JPH09268167A - New beta-alanine derivative, production of the same and cleaning composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound used as a low cost cleaning agent having a low irritation, and excellent in foaming property, cleaning property, rinsing property and feeling in use by reacting iminodipropionic acid with a fatty acid chloride. SOLUTION: This new β-alanine derivative is a compound of formula I [R is a 5-21C alkyl or an alkenyl; M1 , M2 are each H, an alkali (earth) metal, ammonium, a 1-22C alkylammonium, an alkenylammonium, etc.], e.g. N-lauroy- N-carboxyethylβ-alanine, etc. Further, in order to obtain the compound, 0.5-1.5eq fatty acid chloride with iminodipropionic acid are reacted in an aqueous solvent, in the presence of a polar solvent such s acetone as necessary, at 10-60 deg.C for 1-20hr, while neutralizing the generated hydrochloric acid with an alkaline substance such as sodium hydroxide.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a compound represented by the general formula (1):

[0002]

Embedded image (In the formula, R represents a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, and M ₁ and M ₂ are hydrogen atom, alkali metal, alkaline earth metal, ammonium,
Alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridium having 1 to 18 carbon atoms, or basic amino acid or a mixture thereof, wherein M ₁ and M ₂ are the same or different It may be. )

The present invention relates to a novel β-alanine derivative represented by The compound is a useful compound that can be used as a detergent and the like.

[0004]

2. Description of the Related Art Currently, as surfactants used as detergents, acylated amino acid type surfactants, imidazoline type surfactants, alkyl phosphate ester salts, sugar type surfactants such as alkyl glycosides, etc. It has been widely used because it is attracting attention as it is easy to use on the skin. However, it has been pointed out that these surfactants have an excellent feeling in use, but on the other hand, they have insufficient foaming ability and detergency.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel detergent and a detergent composition which are inexpensive and have low irritation, and which are excellent in foaming property, detergency and feeling of use. .

[0006]

Means for Solving the Problems As a result of intensive studies aimed at developing a novel detergent composition, the present inventors have found that an amide type anion having two carboxylic acid groups in the same molecule as ionic groups. It was found that the organic surface-active agent is excellent in foamability, detergency, and feeling in use, and completed the present invention.

That is, the present invention is as follows. . General formula (1)

[0008]

Embedded image (In the formula, R represents a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, and M ₁ and M ₂ are hydrogen atom, alkali metal, alkaline earth metal, ammonium,
Alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridium having 1 to 18 carbon atoms, or basic amino acid or a mixture thereof, wherein M ₁ and M ₂ are the same or different It may be. ) The β-alanine derivative represented by

[0009] A detergent composition containing the described β-alanine derivative. . A method for producing the described β-alanine derivative by reacting iminodipropionic acid with a fatty acid chloride.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1) of the present invention,
R represents a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, and specific examples thereof include
n-pentyl group, n-heptyl group, n-octyl group, n
-Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-pentadecyl group, n
-Heptadecyl group, methylhexadecyl group, ethylpentyl group, heptadecenyl group, etc. are mentioned, and a linear alkyl group having 9 to 13 carbon atoms is preferable.

In the general formula (1) of the present invention, M ₁ and M ₂ are hydrogen atoms, alkali metals, alkaline earth metals, ammonium, alkylammonium or alkenylammonium having 1 to 22 carbon atoms, and 1 to 1 carbon atoms. 18 alkyl- or alkenyl-substituted pyridium, or a basic amino acid or a mixture thereof is shown, and specifically, a hydrogen atom, sodium, potassium, magnesium,
Examples thereof include calcium, zinc, ammonium, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine and propylenediamine.

Β represented by the general formula (1) in the present invention
-Examples of the alanine derivative include N-hexanoyl-
N-carboxyethyl-β-alanine, N-octanoyl-N-carboxyethyl-β-alanine, N-decanoyl-N-carboxyethyl-β-alanine, N-lauroyl-N-carboxyethyl-β-alanine, N- Tetradecanoyl-N-hydroxyethyl-β-alanine, N-hexadecanoyl-N-carboxyethyl-β
-Alanine, N-octadecanoyl-N-carboxyethyl-β-alanine, N-isostearoyl-N-carboxyethyl-β-alanine, N-oleoyl-N-carboxyethyl-β-alanine and salts thereof Furthermore, examples thereof include, but are not limited to, a mixture thereof.

The production method according to the present invention is not particularly limited, but for example, it can be produced inexpensively and easily by reacting iminodipropionic acid with fatty acid chloride. Iminodipropionic acid can be produced by adding acrylonitrile to β-alanine and hydrolyzing a cyano group, or by adding two molecules of acrylonitrile to ammonia and hydrolyzing a cyano group.

The addition reaction of β-alanine and acrylonitrile is carried out by reacting 0.5 to 10 equivalents of acrylonitrile with respect to β-alanine in water at 10 to 100 ° C. for 1 to 20 hours. Outside this range, the residual of the raw materials and the reaction of addition of two molecules of acrylonitrile increase, which is not preferable. During the reaction, it is preferable to add acrylonitrile dropwise to the β-alanine aqueous solution because the yield is improved. In the subsequent hydrolysis reaction, the addition reaction product and 1 to 2 equivalents of an alkali metal hydroxide such as NaOH or KOH or an alkaline earth metal hydroxide such as Ca (OH) _{2 with} respect to the cyano group in an aqueous solution are used. The reaction is carried out at 60 to 100 ° C for 1 to 100 hours. Lower (less) than this range results in extremely low hydrolysis rate, and higher (more) than this range is industrially disadvantageous. It is preferable that the by-produced ammonia is sufficiently removed to the outside of the system during the reaction or after the reaction, since a by-product derived from ammonia does not occur in the final product. The iminodipropionic acid thus obtained can be used in the next step as an aqueous solution, although it can be isolated after solvent removal and carried into the next step.

The addition reaction between ammonia and acrylonitrile is carried out by reacting 1 to 20 equivalents of acrylonitrile with respect to ammonia in water at 10 to 120 ° C. for 0.5 to 20 hours. Outside this range, the residual of the raw materials and the addition reaction of one or three molecules of acrylonitrile increase, which is not preferable. During the reaction, it is preferable to add acrylonitrile dropwise to the β-alanine aqueous solution because the yield is improved. In the subsequent hydrolysis reaction, the addition reaction product and 1 to 2 equivalents of an alkali metal hydroxide such as NaOH or KOH or an alkaline earth metal hydroxide such as Ca (OH) _{2 with} respect to the cyano group in an aqueous solution are used. , 1 to 100 at 60 to 100 ° C
It is performed by reacting for a time. Lower (less) than this range results in extremely low hydrolysis rate, and higher (more) than this range is industrially disadvantageous. It is preferable that the by-produced ammonia is sufficiently removed to the outside of the system during the reaction or after the reaction, since a by-product derived from ammonia does not occur in the final product. The iminodipropionic acid thus obtained can be used in the next step as an aqueous solution, although it can be isolated after solvent removal and carried into the next step.

Then, in the acylation reaction of iminodipropionic acid thus obtained with fatty acid chloride, 0.5 to 1.5 equivalents of fatty acid chloride with respect to iminodipropionic acid are necessary in an aqueous solvent. Depending on the presence of a polar solvent such as acetone, methanol, ethanol, isopropanol, formyldimethylamine, N, N-dimethylimidazolidinone at 10 to 60 ° C., hydrochloric acid generated is sodium hydroxide, potassium hydroxide, ammonia, triethylamine. 1-2 while neutralizing with an alkaline substance such as pyridine
It is carried out by reacting for 0 hours. Examples of the fatty acid chloride used include hexanoic acid chloride, octanoic acid chloride, decanoic acid chloride, dodecanoic acid chloride, tetradecanoic acid chloride, hexadecanoic acid chloride, octadecanoic acid chloride, 2-ethylhexanoic acid chloride, isostearic acid chloride, and olein. Examples thereof include fatty acid chloride having a single composition such as acid chloride, coconut oil fatty acid chloride, and fatty acid chloride having a mixed composition such as beef tallow fatty acid chloride. When the amount of the fatty acid chloride used is less than 0.5 equivalent, the amount of unreacted iminodipropionic acid remains large, and when it is more than 1.5 equivalent, the fatty acid by-product increases. If the reaction temperature is lower than 10 ° C, the reaction rate becomes extremely low, and if it is higher than 60 ° C, the fatty acid by-product increases. The reaction mass can be used as it is, or as a solution after salt exchange by a conventional method, or can be taken out by solvent extraction, crystallization or the like after neutralization with an acidic substance such as hydrochloric acid, sulfuric acid or phosphoric acid. Furthermore, the isolated acid-type β-alanine derivative can be used in the form of salt or adjusted in pH in water.

The detergent composition of the present invention contains the β-alanine derivative represented by the general formula (1), and its content is preferably 0.1 to 99% by weight, more preferably 0.1 to 99% by weight. It is 70% by weight.

The detergent composition of the present invention may be used in combination with the components used in conventional detergents for washing hair, body, dishes, etc. within a range that does not impair the effects of the present invention. Examples of such a combination component include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylbenzene sulfonates, higher fatty acid salts, α-olefin sulfonates, alkyl sulfonates, N-alkylamide alkanol sulfates. Salt, N-alkanoyl ethanolamide sulfate, fatty acid glyceride sulfate, alkyl glyceryl ether sulfate, taurine-based surfactant, sarcosinate-based surfactant, isethionate-based surfactant, N-acylated acidic amino acid-based surfactant And other anionic surfactants, alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants, N-acylation Bisexual Amphoteric surfactants such as mino acid-based surfactants, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, fatty acid monoglycerides, fatty acid sorbitan esters, nonionic surfactants such as alkyl polyglycosides, alkyl trimethyl ammonium chloride, chloride Cationic surfactants such as dialkyldimethylammonium, lanolin ethylsulfate fatty acid aminopropylethyldimethylammonium,
Moisturizers such as glycerin, propylene glycol and ethylene glycol, and other thickeners, bactericides, preservatives, emulsifiers, polymer compounds, fragrances and the like can be mentioned.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to examples and formulation examples, but the present invention is not limited thereto.

Example 1 Synthesis of iminodipropionic acid 89.1 g (1.00 mol) of β-alanine and 49.9
% NaOH aqueous solution 80.2 g and water 250 g were charged, and acrylonitrile 5 was added while stirring and maintaining the internal temperature at 30 ° C.
5.7 g (1.05 mol) was added dropwise over 1 hour, and the mixture was aged at the same temperature for 0.5 hour. Next, this reaction mass is heated to 80 ° C.
The temperature was raised to 84.2 g (1.0%) of 49.9% NaOH water.
(5 mol) was added dropwise over 1 hour. Further, ammonia was removed from the system while aging under reflux for 2 hours. As a result of analysis by high performance liquid chromatography, production of 0.88 mol of iminodipropionic acid was confirmed. The reaction product is neutralized with concentrated hydrochloric acid, dehydrated, and added with 260 g of methanol,
The mixture was stirred at 0 ° C for 0.5 hours. Insoluble matter is filtered off at the same temperature,
After adding a small amount of water and acetone, the mixture was cooled to 10 ° C. The resulting precipitate was collected by filtration and dried to give 103.6 g of a white powder of iminodipropionic acid (purity: 99.8 wt).
%) Was obtained. N-lauroyl-N-carboxyethyl-β-alanine
Synthesis of iminodipropionic acid 16.1 g (0.
(10 mol) and 25 g of water were charged, and the internal temperature was 40 ° C. under stirring.
While maintaining the pH of the system at 11 to 13 with 30% KOH water, 36.2 g of lauryl chloride (0.12 mo
1) was added dropwise in 10 hours. After neutralizing with concentrated hydrochloric acid, 150 g of methanol was added and the temperature was raised to 60 ° C. to dissolve it. 10
The precipitate formed by cooling to ℃ was filtered to give 45.0
g was obtained. Furthermore, 90% acetone water 10
0 g was added and the mixture was stirred at 30 ° C. for 0.5 hours. The crystals were collected by filtration and dried, and 20.8 g of crystals (melting point: 133.5 ° C to 134.5).
° C). It was confirmed by NMR, GC-MS, and IR that the product was N-lauroyl-N-carboxyethyl-β-alanine. ¹ H-NMR δ (CDCl ₃ , 400 MHz); 0.9 ppm, t, 3H, 1.2 ppm, br, 16H, 1.5 ppm, br, 2H, 2.27 ppm, t, 2H, 2.33 ppm, t, 2H, 2.38ppm, t, 2H, 3.38ppm, t, 2H, 3.47ppm, t, 2H, MS (m / z); 342 (M +), IRν max (KBr) cm -1; 1724cm - ¹ , (O-C = O) 1607 cm ^-1 , (RCON)

Formulation Example 1 A shampoo having the following composition was prepared. The obtained shampoo had less irritation, was excellent in foamability and detergency, and had good defoaming during rinsing, and remained moist after washing hair. 30% N-lauroyl-N-carboxyethyl-β-45.0 wt% alanine triethanolamine amine salt aqueous solution Lauroyl glutamic acid polyoxyethylene octyl 2.0 wt% dodecyl ether diester: 2EO polyoxyethylene hydrogenated castor oil 3.0 wt% coconut Oil fatty acid diethanolamide 5.0 wt% Phenoxyethanol 0.7 wt% Cationized cellulose 1.0 wt% Purified water balance

[0022]

According to the present invention, it is inexpensive and hypoallergenic,
It was possible to provide a novel detergent composition which is excellent in foamability, detergency, rinsability and usability.

Claims (3)

[Claims] 1. A β-alanine derivative represented by the following formula (1): Embedded image (In the formula, R represents a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, and M ₁ and M ₂ are hydrogen atom, alkali metal, alkaline earth metal, ammonium,
Alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridium having 1 to 18 carbon atoms, or basic amino acid or a mixture thereof, wherein M ₁ and M ₂ are the same or different It may be. ) 2. A detergent composition containing the β-alanine derivative according to claim 1. 3. The method for producing a β-alanine derivative according to claim 1, wherein iminodipropionic acid is reacted with fatty acid chloride.