JP2001342453A - Chelating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chelating agent composition able to correspond metals in the wider range than in the case of a conventional biodegradable chelating agent and having excellent performance, a cleaning or bleaching agent, and an electroless plating bath composition using the chelating agent composition. SOLUTION: The chelating composition exhibiting performance greater than the sum of the performances of each chelating agent, and further having greater dispersibility which suppresses the growth of particles of insoluble components in water is obtained by combining at least one kind of compound selected from amino acid derivatives such as ethylenediamine-N,N'-diacetic acid and ethylenediamine-N,N'-disuccinic acid, and their salts, and at least one kind of compound selected from amino acid derivatives such as aspartic acid-N-acetic acid and aspartic acid-N,N'-diacetic acid, and their salts. A cleaning agent composition exhibiting high cleaning performance, a bleaching agent composition, and an electroless plating bath which is excellent in its stability and a plating speed, and able to give plated film having excellent properties, are obtained by using such a chelating agent composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aminocarboxylic acid type chelating agent composition having excellent biodegradability and metal chelating performance, and its use. More specifically,
A compound comprising at least one compound selected from the amino acid derivative represented by the general formula (1) and a salt thereof and at least one compound selected from the amino acid derivative represented by the general formula (2) and a salt thereof The present invention relates to a chelating agent composition excellent in decomposability and metal chelating performance, a detergent composition containing the chelating agent and excellent in biodegradability and performance, and an electroless plating bath.

[0002]

2. Description of the Related Art Chelating agents have the following effects and are used for the purpose of improving the performance of detergent compositions, bleaching compositions and electroless plating baths. O Prevent unwanted effects by trapping undesired metal ions in the medium. ○ Improves the solubility of metal by chelating, and is used for the surface coating and the like by collecting and depositing metal ions. ○ Adsorbs to precipitated components, insoluble components, base materials, etc., increases the electrical repulsion and steric repulsion between them, and prevents adhesion and growth of precipitate particles. ○ The alkali metal salt of the chelating agent adjusts the pH of the medium to an optimum value by the alkali metal ions held.

[0003] Ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, aspartic acid-N, N-diacetic acid, iminodisuccinic acid, glutamic acid-N, N-diacetic acid, α-alanine-N, N-diacetic acid, taurine-N, N
Aminopolycarboxylic acids such as diacetic acid or salts thereof, and (S, S) -ethylenediaminedisuccinic acid, (S, S) -ethylenediaminediglutaric acid, which are excellent in biodegradability;
(S) -aspartic acid-N, N-diacetic acid, (S, S)
-Iminodisuccinic acid, (S) -glutamic acid-N, N-
Aminopolycarboxylic acids such as diacetate, (S) -α-alanine-N, N-diacetate, taurine-N, N-diacetic acid and salts thereof are used in detergents and detergents (surfactant raw materials, dishwashing detergents). , Synthetic detergent for clothing, bleach, soap, body soap,
Shampoos, detergents for household goods, detergents for toiletries, stain removal, etc.), industrial cleaning (printed wiring cleaning, semiconductor and metal cutting cleaning, plant cleaning, container cleaning, scale removal, scale prevention, etc.), cosmetics (cream, emulsion) , Lotion, foundation, lipstick, nail polish, hair dye, pack, hairdressing agent, moisturizer, sunscreen, whitening agent, conditioner, etc., hygiene (bactericide, antibacterial agent, deodorant, deodorant, bath agent, water treatment) Etc.), metal industry (degreasing, metal recovery and refining, foreign matter removal, oxide removal, plating, plating exfoliation, corrosion inhibitor, rust inhibitor, cutting, polishing, etc.), textile industry (dye, dyeing, smelting, discharging) , Bleaching, textile treatment, etc.), pulp industry (bleach stabilization, foreign matter removal, stabilizer, paper quality improver, etc.), photography (developer, fixer, bleach-fixer, etc.), medical and agricultural chemicals (pharmaceutical materials, agricultural chemicals) Fee, fertilizers, metal component replenishment, herbicides, enzyme additive and the like), dyes (pigments, inks, dyes raw material,
Colorants), rubber and polymers (chelate resins, polyaminocarboxylic acids, stabilizers, additives, etc.), leather (tanning, coloring, etc.), food additives (stabilizers, antioxidants, anti-tarnish agents, etc.), Chemical industry (quantitative analysis of various metals, catalysts, purification, etc.), water treatment and environment (contaminant removal, water treatment, heavy metal capture, heavy metal removal, fly ash treatment, chemical substance capture, hydrogen sulfide removal, sulfur oxides) , Chelating agents for applications such as nitrogen oxide removal, carbon monoxide removal, dust removal, etc.)
It is used as a raw material, dispersant, active ingredient and the like.

[0004] These aminopolycarboxylic acids are the same as those used in ethylenediaminetetraacetic acid (EDT).
A), propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA) and other active ingredients are used in the same form and composition. For example, in the form of salts, alkali metal salts such as sodium and potassium,
Alkaline earth metal salts such as calcium and barium, heavy metal salts such as iron (III) and vanadium, ammonium salts, amine salts, partially neutralized salts in which the above metal or basic substance is less than or equal to the carboxyl group, A mixture of salts and the like in the same form as EDTA, PDTA, DTPA, etc.,
Used in applications.

[0005] For example, as detergents or cleaning agents for tableware, household goods and body, 0.1 to 60% by mass of at least one of the above aminopolycarboxylic acids or salts thereof, and if necessary, 0.1 to 60% by mass. 1 to 60% by mass of an organic acid such as citric acid, succinic acid, amino acid or chelating agent or a salt thereof, 1 to 80% by mass of a nonionic, anionic, cationic or amphoteric surfactant and a mixture thereof, 0.01 to 20%
Mass% humectant, pH adjuster, bactericide, emulsifier, thickener,
Alkaline agent, inorganic salt, dispersant, enzyme, reducing agent, bleach,
Fluorescent dyes, solubilizers, fragrances, anti-caking agents, enzyme activators, antioxidants, preservatives, pigments, bleach activators,
An enzyme stabilizer, a phase regulator, a penetrant, an organic solvent and the like are blended and used.

For industrial cleaning such as silicon and substrate cutting, cleaning, plant cleaning, and scale removal, 0.1 to 6
0% by mass of at least one of the above aminopolycarboxylic acids or salts thereof, and if necessary, 0.1 to 60% by mass of organic acids or salts thereof such as citric acid, succinic acid, amino acids and chelating agents; 0.005 to 1% by mass of a mineral acid such as hydrofluoric acid and sulfuric acid or a salt thereof, an oxidizing agent such as ozone and hydrogen peroxide, an amine such as bentonite and ethanolamine, 1 to 80% by mass of a nonion, an anion, a cation and Amphoteric surfactants and mixtures thereof, 0.1-30
Mass% alkali metal hydroxides and the like are used in water or organic solvents.

[0007] Drugs and the like used for cosmetics and hygiene are in the range of 0.1 to 10 depending on the form of emulsion, powder, cream and the like.
In addition to 30% by mass of at least one of the above aminopolycarboxylic acids or salts thereof, 0.01 to 2 if necessary.
0% by mass pH adjuster, thickener, thickener, emulsifier, amino acid, organic acid or salt thereof, chelating agent, builder, solvent, flavor, humectant, colorant, inorganic salt, dispersant, enzyme, reducing agent , Fluorescent dyes, solubilizers, anti-caking agents, enzyme activators, antioxidants, preservatives, pigments, enzyme stabilizers,
Penetrants, organic solvent deodorants, flame retardants, antibacterial agents, porous fine particles, nonionic, anionic, cationic and amphoteric surfactants and mixtures thereof, ultraviolet absorbers, ultraviolet scattering agents,
It is used by blending a polyhydric alcohol or the like.

[0008] In the metal industry, in addition to 0.1 to 50% by weight of at least one of the above aminopolycarboxylic acids or salts thereof, and optionally 0.01 to 60% by mass for applications such as surface cleaning and corrosion prevention. Mass% of organic acids or salts thereof such as thioglycolic acid, citric acid, succinic acid, amino acids and chelating agents; inorganic acids or salts thereof such as hydrochloric acid, sulfuric acid, phosphoric acid, polymerized phosphoric acid and boric acid; Mass% to 40
Oxidizing agents such as iron (III) salt, hydrogen peroxide, and persulfate in an amount of 0.1% to 95% by mass of a nonion, an anion;
Cationic and amphoteric surfactants and mixtures thereof,
Drugs containing water, organic solvents and mixtures thereof have been used.

For bleaching pulp and textile fibers, 0.1 to
50% by mass of at least one of the above aminopolycarboxylic acids or salts thereof, 0.01% by mass to 40% by mass of iron
(III) In addition to bleaching agents such as salts, hydrogen peroxide, persulfates and hypochlorites, 0.01-20% by mass of organic acids such as citric acid, succinic acid, amino acids and chelating agents, if necessary. Composition comprising an acid or a salt thereof, an inorganic acid or a salt thereof such as hydrochloric acid, sulfuric acid, phosphoric acid, polymerized phosphoric acid, boric acid, 0.01% by mass to 5% by mass of an enzyme, water, an organic solvent and a mixed solvent thereof. Things are used.

In the dyeing field, in addition to 0.1 to 50% by weight of at least one of the above aminopolycarboxylic acids or salts thereof, 0.05 to 20% by weight of a dye or a dye precursor, and 0.05 to 10% by mass of a coupler, 0.1% to 20% by mass of a nonion, an anion,
Cationic and amphoteric surfactants and mixtures thereof, amino acids, organic acids such as chelating agents or salts thereof, thickeners,
Chemicals containing perfume, sequestering agents, film-forming agents, treatment agents, dispersants, conditioning agents, preservatives, opacifiers, fiber swelling agents, water, organic solvents, and mixtures of these solvents are used. I have.

Resins, chelate resins and paints having functions such as metal capture, flame retardancy, high water absorption, photoresist properties and conductivity are used in an amount of 0.001 to 80% by mass of the aminopolycarboxylic acid. Or at least one of the salts thereof, and if necessary, 0.001 to 10% by mass.
Organic acids such as citric acid, succinic acid, amino acids, and chelating agents or salts thereof, crosslinking agents, vulcanizing agents, curing agents, polymerization regulators, metals, metal salts, metal oxides, and the like.

In environmental fields such as water treatment such as metal collection and fly ash treatment in which incineration of garbage is regenerated, at least one of the aminopolycarboxylic acid or its salt of 1 to 80% by mass is composed of water, organic Solvents and their mixtures are used in the form of a solution or slurry of a solvent or a copolymer or contained in a polymer, and if necessary, 0.1% by mass to 20% by mass.
Amino acids, organic acids such as chelating agents or salts thereof, organic sulfides such as dithiocarbamine, inorganic sulfides such as sodium sulfide and potassium hydrosulfide, metal oxides such as aluminum oxide and silicon dioxide, activated carbon, slaked lime and alkali metals Alkaline components such as hydroxides and alkaline earth metal hydroxides, and phosphates such as di-sodium hydrogen phosphate are used in combination.

For capturing chemical substances from exhaust gas and wastewater, removing hydrogen sulfide, removing sulfur oxides, nitrogen oxides, removing carbon monoxide, etc., 0.001 to 50% by mass of the above aminopolycarboxylic acid or a salt thereof, Furthermore, oxidizing agents such as hypochlorous acid, mineral acids, alkali metal hydroxides, alkaline earth metal compounds such as lime, limestone, calcium silicate, magnesium carbonate, activated carbon, alumina, silica, alumina silicate, zeolite, and acid clay , Activated clay, kaolin, bentonite, porous materials such as allophane, clay minerals such as diatomaceous earth,
Phosphates, sodium silicate, potassium silicate, inorganic adsorbents, cements, iron sulfate, iron chloride, aluminum sulfate, aluminum chloride, and the like are blended and used.

Conventionally, sodium tripolyphosphate, which has been used as a detergent builder, has an excellent chelating ability, but contains phosphorus, so that when it is released into the environment, it causes eutrophication of rivers or lakes. Is a problem.

[0015] Zeolite, which is currently used as a builder for detergents, has the disadvantage that it has low chelating ability and is not biodegradable because it is an inorganic substance. Furthermore, since zeolite is insoluble in water, there is a limitation in use in that it cannot be used as a liquid, especially a clear liquid detergent. In addition, zeolite has many problems, such as sticking to the inner wall of drain pipes and accumulating on the bottom of rivers and causing sludge, and attempts have been made to reduce the amount of zeolite used. There has been a demand for a zeolite substitute having good cleaning performance, but such a substitute has not yet been obtained.

Among aminocarboxylic acids conventionally used as detergent builders, ethylenediaminetetraacetic acid (EDTA) has excellent chelating ability in a wide pH range, but has poor biodegradability and is usually used in activated sludge. It is difficult to perform the decomposition treatment by the wastewater treatment method described above. Further, nitrilotriacetic acid (NTA) has a certain degree of biodegradability, but it is not preferable in terms of environmental hygiene because it has been reported that the nitrilotriacetic acid iron complex is suspected to be carcinogenic. Among other conventional aminocarboxylic acids,
If the biodegradability is low even if the chelating ability is excellent,
When released into the environment, there is a problem that they are accumulated in the environment as harmful heavy metals. As for the amino organic acids as described above, various compounds have been conventionally studied, but some compounds having excellent chelating ability and excellent biodegradability have been reported.

Ethylenediamine-N, N'-disuccinic acid (EDDS) has excellent biodegradability and chelating ability for heavy metals, and US Pat. No. 3,158,635 discloses its use for removing rust, and US Pat. 470423
No. 3 is a cleaning agent to promote the removal of organic stains.
It describes the use of DDS and its biodegradability. Japanese Patent Application Laid-Open No. 63-199295 discloses an ED
Laundry detergent composition using DS is disclosed in JP-A-4-31.
No. 3752 discloses a photographic processing composition containing EDDS.

JP-A-9-13175, JP-A-9-49
No. 084 discloses an electroless plating bath containing, as an active ingredient, at least one selected from a diamine-type biodegradable chelating agent having a basic skeleton of succinic acid, glutaric acid and the like, and an alkali metal salt and an ammonium salt thereof. ing.

Aspartic acid-N, N-diacetic acid (ASD
A) and chelating agents such as glutamic acid-N, N-diacetic acid (GLDA) have excellent biodegradability and chelating performance of alkaline earth metals, and are disclosed in Japanese Patent Application Laid-Open No. 9-176694.
A biodegradability of A and a plant detergent using ASDA are described, and JP-A-9-221697 describes a biodegradability of GLDA and a plant detergent using GLDA. Also, Japanese Patent Application Laid-Open No.
A detergent using SDA or taurine diacetic acid is disclosed.

JP-A-8-296049, JP-A-8-3
No. 25742 discloses an electroless plating bath containing, as an active ingredient, a monoamine type biodegradable chelating agent having a basic skeleton of aspartic acid, glutamic acid, iminodiacetic acid and the like, and at least one selected from alkali metal salts and ammonium salts thereof. Is disclosed.

However, EDDS, ASDA and GLDA may have reduced chelating performance for certain metals depending on the use conditions. For example, EDDS may have a lower ability to chelate calcium and magnesium ions than EDTA and the like, and ASDA and GLDA may have a lower ability to chelate iron and copper ions as compared to EDTA and the like. As described above, when the chelating agent is not suitable for a certain kind of metal, there is a problem that the application is limited and the amount used is reduced.

[0022]

SUMMARY OF THE INVENTION A chelating agent composition which is compatible with a wider range of metals than conventional biodegradable chelating agents and has excellent performance, and a detergent, a bleaching agent, and an electroless plating using them. It is intended to provide a bath composition.

[0023]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have at least one compound selected from the amino acid derivatives represented by the following general formula (1) and salts thereof: By combining at least one compound selected from the amino acid derivative represented by the following general formula (2) and a salt thereof, it exhibits a performance exceeding the ability of individual chelating agents, and further, particles of insoluble components in water The use of these chelating agent compositions increases the dispersing ability that suppresses the growth of a detergent composition and a bleaching composition exhibiting a high cleaning effect, plating bath stability, plating rate, and formed film. It has been found that an electroless plating bath having excellent properties can be obtained, and the present invention has been achieved.

[0024]

Embedded image

In the formula, A ^a and ^Ab are the same or different and each is a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group, a carboxyl group, a phenyl group or an amino group. Wherein Y ^a and Y ^b are the same or different and each represent a carboxyl group or a sulfonic acid group, and W is a linear or branched alkylene having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group. Represents a group. ]

[0026]

Embedded image

[Wherein, R ^a and R ^b are the same or different and each have a linear or branched C 1-12 carbon atom which may be substituted by hydrogen, hydroxyl group, carboxyl group, phenyl group or sulfonic acid group. Represents an alkyl group, but not simultaneously hydrogen. A ^C represents a hydroxyl group, a carboxyl group, a phenyl group or an alkylene group having 1 to 6 carbon atoms which may linear or branched chain optionally substituted amino group, Y ^c represents a carboxyl group or a sulfonic acid group. ]

That is, the composition of the present invention comprises at least one compound selected from the amino acid derivative represented by the general formula (1) or a salt thereof and the amino acid derivative represented by the general formula (2) or a salt thereof. The present invention relates to a chelating agent composition containing at least one selected compound, a detergent composition containing these, a bleaching agent composition, and an electroless plating bath.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the compound of the above formula (1), the linear or branched C1-C6 alkylene group which may be substituted by the hydroxyl group or carboxyl group represented by W includes ethylene, trimethylene, Examples include propylene, tetramethylene, pentamethylene, hexamethylene, 2-hydroxytrimethylene and the like. Among these, an unsubstituted alkylene group having 2 to 6 carbon atoms, particularly ethylene, is preferred.

The amino acid derivatives of the general formula (1) include
Ethylenediamine-N, N'-diacetic acid, ethylenediamine-N, N'-dipropionic acid, ethylenediamine-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Diglutaric acid, ethylenediamine-N, N'-bisethanesulfonic acid, trimethylenediamine-N, N'-diacetate, trimethylenediamine-N, N'-dipropionic acid, trimethylenediamine-N, N'-dichlorobenzene Acid, trimethylenediamine-N, N'-diglutaric acid, trimethylenediamine-N, N'-bisethanesulfonic acid, 2
-Hydroxytrimethylenediamine-N, N'-diacetate, 2-hydroxytrimethylenediamine-N, N'-
Dipropionic acid, 2-hydroxytrimethylenediamine-N, N'-succinic acid, 2-hydroxytrimethylenediamine-N, N'-diglutaric acid, 2-hydroxytrimethylenediamine-N, N'-bisethanesulfonic acid , Ethylenediamine-N-acetic acid-N'-succinic acid, ethylenediamine-N-acetic acid-N'-propionic acid, ethylenediamine-N-propionic acid-N'-succinic acid, ethylenediamine-N-acetic acid-N'-glutaric acid, Ethylenediamine-N-succinic-N'-ethanesulfonic acid,
Trimethylenediamine-N-acetic acid-N'-succinic acid, trimethylenediamine-N-acetic acid-N'-propionic acid,
Trimethylenediamine-N-propionic acid-N'-succinic acid, trimethylenediamine-N-succinic-N'-glutaric acid, trimethylenediamine-N-acetic acid-N'-ethanesulfonic acid, 2-hydroxytrimethylene Diamine-N-acetic acid-N'-succinic acid, 2-hydroxytrimethylenediamine-N-acetic acid-N'-propionic acid, 2-hydroxytrimethylenediamine-N-acetic acid-N'-succinic acid or salts thereof Ethylenediaminedisuccinic acid, trimethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, trimethylenediaminediglutaric acid, 2-hydroxytrimethylenediamine-N, N'-disuccinic acid, 2-hydroxy- Trimethylene diamine diglutaric acid is preferred. The above amino acid derivatives may be used as a mixture.

When the amino acid derivative of the general formula (1) has one or more asymmetric carbons, several kinds of optical isomers may exist. Any of the isomers can be used alone or as a mixture, but an amino acid derivative having an S-form asymmetric carbon having excellent biodegradability is preferable, and an amino acid derivative having all the more asymmetric carbons having a more excellent biodegradability is an S-form. Is particularly preferred.

The amino acid derivative of the general formula (1) can be produced according to a known method, for example, by reacting a diamine with a halide, an olefin compound or the like.
Here, specific examples of the diamine include ethylenediamine, propylenediamine, trimethylenediamine, hexamethylenediamine, and 2-hydroxytrimethylenediamine. Specific examples of halides include:
Chloroacetic acid, bromoacetic acid, sodium chloroacetate, sodium bromoacetate, sodium chloropropionate, sodium bromopropionate, 2-chloroethanol,
3-chloropropanol and the like. Specific examples of the olefin compound include maleic acid, fumaric acid, methyl maleate, methyl fumarate, ethyl maleate, ethyl fumarate, methyl acrylate, ethyl acrylate, acrylonitrile, propyl fumarate, and the like.

The amino acid derivative of the general formula (1)
It can also be produced by a method such as reacting a dihalide or the like with an amino acid. Here, specific examples of the dihalide include dichloroethane, dibromoethane, dichloropropane, dichlorobutane, dibromobutane and the like. Specific examples of the amino acid to be reacted include alanine, valine, leucine, isoleucine, threonine, phenylalanine, glycine, serine, threonine, tyrosine, histidine, lysine, arginine, aspartic acid, and glutamic acid.

In the compound of the above general formula (2) in the present invention, ^a straight-chain or branched-chain carbon atom which may be substituted by a hydroxyl group, a carboxyl group, a phenyl group or a sulfonic acid group represented by R ^a and R ^b. c 1 -C 12 alkyl group, a hydroxyl group represented by a ^c, carboxyl group, specific examples of the alkenyl group having 1 to 6 carbon atoms phenyl or optionally linear or branched chain optionally substituted amino group The following can be mentioned.

Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Examples of the branched alkyl group include methylhexyl, Examples include groups such as ethylhexyl, methylheptyl, ethylheptyl, methylnonyl, and methylundecyl.

Examples of the linear alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl,
Examples include groups such as heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and examples of the branched alkenyl group include methylhexenyl, ethylhexenyl, methylheptenyl, ethylheptenyl, methylnonenyl, and methylundecenyl. it can. Of these, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl,
Groups such as decyl, undecyl, dodecyl, methylhexyl, ethylhexyl, methylheptyl, ethylheptyl, methylnonyl, and methylundecyl; further, methyl, ethyl, propyl, butyl, hexyl, heptyl,
Groups such as octyl, nonyl, decyl, undecyl, dodecyl, methylhexyl, ethylhexyl and the like are preferred.

The amino acid derivatives of the general formula (2) include
Aspartic acid-N-acetic acid, Aspartic acid-N, N-
Diacetic acid, aspartic acid-N-propionic acid, iminodisuccinic acid, aspartic acid-N-methanesulfonic acid, aspartic acid-N-2-ethanesulfonic acid, glutamic acid-N, N-diacetic acid, glutamic acid-N-methanesulfonic acid, Glutamic acid-N-2-ethanesulfonic acid, N-methyliminodiacetic acid, α-alanine-N, N-diacetic acid, β-
Alanine-N, N-diacetic acid, serine-N, N-diacetic acid,
Isoserine-N, N-diacetate, phenylalanine-N,
N-diacetic acid, anthranilic acid-N, N-diacetic acid, sulfanilic acid-N, N-diacetic acid, taurine-N, N-diacetic acid, or a salt thereof. Aspartic acid-N , N-diacetic acid, iminodisuccinic acid, glutamic acid-N, N-diacetic acid, N-methyliminodiacetic acid, α-
Alanine-N, N-diacetate, β-alanine-N, N-diacetate, serine-N, N-diacetate, isoserine-N, N-
Diacetic acid and taurine-N, N-diacetic acid are preferred. The above amino acid derivatives may be used as a mixture.

When the amino acid derivative of the general formula (2) has one or more asymmetric carbons, several kinds of optical isomers may exist. Any of the isomers can be used alone or as a mixture, but an amino acid derivative having an S-form asymmetric carbon having excellent biodegradability is preferable, and an amino acid derivative having all the more asymmetric carbons having a more excellent biodegradability is an S-form. Is particularly preferred.

The amino acid derivative represented by the general formula (2) can be obtained by subjecting an amino acid or sulfonic acid as a raw material to an addition reaction of hydrocyanic acid and formalin, and hydrolyzing the obtained addition product under alkaline conditions. There is a method in which an alkali metal salt of an amino acid or a sulfonic acid is subjected to an addition reaction with a cyanide of an alkali metal and formalin, followed by hydrolysis. Further, it can also be produced by a method of subjecting an amino acid or sulfonic acid to an addition reaction with acrylonitrile and the like, and hydrolyzing the obtained addition product under alkaline conditions, or a method of reacting an amino acid with an olefin compound or a halide.

Specific examples of amino acids include alanine, valine, leucine, isoleucine, threonine, phenylalanine, glycine, serine, threonine, tyrosine,
Examples include histidine, lysine, arginine, aspartic acid, glutamic acid and the like. Specific examples of the halide, chloroacetic acid, bromoacetic acid, sodium chloroacetate, sodium bromoacetate, sodium chloropropionate, sodium bromopropionate, 2-chloroethanol, 3-chloropropanol, and the like, as specific examples of the olefin compound Examples thereof include maleic acid, fumaric acid, methyl maleate, methyl fumarate, ethyl maleate, ethyl fumarate, methyl acrylate, ethyl acrylate, acrylonitrile, propyl fumarate and the like.

The compounds represented by the general formulas (1) and (2) and the salts thereof have a carboxyl group (-COOH) and a sulfonic acid group (-SO ₃ H), and thus have various cations between them. Can form salts. Such salts include, for example, alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts and the like, and specifically, sodium, potassium, lithium, magnesium,
Calcium, trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine,
Examples thereof include salts with choline, ammonia and the like, and among these, sodium salts, potassium salts and ammonium salts are preferred. Further, these salts may be partially neutralized salts. The above salts may be used as a mixture, or may contain a plurality of cations in one molecule.

After completion of the above reaction, the reaction mixture may contain a compound such as an inorganic salt, an unreacted starting material or a salt thereof, or a fatty acid, in addition to the desired derivative of the present invention or a salt thereof. In the present invention, the reaction product can be used as it is, but if necessary, purified by a known method such as a solvent fractionation method, an ion exchange chromatography method, a recrystallization method, or an electrodialysis method, and used. You can also.

The compounds represented by the general formulas (1) and (2) and their salts can be used in combination of one or more of any of these compounds. The combination ratio may be any value, but in order to exhibit the effect of each component, the molar ratio of the compound of the general formula (1) to the compound of the general formula (2) should be 1/99 to 99/1. It is preferable to combine them, and it is more preferable to combine them so as to be 10/90 to 90/10.

At least one compound selected from the amino acid derivatives represented by the general formula (1) or a salt thereof is combined with at least one compound selected from the amino acid derivatives represented by the general formula (2) or a salt thereof. As a result, performance exceeding the sum of the abilities of the individual chelating agents is exhibited, and the dispersing ability for suppressing the growth of particles of the insoluble component in water is increased. In addition, excellent performance can be exhibited under a wide range of pH conditions.

That is, by appropriately blending these chelating agent components, the same or better performance as ethylenediaminetetraacetic acid, which has been conventionally preferably used as an excellent chelating agent, can be obtained over a wide range from neutral to alkaline. It can be obtained under pH conditions.

When the compounds represented by the general formulas (1) and (2) or salts thereof are used, various known surfactants, humectants, bactericides, emulsifiers, thickeners, amino acids, Alkaline agent, inorganic salt, dispersant, enzyme, reducing agent, bleach, fluorescent dye, solubilizer, fragrance, anti-caking agent,
Enzyme activators, antioxidants, preservatives, dyes, bleach activators, enzyme stabilizers, phase regulators, penetrants, organic solvents, buffers, stabilizers, anti-redeposition agents, polyacrylic acid, Salts of polymers such as polymaleic acid, polyaconitic acid, polyacetal carboxylic acid, polyvinylpyrrolidone, carboxymethylcellulose, polyethylene glycol, and salts of organic acids such as citric acid, malic acid, fumaric acid, succinic acid, gluconic acid, tartaric acid, etc. Can be blended.

The detergent composition of the present invention comprises at least one compound selected from the group consisting of the amino acid derivative represented by the general formula (1) and a salt thereof, and the amino acid derivative represented by the general formula (2) and a salt thereof. Including a chelating agent composition comprising at least one compound selected from salts, if necessary, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an anionic surfactant, a silicate, Contains bleach and / or fatty acid salts. These surfactants can be used alone or in combination of two or more.

The nonionic surfactant which can be used in the present invention is not particularly limited, such as ethoxylated nonylphenols, ethoxylated octylphenols, ethoxylated sorbitan fatty acid esters, and propylene oxide adducts thereof. Can be used,
Ethoxylated primary aliphatic alcohols, ethoxylated secondary
Higher aliphatic alcohols and their propylene oxide adducts show particularly high detergency.

Examples of the anionic surfactant which can be used in the present invention include a linear alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms and an α-olefin sulfonate having an average of 10 to 20 carbon atoms. And a salt of an aliphatic lower alkyl sulfonate or an aliphatic sulfonate, an alkyl sulfate having an average of 10 to 20 carbon atoms, a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and Examples thereof include an alkyl ether sulfate or an alkenyl ether sulfate to which 0.5 to 8 mol of ethylene oxide has been added, and a saturated or unsaturated fatty acid salt having an average of 10 to 22 carbon atoms.

Examples of the cationic surfactant which can be used in the present invention include an aliphatic primary amine salt, an aliphatic secondary amine salt and an aliphatic tertiary amine salt having an alkyl group having an average of 8 to 18 carbon atoms. And aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride salts, pyridinium salts and imidazolinium salts.

The silicates that can be used in the present invention include:
These are silicates or aluminosilicates, and these can be used alone or in a mixture at an arbitrary ratio. The amount of the silicate used is 0. 0 in the detergent composition.
It is 5 to 80% by mass, preferably 5 to 40% by mass.

Examples of the bleaching agent that can be used in the present invention include sodium percarbonate and sodium perborate. These bleaching agents are used in an amount of 0.1% in the detergent composition.
It is 5 to 60% by mass, preferably 1 to 40% by mass, and more preferably 2 to 25% by mass.

The fatty acid salts used in the present invention include alkali metal salts, alkaline earth metal salts, ammonium salts or unsubstituted or substituted amine salts of saturated or unsaturated fatty acids having an average of 10 to 24 carbon atoms, preferably alkali metal salts. Salts, alkaline earth metal salts, and more preferably alkali metal salts. These fatty acid salts may be used as a mixture of two or more.

As the fatty acid salts used in the present invention, alkali metal salts, alkaline earth metal salts, ammonium salts or unsubstituted or substituted amine salts such as lauric acid, myristic acid or stearic acid are used. Metal salts, alkaline earth metal salts, and more preferably alkali metal salts are exemplified.

The detergent composition of the present invention further comprises a stabilizer, an alkali salt, an enzyme, a fragrance, a nonionic or anionic or non-cationic surfactant, a scale formation inhibitor, a foaming agent, and an antifoaming agent. For example, various additives can be added.

In applications such as pulp and clothing, hydrogen peroxide and organic peracids are blended for the purpose of bleaching. Chelating agents are used because of the decomposition action of these peroxides catalyzed by heavy metals such as iron. Has the function of protecting.

In the field of food industry, depending on the use of beer bottle washing, dish washing, and plant washing, a detergent composition containing only a chelating agent as a main component without the addition of a surfactant is used for calcium carbonate, ash, and the like. The present invention may be used to remove calcium acid and the like.The present invention also provides salts of tripolyphosphoric acid and pyrophosphoric acid, diethylenetriaminepentaacetic acid,
It does not preclude the use of ethylenediaminetetraacetic acid, nitrilotriacetic acid salts and the like as a chelating agent, but it is desirable to avoid using these existing chelating agents from the viewpoint of reducing the environmental load and safety.

For household use such as kitchen and clothing, neutral detergents are p
In the vicinity of H6.5 to 8.5, it is often used in combination with a surfactant such as dodecylbenzenesulfonate, lauryl alcohol sulfate or polyethylene glycol. Industrial detergents for clothing washing, dish washing, plant washing, bottle washing, etc. have a wide range of pH conditions from neutral to strongly alkaline.

The detergent composition of the present invention is prepared as a high-concentration liquid detergent or powder detergent in which the components, such as a chelating agent and a surfactant, are mixed at a predetermined mixing ratio. When used, it can be used after being diluted to a predetermined concentration with water. In addition, these components can be used by diluting and mixing them in dilution water at a mixing ratio.

The alkali metal salt of gluconic acid imparts gloss to the glass, and the cleaning composition containing the same is particularly suitable for cleaning glass containers.

The compounding amount of the above components in the present hard surface cleaner is 0.5 to 10% by mass of the alkali metal hydroxide.
Preferably, it is in the range of 1 to 5% by mass, and the metal salt of the chelating agent composition of the present invention is in the range of 0.2 to 20% by mass, preferably in the range of 0.2 to 5% by mass. The amount of the scale formation inhibitor is in the range of 10 to 1000 pm, preferably in the range of 20 to 500 ppm.

The hard surface cleaning composition of the present invention is prepared as a high-concentration liquid cleaning agent or powder cleaning agent by blending the respective components in a desired mixing ratio in advance, and this is adjusted to a predetermined concentration with water at the time of use. It can be used after dilution. Also,
It is also possible to dilute and mix these components with dilution water at a predetermined mixing ratio before use.

In the present invention, any metal ions used for plating can be used as long as they are metals used for conventional electroless plating, but copper and Ni plating are preferred from the viewpoint of finishing after plating.

The materials to be plated in the present invention include metals,
Various nonmetals can be used. Rolled steel for general structures, carbon steel for mechanical structures, and catalytically active materials can be directly plated after degreasing or etching.
In addition, special metals such as stainless steel, molybdenum steel, titanium, tungsten, molybdenum, tantalum, copper, silver, gold, aluminum, magnesium, lead, solder, bismuth, antimony, ITO, and plastics such as ABS, ceramics, etc. A film can also be formed on a metal by performing pretreatment and activation according to each characteristic. The plating bath of the present invention has a basic composition of three components of a metal ion supplier, a reducing agent, and a complexing agent.
As the metal ion supply agent, nickel sulfate, nickel chloride, nickel nitrate, copper sulfate, copper chloride, copper hydroxide and the like are used, and nickel sulfate and copper sulfate are preferable. As the reducing agent, aldehydes such as formalin, glyoxal and glyoxalic acid, phosphinates such as sodium hypophosphite, and borohydrides such as dimethylaminoborane, potassium tetrahydroborate and sodium borohydride are used. For the purpose of Ni-P alloy plating, a phosphinate is used, and sodium hypophosphite is preferred.

As the complexing agent used in the present invention, at least one compound selected from the amino acid derivative represented by the general formula (1) or a salt thereof and the amino acid derivative represented by the general formula (2) or a salt thereof A chelating composition comprising at least one compound selected from salts is used.

The amount of the chelating agent composition used as the complexing agent varies depending on the complexing power, but the concentration ranges from 5 to 500 mM.
0.2 to 30 times mol, preferably 0.5 to 10 times mol, particularly preferably 0.7 to 7 times mol of metal ion of
It is used in a double molar amount.

The chelating agent composition used as a complexing agent in the present invention has a strong buffering power, and thus functions as a buffer itself and functions as a pH regulator. Mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids having a low complexing power such as acetic acid and succinic acid can be used for adjusting the pH in the acidic bath.
For pH adjustment in an alkaline bath, an inorganic base such as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate or a nitrogen-containing base having a low complexing power such as ammonia, ethylenediamine or triethanolamine may be used. it can.

The plating of the bath is carried out in a wide range of from 3 to 14, preferably within a range of from 4 to 13. When a phosphinate is used as the reducing agent, N
Although i-P alloy plating is possible, when a Ni film having a high P content is to be obtained at a high speed, it is carried out in a pH range of 4 to 10, preferably in a range of pH 5 to 9. The temperature of the bath is in the range of 30 to 98 ° C., preferably 7 to 98 ° C.
It is carried out in the range of 0 to 95 ° C.

The electroless plating bath in the present invention is usually
A coating excellent in uniformity, adhesion, gloss and wettability is provided with a high number of turns under high bath stability. However, in order to further improve the properties, bath stability and liquid life of the coating, 2, 2 ′ Addition of trace amounts of bipyridyl, orthophenanthrin, potassium ferrocyanide, neocuproin, surfactant, thiourea, lead salts and the like is also an effective means.

The chelating agent composition of the present invention is also effective for forming a Ni film having a high P content at a high speed and has a pH of 8
In a high plating rate region of 10 to 10 (alkaline bath with ammonia), plating having a high P concentration is possible.

In the electroless plating bath using the chelating agent composition according to the present invention as a complexing agent, it is necessary to remove heavy metals and hypophosphite in the waste solution treatment. Since it is rapidly decomposed in the natural environment, it can be treated as general wastewater.

[0073]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
The amino acid derivatives used in the test are abbreviated as follows.

(S, S) -ethylenediamine disuccinic acid: EDDS (S, S) -ethylenediamine diglutaric acid: EDDG (S) -aspartic acid-N, N-diacetate: ASDA (S) -glutamic acid-N, N-diacetate: GLDA (S) -α-alanine-N, N-diacetate: ALDA

Example 1 The following tests were performed on the chelating agent compositions having the compositions shown in Tables 1 and 2, and the ability to capture and disperse metal ions was measured. The results are shown in Tables 3 and 4.

(1) Calcium ion scavenging ability 10 g of a chelating agent having the composition shown in Tables 1 and 2 was placed in a 1-L volumetric flask, and dissolved by adding 900 ml of water and an aqueous solution of sodium hydroxide, and 1% by mass of dodecylbenzene sulfone was used as an indicator. After adding and dissolving 10 g of sodium acid, the pH was adjusted to 12 with an aqueous sodium hydroxide solution and water, and the volume was increased to 1 L. After raising the volume, 50 ml of the solution was placed in a 100 ml beaker, and titration was performed using a 1% by mass aqueous solution of calcium acetate with opacity as an end point.
^{The 2+} capture ability (calculated as acid form) was determined. The larger the value, the stronger the ability of the chelating agent to capture Ca ²⁺ ions.

(2) Heavy metal ion scavenging ability 0.01 mol of chelating agent having the composition shown in Tables 1 and 2 was added to 1
The mixture was placed in an L volumetric flask and dissolved by adding 800 ml of water and aqueous ammonia, and the pH was adjusted to 8 to 9. 100 ml of 0.1 mol / L iron (III) nitrate aqueous solution in a measuring flask
And adjusted to pH 9 by adding aqueous ammonia and water, and the volume was increased to 1 L. After allowing the samples to stand for 7 days, the supernatant of each sample was filtered and then ICP (inductive).
Lysed iron was analyzed by ly coupled plasma spectroscopy. The larger the value is, the stronger the chelating agent is capable of capturing Fe ³⁺ ions.

(3) Dispersibility 10 mg of a chelating agent having the composition shown in Tables 1 and 2 and 1.0 g of Amazon Clay were placed in a 100 cc graduated cylinder and made up to 100 cc with water. This with a magnetic stirrer
After stirring for 0 minutes and standing for 24 hours, the top 10 cc of the graduated cylinder was sampled, the absorbance at UV 380 nm was measured using a 1 cm cell, and the value was regarded as clay dispersibility. The larger the value is, the higher the clay dispersibility is, which means that reattachment of dirt is prevented.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[]: Theoretical value = performance of only A × composition + performance of only B × composition

[0083]

[Table 4]

[]: Theoretical value = performance of A alone × composition +
Performance of only B × composition

As is evident from Tables 3 and 4, the detergent composition of the present invention exhibits better metal ion-capturing ability and dispersibility than using a single chelating agent.

Example 2 A cleaning composition was tested using the chelating agent compositions having the compositions shown in Tables 1 and 2, and the detergency was measured. The results are shown in Tables 6 and 7. The chelating agent compositions are shown in Tables 1 and 2 under Composition No. The one indicated by is used.

[Method of Measuring Detergency] Preparation of Artificial Soil A clay mainly composed of a crystalline mineral such as kaolinite or permiculite was dried at 200 ° C. for 30 hours and used as inorganic soil. 3.5 g of gelatin was dissolved in 950 cc of water at about 40 ° C., and then dissolved in an emulsifying and dispersing machine.
25 g of carbon black was dispersed in water. Next, 14.9 g of inorganic soil was added and emulsified, and further, organic soil 3 was added.
1.35 g was added and emulsified and dispersed with a Polytron to form a stable soil bath. After immersing a predetermined cleaning cloth (cotton cloth No. 60 designated by the Japan Oil Chemistry Association) of 10 cm × 20 cm in the dirt bath, squeezing water with two rubber rolls to equalize the adhesion amount of dirt, Both sides of the dirty cloth were rubbed left and right 25 times. This is cut into 5 cm x 5 cm and the reflectance is 42.
Those having a range of ± 2% were applied to a dirty cloth. The soil composition of the artificial soil cloth thus obtained is shown in Table 5.

[0088]

[Table 5]

(2) Cleaning method S. Terg-O-Tomet made by Testing Company
Then, 10 artificial soiling cloths and a knitted cloth are put into the bath, the bath ratio is adjusted to 30 times, and the washing is performed at 120 rpm and 25 ° C. for 10 minutes. The washing liquid is 900 ml with a detergent concentration of 0.083%, and the rinsing is performed with 900 ml of water for 3 minutes. The water used is 3 ゜ DH.

(3) Evaluation method The cleaning rate was determined by the following equation.

[0091]

(Equation 1)

K / S = (1−R / 100) / (2R / 100) where R is the reflectance (%) measured by a reflectometer.
It is. The evaluation of the detergency was carried out by the average value of 10 test artificial soil cloths.

(4) Detergent A solid content was obtained by using the components shown in Tables 6 and 7 except for nonionic surfactants, some silicates, some sodium carbonate, enzymes and fragrances. Using a countercurrent spray-drying tower, a 60% detergent slurry was used at a hot air temperature of 270 ° C. and a water content of 5%.
% To obtain a spray-dried product.

The spray-dried product, a nonionic surfactant,
And water were introduced into a continuous kneader to obtain a dense and uniform kneaded product. At the outlet of this kneader, a perforated plate (thickness 10 mm) having 80 hole diameters of 5 mmφ was installed, and the kneaded material was weighed about 5 m.
It was a cylindrical pellet of mφ × 10 mm.

The pellets were doubled (by weight) at 15 ° C.
And introduced into the crusher together with the cooling air. The crusher has a cutter with a length of 15 cm and four stages of cloth,
The screen is rotated at 0 rpm, the screen is made of 360-degree punched metal, and has a hole diameter of 20 mmφ and an opening of 20%.

The particles passed through the screen were mixed with the chelating agent compositions of Tables 1 and 2, 6.5% by weight of finely divided sodium carbonate and 2% by weight of silicate powder, and the enzyme, By adding a fragrance, a detergent composition having the composition shown in Tables 6 and 7 below was evaluated, and the detergency was evaluated.

The meanings and details of the abbreviations in Tables 6 and 7 are as follows. EOp represents the average addition mole number of ethylene oxide, and POp represents the average addition mole number of propylene oxide.

(1) Builder chelating agent composition: In Tables 1 and 2, composition N
o. The composition indicated by. Silicates: A-type zeolite Carbonate K: Potassium carbonate Sodium carbonate: Sodium carbonate (2) Anionic surfactant α-SF: α-sulfo fatty acid (C14-C16) sodium methyl ester AOS: C14-C18 α-olefin sulfonic acid Sodium LAS: Sodium alkylbenzene sulfonate (alkyl group C10 to C14) (3) Nonionic surfactant AE: C12 alcohol ethoxylate (EOp = 1)
5) NFE: Nonylphenol ethoxylate (EOp = 1
5) AOE • PO: EO • PO of C12-C13 alcohol
Adduct (EOp = 15, POp = 5) FEE: C ₁₁ H ₂₃ CO (OCH ₂ OCH ₂ ) ₁₅ OCH ₃ (4) Bleach Na percarbonate: sodium percarbonate Na perborate: sodium perborate (5) Enzyme Protease Amylase Cellulase Lipase (6) Other additives Na sulfite: sodium sulfite Glauber's salt: sodium sulfate Fluorescent agent PAa: sodium polyacrylate PEG400: polyethylene glycol # 400

[0099]

[Table 6]

[0100]

[Table 7]

As is evident from Tables 6 and 7, the detergent composition of the present invention shows a better cleaning effect than using a single chelating agent.

Example 3 A 10% aqueous suspension of diatomaceous earth was uniformly applied to a glass plate, and then heated and dried at 105 ° C. for 8 hours to produce an artificially soiled plate. Using this artificial soil plate, cleaning efficiency was evaluated for cleaning solution aqueous solutions (Sample Nos. 17 to 28) having the compositions shown in Table 8. The chelating agent compositions are listed in Tables 1 and 2 under composition No. The one indicated by is used. The washing efficiency is determined by immersing the artificial stain plate in a detergent solution heated to a temperature of 80 ° C. for 10 minutes, washing, rinsing with warm water, and sufficiently drying to reduce the amount of stain remaining on the surface of the artificial stain plate. The measurement was performed using a gloss meter, and the cleaning efficiency was calculated from the measured value and the measured value of the gloss value of the artificial stain plate of the detergent. Table 9 shows the results. The aqueous solution of the detergent has a calcium carbonate concentration of 60 p.
It was prepared using two types of water, pm and 200 ppm.

[0103]

[Table 8]

[0104]

[Table 9]

Table 9 shows that the use effect of the present chelating agent composition can be seen even with respect to inorganic stains adhering to the glass surface. In particular, the effect is high even when the detergent aqueous solution is hard water having a hardness of either 60 ppm or 200 ppm.

Example 4 Copper Plating Table 10 shows the plating rate when the diamine-type biodegradable chelating agent of the present invention was used as a complexing agent. Table 10 also shows the presence or absence of precipitation of cuprous oxide and findings on bath stability. However, the plating rate is shown as the thickness of the copper film formed per hour. (Measurement conditions) Cu ⁺⁺ ion donor concentration: 40.0 m as CuSO4
M Reducing agent concentration: 37.0 mM as HCHO Complexing agent concentration: 50.0 mM 2′-Pipyridyl concentration: 20 ppm Diethylene glycol: 1000 ppm Plating bath temperature: 90 ° C. pH: 12.0 However, the analysis conditions and symbols in Table 1 are as follows: It is as follows. (Analytical conditions) Plating rate: Increase in plating film mass per hour per test plate of 10 cm ² mg (symbol) ：: Extremely stable ○: Stable △: Slightly unstable ×: Unstable, bath decomposition

[0107]

[Table 10]

Example 5 Ni Plating Table 11 shows the maximum plating rate when the diamine type biodegradable chelating agent of the present invention was used as a complexing agent. Table 11 also shows the bath pH and buffering power (change in pH), P content, and bath stability at the maximum plating rate. (Measurement Conditions) Ni ⁺⁺ ion supply _{concentration: NiSO 4 · 6 (H 2} 0) as 0.10M reducing agent _{concentration: NaH 2 PO 2 · (H} 2 0) as 0.2
0 M Complexing agent concentration: 0.07 M Plating temperature: 80 ° C. pH adjustment: H ₂ SO ₄ and NH ₄ OH However, the analysis conditions and symbols in Table 1 are as follows. (Analysis conditions) Speed: Increase in plating film mass per 60 minutes of test plate of 10 cm ² mg Change in pH: Gives the maximum plating speed when the pH of the plating bath is measured in 0.5 steps in the pH range of 4 to 10. p
H value and pH after completion of measurement • P content: P mass% in generated Ni-P alloy coating (symbol) ◎: extremely stable ：: stable ：: slightly unstable ×: unstable, bath decomposition

[0109]

[Table 11]

As is clear from Tables 10 and 11, the plating bath composition of the present invention has better bath stability, plating speed, and formed film formation than using a single chelating agent as a complexing agent. It is an excellent bath from all aspects of properties.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C11D 3/20 C11D 3/20 3/33 3/33 3/37 3/37 3/395 3/395 C23C 18/36 C23C 18/36 18/40 18/40 F term (reference) 4H003 AB15 AB19 AB21 AC08 AC11 AC12 AC23 DA01 DA02 DA03 DA09 DA12 DA14 DA15 DA17 EA12 EB13 EB30 EB36 EC01 EC02 EC03 FA03 FA07 4K022 AA02 AA04 AA05 AA13 BA08 BA14 BA08 DA01 DB01 DB02 DB06

Claims (19)

[Claims] 1. An at least one compound selected from an amino acid derivative represented by the following general formula (1) and a salt thereof, and at least one compound selected from an amino acid derivative represented by the following general formula (2) and a salt thereof: A chelating agent composition comprising the compound of the above. Embedded image [Wherein, A ^a and ^Ab are the same or different and each represent a straight-chain or branched-chain alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group, a phenyl group or an amino group; Y ^a and Y ^b are the same or different and each represent a carboxyl group or a sulfonic acid group, and W represents a straight-chain or branched-chain alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group. . ] [Wherein, R ^a and R ^b are the same or different and each represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by hydrogen, a hydroxyl group, a carboxyl group, a phenyl group or a sulfonic acid group. Shown, but not simultaneously hydrogen. A ^C represents a hydroxyl group, a carboxyl group, a phenyl group or an alkylene group having 1 to 6 carbon atoms which may linear or branched chain optionally substituted amino group,
^Yc represents a carboxyl group or a sulfonic acid group. ] 2. An amino acid derivative represented by the general formula (1) is ethylenediaminedisuccinic acid, trimethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, trimethylenediaminediglutaric acid, 2-hydroxy-trimethylenediaminediamine. The chelating agent composition according to claim 1, comprising at least one compound selected from the group consisting of succinic acid, 2-hydroxy-trimethylenediamine diglutaric acid and salts thereof. 3. The method according to claim 1, wherein the amino acid derivative represented by the general formula (1) is (S, S) -ethylenediaminedisuccinic acid,
(S, S) -trimethylenediamine disuccinic acid, (S,
(S) -ethylenediaminediglutaric acid, (S, S) -trimethylenediaminediglutaric acid, (S, S) -2-hydroxy-trimethylenediaminedisuccinic acid, (S,
The composition according to claim 1, comprising at least one compound selected from the group consisting of S) -2-hydroxy-trimethylenediamine diglutaric acid and salts thereof. 4. An amino acid derivative represented by the general formula (2) is aspartic acid-N-acetic acid, aspartic acid-N,
N-diacetic acid, aspartic acid-N-propionic acid, iminodisuccinic acid, aspartic acid-N-methanesulfonic acid, aspartic acid-N-2-ethanesulfonic acid, glutamic acid-N, N-diacetic acid, glutamic acid-N-methane Sulfonic acid, glutamic acid-N-2-ethanesulfonic acid, N-methyliminodiacetic acid, α-alanine-N, N-
Diacetate, β-alanine-N, N-diacetate, serine-N,
N-diacetate, isoserine-N, N-diacetate, phenylalanine-N, N-diacetate, anthranilic acid-N, N-diacetate, sulfanilic acid-N, N-diacetate, taurine-
2. The composition according to claim 1, comprising at least one compound selected from the group consisting of N, N-diacetate and salts thereof. 5. The amino acid derivative represented by the general formula (2) is (S) -aspartic acid-N-acetic acid, (S) -aspartic acid-N, N-diacetic acid, (S) -aspartic acid- N-propionic acid, (S, S) -iminodisuccinic acid,
(S, R) -iminodisuccinic acid, (S) -aspartic acid-N-methanesulfonic acid, (S) -aspartic acid-
N-2-ethanesulfonic acid, (S) -glutamic acid-
N, N-diacetate, (S) -glutamic acid-N-methanesulfonic acid, (S) -glutamic acid-N-2-ethanesulfonic acid, (S) -α-alanine-N, N-diacetic acid,
2. The composition according to claim 1, comprising at least one compound selected from the group consisting of (S) -serine-N, N-diacetate, (S) -phenylalanine-N, N-diacetate and salts thereof.
A composition as described. 6. The chelating agent composition according to claim 1, wherein the salt is a metal salt, an ammonium salt, or an amine salt. 7. The method according to claim 1, wherein the molar ratio of the amino acid derivative represented by the general formula (1) or a salt thereof to the amino acid derivative represented by the general formula (2) or a salt thereof is 1/99 to 99/1. The chelating composition according to any one of the preceding claims. 8. A cleaning composition comprising the chelating agent composition according to claim 1. 9. A cleaning composition having the following composition. (A) The chelating agent composition according to claim 1: 0.5 to 80.
Mass% (b) nonionic surfactant, anionic surfactant and / or cationic surfactant: 0.2 to 60 mass% 10. A cleaning composition having the following composition.
(A) The chelating agent composition according to claim 1: 0.5 to 80.
(B) Nonionic surfactant, anionic surfactant and / or cationic surfactant: 0.2 to 60% by mass (c) Silicates: 0.5 to 80% by mass (d) Bleaching agent : 0.5 to 60% by mass 11. The cleaning composition according to claim 8, further comprising 0.5 to 60% by mass of a softening agent. 12. A hard surface cleaning composition having the following composition. (A) the chelating agent composition according to claim 1: 0.5 to 20;
Mass% (b) alkali metal hydroxide: 0.2 to 10 mass% (c) gluconic acid: 0.5 to 20 mass% 13. A hard surface cleaning composition having the following composition. (A) the chelating agent composition according to claim 1: 0.5 to 20;
Mass% (b) alkali metal hydroxide: 0.2 to 10 mass% (c) gluconic acid: 0.5 to 20 mass% (d) scale formation inhibitor: 10 to 1000 ppm 14. The scale formation inhibitor is at least one of acrylic acid or an alkali metal salt thereof, a copolymer containing maleic acid or an alkali metal salt thereof, hexametaphosphoric acid and / or an alkali metal salt thereof. The hard surface cleaning composition according to claim 12 or 13, wherein 15. A plating bath containing the chelating agent composition according to claim 1. 16. NaOH, KOH and / or NH
_The electroless plating bath according to claim 15, wherein the bath is made alkaline with ₄ OH. 17. The method according to claim 15, wherein formalin and / or sodium hypophosphite is used as the reducing agent.
Electroless plating bath as described. 18. The method according to claim 15, wherein 2,2′-bipyridyl, orthophenanthrin, potassium ferrocyanide, thiourea, and neofproin are used as the trace additives.
18. The electroless plating bath according to 17. 19. The electroless plating bath according to claim 15, wherein metal ions used for plating are copper and nickel.