JPH0987675A - Chelating agent and detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new chelating agent excellent in chelating performance, having good biodegradability, thus useful as a detergent builder, etc. SOLUTION: This chelating agent consists of a polycarboxylic acid metal salt prepared by reaction between (A) an unsaturated dicarboxylic acid metal salt of the formula [L is (CH2 )m or C2 H4 -(NH-C2 H4 )n ((m) is 2-6; (n) is 1-6); R<1> and R<2> are each H or a 1-8C alkyl; X<1> and X<2> are each an alkali (alkaline earth) metal] and (B) an aminocarboxylic acid metal salt (pref. salt of Gly, Ala, Leu, Ile, Asp, Glu, Se, Thr or '-hydroxyaspartic acid). This chelating agent is preferable when it has a stability constant of 3.5-5.5 (esp. 4.5-5.5), dispersibility of 0.3-0.6 (esp. 0.4-0.6) and a biodegradability of >=60% (esp. >=80%).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel chelating agent and a detergent composition containing the chelating agent. More specifically, the present invention relates to a chelating agent useful as a builder for detergents and the like, and a detergent composition containing the chelating agent, since they have excellent chelating performance and dispersibility and have good biodegradability.

[0002]

2. Description of the Related Art Chelating agents are used in various fields such as fibers, paper pulp, detergents, metal surface treatments, and photography for the purpose of sequestering metal ions, and are indispensable for removing the harmful effects of metal ions. There is no such thing. Among them, removal of calcium and magnesium in hard water is a process required in many fields including detergents, and in the bleaching process of the fiber paper pulp industry, metal such as hydrogen peroxide is used as a bleaching agent. Chelating agents have been used to prevent degradation. Ethylenediaminetetraacetic acid has been widely used as a chelating agent, but it has been pointed out that this compound is not easily biodegraded, and its use is concerned from the viewpoint of environmental protection. Also, detergent builders were converted from phosphate to zeolite due to the problem of eutrophication, but since zeolite is insoluble in water, when used in excess, it causes clogging in sewers and water treatment facilities. have. Therefore, also as a builder for detergents, a chelating agent having excellent chelating ability, that is, ability to trap calcium and magnesium and having good biodegradability is desired.

[0003]

The present invention has been made in view of the above circumstances, and provides a novel chelating agent having excellent chelating performance and dispersibility, and further having good biodegradability. The purpose is to do.

It is another object of the present invention to provide a detergent composition containing the above chelating agent as a builder, which has excellent detergency and water solubility and has good biodegradability.

[0005]

MEANS FOR SOLVING THE PROBLEMS The present inventors have prepared a polyvalent carboxylic acid metal salt obtained by reacting an unsaturated dicarboxylic acid metal salt represented by the following general formula (1) with an aminocarboxylic acid metal salt. Have excellent chelating performance and dispersibility, and have good biodegradability, and have completed the present invention based on this finding.

That is, the present invention provides a compound represented by the general formula (1):

[0007]

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(In the formula, L is-(CH ₂ ) _m --or --C
₂ H ₄ — (NH—C ₂ H ₄ ) _n − (where m is an integer of 2 to 6 and n is an integer of 1 to 6), and R ¹ and R ² are each independently. And hydrogen atom or carbon number 1
To a linear or branched alkyl group, wherein X ¹ and X ² each independently represent an alkali metal or alkaline earth metal atom) and an unsaturated dicarboxylic acid metal salt and an aminocarboxylic acid The present invention relates to a polyvalent carboxylic acid metal salt obtained by reacting with a metal salt, a method for producing the polyvalent carboxylic acid metal salt, and a chelating agent comprising the polyvalent carboxylic acid metal salt.

The present invention also relates to a detergent composition containing the above chelating agent as a builder.

The chelating agent of the present invention can be specified as follows.

(1) The unsaturated dicarboxylic acid metal salt of the general formula (1) has the formula (1) wherein m is 2, 3 or 4,
Alternatively, a chelating agent which is an unsaturated dicarboxylic acid disodium salt in which n is 1 or 2, R ¹ and R ² are both hydrogen atoms, and X ¹ and X ² are both sodium atoms.

(2) The aminocarboxylic acid metal salt is a monosodium salt of monoaminomonocarboxylic acid represented by the following general formula (3), and a disodium salt of monoaminodicarboxylic acid represented by the following general formula (4). And a chelating agent which is at least one selected from the monosodium salts of hydroxyamino acids represented by the general formula (5) described below.

(3) A chelating agent in which the aminocarboxylic acid metal salt is at least one sodium salt selected from glycine, alanine, valine, leucine, isoleucine, aspartic acid, glutamic acid, β-hydroxyaspartic acid, serine and threonine.

(4) A chelating agent obtained by reacting an unsaturated dicarboxylic acid metal salt with 1.5 to 2.5 mol of an aminocarboxylic acid metal salt per mol of the unsaturated dicarboxylic acid metal salt.

(5) A chelating agent obtained by supplying an aminocarboxylic acid and sodium hydroxide to an unsaturated dicarboxylic acid sodium salt and reacting them.

(6) Calcium ion chelate stability constant (pKCa ²⁺ ) (hereinafter sometimes simply referred to as "stability constant") is 3.5 to 5.5 and dispersibility is 0.3 to 0.
6. A chelating agent having a biodegradability of 60% or more.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Preparation of the chelating agent of the present invention includes
As one of the starting materials, the unsaturated dicarboxylic acid metal salt represented by the general formula (1), that is, the alkali metal (for example, sodium, potassium, etc.) and / or the alkaline earth metal (for example, magnesium) of the unsaturated dicarboxylic acid. , Calcium, etc.) salt is used. This unsaturated dicarboxylic acid metal salt has the general formula (2):

[0018]

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An unsaturated dicarboxylic acid represented by the formula (wherein L and R ¹ and R ² have the same meaning as in the general formula (1)) and a hydroxide of an alkali metal and / or an alkaline earth metal. It is easily obtained by reacting with. The unsaturated dicarboxylic acid represented by the general formula (2) is, for example, Indian Journal of C.
chemistry, Vol. 32A, July, 199
3 (589-593), it can be easily prepared by reacting maleic anhydride with a compound having at least two amino groups or alkyl-substituted amino groups in an organic solvent (see below). Synthesis example 1
reference). Representative examples of the amino group-containing compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine and 1,6-hexane. Mention may be made of diamines.

Among the above unsaturated dicarboxylic acid metal salts, in the general formula (1), m is 2, 3 or 4, or n.
Is preferably 1 or 2, R ¹ and R ² are both hydrogen atoms, and X ¹ and X ² are both alkali metal atoms, particularly sodium atoms, and an unsaturated dicarboxylic acid disodium salt is preferably used. Representative examples of these unsaturated dicarboxylic acid disodium salts are shown below.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

Regarding the aminocarboxylic acid metal salt as another starting material, the metal salt of aminocarboxylic acid having an amino group and a carboxyl group in the molecule, that is, alkali metal (eg, sodium, potassium, etc.) and / or alkali metal Any salt of an earth metal (eg, magnesium, calcium, etc.) can be used, and of these, aminocarboxylic acid sodium salt is preferably used. Typical examples of aminocarboxylic acids generally used in the present invention are as follows.

(A) Monoaminomonocarboxylic acids General formula (3): represented by R ³ CH (NH ₂ ) COOH, in which R ³ is a hydrogen atom or has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Aminocarboxylic acid that is a linear or branched alkyl group is preferably used. R ³ may be substituted with a hydroxyl group. Representative examples include glycine, alanine, valine, leucine, isoleucine, and the like. Of these, glycine is particularly preferably used.

(B) Monoaminodicarboxylic acids General formula (4): HOOC-R ⁴ —CH (NH ₂ ) COOH
In particular, R ⁴ has 1 to 8 carbon atoms, preferably 1
An aminocarboxylic acid having a linear or branched alkylene group of 4 to 4, particularly preferably a methylene group or an ethylene group is preferably used. R ⁴ may be substituted with a hydroxyl group, and a hydroxymethylene group is particularly preferable. As a representative example, aspartic acid, glutamic acid, β-hydroxyaspartic acid and the like can be mentioned.

(C) Hydroxyamino acids General formula (5): represented by R ⁵ (OH) -CH (NH ₂ ) COOH, in which R ⁵ particularly has 1 to 8 carbon atoms, preferably 1 to
A linear or branched alkyl group of 4, particularly preferably a methyl group or an aminocarboxylic acid which is a methyl group substituted with an alkyl group having 1 to 3 carbon atoms is preferably used. R ⁵ may be substituted with a hydroxyl group. As a typical example, serine,
Threonine and the like can be mentioned.

(D) Others Representative examples of other aminocarboxylic acids include, in addition to iminodiacetic acid, sulfur-containing aminocarboxylic acids such as cystine and cystine, and aminocarboxylic acids having an aromatic nucleus such as phenylalanine and tyrosine. Examples thereof include aminocarboxylic acids having a heterocycle such as histidine and tryptophan.

Among the above aminocarboxylic acids, glycine, alanine, leucine, isoleucine, aspartic acid, glutamic acid, β-hydroxyaspartic acid, serine and threonine are preferable.

The reaction between the unsaturated dicarboxylic acid metal salt represented by the general formula (1) and the aminocarboxylic acid metal salt is
Usually, it is carried out in an aqueous medium, but it can also be carried out in a medium containing a hydrophilic organic solvent such as dioxane which is inert under the reaction conditions. Specifically, the unsaturated dicarboxylic acid metal salt and 1.5 to 2.5 mol, preferably 1.8 to 2.2 mol of aminocarboxylic acid per 1 mol of the unsaturated dicarboxylic acid metal salt in an aqueous medium. A metal salt is usually added under normal pressure at 40 to 1
The reaction is carried out at a temperature in the range of 40 ° C, preferably 60-100 ° C. As the aminocarboxylic acid metal salt, two kinds of aminocarboxylic acid metal salts may be used so that different aminocarboxylic acid metal salts are added to both ends of the unsaturated dicarboxylic acid metal salt (compound I-16 described later). , -17 and -18).

The unsaturated dicarboxylic acid metal salt is prepared by mixing the unsaturated dicarboxylic acid of the general formula (2) with about 2 molar equivalents of the alkali metal or alkali metal in the same reactor as in the above reaction. It may be prepared by reacting with a hydroxide of an earth metal, or an unsaturated dicarboxylic acid metal salt prepared in advance in another reactor may be used. In addition, instead of the aminocarboxylic acid metal salt, an aminocarboxylic acid and an alkali metal or alkaline earth metal hydroxide in an amount necessary for converting all carboxyl groups of the aminocarboxylic acid into metal salts are separately provided in a reactor. May be introduced into. Also in this case, first, an aminocarboxylic acid and an alkali metal or alkaline earth metal hydroxide are reacted to form an aminocarboxylic acid metal salt, and then the aminocarboxylic acid metal salt is reacted with an unsaturated dicarboxylic acid metal salt. Thus, a polyvalent carboxylic acid metal salt is obtained. The intended polyvalent carboxylic acid metal salt cannot be obtained by using only aminocarboxylic acid instead of the aminocarboxylic acid metal salt. Therefore, in the reaction of the unsaturated dicarboxylic acid metal salt and the aminocarboxylic acid metal salt in the present invention, an aminocarboxylic acid and a hydroxide of the metal are used in place of the aminocarboxylic acid metal salt, and these unsaturated dicarboxylic acid are used. It also includes a method of reacting with a metal salt.

The reaction of the present invention is completed by heating at the reaction temperature under stirring for several hours, and the aqueous medium is distilled off to obtain the desired product as a white solid almost quantitatively. Especially when the reaction is carried out in an aqueous solution, the reaction mixture can be directly used as a product without distilling off water.

The chelate compound of the present invention can be obtained by reacting the unsaturated dicarboxylic acid metal salt represented by the general formula (1) with the aminocarboxylic acid metal salt, and a polyvalent carboxylic acid as a reaction product. Metal salts are considered to be a mixture of compounds rather than a single compound. For example,
When unsaturated dicarboxylic acid disodium salt in which m = 2, R ¹ and R ² = hydrogen atom in the general formula (1) are reacted with aspartic acid disodium salt, three kinds of compounds 1, It is believed that a mixture of 2 and 3 will form, but at present it is not possible to isolate each of these compounds.

[0033]

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Therefore, at least the above compound 1 is contained in the chelate compound comprising the polycarboxylic acid metal salt obtained by reacting the unsaturated dicarboxylic acid metal salt of the general formula (1) with the aminocarboxylic acid metal salt. The compound is included. Examples of the compound corresponding to the above compound 1 obtained when the unsaturated dicarboxylic acid metal salt and the aminocarboxylic acid metal salt shown in Table 1 are reacted are as follows.

[0035]

[Table 1]

[0036]

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[0037]

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[0038]

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[0039]

[Chemical 12]

[0040]

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[0041]

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The chelating agent comprising a polyvalent carboxylic acid metal salt obtained by the present invention has excellent chelating performance and dispersibility, and has good biodegradability. Specifically, the chelating agent of the present invention has a stability constant of 3.5 to
5.5, dispersibility 0.3 to 0.6 and biodegradability 60% or more, especially stability constant 4.5 to 5.5, dispersibility 0.
A chelating agent having 4 to 0.6 and a biodegradability of 80% or more is preferably used. The stability constant, dispersibility and biodegradability described above were measured according to the method described in Example 4 below.

Due to the above characteristics, the chelating agent of the present invention can be widely used as a powder or an aqueous solution of any concentration, and is particularly preferably used as a builder for detergents.

The detergent composition of the present invention contains the above chelating agent and a surfactant. There is no particular limitation on the type of surfactant used here, and it has been conventionally used such as alkyl sulfate, alkylbenzene sulfate, alkylbenzene sulfonate, olefin sulfonate, alkoxylated alcohol, alkylphenol, alkylphenol sulfate, fatty acid sulfonate, and fatty acid ester sulfonate. A variety of known anionic, nonionic and cationic surfactants can be used. These may be used alone or in admixture of two or more.
The surfactant content in the detergent composition of the present invention is usually 1-40.
% By weight, preferably 1 to 30% by weight.

The content of the chelating agent is not particularly limited and may be appropriately determined, but is usually 1 to 30% by weight, preferably 3 to 3% by weight based on the weight of the detergent composition.
It is 20% by weight.

In the detergent composition of the present invention, in addition to the above chelating agent and surfactant, if desired, well-known cleaning auxiliary agents, for example, builders such as zeolite, enzymes such as protease, bleaching such as perboric acid, etc. An agent or a bleaching auxiliary agent, a stain preventing agent, an anti-settling agent, a fabric softening agent and the like can be appropriately contained.

The detergent composition of the present invention may be in the form of powder, liquid,
The paste is not particularly limited. As a method for preparing a powder, for example, a liquid or a slurry containing the above chelating agent and surfactant, and other cleaning auxiliary agent may be powdered by spray drying, or the above chelating agent may be used. It may be pulverized alone or as a mixture with inorganic salts such as zeolite, carbonate and sulfate, and then mixed with a surfactant.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Synthesis Example 1 (Synthesis of Compound II-1) 19.6 g (0.2 mol) of maleic anhydride was dissolved in 50 ml of dimethylformamide (DMF) and then 6.0 g (0.1 mol of ethylenediamine) while cooling. ) Was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour, the solvent was distilled off, and the obtained solid was washed with acetone (yield 98 mol%). The analysis results of the product are shown below.

Elemental analysis C ₁₀ H ₁₂ N ₂ O ₆ C (%) H (%) N (%) Calculated value 46.88 4.72 10.93 Measured value 46.06 4.86 11.02 NMR analysis ¹ _{H-NMR (D 2 O)} [ppm] 6.26 (2H), 5.87 (2H), 3.29 (4
H) From the above analysis results, the product was identified as the above compound II-1.

Example 1 (Synthesis of Polyvalent Carboxylic Acid Metal Salt Containing Compound I-1) 25.6 g of compound II-1 obtained in Synthesis Example 1 (0.
1 mol) and 48% by weight in a four-necked flask containing 50 g of water.
After dropwise adding 16.7 g of an aqueous sodium hydroxide solution, 15.0 g (0.2 mol) of glycine was added, and further 16.7 g of a 48% by weight aqueous sodium hydroxide solution was added. After the completion of dropping, the mixture was heated and stirred at 85 ° C. for 6 hours. After distilling off water with a rotary evaporator, the obtained colorless solid was repeatedly purified with water-methanol. The product is ¹ H-NM
The result analyzed by R is shown below.

NMR analysis ¹ H-NMR (D ₂ O) [ppm] 3.32 (2H), 3.20 (2H), 3.08 (4
H), 2.42 (4H) From the above analysis results, the product was identified as the polyvalent carboxylic acid sodium salt containing the compound I-1. The yield of polyvalent sodium carboxylic acid salt in this reaction was 88 mol%.

Example 2 (Synthesis of Polyvalent Carboxylic Acid Metal Salt Containing Compound I-7) 25.6 g of compound II-1 obtained in Synthesis Example 1 (0.
1 mol) and 48% by weight in a four-necked flask containing 50 g of water.
After dropping 16.7 g of sodium hydroxide aqueous solution, 26.6 g (0.2 mol) of aspartic acid was added, and further 4
33.4 g of an 8 wt% sodium hydroxide aqueous solution was added.
After the completion of dropping, the mixture was heated and stirred at 85 ° C. for 6 hours. After distilling off water with a rotary evaporator, the obtained colorless solid was repeatedly purified with water-methanol. ¹ H product
-The result analyzed by NMR is shown below.

NMR analysis ¹ H-NMR (D ₂ O) [ppm] 3.97 (4H), 3.20 (4H), 2.99-2.
80 (8H) From the above analysis results, the product was identified as a polyvalent carboxylic acid sodium salt containing the compound I-7. The yield of polyvalent sodium carboxylic acid salt in this reaction was 88 mol%.

Example 3 (Synthesis of polyvalent carboxylic acid sodium salt containing compound I-13) The same reaction as in Example 2 was carried out except that β-hydroxyaspartic acid was used in place of aspartic acid in Example 2. went. The results of ¹ H-NMR analysis of the product are shown below.

NMR analysis ¹ H-NMR (D ₂ O) [ppm] 4.14 (2H), 3.38 (2H), 3.29 (2)
H), 3.18 (4H), 2.41 (4H) From the above analysis results, the product was identified as the polyvalent carboxylic acid sodium salt containing the compound I-13. The yield of sodium salt of polycarboxylic acid in this reaction was 86.
It was mol%.

Example 4 (Measurement of characteristic value as chelating agent) The stability constant, dispersibility and dispersibility of the sodium salt of polyvalent carboxylic acid obtained in Examples 1 to 3 as characteristics required for the chelating agent. The biodegradability was measured and the results are shown in Table 2. The measuring methods are as follows.

Stability constant (pKCa ²⁺ (25 ° C.)) (1) Preparation of calibration curve The calcium ion concentration was 10 ⁻⁴ using calcium chloride.
M, 10 ^-3 M and 10 ^-2 M solutions were prepared and the potential of each solution was measured. Based on this measurement value, a calibration curve of the logarithm of the calcium ion concentration and the potential of the solution was prepared.

(2) Measurement of stability constant The concentrations of the sample and calcium ion are each 10 ⁻³ M.
After stirring the solution (100 cc) prepared so that it became like this, the potential of the solution was measured. The calcium ion concentration corresponding to the measured potential was obtained from the calibration curve prepared in (1) above, and the stability constant was calculated according to the following formula. However, the sample and the calcium ion were assumed to form a 1: 1 complex. In addition, the above measurement is pH 1
It was carried out under the conditions of 0.0, ionic strength 0.1 and temperature 25 ° C.

[0060]

[Equation 1]

Dispersibility A sample for measurement was prepared under the following conditions, and the absorbance obtained by measuring after stirring and standing was defined as the clay dispersibility of this sample. The larger this value is, the higher the clay dispersibility is.

<Measurement conditions> Sample: 10 mg Clay: Amazon Clay 1.0 g Stirring time: 10 minutes (using magnetic stirrer) Placing time: 24 hours Measuring method: 100 cc After measuring sample and clay in a graduated cylinder, Make up to 100 cc with water. After stirring and standing this, 10 cc of the uppermost part of the graduated cylinder was sampled, and UV 380 nm was used using a 1 cm cell.
The absorbance at was measured and the value was taken as the clay dispersibility.

Modified MITI specified in the biodegradable OECD test guideline
The measurement was performed under the following conditions with reference to the method.

<Test conditions> Sample concentration: 30 ppm Sludge concentration: 100 ppm (sewage treatment plant sludge) Temperature: 25 ± 1 ° C. Test period: 28 days Measurement item: TOC (total organic carbon content) Citric acid, which is a chelating agent,
Zeolite, nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA) were measured in the same manner, and the results are shown in Table 2.

[0065]

[Table 2]

From the results shown in Table 2, it can be seen that the sodium salt of polyvalent carboxylic acid containing compounds I-1, I-7 and I-13 has excellent chelating performance and dispersibility, and further has good biodegradability.

Example 5 (Detergent composition and its cleaning performance) The chelating agent comprising the polyvalent carboxylic acid sodium salt obtained in Examples 1 to 3 was used as a builder and various surfactants shown in Table 3 were used. Were mixed to prepare the detergent composition shown in Table 3. The detergency of these detergent compositions was measured under the following conditions using an artificial cotton cloth.

Washing condition tester: Targotometer Concentration of washing liquid: 0.12% by weight Water hardness: 3 degrees DH Bath ratio: 4 pieces of contaminated cloth 1 L Washing temperature: 25 ° C. Rotation speed: 200 times / minute Washing time: 10 Rinse rinsing: Once every 5 minutes Measure the surface reflectance of the cloth before and after washing, and according to the following formula
The detergency of each detergent composition was calculated.

Detergency = [(surface reflectance of cloth after washing-reflectance of cloth before washing) / (reflectance of original cloth-reflectance of cloth before washing)] Detergency of each detergent composition Table 3 shows the relative values when the detergency of the detergent composition of A in Table 3 is 100.

[0070]

[Table 3]

[0071]

The chelating agent of the present invention is excellent in chelating performance and dispersibility and has good biodegradability. Therefore, the chelating agent of the present invention is particularly useful as a builder for detergents.

The detergent composition of the present invention is excellent in detergency and water solubility and has good biodegradability.

Claims (4)

[Claims] 1. General formula (1): (Wherein, L is, - (CH _{2) m} - or -C ₂ H ₄ - (NH
-C ₂ H _{4) n} - (wherein, m is an integer of 2-6, n
Is an integer of 1 to 6), R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and X ¹ and X ² are A chelating agent comprising a polyvalent carboxylic acid metal salt obtained by reacting an unsaturated dicarboxylic acid metal salt represented by an alkali metal or alkaline earth metal atom) with an aminocarboxylic acid metal salt. 2. A detergent composition containing the chelating agent according to claim 1 and a surfactant. 3. General formula (1): (Wherein, L is, - (CH _{2) m} - or -C ₂ H ₄ - (NH
-C ₂ H _{4) n} - (wherein, m is an integer of 2-6, n
Is an integer of 1 to 6), R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and X ¹ and X ² are A metal salt of a polycarboxylic acid obtained by reacting an unsaturated dicarboxylic acid metal salt represented by an alkali metal or alkaline earth metal atom) with an aminocarboxylic acid metal salt. 4. The general formula (1): (Wherein, L is, - (CH _{2) m} - or -C ₂ H ₄ - (NH
-C ₂ H _{4) n} - (wherein, m is an integer of 2-6, n
Is an integer of 1 to 6), R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and X ¹ and X ² are A method for producing a polyvalent carboxylic acid metal salt, which comprises independently reacting an unsaturated dicarboxylic acid metal salt represented by an alkali metal or alkaline earth metal atom) with an aminocarboxylic acid metal salt.