JPH1087582A - Stabilized monoaminocarboxylic acids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain stabilized monoaminocarboxylic acids without being discolored while being stored, transported, and used, and useful as a biodegradable chelating agent by specifying the whole amount of a cyanogen ion, hydrogen cyanide and its salt. SOLUTION: In this stabilized monoaminocarboxylic acids of the formula [R<1> is H or a 1-10C (substituted) hydrocarbon; R<2> and R<3> are each H or a 1-8C (substituted) hydrocarbon; R<4> is H, OH, CO2 M, SO3 M (M is H, an alkali metal, etc.)] (preferably aspartic acid-N-monoacetate, etc.) includes the whole amount of a cyanogen ion, hydrogen cyanide and its salt are regulated to <=100ppm, the whole amount of an ammonium ion, ammonia and its salt is regulated to <=1% and the whole amount of formaldehyde is regulated to <=1% based on the carboxylic acids. The carboxylic acids are obtained, e.g. by performing an addition reaction of a raw amino acid with prussic acid and formaldehyde and further hydrating the addition reaction products under an alkaline condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to stabilized monoaminocarboxylic acids. These monoaminocarboxylic acids are widely used as a biodegradable chelating agent in detergent compositions, detergent builders, heavy metal sequestering agents, peroxide stabilizers, and the like.

[0002]

2. Description of the Related Art The monoaminocarboxylic acids of the present invention represented by the following general formula [1] are used as powders, aqueous solutions and slurries. Issues were left.

[0003] (Wherein, R ¹ is hydrogen or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and the substituents are —OH, —CO ₂ M
And at least one selected from the group consisting of -SO ₃ M. R ² and R ³ are hydrogen or one having 1 carbon atom
~ 8 represents an unsubstituted or substituted hydrocarbon group, wherein the substituent is
-OH, at least one selected from the group consisting of -CO ₂ M and -SO ₃ M. R ⁴ is hydrogen, -OH,-
CO represents at least one selected from ₂ M and the group consisting of -SO ₃ M. R ¹ and R ² may form a ring together. M represents hydrogen, an alkali metal, an alkaline earth metal, a heavy metal, or an ammonium group. )

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve these problems of the prior art, and provides stabilized monoaminocarboxylic acids which are free from decomposition and discoloration during storage, transportation and use. Is to do.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. It has been found that it can be handled stably and easily over a long period of time.

That is, the present invention provides a compound represented by the following general formula [1]:
In the monoaminocarboxylic acids represented by the formula, the total amount of cyanide, hydrogen cyanide and salts thereof is 100 ppm or less, the total amount of ammonium ions, ammonia and salts thereof is 1% or less, and formaldehyde is 1% or less based on the monoaminocarboxylic acids. Monoaminocarboxylic acids adjusted to ”.

[0007] (Wherein, R ¹ is hydrogen or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and the substituents are —OH, —CO ₂ M
And at least one selected from the group consisting of -SO ₃ M. R ² and R ³ are hydrogen or one having 1 carbon atom
~ 8 represents an unsubstituted or substituted hydrocarbon group, wherein the substituent is
-OH, at least one selected from the group consisting of -CO ₂ M and -SO ₃ M. R ⁴ is hydrogen, -OH,-
CO represents at least one selected from ₂ M and the group consisting of -SO ₃ M. R ¹ and R ² may form a ring together. M represents hydrogen, an alkali metal, an alkaline earth metal, a heavy metal, or an ammonium group. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the monoaminocarboxylic acids in the present invention include aspartic acid-N-monoacetic acid, aspartic acid-N, N-diacetic acid, aspartic acid-N-propionic acid, S-aspartic acid-N-monoacetic acid, and S-asparagine. Acid-N, N-
Diacetate, S-aspartic acid-N-propionic acid, taurine-N, N-diacetate, anthranilic acid-N, N-diacetate, N-methyliminodiacetic acid, 2-hydroxyethyliminodiacetic acid, 2,2 '-Dimethylnitrilotriacetic acid, sulfanilic acid-N, N-diacetate, phenylalanine-
N, N-diacetate, glutamic acid-N, N-diacetate, serine-N, N-diacetate, isoserine-N, N-diacetate, α
-Alanine-N, N-diacetate, β-alanine-N, N-
Examples include diacetate and their alkali metal salts, alkaline earth metal salts, heavy metal salts, and ammonium salts.
It is not limited to these.

As a method for producing the monoaminocarboxylic acid represented by the general formula [1], there is a method in which a starting amino acid is subjected to an addition reaction of hydrocyanic acid and formalin, and the addition product is obtained by hydrolysis under alkaline conditions. The aminocarboxylic acids produced by this method contain, as impurities, amino acids as unreacted raw materials, as well as side reaction products and decomposition products of the target product. For example, aspartic acid which undergoes hydrolysis after addition of hydrocyanic acid and formalin to aspartic acid
In the synthesis of N, N-diacetate, by-products of ammonia are recognized in addition to unreacted aspartic acid, hydrocyanic acid, and formalin.

In the present invention, the total amount of cyanide, hydrogen cyanide and salts thereof is 100 ppm or less and the total amount of ammonium ions, ammonia and salts thereof is 1 ppm with respect to the monoaminocarboxylic acids represented by the general formula [1]. % And formaldehyde to 1% or less. Preferably, the total amount of cyano ions, hydrogen cyanide and salts thereof is 50 ppm based on monoaminocarboxylic acids.
Hereinafter, the total amount of ammonium ion, ammonia and its salt is adjusted to 0.5% or less, and the formaldehyde is adjusted to 0.5% or less. More preferably, the total amount of ammonium ions, ammonia and salts thereof is 20 ppm or less, the total amount of ammonium ions, ammonia and salts thereof is 0.1% or less, and formaldehyde is 0.1% or less based on monoaminocarboxylic acids. Adjust to When the aminocarboxylic acids obtained by the above reaction satisfy this condition, the reaction solution can be handled as it is. However, when the impurity content exceeds the above condition, an operation for purification is required.

As the most efficient means of purifying monoaminocarboxylic acids, the reaction solution is once subjected to acid precipitation with a mineral acid such as sulfuric acid, and the monoaminocarboxylic acid is isolated as high-purity crystals. There is a method to redissolve in water. Further, when purifying solid crude monoaminocarboxylic acids, a method of removing low-molecular impurities with high solubility by washing with alcohols such as methanol,
It is also effective to introduce an oxidizing agent such as H ₂ O ₂ or air to convert the oxide into an oxide.

By such a method, the total amount of cyanide, hydrogen cyanide and salts thereof is 100 ppm or less, the total amount of ammonium ions, ammonia and salts thereof is 1% or less and formaldehyde is 1% or less based on monoaminocarboxylic acids. The monoaminocarboxylic acids adjusted so as to be used are used as a powder or an aqueous solution or slurry containing 10% by weight or more of water, but from the viewpoint of storage stability and handling properties, the concentration of the powder or the monoaminocarboxylic acids is reduced. It is desirably used as an aqueous solution or slurry of 5 to 80% by weight, preferably 20 to 50%.

The materials of drums, tanks, lorries, storage tanks, stirrers, etc. used for storage, transfer, mixing, etc. are as follows:
Although any material such as an alloy, a glass lining, and a synthetic resin lining may be used, stainless steel is particularly preferable.

The handling temperature is 0 to 250 for powder.
° C, the concentration of monoaminocarboxylic acids is 5 to 40% by weight
In the case of 0 to 75 ° C and 5 to 7 in the case of 40 to 50% by weight.
In the case of 5 ° C and 50 to 80% by weight, the range of 10 to 75 ° C is preferable. Under such conditions, storage for about 3 years is possible, and powder or slurry of monoaminocarboxylic acid, which is not degraded in quality, can be easily taken out and used as needed.

[0015]

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

Example 1 (S) -Aspartic acid- (S-ASMA) containing (S) -aspartic acid containing 80 ppm of hydrogen cyanide, 0.8% of ammonia and 0.6% of formaldehyde. A 25.0% aqueous solution of N-monoacetic acid was prepared. After storing 500 g of the aqueous solution in a stainless steel container equipped with a thermoelectric heater at a temperature of 50 ° C. for 60 days, the components were replaced with H
The solution was analyzed by PLC and the appearance of the solution was observed. The results are shown in Table 1.

Example 2 (S) -Aspartic acid-N, N-diacetate tetraNa salt (S-
ASDA-4Na), 20 ppm of sodium cyanide,
The same experiment as in Example 1 was performed except that a 40.0% aqueous solution of (S) -aspartic acid-N, N-diacetate tetraNa salt containing 0.1% of ammonia and 0.1% of formaldehyde was used. Was. The results are shown in Table 1.

Example 3 (S) -Aspartic acid-N-monopropionic acid trisodium salt (S-ASMP-3Na) was treated with 50 pp of sodium cyanide.
The same experiment as in Example 1 was performed except that a 30.0% aqueous solution of (S) -aspartic acid-N-monopropionic acid tri-Na salt containing m, 0.5% of ammonia and 0.5% of formaldehyde was used. went. The results are shown in Table 1.

Example 4 (S) -α-alanine-N, N-diacetate tri-Na salt (S-AL
DA-3Na), containing 70 ppm of sodium cyanide, 0.8% of ammonia, and 0.5% of formaldehyde.
(S) -α-alanine-N, N-diacetate tri-Na salt 3
The same experiment as in Example 1 was performed except that a 0.0% aqueous solution was used. The results are shown in Table 1.

Example 5 Based on taurine-N, N-diacetate trisodium salt (TUDA-3Na), 60 ppm of sodium cyanide and 0.8 part of ammonia were used.
%, Formaldehyde 0.7%, taurine-N,
The same experiment as in Example 1 was performed except that a 40.0% aqueous solution of N-diacetate triNa salt was used. The results are shown in Table 1.

Example 6 N-Methyliminodiacetic acid disodium salt (MIDA-2Na) was treated with 50 ppm of sodium cyanide and 0.8 ppm of ammonia.
%, Containing a 40.0% aqueous solution of N-methyliminodiacetic acid disodium salt containing 0.6% formaldehyde,
The same experiment as in Example 1 was performed. The results are shown in Table 1.

Example 7 Anthranilic acid-N, N-diacetate tri-Na salt (ANTDA-3Na)
Example 1 except that a 50.0% slurry of tri-Na salt of anthranilic acid-N, N-diacetate containing 80 ppm of sodium cyanide, 0.8% of ammonia and 0.6% of formaldehyde was used. The same experiment was performed.
The results are shown in Table 1.

Example 8 Hydrogen cyanide 80 ppm, ammonia 0.5 ppm with respect to anthranilic acid-N, N-diacetate Fe salt (ANTDA-Fe)
The same experiment as in Example 1 was performed except that a 30.0% aqueous solution of anthranilic acid-N, N-diacetate Fe salt containing 0.6% and 0.6% formaldehyde was used. The results are shown in Table 1.

Example 9 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
The same as Example 1 except that a 25.0% aqueous solution of 2-hydroxyethyliminodiacetic acid disodium salt containing 80 ppm of hydrogen cyanide, 0.8% of ammonia and 0.6% of formaldehyde was used for a). An experiment was performed. The results are shown in Table 1.

Example 10 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 0.5% of ammonia and 0.5% of formaldehyde,
The same experiment as in Example 1 was performed, except that a 25.0% aqueous solution of hydroxyethyliminodiacetic acid disodium salt was used.
The results are shown in Table 1.

Example 11 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
The same as Example 1 except that a 40.0% aqueous solution of 2-hydroxyethyliminodiacetic acid disodium salt containing 70 ppm of hydrogen cyanide, 0.7% of ammonia and 0.6% of formaldehyde was used for a). An experiment was performed. The results are shown in Table 1.

Example 12 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 0.6% of ammonia and 0.5% of formaldehyde,
The same experiment as in Example 1 was performed, except that a 40.0% aqueous solution of hydroxyethyliminodiacetic acid disodium salt was used.
The results are shown in Table 1.

Example 13 (S) -Aspartic acid- (S) -aspartic acid containing 10 ppm of hydrogen cyanide, 0.5% of ammonia and 0.5% of formaldehyde with respect to N-monoacetic acid (S-ASMA). 500 g of N-monoacetic acid powder is sealed in a polyethylene bag and stored in a room at a temperature of 50 ° C. and a relative humidity of 60% for 60 days. The components are analyzed by HPLC and the appearance of the powder is observed. did. The results are shown in Table 1.

Example 14 (S) -aspartic acid- (S-ASDA) containing (S) -aspartic acid containing 30 ppm of hydrogen cyanide, 0.1% of ammonia, and 0.1% of formaldehyde. The same experiment as in Example 13 was performed except that 500 g of N-diacetate powder was used. The results are shown in Table 1.

Example 15 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
The same experiment as in Example 13 was performed except that 500 g of 2-hydroxyethyliminodiacetic acid disodium salt powder containing 10 ppm of hydrogen cyanide, 0.5% of ammonia, and 0.5% of formaldehyde was used for a). went. The results are shown in Table 1.

Example 16 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 0.5% of ammonia and 0.5% of formaldehyde,
Powder of hydroxyethyliminodiacetic acid disodium salt 500g
The same experiment as in Example 13 was performed except that was used. The results are shown in Table 1.

Example 17 2-hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
For a), the same experiment as in Example 13 was performed except that 500 g of 2-hydroxyethyliminodiacetic acid disodium salt powder containing 70 ppm of hydrogen cyanide, 0.7% of ammonia, and 0.6% of formaldehyde was used. went. The results are shown in Table 1.

Example 18 2-Hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 0.6% of ammonia and 0.5% of formaldehyde,
Powder of hydroxyethyliminodiacetic acid disodium salt 500g
The same experiment as in Example 13 was performed except that was used. The results are shown in Table 1.

Comparative Example 1 (S) -Aspartic acid-N- containing 80 ppm of hydrogen cyanide, 0.8% of ammonia and 3.5% of formaldehyde based on (S) -aspartic acid-N-monoacetic acid (ASMA) The same experiment as in Example 1 was performed, except that a 40.0% aqueous solution of monoacetic acid was used. The results are shown in Table 1.

Comparative Example 2 (S) -Aspartic acid-N, N-diacetate tetraNa salt (AS
DA-4Na), containing 80 ppm of sodium cyanide, 2.3% of ammonia, and 0.6% of formaldehyde.
(S) -aspartic acid-N, N-diacetate tetraNa salt 4
The same experiment as in Comparative Example 1 was performed except that a 0.0% aqueous solution was used. The results are shown in Table 1.

Comparative Example 3 200 ppm of sodium cyanide was added to (S) -aspartic acid-N-monopropionic acid trisodium salt (ASMP-3Na).
The same experiment as in Comparative Example 1 was performed except that a 30.0% aqueous solution of (S) -aspartic acid-N-monopropionic acid tri-Na salt containing m, 0.8% of ammonia, and 0.6% of formaldehyde was used. went. The results are shown in Table 1.

Comparative Example 4 Tri-Na salt of (S) -α-alanine-N, N-diacetate (S-AL
DA-3Na), containing 80 ppm of sodium cyanide, 1.6% of ammonia, and 3.3% of formaldehyde.
(S) -α-alanine-N, N-diacetate tri-Na salt 3
The same experiment as in Comparative Example 1 was performed except that a 0.0% aqueous solution was used. The results are shown in Table 1.

Comparative Example 5 Sodium cyanide 80 ppm and ammonia 0.8 based on taurine-N, N-diacetate tri-Na salt (TUDA-3Na)
%, 1.5% formaldehyde, taurine-N,
The same experiment as in Comparative Example 1 was performed, except that a 30.0% aqueous solution of N-diacetate triNa salt was used. The results are shown in Table 1.

Comparative Example 6 N-methyliminodiacetic acid disodium salt (MIDA-2Na) based on sodium cyanide 80 ppm and ammonia 2.4
%, A 40.0% aqueous solution of N-methyliminodiacetic acid disodium salt containing 1.6% formaldehyde,
The same experiment as in Comparative Example 1 was performed. The results are shown in Table 1.

Comparative Example 7 Anthranilic acid-N, N-diacetate tri-Na salt (ANTDA-3Na)
Comparative Example 1 except that a 50.0% aqueous solution of anthranilic acid-N, N-diacetate tri-Na salt containing 130 ppm of sodium cyanide, 3.6% of ammonia and 0.6% of formaldehyde was used. The same experiment was performed.
The results are shown in Table 1.

Comparative Example 8 80 ppm of hydrogen cyanide and 0.8 part of ammonia were added to Fe anthranilic acid-N, N-diacetate (ANTDA-Fe).
The same experiment as in Comparative Example 1 was performed, except that a 30.0% aqueous solution of anthranilic acid-N, N-diacetate Fe salt containing 3.5% and 3.4% formaldehyde was used. The results are shown in Table 1.

Comparative Example 9 2-hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
Comparative Example 1 was the same as Comparative Example 1 except that a 25.0% aqueous solution of 2-hydroxyethyliminodiacetic acid disodium salt containing 80 ppm of hydrogen cyanide, 0.8% of ammonia, and 3.5% of formaldehyde was used for a). An experiment was performed. The results are shown in Table 1.

Comparative Example 10 2-hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 2.2% of ammonia and 0.8% of formaldehyde,
The same experiment as in Comparative Example 1 was performed, except that a 25.0% aqueous solution of hydroxyethyliminodiacetic acid disodium salt was used.
The results are shown in Table 1.

Comparative Example 11 (S) -Aspartic acid- (N-monoacetic acid) (S-ASMA) containing (S) -aspartic acid containing 20 ppm of hydrogen cyanide, 2.5% of ammonia and 0.5% of formaldehyde. The same experiment as in Example 13 was performed, except that 500 g of N-monoacetic acid powder was used. The results are shown in Table 1.

COMPARATIVE EXAMPLE 12 (S) -Aspartic acid containing 50 ppm of hydrogen cyanide, 0.1% of ammonia and 2.3% of formaldehyde, based on (S) -aspartic acid-N-diacetic acid (S-ASDA). The same experiment as in Comparative Example 11 was performed, except that 500 g of N-diacetate powder was used. The results are shown in Table 1.

Comparative Example 13 2-Naethyl 2-hydroxyethyliminodiacetic acid (HIDA-2N
The same experiment as in Comparative Example 11 was performed except that 500 g of 2-hydroxyethyliminodiacetic acid disodium salt powder containing 80 ppm of hydrogen cyanide, 0.8% of ammonia, and 3.5% of formaldehyde was used for a). went. The results are shown in Table 1.

Comparative Example 14 2-hydroxyethyliminodiacetic acid disodium salt (HIDA-2N
a) containing 50 ppm of sodium cyanide, 2.2% of ammonia and 0.8% of formaldehyde,
Powder of hydroxyethyliminodiacetic acid disodium salt 500g
The same experiment as in Comparative Example 11 was performed except that was used. The results are shown in Table 1.

[0048] *% By weight: content of compound of general formula [1] Upper: before storage for 60 days Lower: after storage for 60 days

[0049]

By using the monoaminocarboxylic acids of the present invention, they can be stored, transported and used as powders, aqueous solutions or slurries which are stable for a long period of time without deterioration of purity or coloring due to decomposition of the components. I can do it. Further, when the monoaminocarboxylic acids of the present invention are used as a detergent builder, they have an effect of preventing the enzyme activity in the detergent component from decreasing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 309/14 C07C 309/14 309/18 309/18 // C09K 3/00 108 C09K 3/00 108C C11D 3/33 C11D 3 / 33

Claims (2)

[Claims] 1. In a monoaminocarboxylic acid represented by the following general formula [1], the total amount of cyanide, hydrogen cyanide and a salt thereof is 100 ppm or less, and the total amount of ammonium ion, ammonia and a salt thereof is 100 ppm or less based on the monoaminocarboxylic acid. Is adjusted to 1% or less and formaldehyde to 1% or less. (Wherein, R ¹ is hydrogen or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and the substituents are —OH, —CO ₂ M
And at least one selected from the group consisting of -SO ₃ M. R ² and R ³ are hydrogen or one having 1 carbon atom
~ 8 represents an unsubstituted or substituted hydrocarbon group, wherein the substituent is
-OH, at least one selected from the group consisting of -CO ₂ M and -SO ₃ M. R ⁴ is hydrogen, -OH,-
CO represents at least one selected from ₂ M and the group consisting of -SO ₃ M. R ¹ and R ² may form a ring together. M represents hydrogen, an alkali metal, an alkaline earth metal, a heavy metal, or an ammonium group. ) 2. The monoaminocarboxylic acids are aspartic acid-N-monoacetic acid, aspartic acid-N, N-diacetic acid, aspartic acid-N-monopropionic acid, S-aspartic acid-N-monoacetic acid, S- Aspartic acid-N, N-diacetic acid, S-aspartic acid-N-monopropionic acid, taurine-N, N-diacetic acid, anthranilic acid-N, N-diacetic acid, N-methyliminodiacetic acid, 2-hydroxyethyl Iminodiacetic acid, 2,2′-dimethylnitrilotriacetic acid, sulfanilic acid-N, N-diacetate, phenylalanine-N,
N-diacetate, glutamic acid-N, N-diacetate, serine-
At least one selected from N, N-diacetate, isoserine-N, N-diacetate, α-alanine-N, N-diacetate, β-alanine-N, N-diacetate and salts thereof. Item 1. The monoaminocarboxylic acids according to Item 1.