JPH1135537A - Method for producing amidoaminomonocarboxylic acid compound and surfactant composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an amidoaminomonocarboxylic acid compound via a cyclic amidine obtained by a reaction of an aliphatic nitrile and a diamine as an intermediate, thereby producing diamide, polyacrylic acid and the like as impurities. Provided is a method for producing a high-purity amidoaminomonocarboxylic acid compound containing no amide aminomonocarboxylic acid compound. SOLUTION: A cyclic amidine compound is obtained by reacting an aliphatic nitrile and a diamine in a molar ratio of 1 to 1 in the presence or absence of a catalyst while removing ammonia. Thereafter, hydrolysis is carried out in the presence or absence of an alkali catalyst to form an amidoamine compound. Then, (1) halocarboxylic acid, (2) lower alcohol ester of acrylic acid, or (3) acrylonitrile is added to the cyclic amidine compound. To obtain an amidoaminomonocarboxylic acid compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amidoaminomonocarboxylic acid compound, and a surfactant composition and a detergent composition containing the amidoaminomonocarboxylic acid compound obtained thereby.

[0002]

2. Description of the Related Art Recently, amidoamine surfactants have been used as mild surfactants. Amidoaminomonocarboxylic acid compounds represented by the following general formula (I) are classified as amidoamine-based amphoteric activators and described in U.S. Pat. No. 2,993,918 and Japanese Patent Publication No. 60-4871. RCONH (CH ₂ ) _m NH (CH ₂ ) _n COOM (I) (wherein, R represents a linear or branched alkyl or alkenyl group having 5 to 21 carbon atoms; m represents 2 to 8,
n shows the integer of 1-2. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. )

In US Pat. No. 2,993,918, the general formula (I
II) RCONH (CH ₂ ) _m NH ₂ (III) (wherein R and m are the same as those of the general formula (I)) as an intermediate, followed by reaction with monohaloacetic acid A method is described. However, this amidoamine is obtained by the reaction of a fatty acid and a diamine, and in this reaction, as an impurity, a compound represented by the general formula (IV) RCONH (CH ₂ ) _m NHCOR (IV) (where R and m are the general formula (I) This is the same as that described above.) When a large amount of diamide is generated, when formulated into a detergent, etc., a high melting point diamide is deposited in the product, and the cleaning interface such as foaming power and detergency is used. The disadvantage is that the basic functions required for the activator are not sufficient.

Japanese Patent Publication No. 60-4871 discloses a method in which an acrylic acid is reacted with an amidoamine represented by the general formula (III), and the remaining unreacted acrylic acid is polymerized into polyacrylic acid. Are listed. However, although this composition has a mild effect on the skin, it contains polyacrylic acid and a polymerization initiator as impurities, so when formulated into a detergent or the like, the product viscosity is too high, foaming power, detergency, etc. However, there is a disadvantage that the basic function required for the above-mentioned cleaning surfactant is not sufficient.

The amidoamine represented by the general formula (III) can also be obtained by reacting a fatty acid ester with a diamine as described in JP-A-4-257552. However, also in this case, there is a disadvantage that a large amount of the diamide represented by the general formula (IV) is generated.

Therefore, there is a strong demand for the development of a method for producing an amidoaminomonocarboxylic acid compound which does not contain diamide, polyacrylic acid or the like as impurities.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high-purity amidoaminomonocarboxylic acid compound containing no diamide or polyacrylic acid as impurities.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a production method using a specific cyclic amidine compound as an intermediate achieves the object of the present invention. Thus, the present invention has been completed.

That is, the present invention provides a compound represented by the following general formula (I): RCONH (CH ₂ ) _m NH (CH ₂ ) _n COOM (I) Represents an alkyl or alkenyl group having an atom, m is 2 to 8,
n shows the integer of 1-2. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. ) Wherein the cyclic amidine obtained by the reaction of the aliphatic nitrile and the diamine is ring-opened in the presence of water to obtain (1) a halocarboxylic acid or a salt thereof, 2) A method characterized by reacting with a lower alcohol ester of acrylic acid or (3) acrylonitrile.

As the aliphatic nitrile used in the production of cyclic amidine in the present invention, an aliphatic nitrile represented by the general formula (V) RCN (V) is preferable. And a hydrocarbon group having 11 to 21 carbon atoms is suitable. The hydrocarbon group R 1 is linear or branched, saturated or unsaturated, and may optionally include substituents such as hydroxyl groups. Preferably, R is a hydrocarbon group derived from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, coconut fatty acid, tallow fatty acid. This aliphatic nitrile is produced by reacting the corresponding fatty acid as a raw material with ammonia.

As the diamine used in the production of the cyclic amidine in the present invention, a diamine represented by the following general formula (VI) H ₂ N (CH ₂ ) _m NH ₂ (VI) is preferable. m is an integer of 2 to 8. Preferably ethylene diamine, propylene diamine, 1,4-diaminobutane,
Hexamethylenediamine and the like.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Amidoaminomonocarboxylic acid compounds represented by the general formula (I) can be prepared by the following three production methods <1> and <2>.
Or it can be manufactured in <3>.

Production method <1> In the case where a halocarboxylic acid is used in the amidoaminomonocarboxylic acid compound represented by the general formula (I), the production method of the present invention is specifically represented by the following formula. .

[0014]

Embedded image (In the formula, R, m, n, and M are the same as those in the general formula (I). X is a halogen atom.)

An aliphatic nitrile represented by the general formula (V) and a diamine represented by the general formula (VI) are prepared by mixing an aliphatic nitrile: diamine = 1: 1 to 3 (molar ratio) in the presence of a catalyst. Alternatively, the cyclic amidine compound represented by the general formula (II) used in the present invention can be obtained by performing the reaction while removing ammonia without using a catalyst. Here, catalysts that can be preferably used include Ti (OCH (CH ₃ ) ₂ ) ₄ , TiO ₂ , TiCl ₄ , T
i (OH) _{4 and the} like. When a catalyst is used, it is preferably added in an amount of 0.1 to 5.0% by weight based on the aliphatic nitrile. It is preferable to use water as the solvent, and the compounding amount is preferably 10 to 300% by weight based on the aliphatic nitrile. The reaction conditions are 130 to
It is preferred to carry out the reaction at 250 ° C.

Thereafter, hydrolysis is carried out in the presence or absence of an alkali catalyst to give an amidoamine compound represented by the general formula (III), followed by a halocarboxylic acid represented by the general formula (VII) or a salt thereof. Is reacted in an amount of 1 to 3 moles, preferably 1 mole or more and less than 1.3 moles with respect to the cyclic amidine compound to obtain a compound of the general formula (I-1)
The amide aminomonocarboxylic acid compound represented by is obtained. Here, examples of the halocarboxylic acid include chloroacetic acid, sodium chloroacetate, chloropropionic acid, and sodium chloropropionate. Of these, chloroacetic acid or sodium chloroacetate is preferable. Examples of the alkali catalyst that can be preferably used include sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. The amount of water used for the hydrolysis is 5 to the cyclic amidine compound.
A molar amount of up to 20 times is preferred. It is preferable to use alcohols or a mixture of alcohols and water as the solvent. The reaction conditions are as follows: after stirring the cyclic amidine compound and the solvent at 40 to 90 ° C. for 1 to 4 hours, adding a halocarboxylic acid or a salt thereof, and adding an alkaline aqueous solution to the solution at pH 9;
After dropping over 2-6 hours while adjusting to -10, 1-4
It is preferable to age for a while.

Production method <2> Further, the amidoaminomonopropionic acid compound represented by the following general formula (I-2) is composed of an amidoamine compound (III) and an acrylic acid lower alcohol ester represented by the general formula (VIII) Can also be produced by an addition reaction with The manufacturing method is specifically shown by the following formula.

[0018]

Embedded image (In the formula, R, m, and M are the same as those in formula (I). Y represents an alkyl group having 1 to 5 carbon atoms.)

The cyclic amidine compound (II) and the amidoamine compound (III) were obtained by the method described in the production method <1>. Further, the lower alcohol ester of acrylic acid represented by the general formula (VIII) is added to the amidoamine compound represented by the general formula (III) in a molar amount of 1 to 3 times, preferably 1 to 1 times the molar amount of the cyclic amidine compound. 3
The reaction is carried out in an amount of less than twice the molar amount to obtain an amidoaminopropionic acid ester represented by the general formula (IX), and then saponified with an alkali to obtain an amidoaminomonopropionic acid represented by the general formula (I-2) A compound is obtained. Here, as the acrylic acid lower alcohol ester, ethyl acrylate, methyl acrylate, propyl acrylate, butyl acrylate and the like can be mentioned, and among them, ethyl acrylate or methyl acrylate is preferable.
The amount of water used for the hydrolysis is preferably 5 to 20 times the molar amount of the cyclic amidine compound. As the solvent, it is preferable to use alcohols or a mixture of alcohols and water. The reaction conditions are as follows: the cyclic amidine compound and the solvent are stirred at 40 to 90 ° C. for 1 to 4 hours, and then a lower alcohol ester of acrylic acid diluted with alcohols or the like is added dropwise over 2 to 6 hours, and 1 to 4 hours after the addition. Aging is preferred.

Production method <3> The amidoaminomonopropionic acid compound represented by the following general formula (I-2) can also be produced by an addition reaction between an amidoamine compound (III) and acrylonitrile (X). it can. The manufacturing method is specifically shown by the following formula.

[0021]

Embedded image (In the formula, R, m, and M are the same as those in the general formula (I).)

The cyclic amidine compound (II) and the amidoamine compound (III) were obtained by the method described in the production method <1>. Further, the acrylonitrile represented by the general formula (X) is added to the amidoamine compound represented by the general formula (III) in an amount of 1 to 3 moles, preferably 1 mole or more and less than 1.3 moles of the cyclic amidine compound. To give the amidoaminopropionitrile represented by the general formula (XI), followed by hydrolysis while removing ammonia with an alkali to give the amidoaminopropionyl represented by the general formula (I-2) A monopropionic acid compound is obtained. Here, the amount of water used for hydrolysis is preferably 5 to 20 times the molar amount of the cyclic amidine compound.
As the solvent, it is preferable to use alcohols or a mixture of alcohols and water. As reaction conditions,
The solvent is added to the cyclic amidine compound at 40 to 90 ° C.
After hydrolysis for 6 hours, acrylonitrile was added and the reaction was carried out for 2 to 6 hours.
Preferably, the nitrile is hydrolyzed by dropping over a period of up to 6 hours.

The thus obtained general formula (I)
The amidoaminomonocarboxylic acid compound represented by the formula (1) is produced as an inorganic salt and / or an organic salt as a by-product at the time of production, but is used as it is, or is used after removal and purification by an electrodialysis method, an ion exchange method or the like as necessary. You can also.

According to the production method of the present invention described above, the amidoaminomonocarboxylic acid compound represented by the general formula (I) and the general formula (XII) RCONH (CH ₂ ) _m NH (CH ₂ ) _s CH ( COOM) ₂ (XII) (wherein, R represents a linear or branched alkyl or alkenyl group having 5 to 21 carbon atoms; m represents 2 to 8,
s shows the integer of 0-1. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. ) With the amidoaminodicarboxylic acid compound represented by the formula: amidoaminomonocarboxylic acid compound / amidoaminodicarboxylic acid compound = 60/40 to 99.9 / 0.1, preferably 70 /
30-99.9 / 0.1, more preferably 90/10
A high-purity purified product containing 99.7 / 0.3 (weight ratio) and containing less than 1% by weight of unreacted amidoamine is obtained. Therefore, the amidoaminomonocarboxylic acid compound obtained by the production method of the present invention does not contain impurities such as diamide and polyacrylic acid, and is a compound that has achieved its original purpose, and therefore is used for various purposes. Very suitable as activator.

[0025] Above all, body cleaners, kitchen cleaners,
Use of various cleaning agents, such as cleaning agents for hard surfaces, can positively utilize the advantages of amidoaminomonocarboxylic acid compounds, such as high detergency and high mildness (low skin irritation). Very preferred.

When used as a detergent, either a single agent or a mixture with another surfactant can be suitably used. When mixed, alkyl sulfate, alkyl ethoxy sulfate, α-sulfofatty acid ester salt, alkylbenzene sulfonate, soap, alkyl ether carboxylate, alkyl sulfosuccinate, alkyl phosphate ester, alkyl alaninate, Anionic surfactants such as amino acid derivatives such as alkyl taurates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, fatty acid alkanolamides, alkyl polyglucosides, short-chain alkyl glucoside long-chain fatty acid esters, alkyl methyl Nonionic surfactants represented by glucamide, sucrose fatty acid esters, etc .; alkylamine oxides, alkylcarbobetaines, alkylamidoalkylcarbobetaines, alkylsulfobetaines , Alkyl hydroxy sulfobetaine, alkyl imidazoline or amphoteric surfactants represented by the derivatives and the like. Of these, anionic surfactants are particularly preferred in terms of foaming power and detergency. The compounding ratio is preferably amidoaminocarboxylic acid compound: surfactant = 1: 99 to 99: 1 (weight ratio).

When used as a detergent, components other than surfactants usually used in ordinary detergents, such as alcohol-based hydrotropes such as lower alcohols and polyalkylene glycols, toluene sulfonic acid, Xylene sulfonic acid, cumene sulfonic acid,
Hydrotropes such as benzoic acid and salicylic acid, low molecular aromatic compounds used as antibacterial agents, chelating agents such as citric acid, malic acid and EDTA, dyes, fragrances, viscosity modifiers, and functional substances such as inorganic compounds Can be suitably mixed.

[0028]

Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited by these examples. Note that “%” in the following examples is “% by weight”.

Example 1 (Synthesis of C ₁₁ H ₂₃ CONH (CH ₂ ) ₂ NHCH ₂ COONa) Synthesis of Cyclic Amidine A method for synthesizing 2-undecyl 5-membered cyclic amidine represented by the following formula is shown below.

[0030]

Embedded image

In a 1 liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 362 g (2.0 liters) of lauronitrile and 18 g of Ti (OCH (CH ₃ ) ₂ ) _{4 were} added.
18 g of ion-exchanged water was charged and stirred at 100 ° C. for 30 minutes. Thereafter, topping was performed under reduced pressure for 30 minutes, the temperature was raised to 200 ° C., and 132 g (2.2 mol) of ethylenediamine was added dropwise for 3 hours while maintaining the reaction temperature. After the completion of the dropping, N ₂ was blown in order to remove the by-produced ammonia out of the system.
Aged at 0 ° C. for 5 hours. After completion of the reaction, the excess diamine was distilled off under reduced pressure to obtain 2-undecyl 5-membered cyclic amidine. As a result of gas chromatography, the obtained 2-undecyl 5-membered cyclic amidine had a purity of 99% or more and unreacted nitrile was 0.1% or less. As a result of thin-layer chromatography, no bisamide spot was detected.
The conditions of gas chromatography are shown below.

[Gas chromatography analysis conditions] Apparatus name: HP-5890 Column name: DB-17 Column temperature: 150 → 280 ° C (5 ° C / min) Inlet temperature: 200 ° C Detector: FID Detector temperature: 280 ° C

Amphoterization Reaction A 2-liter 4-neck flask equipped with a stirrer, condenser, thermometer, and dropping funnel was charged with 224 g (1.0 mol) of 2-undecyl 5-membered cyclic amidine, 300 g of ethanol, and ion-exchanged. After adding 180 g of water and stirring at 80 ° C. for 2 hours, 128 g (1.1 mol) of sodium monochloroacetate was added and stirred. Control the pH to 9, 4
112 g of a 0% NaOH aqueous solution was added dropwise over 3.5 hours, and then aged for 1 hour. After the reaction is completed, the pH is adjusted to 6 with hydrochloric acid.
Adjusted to に 7 to obtain sodium N-lauroylethylaminoacetate. Unreacted amidoamine was 0.5% by HPLC analysis. In addition, sodium N-lauroylethylaminodiacetate was 23%. The HPLC analysis conditions are shown below.

[HPLC analysis conditions] Analysis was performed according to the method described in the following literature. J. Kawase, H .; Ueno and K.S. Tsu
ji, J .; Chromatogr. , 264 (198)
3) 415-422

Example 2 (C ₁₁ H ₂₃ CONH (CH ₂ ) ₃ NHCH ₂ CH ₂ COON
Synthesis of a) Synthesis of cyclic amidine A method for synthesizing a 2-undecyl 6-membered cyclic amidine represented by the following formula is shown below.

[0036]

Embedded image

In a 1-liter four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel, 362 g (2.0 mol) of lauronitrile and 18 g of Ti (OCH (CH ₃ ) ₂ ) _{4 were} ion-exchanged. 18 g of water was charged and stirred at 100 ° C. for 60 minutes. Thereafter, the mixture was topped under reduced pressure for 30 minutes and heated to 220 ° C., and then 163 g (2.2 mol) of propylenediamine
Was added dropwise for 2 hours while maintaining the reaction temperature. After dropping,
Blow N ₂ to get the by-product ammonia out of the system,
Aged for 1 hour. After completion of the reaction, excess diamine is distilled off under reduced pressure to obtain 2-undecyl 6-membered cyclic amidine.
As a result of gas chromatography, the obtained 2-undecyl 6-membered cyclic amidine had a purity of 99% or more, unreacted nitrile was 0.1% or less by gas chromatography, and bisamide was not detected by thin-layer chromatography. Was.

Amphoteric reaction In a 1-liter four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel, 252 g (1.0 mol) of 2-undecyl 6-membered cyclic amidine, 144 g of ion-exchanged water,
After adding 350 g of 2-propanol and stirring at 80 ° C. for 2 hours, the mixture was cooled to 60 ° C.
110 g (1.1 mol) of ethyl acrylate diluted with 0 g was dropped from the dropping funnel over 5 hours. After dripping, 2
Aging was performed at the same temperature for a time. After completion of the reaction, the reaction product was distilled under reduced pressure to remove 2-propanol and water.
A white solid was obtained. When this was analyzed by GC-MS, 96% of ethyl N-lauroylpropylaminopropionate, 3.5% of ethyl N-lauroylpropylaminodipropionate and 0.4% of unreacted N-lauroylpropylenediamine were obtained. It was confirmed that there was. The analysis conditions of GC-MS are shown below.

[GC-MS Analysis Conditions] Apparatus name: JMS-AX-500 Sample amount: 1 μl Column name: 5% phenyl Methyl Silicone Column size: 30 m, 0.32 mmφ, 0.25 μ Column temperature: 150 → 280 ° C. 2 min Hold rate = 10 ° C./min) Inlet temperature: 280 ° C. Ion source temperature: 200 ° C. Ionization voltage: 70 eV

Saponification reaction In a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 178 g (0.5 mol) of ethyl N-lauroylpropylaminopropionate was added.
200 g of ethanol and 100 g of ion-exchanged water were added to the mixture, and the temperature was raised to 70 ° C. while stirring. 55 g (0.5 mol) of a 40% NaOH aqueous solution was added dropwise over 3 hours, and ripening was performed for 1 hour after the addition. After completion of the reaction, the pH was adjusted to 6 with hydrochloric acid.
The mixture was adjusted to ７7 to obtain sodium laurylamidopropylaminopropionate.

Example 3 (Synthesis of C ₁₃ H ₂₇ CONH (CH ₂ ) ₃ NHCH ₂ CH ₂ COONa) Synthesis of Cyclic Amidine A method for synthesizing a 2-tridecyl 6-membered cyclic amidine represented by the following formula is shown below. .

[0042]

Embedded image

In a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 418 g (2.0 mol) of myristylnitrile and 18 g of TiO ₂ were charged.
The temperature was raised to 20 ° C., and 156 g of propylene diamine (2.
1 mol) was added dropwise over 10 hours while maintaining the reaction temperature. After completion of the dropwise addition, the mixture was aged at the same temperature for 3 hours, and the excess diamine was distilled off under reduced pressure to obtain 2-tridecyl 6-membered cyclic amidine. As a result of gas chromatography, the obtained 2-tridecyl 6-membered cyclic amidine was unreacted nitrile,
And residual propylene diamine were both 0.1% or less, and no bisamide was detected by thin layer chromatography.

Amphoterization Reaction In a 300 ml four-necked flask equipped with a stirrer, a condenser and a thermometer, 53 g (0.2 mol) of 2-tridecyl 6-membered cyclic amidine, 36 g of ion-exchanged water and 100 g of ethanol were placed. Then, hydrolysis was carried out at 80 ° C. for 2 hours.
Further, 12 g (0.22 mol) of acrylonitrile was added and reacted for 3 hours. Then, 40% NaOH aqueous solution 2
6 g was added dropwise over 3 hours, and the reaction solution was blown with N ₂ to remove by-product ammonia. After the blowing was completed, the pH was adjusted to 6 to 7 by adding hydrochloric acid to obtain sodium N-myrisuloylpropylaminopropionate. This is H
Analysis by PLC showed that 95% of sodium N-myrisuloylpropylaminodipropionate and 4.5% of sodium N-myrisuloylpropylaminodipropionate.
% And unreacted amidoamine 0.5%.

Comparative Example 1 214 g of methyl laurate was placed in a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
(1.0 mol) and 300 g (5.0 mol) of ethylenediamine were charged, and the atmosphere was heated to 40 to 50 ° C. and replaced with nitrogen three times while stirring. The reaction was carried out at 130 ° C. for 6 hours while distilling off by-produced methanol under a nitrogen stream. After completion of the reaction, the pressure was gradually reduced and the temperature was raised to 140 to 150 ° C. until the pressure became 10 torr or less, and excess unreacted ethylenediamine was topped. The obtained reaction product had a purity of laurylamidoethylamine of 87%, a bisamide of 9% and a lauric acid of 3%. Further, the reaction of this reaction product with ethyl acrylate was carried out in the same manner as in the amphoteric reaction of Example 2, except that the reaction of ethyl acrylate with respect to laurylamidoethylamine was carried out in a 1.1-fold molar amount. Then NaOH
The saponification reaction with the aqueous solution was carried out in the same manner as in the saponification reaction of Example 2 to obtain sodium laurylamidoethylaminopropionate.

Comparative Example 2 200 g (1.0 g) of lauric acid was placed in a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
Mol) and 300 g (5.0 mol) of ethylenediamine, heated to 40 to 50 ° C., and stirred with nitrogen for 3 hours.
I went there. The reaction was carried out at 130 ° C. for 6 hours in a nitrogen stream while distilling off by-produced water. After the reaction, 140 ~ 15
The pressure was gradually reduced and the temperature was raised to 0 ° C. until the pressure became 10 torr or less, and excess unreacted ethylenediamine was topped.
The obtained reaction product had a purity of laurylamidoethylamine of 89% and bisamide of 10%. This was heat-dissolved in ethanol and purified by filtration, so that the amidoamine purity was 99% or more and bisamide was 0.1% or less. Further, 1.5 times mole of acrylic acid was reacted with the purified laurylamidoethylamine at 80 ° C. in a mixed solvent of ethanol and water. When the unreacted laurylamidoethylamine disappears, the reaction end point is
Next, 35% hydrogen peroxide solution was added to polymerize unreacted acrylic acid at 60 ° C. to obtain polyacrylic acid, thereby obtaining sodium lauramidoethylaminopropionate.

Next, the present invention will be described with reference to Examples using the amidoaminomonocarboxylic acid compound obtained by the above production method. Prior to that, the outline of the test method adopted in the following examples is shown.

Composition Appearance The compositions shown in Table 1 below were prepared, and their appearance, particularly the dissolved state and viscosity, were visually observed. It is preferred to be a uniform, free of precipitates and a fluid, transparent liquid.

Skin irritation was evaluated by the following method. Surfactant composition 1%
Using an aqueous solution (35 ° C.), evaluation was performed by a immersion test by hand of 10 testers. That is, the immersion-drying operation was performed 15 times every minute, and the degree of skin roughness of the hand after 24 hours was visually judged according to the following criteria. ：: Almost no skin roughness △: Part of the keratinous surface of the skin shows signs of hand roughening such as dry desquamation and red spot change ×: Hand rough symptoms such as dry desquamation and red spot change are clearly observed Be

Foaming force 10 ml of a 1% aqueous solution of the surfactant composition was placed in a 100 ml-volume Epton tube with a stopper, and 3 ml at a constant rate under room temperature conditions.
Shake 60 times in 0 seconds. The volume of the foam at that time was measured.

Detergency 10 g of soybean oil and 10 g of tallow specified in the Japanese Pharmacopoeia for 60 m
1 g of chloroform after dissolving in chloroform
And mix well to prepare a dirty solution. A glass plate is immersed in this solution to contaminate it, and air-dried at a temperature of 25 ° C. for 30 minutes or more to remove chloroform to prepare a contaminated piece (contamination amount: 20 to 30 mg / sheet). 6 pieces of this contaminated piece are 25
20 ° C. in 700 ml of 0.15 wt% detergent solution
After washing by stirring at a rotation speed of pm for 3 minutes, the sample was air-dried, the weight was measured, and the oil removal rate after washing was calculated by the following formula to obtain the detergency.

[0052]

(Equation 1) (Where W ₀ : weight of glass plate W ₁ : weight of glass plate after contamination W ₂ : weight of glass plate after washing and air drying)

Examples 5 to 7 and Comparative Examples 3 to 4 Liquid detergent compositions shown in Table 1 below were prepared, and the appearance, skin irritation, foaming power and detergency of the compositions were determined according to the test methods described above. Was evaluated. The results are shown in the table. In addition, the compounding quantity in a table | surface is all weight%, and pH of a composition is 6.
5 prepared.

[0054]

[Table 1]

As is evident from Table 1, the cleaning compositions of the present invention (Examples 5 to 7) all exhibited excellent liquidity, mildness (low skin irritation), and cleaning performance. On the other hand, the cleaning compositions of Comparative Examples (Comparative Examples 3 and 4) all have problems.

[0056]

The amidoaminomonocarboxylic acid compound obtained by the production method of the present invention does not contain impurities such as diamide, polyacrylic acid and free amine, so that it has high foaming power, high detergency, and low skin irritation. It is a surfactant with excellent properties such as excellent cleaning properties, and it is an excellent base material that does not generate insolubles or abnormal thickening even when formulated as a liquid detergent. It is extremely suitable as a hair cleanser and a skin cleanser.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Nishida 3-17-14 Kugahara, Ota-ku, Tokyo

Claims (7)

[Claims] 1. A compound of the formula (I) RCONH (CH ₂ ) _m NH (CH ₂ ) _n COOM (I) wherein R is a linear or branched alkyl group or alkenyl having 5 to 21 carbon atoms. M represents 2 to 8,
n shows the integer of 1-2. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. ) Wherein the cyclic amidine obtained by the reaction of the aliphatic nitrile and the diamine is ring-opened in the presence of water to obtain (1) a halocarboxylic acid or a salt thereof, 2) A method characterized by reacting with acrylic acid lower alcohol ester or (3) acrylonitrile. 2. The cyclic amidine obtained by the reaction between an aliphatic nitrile and a diamine is opened in the presence of water, and (3) when reacted with acrylonitrile, the nitrile is further hydrolyzed after the reaction. The method according to claim 1, wherein 3. The cyclic amidine is represented by the general formula (II): The method according to claim 1, wherein the compound is a compound represented by the formula: wherein R 1 and m are the same as those in the general formula (I). 4. A surfactant composition containing an amidoaminomonocarboxylic acid compound produced by the method according to claim 1. Description: 5. A cleaning composition containing an amidoaminomonocarboxylic acid compound produced by the method according to claim 1. Description: 6. A detergent composition comprising, as essential components, an amidoaminomonocarboxylic acid compound produced by the method according to claim 1 and an anionic surfactant. Stuff. 7. Formula (I) RCONH (CH ₂ ) _m NH (CH ₂ ) _n COOM (I) wherein R is a linear or branched alkyl group or alkenyl having 5 to 21 carbon atoms. M represents 2 to 8,
n shows the integer of 1-2. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. ) And the general formula (XII) RCONH (CH ₂ ) _m NH (CH ₂ ) _s CH (COOM) ₂ (XII) (wherein R is a linear or branched 5 Represents an alkyl group or an alkenyl group having from 21 to 21 carbon atoms, m represents 2 to 8,
s shows the integer of 0-1. M represents a hydrogen atom, an alkali metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group. A composition comprising the amidoaminodicarboxylic acid compound represented by the formula (1) in a ratio of amidoaminomonocarboxylic acid compound / amidoaminodicarboxylic acid compound = 60/40 to 99.9 / 0.1 (weight ratio).