcosine sodium, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine, cocoyl-N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine sodium, myristoyl-N-methyl-β. Alanine sodium, palmitoyl-N-methyl-β-alanine sodium, stearoyl-N-methyl-β-alanine sodium, lauroyl-
N-methyl-β-alanine potassium, lauroyl-N-
N-, such as methyl-β-alanine triethanolamine
N-acyl aspartates such as acyl-β-alanine salt, sodium N-lauroyl aspartate, triethanolamine N-lauroyl aspartate, sodium N-myristoyl aspartate, sodium N-lauroyl glutamate, sodium N-lauroyl glutamate. Examples thereof include amidocarboxylic acid type surfactants such as amines, N-acylglutamates such as sodium N-cocoylglutamate and triethanolamine N-cocoylglutamate.

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

Examples of the amphoteric surfactant used in the detergent composition of the present invention include alkyl betaine type amphoteric surfactants such as lauryl betaine, amido betaine type amphoteric surfactants such as lauroyl amidopropyl betaine, and 2-alkyl- Imidazoline-type amphoteric surfactants such as N-carboxymethylimidazolinium betaine and 2-alkyl-N-carboxyethylimidazolinium betaine, N-2-hydroxyethyl-N-2-lauric acid amidoethylglycine, N- 2-hydroxyethyl-N-
2-coconut oil fatty acid amide ethylglycine, N-2-hydroxyethyl-N-2-lauric acid amide ethyl-β-
Alanine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethyl-β-alanine, N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) lauric acid amide] ethyl} glycine, N-carboxymethyl-N- {2- [N '-(2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine, N- {2- [N
Amidoamine type amphoteric surfactants such as-(2-hydroxyethyl) lauric acid amide] ethyl} glycine and N- {2- [N- (2-hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, alkylsulfobetaine type Examples thereof include amphoteric surfactants and amide sulfobetaine-type amphoteric surfactants such as coconut oil fatty acid amide dimethylhydroxypropyl sulfobetaine.

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

Among the detergent compositions of the present invention, the general formula (1)
And a component (A) consisting of one or more polyoxypropylene fatty acid alkanolamide phosphate salt or polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate salt represented by Type surfactant (B) at least one component (B
The detergent composition containing a) or a component (Bb) containing at least one amidocarboxylic acid type surfactant or a component (Bc) containing at least one amphoteric surfactant has a foaming power.・ Especially excellent detergency, creamy foam, and extremely low irritation to skin and hair,
It is suitable as a detergent composition for use on the body such as shampoo and body shampoo.

The N-acyl amino acid type surfactant and amidocarboxylic acid type surfactant used as the components (Ba) and (Bb) of the detergent composition of the present invention are, for example, those represented by the following general formula (8).

Embedded image (However, in the formula (8), R ² represents a linear or branched, saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, and R ³ represents an N-acyl amino acid type surfactant. (B
a) represents a member selected from the groups represented by the formulas (a) to (d), and represents an amidecarboxylic acid type surfactant (B
In b), it represents one member selected from the groups represented by formulas (e) to (h), and M ² represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an akanolamine. It represents a cationic residue or a cationic residue of a basic amino acid, and m represents an integer equal to the valence of M ² . ) Is mentioned.

In the acylamino acid type surfactant of the general formula (8), when R ³ represents the group of the formula (a), the formula (8)
Examples of the compound include cocoyl sarcosine sodium, lauroyl sarcosine sodium, myristoyl sarcosine sodium, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine and the like.

In the acylamino acid type surfactant of the general formula (8), when R ³ represents the group of the formula (b), the formula (8)
As the compound of, cocoyl-N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine sodium, myristoyl-N-methyl-β-alanine sodium, palmitoyl-N-methyl-β-alanine sodium, stearoyl Examples include -N-methyl-β-alanine sodium, lauroyl-N-methyl-β-alanine potassium, lauroyl-N-methyl-β-alanine triethanolamine and the like.

In the acylamino acid type surfactant of the general formula (8), when R ³ represents the group of the formula (c), the formula (8)
Examples of the compound include triethanolamine N-lauroyl aspartate, sodium N-myristoyl aspartate, and the like.

In the acylamino acid type surfactant of the general formula (8), when R ³ represents the group of the formula (d), the formula (8)
Examples of compounds include sodium N-lauroyl glutamate, triethanolamine N-lauroyl glutamate, sodium N-cocoyl glutamate, and N-
Examples include cocoyl glutamate triethanolamine.

In the amidocarboxylic acid type surfactant represented by the general formula (8), when R ³ represents the group represented by the formula (e), the compound represented by the formula (8) includes N-2-hydroxyethyl-
N-2-lauric acid amidoethyl glycine, and N-
2-Hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine and the like can be mentioned.

In the amidocarboxylic acid type surfactant of the general formula (8), when R ³ represents the group of the formula (f), the compound of the formula (8) is N-2-hydroxyethyl-
N-2-lauric acid amide ethyl-β-alanine, and N-2-hydroxyethyl-N-2-coconut fatty acid amide ethyl-β-alanine.

In the amidocarboxylic acid type surfactant of the general formula (8), when R ³ represents the group of the formula (g), the compound of the formula (8) is N-carboxymethyl-N-
{2- [N '-(2-hydroxyethyl) lauric acid amide] ethyl} glycine, and N-carboxymethyl-N- {2- [N'-(2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine And so on.

In the amidocarboxylic acid type surfactant of the general formula (8), when R ³ represents the group of the formula (h), the compound of the formula (8) is N- {2- [N- (2 -Hydroxyethyl) lauric acid amide] ethyl} glycine,
And N- {2- [N- (2-hydroxyethyl) coconut fatty acid amide] ethyl} glycine and the like.

Component of the detergent composition of the present invention comprising at least one of the polyoxypropylene fatty acid alkanolamide phosphate ester salt of formula (1) and the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt. Component (Ba) consisting of (A) and at least one N-acyl amino acid salt, at least one amidocarboxylic acid type surfactant (Bb), or component (B) consisting of at least one amphoteric surfactant.
The blending weight ratio (solid content) with c) is preferably 9: 1 to 1: 9, and the components (A), (Ba), and (B).
The total content of b) or (Bc) is preferably 0.1% by weight or more based on the total weight of the composition,
It is more preferably about 30% by weight. If the total compounding ratio of the component (A) and the components (Ba), (Bb) or (Bc) is out of the above range, the resulting detergent may have a strong slimy feel or may not have a sufficient refreshing feel. If the total content of the component (A) and the component (Ba), (Bb) or (Bc) is less than 0.1% by weight, the effect is not sufficient.

If necessary, the following additional components can be added to the cleaning composition of the present invention. That is, examples of the additional component include a cationized polymer and cationized guar gum. Further, the following additional components can also be used if necessary. These additional ingredients include glycerin, propylene glycol,
Polyhydric alcohols such as 1,3-butylene glycol and sorbitol, silicones such as methylpolysiloxane and oxyalkylene-modified organopolysiloxane, antidandruff agents such as zinc pyrithione and piroctone olamine, hyaluronic acid, collagen, elastin chondroitin sulfate , Dermatanic acid, fibronectin, ceramides, chitin, water-soluble polymer substances such as chitosan, aloe extract, cell activating agent such as placenta extract, allantoin, anti-inflammatory agent such as glycyrrhizinate, edetate, pyrophosphate, Chelating agents such as hexametaphosphate, citric acid, malic acid and kruconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2,4,4'-trichloro-2'-hydroxy Diphenyl ether, , 4,4'-Trichlorocarbanito, benzalkonium chloride, hinokitiol, resorcin and other preservatives, bactericides, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, ascorbic acid and other antioxidants, fragrances and pigments, etc. Can be appropriately mixed.

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

The use of the detergent composition of the present invention is not limited, and typical examples thereof include kitchen detergents, hard surface cleaners, face cleansers, cleansing foams, shampoos,
Body shampoo, solid detergent, etc. are mentioned.

[0068]

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)
Uric acid monoethanolamide Sodium phosphate preparation
( Manufactured ) 214 g of methyl laurate, 6 monoethanolamine 6
2 g and sodium methoxide 2 g were added, and the resulting 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, 58 g (1 mol) of propylene oxide was added thereto, and the mixture was stirred at 120 ° C. for 3 hours to obtain 302 g of polyoxypropylene (1) lauric acid monoethanolamide.

The physical properties were as follows. Melting point: 36 ° C. Hydroxyl value: 191 Amine value: 6.0 IR analysis (Hitachi 270-30, KBr tablets): 329
2,3092, 2916, 2848, 1642, 156
4,1470,1378,1124,1052cm^{-1 1} 1 H-NMR (Bruker AC-250, CDCl
_Three, TMS internal standard): δ 0.88 ppm (t, 3H,-
CH_Three), 1.14 ppm (m, 3H, -CH (CH ₃ )
O-), 1.26ppm (br, 16H, -CH₂-),
1.62ppm (t, 2H,-CH ₂ CH₂CONH
−), 2.18 ppm (t, 2H, −CH ₂ CONH
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 7H,-CH ₂ CH ₂ OCH ₂ CH
(CH_Three) O-), 5.86 ppm (br, 1H, N
H),

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

[0072]

[Table 1]

The polyoxypropylene (1) lauric acid monoethanolamide-containing reaction mixture obtained was dissolved in chloroform and cooled to 5 ° C., and 230 g of phosphorus oxychloride was added thereto while maintaining the temperature at 10 ° C. or lower. It dripped over time. Then, the obtained reaction mixture was subjected to a phosphoric acid esterification reaction at room temperature for 3 hours. After the reaction,
The generated hydrogen chloride, unreacted phosphorus oxychloride and chloroform were removed under reduced pressure. The reaction product was neutralized with an aqueous solution of sodium hydroxide to obtain a polyoxypropylene (1) lauric acid monoethanolamide sodium phosphate mixture (anionic active ingredient: 30%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 19H, -CH 2} -, -
_{CH (CH 3) O -)} , 1.60ppm (br, 2H, -
_{CH 2 CH 2 CONH -),} 2.25ppm (t, 2H,
_{- CH 2 CONH -), 3.4~3.7ppm} (m, 7
_{H, - CH 2 CH 2 O} CH 2 CH (CH 3) -OP), 31 P-NMR (Bruker AC-250, D 2 O,
Internal _{standard: H 3 PO 4) 0.95ppm (} -10.98ppm not detected)

From the above results, the obtained phosphoric acid ester salt does not contain a phosphoric acid diester salt, but only sodium mono (polyoxypropylene (1) lauric acid monoethanolamide) phosphoric acid. Was confirmed.

Examples 2-5 and Comparative Examples 1-2 (polio)
Xypropylene lauric acid monoethanolamide phosphoric acid
Preparation of Sodium) In each of Examples 2 to 5 and Comparative Examples 1 to 2, 62 g of monoethanolamine and 2 g of sodium methoxide were added to 214 g of methyl laurate, and the resulting methanol was distilled off under reduced pressure with heating and stirring (20 mmHg. , 14
(0 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. Put this in an autoclave and keep it at 90 ℃
The amount of propylene oxide shown in Table 2 was injected under pressure from a propylene oxide introducer into the mixture while heating and stirring, and the mixture was stirred at 100 ° C. for 3 hours to give various addition mole numbers of polyoxypropylene lauric acid monoethanolamide. Synthesized.

Various physical properties and compositions are shown in Table 2.

[Table 2]

1 mol of polyoxypropylene lauric acid monoethanolamide having various addition mole numbers obtained
Was dissolved in chloroform and cooled, and 230 g of phosphorus oxychloride was added dropwise while keeping it at 10 ° C. or lower, and after completion of the addition, this was phosphoric acid esterified at room temperature for 2 hours and neutralized with an aqueous sodium hydroxide solution. A polyoxypropylene lauric acid monoethanolamide sodium phosphate mixture having an added mole number was synthesized (anionic active ingredient: 2
6%). ^{From 31} P-NMR analysis, it was confirmed that the obtained phosphoric acid ester salt did not contain a phosphoric acid diester salt and was only sodium mono (polyoxypropylenelauric acid monoethanolamide) phosphate. . Table 3 shows the names of the obtained compounds.

[0079]

[Table 3]

Example 6 (polyoxypropylene (1) la
Preparation of Sodium Diglycolamide Phosphate) 214 g of methyl laurate and 10 parts of diglycolamine
6 g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmH
g, 150 ° C., 1 hour) to obtain 290 g of lauric acid diglycolamide. This was placed in an autoclave, and 58 g (1 mol) of gaseous propylene oxide was blown into the autoclave while heating and stirring at 90 ° C.
It stirred at 6 degreeC for 6 hours, and synthesize | combined 346 g of 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 -),
1.62ppm (t, 2H, - CH 2 CH 2 CONH
−), 2.18 ppm (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 CH (CH 3) O} -), 6.09ppm (br, 1
H, NH)

GLC analysis: same as the method described in Example 1.
Table 4 shows the holding time and the composition.

[Table 4]

The obtained polyoxypropylene (1) lauric acid diglycolamide was dissolved in chloroform, and this solution was added dropwise to a slurry obtained by dispersing 142 g of diphosphorus pentoxide in toluene. After completion of the dropwise addition, the reaction mixture was stirred at 60 ° C. for 5 hours for phosphorylation. After the reaction was completed, water was added to the reaction mixture to quench it, and then the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate and the organic layer was washed with water to remove orthophosphoric acid. Ethyl acetate was distilled off from this reaction product under reduced pressure to obtain 493 g of polyoxypropylene (1) lauric acid diglycolamide phosphate. This was neutralized with an aqueous sodium hydroxide solution to obtain a polyoxypropylene (1) sodium diglycolamide laurate phosphate mixture (anionic active ingredient: 26%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 19H, -CH 2} -, -
_{CH (CH 3) O -)} , 1.60ppm (br, 2H, -
_{CH 2 CH 2 CONH -),} 2.25ppm (t, 2H,
_{-CH 2 CONH -), 3.4~3.7ppm (} m, 11
_{H, - (CH 2 CH 2} O) 2 -CH 2 CH (CH 3) O
−), ³¹ P-NMR (Bruker AC-250, D ₂ O,
Internal _{standard: H 3 PO 4) -10.99ppm:} 0.95ppm = 3: 17

According to the method described in JP-B-58-8746, the content of phosphoric acid monoester, phosphoric acid diester and orthophosphoric acid in the product before being neutralized with sodium hydroxide was determined. was gotten. -Mono (polyoxypropylene (1) lauric acid diglycolamide) phosphoric acid ester-68% by weight-Di (polyoxypropylene (1) lauric acid diglycolamide) phosphoric acid ester --- … 31 wt% ・ Orthophosphoric acid ……………………………………………… 1 wt%

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

Table 5 shows the various physical properties and compositions.

[Table 5]

1 mol of the obtained polyoxypropylene lauric acid diglycolamide having various addition mole numbers was dissolved in chloroform, and this solution was dissolved in phosphorus pentoxide.
g was added dropwise to the slurry obtained by dispersing g in toluene. After completion of the dropwise addition, the reaction mixture was subjected to phosphoric esterification while stirring at 60 ° C. for 5 hours. After the reaction,
After water was added to the reaction mixture to quench it, the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate, and the organic layer was washed with water to remove orthophosphoric acid. Ethyl acetate was distilled off from this reaction product under reduced pressure to obtain a phosphoric acid ester. This was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxypropylene lauric acid diglycolamide sodium phosphate mixtures having various addition mole numbers (anionic active ingredient: 26%). Table 6 shows the names and compositions of the compounds obtained.

[0089]

[Table 6]

Example 11 (Polyoxypropylene (2)
Polyoxyethylene (5) lauric acid monoethanol
Preparation of Potassium Midophosphate) 214 g of methyl laurate and monoethanolamine 63
g and 0.5 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mm
Hg, 100 ° C., 1 hour) to obtain 243 g of lauric acid monoethanolamide. Put this in an autoclave and stir by heating at 90 ° C.
0 g of gas was injected under pressure and reacted at 110 ° C. for 2 hours to obtain polyoxyethylene (5) lauric acid monoethanolamide. 116 g (2 times mole) of propylene oxide was press-fitted into this and stirred at 130 ° C. for 4 hours to synthesize a polyoxypropylene (2) polyoxyethylene (5) lauric acid monoethanolamide mixture.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 110 Amine value: 12.6 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 (br,} 6H, -CH (C
_{H 3) O -), 1.26ppm} (br, 16H, -CH 2
−), 1.62 ppm (t, 2H, − CH ₂ CH ₂ CON
H -), 2.18ppm (t, 2H, - CH 2 CONH
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 30H, - ( CH 2 CH 2 O) 6 -
_{(CH 2 CH (CH 3)} O) 2 -), 6.09ppm (b
r, 1H, NH)

230 g of phosphorus oxychloride was added dropwise to the obtained polyoxypropylene (2) polyoxyethylene (5) lauric acid monoethanolamide mixture so that the dropping temperature was kept at 10 ° C or lower. Then, the mixture was stirred at room temperature for 3 hours to form a phosphoric acid ester. This was neutralized with an aqueous potassium hydroxide solution to obtain a potassium mono (polyoxypropylene (2) polyoxyethylene (5) lauric acid monoethanolamide) phosphoric acid mixture (anionic active ingredient: 26
%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 22H, -CH 2} -, -
_{(CH (CH 3) O)} 2 -), 1.60ppm (br, 2
_{H, -CH 2 CH 2 CONH -} ), 2.25ppm (t,
_{2H, -CH 2 CONH -),} 3.4~3.7ppm
(M, 30H, - (CH 2 CH 2 O) 6 - (CH 2 CH
(CH ₃ ) O) ₂ -P), ³¹ P-NMR (Bruker AC-250, D ₂ O,
Internal _{standard: H 3 PO 4) 0.95ppm (} -10.98ppm not detected)

From the above results, the obtained phosphoric acid ester salt does not contain a phosphoric acid diester salt, and mono (polyoxypropylene (2) polyoxyethylene (5) lauric acid monoethanolamide) phosphorus It was confirmed to be the sodium acid mixture only.

Example 12 (Polyoxypropylene (2)
Polyoxyethylene (5) diglycolamilate laurate
Preparation of potassium phosphonate ) 214 g of methyl laurate and diglycolamine 106
g and sodium methoxide 2 g were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(100 ° C., 1 hour) to obtain 290 g of lauric acid diglycolamide. Put this in the autoclave and 90
The mixture was heated and stirred at 0 ° C., 220 g of ethylene oxide was injected under pressure in a gaseous state, and the mixture was reacted at 100 ° C. for 2 hours to prepare a polyoxyethylene (5) lauric acid diglycolamide mixture. 116 g (2 times mole) of propylene oxide was press-fitted into this and stirred at 130 ° C. for 4 hours to synthesize a polyoxypropylene (2) polyoxyethylene (5) lauric acid diglycolamide mixture.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 104 Amine value: 13.4 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 -),
1.62ppm (t, 2H, - CH 2 CH 2 CONH
−), 2.18 ppm (t, 2H, − CH ₂ CONH
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 34H, - ( CH 2 CH 2 O) 7 -
_{(CH 2 CH (CH 3)} O) 2 -), 6.09ppm (b
r, 1H, NH)

The obtained polyoxypropylene (2) polyoxyethylene (5) lauric acid diglycolamide mixture was dissolved in chloroform, and this solution was mixed with phosphorus pentoxide 1
42 g was added dropwise to the slurry obtained by dispersing in toluene. After completion of the dropwise addition, the reaction mixture was stirred at 60 ° C. for 5 hours for phosphoric acid esterification. After the reaction was completed, water was added to the reaction mixture to quench it, and then the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate, and then the organic layer was washed with water to remove orthophosphoric acid. Ethyl acetate was distilled off from this reaction product under reduced pressure to obtain a polyoxypropylene (2) polyoxyethylene (5) lauric acid diglycolamide phosphoric acid ester mixture. This is neutralized with an aqueous solution of potassium hydroxide to give polyoxypropylene (2)
A polyoxyethylene (5) lauric acid diglycolamide potassium phosphate mixture was obtained (anionic active ingredient: 3
0%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 22H, -CH 2} -, -
_{(CH (CH 3) O)} 2 -), 1.60ppm (br, 2
_{H, - CH 2 CH 2 CONH} -), 2.25ppm (t,
_{2H, - CH 2 CONH -)} , 3.4~3.7ppm
(M, 34H, - (CH 2 CH 2 O) 7 - (CH 2 CH
(CH ₃ ) O) ₂ -P), ³¹ P-NMR (Bruker AC-250, D ₂ O,
Internal _{standard: H 3 PO 4) -10.99ppm:} 0.95ppm = 2: 8

According to the method described in JP-B-58-8746, the content of phosphoric acid monoester, phosphoric acid diester and orthophosphoric acid in the product before being neutralized with sodium hydroxide was quantified. was gotten.・ Mono (polyoxypropylene (2) polyoxyethylene (5) lauric acid diglycolamide) phosphoric acid ester ………… 57% by weight ・ Di (polyoxypropylene (2) polyoxyethylene (5) lauric acid diester Glycolamide) Phosphoric acid ester ……………… 42% by weight ・ Orthophosphoric acid …………………………………………………… 1% by weight

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

The physical properties were as follows. Melting point: 24 ° C. Hydroxyl value: 146 Amine value: 2.9 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 -),
1.62ppm (t, 2H, - CH 2 CH 2 CONH
−), 2.18 ppm (t, 2H, − CH ₂ CONH
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 15H, - ( CH 2 CH 2 O) 3 - C
_{H 2 CH (CH 3) O} -), 6.09ppm (br, 1
H, NH)

The obtained polyoxypropylene (1) lauric acid triglycolamide mixture was dissolved in chloroform, and 230 g of phosphorus oxychloride was added dropwise to this solution while maintaining the dropping temperature at 10 ° C or lower. After this time, the mixture was stirred at room temperature for 3 hours for phosphoric acid esterification. It was neutralized with an aqueous sodium hydroxide solution to synthesize sodium mono (polyoxypropylene (1) lauric acid triglycolamide) phosphate (anionic active ingredient: 26%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 19H, -CH 2} -, -
_{CH (CH 3) O -)} , 1.60ppm (br, 2H, -
_{CH 2 CH 2 CONH -),} 2.25ppm (t, 2H,
_{- CH 2 CONH -), 3.4~3.7ppm} (m, 15
_{H, - (CH 2 CH 2} O) 3 - (CH 2 CH (CH 3)
OP), ³¹ P-NMR (Bruker AC-250, D ₂ O,
Internal _{standard: H 3 PO 4) 0.95ppm (} -10.98ppm not detected)

From the above results, the obtained phosphoric acid ester salt mixture contains no phosphoric acid diester salt,
It was confirmed to be the mono (polyoxypropylene (1) lauric acid triglycolamide) sodium phosphate mixture only.

Comparative Example 6 (polyoxypropylene (1)
Lioxyethylene (10) lauronate monoethanol
Preparation of sodium midophosphate) Monoethanolamine 62 was added to 214 g of methyl laurate.
g and sodium methoxide 2 g were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(150 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. Add 10 parts of ethylene oxide to this
Molar addition was carried out (130 ° C., 2 hours) to obtain 332 g of polyoxyethylene (10) lauric acid monoethanolamide. 58 g (1 mol) of propylene oxide was added thereto (140 ° C., 1 hour) to synthesize a polyoxypropylene (1) polyoxyethylene (10) lauric acid monoethanolamide mixture.

The physical properties were as follows. Melting point: -5 ° C or lower Hydroxyl value: 92 Amine value: 14.9 IR analysis (Hitachi 270-30, KBr tablet): 331
2,3080, 2924, 2852, 1650, 154
8, 1466, 1376, 1352, 1286, 111
^{4cm -1 1 H-NMR (Bruker} AC-250, 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 -),
1.62ppm (t, 2H, - CH 2 CH 2 CONH
−), 2.18 ppm (t, 2H, − CH ₂ CONH
-), 2.68 ppm (br, 1H, -OH), 3.2-
4.1ppm (m, 47H, - ( CH 2 CH 2 O) 11 - C
_{H 2 CH (CH 3) O} -), 6.09ppm (br, 1
H, NH)

To the obtained polyoxypropylene (1) polyoxyethylene (10) lauric acid monoethanolamide mixture was added dropwise a slurry obtained by dispersing 142 g of phosphorus pentoxide in toluene. After completion of the dropwise addition, the reaction mixture was stirred at 60 ° C. for 2 hours to perform phosphoric acid esterification. After the reaction was completed, water was added to the reaction mixture to quench it, and then the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate and the organic layer was washed with water to remove orthophosphoric acid. Ethyl acetate was removed from this reaction product under reduced pressure to obtain a polyoxypropylene (1) polyoxyethylene (10) lauric acid monoethanolamide mixture. This was neutralized with an aqueous solution of sodium hydroxide to obtain a polyoxypropylene (1) polyoxyethylene (10) sodium lauric acid monoethanolamide phosphate mixture (anionic active ingredient: 30%).

The NMR measurement results are shown below. ¹ H-NMR (Bruker AC-250, D
₂ O): δ 0.88 ppm (t, 3H, —CH ₃ ), 1.
_{11~1.43ppm (brm, 19H, -CH 2} -, -
_{CH (CH 3) O -)} , 1.60ppm (br, 2H, -
_{CH 2 CH 2 CONH -),} 2.25ppm (t, 2H,
_{- CH 2 CONH -), 3.4~3.7ppm} (m, 47
_{H, - (CH 2 CH 2} O) 11 - (CH 2 CH (CH 3)
OP), ³¹ P-NMR (Bruker AC-250, D ₂ O,
Internal _{standard: H 3 PO 4) -10.99ppm:} 0.95ppm = 2: 8

Further, according to the method described in JP-B-58-8746, the content of phosphoric acid monoester, phosphoric acid diester and orthophosphoric acid in the product before being neutralized with sodium hydroxide was quantified. was gotten. -Mono (polyoxypropylene (1) polyoxyethylene (10) lauric acid diglycolamide) phosphoric acid ester ... 56% by weight-Di (polyoxypropylene (1) polyoxyethylene (10) dilauric acid) Glycolamide) Phosphate ester ……………… 43 wt% ・ Orthophosphoric acid …………………………………………………… 1 wt%

Example 13 (Polyoxypropylene (2)
Preparation of sodium lauric acid monoethanolamide phosphate
Ltd.) and lauric acid monoethanolamide 243g purified in an autoclave, boron trifluoride-ether complex 2.4
g and then 116 g of propylene oxide were added, and the mixture was reacted at 150 ° C. for 1 hour. After completion of the reaction, water was added to the reaction mixture to quench it, and then the solvent was removed under reduced pressure to obtain 360 g of a polyoxypropylene (2) lauric acid monoethanolamide mixture.

Table 7 shows the distribution of oxypropylene groups by GLC analysis.

[Table 7]

[Note in Table 7] 1) Includes oxyethylene group derived from monoethanolamine

Table 7 shows that the oxypropylene group distribution width is slightly narrower than that of the product obtained by using the base catalyst of Example 3. The obtained polyoxypropylene (2) lauric acid monoethanolamide was dissolved in chloroform and cooled to 5 ° C., and phosphorus oxychloride 23
0 g was added dropwise over 1 hour while maintaining the temperature at 10 ° C or lower. Thereafter, the phosphoric acid esterification reaction was carried out at room temperature for 3 hours. After completion of the reaction, the generated hydrogen chloride, unreacted phosphorus oxychloride and chloroform were removed under reduced pressure. This was neutralized with an aqueous sodium hydroxide solution to obtain a polyoxypropylene (2) lauric acid monoethanolamide sodium phosphate mixture (anionic active ingredient: 30%).

Comparative Example 7 (Polyoxypropylene (1)
Preparation of Uric Acid Monoethanolamide) 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 generated during that time, but the distilled water was 80% of the theoretical amount. As a result of GLC analysis, the lauric acid monoethanolamide content was 75%. 58 g of propylene oxide was added thereto, and an addition reaction was carried out at 120 ° C. for 1 hour in an autoclave. As a result of GLC analysis, most of the reaction products were propylene oxide adducts of monoethanolamine, and the content of the target product was 12%.
Met. The obtained product had a blackish brown color.

Comparative Example 8 (Polyoxypropylene (1)
Preparation of uric acid monoethanolamide) Monoethanolamine 62 was added to 214 g of methyl laurate.
g and sodium methoxide 2 g were added, and the resulting methanol was distilled off under reduced pressure while heating and stirring (20 mmHg,
(140 ° C., 1 hour) to obtain 244 g of lauric acid monoethanolamide. The amine value of this product was 6.2. This was dissolved in 3000 ml of xylene and washed twice with 800 ml of 2% by weight hydrochloric acid water. Then, saturated saline solution 800
After washing with ml three times, it was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, recrystallized from THF-toluene to purify lauric acid monoethanolamide 194.
g was obtained (80% yield). The amine value of this product is 0.01
Met. This was put in an autoclave, and 46 g (1 mol) of propylene oxide was added, and the mixture was heated to 150 ° C.
After stirring for 6 hours, the reaction did not proceed and only the raw materials were recovered.

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

[0117]

[Table 8]

Examples 14 to 25 and Comparative Examples 10 to 17 Compounds and mixtures obtained in Examples 1 to 12 and Comparative Examples 1 to 6 and 9, respectively, and commercially available sodium polyoxyethylene (3) lauryl ether sulfate were added. Using Table 9
A detergent composition having the composition shown in 1 was prepared. The obtained product was subjected to the following foaming power, detergency test, pH stability, skin irritation test, sensory test and protein denaturation test.

These test methods were carried out by the following methods. 1) Foaming power test The cleaning agent was diluted with distilled water so that the active agent pure content was 0.25%, and the foaming power was measured according to the method described in JIS K3362. The evaluation criteria were set as follows. ∘: Very good foaming, foaming power of 220 mm or more ○: Good foaming, foaming power of 200 mm or more, less than 220 mm △: Normal foaming, foaming power of 170 mm or more, less than 200 mm × ... Poor foaming, foaming power of 170 mm Less than

2) Detergency test 0.1% SudanIII as an indicator was added to beef tallow, and 5% of this was applied to a porcelain dish (diameter 25 cm), and 30 g of a 10% by weight cleaning solution was impregnated with the solution. Detergency was indicated by the number of dishes that had been scrubbed with sponge and washed until no more beef tallow was washed from the dishes. 3) pH stability test A 2% washing solution adjusted to pH 7.0 was placed in a constant temperature bath at 50 ° C, and the pH after 30 days was measured. 4) Skin irritation (rough hand) test Immerse hand up to wrist in 1% washing solution for 30 minutes a day, and
After repeating for one day, the condition of the skin was determined on the following day based on the following criteria, and the average score of 20 testers was obtained. 3 points: Hand was not rough 2 points: Hand was slightly rough 1 point: rough The evaluation criteria were set as follows. …: Average point 2.1 to 3.0 ○: Average point 1.1 to 2.0 ×: Average point 0 to 1.0

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

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

The test results are shown in Table 9.

[Table 9]

As is clear from the results shown in Table 9, the polyoxypropylene fatty acid alkanolamide phosphate ester salt mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt mixture of the present invention have a foaming power and a detergency. , PH stability was excellent, skin irritation and protein denaturation were low, and the feeling of use was refreshing. On the other hand, in the polyoxypropylene fatty acid alkanolamide phosphate ester salt and the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt and the polyoxyethylene fatty acid alkanolamide phosphate ester salt which are outside the scope of the present invention, It was inferior to the compound mixture of the present invention in any of foaming power, detergency, pH stability, skin irritation, refreshing feeling and protein denaturation.

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

The test results are shown in Table 10.

[Table 10]

As is clear from the results shown in Table 10, the polyoxypropylene fatty acid alkanolamide phosphate ester salt mixture and the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester salt mixture of the present invention, an anionic surfactant and a cationic interface were used. Activator,
The detergents of Examples 26 to 33, which consisted of an amphoteric surfactant or a nonionic surfactant, contained a polyoxypropylene fatty acid alkanolamide phosphate ester salt mixture and a polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester mixture. It was confirmed that the foaming power and the detergency were more excellent and the skin irritation and the protein denaturation were less than the cases (Comparative Examples 18 to 25) that were not present.

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

[0129]

[Table 11]

[0130]

[Table 12]

As is clear from the results shown in Tables 11 and 12, the polyoxypropylene fatty acid alkanolamide phosphate ester mixture or the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester mixture of the present invention and the N-acyl amino acid are used. The detergent composition comprising a combination of an amidocarboxylic acid type surfactant or an amphoteric surfactant was particularly excellent in foaming power and detergency and had a very refreshing feeling. Moreover, it was confirmed that it is suitable for shampoo and body shampoo because it causes less irritation.

Example 44 A rinse-incorporating shampoo having the following composition was prepared, and Example 1 was used.
It used for the same test as 4. Ingredient wt% N-carboxymethyl-N- {2- [2-hydroxyethyl-coconut oil fatty acid amide] ethyl} glycine (30%) 20.0 N-cocoyl-L-glutamate triethanolamine (30%) 5.0-2-coconut oil alkyl-N-carboxyethyl-N-hydroxy-ethyl imidazolinium betaine (30%) 10.0-polyoxypropylene (2) coconut oil fatty acid monoethanolamide sodium phosphate mixture 5. 0-coconut oil fatty acid diethanolamide 1.0-stearyl trimethyl ammonium chloride 1.5-cetyl octanoate 0.5-carboxymethyl chitin 0.1-hyaluronic acid 0.1-sodium edetate 0.1-preservatives 0. 1-Purified water Table 13 shows the balance test results.

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

[0134]Example 46 A pearly shampoo having the following composition was prepared and used in Example 14
It was subjected to the same test. 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 propyl dimethyl betaine 5.0-Lauroyl-N-methyl taurine sodium 5.0-Polyoxypropylene (3) palmitic acid diglycolamide ammonium phosphate mixture 5.0-Palm oil fatty acid diethanolamide 2.0-Palm Oil fatty acid monoethanolamide 1.5 ・ Casodium soda pH = 6 amount ・ Methylparaben 0.1 ・ Perfume proper amount ・ Purified water balance Table 13 shows the test results.

Example 47 A gel shampoo having the following composition was prepared and subjected to the same test as in Example 14. Ingredients wt% Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 20.0 Polyoxypropylene (5) polyoxyethylene (0.5) Isostearic acid monoethanolamide potassium phosphate mixture 5. 0-Lauric acid isopropanolamide 8.0-Carboxymethyl chitin 0.1-Methylparaben 0.1-EDTA 0.1-Citric acid pH = 7.0 Amount-Purified water Residual test results are shown in Table 13.

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

Example 49 A shampoo having the following composition was prepared and subjected to the same tests as in Example 14. Ingredients wt% sodium lauryl sulfate 15.0 polyoxypropylene (20) palm kernel oil fatty acid monoethanol sodium amide phosphate mixture 5.0 POE (3) sodium lauryl ether carboxylate 5.0 mono (polyoxyethylene ( 6) Lauric acid amide) Sodium phosphate 4.0-Methylparaben 0.1-EDTA 0.1-Purified water balance Table 13 shows the test results.

Example 50 A body shampoo having the following composition was prepared and subjected to the same test as in Example 14. Ingredients% by weight 2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30%) 20.0-polyoxypropylene (5) polyoxyethylene (0.8) tallow fatty acid diglycolamide phosphate Potassium mixture 5.0-Triethanolamine monododecylphosphate 5.0-Triethanolamine laurate 7.0-Methylparaben 0.1-EDTA 0.1-Purified water Residual test results are shown in Table 13.

Example 51 A body shampoo having the following composition was prepared and subjected to the same test as in Example 14. Ingredients wt% Polyoxyethylene (3) lauric acid monoethanolamide magnesium sulfate mixture 10.0 ・ Polyoxypropylene (1) polyoxyethylene (5) diglycolamide lauric acid sodium phosphate 10.0 ・ Polyoxyethylene ( 5) Lauric acid monoethanolamide disodium sulfosuccinate (30%) 5.0 ・ Lauroyl sarcosine sodium 5.0 ・ Lauryl dimethylamine oxide 4.0 ・ Lauric acid diethanolamide 3.0 ・ Ethanol 2.0 ・ Purified water balance The test results are shown in Table 13.

Example 52 A face wash having the following composition was prepared and subjected to the same test as in Example 14. Ingredients wt% N-2-hydroxyethyl-N-2-coconut oil fatty acid amide Ethyl-β-alanine (30%) 60.0 Polyoxypropylene (0.5) coconut oil fatty acid monoethanol amide ammonium phosphate mixture 10 0.0-lauric acid diethanolamide 7.0-2-alkyl-N-carboxymethyl-N-hydroxy-ethyl imidazolinium betaine (30%) 5.0-monoammonium glycyrrhizinate 0.2-polyoxyethylene (2 ) Lauric acid monoethanolamide 0.5-Allantoin 0.5-Methylparaben 0.1-Citric acid pH = 6.5 Amount-Purified water Balance Table 13 shows the test results.

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

Example 54 A kitchen detergent having the following composition was prepared and subjected to the same test as in Example 14. Ingredient% by weight- sodium α-olefin sulfonate 15.0-laurylamide dimethyl hydroxypropyl sulfobetaine (30%) 5.0-polyoxypropylene (3) lauric acid myristic acid (75:25) magnesium monoethanolamide phosphate Mixture 5.0-lauryl glucoside 3.0-POE (2) lauric acid monoethanolamide 2.0-edetate 0.1-purified water Residual test results are shown in Table 13.

Example 55 An automatic dishwashing detergent having the following composition was prepared, and Example 14 was prepared.
The same test was performed. Ingredients% by weight- Sodium laurylbenzene sulfonate 20.0-Polyoxypropylene (2) stearic acid monoethanolamide sodium phosphate mixture 6.0-Sodium xylene sulfonate 5.4-Sodium sulfate 1.0-Lauryl alcohol ammonium sulfate 8 .35 ・ Purified water The balance test results are shown in Table 13.

Example 56 An oven cleaner having the following composition was prepared and subjected to the same tests as in Example 14. It was effective in removing oil stains that were thermally altered. Ingredients% by weight • POE (9) sodium nonylphenyl ether sulfate 3.0 • POE (9) sodium nonylsulfophenyl ether sulfate 3.0 • Polyoxypropylene (2) polyoxyethylene (5) lauric acid monoethanolamide phosphoric acid Sodium mixture 2.0-Sodium hydroxide 4.0-Polyoxypropylene (1) coconut oil fatty acid diglycolamide 5.0-Purified water balance Table 13 shows the test results.

[0145]

[Table 13]

As is clear from the results in Table 13, Example 4 containing the polyoxypropylene (polyoxyethylene) fatty acid alkanolamide sulfate ester salt of the present invention.
The cleansing agents Nos. 4 to 56 were excellent in foaming power, detergency and pH stability, and had little skin irritation and protein denaturation. The sensory test showed a refreshing feel.

Example 57 An enzyme-containing detergent having the following composition was prepared and its performance was evaluated. As a result, it showed excellent detergency. Ingredients wt% POE (6) C _10/14 Fatty alcohol ether 17.0 Alkylbenzene sulfonic acid diethanolamine salt 60.0 Polyoxypropylene (2) coconut oil fatty acid monoethanolamide sodium phosphate mixture 5.0 coconut oil Fatty acid monoethanolamide 22.0 Enzyme AP 0.2 Lipase A 0.15 Hard water (100 ppm) 0.65

Example 58 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
When its performance was evaluated, the skin after use showed an excellent refreshing feeling. Ingredients% by weight • Base material for soap (beef tallow: coconut = 8: 2) 92.3 • Sodium N-lauroyl-L-aspartate 2.0 • Polyoxypropylene (2) tallow fatty acid monoethanolamide sodium phosphate mixture 1. 0-titanium oxide 0.1-edetate 0.1-lauric acid diethanolamide 4.5

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

Example 60 A bubble bath agent having the following composition was prepared and its performance was evaluated. As a result, a moist feel to the skin after bathing was given. Ingredients wt% Distearyl dimethyl ammonium chloride 59.0 Palm oil fatty acid amide propyl dimethyl glycine 16.0 Polyoxypropylene (20) Polyoxyethylene (1) Palm oil fatty acid diglycol amide sodium lysine mixture 1.0・ Dimethylmyristylamine oxide 4.0 ・ Palm oil fatty acid diethanolamide 7.0 ・ Fragrance 1.0 ・ Purified water balance

[0151]

The polyoxypropylene fatty acid alkanolamide phosphate salt mixture of the formula (1) and the polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate salt mixture of the formula (1) of the present invention have a foaming power,
It is an excellent surfactant that has excellent detergency and pH stability, has very little irritation to the skin and hair, and has a refreshing usability. In addition, a detergent composition containing this compound mixture has high foaming power and detergency, has almost no decrease in pH over time due to decomposition, and is further irritating to the skin and hair by other surfactants. It shows a mild and refreshing feel with less tingling sensation. Therefore, conventional alkyl ether phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, and / or polyoxyethylene fatty acid monoethanolamide phosphate ester salts are used. It is possible to obtain a cleaner composition which is safer and has excellent performance as compared with the contained cleaner. Further, at least one selected from the compound mixture of the present invention and an N-acyl amino acid salt, an amidocarboxylic acid salt or an amphoteric surfactant.
A detergent composition comprising seeds is suitable for use in shampoos, body shampoos, etc. because it is extremely excellent in foaming power and cleaning power, has less irritation, and has a creamy foam quality.
In addition, the method of the present invention enables efficient and industrially easy production of a polyoxypropylene fatty acid alkanolamide phosphate ester mixture and a polyoxypropylene polyoxyethylene fatty acid alkanolamide phosphate ester mixture.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C11D 1/94 1:02 1:34 1:38 1:66 1:88)

Claims (5)

[Claims] 1. The following general formula (1): (In the formula (1), R represents 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 oxypropylene group, A is RCONH (CH ₂ CH ₂ O) _x (EO) _y
(PO) _z ^- group or -OM _p group, x is 1 or 2
, Y and z each independently represent an integer of 0 or 1 or more, M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of an alkanolamine, or a base. Represents a cationic residue of the amino acid, and p represents the reciprocal of the valence of the atom or group represented by M. And a mean value y'of y is a positive number of 0 or 5 or less and a mean value z'of z is a positive number of 0.3 to 20. Mixtures of polyoxypropylene fatty acid alkanolamide phosphate ester compounds characterized by 2. The following general formula (2): (In the formula (2), R is the same as the above, R ¹ represents an alkyl group having 1 to 3 carbon atoms), and a fatty acid alkyl ester represented by the general formula (3): (In the formula (3), x is the same as the above) and reacted with an alkanolamine in the presence of a base catalyst to give a compound represented by the general formula (4): (In the formula (4), R and x are the same as above.) A fatty acid alkanolamide represented by the formula (4) was prepared, and the compound of the formula (4) was added to the compound of the formula (4) in an amount of 0 to 5
By adding a double mole of ethylene oxide, the following general formula (5): (In the formula (5), R, x, EO and y are the same as above.)
A reaction product mixture containing a polyoxyethylene fatty acid alkanolamide represented by the following formula is prepared, and the reaction product mixture of the general formula (5) contained in the reaction product mixture is prepared without purification of the reaction product mixture. 0.3 to 20 times the molar amount of propylene oxide is added to the compound to give the following general formula (6): (In the formula (6), R, x, EO, y, PO and z are the same as above.) A mixture of two or more polyoxypropylene fatty acid alkanolamide compounds is prepared, and this mixture and phosphoric acid are used. React with an esterifying agent and then neutralize with a neutralizing agent selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal oxides, ammonia, alkanolamines and basic amino acids. General formula (1), characterized by: (In the formula (7), R, x, y, z, EO, PO, M, p and A are the same as the above), and a method for producing a mixture of polyoxypropylene fatty acid alkanolamide phosphate mixed salt compounds. 3. A detergent composition comprising a mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester salt compound according to claim 1. 4. A mixture of the polyoxypropylene fatty acid alkanolamide phosphate ester salt compound according to claim 1, and at least an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant. A cleaning composition comprising one kind of surfactant. 5. A component (A) comprising a mixture of the polyoxypropylene fatty acid alkanolamide phosphate salt compounds according to claim 1 and a component (A) comprising at least one selected from N-acyl amino acids and salts thereof. B
A cleaning composition comprising a), a component (Bb) comprising at least one amidecarboxylic acid type surfactant, or at least one amphoteric surfactant (Bc).