JPH07206878A - Production of fatty acid diglycolamide phosphate or its salt and cleansing agent composition containing the same product - Google Patents

Abstract

PURPOSE:To obtain a fatty acid diglycolamide phosphate useful as a cleansing agent excellent in forming power and cleaning force and hardly having irritation to skin and hair by reacting a fatty acid ester with diglycolamine and then reacting the product with a phosphorylating agent. CONSTITUTION:A fatty acid ester of the formula R<1>COOR (R<1> is a 5-21C hydrocarbon; R is methyl, ethyl or propyl) is reacted with diglycolamine in the presence of a metal alkoxide (e.g. sodium methoxide) at 90-180 deg.C by condensation to afford a fatty acid diglycolamide, which is then reacted with a phosphorylating agent (e.g. phosphorus oxychloride) to provide the objective compound of the formula (A is a R<1>CONHCH2CH2OCH2CH2 group or M; M is H, an alkali metal, an alkaline earth metal, ammonium, a cationic residue of an alkanolamine or a cationic residue of a basic amino acid) or its salt. The compound of the formula is included as an active ingredient to provide the objective cleansing agent composition having excellent characteristics.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in foaming power / detergency, rich in foam amount and creamy, and is excellent in feeling of use without feeling slimy or tingling at the time of rinsing. The present invention relates to a method for producing a fatty acid diglycolamide phosphoric acid ester or a salt thereof which is less irritating and has excellent product stability, and a detergent composition containing the product.

[0002]

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

In recent years, alkyl phosphate ester surfactants have been favorably used for the purpose of reducing skin irritation and improving detergency. However, the alkyl phosphate ester surfactant has problems such as low foaming power and poor solubility in water,
Moreover, there was a point that the refreshing feeling at the time of use was insufficient.

Therefore, for the purpose of improving the solubility in water while maintaining the characteristics of the alkyl phosphate ester surfactant, the following general formula (III):

[Chemical 2] (In the formula, R ¹ and M are the same as those defined in the general formula (I), and A is R ¹ CONHCH ₂ CH ₂ OCH ₂ CH ₂ —.
Represents a group or M, and n is an integer of 1 or more, generally 3 or more. ), Polyoxyethylene fatty acid monoethanolamide phosphate ester salt has been used.

These conventional polyoxyethylene fatty acid monoethanolamide phosphate ester salts have low irritation to the skin, hair and eye mucous membranes, and have a refreshing feeling of use without any slimy feeling after washing. However, it is still unsatisfactory in terms of foaming and detergency, and has a drawback that the creamy feeling of foam is also poor.

A known method for producing a polyoxyethylene fatty acid monoethanolamide phosphate salt represented by the general formula (III) is to add poly (ethylene oxide) to fatty acid monoethanolamide to prepare polyoxyethylene fatty acid monoethanolamide. And to this, phosphorus oxychloride,
This is a method of reacting a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid to form a phosphoric acid ester, and finally neutralizing it with caustic soda to salt the phosphoric acid ester. An ethylene oxide addition step is included in the middle of this method, but at this time, there is a problem that a small amount of dioxane is produced. Due to its high toxicity, dioxane should not be incorporated in detergents.

[0007]

DISCLOSURE OF THE INVENTION The present invention is excellent in foaming power / detergency, has a large amount of foam and is creamy, and is excellent in the feeling of use without slimy feeling or tingling sensation during rinsing, and on skin and It is intended to provide a method for producing a fatty acid diglycolamide phosphoric acid ester salt which is less irritating to hair and is excellent in product stability, and a detergent composition containing the product.

[0008]

Means for Solving the Problems The present inventors
Fatty acid diglycolamide with excellent detergency, abundant foam volume and creamy, excellent feeling of use without stuffiness and crease during rinsing, less irritation to skin and hair, and excellent product stability. As a result of repeated studies to obtain a method for producing a phosphate ester salt and a detergent composition containing the product of this method, a fatty acid diglycolamide phosphate ester salt product produced by a specific method has the above-mentioned characteristics. It was found that by adding a nonionic surfactant, anionic surfactant or amphoteric surfactant to this, a detergent composition having excellent practicability can be obtained. It came to completion.

The method for producing the fatty acid diglycolamide phosphate ester or salt thereof according to the present invention is represented by the following general formula (I):

[Chemical 3](However, in the formula (I), R¹ Has 5 to 21 carbon atoms
Straight or branched chain, saturated or unsaturated hydrocarbons
Represents a group, A is R¹ CONHCH₂ CH₂ OCH ₂ CH
₂ Represents a group or M, M is a hydrogen atom, an alkali metal atom
Child, alkaline earth metal atom, ammonium group, alkano
Cationic residues of basic amines or basic amino acids
Represents a cationic residue. ) Fatty acid diglycol
In order to produce a luamidophosphoric acid ester or a salt thereof, the following general formula (II): R¹ COOR (II) (However, in the formula (II), R¹ Is as defined above,
R represents a methyl group, an ethyl group, or a propyl group. )
A fatty acid ester represented by and diglycolamine
Condensation of fatty acid diglycol in the presence of metal alkoxide
Amide was prepared and reacted with phosphorylating agent
Prepare fatty acid diglycol amide phosphate ester
In the compound of general formula (I), M is an alkali metal precursor
Child, alkaline earth metal atom, ammonium group, alkano
Of cationic residues of basic amines or basic amino acids
When the residue is an on-type residue, the fatty acid diglycolamido
Dolinic acid ester, alkali metal hydroxide, alkali
Earth metal hydroxide, ammonia, alkanolamine,
Or a process of neutralizing with a neutralizing agent consisting of basic amino acids
It is characterized by applying a degree.

The detergent composition according to the present invention is a component (A which is obtained by the above-mentioned method of the present invention and comprises at least one of the fatty acid diglycolamide phosphoric acid ester represented by the general formula (I) and a salt thereof. ) And at least one nonionic surfactant compound (Ba)
It is characterized by containing and.

Another detergent composition according to the present invention is a component which is obtained by the above-mentioned method of the present invention and comprises at least one of fatty acid diglycolamide phosphoric acid ester represented by the general formula (I) and a salt thereof. Component (B) comprising (A) and at least one anionic surfactant compound (B
b) and are included.

Still another detergent composition according to the present invention comprises at least one of the fatty acid diglycolamide phosphate ester represented by the above general formula (I) and the salt thereof, which is obtained by the above-mentioned method of the present invention. The component (A) and the component (Bc) which is at least one amphoteric surfactant compound.

[0013]

The formula (I) obtained by the production method according to the present invention
The fatty acid diglycol amide phosphoric acid ester and the salt thereof are equivalent to the compound when n is 2 in the conventional polyoxyethylene fatty acid monoethanol amide phosphoric acid ester salt compound represented by the formula (III). In the compound of formula (III), when n is 1, that is, the general formula (IV):

[Chemical 4] (However, in the formula (IV), R ¹ , A, and M are as defined above.) The fatty acid monoethanolamide phosphoric acid ester salt is not suitable for practical use because of its extremely poor stability. Further, in the formula (III), the compound in which n is 3 or more has the drawbacks that the foaming power / cleansing power is not sufficient, the creamy feeling of the foam is lacking, and the post-cleansing sensation is present.

In the method of the present invention for producing a fatty acid diglycolamide phosphate ester of the formula (I) or a salt thereof,
The saturated or unsaturated fatty acid (C ₆ -C ₂₂ ) is esterified with a lower alcohol (methyl alcohol, ethyl alcohol, or propyl alcohol) to obtain the formula (I
The fatty acid lower alcohol ester of I) is used as a starting material, and this is condensed with diglycolamine in the presence of a metal alkoxide such as sodium methoxide to prepare a fatty acid diglycolamide. Next, this is reacted with a phosphorylating agent such as phosphorus oxychloride, phosphorus pentoxide, and polyphosphoric acid to form a phosphoric acid ester. As a result, in the formula (I), a compound in which M is —H, that is, a fatty acid diglycolamide phosphate ester is obtained. In the compound of formula (I), M
Is an alkali metal atom, an alkaline earth metal atom, an ammonium salt, or a cationic residue of an alkanolamine, or a cationic residue of a basic amino acid, the fatty acid diglycol amide phosphate ester is treated with an alkali metal water. From oxides (eg sodium hydroxide, potassium hydroxide etc.), alkaline earth metal hydroxides (eg magnesium hydroxide etc.), ammonia, alkanolamines (eg triethanolamine) or basic amino acids (eg lysine) Neutralize with

In the conventional method for synthesizing a fatty acid diglycol amide phosphate ester or a salt thereof using polyoxyethylene fatty acid monoethanolamide produced by the ethylene oxide addition method, the number of oxyethylene groups is selectively limited to 2. Although it was difficult to do so, it became possible to limit the number of oxyethylene groups to 2 by using the method of the present invention. Further, since the method of the present invention does not include an ethylene oxide addition step, toxic dioxane is never mixed in the product, and an extremely safe product can be obtained.

Thus, the fatty acid diglycolamide phosphoric acid ester represented by the formula (I) or a salt thereof obtained in the present invention and the conventional method, that is, 1 mol of ethylene oxide is added to the fatty acid monoethanolamide, and then phosphoric acid is added. Polyoxyethylene obtained by esterification (1E.
O. ) When fatty acid monoethanolamide phosphoric acid ester or its salt is compared, both are the same as represented by formula (III) in that n = 2, but the products of both production methods are clear as described above. Is to be distinguished. That is, in the latter polyoxyethylene (1EO) fatty acid amide phosphate salt, the distribution of the number of oxyethylene groups is as shown in Table 1 below, and the monooxyethylene compound represented by the formula (IV) is It contains 32% and 20% polyoxyethylene (n ≧ 3) compounds, which has the disadvantage that the stability of this product is extremely low and the foaming power is insufficient. However, the product obtained by the method of the present invention has no such drawbacks.

An acyl group (R ¹ -C in the compound of formula (II)
The fatty acid constituting O-) is a linear or branched saturated or unsaturated fatty acid having 6 to 22 carbon atoms, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid. , Coconut oil fatty acid and the like are used.

M in the formula (I) is a hydrogen atom, an alkali metal atom such as sodium or potassium, an alkaline earth metal atom such as magnesium, an ammonium group, a cationic residue of an alkanolamine such as triethanolamine, or lysine. , Arginine, and other basic amino acid cationic residues.

Representative examples of the compound of the formula (I) used in the present invention include mono (coconut oil fatty acid diglycolamide) phosphate triethanolamine and di (coconut oil fatty acid diglycolamide) phosphate triethanolamine. Ethanolamine, sodium mono (lauric acid diglycolamide) phosphate, sodium di (lauric acid diglycolamide) phosphate, mono (myristate diglycolamide) phosphate triethanolamine, di (myristate diglycolamide) phosphorus Examples thereof include acid triethanolamine, mono (diglycolamide stearate) ammonium phosphate, and di (diglycolamide stearate) ammonium phosphate.

In the method of the present invention, the reaction between the fatty acid ester and diglycolamine is carried out using a metal alkoxide such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide and the like, preferably at 90 to 180 ° C. Performed at temperature. This reaction is carried out while distilling off the generated alcohol, more preferably while distilling off the alcohol formed under reduced pressure.

Examples of the phosphorylating agent used in the method of the present invention include phosphorus oxychloride, phosphorus pentoxide, polyphosphoric acid and orthophosphoric acid.

There is no particular limitation on the method and conditions of the phosphoric acid esterification reaction in the method of the present invention, and any known method may be used according to the cognitive conditions. Mono (fatty acid diglycolamide) phosphoric acid ester may be used. In the case of production, phosphorus oxychloride is used as a phosphorylating agent in 1 to 3 moles with respect to the fatty acid diglycolamide, and the reaction temperature is −.
It is preferably carried out at 20 to 50 ° C or lower. In the case of producing di (fatty acid diglycol amide) phosphate, phosphorus pentoxide is used as a phosphorylating agent in an amount of 0.25 to 2 times the molar amount of the fatty acid diglycol amide, and the reaction temperature is 0 to 80 ° C. It is preferable to carry out. In the reaction using phosphorus pentoxide, a mixture of monoester and diester is often produced.

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

When orthophosphoric acid generated from the phosphorylating agent used in excess after the reaction of phosphoric acid esterification is inconvenient, it is extracted from the reaction system once with a solvent, and then water is added to the reaction product to separate it. It can be easily removed by washing with a liquid.

In the detergent composition of the present invention, the formula (I)
The content of the component (A) comprising at least one of the fatty acid diglycol amide phosphate ester and its salt is
The amount is preferably 0.05 to 40% by weight, more preferably 0.1 to 30% by weight.

In the detergent composition of the present invention, the formula (I)
In addition to the component (A) consisting of the fatty acid diglycolamide phosphoric acid ester and its salt, the non-ionic surfactant (Ba) and / or the anionic surfactant (Bb) and / or the amphoteric interface as the combined component (B) Activator (B
By containing c), the foaming power can be further improved without impairing the performance and stability of (1) nonionic surfactant, anionic surfactant, and amphoteric surfactant, and (2) ) The detergency of the fatty acid diglycolamide phosphoric acid ester of the formula (I) and its salt can be further enhanced, and the viscosity of the (3) detergent composition can be easily adjusted. Furthermore, by using the component (B) together, the foam quality becomes creamy, and it is possible to obtain a cleaning agent which is free from the feeling of sliminess and tingling during rinsing and has an excellent feeling of use. Furthermore, the effect of alleviating the irritation of the component (B) itself on the skin, hair and eye mucous membranes by using the component (A) together.

In the detergent composition of the present invention, as the nonionic surfactant compound used as the component (Ba) used in combination with the component (A), fatty acid diethanolamide such as coconut oil fatty acid diethanolamide and lauric acid diethanolamide, Coconut oil fatty acid monoethanolamide, fatty acid monoethanolamide such as lauric acid monoethanolamide, polyoxyethylene (2) coconut oil fatty acid monoethanolamide, polyoxyethylene (5) lauric acid monoethanolamide and other polyoxyethylene fatty acid mono Ethanolamide, fatty acid diglycolamide such as lauric acid diglycolamide, fatty acid isopropanolamide such as lauric acid isopropanolamide, fatty acid ester, alkyl ester such as lauryl dimethylamine oxide Amine oxide, POE higher alcohol ether, POE alkylphenyl ethers, such as alkyl glucosides, such as decyl glucoside.

In the detergent composition of the present invention, as the anionic surfactant used as the combined component (Bb), fatty acid soaps such as sodium laurate and triethanolamine laurate, alkylbenzene sulfonates, α-olefins. Sulfonates, sodium lauryl sulphate, lauryl sulphates such as triethanolamine lauryl sulphate, triethanol monododecyl phosphate, phosphate ester salts such as sodium polyoxyethylene dodecyl ether phosphate, sodium cocoyl methyl taurine, sodium lauroyl methyl taurine Acyl methyl taurine salts such as, Acyl isethionates such as sodium lauroyl isethionate, Disodium lauryl sulfosuccinate, POE (1-4) disodium lauryl sulfosuccinate, Polyoxyethylene (5) monoethanolamide sulfosuccinate disodium lauric acid,
Oleic acid amides Sulfosuccinic acid type surfactants such as disodium sulfosuccinate, alkyl ether carboxylates, polyoxyethylene (3) coconut oil fatty acid amide ethers Amide ether sulfates such as sodium sulfate, cellulose derivatives such as carboxymethyl cellulose, cocoyl N-acyl sarcosine salts such as sarcosine sodium, lauroyl sarcosine sodium, 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, 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, N-lauroyl glutamate triethanol. N-acylglutamates such as amines, sodium N-cocoyl glutamate, triethanolamine N-cocoyl glutamate, 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- (2-hydroxyethyl) lauric acid amide] ethyl} glycine , N- {2- [N- (2
Examples include amidecarboxylic acid type surfactants such as -hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine.

Examples of the amphoteric surfactant compound used as the component (Bc) of the detergent of the present invention include alkyl betaine type amphoteric surfactants such as lauryl betaine, amide betaine type amphoteric surfactants such as lauroyl amidopropyl betaine, Imidazoline-type amphoteric surfactants such as 2-alkyl-N-carboxymethylimidazolinium betaines and 2-alkyl-N-carboxyethylimidazolinium betaines, alkylsulfobetaine-type amphoteric surfactants, coconut oil fatty acid amide dimethylhydroxy Amidosulfobetaine type amphoteric surfactants such as propylsulfobetaine and the like can be mentioned.

In the detergent composition of the present invention, the component (A) consisting of the fatty acid diglycolamide phosphoric acid ester of the formula (I) or its salt and the nonionic surfactant (B).
The blending ratio by weight with the combined component (B) consisting of a) and / or the anionic surfactant (Bb) and / or the amphoteric surfactant (Bc) is preferably 9: 1 to 1: 9. The total content of the component (A) and the component (B) in the detergent composition is preferably 0.1% (weight) or more. When the compounding ratio of the components (A) and (B) is out of the above range, there are disadvantages that the foaming power and detergency of the resulting composition are insufficient and the slimy feeling is high. If the total content of A) and (B) is less than 0.1%, the effect may not be sufficiently exhibited.

Further, the following additional components can be added to the detergent composition of the present invention as required. Quaternary ammonium salt type cationic surfactants such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cationized polymers, and / or cationized guar gum.

If desired, the following additional components can be added to the detergent composition of the present invention. Polyhydric alcohols such as glycerin, propylene glycol, 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, Water-soluble polymer substances such as elastin chondroitin sulfate, dermatan, fibronectin, ceramides, etc., cell activating agents such as aloe extract, placenta extracted Eski, allantoin,
Anti-inflammatory agents such as glycyrrhizinate, edetate, pyrophosphate, hexametaphosphate, chelating agents such as citric acid, malic acid, gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate Acid salt, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanite, benzalkonium chloride, hinokitiol, preservatives such as resorcin, bactericide, dibutylhydroxytoluene, butyl Hydroxyanisole, propyl gallate,
Antioxidants such as ascorbic acid, fragrances, and / or pigments.

When the detergent of the present invention is used as a shampoo, it is generally in a liquid or paste (gel) state, and its appearance is transparent, pearly, or opalescent. However, it is not limited to these properties. In order to produce the detergent of the present invention, a conventionally recognized compounding method may be used.

Further, the use of the detergent composition of the present invention is not limited, but typical examples thereof include kitchen detergents, hard surface cleaners, facial cleansers, cleansing foams, shampoos, body shampoos and the like. .

[0035]

EXAMPLES The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.

Example 1 (Production of compound of formula (I)) To 214 g of methyl laurate, 10 parts of diglycolamine were added.
6 g and 2 g of sodium methoxide were added, and the reaction product was heated and stirred while distilling off the produced methanol under reduced pressure (20 mmHg, 140 ° C., 5 hours) to prepare 290 g of lauric acid diglycolamide. Of this compound
¹ H-NMR (250 MHz, CDCl ₃ ) analysis was performed, but unreacted raw materials and by-products such as methyl laurate, diglycolamine, lauric acid, and N, O-dilauroyl-diglycolamine were not detected.

The lauric acid diglycolamide 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 phosphoric acid esterification reaction was performed 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. 370 g of dilauramide dilauramide phosphate was obtained. This was neutralized with an aqueous sodium hydroxide solution to synthesize sodium diglycolamide laurate phosphate (anionic active ingredient: 30%).

The ¹ H-NMR and ³¹ P-NMR analysis results were as follows. ^{1 H-NMR (250MHz, D} 2 O) 0.88ppm (3H, t, -CH 3) 1.29ppm (16H, br, -CH 2 -) 1.60ppm (2H, t, -C H 2 -CH _{2 -CO-) 2.26ppm (2H, t} , -CH 2 -CO-) 3.40ppm (2H, t, -NH-C H 2 -) 3.67ppm (2H, t, -NH-CH 2 - _{C H 2 -) 3.71ppm (2H} , t, -C H 2 -CH 2 -OP) 3.91ppm (2H, t, -CH 2 -OP) 31 P-NMR (101MHz, D 2 O, internal standard _{: H 3 PO 4) 0.96ppm (} -10.99ppm not detected)

From the above results, it was confirmed that the obtained phosphoric acid ester does not contain phosphoric acid diester and is only sodium mono (lauric acid diglycolamide) phosphoric acid.

Example 2 (Production of Compound of Formula (I)) Coconut oil fatty acid (C ₆ -C ₂₂ ) was methyl-esterified by a conventional method to 119 g of palm oil fatty acid methyl ester, 53 g of diglycolamine and sodium were added. Methoxide 0.5
g was added, and the mixture was heated and stirred while distilling methanol off under reduced pressure (20 mmHg, 120 ° C., 2 hours) to synthesize coconut oil fatty acid glycolamide. ¹ H-NMR (2
50 MHz, CDCl ₃ ) analysis was carried out, but coconut oil fatty acid methyl, diglycolamine, coconut oil fatty acid, N, O-
Unreacted raw materials and by-products such as dicocoyl-diglycolamine were not detected.

The obtained coconut oil fatty acid diglycolamide was dissolved in chloroform, and this solution was mixed with phosphorus pentoxide 71
g was added dropwise to the slurry obtained by dispersing it in hexane. After completion of the dropping, the reaction mixture was stirred at 60 ° C. for 5 hours to perform phosphoric acid esterification.

After completion of the reaction, 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 170 g of coconut oil fatty acid diglycolamide phosphate ester. This was neutralized with an aqueous potassium hydroxide solution to synthesize potassium coconut oil fatty acid diglycolamide phosphate (anionic active ingredient: 30%).

The analysis results of ¹ H-NMR and ³¹ P-NMR are as follows. ^{1 H-NMR (250MHz, D} 2 O) 0.88ppm (3H, t, -CH 3) 1.29ppm (16H, br, -CH 2 -) 1.60ppm (2H, t, -C H 2 -CH _{2 -CO-) 2.26ppm (2H, t} , -CH 2 -CO-) 3.40ppm (2H, t, -NH-C H 2 -) 3.67ppm (2H, t, -NH-CH 2 - _{C H 2 -) 3.73ppm (2H} , t, -C H 2 -CH 2 -OP) 3.95ppm (2H, t, -CH 2 -OP) 31 P-NMR (101MHz, D 2 O, internal standard _{: H 3 PO 4) -10.99ppm:} 0.95ppm = 3: 7

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 potassium hydroxide was determined. was gotten. Phosphoric acid monoester: 68% by weight Phosphoric acid diester: 31% by weight Orthophosphoric acid: 1%

Example 3 (Preparation of compound of formula (I)) To 297 g of methyl oleate, 10 parts of diglycolamine were added.
6 g and 2 g of sodium methoxide were added, and the resulting methanol was distilled off under reduced pressure while stirring with heating (20 mmH
g, 140 ° C., 2 hours), and 371 g of oleic acid diglycolamide was prepared. About this reaction product, ¹ H-
NMR (250 MHz, CDCl ₃ ) analysis was performed, which showed that methyl oleate, diglycolamine, oleic acid,
No unreacted raw materials and by-products such as N, O-dioleyl-diglycolamine were detected.

The obtained oleic acid diglycolamide was dissolved in chloroform, cooled to 5 ° C., and 230 g of oxychlorophosphoric acid was added dropwise thereto over 1 hour while keeping the temperature at 10 ° C. or lower. Then, the phosphoric acid esterification reaction was performed at room temperature for 2 hours.

After completion of the reaction, hydrogen chloride generated, unreacted phosphorus oxychloride and chloroform were removed under reduced pressure to obtain 450 g of oleic acid diglycolamide phosphoric acid ester. This was neutralized with a triethanolamine aqueous solution to synthesize oleic acid diglycolamide phosphate triethanolamine (anionic active ingredient: 30%). ³¹ PN
MR analysis (101MHz, D ₂ O, internal standard: H ₃ PO
₄ ) detected only 0.96ppm signal,
Since -10.99 ppm was not detected, the obtained phosphoric acid esterification product did not contain phosphoric acid diester, and thus mono (oleic acid diglycolamide)
It was confirmed to be only triethanolamine phosphate.

Comparative Example 1 (mono (polyoxyethylene (1
E. O. ) Lauric acid monoethanolamide ) Synthesis of sodium phosphate ester) 214 g of methyl laurate, monoethanolamine 6
2 g and caustic soda 0.4 g were added, and the mixture was heated and stirred while distilling methanol off under reduced pressure (20 mmHg, 90 ° C., 1
Time) Lauric acid monoethanolamide was synthesized. To this, 44 g of ethylene oxide was added and reacted in a pressure vessel at 1.5 kg / cm ² and 140 ° C. for 110 minutes to prepare polyoxyethylene (1EO) lauric acid monoethanolamide.

230 g of oxychlorophosphoric acid was added dropwise thereto while maintaining the temperature at 10 ° C. Then, the mixture was reacted at room temperature for 2 hours to form a phosphoric ester.

After completion of the reaction, hydrogen chloride generated, unreacted phosphorus oxychloride and chloroform were removed under reduced pressure to obtain 370 g of polyoxyethylene (1 EO) lauric acid monoethanolamide phosphate ester. This was neutralized with an aqueous sodium hydroxide solution to synthesize polyoxyethylene lauric acid sodium monoethanolamide phosphate (anionic active ingredient: 30%).

³¹ P-NMR analysis (101 MHz, D ₂ O,
With the internal standard: H ₃ PO ₄ ), only the signal of 0.96 ppm was detected and the signal of −10.99 ppm was not detected. Therefore, the obtained phosphoric ester did not contain diester, (Polyoxyethylene (1E.
O. ) Lauric acid monoethanolamide) It was confirmed to be sodium phosphate ester only.

Comparative Example 2 (mono (lauric acid monoethanol
Luamide) Synthesis of sodium phosphate ester) 243 g of lauric acid monoethanolamide was dissolved in chloroform and cooled to 5 ° C., and 230 g of phosphorus oxychloride was added dropwise thereto over 1 hour while keeping the temperature at 10 ° C. or lower. . Then, it was made to react at room temperature for 5 hours to form a phosphoric acid ester.

After completion of the reaction, hydrogen chloride generated, unreacted phosphorus oxychloride and chloroform were removed under reduced pressure to give 323 g of lauric acid monoethanolamide phosphate ester.
Got This was neutralized with an aqueous sodium hydroxide solution to synthesize sodium lauric acid monoethanolamide phosphate (anionic active ingredient: 30%). This product changed to a brown opaque paste upon standing.

Preparation of Detergent Composition Various detergent compositions were prepared using the above Examples 1 to 3, Comparative Examples 1 and 2, and the following comparative control commercial products 1 and 2. Comparative Control Product 1: Monododecyl Phosphate Sodium Comparative Control Product 2: Polyoxyethylene (6) Coconut Oil Fatty Acid Monoethanolamide Phosphate Ester

Table 1 shows the distribution of the number of oxyethylene groups (n) in the reaction products (products) of Example 1 and Comparative Examples 1 and 2, and Comparative Control Product 2. In that analysis method,
A 2N-NaOH aqueous solution was added to the sample and stirred overnight at room temperature to hydrolyze only the phosphate ester bond, and the liberated organic layer was extracted with ethyl acetate. The extract was subjected to normal phase system as shown below. It was analyzed by HPLC.

Analytical condition column: LiChrosorb 5 Diol (4.6
φ × 250 mm) Eluent: n-hexane / ethanol = 86/14 Flow rate: 1.0 ml / min Temperature: 40 ° C. Detection: UV220 nm

[0058]

[Table 1]

[0059] In each of Examples 4-13 and Comparative Examples 3-10 Examples 4-13 and Comparative Examples 3-10,
The cleaning agents having the compositions shown in Tables 2 and 3 were prepared. The obtained product was subjected to the following foaming power, detergency test, foam creamy test, sensory test, skin irritation test, and protein denaturation test.

These test methods were performed as follows. 1) Foaming power test The test cleaning agent was diluted with distilled water so that the content of the active agent was 0.2%, and the foaming power of the obtained cleaning agent aqueous solution was measured by JI.
It was measured by the method described in S standard K3362. The evaluation criteria were set as follows. ∘: Very good foaming, foaming power of 200 mm or more ○: Good foaming, foaming power of 170 mm or more, less than 200 mm △ ... Normal foaming, foaming power of 130 mm or more, less than 170 mm × ... Poor foaming, foaming power of 130 mm Less than

2) Detergency test Beef tallow was supplemented with 0.1% by weight of Sudan III as an indicator.
Was added and 5 g thereof was applied to a porcelain dish (25 cm in diameter). The dish was scrubbed with a sponge impregnated with 30 g of a 10 wt% solution of the test detergent, and the washing power was expressed by the number of dishes washed until the beef tallow could no longer be washed from the dish.

3) Creamy property The creamy property of the foam is that the hair is divided into two parts and the left and right parts are divided into three parts.
After the standard sample of g and the test sample were foamed, the creamy property of the foam was evaluated by a sensory test by 20 testers by a two-point comparison method, and statistical processing was performed according to the following criteria to evaluate and evaluate. As the standard sample, a 15% aqueous solution of sodium polyoxyethylene (3EO) alkyl ether sulfate (C ₁₂ / C ₁₃ = 1/1) was used. ◯: 5% significant, test sample preferred Δ: no significant difference ×: 5% significant, standard sample preferred

4) Test for sensory feeling (smoothness) 10 panelists aged 20 to 40 were made to wash their hands and forearms three times with warm water of about 40 ° C. using 5 ml of a sample taken as a bath sponge. The sensory evaluation when rinsed with water was performed according to the following criteria, and the average sensory evaluation value after naturally drying was obtained. Sensory evaluation 4 points: No slimy feeling, refreshing 3 points: Almost no slimy feeling, refreshing 2 points… Slightly slimy, refreshing 1 point… Clearly slimy feeling remains The criteria for evaluation labeling that is not refreshing were set as follows. A: Average value 3.1 to 4.0 A: Average value 2.1 to 3.0 B: Average value 1.1 to 2.0 X: Average value 0 to 1.0

5) Skin irritation (rough hand) test 30 testers in 1% test solution of the test solution 30 times a day
Soak your hand for about 3 minutes, repeat this for 3 days,
The next day, judgment was made according to the following criteria, and the average score was calculated. Sensory evaluation: 3 points: Hand was not rough 2 points: Hand was slightly rough 1 point: Rough evaluation The criteria for evaluation display were set as follows. 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 rate test The height of the 220 nm absorption peak of ovalbumin when a sample was added to an ovalbumin pH7 buffer solution at a sample concentration of 1% using aqueous gel filtration high performance liquid chromatography. Was measured, and the denaturation rate of ovalbumin was calculated from the following formula. Denaturation rate (%) = [(Ho-Hs) / Ho] × 100 Ho: height of 220 nm absorption peak of ovalbumin Hs: 2 when sample is added to buffer solution of ovalbumin
The standard for evaluating the height of the absorption peak at 20 nm was set as follows. Ovalbumin denaturation rate less than 30% Ovalbumin denaturation rate 30 to 59% △ Ovalbumin denaturation rate 60 to 79% × Ovalbumin denaturation rate 80% or more

The test results are shown in Tables 2 and 3.

[Table 2]

[0067]

[Table 3]

Example 14 A conditioning shampoo having the following composition was prepared and subjected to the same test as in Example 4. Ingredient weight% Reaction product of Example 1 10.0 Lauroylmethyl-β-alanine sodium (30%) 20.0 Cationized guar gum * 1 0.3 Lauric acid diethanolamide 2.0 Glycerin 3.0 Carboxymethyl chitin 0 .2 EDTA 0.1 Adjust caustic soda pH to 6.5 Water balance [Note] * 1: MEYHALL, trademark: JAGUAR
Table 4 shows the C-120 test results.

Example 15 A pearly shampoo having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine (30%) 15.0 Reaction product of Example 2 10.0 N-coconut oil fatty acid acyl-L-glutamic acid monotriethanol Amine (30%) 5.0 Lauroyl methyl taurine sodium (30%) 5.0 Lauric acid diethanolamide 2.0 Coconut oil fatty acid monoethanolamide 1.5 Sodium hyaluronate 0.5 Caustic soda pH 6.0 Methylparaben 0.1 Fragrance Appropriate amount of water The balance test results are shown in Table 4.

Example 16 A face wash having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% N-2-hydroxyethyl-N-2-coconut oil fatty acid Amidoethyl-β-alanine (30%) 60.0 Reaction product of Example 3 20.0 Lauric acid diethanolamide 7.0 Ethylene glycol distearate Ester 2.0 Monoammonium glycyrrhizinate 0.2 Methylparaben 0.1 Citric acid Adjusted to pH = 6.5 Water balance Test results are shown in Table 4.

Example 17 A transparent antidandruff shampoo having the following composition was prepared, and Example 4 was used.
The same test was performed. Ingredient weight% Reaction product of Example 1 15.0 Lauric acid diglycolamide 5.0 5.0 2-Palm oil alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30%) 10.0 Piroctone ola Min 0.7 Sodium hyaluronate 0.1 Methylparaben 0.1 EDTA 0.1 Citric acid pH = 7 Water balance Table 4 shows the test results.

Example 18 A gel shampoo having the following composition was prepared and subjected to the same test as in Example 4. Ingredient wt% Reaction product of Example 1 5.0 Reaction product of Example 3 10.0 Coconut oil fatty acid amide propyl betaine (30%) 30.0 Carboxymethyl chitin 0.1 Methyl paraben 0.1 EDTA 0.1 Table 4 shows the results of the balance water test with citric acid pH = 7.

Example 19 A rinse-incorporating shampoo having the following composition was prepared, and Example 4 was prepared.
The same test was performed. Ingredient wt% Reaction product of Example 2 8 Lauric acid diglycolamide 2 Lauroylmethyl-β-alanine sodium (30%) 20.0 Stearyltrimethylammonium chloride 2.0 Cetyl octoate 0.5 Methylparaben 0.1 EDTA 0 .1 Citric acid pH = 7 Water balance Table 4 shows the test results.

Example 20 A body shampoo having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% Polyoxyethylene (2) Lauric acid monoethanol sodium amide sulfate (26%) 20.0 Reaction product of Example 3 10.0 Lauric acid diglycolamide 5.0 5.0 Lauric acid triethanolamine 7.0 Methylparaben Table 4 shows the results of the 0.1 EDTA 0.1 water balance test.

Example 21 A transparent kitchen detergent having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% Coconut oil fatty acid amide dimethylhydroxypropyl sulfobetaine (30%) 20.0 Reaction product of Example 3 16.2 Polyoxyethylene (2) Coconut oil fatty acid monoethanolamide 3.0 Palm oil fatty acid diethanolamide 6 0.0 Methylparaben 0.1 EDTA 0.1 Water balance Table 4 shows the test results.

Example 22 A shampoo having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% Polyoxyethylene (5) Lauric acid monoethanol amide Disodium sulfosuccinate 5.0 Reaction product of Example 1 5.0 C _14- α Sodium olefinsulfonate 5.0 Oxyalkylene-modified organopolysiloxane (20 % Modification: 20% by weight of polyoxyethylene group) 1.0 Lauric acid diethanolamide 5.0 Methylparaben 0.1 EDTA 0.1 Water balance Table 4 shows the test results.

Example 23 A shampoo having the following composition was prepared and subjected to the same test as in Example 4. Component Weight% Decyl glucoside (1.7) 5.0 Reaction product of Example 1 5.0 Sodium cocoyl isethionate 5.0 Lauric acid diethanolamide 5.0 Methylparaben 0.1 EDTA 0.1 Water balance test results Is shown in Table 4.

Example 24 A shampoo having the following composition was prepared and subjected to the same test as in Example 4. Ingredient wt% Polyoxyethylene (3) lauryl ether sodium sulfate 5.0 Reaction product of Example 1 11.0 Lauryl dimethylamine oxide 4.0 Lauric acid diethanolamide 3.0 Methylparaben 0.1 EDTA 0.1 Water balance The test results are shown in Table 4.

[0079]

[Table 4]

[0080]

According to the present invention, excellent foaming power / cleaning power,
Diglycol amide phosphorus, a fatty acid with a rich amount of foam, is homogeneous and creamy, has a good feeling of use without slickness or tingling during rinsing, has less irritation to the skin and hair, and has excellent product stability. It is possible to produce acid esters and salts thereof, and to provide a detergent composition having the above-mentioned excellent properties, including the product of this method.

Claims (4)

[Claims] 1. The following general formula (I):(However, in the formula (I), R¹ Has 5 to 21 carbon atoms
Straight or branched chain, saturated or unsaturated hydrocarbons
Represents a group, A is R¹ CONHCH₂ CH₂ OCH ₂ CH
₂ Represents a group or M, M is a hydrogen atom, an alkali metal atom
Child, alkaline earth metal atom, ammonium group, alkano
Cationic residues of basic amines or basic amino acids
Represents a cationic residue. ) Fatty acid diglycol
In order to produce a luamidophosphoric acid ester or a salt thereof, the following general formula (II): R¹ COOR (II) (However, in the formula (II), R¹ Is as defined above, and R
Represents a methyl group, an ethyl group, or a propyl group. )so
The fatty acid ester shown and diglycolamine are
Fatty Acid Diglycol Condensed in the Presence of Genus Alkoxide
Lamide is prepared and reacted with a phosphorylating agent to remove fat.
A fatty acid diglycolamide phosphate is prepared, and in the compound of the general formula (I), M is an alkali metal
Atom, alkaline earth metal atom, ammonium group, alkali
Cationic residue of nolamine or basic amino acid
When the residue is a thione residue, the fatty acid diglycol
Midophosphate ester, alkali metal hydroxide, alkali
Rh earth metal hydroxide, ammonia, alkanol amine
Or a neutralizing agent consisting of basic amino acids
Fatty acid diglycol
A method for producing a midophosphoric acid ester salt or a salt thereof. 2. A component (A) obtained by the method according to claim 1 and comprising at least one of fatty acid diglycol amide phosphate ester represented by the general formula (II) and a salt thereof, and at least 1. A cleaning composition comprising a component (Ba) composed of one kind of nonionic surfactant compound. 3. A component (A) comprising at least one of fatty acid diglycol amide phosphate ester represented by the general formula (II) and a salt thereof, which is obtained by the method according to claim 1, and at least 1. A cleaning composition comprising a component (Bb) composed of one kind of anionic surfactant compound. 4. A component (A) comprising at least one fatty acid diglycol amide phosphate ester represented by the general formula (II) and a salt thereof, which is obtained by the method according to claim 1, and at least 1. A cleaning composition comprising a component (Bc) composed of one kind of amphoteric surfactant compound.